利用多年冻土区湖相沉积物中埋藏植物稳定碳同位素组成重建大气CO2浓度

沉水植物碳同位素分馏同水中溶解无机碳浓度有一定的关系，因而可以通过青藏高原多年冻土区的湖相沉积物中埋藏沉水植物－－龙须眼子菜（Potamogeton pectinatus)植物屑的碳同位素组成重建该地大气CO2浓度的变化情形，研究结果表明，该地在9．17－6．77ka BP间，大气CO2浓度是整个研究时间段中最低的，其后在6．77－4．56ka BP时期大气CO2浓度增加，在4．56－2．17ka BP之间，大气CO2浓度是整个研究时间内CO2浓度最高的阶段，植物屑的碳同位素组成反映了溶解无机碳浓度的变化，从而可用以重建大气CO2浓度的变化情况。     

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

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.     

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

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.     

Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.     

Carbon isotopic fractionation in lipids from methanotrophic bacteria II: the effects of physiology and environmental parameters on the biosynthesis and isotopic signatures of biomarkers

Controls on the carbon isotopic signatures of methanotroph biomarkers have been further explored using cultured organisms. Growth under conditions which select for the membrane-bound particulate form of the methane monooxygenase enzyme (pMMO) leads to a significantly higher isotopic fractionation than does growth based on the soluble isozyme in both RuMP and serine pathway methanotrophs; in an RuMP type the delta delta 13Cbiomass equaled -23.9% for pMMO and -12.6% for sMMO. The distribution of biomarker lipids does not appear to be significantly affected by the dominance of one or the other MMO type and their isotopic compositions generally track those of the parent biomass. The 13C fractionation behaviour of serine pathway methanotrophs is very complex, reflecting the assimilation of both methane and carbon dioxide and concomitant dissimilation of methane-derived carbon. A limitation in CH4 availability leads to the production of biomass which is 13C-enriched with respect to both carbon substrates and this occurs irrespective of MMO type. This startling result indicates that there must be an additional fractionation step downstream from the MMO reaction which leads to incorporation of 13C-enriched carbon at the expense of dissimilation of 13C-depleted CO2. In these organisms, polyisoprenoid lipids are 13C-enriched compared to polymethylenic lipid which is the reverse of that found in the RuMP types. Serine cycle hopanoids, for example, can vary anywhere from 12% depleted to 10% enriched with respect to the CH4 substrate depending on its concentration. Decrease in growth temperature caused an overall increase in isotopic fractionation. In the total biomass, this effect tended to be masked by physiological factors associated with the type of organism and variation in the bulk composition. The effect was, however, clearly evident when monitoring the 13C signature of total lipid and individual biomarkers. Our results demonstrate that extreme carbon isotopic depletion in field samples and fossil biomarker lipids can be indicative of methanotrophy but the converse is not always true. For example, the hopanoids of a serine cycle methanotroph may be isotopically enriched by more than 10% compared to the substrate methane when the latter is limiting. In other words, hopanoids from some methanotrophs such as M. trichosporium would be indistinguishable from those of cyanobacteria or heterotrophic bacteria on the basis of either chemical structure or carbon isotopic signature.     

The C-O and Zn isotopic compositions of the Laochang Ag-Pb-Zn ore bodies in the Changning-Menglian suture zone,and its geological implicationsSCIEI北大核心CSCD

老厂矿床是昌宁-孟连缝合带内唯一大型矿床,本文报道了老厂矿床Ag-Pb-Zn矿体中Ⅰ号矿体群下部块状矿体和上部网脉状矿体的方解石C-O同位素组成,以及Ⅰ、Ⅱ、Ⅳ三个矿体群内闪锌矿的Zn同位素组成。Ⅰ号矿体群下部块状矿体和上部网脉状矿体方解石δ¹³C_PDB的范围分别为-6.17‰～2.71‰和-2.18‰～3.87‰,δ¹⁸O_PDB的范围分别为-19.57‰～-17.23‰和-22.10‰～-16.21‰;计算获得对应成矿流体的δ¹³C_CO2为-6.16‰～1.53‰和-2.39‰～6.43‰,δ¹⁸O_H2O分别为1.62‰～7.62‰和4.36‰～16.92‰,通过与岩浆CO₂(δ¹³C=-2‰～-8‰)和围岩灰岩(δ¹³C=-1.6‰～4.0‰)的δ¹³C值相比较,指示块状矿体成矿流体中的碳主要来自岩浆,网脉状矿体成矿流体中...     

