Spatially-resolved isotopic study of carbon trapped in ∼3.43 Ga Strelley Pool Formation stromatolites

NASA Astrophysics Data System (ADS)

Flannery, David T.; Allwood, Abigail C.; Summons, Roger E.; Williford, Kenneth H.; Abbey, William; Matys, Emily D.; Ferralis, Nicola

2018-02-01

The large isotopic fractionation of carbon associated with enzymatic carbon assimilation allows evidence for life's antiquity, and potentially the early operation of several extant metabolic pathways, to be derived from the stable carbon isotope record of sedimentary rocks. Earth's organic carbon isotope record extends to the Late Eoarchean-Early Paleoarchean: the age of the oldest known sedimentary rocks. However, complementary inorganic carbon reservoirs are poorly represented in the oldest units, and commonly reported bulk organic carbon isotope measurements do not capture the micro-scale isotopic heterogeneities that are increasingly reported from younger rocks. Here, we investigated the isotopic composition of the oldest paired occurrences of sedimentary carbonate and organic matter, which are preserved as dolomite and kerogen within textural biosignatures of the ∼3.43 Ga Strelley Pool Formation. We targeted least-altered carbonate phases in situ using microsampling techniques guided by non-destructive elemental mapping. Organic carbon isotope values were measured by spatially-resolved bulk analyses, and in situ using secondary ion mass spectrometry to target microscale domains of organic material trapped within inorganic carbon matrixes. Total observed fractionation of 13C ranges from -29 to -45‰. Our data are consistent with studies of younger Archean rocks that host biogenic stromatolites and organic-inorganic carbon pairs showing greater fractionation than expected for Rubisco fixation alone. We conclude that organic matter was fixed and/or remobilized by at least one metabolism in addition to the CBB cycle, possibly by the Wood-Ljungdahl pathway or methanogenesis-methanotrophy, in a shallow-water marine environment during the Paleoarchean.

Carbon and Sulfur Isotopic Signatures of Ancient Life and Environment at the Microbial Scale: Neoarchean Shales and Carbonates

NASA Technical Reports Server (NTRS)

Williford, K. H.; Ushikubo, T.; Lepot, K.; Kitajima, K.; Hallmann, C.; Spicuzza, M. J.; Kozdon, R.; Eigenbrode, J. L.; Summons, R. E.; Valley, J. W.

2015-01-01

An approach to coordinated, spatially resolved, in situ carbon isotope analysis of organic matter and carbonate minerals, and sulfur three- and four-isotope analysis of pyrite with an unprecedented combination of spatial resolution, precision, and accuracy is described. Organic matter and pyrite from eleven rock samples of Neoarchean drill core express nearly the entire range of delta(sup 13)C, delta(sup 34)S, Delta(sup 33)S, and Delta(sup 36)S known from the geologic record, commonly in correlation with morphology, mineralogy, and elemental composition. A new analytical approach (including a set of organic calibration standards) to account for a strong correlation between H/C and instrumental bias in SIMS delta(sup 13)C measurement of organic matter is identified. Small (2-3 microns) organic domains in carbonate matrices are analyzed with sub-permil accuracy and precision. Separate 20- to 50-micron domains of kerogen in a single approx. 0.5 cu cm sample of the approx. 2.7 Ga Tumbiana Formation have delta(sup 13)C = -52.3 +/- 0.1per mille and -34.4 +/- 0.1per mille, likely preserving distinct signatures of methanotrophy and photoautotrophy. Pyrobitumen in the approx. 2.6 Ga Jeerinah Formation and the approx. 2.5 Ga Mount McRae Shale is systematically 13C-enriched relative to co-occurring kerogen, and associations with uraniferous mineral grains suggest radiolytic alteration. A large range in sulfur isotopic compositions (including higher Delta(sup 33)S and more extreme spatial gradients in Delta(sup 33)S and Delta(sup 36)S than any previously reported) are observed in correlation with morphology and associated mineralogy. Changing systematics of delta(sup 34)S, Delta(sup 33)S, and Delta(sup 36)S, previously investigated at the millimeter to centimeter scale using bulk analysis, are shown to occur at the micrometer scale of individual pyrite grains. These results support the emerging view that the dampened signature of mass-independent sulfur isotope fractionation

A Modern Analogue for Proterozoic Inverse Carbon Isotope Signatures

NASA Astrophysics Data System (ADS)

Close, H. G.; Diefendorf, A. F.; Freeman, K. H.; Pearson, A.

2008-12-01

The carbon isotope distribution preserved in sedimentary lipids changes near the Neoproterozoic-Cambrian boundary. In older samples, n-alkyl lipids contain more 13C than both isoprenoid lipids and kerogen [1]. In younger samples, the opposite prevails. Although extreme heterotrophy has been invoked as a mechanism to explain the enrichment in 13C [2], here we suggest another explanation. The switch may reflect a fundamental transition from an oligotrophic ocean dominated by prokaryotic biomass, to an ocean in which carbon fixation is more intensive and burial is dominated by eukaryotic biomass. An analogue for Proterozoic ordering is found in the modern, oligotrophic Pacific Ocean, where n-alkyl lipids of picoplankton (0.2-0.5 μm particulate matter) contain excess 13C relative to the same lipids found in larger size classes (> 0.5 μm). Picoplanktonic lipids are heavier isotopically (-18 ‰) than both the sterols of eukaryotes (-23 ‰ to -26 ‰) and the total organic matter (-20 ‰; TOM). The 0.2-0.5 μm size class also has a distinct chain-length abundance profile. Although large particles must be the vehicle for total carbon export, paradoxically the lipid component of export production appears to be dominated by the 0.2-0.5 μm source. The picoplanktonic chain lengths and isotopic composition dominate lipids of TOM at 670 meters. When the ratio of prokaryotic to eukaryotic production is high, as in the modern central Pacific Ocean, it appears that exported material has an inverse carbon isotope signature similar to that preserved in Precambrian samples. [1] Logan, G. A. et al., Nature 376:53-56 (1995). [2] Rothman, D. H. et al., PNAS 100:8124-8129 (2003).

In Situ Carbon and Sulfur Isotope Analysis of Archean Organic Matter and Pyrite

NASA Technical Reports Server (NTRS)

Williford, K. H.; Ushikubo, T.; LePot, K.; Kitajima, K.; Spicuzza, M. J.; Valley, J. W.; Hallman, C.; Summons, R.; Eigenbrode, J. L.

2012-01-01

Stable isotopic compositions of biologically important elements (e.g., C and S) in sedimentary rocks are valuable biosignatures to the extent that they indicate the presence and variable expression of microbial metabolisms in space and time. Strong interactions between the carbon and sulfur cycles (e.g., via organic matter remineralization during microbial sulfate reduction) make coordinated, in situ C and S isotope analysis by secondary ion mass spectrometry (SIMS) a particularly powerful tool. In rocks ranging in age from 2.7-2.5 Ga, expansions in the ranges of delta C-13 of organic matter and delta S-34 of pyrite likely reflect the increasing influence of oxygenic photosynthesis in the surface ocean (as well as methane and sulfur metabolisms in deeper waters), whereas the large range of mass independent sulfur isotope fractionation (Delta S-33) suggests that the atmosphere remained anoxic until approx 2.4 Gyr ago. We report in situ delta C-13 measurements of organic matter in the approx 2.7-2.6 Ga Carawine Dolomite, Marra Mamba Iron Formation, and Jeerinah, Wittenoom, and Tumbiana Formations, as well as the approx 2.5 Ga Mount McRae Shale. We also report in situ delta S-24 and Delta S-33 measurements of pyrite associated with organic matter in a subset of these samples. In a single square cm sample of the Tumbiana Formation with bulk delta C-13(sub org) of -49.7% (VPDB), two distinct kerogen types have delta C-13 values, measured in situ, consistent with oxygenic photosynthesis (-33%) and methane metabolism (-52%). In a sample from the ABDP-9 core, radiobitumen associated with a uraniferous mineral grain is C-13-enriched by 8% (-26.8%0) relative to average in situ kerogen (-34.9%0) and similar in delta C-13 to solvent extractable hydrocarbons from the Mount McRae Shale (avg delta C-13 = -27.1 %). Average reproducibility for delta C-13 was 0.4% (2 SD) using a 6 micron spot and 0.8% using a 3 micron spot. In situ sulfur isotope analyses of 33 authigenic pyrite

Methylhopane Biomarker and Carbon Isotopic Evidence for Late Archean Aerobic Ecosystems

NASA Technical Reports Server (NTRS)

Eigenbrode, Jennifer L.; Freeman, Katherine H.; Summons, Roger E.

2007-01-01

Molecular fossils are particularly valuable in early Earth studies because they provide information about microbial sources and ecology. Here we report on the distribution of 2- methyl and 3-methylhopanes preserved in a 2.72-2.56 billion-year-old section of shallow and deepwater sediments of the Hamersley Province [Eigenbrode et aI., submitted]. These biomarkers are mostly from cyanobacteria and oxygen-respiring methanotrophs, respectively. The relative abundance of 2-methylhopanes increases with carbonate abundance in shallow-water facies indicating cyanobacteria were key microbes in shallow ecosystems and suggesting they supplied both molecular oxygen and fixed carbon. The relative abundance of 3-methylhopane strongly correlates with kerogen-carbon isotopic values, and is more abundant in the samples with 13C-enriched signatures. Thus, molecular data provides evidence for cycling of methane in shallow settings, even though the anoxic deeper environments bear stronger 13C-depletion, which together suggests a more complex methane cycle than previously envisioned. Detailed facies analysis of the Hamersley carbon-isotope record reveals temporal changes suggesting continued oxidation of shallow settings favoring the expansion of aerobic ecosystems and respiring organisms [Eigenbrode et aI., 2006, PNAS, 103: 15759]. Similar analysis of published carbon-isotopic records suggests similar, but diachronous, expansion of oxygenated habitats in shallow then deep waters as anaerobic microbial communities gave way to respiring communities fueled by oxygenic photosynthesis before the post 2.45-Ga atmospheric oxygenation event [Eigenbrode et aI., 2006]. The robust relationships observed provide geochemical support for methanogenesis, aerobic methanotrophy, and oxygenic photosynthesis in the late Archean, as well as major ecological shifts linked to biogeochemical reorganization.

Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogen precursors

NASA Technical Reports Server (NTRS)

Van De Meent, D.; Brown, S. C.; Philp, R. P.; Simoneit, B. R. T.

1980-01-01

A series of kerogens and kerogen precursors isolated from DSDP samples, oil shales and recent algal mats have been examined by Curie point pyrolysis-high resolution gas chromatography and gas chromatography-mass spectrometry. This study has shown that the three main types of kerogens (marine, terrestrial and mixtures of both) can be characterized using these techniques. The marine (algal) kerogens yield principally aliphatic products and the terrestrial kerogens yield more aromatic and phenolic products with some n-alkanes and n-alkenes. The yields of n-alkanes and n-alkenes increase and phenols decrease with increasing geologic age, however, pyrolysis-GC cannot be used to characterize the influence of short term diagenesis on the kerogen structure.

Geochemical significance of alkylbenzene distributions in flash pyrolysates of kerogens, coals, and asphaltenes

NASA Astrophysics Data System (ADS)

Hartgers, Walter A.; Damsté, Jaap S. Sinninghe; de Leeuw, Jan W.

1994-04-01

The distribution of C 0-C 5 alkylbenzenes in flash pyrolysates of forty-seven immature kerogens and coals from different geographical locations and of different ages were studied using gas chromatography (GC) in combination with mass spectrometry (MS) in order to decipher the origin of aromatic moieties in macromolecular matter. All possible structural isomers of the alkylated benzenes were determined, and, in some cases, absolute yields were calculated. Sulphur-rich (Type II-S) kerogens yield higher absolute amounts of alkylbenzenes in comparison to Type I, II, and III kerogens. The variations in internal distribution patterns of C 2-C 4 alkylbenzenes were analyzed using multivariate analysis techniques (principal component analysis; PCA). Major variations in alkylbenzene distributions were due to an increased abundance of specific alkylbenzenes, which are related to specific precursor moieties in the macromolecular structure assuming that they are mainly formed via β-cleavage. Alkylbenzenes possessing "linear" carbon skeletons are enhanced in flash pyrolysates of Guttenberg and Estonian Kukersite kerogens (Type I) and are proposed to be derived from linear precursors which have undergone cyclization/aromatization. Relatively high amounts of 1,2,3,4- and 1,2,3,5-tetramethylbenzenes were found in flash pyrolysates of Womble and Duvernay kerogens (Type II) which are likely to be derived from macromolecularly bound diaromatic carotenoids. The relatively high abundance of 1,2,3-trimethylbenzene and 1,3-/1,4-dimethylbenzene in pyrolysates of Monterey kerogens (Type II-S) is proposed to be indicative of the presence of bound nonaromatic carotenoids (e.g., β,β-carotene) which have undergone aromatization and/or loss of methyl groups upon diagenesis. 1-methyl-4-isopropylbenzene, which appears in relatively high amounts in flash pyrolysates of Walcott Chuar kerogen (Type II) and Catalan coals (Type III), is thought to be derived from a heteroatom-bound precursor. These

Controls on the molecular and carbon isotopic composition of organic matter deposited in a Kimmeridgian euxinic shelf sea: evidence for preservation of carbohydrates through sulfurisation

NASA Astrophysics Data System (ADS)

Van Kaam-Peters, Heidy M. E.; Schouten, Stefan; Köster, Jörgen; Sinninghe Damstè, Jaap S.

1998-10-01

Thirteen samples from the Kimmeridge Clay Formation (KCF) in Dorset, covering all different lithologies, were studied using bulk and molecular geochemical and microscopical techniques. Our data show that the positive correlation between TOC and δ 13C TOC reported for shales (Huc et al., 1992) also holds for other lithologies (e.g., limestones) if we correct for dilution by carbonate (TOC∗). Despite the wide range of δ 13C TOC values (-26.7 to -20.7‰), the δ 13C values of individual biomarkers of algal and green sulfur bacterial origin and of kerogen pyrolysis products (i.e., n-alkanes) show in general only small changes (<2‰). This indicates that changes in the concentration of dissolved inorganic carbon (DIC) or δ 13C of DIC (δ 13C DIC) in the palaeowater column cannot account for the 6‰ difference in δ 13C TOC. Kerogen pyrolysates indicated that with increasing TOC∗, and thus increasing δ 13C TOC, carbon isotopically heavy C 1-C 3 alkylated thiophenes with a linear carbon skeleton become increasingly abundant; in the case of the Blackstone Band kerogen (TOC∗ = 63%) they dominate the pyrolysate. These thiophenes are probably derived from sulfur-bound carbohydrates in the kerogen. Algal carbohydrates are typically 5-10‰ heavier than algal lipids and differences in preservation of labile carbohydrate carbon through sulfurisation may thus explain the range in δ 13C TOC values without the need to invoke any change in water column conditions. The increasing dominance of thiophenes in the kerogen pyrolysate with increasing TOC∗ is consistent with the increasing Sulfur Index (mg S org/g TOC), the decreasing S PYRITE/S TOT ratio, and the increasing dominance of orange amorphous organic matter produced by natural sulfurisation. The organic matter of all sediments was deposited under euxinic conditions as revealed by the occurrence of isorenieratene derivatives indicating (periodic) photic zone euxinia. At times of reduced run-off from the hinterland

From cellulose to kerogen: molecular simulation of a geological process.

PubMed

Atmani, Lea; Bichara, Christophe; Pellenq, Roland J-M; Van Damme, Henri; van Duin, Adri C T; Raza, Zamaan; Truflandier, Lionel A; Obliger, Amaël; Kralert, Paul G; Ulm, Franz J; Leyssale, Jean-Marc

2017-12-01

The process by which organic matter decomposes deep underground to form petroleum and its underlying kerogen matrix has so far remained a no man's land to theoreticians, largely because of the geological (Myears) timescale associated with the process. Using reactive molecular dynamics and an accelerated simulation framework, the replica exchange molecular dynamics method, we simulate the full transformation of cellulose into kerogen and its associated fluid phase under prevailing geological conditions. We observe in sequence the fragmentation of the cellulose crystal and production of water, the development of an unsaturated aliphatic macromolecular phase and its aromatization. The composition of the solid residue along the maturation pathway strictly follows what is observed for natural type III kerogen and for artificially matured samples under confined conditions. After expulsion of the fluid phase, the obtained microporous kerogen possesses the structure, texture, density, porosity and stiffness observed for mature type III kerogen and a microporous carbon obtained by saccharose pyrolysis at low temperature. As expected for this variety of precursor, the main resulting hydrocarbon is methane. The present work thus demonstrates that molecular simulations can now be used to assess, almost quantitatively, such complex chemical processes as petrogenesis in fossil reservoirs and, more generally, the possible conversion of any natural product into bio-sourced materials and/or fuel.

Development of Simultaneous in situ Analysis of Carbon and Nitrogen Isotope Ratios in the Organic Matter by Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Ishida, A.; Kitajima, K.; Williford, K. H.; Kakegawa, T.; Valley, J. W.

2017-12-01

An in-situ analytical method for simultaneous analysis of carbon and nitrogen isotope ratios in organic matter was developed for 12 μm spots by secondary ion mass spectrometry (IMS 1280 at WiscSIMS). Secondary ions of 12C12C-, 12C13C-, 12C14N-, and 12C15N- are simultaneously measured by three Faraday cups and one electron multiplier. Ions of 12C12CH- are measured to monitor hydride interferences. The spot-by-spot reproducibility of δ13C and δ15N values of UWLA-1 anthracite standard (95.7 wt%C and 1.2 wt%N), which was selected as a running reference material, are 0.16‰ and 0.56‰ (2SD), respectively. A negative correlation is observed between the instrumental mass fractionation (mass bias) of carbon and 12C12CH-/12C12C- ratios of examined reference materials. In contrast, there is no correlation of mass bias and hydride cps for nitrogen isotope measurements, suggesting the mass bias of nitrogen can be determined independently of the hydrogen. Values of 22 individual globules of organic matter in a carbonate rock from the 1.9 Ga Gunflint Formation, determined by the new procedure, average δ13C = -33.5 ± 0.25‰ (VPDB) and δ15N = +5.2 ± 0.81‰ (Air). Values of δ13C of both SIMS and bulk kerogen analyses are consistent within analytical error. In contrast, a difference of 1.7‰, which is larger than the 2SD error of each analysis, is observed in δ15N values for in situ vs. bulk kerogen analyses (δ15Nbulk = +6.9 ± 0.6‰). This difference in δ15N might be caused by the preferential removal of low-δ15N components in the organic matter by HCl/HF acid treatment during the bulk kerogen isolation. Simultaneous analyses of carbon and nitrogen in the same micro-volume of organic matter in Precambrian sedimentary rocks will allow correlations with textures and mineralogical occurrences, which will provide more detailed constraints on environments and life of the early Earth. Furthermore, this method is applicable to a wide variety of other research fields

Detecting Kerogen as a Biosignature Using Colocated UV Time-Gated Raman and Fluorescence Spectroscopy.

PubMed

Shkolyar, Svetlana; Eshelman, Evan J; Farmer, Jack D; Hamilton, David; Daly, Michael G; Youngbull, Cody

2018-04-01

The Mars 2020 mission will analyze samples in situ and identify any that could have preserved biosignatures in ancient habitable environments for later return to Earth. Highest priority targeted samples include aqueously formed sedimentary lithologies. On Earth, such lithologies can contain fossil biosignatures as aromatic carbon (kerogen). In this study, we analyzed nonextracted kerogen in a diverse suite of natural, complex samples using colocated UV excitation (266 nm) time-gated (UV-TG) Raman and laser-induced fluorescence spectroscopies. We interrogated kerogen and its host matrix in samples to (1) explore the capabilities of UV-TG Raman and fluorescence spectroscopies for detecting kerogen in high-priority targets in the search for possible biosignatures on Mars; (2) assess the effectiveness of time gating and UV laser wavelength in reducing fluorescence in Raman spectra; and (3) identify sample-specific issues that could challenge rover-based identifications of kerogen using UV-TG Raman spectroscopy. We found that ungated UV Raman spectroscopy is suited to identify diagnostic kerogen Raman bands without interfering fluorescence and that UV fluorescence spectroscopy is suited to identify kerogen. These results highlight the value of combining colocated Raman and fluorescence spectroscopies, similar to those obtainable by SHERLOC on Mars 2020, to strengthen the confidence of kerogen detection as a potential biosignature in complex natural samples. Key Words: Raman spectroscopy-Laser-induced fluorescence spectroscopy-Mars Sample Return-Mars 2020 mission-Kerogen-Biosignatures. Astrobiology 18, 431-453.

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

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

Sorption of phenanthrene and benzene on differently structural kerogen: important role of micropore-filling.

PubMed

Zhang, Yulong; Ma, Xiaoxuan; Ran, Yong

2014-02-01

Shale was thermally treated to obtain a series of kerogen with varied maturation. Their chemical, structural and porous properties were related to the sorption and/or desorption behaviors of phenanthrene and benzene. As the treatment temperature increases, aliphatic and carbonyl carbon of the kerogen samples decrease, while their aromaticity and maturation increase. Meanwhile, the isothermal nonlinearity of phenanthrene and benzene increases whereas the sorption capacity and micropore adsorption volumes (Vo,d) initially increase and then decrease. The Vo,d of benzene is significantly correlated with, but higher than that of phenanthrene, suggesting similar micropore filling mechanism and molecular sieve effect. The benzene desorption exhibits hysteresis, which is related to the pore deformation of the kerogen and the entrapment of solute in the kerogen matrix. The Vo,d of phenanthrene and benzene on the kerogen samples accounts for 23-46% and 36-65% of the maximum sorption volumes, respectively, displaying the importance of the micropore filling. Copyright © 2013 Elsevier Ltd. All rights reserved.

Detecting Kerogen as a Biosignature Using Co-located UV Time-Gated Raman and Fuorescence Spectroscopy

NASA Astrophysics Data System (ADS)

Shkolyar, S.; Eshelman, E.; Farmer, J. D.; Hamilton, D.; Daly, M. G.; Youngbull, C.

2017-12-01

The Mars 2020 mission will analyze samples in situ and identify any that could have preserved biosignatures in ancient habitable environments for later return to Earth. Highest-priority targeted samples include aqueously formed sedimentary lithologies containing fossil biosignatures as aromatic carbon (kerogen). In this study, we analyze non-extracted, naturally preserved kerogen in a diverse suite of realistic Mars analogs using combined UV excitation time-gated (UV-TG) Raman and laser-induced fluorescence spectroscopy. We interrogated kerogen and its host matrix in samples to: (1) explore the capabilities of UV-TG Raman and fluorescence spectroscopy for detecting kerogen in high-priority targets in the search for a Martian fossil record; (2) assess the effectiveness of time-gating and UV laser wavelength in reducing fluorescence; and (3) identify sample-specific issues which could challenge rover-based identifications of kerogen using UV-TG Raman spectroscopy. We found that ungated UV Raman is suited to identify diagnostic kerogen Raman bands without interfering fluorescence and that fluorescence features indicating kerogen are detectable. These data highlight the value of using both co-located Raman and fluorescence data sets together to strengthen the confidence of kerogen detection as a potential biosignature and are obtainable by SHERLOC onboard Mars 2020.

Realistic molecular model of kerogen's nanostructure

NASA Astrophysics Data System (ADS)

Bousige, Colin; Ghimbeu, Camélia Matei; Vix-Guterl, Cathie; Pomerantz, Andrew E.; Suleimenova, Assiya; Vaughan, Gavin; Garbarino, Gaston; Feygenson, Mikhail; Wildgruber, Christoph; Ulm, Franz-Josef; Pellenq, Roland J.-M.; Coasne, Benoit

2016-05-01

Despite kerogen's importance as the organic backbone for hydrocarbon production from source rocks such as gas shale, the interplay between kerogen's chemistry, morphology and mechanics remains unexplored. As the environmental impact of shale gas rises, identifying functional relations between its geochemical, transport, elastic and fracture properties from realistic molecular models of kerogens becomes all the more important. Here, by using a hybrid experimental-simulation method, we propose a panel of realistic molecular models of mature and immature kerogens that provide a detailed picture of kerogen's nanostructure without considering the presence of clays and other minerals in shales. We probe the models' strengths and limitations, and show that they predict essential features amenable to experimental validation, including pore distribution, vibrational density of states and stiffness. We also show that kerogen's maturation, which manifests itself as an increase in the sp2/sp3 hybridization ratio, entails a crossover from plastic-to-brittle rupture mechanisms.

Realistic molecular model of kerogen's nanostructure.

PubMed

Bousige, Colin; Ghimbeu, Camélia Matei; Vix-Guterl, Cathie; Pomerantz, Andrew E; Suleimenova, Assiya; Vaughan, Gavin; Garbarino, Gaston; Feygenson, Mikhail; Wildgruber, Christoph; Ulm, Franz-Josef; Pellenq, Roland J-M; Coasne, Benoit

2016-05-01

Despite kerogen's importance as the organic backbone for hydrocarbon production from source rocks such as gas shale, the interplay between kerogen's chemistry, morphology and mechanics remains unexplored. As the environmental impact of shale gas rises, identifying functional relations between its geochemical, transport, elastic and fracture properties from realistic molecular models of kerogens becomes all the more important. Here, by using a hybrid experimental-simulation method, we propose a panel of realistic molecular models of mature and immature kerogens that provide a detailed picture of kerogen's nanostructure without considering the presence of clays and other minerals in shales. We probe the models' strengths and limitations, and show that they predict essential features amenable to experimental validation, including pore distribution, vibrational density of states and stiffness. We also show that kerogen's maturation, which manifests itself as an increase in the sp(2)/sp(3) hybridization ratio, entails a crossover from plastic-to-brittle rupture mechanisms.

Possible carotenoid-derived structures in fossil kerogens

NASA Astrophysics Data System (ADS)

Machihara, Tsutomu; Ishiwatari, Ryoshi

1987-02-01

The unique KMnO 4 degradation products of β-carotene, previously identified as 2,2-dimethyl succinic acid (C 6) and 2,2-dimethyl glutaric acid (C 7) have been found in the oxidation products of Green River shale (Eocene, 52 × 10 6yr) and Tasmanian Tasmanite (Permian, 220-274 × 10 6yr) kerogens. These two compounds were also detected in KMnO 4 degradation products of young kerogens from lacustrine and marine sediments. The results indicate that kerogens incorporated carotenoids (possibly β-carotene) at the time of kerogen formation in surface sediments. Both acids are useful markers to obtain information on biological precursors contributing to the formation of fossil kerogens.

Characteristics of amorphous kerogens fractionated from terrigenous sedimentary rocks

NASA Astrophysics Data System (ADS)

Suzuki, Noriyuki

1984-02-01

A preliminary attempt to fractionate amorphous kerogens from terrigenous bulk kerogen by a benzene-water two phase partition method under acidic condition was made. Microscopic observation revealed that amorphous kerogens and structured kerogens were fractionated effectively by this method. Characteristics of the amorphous and structured kerogens fractionated by this method were examined by some chemical analyses and compared with those of the bulk kerogen and humic acid isolated from the same rock sample (Haizume Formation, Pleistocene, Japan). The elemental and infrared (IR) analyses showed that the amorphous kerogen fraction had the highest atomic H/C ratio and the lowest atomic N/C ratio and was the richest in aliphatic structures and carbonyl and carboxyl functional groups. Quantities of fatty acids from the saponification products of each geopolymer were in agreement with the results of elemental and IR analyses. Distribution of the fatty acids was suggestive that more animal lipids participate in the formation of amorphous kerogens because of the abundance of relatively lower molecular weight fatty acids (such as C 16 and C 18 acids) in saponification products of amorphous kerogens. On the other hand, although the amorphous kerogen fraction tends to be rich in aliphatic structures compared with bulk kerogen of the same rock samples, van Krevelen plots of elemental compositions of kerogens from the core samples (Nishiyama Oil Field, Tertiary, Japan) reveal that the amorphous kerogen fraction is not necessarily characterized by markedly high atomic H/C ratio. This was attributed to the oxic environment of deposition and the abundance of biodegraded terrestrial amorphous organic matter in the amorphous kerogen fraction used in this work.

Possible carotenoid-derived structures in fossil kerogens

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

Machihara, T.; Ishiwatari, R.

The unique KMnO/sub 4/ degradation products of ..beta..-carotene, previously identified as 2,2-dimethyl succinic acid (C/sub 6/) and 2,2-dimethyl glutaric acid (C/sub 7/) have been found in the oxidation products of Green River shale (Eocene, 52 x 10/sup 6/ yr) and Tasmanian Tasmanite (Permian, 220-274 x 10/sup 6/ yr) kerogens. These two compounds were also detected in KMnO/sub 4/ degradation products of young kerogens from lacustrine and marine sediments. The results indicate that kerogens incorporated carotenoids (possibly ..beta..-carotene) at the time of kerogen formation in surface sediments. Both acids are useful markers to obtain information on biological precursors contributing to themore » formation of fossil kerogens.« less

Re-Os geochronology and Os isotope fingerprinting of petroleum sourced from a Type I lacustrine kerogen: Insights from the natural Green River petroleum system in the Uinta Basin and hydrous pyrolysis experiments

NASA Astrophysics Data System (ADS)

Cumming, Vivien M.; Selby, David; Lillis, Paul G.; Lewan, Michael D.

2014-08-01

Rhenium-osmium (Re-Os) geochronology of marine petroleum systems has allowed the determination of the depositional age of source rocks as well as the timing of petroleum generation. In addition, Os isotopes have been applied as a fingerprinting tool to correlate oil to its source unit. To date, only classic marine petroleum systems have been studied. Here we present Re-Os geochronology and Os isotope fingerprinting of different petroleum phases (oils, tar sands and gilsonite) derived from the lacustrine Green River petroleum system in the Uinta Basin, USA. In addition we use an experimental approach, hydrous pyrolysis experiments, to compare to the Re-Os data of naturally generated petroleum in order to further understand the mechanisms of Re and Os transfer to petroleum. The Re-Os geochronology of petroleum from the lacustrine Green River petroleum system (19 ± 14 Ma - all petroleum phases) broadly agrees with previous petroleum generation basin models (∼25 Ma) suggesting that Re-Os geochronology of variable petroleum phases derived from lacustrine Type I kerogen has similar systematics to Type II kerogen (e.g., Selby and Creaser, 2005a,b; Finlay et al., 2010). However, the large uncertainties (over 100% in some cases) produced for the petroleum Re-Os geochronology are a result of multiple generation events occurring through a ∼3000-m thick source unit that creates a mixture of initial Os isotope compositions in the produced petroleum phases. The 187Os/188Os values for the petroleum and source rocks at the time of oil generation vary from 1.4 to 1.9, with the mode at ∼1.6. Oil-to-source correlation using Os isotopes is consistent with previous correlation studies in the Green River petroleum system, and illustrates the potential utility of Os isotopes to characterize the spatial variations within a petroleum system. Hydrous pyrolysis experiments on the Green River Formation source rocks show that Re and Os transfer are mimicking the natural system. This

Re-Os geochronology and Os isotope fingerprinting of petroleum sourced from a Type I lacustrine kerogen: insights from the natural Green River petroleum system in the Uinta Basin and hydrous pyrolysis experiments

USGS Publications Warehouse

Cumming, Vivien M.; Selby, David; Lillis, Paul G.; Lewan, Michael D.

2014-01-01

Rhenium–osmium (Re–Os) geochronology of marine petroleum systems has allowed the determination of the depositional age of source rocks as well as the timing of petroleum generation. In addition, Os isotopes have been applied as a fingerprinting tool to correlate oil to its source unit. To date, only classic marine petroleum systems have been studied. Here we present Re–Os geochronology and Os isotope fingerprinting of different petroleum phases (oils, tar sands and gilsonite) derived from the lacustrine Green River petroleum system in the Uinta Basin, USA. In addition we use an experimental approach, hydrous pyrolysis experiments, to compare to the Re–Os data of naturally generated petroleum in order to further understand the mechanisms of Re and Os transfer to petroleum. The Re–Os geochronology of petroleum from the lacustrine Green River petroleum system (19 ± 14 Ma – all petroleum phases) broadly agrees with previous petroleum generation basin models (∼25 Ma) suggesting that Re–Os geochronology of variable petroleum phases derived from lacustrine Type I kerogen has similar systematics to Type II kerogen (e.g., Selby and Creaser, 2005a, Selby and Creaser, 2005b and Finlay et al., 2010). However, the large uncertainties (over 100% in some cases) produced for the petroleum Re–Os geochronology are a result of multiple generation events occurring through a ∼3000-m thick source unit that creates a mixture of initial Os isotope compositions in the produced petroleum phases. The 187Os/188Os values for the petroleum and source rocks at the time of oil generation vary from 1.4 to 1.9, with the mode at ∼1.6. Oil-to-source correlation using Os isotopes is consistent with previous correlation studies in the Green River petroleum system, and illustrates the potential utility of Os isotopes to characterize the spatial variations within a petroleum system. Hydrous pyrolysis experiments on the Green River Formation source rocks show that Re and Os transfer

Carbon isotopes in mollusk shell carbonates

NASA Astrophysics Data System (ADS)

McConnaughey, Ted A.; Gillikin, David Paul

2008-10-01

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 δ13C reflects the local mix of C3 and C4 plants consumed. Shell δ13C 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 δ13C is typically a few ‰ lower than ambient DIC, and often decreases with age. Shell δ13C 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.

Impact of kerogen heterogeneity on sorption of organic pollutants. 2. Sorption equilibria

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

Yang, C.; Yu, Z.Q.; Xiao, B.H.

2009-08-15

Phenanthrene and naphthalene sorption isotherms were measured for three different series of kerogen materials using completely mixed batch reactors. Sorption isotherms were nonlinear for each sorbate-sorbent system, and the Freundlich isotherm equation fit the sorption data well. The Freundlich isotherm linearity parameter n ranged from 0.192 to 0.729 for phenanthrene and from 0.389 to 0.731 for naphthalene. The n values correlated linearly with rigidity and aromaticity of the kerogen matrix, but the single-point, organic carbon-normalized distribution coefficients varied dramatically among the tested sorbents. A dual-mode sorption equation consisting of a linear partitioning domain and a Langmuir adsorption domain adequately quantifiedmore » the overall sorption equilibrium for each sorbent-sorbate system. Both models fit the data well, with r{sup 2} values of 0.965 to 0.996 for the Freundlich model and 0.963 to 0.997 for the dual-mode model for the phenanthrene sorption isotherms. The dual-mode model fitting results showed that as the rigidity and aromaticity of the kerogen matrix increased, the contribution of the linear partitioning domain to the overall sorption equilibrium decreased, whereas the contribution of the Langmuir adsorption domain increased. The present study suggested that kerogen materials found in soils and sediments should not be treated as a single, unified, carbonaceous sorbent phase.« less

Factors controlling the abundance of organic sulfur in flash pyrolyzates of Upper Cretaceous kerogens from Sergipe Basin, Brazil

USGS Publications Warehouse

Carmo, A.M.; Stankiewicz, B.A.; Mastalerz, Maria; Pratt, L.M.

1997-01-01

The molecular and elemental composition of immature kerogens isolated from Upper Cretaceous marine carbonates from Sergipe Basin, Brazil were investigated using combined pyrolysis-gas chromatography/mass spectrometry and organic petrographic techniques. The kerogens are predominantly composed of reddish-fluorescing amorphous organic matter (AOM) and variable amounts of yellow-fluorescing alginite and liptodetrinite. The abundance of organic sulfur in the kerogens inferred from the ratio 2-ethyl-5-methylthiophene/(1,2-dimethylbenzene + dec-1-ene) in the pyrolyzates is variable and may be related to changes in the type of primary organic input and/or to variations in rates of bacterial sulfate reduction. A concomitant increase in S/C and O/C ratios determined in situ using the electron microprobe is observed in AOM and alginites and may be related to a progressive oxidation of the organic matter during sulfurization. The S/C ratio of the AOM is systematically higher than the S C ratio of the alginites. Combined with a thiophene distribution characteristic of pyrolyzates of Type II organic matter, the higher S/C of AOM in Sergipe kerogens suggests that sulfurization and incorporation of low-molecular weight lipids derived from normal marine organic matter into the kerogen structure predominated over direct sulfurization of highly aliphatic algal biomacromolecules.The molecular and elemental composition of immature kerogens isolated from Upper Cretaceous marine carbonates from Sergipe Basin, Brazil were investigated using combined pyrolysis-gas chromatography/mass spectrometry and organic petrographic techniques. The kerogens are predominantly composed of reddish-fluorescing amorphous organic matter (AOM) and variable amounts of yellow-fluorescing alginite and liptodetrinite. The abundance of organic sulfur in the kerogens inferred from the ratio 2-ethyl-5-methylthiophene/(1,2-dimethylbenzene+dec-1-ene) in the pyrolyzates is variable and may be related to changes in

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope and Water Chemistry Characterizations

NASA Technical Reports Server (NTRS)

Fu, Qi; Socki, Richard A.; Niles, Paul B.; Romanek, Christopher; Datta, Saugata; Darnell, Mike; Bissada, Adry K.

2013-01-01

estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 C, and higher than the values measured at orifices (77.3 to 90.0 C). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The C-13 fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 C) is suggested as being responsible for the generation of CO2 in SVHS.

Synthetic isotope mixtures for the calibration of isotope amount ratio measurements of carbon

NASA Astrophysics Data System (ADS)

Russe, K.; Valkiers, S.; Taylor, P. D. P.

2004-07-01

Synthetic isotope mixtures for the calibration of carbon isotope amount ratio measurements have been prepared by mixing carbon tetrafluoride highly enriched in 13C with carbon tetrafluoride depleted in 13C. Mixing procedures based on volumetry and gravimetry are described. The mixtures served as primary measurement standards for the calibration of isotope amount ratio measurements of the Isotopic Reference Materials PEF1, NBS22 and USGS24. Thus SI-traceable measurements of absolute carbon isotope amount ratios have been performed for the first time without any hypothesis needed for a correction of oxygen isotope abundances, such as is the case for measurements on carbon dioxide. As a result, "absolute" carbon isotope amount ratios determined via carbon tetrafluoride have smaller uncertainties than those published for carbon dioxide. From the measurements of the Reference Materials concerned, the absolute carbon isotope amount ratio of Vienna Pee Dee Belemnite (VPDB)--the hypothetical material upon which the scale for relative carbon isotope ratio measurements is based--was calculated to be R13(VPDB) = (11 101 +/- 16) × 10-6.

Kerogen extraction from subterranean oil shale resources

DOEpatents

Looney, Mark Dean; Lestz, Robert Steven; Hollis, Kirk; Taylor, Craig; Kinkead, Scott; Wigand, Marcus

2010-09-07

The present invention is directed to methods for extracting a kerogen-based product from subsurface (oil) shale formations, wherein such methods rely on fracturing and/or rubblizing portions of said formations so as to enhance their fluid permeability, and wherein such methods further rely on chemically modifying the shale-bound kerogen so as to render it mobile. The present invention is also directed at systems for implementing at least some of the foregoing methods. Additionally, the present invention is also directed to methods of fracturing and/or rubblizing subsurface shale formations and to methods of chemically modifying kerogen in situ so as to render it mobile.

Kerogen extraction from subterranean oil shale resources

DOEpatents

Looney, Mark Dean [Houston, TX; Lestz, Robert Steven [Missouri City, TX; Hollis, Kirk [Los Alamos, NM; Taylor, Craig [Los Alamos, NM; Kinkead, Scott [Los Alamos, NM; Wigand, Marcus [Los Alamos, NM

2009-03-10

The present invention is directed to methods for extracting a kerogen-based product from subsurface (oil) shale formations, wherein such methods rely on fracturing and/or rubblizing portions of said formations so as to enhance their fluid permeability, and wherein such methods further rely on chemically modifying the shale-bound kerogen so as to render it mobile. The present invention is also directed at systems for implementing at least some of the foregoing methods. Additionally, the present invention is also directed to methods of fracturing and/or rubblizing subsurface shale formations and to methods of chemically modifying kerogen in situ so as to render it mobile.

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

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

McConnaughey, T.A.

1986-01-01

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 organicmore » 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.« less

Mesozoic black shales, source mixing and carbon isotopes

NASA Astrophysics Data System (ADS)

Suan, Guillaume

2016-04-01

Over the last decades, considerable attention has been devoted to the paleoenvironmental and biogeochemical significance of Mesozoic black shales. Black shale-bearing successions indeed often display marked changes in the organic carbon isotope composition (δ13Corg), which have been commonly interpreted as evidence for dramatic perturbations of global carbon budgets and CO2 levels. Arguably the majority of these studies have discarded some more "local" explanations when interpreting δ13Corg profiles, most often because comparable profiles occur on geographically large and distant areas. Based on newly acquired data and selected examples from the literature, I will show that the changing contribution of organic components with distinct δ13C signatures exerts a major but overlooked influence of Mesozoic δ13Corg profiles. Such a bias occurs across a wide spectrum of sedimentological settings and ages, as shown by the good correlation between δ13Corg values and proxies of kerogen proportions (such as rock-eval, biomarker, palynofacies and palynological data) recorded in Mesozoic marginal to deep marine successions of Triassic, Jurassic and Cretaceous age. In most of these successions, labile, 12C-enriched amorphous organic matter of marine origin dominates strata deposited under anoxic conditions, while oxidation-resistant, 13C-rich terrestrial particles dominate strata deposited under well-oxygenated conditions. This influence is further illustrated by weathering profiles of Toarcian (Lower Jurassic) black shales from France, where weathered areas dominated by refractory organic matter show dramatic 13C-enrichment (and decreased total organic carbon and pyrite contents) compared to non-weathered portions of the same horizon. The implications of these results for chemostratigraphic correlations and pCO2 reconstructions of Mesozoic will be discussed, as well as strategies to overcome this major bias.

Carbon isotope geochemistry and geobiology

NASA Technical Reports Server (NTRS)

Desmarais, D.

1985-01-01

Carbon isotope fractionation values were used to understand the history of the biosphere. For example, plankton analyses confirmed that marine extinctions at the end of the Cretaceous period were indeed severe (see Hsu's article in Sundquist and Broeker, 1984). Variations in the isotopic compositions of carbonates and evaporitic sulfates during the Paleozoic reflect the relative abundances of euxinic (anoxic) marine environments and organic deposits from terrestrial flora. The carbon isotopic composition of Precambrian sediments suggest that the enzyme ribulose bisphosphate carboxylase has existed for perhaps 3.5 billion years.

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope aud Water Chemistry Characterizations

NASA Technical Reports Server (NTRS)

Fu, Qi; Socki, Richard A.; Niles, Paul B.; Romanek, Christopher; Datta, Saugata; Darnell, Mike; Bissada, Adry K.

2013-01-01

by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 oC, and higher than the values measured at orifices (77.3 to 90.0 oC). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The 13C fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 oC) is suggested as being responsible for the generation of CO2 in SVHS.

Carbon isotopes in biological carbonates: Respiration and photosynthesis

USGS Publications Warehouse

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

1997-01-01

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.

Carbon isotopes in biological carbonates: Respiration and photosynthesis

NASA Astrophysics Data System (ADS)

McConnaughey, Ted A.; Burdett, Jim; Whelan, Joseph F.; Paull, Charles K.

1997-02-01

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 CO 2/O 2 ratios appear to be the major controlling variable. Atmospheric CO 2/O 2 ratios are about thirty times lower than in most natural waters, hence air breathing animals absorb less environmental CO 2 in the course of obtaining 0 2. Tissue CO 2 therefore, does not isotopically equilibrate with environmental CO 2 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 CO 2 in their tissues. Photosynthetic corals calcify mainly during the daytime when photosynthetic CO 2 uptake is several times faster than respiratory CO 2 release. Photosynthesis, therefore, affects skeletal δ13C 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.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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.

Stable sulfur isotope partitioning during simulated petroleum formation as determined by hydrous pyrolysis of Ghareb Limestone, Israel

USGS Publications Warehouse

Amrani, A.; Lewan, M.D.; Aizenshtat, Zeev

2005-01-01

Hydrous pyrolysis experiments at 200 to 365??C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2 S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2??? in 34S during thermal maturation compared with the initial ??34S values. The ??34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1??? of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21??? lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the ??34S-enriched secondary pyrite decomposes above 300??C resulting in a corresponding decrease in the ??34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen ??34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The

Long-chain carboxylic acids in pyrolysates of Green River kerogen

NASA Technical Reports Server (NTRS)

Kawamura, K.; Tannenbaum, E.; Huizinga, B. J.; Kaplan, I. R.

1986-01-01

Long-chain fatty acids (C10-C32), as well as C14-C21 isoprenoid acids (except for C18), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200-400 degrees C, 2-1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C16 followed by lesser amounts of C18 and C22 acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C14, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C18 and C30. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300 degrees C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.

The carbon isotopic composition of ecosystem breath

NASA Astrophysics Data System (ADS)

Ehleringer, J.

2008-05-01

At the global scale, there are repeatable annual fluctuations in the concentration and isotopic composition of atmospheric carbon dioxide, sometimes referred to as the "breathing of the planet". Vegetation components within ecosystems fix carbon dioxide through photosynthesis into stable organic compounds; simultaneously both vegetation and heterotrophic components of the ecosystem release previously fixed carbon as respiration. These two-way fluxes influencing carbon dioxide exchange between the biosphere and the atmosphere impact both the concentration and isotopic composition of carbon dioxide within the convective boundary layer. Over space, the compounding effects of gas exchange activities from ecosystems become reflected in both regional and global changes in the concentration and isotopic composition of atmospheric carbon dioxide. When these two parameters are plotted against each other, there are significant linear relationships between the carbon isotopic composition and inverse concentration of atmospheric carbon dioxide. At the ecosystem scale, these "Keeling plots" intercepts of C3-dominated ecosystems describe the carbon isotope ratio of biospheric gas exchange. Using Farquhar's model, these carbon isotope values can be translated into quantitative measures of the drought-dependent control of photosynthesis by stomata as water availability changes through time. This approach is useful in aggregating the influences of drought across regional landscapes as it provides a quantitative measure of stomatal influence on photosynthetic gas exchange at the ecosystem-to-region scales. Multi-year analyses of the drought-dependent trends across terrestrial ecosystems show a repeated pattern with water stress in all but one C3-ecosystem type. Ecosystems that are dominated by ring-porous trees appear not to exhibit a dynamic stomatal response to water stress and therefore, there is little dependence of the carbon isotope ratio of gas exchange on site water balance

Changing carbon isotope ratio of atmospheric carbon dioxide: implications for food authentication.

