Model for the distribution of sulfate reduction and methanogenesis in freshwater sediments

A model, based on the in situ physiological characteristics of methanogens and sulfate reducers, was developed to describe the distribution of methanogenesis and sulfate reduction in freshwater sediments. The model predicted the relative importance of methane production and sulfate reduction in lakes of various trophic status and generated profiles of sulfate, acetate, methanogenesis, and sulfate reduction comparable to the profiles that are expected based on field studies. The model indicated that at sulfate concentrations greater than 30μM a sulfate-reducing zone develops because sulfate reducers maintain acetate concentrations too low for methanogens to grow. At lower sulfate concentrations a methanogenic zone develops because the dual limitations of low sulfate concentrations and acetate consumption by methanogens prevents sulfate reducers from growing. The model and a compilation of previously published field data indicate that, within the reported range of sulfate concentrations, the relative importance of methanogenesis and sulfate reduction in freshwater sediments is primarily dependent upon the rates of organic matter decomposition.     

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.     

Sulfate reduction and the nature of organic matter in estuarine sediments

The reduction of sulfate by sulfate reducing bacteria in the anoxic zone is an extremely important process during early diagenesis of marine sediments. Our data from Great Bay, NH reinforce the proposal that the rate of sulfate reduction is directly proportional to the reactivity of the organic matter or the amount of readily metabolizable organic matter present in the sediment and, hence, the source of the organic material in the anoxic zone. It appears that organic matter rich in marine organic remains is more easily degraded in the anoxic zone and that sulfate reduction rates can vary considerably in an estuarine system where many types of organic material may be deposited.     

The dependence of bacterial sulfate reduction on sulfate concentration in marine sediments

The effect of dissolved sulfate concentration on the rate of bacterial sulfate reduction in marine sediment from Long Island Sound was examined using a radio-sulfur technique. The experimental results show that the rate is independent of the dissolved sulfate concentration until low levels are reached (<3 mM), and that, when interpreted using a Monod-type rate law, a saturation constant, K_s, of 1.62 ± 0.16 M results. This weak dependence implies that the dissolved sulfate exerts only a limited influence on the rate of sulfate reduction in marine sediments. Given such a weak dependence, dissolved sulfate profiles in marine sediments must resemble profiles generated by models with sulfate independent kinetics. Initially, this would suggest that currently used sulfate-independent diagenetic models are appropriate in modelling sulfate profiles. However, comparison of these models with those containing weak sulfate-dependent kinetic terms shows that there exists considerable disagreement between these models when the parameter grouping $\text{(D}{}_{\mathrm{s}}\text{k)}\text{1}\text{2}\text{/w}$ is larger than ~0.2 and smaller than ~3.0. (Here D_s is the SO^;₄ diffusion coefficient, k the organic matter decay constant and w the sediment burial velocity.) When the currently used models are corrected by employing physically meaningful boundary conditions, this divergence disappears. The modelling results, therefore, confirm the conclusion that any sulfate dependence inherent to the reduction kinetics does not appreciably affect sulfate pore water profiles, and that previous diagenetic studies using strong sulfate dependent models are erroneous.     

Microscopic gold in marine and oceanic sediments

The present-day contribution of coastal-marine placers into the bulk gold production is insignificant. As usual, only gold of coarse- and medium-grained classes is recovered while the fine-grained and dispersed gold are disposed into tailings. During the sedimentation, such a floating gold is removed far from the wave-surf zone. Despite the common belief about poor prospects of the Black Sea shelf for modern gold placers, we have proved the expediency to study the distribution of floating microscopic gold in Holocene marine sediments and carried out the respective works. Using the special concentrating methods, we enabled to detect the gold in most of the 830 samples collected. Geomorphological, lithological, hydrodynamic, and other factors controlling the gold potential were determined. In some cases, the gold content exceeds the minimal economic grade in continental placers. The prospective sites for further investigation were outlined. It was established that the polygenic microscopic gold can be divided into at least clastic, authigenic, and clastic-authigenic types. According to our data, the alluvial, lagoonal-marine, liman, and other sediments at the adjacent land also contain substantial amounts of microscopic gold. The pre10987nary study of oceanic bottom sediments near the Antarctic Peninsula and within the Argentine Basin proved the possibility of microscopic gold to accumulate under various facies conditions. The microscopic gold, mainly of clastic type, was detected here in 82% of samples. The obtained results testify to the global-scale deposition of floating microscopic gold in sedimentation basins of various age and may serve as a basis for the further comprehensive tackling of the problem in different regions.     