Geochemical implications of induced changes in C13 fractionation by blue-green algae

The photosynthetic fractionation of carbon isotopes by blue-green algae in laboratory culture is dependent in a non-linear fashion on the CO₂ concentration in the feed gas. For the three species tested, the minimum fractionation occurred at a CO₂ concentration of 0.2% in air and was approximately zero for the two marine species tested. Enrichment of C¹² in the reduced carbon is not an inevitable result of photosynthetic carbon fixation. Temperature and pH had no detectable effect on fractionation. The maximum fractionation observed in the laboratory cultures or in recent blue-green algal mats was 18‰. Differences in the isotope ratio of coexisting oxidized and reduced carbon in Precambrian stromatolites are as great as 31‰. Present carbon isotopic evidence is not consistent with the idea that blue-green algae were major contributors to the organic matter in Precambrian sediments.     

Ultrahigh-Temperature Metamorphism in Madurai Granulites, Southern India: Evidence from Carbon Isotope Thermometry

Ultrahigh-temperature (UHT) metamorphism in the Madurai Block of the southern Indian granulite terrain has been verified using the calcite-graphite isotope exchange thermometer. Carbon isotope thermometry has been applied to marbles from a locality near the reported occurrence of sapphirine granulites that have yielded temperature estimates of around 1000 degrees C. The delta(13)C and delta(18)O values of calcite are homogenous, implying equilibration of the isotopes during metamorphism. However, the delta(13)C values of single graphite crystals show variations in the order of 1 per thousand within a hand specimen. Detailed isotopic zonation studies indicate that graphite preserves either the time-integrated crystal growth history or reequilibrium fractionation during its cooling history. The graphite cores preserve higher delta(13)C values than the rims. The fractionation between calcite and graphite cores gives the highest metamorphic temperature of about 1060 degrees C, which matches the petrologically inferred temperature estimates in the high-magnesian pelites. The fractionation between graphite rims and calcite suggests a temperature of around 750 degrees C, which is interpreted to reflect retrograde cooling. This event is also observed in the sapphirine granulites. Calcite-graphite thermometry thus provides a useful tool to define UHT metamorphism in granulite terrains.     

微藻CO2同化过程的稳定碳同位素分馏值

研究微藻CO2同化过程中的碳同位素分馏值,对研究微藻在碳效应过程中的作用具有重要意义。目前还没有获取微藻CO2同化过程的稳定碳同位素分馏值的在体实验方法。文章以莱茵衣藻、蛋白核小球藻、及野外红枫湖混合藻三种岩溶湖泊微藻为例,利用双向标记建立了能在体获得此分馏值的方法,并通过此分馏值定量了微藻的各种无机碳利用途径份额。获得各自CO2同化过程中的碳同位素分馏值分别为15.3‰、14.8‰、21.7‰。三种藻分馏值差异主要与藻的种类及其细胞体积大小有关。利用此分馏值计算出衣藻、小球藻、混合藻自然培养下的碳酸氢根离子途径利用份额分别为100%、81.1%、97.8%,表明了生长在岩溶湖泊的微藻利用无机碳的途径主要为碳酸氢根离子。      

Oxygen-isotope variations in sulfate ions in the water of some Italian lakes

The results obtained by measuring the sulfate content and its $\text{O}{}^{18}\text{O}{}^{16}$ ratios through time in some volcanic, tectonic and dam Italian lakes are reported here. The variations with time of the oxygen isotopic composition of the lake waters are also reported. The measurements refer mainly to surface water; however, a few deep samples were also studied.In the case of all the lakes examined, the variations with time of the oxygen isotopic composition and of the concentration of the dissolved sulfate cannot be explained in terms of the addition and of seasonal variations of the O¹⁸ content of rainwater sulfate. Biological redox processes involving bacterial reduction of sulfate and sulfide oxidation can reasonably account for the results obtained.According to Lloyd (1967), when sulfate is formed by bacterial sulfide oxidation, 68 per cent of the sulfate oxygen is water oxygen, while 32 per cent is dissolved molecular oxygen. The isotopic enrichment of the dissolved molecular oxygen in the lake waters relative to the isotope content of the atmospheric oxygen is mainly related to the biological activity in the waters.Assuming that a stagnation period takes place during summer and fall while a period of strong bio-respiratory activity takes place during winter and spring, it follows that a small isotope fractionation effect on molecular dissolved oxygen can be expected during stagnation while a high isotope fractionation can be expected during winter and spring. The O¹⁸ content of the sulfate dissolved in volcanic and tectonic lakes varies according to this hypothesis. The fact that similar O¹⁸ contents of the dissolved sulfate are or are not found in the same period of different years is probably related to similarities or differences in the climatic conditions.The bio-physical behaviour of the Corbara dam lake is different from that of other lakes. However, because of the continuous feeding by the Tiber River, variations of the sulfate concentration and its oxygen isotopic composition can be caused by the contribution of polluted water.     

