Christopher S. Martens

Field and laboratory studies of methane oxidation in an anoxic marine sediment: Evidence for a methanogen‐sulfate reducer consortium

Field and laboratory studies of anoxic sediments from Cape Lookout Bight, North Carolina, suggest that anaerobic methane oxidation is mediated by a consortium of methanogenic and sulfate-reducing bacteria. A seasonal survey of methane oxidation and CO2 reduction rates indicates that methane production was confined to sulfate-depleted sediments at all times of year, while methane oxidation occurred in two modes. In the summer, methane oxidation was confined to sulfate-depleted sediments and occurred at rates lower than those of CO2 reduction. In the winter, net methane oxidation occurred in an interval at the base of the sulfate-containing zone. Sediment incubation experiments suggest both methanogens and sulfate reducers were responsible for the observed methane oxidation. In one incubation experiment both modes of oxidation were partially inhibited by 2-bromoethanesulfonic acid (a specific inhibitor of methanogens). This evidence, along with the apparent confinement of methane oxidation to sulfate-depleted sediments in the summer, indicates that methanogenic bacteria are involved in methane oxidation. In a second incubation experiment, net methane oxidation was induced by adding sulfate to homogenized methanogenic sediments, suggesting that sulfate reducers also play a role in the process. We hypothesize that methanogens oxidize methane and produce hydrogen via a reversal of CO2 reduction. The hydrogen is efficiently removed and maintained at low concentrations by sulfate reducers. Pore water H2 concentrations in the sediment incubation experiments (while net methane oxidation was occurring) were low enough that methanogenic bacteria could derive sufficient energy for growth from the oxidation of methane. The methanogen-sulfate reducer consortium is consistent not only with the results of this study, but may also be a feasible mechanism for previously documented anaerobic methane oxidation in both freshwater and marine environments.

Methane production in the interstitial waters of sulfate-depleted marine sediments

Methane in the interstitial waters of anoxic Long Island Sound sediments does not reach appreciable concentrations until about 90 percent of seawater sulfate is removed by sulfate-reducing bacteria. This is in agreement with laboratory studies of anoxic marine sediments sealed in jars, which indicate that methane production does not occur until dissolved sulfate is totally exhausted. Upward diffusion of methane or its production in sulfate-free microenvironments, or both, can explain the observed coexistence of measurable concentrations of methane and sulfate in the upper portions of anoxic sediments.

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.

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

The release of remineralized N and P from the organic-rich anoxic sediments of Cape Lookout Bight is controlled by processes occurring within the sediment column and at the sediment-water interface. The relatively rapid rates of temperature dependent microbial degradation of organic matter support seasonally varying nutrient fluxes ranging from 20 to 1200 μmol·m−2·hr−1 for dissolved ammonium and from − 20 to 120 μmol·m−2·hr−1 for total dissolved phosphate (measured in situ over the period October, 1976 to October, 1978). Molecular diffusion along steep vertical pore water concentration gradients measured simultaneously cannot explain the high fluxes observed during warmer months. Gradients for ammonium and phosphate ranged from 0.33 to 1.10 and from 0 to 0.29 μmol·cm−3pw·cm−1s respectively. These high summertime fluxes appear to result from increased sediment-water transport associated with bubble tubes created and maintained by low-tide methane gas bubble ebullition. When these tubes are present, apparent bulk sediment diffusivities calculated from concurrent studies of methane and radon-222 sediment-water exchange are 1.0–3.1 times greater than molecular diffusivities. Nutrient fluxes calculated via Ficks first law taking into account this enhanced transport and the differential diffusive mobilities of dissolved ammonium, phosphate and phosphate ion pairs indicate that removal by aerobic adsorption and/or biological uptake at the sediment-water interface plays an important role in controlling nutrient exchange in these sediments.

Thermodynamic control on hydrogen concentrations in anoxic sediments

Abstract Molecular hydrogen plays a central role in bacterially mediated anoxic sediment chemistry, as both an important electron transfer agent and a key thermodynamic control. We studied the response of hydrogen concentrations to changes in temperature, specific electron acceptor, sulfate concentration, and pH in a series of laboratory experiments using sediments from Cape Lookout Bight, North Carolina. Hydrogen concentrations were found to depend significantly on each of these factors in a fashion that suggests thermodynamic control. In general, the change in hydrogen concentrations was apparently driven by a necessity to maintain a constant ΔG for the predominant terminal electron-accepting process. We hypothesize this situation derives from highly competetive conditions that force terminal metabolic bacteria to operate right at their thermodynamic limits. The response of hydrogen to individual controls in the laboratory experiments was reflected in relatively quantitiative fashion in down-core, seasonal, and inter-environmental variations observed in sediment cores from Cape Lookout Bight and the White Oak River, NC.

