The ecological significance of sulfur in the energy dynamics of salt marsh and coastal marine sediments

Sulfur is an important element in the metabolism of salt marshes and subtidal, coastal marine sediments because of its role as an electron acceptor, carrier, and donor. Sulfate is the major electron acceptor for respiration in anoxic marine sediments. Anoxic respiration becomes increasingly important in sediments as total respiration increases, and so sulfate reduction accounts for a higher percentage of total sediment respiration in sediments where total respiration is greater. Thus, sulfate accounts for 25% of total sediment respiration in nearshore sediments (200 m water depth or less) where total respiration rates are 0.1 to 0.3gCm^–1 day^–1 , for 50% to 70% in nearshore sediments with higher rates of total respiration (0.3 to 3gCm^–2 day^–1), and for 70% to 90% in salt marsh sediments where total sediment respiration rates are 2.5 to 5.5gcm^–2 day^–1 .During sulfate reduction, large amounts of energy from the respired organic matter are conserved in inorganic reduced sulfur compounds such as soluble sulfides, thiosulfate, elemental sulfur, iron monosulfides, and pyrite. Only a small percentage of the reduced sulfur formed during sulfate reduction is accreted in marine sediments and salt marshes. When these reduced sulfur compounds are oxidized, energy is released. Chemolithoautotrophic bacteria which catalyze these oxidations can use the energy of oxidation with efficiencies (the ratio of energy fixed in organic biomass to energy released in sulfur oxidation) of up to 21–37% to fix CO₂ and produce new organic biomass.Chemolithoautotrophic bacterial production may represent a significant new formation of organic matter in some marine sediments. In some sediments, chemolithoautotrophic bacterial production may even equal or exceed organoheterotrophic bacterial production. The combined cycle of anaerobic decomposition through sulfate reduction, energy conservation as reduced sulfur compounds; and chemolithoautotrophic production of new organic carbon serves to take relatively low-quality organic matter from throughout the sediments and concentrate the energy as living biomass in a discrete zone near the sediment surface where it can be readily grazed by animals.Contribution from a symposium on the role of sulfur in ecosystem processes held August 10, 1983, at the annual meeting of the A.I.B.S., Grand Forks, ND; Myron Mitchell, convenor.     

Reduction of Sulfur Compounds in the Sediments of a Eutrophic Lake Basin

Concentrations of various sulfur compounds (SO₄²⁻, H₂S, S⁰, acid-volatile sulfide, and total sulfur) were determined in the profundal sediments and overlying water column of a shallow eutrophic lake. Low concentrations of sulfate relative to those of acid-volatile sulfide and total sulfur and a decrease in total sulfur with sediment depth implied that the contribution of dissimilatory sulfur reduction to H₂S production was relatively minor. Addition of 1.0 mM Na₂³⁵SO₄ to upper sediments in laboratory experiments resulted in the production of H₂³⁵S with no apparent lag. Kinetic experiments with ³⁵S demonstrated an apparent K_m of 0.068 mmol of SO₄²⁻ reduced per liter of sediment per day, whereas tracer experiments with ³⁵S indicated an average turnover time of the sediment sulfate pool of 1.5 h. Total sulfate reduction in a sediment depth profile to 15 cm was 15.3 mmol of sulfate reduced per m² per day, which corresponds to a mineralization of 30% of the particulate organic matter entering the sediment. Reduction of ³⁵S⁰ occurred at a slower rate. These results demonstrated that high rates of sulfate reduction occur in these sediments despite low concentrations of oxidized inorganic compounds and that this reduction can be important in the anaerobic mineralization of organic carbon.     

Methylmercury Oxidative Degradation Potentials in Contaminated and Pristine Sediments of the Carson River, Nevada

