The waste sulfuric acid lake of the TiO2-plant at Armyansk,Crimea, Ukraine. Part I. Self-Sealing as an environmental protection mechanism

The TiO₂-plant at Armyansk, in operation since 1969, discharges its waste sulfuric acid and other effluents into an ‘acid collector’ of 42 km² surface area. Under the semi-arid climatic conditions, such a surface represents the equilibrium between effluent production and evaporation. In the course of its operation, the pH of the lake has slowly decreased to a value of 0.85. At the bottom of the lake a layer of natrojarosite of between 10 and 50 cm has developed, which terminates in a thin crust of Fe oxides cemented by gypsum, separating the jarosite from the underlying clay. Below this Fe crust, that acts as a perfect seal, the pH of the pore-water jumps to a value around 6.2. Heavy elements from the effluent, notably As, V and Cr, are immobilized by isomorphic substitution in the Fe crust. It is suggested that similar self-healing seals can replace conventional isolation mechanisms in disposal sites.     

The impact of pyrite variability, dispersive transport and precipitation of secondary phases on the sulphate release due to pyrite weathering

The objective of this study was to investigate the impact of flow, transport and geochemical parameters in the unsaturated and saturated zones on the release of SO₄ from overburden lignite spoil piles into the adjacent lake. A vertical one-dimensional model was set up using the reactive transport simulator SULFIDOX in order to account for the unsaturated zone. The SULFIDOX model was calibrated for effective diffusion using measured O₂ in the gas phase and SO₄ concentrations in the liquid phase from the unsaturated zone of the heap. The results show high sensitivity to O₂ supply and initially present gypsum, but the inclusion of secondary mineral precipitation in equilibrium is of minor importance for the results. To account for the transport of released SO₄ from the saturated zone into the surface water, scenarios were performed by using SULFIDOX results as input concentration for a two-dimensional vertical model set up with PROCESSING MODFLOW and MT3D. These scenarios indicate a rising discharge of SO₄ into the adjacent lake due to continued pyrite weathering for 80 a. Results are highly sensitive to dispersivity, whereas the spatial variability of pyrite distribution did not show any influence on the results. The consideration of initially present gypsum shows a major effect on the modelled SO₄ release.     

Influence of water chemistry on the distribution of an acidophilic protozoan in an acid mine drainage system at the abandoned Green Valley coal mine,Indiana, USA

Euglena mutabilis, a benthic photosynthetic protozoan that intracellularly sequesters Fe, is variably abundant in the main effluent channel that contains acid mine drainage (AMD) discharging from the Green Valley coal mine site in western Indiana. Samples of effluent (pH 3.0–4.6) taken from the main channel and samples of contaminated stream water (pH 3.3 to 8.0) collected from an adjacent stream were analyzed to evaluate the influence of water chemistry on E. mutabilis distribution. E. mutabilis communities were restricted to areas containing unmixed effluent with the thickest (up to 3 mm) benthic communities residing in effluent containing high concentrations of total Fe (up to 12110 mg/l), SO₄ (up to 2940 mg/l), Al (up to 1846 mg/l), and Cl (up to 629 mg/l). Communities were also present, but much less abundant, in areas with effluent containing lower concentrations of these same constituents. In effluent where SO₄ was most highly concentrated, E. mutabilis was largely absent, suggesting that extremely high concentrations of SO₄ may have an adverse effect on this potentially beneficial Fe-mediating, acidophilic protozoan.     

Hydrochemical evolution and arsenic release in shallow aquifer in the Titas Upazila,Eastern Bangladesh

