Hydrogeochemical characteristics of acid mine drainage in the vicinity of an abandoned mine, Daduk Creek, Korea

Acid mine drainage discharged from the abandoned Daduk mine towards the Daduk creek has a pH of 3.3, and concentrations of Al, Mn, Fe, Zn and SO₄ of 18, 41, 45, 38 and 1940 mg/L, respectively. In particular, As concentration in acid mine drainage is 1000 μg/L. Removing order of metal ions normalized by SO₄ concentration downstream from discharge point is Fe > As > Al > Cu > Zn > Mn > Cd > Pb. In the Daduk creek, Fe and As are the most rapidly depleted downstream from acid mine drainage because As adsorbs, coprecipitates and forms compounds with ferric oxyhydroxide. From the results of geochemical modeling using the Phreeq C program, goethite (FeOOH) is oversaturated, and schwertmannite (Fe₈O₈(OH)_4.5(SO₄)_1.75) is the most stable solid phase at low pH in the Daduk creek. Yellowish red (orange ochre) precipitates that occurred in the study area are probably composed of goethite or schwertmannite.     

Seasonal variations of ochreous precipitates in mine effluents in Finland

Ochreous precipitate and water samples were collected from the surroundings of seven closed sulphide mines in Finland. In the Hammaslahti Zn–Cu–Au mine, Otravaara pyrite mine and Paroistenjärvi Cu–W–As mine, the collection was repeated in different seasons to study mineralogical and geochemical variations of precipitates. The sampling was done in 1999–2002 from the ditches and drainage ponds of the tailings and waste rock piles that are susceptible to seasonal changes. Mineralogy of the precipitates was evaluated by X-ray diffraction (XRD) and infrared spectroscopy (IR), and precipitate geochemistry was examined by selective extractions. Schwertmannite (Fe₈O₈(OH)₆SO₄) was the most typical Fe hydroxide mineral found. Goethite was almost as common as schwertmannite, was often poorly ordered, and contained up to 10 wt.% of SO₄. Goethite and schwertmannite were commonly found as mixtures, and they occurred in similar pH and SO₄ concentrations. Ferrihydrite (nominally Fe₅HO₈ · 4H₂O) was typically found in areas not influenced by acid mine drainage, and also in acid mine waters with high organic matter or As content. Jarosite (KFe₃(SO₄)₂(OH)₆) was found only in one site. In addition, some gypsum (CaSO₄ · 2H₂O) and aluminous sulphate precipitates (presumably basaluminite, Al₄(SO₄)(OH)₁₀ · 5H₂O) were identified. Selective extractions showed that acid extracts Fe_tot/S_tot-ratios of schwertmannite and goethite samples were similar, but the ratio of oxalate-extractable to total Fe, Fe_ox/Fe_tot, of goethite samples were lower than those of the schwertmannite samples. Only Al, Si and As were bound to precipitates in substantial amounts, up to several wt.%. In schwertmannites and goethites, Al, Cu, Co, Mn and Zn were mostly structural, substituting for Fe in an Fe oxyhydroxide structure or bound to surface adsorption sites in pores limited by diffusion. In ferrihydrites, heavy metals were also partly bound in adsorbed form dissolving in acid ammonium acetate. Ferrihydrites and goethites were more enriched in Co, Mn and Zn than schwertmannites, but schwertmannites and ferrihydrites were more enriched in As than goethites. Mineralogical and geochemical evidence showed that in the spring, after the snowmelt, the acid mine drainage precipitates were predominantly schwertmannite, and were partly transformed during warm summer months to goethite. The phase transformation of precipitates was followed by a decrease in pH values and increase in SO₄ concentrations of waters. Adsorbed As retarded the phase transformation.     

