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Carbonate abundances and isotopic compositions in chondrites  

NASA Astrophysics Data System (ADS)

We report the bulk C abundances, and C and O isotopic compositions of carbonates in 64 CM chondrites, 14 CR chondrites, 2 CI chondrites, LEW 85332 (C2), Kaba (CV3), and Semarkona (LL3.0). For the unheated CMs, the total ranges of carbonate isotopic compositions are ?13C ? 25-75‰ and ?18O ? 15-35‰, and bulk carbonate C contents range from 0.03 to 0.60 wt%. There is no simple correlation between carbonate abundance and isotopic composition, or between either of these parameters and the extent of alteration. Unless accretion was very heterogeneous, the uncorrelated variations in extent of alteration and carbonate abundance suggests that there was a period of open system behavior in the CM parent body, probably prior to or at the start of aqueous alteration. Most of the ranges in CM carbonate isotopic compositions can be explained by their formation at different temperatures (0-130 °C) from a single fluid in which the carbonate O isotopes were controlled by equilibrium with water (?18O ? 5‰) and the C isotopes were controlled by equilibrium with CO and/or CH4 (?13C ? -33‰ or -20‰ for CO- or CH4-dominated systems, respectively). However, carbonate formation would have to have been inefficient, otherwise carbonate compositions would have resembled those of the starting fluid. A quite similar fluid composition (?18O ? -5.5‰, and ?13C ? -31‰ or -17‰ for CO- or CH4-dominated systems, respectively) can explain the carbonate compositions of the CIs, although the formation temperatures would have been lower (~10-40 °C) and the relative abundances of calcite and dolomite may play a more important role in determining bulk carbonate compositions than in the CMs. The CR carbonates exhibit a similar range of O isotopes, but an almost bimodal distribution of C isotopes between more (?13C ? 65-80‰) and less altered samples (?13C ? 30-40‰). This bimodality can still be explained by precipitation from fluids with the same isotopic composition (?18O ? -9.25‰, and ?13C ? -21‰ or -8‰ for CO- or CH4-dominated systems, respectively) if the less altered CRs had higher mole fractions of CO2 in their fluids. Semarkona and Kaba carbonates have some of the lightest C isotopic compositions of the meteorites studied here, probably because they formed at higher temperatures and/or from more CO2-rich fluids. The fluids responsible for the alteration of chondrites and from which the carbonates formed were almost certainly accreted as ices. By analogy with cometary ices, CO2 and/or CO would have dominated the trapped volatile species in the ices. The chondrites studied are too oxidized for CO-dominated fluids to have formed in their parent bodies. If CH4 was the dominant C species in the fluids during carbonate formation, it would have to have been generated in the parent bodies from CO and/or CO2 when oxidation of metal by water created high partial pressures of H2. The fact that the chondrite carbonate C/H2O mole ratios are of the order predicted for CO/CO2-H2O ices that experienced temperatures of >50-100 K suggests that the chondrites formed at radial distances of <4-15 AU.

Alexander, C. M. O'd.; Bowden, R.; Fogel, M. L.; Howard, K. T.



Natural abundances of carbon isotopes in acetate from a coastal marine sediment  

NASA Technical Reports Server (NTRS)

Measurements of the natural abundances of carbon isotopes were made in acetate samples isolated from the anoxic marine sediment of Cape Lookout Bight, North Carolina. The typical value of the total acetate carbon isotope ratio (delta 13C) was -16.1 +/- 0.2 per mil. The methyl and carboxyl groups were determined to be -26.4 +/- 0.3 and -6.0 +/- 0.3 per mil, respectively, for one sample. The isotopic composition of the acetate is thought to have resulted from isotopic discriminations that occurred during the cycling of that molecule. Measurements of this type, which have not been made previously in the natural environment, may provide information about the dominant microbial pathways in anoxic sediments as well as the processes that influence the carbon isotopic composition of biogenic methane from many sources.

Blair, N. E.; Martens, C. S.; Des Marais, D. J.



Abundance, distribution, and isotopic composition of particulate black carbon in the northern Gulf of Mexico  

NASA Astrophysics Data System (ADS)

exists increasing evidence supporting the important role of black carbon in global carbon cycles. Particulate black carbon (PBC) is allochthonous and has distinct reactivities compared to the bulk particulate organic carbon (tot-POC) in marine environments. However, the abundance, geochemical behavior of PBC and its importance in oceanic carbon budget remain poorly understood. Here we report the abundance, distribution, and stable isotopic signatures of BC derived from the chemo-thermal oxidation (CTO-375) method (BCCTO) in the Gulf of Mexico. Our results show that BCCTO abundance decreased from shelf to basin, and more than a half of riverine BCCTO could be removed over the shelf. Moreover, BCCTO is much more refractory compared to the tot-POC and has ?13C values lower than those of BC-excluded POC. These results highlight the significance of PBC in marine carbon cycles and potentially suggest the need for a new end-member term in quantifying POC sources in the ocean.

Yang, Weifeng; Guo, Laodong



On the carbon and nitrogen isotope abundance ratios in Comet Halley  

NASA Astrophysics Data System (ADS)

Emission lines attributable to (C-13)(N-14) have been resolved in ground-based spectra of Comet Halley. An analysis of the spectrum using six (C-13)(N-14) lines results in a carbon isotope abundance ratio, (C-12)(C-13) = 63 + 9/-7, and a lower limit N-14/N-15 greater than 200. The carbon isotope ratio is nearly 3-delta less than the bulk solar system ratio, 89. The limit on the nitrogen isotope ratio is consistent with the bulk solar system ratio, 250. The carbon isotope ratio in the comet may be explained by selective fractionation enhancement of C-13 in the parent of the CN molecule, or by a depletion of C-12 relative to C-13.

Wyckoff, S.; Lindholm, E.


Effect of carbon isotopic variations on measured CO2 abundances in reference gas mixtures  

NASA Astrophysics Data System (ADS)

Changes in the Earth's climate caused by global warming are a looming problem that poses serious challenges not only for our generation but for future generations. An accurate determination of CO2 gas plays a critical role in this field of research. The measurement of greenhouse gases is pivotal to understanding the changes in Earth's climate and needs to be carried out with a high degree of accuracy. Precision measurements on a 0.1 ?mol/mol scale may provide research data for precisely monitoring the continuing changes that the planet is undergoing. The World Meteorological Organization (WMO) has recommended that carbon dioxide concentrations in air can be measured by comparing these with national reference gases using a nondispersive infrared (NDIR) analyzer to standardize international data. The CO2 molecules absorb the distinctive resonant frequencies in IR spectrometers. The NDIR analyzers usually use narrow band path filter to determine 12CO2 in all carbon dioxide molecules, which can possibly ignore the measurement of 13CO2 partially or totally. However, if the carbon isotopic abundances of CO2 samples deviate from those in standard CO2 gas, the NDIR measurement will not be exact. For accurate measurements, producers of reference gas mixtures either must use gas with natural isotopic abundances, or report the isotopic abundances of CO2. In order to document shifts based on isotopic variability, we prepared artificial air as CO2 reference gas mixtures gravimetrically with CO2 having different carbon isotopic signatures to study the resulting isotopic variations. We used different ?13C values of two CO2 source gases, A and B, corresponding to -41.97‰ and -14.88‰, respectively, which were measured using an isotope ratio mass spectrometer. One set of reference gas mixtures (A1 to A5) was prepared from the CO2 source of ?13C = -41.97‰, and the other set of reference gas mixtures (B1, B2) was prepared from that of ?13C = -14.88‰. The CO2 abundances of the two sets of mixtures were compared by using NDIR. The reproducibility test for the set A showed that the data are consistent within uncertainty (calibration line was obtained by the best secondary polynomial least squares fit). The uncertainty of CO2 concentration in the reference gas mixtures are 0.06 ?mol/mol with a 95% confidence level. The reproducibility of the NDIR measurement is 0.012 ?mol/mol (standard deviation). The difference between the set A (A1 to A5) and set B (B1, B2) was found to be 0.17 ± 0.01 ?mol/mol, which is in excellent agreement with the theoretically predicted value of 0.17 ?mol/mol.

Lee, Jee-Yon; Yoo, Hee-Soo; Marti, Kurt; Moon, Dong Min; Lee, Jin Bok; Kim, Jin Seog



Abundances in red giant stars - Nitrogen isotopes in carbon-rich molecular envelopes  

NASA Technical Reports Server (NTRS)

Results are presented of millimeter- and submillimeter-wave observations of HCN and HCCCN that were made of the circmustellar envelopes of eight carbon stars, including the two protoplanetary nebulae CRL 618 and CRL 2688. The observations yield a measure of the double ratio (N-14)(C-13)/(N-15)(C-12). Measured C-12/C-13 ratios are used to estimate the N-14/N-15 abundance ratio, with the resulting lower limits in all eight envelopes and possible direct determinations in two envelopes. The two determinations and four of the remaining six lower limits are found to be in excess of the terrestrial value of N-14/N-15 = 272, indicating an evolution of the nitrogen isotope ratio, which is consistent with stellar CNO processing. Observations of thermal SiO (v = 0, J = 2-1) emission show that the Si-29/Si-28 ratio can be determined in carbon stars, and further observations are indicated.

Wannier, P. G.; Andersson, B.-G.; Olofsson, H.; Ukita, N.; Young, K.



Solar Carbon Monoxide, Thermal Profiling, and the Abundances of C, O, and their Isotopes  

E-print Network

A solar photospheric "thermal profiling" analysis is presented, exploiting the infrared rovibrational bands of carbon monoxide (CO) as observed with the McMath-Pierce Fourier transform spectrometer (FTS) at Kitt Peak, and from above the Earth's atmosphere by the Shuttle-borne ATMOS experiment. Visible continuum intensities and center-limb behavior constrained the temperature profile of the deep photosphere, while CO center-limb behavior defined the thermal structure at higher altitudes. The oxygen abundance was self consistently determined from weak CO absorptions. Our analysis was meant to complement recent studies based on 3-D convection models which, among other things, have revised the historical solar oxygen (and carbon) abundance downward by a factor of nearly two; although in fact our conclusions do not support such a revision. Based on various considerations, an oxygen abundance of 700+/-100 ppm (parts per million relative to hydrogen) is recommended; the large uncertainty reflects the model sensitivity of CO. New solar isotopic ratios also are reported for 13C, 17O, and 18O.

Thomas R. Ayres; Claude Plymate; Christoph U. Keller



Natural Abundance Carbon Isotope Composition of Isoprene Reflects Incomplete Coupling between Isoprene Synthesis and Photosynthetic Carbon Flow  

PubMed Central

Isoprene emission from leaves is dynamically coupled to photosynthesis through the use of primary and recent photosynthate in the chloroplast. However, natural abundance carbon isotope composition (?13C) measurements in myrtle (Myrtus communis), buckthorn (Rhamnus alaternus), and velvet bean (Mucuna pruriens) showed that only 72% to 91% of the variations in the ?13C values of fixed carbon were reflected in the ?13C values of concurrently emitted isoprene. The results indicated that 9% to 28% carbon was contributed from alternative, slow turnover, carbon source(s). This contribution increased when photosynthesis was inhibited by CO2-free air. The observed variations in the ?13C of isoprene under ambient and CO2-free air were consistent with contributions to isoprene synthesis in the chloroplast from pyruvate associated with cytosolic Glc metabolism. Irrespective of alternative carbon source(s), isoprene was depleted in 13C relative to mean photosynthetically fixed carbon by 4‰ to 11‰. Variable 13C discrimination, its increase by partially inhibiting isoprene synthesis with fosmidomicin, and the associated accumulation of pyruvate suggested that the main isotopic discrimination step was the deoxyxylulose-5-phosphate synthase reaction. PMID:12692331

Affek, Hagit P.; Yakir, Dan



Isotopic abundances of carbon and nitrogen in Jupiter-family and Oort Cloud comets  

Microsoft Academic Search

The 12C14N\\/12C15N and 12C14N\\/13C14N isotopic ratios are determined for the first time in a Jupiter-family comet, 88P\\/1981 Q1 Howell, and in the chemically peculiar Oort Cloud comet C\\/1999 S4 (LINEAR). By comparing these measurements to previous ones derived for six other Oort Cloud comets (including one of Halley-type), we find that both the carbon and nitrogen isotopic ratios are constant

D. Hutsemékers; J. Manfroid; E. Jehin; C. Arpigny; A. Cochran; R. Schulz; J. A. Stüwe; J.-M. Zucconi



Carbon, nitrogen and sulfur in lunar fines 15012 and 15013 - Abundances, distributions and isotopic compositions  

NASA Technical Reports Server (NTRS)

Lunar fines 15012,16 and 15013,3 were analyzed by stepwise pyrolysis and acid hydrolysis as well as complete combustion in oxygen to determine carbon, nitrogen and sulfur. In addition, hydrogen was analysed during pyrolysis as well as during hydrolysis. By comparison of the distribution frequencies of C, N, S, H2 and Fe with He-4, considered to have arisen from solar wind contribution, it is concluded that nitrogen and hydrogen have largely a solar origin. Carbon has a significant solar contribution, and metallic iron may have resulted from solar wind interaction with ferrous minerals on the lunar surface. Sulfur probably has a predominantly lunar origin. There is no direct evidence for meteorotic contribution to these samples. Solar wind interaction also has a marked effect on the stable isotope distribution of C-13/C-12, N-15/N-14, and S-34/S-32. In all cases, the heavy isotope was most enriched in the smallest grain-size fraction.

Chang, S.; Lawless, J.; Romiez, M.; Kaplan, I. R.; Petrowski, C.; Sakai, H.; Smith, J. W.



Natural-abundance stable carbon isotopes of small-subunit ribosomal RNA (SSU rRNA) from Guaymas Basin (Mexico)  

NASA Astrophysics Data System (ADS)

Small-subunit ribosomal RNA (SSU rRNA) is a phylogenetically informative molecule found in all species. Because it is poorly preserved in most environments, it is a useful marker for active microbial populations. We are using the natural-abundance stable carbon isotopic composition of specific microbial groups to help identify the carbon substrates contributing to microbial biomass in a variety of marine environments. At Guaymas Basin, hydrothermal fluids interact with abundant sedimentary organic carbon to produce natural gas and petroleum. Where this reaches the sediment surface, it can support dense patches of seafloor life, including Beggiatoa mats. We report here on the stable carbon isotopic composition of SSU rRNA from a Beggiatoa mat transect, a cold background site, a warm site with high oil concentration, and a second Beggiatoa mat. The central part of the transect mat overlay the steepest temperature gradient, and was visually dominated by orange Beggiatoa. This was fringed by white Beggiatoa mat and bare, but still warm, sediment. Methane concentrations were saturating beneath the orange and white mats and at the oily site, lower beneath bare sediment, and below detection at the background site. Our initial hypotheses were that rRNA isotopic composition would be strongly influenced by methane supply, and that archaeal rRNA might be lighter than bacterial due to contributions from methanogens and anaerobic methane oxidizers. We used biotin-labeled oligonucleotides to capture Bacterial and Archaeal SSU rRNA for isotopic determination. Background-site rRNA was isotopically heaviest, and bacterial RNA from below 2 cm at the oily site was lightest, consistent with control by methane. Within the transect mat, however, the pattern was more complicated; at some sediment depths, rRNA from the mat periphery was isotopically lightest. Part of this may be due to the spatially and temporally variable paths followed by hydrothermal fluid, which can include horizontal flow. There was no consistent isotopic difference between rRNAs captured by the two probes, although RNA recoveries were too low for isotopic determinations at depths where methanogens and methane oxidizers are expected. Our prediction that rRNA stable carbon isotopic composition would correlate with methane supply was borne out by the comparison between background and mat sediments, but may be an oversimplification for sites within hydrothermal features. Future work will include the isotopic characterization of other potential carbon substrates, such as acetate. We are also investigating cold-seep sediments and brine pools in the Gulf of Mexico, where methane is significantly more 13C-depleted than at Guaymas Basin and may therefore leave a stronger imprint on microbial biomass.table carbon isotopes of rRNA captured with Bacterial and Archaeal probes at mat transect and background sites.

MacGregor, B. J.; Mendlovitz, H.; Albert, D.; Teske, A. P.



Natural Carbon Isotope Abundance of Plasma Metabolites and Liver Tissue Differs between Diabetic and Non-Diabetic Zucker Diabetic Fatty Rats  

PubMed Central

Background ‘You are what you eat’ is an accurate summary for humans and animals when it comes to carbon isotope abundance. In biological material, natural13C/12C ratio is subject to minute variations due to diet composition (mainly from ingestion of C3 and C4 metabolism plants) and to the discrimination between ‘light’ and ‘heavy’ isotopes during biochemical reactions (isotope effects and isotopic fractionation). Methodology/Principal Findings Carbon isotopic abundance was measured in ZDF (fa/+) and ZDF (fa/fa), (lean and obese-diabetic rats respectively) fed the same diet. By analysing plasma metabolites (glucose and non-esterified fatty acids), breath and liver tissue by high-precision isotope ratio mass spectrometry, we demonstrate for the first time statistically distinguishable metabolic carbon isotope abundance between ZDF (fa/+) and ZDF (fa/fa) rats based on plasma glucose, palmitic, oleic, linoleic, arachidonic acids and bulk analysis of liver tissue (P<0.005) resulting into clear isotopic fingerprints using principal component analysis. We studied the variation of isotopic abundance between both groups for each metabolite and through the metabolic pathways using the precursor/product approach. We confirmed that lipids were depleted in 13C compared to glucose in both genotypes. We found that isotopic abundance of linoleic acid (C18: 2n-6), even though both groups had the same feed, differed significantly between both groups. The likely reason for these changes between ZDF (fa/+) and ZDF (fa/fa) are metabolic dysregulation associated with various routing and fluxes of metabolites. Conclusion/Significance This work provides evidence that measurement of natural abundance isotope ratio of both bulk tissue and individual metabolites can provide meaningful information about metabolic changes either associated to phenotype or to genetic effects; irrespective of concentration. In the future measuring the natural abundance ?13C of key metabolites could be used as endpoints for studying in vivo metabolism, especially with regards to metabolic dysregulation, and development and progression of metabolic diseases. PMID:24086387

Godin, Jean-Philippe; Ross, Alastair B.; Cléroux, Marilyn; Pouteau, Etienne; Montoliu, Ivan; Moser, Mireille; Kochhar, Sunil



Temporal variation in mycorrhizal diversity and carbon and nitrogen stable isotope abundance in the wintergreen meadow orchid Anacamptis morio.  


Many adult orchids, especially photoautotrophic species, associate with a diverse range of mycorrhizal fungi, but little is known about the temporal changes that might occur in the diversity and functioning of orchid mycorrhiza during vegetative and reproductive plant growth. Temporal variations in the spectrum of mycorrhizal fungi and in stable isotope natural abundance were investigated in adult plants of Anacamptis morio, a wintergreen meadow orchid. Anacamptis morio associated with mycorrhizal fungi belonging to Tulasnella, Ceratobasidium and a clade of Pezizaceae (Ascomycetes). When a complete growing season was investigated, multivariate analyses indicated significant differences in the mycorrhizal fungal community. Among fungi identified from manually isolated pelotons, Tulasnella was more common in autumn and winter, the pezizacean clade was very frequent in spring, and Ceratobasidium was more frequent in summer. By contrast, relatively small variations were found in carbon (C) and nitrogen (N) stable isotope natural abundance, A. morio samples showing similar (15) N enrichment and (13) C depletion at the different sampling times. These observations suggest that, irrespective of differences in the seasonal environmental conditions, the plant phenological stages and the associated fungi, the isotopic content in mycorrhizal A. morio remains fairly constant over time. PMID:25382295

Ercole, Enrico; Adamo, Martino; Rodda, Michele; Gebauer, Gerhard; Girlanda, Mariangela; Perotto, Silvia



Tracing the source of cooking oils with an integrated approach of using stable carbon isotope and fatty acid abundance.  


We report a new approach to identify swill-cooked oils that are recycled from tainted food and livestock waste from commercial vegetable and animal oils by means of carbon isotope values and relative abundance of fatty acids. We test this method using 40 cooking oil samples of different types with known sources. We found significant differences in both total organic carbon isotope as well as compound-specific isotope values and fatty acid C(14)/C(18) ratios between commercial vegetable oils refined from C(3) plants (from -35.7 to -27.0‰ and from 0 to 0.15) and animal oils (from -28.3 to -14.3‰ and from 0.1 to 0.6). Tested swill-cooked oils, which were generally refined by mixing with animal waste illegally, fall into a narrow ?(13)C/fatty acid ratio distribution: from -25.9 to -24.1‰ and from 0.1 to 0.2. Our data demonstrate that the index of a cross-plotting between fatty acid ?(13)C values and C(14)/C(18) ratios can be used to distinguish clean commercial cooking oils from illegal swill-cooked oils. PMID:22813234

Liu, Weiguo; Yang, Hong; Wang, Zheng; Liu, Jinzhao



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

NASA Technical Reports Server (NTRS)

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

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



Evaluating microbial carbon sources in Athabasca oil sands tailings ponds using natural abundance stable and radiocarbon isotopes  

NASA Astrophysics Data System (ADS)

Natural abundance stable (?13C) and radiocarbon (?14C) isotopes of phospholipid fatty acids (PLFAs) were used to evaluate the carbon sources utilized by the active microbial populations in surface sediments from Athabasca oil sands tailings ponds. The absence of algal-specific PLFAs at three of the four sites investigated, in conjunction with ?13C signatures for PLFAs that were generally within ~3‰ of that reported for oil sands bitumen (~ -30‰), indicated that the microbial communities growing on petroleum constituents were dominated by aerobic heterotrophs. The ?14C values of PLFAs ranged from -906 to -586‰ and pointed to a significant uptake of fossil carbon (up to ~90% of microbial carbon derived from petroleum), particularly in PLFAs (e.g., cy17:0 and cy19:0) often associated with petroleum hydrocarbon degrading bacteria. The comparatively higher levels of 14C in other, less specific PLFAs (e.g., 16:0) indicated the preferential uptake of younger organic matter by the general microbial population (~50-80% of microbial carbon derived from petroleum). Since the main carbon pools in tailings sediment were essentially 'radiocarbon dead' (i.e., no detectable 14C), the principal source for this modern carbon is considered to be the Athabasca River, which provides the bulk of the water used in the bitumen extraction process. The preferential uptake of the minor amount of young and presumably more biodegradable material present in systems otherwise dominated by recalcitrant petroleum constituents has important implications for remediation strategies. On the one hand, it implies that mining-related organic contaminants could persist in the environment long after tailings pond reclamation has begun. Alternatively, it may be that the young, labile organic matter provided by the Athabasca River plays an important role in stimulating or supporting the microbial utilization of petroleum carbon in oil sands tailings ponds via co-metabolism or priming processes. Further research needs to examine the role which priming processes play in controlling the fate of organic contaminants in Athabasca oil sands tailings ponds, such as understanding to what extent the addition of labile material may hinder or enhance microbial uptake of fossil carbon. This knowledge can be subsequently used to optimize conditions which favour natural attenuation processes in reclamation sites following mine closure.

Ahad, J. M.; Pakdel, H.



Natural abundance stable carbon isotope evidence for the routing and de novo synthesis of bone FA and cholesterol.  


This research reported in this paper investigated the relationship between diet and bone FA and cholesterol in rats raised on a variety of isotopically controlled diets comprising 20% C3 or C4 protein (casein) and C3 and/or C4 nonprotein or energy (sucrose, starch, and oil) macronutrients. Compound-specific stable carbon isotope analysis (delta13C) was performed on the FA (16:0, 18:0, 18:1, and 18:2) and cholesterol isolated from the diet (n = 4) and bone (n = 8) of these animals. The dietary signals reflected by the bone lipids were investigated using linear regression analysis. delta13C values of bone cholesterol and stearic (18:0) acid were shown to reflect whole-diet delta13C values, whereas the delta13C values of bone palmitic (16:0), oleic (18:1), and linoleic (18:2) acids reflected dietary FA delta13C values. Dietary signal differences are a result of the balance between direct incorporation (or routing) and de novo synthesis of each of these bone lipids. Estimates of the degree of routing of these bone lipids gleaned from correlations between delta13C(dlipid-wdiet) (= delta13C(diet lipid) - delta13C(whole diet)) spacings and delta13C(blipid-wdiet) (= delta13C(bone lipid) - delta13C(whole diet)) fractionations demonstrated that the extent of routing, where 18:2 > 16:0 > 18:1 > 18:0 > cholesterol, reflected the relative abundances of these lipids in the diet. These findings provide the basis for more accurate insights into diet when the delta13C analysis of bone fatty FA or cholesterol is employed. PMID:12733751

Jim, Susan; Ambrose, Stanley H; Evershed, Richard P



Evolution, Abundance and Biocalcification of Calcareous Nannoplankton During the Aptian (Early Cretaceous): Causes and Consequences for C Isotopic Anomalies, Climate Changes and the Carbon Cycle.  

NASA Astrophysics Data System (ADS)

The mid Cretaceous is marked by extreme greenhouse conditions, coeval with emplacement of large igneous provinces, C isotopic anomalies, major changes in structure and composition of the oceans, and accelerated rates in the evolutionary history of calcareous plankton. The Aptian is a crucial interval to decipher links between biotic evolution and environmental pressure: it is appealing for understanding nannofloral biocalcification and feedbacks in the carbonate system and in the global carbon cycle. Ontong Java, Manihiki and Kerguelen Plateaus formed in the Aptian affecting the ocean-atmosphere system with excess CO2, changes in Ca2+ and Mg2+ concentrations, and varying nutrient cycling. Two large C isotopic anomalies are associated with episodes of prolonged high primary productivity, changes in alkality, global warming and cooling, anoxia, speciations and extinctions in planktonic communities. Nannofossil diversity, abundance and biocalcification are quantified in continuous, complete, pelagic sections to derive biosphere-geosphere interactions at short and long time scales. The early Aptian C isotopic anomaly interrupts a speciation episode in calcareous nannoplankton paralleled by a drastic reduction in nannofossil paleofluxes culminating in the nannoconid crisis preceding the Oceanic Anoxic Event 1a and the negative C isotopic spike linked to clathrate melting presumably triggered by the thermal maximum at the onset of the mid Cretaceous greenhouse climate. No extinctions are recorded. In the early late Aptian resumption of nannoconid production and appearance of several taxa are coeval with a return to normal C isotopic values. The occurrence of calpionellids and diversified planktonic foraminifers indicate successful biocalcification and restoration of the thermocline. In the late Aptian a drop in nannofossil abundance and accelerated extinction rates are associated with another C isotopic excursion under cool conditions possibly due to a prolonged volcanic winter or reversed greenhouse conditions resulting from a draw-down of carbon dioxide after accelerated weathering and massive burial of organic carbon-rich sediments in the oceans.

Erba, E.



Stellar Isotopic Abundances in the Milky Way: Insights into the Origin of Carbon and Neutron-Capture Elements  

NASA Astrophysics Data System (ADS)

Elements heavier than iron are formed by the capture of neutrons onto lighter nuclei. Neutron capture happens via two separate processes: the rapid neutron capture process (r-process) that occurs in supernovae, and slow neutron capture process (s-process) that occurs in less-massive stars. This work used high-resolution spectroscopy, synthetic model spectra, and a least-squares fit to show that the ratio of 12C to 13C increases proportionally with [Fe/H]. The new results agree with the conclusions of Lucatello et al. (2006) and Frebel (2008), and show significant improvement that contains less scattering of data points. Analysis of the obtained isotope ratios suggests that the carbon in most stars of the sample originated in supernovae. This paper also presents a method to calculate the europium isotope ratio by modeling the shapes of absorption lines. The range of europium isotopic ratios agrees with previous theoretical predictions about the classical model of heavy element nucleosynthesis, and the work presents new insight into the origins of life in the universe. We thank the US National Science Foundation, the UCSC Science Internship Program, and the Lick Observatory where the spectra were obtained.

Guo, Michelle; Zhang, A.; Kirby, E. N.; Guhathakurta, P.



Carbon isotope analysis in urea at high 13C-abundances using the 13/12CO2-breath test device FANci2.  


The increasing application of 13C-labelled urea in medicine requires simple and reasonable methods for measuring highly enriched C in urea. The combination: ultimate organic analysis--mass spectrometry so far prescribed is complicated and expensive. For medical diagnosis, however, isotope selective nondispersive infrared spectrometers (NDIRS) have been available for many years. One of these tools is FANci2 which is very reasonable and easily to be operated. By means of such devices also urea highly enriched in 13C can be analysed, provided that the samples are first diluted with a defined amount of urea of natural isotopic composition and then transformed into carbon dioxide by means of urease. The relative abundance of 13C in this carbon dioxide, measured by nondispersive infrared spectrometry, is then a measure of the 13C abundance in the initial urea sample. Comparison of results of such measurements with those attained by mass spectrometry proves that this procedure is feasible and yields precis results. PMID:12546414

Schmidt, G



[Effects of intensive agricultural production on farmland soil carbon and nitrogen contents and their delta13C and delta15N isotope abundances].  


Farmland soil carbon and nitrogen contents under intensive agricultural production are the important indices for the assessment of the soil fertility sustainability. This paper measured the soil pH, electrical conductivity (EC), organic carbon (SOC), total nitrogen (TN), and delta13C and delta15N isotope abundances of four types of farmland, i.e., conventional rice-broad bean rotation field, open vegetable field, 3-year plastic covered greenhouse field, and > 10-year plastic covered greenhouse field, aimed to understand the effects of intensive agricultural production degree on soil properties. In the open vegetable field, 3-year plastic covered greenhouse field, and > 10-year plastic covered greenhouse field, the soil (0-20 cm) pH decreased by 1.1, 0.8, and 0.7, and the soil EC was 4.2, 4.9, and 5.2 folds of that in conventional rice-broad bean rotation field, respectively. With the increasing year of plastic covered greenhouse production, the soil SOC and TN contents decreased after an initial increase. Comparing with those under rice-broad bean rotation, the SOC content in 0-20, 20-40, 40-60, 60-80 and 80-100 cm soil layers in >10-year plastic covered greenhouse decreased by 54%, 46%, 60%, 63%, and 59%, and the TN content decreased by 53%, 53%, 71%, 82%, and 85%, respectively. Intensive agricultural production degree had significant effects on the soil SOC and TN contents and delta13C and delta15N abundances. The delta13C abundance was significantly negatively correlated with the soil SOC, suggesting that the soil delta13C abundance could be regarded as an index for the assessment of carbon cycle in farmland soils under effects of human activities. PMID:22720621

Yang, Guang-Rong; Hao, Xiying; Li, Chun-Li; Wang, Zi-Lin; Li, Yong-Mei



Carbon13 kinetic isotope effects in the decarbonylations of lactic acid containing 13 C at the natural abundance level  

Microsoft Academic Search

The13C kinetic isotope fractionation in the decarbonylation of lactic acid of natural isotopic composition by sulfuric acid has been studied in the temperature range of 20–80°C. The13C(1) isotope separation in the decarbonylation of lactic acid by concentrated sulfuric acid depends strongly on the temperature above 40°C. Below this temperature the13C isotope effect in the decarbonylation of lactic acid by concentrated

M. Zielinski; G. Czarnota; H. Papiernik-Zielinska



Stable Carbon Isotope Ratios of Individual Pollen Grains as a Proxy for C3- Versus C4-Grass Abundance in Paleorecords: A Validation Study  

NASA Astrophysics Data System (ADS)

C3 and C4 grasses have distinct influences on major biogeochemical processes and unique responses to important environmental controls. Difficulties in distinguishing between these two functional groups of grasses have hindered paleoecological studies of grass-dominated ecosystems. We recently developed a technique to analyze the stable carbon isotope composition of individual grass-pollen grains using a spooling- wire microcombustion device interfaced with an isotope-ratio mass spectrometer (Nelson et al. 2007). This technique holds promise for improving C3 and C4 grass reconstructions. It requires ~90% fewer grains than typical methods and avoids assumptions associated with mixing models. However, our previous work was based on known C3 and C4 grasses from herbarium specimens and field collections and the technique had not been test using geological samples. To test the ability of this technique to reproduce the abundance of C3 and C4 grasses on the landscape, we measured ?13C values of >1500 individual grains of grass pollen isolated from the surface sediments of 10 North American lakes that span a large gradient of C3 and C4 grass abundance. Results indicate a strong positive correlation (r=0.94) between % C4-grass pollen (derived from classifying ?13C values from single grains as C3 and C4) and the literature-reported abundance of C4 grasses on the landscape. However, the measured % C4-grass pollen shows some deviation from the actual abundance at sites with high proportions of C4 grasses. This is likely caused by uncertainty in the magnitude, composition, and variability of the analytical blank associated with these measurements. Correcting for this deviation using regression analysis improves the estimation of the abundance of C4 grasses on the landscape. Comparison of the % C4-grass pollen with C/N and ?13C measurements of total organic matter in the same lake-sediment samples illustrates the distinct advantage of grass-pollen ?13C as a proxy for distinguishing C3 and C4 shifts. At 9 of the 10 sites C/N values indicate that surface-sediment organic matter was derived primarily from aquatic production. At the one site where organic matter was produced primarily by vascular plants the ?13C value (-29.3°) suggests organic matter derived exclusively from C3 plants. However, ~80% of the grasses on the landscape at this site are C4 grasses. The C3- like bulk-sediment ?13C value likely represents woody species, which comprise >90% of the pollen spectra. Thus ?13C analysis of single grains of grass pollen offers a new tool to classify grass pollen into two major functional groups and promises to advance our understanding of grassland ecology and evolution. Reference Nelson, D.M., Hu, F.S., Mikucki, J., Tian, J., and Pearson, A., 2007, Carbon isotopic analysis of individual pollen grains from C3 and C4 grasses using a spooling wire microcombustion interface: Geochimica et Cosmochimica Acta, v. 71, p. 4005-4014.

Nelson, D. M.; Hu, F.; Pearson, A.



Site-specific responses to short-term environmental variation are reflected in leaf and phloem-sap carbon isotopic abundance of field grown Eucalyptus globulus.  


The carbon isotopic composition (?(13) C) of plant material has been used extensively as an indirect measure of carbon fixation per volume of water used. More recently, the ?(13) C of phloem sap (?(13) C(phl) ) has been used as a surrogate measure of short-term, canopy scale ?(13) C. Using a combination of ?(13) C physiological, structural and chemical indices from leaves and phloem sap of Eucalyptus globulus at sites of contrasting water availability, we sought to identify short-term, canopy scale resource limitations. Results illustrate that ?(13) C(phl) offers valid reflections of short-term, canopy scale values of leaf ?(13) C and tree water status. Under conditions limited by water, leaf and phloem sap photoassimilates differ in (13) C abundance of a magnitude large enough to significantly influence predictions of water use efficiency. This pattern was not detected among trees with adequate water supply indicating fractionation into heterotrophic tissues that may be sensitive to plant water status. Trees employed a range of physiological, biochemical and structural adaptations to acclimate to resource limitation that differed among sites providing a useful context upon which to interpret patterns in ?(13) C. Our results highlight that such easily characterized properties are ideal for use as minimally invasive tools to monitor growth and resilience of plants to variations in resource availability. PMID:22568657

Merchant, Andrew; Buckley, Thomas N; Pfautsch, Sebastian; Turnbull, Tarryn L; Samsa, Glen A; Adams, Mark A



[Distribution characteristics of soil humus fractions stable carbon isotope natural abundance (delta 13C) in paddy field under long-term ridge culture].  


A 16-year field experiment was conducted in a ridge culture paddy field in the hilly region of Sichuan Basin, aimed to investigate the distribution characteristics of stable carbon isotope natural abundance (delta 13C) in soil humus fractions. The soil organic carbon (SOC) content in the paddy field under different cultivation modes ranked in the order of wide ridge culture > ridge culture > paddy and upland rotation. In soil humus substances (HS), humin (HU) was the main composition, occupying 21% - 30% of the total SOC. In the extracted soil carbon, humic acid (HA) dominated, occupying 17% - 21% of SOC and 38% - 65% of HS. The delta 13C value of SOC ranged from -27.9 per thousand to -25.6 per thousand, and the difference of the delta 13C value between 0-5 cm and 20-40 cm soil layers was about 1.9 per thousand. The delta 13C value of HA under different cultivation modes was 1 per thousand - 2 per thousand lower than that of SOC, and more approached to the delta 13C value of rapeseed and rice residues. As for fulvic acid (FA), its delta 13C value was about 2 per thousand and 4 per thousand higher than that of SOC and HA, respectively. The delta 13C value of HU in plough layer (0-20 cm) and plow layer (20-40 cm) ranged from -23.7 per thousand - -24.9 per thousand and -22.6 per thousand - -24.2 per thousand, respectively, reflecting the admixture of young and old HS. The delta 13C value in various organic carbon fractions was HU>FA>SOC>rapeseed and rice residues>HA. Long-term rice planting benefited the increase of SOC content, and cultivation mode played an important role in affecting the distribution patterns of soil humus delta 13C in plough layer and plow layer. PMID:21774322

Tang, Xiao-hong; Luo, You-jin; Ren, Zhen-jiang; Lü, Jia-ke; Wei, Chao-fu



Helium and Carbon Isotope and Relative Abundance Relationships in Lau Basin Basalts: Resolving Mantle Source Composition from Degassing and Contamination Effects  

NASA Astrophysics Data System (ADS)

The Lau Basin has multiple mantle source components including contributions from the Indian and Pacific MORB sources, Tonga-Kermadec Arc and Samoan plume. In order to characterize the volatile systematics of these various sources and to map their spatial distribution, we have sampled basaltic glasses from over 50 dredge sites covering all known spreading centers in the basin as well as many off-axis seamounts. Here, we report He abundance and isotope results obtained by crushing, in addition to CO2 released through stepped heating, from sites at the Mangatolu Triple Junction (MTJ), Rochambeau Bank (RB), Peggy Ridge, and the Northern, Eastern and Central Lau Spreading Centers. High 3He/4He ratios from RB (up to 23 RA, where RA = air 3He/4He) confirm the presence of a plume component in the northwestern Lau Basin (Poreda, EPSL, 1985). Central and Eastern Lau Spreading Center basalts have 3He/4He ratios between 8.3 and 9.4 RA, consistent with a depleted, MORB-like mantle source with little influence from slab or crustal helium. In contrast, the large range in helium isotope ratios of MTJ samples (0.85 to 7.9 RA) and the correlation between low He abundances (~2 - 3 × 10-9 cm3/g) and low helium isotope ratios suggests the volatiles in this region have been severely affected by degassing and additions of radiogenic (crustal) He. CO2 abundances and carbon isotopes for samples from RB vary from 70 to 119 ppm ([CO2]total) with ?13Cvesicle falling between -12.3 to -14.8 ‰ and ?13Cdissolved lying between -9.3 to -10.7 ‰. In the MTJ, low helium concentration samples have ?13C as low as -27.4 ‰ and [CO2]total as low as 7.6ppm; interestingly, this region also has samples with the highest measured values (up to -6.3 ‰ and 132ppm total C). Combining the carbon and helium data, CO2/3He ratios in the MTJ range from arc-like values (~1010) to sediment or crustal values (~1013) showing the superimposition of degassing and/or contamination effects on a predominant slab-like signature. High 3He/4He samples from RB have CO2 /3He ratios similar to the upper mantle value (2 × 109), as at other back-arc localities exhibiting a high 3He/4He (plume) component (e.g. the Manus Basin; Shaw et al., GCA, 2004). Continuing analytical work will complete our He-C survey of the Lau Basin, identifying samples suitable for further effort involving Ne, Ar, H2O plus other tracers of interest. Presently, we are modeling degassing/contamination effects to identify the nature and distribution of mantle source components throughout the Lau Basin. The volatile characteristics of the high 3He/4He samples are of particular interest as they provide insight into the different recycling and storage histories of volatiles between distinct mantle reservoirs.

Vukajlovich, D. J.; Hilton, D. R.; Castillo, P. R.; Hawkins, J. W.



Variation in soil organic carbon abundance and isotopic composition mediated by landslide activity in the Sierra de Las Minas, Guatemala  

NASA Astrophysics Data System (ADS)

Tropical mountains play an important role in biogeochemical cycles worldwide due to complex interaction between geomorphic and ecosystem processes. The strength of these interactions, however, is likely to vary along the steep environmental gradients found in mountainous terrain. Here we focus on soil organic carbon and ask how landsliding alters soil organic carbon density, C:N ratios and ?13C and ?15N along the broad climatic gradients observed in the Sierra de Las Minas (SLM) of eastern Guatemala. Soils were sampled in intact forest and 14 year-old landside sites underlain by gneiss in the southern dry to mesic (Motagua) and northern wet (Polochic) aspects of the SLM along wide elevation, temperature, and precipitation gradients. Soils samples (10 cm depth increments down to 30 cm) from each site were processed to estimate soil bulk density and obtain total carbon and nitrogen, and ?13C and ?15N. Soil organic carbon density exhibited a greater variability in forests of the Motagua (10-170 MgC ha-1) than the Polochic (40-160 MgC ha-1) whereas the opposite was true in landslides (5-40 MgC ha-1 versus10-90 MgC ha-1 in the Motagua and Polochic, respectively). Soil organic carbon density was related non-linearly with mean annual temperature (MAT) and mean total annual precipitation (MAP) but the strength and sign of the interactions differed with aspect and habitats which suggests that landsliding has different potentials to mobilize and fix carbon along the complex environmental gradients of the SLM. Similarly, the C:N ratios and ?13C and ?15N values varied between forests and landslides of the Motagua and Polochic sides of the SLM suggesting important differences in the carbon cycle and thus functioning of montane ecosystems mediated by landslide activity. Results of our work are critical both for characterizing the size of soil organic carbon stocks and pinpointing the source of carbon mobilized by landsliding in the SLM.

Restrepo, C.



Distribution, abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake, Nevada - An alkaline, meromictic lake  

NASA Technical Reports Server (NTRS)

The study of the distribution and isotopic composition of low molecular weight hydrocarbon gases at the Big Soda Lake, Nevada, has shown that while neither ethylene nor propylene were found in the lake, ethane, propane, isobutane and n-butane concentrations all increased with water column depth. It is concluded that methane has a biogenic origin in both the sediments and the anoxic water column, and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in delta C-13/CH4/ and CH4/(C2H6 + C3H8) with depth in the water column and sedimeents are probably due to bacterial processes, which may include anaerobic methane oxidation and different rates of methanogenesis, and C2-to-C4 alkane production by microorganisms.

Oremland, R. S.; Des Marais, D. J.



1, 393412, 2004 Carbon isotope  

E-print Network

BGD 1, 393­412, 2004 Carbon isotope anomaly in the major plant C1 pool F. Keppler et al. Title Page Biogeosciences Discussions is the access reviewed discussion forum of Biogeosciences Carbon isotope 393 #12;BGD 1, 393­412, 2004 Carbon isotope anomaly in the major plant C1 pool F. Keppler et al. Title

Boyer, Edmond


Isotope-abundance variations of selected elements (IUPAC technical report)  

USGS Publications Warehouse

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

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



Study of the Role of Terrestrial Processes in the Carbon Cycle Based on Measurements of the Abundance and Isotopic Composition of Atmospheric CO2  

SciTech Connect

The main objective of this project was to continue research to develop carbon cycle relationships related to the land biosphere based on remote measurements of atmospheric CO2 concentration and its isotopic ratios 13C/12C, 18O/16O, and 14C/12C. The project continued time-series observations of atmospheric carbon dioxide and isotopic composition begun by Charles D. Keeling at remote sites, including Mauna Loa, the South Pole, and eight other sites. Using models of varying complexity, the concentration and isotopic measurements were used to study long-term change in the interhemispheric gradients in CO2 and 13C/12C to assess the magnitude and evolution of the northern terrestrial carbon sink, to study the increase in amplitude of the seasonal cycle of CO2, to use isotopic data to refine constraints on large scale changes in isotopic fractionation which may be related to changes in stomatal conductance, and to motivate improvements in terrestrial carbon cycle models. The original proposal called for a continuation of the new time series of 14C measurements but subsequent descoping to meet budgetary constraints required termination of measurements in 2007.

Stephen C. Piper; Ralph F. Keeling



Distribution, abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake, Nevada: An alkaline, meromictic lake  

USGS Publications Warehouse

Distribution and isotopic composition (??13C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20-35 m), reached uniform concentrations (55 ??M/l) in the monimolimnion (35-64 m) and again increased with depth in monimolimnion bottom sediments (>400 ??M/kg below 1 m sub-bottom depth). The ??13C[CH4] values in bottom sediment below 1 m sub-bottom depth (<-70 per mil) increased with vertical distance up the core (??13C[CH4] = -55 per mil at sediment surface). Monimolimnion ??13C[CH4] values (-55 to -61 per mil) were greater than most ??13C[CH4] values found in the anoxic mixolimnion (92% of samples had ??13C[CH4] values between -20 and -48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50-60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of CH4 [C2H6 + C3H8] were high (250-620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in ??13C[CH4] and CH4 (C2H6 + C3H8) with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C2 to C4 alkane production by microorganisms. ?? 1983.

Oremland, R.S.; Des Marais, D.J.



Carbon isotopic fractionation in heterotrophic microbial metabolism  

NASA Technical Reports Server (NTRS)

Differences in the natural-abundance carbon stable isotopic compositions between products from aerobic cultures of Escherichia coli K-12 were measured. Respired CO2 was 3.4 percent depleted in C-13 relative to the glucose used as the carbon source, whereas the acetate was 12.3 percent enriched in C-13. The acetate C-13 enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6 percent depleted in C-13, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7 percent, respectively. Aspartic and glutamic acids were -1.6 and +2.7 percent, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle.

Blair, N.; Leu, A.; Munoz, E.; Olsen, J.; Kwong, E.; Des Marais, D.



Carbon isotopic fractionation in heterotrophic microbial metabolism.  

PubMed Central

Differences in the natural-abundance carbon stable isotopic compositions between products from aerobic cultures of Escherichia coli K-12 were measured. Respired CO2 was 3.4% depleted in 13C relative to the glucose used as the carbon source, whereas the acetate was 12.3% enriched in 13C. The acetate 13C enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6% depleted in 13C, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7%, respectively. Aspartic and glutamic acids were -1.6 and +2.7%, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle. PMID:2867741

Blair, N; Leu, A; Muñoz, E; Olsen, J; Kwong, E; Des Marais, D



Variable Carbon Isotopes in ALH84001 Carbonates  

NASA Astrophysics Data System (ADS)

The Martian meteorite ALH84001 contains a small amount of carbonate that was deposited from aqueous fluids on the Martian surface approximately 3.9 Ga.. McKay et al. (1996) proposed evidence for the existence of life preserved within the carbonate grains. In order to determine the nature of the ancient Martian aqueous system we have combined previously collected oxygen isotopic data with new carbon isotopic measurements performed on the Cameca 6f ion microprobe at Arizona State University. Isotopic measurements were made at high mass resolution with a spot size of 10 microns. The measured carbon isotopic values range from 29.2‰ to 64.5‰ (PDB) with an average uncertainty of +/-1.6‰ (1? ). These data agree very well with previous acid dissolution and stepped combustion experiments which range from a ?13C of +32‰ to +41‰ . As observed with the oxygen isotopic data, the carbon isotopic composition is correlated with the chemical composition of the carbonates. This allows us to establish that the earliest (Ca-rich) carbonates had the lightest carbon isotopic composition while the latest forming (Mg-rich) carbonates had the heaviest carbon isotopic composition. The large range of carbon isotopic compositions measured in this study cannot be explained by previously proposed models. Temperature change or a Rayleigh distillation process caused by progressive carbonate precipitation are insufficient to create the observed carbon isotopic compositions. Furthermore, processes such as evaporation or photosynthesis will not produce large carbon isotopic variations due to rapid isotopic equilibration with the atmosphere. We propose two possible models for the formation of the ALH84001 carbonates consistent with the isotopic data collected thus far. Carbonates could have formed from an evolving system where the carbon and oxygen isotopic composition of the carbonates reflects a mixing between magmatic hydrothermal fluids and fluids in equilibrium with an isotopically heavy atmosphere. Alternatively, carbon enrichment could have occurred as a portion of the carbon dioxide is reduced through abiotic Fischer-Tropsch synthesis or biologically mediated methanogenesis. In this scenario, cooling of the system over time would be necessary to create observed oxygen isotopic values.

Niles, P. B.; Leshin, L. A.; Guan, Y.



Carbon isotope and abundance systematics of Icelandic geothermal gases, fluids and subglacial basalts with implications for mantle plume-related CO2 fluxes  

NASA Astrophysics Data System (ADS)

We report new carbon dioxide (CO2) abundance and isotope data for 71 geothermal gases and fluids from both high-temperature (HT > 150 °C at 1 km depth) and low-temperature (LT < 150 °C at 1 km depth) geothermal systems located within neovolcanic zones and older segments of the Icelandic crust, respectively. These data are supplemented by CO2 data obtained by stepped heating of 47 subglacial basaltic glasses collected from the neovolcanic zones. The sample suite has been characterized previously for He-Ne (geothermal) and He-Ne-Ar (basalt) systematics (Füri et al., 2010), allowing elemental ratios to be calculated for individual samples. Geothermal fluids are characterized by a wide range in carbon isotope ratios (?13C), from -18.8‰ to +4.6‰ (vs. VPDB), and CO2/3He values that span eight orders of magnitude, from 1 × 104 to 2 × 1012. Extreme geothermal values suggest that original source compositions have been extensively modified by hydrothermal processes such as degassing and/or calcite precipitation. Basaltic glasses are also characterized by a wide range in ?13C values, from -27.2‰ to -3.6‰, whereas CO2/3He values span a narrower range, from 1 × 108 to 1 × 1012. The combination of both low ?13C values and low CO2 contents in basalts indicates that magmas are extensively and variably degassed. Using an equilibrium degassing model, we estimate that pre-eruptive basaltic melts beneath Iceland contain ?531 ± 64 ppm CO2 with ?13C values of -2.5 ± 1.1‰, in good agreement with estimates from olivine-hosted melt inclusions (Metrich et al., 1991) and depleted MORB mantle (DMM) CO2 source estimates (Marty, 2012). In addition, pre-eruptive CO2 compositions are estimated for individual segments of the Icelandic axial rift zones, and show a marked decrease from north to south (Northern Rift Zone = 550 ± 66 ppm; Eastern Rift Zone = 371 ± 45 ppm; Western Rift Zone = 206 ± 24 ppm). Notably, these results are model dependent, and selection of a lower ?13C fractionation factor will result in lower source estimates and larger uncertainties associated with the initial ?13C estimate. Degassing can adequately explain low CO2 contents in basalts; however, degassing alone is unlikely to generate the entire spectrum of observed ?13C variations, and we suggest that melt-crust interaction, involving a low ?13C component, may also contribute to observed signatures. Using representative samples, the CO2 flux from Iceland is estimated using three independent methods: (1) combining measured CO2/3He values (in gases and basalts) with 3He flux estimates (Hilton et al., 1990), (2) merging basaltic emplacement rates of Iceland with pre-eruptive magma source estimates of ?531 ± 64 ppm CO2, and (3) combining fluid CO2 contents with estimated regional fluid discharge rates. These methods yield CO2 flux estimates from of 0.2-23 × 1010 mol a-1, which represent ?0.1-10% of the estimated global ridge flux (2.2 × 1012 mol a-1; Marty and Tolstikhin, 1998).

Barry, P. H.; Hilton, D. R.; Füri, E.; Halldórsson, S. A.; Grönvold, K.



Exploring Marine Carbon Isotope Excursions  

NSDL National Science Digital Library

David Jones, Geology Department, Amherst College Topic: stable isotopes, geochemistry, oceanography, carbon cycle Course type: Upper level undergraduate course Description The exercise is designed to introduce ...


Climatic/Hydrologic Oscillations since 155,000 yr B.P. at Owens Lake, California, Reflected in Abundance and Stable Isotope Composition of Sediment Carbonate  

USGS Publications Warehouse

Sediment grain size, carbonate content, and stable isotopes in 70-cm-long (???1500-yr) channel samples from Owens Lake core OL-92 record many oscillations representing climate change in the eastern Sierra Nevada region since 155,000 yr B.P. To first order, the records match well the marine ??18O record. At Owens Lake, however, the last interglaciation appears to span the entire period from 120,000 to 50,000 yr B.P., according to our chronology, and was punctuated by numerous short periods of wetter conditions during an otherwise dry climate. Sediment proxies reveal that the apparent timing of glacial-interglacial transitions, notably the penultimate one, is proxy-dependent. In the grain-size and carbonate-content records this transition is abrupt and occurs at ??? 120,000 yr B.P. In contrast, in the isotopic records the transition is gradual and occurs between 145,000 and 120,000 yr B. P. Differences in timing of the transition are attributed to variable responses by proxies to climate change. ?? 1997 University of Washington.

Menking, K.M.; Bischoff, J.L.; Fitzpatrick, J.A.; Burdette, J.W.; Rye, R.O.



Carbon isotopes in mollusk shell carbonates  

NASA Astrophysics Data System (ADS)

Mollusk shells contain many isotopic clues about calcification physiology and environmental conditions at the time of shell formation. In this review, we use both published and unpublished data to discuss carbon isotopes in both bivalve and gastropod shell carbonates. Land snails construct their shells mainly from respired CO2, and shell ?13C reflects the local mix of C3 and C4 plants consumed. Shell ?13C is typically >10‰ heavier than diet, probably because respiratory gas exchange discards CO2, and retains the isotopically heavier HCO3 -. Respired CO2 contributes less to the shells of aquatic mollusks, because CO2/O2 ratios are usually higher in water than in air, leading to more replacement of respired CO2 by environmental CO2. Fluid exchange with the environment also brings additional dissolved inorganic carbon (DIC) into the calcification site. Shell ?13C is typically a few ‰ lower than ambient DIC, and often decreases with age. Shell ?13C retains clues about processes such as ecosystem metabolism and estuarine mixing. Ca2+ ATPase-based models of calcification physiology developed for corals and algae likely apply to mollusks, too, but lower pH and carbonic anhydrase at the calcification site probably suppress kinetic isotope effects. Carbon isotopes in biogenic carbonates are clearly complex, but cautious interpretation can provide a wealth of information, especially after vital effects are better understood.

McConnaughey, Ted A.; Gillikin, David Paul



Interpreting carbon-isotope excursions: carbonates and organic matter  

Microsoft Academic Search

Variations in the carbon isotopic compositions of marine carbonate and organic carbon provide a record of changes in the fraction of organic carbon buried through time and may provide clues to changes in rates of weathering and sources of organic carbon. Paired carbonate and organic carbon isotope determinations provide a possibility of interpreting not only changes in the global carbon

Lee R. Kump; Michael A. Arthur



Decrease in Carbon Isotope Rations  

NSDL National Science Digital Library

This three-panel figure is an infographic showing how carbon and oxygen isotope ratios, temperature, and carbonate sediments have changed during the Palaeocene-Eocene Thermal Maximum. The figure caption provides sources to scientific articles from which this data was derived. A graphic visualization from the Intergovernmental Panel on Climate Change shows the rapid decrease in carbon isotope ratios that is indicative of a large increase in the atmospheric greenhouse gases CO2 and CH4, which was coincident with approximately 5C of global warming.

Intergovernmental Panel on Climate Change (IPCC)


(Carbon isotope fractionation inplants)  

SciTech Connect

The objectives of this research are: To develop a theoretical and experimental framework for understanding isotope fractionations in plants; and to develop methods for using this isotope fractionation for understanding the dynamics of CO{sub 2} fixation in plants. Progress is described.

O'Leary, M.H.



Ultimate Isotope Precision for Carbonates Thermo Scientific  

E-print Network

Ultimate Isotope Precision for Carbonates Thermo Scientific KIEL IV Carbonate Device Part of Thermo integration cycle Ultimate Isotope Precision for Carbonates The Thermo Scientific KIEL IV Carbonate DeviceV Thermo Scientific MAT 253 or the 3-kV DELTA V isotope ratio mass spectrometer meets the requirements

Lachniet, Matthew S.



SciTech Connect

Along with my usual weekly review of the published literature for new nuclear data, I also search for new candidates for best measurements of isotopic abundances from a single source. Most of the published articles, that I previously had found in the Research Library at the Brookhaven Lab, have already been sent to the members of the Atomic Weights Commission, by either Michael Berglund or Thomas Walczyk. In the last few days, I checked the published literature for any other articles in the areas of natural variations in isotopic abundance ratios, measurements of isotopic abundance ratios on samples of extra-terrestrial material and isotopic abundance ratio measurements performed using ICPMS instruments. Hopefully this information will be of interest to members of the Commission, the sub-committee on isotopic abundance measurements (SIAM), members of the former sub-committee on natural isotopic fractionation (SNIF), the sub-committee on extra-terrestrial isotope ratios (SETIR), the RTCE Task Group and the Guidelines Task Group, who are dealing with ICPMS and TIMS comparisons. In the following report, I categorize the publications in one of four areas. Measurements performed using either positive or negative ions with Thermal Ionization Mass Spectrometer, TIMS, instruments; measurements performed on Inductively Coupled Plasma Mass Spectrometer, ICPMS, instruments; measurements of natural variations of the isotopic abundance ratios; and finally measurements on extra-terrestrial samples with instrumentation of either type. There is overlap in these areas. I selected out variations and ET results first and then categorized the rest of the papers by TIMS and ICPMS.