Reactivity of recently deposited organic matter: Degradation of lipid compounds near the sediment-water interface

The usefulness of biomarker compounds buried in marine sediments depends upon a quantita tive understanding of the effects of early diagenesis on their distribution. To address this, a new experimental approach was utilized to determine rates of degradation in a coastal sediment. Rates of degradation for solvent-extractable lipid components were quantified in four sediment horizons composed of newly accumulated organic matter (31–144 days since deposition). Sediment accumulation rate data derived from changes in the inventory of Be-7 (t1/2 = 53.3 days) were combined with concentration data for lipid biomarker compounds, enabling us to evaluate the reactivity of organic matter in the upper 8 cm of the rapidly accumulating sediments of Cape Lookout Bight, North Carolina, USA (CLB). Net rates of loss and rate constants were calculated for individual compounds belonging to three classes of lipids: fatty acids, sterols, and n-alkanes. Individual components showed a range in reactivity, in some cases (fatty acids), attributable to differences in their biological sources. Rates and rate constants were consistently highest in the surficial sediments (0–2.5 cm), indicating that the reactivity of a given molecule(s) decreases over time, and beginning soon after deposition. Comparison with apparent rate constants (k′) calculated over longer timescales (one and ten years) shows that steady-state diagenetic models underestimate rates of degradation at or near the sediment-water interface by an order of magnitude.

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.

Indicators of methane-derived carbonates and chemosynthetic organic carbon deposits: examples from the Florida Escarpment

Abyssal chemosynthetic communities are supported by bacterial oxidation of reduced chemicals in brines which seep out through sediments at the base of the Florida Escarpment. They are surrounded by carbonate hardgrounds and sediments rich in fresh organic carbon that contain a record of the metabolic pathways and geochemical processes which are active at these sites. The isotopic composition of tissue samples (δ 13 C as low as #7576.40∓), carbonate crusts (δ 13 C as low #7545.19∓) and sedimentary organic matter (δ 13 C as low #7567.87∓) indicate that biogenic methane dissolved in the brines (δ 13 C #7583.3 ± 5.8∓) is a major carbon source for many of the locally synthesized compounds

Seasonal variations in the sources and alteration of organic matter associated with recently-deposited sediments

Analysis of lipid biomarker compounds associated with surface sediment (0–0.5 or 0–1.0 cm) deposited monthly in Cape Lookout Bight (CLB), North Carolina, U.S.A. revealed seasonal trends in the relative importance of various sources of organic matter. Seasonality in these sources was reflected through variations of source-specific biomarkers in three classes of extractable lipid components—fatty acids, sterols and hydrocarbons, over an 18 month period. Samples collected during periods of sediment accumulation (winter/spring, generally) showed an increase in the relative abundance of algal-derived components. Summer months were characterized by negligible accumulation of sediment and a threefold increase in fatty acids of bacterial origin (i.e. odd numbered n-alkanoic acids and iso- and anteiso-branched acids). Further evidence for the activity of bacteria during summer months was seen by increases in the 5α(H)-cholestan-3s-ol to cholest-5-en-3s-ol ratio. These data indicate that bacterially-mediated processes incorporate organic matter derived from other sources, and accumulated during other times of the year, into biomass. As a result, in situ processes control the composition of preserved organic matter at least as much as temporal changes in the delivery of materials derived from allochthonous sources.

Apparent minimum free energy requirements for methanogenic Archaea and sulfate‐reducing bacteria in an anoxic marine sediment

Among the most fundamental constraints governing the distribution of microorganisms in the environment is the availability of chemical energy at biologically useful levels. To assess the minimum free energy yield that can support microbial metabolism in situ, we examined the thermodynamics of H2-consuming processes in anoxic sediments from Cape Lookout Bight, NC, USA. Depth distributions of H2 partial pressure, along with a suite of relevant concentration data, were determined in sediment cores collected in November (at 14.5°C) and August (at 27°C) and used to calculate free energy yields for methanogenesis and sulfate reduction. At both times of year, and for both processes, free energy yields gradually decreased (became less negative) with depth before reaching an apparent asymptote. Sulfate-reducing bacteria exhibited an asymptote of −19.1±1.7 kJ (mol SO2−4)−1, while methanogenic Archaea were apparently supported by energy yields as small as −10.6±0.7 kJ (mol CH4)−1.