Iron sulfide oxidation and the chemistry of acid generation

Acid mine drainage, produced from the oxidation of iron sulfides, often contains elevated levels of dissolved aluminum (AI), iron (Fe), and sulfate (SO₄) and low pH. Understanding the interactions of these elements associated with acid mine drainage is necessary for proper solid waste management planning. Two eastern oil shales were leached using humidity cell methods. This study used a New Albany Shale (4.6 percent pyrite) and a Chattanooga Shale (1.5 percent pyrite). The leachates from the humidity cells were filtered, and the filtrates were analyzed for total concentrations of cations and anions. After correcting for significant solution species and complexes, ion activities were calculated from total concentrations. The results show that the activities of Fe³⁺, Fe²⁺, Al³⁺, and SO₄ ²⁻ increased due to the oxidation of pyrite. Furthermore, the oxidation of pyrite resulted in a decreased pH and an increased pe+pH (redox-potential). The Fe³⁺ and Fe²⁺ activities appeared to be controlled by amorphous Fe(OH)₃ solid phase above a pH of 6.0 and below pe+pH 11.0. The Fe³⁺, Fe²⁺, and SO₄ ²⁻ activities reached saturation with respect to FeOHSO₄ solid phase between pH 3.0 and 6.0 and below pe+pH 11.0 Below a pH of 3.0 and above a pe+pH of 11.0, Fe²⁺, Fe³⁺, and SO₄ ²⁻ activities are supported by FeSO₄·7H₂O solid phase. Above a pH of 6.0, the Al³⁺ activity showed an equilibrium with amorphous Al(OH)₃ solid phase. Below pH 6.0, Al³⁺ and SO₄ ²⁻ activities are regulated by the AlOHSO₄ solid phase, irrespective of pe+pH. The results of this study suggest that under oxidizing conditions with low to high leaching potential, activities of Al and Fe can be predicted on the basis of secondary mineral formation over a wide range of pH and redox. As a result, the long-term chemistry associated with disposal environments can be largely predicted (including trace elements).     

Apparent solubilities of schwertmannite and ferrihydrite in natural stream waters polluted by mine drainage

The apparent solubilities of schwertmannite and ferrihydrite were estimated from the H⁺, OH⁻, Fe³⁺, and SO₄²⁻ activities of the natural stream waters in Korea and mine drainage in Ohio, USA. Both chemical composition of the stream waters and the mineralogy of the precipitates were determined for samples from two streams polluted by coal mine drainage. This study combines these new results with previous data from Ohio, USA to redetermine solubilities. The activities of the dissolved species necessary for the solubility determinations were calculated from the chemical compositions of the waters with the WATEQ4F computer code.Laboratory analyses of precipitates indicated that the main minerals present in Imgok and Osheep creek were schwertmannite and ferrihydrite, respectively. The schwertmannite from Imgok creek had a variable chemical formula of Fe₈O₈(OH)_8−2x(SO₄)_x· nH₂O, where 1.74 ≤ x ≤ 1.86 and 8.17 ≤ n ≤ 8.62. The chemical formula of ferrihydrite was Fe₂O₃· 1.6H₂O. With known mineralogy of the precipitates from each stream, the activities of H⁺, OH⁻, Fe³⁺, and SO₄²⁻ in the waters were plotted on logarithmic activity-activity diagrams to determine apparent solubilities of schwertmannite and ferrihydrite. The best estimate for the logarithm of the solubility product of schwertmannite, logK_s, was 10.5 ± 2.5 around 15°C. This value of logK_s constrains the logarithm of the solubility product of ferrihydrite, logK_f, to be 4.3 ± 0.5 to maintain the stability boundary with schwertmannite observed in natural waters.     

Precipitation of Fe and Al compounds from the acid mine waters in the dogyae area, Korea: A qualitative measure of equilibrium modeling applicability and neutralization capacity?

