The evolution of surface layers formed during chalcopyrite leaching

Chalcopyrite (CuFeS₂) leaching in perchloric acid (HClO₄) at an initial pH of one and a temperature of 85 °C has been examined. The rate of leaching of Cu and Fe increased progressively over the duration of the experiment. The Cu leach rate was initially greater (up to 24 h) but thereafter the leach rates for Cu and Fe were approximately equal. After 313 h 81% Cu release was achieved at which time the leach experiment was terminated. Only 25% of the available S was released into solution during the leaching process. Surface speciation over the duration of the leach was examined using X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectrometry (ToF-SIMS) and scanning electron microscopy (SEM). As a result, a three-step reaction pathway is proposed. The first oxidation step involves the release of Cu and Fe into solution and the polymerisation of monosulfide (S²⁻) to polysulfide . The subsequent reduction step does not result in the release of cations to solution but does result in the reformation of surface S²⁻ and other short chain polysulfides, which then on further oxidation restructure to form crystalline elemental sulfur (S⁰). This final oxidation step is accompanied by further cation release.     

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ¹⁸O_H2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O₂ and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε¹⁸O_SO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent ε_SO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O₂ into sulfate. δ³⁴S_SO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ³⁴S_SO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.     

Chemical speciation of redox sensitive elements during hydrocarbon leaching in the Junggar Basin,Northwest China

Bleaching related to seepage of petroleum fluids and subsurface migration of crude oil and natural gas can alter the chemical and mineralogical properties of rocks, while concurrently depleting hydrocarbon reservoirs. Mud volcanoes constitute one type of petroleum seepage present in several areas on the southern margin of the Junggar Basin in the Xinjiang Uygur Autonomous Region, NW China. The results of XRD, XRF, XANES, and Mössbauer spectroscopy on rock samples collected from areas affected by these mud volcanoes revealed an enrichment of certain minerals and elements, as well changes in mineralogical, molecular, or ionic carrier (“species”). After bleaching, reddish sedimentary rocks showed depletion in silica and enrichment of calcium, magnesium, manganese, and iron. Other elements, including aluminum, potassium, sodium, and titanium, were largely unchanged. Reduced iron and sulfur compounds predominated in the bleached rocks, producing changes in color from the original reddish into green, deep gray, and black. Iron and calcium were associated with carbonates, indicating carbonation of these elements during the bleaching processes. Manganese also appeared to be associated with carbonate, though not with sulfate even though sulfate was present in the bleached rocks. Alkaline conditions were apparently the dominant because reduced manganese would have been absent under acidic condition. The alteration of certain minerals, clay minerals in particular, was also observed in bleached rocks, the alteration of smectite-group minerals to chlorite and muscovite, for example. Mineralogical and geochemical changes in rocks bleached by hydrocarbon fluids could provide a better overall understanding of bleaching processes, and may have applications in surface geochemical exploitation and remote imaging.     

Cobalt behavior during natural and technogenic oxidative leaching of Co-containing pyrites (Letnee chalcopyrite deposit,Southern Urals)

Cobalt behavior during the oxidation of sulfide ores, unlike that during the oxidation of Co ores, is poorly known. Moreover, cobalt sulfates are rare in the world. Complex hydrous cobalt-containing and cobalt sulfates have been found in technogenic zones at the Letnee chalcopyrite deposit (Southern Urals). They have been identified at pit bottoms, in the ore stockpile, as well as directly on ore fragments and the evaporation barriers of underdump water puddles. The paper reports the first experimental data on the oxidative leaching of Co-containing sulfide ores in the laboratory. Also, parts of a thermodynamic model for Co behavior in oxidized zones are presented.Experiments have revealed an increase in acidity up to pH = 4.14, along with transport of sulfate sulfur and metals into solution. This suggests acid mine drainage during the development of the Letnee deposit. The published stability diagrams for hydrous Cu, Mg, Zn, Co, and Ni sulfates were analyzed and compared with mineralogical finds in a technogenic oxidized zone. This made it possible to explain the precipitation sequence of minerals from solutions during their concentration by evaporation. As salts of these elements are highly soluble, significant contents of toxic metals will inevitably remain in equilibrium solution, necessitating additional waste-water treatment (for example, creating sorption geochemical barriers). Therefore, the paper describes regularities in Co behavior during its sorption on solid phases.     