Groundwater arsenic (As) concentrations above 10 μg/L (World Health Organization; WHO standard) are frequently found in the Titas Upazila in Bangladesh. This paper evaluates the groundwater chemistry and the mechanisms of As release acting in an underground aquifer in the middle-northeast part of the Titas Upazila in Bangladesh. Previous measurements and analyses of 43 groundwater samples from the region of interest (ROI) are used. Investigation is based on major ions and important trace elements, including total As and Fe in groundwater samples from shallow (8–36 m below ground level: mbgl) and deep (85–295 mbgl) tube wells in the aforementioned ROI. Principal hydrochemical facies are Ca–HCO₃, with circumneutral pH. The different redox-sensitive constituents (e.g., As, Fe, Mn, NH₄, and SO₄) indicate overlapping redox zones, leading to differences regarding the redox equilibrium. Multivariate statistical analysis (factor analysis) was applied to reduce 20 chemical variables to four factors but still explain 81% of the total variance. The component loadings give hints as to the natural processes in the shallow aquifers, in which organic matter is a key reactant. The observed chemistry of As, Fe, and Mn can be explained by simultaneous equilibrium between Fe-oxide and SO₄ reduction and an equilibrium of rhodochrosite precipitation/dissolution. A correlation test indicates the likeliness of As release by the reductive dissolution of Fe-oxides driven by the degradation of sediments organic matter. Other mechanisms could play a role in As release, albeit to a lesser extent. Reactive transport modeling using PHREEQC reproduced the observed chemistry evolution using simultaneous equilibrium between Fe-oxide and SO₄ reduction and the equilibrium of rhodochrosite dissolution/precipitation alongside organic matter oxidation.     

Hydrochemical characterization of acute acid mine drainage at Iron Duke mine, Mazowe, Zimbabwe

 Acid mine drainage (AMD) with a minimum pH of 0.52 was recorded at Iron Duke mine near Mazowe, Zimbabwe during an investigation of the environmental geochemistry of mine waters in the Greenstone Belts of Zimbabwe. Hydrochemical data for waters emanating from the Iron Duke waste-rock pile indicate their super-saturation with respect to Fe and SO₄ ^2–. Extremely high dissolved concentrations of Al, Zn, Cu, Co, Ni, V, Cr, Cd and As also prevail. Substantial losses of metals from solution occur within 400 m of the AMD source through the precipitation of crystalline sulphates, principally melanterite. Further downstream, hydrous oxide precipitation forms the dominant mechanism of metal attenuation in waters characteristically under-saturated with respect to Fe sulphates. Speciation and saturation index data generated using the equilibrium model WATEQ4F, suggest that such codes have broad utility for generic prediction of the mineralogical contraints on metal mobility in acute AMD systems. Major discrepancies between modelled and empirical hydrochemistries are, however, evident for super-saturated waters in which the kinetics of Fe precipitation are slow, and in which total ionic strengths markedly exceed their theoretical maximum. Received: 28 August 1998 · Accepted: 7 December 1998     

The evolution of alkaline, saline ground- and surface waters in the southern Siberian steppes

Groundwaters, river and lake waters have been sampled from the semi-arid Siberian Republic of Khakassia. Despite the relatively sparse data set, from a diversity of hydrological environments, clear salinity-related trends emerge that indicate the main hydrochemical evolutionary processes active in the region. Furthermore, the major ion chemistry of the evolution of groundwater baseflow, via rivers, to terminal saline lake water, can be adequately and simply modelled (using PHREEQCI) by invoking: (i) degassing of CO₂ from groundwater as it emerges as baseflow in rivers (rise in pH); (ii) progressive evapoconcentration of waters (parallel accumulation of Cl⁻, Na⁺, SO₄²⁻, and increase in pH due to common ion effect); and (iii) precipitation of calcite (depletion of Ca from waters, reduced rate of accumulation of alkalinity). Dolomite precipitation is ineffective at constraining Mg accumulation, due to kinetic factors. Silica saturation appears to control dissolved Si in low salinity waters and groundwaters, while sepiolite saturation and precipitation depletes Si from the more saline surface waters. Gypsum and sodium sulphate saturation are only approached in the most saline environments. Halite remains unsaturated in all waters. Sulphate reduction processes are important in the lower part of lakes.     