To investigate the applicability of equilibrium modeling for the estimation of the chemical changes of acid mine waters, the phases predicted to precipitate by equilibrium calculation were compared with what actually precipitates from the stream and acid mine waters in the Dogyae area, Korea. The computer program MINTEQA2 was used for the equilibrium calculations based on the chemical compositional data of the water samples collected in the study area. XRD, IR, thermal and chemical analyses of the collected precipitates were performed to identify their phases.The results of the identification of the collected precipitates are inconsistent with what the equilibrium calculations predict. The equilibrium calculations indicate that ferrihydrite, FeOHSO₄, gibbsite, and AlOHSO₄ should precipitate from the stream and acid mine waters in the study area. However, the experimental analyses show that only ferrihydrite and Al₄(OH)₁₀SO₄ are the recognizable precipitates on the bottom of the stream and mine drainage channels. Comparing the stability relations among the possible precipitates with the field occurrence of the precipitates in the study area suggests that FeOHSO₄ and AIOHSO₄ are kinetically inhibited to precipitate and metastable ferrihydrite and Al₄(OH)₁₀SO₄ appear in their stability field instead. It indicates that the chemical compositional change of the waters due to the solid phase precipitation in the study area must be interpreted and predicted in terms of the precipitation of not the phases predicted by the equilibrium calculation but the actually identified ones.Assuming that the dissolved species in the aqueous phase are in equilibrium with respect to the currently precipitating solid phases in the study area, the water chemistries are attempted to interpret based on the plot of the theoretically calculated activities of the dissolved species on the stability diagram for the identified precipitates and gibbsite. The plot reveals a few evolution paths of the chemical composition of the acid mine water as the acid generation and neutralization progress. The evolution path producing ferrihydrite and then Al₄(OH)₁₀SO₄ precipitation suggests that the system including acid producing pyrite has lost significant amounts of its neutralizing capacity and thus, become intolerable to the impacts from acid mine water.     

Pollution of a water course impacted by acid mine drainage in the Imgok creek of the Gangreung coal field,Korea

The purposes of this study are to (i) determine the geochemical characteristics of Imgok creek impacted by acid mine drainage (AMD) generated from abandoned coal mines, (ii) to assess the pollution of heavy metals in the stream sediments and soils, and (iii) to identify the chemical form of Fe precipitates collected in the study area where there are 4 abandoned coal mines, which belong to the Grangreung coal field at the eastern part of Korea. AMD generated from mine adits and coal refuse piles shows low pH, and high concentrations of Fe, Al and SO₄, especially in the Youngdong coal mine. In Imgok creek, pH values increased, and total dissolved solids (TDS) values decreased with distance. The concentrations of toxic heavy metals and major cations except Fe decreased by dilution, but the concentration of Fe decreased rapidly due to the formation of precipitates. The quality of groundwater samples did not exceed the Korean drinking-water standard. In the stream sediments, the concentrations of Fe are relatively high in the Youngdong tributary and Imgok creek, but the concentrations of heavy metals are similar to those of unpolluted sediments. Pollution indices of agricultural soils range from 0.28 to 0.47. Yellowish red Fe precipitates collected in the study area turned out to be amorphous or poorly crystallized minerals (determined by X-ray diffraction patterns and Fe_ox/Fe_tot ratios) and to contain chemically bonded SO₄ and OH [determined by infra-red (IR) spectral analysis]. With these, the mol ratios of Fe/S ranging from 4.6 to 6.1 determined by electron probe micro-analysis (EPMA) in precipitates strongly support the existence of schwertmannite.     

Identification of the uranium speciation in an underground acid mine drainage environment