FeSO4稳定铬污染土的铬赋存形态及浸出特性研究

采用硫酸亚铁（FeSO4）对Cr(VI)污染土进行稳定化处理。研究了Fe(II)/Cr(VI)摩尔比和养护龄期对污染土稳定过程中的铬赋存形态及浸出特性的影响规律。结果表明：随着Fe(II)/Cr(VI)摩尔比和养护龄期的增加,Cr(VI)和总Cr的浸出浓度降低,稳定土中Cr(VI)的含量降低,当摩尔比为3时,Cr(VI)和总Cr的浸出浓度均低于我国《危险废弃物鉴别标准 浸出毒性鉴别》（GB/T50853―2007）的限值;当摩尔比为10时,稳定土中Cr(VI)的含量低于我国《土壤环境质量标准》（GB15618―2008）中工业和商业用地的限值（30 mg/kg）;当摩尔比为20时,低于居住用地限值（5 mg/kg）。形态提取试验结果表明：FeSO4改变稳定土中铬的赋存形态,可促使铬从弱酸态向可还原态和可氧化态转化,而对残渣态的铬影响不大。Cr(VI)的浸出浓度与稳定土中的Cr(VI)含量均存在指数函数关系,且浸出试验不能全面、客观地评价铬污染土稳定效果。     

Investigation of zinc extraction from different leach residues by acid leaching

With different properties, zinc is one of the most important non-ferrous metals and it is used in various application areas, especially as an anti-corrosion agent. In Turkey, zinc production was based on zinc carbonate ores (ZnCO₃), at Çinkur plant from establishment to 1997 due to high reserves of zinc carbonate. After that, zinc concentrate coming from Iran was used in this plant over the last two decades. Thus, two different leach residues called as Turkish leach residue (TLR) and Iranian leach residue (ILR) were accumulated more than one million ton in Çinkur stock piles. In this study, it is aimed to investigate zinc recovery for each leach residue by use of sulphuric acid (H₂SO₄) and to compare the TLR and the ILR. Initially, detailed chemical, mineralogical and thermal analyses of these different leach residues were carried out. In order to investigate the effect of acid concentration and reaction duration on zinc recovery, leaching experiments were carried out at following conditions: 95 °C, 100 g/L pulp density and 600 rpm stirring rate. According to the characterization results, the chemical compositions for both residues are nearly similar; however, experimental results show that zinc recovery per cent of the ILR was higher than that of TLR for all experimental durations and acid concentrations. This may be due to the presence of Zn-containing compounds in the both residues at different percentages.     

Fractionation of multiple sulfur isotopes during phototrophic oxidation of sulfide and elemental sulfur by a green sulfur bacterium

We present multiple sulfur isotope measurements of sulfur compounds associated with the oxidation of H₂S and S⁰ by the anoxygenic phototrophic S-oxidizing bacterium Chlorobium tepidum. Discrimination between ³⁴S and ³²S was +1.8 ± 0.5‰ during the oxidation of H₂S to S⁰, and −1.9 ± 0.8‰ during the oxidation of S⁰ to , consistent with previous studies. The accompanying Δ³³S and Δ³⁶S values of sulfide, elemental sulfur, and sulfate formed during these experiments were very small, less than 0.1‰ for Δ³³S and 0.9‰ for Δ³⁶S, supporting mass conservation principles. Examination of these isotope effects within a framework of the metabolic pathways for S oxidation suggests that the observed effects are due to the flow of sulfur through the metabolisms, rather than abiotic equilibrium isotope exchange alone, as previously suggested. The metabolic network comparison also indicates that these metabolisms work to express some isotope effects (between sulfide, polysulfides, and elemental sulfur in the periplasm) and suppress others (kinetic isotope effects related to pathways for oxidation of sulfide to sulfate via the same enzymes involved in sulfate reduction acting in reverse). Additionally, utilizing fractionation factors for phototrophic S oxidation calculated from our experiments and for other oxidation processes calculated from the literature (chemotrophic and inorganic S oxidation), we constructed a set of ecosystem-scale sulfur isotope box models to examine the isotopic consequences of including sulfide oxidation pathways in a model system. These models demonstrate how the small δ³⁴S effects associated with S oxidation combined with large δ³⁴S effects associated with sulfate reduction (by SRP) and sulfur disproportionation (by SDP) can produce large (and measurable) effects in the Δ³³S of sulfur reservoirs. Specifically, redistribution of material along the pathways for sulfide oxidation diminishes the net isotope effect of SRP and SDP, and can mask the isotopic signal for sulfur disproportionation if significant recycling of S intermediates occurs. We show that the different sulfide oxidation processes produce different isotopic fields for identical proportions of oxidation, and discuss the ecological implications of these results to interpreting minor S isotope patterns in modern systems and in the geologic record.     

