The carbon and sulfur cycles and atmospheric oxygen from middle Permian to middle Triassic

The results of a theoretical isotope mass balance model are presented for the time dependence of burial and weathering-plus-degassing fluxes within the combined long-term carbon and sulfur cycles. Averaged data for oceanic δ¹³C and δ³⁴S were entered for every million years from 270 to 240 Ma (middle Permian to middle Triassic) to study general trends across the Permian-Triassic boundary. Results show a drop in the rate of global organic matter burial during the late Permian and a predominance of low values during the early-to-middle Triassic. This overall decrease with time is ascribed mainly to epochs of conversion of high biomass forests to low biomass herbaceous vegetation resulting in a decrease in the production of terrestrially derived organic debris. Additional contributions to lessened terrestrial carbon burial were increased aridity and a drop in sea level during the late Permian which led to smaller areas of low-lying coastal wetlands suitable for coal and peat deposition.Mirroring the drop in organic matter deposition was an increase in the burial of sedimentary pyrite, and a dramatic increase in the calculated global mean ratio of pyrite-S to organic-C. High S/C values resulted from an increase of deposition in marine euxinic basins combined with a decrease in the burial of low-pyrite associated terrestrial organic matter. The prediction of increased oceanic anoxia during the late Permian and early Triassic agrees with independent studies of the composition of sedimentary rocks.Weathering plus burial fluxes for organic carbon and pyrite sulfur were used to calculate changes in atmospheric oxygen. The striking result is a continuous drop in O₂ concentration from ∼30% to ∼13% over a twenty million year period. This drop was brought about mainly by a decrease in the burial of terrestrially derived organic matter. but with a possible contribution from the weathering of older organic matter on land. It must have exerted a considerable influence on animal evolution because of the role of O₂ in respiration. Some examples are the extinction of many vertebrates, loss of giant insects and amphibians, and the restriction of animals to low elevations. It is concluded that the extinction of plants may have contributed to the extinction of animals.     

Evolution of photoautotrophy and early atmospheric oxygen levels

Current photochemical models suggest that oxygen levels in the prebiological atmosphere were extremely low, most probably remaining in the range 10⁻⁸–10⁻¹⁴ PAL (present atmospheric level). It is, therefore, reasonable to assume that only life processes were able to overwhelm these minor O₂-pressures, with free oxygen resulting from the reduction of carbon dioxide to the carbohydrate level during photoautotrophic carbon fixation using water as an electron donor (

Full-size image (1K)

). It is by now well established that reduced (organic) carbon is a common constituent of sedimentary rocks from the very start of the geological record 3.8 Ga ago. Both direct assays and inferences derived from a carbon isotope mass balance suggest that the C_org-content of Archaean sediments was not basically different from that of geologically younger rocks. This poses the problem of the existence 3.5 Ga ago of an oxidation equivalent of such a formidable ancient C_org-reservoir which, depending on the model adopted for the growth of the sedimentary mass through time, might have amounted to between 20 and 100% of the present one. Low atmospheric oxygen pressures in the Early Precambrian that are inferred from retarded oxidation reactions, notably in the ancient continental weathering cycle, are likely, therefore, to indicate extremely rapid processes of oxygen consumption in other parts of the system (e.g., hydrosphere) rather than the general absence of photosynthetic oxidation equivalents during this time.     

Role of a strong oxygen-deficient zone in the preservation and degradation of organic matter: a carbon budget for the continental margins of northwest Mexico and Washington State

