Iron monosulfide formation and oxidation in drain-bottom sediments of an acid sulfate soil environment

Iron monosulfide formation and oxidation processes were studied in the extensively drained acid sulfate soil environment of the Tweed River floodplain in eastern Australia. Porewater profiles of pH, Eh, SO₄²⁻, Fe²⁺, Fe³⁺, Cl⁻, HCO₃⁻, and metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) were obtained using in situ dialysis membrane samplers (`peepers'). Concentrations of acid volatile S (AVS), pyrite, total S, reactive Fe, total and organic C, simultaneously extracted metals (SEMs) and total elemental composition by X-ray fluorescence, were determined on sediment samples. The oxidation of pyrite in the surrounding landscape provides a source of acidity, Fe, Al, SO₄ and metals, which are exported into the drainage system where they accumulate in the sediments and porewaters. Negative porewater concentration gradients of SO₄²⁻ and Fe²⁺, and large AVS concentrations in the sediments, indicate Fe monosulfides form rapidly under reducing conditions and consume acidity and metals. Oxidation of the sediments during previous drought episodes has resulted in the conversion of monosulfides and pyrite to oxidised Fe minerals and the release of acidity, SO₄²⁻, Fe³⁺, and metals to the surface waters. These formation and oxidation cycles show that Fe monosulfides play an important role in controlling water quality in the drainage system.     

The variability of δ34S and sulfur speciation in sediments of the Sulejów dam reservoir (Central Poland)

The study was carried out on the Sulejów dam reservoir (Central Poland). Water and sediment samples were collected between February and October 2006. Sulfur compounds in the sediment were chemically extracted and subjected to isotopic analysis.Large variability of SO₄²⁻ concentration in the water column (from 10.3 to 36.2 mg/dm³) and the isotopic composition of sulfur (δ³⁴S from 2.1 to 5.4‰) was observed. The main identified sources of SO₄²⁻ were watercourses, surface runoff, and phosphorus fertilizers.Both oxidized sulfur species (SO₄²⁻) and its reduced forms were found in sediments. Particular sulfur forms were characterized by large variations in both, concentrations and the isotopic composition of sulfur. SO₄²⁻ in the sediment and in the water column had different genesis. Bacterial oxidation of organic sulfur and its binding in SO₄²⁻ were observed in the sediment. Under reducing conditions, oxidized and organic sulfur is converted to H₂S which reacted with Fe or other metallic ions leading to metal sulfide precipitation. Monosulfides were shown to have a very low concentration, ranging up to 0.07 mg/g of sediment. The transformation of elemental sulfur from sulfides through their chemical oxidation occurred in the sediment.     

Elemental sulfur in drain sediments associated with acid sulfate soils

This paper reports the abundance of elemental S in drain sediments associated with acid sulfate soils. The sediments exhibited near-neutral pH (5.97–7.27), high concentrations of pore-water Fe²⁺ (1.37–15.9 mM) and abundant oxalate-extractable Fe (up to 4300 μmol g⁻¹). Maximum acid-volatile sulfide (AVS) concentrations in each sediment profile were high (118–1019 μmol g⁻¹), with AVS often exceeding pyrite-S. Elemental S occurred at concentrations of 13–396 μmol g⁻¹, with the higher concentrations exceeding previous concentrations reported for other sedimentary systems. Up to 62% of reduced inorganic S near the sediment/water interface was present as elemental S, due to reaction between AVS and oxidants such as O₂ and Fe(III). Significant correlation (r = 0.74; P < 0.05) between elemental S and oxalate-extractable Fe(III) is indicative of elemental S formation by in situ oxidation of AVS. The results indicate that AVS oxidation in near-surface sediments is dynamic in acidified coastal floodplain drains, causing elemental S to be a quantitatively important intermediate S fraction. Transformations of elemental S may therefore strongly influence water quality in ASS landscapes.     