Oxidation of chalcopyrite by extended milling

Chalcopyrite has been milled for up to 50 h in oxygen, air and argon atmospheres using a laboratory ball mill. No phase changes were evident in argon but the XRD peaks were weaker and broader indicating crystalline refinement. In oxygen, even after 1 h milling peaks for CuSO₄·5H₂O were present and these became predominant after 20 h milling where the chalcopyrite peaks were absent. In air, partial oxidation to CuSO₄·5H₂O was evident after 50 h. Leaching of the resultant powders with water showed 80% dissolution after 50 h milling in oxygen, significantly greater than the 20% and 6% dissolution after milling for 50 h in air and argon respectively. Solution analyses showed the Cu/Fe ratio increased with milling time in oxygen suggesting selectivity may be possible. The insoluble residue was found to consist of haematite, elemental sulphur and unreacted chalcopyrite.     

Determination of sulfur speciation and oxidation state of olivine hosted melt inclusions

In order to better understand what controls sulfur speciation in melt inclusions, and how that pertains to the original basalt composition, we have conducted a series of heating experiments on naturally quenched and crystalline olivine-hosted melt inclusions. Sulfur speciation was determined from S Kα peak shift measurements by electron microprobe on the experimentally heated inclusions as well as a series of naturally quenched inclusions, and matrix glasses.Naturally quenched olivine-hosted melt inclusions record a similar but more variable sulfur speciation relative to matrix glasses, (up to 45–50% variation in S⁶⁺/S_total). Much of this range can be attributed to the effect of degassing which may either increase or decrease the S⁶⁺/S_total. In addition, olivine melt re equilibration and H diffusion out of the inclusion both potentially result in the oxidation of melt inclusions. Heating of melt inclusions can have different effects on the sulfur speciation under different conditions. A slight decrease in S⁶⁺/S_total and oxygen fugacity (∼0.1 log units) can occur from overheating of inclusions (above the temperature of entrapment), resulting from excess ferrous iron in the melt. An increase in heating times should result in an oxidation of the inclusion generated by increased H diffusion out of the inclusion. However, results of heating experiments on melt inclusions from an Izu backarc basalt for less than 30  min do not show a significant increase in sulfur oxidation. In addition, experiments conducted at both IW and FMQ have measured sulfur speciation consistent with naturally quenched inclusions suggesting that at experimental temperatures near that of olivine crystallization the furnace atmosphere does not exert significant control on the melt fO₂. By taking these parameters into account, sulfur speciation and oxidation state of basaltic melt trapped within inclusions can be accurately determined from both naturally quenched and heated olivine hosted melt inclusions.     

Biogeochemical implications of inverse sulfur isotope effects during reduction of sulfur compounds by Clostridium pasteurianum

Large inverse sulfur isotope effects such as those encountered during SO₃^2? reduction by the non-symbiotic dinitrogen fixing soil anaerobe C. pasteurianum may induce ambiguity into calculations of isotopic and mass balance of sulfur compounds in the environment.     

