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At least 55 records · Page 3

Sulfur and carbon cycling in organic-rich marine sediments

Nearshore, continental shelf, and slope sediments are important sites of microbially mediated carbon and sulfur cycling. Marine geochemists investigated the rates and mechanisms of cycling processes in these environments by chemical distribution studies, in situ rate measurements, and steady state kinetic modeling. Pore water chemical distributions, sulfate reduction rates, and sediment water chemical fluxes were used to describe cycling on a ten year time scale in a small, rapidly depositing coastal basin, Cape Lookout Bight, and at general sites on the upper continental slope off North Carolina, U.S.A. In combination with 210 Pb sediment accumulation rates, these data were used to establish quantitative carbon and sulfur budgets as well as the relative importance of sulfate reduction and methanogeneis as the last steps in the degradation of organic matter.

Martens, C. S.↗

Searching for Biogeochemical Cycles on Mars

The search for life on Mars clearly benefits from a rigorous, yet broad, definition of life that compels us to consider all possible lines of evidence for a martian biosphere. Recent studies in microbial ecology illustrate that the classic definition of life should be expanded beyond the traditional definition of a living cell. The traditional defining characteristics of life are threefold. First, life is capable of metabolism, that is, it performs chemical reactions that utilize energy and also synthesize its cellular constituents. Second, life is capable of self-replication. Third, life can evolve in order to adapt to environmental changes. An expanded, ecological definition of life also recognizes that life is a community of organisms that must interact with their nonliving environment through processes called biogeochemical cycles. This regenerative processing maintains, in an aqueous conditions, a dependable supply of nutrients and energy for growth. In turn, life can significantly affect those processes that control the exchange of materials between the atmosphere, ocean, and upper crust. Because metabolic processes interact directly with the environment, they can alter their surroundings and thus leave behind evidence of life. For example, organic matter is produced from single-carbon-atom precursors for the biosynthesis of cellular constituents. This leads to a reservoir of reduced carbon in sediments that, in turn, can affect the oxidation state of the atmosphere. The harvesting of chemical energy for metabolism often employs oxidation-reduction reactions that can alter the chemistry and oxidation state of the redox-sensitive elements carbon, sulfur, nitrogen, iron, and manganese. Have there ever been biogeochemical cycles on Mars? Certain key planetary processes can offer clues. Active volcanism provides reduced chemical species that biota can use for organic synthesis. Volcanic carbon dioxide and methane can serve as greenhouse gases. Thus the persistence of volcanism on Mars may well have influenced the persistence of a martian biosphere. The geologic processing of the crust can affect the availability of nutrients and also control the deposition of minerals that could have served as a medium for the preservation of fossil information. Finally, the activity of liquid water is crucial to life. Was there ever an Earth-like hydrologic cycle with rainfall? Has aqueous activity instead been restricted principally to hydrothermal activity below the surface? To what extent did the inorganic chemistry driven by sunlight and hydrothermal activity influence organic chemistry (prebiotic chemical evolution)? This paper addresses these and other key questions.

DesMarais, David J.↗

Seasonal variations in the stable carbon isotopic signature of biogenic methane in a coastal sediment

Systematic seasonal variations in the stable carbon isotopic signature of methane gas occur in the anoxic sediments of Cape Lookout Bight, a lagoonal basin on North Carolina's Outer Banks. Values for the carbon isotope ratio of methane range from -57.3 per mil during summer to -68.5 per mil during winter in gas bubbles with an average methane content of 95 percent. The variations are hypothesized to result from changes in the pathways of microbial methane production and cycling of key substrates including acetate and hydrogen. The use of stable isotopic signatures to investigate the global methane cycle through mass balance calculations, involving various sediment and soil biogenic sources, appears to require seasonally averaged data from individual sites.