PubMed

Peck, William H; Tubman, Stephanie C

2010-02-24

Carbon isotopes are often used to detect the addition of foreign sugars to foods. This technique takes advantage of the natural difference in carbon isotope ratio between C(3) and C(4) plants. Many foods are derived from C(3) plants, but the low-cost sweeteners corn and sugar cane are C(4) plants. Most adulteration studies do not take into account the secular shift of the carbon isotope ratio of atmospheric carbon dioxide caused by fossil fuel burning, a shift also seen in plant tissues. As a result statistical tests and threshold values that evaluate authenticity of foods based on carbon isotope ratios may need to be corrected for changing atmospheric isotope values. Literature and new data show that the atmospheric trend in carbon isotopes is seen in a 36-year data set of maple syrup analyses (n = 246), demonstrating that published thresholds for cane or corn sugar adulteration in maple syrup (and other foods) have become progressively more lenient over time.

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

NASA Technical Reports Server (NTRS)

Boehme, Susan E.

1993-01-01

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.

Site-Specific Carbon Isotopes in Organics

NASA Astrophysics Data System (ADS)

Piasecki, A.; Eiler, J. M.

2012-12-01

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 μm. 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 δ13C and the difference in δ13C between the terminal and central carbon position. We tested this method by analyzing mixtures between natural

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

USGS Publications Warehouse

Putschew, A.; Schaeffer-Reiss, C.; Schaeffer, P.; Koopmans, M.P.; De Leeuw, J. W.; Lewan, M.D.; Sinninghe, Damste J.S.; Maxwell, J.R.

1998-01-01

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330??C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH2 and HI/LiAIH4) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis-GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260??C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak Carbon-heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220??C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.

Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

NASA Technical Reports Server (NTRS)

Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

1983-01-01

In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.

Rapid and direct screening of H:C ratio in Archean kerogen via microRaman Spectroscopy

NASA Astrophysics Data System (ADS)

Ferralis, N.; Matys, E. D.; Allwood, A.; Knoll, A. H.; Summons, R. E.

2015-12-01

Rapid evaluation of the preservation of biosignatures in ancient kerogens is essential for the evaluation of the usability of Earth analogues as proxies of Martian geological materials. No single, non-destructive and non-invasive technique currently exists to rapidly determine such state of preservation of the organic matter in relation to its geological and mineral environment. Due to its non-invasive nature, microRaman spectroscopy is emerging as a candidate technique for the qualitative determination maturity of organic matter, by correlating Raman spectral features and aromatic carbon cluster size. Here we will present a novel quantitative method in which before-neglected Raman spectral features are correlated directly and with excellent accuracy with the H:C ratio. In addition to providing a chemical justification of the found direct correlation, we will show its applicability and predictive capabilities in evaluating H:C in Archean kerogens. This novel method opens new opportunities for the use of Raman spectroscopy and mapping. This includes the non-invasively determination of kerogen preservation and microscale chemical diversity within a particular Earth analogue, to be potentially extended to evaluate Raman spectra acquired directly on Mars.

Isotopic fractionation of nitrogen and carbon in Paleoarchean cherts from Pilbara craton, Western Australia: Origin of 15N-depleted nitrogen

NASA Astrophysics Data System (ADS)

Pinti, Daniele L.; Hashizume, Ko; Sugihara, Akiyo; Massault, Marc; Philippot, Pascal

2009-07-01

Nitrogen and carbon isotopic compositions, together with mineralogy and trace element geochemistry, were studied in a few kerogen-rich Paleoarchean cherts, a barite and a dolomitic stromatolite belonging to the eastern (Dixon Island Formation) and western (Dresser and Strelley Pool Chert Formations; North Pole Dome and Marble Bar) terranes of Pilbara Craton, Western Australia. The aim of the study was to search for 15N-depleted isotopic signatures, often found in kerogens of this period, and explain the origin of these anomalies. Trace elements suggest silica precipitation by hydrothermal fluids as the main process of chert formation with a contamination from volcanoclastic detritus. This is supported by the occurrence of hydrothermal-derived minerals in the studied samples indicating precipitation temperatures up to 350 °C. Only a dolomitic stromatolite from Strelley Pool shows a superchondritic Y/Ho ratio of 72 and a positive Eu/Eu * anomaly of 1.8, characteristic of chemical precipitates from the Archean seawater. The bulk δ 13C vs. δ 15N values measured in the cherts show a roughly positive co-variation, except for one sample from the North Pole (PI-85-00). The progressive enrichment in 15N and 13C from a pristine source having δ 13C ⩽ -36‰ and δ 15N ⩽ -4‰ is correlated with a progressive depletion in N content and to variations in Ba/La and Co/As ratios. These trends have been interpreted as a progressive hydrothermal alteration of the cherts by metamorphic fluids. Isotopic exchange at 350 °C between NH 4+(rock) and N 2(fluid) may explain the isotopic and elemental composition of N in the studied cherts. However, we need to assume isotopic exchange at 350 °C between carbonate C and graphite to explain the large 13C enrichment recorded. Only sample PI-85-00 shows a large N loss (90%) with a positive δ 15N value (+11‰), while C (up to 120 ppm and δ 13C -38‰) seems to be unaffected. This pattern has been interpreted as the result of

Electron-probe microanalysis of light elements in coal and other kerogen

USGS Publications Warehouse

Bustin, R.M.; Mastalerz, Maria; Raudsepp, M.

1996-01-01

Recent advances in electron microprobe technology including development of layered synthetic microstructures, more stable electronics and better matrix-correction programs facilitated routine microanalysis of the light elements in coal. Utilizing an appropriately equipped electron microprobe with suitable standards, it is now possible to analyze directly the light elements (C, O and N, if abundant) in coal macerals and other kerogen. The analytical results are both accurate compared to ASTM methods and highly precise, and provide an opportunity to access the variation in coal chemistry at the micrometre scale. Our experiments show that analyses using a 10 kV accelerating voltage and 10 nA beam current yield the most reliable data and result in minimum sample damage and contamination. High sample counts were obtained for C, O and N using a bi-elemental nickel-carbon pseudo-crystal (2d = 9.5 nm) as an analyzing crystal. Vitrinite isolated from anthracite rank coal proves the best carbon standard and is more desirable than graphite which has higher porosity, whereas lower rank vitrinite is too heterogeneous to use routinely as a standard. Other standards utilized were magnesite for oxygen and BN for nitrogen. No significant carbon, oxygen or nitrogen X-ray peak shifts or peak-shape changes occur between standards and the kerogen analyzed. Counting rates for carbon and oxygen were found to be constant over a range of beam sizes and currents for counting times up to 160 s. Probe-determined carbon and oxygen contents agree closely with those reported from ASTM analyses. Nitrogen analyses compare poorly to ASTM values which probably is in response to overlap between the nitrogen Ka peak with the carbon K-adsorption edge and the overall low nitrogen content of most of our samples. Our results show that the electron microprobe technique provides accurate compositional data for both minor and major elements in coal without the necessity and inherent problems associated with

Carbon isotope effects associated with autotrophic acetogenesis

NASA Technical Reports Server (NTRS)

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

1989-01-01

The carbon kinetic isotope effects associated with synthesis of acetate from CO2 and H2 during autotrophic growth of Acetobacterium woodii at 30 degrees 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 account. For the overall reaction, total carbonate --> total acetate, isotope effects measured in replicate experiments ranged from -59.0 +/- 0.9% to -57.2 +/- 2.3%. 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.

Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

NASA Technical Reports Server (NTRS)

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

1986-01-01

The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

Following Carbon Isotopes from Methane to Molecules

NASA Astrophysics Data System (ADS)

Freeman, K. H.

2017-12-01

Continuous-flow methods introduced by Hayes (Matthews and Hayes, 1978; Freeman et al., 1990; Hayes et al., 1990) for compound-specific isotope analyses (CSIA) transformed how we study the origins and fates of organic compounds. This analytical revolution launched several decades of research in which researchers connect individual molecular structures to diverse environmental and climate processes affecting their isotopic profiles. Among the first applications, and one of the more dramatic isotopically, was tracing the flow of natural methane into cellular carbon and cellular biochemical constituents. Microbial oxidation of methane can be tracked by strongly 13C-depleted organic carbon in early Earth sedimentary environments, in marine and lake-derived biomarkers in oils, and in modern organisms and their environments. These signatures constrain microbial carbon cycling and inform our understanding of ocean redox. The measurement of molecular isotopes has jumped forward once again, and it is now possible to determine isotope abundances at specific positions within increasingly complex organic structures. In addition, recent analytical developments have lowered sample sensitivity limits of CSIA to picomole levels. These new tools have opened new ways to measure methane carbon in the natural environment and within biochemical pathways. This talk will highlight how molecular isotope methods enable us to follow the fate of methane carbon in complex environments and along diverse metabolic pathways, from trace fluids to specific carbon positions within microbial biomarkers.

Carbon isotopic fractionation in heterotrophic microbial metabolism

NASA Technical Reports Server (NTRS)

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

1985-01-01

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.

Oxygen isotope analysis of fossil organic matter by secondary ion mass spectrometry

NASA Astrophysics Data System (ADS)

Tartèse, Romain; Chaussidon, Marc; Gurenko, Andrey; Delarue, Frédéric; Robert, François

2016-06-01

We have developed an analytical procedure for the measurement of oxygen isotope composition of fossil organic matter by secondary ion mass spectrometry (SIMS) at the sub-per mill level, with a spatial resolution of 20-30 μm. The oxygen isotope composition of coal and kerogen samples determined by SIMS are on average consistent with the bulk oxygen isotope compositions determined by temperature conversion elemental analysis - isotope ratio mass spectrometry (TC/EA-IRMS), but display large spreads of δ18O of ∼5-10‰, attributed to mixing of remnants of organic compounds with distinct δ18O signatures. Most of the δ18O values obtained on two kerogen residues extracted from the Eocene Clarno and Early Devonian Rhynie continental chert samples and on two immature coal samples range between ∼10‰ and ∼25‰. Based on the average δ18O values of these samples, and on the O isotope composition of water processed by plants that now constitute the Eocene Clarno kerogen, we estimated δ18Owater values ranging between around -11‰ and -1‰, which overall correspond well within the range of O isotope compositions for present-day continental waters. SIMS analyses of cyanobacteria-derived organic matter from the Silurian Zdanow chert sample yielded δ18O values in the range 12-20‰. Based on the O isotope composition measured on recent cyanobacteria from the hypersaline Lake Natron (Tanzania), and on the O isotope composition of the lake waters in which they lived, we propose that δ18O values of cyanobacteria remnants are enriched by about ∼18 ± 2‰ to 22 ± 2‰ relative to coeval waters. This relationship suggests that deep ocean waters in which the Zdanow cyanobacteria lived during Early Silurian times were characterised by δ18O values of around -5 ± 4‰. This study, establishing the feasibility of micro-analysis of Phanerozoic fossil organic matter samples by SIMS, opens the way for future investigations of kerogens preserved in Archean cherts and of the

Catalytic generation of methane at 60-100 °C and 0.1-300 MPa from source rocks containing kerogen Types I, II, and III

NASA Astrophysics Data System (ADS)

Wei, Lin; Schimmelmann, Arndt; Mastalerz, Maria; Lahann, Richard W.; Sauer, Peter E.; Drobniak, Agnieszka; Strąpoć, Dariusz; Mango, Frank D.

2018-06-01

Low temperature (60 and 100 °C) and long-term (6 months to 5 years) heating of pre-evacuated and sterilized shales and coals containing kerogen Types I (Mahogany Shale), II (Mowry Shale and New Albany Shale), and III (Springfield Coal and Wilcox Lignite) with low initial maturities (vitrinite reflectance Ro 0.39-0.62%) demonstrates that catalytically generated hydrocarbons may explain the occurrence of some non-biogenic natural gas accumulations where insufficient thermal maturity contradicts the conventional thermal cracking paradigm. Extrapolation of the observed rate of catalytic methanogenesis in the laboratory suggests that significant amounts of sedimentary organic carbon can be converted to relatively dry natural gas over tens of thousands of years in sedimentary basins at temperatures as low as 60 °C. Our laboratory experiments utilized source rock (shale and coal) chips sealed in gold and Pyrex® glass tubes in the presence of hydrogen-isotopically contrasting waters. Parallel heating experiments applied hydrostatic pressures from 0.1 to 300 MPa. Control experiments constrained the influence of pre-existing and residual methane in closed pores of rock chips that was unrelated to newly generated methane. This study's experimental methane yields at 60 and 100 °C are 5-11 orders of magnitude higher than the theoretically predicted yields from kinetic models of thermogenic methane generation, which strongly suggests a contribution of catalytic methanogenesis. Higher temperature, longer heating time, and lower hydrostatic pressure enhanced catalytic methanogenesis. No clear relationships were observed between kerogen type or total organic carbon content and methane yields via catalysis. Catalytic methanogenesis was strongest in Mowry Shale where methane yields at 60 °C amounted to ∼2.5 μmol per gram of organic carbon after one year of hydrous heating at ambient pressure. In stark contrast to the earlier findings of hydrogen isotopic exchange between

Preservation of carbonate clumped isotopes in sedimentary paleoclimate archives

NASA Astrophysics Data System (ADS)

Henkes, G. A.; Passey, B. H.; Grossman, E. L.; Shenton, B.; Perez-Huerta, A.

2014-12-01

Carbonate clumped isotope thermometry is increasingly used to reconstruct paleotemperatures of ancient terrestrial environments. One promising application is elucidating paleoelevation from carbonate archives such as paleosols, lacustrine marls, and fossil freshwater shells. Unlike conventional stable isotope approaches (e.g., mineral δ18O or δD), clumped isotope thermometry is independent of the isotopic composition of the precipitating waters and can therefore be used to reconstruct elevation by both the temperature-altitude relationship and the rainfall δ18O-altitude relationship. However, interpretation of clumped isotope data is not without its own complications. Like conventional stable isotopes, clumped isotope paleotemperatures can be effectively reset to warmer values by dissolution/reprecipitation-type diagenesis during sedimentary burial. It is also known that carbonate clumped isotope bonds (i.e., 13C-18O) are susceptible to 'reordering' in the solid mineral lattice at warmer burial temperatures, with laboratory studies of natural carbonates indicating activation of this phenomenon at temperatures as low as 100 °C over geologic timescales. A challenge in applying carbonate clumped isotope thermometry to natural samples is now evaluating terrestrial archives with respect to both types of alteration: 'open-system' alteration and 'closed-system' bond reordering. In this talk we will review our experimental efforts to constrain the kinetics of clumped isotope reordering, with relevance to low-temperature carbonates like fossil shells and early diagenetic minerals, and present new laboratory data that further inform our theoretical framework for the mechanism(s) of 13C-18O bond reordering. Together with traditional analytical and petrographic screening for recrystallization, empirical and laboratory studies of carbonate clumped isotope reordering represent the next steps in evaluating isotopic records of paleoclimate, paleobiology, and paleoelevation

Model representations of kerogen structures: An insight from density functional theory calculations and spectroscopic measurements.

PubMed

Weck, Philippe F; Kim, Eunja; Wang, Yifeng; Kruichak, Jessica N; Mills, Melissa M; Matteo, Edward N; Pellenq, Roland J-M

2017-08-01

Molecular structures of kerogen control hydrocarbon production in unconventional reservoirs. Significant progress has been made in developing model representations of various kerogen structures. These models have been widely used for the prediction of gas adsorption and migration in shale matrix. However, using density functional perturbation theory (DFPT) calculations and vibrational spectroscopic measurements, we here show that a large gap may still remain between the existing model representations and actual kerogen structures, therefore calling for new model development. Using DFPT, we calculated Fourier transform infrared (FTIR) spectra for six most widely used kerogen structure models. The computed spectra were then systematically compared to the FTIR absorption spectra collected for kerogen samples isolated from Mancos, Woodford and Marcellus formations representing a wide range of kerogen origin and maturation conditions. Limited agreement between the model predictions and the measurements highlights that the existing kerogen models may still miss some key features in structural representation. A combination of DFPT calculations with spectroscopic measurements may provide a useful diagnostic tool for assessing the adequacy of a proposed structural model as well as for future model development. This approach may eventually help develop comprehensive infrared (IR)-fingerprints for tracing kerogen evolution.

Thermal maturity of type II kerogen from the New Albany Shale assessed by13C CP/MAS NMR

USGS Publications Warehouse

Werner-Zwanziger, U.; Lis, G.; Mastalerz, Maria; Schimmelmann, A.

2005-01-01

Thermal maturity of oil and gas source rocks is typically quantified in terms of vitrinite reflectance, which is based on optical properties of terrestrial woody remains. This study evaluates 13C CP/MAS NMR parameters in kerogen (i.e., the insoluble fraction of organic matter in sediments and sedimentary rocks) as proxies for thermal maturity in marine-derived source rocks where terrestrially derived vitrinite is often absent or sparse. In a suite of samples from the New Albany Shale (Middle Devonian to the Early Mississippian, Illinois Basin) the abundance of aromatic carbon in kerogen determined by 13C CP/MAS NMR correlates linearly well with vitrinite reflectance. ?? 2004 Elsevier Inc. All rights reserved.

An in situ FTIR step-scan photoacoustic investigation of kerogen and minerals in oil shale.

PubMed

Alstadt, Kristin N; Katti, Dinesh R; Katti, Kalpana S

2012-04-01

Step-scan photoacoustic infrared spectroscopy experiments were performed on Green River oil shale samples obtained from the Piceance Basin located in Colorado, USA. We have investigated the molecular nature of light and dark colored areas of the oil shale core using FTIR photoacoustic step-scan spectroscopy. This technique provided us with the means to analyze the oil shale in its original in situ form with the kerogen-mineral interactions intact. All vibrational bands characteristic of kerogen were found in the dark and light colored oil shale samples confirming that kerogen is present throughout the depth of the core. Depth profiling experiments indicated that there are changes between layers in the oil shale molecular structure at a length scale of micron. Comparisons of spectra from the light and dark colored oil shale core samples suggest that the light colored regions have high kerogen content, with spectra similar to that from isolated kerogen, whereas, the dark colored areas contain more mineral components which include clay minerals, dolomite, calcite, and pyrite. The mineral components of the oil shale are important in understanding how the kerogen is "trapped" in the oil shale. Comparing in situ kerogen spectra with spectra from isolated kerogen indicate significant band shifts suggesting important nonbonded molecular interactions between the kerogen and minerals. Copyright © 2011 Elsevier B.V. All rights reserved.

Experimental controls on D/H and 13C/12C ratios of kerogen, bitumen and oil during hydrous pyrolysis

USGS Publications Warehouse

Schimmelmann, A.; Boudou, J.-P.; Lewan, M.D.; Wintsch, R.P.

2001-01-01

Large isotopic transfers between water-derived hydrogen and organic hydrogen occurred during hydrous pyrolysis experiments of immature source rocks, in spite of only small changes in organic 13C/12C. Experiments at 330 ??C over 72 h using chips or powder containing kerogen types I and III identify the rock/water ratio as a main factor affecting ????D for water and organic hydrogen. Our data suggest that larger rock permeability and smaller rock grain size increase the H-isotopic transfer between water-derived hydrogen and thermally maturing organic matter. Increasing hydrostatic pressure may have a similar effect, but the evidence remains inconclusive. ?? 2001 Elsevier Science Ltd. All rights reserved.

Uranium isotope fractionation in biogenic carbonates: biological effects

NASA Astrophysics Data System (ADS)

Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Anbar, A. D.

2017-12-01

Recent laboratory experiments have demonstrated small but potentially significant isotope fractionation ( 0.10 ‰ for 238U/235U) during uranium (U) incorporation into abiotic calcite and aragonite, with heavier U isotopes preferentially enriched in the precipitates [1]. In contrast, measurements of natural biogenic carbonates to date have not been able to resolve significant U isotopic fractionation from seawater although this might be expected given a typical measurement precision of ± 0.10 ‰. Determining whether or not biogenic carbonates display U isotope fractionation similar to abiotic carbonates could have important implications for understanding the mechanisms of U incorporation into various biogenic carbonates. Furthermore, because most marine carbonates are biogenic, the extent of isotopic fractionation, if any, could have important implications for the interpretation of sedimentary carbonates record similar to effects observed for Cr and B isotopes [2, 3]. To resolve this discrepancy, we utilized a higher precision 238U/235U method which uses larger sample sizes to improve measurement precision of natural samples to ± 0.02 ‰ (2 se, N = 6) [4]. Using this method, we have surveyed 238U/235U in primary biogenic skeletal carbonates including scleractinian corals, green and red algae, and mollusks, as well as non-skeletal carbonates such as stromatolites, ooids, and carbonate sands from the Bahamas, Gulf of California, and French Polynesia. New high-precision U isotopes measurements reveal that biogenic skeletal carbonates are typically 0.02 - 0.08 ‰ heavier than modern seawater. Scleractinian corals display values closest to seawater (- 0.37 ‰), while green algae, red algae, mollusks, and echinoderms display variable but larger extents of fractionation up to 0.08 ‰. The direction and magnitude of U isotope fractionation in these biogenic precipitates are generally consistent with results from abiotic coprecipitation experiments, but may be

Raman spectroscopy as a tool to understand Kerogen production potential

NASA Astrophysics Data System (ADS)

Khatibi, S.; Ostadhassan, M.; Mohammed, R. A.; Alexeyev, A.

2017-12-01

A lot attention has given to unconventional reservoirs specifically oil shale in North America during the last decades. Understanding Kerogen properties in terms of maturity and production potential are crucial for unconventional reservoir. Since, the amount of hydrocarbon generation is a function of kerogen type and content in the formation, and the magnitude and duration in which heat and pressure were applied. This study presents a non-destructive and fast method to determine Kerogen properties in terms of Rock-Eval parameters by means of Raman Spectroscopy. Samples were gathered from upper and lower Bakken formation, with different maturities at different depth. Raman spectroscopy as a powerful nondestructive analytical tool for molecular reconstruction was employed to find Raman spectra of different samples. In the next step, Rock-Eval was performed for each sample and different measurements were made. Then in an original approach, correlation between Rock-Eval parameters with Raman Spectroscopy results was established to fully understand how kerogen productivity potentials can be reflected on the Raman response. Results showed, maturity related parameters (RO, Tmax), S1 (already generated oil in the rock), S2 (potential hydrocarbon) and OSI (oil saturation index as indication of potential oil flow zones) can be correlated to band separation, D band intensity, G band intensity and G/D intensity, respectively. Proposed method provide a fast nondestructive method to evaluate Kerogen quality even at field without any special sample preparation.

Model representations of kerogen structures: An insight from density functional theory calculations and spectroscopic measurements

DOE PAGES

Weck, Philippe F.; Kim, Eunja; Wang, Yifeng; ...

2017-08-01

Molecular structures of kerogen control hydrocarbon production in unconventional reservoirs. Significant progress has been made in developing model representations of various kerogen structures. These models have been widely used for the prediction of gas adsorption and migration in shale matrix. However, using density functional perturbation theory (DFPT) calculations and vibrational spectroscopic measurements, we here show that a large gap may still remain between the existing model representations and actual kerogen structures, therefore calling for new model development. Using DFPT, we calculated Fourier transform infrared (FTIR) spectra for six most widely used kerogen structure models. The computed spectra were then systematicallymore » compared to the FTIR absorption spectra collected for kerogen samples isolated from Mancos, Woodford and Marcellus formations representing a wide range of kerogen origin and maturation conditions. Limited agreement between the model predictions and the measurements highlights that the existing kerogen models may still miss some key features in structural representation. A combination of DFPT calculations with spectroscopic measurements may provide a useful diagnostic tool for assessing the adequacy of a proposed structural model as well as for future model development. This approach may eventually help develop comprehensive infrared (IR)-fingerprints for tracing kerogen evolution.« less

Model representations of kerogen structures: An insight from density functional theory calculations and spectroscopic measurements

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

Weck, Philippe F.; Kim, Eunja; Wang, Yifeng

Molecular structures of kerogen control hydrocarbon production in unconventional reservoirs. Significant progress has been made in developing model representations of various kerogen structures. These models have been widely used for the prediction of gas adsorption and migration in shale matrix. However, using density functional perturbation theory (DFPT) calculations and vibrational spectroscopic measurements, we here show that a large gap may still remain between the existing model representations and actual kerogen structures, therefore calling for new model development. Using DFPT, we calculated Fourier transform infrared (FTIR) spectra for six most widely used kerogen structure models. The computed spectra were then systematicallymore » compared to the FTIR absorption spectra collected for kerogen samples isolated from Mancos, Woodford and Marcellus formations representing a wide range of kerogen origin and maturation conditions. Limited agreement between the model predictions and the measurements highlights that the existing kerogen models may still miss some key features in structural representation. A combination of DFPT calculations with spectroscopic measurements may provide a useful diagnostic tool for assessing the adequacy of a proposed structural model as well as for future model development. This approach may eventually help develop comprehensive infrared (IR)-fingerprints for tracing kerogen evolution.« less

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

NASA Technical Reports Server (NTRS)

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

1989-01-01

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.

The fate of river organic carbon in coastal areas: A study in the Rhône River delta using multiple isotopic (δ13C, Δ14C) and organic tracers

NASA Astrophysics Data System (ADS)

Cathalot, C.; Rabouille, C.; Tisnérat-Laborde, N.; Toussaint, F.; Kerhervé, P.; Buscail, R.; Loftis, K.; Sun, M.-Y.; Tronczynski, J.; Azoury, S.; Lansard, B.; Treignier, C.; Pastor, L.; Tesi, T.

2013-10-01

A significant fraction of the global carbon flux to the ocean occurs in River-dominated Ocean Margins (RiOMar) although large uncertainties remain in the cycle of organic matter (OM) in these systems. In particular, the OM sources and residence time have not been well clarified. Surface (0-1 cm) and sub-surface (3-4 cm) sediments and water column particles (bottom and intermediate depth) from the Rhône River delta system were collected in June 2005 and in April 2007 for a multi-proxy study. Lignin phenols, black carbon (BC), proto-kerogen/BC mixture, polycyclic aromatic hydrocarbons (PAHs), carbon stable isotope (δ13COC), and radiocarbon measurements (Δ14COC) were carried out to characterize the source of sedimentary organic material and to address degradation and transport processes. The bulk OM in the prodelta sediment appears to have a predominantly modern terrigenous origin with a significant contribution of modern vascular C3 plant detritus (Δ14COC = 27.9‰, δ13COC = -27.4‰). In contrast, the adjacent continental shelf, below the river plume, seems to be dominated by aged OM (Δ14COC = -400‰, δ13COC = -24.2‰), and shows no evidence of dilution and/or replacement by freshly produced marine carbon. Our data suggest an important contribution of black carbon (50% of OC) in the continental shelf sediments. Selective degradation processes occur along the main dispersal sediment system, promoting the loss of a modern terrestrial OM but also proto-kerogen-like OM. In addition, we hypothesize that during the transport across the shelf, a long term resuspension/deposition loop induces efficient long term degradation processes able to rework such refractory-like material until the OC is protected by the mineral matrix of particles.

Testing Urey's carbonate-silicate cycle using the calcium isotopic composition of sedimentary carbonates

NASA Astrophysics Data System (ADS)

Blättler, Clara L.; Higgins, John A.

2017-12-01

Carbonate minerals constitute a major component of the sedimentary geological record and an archive of a fraction of the carbon and calcium cycled through the Earth's surface reservoirs for over three billion years. For calcium, carbonate minerals constitute the ultimate sink for almost all calcium liberated during continental and submarine weathering of silicate minerals. This study presents >500 stable isotope ratios of calcium in Precambrian carbonate sediments, both limestones and dolomites, in an attempt to characterize the isotope mass balance of the sedimentary carbonate reservoir through time. The mean of the dataset is indistinguishable from estimates of the calcium isotope ratio of bulk silicate Earth, consistent with the Urey cycle being the dominant mechanism exchanging calcium among surface reservoirs. The variability in bulk sediment calcium isotope ratios within each geological unit does not reflect changes in the global calcium cycle, but rather highlights the importance of local mineralogical and/or diagenetic effects in the carbonate record. This dataset demonstrates the potential for calcium isotope ratios to help assess these local effects, such as the former presence of aragonite, even in rocks with a history of neomorphism and recrystallization. Additionally, 29 calcium isotope measurements are presented from ODP (Ocean Drilling Program) Site 801 that contribute to the characterization of altered oceanic crust as an additional sink for calcium, and whose distinct isotopic signature places a limit on the importance of this subduction flux over Earth history.

Stable isotope analysis of Dacryoconarid carbonate microfossils: a new tool for Devonian oxygen and carbon isotope stratigraphy.

PubMed

Frappier, Amy Benoit; Lindemann, Richard H; Frappier, Brian R

2015-04-30

Dacryoconarids are extinct marine zooplankton known from abundant, globally distributed calcite microfossils in the Devonian, but their shell stable isotope composition has not been previously explored. Devonian stable isotope stratigraphy is currently limited to less common invertebrates or bulk rock analyses of uncertain provenance. As with Cenozoic planktonic foraminifera, isotopic analysis of dacryoconarid shells could facilitate higher-resolution, geographically widespread stable isotope records of paleoenvironmental change, including marine hypoxia events, climate changes, and biocrises. We explored the use of Dacryoconarid isotope stratigraphy as a viable method in interpreting paleoenvironments. We applied an established method for determining stable isotope ratios (δ(13) C, δ(18) O values) of small carbonate microfossils to very well-preserved dacryoconarid shells. We analyzed individual calcite shells representing five common genera using a Kiel carbonate device coupled to a MAT 253 isotope ratio mass spectrometer. Calcite shell δ(13) C and δ(18) O values were compared by taxonomic group, rock unit, and locality. Single dacryoconarid calcite shells are suitable for stable isotope analysis using a Kiel-IRMS setup. The dacryoconarid shell δ(13) C values (-4.7 to 2.3‰) and δ(18) O values (-10.3 to -4.8‰) were consistent across taxa, independent of shell size or part, but varied systematically through time. Lower fossil δ(18) O values were associated with warmer water temperature and more variable δ(13) C values were associated with major bioevents. Dacryoconarid δ(13) C and δ(18) O values differed from bulk rock carbonate values. Dacryoconarid individual microfossil δ(13) C and δ(18) O values are highly sensitive to paleoenvironmental changes, thus providing a promising avenue for stable isotope chemostratigraphy to better resolve regional to global paleoceanographic changes throughout the upper Silurian to the upper Devonian. Our results

Gluconeogenesis from labeled carbon: estimating isotope dilution

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

Kelleher, J.K.

1986-03-01

To estimate the rate of gluconeogenesis from steady-state incorporation of labeled 3-carbon precursors into glucose, isotope dilution must be considered so that the rate of labeling of glucose can be quantitatively converted to the rate of gluconeogenesis. An expression for the value of this isotope dilution can be derived using mathematical techniques and a model of the tricarboxylic acid (TCA) cycle. The present investigation employs a more complex model than that used in previous studies. This model includes the following pathways that may affect the correction for isotope dilution: 1) flux of 3-carbon precursor to the oxaloacetate pool via acetyl-CoAmore » and the TCA cycle; 2) flux of 4- or 5-carbon compounds into the TCA cycle; 3) reversible flux between oxaloacetate (OAA) and pyruvate and between OAA and fumarate; 4) incomplete equilibrium between OAA pools; and 5) isotope dilution of 3-carbon tracers between the experimentally measured pool and the precursor for the TCA-cycle OAA pool. Experimental tests are outlined which investigators can use to determine whether these pathways are significant in a specific steady-state system. The study indicated that flux through these five pathways can significantly affect the correction for isotope dilution. To correct for the effects of these pathways an alternative method for calculating isotope dilution is proposed using citrate to relate the specific activities of acetyl-CoA and OAA.« less

Isotopic Signature of the Ancient Biosphere

NASA Technical Reports Server (NTRS)

DesMarais, D. J.; Chang, Sherwood (Technical Monitor)

1997-01-01

The age distribution of 261 field localities, sampled for their well-preserved Archean and Proterozoic sedimentary rocks, revealed a 500-700 Ma episodicity. Assuming that the numbers of sites are a proxy for mass of sediments, the record of well-preserved sediments is more abundant in the intervals 3.5-3.3, 2.8-2.5, 2.1-1.8, 1.5-1.3, and 1.0-0.54 Ga than in the intervening intervals. It is proposed that the crustal inventory of photosynthetic organic carbon was modulated by the volume of sedimentation in sites favorable for the burial and long-term preservation of organic carbon. Tectonic processes controlled this sediment volume. Episodic increases in the organic inventory led to stepwise increases in oxidized reservoirs (e.g., O2, SO4(2-), Fe(3+). The interval 2.9-2.5 Ga recorded a large rise in seawater Sr-87/Sr-86, the oldest-known extensive banded iron formations, and the first evidence (C-13-depleted kerogens) of O2 use by methylotrophic bacteria. The interval 2.2-1.8 Ga has both carbon isotopic evidence for a stepwise increase in the organic reservoir and also paleosol evidence for an O2 increase. The interval 1.1-0.6 Ga shows isotopic evidence for another organic carbon increase. The interval 1.5-1.3 Ga revealed no such increases as yet, perhaps because incomplete rifting of the mid-Proterozoic supercontinent was associated with extensive sedimentation in oxidized continental basins, producing redbeds, coarse clastics, etc. Such sedimentation did not promote the burial of reduced carbon.

Biological marker distribution in coexisting kerogen, bitumen and asphaltenes in Monterey Formation diatomite, California

NASA Technical Reports Server (NTRS)

Tannenbaum, E.; Ruth, E.; Huizinga, B. J.; Kaplan, I. R.

1986-01-01

Organic-rich (18.2%) Monterey Formation diatomite from California was studied. The organic matter consist of 94% bitumen and 6% kerogen. Biological markers from the bitumen and from pyrolysates of the coexisting asphaltenes and kerogen were analyzed in order to elucidate the relationship between the various fractions of the organic matter. While 17 alpha(H), 18 alpha(H), 21 alpha(H)-28,30-bisnorhopane was present in the bitumen and in the pryolysate of the asphaltenes, it was not detected in the pyrolysates of the kerogen. A C40-isoprenoid with "head to head" linkage, however, was present in pyrolysates of both kerogen and asphaltenes, but not in the bitumen from the diatomite. The maturation level of the bitumen, based on the extent of isomerization of steranes and hopanes, was that of a mature oil, whereas the pyrolysate from the kerogen showed a considerably lower maturation level. These relationships indicate that the bitumen may not be indigenous to the diatomite and that it is a mature oil that migrated into the rock. We consider the possibility, however, that some of the 28,30-bisnorhopane-rich Monterey Formation oils have not been generated through thermal degradation of kerogen, but have been expelled from the source rock at an early stage of diagenesis.

Examining Archean methanotrophy

NASA Astrophysics Data System (ADS)

Slotznick, Sarah P.; Fischer, Woodward W.

2016-05-01

The carbon isotope ratios preserved in sedimentary rocks can be used to fingerprint ancient metabolisms. Organic carbon in Late Archean samples stands out from that of other intervals with unusually low δ13C values (∼-45 to -60‰). It was hypothesized that these light compositions record ecosystem-wide methane cycling and methanotrophy, either of the aerobic or anaerobic variety. To test this idea, we studied the petrography and carbon and oxygen isotope systematics of well-known and spectacular occurrences of shallow water stromatolites from the 2.72 Ga Tumbiana Formation of Western Australia. We examined the carbonate cements and kerogen produced within the stromatolites, because methanotrophy is expected to leave an isotopic fingerprint in these carbon reservoirs. Mathematical modeling of Archean carbonate chemistry further reveals that methanotrophy should still have a discernible signature preserved in the isotopic record, somewhat diminished from those observed in Phanerozoic sedimentary basins due to higher dissolved inorganic carbon concentrations. These stromatolites contain kerogen with δ13Corg values of ∼ - 50 ‰. By microsampling different regions and textures within the stromatolites, we determined that the isotopic compositions of the authigenic calcite cements show a low degree of variation and are nearly identical to values estimated for seawater at this time; the lack of low and variable δ13Ccarb values implies that methanotrophy does not explain the low δ13Corg seen in the coeval kerogen. These observations do not support a methanotrophy hypothesis, but instead hint that the Late Archean may constitute an interval wherein autotrophs employed markedly different biochemical processes of energy conservation and carbon fixation.

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

NASA Technical Reports Server (NTRS)

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

1994-01-01

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

Carbon isotope fractionation during microbial methane oxidation

NASA Astrophysics Data System (ADS)

Barker, James F.; Fritz, Peter

1981-09-01

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.

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

NASA Astrophysics Data System (ADS)

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

2003-12-01

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<63μ 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

Mass transfer and carbon isotope evolution in natural water systems

USGS Publications Warehouse

Wigley, T.M.L.; Plummer, Niel; Pearson, F.J.

1978-01-01

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.

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

NASA Technical Reports Server (NTRS)

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

2004-01-01

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.

Characterization of oil shale, isolated kerogen, and post-pyrolysis residues using advanced 13 solid-state nuclear magnetic resonance spectroscopy

USGS Publications Warehouse

Cao, Xiaoyan; Birdwell, Justin E.; Chappell, Mark A.; Li, Yuan; Pignatello, Joseph J.; Mao, Jingdong

2013-01-01

Characterization of oil shale kerogen and organic residues remaining in postpyrolysis spent shale is critical to the understanding of the oil generation process and approaches to dealing with issues related to spent shale. The chemical structure of organic matter in raw oil shale and spent shale samples was examined in this study using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Oil shale was collected from Mahogany zone outcrops in the Piceance Basin. Five samples were analyzed: (1) raw oil shale, (2) isolated kerogen, (3) oil shale extracted with chloroform, (4) oil shale retorted in an open system at 500°C to mimic surface retorting, and (5) oil shale retorted in a closed system at 360°C to simulate in-situ retorting. The NMR methods applied included quantitative direct polarization with magic-angle spinning at 13 kHz, cross polarization with total sideband suppression, dipolar dephasing, CHn selection, 13C chemical shift anisotropy filtering, and 1H-13C long-range recoupled dipolar dephasing. The NMR results showed that, relative to the raw oil shale, (1) bitumen extraction and kerogen isolation by demineralization removed some oxygen-containing and alkyl moieties; (2) unpyrolyzed samples had low aromatic condensation; (3) oil shale pyrolysis removed aliphatic moieties, leaving behind residues enriched in aromatic carbon; and (4) oil shale retorted in an open system at 500°C contained larger aromatic clusters and more protonated aromatic moieties than oil shale retorted in a closed system at 360°C, which contained more total aromatic carbon with a wide range of cluster sizes.

FTIR absorption indices for thermal maturity in comparison with vitrinite reflectance R0 in type-II kerogens from Devonian black shales

USGS Publications Warehouse

Lis, G.P.; Mastalerz, Maria; Schimmelmann, A.; Lewan, M.D.; Stankiewicz, B.A.

2005-01-01

FTIR absorbance signals in kerogens and macerals were evaluated as indices for thermal maturity. Two sets of naturally matured type-II kerogens from the New Albany Shale (Illinois Basin) and the Exshaw Formation (Western Canada Sedimentary Basin) and kerogens from hydrous pyrolysis artificial maturation of the New Albany Shale were characterized by FTIR. Good correlation was observed between the aromatic/aliphatic absorption ratio and vitrinite reflectance R 0. FTIR parameters are especially valuable for determining the degree of maturity of marine source rocks lacking vitrinite. With increasing maturity, FTIR spectra express four trends: (i) an increase in the absorption of aromatic bands, (ii) a decrease in the absorption of aliphatic bands, (iii) a loss of oxygenated groups (carbonyl and carboxyl), and (iv) an initial decrease in the CH2/CH3 ratio that is not apparent at higher maturity in naturally matured samples, but is observed throughout increasing R0 in artificially matured samples. The difference in the CH2/CH 3 ratio in samples from natural and artificial maturation at higher maturity indicates that short-term artificial maturation at high temperatures is not fully equivalent to slow geologic maturation at lower temperatures. With increasing R0, the (carboxyl + carbonyl)/aromatic carbon ratio generally decreases, except that kerogens from the Exshaw Formation and from hydrous pyrolysis experiments express an intermittent slight increase at medium maturity. FTIR-derived aromaticities correlate well with R0, although some uncertainty is due to the dependence of FTIR parameters on the maceral composition of kerogen whereas R0 is solely dependent on vitrinite. ?? 2005 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2014-04-01

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 (Δ13C) between HCHO and fuel isotopic ratios was 7.4 ± 0.7‰, which was higher than that of HCHO from stand-alone gasoline engine (Δ13Cmax = 2.7‰), suggesting additional consumption by the catalytic converter. For diesel vehicle without catalytic converter, Δ13C 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

Origin of petroporphyrins. 2. Evidence from stable carbon isotopes

NASA Technical Reports Server (NTRS)

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

1990-01-01

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.

Carbon isotopic composition of individual Precambrian microfossils

NASA Technical Reports Server (NTRS)

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

2000-01-01

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

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

PubMed

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

2017-12-19

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

Modeling the carbon isotope composition of bivalve shells (Invited)

NASA Astrophysics Data System (ADS)

Romanek, C.

2010-12-01

The stable carbon isotope composition of bivalve shells is a valuable archive of paleobiological and paleoenvironmental information. Previous work has shown that the carbon isotope composition of the shell is related to the carbon isotope composition of dissolved inorganic carbon (DIC) in the ambient water in which a bivalve lives, as well as metabolic carbon derived from bivalve respiration. The contribution of metabolic carbon varies among organisms, but it is generally thought to be relatively low (e.g., <10%) in shells from aquatic organism and high (>90%) in the shells from terrestrial organisms. Because metabolic carbon contains significantly more C-12 than DIC, negative excursions from the expected environmental (DIC) signal are interpreted to reflect an increased contribution of metabolic carbon in the shell. This observation contrasts sharply with modeled carbon isotope compositions for shell layers deposited from the inner extrapallial fluid (EPF). Previous studies have shown that growth lines within the inner shell layer of bivalves are produced during periods of anaerobiosis when acidic metabolic byproducts (e.g., succinic acid) are neutralized (or buffered) by shell dissolution. This requires the pH of EPF to decrease below ambient levels (~7.5) until a state of undersaturation is achieved that promotes shell dissolution. This condition may occur when aquatic bivalves are subjected to external stressors originating from ecological (predation) or environmental (exposure to atm; low dissolved oxygen; contaminant release) pressures; normal physiological processes will restore the pH of EPF when the pressure is removed. As a consequence of this process, a temporal window should also exist in EPF at relatively low pH where shell carbonate is deposited at a reduced saturation state and precipitation rate. For example, EPF chemistry should remain slightly supersaturated with respect to aragonite given a drop of one pH unit (6.5), but under closed conditions

Laser ablation molecular isotopic spectrometry of carbon isotopes

NASA Astrophysics Data System (ADS)

Bol‧shakov, Alexander A.; Mao, Xianglei; Jain, Jinesh; McIntyre, Dustin L.; Russo, Richard E.

2015-11-01

Quantitative determination of carbon isotopes using Laser Ablation Molecular Isotopic Spectrometry (LAMIS) is described. Optical emission of diatomic molecules CN and C2 is used in these measurements. Two quantification approaches are presented: empirical calibration of spectra using a set of reference standards and numerical fitting of a simulated spectrum to the experimental one. Formation mechanisms of C2 and CN in laser ablation plasma are briefly reviewed to provide insights for implementation of LAMIS measurements. A simulated spectrum of the 12C2 Swan system was synthesized using four constituents within 473.5-476.5 nm. Simulation included three branches of 12C2 (1-0), branches R(0-0) and R(1-1), and branch P(9-8) of 12C2. Spectral positions of the tail lines in R(0-0) and R(1-1) were experimentally measured, since they were not accurately known before. The Swan band (1-0) of the isotopologue 13C12C was also simulated. Fitting to the experimental spectrum yielded the ratio 13C/12C = 1.08% in a good agreement with measurements by isotope ratio mass spectrometry. LAMIS promises to be useful in coal, oil and shale exploration, carbon sequestration monitoring, and agronomy studies.

Reactive transport modeling of stable carbon isotope fractionation in a multi-phase multi-component system during carbon sequestration

DOE PAGES

Zhang, Shuo; DePaolo, Donald J.; Zheng, Liange; ...

2014-12-31

Carbon stable isotopes can be used in characterization and monitoring of CO 2 sequestration sites to track the migration of the CO 2 plume and identify leakage sources, and to evaluate the chemical reactions that take place in the CO 2-water-rock system. However, there are few tools available to incorporate stable isotope information into flow and transport codes used for CO 2 sequestration problems. We present a numerical tool for modeling the transport of stable carbon isotopes in multiphase reactive systems relevant to geologic carbon sequestration. The code is an extension of the reactive transport code TOUGHREACT. The transport modulemore » of TOUGHREACT was modified to include separate isotopic species of CO 2 gas and dissolved inorganic carbon (CO 2, CO 3 2-, HCO 3 -,…). Any process of transport or reaction influencing a given carbon species also influences its isotopic ratio. Isotopic fractionation is thus fully integrated within the dynamic system. The chemical module and database have been expanded to include isotopic exchange and fractionation between the carbon species in both gas and aqueous phases. The performance of the code is verified by modeling ideal systems and comparing with theoretical results. Efforts are also made to fit field data from the Pembina CO 2 injection project in Canada. We show that the exchange of carbon isotopes between dissolved and gaseous carbon species combined with fluid flow and transport, produce isotopic effects that are significantly different from simple two-component mixing. These effects are important for understanding the isotopic variations observed in field demonstrations.« less

Tectonic controls on the long-term carbon isotope mass balance.

PubMed

Shields, Graham A; Mills, Benjamin J W

2017-04-25

The long-term, steady-state marine carbon isotope record reflects changes to the proportional burial rate of organic carbon relative to total carbon on a global scale. For this reason, times of high δ 13 C are conventionally interpreted to be oxygenation events caused by excess organic burial. Here we show that the carbon isotope mass balance is also significantly affected by tectonic uplift and erosion via changes to the inorganic carbon cycle that are independent of changes to the isotopic composition of carbon input. This view is supported by inverse covariance between δ 13 C and a range of uplift proxies, including seawater 87 Sr/ 86 Sr, which demonstrates how erosional forcing of carbonate weathering outweighs that of organic burial on geological timescales. A model of the long-term carbon cycle shows that increases in δ 13 C need not be associated with increased organic burial and that alternative tectonic drivers (erosion, outgassing) provide testable and plausible explanations for sustained deviations from the long-term δ 13 C mean. Our approach emphasizes the commonly overlooked difference between how net and gross carbon fluxes affect the long-term carbon isotope mass balance, and may lead to reassessment of the role that the δ 13 C record plays in reconstructing the oxygenation of earth's surface environment.

