Isotopic characteristics of canopies in simulated leaf assemblages

NASA Astrophysics Data System (ADS)

Graham, Heather V.; Patzkowsky, Mark E.; Wing, Scott L.; Parker, Geoffrey G.; Fogel, Marilyn L.; Freeman, Katherine H.

2014-11-01

The geologic history of closed-canopy forests is of great interest to paleoecologists and paleoclimatologists alike. Closed canopies have pronounced effects on local, continental and global rainfall and temperature patterns. Although evidence for canopy closure is difficult to reconstruct from the fossil record, the characteristic isotope gradients of the ;canopy effect; could be preserved in leaves and proxy biomarkers. To assess this, we employed new carbon isotopic data for leaves collected in diverse light environments within a deciduous, temperate forest (Maryland, USA) and for leaves from a perennially closed canopy, moist tropical forest (Bosque Protector San Lorenzo, Panamá). In the tropical forest, leaf carbon isotope values range 10‰, with higher δ13Cleaf values occurring both in upper reaches of the canopy, and with higher light exposure and lower humidity. Leaf fractionation (Δleaf) varied negatively with height and light and positively with humidity. Vertical 13C enrichment in leaves largely reflects changes in Δleaf, and does not trend with δ13C of CO2 within the canopy. At the site in Maryland, leaves express a more modest δ13C range (∼6‰), with a clear trend that follows both light and leaf height. Using a model we simulate leaf assemblage isotope patterns from canopy data binned by elevation. The re-sampling (bootstrap) model determined both the mean and range of carbon isotope values for simulated leaf assemblages ranging in size from 10 to over 1000 leaves. For the tropical forest data, the canopy's isotope range is captured with 50 or more randomly sampled leaves. Thus, with a sufficient number of fossil leaves it is possible to distinguish isotopic gradients in an ancient closed canopy forest from those in an open forest. For very large leaf assemblages, mean isotopic values approximate the δ13C of carbon contributed by leaves to soil and are similar to observed δ13Clitter values at forested sites within Panamá, including the site where leaves were sampled. The model predicts a persistent ∼1‰ difference in δ13Clitter for the two sites which is consistent with higher water availability in the tropical forests. This work provides a new framework for linking contemporary ecological observations to the geochemical record using flux-weighted isotope data and lends insights to the effect of forest architecture on organic and isotopic records of ancient terrestrial ecosystems. How many leaves from a litter assemblage are necessary to distinguish the isotopic gradient characteristics of canopy closure? Are mean δ13Cleaf values for a litter assemblage diagnostic of a forest biome? Can we predict the δ13C values of cumulative litter, soil organic matter, and organic carbon in sedimentary archives using litter flux and isotope patterns in canopies? We determined the δ13C range and mean for different sized assemblages of leaves sampled from data for each forest. We re-sampled very high numbers of leaves in order to estimate the isotopic composition of cumulative carbon delivered to soils as litter, and compared these results to available data from forest soils. Modeled leaf and soil organic carbon isotope patterns in this study offer insights to how forest structure can be derived from carbon isotope measurements of fossil leaves, as well as secondary material - such as teeth, hair, paleosol carbonates, or organic soil carbon (van der Merwe and Medina, 1989; Koch, 1998; Secord et al., 2008; Levin et al., 2011).Distinct climate and seasonal difference in the Panamá and Maryland, USA forests are reflected in their canopy isotope gradients. In the tropical forest of Panamá, leaves are produced throughout the year within a canopy that is both extensively and persistently closed (Leigh, 1975; Lowman and Wittman, 1996). In the temperate forest of Maryland leaves are produced during the spring when canopy conditions are relatively open (Korner and Basler, 2010).

δ 18O(PO 43-) and δ 18O(CO 32-) from belemnite guards from Eastern Europe: implications for palaeoceanographic reconstructions and for the preservation of pristine isotopic values

NASA Astrophysics Data System (ADS)

Longinelli, Antonio; Wierzbowski, Hubert; Di Matteo, Antonella

2003-04-01

The oxygen isotopic composition of coexisting carbonate and phosphate from belemnite rostra was measured according to well established techniques in 42 samples of Early and Middle Jurassic age and in five samples of oyster shells. Most of the samples come from various locations in the Western Carpathians of Slovakia and Ukraine, and from central Poland. Three samples come from the Isle of Skye. The phosphate content of belemnite rostra, though variable, is systematically very low: consistently lower than about 0.3%. However, this phosphate concentration is close to that found in shells of modern marine organisms including pelecypods, gastropods and Sepia cuttlebones which, in some way, could be considered the modern belemnite counterpart. The measured oxygen isotopic composition of carbonate is within the normal range of values obtained from these fossils ranging from about -1.3 to about +0.6‰ (PDB-1) with the exception of three samples; the δ 13C values range from about -0.8 to about +2.8‰ (PDB-1). With the single exception of one sample from the Isle of Skye, the oxygen isotopic composition of phosphate from belemnite rostra ranges from +19.8 to +24.9‰ (V-SMOW), 22 of the samples measured showing δ 18O values equal to or heavier than +23.0‰. In contrast, the oyster values are considerably lighter, in the case of both carbonate and phosphate. 18O-enriched values can hardly be related to diagenetic processes that normally cause an oxygen isotope shift towards light values. If deposition temperatures are calculated from the heavily enriched values by means of the equation of Longinelli and Nuti [Earth Planet. Sci. Lett. 19 (1973) 373-376] and assuming the δ 18O of Jurassic ocean water to be equal to -1‰ taking into account the lack of ice caps during the Jurassic, the obtained temperatures range from about 8°C to about zero. These temperatures are obviously unreliable when Mesozoic palaeoceanographic conditions and palaeoclimate are taken into account. Two different hypotheses are suggested to explain these results, other hypotheses being rejected as unreliable. (1) Phosphate derived from the decaying organic matter of belemnites might have been introduced into belemnite rostra by early diagenetic fluids. If the phosphate of belemnite organic matter was isotopically heavy as happens nowadays in the flesh of molluscs, the inflow of this phosphate into the rostra could be responsible for the very positive δ 18O values shown by many belemnite rostra (this hypothesis is suggested by H.W.); (2) previous oxygen isotope measurements on Upper Cretaceous belemnites yielded δ 18O values very close to the most positive values obtained from Lower Tertiary pelecypods and fish teeth which are known to precipitate their phosphate under isotopic equilibrium conditions with seawater. These data suggest the possibility that the phosphate in belemnite rostra is primary phosphate so that the very positive data reported here can be considered the result of good preservation of the pristine isotopic composition of primary phosphate. Consequently, the only way to explain the very positive δ 18O values is to consider the oxygen isotopic composition of Jurassic ocean water to be more positive than nowadays by at least 3‰. This hypothesis is suggested by A.L. and A.D.M.

Stable isotopes of C and S as indicators of habitat use by fish in small oregon Coast range streams

EPA Science Inventory

We are using stable isotopes of C, N, O and S (H planned) to study the ecology of coho salmon in streams of the Oregon Coast Range. We have found isotopes of C and, surprisingly, S to be very useful in discriminating rearing habitats in our small streams. We found 13C values ...

Fontinalis antipyretica as a bioindicator of environmental conditions in freshwater ecosystem from Sava River watershed and Cerknişko Lake, Slovenia

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Mechora, Špela; Stibilj, Vekoslava

2014-05-01

Polluted waters recharging from agriculture water systems into watersheds have influence on water quality and living habitat. Stable isotopes of carbon and nitrogen in combination with other minor and trace elements are often used to trace biogeochemical processes and contamination of water systems. The aim of the study was to assess state of environment with minor and trace elements and stable isotopes of C and N in selected Slovenian streams. Ten locations in Notranjska region, Slovenia, with different land use in the catchment (town, village, agricultural areas, farms, dairy farms), including reference point considered as non-polluted site, were sampled. Samples of water and aquatic moss F. antipyretica in Slovenian fresh waters were taken in all four seasons during years 2010 and 2012, but for stable isotope analyses of C and N only in three seasons during years 2010 and 2011. The water chemistry of investigated locations is dominated by hydrogen carbonate - calcium - magnesium, concentrations of nitrate seasonally range from 2.07 mg/l to 6.4 mg/l and at reference site does not exceed 1.3 mg/l. Total alkalinity of water at investigated locations ranges from 2.9 to 6.02 mM. The pH of investigated water range from 7.2 to 8.5, waters are saturated with oxygen (up to 134%) and conductivity ranges from 295 to 525 mikroS/cm, while at reference site conductivity is up to 180 mikroS/cm. The content of minor and trace elements in F. antipyretica ranged for Ni 4-38 mikrog/g, Zn 17-105 mikrog/g, Pb 2-28 mikrog/g, Cd 220-1953 ng/g, Cu 4-27 mikrog/g, Cr 4-49 mikrog/g, As 1-6 mikrog/g and Se 0.33-3.24 mikrog/g. The most polluted watershed was Pšata stream (agricultural areas, cattle farm) with highest values for Ni, Cr, Pb, Zn and As. The highest content of Se, was found in village (dairy farms) in Žerovniščica stream. The highest values were measured in February and October. Isotopic composition of dissolved inorganic carbon seasonally range from -13.3 to -8.1‰, and indicate waters dominated by degradation of organic matter and dissolution of carbonates. At the reference point average measured isotopic composition of dissolved inorganic carbon value is -2.7‰ which confirmed that this is a non-polluted site. Isotopic composition of carbon of F. antipyretica seasonally ranges from -45 to -32.9‰ and isotopic composition of nitrogen from -0.2‰ to 6.5‰, respectively. In comparison to C3 terrestrial plants F. antipyretica has more negative isotopic composition of carbon value, which is probably related with the difference in CO2 plant fixation and depends on isotopic composition of dissolved inorganic carbon in water, which is primarily controlled by geological composition and soil thickness in the watershed. Higher isotopic composition of nitrogen value found in F. antipyretica is related to agricultural activity in watershed, while at the reference site measured isotopic composition of nitrogen value is -4.1 ‰. From our study it is evident that isotopic composition of carbon and nitrogen is useful tracer of natural and anthropogenic inputs from terrestrial (fertilizing, sewage sludge) to water system.

Tracing industrial heavy metal inputs to topsoils using using cadmium isotopes

NASA Astrophysics Data System (ADS)

Huang, Y.; Ma, L.; Ni, S.; Lu, H.; Liu, Z.; Zhang, C.; Guo, J.; Wang, N.

2015-12-01

Anthropogenic activities have dominated heavy metal (such as Cd, Pb, and Zn) cycling in many environments. The extent and fate of these metal depositions in topsoils, however, have not been adequately evaluated. Here, we utilize an innovative Cadmium (Cd) isotope tool to trace the sources of metal pollutants in topsoils collected from surrounding a Vanadium Titanium Magnetite smelting plant in Sichuan, China. Topsoil samples and possible pollution end-members such as fly ashes, bottom ashes, ore materials, and coal were also collected from the region surrounding the smelting plant and were analyzed for Cd isotope ratios (d114Cd relative to Cd NIST 3108). Large Cd isotope fractionation (up to 3 ‰) was observed in these industrial end-members: fly ashes possessed higher δ114Cd values ranging from +0.03 to +0.19‰; bottom fly ashes have lower δ114Cd values ranging from -0.35 to -2.46‰; and unprocessed ore and coal samples has δ114Cd value of -0.40‰. This fractionation can be attributed to the smelting processes during which bottom ashes acquired lighter Cd isotope signatures while fly ashes were mainly characterized by heavy isotope ratios, in comparison to the unprocessed ore and coal samples. Indeed, δ114Cd values of topsoils in the smelting area range from 0.29 to -0.56‰, and more than half of the soils analyzed have distinct δ114Cd values > 0‰. Cd isotopes and concentrations measured in topsoils suggested that processed materials (fly and bottom ashes from ore and coal actually used by the smelting plant) were the major source of Cd in soils. In a δ114Cd vs 1/Cd mixing diagram, the soils represent a mixture of three identified end members (fly ash, bottom ash and deep unaffected soil) with distinct Cd isotopic compositions and concentrations. Deep soils have the same δ114Cd values range as the unprocessed ore and coal, which indicated the Cd isotope fractionation did occur during evaporation and condensation processes inside the smelting plant. The signatures of fly ash end member might be even higher according to the δ114Cd increasing trend of topsoils with the increasing of Cd concentration of the topsoils. Our study suggested that δ114Cd values can be used to distinguish sources of anthropogenic Cd and to construct metal budgets in in this studying area.

Silicon isotope fractionation in rice and cucumber plants over a life cycle: Laboratory studies at different external silicon concentrations

NASA Astrophysics Data System (ADS)

Sun, Yan; Wu, Lianghuan; Li, Xiaoyan; Sun, Li; Gao, Jianfei; Ding, Tiping

2016-11-01

Understanding the variations of silicon isotopes in terrestrial higher plants can be helpful toward elucidating the global biogeochemical silicon cycle. We studied silicon isotope fractionation in rice and cucumber plants over their entire life cycles. These two different silicon-absorbing plants were grown hydroponically at different external silicon concentrations. The ranges of δ30Si values in rice were -1.89‰ to 1.69‰, -1.81‰ to 1.96‰, and -2.08‰ to 2.02‰ at 0.17 mM, 1.70 mM, and 8.50 mM silicon concentrations, respectively. The ranges of δ30Si values in cucumber were -1.38‰ to 1.21‰, -1.33‰ to 1.26‰, and -1.62‰ to 1.40‰ at 0.085 mM, 0.17 mM, and 1.70 mM external silicon concentrations, respectively. A general increasing trend in δ30Si values from lower to upper plant parts reflected the preferential incorporation of lighter silicon isotopes from transpired water to biogenic opal. Furthermore, the active uptake mechanism regulated by several transporters might have also played an important role in the preferential transport of heavy silicon isotopes into aboveground plant parts. This suggested that silicon isotope fractionation in both rice and cucumber was a Rayleigh-like process. The data on δ30Si values for the whole plants and nutrient solutions indicated that biologically mediated silicon isotope fractionation occurred during silicon uptake by roots. At lower external silicon concentrations, heavy silicon isotopes entered plants more readily than light silicon isotopes. Conversely, at higher external silicon concentrations, light silicon isotopes entered plants more readily than heavy silicon isotopes.

Stable Isotope Biogeochemistry of Seabird Guano Fertilization: Results from Growth Chamber Studies with Maize (Zea Mays)

PubMed Central

Szpak, Paul; Longstaffe, Fred J.; Millaire, Jean-François; White, Christine D.

2012-01-01

Background Stable isotope analysis is being utilized with increasing regularity to examine a wide range of issues (diet, habitat use, migration) in ecology, geology, archaeology, and related disciplines. A crucial component to these studies is a thorough understanding of the range and causes of baseline isotopic variation, which is relatively poorly understood for nitrogen (δ15N). Animal excrement is known to impact plant δ15N values, but the effects of seabird guano have not been systematically studied from an agricultural or horticultural standpoint. Methodology/Principal Findings This paper presents isotopic (δ13C and δ15N) and vital data for maize (Zea mays) fertilized with Peruvian seabird guano under controlled conditions. The level of 15N enrichment in fertilized plants is very large, with δ15N values ranging between 25.5 and 44.7‰ depending on the tissue and amount of fertilizer applied; comparatively, control plant δ15N values ranged between −0.3 and 5.7‰. Intraplant and temporal variability in δ15N values were large, particularly for the guano-fertilized plants, which can be attributed to changes in the availability of guano-derived N over time, and the reliance of stored vs. absorbed N. Plant δ13C values were not significantly impacted by guano fertilization. High concentrations of seabird guano inhibited maize germination and maize growth. Moreover, high levels of seabird guano greatly impacted the N metabolism of the plants, resulting in significantly higher tissue N content, particularly in the stalk. Conclusions/Significance The results presented in this study demonstrate the very large impact of seabird guano on maize δ15N values. The use of seabird guano as a fertilizer can thus be traced using stable isotope analysis in food chemistry applications (certification of organic inputs). Furthermore, the fertilization of maize with seabird guano creates an isotopic signature very similar to a high-trophic level marine resource, which must be considered when interpreting isotopic data from archaeological material. PMID:22479435

The preliminary result of the δ65Cu and δ34S values of major ore minerals in the Erdenetiin-Ovoo Cu-Mo porphyry deposit, Northern Mongolia

NASA Astrophysics Data System (ADS)

KIM, Y.; Lee, I.; Oyungerel, S.; Jargal, L.; Tsedenbal, T.; Ryu, J. S.

2016-12-01

The copper isotope (δ65Cu) and sulfur isotope (δ34S) compositions of major ore minerals from the Erdenetiin-Ovoo Cu-Mo porphyry deposit were measured to trace sources of copper and sulfur, and to evaluate the precipitation environment of ore minerals. The major ore minerals are pyrite, chalcopyrite, molybdenite and chalcocite developed in the QSP (Quartz-Sericite-Pyrite) alteration zone. The sulfide minerals such as sphalerite and covellite, and carbonate ore minerals like malachite, azurite are also identified. The copper isotope ratios (65Cu/63Cu) of copper ore minerals (chalcopyrite, chalcocite, malachite, azurite, covellite and chrysocolla) were analyzed by the MC-ICPMS in KBSI located in Ochang, South Korea. The measured δ65Cu values relative to NIST 976 range from -1.01 ‰ to 5.76 ‰. The average δ65Cu values of sulfide minerals such as chalcopyrite (1.03 ‰), chalcocite (0.62 ‰) and covellite (0.51 ‰) seem to be relatively lower than those of carbonate and silicate Cu minerals such as malachite (0.24 ‰), azurite (2.17 ‰) and chrysocolla (5.76 ‰). The sulfur isotope ratios (34S/32S) of major sulfide minerals were measured by EA-CF-IRMS (Elemental Analyzer - Continuous Flow - Isotope Ratio Mass Spectrometer) in NCIRF, Seoul National University. The average δ34SV-CDT value is -1.1 ‰ indicating the magmatic signature of sulfur. There is the difference of δ34S values between sulfide minerals. While the δ34S values of pyrite, chalcopyrite and molybdenite range from -0.9 to 0.8 ‰, the δ34S values of chalcocite range from -2.6 ‰ to -1.4 ‰. These lower values might be attributed to the sulfur isotope fractionation during its precipitation.

Iron isotope fractionation in marine invertebrates in near shore environments

NASA Astrophysics Data System (ADS)

Emmanuel, S.; Schuessler, J. A.; Vinther, J.; Matthews, A.; von Blanckenburg, F.

2014-04-01

Chitons (Mollusca) are marine invertebrates that produce radula (teeth or rasping tongue) containing high concentrations of biomineralized magnetite and other iron bearing minerals. As Fe isotope signatures are influenced by redox processes and biological fractionation, Fe isotopes in chiton radula might be expected to provide an effective tracer of ambient oceanic conditions and biogeochemical cycling. Here, in a pilot study to measure Fe isotopes in marine invertebrates, we examine Fe isotopes in modern marine chiton radula collected from different locations in the Atlantic and Pacific oceans to assess the range of isotopic values, and to test whether or not the isotopic signatures reflect seawater values. Furthermore, by comparing two species that have very different feeding habits but collected from the same location, we infer a possible link between diet and Fe isotopic signatures. Values of δ56Fe (relative to IRMM-014) in chiton teeth range from -1.90 to 0.00‰ (±0.05‰ (2σ) uncertainty in δ56Fe), probably reflecting a combination of geographical control and biological fractionation processes. Comparison with published local surface seawater Fe isotope data shows a consistent negative offset of chiton teeth Fe isotope compositions relative to seawater. Strikingly, two different species from the same locality in the North Pacific (Puget Sound, Washington, USA) have distinct isotopic signatures. Tonicella lineata, which feeds on red algae, has a mean δ56Fe of -0.65 ± 0.26‰ (2σ, 3 specimens), while Mopalia muscosa, which feeds primarily on green algae, shows lighter isotopic values with a mean δ56Fe of -1.47 ± 0.98‰ (2σ, 5 specimens). Although chitons are not simple recorders of the ambient seawater Fe isotopic signature, these preliminary results suggest that Fe isotopes provide information concerning Fe biogeochemical cycling in near shore environments, and might be used to probe sources of Fe in the diets of different organisms.

Sulfur Isotopic Composition of Sulfides in Skarn and Vein Mineralization of the Dal'negorsk Ore Region (Primorye)

NASA Astrophysics Data System (ADS)

Rogulina, L. I.; Moiseenko, V. G.; Odarichenko, E. G.; Voropayeva, E. N.

2018-03-01

The S isotopic composition in the ore-forming minerals galena and sphalerite was studied in different Ag-Pb-Zn deposits of the region. It was pointed out that the δ34S modal values range from-1.2 to +6.7‰ in the minerals with a positive value for the skarn mineralization. In the flyschoid formation, the vein-type mineralization is characterized by negative and positive values. The narrow range of δ34S values indicates the marginal-continental type of the mineralization and the multiple origins of its sources.

The early bird gets the shrimp: Confronting assumptions of isotopic equilibrium and homogeneity in a wild bird population

USGS Publications Warehouse

Wunder, Michael B.; Jehl, Joseph R.; Stricker, Craig A.

2012-01-01

1. Because stable isotope distributions in organic material vary systematically across energy gradients that exist in ecosystems, community and population structures, and in individual physiological systems, isotope values in animal tissues have helped address a broad range of questions in animal ecology. It follows that every tissue sample provides an isotopic profile that can be used to study dietary or movement histories of individual animals. Interpretations of these profiles depend on the assumption that metabolic pools are isotopically well mixed and in equilibrium with dietary resources prior to tissue synthesis, and they extend to the population level by assuming isotope profiles are identically distributed for animals using the same proximal dietary resource. As these assumptions are never fully met, studying structure in the variance of tissue isotope values from wild populations is informative. 2. We studied variation in δ13C, δ15N, δ2H and δ18O data for feathers from a population of eared grebes (Podiceps nigricollis) that migrate to Great Salt Lake each fall to moult feathers. During this time, they cannot fly and feed almost exclusively on superabundant brine shrimp (Artemia franciscana). The ecological simplicity of this situation minimized the usual spatial and trophic complexities often present in natural studies of feather isotope values. 3. Ranges and variances of isotope values for the feathers were larger than those from previously published studies that report feather isotopic variance, but they were bimodally distributed in all isotope dimensions. Isotope values for proximal dietary resources and local surface water show that some of the feathers we assumed to have been grown locally must have been grown before birds reached isotopic equilibrium with local diet or immediately prior to arrival at Great Salt Lake. 4. Our study provides novel insights about resource use strategies in eared grebes during migration. More generally, it demonstrates the utility of studying variance structures and questioning assumptions implicit in the interpretation of stable isotope data from wild animals.

Non-lethal sampling of walleye for stable isotope analysis: a comparison of three tissues

USGS Publications Warehouse

Chipps, Steven R.; VanDeHey, J.A.; Fincel, M.J.

2012-01-01

Stable isotope analysis of fishes is often performed using muscle or organ tissues that require sacrificing animals. Non-lethal sampling provides an alternative for evaluating isotopic composition for species of concern or individuals of exceptional value. Stable isotope values of white muscle (lethal) were compared with those from fins and scales (non-lethal) in walleye, Sander vitreus (Mitchill), from multiple systems, size classes and across a range of isotopic values. Isotopic variability was also compared among populations to determine the potential of non-lethal tissues for diet-variability analyses. Muscle-derived isotope values were enriched compared with fins and depleted relative to scales. A split-sample validation technique and linear regression found that isotopic composition of walleye fins and scales was significantly related to that in muscle tissue for both δ13C and δ15N (r2 = 0.79–0.93). However, isotopic variability was significantly different between tissue types in two of six populations for δ15N and three of six populations for δ13C. Although species and population specific, these findings indicate that isotopic measures obtained from non-lethal tissues are indicative of those obtained from muscle.

Tracking Urban Air Deterioration in San Francisco: Carbon and Nitrogen Isotope Study of Weedy Plants.

NASA Astrophysics Data System (ADS)

Colman, A. S.; Wessells, A.; Swaine, M. E.; Fogel, M. L.

2003-12-01

Stable isotopes of carbon and nitrogen have long been used as indicators of ecosystem structure and nutrient cycling in natural and anthropogenically disturbed terrestrial ecosytems. However, relatively few of these studies have targeted urban environments, where nitrogen and CO2 emissions dramatically impact atmospheric composition. Here we present the results of carbon and nitrogen isotope analyses of herbaceous plants growing in and around San Francisco. These plants were collected mainly as part of a public outreach walking tour of San Francisco ("The Weed Walk - Concrete Jungle") sponsored by the San Francisco Exploratorium. In all cases, the plants were sampled in areas with negligible forest canopy. A consortium of species was collected at each of several distinct sites to examine the localized and regional impact of automobile traffic and proximity to the ocean on isotopic compositions of carbon and nitrogen. δ 13C measurements trend towards relatively light values in the range of --26 to --36 permil. In comparison, the leaves from similar types of herbaceous species in relatively unpolluted and unforested environments typically have δ 13C values in the range of --22 to --28 permil. The observed light carbon isotopic compositions potentially reflect input of isotopically light CO2 emissions from fossil fuel burning, boosting atmospheric CO2 concentrations to >10 % above background. δ 15N values range from +4 to +9 permil. This is substantially offset from the --4 to +1 permil values that typify vegetation in regions where nitrogen oxides from fossil fuel combustion dominate the nitrogen inputs. The nitrogen isotope compositions might suggest nitrogen contributions from a marine source (typically +6 permil).

A Stable Isotope Study of Fluid-Rock Interactions in the Saddlebag Lake Roof Pendant, Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Lojasiewicz, I.; Hartman, S. M.; Holk, G. J.; Paterson, S. R.

2015-12-01

The Saddlebag Lake Pendant (SLP) is a ~ 100 km2 zone of Ordovician-Cretaceous metasedimentary and metavolcanic rocks just east of the 95-85 Ma Tuolumne Intrusive Complex (TIC) in the Sierra Nevada of central California. Western SLP and adjacent parts of TIC are affected by the Steelhead Lake Shear Zone (SLSZ), with leucogranitic dikes, abundant qz-tm veins, ductile epidote-chlorite alteration, and massive qz veins. While TIC shows uniform stable isotope values, isotope studies of other Sierra Nevada pendants evidence diversity of fluid sources: Jurassic seawater, Cretaceous magmatic fluids, metamorphic fluids, and meteoric-hydrothermal fluids. We conducted a stable isotope study of 49 samples from units across the SLSZ, focusing on the shear zone. Unlike other pendants, both δ18 O and δD values from SLSZ showed great variability, and most samples were not in isotopic equilibrium. Overall, δ18 O mineral values ranged from -1.5‰(plag) to +15.8‰(bt); mineral δD values ranged from -140‰(tm) to -67‰(bt). TIC δ18 O was +7.8 to +10.0 (plag) and +4.8 to +9.2 (tm), normal magmatic values, and δD were -105 to -75. Paleozoic and Triassic metasedimentary units had most qz δ18 O from +11.3 to +15.8, so within metamorphic range, and δD from -100 to -72 (ep and tm). Jurassic metasedimentary units (Sawmill) and Triassic metavolcanics (Koip) had largest isotopic variability: δ18 O qz from +8.1 to +14.8, plag from -1.1 to +11.8, but ep and tm between +1.3 and +9.3 and δD between -108 and -81. All lower (submagmatic) isotopic values were from a wider, possibly transtensional, part of the SLSZ, transected by Sawmill Canyon. Although TIC and many of the Paleozoic units do not show isotopic evidence for alteration, the Koip and Sawmill units were likely infiltrated by later magmatic waters, and then subjected to very localized meteoric water infiltration in the area surrounding Sawmill Canyon.

Land use and mobility during the Neolithic in Wales explored using isotope analysis of tooth enamel

PubMed Central

Montgomery, Janet; Evans, Jane; Cook, Gordon T.; Scarre, Chris

2017-01-01

Abstract Objectives The nature of land use and mobility during the transition to agriculture has often been debated. Here, we use isotope analysis of tooth enamel from human populations buried in two different Neolithic burial monuments, Penywyrlod and Ty Isaf, in south‐east Wales, to examine patterns of land use and to evaluate where individuals obtained their childhood diet. Materials and Methods We employ strontium (87Sr/86Sr) and oxygen (δ18O) and carbon (δ13C) isotope analysis of enamel from adjacent molars. We compare strontium isotope values measured in enamel to locally bioavailable 87Sr/86Sr values. We combine discussion of these results with evaluation of new radiocarbon dates obtained from both sites. Results The majority of enamel samples from Penywyrlod have strontium isotope ratios above 0.7140. In contrast, the majority of those from Ty Isaf have 87Sr/86Sr values below 0.7140. At Penywyrlod oxygen isotope ratios range between 25.9 and 28.2 ‰ (mean 26.7 ± 0.6 ‰, 1σ, n = 15) and enamel δ13Ccarbonate values range between −18.0 and −15.0 ‰ (mean −16.0 ± 0.8 ‰, 1σ, n = 15). At Ty Isaf oxygen isotope ratios exhibited by Neolithic individuals range between 25.4 and 27.7 ‰ (mean 26.7 ± 0.6 ‰, 1σ, n = 15) and enamel δ13Ccarbonate values range between −16.9 and −14.9 ‰ (mean −16.0 ± 0.6 ‰, 1σ, n = 15). Discussion The strontium isotope results suggest that the majority of individuals buried at Penywyrlod did not source their childhood diet locally. One individual in this group has strontium isotope ratios that exceed all current known biosphere values within England and Wales. This individual is radiocarbon dated to the first few centuries of the 4th millennium BC, consistent with the period in which agriculture was initiated in Wales: the results therefore provide evidence for migration during the transition to farming in Wales. In contrast, all individuals sampled from Ty Isaf post‐date the period in which agriculture is considered to have been initiated and could have sourced their childhood diet from the local region in which they were buried. PMID:28752654

Sources and fractionation processes influencing the isotopic distribution of H, O and C in the Long Valley hydrothermal system, California, U.S.A.

USGS Publications Warehouse

White, A.F.; Peterson, M.L.; Wollenberg, H.; Flexser, S.

1990-01-01

The isotopic ratios of H, O and C in water within the Long Valley caldera, California reflect input from sources external to the hydrothermal reservoir. A decrease in ??D in precipitation of 0.5??? km-1, from west to east across Long Valley, is caused by the introduction of less fractionated marine moisture through a low elevation embayment in the Sierra Nevada Mountain Range. Relative to seasonal fluctuations in precipitation (-158 to -35??.), ??D ranges in hot and cold surface and groundwaters are much less variable (-135 to -105??.). Only winter and spring moisture, reflecting higher precipitation rates with lighter isotopic signatures, recharge the hydrological system. The hydrothermal fluids are mixtures of isotopically heavy recharge (??D = - 115???, ??18O = - 15???) derived from the Mammoth embayment, and isotopically lighter cold water (??D = -135???, ??18O = -18???). This cold water is not representative of current local recharge. The ??13C values for dissolved carbon in hot water are significantly heavier (- 7 to - 3???) than in cold water (-18 to -10???) denoting a separate hydrothermal origin. These ??13C values overlie the range generally attributed to magmatic degassing of CO2. However, ??13C values of metamorphosed Paleozoic basement carbonates surrounding Long Valley fall in a similar range, indicating that hydrothermal decarbonization reactions are a probable source of CO2. The ??13C and ??18O values of secondary travertime and vein calcite indicate respective fractionation with CO2 and H2O at temperatures approximating current hydrothermal conditions. ?? 1990.

Silicon isotope fractionation by marine sponges and the reconstruction of the silicon isotope composition of ancient deep water

NASA Astrophysics Data System (ADS)

de La Rocha, Christina L.

2003-05-01

The silicon isotope composition (δ30Si) of biogenic opal provides a view of the silica cycle at times in the past. Reconstructions require the knowledge of silicon isotope fractionation during opal biomineralization. The δ30Si of specimens of hexactinellid sponges and demosponges growing in the modern ocean ranged from -1.2‰ to -3.7‰ (n = 6), corresponding to the production of opal that has a δ30Si value 3.8‰ ± 0.8‰ more negative than seawater silicic acid and a fractionation factor (α) of 0.9964. This is three times the fractionation observed during opal formation by marine diatoms and terrestrial plants and is the largest fractionation of silicon isotopes observed for any natural process on Earth. The δ30Si values of sponge spicules across the Eocene-Oligocene boundary at Ocean Drilling Program Site 689 on Maud Rise range from -1.1‰ to -3.0‰, overlapping the range observed for sponges growing in modern seawater.

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

NASA Astrophysics Data System (ADS)

Kavner, Abby; Bonet, François; Shahar, Anat; Simon, Justin; Young, Edward

2005-06-01

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from -0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ 56Fe values (relative to IRMM-14) ranging from -0.18(±0.02) to -2.290(±0.006) ‰, and corresponding δ 57Fe values of -0.247(±0.014) and -3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus's theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.

Mass Dependent Fractionation of Hg Isotopes in Source Rocks, Mineral Deposits and Spring Waters of the California Coast Ranges, USA

NASA Astrophysics Data System (ADS)

Smith, C. N.; Kesler, S. E.; Blum, J. D.; Rytuba, J. J.

2007-12-01

We present here the first study of the isotopic composition of Hg in rocks, ore deposits, and active hydrothermal systems from the California Coast Ranges, one of Earth's largest Hg-depositing systems. The Franciscan Complex and Great Valley Sequence, which form the bedrock in the California Coast Ranges, are intruded and overlain by Tertiary volcanic rocks including the Clear Lake Volcanic Sequence. These rocks contain two types of Hg deposits, hot-spring deposits that form at shallow depths (<300 m) and silica-carbonate deposits that extend to greater depths (200 to 1000 m), as well as active springs and geothermal systems that release Hg to the present surface. The Franciscan Complex and Great Valley Sequence contain clastic sedimentary rocks with higher concentrations of Hg than volcanic rocks of the Clear Lake Volcanic Field. Mean Hg isotope compositions for all three rock units are similar, although the range of values in Franciscan Complex rocks is greater than in either Great Valley or Clear Lake rocks. Hot spring and silica-carbonate Hg deposits have similar average isotopic compositions that are indistinguishable from averages for the three rock units, although δ202Hg values for the Hg deposits have a greater variance than the country rocks. Precipitates from dilute spring and saline thermal waters in the area have similarly large variance and a mean δ202Hg value that is significantly lower than the ore deposits and rocks. These observations indicate there is little or no isotopic fractionation during release of Hg from its source rocks into hydrothermal solutions. Isotopic fractionation does appear to take place during transport and concentration of Hg in deposits, especially in their uppermost parts. Boiling of hydrothermal fluids is likely the most important process causing of the observed Hg isotope fractionation. This should result in the release of Hg with low δ202Hg values into the atmosphere from the top of these hydrothermal systems and a consequent enrichment in heavy Hg isotopes in the upper crust through time.

Trophic niche of squids: Insights from isotopic data in marine systems worldwide

NASA Astrophysics Data System (ADS)

Navarro, Joan; Coll, Marta; Somes, Christoper J.; Olson, Robert J.

2013-10-01

Cephalopods are an important prey resource for fishes, seabirds, and marine mammals, and are also voracious predators on crustaceans, fishes, squid and zooplankton. Because of their high feeding rates and abundance, squids have the potential to exert control on the recruitment of commercially important fishes. In this review, we synthesize the available information for two intrinsic markers (δ15N and δ13C isotopic values) in squids for all oceans and several types of ecosystems to obtain a global view of the trophic niches of squids in marine ecosystems. In particular, we aimed to examine whether the trophic positions and trophic widths of squid species vary among oceans and ecosystem types. To correctly compare across systems, we adjusted squid δ15N values for the isotopic variability of phytoplankton at the base of the food web provided by an ocean circulation-biogeochemistry-isotope model. Studies that focused on the trophic ecology of squids using isotopic techniques were few, and most of the information on squids was from studies on their predators. Our results showed that squids occupy a large range of trophic positions and exploit a large range of trophic resources, reflecting the versatility of their feeding behavior and confirming conclusions from food-web models. Clear differences in both trophic position and trophic width were found among oceans and ecosystem types. The study also reinforces the importance of considering the natural variation in isotopic values when comparing the isotopic values of consumers inhabiting different ecosystems.

Lithium and boron in late-orogenic granites - Isotopic fingerprints for the source of crustal melts?

NASA Astrophysics Data System (ADS)

Romer, Rolf L.; Meixner, Anette; Förster, Hans-Jürgen

2014-04-01

Geochemically diverse late- and post-Variscan granites of the Erzgebirge-Vogtland, the Saxon Granulite Massif, and Thuringia (Germany) formed by anatectic melting of Palaeozoic sedimentary successions and associated mafic to felsic volcanic rocks. The compositional diversity of the least evolved of these granites is largely inherited from the protoliths. We present Li and B-isotopic data of these granites and compare them with the isotopic composition of their protoliths, to investigate whether (i) there exist systematic differences in the Li and B-isotopic composition among different granite types and (ii) Li and B-isotopic compositions provide information on the granite sources complementary to information from the isotopic composition of Sr, Nd, and Pb and the trace-element signatures. Low-F biotite and two-mica granite types have flat upper continental crust (UCC)-normalized trace-element pattern with variable enrichments in Li, Rb, Cs, Sn, and W and depletions in Sr, Ba, and Eu. These signatures are least pronounced for the Niederbobritzsch biotite granite, which has the largest contribution of mafic material, and most pronounced for the two-mica granites. The granites show a relatively narrow range of δ7Li values (-3.0 to -0.5) and a broad range of δ11B values (-13.4 to +20.1). The δ11B values are lower in rocks with distinctly higher contents of Li, Rb, Cs, and Sn. The high δ11B of the Niederbobritzsch granite may be explained by the melting of former altered oceanic crust in its source. Relative to UCC, intermediate-F to high-F low-P granites show strong depletions in Sr, Ba, Eu as well as Zr and Hf, strong enrichments in Li, Rb, and Cs as well as Nb, Sn, Ta, and W, and REE pattern with stronger enrichments for HREE than for LREE. These granites show narrow ranges of δ7Li (-2.0 to +1.6) and δ11B values (-14.7 to -9.1), reflecting the smaller variability of the Li and B-isotopic composition in their source lithologies. The anomalously high δ7Li value (14.7) of one granite sample (Burgberg), which is similar to δ7Li values of its wall rocks (up to 14.5), may indicate late-magmatic fluid-rock interaction with external, wall rock-derived fluids. Because of the small compositional range of most source lithologies, the Li and B-isotopic variation in the granites is also small indicating that the isotopic composition of Li and B does not represent a particularly sensitive source tracer, with the exception of source lithologies characterized by extreme δ7Li or δ11B values.

Variation of lithium isotope geochemistry during basalt weathering and secondary mineral transformations in Hawaii

NASA Astrophysics Data System (ADS)

Ryu, Jong-Sik; Vigier, Nathalie; Lee, Sin-Woo; Lee, Kwang-Sik; Chadwick, Oliver A.

2014-11-01

Lithium isotopes are a potential tracer of silicate weathering but the relationship between lithium isotope compositions and weathering state still need to be established with precision. Here, we report Li concentrations and Li isotope compositions of soils developed along a 4 million year humid-environment chronosequence in the Hawaiian Islands. Li concentrations are variable with depth and age, ranging from 0.24 to 21.3 ppm, and significant Li depletions (up to 92%) relative to parent basalts are systematically enhanced towards the surface. Our calculations show that the relative contribution from atmospheric deposits to the Li soil budget remains small, with a maximum contribution from dust Li of 20% at the oldest site. This is explained by the capacity of the weathering products to retain, within the profiles, the Li coming from basalt alteration, and allows us to explore more specifically the role of alteration processes on soil Li isotope signatures. The δ7Li values display a large range between -2.5‰ and +13.9‰. The youngest soils (0.3 ka) display the same δ7Li value as fresh basalt, regardless of depth, despite ∼30% Li loss by leaching, indicating that there is little Li isotope fractionation during the incipient stage of weathering. δ7Li values for the older soils (⩾20 ka) vary non-linearly as a function of time and can be explained by progressive mineral transformations starting with the synthesis of metastable short-range order (nano-crystalline) minerals and followed by their transformation into relatively inert secondary minerals. Results highlight significant Li isotope fractionation during secondary mineral formation and in particular during Li uptake by kaolinite. Finally, we suggest that the non-monotonous evolution of the regolith δ7Li value over the last 4 Ma is consistent with climatic variations, where congruent release of Li isotopes occurs during warmer periods.

Stable Isotope Systematics in Grasshopper Assemblages Along an Elevation Gradient, Colorado

NASA Astrophysics Data System (ADS)

Kohn, M. J.; Evans, S.; Dean, J.; Nufio, C.

2012-12-01

Insects comprise over three quarters of all animal species, yet studies of body water isotopic composition are limited to only the cockroach, the hoverfly, and chironomid flies. These studies suggest that oxygen and hydrogen isotopic compositions in body water are primarily controlled by dietary water sources, with modification from respiratory and metabolic processes. In particular, outward diffusion of isotopically depleted water vapor through insect spiracles at low humidity enriches residual body water in 18O and 2H (D). Stable isotope compositions (δ18O and δD) also respond to gradients in elevation and humidity, but these influences remain poorly understood. In this study, we measured grasshopper body water and local vegetation isotopic compositions along an elevation gradient in Colorado to evaluate three hypotheses: 1) Insect body water isotopic composition is directly related to food source water composition 2) Water vapor transport alters body water isotopic compositions relative to original diet sources, and 3) Elevation gradients influence isotopic compositions in insect body water. Thirty-five species of grasshopper were collected from 14 locations in Colorado grasslands, ranging in elevation from 450 to 800 meters (n=131). Body water was distilled from previously frozen grasshopper specimens using a vacuum extraction line, furnaces (90 °C), and liquid nitrogen traps. Water samples were then analyzed for δ18O and δD on an LGR Liquid Water Isotope Analyzer, housed in the Department of Geosciences, Boise State University. Grasshopper body water isotopic compositions show wide variation, with values ranging between -76.64‰ to +42.82‰ in δD and -3.06‰ to +26.78‰ in δ18O. Precipitation δ18O values over the entire Earth excluding the poles vary by approximately 30‰, comparable to the total range measured in our single study area. Most grasshopper values deviate from the global meteoric water line relating δ18O and δD in precipitation, consistent with evaporative enrichment in food (plants) due to plant transpiration. However, grasshopper body water from any given location is further enriched in 18O and D relative to food. Isotopic values decrease slightly with increasing elevation, but some specific grasshopper species appear more sensitive to elevation. Overall, evaporative enrichment of 18O and D in this relatively dry environment appears the strongest factors influencing grasshopper compositions.

Isotopic assessment of marine food consumption by natural-foraging chacma baboons on the Cape Peninsula, South Africa.

PubMed

Lewis, Matthew C; West, Adam G; O'Riain, M Justin

2018-01-01

Stable isotope analysis has been used to investigate consumption of marine resources in a variety of terrestrial mammals, including humans, but not yet in extant nonhuman primates. We sought to test the efficacy of stable isotope analysis as a tool for such studies by comparing isotope- and observation-based estimates of marine food consumption by a troop of noncommensal, free-ranging chacma baboons. We determined δ 13 C and δ 15 N values of baboon hair (n = 9) and fecal samples (n = 144), and principal food items (n = 362). These values were used as input for diet models, the outputs of which were compared to observation-based estimates of marine food consumption. Fecal δ 13 C values ranged from -29.3‰ to -25.6‰. δ 15 N values ranged from 0.9‰ to 6.3‰ and were positively correlated with a measure of marine foraging during the dietary integration period. Mean (± SD) δ 13 C values of adult male and female baboon hairs were -21.6‰ (± 0.1) and -21.8‰ (± 0.3) respectively, and corresponding δ 15 N values were 5.0‰ (± 0.3) and 3.9‰ (± 0.2). Models indicated that marine contributions were ≤10% of baboon diet within any season, and contributed ≤17% of dietary protein through the year. Model output and observational data were in agreement, both indicating that despite their abundance in the intertidal region, marine foods comprised only a small proportion of baboon diet. This suggests that stable isotope analysis is a viable tool for investigating marine food consumption by natural-foraging primates in temperate regions. © 2017 Wiley Periodicals, Inc.

Re-Os isotopic evidence for an enriched-mantle source for the Noril'sk-type, ore-bearing intrusions, Siberia

USGS Publications Warehouse

Walker, R.J.; Morgan, J.W.; Horan, M.F.; Czamanske, G.K.; Krogstad, E.J.; Fedorenko, V.A.; Kunilov, V.E.

1994-01-01

Magmatic Cu-Ni sulfide ores and spatially associated ultramafic and mafic rocks from the Noril'sk I, Talnakh, and Kharaelakh intrusions are examined for Re-Os isotopic systematics. Neodymium and lead isotopic data also are reported for the ultramafic and mafic rocks. The Re-Os data for most samples indicate closed-system behavior since the ca. 250 Ma igneous crystallization age of the intrusions. There are small but significant differences in the initial osmium isotopic compositions of samples from the three intrusions. Ores from the Noril'sk I intrusion have ??Os values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have ??Os values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have ??Os values that range from +7.8 to +12.9, with an average value of +10.4. The osmium isotopic compositions of the ore samples from the Main Kharaelakh orebody exhibit minimal overlap with those for the Noril'sk I and Talnakh intrusions, indicating that these Kharaelakh ores were derived from a more radiogenic source of osmium than the other ores. Combined osmium and lead data for major orebodies in the three intrusions plot in three distinct fields, indicating derivation of osmium and lead from at least three isotopically distinct sources. Some of the variation in lead isotopic compositions may be the result of minor lower-crustal contamination. However, in contrast to most other isotopic and trace element data, Os-Pb variations are generally inconsistent with significant crustal contamination or interaction with the subcontinental lithosphere. Thus, the osmium and lead isotopic compositions of these intrusions probably reflect quite closely the compositions of their mantle source, and suggest that these two isotope systems were insensitive to lithospheric interaction. Ultramafic and mafic rocks have osmium and lead isotopic compositions that range only slightly beyond the compositions of the ores. These rocks also have relatively uniform ??{lunate}Nd values that range only from -0.8 to + 1.1. This limited variation in neodymium isotopic composition may reflect the characteristics of the mantle sources of the rocks, or it may indicate that somehow similar proportions of crust contaminated the parental melts. The osmium, lead, and neodymium isotopic data for these rocks most closely resemble the mantle sources of certain ocean island basalts (OIB), such as some Hawaiian basalts. Hence, these data are consistent with derivation of primary melts from a mantle source similar to that of some types of hotspot activity. The long-term Re/Os enrichment of this and similar mantle sources, relative to chondritic upper mantle, may reflect 1. (1) incorporation of recycled oceanic crust into the source more than 1 Ga ago, 2. (2) derivation from a mantle plume that originated at the outer core-lower mantle interface, or 3. (3) persistence of primordial stratification of rhenium and osmium in the mantle. ?? 1994.

Temperature effects on the fractionation of multiple sulfur isotopes by Thermodesulfobacterium and Desulfovibrio strains

NASA Astrophysics Data System (ADS)

Wang, P.; Sun, C.; Ono, S.; Lin, L.

2012-12-01

Microbial dissimilatory sulfate reduction is one of the major mechanisms driving anaerobic mineralization of organic matter in global ocean. While sulfate-reducing prokaryotes are well known to fractionate sulfur isotopes during dissimilatory sulfate reduction, unraveling the isotopic compositions of sulfur-bearing minerals preserved in sedimentary records could provide invaluable constraints on the evolution of seawater chemistry and metabolic pathways. Variations in the sulfur isotope fractionations are partly due to inherent differences among species and also affected by environmental conditions. The isotope fractionations caused by microbial sulfate reduction have been interpreted to be a sequence of enzyme-catalyzed isotope fractionation steps. Therefore, the fractionation factor depends on (1) the sulfate flux into and out of the cell, and (2) the flux of sulfur transformation between the internal pools. Whether the multiple sulfur isotope effect could be quantitatively predicted using such a metabolic flux model would provide insights into the cellular machinery catalyzing with sulfate reduction. This study examined the multiple sulfur isotope fractionation patterns associated with a thermophilic Thermodesulfobacterium-related strain and a mesophilic Desulfovibrio gigas over a wide temperature range. The Thermodesulfobacterium-related strain grew between 34 and 79°C with an optimal temperature at 72°C and the highest cell-specific sulfate reduction rate at 77°C. The 34ɛ values ranged between 8.2 and 31.6‰ with a maximum at 68°C. The D. gigas grew between 10 and 45 °C with an optimal temperature at 30°C and the highest cell-specific sulfate reduction rate at 41°C. The 34ɛ values ranged between 10.3 and 29.7‰ with higher magnitude at both lower and higher temperatures. The results of multiple sulfur isotope measurements expand the previously reported range and cannot be described by a solution field of the metabolic flux model, which calculates the Δ33S and 34ɛ values assuming equilibrium fractionation among internal steps. Either larger isotope effects or kinetic fractionation has to be considered in the metabolic flux model to explain the multiple sulfur isotope effect produced by these two strains. Overall, the metabolic flux model warrants further revision and further studies regarding physiological responses to growth conditions may probably offer a linkage between multiple sulfur isotope effects and environmental factors for microbial dissimilatory sulfate reduction.

Labile pools of Pb in vegetable-growing soils investigated by an isotope dilution method and its influence on soil pH.

PubMed

Xie, Hong; Huang, Zhi-Yong; Cao, Ying-Lan; Cai, Chao; Zeng, Xiang-Cheng; Li, Jian

2012-08-01

Pollution of Pb in the surface of agricultural soils is of increasing concern due to its serious impact on the plant growth and the human health through the food chain. However, the mobility, activity and bioavailability of Pb rely mainly on its various chemical species in soils. In the present study, E and L values, the labile pools of isotopically exchangeable Pb, were estimated using the method of isotope dilution in three vegetable-growing soils. The experiments involved adding a stable enriched isotope ((206)Pb > 96%) to a soil suspension and to soils in which plants are subsequently grown, the labile pools of Pb were then estimated by measuring the isotopic composition of Pb in soil solutions and in the plant tissues, respectively. In addition, the correlation of E values and soil pH was investigated at the ranges of pH 4.5-7.0. The amount of labile Pb in soils was also estimated using different single chemical extractants and a modified BCR approach. The results showed that after spiking the enriched isotopes of (206)Pb (>96%) for 24 hours an equilibration of isotopic exchanges in soil suspensions was achieved, and the isotope ratios of (208)Pb/(206)Pb measured at that time was used for calculating the E(24 h) values. The labile pools of Pb by %E(24 h) values, ranging from 53.2% to 61.7% with an average 57%, were found to be significantly higher (p < 0.05) than the values estimated with L values, single chemical extractants and the Σ(BCR) values obtained with the BCR approach, respectively. A strong negative correlation (R(2) = 0.984) between E(24 h) values and soil pH was found in the tested soil sample. The results indicate that the %E(24 h) value can more rapidly and easily predict the labile pools of Pb in soils compared with L values, but it might be readily overestimated because of the artificial soil acidity derived from the spiked isotopic tracer and the excess of spiked enriched isotopes. The results also suggest that the amounts of Pb extracted with EDTA and the Σ(BCR) values extracted with the modified BCR approach are helpful to detect the labile pools of Pb in soils. In addition, the negative correlation between soil pH and the labile pools of Pb in soils may be useful for further remediation to reduce the bioavailability of Pb in contaminated soils.

New reference materials for nitrogen-isotope-ratio measurements

USGS Publications Warehouse

Böhlke, John Karl; Gwinn, C. J.; Coplen, T. B.

1993-01-01

Three new reference materials were manufactured for calibration of relative stable nitrogen-isotope-ratio measurements: USGS25 (ammonium sulfate) d15N' = -30 per mil; USGS26 (ammonium sulfate) d15N' = +54 per mil; USGS32 (potassium nitrate) d15N' = +180 per mil, where d15N', relative to atmospheric nitrogen, is an approximate value subject to change following interlaboratory comparisons. These materials are isotopically homogeneous in aliquots at least as small as 10 µmol N2 (or about 1-2 mg of salt). The new reference materials greatly extend the range of d15N values of internationally distributed standards, and they allow normalization of d15N measurements over almost the full range of known natural isotope variation on Earth. The methods used to produce these materials may be adapted to produce homogeneous local laboratory standards for routine use.

Nicotine, acetanilide and urea multi-level2H-,13C- and15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry

USGS Publications Warehouse

Schimmelmann, A.; Albertino, A.; Sauer, P.E.; Qi, H.; Molinie, R.; Mesnard, F.

2009-01-01

Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ??13C and ??13N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ??2Hnicotine -162 to -45%o, ??13Cnicotine -30.05 to +7.72%, ?? 15Nnicotine -6.03 to +33.62%; ??15N acetanilide +1-18 to +40.57%; ??13Curea -34.13 to +11.71%, ??15Nurea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ??13N values. Comparative ??13C and ??15N on-line EA-IRMS data from 14 volunteering laboratories document the usefulness and reliability of acetanilides and ureas as EA-IRMS reference materials.

Recycling of subducted crustal components into carbonatite melts revealed by boron isotopes

NASA Astrophysics Data System (ADS)

Hulett, Samuel R. W.; Simonetti, Antonio; Rasbury, E. Troy; Hemming, N. Gary

2016-12-01

The global boron geochemical cycle is closely linked to recycling of geologic material via subduction processes that have occurred over billions of years of Earth’s history. The origin of carbonatites, unique melts derived from carbon-rich and carbonate-rich regions of the upper mantle, has been linked to a variety of mantle-related processes, including subduction and plume-lithosphere interaction. Here we present boron isotope (δ11B) compositions for carbonatites from locations worldwide that span a wide range of emplacement ages (between ~40 and ~2,600 Ma). Hence, they provide insight into the temporal evolution of their mantle sources for ~2.6 billion years of Earth’s history. Boron isotope values are highly variable and range between -8.6‰ and +5.5‰, with all of the young (<300 Ma) carbonatites characterized by more positive δ11B values (>-4.0‰), whereas most of the older carbonatite samples record lower B isotope values. Given the δ11B value for asthenospheric mantle of -7 +/- 1‰, the B isotope compositions for young carbonatites require the involvement of an enriched (crustal) component. Recycled crustal components may be sampled by carbonatite melts associated with mantle plume activity coincident with major tectonic events, and linked to past episodes of significant subduction associated with supercontinent formation.

Chromium isotope heterogeneity in the mantle

NASA Astrophysics Data System (ADS)

Xia, Jiuxing; Qin, Liping; Shen, Ji; Carlson, Richard W.; Ionov, Dmitri A.; Mock, Timothy D.

2017-04-01

To better constrain the Cr isotopic composition of the silicate Earth and to investigate potential Cr isotopic fractionation during high temperature geological processes, we analyzed the Cr isotopic composition of different types of mantle xenoliths from diverse geologic settings: fertile to refractory off-craton spinel and garnet peridotites, pyroxenite veins, metasomatised spinel lherzolites and associated basalts from central Mongolia, spinel lherzolites and harzburgites from North China, as well as cratonic spinel and garnet peridotites from Siberia and southern Africa. The δ53CrNIST 979 values of the peridotites range from - 0.51 ± 0.04 ‰ (2SD) to + 0.75 ± 0.05 ‰ (2SD). The results show a slight negative correlation between δ53Cr and Al2O3 and CaO contents for most mantle peridotites, which may imply Cr isotopic fractionation during partial melting of mantle peridotites. However, highly variable Cr isotopic compositions measured in Mongolian peridotites cannot be caused by partial melting alone. Instead, the wide range in Cr isotopic composition of these samples most likely reflects kinetic fractionation during melt percolation. Chemical diffusion during melt percolation resulted in light Cr isotopes preferably entering into the melt. Two spinel websterite veins from Mongolia have extremely light δ53Cr values of - 1.36 ± 0.04 ‰ and - 0.77 ± 0.06 ‰, respectively, which are the most negative Cr isotopic compositions yet reported for mantle-derived rocks. These two websterite veins may represent crystallization products from the isotopically light melt that may also metasomatize some peridotites in the area. The δ53Cr values of highly altered garnet peridotites from southern Africa vary from - 0.35 ± 0.04 ‰ (2SD) to + 0.12 ± 0.04 ‰ (2SD) and increase with increasing LOI (Loss on Ignition), reflecting a shift of δ53Cr to more positive values by secondary alteration. The Cr isotopic composition of the pristine, fertile upper mantle is estimated as δ53Cr = - 0.14 ± 0.12 ‰, after corrections for the effects of partial melting and metasomatism. This value is in line with that estimated for the BSE (- 0.12 ± 0.10 ‰) previously.

Compound-Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer.

PubMed

Clark, Justin A; Stotler, Randy L; Frape, Shaun K; Illman, Walter A

2017-01-01

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis-DCE compound-specific isotope analysis of carbon and chlorine collected over a 16-month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis-DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ 37 Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis-DCE. Carbon isotopic values range between -28.9 and -20.7‰ VPDB for TCE, and -26.5 and -11.8‰ VPDB for cis-DCE. In most wells, isotopic values remained steady over the 15-month study. Isotopic enrichment from TCE to cis-DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine-carbon isotopic enrichment ratios (ϵ Cl /ϵ C ) were 0.18 for TCE and 0.69 for cis-DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume. © 2016, National Ground Water Association.

Predicting the solubility and lability of Zn, Cd, and Pb in soils from a minespoil-contaminated catchment by stable isotopic exchange

NASA Astrophysics Data System (ADS)

Marzouk, E. R.; Chenery, S. R.; Young, S. D.

2013-12-01

The Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (<0.22 μm) colloidal particles (SCP-metal). For most soils, the presence of non-labile SCP-metal caused only minor over-estimation of E-values (<2%) but the effect was greater for soils with particularly large humus or carbonate contents. Approximately 80%, 53% and 66% of the variability in Zn, Cd and Pb %E-values (respectively) could be explained by pH, loss on ignition and total metal content. E-values were affected by the presence of ore minerals at high metal contents leading to an inconsistent trend in the relationship between %E-value and soil metal concentration. Metal solubility, in the soil suspensions used to measure E-values, was predicted using the WHAM geochemical speciation model (versions VI and VII). The use of total and isotopically exchangeable metal as alternative input variables was compared; the latter provided significantly better predictions of solubility, especially in the case of Zn. Lead solubility was less well predicted by either version of WHAM, with over-prediction at low pH and under-prediction at high soil pH values. Quantify the isotopically exchangeable fractions of Zn, Cd and Pb (E-values), and assess their local and regional variability, using multi-element stable isotope dilution, in a diverse range of soil ecosystems within the catchment of an old Pb/Zn mining area. Assess the controlling influences of soil properties on metal lability and develop predictive algorithms for metal lability in the contaminated catchment based on simple soil properties (such as pH, organic matter (LOI), and total metal content). Examine the incidence of non-isotopically-exchangeable metal held within suspended colloidal particles (SCP-metal) in filtered soil solutions (<0.22 μm) by comparing E-values from isotopic abundance in solutions equilibrated with soil and in a resin phase equilibrated with the separated solution. Assess the ability of a geochemical speciation model, WHAM(VII), to predict metal solubility using isotopically exchangeable metal as an input variable.

Sulphur stable isotope systematics in diagenetic pyrite from the North Sea hydrocarbon reservoirs revealed by laser combustion analysis.

PubMed

Fallick, Anthony E; Boyce, Adrian J; McConville, Paul

2012-01-01

Our study focuses on pyrite nodules developed in the Brent Group sandstones, which host the Brent Oilfield, one of the North Sea's greatest oil and gas producers. Timing of nodule formation is equivocal, but due to the forceful, penetrative textures that abound, it is considered late. This pyrite offers a research opportunity because it records the development of the supply of H(2)S in a hydrocarbon reservoir and its sulphur isotopic composition. Laser-based analysis of δ(34)S reveals an extraordinary diversity in values and patterns. The values range from-27 to+72‰, covering half the terrestrial range, with large variations at the submillimetre scale. Isotopically heavy (δ(34)S ∼+30‰ or higher) sulphide is endemic, but low δ(34)S pyrite is also present and appears to represent a temporally though not spatially (on the ∼cm scale) distinct pyritisation event. The distribution of δ(34)S values within individual concretions can be normal (Gaussian), but in some cases may reflect progressive isotope fractionation process(es), conceivably of Rayleigh type. The source of the sulphur and the identity of the isotope fractionation process(es) remain enigmatic.

Stable isotopic constraints on the tectonic, topographic, and climatic evolution of the northern margin of the Tibetan Plateau

NASA Astrophysics Data System (ADS)

Kent-Corson, Malinda L.; Ritts, Bradley D.; Zhuang, Guangsheng; Bovet, Paul M.; Graham, Stephan A.; Page Chamberlain, C.

2009-05-01

This study presents oxygen and carbon isotopic records from lacustrine, paleosol, alluvial, and fluvial carbonate sampled in thirteen Cenozoic sedimentary sections that span the northern margin of the Tibetan Plateau. Isotopic analyses of 1475 carbonate samples yield δ18O values that range from 13.1 to 38.9‰ (SMOW), and δ13C values range from - 11.5 to 3.7‰ (PDB). Based on these analyses, we see two isotopic trends regionally. We interpret a Paleogene decrease in average oxygen isotope values to result from an increase in the mean elevation of the study region's drainages as they tapped waters from a growing Tibetan Plateau to the south of the study area. We interpret a Neogene increase in both carbon and oxygen isotope values to result from the initiation of local mountain building in the study area and the withdrawal of marine waters, which increased basin isolation, aridity, and temperatures. The timing of inferred initiation of uplift in this region is consistent with structural, thermochronological, and sedimentological evidence for a tectonic transition in the early and middle Miocene from accommodation of India-Eurasia convergence through extrusion along the Altyn Tagh fault to accommodation of convergence through active shortening and mountain building in this region. This study also supports tectonic models for the differential uplift of the Tibetan Plateau, in that mountain building in this study region significantly postdates estimates for the attainment of high elevation from isotopic studies of the central Tibetan Plateau.

Osmium Stable Isotope Composition of Chondrites and Iron Meteorites: Implications for Planetary Core Formation

NASA Astrophysics Data System (ADS)

Nanne, J. A. M.; Millet, M. A.; Burton, K. W.; Dale, C. W.; Nowell, G. M.; Williams, H. M.

2016-12-01

Mass-dependent Os stable isotope fractionation is expected to occur during metal-silicate segregation as well as during crystallization of metal alloys due to the different bonding environment between silicate and metals. As such, Os stable isotopes have the potential to resolve questions pertaining to planetary accretion and differentiation. Here, we present stable Os isotope data for a set of chondrites and iron meteorites to examine the processes associated with core solidification. Carbonaceous, ordinary, and enstatite chondrites show no detectable stable isotope variation with a δ190Os weighted average of +0.12±0.04 (n=37). The uniform composition observed for chondrites implies Os stable isotope homogeneity of the bulk solar nebula. Contrary to chondrites, iron meteorites display a large range in Os stable isotope compositions from δ190Os of +0.05 up to +0.49‰. Variation is only observed in the IIAB and IIIAB irons. Type IVB irons display values similar to chondrites (+0.107±0.047 [n=3]) and IVA compositions are slightly different +0.187±0.004 (n=2). The type IIAB and IIIAB groups show values both within the chondritic range and up to heavier values extending up to +0.49‰. Since core formation in small planetary bodies is expected to quantitatively sequester Os in metal phases, bulk planetary cores are expected to display chondritic δ190Os values. Conversely, samples of the IIAB and IIIAB group display significant variation, possibly indicating that stable isotope fractionation occurred during solidification of the parent-body core. However, no covariation is observed between δ190Os and either Os abundance or radiogenic Os isotope ratios. Instead, liquid immiscibility during core crystallization, where the liquid metal splits into separate S- and P-rich liquids, may be a source of Os stable isotope fractionation.

Production of platinum radioisotopes at Brookhaven Linac Isotope Producer (BLIP)

NASA Astrophysics Data System (ADS)

Smith, Suzanne V.; McCutchan, Elizabeth; Gürdal, Gülhan; Lister, Christopher; Muench, Lisa; Nino, Michael; Sonzogni, Alexandro; Herman, Michal; Nobre, Gustavo; Cullen, Chris; Chillery, Thomas; Chowdury, Partha; Harding, Robert

2017-09-01

The accelerator production of platinum isotopes was investigated at the Brookhaven Linac Isotope Producer (BLIP). In this study high purity natural platinum foils were irradiated at 53.2, 65.7, 105.2, 151.9, 162.9 and 173.3.MeV. The irradiated foils were digested in aqua regia and then converted to their hydrochloride salt with concentrated hydrochloric acid before analyzing by gamma spectrometry periodically for at least 10 days post end of bombardment. A wide range of platinum (Pt), gold (Au) and iridium (Ir) isotopes were identified. Effective cross sections at BLIP for Pt-188, Pt-189, Pt-191 and Pt-195m were compared to literature and theoretical cross sections determined using Empire-3.2. The majority of the effective cross sections (<70 MeV) confirm those reported in the literature. While the absolute values of the theoretical cross sections were up to a factor of 3 lower, Empire 3.2 modeled thresholds and maxima correlated well with experimental values. Preliminary evaluation into a rapid separation of Pt isotopes from high levels of Ir and Au isotopes proved to be a promising approach for large scale production. In conclusion, this study demonstrated that with the use of isotopically enriched target material accelerator production of selected platinum isotopes is feasible over a wide proton energy range.

Sources of mercury to San Francisco Bay surface sediment as revealed by mercury stable isotopes

USGS Publications Warehouse

Gehrke, Gretchen E.; Blum, Joel D.; Marvin-DePasquale, Mark

2011-01-01

Mercury (Hg) concentrations and isotopic compositions were examined in shallow-water surface sediment (0–2 cm) from San Francisco (SF) Bay to determine the extent to which historic Hg mining contributes to current Hg contamination in SF Bay, and to assess the use of Hg isotopes to trace sources of contamination in estuaries. Inter-tidal and wetland sediment had total Hg (HgT) concentrations ranging from 161 to 1529 ng/g with no simple gradients of spatial variation. In contrast, inter-tidal and wetland sediment displayed a geographic gradient of δ202Hg values, ranging from -0.30% in the southern-most part of SF Bay (draining the New Almaden Hg District) to -0.99% in the northern-most part of SF Bay near the Sacramento–San Joaquin River Delta. Similar to SF Bay inter-tidal sediment, surface sediment from the Alviso Slough channel draining into South SF Bay had a δ202Hg value of -0.29%, while surface sediment from the Cosumnes River and Sacramento–San Joaquin River Delta draining into north SF Bay had lower average δ202Hg values of -0.90% and -0.75%, respectively. This isotopic trend suggests that Hg-contaminated sediment from the New Almaden Hg District mixes with Hg-contaminated sediment from a low δ202Hg source north of SF Bay. Tailings and thermally decomposed ore (calcine) from the New Idria Hg mine in the California Coast Range had average δ202Hg values of -0.37 and +0.03%, respectively, showing that Hg calcination fractionates Hg isotopes resulting in Hg contamination from Hg(II) mine waste products with higher δ202Hg values than metallic Hg(0) produced from Hg mines. Thus, there is evidence for at least two distinct isotopic signals for Hg contamination in SF Bay: Hg associated with calcine waste materials at Hg mines in the Coast Range, such as New Almaden and New Idria; and Hg(0) produced from these mines and used in placer gold mines and/or in other industrial processes in the Sierra Nevada region and SF Bay area.

Sulfur and Oxygen Isotopic Composition of Sulfate in the Fresh Water, King Sejong Station, King George Island, Antarctica

NASA Astrophysics Data System (ADS)

Kim, M.; Lee, I.; Lee, J.; Park, B.; Mayer, B.; Kaufman, A. J.; Park, S.; Kim, G.; Lee, K.

2008-12-01

Isotopic compositions of sulfur (δ34S) and oxygen (δ18O) were measured for the sulfate of the fresh water near the King Sejong Station, King George Island, Antarctica. Sejong station is located in the Barton peninsular of the King George Island. The geology around King Sejong station mainly composed of basalt-andesite, quart monzodiorite, and granodiorite. Lapilli tuff, conglomerate, sandstone, and siltstone occur along the southern and eastern shore of the Barton peninsula. Lapilli tuff also occurs on the highland located on southeastern part of the Barton peninsula. The δ34S values of sulfate extracted from fresh water samples at King Sejong Station range from 13.7 to 16.3 per mil excluding 1 sample. These sulfur values are very narrow in their range compared with those from anthropogenic sources. These sulfur values are 5 to 7 per mil lower than those of typical present seawater. Considering the rocks occurring near the King Sejong station, these sulfur isotopic values do not seem to be related to any evaporites of certain age. In Antarctic region the natural source of sulfate dissolved in water could be originated from marine biogenic source (DMS), sea-salt, volcanic source, or other continental sources. Most of the δ34S values of sulfate at King Sejong station seems to indicate the dominance of marine biogenic origin for the source of sulfur. The δ18O values of sulfate extracted from fresh water samples at King Sejong Station range from 1.9 to 6.4 per mil excluding 1 sample. These oxygen isotope values are lower than those of the sulfate in the present seawater by 6 per mil. However, both sulfur and oxygen isotope values strongly represent the influence of the seawater sulfate. One sample have 2.6 and -1.1 per mil in its δ34S and δ18O values, respectively, that are quite different from the isotopic values of other samples. This sample was collected in the highland far from the King Sejong station. Therefore this sample might reflect the composition of rather pure precipitation not affected by seawater sulfate. The atmospheric deposition might have been the major source of dissolved sulfate but it is not clear whether the source materials are from natural and/or anthropogenic origin.

Sr and Nd isotopes of suspended sediments from rivers of the Amazon basin

NASA Astrophysics Data System (ADS)

Hatting, Karina; Santos, Roberto V.; Sondag, Francis

2014-05-01

The Rb-Sr and Sm-Nd isotopic systems are important tools to constrain the provenance of sediment load in river systems. This study presents the isotopic composition of Sr and Nd isotopes and major and minor elements in suspended sediments from the Marañón-Solimões, Amazonas and Beni-Madeira rivers. The data were used to constrain the source region of the sediments and to better understand the main seasonal and spatial transport processes within the basin based on the variations of the chemical and isotopic signals. They also allow establishing a relationship between sediment concentrations and flow rate values. The study presents data collected during a hydrological year between 2009 and 2010. The Marañón-Solimões River presents low Sr isotopic values (0.7090-0.7186), broad EpslonNd(0) range (-15.17 to -8.09) and Nd model (TDM) ages varying from 0.99 to 1.81 Ga. Sources of sediments to the Marañón-Solimões River include recent volcanic rocks in northern Peru and Ecuador, as well as rocks with long crustal residence time and carbonates from the Marañón Basin, Peru. The Beni-Madeira River has more radiogenic Sr isotope values (0.7255-0.7403), more negative EpslonNd(0) values (-20.46 to -10.47), and older Nd isotope model ages (from 1.40 to 2.35 Ga) when compared to the Marañón-Solimões River. These isotope data were related to the erosion of Paleozoic and Cenozoic foreland basins that are filled with Precambrian sediments derived from the Amazonian Craton. These basins are located in Bolivian Subandina Zone. The Amazon River presents intermediate isotopic values when compared to those found in the Marañón-Solimões and Beni-Madeira rivers. Its Sr isotope ratios range between 0.7193 and 0.7290, and its EpslonNd(0) values varies between -11.09 and -9.51. The Nd isotope model ages of the suspended sediments vary between 1.28 and 1.77 Ga. Concentrations of soluble and insoluble elements indicate a more intense weathering activity in sediments of the Beni-Madeira River. This river has a larger difference in the Sr isotopic composition between the diluted and solid phases, which has been assigned to the high level of weathering of its sediment source area. In the Beni-Madeira River sub-basin dominates weathering of silicate rocks, while in the Marañón-Solimões River sub-basin there also weathering of carbonate and evaporitic rocks.

Iron isotopic systematics of pyroxenite xenoliths from North China Craton: implications for Melt-rock interaction in the sub-continental lithospheric mantle beneath eastern China

NASA Astrophysics Data System (ADS)

Zhao, X.; Cao, H.; Yu, H.; Huang, F.

2016-12-01

Iron isotope systems have become widely used tools in high temperature geochemistry and provide important constraints on mantle dynamics. Here, we report Fe isotopic data on a series of pyroxenite xenoliths from Hannuoba, North China Craton to further constrain the Fe isotopic composition of the mantle and investigate the behavior of Fe isotopes during mantle processes. These xenoliths range from Cr- pyroxenites, Al-pyroxenites to garnet pyroxenites, and are taken as physical evidence for different episodes of melt injection events. Our results show that both Cr- pyroxenites and Al-pyroxenites have a narrow range of Fe isotopes (δ57Fe=-0.01 to 0.09), similar to that reported typical mantle peridotites and they show equilibrium inter-mineral Fe isotope fractionation between coexisting mantle minerals. In contract, the garnet pyroxenites, which are products of reaction between a silicate melt and peridotite, exhibit larger Fe isotopic variations, with δ57Fe ranging from 0.08 to 0.30. The δ57Fe values of minerals in these garnet pyroxenites also vary widely from -0.25 to -0.03 in olivines, from -0.04 to 0.14 in orthopyroxenes, from -0.07 to 0.31 in clinopyroxenes, from 0.07 to 0.26 in spinels and from 0.30 to 0.39 in garnets. These observed data stand in marked contrast to the calculated equilibrium Fe isotope fractionation between coexisting mantle minerals at mantle temperature from theory, indicating disequilibrium isotope fractionation. The disequilibrium isotope fractionations between coexisting mantle minerals in garnet pyroxenites most likely reflect kinetic isotope fractionation during melt-peridotite interaction. In addition, the phlogopite clinopyroxenite with an apparent metasomatic overprint has the heaviest δ57Fe (as high as 1.00) but lightest δ26Mg (as low as -1.50) values of the investigated samples. Our study shows that mantle metasomatism plays an important role in producing Fe isotopic heterogeneity of the subcontinental mantle.

Patterns in Stable Isotope Values of Nitrogen and Carbon in ...

EPA Pesticide Factsheets

Stable isotope measurements of nitrogen and carbon (15N, 13ddC) are often used to characterize estuarine, nearshore, and open ocean ecosystems. Reliable information about the spatial distribution of base-level stable isotope values, often represented by primary producers, is critical to interpreting values in these ecosystems. While base-level isotope data are generally readily available for estuaries, nearshore coastal waters, and the open ocean, the continental shelf is less studied. To address this, and as a first step toward developing a surrogate for base-level isotopic signature in this region, we collected surface and deep water samples from the United States’ eastern continental shelf in the Western Atlantic Ocean, from the Gulf of Maine to Cape Hatteras, periodically between 2000 and 2013. During the study, particulate matter 15dN values ranged from 0.8 to 17.4‰, and 13dC values from −26.4 to −15.6‰over the region. We used spatial autocorrelation analysis and random forest modeling to examine the spatial trends and potential environmental drivers of the stable isotope values. We observed general trends toward lower values for both nitrogen and carbon isotopes at the seaward edge of the shelf. Conversely, higher 15dN and 13dC values were observed on the landward edge of the shelf, in particular in the southern portion of the sampling area. Across all sites, the magnitude of the difference between the 15dN of subsurface and surface particulate m

Hydrochemical and isotopic characterization of groundwater in the Ghis-Nekor plain (northern Morocco)

NASA Astrophysics Data System (ADS)

Chafouq, D.; El Mandour, A.; Elgettafi, M.; Himi, M.; Chouikri, I.; Casas, A.

2018-03-01

The coastal aquifer of Ghis-Nekor (Morocco) was studied to identify the major processes causing salinization of groundwater. In fact, a geochemical approach multi tracer (general chemistry and isotopes - δ2H, δ18O-H2O, δ34S, δ18O-SO4) was utilized, with the hydrodynamics to explain the processes responsible for the salinization of groundwater, and for identttifying areas most vulnerable to seawater intrusion. The recharge of the aquifer is mainly by the Al-Khattabi dam, the Nekor River and the Ghis River, on the eastern border of the plain. The water that feeds the aquifer shows a relatively high level of salinity and for this reason, the majority of sampled wells indicate high values of electric conductivity and total salinity which arrives at 7.5 g L-1. The plot of the geochemical results analyzes of groundwater in the Piper diagram shows two distinct chemical facies; sodium chloride-facies and chlorinated calcium and magnesium sulfated facies. The concentrations of 18O range between -4.15‰ and -5.73‰, while the values of 2H range between -28.4‰ and -41.7‰. The Nekor river water is depleted in heavy isotopes, and the isotopic compositions are in the order on -6‰ for 18O and -40.5‰ for deuterium. Most of the wells have a slope <8 indicating a slight evaporation before infiltration. The data show low and variable d-excess values (range from -0.02‰ to 11.6‰), reflect recharge during different climatic conditions. The isotopic concentrations of 18O-SO4 vary between 4.35‰ and 8.60‰, while the 34S isotope values range from -4.3‰ to 9.9‰. For Ghis River, these values are between -4.4‰ and 4.95‰, respectively, for sulfur and oxygen. The interpretation of the chemical and isotopic results suggesting the intrusion of seawater to increase salinity of groundwater in the region is low. However, only the NE area shows probable contamination of seawater. In contrast, wells are saline independent of seawater intrusion, the origin of the high salinity can be related to: 1- the accumulation of rivers fluid intake and water dam rich dissolved salts and sulphates, 2- the anthropogenic pollution (domestic sewage, agricultural inputs, septic uses).

Meteoric precipitation at Yucca Mountain, Nevada: Chemical and stable isotope analyses, 2006-09

USGS Publications Warehouse

Moscati, Richard J.; Scofield, Kevin M.

2011-01-01

Cumulatively, &delta18O values range from 3.0 to -20.4 per mil (%o) and &deltaD values range from 10 to -14%o. Winter-season precipitation commonly has isotopically lighter compositions. The cumulative &delta18O plotted against &deltaD shows that precipitation samples define a line with slope of 6.4, less than the 8 of the Global Meteoric Water Line. This difference in slope, typical of arid environments, is chiefly the result of evaporation of falling raindrops due to warmer air temperatures. ;

Oxygen isotope fractionation effects in soil water via interaction with cations (Mg, Ca, K, Na) adsorbed to phyllosilicate clay minerals

NASA Astrophysics Data System (ADS)

Oerter, Erik; Finstad, Kari; Schaefer, Justin; Goldsmith, Gregory R.; Dawson, Todd; Amundson, Ronald

2014-07-01

In isotope-enabled hydrology, soil and vadose zone sediments have been generally considered to be isotopically inert with respect to the water they host. This is inconsistent with knowledge that clay particles possessing an electronegative surface charge and resulting cation exchange capacity (CEC) interact with a wide range of solutes which, in the absence of clays, have been shown to exhibit δ18O isotope effects that vary in relation to the ionic strength of the solutions. To investigate the isotope effects caused by high CEC clays in mineral-water systems, we created a series of monominerallic-water mixtures at gravimetric water contents ranging from 5% to 32%, consisting of pure deionized water of known isotopic composition with homoionic (Mg, Ca, Na, K) montmorillonite. Similar mixtures were also created with quartz to determine the isotope effect of non-, or very minimally-, charged mineral surfaces. The δ18O value of the water in these monominerallic soil analogs was then measured by isotope ratio mass spectrometry (IRMS) after direct headspace CO2 equilibration. Mg- and Ca-exchanged homoionic montmorillonite depleted measured δ18O values up to 1.55‰ relative to pure water at 5% water content, declining to 0.49‰ depletion at 30% water content. K-montmorillonite enriched measured δ18O values up to 0.86‰ at 5% water content, declining to 0.11‰ enrichment at 30% water. Na-montmorillonite produces no measureable isotope effect. The isotope effects observed in these experiments may be present in natural, high-clay soils and sediments. These findings have relevance to the interpretation of results of direct CO2-water equilibration approaches to the measurement of the δ18O value of soil water. The adsorbed cation isotope effect may bear consideration in studies of pedogenic carbonate, plant-soil water use and soil-atmosphere interaction. Finally, the observed isotope effects may prove useful as molecular scale probes of the nature of mineral-water interactions.

Stable-isotope ratios of hydrogen and oxygen in precipitation at Norman, Oklahoma, 1996-2008

USGS Publications Warehouse

Jaeschke, Jeanne B.; Scholl, Martha A.; Cozzarelli, Isabelle M.; Masoner, Jason R.; Christenson, Scott; Qi, Haiping

2011-01-01

Precipitation samples for measurement of stable-isotope ratios of hydrogen (delta2H) and oxygen (delta18O) were collected at the Norman Landfill Research Site in Norman, Oklahoma, from May 1996 to October 2008. Rainfall amounts also were measured at the site (U.S. Geological Survey gaging station 07229053) during the collection period. The delta2H of precipitation samples ranged from -121.9 to +8.3 per mil, and the delta18O of precipitation ranged from -16.96 to +0.50 per mil. The volume-weighted average values for delta2H and delta18O of precipitation over the 12-year measurement period were -31.13 per mil for delta2H and -5.57 per mil for delta18O. Average summer-season delta2H and delta18O values of precipitation usually were more positive (enriched in the heavier isotopes) than winter values.

Determination of Trophic Structure in Selected Freshwater Ecosystems by using Stable Isotope Analysis

PubMed Central

Zainordin, ‘Amila Faqhira; Ab Hamid, Suhaila

2017-01-01

Stable isotope analysis has been used extensively to establish trophic relationships in many ecosystems. Present study utilised stable isotope signatures of carbon and nitrogen to identify trophic structure of aquatic food web in river and rice field ecosystems in Perak, northern peninsular Malaysia. The mean δ13C values of all producers ranged from −35.29 ± 0.21 to −26.00 ± 0.050‰. The greatest δ15N values noted was in zenarchopterid fish with 9.68 ± 0.020‰. The δ15N values of aquatic insects ranged between 2.59 ± 0.107 in Elmidae (Coleoptera) and 8.11 ± 0.022‰ in Nepidae (Hemiptera). Correspondingly, with all the δ13C and δ15N values recorded, it can be deduced that there are four trophic levels existed in the freshwater ecosystems which started with the producer (plants), followed by primary consumer (aquatic insects and non-predatory fish), secondary consumer (invertebrate predators) and lastly tertiary consumer (vertebrate predators). PMID:28890758

An isotopic study of a fluvial-lacustrine sequence: The Plio-Pleistocene koobi fora sequence, East Africa

USGS Publications Warehouse

Cerling, T.E.; Bowman, J.R.; O'Neil, J.R.

1988-01-01

Stable isotopic analyses of Plio-Pleistocene and modern sediments in the fluvial-lacustrine system occupying the Turkana Basin, East Africa provide constraints on the paleoenvironmental and diagenetic histories of the Pliocene through the Recent sediments in the basin. The ??13C values for carbonates in lacustrine sediments range from -15 to +22??? relative to PDB, depending on the varying proportions of CO2 from the atmospheric reservoir and from various metabolic sources. The ??18O values of carbonates in lacustrine sediments indicate that the isotopic composition of paleolake water varied by over 10??? from the Pliocene to the present. The ??13C values for pedogenic carbonates record paleoccologic variations and suggest that C4 plants did not become well established in the preserved depositional parts of the basin until about 1.8 myr ago. The ??18O values pedogenic carbonates suggest a range of over 10??? for the isotopic composition of soil water during this interval. They also suggest a period of major climatic instability from about 3.4 to 3.1 myr and at about 1.8 myr. Together, the ??13C and ??18O values of pedogenic carbonates indicate that the present conditions are as arid and hot as any that had prevailed during deposition of these Plio-Pleistocene sediments. ?? 1988.

Diet-tissue stable isotope (Δ(13)C and Δ(15)N) discrimination factors for multiple tissues from terrestrial reptiles.

PubMed

Steinitz, Ronnie; Lemm, Jeffrey M; Pasachnik, Stesha A; Kurle, Carolyn M

2016-01-15

Stable isotope analysis is a powerful tool for reconstructing trophic interactions to better understand drivers of community ecology. Taxon-specific stable isotope discrimination factors contribute to the best use of this tool. We determined the first Δ(13)C and Δ(15)N values for Rock Iguanas (Cyclura spp.) to better understand isotopic fractionation and estimate wild reptile foraging ecology. The Δ(13)C and Δ(15)N values between diet and skin, blood, and scat were determined from juvenile and adult iguanas held for 1 year on a known diet. We measured relationships between iguana discrimination factors and size/age and quantified effects of lipid extraction and acid treatment on stable isotope values from iguana tissues. Isotopic and elemental compositions were determined by Dumas combustion using an elemental analyzer coupled to an isotope ratio mass spectrometer using standards of known composition. The Δ(13)C and Δ(15)N values ranged from -2.5 to +6.5‰ and +2.2 to +7.5‰, respectively, with some differences among tissues and between juveniles and adults. The Δ(13)C values from blood and skin differed among species, but not the Δ(15)N values. The Δ(13)C values from blood and skin and Δ(15)N values from blood were positively correlated with size/age. The Δ(13)C values from scat were negatively correlated with size (not age). Treatment with HCl (scat) and lipid extraction (skin) did not affect the isotope values. These results should aid in the understanding of processes driving stable carbon and nitrogen isotope discrimination factors in reptiles. We provide estimates of Δ(13)C and Δ(15)N values and linear relationships between iguana size/age and discrimination factors for the best interpretation of wild reptile foraging ecology. Copyright © 2015 John Wiley & Sons, Ltd.

Oxygen isotope values of tree ring α-cellulose as a proxy of hydroclimate variability in arid regions

NASA Astrophysics Data System (ADS)

Dodd, J. P.; Freimuth, E. J.; Olson, E. J.; Diefendorf, A. F.

2015-12-01

One of the main goals of tree ring isotope studies is to reconstruct climate-driven variations in the source water and antecedent precipitation; however, evaporation in the soil and leaves can significantly modify the isotope values of the source water. This is particularly the case in arid environments where evaporative effects are perhaps the most significant unknown variable when attempting to reconstruct regional-scale hydroclimate variations from tree ring isotope proxies. To quantify the effects of extreme aridity on α-cellulose δ18O values, we measured the oxygen isotope values of groundwater, xylem water, leaf water, and tree ring α-cellulose in an endemic species of drought-resistant trees (Prosopis tamarugo) from different microenvironments throughout the Atacama Desert of Northern Chile. Average annual precipitation is <5 mm/yr, and groundwater is the primary water source for P. tamarugo trees in the region. Groundwater δ18O values at the sample locations range from -6.7 to -9.7‰, and xylem water δ18O values record a systematic increase (ave. Δ18Ox-gw =+1.3‰; 2σ =1.0‰). Leaf waters are significantly affected by evaporative enrichment with a range of δ18O values from 7 to 23‰. This range most likely reflects a number of physiological and environmental conditions including tree size, canopy development, and sample time (i.e. morning vs. evening). However, despite the large variation in leaf water δ18O values, the average difference between the α-cellulose and groundwater is very consistent (Δ18Oc-gw = +39.7‰; 2σ =1.3‰). P. tamarugo samples were collected in austral spring, when tree growth was at its maximum; therefore, any seasonal variations in plant physiology not captured with this dataset will have a limited impact on cellulose production. These data demonstrate that despite the variable evaporative enrichment of 18O in the leaf water, the α-cellulose δ18O values provide a remarkably consistent record of variations in groundwater δ18O values in this extremely arid environment.

A 1000-year record of dry conditions in the eastern Canadian prairies reconstructed from oxygen and carbon isotope measurements on Lake Winnipeg sediment organics

USGS Publications Warehouse

Buhay, W.M.; Simpson, S.; Thorleifson, H.; Lewis, M.; King, J.; Telka, A.; Wilkinson, Philip M.; Babb, J.; Timsic, S.; Bailey, D.

2009-01-01

A short sediment core (162 cm), covering the period AD 920-1999, was sampled from the south basin of Lake Winnipeg for a suite of multi-proxy analyses leading towards a detailed characterisation of the recent millennial lake environment and hydroclimate of southern Manitoba, Canada. Information on the frequency and duration of major dry periods in southern Manitoba, in light of the changes that are likely to occur as a result of an increasingly warming atmosphere, is of specific interest in this study. Intervals of relatively enriched lake sediment cellulose oxygen isotope values (??18Ocellulose) were found to occur from AD 1180 to 1230 (error range: AD 1104-1231 to 1160-1280), 1610-1640 (error range: AD 1571-1634 to 1603-1662), 1670-1720 (error range: AD 1643-1697 to 1692-1738) and 1750-1780 (error range: AD 1724-1766 to 1756-1794). Regional water balance, inferred from calculated Lake Winnipeg water oxygen isotope values (??18Oinf-lw), suggest that the ratio of lake evaporation to catchment input may have been 25-40% higher during these isotopically distinct periods. Associated with the enriched d??18Ocellulose intervals are some depleted carbon isotope values associated with more abundantly preserved sediment organic matter (d??13COM). These suggest reduced microbial oxidation of terrestrially derived organic matter and/or subdued lake productivity during periods of minimised input of nutrients from the catchment area. With reference to other corroborating evidence, it is suggested that the AD 1180-1230, 1610-1640, 1670-1720 and 1750-1780 intervals represent four distinctly drier periods (droughts) in southern Manitoba, Canada. Additionally, lower-magnitude and duration dry periods may have also occurred from 1320 to 1340 (error range: AD 1257-1363), 1530-1540 (error range: AD 1490-1565 to 1498-1572) and 1570-1580 (error range: AD 1531-1599 to 1539-1606). ?? 2009 John Wiley & Sons, Ltd.

Carbon isotopic composition of individual Precambrian microfossils

NASA Technical Reports Server (NTRS)

House, C. H.; Schopf, J. W.; McKeegan, K. D.; Coath, C. D.; Harrison, T. M.; Stetter, K. O.

2000-01-01

Ion microprobe measurements of carbon isotope ratios were made in 30 specimens representing six fossil genera of microorganisms petrified in stromatolitic chert from the approximately 850 Ma Bitter Springs Formation, Australia, and the approximately 2100 Ma Gunflint Formation, Canada. The delta 13C(PDB) values from individual microfossils of the Bitter Springs Formation ranged from -21.3 +/- 1.7% to -31.9 +/- 1.2% and the delta 13C(PDB) values from microfossils of the Gunflint Formation ranged from -32.4 +/- 0.7% to -45.4 +/- 1.2%. With the exception of two highly 13C-depleted Gunflint microfossils, the results generally yield values consistent with carbon fixation via either the Calvin cycle or the acetyl-CoA pathway. However, the isotopic results are not consistent with the degree of fractionation expected from either the 3-hydroxypropionate cycle or the reductive tricarboxylic acid cycle, suggesting that the microfossils studied did not use either of these pathways for carbon fixation. The morphologies of the microfossils suggest an affinity to the cyanobacteria, and our carbon isotopic data are consistent with this assignment.

Intra-Shell boron isotope ratios in benthic foraminifera: Implications for paleo-pH reconstructions

NASA Astrophysics Data System (ADS)

Rollion-Bard, C.; Erez, J.

2009-12-01

The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ11B has some limitations: 1) the knowledge of fractionation factor (α4-3) between the two boron dissolved species (boric acid and borate ion), 2) the δ11B of seawater may have varied with time and 3) the amplitude of the "vital effects" of this proxy. Using secondary ion mass spectrometry (SIMS), we looked at the internal variability in the boron isotope ratio of the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24±0.1 °C) in seawater with pH ranging between 7.90 and 8.45. We performed 6 to 8 measurements of δ11B in each foraminifera. Intra-shell boron isotopes show large variability with an upper threshold value of pH ~ 9. The ranges of the skeletal calculated pH values in different cultured foraminifera, show strong correlation with the culture pH values and may thus serve as proxy for pH in the past ocean.

Modeling calcification periods of Cytheridella ilosvayi from Florida based on isotopic signatures and hydrological data

NASA Astrophysics Data System (ADS)

Meyer, Juliane; Wrozyna, Claudia; Leis, Albrecht; Piller, Werner E.

2017-11-01

The isotopic signatures of ostracod shells are the result of the temperature and composition of their host water and the phenology and ecology of the target species. Investigations addressing the influence of site-specific environmental variations on the isotopic ranges of ostracod shells are still rare but can provide important information on habitat-dependent variations and may signify a seasonally restricted timing of calcification periods. Here we present isotopic signatures (δ18Oostr, δ13Costr) of living Cytheridella ilosvayi (Ostracoda) and physical, chemical, and isotopic (δD, δ18Owater, δ13CDIC) compositions of 14 freshwater habitats (rivers, lakes, canals, marshes, sinkholes) in South Florida from winter 2013 and summer 2014. We also present instrumental data of river temperatures and δ18O of precipitation (δ18Oprec) from this region. The physicochemical and isotopic compositions of the selected sites characterize the different habitats and show the influence of the source water, biological activity, and duration of exposure to the surface. Mean δ18Oostr and δ13Costr signatures of C. ilosvayi shells correlate well with the isotopic composition of their host waters. Within-sample variabilities in repeated isotopic measurements of single ostracod shells reflect habitat-dependent ranges. The similarly high range of ostracod δ18O in rivers and one marsh sample indicates that both temperature and δ18Oprec are responsible for their variation in the whole study area. Rivers and canals, which are predominantly influenced by the input and mixing of inorganic carbon from the catchment, show smaller δ13Costr ranges than the marsh dominated by local fluctuations in biological activities. Based on these observations, background data of water temperatures and δ18Oprec were used to calculate monthly δ18O variations in a theoretical calcite formed in rivers in Florida assuming a direct reaction on precipitation changes. The calculated values showed a high variation coupled with low mean values during the summer wet season, while during the winter dry season the variation remains small and mean values increased. Inferred configurations were used to approximate possible calcification periods of C. ilosvayi. For a plausible calcification period, mean values and ranges of δ18Oostr had to be equal to the theoretical calcite with a slight positive offset (vital effect). The applied model suggests a seasonal calcification period of C. ilosvayi in early spring that is probably coupled to the hydrologic cycle of Florida.

Preparation of Authigenic Pyrite from Methane-bearing Sediments for In Situ Sulfur Isotope Analysis Using SIMS.

PubMed

Lin, Zhiyong; Sun, Xiaoming; Peckmann, Jörn; Lu, Yang; Strauss, Harald; Xu, Li; Lu, Hongfeng; Teichert, Barbara M A

2017-08-31

Different sulfur isotope compositions of authigenic pyrite typically result from the sulfate-driven anaerobic oxidation of methane (SO4-AOM) and organiclastic sulfate reduction (OSR) in marine sediments. However, unravelling the complex pyritization sequence is a challenge because of the coexistence of different sequentially formed pyrite phases. This manuscript describes a sample preparation procedure that enables the use of secondary ion mass spectroscopy (SIMS) to obtain in situ δ 34 S values of various pyrite generations. This allows researchers to constrain how SO4-AOM affects pyritization in methane-bearing sediments. SIMS analysis revealed an extreme range in δ 34 S values, spanning from -41.6 to +114.8‰, which is much wider than the range of δ 34 S values obtained by the traditional bulk sulfur isotope analysis of the same samples. Pyrite in the shallow sediment mainly consists of 34 S-depleted framboids, suggesting early diagenetic formation by OSR. Deeper in the sediment, more pyrite occurs as overgrowths and euhedral crystals, which display much higher SIMS δ 34 S values than the framboids. Such 34 S-enriched pyrite is related to enhanced SO4-AOM at the sulfate-methane transition zone, postdating OSR. High-resolution in situ SIMS sulfur isotope analyses allow for the reconstruction of the pyritization processes, which cannot be resolved by bulk sulfur isotope analysis.

Nitrogen isotopic components in the early solar system

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1994-01-01

It is quite common to take the terrestrial atmospheric value of (15)N/(14)N (0.00366) as typical of nitrogen in the early solar system, but in fact there is little reason to suppose that this value had a nebula-wide significance. Indeed, it is not clear that there was a unique solar-system-wide (15)N/(14)N ratio, of whatever value. Here we review what is known about the distribution of the nitrogen isotopes among those solar-system objects that have been sampled so far and conclude that those isotopes reveal widespread inhomogeneity in the early solar system. Whether the isotopically distinct primordial components implied by this analysis were solid or gaseous or a mixture of both is not known. The isotopic composition of N in the Earth's mantle is controversial: estimates range from a 1.1 percent depletion in (15)N to a 1.4 percent enrichment. (Isotopic compositions will be expressed throughout as percent deviations from the terrestrial atmospheric value.) The present-day Martian atmosphere is characterized by a value of plus 62 percent but this enrichment in (15)N is attributed to selective loss of (14)N from the Martian exosphere. Modelling of this fractionation leads to an estimated primordial composition similar to the terrestrial atmospheric value, through the precision of this model-dependent result is unclear.

Sulfur record of rising and falling marine oxygen and sulfate levels during the Lomagundi event.

PubMed

Planavsky, Noah J; Bekker, Andrey; Hofmann, Axel; Owens, Jeremy D; Lyons, Timothy W

2012-11-06

Carbonates from approximately 2.3-2.1 billion years ago show markedly positive δ(13)C values commonly reaching and sometimes exceeding +10‰. Traditional interpretation of these positive δ(13)C values favors greatly enhanced organic carbon burial on a global scale, although other researchers have invoked widespread methanogenesis within the sediments. To resolve between these competing models and, more generally, among the mechanisms behind Earth's most dramatic carbon isotope event, we obtained coupled stable isotope data for carbonate carbon and carbonate-associated sulfate (CAS). CAS from the Lomagundi interval shows a narrow range of δ(34)S values and concentrations much like those of Phanerozoic and modern marine carbonate rocks. The δ(34)S values are a close match to those of coeval sulfate evaporites and likely reflect seawater composition. These observations are inconsistent with the idea of diagenetic carbonate formation in the methanic zone. Toward the end of the carbon isotope excursion there is an increase in the δ(34)S values of CAS. We propose that these trends in C and S isotope values track the isotopic evolution of seawater sulfate and reflect an increase in pyrite burial and a crash in the marine sulfate reservoir during ocean deoxygenation in the waning stages of the positive carbon isotope excursion.

An interlaboratory study to test instrument performance of hydrogen dual-inlet isotope-ratio mass spectrometers

USGS Publications Warehouse

Brand, Willi A.; Coplen, T.B.

2001-01-01

An interlaboratory comparison of forty isotope-ratio mass spectrometers of different ages from several vendors has been performed to test 2H/1H performance with hydrogen gases of three different isotopic compositions. The isotope-ratio results (unsufficiently corrected for H3+ contribution to the m/z = 3 collector, uncorrected for valve leakage in the change-over valves, etc.) expressed relative to one of these three gases covered a wide range of values: -630??? to -790??? for the second gas and -368??? to -462??? for the third gas. After normalizing the isotopic abundances of these test gases (linearly adjusting the ?? values so that the gases with the lowest and highest 2H content were identical for all laboratories), the standard deviation of the 40 measurements of the intermediate gas was a remarkably low 0.85???. It is concluded that the use of scaling factors is mandatory for providing accurate internationally comparable isotope-abundance values. Linear scaling for the isotope-ratio scales of gaseous hydrogen mass spectrometers is completely adequate. ?? Springer-Verlag 2001.

GasBench/isotope ratio mass spectrometry: a carbon isotope approach to detect exogenous CO(2) in sparkling drinks.

PubMed

Cabañero, Ana I; San-Hipólito, Tamar; Rupérez, Mercedes

2007-01-01

A new procedure for the determination of carbon dioxide (CO(2)) (13)C/(12)C isotope ratios, using direct injection into a GasBench/isotope ratio mass spectrometry (GasBench/IRMS) system, has been developed to improve isotopic methods devoted to the study of the authenticity of sparkling drinks. Thirty-nine commercial sparkling drink samples from various origins were analyzed. Values of delta(13)C(cava) ranged from -20.30 per thousand to -23.63 per thousand, when C3 sugar addition was performed for a second alcoholic fermentation. Values of delta(13)C(water) ranged from -5.59 per thousand to -6.87 per thousand in the case of naturally carbonated water or water fortified with gas from the spring, and delta(13)C(water) ranged from -29.36 per thousand to -42.09 per thousand when industrial CO(2) was added. It has been demonstrated that the addition of C4 sugar to semi-sparkling wine (aguja) and industrial CO(2) addition to sparkling wine (cava) or water can be detected. The new procedure has advantages over existing methods in terms of analysis time and sample treatment. In addition, it is the first isotopic method developed that allows (13)C/(12)C determination directly from a liquid sample without previous CO(2) extraction. No significant isotopic fractionation was observed nor any influence by secondary compounds present in the liquid phase. Copyright (c) 2007 John Wiley & Sons, Ltd.

O-stable Isotopes Distribution In Deep-sea Corals From Sims Measurements

NASA Astrophysics Data System (ADS)

Blamart, D.; Cuif, J.-P.; Juillet-Leclerc, A.

Urey's theoretical calculations (Urey, 1947) have predicted that the O-isotope fraction- ations between calcium carbonates and water should be large enough to be used as a paleothermometer. However, stable isotopes studies on aragonitic invertebrates includ- ing corals have also demonstrated departure of several per mil from O-equilibrium. Different tentative explanations have been proposed in the literature: (1) influence of the polymorphism form and chemical composition of the calcium carbonate (2) kinetic effects related to calcification process during rapid growth rate (3) metabolic effect due to respiration and photosynthesis. All these explanations are based on the assumption that the coral skeleton represents a structural homogeneous entity. Early microscopic studies of coral skeletons have suggested that coral skeletons are built by two different structures: (1) fibres and (2) centres of calcification confirmed by recent biominerali- sation studies. SIMS O-stable isotopes measurements have been performed on lines of centres of calcification and the surrounding aragonitic fibre on deep-sea coral (Lophe- lia Pertusa). Different transects of O-isotope distribution have been carried out in the septa and in the thick wall of Lophelia pertusa. O-isotopic values of the fibres of the septa and of the wall show a very large range of variation of around 10L' from -5 to +5L' (PDB). O-measurement performed on line of the centre of calcification from the inner part of the septa to the wall show a restricted range of variation which not exceed 1L'. O-values of the centres of calcification in the septa and in the wall are similar with a mean value of -2.9s0.3L'. Temperature derived from O values of the centre of cal- ´ cification are not consistant with the measured ones in situ indicating also a constant fractionation in this microstructure. Coupled with C-isotopes measurements O-isotope distribution should better constraint the growth mechanism, calcification process and the associated isotopic fractionation

Zhamanshin astrobleme provides evidence for carbonaceous chondrite and post-impact exchange between ejecta and Earth's atmosphere.

PubMed

Magna, Tomáš; Žák, Karel; Pack, Andreas; Moynier, Frédéric; Mougel, Bérengère; Peters, Stefan; Skála, Roman; Jonášová, Šárka; Mizera, Jiří; Řanda, Zdeněk

2017-08-09

Chemical fingerprints of impacts are usually compromised by extreme conditions in the impact plume, and the contribution of projectile matter to impactites does not often exceed a fraction of per cent. Here we use chromium and oxygen isotopes to identify the impactor and impact-plume processes for Zhamanshin astrobleme, Kazakhstan. ε 54 Cr values up to 1.54 in irghizites, part of the fallback ejecta, represent the 54 Cr-rich extremity of the Solar System range and suggest a CI-like chondrite impactor. Δ 17 O values as low as -0.22‰ in irghizites, however, are incompatible with a CI-like impactor. We suggest that the observed 17 O depletion in irghizites relative to the terrestrial range is caused by partial isotope exchange with atmospheric oxygen (Δ 17 O = -0.47‰) following material ejection. In contrast, combined Δ 17 O-ε 54 Cr data for central European tektites (distal ejecta) fall into the terrestrial range and neither impactor fingerprint nor oxygen isotope exchange with the atmosphere are indicated.Identifying the original impactor from craters remains challenging. Here, the authors use chromium and oxygen isotopes to indicate that the Zhamanshin astrobleme impactor was a carbonaceous chrondrite by demonstrating that depleted 17O values are due to exchange with atmospheric oxygen.

Accurate experimental determination of the isotope effects on the triple point temperature of water. I. Dependence on the 2H abundance

NASA Astrophysics Data System (ADS)

Faghihi, V.; Peruzzi, A.; Aerts-Bijma, A. T.; Jansen, H. G.; Spriensma, J. J.; van Geel, J.; Meijer, H. A. J.

2015-12-01

Variation in the isotopic composition of water is one of the major contributors to uncertainty in the realization of the triple point of water (TPW). Although the dependence of the TPW on the isotopic composition of the water has been known for years, there is still a lack of a detailed and accurate experimental determination of the values for the correction constants. This paper is the first of two articles (Part I and Part II) that address quantification of isotope abundance effects on the triple point temperature of water. In this paper, we describe our experimental assessment of the 2H isotope effect. We manufactured five triple point cells with prepared water mixtures with a range of 2H isotopic abundances encompassing widely the natural abundance range, while the 18O and 17O isotopic abundance were kept approximately constant and the 18O  -  17O ratio was close to the Meijer-Li relationship for natural waters. The selected range of 2H isotopic abundances led to cells that realised TPW temperatures between approximately  -140 μK to  +2500 μK with respect to the TPW temperature as realized by VSMOW (Vienna Standard Mean Ocean Water). Our experiment led to determination of the value for the δ2H correction parameter of A2H  =  673 μK / (‰ deviation of δ2H from VSMOW) with a combined uncertainty of 4 μK (k  =  1, or 1σ).

Nicotine, acetanilide and urea multi-level 2H-, 13C- and 15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry.

PubMed

Schimmelmann, Arndt; Albertino, Andrea; Sauer, Peter E; Qi, Haiping; Molinie, Roland; Mesnard, François

2009-11-01

Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the delta values of these reference materials should bracket the isotopic range of samples with unknown delta values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for delta13C and delta15N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: delta2H(nicotine) -162 to -45 per thousand, delta13C(nicotine) -30.05 to +7.72 per thousand, delta15N(nicotine) -6.03 to +33.62 per thousand; delta15N(acetanilide) +1.18 to +40.57 per thousand; delta13C(urea) -34.13 to +11.71 per thousand, delta15N(urea) +0.26 to +40.61 per thousand (recommended delta values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different delta15N values. Comparative delta13C and delta15N on-line EA-IRMS data from 14 volunteering laboratories document the usefulness and reliability of acetanilides and ureas as EA-IRMS reference materials. Copyright 2009 John Wiley & Sons, Ltd.

Stable isotope patterns in micronekton from the Mozambique Channel

NASA Astrophysics Data System (ADS)

Ménard, Frédéric; Benivary, Hermann Doris; Bodin, Nathalie; Coffineau, Nathalie; Le Loc'h, François; Mison, Thomas; Richard, Pierre; Potier, Michel

2014-02-01

We measured the stable carbon (δ13C) and nitrogen (δ15N) isotopic composition of tissues of micronektonic organisms (fishes, squids, crustaceans and gelatinous organisms) collected in the Mozambique Channel during two scientific cruises in 2008 and 2009. The oceanic circulation in the Mozambique Channel is dominated by mesoscale cyclonic and anticyclonic eddies which play a key role in biological processes of less-productive deep-sea ecosystems. We investigated the potential impact of mesoscale features on the δ13C and δ15N values of 32 taxa of micronekton. Fishes, squids, crustaceans and gelatinous organisms encompassed a wide range of isotopic niches, with large overlaps among species. Our results showed that mesoscale features did not really influence the isotopic signatures of the sampled organisms, although cyclonic eddies can occasionally impact the nitrogen signatures of micronekton. We show that δ13C values were intermediate between standard offshore and nearshore signatures, suggesting that pelagic production in the Mozambique Channel could be partly supported by the transport and export of inorganic and organic particles from the Mozambican coast toward the offshore area. Trophic levels calculated from δ15N values ranged from 2.6 to 4.2, showing that micronekton taxa can be tertiary consumers in the Mozambique Channel. Our findings evidenced clusters of micronektonic organisms according to their δ15N or δ13C isotopic signatures, but variations in stable isotope values reflect a complex set of embedded processes linked to physical mesoscale dynamics (rotational dynamics of eddies) and basic biology and ecology of micronektonic organisms (vertical habitat, migration pattern, dietary habits, body length) that are discussed with regard to the stable isotope method based on time-integrated assimilated food.

Stable carbon isotope fractionation by sulfate-reducing bacteria

NASA Technical Reports Server (NTRS)

Londry, Kathleen L.; Des Marais, David J.

2003-01-01

Biogeochemical transformations occurring in the anoxic zones of stratified sedimentary microbial communities can profoundly influence the isotopic and organic signatures preserved in the fossil record. Accordingly, we have determined carbon isotope discrimination that is associated with both heterotrophic and lithotrophic growth of pure cultures of sulfate-reducing bacteria (SRB). For heterotrophic-growth experiments, substrate consumption was monitored to completion. Sealed vessels containing SRB cultures were harvested at different time intervals, and delta(13)C values were determined for gaseous CO(2), organic substrates, and products such as biomass. For three of the four SRB, carbon isotope effects between the substrates, acetate or lactate and CO(2), and the cell biomass were small, ranging from 0 to 2 per thousand. However, for Desulfotomaculum acetoxidans, the carbon incorporated into biomass was isotopically heavier than the available substrates by 8 to 9 per thousand. SRB grown lithoautotrophically consumed less than 3% of the available CO(2) and exhibited substantial discrimination (calculated as isotope fractionation factors [alpha]), as follows: for Desulfobacterium autotrophicum, alpha values ranged from 1.0100 to 1.0123; for Desulfobacter hydrogenophilus, the alpha value was 0.0138, and for Desulfotomaculum acetoxidans, the alpha value was 1.0310. Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO(2) resulted in biomass with a delta(13)C composition intermediate to that of the substrates. The extent of fractionation depended on which enzymatic pathways were used, the direction in which the pathways operated, and the growth rate, but fractionation was not dependent on the growth phase. To the extent that environmental conditions affect the availability of organic substrates (e.g., acetate) and reducing power (e.g., H(2)), ecological forces can also influence carbon isotope discrimination by SRB.

Verification of Egg Farming Systems from The Netherlands and New Zealand Using Stable Isotopes.

PubMed

Rogers, Karyne M; van Ruth, Saskia; Alewijn, Martin; Philips, Andy; Rogers, Pam

2015-09-30

Stable isotopes were used to develop authentication criteria of eggs laid under cage, barn, free range, and organic farming regimens from The Netherlands and New Zealand. A training set of commercial poultry feeds and egg albumen from 49 poultry farms across The Netherlands was used to determine the isotopic variability of organic and conventional feeds and to assess trophic effects of these corresponding feeds and barn, free range, and organic farming regimens on corresponding egg albumen. A further 52 brands of New Zealand eggs were sampled from supermarket shelves in 2008 (18), 2010 (30), and 2014 (4) to characterize and monitor changes in caged, barn, free range, and organic egg farming regimens. Stable carbon (δ(13)C) and nitrogen (δ(15)N) isotopes of 49 commercial poultry feeds and their corresponding egg albumens reveals that Dutch poultry are fed exclusively on a plant-based feed and that it is possible to discriminate between conventional and organic egg farming regimens in The Netherlands. Similarly, it is possible to discriminate between New Zealand organic and conventional egg farming regimens, although in the initial screening in 2008, results showed that some organic eggs had isotope values similar to those of conventional eggs, suggesting hens were not exclusively receiving an organic diet. Dutch and New Zealand egg regimens were shown to have a low isotopic correlation between both countries, because of different poultry feed compositions. In New Zealand, both conventional and organic egg whites have higher δ(15)N values than corresponding Dutch egg whites, due to the use of fishmeal or meat and bone meal (MBM), which is banned in European countries. This study suggests that stable isotopes (specifically nitrogen) show particular promise as a screening and authentication tool for organically farmed eggs. Criteria to assess truthfulness in labeling of organic eggs were developed, and we propose that Dutch organic egg whites should have a minimum δ(15)N value of 4.8‰ to account for an organic plant derived diet. Monitoring of New Zealand egg isotopes over the past 7 years suggests that organic eggs should have a minimum δ(15)N value of 6.0‰, and eggs falling below this value should be investigated further by certification authorities.

Significance of nodule formation for the interpretation of matrix micrite C and O isotope ratios in Upper Jurassic Ammonitico Rosso limestones (Betic Cordillera, SE Spain)

NASA Astrophysics Data System (ADS)

Coimbra, R.; Immenhauser, A.; Olóriz, F.