Martens, C. S.↗

Black Carbon in Estuarine and Coastal Ocean Dissolved Organic Matter

Black carbon (BC) in ultrafiltered high-molecular-weight DOM (UDOM) was measured in surface waters of Delaware Bay, Chesapeake Bay and the adjacent Atlantic Ocean (USA) to ascertain the importance of riverine and estuarine DOM as a source of BC to the ocean. BC comprised 5-72% of UDOM-C (27+/-l7%) and on average 8.9+/-6.5% of dissolved organic carbon (DOC) with higher values in the turbid region of the Delaware Estuary and lower yields in the river and coastal ocean. The spatial and seasonal distributions of BC along the salinity gradient of Delaware Bay suggest that the higher levels of BC in surface water UDOM originated from localized sources, possibly from atmospheric deposition or released from resuspended sediments. Black carbon comprised 4 to 7% of the DOC in the coastal Atlantic Ocean, revealing that river-estuary systems are important exporters of colloidal BC to the ocean. The annual flux of BC from Delaware Bay UDOM to the Atlantic Ocean was estimated at 2.4x10(exp 10) g BC yr(exp -1). The global river flux of BC through DOM to the ocean could be on the order of 5.5x1O(exp 12)g BC yr (exp -1). These results support the hypothesis that the DOC pool is the intermediate reservoir in which BC ages prior to sedimentary deposition.

Mannino, Antonio↗

Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets.

Fu, Qi↗

First-results from the Perseverance SHERLOC Investigation: Aqueous Alteration Processes and Implications for Organic Geochemistry in Jezero Crater, Mars