Stable Carbon and Nitrogen Isotopic  

Microsoft Academic Search

The perennially ice-covered lakes in the McMurdo Dry Valleys, Antarctica, are part of the coldest and driest ecosystem on earth. To understand lacustrine carbon and nitrogen cycling in this end-member ecosystem, and to define paleolimnological proxies for ice-covered lakes, we measured the stable carbon and nitrogen isotopic composition of particulate organic matter (POM) and benthic organic matter (BOM) within the

Jennifer Lawson; PETER T. DORAN; Fabien Kenig; DAVID J. DES MARAIS; JOHN C. PRISCU



Europium Isotopic Abundances in Very Metal-poor Stars  

E-print Network

Europium isotopic abundance fractions are reported for the very metal-poor, neutron-capture-rich giant stars CS 22892-052, HD 115444, and BD +17 3248. The abundance fractions, derived from analysis of several strong Eu II lines appearing in high-resolution spectra of these stars, are in excellent agreement with each other and with their values in the Solar System: fraction(\\iso{Eu}{151}) ~= fraction(\\iso{Eu}{153}) ~= 0.5. Detailed abundance studies of very metal-poor stars have previously shown that the total elemental abundances of stable atoms with atomic numbers z >= 56 typically match very closely those of a scaled solar-system r-process abundance distribution. The present results for the first time extend this agreement to the isotopic level.

Christopher Sneden; John J. Cowan; James E. Lawler; Scott Burles; Timothy C. Beers; George M. Fuller



Isotopic abundance in atom trap trace analysis  


A method and system for detecting ratios and amounts of isotopes of noble gases. The method and system is constructed to be able to measure noble gas isotopes in water and ice, which helps reveal the geological age of the samples and understand their movements. The method and system uses a combination of a cooled discharge source, a beam collimator, a beam slower and magneto-optic trap with a laser to apply resonance frequency energy to the noble gas to be quenched and detected.

Lu, Zheng-Tian; Hu, Shiu-Ming; Jiang, Wei; Mueller, Peter



Carbon-13 isotopic abundance and concentration of atmospheric methane for background air in the Southern and Northern Hemispheres from 1978 to 1989  

SciTech Connect

Atmospheric methane (CH{sub 4}) may become an increasingly important contributor to global warming in future years. Its atmospheric concentration has risen, doubling over the past several hundred years, and additional methane is thought to have a much greater effect on climate, on a per molecule basis, than additional C0{sub 2} at present day concentrations (Shine et al. 1990). The causes of the increase of atmospheric CH{sub 4} have been difficult to ascertain because of a lack of quantitative knowledge of the fluxes (i.e., net emissions) from the numerous anthropogenic and natural sources. The goal of CH{sub 4} isotopic studies is to provide a constraint (and so reduce the uncertainties) in estimating the relative fluxes from the various isotopically distinct sources, whose combined fluxes must result in the measured atmospheric isotopic composition, after the fractionating effect of the atmospheric removal process is considered. In addition, knowledge of the spatial and temporal changes in the isotopic composition of atmospheric CH{sub 4}, along with estimates of the fluxes from some of the major sources, makes it possible to calculate growth rates for sources whose temporal emissions trends would be difficult to measure directly.

Stevens, C.M. [Argonne National Lab., IL (United States); Sepanski; Morris, L.J. [Univ. of Tennessee, Knoxville, TN (United States). Energy, Environment, and Resources Center



Carbon and nitrogen stable isotopic inventory of the most abundant demersal fish captured by benthic gears in southwestern Iceland (North Atlantic)  

NASA Astrophysics Data System (ADS)

Stable isotopes (?13C and ?15N) were used to examine the origin of organic matter for the most representative demersal species of the SW Icelandic fishery, accounting for over 70% of landings of those species in the North Atlantic. Samples were collected during a 2-week period in early September 2004 from landings and directly during fishing cruises. Stable isotopes showed that particulate organic matter and sedimentary organic matter were at the base of the food web and appeared to fill two different compartments: the pelagic and the benthic. The pelagic realm was composed of only capelin and sandeel; krill and redfish occupied an intermediate position between pelagic and benthic realms; while anglerfish, haddock, cod and ling resulted as the true demersal species while tusk, rays and plaice were strongly linked to the benthic habitat.

Sarà, Gianluca; de Pirro, Maurizio; Sprovieri, Mario; Rumolo, Paola; Halldórsson, Halldór Pálmar; Svavarsson, Jörundur



Developing Model Constraints on Northern Extra-Tropical Carbon Cycling Based on measurements of the Abundance and Isotopic Composition of Atmospheric CO2  

SciTech Connect

The objective of this project was to perform CO2 data syntheses and modeling activities to address two central questions: 1) how much has the seasonal cycle in atmospheric CO2 at northern high latitudes changed since the 1960s, and 2) how well do prognostic biospheric models represent these changes. This project also supported the continuation of the Scripps time series of CO2 isotopes and concentration at ten baseline stations distributed globally.

Keeling, Ralph [UCSD-SIO



Report on carbon and nitrogen abundance studies  

NASA Technical Reports Server (NTRS)

The aim of the proposal was to determine the nitrogen to carbon abundance ratios from transition layer lines in stars with different T(sub eff) and luminosities. The equations which give the surface emission line fluxes and the measured ratio of the NV to CIV emission line fluxes are presented and explained. The abundance results are compared with those of photospheric abundance studies for stars in common with the photospheric investigations. The results show that the analyses are at least as accurate as the photospheric determinations. These studies can be extended to F and early G stars for which photospheric abundance determinations for giants are hard to do because molecular bands become too weak. The abundance determination in the context of stellar evolution is addressed. The N/C abundance ratio increases steeply at the point of evolution for which the convection zone reaches deepest. Looking at the evolution of the rotation velocities v sin i, a steep decrease in v sin i is related to the increasing depth of the convection zone. It is concluded that the decrease in v sin i for T(sub eff) less than or approximately = 5800 K is most probably due to the rearrangement of the angular momentum in the stars due to deep convective mixing. It appears that the convection zone is rotating with nearly depth independent angular momentum. Other research results and ongoing projects are discussed.

Boehm-Vitense, Erika



Carbon isotopic composition of Amazon shelf sediments  

SciTech Connect

The distribution of carbon isotopes in Amazon shelf sediment is controlled by the same processes that are forming the modern subaqueous delta. The terrestrial (-27 to -25 per thousand) isotopic carbon signal observed in surficial sediments near the river mouth extends over 400 km northwest along the shelf. Terrestrial carbon is associated with areas of rapid sediment accumulation (topset and foreset regions). A sharp boundary between terrestrial (-27 to -25 per thousand) and marine (-23 to -22 per thousand) isotopic carbon values in surficial sediments is associated with a change in depositional conditions (foreset to bottomset regions) and a decrease in sediment accumulation rate. POC water-column isotopic values (-27 per thousand) near the river mouth are similar to the underlying surficial-sediment TOC isotopic values, but POC water-column samples collected 20 km off the river mouth have marine carbon isotopic values (-22 to -19 per thousand) and differ from the underlying surficial-sediment TOC isotopic values. These water column observations are related to variations in turbidity and productivity. Down-core isotopic variation is only observed in cores taken in areas of lower sediment accumulation rates. These observations indicate that the organic carbon in Amazon shelf sediment is dominantly terrestrial in composition, and the location of deposition of this carbon is controlled by modern processes of sediment accumulation. The modern Amazon shelf is similar to large clinoform shale deposits of the Cretaceous in North America. Thus, the stratigraphic setting may help predict the isotopic variations of carbon in ancient deposits.

Showers, W.J.; Angle, D.G.; Nittrouer, C.A.; Demaster, D.J.



Carbon isotope effects in carbonate systems  

NASA Astrophysics Data System (ADS)

Global carbon cycle models require a complete understanding of the ? 13C variability of the Earth's C reservoirs as well as the C isotope effects in the transfer of the element among them. An assessment of ? 13C changes during CO 2 loss from degassing magmas requires knowledge of the melt-CO 2 carbon isotope fractionation. In order to examine the potential size of this effect for silicate melts of varying composition, 13C reduced partition functions were computed in the temperature range 275 to 4000 K for carbonates of varying bond strengths (Mg, Fe, Mn, Sr, Ba, Pb, Zn, Cd, Li, and Na) and the polymorphs of calcite. For a given cation and a given pressure the 13C content increases with the density of the carbonate structure. For a given structure the tendency to concentrate 13C increases with pressure. The effect of pressure (‰/10 kbar) on the size of the reduced partition function of aragonite varies with temperature; in the pressure range 1 to 10 5 bars the change is given by: ? 13C p average=-0.01796+0.06635? 10 3/T+0.006875? 10 6/T2 For calcite III the pressure effect is on average 1.4× larger than that for aragonite at all temperatures. The nature of the cation in a given structure type has a significant effect on the carbon isotope fractionation properties. The tendency to concentrate 13C declines in the series magnesite, aragonite, dolomite, strontianite, siderite, calcite, smithonite, witherite, rhodochrosite, otavite, cerrusite. For divalent cations a general expression for an estimation of the reduced partition function (?) from the reduced mass (? = [M Cation × M Carbonate]/[M Cation + M Carbonate]) is: 1000 ln?=(0.032367-0.072563? 10 3/T-0.01073? 10 6/T2)??-14.003+29.953? 10 3/T+9.4610? 10 6/T2 For Mg-calcite the 13C content varies with the Mg concentration. The fractionation between Mg-calcite (X = mole fraction of MgCO 3) and calcite is given by: 1000 ln(? MgCalite- Calcite)=[0.013702-0.10957× 10 3/T+1.35940× 10 6/T2-0.329124× 10 9/T3+0.0304160× 10 12/T4]× X1.5 The results of the computations were used together with previously published experimental vaporous CO 2-silicate melt fractionations to determine, at 1200°C, a relationship between melt-CO 213C fractionation and melt composition, expressed as molecular proportions of the cations Mg, Fe, Mn, Ca, Na, K and Si and Al: 1000 ln? Melt- CO2=5.14× Mg+ Fe+ Mn+ Ca+ Na+ K/Si+ Al+0.86 A conceptual model to understand this relationship was developed. The results of the computations approximate closely the experimentally determined vaporous CO 2-CaCO 3 fractionations at high temperatures. Empirically derived dolomite-calcite and calcite-graphite 13C isotope geothermometers agree with results of the present work.

Deines, Peter



Carbon isotope controlled molecular switches  

NASA Astrophysics Data System (ADS)

Single molecules represent one fundamental limit to the downscaling of electronics. As a prototype element for carbon-based nanoscale science and technology, the detailed behavior of carbon monoxide (CO) on the copper surface Cu(111) has been investigated. These investigations span from individual carbon isotope resolution, to single molecules, to compact clusters assembled by molecular manipulation via a homemade scanning tunneling microscope (STM). Sub-nanoscale devices, composed of only a few molecules, which exploit both lone CO properties and molecule-molecule interaction, have been designed and assembled. The devices function as bi-stable switches and can serve as classical bits with densities > 50 Tbits/cm2. Operated in the nuclear mass sensitive regime, each switch can also function as a molecular "centrifuge" capable of identifying the isotope of a single carbon atom in real-time. A model, based on electron-vibron couping and inelastic tunneling, has been developed and explains the dynamic behavior of the switch. The interaction between pairs of switches was also explored and it was found that their behavior ranges from completely independent to strongly coupled. Larger nanostructures, which were composed of many sub-switches organized to leverage the fully coupled interaction, link two spatially separated "bits" on the surface. Such a linked system can set or read a state non-locally, which is equivalent to bidirectional information transfer. The linked system has also exhibited logic functionality. These experiments demonstrate scalable molecular cells for information storage, and for information processing through cellular automata logic schemes.

Foster, Brian K.


Carbon Isotope Ratios in Belowground Carbon Cycle Processes  

Microsoft Academic Search

Abstract Analyses of carbon isotope ratios (?,C values of CO2effluxing from soils, but asof,yet a global,database,is lacking,with which,to test this prediction. Such a global,database,would be a useful input for global carbon cycle models,which,rely on ?values,to constrain source and sink relations. Keywords: global change, ecosystem processes, soil organic carbon, carbon isotope ratio, carbon cycle,

James R. Ehleringer; Nina Buchmann; Lawrence B. Flanagan



The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials  

NASA Technical Reports Server (NTRS)

During the past three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. As part of my startup package I received funds to construct a state-of-the-art experimental facility to study gas-solid reaction kinetics. Much of our effort was spent developing the methodology to measure the abundance and isotopic composition of Hg at ultratrace levels in solid materials. In our first study, the abundance and isotopic composition of Hg was determined in bulk samples of the Murchison (CM) and Allende (CV) carbonaceous chondrites. We have continued our study of mercury in primitive meteorites and expanded the suite of meteorites to include other members of the CM and CV chondrite group as well as CI and CO chondrites. Samples of the CI chondrite Orgueil, the CM chondrites Murray, Nogoya, and Cold Bokkeveld, the CO chondrites Kainsaz, Omans, and Isna, and the CV chondrites Vigarano, Mokoia, and Grosnaja were tested. We have developed a thermal analysis ICP-MS technique and applied it to the study of a suite of thermally labile elements (Zn, As, Se, Cd, In, Sn, Sb, Te, Hg, Au, Tl, Pb, and Bi) in geologic materials as well.

Lauretta, D. S.



The abundance and isotopic composition of Cd in iron meteorites  

NASA Astrophysics Data System (ADS)

Cadmium is a highly volatile element and its abundance in meteorites may help better understand volatility-controlled processes in the solar nebula and on meteorite parent bodies. The large thermal neutron capture cross section of 113Cd suggests that Cd isotopes might be well suited to quantify neutron fluences in extraterrestrial materials. The aims of this study were (1) to evaluate the range and magnitude of Cd concentrations in magmatic iron meteorites, and (2) to assess the potential of Cd isotopes as a neutron dosimeter for iron meteorites. Our new Cd concentration data determined by isotope dilution demonstrate that Cd concentrations in iron meteorites are significantly lower than in some previous studies. In contrast to large systematic variations in the concentration of moderately volatile elements like Ga and Ge, there is neither systematic variation in Cd concentration amongst troilites, nor amongst metal phases of different iron meteorite groups. Instead, Cd is strongly depleted in all iron meteorite groups, implying that the parent bodies accreted well above the condensation temperature of Cd (i.e., ?650 K) and thus incorporated only minimal amounts of highly volatile elements. No Cd isotope anomalies were found, whereas Pt and W isotope anomalies for the same iron meteorite samples indicate a significant fluence of epithermal and higher energetic neutrons. This observation demonstrates that owing to the high Fe concentrations in iron meteorites, neutron capture mainly occurs at epithermal and higher energies. The combined Cd-Pt-W isotope results from this study thus demonstrate that the relative magnitude of neutron capture-induced isotope anomalies is strongly affected by the chemical composition of the irradiated material. The resulting low fluence of thermal neutrons in iron meteorites and their very low Cd concentrations make Cd isotopes unsuitable as a neutron dosimeter for iron meteorites.

Kruijer, Thomas S.; Sprung, Peter; Kleine, Thorsten; Leya, Ingo; Wieler, Rainer



Biomarker and Carbon Isotope Signals from Leaf to Terrestrial Archive  

NASA Astrophysics Data System (ADS)

Biomarker and isotopic signatures of terrestrial organic matter are increasingly used to discern organic matter provenance in transport systems as well as to reconstruct environmental conditions of ancient landscapes. Such tools help scholars evaluate river transport and the influence of climate on terrestrial biomass and soil carbon, the largest reduced carbon inventories within the global surface environment. These signals reflect isotopic fractionation during photosynthesis and the abundance and composition of plant lipids, which are ultimately influenced by plant community, ecosystem structure and climate. Case studies and literature data for plants, biomarkers, litter carbon and soil organic matter refine the framework for evaluating and interpreting ancient terrestrial environments. Such studies reveal isotopic and biomarker patterns primarily track woody cover and moisture gradients in ancient landscapes. This emerging approach is currently limited by a lack of supporting and critical information about carbon isotopic differences between lipids and leaves, which appear to vary with environment as well as plant type. Environmental reconstructions and carbon-cycle studies are also limited by incomplete understanding of carbon isotopic relationships between modern litter, mineral soil, leaf waxes, and ancient archives of these properties. The net imprint of diagenesis on bulk carbon archives can potentially be constrained with companion biomarker studies, provided biomass production, litter delivery and lipid isotopic characteristics are constrained. Soil organic matter isotopic diagenesis is not fully understood, especially on geologic timescales, but appears to vary with both climate and ecosystem properties. This presentation will highlight recent findings and current knowledge gaps in understanding biomarker and ancient soil organic carbon as landscape tracers of past vegetation and climate.

Freeman, K. H.



Carbon isotope effects associated with aceticlastic methanogenesis.  

PubMed Central

The carbon isotope effects associated with synthesis of methane from acetate have been determined for Methanosarcina barkeri 227 and for methanogenic archaea in sediments of Wintergreen Lake, Michigan. At 37 degrees C, the 13C isotope effect for the reaction acetate (methyl carbon) --> methane, as measured in replicate experiments with M. barkeri, was - 21.3% +/- 0.3%. The isotope effect at the carboxyl portion of acetate was essentially equal, indicating participation of both positions in the rate-determining step, as expected for reactions catalyzed by carbon monoxide dehydrogenase. A similar isotope effect, - 19.2% +/- 0.3% was found for this reaction in the natural community (temperature = 20 degrees C). Given these observations, it has been possible to model the flow of carbon to methane within lake sediment communities and to account for carbon isotope compositions of evolving methane. Extension of the model allows interpretation of seasonal fluctuations in 13C contents of methane in other systems. PMID:11536629

Gelwicks, J T; Risatti, J B; Hayes, J M



Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA).  


Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored. PMID:23419016

Chew, Gina; Walczyk, Thomas



Carbon and nitrogen isotope studies in an arctic ecosystem  

SciTech Connect

This proposal requests funding for the completion of our current ecological studies at the MS-117 research site at Toolik Lake, Alaska. We have been using a mix of stable and radioisotope techniques to assess the fluxes of carbon and nitrogen within the ecosystem and the implications for long-term carbon storage or loss from the tundra. Several tentative conclusions have emerged from our study including: Tundra in the foothills is no longer accumulating carbon. Surficial radiocarbon abundances show little or no accumulation since 1000--2500 yrs BP. Coastal plain tundra is still accumulating carbon, but the rate of accumulation has dropped in the last few thousand years. Carbon export from watersheds in the Kuparuk and Imnavait Creek drainages are in excess of that expected from estimated primary productivity; and Nitrogen isotope abundances vary between species of plants and along hydrologic gradients.

Schell, D.M.



Carbon and nitrogen isotope studies in an arctic ecosystem  

SciTech Connect

This proposal requests funding for the completion of our current ecological studies at the MS-117 research site at Toolik Lake, Alaska. We have been using a mix of stable and radioisotope techniques to assess the fluxes of carbon and nitrogen within the ecosystem and the implications for long-term carbon storage or loss from the tundra. Several tentative conclusions have emerged from our study including: Tundra in the foothills is no longer accumulating carbon. Surficial radiocarbon abundances show little or no accumulation since 1000--2500 yrs BP. Coastal plain tundra is still accumulating carbon, but the rate of accumulation has dropped in the last few thousand years. Carbon export from watersheds in the Kuparuk and Imnavait Creek drainages are in excess of that expected from estimated primary productivity; and Nitrogen isotope abundances vary between species of plants and along hydrologic gradients.

Schell, D.M.



Carbon isotope effects associated with autotrophic acetogenesis  

USGS Publications Warehouse

The carbon kinetic isotope effects associated with synthesis of acetate from CO2 and H2 during autotrophic growth of Acetobacterium woodii at 30??C have been measured by isotopic analyses of CO2, methyl-carbon, and total acetate. Closed systems allowing construction of complete mass balances at varying stages of growth were utilized, and the effects of the partitioning of carbon between CO2 and HCO3- were taken into account. For the overall reaction, total carbonate ??? total acetate, isotope effects measured in replicate experiments ranged from -59.0 ?? 0.9% to - 57.2 ?? 2.3z%. Taking into account all measurements, the weighted mean and standard deviation are -58.6 ?? 0.7%. There is no evidence for intramolecular ordering in the acetate. The carbon isotopic composition of sedimentary acetate, otherwise expected to be near that of sedimentary organic carbon, is likely to be depleted in environments in which autotrophic acetogenesis is occurring. ?? 1989.

Gelwicks, J.T.; Risatti, J.B.; Hayes, J.M.



Carbon and oxygen abundances in stellar populations  

NASA Astrophysics Data System (ADS)

Context. Carbon and oxygen abundances in stars are important in many fields of astrophysics including nucleosynthesis, stellar structure, evolution of galaxies, and formation of planetary systems. Still, our knowledge of the abundances of these elements in different stellar populations is uncertain because of difficulties in observing and analyzing atomic and molecular lines of C and O. Aims: Abundances of C, O, and Fe are determined for F and G main-sequence stars in the solar neighborhood with metallicities in the range -1.6 < [Fe/H] < +0.4 in order to study trends and possible systematic differences in the C/Fe, O/Fe, and C/O ratios for thin- and thick-disk stars as well as high- and low-alpha halo stars. In addition, we investigate if there is any connection between C and O abundances in stellar atmospheres and the occurrence of planets. Methods: Carbon abundances are determined from the ?? 5052,5380 C i lines and oxygen abundances from the ?7774 O i triplet and the forbidden [O i] line at 6300 Å. MARCS model atmospheres are applied and non-LTE corrections for the O i triplet are included. Results: Systematic differences between high- and low-alpha halo stars and between thin- and thick-disk stars are seen in the trends of [C/Fe] and [O/Fe]. The two halo populations and thick-disk stars show the same trend of [C/O] versus [O/H], whereas the thin-disk stars are shifted to higher [C/O] values. Furthermore, we find some evidence of higher C/O and C/Fe ratios in stars hosting planets than in stars for which no planets have been detected. Conclusions: The results suggest that C and O in both high- and low-alpha halo stars and in thick-disk stars are made mainly in massive (M> 8 M?) stars, whereas thin-disk stars have an additional carbon contribution from low-mass AGB and massive stars of high metallicity causing a rising trend of the C/O ratio with increasing metallicity. However, at the highest metallicities investigated ([Fe/H] ? + 0.4), C/O does not exceed 0.8, which seems to exclude formation of carbon planets if proto-planetary disks have the same composition as their parent stars. Based on observations made with the Nordic Optical Telescope and on data products from observations made with ESO Telescopes at the La Silla Paranal Observatory under programs given in Table 2 and in Tables 1 and 2 of Nissen & Schuster (2010).Tables 2-5 are available in electronic form at, and also available at the CDS via anonymous ftp to ( or via

Nissen, P. E.; Chen, Y. Q.; Carigi, L.; Schuster, W. J.; Zhao, G.



Carbon and its isotopes in mid-oceanic basaltic glasses  

USGS Publications Warehouse

Three carbon components are evident in eleven analyzed mid-oceanic basalts: carbon on sample surfaces (resembling adsorbed gases, organic matter, or other non-magmatic carbon species acquired by the glasses subsequent to their eruption), mantle carbon dioxide in vesicles, and mantle carbon dissolved in the glasses. The combustion technique employed recovered only reduced sulfur, all of which appears to be indigenous to the glasses. The dissolved carbon concentration (measured in vesicle-free glass) increases with the eruption depth of the spreading ridge, and is consistent with earlier data which show that magma carbon solubility increases with pressure. The total glass carbon content (dissolved plus vesicular carbon) may be controlled by the depth of the shallowest ridge magma chamber. Carbon isotopic fractionation accompanies magma degassing; vesicle CO2 is about 3.8??? enriched in 13C, relative to dissolved carbon. Despite this fractionation, ??13CPDB values for all spreading ridge glasses lie within the range -5.6 and -7.5, and the ??13CPDB of mantle carbon likely lies between -5 and -7. The carbon abundances and ??13CPDB values of Kilauea East Rift glasses apparently are influenced by the differentiation and movement of magma within that Hawaiian volcano. Using 3He and carbon data for submarine hydrothermal fluids, the present-day mid-oceanic ridge mantle carbon flux is estimated very roughly to be about 1.0 ?? 1013 g C/yr. Such a flux requires 8 Gyr to accumulate the earth's present crustal carbon inventory. ?? 1984.

Des Marais, D.J.; Moore, J.G.



Metallicity-Dependent Isotopic Abundances and the Impact of Helium Rate Uncertainties in Massive Stars  

NASA Astrophysics Data System (ADS)

All stellar evolution models for nucleosynthesis require an initial isotopic abundance set to use as a starting point, because nuclear reactions occur between isotopes. Generally, our knowledge of isotopic abundances of stars is fairly incomplete except for the Solar System. We develop a first model for a complete average isotopic decomposition as a function of metallicity. Our model is based on the underlying nuclear astrophysics processes, and is fitted to observational data, rather than traditional forward galactic chemical evolution modeling which integrates stellar yields beginning from big bang nucleosynthesis. We first decompose the isotopic solar abundance pattern into contributions from astrophysical sources. Each contribution is then assumed to scale as a function of metallicity. The resulting total isotopic abundances are summed into elemental abundances and fitted to available halo and disk stellar data to constrain the model's free parameter values. This procedure allows us to use available elemental observational data to reconstruct and constrain both the much needed complete isotopic evolution that is not accessible to current observations, and the underlying astrophysical processes. Our model finds a best fit for Type Ia supernovae contributing ˜0.7 to the solar Fe abundance, and Type Ia onset occurring at [Fe/H]~1.2, in agreement with typical values. The completed model can be used in future nucleosynthesis studies. We also perform a preliminary analysis to assess the impact of our isotopic scaling model on the resulting nucleosynthesis of massive stars, compared to a linear interpolation method. Using these two input methods we compute a limited grid of stellar models, and compare the final nucleosynthesis to observations. The compactness parameter was first used to assess which models would likely explode as successful supernovae, and contribute explosive nucleosynthesis yields. We find a better agreement to solar observations using the scaling model compared to the linear interpolation method, for the six s--only isotopes along the weak s--process path. As a second project, we study the sensitivity of presupernova evolution and supernova nucleosynthesis yields of massive stars to variations of the helium-burning reaction rates within the range of their uncertainties. The current solar abundances from Lodders (2010) are used for the initial stellar composition. We compute a grid of 12 initial stellar masses and 176 models per stellar mass to explore the effects of independently varying the 12C(alpha,gamma)16O and 3alpha reaction rates, denoted Ralpha,12 and R3alpha, respectively. The production factors of both the intermediate-mass elements (A=16--40) and the s--only isotopes along the weak s--process path ( 70Ge, 76Se, 80Kr, 82Kr, 86Sr, and 87Sr) were found to be in reasonable agreement with predictions for variations of R3alpha and Ralpha,12 of +/-25%; the s--only isotopes, however, tend to favor higher values of R3alpha than the intermediate-mass isotopes. The experimental uncertainty (one standard deviation) in R3alpha(Ralpha,12 ) is approximately +/-10%(+/-25%). The results show that a more accurate measurement of one of these rates would decrease the uncertainty in the other as inferred from the present calculations. We also observe sharp changes in production factors and standard deviations for small changes in the reaction rates, due to differences in the convection structure of the star. The compactness parameter was used to assess which models would likely explode as successful supernovae, and hence contribute explosive nucleosynthesis yields. We also provide the approximate remnant masses for each model and the carbon mass fractions at the end of core-helium burning as a key parameter for later evolution stages.

West, Christopher



Carbon IsotopesCarbon Isotopes A Short Course VU March, 2009  

E-print Network

2/25/2009 1 Carbon IsotopesCarbon Isotopes The Basics A Short Course VU March, 2009 Peter Swart Belemnite) V-PDB (Vienna Pee Dee Belemnite) #12;2/25/2009 2 Forms of Carbon · Primordial Carbon (324,000,000 1015 grams) ­ Methane ­ Graphite ­ Diamond ­ Other ?? · Carbonates (60,000,000 1015 grams)Ca bo ates

Miami, University of


Carbon isotope dynamics in Abies amabilis stands in the Cascades  

E-print Network

Carbon isotope dynamics in Abies amabilis stands in the Cascades N. Buchmann, T.M. Hinckley, and J.R. Ehleringer Abstract: Carbon isotope ratios (13 C) of canopy air and carbon isotope discrimination calculated an average 13 C for ecosystem respiration of ­26.4 ± 0.1. Ecosystem carbon isotope discrimination

Ehleringer, Jim


Clumped isotope thermometry of cryogenic cave carbonates  

NASA Astrophysics Data System (ADS)

Freezing of cave pool water that is increasingly oversaturated with dissolved carbonate leads to precipitation of a very specific type of speleothems known as cryogenic cave carbonates (CCC). At present, two different environments for their formation have been proposed, based on their characteristic carbon and oxygen isotope ratios. Rapidly freezing thin water films result in the fast precipitation of fine-grained carbonate powder (CCCfine). This leads to rapid physicochemical changes including CO2 degassing and CaCO3 precipitation, resulting in significantly 13C-enriched carbonates. Alternatively, slow carbonate precipitation in ice-covered cave pools results in coarse crystalline CCC (CCCcoarse) yielding strongly 18O-depleted carbonate. This is due to the formation of relatively 18O-enriched ice causing the gradual depletion of 18O in the water from which the CCC precipitates. Cryogenic carbonates from Central European caves were found to have been formed primarily during the last glacial period, specifically during times of permafrost thawing, based on the oxygen isotope ratios and U-Th dating. Information about the precise conditions of CCCcoarse formation, i.e. whether these crystals formed under equilibrium or disequilibrium conditions with the parent fluid, however, is lacking. An improved understanding of CCCcoarse formation will increase the predictive value of this paleo-permafrost archive. Here we apply clumped isotopes to investigate the formation conditions of cryogenic carbonates using well-studied CCCcoarse from five different cave systems in western Germany. Carbonate clumped isotope measurements yielded apparent temperatures between 3 and 18 °C and thus exhibit clear evidence of isotopic disequilibrium. Although the very negative carbonate ?18O values can only be explained by gradual freezing of pool water accompanied by preferential incorporation of 18O into the ice, clumped isotope-derived temperatures significantly above expected freezing temperatures indicate incomplete isotopic equilibration during precipitation of CCC. Fine-crystalline carbonate powder (<50 ?m, CCCfine) is thought to have formed in thin water films. Fast freezing causes strong isotopic disequilibrium effects related to rapid reaction rates, fast CO2 degassing, and limited isotopic equilibration (Clark and Lauriol, 1992) resulting in very positive ?13C (up to +18‰) and ?18O values (up to -2‰; Lacelle, 2007; Spötl, 2008; Žák et al., 2008). Larger crystals (mm to cm size, CCCcoarse) are thought to have formed in slow gradually freezing pool water (Žák et al., 2008), where super-saturation is created through ion rejection from the forming ice. This leads to slow mineral growth and strongly 18O-depleted CaCO3 (?18O: -24‰ to -10‰; Žák et al., 2012), but it is unknown whether CCCcoarse grows at isotopic equilibrium. Carbonate clumped isotope analyses (reported as ?47) are typically used to determine the formation temperature of carbonate minerals (Eiler, 2007, 2011; Affek, 2012). However, the sensitivity of ?47 to degassing makes it valuable also for the investigation of isotopic disequilibrium (Guo, 2008; Kluge and Affek, 2012). The carbonate clumped isotope thermometry is based on the temperature-dependent overabundance of 13C-18O bonds in the crystal lattice compared to a stochastic distribution.Depending on the conditions during carbonate formation, a varying degree of disequilibrium has been observed in clumped and oxygen isotopes of 'normal' speleothems (e.g., Mickler et al., 2006; Tremaine et al., 2011) complicating their interpretation. For stalagmites, an offset in ?18O of about 1‰ with respect to the isotopic equilibrium value is typically observed (McDermott et al., 2011) with a corresponding large offset in clumped isotopes (Affek et al., 2008; Daëron et al., 2011; Kluge and Affek, 2012). Initial degassing of CO2 from water that enters the low pCO2 cave environment (compared to the high CO2 levels found in soils) leads to an enrichment in 13C and 18O in DIC and depletion in ?47. Oxygen isotope e

Kluge, Tobias; Affek, Hagit P.; Zhang, Yi Ge; Dublyansky, Yuri; Spötl, Christoph; Immenhauser, Adrian; Richter, Detlev K.



The isotopic composition of carbonatite and kimberlite carbonates and their bearing on the isotopic composition of deep-seated carbon  

Microsoft Academic Search

New carbon and oxygen isotopic compositions of carbonates from 14 carbonatite and 11 kimberlite occurrences are reported. A review of the available data on the carbon isotopic composition ranges of carbonatite and kimberlite carbonates shows that they are similar and overlap that of diamonds. The mean carbon isotopic composition of carbonates from 22 selected carbonatite complexes (-5.1%., S = ±

P. Deines; D. P. Gold



[Abundance and activity of microorganisms at the water-sediment interface and their effect on the carbon isotopic composition of suspended organic matter and sediments of the Kara Sea].  


At ten stations of the meridian profile in the eastern Kara Sea from the Yenisei estuary through the shallow shelf and further through the St. Anna trough, total microbial numbers (TMN) determined by direct counting, total activity of the microbial community determined by dark CO2 assimilation (DCA), and the carbon isotopic composition of organic matter in suspension and upper sediment horizons (?13C, per thousand) were investigated. Three horizons were studied in detail: (1) the near-bottom water layer (20-30 cm above the sediment); (2) the uppermost, strongly hydrated sediment horizon, further termed warp (5-10 mm); and (3) the upper sediment horizon (1-5 cm). Due to decrease in the amount of isotopically light carbon of terrigenous origin with increasing distance from the Yenisei estuary, the TMN and DCA values decreased, and the ?13C changed gradually from -29.7 to -23.9 per thousand. At most stations, a noticeable decrease in TMN and DCA values with depth was observed in the water column, while the carbon isotopic composition of suspended organic matter did not change significantly. Considerable changes of all parameters were detected in the interface zone: TMN and DCA increased in the sediments compared to their values in near-bottom water, while the 13C content increased significantly, with ?13C of organic matter in the sediments being at some stations 3.5- 4.0 per thousand higher than in the near-bottom water. Due to insufficient illumination in the near-bottom zone, newly formed isotopically heavy organic matter (?13C(-) -20 per thousand) could not be formed by photosynthesis, active growth of chemoautotrophic microorganisms in this zone is suggested, which may use reduced sulfur, nitrogen, and carbon compounds diffusing from anaerobic sediments. High DCA values for the interface zone samples confirm this hypothesis. Moreover, neutrophilic sulfur-oxidizing bacteria were retrieved from the samples of this zone. PMID:25509411

Ivanov, M V; Lein, A Iu; Savvichev, A S; Rusanov, I I; Veslopolova, E F; Zakharova, E E; Prusakova, T S



The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials  

NASA Technical Reports Server (NTRS)

During the three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. At the time the grant started, our collaborating PI, Dante Lauretts, was a postdoctoral research associate working with Peter Buseck at Arizona State University. The work on chondritic Hg was done in collaboration with Dante Lauretta and Peter Buseck and this study was published in Lauretta et a1 (2001a). In July, 2001 Dante Lauretta accepted a position as an Assistant Professor in the Lunar and Planetary Laboratory at the University of Arizona. His funding was transferred and this grant has supported much of his research activities during his first two years at the U of A. Several other papers are in preparation and will be published soon. We presented papers on this topic at Goldschmidt Conferences, the Lunar and Planetary Science Conferences, and the Annual Meetings of the Meteoritical Society. The work done under this grant has spurred several new directions of inquiry, which we are still pursuing. Included in this paper are the studies of bulk abundances and isotopic compositions of metreoritic Mercury, and the development of a thermal analysis ICP-MS technique applied to thermally liable elements.

Blum, J. D.; Klaue, Bjorn



Organic and carbon isotope biogeochemistry of California coastal sediments  

SciTech Connect

Five studies examined various aspects of carbon cycling in two different marine sedimentary environments. Four of these considered sediment biogeochemistry and microbial ecology near natural hydrocarbon seepage (the Isla Vista seep). The fifth study involved the development and application of a new method for measuring total amounts of, and stable carbon isotopes in, dissolved organic carbon (DOC) of interstitial waters. Sediments at the Isla Vista seep were the most oxygen-limited and had high sulfate reduction rates compared with two non-seep sediments. Compounds which could be used to fuel subsurface anaerobic metabolism were limited. Although detected in high concentrations, sediment methane contribute insignificantly to sulfate reduction. Pore-water acetate was also detected in high concentrations at the seep, and acetate metabolism could potentially account for greater than one-third of total sulfate reduction there. The proportion of acetate assimilated to cellular carbon was lower, while water-soluble metabolites were higher, in seep sediments. Fossil, {sup 14}C-depleted carbon from hydrocarbon seepage was detected in varying amounts in total organic, dissolved inorganic, and meiofaunal and macrofaunal carbon from sediments at three sites near the seep. Using natural {sup 14}C abundances and mass balance considerations, estimates of fossil carbon mineralization or incorporation into faunal biomass were made. Development and subsequent application of a new method of DOC analysis showed that DOC exhibited a concentration maximum in the surface layer of a hypersaline microbial mat, contrasting with invariable total organic and dissolved inorganic carbon profiles. Isotopic abundances of DOC were {approximately}8 per mil lighter at 1.5-2.0-cm depth than in the mat surface (0-0.5 cm) indicating that it was the most isotopically dynamic of the three major carbon pools.

Bauer, J.E.



Elemental and isotopic abundances in the solar wind  

NASA Technical Reports Server (NTRS)

The use of collecting foils and lunar material to assay the isotopic composition of the solar wind is reviewed. Arguments are given to show that lunar surface correlated gases are likely to be most useful in studying the history of the solar wind, though the isotopic abundances are thought to give a good approximation to the solar wind composition. The results of the analysis of Surveyor material are also given. The conditions leading to a significant component of the interstellar gas entering the inner solar system are reviewed and suggestions made for experimental searches for this fraction. A critical discussion is given of the different ways in which the basic solar composition could be modified by fractionation taking place between the sun's surface and points of observation such as on the Moon or in interplanetary space. An extended review is made of the relation of isotopic and elemental composition of the interplanetary gas to the dynamic behavior of the solar corona, especially processes leading to fractionation. Lastly, connection is made between the subject of composition, nucleosynthesis and the convective zone of the sun, and processes leading to modification of initial accretion of certain gases on the Earth and Moon.

Geiss, J.



Evidence from carbon isotope measurements for diverse origins of sedimentary hydrocarbons  

NASA Technical Reports Server (NTRS)

The organic matter found in sedimentary rocks must derive from many sources; not only from ancient primary producers but also from consumers and secondary producers. In all of these organisms, isotope effects can affect the abundance and distribution of 13C in metabolites. Here, by using an improved form of a previously described technique in which the effluent of a gas chromatograph is continuously analysed isotopically, we report evidence of the diverse origins of sedimentary organic matter. The record of 13C abundances in sedimentary carbonate and total organic carbon can be interpreted in terms of variations in the global carbon cycle. Our results demonstrate, however, that isotope variations within sedimentary organic mixtures substantially exceed those observed between samples of total organic carbon. Resolution of isotope variations at the molecular level offers a new and convenient means of refining views both of localized palaeoenvironments and of control mechanisms within the global carbon cycle.

Freeman, K. H.; Hayes, J. M.; Trendel, J. M.; Albrecht, P.



Oxygen isotope fractionation in double carbonates.  


Oxygen isotope fractionations in double carbonates of different crystal structures were calculated by the increment method. Synthesis experiments were performed at 60?°C and 100?°C to determine oxygen and carbon isotope fractionations involving PbMg[CO3]2. The calculations suggest that the double carbonates of calcite structure are systematically enriched in (18)O relative to those of aragonite and mixture structures. Internally consistent oxygen isotope fractionation factors are obtained for these minerals with respect to quartz, calcite and water at a temperature range of 0-1200?°C. The calculated fractionation factors for double carbonate-water systems are generally consistent with the data available from laboratory experiments. The experimentally determined fractionation factors for PbMg[CO3]2, BaMg[CO3]2 and CaMg[CO3]2 against H2O not only fall between fractionation factors involving pure carbonate end-members but are also close to the calculated fractionation factors. In contrast, experimentally determined carbon isotope fractionation factors between PbMg[CO3]2 and CO2 are much closer to theoretical predictions for the cerussite-CO2 system than for the magnesite-CO2 system, similar to the fractionation behavior for BaMg[CO3]2. Therefore, the combined theoretical and experimental results provide insights into the effects of crystal structure and exchange kinetics on oxygen isotope partitioning in double carbonates. PMID:25393769

Zheng, Yong-Fei; Böttcher, Michael E



99 soil carbon .52 Carbon isotope ratios in belowground carbon cycle processes  

E-print Network

99 soil carbon .52 Carbon isotope ratios in belowground carbon cycle processes James R. Ehleringer 801-581-4665 #12;Abstract Analyses of carbon isotope ratios ( 13 C) in soil organic matter (SOM) and soil respired CO 2 provide insights into dynamics of the carbon cycle. 13 C analyses do not provide

Ehleringer, Jim


Preliminary report on isotope abundance measurements in groundwater samples from the Talbert Injection Barrier Area, Orange County Water District  

SciTech Connect

This report discusses isotope abundance measurements made on a collection of groundwater samples from the Orange County Water District. The water samples were collected in May, 1994 as part of a preliminary study conducted by LLNL to assess the feasibility of tracing and dating reclaimed water used in the Talbert Injection Barrier. A set of samples were collected both near to and far from the barrier and also at different depths in available monitoring wells. A variety of elements were selected for isotopic analysis; hydrogen (tritium), helium, neon, carbon, chlorine and strontium. The tritium abundance combined with the {sup 3}He and {sup 20}Ne abundance provides a method for age dating young (< 40 yr.) groundwater. The abundance of {sup 14}C provides an age dating technique for older (1,000--50,000 yr.) groundwater. The concentrations of {sup 36}Cl and {sup 87}Sr/{sup 86}Sr give information on sea water mixing and water-rock chemical interactions.

Hudson, G.B.; Davisson, M.L.; Velsko, C.; Niemeyer, S.; Esser, B.; Beiriger, J. [Lawrence Livermore National Lab., CA (United States). Isotope Sciences Div.



Carbon isotope anomalies in carbonates of the Karelian series  

NASA Astrophysics Data System (ADS)

Results are presented on carbon isotope distributions in carbonates of the Karelian complex. A highly anomalous isotopic composition was found in carbonate rocks aged from 2.6 to 1.9 b.y. In the stromatolitic carbonates of the Onega water table, delta-(C-13) reaches a value of +18 percent, while the shungite layer of the Zaonega horizon is characterized by a wide dispersion (from +7.9 to -11.8 percent). These data are in good agreement with the known geochemical boundary (about 2.2 b.y. ago) in the history of the earth.

Iudovich, Ia. E.; Makarikhin, V. V.; Medvedev, P. V.; Sukhanov, N. V.



Potassium isotope abundances in Australasian tektites and microtektites.  

NASA Astrophysics Data System (ADS)

We report electron microprobe determinations of the elemental compositions of 11 Australasian layered tektites and 28 Australasian microtektites; and ion microprobe determinations of the 41K/39K ratios of all 11 tektites and 13 of the microtektites. The elemental compositions agree well with literature values, although the average potassium concentrations measured here for microtektites, 1.1 1.6 wt%, are lower than published average values, 1.9 2.9 wt%. The potassium isotope abundances of the Australasian layered tektites vary little. The average value of ?41K, 0.02 ± 0.12‰ (1? mean), is indistinguishable from the terrestrial value (= 0 by definition) as represented by our standard, thereby confirming four earlier tektite analyses of Humayun and Koeberl (2004). In agreement with those authors, we conclude that evaporation has significantly altered neither the isotopic nor the elemental composition of Australasian layered tektites for elements less volatile than potassium. Although the average 41K/39K ratio of the microtektites, 1.1 ± 1.7‰ (1? mean), is also statistically indistinguishable from the value for the standard, the individual ratios vary over a very large range, from -10.6 ± 1.4‰ to +13.8 ± 1.5‰ and at least three of them are significantly different from zero. We interpret these larger variations in terms of the evaporation of isotopically light potassium; condensation of potassium in the vapor plume; partial or complete stirring and quenching of the melts; and the possible uptake of potassium from seawater. That the average 41K/39K ratio of the microtektites equals the terrestrial value suggests that the microtektite-forming system was compositionally closed with respect to potassium and less volatile elements. The possibility remains open that 41K/39K ratios of microtektites vary systematically with location in the strewn field.

Herzog, G. F.; O'D. Alexander, C. M.; Berger, E. L.; Delaney, J. S.; Glass, B. P.



The abundances of elements and isotopes in the solar wind  

NASA Technical Reports Server (NTRS)

Solar wind abundances have now been measured for eleven elements and the isotopes of the noble gases. Aside from solar wind protons and alpha particles, which have been studied extensively since the 1960's, information for heavier elements is limited. Nevertheless, two effects stand out. First is the enrichment of abundances of elements with low first ionization potential (FIP), most likely the combined result of an atom-ion separation process in the upper chromosphere, and a marginal coupling of low-charge-state heavy ions to protons and alphas during the acceleration of the solar wind. Second, there is variability in the solar wind composition over a whole range of time scales. Recent measurements carried out in the earth's magnetosheath during times that included high-speed coronal-hole-associated flows indicate a significantly lower overabundance of low FIP elements. Given the fact that the He/H ratio is remarkably constant in the coronal hole solar wind, this result suggests that both enrichment and variability are reduced in such flows.

Gloeckler, George; Geiss, Johannes




EPA Science Inventory

The natural abundance of stable carbon isotopes measured in bacterial nucleic acids that were extracted from estuarine bacterial concentrates were used to trace sources of organic matter for bacteria in.aquatic environments. he stable carbon isotope ratios of P. aeruginosa and nu...


Insights into nitrogen and carbon dynamics of ectomycorrhizal and saprotrophic fungi from isotopic evidence  

Microsoft Academic Search

The successful use of natural abundances of carbon (C) and nitrogen (N) isotopes in the study of ecosystem dynamics suggests\\u000a that isotopic measurements could yield new insights into the role of fungi in nitrogen and carbon cycling. Sporocarps of mycorrhizal\\u000a and saprotrophic fungi, vegetation, and soils were collected in young, deciduous-dominated sites and older, coniferous-dominated\\u000a sites along a successional sequence

Erik A. Hobbie; Stephen A. Macko; Herman H. Shugart



Site-Specific Carbon Isotopes in Organics  

NASA Astrophysics Data System (ADS)

Natural organic molecules exhibit a wide range of internal site-specific isotope variation (i.e., molecules with same isotopic substitution type but different site). Such variations are generally unconstrained by bulk isotopic measurements. If known, site-specific variations might constrain temperatures of equilibrium, mechanisms of formation or consumption reactions, and possibly other details. For example, lipids can exhibit carbon isotope differences of up to 30‰ between adjacent carbon sites as a result of fractionations arising during decarboxylation of pyruvate and other steps in lipid biosynthesis(1). We present a method for site-specific carbon isotope analysis of propane, based on high-resolution, multi-collector gas source mass spectrometry, using a novel prototype instrument - the Thermo MAT 253 Ultra. This machine has an inlet system and electron bombardment ion source resembling those in conventional stable isotope gas source mass spectrometers, and the energy filter, magnet, and detector array resembling those in multi-collector ICPMS and TIMS. The detector array has 7 detector positions, 6 of which are movable, and each of which can collect ions with either a faraday cup (read through amplifiers ranging from 107-1012 ohms) or an SEM. High mass resolving power (up to 27,000, MRP = M/dM definition) is achieved through a narrow entrance slit, adjustable from 250 to 5 ?m. Such resolution can cleanly separate isobaric interferences between isotopologues of organic molecules having the same cardinal mass (e.g., 13CH3 and 12CH2D). We use this technology to analyze the isotopologues and fragments of propane, and use such data to solve for the site-specific carbon isotope fractionation. By measuring isotopologues of both the one-carbon (13CH3) and the two-carbon (13C12CH4) fragment ion, we can solve for both bulk ?13C and the difference in ?13C between the terminal and central carbon position. We tested this method by analyzing mixtures between natural propane and labeled propane (13CH3-12CH2-12CH3). Results are consistent with the expected relative fractionations between the two fragments, indicating limited 'scrambling' of carbon positions of less than 2% in the source. The limits of precision of this method are currently ~0.5 ‰, sufficient to resolve known or suspected position-specific isotope effects in propane. We have explored the expected temperature-dependent equilibrium isotopic distributions of propane using density functional theory and quantum mechanical models of vibrational isotope effects. These models predict the homogeneous isotope exchange equilibria among the various isotopologues of propane, which include several of a wide range of effects that should be measurable by our methods. At 300 K we predict that the central carbon site is 15‰ higher in ?13C and 95 ‰ higher in ?D than the terminal carbon site; similarly the molecule containing both a 13C and D in the central site is enriched by ~120 ‰ relative to a random isotopic distribution at 300 K. These predictions present targets for future experimental and empirical studies of the temperature dependence of isotopic ordering in propane. More generally, the methods we are developing for the study of intramolecular isotopic distributions in propane will serve as a model for future study of similar effects in other organic compounds. [1]DeNiro, Epstein (1977) Science Volume 197, 261-263.

Piasecki, A.; Eiler, J. M.



Carbon isotope fractionation in autotrophic Chromatium  

E-print Network

OF TABLL'5 LIST OI' FIGURES V 3. 3. 3. ix I INTRODUCTION Stable Carbon Isotope Fractionation Isotope Fractionation During Photosynthesis 2 Photosynthetic Pathways C& and C Plants Fractionation During Bacterial Photosyn- thesis Objectives 16 II... in plants, CRAIG (1953, 1954) suggested that photosynthesis is a possible process causing the 13 12 observed C/ C variations in plants. A model consisting of two fractionation steps was proposed by PARK and EPSTEIN (1960) to explain the C/ C 13 12...

Wong, William Wai-Lun




Microsoft Academic Search

A new method, basically distinct from the two most common methods, is ; suggested for calculating the age of the Earth from lead isotope abundances. In ; common with other methods, the new method assumes that the samples used in the ; calculation can be interpreted by equations appropriate to evolution of the lead ; isotope abundances in a single

R. G. Ostic; R. D. Russell; P. H. Reynolds



Coprecipitation and isotopic fractionation of boron in modern biogenic carbonates  

SciTech Connect

The abundances and isotopic composition of boron in modern, biogenic calcareous skeletons from the Gulf of Elat, Israel, the Great Barrier Reef, Australia, and in deep-sea sediments have been examined by negative thermal-ionization mass spectrometry. The selected species (Foraminifera, Pteropoda, corals, Gastropoda, and Pelecypoda) yield large variations in boron concentration that range from 1 ppm in gastropod shells to 80 ppm in corals. The variations of {delta}{sup 11}B may be controlled by isotopic exchange of boron species in which {sup 10}B is preferentially partitioned into the tetrahedral species, and coprecipitation of different proportions of trigonal and tetrahedral species in the calcium carbonates. The B content and {delta}{sup 11}B values of deep-sea sediments, Foraminifera tests, and corals are used to estimate the global oceanic sink of elemental boron by calcium carbonate deposition. As a result of enrichment of B in corals, a substantially higher biogenic sink of 6.4 {plus minus} 0.9 {times} 10{sup 10} g/yr is calculated for carbonates. This is only slightly lower than the sink for desorbable B in marine sediments (10 {times} 10{sup 10} g/yr) and approximately half that of altered oceanic crust (14 {times} 10{sup 10} g/yr). Thus, carbonates are an important sink for B in the oceans being {approximately}20% of the total sinks. The preferential incorporation of {sup 10}B into calcium carbonate results in oceanic {sup 11}B-enrichment, estimated as 1.2 {plus minus} 0.3 {times} 10{sup 12} per mil {center dot} g/yr. The boron-isotope composition of authigenic, well-preserved carbonate skeletons may provide a useful tool to record secular boron-isotope variations in seawater at various times in the geological record.

Vengosh, A. (Australian National Univ., Canberra (Australia) Hebrew Univ., Jerusalem (Israel)); Chivas, A.R.; McCulloch, M.T. (Australian National Univ., Canberra (Australia)); Kolodny, Y.; Starinsky, A. (Hebrew Univ., Jerusalem (Israel))



Stable isotope analysis of carbon and nitrogen in angrites  

NASA Astrophysics Data System (ADS)

Angrites are a small group of ancient basaltic achondrites, notable for their unusual chemistry and extreme volatile depletion. No comprehensive study of indigenous light elements currently exists for the group. Measurement of the abundances and isotopic composition of carbon and nitrogen could provide information pertaining to the evolution of the angrite parent body. Bulk-sample stepped combustion analyses of five angrites and a glass separate from D'Orbigny were combined with earlier data and acid dissolution experiments of carbonates found in D'Orbigny to compile an inventory of indigenous carbon and nitrogen. Indigenous carbon combusted between 700 °C and 1200 °C, with abundances of 10-140 ppm and a mass-weighted ?13C of -25 to -20‰ with the exception of D'Orbigny (?13C approximately -5‰). Nitrogen was released at 850-1200 ºC, 1-20 ppm with a ?15N -3‰ to +4‰; again, D'Orbigny (?15N approximately +20 to +25‰) was an exception. We interpret these components as largely indigenous and decoupled; the carbon in graphitic or amorphous form, while the nitrogen is present as a dissolved component in the silicates. No relationship with the textural sub-classification of angrites is apparent. We suggest that the angrite parent body contains a reservoir of reduced carbon and thus may have undergone a change in redox conditions, although the timing and mechanism for this remain unclear.

Abernethy, F. A. J.; Verchovsky, A. B.; Starkey, N. A.; Anand, M.; Franchi, I. A.; Grady, Monica M.



Carbon abundance and silicate mineralogy of anhydrous interplanetary dust particles  

NASA Astrophysics Data System (ADS)

We have studied nineteen anhydrous chondritic interplanetary dust particles (IDPs) using analytical electron microscopy. We have determined a method for quantitative light element EDX analysis of small particles and have applied these techniques to a group of IDPs. Our results show that some IDPs have significantly higher bulk carbon abundances than do carbonaceous chondrites. We have also identified a relationship between carbon abundance and silicate mineralogy in our set of anhydrous IDPs. In general, these particles are dominated by pyroxene, olivine, or a subequal mixture of olivine and pyroxene. The pyroxene-dominated IDPs have a higher carbon abundance than those dominated by olivines. Members of the mixed mineralogy IDPs can be grouped with either the pyroxene- or olivine-dominated particles based on their carbon abundance. The high carbon, pyroxene-dominated particles have primitive mineralogies and bulk compositions which show strong similarities to cometary dust particles. We believe that the lower carbon, olivine-dominated IDPs are probably derived from asteroids. Based on carbon abundances, the mixed-mineralogy group represents particles derived from either comets or asteroids. We believe that the high carbon, pyroxene-rich anhydrous IDPs are the best candidates for cometary dust.

Thomas, K. L.; Blanford, G. E.; Keller, L. P.; Klock, W.; McKay, D. S.



Carbon isotope fractionation during microbial methane oxidation  

NASA Astrophysics Data System (ADS)

Methane, a common trace constituent of groundwaters, occasionally makes up more than 20% of the total carbon in groundwaters1,2. In aerobic environments CH4-rich waters can enable microbial food chain supporting a mixed culture of bacteria with methane oxidation as the primary energy source to develop3. Such processes may influence the isotopic composition of the residual methane and because 13C/12C analyses have been used to characterize the genesis of methanes found in different environments, an understanding of the magnitude of such effects is necessary. In addition, carbon dioxide produced by the methane-utilizing bacteria can be added to the inorganic carbon pool of affected groundwaters. We found carbon dioxide experimentally produced by methane-utilizing bacteria to be enriched in 12C by 5.0-29.6‰, relative to the residual methane. Where methane-bearing groundwaters discharged into aerobic environments microbial methane oxidation occurred, with the residual methane becoming progressively enriched in 13C. Various models have been proposed to explain the 13C/12C and 14C content of the dissolved inorganic carbon (DIC) of groundwaters in terms of additions or losses during flow in the subsurface4,5. The knowledge of both stable carbon isotope ratios in various pools and the magnitude of carbon isotope fractionation during various processes allows geochemists to use the 13C/12C ratio of the DIC along with water chemistry to estimate corrected 14C groundwater ages4,5. We show here that a knowledge of the carbon isotope fractionation between CH4 and CO2 during microbial methane-utilization could modify such models for application to groundwaters affected by microbial methane oxidation.