Geochemistry of the alginite and amorphous organic matter from type II-S kerogens

USGS Publications Warehouse

Stankiewicz, B.A.; Kruge, M.A.; Mastalerz, Maria; Salmon, G.L.

1996-01-01

Maceral fractions of the Type II-S kerogens from the Monterey Formation (Miocene. California. U.S.A.) and Duwi Formation (Campanian/Maastrichtian, Egypt) were separated by density gradient centrifugation. The Monterey Fm. kerogen sample was comprised chiefly of light red-fluorescing amorphous organic matter (AOM), the flash pyrolyzate of which was characterized by a predominance of alkylbenzenes, alkylthiophenes and alkylpyrroles. In contrast, the pyrolyzates of its alginite concentrate showed a highly aliphatic character, typical of this maceral, with the series of n-alkenes and n-alkanes (C6- C26) predominating. The pyrolyzate of the dominant light brown-fluorescing AOM of the Duwi Fm. kerogen had a relatively high concentration of alkylbenzenes and alkylthiophenes, while its elginite concentrate showed a more aliphatic character upon pyrolysis. There was a marked enrichment of thiophenic sulfur in the light-colored AOM of both samples (and also pyrrolic nitrogen in the case of the Monterey) relative to the alginite. The results support a bacterially-mediated, degradative origin for Type II-S amorphous organic matter, with algal remains as the primary source of the kerogen.

Kerogen maturation data in the Uinta Basin, Utah, USA, constrain predictions of natural hydrocarbon seepage into the atmosphere

NASA Astrophysics Data System (ADS)

Mansfield, Marc L.

2014-03-01

Natural seepage of methane from the lithosphere to the atmosphere occurs in regions with large natural gas deposits. According to some authors, it accounts for roughly 5% of the global methane budget. I explore a new approach to estimate methane fluxes based on the maturation of kerogen, which is the hydrocarbon polymer present in petroleum source rocks and whose decomposition leads to the formation of oil and natural gas. The temporal change in the atomic H/C ratio of kerogen lets us estimate the total carbon mass released by it in the form of oil and natural gas. Then the time interval of active kerogen decomposition lets us estimate the average annual formation rate of oil and natural gas in any given petroleum system, which I demonstrate here using the Uinta Basin of eastern Utah as an example. Obviously, this is an upper bound to the average annual rate at which natural gas seeps into the atmosphere. After adjusting for biooxidation of natural gas, I conclude that the average annual seepage rate in the Uinta Basin is not greater than (3100 ± 900) tonne yr-1. This is (0.5 ± 0.15)% of the total flux of methane into the atmosphere over the Basin, as measured during aircraft flights. I speculate about the difference between the regional 0.5% and the global 5% estimates.

METHOD FOR PRODUCING ISOTOPIC METHANES FROM LITHIUM CARBONATE AND LITHIUM HYDRIDE

DOEpatents

Frazer, J.W.

1959-10-27

A process is descrlbed for the production of methane and for the production of methane containing isotopes of hydrogen and/or carbon. Finely divided lithium hydrlde and litldum carbonate reactants are mixed in intimate contact and subsequently compacted under pressures of from 5000 to 60,000 psl. The compacted lithium hydride and lithium carbenate reactunts are dispised in a gas collecting apparatus. Subsequently, the compact is heated to a temperature in the range 350 to 400 deg C whereupon a solid-solid reaction takes place and gaseous methane is evolved. The evolved methane is contaminated with gaseous hydrogen and a very small amount of CO/sub 2/; however, the desired methane product is separated from sald impurities by well known chemical processes, e.g., condensation in a cold trap. The product methane contalns isotopes of carbon and hydrogen, the Isotopic composition being determined by the carbon isotopes originally present In the lithium carbonate and the hydrogen isotopes originally present in the lithium hydride.

Understanding the Marine Chromium Isotope Record from Modern and Ancient Carbonates

NASA Astrophysics Data System (ADS)

Parkinson, I. J.; Bonnand, P.; James, R. H.; Fairchild, I. J.; Dixon, S.

2011-12-01

Chromium isotopes may provide a powerful tool for reconstructing the redox state of ancient seawater because Cr isotope fractionation is large (up to 7% in δ53Cr) during the reduction of Cr(VI) to Cr(III) in natural waters [1]. Recent studies have demonstrated that although Cr(VI) is predicted to be the thermodynamically stable form in seawater (as CrO42-), significant amounts (5-20%) of Cr(III) may also be present in surface waters [2]. Therefore the δ53Cr of seawater could vary by up to 2%. Marine carbonates potentially provide a means to extracting information about the Cr isotopic composition of seawater in the geological past and we have developed a high-precision double-spike technique for analysing Cr isotopes in carbonates [3]. The δ53Cr of modern Bahamas Bank carbonates (+0.76%) is broadly consistent with these carbonates recording a seawater Cr signature. Moreover, these pure carbonates contain significant amounts of Cr (1-4 ppm), which indicates that Cr is strongly partitioned into calcium carbonate. Therefore carbonates are likely to provide a faithful record of the δ53Cr composition of seawater. Shallow marine carbonates from the Phanerozoic range in δ53Cr from +0.76 to +1.8%, and some Neoproterozoic carbonates also have heavy Cr isotopic compositions of +0.5 to +1.0 %. Such compositions may reflect changes in the inputs of Cr to the oceans and/or changes in the redox state of the oceans. However, to interpret Cr isotopic compositions in ancient carbonates additionally requires a careful assessment of their trace element contents. This study aims to demonstrate how a combination of redox sensitive trace elements, such as Ce, and Cr isotopes allow an assessment of the marine chromium isotope record. [1] Ellis et al., 2002, Science, 295, 2060-2062. [2] Connolly et al., 2006, Deep Sea Res. Part I, 2006 53, 1975-1988. [3] P. Bonnand, et al., 2011, J. Anal. At. Spectr., 26, 528-535.

Tectonic controls on the long-term carbon isotope mass balance

PubMed Central

Mills, Benjamin J. W.

2017-01-01

The long-term, steady-state marine carbon isotope record reflects changes to the proportional burial rate of organic carbon relative to total carbon on a global scale. For this reason, times of high δ13C are conventionally interpreted to be oxygenation events caused by excess organic burial. Here we show that the carbon isotope mass balance is also significantly affected by tectonic uplift and erosion via changes to the inorganic carbon cycle that are independent of changes to the isotopic composition of carbon input. This view is supported by inverse covariance between δ13C and a range of uplift proxies, including seawater 87Sr/86Sr, which demonstrates how erosional forcing of carbonate weathering outweighs that of organic burial on geological timescales. A model of the long-term carbon cycle shows that increases in δ13C need not be associated with increased organic burial and that alternative tectonic drivers (erosion, outgassing) provide testable and plausible explanations for sustained deviations from the long-term δ13C mean. Our approach emphasizes the commonly overlooked difference between how net and gross carbon fluxes affect the long-term carbon isotope mass balance, and may lead to reassessment of the role that the δ13C record plays in reconstructing the oxygenation of earth’s surface environment. PMID:28396434

Carbon and hydrogen isotope fractionation by moderately thermophilic methanogens

NASA Astrophysics Data System (ADS)

Valentine, David L.; Chidthaisong, Amnat; Rice, Andrew; Reeburgh, William S.; Tyler, Stanley C.

2004-04-01

A series of laboratory studies were conducted to increase understanding of stable carbon (13C/12C) and hydrogen (D/H) isotope fractionation arising from methanogenesis by moderately thermophilic acetate- and hydrogen-consuming methanogens. Studies of the aceticlastic reaction were conducted with two closely related strains of Methanosaeta thermophila. Results demonstrate a carbon isotope fractionation of only 7‰ (α = 1.007) between the methyl position of acetate and the resulting methane. Methane formed by this process is enriched in 13C when compared with other natural sources of methane; the magnitude of this isotope effect raises the possibility that methane produced at elevated temperature by the aceticlastic reaction could be mistaken for thermogenic methane based on carbon isotopic content. Studies of H2/CO2 methanogenesis were conducted with Methanothermobacter marburgensis. The fractionation of carbon isotopes between CO2 and CH4 was found to range from 22 to 58‰ (1.023 ≤ α ≤ 1.064). Greater fractionation was associated with low levels of molecular hydrogen and steady-state metabolism. The fractionation of hydrogen isotopes between source H2O and CH4 was found to range from 127 to 275‰ (1.16 ≤ α ≤ 1.43). Fractionation was dependent on growth phase with greater fractionation associated with later growth stages. The maximum observed fractionation factor was 1.43, independent of the δD-H2 supplied to the culture. Fractionation was positively correlated with temperature and/or metabolic rate. Results demonstrate significant variability in both hydrogen and carbon isotope fractionation during methanogenesis from H2/CO2. The relatively small fractionation associated with deuterium during H2/CO2 methanogenesis provides an explanation for the relatively enriched deuterium content of biogenic natural gas originating from a variety of thermal environments. Results from these experiments are used to develop a hypothesis that differential

Site-specific equilibrium isotopic fractionation of oxygen, carbon and calcium in apatite

NASA Astrophysics Data System (ADS)

Aufort, Julie; Ségalen, Loïc; Gervais, Christel; Paulatto, Lorenzo; Blanchard, Marc; Balan, Etienne

2017-12-01

The stable isotope composition of biogenic apatite is an important geochemical marker that can record environmental parameters and is widely used to infer past climates, biomineralization processes, dietary preferences and habitat of vertebrates. In this study, theoretical equilibrium isotopic fractionation of oxygen, carbon and calcium in hydroxyapatite and carbonate-bearing hydroxyapatite is investigated using first-principles methods based on density-functional theory and compared to the theoretical isotopic fractionation properties of calcite, CO2 and H2O. Considering the variability of apatite crystal-chemistry, special attention is given to specific contributions of crystal sites to isotopic fractionation. Significant internal fractionation is calculated for oxygen and carbon isotopes in CO3 between the different structural sites occupied by carbonate groups in apatite (typically 7‰ for both 18O/16O and 13C/12C fractionation at 37 °C). Compared with calcite-water oxygen isotope fractionation, occurrence of A-type substitution in apatite structure, in addition to the main B-type substitution, could explain the larger temperature dependence of oxygen isotope fractionation measured at low temperature between carbonate in apatite and water. Theoretical internal fractionation of oxygen isotopes between carbonate and phosphate in B-type carbonated apatite (∼8‰ at 37 °C) is consistent with experimental values obtained from modern and well-preserved fossil bio-apatites. Concerning calcium, theoretical results suggest a small fractionation between apatite and calcite (-0.17‰ at 37 °C). Internal fractionation reaching 0.8‰ at 37 °C occurs between the two Ca sites in hydroxyapatite. Furthermore, the Ca isotopic fractionation properties of apatite are affected by the occurrence of carbonate groups, which could contribute to the variability observed on natural samples. Owing to the complexity of apatite crystal-chemistry and in light of the theoretical

Magnesium isotope fractionation in bacterial mediated carbonate precipitation experiments

NASA Astrophysics Data System (ADS)

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

2012-12-01

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 δ26Mg 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 μm in diameter, but with the majority have diameters of ~100 μm. 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

Insights into Paleogene biogeochemistry from coupled carbon and sulfur isotopes in foraminiferal calcite.

NASA Astrophysics Data System (ADS)

Rennie, V.; Paris, G.; Abramovitch, S.; Sessions, A. L.; Adkins, J. F.; Turchyn, A. V.

2014-12-01

The Paleogene witnessed large-scale environmental changes, including the beginning of long-term Cenozoic cooling. The carbon isotope composition of foraminiferal calcite suggests a major reorganization of the carbon cycle over the Paleogene, with enhanced organic carbon burial in the Paleocene, and subsequent oxidation of this organic carbon or increased volcanism throughout the Eocene. The sulfur cycle is linked to the carbon cycle via the breakdown of organic carbon during bacterial sulfate reduction. Over geological time, carbon and sulfur isotopic shifts are often coupled due to enhanced pyrite burial being coupled to enhanced organic carbon burial, and enhanced pyrite weathering being coupled to enhanced organic carbon weathering. However, over the Paleogene, carbon and sulfur isotopes are fully decoupled, with the sulfur isotope record showing only one major shift in the early Eocene, after most of the carbon isotope variability is complete. One complication of interpreting the evolution of the sulfur cycle over the Cenozoic, is the fact that the mineral proxies used (typically barite) may not be temporally coincident with those used to reconstruct the carbon cycle (typically carbonate). Furthermore, these minerals are preserved in different locations, and therefore often must be extracted from different sediment cores in different ocean basins, leading to age-model uncertainty when the records are merged. To properly ascertain the phasing between early Cenozoic changes in the carbon cycle and the sulfur cycle, we would ideally measure all isotope records on the same mineral. A new sulfur isotope analytical technique [1] has been optimised for foraminiferal calcite as a proxy for seawater δ34SSO4. The δ34SSO4 in foraminiferal calcite can then be tied to records of carbon isotopes from stratigraphically identical samples, resolving previous age model uncertainties. We present coupled carbon and sulfur isotope records from the same core over the early

Aerosol carbon isotope composition over Baltic Sea

NASA Astrophysics Data System (ADS)

Garbaras, Andrius; Pabedinskas, Algirdas; Masalaite, Agne; Petelski, Tomasz; Gorokhova, Elena; Sapolaite, Justina; Ezerinskis, Zilvinas; Remeikis, Vidmantas

2017-04-01

Particulate carbonaceous matter is significant contributor to ambient particulate matter originating from intervening sources which contribution is difficult to quantify due to source diversity, chemical complexity and processes during atmospheric transport. Carbon isotope analysis can be extremely useful in source apportionment of organic matter due to the unique isotopic signatures associated with anthropocentric (fossil fuel), continental (terrestrial plants) and marine sources, and is particularly effective when these sources are mixed (Ceburnis et al., 2011;Ceburnis et al., 2016). We will present the isotope ratio measurement results of aerosol collected during the cruise in the Baltic Sea. Sampling campaign of PM10 and size segregated aerosol particles was performed on the R/V "Oceania" in October 2015. Air mass back trajectories were prevailing both from the continental and marine areas during the sampling period. The total carbon concentration varied from 1 µg/m3 to 8 µg/m3. Two end members (δ13C = -25‰ and δ13C = -28 ‰ ) were established from the total stable carbon isotope analysis in PM10 fraction. δ13C analysis in size segregated aerosol particles revealed δ13C values being highest in the 1 - 2.5 µm range (δ13C = -24.9 ‰ ) during continental transport, while lowest TC δ13C values (δ13C ≈ -27 ‰ ) were detected in the size range D50 <1 µm during stormy weather when air mass trajectory prevailed from the western direction. These measurements revealed that simplified isotope mixing model can not be applied for the aerosol source apportionment (Masalaite et al., 2015) in the perturbed marine environment. Additionally, concentration of bacteria and fungi were measured in size segregated and PM10 aerosol fraction. We were able to relate aerosol source δ13C end members with the abundance of bacteria and fungi over Baltic Sea combining air mass trajectories, stable isotope data, fungi and bacteria concentrations. Ceburnis, D., Garbaras, A

Geochemistry and organic facies of La Luna-Tres Esquinas cycle: Maturity, biomarkers and kerogen issues

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

Olivares, C.; Lorente, M.A.; Cassani, F.

1996-08-01

Four surface sections from the Venzuelan Andes were chosen for this study. The results show interesting trends for exploration of the Andean Belt. In the Eastern Andes (Trujillo), sections San Lazaro and Chejende yield thick, post-mature, highly tectonically disturbed La Luna Formation. San Lazaro section has a fault contact showing La Luna post-mature, inertinitic shales in contact with gray shales, ftanites and carbonates bearing marginally mature, highly fluorescent organic gels. Biomarkers show a high level of hopanes, predominance of C27/C29, and S/R ratio=64% characteristic of marine, moderate mature organic matter. Chejende section has almost the same pattern of marine organicmore » matter (COT=9%) but post-mature. In the Central Andes (Merida), El Valle and San Javier sections yield extremely rich source rocks with very different organic matter. El Valle section (Tres Esquinas Member) has very rich structured algal matter (COT=8%), marginally mature, which is correlated with a short term carbon isotope ({delta}{sup 13}C) fluctuation found in the Campanian-Santonian (anoxic?) cycle. The abundance of C27/C29, and high levels of hopanes are related to marine anoxic conditions. The San Javier section shows evidence of a very rich type I/II kerogen, bearing algal-bacterial amorphous masses, marginally mature and rich (COT=3%); this pattern matches with the abundance of C27/C29 as well as with the ratio S/R=64%, which means moderate maturity. From these results, two provinces can be separated today: a highly tectonized, post-mature, Eastern Andes Province and a very rich, marginally mature, Central Andes Province.« less

Stable carbon isotope fractionation by sulfate-reducing bacteria

NASA Technical Reports Server (NTRS)

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

2003-01-01

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

Isotopic anomalies from neutron reactions during explosive carbon burning

NASA Technical Reports Server (NTRS)

Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

1978-01-01

The possibility that the newly discovered correlated isotopic anomalies for heavy elements in the Allende meteorite were synthesized in the secondary neutron capture episode during the explosive carbon burning, the possible source of the O-16 and Al-26 anomalies, is examined. Explosive carbon burning calculations under typical conditions were first performed to generate time profiles of temperature, density, and free particle concentrations. These quantities were inputted into a general neutron capture code which calculates the resulting isotopic pattern from exposing the preexisting heavy seed nuclei to these free particles during the explosive carbon burning conditions. The interpretation avoids the problem of the Sr isotopic data and may resolve the conflict between the time scales inferred from 1-129, Pu-244, and Al-26.

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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.

Fractionation of carbon (13C/12C) isotopes in glycine decarboxylase reaction.

PubMed

Ivlev, A A; Bykova, N V; Igamberdiev, A U

1996-05-20

Fractionation of carbon isotopes (13C/12C) by glycine decarboxylase (GDC) was investigated in mitochondrial preparations isolated from photosynthetic tissues of different plants (Pisum, Medicago, Triticum, Hordeum, Spinacia, Brassica, Wolffia). 20 mM glycine was supplied to mitochondria, and the CO2 formed was absorbed and analyzed for isotopic content. CO2 evolved by mitochondria of Pisum was enriched up to 8% in 12C compared to the carboxylic atom of glycine. CO2 evolved by mitochondria of the other plants investigated was enriched by 5-16% in 13C. Carbon isotope effects were sensitive to reaction conditions (pH and the presence of GDC cofactors). Theoretical treatment of the reaction mechanism enabled us to conclude that the value and even the sign of the carbon isotope effect in glycine decarboxylation depend on the contribution of the enzyme-substrate binding step and of the decarboxylation step itself to the overall reaction rate. Therefore, the fractionation of carbon isotopes in GDC reaction was revealed which provides essential isotopic effects in plants in addition to the well-known effect of carbon isotope fractionation by the central photosynthetic enzyme, ribulose-1,5-biphosphate carboxylase.

Estimation of porphyrin concentration in the kerogen fraction of shales using high-resolution reflectance spectroscopy

NASA Technical Reports Server (NTRS)

Holden, Peter N.; Gaffey, Michael J.; Sundararaman, P.

1991-01-01

An interpretive model for estimating porphyrin concentration in bitumen and kerogen from spectral reaflectance data in the visible and near-ultraviolet region of the spectrum is derived and calibrated. Preliminary results obtained using the model are consistent with concentrations determined from the bitumen extract and suggest that 40 to 60 percent of the total porphyrin concentration remains in the kerogen after extraction of bitumen from thermally immature samples. The reflectance technique will contribute to porphyrin and kerogen studies and can be applied at its present level of development to several areas of geologic and paleo-oceanographic research.

Empirical High-Temperature Calibration for the Carbonate Clumped Isotopes Paleothermometer

NASA Astrophysics Data System (ADS)

Kluge, T.; John, C. M.; Jourdan, A.; Davis, S.; Crawshaw, J.

2013-12-01

The clumped isotope paleothermometer is being used in a wide range of applications related to carbonate mineral formation, focusing on temperature and fluid δ18O reconstruction. Whereas the range of typical Earth surface temperatures has been the focus of several studies based on laboratory experiments and biogenic carbonates of known growth temperatures, the clumped isotope-temperature relationship above 70 °C has not been assessed by direct precipitation of carbonates. We investigated the clumped isotope-temperature relationship by precipitating carbonates between 20 and 200°C in the laboratory. The setup consists of a pressurized vessel in which carbonate minerals are precipitated from the mixture of two solutions (CaCl2, NaHCO3). Both solutions are thermally and isotopically equilibrated before injection in the pressure vessel. Minerals precipitated in this setup generally consist of calcite. Samples were reacted with 105% orthophosphoric acid for 10 min at 90°C. The evolved CO2 was continuously collected and subsequently purified with a Porapak trap held at -35°C. Measurements were performed on a MAT 253 using the protocol of Huntington et al. (2009) and Dennis et al. (2011). Clumped isotope values from 20-90°C are consistent with carbonates that were precipitated from a CaCO3 super-saturated solution using the method of McCrea (1950). This demonstrates that the experimental setup does not induce any kinetic fractionation, and can be used for high-temperature carbonate precipitation. The new clumped isotope calibration at high temperature follows the theoretical calculations of Schauble et al. (2006) adjusted for phosphoric acid digestion at 90°C. We gratefully acknowledge funding from Qatar Petroleum, Shell and the Qatar Science and Technology Park.

Yucca Mountain Area Saturated Zone Dissolved Organic Carbon Isotopic Data

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

Thomas, James; Decker, David; Patterson, Gary

2007-06-25

Groundwater samples in the Yucca Mountain area were collected for chemical and isotopic analyses and measurements of water temperature, pH, specific conductivity, and alkalinity were obtained at the well or spring at the time of sampling. For this project, groundwater samples were analyzed for major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC). The U.S. Geological Survey (USGS) performed all the fieldwork on this project including measurement of water chemistry field parameters and sample collection. The major ions dissolved in the groundwater, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC)more » were analyzed by the USGS. All preparation and processing of samples for DOC carbon isotopic analyses and geochemical modeling were performed by the Desert Research Institute (DRI). Analysis of the DOC carbon dioxide gas produced at DRI to obtain carbon-13 and carbon-14 values was conducted at the University of Arizona Accelerator Facility (a NSHE Yucca Mountain project QA qualified contract facility). The major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of DIC were used in geochemical modeling (NETPATH) to determine groundwater sources, flow paths, mixing, and ages. The carbon isotopes of DOC were used to calculate groundwater ages that are independent of DIC model corrected carbon-14 ages. The DIC model corrected carbon-14 calculated ages were used to evaluate groundwater travel times for mixtures of water including water beneath Yucca Mountain. When possible, groundwater travel times were calculated for groundwater flow from beneath Yucca Mountain to down gradient sample sites. DOC carbon-14 groundwater ages were also calculated for groundwaters in the Yucca Mountain area. When possible, groundwater travel times were estimated for groundwater flow from beneath Yucca Mountain to down gradient groundwater sample sites using the DOC calculated

Measurement of natural carbon isotopic composition of acetone in human urine.

PubMed

Yamada, Keita; Ohishi, Kazuki; Gilbert, Alexis; Akasaka, Mai; Yoshida, Naohiro; Yoshimura, Ryoko

2016-02-01

The natural carbon isotopic composition of acetone in urine was measured in healthy subjects using gas chromatography-combustion-isotope ratio mass spectrometry combined with headspace solid-phase microextraction (HS-SPME-GC-C-IRMS). Before applying the technique to a urine sample, we optimized the measurement conditions of HS-SPME-GC-C-IRMS using aqueous solutions of commercial acetone reagents. The optimization enabled us to determine the carbon isotopic compositions within ±0.2 ‰ of precision and ±0.3‰ of error using 0.05 or 0.2 mL of aqueous solutions with acetone concentrations of 0.3-121 mg/L. For several days, we monitored the carbon isotopic compositions and concentrations of acetone in urine from three subjects who lived a daily life with no restrictions. We also monitored one subject for 3 days including a fasting period of 24 h. These results suggest that changes in the availability of glucose in the liver are reflected in changes in the carbon isotopic compositions of urine acetone. Results demonstrate that carbon isotopic measurement of metabolites in human biological samples at natural abundance levels has great potential as a tool for detecting metabolic changes caused by changes in physiological states and disease.

Combined simulation of carbon and water isotopes in a global ocean model

NASA Astrophysics Data System (ADS)

Paul, André; Krandick, Annegret; Gebbie, Jake; Marchal, Olivier; Dutkiewicz, Stephanie; Losch, Martin; Kurahashi-Nakamura, Takasumi; Tharammal, Thejna

2013-04-01

Carbon and water isotopes are included as passive tracers in the MIT general circulation model (MITgcm). The implementation of the carbon isotopes is based on the existing MITgcm carbon cycle component and involves the fractionation processes during photosynthesis and air-sea gas exchange. Special care is given to the use of a real freshwater flux boundary condition in conjunction with the nonlinear free surface of the ocean model. The isotopic content of precipitation and water vapor is obtained from an atmospheric GCM (the NCAR CAM3) and mapped onto the MITgcm grid system, but the kinetic fractionation during evaporation is treated explicitly in the ocean model. In a number of simulations, we test the sensitivity of the carbon isotope distributions to the formulation of fractionation during photosynthesis and compare the results to modern observations of δ13C and Δ14C from GEOSECS, WOCE and CLIVAR. Similarly, we compare the resulting distribution of oxygen isotopes to modern δ18O data from the NASA GISS Global Seawater Oxygen-18 Database. The overall agreement is good, but there are discrepancies in the carbon isotope composition of the surface water and the oxygen isotope composition of the intermediate and deep waters. The combined simulation of carbon and water isotopes in a global ocean model will provide a framework for studying present and past states of ocean circulation such as postulated from deep-sea sediment records.

Inorganic carbon and fossil organic carbon are source of bias for quantification of sequestered carbon in mine spoil

NASA Astrophysics Data System (ADS)

Vindušková, Olga; Frouz, Jan

2016-04-01

Carbon sequestration in mine soils has been studied as a possibility to mitigate the rising atmospheric CO2 levels and to improve mine soil quality (Vindu\\vsková and Frouz, 2013). Moreover, these soils offer an unique opportunity to study soil carbon dynamics using the chronosequence approach (using a set of sites of different age on similar parent material). However, quantification of sequestered carbon in mine soils is often complicated by fossil organic carbon (e.g., from coal or kerogen) or inorganic carbon present in the spoil. We present a methodology for quantification of both of these common constituents of mine soils. Our recommendations are based on experiments done on post-mining soils in Sokolov basin, Czech Republic. Here, fossil organic carbon is present mainly as kerogen Type I and II and represents 2-6 wt.% C in these soils. Inorganic carbon in these soils is present mainly as siderite (FeCO3), calcite (CaCO3), and dolomite (CaMg(CO3)2). All of these carbonates are often found in the overburden of coal seams thus being a common constituent of post-mining soils in the world. Vindu\\vsková O, Frouz J, 2013. Soil carbon accumulation after open-cast coal and oil shale mining in Northern Hemisphere: a quantitative review. ENVIRONMENTAL EARTH SCIENCES, 69: 1685-1698. Vindu\\vsková O, Dvořáček V, Prohasková A, Frouz J. 2014. Distinguishing recent and fossil organic matter - A critical step in evaluation of post-mining soil development - using near infrared spectroscopy. ECOLOGICAL ENGINEERING. 73: 643-648. Vindu\\vsková O, Sebag D, Cailleau G, Brus J, Frouz J. 2015. Methodological comparison for quantitative analysis of fossil and recently derived carbon in mine soils with high content of aliphatic kerogen. ORGANIC GEOCHEMISTRY, 89-90:14-22.

The evolution of Carbon isotopes in calcite in the presence of cyanobacteria

NASA Astrophysics Data System (ADS)

Grimm, Christian; Mavromatis, Vasileios; Pokrovsky, Oleg S.; Oelkers, Eric H.

2016-04-01

Stable isotopic compositions in carbonates are widely used as indicators of environmental conditions prevailing during mineral formation. This reconstruction is substantially based on the assumption that there is no change in the mineral composition over geological time. However, recent experimental studies have shown that carbon and magnesium isotopes in hydrous Mg-carbonates undergo continuous re-equilibration with the ambient solution even after mineral precipitation stopped ([1] and [2], respectively). To verify whether this holds true for anhydrous Ca-bearing carbonates which readily form at earth's surface environments, a series of batch system calcite precipitation experiments were performed in the presence of actively growing cyanobacteria Synechococcus sp. The bacteria were grown at ambient temperature in a BG11 culture medium (SIGMA C3061) and continuous stirring, air-bubbling and illumination. Calcite precipitation was initiated by the addition of 8.5mM CaCl2 and 0-50 mM NaHCO3 or NaHCO3-Na2CO3 mixtures. The presence of cyanobacteria is on one hand promoting CaCO3 formation due to increasing pH resulting from photosynthesis. On the other hand, actively growing cyanobacteria drastically change carbon isotope signature of the aqueous fluid phase by preferably incorporating the lighter 12C isotope into biomass [1]. This study explores the effect of continuously changing carbon isotope compositions in dissolved inorganic carbon (DIC) on precipitated calcite which is in chemical equilibrium with the ambient fluid phase. [1] Mavromatis et al. (2015). The continuous re-equilibration of carbon isotope compositions of hydrous Mg-carbonates in the presence of cyanobacteria. Chem. Geol. 404, 41-51 [2] Mavromatis et al. (2012). Magnesium isotope fractionation during hydrous magnesium carbonate precipitation with and without cyanobacteria. Geochim. Cosmochim. Acta 76, 161-174

Integrated carbon and chlorine isotope modeling: applications to chlorinated aliphatic hydrocarbons dechlorination.

PubMed

Jin, Biao; Haderlein, Stefan B; Rolle, Massimo

2013-02-05

We propose a self-consistent method to predict the evolution of carbon and chlorine isotope ratios during degradation of chlorinated hydrocarbons. The method treats explicitly the cleavage of isotopically different C-Cl bonds and thus considers, simultaneously, combined carbon-chlorine isotopologues. To illustrate the proposed modeling approach we focus on the reductive dehalogenation of chlorinated ethenes. We compare our method with the currently available approach, in which carbon and chlorine isotopologues are treated separately. The new approach provides an accurate description of dual-isotope effects regardless of the extent of the isotope fractionation and physical characteristics of the experimental system. We successfully applied the new approach to published experimental results on dehalogenation of chlorinated ethenes both in well-mixed systems and in situations where mass-transfer limitations control the overall rate of biodegradation. The advantages of our self-consistent dual isotope modeling approach proved to be most evident when isotope fractionation factors of carbon and chlorine differed significantly and for systems with mass-transfer limitations, where both physical and (bio)chemical transformation processes affect the observed isotopic values.

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

NASA Astrophysics Data System (ADS)

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

2008-07-01

The Lomagundi (2.22-2.1 Ga) positive carbon isotope excursion in shallow-marine sedimentary carbonates has been associated with the rise in atmospheric oxygen, but subsequent studies have demonstrated that the carbon isotope excursion was preceded by the rise in atmospheric oxygen. The amount of oxygen released to the exosphere during the Lomagundi excursion is constrained by the average global fractionation between inorganic and organic carbon, which is poorly characterized. Because dissolved inorganic and organic carbon reservoirs were arguably larger in the Paleoproterozoic ocean, at a time of lower solar luminosity and lower ocean redox state, decoupling between these two variables might be expected. We determined carbon isotope values of carbonate and organic matter in carbonates and shales of the Silverton Formation, South Africa and in the correlative Sengoma Argillite Formation, near the border in Botswana. These units were deposited between 2.22 and 2.06 Ga along the margin of the Kaapvaal Craton in an open-marine deltaic setting and experienced lower greenschist facies metamorphism. The prodelta to offshore marine shales are overlain by a subtidal carbonate sequence. Carbonates exhibit elevated 13C values ranging from 8.3 to 11.2‰ vs. VPDB consistent with deposition during the Lomagundi positive excursion. The total organic carbon (TOC) contents range from 0.01 to 0.6% and δ13C values range from - 24.8 to - 13.9‰. Thus, the isotopic fractionation between organic and carbonate carbon was on average 30.3 ± 2.8‰ ( n = 32) in the shallow-marine environment. The underlying Sengoma shales have highly variable TOC contents (0.14 to 21.94%) and δ13C values (- 33.7 to - 20.8‰) with an average of - 27.0 ± 3.0‰ ( n = 50). Considering that the shales were also deposited during the Lomagundi excursion, and taking δ13C values of the overlying carbonates as representative of the δ13C value of dissolved inorganic carbon during shale deposition, a carbon

Evidence from carbon isotope measurements for diverse origins of sedimentary hydrocarbons

NASA Technical Reports Server (NTRS)

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

1990-01-01

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.

Development of a Field-Deployable Methane Carbon Isotope Analyzer

NASA Astrophysics Data System (ADS)

Dong, Feng; Baer, Douglas

2010-05-01

Methane is a potent greenhouse gas, whose atmospheric surface mixing ratio has almost doubled compared with preindustrial values. Methane can be produced by biogenic processes, thermogenic processes or biomass, with different isotopic signatures. As a key molecule involved in the radiative forcing in the atmosphere, methane is thus one of the most important molecules linking the biosphere and atmosphere. Therefore precise measurements of mixing ratios and isotopic compositions will help scientists to better understand methane sources and sinks. To date, high precision isotope measurements have been exclusively performed with conventional isotope ratio mass spectrometry, which involves intensive labor and is not readily field deployable. Optical studies using infrared laser spectroscopy have also been reported to measure the isotopic ratios. However, the precision of optical-based analyses, to date, is typically unsatisfactory without pre-concentration procedures. We present characterization of the performance of a portable Methane Carbon Isotope Analyzer (MCIA), based on cavity enhanced laser absorption spectroscopy technique, that provides in-situ measurements of the carbon isotope ratio (13C/12C or del_13C) and methane mixing ratio (CH4). The sample is introduced to the analyzer directly without any requirement for pretreatment or preconcentration. A typical precision of less than 1 per mill (< 0.1%) with a 10-ppm methane sample can be achieved in a measurement time of less than 100 seconds. The MCIA can report carbon isotope ratio and concentration measurements over a very wide range of methane concentrations. Results of laboratory tests and field measurements will be presented.

Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

USGS Publications Warehouse

Coleman, D.D.; Risatti, J.B.; Schoell, M.

1981-01-01

Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted. We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both 13C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26??C than at 11.5??C. The change in ??D relative to the change in ??13C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway. The change in the ??D value for the residual methane was from 8 to 14 times greater than the change in the ??13C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria. ?? 1981.

Origin and migration of hydrocarbon gases and carbon dioxide, Bekes Basin, southeastern Hungary

USGS Publications Warehouse

Clayton, J.L.; Spencer, C.W.; Koncz, I.; Szalay, A.

1990-01-01

The Bekes Basin is a sub-basin within the Pannonian Basin, containing about 7000 m of post-Cretaceous sedimentary rocks. Natural gases are produced from reservoirs (Precambrian to Tertiary in age) located on structural highs around the margins of the basin. Gas composition and stable carbon isotopic data indicate that most of the flammable gases were derived from humic kerogen contained in source rocks located in the deep basin. The depth of gas generation and vertical migration distances were estimated using quantitative source rock maturity-carbon isotope relationships for methane compared to known Neogene source rock maturity-depth relationships in the basin. These calculations indicate that as much as 3500 m of vertical migration has occured in some cases. Isotopically heavy (> - 7 > 0) CO2 is the predominant species present in some shallow reservoirs located on basin-margin structural highs and has probably been derived via long-distance vertical and lateral migration from thermal decompositon of carbonate minerals in Mesozoic and older rocks in the deepest parts of the basin. A few shallow reservoirs (< 2000m) contain isotopically light (-50 to -60%0) methane with only minor amounts of C2+ homologs (< 3% v/v). This methane is probably mostly microbial in origin. Above-normal pressures, occuring at depths greater than 1800 m, are believed to be the principal driving force for lateral and vertical gas migration. These pressures are caused in part by active hydrocarbon generation, undercompaction, and thermal decomposition of carbonates. 

Environmental forcing of terrestrial carbon isotope excursion amplification across five Eocene hyperthermals

NASA Astrophysics Data System (ADS)

Bowen, G. J.; Abels, H.

2015-12-01

Abrupt changes in the isotope composition of exogenic carbon pools accompany many major episodes of global change in the geologic record. The global expression of this change in substrates that reflect multiple carbon pools provides important evidence that many events reflect persistent, global redistribution of carbon between reduced and oxidized stocks. As the diversity of records documenting any event grows, however, discrepancies in the expression of carbon isotope change among substrates are almost always revealed. These differences in magnitude, pace, and pattern of change can complicate interpretations of global carbon redistribution, but under ideal circumstances can also provide additional information on changes in specific environmental and biogeochemical systems that accompanied the global events. Here we evaluate possible environmental influences on new terrestrial records of the negative carbon isotope excursions (CIEs) associated with multiple hyperthermals of the Early Eocene, which show a common pattern of amplified carbon isotope change in terrestrial paleosol carbonate records relative to that recorded in marine substrates. Scaling relationships between climate and carbon-cycle proxies suggest that that the climatic (temperature) impact of each event scaled proportionally with the magnitude of its marine CIE, likely implying that all events involved release of reduced carbon with a similar isotopic composition. Amplification of the terrestrial CIEs, however, does not scale with event magnitude, being proportionally less for the first, largest event (the PETM). We conduct a sensitivity test of a coupled plant-soil carbon isotope model to identify conditions that could account for the observed CIE scaling. At least two possibilities consistent with independent lines of evidence emerge: first, varying effects of pCO2 change on photosynthetic carbon isotope discrimination under changing background pCO2, and second, contrasting changes in regional

Triple oxygen isotopes in biogenic and sedimentary carbonates

NASA Astrophysics Data System (ADS)

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

2014-09-01

The 17O anomaly (Δ17O) 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 Δ17O than primary meteoric waters. In animal body water, Δ17O relates to the intake of evaporated waters, evaporative effluxes of water, and the Δ17O 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 Δ17O of carbonate. We describe optimized methods based on a sequential acid digestion/reduction/fluorination approach that yield Δ17O data with the high precision (∼0.010‰, 1σ) needed to resolve subtle environmental signals. We report the first high-precision Δ17O 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 δ18O and Δ17O 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 Δ17O values that are similar to or slightly lower than global precipitation. Our results suggest

Forensic utility of the carbon isotope ratio of PVC tape backings

NASA Astrophysics Data System (ADS)

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

2008-12-01

Forensic interest in adhesive tapes with PVC-backings (polyvinyl chloride, electrical tapes) derives from their use in construction of improvised explosive devices, drug packaging and in a variety of other illicit activities. Due to the range of physical characteristics and chemical compositions of such tapes, traditional microscopic and chemical analysis of the tape backings and adhesives offer a high degree of discrimination between tapes from different manufacturers and products. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different tapes of the same product, we assessed the PVC-backings of 87 rolls of black electrical tape for their δ13C values. The adhesive on these tapes was physically removed with hexane, and plasticizers within the PVC tape backings were removed by three-20 minute extractions with chloroform. The δ13C values of the PVC tape backings ranged between -23.8 and -41.5 (‰ V-PDB). The carbon isotopic variation within a product (identical brand and product identification) is significant, based on five products with at least 3 rolls (ranges of 7.4‰ (n=3), 10.0‰ (n=6), 4.2‰ (n=16), 3.8‰ (n=6), and 11.5‰ (n=8), respectively). There was no measurable carbon isotope variation in regards to the following: a) along the length of a roll (4 samples from 1 roll); b) between the center and edge of a strip of tape (1 pair); c) between rolls assumed to be from the same lot of tape (2 pairs); d) between different rolls from the same batch of tape (same product purchased at the same time and place; 5 pairs); and e) between samples of a tape at room temperature, heated to 50° C and 80° C for 1 week. For each sample within the population of 87 tapes, carbon isotopes alone exclude 80 to 100% of the tapes as a potential match, with an average exclusion power of 92.5%, using a window of ± 0.4‰. Carbon isotope variations originate from variations in starting

Using stable isotopes of carbon to investigate the seasonal variation of carbon transfer in a northwestern Arkansas cave

USGS Publications Warehouse

Knierim, Katherine J.; Pollock, Erik; Hays, Phillip D.; Khojasteh, Jam

2015-01-01

Stable-isotope analyses are valuable in karst settings, where characterizing biogeochemical cycling of carbon along groundwater flow paths is critical for understanding and protecting sensitive cave and karst water resources. This study quantified the seasonal changes in concentration and isotopic composition (δ13C) of aqueous and gaseous carbon species—dissolved inorganic carbon (DIC) and gaseous carbon dioxide (CO2)—to characterize sources and transfer of these species along a karst flow path, with emphasis on a cave environment. Gas and water samples were collected from the soil and a cave in northwestern Arkansas approximately once a month for one year to characterize carbon cycling along a conceptual groundwater flow path. In the soil, as the DIC concentration increased, the isotopic composition of the DIC became relatively lighter, indicating an organic carbon source for a component of the DIC and corroborating soil DIC as a proxy for soil respiration. In the cave, a positive correlation between DIC and surface temperature was due to increased soil respiration as the organic carbon signal from the soil was transferred to the cave environment via the aqueous phase. CO2 concentration was lowest in the cave during colder months and increased exponentially with increasing surface temperature, presumably due to higher rates of soil respiration during warmer periods and changing ventilation patterns between the surface and cave atmosphere. Isotopic disequilibrium between CO2 and DIC in the cave was greatest when CO2 concentration was changing during November/ December and March/April, presumably due to the rapid addition or removal of gaseous CO2. The isotopic disequilibrium between DIC and CO2 provided evidence that cave CO2 was a mixture of carbon from several sources, which was mostly constrained by mixture between atmospheric CO2 and soil CO2. The concentration and isotopic composition of gaseous and aqueous carbon species were controlled by month

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

Treesearch

Jeffrey F. Kelly

2000-01-01

Differential fractionation of stable isotopes of carbon during photosynthesis causes C4 plants and C3 plants to have distinct carbon-isotope signatures. In addition, marine C3 plants have stable-isotope ratios of carbon that are intermediate between C4 and terrestrial C3 plants. The direct incorporation of the carbon-isotope ratio (13C/12C) of plants into consumers...

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

NASA Technical Reports Server (NTRS)

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

2007-01-01

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

Chromium Isotopes in Marine Carbonates - an Indicator for Climatic Change?

NASA Astrophysics Data System (ADS)

Frei, R.; Gaucher, C.

2010-12-01

Chromium (Cr) stable isotopes experience an increased interest as a tracer of Cr (VI) reduction in groundwater and thus showed their potential as a monitor of remediation of anthropogenic and natural contamination in water (Berna et al., 2009; Izbicki et al., 2008). Chromium stable isotopes in Fe-rich chemical sediments (BIFs and Fe-cherts) have recently also been used as a tracer for Earth's atmospheric oxygenation through time (Frei et al., 2009). We have applied the Cr isotope system to organic-rich carbonates from a late Ediacaran succession in Uruguay (Polanco Formation), from which we have previously analyzed BIFs with extremely fractionated (δ53Cr up to 5.0 ‰) Cr isotope signatures that are part of an underlying deep water clastic sediment (shale-dominated) sequence (Yerbal Formation) deposited in a glacio-marine environment (Gaucher et al.,2004). δ53Cr values of organic rich carbonates correlate with positive and negative carbon isotope excursions (δ13C PDB between -3 and +3 ‰) and with systematic changes in strontium isotope compositions, commonly interpreted as to reflect fluctuations in organic (photosynthetic algae) production related to fluctuations in atmospheric oxygen and weathering intensities, respectively. Slightly positively fractioned δ53Cr values (up to +0.25‰), paralleling positive (δ13C PDB and 87Sr/86Sr ratio excursions would thereby trace elevated atmospheric oxygen levels/pulses possibly related to glacier retreat/melting stages that caused bioproductivity to increase. While the causal link between these multiple isotopic tracers and the mechanisms of Cr stripping into carbonates has to be further investigated in detail, the first indications from this study point to a potentially promising use of stable Cr isotopes in organic-rich carbonates to monitor fluctuations of atmospheric oxygen, particularly over the Neoproterozoic and Phanerozoic ice age periods. E.C. Berna et al. (2010) Cr stable isotopes as indicators of Cr

Anomalies of natural gas compositions and carbon isotope ratios caused by gas diffusion - A case from the Donghe Sandstone reservoir in the Hadexun Oilfield, Tarim Basin, northwest China

NASA Astrophysics Data System (ADS)

Wang, Yangyang; Chen, Jianfa; Pang, Xiongqi; Zhang, Baoshou; Wang, Yifan; He, Liwen; Chen, Zeya; Zhang, Guoqiang

2018-05-01

Natural gases in the Carboniferous Donghe Sandstone reservoir within the Block HD4 of the Hadexun Oilfield, Tarim Basin are characterized by abnormally low total hydrocarbon gas contents (<65%), low methane contents (<10%) and low dryness coefficients (<0.5), and a reversal of the normal trend of carbon isotope ratios, showing δ13C methane (C1) > δ13C ethane (C2) < δ13C propane (C3) < δ13C butane (C4). Specifically, methane is enriched in 13C with the variations in δ13C1 values between gases from Block HD4 and gases from its neighboring blocks reaching 10‰. This type of abnormal gas has never been reported previously in the Tarim Basin and such large variations in δ13C have rarely been observed in other basins globally. Based on a comprehensive analysis of gas geochemical data and the geological setting of the Carboniferous reservoirs in the Hadexun Oilfield, we reveal that the anomalies of the gas compositions and carbon isotope ratios in the Donghe Sandstone reservoir are caused by gas diffusion through the poorly-sealed caprock rather than by pathways such as gas mixing, microorganism degradation, different kerogen types or thermal maturity degrees of source rocks. The documentation of an in-reservoir gas diffusion during the post entrapment process as a major cause for gas geochemical anomalies may offer important insight into exploring natural gas resources in deeply buried sedimentary basins.

Increasing maturity of kerogen type II reflected by alkylbenzene distribution from pyrolysis-gas chromatography-mass spectrometry

USGS Publications Warehouse

Lis, G.P.; Mastalerz, Maria; Schimmelmann, A.