Formation of pyrite in freshwater sediments: Implications for C/S ratios

The vertical distribution of pyrite, acid volatile sulphide (AVS), carbon, and total S (St) were determined directly in the sediments of three lakes of different trophic status. The results showed that freshwater pyrite formation reflects the redox status of the sediment or overlying waters. It appears to form chiefly in reducing sediments which are subject to oxidizing influences, by either a low turnover of organic carbon or periodic incursions of oxygen. Although there are high concentrations of AVS in the near-surface sediments of productive lakes, very little is diagenetically converted to pyrite.The feasibility of using sulphur ratios to diagnose whether rocks were formed in marine or freshwater environments is assessed. New values for FeS₂/FeS of 0.5-5 show that this ratio does not provide a reliable test. Values of C/Sp, where Sp represents pyrite sulphur, lie within the range of 160–700 and are much higher than previously measured ratios of C/S_t of 1–50. These new determinations show that, if pyrite sulphur is unequivocally measured, C/S ratios may be a more sensitive indicator of salinity than had been previously thought.     

Sedimentary iron geochemistry in acidic waterways associated with coastal lowland acid sulfate soils

We examined the solubility, mineralogy and geochemical transformations of sedimentary Fe in waterways associated with coastal lowland acid sulfate soils (CLASS). The waterways contained acidic (pH 3.26-3.54), Fe^III-rich (27-138 μM) surface water with low molar Cl:SO₄ ratios (0.086-5.73). The surficial benthic sediments had high concentrations of oxalate-extractable Fe(III) due to schwertmannite precipitation (kinetically favoured by 28-30% of aqueous surface water Fe being present as the Fe^III species). Subsurface sediments contained abundant pore-water HCO₃ (6-20 mM) and were reducing (Eh < −100 mV) with pH 6.0-6.5. The development of reducing conditions caused reductive dissolution of buried schwertmannite and goethite (formed via in situ transformation of schwertmannite). As a consequence, pore-water Fe^II concentrations were high (>2 mM) and were constrained by precipitation-dissolution of siderite. The near-neutral, reducing conditions also promoted SO₄-reduction and the formation of acid-volatile sulfide (AVS). The results show, for the first time for CLASS-associated waterways, that sedimentary AVS consisted mainly of disordered mackinawite. In the presence of abundant pore-water Fe^II, precipitation-dissolution of disordered mackinawite maintained very low (i.e. <0.1 μM) S^−II concentrations. Such low concentrations of S^−II caused slow rates for conversion of disordered mackinawite to pyrite, thereby resulting in relatively low concentrations of pyrite (<300 μmol g⁻¹ as Fe) compared to disordered mackinawite (up to 590 μmol g⁻¹ as Fe). This study shows that interactions between schwertmannite, goethite, siderite, disordered mackinawite and pyrite control the geochemical behaviour of sedimentary Fe in CLASS-associated waterways.     

The onset of anthropogenic activity recorded in lake sediments in the vicinity of the Horne smelter in Quebec,Canada: Sulfur isotope evidence

Contents and δ³⁴S values of several S compounds, enumerations of S-reducing bacteria (SRB) and Fe-reducing bacteria (IRB), and Fe, Pb and In concentrations were determined for ²¹⁰Pb-dated sediment cores from two lakes in Quebec, Canada. Both lakes are located approximately 70 km downwind of the Horne smelter and refinery in Rouyn-Noranda. Increases in Fe, Pb and In concentrations and a decrease in the δ³⁴S values of total S in both lake sediment cores coincide with the start-up of the smelter in 1927. The shift towards more negative δ³⁴S values was primarily caused by an increase in the extent of S isotope fractionation during bacterial (dissimilatory) SO₄ reduction due to SO₄ loading of the lakes after smelting began. Consequently, an enhanced accumulation of ³²S-enriched reduced inorganic S compounds is evident in the sediments. δ³⁴S values of organic S in the sediments decreased only slightly due to the smelter emissions between 1930 and 1980. Hence, due to the sulfide depositing mechanisms, S isotope ratios constitute a useful tracer recording the onset of S pollution in sediments of the two previously SO₄-limited lakes investigated. In contrast, total S concentrations alone are not reliable indicators for anthropogenic S loading in lake sediment records.     