Barker, James F.; Fritz, Peter



The CH stars. II - Carbon, nitrogen, and oxygen abundances  

Microsoft Academic Search

Complete CNO abundances are obtained for a sample of red-giant CH stars. Analysis of the abundances shows that there are large excesses of carbon and nitrogen in the atmosphere while all indications are that the oxygen abundances follow the normal pattern observed among field G and K giants. A correlation between the C\\/N and C-13\\/C-12 seems to exist in the

Andrew D. Vanture



Carbon isotopic characterization of formaldehyde emitted by vehicles in Guangzhou, China  

NASA Astrophysics Data System (ADS)

Formaldehyde (HCHO) is the most abundant carbonyl compound in the atmosphere, and vehicle exhaust emission is one of its important anthropogenic sources. However, there is still uncertainty regarding HCHO flux from vehicle emission as well as from other sources. Herein, automobile source was characterized using HCHO carbon isotopic ratio to assess its contributions to atmospheric flux and demonstrate the complex production/consumption processes during combustion in engine cylinder and subsequent catalytic treatment of exhaust. Vehicle exhausts were sampled under different idling states and HCHO carbon isotopic ratios were measured by gas chromatograph-combustion-isotopic ratio mass spectrometry (GC-C-IRMS). The HCHO directly emitted from stand-alone engines (gasoline and diesel) running at different load was also sampled and measured. The HCHO carbon isotopic ratios were from -30.8 to -25.7‰ for gasoline engine, and from -26.2 to -20.7‰ for diesel engine, respectively. For diesel vehicle without catalytic converter, the HCHO carbon isotopic ratios were -22.1 ± 2.1‰, and for gasoline vehicle with catalytic converter, the ratios were -21.4 ± 0.7‰. Most of the HCHO carbon isotopic ratios were heavier than the fuel isotopic ratios (from -29 to -27‰). For gasoline vehicle, the isotopic fractionation (?13C) between HCHO and fuel isotopic ratios was 7.4 ± 0.7‰, which was higher than that of HCHO from stand-alone gasoline engine (?13Cmax = 2.7‰), suggesting additional consumption by the catalytic converter. For diesel vehicle without catalytic converter, ?13C was 5.7 ± 2.0‰, similar to that of stand-alone diesel engine. In general, the carbon isotopic signatures of HCHO emitted from automobiles were not sensitive to idling states or to other vehicle parameters in our study condition. On comparing these HCHO carbon isotopic data with those of past studies, the atmospheric HCHO in a bus station in Guangzhou might mainly come from vehicle emission for the accordance of carbon isotopic data.

Hu, Ping; Wen, Sheng; Liu, Yonglin; Bi, Xinhui; Chan, Lo Yin; Feng, Jialiang; Wang, Xinming; Sheng, Guoying; Fu, Jiamo



Carbon isotopes in biological carbonates: Respiration and photosynthesis  

USGS Publications Warehouse

Respired carbon dioxide is an important constituent in the carbonates of most air breathing animals but is much less important in the carbonates of most aquatic animals. This difference is illustrated using carbon isotope data from freshwater and terrestrial snails, ahermatypic corals, and chemoautotrophic and methanotrophic pelecypods. Literature data from fish otoliths and bird and mammal shell and bone carbonates are also considered. Environmental CO2/O2 ratios appear to be the major controlling variable. Atmospheric CO2/O2 ratios are about thirty times lower than in most natural waters, hence air breathing animals absorb less environmental CO2 in the course of obtaining O2. Tissue CO2 therefore, does not isotopically equilibrate with environmental CO2 as thoroughly in air breathers as in aquatic animals, and this is reflected in skeletal carbonates. Animals having efficient oxygen transport systems, such as vertebrates, also accumulate more respired CO2 in their tissues. Photosynthetic corals calcify mainly during the daytime when photosynthetic CO2 uptake is several times faster than respiratory CO2 release. Photosynthesis, therefore, affects skeletal ??13C more strongly than does respiration. Corals also illustrate how "metabolic" effects on skeletal isotopic composition can be estimated, despite the presence of much larger "kinetic" isotope effects. Copyright ?? 1997 Elsevier Science Ltd.

McConnaughey, T.A.; Burdett, J.; Whelan, J.F.; Paull, C.K.



Carbon and Strontium Abundances of Metal-Poor Stars  

E-print Network

We present carbon and strontium abundances for 100 metal-poor stars measured from R$\\sim $7000 spectra obtained with the Echellette Spectrograph and Imager at the Keck Observatory. Using spectral synthesis of the G-band region, we have derived carbon abundances for stars ranging from [Fe/H]$=-1.3$ to [Fe/H]$=-3.8$. The formal errors are $\\sim 0.2$ dex in [C/Fe]. The strontium abundance in these stars was measured using spectral synthesis of the resonance line at 4215 {\\AA}. Using these two abundance measurments along with the barium abundances from our previous study of these stars, we show it is possible to identify neutron-capture-rich stars with our spectra. We find, as in other studies, a large scatter in [C/Fe] below [Fe/H]$ = -2$. Of the stars with [Fe/H]$<-2$, 9$\\pm$4% can be classified as carbon-rich metal-poor stars. The Sr and Ba abundances show that three of the carbon-rich stars are neutron-capture-rich, while two have normal Ba and Sr. This fraction of carbon enhanced stars is consistent with other studies that include this metallicity range.

David K. Lai; Jennifer A. Johnson; Michael Bolte; Sara Lucatello



Natural gas constituent and carbon isotopic composition in petroliferous basins, China  

NASA Astrophysics Data System (ADS)

There are abundant gas resources in petroliferous basins of China. Large to midsize gas fields are found in Eastern, central and Western of China. However, origin, constituents and isotopic composition of natural gas in different gas fields are varied distinctly, and some present strong chemical secondary alteration and show variation both in age and space. Based on the systematic analysis of constituents and carbon isotope of a large number of gas samples, combined with the geological characteristics, this paper classifies the origins of the gases, explores the gas isotope characteristics and evolutionary regulation with the variation time and space, and further discusses the distinctive geochemistry of the gases in China. These gases are dominated by dry gas, its methane carbon isotope values range from -10‰ to -70‰, ethane from -16‰ to -52‰, propane from -13‰ to -43‰, and butane from -18‰ to -34‰. The carbon isotopes of most gases show the characteristics of humic-derived gas and crude oil cracked gas. In addition, large primary biogenic gas fields have been discovered in the Qaidam basin; inorganic-derived alkane gases have been discovered in deep of the Songliao Basin. Half of these gas fields are characterized by the alkane carbon isotope reversal in different degrees. Research indicates there are several reasons can result in carbon isotope reversal. Firstly, gas charge of different genetic types or different source in one gas reservoir may cause carbon isotope reversal. Besides, high-over mature evolution of gas can also lead to the carbon isotopic reversal of alkanes. Thirdly, secondary alteration of hydrocarbons may also result in abnormal distribution of carbon isotope, isotope transforms to unusual light and heavy.

Zhu, Guangyou; Wang, Zhengjun; Dai, Jinxing; Su, Jing



Atmospheric Trace Gas Abundances and Stable Isotope Ratios via IR-LIF  

NASA Technical Reports Server (NTRS)

We propose to develop new technologies with support provided by PIDDP that will enable the in situ measurements of abundances and stable isotope ratios in important radiatively and biogenically active gases such as carbon dioxide, carbon monoxide, water, methane, nitrous oxide, and hydrogen sulfide to very high precision (0.1 per mil or better for the isotopic ratios, for example). Such measurements, impossible at present, could provide pivotal new constraints on the global (bio)geochemical budgets of these critical species, and could also be used to examine the dynamics of atmospheric transport on Mars, Titan, and other solar system bodies. We believe the combination of solid state light sources with imaging of the IR laser induced fluorescence (IR-LIF) via newly available detector arrays will make such in situ measurements possible for the first time. Even under ambient terrestrial conditions, the LIF yield from vibrational excitation of species such as water and carbon dioxide should produce emission measures well in excess of ten billion photons/sec from samples volumes of order 1 c.c. These count rates can, in principle, yield detection limits into the sub-ppt range that are required for the in situ isotopic study of atmospheric trace gases. While promising, such technologies are relatively immature, but developing rapidly, and there are a great many uncertainties regarding their applicability to in situ IR-LIF planetary studies. We therefore feel PIDDP support will be critical to developing these new tools, and propose a three-year program to combine microchip near-IR lasers with low background detection axes and state-of-the-art HgCdTe detectors developed for astronomical spectroscopy to investigate the sensitivity of IR-LIF under realistic planetary conditions, to optimize the optical pumping and filtering schemes for important species, and to apply the spectrometer to the non-destructive measurement of stable isotopes in a variety of test samples. These studies form the necessary precursors to the development of compact, lightweight stable isotope/trace gas sensors for future planetary missions.

Blake, Geoffrey A.



Carbon isotopic composition of individual Precambrian microfossils  

NASA Technical Reports Server (NTRS)

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

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



Variations in Lead Isotopic Abundances in Sprague-Dawley Rat Tissues: Possible Reason of Formation  

PubMed Central

It has been reported in previous research that the lead isotopic composition of blood, urine and feces samples statistically differed from the given lead sources in Sprague-Dawley (SD) rats. However, the reason for this phenomenon is still unclear. An animal experiment was performed to investigate the lead isotope fractionation in diverse biological samples (i.e., lungs, liver, kidneys, bone) and to explore the possible reasons. SD rats were intratracheally instilled with lead acetate at the concentrations of 0, 0.02, 0.2, and 2 mg/kg body weight. Biological samples were collected for lead isotope analysis using an inductively coupled plasma mass spectrometry (ICP-MS). Significant differences are observed in lead isotope abundances among the diverse biological samples. The lead isotope abundances (206Pb, 207Pb and 208Pb) in diverse biological samples show different degrees and directions of departure from the given lead source. The results suggest that differences in enrichment or depletion capacity for each lead isotope in the various tissues might lead to the variation in lead isotopic abundances in tissues. Moreover, a nonlinear relationship between the blood lead level and the lead isotope abundances in liver and bone is observed. When the whole-blood level is higher than 50 ng/mL, the lead isotopic compositions of biological samples tend to be the same. Thus, the data support the speculation of a fractionation functional threshold. PMID:24587048

Liu, Duojian; Wu, Jing; Ouyang, Li; Wang, Jingyu



Anatomy of a cluster IDP. Part 2: Noble gas abundances, trace element geochemistry, isotopic abundances, and trace organic chemistry of several fragments from L2008#5  

NASA Technical Reports Server (NTRS)

The topics discussed include the following: noble gas content and release temperatures; trace element abundances; heating summary of cluster fragments; isotopic measurements; and trace organic chemistry.

Thomas, K. L.; Clemett, S. J.; Flynn, G. J.; Keller, L. P.; Mckay, David S.; Messenger, S.; Nier, A. O.; Schlutter, D. J.; Sutton, S. R.; Walker, R. M.



Low temperature Rosseland opacities with varied abundances of carbon and nitrogen  

E-print Network

We attempt to produce low temperature opacity data incorporating the effects of varied abundances of the elements carbon and nitrogen. For our temperature range of interest, molecules represent the dominant opacity source. Our dataset covers a wide metallicity range and is meant to provide important input data for stellar evolution models and other applications. We conduct chemical equilibrium calculations to evaluate the partial pressures of neutral atoms, ions, and molecules. Based on a large dataset containing atomic line and continuum data and, most importantly, a plethora of molecular lines, we calculate Rosseland mean opacity coefficients not only for a number of different metallicities, but also for varied abundances of the isotopes ^{12}C and ^{14}N at each metallicity. The molecular data comprise the main opacity sources for either an oxygen-rich or carbon-rich chemistry. We tabulate the opacity coefficients as a function of temperature and, basically, density. Due to the special role of the CO molecule, within a certain chemistry regime an alteration to the carbon abundance causes considerable changes in the Rosseland opacity. The transition from a scaled solar (i. e. oxygen-rich) mixture to a carbon-rich regime results in opacities that can, at low temperatures, differ by orders of magnitude from to the initial situation. The reason is that the mean opacity in either case is due to different molecular absorbers. Variations in the abundance of nitrogen have less pronounced effects but, nevertheless, cannot be neglected. [abridged

Michael T. Lederer; Bernhard Aringer



Determination of lithium isotopes at natural abundance levels by atomic absorption spectrometry  

USGS Publications Warehouse

The relationships of the absorption of 6Li and 7Li hollow cathode lamp emissions are used to determine lithium isotopic composition in the natural abundance range of geologic materials. Absorption was found to have a nonlinear dependence upon total lithium concentration and isotopic composition. A method using nonlinear equations to describe the relationship of the absorption of 6Li and 7Li lamp radiation is proposed as a means of calculating isotopic composition that is independent of total lithium concentration.

Meier, A.L.



Calibration of the carbonate ‘clumped isotope’ paleothermometer for otoliths  

NASA Astrophysics Data System (ADS)

Paleothermometry is an essential tool for understanding past changes in climate. The 'carbonate clumped isotope thermometer' is a temperature proxy related to ordering of 13C and 18O in the carbonate lattice (based on measurements of 13C 18O 16O in CO 2 produced by acid digestion of carbonate). This thermometer has been previously calibrated for inorganic calcite and aragonitic corals [Ghosh P., Adkins J., Affek H., Balta B., Guo W. F., Schauble E. A., Schrag D., and Eiler J. M. (2006) C-13-O-18 bonds in carbonate minerals: a new kind of paleothermometer. Geochim. Cosmochim. Acta70 (6), 1439-1456]. Here we determine the relationship between growth temperatures of aragonitic fish otoliths and abundances of 13C 18O 16O produced by acid digestion of those otoliths. Our calibration is based on analyses of otoliths from six species from four genera of modern fish sampled from a latitudinal transect of the Atlantic Ocean between 54° S and 65° N, plus one species from the tropical western Pacific. The temperatures at which fish otoliths precipitated were estimated by the mean temperature in the waters in which they lived, averaged over their estimated lifetimes. Estimated growth temperatures of our samples vary between 2 and 25 °C. Our results show that the abundance of 13C 18O 16O in CO 2 produced by acid digestion of fish otolith aragonite is a function of growth temperature, following the relationship: ?47={0.0568×106}/{T2}-0.0045, where ?47 is the enrichment, in per mil, of 13C 18O 16O in CO 2 relative to the amount expected for a stochastic (random) distribution of isotopes among all CO 2 isotopologues, and T is the temperature in Kelvin. This relationship closely approaches that previously documented for inorganic calcite and aragonitic coral (Ghosh et al., 2006).

Ghosh, Prosenjit; Eiler, John; Campana, Steven E.; Feeney, Richard F.



ORIGINAL PAPER Carbon isotope ratio measurements of glyphosate  

E-print Network

ORIGINAL PAPER Carbon isotope ratio measurements of glyphosate and AMPA by liquid chromatography chromatography coupled to isotope ratio mass spectrometry. We demon- strate that this analysis can be carried out


ORIGINAL RESEARCH Hydrogen and carbon isotope fractionation during  

E-print Network

ORIGINAL RESEARCH Hydrogen and carbon isotope fractionation during degradation of chloromethane, hydrogen isotope fractionation, methylotrophic bacteria. Correspondence Thierry Nadalig, Universite de-FID equipment by REALISE (http://realise., the Alsace network for research and engineering

Paris-Sud XI, Université de


Mechanism of Carbon Isotope Fractionation Associated with Lipid Synthesis  

Microsoft Academic Search

The low carbon-13\\/carbon-12 ratio of lipids is shown to result from isotopic fractionation during the oxidation of pyruvate to acetyl coenzyme A. In vitro analysis of the kinetic isotope effects of this reaction indicates that there will be a large, temperature-dependent difference in the carbon-13\\/carbon-12 ratio between the methyl and carbonyl carbon atoms of acetyl coenzyme A and between those

Michael J. Deniro; Samuel Epstein




E-print Network


Mellor-Crummey, John


Isotope labeling pattern study of central carbon metabolites using GC/MS.  


Determination of fluxes by (13)C tracer experiments depends on monitoring the (13)C labeling pattern of metabolites during isotope experiments. In metabolome-based (13)C metabolic flux analysis, liquid chromatography combined with mass spectrometry or tandem mass spectrometry (LC/MS or LC/MS/MS, respectively) has been mainly used as an analytical platform for isotope pattern studies of central carbon metabolites. However, gas chromatography with mass spectrometry (GC/MS) has several advantages over LC/MS, such as high sensitivity, low cost, ease of operation, and availability of mass spectra databases for comparison. In this study, analysis of isotope pattern for central carbon metabolites using GC/MS was demonstrated. First, a proper set of mass ions for central carbon metabolites was selected based on carbon backbone information and structural isomers of mass fragment ions. A total of 34 mass fragment ions was selected and used for the quantification of 25 central carbon metabolites. Then, to quantify isotope fractions, a natural mass isotopomer library for selected mass fragment ions was constructed and subtracted from isotopomer mass spectra data. The results revealed a surprisingly high abundance of partially labeled (13)C intermediates, such as 56.4% of fructose 6-phosphate and 47.6% of dihydroxyacetone phosphate at isotopic steady state, which were generated in the pentose phosphate pathway. Finally, dynamic changes of isotope fragments of central metabolites were monitored with a U-(13)C glucose stimulus response experiment in Kluyveromyces marxianus. With a comprehensive study of isotope patterns of central carbon metabolites using GC/MS, 25 central carbon metabolites and their isotopic fractions were successfully quantified. Dynamic and precise acquisition of isotope pattern can then be used in combination with proper kinetic models to calculate metabolic fluxes. PMID:25463204

Jung, Joon-Young; Oh, Min-Kyu



Carbon isotope anomaly in the major plant C1 pool and its global biogeochemical implications  

NASA Astrophysics Data System (ADS)

We report that the most abundant C1 units of terrestrial plants, the methoxyl groups of pectin and lignin, have a unique carbon isotope signature exceptionally depleted in 13C. Plant-derived C1 volatile organic compounds (VOCs) are also anomalously depleted in 13C compared with Cn+1 VOCs. The results confirm that the plant methoxyl pool is the predominant source of biospheric C1 compounds of plant origin such as methanol, chloromethane and bromomethane. Furthermore this pool, comprising ca 2.5% of carbon in plant biomass, could be an important substrate for methanogenesis and thus be envisaged as a possible source of isotopically light methane entering the atmosphere. Our findings have significant implications for the use of carbon isotope ratios in elucidation of global carbon cycling. Moreover methoxyl groups could act as markers for biological activity in organic matter of terrestrial and extraterrestrial origin.

Keppler, F.; Kalin, R. M.; Harper, D. B.; McRoberts, W. C.; Hamilton, J. T. G.


Carbon isotope anomaly in the major plant C1 pool and its global biogeochemical implications  

NASA Astrophysics Data System (ADS)

We report that the most abundant C1 units of terrestrial plants, the methoxyl groups of pectin and lignin, have a unique carbon isotope signature exceptionally depleted in 13C. Plant-derived C1 volatile organic compounds (VOCs) are also anomalously depleted in 13C compared with Cn+1 VOCs. The results confirm that the plant methoxyl pool is the predominant source of biospheric C1 compounds of plant origin such as methanol, chloromethane and bromomethane. Furthermore this pool, comprising ca. 2.5% of carbon in plant biomass, represents an important substrate for methanogenesis and could be a significant source of isotopically light methane entering the atmosphere. Our findings have significant implications for the use of carbon isotope ratios in elucidation of global carbon cycling. Moreover methoxyl groups could act as markers for biological activity in organic matter of terrestrial and extraterrestrial origin.

Keppler, F.; Kalin, R. M.; Harper, D. B.; McRoberts, W. C.; Hamilton, J. T. G.



Barium even-to-odd isotope abundance ratios in thick disk and thin disk stars  

E-print Network

We present the Ba even-to-odd isotope abundance ratios in 25 cool dwarf stars with the metallicity [Fe/H] ranged between 0.25 and --1.35. Our method takes advantage of the hyperfine structure (HFS) affecting the \\ion{Ba}{ii} resonance line of the odd isotopes. The fractional abundance of the odd isotopes of Ba is derived from a requirement that Ba abundances from the resonance line $\\lambda 4554$ and subordinate lines $\\lambda 5853$ and $\\lambda 6496$ must be equal. The results are based on NLTE line formation and analysis of high resolution (R $\\sim60000$) high signal-to-noise (S/N $\\ge 200$) observed spectra. We find that the fraction of the odd isotopes of Ba grows toward the lower Ba abundance (or metallicity) and the mean value in the thick disk stars equals 33 $\\pm$ 4%. This indicates the higher contribution of the $r-$process to barium in the thick disk stars compared to the solar system matter. The obtained fraction increases with the [Eu/Ba] abundance ratio growth in agreement with expectations. A significant fraction of the \\emph{even} isotopes of Ba found in old Galactic stars (the thick disk stars), $\\sim67$%, is in contrast to the prediction of the "classical" model of the $s-$process and favors the value predicted by the "stellar" models of Arlandini et al. (1999) and Travaglio et al. (1999).

L. Mashonkina; G. Zhao



Total carbon and nitrogen abundances in lunar samples.  


Total carbon and nitrogen abundances were determined by using combustion-gas chromatographic techlniques. Weighited mean analyses for butlk fines were 225 and 140 ppm total carbon and 150 anid 100 ppm total nitrogen. Total carbon in fine breccia was 230 ppm; in coarse breccia, 100 ppmn; in fine-grained rock, 70 ppm; and in mediumn-grained rock, 64 ppm. The finest sieved fraction had the highest carbon content. Total nitrogen in fine breccia was 125 ppm; in coarse breccia, 100 ppm; in fine-grained rock, 115 ppm; and in medium-grained rock, 30 ppm. The total carbon and nitrogen finies appeat to be mixtuires of indigenous lunar material togetheer with meteoritic and solar wind components. PMID:17781467

Moore, C B; Lewis, C F; Gibson, E K; Nichiporuk, W



Carbon and nitrogen stable isotope ratios in body tissue and mucus of feeding and fasting earthworms ( Lumbricus festivus )  

Microsoft Academic Search

We used natural abundance stable isotope techniques to estimate carbon and nitrogen turnover rates in body tissue and mucus\\u000a of earthworms. Isotope ratios of carbon (?13C) and nitrogen (?15N) were monitored simultaneously in body tissue and mucus for up to 101?days in feeding or fasting Lumbricus festivus kept in an artificial substrate. When the diet of the earthworms was switched

Olaf Schmidt; Charles M. Scrimgeour; James P. Curry



Biomarker and molecular isotope approaches to deconvolve the terrestrial carbon isotope record: modern and Eocene calibrations  

NASA Astrophysics Data System (ADS)

Climate, biome, and plant community are important predictors of carbon isotope patterns recorded in leaves and leaf waxes. However, signatures recorded by terrestrial organic carbon and lipids that have mixed floral sources (e.g., n-alkanes) potentially reflect both plant community changes and climate. More taxonomically specific proxies for plants (i.e., di- and tri-terpenoids for conifers and angiosperms, respectively), can help to resolve the relative influences of changing community and climate, provided differences in biomarker production and lipid biosynthetic fractionation among plants can be better constrained. We present biomarker abundance and carbon isotope values for lipids from leaves, branches and bark of 44 tree species, representing 21 families including deciduous and evergreen conifers and angiosperms. n-alkane production differs greatly between conifer and angiosperm leaves. Both deciduous and evergreen angiosperms make significantly more n-alkanes than conifers, with n-alkanes not detected in over half of the conifers in our study. Terpenoid abundances scale strongly with leaf habit: evergreen species have significantly higher abundances. We combine these relative differences in lipid production with published estimates of fluxes for leaf litter from conifer and angiosperm trees to develop a new proxy approach for estimating paleo plant community inputs to ancient soils and sediments. To test our modern calibration results, we have evaluated n-alkanes and terpenoids from laterally extensive (~18 km) carbonaceous shales and mudstones in Eocene sediments (52.6 Ma) at Fifteenmile Creek in the Bighorn Basin (WY, USA). Our terpenoid-based proxy predicts on average a 40% conifer community, which is remarkably close in agreement with a fossil-based estimate of 36%. n-alkane carbon isotope fractionation (leaf-lipid) differs among plant types, with conifer n-alkanes about 2-3‰ 13C enriched relative to those in angiosperms. Since conifer leaves are generally 2-3‰ enriched relative to angiosperm leaves, we project that the far more abundant angiosperm lipids will be about 4-6 ‰ depleted relative to small amounts of conifer n-alkanes in natural samples. In addition, we report carbon isotope values of the terpenoids from the MVA (triterpenoids) and MEP (diterpenoids) synthesis pathways for our plant sample set. Bulk leaf tissue-to-lipid fractionation factors for terpenoids are similar and generally small, -0.4 and -0.6‰, for MVA and MEP products, respectively. Estimates of precipitation from fossil leaves at the Fifteenmile site allow us to predict leaf fractionation values for different plant types (bulk) and for triterpenoid and diterpenoid compound classes. Our fractionation factors, when applied to an estimate for the ?13C value of late Eocene CO2, agree well with bulk and molecular data. An understanding of molecular production biases greatly improves our ability to reconstruct both paleovegetation and ?13C of atmospheric CO2.

Diefendorf, A. F.; Freeman, K. H.; Wing, S.; Currano, E. D.



Oxygen and carbon isotopic growth record in a reef coral from the florida keys and a deep-sea coral from blake plateau  

USGS Publications Warehouse

Carbon and oxygen isotope analysis through a 30-year (1944 to 1974) growth of Montastrea annularis from Hen and Chickens Reef (Florida Keys) shows a strong yearly variation in the abundances of both carbon-13 and oxygen-18 and a broad inverse relationship between the two isotopes. Normal annual dense bands are formed during the summer and are characterized by heavy carbon and light oxygen. "Stress bands" are formed during particularly severe winters and are characterized by heavy carbon and heavy oxygen. The isotopic effect of Zooxanthellae metabolism dominates the temperature effect on the oxygen-18/oxygen-16 ratio. The isotopic results on the deep-sea solitary coral Bathypsammia tintinnabulum, where Zooxanthellae are nonexistent, indicates that the abundance of the heavy isotopes carbon-13 and oxygen-18 is inversely related to the growth rate, with both carbon and oxygen approaching equilibrium values with increasing skeletal age.

Emiliani, C.; Harold, Hudson J.; Shinn, E.A.; George, R.Y.



Using computer models of stable isotope abundance to trace and understand NOx transformation to HNO3  

NASA Astrophysics Data System (ADS)

Advances in our understanding of stable isotope fractionation and transformation have occurred recently in the study of the NOx cycle. In particular, stable isotopes have been used to elucidate the transformation of NOx to HNO3, and to understand specific sources of NOx to this important atmospheric cycle. Many uncertainties still exist within this chemistry however, and models of stable isotope abundance within these compounds can help to answer important questions relating to the source and transformation of NOx. Using computer modeling techniques and tools focused on stable isotope abundance, we explore NOx source and transformation in the atmosphere. Two models are the specific focus of this study: a photochemical box model based on the Regional Atmospheric Chemistry Mechanism (RACM) as well as the Community Multiscale Air Quality (CMAQ) model. Modeling results are compared to samples of wet and dry deposition for verification. Implications for future research will also be discussed.

Mase, D. F.; Michalski, G. M.



Oxygen and carbon isotope disequilibria in Galapagos corals: isotopic thermometry and calcification physiology  

SciTech Connect

Biological carbonate skeletons are built largely from carbon dioxide, which reacts to form carbonate ion within thin extracellular solutions. The light isotopes of carbon and oxygen react faster than the heavy isotopes, depleting the resulting carbonate ions in /sup 13/C and /sup 18/O. Calcium carbonate precipitation occurs sufficiently fast that the skeleton remains out of isotopic equilibrium with surrounding fluids. This explanation for isotopic disequilibrium in biological carbonates was partially simulated in vitro, producing results similar to those seen in non-photosynthetic corals. Photosynthetic corals have higher /sup 13/C//sup 12/C ratios due to the preferential removal of /sup 12/C (as organic carbon) from the reservoir of dissolved inorganic carbon. The oxygen isotopic variations in corals can be used to reconstruct past sea surface temperatures to an accuracy of about 0.5/sup 0/C. The carbon isotopic content of photosynthetic corals provides an indication of cloudiness. Using isotopic data from Galapagos corals, it was possible to construct proxy histories of the El Nino phenomenon. The physiology of skeletogenesis appears to be surprisingly similar in calcium carbonate, calcium phosphate, and silica precipitating systems.

McConnaughey, T.A.



High Resolution Carbon and Oxygen Isotope Measurements of Laminations in Pedogenic Carbonate  

Microsoft Academic Search

Stable carbon and oxygen isotope ratios in pedogenic carbonate from buried soils provide a proxy for low-resolution Quaternary climate and environmental conditions. Samples of carbonate are taken from clast rinds, nodules or filaments in calcic soils. Most clast rinds exhibit micro-laminations that may preserve isotopic ratios of formation. The techniques typically utilized to sample pedogenic carbonate, however, are too coarse

D. Breecker; Z. Sharp



Measurement of isotopic abundances in collected stratospheric ozone samples  

SciTech Connect

Enrichment of heavy O{sub 3} isotopes has been measured in collected stratospheric samples. A balloon-borne cryogenic sampler was used to gather six O{sub 3} samples between 26 and 35 km in three flights. Subsequent laboratory mass spectrometer analysis of rare O{sub 3} isotopes at both mass 49 and 50 has resulted in more precise measurements than have previously been reported with in situ and ground-based techniques. In one flight, {sup 50}O{sub 3} was enriched by 12-16% and {sup 49}O{sub 3} by 9-11%, both increasing with altitude. In the remaining two flights, the isotope enrichment was nearly mass-independent at 8-9%. The enrichments in O{sub 3} at mass 50 are less than the large 40% value observed in some stratospheric measurements but similar to {sup 49}O{sub 3} and {sup 50}O{sub 3} fractionations produced in laboratory-generated ozone.

Schueler, B.; Morton, J.; Mauersberger, K. (Univ. of Minnesota, Minneapolis (USA))



A carbon isotope mass balance for an anoxic marine sediment: Isotopic signatures of diagenesis  

NASA Technical Reports Server (NTRS)

A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.

Boehme, Susan E.



Global simulation of the carbon isotope exchange of terrestrial ecosystems  

NASA Astrophysics Data System (ADS)

There remain large uncertainties in our quantification of global carbon cycle, which has close interactions with the climate system and is subject to human-induced global environmental change. Information on carbon isotopes is expected to reduce the uncertainty by providing additional constraints on net atmosphere-ecosystem exchange. This study attempted to simulate the dynamics of carbon isotopes at the global scale, using a process-based terrestrial ecosystem model: Vegetation Integrative SImulator for Trace gases (VISIT). The base-model of carbon cycle (Sim-CYCLE, Ito 2003) has already considered stable carbon isotope composition (13C/12C), and here radioactive carbon isotope (14C) was included. The isotope ratios characterize various aspects of terrestrial carbon cycle, which is difficult to be constrained by sole mass balance. For example, isotopic discrimination by photosynthetic assimilation is closely related with leaf stomatal conductance and composition of C3 and C4 plant in grasslands. Isotopic disequilibrium represents mean residence time of terrestrial carbon pools. In this study, global simulations (spatial resolution 0.5-deg, time-step 1-month) were conducted during the period 1901 to 2100 on the basis of observed and projected atmospheric CO2, climate, and land-use conditions. As anthropogenic CO2 accumulates in the atmosphere, heavier stable carbon isotope (13C) was diluted, while radioactive carbon isotope (14C) is strongly affected by atomic bomb experiments mainly in the 1950s and 1960s. The model simulated the decadal change in carbon isotope compositions. Leaf carbon with shorter mean residence time responded rapidly to the atmospheric change, while plant stems and soil humus showed substantial time-lag, leading to large isotopic disequilibrium. In the future, the isotopic disequilibrium was estimated to augment, due to accelerated rate of anthropogenic CO2 accumulation. Spatial distribution of stable isotope composition (12C/13C, or d13C) was primarily dominated by C3/C4 plant composition and then ancillary environmental conditions. Along latitude, plant and litter carbon pools in northern ecosystems have slower turnover rates (i.e., higher 14C/12C) than those in tropical ecosystems. However, humus carbon in northern ecosystems with very long mean residence times has lower 14C/12C ratio, most of bomb-derived radioactive carbon lingered still in plant biomass. Now, we are attempting to examine the model estimations by comparing with atmospheric measurements.

Ito, A.; Terao, Y.; Mukai, H.



Carbon Isotope Stratigraphy of the Triassic-Jurassic Boundary, Northern Calcareous Alps, Southern Bavaria.  

NASA Astrophysics Data System (ADS)

The end Triassic is recognized as a period of increased marine biotic turnover, culminating in one of the five major mass extinction events of the Phanerozoic at the Triassic-Jurassic boundary. Carbon isotope excursions have been reported globally that may be in response to a perturbation to the earth system. Here we present findings from a succession of early Mesozoic Tethyan carbonate strata from the Northern Calcareous Alps (NCA) of southern Bavaria, Germany. The succession ranges from Carnian to Middle Jurassic in age and is part of the Bavarian Syncline, which trends East-West along the northern extent of the NCA. The two field areas studied, Wallberg and Buchstein, contain the Tr-J boundary, which is marked by an abrupt change from underlying reefal carbonate rocks to a deeper basinal setting dominated by marls, as well as the disappearance of abundant brachiopod, bivalve and colonial coral populations. The boundary is also characterized by a carbonate carbon isotope excursion. Carbonate C isotope values in the underlying reefal carbonate rocks are marked by values of 2.0 to 2.5‰. Above the contact, the carbonate C isotopes show a 1.5 - 2.0‰ decline, which coincides with the change from shallow to deeper marine carbonate sedimentation. Following the excursion, and whilst the succession maintains a basinal palaeoenvironmental setting, the C isotopes return to values similar to those present beneath the Tr-J boundary ranging from 2.0 - 2.5‰. The negative excursion may be recording a global perturbation to the carbon cycle, however the change from a shallow to deep marine depositional environment must also be considered as a possible influence on isotopic composition. Cross-plots of C and O isotopes show no correlation hence we prefer to interpret the carbonate C isotopic data to record original seawater values. Post-depositional diagenetic and lithification processes, however, likely modified the O isotope values. Our results urge caution in identifying C isotopic excursions as global until potential palaeoenvironmental-related changes can be excluded.

Blom, Vincent P. C.; Prave, Anthony R.; Raub, Timothy D.



Upper limits on argon isotope abundances in the Venus thermosphere  

NASA Technical Reports Server (NTRS)

On December 9, 1978 the neutral gas mass spectrometer aboard the NASA Pioneer Venus multiprobe bus has measured density, composition, and temperature of the Venus dayside thermosphere. There was no positive identification of argon down to the lowest measuring altitude of 130 km. For the altitude level of 135 km the following upper limits for the number densities of argon isotopes were derived: n(Ar-36) less than 1.3 times 10 to the 6th power per cu cm and n(Ar-40) less than 2.8 times 10 to the 6th power per cu cm. From our upper atmosphere observations we infer for the troposphere of Venus the following upper limits for the mixing ratios: n(Ar-36)/total number density less than 9 times 10 to the minus 6th power and n(Ar-40)/total number density less than 20 times 10 to the minus 6th power.

Mauersberger, K.; Von Zahn, U.; Krankowsky, D.



Spectroscopy of Neutron Unbound Carbon Isotopes  

NASA Astrophysics Data System (ADS)

Neutron unbound states in neutron-rich carbon isotopes were populated via knockout reactions from a ^22N beam at the National Superconducting Cyclotron Laboratory at Michigan State University. The Modular Neutron Array (MoNA) was used to measure the energy and position of emitted neutrons near zero degrees, while the remaining charged fragments were detected in a series of position and energy-sensitive detectors behind the MSU/FSU Sweeper magnet. The decay energy was then reconstructed event-by-event from the four-momentum vectors of the neutron and fragment. Results from the current analysis, including decay energy spectra for ^19,20,21C and interpretation, will be presented.

Mosby, S.; Thoennessen, M.; Deyoung, P.



Isotope Dependence of Chemical Erosion of Carbon  

SciTech Connect

We study the chemical erosion of hydrogen-supersaturated carbon due to bombardment by hydrogen isotopes H, D, and T at energies of 1 30 eV using classical molecular dynamics simulations. The chemical structure at the hydrogen-saturated interface (the distribution of terminal hydrocarbon moieties, in particular) shows a weak dependence on the mass of the impinging atoms. However the sputtering yields increase considerably with increasing projectile mass. We analyze the threshold energies of chemical sputtering reaction channels and show that they are nearly mass independent, as expected from elementary bond-breaking chemical reactions involving hydrocarbons. Chemical sputtering yields for D impact are compared with new experimental data. Good agreement is found for small hydrocarbons but the simulations overestimate the production of large hydrocarbons for energies larger than 15 eV. We present a thorough analysis of the dependence of our simulations on the parameters of the bombardment schemes and discuss open questions and possible avenues for development.

Reinhold, Carlos O [ORNL; Krstic, Predrag S [ORNL; Stuart, S. J. [Clemson University; Zhang, Hengda [ORNL; Harris, Peter R [ORNL; Meyer, Fred W [ORNL



Diffusive fractionation of carbon isotopes in ?-Fe: Experiment, models and implications for early solar system processes  

NASA Astrophysics Data System (ADS)

Carbon is an abundant element of planets and meteorites whose isotopes provide unique insights into both organic and inorganic geochemical processes. The identities of carbonaceous phases and their textural and isotopic characters shed light on dynamical processes in modern Earth systems and the evolution of the early solar system. In meteorites and their parent bodies, reduced carbon is often associated with Fe-Ni alloys, so knowledge of the mechanisms that fractionate C isotopes in such phases is crucial for deciphering the isotopic record of planetary materials. Here we present the results of a diffusion-couple experiment in which cylinders of polycrystalline Fe containing 11,500 and 150 ?g/g of C were juxtaposed at 1273 K and 1.5 GPa for a duration of 36 min. Diffusion profiles of total C concentration and 13C/12C were measured by secondary ion mass spectrometry (SIMS). The elemental diffusivity extracted from the data is ˜3.0 × 10-11 m2 s-1, where 13C/12C was observed to change significantly along the diffusion profile, reflecting a higher diffusivity of 12C relative to 13C. The maximum isotopic fractionation along the diffusion profile is ˜30-40‰. The relative diffusivities (D) of the carbon isotopes can be related to their masses (M) by D/D=(C/M)?; the exponent ? calculated from our data has a value of 0.225 ± 0.025. Similarly high ? values for diffusion of other elements in metals have been taken as an indication of interstitial diffusion, so our results are consistent with C diffusion in Fe by an interstitial mechanism. The high ?-value reported here means that significant fractionation of carbon isotopes in nature may arise via diffusion in Fe(-Ni) metal, which is an abundant component of planetary interiors and meteorites.

Mueller, Thomas; Watson, E. Bruce; Trail, Dustin; Wiedenbeck, Michael; Van Orman, James; Hauri, Erik H.



Distribution and carbon isotope patterns of diterpenoids and triterpenoids in modern temperate C3 trees and their geochemical significance  

NASA Astrophysics Data System (ADS)

Tricyclic diterpenoids and pentacyclic triterpenoids are nearly exclusively produced by gymnosperms and angiosperms, respectively. Even though both classes of terpenoids have long been recognized as plant biomarkers, their potential use as phylogenetically specific ?13C proxies remains largely unexplored. Little is known of how terpenoid abundance and carbon isotope composition vary either with plant phylogenetic position, functional group, or during synthesis. Here, we report terpenoid abundances and isotopic data for 44 tree species in 21 families, representing both angiosperms and gymnosperms, and both deciduous and evergreen leaf habits. Di- and triterpenoid abundances are significantly higher in evergreens compared to deciduous species, reflecting differences in growth strategies and increased chemical investment in longer-lived leaves. Carbon isotope abundances of terpenoid lipids are similar to leaf tissues, indicating biosynthetic isotope effects are small for both the MVA (-0.4‰) and MEP (-0.6‰) pathways. Leaf and molecular isotopic patterns for modern plants are consistent with observations of amber, resins and plant biomarkers in ancient sediments. The ?13C values of ancient diterpenoids are higher than triterpenoids by 2-5‰, consistent with observed isotopic differences between gymnosperms and angiosperms leaves, and support the relatively small lipid biosynthetic effects reported here. All other factors being equal, evergreen plants will dominate the abundance of terpenoids contributed to soils, sediments and ancient archives, with similar inputs estimated for angiosperm and gymnosperm trees when scaled by litter flux.

Diefendorf, Aaron F.; Freeman, Katherine H.; Wing, Scott L.



Fractionation between inorganic and organic carbon during the Lomagundi (2.222.1 Ga) carbon isotope excursion  

E-print Network

April 2008 Editor: H. Elderfield Keywords: Precambrian carbon cycle Lomagundi Event carbon isotope. carbonate carbon isotopic values on the shallow-marine carbonate platform suggests that the carbon cyclingFractionation between inorganic and organic carbon during the Lomagundi (2.22­2.1 Ga) carbon

Bekker, Andrey


Mass transfer and carbon isotope evolution in natural water systems  

USGS Publications Warehouse

This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1. (1) carbon-14 dating of groundwaters; 2. (2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and 3. (3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of ??C13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation. ?? 1978.

Wigley, T.M.L.; Plummer, L.N.; Pearson, F.J., Jr.



Molecular and stable carbon isotopic compositions of hopanoids in seep carbonates from the South China Sea continental slope  

NASA Astrophysics Data System (ADS)

The lipid biomarkers of hopanoids in cold seep carbonates from the South China Sea continental slope were investigated by gas chromatography-mass spectrometer (GC-MS) and gas chromatography-isotope ratio-mass spectrometer (GC-ir-MS). The distribution of hopanes/hopenes shows a preference for the ‘biological’ 17?(H), 21?(H)-over the ‘geological’ 17?(H), 21?(H)-configuration. This interpretation is in agreement with the strong odd-even preference of long-chain n-alkanes in those samples, suggesting that the ?? hopanes may be the early diagenetic products of biohopanoids and the ??, ?? configurations of hopanes were mainly derived from allochthonous sources contributing to the organic matter of the carbonates. In terms of hopanoid acids, the C30 to C33 17?(H), 21?(H)-hopanoid acids were detected with C32 17?(H), 21?(H)-hopanoid acid being the most abundant. However, there is a significant difference in stable carbon isotopic compostions of the C32 17?(H), 21?(H)-hopanoic acid among samples (-30.7‰ to -69.8‰). The ?13C values match well with the carbon isotopic compositions of SRB-derived iso-/anteiso-C15:0 fatty acids in the samples, which strongly depend on the carbon utilization types by microbe. The most abundant compound of hopanols detected in the samples, C30-17?(H), 21?(H)-hopanol, may be a good indicator of diagenetic product of type I methanotrophs. The molecular and carbon isotopic compositions of hopanoids demonstrate clearly that there is a combination contribution of both SRB and type I or type X methanotrophs to the source organism in the seep carbonates from the South China Sea continental slope.

Guan, Hongxiang; Sun, Yongge; Mao, Shengyi; Zhu, Xiaowei; Wu, Nengyou



Chemical and Isotopic Study of Lab-formed Carbonates Under Cryogenic and Hydrothermal Conditions  

NASA Technical Reports Server (NTRS)

Aqueous environments on early Mars were probably relatively short-lived and localized, as evidenced by the lack of abundant secondary minerals detected by the TES instrument. In order to better understand the aqueous history of early Mars we need to be able to interpret the evidence preserved in secondary minerals formed during these aqueous events. Carbonate minerals, in particular, are important secondary minerals for interpreting past aqueous environments as illustrated by the carbonates preserved in ALH84001. Carbonates formed in short-lived, dynamic aqueous events often preserve kinetic rather than equilibrium chemical and isotopic processes, and predicting the behavior of such systems is facilitated by empirical data.

Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Golden, D. C.; Ming, D. W.; Gibson, E. K.



Isotopic studies of Yucca Mountain soil fluids and carbonate pedogenesis  

SciTech Connect

Secondary carbonates occurring within the soils, faults, and subsurface fractures of Yucca Mountain contain some of the best available records of paleoclimate and palehydrology for the potential radioactive waste repository site. This article discusses conceptual and analytical advances being made with regard to the interpretation of stable isotope data from pedogenic carbonates, specifically related to the {sup 13}C content of soil CO{sub 2}, CaCO{sub 3}, precipitation mechanisms, and isotopic fractionations between parent fluids and precipitating carbonates. The {sup 13}C content of soil carbon dioxide from Yucca Mountain and vicinity shows most of the usual patterns expected in such contexts: Decreasing {sup 13}C content with depth decreasing {sup 13}C with altitude and reduced {sup 13}C during spring. These patterns exist within the domain of a noisy data set; soil and vegetational heterogeneities, weather, and other factors apparently contribute to isotopic variability in the system. Several soil calcification mechanisms appear to be important, involving characteristic physical and chemical environments and isotopic fractionations. When CO{sub 2} loss from thin soil solutions is an important driving factor, carbonates may contain excess heavy isotopes, compared to equilibrium precipitation with soil fluids. When root calcification serves as a proton generator for plant absorption of soil nutrients, heavy isotope deficiencies are likely. Successive cycles of dissolution and reprecipitation mix and redistribute pedogenic carbonates, and tend to isotopically homogenize and equilibrate pedogenic carbonates with soil fluids.

McConnaughey, T.A.; Whelan, J.F.; Wickland, K.P.; Moscati, R.J.



An isotopic study of biogeochemical relationships between carbonates and organic carbon in the Greenhorn Formation  

NASA Technical Reports Server (NTRS)

Carbon-isotopic compositions of total carbonate, inoceramid carbonate, micritic carbonate, secondary cements, total organic carbon, and geoporphyrins have been measured in 76 different beds within a 17-m interval of a core through the Greenhorn Formation, an interbedded limestone and calcareous shale unit of Cretaceous age from the Western Interior Seaway of North America. Results are considered in terms of variations in the processes of primary production and in secondary processes. It is shown that the porphyrin isotopic record reflects primary isotopic variations more closely than the TOC isotopic record and that, in these sediments, TOC is enriched in C-13 relative to its primary precursor by 0.6 to 2.8 percent. This enrichment is attributed to isotope effects within the consumer foodweb and is associated with respiratory heterotrophy. Variation in this secondary enrichment are correlated with variations in the isotopic composition of marine carbonate.

Hayes, J. M.; Popp, Brian N.; Takigiku, Ray; Johnson, Marcus W.



Isotope composition of carbon in amino acids of solid bitumens  

NASA Astrophysics Data System (ADS)

Primary data are presented on the isotope composition of carbon in individual amino acids from solid bitumens and several biological objects. The amino acids of biological objects are characterized by wide variations of the isotope composition of carbon. This fact occurs owing to the difference in biochemical paths of metabolism resulting in the synthesis of individual amino acids. The ?13C values are somewhat decreased for individual amino acids in asphaltenes, varying from -7.7 to -31.7‰. The carbon of amino acids is weighted in kerits from Bad'el' compared to asphaltenes. All the natural bitumens retain the characteristic trend for natural substances: the isotopically heavy and light amino acids by carbon are glycine and leucine, respectively. The isotope composition of amino-acid carbon is lightened compared to natural bitumens in the samples formed under a pronounced thermal impact (asphalt-like crust and kirishite).

Shanina, S. N.; Bushnev, D. A.



Microbial Influences on Local Carbon Isotopic Ratios and Their Preservation in Carbonate  

NASA Astrophysics Data System (ADS)

Analysis of the carbon isotopic composition of carbonates is a valuable tool for studying microbial processes and looking for evidence of life. Microbial fix ation of CO2 and conversion of organic carbon to CO2 can produce measurable ?13C shifts in a microbial mat environment. Diffusion modeling demonstrates that substantial isotopic shifts can develop within the mat and in the diffusion boundary layer in the fluid when CO2 fixation is rapid and prolonged for several hours. Carbonates that precipitate during rapid CO2 fixation can preserve these microbially produced isotopic shifts. However, continued precipitation during intervals when respiration dominates or after the cessation of active microbial growth commonly dilutes autotrophic isotopic signatures. Thus, preserved isotopic signatures rarely reflect the magnitude of isotopic shifts within the mat. Interpretation of observed isotopic shifts in microbial mat carbonate depends on fully characterizing ambient ?13C and eliminating other origins for isotopic shifts. The carbon isotopic composition of reservoirs can vary substantially, both on Earth and on other planets. Characterizing the reservoir composition and any changes through time is critical to evaluating microbially induced shifts. In addition, careful evaluation of non-microbial causes for shifts in isotopic composition is essential for a reliable interpretation. Complicating processes include recrystallization, calcite precipitation over extended periods of time, variable precipitation rates and water chemistry, and mixing of carbonates having different isotopic signatures.

Sumner, Dawn Y.



Carbon and Nitrogen Abundances in Early-type Galaxies  

E-print Network

For the first time, we undertake a systematic examination of the nitrogen abundances for a sample of 35 early-type galaxies spanning a range of masses and local environment. The nitrogen-sensitive molecular feature at 3360\\AA has been employed in conjunction with a suite of atomic- and molecular-sensitive indices to provide unique and definitive constraints on the chemical content of these systems. By employing NH3360, we are now able to break the carbon, nitrogen, and oxygen degeneracies inherent to the use of the CN-index. We demonstrate that the NH3360 feature shows little dependency upon the velocity dispersion (our proxy for mass) of the galaxies, contrary to what is seen for carbon- and magnesium-sensitive indices. At face value, these results are at odds with conclusions drawn previously using indices sensitive to both carbon and nitrogen, such as cyanogen (CN). With the aid of stellar population models, we find that the N/Fe ratios in these galaxies are consistent with being mildly-enhanced with respect to the solar ratio. We also explore the dependence of these findings upon environment, by analyzing the co-added spectra of galaxies in the field and the Coma cluster. We confirm the previously found differences in carbon abundances between galaxies in low- and high-density environments, while showing that these differences do not seem to exist for nitrogen. We discuss the implications of these findings for the derivation of the star formation histories in early-type galaxies, and for the origin of carbon and nitrogen, themselves.

Elisa Toloba; Patricia Sanchez-Blazquez; Javier Gorgas; Brad K. Gibson



Carbon isotopic characterisation of dissolved organic matter during water treatment.  


Water treatment is a series of physio-chemical processes to aid organic matter (OM) removal, which helps to minimise the formation of potentially carcinogenic disinfection by-products and microbial regrowth. Changes in OM character through the treatment processes can provide insight into the treatment efficiency, but radiogenic isotopic characterisation techniques have yet to be applied. Here, we show for the first time that analysis of (13)C and (14)C of dissolved organic carbon (DOC) effectively characterises dissolved OM through a water treatment works. At the sites investigated: post-clarification, DOC becomes isotopically lighter, due to an increased proportion of relatively hydrophilic DOC. Filtration adds 'old' (14)C-DOC from abrasion of the filter media, whilst the use of activated carbon adds 'young' (14)C-DOC, most likely from the presence of biofilms. Overall, carbon isotopes provide clear evidence for the first time that new sources of organic carbon are added within the treatment processes, and that treated water is isotopically lighter and typically younger in (14)C-DOC age than untreated water. We anticipate our findings will precipitate real-time monitoring of treatment performance using stable carbon isotopes, with associated improvements in energy and carbon footprint (e.g. isotopic analysis used as triggers for filter washing and activated carbon regeneration) and public health benefits resulting from improved carbon removal. PMID:24075722

Bridgeman, John; Gulliver, Pauline; Roe, Jessie; Baker, Andy



A Study of Circumstellar Envelopes around Bright Carbon Stars. II. Molecular Abundances  

NASA Astrophysics Data System (ADS)

We have estimated and compared circumstellar and photospheric HCN, CN, and CS abundances for a sample of bright carbon stars. The circumstellar HCN and CS abundances roughly correlate with the photospheric ones, but the former appear to be systematically overestimated by a factor of 5-10. Although we cannot exclude the presence of a circumstellar chemistry that efficiently produces HCN and CS in the inner parts of these relatively hot circumstellar envelopes, we attribute this difference between photospheric and circumstellar abundances to errors in the circumstellar envelope model used. In particular, for the low mass-loss rate objects a systematic underestimate of the mass-loss rate may be suspected. In addition to this general trend, stars that are in some sense peculiar also show circumstellar abundances that deviate significantly from the expected. There is evidence for the presence of maser features in the HCN (J = 1-0) emission toward some of the stars. The estimated circumstellar CN abundances suggest that this species is a photodissociation product of HCN. A search for circumstellar HNC, SiS, and HC3N shows that molecular emission from species other than CO, HCN, CN, and CS is very weak in these low mass-loss rate objects. An attempt has been made to determine the chemistry in the (probably detached) envelope around R Scl. The data suggest a carbon-rich chemistry. Finally, it is shown that the circumstellar 12CO/13CO and H12CN/H13CN intensity ratios roughly correlate with the photospheric 12C/13C isotope ratios for a small number of low mass-loss rate objects, although the former ratios are systematically lower than the latter by a factor of about 2.

Olofsson, H.; Eriksson, K.; Gustafsson, B.; Carlstroem, U.



Carbon Isotopic Ratios of Amino Acids in Stardust-Returned Samples  

NASA Technical Reports Server (NTRS)

NASA's Stardust spacecraft returned to Earth samples from comet 81P/Wild 2 in January 2006. Preliminary examinations revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds could not be identified. Here. we present the carbon isotopic ratios of glycine and E-aminocaproic acid (EACH), the two most abundant amino acids observed, in Stardust-returned foil samples measured by gas chromatography-combustion-isotope ratio crass spectrometry coupled with quadrupole mass spectrometry (GC-QMS/IRMS).

Elsila, Jamie E.; Glavin, Daniel P.; Dworkin, Jason P.



Carbon Isotopic Measurements of Amino Acids in Stardust-Returned Samples  

NASA Technical Reports Server (NTRS)

NASA's Stardust spacecraft returned to Earth samples from comet 81P/Wild 2 in January 2006. Preliminary examinations revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds could not be identified. Here, we present the carbon isotopic ratios of glycine and e-aminocaproic acid (EACA), the two most abundant amino acids, in Stardust-returned foil samples measured by gas chromatography-combustion-isotope ratio mass spectrometry coupled with quadrupole mass spectrometry (GC-CAMS/IRMS).

Elsila, Jamie



A measurement of the isotopic composition of galactic cosmic ray carbon, nitrogen and oxygen  

NASA Technical Reports Server (NTRS)

The paper reports the results of an investigation of the isotopic composition of galactic cosmic ray carbon, nitrogen and oxygen (80-230 MeV/amu) made using the U.C. Berkeley HKH instrument aboard the ISEE-3 spacecraft. The combination of high mass resolution and a large statistical sample makes possible a precise determination of the relative isotopic abundances for these elements. In local interplanetary space the following values are found: C-13/C = 0.067 + or - 0.008, N-15/N = 0.54 + or - 0.03, O-17/O less than 0.027, and O-18/O - 0.019 + or - 0.003.

Wiedenbeck, M. E.; Greiner, D. E.; Bieser, F. S.; Crawford, H. J.; Heckman, H. H.; Lindstrom, P. J.



The Barium Isotopic Abundance in the Metal-Poor Star HD140283  

E-print Network

We derive the mixture of odd to even barium isotopes in the atmosphere of the metal-poor subgiant HD140283 from the analysis of the Ba II transition at 455.4 nm in a high-resolution high signal-to-noise spectrum of the star. The detailed shape of this spectral line depends on the relative contributions of odd and even isotopes via isotopic and hyperfine splitting. We measure the fractional abundance of odd Ba isotopes by modelling the formation of the Ba II 455.4 nm line profile with the use of both a classical 1D hydrostatic and a 3D hydrodynamical model atmosphere of HD140283. We interpret the results in terms of contributions by the slow (s-) and rapid (r-) neutron-capture processes to the isotopic mix. While the result of the 1D analysis of the Ba II feature indicates a (64 +/- 36)% contribution of the r-process to the isotopic mix, the 3D analysis points toward a mere (15 +/- 34)% contribution from this process, that is consistent with a solar-like mixture of barium isotopes.

R. Collet; M. Asplund; P. E. Nissen



Carbon isotope fractionation during calcium carbonate precipitation induced by ureolytic bacteria  

NASA Astrophysics Data System (ADS)

Ureolytic bacteria have been proposed as model organisms to investigate the potential of subsurface microorganisms to enhance carbon capture and storage through solubility- and mineral-trapping of CO2 induced by bacterial ureolysis and carbonate formation. Ideally, CO2 incorporation into carbonates can be readily traced using carbon isotope measurements. However, the carbon isotope systematics of bacterial ureolysis and associated carbonate precipitation is still poorly known. We determined the carbon isotope fractionations expressed during ureolysis and carbonate precipitation induced by Sporosarcina pasteurii at 30 °C. Our results indicate that bacterial ureolysis proceeds as a Rayleigh distillation characterized by a 13C-enrichment factor equal to -12.5‰. As precipitation proceeds, the ?13C value of CaCO3, initially 1-2.1‰ lower than that of dissolved inorganic carbon (DIC), evolves progressively until it is 0.5‰ higher than that of the DIC, i.e. close to the value predicted for isotopic equilibrium. The minor isotope disequilibrium at the onset of precipitation and its rapid evolution towards isotopic equilibrium point to bacterial carbonates as reliable recorders of the carbon isotope composition of DIC. This corroborates the potential utility of 13C-tracing for the quantification of microbially-induced CO2 sequestration into solid carbonates and DIC.

Millo, Christian; Dupraz, S.; Ader, M.; Guyot, F.; Thaler, C.; Foy, E.; Ménez, B.



Origin of petroporphyrins. 2. Evidence from stable carbon isotopes.  