Sediments from mercury-contaminated and uncontaminated reaches of the Carson River, Nevada, were assayed for sulfate reduction, methanogenesis, denitrification, and monomethylmercury (MeHg) degradation. Demethylation of [(sup14)C]MeHg was detected at all sites as indicated by the formation of (sup14)CO(inf2) and (sup14)CH(inf4). Oxidative demethylation was indicated by the formation of (sup14)CO(inf2) and was present at significant levels in all samples. Oxidized/reduced demethylation product ratios (i.e., (sup14)CO(inf2)/(sup14)CH(inf4) ratios) generally ranged from 4.0 in surface layers to as low as 0.5 at depth. Production of (sup14)CO(inf2) was most pronounced at sediment surfaces which were zones of active denitrification and sulfate reduction but was also significant within zones of methanogenesis. In a core taken from an uncontaminated site having a high proportion of oxidized, coarse-grain sediments, sulfate reduction and methanogenic activity levels were very low and (sup14)CO(inf2) accounted for 98% of the product formed from [(sup14)C]MeHg. There was no apparent relationship between the degree of mercury contamination of the sediments and the occurrence of oxidative demethylation. However, sediments from Fort Churchill, the most contaminated site, were most active in terms of demethylation potentials. Inhibition of sulfate reduction with molybdate resulted in significantly depressed oxidized/reduced demethylation product ratios, but overall demethylation rates of inhibited and uninhibited samples were comparable. Addition of sulfate to sediment slurries stimulated production of (sup14)CO(inf2) from [(sup14)C]MeHg, while 2-bromoethanesulfonic acid blocked production of (sup14)CH(inf4). These results reveal the importance of sulfate-reducing and methanogenic bacteria in oxidative demethylation of MeHg in anoxic environments.     

Measurement of bacterial sulfate reduction in sediments: Evaluation of a single-step chromium reduction method

A procedure which includes the Total Reduced Inorganic Sulfur (TRIS) in a single distillation step is described for the radiotracer measurement of sulfate reduction in sediments. The TRIS includes both Acid Volatile Sulfide (AVS: H₂S + FeS) and the remaining Chromium Reducible Sulfur (CRS: S⁰, FeS₂). The single-step distillation was simpler and faster than the consecutive distillations of AVS and CRS. It also resulted in higher (4–50%) sulfate reduction rates than those obtained from the sum of³⁵S in AVS and CRS. The difference was largest when the sediment had been dried after AVS but before CRS distillation. Relative to the³⁵S-AVS distillation alone, the³⁵S-TRIS single-step distallation yielded 8–87% higher reduction rates. The separation and recovery of FeS, S⁰ and FeS₂ was studied under three distillation conditions: 1) cold acid, 2) cold acid with Cr²⁺, and 3) hot acid with Cr²⁺. The FeS was recovered by cold acid alone while pyrite was recovered by cold acid with Cr²⁺. A smaller S⁰ fraction, presumably of the finer crystal sizes, was recovered also in the cold acid with Cr²⁺ while most of the S⁰ required hot acid with Cr²⁺ for reduction to H₂S.     

Sulfate Reduction in Peat from a New Jersey Pinelands Cedar Swamp

Microbial sulfate reduction rates in acidic peat from a New Jersey Pine Barrens cedar swamp in 1986 were similar to sulfate reduction rates in freshwater lake sediments. The rates ranged from a low of 1.0 nmol cm⁻³ day⁻¹ in February at 7.5- to 10.0-cm depth to 173.4 nmol cm⁻³ day⁻¹ in July at 5.0- to 7.5-cm depth. The presence of living Sphagnum moss at the surface generally resulted in reduced rates of sulfate reduction. Pore water sulfate concentrations and water table height also apparently affected the sulfate reduction rate. Concentrations of sulfate in pore water were nearly always higher than those in surface water and groundwater, ranging from 26 to 522 μM. The elevated pore water sulfate levels did not result from the evapotranspiratory concentration of infiltrating stream water or groundwater, but probably resulted from oxidation of reduced sulfur compounds, hydrolysis of ester sulfates present in the peat, or both. The total sulfur content of peat that had no living moss at the surface was 164.64 ± 1.5 and 195.8 ± 21.7 μmol g (dry weight)⁻¹ for peat collected from 2.5 to 5.0 and 7.5 to 10.0 cm, respectively. Organosulfur compounds accounted for 84 to 88% of the total sulfur that was present in the peat. C-bonded sulfur accounted for 91 to 94% of the organic sulfur, with ester sulfate being only a minor constituent. Reduced inorganic sulfur species in peat from 2.5 to 7.5 cm were dominated by H₂S-FeS (68%), while pyritic sulfide was the predominant inorganic sulfur species in the peat from depths of 7.5 to 10.0 cm (75%).     