Nuclear field shift in natural environments

The nuclear field shift (NFS) is an isotope shift in atomic energy levels caused by a combination of differences in nuclear size and shape and electron densities at the nucleus. The effect of NFS in isotope fractionation was theoretically established by Bigeleisen in 1996 [Bigeleisen J. (1996) J. Am. Chem. Soc. 118:3676–3680] and has been analytically measured in laboratory chemical exchange reactions. More recently, some isotopic variations of heavy elements (Hg, Tl, U) measured in natural systems as well as isotopic anomalies measured for lower-mass elements in meteorites have been attributed to the NFS effect. These isotopic variations open up new and exciting fields of investigations in Earth sciences. In this paper, we review the different natural systems in which NFS has been proposed to be the origin of isotopic variations.     

藻类及其有机质的成矿作用试验

通过藻类、细菌聚矿和成矿的模拟试验,讨论了有机成矿的环境、方法和途径,认为有机质螯合,络合、迁移再沉积过程中,水化学环境改变造成矿物沉淀。同时得出如下结论:藻菌聚矿和成矿需要特定的环境背景。环境决定着不同的藻菌类群、有机质及其丰度,而这些藻菌类群、有机质及其丰度又决定着聚矿和成矿的可能性和强度。     

Hydrogen isotope fractionation in freshwater and marine algae: II. Temperature and nitrogen limited growth rate effects

Zhang and Sachs [Hydrogen isotope fractionation in freshwater algae: I. Variations among lipids and species. Organic Geochemistry 38, 582–608, 2007] demonstrated that algal lipid δD values track water δD values with high fidelity (R² > 0.99), but that D/H fractionation varied among lipids and algal species. Here we report on the influence of temperature and nitrogen limitation on D/H fractionation in lipids from cultured microalgae. Two species of freshwater green algae, Eudorina unicocca and Volvox aureus, were grown in batch culture at 15 °C and 25 °C. Increased D/H fractionation of 2?4‰/°C occurred at the higher temperature in all lipids analyzed. The marine diatom Thalassiosira pseudonana was grown in continuous culture under nitrogen replete (NR) and nitrogen limited (NL) conditions, resulting in a growth rate that was 4.4 fold lower under the latter conditions. The fatty acid content of NL cells was approximately 4 fold higher than in NR cells, whereas the sterol content was similar in both. While sterols from the NL culture were enriched in deuterium by 37‰ relative to the NR culture, fatty acids from both cultures had similar δD values, implying that D/H fractionation during isoprenoid (branched) lipid synthesis is affected by nitrogen limitation, but D/H fractionation during acetogenic (linear) lipid synthesis is not. Cross-talk of the precursor isopentenyl diphosphate between the cytosolic MVA and plastidic DOXP/MEP synthetic pathways is a plausible mechanism for the observed D/H differences between isoprenoid and acetogenic lipids. This preliminary study highlights the need to consider both the type of lipid and potential changes in growth conditions in paleoenvironmental studies using lipid D/H ratios.     