Rates of organic carbon oxidation in marine sediments were determined for the continental margins of northwest Mexico and Washington State, with the goal of assessing the role of oxygen in the preservation of organic matter on a margin with a strong oxygen-deficient zone and on a typical western continental margin. Total carbon oxidation rates (including rates for individual electron acceptors: O₂, NO₃⁻, and SO₄⁼) were determined at depths ranging from 100 to 3000 m on both margins. Carbon oxidation rates were generally higher on the Washington margin than on the Mexican margin. The relative importance of the different electron acceptors varied across the two margins and was related primarily to the availability of O₂ and NO₃⁻ from the overlying water. The relative contribution of O₂ consumption increased in deeper sediments (>2000 m) as aerobic processes began to dominate the total carbon oxidation rate. Denitrification rates were highest in Washington sediments; however, denitrification represented a larger fraction of the total carbon oxidation rate in the Mexican sediments (∼40% for Mexico vs. ∼30% for Washington). Sulfate reduction accounted for as much as 79% of the total carbon oxidation rate in shallow sediments and less than 20% in deep sediments on both margins. The offshore trends in carbon oxidation rate appeared to be related to the organic carbon input rate. Pore-water O₂ and NO₃⁻ penetration depths were shallowest in nearshore stations and increased offshore. Regeneration ratios of C:N:P reveal “non-Redfield” behavior on both margins. Carbon budgets for the two margins demonstrate that off Mexico, a much greater percentage of the organic matter produced in the surface ocean reached the sediments (>15% vs. <8% for Mexico and Washington, respectively). On the Mexican margin, ∼8% of the primary production escaped oxidation in the surface sediments to be permanently buried, as compared with only ∼1.2% of the primary production on the Washington margin. This suggests that oxygen-deficient conditions on Mexican margin are linked to enhanced carbon preservation.     

GEOCARBSULF: A combined model for Phanerozoic atmospheric O2 and CO2

A model for the combined long-term cycles of carbon and sulfur has been constructed which combines all the factors modifying weathering and degassing of the GEOCARB III model [Berner R.A., Kothavala Z., 2001. GEOCARB III: a revised model of atmospheric CO₂ over Phanerozoic time. Am. J. Sci. 301, 182-204] for CO₂ with rapid recycling and oxygen dependent carbon and sulfur isotope fractionation of an isotope mass balance model for O₂ [Berner R.A., 2001. Modeling atmospheric O₂ over Phanerozoic time. Geochim. Cosmochim. Acta65, 685-694]. New isotopic data for both carbon and sulfur are used and new feedbacks are created by combining the models. Sensitivity analysis is done by determining (1) the effect on weathering rates of using rapid recycling (rapid recycling treats carbon and sulfur weathering in terms of young rapidly weathering rocks and older more slowly weathering rocks); (2) the effect on O₂ of using different initial starting conditions; (3) the effect on O₂ of using different data for carbon isotope fractionation during photosynthesis and alternative values of oceanic δ¹³C for the past 200 million years; (4) the effect on sulfur isotope fractionation and on O₂ of varying the size of O₂ feedback during sedimentary pyrite formation; (5) the effect on O₂ of varying the dependence of organic matter and pyrite weathering on tectonic uplift plus erosion, and the degree of exposure of coastal lands by sea level change; (6) the effect on CO₂ of adding the variability of volcanic rock weathering over time [Berner, R.A., 2006. Inclusion of the weathering of volcanic rocks in the GEOCARBSULF model. Am. J. Sci.306 (in press)]. Results show a similar trend of atmospheric CO₂ over the Phanerozoic to the results of GEOCARB III, but with some differences during the early Paleozoic and, for variable volcanic rock weathering, lower CO₂ values during the Mesozoic. Atmospheric oxygen shows a major broad late Paleozoic peak with a maximum value of about 30% O₂ in the Permian, a secondary less-broad peak centered near the Silurian/Devonian boundary, variation between 15% and 20% O₂ during the Cambrian and Ordovician, a very sharp drop from 30% to 15% O₂ at the Permo-Triassic boundary, and a more-or less continuous rise in O₂ from the late Triassic to the present.     

Fate of organic carbon reaching the deep sea floor: a status report

The rates of organic carbon oxidation by O₂, NO₃^?, MnO₂, Fe₂O₃ and SO₄^? have been calculated for five pelagic Pacific and Atlantic sites using simple diffusion-reaction models. O₂ everywhere oxidizes > 90% of the raining C_org; the fraction oxidized by the secondary oxidants decreases as the rain rate of organic C to the seafloor decreases. A large fraction of the C_org escaping oxidation by O₂ is oxidized by the secondary oxidants. Hence while these oxidants play a small role in remineralization, they are important in regulating the burial of organic matter and the consequent removal from the oceans of reduced carbon and nutrients.     

