The geochemistry of iodine in oxidised and reduced recent marine sediments

Surface sediments from the South West Africa shelf and the Gulf of California have been analysed for iodine and organic carbon. The iodine contents range from 96 to 1990 ppm. While iodine and organic carbon show certain anomalies on the South West Africa shelf, the trend of the $\text{I}\text{C}$ ratios is smooth and decreases from the shelf edge, an area of oxidising surface sediment, shorewards to reducing sediments, formed as a result of intense water upwelling. In the Gulf of California, a similar distribution of $\text{I}\text{C}$ ratios with surface sediment type occurs; lowest values occur in the reduced sediments and highest in oxidised sediments. Values of the $\text{I}\text{C}\text{(× 10}{}^4\text{)}$ ratio of the oxidised sediments (~250) are more than an order of magnitude higher than in reduced sediments, and are similar to some other surface oxidised sediments.The high I content of oxidised sediments is mostly due to uptake of I on to plankton seston on the seabed. In reduced sediments, I contained in planktonic matter originating in surface waters forms the bulk of iodine in the sediment.With sediment burial, oxidised sediments lose most of the iodine through degradation of unspecified organic constituents. This does not happen to the same extent in reduced sediments. The geological implications of these reactions are briefly discussed.     

Sedimentary pyrite formation: An update

Sedimentary pyrite formation during early diagenesis is a major process for controlling the oxygen level of the atmosphere and the sulfate concentration in seawater over geologic time. The amount of pyrite that may form in a sediment is limited by the rates of supply of decomposable organic matter, dissolved sulfate, and reactive detrital iron minerals. Organic matter appears to be the major control on pyrite formation in normal (non-euxinic) terrigenous marine sediments where dissolved sulfate and iron minerals are abundant. By contrast, pyrite formation in non-marine, freshwater sediments is severely limited by low concentrations of sulfate and this characteristic can be used to distinguish ancient organic-rich fresh water shales from marine shales. Under marine euxinic conditions sufficient H₂S is produced that the dominant control on pyrite formation is the availability of reactive iron minerals.Calculations, based on a sulfur isotope model, indicate that over Phanerozoic time the worldwide average organic carbon-to-pyrite sulfur ratio of sedimentary rocks has varied considerably. High $\text{C}\text{S}$ ratios during Permo-Carboniferous time can be explained by a shift of major organic deposition from the oceans to the land which resulted in the formation of vast coal swamps at that time. Low $\text{C}\text{S}$ ratios, compared to today, during the early Paleozoic can be explained in terms of a greater abundance of euxinic basins combined with deposition of a more reactive type of organic matter in the remaining oxygenated portions of the ocean. The latter could have been due to lower oceanic oxygen levels and/or a lack of transportation of refractory terrestrial organic matter to the marine environment due to the absence of vascular land plants at that time.     

Origin of epigenetic calcite in coal from Antarctica and Ohio based on isotope compositions of oxygen,carbon and strontium

Isotopic compositions of oxygen, carbon and strontium of calcite cleats in coal seams of southern Victoria Land, Antarctica, and Tuscarawas County, Ohio, contain a record of the conditions a the time of their formation. The Antarctic calcites (δ ¹⁸O(SMOW) = +9.14 to +11.82%₀) were deposited from waters enriched in ¹⁶O whose isotopic composition was consistent with that of meteoric precipitation at low temperature and high latitude. The carbon of the calcite cleats (δ ¹³C(PDB) = ?15.6 to ?16.9%₀) was derived in part from the coal (δ ¹³C(PDB) = ?23.5 to ?26.7%₀) as carbon dioxide and by oxidation of methane or other hydrocarbon gases. The strontium (${}^{87}\text{Sr}{}^{86}\text{Sr}\text{= 0.71318–0.72392)}$ originated primarily from altered feldspar grains in the sandstones of the Beacon Supergroup.Calcite cleats in the Kittaning No. 6 coal seam of Ohio (δ ¹⁸O(SMOW) = +26.04 to +27.79%₀) were deposited from waters that had previously exchanged oxygen, possibly with marine carbonate at depth. The carbon (δ ¹³C(PDB) = 0.9 to +2.4%₀) is enriched in ¹³C even though that cleats were deposited in coal that is highly enriched in ¹²C and apparently originated from marine carbonates. Strontium in the cleats ($\text{Sr}\text{87}$ 0.71182–0.71260) is not of marine origin but contains varying amounts of radiogenic ⁸⁷Sr presumably derived from detrital Rb-bearing minerals in the adjacent sedimentary rocks. The results of this study suggest that calcite cleats in coal of southern Victoria Land, Antarctica, were deposited after the start of glaciation in Cenozoic time and that those in Ohio precipitated from formation waters derived from the underlying marine carbonate rocks, probably in the recent geologic past.     

