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1.
Intra-tooth δ18O variations within the carbonate (δ18Oc) and phosphate (δ18Op) components of tooth apatite were measured for Miocene and Pliocene hypsodont mammals from Afghanistan, Greece and Chad in order to evaluate the resistance of enamel to diagenetic alteration. Application of water-apatite interaction models suggest that the different kinetic behaviours of the phosphate-water and carbonate-water systems can be used to detect subtle oxygen isotope disequilibria in fossil enamel when intra-individual variations are considered. Selective alteration of the oxygen isotope composition from the carbonate component of Afghan and Greek enamels suggests inorganic isotopic exchange processes. Microbially-induced isotopic exchange for phosphate is demonstrated for the first time in enamel samples from Chad, in association with extensive recrystallization. In Chad, δ18Op values were derived from partial isotopic exchange with fossil groundwater during early diagenesis. Mass balance calculations using average carbonate content in enamel as a proxy for recrystallization, and the lowest δ18Op value of dentine as a proxy for the isotopic composition of the diagenetic fluid, indicate that diagenesis can alter δ18Op by as much as 3‰ in some enamel samples. This diagenetic alteration is also responsible for a decrease in intra-individual variations of up to 1‰ in affected specimens. The effects of diagenesis on δ18Op values of fossil enamel are not systematic, however, and can only be estimated if sequential δ18Op and δ18Oc analyses are performed on fossil enamel and dentine. Reconstruction of large temporal- or spatial-scale paleoclimates based on δ18Op analyses from mammalian teeth cannot be considered valid if enamel has been affected by bacterial activity or if the data cannot be corrected for diagenetic effects.  相似文献   

2.
The oxygen isotope compositions of phosphate and structural carbonate in mammalian enamel and bone apatite are linked to that of body water at constant body temperature near 37°C, but the isotope systematics of oxygen in structural carbonate are not well understood. Using coupled measurements of the oxygen isotope composition of structural carbonate and phosphate from horse tooth enamel, the apparent oxygen isotope fractionation factor between structural carbonate and body water is estimated to be 1.0263 ± 0.0014. These estimates provide a quantitative basis for using the oxygen isotope composition of structural carbonate in mammalian biogenic apatite for ecological, climatological, and physiological reconstruction.  相似文献   

3.
Recent and fossil (prehistoric, Natufian) gazelle bones, dentin and enamel were analyzed for their oxygen isotopic composition (δ18O) of the phosphate and carbonate, as well as their crystallinity. Fossil bones and dentin have better crystallinity than recent specimens, indicating diagenetic change. Fossil enamel, on the other hand, is identical in crystallinity to recent enamel, indicating the lack of diagenetic alteration. Comparison of δ18O of carbonate and phosphate of the skeletal elements suggests that the coexisting phosphate and carbonate of both the recent and fossil specimens are close to isotopic equilibrium. This might suggest that both phases were affected by the same degree of diagenetic alteration, and that comparison of their δ18O is not useful for the selection of pristine material for paleoclimatic reconstruction purposes. Oxygen isotope analysis of gazelle enamel from the Natufian period from Hayonim Cave, Israel, show depletion in δ18O in comparison with recent enamel. This depletion is interpreted to represent a colder and/or wetter climate in the Natufian of northern Israel. © 1999 John Wiley & Sons, Inc.  相似文献   

4.
《Chemical Geology》1992,94(3):183-192
The Siwalik Sequence of northern Pakistan contains a 16-Ma record of paleosol carbonate and fossil teeth from which a record of paleovegetation can potentially be reconstructed and compared. The carbon isotopic composition of paleosol carbonate and organic matter from Siwalik strata reflects a major paleoecological change on the floodplains of major rivers beginning7.3 Ma ago. By 6 Ma C3-dominated plant communities, probably composed of mostly trees and shrubs, were displaced by nearly continuous C4 grassland. We find that the carbon isotopic ratios in herbivore tooth enamel reflect this dramatic ecologic shift. Carbonate in enamel older than 7 Ma averages −11‰ in δ13CPDB, consistent with a largely C3 diet. Enamel from the Plio-PIeistocene averages +1.9‰ in δ13C, similar to the value displayed by modern C4 grazers. Analysis of post-burial carbonate cements, and the concordance with isotopic evidence from paleosols argues strongly against major isotopic alteration of the enamel, while coexisting bone may have been altered early in burial. This study confirms that enamel apatite is useful for paleodietary reconstruction much further back in the geologic record than was previously thought.  相似文献   