2009-04-01

Three Ammonitico Rosso (AR) sections from the Betic Cordillera in SE Spain were analysed to obtain stable isotope records and access paleoenvironmental information. The study area corresponded to a Late Jurassic distal epioceanic setting and is characterized by the occurrence of more or less calcareous AR horizons ranging from greyish to redish colour. The carbonate materials under scope where retrieved from the Cardador, Salcedo and Cañada del Hornillo sections and consist on matrix micrite, carbonate cements and skeletals and were analysed for their carbon and oxygen isotope signature. At least one bulk sample per ammonite biozone was retrieved under a strict biochronostratigraphic control. The degree of diagenetic imprint was acessed by cathodoluminiscence analysis and carbonate ultrastructure was analysed by scanning electron microscope. Micrite matrix showed dull luminiscence, revealing a low degree of diagenetic overprint, as oposite to carbonate cements and skekeltal materials, that presented bright orange luminiscence. The identification of coccoliths and filaments under SEM attested for the good degree of preservation of the carbonate ultrastructure. The carbon isotope chemostratigraphy resembles the known trends for Jurassic northern Tethyan margins and absolute values (from 1.1 to 3.3 permil) are within the range usually reported for well preserved material. Oxygen isotopes of matrix micrite samples present higher values than those expected for Upper Jurassic materials (ranging from -0.3 to 0.9 permil for the Cardador and Salcedo sections and from -2.1 to 0.4 permil at the Cañada del Hornillo section), whilts commonly well preserved low-Mg calcite skeletal materials, such as belemenite rostra present lower values than matrix micrite, acompanied by a very bright orange luminiscence. In contrast to what is usually reported, matrix micrite presents values closer to what would be the original isotopic composition and skeletal material is more affected by latter diagenesis. In this context, paleoenvironmental considerations are available, and the oxygen curve is interpreted as reasonable approximation of seawater paleo-temperatures and relative depth. Very early marine nodule formation is thought to be determinant for the high isotope values found at these locations. It is proposed that early diagenetic nodule formation preserved near-seawater isotopic signals and inhibited subsequent diagenetic overprint as revealed by several proxies retrieved from intra-nodule samples.

Petrographic and C & O isotopic characteristics of the earliest stages of aqueous alteration of CM chondrites

NASA Astrophysics Data System (ADS)

Vacher, Lionel G.; Marrocchi, Yves; Villeneuve, Johan; Verdier-Paoletti, Maximilien J.; Gounelle, Matthieu

2017-09-01

CM chondrites form the largest group of hydrated meteorites and span a wide range of alteration states, with the Paris meteorite being the least altered CM described to date. Ca-Carbonates are powerful proxies for the alteration conditions of CMs because they are direct snapshots of the chemical and isotopic compositions of the parent fluids. Here, we report a petrographic and a C isotope and O isotope survey of Ca-carbonates in Paris in order to better characterize the earliest stages of aqueous alteration. Petrographic observations show that Paris contains two distinct populations of Ca-carbonates: Type 1a Ca-carbonates, which are surrounded by rims of tochilinite/cronstedtite intergrowths (TCIs), and new Type 0 Ca-carbonates, which do not exhibit the TCI rims. The TCI rims of Type 1a Ca-carbonates commonly outline euhedral crystal faces, demonstrating that these Ca-carbonates were (i) partially or totally pseudomorphosed by TCI and (ii) precipitated at the earliest stages of aqueous alteration, before Type 0 Ca-carbonates. Isotopic measurements show that Paris' Ca-carbonates have δ13C values that range from 19 to 80‰ (PDB), δ18O values that range from 29 to 41%, and δ17O values that range from 13 to 24‰ (SMOW). According to the δ13C-δ18O values of Paris' Ca-carbonates, we developed a new alteration model that involves (i) the equilibration of a primordial 17,18O-rich water (PW) with 16O-rich anhydrous silicates and (ii) varying contribution of 12C- and 13C-rich soluble organic matter (SOMs). It also suggests that many parameters control the C and O isotopic composition of Ca-carbonates, the principles being the degree of isotopic equilibration between the PW and the anhydrous silicates, the respective contribution of 12C and 13C-rich SOMs as well as the thermal evolution of CM parent bodies. Consequently, we suggest that CM Ca-carbonates could record both positive and negative δ13C-δ18O relationships, but a systematic correspondence is probably absent in CM chondrites due to the large number of factors involved in generating the isotopic characteristics of Ca-carbonates. From recent reports of the C-isotopic compositions of SOM in CM chondrites, we propose that water-soluble organic compounds were the most probable source of 13C enrichment in the majority of CM carbonates.

Diverse origins of Arctic and Subarctic methane point source emissions identified with multiply-substituted isotopologues

NASA Astrophysics Data System (ADS)

Douglas, P. M. J.; Stolper, D. A.; Smith, D. A.; Walter Anthony, K. M.; Paull, C. K.; Dallimore, S.; Wik, M.; Crill, P. M.; Winterdahl, M.; Eiler, J. M.; Sessions, A. L.

2016-09-01

Methane is a potent greenhouse gas, and there are concerns that its natural emissions from the Arctic could act as a substantial positive feedback to anthropogenic global warming. Determining the sources of methane emissions and the biogeochemical processes controlling them is important for understanding present and future Arctic contributions to atmospheric methane budgets. Here we apply measurements of multiply-substituted isotopologues, or clumped isotopes, of methane as a new tool to identify the origins of ebullitive fluxes in Alaska, Sweden and the Arctic Ocean. When methane forms in isotopic equilibrium, clumped isotope measurements indicate the formation temperature. In some microbial methane, however, non-equilibrium isotope effects, probably related to the kinetics of methanogenesis, lead to low clumped isotope values. We identify four categories of emissions in the studied samples: thermogenic methane, deep subsurface or marine microbial methane formed in isotopic equilibrium, freshwater microbial methane with non-equilibrium clumped isotope values, and mixtures of deep and shallow methane (i.e., combinations of the first three end members). Mixing between deep and shallow methane sources produces a non-linear variation in clumped isotope values with mixing proportion that provides new constraints for the formation environment of the mixing end-members. Analyses of microbial methane emitted from lakes, as well as a methanol-consuming methanogen pure culture, support the hypothesis that non-equilibrium clumped isotope values are controlled, in part, by kinetic isotope effects induced during enzymatic reactions involved in methanogenesis. Our results indicate that these kinetic isotope effects vary widely in microbial methane produced in Arctic lake sediments, with non-equilibrium Δ18 values spanning a range of more than 5‰.

Potential of IRMS technology for tracing gamma-butyrolactone (GBL).

PubMed

Marclay, François; Pazos, Diego; Delémont, Olivier; Esseiva, Pierre; Saudan, Christophe

2010-05-20

Popularity of gamma-hydroxybutyric acid (GHB) is fairly stable among drug users, while the consumption of its chemical precursor, gamma-butyrolactone (GBL), is a growing phenomenon. Although conventional analytical methods allow to detect this substance in various matrices, linking a trace and a source is still a difficult challenge. However, as several synthesis pathways and chemical precursors exist for the production of GBL, its carbon isotopic signature may vary extensively. For that purpose, a method has been developed to determine the carbon isotopes content of GBL by means of gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The delta(13)C-values of 19 bulk samples purchased worldwide were in the range from -23.1 to -45.8 per thousand (SD<0.3 per thousand). Furthermore, testing on the purification of GBL by distillation has not been found to be consistent with such a large range of delta(13)C-values, which are likely to result from the isotopic composition of the organic precursors used to produce GBL together with the kinetic isotope effect associated with the synthesis routes. Finally, inter- and intra-variability measurements of the delta(13)C-values demonstrated the high potential of IRMS for discriminating between seizures of GBL and for source determination.

Oxygen isotope ranking of late Eocene and Oligocene planktonic foraminifers: Implications for Oligocene sea-surface temperatures and global ice-volume

USGS Publications Warehouse

Poore, R.Z.; Matthews, R.K.

1984-01-01

Oxygen isotope analyses of late Eocene and Oligocene planktonic foraminifers from low and middle latitude sites in the Atlantic Basin show that different species from the same samples can yield significantly different isotopic values. The range of isotopic values observed between species is greatest at low-latitudes and declines poleward. Many planktonic foraminifers exhibit a systematic isotopic ranking with respect to each other and can therefore be grouped on the basis of their isotopic ranking. The isotopic ranking of some taxa, however, appears to vary geographically and/or through time. Isotopic and paleontologic data from DSDP Site 522 indicate that commonly used isotopic temperature scales underestimate Oligocene sea surface temperatures. We suggest these temperature scales require revision to reflect the presence of Oligocene glaciation. Comparison of isotopic and paleontologic data from Sites 522, 511 and 277 suggests cold, low-salinity surface waters were present in high southern latitudes during the early Oligocene. Lowsalinity, high latitude surface waters could be caused by Eocene/Oligocene paleogeography or by the production of warm saline bottom water. ?? 1984.

Tracing chlorine sources of thermal and mineral springs along and across the Cascade Range using halogen and chlorine isotope compositions

USGS Publications Warehouse

Cullen, Jeffrey T.; Barnes, Jaime D.; Hurwitz, Shaul; Leeman, William P.

2015-01-01

In order to provide constraints on the sources of chlorine in spring waters associated with arc volcanism, the major/minor element concentrations and stable isotope compositions of chlorine, oxygen, and hydrogen were measured in 28 thermal and mineral springs along the Cascade Range in northwestern USA. Chloride concentrations in the springs range from 64 to 19,000 mg/L and View the MathML source values range from +0.2‰ to +1.9‰ (average=+1.0±0.4‰), with no systematic variation along or across the arc, nor correlations with their presumed underlying basement lithologies. Additionally, nine geochemically well-characterized lavas from across the Mt. St. Helens/Mt. Adams region of the Cascade Range (Leeman et al., 2004 and Leeman et al., 2005) were analyzed for their halogen concentrations and Cl isotope compositions. In the arc lavas, Cl and Br concentrations from the volcanic front are higher than in lavas from the forearc and backarc. F and I concentrations progressively decrease from forearc to backarc, similar to the trend documented for B in most arcs. View the MathML source values of the lavas range from −0.1 to +0.8‰ (average = +0.4±0.3‰). Our results suggest that the predominantly positive View the MathML source values observed in the springs are consistent with water interaction with underlying 37Cl-enriched basalt and/or altered oceanic crust, thereby making thermal spring waters a reasonable proxy for the Cl isotope compositions of associated volcanic rocks in the Cascades. However, waters with View the MathML source values >+1.0‰ also suggest additional contributions of chlorine degassed from cooling magmas due to subsurface vapor–liquid HCl fractionation in which Cl is lost to the aqueous fluid phase and 37Cl is concentrated in the ascending magmatic HCl vapor. Future work is necessary to better constrain Cl isotope behavior during volcanic degassing and fluid–rock interaction in order to improve volatile flux estimates through subduction zones.

Correlated carbon and oxygen isotope signatures in eclogitic diamonds with coesite inclusions: A SIMS investigation of diamonds from Guaniamo, Argyle and Orapa mines

NASA Astrophysics Data System (ADS)

Schulze, D. J.; Page, Z.; Harte, B.; Valley, J.; Channer, D.; Jaques, L.

2006-12-01

Using ion microprobes and secondary-ion mass spectrometry we have analyzed the carbon and oxygen isotopic composition of eclogite-suite diamonds and their coesite inclusions, respectively, from three suites of diamonds of Proterozoic age. Extremely high (for the mantle) oxygen isotope values (delta 18O of +10.2 to +16.9 per mil VSMOW) are preserved in coesites included in eclogitic diamonds from Guaniamo, Venezuela (Schulze et al., Nature, 2003), providing compelling evidence for an origin of their eclogite hosts by subduction of sea water altered ocean floor basalts. In situ SIMS analyses of their host diamonds yield carbon isotope values (delta 13C) of -12 to -18 per mil PDB. SIMS analyses of coesite inclusions from Argyle, Australia diamonds previously analyzed by combustion methods for d13C composition (Jaques et al., Proc. 4th Kimb. Conf, 1989), also yield anomalously high d18O values (+6.8 to +16.0 per mil VSMOW), that correlate with the anomalously low carbon isotope values (-10.3 to -14.1 per mil PDB). One coesite-bearing diamond from Orapa, Botswana analyzed in situ by SIMS has a d18O value of the coesite of +8.5 per mil VSMOW and a d13C value of the adjacent diamond host of -9.0 per mil PDB. A second Orapa stone has a SIMS carbon isotope compositional range of d13C = -14 to -16 per mil PDB, but the coesite is too small for ion probe analysis. At each of these localities, carbon isotope values of coesite-bearing diamonds that are lower than typical of mantle carbon are correlated with oxygen isotope compositions of included coesites that are substantially above the common mantle oxygen isotope range. Such results are not in accord with diamond genesis models involving formation of eclogitic diamonds from igneous melts undergoing fractionation in the mantle or by crystallization from primordial inhomogeneities in Earth's mantle. By analogy with the oxygen isotope compositions of altered ocean floor basalts and Alpine (subduction zone) eclogites they are, however, consistent with a subduction origin for these eclogite assemblages from altered ocean floor basaltic protoliths, and thus the simplest explanation for the source of the low carbon isotope values of these diamonds is formation from biogenic carbon accumulated on or near the ocean floor and subducted to the depths of eclogite and diamond stability with the altered basalts. Significantly these results, which were not predicted from studies of diamond-bearing eclogites, apply to the mantle beneath three different continental crustal blocks of both Proterozoic (Guaniamo and Argyle) and Archean/Proterozoic (Orapa) age.

Geochemical structure of the Hawaiian plume: Sr, Nd, and Os isotopes in the 2.8 km HSDP-2 section of Mauna Kea volcano

NASA Astrophysics Data System (ADS)

Bryce, Julia G.; Depaolo, Donald J.; Lassiter, John C.

2005-09-01

Sr, Nd, and Os isotopic measurements were made on 110 Mauna Kea lava and hyaloclastite samples from the drillcore retrieved from the second phase of the Hawaii Scientific Drilling Project (HSDP-2). The samples come from depths of 255 to 3098 meters below sea level, span an age range from 200 to about 550-600 kyr, and represent an ordered record of the lava output from Mauna Kea volcano as it drifted a distance of about 40 km over the magma-producing region of the Hawaiian hot spot. The deepest (oldest) samples represent the time when Mauna Kea was closest to the center of the melting region of the Hawaiian plume. The Sr and Os isotopic ratios in HSDP-2 lavas show only subtle isotopic shifts over the ˜400 kyr history represented by the core. Neodymium isotopes (ɛNd values) increase systematically with decreasing age from an average value of nearly +6.5 to an average value of +7.5. This small change corresponds to subtle shifts in 87Sr/86Sr and 187Os/188Os isotope ratios, with small shifts of ɛHf, a large shift in 208Pb/204Pb and 208Pb/207Pb values, and with a very large shift in He isotope ratios from R/RA values of about 7-8 to values as high as 25. When Mauna Kea was closest to the plume core, the magma source did not have primitive characteristics for Nd, Sr, Pb, Hf, and Os isotopes but did have variable amounts of "primitive" helium. The systematic shifts in Nd, Hf, Pb, and He isotopes are consistent with radial isotopic zoning within the melting region of the plume. The melting region constitutes only the innermost, highest-temperature part of the thermally anomalous plume mantle. The different ranges of values observed for each isotopic system, and comparison of Mauna Kea lavas with those of Mauna Loa, suggest that the axial region of the plume, which has a radius of ˜20 km, is a mixture of recycled subducted components and primitive lower mantle materials, recently combined during the formational stages of the plume at the base of the mantle. The proportions of recycled and primitive components are not constant, and this requires there be longitudinal (vertical) heterogeneity within the core of the plume. The remainder of the plume, outside this plume "core zone," is less heterogeneous but distinct from upper mantle as represented by mid-ocean ridge basalt (MORB). The plume structure may provide a detailed view of mantle isotopic composition near the core-mantle boundary.

Production of platinum radioisotopes at Brookhaven Linac Isotope Producer (BLIP)

DOE PAGES

Smith, Suzanne V.; Mccutchan, Elizabeth; Gurdal, Gulhan; ...

2017-09-13

The accelerator production of platinum isotopes was investigated at the Brookhaven Linac Isotope Producer (BLIP). In this paper high purity natural platinum foils were irradiated at 53.2, 65.7, 105.2, 151.9, 162.9 and 173.3 MeV. The irradiated foils were digested in aqua regia and then converted to their hydrochloride salt with concentrated hydrochloric acid before analyzing by gamma spectrometry periodically for at least 10 days post end of bombardment. A wide range of platinum (Pt), gold (Au) and iridiu m (Ir) isotopes were identified. Effective cross sections at BLIP for Pt-188, Pt-189, Pt-191 and Pt-195m were compared to literature and theoreticalmore » cross sections determined using Empire-3.2. The majority of the effective cross sections (<70 MeV) confirm those reported in the literature. While the absolute values of the theoretical cross sections were up to a factor of 3 lower, Empire 3.2 modeled thresholds and maxima correlated well with experimental values. Preliminary evaluation into a rapid separation of Pt isotopes from high levels of Ir and Au isotopes proved to be a promising approach for large scale production. In conclusion, this study demonstrated that with the use of isotopically enriched target material accelerator production of selected platinum isotopes is feasible over a wide proton energy range.« less

Anatomy of the thriple oxygen isotope Terrestrial Fractionatoin Line

NASA Astrophysics Data System (ADS)

Sharp, Z. D.; Pack, A.

2017-12-01

In the triple oxygen isotope system, it is well established that the δ17O value of nearly all terrestrial materials is approximately ½ that of the corresponding δ18O value. In triple isotope space then, all samples plot on a slope 1/2 line, termed the Terrestrial Fractionation Line (TFL). It has recently been recognized that subtle, but significant departures from the TFL exist, given by Δ'17O = δ'17O -λ× δ'18O + γ, where λ is the slope of the TFL (γ is the y-intercept and assumed to be zero in most studies). There have been many published λ values, ranging from 0.52 to 0.5305. λ values determined from a best-fit to rock and mineral samples range from 0.5244 to 0.5266. λ values from meteoric waters are 0.527 to 0.528 (γ = 0.007 to 0.034), explained by equilibrium and kinetic processes. Extreme polar glacial samples define a λ >0.53. As pointed out by Matsuhisia et al. (GCA, 1978), there is no single factor that controls the δ17O-δ18O slope, and clearly there is no `correct' TFL line. However, some generalities can be noted. 1) Meteoric waters generally plot with a λ = 0.528 with a Δ'17O = 0.033. At both high and low δ18O values, the Δ'17O values of meteoritic waters decrease. Mantle derived samples plot in a limited δ space, with δ18O values of 5-9‰ and a Δ'17O of -0.05‰. Rock and mineral samples falling outside this narrow range have undergone interaction with meteoric or ocean water at some point in their history, either by alteration or neoform mineral growth. The quartz-water triple isotope fractionation factor varies with temperatures, ranging from 0.5237 to 0.5266 at 0°C and 200°C, respective. A fit to published rock data gives an overall λ = 0.5237-0.5240. These results are most likely explained by the sum of hydrothermal and low-temperature mineral-water fractionations. Attempting to place any significance on a TFL from a set of data in unwarranted without understanding the processes controlling the isotopic compositions of the phases.

Perchlorate in the Great Lakes: isotopic composition and origin.

PubMed

Poghosyan, Armen; Sturchio, Neil C; Morrison, Candice G; Beloso, Abelardo D; Guan, Yunbin; Eiler, John M; Jackson, W Andrew; Hatzinger, Paul B

2014-10-07

Perchlorate is a persistent and mobile contaminant in the environment with both natural and anthropogenic sources. Stable isotope ratios of oxygen (δ(18)O, Δ(17)O) and chlorine (δ(37)Cl) along with the abundance of the radioactive isotope (36)Cl were used to trace perchlorate sources and behavior in the Laurentian Great Lakes. These lakes were selected for study as a likely repository of recent atmospheric perchlorate deposition. Perchlorate concentrations in the Great Lakes range from 0.05 to 0.13 μg per liter. δ(37)Cl values of perchlorate from the Great Lakes range from +3.0‰ (Lake Ontario) to +4.0‰ (Lake Superior), whereas δ(18)O values range from -4.1‰ (Lake Superior) to +4.0‰ (Lake Erie). Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ(17)O values (+1.6‰ to +2.7‰) divided into two distinct groups: Lake Superior (+2.7‰) and the other four lakes (∼+1.7‰). The stable isotopic results indicate that perchlorate in the Great Lakes is dominantly of natural origin, having isotopic composition resembling that measured for indigenous perchlorate from preindustrial groundwaters of the western USA. The (36)Cl/Cl ratio of perchlorate varies widely from 7.4 × 10(-12) (Lake Ontario) to 6.7 × 10(-11) (Lake Superior). These (36)ClO4(-) abundances are consistent with an atmospheric origin of perchlorate in the Great Lakes. The relatively high (36)ClO4(-) abundances in the larger lakes (Lakes Superior and Michigan) could be explained by the presence of (36)Cl-enriched perchlorate deposited during the period of elevated atmospheric (36)Cl activity following thermonuclear bomb tests in the Pacific Ocean.

Spatial analysis of annual mean stable isotopes in precipitation across Japan based on an intensive observation period throughout 2013.

PubMed

Ichiyanagi, Kimpei; Tanoue, Masahiro

2016-01-01

Spatial distribution of annual mean stable isotopes in precipitation (δ(18)O, δ(2)H) was observed at 56 sites across Japan throughout 2013. Annual mean δ(18)O values showed a strong latitude effect, from -12.4 ‰ in the north to -5.1 ‰ in the south. Annual mean d-excess values ranged from 8 to 21 ‰, and values on the Sea of Japan side in Northern and Eastern Japan were relatively higher than those on the Pacific Ocean side. The local meteoric water line (LMWL) and isotope effects were based on the annual mean values from all sites across Japan as divided into distinct regions: the Sea of Japan side to the Pacific Ocean side and Northeastern to Southwestern Japan. Slopes and intercepts of LMWL ranged from 7.4 to 7.8 and 9.8 to 13.0, respectively. Slopes for latitude, altitude, and temperature effects ranged from -0.27 to -0.48 ‰/°N, -0.0034 to -0.0053 ‰/m, and 0.36 to 0.46 ‰/°C, respectively, with statistically significance at the 99 % level. However, there was no precipitation amount effect. From the result of a multiple regression analysis, the empirical formula of annual mean δ(18)O in precipitation from latitude and altitude for all sites across Japan was determined to be δ(18) O = -0.348 (LAT) - 0.00307 (ALT) + 4.29 (R(2) = 0.59). Slopes for latitude and altitude ranged from - 0.28 to - 0.51, and - 0.0019 to - 0.0045, respectively. Even though site distribution was uneven, these equations are the first trial estimation for annual mean stable isotopes in precipitation across Japan. Further research performed on the monthly basis is required to elucidate factors controlling the spatiotemporal variability of stable isotopes in precipitation across Japan.

Geochemical and Sr isotopic variations in groundwaters of the Edwards aquifer, central Texas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oetting, G.C.; Banner, J.L.; Sharp, J.M. Jr.

1992-01-01

The regionally-extensive Edwards aquifer of central Texas lies on the northwestern edge of the Gulf of Mexico Basin. The aquifer system is composed primarily of lower Cretaceous marine limestones and dolostones with minor evaporitic and siliciclastic confining units of the Edwards Group and associated formations. The eastern and southern boundaries of the freshwater aquifer are defined by an abrupt change in groundwater salinity that is known as the badwater line. Variation in the isotopic composition and concentration of Sr in the mineral phases and waters in this aquifer system provide means to examine groundwater evolution processes. Models of simultaneous variationsmore » in Sr isotopes and major and trace ions are used to constrain processes of groundwater-rock interaction and groundwater mixing. Geochemical variations were examined in Edwards carbonate host rocks and groundwaters in Williamson and Bell Counties. Groundwaters were sampled along and across the badwater line, and range in salinity from 320--2,630 mg/l total dissolved solids. Major ion distributions in the water samples demonstrate a hydrochemical facies transition from Ca-HCO[sub 3] freshwaters to Na-Cl-SO[sub 4]-HCO[sub 3] badwaters. Both water types show a wide range of [sup 87]Sr/[sup 86]Sr values: Ca-HCO[sub 3] waters range from values of 0.7078--0.7093, and Na-Cl-SO[sub 4]-HCO[sub 3] waters range from values of 0.7087--0.7097. The Sr isotope compositions for both water groups are significantly greater than their host marine carbonates ([approximately]0.7075). The high Sr isotopic compositions indicate an extraformational source of Sr in both hydrochemical facies. Fluid mixing processes involving a freshwater and at least two badwater endmembers are required to account for variations in elemental and isotopic compositions in the groundwaters. Mineral-solution reactions may operate during and/or subsequent to mixing to produce the compositional variability observed in some intermediate waters.« less

O and H Isotope Ratios of Syenite Blocks in the El Abrigo Ignimbrite, Tenerife, Canary Islands: A Hydrothermal Fingerprint for Assimilation

NASA Astrophysics Data System (ADS)

Larson, P. B.; Nichols, H. J.; Wolff, J. A.; Marti, J.

2001-12-01

As part of an ongoing project investigating assimilation in ocean island magmas, we are measuring stable isotope ratios of hydrothermally altered lithic fragments in phonolitic pyroclastic deposits from Tenerife, Canary Islands. Nepheline syenite blocks occur in the 0.196 Ma El Abrigo ignimbrite of the Diego Hernandez Formation (DHF). The DHF is the most recent of at least three caldera-forming magmatic cycles on Tenerife. The blocks are fragments of evolved plutons that are chemically similar to phonolites but extend to more strongly differentiated compositions. Distinct major and trace element concentrations suggest that the blocks derive from two intrusions, here referred to as A and B. The B syenites have chemical affinities with the El Abrigo phonolite, and some blocks contain small pockets of residual glass, suggesting that the B pluton may have been coeval with the El Abrigo magma. O isotope ratios of the B syenites lie within the range 4.8 to 7.0 per mil. The B samples are mostly fresh, and their higher O isotope ratios are near pristine magmatic values. Lower values occur in rocks with mild hydrothermal mineralogic alteration, and their values reflect limited high-temperature water-rock isotope exchange. O isotope ratios for A blocks are lower (0.1 to 6.3 per mil, most less than 2.0 per mil), and some samples show extensive mineral alteration. Near-ubiquitous alteration among the A samples, distinct major and trace element compositions, and lack of glass show that this syenite was older than, and unrelated to, the El Abrigo magma. Syenite D/H ratios range from -90 to -120 per mil. O vs H isotope relations indicate that an 18O-depleted meteoric water was the most important reservoir for the high-temperature hydrothermal fluid. Assimilation of altered syenite should provide a distinct stable isotope fingerprint that would be inherited by the product magma. DHF phonolites yield O ratios in the range 5.5 to 7.0 per mil, which may be this fingerprint. Assimilation of variably altered syenites, with accompanying fractionation, is a viable mechanism for producing this stable isotope variability in the magmas.

Fate of process solution cyanide and nitrate at three nevada gold mines inferred from stable carbon and nitrogen isotope measurements

USGS Publications Warehouse

Johnson, C.A.; Grimes, D.J.; Rye, R.O.

2000-01-01

Stable isotope methods have been used to identify the mechanisms responsible for cyanide consumption at three heap-leach operations that process Carlin-type gold ores in Nevada, U.S.A. The reagent cyanide had ??15N values ranging from -5 to -2??? and ??13C values from -60 to -35???. The wide ??13C range reflects the use by different suppliers of isotopically distinct natural-gas feedstocks and indicates that isotopes may be useful in environmental studies where there is a need to trace cyanide sources. In heap-leach circuits displaying from 5 to 98% consumption of cyanide, barren-solution and pregnant-solution cyanide were isotopically indistinguishable. The similarity is inconsistent with cyanide loss predominantly by HCN offgassing (a process that in laboratory experiments caused substantial isotopic changes), but it is consistent with cyanide retention within the heaps as solids, a process that caused minimal isotopic changes in laboratory simulations, or with cyanide oxidation, which also appears to cause minimal changes. In many pregnant solutions cyanide was carried entirely as metal complexes, which is consistent with ferrocyanides having precipitated or cyanocomplexes having been adsorbed within the heaps. It is inferred that gaseous cyanide emissions from operations of this type are less important than has generally been thought and that the dissolution or desorption kinetics of solid species is an important control on cyanide elution when the spent heaps undergo rinsing. Nitrate, nitrite and ammonium had ??15N values of 1-16???. The data reflect isotopic fractionation during ammonia offgassing or denitrification of nitrate - particularly in reclaim ponds - but do not indicate the extent to which nitrate is derived from cyanide or from explosive residues. ?? The Institution of Mining and Metallurgy 2000.

Late Pleistocene Southeast Amazonia Paleoenvironmental reconstruction inferred by bulk, isotopic and molecular organic matter. Saci lake-Para-Brazil

NASA Astrophysics Data System (ADS)

Martins, G. S.; Cordeiro, R. C.; Turcq, B.; Moreira, L. S.; Bouloubassi, I.; Sifeddine, A.

2014-12-01

Bulk, Isotope and biolomecular analysis supported by 22 14C AMS dates, allowed the reconstruction of environmental changes during the last 35 000 years BP in the Southeast Amazonian basin. A terrestrial origin has been inferred for the odd carbon-numbered long-chain (>C27) n-alkanes. The entire n-alkane δ13C range between -31.7‰ and -36.8‰, which is the isotopic range occupied by C3 vegetation. The C29:C31 ratio shows that a gramineae contribution is higher during the Pleistocene than in Holocene. The n-alkanes concentration decrease between 32 000 - 18 000, suggesting a increase in arid conditions. The ACL index confirm this interpretation showing high values due the Pleistocene linked to more hydrological stress. A shift in the abundance of n-alkane and isotopic values are observed across the late Pleistocene glacial-Holocene interglacial climate change, suggesting a climate-induced vegetational change. During the middle Holocene the n-alcanes values decreases indicating rain forest regression accompanied by increase in the ACL values confirming the dry climate conditions. Comparison with other South American records, our record indicates regression/expansion of the rain forest linked to the South American System monsoon activity since 35 kyrs.

Environmental Isotope Characteristics of Landfill Leachates and Gases

USGS Publications Warehouse

Hackley, Keith C.; Liu, Chao-Li; Coleman, D.D.

1996-01-01

The isotopic characteristics of municipal landfill leachate and gases (carbon dioxide and methane) are unique relative to the aqueous and gaseous media in most other natural geologic environments. The ??13 C of the CO2 in landfills is significantly enriched in 13C, with values as high as +20??? reported. The ?? 13C and ??D values of the methane fall within a range of values representative of microbial methane produced primarily by the acetate-fermentation process. The ??D of landfill leachate is strongly enriched in deuterium, by approximately 30??? to nearly 60??? relative to local average precipitation values. This deuterium enrichment is undoubtedly due to the extensive production of microbial methane within the limited reservoir of a landfill. The concentration of the radiogenic isotopes, 14C and 3H, are significantly elevated in both landfill leachate and methane. The 14C values range between approximately 120 and 170 pMC and can be explained by the input of organic material that was affected by the increased 14C content of atmospheric CO2 caused by atmospheric testing of nuclear devices. The tritium measured in leachate, however, is often too high to be explained by previous atmospheric levels and must come from material buried within the landfill. The unique isotopic characteristics observed in landfill leachates and gases provide a very useful technique for confirming whether contamination is from a municipal landfill or some other local source.

The Molybdenum Isotope System as a Tracer of Slab Input in Subduction Zones: An Example From Martinique, Lesser Antilles Arc

NASA Astrophysics Data System (ADS)

Gaschnig, Richard M.; Reinhard, Christopher T.; Planavsky, Noah J.; Wang, Xiangli; Asael, Dan; Chauvel, Catherine

2017-12-01

Molybdenum isotopes are fractionated by Earth-surface processes and may provide a tracer for the recycling of crustal material into the mantle. Here, we examined the Mo isotope composition of arc lavas from Martinique in the Lesser Antilles arc, along with Cretaceous and Cenozoic Deep Sea Drilling Project sediments representing potential sedimentary inputs into the subduction zone. Mo stable isotope composition (defined as δ98Mo in ‰ deviation from the NIST 3134 standard) in lavas older than ˜7 million years (Ma) exhibits a narrow range similar to and slightly higher than MORB, whereas those younger than ˜7 Ma show a much greater range and extend to unusually low δ98Mo values. Sediments from DSDP Leg 78A, Site 543 have uniformly low δ98Mo values whereas Leg 14, Site 144 contains both sediments with isotopically light Mo and Mo-enriched black shales with isotopically heavy Mo. When coupled with published radiogenic isotope data, Mo isotope systematics of the lavas can be explained through binary mixing between a MORB-like end-member and different sedimentary compositions identified in the DSDP cores. The lavas older than ˜7 Ma were influenced by incorporation of isotopically heavy black shales into the mantle wedge. The younger lavas are the product of mixing isotopically light sedimentary material into the mantle wedge. The change in Mo isotope composition of the lavas at ˜7 Ma is interpreted to reflect the removal of the Cretaceous black shale component due to the arrival of younger ocean crust where the age-equivalent Cretaceous sediments were deposited in shallower oxic waters. Isotopic fractionation of Mo during its removal from the slab is not required to explain the observed systematics in this system.

Sulfur record of rising and falling marine oxygen and sulfate levels during the Lomagundi event

PubMed Central

Planavsky, Noah J.; Bekker, Andrey; Hofmann, Axel; Owens, Jeremy D.; Lyons, Timothy W.

2012-01-01

Carbonates from approximately 2.3–2.1 billion years ago show markedly positive δ13C values commonly reaching and sometimes exceeding +10‰. Traditional interpretation of these positive δ13C values favors greatly enhanced organic carbon burial on a global scale, although other researchers have invoked widespread methanogenesis within the sediments. To resolve between these competing models and, more generally, among the mechanisms behind Earth’s most dramatic carbon isotope event, we obtained coupled stable isotope data for carbonate carbon and carbonate-associated sulfate (CAS). CAS from the Lomagundi interval shows a narrow range of δ34S values and concentrations much like those of Phanerozoic and modern marine carbonate rocks. The δ34S values are a close match to those of coeval sulfate evaporites and likely reflect seawater composition. These observations are inconsistent with the idea of diagenetic carbonate formation in the methanic zone. Toward the end of the carbon isotope excursion there is an increase in the δ34S values of CAS. We propose that these trends in C and S isotope values track the isotopic evolution of seawater sulfate and reflect an increase in pyrite burial and a crash in the marine sulfate reservoir during ocean deoxygenation in the waning stages of the positive carbon isotope excursion. PMID:23090989

A mantle origin for Paleoarchean peridotitic diamonds from the Panda kimberlite, Slave Craton: Evidence from 13C-, 15N- and 33,34S-stable isotope systematics

NASA Astrophysics Data System (ADS)

Cartigny, Pierre; Farquhar, James; Thomassot, Emilie; Harris, Jeffrey W.; Wing, Bozwell; Masterson, Andy; McKeegan, Kevin; Stachel, Thomas

2009-11-01

In order to address diamond formation and origin in the lithospheric mantle underlying the Central Slave Craton, we report N- and C-stable isotopic compositions and N-contents and aggregation states for 85 diamonds of known paragenesis (73 peridotitic, 8 eclogitic and 4 from lower mantle) from the Panda kimberlite (Ekati Mine, Lac de Gras Area, Canada). For 12 peridotitic and two eclogitic sulfide inclusion-bearing diamonds from this sample set, we also report multiple-sulfur isotope ratios. The 73 peridotitic diamonds have a mean δ13C-value of - 5.2‰ and range from - 6.9 to - 3.0‰, with one extreme value at - 14.1‰. The associated δ15N-values range from - 17.0 to + 8.5‰ with a mean value of - 4.0‰. N-contents range from 0 to 1280 ppm. The 8 eclogitic diamonds have δ13C-values ranging from - 11.2 to - 4.4‰ with one extreme value at - 19.4‰. Their δ15N ranges from - 2.1 to + 7.9‰ and N-contents fall between 0 and 3452 ppm. Four diamonds with an inferred lower mantle origin are all Type II (i.e. nitrogen-free) and have a narrow range of δ13C values, between - 4.5 and - 3.5‰. The δ34S of the 14 analyzed peridotitic and eclogitic sulfide inclusions ranges from - 3.5 to +5.7‰. None of them provide evidence for anomalous δ33S-values; observed variations in δ33S are from +0.19 to - 0.33‰, i.e. within the 2 sigma uncertainties of mantle sulfur ( δ33S = 0‰). At Panda, the N contents and the δ13C of sulfide-bearing peridotitic diamonds show narrower ranges than silicate-bearing peridotitic diamonds. This evidence supports the earlier suggestion established from eclogitic diamonds from the Kaapvaal that sulfide-(±silicate) bearing diamonds sample a more restricted portion of sublithospheric mantle than silicate-(no sulfide) bearing diamonds. Our findings at Panda suggest that sulfide-bearing diamonds should be considered as a specific diamond population on a global-scale. Based on our study of δ34S, Δ 33S, δ15N and δ13C, we find no evidence for subduction-related isotopic signatures in the mantle sampled by Panda diamonds.

Classification of nine malathion emulsion samples by using carbon isotope ratios and the ratio of organic solvents.

PubMed

Suto, Nana; Kawashima, Hiroto

2017-01-01

The compound specific isotope analysis is nowadays an important and powerful tool in geochemical, environmental and forensics field. On November 2013, Aqli Foods Corporation in Japan dealt with complaints about stench from frozen foods produced. Subsequently, very high concentrations of organophosphorus pesticide as malathion, ethylbenzene and xylene were detected in recovered frozen foods. In particular case, we present the method to measure the stable carbon isotope ratio (δ 13 C) of nine malathion emulsion pesticides using gas chromatography/isotope ratio mass spectrometry (GC/IRMS) to identify the source. The δ 13 C values of malathion ranged from -30.6‰ to -29.5‰. Because malathion used in all malathion emulsions sold in Japan is imported from the same overseas company, Cheminova, Denmark. The δ 13 C values of ethylbenzene ranged from -28.2‰ to -20.8‰ and those of m,p-xylene from -28.7‰ to -25.2‰. The differences in the δ 13 C values may be because of the material itself and chemical processing. We also determined the ratio of ethylbenzene to m,p-xylene and finally categorized the nine malathion samples into five groups on the basis of this ratio and the δ 13 C values of ethylbenzene and m,p-xylene. The results of isotopic fractionation during volatilization (refrigerate, room temperature and incubator) was negligible small. Copyright © 2016 The Chartered Society of Forensic Sciences. Published by Elsevier Ireland Ltd. All rights reserved.

Variability in magnesium, carbon and oxygen isotope compositions, and trace element contents of brachiopod shells: implications for paleoceanographic studies

NASA Astrophysics Data System (ADS)

Rollion-Bard, Claire; Saulnier, Ségolène; Vigier, Nathalie; Schumacher, Aimryc; Chaussidon, Marc; Lécuyer, Christophe

2016-04-01

Magnesium content in the ocean is ≈ 1290 ppm and is one of the most abundant elements. It is involved in the carbon cycle via the dissolution and precipitation of carbonates, especially Mg-rich carbonates as dolomites. The Mg/Ca ratio of the ocean is believed to have changed through time. The causes of these variations, i.e. hydrothermal activity change or enhanced precipitation of dolomite, could be constrained using the magnesium isotope composition (δ26Mg) of carbonates. Brachiopods, as marine environmental proxies, have the advantage to occur worldwide in a depth range from intertidal to abyssal, and have been found in the geological record since the Cambrian. Moreover, as their shell is in low-Mg calcite, they are quite resistant to diagenetic processes. Here we report δ26Mg, δ18O, δ13C values along with trace element contents of one modern brachiopod specimen (Terebratalia transversa) and one fossil specimen (Terebratula scillae, 2.3 Ma). We combined δ26Mg values with oxygen and carbon isotope compositions and trace element contents to look for possible shell geochemical heterogeneities in order to investigate the processes that control the Mg isotope composition of brachiopod shells. We also evaluate the potential of brachiopods as a proxy of past seawater δ26Mg values. The two investigated brachiopod shells present the same range of δ26Mg variation (up to 2 ‰)). This variation cannot be ascribed to changes in environmental parameters, i.e. temperature or pH. As previously observed, the primary layer of calcite shows the largest degree of oxygen and carbon isotope disequilibrium relative to seawater. In contrast, the δ26Mg value of this layer is comparable to that of the secondary calcite layer value. In both T. scillae and T. transversa, negative trends are observable between magnesium isotopic compositions and oxygen and carbon isotopic compositions. These trends, combined to linear relationships between δ26Mg values and REE contents, are best explained by kinetic effects linked to changes in growth rate during the brachiopod life. The innermost calcite layer of T. transversa is in isotopic equilibrium for both oxygen and magnesium and could therefore be the best target for reconstructing past δ26Mg values of seawater.

Integrated Fe- and S-isotope study of seafloor hydrothermal vents at East Pacific Rise 9-10°N

USGS Publications Warehouse

Rouxel, O.; Shanks, Wayne C.; Bach, W.; Edwards, K.J.

2008-01-01

In this study, we report on coupled Fe- and S-isotope systematics of hydrothermal fluids and sulfide deposits from the East Pacific Rise at 9–10°N to better constrain processes affecting Fe-isotope fractionation in hydrothermal environments. We aim to address three fundamental questions: (1) Is there significant Fe-isotope fractionation during sulfide precipitation? (2) Is there significant variability of Fe-isotope composition of the hydrothermal fluids reflecting sulfide precipitation in subsurface environments? (3) Are there any systematics between Fe- and S-isotopes in sulfide minerals? The results show that chalcopyrite, precipitating in the interior wall of a hydrothermal chimney displays a limited range of δ56Fe values and δ34S values, between − 0.11 to − 0.33‰ and 2.2 to 2.6‰ respectively. The δ56Fe values are, on average, slightly higher by 0.14‰ relative to coeval vent fluid composition while δ34S values suggest significant S-isotope fractionation (− 0.6 ± 0.2‰) during chalcopyrite precipitation. In contrast, systematically lower δ56Fe and δ34S values relative to hydrothermal fluids, by up to 0.91‰ and 2.0‰ respectively, are observed in pyrite and marcasite precipitating in the interior of active chimneys. These results suggest isotope disequilibrium in both Fe- and S-isotopes due to S-isotopic exchange between hydrothermal H2S and seawater SO42− followed by rapid formation of pyrite from FeS precursors, thus preserving the effects of a strong kinetic Fe-isotope fractionation during FeS precipitation. In contrast, δ56Fe and δ34S values of pyrite from inactive massive sulfides, which show evidence of extensive late-stage reworking, are essentially similar to the hydrothermal fluids. Multiple stages of remineralization of ancient chimney deposits at the seafloor appear to produce minimal Fe-isotope fractionation. Similar affects are indicated during subsurface sulfide precipitation as demonstrated by the lack of systematic differences between δ56Fe values in both high-temperature, Fe-rich black smokers and lower-temperature, Fe-depleted vents.

The conflict between cheetahs and humans on Namibian farmland elucidated by stable isotope diet analysis.

PubMed

Voigt, Christian C; Thalwitzer, Susanne; Melzheimer, Jörg; Blanc, Anne-Sophie; Jago, Mark; Wachter, Bettina

2014-01-01

Large areas of Namibia are covered by farmland, which is also used by game and predator species. Because it can cause conflicts with farmers when predators, such as cheetahs (Acinonyx jubatus), hunt livestock, we assessed whether livestock constitutes a significant part of the cheetah diet by analysing the stable isotope composition of blood and tissue samples of cheetahs and their potential prey species. According to isotopic similarities, we defined three isotopic categories of potential prey: members of a C4 food web with high δ15N values (gemsbok, cattle, springhare and guinea fowl) and those with low δ15N values (hartebeest, warthog), and members of a C3 food web, namely browsers (eland, kudu, springbok, steenbok and scrub hare). We quantified the trophic discrimination of heavy isotopes in cheetah muscle in 9 captive individuals and measured an enrichment for 15N (3.2‰) but not for 13C in relation to food. We captured 53 free-ranging cheetahs of which 23 were members of groups. Cheetahs of the same group were isotopically distinct from members of other groups, indicating that group members shared their prey. Solitary males (n = 21) and males in a bachelor groups (n = 11) fed mostly on hartebeest and warthogs, followed by browsers in case of solitary males, and by grazers with high δ15N values in case of bachelor groups. Female cheetahs (n = 9) predominantly fed on browsers and used also hartebeest and warthogs. Mixing models suggested that the isotopic prey category that included cattle was only important, if at all, for males living in bachelor groups. Stable isotope analysis of fur, muscle, red blood cells and blood plasma in 9 free-ranging cheetahs identified most individuals as isotopic specialists, focussing on isotopically distinct prey categories as their food.

Relationship between the trajectory of mid-latitude cyclones in the eastern Pacific Ocean and the isotopic composition of snowfall in the Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Vasquez, K. T.; Sickman, J. O.; Heard, A.; Lucero, D.

2013-12-01

Diatoms, preserved in lake sediments, provide a potential archive of snowfall variability in the Sierra Nevada through their sensitivity to changes in water chemistry (a proxy for runoff volume) and by recording the isotopic composition of snow-melt (potentially a proxy for sources of atmospheric moisture). In the Sierra Nevada, we hypothesize that the oxygen isotopic composition of diatom silica is principally controlled by snow and that the isotopic composition of snow varies as a function of the tracks of mid-latitude cyclonic storms in the eastern Pacific Ocean. Snow samples from discrete storms were collected from December 2012 to March 2013 at 2042 meters a.s.l. in Sequoia National Park. The δ18O and δ2H values of the snow samples were measured using a temperature-conversion elemental analyzer coupled to a Delta V isotope ratio mass spectrometer. The isotopic measurements were then coupled to 3, 5 and 7-day air mass back trajectories using the NOAA HYSPLIT model. The measured δ18O values ranged from -17.6 to -7.8 per mil and the δ2H ranged from -119.8 to -73.3 per mil. Both δ18O and δ2H were inversely related to the latitude of the storm origin (R^2 values of 0.67 and 0.57, respectively). Winter storms from the Gulf of Alaska were the most isotopically depleted while storms originating in the subtropical/tropical Pacific were the most isotopically enriched, reflecting the overall latitudinal pattern of ocean-water isotope composition in the Pacific Ocean. Our results suggest that the isotopic composition of Sierra Nevada snowfall is influenced by storm track trajectory and this relationship could be useful in interpreting the climatic significance of δ18O of diatom silica preserved in lake cores.

The Conflict between Cheetahs and Humans on Namibian Farmland Elucidated by Stable Isotope Diet Analysis

PubMed Central

Voigt, Christian C.; Thalwitzer, Susanne; Melzheimer, Jörg; Blanc, Anne-Sophie; Jago, Mark; Wachter, Bettina

2014-01-01

Large areas of Namibia are covered by farmland, which is also used by game and predator species. Because it can cause conflicts with farmers when predators, such as cheetahs (Acinonyx jubatus), hunt livestock, we assessed whether livestock constitutes a significant part of the cheetah diet by analysing the stable isotope composition of blood and tissue samples of cheetahs and their potential prey species. According to isotopic similarities, we defined three isotopic categories of potential prey: members of a C4 food web with high δ15N values (gemsbok, cattle, springhare and guinea fowl) and those with low δ15N values (hartebeest, warthog), and members of a C3 food web, namely browsers (eland, kudu, springbok, steenbok and scrub hare). We quantified the trophic discrimination of heavy isotopes in cheetah muscle in 9 captive individuals and measured an enrichment for 15N (3.2‰) but not for 13C in relation to food. We captured 53 free-ranging cheetahs of which 23 were members of groups. Cheetahs of the same group were isotopically distinct from members of other groups, indicating that group members shared their prey. Solitary males (n = 21) and males in a bachelor groups (n = 11) fed mostly on hartebeest and warthogs, followed by browsers in case of solitary males, and by grazers with high δ15N values in case of bachelor groups. Female cheetahs (n = 9) predominantly fed on browsers and used also hartebeest and warthogs. Mixing models suggested that the isotopic prey category that included cattle was only important, if at all, for males living in bachelor groups. Stable isotope analysis of fur, muscle, red blood cells and blood plasma in 9 free-ranging cheetahs identified most individuals as isotopic specialists, focussing on isotopically distinct prey categories as their food. PMID:25162403

Testing the Late-Veneer hypothesis with selenium isotopes

NASA Astrophysics Data System (ADS)

Labidi, J.; Koenig, S.; Bennett, N.; Kurzawa, T.; Aierken, E.; Shahar, A.; Schoenberg, R.

2016-12-01

Selenium (Se) is a siderophile element displaying an excess abundance in Earth's mantle compared to experimental predictions [1], which may be attributed to the Late-Veneer. As Se is also volatile, testing the late-veneer addition of Se can constrain the origin of other volatile elements on Earth. Here we combine high-precision Se isotope measurements of metal-silicate partitioning experiments and chondrites to assess whether planetary differentiation could leave a measurable Se isotopic signature on planetary mantles. We performed Se isotopic measurements of 5 metal-silicate partitioning experiments and 20 chondrites of all major classes. Experiments were conducted at 1 GPa and 1650 C for 1 to 4 hours using the piston-cylinder apparatus at Carnegie's Geophysical Laboratory. After wet chemistry, data were obtained on a ThermoFisher Scientific™ NeptunePlus MC-ICP-MS at the University of Tübingen with a 74Se/77Se double spike technique. δ82/76Se values are given relative to NIST SRM-3149 and the external reproducibility calculated from duplicate meteorite analyses is ≤ 0.1‰ (2 s.d.). Chondrites vary over a 0.8‰ range of δ82/76Se values. CIs and CMs show evidence for heavier 82Se/76Se ratios, likely due to mixing processes in the proto-planetary nebula. When these isotopically heavier meteorites are excluded, remaining chondrites have δ82/76Se values varying over a 0.3‰ range, within uncertainty of previous results [2]. We suggest that these chondrites may be used to estimate a δ82/76Se value of bulk planets. At the conditions of our experiments, the partition coefficients for Se log Dmetal-silicate range from 0.7±0.1 to 1.9±0.1, consistent with previous work [1]. A small but resolvable Se isotopic fractionation was observed: 82Se/76Se ratios were enriched by ≤ 0.5‰ in the silicates relative to the metals. Thus, given current uncertainties for Se isotopic measurements, marginal differences between planetary mantles and chondrites may be resolved. [1] Rose-Weston et al. 2009, GCA, 73(15), 4598-4615. [2] Vollstaedt et al. 2016, 450, 372-380.

Quantitative measurement of carbon isotopic composition in CO2 gas reservoir by Micro-Laser Raman spectroscopy

NASA Astrophysics Data System (ADS)

Li, Jiajia; Li, Rongxi; Zhao, Bangsheng; Guo, Hui; Zhang, Shuan; Cheng, Jinghua; Wu, Xiaoli

2018-04-01

The use of Micro-Laser Raman spectroscopy technology for quantitatively determining gas carbon isotope composition is presented. In this study, 12CO2 and 13CO2 were mixed with N2 at various molar fraction ratios to obtain Raman quantification factors (F12CO2 and F13CO2), which provide a theoretical basis for calculating the δ13C value. And the corresponding values were 0.523 (0 < C12CO2/CN2 < 2) and 1.11998 (0 < C13CO2/CN2 < 1.5) respectively. It has shown that the representative Raman peak area can be used for the determination of δ13C values within the relative errors range of 0.076% to 1.154% in 13CO2/12CO2 binary mixtures when F12CO2/F13CO2 is 0.466972625. In addition, measurement of δ13C values by Micro-Laser Raman analysis were carried out on natural CO2 gas from Shengli Oil-field at room temperature under different pressures. The δ13C values obtained by Micro-Laser Raman spectroscopy technology and Isotope Ratio Mass Spectrometry (IRMS) technology are in good agreement with each other, and the relative errors range of δ13C values is 1.232%-6.964%. This research provides a fundamental analysis tool for determining gas carbon isotope composition (δ13C values) quantitatively by using Micro-Laser Raman spectroscopy. Experiment of results demonstrates that this method has the potential for obtaining δ13C values in natural CO2 gas reservoirs.

Fingerprints of carbon, nitrogen, and silicon isotopes in small interstellar SiC grains from the Murchison meteorite

NASA Technical Reports Server (NTRS)

Hoppe, Peter; Geiss, Johannes; Buehler, Fritz; Neuenschwander, Juerg; Amari, Sachiko; Lewis, Roy S.

1993-01-01

We report ion microprobe determinations of the carbon, nitrogen, and silicon isotopic compositions of small SiC grains from the Murchison CM2 chondrite. Analyses were made on samples containing variable numbers of grains and on 14 individual grains. In some cases the multiple-grain sample compositions were probably dominated by only one or two grains. Total ranges observed are given. Only a few grains show values near the range limits. Both the total ranges of carbon and nitrogen isotopic compositions, and even the narrower ranges typical for the majority of the grains, are similar to those observed for larger SiC grains. Two rare components appear to be present in the smaller-size fraction, one characterized by C-12/C-13 about 12-16 and the other by very heavy nitrogen. The carbon and nitrogen isotopic compositions qualitatively may reflect hydrostatic H-burning via the CNO cycle and He-burning in red giants, as well as explosive H-burning in novae. The silicon isotopic compositions of most grains qualitatively show what is the signature of He-burning. The silicon isotopic composition of one grain, however, suggests a different process.

Application of sulphur isotope ratios to examine weaning patterns and freshwater fish consumption in Roman Oxfordshire, UK

NASA Astrophysics Data System (ADS)

Nehlich, Olaf; Fuller, Benjamin T.; Jay, Mandy; Mora, Alice; Nicholson, Rebecca A.; Smith, Colin I.; Richards, Michael P.

2011-09-01

This study investigates the application of sulphur isotope ratios (δ 34S) in combination with carbon (δ 13C) and nitrogen (δ 15N) ratios to understand the influence of environmental sulphur on the isotopic composition of archaeological human and faunal remains from Roman era sites in Oxfordshire, UK. Humans ( n = 83), terrestrial animals ( n = 11), and freshwater fish ( n = 5) were analysed for their isotope values from four locations in the Thames River Valley, and a broad range of δ 34S values were found. The δ 34S values from the terrestrial animals were highly variable (-13.6‰ to +0.5‰), but the δ 34S values of the fish were clustered and 34S-depleted (-20.9‰ to -17.3‰). The results of the faunal remains suggest that riverine sulphur influenced the terrestrial sulphur isotopic signatures. Terrestrial animals were possibly raised on the floodplains of the River Thames, where highly 34S-depleted sulphur influenced the soil. The humans show the largest range of δ 34S values (-18.8‰ to +9.6‰) from any archaeological context to date. No differences in δ 34S values were found between the males (-7.8 ± 6.0‰) and females (-5.3 ± 6.8‰), but the females had a linear correlation ( R2 = 0.71; p < 0.0001) between their δ 15N and δ 34S compositions. These δ 34S results suggest a greater dietary variability for the inhabitants of Roman Oxfordshire than previously thought, with some individuals eating solely terrestrial protein resources and others showing a diet almost exclusively based on freshwater protein such as fish. Such large dietary variability was not visible by analysing only the carbon and nitrogen isotope ratios, and this research represents the largest and most detailed application of δ 34S analysis to examine dietary practices (including breastfeeding and weaning patterns) during the Romano-British Period.

[Tracing Sources of Sulfate Aerosol in Nanjing Northern Suburb Using Sulfur and Oxygen Isotopes].

PubMed

Wei, Ying; Guo, Zhao-bing; Ge, Xin; Zhu, Sheng-nan; Jiang, Wen-juan; Shi, Lei; Chen, Shu

2015-04-01

Abstract: To trace the sources of sulfate contributing to atmospheric aerosol, PM2.5 samples for isotopic analysis were collected in Nanjing northern suburb during January 2014. The sulfur and oxygen isotopic compositions of sulfate from these samples were determined by EA-IRMS. Source identification and apportionment were carried out using stable isotopic and chemical evidences, combined with absolute principal component analysis (APCA) method. The Δ34S values of aerosol sulfate ranged from 2.7 per thousand to 6.4 per thousand, with an average of 5.0 per thousand ± 0.9 per thousand, while the Δ18O values ranged from 10.6 per thousand to 16.1 per thousand, with an average of 12.5 per thousand ± 1.37 per thousand. In conjunction with air mass trajectories, the results suggested that aerosol sulfates were controlled by a dominance of local anthropogenic sulfate, followed by the contributions of long-distance transported sulfate. There was a minor effect of some other low-Δ34S valued sulfates, which might be expected from biogenic sources. Absolute principal component analysis results showed that the contributions of anthropogenic sulfate and long-distance transported sulfate were 46.74% and 31.54%, respectively.

Oxygen isotope studies of early Precambrian granitic rocks from the Giants Range batholith, northeastern Minnesota, U.S.A.

USGS Publications Warehouse

Viswanathan, S.

1974-01-01

Oxygen isotope studies of granitic rocks from the 2.7 b.y.-old composite Giants Range batholith show that: (1) ??(O18)quartz values of 9 to 10 permil characterize relatively uncontaminated Lower Precambrian, magmatic granodiorites and granites; (2) granitic rocks thought to have formed by static granitization have ??(O18)quartz values that are 1 to 2 permil higher than magmatic granitic rocks; (3) satellite leucogranite bodies have values nearly identical to those of the main intrusive phases even where they transect O18-rich metasedimentary wall rocks; (4) oxygen isotopic interaction between the granitic melts and their O18-rich wall rocks was minimal; and (5) O18/O18 ratios of quartz grains in a metasomatic granite are largely inherited from the precursor rock, but during the progression - sedimentary parent ??? partially granitized parent ??? metasomatic granite ??? there is gradual decrease in ??(O18)quartz by 1 to 2 permil. ?? 1974.

Isotope geochemistry of mercury in source rocks, mineral deposits and spring deposits of the California Coast Ranges, USA

NASA Astrophysics Data System (ADS)

Smith, Christopher N.; Kesler, Stephen E.; Blum, Joel D.; Rytuba, James J.

2008-05-01

We present here the first study of the isotopic composition of mercury in rocks, ore deposits, and active spring deposits from the California Coast Ranges, a part of Earth's crust with unusually extensive evidence of mercury mobility and enrichment. The Franciscan Complex and Great Valley Sequence, which form the bedrock in the California Coast Ranges, are intruded and overlain by Tertiary volcanic rocks including the Clear Lake Volcanic Sequence. These rocks contain two types of mercury deposits, hot-spring deposits that form at shallow depths (< 300 m) and silica-carbonate deposits that extend to depths of 1000 m. Active springs and geothermal areas continue to precipitate Hg and Au and are modern analogues to the fossil hydrothermal systems preserved in the ore deposits. The Franciscan Complex and Great Valley Sequence contain clastic sedimentary rocks with higher concentrations of mercury than volcanic rocks of the Clear Lake Volcanic Field. Mean mercury isotopic compositions ( δ202Hg) for all three rock units are similar, although the range of values in Franciscan Complex rocks is greater than in either Great Valley or Clear Lake rocks. Hot spring and silica-carbonate mercury deposits have similar average mercury isotopic compositions that are indistinguishable from averages for the three rock units, although δ202Hg values for the mercury deposits have a greater variance than the country rocks. Precipitates from spring and geothermal waters in the area have similarly large variance and a mean δ202Hg value that is significantly lower than the ore deposits and rocks. These observations indicate that there is little or no isotopic fractionation (< ± 0.5‰) during release of mercury from its source rocks into hydrothermal solutions. Isotopic fractionation does appear to take place during transport and concentration of mercury in deposits, however, especially in their uppermost parts. Boiling of hydrothermal fluids, separation of a mercury-bearing CO 2 vapor or reduction and volatilization of Hg (0) in the near-surface environment are likely the most important processes causing the observed Hg isotope fractionation. This should result in the release of mercury with low δ202Hg values into the atmosphere from the top of these hydrothermal systems. Estimates of mass balance suggest that residual Hg reservoirs are not measurably enriched in heavy Hg isotopes as a result of this process because only a small amount of Hg (< 4%) leaves actively ore-forming systems.

Isotope geochemistry of mercury in source rocks, mineral deposits and spring deposits of the California Coast Ranges, USA

USGS Publications Warehouse

Smith, C.N.; Kesler, S.E.; Blum, J.D.; Rytuba, J.J.

2008-01-01

We present here the first study of the isotopic composition of mercury in rocks, ore deposits, and active spring deposits from the California Coast Ranges, a part of Earth's crust with unusually extensive evidence of mercury mobility and enrichment. The Franciscan Complex and Great Valley Sequence, which form the bedrock in the California Coast Ranges, are intruded and overlain by Tertiary volcanic rocks including the Clear Lake Volcanic Sequence. These rocks contain two types of mercury deposits, hot-spring deposits that form at shallow depths (< 300??m) and silica-carbonate deposits that extend to depths of 1000??m. Active springs and geothermal areas continue to precipitate Hg and Au and are modern analogues to the fossil hydrothermal systems preserved in the ore deposits. The Franciscan Complex and Great Valley Sequence contain clastic sedimentary rocks with higher concentrations of mercury than volcanic rocks of the Clear Lake Volcanic Field. Mean mercury isotopic compositions (??202Hg) for all three rock units are similar, although the range of values in Franciscan Complex rocks is greater than in either Great Valley or Clear Lake rocks. Hot spring and silica-carbonate mercury deposits have similar average mercury isotopic compositions that are indistinguishable from averages for the three rock units, although ??202Hg values for the mercury deposits have a greater variance than the country rocks. Precipitates from spring and geothermal waters in the area have similarly large variance and a mean ??202Hg value that is significantly lower than the ore deposits and rocks. These observations indicate that there is little or no isotopic fractionation (< ?? 0.5???) during release of mercury from its source rocks into hydrothermal solutions. Isotopic fractionation does appear to take place during transport and concentration of mercury in deposits, however, especially in their uppermost parts. Boiling of hydrothermal fluids, separation of a mercury-bearing CO2 vapor or reduction and volatilization of Hg(0) in the near-surface environment are likely the most important processes causing the observed Hg isotope fractionation. This should result in the release of mercury with low ??202Hg values into the atmosphere from the top of these hydrothermal systems. Estimates of mass balance suggest that residual Hg reservoirs are not measurably enriched in heavy Hg isotopes as a result of this process because only a small amount of Hg (< 4%) leaves actively ore-forming systems. ?? 2008 Elsevier B.V. All rights reserved.

Deuterium values from volcanic glass: A paleoelevation proxy for Oregon's Cascade Range

NASA Astrophysics Data System (ADS)

Carlson, T. B.; Bershaw, J. T.

2016-12-01

Hydrated volcanic glass has been used as a proxy to constrain Cenozoic paleoclimate across many of the world's mountain ranges. However, there are concerns that volcanic glass may not preserve the isotopic composition of syndepositional meteoric water. The Cascades are an excellent location to study the validity of hydrated volcanic glass as a paleoenvironmental proxy for several reasons. Moisture is derived from a single oceanic source and falls as orographic precipitation in the Cascades, leading to a characteristic altitude effect, or inverse relationship between elevation and the isotopic composition of meteoric water (δD). In addition, past studies have inferred uplift of the Cascades and an increase in the rain shadow effect since the Eocene through independent methods such as changing fossil assemblages, and other isotopic proxies including carbonates and fossil teeth. In this study, δD values of two hydrated tuff samples are compared: one prior to ( 29 Ma) and one following ( 5 Ma) the onset of High Cascade volcanism. The isotopic composition of these samples are interpreted in the context of modern water across the range to understand the potential of volcanic glass as a proxy for paleoelevation in the Pacific Northwest.

15N isotopic analyses: a powerful tool to establish links between seized 3,4-methylenedioxymethamphetamine (MDMA) tablets.

PubMed

Palhol, Fabien; Lamoureux, Catherine; Naulet, Norbert

2003-06-01

In this study the (15)N/(14)N isotopic ratios of 43 samples of 3,4-methylenedioxymethamphetamine (MDMA) samples were measured using Gas Chromatography-Combustion-Isotope-Ratio Mass Spectrometry (GC-C-IRMS). The results show a large discrimination between samples with a range of delta(15)N values between -16 and +19 per thousand. Comparison between delta(15)N values and other physical and chemical parameters shows a strong relationship between delta(15)N and brand logo or composition. Thus, it could be assumed that tablets from different seizures probably originated from the same clandestine manufacturing source. Hence, (15)N isotopic parameters provide an important additional tool to establish common origins between seizures of clandestine synthetic drugs.

Determination of phenylalanine isotope ratio enrichment by liquid chromatography/time- of-flight mass spectrometry.

PubMed

Wu, Zhanpin; Zhang, Xiao-Jun; Cody, Robert B; Wolfe, Robert R

2004-01-01

The application of time-of-flight mass spectrometry to isotope ratio measurements has been limited by the relatively low dynamic range of the time-to-digital converter detectors available on commercial LC/ToF-MS systems. Here we report the measurement of phenylalanine isotope ratio enrichment by using a new LC/ToF-MS system with wide dynamic range. Underivatized phenylalanine was injected onto a C18 column directly with 0.1% formic acid/acetonitrile as the mobile phase. The optimal instrument parameters for the time-of-flight mass spectrometer were determined by tuning the instrument with a phenylalanine standard. The accuracy of the isotope enrichment measurement was determined by the injection of standard solutions with known isotope ratios ranging from 0.02% to 9.2%. A plot of the results against the theoretical values gave a linear curve with R2 of 0.9999. The coefficient of variation for the isotope ratio measurement was below 2%. The method is simple, rapid, and accurate and presents an attractive alternative to traditional GC/MS applications.

Isotopic constraints on ice age fluids in active geothermal systems: Reykjanes, Iceland

NASA Astrophysics Data System (ADS)

Pope, Emily C.; Bird, Dennis K.; Arnórsson, Stefán; Fridriksson, Thráinn; Elders, Wilfred A.; Fridleifsson, Gudmundur Ó.

2009-08-01

The Reykjanes geothermal system is located on the landward extension of the Mid-Atlantic Ridge in southwest Iceland, and provides an on-land proxy to high-temperature hydrothermal systems of oceanic spreading centers. Previous studies of elemental composition and salinity have shown that Reykjanes geothermal fluids are likely hydrothermally modified seawater. However, δD values of these fluids are as low as -23‰, which is indicative of a meteoric water component. Here we constrain the origin of Reykjanes hydrothermal solutions by analysis of hydrogen and oxygen isotope compositions of hydrothermal epidote from geothermal drillholes at depths between 1 and 3 km. δDEPIDOTE values from wells RN-8, -9, -10 and -17 collectively range from -60 to -78‰, and δ18OEPIDOTE in these wells are between -3.0 and 2.3‰. The δD values of epidote generally increase along a NE trend through the geothermal field, whereas δ18O values generally decrease, suggesting a southwest to northeast migration of the geothermal upflow zone with time that is consistent with present-day temperatures and observed hydrothermal mineral zones. For comparative analysis, the meteoric-water dominated Nesjavellir and Krafla geothermal systems, which have a δDFLUID of ˜ -79‰ and -89‰, respectively, show δDEPIDOTE values of -115‰ and -125‰. In contrast, δDEPIDOTE from the mixed meteoric-seawater Svartsengi geothermal system is -68‰; comparable to δDEPIDOTE from well RN-10 at Reykjanes. Stable isotope compositions of geothermal fluids in isotopic equilibrium with the epidotes at Reykjanes are computed using published temperature dependent hydrogen and oxygen isotope fractionation curves for epidote-water, measured isotope composition of the epidotes and temperatures approximated from the boiling point curve with depth. Calculated δD and δ18O of geothermal fluids are less than 0‰, suggesting that fluids of meteoric or glacial origin are a significant component of the geothermal solutions. Additionally, δDFLUID values in equilibrium with geothermal epidote are lower than those of modern-day fluids, whereas calculated δ18OFLUID values are within range of the observed fluid isotope composition. We propose that modern δDEPIDOTE and δDFLUID values are the result of diffusional exchange between hydrous alteration minerals that precipitated from glacially-derived fluids early in the evolution of the Reykjanes system and modern seawater-derived geothermal fluids. A simplified model of isotope exchange in the Reykjanes geothermal system, in which the average starting δDROCK value is -125‰ and the water to rock mass ratio is 0.25, predicts a δDFLUID composition within 1‰ of average measured values. This model resolves the discrepancy between fluid salinity and isotope composition of Reykjanes geothermal fluids, explains the observed disequilibrium between modern fluids and hydrothermal epidote, and suggests that rock-fluid interaction is the dominant control over the evolution of fluid isotope composition in the hydrothermal system.

Isotopic characterization of flight feathers in two pelagic seabirds: Sampling strategies for ecological studies

USGS Publications Warehouse

Wiley, Anne E.; Ostrom, Peggy H.; Stricker, Craig A.; James, Helen F.; Gandhi, Hasand

2010-01-01

We wish to use stable-isotope analysis of flight feathers to understand the feeding behavior of pelagic seabirds, such as the Hawaiian Petrel (Pterodroma sandwichensis) and Newell’s Shearwater (Puffinus auricularis newelli). Analysis of remiges is particularly informative because the sequence and timing of remex molt are often known. The initial step, reported here, is to obtain accurate isotope values from whole remiges by means of a minimally invasive protocol appropriate for live birds or museum specimens. The high variability observed in D13C and D15N values within a feather precludes the use of a small section of vane. We found the average range within 42 Hawaiian Petrel remiges to be 1.3‰ for both D13C and D15N and that within 10 Newell’s Shearwater remiges to be 1.3‰ and 0.7‰ for D13C and D15N, respectively. The D13C of all 52 feathers increased from tip to base, and the majority of Hawaiian Petrel feathers showed an analogous trend in D15N. Although the average range of DD in 21 Hawaiian Petrel remiges was 11‰, we found no longitudinal trend. We discuss influences of trophic level, foraging location, metabolism, and pigmentation on isotope values and compare three methods of obtaining isotope averages of whole feathers. Our novel barb-sampling protocol requires only 1.0 mg of feather and minimal preparation time. Because it leaves the feather nearly intact, this protocol will likely facilitate obtaining isotope values from remiges of live birds and museum specimens. As a consequence, it will help expand the understanding of historical trends in foraging behavior

Uranium-lead isotope systematics of Mars inferred from the basaltic shergottite QUE 94201

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaffney, A M; Borg, L E; Connelly, J N

2006-12-22

Uranium-lead ratios (commonly represented as {sup 238}U/{sup 204}Pb = {mu}) calculated for the sources of martian basalts preserve a record of petrogenetic processes that operated during early planetary differentiation and formation of martian geochemical reservoirs. To better define the range of {mu} values represented by the source regions of martian basalts, we completed U-Pb elemental and isotopic analyses on whole rock, mineral and leachate fractions from the martian meteorite Queen Alexandra Range 94201 (QUE 94201). The whole rock and silicate mineral fractions have unradiogenic Pb isotopic compositions that define a narrow range ({sup 206}Pb/{sup 204}Pb = 11.16-11.61). In contrast, themore » Pb isotopic compositions of weak HCl leachates are more variable and radiogenic. The intersection of the QUE 94201 data array with terrestrial Pb in {sup 206}Pb/{sup 204}Pb-{sup 207}Pb/{sup 204}Pb-{sup 208}Pb/{sup 204}Pb compositional space is consistent with varying amounts of terrestrial contamination in these fractions. We calculate that only 1-7% contamination is present in the purified silicate mineral and whole rock fractions, whereas the HCl leachates contain up to 86% terrestrial contamination. Despite the contamination, we are able to use the U-Pb data to determine the initial {sup 206}Pb/{sup 204}Pb of QUE 94201 (11.086 {+-} 0.008) and calculate the {mu} value of the QUE 94201 mantle source to be 1.823 {+-} 0.008. This is the lowest {mu} value calculated for any martian basalt source, and, when compared to the highest values determined for martian basalt sources, indicates that {mu} values in martian source reservoirs vary by at least 100%. The range of source {mu} values further indicates that the {mu} value of bulk silicate Mars is approximately three. The amount of variation in the {mu} values of the mantle sources ({mu} {approx} 2-4) is greater than can be explained by igneous processes involving silicate phases alone. We suggest the possibility that a small amount of sulfide crystallization may generate large extents of U-Pb fractionation during formation of the mantle sources of martian basalts.« less

Understanding Potassium Isotope Fractionation During Authigenic Clay Formation in Pore-fluid Systems: Implications for the δ41K of Seawater

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Higgins, J. A.

2015-12-01

Improvements in analytical precision on the latest generation multi-collector inductively coupled plasma mass spectrometers (MC-ICP-MS) have revealed a ~2‰ range in the ratios of stable potassium isotopes (41K/39K) in terrestrial materials (Morgan et al., in prep). Preliminary measurements of δ41K values indicate that seawater and silicate rocks are isotopically distinct reservoirs, with seawater having a δ41K value that is ~0.5‰ heavier than the silicate average (-0.5‰; Morgan et al., in prep). The heavy δ41K character of seawater might be related to 1) an isotopically enriched input flux (rivers and high-temperature hydrothermal reactions); or 2) a 41K-depleted sink associated with authigenic clay formation during low-temperature alteration of volcanic rocks. Here we present measurements of the δ41K values of pore-fluids from ODP site 1052 in order to constrain potassium isotope fractionation during secondary clay formation. We find that δ41K values and K concentrations both decline systematically with depth. Results from 1-D diffusion-advection-reaction modeling of potassium concentrations and isotopic compositions indicate that fractionation of K isotopes during diffusion (Bourg et al., 2010) can explain all of the change in δ41K values of the pore-fluid with depth. Although the size of the K sink at site 1052 is a trivial fraction of the global K sink in clay minerals, our results suggest that diffusive fractionation of K isotopes in shallow pore-fluids may be, in part, responsible for the elevated δ41K value of seawater.

Isotopic composition of carbon and nitrogen of suprabenthic fauna in the NW Balearic Islands (western Mediterranean)

NASA Astrophysics Data System (ADS)

Madurell, T.; Fanelli, E.; Cartes, J. E.

Stable isotope (δ 13C and δ 15N) analyses were performed on suprabenthic fauna collected in the western Mediterranean (NW Balearic Islands), at depths ranging between 350 and 780 m. Samples were collected seasonally at bi-monthly intervals during six cruises performed between August 2003 and June 2004, using a Macer-GIROQ suprabenthic sledge (0.5 mm mesh size). Twenty-four separate species (5 mysids, 12 amphipods, 2 cumaceans, 2 isopods, 1 euphausiid, 1 decapod and 1 fish) and bulk copepods were analyzed on a seasonal basis for stable carbon and nitrogen isotopes. Stable nitrogen isotope ratios (δ 15N) ranged from 2.3‰ (the amphipod Lepechinella manco in September 2003) to 13.0‰ (the amphipod Rhachotropis caeca in August 2003). δ 13C values ranged from - 24.2 (the cumacean Campylaspis sulcata in June 2004) to - 16.1 (the amphipod Bruzelia typica in November 2006). Both δ 13C and δ 15N values suggest that there are three trophic levels within the suprabenthic community. However, considering the bathymetric range of the species, the results suggest that the deepest assemblage supported only two trophic levels. The stable isotope ratios of suprabenthic fauna displayed a continuum of values and confirmed a wide spectrum of feeding types (from filter-feeders to predators). In general, and in spite of the poor knowledge about diets available for most suprabenthic species, higher δ 15N were found for carnivorous amphipods (e.g. Rhachotropis spp., Nicippe tumida) consuming copepods. Low overlap for δ 13C and δ 15N values was observed, though δ 15N values where less variable than δ 13C, which suggests high resource partitioning in this assemblage. Seasonal variations in isotopic composition for both δ 13C and δ 15N were low (less than 1‰ and 3‰, respectively) and variable depending on species. Low correlations between δ 13C and δ 15N of suprabenthic fauna were found for all periods studied, though increasing from February 2004 to June 2004 (after the main peak of primary production in surface). C:N ratio (indicator of lipid content) showed higher values in summer than in winter. This suggests that lipid content may explain the seasonal patterns of δ 13C variability and, due to the increase of storage products in phytoplankton and zooplankton, it possibly indicates the peak of primary production at the surface.

Isotope and chemical compositions of meteoric and thermal waters and snow from the greater Yellowstone National Park region

USGS Publications Warehouse

Kharaka, Yousif K.; Thordsen, James J.; White, Lloyd D.

2002-01-01

An intensive hydrogeologic investigation, mandated by U.S. Congress and centered on the Norris-Mammoth corridor was conducted by USGS and other scientists during 1988-90 to determine the effects of using thermal water from a private well located in the Corwin Springs Known Geothermal Resources Area, Montana, on the thermal springs of Yellowstone National Park (YNP), especially Mammoth Hot Springs. As part of this investigation, we carried out a detailed study of the isotopic and chemical compositions of meteoric water from cold springs and wells, of thermal water, especially from the Norris-Mammoth corridor and of snow. Additional sampling of meteoric and thermal waters from YNP and surrounding region in northwest Wyoming, southwest Montana and southeast Idaho was carried out in 1991-92 to characterize the distribution of water isotopes in this mountainous region and to determine the origin and possible recharge locations of thermal waters in and adjacent to the Park. The D and 18O values for 40 snow samples range from ?88 to ?178? and ?12.5 to ?23.9?, respectively, and define a well constrained line given by D = 8.2 18O + 14.7 (r2 = 0.99) that is nearly identical to the Global Meteoric Water Line. The D and 18O values of 173 cold water samples range from ?115 to ?153? and ?15.2 to ?20.2?, respectively, and exhibit a similar relationship although with more scatter and with some shift to heavier isotopes, most likely due to evaporation effects. The spatial distribution of cold-water isotopes shows a roughly circular pattern with isotopically lightest waters centered on the mountains and high plateau in the northwest corner of Yellowstone National Park and becoming heavier in all directions. The temperature effect due to altitude is the dominant control on stable water isotopes throughout the region; however, this effect is obscured in narrow 'canyons' and areas of high topographic relief. The effects due to distance (i.e. 'continental') and latitude on water isotopes probably are relatively minor and difficult to resolve from the major controls. The data indicate that the groundwater are derived predominantly from cold, isotopically light winter precipitation, and that the isotope values of groundwater from elevations above about 2.5-3.0 km in the Gallatin and northern Absaroka Ranges are light enough (The D ?149?) to be the presumed recharge water for the hydrothermal system in the Park. However, estimation of the present-day volume of this recharged, isotopically light water indicates that it is not adequate to supply the high (3-4 m3/s) thermal water discharges from YNP, and cooler temperatures at the time of recharge would be required. The volume of meteoric water with D values lighter than ?145? may be adequate for recharging the hydrothermal system, and this may be a more plausible value than the ?149? originally calculated from data that are subject to moderate uncertainties.

High-resolution carbonate isotopic study of the Mural Formation (Cerro Pimas section), Sonora, México: Implications for early Albian oceanic anoxic events

NASA Astrophysics Data System (ADS)

Madhavaraju, J.; Lee, Yong Il; Scott, R. W.; González-León, C. M.; Jenkyns, H. C.; Saucedo-Samaniego, J. C.; Ramasamy, S.

2018-03-01

The 420-m thick stratigraphic section of the Mural Formation that is exposed in the Cerro Pimas area of northern Sonora, Mexico, is composed of limestone lithofacies ranging from bioclastic wackestone to boundstone, whose biota is characterized by low diversity. Prominent age-diagnostic fossils are benthic foraminifera and long-ranging calcareous algae that indicate the Aptian/Albian boundary is close to the base of the Los Coyotes Member. The carbonates of this formation have negative to positive δ13C values (-4.63 to +2.6‰) and highly depleted δ18O values that range from -12.74 to -8.34‰. The absence of correlation between δ13C and δ18O values supports a primary marine origin for the δ13C values of these limestones. The carbon-isotopic curve of the Cerro Pimas stratigraphic section has well-defined δ13C segments (C8 - C15) that compare with published curves of similar age. In the lower part of the early Albian Los Coyotes Member, the presence of OAE 1b is indicated by an increase followed by a decrease in δ13C values, suggesting correlation with the Kilian Event. The middle part of the Los Coyotes Member has a significant negative carbon-isotope excursion correlated with the globally recognizable early Albian Paquier event. Moreover, another significant negative carbon-isotope shift is observed in the upper part of the Los Coyotes Member, which can be correlated with the Leenhardt Event. The occurrence of the Kilian, Paquier and Leenhardt Events (OAE 1b cluster) in the Cerro Pimas stratigraphy confirms the global nature of these early Albian disturbances of the carbon cycle.

Silicon isotope fractionation in bamboo and its significance to the biogeochemical cycle of silicon

NASA Astrophysics Data System (ADS)

Ding, T. P.; Zhou, J. X.; Wan, D. F.; Chen, Z. Y.; Wang, C. Y.; Zhang, F.

2008-03-01

A systematic investigation on silica contents and silicon isotope compositions of bamboos was undertaken. Seven bamboo plants and related soils were collected from seven locations in China. The roots, stem, branch and leaves for each plant were sampled and their silica contents and silicon isotope compositions were determined. The silica contents and silicon isotope compositions of bulk and water-soluble fraction of soils were also measured. The silica contents of studied bamboo organs vary from 0.30% to 9.95%. Within bamboo plant the silica contents show an increasing trend from stem, through branch, to leaves. In bamboo roots the silica is exclusively in the endodermis cells, but in stem, branch and leaves, the silica is accumulated mainly in epidermal cells. The silicon isotope compositions of bamboos exhibit significant variation, from -2.3‰ to 1.8‰, and large and systematic silicon isotope fractionation was observed within each bamboo. The δ 30Si values decrease from roots to stem, but then increase from stem, through branch, to leaves. The ranges of δ 30Si values within each bamboo vary from 1.0‰ to 3.3‰. Considering the total range of silicon isotope composition in terrestrial samples is only 7‰, the observed silicon isotope variation in single bamboo is significant and remarkable. This kind of silicon isotope variation might be caused by isotope fractionation in a Rayleigh process when SiO 2 precipitated in stem, branches and leaves gradually from plant fluid. In this process the Si isotope fractionation factor between dissolved Si and precipitated Si in bamboo ( αpre-sol) is estimated to be 0.9981. However, other factors should be considered to explain the decrease of δ 30Si value from roots to stem, including larger ratio of dissolved H 4SiO 4 to precipitated SiO 2 in roots than in stem. There is a positive correlation between the δ 30Si values of water-soluble fractions in soils and those of bulk bamboos, indicating that the dissolved silicon in pore water and phytoliths in soil is the direct sources of silicon taken up by bamboo roots. A biochemical silicon isotope fractionation exists in process of silicon uptake by bamboo roots. Its silicon isotope fractionation factor ( αbam-wa) is estimated to be 0.9988. Considering the distribution patterns of SiO 2 contents and δ 30Si values among different bamboo organs, evapotranspiration may be the driving force for an upward flow of a silicon-bearing fluid and silica precipitation. Passive silicon uptake and transportation may be important for bamboo, although the role of active uptake of silicic acid by roots may not be neglected. The samples with relatively high δ 30Si values all grew in soils showing high content of organic materials. In contrast, the samples with relatively low δ 30Si values all grew in soil showing low content of organic materials. The silicon isotope composition of bamboo may reflect the local soil type and growth conditions. Our study suggests that bamboos may play an important role in global silicon cycle.

Preservation of Fe Isotope Proxies in the Rock Record

NASA Astrophysics Data System (ADS)

Johnson, C.; Beard, B.; Valley, J.; Valaas, E.

2005-12-01

Iron isotope variations provide powerful constraints on redox conditions and pathways involved during biogeochemical cycling of Fe in surface and near-surface environments. The relative isotopic homogeneity of igneous rocks and most bulk weathering products contrasts with the significant isotopic variations (4 per mil in 56Fe/54Fe) that accompany oxidation of Fe(II)aq, precipitation of sulfides, and reduction by bacteria. These isotopic variations often reflect intrinsic (equilibrium) Fe isotope fractionations between minerals and aqueous species whose interactions may be directly or indirectly catalyzed by bacteria. In addition, Fe isotope exchange may be limited between reactive Fe pools in low-temperature aqueous-sediment environments, fundamentally reflecting disequilibrium effects. In the absence of significant sulfide, dissimilatory Fe(III) reduction by bacteria produces relatively low 56Fe/54Fe ratios for Fe(II)aq and associated biogenic minerals such as magnetite and siderite. In contrast, Fe(II)aq that exchanges with Fe sulfides (FeS and pyrite) is relatively enriched in 56Fe/54Fe ratios. In modern and ancient environments, anoxic diagenesis tends to produce products that have low 56Fe/54Fe ratios, whereas oxidation of Fe(II)aq from hydrothermal sources tends to produce ferric Fe products that have high 56Fe/54Fe ratios. Redox cycling by bacteria tends to produce reactive ferric Fe reservoirs that have low 56Fe/54Fe ratios. Application of Fe isotopes as a proxy for redox conditions in the ancient rock record depends upon the preservation potential during metamorphism, given the fact that most Archean sedimentary sequences have been subjected to regional greenschist- to granulite-facies metamorphism. The 1.9 Ga banded iron formations (BIFs) of the Lake Superior region that are intruded by large ~1 Ga intrusions (e.g., Duluth gabbro) provide a test of the preservation potential for primary, low-temperature Fe isotope variations in sedimentary rocks. 56Fe/54Fe ratios for re-crystallized magnetite from BIFs of the Biwabik iron formation that have apparent oxygen-isotope (quartz-magnetite) temperatures between 270 and 800 oC span a significant portion of the range measured in lower-grade BIFs from South Africa and Australia. d56Fe values for Biwabik magnetite vary from -0.2 to +0.7 per mil, whereas magnetite from the Dales Gorge member of the Brockman iron formation and the Kuruman iron formation has d56Fe values that lie between -1.2 and +1.3 per mil. Iron isotope fractionations between magnetite and Fe silicates (greenalite, hedenbergite, and fayalite) in the Biwabik iron formation regularly decrease with increasing oxygen-isotope temperatures, approaching the zero fractionation expected at igneous temperatures; apparent magnetite-Fe silicate fractionations range from +0.2 per mil at 650 oC to +0.5 per mil at 300 oC, lying close to those predicted using the revised beta factors of Polyakov et al. (2005, Goldschmidt). During closed-system Fe isotope exchange during metamorphism, the overall range in d56Fe values for magnetite will remain relatively constant, although it may shift to higher d56Fe values relative to primary (low-temperature) magnetite due to the non-zero magnetite-Fe silicate fractionation factor at moderate temperature ranges. If the mineral parageneis is known, and some assumptions regarding primary mineralogy can be made, these small corrections may be made to successfully infer the original Fe isotope compositions of sedimentary minerals and rocks that have been subjected to metamorphism.

Carbon isotope ratios of nandrolone, boldenone, and testosterone preparations seized in Norway compared to those of endogenously produced steroids in a Nordic reference population.

PubMed

Hullstein, Ingunn; Sagredo, Carlos; Hemmersbach, Peter

2014-01-01

Determining the origin of anabolic androgenic steroids (AAS) that also are produced endogenously in the human body is a major issue in doping control. In some cases, the presence of nandrolone and boldenone metabolites might result from endogenous production. The GC-C-IRMS technique (gas chromatography-combustion-isotope ratio mass spectrometry) enables the carbon isotopic ratio (CIR) to be measured to determine the origin of these metabolites. The aim of this study was to use GC-C-IRMS to determine the δ(13) CVPDB values of seized boldenone and nandrolone preparations to decide if the steroids themselves were depleted in (13) C, compared to what is normally seen in endogenously produced steroids. In addition, several testosterone preparations were analyzed. A total of 69 seized preparations were analyzed. The nandrolone preparations showed δ(13) CVPDB values in the range of -31.5 ‰ to -26.7 ‰. The boldenone preparations showed δ(13) CVPDB values in the range of -32.0 ‰ to -27.8 ‰, and for comparison the testosterone preparations showed δ(13) CVPDB values of -31.0 ‰ to -24.2 ‰. The results showed that the values measured in the nandrolone and boldenone preparations were in the same range as those measured in the testosterone preparations. The study also included measurements of CIR of endogenously produced steroids in a Norwegian/Danish reference population. The δ(13) CVPDB values measured for the endogenous steroids in this population were in the range of -21.7 to -26.8. In general, most of the preparations investigated in this study show (13) C-depleted delta values compared to endogenously produced steroids reflecting a northern European diet. Copyright © 2014 John Wiley & Sons, Ltd.

The effects of sex, tissue type, and dietary components on stable isotope discrimination factors (Δ13C and Δ15N) in mammalian omnivores.

PubMed

Kurle, Carolyn M; Koch, Paul L; Tershy, Bernie R; Croll, Donald A

2014-01-01

We tested the effects of sex, tissue, and diet on stable isotope discrimination factors (Δ(13)C and Δ(15)N) for six tissues from rats fed four diets with varied C and N sources, but comparable protein quality and quantity. The Δ(13)C and Δ(15)N values ranged from 1.7-4.1‰ and 0.4-4.3‰, respectively. Females had higher Δ(15)N values than males because males grew larger, whereas Δ(13)C values did not differ between sexes. Differences in Δ(13)C values among tissue types increased with increasing variability in dietary carbon sources. The Δ(15)N values increased with increasing dietary δ(15)N values for all tissues except liver and serum, which have fast stable isotope turnover times, and differences in Δ(15)N values among tissue types decreased with increasing dietary animal protein. Our results demonstrate that variability in dietary sources can affect Δ(13)C values, protein source affects Δ(15)N values even when protein quality and quantity are controlled, and the isotope turnover rate of a tissue can influence the degree to which diet affects Δ(15)N values.

Zircon oxygen isotopes reveal Ivrea-Verbano Zone source characteristics of the Sesia Valley Caldera

NASA Astrophysics Data System (ADS)

Economos, R. C.; Quick, J. E.; Sinigoi, S.; de Silva, S. L.

2013-12-01

The Sesia Valley, in the Italian Alpine foothills, contains >14 km diameter caldera adjacent to and structurally shallower than the famous Ivrea-Verbano Zone deep crustal section. The caldera and its associated eruptive sequence presents opportunity to explore volcanic magmatism in light of exposed and well characterized source candidates, namely lower crustal gabbros and the mid-crustal metasedimentary Kinzigite formation. Original geochemical characteristics of volcanic units have been obscured by the effects of subsequent hydrothermal alteration. The resistance of the mineral zircon to fluid alteration makes it a prime candidate for the preservation and exploration of these geochemical signals, such as O isotopes. Lower crustal gabbros in the Ivrea-Verbano Zone have broadly monotonic whole-rock δ18O values between +8 and +9‰VSMOW (Sinigoi et al., 1994). Kinzigites preserve a much higher and more heterogeneous δ18O values, typically ranging from +10‰ up to +15‰ (Baker, 1990). Zircons from the caldera-forming rhyolitic eruption units and a pre-caldera rhyodacitic unit were analyzed by ion microprobe at UCLA for in-situ oxygen isotope ratios. External reproducibility of within-mount standard R33 grains range from 0.27 to 0.36‰. Rhyolites from the caldera-forming eruption yield a range of δ18O(zircon) values from 6.3‰ to 8.3‰. This range displays rough correlation with CL activity - CL active grains have lower δ18O(zircon) values while CL dark grains have higher δ18O(zircon) values. This variation may correlate with U contents, which are notoriously low in zircons from Ivrea-Verbano Zone gabbros. We argue that the range in O isotope values suggests zircons are a good fit for magmas influenced by gabbro and Kinzigite sources. However, these zircons do not appear to be inherited directly from either the gabbro or Kinzigite sources as their O isotope signatures are typically intermediate between the two. The pre-caldera rhyodacite sample displays a much broader range of δ18O(zircon) values, from +6 to +10‰. These values, when corrected for melt-zircon isotopic fractionation, are an excellent match for mafic and felsic sources in the Ivrea-Verbano Zone. Thus, volcanic rocks of the Sesia Valley share spatial, temporal, and geochemical affinities for Ivrea-Verbano Zone sources, strengthening the body of evidence that the Sesia Valley Caldera represents the upper crustal portions of a complete crustal section contiguous with these mid- and lower-crustal Alpine exposures. These data demonstrate a difference in extent of hybridization of source signals in the rhyodacite (little homogenization) compared to the caldera-forming eruption (more homogenization). This suggests a record of variation in magmatic processes for precursor and climactic eruptions that is potentially related to the thermal maturation of the volcanic system and warrants additional study. Additional work on trace element concentrations, including Ti thermometry, on these grains will further elucidate these processes and their relationship to known zircon-bearing sources in the mid- to deep-crust of the Ivrea-Verbano Zone.

The stable isotopic and chemical composition of pedogenic carbonate in the Minusinsk Basin, South Siberia

NASA Astrophysics Data System (ADS)

Vasilchuk, Jessica; Ivanova, Elena; Krechetov, Pavel; Litvinskiy, Vladimir; Budantseva, Nadine; Chizhova, Julia; Vasil'chuk, Yurij

2017-04-01

Stable isotope composition of carbonate neoformations can be used as a proxy for the reconstructons of environmental conditions of the past. Carbonate coatings on coarse rock framents are studied in order to indicate the climatic conditions and predominant vegetation under which they were formed. Such coatings commonly occur in different types of soils and paleosols of South Siberian intermountain basins mainly in relatively dry modern conditions. The purpose of the research is to characterize the isotopic composition and chemical composition of carbonate pedofeatures in soils of Minusink Hollow and estimate its correlation with defferent factors. The samples of pedogenic carbonates, vegetation, carbonate parent material, soil water and precipitation water were analyzed using the Delta-V mass spectrometer with options of a gas bench and element analyser. The soils we studied are mainly Kastanozems that are poorly moisturized; therefore, soil pore water was extracted by ethanol. Minor and major elements content was also measured by ICP-MS. Carbonates mostly contain calcuim (37-45%) and highly enriched in Pb, Tl and Ba. Oxygen and carbon isotopic composition of pedogenic carbonates was analyzed in 3 key sites. Kazanovka Khakass state national reserve, Hankul salt lake, region of Sayanogorsk aluminum smelter. Vegetation photosynthetic pathway in the region is mainly C3. δ18O values of carbonate coatings in soils of Kazanovka vary in a range from -7.49 to -10.5‰ (vs V-PDB). The lowest values corresponds the coatings found between two buried mid-Holocene soil horizons. That may indicate cooler conditions of late Holocene than nowadays. In Sayanogorsk carbonates' δ18O values' range is -8.3...-11.1‰ and near the Hankul Lake is -9.0...-10.2‰ all ranges are quite similar and may indicate close conditions of pendants formation. δ13C values of carbonate coatings in Kazanovka vary from -2.5 to -6.7‰, the highest values correspond to the soils of Askiz and Syglygkug rivers former floodplains. For Sayanogorsk the range is from -4.9 to -6.8‰ and for Hankul from -2.3 to -5.7‰, where the highest value is for the modern salt crust. δ13C values of coatings decrease from inner (older) to outer (younger) layers of coatings, that can indicate differences connected with the diffusion of organic material. Carbonate parent material δ18O value in the region vary from -11.1 to -12.0‰ and δ13C values vary from -4.9 to -5.7‰. Soil pore water δ18O values that determine the oxygen isotope composition of carbonates vary due to the processes of transpiration and mixing in the studied sites in a wide range of -2.0... -13.5‰ (vs V-SMOW). Precipitation waters show δ18O values from -6.6‰ (spring) -19.0‰ (winter snow). The main conclusions are as follows: pedogenic carbonates δ13C values (-7…-2,5‰) show no correlation with modern C3 vegetation δ13C values but are closer to C4 vegetation. Late Holocene climate for the Minusinsk Hollow according to obtained data on isotope composition of carbonates and soil pore water chemical composition was dryer and cooler than present, that fact does not contradict with paleocarpology data obtained for the region. The research was supported by Russian Science Foundation (grant №14-27-00083). The research was supported by Russian Science Foundation (grant №14-27-00083).

Response of carbon isotopic compositions of Early-Middle Permian coals in North China to palaeo-climate change

NASA Astrophysics Data System (ADS)

Ding, Dianshi; Liu, Guijian; Sun, Xiaohui; Sun, Ruoyu

2018-01-01

To investigate the magnitude to which the carbon isotopic ratio (δ13C) varies in coals in response to their contemporary terrestrial environment, the Early-Middle Permian Huainan coals (including coals from the Shanxi Formation, Lower Shihezi Formation and Upper Shihezi Formation) in North China were systematically sampled. A 2.5‰ variation range of δ13C values (-25.15‰ to -22.65‰) was observed in Huainan coals, with an average value of -24.06‰. As coal diagenesis exerts little influence on carbon isotope fractionation, δ13C values in coals were mainly imparted by those of coal-forming flora assemblages which were linked to the contemporary climate. The δ13C values in coals from the Shanxi and Lower Shihezi Formations are variable, reflecting unstable climatic oscillations. Heavy carbon isotope is enriched in coals of the Capitanian Upper Shihezi Formation, implying a shift to high positive δ13C values of coeval atmospheric CO2. Notably, our study provides evidence of the Kamura event in the terrestrial environment for the first time.

First field-based observations of δ2H and δ18O values of precipitation and other water bodies in the Mongolian Gobi desert

NASA Astrophysics Data System (ADS)

Burnik Šturm, Martina; Ganbaatar, Oyunsaikhan; Voigt, Christian C.; Kaczensky, Petra

2017-04-01

Hydrogen (δ2H) and oxygen (δ18O) isotope values of water are widely used to track the global hydrological cycle and the global δ2H and δ18O patterns of precipitation are increasingly used in studies on animal migration, forensics, food authentication and traceability studies. However, δ2H and δ18O values of precipitation spanning one or more years are available for only a few 100 locations worldwide and for many remote areas such as Mongolia data are still scarce. We obtained the first field-based δ2H and δ18O isotope data of event-based precipitation, rivers and other water bodies in the extreme environment of the Dzungarian Gobi desert in SW Mongolia, covering a period of 16 months (1). Our study area is located over 450 km north-east from the nearest IAEA GNIP station (Fukang station, China) from which it is separated by a mountain range at the international border between China and Mongolia. Isotope values of the collected event-based precipitation showed and extreme range and a high seasonal variability with higher and more variable values in summer and lower in winter. The high variability could not be explained by different origin of air masses alone (i.e. NW polar winds over Russia or westerlies over Central Asia; analyzed using back-trajectory HYSPLIT model), but is likely a result of a combination of different processes affecting the isotope values of precipitation in this area. The calculated field-based local meteoric water line (LMWL, δ2H=(7.42±0.16)δ18O-(23.87±3.27)) showed isotopic characteristics of precipitation in an arid region. We observed a slight discrepancy between the filed based and modelled (Online Isotope in Precipitation Calculator, OIPC) LMWL which highlighted the difficulty of modelling the δ2H and δ18O values for areas with extreme climatic conditions and thus emphasized the importance of collecting long-term field-based data. The collected isotopic data of precipitation and other water bodies provide a basis for future studies in this largely understudied region. (1)Burnik Šturm M., Ganbaatar O., Voigt C.C., Kaczensky P. (2016) First field-based observations of δ2H and δ18O values of precipitation, rivers and other water bodies in the Dzungarian Gobi, SW Mongolia. Isotopes in Environmental and Health Studies, doi: 10.1080/10256016.2016.1231184

Late Pliocene - Early Pleistocene paleoenvironmental reconstruction based on stable isotope compositions of Stephanorhinus sp. and Mammut sp. teeth

NASA Astrophysics Data System (ADS)

Szabó, Péter; Kovács, János; Kocsis, László; Gasparik, Mihály; Vennemann, Torsten; Demény, Attila; Virág, Attila

2014-05-01

Stable isotope measurements of skeletal apatite from herbivorous mammals are often used to provide information on the terrestrial paleoenvironment and paleoclimate. In this study fossil teeth of Stephanorhinus Kretzoi 1942 (rhinoceros) and Mammut Blumenbach 1799 (mastodon), amongst others, were investigated from the Carpathian Basin. According to the biostratigraphy, the age of the samples has a range from Late Pliocene to Early Pleistocene. Reconstructing paleoclimate and paleoenvironment of this era is important as it can be an analogue for the future climate. Oxygen and carbon isotopic compositions were measured from the tooth enamel, because it is believed to be the most resistant to diagenetic alteration (e.g., Kohn & Cerling, 2002). The carbon isotopic composition in the carbonate fraction of apatite can be related to the diet of the animal (Kohn & Cerling, 2002). Hence, it can reflect the photosynthetic pathway (C3 or C4) of the plants consumed by these herbivores. The δ18O values were determined in the phosphate fraction of apatite. In the case of large mammals that are obligate drinkers, the δ18O values closely track those of the environmental water (Bryant & Froelich, 1995). Knowing the δ18O values of environmental water and relating it to local precipitation, the mean annual temperature (MAT) of the site can be calculated (Dansgaard, 1964). The δ13C values range from -10 to -15 o (VPDB). The result clearly shows that these animals consumed C3 plants. Most of the δ13C values indicate mixed grassland-open woodland rather than a closed canopy forest. Although there is variation in the δ18O values (mean 14.2 ± 1.0 o VSMOW, n=17), most of the samples would support a MAT range of 8-12 ° C. This is in good agreement with other proxies for the localities and time period (Kovács et al., 2013). Bryant, D.J. & Froelich, P.N. (1995) A model of oxygen-isotope fractionation in bodywater of large-mammals. Geochimica et Cosmochimica Acta 59, 4523-4537. Dansgaard, W. (1964) Stable isotopes in precipitation. Tellus 16, 436-468. Kohn, M.J. & Cerling, T.E. (2002) Stable isotope compositions of biological apatite. Reviews in Mineralogy and Geochemistry 48, 455-488. Kovács, J. et al. (2013) Clay Mineralogy of Red Clay Deposits from the Central Carpathian Basin (Hungary): Implications for Plio/Pleistocene Chemical Weathering and Paleoclimate. Turkish J. Earth. Sci. 22, 414-426.

Impact of topography, climate and moisture sources on isotopic composition (δ18O &δD) of rivers in the Pyrenees: Implications for topographic reconstructions in small orogens

NASA Astrophysics Data System (ADS)

Huyghe, Damien; Mouthereau, Frédéric; Sébilo, Mathieu; Vacherat, Arnaud; Ségalen, Loïc; Richard, Patricia; Biron, Philippe; Bariac, Thierry

2018-02-01

Understanding how orogenic topography controls the spatial distribution and isotopic composition of precipitation is critical for paleoaltitudinal reconstructions. Here, we determine the isotopic composition (δ18O and δD) of 82 small rivers and springs from small catchments in the Pyrenees. Calculation of the deuterium excess (d-excess) parameter allows the distinction of four distinct isotopic provinces with d-excess values of between 15 and 22‰ in the northwest, between 7 and 14‰ in the central northern Pyrenees and between 3 and 11‰ in the northeast. The southern Pyrenees have a homogenous d-excess signature ranging from 7 to 14‰. Our results show significant local moisture recycling and/or rain amount effect in the northwestern Pyrenees, and control by evaporation processes during rainfall events in the southern Pyrenees and for low elevated samples of the northeast of the range. Based on the distribution of d-excess values, we estimate contrasting isotope lapse rates of -2.9/-21.4‰/km (δ18O/δD) in the northwest, -2.7/-21.4‰/km (δ18O/δD) in the north central and -3.7/-31.7‰/km (δ18O/δD) in the northeastern Pyrenees. The southern Pyrenees show distinctly higher lapse rates of -9.5/-77.5‰/km (δ18O/δD), indicating that in this area the altitudinal effect in not the only parameter driving isotopic composition of rivers. Despite their relatively low topographic gradient, the Pyrenees exert a direct control on the isotopic composition of river waters, especially on their northern side. The variations in isotopic composition-elevation relationships documented along the strike of the range are interpreted to reflect an increasing continentality effect driven by wind trajectories parallel to the range, and mixing with Mediterranean air masses. Despite these effects, the measurable orographic effect on precipitation in the Pyrenees proves that the isotopic composition approach for reconstructing past topography is applicable to low-elevation orogens.

Review of footnotes and annotations to the 1949–2013 tables of standard atomic weights and tables of isotopic compositions of the elements (IUPAC Technical Report)

DOE PAGES

Coplen, Tyler B.; Holden, Norman E.

2016-01-01

Abstract The Commission on Isotopic Abundances and Atomic Weights uses annotations given in footnotes that are an integral part of the Tables of Standard Atomic Weights to alert users to the possibilities of quite extraordinary occurrences, as well as sources with abnormal atomic-weight values outside an otherwise acceptable range. The basic need for footnotes to the Standard Atomic Weights Table and equivalent annotations to the Table of Isotopic Compositions of the Elements arises from the necessity to provide users with information that is relevant to one or more elements, but that cannot be provided using numerical data in columns. Anymore » desire to increase additional information conveyed by annotations to these Tables is tempered by the need to preserve a compact format and a style that can alert users, who would not be inclined to consult either the last full element-by-element review or the full text of a current Standard Atomic Weights of the Elements report. Since 1989, the footnotes of the Tables of Standard Atomic Weights and the annotations in column 5 of the Table of Isotopic Compositions of the Elements have been harmonized by use of three lowercase footnotes, “g”, “m”, and “r”, that signify geologically exceptionally specimens (“g”), modified isotopic compositions in material subjected to undisclosed or inadvertent isotopic fractionation (“m”), and the range in isotopic composition of normal terrestrial material prevents more precise atomic-weight value being given (“r”). As some elements are assigned intervals for their standard atomic-weight values (applies to 12 elements since 2009), footnotes “g” and “r” are no longer needed for these elements.« less

Review of footnotes and annotations to the 1949–2013 tables of standard atomic weights and tables of isotopic compositions of the elements (IUPAC Technical Report)

USGS Publications Warehouse

Coplen, Tyler B.; Holden, Norman E.

2016-01-01

The Commission on Isotopic Abundances and Atomic Weights uses annotations given in footnotes that are an integral part of the Tables of Standard Atomic Weights to alert users to the possibilities of quite extraordinary occurrences, as well as sources with abnormal atomic-weight values outside an otherwise acceptable range. The basic need for footnotes to the Standard Atomic Weights Table and equivalent annotations to the Table of Isotopic Compositions of the Elements arises from the necessity to provide users with information that is relevant to one or more elements, but that cannot be provided using numerical data in columns. Any desire to increase additional information conveyed by annotations to these Tables is tempered by the need to preserve a compact format and a style that can alert users, who would not be inclined to consult either the last full element-by-element review or the full text of a current Standard Atomic Weights of the Elements report. Since 1989, the footnotes of the Tables of Standard Atomic Weights and the annotations in column 5 of the Table of Isotopic Compositions of the Elements have been harmonized by use of three lowercase footnotes, “g”, “m”, and “r”, that signify geologically exceptionally specimens (“g”), modified isotopic compositions in material subjected to undisclosed or inadvertent isotopic fractionation (“m”), and the range in isotopic composition of normal terrestrial material prevents more precise atomic-weight value being given (“r”). As some elements are assigned intervals for their standard atomic-weight values (applies to 12 elements since 2009), footnotes “g” and “r” are no longer needed for these elements.

Tooth enamel stable isotopes of Holocene and Pleistocene fossil fauna reveal glacial and interglacial paleoenvironments of hominins in Indonesia

NASA Astrophysics Data System (ADS)

Janssen, Renée; Joordens, Josephine C. A.; Koutamanis, Dafne S.; Puspaningrum, Mika R.; de Vos, John; van der Lubbe, Jeroen H. J. L.; Reijmer, John J. G.; Hampe, Oliver; Vonhof, Hubert B.

2016-07-01

The carbon (δ13C) and oxygen (δ18O) isotope compositions of fossilized animal tissues have become important proxies of paleodiet and paleoenvironment, but such stable isotope studies have not yet been extensively applied to the fossil assemblages of Sundaland (the biogeographical region comprising most of the Indonesian Archipelago). Here, we use the isotope composition of tooth enamel to investigate the diet and habitat of bovids, cervids, and suids from several Holocene and Pleistocene sites on Java and Sumatra. Our carbon isotope results indicate that individual sites are strongly dominated by either C3-browsers or C4-grazers. Herbivores from the Padang Highlands (Sumatra) and Hoekgrot (Java) cave faunas were mainly C3-browsers, while herbivores from Homo erectus-bearing sites Trinil and Sangiran (Java) utilized an almost exclusive C4 diet. The suids from all sites show a wide range of δ13C values, corroborating their omnivorous diet. For the dataset as a whole, oxygen and carbon isotope values are positively correlated. This suggests that isotopic enrichment of rainwater and vegetation δ18O values coincides with an increase of C4-grasslands. We interpret this pattern to mainly reflect the environmental contrast between glacial (drier, more C4) and interglacial (wetter, more C3) conditions. Intermediate herbivore δ13C values indicating mixed C3/C4 feeding is relatively rare, which we believe to reflect the abruptness of the transition between glacial and interglacial precipitation regimes in Sundaland. For seven Homo erectus bone samples we were not able distinguish between diagenetic overprint and original isotope values, underlining the need to apply this isotopic approach to Homo erectus tooth enamel instead of bone. Importantly, our present results on herbivore and omnivore faunas provide the isotopic framework that will allow interpretation of such Homo erectus enamel isotope data.

Fractionation between inorganic and organic carbon during the Lomagundi (2.22 2.1 Ga) carbon isotope excursion

NASA Astrophysics Data System (ADS)

Bekker, A.; Holmden, C.; Beukes, N. J.; Kenig, F.; Eglinton, B.; Patterson, W. P.

2008-07-01

The Lomagundi (2.22-2.1 Ga) positive carbon isotope excursion in shallow-marine sedimentary carbonates has been associated with the rise in atmospheric oxygen, but subsequent studies have demonstrated that the carbon isotope excursion was preceded by the rise in atmospheric oxygen. The amount of oxygen released to the exosphere during the Lomagundi excursion is constrained by the average global fractionation between inorganic and organic carbon, which is poorly characterized. Because dissolved inorganic and organic carbon reservoirs were arguably larger in the Paleoproterozoic ocean, at a time of lower solar luminosity and lower ocean redox state, decoupling between these two variables might be expected. We determined carbon isotope values of carbonate and organic matter in carbonates and shales of the Silverton Formation, South Africa and in the correlative Sengoma Argillite Formation, near the border in Botswana. These units were deposited between 2.22 and 2.06 Ga along the margin of the Kaapvaal Craton in an open-marine deltaic setting and experienced lower greenschist facies metamorphism. The prodelta to offshore marine shales are overlain by a subtidal carbonate sequence. Carbonates exhibit elevated 13C values ranging from 8.3 to 11.2‰ vs. VPDB consistent with deposition during the Lomagundi positive excursion. The total organic carbon (TOC) contents range from 0.01 to 0.6% and δ13C values range from - 24.8 to - 13.9‰. Thus, the isotopic fractionation between organic and carbonate carbon was on average 30.3 ± 2.8‰ ( n = 32) in the shallow-marine environment. The underlying Sengoma shales have highly variable TOC contents (0.14 to 21.94%) and δ13C values (- 33.7 to - 20.8‰) with an average of - 27.0 ± 3.0‰ ( n = 50). Considering that the shales were also deposited during the Lomagundi excursion, and taking δ13C values of the overlying carbonates as representative of the δ13C value of dissolved inorganic carbon during shale deposition, a carbon isotope fractionation as large as ~ 37‰ appears to characterize the production of bulk organic matter in the deeper part of the Pretoria Basin at that time. This enhanced fractionation relative to that observed in shallow-water environments likely reflects heterotrophic (secondary) and chemotrophic productivity at and below a pronounced redoxcline, consistent with the euxinic conditions inferred from independent evidence for the deeper part of the Pretoria Basin. Greater variability in organic carbon vs. carbonate carbon isotopic values on the shallow-marine carbonate platform suggests that the carbon cycling was dominated by a large dissolved inorganic carbon reservoir during the Lomagundi excursion. Our study suggests that in contrast to the Late Neoproterozoic and Phanerozoic, when carbon isotope fractionation between carbonate and organic carbon in the open ocean was mostly controlled by primary producers, in the Paleoproterozoic redox-stratified ocean heterotrophic and chemotrophic productivity overprinted a signal of primary productivity below the redoxcline. This strong imprint of heterotrophic and chemotrophic productivity on organic carbon isotope records complicates the reconstruction of spatial patterns and secular trends in the δ13C values of dissolved inorganic carbon in the Paleoproterozoic seawater.