A rapid and simple method for estimating sulfate reduction activity and quantifying inorganic sulfides

Volume, 63, no. 4, p. 1627-1630. After publication of this article, it was brought to the attention of the authors that an earlier paper, similar in both methodology and salient findings to ours, was published by Y. P. Hsieh and C. H. Yang. Both papers describe a diffusion method for the extraction and recovery of reduced inorganic sulfides from sediment samples placed in sealed reaction vessels. Our paper describes the application of the method to the measurement of sulfate reduction rates. The earlier work contains important information, but unfortunately, the existence of the work was realized only after publication of our paper. We regret this omission, and the following reference should have been cited in our article. 13a.Hsieh, Y. P., and C. H. Yang. 1989. Diffusion methods for the determination of reduced inorganic sulfur species in sediments. Limnol. Oceanogr. 34: 1126-1130. [This corrects the article on p. 1627 in vol. 63.].     

Sulfhydrolase Activity in Sediments of Wintergreen Lake, Kalamazoo County, Michigan

The hydrolysis of p-nitrophenyl sulfate, p-nitrocatechol sulfate, and [³⁵S]sodium dodecyl sulfate was examined in anoxic sediments of Wintergreen Lake, Michigan. Significant levels of sulfhydrolase activity were observed in littoral, transition, and profundal sediment samples. Rates of sulfate formation suggest that the sulfhydrolase system would represent a major source of sulfate within these sediments. Sulfate formed by ester sulfate hydrolysis can support dissimilatory sulfate reduction as shown by the incorporation of ³⁵S from labeled sodium dodecyl sulfate into H₂³⁵S. Sulfhydrolase activity varied with sediment depth, was greatest in the littoral zone, and was sensitive to the presence of oxygen. Estimations of ester sulfate concentrations in sediments revealed large quantities of ester sulfate (~30% of total sulfur). Both total sulfur and ester sulfate concentrations varied with the sediment type and were two to three orders of magnitude greater than the inorganic sulfur concentration.     

Bacteria in gel probes: comparison of the activity of immobilized sulfate-reducing bacteria with in situ sulfate reduction in a wetland sediment.

A novel method was used to examine the microbial ecology of iron-rich wetland sediments receiving neutral-pH coal mine drainage. Gel probes inserted into the sediments allowed analysis of the distribution and activity of bacterial sulfate reduction (BSR). A mixed population of sulfate-reducing bacteria enriched from anoxic wetland sediments was immobilized in low temperature-gelling agarose held in grooved rods or probes. The probes were inserted vertically into sediments and were allowed to incubate in situ for 48 h. After their retrieval, the gels were sectioned and analyzed for residual BSR activity and were compared to in situ BSR rates and chemical porewater profiles. The depth distribution of residual BSR activity in the immobilized cell gel probes differed significantly from the BSR measured in situ. Approximately 51% of the total integrated residual sulfate reduction activity measured in the gel probes occurred between 0 and 7 cm of the upper 20 cm of sediment. In contrast, ca. 99% of the integrated in situ BSR occurred between 7- and 20-cm depth, and only 1% of the total integrated rate occurred between 0- and 7-cm depth. Lactate-enriched bacteria immobilized in the gel may have been atypical of the majority of sulfate-reducing bacteria in the sediment. Agarose-immobilized sulfate-reducing bacteria might also be able to proliferate in the otherwise inhospitable zone of iron reduction, where sulfate and labile carbon compounds for which they are usually outcompeted can diffuse freely into the gel matrix. Gel probes containing particulate iron monosulfide (FeS) indicated that FeS remained stable in sediments at depths greater than 2 to 3 cm below the sediment-water interface, consistent with the shallow penetration of oxygen into surface sediments.     

