Sulphur cycling in organic-rich marine sediments from a Scottish fjord

In this study, the biogeochemical transformations of sulphur in organic‐rich marine sediments in a Scottish fjord are investigated by a combination of pore water and sediment geochemistry with sulphide diffusive gradient thin‐film probes and sulphate isotopic data (δ³⁴S and δ¹⁸O). Particular attention is paid to sulphur cycling in the upper sediment profile where sulphate reduction occurs but free sulphide is below the detection limits of conventional pore water geochemical analysis but quantifiable by sulphide diffusive gradient thin film. In the uppermost part of the sediment core, δ¹⁸O sulphate decreased from near‐sea water values to +7‰, indicating that anoxic sulphide oxidation dominated during this interval. Sulphate δ³⁴S remained unchanged as there was no net sulphate reduction (i.e. reduction was balanced by re‐oxidation). Below 4 cm depth, there was a slight increase in sulphate δ³⁴S from 20‰ to 23‰ associated with minor accumulation of iron sulphide. The δ¹⁸O of the sulphate also increased, to around +10‰ at 10 cm depth, as a result of the isotopic exchange of sulphate–oxygen with pore water and/or sulphur disproportionation reactions mediated during sulphur cycling. These processes continued to increase the δ¹⁸O of the sulphate to 14‰ at 20 cm depth with no further change in the δ³⁴S of the sulphate. Below 20 cm depth, free sulphide is detectable in pore waters and both the δ³⁴S of the sulphate and sulphide increase with depth with an offset controlled by kinetic fractionation during bacterial sulphate reduction. The δ³⁴S of the sedimentary organic fraction shifted towards lower, more bacteriogenic, values with depth in the profile, without any increase in the size of this sulphur pool. Thus, the organic sulphur fraction was open to interaction with bacteriogenic sulphide without the occurrence of net addition. Therefore, caution should be exercised when using sulphur isotopic compositions to infer simple net addition of bacteriogenic sulphide to the organic sulphur fraction.     

Biogeochemical cycling in an organic-rich coastal marine basin—3. Dissolved gas transport in methane-saturated sediments

The transport of dissolved gases in the anoxic sediments of Cape Lookout Bight, North Carolina, is controlled by diffusion and bubble ebullition and exhibits a distinct seasonal cycle. Detailed seasonal profiles of CH₄, N₂ and ²²²Rn and direct gas flux measurements indicate that ebullition dominates the flux of all dissolved gases across the sediment-water interface during summer months, and is of major importance on an annual basis. Transport within the upper 6–8 cm of sediment appears to be controlled by molecular diffusion of gases. Transport at greater depths is controlled by diffusion in winter and ebullition in summer. Rn-222 profiles were used to estimate the rate of stripping of dissolved gases within the CH₄ production zone (10–30 cm); rates averaged 3–5 percent per day and agreed with estimates derived from N₂ profiles. As a result of summer ebullition, the sediments of the bight are never at saturation with respect to the major gases present in seawater. Evidence from other sites suggests that ebullition may be an important transport process in many coastal sediments, and may provide mechanism for the transport of volatile reduced compounds between anoxic sediments and the atmosphere. ²²²Rn is a useful tracer for quantifying this transport.     

Biogeochemical cycling in an organic-rich coastal marine basin 4. An organic carbon budget for sediments dominated by sulfate reduction and methanogenesis

In situ carbon flux measurements and calculated burial rates are utilized to construct an organic carbon budget for the upper meter of sediment at a single station in Cape Lookout Bight, a small marine basin located on the Outer Banks of North Carolina, U.S.A. (34°37′N, 76°33′W). Of 149 ± 20 mole · m^?2 · yr^?1 of total organic carbon deposited, 35.6 ± 5.2 mole · m^?2 · yr^?1 is recycled to overlying waters, 84 ± 18% as ∑CO₂ and 16 ± 8% as CH₄. Approximately 68 ± 20% of the upward carbon flux is supported by sulfate reduction while 32 ± 16% takes place as the result of underlying methanogenesis. Measured ∑CO₂ and CH₄ sediment-water fluxes range seasonally from 1900–6300 and 50–2500 μmole · m^?2 · hr^?1 respectively.The mean residence time of metabolizable organic carbon in the upper 80 cm of sediment is approximately four months with greater than 98% of the calculated total remineralization taking place within three years. In spite of large upward fluxes of methane, larger molecules derived from metabolizable sedimentary organic carbon appear to be the dominant reductants for dissolved sulfate.     