The Perseverance rover landed in Jezero crater, a site selected to fulfill the Mars-2020 mission goals of characterizing the geology of habitable environments and searching for signs of life while collecting samples for return to Earth [1]. Jezero hosted an open-basin lake during the late Noachian/early Hesperian (~3.7 Ga) [1-2], has units associated with the largest carbonate deposit identified on Mars [3-4], and has a well-preserved delta with clay and carbonate-bearing sediments, well-suited to preservation of organics [1,3-4]. Investigating the nature of organics and aqueous environments within their geologic con-text allows us to understand important aqueous processes and determine habitability within Jezero crater. Previous in situ landed measurements of organics could not resolve their spatial and mineralogical con-text [5-6]. Although Martian meteorites lack geological context, the spatial distribution of organic compounds in Martian meteorites have allowed recognition of an association between aqueous processes and organics [7-8]. Here, we show for the first time in-situ associations between carbonate-forming ultramafic alteration process, later stage aqueous sulfate and perchlorate formation, and organics on the Martian surface. Methodology and geological context: We use the Perseverance rover’s SHERLOC instrument (Scanning Habitable Environments with Raman and Lumines-ence of Organics and Chemicals), a deep-ultraviolet fluorescence and Raman scattering spectrometer capable of mapping the organic and mineral composition with a spatial resolution of 100 μm resolution to report the presence of organics and aqueously formed minerals at Jezero crater [9]. These spectral detections were compared with co-located images obtained with the autofocus context imager (ACI) and the WATSON camera for textural analysis [9]. As of writing, the Per-severance rover has abraded five targets that were measured with the SHERLOC instrument. The five targets are located in two different orbitally-identified geological units within the floor of Jezero crater; the Crater Floor Fractured Rough unit (CF-Fr) and the Séítah region within the Crater Floor Fractured 1 unit (CF-F1) [10]. In orbital infrared spectroscopic data, the CF-Fr unit is associated with pyroxene spectral signatures and minor alteration, while the Séítah region is associated with olivine and minor Mg-rich carbonates and clays [3-4,10]. Carbonation of ultramafic protolith recorded within Jezero crater: All scans of abraded targets within the Séítah region reveal strong peaks at 1080–1090 cm−1 consistent with carbonate and peak singlets or doublets at 820–840 cm−1 attributed to olivine (Fig. 1), consistent with orbital infrared observations. Our detailed micron-scale petrographic and spectroscopic evidence shows that these carbonates formed through carbonation of an ultramafic protolith. The supporting observations include: (1) Carbonate cation compositions match those of olivine, suggesting mixed Fe- and Mg-olivine gave rise to mixed Fe- and Mg-carbonates, similar to observations of ultramafic systems on Earth and within Martian meteorites [3-4,7-8]. (2) The ob-served carbonates co-occur with hydrated materials, gypsum, and potentially aqueously-formed phases, amorphous silicates and phosphate. (3) The spectral and textural variation of olivine and carbonate dominated zones and olivine-carbonate mixtures within both primary grains and interstitial zones are expected for carbonated ultramafic protoliths. (4) These mineral associations and textures closely resemble those observed within the ALH84001 and Nakhlite meteorites attributed to olivine carbonation on Mars [6-7]. Taken together, micron-scale SHERLOC documentation of these phenomena bridge previous orbital and meteorite observations and demonstrate in-situ regionally extensive (~106 km2) ultramafic alteration resulting in geo-logical deposition of carbonates. Furthermore, we observe that olivine carbonation was involved in preserving and possibly synthesizing organics, which makes this environment potentially habitable, as previously suggested in [1,3-4] (Fig. 1). Late-stage aqueous perchlorate and sulfate in Jezero crater: An abrasion target within the CF-Fr unit contains combinations of high intensity 950-955 cm−1 peaks and minor 1090-1095 cm−1 and 1150-1155 cm−1 peaks that are spectral fits to anhydrous perchlorate (Fig. 1). Some spectra show a combination of 950-955 cm−1 peaks with equally strong 1010-1020 cm−1 peaks, low intensity broad features at 1120 cm−1, and occasional broad 3450 cm−1 hydration (-OH) features, indicating a mixture of Ca-sulfate and perchlorate that is minimally hydrated (Fig. 1). The detections of per-chlorates within Jezero crater differ from previous measurements (e.g. Phoenix lander, Curiosity rover, Tissint meteorite [7,11]) because they are observed to be intimately related to aqueous processes including sulfate formation, they present as a secondary white void-fill occurring within the interior of the rock, and they are found to likely be Na-perchlorate. implications for their formation: Three different types of organics embedded within three different lithologies were observed within the abraded targets. Organics associated with low intensity ~340 nm fluorescence were widespread within targets with no apparent association to particular minerals (Fig. 1). Organics associated with ~305 nm and ~275 nm fluorescence correlated with sulfates within the Bellegarde target in the CF-Fr unit, while organics associated with high intensity ~340 nm fluorescence correlated with carbonate, phosphate, and amorphous silicate mixtures within the Garde target in the Séítah region (Fig. 1). Although assignment of fluorescence signatures to specific organic compounds is not conclusive, ~340 nm fluorescence is generally more consistent with 2-ring aromatic organics, ~275 nm fluorescence is more consistent with 1-ring aromatic organics, and ~305 nm fluorescence can be created by either 2- or 1-ring aromatics [12]. These observations indicate that the strongest fluorescence signatures interpreted as organics were found in materials associated with aqueous processes, i.e. sulfate- and carbonate-bearing materials, suggesting both brines and ultramafic carbonation aqueous environments were capable of preserving organics on ancient Mars. In Martian meteorites, simple aromatic organics proposed to have been synthesized through aqueous processes can be found within minerals associated with olivine carbonation and in spatial association with perchlorate and sulfate materials [7-8], similar to SHERLOC observations. Hence, we advance an abiotic aqueous synthesis origin for the organics although we cannot rule out the presence of organics from meteoritic in-fall or putative organic biosignatures. Detailed analyses will be required upon return of these materials to Earth.