Mineralogical, chemical, and crystallographic properties of supergene jarosite-group minerals from the Xitieshan Pb-Zn sulfide deposit, northern Tibetan Plateau, China

Supergene jarosite-group minerals are widespread in weathering profiles overlying Pb-Zn sulfide ores at Xitieshan, northern Tibetan Plateau, China. They consist predominantly of K-deficient natrojarosite, with lesser amounts of K-rich natrojarosite and plumbojarosite. Electron microprobe (EMP) analyses, scanning electron microcopy (SEM) investigation, and X-ray mapping reveal that the jarosite-group minerals are characterized by spectacular oscillatory zoning composed of alternating growth bands of K-deficient and K-bearing natrojarosite (K₂O >1 wt.%). Plumbojarosite, whenever present, occurs as an overgrowth in the outermost bands, and its composition can be best represented by K_0.29Na_0.19Pb_0.31Fe_2.66Al_0.22(SO₄)_1.65(PO₄)_0.31(AsO₄)_0.04(OH)_7.37. The substitution of monovalent for divalent cations at the A site of plumbojarosite is charge balanced by the substitution of five-valent for six-valent anions in XO₄ at the X site. Thermogravimetric analysis (TGA) of representative samples reveal mass losses of 11.46 wt.% at 446.6 °C and 21.42 wt.% at 683.4 °C due to dehydroxylation and desulfidation, respectively. TGA data also indicate that the natrojarosite structure collapses at 446.6 °C, resulting in the formation of NaFe(SO₄)₂ and minor hematite. The decomposition products of NaFe(SO₄)₂ are hematite and Na₂SO₄. Powder X-ray diffraction (XRD) analyses show that the jarosite-group minerals have mean unit-cell parameters of a?=?7.315 Å and c?=?016.598 Å. XRD and EMP data support the view that substitutions of Na for K in the A site and full Fe occupancy in the B site can considerably decrease the unit-cell parameter c, but only slightly increase a. The results from this study suggest that the observed oscillatory zoning of jarosite-group minerals at Xitieshan resulted mainly from substitutions of K for Na at the A site and P for S at the X site.     

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.     

Thermodynamics and organic matter: constraints on neutralization processes in sediments of highly acidic waters

The controls on the internal neutralization of low productivity, highly acidified waters by sulfide accumulation in sediments are yet poorly understood. It is demonstrated that the neutralization process is constrained by organic matter quality and thermodynamic effects which control the relative rates of SO₄ and Fe reduction, and the fate of the reduced Fe and S in the sediments. The investigated sediments were rich in dissolved Fe(II) (0.005–12 mmol l⁻¹) and SO₄ (1.3–22 mmol l⁻¹). The pH ranged from 3.0 to 6.8. Contents of reduced inorganic S (0.1–9.5%), molar C/N ratios of the organic matter (12–80) and metabolic turnover rates (1–110 μeq cm⁻³ a⁻¹) varied strongly. Substantial amounts of Fe sulfides were only found at a simultaneous partial thermodynamic and solubility equilibrium of the involved biogeochemical processes. Sulfide oxidation was apparently inhibited, and SO₄ and Fe reduction coexisted. In this type of sediment increases in C availability cause enhanced neutralization rates. In the absence of a partial equilibrium, the sediments were in a sulfide oxidizing and Fe reducing state, and did not accumulate Fe sulfides. The latter type of sediment will increase neutralization rates in response to decreasing deposition of reactive Fe oxides but not necessarily in response to increases in lake productivity by e.g. fertilization measures.     

Dilution and removal of dissolved metals from acid mine drainage along Imgok Creek,Korea