Carbon isotope geochemistry of the 3.7 × 109-yr-old Isua sediments,West Greenland: implications for the Archaean carbon and oxygen cycles

One hundred and twenty-four carbonate samples from the meta-sedimentary sequence of the 3.7 × 10⁹ yr old Isua supracrustal belt (W-Greenland) have yielded a δ¹³C_carb average of ?2.5 ± 1.7%. vs PDB and a δ¹⁸O_carb average of +13.0 ± 2.5%. vs SMOW. The oxygen mean comes fairly close to the averages of other early Precambrian carbonates. The carbon average, however, is some 2%. more negative than those of younger marine carbonates. In terms of a simple terrestrial ¹³C mass balance, if δ¹³C_carb values are original sedimentary values, this more negative δ¹³C average would imply a considerably smaller $\text{C}{}_{\mathrm{org}}\text{C}{}_{\mathrm{carb}}$ ratio in the sedimentary shell during Isua times, and would thus support the concept of a gradual buildup of a sedimentary reservoir of organic carbon during the early history of the Earth. Since, however, the Isua supracrustal rocks have experienced amphibolite-grade metamorphism, which in other areas has been shown to lower δ¹³C_carb values, it is most likely that the original values of these rocks were approx 0%.. This indicates that C_orx and C_carb were present in the ancient carbon reservoir in about ‘modern’ proportions. Unless this early stabilization of the terrestrial carbon cycle in terms of a constant partitioning of carbon between the reduced and oxidized species is shown to have been caused by some inorganic geochemical process, a considerably earlier start of chemical evolution and spontaneous generation of life must be considered than is presently accepted.     

Ocean chemistry during glacial time

Measurements of CO₂ to air ratios in the gas trapped in bubbles in ice of glacial age suggest that the CO₂ content of the atmosphere was considerably lower during peak glacial time than during Holocene time. The purpose of this paper is to show that such a change must in all likelihood be the result of alterations in the nutrient element chemistry of sea water. Two possible scenarios are presented. One involves alternate storage and erosion of phosphorous leaving residues from shelf sediments. The other involves changes in the $\text{C}\text{P}$ ratio in the organic debris falling to the deep sea. Means of verifying the nutrient cycle hypothesis are also given. It is shown that the ¹³C record as we know it in planktonic and benthic foraminifera, the oxygen record as inferred from benthic foraminifera species distributions, and the early post glacial CaCo₃ preservation event as recorded by aragonitic pteropods are consistent with both of the hypotheses presented. Only if an early post glacial spike in the ¹³C record for planktonic shells could be found would it be possible to eliminate one of these hypotheses (i.e., that involving shelf storage). The implications of these nutrient hypotheses to climate theory are as follows. If shelf storage is responsible for the glacial to interglacial CO₂ increase, then the CO₂ change must be considered an amplifier of some primary cause. The reason is that sea level changes are needed to drive deposition on (and erosion from) the shelves. On the other hand, if changes in the $\text{C}\text{P}$ ratio for falling debris are responsible, then the CO₂ change could either be an amplifier or a primary cause for the major glacial to interglacial climatic cycle. The latter is possible as self-sustained oscillations in ocean chemistry might be driven by interactions between ocean ecology and ocean nutrient chemistry.     