Experimental replacement of chalcopyrite by bornite: Textural and chemical changes during a solid-state process

Chalcopyrite was reacted with covellite and with chalcocite, respectively, between 200°C and 500°C. The ensuing solid-state replacement of chalcopyrite by bornite was studied both texturally and chemically. The relatively oxidizing conditions of the reaction chalcopyrite+covellite result in massive replacement, lacking structural control, where bornite and pyrite form complex intergrowth textures in chalcopyrite. Bornite nucleates around growing pyrite aggregates because of the release of copper and a decrease in volume. Diffusion of sulphur along grain boundaries and fractures largely controls the textural development. Reaction under the relatively reducing conditions involving chalcopyrite+chalcocite results in replacement of chalcopyrite in the sequence where chalcopyrite is replaced by bornite, below about 355°C, and by intermediate solid solution (ISS) and later bornite, above 355°C. The textural development, changing from replacement, apparently uninfluenced by directional properties in the host, to semioriented replacement, is structurally controlled. This suggests that the process is governed by diffusion of copper and iron through a sulphur framework. It is suggested that the observed formation of oriented bornite lamellae in chalcopyrite and in ISS during the chalcopyrite+chalcocite reaction may be explained by replacement exsolution at constant temperature.     

Experimental data on the speciation of sulfur as a function of oxygen fugacity in basaltic melts

The speciation of sulfur as a function of oxygen fugacity was calculated in glasses of basaltic composition saturated experimentally with either sulfide or sulfate phases. The experiments were conducted on mixtures of synthetic and natural materials equilibrated at 1300 °C and 1 GPa in a piston-cylinder apparatus. Sulfur speciation was calculated by measuring the peak shift of the sulfur Kα radiation relative to a sulfide standard, whereas oxygen fugacity was calculated from the composition of olivine and spinel present in the assemblages. The results are consistent with sulfur being present as sulfite (S⁴⁺) in addition to sulfate (S⁶⁺) in oxidized melts. Therefore, sulfur speciation derived from SKα peak shifts should be seen as ”sulfate mole fraction equivalents“ (X(S⁶⁺)_eq.). Using the data available, an empiric function:

X(S6+)_eq.=0.86/(1+exp(2.89−2.23ΔFMQ))     

压实黄土在溶滤作用下的强度特性

为探究压实黄土Q2在溶滤作用下可溶盐对强度的影响,开展了12种应力组合的溶滤试验,测定了不同溶滤时长的离子浓度、可溶盐量与极限正应力。试验结果表明,各离子浓度、可溶盐量及极限正应力均具阶段性减少的特点。应力组合中,溶滤应力水平s影响离子和可溶盐变化曲线的形式及滞后性, 影响溶盐曲线的平滑度,而最终溶盐残余量与s和 均呈正相关。为衡量不同 时的溶盐溶解差异,定义了平均差异性指标 ,其值与s呈正比。为评价溶滤进程,将各溶滤阶段溶盐相对变化量定义为溶盐比 ,其值小于1%时判定溶滤进程结束。在强度方面,极限正应力 随相对可溶盐量 的减少而减小,s决定弱化初期的剧烈程度,不同围压时 值的差异性随s的增大而减弱。 的这3种弱化特性表明,溶滤变形及强度弱化是可溶盐和应力组合共同作用的结果。最后,建立了考虑可溶盐与应力组合影响的强度弱化公式。     

Hydrography of the Santee River during moderate discharge conditions

To harness hydroelectric power, most of the flow of the Santee River, SC was diverted in 1942 into Charleston Harbor, where shoaling promptly became a major problem. For this reason, most of the diverted flow is scheduled to be rediverted to the Santee within the next decade, increasing the mean discharge of the Santee from 74 to 428 m³s^?1. To assess the present hydrogrpahy of the Santee estuary under conditions of moderate discharge, we determined 226 vertical profiles of velocity, salinity, and temperature distributed over 17 stations in February, 1975. We found that 73 and 27% of the discharge reached the ocean via the North and South distributaries, respectively. The 1 ppt isohaline was found no further than 8 km upstream from the mouth, indicating the limited extent of the estuarine zone. The Santee is a partially mixed estuary classified as type 2b. The circulation parameter is approximately 3 and the stratification parameter approximately 0.3. The bulk parameters indicate the importance of tidal, mixing and a weakly developed gravitational circulation. When rediversion is completed, the net salinity in the lower Santee River can be expected to decrease drastically, which in turn is likely to terminate the lucrative oyster and clam fishery.     