The dilution factors (D_i) and removal fractions (R_i) of pollutants from acid mine drainage (AMD) were quantitatively estimated using two different methods, the conservative component and mass balance method, along Imgok Creek in Korea. The conservative component method assumes that SO₄ is a perfectly conservative component and calculates D_i and R_i from the concentration ratios of SO₄. The mass balance method solves the simultaneous equations relating the concentrations of dissolved components to their precipitation stoichiometries to obtain D_i and R_i. The results from both methods are little different, indicating that SO₄ concentration is a good indicator of dilution for Imgok creek. The calculated D_i's of pollutants quickly decrease from the site of AMD input to the site a few km downstream, but then remain more or less constant over the reaches farther downstream. This is because D_i loses its sensitivity in the reaches where difference in SO₄ concentration between the main stream and combining tributaries significantly diminishes. The calculated R_i's show that approximately 90, 95, and 75% of the original Fe input were removed from the streamwater in October 1996, April 1997, and October 1997, respectively. Aluminum was almost completely removed in April 1997, but only 50% of the original Al was removed in October 1997. The removal of Fe was due to the precipitation of schwertmannite or ferrihydrite and Al due to amorphous Al₄(OH)₁₀SO₄. The maximum removal fraction of dissolved SO₄ was only 5%. The other metals from AMD were significantly removed from the stream water only in April 1997. These metals were removed not by precipitation but by adsorption on and/or coprecipitation with Fe/Al-compounds. The relatively abundant freshwater supply in April 1997 might raise stream pH higher than the adsorption edge and consequently, contribute to rapid metal attenuation by forcing not only more precipitation but also more adsorption of the dissolved metals.     

Geochemical modeling approach to predicting arsenic concentrations in a mine pit lake

Between 1968 and 1983, the North pit at the Getchell Mine, Humboldt County, NV, filled with water to form a lake. In 1983, water quality data were collected with the following results: As concentrations of 0.29 to 0.59 mg/L, pH of 7.1 to 7.9, SO₄ concentrations of 1490 to 1640 mg/L, and TDS of 2394 to 2500 mg/L. Using geochemical modeling techniques presented here, pit lake waters have been theoretically allowed to react for 8.5 a, the approximate time that the North pit had been completely full by 1983. Modeling results predict pH of 7.9 to 8.2, SO₄ concentrations of 1503 to 1644 mg/L, TDS of 2054 to 2366 mg/L, and As concentrations ranging from 0.57 in the hypolimnion to 96 mg/L in the epilimnion. In the epilimnion, model results do not match observed As concentrations, suggesting that mechanisms, such as precipitation of arsenate salts or adsorption to mineral surfaces, may control As levels in an actual pit lake system. Adsorption to Fe oxyhydroxide surfaces is questioned by the authors because of the low Fe content in the Getchell system, but adsorption to Al(OH)₃ (gibbsite) and clay mineral surfaces may be important in controlling natural As concentrations.     

Lake water geochemistry on the western Kola Peninsula,north-west Russia

Water samples were taken from 120 lakes spread over the western half of the Kola Peninsula, NW Russia. The samples were analysed for 37 elements, pH and electrical conductivity. Lake water chemistry appears in most cases to be dominated by a Ca/Na–HCO₃ signature, characteristic of natural carbonate/silicate weathering. Input of elements from marine derived salts and from the Ni industry (roasting plant at Zapoljarnij, smelter at Nikel and smelter/refinery at Monchegorsk) emissions are restricted to limited regions. Considering that 3 of the world's largest point source emitters of SO₂ are located within the area, the median lake water pH is surprisingly close to neutral (6.6, range 4.2–7.4). Indeed some of the apparently SO₄ contaminated lakes nearest to the smelters yield the highest pH values. Changes in climate and vegetation from north to south within the survey area probably have an influence on element concentrations and pH as observed in the lake waters. Proton displacement by sea salt cation input provides an explanation of low pH lakes in coastal areas.     

Modelling ion composition in seepage water from a column experiment with an open cut coal mine sediment