The control of Phanerozoic atmosphere and seawater composition by basalt–seawater exchange reactions

We present results from a long term geochemical cycling model, with a focus on the sensitivity of atmospheric carbon dioxide, oxygen, and the major element composition of seawater to seafloor spreading rates. This model incorporates rock weathering, basalt–seawater exchange reactions, and the formation and destruction of chemical sediments and organic matter. Hydrothermal reactions between seafloor and seawater involving calcium, magnesium, sodium, potassium, sulfate and carbon are the high temperature counterparts to low temperature redox, weathering, precipitation and diagenetic reactions. A major source of uncertainty is the extent to which these exchange fluxes are controlled by seafloor spreading rate. In addition, the return fluxes of these components to the atmospheric and primary silicate reservoirs reflect not only the overall rates of subduction and metamorphism, but the distribution of the overlying sedimentary burden and authigenic minerals formed during basalt alteration as well. In particular, we show how the stoichiometry of exchange fluxes (Mg/Ca and SO₄/Ca) may buffer atmospheric CO₂ and O₂ concentrations.     

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.     

CO<Subscript>2</Subscript> Air–Sea Exchange due to Calcium Carbonate and Organic Matter Storage,and its Implications for the Global Carbon Cycle

Release of CO₂ from surface ocean water owing to precipitation of CaCO₃ and the imbalance between biological production of organic matter and its respiration, and their net removal from surface water to sedimentary storage was studied by means of a quotient θ = (CO₂ flux to the atmosphere)/(CaCO₃ precipitated). θ depends not only on water temperature and atmospheric CO₂ concentration but also on the CaCO₃ and organic carbon masses formed. In CO₂ generation by CaCO₃ precipitation, θ varies from a fraction of 0.44 to 0.79, increasing with decreasing temperature (25 to 5°C), increasing atmospheric CO₂ concentration (195–375 ppmv), and increasing CaCO₃ precipitated mass (up to 45% of the initial DIC concentration in surface water). Primary production and net storage of organic carbon counteracts the CO₂ production by carbonate precipitation and it results in lower CO₂ emissions from the surface layer. When atmospheric CO₂ increases due to the ocean-to-atmosphere flux rather than remaining constant, the amount of CO₂ transferred is a non-linear function of the surface layer thickness because of the back-pressure of the rising atmospheric CO₂. For a surface ocean layer approximated by a 50-m-thick euphotic zone that receives input of inorganic and organic carbon from land, the calculated CO₂ flux to the atmosphere is a function of the CaCO₃ and C_org net storage rates. In general, the carbonate storage rate has been greater than that of organic carbon. The CO₂ flux near the Last Glacial Maximum is 17 to 7×10¹² mol/yr (0.2–0.08 Gt C/yr), reflecting the range of organic carbon storage rates in sediments, and for pre-industrial time it is 38–42×10¹² mol/yr (0.46–0.50 Gt C/yr). Within the imbalanced global carbon cycle, our estimates indicate that prior to anthropogenic emissions of CO₂ to the atmosphere the land organic reservoir was gaining carbon and the surface ocean was losing carbon, calcium, and total alkalinity owing to the CaCO₃ storage and consequent emission of CO₂. These results are in agreement with the conclusions of a number of other investigators. As the CO₂ uptake in mineral weathering is a major flux in the global carbon cycle, the CO₂ weathering pathway that originates in the CO₂ produced by remineralization of soil humus rather than by direct uptake from the atmosphere may reduce the relatively large imbalances of the atmosphere and land organic reservoir at 10²–10⁴-year time scales.     

Stabilisation of soil organic matter by interactions with minerals as revealed by mineral dissolution and oxidative degradation

Soil organic matter is known to contain a stable fraction with an old radiocarbon age. Size and stabilisation processes leading to the formation of this old soil carbon pool are still unclear. Our study aims to differentiate old organic matter from young and labile carbon compounds in two acid forest soils (dystric cambisol, haplic podzol). To identify such fractions soil samples were exposed to oxidation with Na₂S₂O₈ and to dissolution by hydrofluoric acid (HF). A negative correlation between ¹⁴C activity and carbon release after dissolution of the mineral matrix by HF indicates a strong association of stabilised carbon compounds with the mineral phase. A negative correlation between the ¹⁴C activity and the relative proportion of carbon resistant to oxidation by Na₂S₂O₈ shows that young carbon is removed preferentially by this treatment. The fraction remaining after oxidation represents a certain stabilised, long residence time carbon pool. This old fraction comprises between 1 and 30% of the total soil organic carbon in the surface horizons, but reaches up to 80% in the sub-surface horizons. Old OC is mainly stabilised by organo-mineral associations with clay minerals and/or iron oxides, whereas intercalation in clay minerals was not found to be important.     