The significance of isotope specific diffusion coefficients for reaction-transport models of sulfate reduction in marine sediments

Modeling isotopic signatures in systems affected by diffusion, advection, and a reaction which modifies the isotopic abundance of a given species, is a discipline in its infancy. Traditionally, much emphasis has been placed on kinetic isotope effects during biochemical reactions, while isotope effects caused by isotope specific diffusion coefficients have been neglected. A recent study by Donahue et al. (2008) suggested that transport related isotope effects may be of similar magnitude as microbially mediated isotope effects. Although it was later shown that the assumed differences in the isotope specific diffusion coefficients were probably overstated by one or two orders of magnitude (Bourg, 2008), this study raises several important issues: (1) Is it possible to directly calculate isotopic enrichment factors from measured concentration data without modeling the respective system? (2) Do changes in porosity and advection velocity modulate the influence of isotope specific diffusion coefficients on the fractionation factor α? (3) If one has no a priori knowledge whether diffusion coefficients are isotope specific or not, what is the nature and magnitude of the error introduced by either assumption? Here we argue (A) That the direct substitution of measured data into a differential equation is problematic and cannot be used as a replacement for a reaction-transport model; (B) That the transport related fractionation scales linearly with the difference between the respective diffusion coefficients of a given isotope system, but depends in a complex non-linear way on the interplay between advection velocity, and downcore changes of temperature and porosity. Last but not least, we argue that the influence of isotope specific diffusion coefficients on microbially mediated sulfate reduction in typical marine sediments is considerably smaller than the error associated with the determination of the fractionation factor.     

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.     

Silicate weathering in anoxic marine sediments

Two sediment cores retrieved at the northern slope of Sakhalin Island, Sea of Okhotsk, were analyzed for biogenic opal, organic carbon, carbonate, sulfur, major element concentrations, mineral contents, and dissolved substances including nutrients, sulfate, methane, major cations, humic substances, and total alkalinity. Down-core trends in mineral abundance suggest that plagioclase feldspars and other reactive silicate phases (olivine, pyroxene, volcanic ash) are transformed into smectite in the methanogenic sediment sections. The element ratios Na/Al, Mg/Al, and Ca/Al in the solid phase decrease with sediment depth indicating a loss of mobile cations with depth and producing a significant down-core increase in the chemical index of alteration. Pore waters separated from the sediment cores are highly enriched in dissolved magnesium, total alkalinity, humic substances, and boron. The high contents of dissolved organic carbon in the deeper methanogenic sediment sections (50-150 mg dm⁻³) may promote the dissolution of silicate phases through complexation of Al³⁺ and other structure-building cations. A non-steady state transport-reaction model was developed and applied to evaluate the down-core trends observed in the solid and dissolved phases. Dissolved Mg and total alkalinity were used to track the in-situ rates of marine silicate weathering since thermodynamic equilibrium calculations showed that these tracers are not affected by ion exchange processes with sediment surfaces. The modeling showed that silicate weathering is limited to the deeper methanogenic sediment section whereas reverse weathering was the dominant process in the overlying surface sediments. Depth-integrated rates of marine silicate weathering in methanogenic sediments derived from the model (81.4-99.2 mmol CO₂ m⁻² year⁻¹) are lower than the marine weathering rates calculated from the solid phase data (198-245 mmol CO₂ m⁻² year⁻¹) suggesting a decrease in marine weathering over time. The production of CO₂ through reverse weathering in surface sediments (4.22-15.0 mmol CO₂ m⁻² year⁻¹) is about one order of magnitude smaller than the weathering-induced CO₂ consumption in the underlying sediments. The evaluation of pore water data from other continental margin sites shows that silicate weathering is a common process in methanogenic sediments. The global rate of CO₂ consumption through marine silicate weathering estimated here as 5-20 Tmol CO₂ year⁻¹ is as high as the global rate of continental silicate weathering.     

Gold,palladium and iridium in marine sediments

The paper presents a preliminary evaluation of some processes affecting the noble metal content of deep-sea sediments. Neutron activation data for Au, Pd and Ir in deep-sea sediments, nearshore Arctic sediments and soils and Tahitian basalts and weathered derivatives are presented. A suite of sediment samples across the East Pacific Rise provide strong evidence that submarine volcanic exhalation has contributed significantly to the Pd and Au contents of these sediments. Limited data on continental weathering indicate that detritus contributed to the marine environment will not differ greatly in Au, Pd or Ir content compared to its continental source rocks.     