Precambrian sedimentary carbonates: carbon and oxygen isotope geochemistry and implications for the terrestrial oxygen budget

Carbon isotope values of 260 Precambrian limestones and dolomites (most of them being substantially unaltered) have yielded an overall mean of $\text{δ}{}^{13}\text{C}\text{= +0.4 ± 2.7‰}$ vs. PDB; the corresponding oxygen values average at $\text{δ}{}^{13}\text{O = +20.0 ± 4.2‰}$ vs. SMOW. Like the overall mean, the δ ¹³C values furnished by individual carbonate occurrences are, as a rule, fairly “modern” and almost constant as from the very beginning of the sedimentary record. A remarkable exception are the “heavy” dolomites of the Middle Precambrian Lomagundi Group, Rhodesia, with $\text{δ}{}^{13}\text{C}\text{= +9.4 ± 2.0‰}$ vs. PDB. As a result of our measurements, the sporadic occurrence in the geological past of anomalously heavy carbonates seems to be established.The approximate constancy around zero per mill of the δ ¹³C values of marine carbonates through geologic time would imply a corresponding constancy of the relative proportion of organic carbon in the total sedimentary carbon reservoir since about 3.3 · 10⁹ y ago (with C_org/C_total ? 0.2). Utilizing this ratio and current models for the accumulation of the sedimentary mass as a function of time, we get a reasonable approximation for the absolute quantity of organic carbon buried in sediments and, accordingly, of photosynthetic oxygen released. Within the constraints of our model (based on a terrestrial degassing constant λ = 1.16 · 10^?9 y^?1) close to 80% of the amount of oxygen contained in the present oxygen budget should have been released prior to 3 · 10⁹ y ago. Since geological evidence indicates an O₂-deficient environment during the Early and most parts of the Middle Precambrian, there is reason to believe that the distribution of this oxygen between the “bound” and the “molecular” reservoir was different from that of today (with effective O₂-consuming reactions bringing about an instantaneous transfer to the crust of any molecular oxygen released). Accordingly, the amount of C_org in the ancient sedimentary reservoir as derived from our isotope data is just a measure of the gross amount of photosynthetic oxygen produced, withholding any information as to how this oxygen was partitioned between the principal geochemical reservoirs. As a whole, the carbon isotope data accrued provide evidence of an extremely early origin of life on Earth since the impact of organic carbon on the geochemical carbon cycle can be traced back to almost 3.5 · 10⁹y.     

Biogenic hydrocarbon gases and sulfate reduction in the Orca Basin brine

The composition of light hydrocarbon gases in the Orca Basin, an anoxic, hypersaline intraslope depression on the continental slope of the northern Gulf of Mexico, indicates that both methane and ethane are biogenic in nature with a $\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3\text{)}$ ratio of 730 and a δ¹³C of methane of ?73%. relative to the PDB standard. The concentrations of methane (750 mM) and ethane (1300 mM) in the Orca Basin brine are higher than any other marine anoxic basin. These high levels result not from high rates of productivity, but from the long residence time of the brine in the basin, due to its high stability toward mixing with overlying seawater ($\text{Δσ}{}_1\text{ΔZ}\text{=}\text{3.2}\text{m}$). Both methane and ethane show well mixed distributions in the brine. These distributions probably result from convective mixing of the isohaline brine pool due to normal heat flow from the basin sediments. Methane and ethane maxima above the pycnocline at the brine/seawater interface reflect in situ production and/or consumption in the aerobic water column. Concurrent maxima in suspended particulate material distributions in this region suggest methane may be produced there in anaerobic microenvironments associated with the suspended matter. Reduced rates of anaerobic decomposition (including sulfate reduction) in the brine sediments are inferred from preserved Sargassum fronds in the sediments, vertical sulfate profiles in most cores, and the sediment organic carbon content which is two to three times higher in sediments below the high salinity brine than in the normal Gulf sediments nearby.     

Stable isotope and organo-geochemical studies on phanerozoic sediments of the Williston Basin,North America

Carbon isotope studies have been carried out on marine Phanerozoic sediments of the Williston Basin, North America. Special attention was given to the recognition of systematic variations with age.δ ¹³C measurements on the carbonate fraction show a 3%₀ depletion from the Cambrian to the Mississippian and a 1–2%₀ enrichment to the Jurassic. Both the sign of these displacements and a good correlation with the organic carbon content suggest that real variations in the rate of photosynthesis may have been the driving force for these changes with age.Because of the large isotopic heterogeneities in the organic biomass, systematic fluctuations with age in the δ ¹³C-values of the total organic carbon record are hard to prove. Nevertheless, a significant 3%₀ depletion was observed from the Devonian to the end of the Carboniferous. This depletion seems to occur on a worldwide scale. It is therefore proposed that a rise in the rate of photosynthesis as a consequence of the colonization of the continents by higher plants is the global cause of this displacement in the isotope record of the total organic carbon.The bitumen fraction does not show any systematic isotope variations with age.Comparison of coexisting δ ¹³C_org?δ ¹³C_bit pairs demonstrates that during the Ordovician-Mississippian time period no significant (> 1%₀) differences in the isotope values of these two organic carbon sources can be observed. In contrast the bitumen fraction is depleted in ¹³C as compared to the total organic carbon in the Cambrian as well as in the Pennsylvanian-Cretaceous time interval. Several parameters, i.e. the depth of burial of these sediments, the $\text{1}\text{2}$(pristane/n-C₁₇ + phytane/n-C₁₈) ratio and the n-alkane distribution pattern support the theory that the rank of the organic matter may be responsible for the observed isotopic pattern.     