Spatial and Temporal Variability of Sediment Organic Matter Recycling in Two Temperate Eutrophicated Estuaries

This paper deals with the spatial and seasonal recycling of organic matter in sediments of two temperate small estuaries (Elorn and Aulne, France). The spatio-temporal distribution of oxygen, nutrient and metal concentrations as well as the organic carbon and nitrogen contents in surficial sediments were determined and diffusive oxygen fluxes were calculated. In order to assess the source of organic carbon (OC) in the two estuaries, the isotopic composition of carbon (δ ¹³C) was also measured. The temporal variation of organic matter recycling was studied during four seasons in order to understand the driving forces of sediment mineralization and storage in these temperate estuaries. Low spatial variability of vertical profiles of oxygen, nutrient, and metal concentrations and diffusive oxygen fluxes were monitored at the station scale (within meters of the exact location) and cross-section scale. We observed diffusive oxygen fluxes around 15 mmol m^?2 day^?1 in the Elorn estuary and 10 mmol m^?2 day^?1 in the Aulne estuary. The outer (marine) stations of the two estuaries displayed similar diffusive O₂ fluxes. Suboxic and anoxic mineralization was large in the sediments from the two estuaries as shown by the rapid removal of very high bottom water concentrations of NO _x ^? (>200 μM) and the large NH₄ ⁺ increase at depth at all stations. OC contents and C/N ratios were high in upstream sediments (11–15 % d.w. and 4–6, respectively) and decreased downstream to values around 2 % d.w. and C/N ≤ 10. δ ¹³C values show that the organic matter has different origins in the two watersheds as exemplified by lower δ ¹³C values in the Aulne watershed. A high increase of δ ¹³C and C/N values was visible in the two estuaries from upstream to downstream indicating a progressive mixing of terrestrial with marine organic matter. The Elorn estuary is influenced by human activities in its watershed (urban area, animal farming) which suggest the input of labile organic matter, whereas the Aulne estuary displays larger river primary production which can be either mineralized in the water column or transferred to the lower estuary, thus leaving a lower mineralization in Aulne than Elorn estuary. This study highlights that (1) meter scale heterogeneity of benthic biogeochemical properties can be low in small and linear macrotidal estuaries, (2) two estuaries that are geographically close can show different pattern of organic matter origin and recycling related to human activities on watersheds, (3) small estuaries can have an important role in recycling and retention of organic matter.     

Anaerobic oxidation of methane in coastal sediment from Guishan Island (Pearl River Estuary), South China Sea

The concentrations of CH₄, SO₄²⁻, σCO₂ and the carbon isotope compositions of ΣCO₂ and CH₄ in the pore-water of the GS sedimentary core collected from Guishan Island (Pearl River Estuary), South China Sea, were determined. The methane concentration in the pore-water shows dramatic changes and sulfate concentration gradients are linear at the base of the sulfate reduction zone for the station. The carbon isotope of methane becomes heavier at the sulfate-methane transition (SMT) likely because of the Raleigh distillation effect; ¹²CH₄ was oxidized faster than ¹³CH₄, and this caused the enrichment of residual methane δ ¹³C and δ ¹³C-ΣCO₂ minimum. The geochemical profiles of the pore-water support the existence of anaerobic oxidation of methane (AOM), which is mainly controlled by the quality and quantity of the sedimentary organic matter. As inferred from the index of δ ¹³C-TOC value and TOC/TN ratio, the organic matter is a mix of mainly refractory terrestrial component plus some labile alga marine-derived in the study area. A large amount of labile organic matter (mainly labile alga marine-derived) is consumed via the process of sedimentary organic matter diagenesis, and this reduces the amount of labile organic matter incorporated into the base of the sulfate reduction zone. Due to the scarcity of labile organic matter, the sulfate will in turn be consumed by its reaction with methane and therefore AOM takes place. Based on a diffussion model, the portion of pore-water sulfate reduction via AOM is 58.6%, and the percentage of ΣCO₂ in the pore-water derived from AOM is 41.4%. Thus, AOM plays an important role in the carbon and sulfur cycling in the marine sediments of Pearl River Estuary.     