5.
不同学者用磷酸平衡法分析古哺乳动物牙齿化石碳酸羟基磷灰石中结构碳酸盐的碳、氧稳定同位素组成时，预处理方法和实验条件也不尽相同。实测结果表明，预处理条件与磷酸法制备CO2的反应温度和反应时间均可能对分析结果产生影响，需在综合运用机械和化学手段除净外表附着碳酸盐的前提下，将样品充分研磨，并彻底分解其中的有机组分和非结构碳酸盐，再制备CO2。70℃的恒温水浴可以使化学反应和同位素分馏均在短时间内结束，且较为完全、彻底，测得的同位素数据重现性好；而25℃时反应进行较缓，氧同位素测试结果有时可能不理想  相似文献   

6.
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.  相似文献   

7.
Water temperature, oxygen isotope composition and the δ13C of dissolved inorganic carbon were measured in 2 southern Michigan rivers, the Huron River and Fleming Creek, between late September 1990 and June 1992. The final full year of shell growth in 3 unionids collected in 1992 from these rivers was sampled for stable isotope analysis with a resolution of 30 μm. The δ18O of both shell nacre and the prismatic layer is accurately predicted by a fractionation relationship developed for biogenic aragonite. High resolution sampling of 3 species and bulk sampling of 3 other species suggest that all unionids adhere to this oxygen isotope fractionation relationship. This relationship is used to show that shell growth ceases below approximately 12°C. In these 2 settings the average δ18O value of shell (PDB scale) is within 0.5‰ of the average δ18O of river water (SMOW scale). Unionids can therefore be used in oxygen-isotope-based paleoclimatic and paleohydrologic reconstructions. In contrast, the carbon isotope ratio of shell is not accurately predicted by published fractionation factors between D.I.C. and carbonate. Shell δ13C is more negative than predicted values and the offset is highly variable suggesting a significant and variable incorporation of metabolic carbon into the shell carbonate.  相似文献   

8.
Isotope geochemistry of caliche developed on basalt   总被引：1，自引：0，他引：1  
Enormous variations in oxygen and carbon isotopes occur in caliche developed on < 3 Ma basalts in 3 volcanic fields in Arizona, significantly extending the range of δ18O and δ13C observed in terrestrial caliche. Within each volcanic field, δ18O is broadly co-variant with δ13C and increases as δ13C increases. The most 18O and 13C enriched samples are for subaerial calcite developed on pinnacles, knobs, and flow lobes that protrude above tephra and soil. The most 18O and 13C depleted samples are for pedogenic carbonate developed in soil atmospheres. The pedogenic caliche has δ18O fixed by normal precipitation in local meteoric waters at ambient temperatures and has low δ13C characteristic of microbial soil CO2. Subaerial caliche has formed from 18O-rich evapoconcentrated meteoric waters that dried out on surfaces after local rains. The associated 13C enrichment is due either to removal of 12C by photosynthesizers in the evaporating drops or to kinetic isotope effects associated with evaporation. Caliche on basalt lava flows thus initially forms with the isotopic signature of evaporation and is subsequently over-layered during burial by calcite carrying the isotopic signature of the soil environment. The large change in carbon isotope composition in subsequent soil calcite defines an isotopic biosignature that should have developed in martian examples if Mars had a “warm, wet” early period and photosynthesizing microbes were present in the early soils. The approach can be similarly applied to terrestrial Precambrian paleocaliche in the search for the earliest record of life on land. Large variations reported for δ18O of carbonate in Martian meteorite ALH84001 do not necessarily require high temperatures, playa lakes, or flood runoff if the carbonate is an example of altered martian caliche.  相似文献   