Constraining magnesium cycling in marine sediments using magnesium isotopes

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid δ²⁶Mg values increase with depth by as much as 2‰. Because carbonates preferentially incorporate ²⁴Mg (low δ²⁶Mg), the increase in pore-fluid δ²⁶Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid δ²⁶Mg values decrease with depth by up to 2‰. The decline in pore-fluid δ²⁶Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion-advection-reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured δ²⁶Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0-2.7‰ depleted in δ²⁶Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in δ²⁶Mg by 0‰ to +1.25‰ relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.     

Biogeochemical cycling in an organic-rich coastal marine basin—I. Methane sediment-water exchange processes

Methane produced in anoxic organic-rich sediments of Cape Lookout Bight, North Carolina, enters the water column via two seasonally dependent mechanisms: diffusion and bubble ebullition. Diffusive transport measured in situ with benthic chambers averages 49 and 163 μmol · m ^?2 · hr ^?1 during November–May and June–October respectively. High summer sediment methane production causes saturation concentrations and formation of bubbles near the sediment-water interface. Subsequent bubble ebullition is triggered by low-tide hydrostatic pressure release. June–October sediment-water gas fluxes at the surface average 411 ml (377 ml STP: 16.8 mmol) · m^?2 per low tide. Bubbling maintains open bubble tubes which apparently enhance diffusive transport. When tubes are present, apparent sediment diffusivities are 1.2–3.1-fold higher than theoretical molecular values reaching a peak value of 5.2 × 10^?5 cm² · sec^?1. Dissolution of 15% of the rising bubble flux containing 86% methane supplies 170μmol · m^?2 · hr^?1 of methane to the bight water column during summer months; the remainder is lost to the troposphere. Bottom water methane concentration increases observed during bubbling can be predicted using a 5–15 μm stagnant boundary layer dissolution model. Advective transport to surrounding waters is the major dissolved methane sink: aerobic oxidation and diffusive atmospheric evasion losses are minor within the bight.     

藏南地区海相白垩系富有机质沉积的影响因素浅析

藏南地区白垩纪时期广泛沉积了一套海相富有机质沉积物,而其中与C-T界线缺氧事件有关的黑色页岩引起了广泛关注。但是,其有机碳含量与西特提斯相比明显偏低。因此,有关该区对海相白垩纪富有机质沉积影响机制的认识显得尤为重要。文中选取前人研究程度较高的岗巴宗山Ⅱ剖面、定日贡扎剖面和江孜加不拉剖面、床得剖面,利用其相关数据,定量计算了这些剖面的沉积速率、堆积速率和古生产力值。结果表明,藏南地区沉积速率以C-T界线时期最高,而岗巴、定日地区与江孜地区的沉积速率表现出较大的差异,这主要与沉积环境有关;并且在沉积速率<4cm/ka时,随着沉积速率的增加,有机碳含量随之增加,而沉积速率较大时,则关系不明显。江孜地区初级生产力较低,其缺氧期黑色页岩的形成并不是高生产力的结果,可能与缺氧条件的保存作用相关;对于岗巴和定日地区而言,尽管计算的古生产力较低,但碳同位素正偏以及推测存在的沿岸上升洋流表明,该区白垩纪富有机质沉积拥有高的初级生产力和缺氧的保存条件,表明该区有良好的古海洋条件,富有机质沉积的形成是高生产力、缺氧的保存条件以及低的沉积速率(<4cm/ka)共同作用的结果。而产生有机碳偏低,从而使得计算的古生产力值偏低的原因,则可能与成岩后期强烈的风化作用,导致有机碳的损失有关;另外定日地区C-T期有机碳含量偏低则还与其沉积物粒度有关。     