Sulfate reduction in lake sediments inhabited by the isoetid macrophytes Littorella uniflora and Isoetes lacustris

Sulfur cycling was examined in sediments inhabited with the isoetids Littorella uniflora and Isoetes lacustris in the oligotrophic soft-water Lake Kalgaard, Denmark. Based on short-term tracer incubations sulfate reduction was measured along a transect from the shore (0.6 m) to profundal sediments (4.6 m). The sulfate reduction rates were low (0.008–0.8 mmol m⁻² d⁻¹) in the sandy shallow sediments with low organic content (<1.3 mmol C g⁻¹ sed DW) and high redox potentials (>100 mV), whereas sulfate reduction was higher at the deeper sites (2.7–4.6 mmol m⁻² d⁻¹) with high organic content (max. 11.5 mmol C g⁻¹ sed DW) and lower redox potentials (<100 mV). High concentrations of dissolved organic carbon (DOC) were found in the low particulate organic sediments (up to 18.4 mM), and most of the DOC pool consisted of acetate (40–77%). Reoxidation of sulfides due to root oxygen release was probably important at all sites and a positive efflux of sulfate across the sediment–water interface was measured, attaining rates (up to 4.8 mmol m⁻² d⁻¹) similar to the sulfate reduction rates. Reoxidation of sulfides was also manifested by high fraction (>80%) of reduced sulfides being accumulated as elemental sulfur or pyrite (chromium reducible sulfur, CRS). The largest pools of CRS were found in high organic sediment with vertical distributions resembling those of the sulfate reduction rates. The overall effect of isoetid growth on sulfur cycling in the rhizosphere is a suppression of sulfate reduction in low organic sediments and the governing of sulfide reoxidation in sediments with higher organic content.     

The selectivity of a sequential extraction procedure for the determination of iron oxyhydroxides andiron sulfides in lake sediments

A popular sequential extraction procedure (Tessier et al. 1979) designed t o extract metals partitioned in various sediment phases, was evaluated for its selectivity. Amorphous FeOOH, FeS, and FeS₂ were added separately to natural lake sediments and sequentially extracted. The selectivity of the sequential procedure for the added solid phases was evaluated by determining the difference in the mass of Fe extracted from treated and control sediments. In the experiments where sulfide minerals were added, total S was measured in the residual solids in order to confirm selectivity of the method. Concentrations of total carbon remaining in the solid phase after each extraction step were also measured to determine the selectivity of the sequential procedure for carbon. The procedure was moderately selective for Fe added as FeOOH; a mean of 77 ± 12% (p < 0.05) of the Fe added was extracted in the step designed to reduce Fe-Mn oxyhydroxides. In experiments where FeS was added, a mean of 69 ± 11% (p < 0.05) of the Fe added as FeS was extracted in the fraction designed to oxidize sulfides and organic matter. Approximately 25% of the Fe added as FeS may have been extracted prematurely. Although less precise, total S analyses confirmed that much of the FeS was extracted in the oxidation step, yielding 104 ± 87% (p < 0.05) of the S added as FeS. The procedure was highly selective for FeS₂; 92 ± 14% (p < 0.05) of the Fe added as pyrite was extracted in the sulfide extraction step. Extraction of 80 ± 54% (p < 0.05) of S added as pyrite confirmed that FeS₂ were selectively extracted in the sulfide extraction step. Carbon in the sediments was also selectively extracted in the oxidation step (77 ± 2.4% of total C; p < 0.05). The applications and limitations of sequential extraction procedures as limnological research tools are discussed in light of our results. Request for offprints     

Biogeochemical cycling of sulfur and iron in sediments of a south-east Asian mangrove,Phuket Island,Thailand

Benthic sulfate reduction and sediment pools of sulfur and iron were examined during January 1992 at 3 stations in the Ao Nam Bor mangrove, Phuket, Thailand. Patterns of sulfate reduction rates (0–53 cm) reflected differences in physical and biological conditions at the 3 stations, and highest rates were found at the vegetated site within the mangrove (Rhizophora apiculata) forest. Due to extended oxidation of mangrove sediments, a large portion of the added³⁵S-label was recovered in the chromium reducible pools (FeS₂ and S⁰) (41–91% of the reduced sulfur). Pyrite was the most important inorganic sulfur component, attaining pool sizes 50–100 times higher than acid volatile pools (FeS). HCl-extractable (0.5 M HCl) iron pools, including Fe(II)_HCl and Fe(III)_HCl, were generally low and Fe(III)_HCl was only present in the upper surface layers (0–5 cm). Maximum concentrations of dissolved Fe²⁺ (35–285 M) occurred just about the depth where dissolved H₂S accumulated. Furthermore Fe²⁺ and H₂S coexisted only where concentrations of both were low. There was an accumulation of organic sulfur in the deep sediment at 2 stations in the inner part of the mangrove. The reoxidation of reduced sulfides was rapid, and storage of sulfur was minor in the upper sediment layers, where factors like bioturbation, the presence of roots, or tidal mixing enhance oxidation processes.Author of correspondence.     