Secular variations in kerogen structure and carbon,nitrogen and phosphorus concentrations in pre-Phanerozoic and Phanerozoic sedimentary rocks

Variations in the chemical composition of sedimentary rocks and the nature of kerogen through geologic time were investigated in order to obtain information on biological and environmental evolution during the pre-Phanerozoic eon. Rock samples differing in lithology, depositional environment, and age were pulverized, pre-extracted with organic solvents, and analyzed for total nitrogen (N), phosphorus (P) and organic carbon (org. C or C_T). Variations in the molecular structure of kerogen were measured by determining the ratio of org. C content after pyrolysis (C_R) to org. C content before pyrolysis (C_T), the $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio being considered an index of the degree of condensed-aromatic (as opposed to aliphatic) character. The rocks included mudstones (Early Archean (> 3 · 10⁹ years old) to Miocene), carbonate rocks (mid-Proterozoic (1.3 · 10⁹ years old) to Eocene), cherts (Early Archean (> 3 · 10⁹ years old) to Late Proterozoic (0.8 · 10⁹ years old)), and coal (Archean (> 2.7 · 10⁹ years old) to Early Proterozoic (～1.8 · 10⁹ years old)).The mudstones and carbonates showed progressive increase in org. C content with decreasing age, as reported by other investigators, but the cherts unexpectedly showed a decrease in org. C content with decreasing age. In all samples, a simple inverse correlation between $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio and org. C was observed, each rock type forming its own trend separate from but parallel to those of the other rock types. Thus, the older cherts tend to be richer in org. C and have lower $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratios, but the older carbonates and mudstones are poorer in org. C and have higher $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratios. For a given org. C concentration, chert has the highest $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio and carbonate rock the lowest, mudstone being intermediate; this may mean that chert is relatively ineffective as a catalyst for the thermal cracking of kerogen or that it inhibits cracking. N appears to be correlated with org. C. The relationship between $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio and org. C or N suggests that the concentrations of org. C and N in sedimentary rocks are largely determined by selective elimination of labile aliphatic and nitrogenous groups of kerogen during post-depositional maturation, although the nature, abundance and depositional environment of the organic source material must be taken into consideration as well. The observed secular variations of org. C, N and $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio may be ascribed to several possible causes, including age-dependent post-depositional alteration of kerogen, secular decrease in the $\text{CO}{}_2\text{O}{}_2$ ratio of the atmosphere and hydrosphere during pre-Phanerozoic time, secular increase in rates of accumulation of organic matter in sediments and evolutionary changes in the composition of the biological source material. The secular variations of the carbonates and mudstones could be accounted for by age-dependent cumulative effects of post-depositional alteration alone, whereas the secular variations of the cherts probably reflect changes in the nature of the biological source material and the composition of the atmosphere and hydrosphere. The available evidence suggests that primary characteristics of kerogen are better preserved in chert than in the other types of sediment.The $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratios of the carbonates and cherts correlate negatively with the $\text{A}{}_{\mathrm{<mtext>465</mtext><mtext>m</mtext><mtext>\mu </mtext>}}\text{A}{}_{\mathrm{<mtext>665</mtext><mtext>m</mtext><mtext>\mu </mtext>}}$ absorbance ratios of “humic matter” extracted from the same rock samples with benzene—methanol. Thus, the greater the degree of condensed-aromatic character of the kerogen, the greater the degree of condensed-aromatic character of the solvent-extractable bituminous “humic matter” with which it is associated. In addition, the ratio of aliphatic to carbonyl-type groups ($\text{CH}{}_2\text{C=O}$) in the extractable “humic matter” of carbonates and cherts correlates with the non-extractable org. C content of the rocks, suggesting that the org. C data are related to the degree of aliphatic character of the kerogen. The chemical similarity between extractable “humic matter” and its associated kerogen is evidence that the “humic matter” is as old as its rock matrix and can be accepted as a valid chemical fossil. It also suggests that information obtainable from kerogen may be gotten more easily, rapidly and cheaply from solvent-extractable organic matter. The mudstones showed little or no relationship between $\text{A}{}_{\mathrm{<mtext>465</mtext><mtext>m</mtext><mtext>\mu </mtext>}}\text{A}{}_{\mathrm{<mtext>665</mtext><mtext>m</mtext><mtext>\mu </mtext>}}$ ratio and $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio, or between $\text{CH}{}_2\text{C=O}$ ratio and org. C content. The data are consistent with the hypothesis that the kerogen in the carbonates and cherts is autochthonous, whereas the kerogen in the mudstones is partly allochthonous, implying the existence of soil humus and soil organisms in pre-Phanerozoic times. Moreover, the existence of coal in Archean sediments is consistent with the existence of very shallow-water and possibly terrestrial microfloras possessing adaptations for protection against ultraviolet solar radiation.The P content of the sediments showed a complicated zig-zag pattern of variation through geologic time. All the different suites of samples gave similar results, indicating that the variations represent phenomena whose effects were worldwide and independent of local environment. P levels are low in the early pre-Phanerozoic but rise with decreasing age until ～ 1 · 10⁹ years B.P., then fall to a minimum at (～0.7–0.8) · 10⁹ years B.P., and rise again to a lower Paleozoic (Ediacarian?) maximum, decline to a later Paleozoic minimum, and then rise again. The low P content of early pre-Phanerozoic sediments could be due to several factors, including high CO₂ content of seawater, anaerobic conditions in the sea, absence of stable-shelf environments, and low rates of primary production. The minimum in the Late Proterozoic is tentatively attributed to the Late Proterozoic glaciations. The data are consistent with the theory that the glacial episode was of worldwide extent.     