Iron isotope fractionation during leaching of granite and basalt by hydrochloric and oxalic acids

Transport of iron (Fe) within hydrothermal and soil environments involves the transferral into aqueous solutions by leaching of complex, polyminerallic rocks. Understanding the isotope fractionation mechanisms during this process is key for any application of the Fe-isotope system to biogeochemical studies. Here, we reacted biotite granite and tholeiite-basalt with 0.5 M hydrochloric acid and 5 mM oxalic acid solutions at ambient temperature. Solution aliquots were recovered over a seven-day period and analysed for major and trace element concentrations and Fe isotopic compositions. In all experiments, Fe initially released into solution was isotopically lighter, with Δ⁵⁶Fe_{solution-rock} as low as −1.80‰ in the granite-hydrochloric acid system. The oxalic acid experiments showed similar patterns but smaller fractionation. In all experiments, the Δ⁵⁶Fe_{solution-rock} reduced over time, which would be in line with the formation of a leached layer as proposed before [Brantley S. L., Liermann L. J., Guynn R. L., Anbar A., Icopini G. A., and Barling J. (2004) Fe isotopic fractionation during mineral dissolution with and without bacteria. Geochim. Cosmochim. Acta68(15), 3189-3204]. Granite and basalts reacting with hydrochloric acid reached apparent steady-state values of −0.60 ± 0.15‰ and −0.40 ± 0.20‰, respectively, whilst experimental values with oxalic acid were −1.0 ± 0.15‰ and −0.50 ± 0.15‰. During the granite experiments, alteration of biotite to chlorite, followed by dissolution of chlorite, were likely the dominant processes, whilst in the basalt experiments, dissolution of pigeonite was likely the principal source of Fe. Variations in pH during the hydrochloric acid experiments were minimal, remaining below 0.5 at all times. In oxalic acid solutions, the pH increased to over 4, leading likely to precipitation of secondary minerals and adsorption/co-precipitation of Fe onto mineral surfaces. These processes could contribute to the greater fractionation observed in the final stages of the oxalic acid experiments. Our results highlight the importance of mineralogy and fluid composition on the Fe-isotope systematics during weathering. The fractionation processes identified for granites and basalts are in line with those inferred from field observations in soils, sediments, groundwater and hydrothermal deposits and from laboratory studies of single-mineral leaching.     

Solubility and speciation of sulfur in silicate melts: The Conjugated Toop-Samis-Flood-Grjotheim (CTSFG) model

A Conjugated Toop-Samis-Flood-Grjotheim (CTSFG) model is developed by combining the framework of the Toop-Samis polymeric approach with the Flood-Grjotheim theoretical treatment of silicate melts and slags. Electrically equivalent ion fractions are computed over the appropriate matrixes (anionic and cationic) in a Temkin notation for fused salts, and are used to weigh the contribution of the various disproportionation reactions of type:

     

Microheterogeneity of element distribution and sulfur speciation in an organic surface horizon of a forested Histosol as revealed by synchrotron-based X-ray spectromicroscopy

In recent years, the relevance of physico-chemical heterogeneity patterns in soils at the micron and submicron scale for the regulation of biogeochemical processes has become increasingly evident. For an organic surface soil horizon from a forested Histosol in Germany, microspatial patterns of element distribution (sulfur, phosphorus, aluminium, silicon) and S speciation were investigated by synchrotron-based X-ray spectromicroscopy. Microspatial patterns of S, P, Al and Si contents in the organic topsoil were assessed for a sample region of 50 μm × 30 μm by spatially resolving μ-XRF. Sulfur speciation at four microsites was investigated by focused X-ray absorption near edge structure (μ-XANES) spectroscopy at the S K-edge. The results show a heterogeneous distribution of the investigated elements on the (sub)micron scale, allowing the identification of diatoms, aluminosilicate mineral particles and sulfide minerals in the organic soil matrix. Evaluation of the S K-edge μ-XANES spectra acquired at four different microsites by linear combination fitting revealed a substantial microspatial heterogeneity of S speciation, characterized by the presence of distinct enrichment zones of inorganic sulfide and zones with dominant organic disulfide S within a few micrometers distance, and coexistence of different S species (e.g. reduced inorganic and organic S compounds) at a spatial scale below the resolution of the instrument (60 nm × 60 nm; X-ray penetration depth: 30 μm).     