Discrimination among iron sulfide species formed in microbial cultures

A quantitative method for the study of iron sulfides precipitated in liquid cultures of bacteria is described. This method can be used to quantify and discriminate among amorphous iron sulfide (FeS(amorph)), iron monosulfide minerals such as mackinawite or greigite (FeS(min)), and iron disulfide minerals such as pyrite or marcasite (FeS(2min)) formed in liquid cultures. Degradation of iron sulfides is performed using a modified Cr(2+) reduction method with reflux distillation. The basic steps of the method are: first, separation of FeS(amorph); second, elimination of interfering species of S such as colloidal sulfur (S(c) degrees ), thiosulphate (S(2)O(3)(2-)) and polysulfides (S(x)(2-)); third, separation of FeS(min); and fourth, separation of FeS(2min). The final product is H(2)S which is determined after trapping. The efficiency of recovery is 96-99% for FeS(amorph), 76-88% for FeS(min), and >97% for FeS(2min). This method has a high reproducibility if the experimental conditions are rigorously applied and only glass conduits are used. A well ventilated fume hood must be used because of the toxicity and volatility of several reagents and products. The advantage relative to previously described methods are better resolution for iron sulfide species and use of the same bottles for both incubation of cultures and acid degradation. The method can also be used for Fe/S stoichiometry with sub-sampling and Fe analysis.     

Sulfate reduction and sediment metabolism in Tomales Bay,California

Sulfate reduction rates (SRR) in subtidal sediments of Tomales Bay, California, were variable by sediment type, season and depth. Higher rates were measured in near-surface muds during summer (up to 45 nmol cm^-3 h^-1), with lower rates in sandy sediments, in winter and deeper in the sediment. Calculations of annual, average SRR throughout the upper 20 cm of muddy subtidal sediments (about 30 mmol S m^-2 d^-1) were much larger than previously reported net estimates of SRR derived from both benthic alkalinity flux measurements and bay wide, budget stoichiometry (3.5 and 2.6 mmol m^-2 d^-1, respectively), indicating that most reduced sulfur in these upper, well-mixed sediments is re-oxidized. A portion of the net alkalinity flux across the sediment surface may be derived from sulfate reduction in deeper sediments, estimated from sulfate depletion profiles at 1.5 mmol m^-2 d^-1. A small net flux of CO₂ measured in benthic chambers despite a large SRR suggests that sediment sinks for CO₂ must also exist (e.g., benthic microalgae).     

Inorganic sulfur turnover in oligohaline estuarine sediments

Inorganic sulfur turnover was examined in oligohaline (salinity < 2 g kg^-1) Chesapeake Bay sediments during the summer. Cores incubated for < 3 hr exhibited higher sulfate reduction (SR) rates (13–58 mmol m^-2 d^-1) than those incubated for 3–8 hr (3–8 mmol m^-2 d^-1). SR rates (determined with³⁵SO ₄ ^2- ) increased with depth over the top few cm to a maximum at 5 cm, just beneath the boundary between brown and black sediment. SR rates decreased below 5 cm, probably due to sulfate limitation (sulfate < 25 μM). Kinetic experiments yielded an apparent half-saturating sulfate concentration (K_s) of 34 μM, ≈ 20-fold lower than that determined for sediments from the mesohaline region of the estuary. Sulfate loss from water overlying intact cores, predicted on the basis of measured SR rates, was not observed over a 28-hr incubation period. Reduction of³⁵SO ₄ ^2- during diffusion experiments with intact core segments from 0–4 and 5–9 cm horizons was less than predicted by non-steady state diagenetic models based on³⁵SO ₄ ^2- reduction in whole core injection experiments. The results indicate that net sulfate flux into sediments was an order of magnitude lower than the gross sulfur turnover rate. Solid phase reduced inorganic sulfur concentrations were only 2–3 times less than those in sediments from the mesohaline region of the Bay, despite the fact that oligohaline bottom water sulfate concentrations were 10-fold lower. Our results demonstrate the potential for rapid SR in low salinity estuarine sediments, which are inhabited by sulfate-reducing bacteria with a high affinity for sulfate, and in which sulfide oxidation processes replenish the pore water sulfate pool on a time scale of hours.     