Relationship between δ 18O values for skeletal apatite from reindeer and foxes and yearly mean δ 18O values of environmental water

NASA Astrophysics Data System (ADS)

Iacumin, Paola; Longinelli, Antonio

2002-07-01

The oxygen isotope composition of bone and tooth phosphate of 50 fox specimens and 30 reindeer specimens from various locations with different climatic and environmental conditions was measured. The existing relationship between these values and the mean oxygen isotope composition of local meteoric water has been calculated. In the case of foxes, specimens belonging to two genera ( Vulpes and Alopex) and three different species were measured. The samples fit a straight line whose equation can be used for paleoclimatological studies either in Arctic or in temperate regions. For reindeer ( Rangifer), a relatively large range of isotopic values was obtained from each location, suggesting imperfect equilibrium conditions with environmental water. The calculated equation can be used for semi-quantitative information on local paleowaters at high latitudes only.

Oxygen isotope systematics of chondrules in the Murchison CM2 chondrite and implications for the CO-CM relationship

NASA Astrophysics Data System (ADS)

Chaumard, Noël; Defouilloy, Céline; Kita, Noriko T.

2018-05-01

High-precision oxygen three-isotope measurements of olivine and pyroxene were performed on 29 chondrules in the Murchison CM2 chondrite by secondary ion mass spectrometry (SIMS). The oxygen isotope ratios of analyzed chondrules all plot very close to the primitive chondrule minerals (PCM) line. In each of 24 chondrules, the olivine and/or pyroxene grains analyzed show indistinguishable oxygen isotope ratios. Exceptions are minor occurrences of isotopically distinguished relict olivine grains, which were found in nine chondrules. The isotope homogeneity of these phenocrysts is consistent with a co-magmatic crystallization of olivine and pyroxene from the final chondrule melts and a significant oxygen isotope exchange between the ambient gas and the melts. Homogeneous type I chondrules with Mg#'s of 98.9-99.5 have host chondrule Δ17O values ranging from -6.0‰ to -4.1‰, with one exception (Δ17O: -1.2‰; Mg#: 99.6). Homogeneous chondrules with Mg#'s <96, including four type II chondrules (Mg# ∼65-70), have Δ17O values of around -2.5‰. Five type I chondrules (Mg# ≥99) have internally heterogeneous oxygen isotope ratios with Δ17O values ranging from -6.5‰ to -4.0‰, similar to those of host chondrule values. These heterogeneous chondrules have granular or porphyritic textures, convoluted outlines, and contain numerous metal grains dispersed within fine-grained silicates. This is consistent with a low degree of melting of the chondrule precursors, possibly because of a low temperature of the melting event and/or a shorter duration of melting. The Δ17O values of relict olivine grains in nine chondrules range from -17.9‰ to -3.4‰, while most of them overlap the range of the host chondrule values. Similar to those reported from multiple carbonaceous chondrites (Acfer 094, Y-82094, CO, and CV), the Δ17O ∼ -5‰ and high Mg# (≥99) chondrules, which might derive from a reduced reservoir with limited dust enrichments (∼50 × Solar System), dominate the population of chondrules in Murchison. Other chondrules in Murchison formed in more oxidizing environment (Mg# < 96) with higher Δ17O values of -2.5‰, in agreement with the low Mg# chondrules in Acfer 094 and CO chondrites and some chondrules in CV and CR chondrites. They might form in environments containing the same anhydrous precursors as for the Δ17O ∼ -5‰ and Mg# ∼99 chondrules, but enriched in 16O-poor H2O ice (∼0.3-0.4× the CI dust; Δ17O > 0‰) and at dust enrichments of ∼300-2000×. Regarding the Mg# and oxygen isotope ratios, the chondrule populations sampled by CM and CO chondrites are similar and indistinguishable. The similarity of these 16O-rich components in CO and CM chondrites is also supported by the common Fe/Mn ratio of olivine in type II chondrules. Although they accreted similar high-temperature silicates, CO chondrites are anhydrous compared to CM chondrites, suggesting they derived from different parent bodies formed inside and outside the snow line, respectively. If chondrules in CO and CM chondrites formed at the same disk locations but the CM parent body accreted later than the CO parent body, the snow line might have crossed the common chondrule-forming region towards the Sun between the time of the CO and CM parent bodies accretion.

Late Paleocene Arctic Ocean shallow-marine temperatures from mollusc stable isotopes

USGS Publications Warehouse

Bice, Karen L.; Arthur, Michael A.; Marincovich, Louie

1996-01-01

Late Paleocene high-latitude (80°N) Arctic Ocean shallow-marine temperatures are estimated from molluscan δ18O time series. Sampling of individual growth increments of two specimens of the bivalve Camptochlamys alaskensis provides a high-resolution record of shell stable isotope composition. The heavy carbon isotopic values of the specimens support a late Paleocene age for the youngest marine beds of the Prince Creek Formation exposed near Ocean Point, Alaska. The oxygen isotopic composition of regional freshwater runoff is estimated from the mean δ18O value of two freshwater bivalves collected from approximately coeval fluviatile beds. Over a 30 – 34‰ range of salinity, values assumed to represent the tolerance of C. alaskensis, the mean annual shallow-marine temperature recorded by these individuals is between 11° and 22°C. These values could represent maximum estimates of the mean annual temperature because of a possible warm-month bias imposed on the average δ18O value by slowing or cessation of growth in winter months. The amplitude of the molluscan δ18O time series probably records most of the seasonality in shallow-marine temperature. The annual temperature range indicated is approximately 6°C, suggesting very moderate high-latitude marine temperature seasonality during the late Paleocene. On the basis of analogy with modern Chlamys species, C. alaskensis probably inhabited water depths of 30–50 m. The seasonal temperature range derived from δ18O is therefore likely to be damped relative to the full range of annual sea surface temperatures. High-resolution sampling of molluscan shell material across inferred growth bands represents an important proxy record of seasonality of marine and freshwater conditions applicable at any latitude. If applied to other regions and time periods, the approach used here would contribute substantially to the paleoclimate record of seasonality.

Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers, nitric acid, and reagent salts.

PubMed

Michalski, Greg; Kolanowski, Michelle; Riha, Krystin M

2015-01-01

Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ(15)N values of synthetic and natural nitrates were 0 ± 2 ‰ similar to the air N2 from which they are derived. The δ(18)O values of synthetic nitrates were 23 ± 3 ‰, similar to air O2, and natural nitrate fertilizer δ(18)O values (55 ± 5 ‰) were similar to those observed in atmospheric nitrate. The Δ(17)O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ(17)O values of 18 ± 2 ‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models.

Strontium stable isotope behaviour accompanying basalt weathering

NASA Astrophysics Data System (ADS)

Burton, K. W.; Parkinson, I. J.; Gíslason, S. G. R.

2016-12-01

The strontium (Sr) stable isotope composition of rivers is strongly controlled by the balance of carbonate to silicate weathering (Krabbenhöft et al. 2010; Pearce et al. 2015). However, rivers draining silicate catchments possess distinctly heavier Sr stable isotope values than their bedrock compositions, pointing to significant fractionation during weathering. Some have argued for preferential release of heavy Sr from primary phases during chemical weathering, others for the formation of secondary weathering minerals that incorporate light isotopes. This study presents high-precision double-spike Sr stable isotope data for soils, rivers, ground waters and estuarine waters from Iceland, reflecting both natural weathering and societal impacts on those environments. The bedrock in Iceland is dominantly basaltic, d88/86Sr ≈ +0.27, extending to lighter values for rhyolites. Geothermal waters range from basaltic Sr stable compositions to those akin to seawater. Soil pore waters reflect a balance of input from primary mineral weathering, precipitation and litter recycling and removal into secondary phases and vegetation. Rivers and ground waters possess a wide range of d88/86Sr compositions from +0.101 to +0.858. Elemental and isotope data indicate that this fractionation primarily results from the formation or dissolution of secondary zeolite (d88/86Sr ≈ +0.10), but also carbonate (d88/86Sr ≈ +0.22) and sometimes anhydrite (d88/86Sr ≈ -0.73), driving the residual waters to heavier or lighter values, respectively. Estuarine waters largely reflect mixing with seawater, but are also be affected by adsorption onto particulates, again driving water to heavy values. Overall, these data indicate that the stability and nature of secondary weathering phases, exerts a strong control on the Sr stable isotope composition of silicate rivers. [1] Krabbenhöft et al. (2010) Geochim. Cosmochim. Acta 74, 4097-4109. [2] Pearce et al. (2015) Geochim. Cosmochim. Acta 157, 125-146.

Chlorine isotopic compositions of apatite in Apollo 14 rocks: Evidence for widespread vapor-phase metasomatism on the lunar nearside ∼4 billion years ago

NASA Astrophysics Data System (ADS)

Potts, Nicola J.; Barnes, Jessica J.; Tartèse, Romain; Franchi, Ian A.; Anand, Mahesh

2018-06-01

Compared to most other planetary materials in the Solar System, some lunar rocks display high δ37Cl signatures. Loss of Cl in a H ≪ Cl environment has been invoked to explain the heavy signatures observed in lunar samples, either during volcanic eruptions onto the lunar surface or during large scale degassing of the lunar magma ocean. To explore the conditions under which Cl isotope fractionation occurred in lunar basaltic melts, five Apollo 14 crystalline samples were selected (14053,19, 14072,13, 14073,9, 14310,171 along with basaltic clast 14321,1482) for in situ analysis of Cl isotopes using secondary ion mass spectrometry. Cl isotopes were measured within the mineral apatite, with δ37Cl values ranging from +14.6 ± 1.6‰ to +40.0 ± 2.9‰. These values expand the range previously reported for apatite in lunar rocks, and include some of the heaviest Cl isotope compositions measured in lunar samples to date. The data here do not display a trend between increasing rare earth elements contents and δ37Cl values, reported in previous studies. Other processes that can explain the wide inter- and intra-sample variability of δ37Cl values are explored. Magmatic degassing is suggested to have potentially played a role in fractionating Cl isotope in these samples. Degassing alone, however, could not create the wide variability in isotopic signatures. Our favored hypothesis, to explain small scale heterogeneity, is late-stage interaction with a volatile-rich gas phase, originating from devolatilization of lunar surface regolith rocks ∼4 billion years ago. This period coincides with vapor-induced metasomastism recorded in other lunar samples collected at the Apollo 16 and 17 landing sites, pointing to the possibility of widespread volatile-induced metasomatism on the lunar nearside at that time, potentially attributed to the Imbrium formation event.

Boron contents and isotopic compositions of hog manure, selected fertilizers, and water in Minnesota

USGS Publications Warehouse

Komor, S.C.

1997-01-01

Boron-isotope (δ11B) values may be useful as surrogate tracers of contaminants and indicators of water mixing in agricultural settings. This paper characterizes the B contents and isotopic compositions of hog manure and selected fertilizers, and presents δ11B data for ground and surface water from two agricultural areas. Boron concentrations in dry hog manure averaged 61 mg/kg and in commercial fertilizers ranged from below detection limits in some brands of ammonium nitrate and urea to 382 mg/kg in magnesium sulfate. Values of δ11B of untreated hog manure ranged from 7.2 to 11.2o/oo and of N fertilizers were −2.0 to 0.7o/oo. In 22 groundwater samples from a sand-plain aquifer in east-central Minnesota, B concentrations averaged 0.04 mg/L and δ11B values ranged from 2.3 to 41.5o/oo. Groundwater beneath a hog feedlot and a cultivated field where hog manure was applied had B-isotope compositions consistent with the water containing hog-manure leachate. In a 775-km2 watershed with silty-loam soils in southcentral Minnesota: 18 samples of subsurface drainage from corn (Zea mays L.) and soybean (Glycine max L. Merr.) fields had average B concentrations of 0.06 mg/L and δ11B values of 5.3 to 15.1o/oo; 27 stream samples had average B concentrations of 0.05 mg/L and δ11B values of 1.0 to 19.0o/oo; and eight groundwater samples had average B concentrations of 0.09 mg/L and δ11B values of −0.3 to 23.0o/oo. Values of δ11B and B concentrations, when plotted against one another, define a curved mixing trend that suggests subsurface drainage and stream water contain mixtures of B from shallow and deep groundwater.

Lignin methoxyl hydrogen isotope ratios in a coastal ecosystem

NASA Astrophysics Data System (ADS)

Feakins, Sarah J.; Ellsworth, Patricia V.; Sternberg, Leonel da Silveira Lobo

2013-11-01

Stable hydrogen isotope ratios of plant lignin methoxyl groups have recently been shown to record the hydrogen isotopic composition of meteoric water. Here we extend this technique towards tracing water source variations across a saltwater to freshwater gradient in a coastal, subtropical forest ecosystem. We measure the hydrogen isotopic composition of xylem water (δDxw) and methoxyl hydrogen (δDmethoxyl) to calculate fractionations for coastal mangrove, buttonwood and hammock tree species in Sugarloaf Key, as well as buttonwoods from Miami, both in Florida, USA. Prior studies of the isotopic composition of cellulose and plant leaf waxes in coastal ecosystems have yielded only a weak correlation to source waters, attributed to leaf water effects. Here we find δDmethoxyl values range from -230‰ to -130‰, across a 40‰ range in δDxw with a regression equation of δDmethoxyl ‰ = 1.8 * δDxw - 178‰ (R2 = 0.48, p < 0.0001, n = 74). This is comparable within error to the earlier published relationship for terrestrial trees which was defined across a much larger 125‰ isotopic range in precipitation. Analytical precision for measurements of δD values of pure CH3I by gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-P-IRMS) is σ = 6‰ (n = 31), which is considerably better than for CH3I liberated through cleavage with HI from lignin with σ = 18‰ (n = 26). Our results establish that δDmethoxyl can record water sources and salinity incursion in coastal ecosystems, where variations sufficiently exceed method uncertainties (i.e., applications with δD excursions >50‰). For the first time, we also report yields of propyl iodide, which may indicate lignin synthesis of propoxyl groups under salt-stress.

Characterization of diesel fuel by chemical separation combined with capillary gas chromatography (GC) isotope ratio mass spectrometry (IRMS).

PubMed

Harvey, Scott D; Jarman, Kristin H; Moran, James J; Sorensen, Christina M; Wright, Bob W

2012-09-15

The purpose of this study was to perform a preliminary investigation of compound-specific isotope analysis (CSIA) of diesel fuels to evaluate whether the technique could distinguish diesel samples from different sources/locations. The ability to differentiate or correlate diesel samples could be valuable for discovering fuel tax evasion schemes or for environmental forensic studies. Two urea adduction-based techniques were used to isolate the n-alkanes from the fuel. Both carbon isotope ratio (δ(13)C) and hydrogen isotope ratio (δD) values for the n-alkanes were then determined by CSIA in each sample. The samples investigated had δ(13)C values that ranged from -30.1‰ to -26.8‰, whereas δD values ranged from -83‰ to -156‰. Plots of δD versus δ(13)C with sample n-alkane points connected in order of increasing carbon number gave well-separated clusters with characteristic shapes for each sample. Principal components analysis (PCA) with δ(13)C, δD, or combined δ(13)C and δD data was applied to extract the maximum information content. PCA scores plots could clearly differentiate the samples, thereby demonstrating the potential of this approach for distinguishing (e.g., fingerprinting) fuel samples using δ(13)C and δD values. Copyright © 2012 Elsevier B.V. All rights reserved.

Stable isotope systematics in mesozoic granites of Central and Northern California and Southwestern Oregon

USGS Publications Warehouse

Masi, U.; O'Neil, J.R.; Kistler, R.W.

1981-01-01

18O, D, and H2O+ contents were measured for whole-rock specimens of granitoid rocks from 131 localitics in California and southwestern Oregon. With 41 new determinations in the Klamath Mountains and Sierra Nevada, initial strontium isotope ratios are known for 104 of these samples. Large variations in ??18O (5.5 to 12.4), ??D (-130 to -31), water contents (0.14 to 2.23 weight percent) and initial strontium isotope ratios (0.7028 to 0.7095) suggest a variety of source materials and identify rocks modified by secondary processes. Regular patterns of variation in each isotopic ratio exist over large geographical regions, but correlations between the ratios are generally absent except in restricted areas. For example, the regular decrease in ??D values from west to east in the Sierra Nevada batholith is not correlative with a quite complex pattern of ??18O values, implying that different processes were responsible for the isotopic variations in these two elements. In marked contrast to a good correlation between (87Sr/86Sr)o and ??18O observed in the Peninsular Ranges batholith to the south, such correlations are lacking except in a few areas. ??D values, on the other hand, correlate well with rock types, chemistry, and (87Sr/86Sr)o except in the Coast Ranges where few of the isotopic signatures are primary. The uniformly low ??D values of samples from the Mojave Desert indicate that meteoric water contributed much of the hydrogen to the rocks in that area. Even so, the ??18O values and 18O fractionations between quartz and feldspar are normal in these same rocks. This reconnaissance study has identified regularities in geochemical parameters over enormous geographical regions. These patterns are not well understood but merit more detailed examination because they contain information critical to our understanding of the development of granitoid batholiths. ?? 1981 Springer-Verlag.

Quantitative measurement of carbon isotopic composition in CO2 gas reservoir by Micro-Laser Raman spectroscopy.

PubMed

Li, Jiajia; Li, Rongxi; Zhao, Bangsheng; Guo, Hui; Zhang, Shuan; Cheng, Jinghua; Wu, Xiaoli

2018-04-15

The use of Micro-Laser Raman spectroscopy technology for quantitatively determining gas carbon isotope composition is presented. In this study, 12 CO 2 and 13 CO 2 were mixed with N 2 at various molar fraction ratios to obtain Raman quantification factors (F 12CO2 and F 13CO2 ), which provide a theoretical basis for calculating the δ 13 C value. And the corresponding values were 0.523 (0

Oxygen isotope reservoirs in the outer asteroid belt inferred from oxygen isotope systematics of chondrule olivines and isolated forsterite and olivine grains in Tagish Lake-type carbonaceous chondrites, WIS 91600 and MET 00432

NASA Astrophysics Data System (ADS)

Yamanobe, Masakuni; Nakamura, Tomoki; Nakashima, Daisuke

2018-03-01

To understand oxygen isotope ratios and redox conditions of the chondrule formation environments of the outer rigions of the asteroid belt, we analyzed major element concentrations and oxygen isotope ratios of olivine grains in chondrules, isolated forsterite, and isolated olivine from the WIS 91600 and MET 00432 carbonaceous chondrites, which are thought to have originated from D-type asteroids located in the outer asteroid belt. The oxygen isotope ratios of individual chondrules and isolated grains show a wide variation in δ18O from -9.9‰ to +9.1‰ along the carbonaceous chondrite anhydrous mineral (CCAM) and primitive chondrule mineral (PCM) lines. The Δ17O (= δ17O - 0.52 × δ18O) values of the measured objects increase with decreasing Mg#; i.e., FeO-poor objects (Mg# > 90; type I chondrules and isolated forsterites) mainly have Δ17O values of ca. -6‰, and FeO-rich objects (Mg# < 90; type II chondrules and isolated olivines) have Δ17O values ranging from -3‰ to +2‰. Similar trends are observed for ferromagnesian silicate particles from comet Wild2 and CR chondrite chondrules, particularly in terms of FeO-rich objects with Δ17O values ranging from -3‰ to +2‰. It is suggested that FeO-rich objects formed in the outer regions of the asteroid belt and were transported to the outer solar nebular regions where comet Wild2 formed.

Geology, geochemistry and genesis of the Eocene Lailishan Sn deposit in the Sanjiang region, SW China

NASA Astrophysics Data System (ADS)

Cao, Hua-Wen; Pei, Qiu-Ming; Zhang, Shou-Ting; Zhang, Lin-Kui; Tang, Li; Lin, Jin-Zhan; Zheng, Luo

2017-04-01

The Lailishan deposit is an important tin deposit that is genetically associated with an Early Eocene biotite granite in the western Yunnan metallogenic belt in the Sanjiang region, SW China. This study reports new zircon U-Pb ages and Hf isotopic data, whole-rock elements, mica Ar-Ar age and C-H-O-S-Pb isotope for the Lailishan Sn deposit. The mineralization-related biotite granite crystallized during the Early Eocene (50.5 Ma), with its zircon εHf(t) values ranging from -11.5 to -7.6 and two-stage Hf model ages (TDM2) ranging from 1.60 to 1.85 Ga. The rocks are peraluminous with A/CNK values of 0.99-1.08. The granites display high Si, Al and K contents but low Mg, Fe and Ca contents. The rocks show flat chondrite-normalized REE patterns with strong Eu negative anomalies. These characteristics indicate that the magma originated from a continental crustal source. The hydrothermal muscovite exhibits an Ar-Ar plateau age of 50.4 ± 0.2 Ma. The δ18O and δD values of hydrothermal quartz from the deposit range from -7.32‰ to 4.01‰ and from -124.9‰ to -87.1‰, respectively. The δ13CPDB and δ18OSMOW values of calcite range from -11.3‰ to -3.7‰ and from +2.2‰ to +12.7‰, respectively. The sulfur isotopic compositions (δ34SV-CDT) range from +3.3‰ to +8.6‰ for sulfide separates, and the lead isotopic ratios 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb range from 18.668 to 18.746, from 15.710 to 15.743 and from 39.202 to 39.295, respectively. These isotopic compositions are similar to those of magma-derived fluids, indicating that the ore-forming fluids and materials mainly originated from magmatic rocks with some input from meteoric water. This evidence suggests that the tin mineralization is closely linked to the Lailishan I-type granites. In combination with previous data, it is proposed in this study that widespread early Eocene magmatism resulted from the slab breakoff of the subducting Neo-Tethyan slab at ca. 55 Ma.

Origin of heavy Fe isotope compositions in high-silica igneous rocks: A rhyolite perspective

NASA Astrophysics Data System (ADS)

Du, De-Hong; Wang, Xiao-Lei; Yang, Tao; Chen, Xin; Li, Jun-Yong; Li, Weiqiang

2017-12-01

The origin of heavy Fe isotope compositions in high-silica (>70 wt% SiO2) igneous rocks remains a highly controversial topic. Considering that fluid exsolution in eruptive rocks is more straight-forward to constrain than in plutonic rocks, this study addresses the problem of Fe isotope fractionation in high-silica igneous rocks by measuring Fe isotope compositions of representative rhyolitic samples from the Neoproterozoic volcanic-sedimentary basins in southern China and the Triassic Tu Le Basin in northern Vietnam. The samples show remarkably varied δ56FeIRMM014 values ranging from 0.05 ± 0.05‰ to 0.55 ± 0.05‰, which is among the highest values reported from felsic rocks. The extensional tectonic setting and short melt residence time in magma chambers for the studied rhyolites rule out Soret diffusion and thermal migration processes as causes of the high δ56Fe values. Effects of volcanic degassing and fluid exsolution on bulk rock δ56Fe values for the rhyolites are also assessed using bulk rock geochemical indicators and Rayleigh fractionation models, and these processes are found to be insufficient to produce resolvable changes in Fe isotope compositions of the residual melt. The most probable mechanism accounting for heavy Fe isotope compositions in the high-silica rhyolites is narrowed down to fractional crystallization processes in the magma before rhyolite eruption. Removal of isotopically light Fe-bearing minerals (i.e. ulvöspinel-rich titanomagnetite, ilmenite and biotite) is proposed as the main cause of Fe isotope variation in silicic melts during magmatic evolution. This study implies that crystal fractionation is the dominant mechanism that controls Fe isotope fractionation in eruptive rocks and Fe isotopes could be used to study magmatic differentiation of high-silica magmas.

Online gas chromatography combustion/pyrolysis-isotope ratio mass spectrometry (HRGC-C/P-IRMS) of (+/-)-Dihydroactinidiolide from tea ( Camellia sinensis ) and rooibos tea ( Aspalathus linearis ).

PubMed

del Mar Caja, María; Preston, Christina; Menzel, Michael; Kempf, Michael; Schreier, Peter

2009-07-08

Online capillary gas chromatography-isotope ratio mass spectrometry in both the combustion and the pyrolysis modes (HRGC-C/P-IRMS) was employed to perform authentication studies of the flavoring agent (+/-)-dihydroactinidiolide. Thus, the delta(13)C(V-PDB) and delta(2)H(V-SMOW) values of synthetic (ex synthetic beta-ionone and natural beta-carotene) as well as enzymatically (ex synthetic and natural beta-carotene) produced references were studied in comparison with those of the natural substance isolated from black (n = 17) and green teas (n = 6) ( Camellia sinensis ) as well as Rooibos tea ( Aspalathus linearis ) (n = 7). The isotope values determined for both the synthetic and enzymatically produced samples of (+/-)-dihydroactinidiolide reflected the influence of the origin of their educts. Hence, in cases when synthetic educts were used, the delta(13)C(V-PDB) and delta(2)H(V-SMOW) values ranged from -27.0 to -28.4 per thousand and from -28 to -169 per thousand, respectively, whereas the use of natural educts led to ranges from -30.3 to -31.6 per thousand and from -154 to -228 per thousand, respectively. As to the tea samples, delta(13)C(V-PDB) and delta(2)H(V-SMOW) values ranging from -29.0 to -34.1 per thousand and from -153 to -274 per thousand, respectively, were recorded for (+/-)-dihydroactinidiolide from black and green teas, whereas that from Rooibos tea showed (2)H/(1)H ratios ranging from -189 to -210 per thousand as well as slightly enriched values in the (13)C/(12)C ratios ranging from -24.4 to -27.1 per thousand.

Isotopic Composition of Methane and Inferred Methanogenic Substrates Along a Salinity Gradient in a Hypersaline Microbial Mat System

NASA Astrophysics Data System (ADS)

Potter, Elyn G.; Bebout, Brad M.; Kelley, Cheryl A.

2009-05-01

The importance of hypersaline environments over geological time, the discovery of similar habitats on Mars, and the importance of methane as a biosignature gas combine to compel an understanding of the factors important in controlling methane released from hypersaline microbial mat environments. To further this understanding, changes in stable carbon isotopes of methane and possible methanogenic substrates in microbial mat communities were investigated as a function of salinity here on Earth. Microbial mats were sampled from four different field sites located within salterns in Baja California Sur, Mexico. Salinities ranged from 50 to 106 parts per thousand (ppt). Pore water and microbial mat samples were analyzed for the carbon isotopic composition of dissolved methane, dissolved inorganic carbon (DIC), and mat material (particulate organic carbon or POC). The POC δ13C values ranged from -6.7 to -13.5%, and DIC δ13C values ranged from -1.4 to -9.6%. These values were similar to previously reported values. The δ13C values of methane ranged from -49.6 to -74.1%; the methane most enriched in 13C was obtained from the highest salinity area. The apparent fractionation factors between methane and DIC, and between methane and POC, within the mats were also determined and were found to change with salinity. The apparent fractionation factors ranged from 1.042 to 1.077 when calculated using DIC and from 1.038 to 1.068 when calculated using POC. The highest-salinity area showed the least fractionation, the moderate-salinity area showed the highest fractionation, and the lower-salinity sites showed fractionations that were intermediate. These differences in fractionation are most likely due to changes in the dominant methanogenic pathways and substrates used at the different sites because of salinity differences.

Seeking excellence: An evaluation of 235 international laboratories conducting water isotope analyses by isotope-ratio and laser-absorption spectrometry.

PubMed

Wassenaar, L I; Terzer-Wassmuth, S; Douence, C; Araguas-Araguas, L; Aggarwal, P K; Coplen, T B

2018-03-15

Water stable isotope ratios (δ 2 H and δ 18 O values) are widely used tracers in environmental studies; hence, accurate and precise assays are required for providing sound scientific information. We tested the analytical performance of 235 international laboratories conducting water isotope analyses using dual-inlet and continuous-flow isotope ratio mass spectrometers and laser spectrometers through a water isotope inter-comparison test. Eight test water samples were distributed by the IAEA to international stable isotope laboratories. These consisted of a core set of five samples spanning the common δ-range of natural waters, and three optional samples (highly depleted, enriched, and saline). The fifth core sample contained unrevealed trace methanol to assess analyst vigilance to the impact of organic contamination on water isotopic measurements made by all instrument technologies. For the core and optional samples ~73 % of laboratories gave acceptable results within 0.2 ‰ and 1.5 ‰ of the reference values for δ 18 O and δ 2 H, respectively; ~27 % produced unacceptable results. Top performance for δ 18 O values was dominated by dual-inlet IRMS laboratories; top performance for δ 2 H values was led by laser spectrometer laboratories. Continuous-flow instruments yielded comparatively intermediate results. Trace methanol contamination of water resulted in extreme outlier δ-values for laser instruments, but also affected reactor-based continuous-flow IRMS systems; however, dual-inlet IRMS δ-values were unaffected. Analysis of the laboratory results and their metadata suggested inaccurate or imprecise performance stemmed mainly from skill- and knowledge-based errors including: calculation mistakes, inappropriate or compromised laboratory calibration standards, poorly performing instrumentation, lack of vigilance to contamination, or inattention to unreasonable isotopic outcomes. To counteract common errors, we recommend that laboratories include 1-2 'known' control standards in all autoruns; laser laboratories should screen each autorun for spectral contamination; and all laboratories should evaluate whether derived d-excess values are realistic when both isotope ratios are measured. Combined, these data evaluation strategies should immediately inform the laboratory about fundamental mistakes or compromised samples. Copyright © 2018 John Wiley & Sons, Ltd.

Seeking excellence: An evaluation of 235 international laboratories conducting water isotope analyses by isotope-ratio and laser-absorption spectrometry

USGS Publications Warehouse

Wassenaar, L. I.; Terzer-Wassmuth, S.; Douence, C.; Araguas-Araguas, L.; Aggarwal, P. K.; Coplen, Tyler B.

2018-01-01

RationaleWater stable isotope ratios (δ2H and δ18O values) are widely used tracers in environmental studies; hence, accurate and precise assays are required for providing sound scientific information. We tested the analytical performance of 235 international laboratories conducting water isotope analyses using dual-inlet and continuous-flow isotope ratio mass spectrometers and laser spectrometers through a water isotope inter-comparison test.MethodsEight test water samples were distributed by the IAEA to international stable isotope laboratories. These consisted of a core set of five samples spanning the common δ-range of natural waters, and three optional samples (highly depleted, enriched, and saline). The fifth core sample contained unrevealed trace methanol to assess analyst vigilance to the impact of organic contamination on water isotopic measurements made by all instrument technologies.ResultsFor the core and optional samples ~73 % of laboratories gave acceptable results within 0.2 ‰ and 1.5 ‰ of the reference values for δ18O and δ2H, respectively; ~27 % produced unacceptable results. Top performance for δ18O values was dominated by dual-inlet IRMS laboratories; top performance for δ2H values was led by laser spectrometer laboratories. Continuous-flow instruments yielded comparatively intermediate results. Trace methanol contamination of water resulted in extreme outlier δ-values for laser instruments, but also affected reactor-based continuous-flow IRMS systems; however, dual-inlet IRMS δ-values were unaffected.ConclusionsAnalysis of the laboratory results and their metadata suggested inaccurate or imprecise performance stemmed mainly from skill- and knowledge-based errors including: calculation mistakes, inappropriate or compromised laboratory calibration standards, poorly performing instrumentation, lack of vigilance to contamination, or inattention to unreasonable isotopic outcomes. To counteract common errors, we recommend that laboratories include 1–2 'known' control standards in all autoruns; laser laboratories should screen each autorun for spectral contamination; and all laboratories should evaluate whether derived d-excess values are realistic when both isotope ratios are measured. Combined, these data evaluation strategies should immediately inform the laboratory about fundamental mistakes or compromised samples.

Implications of 187Os isotopic heterogeneities in a mantle plume: evidence from Gorgona Island and Curaçao

NASA Astrophysics Data System (ADS)

Walker, Richard J.; Storey, Michael; Kerr, Andrew C.; Tarney, John; Arndt, Nicholas T.

1999-03-01

Recent work has suggested that the mafic-ultramafic volcanism in evidence throughout portions of the Caribbean, Central America, and northern South America, including the islands of Gorgona and Curaçao, was generated as part of a middle-Cretaceous, large igneous province. New Re-Os isochron results for tholeiitic basalts from Gorgona and Curaçao indicate crystallization ages of 89.2 ± 5.2 and 85.6 ± 8.1 Ma, respectively, consistent with reported Ar ages. The Gorgona ultramafic suite shows a large range in initial Os isotopic composition, with γ Os values ranging from -0.5 to +12.4. This large range reflects isotopic heterogeneities in the mantle source similar to those observed for modern ocean island basalts. In contrast to ocean island basalts, however, Os isotopic compositions do not correlate with variations in Nd, Sr, or Pb isotopic compositions, which are within the range of depleted mid-ocean ridge basalts. The processes that produced these rocks evidently resulted in the decoupling of Os isotopes from the Nd, Sr, and Pb isotopic systems. Picrites from Curaçao have very uniform, chondritic initial Os isotopic compositions, with initial γ Os values ranging only from -0.4 to ±1.4. Basalts from Curaçao, however, define an isochron with a 187Os-enriched initial isotopic composition (γ Os = +9.5). In contrast to the 187Os-enriched ultramafic rocks from Gorgona, the enrichment in these basalts could have resulted from lithospheric contamination. If the Gorgona and Curaçao rocks were derived from the same plume, Os results, combined with Sr, Nd, and Pb data indicate a heterogeneous plume, with multiple compositionally and isotopically distinct domains. The Os isotopic results require derivation of Os from a minimum of two distinct reservoirs, one with a composition very similar to the chondritic average and one with long-term enriched Re/Os. Oceanic crustal recycling has been invoked to explain most of the 187Os enrichments that have been observed in ocean island basalt sources and could potentially apply to the Gorgona suite. Crustal recycling, however, requires large proportions of very ancient recycled basaltic crust in the sources of the 187Os-enriched ultramafic rocks to explain the magnitude of 187Os enrichments observed. For example, addition of 20% oceanic crust to fertile mantle, and nearly 3 billion years are necessary to generate a reservoir with the Os isotopic composition of the most radiogenic komatiites. If the recycled oceanic crust was added to basalt-depleted mantle, as may be indicated by ɛ Nd values for the komatiites averaging about +10, even larger proportions of older crust are required. Large proportions of oceanic mafic crust in the sources of the 187Os-enriched komatiites, although petrologically conceivable under certain melting conditions, is unlikely here given the limited trace element and lithophile isotope system variations. These results raise questions about the efficacy of using Os isotopes to constrain the proportion of recycled oceanic crust in other plumes. Other possible mechanisms for generating 187Os-enriched mantle include invoking the existence of a 187Os-enriched lower mantle, and minor outer core-lower mantle interactions.

CNO isotopes in red giant stars

NASA Technical Reports Server (NTRS)

Wannier, P. G.

1985-01-01

The production and distribution of the CNO nuclides is discussed in light of observed abundance ratios in red giants and in the interstellar medium. Isotope abundances have been measured in the atmospheres and in the recent ejecta of cool giants, including carbon stars, S-type stars and red supergiants as well as in oxygen-rich giants making their first ascent of the giant branch. Several of the observations suggest revision of currently accepted nuclear cross-sections and of the mixing processes operating in giant envelopes. By comparing red giant abundances with high-quality observations of the interstellar medium, conclusions are reached about the contribution of intermediate-mass stars to galactic nuclear evolution. The three oxygen isotopes, O-16, -17 and -18, are particularly valuable for such comparison because they reflect three different stages of stellar nucleosynthesis. One remarkable result comes from observations of O-17/O-18 in several classes of red giant stars. The observed range of values for red giants excludes the entire range of values seen in interstellar molecular clouds. Furthermore, both the observations of stars and interstellar clouds exclude the isotopic ratio found in the solar system.

Paleomobility in the Tiwanaku diaspora: biogeochemical analyses at Rio Muerto, Moquegua, Peru.

PubMed

Knudson, Kelly J; Goldstein, Paul S; Dahlstedt, Allisen; Somerville, Andrew; Schoeninger, Margaret J

2014-11-01

Paleomobility has been a key element in the study of the expansion of ancient states and empires, including the Tiwanaku polity of the South Central Andes (AD 500-1000). We present radiogenic strontium and oxygen isotope data from human burials from three cemeteries in the Tiwanaku-affiliated Middle Horizon archaeological site complex of Rio Muerto in the Moquegua Valley of southern Peru. At Rio Muerto, archaeological human enamel and bone values range from (87) Sr/(86) Sr = 0.70657-0.72018, with a mean of (87) Sr/(86) Sr = 0.70804 ± 0.00207 (1σ, n = 55). For the subset of samples analyzed for oxygen isotope values (n = 48), the data ranges from δ(18) Ocarbonate(VSMOW)  = +18.1 to +27.0‰. When contextualized with other lines of archaeological evidence, we interpret these data as evidence for an archaeological population in which the majority of individuals had "local" origins, and were likely second-generation, or more, immigrants from the Tiwanaku heartland in the altiplano. Based on detailed life history data, we argue a smaller number of individuals came at different ages from various regions within the Tiwanaku polity. We consider whether these individuals with isotopic values consistent with "nonlocal" geographic origins could represent first-generation migrants, marriage exchange partners, or occupationally mobile herders, traders or other travelers. By combining isotopic life history studies with mortuary treatment data, we use a person-centered migration history approach to state integration and expansion. Isotopic analyses of paleomobility at the Rio Muerto site complex contribute to the role of diversity in ancient states by demonstrating the range of geographic origins rather than simply colonists from the Lake Titicaca Basin. © 2014 Wiley Periodicals, Inc.

Molybdenum isotope systematics in subduction zones

NASA Astrophysics Data System (ADS)

König, Stephan; Wille, Martin; Voegelin, Andrea; Schoenberg, Ronny

2016-08-01

This study presents Mo isotope data for arc lavas from different subduction zones that range between δ 98 / 95 Mo = - 0.72 and + 0.07 ‰. Heaviest isotope values are observed for the most slab fluid dominated samples. Isotopically lighter signatures are related to increasing relevance of terrigenous sediment subduction and sediment melt components. Our observation complements previous conclusions that an isotopically heavy Mo fluid flux likely mirrors selective incorporation of isotopically light Mo in secondary minerals within the subducting slab. Analogue to this interpretation, low δ 98 / 95 Mo flux that coincides with terrigenous sediment subduction and sediment melting cannot be simply related to a recycled input signature. Instead, breakdown of the controlling secondary minerals during sediment melting may release the light component and lead to decreasing δ 98 / 95 Mo influx into subarc mantle sources. The natural range between slab dehydration and hydrous sediment melting may thus cause a large spread of δ 98 / 95 Mo in global subduction zone magmas.

Variability in δ13C values between individual Daphnia ephippia: Implications for palaeo-studies

NASA Astrophysics Data System (ADS)

Schilder, Jos; van Roij, Linda; Reichart, Gert-Jan; Sluijs, Appy; Heiri, Oliver

2018-06-01

The stable carbon isotope ratio (δ13C value) of Daphnia spp. resting egg shells (ephippia) provides information on past changes in Daphnia diet. Measurements are typically performed on samples of ≥20 ephippia, which obscures the range of values associated with individual ephippia. Using a recently developed laser ablation-based technique, we perform multiple δ13C analyses on individual ephippia, which show a high degree of reproducibility (standard deviations 0.1-0.5‰). We further measured δ13C values of 13 ephippia from surface sediments of three Swiss lakes. In the well-oxygenated lake with low methane concentrations, δ13C values are close to values typical for algae (-31.4‰) and the range in values is relatively small (5.8‰). This variability is likely driven by seasonal (or inter-annual) variability in algae δ13C values. In two seasonally anoxic lakes with higher methane concentrations, average values were lower (-41.4 and -43.9‰, respectively) and the ranges much larger (10.7 and 20.0‰). We attribute this variability to seasonal variation in incorporation of methane-derived carbon. In one lake we identify two statistically distinct isotopic populations, which may reflect separate production peaks. The potentially large within-sample variability should be considered when interpreting small-amplitude, short-lived isotope excursions based on samples consisting of few ephippia. We show that measurements on single ephippia can be performed using laser ablation, which allows for refined assessments of past Daphnia diet and carbon cycling in lake food webs. Furthermore, our study provides a basis for similar measurements on other chitinous remains (e.g. from chironomids, bryozoans).

Efficacy of passive sampler collection for atmospheric NO2 isotopes under simulated environmental conditions.

PubMed

Coughlin, Justin G; Yu, Zhongjie; Elliott, Emily M

2017-07-30

Nitrogen oxides or NO x (NO x = NO + NO 2 ) play an important role in air quality, atmospheric chemistry, and climate. The isotopic compositions of anthropogenic and natural NO 2 sources are wide-ranging, and they can be used to constrain sources of ambient NO 2 and associated atmospheric deposition of nitrogen compounds. While passive sample collection of NO 2 isotopes has been used in field studies to determine NO x source influences on atmospheric deposition, this approach has not been evaluated for accuracy or precision under different environmental conditions. The efficacy of NO 2 passive sampler collection for NO 2 isotopes was evaluated under varied temperature and relative humidity (RH) conditions in a dynamic flux chamber. The precision and accuracy of the filter NO 2 collection as nitrite (NO 2 - ) for isotopic analysis were determined using a reference NO 2 gas tank and through inter-calibration with a modified EPA Method 7. The bacterial denitrifer method was used to convert 20 μM of collected NO 2 - or nitrate (NO 3 - ) into N 2 O and was carried out on an Isoprime continuous flow isotope ratio mass spectrometer. δ 15 N-NO 2 values determined from passive NO 2 collection, in conditions of 11-34 °C, 1-78% RH, have an overall accuracy and precision of ±2.1 ‰, and individual run precision of ±0.6 ‰. δ 18 O-NO 2 values obtained from passive NO 2 sampler collection, under the same conditions, have an overall precision of ± 1.3 ‰. Suitable conditions for passive sampler collection of NO 2 isotopes are in environments ranging from 11 to 34 °C and 1 to 78% RH. The passive NO 2 isotope measurement technique provides an accurate method to determine variations in atmospheric δ 15 N-NO 2 values and a precise method for determining atmospheric δ 18 O-NO 2 values. The ability to measure NO 2 isotopes over spatial gradients at the same temporal resolution provides a unique perspective on the extent and seasonality of fluctuations in atmospheric NO 2 isotopic compositions. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Identification of sulfur sources and isotopic equilibria in submarine hot-springs using multiple sulfur isotopes

NASA Astrophysics Data System (ADS)

McDermott, Jill M.; Ono, Shuhei; Tivey, Margaret K.; Seewald, Jeffrey S.; Shanks, Wayne C.; Solow, Andrew R.

2015-07-01

Multiple sulfur isotopes were measured in metal sulfide deposits, elemental sulfur, and aqueous hydrogen sulfide to constrain sulfur sources and the isotopic systematics of precipitation in seafloor hydrothermal vents. Areas studied include the Eastern Manus Basin and Lau Basin back-arc spreading centers and the unsedimented basalt-hosted Southern East Pacific Rise (SEPR) and sediment-hosted Guaymas Basin mid-ocean ridge spreading centers. Chalcopyrite and dissolved hydrogen sulfide (H2S) δ34S values range from -5.5‰ to +5.6‰ in Manus Basin samples, +2.4‰ to +6.1‰ in Lau Basin samples, and +3.7‰ to +5.7‰ in SEPR samples. Values of δ34S for cubic cubanite and H2S range from -1.4‰ to +4.7‰ in Guaymas Basin samples. Multiple sulfur isotope systematics in fluid-mineral pairs from the SEPR and Lau Basin show that crustal host rock and thermochemical reduction of seawater-derived dissolved sulfate (SO4) are the primary sources of sulfur in mid-ocean ridge and some back-arc systems. At PACMANUS and SuSu Knolls hydrothermal systems in the Eastern Manus Basin, a significant contribution of sulfur is derived from disproportionation of magmatic sulfur dioxide (SO2), while the remaining sulfur is derived from crustal host rocks and SO4 reduction. At the sedimented Guaymas Basin hydrothermal system, sulfur sources include crustal host rock, reduced seawater SO4, and biogenic sulfide. Vent fluid flow through fresher, less-mature sediment supplies an increased quantity of reactant organic compounds that may reduce 34S-enriched SO4, while fluid interaction with more highly-altered sediments results in H2S characterized by a small, but isotopically-significant input of 34S-depleted biogenic sulfides. Near-zero Δ33S values in all samples implicate the abiotic processes of SO4 reduction and leaching of host rock as the major contributors to sulfur content at a high temperature unsedimented mid-ocean ridge and at a back-arc system. Δ33S values indicate that SO2 disproportionation is an additional process that contributes sulfur to a different back-arc system and to acid spring-type hydrothermal fluid circulation. At the sedimented Guaymus Basin, near-zero Δ33S values are also observed, despite negative δ34S values that indicate inputs of biogenic pyrite for some samples. In contrast with previous studies reporting isotope disequilibrium between H2S and chalcopyrite, the δ34S values of chalcopyrite sampled from the inner 1-2 mm of a chimney wall are within ±1‰ of δ34S values for H2S in the paired vent fluid, suggesting equilibrium fluid-mineral sulfur isotope exchange at 300-400 °C. Isotopic equilibrium between hydrothermal fluid H2S and precipitating chalcopyrite implies that sulfur isotopes in the chalcopyrite lining across a chimney wall may accurately record past hydrothermal activity.

Stable Te isotope fractionation in tellurium-bearing minerals from precious metal hydrothermal ore deposits

NASA Astrophysics Data System (ADS)

Fornadel, Andrew P.; Spry, Paul G.; Haghnegahdar, Mojhgan A.; Schauble, Edwin A.; Jackson, Simon E.; Mills, Stuart J.

2017-04-01

The tellurium isotope compositions of naturally-occurring tellurides, native tellurium, and tellurites were measured by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) and compared to theoretical values for equilibrium mass-dependent isotopic fractionation of representative Te-bearing species estimated with first-principles thermodynamic calculations. Calculated fractionation models suggest that 130/125Te fractionations as large as 4‰ occur at 100 °C between coexisting tellurates (Te VI) and tellurides (Te -II) or or native tellurium Te(0), and smaller, typically <1‰, fractionations occur between coexisting Te(-I) or Te(-II) (Au,Ag)Te2 minerals (i.e., calaverite, krennerite) and (Au,Ag)2Te minerals (i.e., petzite, hessite). In general, heavyTe/lightTe is predicted to be higher for more oxidized species, and lower for reduced species. Tellurides in the system Au-Ag-Te and native tellurium analyzed in this study have values of δ130/125Te = -1.54‰ to 0.44‰ and δ130/125Te = -0.74‰ to 0.16‰, respectively, whereas those for tellurites (tellurite, paratellurite, emmonsite and poughite) range from δ130/125Te = -1.58‰ to 0.59‰. Thus, the isotopic composition for both oxidized and reduced species are broadly coincident. Calculations of per mil isotopic variation per amu for each sample suggest that mass-dependent processes are responsible for fractionation. In one sample of coexisting primary native tellurium and secondary emmonsite, δ130/125Te compositions were identical. The coincidence of δ130/125Te between all oxidized and reduced species in this study and the apparent lack of isotopic fractionation between native tellurium and emmonsite in one sample suggest that oxidation processes cause little to no fractionation. Because Te is predominantly transported as an oxidized aqueous phase or as a reduced vapor phase under hydrothermal conditions, either a reduction of oxidized Te in hydrothermal liquids or deposition of Te from a reduced vapor to a solid is necessary to form the common tellurides and native tellurium in ore-forming systems. Our data suggest that these sorts of reactions during mineralization may account for a ∼3‰ range of δ130/125Te values. Based on the data ranges for Te minerals from various ore deposits, the underpinning geologic processes responsible for mineralization seem to have primary control on the magnitude of fractionation, with tellurides in epithermal gold deposits showing a narrower range of isotope values than those in orogenic gold and volcanogenic massive sulfide deposits.

High-precision 41K/39K measurements by MC-ICP-MS indicate terrestrial variability of δ41K

USGS Publications Warehouse

Morgan, Leah; Santiago Ramos, Danielle P.; Davidheiser-Kroll, Brett; Faithfull, John; Lloyd, Nicholas S.; Ellam, Rob M.; Higgins, John A.

2018-01-01

Potassium is a major component in continental crust, the fourth-most abundant cation in seawater, and a key element in biological processes. Until recently, difficulties with existing analytical techniques hindered our ability to identify natural isotopic variability of potassium isotopes in terrestrial materials. However, measurement precision has greatly improved and a range of K isotopic compositions has now been demonstrated in natural samples. In this study, we present a new technique for high-precision measurement of K isotopic ratios using high-resolution, cold plasma multi-collector mass spectrometry. We apply this technique to demonstrate natural variability in the ratio of 41K to 39K in a diverse group of geological and biological samples, including silicate and evaporite minerals, seawater, and plant and animal tissues. The total range in 41K/39K ratios is ca. 2.6‰, with a long-term external reproducibility of 0.17‰ (2, N=108). Seawater and seawater-derived evaporite minerals are systematically enriched in 41K compared to silicate minerals by ca. 0.6‰, a result consistent with recent findings1, 2. Although our average bulk-silicate Earth value (-0.54‰) is indistinguishable from previously published values, we find systematic δ41K variability in some high-temperature sample suites, particularly those with evidence for the presence of fluids. The δ41K values of biological samples span a range of ca. 1.2‰ between terrestrial mammals, plants, and marine organisms. Implications of terrestrial K isotope variability for the atomic weight of K and K-based geochronology are discussed. Our results indicate that high-precision measurements of stable K isotopes, made using commercially available mass spectrometers, can provide unique insights into the chemistry of potassium in geological and biological systems. 

Oxygen isotopic determinations of sequentially erupted plagioclases in the 1974 magma of Fuego Volcano, Guatemala

USGS Publications Warehouse

Rose, W.I.; Friedman, I.; Woodruff, L.G.

1980-01-01

Plagioclases in the 1974 high-Al basalt from Fuego Volcano have ??O18 values of +6.0 to +8.5 per mil. Meteoric water cannot have played a significant role in Fuego's magma. Large, weakly zone clear phenocrysts had ??O18 values in the accepted mantle range, while patchyzoned and oscillatory-zoned plagioclases inferred to have formed later and shallower levels have slightly heavier oxygen isotopic ratios. ?? 1980 Intern. Association of Volcanology and Chemistry of the Earth's Interior.

Two Distinct Sets of Magma Sources in Cretaceous Rocks From Magnet Cove, Prairie Creek, and Other Igneous Centers of the Arkansas Alkaline Province, USA

NASA Astrophysics Data System (ADS)

Duke, G. I.; Carlson, R. W.; Eby, G. N.

2008-12-01

Two distinct sets of magma sources from the Arkansas alkaline province (~106-89 Ma) are revealed by Sr-Nd-Pb isotopic compositions of olivine lamproites vs. other alkalic rock types, including carbonatite, ijolite, lamprophyres, tephrite, malignite, jacupirangite, phonolite, trachyte, and latite. Isotopic compositions of diamond-bearing olivine lamproites from Prairie Creek and Dare Mine Knob point to Proterozoic lithosphere as an important source, and previous Re-Os isotopic data indicate derivation from subcontinental mantle lithosphere. Both sources were probably involved in lamproite generation. Magnet Cove carbonatites and other alkalic magmas were likely derived from an asthenospheric source. Lamproite samples are isotopically quite different from other rock types in Sr-Nd-Pb isotopic space. Although three lamproite samples from Prairie Creek have a large range of SiO2 contents (40-60 wt %), initial values of ɛNd (-10 to -13), 206Pb/204Pb (16.61-16.81), 207Pb/204Pb (15.34-15.36), and 208Pb/204Pb (36.57-36.76) are low and similar. Only 87Sr/86Sr(i) displays a wide range in the Prairie Creek lamproites (0.70627-0.70829). A fourth lamproite from Dare Mine Knob has the most negative ɛNd(i) of -19. Lamproite isotope values show a significant crustal component and isotopically overlap subalkalic rhyolites from the Black Hills (SD), which assimilated Proterozoic crust. Six samples of carbonatite, ijolite, and jacupirangite from Magnet Cove and Potash Sulphur Springs exhibit the most depleted Sr-Nd isotopic signatures of all samples. For these rock types, 87Sr/86Sr(i) is 0.70352 - 0.70396, and ɛNd(i) is +3.8 - +4.3. Eight other rock types have a narrow range of ɛNd(i) (+1.9 - +3.7), but a wide range of 87Sr/86Sr(i) (0.70424 - 0.70629). These 14 samples comprise a fairly tight cluster of Pb isotopic values: 206Pb/204Pb (18.22-19.23), 207Pb/204Pb (15.54-15.62), and 208Pb/204Pb (38.38-38.94), suggesting very little crustal assimilation. They are most similar to EM-2 (sub-group of OIB). Published ages of crustal amphibolite xenoliths from the Prairie Creek lamproite are Proterozoic (~1.32- 1.47 Ga), in keeping with isotopic evidence for crustal assimilation, including Tdm = 1.3-1.7 Ga. Published ages of lamproite (~106 Ma) indicate that these magmas intruded first, whereas carbonatites and other alkalic magmas were later (~102 to ~89 Ma). Asthenospheric upwelling first melted lithospheric mantle and crust, producing lamproitic magmas; asthenospheric magmas followed as swelling of the lithosphere ensued.

Fractionation of 238U/235U by reduction during low temperature uranium mineralisation processes

NASA Astrophysics Data System (ADS)

Murphy, Melissa J.; Stirling, Claudine H.; Kaltenbach, Angela; Turner, Simon P.; Schaefer, Bruce F.

2014-02-01

Investigations of ‘stable’ uranium isotope fractionation during low temperature, redox transformations may provide new insights into the usefulness of the 238U/235U isotope system as a tracer of palaeoredox processes. Sandstone-hosted uranium deposits accumulate at an oxidation/reduction interface within an aquifer from the low temperature reduction of soluble U(VI) complexes in groundwaters, forming insoluble U(IV) minerals. This setting provides an ideal environment in which to investigate the effects of redox transformations on 238U/235U fractionation. Here we present the first coupled measurements of 238U/235U isotopic compositions and U concentrations for groundwaters and mineralised sediment samples from the same redox system in the vicinity of the high-grade Pepegoona sandstone-hosted uranium deposit, Australia. The mineralised sediment samples display extremely variable 238U/235U ratios (herein expressed as δUCRM145238, the per-mil deviation from the international NBL standard CRM145). The majority of mineralised sediment samples have δUCRM145238 values between -1.30±0.05 and 0.55±0.12‰, spanning a ca. 2‰ range. However, one sample has an unusually light isotopic composition of -4.13±0.05‰, which suggests a total range of U isotopic variability of up to ca. 5‰, the largest variation found thus far in a single natural redox system. The 238U/235U isotopic signature of the mineralised sediments becomes progressively heavier (enriched in 238U) along the groundwater flow path. The groundwaters show a greater than 2‰ variation in their 238U/235U ratios, ranging from δUCRM145238 values of -2.39±0.07 to -0.71±0.05‰. The majority of the groundwater data exhibit a clear systematic relationship between 238U/235U isotopic composition and U concentration; samples with the lowest U concentrations have the lowest 238U/235U ratios. The preferential incorporation of 238U during reduction of U(VI) to U(IV) and precipitation of uranium minerals leaves the groundwaters enriched in 235U, resulting in a progressive shift in 238U/235U towards lighter values in the aqueous phase as U is removed. These data can be modelled by a closed system Rayleigh fractionation model, with a fractionation factor (α, representing the 238U/235U composition of the groundwater relative to the solid uranium minerals) ranging from ∼0.9996 to 1.0000, with the majority of datapoints ranging from α values of 0.9998 to 0.9999. The sense and magnitude of the results of this study imply that 238U/235U fractionation is likely to be controlled by volume-dependent nuclear field shift effects during the reduction of U(VI) to U(IV) during mineralisation processes. These findings support the use of the 238U/235U isotopic system as a tracer to constrain the nature and timing of palaeoredox conditions.

Multiple Export Production and Sulfur Isotope Records over the Paleocene Eocene Thermal Maximum

NASA Astrophysics Data System (ADS)

Gray, E.; Paytan, A.

2007-12-01

The Paleocene Eocene Thermal Maximum (PETM) was a global climatic event that occurred 55 million years ago. δ18O values from benthic foraminifera indicate that temperatures rose 4-5°C coeval with a precipitous drop in δ13C values that indicate a new source of carbon rapidly entered the global carbon cycle. Marine barite (BaSO4) was used to evaluate the 1) barite accumulation rate that serves a proxy for export production and 2) the sulfur isotopic composition of seawater that reflects the mass balance of oceanic sulfate (SO42-). Increased barite accumulation rates at the PETM suggest that increased export production and CO2 sequestration was in direct response to the carbon isotope excursion, although not all of the increases are accounted for. High resolution δ34S values are lower but within reasonable range of previously observed values and indicate a decrease in sulfate removal by pyrite deposition.

Sulfur and oxygen isotopic study of Paleozoic sediment-hosted Zn-Pb(-Ag-Au-Ba-F) deposits and associated hydrothermal alteration zones in the Nome Complex, Seward Peninsula, Alaska

USGS Publications Warehouse

Shanks, W.C. Pat; Slack, John F.; Till, Alison B.; Thurston, Roland; Gemery-Hill, Pamela

2014-01-01

The stratabound Nelson deposit, and the deformed veins at the Galena and Quarry deposits, may be older than the Aurora Creek-Christophosen and Wheeler North deposits. The Nelson deposit has a lower and narrower range of δ34S values (1.9 to 10.4‰), averaging about 8‰. The Galena and Quarry veins display δ34S values that are similar to those of the stratabound Nelson deposit. Barite samples from the Aurora Creek-Christophosen, Wheeler North, and Quarry deposits have 34S-enriched δ34S values between 25 and 30‰ that are consistent with derivation of the sulfur from coeval (Paleozoic) seawater sulfate. Given their δ34S values, it is likely that the Aurora Creek-Christophosen and Wheeler North deposits formed in closed sub-basins with euxinic conditions that led to extreme Rayleigh distillation to produce the very large range and very high δ34S values. The Nelson deposit probably formed within an anoxic but not euxinic sub-basin. At Nelson, sulfide was likely derived by a subsurface thermochemical sulfate reduction (TSR) reaction, similar to reactions that are inferred to have produced the sulfides in the Galena and Quarry deposits, which are interpreted as feeder veins for the stratabound deposits. Calculations of oxygen isotope temperatures are based on the assumption that evolved seawater with δ18O of 3‰ was the mineralizing and altering fluid related to the formation of the sulfide deposits. Temperatures of aluminous alteration and sulfide mineralization were between 109 and 209 °C, determined on the basis of oxygen isotope fractionations between the mineralizing fluid and proportionate amounts of quartz and muscovite in the rocks. These temperature estimates agree well with known temperatures of SEDEX mineralization worldwide. Sulfur isotope values also are generally consistent with the known ranges in SEDEX deposits worldwide (δ34S ≈ -5 to 25‰).

New biotite and muscovite isotopic reference materials, USGS57 and USGS58, for δ2H measurements–A replacement for NBS 30

USGS Publications Warehouse

Qi, Haiping; Coplen, Tyler B.; Gehre, Matthias; Vennemann, Torsten W.; Brand, Willi A.; Geilmann, Heike; Olack, Gerard; Bindeman, Ilya N.; Palandri, Jim; Huang, Li; Longstaffe, Fred J.

2017-01-01

The advent of continuous-flow isotope-ratio mass spectrometry (CF-IRMS) coupled with a high temperature conversion (HTC) system enabled faster, more cost effective, and more precise δ2H analysis of hydrogen-bearing solids. Accurate hydrogen isotopic analysis by on-line or off-line techniques requires appropriate isotopic reference materials (RMs). A strategy of two-point calibrations spanning δ2H range of the unknowns using two RMs is recommended. Unfortunately, the supply of the previously widely used isotopic RM, NBS 30 biotite, is exhausted. In addition, recent measurements have shown that the determination of δ2H values of NBS 30 biotite on the VSMOW-SLAP isotope-delta scale by on-line HTC systems with CF-IRMS may be unreliable because hydrogen in this biotite may not be converted quantitatively to molecular hydrogen. The δ2HVSMOW-SLAP values of NBS 30 biotite analyzed by on-line HTC systems can be as much as 21 mUr (or ‰) too positive compared to the accepted value of − 65.7 mUr, determined by only a few conventional off-line measurements. To ensure accurate and traceable on-line hydrogen isotope-ratio determinations in mineral samples, we here propose two isotopically homogeneous, hydrous mineral RMs with well-characterized isotope-ratio values, which are urgently needed. The U.S. Geological Survey (USGS) has prepared two such RMs, USGS57 biotite and USGS58 muscovite. The δ2H values were determined by both glassy carbon-based on-line conversion and chromium-based on-line conversion, and results were confirmed by off-line conversion. The quantitative conversion of hydrogen from the two RMs using the on-line HTC method was carefully evaluated in this study. The isotopic compositions of these new RMs with 1-σ uncertainties and mass fractions of hydrogen are:USGS57 (biotite)δ2HVSMOW-SLAP = − 91.5 ± 2.4 mUr (n = 24)Mass fraction hydrogen = 0.416 ± 0.002% (n = 4)Mass fraction water = 3.74 ± 0.02% (n = 4)USGS58 (muscovite)δ2HVSMOW-SLAP = − 28.4 ± 1.6 mUr (n = 24)Mass fraction hydrogen = 0.448 ± 0.002% (n = 4)Mass fraction water = 4.03 ± 0.02% (n = 4).These δ2HVSMOW-SLAP values encompass typical ranges for solid unknowns of crustal and mantle origin and are available to users for recommended two-point calibration.

Ross Sea Ecosystem Responses to Climatic Changes during the Mid-to-Late Holocene as Indicated by Bulk Stable Isotope Analyses of Antarctic Seals

NASA Astrophysics Data System (ADS)

Brault, E.; Koch, P. L.; McCarthy, M. D.; Hall, B. L.; Hoelzel, A. R.; Welch, A. J.; Nye, J. W.; Rosenfield, A. P.

2016-02-01

Substantial environmental changes occurred in the Ross Sea during the Holocene, with sea ice likely significantly increasing around 1,000 years before present (YBP). We are investigating the effects of these environmental changes on the biological community. Previous work demonstrates that the southern elephant seal (Mirounga leonina) colonies in the region began to collapse 1,000 YBP and disappeared from the area by 250 YBP. Ecosystem shifts are also evident in isotopic records. Carbon and nitrogen isotope data from Adélie penguins (Pygoscelis adeliae) differ from animals in the region today, and our isotopic values of fossil southern elephant seals are inconsistent with foraging in the current Ross Sea ecosystem. The dating of these isotopic shifts is uncertain, ranging from 1,000 to 250 YBP. We examined trends in the bulk carbon and nitrogen isotope values of Weddell (Leptonychotes weddellii) and crabeater (Lobodon carcinophagus) seals over the last 5,500 years to clarify the timing of the ecosystem shift, and further explore its effects on top predators. Crabeater seals have stable mean carbon and nitrogen isotope values through the late Holocene period, suggesting stable foraging behavior. However, isotopic data from this species are more variable before 750 YBP, indicating a more diverse foraging ecology. Weddell seals show a clear transition in isotopic values around 500 YBP, similar to that previously observed in penguins. This shift may indicate a change in Weddell seal diet (to lower trophic level prey in more recent times), a changed ecosystem (with the Ross Sea becoming less productive later in the Holocene), or both. Overall, our data shows that the ecology of top predators shifted substantially in response to changes in the Ross Sea around 1,000-500 years ago.

In Situ Carbon Isotope Analysis by Laser Ablation MC-ICP-MS.

PubMed

Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Zhao, Kui-Dong; Duan, Deng-Fei

2017-12-19

Carbon isotopes have been widely used in tracing a wide variety of geological and environmental processes. The carbon isotope composition of bulk rocks and minerals was conventionally analyzed by isotope ratio mass spectrometry (IRMS), and, more recently, secondary ionization mass spectrometry (SIMS) has been widely used to determine carbon isotope composition of carbon-bearing solid materials with good spatial resolution. Here, we present a new method that couples a RESOlution S155 193 nm laser ablation system with a Nu Plasma II MC-ICP-MS, with the aim of measuring carbon isotopes in situ in carbonate minerals (i.e., calcite and aragonite). Under routine operating conditions for δ 13 C analysis, instrumental bias generally drifts by 0.8‰-2.0‰ in a typical analytical session of 2-3 h. Using a magmatic calcite as the standard, the carbon isotopic composition was determined for a suite of calcite samples with δ 13 C values in the range of -6.94‰ to 1.48‰. The obtained δ 13 C data are comparable to IRMS values. The combined standard uncertainty for magmatic calcite is <0.3‰ (1s). No significant matrix effects have been identified in calcite with the amplitude of chemical composition variation (i.e., MnO, SrO, MgO, or FeO) up to 2.5 wt %. Two modern corals were investigated using magmatic calcite as the calibration standard, and the average δ 13 C values for both corals are similar to the bulk IRMS values. Moreover, coral exhibits significant heterogeneity in carbon isotope compositions, with differences up to 4.85‰ within an individual coral. This study indicates that LA-MC-ICP-MS can serve as an appropriate method to analyze carbon isotopes of carbonate minerals in situ.

Stable carbon and nitrogen isotope analysis of avian uric acid.

PubMed

Bird, Michael I; Tait, Elaine; Wurster, Christopher M; Furness, Robert W

2008-11-01

We report results obtained using a new technique developed to measure the stable-isotope composition of uric acid isolated from bird excreta (guano). Results from a diet-switch feeding trial using zebra finches suggest that the delta(13)C of uric acid in the guano equilibrates with the diet of the bird within 3 days of a change in diet, while the equilibration time for delta(15)N may be longer. The average carbon isotope discrimination between uric acid and food before the diet switch was +0.34 +/- 1 per thousand (1sigma) while after the diet switch this increased slightly to +0.83 +/- 0.7 per thousand (1sigma). Nitrogen isotope discrimination was +1.3 +/- 0.3 per thousand (1sigma) and +0.3 +/- 0.3 per thousand (1sigma) before and after the diet switch; however, it is possible that the nitrogen isotope values did not fully equilibrate with diet switch over the course of the experiment. Analyses of other chemical fractions of the guano (organic residue after uric acid extraction and non-uric acid organics solubilised during extraction) suggest a total range of up to 3 per thousand for both delta(13)C and delta(15)N values in individual components of a single bulk guano sample. The analysis of natural samples from a range of terrestrial and marine species demonstrates that the technique yields isotopic compositions consistent with the known diets of the birds. The results from natural samples further demonstrate that multiple samples from the same species collected from the same location yield similar results, while different species from the same location exhibit a range of isotopic compositions indicative of different dietary preferences. Given that many samples of guano can be rapidly collected without any requirement to capture specimens for invasive sampling, the stable-isotope analysis of uric acid offers a new, simple and potentially powerful tool for studying avian ecology and metabolism.

Stable isotope evidence for an atmospheric origin of desert nitrate deposits in northern Chile and southern California, U.S.A.

USGS Publications Warehouse

Böhlke, J.K.; Ericksen, G.E.; Revesz, K.

1997-01-01

Natural surficial accumulations of nitrate-rich salts in the Atacama Desert, northern Chile, and in the Death Valley region of the Mojave Desert, southern California, are well known, but despite many geologic and geochemical studies, the origins of the nitrates have remained controversial. N and O isotopes in nitrate, and S isotopes in coexisting soluble sulfate, were measured to determine if some proposed N sources could be supported or rejected, and to determine if the isotopic signature of these natural deposits could be used to distinguish them from various types of anthropogenic nitrate contamination that might be found in desert groundwaters. High-grade caliche-type nitrate deposits from both localities have ??15N values that range from -5 to +5???, but are mostly near 0???. Values of ??15N near 0??? are consistent with either bulk atmospheric N deposition or microbial N fixation as major sources of the N in the deposits. ??18O values of those desert nitrates with ??15N near 0??? range from about +31 to + 50??? (V-SMOW), significantly higher than that of atmospheric O2 (+ 23.5???). Such high values of ??18O are considered unlikely to result entirely from nitrification of reduced N, but rather resemble those of modern atmospheric nitrate in precipitation from some other localities. Assuming that limited modern atmospheric isotope data are applicable to the deposits, and allowing for nitrification of co-deposited ammonium, it is estimated that the fraction of the nitrate in the deposits that could be accounted for isotopically by atmospheric N deposition may be at least 20% and possibly as much as 100%. ??34S values are less diagnostic but could also be consistent with atmospheric components in some of the soluble sulfates associated with the deposits. The stable isotope data support the hypothesis that some high-grade caliche-type nitrate-rich salt deposits in some of the Earth's hyperarid deserts represent long-term accumulations of atmospheric deposition (possibly in the order of 104 yr for the Death Valley region. 107 yr for the Atacama Desert) in the relative absence of soil leaching or biologic cycling. The combined N and O isotope signature of the nitrate in these deposits is significantly different from those of many other natural and anthropogenic sources of nitrate.

Forensic utility of the carbon isotope ratio of PVC tape backings

NASA Astrophysics Data System (ADS)

Stern, L. A.; Thompson, A. H.; Mehltretter, A. H.; McLaskey, V.; Parish, A.; Aranda, R.

2008-12-01

Forensic interest in adhesive tapes with PVC-backings (polyvinyl chloride, electrical tapes) derives from their use in construction of improvised explosive devices, drug packaging and in a variety of other illicit activities. Due to the range of physical characteristics and chemical compositions of such tapes, traditional microscopic and chemical analysis of the tape backings and adhesives offer a high degree of discrimination between tapes from different manufacturers and products. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different tapes of the same product, we assessed the PVC-backings of 87 rolls of black electrical tape for their δ13C values. The adhesive on these tapes was physically removed with hexane, and plasticizers within the PVC tape backings were removed by three-20 minute extractions with chloroform. The δ13C values of the PVC tape backings ranged between -23.8 and -41.5 (‰ V-PDB). The carbon isotopic variation within a product (identical brand and product identification) is significant, based on five products with at least 3 rolls (ranges of 7.4‰ (n=3), 10.0‰ (n=6), 4.2‰ (n=16), 3.8‰ (n=6), and 11.5‰ (n=8), respectively). There was no measurable carbon isotope variation in regards to the following: a) along the length of a roll (4 samples from 1 roll); b) between the center and edge of a strip of tape (1 pair); c) between rolls assumed to be from the same lot of tape (2 pairs); d) between different rolls from the same batch of tape (same product purchased at the same time and place; 5 pairs); and e) between samples of a tape at room temperature, heated to 50° C and 80° C for 1 week. For each sample within the population of 87 tapes, carbon isotopes alone exclude 80 to 100% of the tapes as a potential match, with an average exclusion power of 92.5%, using a window of ± 0.4‰. Carbon isotope variations originate from variations in starting materials and recycling reactants during manufacture; as a result, tapes may be otherwise physically and chemical indistinguishable, but may have distinct carbon isotope ratios. We compared the carbon isotope ratios of 6 pairs of pre- and post-blast samples of PVC tapes adhered to explosive charges. The carbon isotope ratios of the post-blast samples were 0 to 0.5 ‰ higher than the corresponding pre-blast samples. Possible causes of this carbon isotope increase may be the reaction of the plasticizer and/or adhesive with the PVC backing during the explosion or the addition of debris to the tape backing during the explosion. Even with these minor explosive-induced carbon isotope alterations, the δ13C values of post-blast PVC tape backings were similar enough to the starting material to make carbon isotope ratios of post-blast tape a useful forensic tool. The range of carbon isotope ratios that would be used to exclude potential matches would have to be larger for post-blast samples, but with a 17 ‰ range in the population, this approach may still be useful for post-blast tape samples.

Isotopic studies of authigenic sulfides, silicates and carbonates, and calcite and pyrite veinlets in the Creede Formation, San Juan Mountains, Southwest Colorado

USGS Publications Warehouse

Bethke, Philip M.; Rye, Robert O.; Finkelstein, David B.

2000-01-01

Sulfur isotope analysis of authigenic pyrite in the Creede Formation documents its precipitation by the reaction between iron in the volcaniclastic sediments and H2S formed through bacteriogenic reduction of sulfate added to the lake during and immediately following repeated volcanic eruptions during sedimentation. Pyrite veinlets in the underlying Snowshoe Mountain Tuff were formed by the percolation of H2S-bearing pore waters into fractures in the tuff. Conventional analyses of bulk samples of authigenic pyrite range from -20.4% to 34.5% essentially equivalent to the range of -30% to 40% determined using SHRIMP microprobe techniques. Conventional analyses of bulk samples of pyrite from veinlets in the Snowshow Mountain Tiff range from -3.5% to 17.6% much more limited than the ranges of -23% to 111% and -15.6% to 67.0% determined by SHRIMP and laser ablation microbeam techniques, respectively. The extreme range of δ34S for the veinlets is interpreted to be the result of continued fractionation of the already 34S-depleted pore water. Oxygen isotope analysis of authigenic smectite, kaolinite, and K-feldspar together with fluid-inclusion temperatures and oxygen isotope analysis of calcite coexisting with kaolinite indicate that the smectites formed early during burial diagenesis, in accord with petrographic observations. The 40Ar/39Ar dating of K-feldspar, concorfance of K-feldspar, kaolinite, and calcite δ18O values, and fluid-inclusion temperatures in calcite, indicate that the sediments at core hole CCM-1 were subjected to a hydrothermal event at 17.6 Ma. The minerals formed oxygen-shifted meteoric waters with δ18O values of ~-9% Smecities at CCM-1 at least partially exchanged with these waters. Carbon and oxygen isotope analysis of authigenic calcites in the Creede Formation show that they formed over a wide range of temperatures from fluids having a wide range of isotopic composition, presumably over an extended period time. Some of the cements apparently formed very late from unexchanged meteoric water. Concretions and possibly some cements at CCM-1 appear to have exchanged with the 17.6 Ma oxygen-shifted hydrothermal fluids. Such exchange is consistent with evidence that lacustrine carbonates at CCM-1 exchanged with low 18O waters, whereas those at CCM-2 underwent little, if any, exchange. The δ13C-δ18O values for calcite veinlets in the Creede Formation are similar to those for authegenic calcites. Fluid-inclusion temperatures and δ18O indicate that some were deposited during the 17.6 Ma hydrothermal event and others from unexchanged meteoric water at a later date. The isotope studies confirm that part of the model of Rye et al., proposing that the barites in the southern end of the Creede Mining District were formed by mixing of the Creede hydrotermal system with Lake Creede pore of lake waters. The silicate and carbonate isotope data indicate that the pores of the Creede Formation were occupied by at least three isotopically distinct water since the time of deposition. The original pore fluids were probably shifted to lower δ18O values during burial diagensis as a result of the hydrolysis of the volcanic glass to for smectites and other hydrous silicates. During or prior to a 17.6 Ma hydrothermal event in the vicinity of CCM-1, the Creede Formation was flushed with oxygen-shifted meteoric water, possibly related to the breaching of the east side of the caldera wall sometime between 20 and 22 Ma. Later, the Creede Formation was again flushed, this time with unexchanged meteoric water with δD-δ18O values of present-day waters, possibly during the incision of the Rio Grande drainage during uplifting of the southern Rocky Mountains beginning about 5 Ma.

A heterogeneous lunar interior for hydrogen isotopes as revealed by the lunar highlands samples

NASA Astrophysics Data System (ADS)

Hui, Hejiu; Guan, Yunbin; Chen, Yang; Peslier, Anne H.; Zhang, Youxue; Liu, Yang; Flemming, Roberta L.; Rossman, George R.; Eiler, John M.; Neal, Clive R.; Osinski, Gordon R.

2017-09-01

Knowing the amount and timing of water incorporation into the Moon has fundamental implications for our understanding of how the Earth-Moon system formed. Water has been detected in lunar samples but its abundance, distribution and origin are debated. To address these issues, we report water concentrations and hydrogen isotope ratios obtained by secondary ion mass spectrometry (SIMS) of plagioclase from ferroan anorthosites (FANs), the only available lithology thought to have crystallized directly from the lunar magma ocean (LMO). The measured water contents are consistent with previous results by Fourier transform infrared spectroscopy (FTIR). Combined with literature data, δD values of lunar igneous materials least-degassed at the time of their crystallization range from -280 to + 310 ‰, the latter value being that of FAN 60015 corrected for cosmic ray exposure. We interpret these results as hydrogen isotopes being fractionated during degassing of molecular hydrogen (H2) in the LMO, starting with the magmatic δD value of primordial water at the beginning of LMO being about - 280 ‰, evolving to about + 310 ‰ at the time of anorthite crystallization, i.e. during the formation of the primary lunar crust. The degassing of hydrogen in the LMO is consistent with those of other volatile elements. The wide range of δD values observed in lunar igneous rocks could be due to either various degrees of mixing of the different mantle end members, or from a range of mantle sources that were degassed to different degrees during magma evolution. Degassing of the LMO is a viable mechanism that resulted in a heterogeneous lunar interior for hydrogen isotopes.

Stable isotope ratio profiling of testosterone preparations.

PubMed

Cawley, Adam; Collins, Michael; Kazlauskas, Rymantas; Handelsman, David J; Heywood, Robert; Longworth, Mitchell; Arenas-Queralt, Andrea

2010-01-01

Gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is the preferred method of confirming the administration of exogenous testosterone by athletes. This relies on synthetic testosterone preparations being depleted in (13) C compared to natural testosterone. There is concern, however, about the existence of synthetic testosterone products that are unexpectedly (13) C-enriched and which may allow athletes to circumvent the current GC-C-IRMS test. Further to the reported studies of legitimate pharmaceutical-grade testosterone products, a detailed analysis of seized materials from border-level seizures was required to obtain intelligence concerning trends in 'black market' testosterone manufacture and distribution. The sample set collected for this study between 2006 and 2009 inclusive provided a δ(13) C range (n = 266) of -22.9‰ to -32.6‰ with mean and median values of -28.4‰ and -28.6‰, respectively. Within this distribution there were 24 samples (9%) confirmed to have δ(13) C values in the range reported for endogenous urinary steroid metabolites (≥ -25.8‰). The benefit of δ(13) C profiling for testosterone preparations was demonstrated by the ability to identify specific seized products that can be target tested for future intelligence purposes. In addition, the potential of stable hydrogen isotope ratio ((2) H/(1) H; δ(2) H) discrimination to complement δ(13) C analysis was investigated. Methodologies for the determination of δ(2) H values by gas chromatography-thermal conversion-isotope ratio mass spectrometry (GC-TC-IRMS) were developed to provide a δ(2) H range (n = 173) of -177‰ to -268‰ with mean and median values of -231‰ and -234‰, respectively. Copyright © 2010 John Wiley & Sons, Ltd.

Influence of magmatic volatiles on boron isotope compositions in vent fluids from the Eastern Manus Basin, Papua New Guinea

NASA Astrophysics Data System (ADS)

Wilckens, F. K.; Kasemann, S.; Bach, W.; Reeves, E. P.; Meixner, A.; Seewald, J.

2016-12-01

In this study we present boron (B), lithium (Li) and strontium (Sr) concentrations and isotopic composition of submarine hydrothermal fluids collected in 2006 and 2011 from PACMANUS, DESMOS and SuSu Knolls vent fields located in the Eastern Manus Basin [1,2]. Hydrothermal vent fluids within the Eastern Manus Basin range from high-temperature black smoker fluids to low-temperature diffuse fluids and acid-sulfate fluids. In general, the different fluid types show variable water-rock ratios during water-rock interaction and different inputs of magmatic volatiles. End-member black smoker fluids, which have in general high temperatures (mostly higher than 280°C) and pH values higher than 2 (measured at 25°C) are characterized by low δ7Li values (3.9 to 5.9‰) and 87Sr/86Sr ratios (0.704 to 0.705) similar to the values for island arc basalts. These results suggest low water-rock ratios during hydrothermal circulation. B concentrations and isotopic compositions in these fluids range from 1.0 to 2.6μM and 13 to 20‰, respectively. These data match with other vent fluids from island arc settings in the Western Pacific and plot in a B versus δ11B diagram on a two-component mixing line between seawater and island arc basalts [3]. Sr and Li isotopic composition of white smoker and acid-sulfate fluids overlap generally with the isotopic ratios for the black smoker fluids. However, in some fluids Sr isotope ratios are up to 0.709 near seawater composition suggesting higher water-rock ratios during water-rock interaction. B concentrations and isotope ratios in the white smoker and acid-sulfate fluids range from 0.6 to 2.2μM and 9 to 16‰, respectively which are lower compared with the values of black smoker fluids. In addition, these fluids do not fit on the mixing line between seawater and island arc basalt, and define another mixing trend in a B versus δ11B diagram. To explain this contradictory trend, a third mixing endmember is required that shifts B concentrations and δ11B to lower values. A possible mixing endmember is B volatized from magmatic gases. This endmember seems to be reasonable because it only influences B, whereas Li and Sr stay unaffected. [1] Reeves et al. (2011) GCA 75, 1088-1123 [2] Seewald et al. (2015) GCA 163, 178-199 [3] Yamaoka et al. (2015) CG 392, 9-18

The oxygen isotope composition of Karoo and Etendeka picrites: High δ18O mantle or crustal contamination?

NASA Astrophysics Data System (ADS)

Harris, Chris; le Roux, Petrus; Cochrane, Ryan; Martin, Laure; Duncan, Andrew R.; Marsh, Julian S.; le Roex, Anton P.; Class, Cornelia

2015-07-01

Oxygen isotope compositions of Karoo and Etendeka large igneous province (LIP) picrites and picrite basalts are presented to constrain the effects of crustal contamination versus mantle source variation. Olivine and orthopyroxene phenocrysts from lavas and dykes (Mg# 64-80) from the Tuli and Mwenezi (Nuanetsi) regions of the ca 180 Ma Karoo LIP have δ18O values that range from 6.0 to 6.7 ‰. They appear to have crystallized from magmas having δ18O values about 1-1.5 ‰ higher than expected in an entirely mantle-derived magma. Olivines from picrite and picrite basalt dykes from the ca 135 Ma Etendeka LIP of Namibia and Karoo-age picrite dykes from Dronning Maud Land, Antarctica, do not have such elevated δ18O values. A range of δ18O values from 4.9 to 6.0 ‰, and good correlations between δ18O value and Sr, Nd and Pb isotope ratios for the Etendeka picrites are consistent with previously proposed models of crustal contamination. Explanations for the high δ18O values in Tuli/Mwenezi picrites are limited to (1) alteration, (2) crustal contamination, and (3) derivation from mantle with an abnormally high δ18O. Previously, a variety of models that range from crustal contamination to derivation from the `enriched' mantle lithosphere have been suggested to explain high concentrations of incompatible elements such as K, and average ɛNd and ɛSr values of -8 and +16 in Mwenezi (Nuanetsi) picrites. However, the primitive character of the magmas (Mg# 73), combined with the lack of correlation between δ18O values and radiogenic isotopic compositions, MgO content, or Mg# is inconsistent with crustal contamination. Thus, an 18O-enriched mantle source having high incompatible trace element concentration and enriched radiogenic isotope composition is indicated. High δ18O values are accompanied by negative Nb and Ta anomalies, consistent with the involvement of the mantle lithosphere, whereas the high δ18O themselves are consistent with an eclogitic source. Magma δ18O values about 1 ‰ higher than expected for mantle-derived magma are also a feature of the Bushveld mafic and ultramafic magmas, and the possibility exists that a long-lived 18O-enriched mantle source has existed beneath southern Africa. A mixed eclogite peridotite source could have developed by emplacement of oceanic lithosphere into the cratonic keel during Archaean subduction.

Changing sources of strontium to soils and ecosystems across the Hawaiian Islands

USGS Publications Warehouse

Chadwick, O.A.; Derry, L.A.; Bern, C.R.; Vitousek, P.M.

2009-01-01

Strontium isotope ratios assist ecosystem scientists in constraining the sources of alkaline earth elements, but their interpretation can be difficult because of complexities in mineral weathering and in the geographical and environmental controls on elemental additions and losses. Hawaii is a "natural laboratory" where a number of important biogeochemical variables have either limited ranges or vary in systematic ways, providing a unique opportunity to understand the impact of time, climate, and atmospheric inputs on the evolution of base cation sources to ecosystems. There are three major sources of strontium (Sr) to these ecosystems, each with distinct isotopic compositions: basalt lava, Asian dust, and rainfall. We present Sr isotope and concentration data on both bulk soil digests and NH4Ac extracts from soil profiles covering a wide range of environments and substrate ages. Bulk soil material from dry climates and/or young substrate ages with > 80????g g- 1 Sr retain basalt-like Sr isotopic signatures, whereas those with Sr concentrations < 80????g g- 1 can have isotope signatures that range from basalt-like values to the more radiogenic values associated with continental dust. Although both dust accumulation and lava weathering are time- and rainfall-dependent, the overall concentration of Sr drops with increasing leaching even as quartz and mica derived from continental dust sources increase to > 40% by mass. At elevated dust levels, lava-derived Sr is low and dust-derived Sr is the dominant control of 87Sr/86Sr in bulk soils; however, 87Sr/86Sr of NH4Ac-extractable Sr largely reflects atmospheric deposition of marine aerosol in these situations. Overall, whole-soil Sr isotope values are controlled by complex interactions between Sr provided by lava weathering but partially lost by leaching, and Sr provided by dust but held in more resistant minerals. The isotopic composition of NH4Ac-extractable Sr and of the biota is controlled by lava weathering and rainfall contribution of Sr with only minor contributions from radiogenic dust sources. ?? 2009 Elsevier B.V.

Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures

DOE PAGES

Loyd, S. J.; Sample, J.; Tripati, R. E.; ...

2016-07-22

Here, methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ~0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixingmore » of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings.« less

Stable iron isotopes and microbial mediation in red pigmentation of the Rosso Ammonitico (mid-late Jurassic, Verona area, Italy).

PubMed

Préat, Alain R; de Jong, Jeroen T M; Mamet, Bernard L; Mattielli, Nadine

2008-08-01

The iron (Fe) isotopic composition of 17 Jurassic limestones from the Rosso Ammonitico of Verona (Italy) have been analyzed by Multiple-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). Such analysis allowed for the recognition of a clear iron isotopic fractionation (mean -0.8 per thousand, ranging between -1.52 to -0.06 per thousand) on a millimeter-centimeter scale between the red and grey facies of the studied formation. After gentle acid leaching, measurements of the Fe isotopic compositions gave delta(56)Fe values that were systematically lower in the red facies residues (median: -0.84 per thousand, range: -1.46 to +0.26 per thousand) compared to the grey facies residues (median: -0.08 per thousand, range: -0.34 to +0.23 per thousand). In addition, the red facies residues were characterized by a lighter delta(56)Fe signal relative to their corresponding leachates. These Fe isotopic fractionations could be a sensitive fingerprint of a biotic process; systematic isotopic differences between the red and grey facies residues, which consist of hematite and X-ray amorphous iron hydroxides, respectively, are hypothesized to have resulted from the oxidizing activity of iron bacteria and fungi in the red facies. The grey Fe isotopic data match the Fe isotopic signature of the terrestrial baseline established for igneous rocks and low-C(org) clastic sedimentary rocks. The Fe isotopic compositions of the grey laminations are consistent with the influx of detrital iron minerals and lack of microbial redox processes at the water-interface during deposition. Total Fe concentration measurements were performed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) (confirmed by concentration estimations obtained by MC-ICP-MS analyses of microdrilled samples) on five samples, and resultant values range between 0.30% (mean) in the grey facies and 1.31% (mean) in the red facies. No correlation was observed between bulk Fe content and pigmentation or between bulk Fe content and Fe isotopic compositions. The rapid transformation of the original iron oxyhydroxides to hematite could have preserved the original isotopic composition if it had occurred at about the same temperature. This paper supports the use of Fe isotopes as sensitive tracers of biological activities recorded in old sedimentary sequences that contain microfossils of iron bacteria and fungi. However, a careful interpretation of the iron isotopic fractionation in terms of biotic versus abiotic processes requires supporting data or direct observations to characterize the biological, (geo)chemical, or physical context in relation to the geologic setting. This will become even more pertinent when Fe isotopic studies are expanded to the interplanetary realm.

Fabrication of 12% {sup 240}Pu calorimetry standards

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, S.M.; Hildner, S.; Gutierrez, D.

1995-08-01

Throughout the DOE complex, laboratories are performing calorimetric assays on items containing high burnup plutonium. These materials contain higher isotopic range and higher wattages than materials previously encountered in vault holdings. Currently, measurement control standards have been limited to utilizing 6% {sup 240}Pu standards. The lower isotopic and wattage value standards do not complement the measurement of the higher burnup material. Participants of the Calorimetry Exchange (CALEX) Program have identified the need for new calorimetric assay standards with a higher wattage and isotopic range. This paper describes the fabrication and verification measurements of the new CALEX standard containing 12% {supmore » 240}Pu oxide with a wattage of about 6 to 8 watts.« less

C isotope fractionation during heterotrophic activity driven carbonate precipitation

NASA Astrophysics Data System (ADS)

Balci, Nurgul; Demirel, Cansu

2016-04-01

Stable carbon isotopic fractionation during carbonate precipitation induced by environmentally enriched heterotrophic halophilic microorganims was experimentally investigated under various salinity (% 4.5, %8, %15) conditions at 30 °C. Halophilic heterotrophic microorganims were enriched from a hypersaline Lake Acigöl located in SW Turkey (Balci et al.,2015) and later used for the precipitation experiments (solid and liquid medium). The carbonate precipitates had relatively high δ13C values (-4.3 to -16.9 ‰) compared to the δ13C values of the organic compounds that ranged from -27.5 to -25.4 ‰. At salinity of 4.5 % δ13C values of carbonate ranged from -4.9 ‰ to -10.9 ‰ with a 13C-enrichment factor of +20 to +16 ‰ higher than the δ13C values of the associated DOC (-27.5) . At salinity 8 % δ13C values of carbonate ranged from -16.3 ‰ to -11.7 ‰ with a 13C-enrichment factor of+11.3 to+15.9 ‰ higher than the δ13C values of the associated DOC. The respected values for 15 % salinity ranged from -12.3 ‰ to -9.7 ‰ with a 13C-enrichment factor of +15.2 to+16.8 ‰ higher than the δ13C values of the associated DOC. The carbonate precipitates produced in the solid medium are more enriched in 13C relative to liquid culture experiments. These results suggest that the carbon in the solid was derived from both the bacterial oxidation of organic compounds in the medium and from the atmospheric CO2. A solid medium used in the experiments may have suppressed convective and advective mass transport favouring diffusion-controlled system. This determination suggests that the rate and equilibration of CO2 exchange with the atmosphere is the major control on C isotope composition of carbonate minerals precipitated in the experiments. Key words: Lake Acıgöl, halophilic bacteria, carbonate biomineralization, C isotopes References Nurgul Balci, Meryem Menekşe, Nevin Gül Karagüler, M. Şeref Sönmez,Patrick Meister 2015.Reproducing authigenic carbonate precipitation inthe hypersaline Lake Acıgöl (Turkey) with microbial cultures. Geomicrobiology Journal DOI: 10.1080/01490451.2015.1099763. TUBITAK (The Scientific and Technological Research Council of Turkey) Grant to N. BALCI (113Y464).

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

USGS Publications Warehouse

Coplen, T.B.; Hopple, J.A.; Böhlke, J.K.; Peiser, H.S.; Rieder, S.E.; Krouse, H.R.; Rosman, K.J.R.; Ding, T.; Vocke, R.D.; Revesz, K.M.; Lamberty, A.; Taylor, P.; De Bievre, P.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Mechanisms for Magnesium Isotopic Variation in Low-grade Metamorphosed Mudrocks from the British Caledonides

NASA Astrophysics Data System (ADS)

Wang, S.; Teng, F.; Rudnick, R. L.; Li, S.

2013-12-01

We report Mg isotope ratios for low-grade metamorphosed mudrocks from three lower Paleozoic basins (northern Lake District, southern Lake District and Southern Uplands) in the British Caledonides, previously analyzed for Li, Sr and Nd isotopes (Qiu et al., 2009, GCA), with the aim of understanding the behavior of Mg isotopes during subgreenschist-facies metamorphism, and the processes responsible for Mg isotopic variations in mudrocks. The δ26Mg of mudrocks varies greatly from -0.754 to 0.251, and displays no correlation with metamorphic grade, which ranges from diagenesis to subgreenschist-facies. Thus, low-grade metamorphism has no apparent influence on Mg isotopes. The variations instead likely reflect their provenance and mineralogical components. Samples from the northern Lake District, previously interpreted to derive from ancient, heavily weathered crust have δ26Mg (-0.06 × 0.11 on average) significantly heavier than that of average upper continental crust (~ -0.22), which is consistent with this interpretation. By contrast, mudrocks from the southern Lake District are characterized by low δ26Mg values (from -0.754 to -0.093) that require the presences of an unusually light component. The previously inferred provenance for these rocks of upper continental crust and arc volcanic detritus cannot explain such light isotopic compositions. Rather, such values may reflect the presence of carbonate in these samples and uptake of sea water Mg. Samples from the Southern Uplands, which contain the heaviest Li isotopes and ɛNd, and contain volcanic arc detritus, display Mg isotopic compositions divergent from a 'normal' mantle value (-0.25) towards both high and low δ26Mg values (from -0.742 to -0.079). Therefore, these mudrocks must contain a minimum of three end-members: mature felsic upper continental crust, arc lavas and carbonate. Given that limited Mg isotope fractionation occurs during low-grade metamorphism, Mg isotopes could be a potential tracer of provenance as well as carbonate involvement for fine-grained terrigenous sediments.

Food-web structure and trophodynamics of mesopelagic-suprabenthic bathyal macrofauna of the Algerian Basin based on stable isotopes of carbon and nitrogen

NASA Astrophysics Data System (ADS)

Fanelli, E.; Cartes, J. E.; Rumolo, P.; Sprovieri, M.

2009-09-01

The trophodynamics of mesopelagic (macrozooplankton/micronekton) and benthic boundary layer (suprabenthos=hyperbenthos) faunas from the Algerian Basin were characterized on a seasonal scale through stable carbon and nitrogen isotopic analyses of a total of 34 species and two broad taxa (Copepoda and Cumacea). This is the first study simultaneously focused on trophodynamics of deep-sea zooplankton and suprabenthos. Samples were collected southeast of Mallorca (Algerian Basin, Western Mediterranean), on the continental slope close to Cabrera Archipelago, at 650-780 m depths, ca. bi-monthly between August 2003 and June 2004. Mean δ 13C values of suprabenthos ranged from -21.1‰ ( Munnopsurus atlanticus) to -16.7‰ ( Cyclaspis longicaudata). Values of δ 15N ranged from 2.8‰ ( Lepechinella manco) to 9.9‰ (larvae of Gnathia sp.). The stable isotope ratios of suprabenthic fauna displayed a continuum of values, confirming a wide spectrum of feeding guilds (from filter feeders/surface deposit feeders to predators). According to the available information on diets for suprabenthic species, the highest annual mean δ 15N values were found for the hematophagous isopod Gnathia sp. parasite on fish (represented by Praniza larvae) and carnivorous amphipods (e.g. Rhachotropis spp., Nicippe tumida) consuming copepods, and the lowest δ 15N values were found for two cumaceans ( Cyclaspis longicaudata and Platysympus typicus) feeding on detritus. Assuming a 15N-enrichment factor of 2.5‰ and deposit feeders as baseline, we found three trophic levels in suprabenthic food webs. δ 13C ranges were particularly wide among deposit feeders (ranging from -21.8% to -17.3‰) and omnivores (from -20.5% to -18.8‰), suggesting exploitation of particulate organic matter (POM) of different characteristics. Our isotopic analyses revealed lower ranges of δ 13C and δ 15N for macrozooplankton/micronekton, compared with suprabenthos. δ 13C values of zooplankton taxa ranged from -21.1‰ (the hyperiid Phrosina semilunata) to -19.9‰ (the decapod Pasiphaea multidentata), while δ 15N values ranged from 3.9‰ ( P. semilunata) to 7.5‰ ( P. multidentata). Among zooplankton, more enriched δ 15N values were found among carnivores (e.g. the fish Cyclothone spp. and Pasiphaea multidentata) preying on copepods, hyperiids, euphausiids and small fish. The lowest δ 15N values were found for hyperiids that feed on the mucus nets of salps (e.g. Vibilia armata). After contrasting isotope analysis with dietary data, we conclude there were two trophic levels among zooplankton/micronekton. Strong correlation between the mean annual δ 15N and δ 13C values was found for zooplankton ( R2=0.7), but not for suprabenthos, which suggests a single source of carbon for plankton. We found a general seasonal trend for δ 13C enrichment from late autumn (November) to late winter-spring (February-April) for both suprabenthos and zooplankton. The δ 13C enrichment in February-April was correlated in zooplankton with higher surface chlorophyll a concentration 1 month before sampling. As evidenced by δ 13C-δ 15N correlations, the response of zooplankton to the peak of surface primary production was almost immediate (an increase of δ 13C-δ 15N correlations in February), and stronger than for suprabenthos. The response among suprabenthos was weak, with slight increase in δ 13C-δ 15N relationships in April-June.

Carbon isotope ratios of selected volatiles in Citrus sinensis and in orange-flavoured food.

PubMed

Schipilliti, Luisa; Bonaccorsi, Ivana; Cotroneo, Antonella; Dugo, Paola; Mondello, Luigi

2015-11-01

Twenty genuine samples of industrially cold-pressed sweet orange essential oils, were analysed by gas chromatography-combustion-isotope ratio mass spectrometry to determine the values of the carbon isotope ratios (δ(13)C(VPDB)) of selected volatiles and assess the corresponding range of authenticity. Successively, four commercial orange-flavoured products were analysed under identical conditions to evaluate the authenticity of the orange flavour. The samples were extracted by solid-phase microextraction under optimised conditions. The evaluation was performed by using an internal standard procedure to neglect the contribution due to the original environment to the isotopic abundance of (13)C. The composition of the volatile fraction of the essential oils and of the flavoured products was determined by gas chromatography coupled to mass spectrometry with linear retention indices, and by gas chromatography with a flame ionisation detector. The δ(13)C(VPDB) values of seven secondary metabolites determined here were successfully used to characterise genuine orange essential oil. These values were used to evaluate the quality of orange-flavoured products, revealing the presence of compounds of different origin, not compatible with the values of genuine orange secondary metabolites. This study provides the range of authenticity of δ(13)C(VPDB) of seven different secondary metabolites in sweet orange genuine essential oil, useful for evaluating the genuineness of orange flavour. In accord with a previous study on different essential oils, the values determined here can be successfully applied for the evaluation of a large number of flavoured food stuffs and correlated with their origins. © 2014 Society of Chemical Industry.

Climate in the Great Lakes Region between 14,000 and 4000 years ago from isotopic composition of conifer wood

Treesearch

Steven W. Leavitt; Irina P. Panyushkina; Todd Lange; Alex Wiedenhoeft; Li Cheng; R. Douglas Hunter; John Hughes; Frank Pranschke; Allan F. Schneider; Joseph Moran; Ron Stieglitz

2006-01-01

The isotopic composition of ancient wood has the potential to provide information about past environments. We analyzed the ä13C, ä18O, and ä2H of cellulose of conifer trees from several cross-sections at each of 9 sites around the Great Lakes region ranging from ~4000 to 14,000 cal BP. Isotopic values of Picea, Pinus, and Thuja species seem inter-changeable for ä18O...

Sr-Nd-Hf isotopic fingerprinting of transatlantic dust derived from North Africa

NASA Astrophysics Data System (ADS)

Zhao, Wancang; Balsam, William; Williams, Earle; Long, Xiaoyong; Ji, Junfeng

2018-03-01

Long-range transport of African dust plays an important role in understanding dust-climate relationships including dust source areas, dust pathways and associated atmospheric and/or oceanic processes. Clay-sized Sr-Nd-Hf isotopic compositions can be used as geochemical fingerprints to constrain dust provenance and the pathways of long-range transported mineral dust. We investigated the clay-sized Sr-Nd-Hf isotopic composition of surface samples along four transects bordering the Sahara Desert. The transects are from Mali, Niger/Benin/Togo, Egypt and Morocco. Our results show that the Mali transect on the West African Craton (WAC) produces lower εNd (εNd-mean = -16.38) and εHf (εHf-mean = -9.59) values than the other three transects. The Egyptian transect exhibits the lowest 87Sr/86Sr ratios (87Sr/86Srmean = 0.709842), the highest εHf (εHf-mean = -0.34) and εNd values of the four transects. Comparison of the clay-sized Sr-Nd-Hf isotopic values from our North African samples to transatlantic African dust collected in Barbados demonstrates that the dust's provenance is primarily the western Sahel and Sahara as well as the central Sahel. Summer emission dust is derived mainly from the western Sahel and Sahara regions. The source of transatlantic dust in spring and autumn is more varied than in the summer and includes dust not only from western areas, but also south central areas. Comparison of the Sr-Nd-Hf isotopic fingerprints between the source and sink of transatlantic dust also suggests that a northwestward shift in dust source occurs from the winter, through the spring and into the summer. The isotopic data we develop here provide another tool for discriminating changes in dust archives resulting from paleoenvironmental evolution of source regions.

Isotopic composition of recent shark teeth as a proxy for environmental conditions

NASA Astrophysics Data System (ADS)

Vennemann, T. W.; Hegner, E.; Cliff, G.; Benz, G. W.

2001-05-01

The O, C, and Sr isotope compositions of teeth from ten species, belonging to five families, and three orders of sharks were measured to determine the influence of habitat, diet, and possible species-specific fractionation effects on the isotopic composition of biogenic phosphate from fish. The sharks were recently caught in subtropical waters off the KwaZulu-Natal (KZN) coast of South Africa, as well as from cold waters in Prince William Sound (PWS), Alaska, and Victor Bay (VB), Nunavut, Canada. δ 18O values of tooth phosphate (δ 18O P) range from 20.9 to 23.5‰ for the KZN sharks. For most species the range in measured δ 18O P values is about 0.6‰, but it may be as high as 1.1‰ for different teeth from a single shark. Dentine and enameloid within individual teeth have no apparent differences in δ 18O P values. The δ 18O P values of the KZN shark teeth reflect the typical habitat of the studied species, primarily the thermal structure of the water column off KZN at depths between 20 and 280 m. The δ 18O P values of teeth from different Greenland sharks from VB and Pacific sleeper sharks from PWS are very homogeneous, averaging 25.8 and 24.7‰, respectively. These values appear to be in equilibrium with deep (>500 m) ocean waters in each case at temperatures of about -0.3°C or less. There is little discernable evidence for species-specific fractionation effects for the oxygen isotope composition of phosphate in the studied marine fish. The oxygen isotope composition of carbonate in apatite averages about 9.1‰ higher than corresponding δ 18O P values, in agreement with equilibrium fractionation between carbonate and phosphate, but with a large variance (1σ = ±1.5‰). δ 18O C values also vary by up to 1‰ between enameloid and dentine within single teeth, but in a non-systematic way. Differences in δ 13C values between carbonate in enameloid and dentine is also large (up to 8‰) but the δ 13C values vary systematically. Enameloid is always enriched in 13C compared to dentine and the 13C content increases with developmental stage of the teeth. δ 13C values measured for enameloid (1.6 to 4.8‰) appear to approach equilibrium with dissolved inorganic carbon in seawater. In contrast, δ 13C values for dentine range from -6.4 to -2.3‰ for KZN sharks, and -9.0 to -10.8‰ for the cold-water sleeper sharks, and are compatible with a predominantly dietary carbon source. The 87Sr/ 86Sr ratios of teeth from KZN sharks as well as those from PWS and VB are uniform, averaging 0.709167. Sr content varies from 1270 to 2100 ppm, a range that is similar to that in well preserved fossilized teeth. Seawater Sr is thus clearly incorporated in vivo. Concentrations of Sm and Nd are in the ppb range and contrast the ppm range in fossilized teeth, indicating a postmortem incorporation of rare earth elements in apatite of the teeth.

Controls on the iron isotopic composition of global arc magmas

NASA Astrophysics Data System (ADS)

Foden, John; Sossi, Paolo A.; Nebel, Oliver

2018-07-01

We determined the iron isotope composition of 130 mafic lavas from 15 arcs worldwide with the hypothesis that the results would reflect the relatively high oxidation state of arc magmas. Although this expectation was not realized, this Fe isotope data set reveals important insights into the geodynamic controls and style of the melting regimes in the sub-arc mantle. Samples are from oceanic arcs from the circum-Pacific, the Indonesian Sunda-Banda islands, Scotia and the Lesser Antilles as well as from the eastern Pacific Cascades. Their mean δ57Fe value is +0.075 ± 0.05‰, significantly lighter than MORB (+0.15 ± 0.03‰). Western Pacific arcs extend to very light δ57Fe (Kamchatka = -0.11 ± 0.04‰). This is contrary to expectation, because Fe isotope fractionation factors (Sossi et al., 2016, 2012) and the incompatibility of ferric versus ferrous iron during mantle melting, predict that melts of more oxidized sources will be enriched in heavy Fe isotopes. Subducted oxidation capacity flux may correlate with hydrous fluid release from the slab. If so, a positive correlation between each arc's thermal parameter (ϕ) and δ57Fe is predicted. On the contrary, the sampled arcs mostly contribute to a negative array with the ϕ value. High ϕ arcs, largely in the western Pacific, have primary magmas with lower δ57Fe values than the low ϕ, eastern Pacific arcs. Arcs with MORB-like Sr-, Nd- and Pb-isotopes, show a large range of δ57Fe from heavy MORB-like values (Scotia or the Cascades) to very light values (Kamchatka, Tonga). Although all basalts with light δ57Fe values have MORB-like Pb-, Nd- and Sr-isotope ratios some, particularly those from eastern Indonesia, have heavier δ57Fe and higher Pb- and Sr- and lower Nd-isotope ratios reflecting sediment contamination of the mantle wedge. Because basalts with MORB-like radiogenic isotopes range all the way from heavy to light δ57Fe values this trend is process-, not source composition-driven. Neither the slab-derived influx of fluids with light iron or sediment-derived melts with heavier iron can drive the iron isotopic shifts. The trend to light iron isotopes is partly the result of repeated, hydrous flux-driven, fO2-buffered, melting of initially normal-DMM-like mantle. However the most negative δ57Fe must also reflect re-melting of sources that have experienced prior diffusive (disequilibrium) stripping of heavy Fe isotopes due to rapid melt extraction and metasomatism. Data from intra-arc to back-arc rifts in the western Pacific show that these arc signatures are rapidly dispersed by influx of DMM or OIB mantle once intra- and back-arc rifting and slab rollback gains momentum. We suggest that the characteristic light arc signatures only form when the source is lodged under arcs where sub-arc mantle undergoes corner flow forming an isolated roll. This process of heavy iron depletion is most efficient in the high ϕ arcs of the western Pacific and least prevalent in the low ϕ arcs of the eastern Pacific where δ57Fe values are MORB-like. This implies that there is a fundamental change in character of sub-arc mantle melting between east and west Pacific, percolative and fluid fluxed in the west and diapiric and decompressional in the east.

The chlorine isotope composition of the moon and implications for an anhydrous mantle.

PubMed

Sharp, Z D; Shearer, C K; McKeegan, K D; Barnes, J D; Wang, Y Q

2010-08-27

Arguably, the most striking geochemical distinction between Earth and the Moon has been the virtual lack of water (hydrogen) in the latter. This conclusion was recently challenged on the basis of geochemical data from lunar materials that suggest that the Moon's water content might be far higher than previously believed. We measured the chlorine isotope composition of Apollo basalts and glasses and found that the range of isotopic values [from -1 to +24 per mil (per thousand) versus standard mean ocean chloride] is 25 times the range for Earth. The huge isotopic spread is explained by volatilization of metal halides during basalt eruption--a process that could only occur if the Moon had hydrogen concentrations lower than those of Earth by a factor of approximately 10(4) to 10(5), implying that the lunar interior is essentially anhydrous.

Vanadium isotope heterogeneity of the early solar system

NASA Astrophysics Data System (ADS)

Nielsen, S.; Auro, M. E. E.; Magna, T.; Davis, D. M.; Mezger, K.; Sarafian, A. R.

2017-12-01

Vanadium (V) has two isotopes with masses 50 and 51 that have 51V/50V ratio of 410. This ratio can be modified by production of 50V through cosmic irradiation, heterogeneous distribution of anomalous nucleosynthetic material and stable isotope fractionation. Due to the existence of only two V isotopes in nature, these latter processes cannot directly be distinguished from irradiation processes. Previous data has suggested that Earth is characterized by 51V/50V that is significantly different to that of meteorites. These data are difficult to reconcile with a singular process that caused the V isotope variation in the early Solar System. Here we present new V isotope data for a large range of meteorites in order to investigate the ultimate origin of V isotope variation in the early Solar System. We find limited and non-systematic 51V/50V variation of 0.3‰ for 25 martian meteorites (depleted/intermediate/enriched shergottites, nakhlites, and chassignite and orthopyroxenite ALH 84001), which suggests that igneous processes on Mars did not induce significant V isotope shifts. Our best estimate for V isotope composition of the bulk silicate Mars can thus be approximated by the mean value of the entire Martian meteorite suite. This value is significantly lighter ( 0.4‰) than that measured for pristine terrestrial rocks. In contrast, meteorites from the HED parent body reveal significant 51V/50V variation that may be linked to magmatic processes such as fractional crystallization of Vestan magma ocean. The two data sets illustrate that several processes are likely to explain the V isotope variation found in meteorites. We will also present new V isotope data for carbonaceous and ordinary chondrites and put them in the context of the values found for Earth, Mars and the HED parent body.

Boron isotope systematics of tourmaline formation in the Sullivan Pb-Zn-Ag deposit, British Columbia, Canada

USGS Publications Warehouse

Jiang, S.-Y.; Palmer, M.R.; Slack, J.F.; Shaw, D.R.

1999-01-01

We report here the results of 54 boron isotope analyses of tourmaline associated with the giant Sullivan Pb-Zn-Ag deposit in southeastern British Columbia, Canada. The ??11B values range from -11.1 to -2.9???, which is almost as great as the range found worldwide in tourmalines from 33 massive sulfide deposits and tourmalinites in dominantly clastic metasedimentary terranes. The major control on the overall ??11B values of the Sullivan tourmalinites is the boron source. Potential controls over the large range of the data also include: (1) differences in formation temperatures of the tourmalinites, (2) different stages of tourmaline formation, (3) variations in the proportions of dissolved boron incorporated into the tourmaline (Rayleigh fractionation), (4) seawater entrainment, and (5) post-depositional metamorphism. The boron isotope data at Sullivan are consistent with boron derivation from leaching of footwall clastic sediments. However, the great abundance of tourmaline in the Sullivan deposit suggests that the local clastic sediments were not the sole source of boron, and we argue that non-marine evaporites, buried deep below the orebody, are the most viable source of this additional boron. It is likely that some of the variation in tourmaline ??11B values reflect mixing of boron from these two sources. Comparison of the potential effects of these controls with geologic and other geochemical evidence suggests that major causes for the wide range of ??11B values measured at Sullivan are seawater entrainment and Rayleigh fractionation, although in places, post-depositional alteration and thermal metamorphism were important in determining ??11B values of some of the recrystallized tourmalinites.

Lipid Extraction and the Fugacity of Stable Isotope Values

NASA Astrophysics Data System (ADS)

Padula, V.; Causey, D.; Wolf, N.; Welker, J. M.