SPORE-POLLEN COMPLEXES OF UPPER DEVONIAN OF THE RUSSIAN PLATFORM

Carbonaceous units commonly host or are closely related to lode-gold mineralization in the mesothermal Fazenda Maria Preta (FMP) and Fazenda Canto (FC) deposits of the Paleoproterozoic Rio Itapicuru greenstone belt of northeastern Brazil. In these deposits, the carbonaceous matter occurs mainly as: (1) straight to anastomosing seams (Type I) along or transecting the rock fabric, or as stylolitic structures in quartz veins; (2) single grains composed of an agglomerate of highly anisotropic subgrains (Type II); or (3) single grains with a homogeneous internal texture (Type III), which are either enclosed in Type-I carbonaceous seams or disseminated in the rock matrix. Type-I carbonaceous matter commonly hosts or is overgrown by the gold-related sulfide paragenesis, particularly arsenopyrite, whereas both Type I and Type II enclose crystals of arsenopyrite or occur as inclusions and in sharp contact with the sulfide phases.

The three morphological types of carbonaceous matter exhibit similar Raman spectral characteristics, with distinct D and O peaks at wave numbers between 1351 cm^?1 and 1357 cm^?1, and 1585 cm^?1 and 1598 cm^?1, respectively. In contrast to the FMP deposit, the carbonaceous matter of the FC deposit shows D peaks of higher intensities than the O peaks. The O peaks are accompanied by an additional disorder-induced band on the high wave number side (≈ 1622 cm^?1), and the O/D peak intensity ratios are higher and the half-height O-peak widths smaller. These spectral parameters indicate that the carbonaceous matter in both deposits corresponds to some form of microcrystalline disordered graphitic material and defines a graphitization trend from the FMP to the FC deposit.

The carbonaceous matter of the FMP deposit is isotopically lighter (δ¹³C = ?23.3‰ to ?30.8‰; x = ?27.4 ± 1.8‰ relative to PDB) than the carbonaceous material of the FC (δ¹³C = ?18.5‰ to ?21.0‰, x = ?19.7 ± 0.9‰). These δ¹³C values, together with the geologic evidence, point toward a primarily biogenic organic origin for the carbonaceous matter. The marked differences in the Raman spectral parameters and the δ₁₃C values are interpreted as resulting from different degrees of thermal maturation of carbonaceous matter attained during the regional greenschist metamorphism and granite intrusions of the Rio Itapicuru greenstone belt.

The δ¹³C compositions of CO₂ resulting from the oxidation or hydrolysis of the carbonaceous matter, calculated by applying the equilibrium CO₂-graphite fractionation, fall within the range ?9.7‰ to ?18.8‰ at 360 to 420°C (FMP deposit) and ?6.0° to ?10.0° at 390 to 455°C (FC deposit). These calculated δ¹³C values are lower than those obtained from primary fluid-inclusion CO₂ in gold-bearing veins (?6.0° to ?10.2° for the FMP deposit; ?2.8° to ?4.9° for the FC deposit) and imply that the thermal maturation process of the carbonaceous matter contributed little to changes in the chemistry and isotopic composition of the ore fluid. The presence of the carbonaceous matter may have been an important factor in gold deposition during fluid-carbon interaction, acting: (1) as a chemical trap, by reducing the f(O₂) of the ore fluids or enhancing fluid immiscibility by adding small quantities of CH₄ and N₂ to the fluid phase; and/or (2) as a physical barrier, by adsorbing gold on its surface as activated carbon.     

Influence of the biological carbon pump effect on the sources and deposition of organic matter in Fuxian Lake,a deep oligotrophic lake in southwest China