Sterols in interstitial waters of marine sediments

In order to attempt to elucidate the nature of biogeochemical processes occurring at the water-sediment interface, sterols have been analysed in near bottom sea and interstitial waters collected in the eastern and western intertropical Atlantic ocean. Free and esterified sterol concentrations range from 0.2 to 82 μg l^?1 and are much higher than those found in overlying sea water, which range from 0.2 to 1.7 μg l^?1 for the dissolved fraction and from 0.01 to 0.07 μg l^?1 for the particulate fraction. Cholest-5-en-3β-ol and 24-ethylcholest-5-en-3β-ol are the dominant sterols in sea and interstitial waters. The variability encountered for the relative importance of minor sterols such as 24-methylcholesta-5,24(28)-dien-3β-ol and stanols, 5α-cholest-22(E)-en-3β-ol, 5α-cholestan-3β-ol and 24-ethyl-5α-cholestan-3β-ol in interstitial water and their variation with depth is discussed in terms of diversity of inputs and bacterial activity. For sediments cored off the Mauritanian coast, a productive area characterized by an intense upwelling, the chemical signatures observed in interstitial water through stanol/stenol ratios occur at levels of very high heterotrophic aerobic bacterial biomass estimations. The study of the sterol composition of interstitial water could constitute a valuable tool in appreciating the intensity of chemical and biological processes occurring in the first few metres of recent marine sediments.     

Vanadyl ions in ancient marine carbonaceous sediments

Vanadyl ions in ancient shaly-type sedimentary rocks of marine origin from a variety of world sources and geological periods have been investigated using electron spin resonance. These and other results provide evidence that there are two types of vanadyl ions. The first is inorganically bound in the clay/ silicate fraction of these rocks and the second type is associated with vanadyl porphyrin compounds.     

Two-dimensional pH distributions and dynamics in bioturbated marine sediments

The seafloor is the site of intense biogeochemical and mineral dissolution-precipitation reactions which generate strong gradients in pH near the sediment-overlying water interface. These gradients are usually measured in one-dimension vertically with depth. Two-dimensional pH distributions in marine sediments were examined at high resolution (65 × 65 μm pixel) and analytical precision over areas of ∼150 to 225 cm² using a newly developed pH planar fluorosensor. Dramatic three-dimensional gradients, complex heterogeneity, and dynamic changes of pH occur in the surficial zone of deposits inhabited by macrofauna. pH can vary by ±2 units horizontally as well as vertically over millimeter scales. pH minima zones often form in association with redoxclines within a few millimeters of inner burrow walls, and become more pronounced with time if burrows remain stable and irrigated for extended periods. Microenvironmental pH minima also form locally around decaying biomass and relict burrow tracks, and dissipate with time (∼5 d). H⁺ concentrations and fluxes in sandy mud show complex acid-base reaction distributions with net H⁺ fluxes around burrows up to ∼12 nmol cm⁻² d⁻¹ and maximum net reaction rates varying between −90 (consumption) to 120 (production) μM d⁻¹ (∼90 nmol cm⁻¹ d⁻¹ burrow length). Acid producing zones that surround irrigated burrows are largely balanced by acid titration zones along inner burrow walls and outer radial boundaries. The geometry and scaling of pH microenvironments are functions of diagenetic reaction rates and three-dimensional transport patterns determined by sediment properties, such as diffusive tortuosity, and by benthic community characteristics such as the abundance, mobility, and size of infauna. Previously, undocumented biogeochemical phenomena such as low pH regions associated with in-filled relict biogenic structures and burrowing tracks are readily demonstrated by two-dimensional and time-dependent images of pH and sedimentary structure.     

Distribution of intact and core GDGTs in marine sediments

We conducted a survey of archaeal GDGT (glycerol dibiphytanyl glycerol tetraether) distributions in marine sediments deposited in a range of depositional settings. The focus was comparison of two pools presumed to have distinct geobiological significance, i.e. intact polar GDGTs (IP GDGTs) and core GDGTs (C GDGTs). The former pool has been suggested to be related to living communities of benthic archaea in marine sediments, while the latter is commonly interpreted to consist of molecular fossils from past planktonic archaeal communities that inhabited the surface ocean. Understanding the link between these two pools is important for assessment of the validity of current molecular proxies for sedimentary archaeal biomass and past sea surface temperatures. The relative distributions of GDGTs in the two pools in a core at a CH₄ rich site in the Black Sea provide evidence for in situ production of glycosidic IP GDGTs and their subsequent degradation to corresponding C GDGTs on timescales that are short in geological terms. In addition, we monitored the relationship between the IP GDGT and C GDGT pools in a sample set from various ocean basins with subseafloor depth from a few cm to 320 m and 0 to 4 Myr in age. Notable differences between the two pools can be summarized as follows: the GDGT with acyclic biphytanes, GDGT-0, and its analogues with two and three cyclopentane moieties (GDGT-2 and -3) are generally more abundant in the pool of IP GDGTs, while crenarchaeol tends to be more abundant in the C GDGT pool. Consequently, the ring index is generally higher for the C GDGTs while TEX₈₆, a molecular proxy ratio not considering the two major GDGTs, tends to be higher in the IP GDGT pool. These differences in the proportion of individual GDGTs in the two pools are probably due to in situ production of IP GDGTs with distributions differing from those of C GDGTs. Despite these differences, we observed significant correlation of these two ratios between the two pools. Specifically, in both pools TEX₈₆ is high in sediments from warm oceanic regimes and low in cold regimes. We discuss these relationships and suggest that recycling of core GDGTs by benthic archaea is an important mechanism linking both molecular pools.     

