Strontium and neodymium isotopic evidence for the heterogeneous nature and development of the mantle beneath Afar (Ethiopia)

NASA Astrophysics Data System (ADS)

Betton, P. J.; Civetta, L.

1984-11-01

Neodymium isotope and REE analyses of recent volcanic rocks and spinel lherzolite nodules from the Afar area are reported. The 143Nd/ 144Nd ratios of the volcanic rocks range from 0.51286 to 0.51304, similar to the range recorded from Iceland. However, the 87Sr/ 86Sr ratios display a distinctly greater range (0.70328-0.70410) than those reported from the primitive rocks of Iceland. Whole rock samples and mineral separates from the spinel lherzolite nodules exhibit uniform 143Nd/ 144Nd ratios (ca. 0.5129) but varied 87Sr/ 86Sr ratios in the range 0.70427-0.70528. The Sr sbnd Nd isotope variations suggest that the volcanic rocks may have been produced by mixing between two reservoirs with distinct isotopic compositions. Two possible magma reservoirs in this area are the source which produced the "MORB-type" volcanics in the Red Sea and Gulf of Aden and the anomalous source represented by the nodule suite. The isotopic composition of the volcanics is compatible with mixing between these two reservoirs. It is shown that the anomalous source with a high 87Sr/ 86Sr ratio cannot have been produced by simple processes of partial melting and mixing within normal mantle. Instead the high 87Sr/ 86Sr is equated with a fluid phase. A primitive cognate fluid, subducted seawater or altered oceanic lithosphere may have been responsible for the generation of the source with a high 87Sr/ 86Sr ratio.

Application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed

USGS Publications Warehouse

Borrok, D.M.; Wanty, R.B.; Ian, Ridley W.; Lamothe, P.J.; Kimball, B.A.; Verplanck, P.L.; Runkel, R.L.

2009-01-01

Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, ??56Fe and ??66Zn isotopic signatures of filtered stream water samples varied by ???3.5??? and 0.4???, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in ??56Fe were linked to redox and precipitation reactions occurring in the stream, while changes in ??66Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<-2.0???) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4???). Acidic drainage from mine wastes contributed heavier dissolved Fe (???+0.5???) and lighter Zn (???+0.2???) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe (??56Fe ??? 0???) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds. ?? 2009 Elsevier Ltd.

Using Nd and Sr isotopes to trace dust and volcanic inputs to soils on French Guadeloupe Island

NASA Astrophysics Data System (ADS)

Guo, J.; Pereyra, Y.; Ma, L.; Gaillardet, J.; Sak, P. B.; Bouchez, J.

2017-12-01

Soil is at the central part of the Critical Zone for its important roles in sustaining ecosystems and agriculture. At French Guadeloupe, a tropical humid volcanic island, previous studies have shown that the mineral nutrient elements such as K, Na, Ca, and Mg are highly depleted in the surface soil. And mineral nutrients introduced by dusts are an important mineral nutrient source for vegetation growth in this area. It is important to understand and quantify the sources of the mineral dust added to surface soils. Nd isotope ratios, due to their distinct signatures between two unique end-members in soils for this area: the young volcanic areas like Guadeloupe and the dust source region from the old continental shields like Sahara Desert, can be a robust tracer to understand this critical process. Nevertheless, Sr isotope ratios can trace the inputs of marine aerosols. Here we present a new Nd isotope study on Guadeloupe soil depth profiles, combined with previous Sr isotope data, to fingerprint the sources of dust and volcanic inputs into soils. Soil samples from three surface profiles (0 - 1000cm deep) at different locations of the Guadeloupe Island were systematically analyzed. The results show distinct depth variations for Nd isotope signature along profiles. For all profiles, deep soils are relatively consisted with bedrock value (ɛNd: 5.05). But in surface soils (0-600cm), unlike Sr isotope ratios that are significantly modified by marine aerosol input, Nd isotope ratios show similar decrease (to ɛNd:-10) and frequent fluctuations toward the surface, suggesting dust is the dominant source of Nd in these soils. This conclusion is further supported by REE and other trace element data. Thus, with a simplified two end-member model, Sahara dust contributes the Nd percentages in soils varying from 10.7% at the deepest profiles to 69.5% on surface, showing a significant amount of Nd on the surface soil came from dust source. The deep soil profiles are also characterized by the presence of Nd isotope spikes with negative values, suggesting dust signatures at depth. Such a feature could be related to the presence of a paleo-soil surface at the spike depth that was buried by later volcanic eruption. Both Nd and Sr isotopes hence show dust and volcanic inputs are important factors for soil developments on French Guadeloupe Island.

Lead (Pb) Isotope Baselines for Studies of Ancient Human Migration and Trade in the Maya Region.

PubMed

Sharpe, Ashley E; Kamenov, George D; Gilli, Adrian; Hodell, David A; Emery, Kitty F; Brenner, Mark; Krigbaum, John

2016-01-01

We examined the potential use of lead (Pb) isotopes to source archaeological materials from the Maya region of Mesoamerica. The main objectives were to determine if: 1) geologic terrains throughout the Maya area exhibit distinct lead isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb), and 2) a combination of lead and strontium ratios can enhance sourcing procedures in the Mesoamerica region. We analyzed 60 rock samples for lead isotope ratios and a representative subset of samples for lead, uranium, and thorium concentrations across the Maya region, including the Northern Lowlands of the Mexican Yucatan Peninsula, the Southern Lowlands of Guatemala and Belize, the Volcanic Highlands, the Belizean Maya Mountains, and the Metamorphic Province/Motagua Valley. Although there is some overlap within certain sub-regions, particularly the geologically diverse Metamorphic Province, lead isotopes can be used to distinguish between the Northern Lowlands, the Southern Lowlands, and the Volcanic Highlands. The distinct lead isotope ratios in the sub-regions are related to the geology of the Maya area, exhibiting a general trend in the lowlands of geologically younger rocks in the north to older rocks in the south, and Cenozoic volcanic rocks in the southern highlands. Combined with other sourcing techniques such as strontium (87Sr/86Sr) and oxygen (δ18O), a regional baseline for lead isotope ratios can contribute to the development of lead isoscapes in the Maya area, and may help to distinguish among geographic sub-regions at a finer scale than has been previously possible. These isotope baselines will provide archaeologists with an additional tool to track the origin and movement of ancient humans and artifacts across this important region.

Lead (Pb) Isotope Baselines for Studies of Ancient Human Migration and Trade in the Maya Region

PubMed Central

Kamenov, George D.; Gilli, Adrian; Hodell, David A.; Emery, Kitty F.; Brenner, Mark; Krigbaum, John

2016-01-01

We examined the potential use of lead (Pb) isotopes to source archaeological materials from the Maya region of Mesoamerica. The main objectives were to determine if: 1) geologic terrains throughout the Maya area exhibit distinct lead isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb), and 2) a combination of lead and strontium ratios can enhance sourcing procedures in the Mesoamerica region. We analyzed 60 rock samples for lead isotope ratios and a representative subset of samples for lead, uranium, and thorium concentrations across the Maya region, including the Northern Lowlands of the Mexican Yucatan Peninsula, the Southern Lowlands of Guatemala and Belize, the Volcanic Highlands, the Belizean Maya Mountains, and the Metamorphic Province/Motagua Valley. Although there is some overlap within certain sub-regions, particularly the geologically diverse Metamorphic Province, lead isotopes can be used to distinguish between the Northern Lowlands, the Southern Lowlands, and the Volcanic Highlands. The distinct lead isotope ratios in the sub-regions are related to the geology of the Maya area, exhibiting a general trend in the lowlands of geologically younger rocks in the north to older rocks in the south, and Cenozoic volcanic rocks in the southern highlands. Combined with other sourcing techniques such as strontium (87Sr/86Sr) and oxygen (δ18O), a regional baseline for lead isotope ratios can contribute to the development of lead isoscapes in the Maya area, and may help to distinguish among geographic sub-regions at a finer scale than has been previously possible. These isotope baselines will provide archaeologists with an additional tool to track the origin and movement of ancient humans and artifacts across this important region. PMID:27806065

The Early Differentiation History of Mars from W-182-Nd-142 Isotope Systematics in the SNC Meteorites

NASA Technical Reports Server (NTRS)

Foley, C. Nicole; Wadhwa, M.; Borg, L. E.; Janney, P. E.; Hines, R.; Grove, T. L.

2005-01-01

We report here the results of an investigation of W and Nd isotopes in the SNC (Shergottite-Nakhlite-Chassignite (martian)) meteorites. We have determined that epsilon W-182 values in the nakhlites are uniform within analytical uncertainties and have an average value of approx. 3. Also, while epsilon W-182 values in the shergottites have a limited range (from 0.3-0.7), their epsilon Nd-142 values vary considerably (from -0.2-0.9). There appears to be no correlation between epsilon W-182 and epsilon Nd-142 in the nakhlites and shergottites. These results shed new light on early differentiation processes on Mars, particularly on the timing and nature of fractionation in silicate reservoirs. Assuming a two-stage model, the metallic core is estimated to have formed at approx. 12 Myr after the beginning of the solar system. Major silicate differentiation established the nakhlite source reservoir before approx. 4542 Ma and the shergottite source reservoirs at 4525 [sup +19 sub -21] Ma. These ages imply that, within the uncertainties afforded by the Hf-182-W-182 and Sm-146-Nd-142 chronometers, the silicate differentiation events that established the source reservoirs of the nakhlites and shergottites may have occurred contemporaneously, possibly during crystallization of a global magma ocean. The distinct W-182-Nd-142 isotope systematics in the nakhlites and the shergottites imply the presence of at least three isotopically distinct silicate reservoirs on Mars, two of which are depleted in incompatible lithophile elements relative to chondrites, and the third is enriched. The two depleted silicate reservoirs most likely reside in the Martian mantle, while the enriched reservoir could be either in the crust or the mantle. Therefore, the W-182-Nd-142 isotope systematics indicate that the nakhlites and the shergottites originated from distinct source reservoirs and cannot be petrogenetically related. A further implication is that the source reservoirs of the nakhlites and shergottites on Mars have been isolated since their establishment before approx. 4.5 Ga. Therefore, there has been no giant impact or efficient global mantle convection to thoroughly homogenize the Martian mantle following the establishment of the SNC source reservoirs.

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.

An Ordinary Chondrite Impactor Composition for the Bosumtwi Impact Structure, Ghana, West Africa: Discussion of Siderophile Element Contents and Os and Cr Isotope Data

NASA Technical Reports Server (NTRS)

Koeberl, Christian; Shukolyukov, Alex; Lugmair, Guenter

2004-01-01

Osmium isotope data had shown that Ivory Coast tektites contain an extraterrestrial component, but do not allow distinction between chondritic and iron meteorite contamination. PGE abundances of Ivory Coast tektites and impactites and target rocks from the Bosumtwi crater, the source crater of the Ivory Coast tektites, were all relatively high and did not allow to resolve the presence, or identify the nature, of the meteoritic component. However, Cr isotope analyses of an Ivory Coast tektite yielded a distinct 53Cr excess of 0.30+/-0.06, which indicates that the Bosumtwi impactor was an ordinary chondrite.

Evidence for supernova injection into the solar nebula and the decoupling of r-process nucleosynthesis

PubMed Central

Brennecka, Gregory A.; Borg, Lars E.; Wadhwa, Meenakshi

2013-01-01

The isotopic composition of our Solar System reflects the blending of materials derived from numerous past nucleosynthetic events, each characterized by a distinct isotopic signature. We show that the isotopic compositions of elements spanning a large mass range in the earliest formed solids in our Solar System, calcium–aluminum-rich inclusions (CAIs), are uniform, and yet distinct from the average Solar System composition. Relative to younger objects in the Solar System, CAIs contain positive r-process anomalies in isotopes A < 140 and negative r-process anomalies in isotopes A > 140. This fundamental difference in the isotopic character of CAIs around mass 140 necessitates (i) the existence of multiple sources for r-process nucleosynthesis and (ii) the injection of supernova material into a reservoir untapped by CAIs. A scenario of late supernova injection into the protoplanetary disk is consistent with formation of our Solar System in an active star-forming region of the galaxy. PMID:24101483

Evidence for supernova injection into the solar nebula and the decoupling of r-process nucleosynthesis.

PubMed

Brennecka, Gregory A; Borg, Lars E; Wadhwa, Meenakshi

2013-10-22

The isotopic composition of our Solar System reflects the blending of materials derived from numerous past nucleosynthetic events, each characterized by a distinct isotopic signature. We show that the isotopic compositions of elements spanning a large mass range in the earliest formed solids in our Solar System, calcium-aluminum-rich inclusions (CAIs), are uniform, and yet distinct from the average Solar System composition. Relative to younger objects in the Solar System, CAIs contain positive r-process anomalies in isotopes A < 140 and negative r-process anomalies in isotopes A > 140. This fundamental difference in the isotopic character of CAIs around mass 140 necessitates (i) the existence of multiple sources for r-process nucleosynthesis and (ii) the injection of supernova material into a reservoir untapped by CAIs. A scenario of late supernova injection into the protoplanetary disk is consistent with formation of our Solar System in an active star-forming region of the galaxy.

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.

Use of Lead Isotopes to Identify Sources of Metal and Metalloid Contaminants in Atmospheric Aerosol from Mining Operations

PubMed Central

Félix, Omar I.; Csavina, Janae; Field, Jason; Rine, Kyle P.; Sáez, A. Eduardo; Betterton, Eric A.

2014-01-01

Mining operations are a potential source of metal and metalloid contamination by atmospheric particulate generated from smelting activities, as well as from erosion of mine tailings. In this work, we show how lead isotopes can be used for source apportionment of metal and metalloid contaminants from the site of an active copper mine. Analysis of atmospheric aerosol shows two distinct isotopic signatures: one prevalent in fine particles (< 1 μm aerodynamic diameter) while the other corresponds to coarse particles as well as particles in all size ranges from a nearby urban environment. The lead isotopic ratios found in the fine particles are equal to those of the mine that provides the ore to the smelter. Topsoil samples at the mining site show concentrations of Pb and As decreasing with distance from the smelter. Isotopic ratios for the sample closest to the smelter (650 m) and from topsoil at all sample locations, extending to more than 1 km from the smelter, were similar to those found in fine particles in atmospheric dust. The results validate the use of lead isotope signatures for source apportionment of metal and metalloid contaminants transported by atmospheric particulate. PMID:25496740

Gas chromatographic/mass spectrometric determination of carbon isotope composition in unpurified samples: methamphetamine example.

PubMed

Low, I A; Liu, R H; Legendre, M G; Piotrowski, E G; Furner, R L

1986-10-01

A gas chromatograph/quadrupole mass spectrometer system, operated in electron impact/selected ion monitoring mode, is used to determine the intensity ratio of the m/z 59 and the m/z 58 ions of the [C3H8N]+ fragment derived from methamphetamine samples synthesized with varying amounts of 13C-labeled methylamine. Crude products are introduced into the gas chromatograph without prior cleanup. The ratios measured were in excellent agreement with those calculated. A change in 0.25% use of 13C-methylamine is sufficient for product differentiation. The feasibility of using isotope labeling and subsequent mass spectrometric isotope ratio measurement as the basis of a compound tracing mechanism is discussed. Specifically, if methamphetamine samples manufactured from legal sources are asked to incorporate distinct 13C compositions, their sources can be traced when samples are diverted into illegal channels. Samples derived from illicit preparations can also be traced if the manufacturers of a precursor (methylamine in this case) incorporate distinct 13C compositions in their products.

Isotope investigation on groundwater recharge and dynamics in shallow and deep alluvial aquifers of southwest Punjab.

PubMed

Keesari, Tirumalesh; Sharma, Diana A; Rishi, Madhuri S; Pant, Diksha; Mohokar, Hemant V; Jaryal, Ajay Kumar; Sinha, U K

2017-11-01

Groundwater samples collected from the alluvial aquifers of southwest Punjab, both shallow and deep zones were measured for environmental tritium ( 3 H) and stable isotopes ( 2 H and 18 O) to evaluate the source of recharge and aquifer dynamics. The shallow groundwater shows wide variation in isotopic signature (δ 18 O: -11.3 to -5.0‰) reflecting multiple sources of recharge. The average isotopic signature of shallow groundwaters (δ 18 O: -6.73 ± 1.03‰) is similar to that of local precipitation (-6.98 ± 1.66‰) indicating local precipitation contributes to a large extent compared to other sources. Other sources have isotopically distinct signatures due to either high altitude recharge (canal sources) or evaporative enrichment (irrigation return flow). Deep groundwater shows relatively depleted isotopic signature (δ 18 O: -8.6‰) and doesn't show any evaporation effect as compared to shallow zone indicating recharge from precipitation occurring at relatively higher altitudes. Environmental tritium indicates that both shallow ( 3 H: 5 - 10 T.U.) and deeper zone ( 3 H: 1.5 - 2.5 T.U.) groundwaters are modern. In general the inter-aquifer connections seem to be unlikely except a few places. Environmental isotope data suggests that shallow groundwater is dynamic, local and prone to changes in land use patterns while deep zone water is derived from distant sources, less dynamic and not impacted by surface manifestations. A conceptual groundwater flow diagram is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

Isotopic composition of Pb and Th in interplinian volcanics from Somma-Vesuvius volcano, Italy

USGS Publications Warehouse

Cortini, M.; Ayuso, R.A.; de Vivo, B.; Holden, P.; Somma, R.

2004-01-01

We present a detailed isotopic study of volcanic rocks emitted from Somma-Vesuvius volcano during three periods of interplinian activity: "Protohistoric" (3550 y B.P. to 79 A.D.), "Ancient Historic" (79 to 472 A.D.) and "Medieval" (472 to 1631 A.D.). Pb isotopic compositions of two acid leached fractions and whole rock residues of 37 whole rock samples (determined by Somma et al., 2001) show that each of the three interplinian periods is distinguished by small, systematic, and unique uranogenic and thorogenic Pb isotopic trends. This key and novel feature is compatible with the notion that the Pb isotopic data reflect small-scale source heterogeneity operating over relatively short periods of time. From this representative group of samples, a selected set of nine whole rocks were analysed for Th isotopes. 232Th/238U ratios in the source can be obtained independently from Pb and from Th isotopes. Those obtained from Pb isotopes represent source ratios, time-integrated over the whole age of the Earth; they range from 3.9 to 4.1. 232Th/238U obtained from Th isotopes are those of the present source. They are lower, and cluster around 3.5; this difference probably indicates recent U enrichment of the present source. The behaviour of Pb, as inferred by its isotopic ratios, is quite distinct from that of Sr and Nd isotopes: Pb isotope variations are not correlated to Sr or Nd isotope variations. The isotopic contrast is compatible with the idea that the isotopes were decoupled during magmatic production, evolution, and ascent through the crust. Thus, the Pb isotopes do not reflect the effects of the same processes as in the case of the Sr and Nd isotopes, or, as we also favor, they do not necessarily reflect the same source contributions into the magmas. Moreover, the Pb isotopic evolution of the interplinian rocks chiefly reflects mixing, driven by processes that are superimposed on, and independent of, other source contributions that determine the isotopic compositions of Sr and Nd. We suggest that reactions between magmas and fluids transported Pb and U, but not Sr. These data show that isotope mixing in the mantle is active at different times and scales. ?? Springer-Verlag 2004.

Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems

USGS Publications Warehouse

Young, M.B.; McLaughlin, K.; Kendall, C.; Stringfellow, W.; Rollog, M.; Elsbury, K.; Donald, E.; Paytan, A.

2009-01-01

The oxygen isotopic composition of dissolved inorganic phosphate (δ18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source δ18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for δ18O p to be a useful tool for source tracking, the δ18Op of phosphate sources must be distinguishable from one another; however, the δ18Op of potential sources has not been well characterized. We measured the δ18O p of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of δ18Op values (from +8.4 to +24.9‰) for the various sources, and statistically significant differences were found between several of the source types. δ18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in δ18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and δ18Op can be used for identifying phosphate sources to aquatic systems.

Advances in Methane Isotope Measurements via Direct Absorption Spectroscopy with Applications to Oil and Gas Source Characterization

NASA Astrophysics Data System (ADS)

Yacovitch, T. I.; Herndon, S. C.; Roscioli, J. R.; Petron, G.; Shorter, J. H.; Jervis, D.; McManus, J. B.; Nelson, D. D.; Zahniser, M. S.; Kolb, C. E., Jr.

2015-12-01

Instrumental developments in the measurement of multiple isotopes of methane (12CH4, 13CH4 and 12CH3D) are presented. A first generation 8-micron instrument quantifies 12CH4 and 13CH4 at a 1-second rate via tunable infrared direct absorption spectroscopy (TILDAS). A second generation instrument uses two 3-micron intraband cascade lasers in an Aerodyne dual laser chassis for simultaneous measurement of 12CH4, 13CH4 and 12CH3D. Sensitivity and noise performance improvements are examined. The isotopic signature of methane provides valuable information for emission source identification of this greenhouse gas. A first generation spectrometer has been deployed in the field on a mobile laboratory along with a sophisticated 4-tank calibration system. Calibrations are done on an agressive schedule, allowing for the correction of measured isotope ratios to an absolute isotope scale. Distinct isotopic signatures are found for a number of emission sources in the Denver-Julesburg Basin: oil and gas gathering stations, compressor stations and processing plants; a municipal landfill, and dairy/cattle operations. The isotopic signatures are compared with measured ethane/methane ratios. These direct absorption measurements have larger uncertainties than samples measured via gas chromatography-mass spectrometry, but have several advantages over canister sampling methods: individual sources of short duration are easier to isolate; calibrated isotope ratio results are available immediately; replicate measurements on a single source are easily performed; and the number of sources sampled is not limited by canister availability and processing time.

Pb isotopes of Gorgona Island (Colombia): isotopic variations correlated with magma type

NASA Astrophysics Data System (ADS)

Dupré, B.; Echeverría, L. M.

1984-02-01

Lead isotopic results obtained on komatiites and basalts from Gorgona Island provide evidence of large isotopic variations within a restricted area (8 × 2.5 km). The variations are correlated with differences in volcanic rock type. The highest isotopic ratios ( 206Pb/ 204Pb˜ 19.75 ) correspond to tholeiites which make up most of the island. The lowest ratios (18.3) correspond to the komatiites of the west coast of the island. Other rock types (komatiites of the east coast, K-tholeiites, picrites and tuffs) have isotopic characteristics intermediate between these two extreme values. These results are explained by the existence of two distinct mantle source regions, and by mixing or contamination between them.

An open source Bayesian Monte Carlo isotope mixing model with applications in Earth surface processes

NASA Astrophysics Data System (ADS)

Arendt, Carli A.; Aciego, Sarah M.; Hetland, Eric A.

2015-05-01

The implementation of isotopic tracers as constraints on source contributions has become increasingly relevant to understanding Earth surface processes. Interpretation of these isotopic tracers has become more accessible with the development of Bayesian Monte Carlo (BMC) mixing models, which allow uncertainty in mixing end-members and provide methodology for systems with multicomponent mixing. This study presents an open source multiple isotope BMC mixing model that is applicable to Earth surface environments with sources exhibiting distinct end-member isotopic signatures. Our model is first applied to new δ18O and δD measurements from the Athabasca Glacier, which showed expected seasonal melt evolution trends and vigorously assessed the statistical relevance of the resulting fraction estimations. To highlight the broad applicability of our model to a variety of Earth surface environments and relevant isotopic systems, we expand our model to two additional case studies: deriving melt sources from δ18O, δD, and 222Rn measurements of Greenland Ice Sheet bulk water samples and assessing nutrient sources from ɛNd and 87Sr/86Sr measurements of Hawaiian soil cores. The model produces results for the Greenland Ice Sheet and Hawaiian soil data sets that are consistent with the originally published fractional contribution estimates. The advantage of this method is that it quantifies the error induced by variability in the end-member compositions, unrealized by the models previously applied to the above case studies. Results from all three case studies demonstrate the broad applicability of this statistical BMC isotopic mixing model for estimating source contribution fractions in a variety of Earth surface systems.

Impacts of Dust on Tropical Volcanic Soil Formation: Insights from Strontium and Uranium-Series Isotopes in Soils from Basse-Terre Island, French Guadeloupe

NASA Astrophysics Data System (ADS)

Pereyra, Y.; Ma, L.; Sak, P. B.; Gaillardet, J.; Buss, H. L.; Brantley, S. L.

2015-12-01

Dust inputs play an important role in soil formation, especially for thick soils developed on tropical volcanic islands. In these regions, soils are highly depleted due to intensive chemical weathering, and mineral nutrients from dusts have been known to be important in sustaining soil fertility and productivity. Tropical volcanic soils are an ideal system to study the impacts of dust inputs on the ecosystem. Sr and U-series isotopes are excellent tracers to identify sources of materials in an open system if the end-members have distinctive isotope signatures. These two isotope systems are particularly useful to trace the origin of atmospheric inputs into soils and to determine rates and timescales of soil formation. This study analyzes major elemental concentrations, Sr and U-series isotope ratios in highly depleted soils in the tropical volcanic island of Basse-Terre in French Guadeloupe to determine atmospheric input sources and identify key soil formation processes. We focus on three soil profiles (8 to 12 m thick) from the Bras-David, Moustique Petit-Bourg, and Deshaies watersheds; and on the adjacent rivers to these sites. Results have shown a significant depletion of U, Sr, and major elements in the deep profile (12 to 4 m) attributed to rapid chemical weathering. The top soil profiles (4 m to the surface) all show addition of elements such as Ca, Mg, U, and Sr due to atmospheric dust. More importantly, the topsoil profiles have distinct Sr and U-series isotope compositions from the deep soils. Sr and U-series isotope ratios of the top soils and sequential extraction fractions confirm that the sources of the dust are from the Saharan dessert, through long distance transport from Africa to the Caribbean region across the Atlantic Ocean. During the transport, some dust isotope signatures may also have been modified by local volcanic ashes and marine aerosols. Our study highlights that dusts and marine aerosols play important roles in element cycles and nutrient sources in the highly depleted surface soils of tropical oceanic islands.

Distinct iron isotopic signatures and supply from marine sediment dissolution.

PubMed

Homoky, William B; John, Seth G; Conway, Tim M; Mills, Rachel A

2013-01-01

Oceanic iron inputs must be traced and quantified to learn how they affect primary productivity and climate. Chemical reduction of iron in continental margin sediments provides a substantial dissolved flux to the oceans, which is isotopically lighter than the crust, and so may be distinguished in seawater from other sources, such as wind-blown dust. However, heavy iron isotopes measured in seawater have recently led to the proposition of another source of dissolved iron from 'non-reductive' dissolution of continental margins. Here we present the first pore water iron isotope data from a passive-tectonic and semi-arid ocean margin (South Africa), which reveals a smaller and isotopically heavier flux of dissolved iron to seawater than active-tectonic and dysoxic continental margins. These data provide in situ evidence of non-reductive iron dissolution from a continental margin, and further show that geological and hydro-climatic factors may affect the amount and isotopic composition of iron entering the ocean.

Distinct iron isotopic signatures and supply from marine sediment dissolution

PubMed Central

Homoky, William B.; John, Seth G.; Conway, Tim M.; Mills, Rachel A.

2013-01-01

Oceanic iron inputs must be traced and quantified to learn how they affect primary productivity and climate. Chemical reduction of iron in continental margin sediments provides a substantial dissolved flux to the oceans, which is isotopically lighter than the crust, and so may be distinguished in seawater from other sources, such as wind-blown dust. However, heavy iron isotopes measured in seawater have recently led to the proposition of another source of dissolved iron from ‘non-reductive’ dissolution of continental margins. Here we present the first pore water iron isotope data from a passive-tectonic and semi-arid ocean margin (South Africa), which reveals a smaller and isotopically heavier flux of dissolved iron to seawater than active-tectonic and dysoxic continental margins. These data provide in situ evidence of non-reductive iron dissolution from a continental margin, and further show that geological and hydro-climatic factors may affect the amount and isotopic composition of iron entering the ocean. PMID:23868399

Hf-Nd isotopic variability in mineral dust from Chinese and Mongolian deserts: implications for sources and dispersal

PubMed Central

Zhao, Wancang; Sun, Youbin; Balsam, William; Lu, Huayu; Liu, Lianwen; Chen, Jun; Ji, Junfeng

2014-01-01

Mineral dust provenances are closely related to the orogenic processes which may have distinct Hf-Nd isotopic signatures. Here we report the clay-sized (<2 μm) Hf-Nd isotope data from Asian dust sources to better constrain the source and transport dynamics of dust deposition in the North Pacific. Our results show that there is a more positive radiogenic Hf isotopic composition with clay-sized fractions than the corresponding bulk sample and a decoupling of the Hf-Nd couplets in the clay formation during the weathering process. The clay-sized Hf-Nd isotopic compositions of the desert samples from the Sino-Korean-Tarim Craton (SKTC) are different from those of the Gobi and deserts from the Central Asian Orogeny Belt (CAOB) due to varying tectonic and weathering controls. The Hf-Nd isotopic compositions of dust in the North Pacific central province (NPC) match closely with those from the Taklimakan, Badain Jaran and adjacent Tengger deserts, implying that the NPC dust was mainly transported from these potential sources by the westerly jet. Our study indicates that dusts from the CAOB Gobi deserts either didn't arrive in NPC or were quantitatively insignificant, but they were likely transported to the North Pacific margin province (NPM) by East Asian winter monsoon. PMID:25060781

Hf-Nd isotopic variability in mineral dust from Chinese and Mongolian deserts: implications for sources and dispersal.

PubMed

Zhao, Wancang; Sun, Youbin; Balsam, William; Lu, Huayu; Liu, Lianwen; Chen, Jun; Ji, Junfeng

2014-07-25

Mineral dust provenances are closely related to the orogenic processes which may have distinct Hf-Nd isotopic signatures. Here we report the clay-sized (<2 μm) Hf-Nd isotope data from Asian dust sources to better constrain the source and transport dynamics of dust deposition in the North Pacific. Our results show that there is a more positive radiogenic Hf isotopic composition with clay-sized fractions than the corresponding bulk sample and a decoupling of the Hf-Nd couplets in the clay formation during the weathering process. The clay-sized Hf-Nd isotopic compositions of the desert samples from the Sino-Korean-Tarim Craton (SKTC) are different from those of the Gobi and deserts from the Central Asian Orogeny Belt (CAOB) due to varying tectonic and weathering controls. The Hf-Nd isotopic compositions of dust in the North Pacific central province (NPC) match closely with those from the Taklimakan, Badain Jaran and adjacent Tengger deserts, implying that the NPC dust was mainly transported from these potential sources by the westerly jet. Our study indicates that dusts from the CAOB Gobi deserts either didn't arrive in NPC or were quantitatively insignificant, but they were likely transported to the North Pacific margin province (NPM) by East Asian winter monsoon.

Geographical patterns of human diet derived from stable-isotope analysis of fingernails

USGS Publications Warehouse

Nardoto, G.B.; Silva, S.; Kendall, C.; Ehleringer, J.R.; Chesson, L.A.; Ferraz, E.S.B.; Moreira, M.Z.; Ometto, Jean P. H. B.; Martinelli, L.A.

2006-01-01

Carbon and nitrogen isotope ratios of human fingernails were measured in 490 individuals in the western US and 273 individuals in southeastern Brazil living in urban areas, and 53 individuals living in a moderately isolated area in the central Amazon region of Brazil and consuming mostly locally grown foods. In addition, we measured the carbon and nitrogen isotope ratios of common food items to assess the extent to which these isotopic signatures remain distinct for people eating both omnivorous and vegetarian diets and living in different parts of the world, and the extent to which dietary information can be interpreted from these analyses. Fingernail ??13C values (mean ?? standard deviation) were -15.4 ?? 1.0 and -18.8 ?? 0.8??? and ??15N values were 10.4 ?? 0.7 and 9.4 ?? 0.6??? for southeastern Brazil and western US populations, respectively. Despite opportunities for a "global supermarket" effect to swamp out carbon and nitrogen isotope ratios in these two urbanized regions of the world, differences in the fingernail isotope ratios between southeastern Brazil and western US populations persisted, and appeared to be more associated with regional agricultural and animal production practices. Omnivores and vegetarians from Brazil and the US were isotopically distinct, both within and between regions. In a comparison of fingernails of individuals from an urban city and isolated communities in the Amazonian region, the urban region was similar to southeastern Brazil, whereas individuals from isolated nonurban communities showed distinctive isotopic values consistent with their diets and with the isotopic values of local foods. Although there is a tendency for a "global supermarket" diet, carbon and nitrogen isotopes of human fingernails hold dietary information directly related to both food sources and dietary practices in a region. ?? 2006 Wiley-Liss, Inc.

Geographical patterns of human diet derived from stable-isotope analysis of fingernails.

PubMed

Nardoto, Gabriela B; Silva, Steven; Kendall, Carol; Ehleringer, James R; Chesson, Lesley A; Ferraz, Epaminondas S B; Moreira, Marcelo Z; Ometto, Jean P H B; Martinelli, Luiz A

2006-09-01

Carbon and nitrogen isotope ratios of human fingernails were measured in 490 individuals in the western US and 273 individuals in southeastern Brazil living in urban areas, and 53 individuals living in a moderately isolated area in the central Amazon region of Brazil and consuming mostly locally grown foods. In addition, we measured the carbon and nitrogen isotope ratios of common food items to assess the extent to which these isotopic signatures remain distinct for people eating both omnivorous and vegetarian diets and living in different parts of the world, and the extent to which dietary information can be interpreted from these analyses. Fingernail delta13C values (mean +/- standard deviation) were -15.4 +/- 1.0 and -18.8 +/- 0.8 per thousand and delta15N values were 10.4 +/- 0.7 and 9.4 +/- 0.6 per thousand for southeastern Brazil and western US populations, respectively. Despite opportunities for a "global supermarket" effect to swamp out carbon and nitrogen isotope ratios in these two urbanized regions of the world, differences in the fingernail isotope ratios between southeastern Brazil and western US populations persisted, and appeared to be more associated with regional agricultural and animal production practices. Omnivores and vegetarians from Brazil and the US were isotopically distinct, both within and between regions. In a comparison of fingernails of individuals from an urban city and isolated communities in the Amazonian region, the urban region was similar to southeastern Brazil, whereas individuals from isolated nonurban communities showed distinctive isotopic values consistent with their diets and with the isotopic values of local foods. Although there is a tendency for a "global supermarket" diet, carbon and nitrogen isotopes of human fingernails hold dietary information directly related to both food sources and dietary practices in a region. 2006 Wiley-Liss, Inc.

δ15N values of atmospheric N species simultaneously collected using sector-based samplers distant from sources - Isotopic inheritance and fractionation

NASA Astrophysics Data System (ADS)

Savard, Martine M.; Cole, Amanda; Smirnoff, Anna; Vet, Robert

2017-08-01

The nitrogen isotope ratios (δ15N) of atmospheric N species are commonly suggested as indicators of N emission sources. Therefore, numerous research studies have developed analytical methodologies and characterized primary (gases) and secondary emission products (mostly precipitation and aerosols) from various emitters. These previous studies have generally collected either reduced or oxidized N forms, and sampled them separately prior to determining their δ15N values. Distinctive isotopic signals have been reported for emissions from various sources, and seasonality of the δ15N values has been frequently attributed to shifts in relative contributions from sources with different isotopic signals. However, theoretical concepts suggest that temperature effects on isotopic fractionation may also affect the δ15N values of atmospheric reaction products. Here we use a sector-based multi-stage filter system to simultaneously collect seven reduced and oxidized N species downwind from five different source types in Alberta, Canada. We report δ15N values obtained with a state-of-the-art gold-furnace pre-concentrator online with an isotope ratio mass spectrometer (IRMS) to provide representative results even for oxidized-N forms. We find that equilibrium isotope effects and their temperature dependence play significant roles in determining the δ15N values of the secondary emission products. In the end, seasonal δ15N changes here are mainly caused by temperature effects on fractionation, and the δ15N values of only two N species from one source type can be retained as potential fingerprints of emissions.

Plume dynamics beneath the African plate inferred from the geochemistry of the Tertiary basalts of southern Ethiopia

NASA Astrophysics Data System (ADS)

George, R. M.; Rogers, N. W.

2002-09-01

Southern Ethiopian flood basalts erupted in two episodes: the pre-rift Amaro and Gamo transitional tholeiites (45-35 million years) followed by the syn-extensional Getra-Kele alkali basalts (19-11 million years). These two volcanic episodes are distinct in both trace element and isotope ratios (Zr/Nb ratios in Amaro/Gamo lavas fall between 7 and 14, and 3-4.7 in the Getra-Kele lavas whereas 206Pb/204Pb ratios fall between 18-19 and 18.9-20, respectively). The distinctive chemistries of the two eruptive phases record the tapping of two distinct source regions: a mantle plume source for the Amaro/Gamo phase and an enriched continental mantle lithosphere source for the Getra-Kele phase. Isotope and trace element variations within the Amaro/Gamo lavas reflect polybaric fractional crystallisation initiated at high pressures accompanied by limited crustal contamination. We show that clinopyroxene removal at high (0.5 GPa) crustal pressures provides an explanation for the common occurrence of transitional tholeiites in Ethiopia relative to other, typically tholeiitic flood basalt provinces. The mantle plume signature inferred from the most primitive Amaro basalts is isotopically distinct from that contributing to melt generation in central Ethiopian and Afar. This, combined with Early Tertiary plate reconstructions and similarities with Kenyan basalts farther south, lends credence to derivation of these melts from the Kenyan plume rather than the Afar mantle plume. The break in magmatism between 35 and 19 Ma is consistent with the northward movement away from the Kenya plume predicted from plate tectonic reconstructions. In this model the Getra-Kele magmatism is a response to heating of carbonatitically metasomatised lithosphere by the Afar mantle plume beneath southern Ethiopia at this time.

Nitrate stable isotopes: Tools for determining nitrate sources among different land uses in the Mississippi River Basin

USGS Publications Warehouse

Chang, Cecily C.Y.; Kendall, C.; Silva, S.R.; Battaglin, W.A.; Campbell, D.H.

2002-01-01

A study was conducted to determine whether NO3- stable isotopes (??15N and ??18O), at natural abundance levels, could discriminate among NO3- sources from sites with different land uses at the basin scale. Water samples were collected from 24 sites in the Mississippi River Basin from five land-use categories: (1) large river basins (>34 590 km2) draining multiple land uses and smaller basins in which the predominant land use was (2) urban (3) undeveloped, (4) crops, or (5) crops and livestock. Our data suggest that riverine nitrates from different land uses have overlapping but moderately distinct isotopic signatures. ??18O data were critical in showing abrupt changes in NO3- source with discharge. The isotopic values of large rivers resembled crop sites, sites with livestock tended to have ??15N values characteristic of manure, and urban sites tended to have high ??18O values characteristic of atmospheric nitrate.

Stable carbon isotope ratio of methyl chloride emitted from glasshouse-grown tropical plants and its implication for the global methyl chloride budget

NASA Astrophysics Data System (ADS)

Saito, Takuya; Yokouchi, Yoko

2008-04-01

Stable carbon isotope ratios of methyl chloride (CH3Cl) were measured in foliar emissions from 14 species of tropical plants growing in a glasshouse. The isotopic ratio of CH3Cl (arithmetic mean: -83.2 +/- 15.2‰) ranged from -56‰ to -114‰ that from dipterocarp trees (-87.4 +/- 12.3‰) was on average more depleted in 13C than that from tree ferns (-61.9 +/- 9.7‰). The isotopic ratio was lower than that of CH3Cl produced by other known sources (e.g., biomass burning and salt marshes), with the exception of that by dead leaves. Using the distinctive isotope ratio of CH3Cl emitted from tropical plants together with previously reported isotopic data of CH3Cl sources and sinks to an isotopic mass balance calculation, global CH3Cl emission by tropical plants was estimated to be approximately 1500-3000 Gg yr-1 with uncertainties of 30-60%, which could account for 30-50% of the global emission.

Methane source identification in Boston, Massachusetts using isotopic and ethane measurements

NASA Astrophysics Data System (ADS)

Down, A.; Jackson, R. B.; Plata, D.; McKain, K.; Wofsy, S. C.; Rella, C.; Crosson, E.; Phillips, N. G.

2012-12-01

Methane has substantial greenhouse warming potential and is the principle component of natural gas. Fugitive natural gas emissions could be a significant source of methane to the atmosphere. However, the cumulative magnitude of natural gas leaks is not yet well constrained. We used a combination of point source measurements and ambient monitoring to characterize the methane sources in the Boston urban area. We developed distinct fingerprints for natural gas and multiple biogenic methane sources based on hydrocarbon concentration and isotopic composition. We combine these data with periodic measurements of atmospheric methane and ethane concentration to estimate the fractional contribution of natural gas and biogenic methane sources to the cumulative urban methane flux in Boston. These results are used to inform an inverse model of urban methane concentration and emissions.

Isotopic diversity indices: how sensitive to food web structure?

PubMed

Brind'Amour, Anik; Dubois, Stanislas F

2013-01-01

Recently revisited, the concept of niche ecology has lead to the formalisation of functional and trophic niches using stable isotope ratios. Isotopic diversity indices (IDI) derived from a set of measures assessing the dispersion/distribution of points in the δ-space were recently suggested and increasingly used in the literature. However, three main critics emerge from the use of these IDI: 1) they fail to account for the isotopic sources overlap, 2) some indices are highly sensitive to the number of species and/or the presence of rare species, and 3) the lack of standardization prevents any spatial and temporal comparisons. Using simulations we investigated the ability of six commonly used IDI to discriminate among different trophic food web structures, with a focus on the first two critics. We tested the sensitivity of the IDI to five food web structures along a gradient of sources overlap, varying from two distinct food chains with differentiated sources to two superimposed food chains sharing two sources. For each of the food web structure we varied the number of species (from 10 to 100 species) and the type of species feeding behaviour (i.e. random or selective feeding). Values of IDI were generally larger in food webs with distinct basal sources and tended to decrease as the superimposition of the food chains increased. This was more pronounced when species displayed food preferences in comparison to food webs where species fed randomly on any prey. The number of species composing the food web also had strong effects on the metrics, including those that were supposedly less sensitive to small sample size. In all cases, computing IDI on food webs with low numbers of species always increases the uncertainty of the metrics. A threshold of ~20 species was detected above which several metrics can be safely used.

Water isotope partitioning and ecohydrologic separation in mixed conifer forest explored with a centrifugation water extraction method

NASA Astrophysics Data System (ADS)

Bowers, W.; Mercer, J.; Pleasants, M.; Williams, D. G.

2017-12-01

Isotopic partitioning of water within soil into tightly and loosely bound fractions has been proposed to explain differences between isotopic water sources used by plants and those that contribute to streams and ground water, the basis for the "two water worlds" hypothesis. We examined the isotope ratio values of water in trees, bulk soil, mobile water collected from soil lysimeters, stream water, and GW at three different hillslopes in a mixed conifer forest in southeastern Wyoming, USA. Hillslopes differed in aspect and topographic position with corresponding differences in surface energy balance, snowmelt timing, and duration of soil moisture during the dry summer. The isotopic results support the partitioning of water within the soil; trees apparently used a different pool of water for transpiration than that recovered from soil lysimeters and the source was not resolved with the isotopic signature of the water that was extracted from bulk soil via cryogenic vacuum distillation. Separating and measuring the isotope ratios values in these pools would test the assumption that the tightly bound water within the soil has the same isotopic signature as the water transpired by the trees. We employed a centrifugation approach to separate water within the soil held at different tensions by applying stepwise increases in rotational velocity and pressures to the bulk soil samples. Effluent and the remaining water (cryogenically extracted) at each step were compared. We first applied the centrifugation method in a simple lab experiment using sandy loam soil and separate introductions of two isotopically distinct waters. We then applied the method to soil collected from the montane hillslopes. For the lab experiment, we predicted that effluents would have distinct isotopic signatures, with the last effluent and extracted water more closely representing the isotopic signature of the first water applied. For our field samples, we predicted that the isotopic signature of the water discharged in the last centrifuge step and final extraction would more closely represent the isotopic signature of water extracted from trees. Understanding the isotopic partitioning of water within soil is important for interpreting plant water isotope values within the context of the "two water worlds" hypothesis.

Nd and Sm isotopic composition of spent nuclear fuels from three material test reactors

DOE PAGES

Sharp, Nicholas; Ticknor, Brian W.; Bronikowski, Michael; ...

2016-11-17

Rare earth elements such as neodymium and samarium are ideal for probing the neutron environment that spent nuclear fuels are exposed to in nuclear reactors. The large number of stable isotopes can provide distinct isotopic signatures for differentiating the source material for nuclear forensic investigations. The rare-earth elements were isolated from the high activity fuel matrix via ion exchange chromatography in a shielded cell. The individual elements were then separated using cation exchange chromatography. In conclusion, the neodymium and samarium aliquots were analyzed via MC–ICP–MS, resulting in isotopic compositions with a precision of 0.01–0.3%.

Nd and Sm isotopic composition of spent nuclear fuels from three material test reactors

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

Sharp, Nicholas; Ticknor, Brian W.; Bronikowski, Michael

Rare earth elements such as neodymium and samarium are ideal for probing the neutron environment that spent nuclear fuels are exposed to in nuclear reactors. The large number of stable isotopes can provide distinct isotopic signatures for differentiating the source material for nuclear forensic investigations. The rare-earth elements were isolated from the high activity fuel matrix via ion exchange chromatography in a shielded cell. The individual elements were then separated using cation exchange chromatography. In conclusion, the neodymium and samarium aliquots were analyzed via MC–ICP–MS, resulting in isotopic compositions with a precision of 0.01–0.3%.

Isotopic composition of waters from Ethiopia and Kenya: Insights into moisture sources for eastern Africa

NASA Astrophysics Data System (ADS)

Levin, Naomi E.; Zipser, Edward J.; Cerling, Thure E.

2009-12-01

Oxygen and deuterium isotopic values of meteoric waters from Ethiopia are unusually high when compared to waters from other high-elevation settings in Africa and worldwide. These high values are well documented; however, the climatic processes responsible for the isotopic anomalies in Ethiopian waters have not been thoroughly investigated. We use isotopic data from waters and remote data products to demonstrate how different moisture sources affect the distribution of stable isotopes in waters from eastern Africa. Oxygen and deuterium stable isotopic data from 349 surface and near-surface groundwaters indicate isotopic distinctions between waters in Ethiopia and Kenya and confirm the anomalous nature of Ethiopian waters. Remote data products from the Tropical Rainfall Measuring Mission (TRMM) and National Centers for Environmental Prediction (NCEP) reanalysis project show strong westerly and southwesterly components to low-level winds during precipitation events in western and central Ethiopia. This is in contrast to the easterly and southeasterly winds that bring rainfall to Kenya and southeastern Ethiopia. Large regions of high equivalent potential temperatures (θe) at low levels over the Sudd and the Congo Basin demonstrate the potential for these areas as sources of moisture and convective instability. The combination of wind direction data from Ethiopia and θe distribution in Africa indicates that transpired moisture from the Sudd and the Congo Basin is likely responsible for the high isotopic values of rainfall in Ethiopia.

Ubiquitous tar balls with a California-source signature on the shorelines of Prince William Sound, Alaska

USGS Publications Warehouse

Kvenvolden, K.A.; Hostettler, F.D.; Carlson, P.R.; Rapp, J.B.; Threlkeld, C.N.; Warden, A.

1995-01-01

Although the shorelines of Prince William Sound still bear traces of the 1989 Exxon Valdez oil spill, most of the flattened tar balls that can be found today on these shorelines are not residues of Exxon Valdez oil. Instead, the carbon-isotopic and hydrocarbon-biomarker signatures of 61 tar ball samples, collected from shorelines throughout the northern and western parts of the sound, are all remarkably similar and have characteristics consistent with those of oil products that originated from the Monterey Formation source rocks of California. The carbon-isotopic compositions of the tar balls are all closely grouped (??13CPDB = -23.7 ?? 0.2???), within the range found in crude oils from those rocks, but are distinct from isotopic compositions of 28 samples of residues from the Exxon Valdez oil spill (??13CPDB = -29.4 ?? 0.1???). Likewise, values for selected biomarker ratios in the tar balls are all similar but distinct from values of residues from the 1989 oil spill. Carbon-isotopic and biomarker signatures generally relate the tar balls to oil products used in Alaska before ???1970 for construction and pavements. How these tar balls with such similar geochemical characteristics became so widely dispersed throughout the northern and western parts of the sound is not known with certainty, but the great 1964 Alaska earthquake was undoubtedly an important trigger, causing spills from ruptured storage facilities of California-sourced asphalt and fuel oil into Prince William Sound.

Can Biomass Burning Explain Isotopically Light Fe in Marine Aerosols?

NASA Astrophysics Data System (ADS)

Sherry, A. M.; Anbar, A. D.; Herckes, P.; Romaniello, S. J.

2016-02-01

Iron (Fe) is an important micronutrient that limits primary productivity in large parts of the ocean. In these regions, atmospheric aerosol deposition is an important source of Fe to the surface ocean and thus has a critical impact on ocean biogeochemistry. Fe-bearing aerosols originate from many sources with potentially distinct Fe isotopic compositions. Consequently, Fe isotopes may provide a new tool to trace the sources of aerosol Fe to the oceans. Mead et al. (2013) first discovered that Fe in the fine fraction of Bermuda aerosols is often isotopically lighter than Fe from known anthropogenic and crustal sources. 1 These authors suggested that this light isotopic signature was likely the result of biomass burning, since Fe in plants is the only known source of isotopically light Fe. More recently, Conway et al. found that Fe in the soluble fraction of aerosols collected during 2010-2011 North Atlantic GEOTRACES cruises also showed light isotope values, which they likewise attributed to biomass burning.2 These studies are further supported by new modeling work which suggests that biomass burning aerosols should contribute significant amounts of soluble Fe to tropical and southern oceans.3To test if biomass burning releases aerosols with a light Fe isotope composition, we are conducting lab-scale biomass burning experiments using natural samples of vegetation and leaf litter. Burn aerosols were collected on cellulose filters, then digested and analyzed for trace metal concentrations using inductively-coupled mass spectrometry (ICP-MS). Fe isotopes were determined by using multiple collector ICP-MS following separation and purification of Fe using anion exchange chromatography. We will discuss metal concentration and isotope data from these experiments with implications for the interpretation of Fe isotope signals in aerosol samples. 1Mead, C et al. GRL, 2013, 40, 5722-5727. 2 Conway, T et al. Goldschmidt Abs 2015 593. 3Ito, A. ES&T Lett, 2015, 2, 70-75.

Protein retention assessment of four levels of poultry by-product substitution of fishmeal in rainbow trout (Oncorhynchus mykiss) diets using stable isotopes of nitrogen (δ15N) as natural tracers.

PubMed

Badillo, Daniel; Herzka, Sharon Z; Viana, Maria Teresa

2014-01-01

This is second part from an experiment where the nitrogen retention of poultry by-product meal (PBM) compared to fishmeal (FM) was evaluated using traditional indices. Here a quantitative method using stable isotope ratios of nitrogen (δ(15)N values) as natural tracers of nitrogen incorporation into fish biomass is assessed. Juvenile rainbow trout (Oncorhynchus mykiss) were fed for 80 days on isotopically distinct diets in which 0, 33, 66 and 100% of FM as main protein source was replaced by PBM. The diets were isonitrogenous, isolipidic and similar in gross energy content. Fish in all treatments reached isotopic equilibrium by the end of the experiment. Two-source isotope mixing models that incorporated the isotopic composition of FM and PBM as well as that of formulated feeds, empirically derived trophic discrimination factors and the isotopic composition of fish that had reached isotopic equilibrium to the diets were used to obtain a quantitative estimate of the retention of each source of nitrogen. Fish fed the diets with 33 and 66% replacement of FM by PBM retained poultry by-product meal roughly in proportion to its level of inclusion in the diets, whereas no differences were detected in the protein efficiency ratio. Coupled with the similar biomass gain of fishes fed the different diets, our results support the inclusion of PBM as replacement for fishmeal in aquaculture feeds. A re-feeding experiment in which all fish were fed a diet of 100% FM for 28 days indicated isotopic turnover occurred very fast, providing further support for the potential of isotopic ratios as tracers of the retention of specific protein sources into fish tissues. Stable isotope analysis is a useful tool for studies that seek to obtain quantitative estimates of the retention of different protein sources.

Protein Retention Assessment of Four Levels of Poultry By-Product Substitution of Fishmeal in Rainbow Trout (Oncorhynchus mykiss) Diets Using Stable Isotopes of Nitrogen (δ15N) as Natural Tracers

PubMed Central

Badillo, Daniel; Herzka, Sharon Z.; Viana, Maria Teresa

2014-01-01

This is second part from an experiment where the nitrogen retention of poultry by-product meal (PBM) compared to fishmeal (FM) was evaluated using traditional indices. Here a quantitative method using stable isotope ratios of nitrogen (δ15N values) as natural tracers of nitrogen incorporation into fish biomass is assessed. Juvenile rainbow trout (Oncorhynchus mykiss) were fed for 80 days on isotopically distinct diets in which 0, 33, 66 and 100% of FM as main protein source was replaced by PBM. The diets were isonitrogenous, isolipidic and similar in gross energy content. Fish in all treatments reached isotopic equilibrium by the end of the experiment. Two-source isotope mixing models that incorporated the isotopic composition of FM and PBM as well as that of formulated feeds, empirically derived trophic discrimination factors and the isotopic composition of fish that had reached isotopic equilibrium to the diets were used to obtain a quantitative estimate of the retention of each source of nitrogen. Fish fed the diets with 33 and 66% replacement of FM by PBM retained poultry by-product meal roughly in proportion to its level of inclusion in the diets, whereas no differences were detected in the protein efficiency ratio. Coupled with the similar biomass gain of fishes fed the different diets, our results support the inclusion of PBM as replacement for fishmeal in aquaculture feeds. A re-feeding experiment in which all fish were fed a diet of 100% FM for 28 days indicated isotopic turnover occurred very fast, providing further support for the potential of isotopic ratios as tracers of the retention of specific protein sources into fish tissues. Stable isotope analysis is a useful tool for studies that seek to obtain quantitative estimates of the retention of different protein sources. PMID:25226392

Rb-Sr and Sm-Nd chronology and genealogy of mare basalts from the Sea of Tranquility

NASA Technical Reports Server (NTRS)

Papanastassiou, D. A.; Depaolo, D. J.; Wasserburg, G. J.

1977-01-01

Rb-Sr and Sm-Nd ages of two Apollo 11 mare basalts, high-K basalt 10072 and low-K basalt 10062, are reported. Rb-Sr, Sm-Nd, and Ar-40-Ar-39 ages are in good agreement and indicate an extensive time interval for filling of the Sea of Tranquility, presumably by thin lava flows, in agreement with similar observations for the Ocean of Storms. Initial Sr and Nd isotopic compositions on Apollo 11 basalts reveal at least two parent sources producing basalts. The Sm-Nd isotopic data demonstrate that low-K and high-Ti basalts from Apollo 11 and 17 derived from distinct reservoirs, while low-Ti Apollo 15 mare basalt sources have Sm/Nd similar to the sources of Apollo 11 basalts. Groupings of mare basalt based on Ti content and on isotopic data do not coincide.

Heterogeneity of the Caribbean plateau mantle source: Sr, O and He isotopic compositions of olivine and clinopyroxene from Gorgona Island

NASA Astrophysics Data System (ADS)

Révillon, S.; Chauvel, C.; Arndt, N. T.; Pik, R.; Martineau, F.; Fourcade, S.; Marty, B.

2002-12-01

The composition of the mantle plumes that created large oceanic plateaus such as Ontong Java or the Caribbean is still poorly known. Geochemical and isotopic studies on accreted portions of the Caribbean plateau have shown that the plume source was heterogeneous and contained isotopically depleted and relatively enriched portions. A distinctive feature of samples from the Caribbean plateau is their unusual Sr isotopic compositions, which, at a given Nd isotopic ratio, are far higher than in samples from other oceanic plateaus. Sr, O and He isotopic compositions of whole rocks and magmatic minerals (clinopyroxene or olivine) separated from komatiites, gabbros and peridotites from Gorgona Island in Colombia were determined to investigate the origin of these anomalously radiogenic compositions. Sequentially leached clinopyroxenes have Sr isotopic compositions in the range 87Sr/ 86Sr=0.70271-0.70352, systematically lower than those of leached and unleached whole rocks. Oxygen isotopic ratios of clinopyroxene vary within the range δ 18O=5.18-5.35‰, similar to that recorded in oceanic island basalts. He isotopic ratios are high ( R/ Ra=8-19). The lower 87Sr/ 86Sr ratios of most of the clinopyroxenes shift the field of the Caribbean plateau in Nd-Sr isotope diagrams toward more 'normal' values, i.e. a position closer to the field defined by mid-ocean ridge basalts and oceanic-island basalts. Three clinopyroxenes have slightly higher 87Sr/ 86Sr ratios that cannot be explained by an assimilation model. The high 87Sr/ 86Sr and variations of 143Nd/ 144Nd are interpreted as a source characteristic. Trace-element ratios, however, are controlled mainly by fractionation during partial melting. We combine these isotopic data in a heterogeneous plume source model that accounts for the diversity of isotopic signatures recorded on Gorgona Island and throughout the Caribbean plateau. The heterogeneities are related to old recycled oceanic lithosphere in the plume source; the high 3He/ 4He ratios may indicate that the source material once resided in the lower mantle.

Sediment Fingerprinting Using Carbon and Nitrogen Stable Isotopes in the Upper Palouse Watershed, Northwestern Idaho

NASA Astrophysics Data System (ADS)

Fox, J. F.; Papanicolaou, A. T.

2003-12-01

Unwarranted soil erosion creates detrimental problems for watershed users and for habitats and human infrastructure that experience increased suspended sediment in surface water. Identification and mitigation of erosion prone uplands relies on the realization that land uses (i.e. agriculture, forest, industrial, pasture, etc.) "produce sediment differently" at the watershed scale. Quantification of sediment production from various land uses is deemed feasible by using sediment-particle fingerprinting. This technique utilizes vegetative derived carbon (C) and nitrogen (N) stable isotopes and the carbon/nitrogen (C/N) atomic ratio of sediments to identify sediment producing land uses. Past research has established differences between C and N isotopic signatures and C/N ratios for soils under forest vs. agriculture (i.e. grasses and wheat) land cover. The current research rigorously examines these distinct signatures through isotopic analysis of field soils from the Palouse River Watershed of Northwestern Idaho preceded with statistical analyses to establish soil uniqueness. In addition, stream sediments are preliminarily analyzed to identify their origin with the goal of establishing a blueprint methodology for estimating sediment source and erosion rates within the watershed. Prior to field sampling of source soils, a statistical-experimental design was established with the intent to capture spatial and temporal variations and random errors of C and N isotopic signatures and C/N ratios within the forest and agriculture land uses. Factors including, elevation, slope topography, and season, were assessed by excavating over 300 samples during 4 seasons (i.e. May 2002, August 2002, November 2002, and March 2003) and at numerous locations throughout the watershed. Atomic analyses was performed at the University of Idaho Natural Resources Stable Isotope Laboratory using a Costech 4010 Elemental Combustion System connected with a continuous flow inlet system to the Finnigan MAT Delta Plus isotope ratio mass spectrometer. The statistical analysis of variance (ANOVA) with C and N isotopic signatures and C/N ratios as three independent response variables was administered to identify the agriculture and forested uniqueness, and discriminant analysis was used to create an organic fingerprint parameter which weights the contribution of C and N isotopic signatures and C/N ratios to the land cover separation. Results indicate uniqueness of the N isotope C/N ratio for the forest and agriculture sediment sources and little distinction possible for the C isotope signature. The organic fingerprint parameter was then calculated and coupled with in-stream sediment isotopic data using a simple end-member model. Preliminary results indicate that C and N isotopic signatures and C/N ratios will serve as a useful technique in quantifying erosive source rates and understanding upland erosion processes.

Carbon isotope analyses of n-alkanes released from rapid pyrolysis of oil asphaltenes in a closed system.

PubMed

Chen, Shasha; Jia, Wanglu; Peng, Ping'an

2016-08-15

Carbon isotope analysis of n-alkanes produced by the pyrolysis of oil asphaltenes is a useful tool for characterizing and correlating oil sources. Low-temperature (320-350°C) pyrolysis lasting 2-3 days is usually employed in such studies. Establishing a rapid pyrolysis method is necessary to reduce the time taken for the pretreatment process in isotope analyses. One asphaltene sample was pyrolyzed in sealed ampoules for different durations (60-120 s) at 610°C. The δ(13) C values of the pyrolysates were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The molecular characteristics and isotopic signatures of the pyrolysates were investigated for the different pyrolysis durations and compared with results obtained using the normal pyrolysis method, to determine the optimum time interval. Several asphaltene samples derived from various sources were analyzed using this method. The asphaltene pyrolysates of each sample were similar to those obtained by the flash pyrolysis method on similar samples. However, the molecular characteristics of the pyrolysates obtained over durations longer than 90 s showed intensified secondary reactions. The carbon isotopic signatures of individual compounds obtained at pyrolysis durations less than 90 s were consistent with those obtained from typical low-temperature pyrolysis. Several asphaltene samples from various sources released n-alkanes with distinct carbon isotopic signatures. This easy-to-use pyrolysis method, combined with a subsequent purification procedure, can be used to rapidly obtain clean n-alkanes from oil asphaltenes. Carbon isotopic signatures of n-alkanes released from oil asphaltenes from different sources demonstrate the potential application of this method in 'oil-oil' and 'oil-source' correlations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Stable isotopes in juvenile marine fishes and their invertebrate prey from the Thames Estuary, UK, and adjacent coastal regions

NASA Astrophysics Data System (ADS)

Leakey, Chris D. B.; Attrill, Martin J.; Jennings, Simon; Fitzsimons, Mark F.

2008-04-01

Estuaries are regarded as valuable nursery habitats for many commercially important marine fishes, potentially providing a thermal resource, refuge from predators and a source of abundant prey. Stable isotope analysis may be used to assess relative resource use from isotopically distinct sources. This study comprised two major components: (1) development of a spatial map and discriminant function model of stable isotope variation in selected invertebrate groups inhabiting the Thames Estuary and adjacent coastal regions; and (2) analysis of stable isotope signatures of juvenile bass ( Dicentrarchus labrax), sole ( Solea solea) and whiting ( Merlangius merlangus) for assessment of resource use and feeding strategies. The data were also used to consider anthropogenic enrichment of the estuary and potential energetic benefits of feeding in estuarine nursery habitat. Analysis of carbon (δ 13C), nitrogen (δ 15N) and sulphur (δ 34S) isotope data identified significant differences in the 'baseline' isotopic signatures between estuarine and coastal invertebrates, and discriminant function analysis allowed samples to be re-classified to estuarine and coastal regions with 98.8% accuracy. Using invertebrate signatures as source indicators, stable isotope data classified juvenile fishes to the region in which they fed. Feeding signals appear to reflect physiological (freshwater tolerance) and functional (mobility) differences between species. Juvenile sole were found to exist as two isotopically-discrete sub-populations, with no evidence of mixing between the two. An apparent energetic benefit of estuarine feeding was only found for sole.

Natural uranium and strontium isotope tracers of water sources and surface water-groundwater interactions in arid wetlands: Pahranagat Valley, Nevada, USA

USGS Publications Warehouse

Paces, James B.; Wurster, Frederic C.

2014-01-01

Near-surface physical and chemical process can strongly affect dissolved-ion concentrations and stable isotope compositions of water in wetland settings, especially under arid climate conditions. In contrast, heavy radiogenic isotopes of strontium (87Sr/86Sr) and uranium (234U/238U) remain largely unaffected and can be used to help identify unique signatures from different sources and quantify end-member mixing that would otherwise be difficult to determine. The utility of combined Sr and U isotopes are demonstrated in this study of wetland habitats on the Pahranagat National Wildlife Refuge, which depend on supply from large-volume springs north of the Refuge, and from small-volume springs and seeps within the Refuge. Water budgets from these sources have not been quantified previously. Evaporation, transpiration, seasonally variable surface flow, and water management practices complicate the use of conventional methods for determining source contributions and mixing relations. In contrast, 87Sr/86Sr and 234U/238U remain unfractionated under these conditions, and compositions at a given site remain constant. Differences in Sr- and U-isotopic signatures between individual sites can be related by simple two- or three-component mixing models. Results indicate that surface flow constituting the Refuge’s irrigation source consists of a 65:25:10 mixture of water from two distinct regionally sourced carbonate aquifer springs, and groundwater from locally sourced volcanic aquifers. Within the Refuge, contributions from the irrigation source and local groundwater are readily determined and depend on proximity to those sources as well as water management practices.

Natural uranium and strontium isotope tracers of water sources and surface water-groundwater interactions in arid wetlands - Pahranagat Valley, Nevada, USA

NASA Astrophysics Data System (ADS)

Paces, James B.; Wurster, Frederic C.

2014-09-01

Near-surface physical and chemical process can strongly affect dissolved-ion concentrations and stable-isotope compositions of water in wetland settings, especially under arid climate conditions. In contrast, heavy radiogenic isotopes of strontium (87Sr/86Sr) and uranium (234U/238U) remain largely unaffected and can be used to help identify unique signatures from different sources and quantify end-member mixing that would otherwise be difficult to determine. The utility of combined Sr and U isotopes are demonstrated in this study of wetland habitats on the Pahranagat National Wildlife Refuge, which depend on supply from large-volume springs north of the Refuge, and from small-volume springs and seeps within the Refuge. Water budgets from these sources have not been quantified previously. Evaporation, transpiration, seasonally variable surface flow, and water management practices complicate the use of conventional methods for determining source contributions and mixing relations. In contrast, 87Sr/86Sr and 234U/238U remain unfractionated under these conditions, and compositions at a given site remain constant. Differences in Sr- and U-isotopic signatures between individual sites can be related by simple two- or three-component mixing models. Results indicate that surface flow constituting the Refuge's irrigation source consists of a 65:25:10 mixture of water from two distinct regionally sourced carbonate-aquifer springs, and groundwater from locally sourced volcanic aquifers. Within the Refuge, contributions from the irrigation source and local groundwater are readily determined and depend on proximity to those sources as well as water management practices.

Late Quaternary loess in northeastern Colorado: Part II - Pb isotopic evidence for the variability of loess sources

USGS Publications Warehouse

Aleinikoff, J.N.; Muhs, D.R.; Sauer, R.R.; Fanning, C.M.

1999-01-01

A new application of the Pb isotopic tracer technique has been used to determine the relative importance of different silt sources for late Wisconsin loess in the central Great Plains of eastern Colorado. Samples of the Peoria Loess collected throughout the study area contain K-feldspar derived from two isotopically and genetically distinct sources: (1) glaciogenic material from Early and Middle Proterozoic crystalline rocks of the Colorado province, and (2) volcaniclastic material from the Tertiary White River Group exposed on the northern Great Plains. Pb isotopic compositions of K-feldspar in loess from two dated vertical sections (at Beecher Island and Last Chance, Colorado) vary systematically, implying climatic control of source availability. We propose a model whereby relatively cold conditions promoted the advance of Front Range valley glaciers discharging relatively little glaciogenic silt, but strong winds caused eolian erosion of White River Group silt due to a decrease in vegetation cover. During warmer periods, valley glaciers receded and discharged abundant glaciogenic silt, while surfaces underlain by the White River Group were stabilized by vegetation. Isotopic data from eastern Colorado loess sections record two warm-cold-warm cycles during late Wisconsin time between about 21 000 and 11 000 radiocarbon yr B.P., similar to results from other studies in the United States and Greenland.

Sources and atmospheric processing of size segregated aerosol particles revealed by stable carbon isotope ratios and chemical speciation.

PubMed

Masalaite, A; Holzinger, R; Ceburnis, D; Remeikis, V; Ulevičius, V; Röckmann, T; Dusek, U

2018-05-07

Size-segregated aerosol particles were collected during winter sampling campaigns at a coastal (55°37' N, 21°03'E) and an urban (54°64' N, 25°18' E) site. Organic compounds were thermally desorbed from the samples at different temperature steps ranging from 100 °C to 350 °C. The organic matter (OM) desorbed at each temperature step is analysed for stable carbon isotopes using an isotope ratio mass spectrometer (IRMS) and for individual organic compounds using a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-MS). The OM desorbed at temperatures <200 °C was classified as less refractory carbon and the OM desorbed at temperatures between 200 °C and 350 °C was classified as more refractory carbon. At the coastal site, we identified two distinct time periods. The first period was more frequently influenced by marine air masses than the second time period, which was characterized by Easterly wind directions and continental air masses. During the first period OM contained a large fraction of hydrocarbons and had a carbon isotopic signature typical of liquid fossil fuels in the region. Organic mass spectra provide strong evidence that shipping emissions are a significant source of OM at this coastal site. The isotopic and chemical composition of OM during the second period at the coastal site was similar to the composition at the urban site. There was a clear distinction in source contribution between the less refractory OM and the more refractory OM at these sites. According to the source apportionment method used in this study, we were able to identify fossil fuel burning as predominant source of the less refractory OM in the smallest particles (D 50  < 0.18 μm), and biomass burning as predominant source of the more refractory OM in the larger size range (0.32 < D 50  < 1 μm). Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

Ruthenium isotopic evidence for an inner Solar System origin of the late veneer

NASA Astrophysics Data System (ADS)

Fischer-Gödde, Mario; Kleine, Thorsten

2017-01-01

The excess of highly siderophile elements in the Earth’s mantle is thought to reflect the addition of primitive meteoritic material after core formation ceased. This ‘late veneer’ either comprises material remaining in the terrestrial planet region after the main stages of the Earth’s accretion, or derives from more distant asteroidal or cometary sources. Distinguishing between these disparate origins is important because a late veneer consisting of carbonaceous chondrite-like asteroids or comets could be the principal source of the Earth’s volatiles and water. Until now, however, a ‘genetic’ link between the late veneer and such volatile-rich materials has not been established or ruled out. Such genetic links can be determined using ruthenium (Ru) isotopes, because the Ru in the Earth’s mantle predominantly derives from the late veneer, and because meteorites exhibit Ru isotope variations arising from the heterogeneous distribution of stellar-derived dust. Although Ru isotopic data and the correlation of Ru and molybdenum (Mo) isotope anomalies in meteorites were previously used to argue that the late veneer derives from the same type of inner Solar System material as do Earth’s main building blocks, the Ru isotopic composition of carbonaceous chondrites has not been determined sufficiently well to rule them out as a source of the late veneer. Here we show that all chondrites, including carbonaceous chondrites, have Ru isotopic compositions distinct from that of the Earth’s mantle. The Ru isotope anomalies increase from enstatite to ordinary to carbonaceous chondrites, demonstrating that material formed at greater heliocentric distance contains larger Ru isotope anomalies. Therefore, these data refute an outer Solar System origin for the late veneer and imply that the late veneer was not the primary source of volatiles and water on the Earth.

Isotopes as tracers of the sources of the lunar material and processes of lunar origin.

PubMed

Pahlevan, Kaveh

2014-09-13

Ever since the Apollo programme, isotopic abundances have been used as tracers to study lunar formation, in particular to study the sources of the lunar material. In the past decade, increasingly precise isotopic data have been reported that give strong indications that the Moon and the Earth's mantle have a common heritage. To reconcile these observations with the origin of the Moon via the collision of two distinct planetary bodies, it has been proposed (i) that the Earth-Moon system underwent convective mixing into a single isotopic reservoir during the approximately 10(3) year molten disc epoch after the giant impact but before lunar accretion, or (ii) that a high angular momentum impact injected a silicate disc into orbit sourced directly from the mantle of the proto-Earth and the impacting planet in the right proportions to match the isotopic observations. Recently, it has also become recognized that liquid-vapour fractionation in the energetic aftermath of the giant impact is capable of generating measurable mass-dependent isotopic offsets between the silicate Earth and Moon, rendering isotopic measurements sensitive not only to the sources of the lunar material, but also to the processes accompanying lunar origin. Here, we review the isotopic evidence that the silicate-Earth-Moon system represents a single planetary reservoir. We then discuss the development of new isotopic tracers sensitive to processes in the melt-vapour lunar disc and how theoretical calculations of their behaviour and sample observations can constrain scenarios of post-impact evolution in the earliest history of the Earth-Moon system. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

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.

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.

Joint Application of Concentrations and Isotopic Signatures to Investigate the Global Atmospheric Carbon Monoxide Budget: Inverse Modeling Approach

NASA Astrophysics Data System (ADS)

Park, K.; Emmons, L. K.; Mak, J. E.

2007-12-01

Carbon monoxide is not only an important component for determining the atmospheric oxidizing capacity but also a key trace gas in the atmospheric chemistry of the Earth's background environment. The global CO cycle and its change are closely related to both the change of CO mixing ratio and the change of source strength. Previously, to estimate the global CO budget, most top-down estimation techniques have been applied the concentrations of CO solely. Since CO from certain sources has a unique isotopic signature, its isotopes provide additional information to constrain its sources. Thus, coupling the concentration and isotope fraction information enables to tightly constrain CO flux by its sources and allows better estimations on the global CO budget. MOZART4 (Model for Ozone And Related chemical Tracers), a 3-D global chemical transport model developed at NCAR, MPI for meteorology and NOAA/GFDL and is used to simulate the global CO concentration and its isotopic signature. Also, a tracer version of MOZART4 which tagged for C16O and C18O from each region and each source was developed to see their contributions to the atmosphere efficiently. Based on the nine-year- simulation results we analyze the influences of each source of CO to the isotopic signature and the concentration. Especially, the evaluations are focused on the oxygen isotope of CO (δ18O), which has not been extensively studied yet. To validate the model performance, CO concentrations and isotopic signatures measured from MPI, NIWA and our lab are compared to the modeled results. The MOZART4 reproduced observational data fairly well; especially in mid to high latitude northern hemisphere. Bayesian inversion techniques have been used to estimate the global CO budget with combining observed and modeled CO concentration. However, previous studies show significant differences in their estimations on CO source strengths. Because, in addition to the CO mixing ratio, isotopic signatures are independent tracers that contain the source information, jointly applying the isotope and the concentration information is expected to provide more precise optimization results in CO budget estimation. Our accumulated long-term CO isotope measurement data contribute to having more confidence of the inversions as well. Besides the benefit of adding isotope data on the inverse modeling, a trait of each isotope of CO (oxygen and carbon isotope) contains another advantageous use in the top-down estimation of the CO budget. δ18O and δ13C has a distinctive isotopic signature on a specific source; combustion sources such as a fossil fuel use show clearly different values from other natural sources in the δ18O signatures and the methane source can be easily separated by using δ13C information. Therefore, inversions of the two major sources of CO respond with different sensitivity for the different isotopes. To maximize the strengths of using isotope data in the inverse modeling analysis, various coupling schemes combining [CO], δ18O and δ13C have been investigated to enhance the credibility of the CO budget optimization.

Joint Application of Concentrations and Isotopic Signatures to Investigate the Global Atmospheric Carbon Monoxide Budget: Inverse Modeling Approach

NASA Astrophysics Data System (ADS)

Park, K.; Mak, J. E.; Emmons, L. K.

2008-12-01

Carbon monoxide is not only an important component for determining the atmospheric oxidizing capacity but also a key trace gas in the atmospheric chemistry of the Earth's background environment. The global CO cycle and its change are closely related to both the change of CO mixing ratio and the change of source strength. Previously, to estimate the global CO budget, most top-down estimation techniques have been applied the concentrations of CO solely. Since CO from certain sources has a unique isotopic signature, its isotopes provide additional information to constrain its sources. Thus, coupling the concentration and isotope fraction information enables to tightly constrain CO flux by its sources and allows better estimations on the global CO budget. MOZART4 (Model for Ozone And Related chemical Tracers), a 3-D global chemical transport model developed at NCAR, MPI for meteorology and NOAA/GFDL and is used to simulate the global CO concentration and its isotopic signature. Also, a tracer version of MOZART4 which tagged for C16O and C18O from each region and each source was developed to see their contributions to the atmosphere efficiently. Based on the nine-year-simulation results we analyze the influences of each source of CO to the isotopic signature and the concentration. Especially, the evaluations are focused on the oxygen isotope of CO (δ18O), which has not been extensively studied yet. To validate the model performance, CO concentrations and isotopic signatures measured from MPI, NIWA and our lab are compared to the modeled results. The MOZART4 reproduced observational data fairly well; especially in mid to high latitude northern hemisphere. Bayesian inversion techniques have been used to estimate the global CO budget with combining observed and modeled CO concentration. However, previous studies show significant differences in their estimations on CO source strengths. Because, in addition to the CO mixing ratio, isotopic signatures are independent tracers that contain the source information, jointly applying the isotope and the concentration information is expected to provide more precise optimization results in CO budget estimation. Our accumulated long-term CO isotope measurement data contribute to having more confidence of the inversions as well. Besides the benefit of adding isotope data on the inverse modeling, a trait of each isotope of CO (oxygen and carbon isotope) contains another advantageous use in the top-down estimation of the CO budget. δ18O and δ13C has a distinctive isotopic signature on a specific source; combustion sources such as a fossil fuel use show clearly different values from other natural sources in the δ18O signatures and the methane source can be easily separated by using δ13C information. Therefore, inversions of the two major sources of CO respond with different sensitivity for the different isotopes. To maximize the strengths of using isotope data in the inverse modeling analysis, various coupling schemes combining [CO], δ18O and δ13C have been investigated to enhance the credibility of the CO budget optimization.

Determining the source of house flies (Musca domestica) using stable isotope analysis.

PubMed

Heinrich, Katharina; Weaver, Robert J; Bell, Howard A

2012-01-01

Intensive livestock units frequently produce flies in large numbers that, on migration, cause nuisance to the occupants of neighbouring dwellings. The resolution of such problems is often reliant on the unequivocal identification of the origin of the flies, particularly when several potential sources exist. This study evaluated stable isotope analysis as a method for differentiating adult houseflies (Musca domestica) on the basis of their dietary history so as to determine their likely source. Flies were reared in the laboratory on several substrates, including chicken and cattle manure, laboratory diet and household vegetable waste. Different fly parts (wings, heads and legs) and whole flies were analysed immediately after eclosion and after 10 days. The δ(13) C and δ(15) N values for adults that had developed on each diet type were highly distinct. Both isotopic ratios altered markedly after maintaining the flies for 10 days on a diet of cane sugar solution. Stable isotope analysis readily differentiated flies that had developed on a range of substrates. The technique, therefore, shows potential to be employed to determine the likely source of various nuisance insects, and to contribute to the abatement of such problems. Copyright © 2011 Society of Chemical Industry.

Geochemistry of amphibolites from the Kolar Schist Belt

NASA Technical Reports Server (NTRS)

Balakrishnan, S.; Hanson, G. N.; Rajamani, V.

1988-01-01

How the Nd isotope data suggest that the amphibolites from the schist belt were derived from long-term depleted mantle sources at about 2.7 Ga is described. Trace element and Pb isotope data from the amphibolites also suggest that the sources for the amphibolites on the western and eastern sides of the narrow schist belt were derived from different sources. The Pb data from one outcrop of the central tholeiitic amphibolites lies on a 2.7 Ga isochron with a low model. The other amphibolites (W komatiitic, E komatiitic, and E tholeiitic) do not define isochrons, but suggest that they were derived from sources with distinct histories of U/Pb. There is some suggestion that the E komatiitic amphibolites may have been contaminated by fluids carrying Pb from a long-term, high U/Pb source, such as the old granitic crust on the west side of the schist belt. This is consistent with published galena Pb isotope data from the ore lodes within the belt, which also show a history of long-term U/Pb enrichment.

Evaluating the source of streamwater nitrate using d15N and d18O in nitrate in two watersheds in New Hampshire, USA

Treesearch

Linda H. Pardo; Carol Kendall; Jennifer Pett-Ridge; Cecily C.Y. Chang; Cecily C.Y. Chang

2004-01-01

The natural abundance of nitrogen and oxygen isotopes in nitrate can be a powerful tool for identifying the source of nitrate in streamwater in forested watersheds, because the two main sources of nitrate, atmospheric deposition and microbial nitrification, have distinct d18O values. Using a simple mixing model, we estimated the relative fractions in streamwater...

Lead isotope studies of the Guerrero composite terrane, west-central Mexico: implications for ore genesis

NASA Astrophysics Data System (ADS)

Potra, Adriana; Macfarlane, Andrew W.

2014-01-01

New thermal ionization mass spectrometry and multi-collector inductively coupled plasma mass spectrometry Pb isotope analyses of three Cenozoic ores from the La Verde porphyry copper deposit located in the Zihuatanejo-Huetamo subterrane of the Guerrero composite terrane are presented and the metal sources are evaluated. Lead isotope ratios of 3 Cenozoic ores from the El Malacate and La Esmeralda porphyry copper deposits located in the Zihuatanejo-Huetamo subterrane and of 14 ores from the Zimapan and La Negra skarn deposits from the adjoining Sierra Madre terrane are also presented to look for systematic differences in the lead isotope trends and ore metal sources among the proposed exotic tectonostratigraphic terranes of southern Mexico. Comparison among the isotopic signatures of ores from the Sierra Madre terrane and distinct subterranes of the Guerrero terrane supports the idea that there is no direct correlation between the distinct suspect terranes of Mexico and the isotopic signatures of the associated Cenozoic ores. Rather, these Pb isotope patterns are interpreted to reflect increasing crustal contribution to mantle-derived magmas as the arc advanced eastward onto a progressively thicker continental crust. The lead isotope trend observed in Cenozoic ores is not recognized in the ores from Mesozoic volcanogenic massive sulfide and sedimentary exhalative deposits. The Mesozoic ores formed prior to the amalgamation of the Guerrero composite terrane to the continental margin, which took place during the Late Cretaceous, in intraoceanic island arc and intracontinental marginal basin settings, while the Tertiary deposits formed after this event in a continental arc setting. Lead isotope ratios of the Mesozoic and Cenozoic ores appear to reflect these differences in tectonic setting of ore formation. Most Pb isotope values of ores from the La Verde deposit (206Pb/204Pb = 18.674-18.719) are less radiogenic than those of the host igneous rocks, but plot within the field defined by the Huetamo Sequence, suggesting that these ores may also contain metals from the sedimentary rocks. The Pb isotope ratios of ore samples from the Zimapan deposit (206Pb/204Pb = 18.771-18.848) are substantially higher than the whole-rock Pb isotope compositions of the basement rocks. The similarity of ore Pb to igneous rock Pb in the Zimapan district (206Pb/204Pb = 18.800-18.968) may indicate that the proximal source of ore metals in the hydrothermal system was the igneous activity.

Mass-dependent and -independent fractionation of Fe isotopes in magnetotactic bacteria

NASA Astrophysics Data System (ADS)

Amor, M.; Busigny, V.; Louvat, P.; Gelabert, A.; Cartigny, P.; Durand-Dubief, M.; Ona-Nguema, G.; Alphandéry, E.; Chebbi, I.; Guyot, F. J.

2016-12-01

Magnetotactic bacteria (MTB) perform biomineralization of intracellular magnetite (Fe3O4) nanoparticles. Although they may be among the oldest microorganisms capable of biomineralization on Earth, identification of their activity in the geological record remains poorly resolved because of the lack of reliable signatures. Here, we determined Fe isotope fractionation by the magnetotactic bacterium Magnetospirillum magneticum strain AMB-1 to better understand Fe cycling in MTB and provide new signatures of the contribution of MTB to iron geochemistry. AMB-1 strain was cultivated with either Fe(III)-quinate or Fe(II)-ascorbate as Fe sources. Iron isotope composition of Fe sources, bacterial growth media after AMB-1 cultures, bacterial lysates (corresponding to AMB-1 cells devoid of magnetite) and magnetite samples were analyzed by MC-ICP-MS after column chromatography. In the two culture conditions, growth media after AMB-1 cultures were enriched in light Fe isotopes relative to Fe sources. Two distinct bacterial Fe reservoirs were characterized in AMB-1: (1) magnetite enriched in the light Fe isotopes by 1.5 to 2.5‰ in δ56Fe relative to Fe sources, and (2) lysate enriched in the heavy Fe isotopes by 0.3 to 0.8‰ relative to Fe sources. More importantly, mass-independent fractionations in odd (57Fe) but not in even isotopes (54Fe, 56Fe and 58Fe) were observed for the first time, highlighting a magnetic isotope effect. Magnetite samples were significantly enriched in 57Fe by 0.23‰ relative to 54Fe, 56Fe and 58Fe. Based on our results, we propose a model for Fe cycling and magnetite biomineralization in AMB-1, and propose to use this specific mass-independent signature of Fe isotopes to evaluate the contribution of MTB to the iron biogeochemistry of recent and ancient environmental samples.

Coral-based history of lead and lead isotopes of the surface Indian Ocean since the mid-20th century

NASA Astrophysics Data System (ADS)

Lee, Jong-Mi; Boyle, Edward A.; Suci Nurhati, Intan; Pfeiffer, Miriam; Meltzner, Aron J.; Suwargadi, Bambang

2014-07-01

Anthropogenic lead (Pb) from industrial activities has greatly altered the distribution of Pb in the present-day oceans, but no continuous temporal Pb evolution record is available for the Indian Ocean despite rapidly emerging industries around the region. Here, we present the coral-inferred annual history of Pb concentration and isotope ratios in the surface Indian Ocean since the mid-20th century (1945-2010). We analyzed Pb in corals from the Chagos Archipelago, western Sumatra and Strait of Singapore - which represent the central Indian Ocean via nearshore sites. Overall, coral Pb/Ca increased in the mid-1970s at all the sites. However, coral Pb isotope ratios evolve distinctively at each site, suggesting Pb contamination arises from different sources in each case. The major source of Pb in the Chagos coral appears to be India's Pb emission from leaded gasoline combustion and coal burning, whereas Pb in western Sumatra seems to be largely affected by Indonesia's gasoline Pb emission with additional Pb inputs from other sources. Pb in the Strait of Singapore has complex sources and its isotopic composition does not reflect Pb from leaded gasoline combustion. Higher 206Pb/207Pb and 208Pb/207Pb ratios found at this site may reflect the contribution of Pb from coals and ores from southern China, Indonesia, and Australia, and local Pb sources in the Strait of Singapore. It is also possible that the Pb isotope ratios of Singapore seawater were elevated through isotope exchange with natural fluvial particles considering its delta setting.

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.

SHRIMP-SI Multiple Sulfur Isotope Analysis of Sulfides from Brazilian Deposits: Analytical Capability to Resolve Single Grain Textural Complexities and Distinct Sulfur Sources

NASA Astrophysics Data System (ADS)

Ireland, T. R.; Teles, G. D. S.; Chemale, F., Jr.; Avila, J.

2016-12-01

The Archean atmosphere is thought to be several times more reducing than the present day atmosphere, and the occurrence of Mass Independent Fractionation of Sulfur isotopes (MIF-S) in sulfides of sedimentary and volcanogenic rocks older than 2.45 Ga reinforces it. The most accepted mechanism to generate MIF-S requires photochemical reactions with volcanogenic SO2 in an anoxic atmosphere (O2 levels <10-5 PAL). The identification of MIF-S, noted as Δ33S and Δ36S, requires precise measurements of less abundant 33S and 36S isotopes, which were first attained by bulk isotope analyses. However, in-situ analysis has become essential, as many of ancient sulfide samples have suffered post-depositional processes, and their primary isotopic signature from the atmosphere are now overprinted by mass-dependent fractionation processes. High-precision and resolution in situ measurements of 32S, 33S, 34S and 36S in sulfides can be achieved by SHRIMP-SI, which allows isotopic determinations with internal errors better than 0.05‰ for Δ33S and 0.2‰ for Δ36S (2SE), and reproducibility about 0.1‰ for Δ33S and better than 0.5‰ for Δ36S (2SD). Examples of the SHRIMP-SI capability are provided by multiple sulfur isotope analysis of samples from Brazil, the Au-(U) and pyrite deposits of Jacobina Basin and the massive sulfide deposits of the 3.3 Ga Mundo Novo Greenstone Belt. The level of precision and spatial resolution achievable with SHRIMP-SI allowed the isotopic distinction between sedimentary and post-depositional pyrites in Jacobina Basin, as well as the identification of different sulfur sources in the Mundo Novo Greenstone Belt VMS deposits.

Lead Isotopes in Olivine-Phyric Shergottite Tissint: Implications for the Geochemical Evolution of the Shergottite Source Mantle

NASA Technical Reports Server (NTRS)

Moriwaki, R.; Usui, T.; Simon, J. I.; Jones, J. H.; Yokoyama, T.

2015-01-01

Geochemically-depleted shergottites are basaltic rocks derived from a martian mantle source reservoir. Geochemical evolution of the martian mantle has been investigated mainly based on the Rb-Sr, Sm-Nd, and Lu-Hf isotope systematics of the shergottites [1]. Although potentially informative, U-Th- Pb isotope systematics have been limited because of difficulties in interpreting the analyses of depleted meteorite samples that are more susceptible to the effects of near-surface processes and terrestrial contamination. This study conducts a 5-step sequential acid leaching experiment of the first witnessed fall of the geochemically-depleted olivinephyric shergottite Tissint to minimize the effect of low temperature distrubence. Trace element analyses of the Tissint acid residue (mostly pyroxene) indicate that Pb isotope compositions of the residue do not contain either a martian surface or terrestrial component, but represent the Tissint magma source [2]. The residue has relatively unradiogenic initial Pb isotopic compositions (e.g., 206Pb/204Pb = 10.8136) that fall within the Pb isotope space of other geochemically-depleted shergottites. An initial µ-value (238U/204Pb = 1.5) of Tissint at the time of crystallization (472 Ma [3]) is similar to a time-integrated mu- value (1.72 at 472 Ma) of the Tissint source mantle calculated based on the two-stage mantle evolution model [1]. On the other hand, the other geochemically-depleted shergottites (e.g., QUE 94201 [4]) have initial µ-values of their parental magmas distinctly lower than those of their modeled source mantle. These results suggest that only Tissint potentially reflects the geochemical signature of the shergottite mantle source that originated from cumulates of the martian magma ocean

Factors Affecting Mercury Stable Isotopic Distribution in Piscivorous Fish of the Laurentian Great Lakes.

PubMed

Lepak, Ryan F; Janssen, Sarah E; Yin, Runsheng; Krabbenhoft, David P; Ogorek, Jacob M; DeWild, John F; Tate, Michael T; Holsen, Thomas M; Hurley, James P

2018-03-06

Identifying the sources of methylmercury (MeHg) and tracing the transformations of mercury (Hg) in the aquatic food web are important components of effective strategies for managing current and legacy Hg sources. In our previous work, we measured stable isotopes of Hg (δ 202 Hg, Δ 199 Hg, and Δ 200 Hg) in the Laurentian Great Lakes and estimated source contributions of Hg to bottom sediment. Here, we identify isotopically distinct Hg signatures for Great Lakes trout ( Salvelinus namaycush) and walleye ( Sander vitreus), driven by both food-web and water-quality characteristics. Fish contain high values for odd-isotope mass independent fractionation (MIF) with averages ranging from 2.50 (western Lake Erie) to 6.18‰ (Lake Superior) in Δ 199 Hg. The large range in odd-MIF reflects variability in the depth of the euphotic zone, where Hg is most likely incorporated into the food web. Even-isotope MIF (Δ 200 Hg), a potential tracer for Hg from precipitation, appears both disconnected from lake sedimentary sources and comparable in fish among the five lakes. We suggest that similar to the open ocean, water-column methylation also occurs in the Great Lakes, possibly transforming recently deposited atmospheric Hg deposition. We conclude that the degree of photochemical processing of Hg is controlled by phytoplankton uptake rather than by dissolved organic carbon quantity among lakes.

The Debate on the Prospective Interaction between SWIR 46°-52°E and Crozet hotspot: Constrain from the Geochemical Characteristics and Helium isotopes of MORBs from Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Yu, X.; Dick, H. J. B.; Chu, F.; Li, X.; Tang, L.

2017-12-01

The Southwest Indian Ridge with obvious mantle heterogeneity is often attributed to the influence of nearby hotspots. The Dragon Flag Supersegment between 46°E and 52°E on Marion Rise has thicker crust, shallower axial depth, and lower mantle Bouguer anomaly, which indicates ridge-hotspot interaction. However, the great distance between Crozet hotspot and the supersegment (about 1,000km) and the controversial geochemical data are both against the prospective ridge-hotspot interaction. Here we compiled major element, trace element, Sr-Nd-Pb and He isotopic data of new samples from the supersegment. The mantle source, partial melting process as well as the crystallization history of these basalts are further constrained based on the synthetic analysis of the dataset. Most basalts from the supersegment require 0 to 30% olivine and plagioclase fractionation to account for their present composition, whereas the crystallization of clinopyroxene appears to be rather limited. The parental magmas of the supersegment are distinctive from east to west. Most samples from the Eastern Group can be modeled as the product of 10% partial melting of a DMM-like source, while some extremely depleted samples from the central valley may require two stages of partial melting, i.e. ancient melting of DMM-like source, followed by recent remelting of the residues. The Western Group may be resulted from lower degree of partial melting (5-10%), or a previously less depleted mantle source. The Eastern Group is favor of the involvement of Crozet hotspot in terms of Pb isotope and helium isotope signatures, but the trace element and Sr-Nd isotopes are not supportive for this interaction. The especially high 206Pb/204Pb for some of the samples from the Eastern Group, similar to the Crozet hotspot, requires the sporadical entrainment of blobs of relatively enriched source material, like the Crozet component. The Crozet hotspot is distinctive in its Sr-Nd-Pb-He isotopes among different islands, thus it is more complicate to address the issue of ridge-hotspot interaction. We suggest that the prospective Crozet-SWIR interaction is possible and can explain most of the geological and geochemical signatures.

New insights to the use of ethanol in automotive fuels: a stable isotopic tracer for fossil- and bio-fuel combustion inputs to the atmosphere.

PubMed

Giebel, Brian M; Swart, Peter K; Riemer, Daniel D

2011-08-01

Ethanol is currently receiving increased attention because of its use as a biofuel or fuel additive and because of its influence on air quality. We used stable isotopic ratio measurements of (13)C/(12)C in ethanol emitted from vehicles and a small group of tropical plants to establish ethanol's δ(13)C end-member signatures. Ethanol emitted in exhaust is distinctly different from that emitted by tropical plants and can serve as a unique stable isotopic tracer for transportation-related inputs to the atmosphere. Ethanol's unique isotopic signature in fuel is related to corn, a C4 plant and the primary source of ethanol in the U.S. We estimated a kinetic isotope effect (KIE) for ethanol's oxidative loss in the atmosphere and used previous assumptions with respect to the fractionation that may occur during wet and dry deposition. A small number of interpretive model calculations were used for source apportionment of ethanol and to understand the associated effects resulting from atmospheric removal. The models incorporated our end-member signatures and ambient measurements of ethanol, known or estimated source strengths and removal magnitudes, and estimated KIEs associated with atmospheric removal processes for ethanol. We compared transportation-related ethanol signatures to those from biogenic sources and used a set of ambient measurements to apportion each source contribution in Miami, Florida-a moderately polluted, but well ventilated urban location.

Isotopic Abundances as Tracers of the Processes of Lunar Formation

NASA Astrophysics Data System (ADS)

Pahlevan, K.

2011-12-01

Ever since Apollo, isotopic abundances have been used as tracers to study lunar formation, in particular, to study the sources of the lunar material. In the last decade, however, a number of isotopic similarities have been observed between the lunar samples and the Earth's mantle such that these two reservoirs are now known to be indistinguishable from one another to high precision for a variety of isotopic tracers. This occurs against the backdrop of a Solar System that exhibits widespread heterogeneity with respect to these tracers, a situation that strongly argues that the source of the lunar material is the silicate Earth. To reconcile this observation with the fact that the Moon is thought to result from the collision of two isotopically distinct planetary bodies, a scenario has emerged in which the material from the Moon-forming impactor and the proto-Earth are homogenized in the aftermath of the giant impact. This takes place via turbulent mixing in the time after the giant impact but before lunar accretion while the Earth-Moon system exists in the form of a continuous, high-temperature fluid. Importantly, this high-temperature phase of the evolution occurs in the presence of at least two phases (liquid + vapor) making possible chemical and isotopic fractionation. While equilibrium isotopic fractionation tends to zero at high temperatures, and the post giant impact environment experiences some of the highest temperatures encountered in the Earth sciences, there are several factors that nevertheless make equilibrium isotope effects important probes of this early evolution. (1) Because the vaporization of silicates involves decomposition reactions, the bonding environment for elements in the liquid is often very different from that in the vapor. This difference makes the magnitude of isotopic fractionation intrinsically large, even at the relevant temperatures. (2) Since the isotopic composition of a silicate liquid and co-existing vapor are distinctly different, if the Moon preferentially forms from the liquid or vapor relative to the Earth, mass-dependent isotopic differences at the planetary scale may arise. The large density contrast between liquid and vapor makes phase separation possible. (3) The precision with which planetary isotopic compositions can be determined has increased such that measurements are sensitive to even small degrees of high-temperature phase separation. Using thermodynamic models of silicate liquids to determine the partial vaporization behavior of the major elements, we will present calculations of isotopic fractionation due to liquid-vapor separation for the elements iron, magnesium, silicon, and oxygen. Improvements in analytical precision have largely settled the question of the source of the lunar material - the Earth's mantle - and isotopic measurements are now beginning to yield insight into the high-temperatures processes operating during lunar formation.

Stable Isotope Analysis Reveals Detrital Resource Base Sources of the Tree Hole Mosquito, Aedes triseriatus

PubMed Central

Kaufman, Michael G.; Pelz-Stelinski, Kirsten S.; Yee, Donald A.; Juliano, Steven A.; Ostrom, Peggy H.; Walker, Edward D.

2010-01-01

1. Detritus that forms the basis for mosquito production in tree hole ecosystems can vary in type and timing of input. We investigated the contributions of plant- and animal-derived detritus to the biomass of Aedes triseriatus (Say) pupae and adults by using stable isotope (15N and 13C) techniques in lab experiments and field collections. 2. Lab-reared mosquito isotope values reflected their detrital resource base, providing a clear distinction between mosquitoes reared on plant or animal detritus. 3. Isotope values from field-collected pupae were intermediate between what would be expected if a single (either plant or animal) detrital source dominated the resource base. However, mosquito isotope values clustered most closely with plant-derived values, and a mixed feeding model analysis indicated tree floral parts contributed approximately 80% of mosquito biomass. The mixed model also indicated that animal detritus contributed approximately 30% of mosquito tissue nitrogen. 4. Pupae collected later in the season generally had isotope values that were consistent with an increased contribution from animal detritus, suggesting this resource became more nutritionally important for mosquitoes as plant inputs declined over the summer. PMID:21132121

Compound-Specific Isotope Analysis of Diesel Fuels in a Forensic Investigation

NASA Astrophysics Data System (ADS)

Muhammad, Syahidah; Frew, Russell; Hayman, Alan

2015-02-01

Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin i.e. the very subtle differences in isotopic values between the samples.

Compound-specific isotope analysis of diesel fuels in a forensic investigation

PubMed Central

Muhammad, Syahidah A.; Frew, Russell D.; Hayman, Alan R.