Diagenesis of dissolved aluminum in organic-rich estuarine sediments

The sedimentary geochemistry of dissolved Al is complicated by a number of different reactions. In this study we show that complexation by organic matter, adsorption to Fe-oxyhydroxides, and reaction with Si in solution have important effects on the distribution of dissolved Al in sediments. In the absence of physical resuspension of sediment into overlying waters, dissolved Al is rapidly consumed at the sediment-water interface and is subsequently released upon reduction of Fe-oxyhydroxides. This release does not cause noticeable perturbations in dissolved Al concentrations in sediments because of rapid consumption reactions which mask the true mobility of Al. Results suggest that one of the consumption reactions may be due to formation of an Fe-Al-silicate. The amount of authigenic aluminosilicate formed in estuarine sediments must be very small relative to the detrital component. In the deep-sea, however, the long residence time of Fe-oxyhydroxides at the sediment-water interface, with resulting greater accumulation of adsorbed Al may explain the abundance of Al in Fe-smectites reported from many different areas.     

Biogeochemical cycling in an organic-rich coastal marine basin. 6. Temporal and spatial variations in sulfate reduction rates

Rates of sulfate reduction were measured over a 3 year period in the anoxic nearshore sediments of Cape Lookout Bight, North Carolina, using both a tube incubation method and a ³⁵S-sulfate direct injection technique. The methods yielded similar depth-integrated rates over the upper 30 cm ranging from less than 10 mol SO⁼₄ · m⁻² · y⁻¹ in winter to greater than 50 mol SO⁼₄ · m⁻² · y⁻¹ in summer. There were also seasonal changes in the Arrhenius activation energies for the sulfate reduction rates indicating that the assumption that E_a is constant with temperature is not always valid. The time averaged annual turnover rate for all three years was 20.4 (±11.4) mol SO⁼₄ · m⁻² · y⁻¹. Surface rates ranged seasonally from less than 0.01 to over 3 mM SO⁼₄ · d⁻¹ between winter and summer, respectively. A subsurface rate maximum was observed to develop during the summer months which accounted for 28 percent of the annual depth integrated sulfate reduction rate. Subsurface rate maxima are the result of changes in the chemistry (substrate type and/or concentration) and the microbiology in the sediments. The possibility of the subsurface maximum being an artifact of the ³⁵S method is also discussed. However, the sulfate reduction rates compare well with previous measurements of the carbon sediment-water plus burial fluxes and with a depth integrated CO₂ production rate modelled from a ΣCO₂ concentration profile from the same site.     

Biogeochemical cycling in an organic-rich coastal marine basin: 9. Sources and accumulation rates of vascular plant-derived organic material

The sources, degradation and burial of vascular plant debris deposited over the past several decades in the lagoonal sediments of Cape Lookout Bight, North Carolina, are quantified using alkaline cupric oxide lignin oxidation product (LOP) analysis. Non-woody angiosperms, accounting for 92 ± 32% of the recognizable sedimentary vascular plant debris, are calculated to contribute 23 ± 17% of the total organic carbon buried over the past decade (upper meter of sediment column). When combined with a previously established sedimentary organic carbon budget for this site (Martens and Klump, 1984; Martens et al., 1987, in preparation) a vascular plant derived carbon burial rate of 26 ± 20 mole C m⁻² yr⁻¹ is calculated for this same time interval. The refractory nature and invariant depth distributions of the lignin oxidation products (LOP), when coupled with evidence for constant degradation rates of metabolizable materials, indicate that sediment accumulation at this site has been a steady state process with respect to source and burial of organic carbon since its conversion from an inner-continental shelf to a lagoonal environment during the late 1960's. Thus systematic down-core decreases in labile organic matter result from early diagenetic processes rather than input rate variations.     