Behavior of rare earth elements in acid coal mine drainage in Shanxi Province, China

Rare earth element (REE) concentrations were determined in acid mine drainage (AMD), bedrock, pyrite, and coal samples from the Sitai coal mine and the Malan coal mine in Shanxi province, China. The AMD displayed high REE concentrations with typical convex shale-normalized patterns. The REE concentrations in the bedrock samples are one order of magnitude higher than those found in pyrite and coal samples. The high REE concentrations in AMD most likely come from the acidic solution leached out REE in bedrock. Results from laboratory and field experiments show that pH is the most important factor controlling the fractionation of REE; but Fe, Al, and Mn colloids and secondary minerals also affects their fractionation. As the pH increased from 4 to 6, the concentrations of total dissolved REE decreased from 520 to 0.875???g?L^?1. Fe and Al in AMD has less influence on the fractionation of dissolved REE than low concentrations of Mn. HREE were preferentially removed by secondary minerals and colloids, followed by MREE. Rare earth element??s speciation modeling indicates that sulfate complexes (LnSO₄ ⁺ and Ln(SO₄) ₂ ^? , 79?C91%) and free-metal species (Ln³⁺, 8.8?C21%) are the dominant REE species in the AMD, but the REE-sulfate complexation could not explain the MREE-enriched patterns.     

Temporal dynamics of AVS and SEM in sediment of shallow freshwater floodplain lakes

Acid volatile sulfide (AVS) is an operationally defined sulfide fraction, which is considered important for trace metal fate in reduced sediments. Understanding AVS formation rates is important for the management of metal polluted sediment. However, little is known about the fate and dynamics of AVS in spatially and seasonally variable freshwater environments. The authors monitored in situ AVS formation and degradation and simultaneously extracted metals (SEM) in two floodplain lakes and compared this to AVS formation rates in laboratory experiments with the same sediment. In the laboratory experiments, the formation rates of AVS were studied at 20 °C for initially oxidized sediments that were: (a) untreated; (b) enriched with extra ${\mathrm{SO}}_4^{2-}$; and (c) treated with sodium-azide (biocide). In the field, AVS concentrations were highly variable and were significantly correlated to surface water temperature and O₂ concentrations as well as to sediment composition. Between February and August, AVS formation was approximately linear at a rate of 0.07 μmol g⁻¹ d⁻¹. Degradation rates differed drastically between the lakes due to different degradation mechanisms. In one lake AVS removal was caused by reworking and oxygenation of the sediments by bream (Abrami brama), at a rate of 0.25 μmol g⁻¹ d⁻¹. In the other lake AVS removal was caused by desiccation, at a rate of ±2.6 μmol g⁻¹ d⁻¹. This illustrates the large differences that can be found between similar lakes, and the importance of biological processes. In the laboratory, concentrations of AVS with and without ${\mathrm{SO}}_4^{2-}$ addition were similar during the first weeks, and increased at a rate of 0.15 μmol g⁻¹ d⁻¹. However, ${\mathrm{SO}}_4^{2-}$ addition increased the AVS concentration at the end of the experiment, whereas sodium-azide eliminated AVS formation, as expected. This suggests that AVS formation was ${\mathrm{SO}}_4^{2-}$-limited in the laboratory as well as in these shallow freshwater lakes.     

Sulfur speciation with high performance liquid chromatography as a tool for El Chichón volcano,crater lake monitoring

The monitoring of sulfur species in crater lakes has proven to be useful for forecasting episodes of volcanic unrest in certain active volcanoes, including Poás, Costa Rica; Kusatsu-Shirane, Japan; and Mt. Ruapehu, New Zealand. In this study, we have improved the current geochemical monitoring of El Chichón volcano through the setting of optimal high-performance liquid chromatography conditions (HPLC) for the analysis of S²⁻, SO₃²⁻, S₂O₃²⁻, S₄O₆²⁻ and SO₄²⁻ using a common chromatographic system. The procedure was applied to the analysis of lake samples taken in March, July and October of 2014 and April of 2015. The results were promising, since nearly all species were detected (with the exception of S₂O₃²⁻) in measurable amounts, including S²⁻ (<0.85–5.05 mg/L), SO₃²⁻ (<2.77–26.1 mg/L), S₄O₆²⁻ (108.27–303.82 mg/L) and SO₄²⁻ (489.58–676.26 mg/L). The spatial distribution of these species along the lakeshore showed zones of increased concentrations to the east and southeast of the lake, which provides information on the distribution of faults or cracks that feed hydrothermal fluids to the lake. This method thus provides additional information linked to the volcanic and hydrothermal activity of the volcano.     