2013-12-01

Stable isotope analysis of blood, feathers, and other tissues are often used to infer migration patterns, diet composition and trophic status of seabirds. Tissues contain variable amounts of lipids that are depleted in the heavy carbon isotope (13C) and may introduce a bias in these values. There is evidence that lipid extraction may affect other stable isotope ratios, such as δ15N. Consequently, correction factors need to be applied to appropriately interpret δ13C and δ15N values for individual species and tissue type. In this study, we collected seven species of seabirds from the Near Islands, the western most group of islands in the Aleutian Island archipelago. We sampled kidney, liver, heart and muscle samples from each bird and after freeze drying, individual tissue samples were divided into two subsamples. We left one subsample unaltered and extracted lipids from the other subsample using a 2:1 chloroform-methanol solution. We found that the change in δ13C values after lipid extraction (Δδ13C) varied widely among categories (eg., species, tissue type) from 0 - 4 ‰, while Δδ15N values ranged from 0 to 2‰. Notably, within category variation was nonsignificant and the Δδ values were linear against the covariant C:N ratio of the isotopic data, which allows us to use arithmetic corrections for categorical values. Our data strongly indicate that the effects of lipid extraction on stable isotopic values, while linear within category, vary widely by species, tissue, geographic area, year of collection, and isotope. Fugacity is usually employed as a thermodynamic quantity related to the chemical potential or activity that characterizes the escaping tendency from a phase (eg. Mackay & Paterson 1982). Here we use fugacity in the earlier, broader sense of fleeting, transitory, or instable states (eg., S. Johnson 1751), and its measure may be approximated by the higher order variance of Δδ13C and Δδ15N among data categories. Clearly, understanding the nature of variation and the physiological processes responsible for stable isotope values from biological tissues are critical for their interpretation. Change in carbon and nitrogen stable isotopes (ΔδC13, Δδ15N) after lipid extraction for Tufted Puffins (Fratercula cirrhata) collected July 2010 at Attu Island, Aleutians.

Tritium effect in peroxidation of ehtanol by liver catalase.

PubMed Central

Damgaard, S E

1977-01-01

1. Simultaneous determination of the rate of appearance of 3H in water from [(1R)-1-3H1] ethanol and the rate of acetaldehyde formation in the presence of rat or ox liver catalase under conditions of steady-state generation of H2O2 allowed calculation of the 3H isotope effect. The mean value of 2.52 obtained for rat liver catalase at 37 degrees C and pH 6.3-7.7 was independent of both ethanol concentration and the rate of H2O2 generation over a wide range. At 25 degrees C a slightly lower mean value of 2.40 was obtained with the ox liver catalase. 2. Neither the product, acetaldehyde, nor 4-methylpyrazole influenced the two rates measured in the assay. 3. Relating the value obtained for the 3H isotope effect to a known value for the 2H isotope effect strongly supports the view that both values are close to the true isotope effect with the respective substituted compounds on the rate constant in the catalytic step involving scission of the C-H bond. 4. The constancy of the isotope effect under various conditions makes it possible to use it for interpretations in vivo. 5. It was established that beta-D-galactose dehydrogenase exhibits B-specificity towards the nicotinamide ring in NAD. PMID:22327

Isotopic evidence for closed-system anatexis at midcrustal levels: An example from the Acadian Appalachians of New England

NASA Astrophysics Data System (ADS)

Lathrop, Alison S.; Blum, Joel D.; Chamberlain, C. Page

1994-05-01

We have investigated the Sr and O isotope systematics of granitoid and metasedimentary samples from the Central Main Terrane (CMT) of New England. Granitoid samples were taken from interior and contact zones within the Acadian-aged (approximately 410 m.y.), synmetamorphic and syntectonic Kinsman Quartz Monzonite (KQM), which is a member of the New Hampshire Plutonic Series. Metasedimentary samples were taken from Silurian and Devonian formations hosting the KQM. Initial Sr isotope ratios (Sr(sub i) and delta O-18 values for the KQM range from 0.70799 to 0.71246 and 7.6% to 12.9%, respectively, and Sr(sub i) and delta O-18 values of the metasedimentary rocks range from 0.70770 to 0.75008 and 6.2% to 14.1%, respectively. We observe a linear and slightly positive correlation between Sr(sub i) and delta O-18 for interior KQM samples that can be duplicated by a mixing curve calculated for metasedimentary endmembers, whereas the Sr(sub i) and delta O-18 values of contact KQM samples cluster near the Sr(sub i) and delta O-18 values of the metasedimentary rocks with which they are in contact. Mixing calculations provide no evidence for a measurable primitive mantle component in either interior or contact KQM samples, and we conclude that the Sr-O isotopic composition of the KQM is most likely a reflection of isotopic heterogeneities inherited from a complex package of midcrustal metasedimentary source rocks. We propose that the KQM is the product of midcrustal partial melting that was initiated due to excess thermal energy from the decay of anomalously high concentrations of heat-producing elements in Silurian source rocks within the CMT. Because we see no isotopic evidence for a lower-crustal or mantle component in the KQM, we suggest that midcrustal anatexis may have occurred as a closed-system process, requiring no accompanying mantle-derived magma or above normal mantle heat flow.

Moss stable isotopes (carbon-13, oxygen-18) and testate amoebae reflect environmental inputs and microclimate along a latitudinal gradient on the Antarctic Peninsula.

PubMed

Royles, Jessica; Amesbury, Matthew J; Roland, Thomas P; Jones, Glyn D; Convey, Peter; Griffiths, Howard; Hodgson, Dominic A; Charman, Dan J

2016-07-01

The stable isotope compositions of moss tissue water (δ(2)H and δ(18)O) and cellulose (δ(13)C and δ(18)O), and testate amoebae populations were sampled from 61 contemporary surface samples along a 600-km latitudinal gradient of the Antarctic Peninsula (AP) to provide a spatial record of environmental change. The isotopic composition of moss tissue water represented an annually integrated precipitation signal with the expected isotopic depletion with increasing latitude. There was a weak, but significant, relationship between cellulose δ(18)O and latitude, with predicted source water inputs isotopically enriched compared to measured precipitation. Cellulose δ(13)C values were dependent on moss species and water content, and may reflect site exposure to strong winds. Testate amoebae assemblages were characterised by low concentrations and taxonomic diversity, with Corythion dubium and Microcorycia radiata types the most cosmopolitan taxa. The similarity between the intra- and inter-site ranges measured in all proxies suggests that microclimate and micro-topographical conditions around the moss surface were important determinants of proxy values. Isotope and testate amoebae analyses have proven value as palaeoclimatic, temporal proxies of climate change, whereas this study demonstrates that variations in isotopic and amoeboid proxies between microsites can be beyond the bounds of the current spatial variability in AP climate.

Magnesium Isotope Composition of the Altered Upper Oceanic Crust at ODP Holes 504B and 896A, Costa Rica Rift

NASA Astrophysics Data System (ADS)

Beaumais, A.; Teagle, D. A. H.; James, R. H.; Pearce, C. R.; Milton, J. A.; Alt, J.; Coggon, R. M.

2017-12-01

Alteration of the oceanic crust is thought to be the principal sink of Mg in seawater, but the effect of this process on the Mg isotope (δ26Mg) composition of the oceans remains unclear. Here we present the first measurements of Mg isotopes in altered oceanic crust from ODP Holes 504B and 896A, located in 5.9 Ma crust, 200 km south of the intermediate spreading rate Costa Rica Rift. Hole 504B penetrates: (i) A volcanic section, consisting of partially altered basalt that was open to seawater circulation under oxic-suboxic conditions at temperatures of <150°C. (ii) A transition zone, characterized by mixing between upwelling hydrothermal fluid and seawater between 100 and 350°C. (iii) A sheeted dike complex consisting of diabase partially altered to greenschist facies minerals. Hole 896A penetrates volcanic rocks altered at low temperature (<100 °C) under oxic-suboxic conditions. The overall range in δ26Mg values is -0.53 to -0.01‰; significantly greater than the range observed in unaltered mid-ocean ridge basalts (MORB: -0.25 ± 0.06‰ [1]). δ26Mg values decrease with depth in the volcanic sections of both Holes 504B and 896A. The highest δ26Mg values are found in saponite-bearing basalts at the top of the volcanic sections of both holes, and are attributed to the preferential incorporation of heavy Mg isotopes into secondary clays (Mg-saponite). Lower δ26Mg values recorded in the deeper part of the volcanic section may be a result of fluid-rock interaction with isotopically lighter evolved seawater. The transition zone is characterised by MORB-like to relatively high δ26Mg values in the chlorite-smectite bearing basalts. The sheeted dike complex yields a narrow range of MORB-like δ26Mg values suggesting that limited fractionation occurs during high-temperature alteration and that the fluids have very low Mg concentrations. Low temperature fluid-rock interactions modify the Mg isotopic composition of the upper part of the oceanic crust. Therefore, this process could potentially play a role in balancing the δ26Mg of (i) the seawater via lateral fluid flow through oceanic crust off-axis ridge flanks, and (ii) the mantle via recycling of oceanic lithosphere at subduction zones. [1] Teng et al., (2010) GCA 74, 4150-4166.

Use of stable sulfur isotopes to identify sources of sulfate in Rocky Mountain snowpacks

USGS Publications Warehouse

Mast, M.A.; Turk, J.T.; Ingersoll, G.P.; Clow, D.W.; Kester, C.L.

2001-01-01

Stable sulfur isotope ratios and major ions in bulk snowpack samples were monitored at a network of 52 high-elevation sites along and near the Continental Divide from 1993 to 1999. This information was collected to better define atmospheric deposition to remote areas of the Rocky Mountains and to help identify the major source regions of sulfate in winter deposition. Average annual ??34S values at individual sites ranged from + 4.0 to + 8.2??? and standard deviations ranged from 0.4 to 1.6???. The chemical composition of all samples was extremely dilute and slightly acidic; average sulfate concentrations ranged from 2.4 to 12.2 ??eql-1 and pH ranged from 4.82 to 5.70. The range of ??34S values measured in this study indicated that snowpack sulfur in the Rocky Mountains is primarily derived from anthropogenic sources. A nearly linear relation between ??34S and latitude was observed for sites in New Mexico, Colorado, and southern Wyoming, which indicates that snowpack sulfate in the southern part of the network was derived from two isotopically distinct source regions. Because the major point sources of SO2 in the region are coal-fired powerplants, this pattern may reflect variations in the isotopic composition of coals burned by the plants. The geographic pattern in ??34S for sites farther to the north in Wyoming and Montana was much less distinct, perhaps rflecting the paucity of major point sources of SO2 in the northern part of the network.

A protocol to correct for intra- and interspecific variation in tail hair growth to align isotope signatures of segmentally cut tail hair to a common time line.

PubMed

Burnik Šturm, Martina; Pukazhenthi, Budhan; Reed, Dolores; Ganbaatar, Oyunsaikhan; Sušnik, Stane; Haymerle, Agnes; Voigt, Christian C; Kaczensky, Petra

2015-06-15

In recent years, segmental stable isotope analysis of hair has been a focus of research in animal dietary ecology and migration. To correctly assign tail hair segments to seasons or even Julian dates, information on tail hair growth rates is a key parameter, but is lacking for most species. We (a) reviewed the literature on tail hair growth rates in mammals; b) made own measurements of three captive equid species; (c) measured δ(2)H, δ(13)C and δ(15)N values in sequentially cut tail hairs of three sympatric, free-ranging equids from the Mongolian Gobi, using isotope ratio mass spectrometry (IRMS); and (d) collected environmental background data on seasonal variation by measuring δ(2)H values in precipitation by IRMS and by compiling pasture productivity measured by remote sensing via the normalized difference vegetation index (NDVI). Tail hair growth rates showed significant inter- and intra-specific variation making temporal alignment problematic. In the Mongolian Gobi, high seasonal variation of δ(2)H values in precipitation results in winter lows and summer highs of δ(2)H values of available water sources. In water-dependent equids, this seasonality is reflected in the isotope signatures of sequentially cut tails hairs. In regions which are subject to strong seasonal patterns we suggest identifying key isotopes which show strong seasonal variation in the environment and can be expected to be reflected in the animal tissue. The known interval between the maxima and minima of these isotope values can then be used to correctly temporally align the segmental stable isotope signature for each individual animal. © 2015 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd.

A protocol to correct for intra- and interspecific variation in tail hair growth to align isotope signatures of segmentally cut tail hair to a common time line

PubMed Central

Burnik Šturm, Martina; Pukazhenthi, Budhan; Reed, Dolores; Ganbaatar, Oyunsaikhan; Sušnik, Stane; Haymerle, Agnes; Voigt, Christian C; Kaczensky, Petra

2015-01-01

Rationale In recent years, segmental stable isotope analysis of hair has been a focus of research in animal dietary ecology and migration. To correctly assign tail hair segments to seasons or even Julian dates, information on tail hair growth rates is a key parameter, but is lacking for most species. Methods We (a) reviewed the literature on tail hair growth rates in mammals; b) made own measurements of three captive equid species; (c) measured δ2H, δ13C and δ15N values in sequentially cut tail hairs of three sympatric, free-ranging equids from the Mongolian Gobi, using isotope ratio mass spectrometry (IRMS); and (d) collected environmental background data on seasonal variation by measuring δ2H values in precipitation by IRMS and by compiling pasture productivity measured by remote sensing via the normalized difference vegetation index (NDVI). Results Tail hair growth rates showed significant inter- and intra-specific variation making temporal alignment problematic. In the Mongolian Gobi, high seasonal variation of δ2H values in precipitation results in winter lows and summer highs of δ2H values of available water sources. In water-dependent equids, this seasonality is reflected in the isotope signatures of sequentially cut tails hairs. Conclusions In regions which are subject to strong seasonal patterns we suggest identifying key isotopes which show strong seasonal variation in the environment and can be expected to be reflected in the animal tissue. The known interval between the maxima and minima of these isotope values can then be used to correctly temporally align the segmental stable isotope signature for each individual animal. © 2015 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd. PMID:26044272

Isotopic Ordering in Atmospheric O2 as a Tracer of Ozone Photochemistry and the Tropical Atmosphere

NASA Technical Reports Server (NTRS)

Yeung, Laurence Y.; Murray, Lee T.; Ash, Jeanine L.; Young, Edward D.; Boering, Kristie A.; Atlas, Elliot L.; Schauffler, Sue M.; Lueb, Richard A.; Langenfelds, Ray L.; Krummel, Paul B.;

Oxygen isotope variations in phosphate of deer bones

NASA Astrophysics Data System (ADS)

Luz, Boaz; Cormie, Allison B.; Schwarcz, Henry P.

1990-06-01

Variations of δ 18O of bone phosphate (δ p) of white tailed deer were studied in samples with wide geographic distribution in North America. Bones from the same locality have similar isotopic values, and the difference between specimens (0.4‰) is not large relative to the measurement error (0.3‰). The total range of δ p values is about 12‰. This indicates that deer use water from a relatively small area, and thus their δ p indicates local environmental conditions. Multiple regression analysis between oxygen isotope composition of deer bone phosphate and of local relative humidity and precipitation (δ w) yields a high correlation coefficient (0.95). This correlation is significantly better than the linear correlation (0.81) between δ p and δ w of precipitation alone. Thus δ p depends on both isotopic composition of precipitation and on relative humidity. This is because deer obtain most of their water from leaves, the isotopic composition of which is partly controlled by relative humidity through evaporation/transpiration.

Stable isotope signatures and trophic-step fractionation factors of fish tissues collected as non-lethal surrogates of dorsal muscle.

PubMed

Busst, Georgina M A; Bašić, Tea; Britton, J Robert

2015-08-30

Dorsal white muscle is the standard tissue analysed in fish trophic studies using stable isotope analyses. As muscle is usually collected destructively, fin tissues and scales are often used as non-lethal surrogates; we examined the utility of scales and fin tissue as muscle surrogates. The muscle, fin and scale δ(15) N and δ(13) C values from 10 cyprinid fish species determined with an elemental analyser coupled with an isotope ratio mass spectrometer were compared. The fish comprised (1) samples from the wild, and (2) samples from tank aquaria, using six species held for 120 days and fed a single food resource. Relationships between muscle, fin and scale isotope ratios were examined for each species and for the entire dataset, with the efficacy of four methods of predicting muscle isotope ratios from fin and scale values being tested. The fractionation factors between the three tissues of the laboratory fishes and their food resource were then calculated and applied to Bayesian mixing models to assess their effect on fish diet predictions. The isotopic data of the three tissues per species were distinct, but were significantly related, enabling estimations of muscle values from the two surrogates. Species-specific equations provided the least erroneous corrections of scale and fin isotope ratios (errors < 0.6‰). The fractionation factors for δ(15) N values were in the range obtained for other species, but were often higher for δ(13) C values. Their application to data from two fish populations in the mixing models resulted in significant alterations in diet predictions. Scales and fin tissue are strong surrogates of dorsal muscle in food web studies as they can provide estimates of muscle values within an acceptable level of error when species-specific methods are used. Their derived fractionation factors can also be applied to models predicting fish diet composition from δ(15) N and δ(13) C values. Copyright © 2015 John Wiley & Sons, Ltd.

Methylmercury degradation and exposure pathways in streams and wetlands impacted by historical mining.

PubMed

Donovan, Patrick M; Blum, Joel D; Singer, Michael Bliss; Marvin-DiPasquale, Mark; Tsui, Martin T K

2016-10-15

Monomethyl mercury (MMHg) and total mercury (THg) concentrations and Hg stable isotope ratios (δ(202)Hg and Δ(199)Hg) were measured in sediment and aquatic organisms from Cache Creek (California Coast Range) and Yolo Bypass (Sacramento Valley). Cache Creek sediment had a large range in THg (87 to 3870ng/g) and δ(202)Hg (-1.69 to -0.20‰) reflecting the heterogeneity of Hg mining sources in sediment. The δ(202)Hg of Yolo Bypass wetland sediment suggests a mixture of high and low THg sediment sources. Relationships between %MMHg (the percent ratio of MMHg to THg) and Hg isotope values (δ(202)Hg and Δ(199)Hg) in fish and macroinvertebrates were used to identify and estimate the isotopic composition of MMHg. Deviation from linear relationships was found between %MMHg and Hg isotope values, which is indicative of the bioaccumulation of isotopically distinct pools of MMHg. The isotopic composition of pre-photodegraded MMHg (i.e., subtracting fractionation from photochemical reactions) was estimated and contrasting relationships were observed between the estimated δ(202)Hg of pre-photodegraded MMHg and sediment IHg. Cache Creek had mass dependent fractionation (MDF; δ(202)Hg) of at least -0.4‰ whereas Yolo Bypass had MDF of +0.2 to +0.5‰. This result supports the hypothesis that Hg isotope fractionation between IHg and MMHg observed in rivers (-MDF) is unique compared to +MDF observed in non-flowing water environments such as wetlands, lakes, and the coastal ocean. Copyright © 2016 Elsevier B.V. All rights reserved.

Methylmercury degradation and exposure pathways in streams and wetlands impacted by historical mining

USGS Publications Warehouse

Donovan, Patrick M.; Blum, Joel D.; Singer, Michael B.; Marvin-DiPasquale, Mark C.; Tsui, Martin T.K.

2016-01-01

Monomethyl mercury (MMHg) and total mercury (THg) concentrations and Hg stable isotope ratios (δ202Hg and Δ199Hg) were measured in sediment and aquatic organisms from Cache Creek (California Coast Range) and Yolo Bypass (Sacramento Valley). Cache Creek sediment had a large range in THg (87 to 3870 ng/g) and δ202Hg (−1.69 to −0.20‰) reflecting the heterogeneity of Hg mining sources in sediment. The δ202Hg of Yolo Bypass wetland sediment suggests a mixture of high and low THg sediment sources. Relationships between %MMHg (the percent ratio of MMHg to THg) and Hg isotope values (δ202Hg and Δ199Hg) in fish and macroinvertebrates were used to identify and estimate the isotopic composition of MMHg. Deviation from linear relationships was found between %MMHg and Hg isotope values, which is indicative of the bioaccumulation of isotopically distinct pools of MMHg. The isotopic composition of pre-photodegraded MMHg (i.e., subtracting fractionation from photochemical reactions) was estimated and contrasting relationships were observed between the estimated δ202Hg of pre-photodegraded MMHg and sediment IHg. Cache Creek had mass dependent fractionation (MDF; δ202Hg) of at least −0.4‰ whereas Yolo Bypass had MDF of +0.2 to +0.5‰. This result supports the hypothesis that Hg isotope fractionation between IHg and MMHg observed in rivers (−MDF) is unique compared to +MDF observed in non-flowing water environments such as wetlands, lakes, and the coastal ocean.

The stable carbon isotope ratios in benthic food webs of the gulf of Calvi, Corsica

NASA Astrophysics Data System (ADS)

Dauby, Patrick

1989-02-01

The Gulf of Calvi, Corsica, presents a wide diversity of biocoenoses, amongst which the seagrass Posidonia meadow is prevalent. More than 100 plant, animal and sediment samples from various biotopes were analysed for their stable carbon isotope ratios, to assess carbon flows within the food chains. Marine plants display a wide range of δ 13C values, from -6 to -32‰ but with three relatively well distinct peaks for Posidonia, brown algae and phytoplankton (-9, -19 and -23‰, respectively), which are the main carbon sources. The range of isotopic values of animals is narrower, from -14 to -24‰, suggesting that they feed mainly on algae and plankton. Computations based on simple equations show the proportion of each carbon source in the diet of the animals. Posidonia, notwithstanding their important biomass, appear to be a minor food source; this is possibly because of the transfer of their dead leaves, towards the shorelines, in winter.

Carbon and nitrogen isotopic compositions of particulate organic matter and biogeochemical processes in the eutrophic Danshuei Estuary in northern Taiwan.

PubMed

Liu, Kon-Kee; Kao, Shuh-Ji; Wen, Liang-Saw; Chen, Kuan-Lun

2007-08-15

The Danshuei Estuary is distinctive for the relatively short residence time (1-2 d) of its estuarine water and the very high concentration of ammonia, which is the dominant species of dissolved inorganic nitrogen in the estuary, except near the river mouth. These characteristics make the dynamics of nitrogen cycling distinctively different from previously studied estuaries and result in unusual isotopic compositions of particulate nitrogen (PN). The delta(15)N(PN) values ranging from -16.4 per thousand to 3.8 per thousand lie in the lower end of nitrogen isotopic compositions (-16.4 to +18.7 per thousand) of suspended particulate matter observed in estuaries, while the delta(13)C values of particulate organic carbon (POC) and the C/N (organic carbon to nitrogen) ratios showed rather normal ranges from -25.5 per thousand to -19.0 per thousand and from 6.0 to 11.3, respectively. There were three major types of particulate organic matter (POM) in the estuary: natural terrigenous materials consisting mainly of soils and bedrock-derived sediments, anthropogenic wastes and autochthonous materials from the aquatic system. During the typhoon induced flood period in August 2000, the flux-weighted mean of delta(13)C(POC) values was -24.4 per thousand, that of delta(15)N(PN) values was +2.3 per thousand and that of C/N ratio was 9.3. During non-typhoon periods, the concentration-weighted mean was -23.6 per thousand for delta(13)C(POC), -2.6 per thousand for delta(15)N(PN) and 8.0 for C/N ratio. From the distribution of delta(15)N(PN) values of highly polluted estuarine waters, we identified the waste-dominated samples and calculated their mean properties: delta(13)C(POC) value of -23.6+/-0.7 per thousand, delta(15)N(PN) value of -3.0+/-0.1 per thousand and C/N ratio of 8.0+/-1.4. Using a three end-member mixing model based on delta(15)N(PN) values and C/N ratios, we calculated contributions of the three major allochthonous sources of POC, namely, wastes, soils and bedrock-derived sediments, to the estuary. Their contributions were, respectively, 83%, 12% and 5% under non-typhoon conditions, and 9%, 63% and 28% under typhoon conditions. The autochthonous POM had the most varied isotopic compositions, encompassing the full ranges of delta(13)C(POC) (-25.5 to -19.1 per thousand), delta(15)N(PN) (-16.4-3.8 per thousand) and C/N ratio (6.0-11.3). The heavy end of the carbon isotopic composition reflected the typical marine condition and the lower end the estuarine condition, which probably had elevated concentrations of dissolved inorganic carbon with low delta(13)C values due to input from decomposition of organic matter. The lack of isotopically heavy PN, as found in larger estuaries, was attributed to isotopically light starting materials, namely, anthropogenic wastes, the slow phytoplankton growth within the estuary and the rather short residence time; the latter two factors made (15)N enrichment during ammonia consumption very limited. The most isotopically light PN likely originated from phytoplankton incorporating (15)N-depleted nitrate near the river mouth, where ammonia inhibition of nitrate uptake probably stopped.

Isotope fractionation during the anaerobic consumption of acetate by methanogenic and sulfate-reducing microorganisms

NASA Astrophysics Data System (ADS)

Gövert, D.; Conrad, R.

2009-04-01

During the anaerobic degradation of organic matter in anoxic sediments and soils acetate is the most important substrate for the final step in production of CO2 and/or CH4. Sulfate-reducing bacteria (SRB) and methane-producing archaea both compete for the available acetate. Knowledge about the fractionation of 13C/12C of acetate carbon by these microbial groups is still limited. Therefore, we determined carbon isotope fractionation in different cultures of acetate-utilizing SRB (Desulfobacter postgatei, D. hydrogenophilus, Desulfobacca acetoxidans) and methanogens (Methanosarcina barkeri, M. acetivorans). Including literature values (e.g., Methanosaeta concilii), isotopic enrichment factors (epsilon) ranged between -35 and +2 permil, possibly involving equilibrium isotope effects besides kinetic isotope effects. The values of epsilon were dependent on the acetate-catabolic pathway of the particular microorganism, the methyl or carboxyl position of acetate, and the relative availability or limitation of the substrate acetate. Patterns of isotope fractionation in anoxic lake sediments and rice field soil seem to reflect the characteristics of the microorganisms actively involved in acetate catabolism. Hence, it might be possible using environmental isotopic information to determine the type of microbial metabolism converting acetate to CO2 and/or CH4.

Carbon, hydrogen, and oxygen isotope studies of the regional metamorphic complex at Naxos, Greece

USGS Publications Warehouse

Rye, R.O.; Schuiling, R.D.; Rye, D.M.; Jansen, J.B.H.

1976-01-01

At Naxos, Greece, a migmatite dome is surrounded by schists and marbles of decreasing metamorphic grade. Sillimanite, kyanite, biotite, chlorite, and glaucophane zones are recognized at successively greater distances from the migmatite dome. Quartz-muscovite and quartz-biotite oxygen isotope and mineralogie temperatures range from 350 to 700??C. The metamorphic complex can be divided into multiple schist-rich (including migmatites) and marblerich zones. The ??18O values of silicate minerals in migmatite and schist units and quartz segregations in the schist-rich zones decrease with increase in metamorphic grades. The calculated ??18OH2O values of the metamorphic fluids in the schist-rich zones decrease from about 15??? in the lower grades to an average of about 8.5??? in the migmatite. The ??D values of OH-minerals (muscovite, biotite, chlorite, and glaucophane) in the schist-rich zones also decrease with increase in grade. The calculated ??DH2O values for the metamorphic fluid decrease from -5??? in the glaucophane zone to an average of about -70??? in the migmatite. The ??D values of water in fluid inclusions in quartz segregations in the higher grade rocks are consistent with this trend. The??18O values of silicate minerals and quartz segregations in marble-rich zones are usually very large and were controlled by exchange with the adjacent marbles. The ??D values of the OH minerals in some marble-rich zones may reflect the value of water contained in the rocks prior to metamorphism. Detailed data on 20 marble units show systematic variations of ??18O values which depend upon metamorphic grade. Below the 540??C isograd very steep ??18O gradients at the margins and large ??18O values in the interior of the marbles indicate that oxygen isotope exchange with the adjacent schist units was usually limited to the margins of the marbles with more exchange occurring in the stratigraphic bottom than in the top margins. Above the 540??C isograd lower ??18O values occur in the interior of the marble units reflecting a greater degree of recrystallization and the occurrence of Ca-Mg-silicates. Almost all the ??13C values of the marbles are in the range of unaltered marine limestones. Nevertheless, the ??13C values of most marble units show a general correlation with ??18O values. The CO2 H2O mole ratio of fluid inclusions in quartz segregations range from 0.01 to 2. The??13C values of the CO2 range from -8.0 to 3.6??? and indicate that at some localities CO2 in the metamorphic fluid was not in carbon isotopic equilibrium with the marbles. ?? 1976.

Molecular distributions and stable carbon isotopic compositions of dicarboxylic acids and related compounds in aerosols from Sapporo, Japan: Implications for photochemical aging during long-range atmospheric transport

NASA Astrophysics Data System (ADS)

Aggarwal, Shankar G.; Kawamura, Kimitaka

2008-07-01

Molecular and stable carbon isotopic (δ13C value) compositions of dicarboxylic acids, ketoacids, and dicarbonyls in aerosol samples (i.e., total suspended particles) collected in Sapporo, northern Japan during spring and summer were determined to better understand the photochemical aging of organic aerosols during long-range transport from East Asia and Siberia. Their molecular distributions were characterized by the predominance of oxalic acid (C2) followed by malonic (C3) or occasionally succinic (C4) acids. Concentrations of total diacids ranged from 106-787 ng m-3 with ketoacids (13-81 ng m-3) and dicarbonyls (2.6-28 ng m-3) being less abundant. Water-soluble organic carbon (WSOC) comprised 23-69% of aerosol organic carbon (OC). OC to elemental carbon (EC) ratios were high (3.6-19, mean: 8.7). The ratios of C3/C4 and WSOC/OC did not show significant diurnal changes, suggesting that the Sapporo aerosols were not seriously affected by local photochemical processes and instead they were already aged. δ13C values of the dominant diacids (C2 - C4) ranged from -14.0 to -25.3‰. Largest δ13C values (-14.0 to -22.4‰, mean: -18.8‰) were obtained for C2, whereas smallest values (-25.1 to -31.4‰, mean: -28.1‰) were for azelaic acid (C9). In general, δ13C values of C2 - C4 diacids became less negative with aerosol aging (i.e., WSOC/OC), presumably due to isotopic fractionation during photochemical degradation of diacids. By comparing the δ13C values of diacids in the Sapporo aerosols with different air mass source regions, we suggest that although initial δ13C values of diacids depend on their precursor sources, the enrichment in 13C can be ascribed to aerosol photochemical aging.

Isotopic and chemical evidence concerning the genesis and contamination of basaltic and rhyolitic magma beneath the Yellowstone Plateau Volcanic Field

USGS Publications Warehouse

Hildreth, W.; Halliday, A.N.; Christiansen, R.L.

1991-01-01

Since 2.2 Ma, the Yellowstone Plateau Volcanic Field has produced ~6000 km3 of rhyolite tuffs and lavas in >60 separate eruptions, as well as ~100 km3 of tholeiitic basalt from >50 vents peripheral to the silicic focus. Intermediate eruptive products are absent. Early postcollapse rhyolites show large shifts in Nd, Sr, Pb, and O isotopic composition caused by assimilation of roof rocks and hydrothermal brines during collapse and resurgence. Younger intracaldera rhyolite lavas record partial isotopic recovery toward precaldera ratios. Thirteen extracaldera rhyolites show none of these effects and have sources independent of the subcaldera magma system. Contributions from the Archaean crust have extreme values and wide ranges of Nd-, Sr, and Pb-isotope ratios, but Yellowstone rhyolites have moderate values and limited ranges. This requires their deep-crustal sources to have been pervasively hybridized by distributed intrusion of Cenozoic basalt, most of which was probably contemporaneous with the Pliocene and Quaternary volcanism. Most Yellowstone basalts had undergone cryptic clinopyroxene fractionation in the lower crust or crust-mantle transition zone and, having also ascended through or adjacent to crustal zones of silicic-magma generation, most underwent some crustal contamination. -from Authors

Limited fluid in carbonate-shale hosted thrust faults of the Rocky Mountain Fold-and-Thrust Belt (Sun River Canyon, Montana)

NASA Astrophysics Data System (ADS)

OBrien, V. J.; Kirschner, D. L.

2001-12-01

It is widely accepted that fluids play a fundamental role in the movement of thrust faults in foreland fold-and-thrust belts. We have begun a combined structure-geochemistry study of faults in the Rocky Mountain fold-and-thrust belt in order to provide more insight into the occurrence and role(s) of fluid in the deformation of thrust faults. We focus on faults exposed in the Sun River Canyon of Montana, an area that contains some of the best exposures of the Rocky Mountain fold-and-thrust belt in the U.S. Samples were collected from two well exposed thrusts in the Canyon -- the Diversion and French thrusts. Both faults have thrust Mississippian dolostones over Cretaceous shales. Displacement exceeds several kilometers. Numerous small-displacement, subsidiary faults characterize the deformation in the hanging wall carbonates. The footwall shales accommodated more penetrative deformation, resulting in well developed foliation and small-scale folds. Stable isotope data have been obtained from host rock samples and veins from these faults. The data delimit an arcuate trend in oxygen-carbon isotope space. Approximately 50 host rock carbonate samples from the hanging walls have carbon and oxygen isotope values ranging from +3 to 0 and 28 to 19 per mil, respectively. There is no apparent correlation between isotopic values and distance from thrust fault at either locality. Fifteen samples of fibrous slickensides on small-displacement faults in the hanging walls have similar carbon and lower oxygen isotope values (down to 16 per mil). And 15 veins that either post-date thrusting or are of indeterminate origin have carbon and oxygen isotope values down to -3 and12 per mil, respectively. The isotopic data collected during the initial stages of this project are similar to some results obtained several hundred kilometers north in the Front Ranges of the Canadian Rockies (Kirschner and Kennedy, JGR 2000) and in carbonate fold-thrust belts of the Swiss Helvetic Alps and Italian Apennines. These data are consistent with limited infiltration of fluid through fractures and minor faults into hanging walls of large-displacement thrust faults.

Spring response to precipitation events using δ(18)O and δ(2)H in the Tanour catchment, NW Jordan.

PubMed

Hamdan, Ibraheem; Wiegand, Bettina; Toll, Mathias; Sauter, Martin

2016-12-01

The Tanour spring is one of the several karst springs located in the northern part of Jordan. Water samples from the Tanour spring and precipitation were collected in the area of Ajloun in NW Jordan for the analysis of stable oxygen and hydrogen isotopes to evaluate the spring response to precipitation events. Rainwater and snow samples were collected from different elevations during winters of 2013-2014 and 2014-2015. In addition, spring samples were collected between December 2014 and March 2015. δ(18)O values in rainwater vary from -3.26 to -17.34 ‰ (average: -7.84 ± 3.23 ‰), while δ(2)H values range between -4.4 and -110.4 ‰ (average: -35.7 ± 25.0 ‰). Deuterium excess ranges from 17.8 to 34.1 ‰ (average: 27.1 ± 4.0 ‰). The Local Meteoric Water Line for the study area was calculated to be δ(2)H = 7.66*δ(18)O + 24.43 (R(2) = 0.98). Pre-event spring discharge showed variation in δ(18)O (range -6.29 to -7.17 ‰; average -6.58 ± 0.19 ‰) and δ(2)H values (range -28.8 to -32.7 ‰; average: -30.5 ± 1.0 ‰). In contrast, δ(18)O and δ(2)H rapidly changed to more negative values during rainfall and snowmelt events and persisted for several days before returning to background values. Spring water temperature, spring discharge, and turbidity followed the trend in isotopic composition during and after the precipitation events. The rapid change in the isotopic composition, spring discharge, water temperature, and turbidity in response to recharge events is related to fast water travel times and low storage capacity in the conduit system of the karst aquifer. Based on the changes in the isotopic composition of spring water after the precipitation events, the water travel time in the aquifer is in the order of 5-11 days.

In-Situ Oxygen Isotopic Composition of Tagish Lake: An Ungrouped Type 2 Carbonaceous Chondrite

NASA Technical Reports Server (NTRS)

Zolensky, Michael E.; Engrand, Cecile; Gounelle, Matthieu; Zolensky, Mike E.

2001-01-01

We have measured the oxygen isotopic composition of several components of Tagish Lake by ion microprobe. This meteorite constitutes the best preserved sample of C2 matter presently available for study. It presents two different lithologies (carbonate-poor and -rich) which have fairly comparable oxygen isotopic composition, with regard to both the primary or secondary minerals. For the olivine and pyroxene grains, their delta O-18 values range from - 10.5% to + 7.4% in the carbonate-poor lithology, with a mean Delta O-17 value of - 3.7 2.4%. In the carbonate-rich lithology, delta O-18 varies from - 7.9% to + 3.3%, and the mean Delta O-17 value is - 4.7 +/- 1.4%. Olivine inclusions (Fo(sub >99)) with extreme O-16-enrichment were found in both lithologies: delta O-18 = - 46.1 %, delta O-187= - 48.3% and delta O-18 = - 40.6%, delta O-17 = - 41.2% in the carbonate-rich lithology; delta O-18 = - 41.5%, delta O-17 = -43.4%0 in the carbonate-poor lithology. Anhydrous minerals in the carbonate-poor lithology are slightly more O-16-rich than in the carbonate-rich one. Four low-iron manganese-rich (LIME) olivine grains do not have an oxygen isotopic composition distinct from the other "normal" olivines. The phyllosilicate matrix presents the same range of oxygen isotopic compositions in both lithologies: delta O-18 from approximately 11 % to approximately 6%, with an average Delta. O-17 approximately 0%. Because the bulk Tagish Lake oxygen isotopic composition given by Brown et al. is on the high end of our matrix analyses, we assume that this "bulk Tagish Lake" composition probably only represents that of the carbonate-rich lithology. Calcium carbonates have delta O-18 values up to 35%, with Delta O-17 approximately 0.5%0. Magnetite grains present very high Delta O-17 values approximately + 3.4%0 +/- 1.2%. Given our analytical uncertainties and our limited carbonate data, the matrix and the carbonate seem to have formed in isotopic equilibrium. In that case, their large isotopic fractionation would argue for a low temperature (CM-like, T approximately 0 deg) formation. Magnetite probably formed during a separate event. Tagish Lake magnetite data is surprisingly compatible with that of R-chondrites and unequilibrated ordinary (LL3) chondrites. Our oxygen isotope data strongly supports the hypothesis of a single precursor for both lithologies. Drastic mineralogical changes between the two lithologies not being accompanied with isotopic fractionation seem compatible with the alteration model presented by Young et aI. Tagish Lake probably represents the first well preserved large sample of the C2 matter that dominates interplanetary matter since the formation of the solar system.

Paleoceanographic Inferences from Carbon and Nitrogen Isotopic Compositions of Cenomanian Black Shales from DSDP/ODP Sites 367, 530, 603, 641, 1257-1261, and 1276 in the Atlantic Ocean

NASA Astrophysics Data System (ADS)

Yum, J.; Meyers, P. A.; Bernasconi, S. M.; Arnaboldi, M.

2005-12-01

The mid-Cretaceous (Cenomanian- Turonian) was characterized as a peak global greenhouse period with highest sea level, highest CO2 concentration in atmosphere and low thermal gradients from the poles to the equator. The depositional environment of the organic-carbon-rich black shales that typify this period remains an open question. A total of 180 Cenomanian- Turonian core samples were selected from multiple ODP and DSDP sites in the Atlantic Ocean: 530 (Cape Basin), 603 (Hatteras Rise), 641 (Galicia Bank), 1257-1261 (Demerara Rise), 1276 (Newfoundland Basin). Total organic carbon and nitrogen concentrations and isotopic compositions were measured to investigate variations in the proto-Atlantic Ocean paleoceanographic conditions that contributed to the origin of the black shales for this period. These new data were combined with existing data from Sites 367 (Senegal Rise), 530, and 603. Both the black shales and the organic-carbon-poor background sediments (less than 1 percent) have carbon isotope values between -29 to -22 permil. The C/N ratios of the background sediments are low (less than 20) compared to those of the black shales (20-40). Nitrogen isotope values range from 0 to 4 permil in the background samples. All black shales have similarly low nitrogen isotope values that range between -4 to 0 permil. These exceptionally low values are inferred to reflect the productivity of blue green algae and cyanobacteria under strongly surface stratified oceanic conditions. Although carbon isotope and C/N values of black shales show almost similar patterns at each location, there are site-specific shifts in these data that could be related to the amount of continental run off and/or the effect of latitude. Our multi-site comparison suggests that specially stratified depositional environments that could produce and accumulate the abnormally high carbon concentrations in sediments occurred throughout the proto-Atlantic ocean during the mid-Cretaceous. However, regional factors affected the amount and origin of organic matter delivered to each location.

Comparisons of multiple isotope systems in the aragonitic shells of cultured Arctica islandica clams

NASA Astrophysics Data System (ADS)

Liu, Y. W.; Aciego, S.; Wanamaker, A. D.

2014-12-01

Previous work using oxygen and stable carbon isotopes from Arctica islandica shells has shown that this archive can provide information on past seawater temperatures, carbon cycling and ocean circulation. However, relatively less attention has been devoted to other "non-traditional" isotope systems within this proxy archive. In this study, we report the boron (δ11B) and strontium isotopic values (87Sr/86Sr and δ88/86Sr) from A. islandicashells collected and cultured from the Gulf of Maine. The long-lived ocean quahog, A. islandica was collected and cultured in the Gulf of Maine for 8 months. Our high-resolution δ11B records from the experiment show 5-7‰ of increase through the culture, with low values from January to May and higher values after May. The 87Sr/86Sr ratios from both tank water and shell samples suggest that the shell material reflects ambient ocean chemistry without interferences from terrestrial sources. Although It has been suggested that stable Sr isotopic ratios (δ88/86Sr) in biogenic carbonates are influenced by the temperature of the precipitating fluid, our nearly identical δ88/86Sr data do not support this hypothesis despite a 15 °C temperature change during the experiment. Based on the in-situ measurements of culture seawater temperature, salinity and pH, and two commonly used fractionation factors (α3-4) for corals and forams, we predicted the range in shell δ11B values for the experiment. Our boron results are at the extreme ends of the two prediction lines suggesting the potential usage of the bivalve shells as seawater pH indicator. However, the wider range in δ11B in this experiment than the predictions based on other carbonate organisms (only 2 to 3‰) suggests that a species-specific fractionation factor may be required. Recent work from an additional constant temperature experiment (10 and 15 °C) in the Gulf of Maine will allow us to further evaluate temperature influences and potential vital effects on the shell boron isotope values.

McCall Glacier record of Arctic climate change: Interpreting a northern Alaska ice core with regional water isotopes

NASA Astrophysics Data System (ADS)

Klein, E. S.; Nolan, M.; McConnell, J.; Sigl, M.; Cherry, J.; Young, J.; Welker, J. M.

2016-01-01

We explored modern precipitation and ice core isotope ratios to better understand both modern and paleo climate in the Arctic. Paleoclimate reconstructions require an understanding of how modern synoptic climate influences proxies used in those reconstructions, such as water isotopes. Therefore we measured periodic precipitation samples at Toolik Lake Field Station (Toolik) in the northern foothills of the Brooks Range in the Alaskan Arctic to determine δ18O and δ2H. We applied this multi-decadal local precipitation δ18O/temperature regression to ∼65 years of McCall Glacier (also in the Brooks Range) ice core isotope measurements and found an increase in reconstructed temperatures over the late-20th and early-21st centuries. We also show that the McCall Glacier δ18O isotope record is negatively correlated with the winter bidecadal North Pacific Index (NPI) climate oscillation. McCall Glacier deuterium excess (d-excess, δ2H - 8*δ18O) values display a bidecadal periodicity coherent with the NPI and suggest shifts from more southwestern Bering Sea moisture sources with less sea ice (lower d-excess values) to more northern Arctic Ocean moisture sources with more sea ice (higher d-excess values). Northern ice covered Arctic Ocean McCall Glacier moisture sources are associated with weak Aleutian Low (AL) circulation patterns and the southern moisture sources with strong AL patterns. Ice core d-excess values significantly decrease over the record, coincident with warmer temperatures and a significant reduction in Alaska sea ice concentration, which suggests that ice free northern ocean waters are increasingly serving as terrestrial precipitation moisture sources; a concept recently proposed by modeling studies and also present in Greenland ice core d-excess values during previous transitions to warm periods. This study also shows the efficacy and importance of using ice cores from Arctic valley glaciers in paleoclimate reconstructions.

Water vapor δ(2) H, δ(18) O and δ(17) O measurements using an off-axis integrated cavity output spectrometer - sensitivity to water vapor concentration, delta value and averaging-time.

PubMed

Tian, Chao; Wang, Lixin; Novick, Kimberly A

2016-10-15

High-precision analysis of atmospheric water vapor isotope compositions, especially δ(17) O values, can be used to improve our understanding of multiple hydrological and meteorological processes (e.g., differentiate equilibrium or kinetic fractionation). This study focused on assessing, for the first time, how the accuracy and precision of vapor δ(17) O laser spectroscopy measurements depend on vapor concentration, delta range, and averaging-time. A Triple Water Vapor Isotope Analyzer (T-WVIA) was used to evaluate the accuracy and precision of δ(2) H, δ(18) O and δ(17) O measurements. The sensitivity of accuracy and precision to water vapor concentration was evaluated using two international standards (GISP and SLAP2). The sensitivity of precision to delta value was evaluated using four working standards spanning a large delta range. The sensitivity of precision to averaging-time was assessed by measuring one standard continuously for 24 hours. Overall, the accuracy and precision of the δ(2) H, δ(18) O and δ(17) O measurements were high. Across all vapor concentrations, the accuracy of δ(2) H, δ(18) O and δ(17) O observations ranged from 0.10‰ to 1.84‰, 0.08‰ to 0.86‰ and 0.06‰ to 0.62‰, respectively, and the precision ranged from 0.099‰ to 0.430‰, 0.009‰ to 0.080‰ and 0.022‰ to 0.054‰, respectively. The accuracy and precision of all isotope measurements were sensitive to concentration, with the higher accuracy and precision generally observed under moderate vapor concentrations (i.e., 10000-15000 ppm) for all isotopes. The precision was also sensitive to the range of delta values, although the effect was not as large compared with the sensitivity to concentration. The precision was much less sensitive to averaging-time than the concentration and delta range effects. The accuracy and precision performance of the T-WVIA depend on concentration but depend less on the delta value and averaging-time. The instrument can simultaneously and continuously measure δ(2) H, δ(18) O and δ(17) O values in water vapor, opening a new window to better understand ecological, hydrological and meteorological processes. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Extreme isotopic variations in the upper mantle: evidence from Ronda

NASA Astrophysics Data System (ADS)

Reisberg, Laurie; Zindler, Alan

1986-12-01

The Ronda Ultramafic Complex in southern Spain represents a piece of the Earth's mantle which has been tectonically emplaced into the crust. Nd and Sr isotopic analyses are presented for leached, hand-picked Cr-diopside separates prepared from 15 rock and 18 river sediment samples from Ronda. These results demonstrate that within this small, contiguous body there exists the entire range of Nd isotopic compositions, and much of the range of Sr compositions, found in rocks derived from the sub-oceanic mantle. The sediment cpx samples show that the average isotopic composition of the massif becomes progressively less "depleted" moving from SW to NE along the long axis of the massif. The rock cpx samples document 143Nd/ 144Nd variations from 0.5129 to 0.5126 and 87Sr/ 86Sr variations from 0.7031 to 0.7039 within a uniform outcrop less than 10 m in extent. Thus, extreme isotopic fluctuations exist over a wide range of wavelengths. Sr and Nd isotopes are generally inversely correlated, forming a trend on a Nd-Sr diagram that sharply crosscuts that of the "mantle array". Many of the 143Nd/ 144Nd values, and all of the Sm/Nd values, from one section of the massif are lower than that SCV015SCV0 of the bulk earth, implying that this region existed, or was influenced by a component which existed, in a LREE-enriched environment for a significant period of time. Among the sediment cpxs there is a positive correlation between 143Nd/ 144Nd and 147Sm/ 144Nd. The rock cpx separates display considerably more scatter. A simple, single-stage differentiation event starting with a uniform mantle source cannot explain these results. At least one episode of mixing with a LREE-enriched component is required. If these results from Ronda are typical of the upper mantle, basalts with different isotopic compositions need not derive from spatially separated mantle sources.

The Austrian Network of Isotopes in Precipitation and Surface water: more than 50 years applications and interpretations of basic isotope-hydrological data for Central Europe

NASA Astrophysics Data System (ADS)

Wyhlidal, S.; Rank, D.; Kralik, M.

2017-12-01

Austria runs one of the longest-standing and most dense isotope precipitation collection networks worldwide, resulting in a unique isotope time series. Stable isotope variations in precipitation are a consequence of isotope effects accompanying each step of the water cycle. Therefore, stable isotope ratios of oxygen (18O/16O) and hydrogen (2H/1H) in precipitation provide important information about the origin and atmospheric transport of water vapour. The separation of a remote moisture source signals from local influences is thereby challenging. The amount of precipitation in Austria is highly influenced by the Alpine mountain range (400-3.000 mm/a). The amount of annual precipitation increases towards the mountain ranges. However, strong regional differences exist between the north and south of the Austrian Alps because the Alpine range functions as weather divide. The isotope time series of the stations of the Austrian precipitation network show significant but not uniform long-term trends. While the 10-year running mean of some mountain stations exhibit a highly significant increase in δ18O of about 1 ‰ since 1975, the change of δ18O at the valley stations is less pronounced. The increasing δ18O values can be correlated to an increase mean air temperature in the Alpine area and can be used as an additional indicator of climate change in this region. The differences in δ18O-values of sampling stations at similar altitudes can be explained by the origin of the air moisture. An Atlantic influence causes lower δ18O-values than sources from the Mediterranean. This can be explained by the different distances to the sea. Deuterium excess is a second-order isotopic parameter which is often interpreted as a tracer of the evaporation conditions of water vapor at the moisture source in terms of relative humidity, wind speed, and sea surface temperature, but can also be modified by local influences, such as below-cloud evaporation and equilibrium fractionation under very cold conditions. The long-term variations of d-excess in precipitation at selected stations show a significant difference in the behavior of the d-excess at mountain and valley stations. Deuterium excess and δ18O will be used to explore climate effects on precipitation signatures observed and elicit how they can be integrated in to global climate models.

Diagenetic alteration of biogenic silica oxygen isotope values: implications for use as a paleoenvironmental proxy

NASA Astrophysics Data System (ADS)

Dodd, J. P.; Abbott, T.; Scherer, R. P.

2016-12-01

Oxygen isotope (δ18O) values of biogenic silica have enormous potential as paleoenvironmental proxies in marine and non-marine environments. Isotopic exchange and phase changes (opal-A to opal-CT) can overprint the initial δ18O values, but these diagenetic processes can also provide additional paleoenvironmental information. The timing and magnitude of isotopic exchange reactions are difficult to constrain in natural environments; however, experimental results of diatom aging indicate that changes in the δ18O values of the biogenic silca occur coincident with dehydroxylation of the silica prior to opal-CT formation. Diagenetic alteration of biogenic silica dramatically changes our interpretation of silica isotope data from sedimentary records. For example, diatom δ18O values from a Pliocene ( 4.68 to 3.44 Ma) age marine sediment core (AND-1B) from the Ross Sea, Antarctica range from +28 to +36‰. The silica-water fractionation relationship for marine diatoms of Juillet-Leclerc and Labeyrie (1987) and a standard marine δ18O water value of 0‰ results in unrealistic sea surface temperatures of >20°C. Conversely, if water temperatures of 0 to 10°C are used, the resulting water δ18O values range from -8 to -16‰. A plausible alternate scenario is that the diatom δ18O values are recording sediment pore-water conditions. Pore waters in the AND-2A core had δ18O values of -11‰, possibly as a result cryogenic brine formation (Frank et al., 2010). These low δ18O values are in close agreement with our calculated δ18O water values. Despite diagenetic overprinting of the diatom δ18O values, there is still good agreement between the measured diatom δ18O values and the stacked benthic δ18O record (Lisiecki and Raymo, 2005); biogenic silica δ18O values in the AND-1B core likely record the composition of shallow sediment pore water and cryogenic brine formation. The agreement between our δ18O record and the benthic stack δ18O values suggests that brine formation in the early Pliocene Ross Sea may be driven by regional and global scale climate processes. Sedimentary diatoms most likely represent a combination of growth and diagenetic environments, and the δ18O value of diagenetic water needs to be addressed when reconstructing paleoceanographic and paleoenvironmental conditions.

Os isotope systematics in ocean island basalts

NASA Astrophysics Data System (ADS)

Reisberg, Laurie; Zindler, Alan; Marcantonio, Franco; White, William; Wyman, Derek; Weaver, Barry

1993-12-01

New Re-Os isotopic results for Os-poor basalts from St. Helena, the Comores, Samoa, Pitcairn and Kerguelen dramatically expand the known range of initial Os-186/Os-187 ratios in Ocean Island Basalts (OIBs) to values as high as 1.7. In contrast to the Os isotopic uniformity of Os-rich basalts from the HIMU islands of Tubuai and Mangaia found by Hauri and Hart, our values for St. Helena span most of the known range of Os isotopic variability in oceanic basalts (initial O-187/Os-186 ranges from 1.2 to 1.7). Generation of such radiogenic Os in the mantle requires melting of source materials that contain large proportions of recycled oceanic crust. The very low Os concentrations of most of the basalts analyzed here, however, leave them susceptible to modification via interaction with materials containing radiogenic Os in the near-surface environment. Thus the high Os-186/Os-187 ratios may result from assimilation of radiogenic Os-rich marine sediments, such as Mn oxides, within the volcanic piles traversed by these magmas en route to the surface. Furthermore, the Os isotopic signatures of Os-rich, olivine-laden OIBs may reflect the accumulation of lithospheric olivine, rather than simply their mantle source characteristics. The extent to which these processes alter the view of the mantle obtained via study of Re-Os systematics in oceanic basalts is uncertain. These effects must be quantified before Re-Os systematics in OIBs can be used with confidence to investigate the nature of mantle heterogeneity and its causes.

Continental sedimentary processes decouple Nd and Hf isotopes

NASA Astrophysics Data System (ADS)

Garçon, Marion; Chauvel, Catherine; France-Lanord, Christian; Huyghe, Pascale; Lavé, Jérôme

2013-11-01

The neodymium and hafnium isotopic compositions of most crustal and mantle rocks correlate to form the "Terrestrial Array". However, it is now well established that whereas coarse detrital sediments follow this trend, fine-grained oceanic sediments have high Hf ratios relative to their Nd isotopic ratios. It remains uncertain whether this "decoupling" of the two isotopic systems only occurs in the oceanic environment or if it is induced by sedimentary processes in continental settings. In this study, the hafnium and neodymium isotopic compositions of sediments in large rivers is expressly used to constrain the behavior of the two isotopic systems during erosion and sediment transport from continent to ocean. We report major and trace element concentrations together with Nd and Hf isotopic compositions of bedloads, suspended loads and river banks from the Ganges River and its tributaries draining the Himalayan Range i.e. the Karnali, the Narayani, the Kosi and the Marsyandi Rivers. The sample set includes sediments sampled within the Himalayan Range in Nepal, at the Himalayan mountain front, and also downstream on the floodplain and at the outflow of the Ganges in Bangladesh. Results show that hydrodynamic sorting of minerals explains the entire Hf isotopic range, i.e. more than 10 εHf units, observed in the river sediments but does not affect the Nd isotopic composition. Bedloads and bank sediments have systematically lower εHf values than suspended loads sampled at the same location. Coarse-grained sediments lie below or on the Terrestrial Array in an εHf vs. εNd diagram. In contrast, fine-grained sediments, including most of the suspended loads, deviate from the Terrestrial Array toward higher εHf relative to their εNd, as is the case for oceanic terrigenous clays. The observed Nd-Hf decoupling is explained by mineralogical sorting processes that enrich bottom sediments in coarse and dense minerals, including unradiogenic zircons, while surface sediments are enriched in fine material with radiogenic Hf signatures. The data also show that Nd-Hf isotopic decoupling increases with sediment transport in the floodplain to reach its maximum at the river mouth. This implies that the Nd-Hf isotopic decoupling observed in worldwide oceanic clays and river sediments is likely to have the same origin. Finally, we estimated the Nd-Hf isotopic composition of the present-day mantle if oceanic sediments had never been subducted and conclude that the addition of oceanic sediments with their anomalous Nd-Hf isotopic compositions has slowly shifted the composition of the Earth's mantle towards more radiogenic Hf values through time.

Isotopic studies of the late Archean plutonic rocks of the Wind River Range, Wyoming.

USGS Publications Warehouse

Stuckless, J.S.; Hedge, C.E.; Worl, R.G.; Simmons, K.R.; Nkomo, I.T.; Wenner, D.B.

1985-01-01

Two late Archaean intrusive events were documented in the Wind River Range by isotopic studies of the Rb-Sr and U-Th-Pb systems in whole-rock samples and the U-Pb systematics for zircon. An age of approx 2630(20) m.y. for the Louis Lake batholith and apparent ages of 2504(40) to 2575(50) m.y. for the Bear Ears pluton were obtained. Post-magmatic hydrothermal events approximately Tertiary in age, lowered delta 18O values and disturbed parent-daughter relationships in most of the isotopic systems investigated. The two intrusive units apparently were derived from different protoliths. Initial isotopic ratios and petrochemistry for the Louis Lake batholith are consistent with an early Archaean trondhjemitic to tonalitic source. The protolith for the Bear Ears pluton must have been subjected to high-grade metamorphism that caused loss of Rb and U prior to magma generation. -L.C.H.

The oxygen isotope composition of Almahata Sitta

NASA Astrophysics Data System (ADS)

Rumble, Douglas; Zolensky, Michael E.; Friedrich, Jon M.; Jenniskens, Peter; Shaddad, Muawia H.

2010-10-01

Eleven fragments of the meteorite Almahata Sitta (AHS) have been analyzed for oxygen isotopes. The fragments were separately collected as individual stones from the meteorite's linear strewn field in the Nubian Desert. Each of the fragments represents a sample of a different and distinct portion of asteroid 2008 TC3. Ten of the fragments span the same range of values of δ18O, δ17O, and Δ17O, and follow the same trend along the carbonaceous chondrite anhydrous minerals (CCAM) line as monomict and polymict members of the ureilite family of meteorites. The oxygen isotope composition of fragment #25 is consistent with its resemblance petrographically to an H5 ordinary chondrite. Our results demonstrate that a single small asteroidal parent body, asteroid 2008 TC3, only 4 m in length, encompassed the entire range of variation in oxygen isotope compositions measured for monomict and polymict ureilites.

The Origin of 87Sr/86Sr in Cold Springs and Travertines of the Franciscan Complex near Cazadero, California

NASA Astrophysics Data System (ADS)

Marks, N.; Schiffman, P.; Yin, Q.; Zierenberg, R.

2005-12-01

Ultrabasic springs within the Franciscan Complex of the California Coast Range have been intensely investigated by geochemists and geobiologists. Springs located in Sonoma County in an area historically known as The Cedars are of particular interest to scientists exploring Martian analogues (Johnson et al. 2004) or investigating serpentinization processes (Barnes and O'Neil, 1969; Barnes et al. 1972). Laser ablation and solution phase multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) were used to obtain 87Sr/86Sr isotope ratios in fluid, travertine and serpentinite samples collected at the Cedars. 87Sr/86Sr isotopic ratios in the serpentinizing springs range from 0.70926 to 0.70955; the Mg2+-HCO3- type stream water has an isotopic ratio of 0.70848. The 87Sr/86Sr ratio in the travertines ranges from 0.70931 to 0.70966. The mean 87Sr/86Sr ratio of the travertine (0.7094) is far more radiogenic than typical mantle values of 0.703 to 0.705, indicating that the peridotite is an unlikely source of the radiogenic Sr. Similarly, the measured ratio is much higher than the expected Sr isotope ratio of seawater that might be trapped in Jurassic Franciscan Sediments or oceanic crust. Strontium leached from Franciscan sediments themselves should reflect a Sierran or Klamath source with expected values in the range of 0.705 to 0.706. Indeed the measured isotope ratios even exceed modern seawater values. The observed radiogenic values suggest the presence of older, potassium (and rubidium)-rich rocks within the fluid flow path. Alternatively, the presence of clay minerals that readily substitute Sr for Ca may well account for the radiogenic strontium signal. It is possible that the serpentinization observed at The Cedars initiated along a ridge flank and the Sr isotopic chemistry reflects the site of initiation. The radiogenic strontium in these springs may result from fluid interaction with seafloor sediments deposited along the flank of a slow spreading ridge. If this is the case, it may be possible to use 87Sr/86Sr to determine the location of serpentinization initiation (Gruau et al, 1998). Such a revelation might provide insight into the geochemical processes associated with mid-ocean ridge flank serpentinization at sites like Lost City (Kelley et al., 2005). The implications of this correlation could provide information about the preservation of geochemical systems through obduction of ophiolitic sequences and provide insights into ridge flank hydrothermal and serpentinizing processes.

Are dual isotope and isotopomer ratios of N2O useful indicators for N2O turnover during denitrification in nitrate-contaminated aquifers?

NASA Astrophysics Data System (ADS)

Well, Reinhard; Eschenbach, Wolfram; Flessa, Heinz; von der Heide, Carolin; Weymann, Daniel

2012-08-01

Denitrifying aquifers are sources of the greenhouse gas N2O. Isotopic signatures reflect processes of production and reduction of N2O, but it is not clear to which extent these can be used to quantify those processes. We investigated the spatial distribution of isotopologue values of N2O (δ18O, average δ15N, and 15N site preference, SP) in two denitrifying sandy aquifers to study N2O production and reduction and associated isotope effects in groundwater. For the first time, we combined this approach with direct estimation of N2O reduction from excess-N2 analysis. Groundwater samples were collected from 15 monitoring wells and four multilevel sampling wells and analysed for NO3-, dissolved N2O, dissolved O2, excess N2 from denitrification and isotopic signatures of NO3- and N2O. Both aquifers exhibited high NO3- concentrations with average concentrations of 22 and 15 mg N L-1, respectively. Evidence of intense denitrification with associated N2O formation was obtained from mean excess-N2 of 3.5 and 4.3 mg N L-1, respectively. Isotopic signatures of N2O were highly variable with ranges of 17.6-113.2‰ (δ18O), -55.4 to 89.4‰ (δ15Nbulk) and 1.8-97.9‰ (SP). δ15N and δ18O of NO3- ranged from -2.1‰ to 65.5‰ and from -5‰ to 33.5‰, respectively. The relationships between δ15N of NO3-, δ15Nbulk and SP were not in good agreement with the distribution predicted by a Rayleigh-model of isotope fractionation. The large ranges of δ18O and SP of N2O as well as the close correlation between these values could be explained by the fact that N2O reduction to N2 was strongly progressed but variable. We confirm and explain that a large range in SP and δ18O is typical for N2O from denitrifying aquifers, showing that this source signature can be distinguished from the isotopic fingerprint of N2O emitted from soils without water-logging. We conclude that isotopologue values of N2O in our sites were not suitable to quantify production or reduction of N2O or the contribution of different processes to the total N2O flux, apparently because these values were not only governed by individual pathways but eventually also by the spatial distribution of substrates and activity within the aquifers. These observations could be explained by the dynamics of N2O production, reduction and transport in water-saturated systems with heterogenic distribution of microbial activity and by a combination of diffusive and enzymatic isotope effects.

Global patterns of the isotopic composition of soil and plant nitrogen

USGS Publications Warehouse

Amundson, Ronald; Austin, A.T.; Schuur, E.A.G.; Yoo, K.; Matzek, V.; Kendall, C.; Uebersax, A.; Brenner, D.; Baisden, W.T.

2003-01-01

We compiled new and published data on the natural abundance N isotope composition (??15N values) of soil and plant organic matter from around the world. Across a broad range of climate and ecosystem types, we found that soil and plant ??15N values systematically decreased with increasing mean annual precipitation (MAP) and decreasing mean annual temperature (MAT). Because most undisturbed soils are near N steady state, the observations suggest that an increasing fraction of ecosystem N losses are 15N-depleted forms (NO3, N2O, etc.) with decreasing MAP and increasing MAT. Wetter and colder ecosystems appear to be more efficient in conserving and recycling mineral N. Globally, plant ??15N values are more negative than soils, but the difference Nitrogen isotopes reflect time integrated measures of the controls on N storage that are critical for predictions of how these ecosystems will respond to human-mediated disturbances of the global N cycle.

Identifying recharge from tropical cyclonic storms, Baja California Sur, Mexico.

PubMed

Eastoe, Christopher J; Hess, Greg; Mahieux, Susana

2015-04-01

Groundwater in the Todos Santos watershed in southern Baja California, and throughout the peninsula south of latitude 28°N, has values of (δ18 O‰, δD‰) ranging between (-8.3, -57) and (-10.9, -78). Such negative values are uncharacteristic of the site latitude near the sea level. Altitude effects do not explain the isotope data. Tropical depressions originating along the Pacific coast of North America yield rain with isotopic depletion; rain from these weather systems in southern Arizona commonly has δ18O values<-10‰ in comparison with amount-weighted mean summer and fall rain at -6‰. Isotope data indicate hurricane rain as the predominant source of recharge in southern Baja California, where named tropical depressions bring large rains (>50 mm) at least once every 2 to 3 years, and along the Pacific coast between Jalisco and Oaxaca. © 2014, National Ground Water Association.

Chromium isotope inventory of Cr(VI)-polluted groundwaters at four industrial sites in Central Europe

NASA Astrophysics Data System (ADS)

Novak, Martin; Martinkova, Eva; Chrastny, Vladislav; Stepanova, Marketa; Curik, Jan; Szurmanova, Zdenka; Cron, Marcel; Tylcer, Jiri; Sebek, Ondrej

2016-04-01

Chromium is one of the most toxic elements, especially in its dissolved Cr(VI) form. In the Czech Republic (Central Europe), massive contamination of groundwater has been reported at more than 200 industrial operations. Under suitable conditions, i.e., low Eh, and high availability of reductive agents, Cr(VI) in groundwater may be spontaneously reduced to solid, largely non-toxic Cr(III). This process is associated with a Cr isotope fractionation, with the residual liquid Cr(VI) becoming enriched in the heavier isotope 53Cr. At industrial operations that have been closed and/or where no further leakage of Cr(VI) occurs, the contaminated groundwater plume may be viewed as a closed system. At such sites, an increasing degree of Cr(VI) reduction should result in an increasing del53/52Cr value of the residual liquid. Here we present del53/52Cr systematics at four contaminated Czech sites, focusing on groundwaters. At two of the four sites (Zlate Hory, Loucna) we were also able to analyze the source of contamination. Chromium in the electroplating solutes was isotopically relatively light, with del53/52Cr values <1 per mil. At the remaining two sites (Letnany and Velesin), the Cr isotope signature of the source of contamination was not known. At all four sites, most del53/52Cr values were positive, with means higer than 1 per mil: At Zlate Hory, del53/52Cr ranged between -2.2 and +3.0 per mil (mean of +1.5 per mil); at Loucna, del53/52Cr ranged between 0 and +4.0 per mil (mean of +1.7 per mil); at Letnany, del53/52Cr ranged between +2.0 and +4.5 per mil (mean of +3.2 per mil); and at Velesin, del53/52Cr ranged between +0.5 and +4.5 per mil (mean of +2.7 per mil). Cr(VI) reduction may proceed at Zlate Hory and Loucna, where del53/52Cr(VI) values in groundwater were on average higher than those of the contamination source. At these two sites, our Cr isotope data are not consistent with the existing estimates of the amount of dissolved and precipitated Cr: The pool size of solid Cr(III) in the soil was estimated at 6600 and 500 kg at Zlate Hory and Loucna, respectively. At the same time, the pool size of dissolved Cr(VI) was estimated at 50 and 1.2 kg at Zlate Hory and Loucna, respectively. It follows that, at both sites, less than 1 % of the entire Cr that had leaked into the aquifer an a liquid form remained in the liquid form. If, indeed, most solid Cr now present in the saturated zone had undergone anaerobic reduction, we would expect much higher del53/52Cr values of the residual liquid Cr(VI) than those actually observed. Our understanding of the system is incomplete. Currently, del53/52Cr values of the contaminated soils are being determined in an attempt to close a Cr isotope mass balance.

Isotopic composition of methane and inferred methanogenic substrates along a salinity gradient in a hypersaline microbial mat system.

PubMed

Potter, Elyn G; Bebout, Brad M; Kelley, Cheryl A

2009-05-01

The importance of hypersaline environments over geological time, the discovery of similar habitats on Mars, and the importance of methane as a biosignature gas combine to compel an understanding of the factors important in controlling methane released from hypersaline microbial mat environments. To further this understanding, changes in stable carbon isotopes of methane and possible methanogenic substrates in microbial mat communities were investigated as a function of salinity here on Earth. Microbial mats were sampled from four different field sites located within salterns in Baja California Sur, Mexico. Salinities ranged from 50 to 106 parts per thousand (ppt). Pore water and microbial mat samples were analyzed for the carbon isotopic composition of dissolved methane, dissolved inorganic carbon (DIC), and mat material (particulate organic carbon or POC). The POC delta(13)C values ranged from -6.7 to -13.5 per thousand, and DIC delta(13)C values ranged from -1.4 to -9.6 per thousand. These values were similar to previously reported values. The delta(13)C values of methane ranged from -49.6 to -74.1 per thousand; the methane most enriched in (13)C was obtained from the highest salinity area. The apparent fractionation factors between methane and DIC, and between methane and POC, within the mats were also determined and were found to change with salinity. The apparent fractionation factors ranged from 1.042 to 1.077 when calculated using DIC and from 1.038 to 1.068 when calculated using POC. The highest-salinity area showed the least fractionation, the moderate-salinity area showed the highest fractionation, and the lower-salinity sites showed fractionations that were intermediate. These differences in fractionation are most likely due to changes in the dominant methanogenic pathways and substrates used at the different sites because of salinity differences.

Biogeochemical Mg cycle in the Barton Peninsula, King George Island, West Antarctica

NASA Astrophysics Data System (ADS)

Choi, H. B.; Ryu, J. S.; Lee, J.; Lim, H. S.; Yoon, H.

2016-12-01

Understanding of biogeochemical Mg cycle is important in terms of plant growth as well as global climate because Mg participates in numerous biogeochemical processes. Here, we collected rock, soil, water and moss samples in the Barton peninsula, King George Island, West Antarctica, and measured their elemental and Mg isotope compositions in order to quantify and understand the biogeochemical processes of the Mg cycle. Elemental results show that the input of seawater derived Mg mainly controls dissolved Mg in meltwater. Mg isotope compositions in rocks and soils are consistent within the error, -0.03 ± 0.15‰ (n=6) and +0.03 ± 0.07‰ (n=8), respectively. However, δ26Mg values of meltwater and moss are -0.69 ± 0.09‰ (n=34) and -0.46 ± 0.19‰ (n=16), respectively, indicating that mosses display higher δ26Mg values compared to meltwater they uptake. This implies an isotope fractionation in favor of heavy isotopes during moss growth. The apparent Mg isotope fractionation between moss and meltwater (Δ26Mgmoss-meltwater) ranges from 0.02‰ to 0.55‰, with an average of +0.29‰ (n=6), which is within the range previously reported during higher plant growth. Our finding suggests that enhanced plant growth in Arctic and Antarctica due to climate change and global warming may play an important role in the biogeochemical Mg cycle globally.

Pb concentrations and isotopic record preserved in northwest Greenland snow.

PubMed

Kang, Jung-Ho; Hwang, Heejin; Han, Changhee; Hur, Soon Do; Kim, Seong-Joong; Hong, Sungmin

2017-11-01

We present high-resolution lead (Pb) concentrations and isotopic ratios from a northwest Greenland snow pit covering a six-year period between 2003 and 2009. Pb concentrations ranged widely from 2.7 pg g -1 to 97.3 pg g -1 , with a mean concentration of 21.6 pg g -1 . These values are higher than those recorded for the pre-industrial period. Pb concentrations exhibit seasonal spikes in winter-spring layers. Crustal Pb enrichment factors (EF) suggest that the northwest Greenland snow pit is highly enriched with Pb of predominantly anthropogenic origin. The 206 Pb/ 207 Pb ratios ranged from 1.144 to 1.169 with a mean value of 1.156, which fall between less radiogenic Eurasian-type and more radiogenic Canadian-type signatures. This result suggests that several potential source areas of Pb impact on northwest Greenland. Abrupt changes in Pb concentrations and Pb isotope ratios were observed and related to seasonal shifts in source regions of aerosol transport. The 206 Pb/ 207 Pb isotope ratio increased gradually between 2003 and 2009. The similarity of the three-isotope plot ( 206 Pb/ 207 Pb versus 208 Pb/ 207 Pb) between some of our samples and Chinese urban aerosols suggests a steadily increasing contribution of Chinese Pb to northwest Greenland snow. Copyright © 2017. Published by Elsevier Ltd.

Precipitation isotopes link regional climate patterns to water supply in a tropical mountain forest, eastern Puerto Rico

USGS Publications Warehouse

Scholl, Martha A.; Murphy, Sheila F.

2014-01-01

Like many mountainous areas in the tropics, watersheds in the Luquillo Mountains of eastern Puerto Rico have abundant rainfall and stream discharge and provide much of the water supply for the densely populated metropolitan areas nearby. Projected changes in regional temperature and atmospheric dynamics as a result of global warming suggest that water availability will be affected by changes in rainfall patterns. It is essential to understand the relative importance of different weather systems to water supply to determine how changes in rainfall patterns, interacting with geology and vegetation, will affect the water balance. To help determine the links between climate and water availability, stable isotope signatures of precipitation from different weather systems were established to identify those that are most important in maintaining streamflow and groundwater recharge. Precipitation stable isotope values in the Luquillo Mountains had a large range, from fog/cloud water with δ2H, δ18O values as high as +12 ‰, −0.73 ‰ to tropical storm rain with values as low as −127 ‰, −16.8 ‰. Temporal isotope values exhibit a reverse seasonality from those observed in higher latitude continental watersheds, with higher isotopic values in the winter and lower values in the summer. Despite the higher volume of convective and low-pressure system rainfall, stable isotope analyses indicated that under the current rainfall regime, frequent trade -wind orographic showers contribute much of the groundwater recharge and stream base flow. Analysis of rain events using 20 years of 15 -minute resolution data at a mountain station (643 m) showed an increasing trend in rainfall amount, in agreement with increased precipitable water in the atmosphere, but differing from climate model projections of drying in the region. The mean intensity of rain events also showed an increasing trend. The determination of recharge sources from stable isotope tracers indicates that water supply will be affected if regional atmospheric dynamics change trade- wind orographic rainfall patterns in the Caribbean.

Interannual variability in seagrass carbon and nitrogen stable isotopes from the Florida Keys National Marine Sanctuary, a preliminary study

NASA Astrophysics Data System (ADS)

Fourqurean, J. W.; Fourqurean, J. W.; Anderson, W. T.; Anderson, W. T.

2001-12-01

The shallow marine waters surrounding the southern tip of Florida provide an ideal environment for seagrasses, which are the most common benthic community in the region. Yet, these communities are susceptible to a variety of anthropogenic disturbances, especially changes in water quality caused by an increase the nutrient flux to the near shore environment. In order to better understand the carbon and nitrogen isotopic ratio in marine plants, an extensive times series analysis was constructed from quarterly sampling of Thalassia testudinum (the dominate species in the study area) from 1996 through 1998. Sites for study where selected from permanent stations within the Florida Keys National Marine Sanctuary (FKNMS), from both sides of the Florida Keys - two stations on the bay side and two stations on the reef side. These data will also help to constrain elements of the carbon and nitrogen cycles affecting this region. The data analyzed over the three year study period show unique cyclic trends associated with seasonal changes in primary productivity and potentially changes in the nitrogen and carbon pools. Additionally, the analysis of our time series indicates that isotope food web studies need to take into account spatial and temporal changes when evaluating trophic levels. The mean carbon and nitrogen isotope values of T. testudinum from all 4 stations vary respectively from -7.2 per mil to -10.41 and 1.1 per mil to 2.2 per mil (n = 48). However, certain stations displayed anonymously depleted nitrogen isotope values, values as low as -1.2 per mil. These values potentially indicated that biogeochmical processes like N fixation, ammonification and denitrification cause regional pattern in the isotopic composition of the source DIN. Both carbon and nitrogen isotopes displayed seasonal enrichment-depletion trends, with maximum enrichment occurring during the summer. The overall seasonal variation for carbon 13 from the different stations ranged from 1 per mil to greater than 3 per mil; whereas seasonal variations in d15N between different stations ranged from about 1 per mil to greater than 5 per mil. Additionally certain sites showed a positive isotope values and productivity. These data indicate a high degree of seasonal variability due to changes in productivity, environmental parameters, and oceanographic controls. The more open settings are not restricted by the temperature changes occurring in the shallower water sites. Additionally, carbon and nitrogen sources can change due to the mineralization of OM from different sources from nearby mangrove islands and/or the Everglades to the north.

Carbon, oxygen, and strontium isotopic composition of methane-derived authigenic carbonates in methane seep areas, eastern margin of Japan Sea

NASA Astrophysics Data System (ADS)

Kakizaki, Y.; Ishikawa, T.; Hiruta, A.; Matsumoto, R.

2016-12-01

We report the occurrence, mineralogy, and isotopic composition (δ13C; δ18O) of methane-derived authigenic carbonates (MDACs) from three methane seep areas with shallow gas hydrate (Umitaka Spur, Joetsu Knoll, and off-Tobishima Island), in the southeastern margin of Japan Sea. Furthermore, we present strontium isotopic ratios (87Sr/86Sr) of MDACs, pore waters, and seawater from Umitaka Spur. MDACs range from a few mm to several tens of cm in diameter. Their shape is quite varied, e.g. nodular, platy, and indetermine form. Most MDACs are composed of high-Mg calcite. The δ13C values of MDACs from Umitaka Spur range from -30 to -4 permil. These isotopic values are higher than those of Joetsu Knoll and off-Tobishima Island. This difference is dependent upon the formation depth of MDACs in the sediment column. It probably indicates a difference in the formation environment of MDACs (e.g. methane flux). Meanwhile, range of the δ18O values of MDACs from those three areas is mostly equal. The 87Sr/86Sr ratios in MDACs from shallow sediment depth of Umitaka Spur are equal to those of modern surface seawater just above Umitaka Spur. The 87Sr/86Sr ratios of MDACs from deeper sediment depth are lower, and the Sr-isotopic trend indicates an upward increase. This trend can be correlated to the global Sr-isotopic trend of the seawater from late Pleistocene to present. It means that 87Sr/86Sr ratios of MDACs reflect the 87Sr/86Sr ratio of seawater at the formation age. However, the 87Sr/86Sr ratios in pore water are lower than those of MDACs, yet follow a parallel trend. This would suggest that the pore water includes a source of light Sr, presumably released from tuff and volcaniclastics during diagenetic processes. This study was conducted under the commission from AIST as a part of the methane hydrate research project funded by METI (the Ministry of Economy, Trade and Industry, Japan).

Using stable isotopes of dissolved oxygen for the determination of gas exchange in the Grand River, Ontario, Canada.

PubMed

Jamieson, Terra S; Schiff, Sherry L; Taylor, William D

2013-02-01

Gas exchange can be a key component of the dissolved oxygen (DO) mass balance in aquatic ecosystems. Quantification of gas transfer rates is essential for the estimation of DO production and consumption rates, and determination of assimilation capacities of systems receiving organic inputs. Currently, the accurate determination of gas transfer rate is a topic of debate in DO modeling, and there are a wide variety of approaches that have been proposed in the literature. The current study investigates the use of repeated measures of stable isotopes of O₂ and DO and a dynamic dual mass-balance model to quantify gas transfer coefficients (k) in the Grand River, Ontario, Canada. Measurements were conducted over a longitudinal gradient that reflected watershed changes from agricultural to urban. Values of k in the Grand River ranged from 3.6 to 8.6 day⁻¹, over discharges ranging from 5.6 to 22.4 m³ s⁻¹, with one high-flow event of 73.1 m³ s⁻¹. The k values were relatively constant over the range of discharge conditions studied. The range in discharge observed in this study is generally representative of non-storm and summer low-flow events; a greater range in k might be observed under a wider range of hydrologic conditions. Overall, k values obtained with the dual model for the Grand River were found to be lower than predicted by the traditional approaches evaluated, highlighting the importance of determining site-specific values of k. The dual mass balance approach provides a more constrained estimate of k than using DO only, and is applicable to large rivers where other approaches would be difficult to use. The addition of an isotopic mass balance provides for a corroboration of the input parameter estimates between the two balances. Constraining the range of potential input values allows for a direct estimate of k in large, productive systems where other k-estimation approaches may be uncertain or logistically infeasible. Copyright © 2012 Elsevier Ltd. All rights reserved.

Lead in the Getchell-Turquoise ridge Carlin-type gold deposits from the perspective of potential igneous and sedimentary rock sources in Northern Nevada: Implications for fluid and metal sources

USGS Publications Warehouse

Tosdal, R.M.; Cline, J.S.; Fanning, C.M.; Wooden, J.L.

2003-01-01

Lead isotope compositions of bulk mineral samples (fluorite, orpiment, and realgar) determined using conventional techniques and of ore-stage arsenian pyrite using the Sensitive High Resolution Ion-Microprobe (SHRIMP) in the Getchell and Turquoise Ridge Carlin-type gold deposits (Osgood Mountains) require contribution from two different Pb sources. One Pb source dominates the ore stage. It has a limited Pb isotope range characterized by 208Pb/206Pb values of 2.000 to 2.005 and 207Pb/206Pb values of 0.8031 to 0.8075, as recorded by 10-??m-diameter spot SHRIMP analyses of ore-stage arsenian pyrite. These values approximately correspond to 206Pb/204Pb of 19.3 to 19.6, 207Pb/204Pb of 15.65 to 15.75, and 208Pb/204Pb of 39.2 to 39.5. This Pb source is isotopically similar to that in average Neoproterozoic and Cambrian elastic rocks but not to any potential magmatic sources. Whether those clastic rocks provided Pb to the ore fluid cannot be unequivocally proven because their Pb isotope compositions over the same range as in ore-stage arsenian pyrite are similar to those of Ordovician to Devonian siliciclastic and calcareous rocks. The Pb source in the calcareous rocks most likely is largely detrital minerals, since that detritus was derived from the same sources as the detritus in the Neoproterozoic and Cambrian clastic rocks. The second Pb source is characterized by a large range of 206Pb/204Pb values (18-34) with a limited range of 208Pb/204Pb values (38.1-39.5), indicating low but variable Th/U and high and variable U/Pb values. The second Pb source dominates late and postore-stage minerals but is also found in preore sulfide minerals. These Pb isotope characteristics typify Ordovician to Devonian siliciclastic and calcareous rocks around the Carlin trend in northeast Nevada. Petrologically similar rocks host the Getchell and Turquoise Ridge deposits. Lead from the second source was either contributed from the host sedimentary rock sequences or brought into the hydrothermal system by oxidized ground water as the system collapsed. Late ore- and postore-stage sulfide minerals (pyrite, orpiment, and stibnite) from the Betze-Post and Meikle deposits in the Carlin trend and from the Jerritt Canyon mining district have Pb isotope characteristics similar to those determined in Getchell and Turquoise Ridge. This observation suggests that the Pb isotope compositions of their ore fluids may be similar to those at Getchell and Turquoise Ridge. Two models can explain the Pb isotope compositions of the ore-stage arsenian pyrite versus the late ore or postore sulfide minerals. In either model, Pb from the Ordovician to Devonian siliciclastic and calcareous rock source enters the hydrothermal system late in the ore stage but not to any extent during the main stage of ore deposition. In one model, ore-stage Pb was derived from a source with Pb isotope compositions similar to those of the Neoproterozoic and Cambrian clastic sequence, transported as part of the ore fluid and then deposited in the ore-stage arsenian pyrite and fluorite. The second model is based on the observation that the Pb isotope characteristics of the ore-stage minerals also are found in some Ordovician to Devonian calcareous and siliciclastic rocks. Hence, ore-stage Pb could have been derived locally and simply concentrated during the ore stage. Critical to the second model is the removal of all high 206Pb/204Pb (>20) material during alteration. It Also requires the retention of only the low 206Pb/204Pb component of the Ordovician to Devonian sedimentary rocks. This critical step is possible only if the high 206Pb/204Pb values are contained in readily dissolvable mineral phases, whereas the low 206Pb/204Pb values are found only in refractory minerals that released Pb during a final alteration stage just prior deposition of auriferous arsenian pyrite. Distinguishing between Pb transported with the ore fluid or inherited from the site of mineral deposition is not straightforward

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

USGS Publications Warehouse

Böhlke, John Karl; Mroczkowski, Stanley J.; Sturchio, Neil C.; Heraty, Linnea J.; Richman, Kent W.; Sullivan, Donald B.; Griffith, Kris N.; Gu, Baohua; Hatzinger, Paul B.

2017-01-01

RationalePerchlorate (ClO4−) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO4− source attribution and natural attenuation studies: δ37Cl, δ18O, and δ17O (or Δ17O or 17Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies.MethodsThree large batches of KClO4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O2, and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO4− to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO4 was reprecipitated as AgCl and converted into CH3Cl for DIIRMS.ResultsKClO4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO4− depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO42−, NO3−, ReO42−, and C-bearing contaminants include isotope mixing and fractionation effects on CO and O2, plus direct interference from CO2 in the mass spectrometer. The results highlight the importance of effective purification of ClO4− from environmental samples.ConclusionsKClO4 reference materials are available for testing methods and calibrating isotopic data for ClO4− and other substances with widely varying Cl or O isotopic compositions. Current ClO4−extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO4−, permitting isotopic evaluation of environmental ClO4− sources and natural attenuation.

Variable δ(15)N diet-tissue discrimination factors among sharks: implications for trophic position, diet and food web models.

PubMed

Olin, Jill A; Hussey, Nigel E; Grgicak-Mannion, Alice; Fritts, Mark W; Wintner, Sabine P; Fisk, Aaron T

2013-01-01

The application of stable isotopes to characterize the complexities of a species foraging behavior and trophic relationships is dependent on assumptions of δ(15)N diet-tissue discrimination factors (∆(15)N). As ∆(15)N values have been experimentally shown to vary amongst consumers, tissues and diet composition, resolving appropriate species-specific ∆(15)N values can be complex. Given the logistical and ethical challenges of controlled feeding experiments for determining ∆(15)N values for large and/or endangered species, our objective was to conduct an assessment of a range of reported ∆(15)N values that can hypothetically serve as surrogates for describing the predator-prey relationships of four shark species that feed on prey from different trophic levels (i.e., different mean δ(15)N dietary values). Overall, the most suitable species-specific ∆(15)N values decreased with increasing dietary-δ(15)N values based on stable isotope Bayesian ellipse overlap estimates of shark and the principal prey functional groups contributing to the diet determined from stomach content analyses. Thus, a single ∆(15)N value was not supported for this speciose group of marine predatory fishes. For example, the ∆(15)N value of 3.7‰ provided the highest percent overlap between prey and predator isotope ellipses for the bonnethead shark (mean diet δ(15)N = 9‰) whereas a ∆(15)N value < 2.3‰ provided the highest percent overlap between prey and predator isotope ellipses for the white shark (mean diet δ(15)N = 15‰). These data corroborate the previously reported inverse ∆(15)N-dietary δ(15)N relationship when both isotope ellipses of principal prey functional groups and the broader identified diet of each species were considered supporting the adoption of different ∆(15)N values that reflect the predators' δ(15)N-dietary value. These findings are critical for refining the application of stable isotope modeling approaches as inferences regarding a species' ecological role in their community will be influenced with consequences for conservation and management actions.

Variable δ15N Diet-Tissue Discrimination Factors among Sharks: Implications for Trophic Position, Diet and Food Web Models

PubMed Central

Olin, Jill A.; Hussey, Nigel E.; Grgicak-Mannion, Alice; Fritts, Mark W.; Wintner, Sabine P.; Fisk, Aaron T.

2013-01-01

The application of stable isotopes to characterize the complexities of a species foraging behavior and trophic relationships is dependent on assumptions of δ15N diet-tissue discrimination factors (∆15N). As ∆15N values have been experimentally shown to vary amongst consumers, tissues and diet composition, resolving appropriate species-specific ∆15N values can be complex. Given the logistical and ethical challenges of controlled feeding experiments for determining ∆15N values for large and/or endangered species, our objective was to conduct an assessment of a range of reported ∆15N values that can hypothetically serve as surrogates for describing the predator-prey relationships of four shark species that feed on prey from different trophic levels (i.e., different mean δ15N dietary values). Overall, the most suitable species-specific ∆15N values decreased with increasing dietary-δ15N values based on stable isotope Bayesian ellipse overlap estimates of shark and the principal prey functional groups contributing to the diet determined from stomach content analyses. Thus, a single ∆15N value was not supported for this speciose group of marine predatory fishes. For example, the ∆15N value of 3.7‰ provided the highest percent overlap between prey and predator isotope ellipses for the bonnethead shark (mean diet δ15N = 9‰) whereas a ∆15N value < 2.3‰ provided the highest percent overlap between prey and predator isotope ellipses for the white shark (mean diet δ15N = 15‰). These data corroborate the previously reported inverse ∆15N-dietary δ15N relationship when both isotope ellipses of principal prey functional groups and the broader identified diet of each species were considered supporting the adoption of different ∆15N values that reflect the predators’ δ15N-dietary value. These findings are critical for refining the application of stable isotope modeling approaches as inferences regarding a species’ ecological role in their community will be influenced with consequences for conservation and management actions. PMID:24147026

Sulfur isotopes in Icelandic thermal fluids

NASA Astrophysics Data System (ADS)

Gunnarsson-Robin, Jóhann; Stefánsson, Andri; Ono, Shuhei; Torssander, Peter

2017-10-01

Multiple sulfur isotope compositions of thermal fluids from Iceland were measured in order to evaluate the sources and reactions of sulfur and sulfur isotope fractionation in geothermal systems at Icelandic divergent plate boundaries, characterized by MORB-like basalts. The geothermal systems studied had a wide range of reservoir temperatures of 56-296 °C and Cl concentrations of 18-21,000 ppm. Dissolved sulfide (∑ S- II) and SO4 concentrations in liquid water measured < 0.01-165 ppm and 1.3-300 ppm, respectively, and H2S(g) concentrations in the vapor 4.9-2000 ppm. The δ34S and Δ33S values for different phases and oxidation states were highly variable: δ34S∑ S- II = - 11.6 to 10.5‰ (n = 99), Δ33S∑ S- II = - 0.12 to 0.00‰ (n = 45), δ34SSO4 = - 1.0 to 24.9‰ (n = 125), Δ33SSO4 = - 0.04 to 0.02‰ (n = 50), δ34SH2S(g) = - 2.6 to 5.9‰ (n = 112) and Δ33SH2S(g) = - 0.03 to 0.00‰ (n = 56). The multiple sulfur isotope values of the thermal fluids are interpreted to reflect various sources of sulfur in the fluids, as well as isotope fractionation occurring within the geothermal systems associated with fluid-rock interaction, boiling and oxidation and reduction reactions. The results of isotope geochemical modeling demonstrate that the sources of S- II in the thermal fluid are leaching of basalt (MORB) and seawater SO4 reduction for saline systems with insignificant magma gas input, and that the observed ranges of δ34S and Δ33S for ∑ S- II and H2S(g) reflect isotope fractionation between minerals and aqueous and gaseous species upon fluid-rock interaction and boiling. The sources of SO4 are taken to be multiple, including oxidation of S- II originating from basalt, leaching of SVI from the basalts and the seawater itself in the case of saline systems. In low-temperature fluids, the δ34S and Δ33S values reflect the various sources of sulfur. For high-temperature fluids, fluid-rock interaction, ∑ S- II oxidation and SO4 reduction and sulfide and sulfate mineral formation result in a large range of δ34S and Δ33S values for ∑ S- II and SO4 in the fluids, highlighting the importance and effects of chemical reactions on the isotope systematics of reactive elements like sulfur. Such effects needed to be quantified in order to reveal the various sources of an element.

Sulfur isotope and porewater geochemistry of Florida escarpment seep sediments

USGS Publications Warehouse

Chanton, J.P.; Martens, C.S.; Paull, C.K.; Coston, J.A.

1993-01-01

Distributions of porewater constituents, SO4=, NH4+, Cl-, ???CO2, and H2S, solid phase iron, and sulfur concentrations, and the sulfur isotopic composition of dissolved and solid phases were investigated in sediments from abyssal seeps at the base of the Florida escarpment. Despite the apparent similarity of seep sediment porewater chemistry to that of typical marine sediments undergoing early diagenesis, relationships between chemical distributions and isotopic measurements revealed that the distribution of pore fluid constituents was dominated by processes occurring within the platform rather than by in situ microbial processes. Ammonium and sulfate concentrations were linearly correlated with chloride concentrations, indicating that variations in porewater chemistry were controlled by the admixture of seawater and a sulfate depleted brine with a chlorinity of 27.5 ?? 1.9%. and 2.2 ?? 1.3 mM ammonium concentration. At sites dominated by seepage, dissolved sulfate isotopic composition remained near seawater values despite depletion in porewater concentrations. Porewater ???CO2 concentrations were found to be elevated relative to seawater, but not to the extent predicted from the observed sulfate depletion. Sediment solid phase sulfur was predominantly pyrite, at concentrations as high as 20% S by weight. In contrast to typical marine deposits, pyrite concentrations were not related to the quantity of sedimentary organic matter. Pyrite ??34S values ranged from -29%. to + 21%. (CDT). However, only positive ??34S values were observed at sites associated with high pyrite concentrations. Isotopically heavy pyrite was observed at sites with porewater sulfate of seawater-like isotopic composition. Isotopically light pyrite was associated with sites where porewater sulfate exhibited ??34S values greater than those in seawater, indicating the activity of in situ microbial sulfate reduction. Thus, dual sulfide sources are suggested to explain the range in sediment pyrite isotopic composition: a ??34S enriched (+10 to +20%.) source adverted from within the Florida platform, and a lighter 34S depleted component generated in situ from microbial reduction of seawater sulfate. The degree of pyritization of seep sediments was as high as 0.9 and was controlled by pyrite concentrations, which varied over a wider range than did the non-pyrite solid phase iron concentrations. The highest non-sulfide solid phase iron concentrations were observed in sediments that are believed to be at the "front" of the advancing seep fluids (i.e., hemipelagic sediments newly exposed to the seep fluids), indicating that dissolution of hemipelagic background sediment may be the source of at least half of the iron to the highly pyritized seep sediments. Porewater sulfide concentrations were variable, reaching a maximum of 5.7 mM, and were not correlated with the degree of pyritization of the sediments, suggesting that iron was not particularly limiting to pyrite formation. ?? 1993.

Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements: Caffeines, n-Alkanes, Fatty Acid Methyl Esters, Glycines, L-Valines, Polyethylenes, and Oils.

PubMed

Schimmelmann, Arndt; Qi, Haiping; Coplen, Tyler B; Brand, Willi A; Fong, Jon; Meier-Augenstein, Wolfram; Kemp, Helen F; Toman, Blaza; Ackermann, Annika; Assonov, Sergey; Aerts-Bijma, Anita T; Brejcha, Ramona; Chikaraishi, Yoshito; Darwish, Tamim; Elsner, Martin; Gehre, Matthias; Geilmann, Heike; Gröning, Manfred; Hélie, Jean-François; Herrero-Martín, Sara; Meijer, Harro A J; Sauer, Peter E; Sessions, Alex L; Werner, Roland A

2016-04-19

An international project developed, quality-tested, and determined isotope-δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope-δ scales. The RMs span a range of δ(2)H(VSMOW-SLAP) values from -210.8 to +397.0 mUr or ‰, for δ(13)C(VPDB-LSVEC) from -40.81 to +0.49 mUr and for δ(15)N(Air) from -5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C16 n-alkanes, n-C20-fatty acid methyl esters (FAMEs), glycines, and l-valines, together with polyethylene powder and string, one n-C17-FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a (2)H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ(2)H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain (13)C and carbon-bound organic (2)H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies.

Isotopic variability of cave bears (δ15N, δ13C) across Europe during MIS 3

NASA Astrophysics Data System (ADS)

Krajcarz, Magdalena; Pacher, Martina; Krajcarz, Maciej T.; Laughlan, Lana; Rabeder, Gernot; Sabol, Martin; Wojtal, Piotr; Bocherens, Hervé

2016-01-01

Collagen, the organic fraction of bone, records the isotopic parameters of consumed food for carbon (δ13C) and nitrogen (δ15N). This relationship of isotopic signature between diet and tissue is an important tool for the study of dietary preferences of modern and fossil animal species. Since the first information on the isotopic signature of cave bear was reported, numerous data from Europe have become available. The goal of this work is to track the geographical variation of cave bear collagen isotopic values in Europe during Marine Isotopic Stage 3 (about 60,000-25,000 yr BP). In this study the results of new δ13C and δ15N isotopic analyses of cave bear collagen from four Central-Eastern European sites are presented, as well as a review of all published isotopic data for cave bears of the same period. The main conclusion is a lack of geographical East-West pattern in the variations of δ13C and δ15N values of cave bear collagen. Moreover, no relationship was found between cave bear taxonomy and isotopic composition. The cave bears from Central-Eastern Europe exhibit δ13C and δ15N values near the average of the range of Central, Western and Southern European cave bears. Despite the fact that most cave bear sites follow an altitudinal gradient, separate groups of sites exhibit shift in absolute values of δ13C, what disturbs an altitude-related isotopic pattern. The most distinct groups are: high Alpine sites situated over 1500 m a.s.l. - in terms of δ13C; and two Romanian sites Peştera cu Oase and Urşilor - in case of δ15N. Although the cave bear isotopic signature is driven by altitude, the altitudinal adjustment of isotopic data is not enough to explain the isotopic dissimilarity of these cave bears. The unusually high δ15N signature of mentioned Romanian sites is an isolated case in Europe. Cave bears from relatively closely situated Central-Eastern European sites and other Romanian sites are more similar to Western European than to Romanian populations in terms of isotopic composition, and probably ecology.

Secular variations of iron isotopes in ferromanganese crusts: evidences for deeply sourced iron in the Pacific Ocean?

NASA Astrophysics Data System (ADS)

Rouxel, O. J.; Gueguen, B.

2016-12-01

Ferromanganese (Fe-Mn) crusts are potential archive of the Fe isotope composition of deep seawater through time. Here, we report Fe isotope composition of two pairs of Fe-Mn crusts collected on two volcanic seamounts from the Northern Pacific Ocean (Apuupuu Seamount, Hawaii) and the Southern Pacific Ocean (near Rurutu Island, Austral archipelago of French Polynesia). This approach allows (a) a direct comparison of the Fe isotope record in Fe-Mn crusts from the same seamount in order to address local effects, and (b) a comparison of geochemical composition of crusts between North and South Pacific in order to address the effect of more global geochemical processes. The results show that, despite different growth rates, diagenetic history, textures and geochemical patterns, Fe-Mn crusts from both North and South Pacific Oceans have fairly homogenous Fe isotope compositions over the last 17 Ma, yielding average δ56Fe values of -0.22 ± 0.20‰ (1sd, n = 54). The results also show striking correlations between Fe and Pb isotope ratios, indicating that local mixing between water masses is the main factor controlling Fe isotope composition in FeMn crusts. Recently, Horner et al. (2015) reported a range of δ56Fe values from -1.12‰ to 1.54‰ along a 76 Ma-old FeMn crust from the central pacific. However, secular variations of Fe isotopes inferred from other FeMn crusts in the Central North Pacific and Western Pacific (Yang and Rouxel, unpublished) show different patterns over the last 40 Ma, with δ56Fe ranging from -0.07 to -0.61‰ (n=81). Hence, the application of Fe isotopes as paleoceanographic proxies to trace deeply sourced iron at the scale of oceanic basins should be used with caution, prompting for an integrative approach combining diverse yet complimentary geochemical proxies.

Modified sulfur isotopic compositions of sulfides in the nakhlites and Chassigny

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenwood, J.P.; Riciputi, L.R.; McSween, H.Y. Jr.

Variable sulfur isotopic ratios of sulfide minerals in the nakhlites and Chassigny have been measured by ion microprobe. The ranges and means of {delta}{sup 34}S values of pyrrhotite and pyrite in nakhlites become more negative in the sequence Nakhla > Governador Valadares > Lafayette. This is also the sequence of increasing degrees of subsolidus re-equilibration, suggesting that {sup 32}S enrichment may be related to the subsolidus thermal history. A chalcopyrite vein cross cutting a pyrrhotite in Nakhla, coupled with chalcopyrite having slightly lighter {delta}{sup 34}S values, suggests that subsolidus fluids may have become isotopically lighter (with respect to sulfur) inmore » Nakhla with time. Pyrite has replaced pyrrhotite in Lafayette, suggesting that {line_integral}O{sub 2} and/or {line_integral}S{sub 2} increased after pyrrhotite crystallization. A model involving subsolidus hydrothermal modification of igneous sulfide minerals (with {delta}{sup 34}S {approximately} 0{degree}) due to late-stage oxidation of fluids provides a reasonable explanation for the sulfur isotopic systematics of the nakhlites and Chassigny. Sulfur isotopic alteration is believed to have occurred during the waning stages of nakhlite magmatism, rather than during a much later low-temperature (<100 C) iddingsite formation event, based on the ineffectiveness of abiogenic sulfur isotopic fractionation below 200 C. Variable mixing of two isotopically different fluids also could have produced the observed fractionations, although an isotopically light reservoir of sulfur is problematic. Other possible mechanisms evaluated to explain the sulfur isotopic values of the sulfide minerals include martial mantle heterogeneity, possible influence of martial biological processes, and magmatic degassing of SO{sub 2}.« less

Modeling the effects of diagenesis on carbonate clumped-isotope values in deep- and shallow-water settings

NASA Astrophysics Data System (ADS)

Stolper, Daniel A.; Eiler, John M.; Higgins, John A.

2018-04-01

The measurement of multiply isotopically substituted ('clumped isotope') carbonate groups provides a way to reconstruct past mineral formation temperatures. However, dissolution-reprecipitation (i.e., recrystallization) reactions, which commonly occur during sedimentary burial, can alter a sample's clumped-isotope composition such that it partially or wholly reflects deeper burial temperatures. Here we derive a quantitative model of diagenesis to explore how diagenesis alters carbonate clumped-isotope values. We apply the model to a new dataset from deep-sea sediments taken from Ocean Drilling Project site 807 in the equatorial Pacific. This dataset is used to ground truth the model. We demonstrate that the use of the model with accompanying carbonate clumped-isotope and carbonate δ18O values provides new constraints on both the diagenetic history of deep-sea settings as well as past equatorial sea-surface temperatures. Specifically, the combination of the diagenetic model and data support previous work that indicates equatorial sea-surface temperatures were warmer in the Paleogene as compared to today. We then explore whether the model is applicable to shallow-water settings commonly preserved in the rock record. Using a previously published dataset from the Bahamas, we demonstrate that the model captures the main trends of the data as a function of burial depth and thus appears applicable to a range of depositional settings.

Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

NASA Astrophysics Data System (ADS)

Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

2015-04-01

Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

Nitrogen, Sulfur, and Oxygen Isotope Ratios of Animal- and Plant-Based Organic Fertilizers Used in South Korea.

PubMed

Shin, Woo-Jin; Ryu, Jong-Sik; Mayer, Bernhard; Lee, Kwang-Sik; Kim, Insu

2017-05-01

Organic fertilizers are increasingly used in agriculture in Asia and elsewhere. Tracer techniques are desirable to distinguish the fate of nutrients added to agroecosystems with organic fertilizers from those contained in synthetic fertilizers. Therefore, we determined the nitrogen, sulfur, and oxygen isotope ratios of nitrogen- and sulfur-bearing compounds in animal- and plant-based organic fertilizers (ABOF and PBOF, respectively) used in South Korea to evaluate whether they are isotopically distinct. The δN values of total and organic nitrogen for ABOF ranged from +7 to +19‰ and were higher than those of PBOF (generally <+6‰). This suggests that ABOFs have distinct δN values suitable for tracing these fertilizer compounds in the plant-soil-water system, whereas PBOFs have similar δN values to synthetic fertilizers. However, δO values for nitrate (δO) from organic fertilizer samples (<+17.0‰) were consistently lower than those of synthetic nitrate-containing fertilizers. The δS values of total sulfur, organic sulfur compounds (e.g., carbon-bonded sulfur and hydriodic acid-reducible sulfur), and sulfate for ABOFs yielded wide and overlapping ranges of +0.3 to +6.3, +0.9 to +7.2, and -2.6 to +14.2‰, whereas those for PBOFs varied from -3.4 to +7.7, +1.4 to +9.4, and -4.1 to +12.5‰, respectively, making it challenging to distinguish the fate of sulfur compounds from ABOF and PBOF in the environment using sulfur isotopes. We conclude that the δN values of ABOFs and the O values of organic fertilizers are distinct from those of synthetic fertilizers and are a promising tool for tracing the fate of nutrients added by organic fertilizers to agroecosystems. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Carbon and nitrogen isotope ratios of factory-produced RDX and HMX.

PubMed

Howa, John D; Lott, Michael J; Chesson, Lesley A; Ehleringer, James R

2014-07-01

RDX and HMX are explosive compounds commonly used by the military and also occasionally associated with acts of terrorism. The isotopic characterization of an explosive can be a powerful approach to link evidence to an event or an explosives cache. We sampled explosive products and their reactants from commercial RDX manufacturers that used the direct nitration and/or the Bachmann synthesis process, and then analyzed these materials for carbon and nitrogen isotope ratios. For manufacturers using the Bachmann process, RDX (13)C enrichment relative to the hexamine substrate was small (+0.9‰) compared to RDX produced using the direct nitration process (+8.2‰ to +12.0‰). RDX (15)N depletion relative to the nitrogen-containing substrates (-3.6‰) was smaller in the Bachmann process than in the direct nitration process (-12.6‰ to -10.6‰). The sign and scale of these differences agree with theorized mechanisms of mass-dependent fractionation. We also examined the isotopic relationship between RDX and HMX isolated from explosive samples. The δ(13)C and δ(15)N values of RDX generally matched those of the HMX with few exceptions, most notably from a manufacturer known to make RDX using two different synthesis processes. The range in δ(13)C values of RDX in a survey of 100 samples from 12 manufacturers spanned 33‰ while the range spanned by δ(15)N values was 26‰; these ranges were much greater than any previously published observations. Understanding the relationship between products and reactants further explains the observed variation in industrially manufactured RDX and can be used as a diagnostic tool to analyze explosives found at a crime scene. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Hot N Sour Mantle Soup on Indian Plate During Cretaceous- Evidence from Clumped Isotope and Geochemical Studies of Sung Valley Carbonatite, India

NASA Astrophysics Data System (ADS)

Ghosh, P.; Banerjee, Y.; Tiwari, A.; Srivastava, R. K.

2015-12-01

Geological processes involved in the formation of Carbonatite rocks are complex and so is the understanding about its formational temperature. Fluid inclusion studies (1) on Carbonatite and their associated Ijolites showed a homogenization temperature of 1000-1100°C for Ijoltes and a temperature (T) range of 200-600°C was assigned to the carbonatite melts. Liquid immiscibility process is held responsible for the origin of parental carbonated (ijolititic/ nephelinitic) magma. The homogenization T signifies about a time interval during which there must be a considerable amount of T dropdown soon after the formation of Ijolite and subsequent crystallization of the residual carbonatite magma. However the lack of information about the T of the primary carbonated melt remains as an important area of petrological research. Experimental studies suggest a T range of 950-1400°C for the primary carbonate melt (2). Advent of Clumped isotope thermometry (3) allowed independent method for estimation of the formational T and provide avenues to derive composition of CO2 in equilibrium with carbonate melt. Earlier attempt involving carbonatites from several locations (4) captured range of T between 83°-416°C . Here we present our observation on calcite growth T in the carbonatites from the Cretaceous Sung valley ultramafic-alkaline-carbonatite complex. Based on stable C,O isotope study and Sr, Nd isotopic composition a mantle origin- genetically linked with the Kerguelen plume was proposed (5). Clumped isotope study on the same samples revealed consistent C and O isotope compositions, providing Δ47 values ranging from 0.32 to 0.48. δ13C and δ18O (in VPDB) values of the present study falls within the "Primary Igneous Carbonatite Field" (6). Using high T thermometry equation (7) we obtained a T range of 137-474 °C for the calcite present in the samples. The T recorded in our study is lower than that deduced experimental values of 960-625°C at 0.1 GPa (8) and fluid inclusion based data (1), suggesting involvement of water during calcite crystallization. Ref: 1.Romanchev 1972, Geochem Intern; 2.Gaillard et al., 2008, Science; 3. Ghosh et al.,2006, GCA ; 4. Dennis and Schrag, 2010, GCA; 5. Srivastava et al., 2005. Lithos ; 6.Taylor et al.,1967, GCA; 7. Kluge et al.,2015, GCA, 8. Watkinson and Willey, 1971, Jour. Of Petrology

Carbon and oxygen isotopic composition of coal and carbon dioxide derived from laboratory coal combustion: A preliminary study

USGS Publications Warehouse

Warwick, Peter D.; Ruppert, Leslie F.

2016-01-01

The concentration of carbon dioxide (CO2) in the atmosphere has dramatically increased from the start of the industrial revolution in the mid-1700s to present levels exceeding 400 ppm. Carbon dioxide derived from fossil fuel combustion is a greenhouse gas and a major contributor to on-going climate change. Carbon and oxygen stable isotope geochemistry is a useful tool to help model and predict the contributions of anthropogenic sources of CO2 in the global carbon cycle. Surprisingly few studies have addressed the carbon and oxygen isotopic composition of CO2 derived from coal combustion. The goal of this study is to document the relationships between the carbon and oxygen isotope signatures of coal and signatures of the CO2 produced from laboratory coal combustion in atmospheric conditions.Six coal samples were selected that represent various geologic ages (Carboniferous to Tertiary) and coal ranks (lignite to bituminous). Duplicate splits of the six coal samples were ignited and partially combusted in the laboratory at atmospheric conditions. The resulting coal-combustion gases were collected and the molecular composition of the collected gases and isotopic analyses of δ13C of CO2, δ13C of CH4, and δ18O of CO2 were analysed by a commercial laboratory. Splits (~ 1 g) of the un-combusted dried ground coal samples were analyzed for δ13C and δ18O by the U.S. Geological Survey Reston Stable Isotope Laboratory.The major findings of this preliminary work indicate that the isotopic signatures of δ13C (relative to the Vienna Pee Dee Belemnite scale, VPDB) of CO2 resulting from coal combustion are similar to the δ13CVPDB signature of the bulk coal (− 28.46 to − 23.86 ‰) and are not similar to atmospheric δ13CVPDB of CO2 (~ − 8 ‰, see http://www.esrl.noaa.gov/gmd/outreach/isotopes/c13tellsus.html). The δ18O values of bulk coal are strongly correlated to the coal dry ash yields and appear to have little or no influence on the δ18O values of CO2 resulting from coal combustion in open atmospheric conditions. There is a wide range of δ13C values of coal reported in the literature and the δ13C values from this study generally follow reported ranges for higher plants over geologic time. The values of δ18O (relative to Vienna Standard Mean Ocean Water) of CO2 derived from atmospheric combustion of coal and other high-carbon fuels (peat and coal) range from + 19.03 to + 27.03‰ and are similar to atmospheric oxygen δ18OVSMOW values which average + 23.8‰. Further work is needed on a broader set of samples to better define the relationships between coal composition and combustion-derived gases.

Massive isotopic effect in vacuum UV photodissociation of N2 and implications for meteorite data

PubMed Central

Chakraborty, Subrata; Muskatel, B. H.; Jackson, Teresa L.; Ahmed, Musahid; Levine, R. D.; Thiemens, Mark H.

2014-01-01

Nitrogen isotopic distributions in the solar system extend across an enormous range, from −400‰, in the solar wind and Jovian atmosphere, to about 5,000‰ in organic matter in carbonaceous chondrites. Distributions such as these require complex processing of nitrogen reservoirs and extraordinary isotope effects. While theoretical models invoke ion-neutral exchange reactions outside the protoplanetary disk and photochemical self-shielding on the disk surface to explain the variations, there are no experiments to substantiate these models. Experimental results of N2 photolysis at vacuum UV wavelengths in the presence of hydrogen are presented here, which show a wide range of enriched δ15N values from 648‰ to 13,412‰ in product NH3, depending upon photodissociation wavelength. The measured enrichment range in photodissociation of N2, plausibly explains the range of δ15N in extraterrestrial materials. This study suggests the importance of photochemical processing of the nitrogen reservoirs within the solar nebula. PMID:25267643

Stable Isotope Analysis of Precipitation Samples Obtained via Crowdsourcing Reveals the Spatiotemporal Evolution of Superstorm Sandy

PubMed Central

Good, Stephen P.; Mallia, Derek V.; Lin, John C.; Bowen, Gabriel J.