2015-01-01

Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin, i.e., the very subtle differences in isotopic values between the samples. PMID:25774366

High-Precision Plutonium Isotopic Compositions Measured on Los Alamos National Laboratory’s General’s Tanks Samples: Bearing on Model Ages, Reactor Modelling, and Sources of Material. Further Discussion of Chronometry

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

Spencer, Khalil J.; Rim, Jung Ho; Porterfield, Donivan R.

2015-06-29

In this study, we re-analyzed late-1940’s, Manhattan Project era Plutonium-rich sludge samples recovered from the ''General’s Tanks'' located within the nation’s oldest Plutonium processing facility, Technical Area 21. These samples were initially characterized by lower accuracy, and lower precision mass spectrometric techniques. We report here information that was previously not discernable: the two tanks contain isotopically distinct Pu not only for the major (i.e., 240Pu, 239Pu) but trace ( 238Pu , 241Pu, 242Pu) isotopes. Revised isotopics slightly changed the calculated 241Am- 241Pu model ages and interpretations.

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.

Oxygen isotope variation in stony-iron meteorites.

PubMed

Greenwood, R C; Franchi, I A; Jambon, A; Barrat, J A; Burbine, T H

2006-09-22

Asteroidal material, delivered to Earth as meteorites, preserves a record of the earliest stages of planetary formation. High-precision oxygen isotope analyses for the two major groups of stony-iron meteorites (main-group pallasites and mesosiderites) demonstrate that each group is from a distinct asteroidal source. Mesosiderites are isotopically identical to the howardite-eucrite-diogenite clan and, like them, are probably derived from the asteroid 4 Vesta. Main-group pallasites represent intermixed core-mantle material from a single disrupted asteroid and have no known equivalents among the basaltic meteorites. The stony-iron meteorites demonstrate that intense asteroidal deformation accompanied planetary accretion in the early Solar System.

Between carbonatite and lamproite—Diamondiferous Torngat ultramafic lamprophyres formed by carbonate-fluxed melting of cratonic MARID-type metasomes

NASA Astrophysics Data System (ADS)

Tappe, Sebastian; Foley, Stephen F.; Kjarsgaard, Bruce A.; Romer, Rolf L.; Heaman, Larry M.; Stracke, Andreas; Jenner, George A.

2008-07-01

New U-Pb perovskite ages reveal that diamondiferous ultramafic lamprophyre magmas erupted through the Archean crust of northern Labrador and Quebec (eastern Canada) between ca. 610 and 565 Ma, a period of strong rifting activity throughout contiguous Laurentia and Baltica. The observed Torngat carbonate-rich aillikite/carbonatite and carbonate-poor mela-aillikite dyke varieties show a large spread in Sr-Nd-Hf-Pb isotope ratios with pronounced correlations between isotope systems. An isotopically depleted component is identified solely within aillikites ( 87Sr/ 86Sr i = 0.70323-0.70377; ɛNd i = +1.2-+1.8; ɛHf i = +1.4-+3.5; 206Pb/ 204Pb i = 18.2-18.5), whereas some aillikites and all mela-aillikites range to more enriched isotope signatures ( 87Sr/ 86Sr i = 0.70388-0.70523; ɛNd i = -0.5 to -3.9; ɛHf i = -0.6 to -6.0; 206Pb/ 204Pb i = 17.8-18.2). These contrasting isotopic characteristics of aillikites/carbonatites and mela-aillikites, along with subtle differences in their modal carbonate, SiO 2, Al 2O 3, Na 2O, Cs-Rb, and Zr-Hf contents, are consistent with two distinctive metasomatic assemblages of different age in the mantle magma source region. Integration of petrologic, geochemical, and isotopic information leads us to propose that the isotopically enriched component originated from a reduced phlogopite-richterite-Ti-oxide dominated source assemblage that is reminiscent of MARID suite xenoliths. In contrast, the isotopically depleted component was derived from a more oxidized phlogopite-carbonate dominated source assemblage. We argue that low-degree CO 2-rich potassic silicate melts from the convective upper mantle were preferentially channelled into an older, pre-existing MARID-type vein network at the base of the North Atlantic craton lithosphere, where they froze to form new phlogopite-carbonate dominated veins. Continued stretching and thinning of the cratonic lithosphere during the Late Neoproterozoic remobilized the carbonate-rich vein material and induced volatile-fluxed fusion of the MARID-type veins and the cold peridotite substrate. Isotopic modelling suggests that only 5-12% trace element contribution from such geochemically extreme MARID-type material is required to produce the observed compositional shift from the isotopically most depleted aillikites/carbonatites towards enriched mela-aillikites. We conclude that cold cratonic mantle lithosphere can host several generations of contrasting vein assemblages, and that each may have formed during past tectonic and magmatic events under distinctively different physicochemical conditions. Although cratonic MARID-type and carbonate-bearing veins in peridotite can be the respective sources for lamproite and carbonatite magmas when present as the sole metasome, their concomitant fusion in a complex source region may give rise to a whole new variety of deep volatile-rich magmas and we suggest that orangeites (formerly Group 2 kimberlites), kamafugites, and certain types of ultramafic lamprophyre are formed in this manner.

Isotope Tracing of Long-Term Cadmium Fluxes in an Agricultural Soil.

PubMed

Salmanzadeh, Mahdiyeh; Hartland, Adam; Stirling, Claudine H; Balks, Megan R; Schipper, Louis A; Joshi, Chaitanya; George, Ejin

2017-07-05

Globally widespread phosphate fertilizer applications have resulted in long-term increases in the concentration of cadmium (Cd) in soils. The accumulation of this biotoxic, and bioaccumulative metal presents problems for the management of soil-plant-animal systems, because the magnitude and direction of removal fluxes (e.g., crop uptake, leaching) have been difficult to estimate. Here, Cd isotopic compositions (δ 114/110 Cd) of archived fertilizer and soil samples from a 66 year-long agricultural field trial in Winchmore, New Zealand, were used to constrain the Cd soil mass balance between 1959 and 2015 AD, informing future soil Cd accumulation trajectories. The isotopic partitioning of soil Cd sources in this system was aided by a change in phosphate source rocks in 1998 AD, and a corresponding shift in fertilizer isotope composition. The dominant influence of mixing between isotopically distinct Cd end-members was confirmed by a Bayesian modeling approach. Furthermore, isotope mass balance modeling revealed that Cd removal processes most likely increased in magnitude substantially between 2000 and 2015 AD, implying an increase in Cd bioaccumulation and/or leaching over that interval. Natural-abundance stable isotopes are introduced here as a powerful tool for tracing the fate of Cd in agricultural soils, and potentially the wider environment.

Using stable isotopes of water and strontium to investigate the hydrology of a natural and a constructed wetland

USGS Publications Warehouse

Hunt, R.J.; Bullen, T.D.; Krabbenhoft, D.P.; Kendall, C.

1998-01-01

Wetlands cannot exist without water, but wetland hydrology is difficult to characterize. As a result, compensatory wetland mitigation often only assumes the proper hydrology has been created. In this study, water sources and mass transfer processes in a natural and constructed wetland complex were investigated using isotopes of water and strontium. Water isotope profiles in the saturated zone revealed that the natural wetland and one site in the constructed wetland were primarily fed by ground water; profiles in another constructed wetland site showed recent rain was the predominant source of water in the root zone. Water isotopes in the capillary fringe indicated that the residence time for rain is less in the natural wetland than in the constructed wetland, thus transpiration (an important water sink) was greater in the natural wetland. Strontium isotopes showed a systematic difference between the natural and constructed wetlands that we attribute to the presence or absence of peat. In the peat-rich natural wetland, ??87Sr in the pore water increased along the flowline due to preferential weathering of minerals containing radiogenic Sr in response to elevated Fe concentrations in the water. In the constructed wetland, where peat thickness was thin and Fe concentrations in water were negligible, ??87Sr did not increase along the flowline. The source of the peat (on-site or off-site derived) applied in the constructed wetland controlled the ??87Sr at the top of the profile, but the effects were restricted by strong cation exchange in the underlying fluvial sediments. Based on the results of this study, neither constructed wetland site duplicated the water source and weathering environment of the adjoining natural wetland. Moreover, stable isotopes were shown to be effective tools for investigating wetlands and gaining insight not easily obtained using non-isotopic techniques. These tools have potential widespread application to wetlands that have distinct isotopic endmember sources.

The identification of lead ammunition as a source of lead exposure in First Nations: the use of lead isotope ratios.

PubMed

Tsuji, Leonard J S; Wainman, Bruce C; Martin, Ian D; Sutherland, Celine; Weber, Jean-Philippe; Dumas, Pierre; Nieboer, Evert

2008-04-15

The use of lead shotshell to hunt water birds has been associated with lead-contamination in game meat. However, evidence illustrating that lead shotshell is a source of lead exposure in subsistence hunting groups cannot be deemed definitive. This study seeks to determine whether lead shotshell constitutes a source of lead exposure using lead isotope ratios. We examined stable lead isotope ratios for lichens, lead shotshell and bullets, and blood from residents of Fort Albany and Kashechewan First Nations, and the City of Hamilton, Ontario, Canada. Data were analyzed using ANOVA and regression analyses. ANOVA of isotope ratios for blood revealed significant differences with respect to location, but not sex. Hamilton differed from both Kashechewan and Fort Albany; however, the First Nations did not differ from each other. ANOVA of the isotope ratios for lead ammunition and lichens revealed no significant differences between lichen groups (north and south) and for the lead ammunition sources (pellets and bullets). A plot of (206)Pb/(204)Pb and (206)Pb/(207)Pb values illustrated that lichens and lead ammunition were distinct groupings and only the 95% confidence ellipse of the First Nations group overlapped that of lead ammunition. In addition, partial correlations between blood-lead levels (adjusted for age) and isotope ratios revealed significant (p<0.05) positive correlations for (206)Pb/(204)Pb and (206)Pb/(207)Pb, and a significant negative correlation for (208)Pb/(206)Pb, as predicted if leaded ammunition were the source of lead exposure. In conclusion, lead ammunition was identified as a source of lead exposure for First Nations people; however, the isotope ratios for lead shotshell pellets and bullets were indistinguishable. Thus, lead-contaminated meat from game harvested with lead bullets may also be contributing to the lead body burden.

Sediment Tracking Using Carbon and Nitrogen Stable Isotopes

NASA Astrophysics Data System (ADS)

Fox, J. F.; Papanicolaou, A.

2002-12-01

As landscapes are stripped of valuable, nutrient rich topsoils and streams are clouded with habitat degrading fine sediment, it becomes increasingly important to identify and mitigate erosive surfaces. Particle tracking using vegetative derived carbon (C) and nitrogen (N) isotopic signatures and carbon/nitrogen (C/N) atomic ratios offer a promising technique to identify such problematic sources. Consultants and researchers successfully use C, N, and other stable isotopes of water for hydrologic purposes, such as quantifying groundwater vs. surface water contribution to a hydrograph. Recently, C and N isotopes and C/N atomic ratios of sediment were used to determine sediment mass balance within estuarine environments. The current research investigates C and N isotopes and C/N atomic ratios of source sediment for two primary purposes: (1) to establish a blueprint methodology for estimating sediment source and erosion rates within a watershed using this isotopic technology coupled with mineralogy fingerprinting techniques, radionuclide transport monitoring, and erosion-transport models, and (2) to complete field studies of upland erosion processes, such as, solifluction, mass wasting, creep, fluvial erosion, and vegetative induced erosion. Upland and floodplain sediment profiles and riverine suspended sediment were sampled on two occasions, May 2002 and August 2002, in the upper Palouse River watershed of northern Idaho. Over 300 samples were obtained from deep intermountain valley (i.e. forest) and rolling crop field (i.e. agriculture) locations. Preliminary sample treatment was completed at the Washington State University Water Quality Laboratory where samples were dried, removed of organic constituents, and prepared for isotopic analysis. C and N isotope and C/N atomic ratio analyses was performed at the University of Idaho Natural Resources Stable Isotope Laboratory using a Costech 4010 Elemental Combustion System connected with a continuous flow inlet system to the Finnigan MAT Delta Plus isotope ratio mass spectrometer. Results indicate distinct N isotopic signatures and C/N atomic ratios for forest and agriculture sediment sources. In addition, unique C and N isotopic signatures and C/N atomic ratios exist within floodplain and upland surfaces, and within the 10 centimeter profiles of erosion and deposition locations. Suspended sediment analyses are preliminary at this time. Conclusions indicate that sediment C and N isotopic signature and C/N atomic ratio are dependent upon land use and soil moisture conditions, and will serve as a useful technique in quantifying erosive source rates and understanding upland erosion processes.

Monitoring Lead (Pb) Pollution and Identifying Pb Pollution Sources in Japan Using Stable Pb Isotope Analysis with Kidneys of Wild Rats.

PubMed

Nakata, Hokuto; Nakayama, Shouta M M; Oroszlany, Balazs; Ikenaka, Yoshinori; Mizukawa, Hazuki; Tanaka, Kazuyuki; Harunari, Tsunehito; Tanikawa, Tsutomu; Darwish, Wageh Sobhy; Yohannes, Yared B; Saengtienchai, Aksorn; Ishizuka, Mayumi

2017-01-10

Although Japan has been considered to have little lead (Pb) pollution in modern times, the actual pollution situation is unclear. The present study aims to investigate the extent of Pb pollution and to identify the pollution sources in Japan using stable Pb isotope analysis with kidneys of wild rats. Wild brown ( Rattus norvegicus , n = 43) and black ( R. rattus , n = 98) rats were trapped from various sites in Japan. Mean Pb concentrations in the kidneys of rats from Okinawa (15.58 mg/kg, dry weight), Aichi (10.83), Niigata (10.62), Fukuoka (8.09), Ibaraki (5.06), Kyoto (4.58), Osaka (4.57), Kanagawa (3.42), and Tokyo (3.40) were above the threshold (2.50) for histological kidney changes. Similarly, compared with the previous report, it was regarded that even structural and functional kidney damage as well as neurotoxicity have spread among rats in Japan. Additionally, the possibility of human exposure to a high level of Pb was assumed. In regard to stable Pb isotope analysis, distinctive values of stable Pb isotope ratios (Pb-IRs) were detected in some kidney samples with Pb levels above 5.0 mg/kg. This result indicated that composite factors are involved in Pb pollution. However, the identification of a concrete pollution source has not been accomplished due to limited differences among previously reported values of Pb isotope composition in circulating Pb products. Namely, the current study established the limit of Pb isotope analysis for source identification. Further detailed research about monitoring Pb pollution in Japan and the demonstration of a novel method to identify Pb sources are needed.

Monitoring Lead (Pb) Pollution and Identifying Pb Pollution Sources in Japan Using Stable Pb Isotope Analysis with Kidneys of Wild Rats

PubMed Central

Nakata, Hokuto; Nakayama, Shouta M. M.; Oroszlany, Balazs; Ikenaka, Yoshinori; Mizukawa, Hazuki; Tanaka, Kazuyuki; Harunari, Tsunehito; Tanikawa, Tsutomu; Darwish, Wageh Sobhy; Yohannes, Yared B.; Saengtienchai, Aksorn; Ishizuka, Mayumi

2017-01-01

Although Japan has been considered to have little lead (Pb) pollution in modern times, the actual pollution situation is unclear. The present study aims to investigate the extent of Pb pollution and to identify the pollution sources in Japan using stable Pb isotope analysis with kidneys of wild rats. Wild brown (Rattus norvegicus, n = 43) and black (R. rattus, n = 98) rats were trapped from various sites in Japan. Mean Pb concentrations in the kidneys of rats from Okinawa (15.58 mg/kg, dry weight), Aichi (10.83), Niigata (10.62), Fukuoka (8.09), Ibaraki (5.06), Kyoto (4.58), Osaka (4.57), Kanagawa (3.42), and Tokyo (3.40) were above the threshold (2.50) for histological kidney changes. Similarly, compared with the previous report, it was regarded that even structural and functional kidney damage as well as neurotoxicity have spread among rats in Japan. Additionally, the possibility of human exposure to a high level of Pb was assumed. In regard to stable Pb isotope analysis, distinctive values of stable Pb isotope ratios (Pb-IRs) were detected in some kidney samples with Pb levels above 5.0 mg/kg. This result indicated that composite factors are involved in Pb pollution. However, the identification of a concrete pollution source has not been accomplished due to limited differences among previously reported values of Pb isotope composition in circulating Pb products. Namely, the current study established the limit of Pb isotope analysis for source identification. Further detailed research about monitoring Pb pollution in Japan and the demonstration of a novel method to identify Pb sources are needed. PMID:28075384

Mantle End-Members: The Trace Element Perspective

NASA Astrophysics Data System (ADS)

Willbold, M.; Stracke, A.; Hofmann, A. W.

2004-12-01

On the basis of their isotopic composition, ocean island basalts (OIB) have been classified into three to four end-members; HIMU with the most radiogenic Pb isotope ratios of OIB and Enriched Mantle 1 and 2 (EM1, EM2) with less radiogenic but variable Pb isotope and highly radiogenic Sr isotope signatures. It has also been argued that each of these isotopic families has common trace element characteristics that distinguish them from one another and so substantiated this classification. Here, we present new high-precision trace element data for samples from St. Helena, Tristan da Cunha and Gough in the Atlantic Ocean. The overall data-set is augmented by OIB data from the GEOROC database and includes data from all major isotopic families (HIMU: St. Helena, Mangaia, Tubuai, and Rururtu; EM1: Tristan da Cunha, Gough, Pitcairn; and EM2: Samoa, Marquesas, and Society). For each locality we use only islands defining the most extreme isotopic compositions. The entire data-set has been screened to exclude altered and highly differentiated samples. HIMU basalts have a very uniform trace element composition. Compared to HIMU-type basalts, EM-type basalts are enriched in Rb, Ba, and K, and depleted in U, Nb, and Ta, relative to La. Different EM-type OIBs from the same isotopic family (EM1 or EM2), have distinct trace element characteristics that can ultimately only be caused by different source compositions. For example, Ba/Th ratios in samples from both Tristan da Cunha (EM1) and Samoa (EM2) are similarly high (ca. 110) whereas Ba/Th ratios in samples from Pitcairn (EM1) and Society (EM2) samples are consistently lower (ca. 70). Thus on the basis of their trace element composition, EM-type OIB cannot be classified into EM1 and EM2 type basalts, nor can any other grouping be identified. The remarkably uniform isotopic and trace element composition of HIMU-type basalts suggests derivation from a single common source reservoir, most likely subduction-modified oceanic crust. Although there are some trace element characteristics common to all EM-type basalts, which distinguish them from HIMU-type basalts (e.g. uniformly high Th/U ratios of 4.7 ± 0.3, and enrichment in Cs-U), each suite of EM-type basalts has unique trace element signatures that distinguish them from any other suite of EM-type basalts. This is especially obvious when comparing the trace element composition of EM basalts from one isotopic family, for example EM1-type basalts from Tristan, Gough and Pitcairn. Consequently, the trace element systematics of EM-type basalts suggest that there are many different EM-type sources, whereas the isotopic composition of EM-type basalts suggest derivation from two broadly similar sources, i.e. EM1 and EM2. The large variability in subducting sediments with respect to both parent-daughter (e.g. Rb/Sr, Sm/Nd, U/Pb, Th/Pb,...) and other trace element ratios makes it unlikely that there are reproducible mixtures of sediments leading to two different isotopic evolution paths (EM1 and EM2) while preserving a range of incompatible element contents for each isotopic family, as would be required to reconcile the isotopic and trace element characteristics of EM-type basalts. Although this does not a priori argue against sediments as possible source components for OIB, it does argue against two distinct groups of sediments as EM1 and EM2 sources. Further characterization of sources with the same general origin (e.g. a certain type of crust or lithosphere) or identification of processes leading to reservoirs with similar parent-daughter ratio characteristics but different incompatible trace element contents could resolve the apparent conundrum.

An investigation of mercury sources in the Puyango-Tumbes River: Using stable Hg isotopes to characterize transboundary Hg pollution.

PubMed

Schudel, Gary; Miserendino, Rebecca Adler; Veiga, Marcello M; Velasquez-López, P Colon; Lees, Peter S J; Winland-Gaetz, Sean; Davée Guimarães, Jean Remy; Bergquist, Bridget A

2018-07-01

Mercury (Hg) concentrations and stable isotopes along with other trace metals were examined in environmental samples from Ecuador and Peru's shared Puyango-Tumbes River in order to determine the extent to which artisanal- and small-scale gold mining (ASGM) in Portovelo-Zaruma, Ecuador contributes to Hg pollution in the downstream aquatic ecosystem. Prior studies investigated the relationship between ASGM activities and downstream Hg pollution relying primarily on Hg concentration data. In this study, Hg isotopes revealed an isotopically heavy Hg signature with negligible mass independent fractionation (MIF) in downstream sediments, which was consistent with the signature observed in the ASGM source endmember. This signature was traced as far as ∼120 km downstream of Portovelo-Zaruma, demonstrating that Hg stable isotopes can be used as a tool to fingerprint and trace sources of Hg over vast distances in freshwater environments. The success of Hg isotopes as a source tracer in fresh waters is largely due to the particle-reactive nature of Hg. Furthermore, the magnitude and extent of downstream Hg, lead, copper and zinc contamination coupled with the Hg isotopes suggest that it is unlikely that the smaller artisanal-scale activities, which do not use cyanidation, are responsible for the pollution. More likely it is the scale of ores processed and the cyanide leaching, which can release other metals and enhance Hg transport, used during small-scale gold mining that is responsible. Thus, although artisanal- and small-scale gold mining occur in tandem in Portovelo-Zaruma, a distinction should be made between these two activities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Stable sulfur isotope hydrogeochemical studies using desert shrubs and tree rings, Death Valley, California, USA

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

Yang, Wenbo; Spencer, R.J.; Krouse, H.R.

1996-08-01

The {delta}{sup 34}S values of two dominant xerophytes, Atriplex hymenehytra and Larrea tridentata, in Death Valley, California, vary similarly from +7 to +18{per_thousand}, corresponding isotopically to sulfate in the water supplies at a given location. Going radially outwards, tree ring data from a phreatophyte tree, Tamarix aphylla, show a distinct time dependence, with {delta}{sup 34}S values increasing from +13.5 to +18{per_thousand} for soluble sulfate and from +12 to +17% for total sulfur. These data are interpreted in terms of sulfur sources, water sources and flow paths, and tree root growth. 32 refs., 3 figs., 3 tabs.

Using stable isotopes in tracing contaminant sources in an industrial area: A case study on the hydrological basin of the Olt River, Romania.

PubMed

Popescu, Raluca; Mimmo, Tanja; Dinca, Oana Romina; Capici, Calogero; Costinel, Diana; Sandru, Claudia; Ionete, Roxana Elena; Stefanescu, Ioan; Axente, Damian

2015-11-15

Tracing pollution sources and transformation of nitrogen compounds in surface- and groundwater is an issue of great significance worldwide due to the increased human activity, translated in high demand of water resources and pollution. In this work, the hydrological basin of an important chemical industrial platform in Romania (Ramnicu Valcea industrial area) was characterized in terms of the physico-chemical and isotope composition of δ(18)O and δ(2)H in water samples and δ(15)N of the inorganic nitrogen species. Throughout a period of one year, water samples from the Olt River and its more important tributaries were collected monthly in the industrial area, when the seasonal and spatial isotope patterns of the surface waters and the main sources of pollution were determined. Higher inorganic nitrogen concentrations (up to 10.2 mg N L(-1)) were measured between November 2012 and April 2013, which were designated as anthropogenic additions using the mixing calculations. The main sources of pollution with inorganic nitrogen were agriculture and residential release. The inorganic nitrogen from the industrial waste water duct had a distinct δ(15)N fingerprint (mean of -8.6‰). Also, one industrial release into the environment was identified for Olt River, at Ionesti site, in November 2012. The mean precipitation samples had the lowest inorganic nitrogen concentrations (less than 5.5 mg N L(-1)) with a distinct δ(15)N fingerprint compared to the surface and industrial waters. Copyright © 2015 Elsevier B.V. All rights reserved.

Archean crustal evolution in the Southern São Francisco craton, Brazil: Constraints from U-Pb, Lu-Hf and O isotope analyses

NASA Astrophysics Data System (ADS)

Albert, Capucine; Farina, Federico; Lana, Cristiano; Stevens, Gary; Storey, Craig; Gerdes, Axel; Dopico, Carmen Martínez

2016-12-01

In this study we present U-Pb and Hf isotope data combined with O isotopes in zircon from Neoarchean granitoids and gneisses of the southern São Francisco craton in Brazil. The basement rocks record three distinct magmatic events: Rio das Velhas I (2920-2850 Ma), Rio das Velhas II (2800-2760 Ma) and Mamona (2750-2680 Ma). The three sampled metamorphic complexes (Bação, Bonfim and Belo Horizonte) have distinct εHf vs. time arrays, indicating that they grew as separate terranes. Paleoarchean crust is identified as a source which has been incorporated into younger magmatic rocks via melting and mixing with younger juvenile material, assimilation and/or source contamination processes. The continental crust in the southern São Francisco craton underwent a change in magmatic composition from medium- to high-K granitoids in the latest stages, indicating a progressive HFSE enrichment of the sources that underwent anatexis in the different stages and possibly shallowing of the melting depth. Oxygen isotope data shows a secular trend towards high δ18O (up to 7.79‰) indicating the involvement of metasediments in the petrogenesis of the high potassium granitoids during the Mamona event. In addition, low δ18O values (down to 2.50‰) throughout the Meso- and Neoarchean emphasize the importance of meteoritic fluids in intra-crustal magmatism. We used hafnium isotope modelling from a compilation of detrital zircon compositions to constrain crustal growth rates and geodynamics from 3.50 to 2.65 Ga. The modelling points to a change in geodynamic process in the southern São Francisco craton at 2.9 Ga, from a regime dominated by net crustal growth in the Paleoarchean to a Neoarchean regime marked by crustal reworking. The reworking processes account for the wide variety of granitoid magmatism and are attributed to the onset of continental collision.

The Fine Geochemical Structure of the Hawaiian Mantle Plume: Relation to the Earth's Lowermost Mantle

NASA Astrophysics Data System (ADS)

Weis, D.; Harrison, L.

2017-12-01

The Hawaiian mantle plume has been active for >80 Ma with the highest magmatic flux, also distinctly increasing with time. The identification of two clear geochemical trends (Loa-Kea) among Hawaiian volcanoes in all isotope systems has implications for the dynamics and internal structure of the plume conduit and source in the deep mantle. A compilation of modern isotopic data on Hawaiian shield volcanoes and from the Northwest Hawaiian Ridge (NWHR), focusing specifically on high-precision Pb isotopes integrated with Sr, Nd and Hf isotopes, indicates the presence of source differences for Loa- and Kea-trend volcanoes that are maintained throughout the 1 Ma activity of each volcano. These differences extend back in time on all the Hawaiian Islands ( 5 Ma), and as far back as 47 Ma on the NWHR. In all isotope systems, the Loa-trend basalts are more heterogeneous by a factor of 1.5 than the Kea-trend basalts. The Hawaiian mantle plume overlies the boundary between ambient Pacific lower mantle on the Kea side and the Pacific LLSVP on the Loa side. Geochemical differences between Kea and Loa trends reflect preferential sampling of these two distinct sources of deep mantle material, with additional contribution of ULVZ material sporadically on the Loa side. Plume movement up the gently sloping edge of the LLSVP resulted in entrainment of greater amounts of LLSVP-enriched material over time, and explains why the Hawaiian mantle plume dramatically strengthens over time, contrary to plume models. Similar indications of preferential sampling at the edges of the African LLSVP are found in Kerguelen and Tristan da Cunha basalts in the Indian and Atlantic oceans, respectively. The anomalous low-velocity zones at the core-mantle boundary store geochemical heterogeneities that are enriched in recycled material (EM-I type) with different compositions under the Pacific and under Africa, and that are sampled by strong mantle plumes such as Hawaii and Kerguelen.

Geochemical characteristics of Cretaceous carbonatites from Angola

NASA Astrophysics Data System (ADS)

Alberti, A.; Castorina, F.; Censi, P.; Comin-Chiaramonti, P.; Gomes, C. B.

1999-12-01

The Early Cretaceous (138-130 Ma) carbonatites and associated alkaline rocks of Angola belong to the Paraná-Angola-Etendeka Province and occur as ring complexes and other central-type intrusions along northeast trending tectonic lineaments, parallel to the trend of coeval Namibian alkaline complexes. Most of the Angolan carbonatite-alkaline bodies are located along the apical part of the Moçamedes Arch, a structure representing the African counterpart of the Ponta Grossa Arch in southern Brazil, where several alkaline-carbonatite complexes were also emplaced in the Early Cretaceous. Geochemical and isotopic (C, 0, Sr and Nd) characteristics determined for five carbonatitic occurrences indicate that: (1) the overall geochemical composition, including the OC isotopes, is within the range of the Early and Late Cretaceous Brazilian occurrences from the Paraná Basin; (2) the La versus {La}/{Yb} relationships are consistent with the exsolution of CO i2-rich melts from trachyphonolitic magmas; and (3) the {143Nd}/{144Nd} and {87Sr}/{86Sr} initial ratios are similar to the initial isotopic ratios (129 Ma) of alkaline complexes in northwest Namibia. In contrast, the Lupongola carbonatites have a distinctly different {143Nd}/{144Nd} initial ratio, suggesting a different source. The Angolan carbonatites have SrNd isotopic compositions ranging from bulk earth to time-integrated depleted sources. Since those from eastern Paraguay (at the western fringe of the Paraná-Angola-Etendeka Province) and Brazil appear to be related to mantle-derived melts with time-integrated enriched or B.E. isotopic characteristics, it is concluded that the carbonatites of the Paraná-Angola-Etendeka Province have compositionally distinct mantle sources. Such mantle heterogeneity is attributed to 'metasomatic processes', which would have occurred at ca 0.6-0.7 Ga (Angola, northwest Namibia and Brazil) and ca 1.8 Ga (eastern Paraguay), as suggested by Nd-model ages.

The impact of moisture sources on the oxygen isotope composition of precipitation at a continental site in central Europe

NASA Astrophysics Data System (ADS)

Krklec, Kristina; Domínguez-Villar, David; Lojen, Sonja

2018-06-01

The stable isotope composition of precipitation records processes taking place within the hydrological cycle. Potentially, moisture sources are important controls on the stable isotope composition of precipitation, but studies focused on this topic are still scarce. We studied the moisture sources contributing to precipitation at Postojna (Slovenia) from 2009 to 2013. Back trajectory analyses were computed for the days with precipitation at Postojna. The moisture uptake locations were identified along these trajectories using standard hydrometeorological formulation. The moisture uptake locations were integrated in eight source regions to facilitate its comparison to the monthly oxygen isotope composition (δ18O values) of precipitation. Nearly half of the precipitation originated from continental sources (recycled moisture), and >40% was from central and western Mediterranean. Results show that moisture sources do not have a significant impact on the oxygen isotope composition at this site. We suggest that the large proportion of recycled moisture originated from transpiration rather than evaporation, which produced water vapour with less negative δ18O values. Thus the difference between the oceanic and local vapour source was reduced, which prevented the distinction of the moisture sources based on their oxygen isotope signature. Nevertheless, δ18O values of precipitation are partially controlled by climate parameters, which is of major importance for paleoclimate studies. We found that the main climate control on Postojna δ18O values of precipitation is the surface temperature. Amount effect was not recorded at this site, and the winter North Atlantic Oscillation (NAO) does not impact the δ18O values of precipitation. The Western Mediterranean Oscillation (WeMO) was correlated to oxygen stable isotope composition, although this atmospheric pattern was not a control. Instead we found that the link to δ18O values results from synoptic scenarios affecting WeMO index as well as temperature. Therefore, interpretation of δ18O values of precipitation in terms of climate is limited to surface temperature, although at least half of the variability observed still depends on unknown controls of the hydrological cycle.

Isotopic links between atmospheric chemistry and the deep sulphur cycle on Mars.

PubMed

Franz, Heather B; Kim, Sang-Tae; Farquhar, James; Day, James M D; Economos, Rita C; McKeegan, Kevin D; Schmitt, Axel K; Irving, Anthony J; Hoek, Joost; Dottin, James

2014-04-17

The geochemistry of Martian meteorites provides a wealth of information about the solid planet and the surface and atmospheric processes that occurred on Mars. The degree to which Martian magmas may have assimilated crustal material, thus altering the geochemical signatures acquired from their mantle sources, is unclear. This issue features prominently in efforts to understand whether the source of light rare-earth elements in enriched shergottites lies in crustal material incorporated into melts or in mixing between enriched and depleted mantle reservoirs. Sulphur isotope systematics offer insight into some aspects of crustal assimilation. The presence of igneous sulphides in Martian meteorites with sulphur isotope signatures indicative of mass-independent fractionation suggests the assimilation of sulphur both during passage of magmas through the crust of Mars and at sites of emplacement. Here we report isotopic analyses of 40 Martian meteorites that represent more than half of the distinct known Martian meteorites, including 30 shergottites (28 plus 2 pairs, where pairs are separate fragments of a single meteorite), 8 nakhlites (5 plus 3 pairs), Allan Hills 84001 and Chassigny. Our data provide strong evidence that assimilation of sulphur into Martian magmas was a common occurrence throughout much of the planet's history. The signature of mass-independent fractionation observed also indicates that the atmospheric imprint of photochemical processing preserved in Martian meteoritic sulphide and sulphate is distinct from that observed in terrestrial analogues, suggesting fundamental differences between the dominant sulphur chemistry in the atmosphere of Mars and that in the atmosphere of Earth.

The Upper Mantle Flow Field around South-Africa as Reflected by Isotopic Provinciality

NASA Astrophysics Data System (ADS)

Meyzen, C.; Blichert-Toft, J.; Ludden, J.; Humler, E.; Mevel, C.; Albarede, F.

2006-12-01

Isotopic studies of MORB have established the existence of broad isotopic provinces within the underlying asthenosphere, such as in the Indian Ocean (DUPAL). How these features relate to mantle circulation is, however, still unknown. The steepness of the transition between such isotopic provinces will define the geometry of the velocity field in the upper mantle. In this respect, the transition between the Indian and South Atlantic provinces, two domains that are isotopically contrasted, should be readily identifiable over this long ridge segment. Here, we present Hf isotope data for 60 samples dredged along the SWIR between 35° and 69°E. The new Hf isotope data show that the Indian asthenosphere does not spill directly into the South Atlantic upper mantle: the general decreasing southward gradient observed for ^{176}Hf/^{177}Hf down the mid- Atlantic Ridge, and also for Sr isotopes and model Th/U ratios (derived from Pb isotopes), is overprinted by material with radiogenic Sr, unradiogenic Hf and high Th/U. The Indian domain grades into the South Atlantic around Bouvet, while the South Atlantic collides with the Atlantic province around Tristan. We interpret these features to represent fronts between three adjacent isotopic provinces similar to what has been suggested for the Australian-Antarctic Discordance. The common DUPAL signature of MORB and OIB from the Indian province and the geochemistry of Gulf of Aden MORB and the Afar plume suggest that the source of this distinctive mantle component is deep and lies to the north of the province. This is also what the three-dimensional flow field computed by Behn et al. (2004) from shear-wave splitting shows with a major lower mantle upwelling radiating at the base of the asthenosphere under the Afar plume. Lower mantle gushing out from this source flows southward unimpeded along the Indian ridges, whereas it only reaches the South Atlantic ridge after first having been deflected under the deep roots of the South African Archean cratons. Erosion of these roots by the asthenospheric drift confers a distinct continental signature on the source of South Atlantic MORB. This pattern is also consistent with the observation that the lowest He isotope values occur, on average, along the South Atlantic ridge. To some extent, the dynamics of the North Atlantic upper mantle mirrors the Indian situation: the flow field of Behn et al. (2004) shows that the North Atlantic asthenosphere also fills up through deep mantle upwellings, which is consistent with the Dupal-like isotopic signature of the Arctic ridges. M.D. Behn, C.P. Conrad and P.G. Silver (2004), Detection of upper mantle flow associated with the African Superplume, Earth. Planet. Sci. Lett., 224, 259-274.

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.

Can Transport of Saharan Dust Explain Extensive Clay Deposits in the Amazon Basin? A Test Using Radiogenic Isotopes

NASA Astrophysics Data System (ADS)

Andreae, M. O.; Abouchami, W.; Näthe, K.; Kumar, A.; Galer, S. J.; Jochum, K. P.; Williams, E.; Horbe, A. M.; Rosa, J. W.; Adams, D. K.; Balsam, W. R.

2012-12-01

The Bodélé Depression, located in the Southern Sahara, is a huge source of atmospheric dust and thus an important element in biogeochemical cycles and the radiative budget of Earth's atmosphere. Previous studies have shown that Saharan dust transport across the Atlantic acts as an important source of mineral nutrients to the Amazon rainforest. The Belterra Clay, which outcrops extensively across the Amazon Basin in Brazil, has been proposed to result from dry deposition of African dusts. We have investigated this hypothesis by measuring the radiogenic isotopic composition (Sr, Nd and Pb) of a suite of samples from the Belterra Clay, the Bodélé Depression, dusts deposits collected at various locations along the airmass transport trajectory, as well as loess from the Cape Verde Islands. Radiogenic isotope systems are powerful tracers of provenance and can be used to fingerprint dust sources and atmospheric transport patterns. Our results identify distinct isotopic signatures in the Belterra Clay samples and the African sources. The Belterra Clay display radiogenic Sr and Pb isotope ratios associated with non-radiogenic Nd isotope signatures. In contrast, Bodélé samples and dusts deposits show lower Pb isotope ratios, variable 87Sr/86Sr, and relatively homogeneous Nd isotopic compositions, albeit more radiogenic than those of the Belterra Clay. Our data show unambiguously that the Belterra Clay is not derived from African dust deposition, nor from the Andean chain, as originally suggested by W. Sombroek. Rather, isotopic compositions and Nd model ages are consistent with simple mixing of Archean and younger Proterozoic terranes within the Amazon Basin as a result of weathering and erosion under humid tropical conditions. Whether Saharan dusts contribute to the fertilization in the Amazon Basin cannot be ruled out, however, since the African dust isotopic signature is expected to be entirely overprinted by local sources. Radiogenic isotope data obtained on aerosol filters collected in the US Virgin Islands and Tobago are similar to those of aerosols from Mali, demonstrating that the African dust isotope signal is detectable and transported as far as Central and South America. Thus, while it appears undeniable that Saharan dust reaches the Amazon Basin, its importance for overall soil fertility requires a careful assessment of the dust budget versus bedrock weathering rates for key nutrient elements.

Lunar initial Nd-143/Nd-144 - Differential evolution of the lunar crust and mantle

NASA Technical Reports Server (NTRS)

Lugmair, G. W.; Marti, K.

1978-01-01

The Sm-Nd evolution of Apollo 15 green glass is discussed. The ICE age (intercept with chondritic evolution) of 3.8 + or - 0.4 eons overlaps the range of reported (Ar-39)-(Ar-40) ages and implies a distinct source region for green glass, characterized by very low and unfractionated REE abundances. Evidence is presented that LINd (lunar initial Nd) is compatible with a 'chondritic'-type Nd isotopic evolution as observed in the Juvinas meteorite. This normalization is used to study the Sm-Nd system of various lunar rock types. The results obtained from a limited number of rocks clearly indicate differential Sm-Nd evolution for the lunar crust and mantle. High-Ti basalts returned by the Apollo 11 and 17 missions were derived from distinct source regions. The Nd-143 evolution in KREEP requires a source region which is clearly distinct from any mantle reservoir.

Istopically Defined Source Reservoirs of Primitive Magmas in the East African Rift.

NASA Astrophysics Data System (ADS)

Rooney, T. O.; Furman, T.; Hanan, B.

2005-12-01

Extension within the East African Rift is a function of the interaction between plume-driven uplift and far-field stresses associated with plate tectonic processes. Geochemical and isotopic investigation of primitive basalts from the Main Ethiopian Rift (MER) reveals systematic spatial variations in the contributions from distinct and identifiable source reservoirs that, in turn help identify the mechanisms by which along-axis rifting has progressed. The Sr-Nd-Pb isotopic characteristics of MER basalts can be described by a three-component mixing model involving the long-lived Afar plume, a depleted mantle component similar to the source region for Gulf of Aden MORB from east of 48° E and a reservoir that is likely lithospheric (sub-continental mantle lithosphere, magmatic underplate or lower crust). Quaternary basalts in the central MER exhibit a systematic decrease in plume influence southward from 9.5° N to 8° N, i.e., away from the modern surface expression of the Afar plume in Djibouti and Erta 'Ale. The composition of the Afar plume component is comparable to the "C" mantle reservoir. This southward decrease in plume influence is coupled with an increase in the influence of the lithospheric and depleted mantle components. Linear arrays observed within Pb-Pb isotopic space at each eruptive center require distinctive ratio of lithospheric + depleted mantle components mixing with variable amounts of the "C"-like plume component. This isotopic evidence suggests the depleted mantle and lithosphere mixed prior to the generation of the recent magmas. To the south, the Sr-Nd-Pb isotopic compositions of Turkana (Kenya) rift basalts record a mix of a similar "C"-like plume component and a fourth HIMU-like source component. Low 3He/4He values observed in the HIMU-dominated lavas from Turkana contrast with the higher ratios found in basalts associated with the "C"-like Afar plume. Further analysis of "C"-HIMU lavas at Turkana is required to fully constrain the He isotopic signatures. Thus, along-axis patterns in Quaternary EARS magmatism are compatible with two "C"-like plumes with contributions from the upper mantle and chemically distinct lithospheric components. Alternatively, a single "C"-like plume can account for these relationships. In the single plume scenario, the HIMU source component present in the 30 Ma Turkana lavas may represent melting of metasomatised lithosphere, derived from the accretion of island-arc-backarc basins during Pan-African events (e.g. Schilling et al., 1992). The recent plume-dominated activity in Turkana and Afar are separated by a region characterized by waning plume influence and a greater contribution from the depleted mantle. This intermediate zone, which is located in the south-central MER represents the modern site of contact between the northward propagating Kenya / Turkana Rift and the southward propagating Afar Rift zone.

The Chlorine Isotope Composition of the Solar Nebula & Implications to the Sources of Volatiles to the Terrestrial Planets

NASA Astrophysics Data System (ADS)

Gargano, A. M.; Sharp, Z. D.

2017-12-01

It was originally proposed by Sharp et al., 2016 that the solar nebula was isotopically light based on limited sampling of the Ol-phyric shergottites and two ordinary chondrites (Parnallee LL3.00, and NWA 8276 L3.00). Iron meteorites are remnants of early planetesimals which segregated cores <1Ma after CAI's and have δ37Cl values as low as -7‰, consistent with a light nebular source. Chondrules are relatively younger than iron meteorite parent bodies (2-3Ma after CAI's) and exhibit evidence for mixing with & recycling numerous isotopically distinct precursors as observed by Cl rich chondrules in Semarkona, and Qingzhen. The average δ37Cl values of chondrites are around 0‰, independent of petrologic type or [Cl], suggesting that chondrule forming regions have similar chlorine isotope sources. The average δ37Cl values of chondrites are consistent with a +3 to +6‰ isotopic fractionation of HCl clathrate from HCl gas, which occurred beyond the snow-line at 150K. The recycling of chondritic precursors mixed with HCl clathrate can account for pristine type 3.00 chondrites with δ37Cl values at approximately 0‰ independent of [Cl], or petrologic type. The source of volatiles to the terrestrial planets is commonly assumed to be chondritic in origin. These preliminary chlorine isotope data suggest that early planetesimals and planetary embryos had a solar Cl component at -7‰ or less, and secondary processes has since increased the δ37Cl values of Earth, Mars, and most chondrites. The chlorine isotope system therefore provides a new constraint regarding the sources of volatiles to the terrestrial planets. The δ37Cl value of the bulk Earth is around 0‰, inconsistent with a nebular source as measured in the Martian mantle but similar to that of chondrites with HCl clathrate precursors. The prolonged accretion of heavy chondritic material to Earth can account for the chlorine isotope discrepancy between the Earth and Mars, but is unconstrained by HSE abundances before complete core-mantle differentiation. Here, we examine the amount of chondritic chlorine and water that can added to the Earth allowable by HSE abundances and explore other potential sources of volatiles to the terrestrial planets to account for isotopic and elemental discrepancies.

Hidden cycle of dissolved organic carbon in the deep ocean.

PubMed

Follett, Christopher L; Repeta, Daniel J; Rothman, Daniel H; Xu, Li; Santinelli, Chiara

2014-11-25

Marine dissolved organic carbon (DOC) is a large (660 Pg C) reactive carbon reservoir that mediates the oceanic microbial food web and interacts with climate on both short and long timescales. Carbon isotopic content provides information on the DOC source via δ(13)C and age via Δ(14)C. Bulk isotope measurements suggest a microbially sourced DOC reservoir with two distinct components of differing radiocarbon age. However, such measurements cannot determine internal dynamics and fluxes. Here we analyze serial oxidation experiments to quantify the isotopic diversity of DOC at an oligotrophic site in the central Pacific Ocean. Our results show diversity in both stable and radio isotopes at all depths, confirming DOC cycling hidden within bulk analyses. We confirm the presence of isotopically enriched, modern DOC cocycling with an isotopically depleted older fraction in the upper ocean. However, our results show that up to 30% of the deep DOC reservoir is modern and supported by a 1 Pg/y carbon flux, which is 10 times higher than inferred from bulk isotope measurements. Isotopically depleted material turns over at an apparent time scale of 30,000 y, which is far slower than indicated by bulk isotope measurements. These results are consistent with global DOC measurements and explain both the fluctuations in deep DOC concentration and the anomalous radiocarbon values of DOC in the Southern Ocean. Collectively these results provide an unprecedented view of the ways in which DOC moves through the marine carbon cycle.

Hidden cycle of dissolved organic carbon in the deep ocean

PubMed Central

Follett, Christopher L.; Repeta, Daniel J.; Rothman, Daniel H.; Xu, Li; Santinelli, Chiara

2014-01-01

Marine dissolved organic carbon (DOC) is a large (660 Pg C) reactive carbon reservoir that mediates the oceanic microbial food web and interacts with climate on both short and long timescales. Carbon isotopic content provides information on the DOC source via δ13C and age via Δ14C. Bulk isotope measurements suggest a microbially sourced DOC reservoir with two distinct components of differing radiocarbon age. However, such measurements cannot determine internal dynamics and fluxes. Here we analyze serial oxidation experiments to quantify the isotopic diversity of DOC at an oligotrophic site in the central Pacific Ocean. Our results show diversity in both stable and radio isotopes at all depths, confirming DOC cycling hidden within bulk analyses. We confirm the presence of isotopically enriched, modern DOC cocycling with an isotopically depleted older fraction in the upper ocean. However, our results show that up to 30% of the deep DOC reservoir is modern and supported by a 1 Pg/y carbon flux, which is 10 times higher than inferred from bulk isotope measurements. Isotopically depleted material turns over at an apparent time scale of 30,000 y, which is far slower than indicated by bulk isotope measurements. These results are consistent with global DOC measurements and explain both the fluctuations in deep DOC concentration and the anomalous radiocarbon values of DOC in the Southern Ocean. Collectively these results provide an unprecedented view of the ways in which DOC moves through the marine carbon cycle. PMID:25385632

Sr, Nd, Pb and Hf Isotopic Compositions of Late Cenozoic Alkali Basalts in South Korea: Evidence for Mixing Between the Two Dominant Asthenospheric Mantle Domains beneath East Asia

NASA Astrophysics Data System (ADS)

Choi, S.; Mukasa, S. B.; Kwon, S.; Andronikov, A. V.

2004-12-01

We determined the Sr, Nd, Pb and Hf isotopic compositions of late Cenozoic basaltic rocks from six lava-field provinces in South Korea, including Baengnyeong Island, Jogokni, Ganseong area, Jeju Island, Ulleung Island and Dog Island, in order to understand the nature of the mantle source. The basalts have OIB-like trace element abundance patterns, and also contain mantle-derived xenoliths. Available isotope data of late Cenozoic basalts from East Asia, along with ours, show that the mantle source has a DMM-EM1 array for northeast China and a DMM-EM2 array for Southeast Asia. We note that the basalts falling on an array between DMM and an intermediate end member between EM1 and EM2, are located between the two large-scale isotopic provinces, i.e., around the eastern part of South Korea. The most intriguing observation on the isotopic correlation diagrams is spatial variation from predominantly EM2 signatures in the basaltic lavas toward increasingly important addition of EM1, starting from Jeju Island to Ulleung and Dog Islands to Ganseong area, and to Baengnyeong Island. This is without any corresponding changes in the basement and the lithospheric mantle beneath the region. These observations suggest that the asthenospheric mantle source is dominant for the Cenozoic intraplate volcanism in East Asia, which is characterized by two distinct, large-scale domains. Previous studies on East Asian Cenozoic volcanic rocks have invoked origins by either plume activity or decompressional melting in a rift environment. On the basis of our new trace element and isotopic compositions which have OIB-like characteristics, we prefer a plume origin for these lavas. However, because tomographic images do not show distinct thermal anomaly that would be interpreted as a plume, we suggest that the magmatism might be the product of small, difficult to image multiple plumes that tapped the shallow part of the asthenosphere (probably the transition zone in the upper mantle).

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.

Contrasting sources of Late Paleozoic rhyolite magma in the Polish Lowlands: evidence from U-Pb ages and Hf and O isotope composition in zircon

NASA Astrophysics Data System (ADS)

Słodczyk, Elżbieta; Pietranik, Anna; Glynn, Sarah; Wiedenbeck, Michael; Breitkreuz, Christoph; Dhuime, Bruno

2018-02-01

The Polish Lowlands, located southwest of the Teisseyre-Tornquist Zone, within Trans-European Suture Zone, were affected by bimodal, but dominantly rhyolitic, magmatism during the Late Paleozoic. Thanks to the inherited zircon they contain, these rhyolitic rocks provide a direct source of information about the pre-Permian rocks underlying the Polish Lowland. This paper presents zircon U-Pb geochronology and Hf and O isotopic results from five drill core samples representing four rhyolites and one granite. Based on the ratio of inherited vs. autocrystic zircon, the rhyolites can be divided into two groups: northern rhyolites, where autocrystic zircon is more abundant and southern rhyolites, where inherited zircon dominates. We suggest that the magma sources and the processes responsible for generating high silica magmas differ between the northern and southern rhyolites. Isotopically distinct sources were available during formation of northern rhyolites, as the Hf and O isotopes in magmatic zircon differ between the two analysed localities of northern rhyolites. A mixing between magmas formed from Baltica-derived mudstone-siltstone sediments and Avalonian basement or mantle can explain the diversity between the zircon compositions from the northern localities Daszewo and Wysoka Kamieńska. Conversely, the southern rhyolites from our two localities contain zircon with similar compositions, and these units can be further correlated with results from the North East German Basin, suggesting uniform source rocks over this larger region. Based on the ages of inherited zircon and the isotopic composition of magmatic ones, we suggest that the dominant source of the southern rhyolites is Variscan foreland sediments mixed with Baltica/Avalonia-derived sediments.

The use of stable isotope to evaluate water mixing and water use by flood plain trees along the Garonne valley

USGS Publications Warehouse

Lambs, L.; Loubiat, M.; Richardson, W.

2003-01-01

Before the confluence of the Tarn, the Garonne valley was the driest area in the entire south-west of France, due to the relatively low rainfall and low summer discharge of the Garonne River and its tributaries. The natural abundance of the stable isotope of oxygen (18O) and ionic charge of surface and ground water were used to estimate the water source for the Garonne River and phreatic subsurface water. We also measured these constituents in the sap of trees at several flood plain sites to better understand the source of water used by these trees. 18O signatures and conductivity in the Garonne River indicated that the predominance of water was from high altitude surface runoff from the Pyrenees Mountains. Tributary inputs had little effect on isotopic identity, but had a small effect on the conductivity. The isotopic signature and ionic conductivity of river water (??18O: -9.1??? to -9.0???, conductivity: 217-410??S/cm) was distinctly different from groundwater (??18O: -7.1??? to -6.6???, conductivity: 600-900??S/cm). Isotopic signatures from the sap of trees on the flood plain showed that the water source was shallow subsurface water (1m). Trees at both locations maintained sap with ionic charges much greater (2.3-3.7x) than that of source water. The combined use of 18O signatures and ionic conductivity appears to be a potent tool to determine water sources on geographic scales, and source and use patterns by trees at the local forest scale. These analyses also show promise for better understanding of the effects of anthropogenic land-use and water-use changes on flood plain forest dynamics.

Plume versus plate origin for the Shatsky Rise oceanic plateau (NW Pacific): Insights from Nd, Pb and Hf isotopes

NASA Astrophysics Data System (ADS)

Heydolph, Ken; Murphy, David T.; Geldmacher, Jörg; Romanova, Irina V.; Greene, Andrew; Hoernle, Kaj; Weis, Dominique; Mahoney, John

2014-07-01

Shatsky Rise, an early Cretaceous igneous oceanic plateau in the NW Pacific, comprises characteristics that could be attributed to either formation by shallow, plate tectonic-controlled processes or to an origin by a mantle plume (head). The plateau was drilled during Integrated Ocean Drilling Program (IODP) Expedition 324. Complementary to a recent trace element study (Sano et al., 2012) this work presents Nd, Pb and Hf isotope data of recovered lava samples cored from the three major volcanic edifices of the Shatsky Rise. Whereas lavas from the oldest edifice yield fairly uniform compositions, a wider isotopic spread is found for lavas erupted on the younger parts of the plateau, suggesting that the Shatsky magma source became more heterogeneous with time. At least three isotopically distinct components can be identified in the magma source: 1) a volumetrically and spatially most common, moderately depleted component of similar composition to modern East Pacific Ridge basalt but with low 3He/4He, 2) an isotopically very depleted component which could represent local, early Cretaceous (entrained) depleted upper mantle, and 3) an isotopically enriched component, indicating the presence of (recycled) continental material in the magma source. The majority of analyzed Shatsky lavas, however, possess Nd-Hf-Pb isotope compositions consistent with a derivation from an early depleted, non-chondritic reservoir. By comparing these results with petrological and trace element data of mafic volcanic rock samples from all three massifs (Tamu, Ori, Shirshov), we discuss the origin of Shatsky Rise magmatism and evaluate the possible involvement of a mantle plume (head).

Estimates of lake trout (Salvelinus namaycush) diet in Lake Ontario using two and three isotope mixing models

USGS Publications Warehouse

Colborne, Scott F.; Rush, Scott A.; Paterson, Gordon; Johnson, Timothy B.; Lantry, Brian F.; Fisk, Aaron T.

2016-01-01

Recent development of multi-dimensional stable isotope models for estimating both foraging patterns and niches have presented the analytical tools to further assess the food webs of freshwater populations. One approach to refine predictions from these analyses is to include a third isotope to the more common two-isotope carbon and nitrogen mixing models to increase the power to resolve different prey sources. We compared predictions made with two-isotope carbon and nitrogen mixing models and three-isotope models that also included sulphur (δ34S) for the diets of Lake Ontario lake trout (Salvelinus namaycush). We determined the isotopic compositions of lake trout and potential prey fishes sampled from Lake Ontario and then used quantitative estimates of resource use generated by two- and three-isotope Bayesian mixing models (SIAR) to infer feeding patterns of lake trout. Both two- and three-isotope models indicated that alewife (Alosa pseudoharengus) and round goby (Neogobius melanostomus) were the primary prey items, but the three-isotope models were more consistent with recent measures of prey fish abundances and lake trout diets. The lake trout sampled directly from the hatcheries had isotopic compositions derived from the hatchery food which were distinctively different from those derived from the natural prey sources. Those hatchery signals were retained for months after release, raising the possibility to distinguish hatchery-reared yearlings and similarly sized naturally reproduced lake trout based on isotopic compositions. Addition of a third-isotope resulted in mixing model results that confirmed round goby have become an important component of lake trout diet and may be overtaking alewife as a prey resource.

A Multi-isotope Tracer Approach Linking Land Use With Carbon and Nitrogen Cycling in the San Joaquin River System

NASA Astrophysics Data System (ADS)

Young, M. B.; Kendall, C.; Silva, S. R.; Dahlgren, R. A.; Stringfellow, W. T.

2008-12-01

The San Joaquin River (SJR) is a large hypereutrophic river located in the Central Valley, California, a major agricultural region. Nutrient subsidies, algae, and other organic material from the San Joaquin River contribute to periods of low dissolved oxygen in the Stockton Deep Water Ship Channel, inhibiting salmon migration. We used a multi-isotope approach to link nitrate and particulate organic matter (POM) to different sources and related land uses. The isotope data was also used to better understand the physical and biological processes controlling the distribution of nitrate and POM throughout the river system. Samples collected from the mainstem SJR and tributaries twice-monthly to monthly between March 2005 and December 2007 were analyzed for nitrate, POM, and water isotopes. There are many land uses surrounding the SJR and its tributaries, including multiple types of agriculture, dairies, wetlands, and urban areas. Samples from SJR tributaries containing both major and minor contributions of wetland discharge generally had distinct nitrate and POM isotope signatures compared to other tributaries. Unique nitrate and POM isotope signatures associated with wetland discharges may reflect anaerobic biological processes occurring in flooded soils. For the mainstem SJR, we applied an isotope mass balance approach using nitrate and water isotopes to calculate the expected downstream isotope values based upon measured inputs from known water sources such as drains and tributaries. Differences between the calculated downstream isotope values and the measured values indicate locations and time periods when either biological processes such as algal uptake, or physical process such as the input of unidentified water sources, significantly altered the isotope signatures of water, POM, or nitrate within the SJR. This research will provide a better understanding of how different land uses affect the delivery of carbon and nitrogen to the SJR, and will provide a better understanding of the physical and biological processes occurring within the mainstem SJR.

Stable hydrogen isotope analysis as a method to identify illegally trapped songbirds.

PubMed

Kelly, Andrew; Thompson, Richard; Newton, Jason

2008-06-01

We measured stable hydrogen isotope ratios in the primary feathers of two subspecies of goldfinches, confiscated by the Police and the Royal Society for the Prevention of Cruelty to Animals (RSPCA) on suspicion that they had been illegally taken from the wild. We found significant differences in the delta2H values of the two subspecies indicating that they were sourced from different geographical regions. Our results correlated with isotopic precipitation maps and with the known distribution of the two subspecies of goldfinch. We believe that this technique could be used by law enforcement agencies to determine the origin of birds in cases where the species or subspecies involved are geographically distinct.

Quantifying nutrient sources in an upland catchment using multiple chemical and isotopic tracers

NASA Astrophysics Data System (ADS)

Sebestyen, S. D.; Boyer, E. W.; Shanley, J. B.; Doctor, D. H.; Kendall, C.; Aiken, G. R.

2006-12-01

To explore processes that control the temporal variation of nutrients in surface waters, we measured multiple environmental tracers at the Sleepers River Research Watershed, an upland catchment in northeastern Vermont, USA. Using a set of high-frequency stream water samples, we quantified the variation of nutrients over a range of stream flow conditions with chemical and isotopic tracers of water, nitrate, and dissolved organic carbon (DOC). Stream water concentrations of nitrogen (predominantly in the forms of nitrate and dissolved organic nitrogen) and DOC reflected mixing of water contributed from distinct sources in the forested landscape. Water isotopic signatures and end-member mixing analysis revealed when solutes entered the stream from these sources and that the sources were linked to the stream by preferential shallow subsurface and overland flow paths. Results from the tracers indicated that freshly-leached, terrestrial organic matter was the overwhelming source of high DOC concentrations in stream water. In contrast, in this region where atmospheric nitrogen deposition is chronically elevated, the highest concentrations of stream nitrate were attributable to atmospheric sources that were transported via melting snow and rain fall. These findings are consistent with a conceptual model of the landscape in which coupled hydrological and biogeochemical processes interact to control stream solute variability over time.

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.

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).

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.

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.

Lead Isotope Characterization of Petroleum Fuels in Taipei, Taiwan

PubMed Central

Yao, Pei-Hsuan; Shyu, Guey-Shin; Chang, Ying-Fang; Chou, Yu-Chen; Shen, Chuan-Chou; Chou, Chi-Su; Chang, Tsun-Kuo

2015-01-01

Leaded gasoline in Taiwan was gradually phased out from 1983 to 2000. However, it is unclear whether unleaded gasoline still contributes to atmospheric lead (Pb) exposure in urban areas. In this study, Pb isotopic compositions of unleaded gasolines, with octane numbers of 92, 95, 98, and diesel from two local suppliers in Taipei were determined by multi-collector inductively coupled plasma mass spectrometry with a two-sigma uncertainty of ± 0.02 %. Lead isotopic ratios of vehicle exhaust (208Pb/207Pb: 2.427, 206Pb/207Pb: 1.148, as estimated from petroleum fuels) overlap with the reported aerosol data. This agreement indicates that local unleaded petroleum fuels, containing 10–45 ng·Pb·g−1, are merely one contributor among various sources to urban aerosol Pb. Additionally, the distinction between the products of the two companies is statistically significant in their individual 208Pb/206Pb ratios (p-value < 0.001, t test). Lead isotopic characterization appears to be applicable as a “fingerprinting” tool for tracing the sources of Pb pollution. PMID:25918913

Metal enrichment and lead isotope analysis for source apportionment in the urban dust and rural surface soil.

PubMed

Yu, Yang; Li, Yingxia; Li, Ben; Shen, Zhenyao; Stenstrom, Michael K

2016-09-01

To understand the metal accumulation in the environment and identify its sources, 29 different metal contents and lead (Pb) isotope ratios were determined for 40 urban dust samples, 36 surface soil samples, and one river sediment sample collected in the municipality of Beijing, China. Results showed that cadmium, copper (Cu), mercury, Pb, antimony (Sb), and zinc demonstrated to be the typical urban contaminants and mostly influenced by the adjacent human activities with higher content to background ratios and SD values. Among the 29 metal elements investigated, Cu and Sb were found to be the most distinct elements that were highly affected by the developing level and congestion status of the cities with much higher contents in dust in more developed and congested cities. There was a relatively wider range of Pb isotope ratios of country surface soil than those of urban dust. The results of source identification based on Pb isotope ratios showed that coal combustion was the first largest Pb source and vehicle exhaust was the second largest source. The sum of them accounted for 74.6% mass proportion of overall Pb pollution on average. The surface soil sample collected at an iron mine had the highest (204)Pb/(206)Pb, (207)Pb/(206)Pb, and (208)Pb/(206)Pb ratios indicating ore had much higher ratios than other sources. The fine particle subsamples had higher (204)Pb/(206)Pb, (207)Pb/(206)Pb, and (208)Pb/(206)Pb ratios than the coarse particle subsamples indicating more anthropogenic sources of coal combustion and vehicle exhaust for fine particles and more background influence for coarse particles. These results help with pinpointing the major Pb sources and applying suitable measures for the target sources. Copyright © 2016 Elsevier Ltd. All rights reserved.

Northwest Africa 8159: An approximately 2.3 Billion Year Old Martian Olivine-Bearing Augite Basalt

NASA Technical Reports Server (NTRS)

Simon, J. I.; Peters, T. J.; Tappa, M. J.; Agee, C. B.

2014-01-01

Based on petrology, mineralogy, and bulk composition, the new NWA 8159 martian meteorite is distinct from all known samples from Mars. In particular, the augite compositional trends are unique, but most similar to those of nakhite intercumulus. Whether NWA 8159 represents a new lithology or is related to a known meteorite group remains to be determined. Sr and Nd isotopic analyses will allow comparison of source characteristics with SNC and other new ungrouped meteorites (e.g., NWA 7635). Here we report initial Rb-Sr and Sm-Nd isotopic results for NWA 8159 with the objective to determine its formation age and to potentially identify similarities and potential source affinities with other martian rocks.

Characteristics of lead isotope ratios and elemental concentrations in PM 10 fraction of airborne particulate matter in Shanghai after the phase-out of leaded gasoline

NASA Astrophysics Data System (ADS)

Zheng, Jian; Tan, Mingguang; Shibata, Yasuyuki; Tanaka, Atsushi; Li, Yan; Zhang, Guilin; Zhang, Yuanmao; Shan, Zuci

The stable lead (Pb) isotope ratios and the concentrations of 23 elements, including heavy metals and toxic elements, were measured in the PM 10 airborne particle samples collected at seven monitoring sites in Shanghai, China, to evaluate the current elemental compositions and local airborne Pb isotope ratio characteristics. Some source-related samples, such as cement, coal and oil combustion dust, metallurgic dust, vehicle exhaust particles derived from leaded gasoline and unleaded gasoline, and polluted soils were analyzed for their Pb content and isotope ratio and compared to those observed in PM 10 samples. Airborne Pb concentration ranged from 167 to 854 ng/m 3 in the seven monitored sites with an average of 515 ng/m 3 in Shanghai, indicating that a high concentration of Pb remains in the air after the phasing out of leaded gasoline. Lead isotopic compositions in airborne particles ( 207Pb/ 206Pb, 0.8608±0.0018; 208Pb/ 206Pb, 2.105±0.005) are clearly distinct from the vehicle exhaust particles ( 207Pb/ 206Pb, 0.8854±0.0075; 208Pb/ 206Pb, 2.145±0.006), suggesting that the automotive lead is not currently the major component of Pb in the air. By using a binary mixing equation, a source apportionment based on 207Pb/ 206Pb ratios, indicates that the contribution from automotive emission to the airborne Pb is around 20%. The Pb isotope ratios obtained in the source-related samples confirmed that the major emission sources are metallurgic dust, coal combustion, and cement.

Variable sulfur isotope composition of sulfides provide evidence for multiple sources of contamination in the Rustenburg Layered Suite, Bushveld Complex

NASA Astrophysics Data System (ADS)

Magalhães, Nivea; Penniston-Dorland, Sarah; Farquhar, James; Mathez, Edmond A.

2018-06-01

The Rustenburg Layered Suite (RLS) of the Bushveld Complex (BC) is famous for its platinum group element (PGE) ore, which is hosted in sulfides. The source of sulfur necessary to generate this type of mineralization is inferred to be the host rock of the intrusion. The RLS has a sulfur isotopic signature that indicates the presence of Archean surface-derived material (Δ33 S ≠ 0) in the magma. This signature, with an average value of Δ33 S = 0.112 ± 0.024 ‰, deviates from the expected Δ33 S value of the mantle of 0 ± 0.008 ‰. Previous work suggested that this signature is uniform throughout the RLS, which contrasts with radiogenic isotopes which vary throughout the igneous stratigraphy of the RLS. In this study, samples from key intervals within the igneous stratigraphy were analyzed, showing that Δ33 S values vary in the same stratigraphic levels as Sr and Nd isotopes. However, the variation is not consistent; in some levels there is a positive correlation and in others a negative correlation. This observation suggests that in some cases distinct magma pulses contained assimilated sulfur from different sources. Textural analysis shows no evidence for late addition of sulfur. These results also suggest that it is unlikely that large-scale assimilation and/or efficient mixing of host rock material in a single magma chamber occurred during emplacement. The data do not uniquely identify the source of sulfur in the different layers of the RLS, but the variation in sulfur isotope composition and its relationship to radiogenic isotope data calls for a reevaluation of the models for the formation and evolution of the RLS, which has the potential to impact the knowledge of how PGE deposits form.

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.

Isotopic Composition of Atmospheric Mercury in China: New Evidence for Sources and Transformation Processes in Air and in Vegetation.

PubMed

Yu, Ben; Fu, Xuewu; Yin, Runsheng; Zhang, Hui; Wang, Xun; Lin, Che-Jen; Wu, Chuansheng; Zhang, Yiping; He, Nannan; Fu, Pingqing; Wang, Zifa; Shang, Lihai; Sommar, Jonas; Sonke, Jeroen E; Maurice, Laurence; Guinot, Benjamin; Feng, Xinbin

2016-09-06

The isotopic composition of atmospheric total gaseous mercury (TGM) and particle-bound mercury (PBM) and mercury (Hg) in litterfall samples have been determined at urban/industrialized and rural sites distributed over mainland China for identifying Hg sources and transformation processes. TGM and PBM near anthropogenic emission sources display negative δ(202)Hg and near-zero Δ(199)Hg in contrast to relatively positive δ(202)Hg and negative Δ(199)Hg observed in remote regions, suggesting that different sources and atmospheric processes force the mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) in the air samples. Both MDF and MIF occur during the uptake of atmospheric Hg by plants, resulting in negative δ(202)Hg and Δ(199)Hg observed in litter-bound Hg. The linear regression resulting from the scatter plot relating the δ(202)Hg to Δ(199)Hg data in the TGM samples indicates distinct anthropogenic or natural influences at the three study sites. A similar trend was also observed for Hg accumulated in broadleaved deciduous forest foliage grown in areas influenced by anthropogenic emissions. The relatively negative MIF in litter-bound Hg compared to TGM is likely a result of the photochemical reactions of Hg(2+) in foliage. This study demonstrates the diagnostic stable Hg isotopic composition characteristics for separating atmospheric Hg of different source origins in China and provides the isotopic fractionation clues for the study of Hg bioaccumulation.

Using semi-continuous, in-situ measurements of nitrous oxide isotopic composition at a suburban site to track emission processes

NASA Astrophysics Data System (ADS)

Harris, Eliza; Henne, Stephan; Christoph, Hüglin; Christoph, Zellweger; Béla, Tuzson; Erkan, Ibraim; Lukas, Emmenegger; Joachim, Mohn

2017-04-01

Nitrous oxide (N2O) is a potent greenhouse gas and the strongest ozone-destroying substance emitted this century. The atmospheric N2O mole fraction has been increasing at a rate of 0.2-0.3% per year over the past decades due to anthropogenic emissions; in addition, recent results suggest that the rate of increase is rising - therefore effective mitigation of N2O emissions is a critical point for environmental policy. However, N2O sources are poorly defined and disperse, complicating the development of targeted mitigation strategies. Online isotopic measurements using preconcentration and laser spectroscopy [1,2,3] have great potential to unravel spatial and temporal variations in sources, sinks and chemistry of trace gases such as N2O. Semi-continuous, real-time measurements of N2O isotopic composition (δ18O, site preference [SP = 14N15N16O - 15N14N16O] and δ15Nbulk) were performed at the suburban site of Dübendorf, Switzerland, for 19 months between July 2014 and February 2016. The data precision reached 0.1‰ in the final months, thus the results could clearly identify nocturnal build-up of N2O, with a corresponding decrease in δ18O, SP and δ15Nbulk due to isotopically depleted anthropogenic sources. Daily mean source isotopic composition was calculated by considering the measured and the background mole fraction and isotopic composition. Delta values of the mean emission source were highest in winter, with a seasonal cycle of 12, 8 and 5‰ for δ18O, SP and δ15Nbulk respectively. The chemical and meteorological parameters controlling source isotopic composition were considered using data from the Swiss National Air Pollution Monitoring Network (NABEL) as well as a transport regime cluster analysis. A clear spatial distribution for source isotopic composition was observed for δ18O, as well as a significant relationship with the level of urban pollution, indicating δ18O may be a strong indicator of combustion/industrial vs. agricultural N2O. In contrast, δ15Nbulk and particularly SP appear to vary too strongly in response to other factors affecting emission processes to provide a useful distinction between source categories on a regional scale - these isotopocules may however be useful to distinguish emission pathways on a local scale. For comparison, FLEXPART-COSMO transport simulations [4] were combined with emissions from the EDGAR inventory and estimates of source isotopic composition from literature, to simulate N2O isotopic composition at the sampling site. The model was able to capture variability in N2O mole fraction adequately (R2 = 0.34; p <<0.01). However, the measured variability in source isotopic composition was 1-2 orders of magnitude larger than simulated, illustrating that our knowledge of isotopic source signatures - in particular technical N2O sources - is still too limited to successfully model variations in ambient N2O isotopic composition. [1] Mohn et al. (2012) Atmospheric Measurement Techniques, doi:10.5194/amt-5-1601-2012 [2] Harris et al. (2014) Analytical Chemistry, doi: 10.1021/ac403606u. [3] Röckmann et al. (2016) Atmospheric Chemistry and Physics, doi:10.5194/acp-16-10469-2016. [4] Henne et al. (2016) Atmospheric Chemistry and Physics, doi:10.5194/acp-16-3683-2016.

A molecular and isotopic study of the organic matter from the Paris Basin, France

NASA Technical Reports Server (NTRS)

Lichtfouse, E.; Albrecht, P.; Behar, F.; Hayes, J. M.

1994-01-01

Thirteen Liassic sedimentary rocks of increasing depth and three petroleums from the Paris Basin were studied for 13C/12C isotopic compositions and biological markers, including steranes, sterenes, methylphenanthrenes, methylanthracenes, and triaromatic steroids. The isotopic compositions of n-alkanes from mature sedimentary rocks and petroleums fall in a narrow range (2%), except for the deepest Hettangian rock and the Trias petroleum, for which the short-chain n-alkanes are enriched and depleted in 13C, respectively. Most of the molecular parameters increase over the 2000-2500 m depth range, reflecting the transformation of the organic matter at the onset of petroleum generation. In this zone, carbonate content and carbon isotopic composition of carbonates, as well as molecular parameters, are distinct for the Toarcian and Hettangian source rocks and suggest a migration of organic matter from these two formations. Two novel molecular parameters were defined for this task: one using methyltriaromatic steroids from organic extracts; the other using 1-methylphenanthrene and 2-methylanthracene from kerogen pyrolysates. The anomalous high maturity of the Dogger petroleum relative to the maturity-depth trend of the source rocks is used to estimate the minimal vertical distance of migration of the organic matter from the source rock to the reservoir.

Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs.

PubMed

Sherwood Lollar, B; Westgate, T D; Ward, J A; Slater, G F; Lacrampe-Couloume, G

2002-04-04

Natural hydrocarbons are largely formed by the thermal decomposition of organic matter (thermogenesis) or by microbial processes (bacteriogenesis). But the discovery of methane at an East Pacific Rise hydrothermal vent and in other crustal fluids supports the occurrence of an abiogenic source of hydrocarbons. These abiogenic hydrocarbons are generally formed by the reduction of carbon dioxide, a process which is thought to occur during magma cooling and-more commonly-in hydrothermal systems during water-rock interactions, for example involving Fischer-Tropsch reactions and the serpentinization of ultramafic rocks. Suggestions that abiogenic hydrocarbons make a significant contribution to economic hydrocarbon reservoirs have been difficult to resolve, in part owing to uncertainty in the carbon isotopic signatures for abiogenic versus thermogenic hydrocarbons. Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons. The progressive isotopic trends for the series of C1-C4 alkanes indicate that hydrocarbon formation occurs by way of polymerization of methane precursors. Given that these trends are not observed in the isotopic signatures of economic gas reservoirs, we can now rule out the presence of a globally significant abiogenic source of hydrocarbons.

Multiple sources supply eolian mineral dust to the Atlantic sector of coastal Antarctica: Evidence from recent snow layers at the top of Berkner Island ice sheet

NASA Astrophysics Data System (ADS)

Bory, Aloys; Wolff, Eric; Mulvaney, Robert; Jagoutz, Emil; Wegner, Anna; Ruth, Urs; Elderfield, Harry

2010-03-01

The Sr and Nd isotopic composition of dust extracted from recent snow layers at the top of Berkner Island ice sheet (located within the Filchner-Ronne Ice Shelf at the southern end of the Weddell Sea) enables us, for the first time, to document dust provenance in Antarctica outside the East Antarctic Plateau (EAP) where all previous studies based on isotopic fingerprinting were carried out. Berkner dust displays an overall crust-like isotopic signature, characterized by more radiogenic 87Sr/ 86Sr and much less radiogenic 143Nd/ 144Nd compared to dust deposited on the EAP during glacial periods. Differences with EAP interglacial dust are not as marked but still significant, indicating that present-day Berkner dust provenance is distinct, at least to some extent, from that of the dust reaching the EAP. The fourteen snow-pit sub-seasonal samples that were obtained span a two-year period (2002-2003) and their dust Sr and Nd isotopic composition reveals that multiple sources are at play over a yearly time period. Southern South America, Patagonia in particular, likely accounts for part of the observed spring/summer dust deposition maxima, when isotopic composition is shifted towards "younger" isotopic signatures. In the spring, possible additional inputs from Australian sources would also be supported by the data. Most of the year, however, the measured isotopic signatures would be best explained by a sustained background supply from putative local sources in East Antarctica, which carry old-crust-like isotopic fingerprints. Whether the restricted East Antarctic ice-free areas produce sufficient eolian material has yet to be substantiated however. The fact that large (> 5 μm) particles represent a significant fraction of the samples throughout the entire time-series supports scenarios that involve contributions from proximal sources, either in Patagonia and/or Antarctica (possibly including snow-free areas in the Antarctic Peninsula and other areas as well). This also indicates that additional dust transport, which does not reach the EAP, must occur at low-tropospheric levels to this coastal sector of Antarctica.

D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

USGS Publications Warehouse

Schimmelmann, A.; Lewan, M.D.; Wintsch, R.P.

1999-01-01

Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310-381??C), time (12-144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil-hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330??C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ~ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381 ??C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350??C for 72 h, or 330??C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115??C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected by exchange with water hydrogen at typical reservoir conditions over geologic time. It will be difficult to utilize D/H ratios of thermally mature bulk or fractions of organic matter to quantitatively reconstruct isotopic aspects of paleoclimate and paleoenvironment. Hope resides in compound-specific D/H ratios of thermally stable, extractable biomarkers ('molecular fossils') that are less susceptible to hydrogen exchange with water-derived hydrogen.

Isotopic imprints of mountaintop mining contaminants.

PubMed

Vengosh, Avner; Lindberg, T Ty; Merola, Brittany R; Ruhl, Laura; Warner, Nathaniel R; White, Alissa; Dwyer, Gary S; Di Giulio, Richard T

2013-09-03

Mountaintop mining (MTM) is the primary procedure for surface coal exploration within the central Appalachian region of the eastern United States, and it is known to contaminate streams in local watersheds. In this study, we measured the chemical and isotopic compositions of water samples from MTM-impacted tributaries and streams in the Mud River watershed in West Virginia. We systematically document the isotopic compositions of three major constituents: sulfur isotopes in sulfate (δ(34)SSO4), carbon isotopes in dissolved inorganic carbon (δ(13)CDIC), and strontium isotopes ((87)Sr/(86)Sr). The data show that δ(34)SSO4, δ(13)CDIC, Sr/Ca, and (87)Sr/(86)Sr measured in saline- and selenium-rich MTM impacted tributaries are distinguishable from those of the surface water upstream of mining impacts. These tracers can therefore be used to delineate and quantify the impact of MTM in watersheds. High Sr/Ca and low (87)Sr/(86)Sr characterize tributaries that originated from active MTM areas, while tributaries from reclaimed MTM areas had low Sr/Ca and high (87)Sr/(86)Sr. Leaching experiments of rocks from the watershed show that pyrite oxidation and carbonate dissolution control the solute chemistry with distinct (87)Sr/(86)Sr ratios characterizing different rock sources. We propose that MTM operations that access the deeper Kanawha Formation generate residual mined rocks in valley fills from which effluents with distinctive (87)Sr/(86)Sr and Sr/Ca imprints affect the quality of the Appalachian watersheds.

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.

CO2 dynamics in the Amargosa Desert: Fluxes and isotopic speciation in a deep unsaturated zone

USGS Publications Warehouse

Walvoord, Michelle Ann; Striegl, Robert G.; Prudic, David E.; Stonestrom, David A.

2005-01-01

Natural unsaturated-zone gas profiles at the U.S. Geological Survey's Amargosa Desert Research Site, near Beatty, Nevada, reveal the presence of two physically and isotopically distinct CO2 sources, one shallow and one deep. The shallow source derives from seasonally variable autotrophic and heterotrophic respiration in the root zone. Scanning electron micrograph results indicate that at least part of the deep CO2 source is associated with calcite precipitation at the 110-m-deep water table. We use a geochemical gas-diffusion model to explore processes of CO2 production and behavior in the unsaturated zone. The individual isotopic species 12CO2, 13CO2, and 14CO2 are treated as separate chemical components that diffuse and react independently. Steady state model solutions, constrained by the measured δ13C (in CO2), and δ14C (in CO2) profiles, indicate that the shallow CO2 source from root and microbial respiration composes ∼97% of the annual average total CO2 production at this arid site. Despite the small contribution from deep CO2 production amounting to ∼0.1 mol m−2 yr−1, upward diffusion from depth strongly influences the distribution of CO2 and carbon isotopes in the deep unsaturated zone. In addition to diffusion from deep CO2 production, 14C exchange with a sorbed CO2 phase is indicated by the modeled δ14C profiles, confirming previous work. The new model of carbon-isotopic profiles provides a quantitative approach for evaluating fluxes of carbon under natural conditions in deep unsaturated zones.

Molybdenum mobility and isotopic fractionation during subduction at the Mariana arc

NASA Astrophysics Data System (ADS)

Freymuth, Heye; Vils, Flurin; Willbold, Matthias; Taylor, Rex N.; Elliott, Tim

2015-12-01

The fate of crustal material recycled into the convecting mantle by plate tectonics is important for understanding the chemical and physical evolution of the planet. Marked isotopic variability of Mo at the Earth's surface offers the promise of providing distinctive signatures of such recycled material. However, characterisation of the behaviour of Mo during subduction is needed to assess the potential of Mo isotope ratios as tracers for global geochemical cycles. Here we present Mo isotope data for input and output components of the archetypical Mariana arc: Mariana arc lavas, sediments from ODP Sites 800, 801 and 802 near the Mariana trench and the altered mafic, oceanic crust (AOC), from ODP Site 801, together with samples of the deeper oceanic crust from ODP Site 1256. We also report new high precision Pb isotope data for the Mariana arc lavas and a dataset of Pb isotope ratios from sediments from ODP Sites 800, 801 and 802. The Mariana arc lavas are enriched in Mo compared to elements of similar incompatibility during upper mantle melting, and have distinct, isotopically heavy Mo (high 98Mo/95Mo) relative to the upper mantle, by up to 0.3 parts per thousand. In contrast, the various subducting sediment lithologies dominantly host isotopically light Mo. Coupled Pb and Mo enrichment in the Mariana arc lavas suggests a common source for these elements and we further use Pb isotopes to identify the origin of the isotopically heavy Mo. We infer that an aqueous fluid component with elevated [Mo], [Pb], high 98Mo/95Mo and unradiogenic Pb is derived from the subducting, mafic oceanic crust. Although the top few hundred metres of the subducting, mafic crust have a high 98Mo/95Mo, as a result of seawater alteration, tightly defined Pb isotope arrays of the Mariana arc lavas extrapolate to a fluid component akin to fresh Pacific mid-ocean ridge basalts. This argues against a flux dominantly derived from the highly altered, uppermost mafic crust or indeed from an Indian-like mantle wedge. Thus we infer that the Pb and Mo budgets of the fluid component are dominated by contributions from the deeper, less altered (cooler) portion of the subducting Pacific crust. The high 98Mo/95Mo of this flux is likely caused by isotopic fractionation during dehydration and fluid flow in the slab. As a result, the residual mafic crust becomes isotopically lighter than the upper mantle from which it was derived. Our results suggest that the continental crust produced by arc magmatism should have an isotopically heavy Mo composition compared to the mantle, whilst a contribution of deep recycled oceanic crust to the sources of some ocean island basalts might be evident from an isotopically light Mo signature.

Temporal geochemical evolution of Kilauea Volcano: Comparison of Hilina and Puna Basalt

NASA Astrophysics Data System (ADS)

Chen, C.-Y.; Frey, F. A.; Rhodes, J. M.; Eastern, R. M.

Temporal geochcmical variations in Hawaiian shield-building lavas provide important constraints on the origin and evolution of these lavas. We determined the major and trace element content, and Sr, Nd and Pb isotopic ratios of the oldest subaerially exposed lavas on Kilauea Volcano, i.e., the >25 Ka to perhaps 100 Ka, Hilina Basalt. Except for lower K2O and Rb abundances in Hilina lavas, the compositions of these prehistoric lavas overlap with historical Kilauea lavas. Although the studied Hilina lavas are not highly altered, the lower abundances of K2O and Rb may reflect post-eruptive alteration. Compared with historical Kilauea lavas, Hilina lavas have a similar range in Sr and Nd isotopic ratios, but they range to more radiogenic Pb isotopic ratios. The mantle source of Kilauea lavas is heterogeneous in isotopic ratios and perhaps in abundance ratios of some incompatible elements, but there is no evidence for systematic long-term geochemical variations in the source of Kilauea lavas. None of the prehistoric Kilauea lavas have isotopic characteristics similar to those of subaerial Mauna Loa lavas. Apparently, the sources and ascent paths of lavas forming the adjacent Kilauea and Mauna Loa shields have largely remained distinct during subaerial growth of the Kilauea shield. Compared to lavas from other Hawaiian shields, Kilauea lavas range to relatively high 206Pb/204Pb and low 87Sr/86Sr. These isotopic ratios are correlated with trace element abundance ratios that involve Nb, e.g., Zr/Nb; some Hilina lavas define the upper range in 206Pb/204Pb (˜18.82), and they have low Zr/Nb (˜8). This "Kilauea component" which has isotopic characteristics similar to the FOZO component (e.g., Hauri et al., 1994a] is an intrinsic part of the Hawaiian plume.

Isotopic homogeneity of iron in the early solar nebula.

PubMed

Zhu, X K; Guo, Y; O'Nions, R K; Young, E D; Ash, R D

2001-07-19

The chemical and isotopic homogeneity of the early solar nebula, and the processes producing fractionation during its evolution, are central issues of cosmochemistry. Studies of the relative abundance variations of three or more isotopes of an element can in principle determine if the initial reservoir of material was a homogeneous mixture or if it contained several distinct sources of precursor material. For example, widespread anomalies observed in the oxygen isotopes of meteorites have been interpreted as resulting from the mixing of a solid phase that was enriched in 16O with a gas phase in which 16O was depleted, or as an isotopic 'memory' of Galactic evolution. In either case, these anomalies are regarded as strong evidence that the early solar nebula was not initially homogeneous. Here we present measurements of the relative abundances of three iron isotopes in meteoritic and terrestrial samples. We show that significant variations of iron isotopes exist in both terrestrial and extraterrestrial materials. But when plotted in a three-isotope diagram, all of the data for these Solar System materials fall on a single mass-fractionation line, showing that homogenization of iron isotopes occurred in the solar nebula before both planetesimal accretion and chondrule formation.

Chondritic xenon in the Earth’s mantle

NASA Astrophysics Data System (ADS)

Caracausi, Antonio; Avice, Guillaume; Burnard, Peter G.; Füri, Evelyn; Marty, Bernard

2016-05-01

Noble gas isotopes are powerful tracers of the origins of planetary volatiles, and the accretion and evolution of the Earth. The compositions of magmatic gases provide insights into the evolution of the Earth’s mantle and atmosphere. Despite recent analytical progress in the study of planetary materials and mantle-derived gases, the possible dual origin of the planetary gases in the mantle and the atmosphere remains unconstrained. Evidence relating to the relationship between the volatiles within our planet and the potential cosmochemical end-members is scarce. Here we show, using high-precision analysis of magmatic gas from the Eifel volcanic area (in Germany), that the light xenon isotopes identify a chondritic primordial component that differs from the precursor of atmospheric xenon. This is consistent with an asteroidal origin for the volatiles in the Earth’s mantle, and indicates that the volatiles in the atmosphere and mantle originated from distinct cosmochemical sources. Furthermore, our data are consistent with the origin of Eifel magmatism being a deep mantle plume. The corresponding mantle source has been isolated from the convective mantle since about 4.45 billion years ago, in agreement with models that predict the early isolation of mantle domains. Xenon isotope systematics support a clear distinction between mid-ocean-ridge and continental or oceanic plume sources, with chemical heterogeneities dating back to the Earth’s accretion. The deep reservoir now sampled by the Eifel gas had a lower volatile/refractory (iodine/plutonium) composition than the shallower mantle sampled by mid-ocean-ridge volcanism, highlighting the increasing contribution of volatile-rich material during the first tens of millions of years of terrestrial accretion.

Chondritic xenon in the Earth's mantle.

PubMed

Caracausi, Antonio; Avice, Guillaume; Burnard, Peter G; Füri, Evelyn; Marty, Bernard

2016-05-05

Noble gas isotopes are powerful tracers of the origins of planetary volatiles, and the accretion and evolution of the Earth. The compositions of magmatic gases provide insights into the evolution of the Earth's mantle and atmosphere. Despite recent analytical progress in the study of planetary materials and mantle-derived gases, the possible dual origin of the planetary gases in the mantle and the atmosphere remains unconstrained. Evidence relating to the relationship between the volatiles within our planet and the potential cosmochemical end-members is scarce. Here we show, using high-precision analysis of magmatic gas from the Eifel volcanic area (in Germany), that the light xenon isotopes identify a chondritic primordial component that differs from the precursor of atmospheric xenon. This is consistent with an asteroidal origin for the volatiles in the Earth's mantle, and indicates that the volatiles in the atmosphere and mantle originated from distinct cosmochemical sources. Furthermore, our data are consistent with the origin of Eifel magmatism being a deep mantle plume. The corresponding mantle source has been isolated from the convective mantle since about 4.45 billion years ago, in agreement with models that predict the early isolation of mantle domains. Xenon isotope systematics support a clear distinction between mid-ocean-ridge and continental or oceanic plume sources, with chemical heterogeneities dating back to the Earth's accretion. The deep reservoir now sampled by the Eifel gas had a lower volatile/refractory (iodine/plutonium) composition than the shallower mantle sampled by mid-ocean-ridge volcanism, highlighting the increasing contribution of volatile-rich material during the first tens of millions of years of terrestrial accretion.

Variability of isotope and major ion chemistry in the Allequash Basin, Wisconsin

USGS Publications Warehouse

Walker, John F.; Hunt, Randall J.; Bullen, Thomas D.; Krabbenhoft, David P.; Kendall, Carol

2003-01-01

As part of ongoing research conducted at one of the U.S. Geological Survey's Water, Energy, and Biogeochem-ical Budgets sites, work was undertaken to describe the spatial and temporal variability of stream and ground water isotopic composition and cation chemistry in the Trout Lake watershed, to relate the variability to the watershed flow system, and to identify the linkages of geochemical evolution and source of water in the watershed. The results are based on periodic sampling of sites at two scales along Allequash Creek, a small headwater stream in northern Wisconsin. Based on this sampling, there are distinct water isotopic and geochemical differences observed at a smaller hillslope scale and the larger Allequash Creek scale. The variability was larger than expected for this simple watershed, and is likely to be seen in more complex basins. Based on evidence from multiple isotopes and stream chemistry, the flow system arises from three main source waters (terrestrial-, lake-, or wetland-derived recharge) that can be identified along any flowpath using water isotopes together with geochemical characteristics such as iron concentrations. The ground water chemistry demonstrates considerable spatial variability that depends mainly on the flow-path length and water mobility through the aquifer. Calcium concentrations increase with increasing flowpath length, whereas strontium isotope ratios increase with increasing extent of stagnation in either the unsaturated or saturated zones as waters move from source to sink. The flowpath distribution we identify provides important constraints on the calibration of ground water flow models such as that undertaken by Pint et al. (this issue).

The provenances of asteroids, and their contributions to the volatile inventories of the terrestrial planets.

PubMed

Alexander, C M O'D; Bowden, R; Fogel, M L; Howard, K T; Herd, C D K; Nittler, L R

2012-08-10

Determining the source(s) of hydrogen, carbon, and nitrogen accreted by Earth is important for understanding the origins of water and life and for constraining dynamical processes that operated during planet formation. Chondritic meteorites are asteroidal fragments that retain records of the first few million years of solar system history. The deuterium/hydrogen (D/H) values of water in carbonaceous chondrites are distinct from those in comets and Saturn's moon Enceladus, implying that they formed in a different region of the solar system, contrary to predictions of recent dynamical models. The D/H values of water in carbonaceous chondrites also argue against an influx of water ice from the outer solar system, which has been invoked to explain the nonsolar oxygen isotopic composition of the inner solar system. The bulk hydrogen and nitrogen isotopic compositions of CI chondrites suggest that they were the principal source of Earth's volatiles.

What Drives Hydrogen Isotopic Variability Recorded by Biomarkers in Sediments of Lake Karakul, Pamir?

NASA Astrophysics Data System (ADS)

Aichner, B.; Mischke, S.; Pausata, F. S. R.; Werner, M.; Zhang, Q.; Heinecke, L.; Feakins, S. J.; Sachse, D.; Mahmoudov, Z.; Rajabov, I.

2017-12-01

Central Asia is a climate sensitive region located at the boundary of large scale atmospheric circulation systems. To examine glacial to interglacial hydrological changes in the region, we analysed the hydrogen isotopic composition (δD values) of n-alkanes in a 30-ka record from Lake Karakul, eastern Pamir (altitude: 3,915m, MAT: -3.9 °C, MAP: 82 mm). δD values of both aquatic and terrestrial compounds showed distinct trends throughout the studied time interval, with generally higher values during the glacial and lower values during the Holocene, and variability of up to 60‰. In particular shifts towards higher δD values were observed for aquatic biomarkers at ca. 30, 27, and 15 ka BP. Temperature and precipitation effects alone cannot explain the higher δD values during the glacial and the large isotopic amplitudes. To explain these observations we conducted a set of experiments using atmospheric models with embedded isotope modules (CAM3iso- and ECHAM5-wiso). We assume that terrestrial n-alkanes mainly record the isotopic signature of summer precipitation within the lower elevated parts of the Karakul Basin. Based on the model output we hypothesize that shifts between local and more distant vapour sources are the reason behind the trends within isotopic data. Data derived from aquatic biomarkers are more difficult to explain due to multiple influencing factors on δD of the lake water. Assuming that the lake water integrates an annual isotopic signal from the whole lake catchment, we suggest that a change in precipitation seasonality drives the large variability of hydrogen isotopic values. This is in agreement with the models, which suggest reduced winter (more negative δD) and slightly higher summer precipitation (more positive δD) during the glacial compared to the Holocene. Consequently, a net-increase of isotopically enriched inflow into the lake could explain the three distinct shifts towards higher δD values. Expansion of terrestrial vegetation, indicated by increasing biomarker concentrations, during these periods is another indicator for wetter summers in an arid environment. We conclude that δD values of terrestrial compounds reflect major shifts of vapour sources which are driven by insolation, while aquatic biomarkers are additionally influenced by changes of precipitation seasonality.

Isotopic and trace element constraints on the petrogenesis of lavas from the Mount Adams volcanic field, Washington

USGS Publications Warehouse

Jicha, B.R.; Hart, G.L.; Johnson, C.M.; Hildreth, Wes; Beard, B.L.; Shirey, S.B.; Valley, J.W.

2009-01-01

Strontium, Nd, Pb, Hf, Os, and O isotope compositions for 30 Quaternary lava flows from the Mount Adams stratovolcano and its basaltic periphery in the Cascade arc, southern Washington, USA indicate a major component from intraplate mantle sources, a relatively small subduction component, and interaction with young mafic crust at depth. Major- and trace-element patterns for Mount Adams lavas are distinct from the rear-arc Simcoe volcanic field and other nearby volcanic centers in the Cascade arc such as Mount St. Helens. Radiogenic isotope (Sr, Nd, Pb, and Hf) compositions do not correlate with geochemical indicators of slab-fluids such as (Sr/P)n and Ba/Nb. Mass-balance modeling calculations, coupled with trace-element and isotopic data, indicate that although the mantle source for the calc-alkaline Adams basalts has been modified with a fluid derived from subducted sediment, the extent of modification is significantly less than what is documented in the southern Cascades. The isotopic and trace-element compositions of most Mount Adams lavas require the presence of enriched and depleted mantle sources, and based on volume-weighted chemical and isotopic compositions for Mount Adams lavas through time, an intraplate mantle source contributed the major magmatic mass of the system. Generation of basaltic andesites to dacites at Mount Adams occurred by assimilation and fractional crystallization in the lower crust, but wholesale crustal melting did not occur. Most lavas have Tb/Yb ratios that are significantly higher than those of MORB, which is consistent with partial melting of the mantle in the presence of residual garnet. ??18O values for olivine phenocrysts in Mount Adams lavas are within the range of typical upper mantle peridotites, precluding involvement of upper crustal sedimentary material or accreted terrane during magma ascent. The restricted Nd and Hf isotope compositions of Mount Adams lavas indicate that these isotope systems are insensitive to crustal interaction in this juvenile arc, in stark contrast to Os isotopes, which are highly sensitive to interaction with young, mafic material in the lower crust. ?? Springer-Verlag 2008.

Measurement and Modeling of Site-specific Nitrogen and Oxygen Isotopic Composition of Atmospheric Nitrous Oxide at Mace Head, Ireland

NASA Astrophysics Data System (ADS)

McClellan, M. J.; Saikawa, E.; Prinn, R. G.; Ono, S.

2015-12-01

Global mixing ratios of atmospheric nitrous oxide (N2O), a potent greenhouse gas, have increased nearly linearly from the beginning of the modern industrial period to today, with the current global average in excess of 325 ppb. This increase can be largely attributed to anthropogenic activity above the level of N2O emissions from natural biotic sources. The effect of N2O on Earth's climate is twofold: in the troposphere, N2O is radiatively active and chemically inert, while it serves as a reactive source of ozone-destroying nitrogen oxides in the stratosphere. The marked altitudinal divide in its reactivity means that all stages in the N2O life cycle—emission, transport, and destruction—must be examined to understand the overall effect of N2O on Earth's climate. However, the understanding of the total impact of N2O is incomplete, as there remain significant uncertainties in the global budget of this gas. Due to unique isotopic substitutions (15N and 18O) made by different N2O sources and stratospheric chemical reactions, the measurement of N2O isotopic ratios in ambient air can help identify the distribution and magnitude of distinct source types. We present the first year of site-specific nitrogen and oxygen isotopic composition data from the MIT Stheno-tunable infrared direct absorption spectroscopy (TILDAS) instrument at Mace Head, Ireland. Aided by the Stheno preconcentration system, Stheno-TILDAS can achieve measurement precisions of 0.10‰ or greater for all isotopic ratios (δ15N and δ18O) in ambient N2O. We further compare these data to the results from Model for Ozone and Related Tracers version 4 (MOZART-4) simulations, including N2O isotopic fractionation processes and MERRA/GEOS-5 reanalysis meteorological fields. These results will form the basis of future Bayesian inverse modeling simulations that will constrain global N2O source, circulation, and sink dynamics better.

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.

Source tracing of natural organic matter bound mercury in boreal forest runoff with mercury stable isotopes.