Preserved organic matter in a fossil Ocean Continent Transition in the Alps: the example of Totalp,SE Switzerland

Evidence from ultraslow spreading mid-ocean ridges and both fossil and present-day Ocean–Continent Transitions (OCT) demonstrates that mantle serpentinization resulting from the interaction of mantle rock and water during tectonic exhumation is widespread. Observations at white smokers in modern ocean settings suggest that methane produced by serpentinization can support methanotrophic bio-systems, which use methane as the only source of carbon. An important question is whether such bio-systems are more generally pervasive in their association with serpentinized mantle in the subsurface. In this study, we examined whether there is evidence for such a methanotrophic system in exhumed serpentinized mantle at a magma-poor rifted continental margin, by probing for characteristic biological markers in these and associated sedimentary rocks in the Totalp unit of SE Switzerland. This unit represents a remnant of the former OCT of the southern Alpine Tethyan margin and was chosen because of its mild Alpine tectonic and low-grade metamorphic overprint during Alpine orogeny, hence giving potential for the preservation of indigenous organic matter (OM). Totalp samples are characterized by low organic carbon contents of 11–647 ppm. The majority of the samples contain hydrocarbons in the form of n-alkanes in the range C₁₇–C₃₆. Some sediments contain isoprenoids, for example pristane and phytane and a suite of steranes that are consistent with a marine origin for the OM preserved in the rocks. Traces of marine planktonic and bacterial OM are preserved in the serpentinized mantle and overlying sediments of this ancient Tethyan OCT, but there is no evidence that the OM has been generated from methanotrophic bio-systems.     