2014-01-01

Extra-tropical cyclones, such as 2012 Superstorm Sandy, pose a significant climatic threat to the northeastern United Sates, yet prediction of hydrologic and thermodynamic processes within such systems is complicated by their interaction with mid-latitude water patterns as they move poleward. Fortunately, the evolution of these systems is also recorded in the stable isotope ratios of storm-associated precipitation and water vapor, and isotopic analysis provides constraints on difficult-to-observe cyclone dynamics. During Superstorm Sandy, a unique crowdsourced approach enabled 685 precipitation samples to be obtained for oxygen and hydrogen isotopic analysis, constituting the largest isotopic sampling of a synoptic-scale system to date. Isotopically, these waters span an enormous range of values (21‰ for O, 160‰ for H) and exhibit strong spatiotemporal structure. Low isotope ratios occurred predominantly in the west and south quadrants of the storm, indicating robust isotopic distillation that tracked the intensity of the storm's warm core. Elevated values of deuterium-excess (25‰) were found primarily in the New England region after Sandy made landfall. Isotope mass balance calculations and Lagrangian back-trajectory analysis suggest that these samples reflect the moistening of dry continental air entrained from a mid-latitude trough. These results demonstrate the power of rapid-response isotope monitoring to elucidate the structure and dynamics of water cycling within synoptic-scale systems and improve our understanding of storm evolution, hydroclimatological impacts, and paleo-storm proxies. PMID:24618882

Isotopic composition and origin of indigenous natural perchlorate and co-occurring nitrate in the southwestern United States

USGS Publications Warehouse

Jackson, W. Andrew; Böhlke, John Karl; Gu, Baohua; Hatzinger, Paul B.; Sturchio, Neil C.

2010-01-01

Perchlorate (ClO4−) has been detected widely in groundwater and soils of the southwestern United States. Much of this ClO4− appears to be natural, and it may have accumulated largely through wet and dry atmospheric deposition. This study evaluates the isotopic composition of natural ClO4− indigenous to the southwestern U.S. Stable isotope ratios were measured in ClO4− (δ18O, Δ17O, δ37Cl) and associated NO3− (δ18O, Δ17O, δ15N) in groundwater from the southern High Plains (SHP) of Texas and New Mexico and the Middle Rio Grande Basin (MRGB) in New Mexico, from unsaturated subsoil in the SHP, and from NO3−-rich surface caliche deposits near Death Valley, California. The data indicate natural ClO4− in the southwestern U.S. has a wide range of isotopic compositions that are distinct from those reported previously for natural ClO4− from the Atacama Desert of Chile as well as all known synthetic ClO4−. ClO4− in Death Valley caliche has a range of high Δ17O values (+8.6 to +18.4 ‰), overlapping and extending the Atacama range, indicating at least partial atmospheric formation via reaction with ozone (O3). However, the Death Valley δ37Cl values (−3.1 to −0.8 ‰) and δ18O values (+2.9 to +26.1‰) are higher than those of Atacama ClO4−. In contrast, ClO4− from western Texas and New Mexico has much lower Δ17O (+0.3 to +1.3‰), with relatively high δ37Cl (+3.4 to +5.1 ‰) and δ18O (+0.5 to +4.8 ‰), indicating either that this material was not primarily generated with O3 as a reactant or that the ClO4− was affected by postdepositional O isotope exchange. High Δ17O values in ClO4− (Atacama and Death Valley) are associated with high Δ17O values in NO3−, indicating that both compounds preserve characteristics of O3-related atmospheric production in hyper-arid settings, whereas both compounds have low Δ17O values in less arid settings. Although Δ17O variations in terrestrial NO3− can be attributed to mixing of atmospheric (high Δ17O) and biogenic (low Δ17O) NO3−, variations in Δ17O of terrestrial ClO4− are not readily explained in the same way. This study provides important new constraints for identifying natural sources of ClO4− in different environments by multicomponent isotopic characteristics, while presenting the possibilities of divergent ClO4− formation mechanisms and(or) ClO4− isotopic exchange in biologically active environments.

Tracing sources of crustal contamination using multiple S and Fe isotopes in the Hart komatiite-associated Ni-Cu-PGE sulfide deposit, Abitibi greenstone belt, Ontario, Canada

NASA Astrophysics Data System (ADS)

Hiebert, R. S.; Bekker, A.; Houlé, M. G.; Wing, B. A.; Rouxel, O. J.

2016-10-01

Assimilation by mafic to ultramafic magmas of sulfur-bearing country rocks is considered an important contributing factor to reach sulfide saturation and form magmatic Ni-Cu-platinum group element (PGE) sulfide deposits. Sulfur-bearing sedimentary rocks in the Archean are generally characterized by mass-independent fractionation of sulfur isotopes that is a result of atmospheric photochemical reactions, which produces isotopically distinct pools of sulfur. Likewise, low-temperature processing of iron, through biological and abiotic redox cycling, produces a range of Fe isotope values in Archean sedimentary rocks that is distinct from the range of the mantle and magmatic Fe isotope values. Both of these signals can be used to identify potential country rock assimilants and their contribution to magmatic sulfide deposits. We use multiple S and Fe isotopes to characterize the composition of the potential iron and sulfur sources for the sulfide liquids that formed the Hart deposit in the Shaw Dome area within the Abitibi greenstone belt in Ontario (Canada). The Hart deposit is composed of two zones with komatiite-associated Ni-Cu-PGE mineralization; the main zone consists of a massive sulfide deposit at the base of the basal flow in the komatiite sequence, whereas the eastern extension consists of a semi-massive sulfide zone located 12 to 25 m above the base of the second flow in the komatiite sequence. Low δ56Fe values and non-zero δ34S and Δ33S values of the komatiitic rocks and associated mineralization at the Hart deposit is best explained by mixing and isotope exchange with crustal materials, such as exhalite and graphitic argillite, rather than intrinsic fractionation within the komatiite. This approach allows tracing the extent of crustal contamination away from the deposit and the degree of mixing between the sulfide and komatiite melts. The exhalite and graphitic argillite were the dominant contaminants for the main zone of mineralization and the eastern extension zone of the Hart deposit, respectively. Critically, the extent of contamination, as revealed by multiple S and Fe isotope systematics, is greatest within the deposit and decreases away from it within the komatiite flow. This pattern points to a local source of crustal contamination for the mantle-derived komatiitic melt and a low degree of homogenization between the mineralization and the surrounding lava flow. Coupled S and Fe isotope patterns like those identified at the Hart deposit may provide a useful tool for assessing the potential of a komatiitic sequence to host Ni-Cu-(PGE).

CCQM-K140: carbon stable isotope ratio delta values in honey

NASA Astrophysics Data System (ADS)

Dunn, P. J. H.; Goenaga-Infante, H.; Goren, A. C.; Şimşek, A.; Bilsel, M.; Ogrinc, N.; Armishaw, P.; Hai, L.

2017-01-01

As there can be small but measureable differences in isotope ratios between different sources of the same element/compound/material, isotope ratio measurements are applied in a number of different fields including archaeology, environmental science, geochemistry, forensic science and ecology. Isotope ratios for the light elements (H, C, N, O and S) are typically reported as δ-values which are isotope ratios expressed relative to an internationally agreed standard (this standard is the zero-point on the scale), although absolute isotope ratios which are traceable to the SI have also been reported. The IAWG has been granted a traceability exception for the use of arbitrary delta scales until SI traceability can be established at the required level of uncertainty but this goal is some years away. While the CCQM IAWG has previously organised several pilot studies on isotope ratio determination (CCQM-P75: Stable isotope delta values in methionine, 2006; CCQM-P105: Sr isotope ratios in wine, 2008; CCQM-K98: Pb isotope ratios in bronze with additional delta values in CCQM-P134, 2011), it has been a number of years since delta values of light elements have been considered and there has been no key comparison (KC). Therefore, the IAWG has included the need for a KC (CCQM-K140) based on an arbitrary delta scale in its program to support ongoing requirements to demonstrate core capabilities as well as specific claims of measurement capability (CMCs) in this area. The performance of all five of the CCQM-K140 participants was very good, illustrating their ability to obtain accurate results for carbon isotope ratios, within the calibration range afforded by internationally agreed reference materials (δ13CVPDB-LSVEC between -47.32 % and +535.3 %) with measurement uncertainties of between 0.08 and 0.28 %. This was despite the fact that no two participants used exactly the same approach in terms of instrumentation or data treatment. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

IRMS to study a common cocaine cutting agent: phenacetin.

PubMed

Ladroue, Virginie; Dujourdy, Laurence; Besacier, Fabrice; Jame, Patrick

2017-03-01

Phenacetin is a pharmaceutical closely related to acetaminophen that has been banned in France for a long time due to its nephritic and carcinogenic adverse effects. It frequently appears in cocaine seizures as a cutting agent. Following both sanitary and intelligence motivations, this molecule was chosen for this study, and stable isotopes seemed to be the most appropriate tool. A total of 228 seized samples were collected over a 6-year period, and 8 standards of known origin were purchased. They were submitted to gas chromatography (GC) or elemental analysis - isotope ratio mass spectrometry (EA-IRMS) measurements, depending on their complexity. Stable isotope ratios of carbon, hydrogen, and nitrogen for a part of the sample set, were acquired. The isotopic values of phenacetin standards acquired from various providers located worldwide are quite spread, which indicates that stable isotopes could be used to discriminate manufacturers. However, the measured values of most of the seized samples are concentrated in a narrow range, tending to demonstrate that phenacetin is smuggled from a single source or similar ones. Consequently, stable isotopes could only be used to exclude that several samples come from a common source. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Calcium and magnesium isotope systematics in rivers draining the Himalaya-Tibetan-Plateau region: Lithological or fractionation control?

NASA Astrophysics Data System (ADS)

Tipper, Edward T.; Galy, Albert; Bickle, Mike J.

2008-02-01

In rivers draining the Himalaya-Tibetan-Plateau region, the 26Mg/ 24Mg ratio has a range of 2‰ and the 44Ca/ 42Ca ratio has a range of 0.6‰. The average δ26Mg values of tributaries from each of the main lithotectonic units (Tethyan Sedimentary Series (TSS), High Himalayan Crystalline Series (HHCS) and Lesser Himalayan Series (LHS)) are within 2 standard deviation analytical uncertainty (0.14‰). The consistency of average riverine δ26Mg values is in contrast to the main rock types (limestone, dolostone and silicate) which range in their average δ26Mg values by more than 2‰. Tributaries draining the dolostones of the LHS differ in their δ44Ca values compared to tributaries from the TSS and HHCS. The chemistry of these river waters is strongly influenced by dolostone (solute Mg/Ca close to unity) and both δ26Mg (-1.31‰) and δ44Ca (0.64‰) values are within analytical uncertainty of the LHS dolostone. These are the most elevated δ44Ca values in rivers and rock reported so far demonstrating that both riverine and bedrock δ44Ca values may show greater variability than previously thought. Although rivers draining TSS limestone have the lowest δ26Mgandδ44Ca values at -1.41 and 0.42‰, respectively, both are offset to higher values compared to bedrock TSS limestone. The average δ26Mg value of rivers draining mainly silicate rock of the HHCS is -1.25‰, lower by 0.63‰ than the average silicate rock. These differences are consistent with a fractionation of δ26Mg values during silicate weathering. Given that the proportion of Mg exported from the Himalaya as solute Mg is small, the difference in 26Mg/ 24Mg ratios between silicate rock and solute Mg reflects the 26Mg/ 24Mg isotopic fractionation factor ( αsilicate-dissolvedMg) between silicate and dissolved Mg during incongruent silicate weathering. The value of αsilicate-dissolvedMg of 0.99937 implies that in the TSS, solute Mg is primarily derived from silicate weathering, whereas the source of Ca is overwhelmingly derived from carbonate weathering. The average δ44Ca value in HHCS rivers is within uncertainty of silicate rock at 0.39‰. The widespread hot springs of the High Himalaya have an average δ26Mg value of -0.46‰ and an average δ44Ca value of 0.5‰, distinct from riverine values for δ26Mg but similar to riverine δ44Ca values. Although rivers draining each major rock type have δ44Ca and δ26Mg values in part inherited from bedrock, there is no correlation with proxies for carbonate or silicate lithology such as Na/Ca ratios, suggesting that Ca and Mg are in part recycled. However, in spite of the vast contrast in vegetation density between the arid Tibetan Plateau and the tropical Lesser Himalaya, the isotopic fractionation factor for Ca and Mg between solute and rocks are not systematically different suggesting that vegetation may only recycle a small amount of Ca and Mg in these catchments. The discrepancy between solute and solid Ca and Mg isotope ratios in these rivers from diverse weathering environments highlight our lack of understanding concerning the origin and subsequent path of Ca and Mg, bound as minerals in rock, and released as cations in rivers. The fractionation of Ca and Mg isotope ratios may prove useful for tracing mechanisms of chemical alteration. Ca isotope ratios of solute riverine Ca show a greater variability than previously acknowledged. The variability of Ca isotope ratios in modern rivers will need to be better quantified and accounted for in future models of global Ca cycling, if past variations in oceanic Ca isotope ratios are to be of use in constraining the past carbon cycle.

Zinc isotopes in sphalerite from base metal deposits in the Red Dog district, northern Alaska

USGS Publications Warehouse

Kelley, K.D.; Wilkinson, J.J.; Chapman, J.B.; Crowther, H.L.; Weiss, D.J.

2009-01-01

Analyses of sphalerite samples from shale-hosted massive sulfide and stratigraphically underlying vein breccia deposits in the Red Dog district in northern Alaska show a range ??66Zn values from zero to 0.60 per mil. The lowest values are observed in the vein breccia deposits, and the stratigraphically overlying (but structurally displaced) shale-hosted massive sulfide deposits show a systematic trend of increasing ??66Zn values from south to north (Main-Aqqaluk-Paalaaq-Anarraaq). The ??66Zn values are inversely correlated with sphalerite Fe/Mn ratio and also tend to be higher in low Cu sphalerite, consistent with precipitation of lower ??66Zn sphalerite closer to the principal hydrothermal fluid conduits. The most likely control on isotopic variation is Rayleigh fractionation during sulfide precipitation, with lighter zinc isotopes preferentially incorporated in the earliest sphalerite to precipitate from ore fluids at deeper levels (vein breccias) and close to the principal fluid conduits in the orebodies, followed by precipitation of sulfides with higher ??66Zn values in shallower and/or more distal parts of the flow path. There is no systematic variation among the paragenetic stages of sphalerite from a single deposit, suggesting an isotopically homogeneous zinc source and consistent transport-deposition conditions and/or dissolution-reprecipitation of earlier sphalerite without significant fractionation. Decoupled Zn and S isotope compositions are best explained by mixing of separate metal- and sulfur-bearing fluids at the depositional site. The results confirm that Zn isotopes may be a useful tracer for distinguishing between the central and distal parts of large hydrothermal systems as previously suggested and could therefore be of use in exploration. ?? 2009 by Economic Geology.

Investigating human responses to political and environmental change through paleodiet and paleomobility.

PubMed

Knudson, Kelly J; Torres-Rouff, Christina; Stojanowski, Christopher M

2015-06-01

Bioarchaeological approaches are well suited for examining past responses to political and environmental changes. In the Andes, we hypothesized that political and environmental changes around AD 1100 resulted in behavioral changes, visible as shifts in paleodiet and paleomobility, among individuals in the San Pedro de Atacama oases and Loa River Valley. To investigate this hypothesis, we generated carbon and oxygen isotope data from cemeteries dating to the early Middle Horizon (Larache, Quitor-5, Solor-3), late Middle Horizon (Casa Parroquial, Coyo Oriental, Coyo-3, Solcor-Plaza, Solcor-3, Tchecar), and Late Intermediate Period (Caspana, Quitor-6 Tardío, Toconce, Yaye-1, Yaye-2, Yaye-3, Yaye-4). Carbon isotope data demonstrate a greater range of carbon sources during the late Middle Horizon compared with the Late Intermediate Period; while most individuals consumed largely C3 sources, some late Middle Horizon individuals consumed more C4 sources. Oxygen isotope data demonstrate greater diversity in drinking water sources during the late Middle Horizon compared with the Late Intermediate Period. Water samples were analyzed to provide baseline data on oxygen isotope variability within the Atacama Desert, and demonstrated that oxygen isotope values are indistinguishable in the San Pedro and Loa Rivers. However, oxygen isotope values in water sources in the high-altitude altiplano and coast are distinct from those in the San Pedro and Loa Rivers. In conclusion, instead of utilizing a wider variety of resources after environmental and political changes, individuals exhibited a wider range of paleodietary and paleomobility strategies during the Middle Horizon, a period of environmental and political stability. © 2015 Wiley Periodicals, Inc.

Accurate experimental determination of the isotope effects on the triple point temperature of water. II. Combined dependence on the 18O and 17O abundances

NASA Astrophysics Data System (ADS)

Faghihi, V.; Kozicki, M.; Aerts-Bijma, A. T.; Jansen, H. G.; Spriensma, J. J.; Peruzzi, A.; Meijer, H. A. J.

2015-12-01

This paper is the second of two articles on the quantification of isotope effects on the triple point temperature of water. In this second article, we address the combined effects of 18O and 17O isotopes. We manufactured five triple point cells with waters with 18O and 17O abundances exceeding widely the natural abundance range while maintaining their natural 18O/17O relationship. The 2H isotopic abundance was kept close to that of VSMOW (Vienna Standard Mean Ocean Water). These cells realized triple point temperatures ranging between  -220 μK to 1420 μK with respect to the temperature realized by a triple point cell filled with VSMOW. Our experiment allowed us to determine an accurate and reliable value for the newly defined combined 18, 17O correction parameter of AO  =  630 μK with a combined uncertainty of 10 μK. To apply this correction, only the 18O abundance of the TPW needs to be known (and the water needs to be of natural origin). Using the results of our two articles, we recommend a correction equation along with the coefficient values for isotopic compositions differing from that of VSMOW and compare the effect of this new equation on a number of triple point cells from the literature and from our own institute. Using our correction equation, the uncertainty in the isotope correction for triple point cell waters used around the world will be  <1 μK.

Variation in hair δ13C and δ15N values in long-tailed macaques (Macaca fascicularis) from Singapore

USGS Publications Warehouse

Schillaci, Michael A.; Castellini, J. Margaret; Stricker, Craig A.; Jones-Engel, Lisa; Lee, Benjamin P.Y.-H.

2014-01-01

Much of the primatology literature on stable isotope ratios of carbon (δ13C) and nitrogen (δ15N) has focused on African and New World species, with comparatively little research published on Asian primates. Here we present hair δ13C and δ15N isotope values for a sample of 33 long-tailed macaques from Singapore. We evaluate the suggestion by a previous researcher that forest degradation and biodiversity loss in Singapore have led to a decline in macaque trophic level. The results of our analysis indicated significant spatial variability in δ13C but not δ15N. The range of variation in δ13C was consistent with a diet based on C3 resources, with one group exhibiting low values consistent with a closed canopy environment. Relative to other macaque species from Europe and Asia, the macaques from Singapore exhibited a low mean δ13C value but mid-range mean δ15N value. Previous research suggesting a decline in macaque trophic level is not supported by the results of our study.

[Simultaneous determination of delta13C values of glycerol and ethanol in wine by liquid chromatography coupled with isotope ratio mass spectrometry].

PubMed

Li, Xuemin; Jia, Guangqun; Cao, Yanzhong; Zhang, Jinjie; Wang, Lei; Sun, Huiyuan

2013-12-01

A novel procedure was established for the characterization of delta13C values of glycerol and ethanol in wine by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Several parameters influencing the separation of glycerol and ethanol from wine matrix were optimized. The precision and accuracy of the proposed method were 0.15 per thousand to 0.26 per thousand and 0.11 per thousand to 0.28 per thousand, respectively. The results obtained for 40 wine samples displayed that the delta13C value of glycerol ranged from--26.87 per thousand to--32.96 per thousand and that of ethanol ranged from--24.06 per thousand to--28.29 per thousand. Close correlations (R = 0.82) were obtained between the delta13C values of glycerol and ethanol. The proposed method didn't need complex sample treatment, and the delta13C values of glycerol and ethanol in wine can be simultaneously determined, thus improving the method in terms of simplicity and speed compared with traditional methods.

Mercury Stable Isotopes Discriminate Different Populations of European Seabass and Trace Potential Hg Sources around Europe.

PubMed

Cransveld, Alice; Amouroux, David; Tessier, Emmanuel; Koutrakis, Emmanuil; Ozturk, Ayaka A; Bettoso, Nicola; Mieiro, Cláudia L; Bérail, Sylvain; Barre, Julien P G; Sturaro, Nicolas; Schnitzler, Joseph; Das, Krishna

2017-11-07

Our study reports the first data on mercury (Hg) isotope composition in marine European fish, for seven distinct populations of the European seabass, Dicentrarchus labrax. The use of δ 202 Hg and Δ 199 Hg values in SIBER enabled us to estimate Hg isotopic niches, successfully discriminating several populations. Recursive-partitioning analyses demonstrated the relevance of Hg stable isotopes as discriminating tools. Hg isotopic values also provided insight on Hg contamination sources for biota in coastal environment. The overall narrow range of δ 202 Hg around Europe was suggested to be related to a global atmospheric contamination while δ 202 Hg at some sites was linked either to background contamination, or with local contamination sources. Δ 199 Hg was related to Hg levels of fish but we also suggest a relation with ecological conditions. Throughout this study, results from the Black Sea population stood out, displaying a Hg cycling similar to fresh water lakes. Our findings bring out the possibility to use Hg isotopes in order to discriminate distinct populations, to explore the Hg cycle on a large scale (Europe) and to distinguish sites contaminated by global versus local Hg source. The interest of using Hg sable isotopes to investigate the whole European Hg cycle is clearly highlighted.

Factors controlling shell carbon isotopic composition of land snail Acusta despecta sieboldiana estimated from laboratory culturing experiment

NASA Astrophysics Data System (ADS)

Zhang, N.; Yamada, K.; Suzuki, N.; Yoshida, N.

2014-10-01

The carbon isotopic composition (δ13C) of land snail shell carbonate derives from three potential sources: diet, atmospheric CO2, and ingested carbonate (limestone). However, their relative contributions remain unclear. Under various environmental conditions, we cultured one land snail subspecies, Acusta despecta sieboldiana, collected from Yokohama, Japan, and confirmed that all of these sources affect shell carbonate δ13C values. Herein, we consider the influences of metabolic rates and temperature on the carbon isotopic composition of the shell carbonate. Based on results obtained from previous works and this study, a simple but credible framework is presented to illustrate how each source and environmental parameter affects shell carbonate δ13C values. According to this framework and some reasonable assumptions, we estimated the contributions of different carbon sources for each snail individual: for cabbage-fed (C3 plant) groups, the contributions of diet, atmospheric CO2, and ingested limestone vary in the ranges of 66-80, 16-24, and 0-13%, respectively. For corn-fed (C4 plant) groups, because of the possible food stress (less ability to consume C4 plants), the values vary in the ranges of 56-64, 18-20, and 16-26%, respectively. Moreover, according to the literature and our observations, the subspecies we cultured in this study show preferences towards different plant species for food. Therefore, we suggest that the potential food preference should be considered adequately for some species in paleoenvironment studies. Finally, we inferred that only the isotopic exchange of the calcite-HCO3--aragonite equilibrium during egg laying and hatching of our cultured snails controls carbon isotope fractionation.

Detection of counterfeit antiviral drug Heptodin and classification of counterfeits using isotope amount ratio measurements by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) and isotope ratio mass spectrometry (IRMS).

PubMed

Santamaria-Fernandez, Rebeca; Hearn, Ruth; Wolff, Jean-Claude

2009-06-01

Isotope ratio mass spectrometry (IRMS) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) are highly important techniques that can provide forensic evidence that otherwise would not be available. MC-ICP-MS has proved to be a very powerful tool for measuring high precision and accuracy isotope amount ratios. In this work, the potential of combining isotope amount ratio measurements performed by MC-ICP-MS and IRMS for the detection of counterfeit pharmaceutical tablets has been investigated. An extensive study for the antiviral drug Heptodin has been performed for several isotopic ratios combining MC-ICP-MS and an elemental analyser EA-IRMS for stable isotope amount ratio measurements. The study has been carried out for 139 batches of the antiviral drug and analyses have been performed for C, S, N and Mg isotope ratios. Authenticity ranges have been obtained for each isotopic system and combined to generate a unique multi-isotopic pattern only present in the genuine tablets. Counterfeit tablets have then been identified as those tablets with an isotopic fingerprint outside the genuine isotopic range. The combination of those two techniques has therefore great potential for pharmaceutical counterfeit detection. A much greater power of discrimination is obtained when at least three isotopic systems are combined. The data from these studies could be presented as evidence in court and therefore methods need to be validated to support their credibility. It is also crucial to be able to produce uncertainty values associated to the isotope amount ratio measurements so that significant differences can be identified and the genuineness of a sample can be assessed.

Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

NASA Technical Reports Server (NTRS)

Baur, M. E.; Hayes, J. M.; Studley, S. A.; Walter, M. R.

1985-01-01

Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

Reconstructing diet in Napoleon's Grand Army using stable carbon and nitrogen isotope analysis.

PubMed

Holder, Sammantha; Dupras, Tosha L; Jankauskas, Rimantas; Williams, Lana; Schultz, John

2017-05-01

Historical evidence has provided information regarding disease and mortality in Napoleon Bonaparte's Grand Army, but dietary information beyond individual soldier accounts remains scarce. The purpose of this research is to reconstruct the diets of Napoleon's multiethnic army who were associated with the Russian Campaign of 1812. We conducted stable carbon and nitrogen isotope ratio analysis on femoral bone collagen of 78 individuals recovered from a salvage excavation at the mass gravesite of Šiaurės miestelis in Vilnius, Lithuania. These individuals were later discovered to be Napoleonic soldiers and camp followers who participated in the 1812 Russian Campaign. Stable carbon isotope ratios range from -19.2‰ to -11.8‰, with a mean of -17.8‰ ± 1.5‰ (1 σ). Stable nitrogen isotope ratios range from 7.1‰ to 13.6‰, with a mean of 10.5‰ ± 1.4‰ (1 σ). Both δ 13 C and δ 15 N values show a wide range of variation. Stable isotope data indicate considerable dietary variation in this population associated with a multiethnic and socially stratified military population. Diets ranged from predominantly C 3 -based to predominantly C 4 -based, with varying inputs of terrestrial, freshwater, and marine animal protein. Comparison with other European populations further denotes the exceptional range of dietary variation of soldiers and camp followers in Napoleon's army. © 2017 Wiley Periodicals, Inc.

A reconnaissance study of oxygen, hydrogen and strontium isotopes in geochemically diverse lakes, Western Nebraska, USA

USGS Publications Warehouse

Gosselin, D.C.; Nabelek, P.E.; Peterman, Z.E.; Sibray, S.

1997-01-01

Reconnaissance ??18O,, ??D, and ??87Sr data for fifteen lakes in the Western Lakes Region of the Sand Hills of Nebraska indicate dynamic hydrologic systems. The rather narrow range of ??87Sr from lake water (1.1 to 2.1) and groundwater (0.9 to 1.7) indicates that the groundwater is generally unradiogenic. Groundwater residence times and relatively unradiogenic volcanic ash within the dune sediments control the ??87Sr values. Based on the mutual variations of ??18O and ??D, the lakes can be divided into three groups. In Group 1, both ??18O and ??D values increase from spring to fall. The ??18O and ??D values in Group 2 decreased from spring to fall. Group 3 are ephemeral lakes that went dry some time during 1992. The data and isotopic modeling show that variations in the ratio of evaporation relative to groundwater inflow, local humidity conditions, and the ??(a) has substantial influence on the isotopic composition. In addition, isotopic behavior in ephemeral hakes can be rather unusual because of the changing activities of water and mineral precipitation and redissolution. The annual and interannual isotopic variability of these lakes which is reflected in the paleonvironmental indicators may be the rule rather than the exception in these types of systems.

Paleoenvironmental implications of taxonomic variation among δ 15 N values of chloropigments

NASA Astrophysics Data System (ADS)

Higgins, Meytal B.; Wolfe-Simon, Felisa; Robinson, Rebecca S.; Qin, Yelun; Saito, Mak A.; Pearson, Ann

2011-11-01

Natural variations in the ratios of nitrogen isotopes in biomass reflect variations in nutrient sources utilized for growth. In order to use δ 15N values of chloropigments of photosynthetic organisms to determine the corresponding δ 15N values of biomass - and by extension, surface waters - the isotopic offset between chlorophyll and biomass must be constrained. Here we examine this offset in various geologically-relevant taxa, grown using nutrient sources that may approximate ocean conditions at different times in Earth's history. Phytoplankton in this study include cyanobacteria (diazotrophic and non-diazotrophic), eukaryotic algae (red and green), and anoxygenic photosynthetic bacteria (Proteobacteria), as well as environmental samples from sulfidic lake water. Cultures were grown using N 2, NO 3-, and NH 4+ as nitrogen sources, and were examined under different light regimes and growth conditions. We find surprisingly high variability in the isotopic difference (δ 15N biomass - δ 15N chloropigment) for prokaryotes, with average values for species ranging from -12.2‰ to +11.7‰. We define this difference as ɛpor, a term that encompasses diagenetic porphyrins and chlorins, as well as chlorophyll. Negative values of ɛpor reflect chloropigments that are 15N-enriched relative to biomass. Notably, this enrichment appears to occur only in cyanobacteria. The average value of ɛpor for freshwater cyanobacterial species is -9.8 ± 1.8‰, while for marine cyanobacteria it is -0.9 ± 1.3‰. These isotopic effects group environmentally but not phylogenetically, e.g., ɛpor values for freshwater Chroococcales resemble those of freshwater Nostocales but differ from those of marine Chroococcales. Our measured values of ɛpor for eukaryotic algae (range = 4.7-8.7‰) are similar to previous reports for pure cultures. For all taxa studied, values of ɛpor do not depend on the type of nitrogen substrate used for growth. The observed environmental control of ɛpor suggests that values of ɛpor could be useful for determining the fractional burial of eukaryotic vs. cyanobacterial organic matter in the sedimentary record.

Mo isotope fractionation during hydrothermal evolution of porphyry Cu systems

NASA Astrophysics Data System (ADS)

Shafiei, Behnam; Shamanian, GholamHossein; Mathur, Ryan; Mirnejad, Hassan

2015-03-01

We present Mo isotope compositions of molybdenite types from three successive stages of ore deposition in several porphyry copper deposits of the Kerman region, Iran. The data provide new insights into controlling processes on Mo isotope fractionation during the hydrothermal evolution of porphyry systems. The Mo isotope compositions of 27 molybdenite samples show wide variations in δ97Mo ranging from -0.37 to +0.92 ‰. The data reveal that molybdenites in the early and transitional stages of mineralization (preferentially 2H polytypes; δ97Mo mean = 0.35 ‰) have higher δ97Mo values than late stage (mainly 3R polytypes; δ97Mo mean = 0.02 ‰) molybdenites. This trend suggests that fractionation of Mo isotopes occurred in high-temperature stages of mineralization and that hydrothermal systems generally evolve towards precipitation of molybdenite with lower δ97Mo values. Taking into account the genetic models proposed for porphyry Cu deposits along with the temperature-dependent fractionation of Mo isotope ratios, it is proposed that large variations of Mo isotopes in the early and the transitional stages of ore deposition could be controlled by the separation of the immiscible ore-forming fluid phases with different density, pH, and ƒO2 properties (i.e., brine and vapor). The fractionation of Mo isotopes during fluid boiling and Rayleigh distillation processes likely dominates the Mo isotope budget of the remaining ore-forming fluids for the late stage of mineralization. The lower δ97Mo values in the late stage of mineralization can be explained by depletion of the late ore-forming hydrothermal solutions in 97Mo, as these fluids have moved to considerable distance from the source. Finally, the relationship observed between MoS2 polytypes (2H and 3R) and their Mo isotopic compositions can be explained by the molecular vibration theory, in which heavier isotopes are preferentially partitioned into denser primary 2H MoS2 crystals.

Silicon isotopes reveal recycled altered oceanic crust in the mantle sources of Ocean Island Basalts

NASA Astrophysics Data System (ADS)

Pringle, Emily A.; Moynier, Frédéric; Savage, Paul S.; Jackson, Matthew G.; Moreira, Manuel; Day, James M. D.

2016-09-01

The study of silicon (Si) isotopes in Ocean Island Basalts (OIB) has the potential to discern between different models for the origins of geochemical heterogeneities in the mantle. Relatively large (∼several per mil per atomic mass unit) Si isotope fractionation occurs in low-temperature environments during biochemical and geochemical precipitation of dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes relative to the dissolved Si. In contrast, only a limited range (∼tenths of a per mil) of Si isotope fractionation has been observed from high-temperature igneous processes. Therefore, Si isotopes may be useful as tracers for the presence of crustal material within OIB mantle source regions that experienced relatively low-temperature surface processes in a manner similar to other stable isotope systems, such as oxygen. Characterizing the isotopic composition of the mantle is also of central importance to the use of the Si isotope system as a basis for comparisons with other planetary bodies (e.g., Moon, Mars, asteroids). Here we present the first comprehensive suite of high-precision Si isotope data obtained by MC-ICP-MS for a diverse suite of OIB. Samples originate from ocean islands in the Pacific, Atlantic, and Indian Ocean basins and include representative end-members for the EM-1, EM-2, and HIMU mantle components. On average, δ30Si values for OIB (-0.32 ± 0.09‰, 2 sd) are in general agreement with previous estimates for the δ30Si value of Bulk Silicate Earth (-0.29 ± 0.07‰, 2 sd; Savage et al., 2014). Nonetheless, some small systematic variations are present; specifically, most HIMU-type (Mangaia; Cape Verde; La Palma, Canary Islands) and Iceland OIB are enriched in the lighter isotopes of Si (δ30Si values lower than MORB), consistent with recycled altered oceanic crust and lithospheric mantle in their mantle sources.

Diamonds from Orapa Mine show a clear subduction signature in SIMS stable isotope data

NASA Astrophysics Data System (ADS)

Chinn, Ingrid L.; Perritt, Samantha H.; Stiefenhofer, Johann; Stern, Richard A.

2018-05-01

Spatially resolved analyses reveal considerable isotopic heterogeneity within and among diamonds ranging in size from 0.15 to 4.75 mm from the Orapa Mine, Botswana. The isotopic data are interpreted in conjunction with nitrogen aggregation state data and growth zone relationships from cathodoluminescence images. The integrated information confirms that a distinct diamond growth event (with low IaAB nitrogen aggregation states, moderately high nitrogen contents and δ13C and δ15N values compatible with average mantle values) is younger than the dominant population(s) of Type IaAB diamonds and cores of composite diamonds with more negative and positive δ13C and δ15N values, respectively. A significant proportion of the older diamond generation has high nitrogen contents, well outside the limit sector relationship, and these diamonds are likely to reflect derivation from subducted organic matter. Diamonds with low δ13C values combined with high nitrogen contents and positive δ15N values have not been previously widely recognised, even in studies of diamonds from Orapa. This may have been caused by prior analytical bias towards inclusion-bearing diamonds that are not necessarily representative of the entire range of diamond populations, and because of average measurements from heterogeneous diamonds measured by bulk combustion methods. Two distinct low nitrogen/Type II microdiamond populations were recognised that do not appear to continue into the macrodiamond sizes in the samples studied. Other populations, e.g. those containing residual singly-substituted nitrogen defects, range in size from small microdiamonds to large macrodiamonds. The total diamond content of the Orapa kimberlite thus reflects a complex assortment of multiple diamond populations.

Cosmogenic effects on Cu isotopes in IVB iron meteorites

NASA Astrophysics Data System (ADS)

Chen, Heng; Moynier, Frédéric; Humayun, Munir; Bishop, M. Cole; Williams, Jeffrey T.

2016-06-01

We measured Cu isotope compositions of 12 out of the 14 known IVB iron meteorites. Our results show that IVB iron meteorites display a very large range of δ65Cu values (-5.84‰ < δ65Cu < -0.24‰; defined as per mil deviation of the 65Cu/63Cu ratio from the NIST-976 standard). These Cu isotopic data display clear correlations with W, Pt, and Os isotope ratios, which are very sensitive to secondary neutron capture due to galactic cosmic ray (GCR) irradiation. This demonstrates that δ65Cu in IVB irons is majorly modified by neutron capture by the reaction 62Ni(n,γ)63Ni followed by beta decay to 63Cu. Using correlations with Pt and Os neutron dosimeters, we calculated a pre-exposure δ65Cu of -0.3 ± 0.8‰ (95% conf.) of IVB irons that agrees well with the Cu isotopic compositions of other iron meteorite groups and falls within the range of chondrites. This shows that the volatile depletion of the IVB parent body is not due to evaporation that should have enriched IVB irons in the heavy Cu isotopes.

Isotopic analysis of cometary organic matter

NASA Technical Reports Server (NTRS)

Kerridge, John F.

1991-01-01

Carbon isotope ratios have been measured for CN in the coma of Comet Halley and for several CHON particles emitted by Halley. Of these, only the CHON-particle data may be reasonably related to organic matter in the cometary nucleus, but the true range of (C-13)/(C-12) values in those particles is quite uncertain. The D/H ratio in H2O in the Halley coma resembles that in Titan/Uranus.

Aragonite-Calcite Inversion During Biogenic Carbonate Sampling: Considerations for Interpreting Isotopic Measurements in Paleoclimate Studies

NASA Astrophysics Data System (ADS)

Waite, A. J.; Swart, P. K.

2011-12-01

As aragonite is the metastable polymorph of calcium carbonate, it lends itself to monotropic inversion to the more stable polymorph, calcite. This inversion is possible through an increase in the temperature and pressure conditions to which the sample is exposed and, although first noted nearly a century ago, has been primarily discussed in the context of sample roasting prior to analyses in paleoclimatological studies. Over the last several decades, however, researchers have found evidence to suggest that the friction associated with the sampling of biogenic carbonates via milling/drilling also induces inversion. Furthermore, this inversion may be associated with a shift in measured oxygen isotopic values and ultimately have significant implications for the interpretation of paleoclimatic reconstructions. Despite this, the isotopic heterogeneity of biogenic aragonite skeletons makes the effects of inversion challenging to test and the subject remains underrepresented in the literature. Here we present a first order study into the effects of milling on both the mineralogy and isotopic compositions measured in sclerosponges, corals, and molluscs. X-Ray diffraction analysis of samples hand ground with a mortar and pestle reveal 100% aragonitic skeletons. Conversely, samples milled with a computerized micromill show measurable inversion to calcite. On average, percent inversion of aragonite to calcite for individual specimens was 15% for sclerosponges, 16% for corals, and 9% for molluscs. Isotopic data from these specimens show that the higher the percentage of aragonite inverted to calcite, the more depleted the measured oxygen isotopic values. In the largest of the datasets (sclerosponges), it is evident that the range of oxygen isotope values from milled samples (-0.02 to +0.84%) exceeds the range in values for those samples which were hand ground and showed no inversion (+0.53 to +0.90%). This, coupled with the strong correlation between the two variables, suggests that the isotopic depletion is tied to the polymorphic inversion of aragonite to calcite, and not just random chance based on natural isotopic variability in the skeleton. There appears to be no relationship between the percent inversion and carbon isotopic composition. Elemental ratios also appear to remain stable during the heating and inversion process. The findings of this and published studies present, in many cases, conflicting views of the isotopic fractionation associated with inversion of aragonite to calcite. Discrepancies such as this likely result from subtle differences in sampling protocol related to instruments, drill bits, skeletal density, and possibly even laboratory conditions like temperature and humidity, further complicating our understanding and interpretation of such observations. Preliminary investigation suggests that altering milling conditions or wet milling may reduce the extent of alteration. Unfortunately, milling/drilling remains one of the only practical methods of sampling biogenic carbonates at a high resolution for paleoclimate work and, as such, caution should be taken in the interpretation of oxygen isotopic measurements from specimens of this nature.

Carbon-isotopic analysis of individual pollen grains from C 3 and C 4 grasses using a spooling-wire microcombustion interface

NASA Astrophysics Data System (ADS)

Nelson, David M.; Hu, Feng Sheng; Mikucki, Jill A.; Tian, Jian; Pearson, Ann

2007-08-01

Pollen grains from grasses using the C 3 and C 4 photosynthetic pathways have distinct ranges of δ 13C values that may be used to estimate their relative abundance in paleorecords. We evaluated a spooling-wire microcombustion device interfaced with an isotope-ratio mass spectrometer (SWiM-IRMS) for δ 13C analysis of individual grass-pollen grains. Pollen from four C 3 and four C 4 grass species was isolated through micromanipulation and analyzed as single grains suspended in water. A carbon yield greater than the 2 σ range of the carbon content of blanks containing only water was used to distinguish samples containing pollen ("pollen present") from those not containing pollen. This criterion resulted in the exclusion of ˜45% of the 946 samples applied to the wire. The average δ 13C values (±1 σ) of the remaining samples were -26.9‰ (±6.3‰) and -11.5‰ (±9.6‰) for C 3 grasses and C 4 grasses, respectively, after blank-correcting the δ 13C data. These results suggest that the SWiM-IRMS system can be used to distinguish C 3 from C 4 grass pollen. The high variability in measured δ 13C values is likely caused by a combination of factors. These include natural isotopic variability among individual pollen grains; the relatively poor precision that can be obtained when determining δ 13C values of such small samples; and the uncertainty in the magnitude, isotopic composition, and stability of the analytical blank. Nonetheless, high percentages of individual pollen grains were correctly classified as being of either C 3 or C 4 origin. On average, 90% (range = 78-100%) of pollen grains from C 3 grasses had δ 13C values more negative than the cutoff threshold of -19.2‰; while 84% (range = 77-90%) of pollen grains from C 4 grasses had δ 13C values more positive than -19.2‰. Compared with analysis using an elemental analyzer interfaced with an IRMS (EA-IRMS), the number of pollen grains required for δ 13C-based evaluation of C 3/C 4 grass composition is many times lower with the SWiM-IRMS. Additionally, δ 13C data from the SWiM-IRMS does not need to be incorporated into a mixing model to derive estimates of the abundance of C 3 and C 4 grass pollen. Carbon-isotopic analysis of individual grass-pollen grains using the SWiM-IRMS system may help improve our understanding of the evolutionary and ecological significance of grass taxa in the paleorecord.

A late Miocene-early Pliocene chain of lakes fed by the Colorado River: Evidence from Sr, C, and O isotopes of the Bouse Formation and related units between Grand Canyon and the Gulf of California

USGS Publications Warehouse

Roskowski, J.A.; Patchett, P.J.; Spencer, J.E.; Pearthree, P.A.; Dettman, D.L.; Faulds, J.E.; Reynolds, A.C.

2010-01-01

We report strontium isotopic results for the late Miocene Hualapai Limestone of the Lake Mead area (Arizona-Nevada) and the latest Miocene to early Pliocene Bouse Formation and related units of the lower Colorado River trough (Arizona-California-Nevada), together with parallel oxygen and carbon isotopic analyses of Bouse samples, to constrain the lake-overflow model for integration of the Colorado River. Sr iso topic analyses on the basal 1-5 cm of marl, in particular along a transect over a range of altitude in the lowest-altitude basin that contains freshwater, brackish, and marine fossils, document the 87Sr/86Sr of first-arriving Bouse waters. Results reinforce the similarity between the 87Sr/86Sr of Bouse Formation carbonates and present-day Colorado River water, and the systematic distinction of these values from Neogene marine Sr. Basal Bouse samples show that 87Sr/86Sr decreased from 0.7111 to values in the range 0.7107-0.7109 during early basin filling. 87Sr/86Sr values from a recently identified marl in the Las Vegas area are within the range of Bouse Sr ratios. 87Sr/86Sr values from the Hualapai Limestone decrease upsection from 0.7195 to 0.7137, in the approach to a time soon after 6 Ma when Hualapai deposition ceased and the Colorado River became established through the Lake Mead area. Bouse Formation ??18O values range from -12.9??? to +1.0??? Vienna Pee Dee belemnite (VPDB), and ??13C between -6.5??? and +3.4??? VPDB. Negative ??18O values appear to require a continental origin for waters, and the trend to higher ??18O suggests evaporation in lake waters. Sr and stable isotopic results for sectioned barnacle shells and from bedding planes of the marine fish fossil Colpichthys regis demonstrate that these animals lived in saline freshwater, and that there is no evidence for incursions of marine water, either long-lived or brief in duration. Lack of correlation of Sr and O isotopic variations in the same samples also argue strongly against systematic replacement of Sr in Bouse carbonates after deposition. Our results reinforce the conclusion that the Bouse Formation was deposited in a descending series of basins connected by overflow of Colorado River water. The Hualapai Limestone records a separate and earlier lake that may have been progressively influenced by Colorado River water as the time of river integration approached. ?? 2010 Geological Society of America.

Pleistocene Variations in Delivery and Deposition of Organic Matter Under the Benguela Current Upwelling System - Biomarker Isotopic Evidence From Sediment Light-Dark Color Cycles

NASA Astrophysics Data System (ADS)

Meyers, P. A.; Bouloubassi, I.; Pancost, R. D.; Robinson, R. S.

2007-12-01

The light-dark color cycles that are distinctive features of sediment beneath the Benguela Current Upwelling System imply repetitive alternations in organic matter delivery and deposition. Organic geochemical proxies for paleoproductivity and for depositional conditions were employed to investigate the paleoceanographic processes involved in creating these cycles in two sediment sequences from ODP Site 1084 corresponding to 0.7 and 1.1 Mya. Concentrations of total organic carbon (TOC) vary between 3.5 and 17.1 wt percent, and those of calcium carbonate fluctuate inversely between 68 and 1 percent, suggesting that carbonate dissolution is involved with the light-dark cycles. Bulk organic del 13C and del 15N values that remain constant across the two light-dark sediment intervals indicate that the extent of nutrient utilization did not change in each cycle. Biomarker compositions in both sequences reflect a range of organic matter sources. Abundant n-alkanes and n-alkanols with odd-over-even and even-over-odd distributions, respectively, record land-plant inputs. Other terrestrial biomakers (e.g triterpenoid acids and alcohols) are present but in very low abundances, suggesting that the n- alkyl components derive predominantly from eolian inputs. Carbon isotopic values of n-alkanes range from -25 to -28 permil, suggesting a mixture of C3 and C4 sources. In contrast, n-alkanol isotopic compositions range from -28 to -34 permil, suggesting that they derive solely from C3 plants. Algal biomarkers are abundant and diverse, represented by 1,15-C30 diols (eustigmatophytes), 4-desmethyl and -methylsterols (diatoms, dinoflagellates), and alkenones (haptophytes). These compounds all have del 13C values ranging from ca. -22 to -24 permil, consistent with a marine origin. Systematic differences in isotopic values imply that marine productivity at 1.1 Mya was higher than at 0.7 Mya, but alkenone-based sea-surface temperatures are higher at 1.1 Mya (21 deg) than at 0.7 Mya (15 deg), which indicates that changes in water-mass properties were also involved.

Sources and drains: Major controls of hydrothermal fluid flow in the Kokanee Range, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Beaudoin, Georges; Therrien, René

1999-10-01

Vein fields are fractured domains of the lithosphere that have been infiltrated by hydrothermal fluids, which deposited minerals in response to changing physico-chemical conditions. Because oxygen is a major component of the infiltrating fluid and the surrounding rock matrix, the oxygen isotope composition of minerals found in veins is used to decipher ancient fluid flow within the lithosphere. We use a numerical model to simulate oxygen isotope transport in the Kokanee Range silver-lead-zinc vein field. The model considers advective, dispersive, and reactive transport in a three-dimensional porous rock matrix intersected by high-permeability planes representing fracture zones. Here we show that it is the geometrical configuration of the sources and of the drains of hydrothermal fluids, combined with the fracture pattern, that exerts the main control on the oxygen isotope distribution. Other factors that affect, to a lesser extent, the values and positions of oxygen isopleths are the fluids and rock-matrix isotopic compositions, the isotopic fractionation, the reaction rate constant, and hydraulic conductivities of the rock matrix and fracture zones.

The oxygen isotope partition function ratio of water and the structure of liquid water

USGS Publications Warehouse

O'Neil, J.R.; Adami, L.H.

1969-01-01

By means of the CO2-equilibration technique, the temperature dependence and absolute values of the oxygen isotope partition function ratio of liquid water have been determined, often at 1?? intervals, from -2 to 85??. A linear relationship between In (Q2/Q1) (H2O) and T-1 was obtained that is explicable in terms of the Bigeleisen-Mayer theory of isotopic fractionation. The data are incompatible with conventional, multicomponent mixture models of water because liquid water behaves isotopically as a singly structured homogeneous substance over the entire temperature range studied. A two-species model of water is proposed in which approximately 30% of the hydrogen bonds in ice are broken on melting at 0?? and in which this per cent of monomer changes by only a small amount over the entire liquid range. Because of the high precision and the fundamental property determined, the isotopic fractionation technique is particularly well suited to the detection of thermal anomalies. No anomalies were observed and those previously reported are ascribed to under-estimates of experimental error.

Liquid chromatography coupled to isotope ratio mass spectrometry: a new perspective on honey adulteration detection.

PubMed

Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

2006-12-27

A new procedure to determine individual sugar (sucrose, glucose, and fructose) 13C isotope ratios, using liquid chromatography-isotope ratio mass spectrometry (HPLC-IRMS), has been developed to improve isotopic methods devoted to the study of honey authenticity. For this purpose 79 commercial honey samples from various origins were analyzed. Values of delta13Choney ranged from -14.2 to -27.2", and delta13Cprotein ranged from -23.6 to -26.9". A very strong correlation is observed between the individual sugar 13C ratios, which are altered in the event of sugar addition, even at low levels. The use of Deltadelta13C [fruct-glu], Deltadelta13C [fruct-suc], and Deltadelta13C [gluc-suc] systematic differences as an authenticity criterion permits the sugar addition [C3, beet sugar; or C4, cane sugar, cane syrup, isoglucose syrup, and high-fructose corn syrup (HFCS)] to be reliably detected (DL = 1-10%). The new procedure has advantages over existing methods in terms of analysis time and sensitivity. In addition, it is the first isotopic method developed that allows beet sugar addition detection.

Water, plants, and early human habitats in eastern Africa

PubMed Central

Magill, Clayton R.; Ashley, Gail M.; Freeman, Katherine H.

2013-01-01

Water and its influence on plants likely exerted strong adaptive pressures in human evolution. Understanding relationships among water, plants, and early humans is limited both by incomplete terrestrial records of environmental change and by indirect proxy data for water availability. Here we present a continuous record of stable hydrogen-isotope compositions (expressed as δD values) for lipid biomarkers preserved in lake sediments from an early Pleistocene archaeological site in eastern Africa—Olduvai Gorge. We convert sedimentary leaf- and algal-lipid δD values into estimates for ancient source-water δD values by accounting for biochemical, physiological, and environmental influences on isotopic fractionation via published water–lipid enrichment factors for living plants, algae, and recent sediments. Reconstructed precipitation and lake-water δD values, respectively, are consistent with modern isotopic hydrology and reveal that dramatic fluctuations in water availability accompanied ecosystem changes. Drier conditions, indicated by less negative δD values, occur in association with stable carbon-isotopic evidence for open, C4-dominated grassland ecosystems. Wetter conditions, indicated by lower δD values, are associated with expanded woody cover across the ancient landscape. Estimates for ancient precipitation amounts, based on reconstructed precipitation δD values, range between approximately 250 and 700 mm·y−1 and are consistent with modern precipitation data for eastern Africa. We conclude that freshwater availability exerted a substantial influence on eastern African ecosystems and, by extension, was central to early human proliferation during periods of rapid climate change. PMID:23267102

Water, plants, and early human habitats in eastern Africa.

PubMed

Magill, Clayton R; Ashley, Gail M; Freeman, Katherine H

2013-01-22

Water and its influence on plants likely exerted strong adaptive pressures in human evolution. Understanding relationships among water, plants, and early humans is limited both by incomplete terrestrial records of environmental change and by indirect proxy data for water availability. Here we present a continuous record of stable hydrogen-isotope compositions (expressed as δD values) for lipid biomarkers preserved in lake sediments from an early Pleistocene archaeological site in eastern Africa--Olduvai Gorge. We convert sedimentary leaf- and algal-lipid δD values into estimates for ancient source-water δD values by accounting for biochemical, physiological, and environmental influences on isotopic fractionation via published water-lipid enrichment factors for living plants, algae, and recent sediments. Reconstructed precipitation and lake-water δD values, respectively, are consistent with modern isotopic hydrology and reveal that dramatic fluctuations in water availability accompanied ecosystem changes. Drier conditions, indicated by less negative δD values, occur in association with stable carbon-isotopic evidence for open, C(4)-dominated grassland ecosystems. Wetter conditions, indicated by lower δD values, are associated with expanded woody cover across the ancient landscape. Estimates for ancient precipitation amounts, based on reconstructed precipitation δD values, range between approximately 250 and 700 mm · y(-1) and are consistent with modern precipitation data for eastern Africa. We conclude that freshwater availability exerted a substantial influence on eastern African ecosystems and, by extension, was central to early human proliferation during periods of rapid climate change.

Small-scale studies of roasted ore waste reveal extreme ranges of stable mercury isotope signatures

NASA Astrophysics Data System (ADS)

Smith, Robin S.; Wiederhold, Jan G.; Jew, Adam D.; Brown, Gordon E.; Bourdon, Bernard; Kretzschmar, Ruben

2014-07-01

Active and closed Hg mines are significant sources of Hg contamination to the environment, mainly due to large volumes of mine waste material disposed of on-site. The application of Hg isotopes as source tracer from such contaminated sites requires knowledge of the Hg isotope signatures of different materials potentially released to the environment. Previous work has shown that calcine, the waste residue of the on-site ore roasting process, can exhibit distinct Hg isotope signatures compared with the primary ore. Here, we report results from a detailed small-scale study of Hg isotope variations in calcine collected from the closed New Idria Hg mine, San Benito County, CA, USA. The calcine samples exhibited different internal layering features which were investigated using optical microscopy, micro X-ray fluorescence, micro X-ray absorption spectroscopy (μ-XAS), and stable Hg isotope analysis. Significant Fe, S, and Hg concentration gradients were found across the different internal layers. Isotopic analyses revealed an extreme variation with pronounced isotopic gradients across the internal layered features. Overall, δ202Hg (±0.10‰, 2 SD) describing mass-dependent fractionation (MDF) ranged from -5.96 to 14.49‰, which is by far the largest range of δ202Hg values reported for any environmental sample. In addition, Δ199Hg (±0.06‰, 2 SD) describing mass-independent fractionation (MIF) ranged from -0.17 to 0.21‰. The μ-XAS analyses suggested that cinnabar and metacinnabar are the dominant Hg-bearing phases in the calcine. Our results demonstrate that the incomplete roasting of HgS ores in Hg mines can cause extreme mass-dependent Hg isotope fractionations at the scale of individual calcine pieces with enrichments in both light and heavy Hg isotopes relative to the primary ore signatures. This finding has important implications for the application of Hg isotopes as potential source tracers for Hg released to the environment from closed Hg mines and highlights the need for detailed source signature identification.

Effect of thermal decarbonation on the stable isotope composition of carbonates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durakiewicz, T.; Sharp, Z. D.; Papike, J. J.

2001-01-01

The unusual texture and stable isotope variability of carbonates in AH84001 have been used as evidence for early life on Mars (Romanek et al., 1994; McKay et al., 1996). Oxygen and carbon isotope variability is most commonly attributed to low-temperature processes, including Rayleigh-like fractionation associated with biological activity. Another possible explanation for the isotopic variability in meteoritic samples is thermal decarbonation. In this report, different carbonates were heated in a He-stream until decomposition temperatures were reached. The oxygen and carbon isotope ratios ({delta}{sup 18}O and {delta}{sup 13}C values) of the resulting gas were measured on a continuous flow isotope ratiomore » mass spectrometer. The aim of this work is to evaluate the possibility that large isotopic variations can be generated on a small scale abiogenically, by the process of thermal decarbonation. Oxygen isotope fractionations of >4{per_thousand} have been measured during decarbonation of calcite at high temperatures (McCrea, 1950), and in excess of 6{per_thousand} for dolomite decarbonated between 500 and 600 C (Sharma and Clayton, 1965). Isotopic fractionations of this magnitude, coupled with Rayleigh-like distillation behavior could result in very large isotopic variations on a small scale. To test the idea, calcite, dolomite and siderite were heated in a quartz tube in a He-stream in excess of 1 atmosphere. Simultaneous determinations of {delta}{sup 13}C and {Delta}{sup 18}O values were obtained on 250 {micro}l aliquots of the CO{sub 2}-bearing He gas using an automated 6-way switching valve system (Finnigan MAT GasBench II) and a Finnigan MAT Delta Plus mass spectrometer. It was found that decarbonation of calcite in a He atmosphere begins at 720 C, but the rate significantly increases at temperatures of 820 C. After an initial light {delta}{sup 18}O value of -14.1{per_thousand} at 720 C associated with very early decarbonation, {delta}{sup 18}0 values increase to a constant -11.8{per_thousand}, close to the accepted value of -12.09{per_thousand} (PDB). After 10 minutes at 820 C, the {delta}{sup 18}O values and signal strength both begin to decrease linearly to a {delta}{sup 18}O value of -14.75 and very low amounts of CO{sub 2} (Fig. 1). In contrast, the {delta}{sup 13}C values are extremely constant (0.12 {+-} 0.25{per_thousand}) for all measurements, in very good agreement with accepted values of 0.33{per_thousand} (PDB). There is much less isotopic variability during dolomite decarbonation. CO{sub 2} is first detected at 600 C. The signal strength increases by an order of magnitude between 670 and 700 C and again at 760 C. Both {delta}{sup 13}C and {delta}{sup 18}O values are nearly constant over the entire temperature range and sample size. For oxygen, the measured {delta}{sup 18}O values averaged -20.9 {+-} 0.7{per_thousand} (n = 30). Including only samples over 700 C, the average is -21.2 {+-} 0.2{per_thousand} compared to the accepted value of -21{per_thousand}. Carbon is similarly constant. The average {delta}{sup 13}C value is -2.50{per_thousand} compared to the accepted value of -2.62{per_thousand}. Far more variability is seen during the decomposition of siderite. Two samples were analyzed. In both samples, the initial {delta}{sup 18}O values were far lower than expected.« less

In situ analysis of carbon isotopes in North American diamonds

NASA Astrophysics Data System (ADS)

van Rythoven, A. D.; Hauri, E. H.; Wang, J.; McCandless, T.; Shirey, S. B.; Schulze, D. J.

2010-12-01

Diamonds from three North American kimberlite occurrences were investigated with cathodoluminescence (CL) and secondary ion mass spectrometry (SIMS) to determine their growth history and carbon isotope composition. Diamonds analyzed include fourteen from Lynx (Quebec), twelve from Kelsey Lake (Colorado) and eleven from A154 South (Diavik mine, Northwest Territories). Growth histories for the diamonds vary from simple to highly complex based on their CL images and depending on the individual stone. Deformation laminae are evident in CL images of the Lynx diamonds that typically are brownish in color. Two to five points per diamond were analyzed by SIMS for carbon isotope composition. Sample heterogeneity is minimal in terms of δ13C (vs. PDB) values. Points within single diamond had a maximum range of approximately 1 ‰. The results for the A154 South (-6.4 to -3 ‰) and Kelsey Lake (-11.2 to -2.6 ‰) stones were in accordance with earlier reported values. The Lynx kimberlite stones have anomalously high ratios and range from -3.5 to +0.2 ‰ (average: -1.4 ‰). No previous carbon isotope analyses on diamonds from Lynx or any other eastern Superior craton occurrence have been published. The diamonds possess carbon isotope ratios higher than those for the only other reported analyses of Superior craton diamonds at Wawa, Ontario (-5.5 to -1.1 ‰). In global terms, the only published analyses of diamonds that consistently contain even higher values are those from New South Wales (Australia). However, these diamonds are alluvial and contain eclogitic and/or exotic mineral inclusions. The Lynx diamonds are entirely peridotitic and from a primary deposit. The unusually low (i.e. >-5‰) δ13C values of the Lynx (and Wawa) diamonds may indicate a different carbon reservoir for the Superior craton mantle as compared to other cratons.

Application of multiple-isotope and groundwater-age data to identify factors affecting the extent of denitrification in a shallow aquifer near a river in South Korea

NASA Astrophysics Data System (ADS)

Kaown, Dugin; Koh, Eun-Hee; Mayer, Bernhard; Kim, Heejung; Park, Dong Kyu; Park, Byeong-Hak; Lee, Kang-Kun

2018-01-01

The extent of denitrification in a small agricultural area near a river in Yangpyeong, South Korea, was determined using multiple isotopes, groundwater age, and physicochemical data for groundwater. The shallow groundwater at one monitoring site had high concentrations of NO3-N (74-83 mg L-1). The δ15N-NO3 values for groundwater in the study area ranged between +9.1 and +24.6‰ in June 2014 and +12.2 to +21.6‰ in October 2014. High δ15N-NO3 values (+10.7 to +12.5‰) in both sampling periods indicated that the high concentrations of nitrate in the groundwater originated from application of organic fertilizers and manure. In the northern part of the study area, some groundwater samples showed elevated δ15N-NO3 and δ18O-NO3 values, which suggest that nitrate was removed from the groundwater via denitrification, with N isotope enrichment factors ranging between -4.8 and -7.9‰ and O isotope enrichment factors varying between -3.8 and -4.9‰. Similar δD and δ18O values of the surface water and groundwater in the south appear to indicate that groundwater in that area was affected by surface-water infiltration. The mean residence times (MRTs) of groundwater showed younger ages in the south (10-20 years) than in the north (20-30 years). Hence, it was concluded that denitrification processes under anaerobic conditions with longer groundwater MRT in the northern part of the study area removed considerable amounts of nitrate. This study demonstrates that multi-isotope data combined with physicochemical data and age-dating information can be effectively applied to characterize nitrate contaminant sources and attenuation processes.

Oxygen and carbon isotope ratios of hydrothermal minerals from Yellowstone drill cores

USGS Publications Warehouse

Sturchio, N.C.; Keith, T.E.C.; Muehlenbachs, K.

1990-01-01

Oxygen and carbon isotope ratios were measured for hydrothermal minerals (silica, clay and calcite) from fractures and vugs in altered rhyolite, located between 28 and 129 m below surface (in situ temperatures ranging from 81 to 199??C) in Yellowstone drill holes. The purpose of this study was to investigate the mechanism of formation of these minerals. The ??18O values of the thirty-two analyzed silica samples (quartz, chalcedony, ??-cristobalite, and ??-cristobalite) range from -7.5 to +2.8???. About one third of the silica 7samples have ??18O values that are consistent with isotopic equilibrium with present thermal waters; most of the other silica samples appear to have precipitated from water enriched in 18O (up to 4.7???) relative to present thermal water, assuming precipitation at present in situ temperatures. Available data on fluid-inclusion homogenization temperatures in hydrothermal quartz indicate that silica precipitation occurred mostly at temperatures above those measured during drilling and imply that 15O enrichments in water during silica precipitation were generally larger than those estimated from present conditions. Similarly, clay minerals (celadonite and smectite) have ??18O values higher (by 3.5 to 7.9???) than equilibrium values under present conditions. In contrast, all eight analyzed calcite samples are close to isotopic equilibrium with present thermal waters. The frequent incidence of apparent 18O enrichment in thermal water from which the hydrothermal minerals precipitated may indicate that a higher proportion of strongly 18O-enriched deep hydrothermal fluid once circulated through shallow portions of the Yellowstone system, or that a recurring transient 18O-enrichment effect occurs at shallow depths and is caused either by sudden decompressional boiling or by isotopic exchange at low water/rock ratios in new fractures. The mineralogy and apparent 18O enrichments of hydrothermal fracture-filling minerals are consistent with deposition during transient boiling or rock-water exchange (fracturing) events. ?? 1990.

Selective recharge and isotopic composition of shallow groundwater within temperate, epigenic carbonate aquifers

NASA Astrophysics Data System (ADS)

Florea, Lee J.

2013-05-01

This paper considers the variation of δ18O and δ2H (VSMOW) in precipitation and shallow groundwater from carbonate aquifers that lend insight into the source and timing of recharge within temperate, epigenic karst. The shallow groundwater collected during 2010 and 2011 at Stream Cave (SC) and Natural Bridge Caverns (NBC) represent one input to and the primary output from the Redmond Creek karst aquifer in the Cumberland Plateau of southeast Kentucky, respectively. These data are compared with the isotopic composition of concurrent samples of precipitation from the same watershed that covers some 1900 ha. Values of δ18O and δ2H at SC and NBC are statistically similar and cluster at the midpoint of the local meteoric water line. These values remain surprisingly constant despite seasonal changes in temperature regimens and discharge. Samples in 2012 from regional springs that include Redmond Creek are more depleted in the heavier isotope and similarly stable despite coming from aquifers of a range of sizes and physical characteristics. Applying a Priestly-Taylor model for daily values of potential evapotranspiration, only 43% of the 1.10 m of precipitation in the 2010-2011 dataset remains as potential recharge, primarily during cooler months with lower solar insolation. Weighting δ18O and δ2H values of precipitation by potential recharge creates a better match with the isotopic composition of shallow groundwater than by weighting by precipitation amount. The isotopic composition and deuterium excess of precipitation samples are directly and inversely proportional to temperature, respectively. Deuterium excess in this study and displays intra- and inter-annual variation that ranges from a minimum of +11.1‰ to a maximum of +29.5‰ that demonstrate the higher-than-average deuterium excess in greater Appalachia and the shifting latitude of moisture sources, including a significant winter component of re-evaporated, continental moisture.

An isotopic study of the Coso, California, geothermal area

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fournier, R.O.; Thompson, J.M.

1982-10-01

Thirty-nine water samples were collected from the Coso geothermal system and vicinity and were analyzed for major chemical constituents and deltaD and delta/sup 18/O. Non-thermal ground waters from the Coso Range were found to be isotopically heavier than non-thermal ground waters from the Sierra Nevada to the west. The deltaD value for the deep thermal water at Coso is similar to that of the Sierra water, suggesting that the major recharge for the hydrothermal system comes from the Sierra Nevada rather than from local precipitation on the Coso Range. The delta/sup 18/O values of the thermal water are about 7/supmore » 0//00 heavier than those of the Sierra water. This shift in delta/sup 18/O is the result of water-rock reaction at high temperatures, and the magnitude of the shift indicates that the ratio of rock to total water has been large for the system up to its present stage of development. The isotopic data are compatible with the geochemical model previously proposed by Fournier.« less

Trophic ecology and vertical patterns of carbon and nitrogen stable isotopes in zooplankton from oxygen minimum zone regions

NASA Astrophysics Data System (ADS)

Williams, Rebecca L.; Wakeham, Stuart; McKinney, Rick; Wishner, Karen F.

2014-08-01

The unique physical and biogeochemical characteristics of oxygen minimum zones (OMZs) influence plankton ecology, including zooplankton trophic webs. Using carbon and nitrogen stable isotopes, this study examined zooplankton trophic webs in the Eastern Tropical North Pacific (ETNP) OMZ. δ13C values were used to indicate zooplankton food sources, and δ15N values were used to indicate zooplankton trophic position and nitrogen cycle pathways. Vertically stratified MOCNESS net tows collected zooplankton from 0 to 1000 m at two stations along a north-south transect in the ETNP during 2007 and 2008, the Tehuantepec Bowl and the Costa Rica Dome. Zooplankton samples were separated into four size fractions for stable isotope analyses. Particulate organic matter (POM), assumed to represent a primary food source for zooplankton, was collected with McLane large volume in situ pumps. The isotopic composition and trophic ecology of the ETNP zooplankton community had distinct spatial and vertical patterns influenced by OMZ structure. The most pronounced vertical isotope gradients occurred near the upper and lower OMZ oxyclines. Material with lower δ13C values was apparently produced in the upper oxycline, possibly by chemoautotrophic microbes, and was subsequently consumed by zooplankton. Between-station differences in δ15N values suggested that different nitrogen cycle processes were dominant at the two locations, which influenced the isotopic characteristics of the zooplankton community. A strong depth gradient in zooplankton δ15N values in the lower oxycline suggested an increase in trophic cycling just below the core of the OMZ. Shallow POM (0-110 m) was likely the most important food source for mixed layer, upper oxycline, and OMZ core zooplankton, while deep POM was an important food source for most lower oxycline zooplankton (except for samples dominated by the seasonally migrating copepod Eucalanus inermis). There was no consistent isotopic progression among the four zooplankton size classes for these bulk mixed assemblage samples, implying overlapping trophic webs within the total size range considered.

Molybdenum and zinc stable isotope variation in mining waste rock drainage and waste rock at the Antamina mine, Peru.

PubMed

Skierszkan, E K; Mayer, K U; Weis, D; Beckie, R D

2016-04-15

The stable isotope composition of molybdenum (Mo) and zinc (Zn) in mine wastes at the Antamina Copper-Zn-Mo mine, Peru, was characterized to investigate whether isotopic variation of these elements indicated metal attenuation processes in mine drainage. Waste rock and ore minerals were analyzed to identify the isotopic composition of Mo and Zn sources, namely molybdenites (MoS2) and sphalerites (ZnS). Molybdenum and Zn stable isotope ratios are reported relative to the NIST-SRM-3134 and PCIGR-1 Zn standards, respectively. δ(98)Mo among molybdenites ranged from -0.6 to +0.6‰ (n=9) while sphalerites showed no δ(66)Zn variations (0.11±0.01‰, 2 SD, n=5). Mine drainage samples from field waste rock weathering experiments were also analyzed to examine the extent of isotopic variability in the dissolved phase. Variations spanned 2.2‰ in δ(98)Mo (-0.1 to +2.1‰) and 0.7‰ in δ(66)Zn (-0.4 to +0.3‰) in mine drainage over a wide pH range (pH2.2-8.6). Lighter δ(66)Zn signatures were observed in alkaline pH conditions, which was consistent with Zn adsorption and/or hydrozincite (Zn5(OH)6(CO3)2) formation. However, in acidic mine drainage Zn isotopic compositions reflected the value of sphalerites. In addition, molybdenum isotope compositions in mine drainage were shifted towards heavier values (0.89±1.25‰, 2 SD, n=16), with some overlap, in comparison to molybdenites and waste rock (0.13±0.82‰, 2 SD, n=9). The cause of heavy Mo isotopic signatures in mine drainage was more difficult to resolve due to isotopic heterogeneity among ore minerals and a variety of possible overlapping processes including dissolution, adsorption and secondary mineral precipitation. This study shows that variation in metal isotope ratios are promising indicators of metal attenuation. Future characterization of isotopic fractionation associated to key environmental reactions will improve the power of Mo and Zn isotope ratios to track the fate of these elements in mine drainage. Copyright © 2015 Elsevier B.V. All rights reserved.

Constraints of lithium isotopes on petrogenesis of the Northern Luzon arc in Eastern Taiwan

NASA Astrophysics Data System (ADS)

Hsiao, C. C.; Chu, M. F.; Lai, Y. M.; Lin, T. H.

2017-12-01

Lithium stable isotopes have great potential as a tracer of terrestrial materials in crust-mantle recycling. However, the causes of their variations in arc magmatism remain controversial. The Northern Luzon arc has long been demonstrated incorporation of the sediment melt into its sub-arc mantle. The Li isotopes of volcanic rocks in the Coastal Range, located in Eastern Taiwan, thus are studied to examine the effects of sediment melt on the evolution of Li isotopes in subduction zone and also to constrain the petrogenesis of the northernmost part of Northern Luzon arc. It is worth to note that we had ruled out samples that were significantly influenced by crustal contamination according to the proportion of inherited zircons, trace-elemental and Sr-Nd isotopic geochemistry. Concerning that Li isotopic fractionation is negligible during fractional crystallization and partial melting, the variation of Li/Y and δ7Li in rock samples of this study mainly reflects the geochemistry of magma sources. The overall range of δ7Li is very restricted (δ7Li = +2.9 +5.8) and consistent with that of N-MORB. In addition, ɛNd of the Coastal Range volcanic rocks lowers not only with increasing values of sediment-melt indicators (e.g., Th/Ce, Th/Yb and La/Sm), but also Li/Y (from 0.5 to 1.1 ppm). This suggests the involvement of sediment melt with equivalent δ7Li to and higher Li/Y than those of N-MORB, in magma source of the Coastal Range arc volcanism. In summary, the Li isotopic compositions of the Coastal Range volcanic rocks demonstrate that (1) Li/Y commonly treated as a tracer of fluid in arc magmatism indeed can be significantly affected by the input of sediment melt as well, and (2) sediment melt played a key role in the evolution of Li/Y and lithium isotopes in the mantle wedge, but showed least influence on Li isotopic variation possibly as a result of the similarity between δ7Li of sediments subducted and of the upper mantle.

Effect of deformation on structure and reaction of Al isotopes using relativistic mean field densities in Glauber model

NASA Astrophysics Data System (ADS)

Panda, R. N.; Sharma, Mahesh K.; Panigrahi, M.; Patra, S. K.

2018-02-01

We have examined the ground state properties of Al isotopes towards the proton rich side from A = 22 to 28 using the well known relativistic mean field (RMF) formalism with NLSH parameter set. The calculated results are compared with the predictions of finite range droplet model and experimental data. The calculation is extended to estimate the reaction cross section for ^{22-28} Al as projectiles with ^{12} C as target. The incident energy of the projectiles are taken as 950 MeV/nucleon, for both spherical and deformed RMF densities as inputs in the Glauber model approximation. Further investigation of enhanced values of total reaction cross section for ^{23} Al and ^{24} Al in comparison to rest of the isotopes indicates the proton skin structure of these isotopes. Specifically, the large value of root mean square radius and total reaction cross section of ^{23} Al could not be ruled out the formation of proton halo.

Effect of deformation on structure and reaction of Al isotopes using relativistic mean field densities in Glauber model

NASA Astrophysics Data System (ADS)

Panda, R. N.; Sharma, Mahesh K.; Panigrahi, M.; Patra, S. K.

2018-06-01

We have examined the ground state properties of Al isotopes towards the proton rich side from A = 22 to 28 using the well known relativistic mean field (RMF) formalism with NLSH parameter set. The calculated results are compared with the predictions of finite range droplet model and experimental data. The calculation is extended to estimate the reaction cross section for ^{22-28}Al as projectiles with ^{12}C as target. The incident energy of the projectiles are taken as 950 MeV/nucleon, for both spherical and deformed RMF densities as inputs in the Glauber model approximation. Further investigation of enhanced values of total reaction cross section for ^{23}Al and ^{24}Al in comparison to rest of the isotopes indicates the proton skin structure of these isotopes. Specifically, the large value of root mean square radius and total reaction cross section of ^{23}Al could not be ruled out the formation of proton halo.

Using stable isotopes and major ions to identify hydrological processes and geochemical characteristics in a typical karstic basin, Guizhou, Southwest China.

PubMed

Han, Zhiwei; Tang, Changyuan; Wu, Pan; Zhang, Ruixue; Zhang, Chipeng

2014-01-01

The investigation of hydrological processes is very important for water resource development in karst basins. In order to understand these processes associated with complex hydrogeochemical evolution, a typical basin was chosen in Houzai, southwest China. The basin was hydrogeologically classified into three zones based on hydrogen and oxygen isotopes as well as the field surveys. Isotopic values were found to be enriched in zone 2 where paddy fields were prevailing with well-developed underground flow systems, and heavier than those in zone 1. Zone 3 was considered as the mixture of zones 1 and 2 with isotopic values falling in the range between the two zones. A conceptual hydrological model was thus proposed to reveal the probable hydrological cycle in the basin. In addition, major processes of long-term chemical weathering in the karstic basin were discussed, and reactions between water and carbonate rocks proved to be the main geochemical processes in karst aquifers.

Recent terebratulide brachiopods: Do they faithfully record oceanographic conditions throughout ontogeny?

NASA Astrophysics Data System (ADS)

Kercher, P.; Carlson, S. J.

2012-12-01

Brachiopods have commonly been used to infer secular changes in ocean chemistry over the Phanerozoic Eon since Lowenstam (1961) concluded that Recent brachiopod calcite was precipitated in equilibrium with seawater. In order to infer paleoenvironmental conditions with confidence, however, the impact of potential kinetic and metabolic fractionation effects on the final isotopic signature, as it varies among individuals, must be determined. In this study, we analyzed the oxygen and carbon isotopic composition of closely spaced (~2/mm) samples of calcite along growth transects from individuals of the rhynchonelliform brachiopod, Laqueus californianus. By combining local oceanographic information with knowledge of brachiopod shell structure and growth patterns through ontogeny, in individuals of different ages from the same locality that died simultaneously, we can address the fidelity of brachiopod shell calcite as both an environmental proxy and a recorder of biological activity among conspecific individuals, in real time. This is an essential, but largely ignored, component in the paleoenvironmental interpretation of brachiopod shell calcite. In May 2011, more than 75 live L. californianus specimens were collected by Dr. J. Barry at Monterey Bay Aquarium Research Institute (MBARI) from Monterey Bay at 160 m water depth (36.7322N, 121.9739W) and generously given to us for use in this study. The specimens range in length from 5.75 to 46.16 mm, representing a range of ontogenetic ages. Water temperatures at 160 m range annually from 8C in the spring/summer upwelling season to 10C during the winter, while salinity fluctuates from 33.76 ppt in the winter to 34.11 ppt in the summer. Daily temperature and salinity data collected by MBARI over three decades allow us to calculate approximate equilibrium calcite values. We use these values to evaluate the claim that brachiopods mineralize in isotopic equilibrium with seawater throughout their lifespan with minimal intraspecific variation. We also use the MBARI data to correlate annual temperature fluctuations with δ18O trends within the calcite to estimate ontogenetic ages and growth rates. Full-grown adults were 10-11 years old when collected live, and grow an average of about 4 mm/year over their lifespan, growing faster before sexual maturity and slowing down after. The early results of the ontogenetic sampling tracts indicate calcite δ18O and δ13C values are strongly positively correlated. This relationship suggests kinetic fractionation effects are likely influencing the isotopic composition of the shells. Cyclic isotopic fluctuations are also recorded, in accordance with seasonal temperature oscillations in Monterey Bay, apparent even at 160 m depth. In most of the specimens, the amplitudes of the isotopic fluctuations exceed those of the predicted equilibrium values. Furthermore, our data support the claim made by other researchers that the outer primary layer of the shell is significantly depleted in both oxygen and carbon isotopes, below the range of equilibrium calcite. Isotopic oscillations across individuals align reasonably well both with each other and with ambient water temperature patterns. These results suggest that intraspecific variability is low in L. californianus and that these organisms are recording their environment similarly.

Involvement of magmatic fluids at the Laloki and Federal Flag massive sulfide Cu-Zn-Au-Ag deposits, Astrolabe mineral district, Papua New Guinea: sulfur isotope evidence

NASA Astrophysics Data System (ADS)

Noku, Shadrach K.; Espi, Joseph O.; Matsueda, Hiroharu

2015-01-01

We present the first sulfur (S) isotope data of sulfides, sulfates, pyrite in host mudstone, and bulk sulfur of gabbroic rocks from the Laloki and Federal Flag massive Cu-Zn-Au-Ag deposits in the Astrolabe mineral district, Papua New Guinea. Early-stage pyrite-marcasite, chalcopyrite, and sphalerite from Laloki display wide range of δ34S values from -4.5 to +7.0 ‰ ( n = 16). Late-stage pyrite, chalcopyrite, and sphalerite have restricted δ34S values of -1.9 to +4.7 ‰ ( n = 16). The mineralizing stage these correspond to had moderately saline (5.9-8.4 NaCl eq. wt%) mineralizing fluids of possible magmatic origin. A single analysis of late-stage barite has a value of δ34S +17.9 ‰, which is likely similar to coexisting seawater sulfate. Pyrite from the foot-wall mudstone at Laloki has very light δ34S values of -36.1 to -33.8 ‰ ( n = 2), which suggest an organic source for S. Pyrite-marcasite and chalcopyrite from Federal Flag show δ34S values of -2.4 to -1.9 ‰ ( n = 2), consistent with a magmatic origin, either leached from intrusive magmatic rocks or derived from magmatic-hydrothermal fluids. The very narrow range and near-zero δ34S values (-1.0 to +0.6 ‰) of bulk gabbroic samples is consistent with mantle-derived magmatic S. Sulfur isotope characteristics of sulfides and sulfates are, however, very similar to base metal sulfide accumulations associated with modern volcanic arcs and sedimented mid-ocean ridges. The most reasonable interpretation is that the range of the sulfide and sulfate δ34S values from both Laloki and Federal Flag massive sulfide deposits is indicative of the complex interaction of magmatic fluids, seawater, gabbroic rocks, and mudstone.

Reconstructing the evolution of the submarine Monterey Canyon System from Os, Nd, and Pb isotopes in hydrogenetic Fe-Mn crusts

USGS Publications Warehouse

Conrad, T.A.; Nielsen, S.G.; Peucker-Ehrenbrink, Bernhard; Blusztajn, J.; Winslow, D.; Hein, James; Paytan, A.

2017-01-01

The sources of terrestrial material delivered to the California margin over the past 7 Myr were assessed using 187Os/188Os, Nd, and Pb isotopes in hydrogenetic ferromanganese crusts from three seamounts along the central and southern California margin. From 6.8 to 4.5 (± 0.5) Ma, all three isotope systems show more radiogenic values at Davidson Seamount, located near the base of the Monterey Canyon System, than in Fe-Mn crusts from the more remote Taney and Hoss seamounts. At the Taney seamounts, approximately 225 km farther offshore from Davidson Seamount, 187Os/188Os values, but not Pb and Nd isotope ratios, also deviate from the Cenozoic seawater curve towards more radiogenic values from 6.8 to 4.5 (± 0.5) Ma. However, none of the isotope systems in Fe-Mn crusts deviate from seawater at Hoss Seamount located approximately 450 km to the south. The regional gradients in isotope ratios indicate that substantial input of dissolved and particulate terrestrial material into the Monterey Canyon System is responsible for the local deviations in the seawater Nd, Pb, and Os isotope compositions from 6.8 to 4.5 (± 0.5) Ma. The isotope ratios recorded in Fe-Mn crusts are consistent with a southern Sierra Nevada or western Basin and Range provenance of the terrestrial material which was delivered by rivers to the canyon. The exhumation of the modern Monterey Canyon must have begun between 10 and 6.8 ± 0.5 Ma, as indicated by our data, the age of incised strata, and paleo-location of the Monterey Canyon relative to the paleo-coastline.

Reconstructing the Evolution of the Submarine Monterey Canyon System From Os, Nd, and Pb Isotopes in Hydrogenetic Fe-Mn Crusts

NASA Astrophysics Data System (ADS)

Conrad, T. A.; Nielsen, S. G.; Peucker-Ehrenbrink, B.; Blusztajn, J.; Winslow, D.; Hein, J. R.; Paytan, A.

2017-11-01

The sources of terrestrial material delivered to the California margin over the past 7 Myr were assessed using 187Os/188Os, Nd, and Pb isotopes in hydrogenetic ferromanganese crusts from three seamounts along the central and southern California margin. From 6.8 to 4.5 (±0.5) Ma, all three isotope systems show more radiogenic values at Davidson Seamount, located near the base of the Monterey Canyon System, than in Fe-Mn crusts from the more remote Taney and Hoss Seamounts. At the Taney Seamounts, approximately 225 km farther offshore from Davidson Seamount, 187Os/188Os values, but not Pb and Nd isotope ratios, also deviate from the Cenozoic seawater curve toward more radiogenic values from 6.8 to 4.5 (±0.5) Ma. However, none of the isotope systems in Fe-Mn crusts deviate from seawater at Hoss Seamount located approximately 450 km to the south. The regional gradients in isotope ratios indicate that substantial input of dissolved and particulate terrestrial material into the Monterey Canyon System is responsible for the local deviations in the seawater Nd, Pb, and Os isotope compositions from 6.8 to 4.5 (±0.5) Ma. The isotope ratios recorded in Fe-Mn crusts are consistent with a southern Sierra Nevada or western Basin and Range provenance of the terrestrial material which was delivered by rivers to the canyon. The exhumation of the modern Monterey Canyon must have begun between 10 and 6.8 ± 0.5 Ma, as indicated by our data, the age of incised strata, and paleo-location of the Monterey Canyon relative to the paleo-coastline.

Nitrous oxide as an indicator of nitrogen transformation in a septic system plume

NASA Astrophysics Data System (ADS)

Li, L.; Spoelstra, J.; Robertson, W. D.; Schiff, S. L.; Elgood, R. J.

2014-11-01

This study evaluates the use of ground water N2O concentration and stable isotope composition for providing insights into nitrogen cycling processes in a large septic system plume in southern Ontario, Canada. An extremely large range of dissolved N2O concentrations were measured (0.4-1071 μg N/L) that were higher than atmospheric equilibrium values of ∼0.3 μg N/L, demonstrating substantial N2O production in the subsurface. The highest N2O concentrations occurred around the periphery of a mid-depth zone where NO3- attenuation, elevated DOC concentration, and NO3- stable isotope ratios provided evidence that denitrification was occurring. Broad ranges in δ15N-N2O (-45.8‰ to +30.6‰) and δ18O-N2O (+20.4‰ to +96.0‰) were evident. Using literature isotopic enrichment factors, which differ for N2O produced during nitrification and denitrification, and measured ranges of plume NH4+ and NO3- isotopic ratios, zones of both nitrifier-derived N2O (shallow zone) and denitrifier-N2O (mid-depth and deeper zones) could be identified. Time series sampling showed that nitrifier N2O was present early in the summer season (June) but then denitrifier N2O was more dominant later in the season. In a mid-depth NO3- depleted zone, the production of denitrifier-N2O was evident early in the season when 15N and 18O enrichment of NO3- was not sufficiently advanced to be indicative of denitrification, although δ15N and δ18O values of NO3- increased later in the season. The analysis of N2O concentrations and stable isotopic composition, in conjunction with conventional chemical analyses, provides insights into N-cycling processes in the Long Point ground water septic plume. However, large ranges in the isotopic composition of N2O produced by nitrifiers and denitrifiers meant that δ15N and δ18O analysis of ground water N2O provided qualitative, rather than quantitative, information on denitrifier versus nitrifier production of N2O at this site.

Reconstruction of the Eocene Arctic Ocean Using Ichthyolith Isotope Analyses

NASA Astrophysics Data System (ADS)

Gleason, J. D.; Thomas, D. J.; Moore, T. C.; Waddell, L. M.; Blum, J. D.; Haley, B. A.

2007-12-01

Nd, Sr, O and C isotopic compositions of Eocene fish debris (teeth, bones, scales), and their reduced organic coatings, have been used to reconstruct water mass composition, water column structure, surface productivity and salinities of the Arctic Ocean Basin at Lomonosov Ridge between 55 and 44 Ma. Cleaned ichthyolith samples from IODP Expedition 302 (ACEX) record epsilon Nd values that range from -5.7 to -7.8, distinct from modern Arctic Intermediate Water (-10.5) and North Atlantic Deep Water. These Nd values may record some exchange with Pacific/Tethyan water masses, but inputs from local continental sources are more likely. Sr isotopic values are consistent with a brackish-to-fresh water surface layer (87Sr/86Sr = 0.7079-0.7087) that was poorly mixed with Eocene global seawater (0.7077-0.7078). Leaching experiments show reduced organic coatings to be more radiogenic (>0.7090) than cleaned ichthyolith phosphate. Ichthyolith Sr isotopic variations likely reflect changes in localized river input as a function of shifts in the Arctic hydrologic cycle, and 87Sr/86Sr values might be used as a proxy for surface water salinity. Model mixing calculations indicate salinities of 5 to 20 per mil, lower than estimates based on O isotopes from fish bone carbonate (16 to 26 per mil). Significant salinity drops (i.e., 55 Ma PETM and 48.5 Ma Azolla event) registered in oxygen isotopes do not show large excursions in the 87Sr/86Sr data. Carbon isotopes in fish debris record a spike in organic activity at 48.5 Ma (Azolla event), and otherwise high-productivity waters between 55 and 44 Ma. The combined Sr-Nd-O-C isotopic record is consistent with highly restricted basin-wide circulation in the Eocene, indicative of a highly stratified water column with anoxic bottom waters, a "fresh" water upper layer, and enhanced continental runoff during warm intervals until the first appearance of ice rafted debris at 45 Ma.

Nd, Sr and O isotopic study of the petrogenesis of two syntectonic members of the New Hampshire Plutonic Series

NASA Astrophysics Data System (ADS)

Lathrop, A. S.; Blum, Joel D.; Chamberlain, C. Page

1996-07-01

Nd, Sr and O isotope systematics were used to investigate the petrogenesis of two adjacent plutons of the Bethlehem Gneiss (BG) and the Kinsman Quartz Monzonite (KQM), exposed within the Central Maine Terrane (CMT) of New England. Both are Acadian-aged (≈413 Ma) synmetamorphic and syntectonic members of the New Hampshire Plutonic Series (NHPS). Potential source rocks analyzed for this study include Silurian and Devonian metasedimentary rocks of the CMT, and Ordovician metasedimentary rocks and granitic gneisses of the Bronson Hill Anticlinorium (BHA), which border the CMT to the west. The ɛSr(413), ɛNd(413) and δ18O values for the KQM range from 56.3 to 120.0, 2.8 to -6.4, and 7.6‰ to 12.9‰, respectively; values for the BG range from 7.4 to 144.7, 0.6 to -9.3, and 8.3‰ to 11.3‰, respectively; and values for possible source rocks range from 38.1 to 654.2, -10.7 to 5.4, and 6.2‰ to 14.1‰, respectively. Both the BG and KQM have extremely heterogeneous initial isotopic compositions consistent with mixing of multiple crustal source rocks, and neither contains a volumetrically significant (i.e., ≥10%) mantlederived component. Overlapping values of ɛNd(413), ɛSr(413) and δ18O values for both the BG and KQM samples resemble values for metasedimentary host rocks of the CMT and BHA. We observe no systematic correlations between ɛNd and ɛSr values for either the BG or the KQM. The ɛSr and δ18O values for the BG do not form any simple mixing trends, nor is there any direct correlation between the isotopic compositions of contact BG samples and their adjacent host rocks, in contrast to our observations for the KQM (Lathrop et al. 1994). We propose that the KQM and BG magmas were generated through anatexis of metasedimentary rocks from both the BHA and CMT in response to crystal thickening during the Acadian orogeny. Melting may have been initiated within CMT metasediments in response to high heat production in these mid-crustal rocks combined with crustal thickening, whereas melting of BHA rocks with normal crustal heat production, which were located at lower-crustal levels than CMT rocks, is likely to have been driven by crustal thickening alone. Following upward advection of mobile BHA magmas, BHA- and CMT-derived magmas may have mingled during complex Acadian deformation in the CMT, thus accounting for the isotopic similarities we observe between the BG and the KQM.

The Relative Importance of Convective and Trade-wind Orographic Precipitation to Streamflow in the Luquillo Mountains, Eastern Puerto Rico

NASA Astrophysics Data System (ADS)

Scholl, M. A.; Shanley, J. B.; Occhi, M.; Scatena, F. N.

2012-12-01

Like many mountainous areas in the tropics, watersheds in the Luquillo Mountains of Puerto Rico (18.3° N) have abundant rainfall and stream discharge, but relatively little storage capacity. Therefore, the water supply is vulnerable to drought and water availability may be affected by projected changes in regional temperature and atmospheric dynamics due to global warming. To help determine the links between climate and water availability, precipitation patterns were analyzed, and stable-isotope signatures of precipitation from different seasonal weather systems were established to identify those that are most important in maintaining streamflow and groundwater recharge. Stable isotope data include cloud water, rainfall, throughfall, streamflow, and groundwater from the Rio Mameyes and Rio Icacos/ Rio Blanco watersheds. Precipitation inputs have a wide range of stable isotope values, from fog/cloud water with δ2H and δ18O averaging +3.2‰, -1.74‰ respectively, to tropical storm rain with values as low as -154‰, -20.4‰. Spatial and temporal patterns of water isotopic values on this Caribbean island are different than higher latitude, continental watersheds. The data exhibit a 'reverse seasonality', with higher isotopic values in winter and lower values in summer; and stable isotope values of stream water do not decrease as expected with increasing altitude, because of cloud water input. Rain isotopic values vary predictably with local and mesoscale weather patterns and correlate strongly with cloud altitude. This correlation allows us to assign isotopic signatures to different sources of precipitation, and to investigate which climate patterns contribute to streamflow and groundwater recharge. At a measurement site at 615 m in the Luquillo Mountains, the average length of time between rain events was 15 h, and 45% of the rain events were <2 mm, reflecting the frequent small rain events of the trade-wind orographic rainfall weather pattern. Long-term average streamflow isotopic composition indicates a disproportionately large contribution of this trade-wind precipitation to streamflow, highlighting the importance of this climate pattern to the hydrology of the watersheds. Isotopic composition of groundwater suggests a slightly higher proportion of convective precipitation, but still smaller than in total rainfall. Hydrograph separation experiments yielded information on stormflow characteristics, with quantification of contributing sources determined from water isotopes and solute chemistry. The evidence that intense convective rain events run off and light trade-wind showers appear to contribute much of the baseflow indicates that the area may undergo a change in water supply if the trade-wind orographic precipitation dynamics in the Caribbean are affected by future climate change.

Carbon and nitrogen systematics in nitrogen-rich, ultradeep diamonds from Sao Luiz, Brazil

NASA Astrophysics Data System (ADS)

Navon, Oded; Stachel, Thomas; Stern, Richard A.; Harris, Jeffrey W.

2018-05-01

Three diamonds from Sao Luiz, Brazil carrying nano- and micro-inclusions of molecular δ-N2 that exsolved at the base of the transition zone were studied for their C and N isotopic composition and the concentration of N utilizing SIMS. The diamonds are individually uniform in their C isotopic composition and most spot analyses yield δ13C values of -3.2 ± 0.1‰ (ON-SLZ-390) and - 4.7 ± 0.1‰ (ON-SLZ-391 and 392). Only a few analyses deviate from these tight ranges and all fall within the main mantle range of -5 ± 3‰. Most of the N isotope analyses also have typical mantle δ15N values (-6.6 ± 0.4‰, -3.6 ± 0.5‰ and - 4.1 ± 0.6‰ for ON-SLZ-390, 391 and 392, respectively) and are associated with high N concentrations of 800-1250 atomic ppm. However, some N isotopic ratios, associated with low N concentrations (<400 ppm) and narrow zones with bright luminescence are distinctly above the average, reaching positive δ15N values. These sharp fluctuations cannot be attributed to fractionation. They may reflect arrival of new small pulses of melt or fluid that evolved under different conditions. Alternatively, they may result from fractionation between different growth directions, so that distinct δ15N values and N concentrations may form during diamond growth from a single melt/fluid. Other more continuous variations, in the core of ON-SLZ-390 or the rim of ON-SLZ-392 may be the result of Rayleigh fractionation or mixing.

Geochemical and iron isotopic insights into hydrothermal iron oxyhydroxide deposit formation at Loihi Seamount

NASA Astrophysics Data System (ADS)

Rouxel, Olivier; Toner, Brandy; Germain, Yoan; Glazer, Brian

2018-01-01

Low-temperature hydrothermal vents, such as those encountered at Loihi Seamount, harbor abundant microbial communities and provide ideal systems to test hypotheses on biotic versus abiotic formation of hydrous ferric oxide (FeOx) deposits at the seafloor. Hydrothermal activity at Loihi Seamount produces abundant microbial mats associated with rust-colored FeOx deposits and variably encrusted with Mn-oxyhydroxides. Here, we applied Fe isotope systematics together with major and trace element geochemistry to study the formation mechanisms and preservation of such mineralized microbial mats. Iron isotope composition of warm (<60 °C), Fe-rich and H2S-depleted hydrothermal fluids yielded δ56Fe values near +0.1‰, indistinguishable from basalt values. Suspended particles in the vent fluids and FeOx deposits recovered nearby active vents yielded systematically positive δ56Fe values. The enrichment in heavy Fe isotopes between +1.05‰ and +1.43‰ relative to Fe(II) in vent fluids suggest partial oxidation of Fe(II) during mixing of the hydrothermal fluid with seawater. By comparing the results with experimentally determined Fe isotope fractionation factors, we determined that less than 20% of Fe(II) is oxidized within active microbial mats, although this number may reach 80% in aged or less active deposits. These results are consistent with Fe(II) oxidation mediated by microbial processes considering the expected slow kinetics of abiotic Fe oxidation in low oxygen bottom water at Loihi Seamount. In contrast, FeOx deposits recovered at extinct sites have distinctly negative Fe-isotope values down to -1.77‰ together with significant enrichment in Mn and occurrence of negative Ce anomalies. These results are best explained by the near-complete oxidation of an isotopically light Fe(II) source produced during the waning stage of hydrothermal activity under more oxidizing conditions. Light Fe isotope values of FeOx are therefore generated by subsurface precipitation of isotopically heavy Fe-oxides rather than by the activity of dissimilatory Fe reduction in the subsurface. Overall, Fe-isotope compositions of microbial mats at Loihi Seamount display a remarkable range between -1.2‰ and +1.6‰ which indicate that Fe isotope compositions of hydrothermal Fe-oxide precipitates are particularly sensitive to local environmental conditions where they form, and are less sensitive to abiotic versus biotic origins. It follows that FeOx deposits at Loihi Seamount provides important modern analogues for ancient seafloor Fe-rich deposits allowing for testing hypotheses about the biogeochemical cycling of Fe isotopes on early Earth.

Stable isotope evolution and paleolimnology of ancient Lake Creede

USGS Publications Warehouse

Rye, Robert O.; Bethke, Philip M.; Finkelstein, David B.

2000-01-01

The lacustrine carbonate and travertine (tufa) deposits of ancient Lake Creede preserve a remarkable record of the isotopic evolution of the lake. That record indicates that the δ18O of the lake water, and by analogy its salinity, evolved through evaporation. Limited and less reliable data on hydrous minerals and fluid inclusions in early diagenetic carbonates indicate that the δD of the lake waters also evolved through evaporation. The isotope data place restrictions on models of the physical limnology of the lake and its evolution.The closed-basin Lake Creede formed shortly after collapse of the 26.9 Ma Creede caldera. Throughout most of its history it occupied the northern three quarters of the moat between the resurgent dome and wall of the caldera. The Creede Formation was deposited in the basin, dominantly as lacustrine sediments. Travertine mounds interfinger with Creede Formation sediments along the inner and outer margins of the lake basin. An estimated one-half of the original thickness of the Creede Formation has been lost mainly to erosion although scattered remnants of the upper portion remain on the caldera walls. Two diamond core holes (CCM-1 and CCM-2) sampled the uneroded portion of the Creede Formation as part of the U.S. Continental Drilling Program. Volcaniclastic material, including tuff units deposited directly into the lake and ash washed in from the watershed, compose the main lithologies of the Creede Formation. These volcaniclastic strata were produced by episodic ring-fracture volcanism.Lacustrine carbonates make up about 15% of the section sampled by drill core. They occur as 1 mm to 2 cm low-Mg calcite laminae alternating with siliciclastic laminae in scattered intervals throughout the preserved section. The carbonate laminae are accumulations of 5–20 µm crystallites (microsparites) and brine shrimp fecal pellets (peloids) composed mainly of microsparite particles. Low-Mg calcite also occurs as an early diagenetic replacement of gypsum or ikaite (CaCO3 ·6H2O) crystals grown displacively in the muds and silts near the water-sediment interface (rice grains). Other studies indicate that aragonite was the original CaCO3 precipitate forming the microsparite and peloidal laminae and that it converted to calcite during burial diagenesis. Samples from CCM-2 and nearby outcrop do not appear to have undergone significant isotope exchange during recrystallization. Samples from CCM-1 and nearby outcrop, however, appear to have undergone extensive oxygen isotope exchange with meteoric water-dominated fluids possibly during a local 17.6 Ma hydrothermal event.The δ18O-δ13C data set produced by microsampling of individual carbonate lamellae and rice grains is exceptional in several aspects and provides important clues concerning the evolution of limnologic structure of the lake and its chemical and isotopic composition. Travertine and ikaite pseudomorphs in travertine deposits extend the record an additional 330 m above the collar of CCM-2. The δ18O values on CCM-2 samples range from 10.4‰ to 37.3‰ and δ13C values range from –10.8‰ to 9.6‰. The data fall into two distinct groups, a covariant group and an invariant group. The covariant group shows a strong negative covariance and a large range of δ18O and δ13C values. The negative covariance is opposite that normally reported for lacustrine carbonates. The large range of δ18O and δ13C values requires that the carbonates precipitated from waters have a large range of temperature and carbon and oxygen isotopic composition. The invariant group has a narrow range of large δ18O values (35‰ ± 2‰) and a wide range of δ13C values (–10.8‰ to 9.6‰), indicating precipitation from waters with a narrow range of temperature and δ18O but a wide range in δ13C of aqueous carbon. The ranges of isotope values for microsparite and peloid samples are virtually identical; two-thirds are in the covariant group. By contrast, the values for almost all rice grain samples are in the invariant group. The range in δ18O for all samples reflects precipitation from waters having varying proportions of deep, cold evaporated lake water and shallow, warmer meteoric water. The range for δ13C reflects varying proportions of organic carbon and carbon of volcanic or atmospheric origin, probably dominantly volcanic, in the aqueous carbon.Changes in the detailed carbon-oxygen isotope systematics with stratigraphic position define three periods of isotopic evolution of Lake Creede. Period I is represented by the lowest ~200 m of Creede Formation core in CCM-2. Analyses of individual microsparite and peloidal carbonate laminae within single thin sections of samples from that interval are tightly grouped. The data set as a whole shows a negative covariance. Rice grains are not found in this interval. Period II is represented by the succeeding 120 m of core in CCM-2. In that interval, δ13C-δ18O values for individual microsparite and peloidal carbonate laminae within single thin sections show strong negative covariance, and the set of values for the entire interval also shows strong negative covariance. Rice grains occur near the top of the interval. Period III is represented by the upper 225 m of CCM-2 core. In this interval, rice grains are abundant and δ13C-δ18O values for microsparite and peloidal laminae as well as rice grains fall in the invariant group.During Period I the lake was well mixed and the oxygen isotopic composition of the lake in the productive zone was only slightly influenced by short-term (e.g., annual) variations in the water budget of the lake. In Period II the lake was stratified, possibly with annual overturn. The productive zone included the mixolimnion and the isotopic composition of the microsparites and peloids reflected mixtures of shallow surface (meteoric) water containing volcanic or atmospheric CO2 (epilimnion) and cold underlying waters, the oxygen isotopic compositions of which had evolved through evaporation and were dominated by CO2 produced by the oxidation of organic matter (hypolimnion). During Period III the lake remained stratified. The productive zone was in the hypolimnion, probably due to a thinning of the epilimnion resulting from an increase in the surface area of the lake or a decrease in input waters reflecting a climate change. An upsection increase in values of δ18O for the heaviest samples during Periods I and II indicates evaporative concentration of 18O and, by analogy, salinity in the hypolimnion.The δD-δ18O evolution of the lake is inferred on theoretical evaporation trends, comparison to Mono Lake, and measurement of the δD in fluid inclusions in a calcite pseudomorph after ikaite. The δD-δ18O composition of the lake water followed a curved path that eventually hooked over at a nearly constant δ18O value for the lake of 2‰ ± 2‰Travertine (tufa) mounds formed along the inner and outer margins of the lake in a zone of mixing of warm, volcanic CO2-bearing, meteoric waters and lake water. Ikaite crystals formed on the mounds from unmixed saline lake water, probably below the thermocline. As the position of the thermocline deepened, likely following the spring runoff, the ikaite was replaced by calcite and the resulting “pearls” were covered with travertine deposited from mixed meteoric and lake waters.The upsection increase in δ18O values of the carbonates, the long period of invariance of large δ18OH2O values, the presence of brine shrimp fecal pellets, and the inferred hooked δD-δ18O path are consistent with evidence from other studies that Lake Creede obtained significant salinity rather early in its history and certainly by the time the lake became permanently stratified.

Zinc Isotopes as Tracers of Crust-Mantle Interactions and Mineralization Processes in Layered Intrusions

NASA Astrophysics Data System (ADS)

Day, J. M.; Moynier, F.

2016-12-01

Zinc isotopes are a powerful tool for studying igneous processes and may be useful for distinguishing between mantle or crustal origins for mineralization and for examining crystallization processes. Restricted ranges in δ66Zn for mantle-derived rocks (δ66Zn = 0.28±0.05‰; [{66Zn/64Znsample/66Zn/64ZnJMC-Lyon-1} × 1000] all uncertainties reported are 2SD) contrast the large δ66Zn variations in sedimentary rocks ( 0 to 1‰), or in volcanic and sedimentary hosted ore deposits (e.g., SEDEX; VHMS; MVT = -0.6 to 1.3‰). Here, we use Zn isotopes to investigate magmatic processes in the 1.27 Ga Muskox Intrusion (Canada) and 2.7 Ga Stillwater Intrusion (Montana). The Muskox main chromitite horizon has between 270-330 ppm Zn with δ66Zn ranging from 0.16 to 0.31‰. Zinc isotope compositions negatively correlate with Os isotopes. Chromitite (40a) with the lowest 187Os/188Os (0.132) has δ66Zn of 0.31±0.03‰; indistinguishable from the mantle value. CM19 glass from the co-eval Coppermine Volcanics, which has crust-like O and Nd isotopes but low 187Os/188Os (0.131), has been interpreted as the extrusive manifestation of chromitite genesis. The value of δ66Zn (0.27±0.07‰) for CM19 is within uncertainty of 40A, and permissive of formation during silicic-mafic melt mixing and large-scale chromitite crystallization. Stillwater chromitite seams exhibit a larger range in Zn (166-448 ppm), but generally lower δ66Zn (0.13±0.04‰) than Muskox chromitites, or to a JM Reef bulk sample (69 ppm Zn, δ66Zn = 0.22±0.03‰). These results suggest different sources of Zn for Ultramafic series chromitites versus the JM Reef (Banded series). Correspondingly, variations occur in Os isotopes for PGE poor chromitites (γOs = -2 to +4) versus the PGE-rich JM Reef (γOs = +12 to +34). Zinc isotope variations may be explained by either a mantle source with low δ66Zn that was subsequently contaminated by high δ66Zn crust, or from contamination of the ultramafic series by low δ66Zn continental lithospheric mantle. JM Reef sulphides span a wide range in Zn (1.8-350 ppm) and δ66Zn (-0.03 to 0.68‰) consistent with fractionation of Zn isotopes during sulphide melt-mineral crystallization. These results show promise for using Zn isotopes to study sources of mineralization and to elucidate sulphide crystallization processes.

High arsenic concentrations and enriched sulfur and oxygen isotopes in a fractured-bedrock ground-water system

USGS Publications Warehouse

Lipfert, G.; Sidle, W.C.; Reeve, A.S.; Ayuso, R.A.; Boyce, A.J.

2007-01-01

Ground water with high arsenic concentrations (up to 26.6????mol L- 1) has sulfate enriched in 34S and 18O in the fractured-bedrock, ground-water system of the Kelly's Cove watershed, Northport, Maine, USA. The ranges of sulfur and oxygen isotope values in aqueous sulfate, ??34S[SO4] and ??18O[SO4], at the Kelly's Cove watershed are + 3.4 to + 4.9??? and - 2.0 to + 6.7???, respectively. These isotope values are strikingly similar to those of the Goose River, Maine watershed which has ??34S[SO4] and ??18O[SO4] ranges of + 3.7 to + 4.6 ??? and - 2.6 to + 7.5???, respectively. In both systems, high arsenic concentrations occur with high ??34S[SO4] and ??18O[SO4] values, yet redox conditions and underlying rock types are quite different. The isotope values of sulfide minerals, ??34S[min], from four bedrock cores vary over short distances and range from - 5.1 to + 7.5???. The ??34S[SO4] values are controlled by the ??34S[min] values with minor input of atmospheric SO4. The much narrower range in ??34S[SO4] values than ??34S[min] values is probably due to sufficient ground-water mixing at a scale greater than the ??34S[min] variability. The ??34S[SO4] values are about 2??? higher than the average ??34S[min] value and fall within the range of ??34S[min] values, indicating only minor fractionation due to bacterial reduction of SO4. The highest ??18O[SO4] values were measured in the downgradient, confined, arsenic-rich ground water. High ??18O[SO4] values there cannot be due to aeration by atmospheric oxygen, but may arise from reoxidation of reduced SO4 products. The enrichment factors of ??18O in SO4 compared to H2O, + 7.2 to + 15.5???, in the Kelly's Cove ground water and the negligible 34S enrichment is very similar to those derived from experimental data of anaerobic sulfide oxidation in the presence of Mn and Fe oxides. Sea level at the Kelly's Cove watershed was approximately 80??m above present sea level about 13 000??years before present, imposing reducing conditions on that area of the watershed. Sea level dropped approximately 60??m below present sea level about 11 000??years before present, allowing for possible oxidation of sulfide minerals and precipitation of arsenic in ferric oxyhydroxides during aeration of the ground-water system. Under present redox conditions, there is evidence that bacteria reduction of ferric oxyhydroxides releases arsenic. The fractionation of 18O in the SO4 during anaerobic oxidation of sulfide in the presence of Mn and Fe oxides and subsequent release of arsenic during Mn and Fe oxide reduction may explain the relationship between high arsenic concentrations and elevated 18O[SO4] at Kelly's Cove. ?? 2007 Elsevier B.V. All rights reserved.

Stable carbon and nitrogen isotope enrichment in primate tissues

PubMed Central

Carter, Melinda L.; Karpanty, Sarah M.; Zihlman, Adrienne L.; Koch, Paul L.; Dominy, Nathaniel J.

2010-01-01

Isotopic studies of wild primates have used a wide range of tissues to infer diet and model the foraging ecologies of extinct species. The use of mismatched tissues for such comparisons can be problematic because differences in amino acid compositions can lead to small isotopic differences between tissues. Additionally, physiological and dietary differences among primate species could lead to variable offsets between apatite carbonate and collagen. To improve our understanding of the isotopic chemistry of primates, we explored the apparent enrichment (ε*) between bone collagen and muscle, collagen and fur or hair keratin, muscle and keratin, and collagen and bone carbonate across the primate order. We found that the mean ε* values of proteinaceous tissues were small (≤1‰), and uncorrelated with body size or phylogenetic relatedness. Additionally, ε* values did not vary by habitat, sex, age, or manner of death. The mean ε* value between bone carbonate and collagen (5.6 ± 1.2‰) was consistent with values reported for omnivorous mammals consuming monoisotopic diets. These primate-specific apparent enrichment values will be a valuable tool for cross-species comparisons. Additionally, they will facilitate dietary comparisons between living and fossil primates. Electronic supplementary material The online version of this article (doi:10.1007/s00442-010-1701-6) contains supplementary material, which is available to authorized users. PMID:20628886

Environmental controls on leaf wax δD ratios in surface peats across the monsoonal region of China

NASA Astrophysics Data System (ADS)

Huang, X.; Xue, J.; Wang, X.; Meyers, P. A.

2015-09-01

Leaf wax molecular and isotopic ratios are generally considered robust isotopic paleohydrologic proxies. Here we evaluate the proxy value of the molecular distributions and hydrogen isotopic compositions of long chain n-alkanes (δDalk) in surface peats collected from peatlands across a range of annual air temperatures from 1 to 15 °C and a range of annual mean precipitation from 720 to 2070 mm in the monsoonal region of China. The alkane ratios (ACL and CPI) and δDalk values show relatively large variations in multiple samples from a single site, highlighting the complexity of these ratios at a small spatial scale. In the montane Zoigê peatland, the apparent fractionation between precipitation and δDalk is more positive than in the other six sites, which is possibly an effect of the higher conductivity of the water in this high elevation site (3500 m a.s.l.). At a larger spatial scale, the site-averaged CPI ratios and the δDalk values of n-C29 and n-C31 alkanes show significant correlation with the air temperature and precipitation. These results support the application of the CPI ratio and the δDalk ratios of n-C29 and n-C31 alkanes as sensitive paleohydrologic proxies on millennial and larger timescales.