Compared with the carbon-13 isotopic composition of the ubiquitous C32DPEP (DPEP, deoxophylloerythroetioporphyrin) the heavy but equivalent carbon-13 isotopic composition for the porphyrin structures 15(2)-methyl-15,17-ethano-17-nor-H-C30DPEP and 15,17-butano-, 13,15-ethano-13(2),17-propano-, and 13(1)-methyl-13,15-ethano-13(2),17-propanoporphyrin suggests a common precursor, presumably chlorophyll c, for these petroporphyrins isolated from the marine Julia Creek oil shale and the lacustrine Condor oil shale. Similarly, the heavy but variable carbon-13 isotopic composition of 7-nor-H-C31DPEP compared with C32DPEP is consistent with an origin from both chlorophyll b and chlorophyll c3. The equivalent carbon-13 isotopic composition for 13(2)-methyl-C33DPEP compared with C32DPEP suggests a common origin resulting from a weighted average of chlorophyll inputs. PMID:11538479

Boreham, C J; Fookes, C J; Popp, B N; Hayes, J M



Origin of petroporphyrins. 2. Evidence from stable carbon isotopes  

NASA Technical Reports Server (NTRS)

Compared with the carbon-13 isotopic composition of the ubiquitous C32DPEP (DPEP, deoxophylloerythroetioporphyrin) the heavy but equivalent carbon-13 isotopic composition for the porphyrin structures 15(2)-methyl-15,17-ethano-17-nor-H-C30DPEP and 15,17-butano-, 13,15-ethano-13(2),17-propano-, and 13(1)-methyl-13,15-ethano-13(2),17-propanoporphyrin suggests a common precursor, presumably chlorophyll c, for these petroporphyrins isolated from the marine Julia Creek oil shale and the lacustrine Condor oil shale. Similarly, the heavy but variable carbon-13 isotopic composition of 7-nor-H-C31DPEP compared with C32DPEP is consistent with an origin from both chlorophyll b and chlorophyll c3. The equivalent carbon-13 isotopic composition for 13(2)-methyl-C33DPEP compared with C32DPEP suggests a common origin resulting from a weighted average of chlorophyll inputs.

Boreham, C. J.; Fookes, C. J.; Popp, B. N.; Hayes, J. M.



Fisherfolk and Farmers: Carbon and Nitrogen Isotope Evidence from Middle  

E-print Network

Fisherfolk and Farmers: Carbon and Nitrogen Isotope Evidence from Middle Horizon Anco´n, Peru N. M compared to that of adults, perhaps as a result of nursing activity and/or differential dietary practices of archaeological skeletal remains are based on the well-tested premise that isotopic ratios in human bones

Paytan, Adina


Bromine and carbon isotope effects during photolysis of brominated phenols.  


In the present study, carbon and bromine isotope effects during UV-photodegradation of bromophenols in aqueous and ethanolic solutions were determined. An anomalous relatively high inverse bromine isotope fractionation (?reactive position up to +5.1‰) along with normal carbon isotope effect (?reactive position of -12.6‰ to -23.4‰) observed in our study may be attributed to coexistence of both mass-dependent and mass-independent isotope fractionation of C-Br bond cleavage. Isotope effects of a similar scale were observed for all the studied reactions in ethanol, and for 4-bromophenol in aqueous solution. This may point out related radical mechanism for these processes. The lack of any carbon and bromine isotope effects during photodegradation of 2-bromophenol in aqueous solution possibly indicates that C-Br bond cleavage is not a rate-limiting step in the reaction. The bromine isotope fractionation, without any detectable carbon isotope effect, that was observed for 3-bromophenol photolysis in aqueous solution probably originates from mass-independent fractionation. PMID:24245662

Zakon, Yevgeni; Halicz, Ludwik; Gelman, Faina



Ar-39 Detection at the 10^-16 Isotopic Abundance Level with Atom Trap Trace Analysis  

E-print Network

Atom Trap Trace Analysis (ATTA), a laser-based atom counting method, has been applied to analyze atmospheric Ar-39 (half-life = 269 yr), a cosmogenic isotope with an isotopic abundance of 8x10^-16. In addition to the superior selectivity demonstrated in this work, counting rate and efficiency of ATTA have been improved by two orders of magnitude over prior results. Significant applications of this new analytical capability lie in radioisotope dating of ice and water samples and in the development of dark matter detectors.

W. Jiang; W. D. Williams; K. Bailey; A. M. Davis; S. -M. Hu; Z. -T. Lu; T. P. O'Connor; R. Purtschert; N. C. Sturchio; Y. R. Sun; P. Mueller



Observations of Carbon Isotopic Fractionation in Interstellar Formaldehyde  

NASA Technical Reports Server (NTRS)

Primitive Solar System materials (e.g. chondrites. IDPs, the Stardust sample) show large variations in isotopic composition of the major volatiles (H, C, N, and O ) even within samples, witnessing to various degrees of processing in the protosolar nebula. For ex ample. the very pronounced D enhancements observed in IDPs [I] . are only generated in the cold. dense component of the interstellar medium (ISM), or protoplanetary disks, through ion-molecule reactions in the presence of interstellar dust. If this isotopic anomaly has an interstellar origin, this leaves open the possibility for preservation of other isotopic signatures throughout the form ation of the Solar System. The most common form of carbon in the ISM is CO molecules, and there are two potential sources of C-13 fractionation in this reservoir: low temperature chemistry and selective photodissociation. While gas-phase chemistry in cold interstellar clouds preferentially incorporates C-13 into CO [2], the effect of self-shielding in the presence of UV radiation instead leads to a relative enhancement of the more abundant isotopologue, 12CO. Solar System organic material exhibit rather small fluctuations in delta C-13 as compared to delta N-15 and delta D [3][1], the reason for which is still unclear. However, the fact that both C-13 depleted and enhanced material exists could indicate an interstellar origin where the two fractionation processes have both played a part. Formaldehyde (H2CO) is observed in the gas-phase in a wide range of interstellar environments, as well as in cometary comae. It is proposed as an important reactant in the formation of more complex organic molecules in the heated environments around young stars, and formaldehyde polymers have been suggested as the common origin of chondritic insoluable organic matter (IOM) and cometary refractory organic solids [4]. The relatively high gas-phase abundance of H2CO observed in molecular clouds (10(exp- 9) - 10(exp- 8) relative to H2) makes it feasible to observe its less common isotopologues. As a step in our investigation of C-13 fractionation patterns in the ISM, we here present comparisons between observations of the C-13 fraction in formaldehyde, and chemical fractionation models.

Wirstrom, E. S.; Charnley, S. B.; Geppert, W. D.; Persson, C. M.



Biological control of calcium isotopic abundances in the global calcium cycle  

SciTech Connect

Measurements of {sup 44}Ca/{sup 40}Ca, expressed as {delta}{sup 44}Ca, were made on igneous rocks and on shell and bone material from modern organisms to investigate the magnitude and origins of calcium isotopic fractionation in nature. The results document a span of 4{per_thousand} in {delta}{sup 44}Ca, measured with the double spike technique to a precision of {+-}0.15{per_thousand}. Volcanic rocks, including basalt and rhyolite, show little variability and cluster near {delta}{sup 44}Ca = 0 {+-}0.2. Systematic analysis of biological samples indicates that biological processing of calcium discriminates against heavy isotopes, and that biological fractionation is the primary generator of calcium isotopic fractionation in nature. Preliminary data suggest that calcium becomes isotopically lighter as it moves through food chains. Calcium carbonate shells of marine microorganisms and deep-sea carbonate ooze have {delta}{sup 44}Ca about 1.0{per_thousand}, lower than seawater; this fractionation causes seawater to be enriched in heavy calcium ({delta}{sup 44}Ca = +0.9) relative to igneous rocks. Marine organisms consequently are isotopically heavier than their terrestrial counterparts at similar trophic level. The calcium isotopic composition of living and fossil organisms may record information on diet and environment. 22 refs., 3 figs., 2 tabs.

Skulan, J. [Univ. of California, Berkeley, CA (United States)] [Univ. of California, Berkeley, CA (United States); DePaolo, D.J.; Owens, T.L. [Lawrence Berkeley National Lab., CA (United States)] [Lawrence Berkeley National Lab., CA (United States); [Univ. of California, Berkeley, CA (United States)



[Terrestrial plant stable carbon isotope composition and global change].  


Stable carbon isotope analysis is a rapid and reliable technique developed in recent years, and has been widely applied to reconstruct the sequences of atmospheric CO2 concentration changes, clarify the hysteresis effect and junior effect of temperature and precipitation on tree growth, and distinguish the distributions of plants with different photosynthetic pathways. The water use efficiency (WUE) of different plant functional groups and the variations of plant WUE with tempo-spatial and climatic changes can be also indicated by determining plant carbon isotope composition. In this paper, the effects of environmental factors, e.g., atmospheric CO2 concentration, air temperature, precipitation, and altitude on terrestrial plant carbon isotope composition were discussed, and the advances and applications of carbon isotope technique in global change research were summarized. Furthermore, the existing and disputed problems in carbon isotope analysis were discussed, and the future trends of carbon isotope technique in global change research were prospected, aimed to widen people's knowledge and promote the development of this technique. PMID:16836111

Zheng, Shuxi; Shangguan, Zhouping



Carbon isotope analysis for source identification of atmospheric formaldehyde and acetaldehyde in Dinghushan Biosphere Reserve in South China  

Microsoft Academic Search

Formaldehyde and acetaldehyde are two most abundant carbonyls in ambient air. Biogenic emission has been proposed as a significant source other than anthropogenic emissions and atmospheric secondary formation. Here at a forest site in South China, the carbon isotopic compositions of formaldehyde and acetaldehyde emitted from leaves of three tree species (Litsea rotundifolia, Canarium album and Castanea henryi) were measured

Songjun Guo; Sheng Wen; Xinming Wang; Guoying Sheng; Jiamo Fu; Ping Hu; Yingxin Yu




E-print Network

A FIRST LOOK AT GRAPHITE GRAINS FROM ORGUEIL: MORPHOLOGY, CARBON, NITROGEN AND NEON ISOTOPIC Drive, CB 1105, Saint Louis, MO, USA ( Presolar graphite in Murchison has been exten to a higher presolar graphite abundance in Orgueil, or due to a higher Ne-E concentrations per grain. The Ne


Mercury abundances and isotopic compositions in the Murchison (CM) and Allende (CV) carbonaceous chondrites  

NASA Astrophysics Data System (ADS)

The abundance and isotopic composition of Hg was determined in bulk samples of both the Murchison (CM) and Allende (CV) carbonaceous chondrites using single- and multi-collector inductively coupled plasma mass spectrometry (ICP-MS). The bulk abundances of Hg are 294 ± 15 ng/g in Murchison and 30.0 ± 1.5 ng/g in Allende. These values are within the range of previous measurements of bulk Hg abundances by neutron activation analysis (NAA). Prior studies suggested that both meteorites contain isotopically anomalous Hg, with ? 196/202Hg values for the anomalous, thermal-release components from bulk samples ranging from -260 ‰ to +440 ‰ in Murchison and from -620 ‰ to +540 ‰ in Allende (Jovanovic and Reed, 1976a; 1976b; Kumar and Goel, 1992). Our multi-collector ICP-MS measurements suggest that the relative abundances of all seven stable Hg isotopes in both meteorites are identical to terrestrial values within 0.2 to 0.5 ‰. On-line thermal-release experiments were performed by coupling a programmable oven with the single-collector ICP-MS. Powdered aliquots of each meteorite were linearly heated from room temperature to 900°C over twenty-five minutes under an Ar atmosphere to measure the isotopic composition of Hg released from the meteorites as a function of temperature. In separate experiments, the release profiles of S and Se were determined simultaneously with Hg to constrain the Hg distribution within the meteorites and to evaluate the possibility of Se interferences in previous NAA studies. The Hg-release patterns differ between Allende and Murchison. The Hg-release profile for Allende contains two distinct peaks, at 225° and 343°C, whereas the profile for Murchison has only one peak, at 344°C. No isotopically anomalous Hg was detected in the thermal-release experiments at a precision level of 5 to 30 ‰, depending on the isotope ratio. In both meteorites the Hg peak at ˜340°C correlates with a peak in the S-release profile. This correlation suggests that Hg is associated with S-bearing phases and, thus, that HgS is a major Hg-bearing phase in both meteorites. The Hg peak at 225°C for Allende is similar to release patterns of physically adsorbed Hg on silicate and metal grains. Prior studies suggested that the isotopic anomalies reported from NAA resulted from interference between 203Hg and 75Se. However, the amount of Se released from both meteorites, relative to Hg, is insufficient to produce all of the observed anomalies.

Lauretta, Dante S.; Klaue, Bjoern; Blum, Joel D.; Buseck, Peter R.



Carbon isotope systematics of a mantle ``hotspot'': a comparison of Loihi Seamount and MORB glasses  

NASA Astrophysics Data System (ADS)

The carbon isotope geochemistry of glasses from Loihi Seamount has been compared with that of MORB glasses. Stepped heating shows two carbon components in both sample suites: (1) isotopically light carbon ( avg. ? 13C = -26.3‰ ) released < 600°C, ascribed to surficial contamination, and (2) isotopically heavy carbon released > 600°C, regarded as indigenous. The high-temperature component in MORB samples varied from 52 to 169 ppm C, average ? 13C = -6.6‰ , consistent with previous studies (overall MORD average ? 13C = -6.4 ± 0.9‰ ), and new results for Indian Ocean glasses are similar to Atlantic and Pacific Ocean samples. Carbon release profiles produced by stepped heating may be typical of locality, but there are no significant differences in ? 13C values between MORB samples from different areas. Lower yields (17-110 ppm C) correlated with depth in the Loihi samples suggest that they are partially degassed. This degassing has not affected ? 13C values significantly (avg. -5.8‰). Loihi tholeiites have higher ? 13C (avg. -5.6‰) than the alkali basalts (avg. -7.1‰). Carbon abundances correlate well with He concentration data. Comparison of the ? 13C values with trace element and He, Sr, Nd, and Pb isotope data from the literature suggests that the Loihi samples with highest ? 13C have high 3He/ 4He and possibly the least depleted 143Nd/ 144Nd and 87Sr/ 86Sr. The carbon isotope data are consistent with previous models for Loihi involving several mantle sources, lithospheric contamination, and mixing. The slightly higher ? 13C of Loihi tholeiites suggests that the undegassed "plume" component manifested by high 3He/ 4He values might have ? 13C about 1‰ higher than the MORB average.

Exley, R. A.; Mattey, D. P.; Clague, D. A.; Pillinger, C. T.



The Palaeocene-Eocene carbon isotope excursion: constraints from individual shell planktonic foraminifer records.  


The Palaeocene-Eocene thermal maximum (PETM) is characterized by a global negative carbon isotope excursion (CIE) and widespread dissolution of seafloor carbonate sediments. The latter feature supports the hypothesis that the PETM and CIE were caused by the rapid release of a large mass (greater than 2000Gt C) of 12C-enriched carbon. The source of this carbon, however, remains a mystery. Possible sources include volcanically driven thermal combustion of organic-rich sediment, dissociation of seafloor methane hydrates and desiccation and oxidation of soil/sediment organics. A key constraint on the source(s) is the rate at which the carbon was released. Fast rates would be consistent with a catastrophic event, e.g. massive methane hydrate dissociation, whereas slower rates might implicate other processes. The PETM carbon flux is currently constrained by high-resolution marine and terrestrial records of the CIE. In pelagic bulk carbonate records, the onset of the CIE is often expressed as a single- or multiple-step excursion extending over 10(4) years. Individual planktonic shell records, in contrast, always show a single-step CIE, with either pre-excursion or excursion isotope values, but no transition values. Benthic foraminifera records, which are less complete owing to extinction and diminutive assemblages, show a delayed excursion. Here, we compile and evaluate the individual planktonic shell isotope data from several localities. We find that the most expanded records consistently show a bimodal isotope distribution pattern regardless of location, water depth or depositional facies. This suggests one of several possibilities: (i) the isotopic composition of the surface ocean/atmosphere declined in a geologic instant (<500yr), (ii) that during the onset of the CIE, most shells of mixed-layer planktonic foraminifera were dissolved, or (iii) the abundances or shell production of these species temporarily declined, possibly due to initial pH changes. PMID:17513259

Zachos, James C; Bohaty, Steven M; John, Cedric M; McCarren, Heather; Kelly, Daniel C; Nielsen, Tina



Multiple Group Analysis (MGA): A gamma-ray spectrum analysis code for determining plutonium isotopic abundances  

SciTech Connect

MGA calculates relative isotopic abundances of plutonium and other actinides in a sample. The code performs its analysis using data from a gamma-ray spectrum of the sample taken with a germanium detector. This volume describes the structure of the program and the procedures used for measuring samples and analyzing the spectra. It is assumed that the user is familiar with standard practices and equipment used in gamma-ray spectrometry.

Gunnink, R.; Ruhter, W.D.



Experimental determination of carbon isotope fractionation between graphite and carbonated silicate melt under upper mantle conditions  

NASA Astrophysics Data System (ADS)

Carbon isotope fractionation between graphite and carbonated silicate melt was determined at 5 GPa and in the temperature range between 1400 and 1900 °C. High pressure experiments were carried out in the carbon-saturated model harzbergite system (Enstatite-Magnesite-Olivine-Graphite), where carbonated silicate melt and graphite were the two stable carbon-bearing phases in the run products. Carbonated silicate melting resulted in an isotopic fractionation between graphite and carbon in the silicate melt, where the carbon in the melt is 13C enriched than co-existing graphite. 13C enrichment in carbonate melt when compared to graphite was further confirmed in experiments where redox melting between olivine and graphite produced carbonate melt as well as carbonate reduction experiments to form graphite. Although a quantitative estimate of fractionation between carbonate melt and graphite could not be obtained, our results indicate that mantle melting in the presence of graphite can result in progressive 13C carbon isotope enrichment in carbonate melt and depletion in graphite, which can be an alternate explanation for the carbon isotopic heterogeneity observed in the mantle derived carbon.

Mizutani, Shogo; Satish-Kumar, M.; Yoshino, Takashi



The Abundance of Carbon Monoxide in Neptune's Atmosphere  

NASA Astrophysics Data System (ADS)

The unexpected discovery of carbon monoxide in the stratosphere of Neptune in 1991 and its absence in Uranus have important implications for the origin of the planet. The two potential sources of CO in Neptune are infalling material from the interplanetary medium, and convection due to Neptune's stronger internal heat source. The tropospheric CO abundance would be a key discriminator between these two possibilities. The CO J=3-2 absorption line is strongly pressure-broadened and ideally suited for measurement using a Fourier transform spectrometer (FTS), which offers moderate spectral resolution over a wide spectral range. Observations in 1993 using the University of Lethbridge FTS at the James Clerk Maxwell Telescope (JCMT) resulted in a marginal detection of the CO absorption line (Naylor et al., 1994, A & A 291, L51-L53). The accuracy of the abundance was limited by channel fringing, which is the result of multiple reflections from parallel surfaces within the detector optics and produces a high-frequency modulation in the data. To improve upon this measurement, the instrumentation was upgraded including a completely new FTS in the Mach-Zehnder configuration, a new detector system with better optical design to minimize the effect of channel fringing, and an enhanced data processing pipeline. Analysis of the data obtained during an observing run in September 2002 has confirmed the existence of tropospheric CO in Neptune. These results will be presented. This research is supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada.

Hesman, B. E.; Davis, G. R.; Naylor, D. A.




SciTech Connect

Carbon-enhanced metal-poor (CEMP) stars are believed to show the chemical imprints of more massive stars (M {approx}> 0.8 M{sub Sun }) that are now extinct. In particular, it is expected that the observed abundance of Li should deviate in these stars from the standard Spite lithium plateau. We study here a sample of 11 metal-poor stars and a double-lined spectroscopic binary with -1.8 < [Fe/H] < -3.3 observed with the Very Large Telescope/UVES spectrograph. Among these 12 metal-poor stars, there are 8 CEMP stars for which we measure or constrain the Li abundance. In contrast to previous arguments, we demonstrate that an appropriate regime of dilution permits the existence of 'Li-Spite plateau and C-rich' stars, whereas some of the 'Li-depleted and C-rich' stars call for an unidentified additional depletion mechanism that cannot be explained by dilution alone. We find evidence that rotation is related to the Li depletion in some CEMP stars. Additionally, we report on a newly recognized double-lined spectroscopic binary star in our sample. For this star, we develop a new technique from which estimates of stellar parameters and luminosity ratios can be derived based on a high-resolution spectrum alone, without the need for input from evolutionary models.

Masseron, Thomas; Johnson, Jennifer A. [Department of Astronomy, Ohio State University, 140 W. 18th Ave., Columbus, OH 43210 (United States); Lucatello, Sara [INAF, Osservatorio Astronomico di Padova, vicolo dell'Osservatorio 5, 35122 Padova (Italy); Karakas, Amanda [Research School of Astronomy and Astrophysics, Australian National University, Mount Stromlo Observatory, Cotter Road, Weston, ACT 2611 (Australia); Plez, Bertrand [LUPM cc072, Universite Montpellier II, F-34095 Montpellier cedex 5 (France); Beers, Timothy C. [Department of Physics and Astronomy and JINA: Joint Institute for Nuclear Astrophysics, Michigan State University, E. Lansing, MI 48824 (United States); Christlieb, Norbert, E-mail:, E-mail: [Zentrum fuer Astronomie der Universitaet Heidelberg, Landessternwarte, Koenigstuhl 12, 69117, Heidelberg (Germany)



An investigation of techniques for the measurement and interpretation of cosmic ray isotopic abundances. Ph.D. Thesis  

NASA Technical Reports Server (NTRS)

An instrument, the Caltech High Energy Isotope Spectrometer Telescope was developed to measure isotopic abundances of cosmic ray nuclei by employing an energy loss - residual energy technique. A detailed analysis was made of the mass resolution capabilities of this instrument. A formalism, based on the leaky box model of cosmic ray propagation, was developed for obtaining isotopic abundance ratios at the cosmic ray sources from abundances measured in local interstellar space for elements having three or more stable isotopes, one of which is believed to be absent at the cosmic ray sources. It was shown that the dominant sources of uncertainty in the derived source ratios are uncorrelated errors in the fragmentation cross sections and statistical uncertainties in measuring local interstellar abundances. These results were applied to estimate the extent to which uncertainties must be reduced in order to distinguish between cosmic ray production in a solar-like environment and in various environments with greater neutron enrichments.

Wiedenbeck, M. E.



[Carbon isotope fractionation inplants]. Final report  

SciTech Connect

The objectives of this research are: To develop a theoretical and experimental framework for understanding isotope fractionations in plants; and to develop methods for using this isotope fractionation for understanding the dynamics of CO{sub 2} fixation in plants. Progress is described.

O`Leary, M.H.



Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale  

NASA Technical Reports Server (NTRS)

The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.

Chicarelli, M. I.; Hayes, J. M.; Popp, B. N.; Eckardt, C. B.; Maxwell, J. R.



Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale.  


The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion. PMID:11537805

Chicarelli, M I; Hayes, J M; Popp, B N; Eckardt, C B; Maxwell, J R



Isotopic compositions of carbonates and organic carbon from upper Proterozoic successions in Namibia: stratigraphic variation and the effects of diagenesis and metamorphism  

NASA Technical Reports Server (NTRS)

The carbon isotope geochemistry of carbonates and organic carbon in the late Proterozoic Damara Supergroup of Namibia, including the Nama, Witvlei, and Gariep groups on the Kalahari Craton and the Mulden and Otavi groups on the Congo Craton, has been investigated as an extension of previous studies of secular variations in the isotopic composition of late Proterozoic seawater. Subsamples of microspar and dolomicrospar were determined, through petrographic and cathodoluminescence examination, to represent the "least-altered" portions of the rock. Carbon-isotopic abundances in these phases are nearly equal to those in total carbonate, suggesting that 13C abundances of late Proterozoic fine-grained carbonates have not been significantly altered by meteoric diagenesis, although 18O abundances often differ significantly. Reduced and variable carbon-isotopic differences between carbonates and organic carbon in these sediments indicate that isotopic compositions of organic carbon have been altered significantly by thermal and deformational processes, likely associated with the Pan-African Orogeny. Distinctive stratigraphic patterns of secular variation, similar to those noted in other, widely separated late Proterozoic basins, are found in carbon-isotopic compositions of carbonates from the Nama and Otavi groups. For example, in Nama Group carbonates delta 13C values rise dramatically from -4 to +5% within a short stratigraphic interval. This excursion suggests correlation with similar excursions noted in Ediacaran-aged successions of Siberia, India, and China. Enrichment of 13C (delta 13C> +5%) in Otavi Group carbonates reflects those in Upper Riphean successions of the Akademikerbreen Group, Svalbard, its correlatives in East Greenland, and the Shaler Group, northwest Canada. The widespread distribution of successions with comparable isotopic signatures supports hypotheses that variations in delta 13C reflect global changes in the isotopic composition of late Proterozoic seawater. Within the Damara basin, carbon-isotopic compositions of carbonates provide a potentially useful tool for the correlation of units between the Kalahari and Congo cratons. Carbonates depleted in 13C were deposited during and immediately following three separate glacial episodes in Namibia. The correspondence between ice ages and negative delta 13C excursions may reflect the effects of lowered sea levels; enhanced circulation of deep, cold, O2-rich seawater; and/or the upwelling of 13C-depleted deep water. Iron-formation is additionally associated with one of the glacial horizons, the Chuos tillite. Carbon-13 enriched isotopic abundances in immediately pre-glacial carbonates suggest that oceanographic conditions favored high rates of organic burial. It is likely that marine waters were stratified, with deep waters anoxic. A prolonged period of ocean stratification would permit the build-up of ferrous iron, probably from hydrothermal sources. At the onset of glaciation, upwelling would have brought 13C-depleted and iron-rich deep water onto shallow shelves where contact with cold, oxygenated surface waters led to the precipitation of ferric iron.

Kaufman, A. J.; Hayes, J. M.; Knoll, A. H.; Germs, G. J.



Carbon cycle for Lake Washington - a stable isotope study  

Microsoft Academic Search

The authors investigate the carbon cycle in Lake Washington for the year 1980 using monthly measurements of the dissolved inorganic carbon (DIC) and its ¹³C:¹²C isotopic composition. Mass balances of DIC and its ¹³C:¹²C yield estimates of COâ gas exchange rates and net organic carbon production rates. Between 24 June and 13 August, the calculated COâ gas invasion rate of

P. D. Quay; S. R. Emerson; B. M. Quay; A. H. Devol



Investigation of tubular handling of bicarbonate in man. A new approach utilizing stable carbon isotope fractionation.  

PubMed Central

Two alternative mechanisms have been proposed for tubular reabsorption of bicarbonate: (a) H+ secretion and CO2 reabsorption and (b) direct reabsorption of HCO-3. In an attempt to differentiate between the two mechanisms, the present study utilized the natural abundance of stable carbon isotopes (13C, 12C) in the urinary total CO2. This novel methodology used mass spectrometric analysis of 13C/12C ratios in urinary total CO2 under normal conditions and during acetazolamide treatment. Blood and respiratory CO2 were analyzed to yield reference values. The results demonstrate that alkaline urine is preferentially enriched with 13C relative to the blood. It is suggested that this fractionation results from reaction out of isotopic equilibrium in which HCO-3 converts to CO2 during the reabsorption process in the distal nephron. The presence of carbonic anhydrase in the proximal nephron results in rapid isotopic exchange between CO2 and HCO-3 and keeps them in isotopic equilibrium. The ratio of urinary 13C/12C increases strikingly after acetazolamide administration and consequent inhibition of carbonic anhydrase in the proximal tubule. Although it is possible that in the latter case high HCO-3 generates the CO2 (ampholyte effect), the isotope fractionation indicates that CO2 rather than HCO-3 is reabsorbed. In contrast, at low urinary pH and total CO2 values, the carbon isotope composition approaches that of blood CO2. This indicates rapid CO2 exchange between urine and blood, through luminal membrane highly permeable to CO2. These results could be anticipated by a mathematical model constructed to plot 13C concentration of urinary total CO2. It is concluded that the mechanism of HCO-3 reclamation in man (and, by inference, in other mammals as well) works by conversion of HCO-3 to CO2 and reabsorption of CO2. PMID:6417168

Burbea, Z H; Luz, B; Lazar, B; Winaver, J; Better, O S



M.R. Saltzman and E. Thomas Chapter 11 Carbon Isotope Stratigraphy  

E-print Network

to date and correlate sediments. The stratigraphic record of carbon isotopes is complex because the main OF CARBON ISOTOPE STRATIGRAPHY The potential of marine carbonate d13 C trends and excursions to dateM.R. Saltzman and E. Thomas Chapter 11 Carbon Isotope Stratigraphy Abstract: Variations in the 13 C

Saltzman, Matthew R.


The link between assimilation and below-ground processes - stable isotopes as tools to assess carbon transfer  

NASA Astrophysics Data System (ADS)

At present, there is lack of knowledge on how plant physiological processes, the transfer of carbon within the plant, carbon storage and remobilization in the plant tissues as well as the release of carbon from the roots to the soil interact with ecosystem-scale processes. On the background of global climate change, we need to mechanistically link plant physiology, CO2 net exchange between ecosystems and the atmosphere and plant biomass accumulation. This is the basis for predicting productivity of forests as well as their carbon sequestration potential in future. This paper will give an overview on how stable isotope studies can give insights into the fate of newly assimilated carbon transported within trees and transferred to the soil and atmosphere. The paper includes assessments characterizing temporal and spatial variation in the natural abundance of carbon and oxygen isotopes or applying isotopically enriched tracers. In addition, it highlights the fact that the stable isotope composition of assimilates transported within the plant contains important time integrated information on environmental conditions, leaf physiology, and post-photosynthetic metabolism. The paper on the one hand focuses on the fast turn over carbon pools, which fuel plant respiration and soil microbial activity and on the other hand explores the transfer of the isotope information to long-lived compounds in plant archives such as tree rings.

Gessler, A.; Wingate, L.; Ogeé, J.; Offermann, C.; Kodama, N.



Isotopic composition of carbon and nitrogen in ureilitic fragments of the Almahata Sitta meteorite  

NASA Astrophysics Data System (ADS)

This study characterizes carbon and nitrogen abundances and isotopic compositions in ureilitic fragments of Almahata Sitta. Ureilites are carbon-rich (containing up to 7 wt% C) and were formed early in solar system history, thus the origin of carbon in ureilites has significance for the origin of solar system carbon. These samples were collected soon after they fell, so they are among the freshest ureilite samples available and were analyzed using stepped combustion mass spectrometry. They contained 1.2-2.3 wt% carbon; most showed the major carbon release at temperatures of 600-700 °C with peak values of ?13C from -7.3 to +0.4‰, similar to literature values for unbrecciated ("monomict") ureilites. They also contained a minor low temperature (?500 °C) component (?13C = ca -25‰). Bulk nitrogen contents (9.4-27 ppm) resemble those of unbrecciated ureilites, with major releases mostly occurring at 600-750 °C. A significant lower temperature release of nitrogen occurred in all samples. Main release ?15N values of -53 to -94‰ fall within the range reported for diamond separates and acid residues from ureilites, and identify an isotopically primordial nitrogen component. However, they differ from common polymict ureilites which are more nitrogen-rich and isotopically heavier. Thus, although the parent asteroid 2008TC3 was undoubtedly a polymict ureilite breccia, this cannot be deduced from an isotopic study of individual ureilite fragments. The combined main release ?13C and ?15N values do not overlap the fields for carbonaceous or enstatite chondrites, suggesting that carbon in ureilites was not derived from these sources.

Downes, H.; Abernethy, F. A. J.; Smith, C. L.; Ross, A. J.; Verchovsky, A. B.; Grady, M. M.; Jenniskens, P.; Shaddad, M. H.



Late Glacial Tropical Savannas in Sundaland Inferred From Stable Carbon Isotope Records of Cave Guano  

NASA Astrophysics Data System (ADS)

During the Last Glacial Period (LGP), reduced global sea level exposed the continental shelf south of Thailand to Sumatra, Java, and Borneo to form the contiguous continent of Sundaland. However, the type and extent of vegetation that existed on much of this exposed landmass during the LGP remains speculative. Extensive bird and bat guano deposits in caves throughout this region span beyond 40,000 yr BP, and contain a wealth of untapped stratigraphic palaeoenvironmental information. Stable carbon isotope ratios of insectivorous bird and bat guano contain a reliable record of the animal's diet and, through non-specific insect predation, reflect the relative abundance of major physiological pathways in plants. Various physiological pathways of carbon fixation in plants yield differing stable carbon isotope ratios. Stable carbon isotope values of C3 plants are lower than C4 vegetation due to different enzymatic discriminations of the heavy isotope through the carbon fixing pathways. In tropical locales, grasses nearly always follow the C4 photosynthetic pathway, whereas tropical rainforest uses C3 photosynthesis, providing a proxy for vegetation and therefore climate change in the past. Here we discuss four guano stable-isotope records, based on insect cuticle and n-alkane analysis, supplemented by pollen analysis. All sites suggest a C3 dominated ecosystem for the Holocene, consistent with the wet tropical forest vegetation present at all locations. Two sites from Palawan Island, Philippines, record stable carbon isotope values of guano that document a drastic change from C3 (forest) to C4 (savanna) dominated ecosystems during the Last Glacial Maximum (LGM). A third location, at Niah Great Cave, Malaysia, indicates C3-dominant vegetation throughout the record, but does display variation in stable carbon isotope values likely linked to humidity changes. A fourth location, Batu Caves in Peninsular Malaysia, also indicates open vegetation during the LGM. Vegetation models disagree as to the nature of vegetation during the LGM in Sundaland, but our results suggest major contraction of forest area with significant implications for carbon storage during the LGM and also for understanding the development of modern biogeographic and genetic patterns in the region. Additional cave guano sites will provide further constraints on the nature of environmental change in the region over the last glacial cycle.

Wurster, C. M.; Bird, M. I.; Bull, I.; Dungait, J.; Bryant, C. L.; Ertunç, T.; Hunt, C.; Lewis, H. A.; Paz, V.



Constraints on the Origin of Galactic Cosmic Rays from Direct Measurements of Isotopic and Elemental Abundances  

NASA Astrophysics Data System (ADS)

Recent measurements of galactic cosmic ray (GCR) isotopic and elemental abundances have resulted in constraints on models of the origin of GCRs. The measurement of ^{59}Ni by the Cosmic Ray Isotope Spectrometer (CRIS) on the NASA Advanced Composition Explorer (ACE) has shown that there must be >˜10^{5} years between nucleosynthesis and acceleration. Measurements of a range of isotope ratios, most importantly ^{22}Ne/^{20}Ne and ^{58}Fe/^{56}Fe, have shown that the composition is consistent with source material that is a mix of ˜80% ISM (with Solar System abundances) and 20% outflow from massive stars. Data from the Trans-Iron Galactic Element Recorder (TIGER) and the ACE-CRIS experiments both show that the ordering of refractory and volatile elements with atomic mass is greatly improved when compared to an ˜80%/20% mix rather than pure ISM, that they have similar slopes, and that refractory elements are preferentially accelerated by a factor of ˜4 over volatile elements. We discuss these observations and conclude that our constraints are consistent with a GCR origin in OB associations. This research was supported by NASA under Grants NNX08AI11G and NNX09AC17G, and by NSF under Grant 0807356

Rauch, Brian



Stable Carbon Isotope Fractionation by Methylotrophic Methanogenic Archaea  

PubMed Central

In natural environments methane is usually produced by aceticlastic and hydrogenotrophic methanogenic archaea. However, some methanogens can use C1 compounds such as methanol as the substrate. To determine the contributions of individual substrates to methane production, the stable-isotope values of the substrates and the released methane are often used. Additional information can be obtained by using selective inhibitors (e.g., methyl fluoride, a selective inhibitor of acetoclastic methanogenesis). We studied stable carbon isotope fractionation during the conversion of methanol to methane in Methanosarcina acetivorans, Methanosarcina barkeri, and Methanolobus zinderi and generally found large fractionation factors (?83‰ to ?72‰). We further tested whether methyl fluoride impairs methylotrophic methanogenesis. Our experiments showed that even though a slight inhibition occurred, the carbon isotope fractionation was not affected. Therefore, the production of isotopically light methane observed in the presence of methyl fluoride may be due to the strong fractionation by methylotrophic methanogens and not only by hydrogenotrophic methanogens as previously assumed. PMID:22904062

Penger, Jörn; Conrad, Ralf



Characterizing uranium oxide reference particles for isotopic abundances and uranium mass by single particle isotope dilution mass spectrometry.  


Uranium and plutonium particulate test materials are becoming increasingly important as the reliability of measurement results has to be demonstrated to regulatory bodies responsible for maintaining effective nuclear safeguards. In order to address this issue, the Institute for Reference Materials and Measurements (IRMM) in collaboration with the Institute for Transuranium Elements (ITU) has initiated a study to investigate the feasibility of preparing and characterizing a uranium particle reference material for nuclear safeguards, which is finally certified for isotopic abundances and for the uranium mass per particle. Such control particles are specifically required to evaluate responses of instruments based on mass spectrometric detection (e.g. SIMS, TIMS, LA-ICPMS) and to help ensuring the reliability and comparability of measurement results worldwide. In this paper, a methodology is described which allows quantifying the uranium mass in single micron particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS). This methodology is characterized by substantial improvements recently achieved at IRMM in terms of sensitivity and measurement accuracy in the field of uranium particle analysis by TIMS. The use of monodisperse uranium oxide particles prepared using an aerosol generation technique developed at ITU, which is capable of producing particles of well-characterized size and isotopic composition was exploited. The evidence of a straightforward correlation between the particle volume and the mass of uranium was demonstrated in this study. Experimental results have shown that the uranium mass per particle can be measured via the ID-TIMS method to a relative expanded uncertainty of about 10% (coverage factor k=2). The availability of reliable and validated methods for the characterization of uranium particles is considered to be essential for the establishment of SI-traceable measurement results. It is therefore expected that the method developed in this study is valuable for the certification of particulate materials in which the isotopic composition and the content of uranium must be accurately known. PMID:23021805

Kraiem, M; Richter, S; Erdmann, N; Kühn, H; Hedberg, M; Aregbe, Y



Stable carbon isotope fractionation during aerobic biodegradation of chlorinated ethenes  

Microsoft Academic Search

Stable isotope analysis is recognized as a powerful tool for monitoring, assessing, and validating in-situ bioremediation processes. In this study, kinetic carbon isotope fractionation factors () associated with the aerobic biodegradation of vinyl chloride (VC), cis-1,2-dichloroethylene (cDCE), and trichloroethylene (TCE) were examined. Of the three solvents, the largest fractionation effects were observed for biodegradation of VC. Both metabolic and cometabolic

Kung-Hui Chu; Shaily Mahendra; Donald L. Song; Mark E. Conrad; Lisa Alvarez-Cohen



Stable carbon isotope biogeochemistry of lakes along a trophic gradient  

NASA Astrophysics Data System (ADS)

The stable carbon (C) isotope variability of dissolved inorganic and organic C (DIC and DOC), particulate organic carbon (POC), glucose and polar-lipid derived fatty acids (PLFAs) was studied in a survey of 22 North American oligotrophic to eutrophic lakes. The ?13C of different PLFAs were used as proxy for phytoplankton producers and bacterial consumers. Lake pCO2 was primarily determined by autochthonous production (phytoplankton biomass), especially in eutrophic lakes, and governed the ?13C of DIC. All organic-carbon pools showed overall higher isotopic variability in eutrophic lakes (n = 11) compared to oligo-mesotrophic lakes (n = 11) because of the high variability in ?13C at the base of the food web (both autochthonous and allochthonous carbon). Phytoplankton ?13C was negatively related to lake pCO2 over all lakes and positively related to phytoplankton biomass in eutrophic lakes, which was also reflected in a large range in photosynthetic isotope fractionation (ϵCO2-phyto, 8-25‰). The carbon isotope ratio of allochthonous carbon in oligo-mesotrophic lakes was rather constant, while it varied in eutrophic lakes because of maize cultivation in the watershed.

de Kluijver, A.; Schoon, P. L.; Downing, J. A.; Schouten, S.; Middelburg, J. J.



The influence of authigenic clay formation on the mineralogy and stable isotopic record of lacustrine carbonates  

NASA Astrophysics Data System (ADS)

The mineralogical, compositional and stable isotopic variability of lacustrine carbonates are frequently used as proxies for ancient paleoenvironmental change in continental settings, under the assumption that precipitated carbonates reflect conditions and chemistry of ancient lake waters. In some saline and alkaline lake systems, however, authigenic clay minerals, forming at or near the sediment water interface, are a major sedimentary component. Often these clays are rich in Mg, influencing the geochemical budget of lake waters, and are therefore expected to influence the properties of contemporaneous authigenic carbonate precipitates (which may also contain Mg). This paper documents evidence for a systematic feedback between clay mineral and carbonate authigenesis through multiple precessionally driven, m-scale sedimentary cycles in lacustrine oil-shale deposits of the Eocene Green River Formation from the Uinta Basin (NE Utah). In the studied section, authigenic, Mg-rich, trioctahedral smectite content varies cyclically between 9 and 39 wt.%. The highest concentrations occur in oil-shales and calcareous mudstones deposited during high lake level intervals that favored sedimentary condensation, lengthening the time available for clay diagenesis and reducing dilution by other siliciclastic phases. An inverse relation between dolomite percentage of carbonate and trioctahedral smectite abundance suggests the Mg uptake during clay authigenesis provides a first order control on carbonate mineralogy that better explains carbonate mineralogical trends than the possible alternative controls of (1) variable Mg/Ca ratios in lake water and (2) degree of microbial activity in sediments. We also observe that cyclical change in carbonate mineralogy, believed to be induced by clay authigenesis, also causes isotopic covariation between ?13CPDB and ?18OPDB of bulk sediments because of differences in the equilibrium fractionation factors of dolomite and calcite (˜2‰ and ˜2.6%, respectively). This provides an alternative mechanism for the common pattern of isotopic covariation, which is typically attributed to the effect of simultaneous changes in water balance and biological activity on the carbon and oxygen isotopic composition of lake waters. These findings may help improve paleoenvironmental reconstructions based on lacustrine carbonate records by adding to the factors known to influence the mineralogical, compositional and stable isotopic signals recorded by lacustrine carbonates.

Bristow, Thomas F.; Kennedy, Martin J.; Morrison, Keith D.; Mrofka, David D.



Abundance and Isotopic Composition of Gases in the Martian Atmosphere from the Curiosity Rover  

NASA Astrophysics Data System (ADS)

Volume mixing and isotope ratios secured with repeated atmospheric measurements taken with the Sample Analysis at Mars instrument suite on the Curiosity rover are: carbon dioxide (CO2), 0.960(±0.007); argon-40 (40Ar), 0.0193(±0.0001); nitrogen (N2), 0.0189(±0.0003); oxygen, 1.45(±0.09) × 10-3; carbon monoxide, < 1.0 × 10-3; and 40Ar/36Ar, 1.9(±0.3) × 103. The 40Ar/N2 ratio is 1.7 times greater and the 40Ar/36Ar ratio 1.6 times lower than values reported by the Viking Lander mass spectrometer in 1976, whereas other values are generally consistent with Viking and remote sensing observations. The 40Ar/36Ar ratio is consistent with martian meteoritic values, which provides additional strong support for a martian origin of these rocks. The isotopic signature ?13C from CO2 of ~45 per mil is independently measured with two instruments. This heavy isotope enrichment in carbon supports the hypothesis of substantial atmospheric loss.

Mahaffy, Paul R.; Webster, Christopher R.; Atreya, Sushil K.; Franz, Heather; Wong, Michael; Conrad, Pamela G.; Harpold, Dan; Jones, John J.; Leshin, Laurie A.; Manning, Heidi; Owen, Tobias; Pepin, Robert O.; Squyres, Steven; Trainer, Melissa; Kemppinen, Osku; Bridges, Nathan; Johnson, Jeffrey R.; Minitti, Michelle; Cremers, David; Bell, James F.; Edgar, Lauren; Farmer, Jack; Godber, Austin; Wadhwa, Meenakshi; Wellington, Danika; McEwan, Ian; Newman, Claire; Richardson, Mark; Charpentier, Antoine; Peret, Laurent; King, Penelope; Blank, Jennifer; Weigle, Gerald; Schmidt, Mariek; Li, Shuai; Milliken, Ralph; Robertson, Kevin; Sun, Vivian; Baker, Michael; Edwards, Christopher; Ehlmann, Bethany; Farley, Kenneth; Griffes, Jennifer; Grotzinger, John; Miller, Hayden; Newcombe, Megan; Pilorget, Cedric; Rice, Melissa; Siebach, Kirsten; Stack, Katie; Stolper, Edward; Brunet, Claude; Hipkin, Victoria; Léveillé, Richard; Marchand, Geneviève; Sánchez, Pablo Sobrón; Favot, Laurent; Cody, George; Steele, Andrew; Flückiger, Lorenzo; Lees, David; Nefian, Ara; Martin, Mildred; Gailhanou, Marc; Westall, Frances; Israël, Guy; Agard, Christophe; Baroukh, Julien; Donny, Christophe; Gaboriaud, Alain; Guillemot, Philippe; Lafaille, Vivian; Lorigny, Eric; Paillet, Alexis; Pérez, René; Saccoccio, Muriel; Yana, Charles; Armiens-Aparicio, Carlos; Rodríguez, Javier Caride; Blázquez, Isaías Carrasco; Gómez, Felipe Gómez; Gómez-Elvira, Javier; Hettrich, Sebastian; Malvitte, Alain Lepinette; Jiménez, Mercedes Marín; Martínez-Frías, Jesús; Martín-Soler, Javier; Martín-Torres, F. Javier; Jurado, Antonio Molina; Mora-Sotomayor, Luis; Caro, Guillermo Muñoz; López, Sara Navarro; Peinado-González, Verónica; Pla-García, Jorge; Manfredi, José Antonio Rodriguez; Romeral-Planelló, Julio José; Fuentes, Sara Alejandra Sans; Martinez, Eduardo Sebastian; Redondo, Josefina Torres; Urqui-O'Callaghan, Roser; Mier, María-Paz Zorzano; Chipera, Steve; Lacour, Jean-Luc; Mauchien, Patrick; Sirven, Jean-Baptiste; Fairén, Alberto; Hayes, Alexander; Joseph, Jonathan; Sullivan, Robert; Thomas, Peter; Dupont, Audrey; Lundberg, Angela; Melikechi, Noureddine; Mezzacappa, Alissa; DeMarines, Julia; Grinspoon, David; Reitz, Günther; Prats, Benito; Atlaskin, Evgeny; Genzer, Maria; Harri, Ari-Matti; Haukka, Harri; Kahanpää, Henrik; Kauhanen, Janne; Kemppinen, Osku; Paton, Mark; Polkko, Jouni; Schmidt, Walter; Siili, Tero; Fabre, Cécile; Wray, James; Wilhelm, Mary Beth; Poitrasson, Franck; Patel, Kiran; Gorevan, Stephen; Indyk, Stephen; Paulsen, Gale; Gupta, Sanjeev; Bish, David; Schieber, Juergen; Gondet, Brigitte; Langevin, Yves; Geffroy, Claude; Baratoux, David; Berger, Gilles; Cros, Alain; d'Uston, Claude; Forni, Olivier; Gasnault, Olivier; Lasue, Jérémie; Lee, Qiu-Mei; Maurice, Sylvestre; Meslin, Pierre-Yves; Pallier, Etienne; Parot, Yann; Pinet, Patrick; Schröder, Susanne; Toplis, Mike; Lewin, Éric; Brunner, Will; Heydari, Ezat; Achilles, Cherie; Oehler, Dorothy; Sutter, Brad; Cabane, Michel; Coscia, David; Israël, Guy; Szopa, Cyril; Dromart, Gilles; Robert, François; Sautter, Violaine; Le Mouélic, Stéphane; Mangold, Nicolas; Nachon, Marion; Buch, Arnaud; Stalport, Fabien; Coll, Patrice; François, Pascaline; Raulin, François; Teinturier, Samuel; Cameron, James; Clegg, Sam; Cousin, Agnès; DeLapp, Dorothea; Dingler, Robert; Jackson, Ryan Steele; Johnstone, Stephen; Lanza, Nina; Little, Cynthia; Nelson, Tony; Wiens, Roger C.; Williams, Richard B.; Jones, Andrea; Kirkland, Laurel; Treiman, Allan; Baker, Burt; Cantor, Bruce; Caplinger, Michael; Davis, Scott; Duston, Brian; Edgett, Kenneth; Fay, Donald; Hardgrove, Craig; Harker, David; Herrera, Paul; Jensen, Elsa; Kennedy, Megan R.; Krezoski, Gillian; Krysak, Daniel; Lipkaman, Leslie; Malin, Michael; McCartney, Elaina; McNair, Sean; Nixon, Brian; Posiolova, Liliya; Ravine, Michael; Salamon, Andrew; Saper, Lee; Stoiber, Kevin; Supulver, Kimberley; Van Beek, Jason; Van Beek, Tessa; Zimdar, Robert; French, Katherine Louise; Iagnemma, Karl; Miller, Kristen; Summons, Roger; Goesmann, Fred; Goetz, Walter; Hviid, Stubbe; Johnson, Micah; Lefavor, Matthew; Lyness, Eric; Breves, Elly; Dyar, M. Darby; Fassett, Caleb; Blake, David F.; Bristow, Thomas; DesMarais, David; Edwards, Laurence; Haberle, Robert; Hoehler, Tori; Hollingsworth, Jeff; Kahre, Melinda; Keely, Leslie; McKay, Christopher; Wilhelm, Mary Beth; Bleacher, Lora; Brinckerhoff, William; Choi, David; Dworkin, Jason P.; Eigenbrode, Jennifer; Floyd, Melissa; Freissinet, Caroline; Garvin, James; Glavin, Daniel; Jones, Andrea; Martin, David K.




SciTech Connect

The International Organization for Standardization (ISO) has published a Guide to the expression of Uncertainty in Measurement (GUM). The IUPAC Commission on Isotopic Abundance and Atomic Weight (CIAAW) began attaching uncertainty limits to their recommended values about forty years ago. CIAAW's method for determining and assigning uncertainties has evolved over time. We trace this evolution to their present method and their effort to incorporate the basic ISO/GUM procedures into evaluations of these uncertainties. We discuss some dilemma the CIAAW faces in their present method and whether it is consistent with the application of the ISO/GUM rules. We discuss the attempt to incorporate variations in measured isotope ratios, due to natural fractionation, into the ISO/GUM system. We make some observations about the inconsistent treatment in the incorporation of natural variations into recommended data and uncertainties. A recommendation for expressing atomic weight values using a tabulated range of values for various chemical elements is discussed.




Carbon and hydrogen isotopic compositions of New Zealand geothermal gases  

NASA Astrophysics Data System (ADS)

Carbon and hydrogen isotopic compositions are reported for methane, hydrogen and carbon dioxide from four New Zealand geothermal areas: Ngawha, Wairakei, Broadlands and Tikitere. Carbon-13 contents are between -24.4 and -29.5%. (PDB) for methane, and between -3.2 and -9.1%. for carbon dioxide. Deuterium contents are between -142 and -197%. (SMOW) for methane and between -310 and -600%. for hydrogen. The different areas have different isotopic compositions with some general relationships to reservoir temperature. The isotopic exchange of hydrogen with water indicates acceptable reservoir temperatures of 180-260°C from most spring samples but often higher than measured temperatures in well samples. Indicated temperatures assuming 13C equilibria between CH 4 and CO 2 are 100-200°C higher than measured maxima. This difference may be due to partial isotopic equilibration or may reflect the origin of the methane. Present evidence cannot identify whether the methane is primordial, or from decomposing sediments or from reduction of magmatic CO 2. The isotopic equilibria between CH 4, CO 2, H 2 and H 2O are reviewed and a new semi-empirical temperature scale proposed for deuterium exchange between methane and water.

Lyon, G. L.; Hulston, J. R.



On the volatile inventory of Titan from isotopic abundances in nitrogen and methane.  


We analyze recently published nitrogen and hydrogen isotopic data to constrain the initial volatile abundances on Saturn's giant moon Titan. The nitrogen data are interpreted in terms of a model of non-thermal escape processes that lead to enhancement in the heavier isotope. We show that these data do not, in fact, strongly constrain the abundance of nitrogen present in Titan's early atmosphere, and that a wide range of initial atmospheric masses (all larger than the present value) can yield the measured enhancement. The enrichment in deuterated methane is now much better determined than it was when Pinto et al. (1986. Nature 319, 388-390) first proposed a photochemical mechanism to preferentially retain the deuterium. We develop a simple linear theory to provide a more reliable estimate of the relative dissociation rates of normal and deuterated methane. We utilize the improved data and models to compute initial methane reservoirs consistent with the observed enhancement. The result of this analysis agrees with an independent estimate for the initial methane abundance based solely on the present-day rate of photolysis and an assumption of steady state. This consistency in reservoir size is necessary but not sufficient to infer that methane photolysis has proceeded steadily over the age of the solar system to produce large quantities of less volatile organics. Our analysis indicates an epoch of early atmospheric escape of nitrogen, followed by a later addition of methane by outgassing from the interior. The results also suggest that Titan's volatile inventory came in part or largely from a circum-Saturnian disk of material more reducing than the surrounding solar nebula. Many of the ambiguities inherent in the present analysis can be resolved through Cassini-Huygens data and a program of laboratory studies on isotopic and molecular exchange processes. The value of, and interest in, the Cassini-Huygens data can be greatly enhanced if such a program were undertaken prior to the prime phase of the mission. PMID:11543194

Lunine, J I; Yung, Y L; Lorenz, R D



Microbial carbonate abundance compared with fluctuations in metazoan diversity over geological time  

E-print Network

Microbial carbonate abundance compared with fluctuations in metazoan diversity over geological time diversity and reefal microbial carbonate abundance. These datasets reveal long-term changes over the past in microbial carbo- nates. In addition to overall long-term diversity in- crease, metazoans episodically

Riding, Robert


BOREAS TE-5 Tree Ring and Carbon Isotope Ratio Data  

NASA Technical Reports Server (NTRS)

The BOREAS TE-5 team collected several data sets to investigate the vegetation-atmosphere CO2 and H2O exchange processes. These data include tree ring widths and cellulose carbon isotope data from coniferous trees collected at the BOREAS NSA and SSA in 1993 and 1994 by the BOREAS TE-5 team. Ring width data are provided for both Picea mariana and Pinus banksiana. The carbon isotope data are provided only for Pinus banksiana. The data are provided in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

Hall, Forrest G. (Editor); Curd, Shelaine (Editor); Ehleriinger, Jim; Brooks, J. Renee; Flanagan, Larry



Carbon isotope systematics of a mantle "hotspot": a comparison of Loihi Seamount and MORB glasses  

USGS Publications Warehouse

The carbon isotope geochemistry of glasses from Loihi Seamount has been compared with that of MORB glasses. Stepped heating shows two carbon components in both sample suites: (1) isotopically light carbon (avg. ??13C = -26.3???) released 600??C, regarded as indigenous. The high-temperature component in MORB samples varied from 52 to 169 ppm C, average ??13C = -6.6???, consistent with previous studies (overall MORD average ??13C = -6.4 ?? 0.9???), and new results for Indian Ocean glasses are similar to Atlantic and Pacific Ocean samples. Carbon release profiles produced by stepped heating may be typical of locality, but there are no significant differences in ??13C values between MORB samples from different areas. Lower yields (17-110 ppm C) correlated with depth in the Loihi samples suggest that they are partially degassed. This degassing has not affected ??13C values significantly (avg. -5.8???). Loihi tholeiites have higher ??13C (avg. -5.6???) than the alkali basalts (avg. -7.1???). Carbon abundances correlate well with He concentration data. Comparison of the ??13C values with trace element and He, Sr, Nd, and Pb isotope data from the literature suggests that the Loihi samples with highest ??13C have high 3He/4He and possibly the least depleted 143Nd/144Nd and 87Sr/86Sr. The carbon isotope data are consistent with previous models for Loihi involving several mantle sources, lithospheric contamination, and mixing. The slightly higher ??13C of Loihi tholeiites suggests that the undegassed "plume" component manifested by high 3He/4He values might have ??13C about 1??? higher than the MORB average. ?? 1986.

Exley, R.A.; Mattey, D.P.; Clague, D.A.; Pillinger, C.T.



Combining stable isotope isotope geochemistry and carbonic anhydrase activity to trace vital effect in carbonate precipitation experiments  

NASA Astrophysics Data System (ADS)

Carbonates precipitated by skeleton-forming eukaryotic organisms are often characterized by non-equilibrium isotopic signatures. This specificity is referred to as the "vital effect" and can be used as an isotopic evidence to trace life. Combining stable isotope geochemistry and enzymology (using the enzyme carbonic anhydrase) we aim to demonstrate that prokaryotes are also able to precipitate carbonate with a non-equilibrium d18OCaCO3. Indeed, if in an biomineralization experiment carbonates are precipitated with a vital effect, the addition of carbonic anhydrase should drive the system to isotope equilibrium, And provide a comparison point to estimate the vital effect range. This protocol allowed us to identify a -20‰ vital effect for the d18O of carbonates precipitated by Sporosarcina pasteurii, a bacterial model of carbonatogen metabolisms. This approach is thus a powerfull tool for the understanding of microbe carbonatogen activity and will probably bring new insights into the understanding of bacterial activity in subsurface and during diagenesis.

Thaler, C.; Ader, M.; Menez, B.; Guyot, F. J.