The subsurface acid mine drainage (AMD) environment of an abandoned underground uranium mine in Königstein/Saxony/Germany, currently in the process of remediation, is characterized by low pH, high sulfate concentrations and elevated concentrations of heavy metals, in particular uranium. Acid streamers thrive in the mine drainage channels and are heavily coated with iron precipitates. These precipitates are biologically mediated iron precipitates and related to the presence of Fe-oxidizing microorganisms forming copious biofilms in and on the Fe-precipitates. Similar biomineralisations were also observed in stalactite-like dripstones, called snottites, growing on the gallery ceilings.The uranium speciation in these solutions of underground AMD waters flowing in mine galleries as well as dripping from the ceiling and forming stalactite-like dripstones were studied by time resolved laser-induced fluorescence spectroscopy (TRLFS). The fluorescence lifetime of uranium species in both AMD water environments were best described with a mono-exponential decay, indicating the presence of one major species. The detected positions of the emission bands and by comparing it in a fingerprinting procedure with spectra obtained for acid sulfate reference solutions, in particular Fe(III) - SO₄²⁻ - UO₂²⁺ reference solutions, indicated that the uranium speciation in the AMD environment of Königstein is dominated in the pH range of 2.5-3.0 by the highly mobile aquatic uranium sulfate species UO₂SO_4(aq) and formation of uranium precipitates is rather unlikely as is retardation by sorption processes. The presence of iron in the AMD reduces the fluorescence lifetime of the UO₂SO_4(aq) species from 4.3 μs, found in iron-free uranium sulfate reference solutions, to 0.7 μs observed in both AMD waters of Königstein and also in the iron containing uranium sulfate reference solutions.Colloids were not observed in both drainage water and dripping snottite water as photon correlation spectroscopy analyses and centrifugation experiments at different centrifugal accelerations between 500g and 46000g revealed. Thus transport and uranium speciation at the investigated AMD sites is neither influenced by U(IV) or U(VI) eigencolloids nor by uranium adsorbed on colloidal particles.This study shows that TRLFS is a suitable spectroscopic technique to identify the uranium speciation in bulk solutions of AMD environments.     

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.     

Geochemical and mineralogical impacts of H2SO4 on clays between pH 5.0 and −3.0

Natural and constructed clay liners are routinely used to contain waste and wastewater. The impact of acidic solutions on the geochemistry and mineralogy of clays has been widely investigated in relation to acid mine drainage systems at pH > 1.0. The impact of H₂SO₄ leachate characterized by pH < 1.0 and potentially negative pH values on the geochemistry and mineralogy of clays is, however, not clear. Thus, laboratory batch experiments were conducted on three natural clay samples with different mass ratios of smectite, illite and kaolinite to investigate the impact of H₂SO₄ on the geochemistry and mineralogy of aluminosilicates from pH 5.0 to −3.0. Batch testing was conducted at seven pH treatments (5.0, 3.0, 1.0, 0.0, −1.0, −2.0 and −3.0) using standardized H₂SO₄ solutions for four exposure periods (14, 90, 180, and 365 d). Aqueous geochemical and XRD analyses showed: increased dissolution of aluminosilicates with decreasing pH and increasing exposure period, that smectite was more susceptible to dissolution than illite and kaolinite, precipitation of an amorphous silica phase occurred at pH ? 0.0, and anhydrite precipitated in Ca-rich clays at pH ? −1.0. In addition, global dissolution rates were calculated for the clays and showed good agreement to literature smectite, illite and kaolinite dissolution rates, which suggests global dissolution rates for complex clays could be determined from monomineralic studies. A stepwise conceptual model of the impact of H₂SO₄ on aluminosilicate geochemistry and mineralogy between pH 5.0 and −3.0 is proposed.     

Pressure-oxidation autoclave as an analogue for acid–sulphate alteration in epithermal systems

Gold extraction at the Macraes gold mine in New Zealand involves concentration of pyrite and arsenopyrite, oxidation of those sulphides, then cyanidation. The ore concentrate is predominantly Otago Schist host rock (andesitic composition) with up to 15% sulphides. The oxidation step is conducted on ore concentrate slurry in an autoclave at 225°C and 3,800 kPa oxygen gas pressure with continuous feed. The slurry takes ca. 1 h to pass through the autoclave, during which time the sulphides are almost completely oxidised. Sulphide oxidation causes strong acidification of the slurry, which is maintained at pH of 1–2 by addition of CaCO₃. Scales form on walls in the autoclave, with minerals reflecting progressive oxidation and alteration of the ore through the system. The schist in the ore feed has mineralogy similar to propylitically altered andesite: quartz, albite, muscovite, chlorite, and pyrite. Muscovite undergoes almost complete dissolution, with associated precipitation of quartz and alunite (KAl₃(SO₄)₂(OH)₆). Other principal minerals deposited and discharged include anhydrite (and/or gypsum), jarosite (KFe₃(SO₄)₂(OH)₆), hematite (and/or amorphous iron oxyhydroxide), and amorphous arsenates. Dissolved ferrous iron passes right through the autoclave, and variably hydrated Fe²⁺and Fe³⁺sulphate minerals, including rozenite and szomolnokite (both FeSO₄.hydrate) and ferricopiapite (Fe₅(SO₄)₆O(OH).hydrate), are formed along the way. The autoclave chemical system resembles acid–sulphate hydrothermal activity in geothermal systems and high-sulphidation epithermal mineral deposits formed in arc environments. These natural acid–sulphate systems are pervaded by volcanic vapours in the near-surface environment, where widespread dissolution of host rocks occurs and deposition of quartz, alunite, and anhydrite is common. Some of the volume loss associated with these natural systems may be due to dissolution of soluble sulphate minerals by later-stage groundwater incursion.     