Using geochemical and isotopic techniques for exploration of geothermal energy in Southern Sabalan geothermal field, NW Iran

NASA Astrophysics Data System (ADS)

Masoumi, Rahim

2017-04-01

From a hydrogeochemical point of view the geothermal fluids in the study area can be divided into two categories, (1) Na-Cl and (2) Na-Ca-HCO3. In the study area, the hot water samples depict temperature and pH ranges of 22 °C to 77 °C and 6.4 to 7.3, respectively. The total dissolved solids vary from 456 mg/L to 7006 mg/L. The concentration of rare metallic and non-metallic elements such as Li, Rb, B, Ba, Sr, CS, Se, Al, As, Hg in cold and hot spring waters in the Bushdi area were also analyzed. The utmost concentration belongs to Se which ranges from 135 mg/L to 273 mg/L. Boron also shows notable concentration values, in most samples it exceeds 20 mg/L, and in certain samples it ranges from 28 mg/L to 33.5 mg/L. The concentration value of arsenic ranges from 3 mg/L to 4 mg/L. The maximum concentration value of mercury is 0.01 mg/L. The δ18O values of these samples vary from -12.4 ‰ to -7.5 ‰ and the δD values range from -78.6 ‰ to -70.6 ‰. Plotting δ18O versus δD demonstrates that the data points are clustered close to both, the global meteoric water line (GMWL) with the equation δD = 8 δ18O + 10 and, the national meteoric water line (NMWL) with the equation δD = 6.89 δ18O + 6.57. As can be observed, the geothermal fluids in the Bushdi area show relatively slight increase in δ18O values that may be caused by interaction of hot fluids with host volcanic rocks. In fact, this relatively slight increment in δ18O values may indicate the low to moderate temperature of the geothermal system. The δD values, in general, do not show notable variation because of very low hydrogen content of the host rocks. The slight increase in δD, however, may be in conjunction with vaporization and isotopic interaction with the host rocks. The 3H content of the cold and hot waters in the Bushdi area is relatively high and varies from 0.65 TU to 41.4 TU. This may be caused either by mixing with meteoric sources or rapid fluid flow within the system in a shorter time than the β- disintegration of the isotope 3H. The δ18O versus δD diagram demonstrates that the data for the Bushdi area is plotted in three distinct domains, a, b, c. In a, the 3H content is > 10 TU indicating these waters being modern waters. Domain b belongs to samples whose 3H values are within the range of 1 TU to 10 TU being temporally categorized as sub-modern waters. The water samples in c possess 3H values < 1 TU indicating the oldest waters within the geothermal system in the study area. Key words: Geothermal fluids, Stable isotopes, Tracemetals, Sabalan volcano.

Magnesium isotope geochemistry in arc volcanism.

PubMed

Teng, Fang-Zhen; Hu, Yan; Chauvel, Catherine

2016-06-28

Incorporation of subducted slab in arc volcanism plays an important role in producing the geochemical and isotopic variations in arc lavas. The mechanism and process by which the slab materials are incorporated, however, are still uncertain. Here, we report, to our knowledge, the first set of Mg isotopic data for a suite of arc lava samples from Martinique Island in the Lesser Antilles arc, which displays one of the most extreme geochemical and isotopic ranges, although the origin of this variability is still highly debated. We find the δ(26)Mg of the Martinique Island lavas varies from -0.25 to -0.10, in contrast to the narrow range that characterizes the mantle (-0.25 ± 0.04, 2 SD). These high δ(26)Mg values suggest the incorporation of isotopically heavy Mg from the subducted slab. The large contrast in MgO content between peridotite, basalt, and sediment makes direct mixing between sediment and peridotite, or assimilation by arc crust sediment, unlikely to be the main mechanism to modify Mg isotopes. Instead, the heavy Mg isotopic signature of the Martinique arc lavas requires that the overall composition of the mantle wedge is buffered and modified by the preferential addition of heavy Mg isotopes from fluids released from the altered subducted slab during fluid-mantle interaction. This, in turn, suggests transfer of a large amount of fluid-mobile elements from the subducting slab to the mantle wedge and makes Mg isotopes an excellent tracer of deep fluid migration.

Investigations of Methane Production in Hypersaline Environments

NASA Technical Reports Server (NTRS)

Bebout, Brad M.

2015-01-01

The recent reports of methane in the atmosphere of Mars, as well as the findings of hypersaline paleo-environments on that planet, have underscored the need to evaluate the importance of biological (as opposed to geological) trace gas production and consumption. Methane in the atmosphere of Mars may be an indication of life but might also be a consequence of geologic activity and/or the thermal alteration of ancient organic matter. Hypersaline environments have now been reported to be extremely likely in several locations in our solar system, including: Mars, Europa, and Enceladus. Modern hypersaline microbial mat communities, (thought to be analogous to those present on the early Earth at a period of time when Mars was experiencing very similar environmental conditions), have been shown to produce methane. However, very little is known about the physical and/or biological controls imposed upon the rates at which methane, and other important trace gases, are produced and consumed in these environments. We describe here the results of our investigations of methane production in hypersaline environments, including field sites in Chile, Baja California Mexico, California, USA and the United Arab Emirates. We have measured high concentrations of methane in bubbles of gas produced both in the sediments underlying microbial mats, as well as in areas not colonized by microbial mats in the Guerrero Negro hypersaline ecosystem, Baja California Mexico, in Chile, and in salt ponds on the San Francisco Bay. The carbon isotopic (d13C) composition of the methane in the bubbles exhibited an extremely wide range of values, (ca. -75 per mille ca. -25 per mille). The hydrogen isotopic composition of the methane (d2H) ranged from -60 to -30per mille and -450 to -350per mille. These isotopic values are outside of the range of values normally considered to be biogenic, however incubations of the sediments in contact with these gas bubbles reveals that the methane is indeed being produced by these sediments. Substrate limitation of methanogenesis in these environments, and not methane oxidation, would explain the isotopic values of the methane in these environments. Incubations with both isotopically labeled and unlabeled putative substrates for methanogenesis have shown that the substrates most important for methanogenesis in these environments are the so-called non-competitive substrates, e.g., methylamines, dimethylsulfide, and methanol. Acetate and bicarbonate appear not to be important substrates for methanogens in these environments. Extraction of DNA and analysis of a gene used for methane production (mcrA) has revealed that the community composition of methanogens is consistent with organisms known to use non-competitive substrates. Our work has shown that hypersaline environments have the potential to both produce and preserve methane for analysis, e.g., by capable rovers. Our work expends the range of methane isotopic values now known to be produced by active methanogenesis

Preservation and detection of microstructural and taxonomic correlations in the carbon isotopic compositions of individual Precambrian microfossils

NASA Astrophysics Data System (ADS)

Williford, Kenneth H.; Ushikubo, Takayuki; Schopf, J. William; Lepot, Kevin; Kitajima, Kouki; Valley, John W.

2013-03-01

Here we present techniques for, and new data from, in situ carbon isotope (δ13C) analysis of Precambrian permineralized microscopic fossils with a reproducibility of 1-2‰ using secondary ion mass spectrometry (SIMS). Individual microfossils, selected for their excellent preservation, were analyzed in petrographic thin sections of stromatolitic cherts from the Proterozoic Gunflint (˜1880 Ma), Bitter Springs (˜830 Ma), Min'yar (˜740 Ma), and Chichkan (˜775 Ma) Formations. The range of δ13C values (-34.6‰ to -22.1‰ VPDB) among the 46 individuals analyzed falls within that expected for photoautotrophic carbon fixation by ribulose bisphosphate carboxylase (RuBisCO), consistent with morphology-based taxonomic assignments for these specimens. Microfossils classified as cyanobacteria from the Gunflint, Bitter Springs, and Min'yar Formations (for which published carbonate carbon isotope data can be used to estimate the δ13C of the original dissolved inorganic carbon substrate) exhibit a consistent ˜19‰ total fractionation (δ13C of dissolved inorganic carbon - δ13C of biomass) similar to that observed in living cyanobacteria, over a wide range of δ13Ccarb values (-2.9‰ to 3.4‰). In stromatolitic chert of the Min'yar Formation, morphologically diverse microfossils preserved in a ˜1 mm2 part of a microbial mat exhibit systematic isotopic differences among and within taxa that correlate with their morphologically inferred biological affinities and suggest that isotopic signatures of their original biosynthetic processes (e.g., lipid and peptidoglycan synthesis) are preserved. Isotopic offsets consistent with the different RuBisCO-based fractionations typical of cyanobacteria and photosynthetic eukaryotes are documented by the differing δ13C values of a colonial cyanobacterium (-22.6 ± 0.5‰) and a phytoplanktonic protistan acritarch (-28.9 ± 1.0‰) situated <1 cm apart in the stromatolitic Chichkan chert. These findings show for the first time the possibility of using in situ isotopic microanalysis of fossil microbial mats and ancient sediments in order to distinguish metabolic fingerprints within complex microbial ecosystems and consortia.

Non-Destructive X-ray Computed Tomography (XCT) of Gas Hydrate Bearing Fractures in Marine Sediment

NASA Astrophysics Data System (ADS)

Oti, E.; Buchwalter, E.; Cook, A.; Crandall, D.

2017-12-01

Hydrate-filled fractures are found in many environments, both related to methane vents and constrained to lithologic layers; how hydrate filled fractures form in layered environments is not well understood. We focus on understanding hydrate origins and fracture formation by examining hydrate-bearing fractures in conventional cores taken from Gulf of Mexico sites from JIP Leg 1 and UT-GOM, Keathley Canyon 151. There are two main methane sources available for hydrate formation. The first is the hydrocarbon reservoir underlying the Gulf sediments. This reservoir formed when deeply buried organic matter of high molecular weight was exposed to high temperature and pressures and degraded. A second source is the biogenesis of organic material, which occurs when microbial activity breaks down organic materials. Biogenic methane is more enriched in lighter carbon isotopes as the reduction or fermentation reactions preferentially consume lighter carbon isotopes. As a result, we hypothesize that sediment surrounding biogenically derived methane will have heavier carbon isotopes when compared to non-host sediment, due to the consumption of the lighter carbon isotopes during methanogenesis. We use non-destructive X-ray Computed Tomography (XCT) scanning to visualize and identify hydrate-bearing fractures. The presence of hydrate fractures is further confirmed with a salinity analysis, as hydrate dissociation freshens the pore water and lowers the salinity. After hydrate fracture location is inferred, carbon isotope analysis is used to identify hydrocarbon source. XCT scans of Keathley Canyon core JIP-1 17H-4 revealed 10 total fractures, five of which XCT and salinity analysis indicated as formerly containing hydrate. All ten fractures, in addition to background sediment, underwent a carbon isotope analysis in which organic isotopes were measured. In the background sediment and the non hydrate-bearing fractures, DOC values were relatively light, with dC13 percentages ranging from -27.8% to -30.8%. In the five hydrate fracture regions, DOC was comparatively heavy, with DOC dC13 values ranging from -23.2% to -30.3%. These values suggest that biogenic methane was formed adjacent to the fracture and likely migrated into the hydrate filled fracture.

Investigating chloroperoxidase-catalyzed formation of chloroform from humic substances using stable chlorine isotope analysis.

PubMed

Breider, Florian; Hunkeler, Daniel

2014-01-01

Chloroperoxidase (CPO) is suspected to play an important role in the biosynthesis of natural chloroform. The aims of the present study are to evaluate the variability of the δ(37)Cl value of naturally produced chloroform and to better understand the reaction steps that control the chlorine isotope signature of chloroform. The isotope analyses have shown that the chlorination of the humic substances (HS) in the presence of high H3O(+) and Cl(-) concentrations induces a large apparent kinetic isotope effect (AKIE = 1.010-1.018) likely associated with the transfer of chlorine between two heavy atoms, whereas in the presence of low H3O(+) and Cl(-) concentrations, the formation of chloroform induces a smaller AKIE (1.005-1.006) likely associated with the formation of an HOCl-ferriprotoporphyrin IX intermediate. As the concentration of H3O(+) and Cl(-) in soils are generally at submillimolar levels, the formation of the HOCl-ferriprotoporphyrin IX intermediate is likely rate-limiting in a terrestrial environment. Given that the δ(37)Cl values of naturally occurring chloride tend to range between -1 and +1‰, the δ(37)Cl value of natural chloroform should vary between -5‰ and -8‰. As the median δ(37)Cl value of industrial chloroform is -3.0‰, the present study suggests that chlorine isotopic composition of chloroform might be used to discriminate industrial and natural sources in the environment.

ISO/GUM UNCERTAINTIES AND CIAAW (UNCERTAINTY TREATMENT FOR RECOMMENDED ATOMIC WEIGHTS AND ISOTOPIC ABUNDANCES)

DOE Office of Scientific and Technical Information (OSTI.GOV)

HOLDEN,N.E.

2007-07-23

The International Organization for Standardization (ISO) has published a Guide to the expression of Uncertainty in Measurement (GUM). The IUPAC Commission on Isotopic Abundance and Atomic Weight (CIAAW) began attaching uncertainty limits to their recommended values about forty years ago. CIAAW's method for determining and assigning uncertainties has evolved over time. We trace this evolution to their present method and their effort to incorporate the basic ISO/GUM procedures into evaluations of these uncertainties. We discuss some dilemma the CIAAW faces in their present method and whether it is consistent with the application of the ISO/GUM rules. We discuss the attemptmore » to incorporate variations in measured isotope ratios, due to natural fractionation, into the ISO/GUM system. We make some observations about the inconsistent treatment in the incorporation of natural variations into recommended data and uncertainties. A recommendation for expressing atomic weight values using a tabulated range of values for various chemical elements is discussed.« less

Comparison of δ18O measurements in nitrate by different combustion techniques

USGS Publications Warehouse

Revesz, Kinga; Böhlke, John Karl

2002-01-01

Three different KNO3 salts with δ18O values ranging from about −31 to +54‰ relative to VSMOW were used to compare three off-line, sealed glass tube combustion methods (widely used for isotope studies) with a more recently developed on-line carbon combustion technique. All methods yielded roughly similar isotope ratios for KNO3 samples with δ18O values in the midpoint of the δ18O scale near that of the nitrate reference material IAEA-NO-3 (around +21 to +25‰). This reference material has been used previously for one-point interlaboratory and intertechnique calibrations. However, the isotope ratio scale factors by all of the off-line combustion techniques are compressed such that they are between 0.3 and 0.7 times that of the on-line combustion technique. The contraction of the δ18O scale in the off-line preparations apparently is caused by O isotope exchange between the sample and the glass combustion tubes. These results reinforce the need for nitrate reference materials with δ18O values far from that of atmospheric O2, to improve interlaboratory comparability.

Direct determination of halogens in powdered geological and environmental samples using isotope dilution laser ablation ICP-MS

NASA Astrophysics Data System (ADS)

Boulyga, Sergei F.; Heumann, Klaus G.

2005-04-01

Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) with a special laser ablation system for bulk analyses (LINA-Spark(TM)-Atomiser) was applied for direct determinations of chlorine, bromine, and iodine in rock and sediment samples. Special attention was focused on possible inter-halogen fractionations and analyte/spike isotope fractionations by using LA-ICP-MS and LA-ICP-IDMS, respectively. A variation of Br/Cl and I/Cl element intensity ratios by a factor of 1.3-3 was observed when changing the nebulizer gas flow rate in the range of 0.84-1.0 L min-1 and the laser power density in the range of 2-10 GW cm-2, respectively. When using an internal standard for halogen quantification in LA-ICP-MS, this inter-element fractionation can cause systematic errors, which can be avoided by applying the isotope dilution technique. However, at high laser power densities (>5.7 GW cm-2 for iodine and >4.0 GW cm-2 for bromine and chlorine) the corresponding measured isotope ratio of the isotope-diluted sample deviates significantly from the target value. Under optimised conditions concentrations in the range of 30 [mu]g g-1-16 × 103 [mu]g g-1 for chlorine, <2-140 [mu]g g-1 for bromine, and <0.1-31 [mu]g g-1 for iodine were determined by LA-ICP-IDMS in two sediment reference materials (SRM 1646, SRM 2704) and three rock reference samples (GS-N, Granite; BX-N, Bauxite; DT-N, Disthene), which have not been certified for these halogens. The sediment results agree well within the given uncertainties with indicative values by different methods and the results of the rock samples with those obtained by negative thermal ionisation isotope dilution mass spectrometry. The detection limits of LA-ICP-IDMS are 8 [mu]g g-1 for chlorine, 1.7 [mu]g g-1 for bromine, and 0.1 [mu]g g-1 for iodine.

Re-evaluation of the origin and evolution of > 4.2 Ga zircons from the Jack Hills metasedimentary rocks

NASA Astrophysics Data System (ADS)

Nemchin, A. A.; Pidgeon, R. T.; Whitehouse, M. J.

2006-04-01

New data are presented on internal structures, U-Pb systematics and oxygen isotope compositions of eight detrital zircons with ages greater than 4.2 Ga, from the Jack Hills metasedimentary belt, Australia. Cathodoluminescence imaging, ion-microprobe U-Pb and oxygen isotope results show evidence for an extensive period of complex zircon growth, secondary reaction and U-Pb isotopic disturbance from 4.36 to 3.90 Ga. In addition many of the zircons have discordant U-Pb systems and excess common Pb indicating a superimposed, relatively recent, reaction between radiation damaged zircon and low temperature fluids. The significance of oxygen isotope compositions for zircons with complex internal structures and U-Pb systems is complicated by uncertainty in the origin of the grains and the unknown effect of later reactions. However, a minority of grains with sharp oscillatory zoning, uniform and concordant U-Pb systems, igneous Th-U ratios and low common Pb contents, are interpreted as undisturbed primary magmatic zircons. The oldest identified, oscillatory zoned, magmatic grain, with an age 4363 ± 20 Ma, is one of a few reported magmatic grains with this age, which is interpreted as the oldest reliable age for Hadean magmatic zircons. Mantle δ18O values are reported for these zircons. Younger oscillatory zoned zircon, including oscillatory zoned cores in complex grains, have δ18O values lower than 6.5‰, which are within the range of ion microprobe analysed δ18O values for zircons in high temperature equilibrium with the normal mantle rocks of 5.3 ± 0.6‰ (2 standard deviations). These values are also within the range of δ18O values found in lunar zircons. The absence of heavy oxygen in the grains that can be interpreted as primary magmatic zircons and the complex history over the period from 4.36 to 3.9 Ga, seen in all other Jack Hills zircons and reflected in the internal structures and U-Pb isotopic systems, questions the model for the early Earth involving long intervals of relatively temperate conditions from 4.4 to 4.0 Ga that were conducive to oceans and possibly life.

Elemental and isotopic (C, O, Sr, Nd) compositions of Late Paleozoic carbonated eclogite and marble from the SW Tianshan UHP belt, NW China: Implications for deep carbon cycle

NASA Astrophysics Data System (ADS)

Zhu, Jianjiang; Zhang, Lifei; Lü, Zeng; Bader, Thomas

2018-03-01

Subduction zones are important for understanding of the global carbon cycle from the surface to deep part of the mantle. The processes involved the metamorphism of carbonate-bearing rocks largely control the fate of carbon and contribute to local carbon isotopic heterogeneities of the mantle. In this study, we present petrological and geochemical results for marbles and carbonated eclogites in the Southwestern Tianshan UHP belt, NW China. Marbles are interlayered with coesite-bearing pelitic schists, and have Sr-Nd isotopic values (εNd (T=320Ma) = -3.7 to -8.9, 87Sr/86Sr (i) = 0.7084-0.7089), typical of marine carbonates. The marbles have dispersed low δ18OVSMOW values (ranging from 14 to 29‰) and unaffected carbon isotope (δ13CVPDB = -0.2-3.6‰), possibly due to infiltration of external H2O-rich fluids. Recycling of these marbles into mantle may play a key role in the carbon budget and contributed to the mantle carbon isotope heterogeneity. The carbonated eclogites have high Sr isotopic compositions (87Sr/86Sr (i) = 0.7077-0.7082) and positive εNd (T = 320 Ma) values (from 7.6 to 8.2), indicative of strong seafloor alteration of their protolith. The carbonates in the carbonated eclogites are mainly dolomite (Fe# = 12-43, Fe# = Fe2+/(Fe2+ + Mg)) that were added into oceanic basalts during seafloor alteration and experienced calcite - dolomite - magnesite transformation during the subduction metamorphic process. The uniformly low δ18O values (∼11.44‰) of carbonates in the carbontaed eclogites can be explained by closed-system equilibrium between carbonate and silicate minerals. The low δ13C values (from -3.3 to -7.7‰) of the carbonated eclogites most likely reflect contribution from organic carbon. Recycling of these carbonated eclogites with C isotope similar to typical mantle reservoirs into mantle may have little effect on the mantle carbon isotope heterogeneity.

Determination of the origin of groundwater nitrate at an air weapons range using the dual isotope approach.

PubMed

Bordeleau, Geneviève; Savard, Martine M; Martel, Richard; Ampleman, Guy; Thiboutot, Sonia

2008-06-06

Nitrate is one of the most common contaminants in shallow groundwater, and many sources may contribute to the nitrate load within an aquifer. Groundwater nitrate plumes have been detected at several ammunition production sites. However, the presence of multiple potential sources and the lack of existing isotopic data concerning explosive degradation-induced nitrate constitute a limitation when it comes to linking both types of contaminants. On military training ranges, high nitrate concentrations in groundwater were reported for the first time as part of the hydrogeological characterization of the Cold Lake Air Weapons Range (CLAWR), Alberta, Canada. Explosives degradation is thought to be the main source of nitrate contamination at CLAWR, as no other major source is present. Isotopic analyses of N and O in nitrate were performed on groundwater samples from the unconfined and confined aquifers; the dual isotopic analysis approach was used in order to increase the chances of identifying the source of nitrate. The isotopic ratios for the groundwater samples with low nitrate concentration suggested a natural origin with a strong contribution of anthropogenic atmospheric NOx. For the samples with nitrate concentration above the expected background level the isotopic ratios did not correspond to any source documented in the literature. Dissolved RDX samples were degraded in the laboratory and results showed that all reproduced degradation processes released nitrate with a strong fractionation. Laboratory isotopic values for RDX-derived NO(3)(-) produced a trend of high delta(18)O-low delta(15)N to low delta(18)O-high delta(15)N, and groundwater samples with nitrate concentrations above the expected background level appeared along this trend. Our results thus point toward a characteristic field of isotopic ratios for nitrate being derived from the degradation of RDX.

Oxygen isotopes in crystalline silicates of comet Wild 2: A comparison of oxygen isotope systematics between Wild 2 particles and chondritic materials

NASA Astrophysics Data System (ADS)

Nakashima, Daisuke; Ushikubo, Takayuki; Joswiak, David J.; Brownlee, Donald E.; Matrajt, Graciela; Weisberg, Michael K.; Zolensky, Michael E.; Kita, Noriko T.

2012-12-01

Oxygen three-isotope ratios of nine crystalline silicate particles from comet Wild 2 were measured to investigate oxygen isotope systematics of cometary materials. We are able to analyze particles as small as 4 μm using an ion microprobe with a˜1×2 μm beam by locating the analysis spots with an accuracy of ±0.4 μm. Three particles of Mn-rich forsterite, known as low-iron, manganese-enriched (LIME) olivine, showed extremely 16O-rich signatures (δ18O, δ17O˜-50‰), similar to refractory inclusions in chondrites. The three Mn-rich forsterite particles may have formed by condensation from an 16O-rich solar nebula gas. Other particles consist of olivine and/or pyroxene with a wide range of Mg# [=molar MgO/(FeO+MgO) %] from 60 to 96. Their oxygen isotope ratios plot nearly along the carbonaceous chondrite anhydrous mineral (CCAM) and Young and Russell lines with Δ17O(=δ17O-0.52×δ18O) values of -3.0‰ to +2.5‰. These data are similar to the range observed from previous analyses of Wild 2 crystalline silicates and those of chondrules in carbonaceous chondrites. Six particles extracted from Stardust track 77 show diverse chemical compositions and isotope ratios; two Mn-rich forsterites, FeO-poor pigeonite, and three FeO-rich olivines with a wide range of Δ17O values from -24‰ to +1.6‰. These results confirmed that the original projectile that formed track 77 was an aggregate (>6 μm) of silicate particles that formed in various environments. The Δ17O values of ferromagnesian Wild 2 particles (including data from previous studies) increase from ˜-23‰ to+2.5‰ with decreasing Mg#: Δ17O values of Mn-rich forsterite particles (Mg#=98-99.8) cluster at -23‰, those of FeO-poor particles (Mg#=95-97) cluster at -2‰, and those of FeO-rich particles (Mg#≤90) scatter mainly from -1.5‰ to+2.5‰. Compared to chondrules in primitive chondrites, the systematic trend between Mg# and Δ17O among the Wild 2 particles is most similar to that reported for CR chondrite chondrules. We argue that CR chondrites and some cometary materials share multiple common chemical and isotope characteristics. We suggest that many of the crystalline silicate particles formed in the outer regions of the asteroid belt, or regions that share the common properties, and were transported to comet-forming regions and accreted into comet Wild 2.

Comparison of liquid chromatography-isotope ratio mass spectrometry (LC/IRMS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) for the determination of collagen amino acid δ13C values for palaeodietary and palaeoecological reconstruction.

PubMed

Dunn, Philip J H; Honch, Noah V; Evershed, Richard P

2011-10-30

Results are presented of a comparison of the amino acid (AA) δ(13)C values obtained by gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) and liquid chromatography-isotope ratio mass spectrometry (LC/IRMS). Although the primary focus was the compound-specific stable carbon isotope analysis of bone collagen AAs, because of its growing application for palaeodietary and palaeoecological reconstruction, the results are relevant to any field where AA δ(13)C values are required. We compare LC/IRMS with the most up-to-date GC/C/IRMS method using N-acetyl methyl ester (NACME) AA derivatives. This comparison involves the analysis of standard AAs and hydrolysates of archaeological human bone collagen, which have been previously investigated as N-trifluoroacetyl isopropyl esters (TFA/IP). It was observed that, although GC/C/IRMS analyses required less sample, LC/IRMS permitted the analysis of a wider range of AAs, particularly those not amenable to GC analysis (e.g. arginine). Accordingly, reconstructed bulk δ(13)C values based on LC/IRMS-derived δ(13)C values were closer to the EA/IRMS-derived δ(13)C values than those based on GC/C/IRMS values. The analytical errors for LC/IRMS AA δ(13)C values were lower than GC/C/IRMS determinations. Inconsistencies in the δ(13)C values of the TFA/IP derivatives compared with the NACME- and LC/IRMS-derived δ(13)C values suggest inherent problems with the use of TFA/IP derivatives, resulting from: (i) inefficient sample combustion, and/or (ii) differences in the intra-molecular distribution of δ(13)C values between AAs, which are manifested by incomplete combustion. Close similarities between the NACME AA δ(13)C values and the LC/IRMS-derived δ(13)C values suggest that the TFA/IP derivatives should be abandoned for the natural abundance determinations of AA δ(13)C values. Copyright © 2011 John Wiley & Sons, Ltd.

Experimental evidence shows no fractionation of strontium isotopes ((87)Sr/(86)Sr) among soil, plants, and herbivores: implications for tracking wildlife and forensic science.

PubMed

Flockhart, D T Tyler; Kyser, T Kurt; Chipley, Don; Miller, Nathan G; Norris, D Ryan

2015-01-01

Strontium isotopes ((87)Sr/(86)Sr) can be useful biological markers for a wide range of forensic science applications, including wildlife tracking. However, one of the main advantages of using (87)Sr/(86)Sr values, that there is no fractionation from geological bedrock sources through the food web, also happens to be a critical assumption that has never been tested experimentally. We test this assumption by measuring (87)Sr/(86)Sr values across three trophic levels in a controlled greenhouse experiment. Adult monarch butterflies were raised on obligate larval host milkweed plants that were, in turn, grown on seven different soil types collected across Canada. We found no significant differences between (87)Sr/(86)Sr values in leachable Sr from soil minerals, organic soil, milkweed leaves, and monarch butterfly wings. Our results suggest that strontium isoscapes developed from (87)Sr/(86)Sr values in bedrock or soil may serve as a reliable biological marker in forensic science for a range of taxa and across large geographic areas.

Modes of planetary-scale Fe isotope fractionation

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; von Blanckenburg, Friedhelm

2006-12-01

A comprehensive set of high-precision Fe isotope data for the principle meteorite types and silicate reservoirs of the Earth is used to investigate iron isotope fractionation at inter- and intra-planetary scales. 14 chondrite analyses yield a homogeneous Fe isotope composition with an average δ56Fe/ 54Fe value of - 0.015 ± 0.020‰ (2 SE) relative to the international iron standard IRMM-014. Eight non-cumulate and polymict eucrite meteorites that sample the silicate portion of the HED (howardite-eucrite-diogenite) parent body yield an average δ56Fe/ 54Fe value of - 0.001 ± 0.017‰, indistinguishable to the chondritic Fe isotope composition. Fe isotope ratios that are indistinguishable to the chondritic value have also been published for SNC meteorites. This inner-solar system homogeneity in Fe isotopes suggests that planetary accretion itself did not significantly fractionate iron. Nine mantle xenoliths yield a 2 σ envelope of - 0.13‰ to + 0.09‰ in δ56Fe/ 54Fe. Using this range as proxy for the bulk silicate Earth in a mass balance model places the Fe isotope composition of the outer liquid core that contains ca. 83% of Earth's total iron to within ± 0.020‰ of the chondritic δ56Fe/ 54Fe value. These calculations allow to interprete magmatic iron meteorites ( δ56Fe/ 54Fe = + 0.047 ± 0.016‰; N = 8) to be representative for the Earth's inner metallic core. Eight terrestrial basalt samples yield a homogeneous Fe isotope composition with an average δ56Fe/ 54Fe value of + 0.072 ± 0.016‰. The observation that terrestrial basalts appear to be slightly heavier than mantle xenoliths and that thus partial mantle melting preferentially transfers heavy iron into the melt [S. Weyer, A.D. Anbar, G.P. Brey, C. Munker, K. Mezger and A.B. Woodland, Iron isotope fractionation during planetary differentiation, Earth and Planetary Science Letters 240(2), 251-264, 2005.] is intriguing, but also raises some important questions: first it is questionable whether the Fe isotope composition of lithospheric mantle xenoliths are representative for an undisturbed melt source, and second, HED and SNC meteorites, representing melting products of 4Vesta and Mars silicate mantles would be expected to show a similar fractionation towards heavy isotope compositions. This is not observed. Four international granitoid standards with SiO 2 contents between 60 and 70 wt.% yield δ56Fe/ 54Fe values between 0.118‰ and 0.132‰. An investigation of the alpine Bergell igneous rock suite revealed a positive correlation between Fe isotope compositions and SiO 2 contents — from gabbros and tonalites ( δ56Fe/ 54Fe ≈ 0.03 to 0.09‰) to granodiorites and silicic dykes ( δ56Fe/ 54Fe ≈ 0.14 to 0.23‰). Although in this suite δ56Fe/ 54Fe correlates with δ18O values and radiogenic isotopes, open-system behavior to explain the heavy iron is not undisputed. This is because an obvious assimilant with the required heavy Fe isotope composition has so far not been identified. Alternatively, the relatively heavy granite compositions might be obtained by fractional crystallisation of the melt. Ultimately, further detailed studies on natural rocks and the experimental determination of mineral/melt fractionation factors at magmatic conditions are required to unravel whether or not iron isotope fractionation takes place during partial mantle melting and crystal fractionation.

Seasonal variations in the stable carbon isotopic signature of biogenic methane in a coastal sediment

NASA Technical Reports Server (NTRS)

Martens, C. S.; Green, C. D.; Blair, N. E.; Des Marais, D. J.

1986-01-01

Systematic seasonal variations in the stable carbon isotopic signature of methane gas occur in the anoxic sediments of Cape Lookout Bight, a lagoonal basin on North Carolina's Outer Banks. Values for the carbon isotope ratio of methane range from -57.3 per mil during summer to -68.5 per mil during winter in gas bubbles with an average methane content of 95 percent. The variations are hypothesized to result from changes in the pathways of microbial methane production and cycling of key substrates including acetate and hydrogen. The use of stable isotopic signatures to investigate the global methane cycle through mass balance calculations, involving various sediment and soil biogenic sources, appears to require seasonally averaged data from individual sites.

Antiquity of the biological sulphur cycle: evidence from sulphur and carbon isotopes in 2700 million-year-old rocks of the Belingwe Belt, Zimbabwe.

PubMed Central

Grassineau, N V; Nisbet, E G; Bickle, M J; Fowler, C M; Lowry, D; Mattey, D P; Abell, P; Martin, A

2001-01-01

Sulphur and carbon isotopic analyses on small samples of kerogens and sulphide minerals from biogenic and non-biogenic sediments of the 2.7 x 10(9) years(Ga)-old Belingwe Greenstone Belt (Zimbabwe) imply that a complex biological sulphur cycle was in operation. Sulphur isotopic compositions display a wider range of biological fractionation than hitherto reported from the Archaean. Carbon isotopic values in kerogen record fractionations characteristic of rubisco activity methanogenesis and methylotrophy and possibly anoxygenic photosynthesis. Carbon and sulphur isotopic fractionations have been interpreted in terms of metabolic processes in 2.7 Ga prokaryote mat communities, and indicate the operation of a diverse array of metabolic processes. The results are consistent with models of early molecular evolution derived from ribosomal RNA. PMID:11209879

Os isotope systematics of La Palma, Canary Islands: Evidence for recycled crust in the mantle source of HIMU ocean islands

NASA Astrophysics Data System (ADS)

Marcantonio, Franco; Zindler, Alan; Elliott, Tim; Staudigel, Hubert

1995-07-01

Sub-aerial lavas from the single ocean island of La Palma, Canary Islands show as large a variation in 187Os/186Os isotope ratios (1.13-1.59) as found across all of French Polynesia [1]. The La Palma lavas, however, display a restricted range of chemical composition and have all been erupted within the last 3.5 Ma. The highest Os isotopic compositions are observed in lavas with low Os concentrations. An uplifted sequence of lavas, that represent the early phase of submarine growth of the island, show extremely heterogeneous 187Os/186Os isotope ratios, from 1.21 to 3.53, with the most radiogenic values found in pillow rinds. Assimilation of these pillow rinds by ascending magma can readily account for highly radiogenic ratios ( 187Os/186Os > 1.3 ) found in lavas with Os concentrations below 30 ppt. Samples with Os concentrations too high to be significantly affected by assimilation still display a range in Os isotope ratios from 1.13 to 1.25. We argue that these radiogenic values reflect a HIMU mantle source that contains ancient recycled oceanic crust. Characteristic incompatible trace element ratios suggest further similarities between the mantle beneath La Palma and other HIMU islands. When potentially contaminated low-Os OIBs are screened from literature data, HIMU islands are found to display the highest Os isotope ratios (up to 1.25). PbOs systematics for uncontaminated OIBs do not define a simple two-component mixing relationship between ambient mantle and recycled oceanic crust of a single composition. We suggest that this is due to variable alteration and subduction-induced perturbation of the U/Pb ratio in the recycled material that forms a component of the HIMU source.

Constraining the thermal history of the North American Midcontinent Rift System using carbonate clumped isotopes and organic thermal maturity indices

USGS Publications Warehouse

Gallagher, Timothy M.; Sheldon, Nathan D.; Mauk, Jeffrey L.; Petersen, Sierra V.; Gueneli, Nur; Brocks, Jochen J.

2017-01-01

The Midcontinent Rift System (MRS) is a Late Mesoproterozoic (∼1.1 Ga) sequence of volcanic and sedimentary rocks exposed in the Lake Superior Region of North America. The MRS continues to be the focus of much research due to its economic mineral deposits as well as its archive of Precambrian life and tectonic processes. In order to constrain the post-depositional thermal history of the MRS, samples were analyzed for carbonate clumped isotope composition and organic thermal maturity. Clumped isotope values from sedimentary/early-diagenetic samples were partially reset during burial to temperatures between 68 and 75 °C. Solid-state reordering models indicate that maximum burial temperatures of 125–155 °C would reset the clumped isotope values to the observed temperature range prior to the onset of regional cooling and uplift. Clumped isotope results from late-stage veins in the White Pine Mine encompass a greater temperature range (49–116 °C), indicative of spatially variable hydrothermal activity and vein emplacement after burial temperatures fell below 100 °C during regional cooling and uplift. Clumped isotope and organic thermal maturity data do not indicate significant spatial differences in thermal history along the MRS. Observed variability in bulk organic matter composition and biomarker indices are therefore more likely a result of shifts in primary productivity or early-degradation processes. These results demonstrate that the MRS experienced a spatially consistent, relatively mild thermal history (125–155 °C) and is therefore a valuable archive for understanding the Late Mesoproterozoic environment.

The suitability of a simplified isotope-balance approach to quantify transient groundwater-lake interactions over a decade with climatic extremes

USGS Publications Warehouse

Sacks, Laura A.; Lee, Terrie M.; Swancar, Amy

2013-01-01

Groundwater inflow to a subtropical seepage lake was estimated using a transient isotope-balance approach for a decade (2001–2011) with wet and dry climatic extremes. Lake water δ18O ranged from +0.80 to +3.48 ‰, reflecting the 4 m range in stage. The transient δ18O analysis discerned large differences in semiannual groundwater inflow, and the overall patterns of low and high groundwater inflow were consistent with an independent water budget. Despite simplifying assumptions that the isotopic composition of precipitation (δP), groundwater inflow, and atmospheric moisture (δA) were constant, groundwater inflow was within the water-budget error for 12 of the 19 semiannual calculation periods. The magnitude of inflow was over or under predicted during periods of climatic extreme. During periods of high net precipitation from tropical cyclones and El Niño conditions, δP values were considerably more depleted in 18O than assumed. During an extreme dry period, δA values were likely more enriched in 18O than assumed due to the influence of local lake evaporate. Isotope balance results were most sensitive to uncertainties in relative humidity, evaporation, and δ18O of lake water, which can limit precise quantification of groundwater inflow. Nonetheless, the consistency between isotope-balance and water-budget results indicates that this is a viable approach for lakes in similar settings, allowing the magnitude of groundwater inflow to be estimated over less-than-annual time periods. Because lake-water δ18O is a good indicator of climatic conditions, these data could be useful in ground-truthing paleoclimatic reconstructions using isotopic data from lake cores in similar settings.

Multi-isotope (carbon and chlorine) analysis for fingerprinting and site characterization at a fractured bedrock aquifer contaminated by chlorinated ethenes.

PubMed

Palau, Jordi; Marchesi, Massimo; Chambon, Julie C C; Aravena, Ramon; Canals, Àngels; Binning, Philip J; Bjerg, Poul L; Otero, Neus; Soler, Albert

2014-03-15

The use of compound specific multi-isotope approach (C and Cl) in the characterization of a chlorinated ethenes contaminated fractured aquifer allows the identification of several sources and contaminant plumes, as well as the occurrence of biodegradation and mixing processes. The study site is located in Spain with contamination resulting in groundwater concentrations of up to 50mg/L of trichloroethene (TCE), the most abundant chlorinated ethene, and 7 mg/L of tetrachloroethene (PCE). The potential sources of contamination including abandoned barrels, an underground tank, and a disposal lagoon, showed a wide range in δ(13)C values from -15.6 to -40.5‰ for TCE and from -18.5 to -32.4‰ for PCE, allowing the use of isotope fingerprinting for tracing of the origin and migration of these contaminants in the aquifer. In contrast, there is no difference between the δ(37)Cl values for TCE in the contaminant sources, ranging from +0.53 to +0.66‰. Variations of δ(37)Cl and δ(13)C in the different contaminant plumes were used to investigate the role of biodegradation in groundwater. Moreover, the isotopic data were incorporated into a reactive transport model for determination of whether the isotope pattern observed downstream from the tank's source could be explained by the simultaneous effect of mixing and biodegradation. The results demonstrate that a multi-isotope approach is a valuable tool for characterization of complex sites such as fractured bedrock aquifer contaminated by multiple sources, providing important information which can be used by consultants and site managers to prioritize and design more successful remediation strategies. Copyright © 2013 Elsevier B.V. All rights reserved.

Variations of geothermometry and chemical-isotopic compositions of hot spring fluids in the Rehai geothermal field, southwestern China

NASA Astrophysics Data System (ADS)

Du, Jianguo; Liu, Congqiang; Fu, Bihong; Ninomiya, Yoshiki; Zhang, Youlian; Wang, Chuanyuan; Wang, Hualiu; Sun, Zigang

2005-04-01

Geothermal variations, origins of carbon-bearing components and reservoir temperatures in the Rehai geothermal field (RGF) of Tengchong volcanic area, Yunnan Province, southwestern China, are discussed on the basis of carbon isotope compositions, combined with helium isotope ratios and geothermal data from 1973 to 2000. δ 13C values of CO 2, CH 4, HCO 3-, CO 3= and travertine in the hot springs range from -7.6‰ to -1.18‰, -56.9‰ to -19.48‰, -6.7‰ to -4.2‰, -6.4‰ to -4.2‰ and -27.1‰ to +0.6‰, respectively. The carbon dioxide probably has a mantle/magma origin, but CH 4 and He have multiple origins. HCO 3- and CO 3= in RGF thermal fluids are predominantly derived from igneous carbon dioxide, but other ions originate from rocks through which the fluids circulate. The 13C values of CO 2, HCO 3- (aq) and CO 3= (aq) illustrate that isotopic equilibriums between CO 2 and HCO 3- (aq), and CO 3= (aq) and between DIC and travertine were not achieved, and no carbon isotope fractionation between HCO 3- (aq) and CO 3= (aq) of the hot springs in RGF was found. Using various geothermometers, temperatures of the geothermal reservoirs are estimated in a wide range from 69 °C to 450 °C that fluctuated from time to time. The best estimate of subsurface reservoir temperature may be 250-300 °C. Contributions of mantle fluids and shallow crust fluids in Rehai geothermal field varied with time, which resulted in variations of chemical and isotopic compositions and reservoir temperatures.

A multi‐isotope investigation of diet and subsistence amongst island and mainland populations from early medieval western Britain

PubMed Central

Lamb, Angela L.; Chenery, Carolyn A.; Evans, Jane A.

2016-01-01

Abstract Objectives This is the first investigation of dietary practices amongst multiple early medieval populations (AD 500–1000) from Wales and the Isle of Man using carbon, nitrogen, and sulphur isotope analysis. The analysis will illuminate similarities or differences between the diets and subsistence strategies of populations occupying different geographical regions, specifically those living in marginal coastal regions in comparison to inland populations well‐connected to ecclesiastical centres and high‐status settlements. Materials and Methods One hundred and two human skeletons were sampled for carbon and nitrogen isotope analysis, and 69 human skeletons were sampled for sulphur isotope analysis from nine cemetery sites from western Britain (Isle of Man = 3, southwest Wales = 4, southeast Wales = 2). Thirteen faunal skeletons from St Patrick's Chapel (southwest Wales) were sampled for carbon, nitrogen, and sulphur isotope analysis. Results Human δ13C values range from −19.4‰ to −21.2‰ (δ13C mean=−20.4 ±0.4‰, 1σ, n = 86), and δ15N values range from 9.1‰ to 13.8‰ (δ15N mean = 10.8 ± 0.9‰, 1σ, n = 86). δ34S values range from 1.2‰ to 18.4‰ (δ34S mean = 11.6 ± 4.5‰, 1σ, n = 66). Significant differences were noted between the mean δ13C, δ15N and δ34S values according to geographic region: Isle of Man (δ13C = −20.7 ± 0.4‰, δ15N = 11.4 ±0.6‰, n = 13/86; δ34S mean = 17.1 ±0.6, n = 4/66), southwest Wales (δ13C = −20.5 ± 0.4‰, δ15N = 11.0 ±1‰, n = 32/86; δ34S = 16.1 ± 2.1, n = 21/66), and southeast Wales (δ13C =−20.3 ±0.4‰, δ15N = 10.4 ±0.7‰, n = 41/86; δ34S= 8.8 ±3‰, n = 41/66). Faunal δ13C values range from −23.1‰ to −21.2‰ (δ13C mean= −22.1 ±0.5‰, 1σ, n = 13), and δ15N values range from 6.3‰ to 9.8‰ (δ15N mean = 7.3 ± 1.1‰, 1σ, n = 13). δ34S values range from 4.7‰ to 18.4‰ (δ34S mean= 16.3 ± 3.6‰, 1σ, n = 13). Conclusions The data reveal a reliance on terrestrial protein, however differences are observed between the resource consumption of populations from southwest Wales and the Isle of Man in comparison to the populations from southeast Wales. Populations from the west coast have a marine sulphur signature that reflects their coastal proximity and may also include a reliance on seaweed as a fertiliser/food source. Populations in the southeast were connected to ecclesiastical centres and high‐status settlements and had access to inland‐grown produce. The data add support to the suggestion that δ34S can be used as a mobility indicator. PMID:27858981

Stable Isotope Systematics of Martian Perchlorate

NASA Astrophysics Data System (ADS)

Martin, P.; Farley, K. A.; Archer, D., Jr.; Atreya, S. K.; Conrad, P. G.; Eigenbrode, J. L.; Fairen, A.; Franz, H. B.; Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Malespin, C.; Ming, D. W.; Navarro-Gonzalez, R.; Sutter, B.

2015-12-01

Chlorine isotopic compositions in HCl released during evolved gas analysis (EGA) runs have been detected by the Sample Analysis at Mars (SAM) instrument on the Curiosity rover ranging from approximately -9‰ to -50‰ δ37Cl, with two spatially and isotopically separated groups of samples averaging -15‰ and -45‰. These extremely low values are the first such detection of any known natural material; common terrestrial values very rarely exceed ±5‰, and the most extreme isotopic signature yet detected elsewhere in the solar system are values of around +24‰ on the Moon. The only other known location in the solar system with large negative chlorine isotopes is the Atacama Desert, where perchlorate with -14‰ δ37Cl has been detected. The Atacama perchlorate has unusual Δ17O signatures associated with it, indicating a formation mechanism involving O3, which suggests an atmospheric origin of the perchlorate and associated large isotopic anomalies. Identification of non-zero positive Δ17O signatures in the O2 released during EGA runs would allow definitive evidence for a similar process having occurred on Mars. Perchlorate is thought to be the most likely source of HCl in EGA runs due to the simultaneous onset of O2 release. If perchlorate is indeed the HCl source, atmospheric chemistry could be responsible for the observed isotopic anomalies, with variable extents of perchlorate production producing the isotopic variability. However, chloride salts have also been observed to release HCl upon heating; if the timing of O2 release is merely coincidental, observed HCl could be coming from chlorides. At thermodynamic equilibrium, the fractionation factor of perchlorate reduction is 0.93, meaning that differing amounts of post-deposition reduction of isotopically normal perchlorate to chloride could account for the highly variable Cl isotopes. Additionally, post-deposition reduction could account for the difference between the two Cl isotopic groups if perchlorate is the HCl source, as the residual perchlorate after reduction will be isotopically heavy. Therefore, conclusive determination of the origin of HCl released during EGA is vital to understanding the origin of this large δ37Cl anomaly.

Clumped isotope composition of cold-water corals: A role for vital effects?

NASA Astrophysics Data System (ADS)

Spooner, Peter T.; Guo, Weifu; Robinson, Laura F.; Thiagarajan, Nivedita; Hendry, Katharine R.; Rosenheim, Brad E.; Leng, Melanie J.

2016-04-01

The carbonate clumped isotope thermometer is a promising tool for determining past ocean temperatures. It is based on the temperature dependence of rare isotopes 'clumping' into the same carbonate ion group in the carbonate mineral lattice. The extent of this clumping effect is independent of the isotope composition of the water from which carbonate precipitates, providing unique advantages over many other paleotemperature proxies. Existing calibrations of this thermometer in cold-water and warm-water corals suggest clumped isotope 'vital effects' are negligible in cold-water corals but may be significant in warm-water corals. Here, we test the calibration of the carbonate clumped isotope thermometer in cold-water corals with a recently collected and well characterised sample set spanning a range of coral genera (Balanophyllia, Caryophyllia, Dasmosmilia, Desmophyllum, Enallopsammia and Javania). The clumped isotope compositions (Δ47) of these corals exhibit systematic dependences on their growth temperatures, confirming the basis of the carbonate clumped isotope thermometer. However, some cold-water coral genera show Δ47 values that are higher than the expected equilibrium values by up to 0.05‰ (equivalent to underestimating temperature by ∼9 °C) similar to previous findings for some warm-water corals. This finding suggests that the vital effects affecting corals Δ47 are common to both warm- and cold-water corals. By comparison with models of the coral calcification process we suggest that the clumped isotope offsets in these genera are related to the kinetic isotope effects associated with CO2 hydration/hydroxylation reactions in the corals' calcifying fluid. Our findings complicate the use of the carbonate clumped isotope thermometer in corals, but suggest that species- or genus-specific calibrations could be useful for the future application of this paleotemperature proxy.

Isotopic niches of fishes in coastal, neritic and oceanic waters off Adélie land, Antarctica

NASA Astrophysics Data System (ADS)

Cherel, Yves; Koubbi, Philippe; Giraldo, Carolina; Penot, Florian; Tavernier, Eric; Moteki, Masato; Ozouf-Costaz, Catherine; Causse, Romain; Chartier, Amélie; Hosie, Graham

2011-08-01

We used the stable isotope method to investigate the ecological niches of Antarctic fishes, with δ 13C and δ 15N as proxies of fish habitats and dietary habits, respectively. Muscle isotopic signature was measured for each of 237 delipidated tissue samples from 27 fish species collected offshore Adélie Land, East Antarctica. Overall, δ 13C values ranged from -25.3‰ to -18.2‰, thus allowing characterizing of the fish habitats, with inshore/benthic species having more positive δ 13C signatures than offshore/pelagic ones. No clear difference in the δ 13C values of pelagic fishes was found between species living in neritic and oceanic waters. Overall, the δ 15N signatures of neritic pelagic and epibenthic fishes encompassed ˜1.0 trophic level (3.1‰), a higher difference than that (1.4‰) found within the oceanic assemblage. Fishes with the lowest and highest δ 15N values are primarily invertebrate- and fish-eaters, respectively. The isotopic niches of fishes illustrate the different mechanisms allowing coexistence, with most fishes segregating at least by one of the two niche axes (δ 13C and δ 15N). Muscle isotopic values also document interindividual foraging specialization over the long-term in coastal benthic fishes, but not in more offshore pelagic species. Finally, the δ 15N signatures of fishes overlap with those of penguins and seals, indicating that seabirds and marine mammals share the upper levels of the Antarctic pelagic ecosystem with some large fish species. In conclusion, the concept of isotopic niche is a powerful tool to investigate various aspects of the ecological niche of Antarctic fishes, thus complementing the use of other conventional and non-conventional approaches.

Calibrated sulfur isotope abundance ratios of three IAEA sulfur isotope reference materials and V-CDT with a reassessment of the atomic weight of sulfur

NASA Astrophysics Data System (ADS)

Ding, T.; Valkiers, S.; Kipphardt, H.; De Bièvre, P.; Taylor, P. D. P.; Gonfiantini, R.; Krouse, R.

2001-08-01

Calibrated values have been obtained for sulfur isotope abundance ratios of sulfur isotope reference materials distributed by the IAEA (Vienna). For the calibration of the measurements, a set of synthetic isotope mixtures were prepared gravimetrically from high purity Ag2S materials enriched in32S, 33S, and 34S. All materials were converted into SF6 gas and subsequently, their sulfur isotope ratios were measured on the SF5+ species using a special gas source mass spectrometer equipped with a molecular flow inlet system (IRMM's Avogadro II amount comparator). Values for the 32S/34S abundance ratios are 22.650 4(20), 22.142 4(20), and 23.393 3(17) for IAEA-S-1, IAEA-S-2, and IAEA-S-3, respectively. The calculated 32S/34S abundance ratio for V-CDT is 22.643 6(20), which is very close to the calibrated ratio obtained by Ding et al. (1999). In this way, the zero point of the VCDT scale is anchored firmly to the international system of units SI. The 32S/33S abundance ratios are 126.942(47), 125.473(55), 129.072(32), and 126.948(47) for IAEA-S-1, IAEA-S-2, IAEA-S-3, and V-CDT, respectively. In this way, the linearity of the V-CDT scale is improved over this range. The values of the sulfur molar mass for IAEA-S-1 and V-CDT were calculated to be 32.063 877(56) and 32.063 911(56), respectively, the values with the smallest combined uncertainty ever reported for the sulfur molar masses (atomic weights).

Power law behavior of the isotope yield distributions in the multifragmentation regime of heavy ion reactions

NASA Astrophysics Data System (ADS)

Huang, M.; Wada, R.; Chen, Z.; Keutgen, T.; Kowalski, S.; Hagel, K.; Barbui, M.; Bonasera, A.; Bottosso, C.; Materna, T.; Natowitz, J. B.; Qin, L.; Rodrigues, M. R. D.; Sahu, P. K.; Schmidt, K. J.; Wang, J.

2010-11-01

Isotope yield distributions in the multifragmentation regime were studied with high-quality isotope identification, focusing on the intermediate mass fragments (IMFs) produced in semiviolent collisions. The yields were analyzed within the framework of a modified Fisher model. Using the ratio of the mass-dependent symmetry energy coefficient relative to the temperature, asym/T, extracted in previous work and that of the pairing term, ap/T, extracted from this work, and assuming that both reflect secondary decay processes, the experimentally observed isotope yields were corrected for these effects. For a given I=N-Z value, the corrected yields of isotopes relative to the yield of C12 show a power law distribution Y(N,Z)/Y(12C)~A-τ in the mass range 1⩽A⩽30, and the distributions are almost identical for the different reactions studied. The observed power law distributions change systematically when I of the isotopes changes and the extracted τ value decreases from 3.9 to 1.0 as I increases from -1 to 3. These observations are well reproduced by a simple deexcitation model, with which the power law distribution of the primary isotopes is determined to be τprim=2.4±0.2, suggesting that the disassembling system at the time of the fragment formation is indeed at, or very near, the critical point.

Development of a direct procedure for the measurement of sulfur isotope variability in beers by MC-ICP-MS.

PubMed

Giner Martínez-Sierra, J; Santamaria-Fernandez, R; Hearn, R; Marchante Gayón, J M; García Alonso, J I

2010-04-14

In this work, a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) was evaluated for the direct measurement of sulfur stable isotope ratios in beers as a first step toward a general study of the natural isotope variability of sulfur in foods and beverages. Sample preparation consisted of a simple dilution of the beers with 1% (v/v) HNO(3). It was observed that different sulfur isotope ratios were obtained for different dilutions of the same sample indicating that matrix effects affected differently the transmission of the sulfur ions at masses 32, 33, and 34 in the mass spectrometer. Correction for mass bias related matrix effects was evaluated using silicon internal standardization. For that purpose, silicon isotopes at masses 29 and 30 were included in the sulfur cup configuration and the natural silicon content in beers used for internal mass bias correction. It was observed that matrix effects on differential ion transmission could be corrected adequately using silicon internal standardization. The natural isotope variability of sulfur has been evaluated by measuring 26 different beer brands. Measured delta(34)S values ranged from -0.2 to 13.8 per thousand. Typical combined standard uncertainties of the measured delta(34)S values were < or = 2 per thousand. The method has therefore great potential to study sulfur isotope variability in foods and beverages.

A Carbonate Li Isotope Record Through Earth's History

NASA Astrophysics Data System (ADS)

Asael, D.; Kalderon-Asael, B.; Planavsky, N.

2016-12-01

Lithium (Li) isotopes emerge as a powerful geochemical proxy for tracking continental weathering through time. Extensive work on Li fractionation in modern systems has brought to a profound understanding of the modern Li budget as well as to a consensus that marine carbonates faithfully record seawater Li isotope signature. As such record is essential in order to track global-scale changes in weathering processes and intensity through Earth's history, we have generated Li isotope data from marine carbonates from over 40 units, ranging in age from 3.0 Ga to modern. Preliminary results provide evidence for strongly inhibited weathering-mediated clay formation prior to the Paleozoic, which we attribute to the pre-Paleozoic lack of land plants. The initial rise in the Li isotope values is observed during the Ordovician, which is followed by a subsequent drop to background values and then begins the generally increasing trend that is already well reported. These findings are open for interpretation but they still support the view that the emergence of land plants dramatically changed the process of weathering and it seems that biomass has a potentially significant role in mineral breakdown in soils. Li isotopes provide a novel perspective on weathering and the impact on the Earth system of the rise of land plants - one of the most significant transitions in Earth's history.

The oxygen isotopic composition of phosphate in river water and its potential sources in the Upper River Taw catchment, UK.

PubMed

Granger, Steven J; Heaton, Tim H E; Pfahler, Verena; Blackwell, Martin S A; Yuan, Huimin; Collins, Adrian L

2017-01-01

The need to reduce both point and diffuse phosphorus pollution to aquatic ecosystems is widely recognised and in order to achieve this, identification of the different pollutant sources is essential. Recently, a stable isotope approach using oxygen isotopes within phosphate (δ 18 O PO4 ) has been used in phosphorus source tracing studies. This approach was applied in a one-off survey in September 2013 to the River Taw catchment in south-west England where elevated levels of phosphate have been reported. River water δ 18 O PO4 along the main channel varied little, ranging from +17.1 to +18.8‰. This was no >0.3‰ different to that of the isotopic equilibrium with water (Eδ 18 O PO4 ). The δ 18 O PO4 in the tributaries was more variable (+17.1 to +18.8‰), but only deviated from Eδ 18 O PO4 by between 0.4 and 0.9‰. Several potential phosphate sources within the catchment were sampled and most had a narrow range of δ 18 O PO4 values similar to that of river Eδ 18 O PO4 . Discharge from two waste water treatment plants had different and distinct δ 18 O PO4 from one another ranging between +16.4 and +19.6‰ and similar values to that of a dairy factory final effluent (+16.5 to +17.8‰), mains tap water (+17.8 to +18.4‰), and that of the phosphate extracted from river channel bed sediment (+16.7 to +17.6‰). Inorganic fertilizers had a wide range of values (+13.3 to +25.9‰) while stored animal wastes were consistently lower (+12.0 to +15.0‰) than most other sources and Eδ 18 O PO4 . The distinct signals from the waste water treatment plants were lost within the river over a short distance suggesting that rapid microbial cycling of phosphate was occurring, because microbial cycling shifts the isotopic signal towards Eδ 18 O PO4 . This study has added to the global inventory of phosphate source δ 18 O PO4 values, but also demonstrated the limitations of this approach to identifying phosphate sources, especially at times when microbial cycling is high. Copyright © 2016 Office national des forêts. Published by Elsevier B.V. All rights reserved.

Analysis of δ18O and δD values of environmental waters at high temporal and spatial resolution by continuous diffusion sampling cavity ring-down spectrometry

NASA Astrophysics Data System (ADS)

Munksgaard, Niels; Bass, Adrian; Wurster, Chris; Bird, Michael

2013-04-01

A novel sampling device utilises diffusion through porous PTFE tubing to deliver water vapour continuously from a liquid water source for analysis of δ18O and δD values by Cavity Ring-Down Spectrometry (CRDS). Comparison of isotopic data for a range of water samples analysed by Diffusion Sampling-CRDS (DS-CRDS) and Isotope Ratio Mass Spectrometry (IRMS) shows significant linear correlations between the two methods allowing for accurate standardisation of DS-CRDS data. The internal precision for an integration period of 3 min (standard deviation = 0.1 ‰ and 0.3 ‰ for δ18O and δD values, respectively) is similar to analysis of water by injection/evaporation CRDS of discrete water samples. The isotopic effects of variable air and water temperature, water vapour concentration and water pumping rate were found to be either negligible or correctable by analysis of water standards. Separation of the analysed water vapour from non-volatile dissolved and particulate contaminants in the liquid sample minimises interferences associated with CRDS analyses of many aqueous samples. Coupling of the DS-CRDS instrument to an auto sampler enables rapid analysis (10 min) of discrete water samples. The DS-CRDS system was used in the first continuous shipboard measurement of δ18O and δD of water. Combined with continuous salinity recordings, a data set of nearly 6,000 isotope measurements was made at 30-s intervals during a 3-day voyage through the Great Barrier Reef Lagoon. Precise identification of river plumes within the Great Barrier Reef Lagoon was possible because unique δ18O/δD-salinity relationships of individual plumes were measured at high spatial and temporal resolution. Continuous shipboard measurement of δ18O/δD values by DS-CRDS provides additional discriminatory power for assessing water mass formation processes and histories at a small fraction of the cost of traditional isotope analysis of discrete samples. In a second application of DS-CRDS, continuous real-time analysis, at 30-s intervals, of precipitation at an Australian tropical location revealed extreme and rapidly changing δ18O and δD values related to variations in moisture source areas, transport paths and precipitation histories. The range of δ18O (-19.6 ‰ to +2.6 ‰) and δD (-140 ‰ to +13 ‰) values from almost 6,000 measurements of nine rain events over 15 days during an 8-month period at a single location was comparable with the range measured in 1532 monthly samples from all seven Australian Global Network of Isotopes in Precipitation stations from 1962 to 2002. Extreme variations in δ18O (-8.7 ‰ to -19.6 ‰) and δD (-54 ‰ to -140 ‰) were recorded within a single 4-h period. Real-time stable isotope monitoring of environmental waters at high temporal and spatial resolution enables new and powerful tracer applications in climatology, hydrology, eco-physiology and palaeo-climatology.

Stable Mercury Isotopes in Polished Rice (Oryza sativa L.) and Hair from Rice Consumers

PubMed Central

2017-01-01

Mercury (Hg) isotopic signatures were characterized in polished rice samples from China, U.S., and Indonesia (n = 45). Hg isotopes were also analyzed in paired hair samples for participants from China (n = 21). For the latter, we also quantified the proportion of methylmercury intake through rice (range: 31–100%), and the weekly servings of fish meals (range: 0–5.6 servings/weekly). For these participants, 29% (n = 6) never ingested fish, 52% (n = 11) ingested fish < twice/weekly, and 19% (n = 4) ingested fish ≥ twice/weekly. In rice and hair, both mass-dependent fractionation (MDF, reported as δ202Hg) and mass-independent fractionation (MIF, reported as Δ199Hg) of Hg isotopes were observed. Compared to rice, hair δ202Hg values were enriched on average (±1 standard deviation) by 1.9 ± 0.61‰, although the range was wide (range: 0.45‰, 3.0‰). Hair Δ199Hg was significantly inversely associated with %methylmercury intake from rice (Spearman’s rho = −0.61, p < 0.01, n = 21), i.e., as the proportion of methylmercury intake from rice increased, MIF decreased. Additionally, hair Δ199Hg was significantly higher for participants ingesting fish ≥ twice/weekly compared to those who did not ingest fish or ingested fish < twice/weekly (ANOVA, p < 0.05, n = 21); Overall, results suggest that Hg isotopes (especially MIF) in human hair can be used to distinguish methylmercury intake from rice versus fish. PMID:28482656

Thallium isotope variations in seawater and hydrogenetic, diagenetic, and hydrothermal ferromanganese deposits

USGS Publications Warehouse

Rehkamper, M.; Frank, M.; Hein, J.R.; Porcelli, D.; Halliday, A.; Ingri, J.; Liebetrau, V.

2002-01-01

Results are presented for the first in-depth investigation of TI isotope variations in marine materials. The TI isotopic measurements were conducted by multiple collector-inductively coupled plasma mass spectrometry for a comprehensive suite of hydrogenetic ferromanganese crusts, diagenetic Fe-Mn nodules, hydrothermal manganese deposits and seawater samples. The natural variability of TI isotope compositions in these samples exceeds the analytical reproducibility (?? 0.05???) by more than a factor of 40. Hydrogenetic Fe-Mn crusts have ??205TI of + 10 to + 14, whereas seawater is characterized by values as low as -8 (??205TI represents the deviation of the 205TI/203TI ratio of a sample from the NIST SRM 997 TI isotope standard in parts per 104). This ~ 2??? difference in isotope composition is thought to result from the isotope fractionation that accompanies the adsorption of TI onto ferromanganese particles. An equilibrium fractionation factor of ?? ~ 1.0021 is calculated for this process. Ferromanganese nodules and hydrothermal manganese deposits have variable TI isotope compositions that range between the values obtained for seawater and hydrogenetic Fe-Mn crusts. The variability in ??205TI in diagenetic nodules appears to be caused by the adsorption of TI from pore fluids, which act as a closed-system reservoir with a TI isotope composition that is inferred to be similar to seawater. Nodules with ??205TI values similar to seawater are found if the scavenging of TI is nearly quantitative. Hydrothermal manganese deposits display a positive correlation between ??205TI and Mn/Fe. This trend is thought to be due to the derivation of TI from distinct hydrothermal sources. Deposits with low Mn/Fe ratios and low ??205TI are produced by the adsorption of TI from fluids that are sampled close to hydrothermal sources. Such fluids have low Mn/Fe ratios and relatively high temperatures, such that only minor isotope fractionation occurs during adsorption. Hydrothermal manganese deposits with high Mn/Fe and high ??205Ti are generated by scavenging of TI from colder, more distal hydrothermal fluids. Under such conditions, adsorption is associated with significant isotope fractionation, and this produces deposits with higher ??205TI values coupled with high Mn/Fe. ?? 2002 Elsevier Science B.V. All rights reserved.

Effects of growth and dissolution on the fractionation of silicon isotopes by estuarine diatoms

NASA Astrophysics Data System (ADS)

Sun, Xiaole; Olofsson, Martin; Andersson, Per S.; Fry, Brian; Legrand, Catherine; Humborg, Christoph; Mörth, Carl-Magnus

2014-04-01

Studies of silicon (Si) isotope fractionation during diatom growth in open ocean systems have documented lower Si isotopic values (δ30Si) in the biogenic silica of diatom frustules compared to dissolved silicon. Recent findings also indicate that Si isotope fractionation occurs during dissolution of diatom frustules, producing higher δ30Si values in the remaining biogenic silica. This study focuses on diatoms from high production areas in estuarine and coastal areas that represent approximately 30-50% of the global marine primary production. Two species of diatoms, Thalassiosira baltica and Skeletonema marinoi, were isolated from the brackish Baltic Sea, one of the largest estuarine systems in the world. These species were used for laboratory investigations of Si isotope fractionation during diatom growth and the subsequent dissolution of the diatom frustules. Both species of diatoms give an identical Si isotope fractionation factor during growth of -1.50 ± 0.36‰ (2σ) for 30Si, which falls in the range of -2.09‰ to -0.55‰ of published data. Our results also suggest a dissolution-induced Si isotope fractionation factor of -0.86‰ at early stage of dissolution, but this effect was observed only in DSi and no significant Si isotope change was observed for BSi. The growth and dissolution results are applied to a Baltic Sea sediment core to reconstruct DSi utilization by diatoms, and found to be in agreement with the observed DSi uptake rates in the overlying water column during diatom growth.

Computational Replication of the Abnormal Secondary Kinetic Isotope Effects in a Hydride Transfer Reaction in Solution with a Motion Assisted H-Tunneling Model

PubMed Central

2015-01-01

We recently reported abnormal secondary deuterium kinetic isotope effects (2° KIEs) for hydride transfer reactions from alcohols to carbocations in acetonitrile (Chem. Comm. 2012, 48, 11337). Experimental 2° KIE values were found to be inflated on the 9-C position in the xanthylium cation but deflated on the β-C position in 2-propanol with respect to the values predicted by the semi-classical transition-state theory. No primary (1°) isotope effect on 2° KIEs was observed. Herein, the KIEs were replicated by the Marcus-like H-tunneling model that requires a longer donor–acceptor distance (DAD) in a lighter isotope transfer process. The 2° KIEs for a range of potential tunneling-ready-states (TRSs) of different DADs were calculated and fitted to the experiments to find the TRS structure. The observed no effect of 1° isotope on 2° KIEs is explained in terms of the less sterically hindered TRS structure so that the change in DAD due to the change in 1° isotope does not significantly affect the reorganization of the 2° isotope and hence the 2° KIE. The effect of 1° isotope on 2° KIEs may be expected to be more pronounced and thus observable in reactions occurring in restrictive environments such as the crowded and relatively rigid active site of enzymes. PMID:24498946

Sr isotopic variations in Upper Proterozoic carbonates from Svalbard and East Greenland.

PubMed

Derry, L A; Keto, L S; Jacobsen, S B; Knoll, A H; Swett, K

1989-01-01

We report initial 87Sr/86Sr values from an Upper Proterozoic carbonate succession from Svalbard and East Greenland. This succession, now tectonically separated into three sequences, is thick, relatively continuous, and well preserved. The relative ages of the samples from within the basin are well constrained by litho-, bio-, and chemostratigraphic techniques. The data from this study and related data from the literature are used to construct a curve of 87Sr/86Sr for Upper Proterozoic seawater. The new data reported in this study substantially improve the isotopic record of Sr in seawater for the period between 650 and 800 Ma. The data indicate that delta 87Sr values of seawater were variable but low (delta 87Sr approximately -500 to -250) between 900 and 650 Ma, and rose rapidly to approximately +30 by 600 Ma. The range of variation of delta 87Sr in seawater during the Riphean-Vendian exceeds the entire range of delta 87Sr in seawater during the Phanerozoic. While variation in the average isotopic composition of Sr delivered to the oceans by rivers can account for some of the observed range, changes in the ratio of submarine hydrothermal flux to river water (continental) flux are responsible for the large variation in seawater Sr isotopic composition. Changes in the continental flux of Sr to the oceans can be related to tectonic factors. Large changes in the hydrothermal flux to river water flux ratio indicated by the data could have significant consequences for the chemistry of the ocean-atmosphere system.

Evaluation of the Origin and Fate of Nitrate in the Aquifer System of Southern Baldwin County, Alabama Using Multi-isotopic Data

NASA Astrophysics Data System (ADS)

Murgulet, D.; Tick, G. R.

2008-12-01

Continued and extensive residential and agricultural development of near-shore areas in southern Baldwin County, Alabama has led to increased inputs of nitrogen (N) to groundwater and to the Gulf of Mexico. Nitrate (NO3-) concentrations in several groundwater wells exceeded the regulatory drinking water standards (10 mg/L nitrate-N). Groundwater and surface water samples were analyzed for nitrate, phosphate, salinity, chloride, and total dissolved solids concentrations to assess the extent of nitrate contamination. Nitrogen and oxygen isotopes of nitrate (e.g., δ15N and δ18O of nitrate) were used in conjunction with other isotopic data (e.g., 13C, and 14C, and hydrogen and oxygen isotopes of groundwater) and hydrogeochemical data to place constraints on potential sources of nitrate. The δ15N and δ18O of groundwater nitrate values ranged between +3.1 and +9.6‰ and +4.2 and +8.7‰, respectively. This range of values suggests that nitrate is primarily derived from nitrification of reduced N compounds (primarily ammonia) from fertilizer and manure or septic waste. However, an overwhelming number of samples show isotopic signatures which indicate that the predominant source of nitrate in these aguifers is the fertilizer and to some extent, for deeper wells with older groundwater, the atmospheric nitrate. The narrow range of δ18O values further confirms the primary nitrate sources. The δ15N and δ18O of nitrate data indicate that denitrification was not an important processes in these aquifers. This conclusion is also supported by the 114C data which revealed relatively young groundwaters with sufficiently high oxygen levels. In the absence of denitrification and the presence of a permanent source, it is expected that the elevated groundwater nitrate concentrations will not be readily attenuated posing a potential contamination and degradation problem of coastal discharge zones into the future. The δ13C and δ18O of groundwater data indicates that water in the aquifer system of the study area is most likely to have originated from precipitation and soil infiltration through relatively localized recharge.

Geochemical and strontium isotope characterization of produced waters from Marcellus Shale natural gas extraction.

PubMed

Chapman, Elizabeth C; Capo, Rosemary C; Stewart, Brian W; Kirby, Carl S; Hammack, Richard W; Schroeder, Karl T; Edenborn, Harry M

2012-03-20

Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ~375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (ε(Sr)(SW) = +13.8 to +41.6, where ε(Sr) (SW) is the deviation of the (87)Sr/(86)Sr ratio from that of seawater in parts per 10(4)); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters.

[Trophic niche partitioning of pelagic sharks in Central Eastern Pacific inferred from stable isotope analysis.

PubMed

Li, Yun Kai; Gao, Xiao di; Wang, Lin Yu; Fang, Lin

2018-01-01

As the apex predators of the open ocean ecosystems, pelagic sharks play important roles in stabilizing the marine food web through top-down control. Stable isotope analysis is a powerful tool to investigate the feeding ecology. The carbon and nitrogen isotope ratios can be used to trace food source and evaluate the trophic position of marine organisms. In this study, the isotope values of 130 pelagic sharks from 8 species in Central Eastern Pacific were analyzed and their trophic position and niche were calculated to compare the intra/inter-specific resource partitioning in the Central Eastern Pacific ecosystem. The results exhibited significant differences in both carbon and nitrogen isotope values among the shark species. The trophic levels ranged from 4.3 to 5.4 in the Central Eastern Pacific shark community. The trophic niche of blue sharks and shortfin mako sharks showed no overlap with the other shark species, exhibiting unique ecological roles in the open ocean food web. These data highlighted the diverse roles among pelagic sharks, supporting previous findings that this species is not trophically redundant and the trophic niche of pelagic sharks can not be simply replaced by those of other top predator species.

Iron isotope biogeochemistry of Neoproterozoic marine shales

NASA Astrophysics Data System (ADS)

Kunzmann, Marcus; Gibson, Timothy M.; Halverson, Galen P.; Hodgskiss, Malcolm S. W.; Bui, Thi Hao; Carozza, David A.; Sperling, Erik A.; Poirier, André; Cox, Grant M.; Wing, Boswell A.

2017-07-01

Iron isotopes have been widely applied to investigate the redox evolution of Earth's surface environments. However, it is still unclear whether iron cycling in the water column or during diagenesis represents the major control on the iron isotope composition of sediments and sedimentary rocks. Interpretation of isotopic data in terms of oceanic redox conditions is only possible if water column processes dominate the isotopic composition, whereas redox interpretations are less straightforward if diagenetic iron cycling controls the isotopic composition. In the latter scenario, iron isotope data is more directly related to microbial processes such as dissimilatory iron reduction. Here we present bulk rock iron isotope data from late Proterozoic marine shales from Svalbard, northwestern Canada, and Siberia, to better understand the controls on iron isotope fractionation in late Proterozoic marine environments. Bulk shales span a δ 56Fe range from -0.45 ‰ to +1.04 ‰ . Although δ 56Fe values show significant variation within individual stratigraphic units, their mean value is closer to that of bulk crust and hydrothermal iron in samples post-dating the ca. 717-660 Ma Sturtian glaciation compared to older samples. After correcting for the highly reactive iron content in our samples based on iron speciation data, more than 90% of the calculated δ 56Fe compositions of highly reactive iron falls in the range from ca. -0.8 ‰ to +3 ‰ . An isotope mass-balance model indicates that diagenetic iron cycling can only change the isotopic composition of highly reactive iron by < 1 ‰ , suggesting that water column processes, namely the degree of oxidation of the ferrous seawater iron reservoir, control the isotopic composition of highly reactive iron. Considering a long-term decrease in the isotopic composition of the iron source to the dissolved seawater Fe(II) reservoir to be unlikely, we offer two possible explanations for the Neoproterozoic δ 56Fe trend. First, a decreasing supply of Fe(II) to the ferrous seawater iron reservoir could have caused the reservoir to decrease in size, allowing a higher degree of partial oxidation, irrespective of increasing environmental oxygen levels. Alternatively, increasing oxygen levels would have led to a higher proportion of Fe(II) being oxidized, without decreasing the initial size of the ferrous seawater iron pool. We consider the latter explanation as the most likely. According to this hypothesis, the δ 56Fe record reflects the redox evolution of Earth's surface environments. δ 56Fe values in pre-Sturtian samples significantly heavier than bulk crust and hydrothermal iron imply partial oxidation of a ferrous seawater iron reservoir. In contrast, mean δ 56Fe values closer to that of hydrothermal iron in post-Sturtian shales reflects oxidation of a larger proportion of the ferrous seawater iron reservoir, and by inference, higher environmental oxygen levels. Nevertheless, significant iron isotopic variation in post-Sturtian shales suggest redox heterogeneity and possibly a dominantly anoxic deep ocean, consistent with results from recent studies using iron speciation and redox sensitive trace metals. However, the interpretation of generally increasing environmental oxygen levels after the Sturtian glaciation highlights the need to better understand the sensitivity of different redox proxies to incremental changes in oxygen levels to enable us to reconcile results from different paleoredox proxies.

Pb evolution in the Martian mantle

NASA Astrophysics Data System (ADS)

Bellucci, J. J.; Nemchin, A. A.; Whitehouse, M. J.; Snape, J. F.; Bland, P.; Benedix, G. K.; Roszjar, J.

2018-03-01

The initial Pb compositions of one enriched shergottite, one intermediate shergottite, two depleted shergottites, and Nakhla have been measured by Secondary Ion Mass Spectrometry (SIMS). These values, in addition to data from previous studies using an identical analytical method performed on three enriched shergottites, ALH 84001, and Chassigny, are used to construct a unified and internally consistent model for the differentiation history of the Martian mantle and crystallization ages for Martian meteorites. The differentiation history of the shergottites and Nakhla/Chassigny are fundamentally different, which is in agreement with short-lived radiogenic isotope systematics. The initial Pb compositions of Nakhla/Chassigny are best explained by the late addition of a Pb-enriched component with a primitive, non-radiogenic composition. In contrast, the Pb isotopic compositions of the shergottite group indicate a relatively simple evolutionary history of the Martian mantle that can be modeled based on recent results from the Sm-Nd system. The shergottites have been linked to a single mantle differentiation event at 4504 Ma. Thus, the shergottite Pb isotopic model here reflects a two-stage history 1) pre-silicate differentiation (4504 Ma) and 2) post-silicate differentiation to the age of eruption (as determined by concordant radiogenic isochron ages). The μ-values (238U/204Pb) obtained for these two different stages of Pb growth are μ1 of 1.8 and a range of μ2 from 1.4-4.7, respectively. The μ1-value of 1.8 is in broad agreement with enstatite and ordinary chondrites and that proposed for proto Earth, suggesting this is the initial μ-value for inner Solar System bodies. When plotted against other source radiogenic isotopic variables (Sri, γ187Os, ε143Nd, and ε176Hf), the second stage mantle evolution range in observed mantle μ-values display excellent linear correlations (r2 > 0.85) and represent a spectrum of Martian mantle mixing-end members (depleted, intermediate, enriched).

Examination of chloritization of biotite as a tool for reconstructing the physicochemical parameters of mineralization and associated alteration in the Zafarghand porphyry copper system, Ardestan, Central Iran: mineral-chemistry and stable isotope analyses

NASA Astrophysics Data System (ADS)

Aminroayaei Yamini, Maryam; Tutti, Faramarz; Aminoroayaei Yamini, Mohammad Reza; Ahmadian, Jamshid; Wan, Bo

2017-10-01

The chloritization of biotite and stable isotopes of silicate have been studied for the Zafarghand porphyry copper deposit, Ardestan, Iran. The studied area, in the central part of the Urumieh-Dokhtar magmatic belt, contains porphyry-style Cu mineralization and associated hydrothermal alteration within the Miocene (19-26 Ma, Zircon U-Pb age) granodioritc stock and adjacent andesitic to rhyodacitic volcanic rocks (ca. 56 Ma, zircon U-Pb age). The primary and secondary biotite that formed during potassic alteration in this porphyry and these volcanic host rocks are variably chloritized. Chloritization of biotite pseudomorphically is characterized by an increase in MgO, FeOt, and MnO, with decreasing in SiO2, K2O, and TiO2. Based on the Ti-in-biotite geothermometer of Henry et al. (Am Mineral 90:316-328, 2005) and Al-in-chlorite geothermometer of Cathelineau (Clay Miner 23:417-485, 1988), crystallization temperatures of primary biotite representative of magmatic conditions and later chloritization temperature range from 617° to 675 °C ± 24 °C and 177° to 346 °C, respectively. Calculated isotopic compositions of fluids that chloritized primary and secondary biotite display isotopic compositions of 1.1 to 1.7 per mil for δ18O and -19.9 to -20.5 per mil for δD consistent with meteoric water. Sericite, barren, and A-type-quartz veins from phyllic alteration were produced by mixed magmatic and meteoric water with δ18O values from -2.8 to 2.5 and δD values of ˜ -23 per mil; the narrow range of δD values of the propylitic epidote may be due to a meteoric water with δ18O values from 0.8 to 1.6 and δD values from -14.6 to -16.9 per mil.

Opposing authigenic controls on the isotopic signature of dissolved iron in hydrothermal plumes

NASA Astrophysics Data System (ADS)

Lough, A. J. M.; Klar, J. K.; Homoky, W. B.; Comer-Warner, S. A.; Milton, J. A.; Connelly, D. P.; James, R. H.; Mills, R. A.

2017-04-01

Iron is a scarce but essential micronutrient in the oceans that limits primary productivity in many regions of the surface ocean. The mechanisms and rates of Fe supply to the ocean interior are still poorly understood and quantified. Iron isotope ratios of different Fe pools can potentially be used to trace sources and sinks of the global Fe biogeochemical cycle if these boundary fluxes have distinct signatures. Seafloor hydrothermal vents emit metal rich fluids from mid-ocean ridges into the deep ocean. Iron isotope ratios have the potential to be used to trace the input of hydrothermal dissolved iron to the oceans if the local controls on the fractionation of Fe isotopes during plume dispersal in the deep ocean are understood. In this study we assess the behaviour of Fe isotopes in a Southern Ocean hydrothermal plume using a sampling program of Total Dissolvable Fe (TDFe), and dissolved Fe (dFe). We demonstrate that δ56Fe values of dFe (δ56dFe) within the hydrothermal plume change dramatically during early plume dispersal, ranging from -2.39 ± 0.05‰ to -0.13 ± 0.06‰ (2 SD). The isotopic composition of TDFe (δ56TDFe) was consistently heavier than dFe values, ranging from -0.31 ± 0.03‰ to 0.78 ± 0.05‰, consistent with Fe oxyhydroxide precipitation as the plume samples age. The dFe present in the hydrothermal plume includes stabilised dFe species with potential to be transported to the deep ocean. We estimate that stable dFe exported from the plume will have a δ56Fe of -0.28 ± 0.17‰. Further, we show that the proportion of authigenic iron-sulfide and iron-oxyhydroxide minerals precipitating in the buoyant plume exert opposing controls on the resultant isotope composition of dissolved Fe passed into the neutrally buoyant plume. We show that such controls yield variable dissolved Fe isotope signatures under the authigenic conditions reported from modern vent sites elsewhere, and so ought to be considered during iron isotope reconstructions of past hydrothermalism from ocean sediment records.

Modeling the influence of a reduced equator-to-pole sea surface temperature gradient on the distribution of water isotopes in the Eocene

NASA Astrophysics Data System (ADS)

Speelman, E. N.; Sewall, J. O.; Noone, D. C.; Huber, M.; Sinninghe Damsté, J. S.; Reichart, G.

2009-12-01

Proxy-based climate reconstructions suggest the existence of a strongly reduced equator-to-pole temperature gradient during most of the Early Eocene. With the realization that the Eocene Arctic Ocean was covered with enormous quantities of the free floating freshwater fern Azolla, new questions related to Eocene (global) hydrological cycling facilitating these blooms arose. Changes in hydrological cycling, as a consequence of a reduced temperature gradient, are expected to be most clearly reflected in the isotopic composition (D, 18O) of precipitation. The interpretation of water isotopic records to quantitatively estimate past precipitation patterns is, however, hampered by the lack of detailed information on changes in their spatial and temporal distribution. Using the isotope-enabled global circulation model, Community Atmosphere Model v.3 (isoCAM3), relationships between water isotopes and past climates can be simulated. Here we examine the influence of a reduced meridional sea surface temperature gradient on the spatial distribution of precipitation and its isotopic composition in an Eocene setting. Overall, our combination of Eocene climate forcings, with superimposed TEX86-derived SST estimates and elevated pCO2 concentrations, produces a climate that agrees well with proxy data in locations around the globe. It shows the presence of an intensified hydrological cycle with precipitation exceeding evaporation in the Arctic region. The Eocene model runs with a significantly reduced equator-to-pole temperature gradient in a warmer more humid world predict occurrence of less depleted precipitation, with δD values ranging only between 0 and -140‰ (as opposed to the present-day range of 0 to -300‰). Combining new results obtained from compound specific isotope analyses on terrestrially derived n-alkanes extracted from Eocene sediments, and model calculations, shows that the model not only captures the main features, but reproduces isotopic values quantitatively as well. This combination of modeling outcomes and independent stable isotope records thus confirms independently the validity of the earlier, proxy-based, inferred reduced meridional temperature gradient.

Use of a multi-isotope and multi-tracer approach including organic matter isotopes for quantifying nutrient contributions from agricultural vs wastewater sources

NASA Astrophysics Data System (ADS)

Kendall, C.; Silva, S. R.; Young, M. B.

2013-12-01

While nutrient isotopes are a well-established tool for quantifying nutrients inputs from agricultural vs wastewater treatment plant (WWTP) sources, we have found that combining nutrient isotopes with the C, N, and S isotopic compositions of dissolved and particulate organic matter, as part of a comprehensive multi-isotope and multi-tracer approach, is a much more diagnostic approach. The main reasons why organic matter C-N-S isotopes are a useful adjunct to studies of nutrient sources and biogeochemical processes are that the dissolved and particulate organic matter associated with (1) different kinds of animals (e.g., humans vs cows) often have distinctive isotopic compositions reflecting the different diets of the animals, and (2) the different processes associated with the different land uses (e.g., in the WWTP or associated with different crop types) often result in significant differences in the isotopic compositions of the organics. The analysis of the δ34S of particulate organic matter (POM) and dissolved organic matter (DOM) has been found to be especially useful for distinguishing and quantifying water, nutrient, and organic contributions from different land uses in aquatic systems where much of the organic matter is aquatic in origin. In such environments, the bacteria and algae incorporate S from sulfate and sulfide that is isotopically labeled by the different processes associated with different land uses. We have found that there is ~35 permil range in δ34S of POM along the river-estuary continuum in the San Joaquin/Sacramento River basin, with low values associated with sulfate reduction in the upstream wetlands and high values associated with tidal inputs of marine water into the estuary. Furthermore, rice agriculture results in relatively low δ34S values whereas WWTP effluent in the Sacramento River produces distinctly higher values than upstream of the WWTP, presumably because SO2 is used to treat chlorinated effluent. The fish living downstream of these different land uses become isotopically labeled by the environments, making δ34S a useful tracer of fish derived from these different environments. This presentation will use examples from several large-scale river and wetlands studies to demonstrate useful applications of POM and DOM isotopes for environmental monitoring studies, and will discuss the relative merits of different methods for the collection and analysis of POM and DOM samples for C, N, and S isotopes.

Isotopic composition of sulfate accumulations, Northern Calcareous Alps, Austria

NASA Astrophysics Data System (ADS)

Bojar, Ana-Voica; Halas, Stanislaw; Bojar, Hans-Peter; Trembaczowski, Andrzej

2015-04-01

The Eastern Alps are characterised by the presence of three main tectonic units, such as the Lower, Middle and Upper Austroalpine, which overlie the Penninicum (Tollmann, 1977). The Upper Austroalpine unit consists of the Northern Calcareous Alps (NCA) overlying the Greywacke zone and corresponding to the Graz Paleozoic, Murau Paleozoic and the Gurktal Nappe. Evaporitic rocks are lacking in the later ones. The Northern Calcareous Alps are a detached fold and thrust belt. The sedimentation started in the Late Carboniferous or Early Permian, the age of the youngest sediments being Eocene. The NCA are divided into the Bajuvaric, Tirolic and Juvavic nappe complexes. The evaporitic Haselgebirge Formation occurs in connection with the Juvavic nappe complex at the base of the Tirolic units (Leitner et al., 2013). The Haselgebirge Formation consists mainly of salt, shales, gypsum and anhydrite and includes the oldest sediments of the NCA. The age of the Haselgebirge Formation, established by using spors and geochronological data, is Permian to Lower Triassic. For the Northern Calcareous Alps, the mineralogy of sulphate accumulations consists mainly of gypsum and anhydrite and subordonates of carbonates. The carbonates as magnesite, dolomite and calcite can be found either as singular crystals or as small accumulations within the hosting gypsum. Sulfides (sphalerite, galena, pyrite), sulfarsenides (enargite, baumhauerite) and native sulphur enrichments are known from several deposits (Kirchner, 1987; Postl, 1990). The investigated samples were selected from various gypsum and halite rich deposits of the Northern Calcareous Alps. A total of over 20 samples were investigated, and both oxygen and sulfur isotopic composition were determined for anhydrite, gyps, polyhalite, blödite and langbeinite. The sulfur isotopic values vary between 10.1 to 14 ‰ (CDT), with three values higher than 14 ‰. The Oxygen isotopic values show a range from 9 to 23 ‰ (SMOW). The sulfur isotopic compositon of 14 sulfides as galena, sphalerite, pyrite and native sulfure were determined as well, with values ranging between -17.5 and 2.8 ‰ (CDT). For the investigated sulfates, the sulfur isotopic values show generally low values, which are characteristic for the late Permian. The broad distribution of sulfide values point toward bacterial reduction, fact also reflected by some higher isotopic values of sulfates. The oxygen values show a larger scatter from 9 to 23‰, which is even larger than that found for the Zechstein anhydrites of northern Germany, north-eastern Italian Alps or western Poland. The associated carbonates, as calcite, dolomite and magnesite are in disequilibrium with the sulfates indicating rather primary marine isotopic signature than re-equlibration with the sulfates at higher temperatures. References Leitner, C., Neubauer, F., Genser, J., Borojevic-Sostaric, B., Rantitsch, G., 2013. 40Ar/39Ar ages of recrystallization of rock-forming polyhalite in Alpine rocksalt deposits. In Jordan, F., Mark, D.F., Verati C. (eds.) Advances in 40Ar/39Ar Dating: from Archaeology to Planetary Sciences. Geological Society, London, Special Publications, 378, 207-244. Kirchner, E., 1987: Die Mineral- und Gesteinsvorkommen in den Gipslagerstätten der Lammermasse, innerhalb der Hallstattzone, Salzburg. Jahrbuch Haus der Natur. 10, 156-167. Postl, W., 1990. Enargit und Parnauit aus dem Gips- und Anhydritbergbau Tragöß-Oberort, Steiermark. In: Niedermayr, G. et al. (1990): Neue Mineralfunde aus Österreich XXXIX. Carinthia II, 180/100, 277. Tollmann, A., 1977. Geologie von Österreich. Band 1. Die Zentralalpen. Deuticke, Wien, 766 pp.

Carbon and hydrogen isotope fractionation under continuous light: implications for paleoenvironmental interpretations of the High Arctic during Paleogene warming.

PubMed

Yang, Hong; Pagani, Mark; Briggs, Derek E G; Equiza, M A; Jagels, Richard; Leng, Qin; Lepage, Ben A

2009-06-01

The effect of low intensity continuous light, e.g., in the High Arctic summer, on plant carbon and hydrogen isotope fractionations is unknown. We conducted greenhouse experiments to test the impact of light quantity and duration on both carbon and hydrogen isotope compositions of three deciduous conifers whose fossil counterparts were components of Paleogene Arctic floras: Metasequoia glyptostroboides, Taxodium distichum, and Larix laricina. We found that plant leaf bulk carbon isotopic values of the examined species were 1.75-4.63 per thousand more negative under continuous light (CL) than under diurnal light (DL). Hydrogen isotope values of leaf n-alkanes under continuous light conditions revealed a D-enriched hydrogen isotope composition of up to 40 per thousand higher than in diurnal light conditions. The isotope offsets between the two light regimes is explained by a higher ratio of intercellular to atmospheric CO(2) concentration (C (i)/C (a)) and more water loss for plants under continuous light conditions during a 24-h transpiration cycle. Apparent hydrogen isotope fractionations between source water and individual lipids (epsilon(lipid-water)) range from -62 per thousand (Metasequoia C(27) and C(29)) to -87 per thousand (Larix C(29)) in leaves under continuous light. We applied these hydrogen fractionation factors to hydrogen isotope compositions of in situ n-alkanes from well-preserved Paleogene deciduous conifer fossils from the Arctic region to estimate the deltaD value in ancient precipitation. Precipitation in the summer growing season yielded a deltaD of -186 per thousand for late Paleocene, -157 per thousand for early middle Eocene, and -182 per thousand for late middle Eocene. We propose that high-latitude summer precipitation in this region was supplemented by moisture derived from regionally recycled transpiration of the polar forests that grew during the Paleogene warming.

High-precision determination of 18O/16O ratios of silver phosphate by EA-pyrolysis-IRMS continuous flow technique.

PubMed

Lécuyer, Christophe; Fourel, François; Martineau, François; Amiot, Romain; Bernard, Aurélien; Daux, Valérie; Escarguel, Gilles; Morrison, John

2007-01-01

A high-precision, and rapid on-line method for oxygen isotope analysis of silver phosphate is presented. The technique uses high-temperature elemental analyzer (EA)-pyrolysis interfaced in continuous flow (CF) mode to an isotopic ratio mass spectrometer (IRMS). Calibration curves were generated by synthesizing silver phosphate with a 13 per thousand spread in delta(18)O values. Calibration materials were obtained by reacting dissolved potassium dihydrogen phosphate (KH(2)PO(4)) with water samples of various oxygen isotope compositions at 373 K. Validity of the method was tested by comparing the on-line results with those obtained by classical off-line sample preparation and dual inlet isotope measurement. In addition, silver phosphate precipitates were prepared from a collection of biogenic apatites with known delta(18)O values ranging from 12.8 to 29.9 per thousand (V-SMOW). Reproducibility of +/- 0.2 per thousand was obtained by the EA-Py-CF-IRMS method for sample sizes in the range 400-500 microg. Both natural and synthetic samples are remarkably well correlated with conventional (18)O/(16)O determinations. Silver phosphate is a very stable material and easy to degas and, thus, could be considered as a good candidate to become a reference material for the determination of (18)O/(16)O ratios of phosphate by high-temperature pyrolysis. Copyright 2006 John Wiley & Sons, Ltd.

Isotope-abundance variations of selected elements (IUPAC technical report)

USGS Publications Warehouse

Coplen, T.B.; Böhlke, J.K.; De Bievre, P.; Ding, T.; Holden, N.E.; Hopple, J.A.; Krouse, H.R.; Lamberty, A.; Peiser, H.S.; Revesz, K.; Rieder, S.E.; Rosman, K.J.R.; Roth, E.; Taylor, P.D.P.; Vocke, R.D.; Xiao, Y.K.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

The isotopic effects of electron transfer: an explanation for Fe isotope fractionation in nature

NASA Astrophysics Data System (ADS)

Kavner, A.; Shahar, A.; Bonet, F.; Simon, J. I.; Young, E.

2004-12-01

Recent developments in mass spectrometry techniques have created opportunities to examine the partitioning behavior of stable isotopes of transition metals with a focus on application to iron isotopes. Iron oxidizing and reducing bacteria have been shown to cause isotope fractionations similar in magnitude to those observed in sedimentary environments and it is believed that biological activity is responsible for the most significant Fe isotope fractionation in natural settings. Debate over the use of Fe isotopes as a biological marker resulted from subsequent measurements of fractionations in a variety of abiotic systems. The accumulated evidence, in both biotic and abiotic systems, points to a connection between redox processes and Fe isotope fractionation, however the exact mechanism for isotope fractionation is not yet well understood. Here, we present both a newly-developed theory based on chemical kinetics and preliminary experimental results that quantitatively delineate the relationship between driving force in a charge transfer reaction and resulting Fe isotope fractionation. The theory, based on R. Marcus's chemical kinetics theory for electron transfer (Ann. Rev. Phys. Chem. 15 (1964), 155), predicts that fractionation increases linearly with driving force with a proportionality related to two factors: the difference between isotopic equilibrium exchange of products and reactants, and the reorganization energy along the reaction coordinate. The theoretical predictions were confirmed by measurements of isotopic fractionation associated with electroplating iron metal from a ferrous chloride solution. Isotope fractionation of Fe electroplated under potentiostatic conditions was measured as a function of applied electrochemical potential. As plating voltage was varied from -50 mV to -2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ 56Fe values ranging from -0.106(±0.01) to -2.290(±±0.006)‰ , and corresponding δ 57Fe values of -0.145(±.011) and -3.354(±.019)‰ . The slope of the line created by plotting δ 56Fe vs δ 57Fe is equal to 0.6723(±.0032), consistent with fractionation due to a kinetic process involving unsolvated iron atoms. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. The magnitude of fractionation is similar to observations of Fe reduction by certain bacteria, suggesting that electrochemical processes may be responsible for observed biogeochemical signatures. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.

The sources and evolution of mineralising fluids in iron oxide-copper-gold systems, Norrbotten, Sweden: Constraints from Br/Cl ratios and stable Cl isotopes of fluid inclusion leachates

NASA Astrophysics Data System (ADS)

Gleeson, S. A.; Smith, M. P.

2009-10-01

We have analysed the halogen concentrations and chlorine stable isotope composition of fluid inclusion leachates from three spatially associated Fe-oxide ± Cu ± Au mineralising systems in Norrbotten, Sweden. Fluid inclusions in late-stage veins in Fe-oxide-apatite deposits contain saline brines and have a wide range of Br/Cl molar ratios, from 0.2 to 1.1 × 10 -3 and δ 37Cl values from -3.1‰ to -1.0‰. Leachates from saline fluid inclusions from the Greenstone and Porphyry hosted Cu-Au prospects have Br/Cl ratios that range from 0.2 to 0.5 × 10 -3 and δ 37Cl values from -5.6‰ to -1.3‰. Finally, the Cu-Au deposits hosted by the Nautanen Deformation Zone (NDZ) have Br/Cl molar ratios from 0.4 to 1.1 × 10 -3 and δ 37Cl values that range from -2.4‰ to +0.5‰, although the bulk of the data fall within 0‰ ± 0.5‰. The Br/Cl ratios of leachates are consistent with the derivation of salinity from magmatic sources or from the dissolution of halite. Most of the isotopic data from the Fe-oxide-apatite and Greenstone deposits are consistent with a mantle derived source of the chlorine, with the exception of the four samples with the most negative values. The origin of the low δ 37Cl values in these samples is unknown but we suggest that there may have been some modification of the Cl-isotope signature due to fractionation between the mineralising fluids and Cl-rich silicate assemblages found in the alteration haloes around the deposits. If such a process has occurred then a modified crustal source of the chlorine for all the samples cannot be ruled out although the amount of fractionation necessary to generate the low δ 37Cl values would be significantly larger. The source of Cl in the NDZ deposits has a crustal signature, which suggests the Cl in this system may be derived from (meta-) evaporites or from input from crustal melts such as granitic pegmatites of the Lina Suite.

Sulfur-, oxygen-, and carbon-isotope studies of Ag-Pb-Zn vein-breccia occurrences, sulfide-bearing concretions, and barite deposits in the north-central Brooks Range, with comparisons to shale-hosted stratiform massive sulfide deposits: A section in Geologic studies in Alaska by the U.S. Geological Survey, 1998

USGS Publications Warehouse

Kelley, Karen D.; Leach, David L.; Johnson, Craig A.

2000-01-01

Stratiform shale-hosted massive sulfide deposits, sulfidebearing concretions and vein breccias, and barite deposits are widespread in sedimentary rocks of Late Devonian to Permian age in the northern Brooks Range. All of the sulfide-bearing concretions and vein breccias are hosted in mixed continental-marine clastic rocks of the Upper Devonian to Lower Mississippian Endicott Group. The clastic rocks and associated sulfide occurrences underlie chert and shale of Mississippian-Pennsylvanian(?) age that contain large stratiform massive sulfide deposits like that at Red Dog. The relative stratigraphic position of the vein breccias, as well as previously published mineralogical, geochemical, and lead-isotope data, suggest that the vein breccias formed coevally with overlying shale-hosted massive sulfide deposits and that they may represent pathways of oreforming hydrothermal fluids. Barite deposits are hosted either in Mississippian chert and limestone (at essentially the same stratigraphic position as the shale-hosted massive sulfide deposits) or Permian chert and shale. Although most barite deposits have no associated base-metal mineralization, barite occurs with massive sulfide deposits at the Red Dog deposit.Galena and sphalerite from most vein breccias have δ34S values from –7.3 to –0.7‰ (per mil) and –5.1 to 3.6‰, respectively; sphalerite from sulfide-bearing concretions have δ34S values of 0.7 and 4.7‰. This overall range in δ34S values largely overlaps with the range previously determined for galena and sphalerite from shale-hosted massive sulfide deposits at Red Dog and Drenchwater. The Kady vein-breccia occurrence is unusual in having higher δ34S values for sphalerite (12.1 to 12.9‰) and pyrite (11.3‰), consistent with previously published values for the shale-hosted Lik deposit. The correspondence in sulfur isotopic compositions between the stratiform and vein-breccia deposits suggests that they share a common source of reduced sulfur, or derived reduced sulfur by similar geochemical processes. Most likely, the reduced sulfur was derived by biogenic sulfate reduction (BSR) or thermochemical sulfate reduction (TSR) of seawater sulfate during Devonian-Mississippian time.The δ18O values of quartz from the vein breccias are between 16.6 and 19.9‰. Using the sphalerite-galena sulfur isotopic temperature of 188°±25°C, the calulated hydrothermal fluids had δ18O values of 4.2 to 7.5‰. The calculated range of δ18O values of the fluids is similar to that of pore fluids in equilibrium with sedimentary rocks during diagenesis at 100°– 190°C.

Tracing Cd, Zn and Pb pollution sources in bivalves using isotopes

NASA Astrophysics Data System (ADS)

Shiel, A. E.; Weis, D. A.; Orians, K. J.

2010-12-01

In a multi-tracer study, Cd, Zn and Pb isotopes (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are evaluated as tools to distinguish between natural and anthropogenic sources of these metals in bivalves from western Canada (British Columbia), the eastern USA, Hawaii and France. High Cd concentrations found in BC oysters have elicited economic and health concerns. The source of these high Cd levels is unknown but thought to be largely natural. High Cd levels in BC oysters are largely attributed to the natural upwelling of Cd-rich intermediate waters in the North Pacific as the δ114/110Cd (-0.69 to -0.09‰) and δ66/64Zn (0.28 to 0.36‰) values of BC oysters fall within the range reported for North Pacific seawater. Different contributions from anthropogenic sources account for the variability of Cd isotopic compositions of BC oysters; the lightest of these oysters are from the BC mainland. These oysters also have Pb isotopic compositions that reflect primarily anthropogenic sources (e.g., leaded and unleaded automotive gasoline and smelting of Pb ores, potentially historical). On the contrary, USA East Coast bivalves exhibit relatively light Cd isotopic compositions (δ114/110Cd = -1.20 to -0.54‰; lighter than reported for North Atlantic seawater) due to the high prevalence of industry on this coast. The Pb isotopic compositions of these bivalves indicate contributions from the combustion of coal. The large variability of environmental health among coastal areas in France is reflected in the broad range of Cd isotopic compositions exhibited by French bivalves (δ114/110Cd = -1.08 to -0.20‰). Oysters and mussels from the Marennes-Oléron basin and Gironde estuary have the lightest Cd isotopic compositions of the French oysters consistent with significant historical Cd emissions from the now-closed proximal Zn smelter. In these bivalves, significant declines in the Cd levels between 1984/7 and 2004/5 are not accompanied by a significant shift in the Cd isotopic composition toward natural values. The Mediterranean samples have isotopic compositions within error of the lighter end of the range reported for Mediterranean seawater. The Zn isotopic compositions of French oysters and mussels (δ66/64Zn = 0.39 to 0.46‰) are identical to those reported for North Atlantic seawater, with the exception of the much heavier compositions of oysters (δ66/64Zn = 1.03 to 1.15‰) from the polluted Gironde estuary. In agreement with Cd and Zn isotopic compositions, the Pb isotopic compositions of the French bivalves indicate primarily industrial (as opposed to automotive) sources; this is consistent with the collection of most of the French bivalve samples in 2004, after the complete phase-out of leaded gasoline in France. This study demonstrates the effective use of Cd and Zn isotopes to trace anthropogenic sources in the environment and the benefit of combining these tools with Pb isotope “fingerprinting” techniques to identify processes contributing metals. Use of these new geochemical tools requires site-specific knowledge of potential metal sources and their isotopic compositions.

Evidence for a nonmagmatic component in potassic hydrothermal fluids of porphyry cu-Au-Mo systems, Yukon, Canada

NASA Astrophysics Data System (ADS)

Selby, David; Nesbitt, Bruce E.; Creaser, Robert A.; Reynolds, Peter H.; Muehlenbachs, Karlis

2001-02-01

Isotopic (H, Sr, Pb, Ar) and fluid inclusion data for hydrothermal fluids associated with potassic alteration from three Late Cretaceous porphyry Cu occurrences, west central Yukon, suggest a nonmagmatic fluid component was present in these hydrothermal fluids. Potassic stage quartz veins contain a dominant assemblage of saline and vapor-rich fluid inclusions that have δD values between -120 and -180‰. Phyllic stage quartz veins are dominated by vapor-rich fluid inclusions and have δD values that overlap with but are, on average, heavier (-117 to -132‰) than those in potassic stage quartz veins. These δD values are significantly lower than those from plutonic quartz phenocrysts (-91 to -113‰), and from values typically reported for primary fluids from porphyry-style mineralization (-40 to -100‰). The initial Sr ( 87Sr/ 86Sr i) isotopic values for the plutons are 0.7055 (Casino), 0.7048 (Mt. Nansen), and 0.7055 (Cash). The 87Sr/ 86Sr i compositions of hydrothermal K-feldspar ranges from magmatic Sr i values to more radiogenic compositions (Casino: 0.70551-0.70834, n = 8; Mt. Nansen: 0.7063-0.7070, n = 4; Cash: 0.7058, n = 1). The fluid inclusion waters from potassic quartz veins have 87Sr/ 86Sr i values that are similar to those of co-existing hydrothermal K-feldspar. The Pb isotopic compositions of hydrothermal K-feldspar show a weak positive correlation with Sr i for identical samples. Fluid inclusion waters of phyllic quartz veins also have Sr i compositions more radiogenic than the plutons. The Pb isotopic composition of pyrite and bornite from phyllic alteration veins are similar to, or more radiogenic than, hydrothermal K-feldspar Pb isotopic values. Hydrothermal K-feldspar samples yield 40Ar/ 39Ar ages (Casino = 71.9 ± 0.7 to 73.4 ± 0.8 Ma; Mt. Nansen = 68.2 ± 0.7 and 69.5 ± 0.6 Ma; Cash = 68.3 ± 0.8 Ma) similar to the U-Pb zircon, K-Ar biotite and Re-Os molybdenite ages of the Late Cretaceous plutons, with the age spectra indicating no excess 40Ar or disturbance. The 40Ar/ 36Ar values (285-292) of the K-feldspar samples are similar to the atmospheric compositions (295 ± 5) during Late Cretaceous time. The H, Sr, Pb, and Ar isotopic compositions of hydrothermal K-feldspar and quartz vein fluid inclusion waters that characterize the potassic hydrothermal fluids show evidence for an exotic component in addition to magmatic water (fluid). This component has a low δD, radiogenic Sr and Pb, and an atmospheric Ar composition. The inheritance of pre-existing isotope compositions from the host rocks, postpotassic alteration isotope exchange, or the replenishment of the magma chamber with magma of different isotopic composition cannot explain the isotope data. We suggest that to generate the observed H, Sr, Pb, and Ar isotope compositions, crustal fluids must be a component (15-94%) of potassic hydrothermal fluids in porphyry mineralization in the deposits studied.

Pb-Sr-Nd-O isotopic characterization of Mesozoic rocks throughout the northern end of the Peninsular Ranges batholith: Isotopic evidence for the magmatic evolution of oceanic arc–continental margin accretion during the Late Cretaceous of southern California

USGS Publications Warehouse

Kistler, Ronald W.; Wooden, Joseph L.; Premo, Wayne R.; Morton, Douglas M.

2014-01-01

Within the duration of the U.S. Geological Survey (USGS)–based Southern California Areal Mapping Project (SCAMP), many samples from the northern Peninsular Ranges batholith were studied for their whole-rock radioisotopic systematics (rubidium-strontium [Rb-Sr], uranium-thorium-lead [U-Th-Pb], and samarium-neodymium [Sm-Nd]), as well as oxygen (O), a stable isotope. The results of three main studies are presented separately, but here we combine them (>400 analyses) to produce a very complete Pb-Sr-Nd-O isotopic profile of an arc-continent collisional zone—perhaps the most complete in the world. In addition, because many of these samples have U-Pb zircon as well as argon mineral age determinations, we have good control of the timing for Pb-Sr-Nd-O isotopic variations.The ages and isotopic variations help to delineate at least four zones across the batholith from west to east—an older western zone (126–108 Ma), a transitional zone (111–93 Ma), an eastern zone (94–91 Ma), and a much younger allochthonous thrust sheet (ca. 84 Ma), which is the upper plate of the Eastern Peninsular Ranges mylonite zone. Average initial 87Sr/86 Sr (Sri), initial 206Pb/204Pb (206 Pbi), initial 208Pb/204Pb (average 208Pbi), initial epsilon Nd (average εNdi), and δ18O signatures range from 0.704, 18.787, 38.445, +3.1, and 4.0‰–9.0‰, respectively, in the westernmost zone, to 0.7071, 19.199, 38.777, −5, and 9‰–12‰, respectively, in the easternmost zone. The older western zone is therefore the more chemically and isotopically juvenile, characterized mostly by values that are slightly displaced from a mantle array at ca. 115 Ma, and similar to some modern island-arc signatures. In contrast, the isotopic signatures in the eastern zones indicate significant amounts of crustal involvement in the magmatic plumbing of those plutons. These isotopic signatures confirm previously published results that interpreted the Peninsular Ranges batholith as a progressively contaminated magmatic arc. The Peninsular Ranges batholith magmatic arc was initially an oceanic arc built on Panthalassan lithosphere that eventually evolved into a continental margin magmatic arc collision zone, eventually overriding North American cratonic lithosphere. Our Pb-Sr-Nd data further suggest that the western arc rocks represent a nearshore or inboard oceanic arc, as they exhibit isotopic signatures that are more enriched than typical mid-ocean-ridge basalt (MORB). Isotopic signatures from the central zone are transitional and indicate that enriched crustal magma sources were becoming involved in the northern Peninsular Ranges batholith magmatic plumbing. As the oceanic arc–continental margin collision progressed, a mixture of oceanic mantle and continental magmatic sources transpired. Magmatic production in the northern Peninsular Ranges batholith moved eastward and continued to tap enriched crustal magmatic sources. Similar modeling has been previously proposed for two other western margin magmatic arcs, the Sierra Nevada batholith of central California and the Idaho batholith.Calculated initial Nd signatures at ca. 100 Ma for Permian–Jurassic and Proterozoic basement rocks from the nearby San Gabriel Mountains and possible source areas along the southwestern Laurentian margin of southern California, southwestern Arizona, and northern Sonora strongly suggest their involvement with deep crustal magma mixing beneath the eastern zones of the Peninsular Ranges batholith, as well as farther east in continental lithospheric zones.Last, several samples from the allochthonous, easternmost upper-plate zone, which are considerably younger (ca. 84 Ma) than any of the rocks from the northern Peninsular Ranges batholith proper, have even more enriched average Sri, 206Pbi, 208Pbi, and εNdisignatures of 0.7079, 19.344, 38.881, and −6.6, respectively, indicative of the most-evolved magma sources in the northern Peninsular Ranges batholith and similar to radioisotopic values for rocks from the nearby Transverse Ranges, suggesting a genetic connection between the two.