Deccan traps mantle degassing in the terminal Cretaceous marine extinctions

Mantle degassing continually releases gases onto the earth's surface. Over geologically long time intervals, a general equilibrium probably exists between mantle CO₂ release and uptake by surficial sinks. However, during periods of rapid plate movement, or continental flood basalt volcanism, the increased rate of mantle CO₂ release may exceed that of uptake, leading to CO₂ accumulation in the atmosphere and the marine mixed layer (top 50–100 m). This in turn triggers chemical changes in the mixed layer, climatic warming, and bioevolutionary turnover. The Cretaceous/Tertiary ($\text{K}\text{T}$) transition at 65 Ma seems to have been a time of major mantle degassing which induced a perturbation of the carbon cycle. During the $\text{K}\text{T}$ transition, Deccan Traps volcanism, perhaps the greatest episode of continental flood basalt volcanism in the Phanerozoic, flooded an estimated 2.6 × 10⁶ km² of India with basaltic lavas, releasing 5 × 10¹⁷ moles of CO₂ into the earth's atmosphere over a duration 0.53–1.36 Ma at the rate of 3.9 × 10¹¹ to 9.6 × 10¹¹ moles CO₂ per year. The modern mean annual rate of mantle CO₂ release from all sources is 4.1 × 10¹² moles CO₂ per year; assuming a comparable rate of release prior to the Deccan Traps volcanism, the Deccan Traps addition would have elevated the rate of mantle CO₂ release by 10–25%. Sluggish marine circulation and warm, deep, oceans (14–15°C) would have exacerbated CO₂ buildup in the atmosphere, accounting for the Cretaceous to Tertiary drop in oxygen-18 via climatic warming, and, in the marine mixed layer (top 50–100 m), explaining the selective nature of the terminal Cretaceous marine extinctions via a pH change. The extinctions were most severe amongst the calcareous microplankton of the mixed layer; calcareous microplankton (planktonic foraminifera and coccolithophorids) begin to have pH problems at 7.8 and 7.5, respectively. Failure of the coccolithophorids would have disrupted the Williams-Riley pump (algal productivity-gravity pump of CO₂ from the atmosphere and mixed layer into the deep oceans) producing dead ocean conditions (severely reduced photosynthesis and CaCO₃ production). Failure of the Williams-Riley pump is reflected in the extinctions themselves, and in the loss of biogenic CaCO₃ to the sea floor, causing the $\text{K}\text{T}$ boundary hiatus and (or) the $\text{K}\text{T}$ boundary clay. Failure of the pump today would elevate atmospheric pCO₂ severalfold; the $\text{K}\text{T}$ failure would have responded comparably. Dead ocean conditions would, in themselves, have produced a major CO₂ buildup. Early Tertiary “Strangelove” conditions in the mixed layer, characterized by a dominance of the thoracosphaerids, braarudosphaerids and small planktonic foraminifera, were coeval with the main pulse of Deccan Traps volcanism. Overall, the record is one of gradual $\text{K}\text{T}$ bioevolutionary turnover during a period of disequilibrium between the rate of mantle CO₂ degassing and uptake by sinks. Mantle degassing during the Deccan Traps volcanism unifies the $\text{K}\text{T}$ biological and physicochemical records.     

An assessment of paleodepositional environment and maturity of organic matter in sediments of the Setap Shale and Belait formations in West Sabah,East Malaysia by organic geochemical methods

The black shale samples collected from two Neogene formations in the Klias Peninsula area, West Sabah, have been assessed and characterized in details by gas chromatography, gas chromatography-mass spectrometry and a variety of organic geochemical parameters. The aims of this study are to describe the characteristics of organic matter of these sediments in terms of source/type of the organic matter, assess its thermal maturity and paleoenvironment of deposition, based primarily on biomarker distributions. The results of both formations do not reveal significant differences within the rock extracts. The gas chromatograms of the saturated hydrocarbon fractions of the Setap Shale and the Belait formations displayed monomodal n-alkane distributions and nearly identical regular sterane compositions with a predominance of C₂₇ regular steranes. These are consistent with open marine depositional environments dominated by marine biological matter. Another related feature of these rock extracts is the presence of a high relative abundance of gammacerane, indicating anoxic marine hypersaline source depositional environment. The relatively high abundance of common land plant-derived biomarkers, such as bicadinanes and oleananes, is a clear indication of a major terrigenous input to the source of the extractable organic matter. The predominance of oleanane biomarkers in both formations is indicative of angiospermis input and Tertiary source rocks. The high C₂₉/C₃₀ hopane ratios, moderate development of C₃₃–C₃₅ hopanes, high abundance of tricyclic terpanes and a slight predominance of C₂₇ regular sterane over C₂₈ and C₂₉ steranes are characteristic features tending to suggest a significant marine influence on these source rocks, thereby suggesting a mixed source input. The 22S/(22S+22R)C₃₂ hopane ratio has reached equilibrium, and this is supported by the high maturity level as indicated by the 22S/22SC_31–33 extended hopane ratios and 20S/(20S+20R)C₂₉ regular steranes ratios.     