Secondary reactions occurring in pyrite-containing sediments from open cut coal mines are complex and not fully understood. In this study, the changes in seepage water composition in a column experiment with a sediment containing pyrite (5.6 g kg⁻¹) were evaluated using a chemical equilibrium model. A column experiment with artificial irrigation (730 mm water yr⁻¹) was carried out for 2 yr with a sediment from the open pit mine Garzweiler, Germany, at the Institute of Applied Geology. Tracer (LiCl) was added to the sediment. Seepage water composition at 52 cm depth was sampled weekly. Redox potential and the water potential were also recorded weekly. Sulphate and Fe(II) were the dominant ions in the seepage water with concentration maxima of 500 and 350 mmol l⁻¹ after 50 days (0.7 pore volumes (PV)). Minimum pH values were around 0.8 after 100 days (1.4 PV), but increased subsequently and reached 2.4 after 700 days (9.5 PV). Ion activity product calculations indicated the intermediate formation of gypsum (19th–480th day of the experiment). Solutions were undersaturated with respect to alunite, jarosite, jurbanite, schwertmannite, melanterite, gibbsite and goethite during the whole experiment. The model of coupled equilibria which included inorganic complexation, precipitation/dissolution of gypsum and multiple cation exchange was tested. Pyrite oxidation and pH-dependent silicate weathering were considered using simple input functions. Transport was modelled using a field capacity cascade submodel. Model results showed satisfactory agreement with measured values for pH and concentrations of SO₄, Fe, Mg, Ca and Al. Correlation coefficients lay between 0.7 and 0.9 and linear regression coefficients (modelled against measured) were 1.5 (Ca), 1.0 (Fe, SO₄), 0.8 (Mg), 0.7 (pH) and 0.6 (Al). The results showed that the protons produced during pyrite oxidation (94 mmol_c H⁺ kg⁻¹) were mainly released into seepage water (as HSO₄⁻ and H⁺). Cation exchange reactions buffered 20 mmol_c of H⁺ kg⁻¹ sediment, and Al released by silicate weathering accounted for 3.6 mmol_c H⁺ kg⁻¹. Modelling was useful to further understand the significance of different pH buffer reactions.     

Temporal variations in the chemistry of circum-neutral drainage from the 10-Level portal,Myra Mine,Vancouver Island,British Columbia

The Myra mine, now inactive, produced Zn and Cu concentrates from a Zn-rich, Kuroko-type, volcanogenic massive sulfide deposit located in the mountainous interior of Vancouver Island. The climate at the site is classified as “Marine West Coast”, with annual precipitation exceeding 2200 mm. Water from a losing stream on the mountainside above the mine follows preferential, fracture-controlled pathways to the upper workings before draining through the 10-Level portal. With a view toward mine decommissioning, portal discharge rate was monitored continuously over a 17-month period during which 46 water samples were collected. Effluent chemistry, dominated by Ca, HCO₃ and SO₄, shows moderate to high total base metal concentrations and near-neutral pH. Carbonatization, mainly of mafic rocks in the hangingwall, provides significant acid neutralizing potential. Metal concentrations vary seasonally, with smaller spikes associated with summer storm events, and a main peak associated with flushing of the workings during the first heavy autumn rains. Aqueous speciation modeling suggests that Fe and Al concentrations are controlled by the solubilities of hydrous ferric oxides and microcrystalline gibbsite, respectively. Concentrations of Zn, Cu and Cd appear controlled by sorption rather than by the solubilities of mineral phases. A comparison of precipitate concentrations observed in portal effluent with predictions from mass balance (inverse) modeling results suggests that less than 5% of the precipitated Fe and Al hydroxides are transported from the mine. However, amounts of sorbed Cu, Zn and Cd measured in the effluent are only slightly lower than modeled values. This suggests that the small fraction of (probably finer) Fe precipitates in portal effluent sorbs most of the Zn, Cu and Cd predicted by modeling. Based on mass balance calculations, metal loadings are explained by the oxidation of 3830 kg of pyrite, 600 kg of sphalerite and 190 kg of chalcopyrite, annually. Circum-neutral drainage conditions are maintained by the reaction of almost 19,800 kg of calcite, annually.     

Geochemical reactions and dynamics during titration of a contaminated groundwater with high uranium, aluminum, and calcium