Effect of acid mine drainage on a karst basin: a case study on the high-As coal mining area in Guizhou province,China

Acid mine drainage (AMD) is a common pollution in mining areas due to the oxidation of pyrite and associated sulfide minerals at mines, tailings and mine dumps. Elevated metals (Fe, Mn, Al) and metalloids (As, Hg) in AMD would deteriorate the local aquatic environment and influence the water supply. A carbonate basin with deposits of high-arsenic coal in Xingren County, southwestern China, was chosen to study the behavior of As and other chemical constituents along a river receiving AMD. Heavy metals (Fe, Mn) and major ions such as (Ca²⁺, Mg²⁺, Cl⁻, SO₄ ²⁻) in surface water, and As in sediment and surface water were analyzed. It was found that high concentrations of SO₄ ²⁻ (1,324–7,560 mg/L) and Fe (369–1,472 mg/L) in surface water were mainly controlled by the interactions between water and rocks such as the oxidation of pyrite in the local coal seams, precipitation and adsorption of iron minerals. Although ubiquitous carbonate minerals in the bedrock and the riverbeds, low pH (<3) water was maintained until 2 km downstream from the AMD source due to the Fe(hydro)oxide minerals coating on the surface of carbonate minerals to restrain the neutralization of acidic water. Moreover, the formation of Fe(hydro)oxide precipitations absorbed As was dominated the attenuation of As from water to sediment. Whereas, the dilution also played an important role in decrease of As in river water.     

Distribution and isotopic composition of sulfur in lake sediments of northern Ontario

Sediments from unpolluted and highly polluted lakes in northern Ontario have been fractionated into acid volatile sulfide, HCl-soluble sulfur, elemental sulfur, pyrite sulfur, ester sulfate and carbon-bonded sulfur and the isotopic composition of each fraction determined. In general, reduced inorganic S constitutes 25–50% of the total S in the polluted surficial sediments, but is <20% in the unpolluted samples, with pyrite formation being a minor process of S diagenesis in lake sediment ecosystems. Organic S in the form of ester sulfate and carbon-bonded S predominates and both the C/S ratios and the isotopic data suggest that, in unpolluted lakes, plant detritus can be a major contributor of organic-S to the sediments. The depth profiles observed suggest that the more labile ester sulfate is diagenetically converted to the carbon-bonded form. For the polluted sediments from the Sudbury basin, the isotopic data suggest that (a) the elemental S is derived from the oxidation of acid volatile sulfide in the aerobic surficial sediments, and (b) the isotopically light reduced S species are incorporated into the organic material. S diagenesis in lake sediments generally results in the release of ³⁴S to the overlying water. The suggestion is made that sulfate concentrations over 5 mg/1 accompanied by an enrichment of surficial sediments with isotopically different S may signal significant inputs of pollutant S into the lake and its basin.     