9.
This work deals with the evolution of carbon isotope composition in the Luoyixi (罗依溪) Section, a candidate of the Global Standard Stratotype-section and Point (GSSP), defining the base of the as-yet-undefined seventh stage of Cambrian System at the first appearance of the cosmopolitan agnostoid Lejopyge laevigata. This level is favored in a vote of International Subcommission on Cambrian Stratigraphy (ISCS) as the biohorizon for defining the base of a global stage. Two hundred and sixty-four samples for carbon and oxygen isotope analysis have been collected from the carbonate successions at an interval of 0.25 to 0.5 m in this section. Results of the carbon isotope data exhibit a remarkable disciplinarian trend. The pattern of the carbon isotope evolution is gently undulant with a relatively long period during the underlying Drumian Stage, and then the values of δ13C fluctuate sharply with a short period in provisional seventh stage. The onset of sharp fluctuation in the δ13C values begins at the proposed GSSP level, defining the base of the global seventh stage, where δ13C values change from a gentle trend to a sharp trend. Distinct covariant-relationships among δ13C, δ13O, and sea level fluctuations suggest that a warming change in paleoclimate took place during the early global seventh stage, which led to a positive shift in δ13C values.  相似文献   

10.
《Gondwana Research》2001,4(3):377-386
The Kerala Khondalite belt is a Proterozoic metasupracrustal granulite facies terrain in southern India comprising garnet-biotite gneiss, garnet-sillimanite gneiss and orthopyroxene granulites as major rock types. Calc-silicate rocks and marbles, occurring as minor lithologies in the Kerala Khondalite Belt, show different mineral assemblages and reaction histories of which indicate a metamorphic P-T-fluid history dominated by internal fluid buffering during the peak metamorphism, followed by external fluid influx during decompression. The carbon and oxygen isotopic compositions of calcite from three representative metacarbonate localities show contrasting evolutionary trends. The Ambasamudram marbles exhibit carbon and oxygen isotope ratios (δ13C ∼ 0‰ and δ18O ∼ 20‰) typical of middle to late Proterozoic marine carbonate sediments with minor variation ascribed to the isotopic exchange due to the devolatilization reactions. The δ13C and δ18O values of ∼ −9‰ and 11‰, respectively, for calcite from calc-silicate rocks at Nuliyam are considerably low and heterogeneous. The wollastonite formation here, possibly corresponds to an earlier event of fluid infiltration during prograde to peak metamorphism, which resulted in decarbonation and isotope resetting. Further, petrologic evidence supports a model of late carbonic fluid infiltration that has partially affected the calc-silicate rocks, with subsequent isotope resetting, more towards the contact between calc-silicate rock and charnockite. At Korani, only oxygen isotopes have been significantly lowered (δ18O ∼ 13‰) and the process involved might be a combination of metamorphic devolatilization accompanied by an aqueous fluid influx, supported by petrologic evidence. The stable isotope signatures obtained from the individual localities, thus indicate heterogeneous patterns of fluid evolution history within the same crustal segment.  相似文献   

11.
Three samples from the Mud Tank Carbonatite have very similar isotopic ratios, averaging δ13C=‐4.3 and δ18O=+7.5(SMOW). These isotope values are distinct from those of nearby highly metamorphosed Carpentarian marbles, which have marine limestone values of δ13C=‐1.3±0.5, and δ18O=+17.6+0.7 with n=11. Minor variations in the values for the normal marbles show no correlation with stratigraphy or geographic location; however, somewhat lighter oxygen is found in some other marbles known to be affected by low‐temperature fluids within the Woolanga Lineament. Isotopes of C and O, if discretely used in conjunction with other geochemical features, not only may discriminate between deep‐seated carbona‐tites and marbles, but may also help to identify zones of carbonate metasomatism and define the isotopic characters of the fluids.  相似文献   