E L Scheller↗

KT Boundary Impact Debris from DSDP Site 577

The KT boundary at DSDP Site 577 (Shatsky Rise, western North Pacific) is in a calcareous nannofossil ooze. It is bioturbated so Ir and impact debris are smeared across less than 15 cm of core. An absence of sulfides and chalcophile enrichment and the presence of Mn-micronodules indicate that this boundary did not experience anoxic conditions typical of many other calcareous KT sites. Because of its shallow burial (109 m) ejecta is extremely well preserved and has been the subject of numerous studies. Three high-temperature minerals have been identified at this site. Clinopyroxene (cpx), found only at Site 577 may be precursor to diagenetic sanidine in some European sites. Magnesioferrite spinel has the highest Fe2O3/FeO of any locality and can have and trace inclusions of Ni-magnesiowustite, which is known at only one other site (Site 596). Other debris described includes shocked quartz grains less than 200 microns, hollow spherules possibly related to impact melt glasses found near Chicxulub, and irregular Ir-rich particles that may be derived directly from meteoritic materials. The latter may be related to the fossil meteorite found at Site 576, just 500 km to the east. A large-volume (approx. 10 cc) sample was taken to systematically characterize debris. The less than 60 microns fraction of the carbonate-free sediment contained 44 mg of impact debris. 2700 particles less than l00 microns were classified based on color, shape, and morphology. About 55% are generally light colored, composed mostly of clays, and typically lack magnesioferrite spinel. Less than half of these are quite spherical; many have irregular shapes, possibly from fragmentation. Hollow spherules with smooth shiny surfaces are only 2% of the total but many fragments in the 60 - 100 microns fraction suggest that they were more abundant and that some may have been quite large; 800 microns or more. Cpx-bearing spherules, easily identified by green crystals at the surface, constitute only 2.5% of the total. Three cpx spherules are dumbbells. The other 40% of the debris is a complex assemblage of dark-colored particles, most of which have magnesioferrite spinel. We have currently separated these into 6 groups based on color and morphology, but this hardly describes the diversity of this group. They range from smooth and spherical to rough and irregular in shape. Some have a planar cleavage, similar to some broken cosmic spherules. 220 particles were irradiated for trace element analysis, as groups and as individual particles. It appears that every spherule type as at least a few ng/g Ir. Several of the spinel-bearing particles have been identified with high Ir (200-1500 ng/g), Cr (2-5 mg/g), and Ni (2-10 mg/g), consistent with results. It is hoped that some of these will yield potential fragments of the KT bolide. Only five have been sectioned to date and they are characterized by high concentrations of spinel; two contained traces of magnesiowustite. This debris constitutes a complex assemblage of ejecta materials. The light-colored, spinel-free particles likely derive mainly from target materials. A significant fraction of these are probably alteration products of cpx-spherules. The dark-colored debris is more likely to have high siderophile concentrations, and thus a high extraterrestrial component. However, the majority don't. Most of the larger spinel-bearing spherules have modest Ir concentrations (5-30 ng/g).

Kyte, Frank T.↗

Characterization of Shock Effects in Calcite by Raman Spectroscopy: Results of Experiments

Carbonates comprise approx. 20% by volume of present day Earth's sedimentary rocks and store most of the terrestrial CO2 inventory. Some of the oldest meta-sedimentary rocks found on Earth contain abundant carbonate from which impact-induced release of CO2 could have played a role in the formation and evolution of the atmosphere. Carbonates are also present in the target materials for approx. 30% of all terrestrial impact structures including large impacts such as Chicxulub which happened to occur at a location with extraordinarily thick platform carbonate 3-6 km deep. The impact release of CO2 from carbonates can cause global warming as a result of the well-known greenhouse effect and have subsequent effects on climate and biota. Therefore, the shock behavior of calcite is important in understanding the Cretaceous-Paleogene event and other impacts with carbonate-bearing sediments in their target(s) such as Mars and some asteroids. A comprehensive survey utilizing a variety of techniques to characterize the effects manifest in Calcite (Iceland Spar) experimentally shocked to 60.8 GPa has been completed. Results of analysis by Raman Spectroscopy are reported here.

