Arsenic mobility in alteration products of sulfide-rich, arsenopyrite-bearing mine wastes, Snow Lake, Manitoba, Canada

The Arsenopyrite Residue Stockpile (ARS) in Snow Lake, Manitoba contains approximately 250,000 tons of cyanide treated, refractory arsenopyrite ore concentrate. The residue was deposited between 1950 and 1959 in an open waste rock impoundment, and remained exposed until 2000, when the pile was capped with layers of waste rock and clay. During the time when the ARS was exposed to the atmosphere, arsenopyrite, pyrrhotite, pyrite and chalcopyrite were oxidized producing scorodite, jarosite and two generations of amorphous Fe sulfo-arsenates (AISA). These secondary phases attenuated some of the As released to pore water during oxidation in the upper layers of the ARS. The imposition of the cap prevented further oxidation. The secondary As minerals are not stable in the reduced environment that currently dominates the pile. Therefore, As currently is being released into the groundwater. Water in an adjacent monitoring well has concentrations of >20 mg/L total As with relative predominance of As(III).     

青海玛温根矿区氧化铅银矿工艺矿物学特性及分析研究

结合光学显微镜鉴定、扫描电镜、X射线能谱探针、筛析等技术手段,系统研究了青海省玛温根矿区产出的有代表性的氧化铅矿石的工艺矿物学特征。结果表明:矿石主要有价元素是Pb(2. 76%)和Ag(204. 4×10-6);矿石中铅的赋存状态较复杂,主要赋存于铅铁矾等难溶铅中,其次赋存于氧化铅、硫酸铅中,矿石中的铅矿物主要是铅矾、白铅矿、砷铅铁矾,少量方铅矿、砷铅矿等;银的赋存状态亦较为复杂,独立银矿物为硫铜银矿,含量甚微,部分银呈类质同像赋存于其他的金属硫化物中。通过偏光显微镜和扫描电镜分析发现,主要的铅矿物如铅矾、白铅矿等相互交代连生现象明显,且嵌布粒度细小,这与筛析检测结果相一致,同时矿石中As含量较高,达到了5. 43%,含砷矿物主要为毒砂、臭葱石,经X射线能谱分析,部分铅矿物与砷元素关系密切,并形成了砷铅铁矾、砷铅矿等复杂砷铅矿物。所以预测在选矿过程中,砷会随铅矿物同步富集,银的独立银矿物主要是硫铜银矿,且嵌布粒度微细,大部分银矿物以微细粒包裹态赋存于石英、褐铁矿等硅酸盐或氧化物中。根据以上研究成果,可判定该氧化铅银矿属于极难选矿石,建议采用浮选-化学选矿工艺综合回收铅、银金属的技术路线。     

Mineralogical controls on environmental mobility of arsenic from historic mine processing residues,New Zealand

Processing of arsenopyrite ore took place at Blackwater Au mine, New Zealand, between 1908 and 1951 and no rehabilitation was undertaken after mine closure. High As concentrations in solid processing residues (up to 40 wt% As) are due to secondary As minerals. Site pH regimes vary from 4.1 to circum-neutral. Originally, all processed As was present as arsenolite (arsenic trioxide polymorph, As^III), a by-product of arsenopyrite roasting. Near the roaster, scorodite precipitated as a result of the high dissolved As concentration during arsenolite dissolution. The formation of scorodite has two major consequences. Firstly, the scorodite precipitate cements the ground in the vicinity of the roaster area, thereby creating an impermeable surface crust (up to 30 wt% As) and encapsulating weathered arsenolite grains within the cement. Secondly, formation of scorodite temporarily immobilizes some of the dissolved As that is generated during nearby arsenolite dissolution. Where all the available arsenolite has dissolved, scorodite becomes soluble, and the dissolved As concentrations are controlled by scorodite solubility, which is at least two orders of magnitudes lower than arsenolite solubility. Downstream Eh conditions fall below the As^V/As^III boundary, so that scorodite does not precipitate and dissolved As concentrations are controlled by arsenolite solubility. Dissolved As reaches up to 52 mg/L in places, and exceeds the current WHO drinking water guideline of 0.01 mg/L by 5200 times. This study shows that dissolved As concentrations in discharge waters at historic mine sites are dependent on the processing technology and associated mineralogy.     