Lithium isotope systematics in a forested granitic catchment (Strengbach, Vosges Mountains, France)

Over the last decade it has become apparent that Li isotopes may be a good proxy to trace silicate weathering. However, the exact mechanisms which drive the behaviour of Li isotopes in surface environments are not totally understood and there is a need to better calibrate and characterize this proxy. In this study, we analysed the Li concentrations and isotopic compositions in the various surface reservoirs (soils, rocks, waters and plants) of a small forested granitic catchment located in the Vosges Mountains (Strengbach catchment, France, OHGE http://ohge.u-strasbg.fr). Li fluxes were calculated in both soil profiles and at the basin scale and it was found that even in this forested basin, atmospheric inputs and litter fall represented a minor flux compared to input derived from the weathering of rocks and soil minerals (which together represent a minimum of 70% of dissolved Li). Li isotope ratios in soil pore waters show large depth dependent variations. Average dissolved δ⁷Li decreases from −1.1‰ to −14.4‰ between 0 and −30 cm, but is +30.7‰ at −60 cm. This range of Li isotopic compositions is very large and it encompasses almost the entire range of terrestrial Li isotope compositions that have been previously reported. We interpret these variations to result from both the dissolution and precipitation of secondary phases. Large isotopic variations were also measured in the springs and stream waters, with δ⁷Li varying from +5.3‰ to +19.6‰. δ⁷Li increases from the top to the bottom of the basin and also covaries with discharge at the outlet. These variations are interpreted to reflect isotopic fractionations occurring during secondary phase precipitation along the water pathway through the rocks. We suggest that the dissolved δ⁷Li increases with increasing residence time of waters through the rocks, and so with increasing time of interaction between waters and solids. A dissolution precipitation model was used to fit the dissolved Li isotopic compositions. It was found that the isotopic compositions of springs and stream waters are explicable by an isotopic fractionation of −5‰ to −14‰ (best fit −10.8‰), in agreement with Li incorporation into clay. In soil solutions, it was found that isotopic fractionation during secondary precipitation is larger (at least −23‰), suggesting a major role for different secondary phases, such as iron oxides that maybe incorporate Li with a higher isotope fractionation.     

有孔虫中硼的分离及其同位素组成测定的初步研究

本文初步建立了一种用硼特效树脂和阴、阳混和离子交换树脂相结合进行有孔虫中硼的分离和同位素测定的方法。该方法适用低硼含量 (纳克级 )的微体古生物中的硼的分离和同位素测定 ,分离过程不产生同位素分馏 ,满足了正热电离质谱法测定硼同位素的要求。     

水合物生成过程中碳同位素组成变化的实验研究

天然气水合物是一种新型的洁净能源。甲烷天然气水合物是储量最丰富的一种类型,常出现在深海中或极地大陆上,其生成的过程中会发生同位素的分馏效应。通过实验室模拟水合物生成的过程,利用天然海水与甲烷或二氧化碳气体反应,以及更接近实际生成环境的甲烷-海水-沉积物动态聚散实验,对甲烷水合物和二氧化碳水合物生成前后δ13C值进行测定,研究水合物生成过程中δ13C的变化情况。实验证明,水合物反应中碳同位素分馏是存在的,其变化程度明显小于氧同位素和氢同位素。甲烷水合物碳同位素的分馏系数αC的值为1000 3~1000 9。二氧化碳水合物生成反应后气相的碳、氧同位素变轻,重同位素趋向于进入水合物中,二氧化碳水合物碳同位素的分馏系数αC的值为1000 7~1001 2。海水中溶解的CO2气体在甲烷水合物形成过程中会被水合物捕获,从而使得δ13CDIC值变小,重的碳同位素趋于进入水合物中,而较轻的碳同位素留在海水中。但由于海水中含有的溶解CO2气体有限,经过多轮水合物动态聚散后δ13CDIC值的变化幅度会越来越小。     

Europium isotopic variations in Allende CAIs and the nature of mass-dependent fractionation in the solar nebula

We measured the ¹⁵³Eu/¹⁵¹Eu ratio by MC-ICP-MS for a terrestrial basalt, two terrestrial soils, and four meteorites (whole rocks and/or chondrules of Bjurböle, Forest City, Murchison, and Allende) and found no isotopic variations. By contrast, two CAI separates from two different pieces of Allende show a ¹⁵³Eu deficit of up to one per mil. Such a shortage in the heavy isotopes, which had also been identified in Allende CAIs for Sr [Patchett, P.J. 1980b. Sr isotopic fractionation in Allende chondrules: a reflection of solar nebular processes. Earth Planet. Sci. Lett.50, 181-188], cannot reflect evaporative fractionation. The lack of Sm isotope fractionation in the same samples further makes fractionation by purely kinetic processes an unlikely cause of the anomalous Eu isotopic composition. An alternative interpretation is condensation from a vapor already significantly depleted in Eu, but in such a scenario the fate of the missing material is unclear. We therefore prefer yet another interpretation, based on the low ionization potential of Eu (and Sr), in which electromagnetic separation of the ionized gas preferentially depletes the nebular gas in heavy isotopes.     