Behaviour of Structural Carbonate Stable Carbon and Oxygen Isotope Compositions in Bioapatite During Burning of Bone  

NASA Astrophysics Data System (ADS)

Bioapatite, the principal inorganic phase comprising bone, commonly contains a small fraction of carbonate, which has been substituted into the phosphate structure during bone formation. The isotopic compositions of both the phosphate oxygen and the structural carbonate oxygen are now commonly used in palaeoclimatological and bioarchaeological investigations. The potential for post-mortem alteration of these isotopic compositions, therefore, is of interest, with the behaviour of structural carbonate being of most concern. In bioarchaeological studies, alteration of bone isotopic compositions has the potential to occur not only during low-temperature processes associated with burial but also during food preparation involving heating (burning, boiling). Here, we examine the stable isotopic behaviour of structural carbonate oxygen and carbon, and coexisting phosphate oxygen during the burning of bone. Freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned and incrementally heated from 25 to 900° C, in 25° intervals. The samples were then ground to a standardized grain-size (45<63? m), and changes in bioapatite crystallinity (CI) were determined using powder X-ray diffraction (pXRD), and Fourier transform infra-red spectroscopy (FTIR). Combined differential thermal and thermogravimetric analyses (DTA/TG) were used to evaluate weight loss and associated reactions during heating. Stable carbon isotope compositions of the bioapatite remain relatively constant (+/-1‰ ) during heating to 650° C. A 4‰ increase in stable carbon isotopic composition then occurs between 650-750° C, accompanied by an increase in CI, followed by a 10‰ decline at temperatures above 800° C, as carbonate carbon is lost. Carbonate and phosphate oxygen isotopic compositions are correlated over the entire heating range, with carbonate being enriched relative to phosphate by about 8-10‰ below 500° C, 5-6‰ between 500-700° C, and 8-10‰ above 700° C. CI and oxygen isotopic compositions of carbonate and phosphate are not well correlated. Only modest CI changes are recorded from 25-675° C, compared with much larger changes in oxygen isotopic composition, especially above 300° C. On average, original isotopic compositions are largely preserved for both phosphate (+/-1‰ ) and carbonate (+/-2‰ ) oxygen at <300° C. At higher temperatures, however, both phosphate and carbonate oxygen in the bioapatite are systematically depleted of oxygen-18 relative to original values.

Munro, L. E.; Longstaffe, F. J.; White, C. D.




EPA Science Inventory

Carbon isotope ratios ( 13C) of tree rings are commonly used for paleoclimatic reconstruction and for inferring canopy water-use efficiency (WUE). However, the responsiveness of carbon isotope discrimination ( ) to site disturbance and resource availability has only rarely been ...


Rhenium-osmium isotope and highly-siderophile-element abundance systematics of angrite meteorites  

NASA Astrophysics Data System (ADS)

Coupled 187Os/188Os compositions and highly-siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for eight angrite achondrite meteorites that include quenched- and slowly-cooled textural types. These data are combined with new major- and trace-element concentrations determined for bulk-rock powder fractions and constituent mineral phases, to assess angrite petrogenesis. Angrite meteorites span a wide-range of HSE abundances from <0.005 ppb Os (e.g., Northwest Africa [NWA] 1296; Angra dos Reis) to >100 ppb Os (NWA 4931). Chondritic to supra-chondritic 187Os/188Os (0.1201-0.2127) measured for Angra dos Reis and quenched-angrites correspond to inter- and intra-sample heterogeneities in Re/Os and HSE abundances. Quenched-angrites have chondritic-relative rare-earth-element (REE) abundances at 10-15×CI-chondrite, and their Os-isotope and HSE abundance variations represent mixtures of pristine uncontaminated crustal materials that experienced addition (<0.8%) of exogenous chondritic materials during or after crystallization. Slowly-cooled angrites (NWA 4590 and NWA 4801) have fractionated REE-patterns, chondritic to sub-chondritic 187Os/188Os (0.1056-0.1195), as well as low-Re/Os (0.03-0.13), Pd/Os (0.071-0.946), and relatively low-Pt/Os (0.792-2.640). Sub-chondritic 187Os/188Os compositions in NWA 4590 and NWA 4801 are unusual amongst planetary basalts, and their HSE and REE characteristics may be linked to melting of mantle sources that witnessed prior basaltic melt depletion. Angrite HSE-Yb systematics suggest that the HSE behaved moderately-incompatibly during angrite magma crystallization, implying the presence of metal in the crystallizing assemblage. The new HSE abundance and 187Os/188Os compositions indicate that the silicate mantle of the angrite parent body(ies) (APB) had HSE abundances in chondritic-relative proportions but at variable abundances at the time of angrite crystallization. The HSE systematics of angrites are consistent with protracted post-core formation accretion of materials with chondritic-relative abundances of HSE to the APB, and these accreted materials were rapidly, yet inefficiently, mixed into angrite magma source regions early in Solar System history.

Riches, Amy J. V.; Day, James M. D.; Walker, Richard J.; Simonetti, Antonio; Liu, Yang; Neal, Clive R.; Taylor, Lawrence A.



Stable isotopes of carbon and nitrogen in the study of avian and mammalian trophic ecology  

Microsoft Academic Search

Differential fractionation of stable isotopes of carbon during photosynthesis causes C 4 plants and C3 plants to have distinct carbon-isotope signatures. In addition, marine C 3 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' tissues makes this ratio useful in

Jeffrey F. Kelly



Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment  

NASA Astrophysics Data System (ADS)

Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment, employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e., equivalent to ~8 ng of amino sugar carbon. Compound-specific stable carbon isotopic analysis of amino sugars obtained from marine sediment extracts indicated that glucosamine and galactosamine were mainly derived from organic detritus, whereas muramic acid showed isotopic imprints from indigenous bacterial activities. The ?13C analysis of amino sugars provides a valuable addition to the biomarker-based characterization of microbial metabolism in the deep marine biosphere, which so far has been lipid oriented and biased towards the detection of archaeal signals.

Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.



Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment  

NASA Astrophysics Data System (ADS)

Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e. equivalent to ~ 8 ng of amino sugar carbon. Our results obtained from ?13C analysis of amino sugars in selected marine sediment samples showed that muramic acid had isotopic imprints from indigenous bacterial activities, whereas glucosamine and galactosamine were mainly derived from organic detritus. The analysis of stable carbon isotopic compositions of amino sugars opens a promising window for the investigation of microbial metabolisms in marine sediments and the deep marine biosphere.

Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.



Molecular and carbon isotopic composition of leaf wax in vegetation and aerosols in a northern prairie ecosystem.  


We measured the molecular and carbon isotopic composition of major leaf wax compound classes in northern mixed mesic prairie species (Agropyron smithii, Stipa viridula, Bouteloua gracilis, Tragopogon dubius) and in selected crops (Triticum aestivum, Brassica napus, Hordeum vulgare, Medicago sativa) of southern Alberta and also in aerosols collected 4 m above the prairie canopy. Our aims were to better constrain the wax biosynthetic carbon isotopic fractionation relative to the plant's carbon isotopic discrimination and to quantitatively assess the correspondence between wax composition in vegetation and in boundary layer aerosols. Wax molecular composition of the C(3)prairie species and bulked vegetation was characterized by high abundance of C(28) n-alkanol and C(31) n-alkane compounds whereas the C(4) species B. gracilis had several co-dominant n-alkanol and n-alkane compounds. Wax molecular composition of crop species differed significantly from that of prairie vegetation and was often dominated by a single compound. Results indicate that leaf wax isotopic composition is quantitatively related to the plant's carbon isotopic discrimination. Although species variations were evident, n-alcohol, n-acid and n-alkane wax compounds were on average depleted in (13)C by approximately 6.0+/-1 per thousand relative to total plant carbon. The magnitude of the depletion in wax delta(13)C was unaffected by environmental factors which altered photosynthetic carbon isotopic discrimination. No consistent difference in the magnitude of wax biosynthetic fractionation was observed between C(3) and C(4) species, indicating that photosynthetic pathway has little influence on the isotopic fractionation of wax during biosynthesis. The isotopic composition of ablated waxes in aerosols collected above the canopy was similar to that of the grassland vegetation but the molecular composition differed significantly and indicated that the source "footprint" of the ablated leaf wax particles we sampled in boundary layer air masses was of a regional or larger spatial scale. PMID:12647105

Conte, Maureen H; Weber, John C; Carlson, Peter J; Flanagan, Lawrence B



Reconstructing Past Climates using Carbon Isotopes from Fulvic Acids in Cave Sediments  

E-print Network

Ã?Ã? Ã? Ã?Ã?Ã? Ã? Ã?Ã? Reconstructing Past Climates using Carbon Isotopes from Fulvic Acids in Cave Climates using Carbon Isotopes from Fulvic Acids in Cave Sediments, Chemical Geology (2013), doi: 10.1016/j MANUSCRIPT 1 Reconstructing Past Climates using Carbon Isotopes from Fulvic Acids in Cave Sediments *Jason S

Asmerom, Yemane


Can Mg isotopes be used to trace cyanobacteria-mediated magnesium carbonate precipitation in alkaline lakes?  

NASA Astrophysics Data System (ADS)

The fractionation of Mg isotopes was determined during the cyanobacterial mediated precipitation of hydrous magnesium carbonate precipitation in both natural environments and in the laboratory. Natural samples were obtained from Lake Salda (SE Turkey), one of the few modern environments on the Earth's surface where hydrous Mg-carbonates are the dominant precipitating minerals. This precipitation was associated with cyanobacterial stromatolites which were abundant in this aquatic ecosystem. Mg isotope analyses were performed on samples of incoming streams, groundwaters, lake waters, stromatolites, and hydromagnesite-rich sediments. Laboratory Mg carbonate precipitation experiments were conducted in the presence of purified Synechococcus sp cyanobacteria that were isolated from the lake water and stromatolites. The hydrous magnesium carbonates nesquehonite (MgCO3·3H2O) and dypingite (Mg5(CO3)4(OH)25(H2O)) were precipitated in these batch reactor experiments from aqueous solutions containing either synthetic NaHCO3/MgCl2 mixtures or natural Lake Salda water, in the presence and absence of live photosynthesizing Synechococcus sp. Bulk precipitation rates were not to affected by the presence of bacteria when air was bubbled through the system. In the stirred non-bubbled reactors, conditions similar to natural settings, bacterial photosynthesis provoked nesquehonite precipitation, whilst no precipitation occurred in bacteria-free systems in the absence of air bubbling, despite the fluids achieving a similar or higher degree of supersaturation. The extent of Mg isotope fractionation (?26Mgsolid-solution) between the mineral and solution in the abiotic experiments was found to be identical, within uncertainty, to that measured in cyanobacteria-bearing experiments, and ranges from -1.4 to -0.7 ‰. This similarity refutes the use of Mg isotopes to validate microbial mediated precipitation of hydrous Mg carbonates.

Shirokova, L. S.; Mavromatis, V.; Bundeleva, I.; Pokrovsky, O. S.; Bénézeth, P.; Pearce, C.; Gérard, E.; Balor, S.; Oelkers, E. H.



Biomarkers, carbon isotopic composition and source rock potentials of Awgu coals, middle Benue trough, Nigeria  

NASA Astrophysics Data System (ADS)

Coal and carbonaceous shale samples were collected from two boreholes (BH 94 and BH 120) in Awgu formation of Middle Benue Trough, Nigeria. Source rock potentials of the samples were studied using biomarkers and carbon isotopic composition. Biomarkers in the aliphatic fractions in the samples were studied using Gas Chromatography-Mass Spectrometry (GC-MS). The Carbon isotope analysis of individual n-alkanes in the aliphatic fraction was performed using Gas Chromatography-Combustion-Isotope Ratio Mass Spectrometer (GC-IRMS). The abundance of hopanes, homohopanes (C31-C35), and C29 steranes in the samples indicate terrestrial plant, phytoplankton and cyanobacteria contributions to the organic matter that formed the coal. High (Pr/Ph) ratio (3.04-11.07) and isotopic distribution of individual alkanes showed that the samples consisted of mixed terrestrial/marine organic matter deposited under oxic condition in lacustrine-fluvial/deltaic depositional environment. The maturity parameters derived from biomarker distributions showed that the samples are in the main phase of oil window.

Adedosu, Taofik A.; Sonibare, Oluwadayo O.; Tuo, Jincai; Ekundayo, Olusegun



Carbonate `clumped isotope' thermometry in planktonic foraminifera and coccoliths  

NASA Astrophysics Data System (ADS)

Constraints on past ocean temperatures are critical for documenting climate change and resolving its causes. The carbonate 'clumped isotope' thermometer is a novel tool for the reconstruction of ocean temperatures. 'Clumped isotope' thermometry in general relies on the principle that ordering, or 'clumping', of heavy isotopes into bonds with or near each other in molecules, minerals or organic moieties is a temperature dependent phenomenon [1]. Carbonate clumped isotope thermometry in particular examines the proportion of 13C and 18O that are bound to each other within the carbonate mineral lattice [2,3]. Unlike other temperature proxies, the proportion of 13C-18O bonds in carbonates is independent of the isotopic composition of water in which the carbonate grew. In practice, this thermometer is based on analyses of 13C18O16O in CO2 produced by acid digestion of carbonates, which are reported using the variable, '?47' -- a measure of the enrichment, in per mil, of 13C18O16O above the amount expected for a random distribution of isotopes. We have made the first ?47 measurements of core-top planktonic foraminifera and coccoliths. Our initial results show that multiple species with different ecologies exhibit the same temperature dependence as inorganic calcite. We will present calibration data for mixed coccolith assemblages and multiple species of planktonic foraminifera, including: Globigerina bulloides, Neogloboquadrina dutertrei, Globigerinoides sacculifer, G. ruber, G. inflata, Globorotalia menardii, G. truncatulinoides, G. hirsuta, Globigerinella aequilateralis, and Pulleniatina obliquiloculata. In addition, data for core-top samples from a depth transect on the Ontong- Java Plateau in the Pacific Ocean will be used to assess the impact of dissolution on the ?47 of CO2 evolved from marine carbonates. [1] Wang, Z., Schauble, E., and Eiler, J., 2004, Equilibrium thermodynamics of multiply substituted isotopologues of molecular gases, Geochimica et Cosmochimica Acta, 68, 4779-4797l [2] Schauble, E., Ghosh, P., and Eiler, J. 2006, Preferential formation of 13C-18O bonds in carbonate minerals, estimated using first-principles lattice dynamics, Geochimica et Cosmochimica Acta, 70, 2510-2529. [3] Ghosh, P., Adkins, J., Affek, H, Balta, B., Guo, W., Schauble, E, Schrag, D. and Eiler, J., 2006, 13C-18O bonds in carbonate minerals: A new kind of paleothermometer, Geochimica et Cosmochimica Acta, 70, 1439-1456.

Tripati, A.; Thiagarajan, N.; Eiler, J.



Equilibrium and nonequilibrium oxygen isotope effects in synthetic carbonates  

NASA Astrophysics Data System (ADS)

A suite of divalent metal (Ca, Cd, Ba) carbonates was synthesized over the temperature range 10-40°C by the classical method of slowly bubbling N 2 through a bicarbonate solution. It was discovered that carbonates could be precipitated reproducibly in or out of isotopic equilibrium with the environmental solution by varying the concentrations of bicarbonate and cation. Precipitation rate had little or no influence on the isotopic composition of the product. Relatively high initial concentrations of up to 25 mM in both bicarbonate and cation were prepared by adding solid metal chlorides to solutions of NaHC0 3. On the basis of results of equilibrium experiments and a new determination of the acid fractionation factor, a new expression is proposed for the oxygen isotope fractionation between calcite and water at low temperatures: 10001n?(Calcite-H 2O) = 18.03(10 3T -1) - 32.42 where ? is the fractionation factor, and T is in kelvins. Combining new data for low-temperature precipitations and the high-temperature equilibrium fractionations published by O'Neil et al. (1969) results in a revised expression for the oxygen isotope fractionation between octavite (CdCO 3) and water from 0° to 500°C: 10001n?(CdC0P 3sbnd H 2O) = 2.7 6(10 6T -2) - 3.96 The ability to produce nonequilibrium carbonates allowed assessment to be made, for the first time, of the temperature dependence of nonequilibrium stable isotope fractionations in mineral systems. The temperature coefficients of a(carbonate-water) for nonequilibrium divalent metal carbonates are greater than those for equilibrium carbonates, a finding that may bear on the interpretation of analyses of biogenic carbonates forming out of isotopic equilibrium in nature. New determinations of acid fractionation factors (10001n?) at 25°C for calcite (10.44 - 0.10), aragonite (11.01 ± 0.01), and witherite (10.57 - 0.16) are mildly to strongly different from those published by Sharma and Clayton (1965) and point to a control on this fractionation by some physical property of the mineral. Reproducible values for octavite (CdC0 3) varied from 11.18 to 13.60 depending on the conditions of preparation of the carbonate. These new values need to be considered in determinations of absolute 1880 1660 ratios of international reference standards and in relating analyses of carbonates to those of waters, silicates, and oxides.

Kim, Sang-Tae; O'Neil, James R.



Carbon isotope discrimination by plants follows latitudinal and altitudinal trends  

Microsoft Academic Search

In an earlier paper we provided evidence that carbon isotope discrimination during photosynthesis of terrestrial C3 plants decreases with altitude, and it was found that this was associated with greater carboxylation efficiency at high altitudes. Changing partial pressures of CO2 and O2 and changing temperature are possible explanations, since influences of moisture and light were reduced to a minimum by

Ch. Körner; G. D. Farquhar; S. C. Wong




E-print Network

OXYGEN, CARBON, AND HYDROGEN ISOTOPE STUDIES OF CONTACT METAMORPHISM Thesis by Yuch-Ning Shieh. Hugh P. Taylor, Jr. for encouragement and guidance throughout the course of this research. I om wife, Tiee-leou, for her encouragement and assistance during this study. This research was supported

Winfree, Erik


Stable carbon isotope fractionation by sulfate-reducing bacteria  

NASA Technical Reports Server (NTRS)

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

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



Partitioning peat respiration with stable carbon isotopes  

NASA Astrophysics Data System (ADS)

Equimolar production of CO2 and CH4 is assumed with methanogenesis. However, in both field and incubation studies of peat respiration, CO2 is continually reported to be in higher concentrations than CH4. It was assumed that this is due to loss of methane with ebullition and additional CO2 production by HMW organic matter fermentation. To determine the proportions of CO2 formed from both organic matter fermentation and methanogenesis and to determine the percent loss of CH4 from ebullition, isotope mass balance equations were developed. The 13C-CO2 measured in pore water represents a mixture between the 13C-CO2 from organic matter decomposition and methanogenesis. By collecting and analyzing pore water samples for ?13C and concentrations of both CO2 and CH4, the proportion of CO2 formed from organic matter fermentation and methanogenesis was calculated. It was found that, at 0, 154, and 261 cm depths, the percent CO2 from methanogenesis was 56%, 88%, and 91%, and the percent CH4 loss due to ebullition was 69%, 79%, and 85%, respectively. These findings indicate that with increasing depth both the percent CO2 formed from methanogenesis and the percent CH4 lost increased. Incubation experiments consisting of peat from five depth intervals (30-40, 70-80, 130-140, 170-180, and 270-280cm) were used to determine the accuracy of the isotope mass balance equations based on in situ concentrations and isotopic values. Measurements were made biweekly for concentrations and ?13C of CO2 and CH4. The percents of CO2 formed from methanogenesis based on the isotope mass balance equations were found to be to be 53%, 44%, 12%, 51%, and 54% corresponding to the respective depth ranges. The ratios of CH4/CO2 measured were 51%, 39%, 4%, 41%, and 54%, respectively. The average standard deviation between these sample sets was found to be ± 3.5%. This indicates that the isotope mass balance equations are an appropriate model for determining in situ CO2 partitioning in these systems.

Chanton, J.; Corbett, J.; Burdige, D. J.; Glaser, P. H.; Cooper, W. T.; Tfaily, M. M.



Combined carbonate carbon isotopic and cellular ultrastructural studies of individual benthic foraminifera: Method description  

NASA Astrophysics Data System (ADS)

Carbon isotopes of foraminiferal tests provide a widely used proxy for past oceanographic environmental conditions. This proxy can be calibrated using live specimens, which are reliably identified with observations of cell ultrastructure. Observations of ultrastructures can also be used for studies of biological characteristics such as diet and presence of symbionts. Combining biological and isotopic studies on individual foraminifera could provide novel information, but standard isotopic methods destroy ultrastructures by desiccating specimens and observations of ultrastructure require removal of carbonate tests, preventing isotope measurements. The approach described here preserves cellular ultrastructure during isotopic analyses by keeping the foraminifera in an aqueous buffer (Phosphate Buffered Saline (PBS)). The technique was developed and standardized with 36 aliquots of NBS-19 standard of similar weight to foraminiferal tests (5 to 123 ?g). Standard errors ranged from ± 0.06 to ± 0.85‰ and were caused by CO2 contaminants dissolved in the PBS. The technique was used to measure ?13C values of 96 foraminifera, 10 of which do not precipitate carbonate tests. Calcareous foraminiferal tests had corrected carbon isotope ratios of -8.5 to +3.2‰. This new technique allows comparisons of isotopic compositions of tests made by foraminifera known to be alive at the time of collection with their biological characteristics such as prey composition and presence or absence of putative symbionts. The approach may be applied to additional biomineralizing organisms such as planktonic foraminifera, pteropods, corals, and coccolithophores to elucidate certain biological controls on their paleoceanographic proxy signatures.

Martin, Jonathan B.; Bernhard, Joan M.; Curtis, Jason; Rathburn, Anthony E.



Reaction cross sections of carbon isotopes incident on a proton  

E-print Network

We systematically study total reaction cross sections of carbon isotopes with N=6-16 on a proton target for wide range of incident energies, putting an emphasis on the difference from the case of a carbon target. The analysis includes the reaction cross sections of ^{19,20,22}C at 40 AMeV, the data of which have recently been measured at RIKEN. The Glauber theory is used to calculate the reaction cross sections. To describe the intrinsic structure of the carbon isotopes, we use a Slater determinant generated from a phenomenological mean-field potential, and construct the density distributions. To go beyond the simple mean-field model, we adopt two types of dynamical models: One is a core+n model for odd-neutron nuclei, and the other is a core+n+n model for 16C and 22C. We propose empirical formulas which are useful in predicting unknown cross sections.

B. Abu-Ibrahim; W. Horiuchi; A. Kohama; Y. Suzuki



Method for determination of stable carbon isotope ratio of methylnitrophenols in atmospheric PM  

NASA Astrophysics Data System (ADS)

A technique for the measurement of the stable isotope ratio of methylnitrophenols in atmospheric particulate matter (PM) is presented. It has been found in numerous laboratory studies that these compounds are photooxidation products of toluene in PM. Atmospheric samples from rural and suburban areas were collected for evaluation of the procedure. PM was collected on quartz fibre filters using dichotomous high volume air samplers for PM 2.5. Methylnitrophenols were extracted from the filters using acetonitrile. The sample was then purified using a combination of high-performance liquid chromatography (HPLC) and solid phase extraction (SPE). The final solution was then divided into two aliquots. To one aliquot, a derivatising agent, Bis(trimethylsilyl)trifluoroacetamide (BSTFA), was added to the solution for Gas Chromatography/Mass Spectroscopy (GC/MS) analysis. The second half of the sample was stored at low temperature. When GC/MS analysis showed high enough concentrations the remaining sample was derivatized with BSTFA and analysed for stable isotope ratio using a Gas Chromatography/Isotope Ratio Mass Spectrometry (GC-IRMS). In all atmospheric PM samples analysed, 2-methyl-4-nitrophenol was found to be the most abundant methylnitrophenol. Nevertheless, due to low pollution levels occurring in the rural area, no samples had concentrations high enough to perform stable carbon isotope composition measurements of the methylnitrophenols. Samples collected in the suburban area could be analysed for carbon stable isotope ratio using GC-IRMS. The procedure described in this paper provides a very sensitive and selective method for the analysis of methylnitrophenols in atmospheric PM at concentrations as low as 1 pg m-3. For accurate (within ±0.5‰) stable isotope ratio analysis significantly higher concentrations in the range of 100 pg m-3 or more are required.

Moukhtar, S.; Saccon, M.; Kornilova, A.; Irei, S.; Huang, L.; Rudolph, J.



Amino-group-specific natural abundance nitrogen isotope ratio analysis in amino acids.  


Amino acid (AA) nitrogen (N) stable isotope ratio analysis has found a wide variety of important applications including indication of the trophic level of an organism, tracing N transfer within food webs, and monitoring of AA resynthesis during heterotrophic microbial reworking of organic matter. Despite its utility, the current methodology is difficult to employ consistently for natural abundance level precision. Here, we report a new and robust method for high-precision N-compound-specific isotope analysis (N-PCIA) for single-N-containing AAs and N-position-specific isotope analysis (N-PSIA) for poly-N AAs. First the amino-N in AAs was liberated and oxidized to NO2(-) by hypochlorite at high pH. The NO2(-) produced was then quantified colorimetrically with excess hypochlorite quenched using arsenite. Subsequently, buffered azide was used to reduce NO2(-) to N2O for isotope ratio analysis using a purge-and-trap isotope ratio mass spectrometer. In the case of glycine delta15N, the average precision was SD = 0.3 per thousand. Reaction yields and labeling experiments show that this oxidation reaction is highly specific, targeting the alpha-amino group (peptide-N) of most poly-N AAs. This permits specific determination of the delta15N of peptide-N in arginine, tryptophan, and histidine. In the case of lysine, however, the side-chain amino group was found to be partially labile to hypochlorite oxidation. Using isotope fractionation factors estimated from single-N analogues of lysine, the intramolecular delta15N of lysine was calculated by mass balance, and this generally agreed with results for the same sample material analyzed by a previously published enzymatic method. Our method has the advantages of being relatively rapid, robust, and applicable to all poly-N AAs. We have also found it to work well for determining total delta15N of amino-N in complex sample matrices that have not been susceptible to previous approaches. PMID:18231965

Zhang, Lin; Altabet, Mark A



Magnesium isotope fractionation in bacterial mediated carbonate precipitation experiments  

NASA Astrophysics Data System (ADS)

Magnesium is an essential component of life, with pivotal roles in the generation of cellular energy as well as in plant chlorophyll [1]. The bio-geochemical cycling of Mg is associated with mass dependant fractionation (MDF) of the three stable Mg isotopes [1]. The largest MDF of Mg isotopes has been recorded in carbonates, with foraminiferal tests having ?26Mg compositions up to 5 ‰ lighter than modern seawater [2]. Magnesium isotopes may also be fractionated during bacterially mediated carbonate precipitation and such carbonates are known to have formed in both modern and ancient Earth surface environments [3, 4], with cyanobacteria having a dominant role in carbonate formation during the Archean. In this study, we aim to better constrain the extent to which Mg isotope fractionation occurs during cellular processes, and to identify when, and how, this signal is transferred to carbonates. To this end we have undertaken biologically-mediated carbonate precipitation experiments that were performed in artificial seawater, but with the molar Mg/Ca ratio set to 0.6 and with the solution spiked with 0.4% yeast extract. The bacterial strain used was marine isolate Halomonas sp. (gram-negative). Experiments were run in the dark at 21 degree C for two to three months and produced carbonate spheres of various sizes up to 300 ?m in diameter, but with the majority have diameters of ~100 ?m. Control experiments run in sterile controls (`empty` medium without bacteria) yielded no precipitates, indicating a bacterial control on the precipitation. The carbonate spheres are produced are amenable to SEM, EMP and Mg isotopic analysis by MC-ICP-MS. Our new data will shed light on tracing bacterial signals in carbonates from the geological record. [1] Young & Galy (2004). Rev. Min. Geochem. 55, p197-230. [2] Pogge von Strandmann (2008). Geochem. Geophys. Geosys. 9 DOI:10.1029/2008GC002209. [3] Castanier, et al. (1999). Sed. Geol. 126, 9-23. [4] Cacchio, et al. (2003). Geomicrobiol. J. 20, 85-98.

Parkinson, I. J.; Pearce, C. R.; Polacskek, T.; Cockell, C.; Hammond, S. J.



Silicon isotopic abundance toward evolved stars and its application for presolar grains  

NASA Astrophysics Data System (ADS)

Aims: Galactic chemical evolution (GCE) is important for understanding the composition of the present-day interstellar medium (ISM) and of our solar system. In this paper, we aim to track the GCE by using the 29Si/30Si ratios in evolved stars and tentatively relate this to presolar grain composition. Methods: We used the APEX telescope to detect thermal SiO isotopologue emission toward four oxygen-rich M-type stars. Together with the data retrieved from the Herschel science archive and from the literature, we were able to obtain the 29Si/30Si ratios for a total of 15 evolved stars inferred from their optically thin 29SiO and 30SiO emission. These stars cover a range of masses and ages, and because they do not significantly alter 29Si/30Si during their lifetimes, they provide excellent probes of the ISM metallicity (or 29Si/30Si ratio) as a function of time. Results: The 29Si/30Si ratios inferred from the thermal SiO emission tend to be lower toward low-mass oxygen-rich stars (e.g., down to about unity for W Hya), and close to an interstellar or solar value of 1.5 for the higher-mass carbon star IRC+10216 and two red supergiants. There is a tentative correlation between the 29Si/30Si ratios and the mass-loss rates of evolved stars, where we take the mass-loss rate as a proxy for the initial stellar mass or current stellar age. This is consistent with the different abundance ratios found in presolar grains. Before the formation of the Sun, the presolar grains indicate that the bulk of presolar grains already had 29Si/30Si ratios of about 1.5, which is also the ratio we found for the objects younger than the Sun, such as VY CMa and IRC+10216. However, we found that older objects (up to possibly 10 Gyr old) in our sample trace a previous, lower 29Si/30Si value of about 1. Material with this isotopic ratio is present in two subclasses of presolar grains, providing independent evidence of the lower ratio. Therefore, the 29Si/30Si ratio derived from the SiO emission of evolved stars is a useful diagnostic tool for the study of the GCE and presolar grains. This publication is based on data acquired with the Atacama Pathfinder Experiment (APEX). APEX is a collaboration between the Max-Planck-Institut für Radioastronomie, the European Southern Observatory, and the Onsala Space Observatory. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.Tables 2, 3, and Fig. 4 are available in electronic form at

Peng, T.-C.; Humphreys, E. M. L.; Testi, L.; Baudry, A.; Wittkowski, M.; Rawlings, M. G.; de Gregorio-Monsalvo, I.; Vlemmings, W.; Nyman, L.-A.; Gray, M. D.; de Breuck, C.



Triple oxygen isotopes in biogenic and sedimentary carbonates  

NASA Astrophysics Data System (ADS)

The 17O anomaly (?17O) of natural waters has been shown to be sensitive to evaporation in a way analogous to deuterium excess, with evaporated bodies of water (e.g., leaf waters, lake waters, animal body waters) tending to have lower ?17O than primary meteoric waters. In animal body water, ?17O relates to the intake of evaporated waters, evaporative effluxes of water, and the ?17O value of atmospheric O2, which itself carries signatures of global carbon cycling and photochemical reactions in the stratosphere. Carbonates have the potential to record the triple oxygen isotope compositions of parent waters, allowing reconstruction of past water compositions, but such investigations have awaited development of methods for high-precision measurement of ?17O of carbonate. We describe optimized methods based on a sequential acid digestion/reduction/fluorination approach that yield ?17O data with the high precision (?0.010‰, 1?) needed to resolve subtle environmental signals. We report the first high-precision ?17O dataset for terrestrial carbonates, focusing on vertebrate biogenic carbonates and soil carbonates, but also including marine invertebrates and high-temperature carbonates. We determine apparent three-isotope fractionation factors between the O2 analyte derived from carbonate and the parent waters of the carbonate. These in combination with appropriate temperature estimates (from clumped isotope thermometry, or known or estimated body temperatures) are used to calculate the ?18O and ?17O of parent waters. The clearest pattern to emerge is the strong 17O-depletion in avian, dinosaurian, and mammalian body water (from analyses of eggshell and tooth enamel) relative to meteoric waters, following expected influences of evaporated water (e.g., leaf water) and atmospheric O2 on vertebrate body water. Parent waters of the soil carbonates studied here have ?17O values that are similar to or slightly lower than global precipitation. Our results suggest that ?17O will have useful application to paleoenvironmental studies of continental environments where the effects of evaporation are important, and where vertebrate body water may record an isotopic signal of evaporated water sources and atmospheric oxygen.

Passey, Benjamin H.; Hu, Huanting; Ji, Haoyuan; Montanari, Shaena; Li, Shuning; Henkes, Gregory A.; Levin, Naomi E.



HCNMBC - A pulse sequence for H-(C)-N Multiple Bond Correlations at natural isotopic abundance  

NASA Astrophysics Data System (ADS)

We propose a pulse sequence, HCNMBC for multiple-bond H-(C)-N correlation experiments via one-bond 1J(C,H) and one- or multiple bond nJ(N,C) coupling constants (typically n = 1-3) at the natural isotopic abundance. A new adiabatic refocussing sequence is introduced to provide accurate and robust refocussing of both chemical shift and J-evolution over wide ranges of C-13 and N-15 frequencies. It is demonstrated that the proposed pulse sequence provides high quality spectra even for sub-milligram samples. We show that when a 1.7 mm cryoprobe is available as little as 10 ?g of glycine in D2O is sufficient to obtain the HCNMBC spectrum in ca. 12 h. The preliminary results indicate that the pulse sequence has a great potential in the structure determination of nitrogen heterocycles especially in cases where synthesis produces regioisomers.

Cheatham, Steve; Gierth, Peter; Bermel, Wolfgang; Kup?e, ?riks



Clumped isotope thermometry of modern and early Cretaceous molluscan carbonate from high-latitude seas (Invited)  

NASA Astrophysics Data System (ADS)

The carbonate clumped isotope thermometer is based on the temperature sensitivity of the relative abundance of carbonate ion groups containing 13C-18O bonds. One application of clumped isotope thermometry is to determine the temperature of ancient seawater from the skeletal material of calcium carbonate-secreting marine organisms. The relationship between ?47, a parameter describing isotopic clumping, and the temperature of carbonate biomineralization has been well-defined for fish otoliths, corals, foraminifera, and coccolithophore tests, but few data have been published for brachiopods and bivalve mollusks. A comprehensive evaluation of the ?47-temperature relationship for mollusks is required for paleotemperature interpretations from the marine fossil record. Here we present a more comprehensive calibration for modern mollusks, including bivalves, cephalopods, and gastropods. Further, we focus on a subset of cold water, high-latitude species collected in the northern Barents Sea. The observed ?47-temperature relationship is similar to the theoretical relationship presented by Guo et al. (2009) but deviates at low temperatures from the original Ghosh et al. (2007) calibration curve. This divergence could be related to methodological differences or unaccounted differences in the biomineralization of mollusks versus that of other carbonate-secreting organisms at low temperature. One advantage of clumped isotope thermometry over traditional oxygen isotope thermometry is that it does not require assumptions about the isotopic composition of the water in which the carbonate formed. This may be particularly useful in Mesozoic paleoceanography where the oxygen isotope value of seawater is uncertain. Using clumped isotope thermometry applied to early Cretaceous (Valangian) belemnite carbonate from the Yatria River, sub-polar Urals, Siberia, we find shell growth temperatures of 20-26°C at a paleolatitude of ~60-65°N. Our data imply average seawater ?18O values of 0.5-1.5‰ when used in conjunction with published temperature-?18Ocarb-?18Osw calibrations. This ?18O range is higher than is traditionally assumed for high-latitude Cretaceous seawater. We argue, however, that such values are plausible and may be related to different basin- or global-scale hydrologies or belemnite body fluid that was in isotopic disequilibrium with the seawater. The paired ?47 and ?18O from the fossils rule out isotopic exchange with high temperature fluids or later diagenesis in 18O-depleted meteoric waters. We observe no textual or chemical evidence of recrystallization, and we hypothesize that these shells faithfully record early Cretaceous high-latitude seawater temperatures. The inferred temperature range of 20-26°C is substantially higher than 60-70°N modern mean annual sea surface temperature (˜-1.0 to 10.0°C) and mean summer surface temperatures (˜-0.5 to 14.5°C), implying a substantially shallower latitudinal temperature gradient during the early Cretaceous.

Henkes, G. A.; Price, G. D.; Ambrose, W. G.; Carroll, M. L.; Passey, B. H.



Stable Carbon Isotope Ratios of Lipid Biomarkers of Sulfate-Reducing Bacteria  

PubMed Central

We examined the potential use of natural-abundance stable carbon isotope ratios of lipids for determining substrate usage by sulfate-reducing bacteria (SRB). Four SRB were grown under autotrophic, mixotrophic, or heterotrophic growth conditions, and the ?13C values of their individual fatty acids (FA) were determined. The FA were usually 13C depleted in relation to biomass, with ??13C(FA ? biomass) of ?4 to ?17‰; the greatest depletion occurred during heterotrophic growth. The exception was Desulfotomaculum acetoxidans, for which substrate limitation resulted in biomass and FA becoming isotopically heavier than the acetate substrate. The ?13C values of FA in Desulfotomaculum acetoxidans varied with the position of the double bond in the monounsaturated C16 and C18 FA, with FA becoming progressively more 13C depleted as the double bond approached the methyl end. Mixotrophic growth of Desulfovibrio desulfuricans resulted in little depletion of the i17:1 biomarker relative to biomass or acetate, whereas growth with lactate resulted in a higher proportion of i17:1 with a greater depletion in 13C. The relative abundances of 10Me16:0 in Desulfobacter hydrogenophilus and Desulfobacterium autotrophicum were not affected by growth conditions, yet the ??13C(FA ? substrate) values of 10Me16:0 were considerably greater during autotrophic growth. These experiments indicate that FA ?13C values can be useful for interpreting carbon utilization by SRB in natural environments. PMID:14766550

Londry, K. L.; Jahnke, L. L.; Des Marais, D. J.



Carbon and nitrogen isotope studies in an arctic ecosystem. Final report  

SciTech Connect

The dynamics of carbon fixation and storage in tundra soils has received considerable attention with respect to global carbon cycling. Recent findings by investigators using chamber measurements of fixation/respiration rates in arctic tundra have led to the conclusion that tundra is no longer storing carbon but is instead a source of carbon dioxide to the atmosphere. The author has sought to test these conclusions and to determine methods by which the long-term accumulation or loss of carbon in tundra can be determined. Little is known, however, of the processes that control storage and the current rates of carbon fixation and peat formation in arctic Alaska. This project focused on several aspects of carbon dynamics and the roles of decomposition and herbivory at the DOE research site at Imnavait Creek, Alaska. Through the use of natural abundance stable and radioisotope techniques, several conclusions emerged. Peat carbon continues to accumulate in wetter areas of foothill valleys and on the coastal plain of arctic Alaska. Radiocarbon profiles of bomb {sup 14}C were used to date layers of vegetation and litter to obtain decomposition rates and to extrapolate these values to intersection with the permafrost horizon where further decomposition is assumed to cease. Carbon storage in riparian moss at Imnavait Creek was estimated at 3 g C/m{sup 2}-yr. Profiles of {sup 137}Cs closely matched those of {sup 14}C and may provide a more expeditious means of assessing recent carbon accumulation rates in tundra. Carbon and nitrogen stable isotope ratios in tundra vegetation vary markedly over hydrologic gradients in apparent response to changing growth rates and sources of nitrogenous nutrients. Within a taxon, {delta}{sup 15}N values varied by several {per_thousand} over a tens of meters distance.

Schell, D.M.



Stable carbon isotope fractionation during aerobic biodegradation of chlorinated ethenes  

SciTech Connect

Stable isotope analysis is recognized as a powerful tool for monitoring, assessing, and validating in-situ bioremediation processes. In this study, kinetic carbon isotope fractionation factors () associated with the aerobic biodegradation of vinyl chloride (VC), cis-1,2-dichloroethylene (cDCE), and trichloroethylene (TCE) were examined. Of the three solvents, the largest fractionation effects were observed for biodegradation of VC. Both metabolic and cometabolic VC degradation were studied using Mycobacterium aurum L1 (grown on VC), Methylosinus trichosporium OB3b (grown on methane), Mycobacterium vaccae JOB 5 (grown on propane), and two VC enrichment cultures seeded from contaminated soils of Alameda Point and Travis Air Force Base, CA. M. aurum L1 caused the greatest fractionation (= -5.7) while for the cometabolic cultures, values ranged from -3.2 to -4.8. VC fractionation patterns for the enrichment cultures were within the range of those observed for the metabolic and cometabolic cultures (= -4.5 to -5.5). The fractionation for cometabolic degradation of TCE by Me. trichosporium OB3b was low (= -1.1), while no quantifiable carbon isotopic fractionation was observed during the cometabolic degradation of cDCE. For all three of the tested chlorinated ethenes, isotopic fractionation measured during aerobic degradation was significantly smaller than that reported for anaerobic reductive dechlorination. This study suggests that analysis of compound-specific isotopic fractionation could assist in determining whether aerobic or anaerobic degradation of VC and cDCE predominates in field applications of in-situ bioremediation. In contrast, isotopic fractionation effects associated with metabolic and cometabolic reactions are not sufficiently dissimilar to distinguish these processes in the field.

Chu, Kung-Hui; Mahendra, Shaily; Song, Donald L.; Conrad, Mark E.; Alvarez-Cohen, Lisa



Carbon isotope fractionation of methyl bromide during agricultural soil fumigations  

USGS Publications Warehouse

The isotopic composition of methyl bromide (CH3Br) has been suggested to be a potentially useful tracer for constraining the global CH3Br budget. In order to determine the carbon isotopic composition of CH3Br emitted from the most significant anthropogenic application (pre-plant fumigation) we directly measured the ??13C of CH3Br released during commercial fumigation. We also measured the isotopic fractionation associated with degradation in agricultural soil under typical field fumigation conditions. The isotopic composition of CH3Br collected in soil several hours after injection of the fumigant was -44.5??? and this value increased to -20.7??? over the following three days. The mean kinetic isotope effect (KIE) associated with degradation of CH3Br in agricultural soil (12???) was smaller than the reported value for methylotrophic bacterial strain IMB-1, isolated from previously fumigated agricultural soil, but was similar to methylotrophic bacterial strain CC495, isolated from a pristine forest litter zone. Using this fractionation associated with the degradation of CH3Br in agricultural soil and the mean ??13C of the industrially manufactured CH3Br (-54.4???), we calculate that the agricultural soil fumigation source has a carbon isotope signature that ranges from -52.8??? to -42.0???. Roughly 65% of industrially manufactured CH3Br is used for field fumigations. The remaining 35% is used for structural and post-harvest fumigations with a minor amount used during industrial chemical manufacturing. Assuming that the structural and post-harvest fumigation sources of CH3Br are emitted without substantial fractionation, we calculate that the ??13C of anthropogenically emitted CH3Br ranges from -53.2??? to -47.5???.

Bill, M.; Miller, L.G.; Goldstein, A.H.



Rapid Analysis of Carbon Isotopic Compositions of Sedimentary Algal Sterols  

NASA Astrophysics Data System (ADS)

We are developing a new procedure to produce highly resolved records of the carbon isotopic composition of algal sterols. The procedure includes: (i) recovery of geolipids from dry sediments by extraction in organic solvents; (ii) chromatographic fractionation of the extract on silica gel; and (iii) removal of n-alcohols with Silicalite. Simplifications allow processing of 24 samples per day. Miniaturization has reduced the amount of sediment required to 300 mg. The carbon isotopic composition of the extract is measured using a moving-wire combustion system initially developed to accept the effluent of a liquid chromatograph (Brand and Dobberstein, Isotopes Environ. Health Stud. 32, 275-283, 1996). Analyses are made at 25-sec intervals with an average standard error of 0.15‰ for samples ranging from 200 to 900 ngC. Comparison of the resulting records of the isotopic composition of algal lipids to parallel analyses of inorganic carbon allows calculation of the isotopic fractionation associated with primary production and thus provides information about conditions in the photic zone. It serves also to identify samples in which more detailed, compound-specific analysis would be worthwhile. A highly-resolved record of 13C in polar lipids from a sediment core collected on the Oman Margin (ODP 723B) indicates fractionations between 20 and 25‰ . Events occurring on timescales of a few hundred years have caused variations as large as 4‰ . Increases in the fractionation could be caused by slowed rates of growth, an increase of the surface area/volume ratio of the community or an increase in the concentration of CO2. Such changes could be related to varying strengths of upwelling, supplies of key nutrients, or to changes in the dominant population in the producer community. Characterization of the lipids present at selected depths, as well as the comparison of our profile with existing paleoceanographic records from the Oman Margin, should allow refinement of these possibilities.

Ménot-Combes, G.; Sessions, A. L.; Hayes, J. M.; Altabet, M. A.; Higginson, M. J.



Molecular carbon isotopic evidence for the origin of geothermal hydrocarbons  

USGS Publications Warehouse

Previous interest in light hydrocarbons from geothermal systems has focused principally on the origin of the methane1 and the estimation of subsurface temperatures from the carbon isotopic content of coexisting methane and carbon dioxide1-3. Higher molecular weight hydrocarbons were first reported in gases from Yellowstone National Park4, and have since been found to occur commonly in geothermal emanations in the western United States5. Isotopic measurements of individual geothermal hydrocarbons are now reported which help to explain the origin of these hydrocarbons. The thermal decomposition of sedimentary or groundwater organic matter is a principal source of hydrocarbons in four geothermal areas in western North America. ?? 1981 Nature Publishing Group.

Des Marais, D.J.; Donchin, J.H.; Nehring, N.L.; Truesdell, A.H.



A stable carbon isotope and biological marker study of Polish bituminous coals and carbonaceous shales  

USGS Publications Warehouse

Biological marker and carbon isotopic compositions of coals and carbonaceous shales from the Upper Carboniferous strata of the Upper Silesian (USCB), Lower Silesian (LSCB), and Lublin (LCB) coal basins were determined to assess depositional conditions and sources of the organic matter. n-Alkane, sterane, and isoprenoid distribution, and carbon isotope ratios are consistent with an origin from higher plants. In some cases, pristane/phytane (Pr/Ph) ratios of carbonaceous shales (roof and floor shales) are < 1.0, while the associated coals have high ratios (??? 1.0). This suggests that reducing conditions prevailed during deposition of the shales, but a period of oxidizing conditions accompanied deposition of the coals. Steranes present in coal extracts are dominated by the 14??(H)17??(H)20R C29 stereoisomers, typical, but not conclusive, of higher plant origin. Carbonaceous shales exhibit a wider range of sterane composition, suggesting local, significant input of algal organic matter. Significant amounts of benzohopanes and gammacerane are present in some coals. Although benzohopanes are present at least in small amounts in samples from many different environments, they have been reported to occur most commonly in marine environments. The present study seems to provide the first example where benzohopanes have been reported in significant amounts in terrestrial organic matter. Gammacerane is abundant in rocks or sediments deposited in carbonate or highly saline marine environments. The finding of high gammacerane concentrations in the coals expands the depositional settings in which it has been observed and questions its utility as an independent indicator of hypersaline carbonate environments. Stable carbon isotope composition of coals, and type III kerogen in carbonaceous shales as well as correlation of stable carbon isotope composition of saturated and aromatic hydrocarbons in carbonaceous shales from both the USCB and the LSCB indicate terrigenous origin. Bitumens are always co-genetic with associated coals and kerogens. Isotopic data reveal that Sofer's genetic classification of oils is not applicable to organic matter in coals. ?? 2003 Elsevier B.V. All rights reserved.

Kotarba, M.J.; Clayton, J.L.



Carbon isotopic enrichment in Titan's tholins? Implications for Titan's aerosols  

NASA Astrophysics Data System (ADS)

Since the discovery of the main composition of Titan's atmosphere, many laboratory experiments have been carried out to reproduce its chemical evolution, particularly the formation of organic haze particles found throughout this atmosphere. Some of these simulations have produced solid products - referred to as Titan's tholins - that are assumed to have properties similar to those of Titan's aerosols. In the present work, we focus on the possible isotopic fractionation of carbon during the processes involved in the formation of Titan's tholins. Initial 12C/ 13C isotopic ratios measured on tholins made in the laboratory using cold plasma discharges are presented. Measurements of isotopic enhancement in 13C ( ?13C), both on tholins and on the initial gas mixture (N 2:CH 4 (98:2)) used to produce them do not show any clear deficit or enrichment in 13C relative to 12C in the lab-made tholins compared to the initial gas mixture. Preliminary data recovered from the Aerosol Collector Pyrolyzer (ACP) experiment of the Huygens probe suggests that Titan's aerosols may also be exempt of carbon isotopic enrichment. This observation creates possibilities for deeper analysis of ACP experiment data.

Nguyen, M.-J.; Raulin, F.; Coll, P.; Derenne, S.; Szopa, C.; Cernogora, G.; Israël, G.; Bernard, J.-M.



Variable carbon isotope fractionation expressed by aerobic CH4-oxidizing bacteria  

E-print Network

Variable carbon isotope fractionation expressed by aerobic CH4-oxidizing bacteria Alexis S Engineering, Texas A&M University, College Station, TX 77843-3136, USA d Center for Isotope Geochemistry 2005; accepted in revised form 5 December 2005 Abstract Carbon isotope fractionation factors reported

Alvarez-Cohen, Lisa


From isotope labeled CH3CN to N2 inside single-walled carbon nanotubes  

E-print Network

From isotope labeled CH3CN to N2 inside single-walled carbon nanotubes Christian Kramberger to this peculiar place? We have used N15 and C13 isotope labeled acetonitrile during the synthesis of single-walled carbon nanotubes to investigate this process. The isotope shifts of phonons and vibrons are observed

Maruyama, Shigeo


Carbon isotope chemostratigraphy of the Middle Riphean type section (Avzyan Formation, Southern Urals, Russia)  

E-print Network

Carbon isotope chemostratigraphy of the Middle Riphean type section (Avzyan Formation, Southern preserve all or part of the mid- Mesoproterozoic isotopic shift. This shift represents a significant, the character of the carbon isotopic curve is most similar to that of the Dismal Lakes Group, arctic Canada

Perfect, Ed


Kinetic isotope effects during carbonate mineral formation Z. Sade*, R. Yam, A. Shemesh and I. Halevy  

E-print Network

Kinetic isotope effects during carbonate mineral formation Z. Sade*, R. Yam, A. Shemesh and I. Halevy Weizmann Institute of Science, Rehovot 76100, Israel * The oxygen isotopic ambient water to determine the temperature at which the carbonates formed and the oxygen isotope

Simon, Emmanuel


Isotope-induced elastic scattering of optical phonons in individual suspended single-walled carbon nanotubes  

E-print Network

Isotope-induced elastic scattering of optical phonons in individual suspended single-walled carbon 10, 2011) Isotope-induced scattering of optical phonons in individual single-walled carbon nanotubes (SWNTs) was investigated by resonance Raman scattering measurements of more than 600 sus- pended, isotope

Maruyama, Shigeo



SciTech Connect

This report describes method development and preliminary evaluation for analyzing castor samples for signatures of purifying ricin. Ricin purification from the source castor seeds is essentially a problem of protein purification using common biochemical methods. Indications of protein purification will likely manifest themselves as removal of the non-protein fractions of the seed. Two major, non-protein, types of biochemical constituents in the seed are the castor oil and various carbohydrates. The oil comprises roughly half the seed weight while the carbohydrate component comprises roughly half of the remaining “mash” left after oil and hull removal. Different castor oil and carbohydrate components can serve as indicators of specific toxin processing steps. Ricinoleic acid is a relatively unique fatty acid in nature and is the most abundant component of castor oil. The loss of ricinoleic acid indicates a step to remove oil from the seeds. The relative amounts of carbohydrates and carbohydrate-like compounds, including arabinose, xylose, myo-inositol fucose, rhamnose, glucosamine and mannose detected in the sample can also indicate specific processing steps. For instance, the differential loss of arabinose relative to mannose and N-acetyl glucosamine indicates enrichment for the protein fraction of the seed using protein precipitation. The methods developed in this project center on fatty acid and carbohydrate extraction from castor samples followed by derivatization to permit analysis by gas chromatography-mass spectrometry (GC-MS). Method descriptions herein include: the source and preparation of castor materials used for method evaluation, the equipment and description of procedure required for chemical derivatization, and the instrument parameters used in the analysis. Two types of derivatization methods describe analysis of carbohydrates and one procedure for analysis of fatty acids. Two types of GC-MS analysis is included in the method development, one employing a quadrupole MS system for compound identification and an isotope ratio MS for measuring the stable isotope ratios of deuterium and hydrogen (D/H) in fatty acids. Finally, the method for analyzing the compound abundance data is included. This study indicates that removal of ricinoleic acid is a conserved consequence of each processing step we tested. Furthermore, the stable isotope D/H ratio of ricinoleic acid distinguished between two of the three castor seed sources. Concentrations of arabinose, xylose, mannose, glucosamine and myo-inositol differentiated between crude or acetone extracted samples and samples produced by protein precipitation. Taken together these data illustrate the ability to distinguish between processes used to purify a ricin sample as well as potentially the source seeds.

Wunschel, David S.; Kreuzer-Martin, Helen W.; Antolick, Kathryn C.; Colburn, Heather A.; Moran, James J.; Melville, Angela M.



Can the carbon isotopic composition of methane be reconstructed from multi-site firn air measurements?  

NASA Astrophysics Data System (ADS)

Methane is a strong greenhouse gas and large uncertainties exist concerning the future evolution of its atmospheric abundance. Analyzing methane atmospheric mixing and stable isotope ratios in air trapped in polar ice sheets helps in reconstructing the evolution of its sources and sinks in the past. This is important to improve predictions of atmospheric CH4 mixing ratios in the future under the influence of a changing climate. We present an attempt to reconcile methane carbon isotope (?13C(CH4)) records from 11 boreholes in firn from both Greenland and Antarctica to reconstruct a consistent ?13C(CH4) history over the last 50 years. In the firn, the atmospheric signal is altered mainly by diffusion and gravitation. These processes are taken into account by firn air transport models. We show that (?13C(CH4) reconstructions from individual sites are not always mutually consistent among the different sites. Therefore we apply for the first time a multisite isotope inversion to reconstruct an atmospheric isotope history that is constrained by all individual sites, generating a multisite ?13C(CH4) scenario. The comparison of this scenario with ice core data, atmospheric air archive results and direct atmospheric monitoring data shows that inconsistencies exist between the different types of profiles which may be explained by inter-laboratory calibration differences, by analytical errors or by the lack of constraints on the diffusive fractionation estimates.

Sapart, Célia Julia; Martinerie, Patricia; Chappellaz, Jérôme; van de Wal, Roderik; Witrant, Emmanuel; Sperlich, Peter; van der Veen, Carina; Bernard, Sophie; Sturges, Bill; Blunier, Thomas; Schwander, Jakob; Etheridge, David; Röckmann, Thomas



Method for determination of stable carbon isotope ratio of methylnitrophenols in atmospheric particulate matter  

NASA Astrophysics Data System (ADS)

A technique for the measurement of the stable isotope ratio of methylnitrophenols in atmospheric particulate matter is presented. Atmospheric samples from rural and suburban areas were collected for evaluation of the procedure. Particulate matter was collected on quartz fibre filters using dichotomous high volume air samplers. Methylnitrophenols were extracted from the filters using acetonitrile. The sample was then purified using a combination of high-performance liquid chromatography and solid phase extraction. The final solution was then divided into two aliquots. To one aliquot, a derivatising agent, Bis(trimethylsilyl)trifluoroacetamide, was added for Gas Chromatography-Mass Spectrometry analysis. The second half of the sample was stored in a refrigerator. For samples with concentrations exceeding 1 ng ?l-1, the second half of the sample was used for measurement of stable carbon isotope ratios by Gas Chromatography-Isotope Ratio Mass Spectrometry. The procedure described in this paper provides a method for the analysis of methylnitrophenols in atmospheric particulate matter at concentrations as low as 0.3 pg m-3 and for stable isotope ratios with an accuracy of better than ±0.5‰ for concentrations exceeding 100 pg m-3. In all atmospheric particulate matter samples analysed, 2-methyl-4-nitrophenol was found to be the most abundant methylnitrophenol, with concentrations ranging from the low pg m-3 range in rural areas to more than 200 pg m-3 in some samples from a suburban location.

Moukhtar, S.; Saccon, M.; Kornilova, A.; Irei, S.; Huang, L.; Rudolph, J.