12.
We present a model of bacterial sulfate reduction that includes equations describing the fractionation relationship between the sulfur and the oxygen isotope composition of residual sulfate (δ34SSO4_residual, δ18OSO4_residual) and the amount of residual sulfate. The model is based exclusively on oxygen isotope exchange between cell-internal sulfur compounds and ambient water as the dominating mechanism controlling oxygen isotope fractionation processes. We show that our model explains δ34SSO4_residual vs. δ18OSO4_residual patterns observed from natural environments and from laboratory experiments, whereas other models, favoring kinetic isotope fractionation processes as dominant process, fail to explain many (but not all) observed δ34SSO4_residual vs. δ18OSO4_residual patterns. Moreover, we show that a “typical” δ34SSO4_residual vs. δ18OSO4_residual slope does not exist. We postulate that measurements of δ34SSO4_residual and δ18OSO4_residual can be used as a tool to determine cell-specific sulfate reduction rates, oxygen isotope exchange rates, and equilibrium oxygen isotope exchange factors. Data from culture experiments are used to determine the range of sulfur isotope fractionation factors in which a simplified set of equations can be used. Numerical examples demonstrate the application of the equations. We postulate that, during denitrification, the oxygen isotope effects in residual nitrate are also the result of oxygen isotope exchange with ambient water. Consequently, the equations for the relationship between δ34SSO4_residual, δ18OSO4_residual, and the amount of residual sulfate could be modified and used to calculate the fractionation-relationship between δ15NNO3_residual, δ18ONO3_residual, and the amount of residual nitrate during denitrification.  相似文献   

13.
A 1000-yr history of climate change in the central Yukon Territory, Canada, is inferred from sediment composition and isotope geochemistry from small, groundwater fed, Seven Mile Lake. Recent observations of lake-water δ18O, lake level, river discharge, and climate variations, suggest that changes in regional effective moisture (precipitation minus evaporation) are reflected by the lake’s hydrologic balance. The observations indicate that the lake is currently 18O-enriched by summer evaporation and that during years of increased precipitation, when groundwater inflow rates to the lake increase, lake-water δ18O values decrease. Past lake-water δ18O values are inferred from oxygen isotope ratios of fine-grained sedimentary endogenic carbonate. Variations in carbonate δ18O, supplemented by those in carbonate and organic δ13C, C/N ratios, and organic carbon, carbonate and biogenic silica accumulation rates, document changes in effective moisture at decadal time scales during the early Little Ice Age period to present. Results indicate that between ～AD 1000 and 1600, effective moisture was higher than today. A shift to more arid climate conditions occurred after ～AD 1650. The 19th and 20th centuries have been the driest of the past millennium. Temporal variations correspond with inferred shifts in summer evaporation from Marcella Lake δ18O, a similarly small, stratified, alkaline lake located ～250 km to the southwest, suggesting that the combined reconstructions accurately document the regional paleoclimate of the east-central interior. Comparison with regional glacial activity suggests differing regional moisture patterns during early and late Little Ice Age advances.  相似文献   

14.
《Precambrian Research》2002,113(1-2):43-63
Carbon, oxygen and strontium isotope compositions of carbonate rocks of the Proterozoic Vindhyan Supergroup, central India suggest that they can be correlated with the isotope evolution curves of marine carbonates during the latter Proterozoic. The carbonate rocks of the Lower Vindhyan Supergroup from eastern Son Valley and central Vindhyan sections show δ13C values of ∼0‰ (V-PDB) and those from Rajasthan section are enriched up to +2.8‰. In contrast, the carbonate rocks of the Upper Vindhyan succession record both positive and negative shifts in δ13C compositions. In the central Vindhyan section, the carbonates exhibit positive δ13C values up to +5.7‰ and those from Rajasthan show negative values down to –5.2‰. The δ18O values of most of the carbonate rocks from the Vindhyan Supergroup show a narrow range between –10 and –5‰ (V-PDB) and are similar to the ‘best preserved’ 18O compositions of the Proterozoic carbonate rocks. In the central Vindhyan and eastern Son Valley sections, carbonates from the Lower Vindhyan exhibit best-preserved 87Sr/86Sr compositions of 0.7059±6, which are lower compared to those from Rajasthan (0.7068±4). The carbonates with positive δ13C values from Upper Vindhyan are characterized by lower 87Sr/86Sr values (0.7068±2) than those with negative δ13C values (0.7082±6). A comparison of C and Sr isotope data of carbonate rocks of the Vindhyan Supergroup with isotope evolution curves of the latter Proterozoic along with available geochronological data suggest that the Lower Vindhyan sediments were deposited during the Mesoproterozoic Eon and those from the Upper Vindhyan represent a Neoproterozoic interval of deposition.  相似文献   