Biological carbon pumping (BCP) is a key process in which dissolved inorganic carbon in terrestrial aquatic ecosystems is utilized by aquatic autotrophs for photosynthesis and transformed into autochthonous organic matter (AOC). However, the mechanisms underlying BCP and the amount of generated AOC deposited effectively, are still poorly understood. Therefore, we conducted a systematic study combining modern hydrochemical monitoring and a sediment trap experiment in Fuxian Lake (Yunnan, SW China), the second-deepest plateau, oligotrophic freshwater lake in China. Temperature, pH, EC (electrical conductivity), DO (dissolved O₂), [HCO₃⁻], [Ca²⁺], SI_c, partial CO₂ (pCO₂) pressure, and carbon isotopic compositions of HCO₃⁻ (δ¹³C_DIC) in water from Fuxian Lake all displayed distinct seasonal and vertical variations. This was especially apparent in an inverse correlation between pCO₂ and DO, indicating that variations of hydrochemistry in the lake water were mainly controlled by the metabolism of the aquatic phototrophs. Furthermore, the lowest C/N ratios and highest δ¹³C_org were recorded in the trap sediments. Analyses of the C/N ratio demonstrated that the proportions of AOC ranged from 30% to 100% of all OC, indicating that AOC was an important contributor to sedimentary organic matter (OC). It was calculated that the AOC flux in Fuxian Lake was 20.43 t C km⁻² in 2017. Therefore, AOC produced by carbonate weathering and aquatic photosynthesis could potentially be a significant carbon sink and may have an important contribution to solving the lack of carbon sinks in the global carbon cycle.

     

350 ka Organic δ13C record of the monsoon variability on the Oman continental margin, Arabian Sea

The stable isotope compositions of sedimentary organic carbon and content of organic carbon for sediment cores recovered at two sites (sites 724C and 725C) during Ocean Drilling Program (ODP) Leg. 117 on the Oman continental margin are used to document variability of the monsoon winds for the past 350 ka. Although both sites have a mean δ¹³C value of -20.1‰, three zones depleted in¹³C are observable at site 724C during isotope stages 3, 8 and 10, while only one zone is recognizable at site 725C. Increased coastal upwelling during isotope stage 3 owing to intense SW monsoon winds resulted in higher concentration of CO₂ in the water column causing the formation of organic matter that was depleted in¹³C. The other two zones deposited during oxygen isotope stages 8 and 10, which are also characterized by low values of organic carbon, nitrogen and C/N ratios, could be attributed to the dilution by terrestrial material derived from paleosol by transported by northwester lies. Because of utilization of¹³C enriched dissolved CO₂ during the last glacial maximum Holocene sedimentary organic materials are depleted in¹³C relative to the the fomer. The content of residues organic carbon (ROC) is higher at site 724C (with an average of 2.3 ± 1.2%) relative to site 725C, which averages to 0.9 ± 0.4% probably because of differences in the degree of preservation. Organic material deposited at site 725C has undergone more degradation relative to site 724C as reflected by a systematic downcore decrease in¹³C resulting from a loss of¹³C enriched organic compounds. Owing to lack of good chronology at site 725C, a zone that is characterized by low δ¹³C values it could not be correlated with the other three zones observed at Site 724C.     

Insights on geochemical cycling of U, Re and Mo from seasonal sampling in Boston Harbor, Massachusetts, USA

This study examined the removal of U, Mo, and Re from seawater by sedimentary processes at a shallow-water site with near-saturation bottom water O₂ levels (240-380 μmol O₂/L), very high organic matter oxidation rates (annually averaged rate is 880 μmol C/cm²/y), and shallow oxygen penetration depths (4 mm or less throughout the year). Under these conditions, U, Mo, and Re were removed rapidly to asymptotic pore water concentrations of 2.2-3.3 nmol/kg (U), 7-13 nmol/kg (Mo), and 11-14 pmol/kg (Re). The depth order in which the three metals were removed, determined by fitting a diffusion-reaction model to measured profiles, was Re < U < Mo. Model fits also suggest that the Mo profiles clearly showed the presence of a near-interface layer in which Mo was added to pore waters by remineralization of a solid phase. The importance of this solid phase source of pore water Mo increased from January to October as the organic matter oxidation rate increased, bottom water O₂ decreased, and the O₂ penetration depth decreased. Experiments with in situ benthic flux chambers generally showed fluxes of U and Mo into the sediments. However, when the overlying water O₂ concentration in the chambers was allowed to drop to very low levels, Mn and Fe were released to the overlying water along with the simultaneous release of Mo and U. These experiments suggest that remineralization of Mn and/or Fe oxides may be a source of Mo and perhaps U to pore waters, and may complicate the accumulation of U and Mo in bioturbated sediments with high organic matter oxidation rates and shallow O₂ penetration depths.Benthic chamber experiments including the nonreactive solute tracer, Br⁻, indicated that sediment irrigation was very important to solute exchange at the study site. The enhancement of sediment-seawater exchange due to irrigation was determined for the nonreactive tracer (Br⁻), TCO₂, , U and Mo. The comparisons between these solutes showed that reactions within and around the burrows were very important for modulating the Mo flux, but less important for U. The effect of these reactions on Mo exchange was highly variable, enhancing Mo (and, to a lesser extent, U) uptake at times of relatively modest irrigation, but inhibiting exchange when irrigation rates were faster. These results reinforce the observation that Mo can be released to and removed from pore waters via sedimentary reactions.The removal rate of U and Mo from seawater by sedimentary reactions was found to agree with the rate of accumulation of authigenic U and Mo in the solid phase. The fluxes of U and Mo determined by in situ benthic flux chamber measurements were the largest that have been measured to date. These results confirm that removal of redox-sensitive metals from continental margin sediments underlying oxic bottom water is important, and suggest that continental margin sediments play a key role in the marine budgets of these metals.     