PubMed

Jiskra, Martin; Wiederhold, Jan G; Skyllberg, Ulf; Kronberg, Rose-Marie; Kretzschmar, Ruben

2017-10-18

Terrestrial runoff represents a major source of mercury (Hg) to aquatic ecosystems. In boreal forest catchments, such as the one in northern Sweden studied here, mercury bound to natural organic matter (NOM) represents a large fraction of mercury in the runoff. We present a method to measure Hg stable isotope signatures of colloidal Hg, mainly complexed by high molecular weight or colloidal natural organic matter (NOM) in natural waters based on pre-enrichment by ultrafiltration, followed by freeze-drying and combustion. We report that Hg associated with high molecular weight NOM in the boreal forest runoff has very similar Hg isotope signatures as compared to the organic soil horizons of the catchment area. The mass-independent fractionation (MIF) signatures (Δ 199 Hg and Δ 200 Hg) measured in soils and runoff were in agreement with typical values reported for atmospheric gaseous elemental mercury (Hg 0 ) and distinctly different from reported Hg isotope signatures in precipitation. We therefore suggest that most Hg in the boreal terrestrial ecosystem originated from the deposition of Hg 0 through foliar uptake rather than precipitation. Using a mixing model we calculated the contribution of soil horizons to the Hg in the runoff. At moderate to high flow runoff conditions, that prevailed during sampling, the uppermost part of the organic horizon (Oe/He) contributed 50-70% of the Hg in the runoff, while the underlying more humified organic Oa/Ha and the mineral soil horizons displayed a lower mobility of Hg. The good agreement of the Hg isotope results with other source tracing approaches using radiocarbon signatures and Hg : C ratios provides additional support for the strong coupling between Hg and NOM. The exploratory results from this study illustrate the potential of Hg stable isotopes to trace the source of Hg from atmospheric deposition through the terrestrial ecosystem to soil runoff, and provide a basis for more in-depth studies investigating the mobility of Hg in terrestrial ecosystems using Hg isotope signatures.

Stable sulfur and oxygen isotopes as geochemical tracers of sulfate in karst waters

NASA Astrophysics Data System (ADS)

Sun, Jing; Kobayashi, Tatsuaki; Strosnider, William H. J.; Wu, Pan

2017-08-01

Karst water resources, which are extremely sensitive to mining activities, are critical for the support of human societies and ecological systems in many regions worldwide. In order to determine the sources and fate of dissolved sulfate in low-pH karst waters, hydrochemical variations of karst waters with and without acid mine drainage (AMD) impacts were investigated along with stable isotope dynamics. As expected, hydrochemical characteristics and isotopic compositions of the AMD and AMD-downstream water (ADW) were dramatically different from that of the non-AMD-impacted water (NAW). The sources of sulfur isotopes in sulfate were predominantly pyrite oxidation for the AMD and ADW, and atmospheric deposition for the NAW. Based on the general isotope-balance model, the relative proportions of sulfate oxygen derived from water and air were calculated. The mean proportion of sulfate oxygen derived from water in ADW was roughly double that of AMD. This suggests that the sulfate associated with AMD is predominantly influenced by aerobic pyrite oxidation, while that of ADW is likely affected by the dissolution of pyrite under anaerobic conditions in reservoir sediment. This observation was coincident with the noted variations of hydrochemical characteristics and was supported by principal component analysis. These results provide a better understanding of how stable isotopes of sulfate and water can be used to track mining contamination in karst aquifers, which could benefit remediation planning for these distinctive systems.

Isotopic evolution of the idaho batholith and Challis intrusive province, Northern US Cordillera

USGS Publications Warehouse

Gaschnig, Richard M.; Vervoort, J.D.; Lewis, R.S.; Tikoff, B.

2011-01-01

The Idaho batholith and spatially overlapping Challis intrusive province in the North American Cordillera have a history of magmatism spanning some 55 Myr. New isotopic data from the ???98 Ma to 54 Ma Idaho batholith and ???51 Ma to 43 Ma Challis intrusions, coupled with recent geochronological work, provide insights into the evolution of magmatism in the Idaho segment of the Cordillera. Nd and Hf isotopes show clear shifts towards more evolved compositions through the batholith's history and Pb isotopes define distinct fields correlative with the different age and compositionally defined suites of the batholith, whereas the Sr isotopic compositions of the various suites largely overlap. The subsequent Challis magmatism shows the full range of isotopic compositions seen in the batholith. These data suggest that the early suites of metaluminous magmatism (98-87 Ma) represent crust-mantle hybrids. Subsequent voluminous Atlanta peraluminous suite magmatism (83-67 Ma) results primarily from melting of different crustal components. This can be attributed to crustal thickening, resulting from either subduction processes or an outboard terrane collision. A later, smaller crustal melting episode, in the northern Idaho batholith, resulted in the Bitterroot peraluminous suite (66-54 Ma) and tapped different crustal sources. Subsequent Challis magmatism was derived from both crust and mantle sources and corresponds to extensional collapse of the over-thickened crust. ?? The Author 2011. Published by Oxford University Press. All rights reserved.

Pb-, Sr- and Nd-Isotopic systematics and chemical characteristics of cenozoic basalts, Eastern China

USGS Publications Warehouse

Peng, Z.C.; Zartman, R.E.; Futa, K.; Chen, D.G.

1986-01-01

Forty-eight Paleogene, Neogene and Quaternary basaltic rocks from northeastern and east-central China have been analyzed for major-element composition, selected trace-element contents, and Pb, Sr and Nd isotopic systematics. The study area lies entirely within the marginal Pacific tectonic domain. Proceeding east to west from the continental margin to the interior, the basalts reveal an isotopic transition in mantle source material and/or degree of crustal interaction. In the east, many of the rocks are found to merge both chemically and isotopically with those previously reported from the Japanese and Taiwan island-arc terrains. In the west, clear evidence exists for component(s) of Late Archean continental lithosphere to be present in some samples. A major crustal structure, the Tan-Lu fault, marks the approximate boundary between continental margin and interior isotopic behaviors. Although the isotopic signature of the western basalts has characteristics of lower-crustal contamination, a subcrustal lithosphere, i.e. an attached mantle keel, is probably more likely to be the major contributor of their continental "flavor". The transition from continental margin to interior is very pronounced for Pb isotopes, although Sr and Nd isotopes also combine to yield correlated patterns that deviate strikingly from the mid-ocean ridge basalt (MORB) and oceanic-island trends. The most distinctive chemical attribute of this continental lithosphere component is its diminished U Pb as reflected in the Pb isotopic composition when compared to sources of MORB, oceanic-island and island-arc volcanic rocks. Somewhat diminished Sm Nd and elevated Rb Sr, especially in comparison to the depleted asthenospheric mantle, are also apparent from the Nd- and Sr-isotopic ratios. ?? 1986.

Spatial evolution of Zn-Fe-Pb isotopes of sphalerite within a single ore body: A case study from the Dongshengmiao ore deposit, Inner Mongolia, China

NASA Astrophysics Data System (ADS)

Gao, Zhaofu; Zhu, Xiangkun; Sun, Jian; Luo, Zhaohua; Bao, Chuang; Tang, Chao; Ma, Jianxiong

2018-01-01

Analyses of sphalerite minerals from the characteristic brecciated Zn-Pb ores of the main ore body in the giant Dongshengmiao deposit have revealed variations in δ66Zn from 0.17 to 0.40‰ and in δ56Fe from -1.78 to -0.35‰. Further, the investigated pyrrhotite samples have iron that is isotopically similar to that of associated sphalerite minerals. The most distinctive pattern revealed by the zinc and iron isotope data is the lateral trend of increasing δ66Zn and δ56Fe values from southwest to northeast within the main ore body. The lead isotopic homogeneity of ore sulfides from the main ore body suggests that there is only one significant source for metal, thus precluding the mixing of multiple metal sources as the key factor controlling spatial variations of zinc and iron isotopes. The most likely control on spatial variations is Rayleigh fractionation during hydrothermal fluid flow, with lighter Zn and Fe isotopes preferentially incorporated into the earliest sulfides to precipitate from fluids. Precipitations of sphalerite and pyrrhotite have played vital roles in the Zn and Fe isotopic variations, respectively, of the ore-forming system. Accordingly, the larger isotopic variability for Fe than Zn within the same hydrothermal system perhaps resulted from a larger proportion of precipitation for pyrrhotite than for sphalerite. The lateral trend pattern revealed by the zinc and iron isotope data is consistent with the occurrence of a cystic-shaped breccia zone, which is characterized by marked elevation in Cu. The results further confirm that Zn and Fe isotopes can be used as a vectoring tool for mineral prospecting.

Stable carbon and nitrogen isotope composition of aquatic and terrestrial plants of the San Francisco Bay estuarine system

USGS Publications Warehouse

Cloern, J.E.; Canuel, E.A.; Harris, D.

2002-01-01

We report measurements of seasonal variability in the C-N stable isotope ratios of plants collected across the habitat mosaic of San Francisco Bay, its marshes, and its tributary river system. Analyses of 868 plant samples were binned into 10 groups (e.g., terrestrial riparian, freshwater phytoplankton, salt marsh) to determine whether C-N isotopes can be used as biomarkers for tracing the origins of organic matter in this river-marsh-estuary complex. Variability of ??13C and ??15N was high (???5-10???) within each plant group, and we identified three modes of variability: (1) between species and their microhabitats, (2) over annual cycles of plant growth and senescence, and (3) between living and decomposing biomass. These modes of within-group variability obscure any source-specific isotopic signatures, confounding the application of C-N isotopes for identifying the origins of organic matter. A second confounding factor was large dissimilarity between the ??13C-??15N of primary producers and the organic-matter pools in the seston and sediments. Both confounding factors impede the application of C-N isotopes to reveal the food supply to primary consumers in ecosystems supporting diverse autotrophs and where the isotopic composition of organic matter has been transformed and become distinct from that of its parent plant sources. Our results support the advice of others: variability of C-N stable isotopes within all organic-matter pools is high and must be considered in applications of these isotopes to trace trophic linkages from primary producers to primary consumers. Isotope-based approaches are perhaps most powerful when used to complement other tools, such as molecular biomarkers, bioassays, direct measures of production, and compilations of organic-matter budgets.

Quantifying the relative contribution of natural gas fugitive emissions to total methane emissions in Colorado, Utah, and Texas using mobile δ13CH4 analysis

NASA Astrophysics Data System (ADS)

Rella, C.; Crosson, E.; Petron, G.; Sweeney, C.; Karion, A.

2013-12-01

Fugitive emissions of methane into the atmosphere are a major concern facing the natural gas production industry. Because methane is more energy-rich than coal per kg of CO2 emitted into the atmosphere, it represents an attractive alternative to coal for electricity generation, provided that the fugitive emissions of methane are kept under control. A key step in assessing these emissions in a given region is partitioning the observed methane emissions between natural gas fugitive emissions and other sources of methane, such as from landfills or agricultural activities. One effective method for assessing the contribution of these different sources is stable isotope analysis, using the δ13CH4 signature to distinguish between natural gas and landfills or ruminants. We present measurements of mobile field δ13CH4 using a spectroscopic stable isotope analyzer based on cavity ringdown spectroscopy, in three intense natural gas producing regions of the United States: the Denver-Julesburg basin in Colorado, the Uintah basin in Utah, and the Barnett Shale in Texas. Mobile isotope measurements of individual sources and in the nocturnal boundary layer have been combined to establish the fraction of the observed methane emissions that can be attributed to natural gas activities. The fraction of total methane emissions in the Denver-Julesburg basin attributed to natural gas emissions is 78 +/- 13%. In the Uinta basin, which has no other significant sources of methane, the fraction is 96% +/- 15%. In addition, results from the Barnett shale are presented, which includes a major urban center (Dallas / Ft. Worth). Methane emissions in this region are spatially highly heterogeneous. Spatially-resolved isotope and concentration measurements are interpreted using a simple emissions model to arrive at an overall isotope ratio for the region. (left panel) Distribution of oil and gas well pads (yellow) and landfills (blue) in the Dallas / Ft. Worth area. Mobile nocturnal measurements of methane are shown in red, indicating a strong degree of source heterogeneity. (right panel) Histogram of individual isotopic source signatures, showing distinct signatures for landfills (red) and oil and gas sources (green).

The Oxidation State of Fe in Glasses from the Galapagos Archipelago: Variable Oxygen Fugacity as a Function of Mantle Source

NASA Astrophysics Data System (ADS)

Peterson, M. E.; Kelley, K. A.; Cottrell, E.; Saal, A. E.; Kurz, M. D.

2015-12-01

The oxidation state of the mantle plays an intrinsic role in the magmatic evolution of the Earth. Here we present new μ-XANES measurements of Fe3+/ΣFe ratios (a proxy for ƒO2) in a suite of submarine glasses from the Galapagos Archipelago. Using previously presented major, trace, and volatile elements and isotopic data for 4 groups of glass that come from distinct mantle sources (depleted upper mantle, 2 recycled, and a primitive mantle source) we show that Fe3+/ΣFe ratios vary both with the influence of shallow level processes and with variations in mantle source. Fe3+/ΣFe ratios increase with differentiation (i.e. decreasing MgO), but show a large variation at a given MgO. Progressive degassing of sulfur accompanies decreasing Fe3+/ΣFe ratios, while assimilation of hydrothermally altered crust (as indicated by increasing Sr/Sr*) is shown to increase Fe3+/ΣFe ratios. After taking these processes into account, there is still variability in the Fe3+/ΣFe ratios of the isotopically distinct sample suites studied, yielding a magmatic ƒO2 that ranges from ΔQFM = +0.16 to +0.74 (error < 0.5 log units) and showing that oxidation state varies as a function of mantle source composition in the Galapagos hotspot system. After correcting back to a common MgO content = 8.0 wt%, the trace element depleted group similar to MORB (ITD), and the group similar to Pinta (WD = high Th/La, Δ7/4, Δ8/4 ratios) show Fe3+/ΣFe ratios within the range of MORB (average ITD = 0.162 ± 0.003 and WD = 0.164 ± 0.006). Another trace element enriched group similar to Sierra Negra and Cerro Azul (ITE = enriched Sr and Pb isotopes) shows evidence of mixing between oxidized and reduced sources (ITE oxidized end-member = 0.177). This suggests that mantle sources in the Galapagos that are thought to contain recycled components (i.e., WD and ITE groups) have distinct oxidation states. The high 3He/4He Fernandina samples (HHe group) are shown to be the most oxidized (ave. 0.175 ± 0.006). With C/3He ratios an order of magnitude greater than MORB this suggests that the primitive mantle is a more carbonated and oxidized source than the depleted upper mantle.

A model for Cryogenian iron formation

NASA Astrophysics Data System (ADS)

Cox, Grant M.; Halverson, Galen P.; Poirier, André; Le Heron, Daniel; Strauss, Justin V.; Stevenson, Ross

2016-01-01

The Neoproterozoic Tatonduk (Alaska) and Holowilena (South Australia) iron formations share many characteristics including their broadly coeval (Sturtian) ages, intimate association with glaciogenic sediments, and mineralogy. We show that these shared characteristics extend to their neodymium (εNd) and iron isotope (δ56Fe) systematics. In both regions δ56Fe values display a distinct up-section trend to isotopically heavier values, while εNd values are primitive and similar to non-ferruginous mudstones within these successions. The δ56Fe profiles are consistent with oxidation of ferruginous waters during marine transgression, and the εNd values imply that much of this iron was sourced from the leaching of continental margin sediments largely derived from continental flood basalts. Rare earth element data indicate a secondary hydrothermal source for this iron.

Sedimentary denitrification: Isotope fractionation and its impact on water column nitrate isotopes

NASA Astrophysics Data System (ADS)

Dähnke, K.; Thamdrup, B.

2012-04-01

The global marine nitrogen cycle is constrained by one major source and two processes that act as nitrogen sinks: nitrogen fixation on the one side and denitrification or anammox on the other. These processes with their respective isotope effecst set the marine nitrate 15N-isotope value to a relatively constant average of 5 per mil. This value can be used to better assess the magnitude of these source and sink terms, but the underlying assumption at present is that sedimentary denitrification, a process responsible for approximately one third of global nitrogen removal, has little to no isotope effect on the water column. We tested this hypothesis in sediment incubations, measuring net denitrification and nitrogen and oxygen stable isotope fractionation in surface sediments from the coastal Baltic Sea (Boknis Eck, Northern Germany). We found tremendously high denitrification rates, and regardless of current paradigms assuming little fractionation during sediment denitrification, we measured fractionation factors of 19 per mil for nitrogen and 11 per mil for oxygen in nitrate. These results potentially challenge the current view of fractionation during sedimentary denitrification and imply that nitrogen budget calculation may need to consider this variability. Furthermore, the ratio of fractionation factors for nitrogen and oxygen is distinct from the 1 : 1 ratio otherwise found in marine systems, and suggests that isotope kinetics of sedimentary denitrification might be entirely different from water column denitrification. Acknowledgements: This work was funded by the German Research Foundation (DFG) and in parts by the Danish National Research Foundation.

Water Source and Isotope changes through the Deglaciation and Holocene

NASA Astrophysics Data System (ADS)

LeGrande, A. N.; Carlson, A. E.; Ullman, D. J.; Nusbaumer, J. M.

2017-12-01

The deglacial period saw radical shifts in climate across the globe. Water isotopologues provide some of the most wide-spread proxy archives of these climate changes. Here we present new analyses on a suite of 12 water isotope-enabled coupled atmosphere-ocean GCM simulations from GISS ModelE-R that span 24kya to the pre-industrial period. We show how millennial scale co-variability in water isotopes and climate (temperature, precipitation, humidity, and moist-static energy) is distinct from regional scale spatial slopes, consistent with proxy archives (e.g., Cuffey et al 1995). We supplement this set of simulations with a new ensemble of deglacial simulations that contain a complementary suite of tracers that determine moisture provenance changes through the deglaciation. We diagnose regions that have had significant changes in moisture provenance and compare this information against simulated changes in the water isotope changes.

Carbon, nitrogen, magnesium, silicon, and titanium isotopic compositions of single interstellar silicon carbide grains from the Murchison carbonaceous chondrite

NASA Technical Reports Server (NTRS)

Hoppe, Peter; Amari, Sachiko; Zinner, Ernst; Ireland, Trevor; Lewis, Roy S.

1994-01-01

Seven hundred and twenty SiC grains from the Murchison CM2 chondrite, ranging in size from 1 to 10 micrometers, were analyzed by ion microprobe mass spectrometry for their C-isotopic compositions. Subsets of the grains were also analyzed for N (450 grains), Si (183 grains), Mg (179 grains), and Ti (28 grains) isotopes. These results are compared with previous measurements on 41 larger SiC grains (up to 15 x 26 micrometers) from a different sample of Murchison analyzed by Virag et al. (1992) and Ireland, Zinner, & Amari (1991a). All grains of the present study are isotopically anomalous with C-12/C-13 ratios ranging from 0.022 to 28.4 x solar, N-14/N-15 ratios from 0.046 to 30 x solar, Si-29/Si-28 from 0.54 to 1.20 x solar, Si-30/Si-28 from 0.42 to 1.14 x solar, Ti-49/Ti-48 from 0.96 to 1.95 x solar, and Ti-50/Ti-48 from 0.94 to 1.39 x solar. Many grains have large Mg-26 excesses from the decay of Al-26 with inferred Al-26/Al-27 ratios ranging up to 0.61, or 12,200 x the ratio of 5 x 10(exp -5) inferred for the early solar system. Several groups can be distinguished among the SiC grains. Most of the grains have C-13 and N-14 excesses, and their Si isotopic compositions (mostly excesses in Si-29 and Si-30) plot close to a slope 1.34 line on a Delta Si-29/Si-28 versus Delta Si-30/Si-28 three-isotope plot. Grains with small C-12/C-13 ratios (less than 10) tend to have smaller or no N-14 excesses and high Al-26/Al-27 ratios (up to 0.01). Grains with C-12/C-13 greater than 150 fall into two groups: grains X have N-15 excesses and Si-29 and Si-30 deficits and the highest (0.1 to 0.6) Al-26/Al-27 ratios; grains Y have N-14 excesses and plot on a slope 0.35 line on a Si three-isotope plot. In addition, large SiC grains of the Virag et al. (1992) study fall into three-distinct clusters according to their C-, Si-, and Ti-isotopic compositions. The isotopic diversity of the grains and the clustering of their isotopic compositions imply distinct and multiple stellar sources. The C- and N-isotopic compositions of most grains are consistent with H-burning in the CNO cycle. These and s-process Kr, Xe, Ba, and Nd suggest asymptotic giant branch (AGB) or Wolf-Rayet stars as likely sources for the grains, but existing models of nucleosynthesis in these stellar sites fail to account in detail for all the observed isotopic compositions. Special problems are posed by grains with C-12/C-13 less than 10 and almost normal and heavy N-isotopic compositions. Also the Si- and Ti-isotopic compositions, with excesses in Si-29 and Si-30 relative to Si-28 and excesses in all Ti isotopes relative to Ti-48, do not precisely conform with the compositions predicted for slow neutron capture. Additional theoretical efforts are needed to achieve an understanding of the isotopic composition of the SiC grains and their stellar sources.

Contrasted crustal sources as defined by whole-rock and Sr-Nd-Pb isotope geochemistry of neoproterozoic early post-collisional granitic magmatism within the Southern Brazilian Shear Belt, Camboriú, Brazil

NASA Astrophysics Data System (ADS)

Florisbal, Luana Moreira; de Assis Janasi, Valdecir; de Fátima Bitencourt, Maria; Stoll Nardi, Lauro Valentim; Heaman, Larry M.

2012-11-01

The early phase of post-collisional granitic magmatism in the Camboriú region, south Brazil, is represented by the porphyritic biotite ± hornblende Rio Pequeno Granite (RPG; 630-620 Ma) and the younger (˜610 Ma), equigranular, biotite ± muscovite Serra dos Macacos Granite (SMG). The two granite types share some geochemical characteristics, but the more felsic SMG constitutes a distinctive group not related to RPG by simple fractionation processes, as indicated by its lower FeOt, TiO2, K2O/Na2O and higher Zr Al2O3, Na2O, Ba and Sr when compared to RPG of similar SiO2 range. Sr-Nd-Pb isotopes require different sources. The SMG derives from old crustal sources, possibly related to the Paleoproterozoic protoliths of the Camboriú Complex, as indicated by strongly negative ɛNdt (-23 to -24) and unradiogenic Pb (e.g., 206Pb/204Pb = 16.0-16.3; 207Pb/204Pb = 15.3-15.4) and confirmed by previous LA-MC-ICPMS data showing dominant zircon inheritance of Archean to Paleoproterozoic age. In contrast, the RPG shows less negative ɛNdt (-12 to -15) and a distinctive zircon inheritance pattern with no traces of post-1.6 Ga sources. This is indicative of younger sources whose significance in the regional context is still unclear; some contribution of mantle-derived magmas is indicated by coeval mafic dykes and may account for some of the geochemical and isotopic characteristics of the least differentiated varieties of the RPG. The transcurrent tectonics seems to have played an essential role in the generation of mantle-derived magmas despite their emplacement within a low-strain zone. It may have facilitated their interaction with crustal melts which seem to be to a large extent the products of reworking of Paleoproterozoic orthogneisses from the Camboriú Complex.

Chlorine isotopic composition of perchlorate in human urine as a means of distinguishing among exposure sources.

PubMed

Poghosyan, Armen; Morel-Espinosa, Maria; Valentin-Blasini, Liza; Blount, Benjamin C; Ferreccio, Catterina; Steinmaus, Craig M; Sturchio, Neil C

2016-01-01

Perchlorate (ClO4(-)) is a ubiquitous environmental contaminant with high human exposure potential. Natural perchlorate forms in the atmosphere from where it deposits onto the surface of Earth, whereas synthetic perchlorate is manufactured as an oxidant for industrial, aerospace, and military applications. Perchlorate exposure can potentially cause adverse health effects in humans by interfering with the production of thyroid hormones through competitively blocking iodide uptake. To control and reduce perchlorate exposure, the contributions of different sources of perchlorate exposure need to be quantified. Thus, we demonstrate a novel approach for determining the contribution of different perchlorate exposure sources by quantifying stable and radioactive chlorine isotopes of perchlorate extracted from composite urine samples from two distinct populations: one in Atlanta, USA and one in Taltal, Chile (Atacama region). Urinary perchlorate from the Atlanta region resembles indigenous natural perchlorate from the western USA (δ(37)Cl=+4.1±1.0‰; (36)Cl/Cl=1 811 (±136) × 10(-15)), and urinary perchlorate from the Taltal, Chile region is similar to natural perchlorate in nitrate salt deposits from the Atacama Desert of northern Chile (δ(37)Cl=-11.0±1.0‰; (36)Cl/Cl=254 (±40) × 10(-15)). Neither urinary perchlorate resembled the isotopic pattern found in synthetic perchlorate. These results indicate that natural perchlorate of regional provenance is the dominant exposure source for the two sample populations, and that chlorine isotope ratios provide a robust tool for elucidating perchlorate exposure pathways.

Two billion years of magmatism recorded from a single Mars meteorite ejection site

PubMed Central

Lapen, Thomas J.; Righter, Minako; Andreasen, Rasmus; Irving, Anthony J.; Satkoski, Aaron M.; Beard, Brian L.; Nishiizumi, Kunihiko; Jull, A. J. Timothy; Caffee, Marc W.

2017-01-01

The timing and nature of igneous activity recorded at a single Mars ejection site can be determined from the isotope analyses of Martian meteorites. Northwest Africa (NWA) 7635 has an Sm-Nd crystallization age of 2.403 ± 0.140 billion years, and isotope data indicate that it is derived from an incompatible trace element–depleted mantle source similar to that which produced a geochemically distinct group of 327- to 574-million-year-old “depleted” shergottites. Cosmogenic nuclide data demonstrate that NWA 7635 was ejected from Mars 1.1 million years ago (Ma), as were at least 10 other depleted shergottites. The shared ejection age is consistent with a common ejection site for these meteorites. The spatial association of 327- to 2403-Ma depleted shergottites indicates >2 billion years of magmatism from a long-lived and geochemically distinct volcanic center near the ejection site. PMID:28164153

Assessment of relative Ti, Ta, and Nb (TiTaN) enrichments in global ocean island basalts

NASA Astrophysics Data System (ADS)

Peters, B.; Day, J. M.

2013-12-01

The relative sensitivity of trace element concentrations to processes governing solid-melt and solid-fluid interactions has made them particularly useful for tracing the effects of partial melting, fractional crystallization, metasomatism and similar processes on the composition of a parental melt to a rock or mineral. Radiogenic and stable isotope compositions, in contrast, can provide information on the long-term history and provenance of magmas. Despite the distinct information derived from relative and absolute abundances of trace elements compared with isotopes, numerous studies of ocean island basalts (OIB) have attempted to use trace elements as diagnostic geochemical tracers to understand parental magma compositions. In particular, attempts have been made to correlate 'TiTaN' (Ti, Ta and Nb) anomalies to the He-Os isotopic compositions of OIB based on contributions from recycled eclogite, a theoretical high-TiTaN reservoir, and peridotite, a theoretical high-3He/4He reservoir (Jackson, et al., 2008 G-cubed). These authors have proposed that TiTaN anomalies can be used as independent indicators for recycled oceanic crust and lithospheric mantle in OIB sources, a distinction previously reserved for isotopic data. However, TiTaN anomalies appear uncorrelated to OIB mantle source composition for three reasons. First, a new geochemical compilation of global OIB shows a wide range of Ti (Ti/Ti* = 0.28 - 2.35), Ta (Ta/Ta* = 0.11 - 93.42) and Nb (Nb/Nb* = 0.13 - 17.79) anomalies that do not correlated with each other or noble gas systematics, indicating that: (i) TiTaN anomalies alone do not correspond to the primitive source traced by high-3He/4He or the solar neon component and (ii) Ti, Ta and Nb anomalies may each reflect distinct processes or origins, rather than tracing a single source or process together. Second, positive Ti anomalies can be generated by low-degree (1-10%), non-modal batch partial melting of garnet lherzolite at temperatures and pressures thought to be typical for OIB in many settings (T = 1075 - 1420 °C; P = 1 - 3.5 GPa). Furthermore, Ti, Ta and Nb anomalies can be theoretically created by subjecting the same low-degree partial melt to shallow level assimilation-fractional crystallization processes. If TiTaN anomalies are derived from this ubiquitous process, it presents a challenge to their origin from recycled or deep mantle parental materials. Finally, because clinopyroxene can contain large positive Ti anomalies (up to Ti/Ti* ≈ 1000), clinopyroxene accumulation can result in apparent high positive Ti/Ti* anomalies in ankaramites or other clinopyroxene-bearing rocks, when in reality, these Ti anomalies have been generated independent of primary source composition. Current evidence suggests that TiTaN anomalies do not directly reflect distinct source components in OIB lavas. Even if Ti, Ta and/or Nb enrichments are systematically present in high-3He/4He OIB parental materials, it is unlikely they are preserved due to magma processing at shallow depths.

Enrichments of the mantle sources beneath the Southern Volcanic Zone (Andes) by fluids and melts derived from abraded upper continental crust

NASA Astrophysics Data System (ADS)

Holm, Paul Martin; Søager, Nina; Dyhr, Charlotte Thorup; Nielsen, Mia Rohde

2014-05-01

Mafic basaltic-andesitic volcanic rocks from the Andean Southern Volcanic Zone (SVZ) exhibit a northward increase in crustal components in primitive arc magmas from the Central through the Transitional and Northern SVZ segments. New elemental and Sr-Nd-high-precision Pb isotope data from the Quaternary arc volcanic centres of Maipo (NSVZ) and Infernillo and Laguna del Maule (TSVZ) are argued to reflect mainly their mantle source and its melting. For the C-T-NSVZ, we identify two types of source enrichment: one, represented by Antuco in CSVZ, but also present northward along the arc, was dominated by fluids which enriched a pre-metasomatic South Atlantic depleted MORB mantle type asthenosphere. The second enrichment was by melts having the characteristics of upper continental crust (UCC), distinctly different from Chile trench sediments. We suggest that granitic rocks entered the source mantle by means of subduction erosion in response to the northward increasingly strong coupling of the converging plates. Both types of enrichment had the same Pb isotope composition in the TSVZ with no significant component derived from the subducting oceanic crust. Pb-Sr-Nd isotopes indicate a major crustal compositional change at the southern end of the NSVZ. Modelling suggests addition of around 2 % UCC for Infernillo and 5 % for Maipo.

Tracking nitrate sources in the Chaohu Lake, China, using the nitrogen and oxygen isotopic approach.

PubMed

Yu, Qibiao; Wang, Fang; Li, Xinyan; Yan, Weijin; Li, Yanqiang; Lv, Shucong

2018-05-07

The Chaohu Lake is highly polluted and suffers from severe eutrophication. Nitrate is a key form of nitrogen that can cause water quality degradation. In this study, hydrochemical and dual isotopic approaches were utilized to identify the seasonal variation of nitrate sources in the Chaohu Lake and its inflowing rivers. The average nitrate concentrations ([NO 3 - ]) of the lake and its inflowing rivers were 89.9 and 140.8 μmol L -1 , respectively. The isotopic values of δ 15 N-NO 3 - and δ 18 O-NO 3 - in the lake ranged from - 1.01 to + 16.67‰ and from - 4.39 to + 22.20‰, respectively. The two major rivers had distinct isotopic compositions, with average δ 15 N-NO 3 - values of + 17.52 and + 3.51‰, and average δ 18 O-NO 3 - values of + 2.71 and + 7.47‰ for the Nanfei River and Hangbu River, respectively. The results show that soil organic ammonium and urban wastewater discharge were the main sources of nitrate in the Chaohu Lake, and nitrate assimilation was an important process affected [NO 3 - ] and isotopic compositions, especially in the western Chaohu Lake. The elevated [NO 3 - ] and δ 15 N-NO 3 - values in the western Chaohu Lake indicate the high influence of human activities. Urban wastewater discharge was the primary nitrate source in the Nanfei River and soil organic ammonium was the main source in the Hangbu River. Although nitrate from direct atmospheric deposition was low, its strong flushing effect can substantially improve riverine [NO 3 - ] and nitrate loading from terrestrial ecosystem. The relatively high nitrate fluxes from the Hangbu River indicate that nitrogen loading from agricultural watershed is unneglectable in watershed nitrogen sources reduction strategies.

Identifying sources and processes controlling the sulphur cycle in the Canyon Creek watershed, Alberta, Canada.

PubMed

Nightingale, Michael; Mayer, Bernhard

2012-01-01

Sources and processes affecting the sulphur cycle in the Canyon Creek watershed in Alberta (Canada) were investigated. The catchment is important for water supply and recreational activities and is also a source of oil and natural gas. Water was collected from 10 locations along an 8 km stretch of Canyon Creek including three so-called sulphur pools, followed by the chemical and isotopic analyses on water and its major dissolved species. The δ(2)H and δ(18)O values of the water plotted near the regional meteoric water line, indicating a meteoric origin of the water and no contribution from deeper formation waters. Calcium, magnesium and bicarbonate were the dominant ions in the upstream portion of the watershed, whereas sulphate was the dominant anion in the water from the three sulphur pools. The isotopic composition of sulphate (δ(34)S and δ(18)O) revealed three major sulphate sources with distinct isotopic compositions throughout the catchment: (1) a combination of sulphate from soils and sulphide oxidation in the bedrock in the upper reaches of Canyon Creek; (2) sulphide oxidation in pyrite-rich shales in the lower reaches of Canyon Creek and (3) dissolution of Devonian anhydrite constituting the major sulphate source for the three sulphur pools in the central portion of the watershed. The presence of H(2)S in the sulphur pools with δ(34)S values ∼30 ‰ lower than those of sulphate further indicated the occurrence of bacterial (dissimilatory) sulphate reduction. This case study reveals that δ(34)S values of surface water systems can vary by more than 20 ‰ over short geographic distances and that isotope analyses are an effective tool to identify sources and processes that govern the sulphur cycle in watersheds.

The Importance of CO2 Utilizing Chemolithoautotrophic Microorganisms for Carbon Sequestration and Isotope Signatures of SOM in Tropical Rainforest Soils

NASA Astrophysics Data System (ADS)

Nowak, M. E.; Behrendt, T.; Quesada, B.; Yanez Serrano, A. M.; Trumbore, S.

2015-12-01

Soil organic matter (SOM) is a major compartment of the tropical carbon cycle with up to 26 % of global carbon stocks stored in tropical soils. Understanding factors and processes driving SOM dynamics under changing climate conditions is crucial for predicting the role of tropical forest ecosystems to act as a carbon sink or source. Soil microorganisms are major drivers of the belowground carbon cycle by releasing CO2 by soil respiration but also by stabilizing and storing SOM, as indicated by recent research. Our investigations focus on chemolithoautotrophic microorganisms, a group that relies on CO2 as their carbon source. Chemolithoautotrophic microorganisms have been shown to be highly abundant in soils, whereas their role in SOM sequestration is still poorly understood. In tropical soils, the activity of chemolithoautotropic microbes might be important for generating and stabilizing carbon, especially in the deeper soil, which is rich in CO2 and reduced energy sources like Fe2+. They further might impact carbon isotope signatures (13C and 14C) of SOM, because of enzymatic fractionation during carboxylation and the use of carbon, which has a distinct isotopic composition than other carbon sources at the same depth. In order to study the activity of chemolithoautotropic microbes and their importance for SOM, we conducted isotope and isotope-labelling studies, gas measurements as well as molecular analyses at soils from the Atto site from 0 to 1 meter depth. These soils are classified as Ferralsols and Alisols and represent the most abundant soil types in the Amazon. With this we will be able to gain knowledge about the function and identity of an important group of microorganisms and their contribution to crucial biogeochemical cycles in the world`s most important ecosystem.

Phantom Archean crust in Mangaia hotspot lavas and the meaning of heterogeneous mantle

NASA Astrophysics Data System (ADS)

Herzberg, C.; Cabral, R. A.; Jackson, M. G.; Vidito, C.; Day, J. M. D.; Hauri, E. H.

2014-06-01

Lavas from Mangaia in the Cook-Austral island chain, Polynesia, define an HIMU (or high μ, where μ=U238/Pb204) global isotopic end-member among ocean island basalts (OIB) with the highest 206,207,208Pb/204Pb. This geochemical signature is interpreted to reflect a recycled oceanic crust component in the mantle source. Mass independently fractionated (MIF) sulfur isotopes indicate that Mangaia lavas sampled recycled Archean material that was once at the Earth's surface, likely hydrothermally-modified oceanic crust. Recent models have proposed that crust that is subducted and then returned to the surface in a mantle plume is expected to transform to pyroxenite/eclogite during transit through the mantle. Here we examine this hypothesis for Mangaia using high-precision electron microprobe analysis on olivine phenocrysts. Contrary to expectations of a crustal component and, hence pyroxenite, results show a mixed peridotite and pyroxenite source, with peridotite dominating. If the isotopic compositions were inherited from subduction of recycled oceanic crust, our work shows that this source has phantom-like properties in that it can have its lithological identity destroyed while its isotope ratios are preserved. This may occur by partial melting of the pyroxenite and injection of its silicic melts into the surrounding mantle peridotite, yielding a refertilized peridotite. Evidence from one sample reveals that not all pyroxenite in the melting region was destroyed. Identification of source lithology using olivine phenocryst chemistry can be further compromised by magma chamber fractional crystallization, recharge, and mixing. We conclude that the commonly used terms mantle “heterogeneities” and “streaks” are ambiguous, and distinction should be made of its lithological and isotopic properties.

Development of procedure for measurement of Pb isotope ratios in seawater by application of seaFAST sample pre-treatment system and Sector Field Inductively Coupled Plasma Mass Spectrometry

NASA Astrophysics Data System (ADS)

Vassileva, Emilia; Wysocka, Irena

2016-12-01

Anthropogenic Pb in the oceans, derived from high-temperature industrial processes, fuel combustion and incineration can have an isotopic signature distinct from naturally occurring Pb, supplied by rock weathering. To identify the different pollution sources accurately and to quantify their relative contributions, Pb isotope ratios are widely used. Due to the high salt content (approximately 3.5% of total dissolved solids) and very low levels of Pb (typically from 1 to 100 ng L- 1) in seawater the determination of Pb isotope ratios requires preliminary matrix separation and analyte preconcentration. An analytical protocol for the measurements of Pb isotope ratios in seawater combining seaFAST sample pre-treatment system and Sector Field Inductively Coupled Plasma Mass Spectrometry (SF ICP-MS) was developed. The application of seaFAST system was advantageous, because of its completely closed working cycle and small volumes of chemicals introduced in pre-treatment step, resulting in very low detection limits and procedural blanks. The preconcentration/matrix separation step was also of crucial importance for minimizing the isobaric and matrix interferences, coming from the seawater. In order to differentiate between anthropogenic and natural Pb sources, particular attention was paid to the determination of 204Pb isotope because of its implication in some geological interpretations. The validation of the analytical procedure was effectuated according to the recommendations of the ISO/IEC 17025 standard. The method was validated by processing the common Pb isotope reference material NIST SRM 981. All major sources of uncertainty were identified and propagated together following the ISO/GUM guidelines. The estimation of the total uncertainty associated to each measurement result was fundamental tool for sorting the main sources of possible biases. The developed analytical procedure was applied to the coastal and open seawater samples, collected in different regions of the world and revealed that the procedure is applicable for the measurement of Pb isotope ratios in seawater with combined uncertainty adequate to discuss the origin of Pb pollution in the ocean.

Strontium isotopes delineate fine-scale natal origins and migration histories of Pacific salmon

USGS Publications Warehouse

Brennan, Sean R.; Zimmerman, Christian E.; Fernandez, Diego P.; Cerling, Thure E.; McPhee, Megan V.; Wooller, Matthew J.

2015-01-01

Highly migratory organisms present major challenges to conservation efforts. This is especially true for exploited anadromous fish species, which exhibit long-range dispersals from natal sites, complex population structures, and extensive mixing of distinct populations during exploitation. By tracing the migratory histories of individual Chinook salmon caught in fisheries using strontium isotopes, we determined the relative production of natal habitats at fine spatial scales and different life histories. Although strontium isotopes have been widely used in provenance research, we present a new robust framework to simultaneously assess natal sources and migrations of individuals within fishery harvests through time. Our results pave the way for investigating how fine-scale habitat production and life histories of salmon respond to perturbations—providing crucial insights for conservation.

Rhenium-osmium and samarium-neodymium isotopic systematics of the Stillwater complex

NASA Technical Reports Server (NTRS)

Lambert, David D.; Shirey, Steven B.; Carlson, Richard W.; Morgan, John W.; Walker, Richard J.

1989-01-01

The role of magma mixing in the formation of strategic platinum-group element ore deposits is examined using isotopic data from the Stillwater Complex, Montana. Nd and Os isotopic data show that the intrusion formed from at least two distinct magmas: ultramafic (U-type) affinity magmas and anorthositic (A-type) affinity magmas. The U-type magmas formed from a lithospheric mantle source containing recycled crustal materials and the A-type magmas originated either by crustal contamination of basaltic magmas or by partial melting of basalt in the lower crust. The results also suggest that the platinum-group element ore deposits were derived from A-type magmas which were injected into the U-type magma chamber at several stages during the development of the ultramafic series.

Biogeochemistry Science and Education Part One: Using Non-Traditional Stable Isotopes as Environmental Tracers Part Two: Identifying and Measuring Undergraduate Misconceptions in Biogeochemistry

NASA Astrophysics Data System (ADS)

Mead, Chris

This dissertation is presented in two sections. First, I explore two methods of using stable isotope analysis to trace environmental and biogeochemical processes. Second, I present two related studies investigating student understanding of the biogeochemical concepts that underlie part one. Fe and Hg are each biogeochemically important elements in their own way. Fe is a critical nutrient for phytoplankton, while Hg is detrimental to nearly all forms of life. Fe is often a limiting factor in marine phytoplankton growth. The largest source, by mass, of Fe to the open ocean is windblown mineral dust, but other more soluble sources are more bioavailable. To look for evidence of these non-soil dust sources of Fe to the open ocean, I measured the isotopic composition of aerosol samples collected on Bermuda. I found clear evidence in the fine size fraction of a non-soil dust Fe source, which I conclude is most likely from biomass burning. Widespread adoption of compact fluorescent lamps (CFL) has increased their importance as a source of environmental Hg. Isotope analysis would be a useful tool in quantifying this impact if the isotopic composition of Hg from CFL were known. My measurements show that CFL-Hg is isotopically fractionated, in a unique pattern, during normal operation. This fractionation is large and has a distinctive, mass-independent signature, such that CFL Hg can be uniquely identified from other sources. Misconceptions research in geology has been a very active area of research, but student thinking regarding the related field of biogeochemistry has not yet been studied in detail. From interviews with 40 undergraduates, I identified over 150 specific misconceptions. I also designed a multiple-choice survey (concept inventory) to measure understanding of these same biogeochemistry concepts. I present statistical evidence, based on the Rasch model, for the reliability and validity of this instrument. This instrument will allow teachers and researchers to easily quantify learning outcomes in biogeochemistry and will complement existing concept inventories in geology, chemistry, and biology.

Isotopic data for Late Cretaceous intrusions and associated altered and mineralized rocks in the Big Belt Mountains, Montana

USGS Publications Warehouse

du Bray, Edward A.; Unruh, Daniel M.; Hofstra, Albert H.

2017-03-07

The quartz monzodiorite of Mount Edith and the concentrically zoned intrusive suite of Boulder Baldy constitute the principal Late Cretaceous igneous intrusions hosted by Mesoproterozoic sedimentary rocks of the Newland Formation in the Big Belt Mountains, Montana. These calc-alkaline plutonic masses are manifestations of subduction-related magmatism that prevailed along the western edge of North America during the Cretaceous. Radiogenic isotope data for neodymium, strontium, and lead indicate that the petrogenesis of the associated magmas involved a combination of (1) sources that were compositionally heterogeneous at the scale of the geographically restricted intrusive rocks in the Big Belt Mountains and (2) variable contamination by crustal assimilants also having diverse isotopic compositions. Altered and mineralized rocks temporally, spatially, and genetically related to these intrusions manifest at least two isotopically distinct mineralizing events, both of which involve major inputs from spatially associated Late Cretaceous igneous rocks. Alteration and mineralization of rock associated with the intrusive suite of Boulder Baldy requires a component characterized by significantly more radiogenic strontium than that characteristic of the associated igneous rocks. However, the source of such a component was not identified in the Big Belt Mountains. Similarly, altered and mineralized rocks associated with the quartz monzodiorite of Mount Edith include a component characterized by significantly more radiogenic strontium and lead, particularly as defined by 207Pb/204Pb values. The source of this component appears to be fluids that equilibrated with proximal Newland Formation rocks. Oxygen isotope data for rocks of the intrusive suite of Boulder Baldy are similar to those of subduction-related magmatism that include mantle-derived components; oxygen isotope data for altered and mineralized equivalents are slightly lighter.

Distinct Chlorine Isotopic Reservoirs on Mars: Implications for Character, Extent and Relative Timing of Crustal Interaction with Mantle-Derived Magmas, Evolution of the Martian Atmosphere, and the Building Blocks of an Early Mars

NASA Technical Reports Server (NTRS)

Shearer, C. K.; Messenger, S.; Sharp, Z. D.; Burger, P. V.; Nguyen, N.; McCubbin, F. M.

2017-01-01

The style, magnitude, timing, and mixing components involved in the interaction between mantle derived Martian magmas and Martian crust have long been a point of debate. Understanding this process is fundamental to deciphering the composition of the Martian crust and its interaction with the atmosphere, the compositional diversity and oxygen fugacity variations in the Martian mantle, the bulk composition of Mars and the materials from which it accreted, and the noble gas composition of Mars and the Sun. Recent studies of the chlorine isotopic composition of Martian meteorites imply that although the variation in delta (sup 37) Cl is limited (total range of approximately14 per mille), there appears to be distinct signatures for the Martian crust and mantle. However, there are potential issues with this interpretation. New Cl isotope data from the SAM (Sample Analysis at Mars) instrument on the Mars Science Lab indicate a very wide range of Cl isotopic compositions on the Martian surface. Recent measurements by [10] duplicated the results of [7,8], but placed them within the context of SAM surface data. In addition, Martian meteorite Chassigny contains trapped noble gases with isotopic ratios similar to solar abundance, and has long been considered a pristine, mantle derived sample. However, previous studies of apatite in Chassigny indicate that crustal fluids have interacted with regions interstitial to the cumulus olivine. The initial Cl isotope measurements of apatite in Chassigny suggest an addition of crustal component to this lithology, apparently contradicting the rare gas data. Here, we examine the Cl isotopic composition of multiple generations and textures of apatite in Chassigny to extricate the crustal and mantle components in this meteorite and to reveal the style and timing of the addition of crustal components to mantle-derived magmas. These data reveal distinct Martian Cl sources whose signatures have their origins linked to both the early Solar System and the evolving Martian atmosphere.

Quantitative sediment source attribution with compound-specific isotope analysis in a C3 plant-dominated catchment (central Switzerland)

NASA Astrophysics Data System (ADS)

Alewell, Christine; Birkholz, Axel; Meusburger, Katrin; Schindler Wildhaber, Yael; Mabit, Lionel

2016-03-01

As sediment loads impact freshwater systems and infrastructure, their origin in complex landscape systems is of crucial importance for sustainable management of agricultural catchments. We differentiated the sediment source contribution to a lowland river in central Switzerland by using compound-specific isotope analysis (CSIA). We found a clear distinction of sediment sources originating from forest and agricultural land use. Our results demonstrate that it is possible to reduce the uncertainty of sediment source attribution in: (i) using compound content (in our case, long-chain fatty acids; FAs) rather than soil organic matter content to transfer δ13C signal of FAs to soil contribution and (ii) restricting the investigation to the long-chain FAs (> C22 : 0) not to introduce errors due to aquatic contributions from algae and microorganisms. Results showed unambiguously that during base flow, agricultural land contributed up to 65 % of the suspended sediments, while forest was the dominant sediment source during high flow. This indicates that connectivity of sediment source areas within the river changes between base and high flow conditions. Uncertainty, which might occur in complex, large-scale studies due to undetected source attribution and/or CSSI signature degradation, is low because of limited data complexity in our study (i.e., two-three sources and two tracers). Our findings are the first published results highlighting (i) significant differences in compound-specific stable isotope (CSSI) signature of sediment sources from land uses dominated by C3 plant cultivation and (ii) the use of these differences to quantify sediment contribution to a small river.

Recent and Late Holocene Alaskan Lake Changes Identified from Water Isotopes

NASA Astrophysics Data System (ADS)

Anderson, L.; Birks, S. J.; Rover, J.; Guldager, N.

2014-12-01

To identify the existence and cause of recent lake area changes in the Yukon Flats, a region of discontinuous permafrost in north central Alaska, we evaluate lake water isotope compositions with remotely sensed imagery and hydroclimatic parameters. Estimates of the ratio of water lost by evaporation to that gained by inflow (E/I) were derived from an isotope-based water balance model. The isotope labels are also used to identify the dominant sources for lakes such as rainfall and snowfall, groundwater, rivers, or thawed permafrost. These parameters are then used in conjunction with climatic data and remotely sensed imagery to identify the patterns and causes of recent lake area changes and for evaluation with lake sediment oxygen isotope records of late Holocene lake water isotope variations. Lake water isotope samples from 83 lakes were acquired in July, August or September between 2007 and 2010 by fixed wing aircraft. An additional set of smaller lakes (n = 33) was sampled by helicopter in September 2009. In July 2011 59 lakes were sampled on foot within five distinct 11.2-km2 areas. River water data used here are previously collected during the months of June through October between 2006 and 2008. Isotope compositions indicate that mixtures of precipitation, river water, and groundwater source ~95% of the studied lakes. The remaining minority are more dominantly sourced by snowmelt and/or permafrost thaw. Isotope-based water balance estimates indicate 58% of lakes lose more than half of inflow by evaporation. For 26% of the lakes studied, evaporative losses exceeded supply. Surface area trend analysis indicates that most lakes were near their maximum extent in the early 1980s during a relatively cool and wet period. Subsequent reductions can be explained by moisture deficits and greater evaporation. Comparison with late Holocene isotope values and trends indicates recent changes are within the range of late Holocene variability. The records indicate a drier and warmer than present climate prior to 4000 years ago, whereas it was wetter and cooler between 4000 and 2000 years ago. These findings indicate that attempts to project future high-latitude lake change will benefit from considering the effects of decade to multi-decadal scale hydroclimatic variations.

Concentrations and isotope ratios of mercury in sediments from shelf and continental slope at Campos Basin near Rio de Janeiro, Brazil.

PubMed

Araujo, Beatriz Ferreira; Hintelmann, Holger; Dimock, Brian; Almeida, Marcelo Gomes; Rezende, Carlos Eduardo

2017-07-01

Mercury (Hg) may originate from both anthropogenic and natural sources. The measurement of spatial and temporal variations of Hg isotope ratios in sediments may enable source identification and tracking of environmental processes. In this study we establish the distribution of mercury concentrations and mercury isotope ratios in surface sediments of three transects along the continental shelf and slope in Campos Basin-RJ-Brazil. The shelf showed on average lower total Hg concentrations (9.2 ± 5.3 ng g -1 ) than the slope (24.6 ± 8.8 ng g -1 ). MMHg average concentrations of shelf 0.15 ± 0.12 ng g -1 and slope 0.13 ± 0.06 ng g -1 were not significantly different. Distinct differences in Hg isotope ratio signatures were observed, suggesting that the two regions were impacted by different sources of Hg. The shelf showed more negative δ 202 Hg and Δ 199 Hg values ranging from -0.59 to -2.19‰ and from -0.76 to 0.08‰, respectively. In contrast, the slope exhibited δ 202 Hg values from -0.29 to -1.82‰ and Δ 199 Hg values from -0.23 to 0.09‰. Mercury found on the shelf, especially along the "D" and "I" transects, is depleted in heavy isotopes resulting in more negative δ 202 Hg compared to the slope. Isotope ratios observed in the "D" and "I" shelf region are similar to Hg ratios commonly associated with plants and vegetation and very comparable to those detected in the estuary and adjoining mangrove forest, which suggests that Hg exported from rivers may be the dominating source of Hg in near coastal regions along the northern part of the shelf. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pb, Sr, and Nd isotopic compositions of a suite of Late Archean, igneous rocks, eastern Beartooth Mountains: implications for crust-mantle evolution

USGS Publications Warehouse

Wooden, J.L.; Mueller, P.A.

1988-01-01

A series of compositionally diverse, Late Archean rocks (2.74-2.79 Ga old) from the eastern Beartooth Mountains, Montana and Wyoming, U.S.A., have the same initial Pb, Sr, and Nd isotopic ratios. Lead and Sr initial ratios are higher and Nd initial ratios lower than would be expected for rocks derived from model mantle sources and strongly indicate the involvement of an older crustal reservoir in the genesis of these rocks. Crustal contamination during emplacement can be ruled out for a variety of reasons. Instead a model involving subduction of continental detritus and contamination of the overlying mantle as is often proposed for modern subduction environments is preferred. This contaminated mantle would have all the isotopic characteristics of mantle enriched by internal mantle metasomatism but would require no long-term growth or changes in parent to daughter element ratios. This contaminated mantle would make a good source for some of the Cenozoic mafic volcanics of the Columbia River, Snake River Plain, and Yellowstone volcanic fields that are proposed to come from ancient, enriched lithospheric mantle. The isotopic characteristics of the 2.70 Ga old Stillwater Complex are a perfect match for the proposed contaminated mantle which provides an alternative to crustal contamination during emplacement. The Pb isotopic characteristics of the Late Archean rocks of the eastern Beartooth Mountains are similar to those of other Late Archean rocks of the Wyoming Province and suggest that Early Archean, upper crustal rocks were common in this terrane. The isotopic signatures of Late Archean rocks in the Wyoming Province are distinctive from those of other Archean cratons in North America which are dominated by a MORB-like, Archean mantle source (Superior Province) and/or a long-term depleted crustal source (Greenland). ?? 1988.

Deglacial Dust Provenance Changes in the Eastern Equatorial Pacific and Implications for ITCZ Movement

NASA Astrophysics Data System (ADS)

Xie, R.; Marcantonio, F.

2009-12-01

The provenance of the eolian dust component of deep-sea sediments has the potential to offer insights into changes in past atmospheric circulation patterns. Measuring temporal changes in dust provenance can shed more light on changes in the position of the Intertropical Convergence Zone (ITCZ), a region in which dust is removed from the upper troposphere by deep convection and scavenged by precipitation. The ITCZ should, therefore, act as a barrier separating wind-blown northern versus southern sources. Perhaps the best way to trace for provenance of dust sources is through the measurement of radiogenic isotope ratios. Here, we have analyzed Nd, Sr, and Pb isotope ratios in the detrital components extracted from deep-sea sediments in the eastern equatorial Pacific (EEP) along a meridional transect at 110W from 3S to 7N (ODP Leg 138, Sites 848 - 853). At each site, the sediments ranged in age from 0 to 25 ka. Detrital component extraction involved the chemical removal of the biogenic and authigenic sedimentary fractions. Preliminary detrital Nd isotope ratios show a range of 2.4 ɛNd units (from -5.7 to -3.3). There are distinct latitudinal trends in the ɛNd values, with more radiogenic values further south and less radiogenic values further north. This distinction holds true for both Holocene and glacial time. The difference in Nd isotope ratios at any one site between Holocene and glacial is smaller for the sites furthest North. The greatest Holocene-glacial differences in ɛNd occur at sites south of 3N, suggesting a distinct detrital component boundary at this latitude. The sites furthest north (7N and 5.29N) show the greatest variability in detrital 87Sr/86Sr isotope ratios, while sites furthest south (equator and 1.5N) show negligible variability. The detrital component of sediment at Site 851 (2.77N) has a Sr isotope variability that is intermediate between the northern and southern values, again suggesting a detrital boundary of some sort. We interpreted these preliminary results to suggest that the ITCZ position was displaced toward the south, with a paleo-position located between Site 851 (2.77N) and Site 852 (5.29N), from its average current location, which is approximately 7N. This supports one hypothesis put forward by McGee et al. [1], based on changes in dust flux for the same transect, that the ITCZ was displaced toward the south during the last glacial period. [1] McGee et al., 2007, EPSL 257, 215-230 .

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.

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.

Lead isotope compositions of Late Cretaceous and early Tertiary igneous rocks and sulfide minerals in Arizona: Implications for the sources of plutons and metals in porphyry copper deposits

USGS Publications Warehouse

Bouse, R.M.; Ruiz, J.; Titley, S.R.; Tosdal, R.M.; Wooden, J.L.

1999-01-01

Porphyry copper deposits in Arizona are genetically associated with Late Cretaceous and early Tertiary igneous complexes that consist of older intermediate volcanic rocks and younger intermediate to felsic intrusions. The igneous complexes and their associated porphyry copper deposits were emplaced into an Early Proterozoic basement characterized by different rocks, geologic histories, and isotopic compositions. Lead isotope compositions of the Proterozoic basement rocks define, from northwest to southeast, the Mojave, central Arizona, and southeastern Arizona provinces. Porphyry copper deposits are present in each Pb isotope province. Lead isotope compositions of Late Cretaceous and early Tertiary plutons, together with those of sulfide minerals in porphyry copper deposits and of Proterozoic country rocks, place important constraints on genesis of the magmatic suites and the porphyry copper deposits themselves. The range of age-corrected Pb isotope compositions of plutons in 12 Late Cretaceous and early Tertiary igneous complexes is 206Pb/204Pb = 17.34 to 22.66, 207Pb/204Pb = 15.43 to 15.96, and 208Pb/204Pb = 37.19 to 40.33. These Pb isotope compositions and calculated model Th/U are similar to those of the Proterozoic rocks in which the plutons were emplaced, thereby indicating that Pb in the younger rocks and ore deposits was inherited from the basement rocks and their sources. No Pb isotope differences distinguish Late Cretaceous and early Tertiary igneous complexes that contain large economic porphyry copper deposits from less rich or smaller deposits that have not been considered economic for mining. Lead isotope compositions of Late Cretaceous and early Tertiary plutons and sulfide minerals from 30 metallic mineral districts, furthermore, require that the southeastern Arizona Pb province be divided into two subprovinces. The northern subprovince has generally lower 206Pb/204Pb and higher model Th/U, and the southern subprovince has higher 206Pb/204Pb and lower model Th/U. These Pb isotope differences are inferred to result from differences in their respective post-1.7 Ga magmatic histories. Throughout Arizona, Pb isotope compositions of Late Cretaceous and early Tertiary plutons and associated sulfide minerals are distinct from those of Jurassic plutons and also middle Tertiary igneous rocks and sulfide minerals. These differences most likely reflect changes in tectonic setting and magmatic sources. Within Late Cretaceous and early Tertiary igneous complexes that host economic porphyry copper deposits, there is commonly a decrease in Pb isotope composition from older to younger plutons. This decrease in Pb isotope values with time suggests an increasing involvement of crust with lower U/Pb than average crust in the source(s) of Late Cretaceous and early Tertiary magmas. Lead isotope compositions of the youngest porphyries in the igneous complexes are similar to those in most sulfide minerals within the associated porphyry copper deposit. This Pb isotope similarity argues for a genetic link between them. However, not all Pb in the sulfide minerals in porphyry copper deposits is magmatically derived. Some sulfide minerals, particularly those that are late stage, or distal to the main orebody, or in Proterozoic or Paleozoic rocks, have elevated Pb isotope compositions displaced toward the gross average Pb isotope composition of the local country rocks. The more radiogenic isotopic compositions argue for a contribution of Pb from those rocks at the site of ore deposition. Combining the Pb isotope data with available geochemical, isotopic, and petrologic data suggests derivation of the young porphyry copper-related plutons, most of their Pb, and other metals from a hybridized lower continental crustal source. Because of the likely involvement of subduction-related mantle-derived basaltic magma in the hybridized lower crustal source, an indiscernible mantle contribution is probable in the porphyry magmas. Clearly, in addition

Isotopically distinct reservoirs in the solar nebula: Isotope anomalies in Vigarano meteorite inclusions

NASA Technical Reports Server (NTRS)

Loss, R. D.; Lugmair, G. W.; Davis, A. M.; Macpherson, G. J.

1994-01-01

The isotopic compositions of Mg, Ca, Ti, Cr, Zn, Sr, Ba, Nd, and Sm were measured in four relatively unaltered refractory inclusions from the Vigarano carbonaceous chondrite meteorite. Three of the inclusions (USNM 1623-2, 1623-3, and 1623-8) show similar Mg, Ca, Ti, and Cr isotopic compositions to those found in most inclusions in the Allende carbonaceous chondrite. This indicates that these Vigarano inclusions sampled the same isotopic reservoirs as the majority of the Allende inclusions that isotope signatures in the latter were not significantly modified by the secondary alteration that permeates most Allende inclusions. In contrast, inclusion 1623-5 has large deficits in Mg-26, Ca-48, and Ti-50 and small but distinct Cr-54, Zn-66, Sr-84, Ba-135, Ba-137, and Sm-144 anomalies. The magnitudes of these unusual anomalies in the refractory elements are within analytical uncertainty of those found in the Allende 'FUN" inclusion C1, yet 1623-5 has a very different bulk chemical composition from C1. The fact that 1623-5 and C1 have identical isotopic anomalies yet have significantly distinct major and trace element contents provide convincing evidence for the presence of isotopically distinct reservoirs in the early solar system.

Isotopic signatures of anthropogenic CH4 sources in Alberta, Canada

NASA Astrophysics Data System (ADS)

Lopez, M.; Sherwood, O. A.; Dlugokencky, E. J.; Kessler, R.; Giroux, L.; Worthy, D. E. J.

2017-09-01

A mobile system was used for continuous ambient measurements of stable CH4 isotopes (12CH4 and 13CH4) and ethane (C2H6). This system was used during a winter mobile campaign to investigate the CH4 isotopic signatures and the C2H6/CH4 ratios of the main anthropogenic sources of CH4 in the Canadian province of Alberta. Individual signatures were derived from δ13CH4 and C2H6 measurements in plumes arriving from identifiable single sources. Methane emissions from beef cattle feedlots (n = 2) and landfill (n = 1) had δ13CH4 signatures of -66.7 ± 2.4‰ and -55.3 ± 0.2‰, respectively. The CH4 emissions associated with the oil or gas industry had distinct δ13CH4 signatures, depending on the formation process. Emissions from oil storage tanks (n = 5) had δ13CH4 signatures ranging from -54.9 ± 2.9‰ to -60.6 ± 0.6‰ and non-detectable C2H6, characteristic of secondary microbial methanogenesis in oil-bearing reservoirs. In contrast, CH4 emissions associated with natural gas facilities (n = 8) had δ13CH4 signatures ranging from -41.7 ± 0.7‰ to -49.7 ± 0.7‰ and C2H6/CH4 molar ratios of 0.10 for raw natural gas to 0.04 for processed/refined natural gas, consistent with thermogenic origins. These isotopic signatures and C2H6/CH4 ratios have been used for source discrimination in the weekly atmospheric measurements of stable CH4 isotopes over a two-month winter period at the Lac La Biche (LLB) measurement station, located in Alberta, approximately 200 km northeast of Edmonton. The average signature of -59.5 ± 1.4‰ observed at LLB is likely associated with transport of air after passing over oil industry sources located south of the station.

Carbon isotope systematics of Turrialba volcano, Costa Rica, using a portable cavity ring-down spectrometer

NASA Astrophysics Data System (ADS)

Malowany, K. S.; Stix, J.; de Moor, J. M.; Chu, K.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

2017-07-01

Over the past two decades, activity at Turrialba volcano, Costa Rica, has shifted from hydrothermal to increasingly magmatic in character, with enhanced degassing and eruption potential. We have conducted a survey of the δ13C signatures of gases at Turrialba using a portable field-based CRDS with comparison to standard IRMS techniques. Our δ13C results of the volcanic plume, high-temperature vents, and soil gases reveal isotopic heterogeneity in the CO2 gas composition at Turrialba prior to its recent phase of eruptive activity. The isotopic value of the regional fault system, Falla Ariete (-3.4 ± 0.1‰), is in distinct contrast with the Central crater gases (-3.9 ± 0.1‰) and the 2012 high-temperature vent (-4.4 ± 0.2‰), an indication that spatial variability in δ13C may be linked to hydrothermal transport of volcanic gases, heterogeneities in the source composition, or magmatic degassing. Isotopic values of CO2 samples collected in the plume vary from δ13C of -5.2 to -10.0‰, indicative of mixing between atmospheric CO2 (-9.2 ± 0.1‰), and a volcanic source. We compare the Keeling method to a traditional mixing model (hyperbolic mixing curve) to estimate the volcanic source composition at Turrialba from the plume measurements. The predicted source compositions from the Keeling and hyperbolic methods (-3.0 ± 0.5‰ and -3.9 ± 0.4‰, respectively) illustrate two potential interpretations of the volcanic source at Turrialba. As of the 29 October 2014, Turrialba has entered a new eruptive period, and continued monitoring of the summit gases for δ13C should be conducted to better understand the dominant processes controlling δ13C fractionation at Turrialba.

Chlorine Isotopic Composition of Perchlorate in Human Urine as a Means of Distinguishing Among Natural and Synthetic Exposure Sources

PubMed Central

Poghosyan, Armen; Morel-Espinosa, Maria; Valentín-Blasini, Liza; Blount, Benjamin C.; Ferreccio, Catterina; Steinmaus, Craig M.; Sturchio, Neil C.

2015-01-01

Perchlorate (ClO4−) is a ubiquitous environmental contaminant with high human exposure potential; it has both natural and man-made sources in the environment. Natural perchlorate forms in the atmosphere from where it deposits onto the surface of Earth, whereas synthetic perchlorate is manufactured as an oxidant for industrial, aerospace, and military applications. Perchlorate exposure can potentially cause adverse health effects in humans by interfering with the production of thyroid hormones through competitively blocking iodide uptake. To control and reduce perchlorate exposure, the contributions of different sources of perchlorate exposure need to be quantified. Thus, we demonstrate a novel approach for determining the contribution of different perchlorate exposure sources by quantifying stable and radioactive chlorine isotopes of perchlorate extracted from composite urine samples from two distinct populations: one in Atlanta, USA and one in Taltal, Chile (Atacama region). Urinary perchlorate from the Atlanta region resembles indigenous natural perchlorate from the southwestern USA [δ37Cl = +4.1 ± 1.0 ‰; 36Cl/Cl = 1811 (± 136) × 10−15], and urinary perchlorate from the Taltal, Chile region is similar to natural perchlorate in nitrate salt deposits from the Atacama Desert of northern Chile [δ37Cl = −11.0 ± 1.0 ‰; 36Cl/Cl = 254 (± 40) × 10−15]. Neither urinary perchlorate resembled the isotopic pattern found in synthetic perchlorate. These results indicate that natural perchlorate of regional provenance is the dominant exposure source for the two sample populations, and that chlorine isotope ratios provide a robust tool for elucidating perchlorate exposure pathways. PMID:25805252

Determination of Sr and Ca sources in small tropical catchments (La Selva, Costa Rica) - A comparison of Sr and Ca isotopes

NASA Astrophysics Data System (ADS)

Wiegand, B. A.; Schwendenmann, L.

2013-04-01

SummaryA comparative study of Sr and Ca isotopes was conducted to assess solute sources and effects of biogeochemical processes on surface water and groundwater in four small tropical catchments located at La Selva Biological Station, Costa Rica. Variable concentrations of dissolved Sr2+ and Ca2+ in the catchments are related to mixing of waters from different origin. Three catchments are influenced by high-solute bedrock groundwater, while another catchment is primarily supplied by local recharge. 87Sr/86Sr ratios were employed to discriminate contributions from mineral weathering and atmospheric sources. Solutes in bedrock groundwater have a predominant geogenic origin, whereas local recharge is characterized by low-solute inputs from rainwater and minor in situ weathering releases from nutrient-depleted soils. Bedrock groundwater contributes more than 60% of dissolved Sr2+ to surface discharge in the Salto, Saltito, and Arboleda catchments, whereas the Taconazo catchment receives more than 95% of dissolved Sr2+ from rainwater. δ44/40Ca values of dissolved Ca2+ vary greatly in the catchments, mainly as a result of heterogeneous Ca isotope compositions of the contributing sources. Based on differences in δ44/40Ca values, two distinct bedrock groundwaters discharging at the Salto and the Arboleda catchments are suggested. Effects of biological processes in the plant-soil system on solute generation in the catchments are indicated by variable Ca/Sr ratios. However, these effects cannot clearly be assessed by Ca isotopes due to the strong heterogeneity of δ44/40Ca values of Ca2+ sources and high Ca2+ concentrations in bedrock groundwater.

Pb-isotopic Features of Primitive Rocks from Hess Deep: Distinguishing between EPR and Cocos-Nazca Mantle Source(s)

NASA Astrophysics Data System (ADS)

Jean, M. M.; Falloon, T.; Gillis, K. M.

2014-12-01

We have acquired high-precision Pb-isotopic signatures of primitive lithologies (basalts/gabbros) recovered from IODP Expedition 345.The Hess Deep Rift, located in the vicinity of the Galapagos triple junction (Cocos, Nazca, and Pacific), is viewed as one the best-studied tectonic windows into fast-spreading crust because a relatively young (<1.5 Ma) cross section of oceanic crust. This allows for (1) characterization of the mantle source(s) at Hess Deep, (2) insight into the extent of isotopic homogeneity or heterogeneity in the area, and (3) constrain the relative contributions from the intruding Cocos-Nazca spreading center. The observed Pb-isotopic variation at Hess Deep covers almost the entire range of EPR MORB (10°N to -5°S). Hess Deep samples range from 208Pb (37.3-38.25), 207Pb (15.47-15.58), 206Pb (17.69-18.91). These compositions suggest that this part of Hess Deep mantle is no more isotopically homogeneous than EPR mantle. Two distinct arrays are also observed: 208Pb-enriched (r2=0.985; n=30) and 208Pb-depleted (r2=0.988; n=6). The 208Pb/204Pb isotopes indicates that the Pb-source for some of the samples at Hess Deep had very low Th/U ratios, whereas other areas around the Galapagos microplate seem to have more "normal" ratios. These trends are less apparent when viewed with 207Pb-isotopes. Instead, the majority of basalts and gabbros follow the NHRL, however, at the depleted-end of this array a negative excursion to more enriched compositions is observed. This negative but linear trend could signify an alteration trend or mixing with an EMI-type mantle source, yet this mixing is not observed with 208Pb. This trend is also observed at Pito Deep, which has similar origins to Hess Deep (Barker et al., 2008; Pollack et al., 2009). The Galapagos region has been considered a testing ground for mixing of HIMU, Enriched Mantle, and Depleted Mantle reservoirs (e.g., Schilling et al., 2002). According to our data, however, an EPR-component must also be considered. We model Hess Deep Pb-isotopes as a 4-component system. EPR-DM-EM comprise a 'local' reservoir, but the majority of samples contain a mixture of modified-HIMU-EM-EPR, a product of incoming plume material entrained within the Galapagos Spreading Center.

Midcontinent rift volcanism in the Lake Superior region: Sr, Nd, and Pb isotopic evidence for a mantle plume origin

USGS Publications Warehouse

Nicholson, S.W.; Shirey, S.B.

1990-01-01

Between 1091 and 1098 Ma, most of a 15- to 20-km thickness of dominantly tholeiitic basalt erupted in the Midcontinent Rift System of the Lake Superior region, North America. The Portage Lake Volcanics in Michigan, which are the younget MRS flood basalts, fall into distinctly high- and low-TiO2 types having different liquid lines of descent. Incompatible trace elements in both types of tholeiites are enriched compared to depleted or primitive mantle and both basalt types are isotopically indistinguishable. The isotopic enrichment of the MRS source compared to depleted mantle is striking and must have occurred at least 700 m.y. before 1100 Ma. There are two likely sources for such magmatism: subcontinental lithospheric mantle enriched during the early Proterozoic or enriched mantle derived from an upwelling plume. Decompression melting of an upwelling enriched mantle plume in a region of lithosphere thinned by extension could have successfully generated the enormous volume (850 ?? 103 km3) of relatively homogeneous magma in a restricted time interval. -from Authors

Silicon Isotope Geochemistry of Ocean Island Basalts: Search for Deep Mantle Heterogeneities and Evidence for Recycled Altered Oceanic Crust

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Savage, P. S.; Jackson, M. G.; Moreira, M. A.; Day, J. M.; Moynier, F.

2014-12-01

Analyses of Ocean Island Basalts (OIB) have shown that the Earth's mantle contains isotopically distinct components, but debate about the degree and cause of variability persists. The study of silicon (Si) isotopes in OIBs has the potential to elucidate mantle heterogeneities. Relatively large (~several per mil) Si isotopic fractionation occurs in low-temperature environments during precipitation from dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes [1], but only a limited range (~tenths of a per mil) of Si isotope fractionation has been observed due to high-temperature igneous processes [2]. Therefore, Si isotopes may be useful as tracers for the presence of crustal material in OIB source regions in a manner similar to more conventional stable isotope systems, such as oxygen. Here we present the first comprehensive suite of high-precision Si isotopic data obtained by MC-ICP-MS for a diverse set of OIBs representing the EM-1, EM-2, and HIMU mantle components. In general, the Si isotopic compositions of OIBs analyzed here are agreement with previous estimates for Bulk Silicate Earth (BSE). However, small systematic variations are present; the HIMU end-member Mangaia and HIMU-type Cape Verde island São Nicolau are enriched in the light isotopes of Si (δ30Si = -0.37 ± 0.06‰ and δ30Si = -0.39 ± 0.04‰, respectively; errors are 2sd), with compositions intermediary between Mid Ocean Ridge Basalts and chondritic values. Additionally, Iceland samples from volcanic complexes in the Northern Rift Zone show similar Si isotope compositions (on average, δ30Si = -0.40 ± 0.06‰). In contrast, the δ30Si averages of the EM-1 end-member Pitcairn (-0.28 ± 0.07‰), the EM-2 end-member Samoa (-0.31 ± 0.07‰) and other OIB localities do not show any significant difference from previous estimates for the δ30Si value of BSE [3]. The Si isotopic variability in some HIMU-type and Icelandic OIBs most likely reflects the incorporation of recycled altered oceanic crust in the plume source. However, the sampling of a primitive reservoir enriched in the light isotopes of Si, as suggested by [4], cannot be ruled out as a potential source of Si isotope variations in OIBs. References: [1] Ziegler et al., GCA 2005 [2] Savage et al., GCA 2011 [3] Savage et al., EPSL 2010 [4] Huang et al., GCA 2014

Lu-Hf isotopic memory of plume-lithosphere interaction in the source of layered mafic intrusions, Windimurra Igneous Complex, Yilgarn Craton, Australia

NASA Astrophysics Data System (ADS)

Nebel, O.; Arculus, R. J.; Ivanic, T. J.; Nebel-Jacobsen, Y. J.

2013-10-01

Most layered mafic intrusions (LMI) are formed via multiple magma injections into crustal magma chambers. These magmas are originally sourced from the mantle, likely via plume activity, but may interact with the overriding lithosphere during ascent and emplacement in the crust. The magma injections lead to the establishment of different layers and zones with complex macroscopic, microscopic and cryptic compositional layering through magmatic differentiation and associated cumulate formation, sometimes accompanied by crustal assimilation. These complex mineralogical and petrological processes obscure the nature of the mantle sources of LMI, and typically have limited the degree to which parental liquids can be fully characterised. Here, we present Lu-Hf isotope data for samples from distinct layers of the Upper Zone of the Windimurra Igneous Complex (WIC), an immense late-Archean LMI in the West Australian Yilgarn Craton. Lu-Hf isotope systematics of whole rocks are well correlated (MSWD=5.6, n=17) with an age of ˜3.05±0.05 Ga and initial ɛHf˜+8. This age, however, is older than whole rock Sm-Nd and zircon U-Pb ages of the intrusion, both of which are ca. 2.8 Ga. Stratigraphically-controlled initial Hf isotope variations (associated with multiple episodes of emplacement at ca. 2.8 Ga) indicate isotope mixing between a near-chondritic and an ultra-radiogenic component, the latter with ɛHf[2.8 Ga]>+15. This Hf isotope mixing creates a pseudochron-relationship at the time of intrusion of ˜250 Myr that is superimposed on subsequent radiogenic ingrowth after crystallisation, generating an age that predates the actual emplacement event. Mixing between late-stage crystallisation products (melt + crystals) from the Middle Zone and replenishing, plume-derived liquids was followed by crystal accumulation in a chemically evolving magma chamber. The ultra-radiogenic Hf isotope endmember in the WIC mantle source requires parent-daughter ratios consistent with very early formation in Earth history, akin to early Archean komatiitic plume sources. We propose that plume-derived melts that formed the Windimurra LMI reacted with ancient refractory lithospheric keels already underpinning ancient cratons, creating a melt with extremely high ɛHf[t]. Melting a refractory component with super-chondritic, time-integrated high Lu/Hf, in this case by plume-lithosphere interaction, simultaneously accounts for the extreme Hf isotope signals, Hf-Nd isotope decoupling, and difference in radiometric Lu-Hf and Sm-Nd ages.

Steady state or non-steady state? Identifying driving mechanisms of oxygen isotope signatures of leaf transpiration in functionally distinct plant species

NASA Astrophysics Data System (ADS)

Dubbert, Maren; Kübert, Angelika; Cuntz, Matthias; Werner, Christiane

2015-04-01

Isotope techniques are widely applied in ecosystem studies. For example, isoflux models are used to separate soil evaporation from transpiration in ecosystems. These models often assume that plant transpiration occurs at isotopic steady state, i.e. that the transpired water shows the same isotopic signature as the source water. Yet, several studies found that transpiration did not occur at isotopic steady state, under both controlled and field conditions. Here we focused on identifying the internal and external factors which drive the isotopic signature of leaf transpiration. Using cavity ring-down spectroscopy (CRDS), the effect of both environmental variables and leaf physiological traits on δ18OT was investigated under controlled conditions. Six plant species with distinct leaf physiological traits were exposed to step changes in relative air humidity (RH), their response in δ18OT and gas exchange parameters and their leaf physiological traits were assessed. Moreover, two functionally distinct plant types (tree, i.e. Quercus suber, and grassland) of a semi-arid Mediterranean oak-woodland where observed under natural conditions throughout an entire growth period in the field. The species differed substantially in their leaf physiological traits and their turn-over times of leaf water. They could be grouped in species with fast (<60 min.), intermediate (ca. 120 min.) and slow (>240 min.) turn-over times, mostly due to differences in stomatal conductance, leaf water content or a combination of both. Changes in RH caused an immediate response in δ18OT, which were similarly strong in all species, while leaf physiological traits affected the subsequent response in δ18OT. The turn-over time of leaf water determined the speed of return to the isotopic steady or a stable δ18OT value (Dubbert & Kübert et al., in prep.). Under natural conditions, changes in environmental conditions over the diurnal cycle had a huge impact on the diurnal development of δ18OT in both observed plant functional types. However, in accordance with our findings in the lab, species specific differences in the leaf water turn over time, significantly influenced the amount of time plants transpired at non-steady state during the day (Dubbert et al., 2013, 2014). Our results emphasize the significance of considering isotopic non-steady state of transpiration and specifically to account for the specific differences of plant species resulting from distinct physiological traits of their leaves when applying isoflux models in ecosystem studies. Dubbert, M; Cuntz, M; Piayda, A; Maguas, C; Werner, C: Partitioning evapotranspiration - Testing the Craig and Gordon model with field measurements of oxygen isotope ratios of evaporative fluxes. J Hydrol (2013) Dubbert, M; Piayda, A; Cuntz, M; Correia, AC; Costa e Silva, F; Pereira, JS; Werner, C: Stable oxygen isotope and flux partitioning demonstrates understory of an oak savanna contributes up to half of ecosystem carbon and water exchange, Frontiers in Plant Science (2014a)

Tracking Reactive Nitrogen Sources, Chemistry and Deposition in Urban Environments Using Stable Isotopes

NASA Astrophysics Data System (ADS)

Hastings, M. G.; Clark, S. C.; Chai, J.; Joyce, E.; Miller, D. J.; Schiebel, H.; Walters, W.

2017-12-01

Reactive nitrogen (Nr) includes compounds such as nitrogen oxides (NOx, HONO), ammonia (NH3), nitrate (NO3-), ammonium (NH4+), and organic nitrates. These compounds serve major roles in controlling the composition of our atmosphere, and have a direct impact on ecosystem health and water quality. Our research is focused on using stable isotopes of Nr to investigate variations in sources, chemistry, atmospheric transport, and deposition. Our aim is to fingerprint distinct emission sources - such as vehicles, power plants, aircraft, agriculature, wildfires, and lightning - and track their influence in the environment. We have recently characterized vehicle emission plumes, emissions from agricultural soils under different management practices, and (in the near future) wildfire plumes in the western U.S. Our approach targets characterizing the isotopic composition of NOx, HONO, and NH3 at both the emissions source and the plume scale. In contrast to large ranges found for individual tailpipe emissions of NOx, on-road plumes in the U.S. have a mean δ15N of -4.7 ± 1.7‰. The plume scale approach integrates across the typical U.S. fleet giving a representative value that can be used for tracking the impact of this emission source in the environment. NH3 also tends towards a narrow isotopic range when considered at the roadside scale compared to individual vehicles. In agricultural settings, the isotopes of NOx and HONO released from soils under different fertilizer practices is typically very negative in δ15N (-40 to -10‰) and appears to vary most with soil N properties rather than meteorology. Our work is now extending to discern sources influencing Nr deposition in an urban area at the head of New England's largest estuary. National monitoring of N deposition shows decreases in NO3- (but not NH4+) deposition over the last two decades, following better controls on NOx emissions. Wet deposition collected in an urban area exhibits N concentrations that are often 3-5 times higher than that found in regional monitoring networks. An event-based, year-round record of the isotopic composition of NO3- and NH4+ in wet deposition is currently underway with the aim of constraining local versus transported emissions sources and understanding the implications of very concentrated deposition events on a major urban watershed.

Subducted slab-plume interaction traced by magnesium isotopes in the northern margin of the Tarim Large Igneous Province

NASA Astrophysics Data System (ADS)

Cheng, Zhiguo; Zhang, Zhaochong; Xie, Qiuhong; Hou, Tong; Ke, Shan

2018-05-01

Incorporation of subducted slabs may account for the geochemical and isotopic variations of large igneous provinces (LIPs). However, the mechanism and process by which subducted slabs are involved into magmas is still highly debated. Here, we report a set of high resolution Mg isotopes for a suite of alkaline and Fe-rich rocks (including basalts, mafic-ultramafic layered intrusions, diabase dykes and mantle xenoliths in the kimberlitic rocks) from Tarim Large Igneous Province (TLIP). We observed that δ26 Mg values of basalts range from -0.29 to - 0.45 ‰, -0.31 to - 0.42 ‰ for mafic-ultramafic layered intrusions, -0.28 to - 0.31 ‰ for diabase dykes and -0.29 to - 0.44 ‰ for pyroxenite xenoliths from the kimberlitic rocks, typically lighter than the normal mantle source (- 0.25 ‰ ± 0.04, 2 SD). After carefully precluding other possibilities, we propose that the light Mg isotopic compositions and high FeO contents should be ascribed to the involvement of recycled sedimentary carbonate rocks and pyroxenite/eclogite. Moreover, from basalts, through layered intrusions to diabase dykes, (87Sr/86Sr)i values and δ18OV-SMOW declined, whereas ε (Nd) t and δ26 Mg values increased with progressive partial melting of mantle, indicating that components of carbonate rock and pyroxenite/eclogite in the mantle sources were waning over time. In combination with the previous reported Mg isotopes for carbonatite, nephelinite and kimberlitic rocks in TLIP, two distinct mantle domains are recognized for this province: 1) a lithospheric mantle source for basalts and mafic-ultramafic layered intrusions which were modified by calcite/dolomite and eclogite-derived high-Si melts, as evidenced by enriched Sr-Nd-O and light Mg isotopic compositions; 2) a plume source for carbonatite, nephelinite and kimberlitic rocks which were related to magnesite or periclase/perovskite involvement as reflected by depleted Sr-Nd-O and extremely light Mg isotopes. Ultimately, our study suggests that subducted slabs could make important contributions to LIP generation, and establishes a potential linkage between plate tectonics and mantle plume.

Stable sulfur isotope ratios and chemical compositions of fine aerosols (PM2.5) in Beijing, China.

PubMed

Wei, Lianfang; Yue, Siyao; Zhao, Wanyu; Yang, Wenyi; Zhang, Yingjie; Ren, Lujie; Han, Xiaokun; Guo, Qingjun; Sun, Yele; Wang, Zifa; Fu, Pingqing

2018-08-15

Pervasive particulate pollution has been observed over large areas of the North China Plain. The high level of sulfate, a major component in fine particles, is pronounced during heavy pollution periods. Being different from source apportionments by atmospheric chemistry-transport model and receptor modeling methods, here we utilize sulfur isotopes to discern the potential emission sources. Sixty-five daily PM 2.5 samples were collected at an urban site in Beijing between September 2013 and July 2014. Inorganic ions, organic/elemental carbon and stable sulfur isotopes of sulfate were analyzed. The "fingerprint" characteristics of stable sulfur isotopic composition, together with trajectory clustering modeled by HYSPLIT-4 (HYbrid Single-Particle Lagrangian Integrated Trajectory) and FLEXPART ("FLEXible PARTicle dispersion model"), was employed to identify potential aerosol sources in Beijing. Results exhibited a distinctive seasonality with sulfate, nitrate, ammonium, organic matter, and element carbon being the dominant species of PM 2.5 . Elevated concentrations of chloride with high organic matter were found in autumn and winter as a result of enhanced fossil fuel (mainly coal) combustion. The δ 34 S values of the Beijing aerosols ranged from 2.8‰ to 9.9‰ with an average of 6.0 ± 1.8‰, further indicating that the major sulfur source was direct coal burning emission. Owing to the changing patterns between oxidation pathways of S(IV) in different seasons, δ 34 S values varied with a winter maximum (8.2 ± 1.1‰) and a summer minimum (4.9 ± 1.9‰). The results of trajectory clustering and FLEXPART demonstrated that higher concentrations of sulfate with lower sulfur isotope ratios (4.6 ± 0.8‰) were associated with air masses from the south or east, whereas lower sulfate concentrations with heavier sulfur isotope ratios (6.7 ± 1.6‰) were observed when the air masses were mainly from the north or northwest. These results suggested that the fine aerosol pollution in Beijing, especially sulfate pollution, was mainly due to coal combustion sources from regional and local regions. Copyright © 2018 Elsevier B.V. All rights reserved.

Evidence from Xenon isotopes for limited mixing between MORB sources and plume sources since 4.45 Ga

NASA Astrophysics Data System (ADS)

Mukhopadhyay, S.

2011-12-01

Xenon isotopes provide unique insights into the sources of volatile material for planet Earth, the degassing of the mantle, and the chemical evolution of the mantle [1-4]. 129Xe is produced from 129I, which has a half-life of 16 Myrs, and 131-136Xe are produced from 244Pu, which has a half-life of 80 Myrs. To a smaller extent, 131-136Xe are also produced from 238U fission. Thus, ratios of Pu-derived to U-derived fission xenon and 129I-derived to Pu-derived fission xenon constrain the rate and degree of outgassing of a mantle reservoir. Here, I report on the Pu-derived to U-derived fission xenon and Pu/I ratio of the Iceland plume. I then compare the plume observations with the gas rich popping rock from the North Mid Atlantic Ridge that samples the upper mantle [4]. Through step crushing of multiple aliquots of a basalt glass from Iceland, 51 high-precision He, Ne, Ar, and Xe isotopic compositions were generated. Combined He, Ne, and Xe measurements provide unequivocal evidence that the Iceland plume has a lower 129Xe/130Xe ratio than MORBs because it evolved with a I/Xe ratio distinct from the MORB source and not because of recycled atmosphere (which has low 129Xe/130Xe) in the plume source. Since 129I became extinct 80 Myrs after solar system formation, limited mixing between plume and MORB source is a stringent requirement since 4.45 Ga. Of the 51 different isotopic analyses, 42 data points were distinct from the atmospheric 129Xe/130Xe composition at two standard deviations. These 42 data points were utilized to calculate the ratio of Pu- to U-derived fission xenon. The starting composition of terrestrial Xe is a matter of debate. However, for reasonable starting compositions of air, non-radiogenic atmosphere, solar wind, and U-Xe [5-7], the Iceland plume ,on average, has approximately a factor of two higher Pu-derived xenon than the MORB source. These data thus, provide unequivocal evidence that the Iceland plume is less degassed than the MORB source and that the differences must have existed early on because Pu becomes extinct after ~ 400 Myrs. Thus, the Xe isotopic data suggests that differences between plume and MORB sources are the result of different mantle processing rates and not related to the preferential recycling of atmospheric gases into the plume source. Furthermore, if the plumes are derived from the large low shear wave velocity (LLSVPs) provinces at the base of the lower mantle [8], then our results require that LLSVPs are not made of solely recycled material. Rather, primitive material must constitute some fraction of the LLSVPs, and LLSVPs are ancient, having persisted through most of Earth's history. [1] Holland and Ballentine, Nature, 2006. [2] Yokochi and Marty, EPSL, 2004. [3] Coltice et al., Chem Geol., 2009. [4] Moriera et al., Science, 1998. [5] Caffee et al., Science, 1998. [6] Kunz et al., Science 1998. [7] Pepin and Porcelli, EPSL, 2006. [8] Torsvik et al., Nature, 2010.

Hydrochemical determination of source water contributions to Lake Lungo and Lake Ripasottile (central Italy)

USGS Publications Warehouse

Archer, Claire; Noble, Paula; Kreamer, David; Piscopo, Vincenzo; Petitta, Marco; Rosen, Michael R.; Poulson, Simon R.; Piovesan, Gianluca; Mensing, Scott

2017-01-01

Lake Lungo and Lake Ripasottile are two shallow (4-5 m) lakes located in the Rieti Basin, central Italy, that have been described previously as surface outcroppings of the groundwater table. In this work, the two lakes as well as springs and rivers that represent their potential source waters are characterized physio-chemically and isotopically, using a combination of environmental tracers. Temperature and pH were measured and water samples were analyzed for alkalinity, major ion concentration, and stable isotope (δ2H, δ18O, δ13C of dissolved inorganic carbon, and δ34S and δ18O of sulfate) composition. Chemical data were also investigated in terms of local meteorological data (air temperature, precipitation) to determine the sensitivity of lake parameters to changes in the surrounding environment. Groundwater represented by samples taken from Santa Susanna Spring was shown to be distinct with SO42- and Mg2+ content of 270 and 29 mg/L, respectively, and heavy sulfate isotopic composition(δ34S=15.2 ‰ and δ18O=10‰). Outflow from the Santa Susanna Spring enters Lake Ripasottile via a canal and both spring and lake water exhibits the same chemical distinctions and comparatively low seasonal variability. Major ion concentrations in Lake Lungo are similar to the Vicenna Riara Spring and are interpreted to represent the groundwater locally recharged within the plain. The δ13CDIC exhibit the same groupings as the other chemical parameters, providing supporting evidence of the source relationships. Lake Lungo exhibited exceptional ranges of δ13CDIC (±5 ‰) and δ2H, δ18O (±5 ‰ and ±7 ‰, respectively), attributed to sensitivity to seasonal changes. The hydrochemistry results, particularly major ion data, highlight how the two lakes, though geographically and morphologically similar, represent distinct hydrochemical facies. These data also show a different response in each lake to temperature and precipitation patterns in the basin that may be attributed to lake water retention time. The sensitivity of each lake to meteorological patterns can be used to understand the potential effects from long-term climate variability.

Application of neodymium isotope ratio measurements for the origin assessment of uranium ore concentrates.

PubMed

Krajkó, Judit; Varga, Zsolt; Yalcintas, Ezgi; Wallenius, Maria; Mayer, Klaus

2014-11-01

A novel procedure has been developed for the measurement of (143)Nd/(144)Nd isotope ratio in various uranium-bearing materials, such as uranium ores and ore concentrates (UOC) in order to evaluate the usefulness and applicability of variations of (143)Nd/(144)Nd isotope ratio for provenance assessment in nuclear forensics. Neodymium was separated and pre-concentrated by extraction chromatography and then the isotope ratios were measured by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The method was validated by the measurement of standard reference materials (La Jolla, JB-2 and BCR-2) and the applicability of the procedure was demonstrated by the analysis of uranium samples of world-wide origin. The investigated samples show distinct (143)Nd/(144)Nd ratio depending on the ore type, deposit age and Sm/Nd ratio. Together with other characteristics of the material in question, the Nd isotope ratio is a promising signature for nuclear forensics and suggests being indicative of the source material, the uranium ore. Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

Oxygen Isotopic Analyses of Water Extracted from the Martian Meteorite NWA 7034

NASA Astrophysics Data System (ADS)

Nunn, M.; Agee, C. B.; Thiemens, M. H.

2012-12-01

Introduction: The NWA 7034 meteorite has been identified as Martian, but it is distinct from the Shergottite-Nakhlite-Chassignite (SNC) grouping of meteorites in its petrology (it is the only known Martian basaltic breccia) and bulk silicate oxygen isotopic composition (Δ17O = 0.56 ± 0.06 ‰, where Δ17O = δ17O - 0.528 x δ18O, compared to the average SNC Δ17O ≈ 0.3 ‰) [e.g., 1-2]. We report here measurements of the oxygen isotopic composition of water extracted from NWA 7034 by stepwise heating. Methods: A piece (~1.2g) of NWA 7034 was pumped to vacuum until outgassing had stopped before heating to 50, 150, 320, 500, and 1000°C. The sample was maintained at each temperature step for at least one hour while collecting evolved volatiles in a liquid nitrogen cold trap. Water was selectively converted to molecular oxygen, the oxygen isotopic composition of which was then measured on a double collecting isotope ratio mass spectrometer. Results: Our stepwise heating experiments indicate NWA 7034 contains 3330ppm water, and this water has an average oxygen isotopic composition of Δ17O = 0.330 ± 0.011‰. The oxygen isotopic composition of water in NWA 7034 is unlike that of the silicates from which it is extracted (Δ17O = 0.56 ± 0.06 ‰) but is comparable to the average SNC silicate composition (Δ17O ≈ 0.3 ‰). However, there is no consensus on the oxygen isotopic composition of water in SNCs because aliquots of water extracted from different samples (separate pieces of a single meteorite or from different meteorites) have different oxygen isotopic compositions [3]. Furthermore, carbonates and sulfates extracted from SNCs also possess distinct oxygen isotopic compositions [4]. The variation in oxygen isotopic composition among these phases most likely results from the existence of isotopically distinct oxygen reservoirs on Mars that were not equilibrated. On Earth, interaction of ozone (O3) and carbon dioxide (CO2) leads to a mass independent oxygen isotopic composition of atmospheric CO2 [5]. This anomaly is transferred by exchange from CO2 to water and subsequently to secondary minerals. The much larger CO2 to water ratio on Mars could allow this process to introduce a measurable oxygen isotopic anomaly to sulfates, carbonates, and water. The magnitude and variability of this anomaly would depend on the formation mechanism of the species (particularly the source of oxygen), as is consistent with measurements to date of phases in SNCs. References: [1] Franchi, I.A., et al. (1999) MAPS 34, 657-661. [2] Rumble, D. and Irving, A.J. (2009) LPSC XXXX, #2293 [3] Karlsson, H.R., et al. (1992) Science 255, 1409-1411. [4] Farquhar, J. and Thiemens, M.H. (2000) J. Geophys. Res. 105, 11991-11997. [5] Yung, Y.L., et al. (1991) Geophys. Res. Lett. 18, 13-16.

Exploiting Stable Mercury Isotopic Analysis to Differentiate between Mercury Sources: Gold Mining vs. Land-Use Change (Invited)

NASA Astrophysics Data System (ADS)

Bergquist, B. A.; Adler Miserendino, R. A.; Guimarães, J. R.; Veiga, M.; Velasquez-López, P.; Lees, P. S.; Thibodeau, A. M.; Fernandez, L. E.

2013-12-01

In parts of the developing world, mercury (Hg) is used to extract gold by amalgamation during artisanal and small-scale gold mining (ASGM) and this can lead to contamination of downstream aquatic ecosystems. Differentiation between Hg from ASGM and from other sources of Hg, such as increased erosion from land cover and land use change (LCLUC), is challenging and has lead to heated debates over the dominant sources of elevated Hg in some ecosystems. Here, stable Hg isotopic analysis was applied in two aquatic ecosystems in South America: (1) the Amazonian aquatic ecosystem of Amapá, Brazil downstream of artisanal gold mining (AGM) and (2) the Puyango-Tumbes River ecosystem downstream of Portovelo-Zaruma, Ecuador, a large mining area where both AGM and small-scale gold mining (SGM) are in operation. The Hg isotopic analyses from Amapá, Brazil, do not support AGM as the source of elevated Hg in the downstream aquatic ecosystem. Instead, Hg isotopes are most consistent with the elevated Hg being from preferential migration of Hg from soil erosion, which is likely associated with land use change. Although soils are regarded as Hg sinks in the global Hg cycle, this work suggests that LCLUC can disrupt Hg stores with significant ecological consequences. In contrast in the Southwestern Andean region of Ecuador and Peru, analysis of Hg isotopes and other toxic metals (i.e., Pb, Zn, Cu), which are associated with the larger scale mining and cyanide used during SGM, demonstrate Hg used during gold mining is the predominant source of Hg downstream and can be traced far from the dominant mining area. Although it has been speculated that Hg from SGM in Ecuador was not that mobile or that Hg far downstream of SGM processing plants was from erosion due to LCLUC or from AGM taking place downstream, the isotopically heavy signature of Hg used during gold mining and elevated other metal concentrations were observed ~120 km downstream of Portovelo-Zaruma. Mercury isotopes appear able to differentiate mining Hg from the non-mining background, which includes runoff from soils and atmospheric deposition, but they cannot distinguish between Hg used during mining from different mining regions or Hg used during AGM versus SGM. Thus, other toxic metals were measured that are more likely to be associated with SGM as opposed to AGM. Together, these studies demonstrate that variations in stable Hg isotopes are a viable tool to differentiate between Hg sources. Although there are unconstrained or unknown aspects of the stable Hg isotope cycle, the isotopic differences between Hg used during ASGM and from background soil, sediment and atmospheric deposition are large enough not to be obscured by changes in isotopic distributions that may be induced as Hg is transported through the environment. This is likely because most of the Hg in the above aquatic ecosystems is bound to particles and colloids and transported such that most of the Hg does not undergo transformations that fractionate Hg isotopes. For example, in the Puyango-Tumbes River, greater than 95% of the Hg is transported in the particulate phase. Thus, in areas where Hg is transported primarily in the particulate or colloidal form, it can be traced if Hg sources are isotopically distinct. Additionally, the contrasting results in our two studies show that scale and processing differences between AGM and SGM influence the extent of Hg contamination.

Pb, Sr, and Nd isotopes in seamount basalts from the Juan de Fuca Ridge and Kodiak-Bowie seamount chain, northeast Pacific

USGS Publications Warehouse

Hegner, E.; Tatsumoto, M.