Interplay of S and As in Mekong Delta sediments during redox oscillations

The cumulative effects of periodic redox cycling on the mobility of As,Fe,and S from alluvial sediment to groundwater were investigated in bioreactor experiments.Two particular sediments from the alluvial floodplain of the Mekong Delta River were investigated:Matrix A(14 m deep)had a higher pyrite concentration than matrix B(7 m deep)sediments.Gypsum was present in matrix B but absent in matrix A.In the reactors,the sediment suspensions were supplemented with As(Ⅲ)and SO_4~(2-),and were subjected to three full-redox cycles entailing phases of nitrogen/CO_2,compressed air sparging,and cellobiose addition.Major differences in As concentration and speciation were observed upon redox cycling.Evidences support the fact that initial sediment composition is the main factor controlling arsenic release and its speciation during the redox cycles.Indeed,a high pyrite content associated with a low SO_4~(2-)content resulted in an increase in dissolved As concentrations,mainly in the form of As(Ⅲ),after anoxic half-cycles;whereas a decrease in As concentrations mainly in the form of As(Ⅴ),was instead observed after oxic half-cycles.In addition,oxic conditions were found to be responsible for pyrite and arsenian pyrite oxidation,increasing the As pool available for mobilization.The same processes seem to occur in sediment with the presence of gypsum,but,in this case,dissolved As were sequestered by biotic or abiotic redox reactions occurring in the Fe—S system,and by specific physico-chemical condition(e.g.pH).The contrasting results obtained for two sediments sampled from the same core show that many complexes and entangled factors are at work,and further refinement is needed to explain the spatial and temporal variability of As release to groundwater of the Mekong River Delta(Vietnam).     

A plug flow-through reactor for studying biogeochemical reactions in undisturbed aquatic sediments

A slow flow, plug-through reactor was developed for measuring equilibrium and kinetic parameters of biogeochemical reactions on intact sections of sediment cores. The experimental approach was designed to preserve the structural, geochemical and microbiological integrity of the sediment sections and, hence, retrieve reaction parameters that apply to in-situ conditions.Inert tracer breakthrough experiments were performed on a variety of unconsolidated surface sediments from lacustrine, estuarine and marine depositional environments. The sediments studied cover wide ranges of composition, porosity (46–83%) and mean grain size (10⁻⁴−10⁻² cm). Longitudinal dispersion coefficients were determined from the breakthrough curves of Br⁻. The curves were also used to check for early breakthrough or trailing, that is, features indicative of non-ideal flow conditions. Sediment plugs that exhibited these features were eliminated from further experiments.Dimensionless equilibrium adsorption coefficients (K) of NH₄⁺, were calculated from measured retardation times between the breakthrough of NH₄⁺ and Br⁻. The values of K at 5°C vary between 0.3 and 2.3, with the highest value obtained in a fine-grained marine sediment, the lowest in a coarse-grained lake sediment. The values for the marine and estuarine sediments agree with values reported in the literature. The dependencies of K on ionic strength (range 0.2-0.7m) and temperature (range 5–25°C) in an estuarine sediment confirm that the main sorption mechanism for NH₄⁺ is ion exchange.The reactor was used in recirculation mode to measure steady-state rates of dissimilatory SO₄²⁻ reduction in a salt-marsh sediment. Recirculation homogenizes solute concentrations within the reactor, hence facilitating the derivation of reaction rate expressions that depend on solution composition. The rate of microbial S0₄⁻ reduction was found to be nearly independent of the dissolved SO₄²⁻ concentration in the range of 2.2−1 mM. Fitting of the experimental rates to a Monod relationship resulted in a maximum estimate of the half-saturation concentration, K_s, of 240 μM. This value is comparable to those reported for a pure culture of SO₄²⁻-reducing bacteria, but is significantly smaller than the only other K_s value reported in the literature for SO₄²⁻ utilization in a natural marine sediment.     

Geochemistry and stable isotope composition of the Berkeley pit lake and surrounding mine waters,Butte, Montana

Samples of mine water from Butte, Montana were collected for paired geochemical and stable isotopic analysis. The samples included two sets of depth profiles from the acidic Berkeley pit lake, deep groundwater from several mine shafts in the adjacent flooded underground mine workings, and the acidic Horseshoe Bend Spring. Beginning in July-2000, the spring was a major surface water input into the Berkeley pit lake. Vertical trends in major ions and heavy metals in the pit lake show major changes across a chemocline at 10–20 m depth. The chemocline most likely represents the boundary between pre-2000 and post-2000 lake water, with lower salinity, modified Horseshoe Bend Spring water on top of higher salinity lake water below. Based on stable isotope results, the deep pit lake has lost approximately 12% of its initial water to evaporation, while the shallow lake is up to 25% evaporated. The stable isotopic composition of SO₄ in the pit lake is similar to that of Horseshoe Bend Spring, but differs markedly from SO₄ in the surrounding flooded mine shafts. The latter is heavier in both δ³⁴S and δ¹⁸O, which may be due to dissolution of hypogene SO₄ minerals (anhydrite, gypsum, barite) in the ore deposit. The isotopic and geochemical evidence suggests that much of the SO₄ and dissolved heavy metals in the deep Berkeley pit lake were generated in situ, either by leaching of soluble salts from the weathered pit walls as the lake waters rose, or by subaqueous oxidation of pyrite on the submerged mine walls by dissolved Fe(III). Laboratory experiments were performed to contrast the isotopic composition of SO₄ formed by aerobic leaching of weathered wallrock vs. SO₄ from anaerobic pyrite oxidation. The results suggest that both processes were likely important in the evolution of the Berkeley pit lake.     