卟啉的研究现状及其应用

在前人研究资料及作者近年来的研究成果的基础上，综述了卟啉化合物地球化学研究的现状，包括金属卟啉的类型，卟啉的化学结构系列，高度脱链基卟啉和高碳数咔琳等及其它们在沉积物(如油页岩、煤和现代沉积物)中的分布特征和成因机理。指出了今后需要加强研究的领域，如沉积物中新的金属卟啉类型探讨和卟啉化学结构的确定等。文章还综述了卟啉化合物地球化学指标在地质勘探中的应用，如:评价生油岩质量，油源对比，油气运移研究，古沉积环境研究和有机质热成熟度研究等。     

The geochemical significance in early sedimentation of geolipids obtained by saponification of lacustrine sediments

Significant quantities of solvent-inextractable geolipids, obtained by saponification of solvent extracted sediments, were found in various sedimentary samples including soils, river inlet sediment and lake sediments from Lake Suwa.The carbon isotopic composition ($\text{δ}{}^{13}\text{C}$) of extractable and inextractable geolipids from the same sediment sample were similar. Moreover, the carbon number distributions of sterols in the two geolipid fractions from the same sediment were also similar.Whereas the ratios of both lipids and sterols to total organic carbon for the extractable geolipids in the lake sediments decreased with depth, the former ratio for inextractable giolipids tends to increase with depth and the latter remains fairly constant. On the other hand, the stanol to stenol ratio of the extractable fraction increased with depth but that of the inextractable fraction was lower than that of the extractable fraction and was fairly constant irrespective of sediment depth.The transformation of extractable sterols into inextractable ones was not observed during incubation for 1200 days of sterols with Suwa sediments.Thus, the following conclusions were made: (1) the extractable and inextractable geolipids have similar origins, (2) some constituents of the latter may be protected from chemical or microbiological degradation and transformation in the sediments, and (3) the transformation of some constituents of the former into the inextractable ones virtually does not occur after incorporation into Suwa sediments.These results suggest that some constituents of the inextractable geolipid fraction may provide fundamental information on early diagenetic alteration of geolipids in lake sediments and on the relatively recent paleoenvironment.     

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

Distribution and isotopic composition (δ¹³C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20–35 m), reached uniform concentrations (55 μM/l) in the monimolimnion (35–64 m) and again increased with depth in monimolimnion bottom sediments (>400 μM/kg below 1 m sub-bottom depth). The μ¹³C[CH₄] values in bottom sediment below 1 m sub-bottom depth (<?70 per mil) increased with vertical distance up the core (δ¹³C[CH₄] = ?55 per mil at sediment surface). Monimolimnion δ¹³C[CH₄] values (?55 to ?61 per mil) were greater than most δ¹³C[CH₄] values found in the anoxic mixolimnion (92% of samples had δ¹³C[CH₄] values between ?20 and ?48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50–60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of $\text{CH}{}_4\text{[C}{}_2\text{H}{}_6\text{+ C}{}_3\text{H}{}_8\text{]}$ were high (250–620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C₂-C₄ alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in δ¹³C[CH₄] and $\text{CH}{}_4\text{(C}{}_2\text{H}{}_6\text{+ C}{}_3\text{H}{}_8\text{)}$ with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C₂ to C₄ alkane production by microorganisms.     

A review of various factors influencing the stable carbon isotope ratio of organic lake sediments by the change from glacial to post-glacial environmental conditions

A survey is made of various factors influencing the ${}^{13}\text{C}{}^{12}\text{C}$ ratio of the organic component in lake sediments, focusing on the behaviour at the change from glacial to post-glacial environmental conditions.Increase in the ¹³C content of the organic sediment is caused by increase in temperature and the corresponding decrease of the supply of molecular CO₂ in the water of the lakes. An increase in the rate of organic production in the lakes may also, perhaps, cause a corresponding ¹³C increase. An increase of the fermentation of organic mud in the lakes may also have an effect in the same direction.Decrease in the ¹³C content of the organic sediment is caused by the change of the relative amounts of production of plankton and submersed macrophytes in the lakes from mainly submersed macrophytes to mainly plankton. A decrease towards almost complete absence of bicarbonate and CO₂ originating from carbonate rocks will also lead to a ¹³C decrease in the organic sediments. The same effect has the change of the terrestrial vegetation cover from almost complete absence to complete cover. A possible decrease of the ¹³C content in the atmospheric CO₂ has an effect in the same direction.     