1989-01-01

Pb, Sr, and Nd isotopic ratios and their parent/daughter element concentrations for 28 basalts from 10 hotspot and nonhotspot seamounts are reported. Nd and Sr isotopic compositions (143Nd/144Nd = 0.51325-0.51304; 87Sr/86Sr = 0.70237-0.70275) plot in the envelope for Juan de Fuca-Gorda ridge basalts with tholeiitic basalts showing more depleted sources and a better negative correlation than transitional to alkalic basalts. Pb isotopic ratios in tholeiitic and alkalic basalts overlap (206Pb/204Pb = 18.29-19.44) and display a trend toward more radiogenic Pb in alkalic basalts. The isotopic data for hotspot and nonhotspot basalts are indistinguishable and correlate broadly with rock composition, implying that they are controlled by partial melting. The isotopic variation in the seamount basalts is about 60% (Nd-Sr) to 100% (Pb) of that in East Pacific Rise basalts and is interpreted as a lower limit for the magnitude of mantle heterogeneity in the northeast Pacific. The data indicate absence of a chemically distinct plume component in the linear seamount chains and strongly suggest an origin from mid-ocean ridge basalt-like east Pacific mantle. -Authors

Utilization of carbon sources in a northern Brazilian mangrove ecosystem

NASA Astrophysics Data System (ADS)

Giarrizzo, Tommaso; Schwamborn, Ralf; Saint-Paul, Ulrich

2011-12-01

Carbon and nitrogen stable isotope ratios ( 13C and 15N) and trophic level (TL) estimates based on stomach content analysis and published data were used to assess the contribution of autotrophic sources to 55 consumers in an intertidal mangrove creek of the Curuçá estuary, northern Brazil. Primary producers showed δ 13C signatures ranging between -29.2 and -19.5‰ and δ 15N from 3.0 to 6.3‰. The wide range of the isotopic composition of carbon of consumers (-28.6 to -17.1‰) indicated that different autotrophic sources are important in the intertidal mangrove food webs. Food web segregation structures the ecosystem into three relatively distinct food webs: (i) mangrove food web, where vascular plants contribute directly or indirectly via POM to the most 13C-depleted consumers (e.g. Ucides cordatus and zooplanktivorous food chains); (ii) algal food web, where benthic algae are eaten directly by consumers (e.g. Uca maracoani, mullets, polychaetes, several fishes); (iii) mixed food web where the consumers use the carbon from different primary sources (mainly benthivorous fishes). An IsoError mixing model was used to determine the contributions of primary sources to consumers, based on δ 13C values. Model outputs were very sensitive to the magnitude of trophic isotope fractionation and to the variability in 13C data. Nevertheless, the simplification of the system by a priori aggregation of primary producers allowed interpretable results for several taxa, revealing the segregation into different food webs.

Determination of the origin of dissolved inorganic carbon in groundwater around a reclaimed landfill in Otwock using stable carbon isotopes

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

Porowska, Dorota, E-mail: dorotap@uw.edu.pl

Highlights: • Research showed the origin of DIC in the groundwater around a reclaimed landfill. • Carbon isotope was used to evaluate the contributions of carbon from different sources. • The leachate-contaminated water was isotopically distinct from the natural groundwater. • DIC in the natural groundwater comes from organic matter and dissolution of carbonates. • In the contaminated water, DIC comes from organic matter in the aquifer and landfill. - Abstract: Chemical and isotopic analyses of groundwater from piezometers located around a reclaimed landfill in Otwock (Poland) were performed in order to trace the origin of dissolved inorganic carbon (DIC)more » in the groundwater. Due to differences in the isotopic composition of carbon from different sources, an analysis of stable carbon isotopes in the groundwater, together with the Keeling plot approach and a two-component mixing model allow us to evaluate the relative contributions of carbon from these sources in the groundwater. In the natural (background) groundwater, DIC concentrations and the isotopic composition of DIC (δ{sup 13}C{sub DIC}) comes from two sources: decomposition of organic matter and carbonate dissolution within the aquifer sediments, whereas in the leachate-contaminated groundwater, DIC concentrations and δ{sup 13}C{sub DIC} values depend on the degradation of organic matter within the aquifer sediments and biodegradation of organic matter stored in the landfill. From the mixing model, about 4–54% of the DIC pool is derived from organic matter degradation and 96–46% from carbonate dissolution in natural conditions. In the leachate-contaminated groundwater, about 20–53% of the DIC is derived from organic matter degradation of natural origin and 80–47% from biodegradation of organic matter stored in the landfill. Partial pressure of CO{sub 2} (P CO{sub 2}) was generally above the atmospheric, hence atmospheric CO{sub 2} as a source of carbon in DIC pool was negligible in the aquifer. P CO{sub 2} values in the aquifer in Otwock were always one to two orders of magnitude above the atmospheric P CO{sub 2}, and thus CO{sub 2} escaped directly into the vadose zone.« less

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.

Mass-Dependent and -Independent Fractionation of Mercury Isotopes in Aquatic Systems

NASA Astrophysics Data System (ADS)

Bergquist, B. A.; Joel, B. D.; Jude, D. J.

2008-12-01

Mercury is a globally distributed and highly toxic pollutant. Although Hg is a proven health risk, much of the natural cycle of Hg is not well understood and new approaches are needed to track Hg and the chemical transformations it undergoes in the environment. Recently, we demonstrated that Hg isotopes exhibit two types of isotope fractionation: (1) mass dependent fractionation (MDF) and (2) mass independent fractionation (MIF) of only the odd isotopes (Bergquist and Blum, 2007). The observation of large MIF of Hg isotopes (up to 5 permil) is exciting because only a few other isotopic systems have been documented to display large MIF, the most notable of which are oxygen and sulfur. In both cases, the application of MIF has proven very useful in a variety of fields including cosmochemistry, paleoclimatology, physical chemistry, atmospheric chemistry, and biogeochemistry. Both MDF and MIF isotopic signatures are observed in natural samples, and together they open the door to a new method for tracing Hg pollution and for investigating Hg behavior in the environment. For example, fish record MDF that appears to be related to size and age. Additionally, fish display MIF signatures that are consistent with the photo-reduction of methylmercury (Bergquist and Blum, 2007). If the MDF and MIF in ecosystems can be understood, the signatures in fish could inform us about the sources and processes transforming Hg and why there are differences in the bioaccumulation of Hg in differing ecosystems and populations of fish. This requires sampling of a variety of ecosystems, the sampling of many components of the ecosystems, and the use of other tracers such as carbon and nitrogen isotopes. We have expanded our studies of aquatic ecosystems to include several lakes in North America. Similar to other isotopic systems used to study food web dynamics and structure (i.e., C and N), the MDF of Hg in fish appears to be related to size and age. The MDF recorded in fish likely reflects both the sources of Hg to the fish and the excretion of Hg by the fish. Thus, MDF alone provides new insights into sources and bioaccumulation of Hg in food web. Fish populations from different lakes display distinct MIF and relationships between MDF and MIF. The degree of MIF is likely related to the amount of photo-reduction in a lake and dissolved organic carbon. We also sampled food sources and livers of fish to understand processes of isotopic fractionation in the food web.

Dual element ((15)N/(14)N, (13)C/(12)C) isotope analysis of glyphosate and AMPA by derivatization-gas chromatography isotope ratio mass spectrometry (GC/IRMS) combined with LC/IRMS.

PubMed

Mogusu, Emmanuel O; Wolbert, J Benjamin; Kujawinski, Dorothea M; Jochmann, Maik A; Elsner, Martin

2015-07-01

To assess sources and degradation of the herbicide glyphosate [N-(phosphonomethyl) glycine] and its metabolite AMPA (aminomethylphosphonic acid), concentration measurements are often inconclusive and even (13)C/(12)C analysis alone may give limited information. To advance isotope ratio analysis of an additional element, we present compound-specific (15)N/(14)N analysis of glyphosate and AMPA by a two step derivatization in combination with gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The N-H group was derivatized with isopropyl chloroformate (iso-PCF), and remaining acidic groups were subsequently methylated with trimethylsilyldiazomethane (TMSD). Iso-PCF treatment at pH <10 gave too low (15)N/(14)N ratios indicating an incomplete derivatization; in contrast, too high (15)N/(14)N ratios at pH >10 indicated decomposition of the derivative. At pH 10, and with an excess of iso-PCF by 10-24, greatest yields and accurate (15)N/(14)N ratios were obtained (deviation from elemental analyzer-IRMS: -0.2 ± 0.9% for glyphosate; -0.4 ± 0.7% for AMPA). Limits for accurate δ(15)N analysis of glyphosate and AMPA were 150 and 250 ng injected, respectively. A combination of δ(15)N and δ(13)C analysis by liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) (1) enabled an improved distinction of commercial glyphosate products and (2) showed that glyphosate isotope values during degradation by MnO2 clearly fell outside the commercial product range. This highlights the potential of combined carbon and nitrogen isotopes analysis to trace sources and degradation of glyphosate.

Magma mixing and the generation of isotopically juvenile silicic magma at Yellowstone caldera inferred from coupling 238U–230Th ages with trace elements and Hf and O isotopes in zircon and Pb isotopes in sanidine

USGS Publications Warehouse

Stelten, Mark E.; Cooper, Kari M.; Vazquez, Jorge A.; Reid, Mary R.; Barfod, Gry H.; Wimpenny, Josh; Yin, Qing-Zhu

2013-01-01

The nature of compositional heterogeneity within large silicic magma bodies has important implications for how silicic reservoirs are assembled and evolve through time. We examine compositional heterogeneity in the youngest (~170 to 70 ka) post-caldera volcanism at Yellowstone caldera, the Central Plateau Member (CPM) rhyolites, as a case study. We compare 238U–230Th age, trace-element, and Hf isotopic data from zircons, and major-element, Ba, and Pb isotopic data from sanidines hosted in two CPM rhyolites (Hayden Valley and Solfatara Plateau flows) and one extracaldera rhyolite (Gibbon River flow), all of which erupted near the caldera margin ca. 100 ka. The Hayden Valley flow hosts two zircon populations and one sanidine population that are consistent with residence in the CPM reservoir. The Gibbon River flow hosts one zircon population that is compositionally distinct from Hayden Valley flow zircons. The Solfatara Plateau flow contains multiple sanidine populations and all three zircon populations found in the Hayden Valley and Gibbon River flows, demonstrating that the Solfatara Plateau flow formed by mixing extracaldera magma with the margin of the CPM reservoir. This process highlights the dynamic nature of magmatic interactions at the margins of large silicic reservoirs. More generally, Hf isotopic data from the CPM zircons provide the first direct evidence for isotopically juvenile magmas contributing mass to the youngest post-caldera magmatic system and demonstrate that the sources contributing magma to the CPM reservoir were heterogeneous in 176Hf/177Hf at ca. 100 ka. Thus, the limited compositional variability of CPM glasses reflects homogenization occurring within the CPM reservoir, not a homogeneous source.

Petrogenesis of ultramafic xenoliths from Hawaii inferred from Sr, Nd, and Pb isotopes

NASA Astrophysics Data System (ADS)

Okano, Osamu; Tatsumoto, Mitsunobu

Isotopic compositions of Nd, Sr, and Pb in xenoliths in the Honolulu volcanic series from the Salt Lake Crater (H-type) are similar to those of the host post-erosional basalts, but are distinct from the magma sources of Koolau shield tholeiites and MORB. In contrast, one spinel Iherzolite (K-type) has isotopic compositions of Nd and Sr that are close to those of Koolau tholeiite rather than to the other Hawaiian basalts. Previous studies have shown that Sr isotopic composition of the xenoliths and the host basalt and that trace element concentrations in minerals of garnet Iherzolites from Honolulu basalt were nearly in equilibrium with the host magma, indicating that Honolulu volcanics were derived from garnet Iherzolite or similar material. However, differences exist among the isotopic compositions (especially Nd) of the xenoliths indicating that they are accidental inclusions from upper layers. The similarity in isotopic compositions between xenoliths and Honolulu basalt suggests that the source areas in the mantle are chemically similar. Correlation of 238U/204Pb vs. 206Pb/204Pb of chrome diopside separated from the H-type spinel Iherzolites indicates that the xenoliths are 80±36 Ma, which corresponds to the lithosphere age of the Hawaiian site. This age is consistent with petrological studies [e.g., Sen and Leeman, 1991] which have found that the spinel Iherzolite inclusions are derived from the lithosphere wall rocks. The ɛNd = ˜+8 of the H-xenoliths is slightly lower than that for the East Pacific Rise MORB indicating that the xenoliths are derived from a trace element depleted source similar to the MORB residue. If the garnet Iherzolite xenoliths are derived from mixture of spinel Iherzolite with intrusive pyroxenite, then the source of the pyroxenite contained little plume component. The one exceptional spinel Iherzolite xenolith may be a residue of Koolau-like tholeiitic magma or may have been metasomatized by Koolau volcanism in the deep lithosphere. Isotopic compositions of gabbro in Kaupulehu are similar to MORB, indicating its derivation from the oceanic crust. The Sr and Nd isotopic compositions of dunite are similar to those of Hualalai alkaline magma, consistent with the theory that the dunite is a cumulate from the Hualalai magma.

Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

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

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.

Volcanism and post-magmatism contribute significant annual methane (CH 4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH 4 (as well as carbon dioxide (CO 2) and other gases), but the ultimate sources of this CH 4 flux have not been elucidated. In this paper, we use dual stable isotope analysis (δ 2H and δ 13C) of CH 4 sampled from ten high-temperature geothermalmore » pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ 13C and δ 2H values of CH 4 emitted from hot springs ( 26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ 13C CH4 and δ 13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH 4, or with equilibration of CH 4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ 13C CH4 and δ 13C CO2 ranged from ~ 250–350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ 2H H2O of the thermal springs and the measured δ 2H CH4 values are consistent with equilibration between the source water and the CH 4 at the formation temperatures. Though the ultimate origin of the CH 4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C 1/C 2+ composition of the gases is more consistent with abiotic origins for most of the samples. Finally, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH 4 flux from the Yellowstone National Park volcanic system.« less

Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

DOE PAGES

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.; ...

2017-05-16

Volcanism and post-magmatism contribute significant annual methane (CH 4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH 4 (as well as carbon dioxide (CO 2) and other gases), but the ultimate sources of this CH 4 flux have not been elucidated. In this paper, we use dual stable isotope analysis (δ 2H and δ 13C) of CH 4 sampled from ten high-temperature geothermalmore » pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ 13C and δ 2H values of CH 4 emitted from hot springs ( 26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ 13C CH4 and δ 13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH 4, or with equilibration of CH 4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ 13C CH4 and δ 13C CO2 ranged from ~ 250–350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ 2H H2O of the thermal springs and the measured δ 2H CH4 values are consistent with equilibration between the source water and the CH 4 at the formation temperatures. Though the ultimate origin of the CH 4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C 1/C 2+ composition of the gases is more consistent with abiotic origins for most of the samples. Finally, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH 4 flux from the Yellowstone National Park volcanic system.« less

Dual stable isotopes of CH4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO2

NASA Astrophysics Data System (ADS)

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.; Jennings, Ryan deM.; Beam, Jacob P.; Kreuzer, Helen W.; Inskeep, William P.

2017-07-01

Volcanism and post-magmatism contribute significant annual methane (CH4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH4 (as well as carbon dioxide (CO2) and other gases), but the ultimate sources of this CH4 flux have not been elucidated. Here we use dual stable isotope analysis (δ2H and δ13C) of CH4 sampled from ten high-temperature geothermal pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ13C and δ2H values of CH4 emitted from hot springs (26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ13CCH4 and δ13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH4, or with equilibration of CH4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ13CCH4 and δ13CCO2 ranged from 250-350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ2HH2O of the thermal springs and the measured δ2HCH4 values are consistent with equilibration between the source water and the CH4 at the formation temperatures. Though the ultimate origin of the CH4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C1/C2 + composition of the gases is more consistent with abiotic origins for most of the samples. Thus, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH4 flux from the Yellowstone National Park volcanic system.

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.

The Mantle Isotopic Array: A Tale of Two FOZOs

NASA Astrophysics Data System (ADS)

Apen, F. E.; Mukhopadhyay, S.; Williams, C. D.

2017-12-01

Oceanic basalts display isotopic arrays that suggest mixing between a depleted component, several enriched components, and a primitive component. The topology of the arrays provides information on mantle mixing, the distribution of heterogeneities, and information on mantle structure. Here we use a global compilation of mid-ocean ridge basalt (MORB) and ocean island basalt (OIB) He-Sr-Nd-Pb isotopic data to further analyze the topology of these arrays. Previous work indicated that OIB isotopic arrays converge to a common component [1-3] referred to as the focus zone, or FOZO. Our analyses suggest that while all OIBs do point to a common component with unradiogenic 4He/3He ratios relative to MORBs, this component has to be quite variable in its He, Sr, Nd and Pb isotopic compositions. FOZO cannot be a pure component but must represent a heterogeneous mixture of primitive and recycled material. Our analyses of the MORB and OIB isotopic compositions also indicate that while MORBs and OIBs sample the same components, the topology of their mixing arrays are quite distinct. Different MOR segments show quasi-linear isotopic arrays that all converge to a common component. This component is distinctive from the OIB FOZO being more depleted and more restrictive in its He, Sr, Nd and Pb composition. We suggest two common but distinguishable components are present in the mantle arrays: one common to MORBs and the other to OIBs, and we refer to them as MORB-FOZO and OIB-FOZO, respectively. We interpret the two FOZOs to represent the average composition of small-scale heterogeneities that make up the background matrix in the sources of MORBs and OIBs. The depleted and enriched components that are sampled in MORBs and OIBs reflect relatively large-scale heterogeneities distributed within the matrix, material that have yet to be deformed into the smaller length scales of the matrix material. Differences between the two FOZO compositions reflects the inclusion of a component with primitive He in OIBs along with differences in mixing timescales and mantle processing rates for MORBs and OIBs. The two distinct FOZO compositions must also indicate limited direct mixing between the two over Earth's 4.5 Gyr history. References: [1] Hart et al., Science 1992; [2] Farley et al., EPSL 1992; [3] Hanan and Graham, Science 1996.

Multiple sulphur and oxygen isotopes reveal microbial sulphur cycling in spring waters in the Lower Engadin, Switzerland.

PubMed

Strauss, Harald; Chmiel, Hannah; Christ, Andreas; Fugmann, Artur; Hanselmann, Kurt; Kappler, Andreas; Königer, Paul; Lutter, Andreas; Siedenberg, Katharina; Teichert, Barbara M A

2016-01-01

Highly mineralized springs in the Scuol-Tarasp area of the Lower Engadin and in the Albula Valley near Alvaneu, Switzerland, display distinct differences with respect to the source and fate of their dissolved sulphur species. High sulphate concentrations and positive sulphur (δ(34)S) and oxygen (δ(18)O) isotopic compositions argue for the subsurface dissolution of Mesozoic evaporitic sulphate. In contrast, low sulphate concentrations and less positive or even negative δ(34)S and δ(18)O values indicate a substantial contribution of sulphate sulphur from the oxidation of sulphides in the crystalline basement rocks or the Jurassic sedimentary cover rocks. Furthermore, multiple sulphur (δ(34)S, Δ(33)S) isotopes support the identification of microbial sulphate reduction and sulphide oxidation in the subsurface, the latter is also evident through the presence of thick aggregates of sulphide-oxidizing Thiothrix bacteria.

Paleozoic tectonics of the Ouachita Orogen through Nd isotopes

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

Gleason, J.D.; Patchett, P.J.; Dickinson, W.R.

1992-01-01

A combined isotopic and trace-element study of the Late Paleozoic Ouachita Orogenic belt has the following goals: (1) define changing provenance of Ouachita sedimentary systems throughout the Paleozoic; (2) constrain sources feeding into the Ouachita flysch trough during the Late Paleozoic; (3) isolate the geochemical signature of proposed colliding terranes to the south; (4) build a data base to compare with possible Ouachita System equivalents in Mexico. The ultimate aim is to constrain the tectonic setting of the southern margin of North America during the Paleozoic, with particular emphasis on collisional events leading to the final suturing of Pangea. Ndmore » isotopic data identify 3 distinct groups: (1) Ordovician passive margin sequence; (2) Carboniferous proto-flysch (Stanley Fm.), main flysch (Jackfork and Atoka Fms.) and molasse (foreland Atoka Fm.); (3) Mississippian ash-flow tuffs. The authors interpret the Ordovician signature to be essentially all craton-derived, whereas the Carboniferous signature reflects mixed sources from the craton plus orogenic sources to the east and possibly the south, including the evolving Appalachian Orogen. The proposed southern source is revealed by the tuffs to be too old and evolved to be a juvenile island arc terrane. They interpret the tuffs to have been erupted in a continental margin arc-type setting. Surprisingly, the foreland molasse sequence is indistinguishable from the main trough flysch sequence, suggesting the Ouachita trough and the craton were both inundated with sediment of a single homogenized isotopic signature during the Late Carboniferous. The possibility that Carboniferous-type sedimentary dispersal patterns began as early as the Silurian has important implications for the tectonics and paleogeography of the evolving Appalachian-Ouachita Orogenic System.« less

An Isotopic Map of Dust Source Areas in the McMurdo Sound Sector of Antarctica

NASA Astrophysics Data System (ADS)

Blakowski, M. A.; Aciego, S.; Delmonte, B.; Baroni, C.; Salvatore, M. C.

2014-12-01

The McMurdo Sound sector of Antarctica features a unique, polar desert ecosystem characterized by low temperatures, hyper-aridity, and high-speed winds. These climatic conditions result in limited water sources, sparse vegetation, underdeveloped soils, and abundant unconsolidated sediment easily influenced by wind-driven transport. Radiogenic isotopes (87Sr/86Sr, 143Nd/144Nd) provide constant signatures of dust from source- to sink-areas. Accordingly, aeolian dust derived from arid regions has been recognized in many studies as an important tracer of atmospheric circulation, as well as a tool for deciphering past climatic conditions in dust source regions. However, while major global dust sources (e.g. from South America, Africa, and Asia) are well studied and easily identifiable via distinct isotopic signatures when encountered in different depositional environments (e.g. Antarctic ice cores), local material from sources in and around the ice-free Dry Valleys and surrounding areas have remained in need of further documentation. We analyzed 40 samples of silt, sand, glacial drift, and weathered regolith material in both fine (<5μm) and coarse fractions collected from Victoria Land and the McMurdo Sound sector, including Cape Royds, Cape Bird, and the McMurdo Ice Shelf. Here we present an ArcGIS-generated, high-precision geochemical map of Antarctic PSAs synthesized from our data and combined with geomorphological and stratigraphic information on the studied sites. We believe that our expanded isotopic catalogue and map can be used to enhance and/or prompt regional studies in a variety of disciplines, such as by providing greater constraints on models of regional dust variability and transport pathways and of the melting history of the Antarctic ice sheet, and by determining the provenance of dust archived in ice cores, lake sediment, soil records, and impurities in Antarctic sea-ice.

The geochemistry of primitive volcanic rocks of the Ankaratra volcanic complex, and source enrichment processes in the genesis of the Cenozoic magmatism in Madagascar

NASA Astrophysics Data System (ADS)

Melluso, L.; Cucciniello, C.; le Roex, A. P.; Morra, V.

2016-07-01

The Ankaratra volcanic complex in central Madagascar consists of lava flows, domes, scoria cones, tuff rings and maars of Cenozoic age that are scattered over 3800 km2. The mafic rocks include olivine-leucite-nephelinites, basanites, alkali basalts and hawaiites, and tholeiitic basalts. Primitive samples have high Mg# (>60), high Cr and Ni concentrations; their mantle-normalized patterns peak at Nb and Ba, have troughs at K, and smoothly decrease towards the least incompatible elements. The Ankaratra mafic rocks show small variation in Sr-Nd-Pb isotopic compositions (e.g., 87Sr/86Sr = 0.70377-0.70446, 143Nd/144Nd = 0.51273-0.51280, 206Pb/204Pb = 18.25-18.87). These isotopic values differ markedly from those of Cenozoic mafic lavas of northern Madagascar and the Comoro archipelago, typical Indian Ocean MORB and oceanic basalt end-members. The patterns of olivine nephelinitic magmas can be obtained through 3-10% partial melting of a mantle source that was enriched by a Ca-rich alkaline melt, and that contained garnet, carbonates and phlogopite. The patterns of tholeiitic basalts can be obtained after 10-12% partial melting of a source enriched with lower amounts of the same alkaline melt, in the spinel- (and possibly amphibole-) facies mantle, hence in volumes where carbonate is not a factor. The significant isotopic change from the northernmost volcanic rocks of Madagascar and those in the central part of the island implicates a distinct source heterogeneity, and ultimately assess the role of the continental lithospheric mantle as source region. The source of at least some volcanic rocks of the still active Comoro archipelago may have suffered the same time-integrated geochemical and isotopic evolution as that of the northern Madagascar volcanic rocks.

Atacama perchlorate as an agricultural contaminant in groundwater: Isotopic and chronologic evidence from Long Island, New York

USGS Publications Warehouse

Böhlke, J.K.; Hatzinger, P.B.; Sturchio, N.C.; Gu, B.; Abbene, I.; Mroczkowski, S.J.

2009-01-01

Perchlorate (ClO4-) is a common groundwater constituent with both synthetic and natural sources. A potentially important source of ClO4- is past agricultural application of ClO4--bearing natural NO3- fertilizer imported from the Atacama Desert, Chile, but evidence for this hasbeenlargely circumstantial. Here we report ClO4- stable isotope data (??37Cl, ??18O, and ??17O), along with other supporting chemical and isotopic environmental tracer data, to document groundwater ClO4- contamination sources and history in parts of Long Island, New York. Sampled groundwaters were oxic and ClO4- apparently was not affected by biodegradation within the aquifers. Synthetic ClO4- was indicated by the isotopic method in groundwater near a fireworks disposal site at a former missile base. Atacama ClO4- was indicated in agricultural and urbanizing areas in groundwaters with apparent ages >20 years. In an agricultural area, ClO4- concentrations and ClO4-/NO3- ratios increased withgroundwaterage, possiblybecauseof decreasing application rates of Atacama NO3- fertilizers and/or decreasing ClO4- concentrations in Atacama NO 3- fertilizers in recent years. Because ClO 4-/NO3- ratios of Atacama NO 3- fertilizers imported in the past (???2 ?? 10-3 mol mol-1) were much higher than the ClO 4-/NO3- ratio of recommended drinking-water limits (7 ?? 10-5 mol mol-1 in New York), ClO4- could exceed drinkingwater limits even where NO3- does not, and where Atacama NO3- was only a minor source of N. Groundwater ClO4- with distinctive isotopic composition was a sensitive indicator of past Atacama NO3- fertilizer use on Long Island and may be common in other areas that received NO3- fertilizers from the late 19th century through the 20th century. ?? 2009 American Chemical Society.

Evaluation of 4 years of continuous δ13C(CO2) data using a moving Keeling plot method

NASA Astrophysics Data System (ADS)

Vardag, Sanam Noreen; Hammer, Samuel; Levin, Ingeborg

2016-07-01

Different carbon dioxide (CO2) emitters can be distinguished by their carbon isotope ratios. Therefore measurements of atmospheric δ13C(CO2) and CO2 concentration contain information on the CO2 source mix in the catchment area of an atmospheric measurement site. This information may be illustratively presented as the mean isotopic source signature. Recently an increasing number of continuous measurements of δ13C(CO2) and CO2 have become available, opening the door to the quantification of CO2 shares from different sources at high temporal resolution. Here, we present a method to compute the CO2 source signature (δS) continuously and evaluate our result using model data from the Stochastic Time-Inverted Lagrangian Transport model. Only when we restrict the analysis to situations which fulfill the basic assumptions of the Keeling plot method does our approach provide correct results with minimal biases in δS. On average, this bias is 0.2 ‰ with an interquartile range of about 1.2 ‰ for hourly model data. As a consequence of applying the required strict filter criteria, 85 % of the data points - mainly daytime values - need to be discarded. Applying the method to a 4-year dataset of CO2 and δ13C(CO2) measured in Heidelberg, Germany, yields a distinct seasonal cycle of δS. Disentangling this seasonal source signature into shares of source components is, however, only possible if the isotopic end members of these sources - i.e., the biosphere, δbio, and the fuel mix, δF - are known. From the mean source signature record in 2012, δbio could be reliably estimated only for summer to (-25.0 ± 1.0) ‰ and δF only for winter to (-32.5 ± 2.5) ‰. As the isotopic end members δbio and δF were shown to change over the season, no year-round estimation of the fossil fuel or biosphere share is possible from the measured mean source signature record without additional information from emission inventories or other tracer measurements.

Tracking Nonpoint Source Nitrogen and Carbon in Watersheds of Chesapeake Bay

NASA Astrophysics Data System (ADS)

Kaushal, S.; Pennino, M. J.; Duan, S.; Blomquist, J.

2012-12-01

Humans have altered nitrogen and carbon cycles in rivers regionally with important impacts on coastal ecosystems. Nonpoint source nitrogen pollution is a leading contributor to coastal eutrophication and hypoxia. Shifts in sources of carbon impact downstream ecosystem metabolism and fate and transport of contaminants in coastal zones. We used a combination of stable isotopes and optical tracers to investigate fate and transport of nitrogen and carbon sources in tributaries of the largest estuary in the U.S., the Chesapeake Bay. We analyzed isotopic composition of water samples from major tributaries including the Potomac River, Susquehanna River, Patuxent River, and Choptank River during routine and storm event sampling over multiple years. A positive correlation between δ15N-NO3- and δ18O-NO3- in the Potomac River above Washington D.C. suggested denitrification or biological uptake in the watershed was removing agriculturally-derived N during summer months. In contrast, the Patuxent River in Maryland showed elevated δ15N-NO3- (5 - 12 per mil) with no relationship to δ18O-NO3- suggesting the importance of wastewater sources. From the perspective of carbon sources, there were distinct isotopic values of the δ13C-POM of particulate organic matter and fluorescence excitation emission matrices (EEMS) for rivers influenced by their dominant watershed land use. EEMS showed that there were increases in the humic and fulvic fractions of dissolved organic matter during spring floods, particularly in the Potomac River. Stable isotopic values of δ13C-POM also showed rapid depletion suggesting terrestrial carbon "pulses" in the Potomac River each spring. The δ15N-POM peaked to 10 - 15 per mil each spring suggested a potential manure source or result of biological processing within the watershed. Overall, there were considerable changes in sources and transformations of nitrogen and carbon that varied across rivers and that contribute to nitrogen and carbon loads. Anticipating changes in sources and transformations will be critical for effectively managing nonpoint pollution and ecosystem services such as drinking water quality and coastal habitat.

Understanding N2O sources and sinks with laser based isotopic analysis

NASA Astrophysics Data System (ADS)

Mohn, Joachim; Harris, Eliza; Tuzson, Béla; Emmenegger, Lukas

2015-04-01

Nitrous oxide (N2O) is a potent greenhouse gas and the strongest ozone-destroying substance. The main emissions of N2O are linked to different microbial processes, therefore the sources are disperse and highly variable, complicating the development of effective mitigation strategies. Isotopic measurements have great potential to unravel spatial and temporal variations in sources, sinks and chemistry of N2O. Recent developments in quantum cascade laser spectroscopy (QCLAS) [1] allow both the intermolecular distribution of 15N substitutions ('site preference'; 15N14N16O versus 14N15N16O) and the oxygen isotopic composition (d18O) of N2O to be measured in real-time and at high precision of <0.2 ‰ [2]. Additionally, N2O isotopic analysis by QCLAS has demonstrated excellent compatibility to the standard technique isotope-ratio mass-spectrometry [3]. In a number of laboratory and pilot plant studies we investigated the isotopic signature of distinct microbial and abiotic N2O production and consumption pathways in soil and aqueous solution [e.g. 4]. Specific pathways were favoured by selection of the nitrogen substrates and process conditions and their isotopic signatures identified by real-time laser spectroscopic analysis. Results from our laboratory studies are in accordance with pure culture experiments and can therefore be applied to other ecosystems. Recently, high precision isotopic analysis at ambient N2O is also feasible by combining laser spectroscopy with automated preconcentration [5]. The field deployment was demonstrated by real-time monitoring isotopic composition of N2O emissions from an intensively managed grassland in central Switzerland for three months. The responses of the N2O isotopic signatures were analysed with respect to management events and weather influences [2]. In a follow-up project we intend to combine real-time N2O isotopic analysis at a tall tower in central Switzerland with atmospheric transport simulations and a biogeochemical model of surface fluxes of N2O isotopomers. The working hypothesis is that this approach will allow us to quantify regional N2O sources, identify emission hot spots, and constrain source processes, which will be of upmost importance for developing targeted mitigation options. References: [1] H. Wächter, J. Mohn, B. Tuzson, L. Emmenegger, M. W. Sigrist, Opt. Express (2008), 16, 9239-9244. [2] B. Wolf, L. Merbold, C. Decock, B. Tuzson, E. Harris, J. Six, L. Emmenegger, J. Mohn, Biogeosci. Discuss. (2015), accepted. [3] J. Mohn et al., Rapid Commun. Mass Spectrom. (2014) 28, 1995-2007. [4] P. Wunderlin, M. F. Lehmann, H. Siegrist, B. Tuzson, A. Joss, L. Emmenegger, J. Mohn, Environ. Sci. Technol. (2013), 47, 1339-1348. [5] J. Mohn, B. Tuzson, A. Manninen, N. Yoshida, S. Toyoda, W. A. Brand, L. Emmenegger, Atmos. Meas. Tech. (2012), 5, 1601-1609.

Carbon isotopic variation in ureilites: Evidence for an early, volatile-rich Inner Solar System

NASA Astrophysics Data System (ADS)

Barrat, Jean-Alix; Sansjofre, Pierre; Yamaguchi, Akira; Greenwood, Richard C.; Gillet, Philippe

2017-11-01

We analyzed the C isotopic compositions of 32 unbrecciated ureilites, which represent mantle debris from a now disrupted, C-rich, differentiated body. The δ13C values of their C fractions range from -8.48 to +0.11‰. The correlations obtained between δ13C, δ18O and Δ17O values and the compositions of the olivine cores, indicate that the ureilite parent body (UPB) accreted from two reservoirs displaying distinct O and C isotopic compositions. The range of Fe/Mg ratios shown by its mantle was not the result of melting processes involving reduction with C ("smelting"), but was chiefly inherited from the mixing of these two components. Because smelting reactions are pressure-dependent, this result has strong implications for the size of the UPB, and points to a large parent body, at least 690 km in diameter. It demonstrates that C-rich primitive matter distinct from that represented by carbonaceous chondrites was present in some areas of the early inner Solar System, and could have contributed to the growth of the terrestrial planets. We speculate that differentiated, C-rich bodies, or debris produced by their disruption, were an additional source of volatiles during the later accretion stages of the rocky planets, including Earth.

Integrating Source Apportionment Tracers into a Bottom-up Inventory of Methane Emissions in the Barnett Shale Hydraulic Fracturing Region.

PubMed

Townsend-Small, Amy; Marrero, Josette E; Lyon, David R; Simpson, Isobel J; Meinardi, Simone; Blake, Donald R

2015-07-07

A growing dependence on natural gas for energy may exacerbate emissions of the greenhouse gas methane (CH4). Identifying fingerprints of these emissions is critical to our understanding of potential impacts. Here, we compare stable isotopic and alkane ratio tracers of natural gas, agricultural, and urban CH4 sources in the Barnett Shale hydraulic fracturing region near Fort Worth, Texas. Thermogenic and biogenic sources were compositionally distinct, and emissions from oil wells were enriched in alkanes and isotopically depleted relative to natural gas wells. Emissions from natural gas production varied in δ(13)C and alkane ratio composition, with δD-CH4 representing the most consistent tracer of natural gas sources. We integrated our data into a bottom-up inventory of CH4 for the region, resulting in an inventory of ethane (C2H6) sources for comparison to top-down estimates of CH4 and C2H6 emissions. Methane emissions in the Barnett are a complex mixture of urban, agricultural, and fossil fuel sources, which makes source apportionment challenging. For example, spatial heterogeneity in gas composition and high C2H6/CH4 ratios in emissions from conventional oil production add uncertainty to top-down models of source apportionment. Future top-down studies may benefit from the addition of δD-CH4 to distinguish thermogenic and biogenic sources.

Isotopic evolution of Mauna Kea volcano: Results from the initial phase of the Hawaii Scientific Drilling Project

USGS Publications Warehouse

Lassiter, J.C.; DePaolo, D.J.; Tatsumoto, M.

1996-01-01

We have examined the Sr, Nd, and Pb isotopic compositions of Mauna Kea lavas recovered by the first drilling phase of the Hawaii Scientific Drilling Project. These lavas, which range in age from ???200 to 400 ka, provide a detailed record of chemical and isotopic changes in basalt composition during the shied/postshield transition and extend our record of Mauna Kea volcanism to a late-shield period roughly equivalent to the last ???100 ka of Mauna Loa activity. Stratigraphic variations in isotopic composition reveal a gradual shift over time toward a more depleted source composition (e.g., higher 143Nd/144Nd, lower 87Sr/86Sr, and lower 3He/4He). This gradual evolution is in sharp contrast with the abrupt appearance of alkalic lavas at ???240 ka recorded by the upper 50 m of Mauna Kea lavas from the core. Intercalated tholeiitic and alkalic lavas from the uppermost Mauna Kea section are isotopically indistinguishable. Combined with major element evidence (e.g., decreasing SiO2 and increasing FeO) that the depth of melt segregation increased during the transition from tholeiitic to alkalic volcanism, the isotopic similarity of tholeiitic and alkalic lavas argues against significant lithosphere involvement during melt generation. Instead, the depleted isotopic signatures found in late shield-stage lavas are best explained by increasing the proportion of melt generated from a depleted upper mantle component entrained and heated by the rising central plume. Direct comparison of Mauna Kea and Mauna Loa lavas erupted at equivalent stages in these volcanoes' life cycles reveals persistent chemical and isotopic differences independent of the temporal evolution of each volcano. The oldest lavas recovered from the drillcore are similar to modern Kilauea lavas, but are distinct from Mauna Loa lavas. Mauna Kea lavas have higher 143Nd/144Nd and 206Pb/204Pb and lower 87Sr/86Sr. Higher concentrations of incompatible trace elements in primary magmas, lower SiO2, and higher FeO also indicate that Mauna Kea lavas formed through smaller degrees of partial melting at greater depth than Mauna Loa lavas. These chemical and isotopic differences are consistently found between volcanoes along the western "Loa" and eastern "Kea" trends and reflect large-scale variations in source composition and melting environment. We propose a simple model of a radially zoned plume centered beneath the Loa trend. Loa trend lavas generated from the hot plume axis reflect high degrees of partial melting from a source containing a mixture of enriched plume-source material and entrained lower mantle. Kea trend lavas, in contrast, are generated from the cooler, peripheral portions of the plume, record lower degrees of partial melting, and tap a source containing a greater proportion of depleted upper mantle.

Plutonium in the arctic marine environment--a short review.

PubMed

Skipperud, Lindis

2004-06-18

Anthropogenic plutonium has been introduced into the environment over the past 50 years as the result of the detonation of nuclear weapons and operational releases from the nuclear industry. In the Arctic environment, the main source of plutonium is from atmospheric weapons testing, which has resulted in a relatively uniform, underlying global distribution of plutonium. Previous studies of plutonium in the Kara Sea have shown that, at certain sites, other releases have given rise to enhanced local concentrations. Since different plutonium sources are characterised by distinctive plutonium-isotope ratios, evidence of a localised influence can be supported by clear perturbations in the plutonium-isotope ratio fingerprints as compared to the known ratio in global fallout. In Kara Sea sites, such perturbations have been observed as a result of underwater weapons tests at Chernaya Bay, dumped radioactive waste in Novaya Zemlya, and terrestrial runoff from the Ob and Yenisey Rivers. Measurement of the plutonium-isotope ratios offers both a means of identifying the origin of radionuclide contamination and the influence of the various nuclear installations on inputs to the Arctic, as well as a potential method for following the movement of water and sediment loads in the rivers.

Lithium in tektites and impact glasses: Implications for sources, histories and large impacts

NASA Astrophysics Data System (ADS)

Magna, T.; Deutsch, A.; Mezger, K.; Skála, R.; Seitz, H.-M.; Mizera, J.; Řanda, Z.; Adolph, L.

2011-04-01

Lithium (Li) abundances and isotope compositions were determined in a representative suite of tektites (moldavites, Muong Nong-type tektites and an australite, Ivory Coast tektites and bediasites), impact-related glasses (Libyan Desert Glass, zhamanshinites and irghizites), a glass fragment embedded in the suevite from the Ries impact crater and sedimentary materials in order to test a possible susceptibility of Li to fractionation during hypervelocity impact events and to de-convolve links to their potential parental sources. The overall data show a large spread in Li abundance (4.7-58 ppm Li) and δ 7Li values (-3.2‰ to 26.0‰) but individual groups of tektites and impact glasses have distinctive Li compositions. Most importantly, any significant high-temperature Li isotope fractionation can be excluded by comparing sedimentary lithologies from central Europe with moldavites. Instead, we suggest that Li isotope compositions in tektites and impact-related glasses are probably diagnostic of the precursor materials and their pre-impact geological histories. The Muong Nong-type tektites and australite specimen are identical in terms of Li concentrations and δ 7Li and we tentatively endorse their common origin in a single impact event. Evidence for low-temperature Rayleigh fractionation, which must have operated prior to impact-induced melting and solidification, is provided for a subset of Muong Nong-type tektites. Although Li isotope variations in most tektites are broadly similar to those of the upper continental crust, Libyan Desert Glass carries high δ 7Li ⩾24.7‰, which appears to mirror the previous fluvial history of parental material that was perhaps deposited in lacustrine environment or coastal seawater. Lithium isotopes in impact-related glasses from the Zhamanshin crater define a group distinct from all other samples and point to melting of chemically less evolved mafic lithologies, which is also consistent with their major and trace element patterns. Extreme shock pressures and the related extreme post-shock temperatures alone appear not to have any effect on the Li isotope systematics; therefore, useful information on parental lithologies and magmatic processes may be retrieved from analyses of Martian and lunar meteorites. Moreover, lack of significant Li depletion in tektites provides further constraints on the loss of moderately volatile elements during the Moon-forming impact.

Oxygen isotopic variations in the outer margins and Wark–Lovering rims of refractory inclusions

DOE PAGES

Simon, Justin I.; Matzel, Jennifer E. P.; Simon, Steven B.; ...

2016-05-02

Oxygen isotopic variations across the outer margins and Wark–Lovering (WL) rims of a diverse suite of six coarse-grained Types A and B refractory inclusions from both oxidized and reduced CV3 chondrites suggest that CAIs originated from a 16O-rich protosolar gas reservoir and were later exposed to both relatively 17,18O-rich and 16O-rich reservoirs. The O-isotope profiles of CAIs can be explained by changes in the composition of gas near the protoSun or the migration of CAIs through a heterogeneous nebula. Variability within the inclusion interiors appears to have been set prior to WL rim growth. Modeling the isotopic zoning profiles asmore » diffusion gradients between inclusion interiors and edges establishes a range of permissible time–temperature combinations for their exposure in the nebula. At mean temperatures of 1400 K, models that match the isotope gradients in the inclusions yield timescales ranging from 5 × 10 3 to 3 × 10 5 years. Assuming CAIs originated with a relatively 16O-rich (protosolar) isotopic composition, differences among the melilite interiors and the isotopic gradients in their margins imply the existence of a number of isotopically distinct reservoirs. In addition, evidence at the edges of some CAIs for subsequent isotopic exchange may relate to the beginning of rim formation. In the WL rim layers surrounding the interiors, spinel is relatively 16O-rich but subtly distinct among different CAIs. Melilite is often relatively 16O-poor, but rare relatively 16O-rich grains also exist. Pyroxene generally exhibits intermediate O-isotope compositions and isotopic zoning. Olivine in both WL and accretionary rims, when present, is isotopically heterogeneous. The extreme isotopic heterogeneity among and within individual WL rim layers and in particular, the observed trends of outward 16O-enrichments, suggest that rims surrounding CAIs contained in CV3 chondrites, like the inclusions themselves, formed from a number of isotopically distinct gas reservoirs. Collectively, these results support numerical protoplanetary disk models in which CAIs were transported between several distinct nebular reservoirs multiple times prior to accretion onto a parent body.« less

Oxygen isotopic variations in the outer margins and Wark-Lovering rims of refractory inclusions

NASA Astrophysics Data System (ADS)

Simon, Justin I.; Matzel, Jennifer E. P.; Simon, Steven B.; Hutcheon, Ian D.; Ross, D. Kent; Weber, Peter K.; Grossman, Lawrence

2016-08-01

Oxygen isotopic variations across the outer margins and Wark-Lovering (WL) rims of a diverse suite of six coarse-grained Types A and B refractory inclusions from both oxidized and reduced CV3 chondrites suggest that CAIs originated from a 16O-rich protosolar gas reservoir and were later exposed to both relatively 17,18O-rich and 16O-rich reservoirs. The O-isotope profiles of CAIs can be explained by changes in the composition of gas near the protoSun or the migration of CAIs through a heterogeneous nebula. Variability within the inclusion interiors appears to have been set prior to WL rim growth. Modeling the isotopic zoning profiles as diffusion gradients between inclusion interiors and edges establishes a range of permissible time-temperature combinations for their exposure in the nebula. At mean temperatures of 1400 K, models that match the isotope gradients in the inclusions yield timescales ranging from 5 × 103 to 3 × 105 years. Assuming CAIs originated with a relatively 16O-rich (protosolar) isotopic composition, differences among the melilite interiors and the isotopic gradients in their margins imply the existence of a number of isotopically distinct reservoirs. Evidence at the edges of some CAIs for subsequent isotopic exchange may relate to the beginning of rim formation. In the WL rim layers surrounding the interiors, spinel is relatively 16O-rich but subtly distinct among different CAIs. Melilite is often relatively 16O-poor, but rare relatively 16O-rich grains also exist. Pyroxene generally exhibits intermediate O-isotope compositions and isotopic zoning. Olivine in both WL and accretionary rims, when present, is isotopically heterogeneous. The extreme isotopic heterogeneity among and within individual WL rim layers and in particular, the observed trends of outward 16O-enrichments, suggest that rims surrounding CAIs contained in CV3 chondrites, like the inclusions themselves, formed from a number of isotopically distinct gas reservoirs. Collectively, these results support numerical protoplanetary disk models in which CAIs were transported between several distinct nebular reservoirs multiple times prior to accretion onto a parent body.

ISONITRATE demonstration project: How isotopic monitoring can improve management of nitrate pollution in water

NASA Astrophysics Data System (ADS)

Widory, D.

2008-12-01

Nitrate is one of the major pollutants of drinking water resources worldwide. Recent European directives reduced inputs from intensive agriculture, but in most places NO3 levels are approaching the potable limit of 50 mg.l-1 in groundwater. Determining the source(s) of contamination in groundwater is an important first step for improving its quality by emission control. It is with this aim that we review here the benefit of using a multi-isotope approach (d15N, d180, d11B), in addition to conventional hydrogeological analysis, to constrain the the origin of NO3 pollution in water. The isotopic composition of the dissolved nitrogen species has been used extensively to better constrain the sources and fate of nitrate in groundwater. The possibility of quantifying both origin and secondary processes affecting N concentrations by means of a single tracer appears more limited however. Nitrogen cannot be considered conservative because it is biologically modified through nitrification and denitrification reactions, both during infiltration of the water and in the groundwater body, causing isotopic fractionation that modifies the d15N signatures of the dissolved N species. Discriminating multiple NO3 sources by their N isotopic composition alone becomes impossible whenever heterogenic or autogenic denitrification occurs, thus arising the need for establishing co-migrating discriminators of NO3 sources: addition of the d180 from NO3 and of the d11B. This presentation will strongly rely on our current European Life ISONITRATE project, which aims at showing policy makers how management of nitrate pollution in water can be greatly improved by the incorporation of the multi-isotope monitoring. The pilot site is located in the Alsace region (France and border Germany), part of the Upper Rhine basin, a groundwater body considered as one of the most important drinking water reservoirs in Europe. The demonstration of the multi-isotope approach is based on 4 distinct scenarios: 1. Natural case: corresponds to the natural nitrification of the soil and represents the reference end-member. Samples with NO3 concentration levels higher than this end-member are considered as polluted. 2. Denitrification case: groundwater samples are selected along an identified denitrification gradient in the "Appenweier-Rheinau" region (Germany): the uppermost samples being contaminated by mineral fertilizers used in vineyards (but not denitrified), and the downstream sample being (almost) totally denitrified. 3. Simple case: chosen as being under the influence of a sole type of nitrate pollution source: mineral fertilisation from the "Orschwihr- Bergholtz vineyards". 4. Complex case: where nitrates correspond to a mixing of different pollution sources (mineral and organic fertilisers), located within the "Dietwiller area".

Comparison of pore water samplers and cryogenic distillation under laboratory and field conditions for soil water stable isotope analysis.

PubMed

Thoma, Michael; Frentress, Jay; Tagliavini, Massimo; Scandellari, Francesca

2018-02-15

We used pore water samplers (PWS) to sample for isotope analysis (1) only water, (2) soil under laboratory conditions, and (3) soil in the field comparing the results with cryogenic extraction (CE). In (1) and (2), no significant differences between source and water extracted with PWS were detected with a mean absolute difference (MAD) always lower than 2 ‰ for δ 2 H and 1 ‰ for δ 18 O. In (2), CE water was more enriched than PWS-extracted water, with a MAD respect to source water of roughly 8 ‰ for δ 2 H and 4 ‰ for δ 18 O. In (3), PWS water was enriched relative to CE water by 3 ‰ for δ 2 H and 0.9 ‰ for δ 18 O. The latter result may be due to the distinct water portions sampled by the two methods. Large pores, easily sampled by PWS, likely retain recent, and enriched, summer precipitation while small pores, only sampled by CE, possibly retain isotopically depleted water from previous winter precipitation or irrigation inputs. Accuracy and precision were greater for PWS relative to CE. PWS is therefore suggested as viable tool to extract soil water for stable isotope analysis, particularly for soils used in this study (sandy and silty loams).

Use of strontium isotopes to identify buried water main leakage into groundwater in a highly urbanized coastal area.

PubMed

Leung, Chi-Man; Jiao, Jiu Jimmy

2006-11-01

Previous studies indicate that the local aquifer systems in the Mid-Levels, a highly urbanized coastal area in Hong Kong, have commonly been affected by leakage from water mains. The identification of leakage locations was done by conventional water quality parameters including major and trace elements. However, these parameters may lead to ambiguous results and fail to identify leakage locations especially where the leakage is from drinking water mains because the chemical composition of drinking water is similar to that of natural groundwater. In this study, natural groundwater, seepage in the developed spaces, leakage from water mains, and parent aquifer materials were measured for strontium isotope (87Sr/86Sr) compositions to explore the feasibility of using these ratios to better constrain the seepage sources. The results show that the 87Sr/86Sr ratios of natural groundwater and leakage from water mains are distinctly different and thus, they can provide additional information on the sources of seepage in developed spaces. A classification system based on the aqueous 87Sr/86Sr ratio is proposed for seepage source identification.

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.

Ammunition is the principal source of lead accumulated by California condors re-introduced to the wild.

PubMed

Church, Molly E; Gwiazda, Roberto; Risebrough, Robert W; Sorenson, Kelly; Chamberlain, C Page; Farry, Sean; Heinrich, William; Rideout, Bruce A; Smith, Donald R

2006-10-01

The endangered California Condor (Gymnogyps californianus) was reduced to a total population of 22 birds by the end of 1982. Their captive-bred descendants are now being released back into the wild in California, Arizona, and Baja California, where monitoring indicates they may accumulate lead to toxic levels. Fragments of ammunition in the carcasses of game animals such as deer, elk, and feral pigs not retrieved by hunters or in gut piles left in the field have been considered a plausible source of the lead, though little direct evidence is available to support this hypothesis. Here, we measured lead concentrations and isotope ratios in blood from 18 condors living in the wild in central California, in 8 pre-release birds, and in diet and ammunition samples to determine the importance of ammunition as a source of exposure. Blood lead levels in pre-release condors were low (average 27.7 ng/mL, SD 4.9 ng/ mL) and isotopically similar to dietary and background environmental lead in California. In contrast, blood lead levels in free-flying condors were substantially higher (average 246 ng/mL, SD 229 ng/mL) with lead isotopic compositions that approached or matched those of the lead ammunition. A two-endmember mixing model defined by the background 207Pb/206Pb ratio of representative condor diet samples (0.8346) and the upper 207Pb/206Pb ratio of the ammunition samples (0.8184) was able to account for the blood lead isotopic compositions in 20 out of the 26 live condors sampled in this study (i.e., 77%). Finally, lead in tissues and in a serially sampled growing feather recovered postmortem from a lead-poisoned condor in Arizona evidence acute exposure from an isotopically distinct lead source. Together, these data indicate that incidental ingestion of ammunition in carcasses of animals killed by hunters is the principal source of elevated lead exposure that threatens the recovery in the wild of this endangered species.

Use and legacy of mercury in the Andes.

PubMed

Cooke, Colin A; Hintelmann, Holger; Ague, Jay J; Burger, Richard; Biester, Harald; Sachs, Julian P; Engstrom, Daniel R

2013-05-07

Both cinnabar (HgS) and metallic mercury (Hg(0)) were important resources throughout Andean prehistory. Cinnabar was used for millennia to make vermillion, a red pigment that was highly valued in pre-Hispanic Peru; metallic Hg(0) has been used since the mid-16th century to conduct mercury amalgamation, an efficient process of extracting precious metals from ores. However, little is known about which cinnabar deposits were exploited by pre-Hispanic cultures, and the environmental consequences of Hg mining and amalgamation remain enigmatic. Here we use Hg isotopes to source archeological cinnabar and to fingerprint Hg pollution preserved in lake sediment cores from Peru and the Galápagos Islands. Both pre-Inca (pre-1400 AD) and Colonial (1532-1821 AD) archeological artifacts contain cinnabar that matches isotopically with cinnabar ores from Huancavelica, Peru, the largest cinnabar-bearing district in Central and South America. In contrast, the Inca (1400-1532 AD) artifacts sampled are characterized by a unique Hg isotopic composition. In addition, preindustrial (i.e., pre-1900 AD) Hg pollution preserved in lake sediments matches closely the isotopic composition of cinnabar from the Peruvian Andes. Industrial-era Hg pollution, in contrast, is distinct isotopically from preindustrial emissions, suggesting that pre- and postindustrial Hg emissions may be distinguished isotopically in lake sediment cores.

Lead isotope compositions as guides to early gold mineralization: The North Amethyst vein system, Creede district, Colorado

USGS Publications Warehouse

Foley, Nora K.; Ayuso, Robert A.

1994-01-01

Pb isotope compositions from the late stage of the North Amethyst vein system and from the Bondholder and central and southern Creede mining districts are more radiogenic than the host volcanic rocks of the central cluster of the San Juan volcanic field. Our Pb isotope results indicate that early Au mineralization of the North Amethyst area may represent the product of an older and relatively local hydrothermal system distinct from that of the younger base metal and Ag mineralization found throughout the region. Fluids that deposited Au minerals may have derived their Pb isotope composition by a greater degree of interaction with shallow, relatively less radiogenic volcanic wall rocks. The younger, base metal and Ag-rich mineralization that overprints the Au mineralization in the North Amethyst area clearly has a more radiogenic isotopic signature, which implies that the later mineralization derived a greater component of its Pb from Proterozoic source rocks, or sediments derived from them.Paragenetically early sulfide-rich vein assemblages have the least radiogenic galenas and generally also have the highest Au contents. Thus, identification of paragenetically early vein assemblages with relatively unradiogenic Pb isotope compositions similar to those of the North Amethyst area provides an additional exploration tool for Au in the central San Juan Mountains area.

Toward a better δDalkanes paleoclimate proxy; Partitioning of seasonal water sources and xylem-leaf deuterium enrichment according to plant growth form and phenology

NASA Astrophysics Data System (ADS)

Wispelaere, Lien; Bodé, Samuel; Herve-Fernández, Pedro; Hemp, Andreas; Verschuren, Dirk; Boeckx, Pascal

2016-04-01

The DeepCHALLA consortium is preparing an ICDP (International Continental Drilling Program) deep-drilling project on Lake Challa, a crater lake near Mt. Kilimanjaro in equatorial East Africa, where the climate is tropical semi-arid climate and characterized by two distinct rainy seasons. The main objective of this project is to acquire high-resolution and accurately dated proxy data of continental climate and ecosystem change near the Equator over 250,000 years. One of the paleoclimate proxies to be used is the hydrogen-isotopic composition of sedimentary n-alkanes (δDalkanes) derived from fossil plant leaf wax. However, this requires a better understanding of seasonal variability in the isotopic composition of precipitation, and of the fractionation of its hydrogen during incorporation in the plant waxes. In addition, recent studies have described the existence of "two water worlds", resulting in an additional deviation of the isotopic composition of the water taken up by plants. In this study, we measured the δD and δ18O of local precipitation, lake water, and xylem and leaf water from different plant species, seasons and sites with varying distances to Lake Challa. We use these data to set up a local meteoric water line (LMWL), and to assess spatial and temporal patterns of water utilization by local plants. Our data show a seasonal change in water-isotope partitioning with plants tapping water from isotopically lighter water sources during the dry seasons, as indicated by more negative xylem δD values and higher offsets from precipitation (i.e. greater distances from the LMWL), therefore supporting the "two water worlds" hypothesis. Surprisingly, trees appear to preferentially exploit isotopically more enriched sources of soil water, suggesting shallower water sources, than shrubs. Plants located at the lake shore use a mixture of precipitation and lake water, reflected in enriched xylem δD values and in the intersection of 2H and 18O with the LMWL. Leaf-water deuterium enrichment, averaged over all plant species, sites and seasons equals 23 ± 27‰. Several factors influence the isotopic enrichment between xylem and leaf water, but according to our results, the growth form and phenology of plant species are the primary factors, while the location (proximity to the lake) and season exert relatively minor effects.

Geologically Controlled Isotope-Time Patterns Reveal Early Differentiation and Crust Formation Processes

NASA Astrophysics Data System (ADS)

Bennett, V. C.; Nutman, A. P.

2014-12-01

The mechanisms of continental crust production and evolution in the early Earth remain controversial, as are questions of the relative roles of early differentiation versus subsequent tectonic procssing in creating Earth's chemical signatures. Here we present geologic observations integrated with whole rock major, trace element and Sm-Nd isotopic signatures and combined with U-Pb and Lu-Hf isotopic compositions of zircon populations from the same rocks, from the most extensive early rock record comprising the 3.9 Ga to 3.6 Ga terranes of southwest Greenland. These data reveal repeated patterns of formation of juvenile TTG crust and associated mafic and ultramafic rocks in convergent margin settings followed by formation of more evolved granites [1]. Our new zircon Lu-Hf data from rare 3.6-3.7 Ga tonalites within the Itsaq Gneiss Complex, obtained from single component, non-migmatitic gneisses with simple zircon populations, limited within sample Hf isotopic variability and accurate U-Pb ages, now document extraction of juvenile tonalites from a near chondritic mantle source between 3.9 Ga and 3.6 Ga. The more evolved, granitic rocks in each area show slightly negative initial ɛHf in accord with crustal reworking of the older (3.8-3.9 Ga) gniesses. There is no evidence for Hadean material in the sources of the granitoids. The Hf isotope-time patterns are consistent with juvenile crust production from a mantle source that experienced only modest amounts of prior crustal extraction. They are distinct from those predicted by reprocessing of an enriched Hadean mafic crust, as has been proposed for this region [2] and for the source of the Hadean Jack Hills zircons [3]. The well-documented, time decreasing, positive 142Nd anomalies [e.g., 4] from these rocks are further evidence of crustal derivation from a convecting mantle source, rather than reworking of an enriched mafic lithosphere. The 143Nd isotopic -time patterns are more complex, reflecting the interplay between early Sm/Nd fractionation processes as required by the 142Nd data, juvenile crustal growth and in some cases geologic disturbance of the whole rock Sm-Nd system. [1] Nutman, et al, (2013) Amer. Jour. Sci. 313, 877-911. [2] Naeraa et al.. (2012) Nature 485, 627-631. [3] Kemp et al., (2010) EPSL 296, 45-56. [4] Bennett et al., (20070 Science 318, 1907.

Characterizing the Noble Gas Isotopic Composition of the Barnett Shale and Strawn Group and Constraining the Source of Stray Gas in the Trinity Aquifer, North-Central Texas.

PubMed

Wen, Tao; Castro, M Clara; Nicot, Jean-Philippe; Hall, Chris M; Pinti, Daniele L; Mickler, Patrick; Darvari, Roxana; Larson, Toti

2017-06-06

This study presents the complete set of stable noble gases for Barnett Shale and Strawn Group production gas together with stray flowing gas in the Trinity Aquifer, Texas. It places new constraints on the source of this stray gas and further shows that Barnett and Strawn gas have distinct crustal and atmospheric noble gas signatures, allowing clear identification of these two sources. Like stray gas, Strawn gas is significantly more enriched in crustal 4 He*, 21 Ne*, and 40 Ar* than Barnett gas. The similarity of Strawn and stray gas crustal noble gas signatures suggests that the Strawn is the source of stray gas in the Trinity Aquifer. Atmospheric 22 Ne/ 36 Ar ratios of stray gas mimic also that of Strawn, further reinforcing the notion that the source of stray gas in this aquifer is the Strawn. While noble gas signatures of Strawn and stray gas are consistent with a single-stage water degassing model, a two-stage oil modified groundwater exsolution fractionation model is required to explain the light atmospheric noble gas signature of Barnett Shale production gas. These distinct Strawn and Barnett noble gas signatures are likely the reflection of distinct evolution histories with Strawn gas being possibly older than that of Barnett Shale.

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.

Sr, Nd, and Pb isotopes of ultramafic xenoliths in volcanic rocks of Eastern China: enriched components EMI and EMII in subcontinental lithosphere

USGS Publications Warehouse

Tatsumoto, M.; Basu, A.R.; Wankang, H.; Junwen, W.; Guanghong, X.

1992-01-01

The UThPb, SmNd, and RbSr isotopic systematics of mafic and ultramafic xenolithic rocks and associated megacrystic inclusions of aluminous augite and garnet, that occur in three alkalic volcanic suites: Kuandian in eastern Liaoning Province, Hanluoba in Hebei Province, and Minxi in western Fujian Province, China are described. In various isotopic data plots, the inclusion data invariably fall outside the isotopic ranges displayed by the host volcanic rocks, testifying to the true xenolithic nature of the inclusions. The major element partitioning data on Ca, Mg, Fe, and Al among the coexisting silicate minerals of the xenoliths establish their growth at ambient mantle temperatures of 1000-1100??C and possible depths of 70-80 km in the subcontinental lithosphere. Although the partitioning of these elements reflects equilibrium between coexisting minerals, equilibria of the Pb, Nd, and Sr isotopic systems among the minerals were not preserved. The disequilibria are most notable with respect to the 206Pb 204Pb ratios of the minerals. On a NdSr isotopic diagram, the inclusion data plot in a wider area than that for oceanic basalts from a distinctly more depleted component than MORB with higher 143Nd 144Nd and a much broader range of 87Sr 86Sr values, paralleling the theoretical trajectory of a sea-water altered lithosphere in NdSr space. The garnets consistently show lower ?? and ?? values than the pyroxenes and pyroxenites, whereas a phlogopite shows the highest ?? and ?? values among all the minerals and rocks studied. In a plot of ??207 and ??208, the host basalts for all three areas show lower ??207 and higher ??208 values than do the xenoliths, indicating derivation of basalts from Th-rich (relative to U) sources and xenoliths from U-rich sources. The xenolith data trends toward the enriched mantle components, EMI and EMII-like, characterized by high 87Sr 86Sr and ??207 values but with slightly higher 143Nd 144Nd. The EMI trend is shown more distinctly by the host basalts. The EMII mantle domain may be present in the Chinese continental lithosphere just above the EMI domain of the basalt source at the lower part of the lithosphere. We argue that the ancient depleted continental lithosphere was metasomatized, imparting the EMI signature, in earlier times ( > 1000 m.y.), and U migrated upward, resulting in high Th U ratios in the lower portion of the lithosphere. Observed high Th U, Rb Sr, 87Sr 86Sr and ??208, low Sm Nd ratios, and a large negative ??Nd in phlogopite pyroxenite with a depleted mantle model age of 2.9 Ga, support our contention that metasomatized continental lower mantle lithosphere is the source for the EMI component. We also suggest that the EMII signature may have been introduced later (less than ??? 500 Ma) by another metasomatic event during the subduction of an oceanic plate, which was partially responsible for some of the observed inter-mineral isotopic disequilibria. ?? 1992.

Le complexe annulaire d'âge Oligocène de l'Achkal (hoggar Central, Sud Algérie) : témoin de la transition au Cénozoïque entre les magmatismes tholéitique et alcalin. Évidences par les isotopes du Sr, Nd et Pb

NASA Astrophysics Data System (ADS)

Maza, Mustapha; Briqueu, Louis; Dautria, Jean-Marie; Bosch, Delphine

1998-08-01

The Achkal Oligocene ring complex cross-cuts the Upper Eocene tholeiitic traps located on the top of the Hoggar swell. The plutonic rocks range from tholeiitic gabbros to alkali essexites, monzonites and syenites, whereas the volcanites are restricted to late peralkaline rhyolites. The affinity change linked to the large isotopic heterogeneities (from EM1 to HIMU) suggests that the parental magmas are issued from two distinct mantle sources, first lithospheric then deeper. The Achkal has recorded the magmatic evolution of the Hoggar hot spot, between Eocene and Miocene.

Consensus structures of the Mo(v) sites of sulfite-oxidizing enzymes derived from variable frequency pulsed EPR spectroscopy, isotopic labelling and DFT calculations.

PubMed

Enemark, John H

2017-10-10

Sulfite-oxidizing enzymes from eukaryotes and prokaryotes have five-coordinate distorted square-pyramidal coordination about the molybdenum atom. The paramagnetic Mo(v) state is easily generated, and over the years four distinct CW EPR spectra have been identified, depending upon enzyme source and the reaction conditions, namely high and low pH (hpH and lpH), phosphate inhibited (P i ) and sulfite (or blocked). Extensive studies of these paramagnetic forms of sulfite-oxidizing enzymes using variable frequency pulsed electron spin echo (ESE) spectroscopy, isotopic labeling and density functional theory (DFT) calculations have led to the consensus structures that are described here. Errors in some of the previously proposed structures are corrected.

Using nitrogen concentration and isotopic composition in lichens to spatially assess the relative contribution of atmospheric nitrogen sources in complex landscapes.

PubMed

Pinho, P; Barros, C; Augusto, S; Pereira, M J; Máguas, C; Branquinho, C

2017-11-01

Reactive nitrogen (Nr) is an important driver of global change, causing alterations in ecosystem biodiversity and functionality. Environmental assessments require monitoring the emission and deposition of both the amount and types of Nr. This is especially important in heterogeneous landscapes, as different land-cover types emit particular forms of Nr to the atmosphere, which can impact ecosystems distinctively. Such assessments require high spatial resolution maps that also integrate temporal variations, and can only be feasibly achieved by using ecological indicators. Our aim was to rank land-cover types according to the amount and form of emitted atmospheric Nr in a complex landscape with multiple sources of N. To do so, we measured and mapped nitrogen concentration and isotopic composition in lichen thalli, which we then related to land-cover data. Results suggested that, at the landscape scale, intensive agriculture and urban areas were the most important sources of Nr to the atmosphere. Additionally, the ocean greatly influences Nr in land, by providing air with low Nr concentration and a unique isotopic composition. These results have important consequences for managing air pollution at the regional level, as they provide critical information for modeling Nr emission and deposition across regional as well as continental scales. Copyright © 2017 Elsevier Ltd. All rights reserved.

Zinc isotope systematics of subduction-zone magmas

NASA Astrophysics Data System (ADS)

Huang, J.; Zhang, X. C.; Huang, F.; Yu, H.

2016-12-01

Subduction-zone magmas are generated by partial melting of mantle wedge triggered by addition of fluids derived from subducted hydrothermally altered oceanic lithosphere. Source of the fluids may be sediment, altered oceanic crust and serpentinized peridotite/serpentinite. Knowledge of the exact fluid source can facilitate our better understanding of the mechanism of fluid flux, element cycling and crust-mantle interaction in subduction zones. Zinc isotopes have the potential to place a constraint on this issue, because (1) Zn has an intermediate mobility during fluid-rock interaction and is enriched in subduction-zone fluids (e.g., Li et al., 2013); (2) sediment, altered oceanic crust and serpentinite have distinct Zn isotopic compositions (Pons et al., 2011); and (3) the mantle has a homogeneous Zn isotope composition (δ66Zn = 0.28 ± 0.05‰, Chen et al., 2013). Thus, the Zn isotopic composition of subduction-zone magmas reflects the characteristics of slab-derived fluids of different sources. Here, high-precision Zn isotope analyses were conducted on igneous rocks from arcs of Central America, Kamchatka, South Lesser Antilles, and Aleutian. One rhyolite with 75.1 wt.% SiO2 and 0.2 wt.% FeOT displays the heaviest δ66Zn value of 0.394‰ (relative to JMC Lyon) that probably results from the crystallization of Fe-Ti oxides during the late-stage differentiation. The rest of rocks have Zn isotopic compositions (0.161 to 0.339‰) similar to or lighter than those of the mantle. In an individual arc, the δ66Zn values of rocks show broad negative correlations with Ba/Th and 87Sr/86Sr ratios, suggesting that the slab-derived fluids should have lighter δ66Zn as well as higher Ba/Th and 87Sr/86Sr ratios relative to the mantle. These features are in accordance with those of serpentinites. Thus, addition of serpentinite-derived 66Zn-depleted fluids into the mantle wedge can explain the declined δ66Zn of subduction-zone magmas. ReferenceChen et al. (2013) EPSL 369-370:34-42; Li et al. (2013) GCA 120:326-362; Pons et al. (2011) PNAS 108:17639-17643.

Chondritic Xenon in the Earth's mantle: new constrains on a mantle plume below central Europe

NASA Astrophysics Data System (ADS)

Caracausi, Antonio; Avice, Guillaume; Bernard, Peter; Furi, Evelin; Marty, Bernard

2016-04-01

Due to their inertness, their low abundances, and the presence of several different radiochronometers in their isotope systematics, the noble gases are excellent tracers of mantle dynamics, heterogeneity and differentiation with respect to the atmosphere. Xenon deserves particular attention because its isotope systematic can be related to specific processes during terrestrial accretion (e.g., Marty, 1989; Mukhopadhyay, 2012). The origin of heavy noble gases in the Earth's mantle is still debated, and might not be solar (Holland et al., 2009). Mantle-derived CO2-rich gases are particularly powerful resources for investigating mantle-derived noble gases as large quantities of these elements are available and permit high precision isotope analysis. Here, we report high precision xenon isotopic measurements in gases from a CO2 well in the Eifel volcanic region (Germany), where volcanic activity occurred between 700 ka and 11 ka years ago. Our Xe isotope data (normalized to 130Xe) show deviations at all masses compared to the Xe isotope composition of the modern atmosphere. The improved analytical precision of the present study, and the nature of the sample, constrains the primordial Xe end-member as being "chondritic", and not solar, in the Eifel mantle source. This is consistent with an asteroidal origin for the volatile elements in Earth's mantle and it implies that volatiles in the atmosphere and in the mantle originated from distinct cosmochemical sources. Despite a significant fraction of recycled atmospheric xenon in the mantle, primordial Xe signatures still survive in the mantle. This is also a demonstration of a primordial component in a plume reservoir. Our data also show that the reservoir below the Eifel region contains heavy-radiogenic/fissiogenic xenon isotopes, whose ratios are typical of plume-derived reservoirs. The fissiogenic Pu-Xe contribution is 2.26±0.28 %, the UXe contribution is negligible, the remainder being atmospheric plus primordial. Our data support the notion that the fraction of plutonium-derived Xe in plume sources (oceanic as well as continental) is higher than in the MORB source reservoir. Hence, the MORB - type reservoirs appear to be well distinguished and more degassed than the plume sources (oceanic as well as continental) supporting the heterogeneity of Earth's mantle. Finally this study highlights that xenon isotopes in the Eifel gas have preserved a chemical signature that is characteristic of other mantle plume sources. This is very intriguing because the presence of a mantle plume in this sector of Central Europe was already inferred from geophysical and geochemical studies(Buikin et al., 2005; Goes et al., 1999). Notably, tomographic images show a low-velocity structure down to 2000 km depth, representing deep mantle upwelling under central Europe, that may feed smaller upper-mantle plumes (Eifel volcanic district-Germany). References Buikin A., Trieloff M., HoppJ., Althaus T., Korochantseva E., Schwarz W.H. &Altherr R., (2005), Noble gas isotopessuggestdeepmantleplume source of late Cenozoicmaficalkalinevolcanism in Europe, Earth Planet. Sci. Lett. 230, 143-162. Goes S., Spakman W. &BijwaardH., (1999), A lowermantle source for centraleuropeanvolcanism, Science, 286, 1928-1931.G. Holland, M. Cassidy, C.J. Ballentine, Meteorite Kr in the Earth's mantle suggests a late accretionary source for the atmosphere, Science, 326, 1522-1525, (2009). Marty, B. Neon and xenon isotopes in MORB: implications for the Earth-atmosphere evolution. Earth Planet. Sci. Lett. 94, 45-56 (1989). Mukhopadhyay S., Early differentiation and volatile accretion recorded in deep-mantle neon and xenon Nature, 486, 101-106, (2013).

Compound-specific carbon isotope analysis of instantaneous gas generated from shaly coal during hydrous pyrolysis

NASA Astrophysics Data System (ADS)

Tsai, Wen-Yu; Sun, Chih-Hsien; Huang, Wuu-Liang

2010-05-01

Isotopes of natural gases have provided important information for indicating their maturation, origins and influencing factors during the generation processes. In order to distinguish compositions of gas generated at different intervals of maturities, the present study investigates the variation of compound-specific carbon isotope (CSI) ratios of hydrocarbon gases from a shaly coal by instantaneous hydrous pyrolysis, during which the earlier generated gas was evacuated before the start of next maturation stage. The experiments were conducted at ten different maturity stages (0.65 to 2.02 % Ro) from a terrestrial shaly coal with 0.48 % Ro. The gas products were analyzed by GC-IR-MS. The results show that, in general, the δ13C values of methane (C1), ethane (C2), propane (C3) slightly increase, then decrease and finally increase with increasing maturities. This reverse phenomenon indicates the heterogeneous and complex compositions of the kerogen. The isotope compositions of gases exhibit three distinct clusters in natural gas plot of δ13C values versus 1/n (where n is carbon number of the gaseous molecule), corresponding to three different groups of maturity stages. By linking the same maturity stage of δ13C values, all lines show nearly parallel in each group with consistently reverse trend of δ13C3 < δ13C2 > δ13C1. These three distinct clusters were also observed in the cross plotting of iC4/nC4 versus iC5/nC5 isomer ratios. This may imply that the kerogen is composed of three discrete structural domains which were progressively cracked at three major groups of maturity stages. The reverse trend was inconsistent with data for gas collected cumulatively in most prior pyrolysis experiments and the linear relationship predicted from kinetic isotope effect (KIE) model. Although the non-linear relationship or reverse trend, δ13C3 < δ13C2, was also reported for some natural gases, it was interpreted as a result of mixing from different source rocks or other processes. Our results, however, suggest that this non-linear relationship or reverse phenomenon can also be attributed to the mixing of gases generated from different maturity stages solely from a single source formation. Therefore, our results provide a new interpretation for the variation of isotope data of the cumulative and instantaneous gases in hydrous pyrolysis experiments and isotope variation in natural gas.

Temporal and Spatial Variability in the Geochemistry of Axial and CoAxial Segment Lavas and their Mantle Sources

NASA Astrophysics Data System (ADS)

Smith, M. C.; Perfit, M. R.; Davis, C.; Kamenov, G. D.

2011-12-01

Three spatially related volcanic eruptions along the CoAxial Segment of the Juan de Fuca Ridge (JdFR) have documented emplacements between 1981 and 1993. Two of the historic flows outcrop at the "Flow Site" and were emplaced within less than 12 years and 500 m from one another. The third was emplaced at the "Floc Site" to the south in the 1980s. Previous studies have documented that CoAxial lavas are among the most incompatible element and isotopically depleted lavas along the entire JdFR, whereas the Axial Seamount segment immediately south of CoAxial has erupted the most chemically enriched lavas south of the Endeavor Segment. Geochemical studies have shown little temporal change in the chemistry of recent Axial Seamount eruptives, whereas CoAxial lavas exhibit distinct chemical differences over short time periods. Significant chemical differences observed among depleted CoAxial lavas emplaced close to one another in space and time are in marked contrast to the relatively constant chemical characteristics of enriched lavas erupted at the magmatically more robust Axial segment only 10's of kilometers to the south and west. New trace element and isotopic (Sr, Nd, Pb) geochemical analyses of historic and older CoAxial lavas have resulted in better documentation of interflow and intraflow chemical variation providing an improved understanding of spatial/temporal chemical variability in lavas, and further insight into JdFR magmatic processes. Modeling of major and trace element abundances suggest that the observed intraflow chemical variation within CoAxial lavas is largely due to shallow-level fractional crystallization but that a single fractional crystallization model cannot account for all interflow chemical variation. In fact, elemental and isotopic data require different parental magmas for each of the three recent CoAxial Segment lava flows suggesting very short-term differences or changes in the chemical character of the mantle source region. In particular, the 1980's Flow Site parental magma may have formed at higher pressures and due to smaller extents of melting than those magmas that erupted just over a decade later. A comparative analysis of the chemistry of CoAxial segment lavas with that of lavas from nearby seamounts, including Axial Seamount, and ridge segments show that much (though not all) of the data conforms well to binary mixing arrays, suggesting that many of the parental lavas from this region of the JdFR can be formed from variable amounts of mixing of two or more distinct mantle end-member sources. In addition to one or more depleted mantle (DM) sources, regional isotopic data also likely suggest a high U/Pb (HIMU) source component within the region of mantle melt generation. For most lavas strong correlations exist between long-lived radiogenic isotopes and ratios of the abundances of highly incompatible elements, suggesting that mantle heterogeneities sampled are ancient, however, in some cases elemental data is decoupled from the radiogenic isotope data indicating more recent depletion events.

Spatial and temporal variation in the stable isotope composition (δ18O and δ2H) of rain across the tropical island of Sri Lanka.

PubMed

Edirisinghe, E A N V; Pitawala, H M T G A; Dharmagunawardhane, H A; Wijayawardane, R L

2017-12-01

Seasonal and spatial variation in δ 18 O and δ 2 H in rainwater was determined in three selected transects across Sri Lanka, the tropical island in the Indian Ocean. Local meteoric water lines (LMWLs) for three distinguished climatic zones; wet, dry and intermediate were constructed. LMWLs show slight variations in their gradients and respective d-excess values, depending on the air moisture origin, circulation and environmental conditions of each climatic zone. The elevation effect and amount effect could be identified but the continental effect is not significantly seen in the isotope composition of rain in the concerned areas. The results reasonably revealed that the distinct rainfall regimes; two monsoonal rains and two convectional (inter-monsoon) rains have characteristic isotopic signatures. Also the impact of (i) terrestrial and oceanic moisture sources, (ii) depression and cyclonic conditions of the Bay of Bengal, and (iii) topography of the country on the variation of the isotopic composition of rain in Sri Lanka could be satisfactorily identified.

Isotopic ratio and vertical distribution of radionuclides in soil affected by the accident of Fukushima Dai-ichi nuclear power plants.

PubMed

Fujiwara, Takeshi; Saito, Takumi; Muroya, Yusa; Sawahata, Hiroyuki; Yamashita, Yuji; Nagasaki, Shinya; Okamoto, Koji; Takahashi, Hiroyuki; Uesaka, Mitsuru; Katsumura, Yosuke; Tanaka, Satoru

2012-11-01

The results of γ analyses of soil samples obtained from 50 locations in Fukushima prefecture on April 20, 2011, revealed the presence of a spectrum of radionuclides resulted from the accident of the Fukushima Dai-ichi nuclear power plant (FDNPP). The sum γ radioactivity concentration ranged in more than 3 orders of magnitude, depending on the sampling locations. The contamination of soils in the northwest of the FDNPP was considerable. The (131)I/(137)Cs activity ratios of the soil samples plotted as a function of the distance from the F1 NPPs exhibited three distinctive patterns. Such patterns would reflect not only the different deposition behaviors of these radionuclides, but also on the conditions of associated release events such as temperature and compositions and physicochemical forms of released radionuclides. The (136)Cs/(137)Cs activity ratio, on the other hand, was considered to only reflect the difference in isotopic compositions of source materials. Two locations close to the NPP in the northwest direction were found to be depleted in short-lived (136)Cs. This likely suggested the presence of distinct sources with different (136)Cs/(137)Cs isotopic ratios, although their details were unknown at present. Vertical γ activity profiles of (131)I and (137)Cs were also investigated, using 20-30 cm soil cores in several locations. About 70% or more of the radionuclides were present in the uppermost 2-cm regions. It was found that the profiles of (131)I/(137)Cs activity ratios showed maxima in the 2-4 cm regions, suggesting slightly larger migration of the former nuclide. Copyright © 2012 Elsevier Ltd. All rights reserved.

Isotope partitioning of soil respiration: A Bayesian solution to accommodate multiple sources of variability

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

Ogle, Kiona; Pendall, Elise

Isotopic methods offer great potential for partitioning trace gas fluxes such as soil respiration into their different source contributions. Traditional partitioning methods face challenges due to variability introduced by different measurement methods, fractionation effects, and end-member uncertainty. To address these challenges, we describe in this paper a hierarchical Bayesian (HB) approach for isotopic partitioning of soil respiration that directly accommodates such variability. We apply our HB method to data from an experiment conducted in a shortgrass steppe ecosystem, where decomposition was previously shown to be stimulated by elevated CO 2. Our approach simultaneously fits Keeling plot (KP) models to observationsmore » of soil or soil-respired δ 13C and [CO 2] obtained via chambers and gas wells, corrects the KP intercepts for apparent fractionation (Δ) due to isotope-specific diffusion rates and/or method artifacts, estimates method- and treatment-specific values for Δ, propagates end-member uncertainty, and calculates proportional contributions from two distinct respiration sources (“old” and “new” carbon). The chamber KP intercepts were estimated with greater confidence than the well intercepts and compared to the theoretical value of 4.4‰, our results suggest that Δ varies between 2 and 5.2‰ depending on method (chambers versus wells) and CO 2 treatment. Because elevated CO 2 plots were fumigated with 13C-depleted CO 2, the source contributions were tightly constrained, and new C accounted for 64% (range = 55–73%) of soil respiration. The contributions were less constrained for the ambient CO 2 treatments, but new C accounted for significantly less (47%, range = 15–82%) of soil respiration. Finally, our new HB partitioning approach contrasts our original analysis (higher contribution of old C under elevated CO 2) because it uses additional data sources, accounts for end-member bias, and estimates apparent fractionation effects.« less

Human drinking water compared with river waters throughout the United States with respect to their stable hydrogen and oxygen isotopic composition

NASA Astrophysics Data System (ADS)

Landwehr, J. M.; Coplen, T. B.; Qi, H.

2009-04-01

The composition of stable isotopes of hydrogen (^2H) and oxygen (^18O) in animal tissues, such as hair, nail, teeth and bone, has been used to trace migrations and geographic origin of individuals. Variations of these isotopic ratios in tissue are known to show significant correlations with the isotopic composition of ingested water, as well as with diet and other oxygen sources. Drinking water in natural ecosystems is defined by what is locally available for animal consumption, primarily surface waters such as streams, ponds, lakes, seeps, springs, etc. Tap water provides the drinking water in many human ecosystems. It may derive from local sources but can also draw on more diverse sources, such as large rivers with watersheds larger than those of local creeks, deep ground waters or even imported supplies, which may be isotopically distinct from local ecosystem supplies. Because of the potentially complex hydrologic pathways of water sources available in either animal or human ecosystems, the stable isotopic composition of these supplies may differ significantly from that of the (weighted average) local precipitation which is sometimes used to represent local water supplies. For example, water samples taken from three different taps in Washington, D.C., USA, on August 15, 2007, had measured ^2H and ^18O values of -41.7 per mill and -6.13 per mill, -41.7 per mill and -6.06 per mill, and -42.2 per mill and -6.22 per mill, respectively. A water sample taken on the same day from the Potomac River, which is the source of the D.C. water supply, had ^2H and ^18O values of -41.7 per mill and -6.06 per mill, respectively, consistent with that of the urban tap water. However, precipitation samples collected locally in Reston, Virginia, USA, had ^2H and ^18O values of -16.1 per mill and -3.13 per mill, respectively, for the week ending on August 15, 2007; -17.5 per mill and -3.40 per mill, respectively, for the month preceding August 15, 2007; and -13.6 per mill and -3.39 per mill, respectively, for the average values for the month of August over three years. The isotopic composition of local precipitation was significantly more positive than that for the concurrently available tap water and the river water from which it was drawn. Thus, in order to allow valid geographic inferences for forensic purposes, it is necessary to have available the measured isotopic composition of drinking waters or of their appropriate sources. We have now collected tap water samples concurrently at 345 sites throughout the United States and measured ^2H and ^18O during both summer (2007) and winter (2008) seasons. Since large rivers are frequently the source of urban water supplies, we compare this information with data published for rivers and streams throughout the United States (Coplen and Kendall, 2000). These data and analyses should inform the use of stable isotopes of water for forensic determinations.

Intracellular Cadmium Isotope Fractionation

NASA Astrophysics Data System (ADS)

Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.

2011-12-01

Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

New stable isotope results for reservoir and above zone monitoring in CCS from the Ketzin pilot site, Germany

NASA Astrophysics Data System (ADS)

Nowak, Martin; van Geldern, Robert; Myrttinen, Anssi; Veith, Becker; Zimmer, Martin; Barth, Johannes

2013-04-01

With rising atmospheric greenhouse gas concentrations, CCS technologies are a feasible option to diminish consequences of uncontrolled anthropogenic CO2 emissions and related climate change. However, application of CCS technologies requires appropriate and routine monitoring tools in order to ensure a safe and effective CO2 injection. Stable isotope techniques have proven as a useful geochemical monitoring tool at several CCS pilot projects worldwide. They can provide important information about gas - water - rock interactions, mass balances and CO2 migration in the reservoir and may serve as a tool to detect CO2 leakage in the subsurface and surface. Since the beginning of injection in 2008 at the Ketzin pilot site in Germany, more than 450 samples of fluids and gases have been analysed for their carbon and oxygen isotopic composition. Analytical advancements were achieved by modifying a conventional isotope ratio mass-spectrometer with a He dilution system. This allowed analyses of a larger number of CO2 gas samples from the injection well and observation wells. With this, a high-resolution monitoring program was established over a time period of one year. Results revealed that two isotopical distinct kinds of CO2 are injected at the Ketzin pilot site. The most commonly injected CO2 is so-called 'technical' CO2 with an average carbon isotopic value of about -31 ‰. Sporadically, natural source CO2 with an average δ13C value of -3 ‰ was injected. The injection of natural source CO2 generated a distinct isotope signal at the injection well that can be used as an ideal tracer. CO2 isotope values analysed at the observation wells indicate a highly dispersive migration of the supercritical CO2 that results in mixing of the two kinds of CO2 within the reservoir. Above-reservoir monitoring includes the first overlying aquifer above the cap rock. An observation well within this zone comprises an U-tube sampling device that allows frequent sampling of unaltered brine. The fluids were analysed among others for their carbon isotopic compositions of dissolved inorganic carbon (DIC). δ13CDIC values allowed to assess impacts of the carbonate-based drilling fluid during well development and helped to monitor successive geochemical re-equilibration processes of the brine. Based on the determined δ13C baseline values of the aquifer fluid, first concepts indicate the scale of change of the δ13CDIC values that would be necessary to detect CO2 leakage from the underlying storage reservoir. Recent efforts aim at applications of new laser-based isotope sensors that allow online measurements in the field. These devices are applied for CO2 gas tracer experiments as well as for monitoring of isotope composition of soil gases in the vicinity of the pilot site. This new development will allow much better temporal and spatial resolution of measurements at a lower price. Therefore, stable isotope analyses can become a strong and promising tool for subsurface as well as surface monitoring at future CCS sites.

"Fingerprinting" Vehicle Derived Ammonia Utilizing Nitrogen Stable Isotopes

NASA Astrophysics Data System (ADS)

Walters, W.; Hastings, M. G.; Colombi, N. K.

2017-12-01

Ammonia (NH3) is the primary alkaline molecule in the atmosphere and plays a key role in numerous atmospheric processes that have important implications for human health and climate control. While agriculture activities dominate the global NH3 budget, there are large uncertainties in the urban NH3 emission inventories. The analysis of the nitrogen stable isotope composition of NH3 (δ15N-NH3) might be a useful tool for partitioning NH3 emission sources, as different emission sources tend to emit NH3 with distinctive δ15N signatures or "fingerprints". This novel tool may help improve upon urban emission inventories, which could help to improve modeling of important atmospheric processes involving NH3. However, there is a current lack of δ15N-NH3 measurements of potentially important urban NH3 emission sources, and many of the reported NH3 collection methods have not been verified for its ability to accurately characterize δ15N-NH3. Here we present a laboratory tested method to accurately measure δ15N-NH3 using honeycomb denuders coated with a 2% citric acid solution. Based on laboratory tests, the NH3 collection device has been optimized under a variety of conditions. Near quantitative NH3 collection is found at a sampling rate of 10 SLPM for NH3 concentrations less than 2 ppmv, and δ15N-NH3 precision is found to be approximately 1.0‰. This newly developed NH3 collection device for isotopic characterization has been applied to improve our understanding of the δ15N-NH3 signatures from vehicles. Preliminary results of NH3 collected near a road-side indicate an average δ15N-NH3 of -2.1 ± 1.9‰. This work is ongoing, and plans are in place to collect NH3 directly from tailpipes and from on-road air. Our preliminary results indicate that vehicle derived NH3 has a distinctive δ15N signature compared to agricultural and waste emissions; thus, δ15N(NH3) has the potential to be used to understand urban NH3 emission sources.

Stability of the Orca Basin Brine Interface Determined Using Radium Isotopes

NASA Astrophysics Data System (ADS)

Peterson, R. N.; Peterson, L.; Montoya, J. P.; Joye, S. B.

2016-02-01

The Orca Basin is an intraslope basin in the northern continental slope of the Gulf of Mexico, and contains a deep (up to 220 m) anoxic, hypersaline brine lake. The brine interface extends from ocean salinity (at a water depth of 2125 m) to a constant salinity of 215 psu below a depth of 2250 m. This interface is considered to be among the most stable interfaces on the planet, and contains distinct zones of macrofaunal and microbial assemblages. The brine lake is supported by continued dissolution of exposed rock salt at an estimated rate of 0.5 million t/yr. Such dissolution of salt should serve as a source of radium isotopes, and given their range of half-lives, these isotopes can serve as unique proxies to the location and rate of salt dissolution into this basin. We have collected a series of radon and radium isotope profiles through this brine lake over the past 4 years, which allow us to assess the spatial and temporal stability of this interface. Throughout the brine lake, we observe strong enrichments in unsupported Ra-224, Rn-222, and Ra-226 in a 10 m thick zone near the base of the brine interface, between 2232 m and 2242 m. The strong enrichment in unsupported Ra-224 in this layer must be supported by a continuous source, presumably the dissolution of exposed salt rock. Various degrees of isotopic enrichment throughout the lake provide an assessment of the rates of lateral and vertical dispersion of salt and associated chemical constituents.

A Chlorine-Centric Perspective on Fluid-Mediated Processes at Convergent Plate Boundaries

NASA Astrophysics Data System (ADS)

Selverstone, J.

2014-12-01

The release and migration of metamorphic fluids from subducting slabs into overlying mantle is widely recognized as a major mechanism in producing arc geochemical signatures and returning fluid-mobile elements to earth's crust and surface environments. Although the magnitudes of many geochemical fluxes are well constrained, the processes whereby mass transfer occurs in different portions of the subduction system are less well known. Chlorine stable isotopes provide a new perspective on some of these processes: Cl is hydrophilic, but decarbonation reactions favor Cl retention in minerals. Cl also shows less isotopic fractionation than other fluid-sensitive systems and may thus preserve evidence of specific fluid sources and/or fluid mixing events. Detailed studies of sedimentary sequences show that individual beds are isotopically homogeneous but large heterogeneities in δ37Cl exist across beds on a cm to m scale and vary as a function of depositional environment. Compositionally correlative medium-, high-, and ultrahigh-pressure metamorphic sequences in the Alps record decreases of 30-50% in Cl contents in the earliest stages of metamorphism, but little change thereafter. No statistically significant change in isotopic composition occurs during prograde metamorphism of individual horizons, and the same large degree of isotopic heterogeneity (up to 6‰) persists throughout the prograde devolatilization history of the rocks. Likewise, analysis of HP/UHP serpentinites and altered oceanic crust show that heterogeneous protolith compositions are preserved during transport to sub-arc depths, despite large-scale devolatilization. However, upward transport of rocks within the subduction channel results in highly localized interaction with isotopically distinct, Cl-bearing fluid packets. Overlying forearc wedge rocks also record heterogeneous and channelized interaction with distinct fluid components with different δ37Cl. Within-layer fluid compartmentalization during continuous devolatilization reactions must thus be reconciled with discontinuous, cross-layer fluid percolation out of the slab and into the wedge. The resulting implications of the chlorine data for recent mechanical models of slab-to-wedge fluid transport will be discussed.

Advances in laser ablation MC-ICPMS isotopic analysis of rock materials

NASA Astrophysics Data System (ADS)

Young, E. D.

2007-12-01

Laser ablation multiple-collector inductively coupled plasma-source mass spectrometry (LA-MC-ICPMS) is a rapid method for obtaining high-precision isotope ratio measurements in geological samples. The method has been used with success for measuring isotope ratios of numerous elements, including Pb, Hf, Mg, Si, and Fe in terrestrial and extraterrestrial samples. It fills the gap between the highest precision obtainable with acid digestion together with MC-ICPMS and thermal ionization mass spectrometry (TIMS) and the maximum spatial resolution afforded by secondary ion mass spectrometry (SIMS). Matrix effects have been shown to be negligible for Pb isotopic analysis by LA-MC-ICPMS (Simon et al., 2007). Glass standards NBS 610, 612, and 614 have Pb/matrix ratios spanning two orders of magnitude. Our sample-standard bracketing laser ablation technique gives accurate and precise 208Pb/206Pb and 207Pb/206Pb for these glasses. The accuracy is superior to that obtained when using Tl to correct for mass fractionation. Accuracy and precision (± 0.2 ‰) for Pb in feldspars is comparable to that for double-spike TIMS. Data like these have been used to distinguish distinct sources of magmas in the Long Valley silicic magma system. LA-MC-ICPMS analyses of Mg isotope ratios in calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrite meteorites have revealed a wealth of new information about the history of these objects. A byproduct of this work has been recognition of the importance of different mass fractionation laws among three isotopes of a given element. Kinetic and equilibrium processes define distinct fractionation laws. Reservoir effects can further modify these laws. The result is that the linear coefficient β that relates the logarithms of the ratios n2/n1 and n3/n1 (ni refers to the number of atoms of isotope i) of isotopes with masses m3 > m2 > m1 is not unique. Rather, it is process dependent. In the case of Mg, this coefficient ranges from 0.521 for single-step equilibrium processes to 0.510 or even lower for kinetic processes. Rayleigh fractionation involving a kinetic process with a single-step β of 0.510 produces an effective β of 0.512. Such differences in fractionation laws can be crucial for determining excesses or deficits in isotopes relative to mass fractionation. Contrary to some assertions, Si isotope ratios can be measured with high accuracy and precision using 193 nm excimer lasers with nanosecond pulse widths (Shahar and Young, 2007). Silicon isotope ratios in CAIs measured by 193 nm LA-MC-ICPMS have been combined with Mg isotope ratios to constrain the astrophysical environments in which these oldest solar system materials formed. Accuracy of the measurements was determined using gravimetric standards of various matrix compositions. The results establish that matrix effects for Si are below detection at the ± 0.2 ‰ precision of the laser ablation technique. High mass resolving power (m/Δ m ~ 9000) is necessary to obtain accurate Si isotope ratios by laser ablation. High-precision LA-MC-ICPMS measurements of 176Hf/177Hf in zircons can be obtained by normalizing to 179Hf/177Hf assuming an exponential fractionation law and no mass-dependent Hf, Lu, or Yb stable isotope fractionation. With corrections for interfering 176Lu and 176Yb precision for this method can be on the order of 0.3 epsilon (0.03 ‰). The approach has been used to infer the existence of continental crust on Earth 4.4 billion years before present (Harrison et al., 2005).

Isotope geochemistry of early Kilauea magmas from the submarine Hilina bench: The nature of the Hilina mantle component

USGS Publications Warehouse

Kimura, Jun-Ichi; Sisson, Thomas W.; Nakano, Natsuko; Coombs, Michelle L.; Lipman, Peter W.

2006-01-01

Submarine lavas recovered from the Hilina bench region, offshore Kilauea, Hawaii Island provide information on ancient Kilauea volcano and the geochemical components of the Hawaiian hotspot. Alkalic lavas, including nephelinite, basanite, hawaiite, and alkali basalt, dominate the earliest stage of Kilauea magmatism. Transitional basalt pillow lavas are an intermediate phase, preceding development of the voluminous tholeiitic subaerial shield and submarine Puna Ridge. Most alkalic through transitional lavas are quite uniform in Sr–Nd–Pb isotopes, supporting the interpretation that variable extent partial melting of a relatively homogeneous source was responsible for much of the geochemical diversity of early Kilauea magmas (Sisson et al., 2002). These samples are among the highest 206Pb/204Pb known from Hawaii and may represent melts from a distinct geochemical and isotopic end-member involved in the generation of most Hawaiian tholeiites. This end-member is similar to the postulated literature Kea component, but we propose that it should be renamed Hilina, to avoid confusion with the geographically defined Kea-trend volcanoes. Isotopic compositions of some shield-stage Kilauea tholeiites overlap the Hilina end-member but most deviate far into the interior of the isotopic field defined by magmas from other Hawaiian volcanoes, reflecting the introduction of melt contributions from both “Koolau” (high 87Sr/86Sr, low 206Pb/204Pb) and depleted (low 87Sr/86Sr, intermediate 206Pb/204Pb) source materials. This shift in isotopic character from nearly uniform, end-member, and alkalic, to diverse and tholeiitic corresponds with the major increase in Kilauea's magmatic productivity. Two popular geodynamic models can account for these relations: (1) The upwelling mantle source could be concentrically zoned in both chemical/isotopic composition, and in speed/extent of upwelling, with Hilina (and Loihi) components situated in the weakly ascending margins and the Koolau component in the interior. The depleted component could be refractory and spread throughout or scavenged from the overlying lithosphere. (2) The Hilina (and Loihi) components could be a more fertile material (lower melting temperature) spread irregularly throughout the Hawaiian source in a matrix of more refractory depleted and Koolau compositions. Modest upwelling along the leading hotspot margin melts the fertile domains predominantly, while the refractory matrix also partially melts in the more vigorously upwelling hotspot interior, diluting the Hilina and Loihi components and yielding voluminous isotopically diverse tholeiitic magmas.