Mineralogical components of some thermally decomposed lignite and lignite ash from the Ptolemais basin, Greece

Two samples of Pliocene lignites from the Ptolemais basin of Greece, one from the upper and one from the lower lignite seams, were heated and dried in air at 50°C intervals from 50 to 1200°C. The two lignite samples initially contained the same minerals, namely calcite, dolomite, quartz, kaolinite, illite, pyrite and gypsum, but in different proportions. The lignite sample from the upper lignite seam is rich in Fe₂O₃, CaO and SO₃, while that from the lower lignite seam is rich in SiO₂ and Al₂O₃.Hematite, periclase, melilites, calcium ferrite and brownmillerite are constituents of the 1200°C lignite ash from both samples. The heating conditions and the chemistry of the samples lowered the formation temperatures of brownmillerite, which appeared in both samples at 950°C. In the Fe₂O₃, CaO- and SO₃-rich sample, magnesioferrite is present from 850 to 1100°C and hematite appears at 300°C. In the SiO₂- and Al₂O₃-rich sample, magnesioferrite was not detected at any temperature and hematite appeared at 600°C.Anhydrite, which normally decomposes in air at 1638°C, is the main constituent at 1150°C, on heating the lignite sample that was rich in Fe₂O₃, CaO and SO₃. Anhydrite diminishes at 1200°C. In the SiO₂- and Al₂O₃-rich lignite sample, anhydrite is main constituent at 1100°C, but diminishes considerably at 1150°C and decomposes at 1200°C.     

Experimental Study on Formation Conditions of Ammoniojarosite and Its Environmental Significance

Formation conditions of ammoniojarosite in system Fe2（SO4）3-（NH4）2SO4-H2O are investigated in this paper. The results show that ammoniojarosite can be formed rapidly under normal temperature and pressure by controlling suitable pH value and Fe2（SO4）3 and （NH4）2SO4 concentrations. The pH value, temperature and concentration of Fe2（SO4）3 medium are key factors influencing the formation of ammoniojarosite. Under normal temperature, precipitation of ammoniojarosite can be seen within 24 hours at pH values between 2.6-3.1, and a great quantity of ammoniojarosite is formed within 48 hours. At about 90℃, the pH value range forming ammoniojarosite extends to 1.2-3.1, and within this range the rise of pH value is advantageous to the formation of ammoniojarosite and high Fe2（SO4）3 concentration is also advantageous. Relative pure ammoniojarosite is synthesized under high Fe2（SO4）3 concentration （≥0.05 M） and ammoniojarosite containing melanterite and colloid amorphous hydroxide vitriol iron is formed at low Fe2（SO4）3 concentration. The deposition process of ammoniojarosite can be used to harness wastewater from mines and other industries and remove S, Fe and other toxic and harmful elements, such as As, Cr, Hg, Pb in water. Rapid formation of ammoniojarosite and other jarosite analogs under normal temperature and pressure has a good potential prospect for harnessing acid wastewater by means of precipitation of jarosite and its analogs.     