Benzene Oxidation Coupled to Sulfate Reduction

Highly reduced sediments from San Diego Bay, Calif., that were incubated under strictly anaerobic conditions metabolized benzene within 55 days when they were exposed initially to 1 (mu)M benzene. The rate of benzene metabolism increased as benzene was added back to the benzene-adapted sediments. When a [(sup14)C]benzene tracer was included with the benzene added to benzene-adapted sediments, 92% of the added radioactivity was recovered as (sup14)CO(inf2). Molybdate, an inhibitor of sulfate reduction, inhibited benzene uptake and production of (sup14)CO(inf2) from [(sup14)C]benzene. Benzene metabolism stopped when the sediments became sulfate depleted, and benzene uptake resumed when sulfate was added again. The stoichiometry of benzene uptake and sulfate reduction was consistent with the hypothesis that sulfate was the principal electron acceptor for benzene oxidation. Isotope trapping experiments performed with [(sup14)C]benzene revealed that there was no production of such potential extracellular intermediates of benzene oxidation as phenol, benzoate, p-hydroxybenzoate, cyclohexane, catechol, and acetate. The results demonstrate that benzene can be oxidized in the absence of O(inf2), with sulfate serving as the electron acceptor, and suggest that some sulfate reducers are capable of completely oxidizing benzene to carbon dioxide without the production of extracellular intermediates. Although anaerobic benzene oxidation coupled to chelated Fe(III) has been documented previously, the study reported here provides the first example of a natural sediment compound that can serve as an electron acceptor for anaerobic benzene oxidation.     

An evaluation of the importance of sulfate reduction and temperature to P fluxes from aerobic-surfaced, lacustrine sediments

We examined the influence of temperature and sulfate reduction rates onP-release from aerobic-surfaced, littoral sediments in a coolingreservoir. Annually, significant differences in P release from sediments at twosites (thermal effluent and non-effluent) were related to differenttemperature regimes, with higher rates of P release and decomposition at highertemperatures. Site-specific differences in solute fluxes were mostpronounced in late summer, when water temperatures reached40°Cat the effluent site and solute fluxes increased dramatically. The thermaleffluent site retained 65% of its annual P load, while thenon-effluent site retained 92%. Relative P release(P-release normalized to inorganic carbon fluxes; RPR) data indicatedthat lake sediments retained P selectively (relative to C) throughout the year,except at the effluent site during late summer when stored P was released inexcess of supply rates.Sulfate reduction rates were often typical of those measured in otherfreshwater lakes, but unusually high rates were measured at thethermal-effluent site especially in early fall and suggested higher DICfluxes than we measured. These high rates suggest that sulfate reduction rateswere overestimated and/or that most sulfide was recycled within the sediments.In any case, the highest sulfate reduction rates did not coincide with thehighest P release rates. Furthermore, the total reduced inorganic sulfurcontentof surficial sediments did not significantly correlate to RPR, althoughconcentrations varied widely throughout the year. Temperature was the onlyvariable examined that significantly correlated to RPR (R² =0.53, P-value = 0.017). Coupling between temperature and sedimentP release was likely mediated through temperature effects on bioturbation andmicrobial metabolic rates.     

Comparative Aspects of Sulfur Mineralization in Sediments of a Eutrophic Lake Basin

The net mineralization of organic sulfur compounds in surface sediments of Wintergreen Lake was estimated from a mass-balance budget of sulfur inputs and sediment sulfur concentrations. The net mineralization of organic sulfur inputs is <50% complete, which is consistent with the dominance of organic sulfur (>80% of total sulfur) in sediment. Although sediment sulfur is predominantly organic, sulfate reduction is the most significant process in terms of the quantities of sulfur transformed in surface sediments. Rates of sulfate reduction in these sediments average 7 mmol/m² per day. On an annual basis, this rate is 19-fold greater than net rates of organic sulfur mineralization and 65-fold greater than sulfate ester hydrolysis.     