Food-web dynamics and isotopic niches in deep-sea communities residing in a submarine canyon and on the adjacent open slopes

USGS Publications Warehouse

Demopoulos, Amanda W.J.; McClain-Counts, Jennifer; Ross, Steve W.; Brooke, Sandra; Mienis, Furu

2017-01-01

Examination of food webs and trophic niches provide insights into organisms' functional ecology, yet few studies have examined trophodynamics within submarine canyons, where the interaction of canyon morphology and oceanography influences habitat provision and food deposition. Using stable isotope analysis and Bayesian ellipses, we documented deep-sea food-web structure and trophic niches in Baltimore Canyon and the adjacent open slopes in the US Mid-Atlantic Region. Results revealed isotopically diverse feeding groups, comprising approximately 5 trophic levels. Regression analysis indicated that consumer isotope data are structured by habitat (canyon vs. slope), feeding group, and depth. Benthic feeders were enriched in 13C and 15N relative to suspension feeders, consistent with consuming older, more refractory organic matter. In contrast, canyon suspension feeders had the largest and more distinct isotopic niche, indicating they consume an isotopically discrete food source, possibly fresher organic material. The wider isotopic niche observed for canyon consumers indicated the presence of feeding specialists and generalists. High dispersion in δ13C values for canyon consumers suggests that the isotopic composition of particulate organic matter changes, which is linked to depositional dynamics, resulting in discrete zones of organic matter accumulation or resuspension. Heterogeneity in habitat and food availability likely enhances trophic diversity in canyons. Given their abundance in the world's oceans, our results from Baltimore Canyon suggest that submarine canyons may represent important havens for trophic diversity.

Stable mercury isotope ratios as tracers for Hg cycling at the inoperative New Idria Hg mine, California

NASA Astrophysics Data System (ADS)

Wiederhold, J. G.; Jew, A. D.; Brown, G. E.; Bourdon, B.; Kretzschmar, R.

2010-12-01

The seven stable isotopes of Hg are fractionated in the environment as a result of mass-dependent (MDF) and mass-independent (MIF) fractionation processes that can be studied in parallel by analyzing the ratios of even and odd mass Hg isotopes. MDF and MIF Hg isotope signatures of natural samples may provide a new tool to trace sources and transformations in environmental Hg cycling. However, the mechanisms controlling the extent of kinetic and equilibrium Hg isotope fractionations are still only partially understood. Thus, development of this promising tracer requires experimental calibration of relevant fractionation factors as well as assessment of natural variations of Hg isotope ratios under different environmental conditions. The inoperative Hg mine in New Idria (California, USA) represents an ideal case study to explore Hg isotope fractionation during Hg transformation and transport processes. More than a century of Hg mining and on-site thermal refining to obtain elemental Hg until 1972 produced large volumes of contaminated mine wastes which now represent sources of Hg pollution for the surrounding ecosystems. Here, we present Hg isotope data from various materials collected at New Idria using Cold-Vapor-MC-ICPMS with a long-term δ202Hg reproducibility of ±0.1‰ (2SD). Uncalcined mine waste samples were isotopically similar to NIST-3133 and did not exhibit any MIF signatures. In contrast, calcine samples, which represent the residue of the thermal ore processing at 700°C, had significantly heavier δ202Hg values of up to +1.5‰. In addition, we observed small negative MIF anomalies of the odd-mass Hg isotopes in the calcine samples, which could be caused either by nuclear volume fractionation or a magnetic isotope effect during or after the roasting process. The mass-dependent enrichment of heavy Hg isotopes in the calcine materials indicates that light Hg isotopes were preferentially removed during the roasting process, in agreement with a previous study by Stetson et al. (ES&T, 2009, 43:7331-7336). In order to further elucidate the Hg isotope signatures of the New Idria samples, we performed a three-step sequential extraction procedure to separate different Hg pools. The calcine samples exhibited a higher proportion of leachable Hg phases compared with the unrefined ore waste samples. The most soluble Hg pool (HAc/HCl, pH 2) had a significantly heavier MDF and more negative MIF signature than the bulk calcine samples, suggesting that the dissolution of more soluble Hg phases from calcine materials results in an enhanced flux of leached Hg which is isotopically distinct from the original ore. Moreover, this finding demonstrates that the Hg isotope fractionation during the ore roasting cannot be solely explained by a kinetic Rayleigh-type process which removes light Hg isotopes, but must additionally involve the formation of isotopically heavy secondary Hg phases in the calcine. The analysis of additional samples will enable us to test this hypothesis and to gain further insights into the applicability of stable Hg isotope ratios as source and process tracers in Hg-contaminated environments.

Plate tectonics 2.5 billion years ago: evidence at kolar, South India.

PubMed

Krogstad, E J; Balakrishnan, S; Mukhopadhyay, D K; Rajamani, V; Hanson, G N

1989-03-10

The Archean Kolar Schist Belt, south India, is a suture zone where two gneiss terranes and at least two amphibolite terranes with distinct histories were accrted. Amphibolites from the eastern and western sides of the schist belt have distinct incompatible element and isotopic characteristics sugesting that their volcanic protoliths were derived from dint mantle sources. The amphibolite and gneiss terranes were juxtaposed by horizontal compression and shearing between 2530 and 2420 million years ago (Ma) along a zone marked by the Kolar Schist Belt. This history of accretion of discrete crustal terranes resembles those of Phanerozoic convergent margins and thus suggests that plate tectonics operated on Earth by 2500 Ma.

Plate tectonics 2.5 billion years ago - Evidence at Kolar, south India

NASA Technical Reports Server (NTRS)

Krogstad, E. J.; Hanson, G. N.; Balakrishnan, S.; Rajamani, V.; Mukhopadhyay, D. K.

1989-01-01

The Archean Kolar Schist Belt, south India, is a suture zone where two gneiss terranes and at least two amphibolite terranes with distinct histories were accreted. Amphibolites from the eastern and western sides of the schist belt have distinct incompatible element and isotopic characteristics suggesting that their volcanic protoliths were derived from different mantle sources. The amphibolite and gneiss terranes were juxtaposed by horizontal compression and shearing between 2530 and 2420 million years ago (Ma) along a zone marked by the Kolar Schist Belt. This history of accretion of discrete crustal terranes resembles those of Phanerozoic convergent margins and thus suggests that plate tectonics operated on earth by 2500 Ma.

U-Series Disequilibria across the New Southern Ocean Mantle Province, Australian-Antarctic Ridge

NASA Astrophysics Data System (ADS)

Scott, S. R.; Sims, K. W. W.; Park, S. H.; Langmuir, C. H.; Lin, J.; Kim, S. S.; Blichert-Toft, J.; Michael, P. J.; Choi, H.; Yang, Y. S.

2017-12-01

Mid-ocean ridge basalts (MORB) provide a unique window into the temporal and spatial scales of mantle evolution. Long-lived radiogenic isotopes in MORB have demonstrated that the mantle contains many different chemical components or "flavors". U-series disequilibria in MORB have further shown that different chemical components/lithologies in the mantle contribute differently to mantle melting processes beneath mid-ocean ridges. Recent Sr, Nd, Hf, and Pb isotopic analyses from newly collected basalts along the Australian-Antarctic Ridge (AAR) have revealed that a large distinct mantle province exists between the Australian-Antarctic Discordance and the Pacific-Antarctic Ridge, extending from West Antarctica and Marie Byrd Land to New Zealand and Eastern Australia (Park et al., submitted). This southern mantle province is located between the Indian-type mantle and the Pacific-type mantle domains. U-series measurements in the Southeast Indian Ridge and East Pacific Rise provinces show distinct signatures suggestive of differences in melting processes and source lithology. To examine whether the AAR mantle province also exhibits different U-series systematics we have measured U-Th-Ra disequilibria data on 38 basalts from the AAR sampled along 500 km of ridge axis from two segments that cross the newly discovered Southern Ocean Mantle province. We compare the data to those from nearby ridge segments show that the AAR possesses unique U-series disequilibria, and are thus undergoing distinct mantle melting dynamics relative to the adjacent Pacific and Indian ridges. (230Th)/(238U) excesses in zero-age basalts (i.e., those with (226Ra)/(230Th) > 1.0) range from 1.3 to 1.7, while (226Ra)/(230Th) ranges from 1.0 to 2.3. (226Ra)/(230Th) and (230Th)/(238U) are negatively correlated, consistent with the model of mixing between deep and shallow melts. The AAR data show higher values of disequilibria compared to the Indian and Pacific Ridges, which can be explained by either lower melting rates and porosities, or a higher gt/cpx ratio in their mantle source. That both long-lived radiogenic isotopes and U-series disequilibria are distinct in these three adjacent mantle provinces suggests that lithological differences are strongly influencing the melting process beneath each of these mid-ocean ridges.

Stable-carbon isotope ratios for sourcing the nerve-agent precursor methylphosphonic dichloride and its products

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

Moran, James J.; Fraga, Carlos G.; Nims, Megan K.

The ability to connect a chemical threat agent to a specific batch of a synthetic precursor can provide a fingerprint to contribute to effective forensic investigations. Stable isotope analysis can leverage intrinsic, natural isotopic variability within the molecules of a threat agent to unlock embedded chemical fingerprints in the material. Methylphosphonic dichloride (DC) is a chemical precursor to the nerve agent sarin. It is converted to methylphosphonic difluoride (DF) as part of the sarin synthesis process. We used a suite of commercially available DC stocks to both evaluate the potential for δ13C analysis to be used as a fingerprinting toolmore » in sarin-related investigations and to develop sample preparation techniques (using chemical hydrolysis) that can simplify isotopic analysis of DC and its synthetic products. We demonstrate that natural isotopic variability in DC results in at least three distinct, isotope-resolved clusters within the thirteen stocks we analyzed. Isotopic variability in the carbon feedstock (i.e., methanol) used for DC synthesis is likely inherited by the DC samples we measured. We demonstrate that the hydrolysis of DC and DF to methylphosphonic acid (MPA) can be used as a preparative step for isotopic analysis because the reaction does not impart a measureable isotopic fractionation. MPA is more chemically stable, less toxic, and easier to handle than DC or DF. Further, the hydrolysis method we demonstrated can be applied to a suite of other precursors or to sarin itself, thereby providing a potentially valuable forensic tool.« less

Stable-Carbon Isotope Ratios for Sourcing the Nerve-Agent Precursor Methylphosphonic Dichloride and Its Products

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

Moran, James J.; Fraga, Carlos G.; Nims, Megan K.

The ability to connect a chemical threat agent to a specific batch of a synthetic precursor can provide a fingerprint to contribute to effective forensic investigations. Stable isotope analysis can leverage intrinsic, natural isotopic variability within the molecules of a threat agent to unlock embedded chemical fingerprints in the material. Methylphosphonic dichloride (DC) is a chemical precursor to the nerve agent sarin. DC is converted to methylphosphonic difluoride (DF) as part of the sarin synthesis process. We used a suite of commercially available DC stocks to both evaluate the potential for δ 13C analysis to be used as a fingerprintingmore » tool in sarin-related investigations and to develop sample preparation techniques (using chemical hydrolysis) that can simplify isotopic analysis of DC and its synthetic products. We demonstrate that natural isotopic variability in DC results in at least three distinct, isotope-resolved clusters within the thirteen stocks we analyzed. Isotopic variability in the carbon feedstock (i.e., methanol) used for DC synthesis is likely inherited by the DC samples we measured. Here, we demonstrate that the hydrolysis of DC and DF to methylphosphonic acid (MPA) can be used as a preparative step for isotopic analysis because the reaction does not impart a significant isotopic fractionation. MPA is more chemically stable, less toxic, and easier to handle than DC or DF. Further, the hydrolysis method we demonstrated can be applied to a suite of other precursors or to sarin itself, thereby providing a potentially valuable forensic tool.« less

Stable-Carbon Isotope Ratios for Sourcing the Nerve-Agent Precursor Methylphosphonic Dichloride and Its Products

DOE PAGES

Moran, James J.; Fraga, Carlos G.; Nims, Megan K.

2018-04-01

The ability to connect a chemical threat agent to a specific batch of a synthetic precursor can provide a fingerprint to contribute to effective forensic investigations. Stable isotope analysis can leverage intrinsic, natural isotopic variability within the molecules of a threat agent to unlock embedded chemical fingerprints in the material. Methylphosphonic dichloride (DC) is a chemical precursor to the nerve agent sarin. DC is converted to methylphosphonic difluoride (DF) as part of the sarin synthesis process. We used a suite of commercially available DC stocks to both evaluate the potential for δ 13C analysis to be used as a fingerprintingmore » tool in sarin-related investigations and to develop sample preparation techniques (using chemical hydrolysis) that can simplify isotopic analysis of DC and its synthetic products. We demonstrate that natural isotopic variability in DC results in at least three distinct, isotope-resolved clusters within the thirteen stocks we analyzed. Isotopic variability in the carbon feedstock (i.e., methanol) used for DC synthesis is likely inherited by the DC samples we measured. Here, we demonstrate that the hydrolysis of DC and DF to methylphosphonic acid (MPA) can be used as a preparative step for isotopic analysis because the reaction does not impart a significant isotopic fractionation. MPA is more chemically stable, less toxic, and easier to handle than DC or DF. Further, the hydrolysis method we demonstrated can be applied to a suite of other precursors or to sarin itself, thereby providing a potentially valuable forensic tool.« less

Stable-carbon isotope ratios for sourcing the nerve-agent precursor methylphosphonic dichloride and its products.

PubMed

Moran, James J; Fraga, Carlos G; Nims, Megan K

2018-08-15

The ability to connect a chemical threat agent to a specific batch of a synthetic precursor can provide a fingerprint to contribute to effective forensic investigations. Stable isotope analysis can leverage intrinsic, natural isotopic variability within the molecules of a threat agent to unlock embedded chemical fingerprints in the material. Methylphosphonic dichloride (DC) is a chemical precursor to the nerve agent sarin. DC is converted to methylphosphonic difluoride (DF) as part of the sarin synthesis process. We used a suite of commercially available DC stocks to both evaluate the potential for δ 13 C analysis to be used as a fingerprinting tool in sarin-related investigations and to develop sample preparation techniques (using chemical hydrolysis) that can simplify isotopic analysis of DC and its synthetic products. We demonstrate that natural isotopic variability in DC results in at least three distinct, isotope-resolved clusters within the thirteen stocks we analyzed. Isotopic variability in the carbon feedstock (i.e., methanol) used for DC synthesis is likely inherited by the DC samples we measured. We demonstrate that the hydrolysis of DC and DF to methylphosphonic acid (MPA) can be used as a preparative step for isotopic analysis because the reaction does not impart a significant isotopic fractionation. MPA is more chemically stable, less toxic, and easier to handle than DC or DF. Further, the hydrolysis method we demonstrated can be applied to a suite of other precursors or to sarin itself, thereby providing a potentially valuable forensic tool. Copyright © 2018. Published by Elsevier B.V.

Petrology of Anomalous Mafic Achondrite Polymict Breccia Pasamonte

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Berger, E. L.; Le, L.

2017-01-01

The most common asteroidal igneous meteorites are eucrite-type basalts and gabbros - rocks composed of ferroan pigeonite and augite, calcic plagioclase, silica, ilmenite, troilite, Ca-phosphate, chromite and Fe-metal [1]. These rocks are thought to have formed on a single asteroid, widely considered to be 4 Vesta, along with howardites and diogenites [1, 2]. High precision O-isotopic analyses have shown that some eucrites have small, well-resolved O-isotopic differences from the group mean [3-5]. These Oanomalous eucrites are thought to hail from asteroidal parents that are distinct from that of eucrites [5]. Three O-anomalous eucrites are PCA 82502, PCA 91007 (paired) and Pasamonte, all of which have the same O-isotopic composition [5, 6]. Our petrologic studies have shown that PCA 82502 and PCA 91007 have well-resolved anomalies in low-Ca pyroxene Fe/Mn compared to eucrites [6]. Divalent Mn and Fe are homologous species that do not greatly fractionate during igneous processes; mafic mineral Fe/Mn can be used to fingerprint parent object sources [7]. Previous petrological studies of Pasamonte [8-10] have not yielded sufficiently precise Fe/Mn ratios to allow distinction of anomalies of the scale of those found for the PCA basalts. We have begun petrological study of Pasamonte for comparison with our results on normal and anomalous eucrites [6], and to constrain its origin.

Trophic level and macronutrient shift effects associated with the weaning process in the Postclassic Maya.

PubMed

Williams, Jocelyn S; White, Christine D; Longstaffe, Fred J

2005-12-01

The weaning process was investigated at two Maya sites dominated by Postclassic remains: Marco Gonzalez (100 BC-AD 1350) and San Pedro (1400-AD 1650), Belize. Bone collagen and bioapatite were analyzed from 67 individuals (n < or = 6 years = 15, n > 6 years = 52). Five isotopic measures were used to reconstruct diet and weaning: stable nitrogen- and carbon-isotope ratios in collagen, stable carbon- and oxygen-isotope ratios in bioapatite, and the difference in stable carbon-isotope values of coexisting collagen and bioapatite. Nitrogen-isotope ratios in infant collagen from both sites are distinct from adult females, indicating a trophic level effect. Collagen-to-bioapatite differences in infant bone from both sites are distinct from adult females, indicating a shift in macronutrients. Oxygen-isotope ratios in infant bioapatite from both sites are also distinct from adult females, indicating the consumption of breast milk. Among infants, carbon- and nitrogen-isotope ratios vary, indicating death during different stages in the weaning process. The ethnohistoric and paleopathological literature on the Maya indicate cessation of breast-feeding between ages 3-4 years. Isotopic data from Marco Gonzalez and San Pedro also indicate an average weaning age of 3-4 years. Based on various isotopic indicators, weaning likely began around age 12 months. This data set is not only important for understanding the weaning process during the Postclassic, but also demonstrates the use of collagen-to-bioapatite spacing as an indicator of macronutrient shifts associated with weaning. 2005 Wiley-Liss, Inc.

Interrogating pollution sources in a mangrove food web using multiple stable isotopes.

PubMed

Souza, Iara da C; Arrivabene, Hiulana P; Craig, Carol-Ann; Midwood, Andrew J; Thornton, Barry; Matsumoto, Silvia T; Elliott, Michael; Wunderlin, Daniel A; Monferrán, Magdalena V; Fernandes, Marisa N

2018-06-01

Anthropogenic activities including metal contamination create well-known problems in coastal mangrove ecosystems but understanding and linking specific pollution sources to distinct trophic levels within these environments is challenging. This study evaluated anthropogenic impacts on two contrasting mangrove food webs, by using stable isotopes (δ 13 C, δ 15 N, 87 Sr/ 86 Sr, 206 Pb/ 207 Pb and 208 Pb/ 207 Pb) measured in sediments, mangrove trees (Rhizophora mangle, Laguncularia racemosa, Avicennia schaueriana), plankton, shrimps (Macrobranchium sp.), crabs (Aratus sp.), oysters (Crassostrea rhizophorae) and fish (Centropomus parallelus) from both areas. Strontium and Pb isotopes were also analysed in water and atmospheric particulate matter (PM). δ 15 N indicated that crab, shrimp and oyster are at intermediate levels within the local food web and fish, in this case C. parallelus, was confirmed at the highest trophic level. δ 15 N also indicates different anthropogenic pressures between both estuaries; Vitória Bay, close to intensive human activities, showed higher δ 15 N across the food web, apparently influenced by sewage. The ratio 87 Sr/ 86 Sr showed the primary influence of marine water throughout the entire food web. Pb isotope ratios suggest that PM is primarily influenced by metallurgical activities, with some secondary influence on mangrove plants and crabs sampled in the area adjacent to the smelting works. To our knowledge, this is the first demonstration of the effect of anthropogenic pollution (probable sewage pollution) on the isotopic fingerprint of estuarine-mangrove systems located close to a city compared to less impacted estuarine mangroves. The influence of industrial metallurgical activity detected using Pb isotopic analysis of PM and mangrove plants close to such an impacted area is also notable and illustrates the value of isotopic analysis in tracing the impact and species affected by atmospheric pollution. Copyright © 2018 Elsevier B.V. All rights reserved.

Geochemistry of Intra-Transform Lavas from the Galápagos Transform Fault

NASA Astrophysics Data System (ADS)

Morrow, T. A.; Mittelstaedt, E. L.; Harpp, K. S.

2013-12-01

The Galápagos plume has profoundly affected the development and evolution of the nearby (<250 km) Galápagos Transform Fault (GTF), a ~100km right-stepping offset in the Galápagos Spreading Center (GSC). The GTF can be divided into two sections that represent different stages of transform evolution: the northern section exhibits fully developed transform fault morphology, whereas the southern section is young, and deformation is more diffuse. Both segments are faulted extensively and include numerous small (<0.5km3) monogenetic volcanic cones, though volcanic activity is more common in the south. To examine the composition of the mantle source and melting conditions responsible for the intra-transform lavas, as well as the influence of the plume on GTF evolution, we present major element, trace element, and radiogenic isotope analysis of samples collected during SON0158, EWI0004, and MV1007 cruises. Radiogenic isotope ratio variations in the Galápagos Archipelago require four distinct mantle reservoirs across the region: PLUME, DM, FLO, and WD. We find that Galápagos Transform lavas are chemically distinct from nearby GSC lavas and neighboring seamounts. They have radiogenic isotopic compositions that lie on a mixing line between DM and PLUME, with little to no contribution from any other mantle reservoirs despite their geographic proximity to WD-influenced lavas erupted along the GSC and at nearby (<50km away) seamounts. Within the transform, lavas from the northern section are more enriched in radiogenic isotopes than lavas sampled in the southern section. Transform lavas are anomalously depleted in incompatible trace elements (ITEs) relative to GSC lavas, suggesting unique melting conditions within the transform. Isotopic variability along the transform axis indicates that mantle sources and/or melting mechanisms vary between the northern and southern sections, which may relate to their distances from the plume or the two-stage development and evolution of the Galápagos Transform Fault. We present a melting model that reproduces GTF lava chemistry from a mixture of two partial melts of PLUME and DM. We assume that the DM source has an ITE composition similar to the depleted upper mantle, melting is purely fractional, and lavas do not fractionate during ascent. Solutions were achieved using a Metropolis algorithm and constrained by observed GTF lava chemistry. Model results predict that GTF lavas are produced by a mixture of a ~3%×1% partial melt of the PLUME source and a ~5%×4% partial melt of the DM source. Our model predicts that a larger proportion of PLUME melts contribute to GTF lavas than DM melts. Absence of the WD component and relatively low concentrations of ITEs may indicate that lavas in the GTF are produced from a source that has already undergone partial melting and is being re-melted beneath the TF. Re-melting may be caused by extension across the GTF, or development of the southern section of the GTF via the ~1Ma ridge jump.

A toolkit for determining historical eco-hydrological interactions

NASA Astrophysics Data System (ADS)

Singer, M. B.; Sargeant, C. I.; Evans, C. M.; Vallet-Coulomb, C.

2016-12-01

Contemporary climate change is predicted to result in perturbations to hydroclimatic regimes across the globe, with some regions forecast to become warmer and drier. Given that water is a primary determinant of vegetative health and productivity, we can expect shifts in the availability of this critical resource to have significant impacts on forested ecosystems. The subject is particularly complex in environments where multiple sources of water are potentially available to vegetation and which may also exhibit spatial and temporal variability. To anticipate how subsurface hydrological partitioning may evolve in the future and impact overlying vegetation, we require well constrained, historical data and a modelling framework for assessing the dynamics of subsurface hydrology. We outline a toolkit to retrospectively investigate dynamic water use by trees. We describe a synergistic approach, which combines isotope dendrochronology of tree ring cellulose with a biomechanical model, detailed climatic and isotopic data in endmember waters to assess the mean isotopic composition of source water used in annual tree rings. We identify the data requirements and suggest three versions of the toolkit based on data availability. We present sensitivity analyses in order to identify the key variables required to constrain model predictions and then develop empirical relationships for constraining these parameters based on climate records. We demonstrate our methodology within a Mediterranean riparian forest site and show how it can be used along with subsurface hydrological modelling to validate source water determinations, which are fundamental to understanding climatic fluctuations and trends in subsurface hydrology. We suggest that the utility of our toolkit is applicable in riparian zones and in a range of forest environments where distinct isotopic endmembers are present.

Geochemical and isotopic studies of syenites from the Yamato Mountains, East Antarctica: Implications for the origin of syenitic magmas

NASA Astrophysics Data System (ADS)

Zhao, J.-X.; Shiraishi, K.; Ellis, D. J.; Sheraton, J. W.

1995-04-01

Voluminous syenites were intruded during the waning stage of the granulite facies metamorphism in the Yamato Mountains of East Antarctica. The area has been interpreted as part of a Cambrian continental collision zone with regional upper amphibolite to granulite facies metamorphism occurring during ca. 500-660 Ma period. Regardless of minor geochemical variations between different groups, all syenites are characterised by high K 20 + Na 20 (8-12%), K 20/Na 20 (˜2), Sr (800-3500 ppm), Ba (2000-8500 ppm), and comparatively high TiO 2, P 20 5, Zr, and light REES relative to I-type granites. They are significantly higher in Mg number (50-75) compared with typical calc-alkaline suites, igneous charnockites, or A-type granites and define a distinctive trend on an AFM (alkali-FeO tot-MgO) diagram. Their trace element distribution diagrams are characterised by pronounced enrichment in LIL and REES, large negative Nb and Ti anomalies, and no depletion in Sr or Ba relative to the neighbouring elements. In this regard, they closely resemble the ˜500 Ma post-tectonic mela-syenite to alkali basalt dikes widely occurring in East Antarctica. Such geochemical features are distinct from rift- or hotspot-related syenites, which are usually characterised by low K/Na ratios, negative Ba and Sr anomalies, and a lack of negative Nb anomalies. Initial isotopic compositions of the syenites are characterised by relatively low initial ɛNd values (-2.6 to -5.5) and high Sri ratios (0.7057-0.7088). Since the syenites are extremely enriched in Sr and Nd, such isotopic signatures are interpreted as reflecting the nature of the mantle source, rather than significant crystal contamination. Such isotopic signatures are also distinct from those of the rift- or hotspot-related syenites which are thought to be derived from depleted asthenospheric mantle. Considering the distinctive geochemical signatures of the Yamato syenites and their analogy to posttectonic alkaline mafic dikes in Antarctica, it is proposed that the syenites were generated by fractionation and magma mixing (with a crystal melt) of a Si-undersaturated alkali basaltic magma in a lower-crust magma chamber, followed by further crystal fractionation/cumulate-melt unmixing at middle to upper crustal levels (<5 kbars). Tectonically, it is proposed that the syenites were probably formed within the hinterland of the proposed Cambrian continental collision zone, with the parental magma being derived ultimately by partial melting of the metasomatised mantle wedge above the deepest part of the subduction zone. Similar models may also apply to the origin of some post-tectonic alkaline dikes in East Antarctica, with their sources being the continental lithospheric mantle previously modified by subduction-related processes.

Plan of study to determine if the isotopic ratios [delta]15 N and [delta]18 O can reveal the sources of nitrate discharged by the Mississippi River into the Gulf of Mexico

USGS Publications Warehouse

Battaglin, William A.; Kendall, Carol; Goolsby, Donald A.; Boyer, Laurie L.

1997-01-01

Nitrate and other nutrients discharged from the Mississippi River basin are suspected of causing a zone of depleted dissolved oxygen (hypoxic zone) in the Gulf of Mexico each summer. The hypoxic zone may have an adverse effect on aquatic life and commercial fisheries. Commercial fertilizers are the dominant source of nitrogen input to the Mississippi basin. Other nitrogen sources include animal waste, fixation of atmospheric nitrogen by legumes, precipitation, domestic and industrial effluent, and the soil. The inputs of nitrogen from most of these sources to the Mississippi basin can be estimated and the outputs in surface water can be measured. However, nitrogen from each source is affected differently by physical, chemical, and biological processes that control nitrogen cycling in terrestrial and aquatic systems. Hence, the relative contributions from the various sources of nitrogen to nitrate load in the Mississippi River are unknown because the different sources may not contribute proportionally to their inputs in the basin. It may be possible to determine the relative contributions of the major sources of nitrate in river water using the stable isotopic ratios d15N and d18O of the nitrate ion. A few researchers have used the d15N and/or d18O isotope ratios to determine sources of nitrate in ground water, headwater catchments, and small rivers, but little is known about the isotopic composition of nitrate in larger rivers. The objective of this study is to measure the isotopic composition of nitrate and suspended organic matter in the Mississippi River and its major tributaries, in discharge to the Gulf of Mexico, and in streamflow from smaller watersheds that have distinct sources of nitrogen (row crops, animal wastes, and urban effluents) or are minimally impacted by man (undeveloped). Samples from seven sites on the Mississippi River and its tributaries and from 17 sites in smaller watersheds within the Mississippi River basin will be analyzed for d15N and d18O of dissolved nitrate. Suspended sediment collected from these sites will also be analyzed to determine the d15N, d13C, and d34S of the suspended organic material. Six samples will be collected at each site during the winter, spring, and summer of 1996-97. Results from these samples will be used to identify seasonal and flow-related variability in d15N and d18O ratios from each site and may also help determine the principal sources of the nitrate entering the Gulf of Mexico.

Chemical and isotopic signature of bulk organic matter and hydrocarbon biomarkers within mid-slope accretionary sediments of the northern Cascadia margin gas hydrate system

USGS Publications Warehouse

Kaneko, Masanori; Shingai, Hiroshi; Pohlman, John W.; Naraoka, Hiroshi

2010-01-01

The chemical and isotopic compositions of sedimentary organic matter (SOM) from two mid-slope sites of the northern Cascadia margin were investigated during Integrated Ocean Drilling Program (IODP) Expedition 311 to elucidate the organic matter origins and identify potential microbial contributions to SOM. Gas hydrate is present at both locations (IODP Sites U1327 and U1328), with distinct patterns of near-seafloor structural accumulations at the cold seep Site U1328 and deeper stratigraphic accumulations at the slope-basin Site U1327. Source characterization and evidence that some components of the organic matter have been diagenetically altered are determined from the concentrations and isotopic compositions of hydrocarbon biomarkers, total organic carbon (TOC), total nitrogen (TN) and total sulfur (TS). The carbon isotopic compositions of TOC (δ13CTOC = −26 to −22‰) and long-chain n-alkanes (C27, C29 and C31, δ13C = −34 to − 29‰) suggest the organic matter at both sites is a mixture of 1) terrestrial plants that employ the C3 photosynthetic pathway and 2) marine algae. In contrast, the δ15NTN values of the bulk sediment (+ 4 to + 8‰) are consistent with a predominantly marine source, but these values most likely have been modified during microbial organic matter degradation. The δ13C values of archaeal biomarker pentamethylicosane (PMI) (− 46.4‰) and bacterial-sourced hopenes, diploptene and hop-21-ene (− 40.9 to − 34.7‰) indicate a partial contribution from methane carbon or a chemoautotrophic pathway. Our multi-isotope and biomarker-based conclusions are consistent with previous studies, based only on the elemental composition of bulk sediments, that suggested a mixed marine-terrestrial organic matter origin for these mid-slope sites of the northern Cascadia margin.

Isotopic mapping of age provinces in Precambrian high-grade terrains: Sri Lanka

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

Milisenda, C.C.; Liew, T.C.; Hofmann, A.W.

1988-09-01

Nd model ages of amphibolite- and granulite-grade rocks in Sri Lanka form a simple region pattern that broadly correlates with mappable geological units, and is in effect an isotopic map of the island's basement. The granulite-grade units of the Highland Group and Southwest Group have model ages of 2.2-3.0 Ga indicating derivation mainly from late Archean sources. They are bounded to the east and west by late Proterozoic gneisses of the Vijayan Complex with model ages of 1.1-2.0 Ga. The isotopic data identify three distinct crustal provinces and are not consistent with earlier suggestions that the Vijayan gneisses are retrogrademore » equivalents of the Highland granulites. Sri Lanka is not a direct continuation of the Archean Dharwar Craton of southern India. Identification of Vijayan-type juvenile crustal terrains in other Gondwana fragments may play a key role in determining the precise attachment of southern India-Sri Lanka in eastern Gondwana.« less

Stable-Carbon Isotopic Composition of Maple Sap and Foliage 1

PubMed Central

Leavitt, Steven W.; Long, Austin

1985-01-01

The 13C/12C ratios of Acer grandidentatum sap sugar collected during the dormant period are compared to those of buds, leaves, and wood developed over the following growing season. As the primary carbon source for cellulose manufacture at initiation of annual growth in deciduous trees, sap sucrose would be expected to have an isotopic composition similar to first-formed cellulose. Although constancy in concentration and 13C/12C ratios of the maple sap sugar suggests any gains or losses (e.g. to maintenance metabolism) do not appreciably alter composition, the 13C/12C ratios of cellulose of the enlarging buds in the spring are quite distinct from those of the sap sugar, seemingly precluding a simple direct biochemical pathway of sap sucrose→glucose→cellulose in favor of a more complex pathway with greater likelihood of isotopic fractionation. The 13C/12C ratios of the leaves and in the growth ring were initially similar to the sap sugar but decreased steadily over the growing season. PMID:16664259

Stable-carbon isotopic composition of maple sap and foliage.

PubMed

Leavitt, S W; Long, A

1985-06-01

The (13)C/(12)C ratios of Acer grandidentatum sap sugar collected during the dormant period are compared to those of buds, leaves, and wood developed over the following growing season. As the primary carbon source for cellulose manufacture at initiation of annual growth in deciduous trees, sap sucrose would be expected to have an isotopic composition similar to first-formed cellulose. Although constancy in concentration and (13)C/(12)C ratios of the maple sap sugar suggests any gains or losses (e.g. to maintenance metabolism) do not appreciably alter composition, the (13)C/(12)C ratios of cellulose of the enlarging buds in the spring are quite distinct from those of the sap sugar, seemingly precluding a simple direct biochemical pathway of sap sucrose-->glucose-->cellulose in favor of a more complex pathway with greater likelihood of isotopic fractionation. The (13)C/(12)C ratios of the leaves and in the growth ring were initially similar to the sap sugar but decreased steadily over the growing season.

Fundamental limits to the accuracy of deuterium isotopes for identifying the spatial origin of migratory animals

USGS Publications Warehouse

Farmer, A.; Cade, B.S.; Torres-Dowdall, J.

2008-01-01

Deuterium isotope analyses have revolutionized the study of migratory connectivity because global gradients of deuterium in precipitation (??DP) are expressed on a continental scale. Several authors have constructed continental scale base maps of ??DP to provide a spatial reference for studying the movement patterns of migratory species and, although they are very useful, these maps present a static, 40-year average view of the landscape that ignores much underlying inter-annual variation. To more fully understand the consequences of this underlying variation, we analyzed the GNIP deuterium data, the source for all current ??DP maps, to estimate the minimum separation in ??DP (and latitude) necessary to conclude with a given level of confidence that distinct ??DP values represent different geographic sites. Extending analyses of ??DP successfully to deuterium in tissues of living organisms, e.g., feathers in migratory birds (??DF), is dependent on the existence of geographic separation of ??DP, where every geographic location has a distribution of values associated with temporal variability in ??DP. Analyses were conducted for three distinct geographic regions: North America, eastern North America (east of longitude 100??W), and Argentina. At the 80% confidence level, the minimum separation values were 12, 7, and 14?? of latitude (equivalent to 53, 31, and 32???) for North America, eastern North America, and Argentina, respectively. Hence, in eastern North America, for example, one may not be able to accurately assign individual samples to sites separated by less than about 7?? of latitude as the distributions of ??DP were not distinct at latitudes <7?? apart. Moreover, two samples that differ by less than 31??? cannot be confidently said to originate from different latitudes. These estimates of minimum separation for ??DP do not include other known sources of variation in feather deuterium (??D F) and hence are a first order approximation that may be useful, in the absence of more specific information for the system of interest, for planning and interpreting the results of new stable isotope studies. ?? 2008 Springer-Verlag.

Carbon isotopic constraints on the contribution of plant material to the natural precursors of trihalomethanes

USGS Publications Warehouse

Bergamaschi, B.A.; Fram, M.S.; Kendall, C.; Silva, S.R.; Aiken, G.R.; Fujii, R.

1999-01-01

The ??13C values of individual trihalomethanes (THM) formed on reaction of chlorine with dissolved organic carbon (DOC) leached from maize (corn, Zea maize L) and Scirpus acutus (an aquatic bulrush), and with DOC extracted from agricultural drainage waters were determined using purge and trap introduction into a gas chromatograph-combustion-isotope ratio monitoring mass spectrometer. We observed a 1-6.8??? difference between the ??13C values of THM produced from the maize and Scirpus leachates, similar to the isotopic difference between the whole plant materials. Both maize and Scirpus formed THM 12??? lower in 13C than whole plant material. We suggest that the low value of the THM relative to the whole plant material is evidence of distinct pools of THM-forming DOC, representing different biochemical types or chemical structures, and possessing different environmental reactivity Humic extracts of waters draining an agricultural field containing Scirpus peat soils and planted with maize formed THM with isotopic values intermediate between those of maize and Scirpus leachates, indicating maize may contribute significantly to the THM-forming DOC. The difference between the ??13C values of the whole isolate and that of the THM it yielded was 3 9???, however, suggesting diagenesis plays a role in determining the ??13C value of THM-forming DOC in the drainage waters, and precluding the direct use of isotopic mixing models to quantitatively attribute sources.The ??13C values of individual trihalomethanes (THM) formed on reaction of chlorine with dissolved organic carbon (DOC) leached from maize (corn; Zea maize L.) and Scirpus acutus (an aquatic bulrush), and with DOC extracted from agricultural drainage waters were determined using purge and trap introduction into a gas chromatograph-combustion-isotope ratio monitoring mass spectrometer. We observed a 16.8qq difference between the ??13C values of THM produced from the maize and Scirpus leachates, similar to the isotopic difference between the whole plant materials. Both maize and Scirpus formed THM 12qq lower in 13C than whole plant material. We suggest that the low value of the THM relative to the whole plant material is evidence of distinct pools of THM-forming DOC, representing different biochemical types or chemical structures, and possessing different environmental reactivity. Humic extracts of waters draining an agricultural field containing Scirpus peat soils and planted with maize formed THM with isotopic values intermediate between those of maize and Scirpus leachates, indicating maize may contribute significantly to the THM-forming DOC. The difference between the ??13C values of the whole isolate and that of the THM it yielded was 3.9qq, however, suggesting diagenesis plays a role in determining the ??13C value of THM-forming DOC in the drainage waters, and precluding the direct use of isotopic mixing models to quantitatively attribute sources.

Sources and Contributions of Oxygen During Microbial Pyrite Oxidation: the Triple Oxygen Isotopes of Sulfate

NASA Astrophysics Data System (ADS)

Ziegler, K.; Coleman, M. L.; Mielke, R. E.; Young, E. D.

2008-12-01

The triple isotopes of oxygen (Δ17O' = δ17O'-0.528 × δ18O' using logarithmic deltas) can trace the oxygen sources of sulfate produced during sulfide oxidation, an important biogeochemical process on Earth's surface and possibly also on Mars [1]. δ18OSO4 compositions are determined by the isotopic selectivity of the mechanism(s) responsible for their changes, and the δ18O value of the reactants (O2 vs. H2O). The relative proportional importance and contribution of each of those sources and mechanisms, as well as their associated isotopic fractionations, are not well understood. We are investigating the use of Δ 17O as a quantitative and qualitative tracer for the different processes and oxygen sources involved in sulfate production. Δ17O signatures are distinct fingerprints of these reservoirs, independent of fractionation factors that can be ambiguous. We conducted controlled abiotic and biotic (Acidithiobacillus ferrooxidans, A.f.) laboratory experiments in which water was spiked with 18O, allowing us to quantify the sources of sulfate oxygen and therefore the processes attending sulfate formation. Results of this Δ17O tracer study show that A.f. microbes initiate pyrite S-oxidation within hours of exposure, and that sulfate is produced from ~90% atmospheric oxygen. This initial lag-phase (< 3 days) is characterized by subtle and multiple changes in oxygen source and contribution that is likely due to the adjustment of the microbial metabolism from S to Fe2+-oxidation. A more detailed understanding of the microbial mechanisms and behavior in the initial lag-phase will aid in the understanding of the ecological conditions required for microbial populations to establish and survive. An exponential phase of growth, facilitated by microbial Fe2+-oxidation, follows. The source of sulfate rapidly switches to abiotic sulfide oxidation during exponential growth and the source of oxygen switches from atmospheric O2 to nearly ~100% water. Pending acquisition of complimentary chemistry data (in progress), we interpret our isotope data to indicate that the biotic fractionation factor ɛ18OSO4-O2 of at least ~ -25 to - 35‰ is augmented by microbially induced kinetic fractionation; it is larger than expected based on published equilibrium values [2,3,4]. Our inferred ɛ18OSO4-H2O of at least ~+10‰ is similar to some reported values. These new insights into the close links between microbial life cycle and sources of sulfate oxygen during sulfide oxidation, and their oxygen isotopic expressions, will help elucidate the role of microbial oxidation in natural systems. If microbial populations in natural systems remain in a perpetual lag-phase due to constrains of chemistry, atmospheric oxygen will imprint its isotopic signature onto sulfate deposits. Ultimately, such data could be used as biosignatures on Early Earth or Mars. [1] Brunner and Coleman (2008) EPSL 270, 63-72. [2] Balci et al. (2007) GCA 71, 3796-3811. [3] Pisapia et al. (2007) GCA 71, 2474-2490. [4] Taylor et al. (1984) GCA 48, 2669-2678.

Authigenic carbon entombed in methane-soaked sediments from the northeastern transform margin of the Guaymas Basin, Gulf of California

NASA Astrophysics Data System (ADS)

Paull, Charles K.; Ussler, William; Peltzer, Edward T.; Brewer, Peter G.; Keaten, Rendy; Mitts, Patrick J.; Nealon, Jeffrey W.; Greinert, Jens; Herguera, Juan-Carlos; Elena Perez, M.

2007-06-01

Extensive ROV-based sampling and exploration of the seafloor was conducted along an eroded transform-parallel fault scarp on the northeastern side of the Guaymas Basin in the Gulf of California to observe the nature of fluids venting from the seafloor, measure the record left by methane-venting on the carbonates from this area, and determine the association with gas hydrate. One gas vent vigorous enough to generate a water-column gas plume traceable for over 800 m above the seafloor was found to emanate from a ˜10-cm-wide orifice on the eroded scarp face. Sediment temperature measurements and topography on a sub-bottom reflector recorded in a transform-parallel seismic reflection profile identified a subsurface thermal anomaly beneath the gas vent. Active chemosynthetic biological communities (CBCs) and extensive authigenic carbonates that coalesce into distinct chemoherm structures were encountered elsewhere along the eroded transform-parallel scarp. The carbon isotopic composition of methane bubbles flowing vigorously from the gas vent (-53.6±0.8‰ PDB) is comparable to methane found in sediment cores taken within the CBCs distributed along the scarp (-51.9±8.1‰ PDB). However, the δ13C value of the CO 2 in the vent gas (+12.4±1.1‰ PDB) is very distinct from those for dissolved inorganic carbon (DIC) (-35.8‰ to -2.9‰ PDB) found elsewhere along the scarp, including underneath CBCs. The δ13C values of the carbonate-rich sediments and rocks exposed on the seafloor today also span an unusually large range (-40.9‰ to +12.9‰ PDB) and suggest two distinct populations of authigenic carbonate materials were sampled. Unconsolidated sediments and some carbonate rocks, which have lithologic evidence for near-seafloor formation, have negative δ13C values, while carbonate rocks that clearly formed in the subsurface have positive δ13C values (up to +23.0‰) close to that measured for CO 2 in the vent gas. There appears to be two carbon sources for the authigenic carbonates: (1) deeply-sourced, isotopically heavy CO 2 (˜+12‰); and (2) isotopically light DIC derived from local anaerobic oxidation of methane at the sulfate-methane interface in the shallow subsurface. Addition of isotopically light methane-derived carbon at the seafloor may completely mask the isotopically heavy CO 2 signature (+12.4‰) in the underlying sediments. Thus, the authigenic carbonates may have formed from the same methane- and carbon dioxide-bearing fluid, but under different migration and alteration conditions, depending on how it migrated through the sediment column.

Geochemical Evolution of the Louisville Seamount Chain

NASA Astrophysics Data System (ADS)

Vanderkluysen, L.; Mahoney, J. J.; Koppers, A. A.; Lonsdale, P. F.

2007-12-01

The Louisville seamount chain is a 4300 km long chain of submarine volcanoes in the southwestern Pacific that is commonly thought to represent a hotspot track. It spans an ~80 Myr age range, comparable to that of the Hawaiian-Emperor chain (Koppers et al., G-cubed, 5 (6), 2004). The few previously dredged igneous samples are dominantly basaltic and alkalic, and have been inferred to represent post-shield volcanism (Hawkins et al., AGU Monograph, 43, 235, 1987). Their isotope and trace element signatures suggest an unusually homogenous mantle source (Cheng et al., AGU Monograph, 43, 283, 1987). Dredging in 2006, during the AMAT02RR cruise of the R.V. Revelle, was carried out in the hope of recovering both shield and post-shield samples and of exploring the geochemical evolution of the chain. Igneous rocks were recovered from 33 stations on 23 seamounts covering some 47 Myr of the chain's history. Our study, focusing on the major and trace element and Sr, Nd and Pb isotopic characteristics of these samples, shows that all are alkalic basalts, basanites and tephrites containing normative nepheline. Variations in major and trace elements appear to be controlled predominantly by variable extents of melting and fractional crystallization, with little influence from mantle source heterogeneity. Indeed, age-corrected isotopic values define only a narrow range, in agreement with long-term source homogeneity relative to the scale of melting; e.g., ɛNd varies from +4.1 to +5.7, 206Pb/204Pb from 19.048 to 19.281, and 87Sr/86Sr from 0.70362 to 0.70398. These values broadly fall within the fields of the proposed "C" or "FOZO" mantle end-members. However, small variations are present, with less radiogenic Nd and Pb isotope ratios at the older, western end of the chain, defining a trend toward a broadly EM2-like composition. Although some workers have postulated that the Louisville hotspot was the source of the ~120 Myr Ontong Java Plateau, our samples are isotopically distinct from any known Ontong Java compositions.

Methane Emissions from Landfill: Isotopic Evidence for Low Percentage of Oxidation from Gas Wells, Active and Closed Cells

NASA Astrophysics Data System (ADS)

Lowry, David; Fisher, Rebecca; Zazzeri, Giulia; al-Shalaan, Aalia; France, James; Lanoisellé, Mathias; Nisbet, Euan

2017-04-01

Large landfill sites remain a significant source of methane emissions in developed and developing countries, with a global estimated flux of 29 Tg / yr in the EDGAR 2008 database. This is significantly lower than 20 years ago due to the introduction of gas extraction systems, but active cells still emit significant amounts of methane before the gas is ready for extraction. Historically the methane was either passively oxidized through topsoil layers or flared. Oxidation is still the primary method of methane removal in many countries, and covered, remediated cells across the world continue to emit small quantities of methane. The isotopic signatures of methane from landfill gas wells, and that emitted from active and closed cells have been characterized for more than 20 UK landfills since 2011, with more recent work in Kuwait and Hong Kong. Since 2013 the emission plumes have been identified by a mobile measurement system (Zazzeri et al., 2015). Emissions in all 3 countries have a characteristic δ13C signature of -58 ± 3 ‰ dominated by emissions from the active cells, despite the hot, dry conditions of Kuwait and the hot, humid conditions of Hong Kong. Gas well samples define a similar range. Surface emissions from closed cells and closed landfills are mostly in the range -56 to -52 ‰Ṫhese are much more depleted values than those observed in the 1990s (up to -35 ) when soil oxidation was the dominant mechanism of methane removal. Calculations using isotopic signatures of the amount of methane oxidised in these closed areas before emission to atmosphere range from 5 to 15%, but average less than 10%, and are too small to calculate from the high-emitting active cells. Compared to other major methane sources, landfills have the most consistent isotopic signature globally, and are distinct from the more 13C-enriched natural gas, combustion and biomass burning sources. Zazzeri, G. et al. (2015) Plume mapping and isotopic characterization of anthropogenic methane sources, Atmospheric Environment, 110, 151-162, doi.org/10.1016/j.atmosenv.2015.03.029.

Geochemically distinct carbon isotope distributions in Allochromatium vinosum DSM 180T grown photoautotrophically and photoheterotrophically.

PubMed

Tang, T; Mohr, W; Sattin, S R; Rogers, D R; Girguis, P R; Pearson, A

2017-03-01

Anoxygenic, photosynthetic bacteria are common at redox boundaries. They are of interest in microbial ecology and geosciences through their role in linking the carbon, sulfur, and iron cycles, yet much remains unknown about how their flexible carbon metabolism-permitting either autotrophic or heterotrophic growth-is recorded in the bulk sedimentary and lipid biomarker records. Here, we investigated patterns of carbon isotope fractionation in a model photosynthetic sulfur-oxidizing bacterium, Allochromatium vinosum DSM180 T . In one treatment, A. vinosum was grown with CO 2 as the sole carbon source, while in a second treatment, it was grown on acetate. Different intracellular isotope patterns were observed for fatty acids, phytol, individual amino acids, intact proteins, and total RNA between the two experiments. Photoautotrophic CO 2 fixation yielded typical isotopic ordering for the lipid biomarkers: δ 13 C values of phytol > n-alkyl lipids. In contrast, growth on acetate greatly suppressed intracellular isotopic heterogeneity across all molecular classes, except for a marked 13 C-depletion in phytol. This caused isotopic "inversion" in the lipids (δ 13 C values of phytol < n-alkyl lipids). The finding suggests that inverse δ 13 C patterns of n-alkanes and pristane/phytane in the geologic record may be at least in part a signal for photoheterotrophy. In both experimental scenarios, the relative isotope distributions could be predicted from an isotope flux-balance model, demonstrating that microbial carbon metabolisms can be interrogated by combining compound-specific stable isotope analysis with metabolic modeling. Isotopic differences among molecular classes may be a means of fingerprinting microbial carbon metabolism, both in the modern environment and the geologic record. © 2017 John Wiley & Sons Ltd.

Generation and Reworking of Archaean and Hadean Crust

NASA Astrophysics Data System (ADS)

Hawkesworth, C.; Kemp, T.; Storey, C.; Dhuime, B.

2008-12-01

Combined Hf and O isotopes in well-dated zircons are increasingly used to investigate the age of the crustal source rocks of detrital and inherited zircons. O isotopes are used to screen out samples that may have a sediment contribution in the parental magma, since sediments yield hybrid model ages that are difficult to interpret. Mafic and granitic rocks also have different Lu/Hf ratios, and so in principle the Hf isotope ratios of zircons can be used to investigate the broad composition of the average crust. The unradiogenic Hf isotope compositions of the Jack Hills zircons from Western Australia indicate the existence of enriched (crustal) reservoirs by at least 4.3 Ga (Y. Amelin et al., 1998, Nature v. 399, p. 252- 255; T. M. Harrison et al., 2005, Science, v. 310, p. 1947-1950). We report in situ Hf isotope analyses of the Jack Hills zircons in which the Pb isotope age information is measured concurrently with the Hf isotope data. The simple data arrays provide clear evidence for Earth differentiation at 4.5 Ga, with the production of both continental crust-like material and a mafic crustal reservoir with higher Lu/Hf. The continued resampling of this reservoir over at least 1.5 Ga argues for a substantial stabilised volume of mafic crust, and, in tandem with oxygen isotope data, the existence of Hadean continents. Zircons remain poor windows into the upper mantle. We therefore investigate Nd isotopes in well-dated titanites; they have closure temperatures for Pb in the range 600-750oC and they can retain cores with distinct age and REE chemistry to subsequent rim overgrowths. Nd isotopes offer a complementary approach to Hf in zircon that can be used to construct the both depleted mantle evolution and crustal growth curves.

The problem of isotopic baseline: Reconstructing the diet and trophic position of fossil animals

NASA Astrophysics Data System (ADS)

Casey, Michelle M.; Post, David M.

2011-05-01

Stable isotope methods are powerful, frequently used tools which allow diet and trophic position reconstruction of organisms and the tracking of energy sources through ecosystems. The majority of ecosystems have multiple food sources which have distinct carbon and nitrogen isotopic signatures despite occupying a single trophic level. This difference in the starting isotopic composition of primary producers sets up an isotopic baseline that needs to be accounted for when calculating diet or trophic position using stable isotopic methods. This is particularly important when comparing animals from different regions or different times. Failure to do so can cause erroneous estimations of diet or trophic level, especially for organisms with mixed diets. The isotopic baseline is known to vary seasonally and in concert with a host of physical and chemical variables such as mean annual rainfall, soil maturity, and soil pH in terrestrial settings and lake size, depth, and distance from shore in aquatic settings. In the fossil record, the presence of shallowing upward suites of rock, or parasequences, will have a considerable impact on the isotopic baseline as basin size, depth and distance from shore change simultaneously with stratigraphic depth. For this reason, each stratigraphic level is likely to need an independent estimation of baseline even within a single outcrop. Very little is known about the scope of millennial or decadal variation in isotopic baseline. Without multi-year data on the nature of isotopic baseline variation, the impacts of time averaging on our ability to resolve trophic relationships in the fossil record will remain unclear. The use of a time averaged baseline will increase the amount of error surrounding diet and trophic position reconstructions. Where signal to noise ratios are low, due to low end member disparity (e.g., aquatic systems), or where the observed isotopic shift is small (≤ 1‰) the error introduced by time averaging may severely inhibit the scope of one's interpretations and limit the types of questions one can reliably answer. In situations with strong signal strength, resulting from high amounts of end member disparity (e.g., terrestrial settings), this additional error maybe surmountable. Baseline variation that is adequately characterized can be dealt with by applying multiple end-member mixing models.

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.

Processes affecting δ34S and δ18O values of dissolved sulfate in alluvium along the Canadian River, central Oklahoma, USA

USGS Publications Warehouse

Tuttle, Michele L.W.; Breit, George N.; Cozzarelli, Isabelle M.

2009-01-01

The δ34S and δ18O values for dissolved sulfate in groundwater are commonly used in aquifer studies to identify sulfate reservoirs and describe biogeochemical processes. The utility of these data, however, often is compromised by mixing of sulfate sources within reservoirs and isotope fractionation during sulfur redox cycling. Our study shows that, after all potential sulfate sources are identified and isotopically characterized, the δ34SSO4 and δ18OSO4 values differentiate processes such as sulfate-source mixing, sulfide oxidation, barite dissolution, and organosulfur decomposition. During bacterial reduction of sulfate, the values reflect kinetic sulfur isotope fractionation and exchange of oxygen isotopes between sulfate and water. Detailed analysis of the chemistry (Cl and SO4 concentrations) and isotopic composition (δ2HH2Oand δ18OH2O) of groundwater in an alluvial aquifer in Central Oklahoma, USA allowed the identification of five distinct end members that supply water to the aquifer (regional groundwater flowing into the study area, river water, leachate from a closed landfill that operated within the site, rain, and surface runoff). The δ34SSO4 and δ18OSO4 values in each end member differentiated three sources of sulfate: sulfate dissolved from Early to Late Permian rocks within the drainage basin (δ34SSO4 = 8–12‰ and δ18OSO4 = 10‰), iron sulfides oxidized by molecular oxygen during low water-table levels (δ34SSO4 = − 16‰ and δ18OSO4 = 10‰), and organosulfur compounds (predominately ester sulfates) from decomposition of vegetation on the surface and from landfill trash buried in the alluvium (δ34SSO4 = 8‰ and δ18OSO4 = 6‰). During bacterial reduction of these sulfate sources, similar isotope fractionation processes are recorded in the parallel trends of increasing δ34SSO4 and δ18OSO4 values. When extensive reduction occurs, the kinetic sulfur isotope fractionation (estimated by εH2S–SO4 = − 23‰) results in the steady increase of δ34SSO4values to greater than 70‰. Equilibrium isotope fractionation during exchange of sulfate oxygen and water oxygen, a process not commonly observed in field-based studies, is documented in δ18OSO4 values asymptotically approaching 21‰, the value predicted for conditions at the study site (εSO4–H2O = 27‰). These results show that recognition of all potential sulfate sources is a critical first step to resolving complexities in δ34SSO4 and δ18OSO4 data. The approach taken in this study can be used in other aquifer systems where the identification of multiple sulfate sources and sulfur redox cycling is important to understanding natural processes and anthropogenic influences.

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.

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.

Rhenium-osmium and samarium-neodymium isotopic systematics of the stillwater complex

USGS Publications Warehouse

Lambert, D.D.; Morgan, J.W.; Walker, R.J.; Shirey, S.B.; Carlson, R.W.; Zientek, M.L.; Koski, M.S.

1989-01-01

Isotopic data for the Stillwater Complex, Montana , which formed about 2700 Ma (million years ago), were obtained to evaluate the role of magma mixing in the formation of strategic platinum-group element (PGE) ore deposits. Neodymium and osmium isotopic data indicate that the intrusion formed from at least two geochemically distinct magmas. Ultramafic affinity (U-type) magmas had initial ??Nd of -0.8 to -3.2 and a chondritic initial 187Os/186Os ratio of ???0.88, whereas anorthositic affinity (A-type) magmas had ??Nd of -0.7 to +1.7 and an initial 187Os/186Os ratio of ???1.13. These data suggest that U-type magmas were derived from a lithospheric mantle source containing recycled crustal materials whereas A-type magmas originated either by crustal contamination of basaltic magmas or by partial melting of basalt in the lower crust. The Nd and Os isotopic data also suggest that Os, and probably the other PGEs in ore horizons such as the J-M Reef, was derived from A-type magmas. The Nd and Os isotopic heterogeneity observed in rocks below the J-M Reef also suggests that A-type magmas were injected into the Stillwater U-type magma chamber at several stages during the development of the Ultramafic series.

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.

Lead isotopes in North Pacific deep water - Implications for past changes in input sources and circulation patterns

USGS Publications Warehouse

van de Flierdt, T.; Frank, M.; Halliday, A.N.; Hein, J.R.; Hattendorf, B.; Gunther, D.; Kubik, P.W.

2003-01-01

The sources of non-anthropogenic Pb in seawater have been the subject of debate. Here we present Pb isotope time-series that indicate that the non-anthropogenic Pb budget of the northernmost Pacific Ocean has been governed by ocean circulation and riverine inputs, which in turn have ultimately been controlled by tectonic processes. Despite the fact that the investigated locations are situated within the Asian dust plume, and proximal to extensive arc volcanism, eolian contributions have had little impact. We have obtained the first high-resolution and high-precision Pb isotope time-series of North Pacific deep water from two ferromanganese crusts from the Gulf of Alaska in the NE Pacific Ocean, and from the Detroit Seamount in the NW Pacific Ocean. Both crusts were dated applying 10 Be/9Be ratios and yield continuous time-series for the past 13.5 and 9.6 Myr, respectively. Lead isotopes show a monotonic evolution in 206Pb/204Pb from low values in the Miocene (??? 18.57) to high values at present day (??? 18.84) in both crusts, even though they are separated by more than 3000 km along the Aleutian Arc. The variation exceeds the amplitude found in Equatorial Pacific deep water records by about three-fold. There also is a striking similarity in 207Pb/204Pb and 208Pb/ 204Pb ratios of the two crusts, indicating the existence of a local circulation cell in the sub-polar North Pacific, where efficient lateral mixing has taken place but only limited exchange (in terms of Pb) with deep water from the Equatorial Pacific has occurred. Both crusts display well-defined trends with age in Pb-Pb isotope mixing plots, which require the involvement of at least four distinct Pb sources for North Pacific deep water. The Pb isotope time-series reveal that eolian supplies (volcanic ash and continent-derived loess) have only been of minor importance for the dissolved Pb budget of marginal sites in the deep North Pacific over the past 6 Myr. The two predominant sources have been young volcanic arcs, one located in the northeastern part and one located in the northwestern part of the Pacific margin, from where material has been eroded and delivered to the ocean, most likely via riverine pathways. ?? 2003 Elsevier Science B.V. All rights reserved.

Upper Mississippi Pb as a mid-1800s chronostratigraphic marker in sediments from seasonally anoxic lakes in Eastern Canada

NASA Astrophysics Data System (ADS)

Gobeil, Charles; Tessier, André; Couture, Raoul-Marie

2013-07-01

Sediment cores from eight headwater lakes located in Southern Québec, Eastern Canada, were analyzed for Pb, stable Pb isotopes, and the radioelements 210Pb, 137Cs, 241Am and 226Ra. The depth profiles of stable Pb isotope ratios show, for the post-19th century period, the influence of several isotopically distinct anthropogenic lead sources, mainly including emissions from two Canadian smelters and from leaded gasoline combustion in Canada and in the United States. A most interesting feature of the profiles, however, is the presence of sharp stable Pb isotope ratio peaks near the depth horizon, where excess 210Pb becomes undetectable. Using a binary mixing model and assuming that natural Pb concentrations and isotopic compositions from the catchment are given by the pre-industrial sediments at the bottom of the cores, we find that a significant part of the anthropogenic Pb supplied to the sediments at this horizon originated from smelting activities in the Upper Mississippi Valley. We assess that the Pb isotope ratio peaks, also observed in the laminated sediments of the Pettaquamscutt Estuary, Rhode Island, USA, are an accurate chronostratigraphic marker for the validation of mid-19th century 210Pb-derived dates. Given that the study lakes are located up to 2000 km from the Mississippi Valley, we conclude that this isotopic Pb signal provides a widely distributed time-marker that is key to validate 210Pb chronologies in environmental archives from Eastern North America.

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.

Variations in microbial carbon sources and cycling in the deep continental subsurface

NASA Astrophysics Data System (ADS)

Simkus, Danielle N.; Slater, Greg F.; Lollar, Barbara Sherwood; Wilkie, Kenna; Kieft, Thomas L.; Magnabosco, Cara; Lau, Maggie C. Y.; Pullin, Michael J.; Hendrickson, Sarah B.; Wommack, K. Eric; Sakowski, Eric G.; van Heerden, Esta; Kuloyo, Olukayode; Linage, Borja; Borgonie, Gaetan; Onstott, Tullis C.

2016-01-01

Deep continental subsurface fracture water systems, ranging from 1.1 to 3.3 km below land surface (kmbls), were investigated to characterize the indigenous microorganisms and elucidate microbial carbon sources and their cycling. Analysis of phospholipid fatty acid (PLFA) abundances and direct cell counts detected varying biomass that was not correlated with depth. Compound-specific carbon isotope analyses (δ13C and Δ14C) of the phospholipid fatty acids (PLFAs) and carbon substrates combined with genomic analyses did identify, however, distinct carbon sources and cycles between the two depth ranges studied. In the shallower boreholes at circa 1 kmbls, isotopic evidence indicated microbial incorporation of biogenic CH4 by the in situ microbial community. At the shallowest site, 1.05 kmbls in Driefontein mine, this process clearly dominated the isotopic signal. At slightly deeper depths, 1.34 kmbls in Beatrix mine, the isotopic data indicated the incorporation of both biogenic CH4 and dissolved inorganic carbon (DIC) derived from CH4 oxidation. In both of these cases, molecular genetic analysis indicated that methanogenic and methanotrophic organisms together comprised a small component (<5%) of the microbial community. Thus, it appears that a relatively minor component of the prokaryotic community is supporting a much larger overall bacterial community in these samples. In the samples collected from >3 kmbls in Tau Tona mine (TT107, TT109 Bh2), the CH4 had an isotopic signature suggesting a predominantly abiogenic origin with minor inputs from microbial methanogenesis. In these samples, the isotopic enrichments (δ13C and Δ14C) of the PLFAs relative to CH4 were consistent with little incorporation of CH4 into the biomass. The most 13C-enriched PLFAs were observed in TT107 where the dominant CO2-fixation pathway was the acetyl-CoA pathway by non-acetogenic bacteria. The differences in the δ13C of the PLFAs and the DIC and DOC for TT109 Bh2 were ∼-24‰ and 0‰, respectively. The dominant CO2-fixation pathways were 3-HP/4-HB cycle > acetyl-CoA pathway > reductive pentose phosphate cycle.

Identification of multiple mercury sources to stream sediments near Oak Ridge, TN, USA

DOE PAGES

Donovan, Patrick M.; Blum, Joel D.; Demers, Jason D.; ...

2014-03-03

In this paper, sediments were analyzed for total Hg concentration (THg) and isotopic composition from streams and rivers in the vicinity of the Y-12 National Security Complex (Y12) in Oak Ridge, TN (USA). In the stream directly draining Y12, where industrial releases of mercury (Hg) have been documented, high THg (3.26 to 60.1 μg/g) sediments had a distinct Hg isotopic composition (δ 202Hg of 0.02 ± 0.15‰ and Δ 199Hg of -0.07 ± 0.03‰; mean ± 1SD, n=12) compared to sediments from relatively uncontaminated streams in the region (δ 202Hg = -1.40 ± 0.06‰ and Δ 199Hg of –0.26 ±more » 0.03‰; mean ± 1SD, n=6). Additionally, several streams that are nearby but do not drain Y12 had sediments with intermediate THg (0.06 to 0.21 μg/g) and anomalous δ 202Hg (as low as -5.07‰). We suggest that the low δ 202Hg values in these sediments provide evidence for the contribution of an additional Hg source to sediments, possibly derived from atmospheric deposition. In sediments directly downstream of Y12 this third Hg source is not discernible and the Hg isotopic composition can be largely explained by the mixing of low THg sediments with high THg sediments contaminated by Y12 discharges.« less

Geochemical evidence for the provenance of aeolian deposits in the Qaidam Basin, Tibetan Plateau

NASA Astrophysics Data System (ADS)

Du, Shisong; Wu, Yongqiu; Tan, Lihua

2018-06-01

The main purpose of this study is to analyse the material source of different grain-size components of dune sand in the Qaidam Basin. We determined the trace and rare earth element (REE) compositions and Sr-Nd isotopic compositions of the coarse (75-500 μm) and fine (<75 μm) fractions of surface sediment samples. The comparison of the immobile trace element and REE compositions, Sr-Nd isotopic compositions and multidimensional scaling (MDS) results of the dune sands with those of different types of sediments in potential source areas revealed the following information. (1) The fine- and coarse-grained fractions of dune sands in the Qaidam Basin exhibit distinctly different elemental concentrations, elemental patterns and characteristic parameters of REE. Moreover, Sr-Nd isotopic differences also exist between different grain-size fractions of aeolian sand, which means that different grain-size fractions of these dune sands have different source areas. (2) The geochemical characteristics of the coarse particles of dune sand exhibit obvious regional heterogeneity and generally record a local origin derived from local fluvial sediments and alluvial/proluvial sediments. The coarse- and fine-grained dune sand in the southern Qaidam Basin mainly came from Kunlun Mountains, whereas the coarse- and fine-grained dune sand in the northeastern Qaidam Basin mainly came from Qilian Mountains. (3) The fine-grained fractions of sediments throughout the entire Qaidam Basin may have been affected by the input of foreign materials from the Tarim Basin.

Re-Os isotope and platinum group elements of a FOcal ZOne mantle source, Louisville Seamounts Chain, Pacific ocean

NASA Astrophysics Data System (ADS)

Tejada, Maria Luisa G.; Hanyu, Takeshi; Ishikawa, Akira; Senda, Ryoko; Suzuki, Katsuhiko; Fitton, Godfrey; Williams, Rebecca

2015-02-01

The Louisville Seamount Chain (LSC) is, besides the Hawaiian-Emperor Chain, one of the longest-lived hotspot traces. We report here the first Re-Os isotope and platinum group element (PGE) data for Canopus, Rigil, and Burton Guyots along the chain, which were drilled during IODP Expedition 330. The LSC basalts possess (187Os/188Os)i = 0.1245-0.1314 that are remarkably homogeneous and do not vary with age. A Re-Os isochron age of 64.9 ± 3.2 Ma was obtained for Burton seamount (the youngest of the three seamounts drilled), consistent with 40Ar-39Ar data. Isochron-derived initial 187Os/188Os ratio of 0.1272 ± 0.0008, together with data for olivines (0.1271-0.1275), are within the estimated primitive mantle values. This (187Os/188Os)i range is similar to those of Rarotonga (0.124-0.139) and Samoan shield (0.1276-0.1313) basalts and lower than those of Cook-Austral (0.136-0.155) and Hawaiian shield (0.1283-0.1578) basalts, suggesting little or no recycled component in the LSC mantle source. The PGE data of LSC basalts are distinct from those of oceanic lower crust. Variation in PGE patterns can be largely explained by different low degrees of melting under sulfide-saturated conditions of the same relatively fertile mantle source, consistent with their primitive mantle-like Os and primordial Ne isotope signatures. The PGE patterns and the low 187Os/188Os composition of LSC basalts contrast with those of Ontong Java Plateau (OJP) tholeiites. We conclude that the Re-Os isotope and PGE composition of LSC basalts reflect a relatively pure deep-sourced common mantle sampled by some ocean island basalts but is not discernible in the composition of OJP tholeiites.

Isotopic and trace element compositions of upper mantle and lower crustal xenoliths, Cima volcanic field, California: Implications for evolution of the subcontinental lithospheric mantle

USGS Publications Warehouse

Mukasa, S.B.; Wilshire, H.G.

1997-01-01

Ultramafic and mafic xenoliths from the Cima volcanic field, southern California, provide evidence of episodic modification of the upper mantle and underplating of the crust beneath a portion of the southern Basin and Range province. The upper mantle xenoliths include spinel peridotite and anhydrous and hydrous pyroxenite, some cut by igneous-textured pyroxenite-gabbro veins and dikes and some by veins of amphibole ?? plagioclase. Igneous-textured pyroxenites and gabbros like the dike rocks also occur abundantly as isolated xenoliths inferred to represent underplated crust. Mineral and whole rock trace element compositions among and within the different groups of xenoliths are highly variable, reflecting multiple processes that include magma-mantle wall rock reactions, episodic intrusion and it filtration of basaltic melts of varied sources into the mantle wall rock, and fractionation. Nd, Sr, and Pb isotopic compositions mostly of clinopyroxene and plagioclase mineral separates show distinct differences between mantle xenoliths (??Nd = -5.7 to +3.4; 87Sr/86Sr = 0.7051 - 0.7073; 206Pb/204Pb = 19.045 - 19.195) and the igneous-textured xenoliths (??Nd = +7.7 to +11.7; 87Sr/86Sr = 0.7027 - 0.7036 with one carbonate-affected outlier at 0.7054; and 206Pb/204Pb = 18.751 - 19.068), so that they cannot be related. The igneous-textured pyroxenites and gabbros are similar in their isotopic compositions to the host basaltic rocks, which have ??Nd of+5.1 to +9.3; 87Sr/86Sr of 0.7028 - 0.7050, and 206Pb/204Pb of 18.685 - 21.050. The igneous-textured pyroxenites and gabbros are therefore inferred to be related to the host rocks as earlier cogenetic intrusions in the mantle and in the lower crust. Two samples of peridotite, one modally metasomatized by amphibole and the other by plagioclase, have isotopic compositions intermediate between the igneous-textured xenoliths and the mantle rock, suggesting mixing, but also derivation of the metasomatizing magmas from two separate and distinct sources. Sm-Nd two-mineral "isochrons" yield apparent ages for petrographically identical rocks believed to be coeval ranging from -0 to 113 ?? 26 Ma, indicating the unreliability of dating these rocks with this method. Amphibole and plagioclase megacrysts are isotopically like the host basalts and probably originate by mechanical breakup of veins comagmatic with the host basaltic rocks. Unlike other Basin and Range localities, Cima Cr-diopside group isotopic compositions do not overlap with those of the host basalts. Copyright 1997 by the American Geophysical Union.

Devonian magmatism in the Timan Range, Arctic Russia - subduction, post-orogenic extension, or rifting?

NASA Astrophysics Data System (ADS)

Pease, V.; Scarrow, J. H.; Silva, I. G. Nobre; Cambeses, A.

2016-11-01

Devonian mafic magmatism of the northern East European Craton (EEC) has been variously linked to Uralian subduction, post-orogenic extension associated with Caledonian collision, and rifting. New elemental and isotopic analyses of Devonian basalts from the Timan Range and Kanin Peninsula, Russia, in the northern EEC constrain magma genesis, mantle source(s) and the tectonic process(es) associated with this Devonian volcanism to a rift-related context. Two compositional groups of low-K2O tholeiitic basalts are recognized. On the basis of Th concentrations, LREE concentrations, and (LREE/HREE)N, the data suggest two distinct magma batches. Incompatible trace elements ratios (e.g., Th/Yb, Nb/Th, Nb/La) together with Nd and Pb isotopes indicate involvement of an NMORB to EMORB 'transitional' mantle component mixed with variable amounts of a continental component. The magmas were derived from a source that developed high (U,Th)/Pb, U/Th and Sm/Nd over time. The geochemistry of Timan-Kanin basalts supports the hypothesis that the genesis of Devonian basaltic magmatism in the region resulted from local melting of transitional mantle and lower crust during rifting of a mainly non-volcanic continental rifted margin.

Diffusive Fractionation of Lithium Isotopes in Olivine Grain Boundaries

NASA Astrophysics Data System (ADS)

Homolova, V.; Watson, E. B.

2012-12-01

Diffusive fractionation of isotopes has been documented in silicate melts, aqueous fluids, and single crystals. In polycrystalline rocks, the meeting place of two grains, or grain boundaries, may also be a site of diffusive fractionation of isotopes. We have undertaken an experimental and modeling approach to investigate diffusive fractionation of lithium (Li) isotopes by grain boundary diffusion. The experimental procedure consists of packing a Ni metal capsule with predominantly ground San Carlos olivine and subjecting the capsule to 1100C and 1GPa for two days in a piston cylinder apparatus to create a nominally dry, 'dunite rock'. After this synthesis step, the capsule is sectioned and polished. One of the polished faces of the 'dunite rock' is then juxtaposed to a source material of spodumene and this diffusion couple is subject to the same experimental conditions as the synthesis step. Li abundances and isotopic profiles (ratios of count rates) were analyzed using LA-ICP-MS. Li concentrations linearly decrease away from the source from 550ppm to the average concentration of the starting olivine (2.5ppm). As a function of distance from the source, the 7Li/6Li ratio decreases to a minimum before increasing to the background ratio of the 'dunite rock'. The 7Li/6Li ratio minimum coincides with the lowest Li concentrations above average 'dunite rock' abundances. The initial decrease in the 7Li/6Li ratio is similar to that seen in other studies of diffusive fractionation of isotopes and is thought to be caused by the higher diffusivity (D) of the lighter isotope relative to the heavier isotope. The relationship between D and mass (m) is given by (D1/D2) =(m2/m1)^β, where β is an empirical fractionation factor; 1 and 2 denote the lighter and heavier isotope, respectively. A fit to the Li isotopic data reveals an effective DLi of ~1.2x10^-12 m/s^2 and a β of 0.1. Numerical modelling was utilized to elucidate the relationship between diffusive fractionation produced in the grain boundaries versus the lattices of the individual grains of the 'dunite rock'. The model assumes a linear grain boundary juxtaposed to the long side of a rectangular crystal lattice. During a simulation, the diffusant may directly enter the lattice or the grain boundary. Once in the grain boundary, the diffusant may then continue to diffuse away from the source until the end of the simulation or, alternatively, it may be incorporated into the lattice at some point during its travels down the grain boundary. The model system is similar to that considered by Whipple-LeClaire (1963) and our model results agree well with their analytical solution. Preliminary modeling results show that the distinctive minimum in the isotopic ratio is only produced when diffusive fractionation occurs in the grain boundary and not when the fractionation occurs only in the lattice. This suggests that the isotopic profile observed in the experiments may be a product of diffusive fractionation in grain boundaries. Implications of these results extend to the longevity of Li isotopic heterogeneities in the mantle, and suggest that the isotopes of other elements, which have a large relative mass difference, may also be diffusively fractionated by grain boundary diffusion.

Radiogenic isotope evidence for transatlantic atmospheric dust transport

NASA Astrophysics Data System (ADS)

Kumar, Ashwini; Abouchami, Wafa; Garrison, Virginia H.; Galer, Stephen J. G.; Andreae, Meinrat O.

2013-04-01

Early studies by Prospero and colleagues [1] have shown that African dust reaches all across the Atlantic and into the Caribbean. It may contribute to fertilizing the Amazon rainforest [2,3,4], in addition to enhancing the ocean biological productivity via delivery of iron, a key nutrient element[5]. Radiogenic isotope ratios (Sr, Nd, Pb) are robust tracers of dust sources and can thus provide information on provenance and pathways of dust transport. Here we report Sr, Nd and Pb isotope data on atmospheric aerosols, collected in 2008 on quartz filters, from three different locations in Mali (12.6° N, 8.0° W; 555 m a.s.l.), Tobago (11.3° N, 60.5° W; 329 m a.s.l.) and the U.S. Virgin Islands (17.7° N, 64.6° W; 27 m a.s.l.) to investigate the hypothesis of dust transport across the Atlantic. About 2 cm2 of filter were acid-leached in 0.5 N HBr for selective removal of the anthropogenic labile Pb component (leachate) and possibly the fine soluble particle fraction. The remainder of the filter was subsequently dissolved using a mixture of HF and HNO3 acids, and should be representative of the silicate fraction. Isotopic compositions were measured by TIMS on a ThermoFisher Triton at MPIC, with Pb isotope ratios determined using the triple-spike method. Significant Pb isotope differences between leachates and residues were observed. The variability in Pb isotopic composition among leachates may be attributed to variable and distinct anthropogenic local Pb sources from Africa and South America [6], however, residues are imprinted by filter blank contribution suggesting to avoid the quartz fiber filter for isotopic study of aerosols. The Nd and Sr isotope ratios of aerosol leachates show similar signatures at all three locations investigated. The nearly identical Nd and Sr isotopic compositions in the Mali, Tobago and Virgin islands leachates are comparable to those obtained on samples from the Bodélé depression, Northern Chad [7] and suggest a possible common source origin. These results identify an African source signal, in aerosols from the Virgin Islands and Tobago collected during African dusts incursion, and thus provides evidence for transatlantic dust transport during the spring/summer season. This, in turn, is entirely consistent with 7-day back-trajectory analysis at these locations as well as recent seasonal AOD maps [8]. [1] Prospero et al. (1970) Earth Planet. Sci. Lett. 9, 287-293. [2] Swap et al. (1992) Tellus 44, 133-149. [3] Koren et al. (2006) Environ. Res. Lett. 1, 014005. [4] Ben-Ami et al. (2010) Atmos. Chem. Phys. 10, 7533-7544. [5] Duce & Tindale (1991) Lim Ocean., 36, 1715-1726. [6] Bollhöfer & Rosman (2000) Geochim. Cosmochim. Acta 64, 3251-3262. [7] Abouchami et al. (in prep.) [8] Ridley et al. (2012) J. Geophys. Res. 117, D02202.

Use of radium isotopes to determine the age and origin of radioactive barite at oil-field production sites

USGS Publications Warehouse

Zielinski, R.A.; Otton, J.K.; Budahn, J.R.

2001-01-01

Radium-bearing barite (radiobarite) is a common constituent of scale and sludge deposits that form in oil-field production equipment. The barite forms as a precipitate from radium-bearing, saline formation water that is pumped to the surface along with oil. Radioactivity levels in some oil-field equipment and in soils contaminated by scale and sludge can be sufficiently high to pose a potential health threat. Accurate determinations of radium isotopes (226Ra+228Ra) in soils are required to establish the level of soil contamination and the volume of soil that may exceed regulatory limits for total radium content. In this study the radium isotopic data are used to provide estimates of the age of formation of the radiobarite contaminant. Age estimates require that highly insoluble radiobarite approximates a chemically closed system from the time of its formation. Age estimates are based on the decay of short-lived 228Ra (half-life=5.76 years) compared to 226Ra (half-life=1600 years). Present activity ratios of 228Ra/226Ra in radiobarite-rich scale or highly contaminated soil are compared to initial ratios at the time of radiobarite precipitation. Initial ratios are estimated by measurements of saline water or recent barite precipitates at the site or by considering a range of probable initial ratios based on reported values in modern oil-field brines. At sites that contain two distinct radiobarite sources of different age, the soils containing mixtures of sources can be identified, and mixing proportions quantified using radium concentration and isotopic data. These uses of radium isotope data provide more description of contamination history and can possibly address liability issues. Copyright ?? 2000 .

Storage dynamics in hydropedological units control hillslope connectivity, runoff generation, and the evolution of catchment transit time distributions

PubMed Central

Tetzlaff, D; Birkel, C; Dick, J; Geris, J; Soulsby, C

2014-01-01

We examined the storage dynamics and isotopic composition of soil water over 12 months in three hydropedological units in order to understand runoff generation in a montane catchment. The units form classic catena sequences from freely draining podzols on steep upper hillslopes through peaty gleys in shallower lower slopes to deeper peats in the riparian zone. The peaty gleys and peats remained saturated throughout the year, while the podzols showed distinct wetting and drying cycles. In this region, most precipitation events are <10 mm in magnitude, and storm runoff is mainly generated from the peats and peaty gleys, with runoff coefficients (RCs) typically <10%. In larger events the podzolic soils become strongly connected to the saturated areas, and RCs can exceed 40%. Isotopic variations in precipitation are significantly damped in the organic-rich soil surface horizons due to mixing with larger volumes of stored water. This damping is accentuated in the deeper soil profile and groundwater. Consequently, the isotopic composition of stream water is also damped, but the dynamics strongly reflect those of the near-surface waters in the riparian peats. “pre-event” water typically accounts for >80% of flow, even in large events, reflecting the displacement of water from the riparian soils that has been stored in the catchment for >2 years. These riparian areas are the key zone where different source waters mix. Our study is novel in showing that they act as “isostats,” not only regulating the isotopic composition of stream water, but also integrating the transit time distribution for the catchment. Key Points Hillslope connectivity is controlled by small storage changes in soil units Different catchment source waters mix in large riparian wetland storage Isotopes show riparian wetlands set the catchment transit time distribution PMID:25506098

Storage dynamics in hydropedological units control hillslope connectivity, runoff generation, and the evolution of catchment transit time distributions.

PubMed

Tetzlaff, D; Birkel, C; Dick, J; Geris, J; Soulsby, C

2014-02-01

We examined the storage dynamics and isotopic composition of soil water over 12 months in three hydropedological units in order to understand runoff generation in a montane catchment. The units form classic catena sequences from freely draining podzols on steep upper hillslopes through peaty gleys in shallower lower slopes to deeper peats in the riparian zone. The peaty gleys and peats remained saturated throughout the year, while the podzols showed distinct wetting and drying cycles. In this region, most precipitation events are <10 mm in magnitude, and storm runoff is mainly generated from the peats and peaty gleys, with runoff coefficients (RCs) typically <10%. In larger events the podzolic soils become strongly connected to the saturated areas, and RCs can exceed 40%. Isotopic variations in precipitation are significantly damped in the organic-rich soil surface horizons due to mixing with larger volumes of stored water. This damping is accentuated in the deeper soil profile and groundwater. Consequently, the isotopic composition of stream water is also damped, but the dynamics strongly reflect those of the near-surface waters in the riparian peats. "pre-event" water typically accounts for >80% of flow, even in large events, reflecting the displacement of water from the riparian soils that has been stored in the catchment for >2 years. These riparian areas are the key zone where different source waters mix. Our study is novel in showing that they act as "isostats," not only regulating the isotopic composition of stream water, but also integrating the transit time distribution for the catchment. Hillslope connectivity is controlled by small storage changes in soil unitsDifferent catchment source waters mix in large riparian wetland storageIsotopes show riparian wetlands set the catchment transit time distribution.

Volcanic systems of Iceland and their magma source

NASA Astrophysics Data System (ADS)

Sigmarsson, Olgeir

2017-04-01

Several active hot-spot volcanoes produce magma from mantle sources which composition varies on decadal time scale. This is probably best demonstrated by the recent work of Pietruszka and collaborators on Kilauea, Hawaii. In marked contrast, basalt lavas from volcanic system in Iceland located above the presumed centre of the Iceland mantle plume have uniform isotope composition over the last 10 thousand years. Volcanic systems are composed of a central volcano and a fissure swarm, or a combination of both and they represent a fundamental component of the neovolcanic zones in Iceland. Four such systems, those of Askja, Bárðarbunga, Kverkfjöll and Grímsvötn in central Iceland were chosen for investigation. The last three have central volcanoes covered by the Vatnajökull ice-sheet whereas part of their fissure swarms is ice-free. Tephra produced during subglacial eruptions together with lavas from the fissure swarms of Holocene age have been collected and analysed for Sr, Nd and Th isotope ratios. Those volcanic formations that can be univocally correlated to a given volcanic system display uniform isotope ratio but different from one volcanic system to another. An exception to this regularity is that Askja products have isotope ratios indistinguishable from those of Gímsvötn, but since these volcanic systems lies far apart their lava fields do not overlap. A practical aspect of these findings was demonstrated during the rifting event of Bárðarbunga and fissure eruption forming the Holuhraun lava field. Relatively low, O isotope ratios in these basalts and heterogeneous macrocrystal composition have been ascribed to important metabasaltic crustal contamination with or without crystal mush recycling. In that case a surprisingly efficient magma mixing and melt homogenization must have occurred in the past beneath the volcanic systems. One possibility is that during the rapid deglaciation much mantle melting occurred and melts accumulated at the mantle-crust boundary or within the crust in magma reservoirs that are still feeding the volcanic systems. A second possible explanation for absence of temporal variations of isotope ratios for a given volcanic system during the last 10 thousand years is that the roots of these systems lie at further depths within the mantle. In that case, extensive fertile source rock of recycled origin with distinct isotope composition must feed the volcanic system and that the melt extraction mechanism from these source regions does not alter (or homogenize) the final melt products. The consequences of these two mechanisms and possible discrimination between them will be discussed.

Carbon and nitrogen isotope effects associated with the dioxygenation of aniline and diphenylamine.

PubMed

Pati, Sarah G; Shin, Kwanghee; Skarpeli-Liati, Marita; Bolotin, Jakov; Eustis, Soren N; Spain, Jim C; Hofstetter, Thomas B

2012-11-06

Dioxygenation of aromatic rings is frequently the initial step of biodegradation of organic subsurface pollutants. This process can be tracked by compound-specific isotope analysis to assess the extent of contaminant transformation, but the corresponding isotope effects, especially for dioxygenation of N-substituted, aromatic contaminants, are not well understood. We investigated the C and N isotope fractionation associated with the biodegradation of aniline and diphenylamine using pure cultures of Burkholderia sp. strain JS667, which can biodegrade both compounds, each by a distinct dioxygenase enzyme. For diphenylamine, the C and N isotope enrichment was normal with ε(C)- and ε(N)-values of -0.6 ± 0.1‰ and -1.0 ± 0.1‰, respectively. In contrast, N isotopes of aniline were subject to substantial inverse fractionation (ε(N) of +13 ± 0.5‰), whereas the ε(C)-value was identical to that of diphenylamine. A comparison of the apparent kinetic isotope effects for aniline and diphenylamine dioxygenation with those from abiotic oxidation by manganese oxide (MnO(2)) suggest that the oxidation of a diarylamine system leads to distinct C-N bonding changes compared to aniline regardless of reaction mechanism and oxidant involved. Combined evaluation of the C and N isotope signatures of the contaminants reveals characteristic Δδ(15)N/Δδ(13)C-trends for the identification of diphenylamine and aniline oxidation in contaminated subsurfaces and for the distinction of aniline oxidation from its formation by microbial and/or abiotic reduction of nitrobenzene.

Carbon isotopes of dissolved inorganic carbon reflect utilization of different carbon sources by microbial communities in two limestone aquifer assemblages

NASA Astrophysics Data System (ADS)

Nowak, Martin E.; Schwab, Valérie F.; Lazar, Cassandre S.; Behrendt, Thomas; Kohlhepp, Bernd; Totsche, Kai Uwe; Küsel, Kirsten; Trumbore, Susan E.

2017-08-01

Isotopes of dissolved inorganic carbon (DIC) are used to indicate both transit times and biogeochemical evolution of groundwaters. These signals can be complicated in carbonate aquifers, as both abiotic (i.e., carbonate equilibria) and biotic factors influence the δ13C and 14C of DIC. We applied a novel graphical method for tracking changes in the δ13C and 14C of DIC in two distinct aquifer complexes identified in the Hainich Critical Zone Exploratory (CZE), a platform to study how water transport links surface and shallow groundwaters in limestone and marlstone rocks in central Germany. For more quantitative estimates of contributions of different biotic and abiotic carbon sources to the DIC pool, we used the NETPATH geochemical modeling program, which accounts for changes in dissolved ions in addition to C isotopes. Although water residence times in the Hainich CZE aquifers based on hydrogeology are relatively short (years or less), DIC isotopes in the shallow, mostly anoxic, aquifer assemblage (HTU) were depleted in 14C compared to a deeper, oxic, aquifer complex (HTL). Carbon isotopes and chemical changes in the deeper HTL wells could be explained by interaction of recharge waters equilibrated with post-bomb 14C sources with carbonates. However, oxygen depletion and δ13C and 14C values of DIC below those expected from the processes of carbonate equilibrium alone indicate considerably different biogeochemical evolution of waters in the upper aquifer assemblage (HTU wells). Changes in 14C and 13C in the upper aquifer complexes result from a number of biotic and abiotic processes, including oxidation of 14C-depleted OM derived from recycled microbial carbon and sedimentary organic matter as well as water-rock interactions. The microbial pathways inferred from DIC isotope shifts and changes in water chemistry in the HTU wells were supported by comparison with in situ microbial community structure based on 16S rRNA analyses. Our findings demonstrate the large variation in the importance of biotic as well as abiotic controls on 13C and 14C of DIC in closely related aquifer assemblages. Further, they support the importance of subsurface-derived carbon sources like DIC for chemolithoautotrophic microorganisms as well as rock-derived organic matter for supporting heterotrophic groundwater microbial communities and indicate that even shallow aquifers have microbial communities that use a variety of subsurface-derived carbon sources.

Crustal forensics in arc magmas

NASA Astrophysics Data System (ADS)

Davidson, Jon P.; Hora, John M.; Garrison, Jennifer M.; Dungan, Michael A.

2005-01-01

The geochemical characteristics of continental crust are present in nearly all arc magmas. These characteristics may reflect a specific source process, such as fluid fluxing, common to both arc magmas and the continental crust, and/or may reflect the incorporation of continental crust into arc magmas either at source via subducted sediment, or via contamination during differentiation. Resolving the relative mass contributions of juvenile, mantle-derived material, versus that derived from pre-existing crust of the upper plate, and providing these estimates on an element-by-element basis, is important because: (1) we want to constrain crustal growth rates; (2) we want to quantitatively track element cycling at convergent margins; and (3) we want to determine the origin of economically important elements and compounds. Traditional geochemical approaches for determining the contributions of various components to arc magmas are particularly successful when applied on a comparative basis. Studies of suites from multiple magmatic systems along arcs, for which differentiation effects can be individually constrained, can be used to extrapolate to potential source compositions. In the Lesser Antilles Arc, for example, differentiation trends from individual volcanoes are consistent with open-system evolution. However, such trends do not project back to a common primitive magma composition, suggesting that differentiation modifies magmas that were derived from distinct mantle sources. We propose that such approaches should now be complemented by petrographically constrained mineral-scale isotope and trace element analysis to unravel the contributing components to arc magmas. This innovative approach can: (1) better constrain true end-member compositions by returning wider ranges in geochemical compositions among constituent minerals than is found in whole rocks; (2) better determine magmatic evolution processes from core-rim isotopic or trace element profiles from the phases contained in magmas; and (3) constrain rates of differentiation by applying diffusion-controlled timescales to element profiles. An example from Nguaruhoe Volcano, New Zealand, underscores the importance of such a microsampling approach, showing that mineral isotopic compositions encompass wide ranges, that whole-rock isotopic compositions are consequently simply element-weighted averages of the heterogeneous crystal cargo, and that open-system evolution is proved by core-rim variations in Sr isotope ratios. Nguaruhoe is just one of many systems examined through microanalytical approaches. The overwhelming conclusion of these studies is that crystal cargoes are not truly phenocrystic, but are inherited from various sources. The implication of this realization is that the interpretation of whole-rock isotopic data, including the currently popular U-series, needs careful evaluation in the context of petrographic observations.

Tracing anthropogenic aerosol Fe sources in the North Atlantic Ocean using dissolved Fe isotope ratios

NASA Astrophysics Data System (ADS)

Conway, T. M.; Shelley, R.; Aguilar-Islas, A. M.; Landing, W. M.; Mahowald, N. M.; John, S.

2016-02-01

Supply of iron (Fe) to the surface ocean from atmospheric deposition plays a vital role in marine biogeochemical cycles, especially in Fe-limited areas or regions close to dust sources. However, large uncertainties remain over the fluxes, solubility and bioavailability of Fe supplied by aerosol dust. Additionally, aerosol Fe is likely to consist of a mixture of natural and anthropogenic (urban, biomass burning and combustion) components, which may have very different solubilities in seawater [e.g. 1]. To constrain soluble Fe supply to the oceans, it is thus vitally important to understand the relative contributions of different types of aerosol Fe, their solubilities and spatial distributions. Stable Fe isotopes (δ56Fe) may offer a way to discriminate between different dust sources [2], because of differential fractionation during a range of chemical processes. In this study, we measured δ56Fe in North Atlantic marine aerosols collected during two US GEOTRACES GA03 cruises (Lisbon to Woods Hole via Cape Verde, 2010-11) and we present δ56Fe measurements (relative to IRMM-014) from both the bulk aerosol (HF-HNO3 digested) and the water-soluble (10s ultrapure water leach) fractions. Aerosols collected from different air-masses (Saharan, European and N. American) allowed us to investigate the variability in δ56Fe due to different regional dust sources. The bulk phase was characterized by near-crustal δ56Fe values of +0.1±0.2‰, indicating the dominance of mineral dust. In contrast, the water-soluble fraction showed great variability; aerosols from European and North American air-masses were very isotopically light (-1.2±0.2‰ and -1.1±0.7‰) while those from Saharan air-masses were crustal (+0.1‰). Comparison of this data with isotope-informed model predictions of soluble Fe from mineral and anthropogenic sources (combustion, biofuels and biomass burning) [1], suggests that the data is consistent with mixing of either 1) Fe from mineral dust (+0.1‰) and a distinctly light anthropogenic Fe (-1.6‰), or 2) Fe from crustal mineral dust, isotopically heavy combustion Fe (+0.1 to +0.3‰), and biomass Fe that is both isotopically light (-1.6‰) and very soluble (>50%). [1] Luo, C. et al. (2008), Glob. Biogeochem. Cyc., 22, GB1012. [2] Mead, C. et al. (2013), Geophys. Res. Lett., 40, 5722-5727.

Filling the gap for phosphorus tracing in the eco-hydrological system: are oxygen stable isotopes in phosphate a possible tool?

NASA Astrophysics Data System (ADS)

Stamm, C.; Tamburini, F.; Hahn, C.; Stadelmann, F.; Bernasconi, S. M.; Frossard, E.

2011-12-01

Phosphorus is a limiting nutrient in many ecosystems. However, freshwater systems are experiencing nutrient overload and consequent eutrophication, caused mainly by a poor use of resources and in many situations by the input of a surplus of nutrients from agriculture. The sources of nutrient pollution together with the fate of the nutrients once in the water system need to be identified and understood, so that a better management can be implemented. There are multiple agricultural P-sources like mineral fertilizers, animal excreta, plant residues, soils, and since P has only one stable isotope, no analytical method allows to directly distinguishing P from its different possible source. However, the isotopic signature of oxygen associated to phosphate (δ18O-P) has been considered to be a promising tool for such source tracing in the environment. The main limitation of using this tool as a tracer is that biological activity could erase the original source signature, which is overprinted by a temperature dependent equilibration with oxygen in water. We present data from the region of Lake Baldegg (Central Switzerland), which is characterized by a high animal density (dairy cows, pigs) and intensive grassland cultivation. P losses from the grasslands constitute the main source of P for the freshwater system. Using δ18O-P, we have first characterized animal manure, soil available P, and plant P, the three main possible Pi sources to the system, and we have determined the δ18O-P of three brooks at different time points. Phosphorus concentration, oxygen isotopic composition of water and temperature were also monitored. The three sources of P showed well distinct signatures, with values from animal manures and plants being 12% and higher than 20%, respectively. Depending on the time of sampling, the δ18O-P in the brooks showed deviations from the expected equilibrium, pointing to a contribution of P coming from animal manure. Data from runoff experiments in the same region showed an inverse correlation between δ18O-P in runoff water and P concentration in the soil. This indicated that manure P contributed directly to P mobilized into the surface runoff. The presented results, together with the outcome of other recent studies, indicate the usefulness and potentiality of δ18O-P a tracer for P in hydrological systems.

Stable isotope phenotyping via cluster analysis of NanoSIMS data as a method for characterizing distinct microbial ecophysiologies and sulfur-cycling in the environment

NASA Astrophysics Data System (ADS)

Dawson, K.; Scheller, S.; Dillon, J. G.; Orphan, V. J.

2016-12-01

Stable isotope probing (SIP) is a valuable tool for gaining insights into ecophysiology and biogeochemical cycling of environmental microbial communities by tracking isotopically labeled compounds into cellular macromolecules as well as into byproducts of respiration. SIP, in conjunction with nanoscale secondary ion mass spectrometry (NanoSIMS), allows for the visualization of isotope incorporation at the single cell level. In this manner, both active cells within a diverse population as well as heterogeneity in metabolism within a homogeneous population can be observed. The ecophysiological implications of these single cell stable isotope measurements are often limited to the taxonomic resolution of paired fluorescence in situ hybridization (FISH) microscopy. Here we introduce a taxonomy-independent method using multi-isotope SIP and NanoSIMS for identifying and grouping phenotypically similar microbial cells by their chemical and isotopic fingerprint. This method was applied to SIP experiments in a sulfur-cycling biofilm collected from sulfidic intertidal vents amended with 13C-acetate, 15N-ammonium, and 33S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope (13C/12C, 15N/14N, and 33S/32S) and elemental ratio (C/CN and S/CN) profiles, our analysis partitioned 2200 cellular regions of interest (ROIs) into 5 distinct groups. These isotope phenotype groupings are reflective of the variation in labeled substrate uptake by cells in a multispecies metabolic network dominated by Gamma- and Deltaproteobacteria. Populations independently grouped by isotope phenotype were subsequently compared with paired FISH data, demonstrating a single coherent deltaproteobacterial cluster and multiple gammaproteobacterial groups, highlighting the distinct ecophysiologies of spatially-associated microbes within the sulfur-cycling biofilm from White Point Beach, CA.

Stable Isotope Phenotyping via Cluster Analysis of NanoSIMS Data As a Method for Characterizing Distinct Microbial Ecophysiologies and Sulfur-Cycling in the Environment

PubMed Central

Dawson, Katherine S.; Scheller, Silvan; Dillon, Jesse G.; Orphan, Victoria J.