Sulfur isotope fractionation during bacterial sulfate reduction in organic-rich sediments

Isotope fractionation during sulfate reduction by natural populations of sulfate-reducing bacteria was investigated in the cyanobacterial microbial mats of Solar Lake, Sinai and the sediments of Logten Lagoon sulfuretum, Denmark. Fractionation was measured at different sediment depths, sulfate concentrations, and incubation temperatures. Rates of sulfate reduction varied between 0.1 and 37 micromoles cm-3 d-1, with the highest rates among the highest ever reported from natural sediments. The depletion of 34S during dissimilatory sulfate reduction ranged from 16% to 42%, with the largest 34S-depletions associated with the lowest rates of sulfate reduction and the lowest 34S-depletions with the highest rates. However, at high sulfate reduction rates (>10 micromoles cm-3 d-1) the lowest fractionation was 20% independent of the rates. Overall, there was a similarity between the fractionation obtained by the natural populations of sulfate reducers and previous measurements from pure cultures. This was somewhat surprising given the extremely high rates of sulfate reduction in the experiments. Our results are explained if we conclude that the fractionation was mainly controlled by the specific rate of sulfate reduction (mass cell-1 time-1) and not by the absolute rate (mass volume-1 time-1). Sedimentary sulfides (mainly FeS2) were on average 40% depleted in 34S compared to seawater sulfate. This amount of depletion was more than could be explained by the isotopic fractionations that we measured during bacterial sulfate reduction. Therefore, additional processes contributing to the fractionation of sulfur isotopes in the sediments are indicated. From both Solar Lake and Logten Lagoon we were able to enrich cultures of elemental sulfur-disproportionating bacteria. We suggest that isotope fractionation accompanying elemental sulfur disproportionation contributes to the 34S depletion of sedimentary sulfides at our study sites.     

Volatile organic compounds in Quaternary sediments

The distribution of volatile organic compounds in surface sediments varies widely with the depositional environment. Oxygen and sulfur compounds, alkenes and arenes, are more abundant than alkanes in strongly reducing sediments such as those from around Walvis Bay, West Africa. Among the compounds identified by GC-MS were toluene, benzene, 2-methyl-2-butene, 3,5-dimethylcyclopentene, 3-menthylfuran, 3-methylfuran, 2-methylbutanol, 3-methylbutanol, 3-pentanone, 2-methylthiophene, 3-methylthiophene and dimethylsulfide. Some of these compounds have the isoprene carbon skeleton.In a less reducing environment such as the Arabian Sea-Persian Gulf area, a more diverse alkene assemblage was observed including ethylene, propylene, pentenes, hexenes, cyclohexene, methylpentenes and dimethylcyclopentenes. Also, the sediments contained a few very specific alkane structures. The gem-dimethyl hydrocarbons (neopentane, neohexane, and neoheptane) were dominant among the branched hydrocarbons. The high concentration of volatile alkenes and oxygen and sulfur compounds is not observed in deep sea drilling samples at depths greater than about 100 m.     

一种新的适合富有机质沉积岩的Re-Os同位素分析方法初探

虽然富有机质沉积岩中的Re和Os主要都富集在有机质中,但其中碎屑部分中的Re和Os也会影响其Re-Os等时线的准确度和精度。目前最常用的Cr O3-H2SO4溶样法虽然能尽量避免碎屑物质中Re和Os的溶出,但该方法具有Re流程空白高和环境污染严重等问题。因此,本研究尝试在富有机质沉积岩Re-Os同位素分析中使用H2O2-HNO3溶样来代替Cr O3-H2SO4溶样。本研究利用国际油页岩标样SGR-1b(USGS)为实验研究对象,分别对HCl-HNO3溶样、Cr O3-H2SO4溶样和H2O2-HNO3溶样3种溶样方法进行了对比研究。研究表明,H2O2与HNO3的体积比约为5﹕1的H2O2-HNO3溶液,不仅能保证样品和稀释剂的Re、Os同位素达到同位素交换平衡而且尽可能地避免碎屑物质中Re和Os的溶出。本方法相比于HCl-HNO3溶样,能尽量避免碎屑物质中Re和Os的溶出;而相比于Cr O3-H2SO4溶样,该方法具有本底低、无污染的优点。最后利用H2O2-HNO3溶样方法对广西金秀地区的泥岩样品和广东大宝山地区的碳质页岩样品进行了Re-Os同位素定年分析,分别得到了(404±5)Ma(IOs=1.57±0.13,n=8,MSWD=50)和(211±11)Ma(IOs=0.67±0.09,n=5,MSWD=11.1)的等时线年龄,这一结果与HCl-HNO3溶样得到的结果((412±11)Ma,IOs=1.18±0.38,n=8,MSWD=311;(223±18)Ma,IOs=0.59±0.14,n=5,MSWD=63)在误差范围内一致,但更为精确。     

Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ^44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ^44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ^44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ^44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.     