This study investigated possible geochemical reactions during titration of a contaminated groundwater with a low pH but high concentrations of aluminum, calcium, magnesium, manganese, and trace contaminant metals/radionuclides such as uranium, technetium, nickel, and cobalt. Both Na-carbonate and hydroxide were used as titrants, and a geochemical equilibrium reaction path model was employed to predict aqueous species and mineral precipitation during titration. Although the model appeared to be adequate to describe the concentration profiles of some metal cations, solution pH, and mineral precipitates, it failed to describe the concentrations of U during titration and its precipitation. Most U (as uranyl, UO₂²⁺) as well as Tc (as pertechnetate, TcO₄⁻) were found to be sorbed and coprecipitated with amorphous Al and Fe oxyhydroxides at pH below ∼5.5, but slow desorption or dissolution of U and Tc occurred at higher pH values when Na₂CO₃ was used as the titrant. In general, the precipitation of major cationic species followed the order of Fe(OH)₃ and/or FeCo_0.1(OH)_3.2, Al₄(OH)₁₀SO₄, MnCO₃, CaCO₃, conversion of Al₄(OH)₁₀SO₄ to Al(OH)_3,am, Mn(OH)₂, Mg(OH)₂, MgCO₃, and Ca(OH)₂. The formation of mixed or double hydroxide phases of Ni and Co with Al and Fe oxyhydroxides was thought to be responsible for the removal of Ni and Co in solution. Results of this study indicate that, although the hydrolysis and precipitation of a single cation are known, complex reactions such as sorption/desorption, coprecipitation of mixed mineral phases, and their dissolution could occur simultaneously. These processes as well as the kinetic constraints must be considered in the design of the remediation strategies and modeling to better predict the activities of various metal species and solid precipitates during pre- and post-groundwater treatment practices.     

A mass balance approach to estimate the dilution and removal of the pollutants in stream water polluted by acid mine drainage

 A few simple mass balance equations were developed to simultaneously estimate how much the pollutants from acid mine drainage (AMD) in stream water are diluted and removed during their migration. The application of the equations requires knowledge of the variations in the concentrations of the dissolved pollutants and the stoichiometry of the precipitation reaction of the pollutants when none of the pollutant shows a conservative behavior along the stream path. The calculation should be restricted to the pollutants showing much higher concentrations in the polluted main stream water than in the combining or diluting water of the same target area. The mass balance equations were applied to estimate the dilution factor and precipitation fractions of pollutants in Imgok Creek such as Fe, SO₄ and Al from the AMD of Yeongdong mine. The results show that the estimation, especially for SO₄ and Al, significantly depends on the kinds of the precipitates. When FeOHSO₄ and AlOHSO₄ are assumed to precipitate, the maximum removal fractions of SO₄ and Al by precipitation are respectively 34% and 46% of the original input, which is much higher than the values estimated when SO₄ is considered to be perfectly conservative. It indicates that the stoichiometry of precipitation reaction is very important in the interpretation of the pollutant dilution and migration and assessment of environmental impacts of AMD. The applicability of the mass balance equations may still need to be verified. However, examining the calculated dilution factor and precipitation fractions with the equations can provide invaluable information on not only the behavior but also unexpected input of the pollutants in the stream water polluted by AMD and other point sources. Received: 12 November 1997 · Accepted: 30 March 1998     

Balance of S in a constructed wetland built to treat acid mine drainage, Idaho Springs, Colorado, U.S.A.

The wetland constructed at the Big Five Tunnel in Idaho Springs, Colorado was designed to remove, passively, heavy metals from acid mine drainage. In optimizing the design of such a wetland, an improved understanding of the chemical processes operating there was required, particularly SO₄²⁻ reduction and sulfide precipitation. For this purpose, field and laboratory data were collected to study the balance of S in the system. Field data collected included water analyses of the mine drainage and wetland effluents and measurements of H₂S gas emissions from the wetland. The concentration of sulfide in the wetland effluent ranged from 10⁻⁴ to 10⁻³ mol/l. The average rates of H₂S emission from the surface of the substrate were 150 nmol/cm²/d in the summer and 0.17 and 0.35 nmol/cm²/d in the winter. This maximum estimated loss of sulfide was not significant in reducing the amount of sulfide available for precipitation with metals. Sequential extraction experiments for S on wetland substrates showed that acid volatile sulfides (AVS) increased with time in the wetland substrate. A serum bottle experiment was conducted to study the S balance in the Big Five wetland by quantitatively measuring the amount of S in different phases as microbial SO₄²⁻ reduction progressed. The increase in AVS reasonably balanced the decrease in SO₄²⁻ concentration in the experiment, suggesting that the decrease in SO₄²⁻ concentration represented the amount of SO₄²⁻ reduced and that nearly all of the sulfide produced was precipitated as AVS. Sulfide precipitation was determined to be the primary metal removal process in the wetland system and amorphous FeS is the primary iron sulfide formed in the substrate.     