The role of arsenic-bearing rocks in groundwater pollution at Zimapán Valley, México

 Interaction of groundwater with As-bearing rocks has been proposed as one of three main sources of arsenic at Zimapán valley, México. The complexity of the geology and hydrogeology of the valley make it difficult to identify the natural causes of arsenic poisoning. Samples from the different rock outcrops and water from wells tapping various rock formations were analyzed. The rocks from mineralized areas contained higher concentrations of arsenic with respect to the same formations in non-mineralized areas. The arsenic minerals arsenopyrite, scorodite, and tennantite were identified in some rock samples. Higher temperature and lower Eh values were found for those wells containing more arsenic. The physicochemical characteristics of these naturally polluted well waters could be produced by arsenopyrite oxidation. The geochemical model PHREEQCI was used to perform the inverse modeling of two wells located along the same fault. Arsenopyrite oxidation and scorodite dissolution appear to be the geochemical processes producing the natural pollution according to the model. The release and transport of arsenic mainly occur through fractures within the cretaceous limestones where the most productive wells are drilled. The presence of arsenic should be expected also in other formations near mineralized zones in the Zimapán Valley. Field determinations of Eh and T could be used to detect potentially polluted wells. Received: 29 April 1999 / Accepted: 18 July 2000     

Solubility of nanocrystalline scorodite and amorphous ferric arsenate: Implications for stabilization of arsenic in mine wastes

Solubility experiments were performed on nanocrystalline scorodite and amorphous ferric arsenate. Nanocrystalline scorodite occurs as stubby prismatic crystals measuring about 50 nm and having a specific surface area of 39.88 ± 0.07 m²/g whereas ferric arsenate is amorphous and occurs as aggregated clusters measuring about 50–100 nm with a specific surface area of 17.95 ± 0.19 m²/g. Similar to its crystalline counterpart, nanocrystalline scorodite has a solubility of about 0.25 mg/L at around pH 3–4 but has increased solubilities at low and high pH (i.e. <2 and >6). Nanocrystalline scorodite dissolves incongruently at about pH > 2.5 whereas ferric arsenate dissolution is incongruent at all the pH ranges tested (pH 2–5). It appears that the solubility of scorodite is not influenced by particle size. The dissolution rate of nanocrystalline scorodite is 2.64 × 10⁻¹⁰ mol m⁻² s⁻¹ at pH 1 and 3.25 × 10⁻¹¹ mol m⁻² s⁻¹ at pH 2. These rates are 3–4 orders of magnitude slower than the oxidative dissolution of pyrite and 5 orders of magnitude slower than that of arsenopyrite. Ferric arsenate dissolution rates range from 6.14 × 10⁻⁹ mol m⁻² s⁻¹ at pH 2 to 1.66 × 10⁻⁹ mol m⁻² s⁻¹ at pH 5. Among the common As minerals, scorodite has the lowest solubility and dissolution rate. Whereas ferric arsenate is not a suitable compound for As control in mine effluents, nanocrystalline scorodite that can be easily precipitated at ambient pressure and temperature conditions would be satisfactory in meeting the regulatory guidelines at pH 3–4.     

Arsenic in contaminated soils and anthropogenic deposits at the Mokrsko,Roudný, and Kašperské Hory gold deposits,Bohemian Massif (CZ)

Soil, mine tailing, and waste dump profiles above three mesothermal gold deposits in the Bohemian Massif with different anthropogenic histories have been studied. Their mineralogical, major element, and arsenic (As) contents and the contents of secondary arsenic minerals were analyzed. The As-bearing minerals were concentrated and determined using X-ray diffraction (XRD) analysis, the Debye-Scherrer powder method, scanning electron microscopy (SEM), and energy-dispersive microanalysis (EDAX). The amorphous hydrous ferric oxides (HFO), As-bearing goethite, K-Ba- or Ca-Fe- and Fe- arsenates pharmacosiderite, arseniosiderite, and scorodite, and sulfate-arsenate pitticite were determined as products of arsenopyrite or arsenian pyrite oxidation. The As behaviour in the profiles studied differs in dependence on the surface morphology, chemical and mineralogical composition of the soil, mine wastes or tailings, oxidation conditions, pH, presence of (or distance from) primary As mineralization in the bedrock, and duration of the weathering effect. Although the primary As mineralization and the bedrock chemical composition are roughly similar, there are distinct differences in the As behaviour amongst the Mokrsko, Roudný and Kaperské Hory deposits.     