2016-01-01

Stable isotope probing (SIP) is a valuable tool for gaining insights into ecophysiology and biogeochemical cycling of environmental microbial communities by tracking isotopically labeled compounds into cellular macromolecules as well as into byproducts of respiration. SIP, in conjunction with nanoscale secondary ion mass spectrometry (NanoSIMS), allows for the visualization of isotope incorporation at the single cell level. In this manner, both active cells within a diverse population as well as heterogeneity in metabolism within a homogeneous population can be observed. The ecophysiological implications of these single cell stable isotope measurements are often limited to the taxonomic resolution of paired fluorescence in situ hybridization (FISH) microscopy. Here we introduce a taxonomy-independent method using multi-isotope SIP and NanoSIMS for identifying and grouping phenotypically similar microbial cells by their chemical and isotopic fingerprint. This method was applied to SIP experiments in a sulfur-cycling biofilm collected from sulfidic intertidal vents amended with 13C-acetate, 15N-ammonium, and 33S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope (13C/12C, 15N/14N, and 33S/32S) and elemental ratio (C/CN and S/CN) profiles, our analysis partitioned ~2200 cellular regions of interest (ROIs) into five distinct groups. These isotope phenotype groupings are reflective of the variation in labeled substrate uptake by cells in a multispecies metabolic network dominated by Gamma- and Deltaproteobacteria. Populations independently grouped by isotope phenotype were subsequently compared with paired FISH data, demonstrating a single coherent deltaproteobacterial cluster and multiple gammaproteobacterial groups, highlighting the distinct ecophysiologies of spatially-associated microbes within the sulfur-cycling biofilm from White Point Beach, CA. PMID:27303371

Distinctly different parental magmas for plutons and lavas in the central Aleutian arc

NASA Astrophysics Data System (ADS)

Cai, Y.; Rioux, M. E.; Kelemen, P. B.; Goldstein, S. L.; Bolge, L.; Kylander-Clark, A. R.

2014-12-01

While it is generally agreed that continental crust is generated by arc magmatism, average arc lavas are basaltic while the bulk continental crust is andesitic, and this has led to many models for secondary reprocessing of the arc crust in order to form continental crust. We report new data on calc-alkaline plutons in the central Aleutians showing that they have distinctly different sources compared to Holocene tholeiitic lavas. Therefore the lavas are not representative of the net magmatic transfer from the mantle into the arc crust. Eocene to Miocene (9-39 Ma) intermediate to felsic plutonic rocks from the central Aleutian arc show higher SiO2 at a given Mg#, higher ɛNd- and ɛHf-values, and lower Pb isotope ratios than Holocene volcanic rocks from the same region. Instead, the plutonic rocks resemble volcanics from the western Aleutians isotopically, and have chemical compositions similar to bulk continental crust. These data could reflect temporal variation of Aleutian magma source compositions, from Eocene-Miocene "isotopically depleted" and predominantly calc-alkaline to Holocene "isotopically enriched" and predominantly tholeiitic. Alternatively, they may reflect different transport and emplacement processes for the magmas that form plutons and lavas: calc-alkaline magmas with higher Si content and high viscosity may preferentially form plutons, perhaps after extensive mid-crustal degassing of initially high water contents. The latter case implies that the upper and middle arc crust is more like the calc-alkaline bulk composition of the continental crust than the lavas alone. Crustal reprocessing mechanisms that preserve upper and middle arc crust, while removing lower arc crust, can account for the genesis and evolution of continental crust. Since gabbroic lower arc crust extends from ca 20-40 km depth, and is density stable over most of this depth range, "delamination" of dense lithologies [1] may not be sufficient to accomplish this. Alternatively, subduction erosion of arc crust followed by "relamination" [2] of buoyant calc-alkaline rocks may be more effective. [1] e.g. Ringwood & Green, Tectonophysics 1966; Herzberg et al. Contributions to mineralogy and petrology 1983; [2] e.g. Hacker et al. Earth and Planetary Science Letters 2011.

Developing SNMS for Full-Spectrum High-Sensitivity In-Situ Isotopic Analysis of Individual Comet Grains Collected by Stardust?

NASA Technical Reports Server (NTRS)

Chen, Chun-Yen; Shen, Jason Jiun-San; Lee, Typhoon; Calaway, Wallis; Veryovkin, Igor; Moore, Jerry; Pellin, Michael

2005-01-01

In anticipation of the return of comet (and ISM?) dust grains by the Stardust mission [1] in mid-January next year, Academia Sinica (AS) and Argonne National Laboratory (ANL) have entered into a collaboration to develop instrument and method for the isotopic analysis of these samples. We need to achieve the highest possible sensitivity so that we can analyze individual grains one at a time to the smallest possible size. Only by doing so can we hope to reach one of the main science goals of the mission, namely the recognition of those isotopically distinct grains each carrying the characteristic signature of a particular nucleosynthetic stage of its parent star. In order to facilitate the interpretation of these grains the second requirement of our method is that the measurements must be made over the widest possible mass range before samples exhaustion. For instance, the thermonuclear fusion reactions that produced the isotopes of various major elements of a wide mass range required drastically different temperatures. Therefore their abundances could constrain the conditions at greatly varying depth inside the source star hence its structure and evolution.

A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

NASA Astrophysics Data System (ADS)

Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

2014-12-01

Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar experiments were performed with bacterial nitric oxide reductase from Paracoccus denitrificans (cNOR). In this case both Nα and Nβ exhibited inverse isotope effects, while O had a normal isotope effect. Together, these data highlight the utility in using stable isotopes as both tracers and mechanistic probes when studying metabolic processes.

Implications of Eocene-age Philippine Sea and forearc basalts for initiation and early history of the Izu-Bonin-Mariana arc

NASA Astrophysics Data System (ADS)

Yogodzinski, Gene M.; Bizimis, Michael; Hickey-Vargas, Rosemary; McCarthy, Anders; Hocking, Benjamin D.; Savov, Ivan P.; Ishizuka, Osamu; Arculus, Richard

2018-05-01

Whole-rock isotope ratio (Hf, Nd, Pb, Sr) and trace element data for basement rocks at ocean drilling Sites U1438, 1201 and 447 immediately west of the KPR (Kyushu-Palau Ridge) are compared to those of FAB (forearc basalts) previously interpreted to be the initial products of IBM subduction volcanism. West-of-KPR basement basalts (drill sites U1438, 1201, 447) and FAB occupy the same Hf-Nd and Pb-Pb isotopic space and share distinctive source characteristics with εHf mostly > 16.5 and up to εHf = 19.8, which is more radiogenic than most Indian mid-ocean ridge basalts (MORB). Lead isotopic ratios are depleted, with 206Pb/204Pb = 17.8-18.8 accompanying relatively high 208Pb/204Pb, indicating an Indian-MORB source unlike that of West Philippine Basin plume basalts. Some Sr isotopes show affects of seawater alteration, but samples with 87Sr/86Sr < 0.7034 and εNd > 8.0 appear to preserve magmatic compositions and also indicate a common source for west-of-KPR basement and FAB. Trace element ratios resistant to seawater alteration (La/Yb, Lu/Hf, Zr/Nb, Sm/Nd) in west-of-KPR basement are generally more depleted than normal MORB and so also appear similar to FAB. At Site U1438, only andesite sills intruding sedimentary rocks overlying the basement have subduction-influenced geochemical characteristics (εNd ∼ 6.6, εHf ∼ 13.8, La/Yb > 2.5, Nd/Hf ∼ 9). The key characteristic that unites drill site basement rocks west of KPR and FAB is the nature of their source, which is more depleted in lithophile trace elements than average MORB but with Hf, Nd, and Pb isotope ratios that are common in MORB. The lithophile element-depleted nature of FAB has been linked to initiation of IBM subduction in the Eocene, but Sm-Nd model ages and errorchron relationships in Site U1438 basement indicate that the depleted character of the rocks is a regional characteristic that was produced well prior to the time of subduction initiation and persists today in the source of modern IBM arc volcanic rocks with Sm/Nd > 0.34 and εNd ∼ 9.0.

Isotopic constraints on global atmospheric methane sources and sinks: a critical assessment of recent findings and new data

NASA Astrophysics Data System (ADS)

Schwietzke, S.; Sherwood, O.; Michel, S. E.; Bruhwiler, L.; Dlugokencky, E. J.; Tans, P. P.

2017-12-01

Methane isotopic data have increasingly been used in recent studies to help constrain global atmospheric methane sources and sinks. The added scientific contributions to this field include (i) careful comparisons and merging of atmospheric isotope measurement datasets to increase spatial coverage, (ii) in-depth analyses of observed isotopic spatial gradients and seasonal patterns, and (iii) improved datasets of isotopic source signatures. Different interpretations have been made regarding the utility of the isotopic data on the diagnosis of methane sources and sinks. Some studies have found isotopic evidence of a largely microbial source causing the renewed growth in global atmospheric methane since 2007, and underestimated global fossil fuel methane emissions compared to most previous studies. However, other studies have challenged these conclusions by pointing out substantial spatial variability in isotopic source signatures as well as open questions in atmospheric sinks and biomass burning trends. This presentation will review and contrast the main arguments and evidence for the different conclusions. The analysis will distinguish among the different research objectives including (i) global methane budget source attribution in steady-state, (ii) source attribution of recent global methane trends, and (iii) identifying specific methane sources in individual plumes during field campaigns. Additional comparisons of model experiments with atmospheric measurements and updates on isotopic source signature data will complement the analysis.

A comparative molecular and isotopic investigation of seep carbonates from mussel and tubeworm environments of the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Feng, D.; Guan, H.; Wu, N.; Chen, D.

2017-12-01

At deep-sea hydrocarbon seeps, macrofauna such as mussels and tubeworms and authigenic carbonate outcrops are common. It has been suggested that the distinct metabolic process of the macrofauna could modify the sedimentary geochemistry of their ambient environments. To better understand if the differences in the geochemical environments of mussels and tubeworms can be archived in the associated carbonates, lipid biomarker inventory and compound-specific isotopes of the carbonates from mussel and tubeworm environments from two seep sites were analyzed. The large δ13C offset (-32‰) of SRB-derived fatty acids (FAs) between tubeworm and mussel carbonates were partially attributed to the distinct effects on isotope fraction by specific metabolic process of the macrofauna. In such processes, the isotope fraction of chemosynthetic symbionts and physical action of mussel activities could result in local 13C enrichment, whereas the sufficient sulfate released through the tubeworm roots resulting in a persistent production of methane-derived bicarbonate and the enrichment of lighter carbon at subsurface sediments. Compared to mussel carbonates, the significantly higher concentrations of DAGEs and FAs as well as the smaller δ13C offset (Δδ13CDAGEs-FAs) than that of the mussel carbonates, suggest that the DAGEs and at least part of FAs found in tubeworm carbonates biosynthesized by SRB species other than DSS cluster. This DAGE-producing SRB is most likely involved in the hydrogen-driven SR instead of methane-fueled SR because a variety of SRB other than members of DSS cluster on hydrogen was isolated in presence of ANME-1 assemblage. The substantial amounts of DAGEs with strong 13C-depletions in tubeworm ecosystem may provide an important clue for their sources and role in the AOM process.

Precipitation regime influence on oxygen triple-isotope distributions in Antarctic precipitation and ice cores

NASA Astrophysics Data System (ADS)

Miller, Martin F.

2018-01-01

The relative abundance of 17O in meteoric precipitation is usually reported in terms of the 17O-excess parameter. Variations of 17O-excess in Antarctic precipitation and ice cores have hitherto been attributed to normalised relative humidity changes at the moisture source region, or to the influence of a temperature-dependent supersaturation-controlled kinetic isotope effect during in-cloud ice formation below -20 °C. Neither mechanism, however, satisfactorily explains the large range of 17O-excess values reported from measurements. A different approach, based on the regression characteristics of 103 ln (1 +δ17 O) versus 103 ln (1 +δ18 O), is applied here to previously published isotopic data sets. The analysis indicates that clear-sky precipitation ('diamond dust'), which occurs widely in inland Antarctica, is characterised by an unusual relative abundance of 17O, distinct from that associated with cloud-derived, synoptic snowfall. Furthermore, this distinction appears to be largely preserved in the ice core record. The respective mass contributions to snowfall accumulation - on both temporal and spatial scales - provides the basis of a simple, first-order explanation for the observed oxygen triple-isotope ratio variations in Antarctic precipitation, surface snow and ice cores. Using this approach, it is shown that precipitation during the last major deglaciation, both in western Antarctica at the West Antarctic Ice Sheet (WAIS) Divide and at Vostok on the eastern Antarctic plateau, consisted essentially of diamond dust only, despite a large temperature differential (and thus different water vapour supersaturation conditions) at the two locations. In contrast, synoptic snowfall events dominate the accumulation record throughout the Holocene at both sites.

Geochemistry of mineral waters and associated gases of the Sakhalin Island (Far East of Russia)

NASA Astrophysics Data System (ADS)

Chelnokov, George A.; Bragin, Ivan V.; Kharitonova, Natalia A.

2018-04-01

Isotopic and chemical data on the mineral water, mud volcanoes fluid and associated gases from the biggest Russian island Sakhalin, together with previous stable isotope data (d18O, dD, 13C), allow elucidation of their origin and general evolution. The water fluid circulation is mainly related to marine environment inducing three distinct types: Na-HCO3-Cl alkali carbonate groundwaters, Na-Cl-HCO3 highly evolved saline and Na-Cl mature groundwaters, indicating different evolution. Chemical evolution of groundwater on Sakhalin Island demonstrated cation exchange and salinization as dominant evolutionary pathways. Isotopic composition of groundwaters varies from meteoric to metamorphic waters. These metamorphic waters consist of water hydration from the clay and seawater are traced in fluids of Yuzhno-Sakhalin mud volcano despite modification by mixing with meteoric waters and water-rock interaction processes. Fault systems that define the areas of highly mineralized water circulation appear to play a major role in the CO2 migration to the surface and CH4 generation. The δ13C(CO2) values have pointed that gas phase in high-pCO2 waters mostly consists of mantle-derived CO2. The carbon isotope signature of methane δ13C(CH4) and δD(CH4) indicates its distinct origin which is specified by tectonics. Methane manifestation in the south of the Sakhalin Island is mainly related to thermogenic reservoirs as they are more often dislocate by tectonics, and crossed by active and permeable faults. The sources of biogenous methane in the north of Sakhalin Island is related to younger and shallower reservoirs, and less affected by tectonic processes. The determinations of 222Rn have allowed observing that maximal radon flux is associated with high pCO2 waters.

The Distinct Genetics of Carbonaceous and Non-Carbonaceous Meteorites Inferred from Molybdenum Isotopes

NASA Astrophysics Data System (ADS)

Budde, G.; Burkhardt, C.; Kleine, T.

2017-07-01

Mo isotope systematics manifest a fundamental dichotomy in the genetic heritage of carbonaceous and non-carbonaceous meteorites. We discuss its implications in light of the most recent literature data and new isotope data for primitive achondrites.

Metrology for stable isotope reference materials: 13C/12C and 18O/16O isotope ratio value assignment of pure carbon dioxide gas samples on the Vienna PeeDee Belemnite-CO2 scale using dual-inlet mass spectrometry.

PubMed

Srivastava, Abneesh; Michael Verkouteren, R

2018-07-01

Isotope ratio measurements have been conducted on a series of isotopically distinct pure CO 2 gas samples using the technique of dual-inlet isotope ratio mass spectrometry (DI-IRMS). The influence of instrumental parameters, data normalization schemes on the metrological traceability and uncertainty of the sample isotope composition have been characterized. Traceability to the Vienna PeeDee Belemnite(VPDB)-CO 2 scale was realized using the pure CO 2 isotope reference materials(IRMs) 8562, 8563, and 8564. The uncertainty analyses include contributions associated with the values of iRMs and the repeatability and reproducibility of our measurements. Our DI-IRMS measurement system is demonstrated to have high long-term stability, approaching a precision of 0.001 parts-per-thousand for the 45/44 and 46/44 ion signal ratios. The single- and two-point normalization bias for the iRMs were found to be within their published standard uncertainty values. The values of 13 C/ 12 C and 18 O/ 16 O isotope ratios are expressed relative to VPDB-CO 2 using the [Formula: see text] and [Formula: see text] notation, respectively, in parts-per-thousand (‰ or per mil). For the samples, value assignments between (-25 to +2) ‰ and (-33 to -1) ‰ with nominal combined standard uncertainties of (0.05, 0.3) ‰ for [Formula: see text] and [Formula: see text], respectively were obtained. These samples are used as laboratory reference to provide anchor points for value assignment of isotope ratios (with VPDB traceability) to pure CO 2 samples. Additionally, they serve as potential parent isotopic source material required for the development of gravimetric based iRMs of CO 2 in CO 2 -free dry air in high pressure gas cylinder packages at desired abundance levels and isotopic composition values. Graphical abstract CO 2 gas isotope ratio metrology.

INCORPORATING CONCENTRATION DEPENDENCE IN STABLE ISOTOPE MIXING MODELS

EPA Science Inventory

Stable isotopes are frequently used to quantify the contributions of multiple sources to a mixture; e.g., C and N isotopic signatures can be used to determine the fraction of three food sources in a consumer's diet. The standard dual isotope, three source linear mixing model ass...

INCORPORATING CONCENTRATION DEPENDENCE IN STABLE ISOTOPE MIXING MODELS

EPA Science Inventory

Stable isotopes are often used as natural labels to quantify the contributions of multiple sources to a mixture. For example, C and N isotopic signatures can be used to determine the fraction of three food sources in a consumer's diet. The standard dual isotope, three source li...

Mantle heterogeneity in the source region of mid-ocean ridge basalts along the northern Central Indian Ridge (8°S-17°S)

NASA Astrophysics Data System (ADS)

Kim, Jonguk; Pak, Sang-Joon; Moon, Jai-Woon; Lee, Sang-Mook; Oh, Jihye; Stuart, Finlay M.

2017-04-01

The northern Central Indian Ridge (CIR) between 8°S and 17°S is composed of seven segments whose spreading rates increase southward from ˜35 to ˜40 mm/yr. During expeditions of R/V Onnuri to study hydrothermal activity on the northern CIR in 2009-2011, high-resolution multibeam mapping was conducted and ridge axis basalts were dredged. The major and trace element and Sr-Nd-Pb-He isotopic compositions of basaltic glasses dredged from the spreading axis require three mantle sources: depleted mantle and two distinct enriched mantle sources. The southern segments have Sr, Nd, and Pb that are a mix of depleted mantle and an enriched component as recorded in southern CIR MORB. This enrichment is indistinguishable from Rèunion plume mantle, except for He isotopes. This suggests that the southern segments have incorporated a contribution of the fossil Rèunion plume mantle, as the CIR migrated over hot-spot-modified mantle. The low 3He/4He (7.5-9.2 RA) of this enriched component may result from radiogenic 4He ingrowth in the fossil Rèunion mantle component. Basalts from the northern segments have high 206Pb/204Pb (18.53-19.15) and low 87Sr/86Sr (0.70286-0.70296) that are distinct from the Rèunion plume but consistent with derivation from mantle with FOZO signature, albeit with 3He/4He (9.2-11.8 RA) that are higher than typical. The FOZO-like enriched mantle cannot be attributed to the track of a nearby mantle plume. Instead, this enrichment may have resulted from recycling oceanic crust, possibly accompanied by small plume activity.

The bulk isotopic composition of hydrocarbons in subaerial volcanic-hydrothermal emissions from different tectonic settings

NASA Astrophysics Data System (ADS)

Fiebig, J.; Tassi, F.; Vaselli, O.; Viveiros, M. F.; Silva, C.; Lopez, T. M.; D'Alessandro, W.; Stefansson, A.

2015-12-01

Assuming that methane and its higher chain homologues derive from a common source, carbon isotope patterns have been applied as a criterion to identify occurrences of abiogenic hydrocarbons. Based on these, it has been postulated that abiogenic hydrocarbon production occurs within several (ultra)mafic environments. More evolved volcanic-hydrothermal systems may also provide all the prerequisites necessary for abiogenic hydrocarbon production, such as availability of inorganic CO2, hydrogen and heat. We have investigated the chemical and isotopic composition of n-alkanes contained within subaerial hydrothermal discharges emitted from a range of hot spot, subduction and rift-related volcanoes to determine the origin of hydrocarbons in these systems. Amongst these are Nisyros (Greece), Vesuvio, Campi Flegrei, Ischia, Pantelleria and Vulcano (all Italy), Mt. Mageik and Trident (USA), Copahue (Argentina), Teide (Spain), Furnas and Fogo (Portugal). The carbon isotopic composition of methane emitted from these sites varies from -65 to -8‰ , whereas δ13C of ethane and propane exhibit a much narrower variation from -17‰ to -31‰. Methane that occurs most enriched in 13C is also characterized by relatively positive δD values ranging up to -80‰. Carbon isotope reversals between methane and ethane are only observed for locations exhibiting δ13C-CH4 values > -20‰, such as Teide, Pantelleria, Trident and Furnas. At Furnas, δ13C-CH4 varies by 50‰ within a relatively short distance of <50m between two vents, whereas δ13C-C2H6 varies by less than 2‰ only. For some of the investigated locations apparent carbon isotopic temperatures between methane and CO2 are in agreement with those derived from gas concentration geothermometers. At these locations methane, however seems to be in disequilibrium with ethane and propane. These findings imply that methane on the one hand and the C2+ hydrocarbons on the other hand often might derive from distinct sources.

Volatiles in the Earth and Moon: Constraints on planetary formation and evolution

NASA Astrophysics Data System (ADS)

Parai, Rita

The volatile inventories of the Earth and Moon reflect unique histories of volatile acquisition and loss in the early Solar System. The terrestrial volatile inventory was established after the giant impact phase of accretion, and the planet subsequently settled into a regime of long-term volatile exchange between the mantle and surface reservoirs in association with plate tectonics. Therefore, volatiles in the Earth and Moon shed light on a diverse array of processes that shaped planetary bodies in the Solar System as they evolved to their present-day states. Here we investigate new constraints on volatile depletion in the early Solar System, early outgassing of the terrestrial mantle, and the long-term evolution of the deep Earth volatile budget. We develop a Monte Carlo model of long-term water exchange between the mantle and surface reservoirs. Previous estimates of the deep Earth return flux of water are up to an order of magnitude too large, and incorporation of recycled slabs on average rehydrates the upper mantle but dehydrates the plume source. We find evidence for heterogeneous recycling of atmospheric argon and xenon into the upper mantle from noble gases in Southwest Indian Ridge basalts. Xenon isotope systematics indicate that xenon budgets of mid-ocean ridge and plume-related mantle sources are dominated by recycled atmospheric xenon, though the two sources have experienced different degrees of degassing. Differences between the mid-ocean ridge and plume sources were initiated within the first 100 million years of Earth history, and the two sources have never subsequently been homogenized. New high-precision xenon isotopic data contribute to an emerging portrait of two mantle reservoirs with distinct histories of outgassing and incorporation of recycled material in association with plate tectonics. Xenon isotopes indicate that the Moon likely formed within ˜70 million years of the start of the Solar System. To further investigate early Solar System chronology, we determined strontium isotopic compositions in a suite of planetary materials. If the Moon is derived from proto-Earth material, then rubidium-strontium systematics in the lunar anorthosite 60025 and Moore County plagioclase indicate that Moon formation occurred within ~62 million years of the start of the Solar System.

Coordinates Analyses of Hydrated Interplanetary Dust Particles: Samples of Primitive Solar System Bodies

NASA Technical Reports Server (NTRS)

Keller, L. P.; Snead, C.; McKeegan, K. D.

2016-01-01

Interplanetary dust particles (IDPs) collected in the stratosphere fall into two major groups: an anhydrous group termed the "chondritic-porous (CP) IDPs and a hydrated group, the "chondritic-smooth (CS) IDPs, although rare IDPs with mineralogies intermediate between these two groups are known [1]. The CP-IDPs are widely believed to be derived from cometary sources [e.g. 2]. The hydrated CS-IDPs show mineralogical similarities to heavily aqueously altered carbonaceous chondrites (e.g. CI chondrites), but only a few have been directly linked to carbonaceous meteorite parent bodies [e.g. 3, 4]. Most CS-IDPs show distinct chemical [5] and oxygen isotopic composition differences [6-8] from primitive carbonaceous chondrites. Here, we report on our coordinated analyses of a suite of carbon-rich CS-IDPs focusing on their bulk compositions, mineralogy, mineral chemistry, and isotopic compositions.

Temperature and composition of carbonate cements record early structural control on cementation in a nascent deformation band fault zone: Moab Fault, Utah, USA

NASA Astrophysics Data System (ADS)

Hodson, Keith R.; Crider, Juliet G.; Huntington, Katharine W.

2016-10-01

Fluid-driven cementation and diagenesis within fault zones can influence host rock permeability and rheology, affecting subsequent fluid migration and rock strength. However, there are few constraints on the feedbacks between diagenetic conditions and structural deformation. We investigate the cementation history of a fault-intersection zone on the Moab Fault, a well-studied fault system within the exhumed reservoir rocks of the Paradox Basin, Utah, USA. The fault zone hosts brittle structures recording different stages of deformation, including joints and two types of deformation bands. Using stable isotopes of carbon and oxygen, clumped isotope thermometry, and cathodoluminescence, we identify distinct source fluid compositions for the carbonate cements within the fault damage zone. Each source fluid is associated with different carbonate precipitation temperatures, luminescence characteristics, and styles of structural deformation. Luminescent carbonates appear to be derived from meteoric waters mixing with an organic-rich or magmatic carbon source. These cements have warm precipitation temperatures and are closely associated with jointing, capitalizing on increases in permeability associated with fracturing during faulting and subsequent exhumation. Earlier-formed non-luminescent carbonates have source fluid compositions similar to marine waters, low precipitation temperatures, and are closely associated with deformation bands. The deformation bands formed at shallow depths very early in the burial history, preconditioning the rock for fracturing and associated increases in permeability. Carbonate clumped isotope temperatures allow us to associate structural and diagenetic features with burial history, revealing that structural controls on fluid distribution are established early in the evolution of the host rock and fault zone, before the onset of major displacement.

Influence of nitrogen substrates and substrate C:N ratios on the nitrogen isotopic composition of amino acids from the marine bacterium Vibrio harveyi

NASA Astrophysics Data System (ADS)

Maki, K.; Ohkouchi, N.; Chikaraishi, Y.; Fukuda, H.; Miyajima, T.; Nagata, T.

2014-09-01

Nitrogen (N) isotopic compositions of individual hydrolysable amino acids (δ15NAAs) in N pools have been increasingly used for trophic position assessment and evaluation of sources and transformation processes of organic matter in marine environments. However, there are limited data about variability in δ15NAAs patterns and how this variability influences marine bacteria, an important mediator of trophic transfer and organic matter transformation. We explored whether marine bacterial δ15NAAs profiles change depending on the type and C:N ratio of the substrate. The δ15NAAs profile of a marine bacterium, Vibrio harveyi, was examined using medium containing either glutamate, alanine or ammonium as the N source [substrate C:N ratios (range, 3 to 20) were adjusted with glucose]. The data were interpreted as a reflection of isotope fractionations associated with de novo synthesis of amino acids by bacteria. Principal component analysis (PCA) using the δ15N offset values normalized to glutamate + glutamine δ15N revealed that δ15NAAs profiles differed depending on the N source and C:N ratio of the substrate. High variability in the δ15N offset of alanine and valine largely explained this bacterial δ15NAAs profile variability. PCA was also conducted using bacterial and phytoplankton (cyanobacteria and eukaryotic algae) δ15NAAs profile data reported previously. The results revealed that bacterial δ15NAAs patterns were distinct from those of phytoplankton. Therefore, the δ15NAAs profile is a useful indicator of biochemical responses of bacteria to changes in substrate conditions, serving as a potentially useful method for identifying organic matter sources in marine environments.

STABLE ISOTOPES IN ECOLOGICAL STUDIES: NEW DEVELOPMENTS IN MIXING MODELS

EPA Science Inventory

Stable isotopes are increasingly being used as tracers in ecological studies. One application uses isotopic ratios to quantify the proportional contributions of multiple sources to a mixture. Examples include food sources for animals, water sources for plants, pollution sources...

Stable isotopes of carbon and nitrogen in the study of avian and mammalian trophic ecology

Treesearch

Jeffrey F. Kelly

2000-01-01

Differential fractionation of stable isotopes of carbon during photosynthesis causes C4 plants and C3 plants to have distinct carbon-isotope signatures. In addition, marine C3 plants have stable-isotope ratios of carbon that are intermediate between C4 and terrestrial C3 plants. The direct incorporation of the carbon-isotope ratio (13C/12C) of plants into consumers...

Seasonally Resolved Oxygen Isotope Paleoclimate Proxy in Tree-Ring Cellulose from the Southeastern U.S.

NASA Astrophysics Data System (ADS)

Miller, D. L.; Mora, C. I.; Grissino-Mayer, H. D.; Mock, C. J.

2004-12-01

Stable isotopes in precipitation reflect changes in climate, moisture source, and extreme events such as tropical cyclones, and an oxygen isotope proxy record of these changes through time and space is preserved in tree-ring cellulose. Extreme climate events such as droughts and hurricanes are formidable natural disasters in the southeastern United States, and considerable efforts have been made to understand factors controlling their frequency, whether natural or anthropogenic. Tree rings offer an unusually well-resolved, dateable record of climate events extending beyond modern or historical (documentary) records. Oxygen isotopes in alpha-cellulose of shallowly-rooted conifers predominately reflect the composition of precipitation. Tropical storm convection results in marked 18O depletion in storm precipitation, to -15‰ relative to source seawater (~0‰ ). The depletion increases towards the eyewall of the cyclone, however, isotopically depleted precipitation may extend outward many 100's of km. Storm water 18O depletion translates to soil water 18O depletion that may persist for many weeks until ameliorated by soil water evaporation. Tree growth during that time will take up the anomalous isotopic compositions. Distinctive earlywood (EW ~March-June) versus latewood (LW ~July-October) growth allows the rings to be resolved at an intra-annual (seasonal) scale. By comparison to average soil water, droughts result in 18O-enriched soil water compositions. Seasonal drought or years of continued drought will be similarly captured in the isotope compositions of tree-ring cellulose. A 227-year (1770-1997) seasonally-resolved record of tropical cyclone and drought activity was obtained from cross-sections of felled slash pines (Pinus elliottii Engelm.) and remnant longleaf pines (Pinus palustris Mill.) from southern Georgia. Interpretations of drought or hurricane events were tested by comparison with recent, detailed meteorological records. The 227-year record reveals most previously established hurricane events, including Florence (1953) and the Great Hurricane of 1780. Newly recognized tropical storms such as 1857 are also evident. Significant seasonal droughts such as 1955, 1927, 1904 and 1896, are observed for southeastern Georgia. Larger-scale climate oscillations appear to overprint the EW and LW isotope series, displaying periods of relatively large or small differences in EW and LW δ 18O values. The oscillations are interpreted to reflect dominant climate modes that influence moisture source or seasonal temperature variation. The tree-ring record potentially extends many centuries. A preliminary record through a portion of the North American "Little Ice Age" (1580-1650) indicates a significant reduction in tropical cyclone activity.

The Use of Lead Isotope and Rare Earth Element Geochemistry for Forensic Geographic Provenancing

NASA Astrophysics Data System (ADS)

Carey, A.; Darrah, T.; Harrold, Z.; Prutsman-Pfeiffer, J.; Poreda, R.

2008-12-01

Lead isotope and rare earth element composition of modern human bones are analyzed to explore their utility for geographical provenancing. DNA analysis is the standard for identification of individuals. DNA analysis requires a DNA match for comparison. Thus, DNA analysis is of limited use in cases involving unknown remains. Trace elements are incorporated into bones and teeth during biomineralization, recording the characteristics of an individual's geochemical environment. Teeth form during adolescence, recording the geochemical environment of an individual's youth. Bones remodel throughout an individual's lifetime. Bones consist of two types of bone tissue (cortical and trabecular) that remodel at different rates, recording the geochemical environment at the time of biomineralization. Cortical bone tissue, forming the outer surface of bones, is dense, hard tissue that remodels in 25-30 yrs. Conversely, trabecular bone tissue, the inner cavity of bones, is low density, porous and remodels in 2-5 years. Thus, analyzing teeth and both bone tissues allows for the development of a geographical time line capable of tracking immigration patterns through time instead of only an individual's youth. Geochemical isotopic techniques (Sr, O, C, N) have been used for geographical provenancing in physical anthropology. The isotopic values of Sr, C, O, N are predominantly a function of soil compositions in areas where food is grown or water is consumed. Application of these provenancing techniques has become difficult as an individual's diet may reflect the isotopic composition of foods obtained at the local grocer as opposed to local soil compositions. Thus, we explore the use of REEs and Pb isotopes for geographical provenancing. Pb and REEs are likely more reliable indicators of modern geographical location as their composition are high in bio-available sources such as local soils, atmospheric aerosols, and dust as opposed to Sr, C, O, N that are controlled by food and drinking water. Lead isotope and REE analysis of trabecular and cortical bone tissue of 60 femoral heads resected during hip replacement surgery at the Univ. of Roch. Medical Center were analyzed by a combination of TIMS and ICP-MS. Results show that Pb compositions are consistent with local soil with variable inputs from known environmental sources. Several samples demonstrate inputs from known environmental sources (e.g. Mississippi Valley ore) that was used in paint, solder, and US gasoline. Additionally, results suggest bioincorporation of Pb with isotopic composition consistent with that observed for Canadian gasoline aerosols. Immigrants included in the study show Pb compositions distinctly different than local residents.

Investigation of amino acid δ 13C signatures in bone collagen to reconstruct human palaeodiets using liquid chromatography-isotope ratio mass spectrometry

NASA Astrophysics Data System (ADS)

Choy, Kyungcheol; Smith, Colin I.; Fuller, Benjamin T.; Richards, Michael P.

2010-11-01

This research presents the individual amino acid δ 13C values in bone collagen of humans ( n = 9) and animals ( n = 27) from two prehistoric shell midden sites in Korea. We obtained complete baseline separation of 16 of the 18 amino acids found in bone collagen by using liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). The isotopic results reveal that the humans and animals in the two sites had similar patterns in essential amino acids (EAAs) and non-essential amino acids (NEAAs). The EAA and NEAA δ 13C values in humans are intermediate between those in marine and terrestrial animals. However, the threonine δ 13C values in humans and animals measured in this study are more highly enriched than those of other amino acids. At both sites, all amino acids in marine animals are 13C-enriched relative to those of the terrestrial animals. The isotopic evidence suggests that the Tongsamdong human had EAAs and NEAAs from marine food resources, while the Nukdo humans mainly had EAAs from terrestrial food resources but obtained NEAAs from both terrestrial and marine resources. The δ 13C isotopic differences in amino acids between marine and terrestrial animals were the largest for glycine (NEAA) and histidine (EAA) and the smallest for tyrosine (NEAA) and phenylalanine (EAA). In addition, threonine among the EAAs also had a large difference (˜8‰) in δ 13C values between marine and terrestrial animals, and has the potential to be used as an isotopic marker in palaeodietary studies. Threonine δ 13C values were used in conjunction with the established Δ 13C Glycine-phenylalanine values and produced three distinct dietary groups (terrestrial, omnivorous, and marine). In addition, threonine δ 13C values and Δ 13C Serine-phenylalanine values were discovered to separate between two dietary groups (terrestrial vs. marine), and these δ 13C values may provide a potential new indicator for investigating the distinction between marine and terrestrial protein sources in human diets.

[Research advances in identifying nitrate pollution sources of water environment by using nitrogen and oxygen stable isotopes].

PubMed

Mao, Wei; Liang, Zhi-wei; Li, Wei; Zhu, Yao; Yanng, Mu-yi; Jia, Chao-jie

2013-04-01

Water body' s nitrate pollution has become a common and severe environmental problem. In order to ensure human health and water environment benign evolution, it is of great importance to effectively identify the nitrate pollution sources of water body. Because of the discrepant composition of nitrogen and oxygen stable isotopes in different sources of nitrate in water body, nitrogen and oxygen stable isotopes can be used to identify the nitrate pollution sources of water environment. This paper introduced the fractionation factors of nitrogen and oxygen stable isotopes in the main processes of nitrogen cycling and the composition of these stable isotopes in main nitrate sources, compared the advantages and disadvantages of five pre-treatment methods for analyzing the nitrogen and oxygen isotopes in nitrate, and summarized the research advances in this aspect into three stages, i. e. , using nitrogen stable isotope alone, using nitrogen and oxygen stable isotopes simultaneously, and combining with mathematical models. The future research directions regarding the nitrate pollution sources identification of water environment were also discussed.

Magnesium isotope systematics in Martian meteorites

NASA Astrophysics Data System (ADS)

Magna, Tomáš; Hu, Yan; Teng, Fang-Zhen; Mezger, Klaus

2017-09-01

Magnesium isotope compositions are reported for a suite of Martian meteorites that span the range of petrological and geochemical types recognized to date for Mars, including crustal breccia Northwest Africa (NWA) 7034. The δ26Mg values (per mil units relative to DSM-3 reference material) range from -0.32 to -0.11‰; basaltic shergottites and nakhlites lie to the heavier end of the Mg isotope range whereas olivine-phyric, olivine-orthopyroxene-phyric and lherzolitic shergottites, and chassignites have slightly lighter Mg isotope compositions, attesting to modest correlation of Mg isotopes and petrology of the samples. Slightly heavier Mg isotope compositions found for surface-related materials (NWA 7034, black glass fraction of the Tissint shergottite fall; δ26Mg > -0.17‰) indicate measurable Mg isotope difference between the Martian mantle and crust but the true extent of Mg isotope fractionation for Martian surface materials remains unconstrained. The range of δ26Mg values from -0.19 to -0.11‰ in nakhlites is most likely due to accumulation of clinopyroxene during petrogenesis rather than garnet fractionation in the source or assimilation of surface material modified at low temperatures. The rather restricted range in Mg isotope compositions between spatially and temporally distinct mantle-derived samples supports the idea of inefficient/absent major tectonic cycles on Mars, which would include plate tectonics and large-scale recycling of isotopically fractionated surface materials back into the Martian mantle. The cumulative δ26Mg value of Martian samples, which are not influenced by late-stage alteration processes and/or crust-mantle interactions, is - 0.271 ± 0.040 ‰ (2SD) and is considered to reflect δ26Mg value of the Bulk Silicate Mars. This value is robust taking into account the range of lithologies involved in this estimate. It also attests to the lack of the Mg isotope variability reported for the inner Solar System bodies at current analytical precision, also noted for several other major elements.

Multi-stage mixing in subduction zone: Application to Merapi volcano, Indonesia

NASA Astrophysics Data System (ADS)

Debaille, V.; Doucelance, R.; Weis, D.; Schiano, P.

2003-04-01

Basalts sampling subduction zone volcanism (IAB) often show binary mixing relationship in classical Sr-Nd, Pb-Pb, Sr-Pb isotopic diagrams, generally interpreted as reflecting the involvement of two components in their source. However, several authors have highlighted the presence of minimum three components in such a geodynamical context: mantle wedge, subducted and altered oceanic crust and subducted sediments. The overlying continental crust can also contribute by contamination and assimilation in magma chambers and/or during magma ascent. Here we present a multi-stage model to obtain a two end-member mixing from three components (mantle wedge, altered oceanic crust and sediments). The first stage of the model considers the metasomatism of the mantle wedge by fluids and/or melts released by subducted materials (altered oceanic crust and associated sediments), considering mobility and partition coefficient of trace elements in hydrated fluids and silicate melts. This results in the generation of two distinct end-members, reducing the number of components (mantle wedge, oceanic crust, sediments) from three to two. The second stage of the model concerns the binary mixing of the two end-members thus defined: mantle wedge metasomatized by slab-derived fluids and mantle wedge metasomatized by sediment-derived fluids. This model has been applied on a new isotopic data set (Sr, Nd and Pb, analyzed by TIMS and MC-ICP-MS) of Merapi volcano (Java island, Indonesia). Previous studies have suggested three distinct components in the source of indonesian lavas: mantle wedge, subducted sediments and altered oceanic crust. Moreover, it has been shown that crustal contamination does not significantly affect isotopic ratios of lavas. The multi-stage model proposed here is able to reproduce the binary mixing observed in lavas of Merapi, and a set of numerical values of bulk partition coefficient is given that accounts for the genesis of lavas.

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.

SOURCE PARTITIONING USING STABLE ISOTOPES: COPING WITH TOO MANY SOURCES

EPA Science Inventory

Stable isotopes are increasingly being used as tracers in environmental studies. One application is to use isotopic ratios to quantitatively determine the proportional contribution of several sources to a mixture, such as the proportion of various pollution sources in a waste st...

Industrially synthesized single-walled carbon nanotubes: compositional data for users, environmental risk assessments, and source apportionment

NASA Astrophysics Data System (ADS)

Plata, D. L.; Gschwend, P. M.; Reddy, C. M.

2008-05-01

Commercially available single-walled carbon nanotubes (SWCNTs) contain large percentages of metal and carbonaceous impurities. These fractions influence the SWCNT physical properties and performance, yet their chemical compositions are not well defined. This lack of information also precludes accurate environmental risk assessments for specific SWCNT stocks, which emerging local legislation requires of nanomaterial manufacturers. To address these needs, we measured the elemental, molecular, and stable carbon isotope compositions of commercially available SWCNTs. As expected, catalytic metals occurred at per cent levels (1.3-29%), but purified materials also contained unexpected metals (e.g., Cu, Pb at 0.1-0.3 ppt). Nitrogen contents (up to 0.48%) were typically greater in arc-produced SWCNTs than in those derived from chemical vapor deposition. Toluene-extractable materials contributed less than 5% of the total mass of the SWCNTs. Internal standard losses during dichloromethane extractions suggested that metals are available for reductive dehalogenation reactions, ultimately resulting in the degradation of aromatic internal standards. The carbon isotope content of the extracted material suggested that SWCNTs acquired much of their carbonaceous contamination from their storage environment. Some of the SWCNTs, themselves, were highly depleted in 13C relative to petroleum-derived chemicals. The distinct carbon isotopic signatures and unique metal 'fingerprints' may be useful as environmental tracers allowing assessment of SWCNT sources to the environment.

Integration of metagenomic and stable carbon isotope evidence reveals the extent and mechanisms of carbon dioxide fixation in high-temperature microbial communities

DOE PAGES

Jennings, Ryan de Montmollin; Moran, James J.; Jay, Zackary J.; ...

2017-02-03

Biological fixation of CO 2 is the primary mechanism of C reduction in natural systems, and provides a diverse suite of organic compounds utilized by chemoorganoheterotrophs. The extent and mechanisms of CO 2 fixation were evaluated across a comprehensive set of high-temperature, chemotrophic microbial communities in Yellowstone National Park by combining metagenomic and stable 13C isotope analyses. Fifteen geothermal sites representing three distinct habitat types (iron-oxide mats, anoxic sulfur sediments, and filamentous ‘streamer’ communities) were investigated. Genes of the 3-hydroxypropionate/4-hydroxybutyrate, dicarboxylate/4-hydroxybutyrate, and reverse tricarboxylic acid CO 2 fixation pathways were identified in assembled genome sequence corresponding to the predominant Crenarchaeotamore » and Aquificales observed across this habitat range. Stable 13C analyses of dissolved inorganic and organic C (DIC, DOC), and possible landscape C sources were used to interpret the 13C content of microbial community samples. Isotope mixing models showed that the minimum amounts of autotrophic C in microbial biomass were > 50 % in the majority of communities analyzed, but were also dependent on the amounts of heterotrophy and/or accumulation of landscape C. Furthermore, the significance of CO 2 as a C source in these communities provides a foundation for understanding metabolic linkages among autotrophs and heterotrophs, community assembly and succession, and the likely coevolution of deeply-branching thermophiles.« less

Isotopic and trace element geochemistry of the Seligdar magnesiocarbonatites (South Yakutia, Russia): Insights regarding the mantle evolution beneath the Aldan-Stanovoy shield

NASA Astrophysics Data System (ADS)

Doroshkevich, Anna G.; Prokopyev, Ilya R.; Izokh, Andrey E.; Klemd, Reiner; Ponomarchuk, Anton V.; Nikolaeva, Irina V.; Vladykin, Nikolay V.

2018-04-01

The Paleoproterozoic Seligdar magnesiocarbonatite intrusion of the Aldan-Stanovoy shield in Russia underwent extensive postmagmatic hydrothermal alteration and metamorphic events. This study comprises new isotopic (Sr, Nd, C and O) data, whole-rock major and trace element compositions and trace element characteristics of the major minerals to gain a better understanding of the source and the formation process of the carbonatites. The Seligdar carbonatites have high concentrations of P2O5 (up to 18 wt%) and low concentrations of Na, K, Sr and Ba. The chondrite-normalized REE patterns of these carbonatites display significant enrichments of LREE relative to HREE with an average La/Ybcn ratio of 95. Hydrothermal and metamorphic overprints changed the trace element characteristics of the carbonatites and their minerals. These alteration processes were responsible for Sr loss and the shifting of the Sr isotopic compositions towards more radiogenic values. The altered carbonatites are further characterized by distinct 18O- and 13C-enrichments compared to the primary igneous carbonatites. The alteration most likely resulted from both the percolation of crustal-derived hydrothermal fluids and subsequent metamorphic processes accompanied by interaction with limestone-derived CO2. The narrow range of negative εNd(T) values indicates that the Seligdar carbonatites are dominated by a homogenous enriched mantle source component that was separated from the depleted mantle during the Archean.

Study of medical isotope production facility stack emissions and noble gas isotopic signature using automatic gamma-spectra analysis platform

NASA Astrophysics Data System (ADS)

Zhang, Weihua; Hoffmann, Emmy; Ungar, Kurt; Dolinar, George; Miley, Harry; Mekarski, Pawel; Schrom, Brian; Hoffman, Ian; Lawrie, Ryan; Loosz, Tom

2013-04-01

The nuclear industry emissions of the four CTBT (Comprehensive Nuclear-Test-Ban Treaty) relevant radioxenon isotopes are unavoidably detected by the IMS along with possible treaty violations. Another civil source of radioxenon emissions which contributes to the global background is radiopharmaceutical production companies. To better understand the source terms of these background emissions, a joint project between HC, ANSTO, PNNL and CRL was formed to install real-time detection systems to support 135Xe, 133Xe, 131mXe and 133mXe measurements at the ANSTO and CRL 99Mo production facility stacks as well as the CANDU (CANada Deuterium Uranium) primary coolant monitoring system at CRL. At each site, high resolution gamma spectra were collected every 15 minutes using a HPGe detector to continuously monitor a bypass feed from the stack or CANDU primary coolant system as it passed through a sampling cell. HC also conducted atmospheric monitoring for radioxenon at approximately 200 km distant from CRL. A program was written to transfer each spectrum into a text file format suitable for the automatic gamma-spectra analysis platform and then email the file to a server. Once the email was received by the server, it was automatically analysed with the gamma-spectrum software UniSampo/Shaman to perform radionuclide identification and activity calculation for a large number of gamma-spectra in a short period of time (less than 10 seconds per spectrum). The results of nuclide activity together with other spectrum parameters were saved into the Linssi database. This database contains a large amount of radionuclide information which is a valuable resource for the analysis of radionuclide distribution within the noble gas fission product emissions. The results could be useful to identify the specific mechanisms of the activity release. The isotopic signatures of the various radioxenon species can be determined as a function of release time. Comparison of 133mXe and 133Xe activity ratios showed distinct differences between the closed CANDU primary coolant system and radiopharmaceutical production releases. According to the concept proposed by Kalinowski and Pistner (2006), the relationship between different isotopic activity ratios based on three or four radioxenon isotopes was plotted in a log-log diagram for source characterisation (civil vs. nuclear test). The multiple isotopic activity ratios were distributed in three distinct areas: HC atmospheric monitoring ratios extended to far left; the CANDU primary coolant system ratios lay in the middle; and 99Mo stack monitoring ratios for ANSTO and CRL were located on the right. The closed CANDU primary coolant has the lowest logarithmic mean ratio that represents the nuclear power reactor operation. The HC atmospheric monitoring exhibited a broad range of ratios spreading over several orders of magnitude. In contrast, the ANSTO and CRL stack emissions showed the smallest range of ratios but the results indicate at least two processes involved in the 99Mo productions. Overall, most measurements were found to be shifted towards the reactor domain. The hypothesis is that this is due to an accumulation of the isotope 131mXe in the stack or atmospheric background as it has the longest half-life and extra 131mXe emissions from the decay of 131I. The contribution of older 131mXe to a fresh release shifts the ratio of 133mXe/131mXe to the left. It was also very interesting to note that there were some situations where isotopic ratios from 99Mo production emissions fell within the nuclear test domain. This is due to operational variability, such as shorter target irradiation times. Martin B. Kalinowski and Christoph Pistner, (2006), Isotopic signature of atmospheric xenon released from light water reactors, Journal of Environmental Radioactivity, 88, 215-235.

Eastern Equatorial Pacific Dust Provenance on Deglacial Timescales

NASA Astrophysics Data System (ADS)

Xie, R.; Marcantonio, F.

2008-12-01

Changing patterns of eolian dust deposition preserved in deep-sea sediments have the potential to provide us with a better understanding of changes in past atmospheric circulation. One way in which to determine the provenance of dust in deep-sea sediments is to use radiogenic isotopic tracers which can fingerprint potential dust sources. Models (e.g., [1]) suggest that sources of dust to the Eastern Equatorial Pacific (EEP) are from areas as diverse as Asia, North, Central, and South America, and, perhaps, even Africa. Here, we investigate spatial and temporal changes in the provenance of the eolian component in the EEP by measuring Pb, Sr, and Nd isotope ratios in dust extracted from sediments along a transect at 110oW from 7oN to 3oS (ODP sites 853 - 848). In this region, although fluxes of dust were higher during the last glacial maximum (LGM) than those in the Holocene by up to 100%, the glacial flux of dust displayed a shallower meridional gradient [2]. However, it is unclear whether this shallower gradient is due to a mean southerly displacement of the Intertropical Convergence Zone (ITCZ). Most of the dust trying to pass through the ITCZ will be scavenged and rained out at the ITCZ. Along the meridional gradient, therefore, temporal variations in the Pb, Sr, and Nd isotopic fingerprints of the distinct dust sources will determine the extent to which the position of the ITCZ changes on deglacial timescales. [1] Mahowald et al., 2005, Global Biogeochemical Cycles 19, GB4025. [2] McGee et al., 2007, EPSL 257, 215-230.

Mercury and methylmercury concentrations and loads in the Cache Creek watershed, California

USGS Publications Warehouse

Domagalski, Joseph L.; Alpers, Charles N.; Slotton, D.G.; Suchanek, T.H.; Ayers, S.M.

2004-01-01

Concentrations and loads of total mercury and methylmercury were measured in streams draining abandoned mercury mines and in the proximity of geothermal discharge in the Cache Creek watershed of California during a 17-month period from January 2000 through May 2001. Rainfall and runoff were lower than long-term averages during the study period. The greatest loading of mercury and methylmercury from upstream sources to downstream receiving waters, such as San Francisco Bay, generally occurred during or after winter rainfall events. During the study period, loads of mercury and methylmercury from geothermal sources tended to be greater than those from abandoned mining areas, a pattern attributable to the lack of large precipitation events capable of mobilizing significant amounts of either mercury-laden sediment or dissolved mercury and methylmercury from mine waste. Streambed sediments of Cache Creek are a significant source of mercury and methylmercury to downstream receiving bodies of water. Much of the mercury in these sediments is the result of deposition over the last 100-150 years by either storm-water runoff, from abandoned mines, or continuous discharges from geothermal areas. Several geochemical constituents were useful as natural tracers for mining and geothermal areas, including the aqueous concentrations of boron, chloride, lithium and sulfate, and the stable isotopes of hydrogen and oxygen in water. Stable isotopes of water in areas draining geothermal discharges showed a distinct trend toward enrichment of 18O compared with meteoric waters, whereas much of the runoff from abandoned mines indicated a stable isotopic pattern more consistent with local meteoric water. ?? 2004 Elsevier B.V. All rights reserved.

Discovery and measurement of an isotopically distinct source of sulfate in Earth's atmosphere

PubMed Central

Dominguez, Gerardo; Jackson, Terri; Brothers, Lauren; Barnett, Burton; Nguyen, Bryan; Thiemens, Mark H.

2008-01-01

Sulfate (SO4) and its precursors are significant components of the atmosphere, with both natural and anthropogenic sources. Recently, our triple-isotope (16O, 17O, 18O) measurements of atmospheric sulfate have provided specific insights into the oxidation pathways leading to sulfate, with important implications for models of the sulfur cycle and global climate change. Using similar isotopic measurements of aerosol sulfate in a polluted marine boundary layer (MBL) and primary sulfate (p-SO4) sampled directly from a ship stack, we quantify the amount of p-SO4 found in the atmosphere from ships. We find that ships contribute between 10% and 44% of the non-sea-salt sulfate found in fine [diameter (D) < 1.5 μm) particulate matter in coastal Southern California. These fractions are surprising, given that p-SO4 constitutes ≈2–7% of total sulfur emissions from combustion sources [Seinfed JH, Pandis SN (2006) Atmospheric Chemistry and Physics (Wiley–Interscience, New York)]. Our findings also suggest that the interaction of SO2 from ship emissions with coarse hydrated sea salt particles may lead to the rapid removal of SO2 in the MBL. When combined with the longer residence time of p-SO4 emissions in the MBL, these findings suggest that the importance of p-SO4 emissions in marine environments may be underappreciated in global chemical models. Given the expected increase of international shipping in the years to come, these findings have clear implications for public health, air quality, international maritime law, and atmospheric chemistry. PMID:18753618

Analyses of stomach contents and stable isotopes reveal food sources of estuarine detritivorous fish in tropical/subtropical Taiwan

NASA Astrophysics Data System (ADS)

Lin, Hsing-Juh; Kao, Wen-Yuan; Wang, Ya-Ting

2007-07-01

Detritivorous fish generally refers to fish that primarily ingest unidentified organic detritus. We analyzed stomach contents in combination with stable isotopes to trace and compare the food sources of the large-scale mullet Liza macrolepis and other detritivorous fish species in subtropical mangrove creeks and a tropical lagoon in Taiwan. The volume of organic detritus always contributed >50% of the stomach content of L. macrolepis in the two habitats. However, consumed items were distinct between the two habitats and corresponded to the types in which they reside. The consumed items in the lagoon were more diverse than those observed in the mangroves. In the mangroves, the diet composition of L. macrolepis was primarily determined by season, not by body size. In the lagoon, there were no clear seasonal or size-dependent grouping patterns for the diet composition. There were significant seasonal and spatial variations in δ13C and δ15N values of potential food sources and L. macrolepis. However, neither δ13C nor δ15N values of L. macrolepis were correlated with fish body size. Joint analyses of stomach contents and stable isotopes indicated that benthic microalgae on sediments were the most important assimilated food in both seasons for the dominant detritivorous fish in the mangroves, whereas a greater reliance on microalgal and macroalgal periphyton on oyster-culture pens was observed in the lagoon. Mangrove and marsh plants and phytoplankton, which are mostly locally produced within each habitat, were of minor importance in the assimilated food.

Discovery and measurement of an isotopically distinct source of sulfate in Earth's atmosphere.

PubMed

Dominguez, Gerardo; Jackson, Terri; Brothers, Lauren; Barnett, Burton; Nguyen, Bryan; Thiemens, Mark H

2008-09-02

Sulfate (SO(4)) and its precursors are significant components of the atmosphere, with both natural and anthropogenic sources. Recently, our triple-isotope ((16)O, (17)O, (18)O) measurements of atmospheric sulfate have provided specific insights into the oxidation pathways leading to sulfate, with important implications for models of the sulfur cycle and global climate change. Using similar isotopic measurements of aerosol sulfate in a polluted marine boundary layer (MBL) and primary sulfate (p-SO(4)) sampled directly from a ship stack, we quantify the amount of p-SO(4) found in the atmosphere from ships. We find that ships contribute between 10% and 44% of the non-sea-salt sulfate found in fine [diameter (D) < 1.5 microm) particulate matter in coastal Southern California. These fractions are surprising, given that p-SO(4) constitutes approximately 2-7% of total sulfur emissions from combustion sources [Seinfed JH, Pandis SN (2006) Atmospheric Chemistry and Physics (Wiley-Interscience, New York)]. Our findings also suggest that the interaction of SO(2) from ship emissions with coarse hydrated sea salt particles may lead to the rapid removal of SO(2) in the MBL. When combined with the longer residence time of p-SO(4) emissions in the MBL, these findings suggest that the importance of p-SO(4) emissions in marine environments may be underappreciated in global chemical models. Given the expected increase of international shipping in the years to come, these findings have clear implications for public health, air quality, international maritime law, and atmospheric chemistry.

Gas and isotope chemistry of thermal features in Yellowstone National Park, Wyoming

USGS Publications Warehouse

Bergfeld, D.; Lowenstern, Jacob B.; Hunt, Andrew G.; Shanks, W.C. Pat; Evans, William

2011-01-01

This report presents 130 gas analyses and 31 related water analyses on samples collected from thermal features at Yellowstone between 2003 and 2009. An overview of previous studies of gas emissions at Yellowstone is also given. The analytical results from the present study include bulk chemistry of gases and waters and isotope values for water and steam (delta18O, dealtaD), carbon dioxide (delta13C only), methane (delta13C only), helium, neon, and argon. We include appendixes containing photos of sample sites, geographic information system (GIS) files including shape and kml formats, and analytical results in spreadsheets. In addition, we provide a lengthy discussion of previous work on gas chemistry at Yellowstone and a general discussion of the implications of our results. We demonstrate that gases collected from different thermal areas often have distinct chemical signatures, and that differences across the thermal areas are not a simple function of surface temperatures or the type of feature. Instead, gas chemistry and isotopic composition are linked to subsurface lithologies and varying contributions from magmatic, crustal, and meteoric sources.

Sulphur isotopic compositions of deep-sea hydrothermal vent animals

NASA Technical Reports Server (NTRS)

Fry, B.; Gest, H.; Hayes, J. M.

1983-01-01

The S-34/S-32 ratios of tissues from vestimentiferan worms, brachyuran crabs, and giant clams living around deep hydrothermal vents are reported. Clean tissues were dried, ground, suspended in 0.1 M LiCl, shaken twice at 37 C to remove seawater sulfates, dried at 60 C, combusted in O2 in a Parr bomb. Sulfur was recovered as BaSO4, and the isotopic abundances in SO2 generated by thermal decomposition of 5-30-mg samples were determined using an isotope-ratio mass spectrometer. The results are expressed as delta S-34 and compared with values measured in seawater sulfates and in normal marine fauna. The values ranged from -4.7 to 4.7 per thousand, comparable to vent sulfide minerals (1.3-4.1 per thousand) and distinct from seawater sulfates (20.1 per thousand) and normal marine fauna (about 13-20 per thousand). These results indicate that vent sulfur rather than seawater sulfur is utilized by these animals, a process probably mediated by chemoautotrophic bacteria which can use inorganic sulfur compounds as energy sources.

Noble gas models of mantle structure and reservoir mass transfer

NASA Astrophysics Data System (ADS)

Harrison, Darrell; Ballentine, Chris J.

Noble gas observations from different mantle samples have provided some of the key observational data used to develop and support the geochemical "layered" mantle model. This model has dominated our conceptual understanding of mantle structure and evolution for the last quarter of a century. Refinement in seismic tomography and numerical models of mantle convection have clearly shown that geochemical layering, at least at the 670 km phase change in the mantle, is no longer tenable. Recent adaptations of the mantle-layering model that more successfully reconcile whole-mantle convection with the simplest data have two common features: (i) the requirement for the noble gases in the convecting mantle to be sourced, or "fluxed", by a deep long-lived volatile-rich mantle reservoir; and (ii) the requirement for the deep mantle reservoirs to be seismically invisible. The fluxing requirement is derived from the low mid-ocean ridge basalt (MORB)-source mantle 3He concentration, in turn calculated from the present day 3He flux from mid-ocean ridges into the oceans (T½ ˜ 1,000 yr) and the ocean crust generation rate (T½ ˜ 108 yr). Because of these very different residence times we consider the 3He concentration constraint to be weak. Furthermore, data show 3He/22Ne ratios derived from different mantle reservoirs to be distinct and require additional complexities to be added to any model advocating fluxing of the convecting mantle from a volatile-rich mantle reservoir. Recent work also shows that the convecting mantle 20Ne/22Ne isotopic composition is derived from an implanted meteoritic source and is distinct from at least one plume source system. If Ne isotope heterogeneity between convecting mantle and plume source mantle is confirmed, this result then excludes all mantle fluxing models. While isotopic heterogeneity requires further quantification, it has been shown that higher 3He concentrations in the convecting mantle, by a factor of 3.5, remove the need for the noble gases in the convecting mantle to be sourced from such a deep hidden reservoir. This "zero paradox" concentration [Ballentine et al., 2002] is then consistent with the different mantle source 3He/22Ne and 20Ne/22Ne heterogeneities. Higher convecting mantle noble gas concentrations also eliminate the requirement for a hidden mantle 40Ar rich-reservoir and enables the heat/4He imbalance to be explained by temporal variance in the different mechanisms of heat vs. He removal from the mantle system—two other key arguments for mantle layering. Confirmation of higher average convecting mantle noble gas concentrations remains the key test of such a concept.

Zinc Isotopic Signatures of the Upper Continental Crust

NASA Astrophysics Data System (ADS)

Xia, Y.; Zhang, X.; Zhang, H.; Huang, F.

2016-12-01

To examine the Zn isotope systematics within the Upper Continental Crust (UCC), and isotope fractionation during chemical weathering in large spatial and temporal scales, we analyzed Zn isotopic compositions of loess, glacial diamictites, river sediments, and igneous rocks (samples in total 77). The Zn isotopic compositions (δ66Zn relative to JMC-Lyon) of loess display a limited variation (0.17‰ to 0.29‰), which is negatively correlated with Zn content and proxies for chemical weathering (e.g. CIA values), reflect the impact of chemical weathering. Glacial diamictites have more variable δ66Zn (0.09‰ to 0.48‰), but the average δ66Zn (0.29±0.03‰, 2SD) is similar to loess. δ66Zn of glacial diamictites correlate roughly negatively with CIA values, but have no correlation with Zn content, implying source heterogeneity and effect from chemical weathering. δ66Zn of A-type (0.39‰ to 0.45‰) and S-type (0.28‰ to 0.35‰) granites are both homogeneous, but the latter have systematically lighter δ66Zn. This may reflect no Zn isotopic fractionation during magmatic processes and involvement of isotopically light meta-sedimentary into the sources of S-type granites. Furthermore, δ66Zn in riverine sediments display a small variation from 0.23‰ to 0.37‰, while δ66Zn of the the shales vary from 0.14‰ to 0.53‰, which could result from a combination of processes, such as biological cycling and chemical weathering. Overall, our data suggest that incipient chemical weathering can fractionate Zn isotopes significantly, meanwhile, during this process, heavy Zn are released preferentially. The UCC is estimated to have an average δ66Zn of 0.30 ±0.03‰ (2SD) with data collected in this study, which is similar to the estimated value of Bulk Silicate Earth (0.28±0.05‰)[1] and mean dissolved riverine flux (0.33‰)[2], but distinctly lighter than the bulk composition of dissolved Zn in the ocean (0.51‰)[2]. [1] Chen et al., Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth. Earth and Planetary Science Letters 369, 34-42 (2013). [2] Little et al., The oceanic mass balance of copper and zinc isotopes, investigated by analysis of their inputs, and outputs to ferromanganese oxide sediments. Geochimica et Cosmochimica Acta 125, 673-693 (2014).

Silicon and Zinc Isotopes in Ocean Island Basalts

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Savage, P. S.; Jackson, M. G.; Moreira, M. A.; Day, J. M.; Moynier, F.

2013-12-01

Analyses of Ocean Island Basalts (OIB) have shown that the Earth's mantle contains isotopically distinct components, but current debate about the degree and scale of compositional variability persists. Isotopic heterogeneities in OIB for both radiogenic (e.g. Sr, Nd, Pb) and stable (e.g. Li, O, Ca) isotope systems have been attributed to the presence of recycled materials in different mantle reservoirs [1]. The study of both silicon and zinc isotopes in OIB form a complimentary approach to investigate potential heterogeneities in the mantle. Both isotope systems show limited fractionation during igneous process [2,3]. However, both Si and Zn exhibit larger (>1‰) variability in low-temperature environments (e.g. as a result of chemical weathering and biological utilization). Therefore, Si and Zn isotopes may be useful as tracers for the presence of crustal material (derived from low-T surface processes) in OIB source regions. Furthermore, characterizing the isotopic composition of the mantle is of central importance to the use of these isotopic systems as a basis for interplanetary comparisons. Here we present high-precision Si and Zn isotopic data obtained by MC-ICPMS for a diverse suite of OIB representing the EM-1, EM-2, and HIMU mantle components. Samples represent locations in the Pacific, Atlantic, and Indian Oceans. Data are reported as the permil deviation (×2 sd) from NBS28 for Si (δ30Si) and JMC-Lyon for Zn (δ66Zn). Average δ30Si values for OIB from EM-1 (-0.32×0.09‰), EM-2 (-0.30×0.03‰), and HIMU (-0.34×0.12‰) are all in general agreement with previous estimates for the δ30Si value of Bulk Silicate Earth (BSE) [4]. Similarly, the δ66Zn average values for OIB from the EM-1, EM-2, and HIMU components (0.31×0.06‰, 0.31×0.04‰, 0.31×0.05‰, respectively) agree well with previously published data for the δ66Zn value of BSE [3]. At the current levels of precision, both Si and Zn isotopes exhibit little variation in OIB, confirming the large-scale homogeneity of the mantle for these isotopic systems. Furthermore, when averaged according to surface location, neither Si nor Zn shows any variation in isotopic composition according to oceanic basin. However, some small variations in the data may be present; many HIMU samples (Mangaia, Cape Verde) are enriched in the lighter isotopes of Si (δ30Si tending toward chondritic values), which might reflect preservation of isotopic heterogeneity within the mantle, an incorporation of an isotopically light component in the source of these lavas, or isotopic fractionation during magmatic differentiation. References: [1] Hofmann, RiMG 2007 [2] Savage et al., GCA 2011 [3] Chen et al., EPSL 2013 [4] Savage et al., EPSL 2010

Implications for behavior of volatile elements during impacts—Zinc and copper systematics in sediments from the Ries impact structure and central European tektites

NASA Astrophysics Data System (ADS)

Rodovská, Zuzana; Magna, TomáÅ.¡; Žák, Karel; Kato, Chizu; Savage, Paul S.; Moynier, Frédéric; Skála, Roman; Ježek, Josef

2017-10-01

Moldavites are tektites genetically related to the Ries impact structure, located in Central Europe, but the source materials and the processes related to the chemical fractionation of moldavites are not fully constrained. To further understand moldavite genesis, the Cu and Zn abundances and isotope compositions were measured in a suite of tektites from four different substrewn fields (South Bohemia, Moravia, Cheb Basin, Lusatia) and chemically diverse sediments from the surroundings of the Ries impact structure. Moldavites are slightly depleted in Zn ( 10-20%) and distinctly depleted in Cu (>90%) relative to supposed sedimentary precursors. Moreover, the moldavites show a wide range in δ66Zn values between 1.7 and 3.7‰ (relative to JMC 3-0749 Lyon) and δ65Cu values between 1.6 and 12.5‰ (relative to NIST SRM 976) and are thus enriched in heavy isotopes relative to their possible parent sedimentary sources (δ66Zn = -0.07 to +0.64‰; δ65Cu = -0.4 to +0.7‰). In particular, the Cheb Basin moldavites show some of the highest δ65Cu values (up to 12.5‰) ever observed in natural samples. The relative magnitude of isotope fractionation for Cu and Zn seen here is opposite to oxygen-poor environments such as the Moon where Zn is significantly more isotopically fractionated than Cu. One possibility is that monovalent Cu diffuses faster than divalent Zn in the reduced melt and diffusion will not affect the extent of Zn isotope fractionation. These observations imply that the capability of forming a redox environment may aid in volatilizing some elements, accompanied by isotope fractionation, during the impact process. The greater extent of elemental depletion, coupled with isotope fractionation of more refractory Cu relative to Zn, may also hinge on the presence of carbonyl species of transition metals and electromagnetic charge, which could exist in the impact-induced high-velocity jet of vapor and melts.

A new Mantle Source Tapped During Episode 55 of the Pu'u O'o Eruption From Kilauea Volcano

NASA Astrophysics Data System (ADS)

Marske, J. P.; Pietruszka, A. J.; Garcia, M. O.; Rhodes, J. M.

2005-12-01

Over 22 years of continuous geochemical monitoring of lavas from the current Pu'u O'o eruption allows us to probe the mantle and crustal processes beneath Kilauea Volcano in unparalleled detail. Episode 55 (1997-present) marks the longest and most voluminous Pu'u O'o eruptive interval. Here we present new Pb, Sr, and Nd isotopic ratios and major- and trace-element abundances for the most recent lavas (1999-2005). MgO variation diagrams show that most of the major-element variations are related to olivine fractionation. However, Pu'u O'o lavas display longer-term systematic decreases in their TiO2, K2O, P2O5 and CaO abundances (at a given MgO) due to changes in the parental magma composition. Incompatible element ratios (K2O/TiO2, Nb/Y, Nb/Zr) and MgO-normalized abundances (Sr, Rb, K) in episode 55 lavas delimit the lowest values observed during the Pu'u O'o eruption. Earlier Pu'u O'o lavas displayed a temporal decrease in highly over moderately incompatible trace-element ratios, near constant SiO2 contents, and a gradual increase in 87Sr/86Sr. However, episode 55 lavas (between days 5500-6500) record an increase in MgO-normalized SiO2 contents and even higher 87Sr/86Sr with near constant incompatible trace-element ratios. Neither a single mantle source composition nor a change in partial melting conditions can explain these observations. Based on 226Ra-230Th-238U disequilibria and partial melting modeling of trace elements, we conclude that Pu'u O'o lavas originate from at least two distinct mantle source components: (1) a recently depleted component that was subsequently remelted to explain the overall decreases of incompatible major- and trace-element ratios and abundances, and (2) a compositionally and isotopically distinct mantle component that was not previously melted within the Hawaiian plume to explain the temporal increase in 87Sr/86Sr and SiO2 abundances and the flattening trend of incompatible trace-element ratios. This second component lies within typical Pb, Sr and Nd isotopic space for Kilauea, but represents a new source composition for the Pu'u O'o eruption. These results can be explained by a recent (1999) change in the size or location of Pu'u O'o's melting region, which allowed this new source to be tapped.

Early Precambrian mantle derived rocks in the southern Prince Charles Mountains, East Antarctica: age and isotopic constraints

USGS Publications Warehouse

Mikhalsky, E.V.; Henjes-Kunst, F.; Roland, N.W.

2007-01-01

Mafic and ultramafic rocks occurring as lenses, boudins, and tectonic slabs within metamorphic units in the southern Mawson Escarpment display mantle characteristics of either a highly enriched, or highly depleted nature. Fractionation of these mantle rocks from their sources may be as old as Eoarchaean (ca 3850 Ma) while their tectonic emplacement probably occurred prior to 2550 Ma (U-Pb SHRIMP data). These results provide for the first time evidence for Archaean suturing within East Antarctica. Similar upper mantle sources are likely present in the northern Mawson Escarpment. A younger age limit of these rocks is 2200 Ma, as indicated by presumably metamorphic zircon ages while their magmatic age may be constrained by single zircon dates at 2450-2250 Ma. The area of the northern Mawson Escarpment is most likely of ensimatic origin and includes mafic rocks which were derived from distinct mantle source(s) during Palaeoproterozoic time.

Turbidite geochemistry and evolution of the Izu-Bonin arc and continents

NASA Astrophysics Data System (ADS)

Gill, J. B.; Hiscott, R. N.; Vidal, Ph.

1994-10-01

The major and trace element and NdPb isotopic composition of Oligocene to Pleistocene volcaniclastic sands and sandstones derived from the Izu Bonin island arc has been determined. Many characteristics of the igneous sources are preserved and record the geochemical evolution of juvenile proto-continental crust in an island arc. After an initial boninitic phase, arc geochemistry has varied primarily as the result of backarc basin formation. The Izu arc source became depleted in incompatible trace elements during backarc basin formation, and re-enriched after spreading stopped in the basin. Renewed rifting during the Pliocene to Recent caused felsic magmatism as a result of easier eruption of differentiates rather than as a result of crustal melting. Four isotopically-distinct source components are recognized. Their combination in the sources of the Izu-Bonin and Mariana arcs initially was similar but diverged after backarc basin formation. The Izu arc turbidites are more similar to Archean than post-Archean sedimentary rocks, indicating that the production of new upper crust at subduction zones has changed little over time. The turbidites are similar in major element composition to average continental crust but are depleted in incompatible trace elements, especially Th and Nb. Consequently, the net effect of adding juvenile arc crust to continents is to reverse the trend of planetary trace element differentiation instead of continuing the process.

Isotope source apportionment of carbonaceous aerosol as a function of particle size and thermal refractiveness

NASA Astrophysics Data System (ADS)

Masalaite, Agne; Holzinger, Rupert; Remeikis, Vidmantas; Röckmann, Thomas; Dusek, Ulrike

2016-04-01

The stable carbon isotopes can be used to get information about sources and processing of carbonaceous aerosol. We will present results from source apportionment of carbonaceous aerosol as a function of particle size thermal refractiveness. Separate source apportionment for particles smaller than 200 nm and for different carbon volatility classes are rarely reported and give new insights into aerosol sources in the urban environment. Stable carbon isotope ratios were measured for the organic carbon (OC) fraction and total carbon (TC) of MOUDI impactor samples that were collected on a coastal site (Lithuania) during the winter 2012 and in the city of Vilnius (Lithuania) during the winter of 2009. The 11 impactor stages spanned a size range from 0.056 to 18 μm, but only the 6 stages in the submicron range were analysed. The δ13C values of bulk total carbon (δ13CTC) were determined with an elemental analyser (Flash EA 1112) coupled with an isotope ratio mass spectrometer (Thermo Finnigan Delta Plus Advantage) (EA - IRMS). Meanwhile δ13COC was measured using thermal-desorption isotope ratio mass spectrometry (IRMS) system. This allows a rough separation of the more volatile OC fraction (desorbed in the oven of IRMS up to 250 0C) from the more refractory fraction (desorbed up to 400 0C). In this study we investigated the composition of organic aerosol desorbed from filter samples at different temperatures using the thermal-desorption proton-transfer-reaction mass spectrometry (TD-PTR-MS) technique. During winter-time in Lithuania we expect photochemistry and biogenic emissions to be of minor importance. The main sources of aerosol carbon should be fossil fuel and biomass combustion. In both sites, the coastal and the urban site, δ13C measurements give a clear indication that the source contributions differ for small and large particles. Small particles < 200 nm are depleted in 13C with respect to larger particles by 1 - 2 ‰Ṫhis shows that OC in small particle arises mainly from fossil fuel sources, whereas OC in larger particles from 200 nm to 1 μm has higher contribution from biomass burning/other sources. Moreover, there is a clear distinction in source contribution between the more volatile OC fraction and the more refractory fraction. The more refractory fraction is enriched in 13C by 1 to 2 ‰ for both small and large particles. These results show that the fossil fuel combustion is associated to a larger degree with more volatile carbon, whereas biomass burning is the main source of the more refractory particles. According to our source apportionment, the more volatile carbon fraction in the smallest particles is almost completely from fossil fuels, whereas the more refractory carbon fraction in the large size range is almost complete from biomass burning. The more refractory small particles and the less refractory large particles are roughly an even mix of these two sources. The detailed chemical speciation of the carbonaceous aerosol will be presented as well. Acknowledgements This study was funded by the Dutch Science Foundation (NWO grants Nr. 820.01.001, and 834.08.002).

Mercury and Methylmercury concentrations and loads in Cache Creek Basin, California, January 2000 through May 2001

USGS Publications Warehouse

Domagalski, Joseph L.; Alpers, Charles N.; Slotton, Darrell G.; Suchanek, Thomas H.; Ayers, Shaun M.

2004-01-01

Concentrations and mass loads of total mercury and methylmercury in streams draining abandoned mercury mines and near geothermal discharge in Cache Creek Basin, California, were measured during a 17-month period from January 2000 through May 2001. Rainfall and runoff averages during the study period were lower than long-term averages. Mass loads of mercury and methylmercury from upstream sources to downstream receiving waters, such as San Francisco Bay, were generally the highest during or after winter rainfall events. During the study period, mass loads of mercury and methylmercury from geothermal sources tended to be greater than those from abandoned mining areas because of a lack of large precipitation events capable of mobilizing significant amounts of either mercury-laden sediment or dissolved mercury and methylmercury from mine waste. Streambed sediments of Cache Creek are a source of mercury and methylmercury to downstream receiving bodies of water such as the Delta of the San Joaquin and Sacramento Rivers. Much of the mercury in these sediments was deposited over the last 150 years by erosion and stream discharge from abandoned mines or by continuous discharges from geothermal areas. Several geochemical constituents were useful as natural tracers for mining and geothermal areas. These constituents included aqueous concentrations of boron, chloride, lithium, and sulfate, and the stable isotopes of hydrogen and oxygen in water. Stable isotopes of water in areas draining geothermal discharges were enriched with more oxygen-18 relative to oxygen-16 than meteoric waters, whereas the enrichment by stable isotopes of water from much of the runoff from abandoned mines was similar to that of meteoric water. Geochemical signatures from stable isotopes and trace-element concentrations may be useful as tracers of total mercury or methylmercury from specific locations; however, mercury and methylmercury are not conservatively transported. A distinct mixing trend of trace elements and stable isotopes of hydrogen and oxygen from geothermal waters was apparent in Sulphur Creek and lower Bear Creek (tributaries to Cache Creek), but the signals are lost upon mixing with Cache Creek because of dilution.

Atacama perchlorate as an agricultural contaminant in groundwater: Isotopic and chronologic evidence from Long Island, New York

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

Bohlke, J. K.; Hatzinger, Paul B.; Sturchio, N. C.

2009-01-01

Perchlorate (ClO{sub 4}{sup -}) is a common groundwater constituent with both synthetic and natural sources. A potentially important source of ClO{sub 4}{sup -} is past agricultural application of ClO{sub 4}{sup -}-bearing natural NO{sub 3}{sup -} fertilizer imported from the Atacama Desert, Chile, but evidence for this has been largely circumstantial. Here we report ClO{sub 4}{sup -} stable isotope data ({delta}{sup 37}Cl, {delta}{sup 18}O, and {Delta}{sup 17}O), along with other supporting chemical and isotopic environmental tracer data, to document groundwater ClO{sub 4}{sup -} contamination sources and history in parts of Long Island, New York. Sampled groundwaters were oxic and ClO{sub 4}{supmore » -} apparently was not affected by biodegradation within the aquifers. Synthetic ClO{sub 4}{sup -} was indicated by the isotopic method in groundwater near a fireworks disposal site at a former missile base. Atacama ClO{sub 4}{sup -} was indicated in agricultural and urbanizing areas in groundwaters with apparent ages >20 years. In an agricultural area, ClO{sub 4}{sup -} concentrations and ClO{sub 4}{sup -}/NO{sub 3}{sup -} ratios increased with groundwater age, possibly because of decreasing application rates of Atacama NO{sub 3}{sup -} fertilizers and/or decreasing ClO{sub 4}{sup -} concentrations in Atacama NO{sub 3}{sup -} fertilizers in recent years. Because ClO{sub 4}{sup -}/NO{sub 3}{sup -} ratios of Atacama NO{sub 3}{sup -} fertilizers imported in the past (2 x 10{sup -3} mol mol{sup -1}) were much higher than the ClO{sub 4}{sup -}/NO{sub 3}{sup -} ratio of recommended drinking-water limits (7 x 10{sup -5} mol mol{sup -1} in New York), ClO{sub 4}{sup -} could exceed drinking-water limits even where NO{sub 3}{sup -} does not, and where Atacama NO{sub 3}{sup -} was only a minor source of N. Groundwater ClO{sub 4}{sup -} with distinctive isotopic composition was a sensitive indicator of past Atacama NO{sub 3}{sup -} fertilizer use on Long Island and may be common in other areas that received NO{sub 3}{sup -} fertilizers from the late 19th century through the 20th century.« less

The Significance of Atypical High-Silica Igneous Rocks

NASA Astrophysics Data System (ADS)

Frazer, Ryan Edward

The origins of high-silica igneous rocks are debated, as they may be products of high-degree fractional crystallization or low-degree partial melting. They may play a role in the generation of intermediate igneous rocks and are responsible for large, ash-rich volcanic eruptions. High-silica granites and rhyolites in the Sierra Nevada, California, and the Colorado Mineral Belt (CMB) are investigated using isotope geochemistry to better understand how they bear on these questions. Zircon U-Pb geochronology identifies two intrusive suites comprising large volumes of high-silica granites emplaced in the mid-Cretaceous Sierra Nevada batholith: the 106-98 Ma Shaver Intrusive Suite (SIS) in the central part of the batholith, and the 103-100 Ma Kearsarge intrusive suite (KIS) on the Sierra Crest and Owens Valley. High-silica granites in both suites have relatively high concentrations of middle rare earth and high field strength elements. Data for these and other discrete high-silica plutons in the batholith suggest they were derived from titanite-free sources in the deep crust, unlike similarly felsic parts of zoned intrusive suites. Despite similar trace element signatures, SIS and KIS high-silica granites have divergent isotopic compositions. High-silica granites of the SIS have supracrustal O in zircon, crustal Sr and Nd whole rock isotopic compositions, and negative Ce anomalies suggesting the SIS granites may have been derived from oceanic sedimentary sources. In contrast, KIS granites have mantle-like isotopic compositions. The location and geochemistry of the KIS suggests it may have resulted from backarc magmatism in the mid-Cretaceous Sierra. Volcanic and plutonic rocks in the central CMB were emplaced during the Laramide orogeny and subsequent Oligocene-Eocene volcanic flare-up. Strontium and Nd data suggest the 63-39 Ma Twin Lakes pluton and igneous rocks as young as 24 Ma were derived from a persistent mafic lower crust or enriched lithospheric mantle source. In contrast, the ˜35 Ma Grizzly Peak Tuff and resurgent plutons are isotopically dissimilar from each other and the CMB as a whole, suggesting derivation by partial melting of ancient felsic lower crust. This distinct source could account for the lack Mo mineralization in the Grizzly Peak caldera relative to other high-silica parts of the CMB.

Dust composition changes from Taylor Glacier (East Antarctica) during the last glacial-interglacial transition: A multi-proxy approach

NASA Astrophysics Data System (ADS)

Aarons, Sarah M.; Aciego, Sarah M.; Arendt, Carli A.; Blakowski, Molly A.; Steigmeyer, August; Gabrielli, Paolo; Sierra-Hernández, M. Roxana; Beaudon, Emilie; Delmonte, Barbara; Baccolo, Giovanni; May, Nathaniel W.; Pratt, Kerri A.

2017-04-01

Mineral dust is transported in the atmosphere and deposited in oceans, ice sheets and the terrestrial biosphere. Temporal changes in locations of dust source areas and transport pathways have implications for global climate and biogeochemical cycles. The chemical and physical characterization of the dust record preserved in ice cores is useful for identifying of dust source regions, dust transport, dominant wind direction and storm trajectories. Here, we present a 50,000-year geochemical characterization of mineral dust entrapped in a horizontal ice core from the Taylor Glacier in East Antarctica. Strontium (Sr) and neodymium (Nd) isotopes, grain size distribution, trace and rare earth element (REE) concentrations, and inorganic ion (Cl- and Na+) concentrations were measured in 38 samples, corresponding to a time interval from 46 kyr before present (BP) to present. The Sr and Nd isotope compositions of insoluble dust in the Taylor Glacier ice shows distinct changes between the Last Glacial Period (LGP in this study ranging from ∼46.7-15.3 kyr BP) the early Holocene (in this study ranging from ∼14.5-8.7 kyr BP), and zero-age samples. The 87Sr/86Sr isotopic composition of dust in the Taylor Glacier ice ranged from 0.708 to 0.711 during the LGP, while the variability during the early Holocene is higher ranging from 0.707 to 0.714. The εNd composition ranges from 0.1 to -3.9 during the LGP, and is more variable from 1.9 to -8.2 during the early Holocene. The increased isotopic variability during the early Holocene suggests a shift in dust provenance coinciding with the major climate transition from the LGP to the Holocene. The isotopic composition and multiple physical and chemical constraints support previous work attributing Southern South America (SSA) as the main dust source to East Antarctica during the LGP, and a combination of both local Ross Sea Sector dust sources and SSA after the transition into the Holocene. This study provides the first high time resolution data showing variations in dust provenance to East Antarctic ice during a major climate regime shift, and we provide evidence of changes in the atmospheric transport pathways of dust following the last deglaciation.

Dry season limnological conditions and basin geology exhibit complex relationships with δ13C and δ15N of carbon sources in four Neotropical floodplains.

PubMed

Zaia Alves, Gustavo H; Hoeinghaus, David J; Manetta, Gislaine I; Benedito, Evanilde

2017-01-01

Studies in freshwater ecosystems are seeking to improve understanding of carbon flow in food webs and stable isotopes have been influential in this work. However, variation in isotopic values of basal production sources could either be an asset or a hindrance depending on study objectives. We assessed the potential for basin geology and local limnological conditions to predict stable carbon and nitrogen isotope values of six carbon sources at multiple locations in four Neotropical floodplain ecosystems (Paraná, Pantanal, Araguaia, and Amazon). Limnological conditions exhibited greater variation within than among systems. δ15N differed among basins for most carbon sources, but δ13C did not (though high within-basin variability for periphyton, phytoplankton and particulate organic carbon was observed). Although δ13C and δ15N values exhibited significant correlations with some limnological factors within and among basins, those relationships differed among carbon sources. Regression trees for both carbon and nitrogen isotopes for all sources depicted complex and in some cases nested relationships, and only very limited similarity was observed among trees for different carbon sources. Although limnological conditions predicted variation in isotope values of carbon sources, we suggest the resulting models were too complex to enable mathematical corrections of source isotope values among sites based on these parameters. The importance of local conditions in determining variation in source isotope values suggest that isotopes may be useful for examining habitat use, dispersal and patch dynamics within heterogeneous floodplain ecosystems, but spatial variability in isotope values needs to be explicitly considered when testing ecosystem models of carbon flow in these systems.

Dry season limnological conditions and basin geology exhibit complex relationships with δ13C and δ15N of carbon sources in four Neotropical floodplains

PubMed Central

Hoeinghaus, David J.; Manetta, Gislaine I.; Benedito, Evanilde

2017-01-01

Studies in freshwater ecosystems are seeking to improve understanding of carbon flow in food webs and stable isotopes have been influential in this work. However, variation in isotopic values of basal production sources could either be an asset or a hindrance depending on study objectives. We assessed the potential for basin geology and local limnological conditions to predict stable carbon and nitrogen isotope values of six carbon sources at multiple locations in four Neotropical floodplain ecosystems (Paraná, Pantanal, Araguaia, and Amazon). Limnological conditions exhibited greater variation within than among systems. δ15N differed among basins for most carbon sources, but δ13C did not (though high within-basin variability for periphyton, phytoplankton and particulate organic carbon was observed). Although δ13C and δ15N values exhibited significant correlations with some limnological factors within and among basins, those relationships differed among carbon sources. Regression trees for both carbon and nitrogen isotopes for all sources depicted complex and in some cases nested relationships, and only very limited similarity was observed among trees for different carbon sources. Although limnological conditions predicted variation in isotope values of carbon sources, we suggest the resulting models were too complex to enable mathematical corrections of source isotope values among sites based on these parameters. The importance of local conditions in determining variation in source isotope values suggest that isotopes may be useful for examining habitat use, dispersal and patch dynamics within heterogeneous floodplain ecosystems, but spatial variability in isotope values needs to be explicitly considered when testing ecosystem models of carbon flow in these systems. PMID:28358822

Isotopic Composition and Origin of Indigenous Natural Perchlorate and Co-Occurring Nitrate in the Southwestern United States

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

Jackson, Andrew; Bohlke, J. K.; Gu, Baohua

Perchlorate (ClO4-) has been detected over an expansive area in groundwater and soils in the southwestern United States. Because of its wide distribution, much of the ClO4- is presumed to be from natural sources, primarily atmospheric deposition and accumulation. The objective of this study was to evaluate the range of the isotopic composition of natural ClO4- indigenous to the southwestern U.S. Stable isotope ratios of Cl and O were determined for ClO4- collected from numerous sources, including: groundwater from several locations in the southern high plains (SHP) of Texas and New Mexico and the middle Rio Grande Basin in Newmore » Mexico, vadose zone soil from the SHP, and surface NO3--rich caliches from four locations in Death Valley, CA. The data suggest that natural ClO4- in the southwestern U.S. has at least two distinctive isotope signatures that differ both from each other and from those previously reported for natural ClO4- from the Atacama Desert of Chile and all anthropogenic ClO4- sources tested to date. The ClO4- in four caliche samples collected in Death Valley has high 17O values (8.6 to 18.4 ), similar to those described for ClO4- from the Atacama, and suggesting atmospheric formation via reaction with ozone (O3). However, the Death Valley samples have 37Cl values (-3.1 to -0.8 ) and 18O values (+2.9 to +26.1 ), that are appreciably higher than Atacama perchlorate ( 37Cl; -14.3 to -10.2 and 18O; (-10.5 to -2.2 , respectively). In contrast, samples from 8 locations in West Texas and New Mexico were characterized by only a slight elevation in 17O (0.3 to 1.3 ), suggesting either that this material is not primarily generated with O3 as a reactant or that the ClO4- has been consistently altered post-deposition by one or more processes that caused isotopic exchange of O. The 37Cl values in the SHP perchlorate (+ 3.4 to + 5.1 ) were consistently higher than for the Atacama or Death Valley salts, while the 18O values (+ 0.5 to + 4.8 ) overlapped significantly with those from Death Valley. Additional studies are necessary to better understand the various origins and potential exchange reactions of natural perchlorate, however, the data presented herein provide constraints on natural isotope signatures important for interpretation of isotope values at locations in which ClO4- sources in groundwater or drinking water are unknown.« less

Position-specific 13C distributions within propane from experiments and natural gas samples

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael D.; Eiler, John M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, 'bulk' isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems.

Position-specific 13C distributions within propane from experiments and natural gas samples

USGS Publications Warehouse

Piasecki, Alison; Sessions, Alex L.; Lawson, Michael; Ferreira, A.A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael; Eilers, J.M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, ‘bulk’ isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems.

Radiocarbon as a Novel Tracer of Extra-Antarctic Feeding in Southern Hemisphere Humpback Whales.

PubMed

Eisenmann, Pascale; Fry, Brian; Mazumder, Debashish; Jacobsen, Geraldine; Holyoake, Carlysle Sian; Coughran, Douglas; Bengtson Nash, Susan

2017-06-29

Bulk stable isotope analysis provides information regarding food web interactions, and has been applied to several cetacean species for the study of migration ecology. One limitation in bulk stable isotope analysis arises when a species, such as Southern hemisphere humpback whales, utilises geographically distinct food webs with differing isotopic baselines. Migrations to areas with different baselines can result in isotopic changes that mimic changes in feeding relations, leading to ambiguous food web interpretations. Here, we demonstrate the novel application of radiocarbon measurement for the resolution of such ambiguities. Radiocarbon was measured in baleen plates from humpback whales stranded in Australia between 2007 and 2013, and in skin samples collected in Australia and Antarctica from stranded and free-ranging animals. Radiocarbon measurements showed lower values for Southern Ocean feeding than for extra-Antarctic feeding in Australian waters. While the whales mostly relied on Antarctic-derived energy stores during their annual migration, there was some evidence of feeding within temperate zone waters in some individuals. This work, to our knowledge, provides the first definitive biochemical evidence for supplementary feeding by southern hemisphere humpback whales within temperate waters during migration. Further, the work contributes a powerful new tool (radiocarbon) for tracing source regions and geographical feeding.

The He isotope composition of the earliest picrites erupted by the Ethiopia plume, implications for mantle plume source

NASA Astrophysics Data System (ADS)

Stuart, Finlay; Rogers, Nick; Davies, Marc

2016-04-01

The earliest basalts erupted by mantle plumes are Mg-rich, and typically derived from mantle with higher potential temperature than those derived from the convecting upper mantle at mid-ocean ridges and ocean islands. The chemistry and isotopic composition of picrites from CFB provide constraints on the composition of deep Earth and thus the origin and differentiation history. We report new He-Sr-Nd-Pb isotopic composition of the picrites from the Ethiopian flood basalt province from the Dilb (Chinese Road) section. They are characterized by high Fe and Ti contents for MgO = 10-22 wt. % implying that the parent magma was derived from a high temperature low melt fraction, most probably from the Afar plume head. The picrite 3He/4He does not exceed 21 Ra, and there is a negative correlation with MgO, the highest 3He/4He corresponding to MgO = 15.4 wt. %. Age-corrected 87Sr/86Sr (0.70392-0.70408) and 143Nd/144Nd (0.512912-0.512987) display little variation and are distinct from MORB and OIB. Age-corrected Pb isotopes display a significant range (e.g. 206Pb/204Pb = 18.70-19.04) and plot above the NHRL. These values contrast with estimates of the modern Afar mantle plume which has lower 3He/4He and Sr, Nd and Pb isotope ratios that are more comparable with typical OIB. These results imply either interaction between melts derived from the Afar mantle plume and a lithospheric component, or that the original Afar mantle plume had a rather unique radiogenic isotope composition. Regardless of the details of the origins of this unusual signal, our observations place a minimum 3He/4He value of 21 Ra for the Afar mantle plume, significantly greater than the present day value of 16 Ra, implying a significant reduction over 30 Myr. In addition the Afar source was less degassed than convecting mantle but more degassed than mantle sampled by the proto-Iceland plume (3He/4He ~50 Ra). This suggests that the largest mantle plumes are not sourced in a single deep mantle domain with a common depletion history and that they do not mix with shallower mantle reservoirs to the same extent.

A look inside 'black box' hydrograph separation models: A study at the hydrohill catchment

USGS Publications Warehouse

Kendall, C.; McDonnell, Jeffery J.; Gu, W.

2001-01-01

Runoff sources and dominant flowpaths are still poorly understood in most catchments; consequently, most hydrograph separations are essentially 'black box' models where only external information is used. The well-instrumented 490 m2 Hydrohill artificial grassland catchment located near Nanjing (China) was used to examine internal catchment processes. Since groundwater levels never reach the soil surface at this site, two physically distinct flowpaths can unambiguously be defined: surface and subsurface runoff. This study combines hydrometric, isotopic and geochemical approaches to investigating the relations between the chloride, silica, and oxygen isotopic compositions of subsurface waters and rainfall. During a 120 mm storm over a 24 h period in 1989, 55% of event water input infiltrated and added to soil water storage; the remainder ran off as infiltration-excess overland flow. Only about 3-5% of the pre-event water was displaced out of the catchment by in-storm rainfall. About 80% of the total flow was quickflow, and 10% of the total flow was pre-event water, mostly derived from saturated flow from deeper soils. Rain water with high ??18O values from the beginning of the storm appeared to be preferentially stored in shallow soils. Groundwater at the end of the storm shows a wide range of isotopic and chemical compositions, primarily reflecting the heterogeneous distribution of the new and mixed pore waters. High chloride and silica concentrations in quickflow runoff derived from event water indicate that these species are not suitable conservative tracers of either water sources or flowpaths in this catchment. Determining the proportion of event water alone does not constrain the possible hydrologic mechanisms sufficiently to distinguish subsurface and surface flowpaths uniquely, even in this highly controlled artificial catchment. We reconcile these findings with a perceptual model of stormflow sources and flowpaths that explicitly accounts for water, isotopic, and chemical mass balance. Copyright ?? 2001 John Wiley & Sons, Ltd.

Lead in Martian Meteorites-- Observations and Inconsistencies: I. Chassigny

NASA Technical Reports Server (NTRS)

Jones, J. H.; Simon, J. I.; Usui, T.

2017-01-01

The history of Pb isotope analyses of the martian meteorites (SNC) and their interpretations is laden with difficulties. Two different analytical groups have interpreted their ancient (= 4 Ga) shergottite Pb ages as primary [1-5]. A Nakhla age of approximately 4.3 Ga has been interpreted to be primary as well [2]. This is in stark contrast to the young (= 1.4 Ga) crystallization ages defined by the Rb-Sr, Sm-Nd, Lu-Hf, and KAr systems [6]. Possibly, a better interpretation for the ancient Pb ages is that they reflect the formation times of the various SNC source regions [7]. A difficulty in dealing with Pb is that terrestrial contamination is ubiquitous, unlike the other chronometer systems noted above. This issue is complicated by the fact that radioactive decay causes localized mineral damage. So washing and leaching to remove Pb contamination tends to remove in situ radiogenic Pb. This issue is further compounded because U and Th are often concentrated in phosphates and other minor phases, so the leaching process tends to remove these, especially phosphates. Another difficulty is that it is not clear whether the observed Pb isotopic variation in leachates, residues, and ion-microprobe analyses is due to terrestrial or to indigenous martian Pb contamination [e.g., 8]. A third difficulty is that the shergottites on the one hand, and the nakhlites and chassignites on the other, appear to have come from separate source regions with different chemical compositions [e.g., 7]. Thus, it is expected that their Pb isotopic characteristics would be different. And even if all these meteorite types came from the same source region, their igneous ages differ considerably. The nakhlites and chassignites are 1.4 Ga and the shergottites are = 600 Ma [e.g., 6]. This age difference alone should assure that the two distinct SNC groups have differing Pb isotopic signatures.

A quantitative approach to combine sources in stable isotope mixing models

EPA Science Inventory

Stable isotope mixing models, used to estimate source contributions to a mixture, typically yield highly uncertain estimates when there are many sources and relatively few isotope elements. Previously, ecologists have either accepted the uncertain contribution estimates for indiv...

Isotopic source signatures: Impact of regional variability on the δ13CH4 trend and spatial distribution

NASA Astrophysics Data System (ADS)

Feinberg, Aryeh I.; Coulon, Ancelin; Stenke, Andrea; Schwietzke, Stefan; Peter, Thomas

2018-02-01

The atmospheric methane growth rate has fluctuated over the past three decades, signifying variations in methane sources and sinks. Methane isotopic ratios (δ13CH4) differ between emission categories, and can therefore be used to distinguish which methane sources have changed. However, isotopic modelling studies have mainly focused on uncertainties in methane emissions rather than uncertainties in isotopic source signatures. We simulated atmospheric δ13CH4 for the period 1990-2010 using the global chemistry-climate model SOCOL. Empirically-derived regional variability in the isotopic signatures was introduced in a suite of sensitivity simulations. These simulations were compared to a baseline simulation with commonly used global mean isotopic signatures. We investigated coal, natural gas/oil, wetland, livestock, and biomass burning source signatures to determine whether regional variations impact the observed isotopic trend and spatial distribution. Based on recently published source signature datasets, our calculated global mean isotopic signatures are in general lighter than the commonly used values. Trends in several isotopic signatures were also apparent during the period 1990-2010. Tropical livestock emissions grew during the 2000s, introducing isotopically heavier livestock emissions since tropical livestock consume more C4 vegetation than midlatitude livestock. Chinese coal emissions, which are isotopically heavy compared to other coals, increase during the 2000s leading to higher global values of δ13CH4 for coal emissions. EDGAR v4.2 emissions disagree with the observed atmospheric isotopic trend for almost all simulations, confirming past doubts about this emissions inventory. The agreement between the modelled and observed δ13CH4 interhemispheric differences improves when regional source signatures are used. Even though the simulated results are highly dependent on the choice of methane emission inventories, they emphasize that the commonly used global mean signatures are inadequate. Regional isotopic signatures should be employed in modelling studies that try to constrain methane emission inventories.