Compositional similarities of non-solvent extractable fatty acids from recent marine sediments deposited in differing environments

Five recent sediment samples from a variety of North American continental shelves were analyzed for fatty acids (FAs) in the solvent-extractable (SOLEX) lipids as well as four types of non-solvent extractable (NONEX) lipids. The NONEX lipids were operationally defined by the succession of extraction procedure required to recover them. The complete procedure included (i) very mild acid treatment, (ii) HF digestion and (iii) saponification of the sediment residue following exhaustive solvent extraction.The distribution pattern and various compositional parameters of SOLEX FAs in the five sediments were divided into three different groups, indicating the difference of biological sources and also diagenetic factors and processes among the three groups of samples. Nevertheless, the compositions of the corresponding NONEX FAs after acid treatment were surprisingly very similar. This was also true for the remaining NONEX FA groups in the five sediment samples.The findings implied that most of the NONEX FAs reported here are derived directly from living organisms. It is also concluded that a large part of NONEX FAs are much more resistant to biodegradation than we have thought, so that they can form the large percentage of total lipids with increasing depth of water and sediments.     

Early diagenesis of fatty acids in lacustrine sediments—III. Changes in fatty acid composition in the sediments from a brackish water lake

A 3-m sediment core taken from Lake Suigetsu, in which a shift from fresh to brackish water occurred about three hundred years ago, has been examined for variation with depth of organic carbon and fatty acids. From the difference in total amounts of sulphur between sediments under fresh and brackish water environments, the surface sediments above approximately 35 cm depth were deduced to be accumulated under a brackish water environment. The total contents of organic carbon and fatty acids, and percentage composition of fatty acids gave discontinuous profiles above and below the 35–40 cm sediment layer. At a depth of 12.5 cm, the distribution in chain length of the fatty acids changed from a unimodal (the predominance of C₁₂-C₁₈ over C₂₀-C₃₄) to a bimodal pattern, which was mirrored by the composition diversity index (CDI).Although the fatty acids in the surface sediments (0–40 cm) from Lake Suigetsu seemed to suffer milder degradation through microbial activity than those in a core (0–150 cm) from Lake Suwa, a freshwater eutrophic lake, both lacustrine sediments showed similar trends in the alteration of fatty acid composition with depth.     

Selective sequential dissolution of organic-rich stream sediments from Talvivaara, Finland

Organic-rich stream sediments, a widely used material in geochemical prospecting in Finland, were investigated by analyzing Mn, Fe, Co, Ni, Cu and Zn after a series of selective extractions.Forty-seven organic-rich stream-sediment samples were collected in the vicinity of a sulphide mineralization in Talvivaara, eastern Finland. Loss on ignition of the samples at 500°C was 20–95%. pH of the samples, measured in the water pressed from the samples, was 3.4–6.2 with a mean of 4.2.The < 0.5 mm grain-size fraction was subjected to a sequential extraction as follows: NH₄-acetate for exchangeable cations; cold NH₂OH·HCl for dissolution of Mn oxides; H₂O₂ for destruction of organic material; hot NH₂OH·HCl for dissolution of Fe oxides; HF/HClO₄/aqua regia for dissolving the residue. Each extraction was analyzed by flame AAS for Mn, Fe, Co, Ni, Cu and Zn.Manganese and Co are mostly in exchangeable form and in the residue, while the proportion complexed by the organic components is minimal. Iron and Ni own a lot of exchangeable character although a significant proportion of these elements is complexed by the organic components. Most of Cu is in organic form. Zinc is the element most evenly distributed between extractions.