O-Sr isotopic variations in Miocene granitoids from the Aegean: evidence for an origin by combined assimilation and fractional crystallization

Sr, O, and D/H isotopic compositions have been analyzed in Miocene metaluminous to slightly peraluminous (I-type) granitoids of the central Aegean. Individual plutonic complexes display significant variations in their ¹⁸O and initial⁸⁷Sr/⁸⁶Sr compositions.D and ¹⁸O compositions of minerals and whole-rocks are mostly in the magmatic range. Some samples from Naxos and Mykonos/Delos show low D and ¹⁸O values characteristic of meteoric-water-hydrothermal interaction, but as a whole the changes in ¹⁸O and Sr isotopic compositions as a result of hydrothermal alteration were slight, even in instances where marked alteration is petrographically observable. Consequently, the bulk-rock variations of ¹⁸O from 8.1 to 12.0 and of⁸⁷Sr/⁸⁶Sr from 0.70438 to 0.71450 may be regarded as primary and indicative of the conditions of their evolution. Heterogeneous isotopic compositions observed in the individual plutons of Serifos, Ikaria, Samos and Kos may be caused by the multiple intrusion of chemically and isotopically distinct magma pulses, with high viscosities and relatively rapid consolidation in most cases preventing complete homogenization. The granitoids of Serifos, Ikaria and Kos display weak correlations between the initial⁸⁷Sr/⁸⁶Sr and ¹⁸O and 1/Sr. The granitoid province shows a positive correlation between⁸⁷Sr/⁸⁶Sr and ¹⁸O and a non-linear relationship between⁸⁷Sr/⁸⁶Sr and 1/Sr, whereby 1/Sr increases more rapidly than the isotopic ratio as the degree of fractionation of the rocks increases. It is argued that assimilation of older continental material by mantle-derived arc magmas with combined fractionation (AFC) is the most plausible model to explain the chemical and isotopic characteristics of the granitoids and the geological situation in which rock-types trend from granodiorites in the (south)west, near the inferred Oligocene-Miocene suture, to granites in the center and monzonites in the (north)east of the province.     

Colloidal Stability and Toxicity of Gold Nanoparticles and Gold Chloride on <Emphasis Type="Italic">Chlamydomonas reinhardtii</Emphasis>

Here we have examined interactions of gold nanoparticles differing in primary particle size and coating with the green algae Chlamydomonas reinhardtii as function of the colloidal stability of the particles in the experimental media used for toxicity studies. Interactions of dissolved Au³⁺ ions with algae were also examined. Included endpoints were photosynthetic yield and algal growth. Morphological and structural effects were examined microscopically and by flow cytometry. The results indicate no significant toxicity of gold nanoparticles to C. reinhardtii. Analysis of published data suggests toxicity of gold nanoparticles on algal growth to relate rather to particular coatings than to the gold core.     

Predictive isotopic biogeochemistry: hydrocarbons from anoxic marine basins

Carbon isotopic compositions were determined for individual hydrocarbons in water column and sediment samples from the Cariaco Trench and Black Sea. In order to identify hydrocarbons derived from phytoplankton, the isotopic compositions expected for biomass of autotrophic organisms living in surface waters of both localities were calculated based on the concentrations of CO2(aq) and the isotopic compositions of dissolved inorganic carbon. These calculated values are compared to measured delta values for particulate organic carbon and for individual hydrocarbon compounds. Specifically, we find that lycopane is probably derived from phytoplankton and that diploptene is derived from the lipids of chemoautotrophs living above the oxic/anoxic boundary. Three acyclic isoprenoids that have been considered markers for methanogens, pentamethyleicosane and two hydrogenated squalenes, have different delta values and apparently do not derive from a common source. Based on the concentration profiles and isotopic compositions, the C31 and C33 n-alkanes and n-alkenes have a similar source, and both may have a planktonic origin. If so, previously assigned terrestrial origins of organic matter in some Black Sea sediments may be erroneous.