Dissolution of lead- and lead-arsenic-jarosites at pH 2 and 8 and 20 °C: Insights from batch experiments

Lead- and Pb-As-jarosites are minerals common to acidic, sulphate-rich environments, including weathering zones of sulphide ore deposits and acid rock or acid mine drainage (ARD/AMD) sites, and often form on or near galena. The structures of these jarosites are based on linear tetrahedral-octahedral-tetrahedral (T-O-T) sheets, comprised of slightly distorted FeO₆ octahedra and SO₄²⁻ (-AsO₄³⁻ in Pb-As-jarosites) tetrahedra. To better understand the dissolution mechanisms and products of the break down of Pb- and Pb-As-jarosite, preliminary batch dissolution experiments were conducted on synthetic Pb- and Pb-As-jarosite at pH 2 and 20 °C, to mimic environments affected by ARD/AMD, and at pH 8 and 20 °C, to simulate ARD/AMD environments recently remediated with slaked lime (Ca(OH)₂). All four dissolutions are incongruent. Dissolution of Pb-jarosite at pH 2 yields aqueous Pb, Fe and SO₄²⁻. The pH 8 Pb-jarosite dissolution yields aqueous Pb, SO₄²⁻ and poorly crystalline Fe(OH)₃, which does not appear to resorb Pb or SO₄²⁻, possibly due to the low solution pH (3.44-3.54) at the end of the experiment. The pH 2 and 8 dissolutions of Pb-As-jarosite result in the formation of secondary compounds (poorly crystalline PbSO₄ for pH 2 dissolution; poorly crystalline PbSO₄ and Fe(OH)₃ for pH 8 dissolution), which may act as dissolution inhibitors after 250 to 300 h of dissolution. In the pH 2 dissolution, aqueous Fe, SO₄²⁻ and AsO₄³⁻ also form, and in the pH 8 dissolution, Fe(OH)₃ precipitates then subsequently resorbs aqueous AsO₄³⁻. The dissolutions probably proceed by preferred dissolution of the A- and T-sites, which contain Pb, and SO₄²⁻ and AsO₄³⁻, respectively, rather than Fe, which is sterically remote, within the T-O-T Pb- and Pb-As-jarosite structures. These data provide the foundation necessary for further, more detailed investigations into the dissolution of Pb- and Pb-As-jarosites.     

Geochemical modeling of coal mine drainage, Summit County, Ohio

 Geochemical modeling was used to investigate downstream changes in coal mine drainage at Silver Creek Metro-park, Summit County, Ohio. A simple mixing model identified the components that are undergoing conservative transport (Cl^–, PO₄ ^3–, Ca²⁺, K⁺, Mg²⁺ and Na⁺) and those undergoing reactive transport (DO, HCO₃ ^–, SO₄ ^2–, Fe²⁺, Mn²⁺ and Si). Fe²⁺ is removed by precipitation of amorphous iron-hydroxide. Mn²⁺ are removed along with Fe²⁺ by adsorption onto surfaces of iron-hydroxides. DO increases downstream due to absorption from the atmosphere. The HCO₃ ^– concentration increases downstream as a result of oxidation of organic material. The rate of Fe²⁺ removal from the mine drainage was estimated from the linear relationship between Fe⁺² concentration and downstream distance to be 0.126 mg/s. Results of this study can be used to improve the design of aerobic wetlands used to treat acid mine drainage. Received: 4 June 1996 · Accepted: 17 September 1996     

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.     

Sideronatrite: A mineral with a {Fe2(SO4)4(OH)2} guildite type chain?

Summary Recently several natural and artificial ferric iron sulphate crystal structures have been solved. Sideronatrite, Na₂Fe³⁺(SO₄)₂(OH)·3H₂O, does not provide good crystals for structural purposes. However if we examine crystallographic, chemical and physical data some useful information about the ...Fe–O–S... structural topology can be inferred. In fact this analysis strengthens the hypothesis that there is a {Fe ₂ ³⁺ (SO₄)₄(OH)₂} chain in sideronatrite like that found in guildite, Cu²⁺Fe³⁺(SO₄)₂(OH)·4H₂O.

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Sideronatrit: Ein Mineral mit einer {Fe₂(SO₄)₄(OH)₂}-Kette vom Typ Guildit?