Masses of carbon in the Earth’s hydrosphere

Recent data were summarized on the concentration and mass of inorganic and organic carbon in reservoirs of the Earth’s hydrosphere. We compared carbon masses and accumulation conditions in the surface hydrosphere and waters of the sedimentary shell and proportions between carbonate, dissolved, and suspended particulate organic carbon. It was shown that the total masses of carbon in the surface hydrosphere and in the waters of the sedimentary shell are approximately equal to 80 × 10¹⁸ g C at an organic to carbonate carbon ratio of 1 : 36 and 1 : 43, respectively. Three main forms of organic compounds in the ocean (living organisms, suspended particles, and dissolved species) occur in the proportion 1 : 13 : 250 and form the pyramid of masses 4 × 10¹⁵ g, 50 × 10¹⁵ g, and 1000 × 10¹⁵ g C_org. The descending sequence of the organic to carbonate carbon ratio in water, ocean (1 : 36) > glaciers (1 : 8) > lakes (1 : 2) > rivers (1 : 0.6) > wetlands (1 : 0.3), is in general consistent with an increase in the same direction in the mean concentrations of organic matter: 0.77 mg C_org/L in the ocean, 0.7 mg C_org/L in glaciers, 6–30 mg C_org/L in lakes, 15 mg C_org/L in rivers, and 75 mg C_org/L in wetlands. Both the mean concentrations and masses of dissolved organic matter in the pore waters of oceanic sediments and in the waters of the sedimentary shell are similar: 36–37 mg/L and 5 × 10¹⁸ and 5.6 × 10¹⁸ g, respectively. The mass of carbonate carbon in the pore waters of the ocean, (19–33) × 10¹⁸ g, is comparable with its mass in the water column, 38.1 × 10¹⁸ g.     

Atmospheric weathering of Scandinavian alum shales and the fractionation of C,N and S isotopes

Subaerial exposure and oxidation of organic carbon (C_org)-rich rocks is believed to be a key mechanism for the recycling of buried C and S back to Earth's surface. Importantly, processes coupled to microbial C_org oxidation are expected to shift new biomass δ¹³C_org composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting δ¹³C_org at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, C_org-rich alum shale units of the Baltoscandian Basin believed to constitute a strong source of metal contaminants to the natural environment, following subaerial exposure and weathering. Consistent with independent support, we show that atmospheric oxidation of the sulfidic, C_org-rich alum shale sequence of the Cambrian-Devonian Baltoscandian Basin induces intense acid rock drainage at the expense of progressive oxidation of Fe sulfides. Sulfide oxidation takes priority over microbial organic matter decomposition, enabling quantitative massive erosion of C_org without producing a δ¹³C shift between acid rock drainage precipitates and shale. Moreover, ¹³C enrichment in inorganic carbon of precipitates does not support microbial C_org oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Δ³⁴S = δ³⁴S_shale − δ³⁴S_precipitates ≈ 0, accompanied by elevated S levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales, provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering. Slight δ¹⁵N depletion in the new surface precipitates relative to shale, coincides with dramatic loss of N from shales. Collectively, the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock-atmosphere interface, indicating that quantitative mass release of C_org, N, S, and key metals to the environment is a response to intense sulfide oxidation. Consequently, large-scale acidic weathering of the sulfide-rich alum shale units is suggested to influence the fate and redistribution of the isotopes of C, N, and S from shale to the immediate environment.     