Particulate sulfur species in the water column of the Cariaco Basin

The biogeochemistry of iron sulfide minerals in the water column of the Cariaco Basin was investigated in November 2007 (non-upwelling season) and May 2008 (upwelling season) as part of the on-going CARIACO (CArbon Retention In A Colored Ocean) time series project. The concentrations of particulate sulfur species, specifically acid volatile sulfur (AVS), greigite, pyrite, and particulate elemental sulfur, were determined at high resolution near the O₂/H₂S interface. In November 2007, AVS was low throughout the water column, with the highest concentration at the depth where sulfide was first detected (260 m) and with a second peak at 500 m. Greigite, pyrite, and particulate elemental sulfur showed distinct concentration maxima near the interface. In May 2008, AVS was not detected in the water column. Maxima for greigite, pyrite, and particulate elemental sulfur were again observed near the interface. We also studied the iron sulfide flux using sediment trap materials collected at the Cariaco station. Pyrite comprised 0.2-0.4% of the total particulate flux in the anoxic water column, with a flux of 0.5-1.6 mg S m⁻² d⁻¹.Consistent with the water column concentration profiles for iron sulfide minerals, the sulfur isotope composition of particulate sulfur found in deep anoxic traps was similar to that of dissolved sulfide near the O₂/H₂S interface. We conclude that pyrite is formed mainly within the redoxcline where sulfur cycling imparts a distinct isotopic signature compared to dissolved sulfide in the deep anoxic water. This conclusion is consistent with our previous study of sulfur species and chemoautotrophic production, which suggests that reaction of sulfide with reactive iron is an important pathway for sulfide oxidation and sulfur intermediate formation near the interface. Pyrite and elemental sulfur distributions favor a pathway of pyrite formation via the reaction of FeS with polysulfides or particulate elemental sulfur near the interface. A comparison of thermodynamic predictions with actual concentration profiles for iron sulfides leads us to argue that microbes may mediate this precipitation.     

Sulfide Inhibition of Nitrate Removal in Coastal Sediments

Microbial nitrate (NO₃⁻) removal via denitrification (DNF) at high sulfide (H₂S) concentrations was compared in sediment from a coastal freshwater pond in a developed area that receives salt-water influx during storm events, and a saline pond proximal to an undeveloped estuary. Sediments were incubated with added SO₄²⁻ (1,000 μg per gram dry weight basis (gdw)) to determine whether acid volatile sulfides (AVS) were formed. DNF in the sediments was measured with NO₃–N (300 μg gdw⁻¹) alone, and with NO₃–N and H₂S (1,000 μg S²⁻ gdw⁻¹). SO₄²⁻ addition to the freshwater sediments resulted in AVS formation (970 ± 307 μg S gdw⁻¹) similar to the wetland with no added SO₄²⁻ (986 ± 156 μg S gdw⁻¹). DNF rates measured with no added H₂S were greater in the freshwater than the wetland site (10.6 ± 0.6 vs. 6.4 ± 0.1 μg N₂O–N gdw⁻¹ h⁻¹, respectively). High H₂S concentrations retained NH₄–N in the undeveloped wetland and retained NO₃–N in the developed freshwater site, suggesting that potential salt-water influx may reduce the ability of the freshwater sediments to remove NO₃–N.     