Zusammenfassung Kürzlich wurden die Kristallstrukturen mehrerer natürlicher und künstlicher Ferrisulfate gelöst. Sideronatrit, Na₂Fe³⁺(SO₄)₂(OH)·3H₂O, liefert keine für die Strukturuntersuchung gut geeigneten Kristalle. Dennoch erhält man aus der Untersuchung der kristallographischen, chemischen und physikalischen Daten nützliche Information über die ...Fe–O–S...-Topologie der Struktur. Eine solche Analyse spricht für die Hypothese, daß der Sideronatrit eine {Fe ₂ ³⁺ (SO₄)₄(OH₂)}-Kette enthält, wie sie im Guildit, Cu²⁺Fe³⁺(SO₄)₂(OH)·4H₂O, gefunden wurde.

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With 1 Figure

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Paper presented at the Sixth European Crystallographic Meeting. Barcelona, Spain 1980.     

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.     

Geochemical models of the impact of acidic groundwater and evaporative sulfate salts on Boulder Creek at Iron Mountain,California

During dry season baseflow conditions approximately 20% of the flow in Boulder Creek is comprised of acidic metals-bearing groundwater. Significant amounts of efflorescent salts accumulate around intermittent seeps and surface streams as a result of evaporation of acid rock drainage. Those salts include the Fe-sulfates — rhomboclase ((H₃O)Fe³⁺(SO₄)₂·3H₂O), ferricopiapite (Fe³⁺₅(SO₄)₆O(OH)·20H₂O), and bilinite (Fe²⁺Fe₂³⁺(SO₄)₄·22H₂O); Al-sulfates — alunogen (Al₂(SO₄)₃·17H₂O) and kalinite (KAl(SO₄)₂·11H₂O); and Ca- and Mg-sulfates — gypsum (CaSO₄·2H₂O), and hexahydrite (MgSO₄·6H₂O). The dissolution of evaporative sulfate salt accumulations during the first major storm of the wet season at Iron Mountain produces a characteristic hydrogeochemical response (so-called “rinse-out”) in surface waters that is subdued in later storms. Geochemical modeling shows that the solutes from relatively minor amounts of dissolved sulfate salts will maintain the pH of surface streams near 3.0 during a rainstorm. On a weight basis, Fe-sulfate salts are capable of producing more acidity than Al- or Mg-sulfate salts. The primary mechanism for the production of acidity from salts involves the hydrolysis of the dissolved dissolved metals, especially Fe³⁺. In addition to the lowering of pH values and providing dissolved Fe and Al to surface streams, the soluble salts appear to be a significant source of dissolved Cu, Zn, and other metals during the first significant storm of the season.     

Dissolution of jarosite [KFe3(SO4)2(OH)6] at pH 2 and 8: Insights from batch experiments and computational modelling

Jarosite [KFe₃(SO₄)₂(OH)₆] is a mineral that is common in acidic, sulphate-rich environments, such as acid sulphate soils derived from pyrite-bearing sediments, weathering zones of sulphide ore deposits and acid mine or acid rock drainage (ARD/AMD) sites. The structure of jarosite is based on linear tetrahedral-octahedral-tetrahedral (T-O-T) sheets, made up from slightly distorted FeO₆ octahedra and SO₄ tetrahedra. Batch dissolution experiments carried out on synthetic jarosite at pH 2, to mimic environments affected by ARD/AMD, and at pH 8, to simulate ARD/AMD environments recently remediated with slaked lime (Ca(OH)₂), suggest first order dissolution kinetics. Both dissolution reactions are incongruent, as revealed by non-ideal dissolution of the parent solids and, in the case of the pH 8 dissolution, because a secondary goethite precipitate forms on the surface of the dissolving jarosite grains. The pH 2 dissolution yields only aqueous K, Fe, and SO₄. Aqueous, residual solid, and computational modelling of the jarosite structure and surfaces using the GULP and MARVIN codes, respectively, show for the first time that there is selective dissolution of the A- and T-sites, which contain K and SO₄, respectively, relative to Fe, which is located deep within the T-O-T jarosite structure. These results have implications for the chemistry of ARD/AMD waters, and for understanding reaction pathways of ARD/AMD mineral dissolution.