Isotope Effects on Heat Conduction of Carbon Nanotubes Shigeo Maruyama, Yuki Taniguchi and Yasushi Shibuta  

E-print Network

Isotope Effects on Heat Conduction of Carbon Nanotubes Shigeo Maruyama, Yuki Taniguchi and Yasushi that the inclusion of only 1 % of 13 C natural isotope dramatically reduces the thermal conductivity of diamond. However, isotope effects on heat conduction of SWNTs have not been elucidated. We estimated isotope

Maruyama, Shigeo


The use of stable carbon isotope analysis in rooting studies  

Microsoft Academic Search

Stable carbon isotope analysis was evaluated as a means of predicting the relative proportions of C3 and C4 root phytomass in species mixtures. The following mixtures of C3 and C4 species were used: 1) big bluestem (Andropogon gerardii)\\/cheatgrass (Bromus tectorum), 2) little bluestem (Schizachyrium scoparium)\\/cheatgrass, and 3) sorghum (Sorghum bicolor)\\/sunflower (Helianthus annuus). There was a significant correlation (P4 phytomass and

Tony J. Svejcar; Thomas W. Boutton



Stable carbon and nitrogen isotope biogeochemistry in the Delaware estuary  

Microsoft Academic Search

,Qbstract Seasonal variability in stable carbon (S'XZ) and nitrogen (b15N) isotope ratios was observed in suspended particulate matter of the Delaware estuary. Two major pools of organic matter were found in the estuary-phytoplankton growing in situ and a mixture of planktonic and terrestrial detritus. In general, the 6°C and 615N of suspended particulate matter reflected planktonic dom- inance. With the

L. A. Cifuentesl; J. H. SHARP; MARILYN L. FOGEL



Carbon isotopes in xenoliths from the Hualalai Volcano, Hawaii, and the generation of isotopic variability  

SciTech Connect

The isotopic composition of carbon has been determined in a suite of xenoliths from lava of the 1800-1801 Kaupulehu eruption of Hualalai Volcano, Hawaii. Several lithologies are represented in the suite, including websterite, dunite, wehrlite, pyroxenite, and gabbro. In addition, there are composite xenoliths in which contacts between lithologies are preserved. Most of the xenoliths represent deformed cumulates. The contact relations in the composite samples indicate that the lithologies originated from the same source region, which, based on pressures determined from fluid inclusions, is estimated to be at a depth of {approx}20 km, or near the crust-mantle boundary. The observations and isotopic results demonstrate that isotopic variability can be generated by multistage fractionation processes such as degassing of CO{sub 2} from magma and precipitation of CO{sub 2}-rich fluids to form graphitic compounds. Such processes operated over regions the scales of which were determined by style and intensity of deformation and by lithology.

Pineau, F. (Univ. de Paris (France)); Mathez, E.A. (American Museum of Natural History, New York (USA))



The use of carbon stable isotope ratios in drugs characterization  

SciTech Connect

Isotopic Ratio Mass Spectrometry (IRMS) is an effective toll to be used for drug product authentication. The isotopic composition could be used to assist in the differentiation between batches of drugs and assist in the identification of counterfeit materials on the market. Only two factors affect the isotopic ratios in pharmaceutical components: the isotopic composition of the raw materials and the synthetic processes performed upon them. Counterfeiting of pharmaceutical drugs threatens consumer confidence in drug products companies' economical well-being. In this preliminary study, the analyzed samples consist in two types of commercially available analgesics, which were purchases from Romanian pharmacies. Differences in ?{sup 13}C between batches from ?29.7 to ?31.6% were observed, demonstrating that this method can be used to differentiate among individual drug batches and subsequently identify counterfeits on the market. On the other hand, carbon isotopic ratios differences among producers were recorded, the variations being between ?31.3 to ?34.9% for the same type of analgesic, but from different manufactures.

Magdas, D. A., E-mail:; Cristea, G., E-mail:; Bot, A., E-mail:; Mirel, V., E-mail: [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath Str., 400293 Cluj-Napoca (Romania)



Ratios of Carbon Isotopes in Microbial Lipids as an Indicator of Substrate Usage  

PubMed Central

The occurrence and abundance of microbial fatty acids have been used for the identification of microorganisms in microbial communities. However, these fatty acids can also be used as indicators of substrate usage. For this, a systematic investigation of the discrimination of the stable carbon isotopes by different microorganisms is necessary. We grew 11 strains representing major bacterial and fungal species with four different isotopically defined carbon sources and determined the isotope ratios of fatty acids of different lipid fractions. A comparison of the differences of ?13C values of palmitic acid (C16:0) with the ?13C values of the substrates revealed that the isotope ratio is independent of the growth stage and that most microorganisms showed enrichment of C16:0 with 13C when growing on glycerol. With the exception of Burkholderia gladioli, all microorganism showed depletion of 13C in C16:0 while incorporating the carbons of glucose, and most of them were enriched with 13C from mannose, with the exception of Pseudomonas fluorescens and the Zygomycotina. Usually, the glycolipid fractions are depleted in 13C compared to the phospholipid fractions. The ?13C pattern was not uniform within the different fatty acids of a given microbial species. Generally, tetradecanoic acid (C14:0) was depleted of 13C compared to palmitic acid (C16:0) while octadecanoic acid (C18:0) was enriched. These results are important for the calibration of a new method in which ?13C values of fatty acids from the environment delineate the use of bacterial substrates in an ecosystem. PMID:9797266

Abraham, Wolf-Rainer; Hesse, Christian; Pelz, Oliver



The R Coronae Borealis stars - carbon abundances from forbidden carbon lines  

E-print Network

Spectra of several R Coronae Borealis (RCB) stars at maximum light were examined for the [C I] 9850 A and 8727 A absorption lines. The 9850 A line is variously blended with a Fe II and CN lines but positive identifications of the [C I] line are made for R CrB and SU Tau. The 8727 A line is detected in the spectrum of the five stars observed in this wavelength region. Carbon abundances are derived from the [C I] lines using the model atmospheres and atmospheric parameters used by Asplund et al. (2000). Although the observed strength of a C I line is constant from cool to hot RCB stars, the strength is weaker than predicted by an amount equivalent to a factor of four reduction of a line's gf-value. Asplund et al. dubbed this 'the carbon problem' and discussed possible solutions. The [C I] 9850 A line seen clearly in R CrB and SU Tau confirms the magnitude of the carbon problem revealed by the C I lines. The [C I] 8727 A line measured in five stars shows an enhanced carbon problem. The gf-value required to fit the observed [C I] 8727 A line is a factor of 15 less than the well-determined theoretical gf-value. We suggest that the carbon problem for all lines may be alleviated to some extent by a chromospheric-like temperature rise in these stars. The rise far exceeds that predicted by our non-LTE calculations, and requires a substantial deposition of mechanical energy.

Gajendra Pandey; David L. Lambert; N. Kameswara Rao; Bengt Gustafsson; Nils Ryde; David Yong



Kinetic fractionation of carbon and oxygen isotopes during hydration of carbon dioxide  

NASA Astrophysics Data System (ADS)

Kinetic isotope effects (KIEs) during the inorganic hydration of carbon dioxide (CO2) in aqueous solution cause reduced stable carbon and oxygen isotope ratios (13C/12C and 18O/16O) in the reaction product carbonic acid (H2CO3) or bicarbonate ion (HCO3-), relative to CO2. While such KIEs are of importance in various physicochemical, geochemical, and biological systems, very few experimental and theoretical studies have attempted to determine the magnitude of the carbon and oxygen kinetic isotope fractionation (KIF) during hydration of CO2. Here I use transition state theory (TST) and quantum chemistry calculations to investigate the reaction rates of isotopic reactants CO2+nH2O (n = 1-8) along the hydration pathway to H2CO3 or HCO3-. Locating transition states is difficult and the quantum chemistry calculations time-consuming at large n. My results suggest that the hydration mechanism for n = 1-3 is unlikely to be the dominant pathway producing KIFs during CO2 hydration in aqueous solution; hydration mechanisms for n ? 4 appear more likely. For n = 4-8, the predicted KIF based on MP2/aug-cc-pVDZ calculations at 25 °C is ?1.023-1.033 and ?1.013-1.015, for carbon and oxygen, respectively. However, these values are uncertain and the results of the present study suggest that new experimental work is required to accurately determine the KIF of carbon and oxygen during CO2 hydration.

Zeebe, Richard E.



The Distribution of Carbon Abundances in Stars in the Milky Way’s Satellite Galaxies  

NASA Astrophysics Data System (ADS)

There is evidence that the Milky Way halo is comprised in part of disrupted dwarf satellite galaxies; however, the extent to which they contribute to the halo’s formation is unclear. To further examine the role of dwarf galaxies in building the halo, we compared the degrees of carbon enhancement of the dwarf spheroidal (dSph) galaxies and field halo populations. We generated a grid of high-resolution synthetic spectra for hypothetical stars of specific effective temperature, surface gravity, metallicity, alpha element abundance, and carbon abundance for comparison with medium-resolution observed spectra of dSph stars of unmeasured [C/Fe] but otherwise known properties. After smoothing, rebinning, and normalizing the two data sets, we varied carbon abundance to find the best carbon abundance by determining the synthetic spectrum that gave the minimal deviation. We found a lower Carbon-Enhanced Metal-Poor (CEMP) fraction in the dSph galaxies, which suggests that they have evolved over time. Whereas star formation and chemical evolution stopped for accreted galaxies, the surviving galaxies evolved to became less carbon enhanced and more metal rich. The variation in carbon abundances supports prior knowledge of dSph stars and provide a deeper understanding the formation of stars such as those of the Milky Way halo. We thank the US National Science Foundation, the UCSC Science Internship Program, and the W. M. Keck Observatory where the spectra were obtained.

Guo, Michelle; Zhang, A.



The cause of carbon isotope minimum events on glacial terminations.  


The occurrence of carbon isotope minima at the beginning of glacial terminations is a common feature of planktic foraminifera carbon isotopic records from the Indo-Pacific, sub-Antarctic, and South Atlantic. We use the delta13C record of a thermocline-dwelling foraminifera, Neogloboquadrina dutertrei, and surface temperature estimates from the eastern equatorial Pacific to demonstrate that the onset of delta13C minimum events and the initiation of Southern Ocean warming occurred simultaneously. Timing agreement between the marine record and the delta13C minimum in an Antarctic atmospheric record suggests that the deglacial events were a response to the breakdown of surface water stratification, renewed Circumpolar Deep Water upwelling, and advection of low delta13C waters to the convergence zone at the sub-Antarctic front. On the basis of age agreement between the absolute delta13C minimum in surface records and the shift from low to high delta13C in the deep South Atlantic, we suggest that the delta13C rise that marks the end of the carbon isotope minima was due to the resumption of North Atlantic Deep Water influence in the Southern Ocean. PMID:11964477

Spero, Howard J; Lea, David W



The Determination of the Natural Abundance of the Isotopes of Chlorine: An Introductory Experiment in Mass Spectrometry.  

ERIC Educational Resources Information Center

Describes a laboratory experiment which introduces basic principles and experimental techniques of mass spectrometry for fourth year undergraduate (B.Sc.) students. Laboratory procedures, background information, and discussion of results are provided for the experiment in which the natural isotopic abundance of chlorine is determined. (Author/JN)

O'Malley, Rebecca M.



Natural abundance-level measurement of the nitrogen isotopic composition of oceanic nitrate: an adaptation of the ammonia diffusion method  

Microsoft Academic Search

We have adapted the “ammonia diffusion” method of nitrate extraction for natural-abundance level nitrogen isotopic measurement of oceanic nitrate. The method involves: (1) sample concentration (by boiling or evaporation); (2) conversion of nitrate to ammonia using Devarda's alloy; and (3) the gas-phase diffusion of ammonia onto an acidified glass fiber disk which is sandwiched between two porous Teflon membranes. We

D. M. Sigman; M. A. Altabet; R. Michener; D. C. McCorkle; B. Fry; R. M. Holmes



Isotopic Composition and Trace Element Abundances of a Presolar SiC AB Grain Reconstructed by Atom-Probe Tomography  

NASA Astrophysics Data System (ADS)

C and Si isotopic ratios of a previously characterized SiC AB grain are consistent with earlier NanoSIMS results. N, Al and Ti are abundant and distributed uniformly throughout the grain; s-process elements such as Zr, Mo and Ba were not detected.

Lewis, J. B.; Isheim, D.; Floss, C.; Groopman, E.; Gyngard, F.; Seidman, D. N.



Noble gas abundance and isotope ratios in the atmosphere of Jupiter from the Galileo Probe Mass Spectrometer  

Microsoft Academic Search

The Galileo Probe Mass Spectrometer provided the first data on the noble gas mixing and isotope ratios in the Jovian atmosphere. These measurements and the comparison with solar values constrain models of Jupiter's formation. Significant refinements to the initially reported abundances of argon, krypton, and xenon have been enabled through post-encounter laboratory calibrations using a refurbished engineering unit mass spectrometer

P. R. Mahaffy; H. B. Niemann; A. Alpert; S. K. Atreya; J. Demick; T. M. Donahue; D. N. Harpold; T. C. Owen



The clumped isotope geothermometer in soil and paleosol carbonate  

NASA Astrophysics Data System (ADS)

We studied both modern soils and buried paleosols in order to understand the relationship of temperature (T°C(47)) estimated from clumped isotope compositions (?47) of soil carbonates to actual surface and burial temperatures. Carbonates from modern soils with differing rainfall seasonality were sampled from Arizona, Nevada, Tibet, Pakistan, and India. T°C(47) obtained from these soils shows that soil carbonate forms in the warmest months of the year, in the late morning to afternoon, and probably in response to intense soil dewatering. T°C(47) obtained from modern soil carbonate ranges from 10.8 to 39.5 °C. On average, T°C(47) exceeds mean annual temperature by 10-15 °C due to summertime bias in soil carbonate formation, and to summertime ground heating by incident solar radiation. Secondary controls on T°C(47) are soil depth and shading. Site mean annual air temperature (MAAT) across a broad range (0-30 °C) of site temperatures is highly correlated with T°C(47) from soils, following the equation: MAAT(°C)=1.20(T°C(47)0)-21.72(r2=0.92) where T°C(47)0 is the effective air temperature at the site estimated from T°C(47). The effective air temperature represents the air temperature required to account for the T°C(47) at each site, after consideration of variations in T°C(47) with soil depth and ground heating. The highly correlated relationship in this equation should now permit mean annual temperature in the past to be reconstructed from T°C(47) in paleosol carbonate, assuming one is studying paleosols that formed in environments generally similar in seasonality and ground cover to our calibration sites. T°C(47)0 decreases systematically with elevation gain in the Himalaya, following the equation: elevation(m)=-229(T°C(47)0)+9300(r2=0.95) Assuming that temperature varied similarly with elevation in the past, this equation can be used to reconstruct paleoelevation from clumped isotope analysis of ancient soil carbonates. We also measured T°C(47) from long sequences of deeply buried (?5 km) paleosol carbonate in the Himalayan foreland in order to evaluate potential diagenetic resetting of clumped isotope composition. We found that paleosol carbonate faithfully records plausible soil T°C(47) down to 2.5-4 km burial depth, or ˜90-125 °C. Deeper than this and above this temperature, T°C(47) in paleosol carbonate is reset to temperatures >40 °C. We observe ˜40 °C as the upper limit for T°C(47) in modern soils from soil depths >25 cm, and therefore that T°C(47) >40 °C obtained from ancient soil carbonate indicates substantially warmer climate regimes compared to the present, or non-primary temperatures produced by resetting during diagenesis. If representative, this limits the use of T°C(47) to reconstruct ancient surface temperature to modestly buried (<3-4 km) paleosol carbonates. Despite diagenetic resetting of ?47 values, ?18O and ?13C values of the same deeply buried paleosol carbonate appear unaltered. We conclude that solid-state reordering or recrystallization of clumping of carbon and oxygen isotopes can occur in the absence of open-system exchange of paleosol carbonate with significant quantities of water or other phases.

Quade, J.; Eiler, J.; Daëron, M.; Achyuthan, H.



A survey of methane isotope abundance (14C, 13C, 2H) from five nearshore marine basins that reveals unusual radiocarbon levels in subsurface waters  

NASA Astrophysics Data System (ADS)

Methane (CH4) in the subsurface ocean is often supersaturated compared to equilibrium with the modern atmosphere. In order to investigate sources of CH4 to the subsurface ocean, isotope surveys (14C-CH4,?13C-CH4, ?2H-CH4) were conducted at five locations: Skan Bay (SB), Santa Barbara Basin (SBB), Santa Monica Basin (SMB), Cariaco Basin (CB), and the Guaymas Basin (GB). Depth distributions of CH4 concentration and isotopic abundance were determined for both the sediment and water column at the SB, SBB, SMB, and CB sites; CH4 emitted from seeps on the continental shelf adjacent to the SBB as well as seeps and decomposing clathrate hydrates in the GB was also collected, purified, and analyzed. Methane isotope distributions in the sediments were consistent with known methanogenic and methanotrophic activity; seep- and clathrate-hydrate-derived CH4 was found to be depleted in radiocarbon. However, surprising results were obtained in the water column at all sites investigated. In SB the radiocarbon content of the subsurface CH4 concentration maximum was on average 41% less than its suspected sediment CH4 source, suggesting CH4 seepage in the bay. In the SBB, SMB, and CB, the 14C-CH4 contents in the subsurface ocean were 1.2 to 3.6 times greater than modern carbon quantities suggesting a source of 14C from atmospheric nuclear weapons testing, nuclear power plant effluents, or cosmogenic isotope production.

Kessler, J. D.; Reeburgh, W. S.; Valentine, D. L.; Kinnaman, F. S.; Peltzer, E. T.; Brewer, P. G.; Southon, J.; Tyler, S. C.



Insights from Stable Isotopes on the Role of Terrestrial Ecosystems in the Global Carbon Cycle  

Microsoft Academic Search

The use of isotopic tracers in organic matter, water, and atmospheric gases has become an important component of the study of ecology and global change. Physiological and physical processes discriminate against heavy isotopes in predictable ways, so that measurements of isotopes at natural abundance, i.e., naturally occurring concentrations as opposed to artificial labeling experiments, can provide useful information about biological

Diane E. Pataki; Chun-Ta Lai; Charles D. Keeling; James R. Ehleringer



EPA Science Inventory

Stable isotopes in sporocarps have proven useful for inferring ectomycorrhizal or saprotrophic status and understanding carbon (C) and nitrogen (N) utilization. However, greater understanding of processes producing isotopic concentrations is needed. We measured natural abundanc...


A continuous 250,000 yr record of oxygen and carbon isotopes in ostracode and bulk-sediment carbonate from Bear Lake, Utah-Idaho  

USGS Publications Warehouse

Oxygen and carbon isotopes from a continuous, 120-m-long, carbonate-rich core from Bear Lake, Utah-Idaho, document dramatic fluctuations in the hydrologic budget of the lake over the last 250,000 yr. Isotopic analyses of bulk sediment samples capture millennial-scale variability. Ostracode calcite was analyzed from 78 levels, mainly from the upper half of the core where valves are better preserved, to compare the isotopic value of purely endogenic carbonate with the bulk sediment, which comprises both endogenic and detrital components. The long core exhibits three relatively brief intervals with abundant endogenic aragonite (50??10%) and enriched ??18O and ??13C. These intervals are interpreted as warm/dry periods when the lake retracted into a topographically closed basin. We correlate these intervals with the interglacial periods of marine oxygen-isotope stages 1, 5e, and 7a, consistent with the presently available geochronological control. During most of the time represented by the core, the lake was fresher than the modern lake, as evidenced by depleted ??18O and ??13C in bulk-sediment carbonate. ?? 2006 Elsevier Ltd. All rights reserved.

Bright, J.; Kaufman, D.S.; Forester, R.M.; Dean, W.E.



Perturbing phytoplankton: response and isotopic fractionation with changing carbonate chemistry in two coccolithophore species  

NASA Astrophysics Data System (ADS)

All species of coccolithophore appear to respond to perturbations of carbonate chemistry in a different way. Here, we show that the degree of malformation, growth rate and stable isotopic composition of organic matter and carbonate produced by two contrasting species of coccolithophore (Gephyrocapsa oceanica and Coccolithus pelagicus ssp. braarudii) are indicative of differences between their photosynthetic and calcification response to changing DIC levels (ranging from ~1100 to ~7800 ?mol kg-1) at constant pH (8.13 ± 0.02). Gephyrocapsa oceanica thrived under all conditions of DIC, showing evidence of increased growth rates at higher DIC, but C. braarudii was detrimentally affected at high DIC showing signs of malformation, and decreased growth rates. The carbon isotopic fractionation into organic matter and the coccoliths suggests that C. braarudii utilises a common internal pool of carbon for calcification and photosynthesis but G. oceanica relies on independent supplies for each process. All coccolithophores appear to utilize bicarbonate as their ultimate source of carbon for calcification resulting in the release of a proton. But, we suggest that this proton can be harnessed to enhance the supply of CO2(aq) for photosynthesis either from a large internal HCO3- pool which acts as a pH buffer (C. braarudii), or pumped externally to aid the diffusive supply of CO2 across the membrane from the abundant HCO3- (G. oceanica), likely mediated by an internal and external carbonic anhydrase respectively. Our simplified hypothetical spectrum of physiologies may provide a context to understand different species response to changing pH and DIC, the species-specific ?p and calcite "vital effects", as well as accounting for geological trends in coccolithophore cell size.

Rickaby, R. E. M.; Henderiks, J.; Young, J. N.



Dear Editor, Carbon and oxygen isotope analysis of small carbonate  

E-print Network

Finnigan (Bremen, Germany, now Thermo Fisher Scientific) GasBench II, equipped with a CTC autosampler (CTC spectrometer (both Thermo Fisher Scientific) at the ETH Zurich (Zurich, Switzerland). The system setup µg of carbonate are possible. For the experiments described below we employ the Thermo

Gilli, Adrian



E-print Network; Compound-specific hydrogen isotope analyses are gaining increasing interestHYDROGEN ISOTOPE PROFILE OF METHYL GROUPS IN MILIACIN (OLEAN- 18-EN-3OL ME) BY NATURAL ABUNDANCE to which extent these modifications can be accompanied by a hydrogen isotope fractionation process

Paris-Sud XI, Université de


SIO269 Special Topics in Marine Chemistry Seminar Carbon Cycle from an Isotope Perspective  

E-print Network

SIO269 Special Topics in Marine Chemistry Seminar ­ Carbon Cycle from an Isotope Perspective 1 Changes in the ocean carbon cycle readings: Broecker et al. (2007) Quay et al. (2003) November 27th Stable Carbon Isotopes: A quick introduction (Reading: Gruber et al., 1999; Kroopnick, 1985) October 9th

Aluwihare, Lihini


Sensitivity analysis and quantification of uncertainty for isotopic mixing relationships in carbon cycle research  

E-print Network

relationships is critical to isotopic applications in carbon cycle studies at all spatial and temporal scales ecosystems represents one of the current challenges in carbon cycle research (Schimel et al., 1994, 2001Sensitivity analysis and quantification of uncertainty for isotopic mixing relationships in carbon

Keener, James P.


Carbon and Nitrogen Isotope Variation in Sphagnum from Peat Bogs in the Midwestern Us: Implications for Holocene Climate Reconstruction  

NASA Astrophysics Data System (ADS)

A peat core taken from near the center of Minden Bog in Michigan, representing about 3500 years of accumulation was previously analyzed for plant macrofossils, colorimetric humification, and testate amoebae to yield three independent climate proxies. The data show the site to be sensitive to bog water table fluctuations and suggest that this may be related to regional climatic changes. We analyzed the carbon and nitrogen isotopes and the carbon-nitrogen ratios in the bulk peat samples and determined that the changes in these isotopes and ratios can be attributed to one or more of the following: (1) changes in the relative abundance of vegetation taxa in the site, (2) changes in the metabolism that impact isotope ratios in the vegetation contributing to the bulk organic, and (3) selective preservation and regeneration of specific organic compounds within the bulk organic matter. We analyzed the carbon and nitrogen isotopes and the carbon-nitrogen ratios in a specific taxum, Sphagnum, to differentiate between these mechanisms and relate the record to water level and climate in the region.

Wong, D.; Paytan, A.; Jackson, S. T.



A Comparison of Oxidized Carbon Abundances among Comets  

NASA Technical Reports Server (NTRS)

Comets contain relatively well preserved icy material remaining from the epoch of Solar System formation, however the extent to which these ices are modified from their initial state remains a fundamental question in cometary science. As a comet approaches the Sun, sublimation of the ices contained in its nucleus (termed " native ices") releases parent volatiles into the coma, where they can be measured spectroscopically. One means of assessing the degree to which interstellar ices were processed prior to their incorporation into cometary nuclei is to measure the relative abundances of chemically-related parent volatiles. For example, formation of C2H6 by hydrogen atom addition (e.g., to C2H2) on surfaces of ice-mantled grains was proposed to explain the high C2H6 to CH4 abundance observed in C/1996 B2 (Hyakutake) [1]. The large C2H6/CH4 abundance ratios measured universally in comets, compared with those predicted by gas phase production of C2H6, establishes H-atom addition as an important and likely ubiquitous process. CO should also be hydrogenated on grain surfaces. Laboratory irradiation experiments on interstellar ice analogs indicate this to require very low temperatures (T approx. 10-25 K), the resulting yields of H2CO and CH3OH being highly dependent both on hydrogen density (i.e., fluence) and on temperature ([2],[3]). This relatively narrow range in temperature reflects a lack of mobility below 8-10 K on the one hand, and reduced sticking times for H-atoms as grain surfaces are warmed above 20 K on the other. The relative abundances of these three chemically-related molecules in comets provides one measure of the efficiency of H-atom addition to CO on pre-cometary grains (Fig. 1).

DiSanti, M. A.; Mumma, M. J.; Bonev, B. P.; Villanueva, G. L.; Radeva, Y. L.; Magee-Sauer, K.; Gibb, E. L.




EPA Science Inventory

Exposure of riverine waters to natural sunlight initiated alterations in stable carbon isotope ratios (delta C-13) of the associated dissolved organic carbon (DOC). Water samples were collected from two compositionally distinct coastal river systems in the southeastern United Sta...


Dynamic and transfert of carbon in Loire catchment using carbon isotopes  

NASA Astrophysics Data System (ADS)

Rivers have a major role in carbon transfer between continent and ocean. The organic matter exported from land represents a major source of DOC and POC in oceans. The composition and reactivity of this matter will influence its behavior and fate within the coastal areas and continental shelf. It is thus important to characterize the exported matter and its temporal variability. Stable carbon isotope ratios (d13C) and 14C activity can provide unique information on carbon sources, turnover and exchange processes. We present here a study of the carbon cycle in the Loire River and its major tributaries by combining carbon isotopes measurements and classical biogeochemical parameters (DOC, POC, DIC, pH, Temperature, Alkalinity, pH, chlorophyll …). Three campaigns were performed in April, July and October 2013. The changes in 14C signature due to the controlled liquid release of five nuclear power plants are used to get additional information on the carbon dynamics within the river. First results show a conservative behavior of the organic carbon concentrations contrary to the inorganic carbon all along the Loire River. However, the reactivity of the organic matter varies with rivers catchments and seasons. An inventory of the distribution of the different carbon phases within the Loire River and its tributaries is presented.

Coularis, Cindy; Fontugne, Michel; Tisnérat-Laborde, Nadine; Pastor, Lucie; Siclet, Françoise



The distribution and stable carbon isotopic composition of dissolved organic carbon in estuaries  

Microsoft Academic Search

The distributions of dissolved organic carbon (DOC) and the natural carbon isotope ratio of DOC (DO13C) in estuaries reflect the predominant sources and sinks of organic matter from both allochthonous and autochthonous origins.\\u000a The traditional view is that DOC in land-margin ecosystems reflects mainly the mixing of land-derived and oceanic DOC. However,\\u000a this view is not consistent with the bulk

Bruce Peterson; Brian Fry; Meredith Hullar; Susan Saupe; Richard Wright



Rapid carbon-carbon bond formation and cleavage revealed by carbon isotope exchange between the carboxyl carbon and inorganic carbon in hydrothermal fluids  

NASA Astrophysics Data System (ADS)

The carbon isotopic composition of organic compounds in water-rock systems (e.g., hydrothermal vents, sedimentary basins, and carbonaceous meteorites) is generally interpreted in terms of the isotopic composition of the sources of such molecules, and the kinetic isotope effects of metabolic or abiotic reactions that generate or transform such molecules. This hinges on the expectation that the carbon isotopic composition of many organic compounds is conserved under geochemical conditions. This expectation is reasonable in light of the strength of carbon-carbon bonds (ca. 81 kcal/mol); in general, environmental conditions conducive to carbon-carbon bond cleavage typically lead to transformations of organic molecules (decarboxylation is a notable example). Geochemically relevant reactions that involve isotopic exchange between carbon atoms in organic molecules and inorganic forms of carbon with no change in molecular structure appear to be rare. Notwithstanding such rarity, there have been preliminary reports of relatively rapid carbon isotope exchange between the carboxyl group in carboxylic acids and carbon dioxide in hot water [1,2]. We have performed laboratory hydrothermal experiments to gain insights into the mechanism of this surprising reaction, using phenylacetate as a model structure. By mass spectrometry, we confirm that the carboxyl carbon undergoes facile isotopic exchange with 13C-labeled bicarbonate at moderate temperatures (i.e., 230 C). Detailed kinetic analysis reveals that the reaction rate is proportional to the concentrations of both reactants. Further experiments demonstrate that the exchange reaction only occurs if the carbon atom adjacent to the carboxyl carbon is bonded to a hydrogen atom. As an example, no carbon isotope exchange was observed for benzoate in experiments lasting up to one month. The requirement of an alpha C-H bond suggests that enolization (i.e., deprotonation of the H) is a critical step in the mechanism of the exchange reaction. We confirmed this by determining the exchange kinetics for various ring-substituted phenylacetates, and we find that the observed rate constants are consistent with the amount of negative charge that would be expected on the alpha carbon of the enolate. The emerging picture of the reaction mechanism is that enolization allows fixation of labeled carbon dioxide as a beta-carboxy group, where subsequent heterolytic decarboxylation of the unlabeled carboxy group completes the exchange process. Solvent stabilization of ionic reaction intermediates would lead to faster than expected rates of exchange, and ultimately to an isotopic equilibrium over even short geologic timescales. For enolizable carboxylic acids in natural systems, one has to consider this exchange mechanism when interpreting the carbon isotopic composition. [1] Dias R.F. (2000) Ph.D. Dissertation, Penn. State Univ. [2] Seewald J.S. & Boekelheide N. (2005) Goldschmidt Conf., A558.

Glein, C. R.; Cody, G. D.



Methodologies for extraction of dissolved inorganic carbon for stable carbon isotope studies : evaluation and alternatives  

USGS Publications Warehouse

The gas evolution and the strontium carbonate precipitation techniques to extract dissolved inorganic carbon (DIC) for stable carbon isotope analysis were investigated. Theoretical considerations, involving thermodynamic calculations and computer simulation pointed out several possible sources of error in delta carbon-13 measurements of the DIC and demonstrated the need for experimental evaluation of the magnitude of the error. An alternative analytical technique, equilibration with out-gassed vapor phase, is proposed. The experimental studies revealed that delta carbon-13 of the DIC extracted from a 0.01 molar NaHC03 solution by both techniques agreed within 0.1 per mil with the delta carbon-13 of the DIC extracted by the precipitation technique, and an increase of only 0.27 per mil in that extracted by the gas evolution technique. The efficiency of extraction of DIC decreased with sulfate concentration in the precipitation technique but was independent of sulfate concentration in the gas evolution technique. Both the precipitation and gas evolution technique were found to be satisfactory for extraction of DIC from different kinds of natural water for stable carbon isotope analysis, provided appropriate precautions are observed in handling the samples. For example, it was found that diffusion of atmospheric carbon dioxide does alter the delta carbon-13 of the samples contained in polyethylene bottles; filtration and drying in the air change the delta carbon-13 of the samples contained in polyethylene bottles; filtration and drying in the air change the delta carbon-13 of the precipitation technique; hot manganese dioxide purification changes the delta carbon-13 of carbon dioxide. (USGS)

Hassan, Afifa Afifi




EPA Science Inventory

We describe a method for rapid preparation, concentration and stable isotopic analysis of dissolved inorganic carbon (d13C-DIC). Liberation of CO2 was accomplished by placing 100 ?l phosphoric acid and 0.9 ml water in an evacuated 1.7-ml gas chromatography (GC) injection vial. Fo...


Oxygen isotope systematics in carbonate-water systems : influence of temperature, solution chemistry, and kinetic isotope fractionation.  

E-print Network

??The oxygen isotope fractionation between HCO3-/CO 32- and H2O was determined experimentally in order to elucidate the precipitation mechanisms of orthorhombic carbonate minerals in solutions.… (more)

Kim, Sang-Tae, 1970-



Stable isotopes, ecological integration and environmental change: wolves record atmospheric carbon isotope trend better than tree rings  

Microsoft Academic Search

Large-scale patterns of isotope ratios are detectable in the tissues of organisms, but the variability in these patterns often obscures detection of environmental trends. We show that plants and animals at lower trophic levels are relatively poor indicators of the temporal trend in atmospheric carbon isotope ratios (d13C) when compared with animals at higher trophic levels. First, we tested how

Joseph K. Bump; Kena Fox-Dobbs; Jeffrey L. Bada; Paul L. Koch; Rolf O. Peterson; John A. Vucetich



Carbon isotopic enrichment in Titan's tholins? Implications for Titan's aerosols  

NASA Astrophysics Data System (ADS)

Since the discovery of the main composition of Titan's atmosphere, many laboratory experiments have been carried out to mimic its chemical evolution, and more particularly the formation of the organic haze particles widespread in this atmosphere. Indeed, some of these simulation experiments produce a solid phase - named Titan's tholins - that is assumed to get properties analogous to the Titan's aerosols ones. We have studied the possible isotopic fractionation of carbon during the processes involved in the formation of Titan's tholins, using tholins obtained from different simulation experiments. It's an important issue because it can provide information on the processes of tholins formation. We will present the first results obtained on the 12 C/13 C isotopic ratios measured on Titan's tholins synthesized in laboratory with cold plasma discharges. Measurements of isotopic enhancement in 13 C (? 13 C), done both on tholins and on the initial gas mixture (N2 :CH4 (98:2)) used to produce them, do not show any clear deficit or enrichment in 13 C relatively to 12 C in the synthesised tholins, compared to the initial gas mixture. Preliminary retrieving of the data of the Aerosol Collector and Pyrolyzer (ACP) experiment of the Huygens probe suggests that Titan's aerosols may also not present carbon isotopic enrichment. This observation allows to go further in the analyses of the ACP experiment data. We are also focusing on the evolution of Titan's tholins under acid hydrolysis treatment. This strong treatment aims to reproduce the evolution of Titan's aerosols in contact with ice water under a longer time scale. Preliminary results on the analyses of the obtained products could give guides lines to identify the still unspecified matter that takes part to the Titan's surface reflectivity decrease as observed by the DISR instrument. This study is still in progress.

Nguyen, M.-J.; Raulin, F.; Coll, P.; Derenne, S.; Szopa, C.; Cernogora, G.; Israel, G.; Bernard, J.-M.


{sup 39}Ar Detection at the 10{sup -16} Isotopic Abundance Level with Atom Trap Trace Analysis  

SciTech Connect

Atom trap trace analysis, a laser-based atom counting method, has been applied to analyze atmospheric {sup 39}Ar (half-life=269 yr), a cosmogenic isotope with an isotopic abundance of 8x10{sup -16}. In addition to the superior selectivity demonstrated in this work, the counting rate and efficiency of atom trap trace analysis have been improved by 2 orders of magnitude over prior results. The significant applications of this new analytical capability lie in radioisotope dating of ice and water samples and in the development of dark matter detectors.

Jiang, W.; Williams, W.; Bailey, K.; O'Connor, T. P.; Mueller, P. [Physics Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Davis, A. M. [Enrico Fermi Institute, University of Chicago, Chicago, Illinois 60637 (United States)] [Department of Geophysical Sciences, University of Chicago, Chicago, Illinois 60637 (United States); Hu, S.-M.; Sun, Y. R. [Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Lu, Z.-T. [Physics Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)] [Enrico Fermi Institute, University of Chicago, Chicago, Illinois 60637 (United States)] [Department of Physics, University of Chicago, Chicago, Illinois 60637 (United States); Purtschert, R. [Climate and Environmental Physics, University of Bern, CH-3012 Bern (Switzerland); Sturchio, N. C. [Department of Earth and Environmental Sciences, University of Illinois at Chicago, Chicago, Illinois 60607 (United States)



Calibrated sulfur isotope abundance ratios of three IAEA sulfur isotope reference materials and V-CDT with a reassessment of the atomic weight of sulfur  

NASA Astrophysics Data System (ADS)

Calibrated values have been obtained for sulfur isotope abundance ratios of sulfur isotope reference materials distributed by the IAEA (Vienna). For the calibration of the measurements, a set of synthetic isotope mixtures were prepared gravimetrically from high purity Ag 2S materials enriched in 32S, 33S, and 34S. All materials were converted into SF 6 gas and subsequently, their sulfur isotope ratios were measured on the SF 5+ species using a special gas source mass spectrometer equipped with a molecular flow inlet system (IRMM's Avogadro II amount comparator). Values for the 32S/ 34S abundance ratios are 22.650 4(20), 22.142 4(20), and 23.393 3(17) for IAEA-S-1, IAEA-S-2, and IAEA-S-3, respectively. The calculated 32S/ 34S abundance ratio for V-CDT is 22.643 6(20), which is very close to the calibrated ratio obtained by Ding et al. (1999). In this way, the zero point of the VCDT scale is anchored firmly to the international system of units SI. The 32S/ 33S abundance ratios are 126.942(47), 125.473(55), 129.072(32), and 126.948(47) for IAEA-S-1, IAEA-S-2, IAEA-S-3, and V-CDT, respectively. In this way, the linearity of the V-CDT scale is improved over this range. The values of the sulfur molar mass for IAEA-S-1 and V-CDT were calculated to be 32.063 877(56) and 32.063 911(56), respectively, the values with the smallest combined uncertainty ever reported for the sulfur molar masses (atomic weights).

Ding, T.; Valkiers, S.; Kipphardt, H.; De Bièvre, P.; Taylor, P. D. P.; Gonfiantini, R.; Krouse, R.



[The determination of porphyrin carbon isotope composition by gas chromatography-isotope ratio monitoring mass spectrometry technique].  


The porphyrin carbon isotope composition can be used to explore the precursor of porphyrin, oil-oil and oil-source rock correction and calculation of paleo P CO2. The conventional method is limited because of its time consuming and large sample size (several mg of individual porphyrin) required. Therefore, it hampers the application of porphyrin carbon isotope composition into the chemistry and geoscience. The present paper describes a quantification method to prepare bis-(tert-butyldimethylsiloxy) silicon (IV) [(TBDMSO)2Si(IV)] porphyrin which is sufficiently volatile at 300 degrees C and can be used for GC-IRMS analysis. The analysis of carbon isotope composition of aetio I as the form of free base, nickel, demetalization derivative, silicon(IV) and (TBDMSO)2Si(IV) have shown that aetio I porphyrin has no obvious isotope fractionation in the whole synthesis procedure for (TBDMSO)2Si(IV) porphyrin. The carbon isotope study on the porphyrin mixtures of aetio I and OEP indicates that isotope exchange between porphyrins during the synthesis of (TBDMSO)2Si(IV) porphyrin is absent. The method can be applied to the determination of porphyrin carbon isotope compositions. The advantages of the method are time saving, less sample size and lower standard deviation. PMID:12541647

Yu, Z Q; Peng, P A; Fu, J M; Sheng, G Y



The Abundances and Time Evolution of Carbon, Nitrogen and Oxygen in Star-Forming Galaxies  

Microsoft Academic Search

We propose to observe UV emission lines of carbon, nitrogen, and oxygen from high-surface brightness extragalactic H II regions drawn from a sample of irregular and spiral galaxies having a large spread of known oxygen abundance (2% solar to nearly solar). From the emission-line data we will derive C\\/O and N\\/O abundance ratios for which systematic uncertainties - due to

Evan Skillman



Modeling Chemical and Isotopic Variations in Lab Formed Hydrothermal Carbonates  

NASA Technical Reports Server (NTRS)

Chemical and mineralogical data (e.g. [1]) from Mars suggest that the history of liquid water on the planet was more sporadic in nature than long-lived. The non-equilibrium chemical and isotopic compositions of the carbonates preserved in the martian meteorite ALH84001 are direct evidence of ancient secondary minerals that have not undergone significant diagenesis or stabilization processes typical of long-lived aqueous systems on Earth. Thus secondary minerals and sediments on Mars may primarily record the characteristics of the aqueous environment in which they formed without being significantly overprinted by subsequent diagenetic processes during burial.

Niles, P. B.; Leshin, L. A.; Golden, D. C.; Socki, R. A.; Guan, Y.; Ming, D. W.



The carbon isotopic composition of Novo Urei diamonds  

NASA Technical Reports Server (NTRS)

The carbon isotopic composition of diamond grains isolated from the Novo Urei meteorite are discussed. A diamond separate was obtained from 2g of whole rock using the chemical treatments described aimed at obtaining very pure diamond. X ray diffraction of the residue, which represented 5000 ppm of the parent mass, indicated only the presence of the desired mineral. The diamond crystals were 1-30 microns in diameter, and some grains had a yellow color. The chemical treatments were followed by a size separation to give a 1-10 microns and a 5-30 microns fraction, which were named DNU-1 and DNU-2, respectively.

Fisenko, A. V.; Semjenova, L. F.; Verchovsky, A. B.; Russell, S. S.; Pillinger, C. T.



Helium-carbon isotopic composition of thermal waters from Tunisia  

NASA Astrophysics Data System (ADS)

Tunisia has numerous thermo-mineral springs. Previous studies have shown that their chemical composition and occurrence are strongly influenced by the regional geology, however little work has been conducted to date to investigate the isotopic composition of volatiles associated with these geothermal manifestations. Here, we report the results of an extensive survey of both natural hot springs and production wells across Tunisia aimed at investigating the spatial distribution of the 3He/4He ratio and associated carbon isotopic compositions. With respect to helium isotopes, not unexpectedly, the lowest 3He/4He values (0.01-0.02 Ra) are associated with the old groundwaters of the “Continental Intercalaire” aquifer of the stable Saharan Platform. The 3He/4He values are equal to the crustal production ratio, with no detectable amount of mantle-derived 3He, in agreement with previous studies of helium isotopes in sedimentary basin, which conclude that tectonically-stable regions are essentially impermeable to mantle volatiles. The low 3He/4He domain extends to the entire Atlasic domain of central Tunisia. This Atlasic domain also displays the highest helium concentrations : along the Gafsa Fault, helium concentrations of 1777 and 4723 x 10-8 cm3STP/g (the highest value of our data set) are observed in the production wells of Sidi Ahmed Zarrouk. This emphasizes the role of deep tectonic features in channelling and transporting deep crustal volatiles to shallow levels. The eastern margin of Tunisia displays higher 3He/4He values indicative of a substantial mantle volatile input. The highest value is recorded in the carbo-gaseous mineral water of Ain Garci (2.4 Ra). This northeastern part of the African plate commonly referred to as the Pelagian block extends from Tunisia to Sicily and is characterized by strong extensional tectonics (Pantelleria rift zone) and present-day magmatic activity. This lithospheric stretching and decompressional mantle melts production in the central portion of the Pelagian Block may facilitate the transport of mantle helium through the thinned crust away from the rift zone across the existing network of fractures and deep faults. Samples were also collected for water chemistry, ?D, ?18O, and carbon isotopic composition. ?13C(TDC) data are highly heterogeneous (ranging from -11.2 to +2.9 ‰ vs. V-PDB), in particular, revealing a complex origin for total dissolved carbon (TDC) in groundwaters. We interpret these variable isotopic compositions as reflecting mixture of biogenically derived carbon with abiogenic (mantle-derived or metamorphic) CO2. A detailed discussion of the whole chemistry and isotopic data set will be presented and the results will be examined in relation to the geological and structural framework of Tunisia.

Fourré, E.; Aiuppa, A.; di Napoli, R.; Parello, F.; Gaubi, E.; Jean-Baptiste, P.; Allard, P.; Calabrese, S.; Ben Mammou, A.



Ca isotope fractionation in modern and fossil bivalve shell carbonate  

NASA Astrophysics Data System (ADS)

Ca isotopes of bivalve carbonate, used in combination with light stable isotopes and metal/Ca ratios may provide a useful archive of annual and seasonal parameters such as temperature, salinity or nutrient level, and therefore for high-resolution palaeoclimate reconstructions, but the reliability of these proxies remains questionable given potential vital/ontogenetic and microenvironmental effects. Furthermore, in order to test the applicability of bivalve-based environmental proxies on geological time-scales, it is of crucial importance to assess the sensitivity of shell geochemistry to early diagenesis. We investigated these potential effects, first by using field cultured, intertidal and subtidal bivalve species cultured in the Dutch Wadden Sea, and second by using selected fossil bivalve shells from Pleistocene (MIS 5e) uplifted marine terraces located in the SE Gulf of Corinth area, Greece. Cultured individuals offer the chance to compare time series of instrumental environmental data directly to growth rate and shell chemistry, whereas fossil samples, which were exposed to meteoric conditions for an extended period, are perfect for studying potential diagenetic influences on the Ca isotope system. Ca isotope signatures of both cultured bivalve species are positively correlated with ambient seawater temperature. The slope of the temperature-fractionation relation is similar to inorganic calcite and aragonite precipitates. However, the Ca isotope values are offset from the inorganic curves of about 0.5 permil. The most likely explanation for this offset is a biological induced fractionation, which can be attributed to the active transport of calcium through different cell layers to the site of calcification. In contrast, the studied fossil shells show little variations in Ca isotope composition. We observed that fossil biogenic aragonite from the same chronostratigraphic unit is considerably less fractionated than fossil biogenic calcite, which can be either explained by an implausible temperature effect of approximately 10 degree Celsius or by weak diagenetic overprinting. To summarize, these results provide new insights into biomineralization processes and indicate however a limited use of Ca isotopes in bivalves as temperature proxy.

Hippler, D.; Witbaard, R.; Buhl, D.; Immenhauser, A.



Carbon isotope fractionation of sapropelic organic matter during early diagenesis  

USGS Publications Warehouse

Study of an algal, sapropelic sediment from Mangrove Lake, Bermuda shows that the mass balance of carbon and stable carbon isotopes in the major organic constituents is accounted for by a relatively straightforward model of selective preservation during diagenesis. The loss of 13C-enriched carbohydrates is the principal factor controlling the intermolecular mass balance of 13C in the sapropel. Results indicate that labile components are decomposed leaving as a residual concentrate in the sediment an insoluble humic substance that may be an original biochemical component of algae and associated bacteria. An overall decrease of up to about 4??? in the ?? 13C values of the organic matter is observed as a result of early diagenesis. ?? 1984.

Spiker, E. C.; Hatcher, P.G.




SciTech Connect

{sup 12}C/{sup 13}C isotopologue abundance anomalies have long been predicted for gas-phase chemistry in molecules other than CO and have recently been observed in the Taurus molecular cloud (TMC) in several species hosting more than one carbon atom, i.e., CCH, CCS, CCCS, and HC{sub 3}N. Here we work to ascertain whether these isotopologic anomalies actually result from the predicted depletion of the {sup 13}C{sup +} ion in an oxygen-rich optically shielded dense gas, or from some other more particular mechanism or mechanisms. We observed {lambda}3mm emission from carbon-, sulfur-, and nitrogen-bearing isotopologues of HNC, CS, and H{sub 2}CS at three positions in Taurus (TMC1, L1527, and the NH{sub 3} peak) using the ARO 12 m telescope. We saw no evidence of {sup 12}C/{sup 13}C anomalies in our observations. Although the pool of C{sup +} is likely to be depleted in {sup 13}C, {sup 13}C is not depleted in the general pool of carbon outside CO, which probably exists mostly in the form of C{sup 0}. The observed isotopologic abundance anomalies are peculiar to those species in which they are found.

Liszt, H. S. [National Radio Astronomy Observatory, 520 Edgemont Road, Charlottesville, VA 22903-2475 (United States); Ziurys, L. M., E-mail: [Arizona Radio Observatory, University of Arizona, 933 North Cherry Avenue, Tucson, AZ 85721 (United States)



Mass Accuracy and Isotopic Abundance Measurements for HR-MS Instrumentation: Capabilities for Non-Targeted Analyses  

NASA Astrophysics Data System (ADS)

The development of automated non-targeted workflows for small molecule analyses is highly desirable in many areas of research and diagnostics. Sufficient mass and chromatographic resolution is necessary for the detectability of compounds and subsequent componentization and interpretation of ions. The mass accuracy and relative isotopic abundance are critical in correct molecular formulae generation for unknown compounds. While high-resolution instrumentation provides accurate mass information, sample complexity can greatly influence data quality and the measurement of compounds of interest. Two high-resolution instruments, an Orbitrap and a Q-TOF, were evaluated for mass accuracy and relative isotopic abundance with various concentrations of a standard mixture in four complex sample matrices. The overall average ± standard deviation of the mass accuracy was 1.06 ± 0.76 ppm and 1.62 ± 1.88 ppm for the Orbitrap and the Q-TOF, respectively; however, individual measurements were ± 5 ppm for the Orbitrap and greater than 10 ppm for the Q-TOF. Relative isotopic abundance measurements for A + 1 were within 5% of the theoretical value if the intensity of the monoisotopic peak was greater than 1E7 for the Orbitrap and 1E5 for the Q-TOF, where an increase in error is observed with a decrease in intensity. Furthermore, complicating factors were found in the data that would impact automated data analysis strategies, including coeluting species that interfere with detectability and relative isotopic abundance measurements. The implications of these findings will be discussed with an emphasis on reasonable expectations from these instruments, guidelines for experimental workflows, data analysis considerations, and software design for non-targeted analyses.

Knolhoff, Ann M.; Callahan, John H.; Croley, Timothy R.



Mass accuracy and isotopic abundance measurements for HR-MS instrumentation: capabilities for non-targeted analyses.  


The development of automated non-targeted workflows for small molecule analyses is highly desirable in many areas of research and diagnostics. Sufficient mass and chromatographic resolution is necessary for the detectability of compounds and subsequent componentization and interpretation of ions. The mass accuracy and relative isotopic abundance are critical in correct molecular formulae generation for unknown compounds. While high-resolution instrumentation provides accurate mass information, sample complexity can greatly influence data quality and the measurement of compounds of interest. Two high-resolution instruments, an Orbitrap and a Q-TOF, were evaluated for mass accuracy and relative isotopic abundance with various concentrations of a standard mixture in four complex sample matrices. The overall average ± standard deviation of the mass accuracy was 1.06 ± 0.76 ppm and 1.62 ± 1.88 ppm for the Orbitrap and the Q-TOF, respectively; however, individual measurements were ± 5 ppm for the Orbitrap and greater than 10 ppm for the Q-TOF. Relative isotopic abundance measurements for A + 1 were within 5% of the theoretical value if the intensity of the monoisotopic peak was greater than 1E7 for the Orbitrap and 1E5 for the Q-TOF, where an increase in error is observed with a decrease in intensity. Furthermore, complicating factors were found in the data that would impact automated data analysis strategies, including coeluting species that interfere with detectability and relative isotopic abundance measurements. The implications of these findings will be discussed with an emphasis on reasonable expectations from these instruments, guidelines for experimental workflows, data analysis considerations, and software design for non-targeted analyses. PMID:24729191

Knolhoff, Ann M; Callahan, John H; Croley, Timothy R



Resolving Isotopic Fine Structure to Detect and Quantify Natural Abundance- and Hydrogen/Deuterium Exchange-Derived Isotopomers  

PubMed Central

Hydrogen/deuterium exchange (HDX) mass spectrometry (MS) is used for analyzing protein dynamics, protein folding/unfolding, and molecular interactions. Until this study, HDX MS experiments employed mass spectral resolving powers that afforded only one peak per nominal mass in a given peptide’s isotope distribution, and HDX MS data analysis methods were developed accordingly. A level of complexity that is inherent to HDX MS remained unaddressed, namely, various combinations of natural abundance heavy isotopes and exchanged deuterium shared the same nominal mass and overlapped at previous resolving powers. For example, an A + 2 peak is comprised of (among other isotopomers) a two-2H-exchanged/zero-13C isotopomer, a one-2H-exchanged/one-13C isotopomer, and a zero-2H-exchanged/two-13C isotopomer. Notably, such isotopomers differ slightly in mass as a result of the ~3 mDa mass defect between 2H and 13C atoms. Previous HDX MS methods did not resolve these isotopomers, requiring a natural-abundance-only (before HDX or “time zero”) spectrum and data processing to remove its contribution. It is demonstrated here that high-resolution mass spectrometry can be used to detect isotopic fine structure, such as in the A + 2 profile example above, deconvolving the isotopomer species resulting from deuterium incorporation. Resolving isotopic fine structure during HDX MS therefore permits direct monitoring of HDX, which can be calculated as the sum of the fractional peak magnitudes of the deuterium-exchanged isotopomers. This obviates both the need for a time zero spectrum as well as data processing to account for natural abundance heavy isotopes, saving instrument and analysis time. PMID:24328359

Liu, Qian; Easterling, Michael L.; Agar, Jeffrey N.



Carbon stable isotopes as indicators of coastal eutrophication.  


Coastal ecologists and managers have frequently used nitrogen stable isotopes (delta15N) to trace and monitor sources of anthropogenic nitrogen (N) in coastal ecosystems. However, the interpretation of delta15N data can often be challenging, as the isotope values fractionate substantially due to preferential retention and uptake by biota. There is a growing body of evidence that carbon isotopes may be a useful alternative indicator for eutrophication, as they may be sensitive to changes in primary production that result from anthropogenic nutrient inputs. We provide three examples of systems where delta13C values sensitively track phytoplankton production. First, earlier (1980s) mesocosm work established positive relationships between delta13C and dissolved inorganic nitrogen and dissolved silica concentrations. Consistent with these findings, a contemporary mesocosm experiment designed to replicate a temperate intertidal salt marsh environment also demonstrated that the system receiving supplementary nutrient additions had higher nutrient concentrations, higher chlorophyll concentrations, and higher delta13C values. This trend was particularly pronounced during the growing season, with differences less evident during senescence. And finally, these results were replicated in the open waters of Narragansett Bay, Rhode Island, USA, during a spring phytoplankton bloom. These three examples, taken together with the pre-existing body of literature, suggest that, at least in autotrophic, phytoplankton-dominated systems, delta13C values can be a useful and sensitive indicator of eutrophication. PMID:24834733

Oczkowski, Autumn; Markham, Erin; Hanson, Alana; Wigand, Cathleen



A history of methane hydrate release and formation from the detailed carbon isotope stratigraphy of the apticore  

NASA Astrophysics Data System (ADS)

Oceanic Anoxic Event 1a (OAE 1a) is the longest and most pronounced OAE to take place on Earth in the past 200 m.y. Detailed ?13C records through expanded marine sections of OAE 1a, known in Italy as the Selli Event, present Earth Scientists with a number of mysteries to explain. Initially, marine sediments from around the globe became dramatically enriched in organic carbon and the carbon isotope record becomes sharply negative. Second, as the organic rich deposition continues, the global carbon isotopic record does not move above the initial values, as would be expected, for hundreds of thousands of years. And finally, as the excess organic carbon concentrations decline in marine sediments around the globe, only then does the carbon isotope record move to significantly positive values and persists at these unusual levels for more than a million years. In all, three of these phases in the ?13C record appear to contradict the sedimentary record. Here we can create a working hypothesis using a combination of stratigraphic records with outstanding age control from a cored section in northern Italy and a stable carbon isotope box model for the global ocean. The initial conundrum, the negative shift that begins the OAE, has been associated with the injection of isotopically negative carbon (-60 ppm) into the ocean/atmosphere system via the melting of marine methane hydrates (an approximate input of 1664Gt of methane over 65,000 years). The second phase is explained here by a slow "bleed" of methane from clathrates into the exogenic system for a million years in a "super green house" world. This accounts for a further 6830Gt of methane release. The third phase is the direct result of the end of the methane release episode. We suggest that in the million years following the OAE, the relatively labile and abundant organic matter in the shallowly buried organic carbon rich sediments was the source for about 8800Gt of new methane hydrate, which is then stored in the overlying hemipelagic sediment. This suggestion, along with a syncronous cooling in the ocean at the time, could explain the extended positive ?13C interval. This hypothesis can serve as a more general model to explain positive carbon isotope excursions that follow OAE emplacement.

Opdyke, B.; Erba, E.; Larson, R.; Herbert, T.



Carbon allocation and carbon isotope fluxes in the plant-soil-atmosphere continuum: a review  

NASA Astrophysics Data System (ADS)

The terrestrial carbon (C) cycle has received increasing interest over the past few decades, however, there is still a lack of understanding of the fate of newly assimilated C allocated within plants and to the soil, stored within ecosystems and lost to the atmosphere. Stable carbon isotope studies can give novel insights into these issues. In this review we provide an overview of an emerging picture of plant-soil-atmosphere C fluxes, as based on C isotope studies, and identify processes determining related C isotope signatures. The first part of the review focuses on isotopic fractionation processes within plants during and after photosynthesis. The second major part elaborates on plant-internal and plant-rhizosphere C allocation patterns at different time scales (diel, seasonal, interannual), including the speed of C transfer and time lags in the coupling of assimilation and respiration, as well as the magnitude and controls of plant-soil C allocation and respiratory fluxes. Plant responses to changing environmental conditions, the functional relationship between the physiological and phenological status of plants and C transfer, and interactions between C, water and nutrient dynamics are discussed. The role of the C counterflow from the rhizosphere to the aboveground parts of the plants, e.g. via CO2 dissolved in the xylem water or as xylem-transported sugars, is highlighted. The third part is centered around belowground C turnover, focusing especially on above- and belowground litter inputs, soil organic matter formation and turnover, production and loss of dissolved organic C, soil respiration and CO2 fixation by soil microbes. Furthermore, plant controls on microbial communities and activity via exudates and litter production as well as microbial community effects on C mineralization are reviewed. A further part of the paper is dedicated to physical interactions between soil CO2 and the soil matrix, such as CO2 diffusion and dissolution processes within the soil profile. Finally, we highlight state-of-the-art stable isotope methodologies and their latest developments. From the presented evidence we conclude that there exists a tight coupling of physical, chemical and biological processes involved in C cycling and C isotope fluxes in the plant-soil-atmosphere system. Generally, research using information from C isotopes allows an integrated view of the different processes involved. However, complex interactions among the range of processes complicate or currently impede the interpretation of isotopic signals in CO2 or organic compounds at the plant and ecosystem level. This review tries to identify present knowledge gaps in correctly interpreting carbon stable isotope signals in the plant-soil-atmosphere system and how future research approaches could contribute to closing these gaps.