2008-01-01

A series of Late Devonian to Early Mississippian type II kerogens with vitrinite reflectance values Ro 0.29-2.41% were analyzed using py-GC-MS. In addition, a low maturity kerogen with Ro 0.44% was separated into fractions via density gradient centrifugation, followed by py-GC-MS of the alginite and amorphinite maceral concentrates. Alkylbenzenes and n-alk-1-ene/n-alkane doublets represented the main compound classes identified in all pyrolysates. The pyrolysate from alginite featured 1,2,4-trimethylbenzene and toluene as the two most prominent alkylbenzenes. In contrast, alkylbenzenes in pyrolysates from amorphinite and low maturity bulk kerogens with Ro 0.29-0.63% were dominated by 1,2,3,4-tetramethylbenzene. With increasing thermal maturity, pyrolysates were increasingly dominated by (i) alkylbenzenes with fewer methyl groups, namely by tri- and dimethylbenzenes at medium maturity (Ro 0.69-1.19%), and (ii) by toluene at higher maturity (Ro 1.30-2.41%). With increasing maturity of kerogen type II, the decreasing abundance of highly methyl-substituted alkylbenzenes and the parallel increase in less methyl-substituted alkylbenzenes in flash pyrolysates suggest that demethylation is an important chemical process in the thermal maturation of kerogen type II. ?? 2008 Elsevier Ltd. All rights reserved.

Carbon isotopic studies of organic matter in Precambrian rocks.

NASA Technical Reports Server (NTRS)

Oehler, D. Z.; Schopf, J. W.; Kvenvolden, K. A.

1972-01-01

A survey has been undertaken of the carbon composition of the total organic fraction of a suite of Precambrian sediments to detect isotopic trends possibly correlative with early evolutionary events. Early Precambrian cherts of the Fig Tree and upper and middle Onverwacht groups of South Africa were examined for this purpose. Reduced carbon in these cherts was found to be isotopically similar to photosynthetically produced organic matter of younger geological age. Reduced carbon in lower Onverwacht cherts was found to be anomalously heavy; it is suggested that this discontinuity may reflect a major event in biological evolution.

Experimental high temperature carbon isotope fractionation involving graphite

NASA Astrophysics Data System (ADS)

Kueter, N.; Schmidt, M. W.; Lilley, M. D.; Bernasconi, S. M.

2016-12-01

Graphite/carbonate carbon isotope fractionation was mainly investigated at 400- 800°C and is based on empirical calibrations, theoretical calculations and few experiments [1,2]. Own work on COH-fluid/graphite isotope fractionation shows that in experiments up to 1000oC a fluid phase is always enriched in 13C compared to coexisting graphitic carbon. The eventual kinetic isotope effect in these experiments is best displayed by the graphitic carbon being at least 3 ‰ lighter than methane. Only few experiments done in the graphite/carbonate pair dealt with higher temperatures reaching 1400°C, indicating a fractionation of up to 2 ‰ at temperatures of the Earth's mantle [2-4]. To better understand carbon isotope fractionation in crustal systems and still overcome kinetic effects, we study the graphite/carbonatite pair with piston cylinder experiments in the Na2CO3-CaCO3-CaO-COH system. Tartaric acid (C4H6O6) supplies reduced carbon, time series are performed at 10 kbar, 1300-1800°C. Initial experiments at 1300°C produce well-ordered, micron-sized graphite flakes growing attached to the capsule walls while the Na-Ca-carbonatite-melt quenches to dendritic textures. No gaseous phase was observed. Conditions well above the liquidus of the Na2CO3-CaCO3-binary lead to dissolution of the H2O from tartaric acid decomposition in the melt, any CO2-component is bound by the excess CaO to CaCO3melt while in the relatively oxidizing capsule environment any CH4-component reacts with CO2 to carbon and H2O. The graphite and the carbonatite quench are measured for their δ13C composition using a GasBench II (carbonate-dissolution in phosphoric acid) and TC/EA (residual graphite combusted in oxygen atmosphere) system coupled to a Thermo Fischer IRMS. Our results expand from the graphite-carbonate system to graphite-fluid system when adding available fluid-carbonate fractionation factors, but are also directly applicable to diamond synthesis as graphite is often found as a

Carbon isotope effect during abiogenic oxidation of methane

NASA Astrophysics Data System (ADS)

Kiyosu, Yasuhiro; Roy Krouse, H.

1989-11-01

The oxidation of methane during flow over CuO and Fe 2O 3 has been examined in the temperature range of 400-650°C. The reaction rate and carbon isotope fractionation are dependent upon the choice of oxide and temperature. The activation energy is lower for hematite (8.0 kcal mole -1) than for cupric oxide (16.6 kcal mole -1). The measured ratios of the isotopic rate constants α =k 12/k 13 were found to have temperature dependences given by: 10 3(α - 1) =2.93 × 10 6/T 2 + 8.11 (cupric oxide) 10 3(α - 1) =7.44 × 10 6/T 2 + 6.56 (hematite) Abiogenic oxidation of methane is probably a significant mechanism for fractionating carbon isotopes in nature.

Does burial diagenesis reset pristine isotopic compositions in paleosol carbonates?

NASA Astrophysics Data System (ADS)

Bera, M. K.; Sarkar, A.; Tandon, S. K.; Samanta, A.; Sanyal, P.

2010-11-01

Sedimentological study of early Oligocene continental carbonates from the fluvial Dagshai Formation of the Himalayan foreland basin, India resulted in the recognition of four different types namely, soil, palustrine, pedogenically modified palustrine and groundwater carbonates. Stable oxygen and carbon isotopic ( δ18O and δ13C) analyses of fabric selective carbonate microsamples show that although the pristine isotopic compositions are largely altered during deep-burial diagenesis, complete isotopic homogenization does not occur. δ18O and δ13C analyses of ~ 200 calcrete and palustrine carbonates from different stratigraphic horizons and comparison with δ18O of more robust bioapatite (fossil vertebrate tooth) phase show that dense micrites (~ > 70% carbonate) invariably preserve the pristine δ18O value (mean) of ~ - 9.8‰, while altered carbonates show much lower δ18O value ~ - 13.8‰. Such inhomogeneity causes large intra-sample and intra-soil profile variability as high as > 5‰, suggesting that soils behave like a closed system where diagenetic overprinting occurs in local domains. A simple fluid-rock interaction model suggests active participation of clay minerals to enhance the effect of fluid-rock ratio in local domains during diagenesis. This places an upper limit of 70% micrite concentration above which the effect of diagenetic alteration is minimal. Careful sampling of dense micritic part of the soil carbonate nodules, therefore, does provide pristine isotopic composition and it is inappropriate, as proposed recently, to reject the paleoclimatic potential of all paleosol carbonates affected by burial diagenesis. Based on pristine δ13C value of - 8.8 ± 0.2‰ in soil carbonates an atmospheric CO 2 concentration between ~ 764 and ~ 306 ppmv is estimated for the early Oligocene (~ 31 Ma) Dagshai time. These data show excellent agreement between two independent proxy records (viz. soil carbonate and marine alkenone) and support early Oligocene

Carbon and hydrogen isotope fractionation during aerobic biodegradation of quinoline and 3-methylquinoline.

PubMed

Cui, Mingchao; Zhang, Wenbing; Fang, Jun; Liang, Qianqiong; Liu, Dongxuan

2017-08-01

Compound-specific isotope analysis has been used extensively to investigate the biodegradation of various organic pollutants. To date, little isotope fractionation information is available for the biodegradation of quinolinic compounds. In this study, we report on the carbon and hydrogen isotope fractionation during quinoline and 3-methylquinoline aerobic microbial degradation by a Comamonas sp. strain Q10. Degradation of quinoline and 3-methylquinoline was accompanied by isotope fractionation. Large hydrogen and small carbon isotope fractionation was observed for quinoline while minor carbon and hydrogen isotope fractionation effects occurred for 3-methylquinoline. Bulk carbon and hydrogen enrichment factors (ε bulk ) for quinoline biodegradation were -1.2 ± 0.1 and -38 ± 1‰, respectively, while -0.7 ± 0.1 and -5 ± 1‰ for 3-methylquinoline, respectively. This reveals a potential advantage for employing quinoline as the model compound and hydrogen isotope analysis for assessing aerobic biodegradation of quinolinic compounds. The apparent kinetic isotope effects (AKIE C ) values of carbon were 1.008 ± 0.0005 for quinoline and 1.0048 ± 0.0005 for 3-methylquinoline while AKIE H values of hydrogen of 1.264 ± 0.011 for quinoline and 1.0356 ± 0.0103 for 3-methylquinoline were obtained. The combined evaluation of carbon and hydrogen isotope fractionation yields Λ values (Λ = Δδ 2 H/Δδ 13 C ≈ εH bulk /εC bulk ) of 29 ± 2 for quinoline and 8 ± 2 for 3-methylquinoline. The results indicate that the substrate specificity may have a significant influence on the isotope fractionation for the biodegradation of quinolinic compounds. The substrate-specific isotope enrichment factors would be important for assessing the behavior and fate of quinolinic compounds in the environment.

Experimental Assessment of Carbon Isotopes of Light Hydrocarbons under Different Redox Conditions

NASA Astrophysics Data System (ADS)

Fu, Q.; Chen, X.

2017-12-01

Hydrocarbons can be derived from a variety of carbon sources, by different processes, and under a wide range of physicochemical conditions. Other than bacterial activities facilitating biogenic hydrocarbon formation at low temperatures, decomposition of complex organic matter in sedimentary rocks at elevated temperatures produce thermogenic hydrocarbons, whereas abiogenic hydrocarbons are mainly generated through Fischer-Tropsch type synthesis with mineral catalysts. The carbon isotope has been used extensively to distinguish hydrocarbons of different origins and their formation conditions. For each type of hydrocarbons, however, environmental conditions may change reaction pathways and corresponding isotope fractionations. To better understand the variation of carbon isotopes caused by environmental variables, mineral constraints in particular, a series of laboratory experiments are conducted. In experiments where thermogenic hydrocarbons are formed, oil shale is the source material with different gypsum contents (0, 0.3, 0.5, and 1 wt.%). The abundance of generated light straight chain hydrocarbons decreases with increasing gypsum content, but their carbon isotopes become heavier. For example, the δ13C value of methane increases from -55.1‰ to -41.4‰ with gypsum varying between 0 and 1 wt.%. In similar experiments with the presence of MnO2, carbon isotope values of light alkanes are also higher, but with limited magnitudes (e.g., 3 to 4‰ for methane). In another experiment with dissolved H2 gas of 100 mmol/kg, light alkanes become depleted in 13C than experiments without H2. For example, there is a depletion of 2.7‰ for methane. The variation of carbon isotope values of light alkanes suggests the redox condition, constrained by mineral assemblage, fluid composition, and physical environment, play an important role in isotope fractionation. The pathway of hydrocarbon generation may be different under oxidized or reducing conditions. A set of experiments

Stable carbon and sulfur isotopes as records of the early biosphere

NASA Technical Reports Server (NTRS)

Desmarais, David J.

1989-01-01

The abundance ratios of the stable isotopes of light elements such as carbon and sulfur can differ between various naturally-occurring chemical compounds. If coexisting compounds have achieved mutual chemical and isotopic equilibrium, then the relative isotopic composition can record the conditions at which equilibrium was last maintained. If coexisting chemical compounds indeed formed simultaneously but had not achieved mutual equilibrium, then their relative isotopic compositions often reflect the conditions and mechanisms associated with the kinetically controlled reactions responsible for their production. In the context of Mars, the stable isotopic compositions of various minerals might record not only the earlier environmental conditions of the planet, but also whether or not the chemistry of life ever occurred there. Two major geochemical reservoirs occur in Earth's crust, both for carbon and sulfur. In rocks formed in low temperature sedimentary environments, the oxidized forms of these elements tend to be enriched in the isotope having the larger mass, relative to the reduced forms. In sediments where the organics and sulfides were formed by biological processes, these isotopic contrasts were caused by the processes of biological CO2 fixation and dissimilatory sulfate reduction. Such isotopic contrasts between oxidized and reduced forms of carbon and sulfur are permitted by thermodynamics at ambient temperatures. However, nonbiological chemical reactions associated with the production of organic matter and the reduction of organics and sulfides are extremely slow at ambient temperatures. Thus the synthesis of organics and sulfides under ambient conditions illustrates life's profound role as a chemical catalyst that has altered the chemistry of Earth's crust. Because the stable isotopes of carbon and sulfur can reflect their chemistry, they are useful probes of the Martian surface.

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

NASA Technical Reports Server (NTRS)

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

1987-01-01

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.

Aptian Carbon Isotope Stratigraphy in Sierra del Rosario, Northeastern Mexico

NASA Astrophysics Data System (ADS)

Barragan-Manzo, R.; Moreno-Bedmar, J.; Nuñez, F.; Company, M.

2013-05-01

In most recent years Aptian carbon isotope stratigraphy has been widely studied in Europe where isotopic stages have been developed to correlate global events. Two negative excursions have been recorded in the Lower Aptian, the older is OAE 1a in the middle part, and a younger negative excursion labeled "Aparein level", which occurs in the uppermost part of the Lower Aptian. In Mexico previous works reported a carbon isotope negative excursion in the lowermost part of the La Peña Formation that was assigned to the onset of Oceanic Anoxic Event 1a (=OAE 1a). In this work we study the isotopic record of the δ13Ccarb of 32 bulk rock samples of limestone from the uppermost part of the Cupido Formation and the lower part of the La Peña Formation at the Francisco Zarco Dam Section (=FZD), Durango State, northeastern Mexico. The isotopic data are calibrated using the latest ammonite biostratigraphic biozonation of the Aptian. This age calibration allows us to make a precise correlation between the carbon isotopic record of Mexico and several European sections (e.g. Spain and France). In the studied Francisco Zarco Dam section we recognize a negative carbon isotopic excursion in the Dufrenoyia justinae ammonite Zone that corresponds to the "Aparein level", which we correlate using the ammonite zonation of others European sections (Figure 1). This correlation allows us to see how the negative excursion that characterizes the "Aparein level" is consistent with the C7 segment. Thus, our recent stratigraphic study allows us to conclude that the ammonite record in the lowermost part of the La Peña Formation is regionally isochronous, and correlates with the Dufrenoyia justinae Zone and Lower Aptian isotope interval C7. In agreement to these biostratigraphic data, the supposed record of the OAE 1a in the lowermost part of the La Peña Formation is not correct, and the carbon isotope negative excursion must be assigned to the younger event "Aparein level". Taking this into

Nitrogen isotope record of a perturbed paleoecosystem in the aftermath of the end-Triassic crisis, Doniford section, SW England

NASA Astrophysics Data System (ADS)

Paris, Guillaume; Beaumont, ValéRie; Bartolini, Annachiara; CléMence, Marie-Emilie; Gardin, Silvia; Page, Kevin

2010-08-01

The Triassic-Jurassic transition (TJ) is characterized by successive perturbations of the carbon cycle during a time of biotic disruption as recorded by the carbon isotopic composition of organic matter (δ13Corg). The nitrogen isotopic composition of sedimentary organic matter (δ15Norg) constitutes a key parameter to explore the functioning of the ecosystem during carbon cycle perturbations and biological crises, because it provide information on seawater redox conditions and/or nutrient cycling. Here we report the first continuous δ15Norg record across the TJ transition at the Doniford Bay section (Bristol Channel Basin, UK), combined with δ13Corg, kerogen typology and carbon (δ13Cmin) and oxygen (δ18Omin) isotopic composition of bulk carbonates. The end Triassic is characterized by a major negative excursion both in δ13Corg and δ13Cmin, very low TOC (Total Organic Carbon, wt%) and high δ15Norg values, associated with a sea level lowstand. A second δ13Corg negative excursion occurs during the lower Hettangian. This interval is characterized by phases of carbonate production increase alternated with phases of exceptional accumulations of type I organic matter (up to 12%) associated with lower δ15Norg and δ13Corg. This alternation likely reflects a succession of nutrient input increase to the basin leading to enhanced productivity and eutrophication, which promoted a primary production driven by organic-walled prokaryotic organisms. The following OM export increase generates anaerobic conditions within the basin. These events occur between periods of relatively good seawater column ventilation and nutrient recycling boosting the carbonate producer recovery. Ecosystems remain perturbed in the Bristol Channel Basin during the aftermath of the end-Triassic crisis.

How the oxygen isotope ratio of rain water influences the isotope ratio of chicken eggshell carbonate

NASA Astrophysics Data System (ADS)

Price, Gregory; Grimes, Stephen

2015-04-01

The stable oxygen isotope ratio of chicken eggshell carbonate was analysed from chicken eggs laid under free range, and organic farming regimes from across the UK. The eggshell carbonate oxygen isotope data shows a clear depletion in delta18O distribution from the southwest to the northeast. Although consistently offset by around 1 permil, the same isotopic distribution as that seen in eggshell carbonate is observed in the delta18O ratio of rainfall and groundwater from across the UK. This distribution is related to the Rayleigh distillation of rainfall driven by westerly winds across the UK landmass. The clear relationship observed between eggshell delta18O values and that of rainwater presumably reflects the nature of free range chickens which must be drinking locally derived rainwater and supplementing their diet and water intake with locally derived food. These results suggest that the oxygen isotope value of chicken eggshells can be used as a forensic tool to identify the locality that free range and organic eggs were laid within the UK. Furthermore, if suitable material is preserved in the archaeological and geological record then such a relationship can potentially be used to establish the oxygen isotope value of rainwater from which ancient and / or ancestral birds lived.

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

NASA Astrophysics Data System (ADS)

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

2013-08-01

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 μM 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.

CO2-dependent carbon isotope fractionation in the dinoflagellate Alexandrium tamarense

NASA Astrophysics Data System (ADS)

Wilkes, Elise B.; Carter, Susan J.; Pearson, Ann

2017-09-01

The carbon isotopic composition of marine sedimentary organic matter is used to resolve long-term histories of pCO2 based on studies indicating a CO2-dependence of photosynthetic carbon isotope fractionation (εP). It recently was proposed that the δ13C values of dinoflagellates, as recorded in fossil dinocysts, might be used as a proxy for pCO2. However, significant questions remain regarding carbon isotope fractionation in dinoflagellates and how such fractionation may impact sedimentary records throughout the Phanerozoic. Here we investigate εP as a function of CO2 concentration and growth rate in the dinoflagellate Alexandrium tamarense. Experiments were conducted in nitrate-limited chemostat cultures. Values of εP were measured on cells having growth rates (μ) of 0.14-0.35 d-1 and aqueous carbon dioxide concentrations of 10.2-63 μmol kg-1 and were found to correlate linearly with μ/[CO2(aq)] (r2 = 0.94) in accord with prior, analogous chemostat investigations with eukaryotic phytoplankton. A maximum fractionation (εf) value of 27‰ was characterized from the intercept of the experiments, representing the first value of εf determined for an algal species employing Form II RubisCO-a structurally and catalytically distinct form of the carbon-fixing enzyme. This value is larger than theoretical predictions for Form II RubisCO and not significantly different from the ∼25‰ εf values observed for taxa employing Form ID RubisCO. We also measured the carbon isotope contents of dinosterol, hexadecanoic acid, and phytol from each experiment, finding that each class of biomarker exhibits different isotopic behavior. The apparent CO2-dependence of εP values in our experiments strengthens the proposal to use dinocyst δ13C values as a pCO2 proxy. Moreover, the similarity between the εf value for A. tamarense and the consensus value of ∼25‰ indicates that the CO2-sensitivity of carbon isotope fractionation saturates at similar CO2 levels across all three

What Drives Carbon Isotope Fractionation by the Terrestrial Biosphere?

NASA Astrophysics Data System (ADS)

Still, Christopher; Rastogi, Bharat

2017-11-01

During photosynthesis, terrestrial plants preferentially assimilate the lighter and much more abundant form of carbon, 12C, which accounts for roughly 99% of naturally occurring forms of this element. This photosynthetic preference for lighter carbon is driven principally by differences in molecular diffusion of carbon dioxide with differing 13C/12C across stomatal pores on leaves, followed by differences in carboxylation rates by the Rubisco enzyme that is central to the process of photosynthesis. As a result of these slight preferences, which work out to about a 2% difference in the fixation rates of 12CO2 versus 13CO2 by C3 vegetation, plant tissues are depleted in the heavier form of carbon (13C) relative to atmospheric CO2. This difference has been exploited in a wide range of scientific applications, as the photosynthetic isotope signature is passed to ecosystem carbon pools and through ecological food webs. What is less appreciated is the signature that terrestrial carbon exchanges leave on atmospheric CO2, as the net uptake of carbon by land plants during their growing season not only draws down the local CO2 concentration, it also leaves behind relatively more CO2 molecules containing 13C. The converse happens outside the growing season, when autotrophic and heterotrophic respiration predominate. During these periods, atmospheric CO2 concentration increases and its corresponding carbon isotope composition becomes relatively depleted in 13C as the products of photosynthesis are respired, along with some small isotope fractionation that happen downstream of the initial photosynthetic assimilation. Similar phenomena were first observed at shorter time scales by the eminent carbon cycle scientist, Charles (Dave) Keeling. Keeling collected samples of air in glass flasks from sites along the Big Sur coast that he later measured for CO2 concentration and carbon isotope composition (δ13C) in his lab (Keeling, 1998). From these samples, Keeling observed increasing

Steranes and triterpanes generated from kerogen pyrolysis in the absence and presence of minerals

NASA Technical Reports Server (NTRS)

Tannenbaum, E.; Ruth, E.; Kaplan, I. R.

1986-01-01

Changes in the degree of isomerization of steranes and triterpanes during kerogen pyrolysis in the absence or presence of minerals are described. Kerogen from a Monterey Formation diatomite core sample was pyrolyzed under reduced pressure at 300 C for 2-1000 hrs in the presence or absence of calcite, illite, and montmorillonite. It is observed that the extent of isomerization of biomakers in C-20 in 14 alpha(H), 17 alpha(H)-steranes, at C-22 in 17 alpha(H), 21 beta(H)-hopanes and of 17 beta(H), 21 beta(H)-hopanes correlates to early diagenetic stages in rock extracts from sedimentary basins, and faster isomerization for steranes and triterpanes in the bitumen then for those in the kerogen structure are detected. The effects of the minerals on the isomerization reactions are examined; calcite inhibits, and illite and montmorillonite catalyze the reactions.

Speleothems as proxy for the carbon isotope composition of atmospheric CO2

NASA Astrophysics Data System (ADS)

Baskaran, M.; Krishnamurthy, R. V.

1993-12-01

We have measured the stable isotope ratios of carbon in a suite of recent cave deposits (less than 200 years) from the San Saba County, Texas, USA. The methodology for dating these deposits using excess Pb-210 was recently established (Baskaran and Iliffe, 1993). The carbon isotope ratios of these samples, spanning the time period approximately 1800-1990 AD, reflect the carbon isotope ratio of atmospheric CO2 for the same period. The pathways by which the delta C-13 of atmospheric CO2 is imprinted on these speleothems can be explained using a model developed by Cerling (1984). The results suggest that the carbon isotope ratios of speleothems can be used to develop long-term, high-resolution chronologies of the delta C-13 of atmospheric CO2 and, by implication, the concentration of the atmospheric CO2.

Molecular Imaging of Kerogen and Minerals in Shale Rocks across Micro- and Nano- Scales

NASA Astrophysics Data System (ADS)

Hao, Z.; Bechtel, H.; Sannibale, F.; Kneafsey, T. J.; Gilbert, B.; Nico, P. S.

2016-12-01

Fourier transform infrared (FTIR) spectroscopy is a reliable and non-destructive quantitative method to evaluate mineralogy and kerogen content / maturity of shale rocks, although it is traditionally difficult to assess the organic and mineralogical heterogeneity at micrometer and nanometer scales due to the diffraction limit of the infrared light. However, it is truly at these scales that the kerogen and mineral content and their formation in share rocks determines the quality of shale gas reserve, the gas flow mechanisms and the gas production. Therefore, it's necessary to develop new approaches which can image across both micro- and nano- scales. In this presentation, we will describe two new molecular imaging approaches to obtain kerogen and mineral information in shale rocks at the unprecedented high spatial resolution, and a cross-scale quantitative multivariate analysis method to provide rapid geochemical characterization of large size samples. The two imaging approaches are enhanced at nearfield respectively by a Ge-hemisphere (GE) and by a metallic scanning probe (SINS). The GE method is a modified microscopic attenuated total reflectance (ATR) method which rapidly captures a chemical image of the shale rock surface at 1 to 5 micrometer resolution with a large field of view of 600 X 600 micrometer, while the SINS probes the surface at 20 nm resolution which provides a chemically "deconvoluted" map at the nano-pore level. The detailed geochemical distribution at nanoscale is then used to build a machine learning model to generate self-calibrated chemical distribution map at micrometer scale with the input of the GE images. A number of geochemical contents across these two important scales are observed and analyzed, including the minerals (oxides, carbonates, sulphides), the organics (carbohydrates, aromatics), and the absorbed gases. These approaches are self-calibrated, optics friendly and non-destructive, so they hold the potential to monitor shale gas

A carbon isotope challenge to the snowball Earth.

PubMed

Sansjofre, P; Ader, M; Trindade, R I F; Elie, M; Lyons, J; Cartigny, P; Nogueira, A C R

2011-10-05

The snowball Earth hypothesis postulates that the planet was entirely covered by ice for millions of years in the Neoproterozoic era, in a self-enhanced glaciation caused by the high albedo of the ice-covered planet. In a hard-snowball picture, the subsequent rapid unfreezing resulted from an ultra-greenhouse event attributed to the buildup of volcanic carbon dioxide (CO(2)) during glaciation. High partial pressures of atmospheric CO(2) (pCO2; from 20,000 to 90,000 p.p.m.v.) in the aftermath of the Marinoan glaciation (∼635 Myr ago) have been inferred from both boron and triple oxygen isotopes. These pCO2 values are 50 to 225 times higher than present-day levels. Here, we re-evaluate these estimates using paired carbon isotopic data for carbonate layers that cap Neoproterozoic glacial deposits and are considered to record post-glacial sea level rise. The new data reported here for Brazilian cap carbonates, together with previous ones for time-equivalent units, provide estimates lower than 3,200 p.p.m.v.--and possibly as low as the current value of ∼400 p.p.m.v. Our new constraint, and our re-interpretation of the boron and triple oxygen isotope data, provide a completely different picture of the late Neoproterozoic environment, with low atmospheric concentrations of carbon dioxide and oxygen that are inconsistent with a hard-snowball Earth.

BOREAS TE-5 Leaf Carbon Isotope Data

NASA Technical Reports Server (NTRS)

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

2000-01-01

The BOREAS TE-5 team collected measurements in the NSA and SSA on gas exchange, gas composition, and tree growth. This documentation describes leaf carbon isotope data that were collected in 1993 and 1994 at the NSA and SSA OJP sites, the SSA OBS site, and the NSA UBS site. In addition, leaf carbon isotope data were collected in 1994 only at the NSA and SSA OA sites. These data was collected to provide seasonal integrated physiological information for 10 to 15 common species at these 6 BOREAS sites. The data are stored 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).

Stable isotopic compositions of carbonates from the Mesoproterozoic Bangemall Group, northwestern Australia

NASA Technical Reports Server (NTRS)

Buick, R.; Des Marais, D. J.; Knoll, A. H.

1995-01-01

Marine carbonate rocks from the Mesoproterozoic Bangemall Group of northwestern Australia show little deviation (+/-1.3%) in whole-rock delta 13C(carb)-values about a mean of -0.5%. This narrow range persists despite close sampling (every 10-20 m) through long sections (up to 2500 m) that are geographically widespread (up to 250 km apart), over many depositional environments (supralittoral to outer shelf), sediment sources (stromatolitic bioherms to detrital calcilutites) and rock types (pure limestones to dolomitic shales). The only major excursions from the norm seem related to unusual environmental or post-depositional processes, as they are correlated with large enrichments (to -3%) or depletions (to -16%) in 18O. Relatively heavy delta 13C-values, up to +2.5%, occur in a single bed of brecciated ferruginous dolostone at a single locality; these abnormal values may result from local evaporitic conditions. Limey and shaley nodular dolostones have delta 13C-values as low as -4.3%, probably caused by remineralization of organic matter during late and patchy dolomitization. Most notably, sharp negative excursions in delta 13C, up to -8.4%, occur in bleached kerogen-free rocks with mineral assemblages of dolomite + quartz + calcite +/- tremolite + talc, reflecting isotopic re-equilibration in thick metamorphic aureoles around dolerite intrusions. General environmental variations are minor, with delta 13C-values of peritidal facies tending to be slightly positive whereas those of subtidal facies are slightly negative. There are no strong secular trends, but subtle fluctuations within the range -2 to +l% can be correlated along the northwestern margin of the basin. This resembles the pattern seen in other Mesoproterozoic successions, but is markedly unlike the heavy background (> +5%) and extreme variations (up to l0%) in delta 13C evident in Neoproterozoic successions of similar thickness and environmental setting. Hence, in contrast to the Neoproterozoic, the global

New Carbonate Standard Reference Materials for Boron Isotope Geochemistry

NASA Astrophysics Data System (ADS)

Stewart, J.; Christopher, S. J.; Day, R. D.

2015-12-01

The isotopic composition of boron (δ11B) in marine carbonates is well established as a proxy for past ocean pH. Yet, before palaeoceanographic interpretation can be made, rigorous assessment of analytical uncertainty of δ11B data is required; particularly in light of recent interlaboratory comparison studies that reported significant measurement disagreement between laboratories [1]. Well characterised boron standard reference materials (SRMs) in a carbonate matrix are needed to assess the accuracy and precision of carbonate δ11B measurements throughout the entire procedural chemistry; from sample cleaning, to ionic separation of boron from the carbonate matrix, and final δ11B measurement by multi-collector inductively coupled plasma mass spectrometry. To date only two carbonate reference materials exist that have been value-assigned by the boron isotope measurement community [2]; JCp-1 (porites coral) and JCt-1 (Giant Clam) [3]. The National Institute of Standards and Technology (NIST) will supplement these existing standards with new solution based inorganic carbonate boron SRMs that replicate typical foraminiferal and coral B/Ca ratios and δ11B values. These new SRMs will not only ensure quality control of full procedural chemistry between laboratories, but have the added benefits of being both in abundant supply and free from any restrictions associated with shipment of biogenic samples derived from protected species. Here we present in-house δ11B measurements of these new boron carbonate SRM solutions. These preliminary data will feed into an interlaboratory comparison study to establish certified values for these new NIST SRMs. 1. Foster, G.L., et al., Chemical Geology, 2013. 358(0): p. 1-14. 2. Gutjahr, M., et al., Boron Isotope Intercomparison Project (BIIP): Development of a new carbonate standard for stable isotopic analyses. Geophysical Research Abstracts, EGU General Assembly 2014, 2014. 16(EGU2014-5028-1). 3. Inoue, M., et al., Geostandards and

Isotope Variations in Terrestrial Carbonates and Thermal Springs as Biomarkers: Analogs for Martian Processes

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Gibson, Everett K., Jr.; Bissada, K. K.

2006-01-01

Stable isotope measurements of carbonate minerals contained within ALH84001 [1] suggest that fluids were present at 3.9 Gy on Mars [2, 3, 4, 5]. Both oxygen and carbon isotopes provide independent means of deciphering paleoenvironmental conditions at the time of carbonate mineral precipitation. In terrestrial carbonate rocks oxygen isotopes not only indicate the paleotemperature of the precipitating fluid, but also provide clues to environmental conditions that affected the fluid chemistry. Carbon isotopes, on the other hand, can indicate the presence or absence of organic compounds during precipitation (i.e. biogenically vs. thermogenically-generated methane), thus serving as a potential biomarker. We have undertaken a study of micro scale stable isotope variations measured in some terrestrial carbonates and the influence of organic compounds associated with the formation of these carbonates. Preliminary results indicate that isotope variations occur within narrow and discrete intervals, providing clues to paleoenvironmental conditions that include both biological and non-biological activity. These results carry implications for deciphering Martian isotope data and therefore potential biological prospecting on the planet Mars. Recently, Fourier Transform Spectrometer observations have detected methane occurring in the Martian atmosphere [6] that could be attributed to a possible biogenic source. Indeed, Mars Express has detected the presence of methane in the Martian atmosphere [7], with evidence indicating that methane abundances are greatest above those basins with high water concentrations.

Discrimination factors of carbon and nitrogen stable isotopes in meerkat feces

PubMed Central

2017-01-01

Stable isotope analysis of feces can provide a non-invasive method for tracking the dietary habits of nearly any mammalian species. While fecal samples are often collected for macroscopic and genetic study, stable isotope analysis can also be applied to expand the knowledge of species-specific dietary ecology. It is somewhat unclear how digestion changes the isotope ratios of animals’ diets, so more controlled diet studies are needed. To date, most diet-to-feces controlled stable isotope experiments have been performed on herbivores, so in this study I analyzed the carbon and nitrogen stable isotope ratios in the diet and feces of the meerkat (Suricata suricatta), a small omnivorous mammal. The carbon trophic discrimination factor between diet and feces (Δ13Cfeces) is calculated to be 0.1 ± 1.5‰, which is not significantly different from zero, and in turn, not different than the dietary input. On the other hand, the nitrogen trophic discrimination factor (Δ15Nfeces) is 1.5 ± 1.1‰, which is significantly different from zero, meaning it is different than the average dietary input. Based on data generated in this experiment and a review of the published literature, carbon isotopes of feces characterize diet, while nitrogen isotope ratios of feces are consistently higher than dietary inputs, meaning a discrimination factor needs to be taken into account. The carbon and nitrogen stable isotope values of feces are an excellent snapshot of diet that can be used in concert with other analytical methods to better understand ecology, diets, and habitat use of mammals. PMID:28626611

Bringing organic carbon isotopes and phytoliths to the table as additional constraints on paleoelevation

NASA Astrophysics Data System (ADS)

Sheldon, N. D.; Cotton, J. M.; Hren, M. T.; Hyland, E. G.; Smith, S. Y.; Strömberg, C. A. E.

2015-12-01

A commonly used tool in paleotectonic and paleoaltimetry studies is the oxygen isotopic composition of authigenic carbonates formed that formed in lakes or soils, with both spatial (e.g., shoreline to mountain top) or temporally resolved records potentially providing constraints. However, in many cases there is a substantial spread in the oxygen isotope data for a given time period, often to the point of allowing for essentially any interpretation of the data depending upon how they have been used by the investigator. One potential way of distinguishing between different potential paleotectonic or paleoaltimetric interpretations is to use carbon isotope and plant microfossil (phytolith) analyses from the same paleosols to screen the oxygen isotope data by looking for evidence of evaporative enrichment. For example, if both inorganic (carbonate) and organic carbon isotopes are measured from the same paleosol, then in it possible to determine if the two isotope record equilibrium conditions or if they record disequilibrium driven by kinetic effects. In the former case, the oxygen isotope results can be considered reliable whereas in the latter case, the oxygen isotope results can be considered unreliable and could be culled from the interpretation. Similarly, because the distribution of C4 plants varies as a function of temperature and elevation, the presence/absence or abundance of C4 plant phytoliths, or of carbon isotope compositions that require a component of C4 vegetation can also be used to constrain paleoelevation by providing a maximum elevation constraint. Worked examples will include the late Miocene-Pliocene of Catamarca, Argentina, where phytoliths and organic carbon isotopes provide a maximum elevation constraint and can be used to demonstrate that oxygen isotopes do not provide a locally useful constraint on paleoelevation, and Eocene-Miocene of southwestern Montana where organic matter and phytoliths can be used to select between different potential

Carbonic Anhydrase, Calcification Dynamics and Stable Isotope Vital Effects: Deep Sea Corals and Beyond

NASA Astrophysics Data System (ADS)

Chen, S.; Gagnon, A. C.; Adkins, J. F.

2017-12-01

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed "vital effects". A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ18O and δ13C in a range of values that are depleted from equilibrium. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO2(aq)-HCO3- inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO2(aq)-HCO3- inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ18O-δ13C correlation. With this model, we are not only able to fit deep sea coral data, but also explain the stable isotope vital effects of other calcifying organisms. This fully kinetic model of stable isotope vital effects and the underlying calcification dynamics may also help us better understand mechanisms of other paleoceanographic tracers in biogenic carbonates, including boron isotopes and trace metal proxies.

Carbon isotopic evidence for microbial control of carbon supply to Orca Basin at the seawater-brine interface

NASA Astrophysics Data System (ADS)

Shah, S. R.; Joye, S. B.; Brandes, J. A.; McNichol, A. P.

2013-05-01

Orca Basin, an intraslope basin on the Texas-Louisiana continental slope, hosts a hypersaline, anoxic brine in its lowermost 200 m in which limited microbial activity has been reported. This brine contains a large reservoir of reduced and aged carbon, and appears to be stable at decadal time scales: concentrations and isotopic composition of dissolved inorganic (DIC) and organic carbon (DOC) are similar to measurements made in the 1970s. Both DIC and DOC are more "aged" within the brine pool than in overlying water, and the isotopic contrast between brine carbon and seawater carbon is much greater for DIC than DOC. While the stable carbon isotopic composition of brine DIC points towards a combination of methane and organic carbon remineralization as its source, radiocarbon and box model results point to the brine interface as the major source region for DIC, allowing for only limited oxidation of methane diffusing upwards from sediments. This conclusion is consistent with previous studies that identify the seawater-brine interface as the focus of microbial activity associated with Orca Basin brine. Isotopic similarities between DIC and DOC suggest a different relationship between these two carbon reservoirs than is typically observed in deep ocean basins. Radiocarbon values implicate the seawater-brine interface region as the likely source region for DOC to the brine as well as DIC.

The use of kerogen data in understanding the properties and evolution of interstellar carbonaceous dust

NASA Astrophysics Data System (ADS)

Papoular, R.

2001-11-01

A number of authors have, in the past decade, pointed to the similarity of the 3.4-mu m band of kerogen with that of the Galactic Centre (GC). Kerogen is a family of solid terrestrial sedimentary materials essentially made of C, H and O interlocked in a disordered, more or less aliphatic, structure. Here, the most recent results of the astronomical literature and the rich quantitative geochemical literature are tapped with two purposes in mind: extend the analogy to the mid-IR bands and, based on these new constraints, quantitatively assess the properties of the carrier dust. It is shown that the great diversity of IR astronomical IS (interstellar) dust is paralleled by the changes in kerogen spectra as the material spontaneously and continuously evolves (aromatizes) in the earth. Since the composition and structure of kerogen are known all along its evolution, it is possible, by spectral analogy, to estimate these properties for the corresponding astronomical carriers. The Galactic Centre 3.4 mu m feature is thus found to correspond to an early stage of evolution, for which the composition in C, H and O and the structure of the corresponding kerogen are known and reported here. The role of oxygen in the subsequent evolution and its contribution to different bands are stressed. The above provides new arguments in favour of the 3.4-mu m band, as well as the observed accompanying mid-IR bands, being carried by kerogen-like dust born in CS (circumstellar) envelopes, mostly of AGB (asymptotic giant branch) objects. Subsequent dust evolution in composition and structure (aromatization) is fast enough that the unidentified infrared bands can already show up in well-developed planetary nebulae (PNe), as observed. A fraction of incompletely evolved dust can escape into the diffuse IS medium and molecular clouds. As a consequence, aliphatic and aromatic features can both be detected in the sky, in emission (Proto-PNe, PNe and PDRs (photo-dissociation regions)) as well as in

Role of NSO compounds during primary cracking of a Type II kerogen and a Type III lignite

USGS Publications Warehouse

Behar, F.; Lorant, F.; Lewan, M.

2008-01-01

The aim of this work is to follow the generation of NSO compounds during the artificial maturation of an immature Type II kerogen and a Type III lignite in order to determine the different sources of the petroleum potential during primary cracking. Experiments were carried out in closed system pyrolysis in the temperature range from 225 to 350 ??C. Two types of NSOs were recovered: one is soluble in n-pentane and the second in dichloromethane. A kinetic scheme was optimised including both kerogen and NSO cracking. It was validated by complementary experiments carried out on isolated asphaltenes generated from the Type II kerogen and on the total n-pentane and DCM extracts generated from the Type III lignite. Results show that kerogen and lignite first decompose into DCM NSOs with minor generation of hydrocarbons. Then, the main source of petroleum potential originates from secondary cracking of both DCM and n-pentane NSOs through successive decomposition reactions. These results confirm the model proposed by Tissot [Tissot, B., 1969. Premie??res donne??es sur les me??canismes et la cine??tique de la formation du pe??trole dans les bassins se??dimentaires. Simulation d'un sche??ma re??actionnel sur ordinateur. Oil and Gas Science and Technology 24, 470-501] in which the main source of hydrocarbons is not the insoluble organic matter, but the NSO fraction. As secondary cracking of the NSOs largely overlaps that of the kerogen, it was demonstrated that bulk kinetics in open system is a result of both kerogen and NSO cracking. Thus, another kinetic scheme for primary cracking in open system was built as a combination of kerogen and NSO cracking. This new kinetic scheme accounts for both the rate and amounts of hydrocarbons generated in a closed pyrolysis system. Thus, the concept of successive steps for hydrocarbon generation is valid for the two types of pyrolysis system and, for the first time, a common kinetic scheme is available for extrapolating results to natural

Carbon and hydrogen isotopic effects of stomatal density in Arabidopsis thaliana

NASA Astrophysics Data System (ADS)

Lee, Hyejung; Feakins, Sarah J.; Sternberg, Leonel da S. L.

2016-04-01

Stomata are key gateways mediating carbon uptake and water loss from plants. Varied stomatal densities in fossil leaves raise the possibility that isotope effects associated with the openness of exchange may have mediated plant wax biomarker isotopic proxies for paleovegetation and paleoclimate in the geological record. Here we use Arabidopsis thaliana, a widely used model organism, to provide the first controlled tests of stomatal density on carbon and hydrogen isotopic compositions of cuticular waxes. Laboratory grown wildtype and mutants with suppressed and overexpressed stomatal densities allow us to directly test the isotope effects of stomatal densities independent of most other environmental or biological variables. Hydrogen isotope (D/H) measurements of both plant waters and plant wax n-alkanes allow us to directly constrain the isotopic effects of leaf water isotopic enrichment via transpiration and biosynthetic fractionations, which together determine the net fractionation between irrigation water and n-alkane hydrogen isotopic composition. We also measure carbon isotopic fractionations of n-alkanes and bulk leaf tissue associated with different stomatal densities. We find offsets of +15‰ for δD and -3‰ for δ13C for the overexpressed mutant compared to the suppressed mutant. Since the range of stomatal densities expressed is comparable to that found in extant plants and the Cenozoic fossil record, the results allow us to consider the magnitude of isotope effects that may be incurred by these plant adaptive responses. This study highlights the potential of genetic mutants to isolate individual isotope effects and add to our fundamental understanding of how genetics and physiology influence plant biochemicals including plant wax biomarkers.

Carbon isotopic evidence for photosynthesis in Early Cambrian oceans

NASA Astrophysics Data System (ADS)

Surge, Donna M.; Savarese, Michael; Dodd, J. Robert; Lohmann, Kyger C.

1997-06-01

Were the first metazoan reefs ecologically similar to modern tropical reefs, enabling them to persist under oligotrophic conditions? We tested the hypothesis of ecological similarity by employing a geochemical approach. Petrography, cathodoluminescence, trace elements, and stable isotope analyses of primary precipitates of the Lower Cambrian Ajax Limestone, South Australia, indicate preservation of original C isotopic composition. All primary carbonate components exhibit C isotopic values similar to the composition of inorganically precipitated fibrous marine cements, suggesting that archaeocyaths and the calcimicrobe Epiphyton precipitated skeletal carbonate in equilibrium with ambient seawater in the absence of vital effects. Such data do not support the contention that archaeocyaths possessed photosymbionts. However, a +0.55‰ shift in δ13C occurs in reefs developed under shallower-water conditions relative to deeper reefs. This shift suggests the stratification of primary production in Early Cambrian oceans. The pattern is similar to that seen in the modern ocean, whereby significant photosynthesis modulates the C isotopic composition of the photic zone.

Organic carbon isotope constraints on the dissolved organic carbon (DOC) reservoir at the Cryogenian-Ediacaran transition

NASA Astrophysics Data System (ADS)

Jiang, Ganqing; Wang, Xinqiang; Shi, Xiaoying; Zhang, Shihong; Xiao, Shuhai; Dong, Jin

2010-10-01

Prominent negative carbonate carbon isotope (δ 13C carb) anomalies from some Ediacaran successions are accompanied by invariant or decoupled organic carbon isotope (δ 13C org) values and have been interpreted as resulting from the remineralization of a large dissolved organic carbon (DOC) reservoir capable of buffering carbon isotopes of organic matter. This inferred oceanic DOC reservoir was thought to have initiated with the onset of Cryogenian glaciations (ca. 720 Ma) and lasted for millions of years until the late Ediacaran Period (< 560 Ma). Carbon isotope analyses of the basal Doushantuo Formation (ca. 635 Ma) in south China reveal that (1) the cap carbonate has δ 13C org around -26‰ (VPDB) and relatively low Δδ 13C (22 ± 2‰) and (2) the overlying organic-rich black shale and shaly dolostone have more negative δ 13C org (-28‰ to -35‰) and higher Δδ 13C (28‰-30‰). Both δ 13C carb and δ 13C org show a + 6‰ shift within a 4-m-thick interval overlying the Doushantuo cap carbonate. The δ 13C org values of the cap carbonate are associated with low TOC (mostly < 0.1%); their paleoceanographic significance requires further tests in other Ediacaran basins. The co-varying positive shift in δ 13C carb and δ 13C org following cap carbonate deposition is best interpreted as resulting from a rapid increase in organic carbon burial, which may have resulted in the rise of oxygen and heralded the first appearance of animals a few meters above the Doushantuo cap carbonate. The data suggest that a large oceanic DOC reservoir did not exist in the early Ediacaran ocean. Excess oceanic DOC required to explain the Ediacaran Shuram and upper Doushantuo δ 13C excursions, if it existed, had to be developed during the Ediacaran Period after cap carbonate deposition.

Effect of Thermal Maturation on n-alkanes and Kerogen in Preserved Organic Matter: Implications for Paleoenvironment Biomarkers

NASA Astrophysics Data System (ADS)

Craven, O. D.; Longbottom, T. L.; Hockaday, W. C.; Blackaby, E.