Silicon Isotope Geochemistry of Ocean Island Basalts: Mantle Heterogeneities and Contribution of Recycled Oceanic Crust and Lithosphere

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.; Savage, P. S.; Jackson, M. G.; Moreira, M. A.; Day, J. M.

2015-12-01

The study of Silicon (Si) isotopes in Ocean Island Basalts (OIB) has the potential to elucidate between possible heterogeneities in the mantle. Relatively large (~several per mil per atomic mass unit) Si isotope fractionation occurs in low-temperature environments during biochemical and geochemical precipitation of dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes [1]. In contrast, only a limited range (~tenths of a per mil) of Si isotope fractionation has been observed in high-temperature igneous processes [2]. Therefore, Si isotopes may be useful as tracers for the presence of crustal material (derived from low-temperature surface processes) in OIB source regions in a manner similar to more conventional stable isotope systems, such as O. Here we present the first comprehensive set of high-precision Si isotope data obtained by MC-ICP-MS for a diverse suite of OIBs, including new data for the Canary Islands. Samples represent the Pacific, Atlantic, and Indian Ocean basins and include representative end-members for the EM-1, EM-2, and HIMU mantle components. Average δ30Si values for OIBs representing the EM-1 (-0.32 ± 0.06‰, 2 sd), EM-2 (-0.30 ± 0.01‰, 2 sd), and HIMU (-0.34 ± 0.09‰, 2 sd) mantle components are all in general agreement with previous estimates for the δ30Si value of Bulk Silicate Earth [3]. However, small systematic variations are present; HIMU (Mangaia, Cape Verde, La Palma) and Iceland OIBs are enriched in the lighter isotopes of Si (δ30Si values lower than MORB). Further, the difference in Si isotope composition between La Palma and El Heirro (Canary Islands) has previously been observed for O isotopes [4], suggesting a relationship between the Si and O isotope mantle systematics. The Si isotope variations among OIBs may be explained by the sampling of a primitive mantle reservoir enriched in the light isotopes of Si, as suggested by [5], but most likely reflects the incorporation of recycled altered oceanic crust and lithosphere in the plume source. References: [1] Ziegler et al., GCA 2005 [2] Savage et al., GCA 2011 [3] Savage et al., EPSL 2010 [4] Day et al., Geology 2009 [5] Huang et al., GCA 2014

Stable isotope and petrologic evidence for open-system degassing during the climactic and pre-climactic eruptions of Mt. Mazama, Crater Lake, Oregon

USGS Publications Warehouse

Mandeville, C.W.; Webster, J.D.; Tappen, C.; Taylor, B.E.; Timbal, A.; Sasaki, A.; Hauri, E.; Bacon, C.R.

2009-01-01

Evaluation of the extent of volatile element recycling in convergent margin volcanism requires delineating likely source(s) of magmatic volatiles through stable isotopic characterization of sulfur, hydrogen and oxygen in erupted tephra with appropriate assessment of modification by degassing. The climactic eruption of Mt. Mazama ejected approximately 50 km3 of rhyodacitic magma into the atmosphere and resulted in formation of a 10-km diameter caldera now occupied by Crater Lake, Oregon (lat. 43??N, long. 122??W). Isotopic compositions of whole-rocks, matrix glasses and minerals from Mt. Mazama climactic, pre-climactic and postcaldera tephra were determined to identify the likely source(s) of H2O and S. Integration of stable isotopic data with petrologic data from melt inclusions has allowed for estimation of pre-eruptive dissolved volatile concentrations and placed constraints on the extent, conditions and style of degassing. Sulfur isotope analyses of climactic rhyodacitic whole rocks yield ??34S values of 2.8-14.8??? with corresponding matrix glass values of 2.4-13.2???. ??34S tends to increase with stratigraphic height through climactic eruptive units, consistent with open-system degassing. Dissolved sulfur concentrations in melt inclusions (MIs) from pre-climactic and climactic rhyodacitic pumices varies from 80 to 330 ppm, with highest concentrations in inclusions with 4.8-5.2 wt% H2O (by FTIR). Up to 50% of the initial S may have been lost through pre-eruptive degassing at depths of 4-5 km. Ion microprobe analyses of pyrrhotite in climactic rhyodacitic tephra and andesitic scoria indicate a range in ??34S from -0.4??? to 5.8??? and from -0.1??? to 3.5???, respectively. Initial ??34S values of rhyodacitic and andesitic magmas were likely near the mantle value of 0???. Hydrogen isotope (??D) and total H2O analyses of rhyodacitic obsidian (and vitrophyre) from the climactic fall deposit yielded values ??f -103 to -53??? and 0.23-1.74 wt%, respectively. Values of ??D and wt% H2O of obsidian decrease towards the top of the fall deposit. Samples with depleted ??D, and mantle ??18O values, have elevated ??34S values consistent with open-system degassing. These results imply that more mantle-derived sulfur is degassed to the Earth's atmosphere/hydrosphere through convergent margin volcanism than previously attributed. Magmatic degassing can modify initial isotopic compositions of sulfur by >14??? (to ??34S values of 14??? or more here) and hydrogen isotopic compositions by 90??? (to ??D values of -127??? in this case). ?? 2009 Elsevier Ltd.

Using "isotopic spike" from tropical storm to understand water exchange on large scale: case study of Hurricane Rafael in the Lesser Antilles archipelago, October 2012.

PubMed

Lambs, Luc; Bompy, Félix; Dulormne, Maguy

2018-01-03

Studies of wetland eco-hydrology in tropical coastal area are scarce, and the use of water stable isotopes can be of great help. Key constraints for their analysis are (i) the small difference in δ 18 O values between seawater and old evaporated freshwater, and (ii) the fact that the presence of old brackish water limits the determination of the water origin and dynamic. The water of tropical storms displays distinctively depleted heavy stable isotopes, in comparison with usual tropical rainfall without strong convective thunderstorms. During tropical storms, such as Hurricane Rafael in mid-October 2012, the rainfall δ 18 O signal can be decreased by many units. This effect is called an "isotopic spike", and it could be used as a temporal marker of the water fluxes. Water samples, with δ 18 O values as low as = -8.9 ‰, were collected in the islands of Guadeloupe and Saint-Martin during Hurricane Rafael, whereas the usual range of groundwater or mean rainfall δ 18 O values is around -2.8 ± 0.5 ‰, as measured from 2009 to 2012. These water "isotopic spikes" allow us to show a surface fresh water uptake by mangrove trees in Guadeloupe, and in Saint-Martin, to calculate the water renewal of the salt ponds and pools. The "isotopic spikes" generated by tropical storms, are generally used to track back past storm events, as recorded in trees and stalagmites. Here, the propagation of isotopic spike is followed to improve the understanding of the freshwater circulation and the water dynamic within coastal ecosystems influenced by seawater. This article is protected by copyright. All rights reserved.

Molecular carbon isotope variations in core samples taken at the Permian-Triassic boundary layers in southern China

NASA Astrophysics Data System (ADS)

Wang, Ruiliang; Zhang, Shuichang; Brassell, Simon; Wang, Jiaxue; Lu, Zhengyuan; Ming, Qingzhong; Wang, Xiaomei; Bian, Lizeng

2012-07-01

Stable carbon isotope composition (δ13C) of carbonate sediments and the molecular (biomarker) characteristics of a continuous Permian-Triassic (PT) layer in southern China were studied to obtain geochemical signals of global change at the Permian-Triassic boundary (PTB). Carbonate carbon isotope values shifted toward positive before the end of the Permian period and then shifted negative above the PTB into the Triassic period. Molecular carbon isotope values of biomarkers followed the same trend at and below the PTB and remained negative in the Triassic layer. These biomarkers were acyclic isoprenoids, ranging from C15 to C40, steranes (C27 dominates) and terpenoids that were all significantly more abundant in samples from the Permian layer than those from the Triassic layer. The Triassic layer was distinguished by the dominance of higher molecular weight (waxy) n-alkanes. Stable carbon isotope values of individual components, including n-alkanes and acyclic isoprenoids such as phytane, isop-C25, and squalane, are depleted in δ13C by up to 8-10‰ in the Triassic samples as compared to the Permian. Measured molecular and isotopic variations of organic matter in the PT layers support the generally accepted view of Permian oceanic stagnation followed by a massive upwelling of toxic deep waters at the PTB. A series of large-scale (global) outgassing events may be associated with the carbon isotope shift we measured. This is also consistent with the lithological evidence we observed of white thin-clay layers in this region. Our findings, in context with a generally accepted stagnant Permian ocean, followed by massive upwelling of toxic deep waters might be the major causes of the largest global mass extinction event that occurred at the Permian-Triassic boundary.

Monitoring Natural Biodegradation of TCE in Fractured Sedimentary Rocks Using delta 13C of TCE and its Degradation Products: Estimating Isotopic Fractionation Factor under Field Conditions

NASA Astrophysics Data System (ADS)

Revesz, K.; Shapiro, A. M.; Tiedeman, C.; Goode, D. J.; Lacombe, P. J.; Imbrigiotta, T. E.

2008-12-01

The isotopic ratio of 13C/12C, expressed in delta13CVPDB per mill for trichloroethene (TCE), can differentiate between microbial degradation and other processes (dilution, dispersion, and sorption) that can also affect the concentration of TCE and its degradation products. The delta13C of TCE isotopically fractionates during microbial degradation; however, it remains practically unchanged during other processes. The isotope fractionation factor (alpha) estimated under laboratory conditions, however, may not be representative of microbial degradation in natural ground waters. Estimating alpha under field conditions provides evidence of the presence or absence of in situ microbial degradation and provides valuable information on the in situ processes that affect the fate and transport of chlorinated hydrocarbons. Our modified analytical method of analyzing for the isotopic ratio proved to be comparable to previously published methods. Isotope values were stable within analytical uncertainty in sample sizes ranging from 22 to 2200 nanomoles. Prepared standard mixtures of TCE and DCEs (trans- and cis- dichloroethene) were analyzed after every five field samples, and were stable during the time period that field samples were processed (a year). Water samples were collected from multiple boreholes completed in the fractured mudstone underlying the former Naval Air Warfare Center, West Trenton, NJ, and analyzed for delta13C of the chlorinated hydrocarbons. The results showed an ongoing natural microbial degradation following the typical dehalogenation pathway: TCE to DCE (trans- and cis-dichloroethene) to VC (vinyl chloride). The carbon isotope enrichment due to fractionation was smaller between TCE to DCE degradation than the enrichment between DCE to VC degradation, which is consistent with previous investigations. Results also showed a correlation between delta13C of TCE and the transmissivity of the boreholes where water samples were collected. We assumed that boreholes with extremely low transmissivity behaved analogously to microbial batch reactors. The value of alpha obtained from the borehole interval with the lowest transmissivity was 0.99345, which is in the range of published values: 0.9862 to 0.9934. We consider this value to represent the "field alpha" for microbial degradation in the absence of other processes. Values of alpha in other boreholes that differ from the field alpha could point to other processes affecting the delta13C and concentration of TCE. The value of alpha from the various monitored intervals is referred to as the "apparent alpha". The apparent alpha is characteristic of the borehole and the time at which the concentrations and the isotope values were measured. The difference between the apparent alpha and the field alpha provides insight into hydrologic conditions around the well. Results from one well showed fluctuation in the TCE concentrations, which were correlated with the calculated apparent alpha, and pointed to the recent introduction of TCE into the ground water that had not been significantly degraded. Recent drilling in the vicinity of this well may have remobilized free-phase TCE.

Large sulfur isotope fractionations in Martian sediments at Gale crater

NASA Astrophysics Data System (ADS)

Franz, H. B.; McAdam, A. C.; Ming, D. W.; Freissinet, C.; Mahaffy, P. R.; Eldridge, D. L.; Fischer, W. W.; Grotzinger, J. P.; House, C. H.; Hurowitz, J. A.; McLennan, S. M.; Schwenzer, S. P.; Vaniman, D. T.; Archer, P. D., Jr.; Atreya, S. K.; Conrad, P. G.; Dottin, J. W., III; Eigenbrode, J. L.; Farley, K. A.; Glavin, D. P.; Johnson, S. S.; Knudson, C. A.; Morris, R. V.; Navarro-González, R.; Pavlov, A. A.; Plummer, R.; Rampe, E. B.; Stern, J. C.; Steele, A.; Summons, R. E.; Sutter, B.

2017-09-01

Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA’s Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in 34S. Measured values of δ34S range from -47 +/- 14‰ to 28 +/- 7‰, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

Measurement of energy transitions for the decay radiations of 75Ge and 69Ge in a high purity germanium detector

NASA Astrophysics Data System (ADS)

Aydın, Güral; Usta, Metin; Oktay, Adem

2018-06-01

Photoactivation experiments have a wide range of application areas in nuclear, particle physics, and medical physics such as measuring energy levels and half-lifes of nuclei, experiments for understanding imaging methods in medicine, isotope production for patient treatment, radiation security and transportation, radiation therapy, and astrophysics processes. In this study, some energy transition values of the decay radiations of 75Ge and 69Ge, which are the products of photonuclear reactions (γ, n) with germanium isotopes (75Ge and 69Ge), were measured. The gamma spectrum as a result of atomic transitions were analysed by using a high purity semiconductor germanium detector and the energy transition values which are presented here were compared with the ones which are the best in literature. It was observed that the results presented are in agreement with literature in error range and some results have better precisions.

Water consumption in Iron Age, Roman, and Early Medieval Croatia.

PubMed

Lightfoot, E; Slaus, M; O'Connell, T C

2014-08-01

Patterns of water consumption by past human populations are rarely considered, yet drinking behavior is socially mediated and access to water sources is often socially controlled. Oxygen isotope analysis of archeological human remains is commonly used to identify migrants in the archeological record, but it can also be used to consider water itself, as this technique documents water consumption rather than migration directly. Here, we report an oxygen isotope study of humans and animals from coastal regions of Croatia in the Iron Age, Roman, and Early Medieval periods. The results show that while faunal values have little diachronic variation, the human data vary through time, and there are wide ranges of values within each period. Our interpretation is that this is not solely a result of mobility, but that human behavior can and did lead to human oxygen isotope ratios that are different from that expected from consumption of local precipitation. © 2014 Wiley Periodicals, Inc.

Geochemistry of Precambrian carbonates. IV - Early Paleoproterozoic (2.25 +/- 0.25 Ga) seawater

NASA Technical Reports Server (NTRS)

Veizer, Jan; Clayton, R. N.; Hinton, R. W.

1992-01-01

The mineralogy, chemistry, and isotopic composition of the Malmani Dolomite, Duck Creek Dolomite, and Bruce 'Limestone' Member of the Espanola Formation are studied in an effort to restrict the first- and second-order variations in isotopic composition of Early Paleoproterozoic seawater. The diagenetic rank is found to increase in the order Duck Creek less than Bruce less than Malmani. The interpolation of alteration trends to 'best' value yields an estimate of 0.70550 for Sr-87/Sr-86. For delta C-13, the measured range of 0 +/- 1.5 percent PDB is similar to that observed for Phanerozoic marine carbonates, while the 'best' delta O-18 value for dolostones is -5 percent PDB, depleted in O-18 relative to Phanerozoic counterparts but comparable to estimates obtained for Archean facies. The isotope geochemistry and mineralogy of Bruce 'Limestone' Member is consistent with the proposition that the sequence was deposited in a lacustrine environment.

δ18O and δD variations in Holocene massive ice in the Sabettayakha river mouth, northern Yamal Peninsula

NASA Astrophysics Data System (ADS)

Vasil'chuk, Yu. K.; Podborny, Ye. Ye.; Budantseva, N. A.; Vasil'chuk, A. C.; Sullina, A. N.; Chizhova, Ju. N.

2016-10-01

The conditions of formation of massive ice near the South Tambey gas-condensate field in northern Yamal Peninsula are studied. It is shown that massive ice bodies up to 4.5 m thick occur in the Holocene deposits of the high laida and the first terrace. Therefore, they cannot be the remains of glaciers; they are ground ice formations. All three types of massive ice have quite various isotopic compositions: the values of δD range from-107 to-199.7, and δ18O from-15.7 to-26.48‰. Such a significant differentiation in isotopic composition is a result of cryogenic fractionation in a freezing water-saturated sediment. The most negative isotope values are even lower in this Holocene massive ice than in the Late Pleistocene ice-wedge ice of Yamal Peninsula.

Discovering the Importance of Bi-directional Water Fluxes in Leaves

NASA Astrophysics Data System (ADS)

Kayler, Z. E.; Saurer, M.; Siegwolf, R.

2007-12-01

The stable isotope ratio 18O/16O is used for constraining climate change models, partitioning ecosystem water fluxes and for studies of plant ecophysiology. Leaf water enrichment is an essential starting point for each of these applications. In order to obtain a complete picture of the role leaf water plays, not only the 18O values from leaf water but also the signature of transpired water must be accurately predicted for plants under varying environmental conditions. We used a novel chamber approach using highly depleted water (-330 ‰) as a vapor source to leaves of the velvet bean (Mucuna pruriens). We used a Walz gas exchange system consisting of a chamber that is controlled for humidity, light, and temperature. Water and carbon dioxide fluxes were measured by an infrared gas analyzer and chamber vapor was collected in cold traps chilled to - 60°C. Three leaves were collected after 2 hours to insure isotopic steady-state followed by leaf water extraction and isotope analysis. From this experiment we were able to measure the outward flux of soil source water and the inward flux of ambient vapor over a range of environments that varied in relative humidity (80%, 45%, 20%), light (50, 1000 μmolm-2s-1) and CO2 (50, 800 ppm). Leaf water isotopic values were below the source water values reflecting the influx of the labeled vapor. The degree to which leaf water values were depleted was strongly related to the relative humidity. The Craig-Gordon model overestimated depletion of leaf water under high relative humidity and predictions were improved with the Péclet correction. However, our initial analysis indicates that these models may not fully account for stomatal conductance in predicting leaf water isotopic values.

Effect of 13C enrichment and sugar type on analysis of sugars by gas chromatography/combustion/isotope ratio mass spectrometry.

PubMed

Baumann, Karen; Dignac, Marie-France; Bardoux, Gérard; Rumpel, Cornelia

2012-09-15

The objective of this investigation was to test gas-chromatographic compound-specific analysis for studies on the isotopic composition of (13)C-enriched sugar molecules. The effects of (13)C enrichment and type of sugar (C5, C6) will provide valuable information on isotopic correction for future studies employing (13)C-enriched sugars. Five sugar solutions of xylose, mannose and glucose with (13)C enrichments ranging between 1.1 and 1.5 atom-% were prepared. The (13)C enrichments of the initial sugars were measured by elemental analyser/isotope ratio mass spectrometry (EA/IRMS); (13)C enrichments for derivatised sugars were obtained by gas chromatography/combustion/IRMS (GC/C/IRMS). The linear relationships between the (13)C enrichments of the initial sugars and the values for the derivatised sugars were sugar-type dependent. Corrections for GC/C/IRMS values took into account the kinetic isotope effect (KIE) of the derivatising agent associated with the coefficient (K(d)) and a newly introduced second coefficient (K(c)) associated with the KIE of the sugar. While K(d) was constant, K(c) varied with sugar type. During derivatisation acetate groups with (12)C and sugars with more (13)C reacted faster. Coefficients for the specific ranges of (13)C enrichments under study have to be assessed and the reactions of different sugar types have to be taken into account to avoid underestimation of (13)C enrichment of up to 9% (C5) or overestimation of up to 4% (C6). Copyright © 2012 John Wiley & Sons, Ltd.

Speciation and isotopic exchangeability of nickel in soil solution.

PubMed

Nolan, Annette L; Ma, Yibing; Lombi, Enzo; McLaughlin, Mike J

2009-01-01

Knowledge of trace metal speciation in soil pore waters is important in addressing metal bioavailability and risk assessment of contaminated soils. In this study, free Ni(2+) activities were determined in pore waters of long-term Ni-contaminated soils using a Donnan dialysis membrane technique. The pore water free Ni(2+) concentration as a percentage of total soluble Ni ranged from 21 to 80% (average 53%), and the average amount of Ni bound to dissolved organic matter estimated by Windermere Humic Aqueous Model VI was < or = 17%. These data indicate that complexed forms of Ni can constitute a significant fraction of total Ni in solution. Windermere Humic Aqueous Model VI provided reasonable estimates of free Ni(2+) fractions in comparison to the measured fractions (R(2) = 0.83 with a slope of 1.0). Also, the isotopically exchangeable pools (E value) of soil Ni were measured by an isotope dilution technique using water extraction, with and without resin purification, and 0.1 mol L(-1) CaCl(2) extraction, and the isotopic exchangeability of Ni species in soil water extracts was investigated. The concentrations of isotopically non-exchangeable Ni in water extracts were <9% of total water soluble Ni concentrations for all soils. The resin E values expressed as a percentage of the total Ni concentrations in soil showed that the labile Ni pool ranged from 0.9 to 32.4% (average 12.4%) of total soil Ni. Therefore the labile Ni pool in these well-equilibrated contaminated soils appears to be relatively small in relation to total Ni concentrations.

A new approach to the solution of the linear mixing model for a single isotope: application to the case of an opportunistic predator.

PubMed

Hall-Aspland, S A; Hall, A P; Rogers, T L

2005-03-01

Mixing models are used to determine diets where the number of prey items are greater than one, however, the limitation of the linear mixing method is the lack of a unique solution when the number of potential sources is greater than the number (n) of isotopic signatures +1. Using the IsoSource program all possible combinations of each source contribution (0-100%) in preselected small increments can be examined and a range of values produced for each sample analysed. We propose the use of a Moore Penrose (M-P) pseudoinverse, which involves the inverse of a 2x2 matrix. This is easily generalized to the case of a single isotope with (p) prey sources and produces a specific solution. The Antarctic leopard seal (Hydrurga leptonyx) was used as a model species to test this method. This seal is an opportunistic predator, which preys on a wide range of species including seals, penguins, fish and krill. The M-P method was used to determine the contribution to diet from each of the four prey types based on blood and fur samples collected over three consecutive austral summers. The advantage of the M-P method was the production of a vector of fractions f for each predator isotopic value, allowing us to identify the relative variation in dietary proportions. Comparison of the calculated fractions from this method with 'means' from IsoSource allowed confidence in the new approach for the case of a single isotope, N.

New organic reference materials for hydrogen, carbon, and nitrogen stable isotope-ratio measurements: caffeines, n-alkanes, fatty acid methyl esters, glycines, L-valines, polyethylenes, and oils

USGS Publications Warehouse

Schimmelmann, Arndt; Qi, Haiping; Coplen, Tyler B.; Brand, Willi A.; Fong, Jon; Meier-Augenstein, Wolfram; Kemp, Helen F.; Toman, Blaza; Ackermann, Annika; Assonov, Sergey; Aerts-Bijma, Anita; Brejcha, Ramona; Chikaraishi, Yoshito; Darwish, Tamim; Elsner, Martin; Gehre, Matthias; Geilmann, Heike; Gröning, Manfred; Hélie, Jean-François; Herrero-Martín, Sara; Meijer, Harro A.J.; Sauer, Peter E.; Sessions, Alex L.; Werner, Roland A.

2016-01-01

An international project developed, quality-tested, and determined isotope−δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope−δ scales. The RMs span a range of δ2HVSMOW-SLAP values from −210.8 to +397.0 mUr or ‰, for δ13CVPDB-LSVEC from −40.81 to +0.49 mUr and for δ15NAir from −5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C16 n-alkanes, n-C20-fatty acid methyl esters (FAMEs), glycines, and l-valines, together with polyethylene powder and string, one n-C17-FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a 2H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ2H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain 13C and carbon-bound organic 2H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies.

Effects of diagenesis on strontium, carbon, nitrogen and oxygen concentration and isotopic composition of bone

NASA Astrophysics Data System (ADS)

Nelson, Bruce K.; Deniro, Michael J.; Schoeninger, Margaret J.; De Paolo, Donald J.; Hare, P. E.

1986-09-01

Paleodietary analysis based on variations in the trace element and stable isotopic composition of inorganic and organic phases in fossil bone depends on the assumption that measured values reflect in vivo values. To test for postmortem alteration, we measured 87Sr /86Sr , 13C /12C , 18O /16O and 15N /14N ratios and Sr concentrations in modern and prehistoric (610 to 5470 yr old) bones of animals with marine or terrestrial diets from Greenland. Bones from modern terrestrial feeders have substantially lower Sr concentrations and more radiogenic 87Sr /86Sr ratios than those from modern marine feeders. This contrast was not preserved in the prehistoric samples, which showed almost complete overlap for both Sr concentration and isotopic composition in bones from the two types of animals. Leaching experiments, X-ray diffraction analysis and infrared spectroscopy indicate that alteration of the Sr concentration and isotopic composition in prehistoric bone probably results from nearly complete exchange with groundwater. Oxygen isotope ratios in fossil apatite carbonate also failed to preserve the original discrimination between modern terrestrial and marine feeders. The C isotope ratio of apatite carbonate did not discriminate between animals with marine or terrestrial diets in the modern samples. Even so, the ranges of apatite δ 13C values in prehistoric bone are more scattered than in modern samples for both groups, suggesting alteration had occurred. δ 13C and δ 15N values of collagen in modern bone are distinctly different for the two feeding types, and this distinction is preserved in most of the prehistoric samples. Our results suggest that postmortem alteration of dietary tracers in the inorganic phases of bone may be a problem at all archaeological sites and must be evaluated in each case. While collagen analyzed in this study was resistant to alteration, evaluation of the possibility of diagenetic alteration of its isotopic composition in bones from other contexts is also warranted.

Validation of GC-IRMS techniques for δ13C and δ2H CSIA of organophosphorus compounds and their potential for studying the mode of hydrolysis in the environment.

PubMed

Wu, Langping; Kümmel, Steffen; Richnow, Hans H

2017-04-01

Compound-specific stable isotope analysis (CSIA) is among the most promising tools for studying the fate of organic pollutants in the environment. However, the feasibility of multidimensional CSIA was limited by the availability of a robust method for precise isotope analysis of heteroatom-bearing organic compounds. We developed a method for δ 13 C and δ 2 H analysis of eight organophosphorus compounds (OPs) with different chemical properties. In particular, we aimed to compare high-temperature conversion (HTC) and chromium-based HTC (Cr/HTC) units to explore the limitations of hydrogen isotope analysis of heteroatom-bearing compounds. Analysis of the amount dependency of the isotope values (linearity analysis) of OPs indicated that the formation of HCl was a significant isotope fractionation process leading to inaccurate δ 2 H analysis in HTC. In the case of nonchlorinated OPs, by-product formation of HCN, H 2 S, or PH 3 in HTC was observed but did not affect the dynamic range of reproducible isotope values above the limit of detection. No hydrogen-containing by-products were found in the Cr/HTC process by use of ion trap mass spectrometry analysis. The accuracy of gas chromatography - isotope ratio mass spectrometry was validated in comparison with elemental analyzer - isotope ratio mass spectrometry. Dual-isotope fractionation yielded Λ values of 0 ± 0 at pH 7, 7 ± 1 at pH 9, and 30 ± 6 at pH 12, indicating the potential of 2D CSIA to characterize the hydrolysis mechanisms of OPs. This is the first report on the combination of δ 2 H and δ 13 C isotope analysis of OPs, and this is the first study providing a systematic evaluation of HTC and Cr/HTC for hydrogen isotope analysis using OPs as target compounds. Graphical Abstract Comparison of δ 2 H measurement of non-chlorinated and chlorinated OPs via GC-Cr/HTC-IRMS and GC-HTC-IRMS system.

Tracking Movement of Plant Carbon Through Soil to Water by Lignin Phenol Stable Carbon Isotope Composition in a Small Agricultural Watershed

NASA Astrophysics Data System (ADS)

Crooker, K.; Filley, T.; Six, J.; Frey, J.

2005-12-01

Few studies integrate land cover, soil physical structure, and aquatic physical fractions when investigating the fate of agricultural carbon in watersheds. In crop systems that involve rotations of soy (a C3 plant) and corn (a C4 plant) the large intrinsic differences in stable carbon isotope values and lignin plus cutin chemistry enable tracking of plant carbon movement from soil fractions to DOM and overland flow during precipitation events. In a small (~3Km2) agricultural basin in central Indiana, we studied plant carbon dynamics in a soy/corn agricultural rotation (2004-2005) to determine the relative inputs of these two plants to soil fractions and the resultant contributions to dissolved, colloidal, and particulate organic matter when mobilized. Using bulk isotope values the fraction of carbon derived from corn in macroaggregates (>250 micron), microaggregates (53-250 mm), and silts plus clays (<53 mm) ranged from 39, 49, to 42%, respectively. Unlike bulk analyses, compound specific isotope analysis of lignin in the soil fractions revealed a wide range of relative inputs among the monomers with cinnamyl phenols being almost exclusively (~ 93%) derived from corn. Syringyl phenols ranged from 75-56% corn and vanillyl phenols ranged from 37-40% corn carbon. The relative input among the fractions mirrors closely the comparative plant chemistry abundances between soy and corn. During export of DOM from the land to the stream the relative abundance of plant source varied with discharge (0.05-1.8 m3/sec) as increases in flow increased the relative export of corn-derived C from the fields. Over the full range of flows lignin phenols varied from 0.05 to 82% corn-derived with the greatest relative corn input for cinnamyl and syringyl carbon. The trend with stream discharge indicates a progressive movement of particulate corn residues with overland flow. Ongoing studies look to resolve contributions of algae, bacteria and terrestrial plants to soil fractions and their mobilized components.

Sulfur and lead isotope geochemistry of hypogene mineralization at the Barite Hill Gold Deposit, Carolina Slate Belt, southeastern United States: A window into and through regional metamorphism

USGS Publications Warehouse

Seal, Robert R.; Ayuso, Robert A.; Foley, Nora K.; Clark, Sandra H.B.

2001-01-01

The Barite Hill gold deposit, at the southwestern end of the Carolina slate belt in the southeastern United States, is one of four gold deposits in the region that have a combined yield of 110 metric tons of gold over the past 10 years. At Barite Hill, production has dominantly come from oxidized ores. Sulfur isotope data from hypogene portions of the Barite Hill gold deposit vary systematically with pyrite–barite associations and provide insights into both the pre-metamorphic Late Proterozoic hydrothermal and the Paleozoic regional metamorphic histories of the deposit. The δ34S values of massive barite cluster tightly between 25.0 and 28.0‰, which closely match the published values for Late Proterozoic seawater and thus support a seafloor hydrothermal origin. The δ34S values of massive sulfide range from 1.0 to 5.3‰ and fall within the range of values observed for modern and ancient seafloor hydrothermal sulfide deposits. In contrast, δ34S values for finer-grained, intergrown pyrite (5.1–6.8‰) and barite (21.0–23.9‰) are higher and lower than their massive counterparts, respectively. Calculated sulfur isotope temperatures for the latter barite–pyrite pairs (Δ=15.9–17.1‰) range from 332–355 °C and probably reflect post-depositional equilibration at greenschist-facies regional metamorphic conditions. Thus, pyrite and barite occurring separately from one another provide pre-metamorphic information about the hydrothermal origin of the deposit, whereas pyrite and barite occurring together equilibrated to record the metamorphic conditions. Preliminary fluid inclusion data from sphalerite are consistent with a modified seawater source for the mineralizing fluids, but data from quartz and barite may reflect later metamorphic and (or) more recent meteoric water input. Lead isotope values from pyrites range for 206Pb/204Pb from 18.005–18.294, for 207Pb/204Pb from 15.567–15.645, and for 208Pb/204Pb from 37.555–38.015. The data indicate derivation of the ore leads from the country rocks, which themselves show evidence for contributions from relatively unradiogenic, mantle-like lead, and more evolved or crustal lead. Geological relationships, and stable and radiogenic isotopic data, suggest that the Barite Hill gold deposit formed on the Late Proterozoic seafloor through exhalative hydrothermal processes similar to those that were responsible for the massive sulfide deposits of the Kuroko district, Japan. On the basis of similarities with other gold-rich massive sulfide deposits and modern seafloor hydrothermal systems, the gold at Barite Hill was probably introduced as an integral part of the formation of the massive sulfide deposit.

Reassessing the stable isotope composition assigned to methane flux from natural wetlands in isotope-constrained budgets

NASA Astrophysics Data System (ADS)

Hornibrook, Edward; Maxfield, Peter; Gauci, Vincent; Stott, Andrew

2013-04-01

Stable isotope ratios in CH4 preserve information about its origin and history, and are commonly used to constrain global CH4 budgets. Wetlands are key contributors to the atmospheric burden of CH4 and typically are assigned a stable carbon isotope composition of ~-60 permil in isotope-weighted stable isotope models despite the considerable range of δ13C(CH4) values (~ -100 to -40 permil) known to occur in these diverse ecosystems. Kinetic isotope effects (KIEs) associated with the metabolism of CH4-producing microorganisms generate much of the natural variation but highly negative and positive δ13C(CH4) values generally result from secondary processes (e.g., diffusive transport or oxidation by soil methanotrophs). Despite these complexities, consistent patterns exist in the isotope composition of wetland CH4 that can be linked conclusively to trophic status and consequently, natural succession or human perturbations that impact nutrient levels. Another challenge for accurate representation of wetlands in carbon cycle models is parameterisation of sporadic CH4 emission events. Abrupt release of large volumes of CH4-rich bubbles in short periods of time can account for a significant proportion of the annual CH4 flux from a wetland but such events are difficult to detect using conventional methods. New infrared spectroscopy techniques capable of high temporal resolution measurements of CH4 concentration and stable isotope composition can readily quantify short-lived CH4 pulses. Moreover, the isotope data can be used conclusively to determine shifts in the mode of CH4 transport and provide the potential to link initiation of abrupt emission events to forcing by internal or external factors.

Modern reindeer and mice: revised phosphate-water isotope equations

NASA Astrophysics Data System (ADS)

Longinelli, Antonio; Iacumin, Paola; Davanzo, Silvana; Nikolaev, Vladimir

2003-09-01

The oxygen isotope composition of bone and tooth phosphate of 34 mice specimens ( Pitymus sp., Microtus arvalis and Arvicola terrestris) coming from seven different locations in Italy, Germany and Switzerland was measured by means of well-established techniques. These measurements were carried out with the purpose of establishing quantitative relationships between the δ 18O p from different mice genera and the mean δ 18O w values and to compare these data to previous measurements carried out on various specimens belonging to the genus Apodemus. The three genera studied showed a similar behaviour when compared to the mean δ 18O w values. The slope of the equation calculated for these three genera is significantly different from the slope obtained from Apodemus specimens. Reconsidering the δ 18O w values suggested in the case of Apodemus due to the small number of data available at that time, it seems that these values are too negative by 0.5 to about 1.5‰. If so, the Apodemus equation becomes almost identical to the equation calculated for the new mice values and, consequently, one could conclude that several micromammal genera and species might behave in the same way and obey the same relationship with the mean δ 18O w values. A set of 25 samples of modern reindeer skeletal material from Spitzbergen, Russia and Siberia was also studied with the aim of improving the reindeer isotope equation obtained from a previous study. In fact, the slope of that equation was somehow uncertain due to a rather large range of isotope values obtained from each group of reindeers coming from the same location. The new results confirm such 'anomalous' behaviour already shown by other mammals and probably related to dietary behaviours, water fluxes with the environment and isotopic composition of ingested food and water rather than to imperfect equilibrium conditions with environmental water. However, the equation calculated from both the old and new, statistically more significant, isotope results is not far from the previous one.

Isotopologue fractionation during N(2)O production by fungal denitrification.

PubMed

Sutka, Robin L; Adams, Gerard C; Ostrom, Nathaniel E; Ostrom, Peggy H

2008-12-01

Identifying the importance of fungi to nitrous oxide (N2O) production requires a non-intrusive method for differentiating between fungal and bacterial N2O production such as natural abundance stable isotopes. We compare the isotopologue composition of N2O produced during nitrite reduction by the fungal denitrifiers Fusarium oxysporum and Cylindrocarpon tonkinense with published data for N2O production during bacterial nitrification and denitrification. The fractionation factors for bulk nitrogen isotope values for fungal denitrification were in the range -74.7 to -6.6 per thousand. There was an inverse relationship between the absolute value of the fractionation factors and the reaction rate constant. We interpret this in terms of variation in the relative importance of the rate constants for diffusion and enzymatic reduction in controlling the net isotope effect for N2O production during fungal denitrification. Over the course of nitrite reduction, the delta(18)O values for N2O remained constant and did not exhibit a relationship with the concentration characteristic of an isotope effect. This probably reflects isotopic exchange with water. Similar to the delta(18)O data, the site preference (SP; the difference in delta(15)N between the central and outer N atoms in N2O) was unrelated to concentration during nitrite reduction and, therefore, has the potential to act as a conservative tracer of production from fungal denitrification. The SP values of N2O produced by F. oxysporum and C. tonkinense were 37.1 +/- 2.5 per thousand and 36.9 +/- 2.8 per thousand, respectively. These SP values are similar to those obtained in pure culture studies of bacterial nitrification but quite distinct from SP values for bacterial denitrification. The large magnitude of the bulk nitrogen isotope fractionation and the delta(18)O values associated with fungal denitrification are distinct from bacterial production pathways; thus multiple isotopologue data holds much promise for resolving bacterial and fungal production. Our work further provides insight into the role that fungal and bacterial nitric oxide reductases have in determining site preference during N2O production. Copyright 2008 John Wiley & Sons, Ltd.

Crustal contamination processes traced by helium isotopes: Examples from the Sunda arc, Indonesia

NASA Astrophysics Data System (ADS)

Gasparon, M.; Hilton, D. R.; Varne, R.

1994-08-01

Helium isotope data have been obtained on well-characterised olivine and clinopyroxene phenocrysts and xenocrysts from thirteen volcanic centres located between central Sumatra and Sumbawa in the Sunda arc of Indonesia. Olivine crystals in mantle xenoliths (Iherzolite) from Bukit Telor basalts are primitive (Mg# = 90), and their He-3/He-4 value (R/R(sub A) = 8.8) indicates that the Sumatran mantle wedge is MORB-like in helium isotope composition. All other samples have lower He-3/He-4 ratios ranging from 8.5R(sub A) to 4.5R(sub A), with most (thirteen out of eighteen) following a trend of more radiogenic He-3/He-4 values with decreasing Mg#. The only exceptions to this trend are phenocrysts from Batur, Agung and Kerinci, which have MORB-like He-3/He-4 values but relatively low Mg# (Mg# = 70-71), and two highly inclusion-rich clinopyroxenes which have He-3/He-4 values lower than other samples of similar Mg#. The results indicate that crustal contamination unrelated to subduction in the Sunda arc is clearly recorded in the He-3/He-4 characteristics of mafic phenocrysts of subaerial volcanics, and that addition of radiogenic helium is related to low-pressure differentiation processes affecting the melts prior to eruption. These conclusions may have widespread applicability and indicate that helium isotope variations can act as an extremely sensitive tracer of upper crustal contamination.

Paleoenvironmental implications of taxonomic variation among δ15N values of chloropigments

USGS Publications Warehouse

Higgins, Meytal B.; Wolfe-Simon, Felisa; Robinson, Rebecca S.; Qin, Yelun; Saito, Mark A.; Pearson, Ann

2011-01-01

Natural variations in the ratios of nitrogen isotopes in biomass reflect variations in nutrient sources utilized for growth. In order to use δ15N values of chloropigments of photosynthetic organisms to determine the corresponding δ15N values of biomass – and by extension, surface waters – the isotopic offset between chlorophyll and biomass must be constrained. Here we examine this offset in various geologically-relevant taxa, grown using nutrient sources that may approximate ocean conditions at different times in Earth’s history. Phytoplankton in this study include cyanobacteria (diazotrophic and non-diazotrophic), eukaryotic algae (red and green), and anoxygenic photosynthetic bacteria (Proteobacteria), as well as environmental samples from sulfidic lake water. Cultures were grown using N2, NO3−, and NH4+ as nitrogen sources, and were examined under different light regimes and growth conditions. We find surprisingly high variability in the isotopic difference (δ15Nbiomass − δ15Nchloropigment) for prokaryotes, with average values for species ranging from −12.2‰ to +11.7‰. We define this difference as εpor, a term that encompasses diagenetic porphyrins and chlorins, as well as chlorophyll. Negative values of εpor reflect chloropigments that are 15N-enriched relative to biomass. Notably, this enrichment appears to occur only in cyanobacteria. The average value of εpor for freshwater cyanobacterial species is −9.8 ± 1.8‰, while for marine cyanobacteria it is −0.9 ± 1.3‰. These isotopic effects group environmentally but not phylogenetically, e.g., εpor values for freshwater Chroococcales resemble those of freshwater Nostocales but differ from those of marine Chroococcales. Our measured values of εpor for eukaryotic algae (range = 4.7–8.7‰) are similar to previous reports for pure cultures. For all taxa studied, values of εpor do not depend on the type of nitrogen substrate used for growth. The observed environmental control of εpor suggests that values of εpor could be useful for determining the fractional burial of eukaryotic vs. cyanobacterial organic matter in the sedimentary record.

Stable Cl isotope composition of the Changjiang River water

NASA Astrophysics Data System (ADS)

Lang, Y.; Liu, C. Q.; LI, S. L.; Aravena, R.; Ding, H.; WANG, B.; Benjamin, C.

2017-12-01

To understand chemical wreathing, nutrient cycling, and the impact of human activities on eco-environments of the Changjiang River (Yangtze River) Basin, we carried out a geochemical study on water chemistry and multiple isotopes (C, N, S, Sr…...) of Changjiang River water in the summer season. Some of the research results about the water chemistry, boron isotope geochemistry and suspended matter have been published (Chetelat et al., 2008; Li et al., 2010). Ten samples were selected for the measurement of δ37Cl values, among which 7 samples were collected from main stream and 3 samples from tributaries. The range of δ37Cl values varies between 0.02‰ and 0.33‰ in the main stream and between 0.16‰ and 0.71‰ in the tributary waters. The δ37Cl values in general are negatively correlated with Cl- concentrations for both main stream and tributary waters. δ37Cl value of Wujiang, which is one of the large tributaries in the upper reach of Changjiang and dominated by carbonate rocks in lithology of the watershed, has the maximum value but minimum value of Cl- concentration in this study. The lowest δ37Cl value was measured for the water collected from the estuary of Changjiang River. The variation of δ37Cl values in the waters would be attributed to mixing of different sources of chlorine, which most likely include rain water, ground water, seawater, and pollutants. Systematic characterization of different Cl sources in terms of their chlorine isotope composition is imperative for better understanding of sources and processes of chlorine cycling. Acknowledgements: This work was financially supported by NSFC through project 41073099. (Omit references)

Carbon isotope signature of dissolved inorganic carbon (DIC) in precipitation and atmospheric CO2.

PubMed

Górka, Maciej; Sauer, Peter E; Lewicka-Szczebak, Dominika; Jędrysek, Mariusz-Orion

2011-01-01

This paper describes results of chemical and isotopic analysis of inorganic carbon species in the atmosphere and precipitation for the calendar year 2008 in Wrocław (SW Poland). Atmospheric air samples (collected weekly) and rainwater samples (collected after rain episodes) were analysed for CO2 and dissolved inorganic carbon (DIC) concentrations and for δ13C composition. The values obtained varied in the ranges: atmospheric CO2: 337-448 ppm; δ13CCO2 from -14.4 to -8.4‰; DIC in precipitation: 0.6-5.5 mg dm(-3); δ13CDIC from -22.2 to +0.2‰. No statistical correlation was observed between the concentration and δ13C value of atmospheric CO2 and DIC in precipitation. These observations contradict the commonly held assumption that atmospheric CO2 controls the DIC in precipitation. We infer that DIC is generated in ambient air temperatures, but from other sources than the measured atmospheric CO2. The calculated isotopic composition of a hypothetical CO2 source for DIC forming ranges from -31.4 to -11.0‰, showing significant seasonal variations accordingly to changing anthropogenic impact and atmospheric mixing processes. Copyright © 2010 Elsevier Ltd. All rights reserved.

Strontium isotope systematics of mixing groundwater and oil-field brine at Goose Lake in northeastern Montana, USA

USGS Publications Warehouse

Peterman, Zell E.; Thamke, Joanna N.; Futa, Kiyoto; Preston, Todd

2012-01-01

Groundwater, surface water, and soil in the Goose Lake oil field in northeastern Montana have been affected by Cl−-rich oil-field brines during long-term petroleum production. Ongoing multidisciplinary geochemical and geophysical studies have identified the degree and local extent of interaction between brine and groundwater. Fourteen samples representing groundwater, surface water, and brine were collected for Sr isotope analyses to evaluate the usefulness of 87Sr/86Sr in detecting small amounts of brine. Differences in Sr concentrations and 87Sr/86Sr are optimal at this site for the experiment. Strontium concentrations range from 0.13 to 36.9 mg/L, and corresponding 87Sr/86Sr values range from 0.71097 to 0.70828. The local brine has 168 mg/L Sr and a 87Sr/86Sr value of 0.70802. Mixing relationships are evident in the data set and illustrate the sensitivity of Sr in detecting small amounts of brine in groundwater. The location of data points on a Sr isotope-concentration plot is readily explained by an evaporation-mixing model. The model is supported by the variation in concentrations of most of the other solutes.

Molecular and isotopic analyses of Tagish Lake alkyl dicarboxylic acids

NASA Astrophysics Data System (ADS)

Pizzarello, Sandra; Huang, Yongsong

2002-05-01

The Tagish Lake meteorite soluble organic suite has a general composition that differs from those of both CI- and CM chondrites. These differences suggest that distinct processes may have been involved in the formation of different groups of organics in meteorites. Tagish Lake alkyl dicarboxylic acids have a varied, abundant distribution and are, with carboxylated pyridines, the only compounds to have an occurrence comparable to that of the Murchison meteorite. This study has undertaken their molecular and isotopic characterization, with the aim to understand their origin and to gain insights into the evolutionary history of the meteorite parent body. Tagish Lake alkyl dicarboxylic acids are present as a homologous series of saturated and unsaturated species with three through ten-carbon atom chain length. Linear saturated acids are predominant and show decreasing amounts with increasing chain length. A total of forty-four of these compounds were detected with the most abundant, succinic acid, present at ~40 nmoles/g. met. Overall the molecular distribution of Tagish Lake dicarboxylic acids shows a remarkable compound to compound correspondence with those observed in the Murchison and Murray meteorites. In both Tagish Lake and Murchison, the imides of the more abundant dicarboxylic acids were also observed. The hydrogen and carbon isotopic compositions of individual Tagish Lake dicarboxylic acids were determined and compared to those of the corresponding acids in the Murchison meteorite. All delta D and delta 13C values for Tagish Lake acids are positive and show a substantial isotopic enrichment. Delta D values vary from, approximately, + 1120 deg for succinic acid to + 1530 deg for methyl glutaric acid. Delta 13C values ranged from + 12.6 deg for methyl glutaric acid to + 22.9 deg for glutaric acid, with adipic acid having a significantly lower value (+ 5.5 deg). Murchison dicarboxylic acid showed similar isotopic values: their delta 13C values were generally higher by an average 17% and delta D values were lower for succinic and glutaric acids, possibly due to contamination. The molecular and isotopic data collected for these compounds restrict their possible origin to processes, either interstellar or of very cold nebular regions, that produced significant isotopic enrichments. Saturated or partially unsaturated nitriles and dinitriles appear to be good precursor candidates as their hydrolysis, upon water exposure, would produce dicarboxylic acids and other carboxylated species found in Tagish Lake. This evolutionary course could possibly include pre-accretionary processes.

Application of stable isotope (δ13C and δ18O) composition of mollusc shells in palaeolimnological studies - possibilities and limitations

NASA Astrophysics Data System (ADS)

Apolinarska, Karina; Pełechaty, Mariusz; Kossler, Annette; Pronin, Eugeniusz; Noskowiak, Daria

2017-04-01

Carbon (δ13C) and oxygen (δ18O) stable isotope analyses are among the standard methods applied in the studies of past environment, including climate. In lacustrine sediments, δ13C and δ18O values can be measured in fine carbonate fraction (carbonate mud), in charophyte encrustations, ostracod carapaces and mollusc shells. Application of the stable isotope record of each of the above-mentioned components of the lake sediment requires knowledge about possibilities and limitations of the method. The present research discusses the most important results of the studies carried out between 2011 and 2013, concentrated on the stable isotope composition of snail shells, primarily, the species commonly preserved in central European Quaternary lacustrine sediments. The stable isotope studies involved also, the zebra mussel (Dreissena polymorpha), one of the most invasive freshwater species in the world. The research involved shell isotope studies of both recent (Apolinarska, 2013; Apolinarska et al., 2016; Apolinarska and Pełechaty, in press) and fossil molluscs derived from the Holocene sediments (Apolinarska et al., 2015a, b). Shell δ13C values were species-specific and among the gastropods studied the same order of species from the most to the least 13C-depleted was observed at all sites sampled. Shell δ18O values were more uniform. The wide range of δ13C and δ18O values were observed in population and subpopulation, i.e. when live snails were sampled live from restricted area within the lake littoral zone. Carbon and oxygen stable isotope values of the mono-specific shells sampled from 1 cm thick sediment samples were highly variable. Those intra-specific differences (n=20) were as large as several permill. Such significant variability in δ13C and δ18O values indicates that stable isotope composition of single shells is unlikely to be representative of the sediment sample. In conclusion, samples of freshwater molluscs for stable isotope analyses should be monospecific and composed of at least several shells. The number of shells being dependent on the difference between the minimum and maximum values within the sediment layer. The research was funded by the Polish Ministry of Science and Higher Education, Iuventus Plus Program, grant No. IP2010 000670. Apolinarska, K., 2013. Stable isotope compositions of recent Dreissena polymorpha (Pallas) shells: paleoenvironmental implications. Journal of Paleolimnology 50, 353-364. Apolinarska, K., Pełechaty, M. & Kossler, A., 2015a. Within-sample variability of δ13C and δ18O values of freshwater gastropod shells and the optimum number of shells to measure per sediment layer in the Paddenluch palaeolacustrine sequence, Germany. Journal of Paleolimnology 54, 305-323. Apolinarska, K., Pełechaty, M. & Noskowiak, D., 2015b. Differences in stable isotope compositions of freshwater snails from surface sediments of two Polish shallow lakes. Limnologica 53, 95-105. Apolinarska, K., Pełechaty, M. & Pronin, E., 2016. Discrepancies between the stable isotope compositions of water, macrophyte carbonates and organics, and mollusc shells in the littoral zone of a charophyte-dominated lake (Lake Lednica, Poland). Hydrobiologia 768, 1-17. Apolinarska, K. & Pełechaty, M., Inter- and intra-specific variability in δ13C and δ18O values of freshwater gastropod shells from Lake Lednica, western Poland. DOI: 10.1515/agp-2016-0028

Unexpected hydrogen isotope variation in oceanic pelagic seabirds

USGS Publications Warehouse

Ostrom, Peggy H.; Wiley, Anne E.; Rossman, Sam; Stricker, Craig A.; James, Helen F.

2014-01-01

Hydrogen isotopes have significantly enhanced our understanding of the biogeography of migratory animals. The basis for this methodology lies in predictable, continental patterns of precipitation δD values that are often reflected in an organism's tissues. δD variation is not expected for oceanic pelagic organisms whose dietary hydrogen (water and organic hydrogen in prey) is transferred up the food web from an isotopically homogeneous water source. We report a 142% range in the δD values of flight feathers from the Hawaiian petrel (Pterodroma sandwichensis), an oceanic pelagic North Pacific species, and inquire about the source of that variation. We show δD variation between and within four other oceanic pelagic species: Newell's shearwater (Puffinus auricularis newellii), Black-footed albatross (Phoebastria nigripes), Laysan albatross (Phoebastria immutabilis) and Buller's shearwater (Puffinus bulleri). The similarity between muscle δD values of hatch-year Hawaiian petrels and their prey suggests that trophic fractionation does not influence δD values of muscle. We hypothesize that isotopic discrimination is associated with water loss during salt excretion through salt glands. Salt load differs between seabirds that consume isosmotic squid and crustaceans and those that feed on hyposmotic teleost fish. In support of the salt gland hypothesis, we show an inverse relationship between δD and percent teleost fish in diet for three seabird species. Our results demonstrate the utility of δD in the study of oceanic consumers, while also contributing to a better understanding of δD systematics, the basis for one of the most commonly utilized isotope tools in avian ecology.

Ecophysiology of the hydrothermal vent snail Ifremeria nautilei and barnacle Eochionelasmus ohtai manusensis, Manus Basin, Papua New Guinea: Insights from shell mineralogy and stable isotope geochemistry

NASA Astrophysics Data System (ADS)

Bojar, Ana-Voica; Lécuyer, Christophe; Bojar, Hans-Peter; Fourel, François; Vasile, Ştefan

2018-03-01

Deep-sea vent communities live on a limited area characterized by sharp physico-chemical (temperature, salinity, pH) gradients. Around the vent, the fauna is distributed accordingly, showing characteristic niche partitioning for different groups of animals. In this study we investigate shell microstructure, minor elements and stable isotope compositions of two groups of organisms such as a snail, Ifremeria nautilei, and a crustacean, Eochionelasmus ohtai manusensis. Both organisms occupy distinct niches within the same hydrothermal vent field of the Manus Basin, Western Pacific. Powder XRD and electron microbeam analysis of a polished cross-section indicate that the shells are composed of microcrystalline calcite, with distinct Na, Mg, Sr, and S element contents. For both specimens 20-30 μm large weddellite crystals were found. The δ18O profiles were obtained perpendicular to the growth increments of I. nautilei and E. o. manusensis calcitic shells. Those profiles reveal isotopic variations of 0.5 and 0.6‰, respectively for both intra- and inter-shell measurements. For E. o. manusensis, the Mg content suggests continuous shell growth during the year, both δ18O and Mg data supporting cyclical variation of temperature at vent site. The calculated temperatures at sites with I. nautilei and E. o. manusensis range from 17° to 21.5°C and from 2.1° to 7.2°C, respectively, showing a similar variability of 5-6 °C. The δ13C values of the Ifremeria calcitic shell range from 3‰ to 4.6‰ (V-PDB), the isotopic composition being 13C-enriched relative to the surrounding inorganic pool. The δ13C values of the chitine layer covering the shell range from - 33 to - 31.1‰. The δ13C values of Eochionelasmus vary between 0‰ and 1‰, reflecting the surrounding inorganic DIC pool.

An experiment to assess the effects of diatom dissolution on oxygen isotope ratios.

PubMed

Smith, Andrew C; Leng, Melanie J; Swann, George E A; Barker, Philip A; Mackay, Anson W; Ryves, David B; Sloane, Hilary J; Chenery, Simon R N; Hems, Mike

2016-01-30

Current studies which use the oxygen isotope composition from diatom silica (δ(18) Odiatom ) as a palaeoclimate proxy assume that the δ(18) Odiatom value reflects the isotopic composition of the water in which the diatom formed. However, diatoms dissolve post mortem, preferentially losing less silicified structures in the water column and during/after burial into sediments. The impact of dissolution on δ(18) Odiatom values and potential misinterpretation of the palaeoclimate record are evaluated. Diatom frustules covering a range of ages (6 samples from the Miocene to the Holocene), environments and species were exposed to a weak alkaline solution for 48 days at two temperatures (20 °C and 4 °C), mimicking natural dissolution post mucilage removal. Following treatment, dissolution was assessed using scanning electron microscope images and a qualitative diatom dissolution index. The diatoms were subsequently analysed for their δ(18) O values using step-wise fluorination and isotope ratio mass spectrometry. Variable levels of diatom dissolution were observed between the six samples; in all cases higher temperatures resulted in more frustule degradation. Dissolution was most evident in younger samples, probably as a result of the more porous nature of the silica. The degree of diatom dissolution does not directly equate to changes in the isotope ratios; the δ(18) Odiatom value was, however, lower after dissolution, but in only half the samples was this reduction outside the analytical error (2σ analytical error = 0.46‰). We have shown that dissolution can have a small negative impact on δ(18) Odiatom values, causing reductions of up to 0.59‰ beyond analytical error (0.46‰) at natural environmental temperatures. These findings need to be considered in palaeoenvironmental reconstructions using δ(18) Odiatom values, especially when interpreting variations in these values of <1‰. Copyright © 2015 John Wiley & Sons, Ltd.

Hg isotopes reveal in-stream processing and legacy inputs in East Fork Poplar Creek, Oak Ridge, Tennessee, USA

DOE PAGES

Demers, Jason D.; Blum, Joel D.; Brooks, Scott C.; ...

2018-03-01

In this paper, natural abundance stable Hg isotope measurements were used to place new constraints on sources, transport, and transformations of Hg along the flow path of East Fork Poplar Creek (EFPC), a point-source contaminated headwater stream in Oak Ridge, Tennessee. Particulate-bound Hg in the water column of EFPC within the Y-12 National Security Complex, was isotopically similar to average metallic Hg(0) used in industry, having a mean δ 202Hg value of -0.42 ± 0.09‰ (1SD) and near-zero Δ 199Hg. On average, particulate fraction δ 202Hg values increased downstream by 0.53‰, while Δ 199Hg decreased by -0.10‰, converging with themore » Hg isotopic composition of the fine fraction of streambed sediment along the 26 km flow path. The dissolved fraction behaved differently. Although initial Δ 199Hg values of the dissolved fraction were also near-zero, these values increased transiently along the flow path. Initial δ 202Hg values of the dissolved fraction were more variable than in the particulate fraction, ranging from -0.44 to 0.18‰ among three seasonal sampling campaigns, but converged to an average δ 202Hg value of 0.01 ± 0.10‰ (1SD) downstream. Dissolved Hg in the hyporheic and riparian pore water had higher and lower δ 202Hg values, respectively, compared to dissolved Hg in stream water. Finally, variations in Hg isotopic composition of the dissolved and suspended fractions along the flow path suggest that: (1) physical processes such as dilution and sedimentation do not fully explain decreases in total mercury concentrations along the flow path; (2) in-stream processes include photochemical reduction, but microbial reduction is likely more dominant; and (3) additional sources of dissolved mercury inputs to EFPC at baseflow during this study predominantly arise from the hyporheic zone.« less

Hg isotopes reveal in-stream processing and legacy inputs in East Fork Poplar Creek, Oak Ridge, Tennessee, USA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Demers, Jason D.; Blum, Joel D.; Brooks, Scott C.

In this paper, natural abundance stable Hg isotope measurements were used to place new constraints on sources, transport, and transformations of Hg along the flow path of East Fork Poplar Creek (EFPC), a point-source contaminated headwater stream in Oak Ridge, Tennessee. Particulate-bound Hg in the water column of EFPC within the Y-12 National Security Complex, was isotopically similar to average metallic Hg(0) used in industry, having a mean δ 202Hg value of -0.42 ± 0.09‰ (1SD) and near-zero Δ 199Hg. On average, particulate fraction δ 202Hg values increased downstream by 0.53‰, while Δ 199Hg decreased by -0.10‰, converging with themore » Hg isotopic composition of the fine fraction of streambed sediment along the 26 km flow path. The dissolved fraction behaved differently. Although initial Δ 199Hg values of the dissolved fraction were also near-zero, these values increased transiently along the flow path. Initial δ 202Hg values of the dissolved fraction were more variable than in the particulate fraction, ranging from -0.44 to 0.18‰ among three seasonal sampling campaigns, but converged to an average δ 202Hg value of 0.01 ± 0.10‰ (1SD) downstream. Dissolved Hg in the hyporheic and riparian pore water had higher and lower δ 202Hg values, respectively, compared to dissolved Hg in stream water. Finally, variations in Hg isotopic composition of the dissolved and suspended fractions along the flow path suggest that: (1) physical processes such as dilution and sedimentation do not fully explain decreases in total mercury concentrations along the flow path; (2) in-stream processes include photochemical reduction, but microbial reduction is likely more dominant; and (3) additional sources of dissolved mercury inputs to EFPC at baseflow during this study predominantly arise from the hyporheic zone.« less

Stable isotopic and molecular compositions of void and hydrate-bound gases in typical seismic chimney setting of the Ulleung Basin, East Sea, Korea

NASA Astrophysics Data System (ADS)

Chun, J.; Lee, J.; Kim, J.; Bahk, J.; Ryu, B.

2009-12-01

Two UBGH cores were collected at vertical seismic chimney setting in the deep-water (> 2,000 m) Ulleung Basin, East Sea during UBGH-Expedition-01 in 2007. Gas hydrates were recovered from UBGH-10 and UBGH-09 sites with different occurrences associated with seismic chimney blanking zone. Site UBGH-10 is characterized by a small mound as well as a near-surface structure, indicated by a seafloor extension of vertical seismic chimney. Site UBGH-09 consists of acoustic blanking in the shallow section and seismic chimney in the deep section. Highly GH-concentrated zones have been found in vertical seismic chimney interval at these two sites from the Ulleung Basin. Methane is the dominant component of void gases with traces of C2 and C3 at UBGH-09. No C4 hydrocarbon gases were determined. The C1/C2+C3 ratio range from 3222 to 31654. The stable carbon (δ13C) and hydrogen (δD) isotope values of CH4 range from -71.8‰ to -59.8‰ PDB and -203.6‰ to -185.6 ‰ SMOW, respectivley. Methane is the main component of void gases at UBGH-10. The C1/C2+C3 ratio range from 657 to 7968. The δ13C of CH4 varies from -67.7‰ to -60.6‰ PDB, and δD of CH4 ranges from -201.9‰ to -183.3 ‰ SMOW. Isotopic properties of void gases from the two sites suggest that CH4 is largely microbial with CO2 reduction environment. In the vertical seismic chimney interval, void gases have low C1/C2+C3 ratio (> 10,000). At shallow depth (0-67 mbsf) in UBGH-09 contain relatively high C1/C2+C3 ratio (11115 to 31654). The stable carbon and hydrogen isotope values of hydrate-bound gases range from -63.1‰ to 61.9‰ PDB and -200.2‰ to -191.4‰ SMOW, respectively. The C1/C2+C3 ratio range from 979 to 5085. The molecular and stable isotopic compositions of hydrate-bound gases suggest that CH4 is largely microbial with CO2 reduction.

Chromium Stable Isotope Fractionation - An Indicator of Hexavalent Chromium Reduction.

NASA Astrophysics Data System (ADS)

Ellis, A.; Johnson, T. M.; Bullen, T. D.

2001-12-01

Chromium is a common anthropogenic contaminant in surface water and ground water, and is also of interest in oceanography. It is redox-active; the two common valences in natural waters are Cr(VI), which is highly soluble and toxic, and Cr(III), which is relatively insoluble. Redox reactions thus control Cr mobility in aqueous solutions, and reduction of Cr(VI) to Cr(III) is the most important reaction controlling attenuation of Cr in groundwater. Our results show that Cr(VI) reduction favors the lighter isotopes and leads to enrichment of heavier isotopes in the remaining Cr(VI). Cr isotope measurements thus show great promise as indicators of Cr(VI) reduction. We report here the first measurements of the magnitude of Cr isotope fractionation during Cr(VI) reduction and variations in δ 53Cr values obtained from three contaminated sites. Experiments were conducted to measure Cr isotope fractionation during Cr(VI) reduction by suspensions of magnetite and unamended sediments from a local pond, Urbana, IL and San Francisco Estuary near Martinez, CA. Suspensions were incubated anaerobically with constant shaking, and complete Cr(VI) reduction occurred within a few days. Cr(VI) from intermediate time points in the experiments was purified via ion exchange and 53Cr/52Cr ratios were measured via TIMS with a double isotope spike. The instantaneous per mil fractionation, ɛ , was calculated assuming a Rayleigh fractionation model. The ɛ for Cr(VI) reduction on magnetite surfaces yielded a fractionation of -3.5 ‰ . The ɛ values for the pond and estuary sediments were -3.5 ‰ and -3.3 ‰ respectively. The size of this Cr isotope fractionation is encouraging, as current precision is 0.2 \\permil. δ 53Cr values in dissolved Cr(VI) from three contaminated sites range from 1.1 ‰ to 5.8 ‰ , suggesting that Cr(VI) reduction has occurred and has induced isotopic fractionation in these settings. δ 53Cr values measured from Cr(VI) in plating baths show little or no fractionation during plating operations during up to 5 years of use. These results demonstrate that Cr stable isotope analyses should be a highly practical indicator of the critical chromate reduction reaction, and an otherwise useful geologic and oceanographic tool.

On-line Differential Thermal Isotope Analysis: A New Method for Measuring Oxygen and Hydrogen Isotopes of Hydration Water in Minerals

NASA Astrophysics Data System (ADS)

Bauska, T.; Hodell, D. A.; Walters, G.

2016-12-01

Oxygen (16O,17O,18O) and hydrogen (H,D) isotopes of hydration water in minerals provide a rich source of information about the conditions under which hydrated minerals form on Earth and other planetary bodies (e.g. Mars). We have developed a new method for measuring different types of bonded water (e.g., molecular, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves step heating a mineral sample, precisely measuring the weight loss and enthalpy as the sample undergoes dehydration and dehydroxylation, whilst simultaneously determining the oxygen and hydrogen isotopes of the water vapor evolved from the mineral sample by cavity ring-down laser spectroscopy (CRDS). Nitrogen carrier gas is used to transfer the sample from the TG to the CRDS via a heated line and interface box. The interface includes the capability of (i) cryogenic trapping discrete types of water for samples containing small amounts of water; (ii) injecting small quantities of water of known isotopic value for calibration; and (iii) converting volatile organic compounds to nascent amounts of water using a catalyst. The CRDS continually measures water vapor concentration in the optical cavity and hydrogen and oxygen isotope ratios. Isotopic values are calculated by integrating the product of the water amount and its isotopic value for the separated peaks after correcting for background. Precision of the method was estimated by comparing isotope results of total water for gypsum measured by DTIA with our conventional method of extraction and analysis (Gázquez et al., 2015. Rapid Communications in Mass Spectrometry, 29, 1997-2006). Errors for the isotopic values of total hydration water vary between ±0.08 and ±0.34 ‰ for δ18O and between ±0.16 and ±0.86 ‰ for δD. We demonstrate the application of the DTIA method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous silica (opal, glass, chert). The DTIA method has wide ranging application for addressing fundamental problems across many disciplines in Earth and Planetary Sciences, including: paleoclimatology, sedimentology, volcanology, water exchange between the solid earth and hydrosphere, and water on Mars and other planetary bodies.

Stable isotope analysis at the molecular level: A new approach for determining the origins of amino acids in the Murchison meteorite

NASA Technical Reports Server (NTRS)

Engel, M. H.; Macko, S. A.; Qian, Y.; Silfer, J. A.

1995-01-01

A combined gas chromatography/isotope ratio mass spectrometry (GC/IRMS) method has been developed that permits the direct stable carbon isotope analysis of N(O)-trifluoroacetyl-isopropyl esters of individual amino acids and their respective enantiomers at nanomole abundances. Calculation of the original delta C-13 values of the amino acids is accomplished via a correction for the carbon introduced during the derivatization process. Previous GC/IRMS analyses of individual amino acids in the non-hydrolyzed water extract of an interior sample of a Murchison meteorite stone revealed an enrichment in C-13 relative to terrestrial organic matter, in agreement with previous findings for bulk extracts. The range of amino acid delta C-13 values (+5 to +30 per mill, PDB) suggests possible kinetic effects during synthesis. In this study, an apparent kinetic isotope effect was also observed for the amino acid products of a spark discharge experiment. These preliminary resutls are supportive of a similar mechanism for the abiotic synthesis of amino acids in the Murchison meteorite.

In Vivo Mass-independent Fractionation of Mercury Isotopes in Fish

NASA Astrophysics Data System (ADS)

Das, R.; Odom, L. A.

2008-12-01

Recent experimental work and analyses of natural samples have revealed both mass-dependent and mass- independent isotope fractionation effects in mercury. These findings portend new avenues toward understanding the global mercury cycle. It has been shown experimentally that photo reduction of Hg+2 and methylmercury in water with concomitant release of the reduced, gaseous species Hg° results in the residual methylmercury possessing a mass-independent isotope effect. This effect is a relative enrichment of isotopes 199Hg and 201Hg over the even mass number isotopes when compared to the mercury standard NIST SRM3133. Large mass independent fractionation (MIF) effects (Δ199Hg values of a few ‰) have been found in mercury in fish and interpreted as isotope effects inherited from the water. To evaluate the possibility that MIF might be produced within the fish, we have analyzed 38 samples that include zooplankton and twelve different species of fish from a single lake collected over a 2-month time period for mercury isotopic compositions. Trophic levels of the same fish specimens had previously been determined from stomach contents and nitrogen isotopes. Zooplankton in the lake contain mercury with Δ199Hg and Δ201Hg values of +0.43 (±0.07) and +0.44 (±0.07) respectively. Among the fish species there is a striking correspondence between trophic level and Δ199Hg and Δ201Hg values for primary, secondary, and tertiary consumers. The Δ199Hg values ranges over ~1‰ from ~+0.4 in zooplankton, juvenile bluegill and several other small fishes to Δ199Hg = + 1.36 for the Florida gar that is the top predator fish in the lake. These observations indicate that the MIF effect, rather than being an artifact of the water column is produced in vivo. Partial separation of 199Hg and 201Hg from isotopes of even neutron number can be achieved by the magnetic isotope effect in reactions involving sufficiently long-lived intermediate free radicals, where nuclear - electron hyperfine coupling influence radical recombination and thus reaction kinetics. There is experimental evidence that this can occur during the inhibiting activity of methylmercury on creatine kinase. Here the enzyme provides the free radicals. Previously, reports of chemical mass- independent fractionation of isotopes in nature have involved gas phase reactions and largely explained by photolysis. It now seems that isotopic MIF can occur during metabolic processes as well.

Copper and Zinc isotope composition of CR, CB and CH-like meteorites.

NASA Astrophysics Data System (ADS)

Russell, S.; Zhu, X.; Guo, Y.; Mullane, E.; Gounelle, M.; Mason, T.; Coles, B.

2003-04-01

Copper and zinc isotopes have recently been shown to be variable in isotopic composi-tion among terrestrial and extraterrestrial materials [1-3]. For this study, we have se-lected samples (bulk meteorite and chondrule separates) from the CR meteorite clan: Bencubbin (CB), Renazzo (CR2), NWA 801 (CR2), and HaH237 (CH-like). These meteorites were selected because meteorites from this clan have experienced very little alteration since their initial formation [4] and for their extremely high refrac-tory/volatile element ratios. The latter characteristic may allow a test of the correlation observed by [2] between element ratios and Cu isotope composition. Measurements were performed on NHM/IC Micromass Isoprobe and Oxford Nu MC-ICP-MS using techniques described elsewhere [1,5]. Each of the meteorites measured so far for Cu and Zn are isotopically light compared to the terrestrial mantle. This suggests that the terrestrial value may have been altered from the pristine solar system value, or else there were multiple early solar system components. Zinc isotopic com-positions lie on a fractionation line and range from δ66ZnNIST = -1.4±0.1ppm (bulk NWA801) to -1.9±0.1ppm (separated chondrule, NWA 801). Copper isotope compositions vary from δ65CuNIST976 = -1.5±0.1ppm (bulk Renazzo) to -3.1±0.1ppm (separated chondrule, NWA 801). Two chondrules from NWA 801 have differing Cu isotope values (-3.1±0.1 and -2.0±0.1ppm) and both are lighter than the bulk meteorite (-1.9±0.1ppm), suggesting a lack of equilibration with respect to Cu in this meteorite. The light values for the two separated chondrules, compared the bulk meteorite, hints that chondrules may be isotopically lighter than co-existing matrix, metal and sulphides with respect to Cu. The copper isotope compositions are not as isotopically light as expected for the high refractory/volatile element ratio observed in these chondrites. Thus a model to account for the Cu isotopes in chondrites may require greater com-plexity than one involving simple mixing of two primordial components. References: [1] Zhu et al., Chem. Geol. 163,139-149 (2000). [2] Luck et al., GCA 67 143 (2002). [3] Luck et al., MAPS 35 A100 (2000) [4] Krot et al., MAPS 37 1451-1490 (2002) [5] Mason et al. EOS Trans. AGU abstract V21A-0966 82 (2001)

Microbial H2 cycling does not affect δ2H values of ground water

USGS Publications Warehouse

Landmeyer, J.E.; Chapelle, F.H.; Bradley, P.M.

2000-01-01

Stable hydrogen-isotope values of ground water (δ2H) and dissolved hydrogen concentrations (H(2(aq)) were quantified in a petroleum-hydrocarbon contaminated aquifer to determine whether the production/consumption of H2 by subsurface microorganisms affects ground water &delta2H values. The range of &delta2H observed in monitoring wells sampled (-27.8 ‰c to -15.5 ‰c) was best explained, however, by seasonal differences in recharge temperature as indicated using ground water δ18O values, rather than isotopic exchange reactions involving the microbial cycling of H2 during anaerobic petroleum-hydrocarbon biodegradation. The absence of a measurable hydrogen-isotope exchange between microbially cycled H2 and ground water reflects the fact that the amount of H2 available from the anaerobic decomposition of petroleum hydrocarbons is small relative to the amount of hydrogen present in water, even though milligram per liter concentrations of readily biodegradable contaminants are present at the study site. Additionally, isotopic fractionation calculations indicate that in order for H2 cycling processes to affect δ2H values of ground water, relatively high concentrations of H2 (>0.080 M) would have to be maintained, considerably higher than the 0.2 to 26 nM present at this site and characteristic of anaerobic conditions in general. These observations suggest that the conventional approach of using δ2H and δ18O values to determine recharge history is appropriate even for those ground water systems characterized by anaerobic conditions and extensive microbial H2 cycling.

Stable Oxygen isotopes in otoliths to reconstruct salmon and striped bass habitat use within the San Francisco Bay estuary

NASA Astrophysics Data System (ADS)

Malamud-Roam, F.; Phillis, C.; Ingram, B. L.; Schmitt, A. K.; Weber, P. K.

2008-12-01

Understanding the habitat use of anadromous fish species within major riverine and estuarine settings can provide useful information for protecting these fish populations. The inner ear bone, or otolith, of these fish is an accretionary carbonate structure that contains a high-resolution record of the life history of the fish, including certain chemical properties of the ambient waters occupied by the fish. Stable isotopes measured in the daily-accreting otolith layers can provide highly-resolved histories of habitat occupation. For the salmon, the juvenile phase is a critical life history period and researchers, as well as agencies charged with protecting these fish, seek detailed information about habitat use during this phase. We have measured isotopic ratios of 18O/16O (δ18O permil) in the otoliths of Chinook Salmon and striped bass, sampling along the growth axis, to produce a history of habitat use by these fish. The 18O/16O ratios of the carbonate otolith samples are primarily influenced by the 18O/16O ratio of the surrounding waters (which range from ~0 permil near the Golden Gate to -11 permil for river water), modified by temperature (- 0.326 permil/°C, so a range of approximately 1.6 permil over the course of a year. We have modeled the expected values for carbonate samples for locations throughout the estuary based upon seasonally averaged salinity and temperature values for these locations; for example, we expect delta 18O values of about -7.5 permil in otoliths for fish at the entrance to the estuary and about 2.7 permil in the ocean. We find good agreement between the δ18O data and 87/86Sr data collected earlier on the same fish samples (which also varies as a function of salinity). The value of the oxygen isotope data is that they provide great dynamic range in the brackish to saline portion of the estuary. The combined data provide a record of where the fish spent significant portions of their lives.

Investigating controls on boron isotope ratios in shallow marine carbonates

NASA Astrophysics Data System (ADS)

Zhang, Shuang; Henehan, Michael J.; Hull, Pincelli M.; Reid, R. Pamela; Hardisty, Dalton S.; Hood, Ashleigh v. S.; Planavsky, Noah J.

2017-01-01

The boron isotope-pH proxy has been widely used to reconstruct past ocean pH values. In both planktic foraminifera and corals, species-specific calibrations are required in order to reconstruct absolute values of pH, due to the prevalence of so-called vital effects - physiological modification of the primary environmental signals by the calcifying organisms. Shallow marine abiotic carbonate (e.g. ooids and cements) could conceivably avoid any such calibration requirement, and therefore provide a potentially useful archive for reconstructions in deep (pre-Cenozoic) time. However, shallow marine abiotic carbonates could also be affected by local shifts in pH caused by microbial photosynthesis and respiration, something that has up to now not been fully tested. In this study, we present boron isotope measurements from shallow modern marine carbonates, from the Bahama Bank and Belize to investigate the potential of using shallow water carbonates as pH archives, and to explore the role of microbial processes in driving nominally 'abiogenic' carbonate deposition. For Bahama bank samples, our boron-based pH estimates derived from a range of carbonate types (i.e. ooids, peloids, hardground cements, carbonate mud, stromatolitic micrite and calcified filament micrite) are higher than the estimated modern mean-annual seawater pH values for this region. Furthermore, the majority (73%) of our marine carbonate-based pH estimates fall out of the range of the estimated pre-industrial seawater pH values for this region. In shallow sediment cores, we did not observe a correlation between measured pore water pH and boron-derived pH estimates, suggesting boron isotope variability is a depositional rather than early diagenetic signal. For Belize reef cements, conversely, the pH estimates are lower than likely in situ seawater pH at the time of cement formation. This study indicates the potential for complications when using shallow marine non-skeletal carbonates as marine pH archives. In addition, variability in δ11B based pH estimates provides additional support for the idea that photosynthetic CO2 uptake plays a significant role in driving carbonate precipitation in a wide range of shallow water carbonates.

Oxygen isotope fractionation between analcime and water - An experimental study

NASA Technical Reports Server (NTRS)

Karlsson, Haraldur R.; Clayton, Robert N.

1990-01-01

The oxygen isotope fractionation between analcime and water is studied to test the feasibility of using zeolites as low-temperature thermometers. The fractionation of oxygen isotopes between natural analcime and water is determined at 300, 350, and 400 C, and at fluid pressures ranging from 1.5 to 5.0 kbar. Also, isotope ratios for the analcime framework, the channel water, and bulk water are obtained. The results suggest that the channel water is depleted in O-18 relative to bulk water by a constant value of about 5 percent, nearly independent of temperature. The analcime-water fractionation curve is presented, showing that the exchange has little effect on grain morphology and does not involve recrystallization. The exchange is faster than any other observed for a silicate. The exchange rates suggest that zeolites in active high-temperature geothermal areas are in oxygen isotopic equilibrium with ambient fluids. It is concluded that calibrated zeolites may be excellent low-temperature oxygen isotope geothermometers.

Trace-element and Sr, Nd, Pb, and O isotopic composition of Pliocene and Quaternary alkali basalts of the Patagonian Plateau lavas of southernmost South America

USGS Publications Warehouse

Stern, C.R.; Frey, F.A.; Futa, K.; Zartman, R.E.; Peng, Z.; Kurtis, Kyser T.

1990-01-01

The Pliocene and Quaternary Patagonian alkali basalts of southernmost South America can be divided into two groups. The "cratonic" basalts erupted in areas of Cenozoic plateau volcanism and continental sedimentation and show considerable variation in 87Sr/86Sr (0.70316 to 0.70512), 143Nd/144Nd (e{open}Nd) and 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios (18.26 to 19.38, 15.53 to 15.68, and 38.30 to 39.23, respectively). These isotopic values are within the range of oceanic island basalts, as are the Ba/La, Ba/Nb, La/Nb, K/Rb, and Cs/Rb ratios of the "cratonic" basalts. In contrast, the "transitional" basalts, erupted along the western edge of the outcrop belt of the Pliocene and Quaternary plateau lavas in areas that were the locus of earlier Cenozoic Andean orogenic arc colcanism, have a much more restricted range of isotopic composition which can be approximated by 87Sr/86Sr=0.7039??0.0004, e{open}Nd, 206Pb/204Pb=18.60??0.08, 207Pb/204Pb=15.60??0.01, and 208Pb/204Pb=38.50??0.10. These isotopic values are similar to those of Andean orogenic are basalts and, compared to the "cratonic" basalts, are displaced to higher 87Sr/86Sr at a given 143Nd/144Nd and to higher 207Pb/204Pb at a given 208Pb/204Pb. The "transitional" basalts also have Ba/La, Ba/Nb, La/Nb, and Cs/Rb ratios higher than the "cratonic" and oceanic island basalts, although not as high as Andean orogenic are basalts. In contrast to the radiogenic isotopes, ??18O values for both groups of the Patagonian alkali basalts are indistinguishable and are more restricted than the range reported for Andean orogenic are basalts. Whole rock ??18O values calculated from mineral separates for both groups range from 5.3 to 6.5, while measured whole rock ??18O values range from 5.1 to 7.8. The trace element and isotopic data suggest that decreasing degrees of partial melting in association with lessened significance of subducted slabderived components are fundamental factors in the west to east transition from arc to back-arc volcanism in southern South America. The "cratonic" basalts do not contain the slab-derived components that impart the higher Ba/La, Ba/Nb, La/Nb, Cs/Rb, 87Sr/86Sr at a given 143Nd/144Nd, 207Pb/204Pb at a given 208Pb/204Pb, and ??18O to Andean orogenic arc basalts. Instead, these basalts are formed by relatively low degrees of partial melting of heterogeneous lower continental lithosphere and/or asthenosphere, probably due to thermal and mechanical pertubation of the mantle in response to subduction of oceanic lithosphere below the western margin of the continent. The "transitional" basalts do contain components added to their source region by either (1) active input of slab-derived components in amounts smaller than the contribution to the mantle below the arc and/or with lower Ba/La, Ba/Nb, La/Nb, and Cs/Rb ratios than below the arc due to progressive downdip dehydration of the subducted slab; or (2) subarc source region contamination processes which affected the mantle source of the "transitional" basalts earlier in the Cenozoic. ?? 1990 Springer-Verlag.

Chlorine Isotope Ratios in M Giants and S Stars

NASA Astrophysics Data System (ADS)

Maas, Zachary; Pilachowski, C. A.

2018-01-01

Chlorine is an odd-Z, light element that has been poorly studied in stars. Recently, the first stellar abundance measurements of the isotopologue 35Cl were made and the 35Cl/37Cl ratio was derived in RZ Ari (Maas et al. 2016). Additional abundance measurements are necessary to understand the Galactic chemical evolution and complex nucleosynthesis of Cl. The Cl isotope ratio in particular is important in distinguishing contributions from different nucleosynthesis sites to the surface abundances of stars. For example, current nucloesynthesis models predict that both isotopes of Cl are produced primarily during core collapse supernovae (CCSNe) with the energy and progenitor mass impacting the isotopic ratio of the ejected material. In addition to CCSNe, 37Cl is formed by the s-process both in massive stars and in AGB stars, and 35Cl may be produced from neutrino spallation. Understanding the formation of the Cl isotopes is also important to studies of the interstellar medium (ISM). A range of Cl isotope ratios mainly between 2 - 3.5 have been measured in star forming regions, in the circumstellar envelopes of evolved stars, and in proto-stellar cores using Cl bearing molecules. Additional measurements of the Cl isotope ratio in nearby stars will test nucleosynthesis models and allow comparisons with the range of isotope ratios observed in the ISM.We build on the results of Maas et al. (2016) by measuring the Cl isotope ratio in six M giants and four S stars using R~50,000 resolution spectra from Phoenix on Gemini South. We find no significant difference between the average Cl isotope ratios in the M stars and S stars and our measurements are consistent with the range of values seen in the ISM. We also find the average Cl ratio to be larger than the predicted isotope ratio of 1.8 for the solar neighborhood. Finally, two S stars, GG Pup and WY Pyx, show anomalously strong HCl features with equivalent widths ~3-5 times larger than the HCl features of other stars of similar temperature.

Combined use of 15N and 18O of nitrate and 11B to evaluate nitrate contamination in groundwater

USGS Publications Warehouse

Seiler, R.L.

2005-01-01

Isotopic composition of NO3 (??15NNO3 and ??18ONO3) and B (??11B) were used to evaluate NO3 contamination and identify geochemical processes occurring in a hydrologically complex Basin and Range valley in northern Nevada with multiple potential sources of NO3. Combined use of these isotopes may be a useful tool in identifying NO3 sources because NO3 and B co-migrate in many environmental settings, their isotopes are fractionated by different environmental processes, and because wastewater and fertilizers may have distinct isotopic signatures for N and B. The principal cause of elevated NO3 concentrations in residential parts of the study area is wastewater and not natural NO3 or fertilizers. This is indicated by some samples with elevated NO3 concentrations plotting along ??15NNO3 and NO3 mixing lines between natural NO3 from the study area and theoretical septic-system effluent. This conclusion is supported by the presence of caffeine in one sample and the absence of samples with elevated NO3 concentrations that fall along mixing lines between natural NO3 and theoretical percolate below fertilized lawns. Nitrogen isotopes alone could not be used to determine NO3 sources in several wells because denitrification blurred the original isotopic signatures. The range of ??11B values in native ground water in the study area (-8.2??? to +21.2???) is large. The samples with the low ??11B values have a geochemical signature characteristic of hydrothermal systems. Physical and chemical data suggest B is not being strongly fractionated by adsorption onto clays. ??11B values from local STP effluent (-2.7???) and wash water from a domestic washing machine (-5.7???) were used to plot mixing lines between wastewater and native ground water. In general, wells with elevated NO3 concentrations fell along mixing lines between wastewater and background water on plots of ??11B against 1/B and Cl/B. Combined use of ??15N and ??11B in the study area was generally successful in identifying contaminant sources and processes that are occurring, however, it is likely to be more successful in simpler settings with a well-characterized ??11B value for background wells.

Food web structure of deep-sea macrozooplankton and micronekton off the Catalan slope: Insight from stable isotopes

NASA Astrophysics Data System (ADS)

Fanelli, E.; Cartes, J. E.; Papiol, V.

2011-07-01

Food web structure of the macroplankton/micronekton fauna on the continental slope of the Catalan Sea (Balearic basin, NW Mediterranean) was investigated using carbon and nitrogen stable isotope tracers on a total of 34 taxa. Samples were collected close to Barcelona, Spain, on the middle slope, at a seasonal scale. Mean δ 13C values ranged from - 22.1‰ ( Salpa maxima) to - 16.9‰ (the mysid Eucopia hanseni). Values of δ 15N ranged from 2.5‰ (the hyperiid Vibilia armata) to 9.8‰ (the pelagic polychaete Tomopteris sp.). The stable isotope ratios of this fauna displayed a continuum of values over the δ 15N range of 7‰, confirming a wide spectrum of feeding strategies (from filter feeders to predators). High annual mean δ 15N values were found among carnivorous large zooplankton and micronekton, including species that prey on gelatinous plankton (i.e. salps, siphonophores), euphausiids, natantian decapod crustaceans and fish (i.e. myctophids and stomiiformes). In agreement with the available information on diets of planktonic taxa, the lowest isotope ratios were found for filter feeders ( V. armata, S. maxima, the pteropods Cymbulia peroni and Cavolinia inflexa, ostracods and the thaliacean Pyrosoma atlanticum), all of which feed on particulate organic matter. We found three trophic levels in macroplankton/micronekton food webs based on a 15N-enrichment factor of ~ 2.5‰ per level. The range of δ 13C was particularly wide among carnivores (- 20.7‰ to - 16.6‰), suggesting predation on a variety of prey from gelatinous zooplankton (which displayed more depleted δ 13C signatures) to small fishes and decapods. Correlation between δ 13C-δ 15N was generally weak, likely due to the consumption of different kinds of sinking particles (e.g. marine snow, phytodetritus), some constituted of multiply recycled particulate organic matter (POM). However, higher δ 13C-δ 15N correlations were observed during winter and spring, periods of water column homogenization, suggesting that the planktonic community assimilates pulses of new production from the photic zone (peaking in January-February). Low correlations were observed during periods of water column stratification, particularly in summer, when production is especially low, suggesting that in this period macroplankton-micronekton community rely on sources other than surface primary production such as POM derived from river discharge.

Investigating the behaviour of Mg isotopes during the formation of clay minerals

NASA Astrophysics Data System (ADS)

Wimpenny, Joshua; Colla, Christopher A.; Yin, Qing-Zhu; Rustad, James R.; Casey, William H.

2014-03-01

We present elemental and isotopic data detailing how the Mg isotope system behaves in natural and experimentally synthesized clay minerals. We show that the bulk Mg isotopic composition (δ26Mg) of a set of natural illite, montmorillonite and kaolinite spans a 2‰ range, and that their isotopic composition depends strongly on a balance between the relative proportions of structural and exchangeable Mg. After acid leaching, these natural clays become relatively enriched in isotopically heavy Mg by between 0.2‰ and 1.6‰. Results of exchange experiments indicate that the Mg that has adsorbed to interlayer spaces and surface charged sites is relatively enriched in isotopically light Mg compared to the residual clay. The isotopic composition of this exchangeable Mg (-1.49‰ to -2.03‰) is characteristic of the isotopic composition of Mg found in many natural waters. Further experiments with an isotopically characterized MgCl2 solution shows that the clay minerals adsorb this exchangeable Mg with little or no isotopic fractionation, although we cannot discount the possibility that the uptake of exchangeable Mg does so with a slight preference for 24Mg. To characterize the behaviour of Mg isotopes during clay mineral formation we synthesized brucite (Mg(OH)2), which we consider to be a good analogue for the incorporation of Mg into the octahedral sheet of Mg-rich clay minerals or into the brucitic layer of clays such as chlorite. In our experiment the brucite mineral becomes enriched in the heavy isotopes of Mg while the corresponding solution is always relatively enriched in isotopically light Mg. The system reaches a steady state after 10 days with a final fractionation factor (αsolid-solution) of 1.0005 at near-neutral pH. This result is consistent with the general consensus that secondary clay minerals preferentially take up isotopically heavy Mg during their formation. However our results also show that exchangeable Mg is an important component within bulk clay minerals and can have an important influence over the bulk clay δ26Mg value. Modeling shows that in certain soils or sediments where the percentage of exchangeable Mg is >30% and the isotopic composition of the exchangeable Mg is around -2‰, the generation of bulk δ26Mg values of <-0.5‰ is likely. On a broader scale, Mg-rich minerals such as smectite and illite are likely to impart a stronger control over the Mg budget in clay rich sediments, and their high structural Mg component is likely to result in bulk sediment δ26Mg values that are closer in composition to the UCC. Despite this, results of modeling, together with experimental observation suggests that the uptake of exchangeable Mg into these clay rich sediments could cause a decrease in the bulk δ26Mg value by up to ˜0.3-0.4‰. This should be accounted for when assessing the δ26Mg value of sediments on a crustal scale.

The symmetry energy, neutron skin thickness and isovector dipole response of neutron-rich nuclei

NASA Astrophysics Data System (ADS)

Horvat, A.; Paar, N.

2015-04-01

The isotopic evolution of the relationship between the symmetry energy at saturation density of nuclear matter (J), neutron skin thickness (ΔR) and relevant observables related to isovector dipole excitations in neutron rich 116-136Sn isotopes has been investigated in the framework of relativistic nuclear energy density functional theory. The description employs a family of effective interactions with density dependent meson-nucleon couplings (DDME) spanning the range of values J = 30 - 38 MeV.

Potential of ion chromatography coupled to isotope ratio mass spectrometry via a liquid interface for beverages authentication.

PubMed

Guyon, Francois; Gaillard, Laetitia; Brault, Audrey; Gaultier, Nicolas; Salagoïty, Marie-Hélène; Médina, Bernard

2013-12-27

New tools for the determination of characteristic parameters for food authentication are requested to prevent food adulteration from which health concerns, unfair competition could follow. A new coupling in the area of compound-specific carbon 13 isotope ratio (δ(13)C) analysis was developed to simultaneously quantify δ(13)C values of sugars and organic acids. The coupling of ion chromatography (IC) together with isotope ratio mass spectrometry (IRMS) can be achieved using a liquid interface allowing a chemical oxidation (co) of organic matter. Synthetic solutions containing 1 polyol (glycerol), 3 carbohydrates (sucrose, glucose and fructose) and 12 organic acids (gluconic, lactic, malic, tartaric, oxalic, fumaric, citric and isocitric) were used to optimize chromatographic conditions (concentration gradient and 3 types of column) and the studied isotopic range (-32.28 to -10.65‰) corresponds to the values found in food products. Optimum chromatographic conditions are found using an IonPac AS15, an elution flow rate of 0.3mLmin(-1) and a linear concentration gradient from 2 to 76mM (rate 21mMmin(-1)). Comparison between δ(13)C value individually obtained for each compound with the coupling IRMS and elemental analyzer, EA-IRMS, and the ones measured on the mixture of compounds by IC-co-IRMS does not reveal any isotope fractionation. Thus, under these experimental conditions, IC-co-IRMS results are accurate and reproducible. This new coupling was tested on two food matrices, an orange juice and a sweet wine. Some optimization is necessary as the concentration range between sugars and organic acids is too large: an increase in the filament intensity of the IRMS is necessary to simultaneously detect the two compound families. These first attempts confirm the good results obtained on synthetic solutions and the strong potential of the coupling IC-co-IRMS in food authentication area. Copyright © 2013 Elsevier B.V. All rights reserved.

Isotopic Evidence for Microbial Activity in Crystalline Bedrock Fractures - a Case Study from Olkiluoto, SW Finland

NASA Astrophysics Data System (ADS)

Sahlstedt, E. K.; Karhu, J.; Pitkänen, P.

2015-12-01

Changes in the geochemical environment in crystalline bedrock fractures were investigated using the stable isotopes of C, O and S in fracture filling minerals as tracers. Of special interest were the possible changes which may occur in the subsurface at low temperatures. Especially, the influence of microbial activity was recognized as a catalyst for inducing changes in the geochemical environment. The study site is the Olkiluoto island located on the western coast of Finland, planned to host a geological repository for nuclear waste. Fracture surfaces were investigated to recognize the latest mineralizations at the site. These fillings were comprised of thin plates or small euhedral crystals of calcite and pyrite. The carbon and sulfur isotope compositions of calcite and pyrite were measured from bulk material by conventional IRMS, and in situ by secondary ion mass spectrometry. A notable feature of the late-stage fillings was high variabilities in the δ13C values of calcite and the δ34S values of pyrite, which ranged from -53.8 ‰ to +31.6 ‰ and from -50.4 ‰ to +77.7 ‰, respectively. Based on the isotopic compositions of the fillings, several features in the past hydrogeochemical environment could be recognized. The isotopic composition of the fracture fillings indicate an environment which was stratified with respect to depth. Characteristic features include bacterial sulfate reduction (BSR) occurring at depths <111 m (bsl), and a methanogenetic environment at depths >50 m. It appears that methanic conditions were replaced by sulfate reduction at depths >50 m likely due to infiltration of SO42--rich brackish waters. Sulfate reducing bacteria used mainly surface derived organic carbon as electron donors. Some indication of minor methanotrophic activity was recognized in anomalously low δ13C values of calcite, down to -53.8 ‰, at the depth range of 34-54 m. This methanotrophic activity may have been related to bacteria using CH4 as an electron donor in BSR.

Extreme variation of sulfur isotopic compositions in pyrite from the Qiuling sediment-hosted gold deposit, West Qinling orogen, central China: An in situ SIMS study with implications for the source of sulfur

USGS Publications Warehouse

Chen, Lei; Li, Xian-hua; Li, Jian-wei; Hofstra, Albert H.; Liu, Yu; Koenig, Alan E.

2015-01-01

High spatial resolution textural (scanning electron microscope (SEM)), chemical (electron microprobe (EMP)) and laser ablation-inductively coupled plasma-mass spec- trometry (LA-ICP-MS)), and sulfur isotopic (secondary ion mass spectrometry (SIMS)) analyses of pyrite from the Qiuling sediment-hosted gold deposit (232±4 Ma) in the West Qinling orogen, central China were conducted to distinguish pyrite types and gain insights into the source and evolution of sulfur in hydrothermal fluids. The results reveal an enormous variation (−27.1 to +69.6‰) in sulfur isotopic composition of pyrite deposited during three paragenetic stages. Pre-ore framboidal pyrite, which is characterized by low concentra- tions of As, Au, Cu, Co, and Ni, has negative δ34S values of −27.1 to −7.6‰ that are interpreted in terms of bacterial re- duction of marine sulfate during sedimentation and diagenesis of the Paleozoic carbonate and clastic sequences, the predom- inant lithologies in the deposit area, and the most important hosts of many sediment-hosted gold deposits throughout the West Qinling orogen. The ore-stage hydrothermal pyrite con- tains high concentrations of Au, As, Cu, Sb, Tl, and Bi and hasa relatively narrow range of positive δ34S values ranging from +8.1 to +15.2‰. The sulfur isotope data are comparable to those of ore pyrite from many Triassic orogenic gold deposits and Paleozoic sedimentary exhalative (SEDEX) Pb-Zn de- posits in the West Qinling orogen, both being hosted mainly in the Devonian sequence. This similarity indicates that sulfur, responsible for the auriferous pyrite at Qiuling, was largely derived from the metamorphic devolatization of Paleozoic marine sedimentary rocks. Post-ore-stage pyrite, which is sig- nificantly enriched in Co and Ni but depleted in Au and As, has unusually high δ34S values ranging from +37.4 to +69.6 ‰, that are interpreted to result from thermochemical reduc- tion of evaporite sulfates in underlying Cambrian sedimentary rocks with very high δ34S values. The variations in Au content and sulfur isotopic compositions across a single ore-stage py- rite grain may reflect displacement of indigenous groundwater with low δ34S values by auriferous metamorphic fluids with high δ34S values. The very low-grade metamorphism of the host rocks and the metamorphic derivation of sulfur for the ore pyrite indicate that the Qiuling sediment-hosted gold deposit is an epizonal manifestation of an orogenic gold system in the West Qinling orogen.

Preparative chromatography for specific δ13C isotopic analysis of individual carbohydrates in environmental samples

NASA Astrophysics Data System (ADS)

Nouara, Amel; Panagiotopoulos, Christos; Balesdent, Jérôme; Sempéré, Richard

2017-04-01

Carbohydrates are among the most abundant organic molecules on the Earth and are present in all geochemical systems. Despite their high abundance in the environment, very few studies assessed their origin using molecular carbohydrate isotopic analyses. In contrast with bulk stable isotope analysis (BSIA), which gives the isotopic signature of the entire sample without any specification about its chemical composition, compound specific 13C isotopic analysis of individual sugars (CSIA) offers valuable information about the origin of single molecules. Previous investigations used gas or liquid chromatography coupled with isotope ratio mass spectroscopy (GC-IRMS; HPLC-IRMS) for CSIA of sugars however the former requires δ13C corrections due to the carbon added to the sugar (derivatization) while the later does not provide always adequate separations among monosaccharides. Here we used cation preparative chromatography (Ca2+, Pb2+ and Na+) with refractive index detection in order to produce pure monosaccharide targets for subsequent EA-IRMS analyses. Milli-Q water was used as eluant at a flow rate 0.6 ml min-1. In general, three successive purifications (Ca2+, Pb2+, Ca2+) were sufficient to produce pure compounds. Pure monosaccharides were compared with authentic monosaccharide standards using 1H NMR and/or mass spectroscopy. The detection limit of our technique was about 1µM/sugar with a precision of 10% (n=6). Blanks run with Milli-Q water after three successive purifications resulted in carbon content of 0.13 to 2.77 µgC per collected sugar. These values are much lower than the minimum required amount (5 µgC) of the EA-IRSMS system with a precision of ± 0.35 ‰. Application of our method to environmental samples resulted in δ13C values of glucose, fructose, and levoglucosan in the range of -24 to -26 ‰ (PM10 atmospheric particles), and -15‰ to -22 ‰ for arabinose, glucose, and xylose (marine high molecular dissolved organic matter). These results fall in the range of previous reported values for terrestrial and aquatic ecosystems.

Variation in stable isotopes of freshwater mussel shells in a Kentucky river system

NASA Astrophysics Data System (ADS)

Erhardt, A. M.; Haag, W.; Price, S.; Weisrock, D.

2017-12-01

Isotopic signatures in freshwater mussel shells can reflect environmental differences among streams and human impacts on river systems. In the southeastern United States, mussels exhibit extraordinary biodiversity, serve an important role as filter feeders, and are sensitive to environmental change. Additionally, their long life-span (up to 50 years) and seasonal shell deposition can permit high-resolution environmental reconstructions. We examined variation in shell stable isotope values among mussel species and locations throughout the Licking River system in Kentucky. We sampled 8 species at 11 locations. These species represented a range of life-history traits, and locations were distributed among tributaries and the main stem of the Licking River. Samples of the outer organic periostracum layer were analysed for organic δ13C and δ15N, while organic δ15N and inorganic δ13C and δ18O were measured in the inner carbonate portion of the shell. At the same location, preliminary results show variations 2‰ in δ13C and 1‰ in δ15N between different species. We suspect these relationships are due to variations in diet and/or body size. Some, though not all, specimens show variation along the growth axis. For the same species at different locations, preliminary results showed a range of 4‰ in δ13C and 10‰ in δ15N values. Isotope ratios of specimens from the main stem were distinct from those of specimens from the river's largest tributary. Overall, δ13C shows distinct values for each tributary, while δ15N shows a general decline downstream. These variations are likely the result of environmental factors such as the degree of karstification and the ratio of forest to pasture within the catchment. We hope to use this study to identify if any isotopically distinct sources, such as fertilizers or animal manure, contribute to the high nutrient load in these systems. These results represent an exploratory effort to describe watershed-scale and mussel community patterns of isotope variation, allowing us to attempt to unravel the anthropogenic influence on this highly biodiverse and environmentally sensitive organism.

Sulfur, carbon, and oxygen isotope variations in submarine hydrothermal deposits of Guaymas Basin, Gulf of California, USA

USGS Publications Warehouse

Peter, J.M.; Shanks, Wayne C.

1992-01-01

Sulfur, carbon, and oxygen isotope values were measured in sulfide, sulfate, and carbonate from hydrothermal chimney, spire, and mound samples in the southern trough of Guaymas Basin, Gulf of California, USA. ??34S values of sulfides range from -3.7 to 4.5%. and indicate that sulfur originated from several sources: 1. (1) dissolution of 0??? sulfide contained within basaltic rocks, 2. (2) thermal reduction of seawater sulfate during sediment alteration reactions in feeder zones to give sulfide with positive ??34S, and 3. (3) entrainment or leaching of isotopically light (negative-??34S) bacteriogenic sulfide from sediments underlying the deposits. ??34S of barite and anhydrite indicate sulfur derivation mainly from unfractionated seawater sulfate, although some samples show evidence of sulfate reduction and sulfide oxidation reactions during mixing within chimneys. Oxygen isotope temperatures calculated for chimney calcites are in reasonable agreement with measured vent fluid temperatures and fluid inclusion trapping temperatures. Hydrothermal fluids that formed calcite-rich chimneys in the southern trough of Guaymas Basin were enriched in 18O with respect to seawater by about 2.4??? due to isotopic exchange with sedimentary and/or basaltic rocks. Carbon isotope values of calcite range from -9.6 to -14.0??? ??34CpDB, indicating that carbon was derived in approximately equal quantities from the dissolution of marine carbonate minerals and the oxidation of organic matter during migration of hydrothermal fluid through the underlying sediment column. Statistically significant positive, linear correlations of ??34S, ??34C, and ??18O of sulfides and calcites with geographic location within the southern trough of Guaymas Basin are best explained by variations in water/rock ( w r) ratios or sediment reactivity within subsurface alteration zones. Low w r ratios and the leaching of detrital carbonates and bacteriogenic sulfides at the southern vent sites result in relatively high ??13C and low ??34S in chimney carbonates and sulfides, respectively. In the north, where the depletion of alkalis in vent fluids indicates higher w r ratios, positive ??34S and more negative ??13c are due to increased contributions from organic matter oxidation and sulfate reduction reactions. ?? 1992.

Stable isotope tracing of Ni and Cu pollution in North-East Norway: Potentials and drawbacks.

PubMed

Šillerová, Hana; Chrastný, Vladislav; Vítková, Martina; Francová, Anna; Jehlička, Jan; Gutsch, Marissa R; Kocourková, Jana; Aspholm, Paul E; Nilsson, Lars O; Berglen, Tore F; Jensen, Henning K B; Komárek, Michael

2017-09-01

The use of Ni and Cu isotopes for tracing contamination sources in the environment remains a challenging task due to the limited information about the influence of various biogeochemical processes influencing stable isotope fractionation. This work focuses on a relatively simple system in north-east Norway with two possible endmembers (smelter-bedrock) and various environmental samples (snow, soil, lichens, PM 10 ). In general, the whole area is enriched in heavy Ni and Cu isotopes highlighting the impact of the smelting activity. However, the environmental samples exhibit a large range of δ 60 Ni (-0.01 ± 0.03‰ to 1.71 ± 0.02‰) and δ 65 Cu (-0.06 ± 0.06‰ to -3.94 ± 0.3‰) values which exceeds the range of δ 60 Ni and δ 65 Cu values determined in the smelter, i.e. in feeding material and slag (δ 60 Ni from 0.56 ± 0.06‰ to 1.00 ± 0.06‰ and δ 65 Cu from -1.67 ± 0.04‰ to -1.68 ± 0.15‰). The shift toward heavier Ni and Cu δ values was the most significant in organic rich topsoil samples in the case of Ni (δ 60 Ni up to 1.71 ± 0.02‰) and in lichens and snow in the case of Cu (δ 65 Cu up to -0.06 ± 0.06‰ and -0.24 ± 0.04‰, respectively). These data suggest an important biological and biochemical fractionation (microorganisms and/or metal uptake by higher plants, organo-complexation etc.) of Ni and Cu isotopes, which should be quantified separately for each process and taken into account when using the stable isotopes for tracing contamination in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Isotopic identification of the source of methane in subsurface sediments of an area surrounded by waste disposal facilities

USGS Publications Warehouse

Hackley, Keith C.; Liu, Chao-Li; Trainor, D.

1999-01-01

The major source of methane (CH4) in subsurface sediments on the property of a former hazardous waste treatment facility was determined using isotopic analyses measured on CH4 and associated groundwater. The site, located on an earthen pier built into a shallow wetland lake, has had a history of waste disposal practices and is surrounded by landfills and other waste management facilities. Concentrations of CH4 up to 70% were found in the headspace gases of several piezometers screened at 3 different depths (ranging from 8 to 17 m) in lacustrine and glacial till deposits. Possible sources of the CH4 included a nearby landfill, organic wastes from previous impoundments and microbial gas derived from natural organic matter in the sediments. Isotopic analyses included ??13C, ??D, 14C, and 3H on select CH4 samples and ??D and ??18O on groundwater samples. Methane from the deepest glacial till and intermediate lacustrine deposits had ??13C values from -79 to -82???, typical of natural 'drift gas' generated by microbial CO2-reduction. The CH4 from the shallow lacustrine deposits had ??13C values from -63 to -76???, interpreted as a mixture between CH4 generated by microbial fermentation and the CO2-reduction processes within the subsurface sediments. The ??D values of all the CH4 samples were quite negative ranging from -272 to -299???. Groundwater sampled from the deeper zones also showed quite negative ??D values that explained the light ??D observed for the CH4. Radiocarbon analyses of the CH4 showed decreasing 14C activity with depth, from a high of 58 pMC in the shallow sediments to 2 pMC in the deeper glacial till. The isotopic data indicated the majority of CH4 detected in the fill deposits of this site was microbial CH4 generated from naturally buried organic matter within the subsurface sediments. However, the isotopic data of CH4 from the shallow piezometers was more variable and the possibility of some mixing with oxidized landfill CH4 could not be completely ruled out.

Using Archean and Paleoproterozoic Shales and Tillites as a Window into Crustal Evolution and Surface Conditions

NASA Astrophysics Data System (ADS)

Bindeman, I. N.; Bekker, A.; Zakharov, D. O.

2014-12-01

Precambrian shales and tillites have been insufficiently studied so far. We present oxygen and hydrogen isotope data for 103 bulk shale and tillites that were collected from drillholes on all continents from 3.2 to 1.4Ga. These samples have also been analyzed for total organic and inorganic carbon, total sulfur, δ13Corg values and by XRF for major and trace elements to calculate chemical index of alteration (CIA). Having uncompromised fresh samples from drillcores is a must for this kind of investigation. We have a particularly good coverage for the ca. 2.7-2.2 Ga time interval when Earth experienced 3-4 Snowball Earth glaciations associated with the rapid rise in atmospheric O2 and fluctuations in CO2, thus affecting weathering cycle and attainment of isotopic fractionation. All units have similar to Phanerozoic ranges in δ13Corg values (-23 to -33‰ PDB) and Corg content (0.1 to 10 wt. %). Compared to Phanerozoic shales, Precambrian shales have comparable ranges in δ18O values (+7 to +20‰), with slightly decreasing means with increasing age, and identical δ17O-δ18O slope (0.528). Shales in some drill holes display wide δ18O ranges over short stratigraphic intervals suggesting significant variability in the provenance. We however observe a significant, several permil downward shift and decrease in the range of δ18O values (7-9‰) in 2.2-2.5 Ga shales from several continents that are associated with the Paleoproterozoic glaciations. Scattered negative correlation of CIA with δ18O, for some of these shales broadly associated with the Paleoproterozoic glaciations suggest contact with glacial meltwater having ultra-low-δ18O values during deposition or diagenesis of these shales. The δD values of shales range from -50 to -75‰, and are comparable to Phanerozoic values, with the exception of the ~2.5-2.2 Ga shales that reach to -100‰. We also compare O isotope values of ultra-low-δ18O, +8 to -27‰ SMOW subglacial hydrothermal rocks recently discovered in Karelia (Russia), quartz amygdules in mafics and their relations to our global shale dataset. The overall conclusion is that despite first-order changes in areal mass, exposed surface conditions, pCO2, pO2 affecting chemical/physical weathering cycle, it was not dramatically different before and after the rise of atmospheric oxygen at ~2.3-2.4 Ga.

Isotopic composition of reduced and oxidized sulfur in the Canary Islands: implications for the mantle S cycle

NASA Astrophysics Data System (ADS)

Beaudry, P.; Longpre, M. A.; Wing, B. A.; Bui, T. H.; Stix, J.

2017-12-01

The Earth's mantle contains distinct sulfur reservoirs, which can be probed by sulfur isotope analyses of volcanic rocks and gases. We analyzed the isotopic composition of reduced and oxidized sulfur in a diverse range of volcanically derived materials spanning historical volcanism in the Canary Islands. Our sample set consists of subaerial volcanic tephras from three different islands, mantle and sedimentary xenoliths, as well as lava balloon samples from the 2011-2012 submarine El Hierro eruption and associated crystal separates. This large sample set allows us to differentiate between the various processes responsible for sulfur isotope heterogeneity in the Canary archipelago. Our results define an array in triple S isotope space between the compositions of the MORB and seawater sulfate reservoirs. Specifically, the sulfide values are remarkably homogeneous around d34S = -1 ‰ and D33S = -0.01 ‰, while sulfate values peak at d34S = +4 ‰ and D33S = +0.01 ‰. Lava balloons from the El Hierro eruption have highly enriched sulfate d34S values up to +19.3 ‰, reflecting direct interaction between seawater sulfate and the erupting magma. Several sulfate data points from the island of Lanzarote also trend towards more positive d34S up to +13.8 ‰, suggesting interaction with seawater sulfate-enriched lithologies or infiltration of seawater within the magmatic system. On the other hand, the modal values and relative abundances of S2- and S6+ in crystal separates suggest that the Canary Island mantle source has a d34S around +3 ‰, similar to the S-isotopic composition of a peridotite xenolith from Lanzarote. We infer that the S2- and S6+ modes reflect isotopic equilibrium between those species in the magmatic source, which requires 80 % of the sulfide to become oxidized after melting, consistent with measured S speciation. This 34S enrichment of the source could be due to the recycling of hydrothermally-altered oceanic crust, which has been previously suggested for the Canary Island hotspot on the basis of radiogenic isotope characteristics.