Accelerated aqueous leaching of selenium and arsenic from coal associated rock samples with selenium speciation using ultrasound extraction

Ultrasound extraction was used to compare the accelerated release rates of selenium and arsenic from three rocks (BT700, BT 571 and BT 60) that are associated with mountaintop mining and valley fill coal mining practiced in southern parts of West Virginia, USA. The concentrations of arsenic released from rocks were found to be three orders of magnitude higher than that of selenium. The accelerated leaching rate constants were ten times higher for arsenic compared to selenium. Se (IV) was found to be stable under ultrasound extraction conditions used whereas As (III) was quickly oxidized to As (V). BT700 was found to have more Se (IV) compared to BT571 while BT60 did not have any significant Se (IV) concentrations. Such compositional and kinetic information becomes important when determining suitable mining waste treatment protocols that have to be undertaken to different types of overburden before it is dumped in valleys.     

Transformations of mercury, iron, and sulfur during the reductive dissolution of iron oxyhydroxide by sulfide

Methylmercury can accumulate in fish to concentrations unhealthy for humans and other predatory mammals. Most sources of mercury (Hg) emit inorganic species to the environment. Therefore, ecological harm occurs when inorganic Hg is converted to methylmercury. Sulfate- and iron-reducing bacteria (SRB and FeRB) methylate Hg, but the effects of processes involving oxidized and reduced forms of sulfur and iron on the reactivity of Hg, including the propensity of inorganic Hg to be methylated, are poorly understood. Under abiotic conditions, using a laboratory flow reactor, bisulfide (HS⁻) was added at 40 to 250 μM h⁻¹ to 5 g L⁻¹ goethite (α-FeOOH) suspensions to which Hg(II) was adsorbed (30-100 nmol m⁻²) at pH 7.5. Dissolved Hg initially decreased from 10³ or 10⁴ nM (depending on initial conditions) to 10⁻¹ nM, during which the concentration of Hg(II) adsorbed to goethite decreased by 80% and metacinnabar (β-HgS_(s)) formed, based on identification using Hg L_III-edge extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The apparent coordination of oxygens surrounding Hg(II), measured with EXAFS spectroscopy, increased during one flow experiment, suggesting desorption of monodentate-bound Hg(II) while bidentate-bound Hg(II) persisted on the goethite surface. Further sulfidation increased dissolved Hg concentrations by one to two orders of magnitude (0.5 to 10 nM or 30 nM), suggesting that byproducts of bisulfide oxidation and Fe(III) reduction, primarily polysulfide and potentially Fe(II), enhanced the dissolution of β-HgS_(s) and/or desorption of Hg(II). Rapid accumulation of Fe(II) in the solid phase (up to 40 μmol g⁻¹) coincided with faster elevation of dissolved Hg concentrations. Fe(II) served as a proxy for elemental sulfur [S(0)], as S(0) was the dominant bisulfide oxidation product coupled to Fe(III) reduction, based on sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy. In one experiment, dissolved Hg concentrations tracked those of all sulfide species [S(-II)]. These results suggest that S(-II) reacted with S(0) to form polysulfide, which then caused the dissolution of β-HgS_(s). A secondary Fe-bearing phase resembling poorly formed green rust was observed in sulfidized solids with scanning electron microscopy, although there was no clear evidence that either surface-bound or mineralized Fe(II) strongly affected Hg speciation. Examination of interrelated processes involving S(-II) and Fe(III) revealed new modes of Hg solubilization previously not considered in Hg reactivity models.