Brüggemann, N.; Gessler, A.; Kayler, Z.; Keel, S. G.; Badeck, F.; Barthel, M.; Boeckx, P.; Buchmann, N.; Brugnoli, E.; Esperschütz, J.; Gavrichkova, O.; Ghashghaie, J.; Gomez-Casanovas, N.; Keitel, C.; Knohl, A.; Kuptz, D.; Palacio, S.; Salmon, Y.; Uchida, Y.; Bahn, M.



Seasonality of Leaf Carbon Isotopic Composition and Leaf Water Isotopic Enrichment in a Mixed Evergreen Forest in Southern California  

NASA Astrophysics Data System (ADS)

Leaf carbon isotopic composition and leaf water isotopic enrichment reflect physiological processes and are important for linking local and regional scale processes to global patterns. We investigated how seasonality affects the isotopic composition of bulk leaf carbon, leaf sugar carbon, and leaf water hydrogen under a Mediterranean climate. Leaf and stem samples were collected monthly from four tree species (Calocedrus decurrens, Pinus lambertiana, Pinus ponderosa, and Quercus chrysolepis) at the James San Jacinto Mountain Reserve in southern California. Mean monthly bulk leaf carbon isotopic composition varied from -34.5 % in P. ponderosa to -24.7 % in P. lambertiana and became more depleted in 13C from the spring to the summer. Mean monthly leaf sugar varied from -29.3 % in P. ponderosa to -21.8 % in P. lambertiana and was enriched in 13C during the winter, spring and autumn, but depleted during the mid-summer. Leaf water hydrogen isotopic composition was 28.4 to 68.8 % more enriched in deuterium than source water and this enrichment was greater as seasonal drought progressed. These data indicate that leaf carbon and leaf water hydrogen isotopic composition provide sensitive measures that connect plant physiological processes to short-term climatic variability.

Santiago, L. S.; Sickman, J. O.; Goulden, M.; DeVan, C.; Pasquini, S. C.; Pivovaroff, A. L.



Isotope Tutorial (title provided or enhanced by cataloger)  

NSDL National Science Digital Library

This isotope tutorial explains what isotopes are and what units are used to express them, how measurements of isotopes are made, and how natural variation in stable isotope abundances come about. The site describes processes affecting isotope ratios such as photosynthesis, evapotranspiration, and respiration; biosphere-atmosphere exchange of isotopes in water and carbon; and how stable isotopes are used to study environmental history. There is information on courses in stable isotopes and the Biosphere - Atmosphere Stable Isotope Network (BASIN) project aimed at improving understanding of carbon cycle processes at the ecosystem, regional, and global scale. Links are provided to analytical labs.

Pataki, Diane


Remote Detection of Carbon Stable Isotope of CO2 for Carbon Sequestration  

NASA Astrophysics Data System (ADS)

Carbon storage in geologic formations is one method to prevent carbon dioxide (CO2), produced by fossil fuel combustion, from entering the Earth's atmosphere. The monitoring, verification and accounting (MVA) of geologically sequestered CO2 is critical to measure the operation and functioning of a geologic storage site. Surface monitoring techniques need to identify seepage from the sequestration reservoir at or below ambient CO2 concentrations. The Zero Emissions Research & Technology (ZERT) group at Montana State University established a field test site where controlled amounts of CO2 are released to test the performance of CO2 detection instruments and measurement techniques. The field site allows a controlled flow rate of CO2 to be released into the near surface, just below the water table, through a 100 m long horizontal pipe. In July of 2009, a release was conducted, with a uniform flow rate of 0.2 tons per day, and the seepage rate was measured. The carbon stable isotope ratio of CO2 is a sensitive diagnostic signature to distinguish between anthropogenic and natural sources of CO2. However, natural concentrations of 13C16O2 are approximately 100 times smaller than 12C16O2. Frequency-modulated spectroscopy (FMS) is an ultra-sensitive technique developed to detect the CO2 stable carbon isotopes. An instrument has been developed that uses this FMS technique and an integrated volume over a long, open-air path to detect changes in the carbon isotope ratio. This paper will briefly describe the FMs technique and present results from instrument deployment to the ZERT field site to monitor the 13C16O2/12C16O2 stable isotope ratio. LA-UR 09-05648

Humphries, S. D.; Clegg, S. M.; Fessenden, J. E.; Dobeck, L.; Spangler, L.



A Widely Tunable Infrared Laser Spectrometer for Measurements of Isotopic Ratios of Carbon Cycle Gases  

SciTech Connect

The atmospheric abundances of carbon dioxide and methane have increased dramatically during the industrial era. Measurements of the isotopic composition of these gases can provide a powerful tool for quantifying their sources and sinks. This report describes the development of a portable instrument for isotopic analysis CO{sub 2} and CH{sub 4} using tunable infrared laser absorption spectroscopy. This instrument combines novel optical design and signal processing methods with a widely tunable mid-infrared laser source based on difference frequency generation (DFG) which will can access spectral regions for all the isotopes of CO{sub 2} and CH{sub 4} with a single instrument. The instrument design compensates for the large difference in concentration between major and minor isotopes by measuring them with path lengths which differ by a factor of 100 within the same multipass cell. During Phase I we demonstrated the basic optical design and signal processing by determining {sup 13}CO{sub 2} isotopic ratios with precisions as small as 0.2{per_thousand} using a conventional lead salt diode laser. During Phase II, the DFG laser source was coupled with the optical instrument and was demonstrated to detect {sup 13}CH{sub 4}/{sup 12}CH{sub 4} ratios with a precision of 0.5{per_thousand} and an averaging time of 20 s using concentrated methane in air with a mixing ratio of 2700 ppm. Methods for concentrating ambient air for isotopic analysis using this technique have been evaluated. Extensions of this instrument to other species such as {sup 13}CO{sub 2}, C{sup 18}OO, and CH{sub 3}D are possible by substituting lasers at other wavelengths in the DFG source module. The immediate commercial application of this instrument will be to compete with existing mass spectrometric isotope instruments which are expensive, large and relatively slow. The novel infrared source developed in this project can be applied to the measurement of many other gas species and will have wide application in atmospheric monitoring, industrial process control, and medical research and diagnostic development.

Joanne H. Shorter; J. Barry McManus; David D. Nelson; Charles E. Kolb; Mark S. Zahniser; Ray Bambha; Uwe Lehmann; Tomas Kulp; Stanley C. Tyler



Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria  

Microsoft Academic Search

Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by

Dennis D. Coleman; M SCHOELL



Heat conduction of single-walled carbon nanotube isotope-superlattice structures: A molecular dynamics study  

E-print Network

1 Heat conduction of single-walled carbon nanotube isotope-superlattice structures: A molecular-mail address: Heat conduction of single-walled carbon nanotubes (SWNTs) isotope and junctions, which alter the heat conduction. In general, these nanoscale impurities, having scales comparable

Maruyama, Shigeo


Stable Isotopes James R Ehleringer and Thure E Cerling  

E-print Network

for introduction into the mass spectrometer. The most commonly used approaches involve introducing hydrogen as H2 Element Isotope Abundance (%) Hydrogen 1 H 99.985 2 H 0.015 Carbon 12 C 98.89 13 C 1.11 Nitrogen 14 N 99? Of particular interest for global change studies are vari- ations in the isotopic abundances of hydrogen, carbon

Ehleringer, Jim


The Abundance of Very Large Hydrocarbons and Carbon Clusters in the Diffuse Interstellar Medium  

NASA Astrophysics Data System (ADS)

Two current gas-phase chemical models of interstellar clouds have been extended to include hydrocarbons and bare carbon clusters through 64 carbon atoms in size. The new molecules comprise linear, monocyclic, tricyclic, and fullerene/ane species but do not include polycyclic aromatic hydrocarbons (PARs). The reaction networks used to produce and destroy these species have been adopted from a laboratory synthesis of fullerenes. The models have been used to investigate the chemistry of complex molecules in a number of dispersive clouds, which begin as dense clouds but end up as diffuse material. The calculated abundances of large molecules are discussed in terms of candidates for the carriers of the diffuse interstellar bands (DIBs). We find that both gas-phase models utilized can produce large abundances of 64 carbon atom species, considered to represent molecules of this size and larger. Such species are DIB candidates only if the abundances are not spread too thinly over many species. One of the two gas-phase models used leads to large abundances of fullerenes and fulleranes. If this model is accurate, the fullerenes/anes represent reasonable candidates for the carriers of the DIBs. If small hydrocarbon "seeds" are assumed to be present on dust particles and to photodesorb during cloud dispersion, we find that large abundances of linear and monocyclic hydrocarbons can also be produced and maintained via gas-phase chemistry, so that these molecules become additional DIB-carrier candidates.

Bettens, R. P. A.; Herbst, Eric



Stable carbon isotope values document how a Late Holocene expansion in grasslands impacted vertebrates in northwestern Madagascar  

NASA Astrophysics Data System (ADS)

Madagascar is home to some of the world's most distinctive plants and animals. Unfortunately, forest loss and habitat degradation has had a dramatic impact on both floral and faunal communities. Here we use carbon isotope values in radiocarbon-dated bones to examine how the vertebrate community at Anjohibe Cave, northwestern Madagascar, responded to a Late Holocene increase in C4 grass abundance. Our data demonstrate that major changes in the vegetation and animal community are recent phenomena at Anjohibe. Extinct lemurs and hippopotamuses were present until ca. 1500 years ago. These taxa relied exclusively on C3 resources. Locally extirpated fauna were present until 300 years ago. The majority of these species also relied on C3 resources. Their presence strongly suggests that the region surrounding the cave was more wooded than it is now, possibly as recently as 300 years ago. All introduced individuals are modern. Rats (Rattus sp.), shrews (Suncus murinus), and the giant frog Hoplobatrachus cf. tigrinus, have remarkably high carbon isotope values, implicating substantial ingestion of C4 foods. It is possible that grass abundance has increased dramatically in the past 100 years. Alternatively, opportunistically granivorous rats and shrews may selectively consume seeds from C4 grasses. In agreement with previous studies, stable isotope data reveal details of vegetation and faunal turnover in Northwestern Madagascar. Grasses have increased, forest dwelling species have vanished, and introduced taxa are exploiting a novel niche.

Crowley, B. E.; Samonds, K.



Carbon isotope ratios are correlated with irradiance levels in the Panamanian orchid Catasetum viridiflavum  

Microsoft Academic Search

Carbon isotope composition (13C\\/12C) in leaves of the Panamanian epiphytic orchid Catasetum viridiflavum were measured on individuals growing in canopies over a water surface to distinguish the effects of a change in source CO2 and humidity from those of intercellular CO2 concentration in determining isotopic composition. Carbon isotope ratios were observed to vary by over 4 in response to changes

Jess K. Zimmerman; James R. Ehleringer



Evidence for recurrent Early Triassic massive volcanism from quantitative interpretation of carbon isotope fluctuations  

Microsoft Academic Search

Carbon cycle disturbance associated with mass extinction at the end of the Permian Period continued through the Early Triassic, an interval of approximately 5 million years. Coincidence of carbon cycle stabilization with accelerated Middle Triassic biotic recovery suggests a link between carbon cycling and biodiversity, but the cause of Early Triassic carbon isotope excursions remains poorly understood. Previous modeling studies have

Jonathan L. Payne; Lee R. Kump



Carbonate dissolution and temporal abundances of Foraminifera in Long Island Sound sediments  

Microsoft Academic Search

The dynamics of benthic Foraminifera assemblages can be used to examine carbonate dissolution processes in nearshore sediments and as a general assay of physical-chemical factors affecting survival of juvenile benthos. Abundances of total Foraminifera (live and dead) fluctuate regularly throughout the year in Long Island Sound (LIS) mud deposits, with highest numbers in spring-summer and lowest in winter. Essentially all




Abundance anomalies of carbon and nitrogen in the IUE spectra of Algol-type interacting binaries  

NASA Technical Reports Server (NTRS)

There are two primary ways in which the products of nucleosynthesis in stellar interiors may appear at the surface of a star. These are mixing and/or loss of the original unburned stellar envelope. In interacting binaries, overflow can contribute dramatically to envelope loss. The simplest abundance anomalies to be expected from nuclear burning of hydrogen, helium, or carbon would be under or over abundances H, He, C, O, Ne, and Mg. In addition, it is expected that carbon is initially severely depleted, while nitrogen is enhanced during hydrogen burning via the CNO cycle in stars above two solar masses. Other, more subtle anomalies are also expected, and elements heavier than magnesium can be created during very late evolution by nuclear burning in massive stars. Consequently, it is expected that abundance anomalies of various kinds should occur in interacting binaries where one or both stars have lost significant amounts of mass.

Mccluskey, Carolina P. S.



Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates  

NASA Technical Reports Server (NTRS)

Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Ming, D. W.; Gibson, E. K.



Modelling carbon isotope composition of dissolved inorganic carbon and methane in marine porewaters  

NASA Astrophysics Data System (ADS)

Carbon isotope compositions of dissolved inorganic carbon (DIC) and methane (CH4) in marine sedimentary porewaters at near surface temperatures show extremely large variation in apparent fractionation covering a range from -100 ‰ to +30 ‰. This fractionation is essentially the result of microbial activity, but the mechanisms and factors controlling this fractionation are still incompletely understood. This study provides a reaction transport model approach to evaluate the effects of the most important processes and factors on carbon isotope distribution with the goal to better understand carbon isotope distribution in modern sediment porewaters and in the geological record. Our model results show that kinetic fractionation during methanogenesis, both through the acetoclastic and autotrophic pathways, results in a nearly symmetrical distribution of ?13C values in DIC and CH4 with respect to the isotope value of buried organic matter. An increased fractionation factor during methanogenesis leads to a larger difference between ?13CDIC and ?13CCH4. Near the sulphate methane transition zone, DIC is more depleted in 13C due to diffusive mixing with DIC produced by anaerobic oxidation of methane (AOM) and organoclastic sulphate reduction. The model also shows that an upward decrease in ?13CCH4 near the SMT can only be caused by equilibrium fractionation during AOM including a backward "leakage" of carbon from DIC to CH4 through the enzymatic pathway. However, this effect of reversibility has no influence on the DIC pool as long as methane is completely consumed at the SMT. Only a release of methane at the sediment-water interface, due to a fraction of the methane escaping re-oxidation, results in a small shift towards more positive ?13CDIC values. Methane escape at the SMT is possible if either the methane flux is too high to be entirely oxidized by AOM, or if bubbles of methane gas by-pass the sulphate reduction zone and escape episodically into the water column. A small but significant isotope effect is also caused by differential diffusion of the 12C and 13C isotopes of CH4 leading to somewhat more positive ?13CCH4 values, while DIC remains unaffected by this process. The consideration of all these effects allows a relatively good reproduction of ?13CDIC and ?13CCH4 profiles in marine sediments in diffusive systems. However, the model cannot reproduce profiles measured in seep environments, where CH4 and DIC profiles are perturbed by upward advecting, possibly thermogenic methane from greater depth. The model is now available to be applied for non-steady state systems, which ultimately will help to understand past dynamics of ?13C compositions and their diagenetic records as a result of changing microbial activity.

Meister, Patrick; Liu, Bo; Khalili, Arzhang; Barker Jørgensen, Bo



Oxygen-18 Carbon Dioxide Isotope Ratio in Mars Atmosphere  

NASA Astrophysics Data System (ADS)

The determination of isotopic ratios on Mars is important to the study of atmospheric evolution [1]. The relative abundance of isotopes of CO2 provides insight into the loss of Mars' primordial atmosphere. Isotopic ratios also provide markers in the study of geochemistry of Mars meteorites and future returned samples formed in equilibrium with ambient atmosphere, and are probes of biogenic and abiotic chemistry, which differ in isotope fractionation. Due to its lesser gravity and relatively thin residual atmosphere, Mars' atmosphere should be enriched in heavy isotopes [1]. However Viking [2] results indicated an Earth-like singly substituted oxygen-18 CO2 isotopic ratio, 18OCO/OCO, with ?18O = 0±50‰ relative to Vienna Standard Mean Ocean Water (VSMOW). By comparison, isotopic ratios in Earth atmospheric CO2 are not uniquely defined due to seasonal and biotic variability, but have a range 0-41‰ relative to VSMOW [3, 4]. Phoenix lander TEGA [3] measurements found a modest enrichment of ?18O = 31.0±5.7‰. Only the Viking and Phoenix landers have carried a mass spectrometer to Mars, so far, until the arrival of Mars Science Laboratory in August 2012. Using ground-based spectroscopic techniques Krasnopolsky et al. [5] also found modest enrichment ?18O = 18±18‰. We present results from fully resolved spectroscopic measurements near 10.6 ?m of both the normal and singly substituted oxygen- 18 CO2 lines, taken with the Goddard Space Flight Center Heterodyne Instrument for Planetary Winds And Composition (HIPWAC) at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. Measurements with spectral resolving power ?/??=107 were obtained in October 2007 with an instantaneous field-of-view on the planet of ~1 arcsec, at the locations shown in Fig. 1 as open squares. The solid and broken line tracks show Mars SPICAM measurements of ozone corresponding to ozone measurements also obtained with HIPWAC and shown as hatched and solid regions [6]. Figure 1: Locations of measured 18O12C16O fractional abundance on Mars (open squares). The colored tracks are Mars Express SPICAM measurements of ozone; the solid and hatched areas show contemporaneous HIPWAC measurements of ozone [6]. Figure 2 illustrates the CO2 normal-isotope and O-18 isotopologue lines measured on Mars at ~1 MHz (0.0003 cm-1) spectral resolution. The strong absorption line constrains the temperature simultaneously at the position of the measurement. The narrow mesospheric non- LTE line emission is also seen at the core of the absorption. The standard Mars Global Surveyor temperature profile was used to obtain the modeled emergent spectrum in blue. It clearly does not fit as well as the thermal profile retrieved from the CO2 absorption line profile (red fit). EPSC Abstracts Vol. 7 EPSC2012-432 2012 European Planetary Science Congress 2012 c Author(s) 2012 EPSC European Planetary Science Congress Figure 2: HIPWAC measurements of CO2 spectrum on Mars near 10.5 ?m. The broad absorption retrieves the temperature. The fitted model spectra correspond to using the standard MGS thermal profile (blue), and our retrieved profile (red). The fit to the isotopic line is excellent and yields ?18O = +9±14‰. Radiative-transfer software developed in-house at GSFC to be compatible with very high spectral resolving power [7] was used to obtain the temperature profile and spectral fit. The fit on the 952.8629 cm-1 18OC16O line retrieves ?18O = +9±14‰. There appears to be no significant enhancement in the average over the extended region measured. Additional, more global, measurements were acquired in May 2012 and these data are being analyzed. These and additional high spectral resolution ground-based global measurements of ?18O can investigate Mars' atmospheric history; help define Mars Science Laboratory (MSL) protocols to sample isotopic ratios diurnally and seasonally, throughout its prime mission; and investigate possible meridional variability due to mass-fractionation in the polar freeze-sublimate cycle, similar to effects in terrestrial polar ice formation [

Kostiuk, T.; Livengood, T. A.; Hewagama, T.; Smith, R.; Fast, K. E.; Annen, J.; Sonnabend, G.; Sornig, M.



Neodymium isotopes in biogenic carbonates: reliable archives of ?Nd  

NASA Astrophysics Data System (ADS)

Neodymium isotope (143Nd/144Nd) compositions from dispersed authigenic ferromanganese oxide fraction in marine sediments, ferromanganese crusts, foraminiferal shells and fossil fish teeth are employed to trace provenance and water mass mixing in the past, having the advantage of not being fractionated by biological processes in the water column. In the modern ocean the different water masses ultimately derive their ?Nd values through continental weathering, erosion and particle-seawater interactions. This geochemical tracer has been only recently applied to scleractinian deep-water coral skeletons sourced from various sites and depths in the Atlantic ocean. Aragonitic corals can be precisely dated by U-series, potentially providing century-long records of intermediate and bathyal zone variability at sub-decadal resolution. Motivated by these recent findings we have investigated the Nd isotopic compositions of living specimens of various calcifying organisms collected in two key locations of the Mediterranean Sea and in the Southern Ocean. In particular, we analyzed several specimens of the aragonitic deep-water corals Desmophyllum dianthus, Lophelia pertusa, Madrepora oculata, Flabellum impensum, the temperate coral Cladocora caespitosa, the calcitic gorgonian coral Corallium rubrum, the bivalves Glans aculeata and Karnekampia bruei and the polychate Serpula vermicularis. Most of the samples were retrieved from the Strait of Sicily and the Southern Adriatic Sea at different water depths. Ten seawater samples from three new profiles in the Mediterranean were also collected at the same locations and depths, offering a unique opportunity to compare the Nd isotopic composition of biogenic carbonates directly with the surrounding ambient seawater. The Mediterranean Sea is particularly suited for this comparison exercise since it is characterized by water masses displaying a large range of ?Nd values, from -10.5 in the Western Mediterranean to -4.8 in the Eastern Mediterranean. In addition, specimens of living and fossil Desmophyllum dianthus and Lophelia pertusa were analysed for Nd concentration at fine-scale resolution using a laser ablation ICP-MS, with the aim to understand the effect of the coral microstructures on the Nd distribution. Nd isotopes in the modern biogenic carbonates analyzed thus far match the surrounding seawater and unless diagenesis is significant, we expect that these calcifying organisms can serve as reliable archives for past ocean circulation.

Montagna, P.; Goldstein, S. L.; Taviani, M.; Frank, N.; McCulloch, M. T.



Stable isotope analysis of dissolved carbon species of Hot Lake, WA  

NASA Astrophysics Data System (ADS)

Hot Lake is a hypersaline, meromictic lake in north-central Washington. The lake is epsomitic, with seasonably-variable salinity (.2 to 2 M magnesium sulfate) and produces carbonates and salt precipitates. The maximum depth of the lake is around 2.5 m, and below a thermocline there is intense solar heat retention in the monolimnion, often exceeding 50°C. Despite these extreme and variable conditions, a microbial mat of up to 1.5 cm thick thrives annually in Hot Lake. The mat is widespread throughout the lake at water depths (during our experiments) ranging from 60cm-140cm. It is comprised of a variety of cyanobacteria along with other autotrophic and heterotrophic bacteria. These populations are visibly stratified with four consistent laminae displaying differences in bacterial pigmentation. Many of the layers contain carbonate species, but the full relationship between the mat and the carbonate crystallization is not known. We are studying the microbial interactions and carbon cycling of the mat communities, using stable isotope analysis of the mat and the lake water, both in situ and ex situ. We are exploring the incorporation and movement of carbon in the mat, spatially and temporally, to understand the fixation mechanisms and metabolic processes at play in this environment. This was done primarily using stable isotope ratio mass spectrometry. The focus of this work is on the study and measurement of dissolved organic and inorganic carbon using a GasBench and IRMS setup, following methods adapted from Lang et al. (2012). To account for the unique chemistry of Hot Lake, trials on the effects of oxidation conditions and salinity were done on lab-synthesized samples to compare to Hot Lake results. The majority of lake water analyses were done in conjunction with a stable isotope probing (SIP) experiment, completed during two 24-hour periods at Hot Lake in June and July of 2013. The SIP experiments included ex situ incubations (in separate glass containers on the shore of the lake immediately after removal from the lake) under various conditions (with labeled and unlabeled substrate, in the presence and absence of daylight, with and without undermat sediment) performed as both constant labeling and pulse-chase experiments. We incubated mat sections in lake water (from equivalent depth to the collected mat) spiked either with 13C-labeled or natural abundance organic (acetate or glucose) or inorganic (bicarbonate) substrates. For those conditions in which inorganic carbon was added, we measured the DOC of the water in each condition to measure conversion from DIC to DOC and vice versa for consumption/conversion of DOC to DIC. By comparing the GasBench DIC/DOC results of these various conditions over the course of the experiments, we assessed carbon flow into and out of the mat around a daily cycle. The assessments were made using the ?13C values and data of the lake water samples from the IRMS in conjunction with bulk mat isotope values. Our data show significant interactions between DIC and DOC pools and allow us to estimate the daily balance between carbon fixation and remineralization mediated by the microbial mat.

Courtney, S.; Moran, J.; Cory, A. B.; Lindemann, S. R.; Fredrickson, J.



Carbon Isotope Ratio in 12 CO/ 13 CO toward Local Molecular Clouds with Near-Infrared High Resolution Spectroscopy of  

E-print Network

Carbon Isotope Ratio in 12 CO/ 13 CO toward Local Molecular Clouds with Near-Infrared ABSTRACT We report the carbon monoxide isotope ratio in local molecular clouds toward LkH#11; 101, AFGL 490 The main isotope of carbon ( 12 C) is a primary product of the 3 #11; process in the stellar

Usuda, Tomonori


New integrated stratigraphic data from Hungary and a global carbon isotope stack across the Jurassic-Cretaceous boundary  

NASA Astrophysics Data System (ADS)

Late Jurassic-Early Cretaceous carbon isotope stratigraphies derived from measured sections in the Bakony and the Gerecse Mts. (Hungary), constrained by ammonite, belemnite and calpionellid biostratigraphy together with magnetostratigraphy are presented. We evaluate whether a consistent pattern in carbon (and oxygen) isotope variation can be established, particularly with respect to the Jurassic-Cretaceous boundary. We also assess the possible controls on carbon isotope variation and the correlation potential. Oxygen isotopes point to warming through this interval. We observe a decrease in carbon isotopes through the Late Jurassic, consistent with carbon isotope stratigraphies of the Western Tethys. A change to more positive carbon isotope values in the Early Cretaceous is manifest in the Valanginian Weissert event, potentially reflecting a change to increasingly nutrient-rich conditions and enhanced carbon cycling. Biostratigraphic and magnetostratigraphic data allow us to accurately place the low point seen in the carbon isotope curve within these schemes. Locally a carbon isotope minimum appears in the upper part of magneto subzone M19n2n and towards the middle of calpionellid Zone B (i.e. the Alpina Subzone), but not resolved in the carbon isotope stack from across Tethys and the Atlantic. Aside from the well-defined Valanginian event, chemostratigraphic correlation across the Jurassic-Cretaceous boundary using the carbon isotope record is challenging due to relatively stable carbon isotope values resulting in a curve with a slope too slight.

Price, Gregory; F?zy, István; Pálfy, József



The magnesium isotope record of cave carbonate archives  

NASA Astrophysics Data System (ADS)

Here we explore the potential of magnesium (?26Mg) isotope time-series data as continental climate proxies in speleothem calcite archives. For this purpose, a total of six Pleistocene and Holocene stalagmites from caves in Germany, Morocco and Peru and two flowstones from a cave in Austria were investigated. These caves represent the semi-arid to arid (Morocco), the warm-temperate (Germany), the equatorial-humid (Peru) and the cold-humid (Austria) climate zones. Changes in the calcite magnesium isotope signature with time are compared against carbon and oxygen isotope records from these speleothems. Similar to other proxies, the non-trivial interaction of a number of environmental, equilibrium and disequilibrium processes governs the ?26Mg fractionation in continental settings. These include the different sources of magnesium isotopes such as rainwater or snow as well as soil and host rock, soil zone biogenic activity, shifts in silicate versus carbonate weathering ratios and residence time of water in the soil and karst zone. Pleistocene stalagmites from Morocco show the lowest mean ?26Mg values (GDA: -4.26 ± 0.07‰ and HK3: -4.17 ± 0.15‰), and the data are well explained in terms of changes in aridity over time. The Pleistocene to Holocene stalagmites from Peru show the highest mean value of all stalagmites (NC-A and NC-B ?26Mg: -3.96 ± 0.04‰) but only minor variations in Mg-isotope composition, which is consistent with the rather stable equatorial climate at this site. Holocene stalagmites from Germany (AH-1 mean ?26Mg: -4.01 ± 0.07‰; BU 4 mean ?26Mg: -4.20 ± 0.10‰) suggest changes in outside air temperature was the principal driver rather than rainfall amount. The alpine Pleistocene flowstones from Austria (SPA 52: -3.00 ± 0.73‰; SPA 59: -3.70 ± 0.43‰) are affected by glacial versus interglacial climate change with outside air temperature affecting soil zone activity and weathering balance. Several ?26Mg values of the Austrian and two ?26Mg values of the German speleothems are shifted to higher values due to sampling in detrital layers (Mg-bearing clay minerals) of the speleothems. The data and their interpretation shown here highlight the potential but also the limitations of the magnesium isotope proxy applied in continental climate research. An obvious potential lies in its sensitivity for even subtle changes in soil-zone parameters, a hitherto rather poorly understood but extremely important component in cave archive research. Limitations are most obvious in the low resolution and high sample amount needed for analysis. Future research should focus on experimental and conceptual aspects including quantitative and well-calibrated leaching and precipitation experiments.

Riechelmann, S.; Buhl, D.; Schröder-Ritzrau, A.; Riechelmann, D. F. C.; Richter, D. K.; Vonhof, H. B.; Wassenburg, J. A.; Geske, A.; Spötl, C.; Immenhauser, A.



The magnesium isotope record of cave carbonate archives  

NASA Astrophysics Data System (ADS)

Here we explore the potential of time-series magnesium (?26Mg) isotope data as continental climate proxies in speleothem calcite archives. For this purpose, a total of six Pleistocene and Holocene stalagmites from caves in Germany, Morocco and Peru and two flowstones from a cave in Austria were investigated. These caves represent the semi-arid to arid (Morocco), the warm-temperate (Germany), the equatorial-humid (Peru) and the cold-humid (Austria) climate zones. Changes in the calcite magnesium isotope signature with time are placed against carbon and oxygen isotope records from these speleothems. Similar to other proxies, the non-trivial interaction of a number of environmental, equilibrium and non-equilibrium processes governs the ?26Mg fractionation in continental settings. These include the different sources of magnesium isotopes such as rain water or snow as well as soil and hostrock, soil zone biogenic activity, shifts in silicate versus carbonate weathering ratios and residence time of water in the soil and karst zone. Pleistocene stalagmites from Morocco show the lowest mean ?26Mg values (GDA: -4.26 ± 0.07 ‰ and HK3: -4.17 ± 0.15 ‰) and the data are well explained in terms of changes in aridity over time. The Pleistocene to Holocene stalagmites from Peru show the highest mean value (NC-A and NC-B ?26Mg: -3.96 ± 0.04 ‰) but only minor variations in Mg-isotope composition, which is in concert with the rather stable equatorial climate at this site. Holocene stalagmites from Germany (AH-1 mean ?26Mg: -4.01 ± 0.07 ‰; BU 4 mean ?26Mg: -4.20 ± 0.10 ‰) record changes in outside air temperature as driving factor rather than rainfall amount. The alpine Pleistocene flowstones from Austria (SPA 52: -3.00 ± 0.73 ‰; SPA 59: -3.70 ± 0.43 ‰) are affected by glacial versus interglacial climate change with outside air temperature affecting soil zone activity and weathering balance. Several data points in the Austrian and two data points in the German speleothems are shifted to higher values due to sampling in detrital layers (Mg-bearing clay minerals) of the speleothems. The data and their interpretation shown here highlight the potential but also the limitations of the magnesium isotope proxy applied in continental climate research. An obvious potential lies in its sensitivity for even subtle changes in soil-zone parameters, a hitherto rather poorly understood but extremely important component in cave archive research. Limitations are most obvious in the low resolution and high sample amount needed for analysis. Future research should focus on experimental and conceptual aspects including quantitative and well calibrated leaching and precipitation experiments.

Riechelmann, S.; Buhl, D.; Schröder-Ritzrau, A.; Riechelmann, D. F. C.; Richter, D. K.; Vonhof, H. B.; Wassenburg, J. A.; Geske, A.; Spötl, C.; Immenhauser, A.



Correlations Between Os Isotopic Composition and Trace Element Abundance in Chinese Cu-Ni Deposit Sulfides  

NASA Astrophysics Data System (ADS)

We have determined the Os isotopic composition (ID-MC-ICPMS) and trace element abundances (LA-ICPMS) in sulfide minerals from 4 Cu-Ni deposits in southern China. The samples separate into 2 groups based on Re/Os ratio. The high Re/Os deposits yield a 278 ± 35 Ma isochron (MSWD = 3.7) and an initial ? Os of 255. The low Re/Os deposits define a 278 ± 20 Ma isochron (MSWD = 15), and an initial ? Os of 49, showing that mineralization was contemporaneous, but the amount of crustal contamination and/or R-factor in the two groups was different. These differences and are also reflected in sulfide mineral trace element variations. Laser ablation shows that Re, Os, and Ir are in solid solution with pentlandite and pyrrhotite and Au and Pd are enriched in pentlandite over pyrrhotite. Pt was rarely observed above detection, but when present occurs as isolated Pt peaks. For the high Re/Os whole rock samples the average sulfide Re and Os concentration agree with the whole rock data, but in the low Re/Os whole rock samples the sulfide Re and Os are higher, suggesting that chalcopyrite with its Re/Os of >5 is an important mass balance component. Trace element modeling is complicated by the fact that Cu, Zn, Ga, As, Cd, Te, Ag, Au, Pb and Bi while occurring in solid solution with pentlandite and pyrrhotite are often present as sulfide mineral inclusions. Examination of ablation signals shows anti-correlation between some elements (e.g. Te and Pb) and that numerous off-set peaks also occur within single ablations. None-the-less, Ag tends to be enriched in pentlandite over pyrrhotite in the low Re/Os group and evenly distributed between the sulfides in the high Re/Os group. Cd, Pb and Bi are enriched in high Re/Os group sulfides suggesting that while the difference in initial ? Os can be modeled as variation in R-factor, the degree of radiogenicness of the initial ? Os in mafic-ultramafic ore deposits is ultimately controlled by the degree of crustal contamination.

Graham, S.; Griffin, W.; Barnes, S.; Begg, G.



Double-comparison method for mass spectrometric determination of hydrogen isotopic abundances  

Microsoft Academic Search

Hydrogen isotope ratio analysis is subject to interference from Hâ\\/sup +\\/, and the uncertainty in the Hâ\\/sup +\\/ correction is generally the limiting factor in the precision of hydrogen isotopic analyses. Mathematical modeling indicates that the precision of the analysis can be improved through the use of a double-comparison technique employing a second reference gas. In order to compare the

D. A. Schoeller; D. W. Peterson; J. M. Hayes



Near-infrared spectroscopy of M dwarfs. I. CO molecule as an abundance indicator of carbon  

NASA Astrophysics Data System (ADS)

Based on the near-infrared spectra of 42 M dwarfs, carbon abundances are determined from the ro-vibrational lines of the CO (2-0) band. We apply Teff values based on the angular diameters if available or use the Teff values in a log Teff-M3.4 relation (M3.4 is the absolute magnitude at 3.4 ?m based on the WISE W1 flux and the Hipparcos parallax) to estimate Teff values of objects for which angular diameters are unknown. Also, we discuss briefly the HR diagram of low-mass stars. On the observed spectrum of the M dwarf, the continuum is depressed by the numerous weak lines of H2O and only the depressed continuum or the pseudo-continuum can be seen. On the theoretical spectrum of the M dwarf, the true continuum can be evaluated easily but the pseudo-continuum can also be evaluated accurately thanks to the recent H2O line database. Then spectroscopic analysis of the M dwarf can be done by referring to the pseudo-continuum both on the observed and theoretical spectra. Since the basic principle of the spectroscopic analysis should be the same whether the true- or pseudo-continuum is referred to, the difficulty related to the continuum in cool stars can in principle be overcome. Then, the numerous CO lines can be excellent abundance indicators of carbon, since almost all the carbon atoms are in stable CO molecules which suffer little effect of the uncertainties in photospheric structure, and carbon abundances in late-type stars can best be determined in M dwarfs rather than in solar type stars. The resulting C/Fe ratios for most M dwarfs are nearly constant at about the solar value based on the classical high carbon abundance rather than on the recently revised lower value. This result implies that the solar carbon abundance is atypical for its metallicity among the stellar objects in the solar neighborhood if the downward revised carbon abundance is correct.

Tsuji, Takashi; Nakajima, Tadashi



On strontium isotopic anomalies and odd-A p-process abundances. [in solar system  

NASA Technical Reports Server (NTRS)

Several aspects of the nucleosynthesis of Sr isotopes are considered in an attempt to shed light on the problem of the Sr isotopic anomalies discovered in an inclusion of the Allende meteorite. Decomposition of the Sr isotopes into average r-, s-, and p-process nucleosynthetic classes is performed. It is suggested that the Allende inclusion most likely has an excess of s-process Sr and that the initial Sr-87/Sr-86 isotopic ratio is probably slightly more primitive than basaltic achondrites. The results also show that Sn-115 is mostly due to the r-process and that odd-A yields are very small. It is concluded that if the Sr anomaly in the inclusion is an average s enhancement, it argues somewhat in favor of a model of gas/dust fractionation of s and r isotopes during accumulation of the inclusion parent in the protosolar cloud.

Clayton, D. D.



Carbon isotopic evidence for methane hydrate instability during quaternary interstadials  


Large (about 5 per mil) millennial-scale benthic foraminiferal carbon isotopic oscillations in the Santa Barbara Basin during the last 60,000 years reflect widespread shoaling of sedimentary methane gradients and increased outgassing from gas hydrate dissociation during interstadials. Furthermore, several large, brief, negative excursions (up to -6 per mil) coinciding with smaller shifts (up to -3 per mil) in depth-stratified planktonic foraminiferal species indicate massive releases of methane from basin sediments. Gas hydrate stability was modulated by intermediate-water temperature changes induced by switches in thermohaline circulation. These oscillations were likely widespread along the California margin and elsewhere, affecting gas hydrate instability and contributing to millennial-scale atmospheric methane oscillations. PMID:10753115

Kennett; Cannariato; Hendy; Behl



Carbon isotopic enrichment in Titan's Tholins: implications for Titan's aerosols  

NASA Astrophysics Data System (ADS)

Since the discovery of the main composition of Titan s atmosphere many laboratory experiments have been carried out to mimic its chemical evolution and in particular the formation of the haze particles of this atmosphere Indeed the solid products obtained during these simulation experiments -- often named Titan s tholins -- are supposed to be analogues of Titan s aerosols and many studies have already been achieved on these tholins We have studied the possible isotopic fractionation of carbon during the processes involved in the formation of Titan s tholins using tholins obtained from different simulation experiments We will present the first results obtained on the isotopic ratios of 13 C 12 C measured on the analogues of Titan s aerosols synthesized in laboratory Measurement of delta 13 C leaded both on laboratory aerosols and on the initial gas mixture N 2 CH 4 98 2 used in the simulations doesn t show any evident deficit or enrichment of 13 C in comparison with 12 C in the aerosols synthesised compared to the initial gas mixture Preliminary retrieving of the data of the ACP instrument on the Huygens probe suggests that Titan s aerosols may present also no enrichment This allows us to go further in the analyses of the ACP data in comparison with the first conclusions newly published in Nature Isra e l et al Nature 2005

Nguyen, N.; Raulin, R.; Coll, C.; Derenne, D.; Szopa, S.; Israël, I.; Cernogora, C.; Bernard, B.


Carbon and hydrogen isotopic compositions of stratospheric methane: 2. Two-dimensional model results and implications for kinetic isotope effects  

Microsoft Academic Search

New high-precision measurements of the carbon and hydrogen isotopic compositions of stratospheric CH4 made on whole air samples collected aboard the NASA ER-2 aircraft are compared with results from the Lawrence Livermore National Laboratory 2-D model. Model runs incorporating sets of experimentally determined kinetic isotope effects (KIEs) for the reactions of CH4 with each of the oxidants OH, O(1D), and

M. C. McCarthy; K. A. Boering; A. L. Rice; S. C. Tyler; P. Connell; E. Atlas



Relationships between gas exchange and carbon isotope discrimination of Sitka x interior spruce introgressive genotypes and ribosomal DNA markers.  


Effects of hybridization on physiological performance were investigated in seven natural introgressive populations and one F(1) population of Sitka (Picea sitchensis (Bong.) Carr.) x interior spruce (P. glauca (Moench) Voss. x P. engelmannii Parry ex Engelm.). Each population was represented by a Sitka-interior spruce ribosomal DNA (Si rDNA) index that was calculated from the relative abundance of species-specific DNA polymorphisms. Gas exchange parameters were measured under well-watered conditions on current-year needle tissues, which were also analyzed for carbon isotope discrimination. Sitka spruce populations had higher gas exchange rates (net photosynthesis, stomatal conductance to water vapor), but lower carbon isotope discrimination values than interior spruce populations. The natural hybrid populations had intermediate values of these parameters consistent with their Si rDNA index. The F(1) population had gas exchange parameters resembling those of Sitka spruce populations, but its carbon isotope discrimination was skewed toward that of interior spruce populations. These results confirmed previous findings that physiological performance of introgressive hybrid spruce populations varied as their DNA constitution changed. PMID:12651325

Fan, Shihe; Grossnickle, Steven C.; Sutton, Ben C. S.



Carbon isotopic composition of Ambrosia and Artemisia pollen: assessment of a C?-plant paleophysiological indicator.  


There is limited evidence on how shifts in plant physiological performance influence vegetation variations in the paleorecord. To evaluate ?¹³C of pollen from C? plants as an indicator of community-level physiology, small quantities (10-30 grains) of untreated pollen and sporopollenin from herbarium specimens of Ambrosia (A. tomentosa and A. psilostachya) and Artemisia (A. frigida, A. ludoviciana and A. dracunculus), genera abundant in grassland pollen profiles, were isolated by micromanipulation. Their ?¹³C values were measured using a spooling-wire microcombustion device interfaced with an isotope-ratio mass spectrometer. Leaf ?¹³C was also measured. Carbon isotope discrimination (?) for untreated pollen, sporopollenin and leaves was compared with historic records of seasonal precipitation amount, vapor pressure deficit and the Palmer Drought Severity Index (PDSI). Each species showed positive correlations between ? of untreated pollen and sporopollenin. Sporopollenin ? was most strongly correlated with PDSI. Correlations among leaf ? and moisture indicators were stronger for Ambrosia than Artemisia. These results suggest that sporopollenin ? indicates the level of moisture stress in C? plants. Therefore, ?¹³C analysis of pollen promises to help address important paleoecological questions, such as how community-level physiology contributes to shifts in vegetation composition. PMID:22742492

Nelson, David M



Tracing carbonate-silicate interaction during subduction using magnesium and oxygen isotopes.  


Subduction of carbonates and carbonated eclogites into the mantle plays an important role in transporting carbon into deep Earth. However, to what degree isotopic exchanges occur between carbonate and silicate during subduction remains unclear. Here we report Mg and O isotopic compositions for ultrahigh pressure metamorphic marbles and enclosed carbonated eclogites from China. These marbles include both calcite- and dolomite-rich examples and display similar O but distinct Mg isotopic signatures to their protoliths. Their ?(26)Mg values vary from -2.508 to -0.531‰, and negatively correlate with MgO/CaO ratios, unforeseen in sedimentary carbonates. Carbonated eclogites have extremely heavy ?(18)O (up to +21.1‰) and light ?(26)Mg values (down to -1.928‰ in garnet and -0.980‰ in pyroxene) compared with their protoliths. These unique Mg-O isotopic characteristics reflect differential isotopic exchange between eclogites and carbonates during subduction, making coupled Mg and O isotopic studies potential tools for tracing deep carbon recycling. PMID:25367068

Wang, Shui-Jiong; Teng, Fang-Zhen; Li, Shu-Guang



Carbon isotopic composition of assimilated and respired CO2 in Southeastern US pine forests  

NASA Astrophysics Data System (ADS)

We measured the 13C of assimilated carbon [foliage organic matter (?COM), leaf soluble carbohydrates ((?CSC), and leaf waxes ((?CW)] and respiratory carbon [foliage (?CF), soil (?CS) and ecosystem respired CO2 (?CR)] over a two-year period at two sites in central Florida that are typical of Southeastern US coastal plain pine ecosystems. Our objective was to determine how climatic variables, operating by affecting plant physiology and photosynthetic discrimination (?), influence the isotopic composition of assimilated carbon pools and of ecosystem respired CO2. The first site was a naturally regenerated 32 m tall stand of mature longleaf pine (Pinus palustris Mill.) with mature slash pine (Pinus elliottii) subdominants, while the second was a planted, mid-rotation 13 m tall stand of slash pine (Pinus elliottii var. elliottii Engelm.). ?COM, ?CSC, ?CW, and ?CF of P. palustris were 13C enriched by about 2‰ relative to that of P. elliottii in the mid-rotation plantation. Despite this enrichment, mean ?CR of the P. palustris stand was similar to that at the P. elliottii plantation, reflecting additional respiratory inputs from the more isotopically depleted P. elliottii subdominant and understory. In both P. palustris and P. elliottii, a small decrease was observed in ?COM over the two year study, but not in ?CSC, ?CF, ?CS or ?CR. Intriguingly, a significant 2‰ decrease was also observed in the very long chain needlewaxes (C32-36 n-alkanoic acids), but not the more abundant C24-28 waxes. As the carbon in waxes is supplied by internal storage reserves, our data suggest there may be distinct carbon source pathways for waxes of differing chain lengths. The long-term decrease in the 13C of foliar carbon and waxes also suggests recovery from severe drought conditions prior to our study. ?CF and ?CR were consistently 13C enriched relative to assimilated C and were insensitive to variations in vapor pressure deficit (D). The small variability in ?CA and ?CR at this site is likely due to the shallow water table that mediates moisture stress as well as the low sensitivity of stomatal conductance to D in these species.

Mortazavi, B.; Conte, M. H.; Chanton, J.; Martin, T.; Teklemerian, T.; Cropper, W.; Weber, J.



The Suess Effect and Additional Impacts on the Carbon Isotope Composition of a Belizean Coral  

NASA Astrophysics Data System (ADS)

Recent work has shown that the geochemistry of coral skeletons can reflect large-scale changes in the ocean carbon isotope budget as influenced by the anthropogenic influx of fossil fuel carbon to the atmosphere (the Suess Effect). Yet not all coral carbon records reflect just atmospheric controls on carbon. This study assesses the relative influence of the Suess Effect on carbon chemistry within a Belizean Montastrea faveolota colony and interprets deviations from the Suess Effect signal. The coral sample used for this study was collected off Wee Wee Caye, in South-Central Belize offshore of the Sittee River, Stann Creek District in 2003. Coral carbonate was sampled at an average resolution of 15 samples per coral year. Carbon isotope data from the Belizean coral were compared with mean annual carbon isotope data from Atlantic corals in a study by Swart et. al (2010) to analyze the relative contribution of the Suess Effect and competing controls on the carbon isotope composition of Belizean waters. The observed pattern in the Belize coral suggested two distinct trends in carbon isotopic composition, and segmented regression analysis indicated a significant breakpoint occurs in this record in approximately 1965. Deforestation rates in Belize after the 1960's have been almost double that for the rest of Central America (2.3% vs. 1.2% annually) corresponding with a general shift from rural farming to large scale agriculture in Belize. Consequently, increased rates of deforestation in Belize may have been an important factor in carbon isotope budgets of the area over the last several decades. Compared with data averaged from Atlantic coral samples, annual carbon isotope values in Belizean coral declined more rapidly since the 1960's. We attribute this sharper decline in the Belizean coral to enhanced influx of terrestrial 'light' organic carbon to the reef over the study period.

Greer, L.; Bunn, S.; Humston, R.; Swart, P. K.; Curran, H.; Rose, L. E.



Carbon isotope systematics of individual hydrocarbons in hydrothermal petroleum from Escanaba Trough, Northeastern Pacific Ocean  

USGS Publications Warehouse

We submitted individual aliphatic and polycyclic aromatic hydrocarbons in samples of hydrothermal petroleum from Escanaba trough to compound specific isotope analysis to trace their origins. The carbon isotope compositions of the alkanes and polycyclic aromatic hydrocarbons (means -27.5 and -24.7%, respectively) reflect a primarily terrestrial organic matter source.We submitted individual aliphatic and polycyclic aromatic hydrocarbons in samples of hydrothermal petroleum from Escanaba Trough to compound specific isotope analysis to trace their origins. The carbon isotope compositions of the alkanes and polycyclic aromatic hydrocarbons (means -27.5 and -24.7 per mill, respectively) reflect a primarily terrestrial organic matter source.

Simoneit, B.R.T.; Schoell, M.; Kvenvolden, K.A.



Decarboxylation of glycine contributes to carbon isotope fractionation in photosynthetic organisms.  


Carbon isotope effects were investigated for the reaction catalyzed by the glycine decarboxylase complex (GDC; EC Mitochondria isolated from leaves of pea (Pisum sativum L.) and spinach (Spinacia oleracea L.) were incubated with glycine, and the CO(2) evolved was analyzed for the carbon isotope ratio (delta(13)C). Within the range of parameters tested (temperature, pH, combination of cofactors NAD(+), ADP, pyridoxal 5-phosphate), carbon isotope shifts of CO(2) relative to the C(1)-carboxyl carbon of glycine varied from +14 per thousand to -7 per thousand. The maximum effect of cofactors was observed for NAD(+), the removal of which resulted in a strong (12)C enrichment of the CO(2) evolved. This indicates the possibility of isotope effects with both positive and negative signs in the GDC reaction. The measurement of delta(13)C in the leaves of the GDC-deficient barley (Hordeum vulgare L.) mutant (LaPr 87/30) plants indicated that photorespiratory carbon isotope fractionation, opposite in sign when compared to the carbon isotope effect during CO(2) photoassimilation, takes place in vivo. Thus the key reaction of photorespiration catalyzed by GDC, together with the key reaction of CO(2) fixation catalyzed by ribulose-1,5-bisphosphate carboxylase, both contribute to carbon isotope fractionation in photosynthesis. PMID:16228305

Igamberdiev, A U; Ivlev, A A; Bykova, N V; Threlkeld, C N; Lea, P J; Gardeström, P



Ground penetrating radar measurements show a spatial relationship between coarse root biomass and soil carbon abundance  

NASA Astrophysics Data System (ADS)

In savanna ecosystems, the dynamics of soil organic carbon are complicated by multiple sources of inputs, created by the coexistance of trees and grasses, and by spatial heterogeneity induced by a patchy vegetation structure. A previous study on the spatial pattern of soil carbon abundance on the Kalahari Transect in Southern Africa found that for savannas with sparse woody cover the semivariogram of soil carbon abundance demonstrates periodicity. It is hypothesized that the periodicity is induced by the patchy spatial distribution of canopies and root systems of woody plants. We tested this by mapping the abundance of coarse woody roots with ground penetrating radar. Spatial patterns of soil carbon abundance were measured at our research site in a previous study. The site is on the Botswana portion of the Kalahari Transect, and has deep, homogeneous, sandy soil. We ran the ground penetrating radar over three 20 by 20 meter square plots in two perpendicular directions. We filtered the radar images to remove background noise and applied a Hilbert transform to reduce echoes. In each plot, we also dug 20 root biomass sampling pits. Using the sampling pit data, we were able to verify that there is a log-linear relationship (r2 = 0.80) between radar signal return and coarse root biomass in the upper 50 cm of soil. Semivariograms of coarse root biomass inferred from radar returns showed periodicity at similar spatial scales to the periodicity in soil carbon abundance. Our results suggest that the belowground components of woody plants, which may extend well beyond their canopies, exert a stronger influence on soil carbon cycling than the aboveground components, illustrating a key issue with the common practice of dividing arid and semiarid landscapes into "under canopy" and "inter-canopy" components in analyses of soil biogeochemistry. We were able to show that a relationship exists between ground penetrating radar returns and coarse root biomass for dry, sandy soils. However, the large amount of information needed to determine a predictive relationship suggests that ground penetrating radar may be more useful in investigating spatial patterns of root biomass than as a tool for quantifying absolute biomass abundance.

O'Donnell, F. C.; Gerlein, C.; Bhattachan, A.; Caylor, K. K.



Ground penetrating radar measurements show a spatial relationship between coarse root biomass and soil carbon abundance  

NASA Astrophysics Data System (ADS)

In savanna ecosystems, the dynamics of soil organic carbon are complicated by multiple sources of inputs, created by the coexistance of trees and grasses, and by spatial heterogeneity induced by a patchy vegetation structure. A previous study on the spatial pattern of soil carbon abundance on the Kalahari Transect in Southern Africa found that for savannas with sparse woody cover the semivariogram of soil carbon abundance demonstrates periodicity. It is hypothesized that the periodicity is induced by the patchy spatial distribution of the canopies and root systems of woody plants. We tested this by mapping the abundance of coarse woody roots with ground penetrating radar. Spatial patterns of soil carbon abundance were measured at our research site in a previous study. The site is on the Botswana portion of the Kalahari Transect, and has deep, homogeneous, sandy soil. We ran the ground penetrating radar over three 20 by 20 meter square plots in two perpendicular directions. We filtered the radar images to remove background noise and applied a Hilbert transform to reduce echoes. In each plot, we also dug 20 root biomass sampling pits. Using the sampling pit data, we were able to verify that there is a log-linear relationship (r2 = 0.80) between radar signal return and coarse root biomass in the upper 50 cm of soil. Semivariograms of coarse root biomass inferred from radar returns showed periodicity at similar spatial scales to the periodicity in soil carbon abundance. Our results suggest that the belowground components of woody plants, which may extend well beyond their canopies, exert a stronger influence on soil carbon cycling than the aboveground components, illustrating a key issue with the common practice of dividing arid and semiarid landscapes into "under canopy" and "inter-canopy" components in analyses of soil biogeochemistry. We were able to show that a relationship exists between ground penetrating radar returns and coarse root biomass for dry, sandy soils. However, the large amount of information needed to determine a predictive relationship suggests that ground penetrating radar may be more useful in investigating spatial patterns of root biomass than as a tool for quantifying absolute biomass abundance.

O'Donnell, F. C.; Caylor, K. K.; Gerlein, C.; Bhattachan, A.



Standard test method for uranium and plutonium concentrations and isotopic abundances by thermal ionization mass spectrometry  

E-print Network

1.1 This test method covers the determination of the concentration and isotopic composition of uranium and plutonium in solutions. The purified uranium or plutonium from samples ranging from nuclear materials to environmental or bioassay matrices is loaded onto a mass spectrometric filament. The isotopic ratio is determined by thermal ionization mass spectrometry, the concentration is determined by isotope dilution. 1.2 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish safety and health practices and determine the applicability of regulatory limitations prior to use.

American Society for Testing and Materials. Philadelphia



Analysis of dissolved organic carbon concentration and 13C isotopic signature by TOC-IRMS - assessment of analytical performance  

NASA Astrophysics Data System (ADS)

Stable carbon isotopes provide a powerful tool to assess carbon pools and their dynamics. Dissolved organic carbon (DOC) has been recognized to play an important role in ecosystem functioning and carbon cycling and has therefore gained increased research interest. However, direct measurement of 13C isotopic signature of carbon in the dissolved phase is technically challenging particularly using high temperature combustion. Until recently, mainly custom-made systems existed which were modified for coupling of TOC instruments with IRMS for simultaneous assessment of C content and isotopic signature. The variety of coupled systems showed differences in their analytical performances. For analysis of DOC high temperature combustion is recognized as best performing method, owing to its high efficiency of conversion to CO2 also for highly refractory components (e.g. humic, fulvic acids) present in DOC and soil extracts. Therefore, we tested high temperature combustion TOC coupled to IRMS (developed by Elementar Group) for bulk measurements of DOC concentration and 13C signature. The instruments are coupled via an Interface to exchange the carrier gas from O2 to He and to concentrate the derived CO2 for the isotope measurement. Analytical performance of the system was assessed for a variety of organic compounds characterized by different stability and complexity, including humic acid and DOM. We tested injection volumes between 0.2-3 ml, thereby enabling measurement of broad concentration ranges. With an injection volume of 0.5 ml (n=3, preceded by 1 discarded injection), DOC and 13C signatures for concentrations between 5-150 mg C/L were analyzed with high precision (standard deviation (SD) predominantly <0.1‰), good accuracy and linearity (overall SD <0.9‰). For the same settings, slightly higher variation in precision was observed among the lower concentration range and depending upon specific system conditions. Differences in 13C signatures of about 50‰ among samples did not affect the precision of the analysis of natural abundance and labeled samples. Natural DOM, derived from different soils and assessed at various concentrations, was measured with similar good analytical performance, and also tested for the effect of freezing and re-dissolving. We found good performance of TOC-IRMS in comparison with other systems capable of determining C concentration and isotopic signatures. We recognize the advantages of this system providing: - High sample throughput, short measurement time (15 minutes), flexible sample volume - Easy maintenance, handling, rapid sample preparation (no pretreatment) This preliminary assessment highlights wide-ranging opportunities for further research on concentrations and isotopic signatures by TOC-IRMS to elucidate the role of dissolved carbon in terrestrial and aquatic systems.