2017-12-01

Understanding the effects of maturity on biomarkers is vital in assessing biomarker reliability in mature sediments. It is well known for n-alkanes that increased maturity shortens chain lengths and decreases the odd over even preference however, the amount of change in these variables has not been determined for different maturities and types of preserved organic matter. For this reason, it is difficult to judge the trustworthiness of even lightly matured samples for paleoenvironment reconstruction. Another complication is the difficulty of accurately determining maturity as many maturity indicators are error-prone or not appropriate at low maturities. Using hydrous pyrolysis, we artificially matured black shale samples with type I (lacustrine) and type II (marine) kerogen to measure changes in n-alkane length and odd over even preference. Whole rock samples underwent hydrous pyrolysis for 72 hours, at 250 °C, 300 °C, 325 °C, 350 °C, and 375 °C to cover a wide maturity range. From the immature and artificially matured samples, the bitumen was extracted and the saturate fraction was separated using column chromatography. The saturate fraction was analyzed for n-alkanes using gas chromatography-mass spectroscopy. Kerogen structural changes were also measured using solid-state 13C NMR to relate changes in n-alkane biomarkers to changes in kerogen structure. Results show that for type I bitumen the n-alkanes did not change at low maturities considered premature in terms of oil generation (<325 °C). The NMR spectra of the type I kerogen support the lack of change, at low maturities no changes in the aliphatic portion (Fal) were observed, however, after 325 °C Fal decreased with increasing maturity. The loss of Fal indicates kerogen contributing hydrocarbons to bitumen that cause changes in n-alkane measurements. The type II kerogen's Fal also decreased with increasing maturity, but unlike the type I kerogen Fal loss started at low maturities. The differences

Prediction of brittleness based on anisotropic rock physics model for kerogen-rich shale

NASA Astrophysics Data System (ADS)

Qian, Ke-Ran; He, Zhi-Liang; Chen, Ye-Quan; Liu, Xi-Wu; Li, Xiang-Yang

2017-12-01

The construction of a shale rock physics model and the selection of an appropriate brittleness index ( BI) are two significant steps that can influence the accuracy of brittleness prediction. On one hand, the existing models of kerogen-rich shale are controversial, so a reasonable rock physics model needs to be built. On the other hand, several types of equations already exist for predicting the BI whose feasibility needs to be carefully considered. This study constructed a kerogen-rich rock physics model by performing the selfconsistent approximation and the differential effective medium theory to model intercoupled clay and kerogen mixtures. The feasibility of our model was confirmed by comparison with classical models, showing better accuracy. Templates were constructed based on our model to link physical properties and the BI. Different equations for the BI had different sensitivities, making them suitable for different types of formations. Equations based on Young's Modulus were sensitive to variations in lithology, while those using Lame's Coefficients were sensitive to porosity and pore fluids. Physical information must be considered to improve brittleness prediction.

Carbon, Hydrogen, and Oxygen Isotope Ratios of Cellulose from Plants Having Intermediary Photosynthetic Modes 1

PubMed Central

Sternberg, Leonel O'Reilly; Deniro, Michael J.; Ting, Irwin P.

1984-01-01

Carbon and hydrogen isotope ratios of cellulose nitrate and oxygen isotope ratios of cellulose from species of greenhouse plants having different photosynthetic modes were determined. When hydrogen isotope ratios are plotted against carbon isotope ratios, four clusters of points are discernible, each representing different photosynthetic modes: C3 plants, C4 plants, CAM plants, and C3 plants that can shift to CAM or show the phenomenon referred to as CAM-cycling. The combination of oxygen and carbon isotope ratios does not distinguish among the different photosynthetic modes. Analysis of the carbon and hydrogen isotope ratios of cellulose nitrate should prove useful for screening different photosynthetic modes in field specimens that grew near one another. This method will be particularly useful for detection of plants which show CAM-cycling. PMID:16663360

Palaeo-equatorial temperatures and carbon-cycle evolution at the Triassic- Jurassic boundary: A stable isotope perspective from shallow-water carbonates from the UAE

NASA Astrophysics Data System (ADS)

Honig, M. R.; John, C. M.

2013-12-01

The Triassic-Jurassic boundary was marked by global changes including carbon-cycle perturbations and the opening of the Atlantic Ocean. These changes were accompanied by one of the major extinction events of the Phanerozoic. The carbon-cycle perturbations have been recorded in carbon isotope curves from bulk carbonates, organic carbon and fossil wood in several Tethyan locations and have been used for chemostratigraphic purposes. Here we present data from shallow-marine carbonates deposited on a homoclinal Middle Eastern carbonate ramp (United Arab Emirates). Our site was located at the equator throughout the Late Triassic and the Early Jurassic, and this study provides the first constraints of environmental changes at the low-latitudes for the Triassic-Jurassic boundary. Shallow-marine carbonate depositional systems are extremely sensitive to palaeoenvironmental changes and their usefulness for chemostratigraphy is being debated. However, the palaeogeographic location of the studied carbonate ramp gives us a unique insight into a tropical carbonate factory at a time of severe global change. Stable isotope measurements (carbon and oxygen) are being carried out on micrite, ooids and shell material along the Triassic-Jurassic boundary. The stable isotope results on micrite show a prominent negative shift in carbon isotope values of approximately 2 ‰ just below the inferred position of the Triassic-Jurassic boundary. A similar isotopic trend is also observed across the Tethys but with a range of amplitudes (from ~2 ‰ to ~4 ‰). These results seem to indicate that the neritic carbonates from our studied section can be used for chemostratigraphic purposes, and the amplitudes of the carbon isotope shifts provide critical constraints on the magnitude of carbon-cycle perturbations at low latitudes across the Triassic-Jurassic boundary. Seawater temperatures across the Triassic-Jurassic boundary will be constrained using the clumped isotope palaeo-thermometer applied

A Carbonate Li Isotope Record Through Earth's History

NASA Astrophysics Data System (ADS)

Asael, D.; Kalderon-Asael, B.; Planavsky, N.

2016-12-01

Lithium (Li) isotopes emerge as a powerful geochemical proxy for tracking continental weathering through time. Extensive work on Li fractionation in modern systems has brought to a profound understanding of the modern Li budget as well as to a consensus that marine carbonates faithfully record seawater Li isotope signature. As such record is essential in order to track global-scale changes in weathering processes and intensity through Earth's history, we have generated Li isotope data from marine carbonates from over 40 units, ranging in age from 3.0 Ga to modern. Preliminary results provide evidence for strongly inhibited weathering-mediated clay formation prior to the Paleozoic, which we attribute to the pre-Paleozoic lack of land plants. The initial rise in the Li isotope values is observed during the Ordovician, which is followed by a subsequent drop to background values and then begins the generally increasing trend that is already well reported. These findings are open for interpretation but they still support the view that the emergence of land plants dramatically changed the process of weathering and it seems that biomass has a potentially significant role in mineral breakdown in soils. Li isotopes provide a novel perspective on weathering and the impact on the Earth system of the rise of land plants - one of the most significant transitions in Earth's history.

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)

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

1991-01-01

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

The role of fossil organic matter in the ecosystem development of post-mining sites revealed by isotope analyses

NASA Astrophysics Data System (ADS)

Jandova, Katerina; Hyodo, Fujio; Vindušková, Olga; Moradi, Jabbar; Frouz, Jan

2017-04-01

Sediments rich in kerogen ( 19 Ma old, 14C-free) are present in the overburden at post-mining area in Western Bohemia, near Sokolov city, the Czech Republic. There are two successional chronosequences, an alder reclamation and spontaneous succession, consisting of sites that differ in time since heaping. Both chronosequences accumulate recent organic matter over time, although the process is initially faster at reclamation. We hypothesized that (i) radiocarbon age of soil organic matter would be decreasing with time since spoil heaping; (ii) the detrital food web would show the assimilation of fossil carbon by heterotrophic organisms in the initial stages of succession when fossil organic matter is the predominant source of carbon; (iii) the isotopic track of fossil organic matter in the detrital food web would be more prominent at sites with lower vegetation cover and litter production. Nitrogen isotopic ratios of soils were high at the young sites and the decrease in δ15N was correlated with the increase in content of recent organic carbon. Nitrogen isotopic ratios of soil detritivores equalled to that of tree leaves at reclamation but were higher at successional sites. Possibly, other food sources were used apart from tree leaves litter at the latter. Interestingly, soil animals but not primary producers were 14C depleted in the youngest relative to the oldest sites. The depletion in 14C of detritivores relative to primary producers was likely due to the geophagy behaviour of the millipedes at the young sites where fossil organic matter is the largest carbon pool.

Carbon Isotope Chemistry in Molecular Clouds

NASA Technical Reports Server (NTRS)

Robertson, Amy N.; Willacy, Karen

2012-01-01

Few details of carbon isotope chemistry are known, especially the chemical processes that occur in astronomical environments like molecular clouds. Observational evidence shows that the C-12/C-13 abundance ratios vary due to the location of the C-13 atom within the molecular structure. The different abundances are a result of the diverse formation pathways that can occur. Modeling can be used to explore the production pathways of carbon molecules in an effort to understand and explain the chemical evolution of molecular clouds.

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

USGS Publications Warehouse

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

1985-01-01

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.

Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria

USGS Publications Warehouse

Miller, L.G.; Kalin, Robert M.; McCauley, S.E.; Hamilton, John T.G.; Harper, D.B.; Millet, D.B.; Oremland, R.S.; Goldstein, Allen H.

2001-01-01

The largest biological fractionations of stable carbon isotopes observed in nature occur during production of methane by methanogenic archaea. These fractionations result in substantial (as much as ???70???) shifts in ??13C relative to the initial substrate. We now report that a stable carbon isotopic fractionation of comparable magnitude (up to 70???) occurs during oxidation of methyl halides by methylotrophic bacteria. We have demonstrated biological fractionation with whole Cells of three methylotrophs (strain IMB-1, strain CC495, and strain MB2) and, to a lesser extent, with the purified cobalamin-dependent methyltransferase enzyme obtained from strain CC495. Thus, the genetic similarities recently reported between methylotrophs, and methanogens with respect to their pathways for C1-unit metabolism are also reflected in the carbon isotopic fractionations achieved by these organisms. We found that only part of the observed fractionation of carbon isotopes could be accounted for by the activity of the corrinoid methyltransferase enzyme, suggesting fractionation by enzymes further along the degradation pathway. These observations are of potential biogeochemical significance in the application of stable carbon isotope ratios to constrain the tropospheric budgets for the ozone-depleting halocarbons, methyl bromide and methyl chloride.

Precambrian organic geochemistry - Preservation of the record

NASA Technical Reports Server (NTRS)

Hayes, J. M.; Wedeking, K. W.; Kaplan, I. R.

1983-01-01

A review of earlier studies is presented, and new results in Precambrian organic geochemistry are discussed. It is pointed out that two lines of evidence can be developed. One is based on structural organic chemistry, while the other is based on isotopic analyses. In the present investigation, the results of both structural and isotopic investigations of Precambrian organic matter are discussed. Processes and products related to organic geochemistry are examined, taking into account the carbon cycle, an approximate view of the principal pathways of carbon cycling associated with organic matter in the present global ecosystem, processes affecting sedimentary organic matter, and distribution and types of organic matter. Attention is given to chemical fossils in Precambrian sediments, kerogen analyses, the determination of the structural characteristics of kerogen, and data concerning the preservation of the Precambrian organic geochemical record.

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

NASA Technical Reports Server (NTRS)

Socki, Richard; Niles, Paul B.; Sun, Tao; Fu, Qi; Romanek, Christopher S.; Gibson, Everett K.

2013-01-01

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 delta13C(DIC-CARB) values of 20.5%0 which exceed the expected equilibrium fractionation factor of [10(sup 3) ln alpha = 13%0] at 0 degC. Oxygen isotopes showed a smaller enrichment with delta18O(H2O-CARB) values of 35.5%0, slightly exceeding the equilibrium fractionation factor of [10(sup 3) ln alpha = 34%0 ] at 0degC. 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

Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin.

PubMed

Shen, Xiaoli; Xu, Zemin; Zhang, Xichang; Yang, Fangxing

2015-11-01

In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from -29.0‰ to -26.5‰ in soil spiked with 2mg/kg lambda-cyhalothrin, and to -27.5‰ with 10mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as -2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. Copyright © 2015 Elsevier B.V. All rights reserved.

Could a secular increase in organic burial explain the rise of oxygen? Insights from a geological carbon cycle model constrained by the carbon isotope record

NASA Astrophysics Data System (ADS)

Krissansen-Totton, J.; Kipp, M.; Catling, D. C.

2017-12-01

The stable isotopes of carbon in marine sedimentary rock provide a window into the evolution of the Earth system. Conventionally, a relatively constant carbon isotope ratio in marine sedimentary rocks has been interpreted as implying constant organic carbon burial relative to total carbon burial. Because organic carbon burial corresponds to net oxygen production from photosynthesis, it follows that secular changes in the oxygen source flux cannot explain the dramatic rise of oxygen over Earth history. Instead, secular declines in oxygen sink fluxes are often invoked as causes for the rise of oxygen. However, constant fractional organic burial is difficult to reconcile with tentative evidence for low phosphate concentrations in the Archean ocean, which would imply lower marine productivity and—all else being equal—less organic carbon burial than today. The conventional interpretation of the carbon isotope record rests on the untested assumption that the isotopic ratio of carbon inputs into the ocean reflect mantle isotopic values throughout Earth history. In practice, differing rates of carbonate and organic weathering will allow for changes in isotopic inputs, as suggested by [1] and [2]. However, these inputs can not vary freely because large changes in isotopic inputs would induce secular trends in carbon reservoirs, which are not observed in the isotope record. We apply a geological carbon cycle model to all Earth history, tracking carbon isotopes in crustal, mantle, and ocean reservoirs. Our model is constrained by the carbon isotope record such that we can determine the extent to which large changes in organic burial are permitted. We find both constant organic burial and 3-5 fold increases in organic burial since 4.0 Ga can be reconciled with the carbon isotope record. Changes in the oxygen source flux thus need to be reconsidered as a possible contributor to Earth's oxygenation. [1] L. A. Derry, Organic carbon cycling and the lithosphere, in Treatise on

Triple oxygen isotope composition of tropospheric carbon dioxide and terrestrial carbonates

NASA Astrophysics Data System (ADS)

Hofmann, M. E.; Horváth, B.; Pack, A.

2011-12-01

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 Δ17OTFL values relative to the terrestrial fractionation line (TFL) with a slope βTFL=0.5251 and an intercept γTFL=-0.014%. On average, the Δ17OTFL value of ambient CO2 was -0.11±0.05% (SD) with a seasonal cycle of 0.04±0.01%. Lower Δ17O values were observed during wintertime. In order to test the potential of Δ17O as a tracer for anthropogenic CO2, we analyzed CO2 from different combustion processes. Our results showed that the Δ17O 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 Δ17O 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 β for CO2-water equilibrium, we assume that βCO2-water=0.522±0.001 [6]. Furthermore, we took into account that the Δ17OTFL value of CO2 released from soils is affected by kinetic fractionation. Thus, we obtained a Δ17OTFL value for global tropospheric CO2 of -0.13%. The model calculation agrees well with the Δ17OTFL value determined for

Improvement of 2,4-dinitrophenylhydrazine derivatization method for carbon isotope analysis of atmospheric acetone.

PubMed

Wen, Sheng; Yu, Yingxin; Guo, Songjun; Feng, Yanli; Sheng, Guoying; Wang, Xinming; Bi, Xinhui; Fu, Jiamo; Jia, Wanglu

2006-01-01

Through simulation experiments of atmospheric sampling, a method via 2,4-dinitrophenylhydrazine (DNPH) derivatization was developed to measure the carbon isotopic composition of atmospheric acetone. Using acetone and a DNPH reagent of known carbon isotopic compositions, the simulation experiments were performed to show that no carbon isotope fractionation occurred during the processes: the differences between the predicted and measured data of acetone-DNPH derivatives were all less than 0.5 per thousand. The results permitted the calculation of the carbon isotopic compositions of atmospheric acetone using a mass balance equation. In this method, the atmospheric acetone was collected by a DNPH-coated silica cartridge, washed out as acetone-DNPH derivatives, and then analyzed by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using this method, the first available delta13C data of atmospheric acetone are presented. Copyright 2006 John Wiley & Sons, Ltd.

Relationships between tree height and carbon isotope discrimination

Treesearch

Nate G. McDowell; Barbara J. Bond; Lee T. Dickman; Michael G. Ryan; David Whitehead

2011-01-01

Understanding how tree size impacts leaf- and crown-level gas exchange is essential to predicting forest yields and carbon and water budgets. The stable carbon isotope ratio of organic matter has been used to examine the relationship of gas exchange to tree size for a host of species because it carries a temporally integrated signature of foliar photosynthesis and...

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

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

Coordinated In Situ Nanosims Analyses of H-C-O Isotopes in ALH 84001 Carbonates

NASA Technical Reports Server (NTRS)

Usui, T.; Alexander, C. M. O'D.; Wang, J.; Simon, J. I.; Jones, J. H.

2016-01-01

The surface geology and geomorphology of Mars indicate that it was once warm enough to maintain a large body of liquid water on its surface, though such a warm environment might have been transient. This study reports the hydrogen, carbon, and oxygen isotope compositions of the ancient atmosphere/hydrosphere of Mars based on in situ ion microprobe analyses of approximately 4 Ga-old carbonates in Allan Hills (ALH) 84001. The ALH 84001 carbonates are the most promising targets because they are thought to have formed from fluid that was closely associated with the Noachian atmosphere. While there are a number of carbon and oxygen isotope studies of the ALH 84001 carbonates, in situ hydrogen isotope analyses of these carbonates are limited and were reported more than a decade ago. Well-documented coordinated in situ analyses of carbon, oxygen and hydrogen isotopes provide an internally consistent dataset that can be used to constrain the nature of the Noachian atmosphere/hydrosphere and may eventually shed light on the hypothesis of ancient watery Mars.

Grasland Stable Isotope Flux Measurements: Three Isotopomers of Carbon Dioxide Measured by QCL Spectroscopy

NASA Astrophysics Data System (ADS)

Zeeman, M. J.; Tuzson, B.; Eugster, W.; Werner, R. A.; Buchmann, N.; Emmenegger, L.

2007-12-01

To improve our understanding of greenhouse gas dynamics of managed ecosystems such as grasslands, we not only need to investigate the effects of management (e.g., grass cuts) and weather events (e.g., rainy days) on carbon dioxide fluxes, but also need to increase the time resolution of our measurements. Thus, for the first time, we assessed respiration and assimilation fluxes with high time resolution (5Hz) stable isotope measurements at an intensively managed farmland in Switzerland (Chamau, 400m ASL). Two different methods were used to quantify fluxes of carbon dioxide and associated fluxes of stable carbon isotopes: (1) the flux gradient method, and (2) the eddy covariance method. During a week long intensive measurement campaign, we (1) measured mixing ratios of carbon dioxide isotopomers (12C16O2, 12C16O18O, 13C16O2) with a Quantum Cascade Laser (QCL, Aerodyne Inc.) spectroscope and (2) collected air samples for isotope analyses (13C/12C) and (18O/16O) of carbon dioxide by Isotope Ratio Mass Spectrometry (IRMS, Finnigan) every two hours, concurrently along a height profile (z = 0.05; 0.10; 0.31; 2.15m). In the following week, the QCL setup was used for closed-path eddy covariance flux measurement of the carbon dioxide isotopomers, with the air inlet located next to an open-path Infra Red Gas Analyzers (IRGA, LiCor 7500) used simultaneously for carbon dioxide measurements. During this second week, an area of grass inside the footprint was cut and harvested after several days. The first results of in-field continuous QCL measurements of carbon dioxide mixing ratios and their stable isotopic ratios show good agreement with IRGA measurements and isotope analysis of flask samples by IRMS. Thus, QCL spectroscopy is a very promising tool for stable isotope flux investigations.

Sulfur isotopes of organic matter preserved in 3.45-billion-year-old stromatolites reveal microbial metabolism

PubMed Central

Bontognali, Tomaso R. R.; Sessions, Alex L.; Allwood, Abigail C.; Fischer, Woodward W.; Grotzinger, John P.; Summons, Roger E.; Eiler, John M.

2012-01-01

The 3.45-billion-year-old Strelley Pool Formation of Western Australia preserves stromatolites that are considered among the oldest evidence for life on Earth. In places of exceptional preservation, these stromatolites contain laminae rich in organic carbon, interpreted as the fossil remains of ancient microbial mats. To better understand the biogeochemistry of these rocks, we performed microscale in situ sulfur isotope measurements of the preserved organic sulfur, including both Δ33S and . This approach allows us to tie physiological inference from isotope ratios directly to fossil biomass, providing a means to understand sulfur metabolism that is complimentary to, and independent from, inorganic proxies (e.g., pyrite). Δ33S values of the kerogen reveal mass-anomalous fractionations expected of the Archean sulfur cycle, whereas values show large fractionations at very small spatial scales, including values below -15‰. We interpret these isotopic patterns as recording the process of sulfurization of organic matter by H2S in heterogeneous mat pore-waters influenced by respiratory S metabolism. Positive Δ33S anomalies suggest that disproportionation of elemental sulfur would have been a prominent microbial process in these communities. PMID:22949693

Abundances in red giant stars - Carbon and oxygen isotopes in carbon-rich molecular envelopes

NASA Technical Reports Server (NTRS)

Wannier, P. G.; Sahai, R.

1987-01-01

Millimeter-wave observations have been made of isotopically substituted CO toward the envelopes of 11 carbon-rich stars. In every case, C-13O was detected and model calculations were used to estimate the C-12/C-13 abundance ratio. C-17O was detected toward three, and possibly four, envelopes, with sensitive upper limits for two others. The CO-18 variant was detected in two envelopes. New results include determinations of oxygen isotopic ratios in the two carbon-rich protoplanetary nebulae CRL 26688 and CRL 618. As with other classes of red giant stars, the carbon-rich giants seem to be significantly, though variably, enriched in O-17. These results, in combination with observations in interstellar molecular clouds, indicate that current knowledge of stellar production of the CNO nuclides is far from satisfactory.

Coprecipitation and isotopic fractionation of boron in modern biogenic carbonates

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

Vengosh, A.; Chivas, A.R.; McCulloch, M.T.

1991-10-01

The abundances and isotopic composition of boron in modern, biogenic calcareous skeletons from the Gulf of Elat, Israel, the Great Barrier Reef, Australia, and in deep-sea sediments have been examined by negative thermal-ionization mass spectrometry. The selected species (Foraminifera, Pteropoda, corals, Gastropoda, and Pelecypoda) yield large variations in boron concentration that range from 1 ppm in gastropod shells to 80 ppm in corals. The 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 themore » 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.« less

Sediment Tracking Using Carbon and Nitrogen Stable Isotopes

NASA Astrophysics Data System (ADS)

Fox, J. F.; Papanicolaou, A.

2002-12-01

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

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

DOE PAGES

Jahn, A.; Lindsay, K.; Giraud, X.; ...

2015-08-05

Carbon isotopes in the ocean are frequently used as paleoclimate 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 data set, 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, themore » 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 fewer 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. Lastly, at the same time, the carbon isotopes reveal biases in the physical model, for example, too sluggish ventilation of the deep Pacific Ocean.« less

Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water

NASA Astrophysics Data System (ADS)

Jones, Sam; Sauze, Joana; Ogée, Jérôme; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

2016-04-01

Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the

Boron isotope fractionation in magma via crustal carbonate dissolution

NASA Astrophysics Data System (ADS)

Deegan, Frances M.; Troll, Valentin R.; Whitehouse, Martin J.; Jolis, Ester M.; Freda, Carmela

2016-08-01

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to -41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

Boron isotope fractionation in magma via crustal carbonate dissolution.

PubMed

Deegan, Frances M; Troll, Valentin R; Whitehouse, Martin J; Jolis, Ester M; Freda, Carmela

2016-08-04

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ(11)B values down to -41.5‰, reflecting preferential partitioning of (10)B into the assimilating melt. Loss of (11)B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports (11)B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ(11)B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

Calibration strategies for the determination of stable carbon absolute isotope ratios in a glycine candidate reference material by elemental analyser-isotope ratio mass spectrometry.

PubMed

Dunn, Philip J H; Malinovsky, Dmitry; Goenaga-Infante, Heidi

2015-04-01

We report a methodology for the determination of the stable carbon absolute isotope ratio of a glycine candidate reference material with natural carbon isotopic composition using EA-IRMS. For the first time, stable carbon absolute isotope ratios have been reported using continuous flow rather than dual inlet isotope ratio mass spectrometry. Also for the first time, a calibration strategy based on the use of synthetic mixtures gravimetrically prepared from well characterised, highly (13)C-enriched and (13)C-depleted glycines was developed for EA-IRMS calibration and generation of absolute carbon isotope ratio values traceable to the SI through calibration standards of known purity. A second calibration strategy based on converting the more typically determined delta values on the Vienna PeeDee Belemnite (VPDB) scale using literature values for the absolute carbon isotope ratio of VPDB itself was used for comparison. Both calibration approaches provided results consistent with those previously reported for the same natural glycine using MC-ICP-MS; absolute carbon ratios of 10,649 × 10(-6) with an expanded uncertainty (k = 2) of 24 × 10(-6) and 10,646 × 10(-6) with an expanded uncertainty (k = 2) of 88 × 10(-6) were obtained, respectively. The absolute carbon isotope ratio of the VPDB standard was found to be 11,115 × 10(-6) with an expanded uncertainty (k = 2) of 27 × 10(-6), which is in excellent agreement with previously published values.

Preliminary Study: Application of Off-Axis ICOS to Determine Stable Carbon Isotope in Dissolved Inorganic Carbon

NASA Astrophysics Data System (ADS)

Kim, Y. T.; Lee, J. M.; Hwang, J. H.; Piao, J.; Woo, N. C.

2015-12-01

CO2 is one of the major causes for global climate change. Because stable carbon isotope ratio is used to trace carbon source, several analytical techniques likes IRMS (Isotope Ratio Mass Spectrometry) and LAS (Laser Absorption Spectrometry) were extensively used. Off-axis ICOS, a kind of LAS, has merits on long-term stability and field application, therefore it is widely being used in CCS (Carbon Capture and Storage) field. The aim of this study is to extend the application scope of OA-ICOS to determine dissolved inorganic carbon (DIC). Because OA-ICOS showed dependence of δ13C on CO2 concentration, data processing is required. We tested CO2 Carbon Isotope Analyzer (CCIA-36-EP, Los Gatos Research) with both reference gas (δ13C= -28.28‰) and aqueous solutions prepared by dissolving sodium bicarbonate standards (δ13C= -12.26‰ and +3.96‰). The differences of δ13C between reference and measurement values are plotted by CO2 concentrations, then compared. At first, we checked the similarity between our curve pattern for reference gas and Guillon's research (δ13C= -43.99‰) by other Analyzer. To analyze aqueous samples, more errors can be caused than gas analysis. The carbon isotope fractionation occurs during dissolving standard reagents and extracting DIC as CO2 gas form. This effect is mixed with CO2 concentration dependence effect, therefore the curve patterns are different with that for reference gas. Our experiments are done for various δ13C values. It could be an important point to use OA-ICOS to analyze DIC, too.

Fractionation of carbon isotopes by phytoplankton and estimates of ancient CO2 levels

NASA Technical Reports Server (NTRS)

Freeman, K. H.; Hayes, J. M.

1992-01-01

Reports of the 13C content of marine particulate organic carbon are compiled and on the basis of GEOSECS data and temperatures, concentrations, and isotopic compositions of dissolved CO2 in the waters in which the related phytoplankton grew are estimated. In this way, the fractionation of carbon isotopes during photosynthetic fixation of CO2 is found to be significantly correlated with concentrations of dissolved CO2. Because ancient carbon isotopic fractionations have been determined from analyses of sedimentary porphyrins [Popp et al., 1989], the relationship between isotopic fractionation and concentrations of dissolved CO2 developed here can be employed to estimate concentrations of CO2 dissolved in ancient oceans and, in turn, partial pressures of CO2 in ancient atmospheres. The calculations take into account the temperature dependence of chemical and isotopic equilibria in the dissolved-inorganic-carbon system and of air-sea equilibria. Paleoenvironmental temperatures for each sample are estimated from reconstructions of paleogeography, latitudinal temperature gradients, and secular changes in low-latitude sea surface temperature. It is estimated that atmospheric partial pressures of CO2 were over 1000 micro atm 160 - 100 Ma ago, then declined to values near 300 micro atm during the next 100 Ma. Analysis of a high-resolution record of carbon isotopic fractionation at the Cenomanian-Turonian boundary suggests that the partial pressure of CO2 in the atmosphere was drawn down from values near 840 micro atm to values near 700 micro atm during the anoxic event.

Nature of POC transport in a mangrove ecosystem: A carbon stable isotopic study

NASA Astrophysics Data System (ADS)

Rezende, C. E.; Lacerda, L. D.; Ovall, A. R. C.; Silva, C. A. R.; Martinelli, L. A.

1990-06-01

The isotopic composition of particulate organic carbon (POC) was studied during five tidal cycles in a mangrove creek of Sepetiba Bay, Rio de Janeiro, Brazil. The results show that a mixture of organic carbon from mangrove and marine origins is always present in the creek. Mean mangrove contribution to the POC varied from 16% to 100% and was dependent on tidal amplitude. The results suggest that oceanic carbon can be an important component of carbon balance in mangrove ecosystems. Therefore, earlier carbon balance studies from mangroves which did not include measurements of carbon isotopic composition should be interpreted with care.

Climatic forcing of carbon-oxygen isotopic covariance in temperate-region marl lakes

NASA Technical Reports Server (NTRS)

Drummond, C. N.; Patterson, W. P.; Walker, J. C.

1995-01-01

Carbon and oxygen stable isotopic compositions of lacustrine carbonate from a southeastern Michigan marl lake display linear covariance over a range of 4.0% Peedee belemnite (PDB) in oxygen and 3.9% (PDB) in carbon. Mechanisms of delta 13 C-delta 18 O coupling conventionally attributed to lake closure in arid-region basins are inapplicable to hydrologically open lake systems. Thus, an alternative explanation of isotopic covariance in temperate region dimictic marl lakes is required. We propose that isotopic covariance is a direct record of change in regional climate. In short-residence-time temperate-region lake basins, summer meteoric precipitation is enriched in 18O relative to winter values, and summer organic productivity enriches epilimnic dissolved inorganic carbon in 13C. Thus, climate change toward longer summers and/or shorter winters could result in greater proportions of warm-month meteoric precipitation, longer durations of warm-month productivity, and net long-term enrichment in carbonate 18O and 13C. Isotopic covariance observed in the Michigan marl lake cores is interpreted to reflect postglacial warming from 10 to 3 ka followed by cooler mean annual temperature, a shift toward greater proportions of seasonal summer precipitation, a shortening of the winter season, or some combination of these three factors.

Early Triassic fluctuations of the global carbon cycle: New evidence from paired carbon isotopes in the western USA basin

NASA Astrophysics Data System (ADS)

Caravaca, Gwénaël; Thomazo, Christophe; Vennin, Emmanuelle; Olivier, Nicolas; Cocquerez, Théophile; Escarguel, Gilles; Fara, Emmanuel; Jenks, James F.; Bylund, Kevin G.; Stephen, Daniel A.; Brayard, Arnaud

2017-07-01

In the aftermath of the catastrophic end-Permian mass extinction, the Early Triassic records recurrent perturbations in the carbon isotope signal, most notably during the Smithian and through the Smithian/Spathian Boundary (SSB; 1.5 myr after the Permian/Triassic boundary), which show some of the largest excursions of the Phanerozoic. The late Smithian also corresponds to major biotic turnovers and environmental changes, such as temperature fluctuations, that deeply impacted the recovery after the end-Permian mass extinction. Here we document the paired carbon isotope signal along with an analysis of the trace and major elements at the long-known Hot Springs section (southeastern Idaho, USA). This section records Early Triassic sediments from the Griesbachian-Dienerian up to the lower Spathian. We show that the organic and carbonate δ13C variations mirror the signals identified at a global scale. Particularly, the middle Smithian-SSB event represented by a negative-positive isotopic couplet is well identified and is not of diagenetic origin. We also document a positive excursion potentially corresponding to the Dienerian/Smithian Boundary. Observed Smithian-Spathian excursions are recorded similarly in both the organic and carbonate reservoirs, but the organic matter signal systematically shows unexpectedly dampened variations compared to its carbonate counterpart. Additionally, we show that variations in the net isotopic effect (i.e., Δ13C) probably resulted from a complex set of forcing parameters including either a mixing between terrestrial and marine organic matter depending on the evolution of the depositional setting, or variations in the biological fractionation. We establish that the Δ13C signal cannot be directly related to CO2-driven temperature variations at Hot Springs. Even though the carbon isotope signal mirrors the Early Triassic variations known at the global scale, the Hot Springs signal probably also reflects local influences on the carbon

Stable carbon isotope analyses of nanogram quantities of particulate organic carbon (pollen) with laser ablation nano combustion gas chromatography/isotope ratio mass spectrometry

PubMed Central

Sluijs, Appy; Laks, Jelmer J.; Reichart, Gert‐Jan

2016-01-01

Rationale Analyses of stable carbon isotope ratios (δ 13C values) of organic and inorganic matter remains have been instrumental for much of our understanding of present and past environmental and biological processes. Until recently, the analytical window of such analyses has been limited to samples containing at least several μg of carbon. Methods Here we present a setup combining laser ablation, nano combustion gas chromatography and isotope ratio mass spectrometry (LA/nC/GC/IRMS). A deep UV (193 nm) laser is used for optimal fragmentation of organic matter with minimum fractionation effects and an exceptionally small ablation chamber and combustion oven are used to reduce the minimum sample mass requirement compared with previous studies. Results Analyses of the international IAEA CH‐7 polyethylene standard show optimal accuracy, and precision better than 0.5‰, when measuring at least 42 ng C. Application to untreated modern Eucalyptus globulus (C3 plant) and Zea mays (C4 plant) pollen grains shows a ~ 16‰ offset between these species. Within each single Z. mays pollen grain, replicate analyses show almost identical δ 13C values. Conclusions Isotopic offsets between individual pollen grains exceed analytical uncertainties, therefore probably reflecting interspecimen variability of ~0.5–0.9‰. These promising results set the stage for investigating both δ 13C values and natural carbon isotopic variability between single specimens of a single population of all kinds of organic particles yielding tens of nanograms of carbon. © 2016 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd. PMID:27766694

Basal area growth, carbon isotope discrimination, and intrinsic ...

EPA Pesticide Factsheets

Many hectares of intensively managed Douglas-fir (Pseudotsuga menziesii Mirb. Franco) stands in western North America are fertilized with nitrogen to increase growth rates. Understanding the mechanisms of response facilitates prioritization of stands for treatment. The objective of this study was to test the hypothesis that the short-term basal area growth response to a single application of 224 kg N ha-1 as urea was associated with reduced stable carbon isotope discrimination (∆13C) and increased intrinsic water use efficiency (iWUE) in a 20-yr-old plantation of Douglas-fir in the Oregon Coast Range, USA. Increment cores were measured to estimate earlywood, latewood, and total basal area increment over a time series from 1997 to 2015. Stable carbon isotope discrimination and iWUE were estimated using earlywood and latewood stable carbon isotope concentrations in tree-ring holocellulose starting seven years before fertilization in early 2009 and ending seven years after treatment. A highly significant interaction effect between fertilization treatment and year was found for total basal area growth and earlywood basal area increment. Fertilized trees showed significant total basal area growth and earlywood basal area increment in the first (2009) and second (2010) growing seasons after fertilization in 2009. A marginally significant fertilization effect was found for latewood basal area increment only in the first growing season after treatment. A significant i

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

PubMed

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

2017-03-01

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

Carbon kinetic isotope effect in the reaction of CH4 with HO

NASA Technical Reports Server (NTRS)

Davidson, J. A.; Cantrell, C. A.; Tyler, S. C.; Shetter, R. E.; Cicerone, R. J.

1987-01-01

The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

Single Species Dinoflagellate Cyst Carbon Isotope Ecology across the Paleocene-Eocene Thermal Maximum

NASA Astrophysics Data System (ADS)

Sluijs, A.; Roij, L. V.; Frieling, J.; Laks, J.; Reichart, G. J.

2017-12-01

We present the first ever species-specific records of fossil dinoflagellate cyst stable carbon isotope ratios (δ13C). These records across a Paleocene-Eocene Thermal Maximum section in New Jersey were established using a novel coupled laser ablation - isotope ratio mass spectrometer setup. The overall good correspondence with carbonate δ13C records across the characteristic PETM carbon isotope excursion indicates that the δ13C of dissolved inorganic carbon exerts a major control on dinocysts δ13C. Pronounced and consistent differences between species, however, reflect the differential physiological response to changing seawater carbonate chemistry following PETM carbon injection. Moreover, they reflect different habitats or life cycle processes, notably related to bloom intensity. Intriguingly, decreased inter-specimen variability during the PETM in a species that also drops in abundance suggests a more limited niche, either in time (seasonal) or space. This opens a new approach for ecological and evolutionary reconstructions based on organic microfossils.

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

DOE PAGES

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

2016-07-22

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

Stable carbon isotopes: possible clues to early life on Mars.

PubMed

Schidlowski, M

1992-01-01

Organic and inorganic carbon in terrestrial near-surface environments are characterized by a marked difference in their 13C/12C ratios which can be traced back in the Earth's sedimentary record over almost 4 billion years. There is no doubt that the bias in favour of 12C displayed by biogenic matter derives, for the most part, from the isotope-selecting properties of the carbon-fixing enzyme (ribulose-1,5-bisphosphate carboxylase) that is operative in the principal photosynthetic pathway and promotes most of the carbon transfer from the non-living to the living realm. Postulating a universality of biological principles in analogy to the proven universality of the laws of physics and chemistry, we may expect enzymatic reactions in exobiological systems to be beset with B similar kinetic fractionation effects. Hence, the retrieval from the oldest Martian sediments of isotopic fractionations between reduced and oxidized (carbonate) carbon may substantially constrain current conjectures on the possible existence of former life on Mars.

Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars.

PubMed

Shaheen, R; Abramian, A; Horn, J; Dominguez, G; Sullivan, R; Thiemens, Mark H

2010-11-23

The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess (17)O (0.4-3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O(3) reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth.

Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars

PubMed Central

Shaheen, R.; Abramian, A.; Horn, J.; Dominguez, G.; Sullivan, R.; Thiemens, Mark H.

2010-01-01

The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess 17O (0.4–3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O3 reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth. PMID:21059939

Coprecipitation and isotopic fractionation of boron in modern biogenic carbonates

NASA Astrophysics Data System (ADS)

Vengosh, Avner; Kolodny, Yehoshua; Starinsky, Abraham; Chivas, Allan R.; McCulloch, Malcolm T.

1991-10-01

The abundances and isotopic composition of boron in modern, biogenic calcareous skeletons from the Gulf of Elat, Israel, the Great Barrier Reef, Australia, and in deep-sea sediments have been examined by negative thermal-ionization mass spectrometry. The selected species (Foraminifera, Pteropoda, corals, Gastropoda, and Pelecypoda) yield large variations in boron concentration that range from 1 ppm in gastropod shells to 80 ppm in corals. The boron content of the biogenic skeletons is independent of mineralogical composition and is probably related to biological (vital) effects. The δ11B values of the carbonates range from 14.2 to 32.2%. (relative to NBS SRM 951) and overlap with the δ11B values of modern deep-sea carbonate sediments ( δ11B = 8.9 to 26.2%.). The variations of δ11B may be controlled by isotopic exchange of boron species in which 10B is preferentially partitioned into the tetrahedral species, and coprecipitation of different proportions of trigonal and tetrahedral species in the calcium carbonates. Carbonates with low δ11B values (~ 15%.) may indicate preferential incorporation of tetrahedral species, whereas the higher δ11B values (~30%.) may indicate (1) uptake of both boron species assuming equilibrium with seawater (2) preferential incorporation of B(OH) 4- from in situ high-pH internal fluids of organisms that are isolated from seawater. The B content and δ11B values of deep-sea sediments, Foraminifera tests, and corals are used to estimate the global oceanic sink of elemental boron by calcium carbonate deposition. As a result of enrichment of B in corals, a substantially higher biogenic sink of 6.4 ± 0.9 × 10 10 g/yr is calculated for carbonates. This is only slightly lower than the sink for desorbable B in marine sediments (10 × 10 10 g/yr) and approximately half that of altered oceanic crust (14 × 10 10 g/yr). Thus, carbonates are an important sink for B in the oceans being ~20% of the total sinks. The preferential incorporation of

Paleovegetation changes recorded by n-alkyl lipids bound in macromolecules of plant fossils and kerogens from the Cretaceous sediments in Japan

NASA Astrophysics Data System (ADS)

Miyata, Y.; Sawada, K.; Nakamura, H.; Takashima, R.; Takahashi, M.

2014-12-01

Resistant macromolecules composing living plant tissues tend to be preserved through degradation and diagenesis, hence constituate major parts of sedimentary plant-derived organic matter (kerogen), and their monomer compositions vary widely among different plant taxa, organs and growth stages. Thus, analysis of such macromolecule may serve as new technique for paleobotanical evaluation distinctive from classical paleobotnical studies depends on morphological preservation of fossils. In the present study, we analyzed plant fossils and kerogens in sediments from the Cretaceous strata in Japan to examine chemotaxonomic characteristics of fossil macromolecules and to reconstruct paleovegetation change by kerogen analysis. The kerogens were separated from the powdered sediments of Cretaceous Yezo Group, Hokkaido, Japan. All kerogens have been confirmed to be mostly originated from land plant tissues by microscopic observation. Mummified angiosperm and gymnosperm fossil leaves were separated from carbonaceous sandstone of the Cretaceous Ashizawa Formation, Futaba Group. The kerogens and plant fossils were extracted with methanol and dichloromethane, and were subsequently refluxed under 110°C to remove free compounds completely. The residues are hydrolyzed by KOH/methanol under 110°C. These released compounds are analyzed by GC-MS. As main hydrolyzed products (ester-bound molecular units) from all kerogens, C10-C28 n-alkanoic acids and C10-C30 n-alkanols were detected. Recent studies on the hydrolysis products of plant tissues suggested the long chain (>C20) n-alkanols were predominantly abundant in deciduous broadleaved angiosperms. Correspondingly, the stratigraphic variation of the ratios of long chain (>C20) n-alkanols to fatty acids was concordant with the variation of angiosperm/gymnosperm ratios recorded by land plant-derived terpenoid biomarkers. In addition, we found that the long chain n-alkanols/fatty acids ratio in the angiosperm fossil leaf was

Carbon and nitrogen isotope systematics in diamond: Different sensitivities to isotopic fractionation or a decoupled origin?

NASA Astrophysics Data System (ADS)

Hogberg, K.; Stachel, T.; Stern, R. A.

2016-11-01

Using stable isotope data obtained on multiple aliquots of diamonds from worldwide sources, it has been argued that carbon and nitrogen in diamond are decoupled. Here we re-investigate the carbon-nitrogen relationship based on the most comprehensive microbeam data set to date of stable isotopes and nitrogen concentrations in diamonds (n = 94) from a single locality. Our diamond samples, derived from two kimberlites in the Chidliak Field (NE Canada), show large variability in δ13C (- 28.4 ‰ to - 1.1‰, mode at - 5.8‰), δ15N (- 5.8 to + 18.8‰, mode at - 3.0‰) and nitrogen contents ([N]; 3800 to less than 1 at.ppm). In combination, cathodoluminescence imaging and microbeam analyses reveal that the diamonds grew from multiple fluid pulses, with at least one major hiatus documented in some samples that was associated with a resorption event and an abrupt change from low δ13C and [N] to mantle-like δ13C and high [N]. Overall, δ13C appears to be uncorrelated to δ15N and [N] on both the inter- and intra-diamond levels. Co-variations of δ15N-log[N], however, result in at least two parallel, negatively correlated linear arrays, which are also present on the level of the individual diamonds falling on these two trends. These arrays emerge from the two principal data clusters, are characterized by slightly negative and slightly positive δ15N (about - 3 and + 2‰, respectively) and variable but overall high [N]. Using published values for the diamond-fluid nitrogen isotope fractionation factor and nitrogen partition coefficient, these trends are perfectly reproduced by a Rayleigh fractionation model. Overall, three key elements are identified in the formation of the diamond suite studied: (1.) a low δ13C and low [N] component that possibly is directly associated with an eclogitic diamond substrate or introduced during an early stage fluid event. (2.) Repeated influx of a variably nitrogen-rich mantle fluid (mildly negative δ13C and δ15N). (3.) In waning

Kinetic Fractionation of Stable Isotopes in Carbonates on Mars: Terrestrial Analogs

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Gibson, Everett K., Jr.; Golden, D. C.; Ming, Douglas W.; McKay, Gordon A.

2003-01-01

An ancient Martian hydrosphere consisting of an alkali-rich ocean would likely produce solid carbonate minerals through the processes of evaporation and/or freezing. We postulate that both (or either) of these kinetically-driven processes would produce carbonate minerals whose stable isotopic compositions are highly fractionated (enriched) with respect to the source carbon. Various scenarios have been proposed for carbonate formation on Mars, including high temperature formation, hydrothermal alteration, precipitation from evaporating brines, and cryogenic formation. 13C and 18O -fractionated carbonates have previously been shown to form kinetically under some of these conditions, ie.: 1) alteration by hydrothermal processes, 2) low temperature precipitation (sedimentary) from evaporating bicarbonate (brine) solutions, and 3) precipitation during the process of cryogenic freezing of bicarbonate-rich fluids. Here we examine several terrestrial field settings within the context of kinetically controlled carbonate precipitation where stable isotope enrichments have been observed.

Biodegradation of Chlorofluorocarbons in a Groundwater Plume using Compound Specific Carbon Isotope Analysis

NASA Astrophysics Data System (ADS)

Phillips, E.; Manna, J.; Horst, A.; Gilevska, T.; Sherwood Lollar, B.; Mack, E. E.; Seger, E.; Lutz, E. J.; Norcoss, S.; Morgan, S. E.; West, K. A.; Dworatzek, S.; Webb, J.