15.
Nineteen samples of metamorphosed carbonate-bearing rocks were analyzed for carbon and oxygen isotope ratios by ion microprobe with a ∼5-15 μm spot, three from a regional terrain and 16 from five different contact aureoles. Contact metamorphic rocks further represent four groups: calc-silicate marble and hornfels (6), brucite marble (2), samples that contain a reaction front (4), and samples with a pervasive distribution of reactants and products of a decarbonation reaction (4). The average spot-to-spot reproducibility of standard calcite analyses is ±0.37‰ (2 standard deviations, SD) for δ18O and ±0.71‰ for δ13C. Ten or more measurements of a mineral in a sample that has uniform isotope composition within error of measurement can routinely return a weighted mean with a 95% confidence interval of 0.09-0.16‰ for δ18O and 0.10-0.29‰ for δ13C. Using a difference of >6SD as the criterion, only four of 19 analyzed samples exhibit significant intracrystalline and/or intercrystalline inhomogeneity in δ13C at the 100-500 μm scale, with differences within individual grains up to 3.7‰. Measurements are consistent with carbon isotope exchange equilibrium between calcite and dolomite in five of six analyzed samples at the same scale. Because of relatively slow carbon isotope diffusion in calcite and dolomite, differences in δ13C can survive intracrystalline homogenization by diffusion during cooling after peak metamorphism and likely represent the effects of prograde decarbonation and infiltration. All but 2 of 11 analyzed samples exhibit intracrystalline differences in δ18O (up to 9.4‰), intercrystalline inhomogeneity in δ18O (up to 12.5‰), and/or disequilibrium oxygen isotope fractionations among calcite-dolomite, calcite-quartz, and calcite-forsterite pairs at the 100-500 μm scale. Inhomogeneities in δ18O and δ13C are poorly correlated with only a single mineral (dolomite) in a single sample exhibiting both. Because of relatively rapid oxygen isotope diffusion in calcite, intracrystalline inhomogeneities in δ18O likely represent partial equilibration between calcite and fluid during retrograde metamorphism. Calcite is in oxygen isotope exchange equilibrium with forsterite in one of four analyzed samples, in equilibrium with dolomite in none of six analyzed samples, and in equilibrium with quartz in neither of two analyzed samples. There are no samples of contact metamorphic rock with analyzed reactants and products of an arrested metamorphic reaction that are in oxygen isotope equilibrium with each other. The degree of departure from equilibrium in analyzed samples is variable and is often related, at least in part, to alteration of δ18O of calcite during retrograde fluid-rock reaction. In situ sub-grain-scale carbon and oxygen isotope analyses of minerals are advisable in the common applications of stable isotope geochemistry to metamorphic petrology. Correlation of sub-mm scale stable isotope data with imaging will lead to improved understanding of reaction kinetics, reactive fluid flow, and thermal histories during metamorphism.  相似文献   

16.
Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.  相似文献   

17.
Peter K. Swart 《Sedimentology》2015,62(5):1233-1304
Stable carbon and oxygen isotopes (δ18O and δ13C values) and trace elements have been applied to the study of diagenesis of carbonate rocks for over 50 years. As valuable as these insights have been, many problems regarding the interpretation of geochemical signals within mature rocks remain. For example, while the δ18O values of carbonate rocks are dependent both upon the temperature and the δ18O value of the fluid, and additional information including trace element composition aids in interpreting such signals, direct evidence of either the temperature or the composition of the fluids is required. Such information can be obtained by analysing the δ18O value of any fluid inclusions or by measuring the temperature using a method such as the ‘clumped’ isotope technique. Such data speak directly to a large number of problems in interpreting the oxygen isotope record including the well‐known tendency for δ18O values of carbonate rocks to decrease with increasing age. Unlike the δ18O, δ13C values of carbonates are considered to be less influenced by diagenesis and more a reflection of primary changes in the global carbon cycle through time. However, many studies have not sufficiently emphasized the effects of diagenesis and other post‐depositional influences on the eventual carbon isotopic composition of the rock with the classic paradigm that the present is the key to the past being frequently ignored. Finally, many additional proxies are poised to contribute to the interpretation of carbonate diagenesis. Although the study of carbonate diagenesis is at an exciting point with an explosion of new proxies and methods, care should be taken to understand both old and new proxies before applying them to the ancient record.  相似文献   