Sulfur cycling and seagrass (Posidonia oceanica) status in carbonate sediments

Sulfur cycling was investigated in carbonate-rich and iron-poor sediments vegetated with Posidonia oceanica in oligotrophic Mediterranean around Mallorca Island, Spain, to quantify sulfate reduction and pools of sulfide in seagrass sediments. The oxygen penetration depth was low (< 4.5 mm) and sulfate reduction rates were relatively high (0.7–12 mmol m^–2d^–1). The total pools of reduced sulfides were remarkably low (< 5 mol S m^–2) indicating a fast turnover of reduced sulfides in these iron-poor sediments. The sulfate reduction rates were generally higher in vegetated compared to bare sediments possible due to enhanced sedimentation of sestonic material inside the seagrass meadows. The sulfate reduction rates were positively correlated with the seasonal variation in water temperature and negatively correlated with the shoot density indicating that the microbial activity was controlled by temperature and release of oxygen from the roots. The pools of reduced sulfides were low in these iron-poor sediments leading to high oxygen consumption for reoxidation. The sediments were highly anoxic as shown by relatively low oxygen penetration depths (< 4.5 mm) in these low organic sediments. The net shoot recruitment rate was negative in sediments enriched with organic matter, suggesting that organic matter enrichment may be an important factor for seagrass status in these iron-depleted carbonate sediments.     

Ecophysiological Evidence that Achromatium oxaliferum Is Responsible for the Oxidation of Reduced Sulfur Species to Sulfate in a Freshwater Sediment

Achromatium oxaliferum is a large, morphologically conspicuous, sediment-dwelling bacterium. The organism has yet to be cultured in the laboratory, and very little is known about its physiology. The presence of intracellular inclusions of calcite and sulfur have given rise to speculation that the bacterium is involved in the carbon and sulfur cycles in the sediments where it is found. Depth profiles of oxygen concentration and A. oxaliferum cell numbers in a freshwater sediment revealed that the A. oxaliferum population spanned the oxic-anoxic boundary in the top 3 to 4 cm of sediments. Some of the A. oxaliferum cells resided at depths where no oxygen was detectable, suggesting that these cells may be capable of anaerobic metabolism. The distributions of solid-phase and dissolved inorganic sulfur species in the sediment revealed that A. oxaliferum was most abundant where sulfur cycling was most intense. The sediment was characterized by low concentrations of free sulfide. However, a comparison of sulfate reduction rates in sediment cores incubated with either oxic or anoxic overlying water indicated that the oxidative and reductive components of the sulfur cycle were tightly coupled in the A. oxaliferum-bearing sediment. A positive correlation between pore water sulfate concentration and A. oxaliferum numbers was observed in field data collected over an 18-month period, suggesting a possible link between A. oxaliferum numbers and the oxidation of reduced sulfur species to sulfate. The field data were supported by laboratory incubation experiments in which sodium molybdate-treated sediment cores were augmented with highly purified suspensions of A. oxaliferum cells. Under oxic conditions, rates of sulfate production in the presence of sodium molybdate were found to correlate strongly with the number of cells added to sediment cores, providing further evidence for a role for A. oxaliferum in the oxidation of reduced sulfur.     

Isolation and partial characterization of forest floor and soil organic sulfur

The formation of organic sulfur from inorganic sulfate was investigated in hardwood forest floor and mineral horizons. All samples converted sulfate-sulfur into a non-salt extractable form which was recoverable only under conditions which release organic matter. This conversion was inhibited by azide, and depending upon the horizon, by erythromycin, candicidin, chloramphenicol and tetracycline. The form of sulfur generated in the 02 forest floor layer and in Al-horizon soil was characterized after isolation by pyrophosphate extraction at pH 8. The organosulfur extracts exhibited an average C:N:S ratio of 103:6:1. The ester sulfate content of the 02 extract was 61% by hydriodic acid (HI) reduction and 62% by hydrolysis in 3N HCl at 121 °C. However, compared to hydrolysis, reduction yielded lower estimates of ester sulfate for two of the three soil extracts analyzed. In view of the electrophoretic heterogeneity of all extracts, it is suggested that some may contain stable ester linkages that hydrolyze only after prolonged treatment and that the standard procedure for HI-reduction may provide conditions of temperature and contact time with the acid which are insufficient for the release of sulfate from these esters.Author to whom reprint requests should be addressed