Bell, M. S.↗

Southern California Water Resources: Using NASA Earth Observations to Monitor Seagrass Extent and Water Quality Parameters in Southern California

Eelgrass (Zostera marina) is a species of submerged aquatic vegetation found in shallow bays and estuaries with soft seafloors. Eelgrass is recognized for providing ecosystem benefits, such as carbon sequestration, sediment stabilization, water clarification, and fish and wildlife habitats. However, eelgrass is impacted by both marine and terrestrial threats associated with climate change. In this project, we worked with the Southern California Coastal Water Research Project, the National Oceanic and Atmospheric Administration’s National Marine Fisheries Service, and the State of California San Diego Regional Water Quality Control Board to investigate water quality parameters (i.e., chlorophyll-a concentration, sea surface temperature, and turbidity) associated with eelgrass in Newport Bay and Mission Bay, California. The team used Landsat 8 Operational Land Imager and Thermal Infrared Sensor, Landsat 9 Operational Land Imager-2 and Thermal Infrared Sensor-2, Sentinel-2 MultiSpectral Instrument, and ECOsystem Spaceborne Thermal Radiometer Experiment on Space Station land surface temperature and cloud mask to create a time series of these water quality parameters from 2019–2023. We found that the parameters followed cyclical, seasonal patterns with turbidity and sea surface temperature peaking in the summer. We did not find that the parameters had changed significantly over longer time periods. These results will be used in a model developed by the Southern California Coastal Water Research Project to assess eelgrass ecosystem health and predict ecosystem occupancy in the future.

Katya Beener↗

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

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

NASA Program Exobiology↗

Biogenic Methane and the Rise of Oxygen

Oxygenic photosynthesis does not make the rise of oxygen inevitable. What is required is that reductant and oxygen be separated and permanently segregated. The usual picture for Earth is that oxygenic photosynthesis split CO2 into carbon and oxygen, with the carbon buried in sediments and the oxygen mostly taken up by oxides of iron and sulfur. The relatively small atmospheric reservoir of O2 is regulated by the carbon burial rate, reaction with volcanic and metamorphic gases, and oxidation of reduced carbon released as old sediments weather. Absent from this picture is a distinction between the Archean and modern times: on average, carbon burial fluxes would have been matched by oxygen losses then as now. Separation of reductant from oxidant is only provisional. No net oxidation of the continents occurs, and so no change of diagenetic, metamorphic, or volcanic gases is expected. Nor would any change in oxidative weathering be expected. Something more than carbon burial is required to make the Archean different. The escape of hydrogen to space permanently separates the reductant from the oxidant. Hydrogen escape is widely believed to have led to the present highly oxidized states of Mars and Venus. Hydrogen escape has usually been thought small for Archaean Earth, because water vapor is cold-trapped at the troposphere and thus held to levels of a few ppmv in the stratosphere. This cold trapping renders hydrogen escape negligible. However, methane is not cold trapped, and its expected abundance in the Archaean, given low oxygen levels and a biogenic source, would have been high, probably more than 100 times present. At such levels methane would have driven geologically significant levels of hydrogen escape. Additional information is contained in the original extended abstract.

Catling, David↗

Isotopic Composition of Carbon Dioxide Released from Confidence Hills Sediment as Measured by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

In October 2014, the Mars Science Laboratory (MSL) "Curiosity" rover drilled into the sediment at the base of Mount Sharp in a location namsed Cionfidence Hills (CH). CH marked the fifth sample pocessed by the Sample Analysis at Mars (SAM) instrument suite since Curiosity arrived in Gale Crater, with previous analyses performed at Rocknest (RN), John Klein (JK), Cumberland (CB), and Windjana (WJ). Evolved gas analysis (EGA) of all samples has indicated H2O as well as O-, C- and S-bearing phases in the samples, often at abundances that would be below the detection limit of the CheMin instrument. By examining the temperatures at which gases are evolved from samples, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases when their identities are unclear to CheMin. SAM may also detect gases evolved from amorphous material in solid samples, which is not suitable for analysis by CheMin. Finally, the isotopic composition of these gases may suggest possible formation scenarios and relationships between phases. We will discuss C isotope ratios of CO2 evolved from the CH sample as measured with SAM's quadrupole mass spectrometer (QMS) and draw comparisons to samples previously analyzed by SAM.