Kirkels, Frédérique; Cerli, Chiara; Federherr, Eugen; Kalbitz, Karsten



Global synchronous changes in the carbon isotopic composition of carbonate sediments unrelated to changes in the global carbon cycle  

PubMed Central

The carbon isotopic (?13C) composition of bulk carbonate sediments deposited off the margins of four carbonate platforms/ramp systems (Bahamas, Maldives, Queensland Plateau, and Great Australian Bight) show synchronous changes over the past 0 to 10 million years. However, these variations are different from the established global pattern in the ?13C measured in the open oceans over the same time period. For example, from 10 Ma to the present, the ?13C of open oceanic carbonate has decreased, whereas platform margin sediments analyzed here show an increase. It is suggested that the ?13C patterns in the marginal platform deposits are produced through admixing of aragonite-rich sediments, which have relatively positive ?13C values, with pelagic materials, which have lower ?13C values. As the more isotopically positive shallow-water carbonate sediments are only produced when the platforms are flooded, there is a connection between changes in global sea level and the ?13C of sediments in marginal settings. These data indicate that globally synchronous changes in ?13C can take place that are completely unrelated to variations in the global carbon cycle. Fluctuations in the ?13C of carbonate sediments measured during previous geological periods may also be subject to similar processes, and global synchroniety of ?13C can no longer necessarily be considered an indicator that such changes are related to, or caused by, variations in the burial of organic carbon. Inferences regarding the interpretation of changes in the cycling of organic carbon derived from ?13C records should be reconsidered in light of the findings presented here. PMID:18772393

Swart, Peter K.



Carbon allocation and carbon isotope fluxes in the plant-soil-atmosphere continuum: a review  

NASA Astrophysics Data System (ADS)

The terrestrial carbon (C) cycle has received increasing interest over the past few decades, however, there is still a lack of understanding of the fate of newly assimilated C allocated within plants and to the soil, stored within ecosystems and lost to the atmosphere. Stable carbon isotope studies can give novel insights into these issues. In this review we provide an overview of an emerging picture of plant-soil-atmosphere C fluxes, as based on C isotope studies, and identify processes determining related C isotope signatures. The first part of the review focuses on isotopic fractionation processes within plants during and after photosynthesis. The second major part elaborates on plant-internal and plant-rhizosphere C allocation patterns at different time scales (diel, seasonal, interannual), including the speed of C transfer and time lags in the coupling of assimilation and respiration, as well as the magnitude and controls of plant-soil C allocation and respiratory fluxes. Plant responses to changing environmental conditions, the functional relationship between the physiological and phenological status of plants and C transfer, and interactions between C, water and nutrient dynamics are discussed. The role of the C counterflow from the rhizosphere to the aboveground parts of the plants, e.g. via CO2 dissolved in the xylem water or as xylem-transported sugars, is highlighted. The third part is centered around belowground C turnover, focusing especially on above- and belowground litter inputs, soil organic matter formation and turnover, production and loss of dissolved organic C, soil respiration and CO2 fixation by soil microbes. Furthermore, plant controls on microbial communities and activity via exudates and litter production as well as microbial community effects on C mineralization are reviewed. The last part of the paper is dedicated to physical interactions between soil CO2 and the soil matrix, such as CO2 diffusion and dissolution processes within the soil profile. From the presented evidence we conclude that there exists a tight coupling of physical, chemical and biological processes involved in C cycling and C isotope fluxes in the plant-soil-atmosphere system. Generally, research using information from C isotopes allows an integrated view of the different processes involved. However, complex interactions among the range of processes complicate or impede the interpretation of isotopic signals in CO2 or organic compounds at the plant and ecosystem level. This is where new research approaches should be aimed at.

Brüggemann, N.; Gessler, A.; Kayler, Z.; Keel, S. G.; Badeck, F.; Barthel, M.; Boeckx, P.; Buchmann, N.; Brugnoli, E.; Esperschütz, J.; Gavrichkova, O.; Ghashghaie, J.; Gomez-Casanovas, N.; Keitel, C.; Knohl, A.; Kuptz, D.; Palacio, S.; Salmon, Y.; Uchida, Y.; Bahn, M.



A molecular organic carbon isotope record of miocene climate changes  

SciTech Connect

The difference in carbon-13 ([sup 13]C) contents of hopane and sterane biomarkers in the Monterey formation (Naples Beach, California) parallels the Miocene inorganic record of the change in [sup 18]O ([delta][sup 18]O), reflecting the Miocene evolution from a well-mixed to a highly stratified photic zone (upper 100 meters) in the Pacific. Steranes ([delta][sup 13]C = 25.4 [+-] 0.7 per mil versus the Pee Dee belemnite standard) from shallow photic-zone organisms do not change isotopically throughout the Miocene. In contrast, sulfur-bound C[sub 35] hopanes (likely derived from bacterial plankton living at the base of the photic zone) have systematically decreasing [sup 13]C concentrations in Middle and Late Miocene samples ([delta][sup 13]C = 29.5 to [minus]31.5 per mil), consistent with the Middle Miocene formation of a carbon dioxide-rich cold water mass at the base of the photic zone.

Schoell, M. (Chevron Petroleum Technology Co., La Habra, CA (United States)); Schouten, S.; Sinninghe Damste', J.S.; Leeuw, J.W. de (Netherlands Institute of Sea Research, Texel (Netherlands)); Summons, R.E. (Australian Geological Survey Organization, Canberra (Australia))



Abundances and isotopic compositions of rhenium and osmium in pyrite samples from the Huaibei coalfield, Anhui, China  

USGS Publications Warehouse

Two pyrite samples from the Shihezi Formation (Lower Permian), Huaibei coalfield, Anhui, China, have been analyzed for abundances and isotopic compositions of rhenium and osmium using negative thermal ion mass spectrometry. The Re-Os ages of the pyrites are 64.4 and 226 Ma, which are younger than the formation age of the coal seam. The pyrite samples may consist of pyrite formed at various stages during the history of coal formation. The ??Osvalues of the two pyrite samples are +17 and +18, respectively. Such high ??Osvalues are reported for the first time for recycles crustal materials from a sedimentary basin. ?? Springer-Verlag 2007.

Liu, G.; Chou, C.-L.; Peng, Z.; Yang, G.



Miocene Global Carbon Isotope Shifts and Marine Biological Productivity.  

NASA Astrophysics Data System (ADS)

The Miocene contains two major global carbon isotope shifts: a negative shift during the late Miocene (~8-6 Ma) and a positive shift during the mid-Miocene (16-14 Ma). We aim at deciphering possible changes in marine biological export productivity during these shifts by calculating paleoproductivity in gC/cm*ky from benthic foraminiferal numbers and accumulation rates at a number of sites spanning the world oceans. Our previous work has illustrated that the onset of the late Miocene negative d 13C shift, which has been attributed to enhanced erosion of terrestrial biomass and expansion of C4 plants, is also accompanied by an increase in marine export productivity from lower than present day values up to 2-3 times modern values at six sites (982, 1088, 721, 846, 1146, 1172; Diester-Haass et al, in press; Diester-Haass et al., in preparation). The Mid-Miocene 'Monterey Event', on the other hand, has been attributed to sequestration of organic material in circum-Pacific basins (Vincent and Berger, 1985) or wide spread deposition of brown coal and drowning of carbonate platforms (Föllmi et al., 2005) . For this particular time interval, our initial results from Site 608 (Atlantic Ocean) reveal relatively constant paleoproductivity values similar to modern ones ( about 10 gC/cm*ky) until 16.5 Ma, after which time paleoproductivity begins to increase until the end of our record at 11 Ma. Superimposed on the trend of generally increasing productivity, there are a number of productivity minima spaced roughly 0.5 million years apart. The long term trend in the paleoproductivity finds some similarities in the global composite benthic foraminiferal d 13C record as both proxies show an overall increase until ~14 Ma. Thereafter, however, paleoproductivity continues to increase while d 13C values decrease marking the end of the Monterey excursion. Stable isotope analyses from these same intervals will show to what extend the smaller scale fluctuations in paleoproductivity can be related to changes in the d13C of the oceanic reservoir or regional water masses. Diester-Haass, L., Billups, K., Emeis, K-C., 2005, Paleoceanography, in press. Vincent, E. and Berger, W., 1985, In: The carbon cycle and atmospheric CO2: Natural variations Archaen to present, edited by Sunquist, E.T. and Broecker, W.S., Am.Geophys. Union Monogr. 32,455-468 Föllmi, K.B. et al., 2005, Geol.Soc.Am.Bull., 117/5, 589-619.

Diester-Haass, L.; Billups, K.



The influence of kinetics on the oxygen isotope composition of calcium carbonate  

NASA Astrophysics Data System (ADS)

Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 ?M dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.



Isotopic composition of Murchison organic compounds: Intramolecular carbon isotope fractionation of acetic acid. Simulation studies of cosmochemical organic syntheses  

NASA Technical Reports Server (NTRS)

Recently, in our laboratories, samples of Murchison acetic acid were decarboxylated successfully and the carbon isotopic composition was measured for the methane released by this procedure. These analyses showed significant differences in C-13/C-12 ratios for the methyl and carboxyl carbons of the acetic acid molecule, strongly suggesting that more than one carbon source may be involved in the synthesis of the Murchison organic compounds. On the basis of this finding, laboratory model systems simulating cosmochemical synthesis are being studied, especially those processes capable of involving two or more starting carbon sources.

Yuen, G. U.; Cronin, J. R.; Blair, N. E.; Desmarais, D. J.; Chang, S.



Estimation of riverine carbon and organic matter source contributions using time-based isotope mixing models  

NASA Astrophysics Data System (ADS)

Rivers transport globally significant amounts of carbon (C) from terrestrial ecosystems to ocean margins. Understanding and quantifying the sources and respective contributions to riverine C has emerged as an important biogeochemical problem that can be approached through natural-abundance isotope mass balance. Traditionally, the sources of riverine C have been identified either qualitatively or quantitatively through application of static mixing models. However, both source signatures and contributions can vary significantly with time. Here we apply two time-based mixing models to a study of six rivers draining the northeast U.S. In the first model, a time-averaged mixing model (TAMM), we vary only the source isotopic (?13C and ?14C) signatures. In the second model, a time-varying mixing model (TVMM), we allow both isotopic signatures and contributions to vary with time. Based on results from the TVMM, drivers of variation in riverine particulate organic C (POC), dissolved organic C (DOC), and dissolved inorganic C (DIC) include stream discharge, stream discharge and water temperature, and water temperature and vegetation phenology, respectively. Major sources include C3plant material, algal material and slow-turnover soil OC ("slow SOC"), which together account for 50%-100% (95% CI) of riverine POC; C3plant material and slow SOC, which together typically account for 60%-100% (95% CI) of DOC; and atmospheric exchange which alone typically accounts for 40%-60% (95% CI) of DIC. Seasonal change in relative contributions from algal material, slow SOC, and photosynthesis (in response to the identified drivers) dominates the observed variation in POC, DOC and DIC, respectively. The TVMM is a novel tool to identify component contributions under more realistic non-static conditions, and with potential application to a broad range of biogeochemical studies.

Hossler, Katie; Bauer, James E.



Evaporation and carbonic anhydrase activity recorded in oxygen isotope signatures of net CO2 fluxes from  

E-print Network

Evaporation and carbonic anhydrase activity recorded in oxygen isotope signatures of net CO2 fluxes carbonic anhydrase, reducing CO2 hydration times, have been proposed recently to explain field observations in atmospheric CO2. Keywords: atmospheric invasion, carbonic anhydrase, drought, Mediterranean forests, oxygen

Mencuccini, Maurizio


Calculation of isotope shifts and relativistic shifts in C I, C II, C III, and C IV J. C. Berengut*  

E-print Network

Calculation of isotope shifts and relativistic shifts in C I, C II, C III, and C IV J. C. Berengut of calculating isotope shifts and relativistic shifts in atomic spectra. We test the method on neutral carbon the lifetime of the Universe. Carbon isotope shifts can be used to measure isotope abundances in gas clouds

Kozlov, Mikhail G


Analysis of Fragments from Cluster Particles: Carbon Abundances, Bulk Chemistry, and Mineralogy  

NASA Astrophysics Data System (ADS)

Anhydrous interplanetary dust particles (IDPs) containing fine-grained aggregates (FGAs) have chondritic element abundances, characteristic textures, and high 4He and Zn abundances. These FGAs can account for >75 vol% of some anhydrous IDPs [1]. We previously noted a correlation of carbon abundance with modal pyroxene content in anhydrous particles [2]. In this study, we analyzed multiple fragments from individual cluster particles to determine (1) if carbon content is correlated with the abundance of FGAs and (2) the extent of chemical and mineralogical heterogeneities of particle clusters. We examined 15 IDPs from 7 distinct clusters of particles on the large area collectors using methods described in [2]. Optically light and dark fragments were selected from each cluster in order to sample a variety of material. Major-, minor-, and light-element compositions and mineralogical data are given for the cluster particle fragments in Table 1. Of the seven clusters sampled, two are coarse-grained and five are dominated by FGAs (>50% of the particle volume). Four of the seven clusters have pyroxene as the dominant crystalline silicate, one has a subequal mixture of pyroxene and olivine, one is dominated by sulfides, and one is dominated by olivine. L2005, #17 and L2005, #26 contain FeZnS grains. The C abundance is chondritic (<3x CI) for five of the clusters; only two clusters have high C abundances. All major and minor elements are within 2x CI for all clusters with the exception of Na, which is typically >2x CI. Solar flare tracks were observed in L2005,, #19. Compositional differences were observed between light and dark fragments from all clusters except cluster L2006, #28, indicating that most clusters are heterogeneous at the 10-micrometer scale. In general, the C abundance and the sulfide content in the dark fragments are greater than or equal to that in the light fragments. Carbon abundance does not appear to correlate with the content of FGAs. Another example of heterogeneity within clusters is L2005, #26; mineralogical analysis of one of the fragments of this cluster showed it to be dominated by Fe sulfides, whereas SEM analysis of two other fragments showed no evidence of sulfide enrichment. Our study suggests that conclusions drawn from one fragment of a cluster are not necessarily representative of other fragments from the same cluster. Acknowledgments: This work was supported by NASA RTOPs 152-17-40-23 and 199- 52-11-02. References: [1] Bradley J. P.(1992) LPSC, 24, 171-172. [2] Thomas K. L. et al. (1993) GCA, 57, 1551-1566.

Thomas, K. L.; Klock, W.; Keller, L. P.; Blanford, G. E.; McKay, D. S.



Comparison of Bulk and Compound-Specific Carbon Isotope Analyses and Determination of Carbon Sources to Salt Marsh Sediments Using n-Alkane Distributions (Maine, USA)  

NASA Astrophysics Data System (ADS)

Sources of sedimentary organic matter to a Morse River, Maine (USA) salt marsh over the last 3390+/-60 RCYBP are determined using distribution patterns of n-alkanes as well as bulk and compound-specific carbon isotopic analysis. Marsh foraminiferal counts indicate the ubiquitous presence of zone 1B deposits, suggesting that the deposits were laid down ~0.2 to 0.5m above mean high water. Distributions of n-alkanes show a primary contribution from higher plants, confirmed by an average ACL value of 27.5 for the core sediments and CPI values above 3. Many sample depths have a maximum abundance at the C25 alkane. Ten low marsh, high marsh, and higher-high marsh plant species common to Maine salt marshes were sampled, including Spartina alterniflora, Spartina patens, Juncus gerardi and Solidago sempervirens. The ACL value for the average of the 10 marsh species is 29.1. Salicornia europa, usually not considered to be a dominant species in Maine marshes, has a similar n-alkane distribution to many of the salt marsh sediments, suggesting that it is an important source to the biomass of the marsh through time. Bacterial degradation or algal inputs to the marsh sediments appear to be minor. Compound specific carbon isotopic analyses of the C27 alkanes are, on average, 7.2ppt. depleted relative to bulk values, but the two records are strongly correlated (R2 = 0.87), suggesting that marsh plants are "swamping" the bulk carbon isotopic signal. The apparent abundance of a subordinate (though common) salt marsh plant species (Salicornia europa) within our core underscores the importance of using caution when applying mixing models of relatively few plant species to marsh sediments.

Tanner, B. R.; Uhle, M. E.; Kelley, J. T.; Mora, C. I.



Carbon isotopes in the ocean model of the Community Earth System Model (CESM1)  

NASA Astrophysics Data System (ADS)

Carbon isotopes in the ocean are frequently used as paleo climate proxies and as present-day geochemical ocean tracers. In order to allow a more direct comparison of climate model results with this large and currently underutilized dataset, we added a carbon isotope module to the ocean model of the Community Earth System Model (CESM), containing the cycling of the stable isotope 13C and the radioactive isotope 14C. We implemented the 14C tracer in two ways: in the "abiotic" case, the 14C tracer is only subject to air-sea gas exchange, physical transport, and radioactive decay, while in the "biotic" version, the 14C additionally follows the 13C tracer through all biogeochemical and ecological processes. Thus, the abiotic 14C tracer can be run without the ecosystem module, requiring significantly less computational resources. The carbon isotope module calculates the carbon isotopic fractionation during gas exchange, photosynthesis, and calcium carbonate formation, while any subsequent biological process such as remineralization as well as any external inputs are assumed to occur without fractionation. Given the uncertainty associated with the biological fractionation during photosynthesis, we implemented and tested three parameterizations of different complexity. Compared to present-day observations, the model is able to simulate the oceanic 14C bomb uptake and the 13C Suess effect reasonably well compared to observations and other model studies. At the same time, the carbon isotopes reveal biases in the physical model, for example a too sluggish ventilation of the deep Pacific Ocean.

Jahn, A.; Lindsay, K.; Giraud, X.; Gruber, N.; Otto-Bliesner, B. L.; Liu, Z.; Brady, E. C.



Quantifying biological and atmospheric processes with in-situ measurements of carbon dioxide and water vapor isotopes (Invited)  

NASA Astrophysics Data System (ADS)

The ability to make real-time, high-frequency measurements of CO2 and H2O isotopes in the atmosphere opens a new channel of scientific pursuit. The objectives of this paper are (1) to examine practical issues on using these measurements in biospheric and atmospheric research, and (2) to compare two different perspectives on isotopic surface-air fluxes. From the user’s perspective, three issues should be resolved in order to further realize the power of these in-situ measurements. The first one is related to instrument calibration. By their nature, isotopologue measurements by optical methods are prone to biases from nonlinear concentration dependence. Overcoming the nonlinear effect via calibration is important for the measurement of the isotopic abundance of CO2 or H2O and even more so for the measurement of the isotopic signal of their fluxes. Further, a portable calibration system is essential for deployment in remote sites. The second challenge that researchers face is instrument cost. We envision the development of a new flux network with real-time observations of isotopic fluxes of CO2 and H2O to help diagnose changes in atmospheric and biospheric processes. This can become a realistic goal if the instrument cost is brought down to a level comparable to that of broadband infrared analyzers. Third, speed of detection also deserves attention. In-situ measurements of CO2 and H2O isotope ratios in ambient air, especially if made on a long-term basis and calibrated precisely, can aid atmospheric inverse analysis of land carbon sink and the tracking of water transport in the atmosphere. Ambient monitoring alone is however not very useful in ecological studies. To measure the source/sink signature properly, one should interface the isotopic analyzer with a plant or soil chamber, deploy it in the gradient-diffusion mode either over a plant canopy or over the soil surface inside the canopy, or combine it with a sonic anemometer for direct eddy covariance measurement of isotopic fluxes. In all these configurations, fast instrument response is essential. Along with technical advances in the measurement technology emerge two perspectives on surface-air isotopic exchanges. The traditional “bottom-up” perspective emphasizes biological discrimination mechanisms and end member isotopic flux signals. Considerations of isotopic budgets in the atmosphere call for a “top-down” perspective, requiring that the exchanges be quantified as “isoforcing” analogously to the eddy fluxes of other atmospheric scalar constituents. These two perspectives are complementary but require different measurement and modeling protocols.

Lee, X.



Carbon isotope stratigraphy of an ancient (Ordovician) Bahamian-type carbonate platform: Implications for preservation of global seawater trends  

NASA Astrophysics Data System (ADS)

Carbon isotope stratigraphy has a unique role in the interpretation of Earth history as one of the few geochemical proxies that have been widely applied throughout the geologic time scale, from the Precambrian to the Recent, as both a global correlation tool and proxy for the carbon cycle. However, in addition to consideration of the role of diagenesis, numerous studies have raised awareness of the fact that C-isotope trends derived from ancient carbonate platforms may not be representative of dissolved inorganic carbon from a well-mixed global ocean reservoir. Furthermore, the larger carbon isotopic fractionation in the formation of aragonite versus calcite from seawater must be taken into account. All three of these variables (diagenesis, water mass residence time, % aragonite) may change in response to sea level, producing trends in C-isotopes on ancient carbonate platforms that are unrelated to the global carbon cycle. Global carbon cycle fluxes may also have a cause-effect relationship with sea level changes, further complicating interpretations of stratigraphic trends in carbon isotopes from ancient platform environments. Studies of C-isotopes in modern carbonate platform settings such as the Great Bahama Bank (GBB) provide important analogues in addressing whether or not ancient platforms are likely to preserve a record of carbon cycling in the global ocean. Swart et al. (2009) found that waters of the GBB had generally the same or elevated values (ranging from +0.5‰ to +2.5‰) compared to the global oceans, interpreted as reflecting differential photosynthetic fractionation and precipitation of calcium carbonate (which lowers pH and converts bicarbonate into 12-C enriched carbon dioxide, leaving residual bicarbonate heavier). Carbonate sediments of the GBB have elevated C-isotopes, not only because of the high C-isotope composition of the overlying waters, but also due to the greater fractionation associated with precipitation of aragonite versus calcite. Few studies of ancient carbonates have attempted to explicitly compare C-isotope trends in both restricted platform settings and open marine settings (e.g., Immenhauser et al. 2002). We studied a restricted Bahamian-type carbonate platform of Middle-Late Ordovician (Darriwilian-early Sandbian) age included in the St. Paul Group of Maryland, notable for sedimentologic evidence of severe restriction and a general lack of open marine macrofauna. We are able to correlate the C-isotope curve from the St. Paul Group to other sections globally by using a combination of conodont microfossils and measurement of Sr isotopes on conodont apatite. Coeval C-isotope trends from open marine settings in the western United States and Estonia are comparable to the restricted platform in Maryland. In our Ordovician example, local factors appear to have modified the magnitude of the global trends, but not the timing and direction. A remaining question is whether magnitude differences are a function of sedimentation rate and completeness. We continue to test hypotheses of global correlations of C-isotope trends in the Middle-Late Ordovician by utilizing the rapidly changing Sr isotope curve at that time.

Saltzman, M.; Leslie, S. A.; Edwards, C. T.; Diamond, C. W.; Trigg, C. R.; Sedlacek, A. R.



Triple oxygen isotope composition of tropospheric carbon dioxide and terrestrial carbonates  

NASA Astrophysics Data System (ADS)

The triple oxygen isotope composition of tropospheric CO2 is a potential new tracer in urban air studies and for biosphere-atmosphere interactions [1]. In this study, we are analyzing CO2 from different provenances in order to trace the influx of anthropogenic CO2 to urban air and to test predictions on the stratosphere-troposphere exchange flux. Since July 2010, we are monitoring the triple oxygen isotope composition of CO2 in urban air in a two-week interval. For this purpose, carbon dioxide was extracted from ~450L of ambient air on the campus of the University of Göttingen using a Russian Doll type cryogenic trap [2]. The CO2 was analyzed by CO2-CeO2 equilibration at 685°C and subsequent IR laser fluorination of CeO2 and CF-irmMS [3]. All triple oxygen isotope data are reported as ?17OTFL values relative to the terrestrial fractionation line (TFL) with a slope ?TFL=0.5251 and an intercept ?TFL=-0.014%. On average, the ?17OTFL value of ambient CO2 was -0.11±0.05% (SD) with a seasonal cycle of 0.04±0.01%. Lower ?17O values were observed during wintertime. In order to test the potential of ?17O as a tracer for anthropogenic CO2, we analyzed CO2 from different combustion processes. Our results showed that the ?17O anomaly of tropospheric O2 [4] is passed on fully, or partially to the combustion CO2 [5]. We estimate that elevated anthropogenic emission during wintertime could be responsible for a decrease in ?17O of urban air CO2 of -0.02±0.01%. In order to predict the triple oxygen isotope composition of tropospheric CO2 on a global scale, we revised the box model calculation from Hoag et al. [1]. For the exponent ? for CO2-water equilibrium, we assume that ?CO2-water=0.522±0.001 [6]. Furthermore, we took into account that the ?17OTFL value of CO2 released from soils is affected by kinetic fractionation. Thus, we obtained a ?17OTFL value for global tropospheric CO2 of -0.13%. The model calculation agrees well with the ?17OTFL value determined for ambient air CO2. The triple oxygen isotope composition of terrestrial carbonates should provide additional information on the formation process of biogenic and abiotic carbonates. In order to determine the triple oxygen isotope composition on carbonates, phosphoric acid decomposition of carbonates was carried out. Subsequently, the liberated CO2 was also analyzed by the CO2-CeO2 equilibration method [3]. The ?17OTFL of CO2 released from Solnhofen limestone was -0.11±0.09% (SE, t0.95, n=6). We are currently determining the exponent ? for phosphoric acid decomposition. [1] Hoag, K.J., et al., Geophys. Res. Lett., 2005. 32: p. 1-5. [2] Brenninkmeijer, C.A.M. and T. Röckmann, Anal. Chem., 1996. 68(17): p. 3050-3053. [3] Hofmann, M. and A. Pack, Anal. Chem., 2010. 82: p. 4357-4361. [4] Barkan, E. and B. Luz, Rapid Commun. Mass Spec., 2005. 19(24): p. 3737-3742. [5] Horváth, B., M.E.G. Hofmann, and A. Pack, 2011. XI Isotope Workshop. Budapest. [6] Hofmann, M., et al., 2011. EGU. Vienna.

Hofmann, M. E.; Horváth, B.; Pack, A.



[Seasonality and contribution to acid rain of the carbon abundance in rainwater].  


This paper reports the results from a study of the carbon abundance in rainwater of Guangzhou city, China. The determination of TOC, DOC, POC and PEC helps to study the seasonality of carbon abundance and its contribution to the acid rain. The results display the fact that the average contents of TOC, DOC, POC and PEC are 7.10 mg/L, 3.58 mg/L, 3.60 mg/L and 0.72 mg/L, respectively. These results confirm the deep effect of the organic pollutant to the rain. The seasonality exists in the carbon abundance of rainwater. The contents of TOC and DOC are up to the maximum in spring and the minimum in summer; the contribution of POC to TOC in summer is obviously higher than that in other seasons; and the relative content of POC is clearly higher in dry season than that in wet season. The seasonality reflects the more emission of the total pollutant in spring and the solid particle pollutant in summer than those in other seasons. Moreover, the emission of the organic pollutant from the mobile vehicles is more obvious in dry season than that in wet season. The contents of TOC and DOC have the negative correlation to the pH values, which confirms the contribution effect of the organic pollutant, such as vehicle emission, to the acid rain. PMID:18613499

Xu, Tao; Song, Zhi-guang; Liu, Jun-feng; Wang, Cui-ping



Of Island Arcs and Icebergs? Strontium and Carbon Isotope Stratigraphy of Ethiopian Snowball Earth Sequences  

NASA Astrophysics Data System (ADS)

Neoproterozoic low-grade metasedimentary exposures uniquely preserved in synclinoria of the Tigrai region of northern Ethiopia offer excellent opportunities to assess the sedimentary response to extreme climatic changes encompassed by the Snowball Earth Hypothesis within the framework of the tectonic evolution of the Arabian-Nubian shield. Basement exposures consist of two major sequences; an older predominantly island arc metavolcanic sequence named the Tsaliet Group, and a younger metasedimentary succession named the Tambien Group. An intervening phyllite unit displays a transitional lithology variously interpreted by previous workers as metasedimentary and metavolcanic. We report Sr and C isotope results for Tambien Group carbonates from three prospective Snowball Earth successions flanking the Mekelle outlier: Negash, Mai Kenetal, and Samre. These localities display excellent exposures of the transition from Tsaliet metavolcaniclastics into distinctive carbonate exposures of the Tambien Group. Distinctive volcanic polymict conglomerates occur close to the basal Tambien contact in the upper Tsaliet Group in two localities. Presence of evaporite pseudomorphs and persistence of microbially laminated lithologies including stromatolites suggests that Tambien carbonate deposition occurred in a shallow marine setting that was initially hypersaline. A distinct black limestone unit, with abundant organic matter and indications of variable energy conditions in a slope setting, occurs higher in the section. Accompanying this transition in gross carbonate depositional style is a pronounced enrichment of carbon isotopes from values between -4 and -1 per mil in the lower interval to values between +4 and +7 per mil in the overlying black limestone. A similar excursion to more radiogenic 87Sr/87Sr compositions is observed from values between 0.7060 to 0.7064 in the lower interval to values "plateauing" between 0.7067 and 0.7069 in the black limestone. Thus far, only the Negash syncline preserves a diamictite of probable glacial origin (i.e., dropstones, faceted clasts, cobbles of diverse composition) where a pronounced negative carbon excursion from values of +7 to -2 per mil accompanies the transition from upper black carbonate to diamictite deposition. The diamictite is the youngest preserved unit within the investigated structures so it is unknown if a superjacent cap carbonate was ever deposited. Zircon evaporation dates from granites intruding the base of the sequence but post-dating early deformation of the entire sequence suggest that the Tambien Group is older than 613Ma, and therefore diamictite genesis is incompatible with younger Varanger, or `Ediacaran' glacial intervals. Ages of ~800 Ma for Tsaliet equivalents in Eritrea provide an upper age constraint. The range of measured Sr isotopic compositions best overlaps Sturtian portions of available reference curves (ca. 720-750 Ma or a little older) and strongly supports the prospect that the Negash diamictite is the product of a Sturtian glacial episode.

Miller, N. R.; Stern, R. J.; Avigad, D.; Beyth, M.; Küster, D.; Gebresilassie, S.; Mehari, K.



Carbon and Sulfur Stable Isotope Records of the Early Paleogene  

NASA Astrophysics Data System (ADS)

Secular records of stable carbon isotopes and stable sulfur isotopes from marine sediment provide primary tools for understanding past changes in global biogeochemical cycling. Over the Cenozoic, the most pronounced changes in ?13C and ?34S records happened during the late Paleocene and Early Eocene. The cause of these variations remains the source of debate, in part because the ?13C and ?34S records are not linked very well in the time domain. The early Cenozoic ?34S record principally comes from analyses of barite extracted from DSDP Sites 366 and 577 (Paytan et al., Science, 1996). However, Site 366 has no ?13C record and poorly preserved microfossil assemblages, and Site 577 has a problematic stratigraphy because of misplaced datums, and unrecognized core gaps and core overlaps. Here we generate a ?13C record at Site 366, realign the stratigraphy at Site 577, and place both records on a current time scale for the early Paleogene (Option 1; Westerhold et al., P3, 2008). There is now very little play in the relative and absolute timing of ?13C and ?34S changes across the early Paleogene. Between about 62 and 58 Ma, the ?13C of carbonate increased while the ? 34S of barite decreased. A marked change occurred at about 58 Ma: form this time to about 52 Ma, the ?13C of carbonate decreased but the ? 34S of barite continued to decrease. At about 52 Ma and a few million years after, both ?13C and ? 34S increased. Thus, the records are coupled but in a complex manner, and the series of hyperthermals happened when both ?13C and ? 34S decreased together. No model to date explains these basic observations satisfactorily. For example, volcanism as a cause for the ?34C drop does not explain the initial 4 Myr rise in ?13C and apparent coeval removal of carbon from the ocean and atmosphere; storage and release of terrestrial organic carbon as a cause for the rise and fall in ?13C does not explain the drop or subsequent rise in ?34S. Clearly, however, the idea that methane build-up in marine sediment during the late Paleocene and its subsequent discharge over the early Eocene is wrong, at least as presented (Dickens, Clim. Past, 2011). This is because such storage and release must drive significant anaerobic oxidation of methane (AOM) and the formation of Fe sulfides, which if depleted in 34S relative to seawater, would cause a positive ?34S excursion. Indeed, seafloor methane cannot be a significant player in global biogeochemical cycling during the early Paleogene, unless one invokes an unconventional notion: AOM leads to burial of 34S-enriched Fe sulfides.

Dickens, G.; Backman, J.



Nitrogen and Carbon Isotopes in Presolar Diamond Samples with Known Noble Gas Isotope Signature  

NASA Astrophysics Data System (ADS)

Since the first analyses of C and N isotopes in presolar diamonds with known noble gas isotope composition more than a decade ago [1,2] the investigation of these isotope systems in the diamonds were developed practicallly independently. During this time many interesting details in isotopic systematics of all the elements involved were found and reviewed [3-5]. The main conclusion now reached from a decade of investigation is that presolar diamonds from different meteorites are not identical but appear to consist of several populations [6-8]. Therefore a variety of circumstellar conditions may be involved through a type II supernova model is a good start point in trying to understand diamond synthesis [9]. The evidences from experimental data for all the isotope systems however are still not entirely consistent in the sense that we actually do not know how many carriers the diamonds represent and how the various noble gas carriers are related to those for nitrogen. The finding of a consensus between noble gas and light element analyses would seem to be a vital step so that more detailed nucleosynthesis models may be developed tor the diamond formation. A first point is to answer the question whether HL noble gases and light nitrogen must have been formed at the same astrophysical site. Another important achievement in terms of presolar diamond investigations during the last decade is the purity and number of samples now available. However a well known difficulty is that C, N, and noble gases are never measured all together on the same sample. The purpose of collaboration initiated in this paper is to exploit the availability of good quality samples and to go some way towards overcoming the difficulties of measurement technique incompatibility. We have analyzed three pure diamond samples separated at CalTech from Allende, Orgueil, (henceforth CT samples) and Leoville for N and C isotopic composition by stepped pyrolysis and combustion. The samples preparation and the noble gas results are described in detail elsewhere [7]. It should be noted that sample purity is supposed to be an important condition affecting release pattern of noble gases and N due to chemical reaction between coexisting minerals (for further discussion see [10]. Therefore we expected the influence of the reactions to be eliminated or significantly reduced for the samples studied here compared to those (OU samples) analyzed [6,8] before. Surprisingly we did not find any particular difference in C and N isotope systematics for the CT and OU samples. In particular they have the same carbon and N release profiles and isotope systematics (Figs. 1,2) although OU samples were measured without any attempt to remove spinel, SiC, or other oxidizing acid resistant phases. At low temperature pyrolysis steps, the CT samples have a similar peak of C, which we have previously correlated with P3 noble gases [11]. More important, release temperature of the light nitrogen from the CT samples (Fig. 2) is now confirmed to be significantly lower than that for HL noble gases supporting the hypothesis [11,12] of different carriers for the components or an entirely different release mechanism. Perhaps the most surprising outcome of our investigation was that none of the CT samples measured appeared to be 100% carbon; the reason for this apparent discrepancy ;the at present not clear. References: [1] Swart P. K. et al. (1983) Science, 220, 406-410. [2] Lewis R. S. et a1. (1983) Nature, 305, 767-771. [3] Pillinger C. T. (1993) Phil. Trans. Roy. Soc. Lond. A, 343, 73-76. [4] Anders E. and Zinner E. (1993) Meteoritics, 28, 490-514. [5] Ott U. (1993) Nature, 364, 25-33. [6] Russell S. S. et al. (1991) Science, 254, 1188-1191. [7] Huss G. R. and Lewis R. S. (1994) Meteoritics, in press. [8] Verchovsky A. B. et al. (1993) LPS XXV, 1435-1436. [9] Clayton D. D. et al. (1994) Astrophysics J., in press. [10] Verchovsky A. B. et al. (1994) Meteoritics, this volume. [11] Verchovsky A. B. et al. (1993) Meteoritics, 28, 52-53. [12] Verchovsky A. B. et a1. (1993) LPS XXIV, 1461-1462. Fig. 1

Verchovsky, A. B.; Huss, G. R.; Pillinger, C. T.



Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate  

USGS Publications Warehouse

A simple procedure for preparing barite samples for chemical and isotopic analysis is described. Sulfate ion, in barite, in the presence of high concentrations of aqueous sodium carbonate, is replaced by carbonate. This replacement forms insoluble carbonates with the cations commonly in barite: Ba, Sr, Ca and Pb. Sulfate is released into the solution by the carbonate replacement and is separated by filtration. The aqueous sulfate can then be reprecipitated for analysis of the sulfur and oxygen isotopes. The cations in the carbonate phase can be dissolved by acidifying the solid residue. Sr can be separated from the solution for Sr isotope analysis by ion-exchange chromatography. The sodium carbonate used contains amounts of Sr which will affect almost all barite 87Sr 86Sr ratios by less than 0.00001 at 1.95?? of the mean. The procedure is preferred over other techniques used for preparing barite samples for the determination of 87Sr 86Sr ratios because it is simple, rapid and enables simultaneous determination of many compositional parameters on the same material. ?? 1985.

Breit, G.N.; Simmons, E.C.; Goldhaber, M.B.



A New Method for Evaluating the Carbon Isotope Characteristics of Carbonate Formed Under Cryogenic Conditions Analogous to Mars  

NASA Technical Reports Server (NTRS)

The two upcoming robotic missions to Mars, Phoenix and MSL, will both have the capability of measuring the carbon isotopic composition of CO2 in the martian atmosphere, as well as possible CO2 trapped in carbonate minerals in the Martian soil. Results from orbital and landed missions now clearly indicate that no large scale deposits of carbonate materials exist at the surface. However, some results from orbital remote sensing have been interpreted to indicate that carbonate minerals are present as fine particles interspersed at low concentrations (approx. 2%) in the martian dust. One likely mechanism for the production of these carbonates is during the freezing of transient water near the surface. Large deposits of near surface ice and photographic evidence for flowing water on the surface suggest that transient melting and refreezing of H2O is an active process on Mars. Any exposure of these fluids to the CO2 rich atmosphere should al-low the production of HCO3- solutions. Carbonates are likely precipitates from these solutions during freezing as extensive CO2 degassing, driven by the fluid s decreasing volume, drives CO2 out. This rapid CO2 degassing increases the pH of the solution and drives carbonate precipitation. It has been shown in previous studies that this rapid CO2 degassing also results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing a large isotope enrichment of C-13 in the precipitated carbonate. This kinetic isotope enrichment may be very common in the current martian environment, and may be a very important factor in understanding the very high deltaC-13 values of carbonates found in the martian meteorites. However, while previous studies have succeeded in generally quantifying the magnitude of this effect, detailed studies of the consistency of this effect, and the freezing rates needed to produce it are needed to understand any carbon isotope analyses from carbonate minerals in the martian soil or dust. This study demonstrates an innovative new method for measuring the isotopic composition of gas evolved from the freezing of carbonate solutions in real time, which allows for a much clearer view of the chemical processes involved. This method now sets the stage for detailed analysis of the chemical and isotopic mechanisms that produce cryogenic carbonates.

Niles, P. B.; Socki, R. A.; Hredzak, P. L.



Atmospheric Aerosol Investigation In Vilnius using Stable Carbon Isotopes  

NASA Astrophysics Data System (ADS)

The effects of aerosols on the atmosphere, climate, and public health are among the central topics in current environmental research. Spatially urban air pollution is a major public concern world-wide.In this study the results of experimental research are presented, the basis of which is the investigation of 13C/12C variations ?13C of stable carbon isotopes in total carbonaceous aerosols in Vilnius city, Lithuania. The main aim of the work is to identify the origin of carbonaceous aerosols. Two autumns and one spring sampling campaign were designed with the aim to determine the changes in the air caused by the beginning/end of the heating season. The experiment was performed during several sampling periods. The first period lasted from 26 November to 06 December 2010. The second was from 04 April to 16 May 2011. The third was from 12 to 29 October 2012. Atmospheric aerosols, according to their aerodynamic diameters, were collected with an eleven-stage impactor "MOUDI". The stages have 50% aerodynamic diameter cut-offs of 18.0, 10.0, 5.6, 3.2, 1.8, 1.0, 0.56, 0.32, 0.18, 0.1 and 0.056 ?m, for stages 1-11, respectively. The analysis proceeds essentially in two stages. In the first, MOUDI foils were analyzed with EA-IRMS (FlashEA 1112 coupled to ThermoFinnigan Delta Plus Advantage). Half of the foil was measured directly (TC ?13C values). The rest was heated in the oven (400 °C) to remove organic part and measured EC+CC ?13C values (carbonates were not removed with acid). During the second stage of the analysis, corrections are made and OC ?13C values were calculated using isotopic balance equation: . As the main aim of the study was to identify the origin of incoming carbonaceous aerosols, air mass back trajectories were calculated using the HYbrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model.

Masalaite, Agne; Garbaras, Andrius; Remeikis, Vidmantas



Clumped Isotope Thermometry in Deeply Buried Sedimentary Carbonates: The Effects of Bond Reordering Kinetics and Recrystallization  

E-print Network

I utilize clumped isotope thermometry to explore the diagenetic and thermal histories of exhumed brachiopods, crinoids, cements, and host rock in the Palmarito Formation, Venezuela and the Bird Spring Formation, Nevada, USA. Carbonate components...

Shenton, Brock Jay




EPA Science Inventory

Stable hydrogen (D) and carbon (13C) isotope ratios of sedimentary methane from five subtropical Florida freshwater sites exhibited smaller, less distinct seasonal variations than previously observed in temperate sediments, apparently due to the smaller range of temperatures forc...


Analytical system for carbon stable isotope measurements of light non-methane hydrocarbons  

Microsoft Academic Search

Isotope analysis can be a useful tool in constraining the budgets (sources and sinks) of atmospheric trace species and is increasingly applied for organic constituents. This may be useful in particular for investigating the oxidative capacity of the atmosphere and studying long-range. We present setup, testing and initial results from a new automated system for carbon stable isotope ratio measurements

A. Zuiderweg; R. Holzinger; T. Röckmann



Carbon and nitrogen isotopic analysis of Pleistocene mammals from the Saltville Quarry (Virginia, USA): Implications for  

E-print Network

Carbon and nitrogen isotopic analysis of Pleistocene mammals from the Saltville Quarry (Virginia, including several families of giant mammals, representing a range of potential feeding strategies (browsers noted "juvenile effect" observed in the isotopic analyses of sub-adult mammals. In addition

Kaufman, Alan Jay


Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite  

Microsoft Academic Search

Carbon isotopic compositions have been measured for individual hydrocarbons and monocarboxylic acids from the Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of C-13 to C-12 decreases with increasing

George Yuen; Neal Blair; D. J. Des Marais; Sherwood Chang



Soil drying effects on the carbon isotope composition of soil respiration  

EPA Science Inventory

Stable isotopes are used widely as a tool for determining sources of carbon (C) fluxes in ecosystem C studies. Environmental factors that change over time, such as moisture, can create dynamic changes in the isotopic composition of C assimilated by plants, and offers a unique opp...


Stable carbon and oxygen isotopes in Sphagnum fuscum peat from subarctic Canada: Implications for palaeoclimate studies  

Microsoft Academic Search

Stable carbon and oxygen isotope ratios in single plant components in Sphagnum peat have a good potential to reveal environmental changes in peat archives. Two peat profiles, covering the past ?6000years, and a Sphagnum hummock from a discontinuous permafrost area in west central Canada were studied in order to evaluate the effect of decomposition rate on isotope records and to

Päivi Kaislahti Tillman; Steffen Holzkämper; Peter Kuhry; A. Britta K. Sannel; Neil J. Loader; Iain Robertson



Lipid Correction for Carbon Stable Isotope Analysis of Deep-sea Fishes  

EPA Science Inventory

Lipid extraction is used prior to stable isotope analysis of fish tissues to remove variability in the carbon stable isotope ratio (d13C) caused by varying lipid content among samples. Our objective was to evaluate an application of a mass balance correction for the effect of lip...


Using Carbon and Nitrogen Isotopes in Lake Sediments to Detect Land Use Change  

NASA Astrophysics Data System (ADS)

Stable isotopes in lakes sediments are often used to reconstruct past environmental conditions. Carbon and nitrogen isotopes can provide information about both internal processes and terrestrial inputs to a lake. As such, they offer a powerful approach to detecting human impacts on aquatic systems. We investigated the potential of stable isotopes to trace anthropogenic land use changes by comparing stable isotopic composition of sedimentary organic matter at several river deltas in Lake Tanganyika, East Africa. Lake Tanganyika is a large rift valley lake draining watersheds that differ greatly in size, with land use patterns that vary from low-impact, protected areas (such as Gombe Steam National Park) to deforested and intensely cultivated regions. We found that carbon isotopes were related to both watershed disturbance and size, while nitrogen isotopes were related only to watershed disturbance. The direct relationship between 13C and C:N ratios across all watersheds suggests that differences in ? 13C may be attributed to terrestrial inputs rather than internal changes in the lake, such as increased productivity. Stable isotope analyses of cores taken at two sites were consistent with patterns seen in surface sediments. Our results suggest that nitrogen isotopes may be a better indicator of land use than carbon isotopes and that watershed size can be a confounding factor in the interpretation of geochemical signals in lake sediments.

O'Reilly, C. M.; Dettman, D. L.; Cohen, A. S.



Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variations Seen in Cryogenic Laboratory Studies of Carbonate Salts  

NASA Astrophysics Data System (ADS)

The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average ?13C(DIC-CARB) values of ~20.5‰ which exceed the expected equilibrium fractionation factor of [103 ln ? = ~13‰] at 0°C. Oxygen isotopes showed a smaller enrichment with ?18O(H2O-CARB) values of ~35.5‰, slightly exceeding the equilibrium fractionation factor of [103 ln ? = ~34‰] at 0°C. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the relative paucity of carbonate minerals in the martian crust.

Socki, R.; Niles, P. B.; Sun, T.; Fu, Q.; Romanek, C. S.; Gibson, E. K.



Stable carbon isotope ratios and the existence of a gas phase in the evolution of carbonate ground waters  

Microsoft Academic Search

The chemical and stable isotope compositions of unpolluted ground waters in carbonate terranes are a function of the pH, P CO 2 , 13 C content of the ground water recharge, the 13 C content of the carbonate rock, and the manner in which the rock is dissolved or precipitated. Physico-chemical models show that significantly different relationships exist between Ca

Peter Deines; Russell S. Harmon; Donald Langmuir



The carbon isotopic composition of dissolved inorganic carbon in perennially ice-covered Antarctic lakes: searching for a biogenic  

E-print Network

lakes: searching for a biogenic signature Klaus Neumann,1 W. Berry Lyons,2 John C. Priscu,3 David J-isotopic signature of dissolved inorganic carbon (DIC) has been routinely used in temperate lake systems to investigate the biogeochemical dynamics of carbon. We studied seven perennially ice-covered lakes in the Mc

Priscu, John C.



EPA Science Inventory

Analyses of soil gas compositions and stable and radioactive carbon isotopes in the vadose zone above an alluvial aquifer were conducted at an organic solvent disposal site in southeast Phoenix, AZ. The study investigated the source and movement of carbon dioxide above a plume of...



EPA Science Inventory

Analyses of soil gas compositions and stable and radioactive carbon isotopes in the vadose zone above an alluvial aquifer were conducted at an organic solvent disposal site in southeast Phoenix, AZ. he study investigated the source and movement of carbon dioxide above a plume of ...


Growth of single wall carbon nanotubes from 13C isotope labelled organic solvents inside single wall carbon nanotube hosts  

Microsoft Academic Search

We present the growth of single wall carbon nanotubes (SWCNTs) from organic solvents such as benzene and toluene inside a host SWCNT. The solvents encapsulated in SWCNTs are transformed to an inner tube when subject to a heat treatment under dynamic vacuum at 1270°C. We used isotope labeling of the different carbon sources to prove that the source of the

Ferenc Simon; Hans Kuzmany



Strontium and carbon isotope stratigraphy of the Late Jurassic shallow marine limestone in western Palaeo-Pacific, northwest Borneo  

E-print Network

Strontium and carbon isotope stratigraphy of the Late Jurassic shallow marine limestone in western-Pacific a b s t r a c t Strontium and carbon isotope stratigraphy was applied to a 202 m-thick shallow marine, which was deposited in the western Palaeo-Pacific. Strontium isotopic ratios of rudist specimens suggest

Gilli, Adrian


Calcification rate and the stable carbon, oxygen, and nitrogen isotopes in the skeleton, host tissue, and zooxanthellae  

E-print Network

Calcification rate and the stable carbon, oxygen, and nitrogen isotopes in the skeleton, host and oxygen isotopic compositions of the skeleton (d13 Cs; d18 Os) and nitrogen and carbon isotopic the warming event. During the remaining months of recovery, d13 Cs and d18 Os were more enriched in treatment

Grottoli, Andréa G.


Methane flux and carbon isotope composition correlate to shifting plant and microbial communities along a permafrost thaw gradient  

NASA Astrophysics Data System (ADS)

Methane flux from high latitude wetlands is a critical component of the global carbon budget and is highly sensitive to climate change, with observed and predicted increases as permafrost thaws. Microorganisms mediate wetland methane cycling, but connections between ecosystem-scale flux and underlying microbial dynamics are poorly understood. To address this gap we used isotopic (laser absorption spectrometry) and molecular (16S rRNA gene amplicon sequencing) techniques in a high latitude (68° N) wetland to investigate the relationship between microbial community composition and methane emissions across a permafrost thaw gradient. The transition from permafrost dominated, well drained palsas, through intermediate thaw sites dominated by Sphagnum spp., to wet sites with no underlying permafrost dominated by Eriophorum angustifolium is associated with substantial increases in methane emission. Across this thaw progression the carbon isotopic composition of emitted methane increased from -79.5 ‰ in the intermediate-thawing site to -66.4 ‰ in the thawed site, indicating a relative shift from CO2-reductive towards acetoclastic methanogenesis. Increases in methane flux under thaw were correlated with increasing abundance of methane-producing archaeal clades and increases in methane isotopic composition were associated with shifts in the archaeal community. While CO2 reducing methanogens were found throughout thawing and thawed sites, methanogens of the Methanosarcina (the order of Archaea that contains all known acetoclastic methanogens) were most associated with the fully thawed site. These results directly link microbial community composition to ecosystem scale changes in the magnitude and isotopic composition of methane emissions under permafrost thaw. If isotopic shifts of this magnitude are characteristic of methane dynamics under permafrost loss they should also become detectable in global atmospheric methane observations, providing a global scale tracer of shifting microbial communities associated with permafrost thaw.

McCalley, C. K.; Mondav, R.; Chanton, J.; Crill, P. M.; Hodgkins, S. B.; Kim, E.; Rich, V. I.; Wehr, R.; Woodcroft, B. J.; Tyson, G. W.; Saleska, S. R.



Effects of pre-treatments and organic matter on oxygen and carbon isotope analyses of skeletal and inorganic calcium carbonate  

NASA Astrophysics Data System (ADS)

The oxygen and carbon isotope composition of skeletal and inorganic calcites and aragonites was measured with or without pre-treatments (vacuum roasting, NaOCl and H2O2 treatments) used for removing organic matter. In addition, mixtures of pure calcium carbonate and organic matter (simple organic compounds, coal and kerogen) were analyzed with or without the thermal and oxidizing treatments. The studied organic substances have no effect on isotope analyses of untreated samples carried out by using the phosphoric acid method. The experimental results indicate that the roasting treatment may produce carbon isotope exchange between calcium carbonate and organic matter. Changes in original [delta]18O and [delta]13C values of calcites and [delta]13C values of aragonites were observed after the NaOCl treatment of the skeletal and inorganic samples. The H2O2 treatment causes minor deviations in original [delta] values, although may cause partial dissolution of calcium carbonate. Unnecessary usage of pre-treatment methods may be a source of errors in stable isotope analyses and palaeotemperature determinations based on the oxygen isotope composition of skeletal carbonates.

Wierzbowski, Hubert



Stable carbon isotopes as an indicator of petroleum biodegradation in estuarine sediments  

E-print Network

STABLE CARBON ISOTOPES AS AN INDICATOR OF PETROLEUM BIODEGRADATION IN ESTUARINE SEDIMENTS A Thesis by DEBORAH LOUISE HESSE Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements... for the degree of MASTER OF SCIENCE May 1994 Major Subject: Oceanography STABLE CARBON ISOTOPES AS INDICATORS OF PETROLEUM BIODEGRADATION IN ESTUARINE SEDIMENTS A Thesis by DEBORAH LOUISE HESSE Submitted to Texas A8 M University in partial fulfillment...

Hesse, Deborah Louise



Oxygen isotopes of detrital carbonate in Heinrich Layers: Implications for reconstructing surface water delta18O  

Microsoft Academic Search

We measured oxygen isotopes of individual detrital carbonate grains in Heinrich layers at three North Atlantic sites, including Core HU90-013-028 from the Labrador slope, IODP Site U1302\\/03 at Orphan Knoll, and IODP Site U1308 (re-occupation of DSDP Site 609) in the eastern North Atlantic. Oxygen isotopic values of individual detrital carbonate grains from all Heinrich events at all sites average

D. Hodell; J. Curtis



Carbon-bearing iron phases and the carbon isotope composition of the deep Earth.  


The carbon budget and dynamics of the Earth's interior, including the core, are currently very poorly understood. Diamond-bearing, mantle-derived rocks show a very well defined peak at ?(13)C ? -5 ± 3‰ with a very broad distribution to lower values (?-40‰). The processes that have produced the wide ?(13)C distributions to the observed low ?(13)C values in the deep Earth have been extensively debated, but few viable models have been proposed. Here, we present a model for understanding carbon isotope distributions within the deep Earth, involving Fe-C phases (Fe carbides and C dissolved in Fe-Ni metal). Our theoretical calculations show that Fe and Si carbides can be significantly depleted in (13)C relative to other C-bearing materials even at mantle temperatures. Thus, the redox freezing and melting cycles of lithosphere via subduction upwelling in the deep Earth that involve the Fe-C phases can readily produce diamond with the observed low ?(13)C values. The sharp contrast in the ?(13)C distributions of peridotitic and eclogitic diamonds may reflect differences in their carbon cycles, controlled by the evolution of geodynamical processes around 2.5-3 Ga. Our model also predicts that the core contains C with low ?(13)C values and that an average ?(13)C value of the bulk Earth could be much lower than ?-5‰, consistent with those of chondrites and other planetary body. The heterogeneous and depleted ?(13)C values of the deep Earth have implications, not only for its accretion-differentiation history but also for carbon isotope biosignatures for early life on the Earth. PMID:25512520

Horita, Juske; Polyakov, Veniamin B



Determining the Local Abundance of Martian Methane and its 13-C/l2-C and D/H Isotopic Ratios for Comparison with Related Gas and Soil Analysis on the 2011 Mars Science Laboratory (MSL) Mission  

NASA Technical Reports Server (NTRS)

Understanding the origin of Martian methane will require numerous complementary measurements from both in situ and remote sensing investigations and laboratory work to correlate planetary surface geophysics with atmospheric dynamics and chemistry. Three instruments (Quadrupole Mass Spectrometer (QMS), Gas Chromatograph (GC) and Tunable Laser Spectrometer (TLS)) with sophisticated sample handling and processing capability make up the Sample Analysis at Mars (SAM) analytical chemistry suite on NASA s 2011 Mars Science Laboratory (MSL) Mission. Leveraging off the SAM sample and gas processing capability that includes methane enrichment, TLS has unprecedented sensitivity for measuring absolute methane (parts-per-trillion), water, and carbon dioxide abundances in both the Martian atmosphere and evolved from heated soil samples. In concert with a wide variety of associated trace gases (e.g. SO2, H2S, NH3, higher hydrocarbons, organics, etc.) and other isotope ratios measured by SAM, TLS will focus on determining the absolute abundances of methane, water and carbon dioxide, and their isotope ratios: 13C/12C and D/H in methane; 13C/12C and 18O/17O/16O in carbon dioxide; and 18O/17O/16O and D/H in water. Measurements near the MSL landing site will be correlated with satellite (Mars Express, Mars 2016) and ground-based observations.

Webster, Christopher R.; Mahaffy, Paul R.



Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa  

NASA Technical Reports Server (NTRS)

The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic sparites are most depleted in 13C. Carbonates in oxide-rich iron-formations are more depleted in 13C than those in siderite-rich iron-formation whereas the kerogens in oxide banded iron-formations (BIF) are more enriched. This implies that the siderite-rich iron-formations were not derived from oxide-rich iron-formation through reduction of ferric iron by organic matter. Organic matter oxidation by ferric iron did, however, decrease the abundance of kerogen in oxide-rich iron-formation and led to the formation of isotopically very light sparry carbonates. Siderite and calcmicrosparite both represent recrystallized primary micritic precipitates but differ in their 13C composition, with the siderites depleted in 13C by 4.6 per mil on average relative to calcmicrosparite. This means that the siderites were precipitated from water with dissolved inorganic carbon depleted in 13C by about 9 per mil relative to that from which the limestones precipitated. This implies an ocean system stratified with regard to total carbonate, with the deeper water, from which siderite-rich iron-formation formed, depleted in 13C. Iron-formations were deposited in areas of very low organic matter supply. Depletion of 13C may, therefore, derive not from degradation of organic matter but from hydrothermal activity, a conclusion which is supported by 18O composition of the carbonate minerals and trace element and rare earth element (REE) compositions of the iron-formations.

Beukes, N. J.; Klein, C.; Kaufman, A. J.; Hayes, J. M.