Isotopic evidence for enhanced fossil fuel sources of aerosol ammonium in the urban atmosphere.

PubMed

Pan, Yuepeng; Tian, Shili; Liu, Dongwei; Fang, Yunting; Zhu, Xiaying; Gao, Meng; Gao, Jian; Michalski, Greg; Wang, Yuesi

2018-07-01

The sources of aerosol ammonium (NH 4 + ) are of interest because of the potential of NH 4 + to impact the Earth's radiative balance, as well as human health and biological diversity. Isotopic source apportionment of aerosol NH 4 + is challenging in the urban atmosphere, which has excess ammonia (NH 3 ) and where nitrogen isotopic fractionation commonly occurs. Based on year-round isotopic measurements in urban Beijing, we show the source dependence of the isotopic abundance of aerosol NH 4 + , with isotopically light (-33.8‰) and heavy (0 to +12.0‰) NH 4 + associated with strong northerly winds and sustained southerly winds, respectively. On an annual basis, 37-52% of the initial NH 3 concentrations in urban Beijing arises from fossil fuel emissions, which are episodically enhanced by air mass stagnation preceding the passage of cold fronts. These results provide strong evidence for the contribution of non-agricultural sources to NH 3 in urban regions and suggest that priority should be given to controlling these emissions for haze regulation. This study presents a carefully executed application of existing stable nitrogen isotope measurement and mass-balance techniques to a very important problem: understanding source contributions to atmospheric NH 3 in Beijing. This question is crucial to informing environmental policy on reducing particulate matter concentrations, which are some of the highest in the world. However, the isotopic source attribution results presented here still involve a number of uncertain assumptions and they are limited by the incomplete set of chemical and isotopic measurements of gas NH 3 and aerosol NH 4 + . Further field work and lab experiments are required to adequately characterize endmember isotopic signatures and the subsequent isotopic fractionation process under different air pollution and meteorological conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

[Research progress on food sources and food web structure of wetlands based on stable isotopes].

PubMed

Chen, Zhan Yan; Wu, Hai Tao; Wang, Yun Biao; Lyu, Xian Guo

2017-07-18

The trophic dynamics of wetland organisms is the basis of assessing wetland structure and function. Stable isotopes of carbon and nitrogen have been widely applied to identify trophic relationships in food source, food composition and food web transport in wetland ecosystem studies. This paper provided an overall review about the current methodology of isotope mixing model and trophic level in wetland ecosystems, and discussed the standards of trophic fractionation and baseline. Moreover, we characterized the typical food sources and isotopic compositions of wetland ecosystems, summarized the food sources in different trophic levels of herbivores, omnivores and carnivores based on stable isotopic analyses. We also discussed the limitations of stable isotopes in tra-cing food sources and in constructing food webs. Based on the current results, development trends and upcoming requirements, future studies should focus on sample treatment, conservation and trophic enrichment measurement in the wetland food web, as well as on combing a variety of methodologies including traditional stomach stuffing, molecular markers, and multiple isotopes.

STABLE ISOTOPES IN ECOLOGICAL STUDIES: NEW DEVELOPMENTS IN MIXING MODELS (URUGUAY)

EPA Science Inventory

Stable isotopes are increasingly being used as tracers in ecological studies. One application uses isotopic ratios to quantify the proportional contributions of multiple sources to a mixture. Examples include pollution sources for air or water bodies, food sources for animals, ...

STABLE ISOTOPES IN ECOLOGICAL STUDIES: NEW DEVELOPMENTS IN MIXING MODELS (BRAZIL)

EPA Science Inventory

Stable isotopes are increasingly being used as tracers in ecological studies. One application uses isotopic ratios to quantify the proportional contributions of multiple sources to a mixture. Examples include pollution sources for air or water bodies, food sources for animals, ...

Regional Distribution of Metals and C and N Stable Isotopes in the Epiphytic Ball Moss (Tillandsia Recurvata) at the Mezquital Valley, Hidalgo State

NASA Astrophysics Data System (ADS)

Zambrano-Garcia, A.; López-Veneroni, D.; Rojas, A.; Torres, A.; Sosa, G.

2007-05-01

As a part of the MILAGRO Field Campaign 2006, the influence of anthropogenic sources to metal air pollution in the Mezquital Valley, Hidalgo State, was explored by biomonitoring techniques. This valley is a major industrial- agriculture area located in central Mexico. An oil refinery, an electrical power plant, several cement plants with open-pit mines, as well as intensive wastewater-based agricultural areas, all within a 50 km radius, are some of the most important local sources of particulate air pollution. The concentrations of 25 metals and elements were determined by ICP-AES (EPA 610C method) for triplicate composite samples of the "ball moss" (T. recurvata ) collected at 50 sites. In addition, the ratios of two stable isotopes ((13C/12C and 15N/14N) were determined by continuous-flow isotope-ratio mass spectrometry in order to assess their potential as tracers for industrial emissions. Preliminary results showed high to very high average contents of several metals in the biomonitor compared to values from similar studies in other world regions, indicating a high degree of local air pollution. In contrast, most samples had Ag, As, Be, Se and Tl contents below detection levels (DL = 0.05 mg/kg of sample dry weight) indicating low levels of pollution by these metals. Metals such as Al, Ba, Ca, Fe, Li, Mo, Ni, Sr, Ti, V and Zn concentrated the most at the South portion of the valley, where the Tepeji-Tula-Apaxco industrial corridor is located. A transect parallel to the along-wind direction (N-S) showed a higher concentration of metals farther away from the sources relative to a cross-wind transect, which is consistent with the eolian transport of metal-enriched particles. Regional distribution maps of metals in the biomonitor showed that Al, Ba, Fe, Mo, Ni, Sr, Ti and V had higher levels at the industrial sampling sites; whereas K, Na and P were more abundant near to agriculture areas. Vanadium, a common element of crude oil, reflected better the influence from the local oil refinery and the oil- fueled power plant. Two distinct Ni:V scatterplot trends suggest that there are two main petrogenic emission sources in the region. Calcium and, to some extent, Mg were higher near the mining areas and a calcium carbonate factory. Lead had a diffuse distribution, probably related to former gasoline vehicle exhaust emissions, rather than to current emissions. Antimony was more abundant at sites far from agriculture and industrial areas, which suggests a natural origin (rocks or soils). The spatial distribution of stable isotopes also showed distinct patterns near the industrial sources with relatively 13C -depleted and 15N -enriched values near the oil refinery and the electrical power plant. Although it is not yet possible to provide quantitative estimates for emission contributions per source type, biomonitoring with T. recurvata provided for the first time a clear picture of the relative deposition patterns for several airborne metals in the Mezquital Valley.

Hydrologic and environmental controls on uranium-series and strontium isotope ratios in a natural weathering environment

NASA Astrophysics Data System (ADS)

White, A. M.; Ma, L.; Moravec, B. G.; McIntosh, J. C.; Chorover, J.

2017-12-01

In a remote, volcanic headwater catchment of the Jemez River Basin Critical Zone Observatory (JRB-CZO) in NM, stable water isotopes and solute chemistry have shown that snowmelt infiltrates and is stored before later discharging into springs and streams via subsurface flowpaths that vary seasonally. Therefore, water-rock reactions are also expected to change with season as hydrologic flowpaths transport water, gases and solutes through different biogeochemical conditions, rock types and fracture networks. Uranium-series isotopes have been shown to be a novel tracer of water-rock reactions and source water contributions while strontium isotopes are frequently used as indicators of chemical weathering and bedrock geology. This study combines both isotopes to understand how U and Sr isotope signatures evolve through the Critical Zone (CZ). More specifically, this work examines the relationship between seasonality, water transit time (WTT), and U-series and Sr isotopes in stream and spring waters from three catchments within the JRB-CZO, as well as lithology, rock type and CZ structure in solid phase cores. Samples from ten springs with known WTTs were analyzed for U and Sr isotopes to determine the effect of WTT on the isotopic composition of natural waters. Results suggest that WTT alone cannot explain the variability of U and Sr isotopes in JRB-CZO springs. Stream samples were also collected across two water years to establish how seasonality controls surface water isotopic composition. U and Sr isotope values vary with season, consistent with a previous study from the La Jara catchment; however, this study revealed that these changes do not show a systematic pattern among the three catchments suggesting that differences in the mineralogy and structure of the deep CZ in individual catchments, and partitioning of water along deep vs surficial and fracture vs matrix flow paths, likely also control isotopic variability. The distribution of U-series and Sr isotopes in core samples with depth shows distinct weathering profiles with variable 234U/238U activity and Sr isotope ratios. Comparison of the isotopic composition of cores and groundwaters from similar depths, as well as surface waters in the JRB-CZO will be vital for the characterization of hydrogeologic controls on isotopic composition in this complex terrain.

Petrology of the axial ridge of the Mariana Trough backarc spreading center

NASA Astrophysics Data System (ADS)

Hawkins, J. W.; Lonsdale, P. F.; Macdougall, J. D.; Volpe, A. M.

1990-10-01

The axial ridge of the Mariana Trough backarc basin, between 17°40'N and 18°30'N rises as much as 1 km above the floor of a 10-15 km wide rift valley. Physiographic segmentation, with minor ridge offsets and overlaps, coincides with a petrologic segmentation seen in trace element and isotope chemistry. Analyses of 239 glass and 40 aphyric basalt samples, collected with ALVIN and by dredging, show that the axial ridge is formed largely of (olivine) hypersthene-normative tholeiitic basalt. About half of these are enriched in both LIL elements and volatiles, but are depleted in HFS elements like other rocks found throughout much of the Mariana Trough. The LIL enrichments distinguish these rocks from N-MORB even though Nd and Sr isotope ratios indicate that much of the crust formed from a source similar to that for N-MORB. In addition to LIL-enriched basalt there is LIL depleted basalts even more closely resembling N-MORB in major and trace elements as well as Sr, Nd and Pb isotopes. Both basalt varieties have higher Al and lower total Fe than MORB at equivalent Mg level. Mg# ranges from relatively "primitive" (e.g. Mg# 65-70) to more highly fractionated (e.g. Mg# 45-50). Highest parts of the axial ridge are capped by pinnacles with elongated pillows of basaltic andesite (e.g. 52-56%) SiO 2. These are due to extreme fractional crystallization of basalts forming the axial ridge. Active hydrothermal vents with chimneys and mats of opaline silica, barite, sphalerite and lesser amounts of pyrite, chalcopyrite and galena formed near these silicic rocks. The vents are surrounded by distinctive vent animals, polychaete worms, crabs and barnacles. Isotope data indicate that the Mariana Trough crust was derived from a heterogeneous source including mantle resembling the MORB-source and an "arc-source" component. The latter was depleted in HFS elements in previous melting events and later modified by addition of H 2O and LIL elements.

Geochemistry of the mantle beneath the Rodriguez Triple Junction and the South-East Indian Ridge

NASA Astrophysics Data System (ADS)

Michard, A.; Montigny, R.; Schlich, R.

1986-05-01

Rare earth element abundances and Sr, Nd. Pb isotope compositions have been measured on zero-age dredge samples from the Rodriguez Triple Junction (RTJ) and the South-East Indian Ridge (SEIR), Along the SEIR. the geochemical "halo" of the St. Paul hot spot has a half-width of about 400 km and the data may be fairly well accounted for by a binary mixing between an Indian MORB-type component ( 87Sr/ 86Sr = 0.7028. 143Nd/ 144Nd = 0.51304. 206Pb/ 204Pb = 17.8) and the plume-type St. Paul component (0.7036, 0.5129, and 18.7 respectively). The alignment of the lead isotope data is particularly good with an apparent age of 1.95 ± 0.13 Ga and Th/U source value of 3.94. One sample dredged on the ridge 60 km southeast of St. Paul bears a definite Kerguelen isotopic signature. The RTJ has distinctive geochemical properties which contrast with those of the adjacent ridge segments. Low 206Pb/ 204Pb ratios which plots to the left of the geochron, rather high 208Pb/ 204Pb and 87Sr/ 87Sr ratios (17.4. 37.4, and 0.7031 respectively), a striking isotopic homogeneity, and variable LREE/HREE fractionation with (La/Sm) N, = 0.3-0.8 make this triple junction an anomalous site. The geochemical properties of the Indian Ocean basats have been examined using a three-component mantle model involving (a) a normal MORB-type source though to represent the depleted upper mantle matrix, (b) an OIB-type source of uncertain parentage (recycled oceanic crust?), and (c) a component with low μ. low Sm/Nd. high Rb/Sr (time-averaged value) which is tentatively assigned to ancient hydrothermal and abyssal sediments recycled in the mantle. The high 208Pb/ 204Pb and 87Sr/ 86Sr ratios typical of the Dupal anomaly are likely due to the widespread distribution of this latter component in the basalt source from this area. including that for MORBs.

Tracing groundwater recharge sources in the northwestern Indian alluvial aquifer using water isotopes (δ18O, δ2H and 3H)

NASA Astrophysics Data System (ADS)

Joshi, Suneel Kumar; Rai, Shive Prakash; Sinha, Rajiv; Gupta, Sanjeev; Densmore, Alexander Logan; Rawat, Yadhvir Singh; Shekhar, Shashank

2018-04-01

Rapid groundwater depletion from the northwestern Indian aquifer system in the western Indo-Gangetic basin has raised serious concerns over the sustainability of groundwater and the livelihoods that depend on it. Sustainable management of this aquifer system requires that we understand the sources and rates of groundwater recharge, however, both these parameters are poorly constrained in this region. Here we analyse the isotopic (δ18O, δ2H and tritium) compositions of groundwater, precipitation, river and canal water to identify the recharge sources, zones of recharge, and groundwater flow in the Ghaggar River basin, which lies between the Himalayan-fed Yamuna and Sutlej River systems in northwestern India. Our results reveal that local precipitation is the main source of groundwater recharge. However, depleted δ18O and δ2H signatures at some sites indicate recharge from canal seepage and irrigation return flow. The spatial variability of δ18O, δ2H, d-excess, and tritium reflects limited lateral connectivity due to the heterogeneous and anisotropic nature of the aquifer system in the study area. The variation of tritium concentration with depth suggests that groundwater above c. 80 mbgl is generally modern water. In contrast, water from below c. 80 mbgl is a mixture of modern and old waters, and indicates longer residence time in comparison to groundwater above c. 80 mbgl. Isotopic signatures of δ18O, δ2H and tritium suggest significant vertical recharge down to a depth of 320 mbgl. The spatial and vertical variations of isotopic signature of groundwater reveal two distinct flow patterns in the aquifer system: (i) local flow (above c. 80 mbgl) throughout the study area, and (ii) intermediate and regional flow (below c. 80 mbgl), where water recharges aquifers through large-scale lateral flow as well as vertical infiltration. The understanding of spatial and vertical recharge processes of groundwater in the study area provides important base-line knowledge for developing a sustainable groundwater management plan for the northwestern Indian aquifer system.

Distribution of mercury species and mercury isotope ratios in soils and river suspended matter of a mercury mining area.

PubMed

Baptista-Salazar, Carluvy; Hintelmann, Holger; Biester, Harald

2018-04-25

Mercury (Hg) released by mining activities can be dispersed in the environment, where it is subject to species transformations. Hg isotope ratios have been used to track sources in Hg contaminated areas, although it is unclear to what extent variations in δ-values are attributed to distinct Hg species. Hg was mined as Hg sulphide (cinnabar) in Idrija, Slovenia for centuries. Sediments are loaded with mining-residues (cinnabar and calcine), whereas contaminated soils mainly contain Hg bound to natural organic matter (NOM-Hg) related to atmospheric Hg deposition. Hg released from soils and sediments is transported as suspended matter (SM) in the Idrijca river to the Gulf of Trieste (GT), Italy. We determine Hg isotope ratios in river SM, sediments and soils from the Idrijca-catchment to decipher the Hg isotope ratio variability related to Hg species distribution in different grain-size fractions. δ202Hg values of SM collected from tributaries corresponded to those found in soils ranging from -2.58 to 0.19‰ and from -2.27 to -0.88‰, respectively. Speciation measurements reveal that fine fractions (0.45-20 μm) are dominated by NOM-Hg, while larger fractions contain more cinnabar. More negative δ202Hg values were related to higher proportions of NOM-Hg, which are predominant in soils and SM. Rain events increase SM-loads in the river, mainly due to resuspension of coarse grain-size fractions of bottom sediments bearing larger proportions of cinnabar, which leads to more positive δ202Hg values. The large magnitude of variation in δ202Hg and the smaller magnitude of variation in Δ199Hg (-0.37 to 0.09‰) are likely related to fractionation during ore roasting. Soil samples with high NOM-Hg content show more negative δ202Hg values and larger variation of Δ199Hg. More negative δ202Hg values in GT sediments were rather linked to distant sedimentation of soil derived NOM-Hg than to sedimentation of autochthonous marine material. Heterogeneity in the Idrija ore and ore processing likely produce large variations in the Hg isotopic composition of cinnabar and released metallic Hg, which complicate the differentiation of Hg sources. Combining Hg isotope measurements with solid phase Hg speciation reveals that Hg isotope ratios rather indicate different Hg species and are not necessarily symptomatic for Hg pollution sources.

Sr isotopic composition as a tracer of Ca sources in two forest ecosystems in Belgium.

NASA Astrophysics Data System (ADS)

Drouet, T.; Herbauts, J.; Demaiffe, D.

2003-04-01

The two main sources of Ca in forest ecosystem are the mineral weathering release and atmospheric inputs. We use the 87Sr/86Sr isotopic ratio (Sr is a proxy for Ca) to determine the Ca contribution from rain input in two forest ecosystems (beech stands) growing on soils formed from parent materials with distinct total Ca contents and contrasted isotopic ratios: Pleistocene loess in Central Belgium (leached brown soil) with present-day 87Sr/86Sr =0.72788 and Lower Devonian shales and sandstones in Ardennes (ochreous brown earth) with 87Sr/86Sr = 0.76913. The 87Sr/86Sr ratios and the Ca and Sr contents were measured in rainwater, vegetation (beech wood growth rings and leaves) and main soil horizons (total, labile and HCl 0.1 M soluble forms). The relative contributions of atmospheric input and soil mineral weathering to vegetation were calculated using mixing equations. Calculations based on the Sr isotope ratios of rainwater (endmember 1; 87Sr/86Sr close to seawater: 0.7090), labile soil fraction (endmember 2; 87Sr/86Sr: 0.71332 to 0.71785) and beech wood (mixing compartment) indicate that about 50 % (Central Belgium) to 35 % (Ardennes) of Ca uptake originate from atmospheric inputs. The choice of the appropriate 87Sr/86Sr ratio for the weathering endmember is however critical. The isotopic composition of the mineral source is theoretically determined by the mineralogical composition of the soil and the relative weatherability of the Sr-bearing minerals. Due to soil processes (weathering and clay illuviation), the distribution of minerals in both soil profiles is not homogeneous and varies from horizon to horizon. Which horizons are relevant and which kind of soil extract (labile soil fraction, acid soluble fraction, total soil,...) should be selected for isotopic measurement of weathering endmember, is therefore questionable. The different ways of estimation are discussed. Quantitative mineralogical reconstitutions of soil horizons and isotopic data indicate preferential weathering of plagioclase (high Sr content with low 87Sr/86Sr) rather than mica or K-feldspar (high 87Sr/86Sr). Our results emphasize the importance of the Ca atmospheric contribution to the tree mineral nutrition in these forest ecosystems. It is plausible that acid depositions associated with decreasing input of atmospheric cations (“acid rains”) could increase the depletion of soil available cation pool at a short-time scale.

Aleutian terranes from Nd isotopes

NASA Technical Reports Server (NTRS)

Kay, R. W.; Kay, S. M.; Rubenstone, J. L.

1986-01-01

Nd isotope ratios substantiate the identification of oceanic crustal terranes within the continental crustal basement of the Aleutian island arc. The oceanic terranes are exposed in the westernmost Aleutians, but to the east, they are completely buried by isotopically distinct arc-volcanic rocks. Analogous oceanic terranes may be important components of the terrane collages that comprise the continents.

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).

Osmium isotopes demonstrate distal transport of contaminated sediments in Chesapeake Bay

USGS Publications Warehouse

Helz, G.R.; Adelson, J.M.; Miller, C.V.; Cornwell, J.C.; Hill, J.M.; Horan, M.; Walker, R.J.

2000-01-01

Because the isotopic composition of anthropogenic Os is normally distinctive in comparison to continental crust and is precisely measurable, this platinum-group element is attractive as a tracer of transport pathways for contaminated sediments in estuaries. Evidence herein and elsewhere suggest that biomedical research institutions are the chief source of anthropogenic Os. In the Chesapeake Bay region, uncontaminated sediments bear a crustal 187Os/188Os signature of 0.73 ?? 0.10. Slightly higher 187Os/188Os ratios occur in Re-rich Coastal Plain deposits due to post- Miocene 187Re decay. The upper Susquehanna Basin yields sediments also with higher 187Os/188Os. Beginning in the late 1970s, this signal was overprinted by a low 187Os/188Os (anthropogenic) source in the lower Susquehanna Basin. In the vicinity of Baltimore, which is a major center of heavy industry as well as biomedical research, anthropogenic Os has been found only in sediments impacted by the principal wastewater treatment plant. Surprisingly, a mid-Bay site distant from anthropogenic sources contains the strongest anthropogenic Os signal in the data set, having received anthropogenic Os sporadically since the mid-20th Century. Transport of particles to this site overrode the northward flowing bottom currents. Finding anthropogenic Os at this site cautions that other particle-borne substances, including hazardous ones, could be dispersed broadly in this estuary.Because the isotopic composition of anthropogenic Os is normally distinctive in comparison to continental crust and is precisely measurable, this platinum-group element is attractive as a tracer of transport pathways for contaminated sediments in estuaries. Evidence herein and elsewhere suggest that biomedical research institutions are the chief source of anthropogenic Os. In the Chesapeake Bay region, uncontaminated sediments bear a crustal 187Os/188Os signature of 0.73 ?? 0.10. Slightly higher 187Os/188Os ratios occur in Re-rich Coastal Plain deposits due to post-Miocene 187Re decay. The upper Susquehanna Basin yields sediments also with higher 187Os/188Os. Beginning in the late 1970s, this signal was overprinted by a low 187Os/188Os (anthropogenic) source in the lower Susquehanna Basin. In the vicinity of Baltimore, which is a major center of heavy industry as well as biomedical research, anthropogenic Os has been found only in sediments impacted by the principal wastewater treatment plant. Surprisingly, a mid-Bay site distant from anthropogenic sources contains the strongest anthropogenic Os signal in the data set, having received anthropogenic Os sporadically since the mid-20th Century. Transport of particles to this site overrode the northward flowing bottom currents. Finding anthropogenic Os at this site cautions that other particle-borne substances, including hazardous ones, could be dispersed broadly in this estuary.

The Hadean upper mantle conundrum: evidence for source depletion and enrichment from Sm-Nd, Re-Os, and Pb isotopic compositions in 3.71 Gy boninite-like metabasalts from the Isua Supracrustal Belt, Greenland

NASA Astrophysics Data System (ADS)

Frei, Robert; Polat, Ali; Meibom, Anders

2004-04-01

Here we present Sm-Nd, Re-Os, and Pb isotopic data of carefully screened, least altered samples of boninite-like metabasalts from the Isua Supracrustal Belt (ISB, W Greenland)that characterize their mantle source at the time of their formation. The principal observations of this study are that by 3.7-3.8 Ga melt source regions existed in the upper mantle with complicated enrichment/depletion histories. Sm-Nd isotopic data define a correlation line with a slope corresponding to an age of 3.69 ± 0.18 Gy and an initial εNd value of +2.0 ± 4.7. This Sm-Nd age is consistent with indirect (but more precise) U-Pb geochronological estimates for their formation between 3.69-3.71 Ga. Relying on the maximum formation age of 3.71 Gy defined by the external age constraints, we calculate an average εNd [T = 3.71 Ga] value of +2.2 ± 0.9 (n = 18, 1σ) for these samples, which is indicative of a strongly depleted mantle source. This is consistent with the high Os concentrations, falling in the range between 1.9-3.4 ppb, which is similar to the estimated Os concentration for the primitive upper mantle. Re-Os isotopic data (excluding three outliers) yield an isochron defining an age of 3.76 ± 0.09 Gy (with an initial γOs value of 3.9 ± 1.2), within error consistent with the Sm-Nd age and the indirect U-Pb age estimates. An average initial γOs [T = 3.71 Ga] value of + 4.4 ± 1.2 (n = 8; 2σ) is indicative of enrichment of their source region during, or prior to, its melting. Thus, this study provides the first observation of an early Archean upper mantle domain with a distinctly radiogenic Os isotopic signature. This requires a mixing component characterized by time-integrated suprachondritic Re/Os evolution and a Os concentration high enough to strongly affect the Os budget of the mantle source; modern sediments, recycled basaltic crust, or the outer core do not constitute suitable candidates. At this point, the nature of the mantle or crustal component responsible for the radiogenic Os isotopic signature is not known. Compared with the Sm-Nd and Re-Os isotope systems, the Pb isotope systematics show evidence for substantial perturbation by postformational hydrothermal-metasomatic alteration processes accompanying an early Archean metamorphic event at 3510 ± 65 Ma and indicate that the U-Th-Pb system was partially opened to Pb-loss on a whole rock scale. Single stage mantle evolution models fail to provide a solution to the Pb isotopic data, which requires that a high-μ component was mixed with the depleted mantle component before or during the extrusion of the basalts. Relatively high 207Pb/204Pb ratios (compared to contemporaneous mantle), support the hypothesis that erosion products of the ancient terrestrial protocrust existed for several hundred My before recycling into the mantle before ∼3.7 Ga. Our results are broadly consistent with models favoring a time-integrated Hadean history of mantle depletion and with the existence of an early Hadean protocrust, the complement to the Hadean depleted mantle, which after establishment of subduction-like processes was, at least locally, recycled into the upper mantle before 3.7 Ga. Thus, already in the Hadean, the upper mantle seems to be characterized by geochemical heterogeneity on a range of length scales; one property that is shared with the modern upper mantle. However, a simple two component mixing scenario between depleted mantle and an enriched-, crustal component with a modern analogue can not account for the complicated and contradictory geochemical properties of this particular Hadean upper mantle source.

Precipitation induced stream flow: An event based chemical and isotopic study of a small stream in the Great Plains region of the USA

USGS Publications Warehouse

Machavaram, M.V.; Whittemore, Donald O.; Conrad, M.E.; Miller, N.L.

2006-01-01

A small stream in the Great Plains of USA was sampled to understand the streamflow components following intense precipitation and the influence of water storage structures in the drainage basin. Precipitation, stream, ponds, ground-water and soil moisture were sampled for determination of isotopic (D, 18O) and chemical (Cl, SO4) composition before and after two intense rain events. Following the first storm event, flow at the downstream locations was generated primarily through shallow subsurface flow and runoff whereas in the headwaters region - where a pond is located in the stream channel - shallow ground-water and pond outflow contributed to the flow. The distinct isotopic signatures of precipitation and the evaporated pond water allowed separation of the event water from the other sources that contributed to the flow. Similarly, variations in the Cl and SO4 concentrations helped identify the relative contributions of ground-water and soil moisture to the streamflow. The relationship between deuterium excess and Cl or SO4 content reveals that the early contributions from a rain event to streamflow depend upon the antecedent climatic conditions and the position along the stream channel within the watershed. The design of this study, in which data from several locations within a watershed were collected, shows that in small streams changes in relative contributions from ground water and soil moisture complicate hydrograph separation, with surface-water bodies providing additional complexity. It also demonstrates the usefulness of combined chemical and isotopic methods in hydrologic investigations, especially the utility of the deuterium excess parameter in quantifying the relative contributions of various source components to the stream flow. ?? 2006 Elsevier B.V. All rights reserved.

Compound-specific stable carbon isotope composition as a fingerprint for sediment transport: Reproducibility, homogeneity and application in a catchment of the Swiss plateau.

NASA Astrophysics Data System (ADS)

Birkholz, Axel; Niemann, Helge; Alewell, Christine

2014-05-01

A new field for the applications of compound-specific isotope analyses (CSIA) has opened in the recent years. The isotopic signature in fatty acids (FA) can be used to track sediment transport pathways from erosional areas to river systems. In this approach distinct FA d13C values of even numbered saturated and/or unsaturated FAs from soils are traced in suspended river sediments, ie. the place of deposition. CSIA has been shown to be particularly useful in catchment areas with C4 plant crops because, compared to the regularly occurring C3-plants, they are (naturally) depleted in 13C. However, in theory, all plant species even among C3 plants should inherit significant differences in their d13C of FAs. Thus, we tried to differentiate between source areas for suspended sediments from three different land use types: forest (C3 plants), grassland (C3 plants) and arable land (mixture of C3 and C4 plants). Statistical geo software (eg. Isosource) can be used to additionally model the spatial and temporal variability of erosion. We present d13C values of FAs from 8 erosion areas from the Enziwigger catchment of the Swiss plateau (Canton of Lucerne). Each area was assessed through randomised triplicate sampling to test the spatial homogeneity of each one. The homogeneity of a single sample, as well as the reproducibility of our measurements was tested by extracting and analysing the same sample bag in triplicates. We compare compound-specific stable isotope (CSSI) fingerprints of source areas to d13C-values of FAs from suspended sediments of two high-flow events and one base flow period at 3 different sites of the Enziwiger river (upstream, midstream, downstream).

Pb-isotopic systematics of lunar highland rocks (>3.9 Ga): Constraints on early lunar evolution

USGS Publications Warehouse

Premo, W.R.; Tatsumoto, M.; Misawa, K.; Nakamuka, N.; Kita, N.I.

1999-01-01

The present lead (Pb)-isotopic database of over 200 analyses from nearly 90 samples of non-mare basalt, lunar highland rocks (>3.9 Ga) delineate at least three isotopically distinct signatures that in some combination can be interpreted to characterize the systematics of the entire database. Two are fairly new sets of lunar data and are typical of Pb data from other solar-system objects, describing nearly linear arrays slightly above the 'geochron' values, with 207Pb/206Pb values 500). Although the age and origin of this exotic Pb is not well constrained, it is interpreted to be related to the entrapment of incompatible-element-rich (U, Th) melts within the lunar upper mantle and crust between 4.36 and 4.46 Ga (urKREEP residuum?). The latest discovered Pb signature is found only in lunar meteorites and is characterized by relatively low source ?? values between 10 and 50 at 3.9 Ga. The fact that most lunar crustal rocks (>3.9 Ga) exhibit high 207Pb/206Pb values requires that they were derived from, mixed with, or contaminated by Pb produced from early-formed, high-?? sources. The ubiquity of these U-Pb characteristics in the sample collection is probably an artifact of Apollo and Luna sampling sites, all located on the near side of the Moon, which was deeply excavated during the basin-forming event(s). However, the newest Pb-isotopic data support the idea that the Moon originally had a ?? value of ~8 to 35, slightly elevated from Earth values, and that progressive U-Pb fractionations occurred within the Moon during later stages of differentiation between 4.36 and 4.46 Ga.

sources and processes identification for Zn cycling in the Seine river, France

NASA Astrophysics Data System (ADS)

gelabert, A.; Jouvin, D.; Morin, G.; Louvat, P.; Guinoiseau, D.; Benedetti, M. F.

2011-12-01

Because the availability of global freshwater stocks is predicted to become a major problem in a near future, new directives on water policy have been established in Europe. As a result, an accurate determination of the ecological status of the Seine river watershed is required. However, important evaluation limitation still exist, partly because the metal cycling in this system is not fully understood with for instance half the Seine river Zn not having clearly identified sources. Recent developments in isotopic measurements for new stable isotopes (Zn, Cu) allow many progresses in understanding the dynamics of metals in natural systems. But this technique alone does not always provide a precise distinction between mixing of water sources and biochemical processes able to induce isotopic fractionation. Along with an isotopic approach, this study propose to use XAS (X-ray Absorption Spectroscopy) to determine precisely the speciation of Zn complexes, and thus to define the proportion of water mixing vs. processes for Zn transfer in the watershed. A geographical sampling transect has been performed downstream Paris. Significant isotopic signature variations have been observed, varying from δ66Zn = 0.04 ± 0.04 to 0.18 ± 0.04 in the particulate part, and from δ66Zn= -0.28 ± 0.04 to 0.08 ± 0.04 for the dissolved part. The XAS analysis performed on the same samples at the Zn K-edge confirmed this heterogeneity by showing different speciations with a major contribution of sulfides, iron oxides and organic ligands. Interestingly, the wastewater treatment plant in Achères constitutes an important location in the system by contributing to the enrichment of heavy Zn to the Seine River particulate material. This change in isotopic signature follows a change in Zn speciation with decrease in sulfides contribution after Achères. A second important location is the confluence between the Seine and a minor river (Epte river) with a significant decrease in the δ66Zn for the particulate part. However, no major changes in Zn speciation have been observed. The cause for this isotopic decrease remains unclear but could be either 1) the mobilization of unknown sources, especially in this area (for the sampling point after the convergence) where the river is connected to numerous small lakes, or 2) the presence of biogeochemical processes able to induce a Zn isotopic fractionation. For instance, microorganisms present in freshwaters are known to be able to fractionate Zn during sorption processes, and they do not necessarily induce a change in the first shells of the Zn complexes if the sorbed metal was previously complexed with organic ligands in the river (fulvic substances with carboxylic or phenolic functional groups for instance). Although additional studies on the Seine river need to be conducted in order to reach a more complete understanding of this watershed functioning, these important results demonstrate the value of combining both the XAS and isotopic approaches in order to understand the behaviour of metals in such complex environments.

Fingerprinting two metal contaminants in streams with Cu isotopes near the Dexing Mine, China.

PubMed

Song, Shiming; Mathur, Ryan; Ruiz, Joaquin; Chen, Dandan; Allin, Nicholas; Guo, Kunyi; Kang, Wenkai

2016-02-15

Transition metal isotope signatures are becoming useful for fingerprinting sources in surface waters. This study explored the use of Cu isotope values to trace dissolved metal contaminants in stream water throughout a watershed affected by mining by-products of the Dexing Mine, the largest porphyry Cu operation in Asia. Cu isotope values of stream water were compared to potential mineral sources of Cu in the mining operation, and to proximity to the known Cu sources. The first mineral source, chalcopyrite, CuFeS2 has a 'tight' cluster of Cu isotope values (-0.15‰ to +1.65‰; +0.37 ± 0.6‰, 1σ, n=10), and the second mineral source, pyrite (FeS2), has a much larger range of Cu isotope values (-4‰ to +11.9‰; 2.7 ± 4.3‰, 1σ, n=16). Dissolved Cu isotope values of stream water indicated metal derived from either chalcopyrite or pyrite. Above known Cu mineralization, stream waters are approximately +1.5‰ greater than the average chalcopyrite and are interpreted as derived from weathering of chalcopyrite. In contrast, dissolved Cu isotope values in stream water emanating from tailings piles had Cu isotope values similar to or greater than pyrite (>+6‰, a common mineral in the tailings). These values are interpreted as sourced from the tailings, even in solutions that possess significantly lower concentrations of Cu (<0.05 ppm). Elevated Cu isotope values were also found in two soil and two tailings samples (δ(65)Cu ranging between +2 to +5‰). These data point to the mineral pyrite in tailings as the mineral source for the elevated Cu isotope values. Therefore, Cu isotope values of waters emanating from a clearly contaminated drainage possess different Cu isotope values, permitting the discrimination of Cu derived from chalcopyrite and pyrite in solution. Data demonstrate the utility of Cu isotopic values in waters, minerals, and soils to fingerprint metallic contamination for environmental problems. Copyright © 2015 Elsevier B.V. All rights reserved.

Glacial-interglacial cycles in detrital sediment supply to the Amundsen Sea: Implications for West Antarctic Ice Sheet dynamics during the Late Pleistocene

NASA Astrophysics Data System (ADS)

Simoes Pereira, P.; van de Flierdt, T.; Hillenbrand, C. D.; Hemming, S. R.; Kuhn, G.

2017-12-01

The West Antarctic Ice Sheet (WAIS) plays a key role in the global climate system and its collapse could contribute up to 4.3 m of sea-level rise. Mass loss of this marine-based ice sheet is largely caused by ocean-driven melting of ice shelves. This is confimed by modern observational data which show significant glacier thinning and retreat of grounding lines, particularly in the Amundsen Sea area. We here apply an integrated approach to determine provenance of marine sediments, which enables us to trace erosion of different bedrock lithologies, ultimately tied to the location of the eroding ice through time. We present provenance analysis on detrital Holocene seafloor sediments from the Amundsen Sea Embayment as well as from two marine cores PS58/254 (69°19´S, 108°27´W) and PC493 (71°09´S, 119°57´W), located on the continental rise of the Amundsen Sea and covering glacial-interglacial cycles of the past 800 kyrs. We use strontium (Sr) and neodymium (Nd) isotopic compositions of fine terrigenous grains (<63μm), and 40Ar/39Ar ages on ice-rafted (>150μm) hornblende and biotite grains. Our Holocene mapping results reveal drainage pathways with distinct signatures in the eastern and western Amundsen Sea Embayment. The western embayment records a homogenous provenance signature, pointing to a local source area in the hinterland, while the eastern embayment shows a range of compositions indicating erosion of the eastern coastal margin and a distinct, but unexposed source lithology under Pine Island Glacier and/or its drainage basin. Systematic isotope variations are detected between glacial and interglacial stages in both downcore records. Core PS58/254 exhibits a radiogenic fingerprint throughout the Late Pleistocene and systematic glacial-interglacial fluctuations in the order of three ɛNd units. They correlate with physical properties of the sediments (i.e. magnetic susceptibility) and trend towards lower values during interglacials, notably during Marine Isotope Stage (MIS) 5 and MIS 7. Core PC493 exhibits similar radiogenic Nd isotope composition, but a slightly reduced magnitude of glacial-interglacial changes. Detailed analysis of our results will offer a framework for interpreting sediment records from the area, including those from a recent MeBo expedition (PS104) and upcoming IODP expedition 379.

Constraints on the origin of Os-isotope disequilibrium in included and interstitial sulfides in mantle peridotites: Implications for the interpretation of Os-isotope signatures in MORB and Abyssal Peridotites

NASA Astrophysics Data System (ADS)

Lassiter, J. C.

2016-12-01

The use of isotope variations in basalts to probe the composition and evolution of the mantle is predicated on the assumption of local (i.e., grain-scale) isotopic equilibrium during mantle melting (Hofmann & Hart, 1978). However, several studies report Os-isotope disequilibrium in distinct populations of sulfides in some peridotites. In principle, grain-scale isotopic heterogeneity could reflect variable radiogenic ingrowth in ancient sulfides with variable Re/Os, or partial re-equilibration of low-Re/Os sulfides with high-Re/Os silicate phases along grain boundaries during mantle melting (e.g., Alard et al., 2005). Both cases require that sulfides fail to maintain isotopic equilibrium with neighboring phases over geologically long ( Ga) time scales. The preservation of Os-isotope disequilibrium in peridotites has been ascribed to the armoring effect of low-[Os] silicates, which limit diffusive exchange between isolated Os-rich phases. This raises the prospect that peridotite-derived melts may not inherit the Os-isotope composition of their source. The timescale required for diffusive equilibration between separate sulfide grains or between Os-rich sulfides and Os-poor silicates is a function of average sulfide size and spacing, Os diffusivity in armoring silicate minerals, and Os partitioning between silicate and sulfide phases. For typical sulfide abundances and sizes in mantle peridotites, neighboring sulfides are expected to re-equilibrate in less than a few 10s of m.y. at adiabatic mantle temperatures, even for very high (>106) sulfide/silicate KD values. Maintenance of disequilibrium requires very large sulfides (>100 um) separated by several mm and diffusion rates (D < 10-20 m2/s) slower than for most other elements in olivine. Equilibration timescales between sulfides and surrounding silicates are similar, so that large-scale isotopic disequilibrium between sulfides and silicates is also unlikely within the convecting mantle. Instead, observed grain-scale Os-isotope disequilibrium in mantle peridotites likely reflects recent sulfide metasomatism linked to interaction with eclogite- or pyroxenite-derived melts. Interstitial sulfides with radiogenic Os-isotopes provide further evidence for a role of eclogite melting in MORB genesis.

Trace element and isotopic composition of apatite in carbonatites from the Blue River area (British Columbia, Canada) and mineralogy of associated silicate rocks

NASA Astrophysics Data System (ADS)

Mitchell, Roger; Chudy, Thomas; McFarlane, Christopher R. M.; Wu, Fu-Yuan

2017-08-01

Apatites from the Verity, Fir, Gum, Howard Creek and Felix carbonatites of the Blue River (British Columbia, Canada) area have been investigated with respect to their paragenesis, cathodoluminescence, trace element and Sr-Nd isotopic composition. Although all of the Blue River carbonatites were emplaced as sills prior to amphibolite grade metamorphism and have undergone deformation, in many instances magmatic textures and mineralogy are retained. Attempts to constrain the U-Pb age of the carbonatites by SIMS, TIMS and LA-ICP-MS studies of zircon and titanite were inconclusive as all samples investigated have experienced significant Pb loss during metamorphism. The carbonatites are associated with undersaturated calcite-titanite amphibole nepheline syenite only at Howard Creek although most contain clasts of disaggregated phoscorite-like rocks. Apatite from each intrusion is characterized by distinct, but wide ranges, in trace element composition. The Sr and Nd isotopic compositions define an array on a 87Sr/86Sr vs²Nd diagram at 350 Ma indicating derivation from depleted sub-lithospheric mantle. This array could reflect mixing of Sr and Nd derived from HIMU and EM1 mantle sources, and implies that depleted mantle underlies the Canadian Cordillera. Although individual occurrences of carbonatites in the Blue River region are mineralogically and geochemically similar they are not identical and thus cannot be considered as rocks formed from a single batch of parental magma at the same stage of magmatic evolution. However, a common origin is highly probable. The variations in the trace element content and isotopic composition of apatite from each occurrence suggest that each carbonatite represents a combination of derivation of the parental magma(s) from mineralogically and isotopically heterogeneous depleted mantle sources coupled with different stages of limited differentiation and mixing of these magmas. We do not consider these carbonatites as primary direct partial melts of the sub-lithospheric mantle which have ascended from the asthenosphere without modification of their composition.

Tracing dust transport from Middle-East over Delhi in March 2012 using metal and lead isotope composition

NASA Astrophysics Data System (ADS)

Kumar, S.; Aggarwal, S. G.; Malherbe, J.; Barre, J. P. G.; Berail, S.; Gupta, P. K.; Donard, O. F. X.

2016-05-01

A severe dust-storm which was originated in Middle-East crossed over Delhi during March 20-22, 2012. We have collected these dust-storm (DS) aerosol samples, and analyzed them for selected metals (As, Cd, Cr, Cu, Fe, Ni, Pb, Sb, Se, Sn, Sr, V and Zn) together with after dust-storm (ADS) and winter (WS) samples. High aerosol mass loadings were observed in DS samples (1097-1965 μg/m3). On the contrary, metals derived prominently from the anthropogenic sources were found lower in concentration compared to that of ADS and WS aerosols. We observed significantly high concentrations of Ni and V (which are abundantly found in crude oils of Middle-East origin) in the DS samples than that of ADS and WS samples. Also enrichment factor (EF) of these metals with respect to Fe shows no significant enrichment (<10). Fe (and Sr) concentrations were also 3-5 fold higher in DS samples compared to ADS and WS. These results suggest that Ni and V can be used as tracers for dust aerosols transported from Middle-East region. Lead isotope signatures can tell about the variation in the sources of urban aerosols. Therefore Pb isotope analyses of these samples were performed using MC-ICP-MS. The isotope ratios, 208Pb/206Pb is determined to be (mean ± sd) 2.1315 ± 0.0018, 2.1370 ± 0.0022 and 2.1389 ± 0.0016, whereas 206Pb/207Pb is 1.1311 ± 0.0022, 1.1244 ± 0.0017 and 1.1233 ± 0.0016 in DS, ADS and WS aerosols, respectively. There is a clear distinction in Pb isotope composition between DS and urban (ADS and WS) aerosols. Further, these results suggest that in urban aerosols, Pb is less radiogenic in nature compared to that of in transported dust aerosols collected in New Delhi.

Barium-isotopic fractionation in seawater mediated by barite cycling and oceanic circulation

NASA Astrophysics Data System (ADS)

Horner, Tristan J.; Kinsley, Christopher W.; Nielsen, Sune G.

2015-11-01

The marine biogeochemical cycle of Ba is thought to be controlled by particulate BaSO4 (barite) precipitation associated with the microbial oxidation of organic carbon and its subsequent dissolution in the BaSO4-undersaturated water column. Despite many of these processes being largely unique to Ba cycling, concentrations of Ba and Si in seawater exhibit a strong linear correlation. The reasons for this correlation are ambiguous, as are the depth ranges corresponding to the most active BaSO4 cycling and the intermediate sources of Ba to particulate BaSO4. Stable isotopic analyses of dissolved Ba in seawater should help address these issues, as Ba-isotopic compositions are predicted to be sensitive to the physical and biogeochemical process that cycle Ba. We report a new methodology for the determination of dissolved Ba-isotopic compositions in seawater and results from a 4500 m depth profile in the South Atlantic at 39.99° S, 0.92° E that exhibit oceanographically-consistent variation with depth. These data reveal that water masses obtain their [Ba] and Ba-isotopic signatures when at or near the surface, which relates to the cycling of marine BaSO4. The shallow origin of these signatures requires that the substantial Ba-isotopic variations in the bathypelagic zone were inherited from when those deep waters were last ventilated. Indeed, the water column below 600 m is well explained by conservative mixing of water masses with distinct [Ba] and Ba-isotopic compositions. This leads us to conclude that large scale oceanic circulation is important for sustaining the similar oceanographic distributions of Ba and Si in the South Atlantic, and possibly elsewhere. These data demonstrate that the processes of organic carbon oxidation, BaSO4 cycling, and Ba-isotopic fractionation in seawater are closely coupled, such that Ba-isotopic analyses harbor great potential as a tracer of the carbon cycle in the modern and paleo-oceans.

Sr Isotopes and Migration of Prairie Mammoths (Mammuthus columbi) from Laguna de las Cruces, San Luis Potosi, Mexico

NASA Astrophysics Data System (ADS)

Solis-Pichardo, G.; Perez-Crespo, V.; Schaaf, P. E.; Arroyo-Cabrales, J.

2011-12-01

Asserting mobility of ancient humans is a major issue for anthropologists. For more than 25 years, Sr isotopes have been used as a resourceful tracer tool in this context. A comparison of the 87Sr/86Sr ratios found in tooth enamel and in bone is performed to determine if the human skeletal remains belonged to a local or a migrant. Sr in bone approximately reflects the isotopic composition of the geological region where the person lived before death; whereas the Sr isotopic system in tooth enamel is thought to remain as a closed system and thus conserves the isotope ratio acquired during childhood. Sr isotope ratios are obtained through the geologic substrate and its overlying soil, from where an individual got hold of food and water; these ratios are in turn incorporated into the dentition and skeleton during tissue formation. In previous studies from Teotihuacan, Mexico we have shown that a three-step leaching procedure on tooth enamel samples is important to assure that only the biogenic Sr isotope contribution is analyzed. The same Sr isotopic tools can function concerning ancient animal migration patterns. To determine or to discard the mobility of prairie mammoths (Mammuthus columbi) found at Laguna de las Cruces, San Luis Potosi, México the leaching procedure was applied on six molar samples from several fossil remains. The initial hypothesis was to use 87Sr/86Sr values to verify if the mammoth population was a mixture of individuals from various herds and further by comparing their Sr isotopic composition with that of plants and soils, to confirm their geographic origin. The dissimilar Sr results point to two distinct mammoth groups. The mammoth population from Laguna de Cruces was then not a family unit because it was composed by individuals originated from different localities. Only one individual was identified as local. Others could have walked as much as 100 km to find food and water sources.

Variation of the stable isotopes of water with altitiude in the Saint Elias Mountains of Canada

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

Holdsworth, G.; Fogarasi, S.; Krouse, H.R.

1991-04-20

The stable isotopes of water, measured in melt samples taken from snow pits and cores at locations between 1,750- and 5,930-m altitude on Mount Logan and between 2,900 and 4,900 m on Mount Steele, in the Saint Elias Mountains, Yukon, show a distinctive altitudinal distribution. Several {delta}{sup 18}O and {delta}D versus altitude profiles indicate the general persistence of a nearly iso-{delta} step, or staircase structure, separating a lower region of altitude dependent isotopic fractionation between 1,750 and 3,350 m from another apparent frictionation sequence appearing above about 5,300 m. On the one hand, postdepositional changes to isotope ratios in snowmore » at different altitudes may cause distortions to an otherwise nearly monotonic isotope fractionation sequence, but the main anomaly appears to be far too large to be explained this way. On the other hand, an explanation linked to processes occuring in the lower and midtroposphere is based on established meteorological principles as well as on upper air data. This hypothesis is proposed as the primary one to explain the gross features of the observed isotope profiles. It is compatible with the concept of secondary-source moisture arriving via the upper troposphere, and it does not exclude the effects of postdepositional stratigraphic and stable isotope ratio changes. Over interannual time scales, any vertical modulation of the observed isotope-altitude structure, from, for example, changes in wind regime, would give rise to an additional signal in any ice core {delta} time series. These findings identify a potential difficulty in the interpretation of stable isotope records obtained from high mountain ice core sites. It is possible that the results may have application to atmospheric circulation modeling, where the effects of extreme topography are being studied.« less

Coupled Hf-Nd-Pb isotope co-variations of HIMU oceanic island basalts from Mangaia, Cook-Austral islands, suggest an Archean source component in the mantle transition zone

NASA Astrophysics Data System (ADS)

Nebel, Oliver; Arculus, Richard J.; van Westrenen, Wim; Woodhead, Jon D.; Jenner, Frances E.; Nebel-Jacobsen, Yona J.; Wille, Martin; Eggins, Stephen M.

2013-07-01

Although it is widely accepted that oceanic island basalts (OIB) sample geochemically distinct mantle reservoirs including recycled oceanic crust, the composition, age, and locus of these reservoirs remain uncertain. OIB with highly radiogenic Pb isotope signatures are grouped as HIMU (high-μ, with μ = 238U/204Pb), and exhibit unique Hf-Nd isotopic characteristics, defined as ΔɛHf, deviant from a terrestrial igneous rock array that includes all other OIB types. Here we combine new Hf isotope data with previous Nd-Pb isotope measurements to assess the coupled, time-integrated Hf-Nd-Pb isotope evolution of the most extreme HIMU location (Mangaia, French Polynesia). In comparison with global MORB and other OIB types, Mangaia samples define a unique trend in coupled Hf-Nd-Pb isotope co-variations (expressed in 207Pb/206Pb vs. ΔɛHf). In a model employing subducted, dehydrated oceanic crust, mixing between present-day depleted MORB mantle (DMM) and small proportions (˜5%) of a HIMU mantle endmember can re-produce the Hf-Nd-Pb isotope systematics of global HIMU basalts (sensu stricto; i.e., without EM-1/EM-2/FOZO components). An age range of 3.5 to <2 Ga is required for HIMU endmember(s) that mix with DMM to account for the observed present-day HIMU isotope compositions, suggesting a range of age distributions rather than a single component in the mantle. Our data suggest that mixing of HIMU mantle endmembers and DMM occurs in the mantle transition zone by entrainment in secondary plumes that rise at the edge of the Pacific Large Low Seismic Velocity Zone (LLSVP). These create either pure HIMU (sensu stricto) or HIMU affected by other enriched mantle endmembers (sensu lato). If correct, this requires isolation of parts of the mantle transition zone for >3 Gyr and implies that OIB chemistry can be used to test geodynamic models.

Evaluating methane inventories by isotopic analysis in the London region.

PubMed

Zazzeri, G; Lowry, D; Fisher, R E; France, J L; Lanoisellé, M; Grimmond, C S B; Nisbet, E G

2017-07-07

A thorough understanding of methane sources is necessary to accomplish methane reduction targets. Urban environments, where a large variety of methane sources coexist, are one of the most complex areas to investigate. Methane sources are characterised by specific δ 13 C-CH 4 signatures, so high precision stable isotope analysis of atmospheric methane can be used to give a better understanding of urban sources and their partition in a source mix. Diurnal measurements of methane and carbon dioxide mole fraction, and isotopic values at King's College London, enabled assessment of the isotopic signal of the source mix in central London. Surveys with a mobile measurement system in the London region were also carried out for detection of methane plumes at near ground level, in order to evaluate the spatial allocation of sources suggested by the inventories. The measured isotopic signal in central London (-45.7 ±0.5‰) was more than 2‰ higher than the isotopic value calculated using emission inventories and updated δ 13 C-CH 4 signatures. Besides, during the mobile surveys, many gas leaks were identified that are not included in the inventories. This suggests that a revision of the source distribution given by the emission inventories is needed.

USING STABLE ISOTOPES FOR FISH DIETARY ANALYSES: COPING WITH TOO MANY SOURCES

EPA Science Inventory

Stable isotope analysis can provide a useful tool for determining time-integrated measures of proportional food source contributions to fish diets. Ratios of stable (non-radioactive) isotopes of common elements (e.g., C,N,S) vary among food sources, and tissues of consumers (e.g...

Laser ion source for isobaric heavy ion collider experiment.

PubMed

Kanesue, T; Kumaki, M; Ikeda, S; Okamura, M

2016-02-01

Heavy-ion collider experiment in isobaric system is under investigation at Relativistic Heavy Ion Collider. For this experiment, ion source is required to maximize the abundance of the intended isotope. The candidate of the experiment is (96)Ru + (96)Zr. Since the natural abundance of particular isotope is low and composition of isotope from ion source depends on the composites of the target, an isotope enriched material may be needed as a target. We studied the performance of the laser ion source required for the experiment for Zr ions.

New insight on Li and B isotope fractionation during serpentinization derived from batch reaction investigations

NASA Astrophysics Data System (ADS)

Hansen, Christian T.; Meixner, Anette; Kasemann, Simone A.; Bach, Wolfgang

2017-11-01

Multiple batch experiments (100 °C, 200 °C; 40 MPa) were conducted, using Dickson-type reactors, to investigate Li and B partitioning and isotope fractionation between rock and water during serpentinization. We reacted fresh olivine (5 g; Fo90; [B] = <0.02 μg/g; δ11BOlivine -14‰; [Li] = 1.7 μg/g; δ7LiOlivine = +5.3‰) with seawater-like fluids (75 ml, 3.2 wt.% NaCl) adjusted with respect to their Li (0.2, 0.5 μg/ml; and δ7LiFluid +55‰) and B (∼10 μg/ml and δ11BFluid -0.3‰) characteristics. At 200 °C a reaction turnover of about 70% and a serpentinization mineral assemblage matching equilibrium thermodynamic computational results (EQ3/6) developed after 224 days runtime. Characterization of concomitant fluid samples indicated a distinct B incorporation into solid phases ([B]final_200 °C = 55.61 μg/g; DS/FB200 °C = 13.42) and a preferential uptake of the lighter 10B isotope (Δ11BS-F = -3.46‰). Despite a low reaction turnover at 100 °C (<12%), considerable amounts of B were again incorporated into solid phases ([B]final_100 °C = 25.33 μg/g; DS/FB100 °C = 24.2) with even a larger isotope fractionation factor (Δ11BS-F = -9.97‰). While magnitude of isotope fraction appears anti-correlated with temperature, we argue for an overall attenuation of the isotopic effect through changes in B speciation in saline solutions (NaB(OH)4(aq) and B(OH)3Cl-) as well as variable B fixation and fractionation for different serpentinization product minerals (brucite, chrysotile). Breakdown of the Li-rich olivine and limited Li incorporation into product mineral phases resulted in an overall lower Li content of the final solid phase assemblage at 200 °C ([Li]final_200 °C = 0.77 μg/g; DS/FLi200 °C = 1.58). First order changes in Li isotopic compositions were defined by mixing of two isotopically distinct sources i.e. the fresh olivine and the fluid rather than by equilibrium isotope fraction. At 200 °C primary olivine is dissolved, releasing its Li budget into the fluid which shifts towards a lower δ7LiF of +38.62‰. Newly formed serpentine minerals (δ7LiS = +30.58‰) incorporate fluid derived Li with a minor preference of the 6Li isotope. At 100 °C Li enrichment of secondary phases exceeded Li release by olivine breakdown ([Li]final_100 °C = 2.10 μg/g; DS/FLi100 °C = 11.3) and it was accompanied by preferential incorporation of heavier 7Li isotope that might be due to incorporation of a 7Li enriched fluid fraction into chrysotile nanotubes.

Sources of granite magmatism in the Embu Terrane (Ribeira Belt, Brazil): Neoproterozoic crust recycling constrained by elemental and isotope (Sr-Nd-Pb) geochemistry

NASA Astrophysics Data System (ADS)

Alves, Adriana; Janasi, Valdecir de Assis; Campos Neto, Mario da Costa

2016-07-01

Whole rock elemental and Sr-Nd isotope geochemistry and in situ K-feldspar Pb isotope geochemistry were used to identify the sources involved in the genesis of Neoproterozoic granites from the Embu Terrane, Ribeira Belt, SE Brazil. Granite magmatism spanned over 200 Ma (810-580 Ma), and is dominated by crust-derived relatively low-T (850-750 °C, zircon saturation) biotite granites to biotite-muscovite granites. Two Cryogenian plutons show the least negative εNdt (-8 to -10) and highest mg# (30-40) of the whole set. Their compositions are strongly contrasted, implying distinct sources for the peraluminous (ASI ∼ 1.2) ∼660 Ma Serra do Quebra-Cangalha batholith (metasedimentary rocks from relatively young upper crust with high Rb/Sr and low Th/U) and the metaluminous (ASI = 0.96-1.00) ∼ 630 Ma Santa Catarina Granite. Although not typical, the geochemical signature of these granites may reflect a continental margin arc environment, and they could be products of a prolonged period of oceanic plate consumption started at ∼810 Ma. The predominant Ediacaran (595-580 Ma) plutons have a spread of compositions from biotite granites with SiO2 as low as ∼65% (e.g., Itapeti, Mauá, Sabaúna and Lagoinha granites) to fractionated muscovite granites (Mogi das Cruzes, Santa Branca and Guacuri granites; up to ∼75% SiO2). εNdT are characteristically negative (-12 to -18), with corresponding Nd TDM indicating sources with Paleoproterozoic mean crustal ages (2.0-2.5 Ga). The Guacuri and Santa Branca muscovite granites have the more negative εNdt, highest 87Sr/86Srt (0.714-0.717) and lowest 208Pb/206Pb and 207Pb/206Pb, consistent with an old metasedimentary source with low time-integrated Rb/Sr. However, a positive Nd-Sr isotope correlation is suggested by data from the other granites, and would be consistent with mixing between an older source predominant in the Mauá granite and a younger, high Rb/Sr source that is more abundant in the Lagoinha granite sample. The Ediacaran granites are coeval with profuse granite magmatism attributed to continental arc magmatism in northern Ribeira and Araçuaí belts. However, their evolved compositions with low mg# and dominantly peraluminous character are unlike those of magmatic arc granites, and they are more likely products of post-collisional magmatism or correspond to an inner belt of crust-derived granites.

Geology, geochronology, and geochemistry of basaltic flows of the Cat Hills, Cat Mesa, Wind Mesa, Cerro Verde, and Mesita Negra, central New Mexico

USGS Publications Warehouse

Maldonado, F.; Budahn, J.R.; Peters, L.; Unruh, D.M.

2006-01-01

The geochronology, geochemistry, and isotopic compositions of basaltic flows erupted from the Cat Hills, Cat Mesa, Wind Mesa, Cerro Verde, and Mesita Negra volcanic centres in central New Mexico indicate that each of these lavas had unique origins and that the predominant mantle involved in their production was an ocean-island basalt type. The basalts from Cat Hills (0.11 Ma) and Cat Mesa (3.0 Ma) are similar in major and trace element composition, but differences in MgO contents and Pb isotopic values are attributed to a small involvement of a lower crustal component in the genesis of the Cat Mesa rocks. The Cerro Verde rock is comparable in age (0.32 Ma) to the Cat Hills lavas, but it is more radiogenic in Sr and Nd, has higher MgO contents, and has a lower La/Yb ratio. This composition is explained by the melting of an enriched mantle source, but the involvement of another crustal component cannot be disregarded. The Wind Mesa rock is characterized by similar age (4.01 Ma) and MgO contents, but it has enriched rare-earth element contents compared with the Cat Mesa samples. These are attributed to a difference in the degree of partial melting of the Cat Mesa source. The Mesita Negra rock (8.11 Ma) has distinctive geochemical and isotopic compositions that suggest a different enriched mantle and that large amounts of a crustal component were involved in generating this magma. These data imply a temporal shift in magma source regions and crustal involvement, and have been previously proposed for Rio Grande rift lavas. ?? 2006 NRC Canada.

Trophic ecology influence on metal bioaccumulation in marine fish: Inference from stable isotope and fatty acid analyses.

PubMed

Le Croizier, Gaël; Schaal, Gauthier; Gallon, Régis; Fall, Massal; Le Grand, Fabienne; Munaron, Jean-Marie; Rouget, Marie-Laure; Machu, Eric; Le Loc'h, François; Laë, Raymond; De Morais, Luis Tito

2016-12-15

The link between trophic ecology and metal accumulation in marine fish species was investigated through a multi-tracers approach combining fatty acid (FA) and stable isotope (SI) analyses on fish from two contrasted sites on the coast of Senegal, one subjected to anthropogenic metal effluents and another one less impacted. The concentrations of thirteen trace metal elements (As, Cd, Co, Cr, Cu, Fe, Li, Mn, Ni, Pb, Sn, U, and Zn) were measured in fish liver. Individuals from each site were classified into three distinct groups according to their liver FA and muscle SI compositions. Trace element concentrations were tested between groups revealing that bioaccumulation of several metals was clearly dependent on the trophic guild of fish. Furthermore, correlations between individual trophic markers and trace metals gave new insights into the determination of their origin. Fatty acids revealed relationships between the dietary regimes and metal accumulation that were not detected with stable isotopes, possibly due to the trace metal elements analysed in this study. In the region exposed to metallic inputs, the consumption of benthic preys was the main pathway for metal transfer to the fish community while in the unaffected one, pelagic preys represented the main source of metals. Within pelagic sources, metallic transfer to fish depended on phytoplankton taxa on which the food web was based, suggesting that microphytoplankton (i.e., diatoms and dinoflagellates) were a more important source of exposition than nano- and picoplankton. This study confirmed the influence of diet in the metal accumulation of marine fish communities, and proved that FAs are very useful and complementary tools to SIs to link metal accumulation in fish with their trophic ecology. Copyright © 2016 Elsevier B.V. All rights reserved.

'Trophic' and 'source' amino acids in trophic estimation: a likely metabolic explanation.

PubMed

O'Connell, T C

2017-06-01

Amino acid nitrogen isotopic analysis is a relatively new method for estimating trophic position. It uses the isotopic difference between an individual's 'trophic' and 'source' amino acids to determine its trophic position. So far, there is no accepted explanation for the mechanism by which the isotopic signals in 'trophic' and 'source' amino acids arise. Yet without a metabolic understanding, the utility of nitrogen isotopic analyses as a method for probing trophic relations, at either bulk tissue or amino acid level, is limited. I draw on isotopic tracer studies of protein metabolism, together with a consideration of amino acid metabolic pathways, to suggest that the 'trophic'/'source' groupings have a fundamental metabolic origin, to do with the cycling of amino-nitrogen between amino acids. 'Trophic' amino acids are those whose amino-nitrogens are interchangeable, part of a metabolic amino-nitrogen pool, and 'source' amino acids are those whose amino-nitrogens are not interchangeable with the metabolic pool. Nitrogen isotopic values of 'trophic' amino acids will reflect an averaged isotopic signal of all such dietary amino acids, offset by the integrated effect of isotopic fractionation from nitrogen cycling, and modulated by metabolic and physiological effects. Isotopic values of 'source' amino acids will be more closely linked to those of equivalent dietary amino acids, but also modulated by metabolism and physiology. The complexity of nitrogen cycling suggests that a single identifiable value for 'trophic discrimination factors' is unlikely to exist. Greater consideration of physiology and metabolism should help in better understanding observed patterns in nitrogen isotopic values.

Detection of Human Sewage in Urban Stormwater Using DNA Based Methods and Stable Isotope Analysis

NASA Astrophysics Data System (ADS)

McLellan, S. L.; Malet, N.; Sauer, E.; Mueller-Spitz, S.; Borchardt, M.

2008-12-01

Urban stormwater is a major source of fecal indicator bacteria in the Milwaukee River Basin, a major watershed draining to Lake Michigan. Much of the watershed is in highly urbanized areas and Escherichia coli (E. coli) levels have been found to be 20,000 CFU per 100 ml in the estuary leading to Lake Michigan. Aging infrastructure and illicit cross connections may allow sewage to infiltrate the stormwater system and could contribute both fecal indicator bacteria and human pathogens to these waters. We conducted extensive sampling of stormwater outfalls in the lower reaches of three major tributaries. Three outfalls along the heavily urbanized Kinnickinnick (KK) were found to have geometric mean E. coli and enterococci levels of 16,200 and 28,700 CFU/100 ml, respectively. Four outfalls along the Menomonee River, draining both suburban and urban areas, had geometric mean E. coli and enterococci levels of 14,700 and 12,800 CFU/100 ml, respectively. These seven outfalls had more than 60% of the samples positive for human specific Bacteroides genetic marker (n=46), suggesting the presence of human sources. In addition, two outfalls on Lincoln Creek, a smaller tributary of the Milwaukee River, had geometric mean E. coli and enterococci levels of 16,700 and 14,900 CFU per 100 ml, respectively. The human specific Bacteroides marker was positive in nearly 90% of the samples (n=24). Subsequent virus testing at one of these outfalls confirmed human pathogens were present with adenovirus detected at 1.3 x 10E3 genomic equivalents (ge)/L, enterovirus at 1.9 x 10E4 ge/L and G1 norovirus at 1.5 x 10E3 ge/L; these values are similar to concentrations found in sewage. Stable isotope studies were conducted in the three tributaries to investigate the relationship between delta C and delta N isotopic composition and microbiological quality of this urban freshwater system. This work is based on the premise that the organic matter of the stormwater will have a stable isotopic signature related to the mixed organic matter sources in polluted stormwater runoff, and that this signal will distinct from untreated sanitary sewage. Stable isotope signatures of stormwater and untreated sewage were determined and compared with the rivers. Isotopic values of stormwater was delta 15N = 1.1 ± 2 %; delta 13C = -25.5 ± 3 % and sewage was delta 15N = -1.9 ± 0.2 %; delta 13C = -23.6 ± 0.3. Suspended particular organic matter (SPOM) of Milwaukee River showed depleted delta 13C (-28.6 ± 1.6 %) and enriched delta 15N (7.7 ± 1.9 %) values. SPOM of the KK River exhibited the most depleted delta 15N (0.2 ± 1.6 %) and enriched delta 13C (-24.8 ± 1.8 %) isotopic values. Menomonee River SPOM showed intermediate isotopic values. The delta 13C values of each river and the estuary enriched significantly throughout the summer storm periods. The isotope signals in the KK and Menomonee were indicative of stormwater runoff and sewage contamination. These results suggest that unrecognized sewage inputs are chronically present and may be delivered through urban stormwater systems. DNA based methods combined with isotope analysis may provide a useful tool for urban watershed assessments and to identify sewage inputs. Delineating the relative contribution of stormwater and sewage to overall degraded water quality might give the first indication of the impact of these sources on the Michigan Lake waters.

Mercury exposure and source tracking in distinct marine-caged fish farm in southern China.

PubMed

Xu, Xiaoyu; Wang, Wen-Xiong

2017-01-01

Coasts of South China have experienced an unprecedented growth in its marine-caged fish industry. We analyzed mercury concentrations and stable mercury isotope ratios in fourteen fish species from two cage-cultured farms in Southern China. Total mercury concentrations of all species were lower than the human health screening values, but the human exposures through consumption of several carnivorous fish exceeded the USEPA's reference dose. Isotopic compositions in the sediment (δ 202 Hg: -1.45‰ to -1.23‰; Δ 199 Hg: -0.04‰ to -0.01‰) suggested that mercury in these farms were from coal combustion and industrial inputs. Commercial food pellets and fresh fish viscera provided the major sources of methylmercury to the farmed fish and dominated their mercury isotopic signatures. Non-carnivorous fish presented lower δ 202 Hg and Δ 199 Hg values than the carnivorous fish. Using a mixing model, we demonstrated that the majority of mercury in non-carnivorous species came from pellets and in carnivorous fish came from combined diets of pellets and viscera. Meanwhile, methylmercury concentrations and % methylmercury in the fish were positively correlated with δ 202 Hg values but not with Δ 199 Hg values, mainly because fish eating similar feeds maintained similar Δ 199 Hg values. Environmental influences of cage farming such as fish feces and uneaten viscera that continuously provide organic mercury to the environments need to be considered. Copyright © 2016 Elsevier Ltd. All rights reserved.

Natural abundance N stable isotopes in plants and soils as an indicator of N deposition hotspots in urban environments

NASA Astrophysics Data System (ADS)

Trammell, T. L.

2017-12-01

The natural abundance of stable isotopes in plants and soils has been utilized to understand ecological phenomenon. Foliar δ15N is an integrator of soil δ15N, atmospheric N sources, and fractionation processes that occur during plant N uptake, plant N assimilation, and mycorrhizal associations. The amount of reactive N in the environment has greatly increased due to human activities, and urban ecosystems experience excess N deposition that can have cascading effects on plants and soils. Foliar δ15N has been shown to increase with increasing N deposition and nitrification rates suggesting increased foliar δ15N occurs with greater N inputs as a result of accelerated soil N cycling. Thus, foliar δ15N can be an indication of soil N availability for plant uptake and soil N cycling rates, since high N availability results in increased soil N cycling and subsequent loss of 14N. Limited research has utilized foliar and soil δ15N in urban forests to assess the importance of plant uptake of atmospheric N deposition and to gain insight about ecosystem processes. Previous investigations found foliar δ15N of mature trees in urban forests is not only related to elevated pollutant-derived N deposition, but also to soil N availability and soil N cycling rates. Similarly, enriched foliar δ15N of urban saplings was attributed to soil characteristics that indicated higher nitrification, thus, greater nitrate leaching and low N retention in the urban soils. These studies demonstrate the need for measuring the δ15N of various plant and soil N sources while simultaneously measuring soil N processes (e.g., net nitrification rates) in order to use natural abundance δ15N of plants and soils to assess N sources and cycling in urban forests. A conceptual framework that illustrates biogenic and anthropogenic controls on nitrogen isotope composition in urban plants and soils will be presented along with foliar and soil δ15N from urban forests across several cities as a proof of concept. Foliar and soil 15N can be extremely useful when N sources are isotopically distinct, patterns are detectable, or multiple tools are used simultaneously to understand N cycling. N cycles tightly in most ecosystems, thus δ15N in plants and soils can provide information about N source and availability to ecosystems.

2007 California Aerosol Study: Evaluation of δ15N as a Tracer Of NOx Sources and Chemsitry

NASA Astrophysics Data System (ADS)

Katzman, T. L.

2017-12-01

Although stable isotopes of N are commonly used as a source tracer, how this tracer is applied is a point of contention. The "source" hypothesis argues that the δ15N value of NO3- reflects the δ15N value of NOx source inputs into the environment, and any observed variation is solely the result of differences in source contributions. Conversely, the "chemistry" hypothesis argues that N isotopes are influenced by chemical reactions, atmospheric or biologic processing, and post-depositional effects. Previous studies often apply the source hypothesis, writing off the chemistry hypothesis as "minor," but others have noted the impact chemistry should has on δ15N values. Given the known complications, this work seeks to assess the use of stable isotopes as tracers, specifically, the assumption that the δ15N value is a tracer of source alone without significant influence from chemical reactions. If the "source" hypothesis is correct, source emission data, known source δ15N values, and isotope mass balance should be able to approximate measured δ15NNO3 values and determine the δ15N value associated with wildfire derived NOx, which is currently unknown. Significant deviations from observed values would support the significance of equilibrium and kinetic isotope effects associated with chemical reactions and processing in the atmosphere. Aerosols collected in during 2007, emission data, and isotopic analysis were utilized to determine the utility of δ15N as tracer of NOx sources. San Diego, California is a coastal urban area influenced by sea salt aerosols, anthropogenic combustion emissions, and seasonal wildfires. Wildfires also have a significant influence on local atmospheric chemistry and 2007 was notable for being one of the worst fire seasons in the San Diego region on record. Isotopic analysis of collected NO3- has suggested that source δ15N values are likely not conserved as NOx is oxidized into NO3-. Given known source contributions and known δ15N values of NOx sources, isotope mass balance predicts that a NOx source with highly positive δ15N value must exist for the source hypothesis to be valid. Furthermore, isotopic analysis has also suggested that wildfire emissions may produce a depleted δ15N, disagreeing with previously predicted δ15N values.

Variation of atmospheric CO, δ13C, and δ18O at high northern latitude during 2004-2009: Observations and model simulations

NASA Astrophysics Data System (ADS)

Park, Keyhong; Wang, Zhihui; Emmons, Louisa K.; Mak, John E.

2015-10-01

Atmospheric CO mixing ratios and stable isotope ratios (δ13C and δ18O) were measured at a high northern latitude site (Westman Islands, Iceland) from January 2004 to March 2010 in order to investigate recent multiyear trends of the sources of atmospheric carbon monoxide in the extratropical Northern Hemisphere. During this period, we observed a decrease of about 2% per year in CO mixing ratios with little significant interannual variability. The seasonal cycles for δ13C and δ18O in CO are similar to that in the CO mixing ratio, and there is a pronounced interannual variation in their seasonal extremes occurring in summer and fall, which is driven by changes in the relative contribution of different sources. Some of the sources of CO are anthropogenic in character (e.g., fossil fuel and biofuel combustion and agricultural waste burning), and some are primarily natural (e.g., oxidation atmospheric methane and other hydrocarbons and wildfires), and distinction among the various major sources can, more or less, be distinguished by the stable isotopic composition of CO. We compare our observations with simulations from a 3-D global chemical transport model (MOZART-4, Model for Ozone and Related Chemical Tracers, version 4). Our results indicate the observed trend of anthropogenic CO emissions is mostly responsible for the observed variation in δ13C and δ18O of CO during 2004-2009. Especially, the δ18O enriched sources such as fossil fuel and biofuel sources are controlling the variation. The modeling results indicate decreasing trends in the fossil fuel and biofuel source contributions at Iceland of -0.61 ± 0.26 ppbv/yr and -0.38 ± 0.10 ppbv/yr, respectively, during the observation period.

Chemometric differentiation of crude oil families in the San Joaquin Basin, California

USGS Publications Warehouse

Peters, Kenneth E.; Coutrot, Delphine; Nouvelle, Xavier; Ramos, L. Scott; Rohrback, Brian G.; Magoon, Leslie B.; Zumberge, John E.

2013-01-01

Chemometric analyses of geochemical data for 165 crude oil samples from the San Joaquin Basin identify genetically distinct oil families and their inferred source rocks and provide insight into migration pathways, reservoir compartments, and filling histories. In the first part of the study, 17 source-related biomarker and stable carbon-isotope ratios were evaluated using a chemometric decision tree (CDT) to identify families. In the second part, ascendant hierarchical clustering was applied to terpane mass chromatograms for the samples to compare with the CDT results. The results from the two methods are remarkably similar despite differing data input and assumptions. Recognized source rocks for the oil families include the (1) Eocene Kreyenhagen Formation, (2) Eocene Tumey Formation, (3–4) upper and lower parts of the Miocene Monterey Formation (Buttonwillow depocenter), and (5–6) upper and lower parts of the Miocene Monterey Formation (Tejon depocenter). Ascendant hierarchical clustering identifies 22 oil families in the basin as corroborated by independent data, such as carbon-isotope ratios, sample location, reservoir unit, and thermal maturity maps from a three-dimensional basin and petroleum system model. Five families originated from the Eocene Kreyenhagen Formation source rock, and three families came from the overlying Eocene Tumey Formation. Fourteen families migrated from the upper and lower parts of the Miocene Monterey Formation source rocks within the Buttonwillow and Tejon depocenters north and south of the Bakersfield arch. The Eocene and Miocene families show little cross-stratigraphic migration because of seals within and between the source rocks. The data do not exclude the possibility that some families described as originating from the Monterey Formation actually came from source rock in the Temblor Formation.

Day-night differences in the composition and sources of carbonaceous aerosol at a polluted regional background site in the Netherlands

NASA Astrophysics Data System (ADS)

Dusek, Ulrike; Broekema, Elise; Holzinger, Rupert; Röckmann, Thomas; Meijer, Harro

2017-04-01

The origin of carbonaceous aerosol differs during day- and night-time, because emissions from major sources such as traffic, biomass combustion, and secondary organic aerosol formation show a distinct diurnal pattern. Moreover, photochemical processing and evaporation of semi-volatile organic compounds are enhanced during day-time, due to the availability of sunlight and higher temperatures. Assessing day-night differences in sources and chemical composition can give an indication of the importance of local/regional carbon sources and processing, since day-night differences should be averaged out during long-range transport. If local sources dominate, one could expect a strong diurnal variation in the source profile, but if long-range transport dominates the diurnal variation would be much weaker. In this study we measure the isotopic (14C and 13C) and detailed chemical composition of the organic fraction of the aerosol on high volume PM2.5 filter samples that were collected separately during day and night time. Radiocarbon (14C) measurements are used to estimate three main aerosol sources of organic and elemental carbon (OC and EC): Fossil fuel combustion (ff), biomass combustion (bb), and biogenic sources (bio). The detailed chemical and stable isotopic composition are measured at different desorption temperatures from the filter, which separates the more and less refractory organic compounds. The composition of the organic aerosol is measured using an thermal-desporption Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS) method (Holzinger et al, 2010) and the stable isotopic composition is measured using a thermal desorption IRMS method (Dusek et al., 2013). Source apportionment results using 14C show that the contribution of fossil fuel combustion to EC and OC is higher during day-time than during night-time. This is valid for all seasons. During night-time biomass combustion plays a bigger role as a source of carbonaceous aerosol. Even in the summer, when biomass combustion is a small source, its relative contribution increases between 19:00 and 07:00. However, the diurnal changes in source contributions are relatively moderate (e.g., the biomass burning contribution to TC increased from 31% to 43% for the winter sample with the most distinct day-night difference.) This highlights the importance of long-range transport as a source of the carbonaceous aerosol in this region. First results from chemical composition measurements on four of the samples show that the concentration of less refractory organic carbon (desorption temperature up to 200 °C) increases at night-time much more strongly than the concentration of the more refractory carbon. Similarly, the concentration of small organic compounds with m/z < 100 also increases more strongly than heavier compounds. This indicates partitioning of semi-volatile OC as a possible additional night-time source. The chemical composition will be studied in more detail, focusing on diurnal changes in O/C ratios, individual compounds and compound classes, such as hydrocarbons or organic acids. Dusek, U., Meusinger, C., Oyama, B., Ramon, W., de Wilde, P., Holzinger, R., and Röckmann, T.: A thermal desorption system for measuring δ 13 C ratios on organic aerosol, Journal of aerosol science, 66, 72-82, 2013. Holzinger, R., Williams, J., Herrmann, F., Lelieveld, J., Donahue, N., Röckmann, T., 2010. Aerosol analysis using a Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS): a new approach to study processing of organic aerosols. Atmospheric chemistry and physics 10, 2257-2267.

Interrogating trees as archives of sulphur deposition

NASA Astrophysics Data System (ADS)

Wynn, P. M.; Loader, N. J.; Fairchild, I. J.

2012-04-01

A principal driver of climatic variability over the past 1,000 years and essential forcing mechanism for climate, are the changes in atmospheric composition resulting from sulphur aerosols. Natural and anthropogenic aerosols released into the atmosphere disrupt the radiative balance through backscattering and absorption of incoming solar radiation and increase cloud albedo by acting as condensation nuclei. Understanding the impact of sulphur emissions upon climate beyond the last few hundred years however is not straightforward and natural archives of environmental information must be explored. Tree-rings represent one such archive as they are widely distributed and preserve environmental information within a precisely dateable, annually resolved timescale. Until recently the sulphur contained within tree-rings has largely remained beyond the reach of environmental scientists and climate modelers owing to difficulties associated with the extraction of a robust signal and uncertainties regarding post-depositional mobility. Our recent work using synchrotron radiation has established that the majority of non-labile sulphur in two conifer species is preserved within the cellular structure of the woody tissue after uptake and demonstrates an increasing trend in sulphur concentration during the 20th century and during known volcanic events. Due to the clear isotopic distinction between marine (+21), geological (+10 to +30), atmospheric pollution (-3 to +9 ) and volcanic sources of sulphur (0 to +5), isotopic ratios provide a diagnostic tool with which changes in the source of atmospheric sulphur can be detected in a more reliable fashion than concentration alone. Sulphur isotopes should thereby provide a fingerprint of short lived events including volcanic activity when extracted at high resolution and in conjunction with high resolution S concentrations defining the event. Here we present methodologies associated with extracting the sulphur isotopic signal from tree-rings using both elemental analyser isotope ratio mass spectrometry and ion probe technology. Preliminary data indicate success at extracting the sulphur isotopic signal from woody tissues at 2-3 year resolution. In conjunction with analytical developments in ion probe technology, high resolution records of localised sulphur forcing from tree-ring archives, including volcanic activity, no longer seem too far beyond the reach of climate scientists.

Determining and quantifying specific sources of light alkane

NASA Astrophysics Data System (ADS)

Bill, M.; Conrad, M. E.

2015-12-01

Determining and quantifying specific sources of emission of methane (an important greenhouse gas) and light alkanes from abandoned gas and oil wells, hydraulic fracturing or associated with CO2 sequestration are a challenge in determining their contribution to the atmospheric greenhouse gas budget or to identify source of groundwater contamination. Here, we review organic biogeochemistry proprieties and isotopic fingerprinting of C1-C5 alkanes to address this problem. For instance, the concentration ratios of CH4 to C2-C5 alkanes can be used to distinguish between thermogenic and microbial generated CH4. Together C and H isotopes of CH4 are used to differentiate bacterial generated sources and thermogenic CH4 and may also identify processes such as alteration and source mixing. Carbon isotope ratios pattern of C1-C5 alkanes highlight sources and oxidation processes in the gas reservoirs. Stable carbon isotope measurements are a viable tool for monitoring the degradation progress of methane and light hydrocarbons. The carbon isotope ratios of the reactants and products are independent of the concentration and only depend on the relative progress of the particular reaction. Oxidation/degradation of light alkanes are typically associated with increasing ð13C values. Isotopic mass balances offer the possibility to independently determine the fractions coming from microbial versus thermogenic and would also permit differentiation of the isotope fractionations associated with degradation. Unlike conventional concentration measurements, this approach is constrained by the different isotopic signatures of various sources and sinks.

Lithium isotope fractionation by diffusion in minerals Part 2: Olivine

NASA Astrophysics Data System (ADS)

Richter, Frank; Chaussidon, Marc; Bruce Watson, E.; Mendybaev, Ruslan; Homolova, Veronika

2017-12-01

Recent experiments have shown that lithium isotopes can be significantly fractionated by diffusion in silicate liquids and in augite. Here we report new laboratory experiments that document similarly large lithium isotopic fractionation by diffusion in olivine. Two types of experiments were used. A powder-source method where lithium from finely ground spodumene (LiAlSi2O6) diffused into oriented San Carlos olivine, and piston cylinder annealing experiments where Kunlun clinopyroxene (∼30 ppm lithium) and oriented San Carlos olivine (∼2 ppm lithium) were juxtaposed. The lithium concentration along traverses across the run products was measured using both laser ablation as a source for a Varian 820-MS quadrupole mass spectrometer and a CAMECA 1270 secondary ion mass spectrometer. The CAMECA 1270 was also used to measure the lithium isotopic fractionation across olivine grains recovered from the experiments. The lithium isotopes were found to be fractionationed by many tens of permil in the diffusion boundary layer at the grain edges as a result of 6Li diffusing significantly faster than 7Li. The lithium concentration and isotopic fractionation data across the olivine recovered from the different experiments were modeled using calculations in which lithium was assumed to be of two distinct types - one being fast diffusing interstitial lithium, the other much less mobile lithium on a metal site. The two-site diffusion model involves a large number of independent parameters and we found that different choices of the parameters can produce very comparable fits to the lithium concentration profiles and associated isotopic fractionation. Because of this nonuniqueness we are able to determine only a range for the relative diffusivity of 6Li compared to 7Li. When the mass dependence of lithium diffusion is parameterized as D6Li /D7Li =(7 / 6) β , the isotope fractionation for diffusion along the a and c crystallographic direction of olivine can be fit by β = 0.4 ± 0.1 while the fractionation in the b direction appears to be somewhat lower. Model calculations were also used to fit the lithium concentration and isotopic fractionation across a natural olivine grain from a peridotite xenolith from the Eastern North China Craton. The isotopic data were fit using β values (0.3-0.36) similar to that of the laboratory experiments. This, along with the fact that the isotopic fractionation is restricted to that part of the mineral with a gradient in lithium concentration, is strong evidence that the lithium zoning of this mineral grain is the result of lithium loss by diffusion and thus that it can be used, as illustrated, to constrain the cooling history.

Assessing site-specific spatio-temporal variations in hydrogen and oxygen stable isotopes of human drinking water

NASA Astrophysics Data System (ADS)

Kennedy, C. D.; Bowen, G. J.; Ehleringer, J. R.

2008-12-01

Stable isotope ratios of hydrogen and oxygen (δ2H and δ18O) are environmental forensic tracers that can be used to constrain the origin and movement of animals, people, and products. The fundamental assumption underlying this method is that water resources at different geographic locations have distinct and characteristic isotopic signatures that are assimilated into organic tissues. Although much is known about regional-scale spatio-temporal variability in δ2H and δ18O of water, few studies have addressed the question of how distinct these geographic and seasonal patterns are for any given site. To address this question, a 2-year survey of δ2H and δ18O in tap water from across the contiguous U.S. and Canada was conducted. The data show that seasonal variability in δ2H and δ18O of tap water is generally low (<10 ‰ for δ2H), and those with the highest variability can be classified as: a) cities or towns in areas of high climate seasonality, or b) large cities in arid or seasonally arid regions which access and switch among multiple water sources throughout the year. The data suggest that inter-annual variation in tap water isotope ratios is typically low, with a median difference for month-month pairs during the 2 sampling years of 2.7 (δ2H). The results from this study confirm the existence of temporal variability in δ2H and δ18O of tap water, but suggest that this variability in human-managed systems is highly damped and may be amenable to classification, modeling, and prediction. In all, the data provide the foundation for incorporating temporal variation in predictive models of water and organic δ2H and δ18O, leading to more robust and statistically defensible tests of geographic origin.

Uranium isotopes distinguish two geochemically distinct stages during the later Cambrian SPICE event

PubMed Central

Dahl, Tais W.; Boyle, Richard A.; Canfield, Donald E.; Connelly, James N.; Gill, Benjamin C.; Lenton, Timothy M.; Bizzarro, Martin

2015-01-01

Anoxic marine zones were common in early Paleozoic oceans (542–400 Ma), and present a potential link to atmospheric pO2 via feedbacks linking global marine phosphorous recycling, primary production and organic carbon burial. Uranium (U) isotopes in carbonate rocks track the extent of ocean anoxia, whereas carbon (C) and sulfur (S) isotopes track the burial of organic carbon and pyrite sulfur (primary long-term sources of atmospheric oxygen). In combination, these proxies therefore reveal the comparative dynamics of ocean anoxia and oxygen liberation to the atmosphere over million-year time scales. Here we report high-precision uranium isotopic data in marine carbonates deposited during the Late Cambrian ‘SPICE’ event, at ca. 499 Ma, documenting a well-defined −0.18‰ negative δ238U excursion that occurs at the onset of the SPICE event’s positive δ13C and δ34S excursions, but peaks (and tails off) before them. Dynamic modelling shows that the different response of the U reservoir cannot be attributed solely to differences in residence times or reservoir sizes - suggesting that two chemically distinct ocean states occurred within the SPICE event. The first ocean stage involved a global expansion of euxinic waters, triggering the spike in U burial, and peaking in conjunction with a well-known trilobite extinction event. During the second stage widespread euxinia waned, causing U removal to tail off, but enhanced organic carbon and pyrite burial continued, coinciding with evidence for severe sulfate depletion in the oceans (Gill et al., 2011). We discuss scenarios for how an interval of elevated pyrite and organic carbon burial could have been sustained without widespread euxinia in the water column (both non-sulfidic anoxia and/or a more oxygenated ocean state are possibilities). Either way, the SPICE event encompasses two different stages of elevated organic carbon and pyrite burial maintained by high nutrient fluxes to the ocean, and potentially sustained by internal marine geochemical feedbacks. PMID:25684783

Hercynian Pb-Zn mineralization types in the Alcudia Valley mining district (Spain) and their reflect in Pb isotopic signatures

NASA Astrophysics Data System (ADS)

García de Madinabeitia, S.; Santos Zalduegui, J. F.; Palero, F.; Gil Ibarguchi, J. I.; Carracedo, M.

2003-04-01

More than 450 ore deposits indexed within the Alcudia Valley of the Central-Iberian Zone (Spain) may be grouped by their tectonic and lithologic characteristics (1,2) as follows: type A of rare stratabound mineralizations, and types B, C, D and E represented by abundant Hercynian veins (post-Namurian). 86 new Pb isotope analyses of galenas from the four vein types reveal that types B and C have similar isotopic ratios with values of μ_2 = 10.07, ω_2 = 40.6 and a mean model age of 564 Ma. Types D and E have μ_2 and ω_2 values of 9.79 and 38.5, respectively, but differ each other with respect to their model ages, 600 Ma (type D) and 335 Ma (type E). The observed variations appear to be related to the geochemical features of the metasedimentary host-rocks of the mineralizations where two distinct types of Pb isotopic ratios have been reported (3): one with μ_2 and ω_2 comparable to those of the D and E types and another with a more radiogenic composition, close to those of the B and C types of galenas. Nägler et al. have suggested partial rehomogeneization of Pb isotopic composition within the metasediments at ca. 330 Ma, that is, prior to the mineralization events, but the extent of this process and its effects on the ore bodies isotopic features is not evident. The origin of the more abundant E type ore bodies has been related to the Hercynian granitic rocks in the area (2, and references therein). Other plutons within this sector of the Central Iberian Zone (e.g., Linares, etc.; cf. accompanying Abstract) associate ore bodies whose Pb isotopic composition is very similar to that of the E type galenas from the Alcudia Valley. The isotopic data obtained thus point to a related or common source material for the various types of granites within the area studied. Yet, the Pb isotopic composition of other mineralizations (B, C, D), likewise located in Hercynian veins, allow to consider different types of Pb-Zn ore bodies and point therefore to different sources of Pb at a regional scale. (1) Palero, F.J. Ph. D., University of Salamanca, Spain (1991). (2) Palero, F.; Both, R.A.; Arribas, A.; Boyce, A.J.; Mangas, J. &Martín-Izard, A. Economic Geology (in press). (3) Nägler, T. Ph. D., Diss ETH, Zurich N^o 9245 (1990).

Tracing water sources of terrestrial animal populations with stable isotopes: laboratory tests with crickets and spiders.

PubMed

McCluney, Kevin E; Sabo, John L

2010-12-31

Fluxes of carbon, nitrogen, and water between ecosystem components and organisms have great impacts across levels of biological organization. Although much progress has been made in tracing carbon and nitrogen, difficulty remains in tracing water sources from the ecosystem to animals and among animals (the "water web"). Naturally occurring, non-radioactive isotopes of hydrogen and oxygen in water provide a potential method for tracing water sources. However, using this approach for terrestrial animals is complicated by a change in water isotopes within the body due to differences in activity of heavy and light isotopes during cuticular and transpiratory water losses. Here we present a technique to use stable water isotopes to estimate the mean mix of water sources in a population by sampling a group of sympatric animals over time. Strong correlations between H and O isotopes in the body water of animals collected over time provide linear patterns of enrichment that can be used to predict a mean mix of water sources useful in standard mixing models to determine relative source contribution. Multiple temperature and humidity treatment levels do not greatly alter these relationships, thus having little effect on our ability to estimate this population-level mix of water sources. We show evidence for the validity of using multiple samples of animal body water, collected across time, to estimate the isotopic mix of water sources in a population and more accurately trace water sources. The ability to use isotopes to document patterns of animal water use should be a great asset to biologists globally, especially those studying drylands, droughts, streamside areas, irrigated landscapes, and the effects of climate change.

Spatial distribution of helium isotopes in volcanic gases and thermal waters along the Vanuatu (New Hebrides) volcanic arc

NASA Astrophysics Data System (ADS)

Jean-Baptiste, P.; Allard, P.; Fourré, E.; Bani, P.; Calabrese, S.; Aiuppa, A.; Gauthier, P. J.; Parello, F.; Pelletier, B.; Garaebiti, E.

2016-08-01

We report the first helium isotope survey of volcanic gases, hot springs and some olivine phenocrysts along the Vanuatu island arc, from Tanna in the south to Vanua Lava in the north. Low CO2 content and low 3He/4He ratios in thermal fluids of Epi (4.0 ± 0.1 Ra), Efate (4.5 ± 0.1 Ra) and Pentecost (5.3 ± 0.5 Ra) islands coherently indicate reduced mantle gas leakage and crustal contamination by radiogenic helium on these extinct volcanic systems of the former (Pliocene) arc. Instead, presently active Vanuatu volcanoes display 3He/4He and C/3He ratios typical of subduction-related volcanic arcs: 3He/4He ratios range from 6.4 ± 0.5 Ra in southernmost Tanna and 7.23 ± 0.09 Ra in northernmost Vanua Lava to typical MORB values in the central islands of Gaua (7.68 ± 0.06 Ra), Ambrym (7.6 ± 0.8 Ra) and Ambae (7 ± 2 Ra in groundwaters, 7.9 ± 1.4 Ra in olivine phenocrysts, and 8.0 ± 0.1 Ra in summit fumaroles of Aoba volcano). On Ambrym, however, we discover that hydrothermal manifestations separated by only 10-15 km on both sides of a major E-W transverse fault zone crossing the island are fed by two distinct helium sources, with different 3He/4He signatures: while fluids in southwest Ambrym (Baiap and Sesivi areas) have typical arc ratios (7.6 ± 0.8 Ra), fluids on the northwest coast (Buama Bay area) display both higher 3He/4He ratios (9.8 ± 0.2 Ra in waters to 10.21 ± 0.08 Ra in bubbling gases) and lower C/3He ratios that evidence a hotspot influence. We thus infer that the influx of Indian MORB mantle beneath the central Vanuatu arc, from which Ambrym magmas originate, also involves a 3He-rich hotspot component, possibly linked to a westward influx of Samoan hotspot material or another yet unknown local source. This duality in magmatic He source at Ambrym fits with the bimodal composition and geochemistry of the erupted basalts, implying two distinct magma sources and feeding systems. More broadly, the wide He isotopic variations detected along the Vanuatu arc further verify the complex tectonic and magmatic framework of this intra-oceanic island arc.

Osmium isotopes suggest fast and efficient mixing in the oceanic upper mantle.

NASA Astrophysics Data System (ADS)

Bizimis, Michael; Salters, Vincent

2010-05-01

The depleted upper mantle (DUM; the source of MORB) is thought to represent the complementary reservoir of continental crust extraction. Previous studies have calculated the "average" DUM composition based on the geochemistry of MORB. However the Nd isotope compositions of abyssal peridotites have been shown to extend to more depleted compositions than associated MORB. While this argues for the presence of both relatively depleted and enriched material within the upper mantle, the extent of compositional variability, length scales of heterogeneity and timescales of mixing in the upper mantle are not well constrained. Model calculations show that 2Ga is a reasonable mean age of depletion for DUM while Hf - Nd isotopes show the persistence of a depleted terrestrial reservoir by the early Archean (3.5-3.8Ga). U/Pb zircon ages of crustal rocks show three distinct peaks at 1.2, 1.9, and 2.7Ga and these are thought to represent the ages of three major crustal growth events. A fundamental question therefore is whether the present day upper mantle retains a memory of multiple ancient depletion events, or has been effectively homogenized. This has important implications for the nature of convection and time scales of survival of heterogeneities in the upper mantle. Here we compare published Os isotope data from abyssal peridotites and ophiolitic Os-Ir alloys with new data from Hawaiian spinel peridotite xenoliths. The Re-Os isotope system has been shown to yield useful depletion age information in peridotites, so we use it here to investigate the distribution of Re-depletion ages (TRD) in these mantle samples as a proxy for the variability of DUM. The probability density functions (PDF) of TRD from osmiridiums, abyssal and Hawaiian peridotites are all remarkably similar and show a distinct peak at 1.2-1.3 Ga (errors for TRD are set at 0.2Ga to suppress statistically spurious age peaks). The Hawaiian peridotites further show a distinct peak at 1.9-2Ga, but no oceanic mantle samples with TRD older than 2Ga have been reported. The TRD age peaks overlap with two major crustal building events recorded in the U/Pb crustal zircon ages. Therefore, peridotites from the convecting upper mantle can retain some memory of ancient depletion events, and these depletions are perhaps linked to major crustal building or large-scale mantle melting events. In the case of the Hawaiian peridotites, an ancient depletion event is further supported by some extremely radiogenic Hf isotope compositions. However, the vast majority of oceanic mantle samples show a narrow rage of Os isotope compositions (187Os/188Os = 0.123-0.126) with TRDs at 300-600 Ma. If the upper mantle has been produced continuously (or episodically) since at least the early Archean, it is then surprising that almost all oceanic mantle samples record such young depletion ages. We suggest that convective mixing in the mantle is rigorous enough that effectively re-homogenizes and resets the Os isotope composition of previously depleted peridotites within short time scales (<500Ma). Similarly recent ages have been derived from modeling the Sr, Nd, Hf, Pb isotopic composition of MORBs. This resetting and homogenization can be due to re-equilibration of depleted mantle with enriched components, e.g. recycled basaltic crust or more fertile mantle. Ancient depletion events are only effectively preserved in the sublithospheric mantle samples (e.g. Kaapval, Slave, Wyoming cratons) because they remain isolated from the convective mantle.

Circum-Arctic petroleum systems identified using decision-tree chemometrics

USGS Publications Warehouse

Peters, K.E.; Ramos, L.S.; Zumberge, J.E.; Valin, Z.C.; Scotese, C.R.; Gautier, D.L.