2017-12-01

Compound specific isotope analysis (CSIA) measures isotope ratios of organic hydrocarbons to monitor intrinsic bioremediation processes that can transform contaminants in field settings. The fraction of original contaminant remaining can be determined using the measured isotope ratio of the contaminant by an experimentally determined fractionation factor. In this study, two separate biotransformation experiments were performed in the Stable Isotope Laboratory at the University of Toronto using CSIA. In these two experiments, a mixed culture derived from a contaminated site was amended with trichlorotrifluoroethane (CFC-113), or trichlorofluoromethane (CFC-11), respectively. The concentrations and carbon isotope ratios of CFC-113, or CFC-11 were analyzed to calculate the fractionation factor for the transformation of each compound. Subsequently, groundwater samples from 9 wells at a historically contaminated site were collected and analyzed. The experimentally determined fractionation factors were then used to evaluate the extent of transformation that had occurred at the field site. In the laboratory studies, significant carbon isotope fractionation was observed for both CFC-113 and CFC-11 as biotransformation proceeded. This significant fractionation is beneficial when evaluating biotransformation at field sites as it can be clearly differentiated from the effects of other physical processes such as transport, or volatilization. Although there was significant variation in the carbon isotope values of CFC-113 between different well locations at the field site, these variations may be due to differences in source carbon isotope signatures. For CFC-11, much more significant isotopic variation was observed within the same well and between wells, showing trends consistent with in situ biotransformation. Results from this study demonstrate that CSIA can be successfully applied to evaluate the extent of transformation of chlorofluorocarbons (CFCs) at contaminated field

Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia

NASA Astrophysics Data System (ADS)

Brookman, Tom H.; Ambrose, Stanley H.

2012-09-01

Serial sampling of tooth enamel growth increments for carbon and oxygen isotopic analyses of Macropus (kangaroo) teeth was performed to assess the potential for reconstructing paleoseasonality. The carbon isotope composition of tooth enamel apatite carbonate reflects the proportional intake of C3 and C4 vegetation. The oxygen isotopic composition of enamel reflects that of ingested and metabolic water. Tooth enamel forms sequentially from the tip of the crown to the base, so dietary and environmental changes during the tooth's formation can be detected. δ13C and δ18O values were determined for a series of enamel samples drilled from the 3rd and 4th molars of kangaroos that were collected along a 900 km north-south transect in southern Australia. The serial sampling method did not yield pronounced seasonal isotopic variation patterns in Macropus enamel. The full extent of dietary isotopic variation may be obscured by attenuation of the isotopic signal during enamel mineralisation. Brachydont (low-crowned) Macropus teeth may be less sensitive to seasonal variation in isotopic composition due to time-averaging during mineralisation. However, geographic variations observed suggest that there may be potential for tracking latitudinal shifts in vegetation zones and seasonal environmental patterns in response to climate change.

Boron isotope fractionation in magma via crustal carbonate dissolution

PubMed Central

Deegan, Frances M.; Troll, Valentin R.; Whitehouse, Martin J.; Jolis, Ester M.; Freda, Carmela

2016-01-01

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to −41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle. PMID:27488228

In situ analysis of carbon isotopes in North American diamonds

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

Precise and traceable carbon isotope ratio measurements by multicollector ICP-MS: what next?

PubMed

Santamaria-Fernandez, Rebeca

2010-06-01

This article reviews recent developments in the use of multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) to provide high-precision carbon isotope ratio measurements. MC-ICP-MS could become an alternative method to isotope ratio mass spectrometry (IRMS) for rapid carbon isotope ratio determinations in organic compounds and characterisation and certification of isotopic reference materials. In this overview, the advantages, drawbacks and potential of the method for future applications are critically discussed. Furthermore, suggestions for future improvements in terms of precision and sensitivity are made. No doubt, this is an exciting analytical challenge and, as such, hurdles will need to be cleared.

Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment.

PubMed

Marchesi, Massimo; Thomson, Neil R; Aravena, Ramon; Sra, Kanwartej S; Otero, Neus; Soler, Albert

2013-09-15

The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S₂O₈(2-)) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ∼12. An increase in the NaOH:S₂O₈(2-) molar ratio from 0.2:1 to 8:1 enhanced the reaction rate of 1,1,1-TCA by a factor of ∼5 to yield complete (>99.9%) destruction. An average carbon isotope enrichment fractionation factor which was independent of the NaOH:S₂O₈(2-) molar ratio of -7.0 ± 0.2‰ was obtained. This significant carbon isotope fractionation and the lack of dependence on changes in the NaOH:S₂O₈(2-) molar ratio demonstrates that carbon isotope analysis can potentially be used in situ as a performance assessment tool to estimate the degradation effectiveness of 1,1,1-TCA by a base-catalyzed persulfate system. Copyright © 2013 Elsevier B.V. All rights reserved.

Carbon isotope fractionation between Fe-carbide and diamond; a light C isotope reservoir in the deep Earth and Core?

NASA Astrophysics Data System (ADS)

Mikhail, S.; Jones, A. P.; Hunt, S. A.; Guillermier, C.; Dobson, D. P.; Tomlinson, E.; Dan, H.; Milledge, H.; Franchi, I.; Wood, I.; Beard, A.; Verchovsky, S.

2010-12-01

The largest accessible reservoir for terrestrial carbon is the mantle; however the core may yield even more. Carbon is commonly proposed as the light element (or one of) to make up the observed density deficit in the earth’s metallic core (NAKAJIMA et al., 2009). The potential isotopic effects of carbon incorporation into the core have not yet been investigated. In-situ ion probe (nanoSIMS) mapping and imaging of carbon isotope variations across rare sub-mm-scale Fe-rich carbide inclusions in mantle diamond (from Jagersfontein, South Africa) show the carbide to be significantly depleted in 13C relative to their diamond host. Distinctive textures suggest metallic liquid precipitates similar in geometry to (giant) nitrogen platelets, controlled by the octahedral symmetry of diamond, which we interpret as syngenic formation. The difference in δ13C values between the two natural phases for diamond-Fe carbide, gives an isotopic fractionation factor (ΔC) which agrees well with HPHT multi-anvil experiments (5-9 GPa and >1400°C). Our measured ΔC between Fe-carbide and diamond may only have local significance, but the measured isotopic values represent characterization of the highest PT carbide known (i.e. > minimum depth of the diamond stability field ≈ 150 km). The direction and magnitude of ΔC agrees with observations of the ΔC between cohenite-graphite in iron meteorites (DEINES and WICKMAN, 1975) and both agree with HPHT experiments, thus suggesting that carbon in the deep Earth, and particularly in the core, may be similarly fractionated (i.e. depleted in the 13C). Since metallic liquid drained from the silicate mantle to form the core during the early Earth, we can use our values as a proxy to constrain evolution of deep carbon reservoirs such as the core and bulk silicate Earth. For example, we can test the suggestion of Grady et al (2004) that the upper mantle value of δ13C ≈ -5 ‰ may not be representative of the bulk Earth, since solar system

Chemical and carbon isotopic composition of dissolved organic carbon in a regional confined methanogenic aquifer

USGS Publications Warehouse

Aravena, R.; Wassenaar, L.I.; Spiker, E. C.

2004-01-01

This study demonstrates the advantage of a combined use of chemical and isotopic tools to understand the dissolved organic carbon (DOC) cycle in a regional confined methanogenic aquifer. DOC concentration and carbon isotopic data demonstrate that the soil zone is a primary carbon source of groundwater DOC in areas close to recharge zones. An in-situ DOC source linked to organic rich sediments present in the aquifer matrix is controlling the DOC pool in the central part of the groundwater flow system. DOC fractions, 13C-NMR on fulvic acids and 14C data on DOC and CH4 support the hypothesis that the in-situ DOC source is a terrestrial organic matter and discard the Ordovician bedrock as a source of DOC. ?? 2004 Taylor and Francis Ltd.

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

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

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

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

Surface ocean carbon isotope anomalies on glacial terminations: An alternative view

NASA Astrophysics Data System (ADS)

Lund, D. C.; Cote, M.; Schmittner, A.

2016-12-01

Late Pleistocene glacial terminations are characterized by surface ocean carbon isotope minima on a global scale. During the last deglaciation (i.e. Termination 1), planktonic foraminiferal δ13C anomalies occurred in the Atlantic, Indian, Pacific, and Southern Oceans. Despite the apparently ubiquitous nature of δ13C anomalies on glacial terminations, their cause remains a matter of ongoing debate. The prevailing view is that isotopically light carbon from the abyss was upwelled in the Southern Ocean, resulting in outgassing of 13C-depleted carbon to the atmosphere and its advection to lower latitudes via mode and intermediate waters (Spero and Lea, 2002). Alternatively, carbon isotope minima may be driven by weakening of the biological pump related to circulation-driven changes in the oceanic preformed nutrient budget (Schmittner and Lund, 2015). Here we assess the deep upwelling and biological pump hypotheses using a new compilation of 70 globally-distributed planktonic δ13C records from the published literature. We find that 1) the mean deglacial δ13C anomaly is similar in all ocean basins, 2) the eastern tropical Pacific yields smaller mean δ13C anomalies than the western tropical Pacific, and 3) δ13C anomalies in the Southern Ocean decrease with increasing latitude. Our results are generally inconsistent with the deep upwelling hypothesis, which predicts that the δ13C signal should be largest in the Southern Ocean and upwelling regions. Instead, the spatial pattern in δ13C anomalies supports the biological pump hypothesis, which predicts that reduced export of light carbon from the euphotic zone triggers negative carbon isotope anomalies in the surface ocean and positive anomalies at intermediate depths. Upwelling of relatively 13C-enriched intermediate waters tends to moderate carbon isotope minima in upwelling regions. Our results suggest that the initial rise in atmospheric CO2 during Termination 1 was likely due to weakening of the biological pump

Carbon isotope equilibration during sulphate-limited anaerobic oxidation of methane

NASA Astrophysics Data System (ADS)

Yoshinaga, Marcos Y.; Holler, Thomas; Goldhammer, Tobias; Wegener, Gunter; Pohlman, John W.; Brunner, Benjamin; Kuypers, Marcel M. M.; Hinrichs, Kai-Uwe; Elvert, Marcus

2014-03-01

Collectively, marine sediments comprise the largest reservoir of methane on Earth. The flux of methane from the sea bed to the overlying water column is mitigated by the sulphate-dependent anaerobic oxidation of methane by marine microbes within a discrete sedimentary horizon termed the sulphate-methane transition zone. According to conventional isotope systematics, the biological consumption of methane leaves a residue of methane enriched in 13C (refs , , ). However, in many instances the methane within sulphate-methane transition zones is depleted in 13C, consistent with the production of methane, and interpreted as evidence for the intertwined anaerobic oxidation and production of methane. Here, we report results from experiments in which we incubated cultures of microbial methane consumers with methane and low levels of sulphate, and monitored the stable isotope composition of the methane and dissolved inorganic carbon pools over time. Residual methane became progressively enriched in 13C at sulphate concentrations above 0.5 mM, and progressively depleted in 13C below this threshold. We attribute the shift to 13C depletion during the anaerobic oxidation of methane at low sulphate concentrations to the microbially mediated carbon isotope equilibration between methane and carbon dioxide. We suggest that this isotopic effect could help to explain the 13C-depletion of methane in subseafloor sulphate-methane transition zones.

Role of water in hydrocarbon generation from Type-I kerogen in Mahogany oil shale of the Green River Formation

USGS Publications Warehouse

Lewan, M.D.; Roy, S.

2011-01-01

Hydrous and anhydrous closed-system pyrolysis experiments were conducted on a sample of Mahogany oil shale (Eocene Green River Formation) containing Type-I kerogen to determine whether the role of water had the same effect on petroleum generation as reported for Type-II kerogen in the Woodford Shale. The experiments were conducted at 330 and 350??C for 72h to determine the effects of water during kerogen decomposition to polar-rich bitumen and subsequent bitumen decomposition to hydrocarbon-rich oil. The results showed that the role of water was more significant in bitumen decomposition to oil at 350??C than in kerogen decomposition to bitumen at 330??C. At 350??C, the hydrous experiment generated 29% more total hydrocarbon product and 33% more C15+ hydrocarbons than the anhydrous experiment. This is attributed to water dissolved in the bitumen serving as a source of hydrogen to enhance thermal cracking and facilitate the expulsion of immiscible oil. In the absence of water, cross linking is enhanced in the confines of the rock, resulting in formation of pyrobitumen and molecular hydrogen. These differences are also reflected in the color and texture of the recovered rock. Despite confining liquid-water pressure being 7-9 times greater in the hydrous experiments than the confining vapor pressure in the anhydrous experiments, recovered rock from the former had a lighter color and expansion fractures parallel to the bedding fabric of the rock. The absence of these open tensile fractures in the recovered rock from the anhydrous experiments indicates that water promotes net-volume increase reactions like thermal cracking over net-volume decrease reactions like cross linking, which results in pyrobitumen. The results indicate the role of water in hydrocarbon and petroleum formation from Type-I kerogen is significant, as reported for Type-II kerogen. ?? 2010.

Unique distributions of hydrocarbons and sulphur compounds released by flash pyrolysis from the fossilised alga Gloeocapsomorpha prisca , a major constituent in one of four Ordovician kerogens

NASA Astrophysics Data System (ADS)

Douglas, A. G.; Damsté, J. S. Sinninghe; Fowler, M. G.; Eglinton, T. I.; de Leeuw, J. W.

1991-01-01

Kerogens isolated from four rocks of Ordovician age from North America have been analysed by combined pyrolysis-gas chromatography-mass spectrometry to compare and contrast the type and distribution of sulphur-containing compounds and aromatic and aliphatic hydrocarbons present in the pyrolysates. When pyrolysed, all of the kerogens released several series of heterocyclic sulphur compounds including alkylthiophenes, alkylthiolanes, alkylthianes and alkylbenzothiophenes together with n-alkanes, n-alklenes and alkylcyclohexanes as well as alkyl-substituted benzenes and naphthalenes. One of the kerogens, isolated from the Guttenberg oil rock, consisted predominantly of the alga Gloeocapsomorpha prisca, which produced sulphur compounds and hydrocarbons with fingerprint pyrograms that were different from those of the other three kerogens. The data provide prima facie evidence that these distributions may act as pseudo "biological markers" for this species of alga, namely that unsaturated kerogen moieties available for the uptake of sulphur, or which can cyclise to form hydrocarbons, distinguish Gloeocapsomorpha prisca from the contributing organisms of the other kerogens analysed.

[A review of water and carbon flux partitioning and coupling in SPAC using stable isotope techniques].

PubMed

Xu, Xiao Wu; Yu, Xin Xiao; Jia, Guo Dong; Li, Han Zhi; Lu, Wei Wei; Liu, Zi Qiang

2017-07-18

Soil-vegetation-atmosphere continuum (SPAC) is one of the important research objects in the field of terrestrial hydrology, ecology and global change. The process of water and carbon cycling, and their coupling mechanism are frontier issues. With characteristics of tracing, integration and indication, stable isotope techniques contribute to the estimation of the relationship between carbon sequestration and water consumption in ecosystems. In this review, based on a brief introduction of stable isotope principles and techniques, the applications of stable isotope techniques to water and carbon exchange in SPAC using optical stable isotope techniques were mainly explained, including: partitioning of net carbon exchange into photosynthesis and respiration; partitioning of evapotranspiration into transpiration and evaporation; coupling of water and carbon cycle at the ecosystem scale. Advanced techniques and methods provided long-term and high frequency measurements for isotope signals at the ecosystem scale, but the issues about the precision and accuracy for measurements, partitioning of ecosystem respiration, adaptability for models under non-steady state, scaling up, coupling mechanism of water and carbon cycles, were challenging. The main existing research findings, limitations and future research prospects were discussed, which might help new research and technology development in the field of stable isotope ecology.

Applications of Cavity Ring-Down Spectroscopy (CRDS) to Analysis of Carbon Stable Isotope Composition of Groundwater

NASA Astrophysics Data System (ADS)

Jeong, T.; Woo, N. C.; Choi, H.

2014-12-01

Carbon Capture and Storage (CCS) has been considered as an effective strategy to reduce atmospheric carbon dioxide (CO2) concentration. However, unintended leakage of CO2 leakage from storage sites could occur through highly permeable conduits such as fractures in low-K formations during the injection and storage of SCCO2 (supercritical phase CO2). Therefore, prediction and detection of CO2 leakage and relevant analysis of carbon isotope are crucial to assure environmental and public safety. Until recently, Isotope Ratio Mass Spectrometry (IRMS) has been utilized to measure the stable isotope ratio of water. However, IRMS is time-consuming operation due to complicated pretreatment, and thus not a practical methodology under field conditions. Carbon Isotope Analyzer (CCIA), which is a kind of Cavity Ring-Down Spectroscopy (CRDS) and has a wide measurement range from 300 to 25000 ppmv, can facilitate the rate of measurements up to 1 Hz by using continuous flow method so that it can be readily applied to field. In this study, carbon stable isotope ratio of groundwater will be analyzed using CCIA. Then, the CCIA results will be compared with IRMS to validate its accuracy and stability. This research will provide an appropriate method for analyzing carbon stable isotope in groundwater, using a continuous flow mode.

Martian carbon dioxide: Clues from isotopes in SNC meteorites

NASA Technical Reports Server (NTRS)

Karlsson, H. R.; Clayton, R. N.; Mayeda, T. K.; Jull, A. J. T.; Gibson, E. K., Jr.

1993-01-01

Attempts to unravel the origin and evolution of the atmosphere and hydrosphere on Mars from isotopic data have been hampered by the impreciseness of the measurements made by the Viking Lander and by Earth-based telescopes. The SNC meteorites which are possibly pieces of the Martian surface offer a unique opportunity to obtain more precise estimates of the planet's volatile inventory and isotopic composition. Recently, we reported results on oxygen isotopes of water extracted by pyrolysis from samples of Shergotty, Zagami, Nakhla, Chassigny, Lafayette, and EETA-79001. Now we describe complementary results on the stable isotopic composition of carbon dioxide extracted simultaneously from those same samples. We will also report on C-14 abundances obtained by accelerator mass spectrometry (AMS) for some of these CO2 samples.

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

NASA Astrophysics Data System (ADS)

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.

2011-11-01

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

USE OF FATTY ACID STABLE CARBON ISOTOPE RATIO TO INDICATE MICROBIAL CARBON SOURCE IN TROPICAL SOILS

EPA Science Inventory

We use measurements of the concentration and stable carbon isotope ratio of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels, broad microbial community structure, and microbial carbon source. For studies of soil o...

PHOTOCHEMICALLY-INDUCED ALTERATION OF STABLE CARBON ISOTOPE RATIOS (DELTA C-13) IN TERRIGENOUS DISSOLVED ORGANIC CARBON

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...

Isotope excursions and shifting oxidation states recorded in the Paleoproterozoic Franceville Basin

NASA Astrophysics Data System (ADS)

Wang, V.; Junium, C. K.; Lu, Z.; Préat, A.

2014-12-01

Geochemical studies of Paleoproterozoic rocks have revealed that the initial rise of oxygen was protracted and that Earth's surface environments fluctuated between oxic and anoxic states over hundreds of millions of years. Marine sediments of the 2.1 Gyr-old Franceville Basin of west central Africa are only lightly metamorphosed, and their geochemistry may thus reveal unique insights into the environmental and metabolic conditions during the history of rising oxygen levels. In the Franceville Basin stratigraphic variation totaling 10‰ in δ13Ccarb was previously documented. This contribution builds on this work and characterizes changes in C, N, and S cycles using stable isotope values. The results from systematic analysis of several biologically mediated redox proxies preserved in carbonates from the Franceville Basin will be presented, including δ34S values of pyrite and δ13C and δ15N values of bulk organic carbon and kerogens. Consistent with independent reports of an excursion in δ13Corg in the Franceville Basin and elsewhere, we find ~20‰ stratigraphic variation in δ13C of bulk organic carbon. Initial results for δ15N of bulk organic matter range from -6 to 6 ‰, a wider distribution of values than previously reported for the Franceville Basin and more negative than values reported for the similarly aged Onega Basin in Fennoscandia. I/Ca ratios range from near zero to near Phanerozoic levels and are consistent with the presence of iodate. Chromium reducible sulfide has been extracted from all but one sample, confirming the presence of pyrite. δ34S of pyrite as well as δ13C and δ15N of kerogen will also be presented. The biochemically diverse array of proxy analyses presented here have varying thresholds of sensitivity to oxygen levels and hence will allow detailed reconstruction of the redox history of basin waters. As minimum O2 thresholds are often needed for certain biochemical processes, the resulting data will also have implications for key

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...

Regional prediction of carbon isotopes in soil carbonates for Asian dust source tracer

NASA Astrophysics Data System (ADS)

Chen, Bing; Cui, Xinjuan; Wang, Yaqiang

2016-10-01

Dust particles emitted from deserts and semi-arid lands in northern China cause particulate pollution that increases the burden of disease particularly for urban population in East Asia. The stable carbon isotopes (δ13C) of carbonates in soils and dust aerosols in northern China were investigated. We found that the δ13C of carbonates in surface soils in northern China showed clearly the negative correlation (R2 = 0.73) with Normalized Difference Vegetation Index (NDVI). Using Moderate Resolution Imaging Spectroradiometer (MODIS) satellite-derived NDVI, we predicted the regional distribution of δ13C of soil carbonates in deserts, sandy lands, and steppe areas. The predictions show the mean δ13C of -0.4 ± 0.7‰ in soil carbonates in Taklimakan Desert and Gobi Deserts, and the isotope values decrease to -3.3 ± 1.1‰ in sandy lands. The increase in vegetation coverage depletes 13C in soil carbonates, thus the steppe areas are predicted by the lowest δ13C levels (-8.1 ± 1.7‰). The measurements of atmospheric dust samples at eight sites showed that the Asian dust sources were well assigned by the 13C mapping in surface soils. Predicting 13C in large geographical areas with fine resolution offers a cost-effective tracer to monitor dust emissions from sandy lands and steppe areas which show an increasing role in Asian dust loading driven by climate change and human activities.

Carbon and nitrogen isotope variations in tree-rings as records of perturbations in regional carbon and nitrogen cycles.

PubMed

Bukata, Andrew R; Kyser, T Kurtis

2007-02-15

Increasing anthropogenic pollution from urban centers and fossil fuel combustion can impact the carbon and nitrogen cycles in forests. To assess the impact of twentieth century anthropogenic pollution on forested system carbon and nitrogen cycles, variations in the carbon and nitrogen isotopic compositions of tree-rings were measured. Individual annual growth rings in trees from six sites across Ontario and one in New Brunswick, Canada were used to develop site chronologies of tree-ring delta 15N and delta 13C values. Tree-ring 615N values were approximately 0.5% per hundred higher and correlated with contemporaneous foliar samples from the same tree, but not with delta 15N values of soil samples. Temporal trends in carbon and nitrogen isotopic compositions of these tree-rings are consistent with increasing anthropogenic influence on both the carbon and nitrogen cycles since 1945. Tree-ring delta 13C values and delta 15N values are correlated at both remote and urban-proximal sites, with delta 15N values decreasing since 1945 and converging on 1% per hundred at urban-proximal sites and decreasing but not converging on a single delta 15N value in remote sites. These results indicate that temporal trends in tree-ring nitrogen and carbon isotopic compositions record the regional extent of pollution.

A Test of Carbon and Oxygen Stable Isotope Ratio Process Models in Tree Rings.

NASA Astrophysics Data System (ADS)

Roden, J. S.; Farquhar, G. D.

2008-12-01

Stable isotopes ratios of carbon and oxygen in tree ring cellulose have been used to infer environmental change. Process-based models have been developed to clarify the potential of historic tree ring records for meaningful paleoclimatic reconstructions. However, isotopic variation can be influenced by multiple environmental factors making simplistic interpretations problematic. Recently, the dual isotope approach, where the variation in one stable isotope ratio (e.g. oxygen) is used to constrain the interpretation of variation in another (e.g. carbon), has been shown to have the potential to de-convolute isotopic analysis. However, this approach requires further testing to determine its applicability for paleo-reconstructions using tree-ring time series. We present a study where the information needed to parameterize mechanistic models for both carbon and oxygen stable isotope ratios were collected in controlled environment chambers for two species (Pinus radiata and Eucalyptus globulus). The seedlings were exposed to treatments designed to modify leaf temperature, transpiration rates, stomatal conductance and photosynthetic capacity. Both species were grown for over 100 days under two humidity regimes that differed by 20%. Stomatal conductance was significantly different between species and for seedlings under drought conditions but not between other treatments or humidity regimes. The treatments produced large differences in transpiration rate and photosynthesis. Treatments that effected photosynthetic rates but not stomatal conductance influenced carbon isotope discrimination more than those that influenced primarily conductance. The various treatments produced a range in oxygen isotope ratios of 7 ‰. Process models predicted greater oxygen isotope enrichment in tree ring cellulose than observed. The oxygen isotope ratios of bulk leaf water were reasonably well predicted by current steady-state models. However, the fractional difference between models that

Experimental Determination of Carbon Isotope Fractionation in C-O-H-Fluids and the Carbonate-melt - Graphite System at High Temperatures

NASA Astrophysics Data System (ADS)

Kueter, N.; Schmidt, M. W.; Lilley, M. D.; Bernasconi, S. M.

2017-12-01

The understanding of deep-earth carbon fluxes depends greatly on the investigation of carbon isotope systematics in C-O-H-fluids and carbon minerals, such as graphite and diamond (C0). The isotope fractionation factors between the different C-phases and species (in e.g. a fluid) thus govern the observed isotope fractionation patterns. C-isotope fractionation factors relevant for high temperatures are mainly derived from theoretical calculations [e.g. 1,2,3] and, with few exceptions, lack experimental determinations [e.g. 4]. Hundreds of own experiments aimed at equilibrating elemental carbon (C0, graphite/diamond) with C-O-H-fluids demonstrate that kinetics reigns as no system would be closed for H on time scales and temperatures allowing for graphite to equilibrate. To overcome this problem, we performed two studies to determine the C-isotope fractionation in 1) the CO2-CO-CH4 system and 2) the carbonate-melt - graphite system. Equilibrium C-isotope fractionation factors were obtained for CO2 - CO and CH4 - CO pairs (600 - 1200°C) and graphite - Na2CO3/CaCO3melt (900 - 1500°C). Combined with the already available fractionation data for the CaCO3-CO2 pair (400-950°C) from Chacko et al. [4], we determined experimentally based C-isotope fractionation factors for C0 - CH4 and CO2 - C0 pairs by 1) Δ13CCO2-graphite = Δ13CCO2-carbonate + Δ13CCarbonate-graphite and 2) Δ13Cgraphite-CH4 = Δ13CCO2-CH4 - Δ13CCO2-graphite . Current calculated fractionation factors relevant for mantle temperatures (1100 - 1500°C) suggest C-isotope partitioning in the CO2 - C0 pair on the order of 4.2 to 2.4‰, about 2‰ less than predicted by theoretically derived factors [3]. In contrast, our calculations suggest fractionation of about 1.4 to 1.1‰ for the C0 - CH4 pair, about 1‰ higher than expected by theory [3]. [1] Richet et al. (1977) Ann. Rev. Earth Planet. Sci.; [2] Polyakov & Kharlashina (1995) GCA; [3] Bottinga (1969) GCA; [4] Chacko et al. (2001) Rev Mineral Geochem

Carbon Isotopic Fractionation in Fischer-Tropsch Type Reactions and Relevance to Meteorite Organics

NASA Technical Reports Server (NTRS)

Johnson, Natasha M; Elsila, Jamie E.; Kopstein, Mickey; Nuth, Joseph A., III

2012-01-01

Fischer-Tropsch-Type (FTT) reactions have been hypothesized to contribute to the formation of organic compounds in the early solar system, but it has been difficult to identify a signature of such reactions in meteoritic organics. The work reported here examined whether temperature-dependent carbon isotopic fractionation of FTT reactions might provide such a signature. Analyses of bulk organic deposits resulting from FTT experiments show a slight trend towards lighter carbon isotopic ratios with increasing temperature. It is unlikely, however, that these carbon isotopic signatures could provide definitive provenance for organic compounds in solar system materials produced through FTT reactions, because of the small scale of the observed fractionations and the possibility that signatures from many different temperatures may be present in any specific grain.

[Quantitative estimation source of urban atmospheric CO2 by carbon isotope composition].

PubMed

Liu, Wei; Wei, Nan-Nan; Wang, Guang-Hua; Yao, Jian; Zeng, You-Shi; Fan, Xue-Bo; Geng, Yan-Hong; Li, Yan

2012-04-01

To effectively reduce urban carbon emissions and verify the effectiveness of currently project for urban carbon emission reduction, quantitative estimation sources of urban atmospheric CO2 correctly is necessary. Since little fractionation of carbon isotope exists in the transportation from pollution sources to the receptor, the carbon isotope composition can be used for source apportionment. In the present study, a method was established to quantitatively estimate the source of urban atmospheric CO2 by the carbon isotope composition. Both diurnal and height variations of concentrations of CO2 derived from biomass, vehicle exhaust and coal burning were further determined for atmospheric CO2 in Jiading district of Shanghai. Biomass-derived CO2 accounts for the largest portion of atmospheric CO2. The concentrations of CO2 derived from the coal burning are larger in the night-time (00:00, 04:00 and 20:00) than in the daytime (08:00, 12:00 and 16:00), and increase with the increase of height. Those derived from the vehicle exhaust decrease with the height increase. The diurnal and height variations of sources reflect the emission and transport characteristics of atmospheric CO2 in Jiading district of Shanghai.

CARBON ISOTOPE DISCRIMINATION AND GROWTH RESPONSE TO STAND DENSITY REDUCTIONS IN OLD PINUS PONDEROSA TREES

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 ...

Thermal alteration of young kerogen in relation to petroleum genesis

NASA Technical Reports Server (NTRS)

Ishiwatari, R.; Ishiwatari, M.; Kaplan, I. R.; Rohrback, B. G.

1976-01-01

Kerogen, humic acid, and lipid material were separated from a young marine sediment and heated in sealed tubes in a nitrogen atmosphere at 150 and 410 C. Gaseous and liquid products generated during heating, and also the residual organic material, were characterized by gas-liquid chromatography, elemental analysis, infrared and electron spin resonance spectroscopy, and X-ray diffraction.

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

USGS Publications Warehouse

Hassan, Afifa Afifi

1982-01-01

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)

Stable Carbon Isotopic Signatures of Abiotic Organics from Hydrothermal Synthesis Experiments

NASA Technical Reports Server (NTRS)

Stern, Jennifer C.; Summers, David P.; Kubo, Mike; Yassar, Saima

2006-01-01

Stable carbon isotopes can be powerful biogeochemical markers in the study of life's origins. Biogenic carbon fixation produces organics that are depleted in C-13 by about -20 to -30%0. Less attention has been paid to the isotopic signatures of abiotic processes. The possibility of abiotic processes producing organics with morphologies and isotopic signatures in the biogenic range has been at the center of recent debate over the Earth's earliest microfossils. The abiotic synthesis of organic compounds in hydrothermal environments is one possible source of endogenous organic matter to the prebiotic earth. Simulated hydrothermal settings have been shown to synthesize, among other things, single chain amphiphiles and simple lipids from a mix of CO, CO2, and H2. A key characteristic of these amphiphilic molecules is the ability to self-assemble in aqueous phases into more organized structures called vesicles, which form a selectively permeable boundary and serve the function of containing and concentrating other organic molecules. The ability to form cell like structures also makes these compounds more likely to be mistaken for biogenic. Hydrothermal simulation experiments were conducted from oxalic or formic acid in water at 175 C for 72 hr. The molecular and isotopic composition of the products of these reactions were determined and compared to biogenic fractionations . Preliminary results indicate isotopic fractionation during abiotic hydrocarbon synthesis in hydrothermal environments is on par with biological carbon fixation.

BOREAS TE-5 Tree Ring and Carbon Isotope Ratio Data

NASA Technical Reports Server (NTRS)

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

2000-01-01

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).

Analysis of the site-specific carbon isotope composition of propane by gas source isotope ratio mass spectrometer

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Neto, E. V. Santos; Eiler, John M.

2016-09-01

Site-specific isotope ratio measurements potentially provide valuable information about the formation and degradation of complex molecules-information that is lost in conventional bulk isotopic measurements. Here we discuss the background and possible applications of such measurements, and present a technique for studying the site-specific carbon isotope composition of propane at natural abundance based on mass spectrometric analysis of the intact propane molecule and its fragment ions. We demonstrate the feasibility of this approach through measurements of mixtures of natural propane and propane synthesized with site-specific 13C enrichment, and we document the limits of precision of our technique. We show that mass balance calculations of the bulk δ13C of propane based on our site-specific measurements is generally consistent with independent constraints on bulk δ13C. We further demonstrate the accuracy of the technique, and illustrate one of its simpler applications by documenting the site-specific carbon isotope signature associated with gas phase diffusion of propane, confirming that our measurements conform to the predictions of the kinetic theory of gases. This method can be applied to propane samples of moderate size (tens of micromoles) isolated from natural gases. Thus, it provides a means of studying the site-specific stable isotope systematics of propane at natural isotope abundances on sample sizes that are readily recovered from many natural environments. This method may also serve as a model for future techniques that apply high-resolution mass spectrometry to study the site-specific isotopic distributions of larger organic molecules, with potential applications to biosynthesis, forensics and other geochemical subjects.

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...

Carbon Monoxide Isotopes: On the Trail of Galactic Chemical Evolution

NASA Technical Reports Server (NTRS)

Langer, W.

1995-01-01

From the early days of the discovery of radio emission from carbon monoxide it was realized that it offered unusual potential for under- standing the chemical evolution of the Galaxy and external galaxies through measurements of molecular isotopes. These results bear on stellar nucleosynthesis, star formation, and gases in the interstellar medium. Progress in isotopic radio measurements will be reviewed.

Assessing the statistical robustness of inter- and intra-basinal carbon isotope chemostratigraphic correlation

NASA Astrophysics Data System (ADS)

Hay, C.; Creveling, J. R.; Huybers, P. J.

2016-12-01

Excursions in the stable carbon isotopic composition of carbonate rocks (δ13Ccarb) can facilitate correlation of Precambrian and Phanerozoic sedimentary successions at a higher temporal resolution than radiometric and biostratigraphic frameworks typically afford. Within the bounds of litho- and biostratigraphic constraints, stratigraphers often correlate isotopic patterns between distant stratigraphic sections through visual alignment of local maxima and minima of isotopic values. The reproducibility of this method can prove challenging and, thus, evaluating the statistical robustness of intrabasinal composite carbon isotope curves, and global correlations to these reference curves, remains difficult. To assess the reproducibility of stratigraphic alignment of δ13Ccarb data, and correlations between carbon isotope excursions, we employ a numerical dynamic time warping methodology that stretches and squeezes the time axis of a record to obtain an optimal correlation (in a least-squares sense) between time-uncertain series of data. In particular, we assess various alignments between series of Early Cambrian δ13Ccarb data with respect to plausible matches. We first show that an alignment of these records obtained visually, and published previously, is broadly reproducible using dynamic time warping. Alternative alignments with similar goodness of fits are also obtainable, and their stratigraphic plausibility are discussed. This approach should be generalizable to an algorithm for the purposes of developing a library of plausible alignments between multiple time-uncertain stratigraphic records.

Dual-Carbon sources fuel the OCS deep-reef Community, a stable isotope investigation

USGS Publications Warehouse

Sulak, Kenneth J.; Berg, J.; Randall, Michael T.; Dennis, George D.; Brooks, R.A.

2008-01-01

The hypothesis that phytoplankton is the sole carbon source for the OCS deep-reef community (>60 m) was tested. Trophic structure for NE Gulf of Mexico deep reefs was analyzed via carbon and nitrogen stable isotopes. Carbon signatures for 114 entities (carbon sources, sediment, fishes, and invertebrates) supported surface phytoplankton as the primary fuel for the deep reef. However, a second carbon source, the macroalga Sargassum, with its epiphytic macroalgal associate, Cladophora liniformis, was also identified. Macroalgal carbon signatures were detected among 23 consumer entities. Most notably, macroalgae contributed 45 % of total carbon to the 13C isotopic spectrum of the particulate-feeding reef-crest gorgonian Nicella. The discontinuous spatial distribution of some sessile deep-reef invertebrates utilizing pelagic macroalgal carbon may be trophically tied to the contagious distribution of Sargassum biomass along major ocean surface features.

The clumped isotope geothermometer in soil and paleosol carbonate

NASA Astrophysics Data System (ADS)

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

2013-03-01

We studied both modern soils and buried paleosols in order to understand the relationship of temperature (T°C(47)) estimated from clumped isotope compositions (Δ47) 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

Stable carbon and nitrogen isotope enrichment in primate tissues

PubMed Central

Carter, Melinda L.; Karpanty, Sarah M.; Zihlman, Adrienne L.; Koch, Paul L.; Dominy, Nathaniel J.

2010-01-01

Isotopic studies of wild primates have used a wide range of tissues to infer diet and model the foraging ecologies of extinct species. The use of mismatched tissues for such comparisons can be problematic because differences in amino acid compositions can lead to small isotopic differences between tissues. Additionally, physiological and dietary differences among primate species could lead to variable offsets between apatite carbonate and collagen. To improve our understanding of the isotopic chemistry of primates, we explored the apparent enrichment (ε*) between bone collagen and muscle, collagen and fur or hair keratin, muscle and keratin, and collagen and bone carbonate across the primate order. We found that the mean ε* values of proteinaceous tissues were small (≤1‰), and uncorrelated with body size or phylogenetic relatedness. Additionally, ε* values did not vary by habitat, sex, age, or manner of death. The mean ε* value between bone carbonate and collagen (5.6 ± 1.2‰) was consistent with values reported for omnivorous mammals consuming monoisotopic diets. These primate-specific apparent enrichment values will be a valuable tool for cross-species comparisons. Additionally, they will facilitate dietary comparisons between living and fossil primates. Electronic supplementary material The online version of this article (doi:10.1007/s00442-010-1701-6) contains supplementary material, which is available to authorized users. PMID:20628886

Helium-carbon isotopic composition of thermal waters from Tunisia

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

Growth versus metabolic tissue replacement in mouse tissues determined by stable carbon and nitrogen isotope analysis

NASA Astrophysics Data System (ADS)

Macavoy, S. E.; Jamil, T.; Macko, S. A.; Arneson, L. S.

2003-12-01

Stable isotope analysis is becoming an extensively used tool in animal ecology. The isotopes most commonly used for analysis in terrestrial systems are those of carbon and nitrogen, due to differential carbon fractionation in C3 and C4 plants, and the approximately 3‰ enrichment in 15N per trophic level. Although isotope signatures in animal tissues presumably reflect the local food web, analysis is often complicated by differential nutrient routing and fractionation by tissues, and by the possibility that large organisms are not in isotopic equilibrium with the foods available in their immediate environment. Additionally, the rate at which organisms incorporate the isotope signature of a food through both growth and metabolic tissue replacement is largely unknown. In this study we have assessed the rate of carbon and nitrogen isotopic turnover in liver, muscle and blood in mice following a diet change. By determining growth rates, we were able to determine the proportion of tissue turnover caused by growth versus that caused by metabolic tissue replacement. Growth was found to account for approximately 10% of observed tissue turnover in sexually mature mice (Mus musculus). Blood carbon was found to have the shortest half-life (16.9 days), followed by muscle (24.7 days). Liver carbon turnover was not as well described by the exponential decay equations as other tissues. However, substantial liver carbon turnover was observed by the 28th day after diet switch. Surprisingly, these tissues primarily reflect the carbon signature of the protein, rather than carbohydrate, source in their diet. The nitrogen signature in all tissues was enriched by 3 - 5‰ over their dietary protein source, depending on tissue type, and the isotopic turnover rates were comparable to those observed in carbon.

Stable carbon isotope ratios of intact GDGTs indicate heterogeneous sources to marine sediments

NASA Astrophysics Data System (ADS)

Pearson, Ann; Hurley, Sarah J.; Walter, Sunita R. Shah; Kusch, Stephanie; Lichtin, Samantha; Zhang, Yi Ge

2016-05-01

Thaumarchaeota, the major sources of marine glycerol dibiphytanyl glycerol tetraether lipids (GDGTs), are believed to fix the majority of their carbon directly from dissolved inorganic carbon (DIC). The δ13C values of GDGTs (δ13CGDGT) may be powerful tools for reconstructing variations in the ocean carbon cycle, including paleoproductivity and water mass circulation, if they can be related to values of δ13CDIC. To date, isotope measurements primarily are made on the C40 biphytane skeletons of GDGTs, rather than on complete tetraether structures. This approach erases information revealed by the isotopic heterogeneity of GDGTs within a sample and may impart an isotopic fractionation associated with the ether cleavage. To circumvent these issues, we present δ13C values for GDGTs from twelve recent sediments representing ten continental margin locations. Samples are purified by orthogonal dimensions of HPLC, followed by measurement of δ13C values by Spooling Wire Microcombustion (SWiM)-isotope ratio mass spectrometry (IRMS) with 1σ precision and accuracy of ±0.25‰. Using this approach, we confirm that GDGTs, generally around -19‰, are isotopically ;heavy; compared to other marine lipids. However, measured δ13CGDGT values are inconsistent with predicted values based on the 13C content of DIC in the overlying water column and the previously-published biosynthetic isotope fractionation for a pure culture of an autotrophic marine thaumarchaeon. In some sediments, the isotopic composition of individual GDGTs differs, indicating multiple source inputs. The data appear to confirm that crenarchaeol primarily is a biomarker for Thaumarchaeota, but its δ13C values still cannot be explained solely by autotrophic carbon fixation. Overall the complexity of the results suggests that both organic carbon assimilation (ca. 25% of total carbon) and multiple source(s) of exogenous GDGTs (contributing generally <30% of input to sediments) are necessary to explain the observed

C isotope fractionation during heterotrophic activity driven carbonate precipitation

NASA Astrophysics Data System (ADS)

Balci, Nurgul; Demirel, Cansu

2016-04-01

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

New carbon-isotope evidence from the Polish Basin for a major carbon-cycle perturbation at the Triassic-Jurassic Boundary

NASA Astrophysics Data System (ADS)

Pointer, Robyn; Hesselbo, Stephen; Littler, Kate; Pieńkowski, Grzegorz; Hodbod, Marta

2016-04-01

Carbon-isotope analysis of fossil plant material from a Polish core provides new evidence of a perturbation to the atmospheric carbon-cycle at the Triassic-Jurassic boundary (~201 Ma). The Triassic-Jurassic boundary was a time of extreme climate change which also coincided with the end-Triassic mass extinction. The new data will allow us to identify climatic changes in the Polish Basin across the Triassic-Jurassic boundary and evaluate these changes on a broader scale by comparison to data from other sites located around the world. The Niekłan borehole core, located in the southern Polish Basin, provides a ~200 metre-long terrestrial record spanning the Rhaetian and Hettangian, including the Triassic-Jurassic boundary (~208-199 Ma). The Niekłan core consists of interbedded fluvial and lacustrine sediments containing preserved plant material and thus provides an excellent opportunity to study both terrestrial palaeoenvironmental changes in the Polish Basin and perturbations in the carbon-cycle more broadly. Carbon-isotope analysis of macrofossil plant material and microscopic woody phytoclasts from the Niekłan core reveals a negative carbon-isotope excursion (CIE) of ~-3‰ at the end of the Rhaetian, before a gradual return to more positive values thereafter. The negative CIE suggests an injection of isotopically-light carbon into the atmosphere occurred just before the Triassic-Jurassic boundary. Likely sources of this carbon include volcanogenic gases, methane released from gas hydrates, or a combination of the two. The negative CIE seen in plant material at Niekłan is also recorded in a variety of geological materials from contemporaneous sites world-wide. These time-equivalent, but geographically separated, records indicate that the negative CIE recorded in the Niekłan plant material is the result of a regional or global carbon-cycle perturbation and is not merely a local signal. Future work will focus on using a range of palaeoenvironmental proxies in

The puzzle of the CNO isotope ratios in asymptotic giant branch carbon stars

NASA Astrophysics Data System (ADS)

Abia, C.; Hedrosa, R. P.; Domínguez, I.; Straniero, O.

2017-03-01

Context. The abundance ratios of the main isotopes of carbon, nitrogen and oxygen are modified by the CNO-cycle in the stellar interiors. When the different dredge-up events mix the burning material with the envelope, valuable information on the nucleosynthesis and mixing processes can be extracted by measuring these isotope ratios. Aims: Previous determinations of the oxygen isotopic ratios in asymptotic giant branch (AGB) carbon stars were at odds with the existing theoretical predictions. We aim to redetermine the oxygen ratios in these stars using new spectral analysis tools and further develop discussions on the carbon and nitrogen isotopic ratios in order to elucidate this problem. Methods: Oxygen isotopic ratios were derived from spectra in the K-band in a sample of galactic AGB carbon stars of different spectral types and near solar metallicity. Synthetic spectra calculated in local thermodynamic equillibrium (LTE) with spherical carbon-rich atmosphere models and updated molecular line lists were used. The CNO isotope ratios derived in a homogeneous way, were compared with theoretical predictions for low-mass (1.5-3 M⊙) AGB stars computed with the FUNS code assuming extra mixing both during the RGB and AGB phases. Results: For most of the stars the 16O/17O/18O ratios derived are in good agreement with theoretical predictions confirming that, for AGB stars, are established using the values reached after the first dredge-up (FDU) according to the initial stellar mass. This fact, as far as the oxygen isotopic ratios are concerned, leaves little space for the operation of any extra mixing mechanism during the AGB phase. Nevertheless, for a few stars with large 16O/17O/18O, the operation of such a mechanism might be required, although their observed 12C/13C and 14N/15N ratios would be difficult to reconcile within this scenario. Furthermore, J-type stars tend to have lower 16O/17O ratios than the normal carbon stars, as already indicated in previous studies

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

NASA Technical Reports Server (NTRS)

Hollander, D. J.; Sinninghe Damste, J. S.; Hayes, J. M.; de Leeuw, J. W.; Huc, A. Y.

1993-01-01

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.

Martian Cryogenic Carbonate Formation: Stable Isotope Variations Observed in Laboratory Studies

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Niles, Paul B.; Sun, Tao; Fu, Qi; Romanek, Christopher S.; Gibson, Everett K. Jr.

2014-01-01

The history of water on Mars is tied to the formation of carbonates through atmospheric CO2 and its control of the climate history of the planet. 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 easily from freezing solutions when carbon dioxide degasses quickly from Ca-bicarbonate-rich water, a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lake beds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. A series of laboratory experiments were conducted that simulated cryogenic carbonate formation on Mars in order to understand their isotopic systematics. The results indicate that carbonates grown under martian conditions show variable enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values.

Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt

USGS Publications Warehouse

Johnson, Craig A.; Bookstrom, Arthur A.; Slack, John F.

2012-01-01

Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ34S values are nearly uniform throughout the Blackbird dis- trict, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ (n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore for- mation as H2S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form vol- canogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit

Investigating controls on boron isotope ratios in shallow marine carbonates

NASA Astrophysics Data System (ADS)

Zhang, Shuang; Henehan, Michael J.; Hull, Pincelli M.; Reid, R. Pamela; Hardisty, Dalton S.; Hood, Ashleigh v. S.; Planavsky, Noah J.