Trace element source terms for mineral dissolution

We present an approach for determining source terms for modeling trace element release from minerals, using arsenic (As) as an example. The source term function uses laboratory-measured mineral dissolution rates to predict the time rate of change of As concentrations (mol/L s) released to water by the dissolving mineral. Application of this function to As-bearing minerals (realgar, orpiment, arsenopyrite, scorodite, pyrite, and jarosite) in air saturated water at 25 °C shows that mineralogy, grain size and pH are important factors affecting the As source term while DO concentration and temperature are relatively unimportant for conditions found in typical aquifers. The derived function shows that the source term decreases as a function of (1 − t/t_L)², where t_L is the grain lifetime, due to the shrinkage of the mineral grains as they dissolve. For some models, either a constant or an instantaneous term might be used, provided that certain time constraints are met. The methods outlined in this paper are intended to help bridge the gap between laboratory measurements and field-based models. Although this paper uses As as an example, the methods are general and can be used to predict source terms for other mineral-derived trace elements to groundwater.     

Progressive oxidation of pyrite in five bituminous coal samples: An As XANES and Fe Mössbauer spectroscopic study

Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period of 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32–1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26–0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O₂ atmosphere; (3) room atmosphere (relative humidity ∼20–60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and ⁵⁷Fe Mössbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. ⁵⁷Fe Mössbauer spectroscopy also shows a much greater proportion of Fe³⁺ forms (jarosite, Fe³⁺ sulfate, FeOOH) for samples stored under wet conditions, but much less difference among samples stored under dry conditions in different atmospheres. The air-wet experiments show evidence of pyrite re-precipitation from soluble ferric sulfates, with As retention in the jarosite phase. Extents of As and Fe oxidation were similar for samples having differing As substitution in pyrite, suggesting that environmental conditions outweigh the composition and amount of pyrite as factors influencing the oxidation rate of Fe sulfides in coal.     

Arsenic distribution during formation and capping of an oxidised sulphidic minesoil, Macraes mine, New Zealand

A minesoil has developed over 5 years oxidative exposure on sulphide concentrate tailings (ca. 1 wt.% As) at the Macraes mesothermal gold mine, New Zealand. The minesoil has a dry crust which has formed due to evaporative drying. This dry crust is enriched in arsenic (ca. 5 wt.% As) as scorodite (FeAsO₄·2H₂O) because of upward mobility of dissolved arsenic during drying. Similar enrichment of arsenic has occurred along the walls of desiccation cracks which extend over 1 m into the minesoil. Capping of the tailings and minesoil with wet tailings (pH=8) results in dissolution of scorodite and remobilization of arsenic on the millimetre scale. Experimental capping of the minesoil with wet calcium carbonate remobilized some arsenic from scorodite on the centimetre scale, but much original arsenic enrichment was preserved after 400 days. A layer of gypsum (CaSO₄·2H₂O) and iron oxyhydroxide cementation developed at the interface between the minesoil and the experimental calcium carbonate cap, restricting water flow. This layer was ca. 1 mm thick after 400 days. Theoretical comparison between advection and diffusion in the minesoil suggests that diffusion is an important mechanism for chemical mobility on the 1–50-year time scale. However, advection can be important in secondary porosity of the dry crust of the minesoil and water penetrates this zone at a rate of 1.5 mm/day.     

An integrated geophysical study of arsenic contaminated area in the peninsular Thailand

Geophysical surveys were carried out in an arsenic contaminated area, in the Ron Phibun District in southern Thailand. Here, tin and associated minerals, i.e. arsenopyrite and pyrite, have been extracted from granites and natural processes and the mining activities led to arsenic contamination in the environment. Electrical resistivity and self-potential (SP) were used to define the distribution of arsenic contamination in the groundwater. Resistivities of 25–100 Ωm and a positive SP anomaly of 66.0 mV were observed in an area where the arsenic content in auger water at 3.5–5.0 m depths was high, 0.5–5.0 mg/l. Integrated interpretation of resistivity, seismic refraction, GPR and gravity data gave a clear image of subsurface shallow structures (< 30 m depths). There was a good correlation between the resistivity and the gravity data. A subsurface rise was found, which possibly acts as a naturally buried dam, separating a high-contaminated area from a low contaminated area.     