Organic geochemistry and petroleum potential of Jurassic and Cretaceous deposits of the Yenisei–Khatanga regional trough

We present results of geochemical studies of organic matter of the Jurassic–Cretaceous deposits in the west of the Yenisei–Khatanga regional trough. The studies were carried out on a representative set of well cores by a complex of modern organic-geochemistry methods (determination of organic-carbon content in rocks, pyrolysis, estimation of the carbon isotope composition in the kerogen of rocks, extraction, liquid and gas–liquid chromatography, and chromato-mass spectrometry). Based on the distribution of biomarkers in the studied bitumens and pyrolysis of rocks, two groups of the samples were recognized: with terrigenous (type III) and marine (type II) organic matter. The terrigenous bitumens are characterized by a low hydrogen index (HI) and a predominance of hydrocarbons C₂₉ among steranes and C₁₉ and C₂₀ among tricyclanes. The marine bitumens, revealed in stratigraphic analogs of the Bazhenovo Formation and in the Malyshevka, Nizhnyaya Kheta, and Shuratovka Formations, show an even distribution of sterane homologues and a predominance of medium-molecular tricyclanes. The Pr/Ph and C₃₅/C₃₄ ratios and the presence of diahopanes testify to the burial of organic matter in suboxidizing sea coast environments. In the Yanov Stan (J₃–K₁), Gol’chikha (J₂–K₁), and, to a lesser extent, Malyshevka (J₂), Nizhnyaya Kheta, and Shuratovka (K₁) Formations, we have recognized widespread stratigraphic levels with marine organic matter of rocks. Its contents and degree of maturity permit these rocks to be considered oil-generating.     

Aerobic respiration in pelagic marine sediments

Analyses for dissolved oxygen, nitrate and total CO₂ in the interstitial water have been combined with solid phase sediment analyses of carbon and nitrogen to calculate the rates of reaction and stoichiometry of decomposing organic matter in central Equatorial Pacific pelagic sediments. The diagenesis is dominated by aerobic respiration and nitrification.Organic carbon and total nitrogen decrease exponentially with depth in both red clay and carbonate ooze sediments. In addition, there is a correlation between surface organic carbon and total nitrogen with distance from the equator. Fixed NH₄ is relatively constant with depth and constitutes 12 to 64% of the total nitrogen. The remainder is considered to be organic nitrogen.The $\text{C}\text{N}$ ratio of the decomposing organic matter was obtained using three approaches. Using the correlations of organic carbon with total nitrogen or organic nitrogen the molar ratios varied from 3.4 to 18.1. The average of all stations was 12.6 using total nitrogen and 13.7 using organic nitrogen. The Redfield ratio is 6.6. Approaches using interstitial water chemistry gave lower ratios. The average value using correlations between dissolved oxygen and nitrate was 8.1. The same approach using total CO₂ and nitrate gave an average of 9.1. Due to difficulties in unambiguously interpreting the solid phase data we favor the ratios obtained from the pore water analyses.The rate of organic matter decomposition can be obtained from model calculations using the dissolved oxygen and solid organic carbon data. Most gradients occur in the upper 10 to 20 cm of the sediments. Assuming that bioturbation is more important than sedimentation we have calculated first order rate constants. The average values using organic carbon and dissolved oxygen was 3.9 kyr^? and 4.2 kyr^? respectively using a biological mixing coefficient of 100 cm² kyr^?1. These rate constants decrease in direct proportions to the mixing coefficient.     

Carbon content and carbonate 13C abundances in the Early Precambrian Swaziland sediments of South Africa

Carbon content (0.02–0.68% organic), carbonate content (0–69.7%) and carbonate ¹³C abundances (${}^{\mathrm{?}}\text{7.5?+2.3‰}$) were obtained on samples from the Swaziland sediments of South Africa, which are among the oldest known sedimentary rocks on earth (> 3·10⁹ years old). The carbon chemistry of these sediments may serve as evidence for early life and/or for products of chemical evolution. The variation of organic and carbonate carbon concentrations in different sedimentary horizons seems to be controlled by differences in depositional and diagenetic histories. The carbonate δ ¹³C values did not vary significantly from the ordinary range of Phanerozoic limestone values.