2017-01-01

The boron isotope-pH proxy has been widely used to reconstruct past ocean pH values. In both planktic foraminifera and corals, species-specific calibrations are required in order to reconstruct absolute values of pH, due to the prevalence of so-called vital effects - physiological modification of the primary environmental signals by the calcifying organisms. Shallow marine abiotic carbonate (e.g. ooids and cements) could conceivably avoid any such calibration requirement, and therefore provide a potentially useful archive for reconstructions in deep (pre-Cenozoic) time. However, shallow marine abiotic carbonates could also be affected by local shifts in pH caused by microbial photosynthesis and respiration, something that has up to now not been fully tested. In this study, we present boron isotope measurements from shallow modern marine carbonates, from the Bahama Bank and Belize to investigate the potential of using shallow water carbonates as pH archives, and to explore the role of microbial processes in driving nominally 'abiogenic' carbonate deposition. For Bahama bank samples, our boron-based pH estimates derived from a range of carbonate types (i.e. ooids, peloids, hardground cements, carbonate mud, stromatolitic micrite and calcified filament micrite) are higher than the estimated modern mean-annual seawater pH values for this region. Furthermore, the majority (73%) of our marine carbonate-based pH estimates fall out of the range of the estimated pre-industrial seawater pH values for this region. In shallow sediment cores, we did not observe a correlation between measured pore water pH and boron-derived pH estimates, suggesting boron isotope variability is a depositional rather than early diagenetic signal. For Belize reef cements, conversely, the pH estimates are lower than likely in situ seawater pH at the time of cement formation. This study indicates the potential for complications when using shallow marine non-skeletal carbonates as marine pH archives

Cellulose and Lignin Carbon Isotope Signatures in Sphagnum Moss Reveal Complementary Environmental Properties

NASA Astrophysics Data System (ADS)

Loisel, J.; Nichols, J. E.; Kaiser, K.; Beilman, D. W.; Yu, Z.

2016-12-01

The carbon isotope signature (δ13C) of Sphagnum moss is increasingly used as a proxy for past surface wetness in peatlands. However, conflicting interpretations of these carbon isotope records have recently been published. While the water film hypothesis suggests that the presence of a thick (thin) water film around hollow (hummock) mosses leads to less (more) negative δ13C values, the carbon source hypothesis poses that a significant (insignificant) amount of CH4 assimilation by hollow (hummock) mosses leads to more (less) negative δ13C values. To evaluate these competing mechanisms and their impact on moss δ13C, we gathered 30 moss samples from 6 peatlands in southern Patagonia. Samples were collected along a strong hydrological gradient, from very dry hummocks (80 cm above water table depth) to submerged hollows (5 cm below water surface). These peat bogs have the advantage of being colonized by a single cosmopolitan moss species, Sphagnum magellanicum, limiting potential biases introduced by species-specific carbon discrimination. We measured δ13C from stem cellulose and leaf waxes on the same samples to quantify compound-specific carbon signatures. We found that stem cellulose and leaf-wax lipids were both strongly negatively correlated with moss water content, suggesting a primary role of water film thickness on carbon assimilation. In addition, isotopic fractionation during wax synthesis was greater than for cellulose. This offset decreases as conditions get drier, due to (i) a more effective carbon assimilation, or (ii) CH4 uptake through symbiosis with methanotrophic bacteria within the leaves of wet mosses. Biochemical analysis (carbohydrates, amino acids, hydrophenols, cutin acids) of surface moss are currently being conducted to characterize moss carbon allocation under different hydrological conditions. Overall, this modern calibration work should be of use for interpreting carbon isotope records from peatlands.

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

NASA Astrophysics Data System (ADS)

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-06-01

Despite massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix-a limiting step in shale gas extraction. Using molecular simulations, we here show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30-47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3-35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

PubMed Central

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-01-01

Despite massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Using molecular simulations, we here show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release. PMID:27306967

Carbon isotope records reveal synchronicity between carbon cycle perturbation and the "Carnian Pluvial Event" in the Tethys realm (Late Triassic)

NASA Astrophysics Data System (ADS)

Dal Corso, Jacopo; Gianolla, Piero; Newton, Robert J.; Franceschi, Marco; Roghi, Guido; Caggiati, Marcello; Raucsik, Béla; Budai, Tamás; Haas, János; Preto, Nereo

2015-04-01

In the early Late Triassic a period of increased rainfall, named the Carnian Pluvial Event (CPE), is evidenced by major lithological changes in continental and marine successions worldwide. The environmental change seems to be closely associated with a negative carbon isotope excursion that was identified in a stratigraphic succession of the Dolomites (Italy) but the temporal relationship between these phenomena is still not well defined. Here we present organic-carbon isotope data from Carnian deep-water stratigraphic sections in Austria and Hungary, and carbonate petrography of samples from a marginal marine section in Italy. A negative 2-4‰ δ13C shift is recorded by bulk organic matter in the studied sections and is coincident with a similar feature highlighted in higher plant and marine algal biomarker carbon-isotope records from the Dolomites (Italy), thus testifying to a global change in the isotopic composition of the reservoirs of the exchangeable carbon. Our new observations verify that sedimentological changes related to the CPE coincide with the carbon cycle perturbation and therefore occurred synchronously within the western Tethys. Consistent with modern observations, our results show that the injection of 13C-depleted CO2 into the Carnian atmosphere-ocean system may have been directly responsible for the increase in rainfall by intensifying the Pangaean mega-monsoon activity. The consequent increased continental weathering and erosion led to the transfer of large amounts of siliciclastics into the basins that were rapidly filled up, while the increased nutrient flux triggered the local development of anoxia. The new carbonate petrography data show that these changes also coincided with the demise of platform microbial carbonate factories and their replacement with metazoan driven carbonate deposition. This had the effect of considerably decreasing carbonate deposition in shallow water environments.

Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion

NASA Astrophysics Data System (ADS)

Balan, Etienne; Noireaux, Johanna; Mavromatis, Vasileios; Saldi, Giuseppe D.; Montouillout, Valérie; Blanchard, Marc; Pietrucci, Fabio; Gervais, Christel; Rustad, James R.; Schott, Jacques; Gaillardet, Jérôme

2018-02-01

The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33-, BO2(OH)2- and B(OH)4- anions substituted for carbonate groups, as well as those of B(OH)4- and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, Bsbnd O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7-15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10-13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at

Carbon and oxygen isotope variations of the Middle-Late Triassic Al Aziziyah Formation, northwest Libya

NASA Astrophysics Data System (ADS)

Moustafa, Mohamed S. H.; Pope, Michael C.; Grossman, Ethan L.; Mriheel, Ibrahim Y.

2016-06-01

This study presents the δ13C and δ18O records from whole rock samples of the Middle-Late Triassic (Ladinian-Carnian) Al Aziziyah Formation that were deposited on a gently sloping carbonate ramp within the Jifarah Basin of Northwest Libya. The Al Aziziyah Formation consists of gray limestone, dolomite, and dolomitic limestone interbedded with shale. The Ghryan Dome and Kaf Bates sections were sampled and analyzed for carbon and oxygen isotope chemostratigraphy to integrate high-resolution carbon isotope data with an outcrop-based stratigraphy, to provide better age control of the Al Aziziyah Formation. This study also discusses the relation between the facies architecture of the Al Aziziyah Formation and the carbon isotope values. Seven stages of relative sea level rise and fall within the Ghryan Dome were identified based on facies stacking patterns, field observations and carbon stable isotopes. The Al Aziziyah Formation δ13C chemostratigraphic curve can be partially correlated with the Triassic global δ13C curve. This correlation indicates that the Al Aziziyah Formation was deposited during the Ladinian and early Carnian. No straight-forward relationship is seen between δ13C and relative sea level probably because local influences complicated systematic environmental and diagenetic isotopic effects associated with sea level change.

Position-specific 13C distributions within propane from experiments and natural gas samples

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael D.; Eiler, John M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, 'bulk' isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in

Position-specific 13C distributions within propane from experiments and natural gas samples

USGS Publications Warehouse

Piasecki, Alison; Sessions, Alex L.; Lawson, Michael; Ferreira, A.A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael; Eilers, J.M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, ‘bulk’ isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in

Carbonate stable isotope constraints on sources of arsenic contamination in Neogene tufas and travertines of Attica, Greece

NASA Astrophysics Data System (ADS)

Kampouroglou, Evdokia E.; Tsikos, Harilaos; Economou-Eliopoulos, Maria

2017-11-01

We presented new C and O isotope data of rockforming calcite in terrestrial carbonate deposits from Neogene basins of Attica (Greece), coupled with standard mineralogical and bulk geochemical results. Whereas both isotope datasets [δ18O from -8.99 to -3.20‰(VPDB); δ13C from -8.17 to +1.40‰(VPDB)] could be interpreted in principle as indicative of a meteoric origin, the clear lack of a statistical correlation between them suggests diverse sources for the isotopic variation of the two elements. On the basis of broad correlations between lower carbon isotope data with increasing Fe and bulk organic carbon, we interpreted the light carbon isotope signatures and As enrichments as both derived mainly from a depositional process involving increased supply of metals and organic carbon to the original basins. Periodically augmented biological production and aerobic cycling of organic matter in the ambient lake waters, would have led to the precipitation of isotopically light calcite in concert with elevated fluxes of As-bearing iron oxy-hydroxide and organic matter to the initial terrestrial carbonate sediment. The terrestrial carbonate deposits of Attica therefore represented effective secondary storage reservoirs of elevated As from the adjacent mineralized hinterland; hence these and similar deposits in the region ought to be regarded as key geological candidates for anomalous supply of As to local soils, groundwater and related human activities.

Oil-generation kinetics for organic facies with Type-II and -IIS kerogen in the Menilite Shales of the Polish Carpathians

USGS Publications Warehouse

Lewan, M.D.; Kotarba, M.J.; Curtis, John B.; Wieclaw, D.; Kosakowski, P.

2006-01-01

The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S2 generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S2 generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S2 generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as

Molecular carbon isotopic evidence for the origin of geothermal hydrocarbons

USGS Publications Warehouse

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

1981-01-01

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.

Highly Efficient Quantum Sieving in Porous Graphene-like Carbon Nitride for Light Isotopes Separation

NASA Astrophysics Data System (ADS)

Qu, Yuanyuan; Li, Feng; Zhou, Hongcai; Zhao, Mingwen

2016-01-01

Light isotopes separation, such as 3He/4He, H2/D2, H2/T2, etc., is crucial for various advanced technologies including isotope labeling, nuclear weapons, cryogenics and power generation. However, their nearly identical chemical properties made the separation challenging. The low productivity of the present isotopes separation approaches hinders the relevant applications. An efficient membrane with high performance for isotopes separation is quite appealing. Based on first-principles calculations, we theoretically demonstrated that highly efficient light isotopes separation, such as 3He/4He, can be reached in a porous graphene-like carbon nitride material via quantum sieving effect. Under moderate tensile strain, the quantum sieving of the carbon nitride membrane can be effectively tuned in a continuous way, leading to a temperature window with high 3He/4He selectivity and permeance acceptable for efficient isotopes harvest in industrial application. This mechanism also holds for separation of other light isotopes, such as H2/D2, H2/T2. Such tunable quantum sieving opens a promising avenue for light isotopes separation for industrial application.

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

EPA Pesticide Factsheets

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

Carbon Isotope Fractionation Effects During Degradation of Methyl Halides in Agricultural Soils

NASA Astrophysics Data System (ADS)

Miller, L. G.; Baesman, S. M.; Oremland, R. S.; Bill, M.; Goldstein, A. H.

2001-12-01

Fumigation of agricultural soils prior to planting row crops constitutes the largest anthropogenic source of methyl bromide (MeBr) to the atmosphere. Typically, more than 60% of the MeBr added is lost to the atmosphere during the 5-6 day fumigation period. The remainder is oxidized by bacteria or otherwise degraded in the soil. In experiments using washed cells of methylotrophic bacteria isolated from agricultural soil (strain IMB-1), oxidation of MeBr, methyl chloride (MeCl) and methyl iodide to CO2 resulted in large (up to 70‰ ) fractionation of stable carbon isotopes (Miller, et al. 2001). By contrast, fractionation measured in field soils using both in situ techniques and bottle incubations with MeBr was less than 35‰ . This discrepancy was initially attributed to the large transportation losses that occur without isotopic fractionation during field fumigation. However, this rationale cannot explain why bottle incubations with soil resulted in lower fractionation factors than incubations with bacterial cultures. We conducted additional laboratory bottle experiments to examine the biological and chemical controls of carbon isotope fractionation during degradation of MeBr and MeCl by soils and bacteria. Soils were collected from a strawberry field in Santa Cruz County, California within two weeks of the start of each experiment. The rate of removal of methyl halides from the headspace was greatest during incubations at soil moisture contents around 8%. Increasing the amount of soil and hence native bacteria in each bottle minimized the lag in uptake by up to several days. No lag was observed during incubations of soils with added IMB-1. Stable isotope fractionation factors were similar for degradation by live soil and live soil with added IMB-1. Heat-killed controls of cell cultures showed little uptake (<10% over 5 days) and no isotope fractionation. Heat-killed soil controls, by contrast, demonstrated significant loss of MeBr (20-30%) with isotope

Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

NASA Astrophysics Data System (ADS)

Turchyn, Alexandra V.; DePaolo, Donald J.

2011-11-01

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ 44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ 44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ 44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ 44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these

Correlating carbon and oxygen isotope events in early to middle Miocene shallow marine carbonates in the Mediterranean region using orbitally tuned chemostratigraphy and lithostratigraphy

PubMed Central

Piller, Werner E.; Reuter, Markus; Harzhauser, Mathias

2015-01-01

Abstract During the Miocene prominent oxygen isotope events (Mi‐events) reflect major changes in glaciation, while carbonate isotope maxima (CM‐events) reflect changes in organic carbon burial, particularly during the Monterey carbon isotope excursion. However, despite their importance to the global climate history they have never been recorded in shallow marine carbonate successions. The Decontra section on the Maiella Platform (central Apennines, Italy), however, allows to resolve them for the first time in such a setting during the early to middle Miocene. The present study improves the stratigraphic resolution of parts of the Decontra section via orbital tuning of high‐resolution gamma ray (GR) and magnetic susceptibility data to the 405 kyr eccentricity metronome. The tuning allows, within the established biostratigraphic, sequence stratigraphic, and isotope stratigraphic frameworks, a precise correlation of the Decontra section with pelagic records of the Mediterranean region, as well as the global paleoclimatic record and the global sea level curve. Spectral series analyses of GR data further indicate that the 405 kyr orbital cycle is particularly well preserved during the Monterey Event. Since GR is a direct proxy for authigenic uranium precipitation during increased burial of organic carbon in the Decontra section, it follows the same long‐term orbital pacing as observed in the carbon isotope records. The 405 kyr GR beat is thus correlated with the carbon isotope maxima observed during the Monterey Event. Finally, the Mi‐events can now be recognized in the δ18O record and coincide with plankton‐rich, siliceous, or phosphatic horizons in the lithology of the section. PMID:27546980

Correlating carbon and oxygen isotope events in early to middle Miocene shallow marine carbonates in the Mediterranean region using orbitally tuned chemostratigraphy and lithostratigraphy

NASA Astrophysics Data System (ADS)

Auer, Gerald; Piller, Werner E.; Reuter, Markus; Harzhauser, Mathias

2015-04-01

During the Miocene prominent oxygen isotope events (Mi-events) reflect major changes in glaciation, while carbonate isotope maxima (CM-events) reflect changes in organic carbon burial, particularly during the Monterey carbon isotope excursion. However, despite their importance to the global climate history they have never been recorded in shallow marine carbonate successions. The Decontra section on the Maiella Platform (central Apennines, Italy), however, allows to resolve them for the first time in such a setting during the early to middle Miocene. The present study improves the stratigraphic resolution of parts of the Decontra section via orbital tuning of high-resolution gamma ray (GR) and magnetic susceptibility data to the 405 kyr eccentricity metronome. The tuning allows, within the established biostratigraphic, sequence stratigraphic, and isotope stratigraphic frameworks, a precise correlation of the Decontra section with pelagic records of the Mediterranean region, as well as the global paleoclimatic record and the global sea level curve. Spectral series analyses of GR data further indicate that the 405 kyr orbital cycle is particularly well preserved during the Monterey Event. Since GR is a direct proxy for authigenic uranium precipitation during increased burial of organic carbon in the Decontra section, it follows the same long-term orbital pacing as observed in the carbon isotope records. The 405 kyr GR beat is thus correlated with the carbon isotope maxima observed during the Monterey Event. Finally, the Mi-events can now be recognized in the δ18O record and coincide with plankton-rich, siliceous, or phosphatic horizons in the lithology of the section.

USE OF THE COMPOSITION AND STABLE CARBON ISOTOPE RATIO OF MICROBIAL FATTY ACIDS TO STUDY CARBON CYCLING

EPA Science Inventory

We use measurements of the concentration and stable carbon isotopic ratio (Gamma 13C) of individual microbial phospholipid fatty acids (PLFAS) in soils and sediments as indicators of live microbial biomass levels and microbial carbon source. For studies of soil organic matter (SO...

USE OF STABLE CARBON ISOTOPE RATIOS OF FATTY ACIDS TO EVALUATE MICROBIAL CARBON SOURCES IN TERRESTRIAL ENVIRONMENTS

EPA Science Inventory

We use measurements of the concentration and stable carbon isotopic ratio (D 13C) of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels and microbial carbon source. We found that intensive sugar cane cultivation leads to ...

Organic sulphur in macromolecular sedimentary organic matter: I. Structure and origin of sulphur-containing moieties in kerogen, asphaltenes and coal as revealed by flash pyrolysis

NASA Astrophysics Data System (ADS)

Sinninghe Damsté, Jaap S.; Eglinton, Timothy I.; De Leeuw, Jan W.; Schenck, P. A.

1989-04-01

The distributions of sulphur-containing compounds generated by flash pyrolysis of macromolecular sedimentary organic matter (kerogen, coal, asphaltenes) were studied by gas chromatography in combination with Sselective flame photometric detection or mass spectrometry. The abundance of S-containing pyrolysis products in the pyrolysates relative to other products was highly variable depending on the sample but the types of products were generally similar, being mainly composed of "gaseous" compounds ( e.g., hydrogen sulphide) and low molecular weight alkylthiophenes and alkylbenzothiophenes. The distribution patterns of the alkylated thiophenes were dominated by a limited number of all theoretically possible isomers. The alkyl substitution patterns of the dominant isomers bear a strong similarity to those of the organic S compounds present in the GC-amenable fractions of bitumens and immature oils. Therefore, it is suggested that these S-containing pyrolysis products are formed by pyrolysis of related thiophenic and benzothiophenic moieties present in the macromolecular sedimentary substances. Specific examples include those with linear alkyl, iso and anteiso alkyl, isoprenoid alkyl and steroidal carbon skeletons. The presence of higher molecular weight alkylthiophenes and alkylbenzothiophenes with these same carbon skeletons in pyrolysates of S-rich kerogens provided further evidence for the presence of these S-containing moieties. It is likely that these moieties have been formed by abiogenic S incorporation into sedimentary organic matter during early diagenesis.

The stable carbon isotope biogeochemistry of acetate and other dissolved carbon species in deep subseafloor sediments at the northern Cascadia Margin

USGS Publications Warehouse

Heuer, Verena B.; Pohlman, John W.; Torres, Marta E.; Elvert, Marcus; Hinrichs, Kai-Uwe

2009-01-01

Ocean drilling has revealed the existence of vast microbial populations in the deep subseafloor, but to date little is known about their metabolic activities. To better understand the biogeochemical processes in the deep biosphere, we investigate the stable carbon isotope chemistry of acetate and other carbon-bearing metabolites in sediment pore-waters. Acetate is a key metabolite in the cycling of carbon in anoxic sediments. Its stable carbon isotopic composition provides information on the metabolic processes dominating acetate turnover in situ. This study reports our findings for a methane-rich site at the northern Cascadia Margin (NE Pacific) where Expedition 311 of the Integrated Ocean Drilling Program (IODP) sampled the upper 190 m of sediment. At Site U1329, δ13C values of acetate span a wide range from −46.0‰ to −11.0‰ vs. VPDB and change systematically with sediment depth. In contrast, δ13C values of both the bulk dissolved organic carbon (DOC) (−21.6 ± 1.3‰ vs. VPDB) and the low-molecular-weight compound lactate (−20.9 ± 1.8‰ vs. VPDB) show little variability. These species are interpreted to represent the carbon isotopic composition of fermentation products. Relative to DOC, acetate is up to 23.1‰ depleted and up to 9.1‰ enriched in 13C. Broadly, 13C-depletions of acetate relative to DOC indicate flux of carbon from acetogenesis into the acetate pool while 13C-enrichments of pore-water acetate relative to DOC suggest consumption of acetate by acetoclastic methanogenesis. Isotopic relationships between acetate and lactate or DOC provide new information on the carbon flow and the presence and activity of specific functional microbial communities in distinct biogeochemical horizons of the sediment. In particular, they suggest that acetogenic CO2-reduction can coexist with methanogenic CO2-reduction, a notion contrary to the hypothesis that hydrogen levels are controlled by the thermodynamically most favorable electron

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

NASA Astrophysics Data System (ADS)

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-10-01

;Clumped-isotope; thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope ;clumps;). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3- and CO32-. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two

Soil moisture effects on the carbon isotopic composition of soil respiration

EPA Science Inventory

The carbon isotopic composition ( 13C) of recently assimilated plant carbon is known to depend on water-stress, caused either by low soil moisture or by low atmospheric humidity. Air humidity has also been shown to correlate with the 13C of soil respiration, which suggests indir...

Clumped-isotope thermometry of magnesium carbonates in ultramafic rocks

DOE PAGES

Garcia del Real, Pablo; Maher, Kate; Kluge, Tobias; ...

2016-08-19

Here, magnesium carbonate minerals produced by reaction of H 2O–CO 2 with ultramafic rocks occur in a wide range of paragenetic and tectonic settings and can thus provide insights into a variety of geologic processes, including deposition of ore-grade, massive-vein cryptocrystalline magnesite; formation of hydrous magnesium carbonates in weathering environments; and metamorphic carbonate alteration of ultramafic rocks. However, the application of traditional geochemical and isotopic methods to infer temperatures of mineralization, the nature of mineralizing fluids, and the mechanisms controlling the transformation of dissolved CO 2 into magnesium carbonates in these settings is difficult because the fluids are usually notmore » preserved.« less

Clumped-isotope thermometry of magnesium carbonates in ultramafic rocks

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

Garcia del Real, Pablo; Maher, Kate; Kluge, Tobias

Here, magnesium carbonate minerals produced by reaction of H 2O–CO 2 with ultramafic rocks occur in a wide range of paragenetic and tectonic settings and can thus provide insights into a variety of geologic processes, including deposition of ore-grade, massive-vein cryptocrystalline magnesite; formation of hydrous magnesium carbonates in weathering environments; and metamorphic carbonate alteration of ultramafic rocks. However, the application of traditional geochemical and isotopic methods to infer temperatures of mineralization, the nature of mineralizing fluids, and the mechanisms controlling the transformation of dissolved CO 2 into magnesium carbonates in these settings is difficult because the fluids are usually notmore » preserved.« less

BIODEGRADATION OF FLUORANTHENE AS MONITORED USING STABLE CARBON ISOTOPES

EPA Science Inventory

The measurement of stable isotope ratios of carbon (d13C values) was investigated as a viable technique to monitor the intrinsic bioremediation of polycyclic aromatic hydrocarbons (PAHs). Biometer-flask experiments were conducted in which the bacterium, Sphingomonas paucimobilis,...

Biogeochemical Cycling of Methane in the Proterozoic and Its Role in the Carbon Isotope Budget

NASA Astrophysics Data System (ADS)

Schrag, D. P.; Laakso, T.

2016-12-01

Various studies have proposed that the biogeochemical cycle of methane has played an important role throughout Earth history, both in contributing to greenhouse stability of climate in the Archean and producing carbon isotope variations and climate fluctuations in the Proterozoic and Phanerozoic. Using a simple box model that couples the geochemical cycles on carbon, oxygen, hydrogen, iron, and sulfur, combined with recent studies of methane cycling in anoxic environments, we reexamine the role of methane in both the Archean and Proterozoic, focusing on methane's role in the carbon isotope budget. We find that methane plays a much more modest role at all times of relative anoxia in the deep ocean, which requires an alternative explanation for the carbon isotope record, in particular the "boring billion" during the Mesoproterozoic. In particular, the high burial efficiency driven by lower oxygen levels drives primary production to much lower levels than has been previously described, resulting in relatively little organic matter available for methanogenesis. In addition, the anoxia in deep water results in a reduced role for methanotrophy at these times, and therefore a change in the mechanisms for production of authigenic carbonate, which may have played a significant role in the carbon isotope budget.

The effects of atmospheric [CO2] on carbon isotope fractionation and magnesium incorporation into biogenic marine calcite

NASA Technical Reports Server (NTRS)

Vieira, Veronica

1997-01-01

The influences of atmospheric carbon dioxide on the fractionation of carbon isotopes and the magnesium incorporation into biogenic marine calcite were investigated using samples of the calcareous alga Amphiroa and benthic foraminifer Sorites grown in the Biosphere 2 Ocean system under variable atmospheric CO2 concentrations (approximately 500 to 1200 ppm). Carbon isotope fractionation was studied in both the organic matter and the skeletal carbonate. Magnesium analysis was to be performed on the carbonate removed during decalcification. These data have not been collected due to technical problems. Carbon isotope data from Amphiroa yields a linear relation between [CO2] and Delta(sup 13)C(sub Corg)values suggesting that the fractionation of carbon isotopes during photosynthesis is positively correlated with atmospheric [CO2]. [CO2] and Delta(sup 13)C(sub Corg) values for Sorites produce a relation that is best described by a hyperbolic function where Delta(sup 13)C(sub Corg) values increase between 300 and 700 ppm and decrease from 700 to 1200 ppm. Further investigation of this relation and Sorites physiology is needed.

Oxygen and carbon isotope compositions of carbonates in a prominent lithologically mixed unit in the central South Norwegian Caledonides

NASA Astrophysics Data System (ADS)

Jakob, Johannes; Boulvais, Philippe; Andersen, Torgeir B.

2018-06-01

A prominent pre-Scandian lithologically mixed unit in the central South Norwegian Caledonides contains more than 100 partly carbonated and hydrated metaperidotite bodies and locally fossiliferous detrital serpentinites. The lateral consistency of this mixed unit was not fully appreciated in the past. Therefore, parts of the mixed unit along strike were interpreted to belong to several different tectonostratigraphic levels. Here, we present new carbonate stable isotope data that suggest that the carbonates of the mixed unit between Bergen and Otta (re-)equilibrated at unit-wide similar peak metamorphic conditions. The isotope compositions are characteristic for this unit and indicate that it represented one single tectonic unit during the Scandian Orogeny. The carbonates in the mélange are characterized by a narrow range of δ18O (SMOW) values between + 11 and + 15.5‰ and three groups of δ13C (PDB) values: (I) + 1.6 to + 0.3‰, (II) - 1.8 to - 3.9‰, and (III) - 6 to - 8.6‰. Carbonates of group III probably were affected by decarbonation or by a fluid containing organic carbon, whereas carbonates of group I and II overlap with δ13C values typical for Ediacaran-Silurian marine carbonates and may have retained their initial δ13C imprint. We suggest that the δ18O values (re-)equilibrated with unit-wide released metamorphic fluids during Scandian metamorphism. An outcrop-scale homogenisation of the δ13C values reflects the local carbon isotope signature of the released metamorphic fluids that circulated channelized through the mélange unit.

Oxygen and carbon isotope compositions of carbonates in a prominent lithologically mixed unit in the central South Norwegian Caledonides

NASA Astrophysics Data System (ADS)

Jakob, Johannes; Boulvais, Philippe; Andersen, Torgeir B.

2017-11-01

A prominent pre-Scandian lithologically mixed unit in the central South Norwegian Caledonides contains more than 100 partly carbonated and hydrated metaperidotite bodies and locally fossiliferous detrital serpentinites. The lateral consistency of this mixed unit was not fully appreciated in the past. Therefore, parts of the mixed unit along strike were interpreted to belong to several different tectonostratigraphic levels. Here, we present new carbonate stable isotope data that suggest that the carbonates of the mixed unit between Bergen and Otta (re-)equilibrated at unit-wide similar peak metamorphic conditions. The isotope compositions are characteristic for this unit and indicate that it represented one single tectonic unit during the Scandian Orogeny. The carbonates in the mélange are characterized by a narrow range of δ18O (SMOW) values between + 11 and + 15.5‰ and three groups of δ13C (PDB) values: (I) + 1.6 to + 0.3‰, (II) - 1.8 to - 3.9‰, and (III) - 6 to - 8.6‰. Carbonates of group III probably were affected by decarbonation or by a fluid containing organic carbon, whereas carbonates of group I and II overlap with δ13C values typical for Ediacaran-Silurian marine carbonates and may have retained their initial δ13C imprint. We suggest that the δ18O values (re-)equilibrated with unit-wide released metamorphic fluids during Scandian metamorphism. An outcrop-scale homogenisation of the δ13C values reflects the local carbon isotope signature of the released metamorphic fluids that circulated channelized through the mélange unit.

The Carbon Isotope Ratio in Local Molecular Clouds

NASA Astrophysics Data System (ADS)

Goto, Miwa; Usuda, Tomonori; Takato, Naruhisa; Masahiko, Hayashi; Sakamoto, Seiichi; Mitchell, George

We report the carbon isotope ratio in nearby molecular clouds LkHα 101, AFGL 490, and Mon R2 IRS 3. The vibrational transition bands of 12CO ν = 2 ← 0 and 13CO ν = 1 ← 0 were observed with high resolution near-infrared spectroscopy (R = 23,000) to measure the relative abundance of 13CO to 12CO. The isotopic ratios are 12CO/13CO = 1379 (LkHα 101), 8649 (AFGL 490), and 158 (Mon R2 IRS 3), which is twice higher than in the solar neighborhood. The molecular clouds are with high visible extinction (AV = 10 70 mag), well shielded from destructive FUV field. It is questionable that the selective photo-destruction of 13CO plays a major role in biasing isotope ratio. Uncertainty in the Doppler parameters of the unresolved absorption lines, and possible emission filling of fundamental transitions are suspected to account for the high 12CO/13CO ratio. Higher resolution spectroscopy (R ~ 100,000) is the key to go for the accurate measurement of isotope ratio.

A reconstruction of atmospheric carbon dioxide and its stable carbon isotopic composition from the penultimate glacial maximum to the last glacial inception

NASA Astrophysics Data System (ADS)

Schneider, R.; Schmitt, J.; Köhler, P.; Joos, F.; Fischer, H.

2013-11-01

The reconstruction of the stable carbon isotope evolution in atmospheric CO2 (δ13Catm), as archived in Antarctic ice cores, bears the potential to disentangle the contributions of the different carbon cycle fluxes causing past CO2 variations. Here we present a new record of δ13Catm before, during and after the Marine Isotope Stage 5.5 (155 000 to 105 000 yr BP). The dataset is archived on the data repository PANGEA® (www.pangea.de) under 10.1594/PANGAEA.817041. The record was derived with a well established sublimation method using ice from the EPICA Dome C (EDC) and the Talos Dome ice cores in East Antarctica. We find a 0.4‰ shift to heavier values between the mean δ13Catm level in the Penultimate (~ 140 000 yr BP) and Last Glacial Maximum (~ 22 000 yr BP), which can be explained by either (i) changes in the isotopic composition or (ii) intensity of the carbon input fluxes to the combined ocean/atmosphere carbon reservoir or (iii) by long-term peat buildup. Our isotopic data suggest that the carbon cycle evolution along Termination II and the subsequent interglacial was controlled by essentially the same processes as during the last 24 000 yr, but with different phasing and magnitudes. Furthermore, a 5000 yr lag in the CO2 decline relative to EDC temperatures is confirmed during the glacial inception at the end of MIS5.5 (120 000 yr BP). Based on our isotopic data this lag can be explained by terrestrial carbon release and carbonate compensation.

Elemental and isotopic (C, O, Sr, Nd) compositions of Late Paleozoic carbonated eclogite and marble from the SW Tianshan UHP belt, NW China: Implications for deep carbon cycle

NASA Astrophysics Data System (ADS)

Zhu, Jianjiang; Zhang, Lifei; Lü, Zeng; Bader, Thomas

2018-03-01

Subduction zones are important for understanding of the global carbon cycle from the surface to deep part of the mantle. The processes involved the metamorphism of carbonate-bearing rocks largely control the fate of carbon and contribute to local carbon isotopic heterogeneities of the mantle. In this study, we present petrological and geochemical results for marbles and carbonated eclogites in the Southwestern Tianshan UHP belt, NW China. Marbles are interlayered with coesite-bearing pelitic schists, and have Sr-Nd isotopic values (εNd (T=320Ma) = -3.7 to -8.9, 87Sr/86Sr (i) = 0.7084-0.7089), typical of marine carbonates. The marbles have dispersed low δ18OVSMOW values (ranging from 14 to 29‰) and unaffected carbon isotope (δ13CVPDB = -0.2-3.6‰), possibly due to infiltration of external H2O-rich fluids. Recycling of these marbles into mantle may play a key role in the carbon budget and contributed to the mantle carbon isotope heterogeneity. The carbonated eclogites have high Sr isotopic compositions (87Sr/86Sr (i) = 0.7077-0.7082) and positive εNd (T = 320 Ma) values (from 7.6 to 8.2), indicative of strong seafloor alteration of their protolith. The carbonates in the carbonated eclogites are mainly dolomite (Fe# = 12-43, Fe# = Fe2+/(Fe2+ + Mg)) that were added into oceanic basalts during seafloor alteration and experienced calcite - dolomite - magnesite transformation during the subduction metamorphic process. The uniformly low δ18O values (∼11.44‰) of carbonates in the carbontaed eclogites can be explained by closed-system equilibrium between carbonate and silicate minerals. The low δ13C values (from -3.3 to -7.7‰) of the carbonated eclogites most likely reflect contribution from organic carbon. Recycling of these carbonated eclogites with C isotope similar to typical mantle reservoirs into mantle may have little effect on the mantle carbon isotope heterogeneity.

Carnivore specific bone bioapatite and collagen carbon isotope fractionations: Case studies of modern and fossil grey wolf populations

NASA Astrophysics Data System (ADS)

Fox-Dobbs, K.; Wheatley, P. V.; Koch, P. L.

2006-12-01

Stable isotope analyses of modern and fossil biogenic tissues are routinely used to reconstruct present and past vertebrate foodwebs. Accurate isotopic dietary reconstructions require a consumer and tissue specific understanding of how isotopes are sorted, or fractionated, between trophic levels. In this project we address the need for carnivore specific isotope variables derived from populations that are ecologically well- characterized. Specifically, we investigate the trophic difference in carbon isotope values between mammalian carnivore (wolf) bone bioapatite and herbivore (prey) bone bioapatite. We also compare bone bioapatite and collagen carbon isotope values collected from the same individuals. We analyzed bone specimens from two modern North American grey wolf (Canis lupus) populations (Isle Royale National Park, Michigan and Yellowstone National Park, Wyoming), and the ungulate herbivores that are their primary prey (moose and elk, respectively). Because the diets of both wolf populations are essentially restricted to a single prey species, there were no confounding effects due to carnivore diet variability. We measured a trophic difference of approximately -1.3 permil between carnivore (lower value) and herbivore (higher value) bone bioapatite carbon isotope values, and an average inter-tissue difference of 5.1 permil between carnivore bone collagen (lower value) and bioapatite (higher value) carbon isotope values. Both of these isotopic differences differ from previous estimates derived from a suite of African carnivores; our carnivore-herbivore bone bioapatite carbon isotope spacing is smaller (-1.3 vs. -4.0 permil), and our carnivore collagen-bioapatite carbon difference is larger (5.1 vs. 3.0 permil). These discrepancies likely result from comparing values measured from a single hypercarnivore (wolf) to average values calculated from several carnivore species, some of which are insectivorous or partly omnivorous. The trophic and inter

Descriptions of carbon isotopes within the energy density functional theory

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

Ismail, Atef; Cheong, Lee Yen; Yahya, Noorhana

2014-10-24

Within the energy density functional (EDF) theory, the structure properties of Carbon isotopes are systematically studied. The shell model calculations are done for both even-A and odd-A nuclei, to study the structure of rich-neutron Carbon isotopes. The EDF theory indicates the single-neutron halo structures in {sup 15}C, {sup 17}C and {sup 19}C, and the two-neutron halo structures in {sup 16}C and {sup 22}C nuclei. It is also found that close to the neutron drip-line, there exist amazing increase in the neutron radii and decrease on the binding energies BE, which are tightly related with the blocking effect and correspondingly themore » blocking effect plays a significant role in the shell model configurations.« less

Stable isotopes of pedogenic carbonates from the Somma-Vesuvius area, southern Italy, over the past 18 kyr: palaeoclimatic implications

NASA Astrophysics Data System (ADS)

Zanchetta, G.; di Vito, M.; Fallick, A. E.; Sulpizio, R.

2000-12-01

Stable isotopes were measured in the carbonate and organic matter of palaeosols in the Somma-Vesuvius area, southern Italy in order to test whether they are suitable proxy records for climatic and ecological changes in this area during the past 18000 yr. The ages of the soils span from ca. 18 to ca. 3 kyr BP. Surprisingly, the Last Glacial to Holocene climate transition was not accompanied by significant change in 18O of pedogenic carbonate. This could be explained by changes in evaporation rate and in isotope fractionation between water and precipitated carbonate with temperature, which counterbalanced the expected change in isotope composition of meteoric water. Because of the rise in temperature and humidity and the progressive increase in tree cover during the Holocene, the Holocene soil carbonates closely reflect the isotopic composition of meteoric water. A cooling of about 2°C after the Avellino eruption (3.8 ka) accounts for a sudden decrease of about 1 in 18O of pedogenic carbonate recorded after this eruption. The 13C values of organic matter and pedogenic carbonate covary, indicating an effective isotope equilibrium between the organic matter, as the source of CO2, and the pedogenic carbonate. Carbon isotopes suggest prevailing C3 vegetation and negligible mixing with volcanogenic or atmospheric CO2.

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

PubMed

Porowska, Dorota

2015-05-01

Chemical and isotopic analyses of groundwater from piezometers located around a reclaimed landfill in Otwock (Poland) were performed in order to trace the origin of dissolved inorganic carbon (DIC) in the groundwater. Due to differences in the isotopic composition of carbon from different sources, an analysis of stable carbon isotopes in the groundwater, together with the Keeling plot approach and a two-component mixing model allow us to evaluate the relative contributions of carbon from these sources in the groundwater. In the natural (background) groundwater, DIC concentrations and the isotopic composition of DIC (δ(13)CDIC) comes from two sources: decomposition of organic matter and carbonate dissolution within the aquifer sediments, whereas in the leachate-contaminated groundwater, DIC concentrations and δ(13)CDIC values depend on the degradation of organic matter within the aquifer sediments and biodegradation of organic matter stored in the landfill. From the mixing model, about 4-54% of the DIC pool is derived from organic matter degradation and 96-46% from carbonate dissolution in natural conditions. In the leachate-contaminated groundwater, about 20-53% of the DIC is derived from organic matter degradation of natural origin and 80-47% from biodegradation of organic matter stored in the landfill. Partial pressure of CO2 (P CO2) was generally above the atmospheric, hence atmospheric CO2 as a source of carbon in DIC pool was negligible in the aquifer. P CO2 values in the aquifer in Otwock were always one to two orders of magnitude above the atmospheric P CO2, and thus CO2 escaped directly into the vadose zone. Copyright © 2015 Elsevier Ltd. All rights reserved.

Biological markers from Green River kerogen decomposition

NASA Astrophysics Data System (ADS)

Burnham, A. K.; Clarkson, J. E.; Singleton, M. F.; Wong, C. M.; Crawford, R. W.

1982-07-01

Isoprenoid and other carbon skeletons that are formed in living organisms and preserved essentially intact in ancient sediments are often called biological markers. The purpose of this paper is to develop improved methods of using isoprenoid hydrocarbons to relate petroleum or shale oil to its source rock. It is demonstrated that most, but not all, of the isoprenoid hydrocarbon structures are chemically bonded in kerogen (or to minerals) in Green River oil shale. The rate constant for thermally producing isoprenoid, cyclic, and aromatic hydrocarbons is substantially greater than for the bulk of shale oil. This may be related to the substantial quantity of CO 2 which is evolved coincident with the isoprenoid hydrocarbons but prior to substantial oil evolution. Although formation of isoprenoid alkenes is enhanced by rapid heating and high pyrolysis temperatures, the ratio of isoprenoid alkenes plus alkanes to normal alkenes plus alkanes is independent of heating rate. High-temperature laboratory pyrolysis experiments can thus be used to predict the distribution of aliphatic hydrocarbons in low temperature processes such as in situ shale oil production and perhaps petroleum formation. Finally, we demonstrate that significant variation in biological marker ratios occurs as a function of stratigraphy in the Green River formation. This information, combined with methods for measuring process yield from oil composition, enables one to relate time-dependent processing conditions to the corresponding time-dependent oil yield in a vertical modified- in situ retort even if there is a substantial and previously undetermined delay in drainage of shale oil from the retort.

Degradation of Perchloroethene by zero-valent iron evaluated by carbon isotope fractionation

NASA Astrophysics Data System (ADS)

Leitner, Simon; Watzinger, Andrea; Reichenauer, Thomas G.

2014-05-01

Perchloroethene (PCE) is a widely spread groundwater contaminant in formally used industrial sites. Zero valent iron (ZVI) is used for in situ chemical reduction (ISCR) of PCE contaminants in the groundwater. A key factor in the application of in situ remediation technologies is a proper monitoring of contaminant reduction. The measurement of the stable isotope ratio is a promising method that is already used for quantifying microbial degradation of chlorinated contaminants. The carbon isotope ratio of PCE, measured by - isotope ratio mass spectrometry coupled to a gas chromatograph via a combustion interface (GC-C-IRMS), increases during degradation of PCE and can be directly related to the degree of degradation. It can be used to directly quantify chemical degradation and thus serves as a useful monitoring tool for groundwater remediation. An experiment to determine the carbon isotopic fractionation factor was performed as a lab experiment using Nanofer Star (NANOIRON). Two different PCE concentrations (c1: 220mgL-1, c2: 110mgL-1) mixed with 0.5 g of ZVI were sealed under deoxygenated conditions in 250 ml glas bottles locked with mininert caps. The bottles were incubated on a shaker for 865 h. Samples were taken weekly to measure the change in the carbon isotopic ratio of PCE as well as its concentration. Results showed a strong increase in the carbon isotope ratio (δ-value) of PCE (start: -27 o end: -4 ), which indicates a significant dechlorination process of PCE. Beside PCE also one degradation product (Trichloroethylene - TCE) was measured. TCE was further dechlorinated as indicated by the δ-value change of TCE from -26 o to -4 oȦn unexpected intermediate value of -45 o for TCE was observed in the experiment. This fluctuation could be induced by the time depending concentration due to degradation and conversation processes. Furthermore, it seems that the progress of the δ-value is affected by the starting concentration of PCE (δ-value of c1 < c2) as

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

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

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

In spite of the massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Here we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases, and we usemore » molecular simulations to demonstrate it. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Finally, our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.« less

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

DOE PAGES

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-06-16

In spite of the massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Here we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases, and we usemore » molecular simulations to demonstrate it. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Finally, our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.« less

Isotopic analysis of groundwater and carbonate system in the Surdulica geothermal aquifer

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

Hadzisehovic, M; Miljevic, N.; Sipka, V.

1993-01-01

The authors present here results of their investigation of the isotopic chemical composition of groundwater and carbonates in the Surdulica geothermal aquifer, Serbia. They considered the effects of carbonate dissolution and measured [sup 13]C, [sup 14]C, D, [sup 18]O, [sup 3]H, field pH, temperature, Na[sup +], CA [sup 2+], Mg[sup 2+], HCO[sub 3] and other aqueous species from 30 springs and boreholes. Geothermal waters are supersaturated with calcite. Carbon isotope compositions vary with carbonate mineral dissolution. The [delta]D and [delta][sup 18]O of groundwater samples fit the meteoric water line, and indicate that groundwater is recharged mainly from higher altitudes andmore » the cold season. Different groundwater residence times point out two mechanisms for their formation: fissure flow for young waters and standard diffusion processes for old ones.« less

Effect of thermal decarbonation on the stable isotope composition of carbonates

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

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

2001-01-01

The unusual texture and stable isotope variability of carbonates in AH84001 have been used as evidence for early life on Mars (Romanek et al., 1994; McKay et al., 1996). Oxygen and carbon isotope variability is most commonly attributed to low-temperature processes, including Rayleigh-like fractionation associated with biological activity. Another possible explanation for the isotopic variability in meteoritic samples is thermal decarbonation. In this report, different carbonates were heated in a He-stream until decomposition temperatures were reached. The oxygen and carbon isotope ratios ({delta}{sup 18}O and {delta}{sup 13}C values) of the resulting gas were measured on a continuous flow isotope ratiomore » mass spectrometer. The aim of this work is to evaluate the possibility that large isotopic variations can be generated on a small scale abiogenically, by the process of thermal decarbonation. Oxygen isotope fractionations of >4{per_thousand} have been measured during decarbonation of calcite at high temperatures (McCrea, 1950), and in excess of 6{per_thousand} for dolomite decarbonated between 500 and 600 C (Sharma and Clayton, 1965). Isotopic fractionations of this magnitude, coupled with Rayleigh-like distillation behavior could result in very large isotopic variations on a small scale. To test the idea, calcite, dolomite and siderite were heated in a quartz tube in a He-stream in excess of 1 atmosphere. Simultaneous determinations of {delta}{sup 13}C and {Delta}{sup 18}O values were obtained on 250 {micro}l aliquots of the CO{sub 2}-bearing He gas using an automated 6-way switching valve system (Finnigan MAT GasBench II) and a Finnigan MAT Delta Plus mass spectrometer. It was found that decarbonation of calcite in a He atmosphere begins at 720 C, but the rate significantly increases at temperatures of 820 C. After an initial light {delta}{sup 18}O value of -14.1{per_thousand} at 720 C associated with very early decarbonation, {delta}{sup 18}0 values

Carbon isotopic patterns of amino acids associated with various microbial metabolic pathways and physiological conditions

NASA Astrophysics Data System (ADS)

Wang, P. L.; Hsiao, K. T.; Lin, L. H.