Reductive transformation of iron and sulfur in schwertmannite-rich accumulations associated with acidified coastal lowlands

We examined the transformations of Fe and S associated with schwertmannite (Fe₈O₈(OH)₆SO₄) reduction in acidified coastal lowlands. This was achieved by conducting a 91 day diffusive-flux column experiment, which involved waterlogging of natural schwertmannite- and organic-rich soil material. This experiment was complemented by short-term batch experiments utilizing synthetic schwertmannite. Waterlogging readily induced bacterial reduction of schwertmannite-derived Fe(III), producing abundant pore-water Fe^II, SO₄ and alkalinity. Production of alkalinity increased pH from pH 3.4 to pH ∼6.5 within the initial 14 days, facilitating the precipitation of siderite (FeCO₃). Interactions between schwertmannite and Fe^II at pH ∼6.5 were found, for the first time, to catalyse the transformation of schwertmannite to goethite (αFeOOH). Thermodynamic calculations indicate that this Fe^II-catalysed transformation shifted the biogeochemical regime from an initial dominance of Fe(III)-reduction to a subsequent co-occurrence of both Fe(III)- and SO₄-reduction. This lead firstly to the formation of elemental S via H₂S oxidation by goethite, and later also to formation of nanoparticulate mackinawite (FeS) via H₂S precipitation with Fe^II. Pyrite (FeS₂) was a quantitatively insignificant product of reductive Fe and S mineralization. This study provides important new insights into Fe and S geochemistry in settings where schwertmannite is subjected to reducing conditions.     

Trace metal deposition and mobility in the sediments of two lakes near Sudbury,Ontario

The accumulation and mobility of Fe, Mn, Al, Cu, Ni and Pb in the sediments of two lakes (Clearwater, pH 4.5; and McFarlane, pH 7.5) near Sudbury, Ontario have been investigated. The Al, Cu and Ni concentrations are expectedly relatively high in the overlying waters of Clearwater Lake and much lower for Al and Cu in McFarlane Lake. The low trace metal concentrations found in the anoxic porewaters of Clearwater Lake could be explained by a sharp increase in porewater pH concomitant with SO₄² reduction and H₂S production within the first 1–2 cm of the sediments, which has conceivably led to the precipitation of mineral phases such as AL(OH)₃, NiS, and CuS. In both lakes, Fe concentrations in anoxic porewaters appear to be controlled by FeS and/or FeCO₃ formation. Solubility calculations also indicate MnCO₃ precipitation in McFarlane Lake. In Clearwater Lake, however, both porewater and total Mn were relatively low, a possible result of the continuous loss of Mn(II) through the acidic interface. It is suggested that upwardly decreasing total Mn profiles resulting from the removal of Mn from the top sediment layers under acidic conditions may constitute a reliable symptom of recent lake acidification.The downward diffusion of AI, Cu and Ni from the overlying water to the sediments has been estimated from their concentration gradients at the interface and compared to their total accumulation rates in the sediments. In both lakes the diffusion of Al is negligible compared to its accumulation rate. However, diffusion accounts for 24–52% of the accumulation of Cu in the sediments of Clearwater Lake, but appears negligible in McFarlane Lake. The downward diffusive flux of Ni is important and may explain 76–161% of the estimated Ni accumulation rate in Clearwater Lake, and 59% in McFarlane Lake. The porewater Cu and Ni profiles suggest that the subsurface sedimentary trace metal peaks observed in Clearwater Lake (as in other acid lakes) may not be caused by sediment leaching or by a recent reduction in sedimentation but may have a diagenetic origin instead. Diffusion to the sediments thus appears to be an important and previously overlooked trace metal deposition mechanism, particularly in acid lakes.