2007-01-01

Source- and age-related biomarker and isotopic data were measured for more than 1000 crude oil samples from wells and seeps collected above approximately 55??N latitude. A unique, multitiered chemometric (multivariate statistical) decision tree was created that allowed automated classification of 31 genetically distinct circumArctic oil families based on a training set of 622 oil samples. The method, which we call decision-tree chemometrics, uses principal components analysis and multiple tiers of K-nearest neighbor and SIMCA (soft independent modeling of class analogy) models to classify and assign confidence limits for newly acquired oil samples and source rock extracts. Geochemical data for each oil sample were also used to infer the age, lithology, organic matter input, depositional environment, and identity of its source rock. These results demonstrate the value of large petroleum databases where all samples were analyzed using the same procedures and instrumentation. Copyright ?? 2007. The American Association of Petroleum Geologists. All rights reserved.

Nitrogen-isotopes and multi-parameter sewage water test for identification of nitrate sources: Groundwater body Marchfeld East of Vienna

NASA Astrophysics Data System (ADS)

Kralik, Martin

2017-04-01

The application of nitrogen and oxygen isotopes in nitrate allows, under favourable circumstances, to identify potential sources such as precipitation, chemical fertilisers and manure or sewage water. Without any additional tracer, the source distinction of nitrate from manure or sewage water is still difficult. Even the application of boron isotopes can in some cases not avoid ambiguous interpretation. Therefore, the Environment Agency Austria developed a new multi parametrical indicator test to allow the identification and quantification of pollution by domestic sewage water. The test analyses 8 substances well known to occur in sewage water: Acesulfame and sucralose (two artificial, calorie-free sweeteners), benzotriazole and tolyltriazole (two industrial chemicals/corrosion inhibitors), metoprolol, sotalol, carbamazepine and the metabolite 10,11-Dihydro-10,11-dihydroxycarbamazepine (pharmaceuticals) [1]. These substances are polar and degradation in the aquatic system by microbiological processes is not documented. These 8 Substances do not occur naturally which make them ideal tracers. The test can detect wastewater in the analysed water sample down to 0.1 %. This ideal coupling of these analytic tests helps to identify the nitrogen sources in the groundwater body Marchfeld East of Vienna to a high confidence level. In addition, the results allow a reasonable quantification of nitrogen sources from different types of fertilizers as well as sewage water contributions close to villages and in wells recharged by bank filtration. Recent investigations of groundwater in selected wells in Marchfeld [2] indicated a clear nitrogen contribution by wastewater leakages (sewers or septic tanks) to the total nitrogen budget. However, this contribution is shrinking and the main source comes still from agricultural activities. [1] Humer, F.; Weiss, S.; Reinnicke, S.; Clara, M.; Grath, J.; Windhofer, G. (2013): Multi parametrical indicator test for urban wastewater influence. EGU General Assembly 2013, held 7-12 April, 2013 in Vienna, Austria, id. EGU2013-5332, EGU2013-5332. [2] Kralik, M.; Humer, F. & Grath, J. (2008): Pilotprojekt Grundwasseralter: Herkunftsanalyse von Nitrat mittels Stickstoff-, Sauerstoff-, Schwefel und Kohlenstoffisotopen. 57 S.2, Environment Agency Austria/Ministry of Agriculture, Forestry, Environment and Water Management, Vienna.

Discovery of a Triassic magmatic arc source for the Permo-Triassic Karakaya subduction complex, NW Turkey

NASA Astrophysics Data System (ADS)

Ayda Ustaömer, Petek; Ustaömer, Timur; Gerdes, Axel; Robertson, Alastair H. F.; Zulauf, Gernold

2014-05-01

The Permo-Triassic Karakaya Complex is well explained by northward subduction of Palaeotethys but until now no corresponding magmatic arc has been identified in the region. With the aim of determining the compositions and ages of the source units, ten sandstone samples were collected from the mappably distinct Ortaoba, Hodul, Kendirli and Orhanlar Units. Zircon grains were extracted from these sandstones and >1300 were dated by the U-Pb method and subsequently analysed for the Lu-Hf isotopic compositions by LA-MC-ICPMS at Goethe University, Frankfurt. The U-Pb-Hf isotope systematics are indicative of two different sediment provenances. The first, represented by the Ortaoba, Hodul and Kendirli Units, is dominated by igneous rocks of Triassic (250-220 Ma), Early Carboniferous-Early Permian (290-340 Ma) and Early to Mid-Devonian (385-400 Ma) ages. The second provenance, represented by the Orhanlar Unit, is indicative of derivation from a peri-Gondwanan terrane. In case of the first provenance, the Devonian and Carboniferous source rocks exibit intermediate eHf(t) values (-11 to -3), consistent with the formation at a continental margin where juvenile mantle-derived magmas mixed with (recycled) old crust having Palaeoproterozoic Hf model ages. In contrast, the Triassic arc magma exhibits higher eHf(t) values (-6 to +6), consistent with the mixing of juvenile mantle-derived melts with (recycled) old crust perhaps somewhat rejuvanated during the Cadomian period. We have therefore identified a Triassic magmatic arc as predicted by the interpretation of the Karakaya Complex as an accretionary complex related to northward subduction (Carboniferous and Devonian granites are already well documented in NW Turkey). Possible explanations for the lack of any outcrop of the source magmatic arc are that it was later subducted or the Karakaya Complex was displaced laterally from its source arc (both post 220 Ma). Strike-slip displacement (driven by oblique subduction?) can also explain the presence of two different sandstone source areas as indicated by the combined U-Pb-Hf isotope and supporting petrographic data. This study was supported by TUBITAK, Project no: 111R015

Sources and transformations of nitrate from streams draining varying land uses: Evidence from dual isotope analysis

USGS Publications Warehouse

Burns, Douglas A.; Boyer, E.W.; Elliott, E.M.; Kendall, C.

2009-01-01

Knowledge of key sources and biogeochemical processes that affect the transport of nitrate (NO3-) in streams can inform watershed management strategies for controlling downstream eutrophication. We applied dual isotope analysis of NO3- to determine the dominant sources and processes that affect NO3- concentrations in six stream/river watersheds of different land uses. Samples were collected monthly at a range of flow conditions for 15 mo during 2004-05 and analyzed for NO3- concentrations, ?? 15NNO3, and ??18ONO3. Samples from two forested watersheds indicated that NO3- derived from nitrification was dominant at baseflow. A watershed dominated by suburban land use had three ??18ONO3 values greater than +25???, indicating a large direct contribution of atmospheric NO 3- transported to the stream during some high flows. Two watersheds with large proportions of agricultural land use had many ??15NNO3 values greater than +9???, suggesting an animal waste source consistent with regional dairy farming practices. These data showed a linear seasonal pattern with a ??18O NO3:??15NNO3 of 1:2, consistent with seasonally varying denitrification that peaked in late summer to early fall with the warmest temperatures and lowest annual streamflow. The large range of ?? 15NNO3 values (10???) indicates that NO 3- supply was likely not limiting the rate of denitrification, consistent with ground water and/or in-stream denitrification. Mixing of two or more distinct sources may have affected the seasonal isotope patterns observed in these two agricultural streams. In a mixed land use watershed of large drainage area, none of the source and process patterns observed in the small streams were evident. These results emphasize that observations at watersheds of a few to a few hundred km2 may be necessary to adequately quantify the relative roles of various NO 3- transport and process patterns that contribute to streamflow in large basins. Copyright ?? 2009 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Perchlorate isotope forensics

USGS Publications Warehouse

Böhlke, J.K.; Sturchio, N.C.; Gu, B.; Horita, J.; Brown, G.M.; Jackson, W.A.; Batista, J.; Hatzinger, P.B.

2005-01-01

Perchlorate has been detected recently in a variety of soils, waters, plants, and food products at levels that may be detrimental to human health. These discoveries have generated considerable interest in perchlorate source identification. In this study, comprehensive stable isotope analyses ( 37Cl/35Cl and 18O/17O/ 16O) of perchlorate from known synthetic and natural sources reveal systematic differences in isotopic characteristics that are related to the formation mechanisms. In addition, isotopic analyses of perchlorate extracted from groundwater and surface water demonstrate the feasibility of identifying perchlorate sources in contaminated environments on the basis of this technique. Both natural and synthetic sources of perchlorate have been identified in water samples from some perchlorate occurrences in the United States by the isotopic method. ?? 2005 American Chemical Society.

δ2H and δ18O of human body water: a GIS model to distinguish residents from non-residents in the contiguous USA.

PubMed

Podlesak, David W; Bowen, Gabriel J; O'Grady, Shannon; Cerling, Thure E; Ehleringer, James R

2012-06-01

An understanding of the factors influencing the isotopic composition of body water is important to determine the isotopic composition of tissues that are used to reconstruct movement patterns of humans. The δ(2)H and δ(18)O values of body water (δ(2)H(bw) and δ(18)O(bw)) are related to the δ(2)H and δ(18)O values of drinking water (δ(2)H(dw) and δ(18)O(dw)), but clearly distinct because of other factors including the composition of food. Here, we develop a mechanistic geographical information system (GIS) model to produce spatial projections of δ(2)H(bw) and δ(18)O(bw) values for the USA. We investigate the influence of gender, food, and drinking water on the predicted values by comparing them with the published values. The strongest influence on the predicted values was related to the source of δ(2)H(dw) and δ(18)O(dw) values. We combine the model with equations that describe the rate of turnover to produce estimates for the time required for a non-resident to reach an isotopic equilibrium with a resident population.

Improved estimation of sediment source contributions by concentration-dependent Bayesian isotopic mixing model

NASA Astrophysics Data System (ADS)

Ram Upadhayay, Hari; Bodé, Samuel; Griepentrog, Marco; Bajracharya, Roshan Man; Blake, Will; Cornelis, Wim; Boeckx, Pascal

2017-04-01

The implementation of compound-specific stable isotope (CSSI) analyses of biotracers (e.g. fatty acids, FAs) as constraints on sediment-source contributions has become increasingly relevant to understand the origin of sediments in catchments. The CSSI fingerprinting of sediment utilizes CSSI signature of biotracer as input in an isotopic mixing model (IMM) to apportion source soil contributions. So far source studies relied on the linear mixing assumptions of CSSI signature of sources to the sediment without accounting for potential effects of source biotracer concentration. Here we evaluated the effect of FAs concentration in sources on the accuracy of source contribution estimations in artificial soil mixture of three well-separated land use sources. Soil samples from land use sources were mixed to create three groups of artificial mixture with known source contributions. Sources and artificial mixture were analysed for δ13C of FAs using gas chromatography-combustion-isotope ratio mass spectrometry. The source contributions to the mixture were estimated using with and without concentration-dependent MixSIAR, a Bayesian isotopic mixing model. The concentration-dependent MixSIAR provided the closest estimates to the known artificial mixture source contributions (mean absolute error, MAE = 10.9%, and standard error, SE = 1.4%). In contrast, the concentration-independent MixSIAR with post mixing correction of tracer proportions based on aggregated concentration of FAs of sources biased the source contributions (MAE = 22.0%, SE = 3.4%). This study highlights the importance of accounting the potential effect of a source FA concentration for isotopic mixing in sediments that adds realisms to mixing model and allows more accurate estimates of contributions of sources to the mixture. The potential influence of FA concentration on CSSI signature of sediments is an important underlying factor that determines whether the isotopic signature of a given source is observable even after equilibrium. Therefore inclusion of FA concentrations of the sources in the IMM formulation is standard procedure for accurate estimation of source contributions. The post model correction approach that dominates the CSSI fingerprinting causes bias, especially if the FAs concentration of sources differs substantially.

2-Methylhopanoids: Biomarkers for Cyanobacteria and for Oxygenic Photosynthesis

NASA Technical Reports Server (NTRS)

Summons, R. E.; Jahnke, L. L.; Hope, J. M.; Logan, G. A.

1999-01-01

This paper reports new biomarker and carbon isotopic data for cultured cyanobacteria, cyano-bacterially- dominated ecosystems and ancient sedi-ments and petroleum. We found that cyanobacteria are the predominant source of a distinctive membrane lipid biomarker, namely 2- methylbacteriohopanepolyol (2-Me-BHP). We then sought evidence for a geochemical record of the fossil hydrocarbon analogues of these compounds (2- methylhopanes) and found a trend toward their in-creased relative abundance in marine sediments going back through geological time to 2500 Ma. We conclude that cyanobacteria were the dominant form of phytoplankton and source of molecular oxygen in the Proterozoic ocean. Extending the geological record of cyanobacteria further to Archean times is now a matter of finding a suitably preserved rock record. Additional information is contained in the original extended abstract.

Isotope effect of mercury diffusion in air

PubMed Central

Koster van Groos, Paul G.; Esser, Bradley K.; Williams, Ross W.; Hunt, James R.

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature. PMID:24364380

Isotope effect of mercury diffusion in air.

PubMed

Koster van Groos, Paul G; Esser, Bradley K; Williams, Ross W; Hunt, James R

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature.

[Sources of Methane in the Boreal Region

NASA Technical Reports Server (NTRS)

1998-01-01

In determining the global methane budget the sources of methane must be balanced with the sinks and atmospheric inventory. The approximate contribution of the different methane sources to the budget has been establish showing the major terrestrial inputs as rice, wetlands, bogs, fens, and tundra. Measurements and modeling of production in these sources suggest that temperature, water table height and saturation along with substratum composition are important in controlling methane production and emission. The isotopic budget of 13 C and D/H in methane can be used as a tool to clarify the global budget. This approach has achieved success at constraining the inputs. Studies using the isotopic approach place constraints on global methane production from different sources. Also, the relation between the two biogenic production pathways, acetate fermentation and CO2 reduction, and the effect of substratum composition can be made using isotope measurements shows the relation between the different biogenic, thermogenic and anthropogenic sources of methane as a function of the carbon and hydrogen isotope values for each source and the atmosphere, tropospheric composition. Methane emissions from ponds and fens are a significant source in the methane budget of the boreal region. An initial study in 1993 and 1994 on the isotopic composition of this methane source and the isotopic composition in relation to oxidation of methane at the sediment surface of the ponds or fen was conducted as part of our BOREAS project. The isotopic composition of methane emitted by saturated anoxic sediment is dependent on the sediment composition and geochemistry, but will be influenced by in situ oxidation, in part, a function of rooted plant activity. The influence of oxidation mediated by rooted plant activities on the isotopic composition of methane is not well known and will depend on the plant type, sediment temperature, and numerous other variables. Information on this isotopic composition is important in both understanding the bio-geochemistry of the system and also in determining the regional and global inputs for the methane isotope budget. In determining the destruction of methane for balancing the atmospheric methane budget soil oxidation must be considered.

Petrology and Physics of Magma Ocean Crystallization

NASA Technical Reports Server (NTRS)

Elkins-Tanton, Linda T.; Parmentier, E. M.; Hess, P. C.

2003-01-01

Early Mars is thought to have been melted significantly by the conversion of kinetic energy to heat during accretion of planetesimals. The processes of solidification of a magma ocean determine initial planetary compositional differentiation and the stability of the resulting mantle density profile. The stability and compositional heterogeneity of the mantle have significance for magmatic source regions, convective instability, and magnetic field generation. Significant progress on the dynamical problem of magma ocean crystallization has been made by a number of workers. The work done under the 2003 MFRP grant further explored the implications of early physical processes on compositional heterogeneity in Mars. Our goals were to connect early physical processes in Mars evolution with the present planet's most ancient observable characteristics, including the early, strong magnetic field, the crustal dichotomy, and the compositional characteristics of the SNC meteorite's source regions as well as their formation as isotopically distinct compositions early in Mars's evolution. We had already established a possible relationship between the major element compositions of SNC meteorite sources and processes of Martian magma ocean crystallization and overturn, and under this grant extended the analysis to the crucial trace element and isotopic SNC signatures. This study then demonstrated the ability to create and end the magnetic field through magma ocean cumulate overturn and subsequent cooling, as well as the feasibility of creating a compositionally- and volumetrically-consistent crustal dichotomy through mode-1 overturn and simultaneous adiabatic melting.

Chlorine-36 as a tracer of perchlorate origin

USGS Publications Warehouse

Sturchio, N.C.; Caffee, M.; Beloso, Abelardo D.; Heraty, L.J.; Böhlke, J.K.; Hatzinger, P.B.; Jackson, W.A.; Gu, B.; Heikoop, J.M.; Dale, M.

2009-01-01

Perchlorate (ClO4-) is ubiquitous in the environment. It is produced naturally by atmospheric photochemical reactions, and also is synthesized in large quantities for military, aerospace, and industrial applications. Nitrate-enriched salt deposits of the Atacama Desert (Chile) contain high concentrations of natural ClO4-, and have been exported worldwide since the mid-1800s for use in agriculture. The widespread introduction of synthetic and agricultural ClO4- into the environment has contaminated numerous municipal water supplies. Stable isotope ratio measurements of Cl and O have been applied for discrimination of different ClO4- sources in the environment. This study explores the potential of 36Cl measurements for further improving the discrimination of ClO4- sources. Groundwater and desert soil samples from the southwestern United States (U.S.) contain ClO4- having high 36Cl abundances (36Cl/Cl = 3100 ?? 10-15 to 28,800 ?? 10 -15), compared with those from the Atacama Desert (36Cl/Cl = 0.9 ?? 10-15 to 590 ?? 10-15) and synthetic ClO4- reagents and products (36Cl/Cl = 0.0 ?? 10-15 to 40 ?? 1015). In conjunction with stable Cl and O isotope ratios, 36Cl data provide a clear distinction among three principal. ClO4- source types in the environment of the southwestern U.S. ?? 2009 American Chemical Society.

Apparatus and method for detecting gamma radiation

DOEpatents

Sigg, Raymond A.

1994-01-01

A high efficiency radiation detector for measuring X-ray and gamma radiation from small-volume, low-activity liquid samples with an overall uncertainty better than 0.7% (one sigma SD). The radiation detector includes a hyperpure germanium well detector, a collimator, and a reference source. The well detector monitors gamma radiation emitted by the reference source and a radioactive isotope or isotopes in a sample source. The radiation from the reference source is collimated to avoid attenuation of reference source gamma radiation by the sample. Signals from the well detector are processed and stored, and the stored data is analyzed to determine the radioactive isotope(s) content of the sample. Minor self-attenuation corrections are calculated from chemical composition data.

Horizon Partitioning of Soil CO2 Sources and their Isotopic Composition (13C) in a Pinus Sylvestris Stand

NASA Astrophysics Data System (ADS)

Goffin, S.; Parent, F.; Plain, C.; Maier, M.; Schack-Kirchner, H.; Aubinet, M.; Longdoz, B.

2012-12-01

The overall aim of this study is to contribute to a better understanding of mechanisms behind soil CO2 efflux using carbon stable isotopes. The approach combines a soil multilayer analysis and the isotopic tool in an in situ study. The specific goal of this work is to quantify the origin and the determinism of 13CO2 and 12CO2 production processes in the different soil layers using the gradient-efflux approach. To meet this, the work includes an experimental setup and a modeling approach. The experimental set up (see also communication of Parent et al., session B008) comprised a combination of different systems, which were installed in a Scot Pine temperate forest at the Hartheim site (Southwestern Germany). Measurements include (i) half hourly vertical profiles of soil CO2 concentration (using soil CO2 probes), soil water content and temperature; (ii) half hourly soil surface CO2 effluxes (automatic chambers); (iii) half hourly isotopic composition of surface CO2 efflux and soil CO2 concentration profile and (iv) estimation of soil diffusivity through laboratory measurements conducted on soil samples taken at several depths. Using the data collected in the experimental part, we developed and used a diffusive transport model to simulate CO2 (13CO2 and 12CO2) flows inside and out of the soil based on Fick's first law. Given the horizontal homogeneity of soil physical parameters in Hartheim, we treated the soil as a structure consisting of distinctive layers of 5 cm thick and expressed the Fick's first law in a discrete formalism. The diffusion coefficient used in each layer was derived from (i) horizon specific relationships, obtained from laboratory measurements, between soil relative diffusivity and its water content and (ii) the soil water content values measured in situ. The concentration profile was obtained from in situ measurements. So, the main model inputs are the profiles of (i) CO2 (13CO2 and 12CO2) concentration, (ii) soil diffusion coefficient and (iii) soil water content. Once the diffusive fluxes deduced at each layer interface, the CO2 (13CO2 and 12CO2) production profile was calculated using the (discretized) mass balance equation in each layer. The results of the Hartheim measurement campaign will be presented. The CO2 source vertical profile and its link with the root and the Carbon organic content distribution will be showed. The dynamic of CO2 sources and their isotopic signature will be linked to climatic variables such soil temperature and soil water content. For example, we will show that the dynamics of CO2 sources was mainly related to temperature while changing of isotopic signature was more correlated to soil moisture.

Dietary Plasticity of Generalist and Specialist Ungulates in the Namibian Desert: A Stable Isotopes Approach

PubMed Central

Lehmann, David; Mfune, John Kazgeba Elijah; Gewers, Erick; Cloete, Johann; Brain, Conrad; Voigt, Christian Claus

2013-01-01

Desert ungulates live in adverse ecosystems that are particularly sensitive to degradation and global climate change. Here, we asked how two ungulate species with contrasting feeding habits, grazing gemsbok (Oryx g. gazella) and browsing springbok (Antidorcas marsupialis), respond to an increase in food availability during a pronounced rain period. We used a stable isotope approach to delineate the feeding habits of these two ungulates in the arid Kunene Region of Namibia. Our nineteen months field investigation included two time periods of drought when food availability for ungulates was lowest and an intermediate period with extreme, unusual rainfalls. We documented thirteen isotopically distinct food sources in the isotopic space of the study area. Our results indicated a relatively high dietary plasticity of gemsbok, which fed on a mixture of plants, including more than 30% of C3 plants during drought periods, but almost exclusively on C4 and CAM plant types when food was plentiful. During drought periods, the inferred gemsbok diets also consisted of up to 25% of Euphorbia damarana; an endemic CAM plant that is rich in toxic secondary plant compounds. In contrast, springbok were generalists, feeding on a higher proportion of C3 than C4/CAM plants, irrespective of environmental conditions. Our results illustrate two dietary strategies in gemsbok and springbok which enable them to survive and coexist in the hostile Kunene arid ecosystem. PMID:23977249

Dietary plasticity of generalist and specialist ungulates in the Namibian Desert: a stable isotopes approach.

PubMed

Lehmann, David; Mfune, John Kazgeba Elijah; Gewers, Erick; Cloete, Johann; Brain, Conrad; Voigt, Christian Claus

2013-01-01

Desert ungulates live in adverse ecosystems that are particularly sensitive to degradation and global climate change. Here, we asked how two ungulate species with contrasting feeding habits, grazing gemsbok (Oryx g. gazella) and browsing springbok (Antidorcas marsupialis), respond to an increase in food availability during a pronounced rain period. We used a stable isotope approach to delineate the feeding habits of these two ungulates in the arid Kunene Region of Namibia. Our nineteen months field investigation included two time periods of drought when food availability for ungulates was lowest and an intermediate period with extreme, unusual rainfalls. We documented thirteen isotopically distinct food sources in the isotopic space of the study area. Our results indicated a relatively high dietary plasticity of gemsbok, which fed on a mixture of plants, including more than 30% of C3 plants during drought periods, but almost exclusively on C4 and CAM plant types when food was plentiful. During drought periods, the inferred gemsbok diets also consisted of up to 25% of Euphorbia damarana; an endemic CAM plant that is rich in toxic secondary plant compounds. In contrast, springbok were generalists, feeding on a higher proportion of C3 than C4/CAM plants, irrespective of environmental conditions. Our results illustrate two dietary strategies in gemsbok and springbok which enable them to survive and coexist in the hostile Kunene arid ecosystem.

Oxygen, hydrogen, sulfur, and carbon isotopes in the Pea Ridge magnetite-apatite deposit, southeast Missouri, and sulfur isotope comparisons to other iron deposits in the region

USGS Publications Warehouse

Johnson, Craig A.; Day, Warren C.; Rye, Robert O.

2016-01-01

Oxygen, hydrogen, sulfur, and carbon isotopes have been analyzed in the Pea Ridge magnetite-apatite deposit, the largest historic producer among the known iron deposits in the southeast Missouri portion of the 1.5 to 1.3 Ga eastern granite-rhyolite province. The data were collected to investigate the sources of ore fluids, conditions of ore formation, and provenance of sulfur, and to improve the general understanding of the copper, gold, and rare earth element potential of iron deposits regionally. The δ18O values of Pea Ridge magnetite are 1.9 to 4.0‰, consistent with a model in which some magnetite crystallized from a melt and other magnetite—perhaps the majority—precipitated from an aqueous fluid of magmatic origin. The δ18O values of quartz, apatite, actinolite, K-feldspar, sulfates, and calcite are significantly higher, enough so as to indicate growth or equilibration under cooler conditions than magnetite and/or in the presence of a fluid that was not entirely magmatic. A variety of observations, including stable isotope observations, implicate a second fluid that may ultimately have been meteoric in origin and may have been modified by isotopic exchange with rocks or by evaporation during storage in lakes.Sulfur isotope analyses of sulfides from Pea Ridge and seven other mineral deposits in the region reveal two distinct populations that average 3 and 13‰. Two sulfur sources are implied. One was probably igneous melts or rocks belonging to the mafic- to intermediate-composition volcanic suite that is present at or near most of the iron deposits; the other was either melts or volcanic rocks that had degassed very extensively, or else volcanic lakes that had trapped rising magmatic gases. The higher δ34S values correspond to deposits or prospects where copper is noteworthy—the Central Dome portion of the Boss deposit, the Bourbon deposit, and the Vilander prospective area. The correspondence suggests that (1) sulfur either limited the deposition of copper or was cotransported with copper, and (2) sulfur isotope analysis may be useful in evaluating southeast Missouri iron deposits for copper and possibly for gold.

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.

Measurements of actinides in soil, sediments, water and vegetation in Northern New Mexico

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

Gallaher, B. M.; Efurd, D. W.

2002-01-01

This study was undertaken during 1991 - 1998 to identify the origin of plutonium uranium in northern New Mexico Rio Grande and tributary stream sediments. Isotopic fingerprinting techniques help distinguish radioactivity from Los Alamos National Laboratory (LANL) and from global fallout or natural sources. The geographic area covered by the study extended from the headwaters of the Rio Grande in southern Colorado to Elephant Butte Reservoir in southern New Mexico. Over 100 samples of stream channel and reservoir bottom sediments were analyzed for the atom ratios of plutonium and uranium isotopes using thermal ionization mass spectrometry (TIMS). Comparison of thesemore » ratios against those for fallout or natural sources allowed for quantification of the Laboratory impact. Of the seven major drainages crossing LANL, movement of LANL plutonium into the Rio Grande can only be traced via Los Alamos Canyon. The majority of sampled locations within and adjacent to LANL have little or no input of plutonium from the Laboratory. Samples collected upstream and distant to L A N show an average (+ s.d.) fallout 240Pu/239Pauto m ratio of 0.169 + 0.012, consistent with published worldwide global fallout values. These regional background ratios differ significantly from the 240Pu/239Pu atom ratio of 0.015 that is representative of LANL-derived plutonium entering the Rio Grande at Los Alamos Canyon. Mixing calculations of these sources indicate that the largest proportion (60% to 90%) of the plutonium in the Rio Grande sediments is from global atmospheric fallout, with an average of about 25% from the Laboratory. The LANL plutonium is identifiable intermittently along the 35-km reach of the Rio Grande to Cochiti Reservoir. The source of the LANL-derived plutonium in the Rio Grande was traced primarily to pre-1960 discharges of liquid effluents into a canyon bottom at a distance approximately 20 km upstream of the river. Plutonium levels decline exponentially with distance downstream after mixing with cleaner sediments, yet the LANL isotopic fingerprint remains distinct for at least 55 km from the effluent source. Plutonium isotopes in Rio Grande and Pajarito Plateau sediments are not at levels known to adversely affect public health. Activities of 239+240pwui thin this sample set ranged from 0.001- 0.046 pCUg in the Rio Grande to 3.7 pCi/g near the effluent discharge point. Levels in the Rio Grande are usually more than 1000 times. lower than prescribed cleanup standards. Uranium in stream and reservoir sediments is predominantly within natural concentration ranges and is of natural uranium isotopic composition. None of the sediments from the Rio Grande show identifiable Laboratory uranium, using the isotopic ratios. These results suggest that the mass of Laboratory-derived uranium entering the Rio Grande is small relative to the natural load carried with river sediments.« less

Using nitrate dual isotopic composition (δ15N and δ18O) as a tool for exploring sources and cycling of nitrate in an estuarine system: Elkhorn Slough, California

USGS Publications Warehouse

Wankel, Scott D.; Kendall, Carol; Paytan, Adina

2009-01-01

Nitrate (NO-3 concentrations and dual isotopic composition (??15N and ??18O) were measured during various seasons and tidal conditions in Elkhorn Slough to evaluate mixing of sources of NO-3 within this California estuary. We found the isotopic composition of NO-3 was influenced most heavily by mixing of two primary sources with unique isotopic signatures, a marine (Monterey Bay) and terrestrial agricultural runoff source (Old Salinas River). However, our attempt to use a simple two end-member mixing model to calculate the relative contribution of these two NO-3 sources to the Slough was complicated by periods of nonconservative behavior and/or the presence of additional sources, particularly during the dry season when NO-3 concentrations were low. Although multiple linear regression generally yielded good fits to the observed data, deviations from conservative mixing were still evident. After consideration of potential alternative sources, we concluded that deviations from two end-member mixing were most likely derived from interactions with marsh sediments in regions of the Slough where high rates of NO-3 uptake and nitrification result in NO-3 with low ?? 15N and high ??18O values. A simple steady state dual isotope model is used to illustrate the impact of cycling processes in an estuarine setting which may play a primary role in controlling NO -3 isotopic composition when and where cycling rates and water residence times are high. This work expands our understanding of nitrogen and oxygen isotopes as biogeochemical tools for investigating NO -3 sources and cycling in estuaries, emphasizing the role that cycling processes may play in altering isotopic composition. Copyright 2009 by the American Geophysical Union.

Identifying regional moisture source during the last deglaciation through analysis of central Texas speleothems

NASA Astrophysics Data System (ADS)

James, C.; Charlton, T.; Banner, J.; Koleszar, A. M.; James, E. W.; Breecker, D.; Miller, N. R.; Edwards, R. L.

2016-12-01

Precipitation in the drought-prone Southwest US is principally sourced from the Gulf of Mexico (GoM) and/or Pacific Ocean, each with distinctive δ18O compositions. Temporal changes in moisture source in this region have been reconstructed from speleothem proxies for the last deglaciation ( 19 - 11 ka). In this study we focus on how moisture sources in Texas speleothem records varied in response to abrupt deglacial warming/cooling events, namely the Bølling-Allerod (BA) interstadial (14.7-14.1 ka) and the Younger Dryas stadial (12.9-11.5 ka). A recent speleothem oxygen isotope record (CWN-4) in a stalagmite from Cave Without A Name near Boerne, Texas, suggests that both the magnitude and timing of changes in δ18O values during the deglaciation closely match δ18O values from a seawater proxy record based on GoM foraminifera (Feng et al., 2014; Flower et al., 2004). A distinct negative δ18O excursion of -3‰ is observed in both records at the onset of the BA, with a subsequent 3‰ increase occurring at the end of the BA. Based on these similarities, regional moisture was hypothesized to be predominantly sourced from the GoM. In order to test the hypothesis that the CWN-4 record captures a regional climate signal, as opposed to recording local variations in in-cave processes, we analyze multiple central Texas speleothem δ18O records. We present oxygen isotope records of a flowstone (IC-2) from a cave 130 km WSW of CWN and a stalagmite (McN-1) from a cave 140 km NE of CWN, with both records spanning the onset of the deglaciation through the Holocene. The IC-2 δ18O record is consistent with that of CWN-4, however, the age model relies on several dates with high uncertainties related to elevated concentrations of detritus containing common Th. The McN-1 record is anticipated to have a more robust age model as it appears to contain less detrital material based on low 232Th concentrations (< 0.009 ppb) in the growth layers that have been selected for U-series analysis. Preliminary δ18O values for the pre-BA period of McN-1 cover a similar range of δ18O values (-4.5 to -2.5‰) compared with the pre-BA portions of the CWN-4 and IC-2 records. These results are consistent with the regional climate hypothesis, which will be tested further by building a complete, high-resolution oxygen isotope time series for McN-1.

Rb-Sr, Sm-Nd, K-Ca, O, and H isotopic study of Cretaceous-Tertiary boundary sediments, Caravaca, Spain: evidence for an oceanic impact site

USGS Publications Warehouse

DePaolo, D.J.; Kyte, F.T.; Marshall, B.D.; O'Neil, J.R.; Smit, J.

1983-01-01

Isotopic ratios and trace element abundances were measured on samples of Ir-enriched clay at the Cretaceous-Tertiary boundary, and in carbonate and marl from 5 cm below and 3 cm above the boundary. Samples were leached with acetic acid to remove carbonate, and with hydrochloric acid. Leachates and residues were measured. The Sr, Nd, O and H isotopic compositions of the boundary clay residues are distinct from those of the stratigraphically neighboring materials. The data indicate that most of the clay material was derived from a terrestrial source with relatively low 87Sr/86Sr and high 143Nd/144Nd ratios. The ??18O data suggest that the detritus has been modified by submarine weathering. K-Ca and Rb-Sr systematics, as well as O isotope ratios of K-feldspar spherules within the boundary clay, suggest that they are predominantly authigenic and may have formed after the time of deposition. However, Sm-Nd and Rb-Sr isotopic data indicate that the spherules contain relict material that provides information on the nature of the original detritus. The isotopic evidence for foreign terrestrial detritus in the boundary clay, the low rare earth element concentrations and high Ni concentration, support the hypothesis of a terminal Cretaceous asteroidal impact that produced a global layer of fallout. The data are most easily explained if the impact site was on oceanic crust rather than continental crust, and if a substantial fraction of the fallout was derived from relatively deep within the lithosphere (>3 km). This would probably require a single large impactor. ?? 1983.

Atomic and Molecular Beam Scattering: Characterizing Structure and Dynamics of Hybrid Organic-Semiconductor Interfaces and Introducing Novel Isotope Separation Techniques

NASA Astrophysics Data System (ADS)

Nihill, Kevin John

This thesis details a range of experiments and techniques that use the scattering of atomic beams from surfaces to both characterize a variety of interfaces and harness mass-specific scattering conditions to separate and enrich isotopic components in a mixture of gases. Helium atom scattering has been used to characterize the surface structure and vibrational dynamics of methyl-terminated Ge(111), thereby elucidating the effects of organic termination on a rigid semiconductor interface. Helium atom scattering was employed as a surface-sensitive, non-destructive probe of the surface. By means of elastic gas-surface diffraction, this technique is capable of providing measurements of atomic spacing, step height, average atomic displacement as a function of surface temperature, gas-surface potential well depth, and surface Debye temperature. Inelastic time-of-flight studies provide highly resolved energy exchange measurements between helium atoms and collective lattice vibrations, or phonons; a collection of these measurements across a range of incident kinematic parameters allowed for a thorough mapping of low-energy phonons (e.g., the Rayleigh wave) across the surface Brillouin zone and subsequent comparison with complementary theoretical calculations. The scattering of molecular beams - here, hydrogen and deuterium from methyl-terminated Si(111) - enables the measurement of the anisotropy of the gas-surface interaction potential through rotationally inelastic diffraction (RID), whereby incident atoms can exchange internal energy between translational and rotational modes and diffract into unique angular channels as a result. The probability of rotational excitations as a function of incident energy and angle were measured and compared with electronic structure and scattering calculations to provide insight into the gas-surface interaction potential and hence the surface charge density distribution, revealing important details regarding the interaction of H2 with an organic-functionalized semiconductor interface. Aside from their use as probes for surface structure and dynamics, atomic beam sources are also demonstrated to enable the efficient separation of gaseous mixtures of isotopes by means of diffraction and differential condensation. In the former method, the kinematic conditions for elastic diffraction result in an incident beam of natural abundance neon diffracting into isotopically distinct angles, resulting in the enrichment of a desired isotope; this purification can be improved by exploiting the difference in arrival times of the two isotopes at a given final angle. In the latter method, the identical incident velocities of coexpanded isotopes lead to minor but important differences in their incident kinetic energies, and thus their probability of adsorbing on a sufficiently cold surface, resulting in preferential condensation of a given isotope that depends on the energy of the incident beam. Both of these isotope separation techniques are made possible by the narrow velocity distribution and velocity seeding effect offered only by high-Mach number supersonic beam sources. These experiments underscore the utility of supersonically expanded atomic and molecular beam sources as both extraordinarily precise probes of surface structure and dynamics and as a means for high-throughput, non-dissociative isotopic enrichment methods.

5 Ma of plume source evolution in the Niihau - Kauai - North Arch magmas, Hawaii

NASA Astrophysics Data System (ADS)

Beguelin, P.; Bizimis, M.; McIntosh, E. C.; Cousens, B.; Clague, D. A.

2017-12-01

The Hawaiian islands of Kauai, Niihau and Kaula form a 200 km wide platform across the plume track and record the longest activity record of Hawaiian volcanism ( > 5Ma) [1]. We present new Hf and high precision Pb (MC-ICP-MS with Tl addition) isotope data on 56 previously characterized [2] shield, post-shield and rejuvenated stage lavas from Kauai and Niihau, and on rejuvenated lavas from the North Arch volcanic field, 250 km NE of Kauai. These samples cover nearly the full eruptive history of Kauai and Niihau, and complete an across-plume transect of rejuvenated volcanism, along with published Kaula values [3]. In Nd-Hf-Sr-Pb isotope spaces [2], shield and post-shield lavas from Kauai and Niihau partially overlap the Koolau shield lavas (KSDP, Oahu [4]). Rejuvenated lavas from Kauai and Niihau show a 3 ɛNd units variability and overlap North Arch at a common depleted composition at ɛNd 9 and ɛHf 14. Kauai rejuvenated lavas in part overlap shield and post-shield lavas in Nd-Hf, but extend to lower ɛHf values for a given 87Sr/86Sr and ɛNd. In contrast Niihau rejuvenated lavas have higher ɛHf for a given ɛNd and 87Sr/86Sr compared to all Hawaiian shield lavas. The Niihau data cannot be explained by contribution of a proximal shield stage plume source (e.g. Niihau or Kauai). Instead it is consistent with mixing between a depleted mantle source and an enriched component with high Nd/Hf, Sr/Hf ratios, akin to a carbonatite with low ɛHf and ɛNd, and with their trace element systematics [5] . ICP-MS Pb isotope data for rejuvenated lavas from Kaula, Niihau, Kauai, and North Arch form three distinct arrays, confirming heterogeneity in the rejuvenated source. Our data is consistent with the presence of an enriched, Koolau-like component in the source of shield, post-shield and rejuvenated volcanism in Kauai and Niihau. The rejuvenated sources are heterogeneous across the plume, with the most isotopically depleted values seen in the distal North Arch volcanic field. [1] Garcia et al. (2016) GCA 185 278-301. [2] Cousens & Clague (2015) J. of Pet., egv045 [3] Bizimis et al. (2013) G3, 14(10), 4458-4478. [4] Salters et al. (2006) Contrib. to Min. and Pet. 151(3), 297-312. [5] Dixon et al. (2008) G3 9(9).

Identifying sources of stream water sulfate after a summer drought in the Sleepers River watershed (Vermont, USA) using hydrological, chemical, and isotopic techniques

USGS Publications Warehouse

Mayer, B.; Shanley, J.B.; Bailey, S.W.; Mitchell, M.J.

2010-01-01

In many forested headwater catchments, peak SO42 - concentrations in stream water occur in the late summer or fall following drought potentially resulting in episodic stream acidification. The sources of highly elevated stream water SO42 - concentrations were investigated in a first order stream at the Sleepers River watershed (Vermont, USA) after the particularly dry summer of 2001 using a combination of hydrological, chemical and isotopic approaches. Throughout the summer of 2001 SO42 - concentrations in stream water doubled from ???130 to 270 ??eq/L while flows decreased. Simultaneously increasing Na+ and Ca2+ concentrations and ??34S values increasing from +7??? towards those of bedrock S (???+10.5???) indicated that chemical weathering involving hydrolysis of silicates and oxidation of sulfide minerals in schists and phyllites was the cause for the initial increase in SO42 - concentrations. During re-wetting of the watershed in late September and early October of 2001, increasing stream flows were accompanied by decreasing Na+ and Ca2+ concentrations, but SO42 - concentrations continued to increase up to 568 ??eq/L, indicating that a major source of SO42 - in addition to bedrock weathering contributed to peak SO42 - concentrations. The further increase in SO42 - concentrations coincided with an abrupt decrease of ??34S values in stream water SO42 - from maximum values near +10??? to minimum values near -3???. Soil investigations revealed that some C-horizons in the Spodsols of the watershed contained secondary sulfide minerals with ??34S values near -22???. The shift to negative ??34S values of stream water SO42 - indicates that secondary sulfides in C-horizons were oxidized to SO42 - during the particularly dry summer of 2001. The newly formed SO42 - was transported to the streams during re-wetting of the watershed contributing ???60% of the SO42 - during peak concentrations in the stream water. Thereafter, the contribution of SO42 - from oxidation of secondary sulfides in C-horizons decreased rapidly and pedogenic SO42 - reemerged as a dominant SO42 - source in concert with decreasing SO42 - concentrations in spring of 2002. The study provides evidence that a quantitative assessment of the sources of stream water SO42 - in forested watersheds is possible by combining hydrological, chemical and isotopic techniques, provided that the isotopic compositions of all potential SO42 - sources are distinctly different. ?? 2010 Elsevier Ltd.

Holocene Climate Change in Sub-Alpine Southwestern Alberta: Evidence from Oxygen and Carbon Isotope values of Hogarth Lake Marl.

NASA Astrophysics Data System (ADS)

Matkowski, D.; Patterson, W. P.; Timsic, S.

2017-12-01

A 3.6-meter lake sediment core was recovered from Upper Hogarth Lake, providing proxy evidence for climate variability over the last 11,500 years. The core was sampled at millimeter scale for high-resolution oxygen and carbon isotope values. Large variations (up to 6‰) in the carbon isotope values are attributed to the increasingly dominant role of terrestrial-sourced organic matter over bedrock-sourced DIC during initial lake formation and subsequent changes in regional humidity. Variations (up to 4‰) in oxygen isotope values of the marl are interpreted as representing changes in meteoric water source and regional temperature. The hydrologically-open, fresh-water lake is hosted in Devonian-Carboniferous carbonates, recharged via groundwater, surface flow and precipitation. Marl sediment is generated by the green algae Chara sp., with marl deposition beginning approximately 11,500 cal yBP. Our age model was constructed using tephrochronology and radiocarbon dating of 8 terrestrial plant samples, then calibrated using the University of Minnesota's "Bacon" software. The presence of an ash layer in the core was associated with the Mazama ash layer dated 7,627 ±150 yBP, and was used to support the 14C age model. Sediment deposition is characterized by 3 stages: from the recent, dating back to 11,500 cal yBP, the core is marl dominated, comprising 70% of the 3.6m core. Prior to marl deposition there is a 500-year depositional period of carbonate and allochthonous clastic material. Below 2.65 meters, the sediment consists of fine sand and mud; sourced from the weathering of surrounding bedrock. Isotope data are characterized by 5 distinct periods. 7,800 cal yBP to the end Younger Dryas ( 11,500 cal yBP) exhibits irregular, and generally decreasing, δ13C and δ18O values, with a positive excursion in δ18O values occurring around 9,000 cal yBP. Climate was stable, cool and dry from 5,000-7,000 cal yBP, evidenced by relatively invariant δ13C and δ18O values. The period from 3,000-5,000 cal yBP exhibits decreasing δ13C values and increasing δ18O values, suggesting regional climate warming, possibly accompanied by an increase in humidity. From 3,000 cal yBP to the present, δ13C and δ18O values coincidently decrease, suggesting an increase in regional humidity along with a general cooling trend.

Further analysis of the IRIS iron isotope experiment

NASA Technical Reports Server (NTRS)

Tarle, G.; Ahlen, S. P.; Cartwright, B. G.; Solarz, M.

1980-01-01

The IRIS Fe isotope experiment was extended to atomic charges of Z = 19, with isotopic distributions for 500 events ranging from 18 to 28. Normalization of the detector response functions at Fe-56 produced a single well resolved peak at Sc-45, establishing the resolution and mass scale of the device over the entire charge region. The abundance distributions for the predominantly primary isotopes Ca-40, Fe-54, Fe-56, Ni-58, and Ni-60 do not indicate a large admixture of material with distinctly nonsolar abundances.

Source indicators of humic substances and proto-kerogen - Stable isotope ratios, elemental compositions and electron spin resonance spectra

NASA Technical Reports Server (NTRS)

Stuermer, D. H.; Peters, K. E.; Kaplan, I. R.

1978-01-01

Stable isotope ratios of C, N and H, elemental compositions, and electron spin resonance (ESR) data of humic acids and proto-kerogens from twelve widely varying sampling locations are presented. Humic acids and proto-kerogens from algal sources are more aliphatic and higher in N than those from higher plant sources. Oxygen content appears to represent a measure of maturation, even in Recent sediments, and S content may reflect redox conditions in the environment of deposition. The ESR data indicate that the transformation of humic substances to proto-kerogens in Recent sediments is accompanied by an increase in aromatic character. A combination of stable carbon isotope ratio and H/C ratio may be a simple but reliable source indicator which allows differentiation of marine-derived from terrestrially-derived organic matter. The stable nitrogen isotope ratios are useful indicators of nitrogen nutrient source. Deuterium/hydrogen isotope ratios appear to reflect variations in meteoric waters and are not reliable source indicators.

Nitrate source apportionment using a combined dual isotope, chemical and bacterial property, and Bayesian model approach in river systems

NASA Astrophysics Data System (ADS)

Xia, Yongqiu; Li, Yuefei; Zhang, Xinyu; Yan, Xiaoyuan

2017-01-01

Nitrate (NO3-) pollution is a serious problem worldwide, particularly in countries with intensive agricultural and population activities. Previous studies have used δ15N-NO3- and δ18O-NO3- to determine the NO3- sources in rivers. However, this approach is subject to substantial uncertainties and limitations because of the numerous NO3- sources, the wide isotopic ranges, and the existing isotopic fractionations. In this study, we outline a combined procedure for improving the determination of NO3- sources in a paddy agriculture-urban gradient watershed in eastern China. First, the main sources of NO3- in the Qinhuai River were examined by the dual-isotope biplot approach, in which we narrowed the isotope ranges using site-specific isotopic results. Next, the bacterial groups and chemical properties of the river water were analyzed to verify these sources. Finally, we introduced a Bayesian model to apportion the spatiotemporal variations of the NO3- sources. Denitrification was first incorporated into the Bayesian model because denitrification plays an important role in the nitrogen pathway. The results showed that fertilizer contributed large amounts of NO3- to the surface water in traditional agricultural regions, whereas manure effluents were the dominant NO3- source in intensified agricultural regions, especially during the wet seasons. Sewage effluents were important in all three land uses and exhibited great differences between the dry season and the wet season. This combined analysis quantitatively delineates the proportion of NO3- sources from paddy agriculture to urban river water for both dry and wet seasons and incorporates isotopic fractionation and uncertainties in the source compositions.

Chemical and isotopic signature of old groundwater and magmatic solutes in a Costa Rican rain forest: Evidence from carbon, helium, and chlorine

NASA Astrophysics Data System (ADS)

Genereux, David P.; Webb, Mathew; Solomon, D. Kip

2009-08-01

C, He, and Cl concentrations and isotopes in groundwater and surface water in a lowland Costa Rican rain forest are consistent with the mixing of two distinct groundwaters: (1) high-solute bedrock groundwater representing interbasin groundwater flow (IGF) into the rain forest and (2) low-solute local groundwater recharged in the lowlands. In bedrock groundwater, high δ13C (-4.89‰), low 14C (7.98 pM), high R/RA for He (6.88), and low 36Cl/Cl (17 × 10-15) suggest that elevated tracer concentrations are derived from magmatic outgassing and/or weathering of volcanic rock beneath nearby Volcan Barva. In local groundwater, the magmatic signature is absent, and data suggest atmospheric sources for He and Cl and a biogenic soil gas CO2 source for dissolved inorganic carbon. Dating of 14C suggests that the age of bedrock groundwater is 2400-4000 years (most likely at the lower end of the range). Local groundwater has 14C > 100 pM, indicating the presence of "bomb carbon" and thus ages less than ˜55 years. Overall, data are consistent with a conceptual hydrologic model originally proposed on the basis of water budget and major ion data: (1) large variation in solute concentrations can be explained by mixing of the two distinct groundwaters, (2) bedrock groundwater is much older than local groundwater, (3) elevated solute concentrations in bedrock groundwater are derived from volcanic fluids and/or rock, and (4) local groundwater has not interacted with volcanic rock. Tracers with different capabilities converge on the same hydrologic interpretation. Also, transport of magmatic CO2 into the lowland rain forest via IGF seems to be significant relative to other large ecosystem-level carbon fluxes.

Comparison of Forced ENSO-Like Hydrological Expressions in Simulations of the Preindustrial and Mid-Holocene

NASA Technical Reports Server (NTRS)

Lewis, Sophie C.; LeGrande, Allegra N.; Schmidt, Gavin A.; Kelley, Maxwell

2014-01-01

Using the water isotope- and vapor source distribution (VSD) tracer-enabled Goddard Institute for Space Studies ModelE-R, we examine changing El Nino-Southern Oscillation (ENSO)-like expressions in the hydrological cycle in a suite of model experiments. We apply strong surface temperature anomalies associated with composite observed El Nino and La Nina events as surface boundary conditions to preindustrial and mid-Holocene model experiments in order to investigate ENSO-like expressions in the hydrological cycle under varying boundary conditions. We find distinct simulated hydrological anomalies associated with El Nino-like ("ENSOWARM") and La Nina-like ("ENSOCOOL") conditions, and the region-specific VSD tracers show hydrological differences across the Pacific basin between El Nino-like and La Nina-like events. The application of ENSOCOOL forcings does not produce climatological anomalies that represent the equal but opposite impacts of the ENSOWARM experiment, as the isotopic anomalies associated with ENSOWARM conditions are generally stronger than with ENSOCOOL and the spatial patterns of change distinct. Also, when the same ENSO-like surface temperature anomalies are imposed on the mid-Holocene, the hydrological response is muted, relative to the preindustrial. Mid-Holocene changes in moisture sources to the analyzed regions across the Pacific reveal potentially complex relationships between ENSO-like conditions and boundary conditions. Given the complex impacts of ENSO-like conditions on various aspects of the hydrological cycle, we suggest that proxy record insights into paleo-ENSO variability are most likely to be robust when synthesized from a network of many spatially diverse archives, which can account for the potential nonstationarity of ENSO teleconnections under different boundary conditions.

Identification of anthropogenic and natural inputs of sulfate into a karstic coastal groundwater system in northeast China: evidence from major ions, δ13CDIC and δ34SSO4

NASA Astrophysics Data System (ADS)

Han, Dongmei; Song, Xianfang; Currell, Matthew J.

2016-05-01

The hydrogeochemical processes controlling groundwater evolution in the Daweijia area of Dalian, northeast China, were characterised using hydrochemistry and isotopes of carbon and sulfur (δ13CDIC and δ34SSO4). The aim was to distinguish anthropogenic impacts as distinct from natural processes, with a particular focus on sulfate, which is found at elevated levels (range: 54.4 to 368.8 mg L-1; mean: 174.4 mg L-1) in fresh and brackish groundwater. The current investigation reveals minor seawater intrusion impact (not exceeding 5 % of the overall solute load), in contrast with extensive impacts observed in 1982 during the height of intensive abstraction. This indicates that measures to restrict groundwater abstraction have been effective. However, hydrochemical facies analysis shows that the groundwater remains in a state of ongoing hydrochemical evolution (towards Ca-Cl type water) and quality degradation (increasing nitrate and sulfate concentrations). The wide range of NO3 concentrations (74.7-579 mg L-1) in the Quaternary aquifer indicates considerable input of fertilisers and/or leakage from septic systems. Both δ13C (-14.5 to -5.9 permil) and δ34SSO4 (+5.4 to +13.1 permil) values in groundwater show increasing trends along groundwater flow paths. While carbonate minerals may contribute to increasing δ13CDIC and δ34SSO4 values in deep karstic groundwater, high loads of agricultural fertilisers reaching the aquifer via irrigation return flow are likely the main source of the dissolved sulfate in Quaternary groundwater, as shown by distinctive isotopic ratios and a lack of evidence for other sources in the major ion chemistry. According to isotope mass balance calculations, the fertiliser contribution to overall sulfate has reached an average of 62.1 % in the Quaternary aquifer, which has a strong hydraulic connection to the underlying carbonate aquifer. The results point to an alarming level of impact from the local intensive agriculture on the groundwater system, a widespread problem throughout China.

Identification of anthropogenic and natural inputs of sulfate into a karstic coastal groundwater system in northeast China: evidence from major ions, δ13CDIC and δ34SSO4

NASA Astrophysics Data System (ADS)

Han, D.; Song, X.; Currell, M. J.

2015-11-01

The hydrogeochemical processes controlling groundwater evolution in the Daweijia area of Dalian, northeast China, were characterized using hydrochemistry and isotopes of carbon and sulfur (δ13CDIC and δ34SSO4). The aim was to distinguish anthropogenic impacts as distinct from natural processes, with a particular focus on sulfate, which is found at elevated levels (range: 54.4 to 368.8 mg L-1; mean: 174.4 mg L-1) in fresh and brackish groundwater. The current investigation reveals minor seawater intrusion impact (not exceeding 5 % of overall solute load), in contrast with extensive impacts observed in 1982 during the height of intensive abstraction. This indicates that measures to restrict groundwater abstraction have been effective. However, hydrochemical facies analysis shows that the groundwater remains in a state of ongoing hydrochemical evolution (towards Ca-Cl type water) and quality degradation (increasing nitrate and sulphate concentrations). The wide range of NO3 concentrations (74.7-579 mg L-1) in the Quaternary aquifer indicates considerable input of fertilizers and/or leakage from septic systems. Both δ13C (-14.5 to -5.9 ‰) and δ34SSO4 (+5.4-+13.1 ‰) values in groundwater show increasing trends along groundwater flow paths. While carbonate minerals may contribute to increasing δ13CDIC and δ34SSO4 values in deep karstic groundwater, high loads of agricultural fertilizers reaching the aquifer via irrigation return flow are likely the main source of the dissolved sulfate in Quaternary groundwater, as shown by distinctive isotopic ratios and a lack of evidence for other sources in the major ion chemistry. According to isotope mass balance calculations, the fertilizer contribution to overall sulfate has reached an average of 62.1 % in the Quaternary aquifer, which has a strong hydraulic connection to the underlying carbonate aquifer. The results point to an alarming level of impact from the local intensive agriculture on the groundwater system, a widespread problem throughout China.

Spatial distribution and controlling factors of stable isotopes in meteoric waters on the Tibetan Plateau: Implications for paleoelevation reconstruction

NASA Astrophysics Data System (ADS)

Li, Lin; Garzione, Carmala N.

2017-02-01

Debates persist about the interpretations of stable isotope based proxies for the surface uplift of the central-northern Tibetan Plateau. These disputes arise from the uncertain relationship between elevation and the δ18 O values of meteoric waters, based on modern patterns of isotopes in precipitation and surface waters. We present a large river water data set (1,340 samples) covering most parts of the Tibetan Plateau to characterize the spatial variability and controlling factors of their isotopic compositions. Compared with the amount-weighted mean annual oxygen isotopic values of precipitation, we conclude that river water is a good substitute for isotopic studies of precipitation in the high flat (e.g., elevation >3,300 m) interior of the Tibetan Plateau in the mean annual timescale. We construct, for the first time based on field data, contour maps of isotopic variations of meteoric waters (δ18 O, δD and d-excess) on the Tibetan Plateau. In the marginal mountainous regions of the Plateau, especially the southern through eastern margins, the δ18 O and δD values of river waters decrease with increasing mean catchment elevation, which can be modeled as a Rayleigh distillation process. However, in the interior of the Plateau, northward increasing trends in δ18 O and δD values are pronounced and present robust linear relations; d-excess values are lower than the marginal regions and exhibit distinct contrasts between the eastern (8 ‰- 12 ‰) and western (<8‰) Plateau. We suggest that these isotopic features of river waters in the interior of the Tibetan Plateau result from the combined effects of: 1) mixing of different moisture sources transported by the South Asian monsoon and Westerly winds; 2) contribution of moisture from recycled surface water; and 3) sub-cloud evaporation. We further provide a sub-cloud evaporation modified Rayleigh distillation and mixing model to simulate the isotopic variations in the western Plateau. Results of this work suggest that stable isotope-based paleoaltimetry studies are reliable in the southern through eastern Plateau margins; towards the central-northern Plateau, this method cannot be applied without additional constraints and/or large uncertainties.

Mantle amphibole control on arc and within-plate chemical signatures: Quaternary lavas from Kurdistan Province, Iran

NASA Astrophysics Data System (ADS)

Kheirkhah, M.; Allen, M. B.; Neill, I.; Emami, M. H.; McLeod, C.

2012-04-01

New analyses of Quaternary lavas from Kurdistan Province in west Iran shed light on the nature of collision zone magmatism. The rocks are from the Turkish-Iranian plateau within the Arabia-Eurasia collision. Compositions are typically basanite, hawaiite and alkali basalt. Sr-Nd isotope values are close to BSE, which is similar to Quaternary alkali basalts of NW Iran, but distinct from a depleted source melting under Mount Ararat. The chemical signatures suggests variable melting of two distinct sources. One inferred source produced melts with La/Nb from~3.5 to~1.2, which we model as the result of depletion of amphibole during ≤1% melting in the garnet stability field. We infer phlogopite in the source of potassic lavas from Takab. Lithosphere delamination or slab break-off mechanisms for triggering melting are problematic, as the lithosphere is~150-200km thick. It is possible that the negative dT/dP section of the amphibole peridotite solidus was crossed as a result of lithospheric thickening in the collision zone. This explanation is conditional upon the mantle source being weakly hydrated and so only containing a small proportion of amphibole, which can be exhausted during small degrees of partial melting. Our model maybe viable for other magmatic areas within orogenic plateaux, e.g. northern Tibet. Depletion of mantle amphibole may also help explain larger scale transitions from arc to within-plate chemistry in orogens, such as the Palaeogene Arabia-Eurasia system.

Partitioning Ecosystem Respiration Using Stable Carbon Isotopes in a Mixed C3 Annual Grassland

NASA Astrophysics Data System (ADS)

Tu, K. P.

2001-12-01

The stable carbon isotope ratio (δ 13C) of respired CO2 has been used to partition soil respiration into root and microbial components by exploiting the different δ 13C signals from C3 plants growing in a previously C4 dominated system (Rouchette, Angers and Flanagan 1999). We extend this approach and present data that attempts to partition ecosystem respiration using δ 13C analyses of all of the ecosystem compartments in a mixed C3 annual grassland that has not experienced recent C4 inputs. From December 2000 to February 2001 we measured δ 13C-CO2 respired from leaves, roots and sieved soil collected from a winter-active grassland near Ione, California. Two-source mixing models were used to calculate the contribution of each source to total system respiration by comparing their isotope signals to those from whole ecosystem respiration and soil surface efflux. Isotope ratios were measured on 10mL air samples in septum-capped vials using a Finnigan MAT Delta PlusXL IRMS/Gas Bench II interfaced to an autosampler (after Tu et al. 2001). The vials were filled with sample air in the field using a double-holed needle connected in a closed loop to a LI-6200 IRGA and a bottle containing the isolated samples (leaf, root, sieved soil, etc.). Leaves were clipped at ground level and roots and soil were separated by sieving soil cores. Sample δ 13CO2 signatures were determined by plotting the change in δ 13C against the inverse of CO2 concentration. On average, CO2 respired from sieved soil (-27.4o/oo+/-1.4) was slightly more depleted than that from leaves (-27.2o/oo+/-0.5), but much more depleted than the whole ecosystem (-24.9o/oo+/-0.6), the soil surface efflux (-23.8o/oo+/-0.9), and plant roots (-20.5o/oo+/-0.8). Based on these isotope values, leaf respiration comprised 33% of ecosystem respiration with 36% from roots and 31% from soil microbial respiration. Thus, over two-thirds of ecosystem respiration was autotrophic (plant-based) in origin with roughly one-third being heterotrophic. Belowground respiration, comprised of both autotrophic (root) and heterotrophic (microbial) components, accounted for nearly two-thirds of total ecosystem respiration. Root and microbial respiration each contributed to nearly half of total belowground respiration (53% and 47%, respectively). Similarly, plant respiration was divided nearly equally between that from roots (52%) and leaves (48%). Partitioning using natural abundance stable carbon isotope ratios was made possible because of the relatively large differences in δ 13C values among the various sources in this entirely C3 system. To our knowledge, such large isotopic differences in respired CO2 among different plant tissues and belowground components have not been documented before. Further research is needed to determine how such differences may arise and to establish if similar differences exist in other ecosystems or at different times of the growing season. Our results also imply that interpretation of above-canopy Keeling plot intercepts may be complicated by both multiple (and isotopically distinct) sources and by isotopic fractionation that occurs either during the respiration process itself or during the transfer of carbon compounds prior to respiration.

New isotopic evidence for the origin of groundwater from the Nubian Sandstone Aquifer in the Negev, Israel

USGS Publications Warehouse

Vengosh, A.; Hening, S.; Ganor, J.; Mayer, B.; Weyhenmeyer, C.E.; Bullen, T.D.; Paytan, A.

2007-01-01

The geochemistry and isotopic composition (H, O, S, Osulfate, C, Sr) of groundwater from the Nubian Sandstone (Kurnub Group) aquifer in the Negev, Israel, were investigated in an attempt to reconstruct the origin of the water and solutes, evaluate modes of water-rock interactions, and determine mean residence times of the water. The results indicate multiple recharge events into the Nubian sandstone aquifer characterized by distinctive isotope signatures and deuterium excess values. In the northeastern Negev, groundwater was identified with deuterium excess values of ???16???, which suggests local recharge via unconfined areas of the aquifer in the Negev anticline systems. The ??18OH2O and ??2H values (-6.5??? and -35.4???) of this groundwater are higher than those of groundwater in the Sinai Peninsula and southern Arava valley (-7.5??? and -48.3???) that likewise have lower deuterium excess values of ???10???. Based on the geochemical differences between groundwater in the unconfined and confined zones of the aquifer, a conceptual geochemical model for the evolution of the groundwater in the Nubian sandstone aquifer has been reconstructed. The isotopic composition of shallow groundwater from the unconfined zone indicates that during recharge oxidation of pyrite to SO4 (??34SSO4 ???-13???; ??18OSO4 ???+7.7???) and dissolution of CaCO3 (87Sr/86Sr ???0.70787; ??13CDIC = -3.7???) occur. In the confined zone of the aquifer, bacterial SO4 reduction removes a significant part of dissolved SO42 -, thereby modifying its isotopic composition (??34SSO4 ???-2???; ??18OSO4 ???+8.5???) and liberating dissolved inorganic C that contains little or no radiocarbon (14C-free) with low ??13CDIC values (<-12???). In addition to local recharge, the Sr and S isotopic data revealed contribution of external groundwater sources to the Nubian Sandstone aquifer, resulting in further modifications of the groundwater chemical and isotopic signatures. In the northeastern Negev, it is shown that SO4-rich groundwater from the underlying Jurassic aquifer contributes significantly to the salt budget of the Nubian Sandstone aquifer. The unique chemical and isotopic composition of the Jurassic groundwater (??34SSO4 ??? +14???; ??18OSO4 ??? 14???; 87Sr/86Sr ???0.70764) is interpreted as reflecting dissolution of Late Triassic marine gypsum deposits. In the southern Arava Valley the authors postulate that SO4-rich groundwater with distinctively high Br/Cl (3 ?? 10-3) low 87Sr/86Sr (0.70734), and high ??34SSO4 values (+15???) is derived from mixing with underlying brines from the Paleozoic units. The radiocarbon measurements reveal low 14C activities (0.2-5.8 pmc) in both the northeastern Negev and southern Arava Valley. Taking into account dissolution of carbonate rocks and bacterial SO4 reduction in the unconfined area, estimated mean residence times of groundwater in the confined zone in the northeastern Negev are on the order of 21-38 ka, which suggests recharge predominantly during the last glacial period. The 14C signal in groundwater from the southern Arava Valley is equally low but due to evidence for mixing with external water sources the residence time estimates are questionable. ?? 2007 Elsevier Ltd. All rights reserved.

Source Signature of Sr Isotopes in Fluids Emitting From Mud volcanoes in Taiwan

NASA Astrophysics Data System (ADS)

Chung, C.; You, C.; Chao, H.

2003-12-01

Located at the boundary between the Philippine Sea Plate and the Asia Continental Plate, abundance of mud volcanoes were erupted on land in Taiwan. According to their occurrences and associated tectonic settings, these mud volcanoes were classified into four groupies. The group (I) mud volcanoes are located in the western coastal plane, whereas group (II) and (III) are situated near the Kutinkung anticline axis and the Chishan fault respectively. The group (IV) mud volcanoes are discovered at the Coastal Range. Although there are numerous studies focused on morphology, possible fluid migration paths and sources are poorly understood. We have collected and analyzed major ions and Sr isotopic ratios in fluids separated from various mud volcanoes in Taiwan. Chemical contents of these fluids were measured by IC and the emitted gasses were analyzed by GC. The Sr concentrations in these fluids were determined using AA and the isotopic compositions were analyzed by TIMS. The dominated ions in fluids are Na and Cl which account for 98% of dissolved materials. All fluids show similar Na/Cl ratios(0.7-0.8), slightly higher than seawater but each group has unique Sr isotopic signature. Waters expelled from group I mud volcanoes featured with low salinity and high Sr isotopic ratios ranged from 0.71150 to 0.71175. Groups II and III were outcroped in the Kutinkung formation but show distinctive chemical compositions. Group II fluids have four times Cl concentrations(358-522mM) compared with those of group III(85-162mM). The latter fluids appear to be more radiogenic(0.71012- 0.71075) indicating possible influence due to water-rock interactions. Low 87Sr/86Sr(0.70692-0.70939) is typical characteristic of mud volcano fluids in group IV where large Mg and K depletion were discovered, suggesting effects due to sediment diagenetic processes. The chemical compositions of mud volcano associated gasses show similar distribution pattern. The major gas constituents in mud volcano zones II and III are methane(>80%), air(1-10%) and carbon dioxide(1-5%). Gases collected from zone IV display significantly higher air content(5-20%) with low carbon dioxide(<0.2%). These results are useful for gaining a better understanding of mud volcano fluid sources.

Thallium as a tracer of fluid-rock interaction in the shallow Mariana forearc

NASA Astrophysics Data System (ADS)

Nielsen, Sune G.; Klein, Frieder; Kading, Tristan; Blusztajn, Jerzy; Wickham, Katie

2015-11-01

Fluids driven off the subducting Pacific plate infiltrate the shallow Mariana forearc and lead to extensive serpentinization of mantle peridotite. However, the sources, pathways, and chemical modifications of ascending, slab-derived fluids remain poorly constrained and controversial. In this study, we use thallium (Tl) concentrations and isotopic ratios of serpentinized peridotite and rodingitized diabase from the South Chamorro and Conical Seamounts to discriminate between potential fluid sources with distinct Tl isotope compositions. Serpentinite samples from the Mariana forearc all display ε205 Tl > - 0.5 (where ε205 Tl = 10 , 000 × (205Tl /Tl203sample -205Tl /SRM 997 203Tl ) / (205Tl / SRM 997 203Tl )), which is significantly enriched in 205Tl compared to the normal mantle (ε205 Tl = - 2). Given that high temperature hydrothermal processes do not impart significant Tl isotope fractionation, the isotope compositions of the serpentinites must reflect that of the serpentinizing fluid. Pelagic sediments are the only known slab component that consistently displays ε205 Tl > - 0.5 and, therefore, we interpret the heavy Tl isotope signatures as signifying that the serpentinizing fluids were derived from subducting pelagic sediments. A rodingitized diabase from Conical Seamount was found to have an ε205 Tl of 0.8, suggesting that sediment-sourced serpentinization fluids could also affect diabase and other mafic lithologies in the shallow Mariana forearc. Forearc rodingitization of diabase led to a strong depletion in Tl content and a virtually complete loss of K, Na and Rb. The chemical composition of hybrid fluids resulting from serpentinization of harzburgite with concomitant rodingitization of diabase can be highly alkaline, depleted in Si, yet enriched in Ca, Na, K, and Rb, which is consistent with the composition of fluids emanating from mud volcanoes in the Mariana forearc. Our study suggests that fluid-rock interactions between sedimentary, mafic, and ultramafic lithologies are strongly interconnected even in the shallowest parts of subduction zones. We conclude that transfer of fluids and dissolved elements at temperatures and pressures below 400 °C and 1 GPa, respectively, must be taken into account when elemental budgets and mass transfer between the subducting plate, the forearc, the deep mantle and the ocean are evaluated.

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.

Optimizing isotope substitution in graphene for thermal conductivity minimization by genetic algorithm driven molecular simulations

NASA Astrophysics Data System (ADS)

Davies, Michael; Ganapathysubramanian, Baskar; Balasubramanian, Ganesh

2017-03-01

We present results from a computational framework integrating genetic algorithm and molecular dynamics simulations to systematically design isotope engineered graphene structures for reduced thermal conductivity. In addition to the effect of mass disorder, our results reveal the importance of atomic distribution on thermal conductivity for the same isotopic concentration. Distinct groups of isotope-substituted graphene sheets are identified based on the atomic composition and distribution. Our results show that in structures with equiatomic compositions, the enhanced scattering by lattice vibrations results in lower thermal conductivities due to the absence of isotopic clusters.

Apparatus and method for detecting gamma radiation

DOEpatents

Sigg, R.A.

1994-12-13

A high efficiency radiation detector is disclosed for measuring X-ray and gamma radiation from small-volume, low-activity liquid samples with an overall uncertainty better than 0.7% (one sigma SD). The radiation detector includes a hyperpure germanium well detector, a collimator, and a reference source. The well detector monitors gamma radiation emitted by the reference source and a radioactive isotope or isotopes in a sample source. The radiation from the reference source is collimated to avoid attenuation of reference source gamma radiation by the sample. Signals from the well detector are processed and stored, and the stored data is analyzed to determine the radioactive isotope(s) content of the sample. Minor self-attenuation corrections are calculated from chemical composition data. 4 figures.

The Amazon-Laurentian connection as viewed from the Middle Proterozoic rocks in the central Andes, western Bolivia and northern Chile

USGS Publications Warehouse

Tosdal, R.M.

1996-01-01

Middle Proterozoic rocks underlying the Andes in western Bolivia, western Argentina, and northern Chile and Early Proterozoic rocks of the Arequipa massif in southern Peru?? from the Arequipa-Antofalla craton. These rocks are discontinuously exposed beneath Mesozoic and Cenozoic rocks, but abundant crystalline clasts in Tertiary sedimentary rocks in the western altiplano allow indirect samples of the craton. Near Berenguela, western Bolivia, the Oligocene and Miocene Mauri Formation contains boulders of granodiorite augen gneiss (1171??20 Ma and 1158??12 Ma; U-Pb zircon), quartzose gneiss and granofels that are inferred to have arkosic protoliths (1100 Ma source region; U-Pb zircon), quartzofeldspathic and mafic orthogneisses that have amphibolite- and granulite-facies metamorphic mineral assemblages (???1080 Ma metamorphism; U-Pb zircon), and undeformed granitic rocks of Phanerozoic(?) age. The Middle Proterozoic crystalline rocks from Berenguela and elsewhere in western Bolivia and from the Middle Proterozoic Bele??n Schist in northern Chile generally have present-day low 206Pb/204Pb ( 15.57), and elevated 208Pb/204Pb (37.2 to 50.7) indicative of high time-averaged Th/U values. The Middle Proterozoic rocks in general have higher presentday 206Pb/204Pb values than those of the Early Proterozoic rocks of the Arequipa massif (206Pb/204Pb between 16.1 and 17.1) but lower than rocks of the southern Arequipa-Antofalla craton (206Pb/204Pb> 18.5), a difference inferred to reflect Grenvillian granulite metamorphism. The Pb isotopic compositions for the various Proterozoic rocks lie on common Pb isotopic growth curves, implying that Pb incorporated in rocks composing the Arequipa-Antofalla craton was extracted from a similar evolving Pb isotopic reservoir. Evidently, the craton has been a coherent terrane since the Middle Proterozoic. Moreover, the Pb isotopic compositions for the Arequipa-Antofalla craton overlap those of the Amazon craton, thereby supporting a link between these cratons and seemingly precluding part of the Arequipa-Antofalla craton from being a detached fragment of another craton such as eastern Laurentia, which has been characterized by a different U/Pb history. Pb isotopic compositions for the Arequipa-Antofalla craton are, furthermore, distinct from those of the Proterozoic basement in the Precordillera terrane, western Argentina, indicating a Pb isotopic and presumably a tectonic boundary between them. The Pb isotopic compositions for the Precordillera basement are similar to those of eastern Laurentia, and support other data indicating that these rocks are a detached fragment of North America. Finally, the distinct Pb isotopic evolution history of the Arequipa-Antofalla craton and eastern Laurentia require minor modification to tectonic models linking eastern North America-Scotland to the oroclinal bend in western South America.

Integrating Stomach Content and Stable Isotope Analyses to Quantify the Diets of Pygoscelid Penguins

PubMed Central

Polito, Michael J.; Trivelpiece, Wayne Z.; Karnovsky, Nina J.; Ng, Elizabeth; Patterson, William P.; Emslie, Steven D.

2011-01-01

Stomach content analysis (SCA) and more recently stable isotope analysis (SIA) integrated with isotopic mixing models have become common methods for dietary studies and provide insight into the foraging ecology of seabirds. However, both methods have drawbacks and biases that may result in difficulties in quantifying inter-annual and species-specific differences in diets. We used these two methods to simultaneously quantify the chick-rearing diet of Chinstrap (Pygoscelis antarctica) and Gentoo (P. papua) penguins and highlight methods of integrating SCA data to increase accuracy of diet composition estimates using SIA. SCA biomass estimates were highly variable and underestimated the importance of soft-bodied prey such as fish. Two-source, isotopic mixing model predictions were less variable and identified inter-annual and species-specific differences in the relative amounts of fish and krill in penguin diets not readily apparent using SCA. In contrast, multi-source isotopic mixing models had difficulty estimating the dietary contribution of fish species occupying similar trophic levels without refinement using SCA-derived otolith data. Overall, our ability to track inter-annual and species-specific differences in penguin diets using SIA was enhanced by integrating SCA data to isotopic mixing modes in three ways: 1) selecting appropriate prey sources, 2) weighting combinations of isotopically similar prey in two-source mixing models and 3) refining predicted contributions of isotopically similar prey in multi-source models. PMID:22053199

Hf-Nd Isotopic Correlation in the Deccan Flood Basalt Province

NASA Astrophysics Data System (ADS)

Saha, A.; Basu, A. R.; Barling, J.; Anbar, A. D.; Hooper, P. R.

2001-12-01

Hafnium isotopes along with other isotopic and geochemical characteristics, including incompatible trace elements, of several of the lower formations of the Deccan Flood Basalt Province were analyzed to characterize petrogenesis of different tholeiitic lava suites, especially with respect to potential mantle and crustal sources. The rare earth elements of the different formations (from top to bottom- Mahabaleshwar, Ambenali, Bushe, Khandala and Neral) all show an LREE-enriched signature, concentrations varying between 30 to 60 times chondrite for La. (La/Lu)n values range from 4.1 to above 8 with the exception of Ambenali, which has a less LREE-enriched signature with (La/Lu)n values ranging between 3.6 to 5.3. Hafnium isotopic data of the lower formations of the Deccan show initial \\epsilonHf(T) values covering a range from -3 to -28. 176Lu/177Hf varies between 0.20 to 0.70. f(Lu/Hf) varies within a narrow range, between -0.90 to -0.97 while f(Sm/Nd) ranges from -0.84 to -0.86. Bushe gives the lowest range of \\epsilonHf(T) from -21 to -28 with the corresponding \\epsilonNd(T) varying between -4.0 and -16.9, while Khandala for almost the same range of neodymium isotopic values has \\epsilonHf(T) between -11 and -15. The \\epsilonHf(T) values of Neral is in between those of Khandala and Bushe, around -19. Ambenali, has the narrowest range with \\epsilonHf(T) of -3 and \\epsilonNd(T) between 3 and 5. The Ambenali suite reflects the least contaminated of the Deccan suite of lavas as analyzed here and previously confirmed by other isotopic studies. In Hf-Nd isotope correlation plot, the lower Deccan formations of Neral, Khandala and Bushe define individual subparallel arrays that are shallower than the oceanic basalt array and the overall terrestrial array, including the crustal array, although the bulk of the lower formation data fall within the crustal array of Vervoort et al (1999). From these subparallel Hf-Nd arrays, it is evident that the other end-members contributing to the Ambenali-type source magmas are distinctly different for each of these lava suites, and can be characterized by their \\epsilonHf(T) values as mentioned above. Although these end-members are discernible in \\epsilonNd vs \\epsilonSr plot (e.g., Peng et al, 1994) of previous studies, our new Hf-isotopic data provide clear evidence of major contributions from the ancient Indian continental crustal reservoirs in the petrogenesis of the lower lava formations of the Deccan Flood Basalt Province.

The carbon isotope biogeochemistry of the individual hydrocarbons in bat guano and the ecology of insectivorous bats in the region of Carlsbad, New Mexico

NASA Technical Reports Server (NTRS)

Desmarais, D. J.; Mitchell, J. M.; Meinschein, W. G.; Hayes, J. M.

1980-01-01

The structures and C-13 contents of individual alkanes extracted from bat guano found in the Carlsbad region of New Mexico can be related to both the photosynthetic pathways of the local plants and the feeding habits of the insects that support the bats. Carbon isotopic analyses of the 62 most important plant species in the Pecos River Valley, the most significant feeding area for the Carlsbad bats, reveal the presence of 29 species with C3 photosynthesis and 33 species, mostly grasses, with C4 photosynthesis. Although the abundances of nonagricultural C3 and C4 plants are similar, alfalfa and cotton, both C3 plants, constitute over 95 per cent of the crop biomass. The molecular composition of the bat guano hydrocarbons is fully consistent with an insect origin. Two isotopically distinct groups of insect branched alkanes were discerned. These two groups of alkanes derived from two chemotaxonomically distinct populations of insects possessing distinctly different feeding habits. It is likely that one population grazes predominantly on crops whereas the other population prefers native vegetation. This and other isotopic evidence supports the notion that crop pests constitute a major percentage of the bats' diet.

Application of carbon isotope stratigraphy to late miocene shallow marine sediments, new zealand.

PubMed

Loutit, T S; Kennett, J P

1979-06-15

A distinct (0.5 per mil) carbon-13/carbon-12 isotopic shift in the light direction has been identified in a shallow marine sedimentary sequence of Late Miocene age at Blind River, New Zealand, and correlated with a similar shift in Late Miocene Deep Sea Drilling Project sequences throughout the Indo-Pacific. A dated piston core provides an age for the shift of 6.2 +/- 0.1 million years. Correlations based on the carbon isotopic change require a revision of the previously established magnetostratigraphy at Blind River. The carbon shift at Blind River occurs between 6.2 and 6.3 +/- 0.1 million years before present. A new chronology provides an age for the evolutionary first appearance datum of Globorotalia conomiozea at 6.1 +/- 0.1 million years, the beginning of a distinct latest Miocene cooling event associated with the Kapitean stage at 6.2 +/- 0.1 million years, and the beginning of a distinct shallowing of water depths at 6.1 +/- 0.1 million years. The Miocene-Pliocene boundary as recognized in New Zealand is now dated at 5.3 +/- 0.1 million years. Extension of carbon isotope stratigraphy to other shallow Late Miocene sequences should provide an important datum for international correlation of Late Miocene shallow and deep marine sequences.

The influence of low latitude forcing on European Ice sheet dynamics

NASA Astrophysics Data System (ADS)

Kaboth, Stefanie; Bahr, André; Lourens, Lucas J.

2017-04-01

Distinct mid-glacial δ18O enrichment events found at Site U1386 in the Gulf of Cadiz during Marine Isotope Stages 6 and 8 represent a striking feature absent in most deep-sea benthic δ18O records studied worldwide. These δ18O enrichment events are closely related to periods of maximum precession and aligned with previous findings from the Mediterranean and Red Seas. Here we present paired planktic and benthic stable isotope (δ18O and δ13C) and Mg/Ca-based temperature records of Site U1386 of the last 300.000 years. Our results show that these δ18O enrichment events are recorded in both subsurface and bottom water masses and pre-date the largest cooling events along the Iberian Margin and associated European sourced meltwater pulses of the Drenthe and Fuhne major ice-sheet advances, suggesting that they instead correspond to periods of maximum ice volume extend in Europe.

Formation and Preservation of the Depleted and Enriched Shergottite Isotopic Reservoirs in a Convecting Martian Mantle

NASA Technical Reports Server (NTRS)

Kiefer, Walter S.; Jones, John H.

2015-01-01

There is compelling isotopic and crater density evidence for geologically recent volcanism on Mars, in the last 100-200 million years and possibly in the last 50 million years. This volcanism is due to adiabatic decompression melting and thus requires some type of present-day convective upwelling in the martian mantle. On the other hand, martian meteorites preserve evidence for at least 3 distinct radiogenic isotopic reservoirs. Anomalies in short-lived isotopic systems (Sm-146, Nd-142, Hf-182, W-182) require that these reservoirs must have developed in the first 50 to 100 million years of Solar System history. The long-term preservation of chemically distinct reservoirs has sometimes been interpreted as evidence for the absence of mantle convection and convective mixing on Mars for most of martian history, a conclusion which is at odds with the evidence for young volcanism. This apparent paradox can be resolved by recognizing that a variety of processes, including both inefficient mantle mixing and geographic separation of isotopic reservoirs, may preserve isotopic heterogeneity on Mars in an actively convecting mantle. Here, we focus on the formation and preservation of the depleted and enriched isotopic and trace element reservoirs in the shergottites. In particular, we explore the possible roles of processes such as chemical diffusion and metasomatism in dikes and magma chambers for creating the isotopically enriched shergottites. We also consider processes that may preserve the enriched reservoir against convective mixing for most of martian history.

New Hafnium Isotope and Trace Element Constraints on the Role of a Plume in Genesis of the Eastern Snake River Plain Basalts, Idaho

NASA Astrophysics Data System (ADS)

Taylor, R. D.; Reid, M. R.; Blichert-Toft, J.

2009-12-01

Bimodal volcanism associated with the eastern Snake River Plain (ESRP)-Yellowstone Plateau province has persisted since approximately 16 Ma. A time-transgressive track of rhyolitic eruptions which young progressively to the east and parallel the motion of the North American plate are overlain by younger basalts with no age progression. Interpretations for the origin of these basalts range from a thermo-chemical mantle plume to incipient melting of the shallow upper mantle, and remain controversial. The enigmatic ESRP basalts are characterized by high 3He/4He, diagnostic of a plume source, but also by lithophile radiogenic isotope signatures that are more enriched than expected for plume-derived OIBs. These features could possibly be caused by isotopic decoupling associated with shallow melting of a hybridized upper mantle, or derivation from an atypical mantle plume, or both by way of mixing. New Hf isotope and trace element data further constrain potential sources for the ESRP basalts. Their Hf isotopic signatures (ɛHf = +0.1 to -5.8) are moderately enriched and consistently fall above or in the upper part of the field of OIBs, with similar Nd isotope signatures (ɛNd = -2.0 to -5.8), indicating a source with high time-integrated Lu/Hf compared with Sm/Nd. The isotopic compositions of the basalts lie between those of Archean SCML and a more depleted end-member source, suggestive of contributions from at least two sources. The grouping of isotopic characteristics is compact compared to other regional volcanism, implying that the hybridization process is highly reproducible within the ESRP. Minor localized differences in isotopic composition may signify local variations in the relative proportions of the end-members. Trace element patterns also support genesis of the ESRP basalts from an enriched source. Our data detect evidence of deeper contributions derived from the garnet-stability field, and a greater affinity of the trace element signatures to plume sources than to sources in the mantle lithosphere. The Hf isotope and trace element characteristics of the ESRP basalts thus support a model of derivation from a deep mantle plume with additional melt contributions and isotopic overprinting from SCML.

Potential Nucleosynthetic Sources of the Titanium Isotope Variations in Solar System Materials

NASA Astrophysics Data System (ADS)

Williams, N. H.; Fehr, M. A.; Akram, W. M.; Parkinson, I. J.; Schönbächler, M.

2012-09-01

The Ti isotope ratios of a comprehensive sample suite of solar system material were analyzed by MC-ICPMS. This data was then used to evaluate nucleosynthetic models for the source of isotopic correlations observed in Iron group elements and Zr.

Laurentide Ice-Sheet Meltwater Sources to the Gulf of Mexico During the Last Deglaciation: Assessing Data Reconstructions Using Water Isotope Enabled Simulations

NASA Astrophysics Data System (ADS)

Vetter, L.; LeGrande, A. N.; Ullman, D. J.; Carlson, A. E.

2017-12-01

Sediment cores from the Gulf of Mexico show evidence of meltwater derived from the Laurentide Ice Sheet during the last deglaciation. Recent studies using geochemical measurements of individual foraminifera suggest changes in the oxygen isotopic composition of the meltwater as deglaciation proceeded. Here we use the water isotope enabled climate model simulations (NASA GISS ModelE-R) to investigate potential sources of meltwater within the ice sheet. We find that initial melting of the ice sheet from the southern margin contributed an oxygen isotope value reflecting a low-elevation, local precipitation source. As deglacial melting proceeded, meltwater delivered to the Gulf of Mexico had a more negative oxygen isotopic value, which the climate model simulates as being sourced from the high-elevation, high-latitude interior of the ice sheet. This study demonstrates the utility of combining stable isotope analyses with climate model simulations to investigate past changes in the hydrologic cycle.

Is the Hawaiian Archipelago dominantly Loa-trend?

NASA Astrophysics Data System (ADS)

Weis, D.; Harrison, L.; Garcia, M. O.; Rhodes, M. M.

2015-12-01

Hawaiian volcanoes are distributed en echelon on the islands along two chains, the Loa and Kea trends, that are geographically and geochemically distinct1,2. These geochemical differences may be attributed to source zoning (concentric or bilateral) of the Hawaiian mantle plume (HMP) or to variations in pressure and temperature of melting. Most of these models assume a degree of independence of the two trends that is perhaps not realistic. To explore the isotopic characteristics of two "Kea"-trend volcanoes with transitional signatures, we analyzed 11 samples of Kohala shield-stage tholeiitic lavas and three from Haleakala for high-precision Pb-Nd-Sr-Hf isotopes. These samples are transitional in all isotopic systems between Loa and Kea compositions and cross-over the Pb-Pb boundary3. Minor cross-overs had been documented in Mauna Kea4, Kilauea5, and W Molokai6 basalts. A bilateral or concentric view of the HMP is thus too simplistic. Statistical analysis of the MC-ICP-MS or triple-spike shield tholeiite data (n>600) and the existence of three Pb-Pb trends originating from average Loa indicate that Loa is the dominant mantle source composition on the archipelago. Isotopically, four geochemical groups are identified: Kea (Mauna Kea, Kilauea), average Loa (Mauna Loa, Hualalai, Kauai, Waianae, W. Molokai, Loihi), enriched Loa (Koolau Makapuu, Lanai, Kahoolawe) and transitional Kea (E. Molokai, W. Maui, Haleakala, Kohala). The implications are: 1) HMP source components refresh and grade into and out of existence on a smaller timescale than previously thought; 2) the Kea trend is also heterogeneous; and 3) vertical heterogeneity of the plume is important on a regional scale as well as at the scale of individual volcanoes6. 1Jackson et al., 1972, GSA Bull. 83, 1-17. 2Weis et al., 2011, Nat. Geosci., 4, 831-838. 3Abouchami et al., 2005, Nature, 434, 851-856. 4Eisele et al., 2003, G-cubed, 4, 5, 32 pages. 5Marske et al., 2007, EPSL, 259, 34-50. 6Xu et al., 2014, GCA, 132, 241-237.

Isotopic signatures suggest important contributions from recycled gasoline, road dust and non-exhaust traffic sources for copper, zinc and lead in PM10 in London, United Kingdom

NASA Astrophysics Data System (ADS)

Dong, Shuofei; Ochoa Gonzalez, Raquel; Harrison, Roy M.; Green, David; North, Robin; Fowler, Geoff; Weiss, Dominik

2017-09-01

The aim of this study was to improve our understanding of what controls the isotope composition of Cu, Zn and Pb in particulate matter (PM) in the urban environment and to develop these isotope systems as possible source tracers. To this end, isotope ratios (Cu, Zn and Pb) and trace element concentrations (Fe, Al, Cu, Zn, Sb, Ba, Pb, Cr, Ni and V) were determined in PM10 collected at two road sites with contrasting traffic densities in central London, UK, during two weeks in summer 2010, and in potential sources, including non-combustion traffic emissions (tires and brakes), road furniture (road paint, manhole cover and road tarmac surface) and road dust. Iron, Ba and Sb were used as proxies for emissions derived from brake pads, and Ni, and V for emissions derived from fossil fuel oil. The isotopic composition of Pb (expressed using 206Pb/207Pb) ranged between 1.1137 and 1.1364. The isotope ratios of Cu and Zn expressed as δ65CuNIST976 and δ66ZnLyon ranged between -0.01‰ and +0.51‰ and between -0.21‰ and +0.33‰, respectively. We did not find significant differences in the isotope signatures in PM10 over the two weeks sampling period and between the two sites, suggesting similar sources for each metal at both sites despite their different traffic densities. The stable isotope composition of Pb suggests significant contribution from road dust resuspension and from recycled leaded gasoline. The Cu and Zn isotope signatures of tires, brakes and road dust overlap with those of PM10. The correlation between the enrichments of Sb, Cu, Ba and Fe in PM10 support the previously established hypothesis that Cu isotope ratios are controlled by non-exhaust traffic emission sources in urban environments (Ochoa Gonzalez et al., 2016). Analysis of the Zn isotope signatures in PM10 and possible sources at the two sites suggests significant contribution from tire wear. However, temporary additional sources, likely high temperature industrial emissions, need to be invoked to explain the isotopically light Zn found in 3 out of 18 samples of PM10.

Mantle sources for Central Atlantic Magmatic Province basalts from Hf isotopes

NASA Astrophysics Data System (ADS)

Elkins, L. J.; Marzoli, A.; Bizimis, M.; Meyzen, C. M.; Callegaro, S.; Sorsen, N.; Lassiter, J. C.; Ernesto, M.

2017-12-01

The Central Atlantic Magmatic Province (CAMP) was one of the most voluminous LIP events in Earth history and likely triggered the end-Triassic mass extinction. The tectonic and mantle processes that produced such significant magmatic emplacement are thus of great interest. To further explore the origins of CAMP, we present new 176Hf/177Hf isotope data for a broad geographic sampling of CAMP dikes, sills, and basalt flows. We find that basaltic intrusions from the Carolinas in Eastern North America trend along a shallower slope than the terrestrial array on a diagram of 176Hf/177Hf vs. 143Nd/144Nd. This trend may reflect the presence of variable quantities of sediment-derived material in the mantle source region. This is consistent with previous suggestions that the asthenosphere beneath CAMP has been partially metasomatised by fluids derived from subducted sediments, as well as with isotopic trends observed in other LIP, such as Karoo [Jourdan et al., 2007, Jour. Petrology, doi:10.1093/petrology/egm010]. Distinct from the Carolina trend, we further observe that high-TiO2 basalts from Amazonia exhibit unusually radiogenic 176Hf/177Hf for a given 208Pb/206Pb ratio. The high-TiO­2 basalts, which trend towards EM1-type compositions, may be asthenospheric melts that have experienced the addition of melts from local subcontinental lithospheric mantle (SCLM). Similarly high-TiO2 CAMP rocks from Sierra Leone may likewise have incorporated enriched lithospheric melts of lamproite-like composition in the source region [Callegaro et al., JPet, accepted; GSA Abstract #302853, 2017]. Low-TiO2 basalts from the same region in Brazil and of similar age to the high-TiO2 basalts lack the observed radiogenic 176Hf/177Hf ratios. This suggests that the melt source region beneath Brazil was heterogeneous, containing variable material with relatively radiogenic 176Hf/177Hf ratios, perhaps due to the greater age of subcontinental lithosphere and the presence of garnet. It remains unclear, however, whether the hypothesized SCLM source represents lithospheric domains which are still intact, or if this material reentered the convecting mantle by delamination prior to melting.

Cainozoic Orogenic Magmatism In The Western-central Mediterranean Area: Implications For The Subduction-modified Mantle Sources

NASA Astrophysics Data System (ADS)

Beccaluva, L.; Bianchini, G.; Coltorti, M.; Siena, F.; Verde, M.

In this contribution new REE and Sr-Nd isotopic data carried out on Cainozoic subduction-related volcanic rocks from the western-central Mediterranean are dis- cussed within a general review of the Cainozoic orogenic magmatism of the area. These volcanic events are related to subduction processes which occurred along the Paleo-European margin at least since Eocene and migrated (trough passive sinking and slab roll-back) southeastward up to the present in the peri-Tyrrhenian margin of Italy. Orogenic rocks from Provence (34-20 Ma) are characterised by 87Sr/86Sr be- tween 0.70453 and 0.70579, and 143Nd/144Nd between 0.51292 and 0.51265, which are consistent with mantle sources modified by subduction fluids released by altered oceanic crust. Sr-Nd isotopic composition of orogenic rocks from Sardinia (32-13 Ma), show a more complex picture: some compositions with relatively low 87Sr/86Sr (<0.706) and high 143Nd/144Nd (>0.5125), are compatible with the subduction of pure oceanic crust, while compositions with very high 87Sr/86Sr (up to 0.7113) and low 143Nd/144Nd (down to 0.51219) require additional components of continental crust affinity in the mantle wedge (partial fusion of subducted terrigenous sediments?). As concerns the Aeolian volcanics (< 1.3 Ma), compositions are compatible with man- tle sources solely enriched by fluid components from subducted oceanic crust. How- ever, it is interesting to note that shoshonites from the younger series of Stromboli display distinctly higher 87Sr/86Sr (up to 0.7075) and lower 143Nd/144Nd composi- tion (down to 0.51242), thus requiring once again recycle of continental crust materials in their mantle sources. The influence of such continental crust-derived components appear to be even more important in the mantle sources of the Campania volcanics, where extreme Sr-Nd isotopic compositions are recorded (87Sr/86Sr up to 0.7097; 143Nd/144Nd down to 0.5122).

Late Early-Cretaceous quartz diorite-granodiorite-monzogranite association from the Gaoligong belt, southeastern Tibet Plateau: Chemical variations and geodynamic implications

NASA Astrophysics Data System (ADS)

Zhu, Ren-Zhi; Lai, Shao-Cong; Qin, Jiang-Feng; Zhao, Shao-Wei; Wang, Jiang-Bo

2017-09-01

Geochemical variations in granitic rocks may be controlled by their source rocks, melting reactions and subsequent magmatic processes, which resulted from various geodynamic processes related to subduction, collision, or slab break-off. Here we report new LA-ICP-MS zircon U-Pb ages and Hf isotopes, whole-rock chemistry and Sr-Nd isotopes for the late Early Cretaceous quartz diorite, granodiorite and monzogranite in the Gaoligong belt, southeastern Tibet Plateau. The zircon U-Pb dating yield ages of 113.9 ± 1.6, 111.7 ± 0.8, and 112.8 ± 1.7 Ma for the quartz diorite, granodiorite, and monzogranite, respectively, which are coeval with bimodal magmatism in the central and northern Lhasa sub-terrane. There are the distinct sources regions for the quartz diorite and granodiorite-monzogranite association. The quartz diorites are sodic, calc-alkaline and have high Mg# (52-54) values. They also have elevated initial 87Sr/86Sr (0.707019 to 0.709176) and low εNd(t) (- 5.16 to - 7.63), with variable zircon εHf(t) values (+ 5.65 to - 9.02). Zircon chemical data indicate a typical crustal-derived character with high Th (142-1260 ppm) and U (106-1082 ppm) and moderate U/Yb ratios (0.30 to 2.32) and Y content (705-1888 ppm). Those data suggest that the quartz diorites were derived from partial melting of ancient basaltic lower crust by a mantle-derived magma in source region. The granodiorite-monzogranite association has high-K calc-alkaline, weakly peraluminous characters. They show lower Nb/Ta (5.57 to 13.8), CaO/Na2O (0.62 to 1.21), higher Al2O3/TiO2 (24.4 to 44.4) ratios, more evolved whole-rock Sr-Nd and zircon Hf isotopic signatures, all of which suggest derivation from mixed basaltic and metasedimentary source rocks in a deep crustal zone. We propose that the granitic magmatisms at ca. 113-110 Ma in the Gaologong belt was triggered by the slab break-off of Bangong-Nujiang Tethyan oceanic lithosphere. Supplementary Dataset Table 2. Single-grain zircon Hf isotopic data for granitic rocks in the Gaoligong belt, SW China.

Fluid Characteristics and Evolution of Chelungpu fault of Taiwan

NASA Astrophysics Data System (ADS)

Song, S. R.

2017-12-01

We analyzed geochemical characteristics, such as hydrogen and oxygen isotopes, and ionic concentrations, of fluid samples retrieved from various depth along boreholes of the Hole A and Hole B of Taiwan Chelungpu fault Drilling Project(TCDP) to trace the fluid sources. The results show that the source of fluid in the Hole B is mainly the tap water, while there are two probable sources in the Hole A owing to the abrupt shift of ionic concentrations at the depth of 200-300 m. The shallower fluid might be from the leakage above the depth of 300 m and is characteristic of lower ionic concentrations and the isotopic ratios are close to those of adjacent river water. However, the deeper fluid should be the thermal water from Kueichulin formation because of high ionic concentrations, especially HCO3-, and higher oxygen isotope, which suggests higher temperature and more isotope exchange. Two sources of fluid of the Hole A are representative of the fluid systems in the hanging wall and foot wall respectively. The characteristics of fluids in the Hole A imply that the fault zone serves as a barrier in the inter-seismic period, resulting in distinctly different fluid between the Hanging wall and the foot wall. The frequent occurrence and the distribution of calcite veins provide the evidence of the upwelling of HCO3-rich fluid of Kueichulin formation and indicate that the fault served as fluid conduit during faulting and allowed the fluid flow across the fault zone to precipitate calcite veins in fractures of the hanging wall. Thus, we can deduce the mechanism of local groundwater flow during different stages of fault development by evidences such as calcite veins distribution, regional groundwater geology, and fluids characteristics in boreholes of the Hole-A and Hole B. During inter-seismic period, groundwater flows below and above the fault zone are separated by the impermeable fault gouge layer. In co-seismic time, faulting breaks the gouge layer, providing openings that let the over-pressured thermal water which contained high concentration of bicarbonate ion to surge up. After co-seismic period, the gouge layer is sealed again, residual thermal water which contained high concentration of bicarbonate ion in the hanging wall gradually precipitated calcite in fractures and the closer precipitation took place, the more calcite veins.