2017-12-01

Amino acids represent one of the most important categories of biomolecule. Their abundance and isotopic patterns have been broadly used to address issues related to biochemical processes and elemental cycling in natural environments. Previous studies have shown that various carbon assimilative pathways of microorganisms (e.g. autotrophy, heterotrophy and acetotrophy) could be distinguished by carbon isotopic patterns of amino acids. However, the taxonomic and catabolic coverage are limited in previous examination. This study aims to uncover the carbon isotopic patterns of amino acids for microorganisms remaining uncharacterized but bearing biogeochemical and ecological significance in anoxic environments. To fulfill the purpose, two anaerobic strains were isolated from riverine wetland and mud volcano in Taiwan. One strain is a sulfate reducing bacterium (related to Desulfovibrio marrakechensis), which is capable of utilizing either H2 or lactate, and the other is a methanogen (related to Methanolobus profundi), which grows solely with methyl-group compounds. Carbon isotope analyses of amino acids were performed on cells grown in exponential and stationary phase. The isotopic patterns were similar for all examined cultures, showing successive 13C depletion along synthetic pathways. No significant difference was observed for the methanogen and lactate-utilizing sulfate reducer harvested in exponential and stationary phases. In contrast, the H2-utilizing sulfate reducer harvested in stationary phase depleted and enriched 13C in aspartic acid and glycine, respectively when compared with that harvested in exponential phase. Such variations might infer the change of carbon flux during synthesis of these two amino acids in the reverse TCA cycle. In addition, the discriminant function analysis for all available data from culture studies further attests the capability of using carbon isotope patterns of amino acids in identifying microbial metabolisms.

Reconstruction of limnology and microbialite formation conditions from carbonate clumped isotope thermometry.

PubMed

Petryshyn, V A; Lim, D; Laval, B L; Brady, A; Slater, G; Tripati, A K

2015-01-01

Quantitative tools for deciphering the environment of microbialite formation are relatively limited. For example, the oxygen isotope carbonate-water geothermometer requires assumptions about the isotopic composition of the water of formation. We explored the utility of using 'clumped' isotope thermometry as a tool to study the temperatures of microbialite formation. We studied microbialites recovered from water depths of 10-55 m in Pavilion Lake, and 10-25 m in Kelly Lake, spanning the thermocline in both lakes. We determined the temperature of carbonate growth and the (18)O/(16)O ratio of the waters that microbialites grew in. Results were then compared to current limnological data from the lakes to reconstruct the history of microbialite formation. Modern microbialites collected at shallow depths (11.7 m) in both lakes yield clumped isotope-based temperatures of formation that are within error of summer water temperatures, suggesting that clumped isotope analyses may be used to reconstruct past climates and to probe the environments in which microbialites formed. The deepest microbialites (21.7-55 m) were recovered from below the present-day thermoclines in both lakes and yield radioisotope ages indicating they primarily formed earlier in the Holocene. During this time, pollen data and our reconstructed water (18)O/(16)O ratios indicate a period of aridity, with lower lake levels. At present, there is a close association between both photosynthetic and heterotrophic communities, and carbonate precipitation/microbialite formation, with biosignatures of photosynthetic influences on carbonate detected in microbialites from the photic zone and above the thermocline (i.e., depths of generally <20 m). Given the deeper microbialites are receiving <1% of photosynthetically active radiation (PAR), it is likely these microbialites primarily formed when lower lake levels resulted in microbialites being located higher in the photic zone, in warm surface waters. © 2014 John

The synthesis of a tritium, carbon-14, and stable isotope-labeled cathepsin C inhibitors.

PubMed

Allen, Paul; Bragg, Ryan A; Caffrey, Moya; Ericsson, Cecilia; Hickey, Michael J; Kingston, Lee P; Elmore, Charles S

2017-02-01

As part of a medicinal chemistry program aimed at developing a highly potent and selective cathepsin C inhibitor, tritium, carbon-14, and stable isotope-labeled materials were required. The synthesis of tritium-labeled methanesulfonate 5 was achieved via catalytic tritiolysis of a chloro precursor, albeit at a low radiochemical purity of 67%. Tritium-labeled AZD5248 was prepared via a 3-stage synthesis, utilizing amide-directed hydrogen isotope exchange. Carbon-14 and stable isotope-labeled AZD5248 were successfully prepared through modifications of the medicinal chemistry synthetic route, enabling the use of available labeled intermediates. Copyright © 2016 John Wiley & Sons, Ltd.

Compiled records of carbon isotopes in atmospheric CO2 for historical simulations in CMIP6

NASA Astrophysics Data System (ADS)

Graven, Heather; Allison, Colin E.; Etheridge, David M.; Hammer, Samuel; Keeling, Ralph F.; Levin, Ingeborg; Meijer, Harro A. J.; Rubino, Mauro; Tans, Pieter P.; Trudinger, Cathy M.; Vaughn, Bruce H.; White, James W. C.

2017-12-01

The isotopic composition of carbon (Δ14C and δ13C) in atmospheric CO2 and in oceanic and terrestrial carbon reservoirs is influenced by anthropogenic emissions and by natural carbon exchanges, which can respond to and drive changes in climate. Simulations of 14C and 13C in the ocean and terrestrial components of Earth system models (ESMs) present opportunities for model evaluation and for investigation of carbon cycling, including anthropogenic CO2 emissions and uptake. The use of carbon isotopes in novel evaluation of the ESMs' component ocean and terrestrial biosphere models and in new analyses of historical changes may improve predictions of future changes in the carbon cycle and climate system. We compile existing data to produce records of Δ14C and δ13C in atmospheric CO2 for the historical period 1850-2015. The primary motivation for this compilation is to provide the atmospheric boundary condition for historical simulations in the Coupled Model Intercomparison Project 6 (CMIP6) for models simulating carbon isotopes in the ocean or terrestrial biosphere. The data may also be useful for other carbon cycle modelling activities.

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

EPA Pesticide Factsheets

Data set from “Patterns in stable isotope values of nitrogen and carbon in particulate matter from the Northwest Atlantic Continental Shelf, from the Gulf of Maine to Cape Hatteras” by Oczkowski et al. These are the data upon which all results and conclusion are made. Publishing the data allow for use by wider audience. Stable isotope dynamics on the shelf can inform both nearshore and open ocean research efforts, providing an important link along the marine continuum. To our knowledge, this data set is unique in its spatial coverage and variables measured.

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

NASA Technical Reports Server (NTRS)

Yuen, G.; Blair, N.; Des Marais, D. J.; Chang, S.

1984-01-01

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 carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar, and impose constraints on the identity of the reactant species.

Carbonate “clumped” isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

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

Kimball, Justine; Eagle, Robert; Dunbar, Robert

Here, deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop “clumped” isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C 18O 16O 2 inmore » carbonate minerals, analyzed in CO 2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ 47 values. We analyzed Δ 47 in live-collected aragonitic scleractinian ( Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ 47 values were compared to in situ temperatures, and the relationship between Δ 47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ 47–temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ 47–temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO 2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these

Carbonate “clumped” isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

DOE PAGES

Kimball, Justine; Eagle, Robert; Dunbar, Robert

2016-12-12

Here, deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop “clumped” isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C 18O 16O 2 inmore » carbonate minerals, analyzed in CO 2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ 47 values. We analyzed Δ 47 in live-collected aragonitic scleractinian ( Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ 47 values were compared to in situ temperatures, and the relationship between Δ 47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ 47–temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ 47–temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO 2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these

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

USGS Publications Warehouse

Warwick, Peter D.; Ruppert, Leslie F.

2016-01-01

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

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

USGS Publications Warehouse

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-01-01

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals.We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect.Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3− and CO32−. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many

Surface area dependence of calcium isotopic reequilibration in carbonates: Implications for isotopic signatures in the weathering zone

NASA Astrophysics Data System (ADS)

Fernandez, N. M.; Druhan, J. L.; Potrel, A.; Jacobson, A. D.

2016-12-01

The concept of dynamic equilibrium carries the implicit assumption of continued isotopic exchange between a mineral and the surrounding fluid. While this effect has received much attention in the marine paleoproxy literature, it has been relatively overlooked in application to the terrestrial environment. In weathering systems, a potential consequence is that rapid reequilibration may alter or erase isotopic signatures generated during secondary mineral formation. The extent and timescale over which isotopic signatures are reset in these hydrologic systems is unknown. Using reactive transport modeling, we show isotopic reequilibration under conditions reflecting terrestrial hydrologic settings to be significant and dependent on the reactive surface area of the solid. In particular, we suggest that the non-traditional stable isotopes commonly used in application to carbonates (e.g., Ca, Mg, Sr) are sensitive to these effects due to their rapid reaction rates. We aim to characterize the dependence of Ca isotopic reequilibration on surface area during calcite precipitation via batch experiments conducted at ambient temperature over 48-hour time periods. Calcite precipitation was performed in a closed batch reactor utilizing a controlled free-drift method. The batch reactors contained mixed supersaturated solutions of CaCl2 and NaHCO3 at an initial pH of 8.54. Precipitation was initiated by seed inoculation of calcite crystals with two distinct, pre-constrained surface areas. All experiments achieved the same final state of chemical equilibrium, but as expected, the fastest approach to equilibrium occurred for experiments employing calcite seeds with the highest surface area. This implies that differences in equilibrated Ca isotope ratios (δ44/40Ca) should reflect differences in surface area. This prediction is upheld by models of the experiments, indicating a measureable difference in δ44Ca during calcite precipitation where the higher surface area corresponds to

Uranium Isotopes in Calcium Carbonate: A Possible Proxy for Paleo-pH and Carbonate Ion Concentration?

NASA Astrophysics Data System (ADS)

Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Wasylenki, L. E.; Anbar, A. D.

2015-12-01

Natural variations of 238U/235U in marine carbonates are being explored as a paleoredox proxy. However, in order for this proxy to be robust, it is important to understand how pH and alkalinity affect the fractionation of 238U/235U during coprecipitation with calcite and aragonite. Recent work suggests that the U/Ca ratio of foraminiferal calcite may vary with seawater [CO32-] concentration due to changes in U speciation[1]. Here we explore analogous isotopic consequences in inorganic laboratory co-precipitation experiments. Uranium coprecipitation experiments with calcite and aragonite were performed at pH 8.5 ± 0.1 and 7.5 ± 0.1 using a constant addition method [2]. Dissolved U in the remaining solution was periodically collected throughout the experiments. Samples were purified with UTEVA resin and 238U/235U was determined using a 233U-236U double-spike and MC-ICP-MS, attaining a precision of ± 0.10 ‰ [3]. Small but resolvable U isotope fractionation was observed in aragonite experiments at pH ~8.5, preferentially enriching heavier U isotopes in the solid phase. 238U/235U of the dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00002 - 1.00009. In contrast, no resolvable U isotope fractionation was detected in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among dissolved U species is the most likely mechanism driving these isotope effects. Our quantitative model of this process assumes that charged U species are preferentially incorporated into CaCO3 relative to the neutral U species Ca2UO2(CO3)3(aq), which we hypothesize to have a lighter equilibrium U isotope composition than the charged U species. According to this model, the magnitude of U isotope fractionation should scale with the fraction of the neutral U species in the solution, in agreement with our experimental results. These findings suggest that U isotope variations in

Springtime carbon emission episodes at the Gosan background site revealed by total carbon, stable carbon isotopic composition, and thermal characteristics of carbonaceous particles

NASA Astrophysics Data System (ADS)

Jung, J.; Kawamura, K.

2011-11-01

In order to investigate the emission of carbonaceous aerosols at the Gosan background super-site (33.17° N, 126.10° E) in East Asia, total suspended particles (TSP) were collected during spring of 2007 and 2008 and analyzed for particulate organic carbon, elemental carbon, total carbon (TC), total nitrogen (TN), and stable carbon isotopic composition (δ13C) of TC. The stable carbon isotopic composition of TC (δ13CTC) was found to be lowest during pollen emission episodes (range: -26.2‰ to -23.5‰, avg. -25.2 ± 0.9‰), approaching those of the airborne pollen (-28.0‰) collected at the Gosan site. Based on a carbon isotope mass balance equation, we found that ~42% of TC in the TSP samples during the pollen episodes was attributed to airborne pollen from Japanese cedar trees planted around tangerine farms in Jeju Island. A negative correlation between the citric acid-carbon/TC ratios and δ13CTC was obtained during the pollen episodes. These results suggest that citric acid emitted from tangerine fruit may be adsorbed on the airborne pollen and then transported to the Gosan site. Thermal evolution patterns of organic carbon during the pollen episodes were characterized by high OC evolution in the OC2 temperature step (450 °C). Since thermal evolution patterns of organic aerosols are highly influenced by their molecular weight, they can be used as additional information on the formation of secondary organic aerosols and the effect of aging of organic aerosols during the long-range atmospheric transport and sources of organic aerosols.

The carbon and oxygen isotope records of reef-dwelling foraminifers subjected to five varied pCO2 seawater

NASA Astrophysics Data System (ADS)

Hikami, M.; Ishimura, T.; Suzuki, A.; Nojiri, Y.; Kawahata, H.

2013-12-01

Ocean acidification (OA) in response to rising atmospheric pCO2 is generally expected to reduce rates of calcification by reef calcifying organisms, with potentially severe implications for coral reef ecosystems. Reef dwelling foraminifera is one of the most important primary and carbonate producers in coral reef environments. Their shells are composed of high-Mg calcite and they are host to algal endosymbionts. In our previous culture experiment with two algal reef dwelling foraminifers, Amphisorus kudakajimensis and Calcarina gaudichaudii in the seawater of five different pCO2 conditions, net calcification of A. kudakajimensis was reduced under higher pCO2, whereas net calcification of C. gaudichaudii showed continued increasing trend with pCO2. These contrasting responses between the two species are possibly due to differences in calcification mechanisms and to links between calcification by the foraminifers and photosynthesis by the algal endosymbionts. But the factors affecting these calcification mechanisms are poorly understood. In this study, to get a better understanding of the effect of OA on their calcification, we cultured three reef dwelling foraminifers: Amphisorus hemprichii, belong to imperforate species, Baculogypsina sphaerulata, and C. gaudichaudii belong to perforate species, in the seawater of five different pCO2 conditions and we address the response of carbon and oxygen isotopes of the carbonate shells of foraminifers. The oxygen isotope ratio of cultured foraminiferal tests under five varied pCO2 seawater indicated no significant correlation to pCO2 values. On the other hand, the carbon isotope ratio of foraminiferal tests indicated heavy trend with rising pCO2 in all species. Alteration of carbonate chemistry result from ocean acidification may be effect strongly on carbon isotope composition relate to metabolic system (i.e. photosynthesis and respiration). In perforate species, both of oxygen and carbon isotope ratio were lighter than that

Stable carbon and nitrogen isotopes in vertical peat profiles of natural and drained boreal peatlands

NASA Astrophysics Data System (ADS)

Nykänen, Hannu; Mpamah, Promise; Rissanen, Antti; Pitkänen, Aki; Turunen, Jukka; Simola, Heikki

2015-04-01

Peatlands form a significant carbon pool in the global carbon cycle. Change in peat hydrology, due to global warming is projected to change microbiological processes and peat carbon pool. We tested if bulk stable carbon and nitrogen isotopes serve as indicators of severe long term drying in peatlands drained for forestry. Depth profile analysis of peat, for their carbon and nitrogen content as well as their carbon and nitrogen stable isotopic signatures, were conducted for peatlands in southern and eastern Finland, having ombrotrophic and minerotrophic natural and corresponding drained pairs or separate drained sites. The selection of sites allowed us to compare changes due to different fertility and changes due to long term artificial drying. Drainage lasting over 40 years has led to changes in hydrology, vegetation, nutrient mineralization and respiration. Furthermore, increased nutrient uptake and possible recycling of peat nitrogen and carbon trough vegetation back to the peat surface, also possibly has an effect on the stable isotopic composition of peat carbon and nitrogen. We think that drainage induced changes somehow correspond to those caused by changed hydrology due to climate change. We will present data from these measurements and discuss their implications for carbon and nitrogen flows in peatlands.

Application of carbon isotope stratigraphy to late miocene shallow marine sediments, new zealand.

PubMed

Loutit, T S; Kennett, J P

1979-06-15

A distinct (0.5 per mil) carbon-13/carbon-12 isotopic shift in the light direction has been identified in a shallow marine sedimentary sequence of Late Miocene age at Blind River, New Zealand, and correlated with a similar shift in Late Miocene Deep Sea Drilling Project sequences throughout the Indo-Pacific. A dated piston core provides an age for the shift of 6.2 +/- 0.1 million years. Correlations based on the carbon isotopic change require a revision of the previously established magnetostratigraphy at Blind River. The carbon shift at Blind River occurs between 6.2 and 6.3 +/- 0.1 million years before present. A new chronology provides an age for the evolutionary first appearance datum of Globorotalia conomiozea at 6.1 +/- 0.1 million years, the beginning of a distinct latest Miocene cooling event associated with the Kapitean stage at 6.2 +/- 0.1 million years, and the beginning of a distinct shallowing of water depths at 6.1 +/- 0.1 million years. The Miocene-Pliocene boundary as recognized in New Zealand is now dated at 5.3 +/- 0.1 million years. Extension of carbon isotope stratigraphy to other shallow Late Miocene sequences should provide an important datum for international correlation of Late Miocene shallow and deep marine sequences.

Carbon isotope ratios of human tooth enamel record the evidence of terrestrial resource consumption during the Jomon period, Japan.

PubMed

Kusaka, Soichiro; Uno, Kevin T; Nakano, Takanori; Nakatsukasa, Masato; Cerling, Thure E

2015-08-17

Archaeological remains strongly suggest that the Holocene Japanese hunter-gatherers, the Jomon people, utilized terrestrial plants as their primary food source. However, carbon and nitrogen isotope analysis of bone collagen indicates that they primarily exploited marine resources. We hypothesize that this inconsistency stems from the route of protein synthesis and the different proportions of protein-derived carbon in tooth enamel versus bone collagen. Carbon isotope ratios from bone collagen reflect that of dietary protein and may provide a biased signal of diet, whereas isotope ratios from tooth enamel reflect the integrated diet from all macronutrients (carbohydrates, lipids, and proteins). In order to evaluate the differences in inferred diet between the archaeological evidence and bone collagen isotope data, this study investigated carbon isotopes in Jomon tooth enamel from four coastal sites of the Middle to Late-Final Jomon period (5,000-2,300 years BP). Carbon isotope ratios of human teeth are as depleted as coeval terrestrial mammals, suggesting that C 3 plants and terrestrial mammals were major dietary resources for the Jomon people. Dietary dependence on marine resources calculated from enamel was significantly lower than that calculated from bone collagen. The discrepancy in isotopic ratios between enamel and collagen and the nitrogen isotope ratio in collagen shows a negative correlation on individual and population levels, suggesting diets with variable proportions of terrestrial and marine resources. This study highlights the usefulness of coupling tooth enamel and bone collagen in carbon isotopic studies to reconstruct prehistoric human diet. Am J Phys Anthropol, 2015. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

Cerium anomaly across the mid-Tournaisian carbon isotope excursion (TICE)

NASA Astrophysics Data System (ADS)

Jiang, G.; Morales, D. C.; Maharjan, D. K.

2015-12-01

The Early Mississippian (ca. 359-345 Ma) represents one of the most important greenhouse-icehouse climate transitions in Earth history. Closely associated with this critical transition is a prominent positive carbon isotope excursion (δ13C ≥ +5‰) that has been documented from numerous stratigraphic successions across the globe. This δ13C excursion, informally referred to as the TICE (mid-Tournaisian carbon isotope excursion) event, has been interpreted as resulting from enhanced organic carbon burial, with anticipated outcomes including the lowering of atmospheric CO2 and global cooling, the growth of continental ice sheets and sea-level fall, and the increase of ocean oxygenation and ocean redox changes. The casual relationship between these events has been addressed from various perspectives but not yet clearly demonstrated. To document the potential redox change associated with the perturbation of the carbon cycle, we have analyzed rare earth elements (REE) and trace elements across the TICE in two sections across a shallow-to-deep water transect in the southern Great Basin (Utah and Nevada), USA. In both sections, the REE data show a significant positive cerium (Ce) anomaly (Ce/Ce* = Ce/(0.5La+0.5Pr)). Prior to the positive δ13C shift, most Ce/Ce* values are around 0.3 (between 0.2 and 0.4). Across the δ13C peak, Ce/Ce* values increase up to 0.87, followed by a decrease back to 0.2~0.3 after the δ13C excursion (Figure 1). The positive Ce anomaly is best interpreted as recording expansion of oxygen minimum zone and anoxia resulted from increased primary production. This is consistent with a significant increase of nitrogen isotopes (δ15N) across the δ13C peak. Integration of the carbon, nitrogen, and REE data demonstrates a responsive earth systems change linked to the perturbation of the Early Mississippian carbon cycle.

The use of carbon stable isotope ratios in drugs characterization

NASA Astrophysics Data System (ADS)

Magdas, D. A.; Cristea, G.; Bot, A.; Mirel, V.

2013-11-01

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 δ13C 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.

Stable Isotope Measurements of Carbon Dioxide, Methane, and Hydrogen Sulfide Gas Using Frequency Modulation Spectroscopy

NASA Astrophysics Data System (ADS)

Nowak-Lovato, K.

2014-12-01

Seepage from enhanced oil recovery, carbon storage, and natural gas sites can emit trace gases such as carbon dioxide, methane, and hydrogen sulfide. Trace gas emission at these locations demonstrate unique light stable isotope signatures that provide information to enable source identification of the material. Light stable isotope detection through surface monitoring, offers the ability to distinguish between trace gases emitted from sources such as, biological (fertilizers and wastes), mineral (coal or seams), or liquid organic systems (oil and gas reservoirs). To make light stable isotope measurements, we employ the ultra-sensitive technique, frequency modulation spectroscopy (FMS). FMS is an absorption technique with sensitivity enhancements approximately 100-1000x more than standard absorption spectroscopy with the advantage of providing stable isotope signature information. We have developed an integrated in situ (point source) system that measures carbon dioxide, methane and hydrogen sulfide with isotopic resolution and enhanced sensitivity. The in situ instrument involves the continuous collection of air and records the stable isotope ratio for the gas being detected. We have included in-line flask collection points to obtain gas samples for validation of isotopic concentrations using our in-house isotope ratio mass spectroscopy (IRMS). We present calibration curves for each species addressed above to demonstrate the sensitivity and accuracy of the system. We also show field deployment data demonstrating the capabilities of the system in making live dynamic measurements from an active source.

Enantioselective carbon stable isotope fractionation of hexachlorocyclohexane during aerobic biodegradation by Sphingobium spp.

PubMed

Bashir, Safdar; Fischer, Anko; Nijenhuis, Ivonne; Richnow, Hans-Hermann

2013-10-15

Carbon isotope fractionation was investigated for the biotransformation of γ- and α- hexachlorocyclohexane (HCH) as well as enantiomers of α-HCH using two aerobic bacterial strains: Sphingobium indicum strain B90A and Sphingobium japonicum strain UT26. Carbon isotope enrichment factors (ε(c)) for γ-HCH (ε(c) = -1.5 ± 0.1 ‰ and -1.7 ± 0.2 ‰) and α-HCH (ε(c) = -1.0 ± 0.2 ‰ and -1.6 ± 0.3 ‰) were similar for both aerobic strains, but lower in comparison with previously reported values for anaerobic γ- and α-HCH degradation. Isotope fractionation of α-HCH enantiomers was higher for (+) α-HCH (ε(c) = -2.4 ± 0.8 ‰ and -3.3 ± 0.8 ‰) in comparison to (-) α-HCH (ε(c) = -0.7 ± 0.2 ‰ and -1.0 ± 0.6 ‰). The microbial fractionation between the α-HCH enantiomers was quantified by the Rayleigh equation and enantiomeric fractionation factors (ε(e)) for S. indicum strain B90A and S. japonicum strain UT26 were -42 ± 16% and -22 ± 6%, respectively. The extent and range of isomer and enantiomeric carbon isotope fractionation of HCHs with Sphingobium spp. suggests that aerobic biodegradation of HCHs can be monitored in situ by compound-specific stable isotope analysis (CSIA) and enantiomer-specific isotope analysis (ESIA). In addition, enantiomeric fractionation has the potential as a complementary approach to CSIA and ESIA for assessing the biodegradation of α-HCH at contaminated field sites.

Evaluating Uranium Isotopes in Carbonates and Implications for Reconstructing Marine Paleoredox Conditions

NASA Astrophysics Data System (ADS)

Aharony, Ofer; Gubser, Steven S.; Maldacena, Juan; Ooguri, Hirosi; Oz, Yaron

2016-12-01

Uranium isotope ratios (238U/235U, reported as δ238U) have emerged as a promising proxy for marine redox conditions. This proxy relies on isotopic fractionation that occurs during reduction of soluble U(VI) to insoluble U(IV), wherein 238U is preferentially reduced and incorporated via authigenic processes into anoxic sediments, leaving the residual seawater U and resulting carbonates 238U-depleted. Because carbonates are generally well preserved in the rock record, they are useful archives of seawater chemistry throughout Earth history, including δ238U. In principle, the long residence time of U in the ocean permits quantitative inferences of global paleoredox conditions using carbonate δ238U records. To assess the performance of the proxy, we compile all published δ238U measurements from carbonate rocks and sediments, which span the Cryogenian through the modern. The potential for δ238U to serve as a quantitative, global paleoredox proxy is supported by reproducible trends across depositional environments and paleogeographic regions in the Cryogenian non-glacial interlude and across the Permian-Triassic and Triassic-Jurassic boundaries, although carbonates deposited in deeper waters (>200 m) may be subject to local effects. Using a box model, we highlight the key levers associated with seawater δ238U and the timescales of such variability. Like all sedimentary archives, carbonate rocks are prone to diagenetic alteration and additional controls that cause δ238U in carbonates to deviate from global seawater values. Specifically, the U isotopic composition of carbonate sediments can be influenced by diagenesis, carbonate mineralogy, dolomitization, detrital input, local organic matter deposition, and pore water chemistry. We evaluate indicators of these factors in the context of a diagenetic model to assess the sensitivity of carbonate δ238U to local syndepositional or post-depositional processes. These results improve the framework for interpreting

A Carbon Source Apportionment Shift in Mexico City Atmospheric Particles During 2003-2004 as Determined with Stable Carbon Isotopes

NASA Astrophysics Data System (ADS)

Lopez-Veneroni, D. G.; Vega, E.

2013-05-01

The stable carbon isotope composition of atmospheric particles (PM2.5) was measured at La Merced (MER), a commercial site in the eastern sector, and at Xalostoc (XAL) an industrial site in the NE sector of Mexico City, during three sampling periods in autumn 2003, and spring and autumn 2004. At each site and sampling campaign particle samples were collected daily with minivol samplers during two week periods. Ancillary data included organic and elemental carbon, trace elements and ionic species. This data base was complement with air quality data from the RAMA (Automatic Atmospheric Monitoring Network). In general, particle concentrations, ionic species and some air quality species showed higher concentrations in autumn and lowest values in spring. Moreover, the concentrations of these chemical species were highest at XAL compared to MER. The stable carbon isotope composition of PM2.5 during autumn 2003 and spring 2004 had and average value of -26.04 (± 1.54) ‰ vs. PDB. Differences in the isotopic composition between the two sites were non significant. The average δ13C during these seasons were 1 ‰ lighter relative to data collected previously at these sites during 2000 and 2001, and is consistent with a predominant source of hydrocarbon combustion. In autumn 2004, however, average δ13C at XAL and MER increased to -22.8 (± 0.9) and -20.6 (± 3.1) ‰, respectively. Organic carbon concentrations during this period increased concomitantly at these sites. The shift in the isotopic composition in ambient particles suggests a predominance of soil-derived carbon during this period. The possible causes and implications of this are discussed.

PRODUCTION AND TRANSPORT OF CARBON DIOXIDE IN A CONTAMINATED VADOSE ZONE: A STABLE AND RADIOACTIVE CARBON ISOTOPE STUDY

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...

Soil moisture effects on the carbon isotope composition of soil respiration

Treesearch

Claire L. Phillips; Nick Nickerson; David Risk; Zachary E. Kayler; Chris Andersen; Alan Mix; Barbara J. Bond

2010-01-01

The carbon isotopic composition (δ13C) of recently assimilated plant carbon is known to depend on water-stress, caused either by low soil moisture or by low atmospheric humidity. Air humidity has also been shown to correlate with the δ13C of soil respiration, which suggests indirectly that recently fixed photosynthates...

STABLE ISOTOPIC EVIDENCE OF CARBON AND NITROGEN USE IN CULTURED ECTOMYCORRHIZAL AND SAPROTROPHIC FUNGI

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

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

2006-01-01

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.

Carbon and Hydrogen Isotope Fractionation in Lipid Biosynthesis of Piezophilic Bacteria - Implications for Studying Microbial Metabolism and Carbon Cycle in Deep Biosphere

NASA Astrophysics Data System (ADS)

Fang, J.; Dasgupta, S.; Zhang, L.; Li, J.; Kato, C.; Bartlett, D.

2012-12-01

Piezophiles are pressure-loving microorganisms, which reproduce preferentially or exclusively at pressures greater than atmospheric pressure. In this study, we examined stable carbon and hydrogen isotope fractionation in fatty acid biosynthesis of a piezophilic bacterium Moritella japonica DSK1. The bacterium was grown to stationary phase at hydrstatic pressures of 0.1, 10, 20, and 50 MPa (mega-passcal) in media prepared using sterilized natural seawater supplied with glucose as the sole carbon source. Bacterial cell biomass and individual fatty acids exhibited consistent pressure-dependent carbon and hydrogen isotope fractionations relative to substrates. Average carbon isotope fractionation (delta(FA-glucose)) at high pressures was much higher than that for surface bacteria: -15.7, -15.3, and -18.3‰ at 10, 20, and 50 MPa, respectively. For deltaD, fatty acids are more depleted in D relative to glucose than to water. Monounsaturated fatty acids are more depleted in D than corresponding saturated fatty acids by as much as 36‰. Polyunsaturated fatty acids are most depleted in D. For example, DHA (22:6omega3) has the most negative hydrogen isotope ratio (-170.91‰) (delta(FA-glucose) = -199, delta(FA-water) = -176). The observed isotope effects can be ascribed to the kinetics of enzymatic reactions that are affected by hydrostatic pressure and to operating of two independent lipid biosynthetic pathways of the piezophilic bacteria. Given that most of the biosphere lives under high pressures, our results have important important implications for studying microbial metabolism and carbon cycle in the deep biosphere.

Large Carbonate Associated Sulfate isotopic variability between brachiopods, micrite, and other sedimentary components in Late Ordovician strata

NASA Astrophysics Data System (ADS)

Present, Theodore M.; Paris, Guillaume; Burke, Andrea; Fischer, Woodward W.; Adkins, Jess F.

2015-12-01

Carbonate Associated Sulfate (CAS) is trace sulfate incorporated into carbonate minerals during their precipitation. Its sulfur isotopic composition is often assumed to track that of seawater sulfate and inform global carbon and oxygen budgets through Earth's history. However, many CAS sulfur isotope records based on bulk-rock samples are noisy. To determine the source of bulk-rock CAS variability, we extracted CAS from different internal sedimentary components micro-drilled from well-preserved Late Ordovician and early Silurian-age limestones from Anticosti Island, Quebec, Canada. Mixtures of these components, whose sulfur isotopic compositions vary by nearly 25‰, can explain the bulk-rock CAS range. Large isotopic variability of sedimentary micrite CAS (34S-depleted from seawater by up to 15‰) is consistent with pore fluid sulfide oxidation during early diagenesis. Specimens recrystallized during burial diagenesis have CAS 34S-enriched by up to 9‰ from Hirnantian seawater, consistent with microbial sulfate reduction in a confined aquifer. In contrast to the other variable components, brachiopods with well-preserved secondary-layer fibrous calcite-a phase independently known to be the best-preserved sedimentary component in these strata-have a more homogeneous isotopic composition. These specimens indicate that seawater sulfate remained close to about 25‰ (V-CDT) through Hirnantian (end-Ordovician) events, including glaciation, mass extinction, carbon isotope excursion, and pyrite-sulfur isotope excursion. The textural relationships between our samples and their CAS isotope ratios highlight the role of diagenetic biogeochemical processes in setting the isotopic composition of CAS.

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

PubMed

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

2007-01-01

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

Carbon isotope fractionation by sulfate-reducing bacteria using different pathways for the oxidation of acetate.

PubMed

Goevert, Dennis; Conrad, Ralf

2008-11-01

Acetate is a key intermediate in the anaerobic degradation of organic matter. In anoxic environments, available acetate is a competitive substrate for sulfate-reducing bacteria (SRB) and methane-producing archaea. Little is known about the fractionation of carbon isotopes by sulfate reducers. Therefore, we determined carbon isotope compositions in cultures of three acetate-utilizing SRB, Desulfobacter postgatei, Desulfobacter hydrogenophilus, and Desulfobacca acetoxidans. We found that these species showed strong differences in their isotope enrichment factors (epsilon) of acetate. During the consumption of acetate and sulfate, acetate was enriched in 13C by 19.3% per hundred in Desulfobacca acetoxidans. By contrast, both D. postgatei and D. hydrogenophilus showed a slight depletion of 13C resulting in epsilon(ac)-values of 1.8 and 1.5% per hundred, respectively. We suggest that the different isotope fractionation is due to the different metabolic pathways for acetate oxidation. The strongly fractionating Desulfobacca acetoxidans uses the acetyl-CoA/carbon monoxide dehydrogenase pathway, which is also used by acetoclastic methanogens that show a similar fractionation of acetate (epsilon(ac) = -21 to -27% per hundred). In contrast, Desulfobacter spp. oxidize acetate to CO2 via the tricarboxylic acid (TCA) cycle and apparently did not discriminate against 13C. Our results suggestthat carbon isotope fractionation in environments with sulfate reduction will strongly depend on the composition of the sulfate-reducing bacterial community oxidizing acetate.

Simulation of dual carbon-bromine stable isotope fractionation during 1,2-dibromoethane degradation.

PubMed

Jin, Biao; Nijenhuis, Ivonne; Rolle, Massimo

2018-06-01

We performed a model-based investigation to simultaneously predict the evolution of concentration, as well as stable carbon and bromine isotope fractionation during 1,2-dibromoethane (EDB, ethylene dibromide) transformation in a closed system. The modelling approach considers bond-cleavage mechanisms during different reactions and allows evaluating dual carbon-bromine isotopic signals for chemical and biotic reactions, including aerobic and anaerobic biological transformation, dibromoelimination by Zn(0) and alkaline hydrolysis. The proposed model allowed us to accurately simulate the evolution of concentrations and isotope data observed in a previous laboratory study and to successfully identify different reaction pathways. Furthermore, we illustrated the model capabilities in degradation scenarios involving complex reaction systems. Specifically, we examined (i) the case of sequential multistep transformation of EDB and the isotopic evolution of the parent compound, the intermediate and the reaction product and (ii) the case of parallel competing abiotic pathways of EDB transformation in alkaline solution.

Hydrogen and carbon isotope fractionation during degradation of chloromethane by methylotrophic bacteria

PubMed Central

Nadalig, Thierry; Greule, Markus; Bringel, Françoise; Vuilleumier, Stéphane; Keppler, Frank

2013-01-01

Chloromethane (CH3Cl) is a widely studied volatile halocarbon involved in the destruction of ozone in the stratosphere. Nevertheless, its global budget still remains debated. Stable isotope analysis is a powerful tool to constrain fluxes of chloromethane between various environmental compartments which involve a multiplicity of sources and sinks, and both biotic and abiotic processes. In this study, we measured hydrogen and carbon isotope fractionation of the remaining untransformed chloromethane following its degradation by methylotrophic bacterial strains Methylobacterium extorquens CM4 and Hyphomicrobium sp. MC1, which belong to different genera but both use the cmu pathway, the only pathway for bacterial degradation of chloromethane characterized so far. Hydrogen isotope fractionation for degradation of chloromethane was determined for the first time, and yielded enrichment factors (ε) of −29‰ and −27‰ for strains CM4 and MC1, respectively. In agreement with previous studies, enrichment in 13C of untransformed CH3Cl was also observed, and similar isotope enrichment factors (ε) of −41‰ and −38‰ were obtained for degradation of chloromethane by strains CM4 and MC1, respectively. These combined hydrogen and carbon isotopic data for bacterial degradation of chloromethane will contribute to refine models of the global atmospheric budget of chloromethane. PMID:24019296

Toward estimation of origin of methane at ancient seeps — Carbon isotopes of seep carbonates, lipid biomarkers, and adsorbed gas

NASA Astrophysics Data System (ADS)

Miyajima, Yusuke; Watanabe, Yumiko; Ijiri, Akira; Goto, Akiko; Jenkins, Robert; Hasegawa, Takashi; Sakai, Saburo; Matsumoto, Ryo

2017-04-01

Methane is generated mainly by microbial or thermal degradation of organic matter, and the origin of methane can be estimated based on its stable carbon isotopic signature. Seafloor seepages of methane-charged fluids have been a major source of methane to the ocean, and knowing the origin of methane at the methane seeps can provide valuable insights into the subsurface fluid circulation and biogeochemical processes. Methane seeps in the geological past are archived as authigenic methane-derived carbonate rocks, which precipitate via an alkalinity increase facilitated by microbially mediated anaerobic oxidation of methane. Here we attempted to estimate origins of methane at ancient seeps, based on several proxies preserved within the seep carbonates. We examined methane-seep carbonate rocks in the Japan Sea region, collected from lower Miocene to middle Pleistocene sediments at 11 sites on land, and also carbonate nodules collected from the seafloor off Joetsu, where thermogenic methane is seeping. Carbon isotopic compositions of the carbonates and lipid biomarkers of methane-oxidizing archaea within them were analyzed. In order to directly know original isotopic signatures of methane, we also attempted to extract adsorbed methane through acid dissolution of the powdered carbonates. Early-diagenetic carbonate phases show various δ13C values between -64.7 and -4.7‰ vs. VPDB, suggesting either biogenic or thermogenic, or both origins of methane. A lipid biomarker pentamethylicosane (PMI) extracted from the ancient carbonates has δ13C values mostly lower than -100‰ , whereas that from the modern methane-derived carbonate nodule has a higher value (-80‰ ). The δ13C values of the seeping methane (-36‰ ) and PMI in the modern Joetsu seep carbonate shows an offset of -44‰ . If this carbon isotope offset was similar at the ancient seeps, the δ13C values of PMI indicate that methane at ancient seeps in the Japan Sea region was biogenic in origin, with δ13C

Altitude effect on leaf wax carbon isotopic composition in humid tropical forests

NASA Astrophysics Data System (ADS)

Wu, Mong Sin; Feakins, Sarah J.; Martin, Roberta E.; Shenkin, Alexander; Bentley, Lisa Patrick; Blonder, Benjamin; Salinas, Norma; Asner, Gregory P.; Malhi, Yadvinder

2017-06-01

The carbon isotopic composition of plant leaf wax biomarkers is commonly used to reconstruct paleoenvironmental conditions. Adding to the limited calibration information available for modern tropical forests, we analyzed plant leaf and leaf wax carbon isotopic compositions in forest canopy trees across a highly biodiverse, 3.3 km elevation gradient on the eastern flank of the Andes Mountains. We sampled the dominant tree species and assessed their relative abundance in each tree community. In total, 405 sunlit canopy leaves were sampled across 129 species and nine forest plots along the elevation profile for bulk leaf and leaf wax n-alkane (C27-C33) concentration and carbon isotopic analyses (δ13C); a subset (76 individuals, 29 species, five forest plots) were additionally analyzed for n-alkanoic acid (C22-C32) concentrations and δ13C. δ13C values display trends of +0.87 ± 0.16‰ km-1 (95% CI, r2 = 0.96, p < 0.01) for bulk leaves and +1.45 ± 0.33‰ km-1 (95% CI, r2 = 0.94, p < 0.01) for C29n-alkane, the dominant chain length. These carbon isotopic gradients are defined in multi-species sample sets and corroborated in a widespread genus and several families, suggesting the biochemical response to environment is robust to taxonomic turnover. We calculate fractionations and compare to adiabatic gradients, environmental variables, leaf wax n-alkane concentrations, and sun/shade position to assess factors influencing foliar chemical response. For the 4 km forested elevation range of the Andes, 4-6‰ higher δ13C values are expected for upland versus lowland C3 plant bulk leaves and their n-alkyl lipids, and we expect this pattern to be a systematic feature of very wet tropical montane environments. This elevation dependency of δ13C values should inform interpretations of sedimentary archives, as 13C-enriched values may derive from C4 grasses, petrogenic inputs or upland C3 plants. Finally, we outline the potential for leaf wax carbon isotopes to trace biomarker

Modelling the 13C and 12C isotopes of inorganic and organic carbon in the Baltic Sea

NASA Astrophysics Data System (ADS)

Gustafsson, Erik; Mörth, Carl-Magnus; Humborg, Christoph; Gustafsson, Bo G.

2015-08-01

In this study, 12C and 13C contents of all carbon containing state variables (dissolved inorganic and organic carbon, detrital carbon, and the carbon content of autotrophs and heterotrophs) have for the first time been explicitly included in a coupled physical-biogeochemical Baltic Sea model. Different processes in the carbon cycling have distinct fractionation values, resulting in specific isotopic fingerprints. Thus, in addition to simulating concentrations of different tracers, our new model formulation improves the possibility to constrain the rates of processes such as CO2 assimilation, mineralization, and air-sea exchange. We demonstrate that phytoplankton production and respiration, and the related air-sea CO2 fluxes, are to a large degree controlling the isotopic composition of organic and inorganic carbon in the system. The isotopic composition is further, but to a lesser extent, influenced by river loads and deep water inflows as well as transformation of terrestrial organic carbon within the system. Changes in the isotopic composition over the 20th century have been dominated by two processes - the preferential release of 12C to the atmosphere in association with fossil fuel burning, and the eutrophication of the Baltic Sea related to increased nutrient loads under the second half of the century.

RAPID AND PRECISE METHOD FOR MEASURING STABLE CARBON ISOTOPE RATIOS OF DISSOLVED INORGANIC CARBON

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...

Carbon and Oxygen Isotope Measurements of Ordinary Chondrite (OC) Meteorites from Antarctica Indicate Distinct Terrestrial Carbonate Species using a Stepped Acid Extraction Procedure Impacting Mars Carbonate Research

NASA Astrophysics Data System (ADS)

Evans, M. E.; Niles, P. B.; Locke, D.

2015-12-01

The purpose of this study is to characterize the stable isotope values of terrestrial, secondary carbonate minerals from five OC meteorites collected in Antarctica. These samples were selected for analysis based upon their size and collection proximity to known Martian meteorites. They were also selected based on petrologic type (3+) such that they were likely to be carbonate-free before falling to Earth. This study has two main tasks: 1) characterize the isotopic composition of terrestrial, secondary carbonate minerals formed on meteorites in Antarctica, and 2) study the mechanisms of carbonate formation in cold and arid environments with Antarctica as an analog for Mars. Two samples from each meteorite, each ~0.5g, was crushed and dissolved in pure phosphoric acid for 3 sequential reactions: a) Rx0 for 1 hour at 30°C, b) Rx1 for 18 hours at 30°C, and c) Rx2 for 3 hours at 150°C. CO2 was distilled by freezing with liquid nitrogen from each sample tube, then separated from organics and sulfides with a TRACE GC using a Restek HayeSep Q 80/100 6' 2mm stainless column, and then analyzed on a Thermo MAT 253 IRMS in Dual Inlet mode. This system was built at NASA/JSC over the past 3 years and proof tested with known carbonate standards to develop procedures, assess yield, and quantify expected uncertainties. Two distinct species of carbonates are found based on the stepped extraction technique: 1) Ca-rich carbonate released at low temperatures, and 2) Mg, or Fe-rich carbonate released at high temperatures. Preliminary results indicate that most of the carbonates present in the ordinary chondrites analyzed have δ13C=+5‰, which is consistent with formation from atmospheric CO2 δ13C=-7‰ at -20°C. The oxygen isotopic compositions of the carbonates vary between +4‰ and +34‰ with the Mg-rich and/or Fe-rich carbonates possessing the lowest δ18O values. This suggests that the carbonates formed under a wide range of temperatures. However, the carbonate oxygen

Constraining the cause of the end-Guadalupian extinction with coupled records of carbon and calcium isotopes

NASA Astrophysics Data System (ADS)

Jost, A. B.; Mundil, R.; He, B.; Brown, S. T.; Altiner, D.; Sun, Y.; DePaolo, D. J.; Payne, J.

2013-12-01

A negative δ13C excursion in carbonate sediments from Guadalupian (Middle Permian) and Lopingian (Late Permian) stratigraphic sections has been interpreted to result from a large carbon cycle disturbance during end-Guadalupian extinction event (ca. 260 Ma). However, the carbon isotope data alone are insufficient to uniquely determine the type and magnitude of perturbations to the global carbon cycle. The carbon and calcium cycles are coupled via CaCO3 burial, so changes in calcium isotopes can be used to constrain the cause of a carbon isotope excursion. In this study, we present coupled carbon and calcium isotope records from three Guadalupian-Lopingian (G/L) sections in China and Turkey. Isotope records among our studied sections are inconsistent in both their δ13C and δ44/40Ca records. Similar inconsistencies in δ13C among sections occur across previously published datasets. Sections with large (>3‰) changes in δ13C either show evidence for diagenetic alteration or do not show δ13C and δ44/40Ca changes consistent with severe volcanic degassing from Emeishan or methane clathrate destabilization. We conclude that the large isotopic changes are more likely the result of local burial conditions or diagenetic effects, rather than a large carbon cycle disturbance. Perturbations to the global carbon and calcium cycles appear to have been much smaller across the G/L transition than across the subsequent Permian-Triassic boundary. This finding is consistent with recent paleobiological data showing that the end-Guadalupian extinction was much less severe than previously believed, and was indistinguishable in magnitude from background intervals. However, selective extinction of marine animals with passive respiratory physiology indicates that the G/L extinction cannot simply be due to background extinction or sampling failure, and that it was triggered by some environmental event. Therefore, any environmental event must have been small enough to not generate large

Carbon Isotopic Ratios of Amino Acids in Stardust-Returned Samples

NASA Technical Reports Server (NTRS)

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

2009-01-01

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).

Carbon Isotopic Measurements of Amino Acids in Stardust-Returned Samples