Sediment petrography,mineralogy and geochemistry of the Miocene Islam Dağ Section (Eastern Azerbaijan): Implications for the evolution of sediment provenance,palaeo-environment and (post-)depositional alteration patterns

The reconstruction of regional long-term patterns recorded in marine sedimentary successions of the Eastern Paratethys is important in understanding the role of Cenozoic climate change and orogenic activity on the depositional environment and sedimentation dynamics in Western Asia. In this study, the environmental conditions in the early to middle Miocene (Islam Dağ section) in eastern Azerbaijan are elucidated using petrographic–mineralogical relations, detrital indicators, weathering indices and δ¹³C and δ¹⁸O signatures of organic-rich (total organic carbon: ca 3 to 6 wt. %) argillites. Sedimentary facies and chemical proxies (Na/K, K/Al, Si/Al, Ti/Al ratios, chemical index of alteration values) indicate arid conditions, reduced weathering rates in the hinterland and sediment deposition in an euhaline and poorly oxygenated deep-water basin during the early Miocene, followed by a shift to humid conditions, higher weathering rates and an oxygenated water column in the mid-early Miocene. Long-term aridification and deposition of gypsiferous and calcareous argillites under generally more oxygenated, euhaline to polyhaline conditions in a lacustrine or restricted shelf setting until the middle Miocene is evidenced by gradual changes in element ratios and the chemical index of alteration. Discriminant function analysis suggests the Russian Platform, drained by the Palaeo-Volga and Palaeo-Don river systems, to be the source area for the siliciclastic input throughout the Miocene, although a minor contribution of volcanogenic detritus and mafic components from the Greater Caucasus is possible. The C–S–Fe associations and increasing Fe/Al ratios towards the middle Miocene support the concept of continuous influx of detrital Fe and total organic carbon. The formation of ferruginous smectite from alteration of volcanic ash layers could have affected the preservation of total organic carbon and therefore the sedimentary C and Fe budget in the Eastern Paratethys basins. Palaeo-climatic reconstructions based on δ¹³C (−34·5 to +1·7‰ Vienna Pee Dee Belemnite) and δ¹⁸O (−34·7 to −4·8‰ Vienna Pee Dee Belemnite) records of authigenic carbonates should be made with great caution, as the pristine marine signatures may be affected by the oxidation of organic matter and meteoric diagenesis.     

Clay mineralogy, organic carbon burial, and redox evolution in Proterozoic oceans

Clay minerals formed through chemical weathering have long been implicated in the burial of organic matter (OM), but because diagenesis and metamorphism commonly obscure the signature of weathering-derived clays in Precambrian rocks, clay mineralogy and its role in OM burial through much of geologic time remains incompletely understood. Here we have analyzed the mineralogy, geochemistry and total organic carbon (TOC) of organic rich shales deposited in late Archean to early Cambrian sedimentary basins. Across all samples we have quantified the contribution of 1M and 1M_d illite polytypes, clay minerals formed by diagenetic transformation of smectite and/or kaolinite-rich weathering products. This mineralogical signal, together with corrected paleo-weathering indices, indicates that late Archean and Mesoproterozoic samples were moderately to intensely weathered. However, in late Neoproterozoic basins, 2M₁ illite/mica dominates clay mineralogy and paleo-weathering indices sharply decrease, consistent with an influx of chemically immature and relatively unweathered sediment. A late Neoproterozoic switch to micaceous clays is inconsistent with hypotheses for oxygen history that require an increased flux of weathering-derived clays (i.e., smectite or kaolinite) across the Precambrian-Cambrian boundary. Compared to previous studies, our XRD data display the same variation in Schultz Ratio across the late Neoproterozoic, but we show the cause to be micaceous clay and not pedogenic clay; paleo-weathering signals cannot be recovered from bulk mineralogy without this distinction. We find little evidence to support a link between these mineralogical variations and organic carbon in our samples and conclude that modal clay mineralogy cannot by itself explain an Ediacaran increase in atmospheric oxygen driven by enhanced OM burial.     

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.