Weathering fluxes to the Gulf of Mexico from the Pliocene to Holocene based on radiogenic isotopes

NASA Astrophysics Data System (ADS)

Portier, A. M.; Martin, E. E.; Hemming, S. R.; Thierens, M. M.; Raymo, M. E.

2014-12-01

Chemical weathering of the continents plays a key role in the global carbon cycle and delivers solutes to the ocean. Past studies, documented using radiogenic isotopes of detrital and seawater samples, show the intensity of weathering varies with climate over a range of time scales.. We analyzed Pb and Nd isotopic values of seawater extracted from dispersed Fe-Mn oxides, <2μm (clay) and <63μm (silt) detrital fractions of Pliocene to Holocene sediment from Gulf of Mexico ODP Site 625B to evaluate long term variations in weathering fluxes for three time slices: the Pliocene/early Pleistocene, Mid Pleistocene Transition (MPT), and late Pleistocene/Holocene. We also examine short term glacial/interglacial variations. Little variation is seen in Nd isotopes of detrital fractions with age, suggesting little change in the average age of material delivered to the Gulf. Seawater Nd values become less radiogenic over the Pleistocene, consistent with observed changes in Caribbean seawater. Pb isotopes of silt fractions are also relatively constant through time, but clay fractions are more radiogenic at the MPT and dispersed Fe-Mn oxides trend to more radiogenic values in the late Pleistocene. Consequently, the Pb isotopes of dispersed Fe-Mn oxides tend to be less radiogenic than the detrital fractions in samples older than 2000 ka and more radiogenic than the detrital fractions, particularly clays, at the MPT. This may reflect greater incongruent silicate weathering during the MPT, a change in weathering conditions that could be consistent with the Regolith Hypothesis. Over glacial/interglacial timescales, dispersed Fe-Mn oxides Pb isotopes become more radiogenic than detrital fractions, and clay fractions become more radiogenic than silt fractions, during glacial periods. However, all fractions have similar values during interglacials. This pattern is distinct from previous studies that found enhanced incongruent silicate weathering during warm intervals, but is consistent with recent work finding a correlation with carbonate content, whereby low carbonate during glacials at Site 625 corresponds to a greater offset between leachate and detrital Pb isotopes. Biases from "heavy mineral effects" and changes in circulation during periods of lower sea level also need to be considered.

A First Look at Oxygen and Silicon Isotope Variations in Diatom Silica from a Pliocene Antarctic Marine Sediment Core

NASA Astrophysics Data System (ADS)

Abbott, T.; Dodd, J. P.; Hackett, H.; Scherer, R. P.

2016-02-01

Coupled oxygen (δ18O) and silicon (δ30Si) isotope variations in diatom silica (opal-A) are increasingly used as a proxy to reconstruct paleoenvironmental conditions (water temperatures, water mass mixing, nutrient cycling) in marine environments. Diatom silica is a particularly significant paleoenvironmental proxy in high latitude environments, such as the Southern Ocean, where diatom blooms are abundant and diatom frustules are well preserved in the sediment. The Andrill-1B (AND-1B) sediment core from the Ross Sea (Antarctica) preserves several Pliocene ( 4.5 Ma) age diatomite units. Here we present preliminary δ18O and δ30Si values for a diatomite subunit in the AND-1B sediment core. Initial isotope values for the AND-1B diatoms silica record relatively high variability (range δ18O: 36.3‰ to 39.9‰) that could be interpreted as large-scale changes in the water temperature and/or freshwater mixing in the Ross Sea; however, a significant concern with marine sediment of this age is isotope fractionation during diagenesis and the potential formation of opal-CT lepispheres. The effects of clay contamination on the diatom silica δ18O values have been addressed through sample purification and quantified through chemical and physical analyses of the diatom silica. The isotopic effects of opal-CT are not as clearly understood and more difficult to physically separate from the primary diatom silica. In order to better understand the isotope variations in the AND-1B diatoms, we also evaluated silicon and oxygen isotope fractionation during the transition from opal-A to opal-CT in a controlled laboratory experiment. Opal-A from cultured marine diatoms (Thalassiosira weissflogii) was subjected to elevated temperatures (150°C) in acid digestion vessels for 4 weeks to initiate opal-CT precipitation. Quantifying the effects of opal-CT formation on δ18O and δ30Si variations in biogenic silica improves our understanding of the use of diatom silica isotope values a paleoenvironmental proxy throughout the Cenozoic.

Variation in δ15N and δ13C values of forages for Arctic caribou: Effects of location, phenology and simulated digestion

USGS Publications Warehouse

Vansomeren, Lindsey L.; Barboza, Perry S.; Gustine, David D.; Bret-Harte, M. Syndonia

2017-01-01

RationaleThe use of stable isotopes for dietary estimates of wildlife assumes that there are consistent differences in isotopic ratios among diet items, and that the differences in these ratios between the diet item and the animal tissues (i.e., fractionation) are predictable. However, variation in isotopic ratios and fractionation of δ13C and δ15N values among locations, seasons, and forages are poorly described for arctic herbivores especially migratory species such as caribou (Rangifer tarandus).MethodsWe measured the δ13C and δ15N values of seven species of forage growing along a 200-km transect through the range of the Central Arctic caribou herd on the North Slope of Alaska over 2 years. We compared forages available at the beginning (May; n = 175) and the end (n = 157) of the growing season (September). Purified enzymes were used to measure N digestibility and to assess isotopic fractionation in response to nutrient digestibility during simulated digestion.ResultsValues for δ13C declined by 1.38 ‰ with increasing latitude across the transect, and increased by 0.44 ‰ from the beginning to the end of the season. The range of values for δ15N was greater than that for δ13C (13.29 vs 5.60 ‰). Differences in values for δ13C between graminoids (Eriophorum and Carex spp.) and shrubs (Betula and Salix spp.) were small but δ15N values distinguished graminoids (1.87 ± 1.02 ‰) from shrubs (−2.87 ± 2.93 ‰) consistently across season and latitude. However, undigested residues of forages were enriched in 15N when the digestibility of N was less than 0.67.ConclusionsAlthough δ15N values can distinguish plant groups in the diet of arctic herbivores, variation in the digestibility of dietary items may need to be considered in applying fractionation values for 15N to caribou and other herbivores that select highly digestible items (e.g. forbs) as well as heavily defended plants (e.g. woody browse).

Constraining mechanisms of quartz precipitation in the Archean ocean using silicon isotopes

NASA Astrophysics Data System (ADS)

Brengman, L. A.; Fedo, C.; Martin, W.

2017-12-01

To constrain reservoir values for the Archean silica cycle we measured silicon isotope compositions (δ30Si) of 28 igneous, siliciclastic sedimentary, hydrothermal, and chemical sedimentary rock samples from three Archean greenstone belts representing different times (>3.7 - 2.7 Ga) and tectonic regimes. We posit that silicon isotope compositions of quartz (746 analyses measured in situ by secondary ion mass spectrometry at the NORDSIM facility) are linked to changes in key geochemical parameters that vary within local depositional environments, coupled with a dependency on size and δ30Si composition of the source reservoir. Collectively, siliceous precipitates from even a single basin span a 7‰ range in δ30Si values. Such heterogeneity, regardless of basinal position or presence of Fe-phases demonstrates that δ30Si values of chemical sediments are linked to neither a well-mixed water column representative of a single ocean composition, nor a specific time in Earth history. Combining data from all three greenstone belts we discern that all measured Algoma-type iron formation (IF) and about 50% of associated chert samples possess δ30Si values <0‰, while the majority of silicified volcanic rocks and the remaining 50% of chert samples have δ30Si values >0‰. Negative values of Algoma-type IF can be explained by rate-dependent fractionation during precipitation and/or adsorption to Fe/Al. Combined experimental and natural data for quartz precipitates suggest slow precipitation rates coupled with closed system, Rayleigh type distillation could produce the isotopically heavy values. Such results suggest the quartz-precipitating fluid for these rocks evolves from an open system in disequilibrium, to one that is closed, and in equilibrium with the host rock. In contrast to the static range of values through time for Algoma-type IF, associated cherts and silicified rocks, compiled data for Superior-type IF from 3 - 1.8 Ga record a systematic increasing trend from dominantly 30Si-depleted to 30Si-enriched values over the Archean-Paleoproterozoic transition. Interpreted in the context of our provisional, mass-balance based flux model for the Precambrian silicon cycle, we conclude the 30Si-enrichment to reflect the evolving δ30Si composition of the ocean due to the addition of continentally derived silica.

Above detection limits - Prebiotic organics in comets and carbonaceous meteorites

NASA Astrophysics Data System (ADS)

Stern, J. C.; Elsila, J. E.; Callahan, M. P.; Glavin, D. P.; Martin, M. G.; Dworkin, J. P.

2009-12-01

The delivery of organic compounds such as amino acids and nucleobases by comets, asteroids, and their fragments may have contributed feedstock for prebiotic chemistry leading to the first self-replicating systems of the early Earth. In order to determine the isotopic composition, distribution, and abundance of prebiotic organic compounds in extraterrestrial samples we have recently optimized a highly sensitive liquid chromatography tandem quadupole mass spectrometer (LC-QqQ-MS) and a gas chromatography mass spectrometer coupled with an isotope ratio mass spectrometer (GC-MS/IRMS). This suite of instruments not only allows us to identify and quantify extremely trace amounts of organics of astrobiological interest, but also to confirm their extraterrestrial origins by stable isotopic measurements. The amino acid glycine was detected upon preliminary examinations of foils from NASA’s Stardust mission, which returned cometary material from comet 81P/Wild 2. To rule out the possibility of terrestrial contamination as the source of the glycine, the carbon isotopic ratio was measured. The δ13C value for glycine was determined to be +29 ± 6‰, well outside the terrestrial range for organic carbon of +6 ‰ to -40 ‰. The Stardust glycine δ13C value falls in the range previously reported for glycine (+22‰ to +41‰) in the carbonaceous meteorites Murchison and Orgueil. This represents the first detection of glycine or any other amino acid in a comet. Recent investigations of carbonaceous meteorite organic matter have revealed the presence of several nucleobases in the Murchison meteorite and several Antarctic CR meteorites never before analyzed for nucleobases using LC-QqQ-MS. This analytical tool is a sensitive and highly selective method for measuring the trace amounts of these organics in meteorites. In particular, the unusual Antarctic C2 meteorite, LON 94102, shows high abundances of guanine, hypoxanthine, and xanthine with concentrations ranging from 70 to 200 ppb. Nitrogen isotopic measurements will be made to determine the origin (extraterrestrial or terrestrial) of these compounds.

Water vapor δ17O measurements using an off-axis integrated cavity output spectrometer and seasonal variation in 17O-excess of precipitation in the east-central United States

NASA Astrophysics Data System (ADS)

Tian, C.; Wang, L.; Novick, K. A.

2016-12-01

High-precision triple oxygen isotope analysis can be used to improve our understanding of multiple hydrological and meteorological processes. Recent studies focus on understanding 17O-excess variation of tropical storms, high-latitude snow and ice-core as well as spatial distribution of meteoric water (tap water). The temporal scale of 17O-excess variation in middle-latitude precipitation is needed to better understand which processes control on the 17O-excess variations. This study focused on assessing how the accuracy and precision of vapor δ17O laser spectroscopy measurements depend on vapor concentration, delta range, and averaging-time. Meanwhile, we presented 17O-excess data from two-year, event based precipitation sampling in the east-central United States. A Triple Water Vapor Isotope Analyzer (T-WVIA) was used to evaluate the accuracy and precision of δ2H, δ18O and δ17O measurements. GISP and SLAP2 from IAEA and four working standards were used to evaluate the sensitivity in the three factors. Overall, the accuracy and precision of all isotope measurements were sensitive to concentration, with higher accuracy and precision generally observed under moderate vapor concentrations (i.e., 10000-15000 ppm) for all isotopes. Precision was also sensitive to the range of delta values, though the effect was not as large when compared to the sensitivity to concentration. The precision was much less sensitive to averaging time when compared with concentration and delta range effects. The preliminary results showed that 17O-excess variation was lower in summer (23±17 per meg) than in winter (34±16 per meg), whereas spring values (30±21 per meg) was similar to fall (29±13 per meg). That means kinetic fractionation influences the isotopic composition and 17O-excess in different seasons.

Stable Isotope (δ13C, δ15N, δ34S) Analysis and Satellite Telemetry Depict the Complexity of Gray Wolf (Canis lupus) Diets in Southwest Alaska

NASA Astrophysics Data System (ADS)

Stanek, A.; Watts, D. E.; Cohn, B. R.; Spencer, P.; Mangipane, B.; Welker, J. M.

2010-12-01

Throughout Alaska, gray wolves (Canis lupus) are a top predator of large ungulates. While they primarily rely on ungulates such as moose (Alces alces) and caribou (Rangifer tarandus) as food, they are opportunistic and use alternative resources. The variation and supplemental protein sources in wolf diet has not been studied extensively on live animals currently using the landscape. With large seasonal influxes of Pacific salmon (Oncorhynchus sp.) into Alaska, terrestrial carnivore use of marine species is of particular interest. Using stable isotope (δ13C, δ15N, δ34S) analysis of wolf guard hair and blood, this study aims to determine the proportion of marine derived nutrients (MDN) in the diet of wolf packs within and surrounding Lake Clark National Park and Preserve and Alaska Peninsula and Becharof National Wildlife Refuges in Southwest Alaska. Satellite telemetry from the animals sampled facilitates quantification of landscape use patterns in correspondence with isotopic traits. Wolf pack territories within and surrounding the Lake Clark region appear to vary in spatial extent and in availability of MDN, such as salmon. Initial analysis shows that two packs with smaller home ranges, centrally located around areas with greater salmon availability, have enriched δ15N values compared to packs that have larger home ranges not centralized around salmon spawning waters. This pattern of isotopic enrichment is found in red blood cells, blood serum and hair, representing diets over different time scales. The enrichment in both blood and hair indicates a sustained use of MDN over the previous six to nine months. In the Lake Clark region, simple mixing model estimates suggest that up to 30% of wolf pack diets may be from marine sources. In contrast, packs with larger home ranges and less access to salmon have stable isotope values representative of a terrestrial diet.

An improved procedure for separation/purification of boron from complex matrices and high-precision measurement of boron isotopes by positive thermal ionization and multicollector inductively coupled plasma mass spectrometry.

PubMed

Wei, Hai-Zhen; Jiang, Shao-Yong; Hemming, N Gary; Yang, Jing-Hong; Yang, Tao; Wu, He-Pin; Yang, Tang-Li; Yan, Xiong; Pu, Wei

2014-06-01

In order to eliminate boron loss and potential isotopic fractionation during chemical pretreatment of natural samples with complex matrices, a three-column ion-exchange separation/purification procedure has been modified, which ensures more than 98% recovery of boron from each step for a wide range of sample matrices, and is applicable for boron isotope analysis by both TIMS and MC-ICP-MS. The PTIMS-Cs2BO2(+)-static double collection method was developed, ensuring simultaneous collection of (133)Cs2(11)B(16)O2(+)(m/z 309) and (133)Cs2(10)B(16)O2(+) (m/z 308) ions in adjacent H3-H4 Faraday cups with typical zoom optics parameters (Focus Quad: 15 V, Dispersion Quad: -85 V). The external reproducibilities of the measured (11)B/(10)B ratios of the NIST 951 boron standard solutions of 1000 ng, 100 ng and 10 ng of boron by PTIMS method are ±0.06‰, ±0.16‰ and ±0.25‰, respectively, which indicates excellent precision can be achieved for boron isotope measurement at nanogram level boron in natural samples. An on-peak zero blank correction procedure was employed to correct the residual boron signals effect in MC-ICP-MS, which gives consistent δ(11)B values with a mean of 39.66±0.35‰ for seawater in the whole range of boron content from 5 ppb to 200 ppb, ensuring accurate boron isotope analysis in few ppb boron. With the improved protocol, consistent results between TIMS and MC-ICP-MS data were obtained in typical geological materials within a wide span of δ(11)B values ranging from -25‰ to +40‰. Copyright © 2014 Elsevier B.V. All rights reserved.

Iron isotope behavior during fluid/rock interaction in K-feldspar alteration zone - A model for pyrite in gold deposits from the Jiaodong Peninsula, East China

NASA Astrophysics Data System (ADS)

Zhu, Zhi-Yong; Jiang, Shao-Yong; Mathur, Ryan; Cook, Nigel J.; Yang, Tao; Wang, Meng; Ma, Liang; Ciobanu, Cristiana L.

2018-02-01

Mechanisms for Fe isotope fractionation in hydrothermal mineral deposits and in zones of associated K-feldspar alteration remain poorly constrained. We have analyzed a suite of bulk samples consisting of granite displaying K-feldspar alteration, Precambrian metamorphic rocks, and pyrite from gold deposits of the Jiaodong Peninsula, East China, by multi-collector inductively-coupled plasma mass spectrometry. Pyrites from disseminated (J-type) ores show a δ56Fe variation from +0.01 to +0.64‰, overlapping with the signature of the host granites (+0.08 to +0.39‰). In contrast, pyrites from quartz veins (L-type ores) show a wide range of Fe-isotopic composition from -0.78 to +0.79‰. Negative values are never seen in the J-type pyrites. The Fe isotope signature of the host granite with K-feldspar alteration is significantly heavier than that of the bulk silicate Earth. The Fe isotopic compositions of Precambrian metamorphic rocks across the district display a narrow range between -0.16‰ and +0.19‰, which is similar to most terrestrial rocks. Concentrations of major and trace elements in bulk samples were also determined, so as to evaluate any correlation between Fe isotope composition and degree of alteration. We note that during progressive K-feldspar alteration to rocks containing >70 wt% SiO2, >75 ppm Rb, and <1.2 wt% total Fe2O3, the Fe isotope composition of the granite changes systematically. The Fe isotope signature becomes heavier as the degree of alteration increases. The extremely light Fe isotopic compositions in L-type gold deposits may be explained by Rayleigh fractionation during pyrite precipitation in an open fracture system. We note that the sulfur isotopic compositions of pyrite in the two types of ores are also different. Pyrite from J-type ores has a systematically 3.5‰-higher δ34S value (11.2‰) than those of pyrite from the L-type ores (7.7‰). There is, however, no correlation between Fe and S isotope signatures. The isotopic fractionation of sulfur is used to constrain a change in the fO2 of the hydrothermal fluids from which pyrite precipitated. This work demonstrates that the Fe isotope composition of pyrite displays a significant response to the process of pyrite precipitation in hydrothermal systems, and that systematic fractionation of iron isotopes occurs during fluid/rock reaction in the K-feldspar alteration zone of the Linglong granite. The implications of the results are that processes of mineralization and associated fluid-rock interaction, which are ubiquitously observed in porphyry-style Cu-Au-Mo and other hydrothermal deposits, may be readily traceable using Fe isotopes.

Ubiquitous radiogenic Os in Miocene to recent basalts from diverse mantle domains beneath the Colorado Plateau, USA

NASA Astrophysics Data System (ADS)

Schlieder, T.; Reid, M. R.; Widom, E.; Blichert-Toft, J.

2015-12-01

The source of magmatism and mechanisms responsible for the observed geochemical signatures in Miocene to Recent Colorado Plateau (CP) basalts has been a renewed focus of investigation in light of Earthscope results. We report new Os and Nd isotopic data for magnesian basalts (Mg#=62-72) and interpret them in light of previously reported Hf isotope data to help constrain contributions from olivine-poor source lithologies and subduction-derived metasomatism in the genesis of recent CP volcanism. The basalts studied span a large range in Hf isotope compositions and represent melts last equilibrated at a variety of depths beneath the Colorado Plateau and its transition zones. We distinguished at least three mantle domains on the basis of paired Hf-Nd isotope, other isotopic, and geochemical characteristics of CP lavas. Domain 1 likely represents a depleted, variably metasomatized, lithospheric source, with relatively radiogenic ɛHf (+5.2 to +11.8) and highly variable ɛNd (-6.2 to +6.2). Domain 2 could represent either ancient or Farallon subduction-modified mantle and is displaced above the Hf-Nd mantle array (ɛHf=+1.0 to +7.3; ɛNd=-6.1 to -3.5). Domain 3 may be melts of pyroxenite/mica-rich veins or layers within lithospheric mantle and is characterized by unradiogenic Hf and Nd (ɛHf=-12.9 to +0.6; ɛNd=-10.0 to -2.9). The isotopic variability in CP-related lavas can largely be attributed to contributions from these mantle domains. Preliminary Os isotope data show no correlation with proxies for differentiation or crustal contamination. Osmium and Hf isotope compositions are negatively correlated between domains 1 and 2 (187Os/188Os=0.31 to 0.59), whereas the Os isotope ratios in two domain 3 basalts have both lower and higher values (187Os/188Os=0.25 and 0.68). Significantly, Os isotope signatures are highly radiogenic (vs. values of <0.12 for SW US peridotite xenoliths [1]), overlapping and extending the range for inferred melts of pyroxene- and mica-rich veins and/or layers [2]. Thus mafic magmatism associated with the CP appears to ubiquitously tap sources at least locally modified by processes such as recycling of ancient oceanic crust, introduction of terrigenous sediments, or subduction-related metasomatism. [1] Lee et al., Nature, 2001. [2] Carlson and Nowell, G-Cubed, 2001.

Late Pleistocene C4 plant dominance and summer rainfall in the southwestern United States from isotopic study of herbivore teeth

USGS Publications Warehouse

Connin, S.L.; Betancourt, J.; Quade, Jay

1998-01-01

Patterns of climate and C4 plant abundance in the southwestern United States during the last glaciation were evaluated from isotopic study of herbivore tooth enamel. Enamel ??13C values revealed a substantial eastward increase in C4 plant consumption for Mammuthus spp., Bison spp., Equus spp., and Camelops spp. The ??13C values were greatest in Bison spp. (-6.9 to + 1.7???) and Mammuthus spp. (-9.0 to +0.3???), and in some locales indicated C4-dominated grazing. The ??13C values of Antilocaprids were lowest among taxa (-12.5 to -7.9???) and indicated C3 feeding at all sites. On the basis of modern correlations between climate and C4 grass abundance, the enamel data imply significant summer rain in parts of southern Arizona and New Mexico throughout the last glaciation. Enamel ??18O values range from +19.0 to +31.0??? and generally increase to the east. This pattern could point to a tropical or subtropical source of summer rainfall. At a synoptic scale, the isotope data indicate that interactions of seasonal moisture, temperature, and lowered atmospheric pCO2 determined glacial-age C4 abundance patterns.

Assimilation of sediments embedded in the oceanic arc crust: myth or reality?

NASA Astrophysics Data System (ADS)

Bezard, Rachel; Davidson, Jon P.; Turner, Simon; Macpherson, Colin G.; Lindsay, Jan M.; Boyce, Adrian J.

2014-06-01

Arc magmas are commonly assumed to form by melting of sub-arc mantle that has been variably enriched by a component from the subducted slab. Although most magmas that reach the surface are not primitive, the impact of assimilation of the arc crust is often ignored with the consequence that trace element and isotopic compositions are commonly attributed only to varying contributions from different components present in the mantle. This jeopardises the integrity of mass balance recycling calculations. Here we use Sr and O isotope data in minerals from a suite of volcanic rocks from St Lucia, Lesser Antilles arc, to show that assimilation of oceanic arc basement can be significant. Analysis of 87Sr/86Sr in single plagioclase phenocrysts from four Soufrière Volcanic Complex (SVC; St Lucia) hand samples with similar composition (87Sr/86Sr = 0.7089-0.7091) reveals crystal isotopic heterogeneity among hand samples ranging from 0.7083 to 0.7094 with up to 0.0008 difference within a single hand sample. δO18 measurements in the SVC crystals show extreme variation beyond the mantle range with +7.5 to +11.1‰ for plagioclase (n=19), +10.6 to +11.8‰ for quartz (n=10), +9.4 to +9.8‰ for amphibole (n=2) and +9 to +9.5‰ for pyroxene (n=3) while older lavas (Pre-Soufriere Volcanic Complex), with less radiogenic whole rock Sr composition (87Sr/86Sr = 0.7041-0.7062) display values closer to mantle range: +6.4 to +7.9‰ for plagioclase (n=4) and +6 to +6.8‰ for pyroxene (n=5). We argue that the 87Sr/86Sr isotope disequilibrium and extreme δO18 values provide compelling evidence for assimilation of material located within the arc crust. Positive correlations between mineral δO18 and whole rock 87Sr/86Sr, 143Nd/144Nd and 206,207,208Pb/204Pb shows that assimilation seems to be responsible not only for the isotopic heterogeneity observed in St Lucia but also in the whole Lesser Antilles since St Lucia encompasses almost the whole-arc range of isotopic compositions. This highlights the need for detailed mineral-scale investigation of oceanic arc suites to quantify assimilation that could otherwise lead to misinterpretation of source composition and subduction processes.

Source area and seasonal variation of dissolved Sr isotope composition in rivers of the Amazon basin

NASA Astrophysics Data System (ADS)

Santos, Roberto V.; Sondag, Francis; Cochonneau, Gerard; Lagane, Christelle; Brunet, Pierre; Hattingh, Karina; Chaves, Jeane G. S.

2014-05-01

We present dissolved Sr isotope data collected over 8 years from three main river systems from the Amazon Basin: Beni-Madeira, Solimões, Amazon, and Negro. The data show large 87Sr/86Sr ratio variations that were correlated with the water discharge and geology of the source areas of the suspended sediments. The Beni-Madeira system displays a high average 87Sr/86Sr ratio and large 87Sr/86Sr fluctuations during the hydrological cycle. This large average value and fluctuations were related to the presence of Precambrian rocks and Ordovician sediments in the source area of the suspended sediment of the river. In contrast, the Solimões system displays a narrow range of Sr isotope ratio variations and an average value close to 0.709. This river drains mostly Phanerozoic rocks of northern Peru and Ecuador that are characterized by low Sr isotope ratios. Despite draining areas underlain by Precambrian rocks and having high 87Sr/86Sr ratios, such rivers as the Negro and Tapajós play a minor role in the total Sr budget of the Amazon Basin. The isotopic fluctuations in the Beni-Madeira River were observed to propagate downstream at least as far as Óbidos, in the Amazon River. This signal is characterized by an inverse relationship between the concentration of elemental Sr and its isotopic ratios. During the raining season there is an increase in Sr isotopic ratio accompanied by a decrease in elemental Sr concentration. During the dry season, the Sr isotopic ration decreases and the elemental Sr concentration increases.

Seabird satellite tracking validates the use of latitudinal isoscapes to depict predators' foraging areas in the Southern Ocean.

PubMed

Jaeger, Audrey; Lecomte, Vincent J; Weimerskirch, Henri; Richard, Pierre; Cherel, Yves

2010-12-15

Stable isotopes are increasingly being used to trace wildlife movements. A fundamental prerequisite of animal isotopic tracking is a good knowledge of spatial isotopic variations in the environment. Few accessible reference maps of the isotopic landscape ("isoscapes") are available for marine predators. Here, we validate for the first time an isotopic gradient for higher trophic levels by using a unique combination of a large number of satellite-tracks and subsequent blood plasma isotopic signatures from a wide-ranging oceanic predator. The plasma δ(13)C and δ(15)N values of wandering albatrosses (n = 45) were highly and positively correlated to the Southern Ocean latitudes at which the satellite-tracked individuals foraged. The well-defined latitudinal baseline carbon isoscapes in the Southern Ocean is thus reflected in the tissue of consumers, but with a positive shift due to the cumulative effect of a slight (13)C-enrichment at each trophic level. The data allowed us to estimate the carbon isotopic position of the main oceanic fronts in the area, and thus to delineate robust isoscapes of the main foraging zones for top predators. The plasma δ(13)C and δ(15)N values were positively and linearly correlated, thus suggesting that latitudinal isoscapes also occur for δ(15)N at the base of the food web in oceanic waters of the Southern Ocean. The combination of device deployments with sampling of relevant tissues for isotopic analysis appears to be a powerful tool for investigating consumers' isoscapes at various spatio-temporal scales. Copyright © 2010 John Wiley & Sons, Ltd.

Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

2018-04-01

Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy Fe isotopes compositions of the sulfides from the SMAR may suggest the equilibrium fractionation process under high temperature conditions. The red Fe oxides are enriched in heavy Fe isotopes, indicating that the oxidative weathering processes result in the occurrence of significant Fe-isotope fractionation and the preferential enrichment of heavy Fe isotopes in the oxidation product.

Development of an enantiomer-specific stable carbon isotope analysis (ESIA) method for assessing the fate of α-hexachlorocyclo-hexane in the environment.

PubMed

Badea, Silviu-Laurentiu; Vogt, Carsten; Gehre, Matthias; Fischer, Anko; Danet, Andrei-Florin; Richnow, Hans-Hermann

2011-05-30

α-Hexachlorocyclohexane (α-HCH) is the only chiral isomer of the eight 1,2,3,4,5,6-HCHs and we have developed an enantiomer-specific stable carbon isotope analysis (ESIA) method for the evaluation of its fate in the environment. The carbon isotope ratios of the α-HCH enantiomers were determined for a commercially available α-HCH sample using a gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) system equipped with a chiral column. The GC-C-IRMS measurements revealed δ-values of -32.5 ± 0.8‰ and -32.3 ± 0.5‰ for (-) α-HCH and (+) α-HCH, respectively. The isotope ratio of bulk α-HCH was estimated to be -32.4 ± 0.6‰ which was in accordance with the δ-values obtained by GC-C-IRMS (-32.7 ± 0.2‰) and elemental analyzer-isotope ratio mass spectrometry (EA-IRMS) of the bulk α-HCH (-32.1 ± 0.1‰). The similarity of the isotope ratio measurements of bulk α-HCH by EA-IRMS and GC-C-IRMS indicates the accuracy of the chiral GC-C-IRMS method. The linearity of the α-HCH ESIA method shows that carbon isotope ratios can be obtained for a signal size above 100 mV. The ESIA measurements exhibited standard deviations (2σ) that were mostly < ± 0.5‰. In order to test the chiral GC-C-IRMS method, the isotope compositions of individual enantiomers in biodegradation experiments of α-HCH with Clostridium pasteurianum and samples from a contaminated field site were determined. The isotopic compositions of the α-HCH enantiomers show a range of enantiomeric and isotope patterns, suggesting that enantiomeric and isotope fractionation can serve as an indicator for biodegradation and source characterization of α-HCH in the environment. Copyright © 2011 John Wiley & Sons, Ltd.

Experimental Assessment of Carbon Isotopes of Light Hydrocarbons under Different Redox Conditions

NASA Astrophysics Data System (ADS)

Fu, Q.; Chen, X.

2017-12-01

Hydrocarbons can be derived from a variety of carbon sources, by different processes, and under a wide range of physicochemical conditions. Other than bacterial activities facilitating biogenic hydrocarbon formation at low temperatures, decomposition of complex organic matter in sedimentary rocks at elevated temperatures produce thermogenic hydrocarbons, whereas abiogenic hydrocarbons are mainly generated through Fischer-Tropsch type synthesis with mineral catalysts. The carbon isotope has been used extensively to distinguish hydrocarbons of different origins and their formation conditions. For each type of hydrocarbons, however, environmental conditions may change reaction pathways and corresponding isotope fractionations. To better understand the variation of carbon isotopes caused by environmental variables, mineral constraints in particular, a series of laboratory experiments are conducted. In experiments where thermogenic hydrocarbons are formed, oil shale is the source material with different gypsum contents (0, 0.3, 0.5, and 1 wt.%). The abundance of generated light straight chain hydrocarbons decreases with increasing gypsum content, but their carbon isotopes become heavier. For example, the δ13C value of methane increases from -55.1‰ to -41.4‰ with gypsum varying between 0 and 1 wt.%. In similar experiments with the presence of MnO2, carbon isotope values of light alkanes are also higher, but with limited magnitudes (e.g., 3 to 4‰ for methane). In another experiment with dissolved H2 gas of 100 mmol/kg, light alkanes become depleted in 13C than experiments without H2. For example, there is a depletion of 2.7‰ for methane. The variation of carbon isotope values of light alkanes suggests the redox condition, constrained by mineral assemblage, fluid composition, and physical environment, play an important role in isotope fractionation. The pathway of hydrocarbon generation may be different under oxidized or reducing conditions. A set of experiments, in which abiogenic hydrocarbons are formed, is currently in progress. Combined together, they would facilitate our understanding of carbon isotope fractionation under geological conditions, and effective use of carbon isotopes as a diagnostic tool for hydrocarbons that are poorly understood in terms of origin and evolution.

Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

USGS Publications Warehouse

Coleman, D.D.; Risatti, J.B.; Schoell, M.

1981-01-01

Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted. We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both 13C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26??C than at 11.5??C. The change in ??D relative to the change in ??13C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway. The change in the ??D value for the residual methane was from 8 to 14 times greater than the change in the ??13C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria. ?? 1981.

Authenticity of carbon dioxide bubbles in French ciders through multiflow-isotope ratio mass spectrometry measurements.

PubMed

Gaillard, Laetitia; Guyon, Francois; Salagoïty, Marie-Hélène; Médina, Bernard

2013-12-01

A procedure to detect whether carbon dioxide was added to French ciders has been developed. For this purpose, an optimised and simplified method is proposed to determine (13)C/(12)C isotope ratio of carbon dioxide (δ(13)C) in ciders. Three critical steps were checked: (1) influence of atmospheric CO2 remaining in the loaded vial, (2) impact of helium flush, (3) sampling speed. This study showed that atmospheric CO2 does not impact the measurement, that helium flush can lead to isotopic fractionation and finally, that a fractionation occurs only 5h after bottle opening. The method, without any other preparation, consists in sampling 0.2 mL of cold (4 °C) cider in a vial that is passed in an ultrasonic bath for 10 min at room temperature to enhance cider de-carbonation. The headspace CO2 is then analysed using the link Multiflow®-isotope ratio mass spectrometer. Each year, a data bank is developed by fermenting authentic apples juices in order to control cider authenticity. Over a four year span (2008-2011), the CO2 produced during the fermentation step was studied. This set of 61 authentic ciders, from various French production areas, was used to determine a δ(13)C value range of -22.59±0.92‰ for authentic ciders CO2 bubbles. 75 commercial ciders were analysed with this method. Most of the samples analysed present a gas δ(13)C value in the expected range. Nevertheless, some ciders have δ(13)C values outside the 3σ limit, revealing carbonation by technical CO2. This practice is not allowed for organic, "Controlled Appellation of Origin" ciders and ciders specifying natural carbonation on the label. Copyright © 2013 Elsevier Ltd. All rights reserved.

Methane production and isotopic fingerprinting in ethanol fuel contaminated sites.

PubMed

Freitas, Juliana G; Fletcher, Barbara; Aravena, Ramon; Barker, James F

2010-01-01

Biodegradation of organic compounds in groundwater can be a significant source of methane in contaminated sites. Methane might accumulate in indoor spaces posing a hazard. The increasing use of ethanol as a gasoline additive is a concern with respect to methane production since it is easily biodegraded and has a high oxygen demand, favoring the development of anaerobic conditions. This study evaluated the use of stable carbon isotopes to distinguish the methane origin between gasoline and ethanol biodegradation, and assessed the occurrence of methane in ethanol fuel contaminated sites. Two microcosm tests were performed under anaerobic conditions: one test using ethanol and the other using toluene as the sole carbon source. The isotopic tool was then applied to seven field sites known to be impacted by ethanol fuels. In the microcosm tests, it was verified that methane from ethanol (δ¹³C = -11.1‰) is more enriched in ¹³C, with δ¹³C values ranging from -20‰ to -30‰, while the methane from toluene (δ¹³C = -28.5‰) had a carbon isotopic signature of -55‰. The field samples had δ¹³C values varying over a wide range (-10‰ to -80‰), and the δ¹³C values allowed the methane source to be clearly identified in five of the seven ethanol/gasoline sites. In the other two sites, methane appears to have been produced from both sources. Both gasoline and ethanol were sources of methane in potentially hazardous concentrations and methane could be produced from organic acids originating from ethanol along the groundwater flow system even after all the ethanol has been completed biodegraded. Copyright © 2010 The Author(s). Journal compilation © 2010 National Ground Water Association.

Rapid and high-precision measurement of sulfur isotope and sulfur concentration in sediment pore water by multi-collector inductively coupled plasma mass spectrometry.

PubMed

Bian, Xiao-Peng; Yang, Tao; Lin, An-Jun; Jiang, Shao-Yong

2015-01-01

We have developed a technique for the rapid, precise and accurate determination of sulfur isotopes (δ(34)S) by MC-ICP-MS applicable to a range of sulfur-bearing solutions of different sulfur content. The 10 ppm Alfa-S solution (ammonium sulfate solution, working standard of the lab of the authors) was used to bracket other Alfa-S solutions of different concentrations and the measured δ(34)SV-CDT values of Alfa-S solutions deviate from the reference value to varying degrees (concentration effect). The stability of concentration effect has been verified and a correction curve has been constructed based on Alfa-S solutions to correct measured δ(34)SV-CDT values. The curve has been applied to AS solutions (dissolved ammonium sulfate from the lab of the authors) and pore water samples successfully, validating the reliability of our analytical method. This method also enables us to measure the sulfur concentration simultaneously when analyzing the sulfur isotope composition. There is a strong linear correlation (R(2)>0.999) between the sulfur concentrations and the intensity ratios of samples and the standard. We have constructed a regression curve based on Alfa-S solutions and this curve has been successfully used to determine sulfur concentrations of AS solutions and pore water samples. The analytical technique presented here enable rapid, precise and accurate S isotope measurement for a wide range of sulfur-bearing solutions - in particular for pore water samples with complex matrix and varying sulfur concentrations. Also, simultaneous measurement of sulfur concentrations is available. Copyright © 2014 Elsevier B.V. All rights reserved.

Hydrogen isotope correction for laser instrument measurement bias at low water vapor concentration using conventional isotope analyses: application to measurements from Mauna Loa Observatory, Hawaii.

PubMed

Johnson, L R; Sharp, Z D; Galewsky, J; Strong, M; Van Pelt, A D; Dong, F; Noone, D

2011-03-15

The hydrogen and oxygen isotope ratios of water vapor can be measured with commercially available laser spectroscopy analyzers in real time. Operation of the laser systems in relatively dry air is difficult because measurements are non-linear as a function of humidity at low water concentrations. Here we use field-based sampling coupled with traditional mass spectrometry techniques for assessing linearity and calibrating laser spectroscopy systems at low water vapor concentrations. Air samples are collected in an evacuated 2 L glass flask and the water is separated from the non-condensable gases cryogenically. Approximately 2 µL of water are reduced to H(2) gas and measured on an isotope ratio mass spectrometer. In a field experiment at the Mauna Loa Observatory (MLO), we ran Picarro and Los Gatos Research (LGR) laser analyzers for a period of 25 days in addition to periodic sample collection in evacuated flasks. When the two laser systems are corrected to the flask data, they are strongly coincident over the entire 25 days. The δ(2)H values were found to change by over 200‰ over 2.5 min as the boundary layer elevation changed relative to MLO. The δ(2)H values ranged from -106 to -332‰, and the δ(18)O values (uncorrected) ranged from -12 to -50‰. Raw data from laser analyzers in environments with low water vapor concentrations can be normalized to the international V-SMOW scale by calibration to the flask data measured conventionally. Bias correction is especially critical for the accurate determination of deuterium excess in dry air. Copyright © 2011 John Wiley & Sons, Ltd.

Relating carbon and nitrogen isotope effects to reaction mechanisms during aerobic or anaerobic degradation of RDX (Hexahydro-1,3,5-Trinitro-1,3,5-Triazine) by pure bacterial cultures

USGS Publications Warehouse

Fuller, Mark E.; Heraty, Linnea J.; Condee, Charles W.; Vainberg, Simon; Sturchio, Neil C.; Böhlke, John Karl; Hatzinger, Paul B.

2016-01-01

Kinetic isotopic fractionation of carbon and nitrogen during RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) biodegradation was investigated with pure bacterial cultures under aerobic and anaerobic conditions. Relatively large bulk enrichments in 15N were observed during biodegradation of RDX via anaerobic ring cleavage (ε15N = −12.7‰ ± 0.8‰) and anaerobic nitro reduction (ε15N = −9.9‰ ± 0.7‰), in comparison to smaller effects during biodegradation via aerobic denitration (ε15N = −2.4‰ ± 0.2‰). 13C enrichment was negligible during aerobic RDX biodegradation (ε13C = −0.8‰ ± 0.5‰) but larger during anaerobic degradation (ε13C = −4.0‰ ± 0.8‰), with modest variability among genera. Dual-isotope ε13C/ε15N analyses indicated that the three biodegradation pathways could be distinguished isotopically from each other and from abiotic degradation mechanisms. Compared to the initial RDX bulk δ15N value of +9‰, δ15N values of the NO2− released from RDX ranged from −7‰ to +2‰ during aerobic biodegradation and from −42‰ to −24‰ during anaerobic biodegradation. Numerical reaction models indicated that N isotope effects of NO2− production were much larger than, but systematically related to, the bulk RDX N isotope effects with different bacteria. Apparent intrinsic ε15N-NO2− values were consistent with an initial denitration pathway in the aerobic experiments and more complex processes of NO2− formation associated with anaerobic ring cleavage. These results indicate the potential for isotopic analysis of residual RDX for the differentiation of degradation pathways and indicate that further efforts to examine the isotopic composition of potential RDX degradation products (e.g., NOx) in the environment are warranted.

Unraveling of permafrost hydrological variabilities on Central Qinghai-Tibet Plateau using stable isotopic technique.

PubMed

Yang, Yuzhong; Wu, Qingbai; Hou, Yandong; Zhang, Zhongqiong; Zhan, Jing; Gao, Siru; Jin, Huijun

2017-12-15

Permafrost degradation on the Qinghai-Tibet Plateau (QTP) will substantially alter the surface runoff discharge and generation, which changes the recharge processes and influences the hydrological cycle on the QTP. Hydrological connections between different water bodies and the influence of thawing permafrost (ground ice) are not well understood on the QTP. This study applied water stable isotopic method to investigate the permafrost hydrological variabilities in Beiluhe Basin (BLB) on Central QTP. Isotopic variations of precipitation, river flow, thermokarst lake, and near-surface ground ice were identified to figure out the moisture source of them, and to elaborate the hydrological connections in permafrost region. Results suggested that isotopic seasonalities in precipitation is evident, it is showing more positive values in summer seasons, and negative values in winter seasons. Stable isotopes of river flow are mainly distributed in the range of precipitation which is indicative of important replenishment from precipitation. δ 18 O, δD of thermokarst lakes are more positive than precipitation, indicating of basin-scale evaporation of lake water. Comparison of δ I values in different water bodies shows that hydrology of thermokarst lakes was related to thawing of permafrost (ground ice) and precipitation. Near-surface ground ice in BLB exhibits different isotopic characteristics, and generates a special δD-δ 18 O relationship (freezing line): δD=5.81δ 18 O-23.02, which reflects typical freezing of liquid water. From isotopic analysis, it is inferred that near-surface ground ice was mainly recharged by precipitation and active layer water. Stable isotopic and conceptual model is suggestive of striking hydrological connections between precipitation, river flow, thermokarst lake, and ground ice under degrading permafrost. This research provides fundamental comprehensions into the hydrological processes in permafrost regions on QTP, which should be considered in investigating the influence of thawing permafrost on the hydrological cycle on QTP. Copyright © 2017 Elsevier B.V. All rights reserved.

In Situ Carbon and Sulfur Isotope Analysis of Archean Organic Matter and Pyrite

NASA Technical Reports Server (NTRS)

Williford, K. H.; Ushikubo, T.; LePot, K.; Kitajima, K.; Spicuzza, M. J.; Valley, J. W.; Hallman, C.; Summons, R.; Eigenbrode, J. L.

2012-01-01

Stable isotopic compositions of biologically important elements (e.g., C and S) in sedimentary rocks are valuable biosignatures to the extent that they indicate the presence and variable expression of microbial metabolisms in space and time. Strong interactions between the carbon and sulfur cycles (e.g., via organic matter remineralization during microbial sulfate reduction) make coordinated, in situ C and S isotope analysis by secondary ion mass spectrometry (SIMS) a particularly powerful tool. In rocks ranging in age from 2.7-2.5 Ga, expansions in the ranges of delta C-13 of organic matter and delta S-34 of pyrite likely reflect the increasing influence of oxygenic photosynthesis in the surface ocean (as well as methane and sulfur metabolisms in deeper waters), whereas the large range of mass independent sulfur isotope fractionation (Delta S-33) suggests that the atmosphere remained anoxic until approx 2.4 Gyr ago. We report in situ delta C-13 measurements of organic matter in the approx 2.7-2.6 Ga Carawine Dolomite, Marra Mamba Iron Formation, and Jeerinah, Wittenoom, and Tumbiana Formations, as well as the approx 2.5 Ga Mount McRae Shale. We also report in situ delta S-24 and Delta S-33 measurements of pyrite associated with organic matter in a subset of these samples. In a single square cm sample of the Tumbiana Formation with bulk delta C-13(sub org) of -49.7% (VPDB), two distinct kerogen types have delta C-13 values, measured in situ, consistent with oxygenic photosynthesis (-33%) and methane metabolism (-52%). In a sample from the ABDP-9 core, radiobitumen associated with a uraniferous mineral grain is C-13-enriched by 8% (-26.8%0) relative to average in situ kerogen (-34.9%0) and similar in delta C-13 to solvent extractable hydrocarbons from the Mount McRae Shale (avg delta C-13 = -27.1 %). Average reproducibility for delta C-13 was 0.4% (2 SD) using a 6 micron spot and 0.8% using a 3 micron spot. In situ sulfur isotope analyses of 33 authigenic pyrite grains in 3 samples of the ABDP-9 core using a 10 micron spot (2 SD reproducibility = 0.4% for delta S-34 and -0.1% for Delta S-33) show a range of 28.1 % in delta S-34 (-10.3 to 17.8%) and 13.3%0 in Delta S-33 (-3.8 to 9.5%), whereas the range from 132 bulk analyses across 84 m of core is 19.4% for delta S-34 and 11.5% for Delta S-33. Coordinated, in situ carbon and sulfur isotope analyses in one ABDP-9 sample are shown. In situ values from this kerogen-pyrite association are within 0.1% of the bulk value in the case of delta C-13 and higher by several permil in the case of delta S-34 and Delta S-33. Coordinated in situ carbon and sulfur isotope analyses in rocks deposited during key intervals of environmental change (e.g., the Great Oxidation Event) can refine our understanding of the mode and tempo of change. In Earth's oldest sedimentary rocks, and in extraterrestrial samples, these coordinated in situ analyses may reveal biosignatures in the form of isotopic correlations at the scale of individual microorganisms and their microhabitats.

Comprehensive authentication of (E)-alpha(beta)-ionone from raspberries, using constant flow MDGC-C/P-IRMS and enantio-MDGC-MS.

PubMed

Sewenig, Sabine; Bullinger, Dino; Hener, Uwe; Mosandl, Armin

2005-02-23

A new coupling system of GC-GC, connected via a Multi Column Switching Device MCS2 for measuring isotope ratios, is introduced. By means of several standard substances the precise and accurate measurement of isotopic values is proved. First applications concerning the authentication of raspberry aroma compounds are established. Consequently, the combination of constant flow multidimensional gas chromatography-combustion/pyrolysis-isotope ratio mass spectrometry (MDGC-C/P-IRMS) is applied to the authenticity assessment of (E)-alpha(beta)-ionone from six different raspberry cultivars. Furthermore, 12 commercially available raspberry products and samples of (E)-alpha(beta)-ionone, some declared to be natural, are investigated. delta(2)Eta(V)(-)(SMOW) and delta(13)C(V)(-)(PDB) values of (E)-alpha(beta)-ionone are determined, and characteristic authenticity ranges were concluded from raspberries by correlation of both delta(2)Eta(V)(-)(SMOW) and delta(13)C( V)(-)(PDB) values. The results are correlated with the determination of enantiomeric purities of (E)-alpha-ionone, using stir bar sorptive extraction enantio-multidimensional gas chromatography mass spectrometry (SBSE-enantio-MDGC-MS).

Multiple oxygen and sulfur isotope compositions of secondary atmospheric sulfate in the city of Wuhan, central China

NASA Astrophysics Data System (ADS)

Li, X.; Bao, H.; Zhou, A.; Wang, D.

2012-12-01

Secondary atmospheric sulfate (SAS) is the oxidation product and sink for sulfur gases of biological, volcanic, and anthropogenic origins on Earth. SAS can be produced from gas-phase OH-radical oxidation and five aqueous-phase chemical reactions including aqueous-phase S (IV) oxidation reactions by H2O2, O3, oxygen catalyzed by Fe3+ and Mn2+, and methyle hydrogen peroxide and peroxyacetic acid. The tropospheric sulfur oxidation pathway is therefore determined by cloud-water pH, dissolved [Fe2+] or [Mn2+] content, S emission rate, meteorological condition, and other factors. The S isotope composition is a good tracer for the source while the O isotopes, especially the triple O isotope compositions are a good tracer for S oxidation pathway. Jerkins and Bao (2006) provided the first set of multiple stable isotope compositions (δ34S, δ18O and Δ17O) for SAS collected from bulk atmosphere in Baton Rouge in the relatively rural southern USA. Their study revealed a long-tern average Δ17O value of ~+0.7‰ for SAS, and speculated that much of the Earth mid-latitudes may have a similar average SAS Δ17O value. Additional sampling campaign at different sites is necessarily for constructing and testing models on sulfur oxidation and transport in the troposphere. A total of 33 sulfate samples were collected from bulk atmospheric deposition over a 950-day period from May 2009 to December 2011 in the city of Wuhan, Hubei Province, China. Differing from Baton Rouge, Wuhan is an industrial metropolis with a population of 9.8 million and a high particulate matter content (115 μg/m3). It also has a subtropical monsoon climate, with rainwater pH at ~5.3 year-around. The rainwater ion concentrations have seasonal variations, typically low in summer and high in winter. The anions are dominated by SO42-, at an average concentration of 8.5 mg/L. There is little sulfate contribution from sea-salt (SS) sulfate or dusts in Wuhan. The isotopic compositions for bulk atmospheric sulfate range from 0.00‰ to 1.02‰ for the Δ17O, 8.0‰ to 17.8‰ for the δ18O, and 2.1‰ to 24.1‰ for the δ34S. No apparent correlation is found among Δ17O, δ18O, or δ34S values. No significant temporal pattern exists for the Δ17O over the collection period. The positive Δ17O values for SAS have a time-weighted average of 0.52 ± 0.23‰, lower than the average in Baton Rouge, raising the possibility that the high particulate matter content in Wuhan may have played a role in promoting S oxidation via surface and/or Fe(III)-catalyzed pathways that do not generate positive 17O anomaly in product sulfate. The average Δ17O value also supports the assertion that the long-term average Δ17O value for SAS in the mid-latitude sites fall within a range (0.6~0.8‰) that is much lower than that in polar areas. The SAS δ18O values in Wuhan lie within the range reported for other sites (+5.0‰ to +19.6‰), with a time-weighted average value of 12.0 ± 2.3‰. Not counting three outlier (>13‰), the δ34S values are at a narrow range with a time-weighted average of +4.5 ±1.3‰ (n=30), which is higher than those from Baton Rouge but is typical for the heavily populated regions in China.

Calcium Isotopic Systematics of Peridotite Xenoliths from eastern North China Craton: Implications for Melt-rock Interaction

NASA Astrophysics Data System (ADS)

Zhang, Z.; Zhao, X.; Huang, S.; Xiao, Y.; Li, X.

2017-12-01

In order to better constrain and understand the Ca isotopic variations in the mantle, we report high-precision Ca isotopic data of orthopyroxene (Opx) and clinopyroxene (Cpx) for a set of peridotitic xenoliths from ChangLe, eastern North China craton (NCC). These xenoliths range from lherzolites, Cpx-rich lherzolites to wehrlites, and are variably metasomatised. Lherzolites (Fo≈91) are fertile in mineral composition, and have spoon-shaped to slightly LREE-enriched rare earth element (REE) patterns. They may represent fragments of newly accreted lithospheric mantle that makes up parts of the Late Mesozoic-Cenozoic lithosphere beneath the eastern NCC. Cpx-rich lherzolites and wehrlites formed by reaction of refractory residual peridotites with evolved, Fe-rich silicate melts at high melt/rock ratios, as evidenced by partial to complete replacement of Opx with Cpx, relatively lower Fo contents of Ol (<88) than that from the lherzolites and convex-upward trace element patterns. Our results show that there are large δ44/40Ca variations (1‰) in these peridotitic xenoliths. Lherzolites have δ44/40Ca similar to typical upper mantle value(1.05 ± 0.04). Specifically, lherzolites orthopyroxenes have δ44/40Ca ranging from 1.04 to 1.79, and lherzolites clinopyroxenes have δ44/40Ca from 0.80 to 1.04. In contrast, δ44/40Ca in Cpx-rich lherzolites and wehrlites tend to have lower values reltaive to those of lherzolites. Their clinopyroxenes have δ44/40Ca ranging from 0.42 to 0.92, and their orthopyroxenes have δ44/40Ca ranging from 0.80 to 1.04. Collectively, we identify a positive correlation between clinopyroxene δ44/40Ca and Mg#. Model calculations show that kinetic isotopic fractionation caused by diffusion, probably during mantle melt-rock interaction, is responsible for the positive correlation between clinopyroxene δ44/40Ca and Mg# in these NCC peridotites. Our study shows that melt-rock interaction plays an important role in producing Ca isotopic heterogeneity of the subcontinental mantle.

Nickel isotopic composition of the mantle

NASA Astrophysics Data System (ADS)

Gall, Louise; Williams, Helen M.; Halliday, Alex N.; Kerr, Andrew C.

2017-02-01

This paper presents a detailed high-precision study of Ni isotope variations in mantle peridotites and their minerals, komatiites as well as chondritic and iron meteorites. Ultramafic rocks display a relatively large range in δ60 Ni (permil deviation in 60 Ni /58 Ni relative to the NIST SRM 986 Ni isotope standard) for this environment, from 0.15 ± 0.07‰ to 0.36 ± 0.08‰, with olivine-rich rocks such as dunite and olivine cumulates showing lighter isotope compositions than komatiite, lherzolite and pyroxenite samples. The data for the mineral separates shed light on the origin of these variations. Olivine and orthopyroxene display light δ60 Ni whereas clinopyroxene and garnet are isotopically heavy. This indicates that peridotite whole-rock δ60 Ni may be controlled by variations in modal mineralogy, with the prediction that mantle melts will display variable δ60 Ni values due to variations in residual mantle and cumulate mineralogy. Based on fertile peridotite xenoliths and Phanerozoic komatiite samples it is concluded that the upper mantle has a relatively homogeneous Ni isotope composition, with the best estimate of δ60Nimantle being 0.23 ± 0.06‰ (2 s.d.). Given that >99% of the Ni in the silicate Earth is located in the mantle, this also defines the Ni isotope composition of the Bulk Silicate Earth (BSE). This value is nearly identical to the results obtained for a suite of chondrites and iron meteorites (mean δ60 Ni 0.26 ± 0.12‰ and 0.29 ± 0.10‰, respectively) showing that the BSE is chondritic with respect to its Ni isotope composition, with little to no Ni mass-dependent isotope fractionation resulting from core formation.

The silicon isotope composition of the upper continental crust

NASA Astrophysics Data System (ADS)

Savage, Paul S.; Georg, R. Bastian; Williams, Helen M.; Halliday, Alex N.

2013-05-01

The upper continental crust (UCC) is the major source of silicon (Si) to the oceans and yet its isotopic composition is not well constrained. In an effort to investigate the degree of heterogeneity and provide a robust estimate for the average Si isotopic composition of the UCC, a representative selection of well-characterised, continentally-derived clastic sediments have been analysed using high-precision MC-ICPMS. Analyses of loess samples define a narrow range of Si isotopic compositions (δ30Si = -0.28‰ to -0.15‰). This is thought to reflect the primary igneous mineralogy and predominance of mechanical weathering in the formation of such samples. The average loess δ30Si is -0.22 ± 0.07‰ (2 s.d.), identical to average granite and felsic igneous compositions. Therefore, minor chemical weathering does not resolvably affect bulk rock δ30Si, and loess is a good proxy for the Si isotopic composition of unweathered, crystalline, continental crust. The Si isotopic compositions of shales display much more variability (δ30Si = -0.82‰ to 0.00‰). Shale Si isotope compositions do not correlate well with canonical proxies for chemical weathering, such as CIA values, but do correlate negatively with insoluble element concentrations and Al/Si ratios. This implies that more intensive or prolonged chemical weathering of a sedimentary source, with attendant desilicification, is required before resolvable negative Si isotopic fractionation occurs. Shale δ30Si values that are more positive than those of felsic igneous rocks most likely indicate the presence of marine-derived silica in such samples. Using the data gathered in this study, combined with already published granite Si isotope analyses, a weighted average composition of δ30Si = -0.25 ± 0.16‰ (2 s.d.) for the UCC has been calculated.

Mercury Abundances and Isotopic Compositions in the Murchison (CM) and Allende (CV)Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Lauretta, D. S.; Klaue, B.; Blum, J. D.; Buseck, P. R.

2001-01-01

The abundance and isotopic composition of Hg was determined in bulk samples of both the Murchison (CM) and Allende (CV) carbonaceous chondrites using single- and multi-collector inductively coupled plasma mass spectrometry (ICP-MS). The bulk abundances of Hg are 294 6 15 ng/g in Murchison and 30.0 6 1.5 ng/g in Allende. These values are within the range of previous measurements of bulk Hg abundances by neutron activation analysis (NAA). Prior studies suggested that both meteorites contain isotopically anomalous Hg, with d l 96/202Hg values for the anomalous, thermal-release components from bulk samples ranging from 2260 %o to 1440 9/00 in Murchison and from 2620 9/00 to 1540 9/00 in Allende (Jovanovic and Reed, 1976a; 1976b; Kumar and Goel, 1992). Our multi-collector ICP-MS measurements suggest that the relative abundances of all seven stable Hg isotopes in both meteorites are identical to terrestrial values within 0.2 to 0.5 9/00m. On-line thermal-release experiments were performed by coupling a programmable oven with the singlecollector ICP-MS. Powdered aliquots of each meteorite were linearly heated from room temperature to 900 C over twenty-five minutes under an Ar atmosphere to measure the isotopic composition of Hg released fiom the meteorites as a h c t i o n of temperature. In separate experiments, the release profiles of S and Se were determined simultaneously with Hg to constrain the Hg distribution within the meteorites and to evaluate the possibility of Se interferences in previous NAA studies. The Hg-release patterns differ between Allende and Murchison. The Hg-release profile for Allende contains two distinct peaks, at 225" and 343"C, whereas the profile for Murchison has only one peak, at 344 C. No isotopically anomalous Hg was detected in the thermal-release experiments at a precision level of 5 to 30 9/00, depending on the isotope ratio. In both meteorites the Hg peak at ;340"C correlates with a peak in the S-release profile. This correlation suggests that Hg is associated with S-bearing phases and, thus, that HgS is a major Hg-bearing phase in both meteorites. The Hg peak at 225 C for Allende is similar to release patterns of physically adsorbed Hg on silicate and metal grains.

The impact of pCO2 and climate on D/H and 13C/12C fractionation of higher-plant biomarkers: Implications for paleoclimate and paleoelevation reconstruction during global warm periods

NASA Astrophysics Data System (ADS)

Hren, M. T.; Tipple, B. J.; Pagani, M.

2012-12-01

Stable hydrogen isotope compositions (D/H) of plant biomarkers record the hydrogen isotopic composition of leaf water at the time of plant growth. However, the magnitude of the apparent hydrogen isotope fractionation between biomarkers and precipitation can vary due to soil- or leaf-water evaporation or differing water-use strategies. As a result, climate-induced changes in soil- or leaf-water evaporation rates and/or changes in plant assemblages during periods of global warming and high atmospheric CO2 could impact apparent carbon and hydrogen isotope fractionations. We measured hydrogen and carbon isotope ratios of long-carbon chain n-alkanes from modern and ~50 million year old fossil leaves preserved in paleo-Sierra Nevada riverine sediments to determine how climate and ecosystem differences during a period of extremely high pCO2 impact the magnitude and variability of D/H and 13C/12C ratios of leaf-waxes across a topographic gradient. δDalkanes (nC27 to nC31) of individual fossil and modern leaves decrease systematically across the topographic gradient and follow the change in the D/H of precipitation due to orographic lifting and continuous rainout. Using estimated values of Eocene δDprecip at the Pacific margin (-43 to -61‰), apparent fractionations (ɛalkane - precip) for Eocene angiosperm trees are similar to that seen for modern, humid environments (~ -106 to -124‰ ±10‰ 1σ), and more negative than observed in modern sun-exposed leaves in the Sierra Nevada (-96 to -102‰) or soils (-87 to -92‰). Single site variability in leaf-wax δD from individual fossil angiosperms can exceed 20‰, but is considerably smaller than observed for modern, mixed angiosperm/gymnosperm forests of the seasonally dry Sierra Nevada range. δ13Calkane values show little or no systematic variation across the range. However, carbon isotope discrimination in ancient and modern leaves is similar, suggesting strong climatic and weak pCO2 controls on D/H and 13C/12C fractionation. Site average δDalkane of multiple leaves closely mirrors bulk sediment δD values and suggests that the isotopic composition of bulk sediments provides a more robust record of local environmental and hydrologic conditions than analyses of biomarkers from individual leaves.

Gas geochemistry and preliminary CO2 output estimation from the island of Kos (Greece)

NASA Astrophysics Data System (ADS)

D'Alessandro, Walter; Daskalopoulou, Kyriaki; Calabrese, Sergio; Longo, Manfredi; Kyriakopoulos, Konstantinos; Gagliano, Antonina Lisa

2017-04-01

Several gas samples have been collected from natural gas manifestations at the island of Kos. Most of them are found underwater along the southern coast of the island. On land two anomalous degassing areas have been recognized. These are characterised by lack of vegetation and after long dry periods by the presence of sulfate salts efflorescences. Almost all the gases are CO2-dominated (CO2 ranging from 88 to 99%) with minor amounts of N2 (up to 7%) and CH4 (up to 2.6%). Only the on-land manifestations have also significant contents of H2 (up to 0.2%) and H2S (up to 0.3%). Only one underwater manifestation is N2-dominated (61-99%) with CH4 (0.6-11%) and low CO2 (0.1-26%). The isotopic composition of He shows values ranging from 0.84 to 6.72 R/RA indicating a sometimes strong mantle contribution with the highest values measured in two of the most strongly degassing areas (Paradise Beach and Volcania). C-isotopic composition of CO2 is in the range from -3.6 to 0.6 ‰ vs V-PDB with most of the values around -1‰ indicating a mixed mantle - limestones origin. Isotopic composition of CH4, ranging from -21.5 to 2.8‰ for C and from -143 to 36‰ for H, points to a geothermal origin with sometimes evident secondary oxidation processes. CO2-flux measurements showed values up to about 10,000 g/m2/day in the areas of Volcania and Kokkino Nero and up to about 50,000 g/m2/day at Paradise beach. Preliminary CO2 output estimations gave values of 8.8 and 4 tons/day for the first two areas respectively and of 2.7 tons/day for the latter. The total output of the island (15.5 tons/day) should be considered a minimum estimation because of the incomplete coverage of the area and is comparable to the other active volcanic/geothermal systems of Greece (Nisyros, Nea Kameni and Methana).

Oxygen isotope fractionation in the vacuum ultraviolet photodissociation of carbon monoxide: Wavelength, pressure and temperature dependency.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chakraborty, Subrata; Davis, Ryan; Ahmed, Musahid

Several absorption bands exist in the VUV region of Carbon monoxide (CO). Emission spectra indicate that these bands are all predissociative. An experimental investigation of CO photodissociation by vacuum ultraviolet photons (90 to 108 nm; ~13 to 11 eV) from the Advanced Light Source Synchrotron and direct measurement of the associated oxygen isotopic composition of the products are presented here. A wavelength dependency of the oxygen isotopic composition in the photodissociation product was observed. Slope values (δ'{sup 18}O/ δ'{sup 17}O) ranging from 0.76 to 1.32 were observed in oxygen three-isotope space (δ'{sup 18}O vs. δ'{sup 17}O) which correlated with increasingmore » synchrotron photon energy, and indicate a dependency of the upper electronic state specific dissociation dynamics (e.g., perturbation and coupling associated with a particular state). An unprecedented magnitude in isotope separation was observed for photodissociation at the 105 and 107 nm synchrotron bands and are found to be associated with accidental predissociation of the vibrational states ({nu} = 0 and 1) of the upper electronic state E{sup 1}Π. For each synchrotron band, a large (few hundred per mil) extent of isotopic fractionation was observed and the range of fractionation is a combination of column density and exposure time. A significant temperature dependency in oxygen isotopic fractionation was observed, indicating a rotational level dependency in the predissociation process.« less

Sr isotopic variations in Upper Proterozoic carbonates from Svalbard and East Greenland

DOE Office of Scientific and Technical Information (OSTI.GOV)

Derry, L.A.; Keto, L.S.; Jacobsen, S.B.

1989-09-01

The authors report initial {sup 87}Sr/{sup 86}Sr values from an Upper Proterozoic carbonate succession from Svalbard and East Greenland. This succession, now tectonically separated into three sequences, is thick, relatively continuous, and well preserved. The relative ages of the samples from within the basin are well constrained by litho-, bio-, and chemostratigraphic techniques. The data from this study and related data from the literature are used to construct a curve of {sup 87}Sr/{sup 86}Sr for Upper Proterozoic seawater. The new data reported in this study substantially improve the isotopic record of Sr in seawater for the period between 650 andmore » 800 Ma. The data indicate that {Delta}{sup 87}Sr values of seawater were variable but low ({Delta}{sup 87}Sr {approximately}{minus}500 to {minus}250) between 900 and 650 Ma, and rose rapidly to {approximately} +30 by 600 Ma. The range of variation of {Delta}{sup 87}Sr in seawater during the Riphean-Vendian exceeds the entire range of {Delta}{sup 87}Sr in seawater during the Phanerozoic. While variation in the average isotopic composition of Sr delivered to the oceans by rivers can account for some of the observed range, changes in the ratio of submarine hydrothermal flux to river water (continental) flux are responsible for the large variation in seawater Sr isotopic composition. Changes in the continental flux of Sr to the oceans can be related to tectonic factors. Large changes in the hydrothermal flux to river water flux ratio indicated by the data could have significant consequences for the chemistry of the ocean-atmosphere system.« less

Seasonality and growth patterns using isotope sclerochronology in shells of the Pliocene scallop Chesapecten madisonius

NASA Astrophysics Data System (ADS)

Goewert, Ann E.; Surge, Donna

2008-10-01

Growth lines and variation in oxygen and carbon isotope ratios (δ18O and δ13C) in shells of the Pliocene scallop Chesapecten madisonius preserve seasonal chronologies of biological and environmental change. This study evaluated whether (1) prominent growth lines were formed annually, and (2) growth rates estimated using isotope sclerochronology were comparable to rates estimated using visual inspection (measuring the width between external growth lines). We compared both techniques for estimating growth rates and age on three late to mid-Pliocene C. madisonius shells. The first approach located prominent growth lines on the δ18O time series, and differentiated between annual and non-annual (disturbance) growth lines. The second approach assumed all prominent lines were annual. This comparison showed that visual inspection underestimated growth rates and overestimated age. Seasonal timing of annual growth line formation using isotope sclerochronology provided unexpected results. Because this region fell within the warm-temperate paleobiogeographic province, we predicted annual lines formed during summers (most negative δ18O values). Instead, annual growth lines coincided with the most positive δ18O values (winter), typical of bivalves from cold-temperate regions. Moreover, shells recorded seasonal temperatures ranging from 3.2-20.8°C, a range lower than the thermal regime defined for warm-temperate environments (8-25°C). Possibly, the Sea Slope Gyre, which mixed eddies and cold filaments of the Labrador Current and warm waters of the Gulf Stream, penetrated the warm-temperate environment in this region. Alternatively, warm-water fauna from the zoogeographic Carolinian subprovince migrated northward and endured by virtue of warm summer temperatures. Regardless of the explanation, our findings provide a glimpse of mid-latitude seasonal temperature range for a warm climate episode during the mid-Pliocene.

Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oerter, Erik; Singleton, Michael; Davisson, Lee

The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

DOE PAGES

Oerter, Erik; Singleton, Michael; Davisson, Lee

2017-10-22

The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

Coprecipitation and isotopic fractionation of boron in modern biogenic carbonates

NASA Astrophysics Data System (ADS)

Vengosh, Avner; Kolodny, Yehoshua; Starinsky, Abraham; Chivas, Allan R.; McCulloch, Malcolm T.

1991-10-01

The abundances and isotopic composition of boron in modern, biogenic calcareous skeletons from the Gulf of Elat, Israel, the Great Barrier Reef, Australia, and in deep-sea sediments have been examined by negative thermal-ionization mass spectrometry. The selected species (Foraminifera, Pteropoda, corals, Gastropoda, and Pelecypoda) yield large variations in boron concentration that range from 1 ppm in gastropod shells to 80 ppm in corals. The boron content of the biogenic skeletons is independent of mineralogical composition and is probably related to biological (vital) effects. The δ11B values of the carbonates range from 14.2 to 32.2%. (relative to NBS SRM 951) and overlap with the δ11B values of modern deep-sea carbonate sediments ( δ11B = 8.9 to 26.2%.). The variations of δ11B may be controlled by isotopic exchange of boron species in which 10B is preferentially partitioned into the tetrahedral species, and coprecipitation of different proportions of trigonal and tetrahedral species in the calcium carbonates. Carbonates with low δ11B values (~ 15%.) may indicate preferential incorporation of tetrahedral species, whereas the higher δ11B values (~30%.) may indicate (1) uptake of both boron species assuming equilibrium with seawater (2) preferential incorporation of B(OH) 4- from in situ high-pH internal fluids of organisms that are isolated from seawater. The B content and δ11B values of deep-sea sediments, Foraminifera tests, and corals are used to estimate the global oceanic sink of elemental boron by calcium carbonate deposition. As a result of enrichment of B in corals, a substantially higher biogenic sink of 6.4 ± 0.9 × 10 10 g/yr is calculated for carbonates. This is only slightly lower than the sink for desorbable B in marine sediments (10 × 10 10 g/yr) and approximately half that of altered oceanic crust (14 × 10 10 g/yr). Thus, carbonates are an important sink for B in the oceans being ~20% of the total sinks. The preferential incorporation of 10B into calcium carbonate results in oceanic 11B-enrichment, estimated as 1.2 ± 0.3 × 10 12 per mil · g/yr. The boron-isotope composition of authigenic, well-preserved carbonate skeletons may provide a useful tool to record secular boron-isotope variations in seawater at various times in the geological record. The potential use of boron-isotope geochemistry in skeletons as a tracer for palaeoenvironments is demonstrated in Ostracoda and Foraminifera from the Gulf of Carpentaria, Australia. The δ11B values of glacial-age, buried skeletons (4.0 and 4.9%., respectively) are lower than that of their modern equivalents (17.6 and 13.3%., respectively). This may reflect a "terrestrial" boron-isotope signature of the water in the gulf during the Late Quaternary when it was isolated from the ocean.

Elucidating the nutritional dynamics of fungi using stable isotopes.

PubMed

Mayor, Jordan R; Schuur, Edward A G; Henkel, Terry W

2009-02-01

Mycorrhizal and saprotrophic (SAP) fungi are essential to terrestrial element cycling due to their uptake of mineral nutrients and decomposition of detritus. Linking these ecological roles to specific fungi is necessary to improve our understanding of global nutrient cycling, fungal ecophysiology, and forest ecology. Using discriminant analyses of nitrogen (delta(15)N) and carbon (delta(13)C) isotope values from 813 fungi across 23 sites, we verified collector-based categorizations as either ectomycorrhizal (ECM) or SAP in > 91% of the fungi, and provided probabilistic assignments for an additional 27 fungi of unknown ecological role. As sites ranged from boreal tundra to tropical rainforest, we were able to show that fungal delta(13)C (26 sites) and delta(15)N (32 sites) values could be predicted by climate or latitude as previously shown in plant and soil analyses. Fungal delta(13)C values are likely reflecting differences in C-source between ECM and SAP fungi, whereas (15)N enrichment of ECM fungi relative to SAP fungi suggests that ECM fungi are consistently delivering (15)N depleted N to host trees across a range of ecosystem types.

New bulk and in situ isotopic and elemental geochemistry of shallow drill core from Atlantis Massif: insights into the sources and paths of fluids and clasts

NASA Astrophysics Data System (ADS)

Bilenker, L.; Weis, D.; Scoates, J. S.

2017-12-01

We present stable Fe and radiogenic isotope and complementary trace element data for samples from Atlantis Massif. This oceanic core complex is located at 30°N where the Atlantis Transform Fault intersects the Mid-Atlantic Ridge (MAR) and is associated with the Lost City Hydrothermal Field (LCHF). It is a unique place to investigate the abiotic and biotic geochemical processes that play a role in the alteration of both crustal and mantle seafloor rocks. The samples analyzed represent a shallow (<15 m) survey of five drill sites (IODP Expedition 357) within Atlantis Massif, varying in distance from the LCHF and MAR. Analyses were performed on a sample set spanning a wide range in degree of alteration and lithology. Bulk measurements involved dissolving whole rock powders, whereas in situ analyses were performed on digested microdrilled samples or by laser ablation. Bulk rock Fe isotope values (n = 34) are correlated with loss-on-ignition (LOI) by sample lithology and location relative to LCHF. Using LOI as a proxy for degree of alteration, this observation indicates that the Fe isotope systematics of seafloor crustal and mantle rocks preserve indicators of fluid flow and source. The Hf and Nd isotope compositions for various lithologies form all analyzed sites are homogeneous, indicating minimal alteration of these isotopic systems. Bulk Sr values provide insight into elemental exchange between seawater and the surface of Atlantis Massif and bulk Pb isotopes allow for fingerprinting of the source of basalt breccias through comparison with published Pb isotope values of MAR basalts. The new results cluster around the Pb, Hf, Nd isotopic composition of mid-ocean ridge basalt from 30.68°N and do not match samples north or south of that location. In situ Fe isotope data within three altered samples reflect varying degrees of hydrothermal and seawater interaction, where the Fe isotope ratios within each sample are likely correlated with extent of exchange or redox. Laser trace element and Pb isotope data in progress will allow us to investigate this further. This study contributes to our understanding of element mobility and mass transfer during chemical reactions within the seafloor, provides insight into the source of the lithological units and fluid flow, and allows for quantification of alteration processes.

Discriminating fluid source regions in orogenic gold deposits using B-isotopes

NASA Astrophysics Data System (ADS)

Lambert-Smith, James S.; Rocholl, Alexander; Treloar, Peter J.; Lawrence, David M.

2016-12-01

The genesis of orogenic gold deposits is commonly linked to hydrothermal ore fluids derived from metamorphic devolatilization reactions. However, there is considerable debate as to the ultimate source of these fluids and the metals they transport. Tourmaline is a common gangue mineral in orogenic gold deposits. It is stable over a very wide P-T range, demonstrates limited volume diffusion of major and trace elements and is the main host of B in most rock types. We have used texturally resolved B-isotope analysis by secondary ion mass spectrometry (SIMS) to identify multiple fluid sources within a single orogenic gold ore district. The Loulo Mining District in Mali, West Africa hosts several large orogenic gold ore bodies with complex fluid chemistry, associated with widespread pre-ore Na- and multi-stage B-metasomatism. The Gara deposit, as well as several smaller satellites, formed through partial mixing between a dilute aqueous-carbonic fluid and a hypersaline brine. Hydrothermal tourmaline occurs as a pre-ore phase in the matrix of tourmalinite units, which host mineralization in several ore bodies. Clasts of these tourmalinites occur in mineralized breccias. Disseminated hydrothermal and vein hosted tourmaline occur in textural sites which suggest growth during and after ore formation. Tourmalines show a large range in δ11B values from -3.5 to 19.8‰, which record a change in fluid source between paragenetic stages of tourmaline growth. Pre-mineralization tourmaline crystals show heavy δ11B values (8-19.8‰) and high X-site occupancy (Na ± Ca; 0.69-1 apfu) suggesting a marine evaporite source for hydrothermal fluids. Syn-mineralization and replacement phases show lighter δ11B values (-3.5 to 15.1‰) and lower X-site occupancy (0.62-0.88 apfu), suggesting a subsequent influx of more dilute fluids derived from devolatilization of marine carbonates and clastic metasediments. The large, overlapping range in isotopic compositions and a skew toward the opposing population in the δ11B data for both tourmaline groups reflects continual tourmaline growth throughout mineralization, which records the process of fluid mixing. A peak in δ11B values at ∼8‰ largely controlled by tourmalines of syn- to post-ore timing represents a mixture of the two isotopically distinct fluids. This paper demonstrates that B-isotopes in tourmaline can be instrumental in interpreting complex and dynamic hydrothermal systems. The importance of B as an integral constituent of orogenic ore forming fluids and as a gangue phase in orogenic gold deposits makes B-isotope analysis a powerful tool for testing the level of source region variability in these fluids, and by extension, that of metal sources.

Quantification of Labile Soil Mercury by Stable Isotope Dilution Techniques

NASA Astrophysics Data System (ADS)

Shetaya, Waleed; Huang, Jen-How; Osterwalder, Stefan; Alewell, Christine

2016-04-01

Mercury (Hg) is a toxic element that can cause severe health problems to humans. Mercury is emitted to the atmosphere from both natural and anthropogenic sources and can be transported over long distances before it is deposited to aquatic and terrestrial environments. Aside from accumulation in soil solid phases, Hg deposited in soils may migrate to surface- and ground-water or enter the food chain, depending on its lability. There are many operationally-defined extraction methods proposed to quantify soil labile metals. However, these methods are by definition prone to inaccuracies such as non-selectivity, underestimation or overestimation of the labile metal pool. The isotopic dilution technique (ID) is currently the most promising method for discrimination between labile and non-labile metal fractions in soil with a minimum disturbance to soil-solid phases. ID assesses the reactive metal pool in soil by defining the fraction of metal both in solid and solution phases that is isotopically-exchangeable known as the 'E-value'. The 'E-value' represents the metal fraction in a dynamic equilibrium with the solution phase and is potentially accessible to plants. This is carried out by addition of an enriched metal isotope to soil suspensions and quantifying the fraction of metal that is able to freely exchange with the added isotope by measuring the equilibrium isotopic ratio by ICP-MS. E-value (mg kg-1) is then calculated as follows: E-Value = (Msoil/ W) (CspikeVspike/ Mspike) (Iso1IAspike -Iso2IAspikeRss / Iso2IAsoil Rss - Iso1IAsoil) where M is the average atomic mass of the metal in the soil or the spike, W is the mass of soil (kg), Cspike is the concentration of the metal in the spike (mg L-1), Vspike is the volume of spike (L), IA is isotopic abundance, and Rss is the equilibrium ratio of isotopic abundances (Iso1:Iso2). Isotopic dilution has been successfully applied to determine E-values for several elements. However, to our knowledge, this method has not yet been applied to estimate the labile pool of mercury in contaminated soils. We performed a series of soil incubations spiked with 196Hg2+aiming at measuring and modelling the progressive assimilation of Hg ions into less labile forms. Soils with a wide range of characteristics are taken for our research purpose, inclusive of Hg concentrations ranging from 0.1 to 390 mg kg-1, pH between 3.5 - 7.5 and total organic carbon (TOC) between 2.5 - 8 %. In parallel, the labile pool of Hg estimated using ID will be compared with that determined using conventional extraction methods, e.g. sequential extraction procedures. These altogether allows us to answer (1) how the E-value of Hg in soils is comparable to those estimated based on selective extraction methods, (2) how the labile Hg correlates with the total soil Hg, soil pH and TOC, and (3) how the solubility of added Hg (e.g. via rainfall) decreased in soils of different properties during aging. The obtained results fills the knowledge gap concerning Hg biogeochemistry in the terrestrial environment and serves as a basis for estimating (and predicting) the risk of soil Hg diffusion from a point source to the adjacent environments.

Stable isotope ratio mass spectrometry and physical comparison for the forensic examination of grip-seal plastic bags.

PubMed

Taylor, Erica; Carter, James F; Hill, Jenny C; Morton, Carolyn; Daeid, Niamh Nic; Sleeman, Richard

2008-05-20

Plastic bags are frequently used to package drugs, explosives and other contraband. There exists, therefore, a requirement in forensic casework to compare bags found at different locations. This is currently achieved almost exclusively by the use of physical comparisons such as birefringence patterns. This paper discusses some of the advantages and shortcomings of this approach, and presents stable isotope ratio mass spectrometry (IRMS) as a supplementary tool for effecting comparisons of this nature. Carbon and hydrogen isotopic data are presented for sixteen grip-seal plastic bags from a wide range of sources, in order to demonstrate the range of values which is likely to be encountered. Both isotopic and physical comparison (specifically birefringence) techniques are then applied to the analysis of rolls of bags from different manufacturing lots from a leading manufacturer. Both approaches are able to associate bags from a common production batch. IRMS can be applied to small fragments which are not amenable to physical comparisons, and is able to discriminate bags which could be confused using birefringence patterns alone. Similarly, in certain cases birefringence patterns discriminate bags with similar isotopic compositions. The two approaches are therefore complementary. When more than one isotopically distinct region exists within a bag (e.g. the grip-seal is distinct from the body) the ability to discriminate and associate bags is greatly increased.

Converting isotope ratios to diet composition - the use of mixing models - June 2010

EPA Science Inventory

One application of stable isotope analysis is to reconstruct diet composition based on isotopic mass balance. The isotopic value of a consumer’s tissue reflects the isotopic values of its food sources proportional to their dietary contributions. Isotopic mixing models are used ...

Selenium stable isotope investigation into selenium biogeochemical cycling in a lacustrine environment: Sweitzer Lake, Colorado.

PubMed

Clark, Scott K; Johnson, Thomas M

2010-01-01

We present a comprehensive set of Se concentration and isotope ratio data collected over a 3-yr period from dissolved, sediment-hosted, and organically bound Se in a Se-contaminated lake and littoral wetland. Median isotope ratios of these various pools of Se spanned a narrow isotopic range (delta80/76Se(SRM-3149)) = 1.14-2.40 per thousand). Selenium (VI) reduction in the sediments is an important process in this system, but its isotopic impact is muted by the lack of direct contact between surface waters and reduction sites within sediments. This indicates that using Se isotope data as an indicator of microbial or abiotic Se oxyanion reduction is not effective in this or other similar systems. Isotopic data suggest that most Se(IV) in the lake originates from oxidation of organically bound Se rather than directly through Se(VI) reduction. Mobilization of Se(VI) from bedrock involves only a slight isotopic shift. Temporally constant isotopic differences observed in Se(VI) from two catchment areas suggest the potential for tracing Se(VI) from different source areas. Phytoplankton isotope ratios are close to those of the water, with a small depletion in heavy isotopes (0.56 per thousand). Fish tissues nearly match the phytoplankton, being only slightly depleted in the heavier isotopes. This suggests the potential for Se isotopes as migration indicators. Volatile, presumably methylated Se was isotopically very close to median values for phytoplankton and macrophytes, indicating a lack of isotopic fractionation during methylation.

Oxygen isotope study of the Long Valley magma system, California: isotope thermometry and convection in large silicic magma bodies

NASA Astrophysics Data System (ADS)

Bindeman, Ilya; Valley, John

2002-07-01

Products of voluminous pyroclastic eruptions with eruptive draw-down of several kilometers provide a snap-shot view of batholith-scale magma chambers, and quench pre-eruptive isotopic fractionations (i.e., temperatures) between minerals. We report analyses of oxygen isotope ratio in individual quartz phenocrysts and concentrates of magnetite, pyroxene, and zircon from individual pumice clasts of ignimbrite and fall units of caldera-forming 0.76 Ma Bishop Tuff (BT), pre-caldera Glass Mountain (2.1-0.78 Ma), and post-caldera rhyolites (0.65-0.04 Ma) to characterize the long-lived, batholith-scale magma chamber beneath Long Valley Caldera in California. Values of δ18O show a subtle 1‰ decrease from the oldest Glass Mountain lavas to the youngest post-caldera rhyolites. Older Glass Mountain lavas exhibit larger ( 1‰) variability of δ18O(quartz). The youngest domes of Glass Mountain are similar to BT in δ18O(quartz) values and reflect convective homogenization during formation of BT magma chamber surrounded by extremely heterogeneous country rocks (ranging from 2 to +29‰). Oxygen isotope thermometry of BT confirms a temperature gradient between "Late" (815 °C) and "Early" (715 °C) BT. The δ18O(quartz) values of "Early" and "Late" BT are +8.33 and 8.21‰, consistent with a constant δ18O(melt)=7.8+/-0.1‰ and 100 °C temperature difference. Zircon-melt saturation equilibria gives a similar temperature range. Values of δ18O(quartz) for different stratigraphic units of BT, and in pumice clasts ranging in pre-eruptive depths from 6 to 11 km (based on melt inclusions), and document vertical and lateral homogeneity of δ18O(melt). Worldwide, five other large-volume rhyolites, Lava Creek, Lower Bandelier, Fish Canyon, Cerro Galan, and Toba, exhibit equal δ18O(melt) values of earlier and later erupted portions in each of the these climactic caldera-forming eruptions. We interpret the large-scale δ18O homogeneity of BT and other large magma chambers as evidence of their longevity (>105 years) and convection. However, remaining isotopic zoning in some quartz phenocrysts, trace element gradients in feldspars, and quartz and zircon crystal size distributions are more consistent with far shorter timescales (102-104 years). We propose a sidewall-crystallization model that promotes convective homogenization, roofward accumulation of more evolved and stagnant, volatile-rich liquid, and develops compositional and temperature gradients in pre-climactic magma chamber. Crystal + melt + gas bubbles mush near chamber walls of variable δ18O gets periodically remobilized in response to chamber refill by new hotter magmas. One such episode of chamber refill by high-Ti, Sr, Ba, Zr, and volatile-richer magma happened 103-104 years prior to the 0.76-Ma caldera collapse that caused magma mixing at the base, mush thawing near the roof and walls, and downward settling of phenocrysts into this hybrid melt.

Theoretical estimates of equilibrium sulfur isotope effects in aqueous sulfur systems: Highlighting the role of isomers in the sulfite and sulfoxylate systems

NASA Astrophysics Data System (ADS)

Eldridge, D. L.; Guo, W.; Farquhar, J.

2016-12-01

We present theoretical calculations for all three isotope ratios of sulfur (33S/32S, 34S/32S, 36S/32S) at the B3LYP/6-31+G(d,p) level of theory for aqueous sulfur compounds modeled in 30-40H2O clusters spanning the range of sulfur oxidation state (Sn, n = -2 to +6) for estimating equilibrium fractionation factors in aqueous systems. Computed 34β values based on major isotope (34S/32S) reduced partition function ratios (RPFRs) scale to a first order with sulfur oxidation state and coordination, where 34β generally increase with higher oxidation state and increasing coordination of the sulfur atom. Exponents defining mass dependent relationships based on β values (x/34κ = ln(xβ)/ln(34β), x = 33 or 36) conform to tight ranges over a wide range of temperature for all aqueous compounds (33/34κ ≈ 0.5148-0.5159, 36/34κ ≈ 1.89-1.90 from T ⩾ 0 °C). The exponents converge near a singular value for all compounds at the high temperature limit (33/34κT→∞ = 0.51587 ± 0.00003 and 36/34κT→∞ = 1.8905 ± 0.0002; 1 s.d. of all computed compounds), and typically follow trends based on oxidation state and coordination similar to those seen in 34β values at lower temperatures. Theoretical equilibrium fractionation factors computed from these β-values are compared to experimental constraints for HSO3-T(aq)/SO2(g, aq), SO2(aq)/SO2(g), H2S(aq)/H2S(g), H2S(aq)/HS-(aq), SO42-(aq)/H2ST(aq), S2O32-(aq) (intramolecular), and S2O32-(aq)/H2ST(aq), and generally agree within a reasonable estimation of uncertainties. We make predictions of fractionation factors where other constraints are unavailable. Isotope partitioning of the isomers of protonated compounds in the sulfite and sulfoxylate systems depend strongly on whether protons are bound to either sulfur or oxygen atoms. The magnitude of the HSO3-T/SO32- major isotope (34S/32S) fractionation factor is predicted to increase with temperature from 0 to 70 °C due to the combined effects of the large magnitude (HS)O3-/SO32- fractionation factor (1000ln34α(HS)bisulfite-sulfite = 19.9‰, 25 °C) relative to the (HO)SO2-/SO32- fractionation factor (1000ln34α(HO)bisulfite-sulfite = -2.2‰, 25 °C), and the increased stability of the (HS)O3- isomer with increasing temperature. We argue that isomerization phenomenon should be considered in models of the sulfur cycle, including models that describe the overall sulfur isotope fractionations associated with microbial metabolism (e.g., microbial sulfate reduction).

Multiple sources of selenium in ancient seafloor hydrothermal systems: Compositional and Se, S, and Pb isotopic evidence from volcanic-hosted and volcanic-sediment-hosted massive sulfide deposits of the Finlayson Lake District, Yukon, Canada

NASA Astrophysics Data System (ADS)

Layton-Matthews, Daniel; Leybourne, Matthew I.; Peter, Jan M.; Scott, Steven D.; Cousens, Brian; Eglington, Bruce M.

2013-09-01

Volcanic-hosted massive sulfide (VHMS) and volcanic-sediment-hosted massive sulfide (VSHMS; i.e., hosted by both volcanic and sedimentary rocks) deposits in the Finlayson Lake District, Yukon, Canada, provide a unique opportunity to study the influence of seafloor and sub-seafloor hydrothermal processes on the formation of Se-poor (GP4F VHMS deposit; 7 ppm Se average), intermediate (Kudz Ze Kayah—KZK VHMS deposit; 200 ppm Se average), and Se-enriched (Wolverine VSHMS deposit; 1100 ppm Se average) mineralization. All three deposits are hosted by mid-Paleozoic (˜360-346 Ma) felsic volcanic rocks, but only the Wolverine deposit has voluminous coeval carbonaceous argillites (black shales) in the host rock package. Here we report the first application of Se isotope analyses to ancient seafloor mineralization and use these data, in conjunction with Pb and S isotope analyses, to better understand the source(s) and depositional process(es) of Se within VHMS and VSHMS systems. The wide range of δ82Se (-10.2‰ to 1.3‰, relative to NIST 3149), δ34S (+2.0‰ to +12.8‰ CDT), and elevated Se contents (up to 5865 ppm) within the Wolverine deposit contrast with the narrower range of δ82Se (-3.8‰ to -0.5‰), δ34S (9.8‰ to 13.0‰), and lower Se contents (200 ppm average) of the KZK deposit. The Wolverine and KZK deposits have similar sulfide depositional histories (i.e., deposition at the seafloor, with concomitant zone refining). The Se in the KZK deposit is magmatic (leaching or degassing) in origin, whereas the Wolverine deposit requires an additional large isotopically negative Se source (i.e. ˜-15‰ δ82Se). The negative δ82Se values for the Wolverine deposit are at the extreme light end for measured terrestrial samples, and the lightest observed for hypogene sulfide minerals, but are within calculated equilibrium values of δ82Se relative to NIST 3149 (˜30‰ at 25 °C between SeO4 and Se2-). We propose that the most negative Se isotope values at the Wolverine deposit record the δ82Se of the Se-source, and that the wide range in δ82Se values results from the combined effects of thermal and chemical degradation and Se-loss from the carbonaceous argillite source to a hydrothermal fluid (including magmatic Se i.e., leached and/or magmatic-hydrothermal) with deposition at or near the paleoseafloor. Pristine unaltered black shales show little variation in δ82Se relative to bulk earth; Se accumulation and fractionation to more negative isotopic values is interpreted to have been produced by post-sediment deposition, but pre-ore stage, reduction of seawater Se within the black shales.

A multi-proxy isotope study (δ41K, δ26Mg, 87Sr/86Sr) of low-temperature oceanic crust alteration: the Troodos Ophiolite and Ocean Drilling Program Hole 801C

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Higgins, J. A.

2017-12-01

Low-temperature alteration of oceanic crust plays an important role in a number of geochemical cycles, thus modulating the chemical composition of the oceans. In particular, it has been established that low-temperature (<150oC) alteration of basalt is a major sink of seawater potassium. However, little is known about the effects of this process on the potassium isotope composition of seawater, which is 0.5‰ enriched relative to bulk silicate Earth (δ41KBSE=-0.54‰). Here we measure a number of isotope systems (δ41K, δ26Mg, 87Sr/86Sr) in both host rock and vein material from the upper volcanic section of Cretaceous (Troodos Ophiolite) and Jurassic (ODP 801C) oceanic crust using a MC-ICP-MS. The goal is to estimate the K isotopic fractionation associated with basalt alteration in low-temperature conditions, and how it might affect the K isotope enrichment of seawater relative to BSE. We find that marine hydrothermal samples from Troodos and ODP site 801C are enriched in potassium relative to the unaltered glass compositions and have δ41K values both higher and lower than BSE, ranging from -0.45‰ to -0.69‰ (n = 9) and -0.32‰ to -0.71‰ (n = 5), respectively. The low measured δ41K values could represent 1) fractionation (α<1) of K isotopes during uptake from seawater (δ41KSW 0‰), or 2) remobilized mantle-sourced K (δ41KBSE=-0.54‰) from deeper within the ophiolite sequence. Measurements of δ26Mg (n=15) and 87Sr/86Sr (n=12) in these samples yield enriched values relative to bulk silicate Earth, suggesting that alteration of oceanic crust likely happened under high water-to-rock ratios in both Troodos and ODP 801C, and that the added potassium is seawater-sourced. We thus suggest that the isotopically light δ41K values measured in both sites are associated with the formation of secondary clays enriched in the 39K isotope. This light isotope enrichment could be intensified if seawater K sourcing is a diffusion-limited process, as aqueous potassium diffusion has been associated with K isotope fractionations between 0.9967 and 0.9984. Our results indicate that the uptake of potassium in altered oceanic crust could be responsible, in part, for the observed K isotope enrichment of seawater relative to bulk silicate Earth.

Results from stable isotope investigations of river waters in Western Croatia

NASA Astrophysics Data System (ADS)

Häusler, H.; Frančišković-Bilinski, S.; Rank, D.; Stadler, P.; Bilinski, H.

2012-04-01

During a campaign lasting from 27 October to 21 November 2010, sixty-one water samples were taken from the Kupa River, the catchment of which is about ten thousand square kilometres in size. Due to the fact that the upper tributaries of e.g. the Čabranka-, Dobra-, Korana-, Mrežnica- and Petrinjčica River comprise karstified Mesozoic carbonate formations, the hydrogeologic catchment of Kupa River extends the hydrologic one by far. The upper Kupa River is mainly charged by springs from big karst reservoirs in the Gorski Kotar mountain range, where a mean groundwater residence time of up to one year has to be considered. The rapid increase of discharge of these tributary rivers results from the rapid increase of discharge of karst wells after melting in springtime as well as from storm events. In general, the minimum mean discharge for all hydrographs in July reveals a dry summer season, with the maximum discharge in August/September resulting from an increase in precipitation. We interpret the d O-18 values of the Čabranka River (of about -8, 07‰) as signals from maritime precipitation in this karstified catchment area. The d O-18 value of upper Kupa River diminishes along its course from -8,09‰ near Osilnica to -9,06‰ west of Karlovac. After the inflow of tributaries south of Karlovac, the oxygen isotope ratio of Kupa River water reveals a significant change because the d O-18 values of the Dobra-, Korana- and Mrežnica River range from -10,45‰ to -9,58‰ . Due to the fact that the catchment of Dobra- and Korana River rises between 400 and 880 metres, we interpret the lower d O-18 values of river waters from recharge areas at those low mean altitudes as not caused by an altitude effect, but instead by precipitation out of more continental air masses. Our interpretation of stable isotope ratios in river waters is based on the relation between the weighted mean d O-18 and the altitude obtained from stations of the Global Network of Isotopes in Precipitation (GNIP), revealing an approximate vertical d O-18 gradient of -0,30‰ per 100 m, as reported by Vreča et al. (2006). In addition, this stable isotope data for the GNIP station Zavižan predominantly indicates precipitation from the Adriatic coast, in contrary to the GNIP station Zagreb, the precipitation of which is more influenced by continental air masses. Due to the lack of local precipitation isotope data in the Kupa drainage basin it is not possible to directly analyse the modification of the isotopic signature and its temporal variation in river waters. To sum up, the isotopic composition of river waters in the Kupa Basin is controlled by two factors: the mean altitude of the recharge areas, and differences in the isotope composition of air moisture of more maritime or more continental influence. Along with use for hydrological investigations, the presented isotope data set can serve as a base line of isotope data for assessing future climate impacts within the Kupa Basin, such as temperature changes and change of precipitation distribution. Vreča, P., Bronić, I. K., Horvatinčić, N., Baresić, J. (2006): Isotopic characteristics of precipitation in Slovenia and Croatia: Comparison of continental and marine stations.- Journal of Hydrology, 330, 457-469.

Amino Acid Isotope Incorporation and Enrichment Factors in Pacific Bluefin Tuna, Thunnus orientalis

PubMed Central

Bradley, Christina J.; Madigan, Daniel J.; Block, Barbara A.; Popp, Brian N.

2014-01-01

Compound specific isotopic analysis (CSIA) of amino acids has received increasing attention in ecological studies in recent years due to its ability to evaluate trophic positions and elucidate baseline nutrient sources. However, the incorporation rates of individual amino acids into protein and specific trophic discrimination factors (TDFs) are largely unknown, limiting the application of CSIA to trophic studies. We determined nitrogen turnover rates of individual amino acids from a long-term (up to 1054 days) laboratory experiment using captive Pacific bluefin tuna, Thunnus orientalis (PBFT), a large endothermic pelagic fish fed a controlled diet. Small PBFT (white muscle δ15N∼11.5‰) were collected in San Diego, CA and transported to the Tuna Research and Conservation Center (TRCC) where they were fed a controlled diet with high δ15N values relative to PBFT white muscle (diet δ15N∼13.9‰). Half-lives of trophic and source amino acids ranged from 28.6 to 305.4 days and 67.5 to 136.2 days, respectively. The TDF for the weighted mean values of amino acids was 3.0 ‰, ranging from 2.2 to 15.8 ‰ for individual combinations of 6 trophic and 5 source amino acids. Changes in the δ15N values of amino acids across trophic levels are the underlying drivers of the trophic 15N enrichment. Nearly all amino acid δ15N values in this experiment changed exponentially and could be described by a single compartment model. Significant differences in the rate of 15N incorporation were found for source and trophic amino acids both within and between these groups. Varying half-lives of individual amino acids can be applied to migratory organisms as isotopic clocks, determining the length of time an individual has spent in a new environment. These results greatly enhance the ability to interpret compound specific isotope analyses in trophic studies. PMID:24465724

Patterns of mortality among South Florida Manatees: Evidence from oxygen, sulfur and deuterium stable isotopes

NASA Astrophysics Data System (ADS)

MacAvoy, S. E.; Bacalan, V.; Kazantseva, M.; Rhodes, J.; Kim, K.

2012-12-01

The Florida manatee (Trichechus manatus latirostris) is an endangered marine mammal whose coastal habitat has been heavily altered by human development. Sources of mortality include anthropogenic and environmental causes. Necropsies were completed on 75 deceased individuals, and tissues, including bone samples, were collected for later analysis. This study investigates the utility of manatee bone stable oxygen (δ18O), sulfur (δ34S) and deuterium (δD) for determining where the animals lived (which may not be where they where their bodies were recovered), and the relative importance of marine versus freshwater for the individual animals. The isotopes can provide a "geochemical map" showing the distribution of mortality, aiding in the evaluation of geographical patterns in mortality. The δ18O signatures of the bones ranged from 14 to 18.5‰, with no significant difference between male and female mean values. δ18O significantly decreased with increasing latitude (p=.0016), a trend positively correlated with coastal Florida seawater δ18O literature values obtained from the NASA Global Seawater Oxygen-18 Database (http://data.giss.nasa.gov/o18data/) and the EAIA stable isotope database (http://www.univie.ac.at/cartography/project/wiser/). Bone δ34S indicated the influence of marine versus coastal freshwater dietary sources on the animals. Most individuals showed 34S-depleted signatures, which indicated a non-marine sulfur source; however some individuals clearly had taken up marine sulfate (mean 4.9 ± 3.7‰, range 0.8 to 13.8‰). Deuterium values were not available at the time this abstract was written, however we hypothesize that those values will co-vary with δ18O. We conclude that manatee diets are based on both marine and freshwater sources, but freshwater sources exert more influence. Marine water and manatee δ18O co-vary with latitude, suggesting that stable oxygen isotopes may be useful indicators of the latitude where manatees lived.

Principles and limitations of stable isotopes in differentiating organic and conventional foodstuffs: 1. Plant products.

PubMed

Inácio, Caio Teves; Chalk, Phillip Michael; Magalhães, Alberto M T

2015-01-01

Among the lighter elements having two or more stable isotopes (H, C, N, O, S), δ(15)N appears to be the most promising isotopic marker to differentiate plant products from conventional and organic farms. Organic plant products vary within a range of δ(15)N values of +0.3 to +14.6%, while conventional plant products range from negative to positive values, i.e. -4.0 to +8.7%. The main factors affecting δ(15)N signatures of plants are N fertilizers, biological N2 fixation, plant organs and plant age. Correlations between mode of production and δ(13)C (except greenhouse tomatoes warmed with natural gas) or δ(34)S signatures have not been established, and δ(2)H and δ(18)O are unsuitable markers due to the overriding effect of climate on the isotopic composition of plant-available water. Because there is potential overlap between the δ(15)N signatures of organic and conventionally produced plant products, δ(15)N has seldom been used successfully as the sole criterion for differentiation, but when combined with complementary analytical techniques and appropriate statistical tools, the probability of a correct identification increases. The use of organic fertilizers by conventional farmers or the marketing of organic produce as conventional due to market pressures are additional factors confounding correct identification. The robustness of using δ(15)N to differentiate mode of production will depend on the establishment of databases that have been verified for individual plant products.

Uranium Isotope Systematic in Saanich Inlet

NASA Astrophysics Data System (ADS)

Amini, M.; Holmden, C.; Francois, R.

2008-12-01

As a redox-sensitive element Uranium has become the focus of stable isotope studies. Based on the nuclear field shift effect [1], U isotope fractionation was predicted as a function of U(IV)-U(VI) exchange reactions with the insoluble reduced U(IV) species being heavier than the soluble oxidized U(VI) species. Recently, variations in 238U/235U were reported in low temperature aqueous and sedimentary environments [2,3] indicating that U deposited in well-oxygenated environments is characterized by light isotopic composition, whereas suboxic and anoxic deposits tend towards a heavy isotopic signature. U isotope fractionation has been hence proposed as a promising new paleo-redox proxy. In order to test the efficacy of U isotope fractionation to record oxidation states in marine systems, we are investigating sediment samples deposited over a range of redox conditions in the seasonally anoxic Saanich Inlet, on the east coast of Vancouver Island. We have also made δ238U measurements for water samples from above and below the redoxcline. The measurements were carried out by MC-ICPMS using 233U/236U-double spike technique. The data are reported as δ238U relative to NBL 112a with a 238U/235U ratio of 137.88 (2sd). External precision is better than 0.10 permil (2sd). Eleven analyses of seawater performed over the course of this work yielded δ238U of -0.41±0.07 permil (2sd). No clear difference in δ238U values has been found, thus far, in water samples collected at 10m (O2~380μM) and 200m (O2~1μM) depths from a single location in the middle of the inlet. The mean of two measurements of the deepwater sample yielded -0.43±0.01 permil (2sd). Two measurements of the shallow water sample yielded a mean value of -0.38±0.03 permil (2sd). The δ238U values for HF-HNO3 digestions of the organic rich sediments, one taken in the middle of the basin (3.11% organic carbon) below seasonally anoxic bottom waters (-0.22±0.01 permil, n=2), and the other taken from the sill (1.29% organic carbon) below well-oxygenated bottom waters (-0.22 permil, n=1) are identical. The δ238U value matches previously reported values for suboxic sediments from the Peru margin [3], but is lighter than organic rich sediments from the Black Sea [3], where the bottom waters are strongly euxinic. The consistency in δ238U vaues between previously investigated suboxic sediment samples [3] and our two sediment samples indicates that the magnitude of the U isotopic fractionation is identical between seawater and sediments deposited under a range of bottom water oxygen conditions from oxygenated to anoxic. However, differences between the U isotope compositions in Saanich Inlet and those from the Black Sea remain to be explained, if U isotope fractionation is be used as a quantitative proxy for paleoredox in ancient oceans. [1] Schauble (2007) GCA 71, 2170- 2189. [2] Stirling et al. (2007) EPSL 264, 208-225. [3] Weyer et al. (2007) GCA 72, 345-399.

Characterization of coal-derived hydrocarbons and source-rock potential of coal beds, San Juan Basin, New Mexico and Colorado, U.S.A.

USGS Publications Warehouse

Rice, D.D.; Clayton, J.L.; Pawlewicz, M.J.

1989-01-01

Coal beds are considered to be a major source of nonassociated gas in the Rocky Mountain basins of the United States. In the San Juan basin of northwestern New Mexico and southwestern Colorado, significant quantities of natural gas are being produced from coal beds of the Upper Cretaceous Fruitland Formation and from adjacent sandstone reservoirs. Analysis of gas samples from the various gas-producing intervals provided a means of determining their origin and of evaluating coal beds as source rocks. The rank of coal beds in the Fruitland Formation in the central part of the San Juan basin, where major gas production occurs, increases to the northeast and ranges from high-volatile B bituminous coal to medium-volatile bituminous coal (Rm values range from 0.70 to 1.45%). On the basis of chemical, isotopic and coal-rank data, the gases are interpreted to be thermogenic. Gases from the coal beds show little isotopic variation (??13C1 values range -43.6 to -40.5 ppt), are chemically dry (C1/C1-5 values are > 0.99), and contain significant amounts of CO2 (as much as 6%). These gases are interpreted to have resulted from devolatilization of the humic-type bituminous coal that is composed mainly of vitrinite. The primary products of this process are CH4, CO2 and H2O. The coal-generated, methane-rich gas is usually contained in the coal beds of the Fruitland Formation, and has not been expelled and has not migrated into the adjacent sandstone reservoirs. In addition, the coal-bed reservoirs produce a distinctive bicarbonate-type connate water and have higher reservoir pressures than adjacent sandstones. The combination of these factors indicates that coal beds are a closed reservoir system created by the gases, waters, and associated pressures in the micropore coal structure. In contrast, gases produced from overlying sandstones in the Fruitland Formation and underlying Pictured Cliffs Sandstone have a wider range of isotopic values (??13C1 values range from -43.5 to -38.5 ppt), are chemically wetter (C1/C1-5 values range from 0.85 to 0.95), and contain less CO2 (< 2%). These gases are interpreted to have been derived from type III kerogen dispersed in marine shales of the underlying Lewis Shale and nonmarine shales of the Fruitland Formation. In the underlying Upper Cretaceous Dakota Sandstone and Tocito Sandstone Lentil of the Mancos Shale, another gas type is produced. This gas is associated with oil at intermediate stages of thermal maturity and is isotopically lighter and chemically wetter at the intermediate stage of thermal maturity as compared with gases derived from dispersed type III kerogen and coal; this gas type is interpreted to have been generated from type II kerogen. Organic matter contained in coal beds and carbonaceous shales of the Fruitland Formation has hydrogen indexes from Rock-Eval pyrolysis between 100 and 350, and atomic H:C ratios between 0.8 and 1.2. Oxygen indexes and atomic O:C values are less than 24 and 0.3, respectively. Extractable hydrocarbon yields are as high as 7,000 ppm. These values indicate that the coal beds and carbonaceous shales have good potential for the generation of liquid hydrocarbons. Voids in the coal filled with a fluorescent material that is probably bitumen is evidence that liquid hydrocarbon generation has taken place. Preliminary oil-source rock correlations based on gas chromatography and stable carbon isotope ratios of C15+ hydrocarbons indicate that the coals and (or) carbonaceous shales in the Fruitland Formation may be the source of minor amounts of condensate produced from the coal beds at relatively low levelsof thermal maturity (Rm=0.7). ?? 1989.

Isotopic Composition of Carbonates in Antarctic Ordinary Chondrites and Miller Range Nakhlites: Insights into Martian Amazonian Aqueous Alteration

NASA Technical Reports Server (NTRS)

Evans, M. E.; Niles, P. B.; Chapman, P.

2017-01-01

The martian surface contains features of ancient fluvial systems. Stable isotope analysis of carbonates that form in aqueous systems can reveal their formation conditions. The Nakhlite meteorites originally formed on Mars 1.3 Ga and were later exposed to aqueous fluids that left behind carbonate minerals [1], thus analysis of these carbonates can provide data to understand Amazonian climate conditions on Mars. Carbonates found in the Nakhlite meteorites contain a range of delta(sup 13)C values, which may be either martian carbonates or terrestrial contamination. To better under-stand terrestrial weathering products and martian carbonate formation processes, we conducted a set of carbonate isotope analyses on Antarctic meteorites focusing on Miller Range (MIL) Nakhlites as well as Ordinary Chondrites (OCs) (Figure 1)[1-11] [12]. OCs of petrology type H, L, and LL 3-6 were selected since they are not expected to contain preterrestrial carbonates, yet they have visible evaporite minerals on the fusion crust indicating terrestrial alteration. These cryogenically formed terrestrial carbonates may also provide an analog for cryogenic carbonate formation on Mars.

Studying Antarctic Ordinary Chondrite (OC) and Miller Range (MIL) Nakhlite Meteorites to Assess Carbonate Formation on Earth and Mars

NASA Astrophysics Data System (ADS)

Evans, Michael Ellis

Carbonates are found in meteorites collected from Antarctica. The stable isotope composition of these carbonates records their formation environment on either Earth or Mars. The first research objective of this dissertation is to characterize the delta18O and delta 13C values of terrestrial carbonates formed on Ordinary Chondrites (OCs) collected in regions near known martian meteorites. The second objective is to characterize the delta18O and delta13C values of martian carbonates from Nakhlites collected from the Miller Range (MIL). The third objective is to assess environmental changes on Mars since the Noachian period. The OCs selected had no pre-terrestrial carbonates so any carbonates detected are presumed terrestrial in origin. The study methodology is stepped extraction of CO2 created from phosphoric acid reaction with meteorite carbonate. Stable isotope results show that two distinct terrestrial carbonate species (Ca-rich and Fe/Mg-rich) formed in Antarctica on OCs from a thin-film of meltwater containing dissolved CO2. Carbon isotope data suggests the terrestrial carbonates formed in equilibrium with atmospheric CO2 delta 13C = -7.5‰ at >15°C. The wide variation in delta 18O suggests the carbonates did not form in equilibrium with meteoric water alone, but possibly formed from an exchange of oxygen isotopes in both water and dissolved CO2. Antarctica provides a model for carbonate formation in a low water/rock ratio, near 0°C environment like modern Mars. Nakhlite parent basalt formed on Mars 1.3 billion years ago and the meteorites were ejected by a single impact approximately 11 million years ago. They traveled thru space before eventually falling to the Earth surface 10,000-40,000 years ago. Nakhlite samples for this research were all collected from the Miller Range (MIL) in Antarctica. The Nakhlite stable isotope results show two carbonate species (Ca-rich and Fe/Mg-rich) with a range of delta18O values that are similar to the terrestrial OC carbonates. The Nakhlite carbonates have distinctly different, heavier delta13C values from a presumed martian carbon reservoir. These carbonates cannot form in equilibrium at 15°C with the modern Mars atmospheric CO2 (measured by the Curiosity rover) delta13C = 46‰, but may reflect kinetic carbonate formation from a high pH fluid. Alternatively, the Nakhlite carbonates may have formed with a lighter, early Amazonian atmosphere of delta 13C ≈ 30‰. Assuming the martian carbonates formed in a thin-film environment like the OC terrestrial carbonates, an oxygen mixing model predicts early Amazonian martian meteoric water delta18O = -30‰.