Franz, H. B.↗

Earth's early atmosphere as seen from carbon and nitrogen isotopic analysis of Archean sediments

The origin and evolution of the Earth's early atmosphere has long been a topic of great interest but determination of actual compositions over geologic time is a difficult problem. However, recent systematic studies of stromatolite deposits (Precambrian Paleobiology Research Group) has extended our knowledge of Archean ecosystems. It has been shown that many stromatolite deposits have undergone negligible alteration since their time of formation. The discovery of primary fluid inclusions within unaltered 3.5 b.y. old Archiean sediments and the observation that the 3.3 b.y. old Barberton cherts have remained closed to argon loss and have not been subjected to thermal metamorphism suggests that an opportunity exists for the direct measurement of the volatile constituents present at their time of formation. Of primary interest to this study was the possibility that the stromatolites and other Archean sediments might retain a vestige of the atmosphere and thus afford an indication of the variations in carbon dioxide and nitrogen isotopic compositions with time. A suite of essentially unaltered Archean stromatolites and the cherts of different ages and geologic sites have been analyzed for their trapped carbon dioxide and nitrogen compositions by the stepped combustion extraction tech nique utilizing static mass spectrometers for the isotope measurements.

Gibson, E. K., Jr.↗

Biologically mediated isotope fractionations - Biochemistry, geochemical significance and preservation in the earth's oldest sediments

Preferential metabolization of isotopically light carbon and sulfur has resulted in a fractionation of the stable isotopes of these elements on a global scale, with the light species (C-12, S-32) markedly concentrated in biogenic materials. Since the biological effects are basically retained when carbon and sulfur are incorporated in sediments, the respective fractionations are propagated into the rock section of the geochemical cycle, this having consequently caused a characteristic bipartition of both elements between 'light' and 'heavy' crustal reservoirs. Preservation of the biological isotope effects in sedimentary rocks makes it possible to trace the underlying biochemical processes back over most of the geological record. According to the available evidence, biological (autotrophic) carbon fixation arose prior to 3.5(if not 3.8) billion years ago, while the emergence of dissimilatory sulfate reduction antedates the appearance of the oldest presumably bacteriogenic sulfur isotope patterns in rocks between 2.7 and 2.8 billion years old. Hence, biological control of the terrestrial carbon and sulfur cycles has been established very early in the earth's history.

Schidlowski, M.↗

Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)

On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

Freeman, K. H.↗

The oxygen content of ocean bottom waters, the burial efficiency of organic carbon, and the regulation of atmospheric oxygen

Data for the burial efficiency of organic carbon with marine sediments have been compiled for 69 locations. The burial efficiency as here defined is the ratio of the quantity of organic carbon which is ultimately buried to that which reaches the sediment-water interface. As noted previously, the sedimentation rate exerts a dominant influence on the burial efficiency. The logarithm of the burial efficiency is linearly related to the logarithm of the sedimentation rate at low sedimentation rates. At high sedimentation rates the burial efficiency can exceed 50% and becomes nearly independent of the sedimentation rate. The residual of the burial efficiency after the effect of the sedimentation rate has been subtracted is a weak function of the O2 concentration in bottom waters. The scatter is sufficiently large, so that the effect of the O2 concentration in bottom waters on the burial efficiency of organic matter could be either negligible or a minor but significant part of the mechanism that controls the level of O2 in the atmosphere.

Non-NASA Center↗

The combined application of organic sulphur and isotope geochemistry to assess multiple sources of palaeobiochemicals with identical carbon skeletons

Five immature sediments from a Messinian evaporitic basin, representing one evaporitic cycle, were studied using molecular organic sulphur and isotope geochemistry. It is shown that a specific carbon skeleton which is present in different "modes of occurrence" ("free" hydrocarbon, alkylthiophene, alkylthiolane, alkyldithiane, alkylthiane, and sulphur-bound in macromolecules) may have different biosynthetic precursors which are possibly derived from different biota. It is demonstrated that the mode of occurrence and the carbon isotopic composition of a sedimentary lipid can be used to "reconstruct" its biochemical precursor. This novel approach of recognition of the suite of palaeobiochemicals present during the time of deposition allows for identification of the biological sources with an unprecedented specificity.

Non-NASA Center↗