18.
In-situ ion microprobe measurements of carbon isotopic compositions of graphite were made in seven metasediments and two carbonate rocks from the ca. 3.8 Ga Isua supracrustal belt, West Greenland. The δ13C values of micron-scale graphite globules in the metasediments and the carbonate rocks vary from -18 to +2‰ and from -7 to -3‰, respectively. The maximum δ13C value of graphite globules in the metasediment rises from -14 to -5‰, as the metamorphic grade increases from epidote-amphibolite to upper amphibolite facies. In a single hand specimen, the δ13C values of graphite inclusions in garnet are ∼7‰ lower on average than those outside garnet. Similarly, graphite armored by quartz apparently shows a few permil lower δ13C values than those on grain boundaries between noncarbonate minerals. The fact that early crystallized minerals include relatively 13C-depleted graphite indicates that the regional metamorphism increased the δ13C values of the Isua graphite. This is consistent with the regional trend of 13C-enrichment accompanied by the increase of metamorphic grade. The minimum fractionation between graphite and carbonate is consistent with the equilibrium fractionation at about 400 to 550 °C. These observations indicate that isotopic exchange with isotopically heavy carbonate caused 13C-enrichment of Isua graphite. The δ13C values of graphite reported here (δ13C > -18‰) were produced either as a metamorphic modification of organic carbon with initially much lower δ13C values, or as an abiological reaction such as decomposition of carbonate. If the isotopic exchange between carbonate and graphite during regional metamorphism controlled the 13C-enrichment of Isua graphite, previously reported large 13C-depletion of graphite, especially armored by apatite (Mojzsis et al., 1996) was probably premetamorphic in origin. This supports the existence of life at Isua time (ca. 3.8 Ga).  相似文献   

19.
Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ34SSO4 and δ18OSO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ18OH2O and initial δ18OSO4, all strains show 34S enrichment, whereas only six strains show significant 18O enrichment. The remaining six show no (or minimal) change in δ18OSO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO32−), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.  相似文献   

20.
Rats were raised on a variety of isotopically controlled diets comprising 20% C3, C4 or marine protein and C3 and/or C4 non-protein or energy (i.e. sucrose, starch and oil) macronutrients. Compound specific stable carbon isotope (δ13C) analysis was performed on the cholesterol isolated from the diet (n=7 ) and bone (n=15 ) of these animals and the values compared with bulk δ13C measurements of bone collagen and apatite. The dietary signals reflected by these three bone biochemical components were investigated using linear regression analysis. δ13C values of bone cholesterol were shown to reflect whole diet δ13C values, collagen to reflect mainly dietary protein values and apatite to reflect whole diet values. Further correlations between dietary protein-to-energy spacings (Δ13Cprot-engy = δ13Cprotein - δ13Cenergy) and whole diet-to-bone component fractionations (Δ13Cbcomp-wdiet = δ13Cbone component - δ13Cwhole diet) indicates that for hypothetical diets where protein δ13C values are equal to energy values, fractionations between whole diet and bone biochemical fractions are -3.3‰ for cholesterol, +5.4‰ for collagen and +9.5‰ for apatite. Moreover, the narrow range of variation observed in apatite-to-cholesterol spacings (Δ13Capat-bchol) suggests that cholesterol δ13C values can potentially also be used as an independent test for the isotopic integrity of apatite δ13C values. These insights into bone cholesterol, collagen and apatite dietary signals, diet-to-bone fractionations and bone component-to-bone component spacings provide the basis for more accurate interpretations of the dietary behaviour of archaeological populations and food webs when the δ13C analysis of bone is employed.  相似文献   

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