Germanium isotopic variations in igneous rocks and marine sediments

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICPMS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of ⁷⁴Ge/⁷⁰Ge ratios are expressed as δ⁷⁴Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2‰ for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4‰ in δ⁷⁴Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of ⁷⁴Ge/⁷⁰Ge, ⁷³Ge/⁷⁰Ge and ⁷²Ge/⁷⁰Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of δ⁷⁴Ge in igneous rocks is only 0.25‰ without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a δ⁷⁴Ge of 1.3 ± 0.2‰ can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher δ⁷⁴Ge values between 2.0‰ and 3.0‰. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the δ⁷⁴Ge of the seawater to +3.0‰.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have δ⁷⁴Ge values ranging from 0.7‰ to 2.0‰. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.     

Volatile fatty acid cycling in organic-rich marine sediments

Volatile fatty acid (VFA) apparent turnover rates were determined by measuring whole sediment VFA concentrations and the corresponding reaction rate constants. The following ranges of VFA concentrations were measured in Cape Lookout Bight, N.C. sediments (μmole·l_s^?1): acetate 54–660, propionate 1–24, butyrate <0.5–22, iso-butyrate <0.5–6. Apparent turnover rates measured over a one-year period ranged from 18–600 μmole·l_s^?1·h^?1 for acetate and 0.7–7 μmole·l_s^?1·h^?1 for the carboxyl carbon of propionate. Methane production was observed only with acetate and only in sulfatedepleted sediments; total acetate turnover attained approximately the same maximum value in both sulfate-reducing and sulfate-depleted sediments.Apparent turnover rates for acetate and propionate appeared to be controlled by similar factors: in sulfate-reducing (surface) sediments the turnover rates were stimulated by autumn storm-mediated deposition/resuspension events; in deeper sulfate-depleted sediments the turnover rates followed changes in the ambient temperature. Changes in VFA poolsizes were proportionally much larger than changes in corresponding rate constants. The ratio of CO₂ to CH₄ produced from acetate vs. depth suggested that non-methanogenic bacteria accounted for 60% of the acetate turnover in sulfate-depleted sediments.VFA concentrations were much lower in N.C. continental slope mud than in Cape Lookout sediments; acetate was the only VFA detectable throughout the top 40 cm of the slope sediments. The estimated production rate of CO₂ from acetate decreased rapidly with depth. The surface rate was approximately 20 times less than that measured at similar temperatures in sulfate-reducing Cape Lookout sediments.     

Laboratory simulation of diffusion in contaminated marine sediments

Wastes from offshore oil drilling activities are often discharged to the marine environment. Solid wastes that settle onto the bottom sediment may pose a health threat to marine organisms and eventually to man through the food chain. We need to understand their fate in order to predict the chemical concentration levels and life-times in the sediment and adjoining aquatic boundary layer. A laboratory simulation of selected in-bed processes that addresses contaminant leaching from the sediment is proposed. The process chosen for simulation in this study is the coupled desorption-diffusion of contaminants from the bed to the water column. A simple mathematical model of the process is also proposed. Preliminary results using organic chemicals for both the simulation and the model are presented. The results suggest that the experimental procedure represents a good way of estimating the diffusive leaching rates of hydrophobic compounds from contaminated sediments.     

Preservation of particulate non-lithogenic uranium in marine sediments

Particulate non-lithogenic uranium (PNU), excess U above detrital background levels found in marine particulate matter, is formed in surface waters throughout the ocean. Previous studies have shown that PNU is regenerated completely prior to burial of particles in sediments within well-oxygenated open-ocean regions. However, the fate of PNU has never been examined in ocean margin regions or in anoxic basins. Here we evaluate the preservation of PNU in ocean margin sediments and within semi-enclosed basins using samples from sediment traps deployed at multiple depths and surface sediments. Organic carbon fluxes at the sediment trap locations ranged from 0.1 to 4.3 g/cm² kyr, while the dissolved oxygen concentration in the water column ranged from <3 μM to ∼ 270 μM. Preservation of PNU increases with decreasing dissolved oxygen concentration, approaching 100% preservation at oxygen concentration < 25 μM. PNU contributes as much as 40 to 70% of the total authigenic U in sediments in the Santa Barbara Basin and seasonally anoxic Saanich Inlet, and some 10% to 50% of the total authigenic U in sediments off the central California Margin.