Seasonal variations in sediment sulfur cycling in the Ballastplaat mudflat, Belgium

Sulfate reduction rate (SRR) and pools of reduced inorganic sulfur, acid volatile sulfide (AVS), chromium reducible sulfur (CRS), and elemental sulfur (S^o), were studied from June 1990 till March 1992 at two locations on the Ballastplaat mudflat in the Scheldt estuary. The sediment composition at station A was mainly sand with low organic content whereas sediments at station B were dominated by silt and clay with high organic content. SRR was positively related to temperature; more pronounced at station B (Ea=190 kJ mol⁻¹) than at station A (Ea=110 kJ mol⁻¹). The maximum SRR values observed equalled 14 μmol cm⁻³ d⁻¹ at station B and 1 μmol cm⁻³ d⁻¹ at station A. AVS was the dominant radiolabelled end product of the sulfate reduction reaction, except in surface sediments where pyrite and S^o were more dominant. However, CRS was the predominant reduced inorganic sulfur pool in the sediments. Both AVS and CRS pools showed temporal variations out of phase with SRR. SRR peaked in summer, while the concentrations of AVS and CRS were highest in fall. The accumulation of AVS and CRS started late summer after depletion of oxidants, which had accumulated during winter and spring. The estimated annual SRR and thus sulfide production in the upper 15 cm of station B was of the order of 100 mol m⁻² yr⁻¹, and at station A of the order of 12 mol m⁻² yr⁻¹. The sulfur mass balance shows that only a very small fraction, if any, of the produced sulfide is retained as reduced inorganic sulfur in the sediment.     

Sulphur,organic carbon and iron relationships in estuarine and freshwater sediments: effects of sedimentation rate

Concentrations of S, organic C and Fe were investigated in profiles of sediments from two estuarine systems in the SW of Western Australia. In marine-affected sediments, inorganic S dominates total S and concentrations of total S correlate with Fe and not with organic C. In freshwater sediments, organic S dominates total S and concentrations of total S correlate with organic C and not with Fe. Molar Fe/S ratios in the estuarine sediments decrease with increasing salinity and approach unity for marine conditions. Net accumulation rates of S in sediments were estimated with a numerical computer model, calibrated with published data on profiles of marine sediments for diffusion of SO²⁻₄, sedimentation rates and distributions of S. Measured depth-integrated reduction rates of SO²⁻₄ in the marine-affected estuarine sediments approach those obtained for Fe-limited marine conditions at similar rates of sedimentation. Measured concentrations of inorganic S in anoxic freshwater sediments fit a numerically calculated relationship between inorganic S and sedimentation rate.     

Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H₂S of Cu and Cd, relative to Zn; (2) stable isotope ratios of ³⁴S/³²S and ¹⁸O/¹⁶O in dissolved SO₄ that are 2–3 ‰ heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures.     

Reaction time scales for sulphate reduction in sediments of acidic pit lakes and its relation to in-lake acidity neutralisation

Sulphate reduction is a key reaction to remove acidity from water bodies affected by acid mine drainage. In this study, ³⁵SSO₄²⁻ reduction rates determined in sediments from a variety of acidic lignite pit lakes have been compiled. The rates decreased with pH and are strongly dependent on carbon substrate. The rates were fitted to a Monod model adapted to the specific conditions of acidic pit lakes (APL) sediments: i) sulphate reduction rate is independent from sulphate concentration due to the high concentration typically observed in APL systems (10–30 mM), ii) the observed pH dependency of sulphate reduction was accounted for by an inhibition function F_inihibt which considers the occurrence of low cell numbers of sulphate reducing bacteria at pH values < 4.75. Simulated steady-state sulphate reduction rates are predicting measured rates at carbon substrate concentrations of <10 μM. Estimated steady-state reaction time scales range between 2.4 h at pH 7 and 41 h at pH 3 at a carbon half-saturation constant of K_C−S = 100 μM and are increasing with increasing K_C−S values. Time scales at low pH are too long to allow for significant generation of alkalinity during the time of residence of groundwater passing through the top and hence most reactive zone of APL sediments which has important implications for the remediation of acidic pit lakes.