Arsenic speciation in pyrite and secondary weathering phases,Mother Lode Gold District,Tuolumne County,California

Arsenian pyrite, formed during Cretaceous gold mineralization, is the primary source of As along the Melones fault zone in the southern Mother Lode Gold District of California. Mine tailings and associated weathering products from partially submerged inactive gold mines at Don Pedro Reservoir, on the Tuolumne River, contain ∼20–1300 ppm As. The highest concentrations are in weathering crusts from the Clio mine and nearby outcrops which contain goethite or jarosite. As is concentrated up to 2150 ppm in the fine-grained (<63 μm) fraction of these Fe-rich weathering products.Individual pyrite grains in albite-chlorite schists of the Clio mine tailings contain an average of 1.2 wt.% As. Pyrite grains are coarsely zoned, with local As concentrations ranging from ∼0 to 5 wt.%. Electron microprobe, transmission electron microscope, and extended X-ray absorption fine-structure spectroscopy (EXAFS) analyses indicate that As substitutes for S in pyrite and is not present as inclusions of arsenopyrite or other As-bearing phases. Comparison with simulated EXAFS spectra demonstrates that As atoms are locally clustered in the pyrite lattice and that the unit cell of arsenian pyrite is expanded by ∼2.6% relative to pure pyrite. During weathering, clustered substitution of As into pyrite may be responsible for accelerating oxidation, hydrolysis, and dissolution of arsenian pyrite relative to pure pyrite in weathered tailings. Arsenic K-edge EXAFS analysis of the fine-grained Fe-rich weathering products are consistent with corner-sharing between As(V) tetrahedra and Fe(III)-octahedra. Determinations of nearest-neighbor distances and atomic identities, generated from least-squares fitting algorithms to spectral data, indicate that arsenate tetrahedra are sorbed on goethite mineral surfaces but substitute for SO₄ in jarosite. Erosional transport of As-bearing goethite and jarosite to Don Pedro Reservoir increases the potential for As mobility and bioavailability by desorption or dissolution. Both the substrate minerals and dissolved As species are expected to respond to seasonal changes in lake chemistry caused by thermal stratification and turnover within the monomictic Don Pedro Reservoir. Arsenic is predicted to be most bioavailable and toxic in the reservoir’s summer hypolimnion.     

Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As−1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O₂), hypoxic (2% O₂, 98% N₂), and anoxic (5% H₂, 95% N₂) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (−1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations.     

紫木凼金矿床载金矿物及金的赋存状态

紫木凼金矿床主要载金矿物为含砷黄铁矿和毒砂,氧化矿石中,金呈显微粒状自然金－显微金嵌布于褐铁矿,石英水云母,方解石的颗粒间或孔隙中,原生矿石中,金主要呈次显微粒自然金－次显微金包裹体,其次是类质同像形式赋存在含砷黄铁矿和毒砂矿物中。     

Mineralogy and environmental geochemistry of historical iron slag,Hopewell Furnace National Historic Site,Pennsylvania, USA

The Hopewell Furnace National Historic Site in southeastern Pennsylvania, which features an Fe smelter that was operational in the 18th and 19th centuries, is dominated by three slag piles. Pile 1 slag, from the Hopewell Furnace, and pile 2 slag, likely from the nearby Cornwall Furnace, were both produced in cold-blast charcoal-fired smelters. In contrast, pile 3 slag was produced in an anthracite furnace. Ore samples from the nearby Jones and Hopewell mines that fed the smelter are mainly magnetite-rich with some sulfides (pyrite, chalcopyrite, sphalerite) and accessory silicates (quartz, garnet, feldspar, and clay minerals). Slag piles 1 and 2 are similar mineralogically containing predominantly skeletal and dendritic aluminian diopside and augite, skeletal forsteritic olivine, glass, rounded blebs of metallic Fe, and exotic quartz. Olivine is a major phase in all samples from pile 2, whereas it occurs in only a few samples from pile 1. Samples of the <2 mm-size fraction of surface composite slag material or crushed slag from at depth in piles 1 and 2 are mineralogically similar to the large surface slag fragments from those piles with the addition of phases such as feldspars, Fe oxides, and clay minerals that are either secondary weathering products or entrained from the underlying bedrock. Pile 3 slag contains mostly skeletal forsteritic olivine and Ti-bearing aluminian diopside, dendritic or fine-grained subhedral melilite, glass, euhedral spinel, metallic Fe, alabandite–oldhamite solid solution, as well as a sparse Ti carbonitride phase. The bulk chemistry of the slag is dominated by Al₂O₃ (8.5–16.2 wt.%), CaO (8.2–26.2 wt.%), MgO (4.2–24.7 wt.%), and SiO₂ (36.4–59.8 wt.%), constituting between 81% and 97% of the mass of the samples. Piles 1 and 2 are chemically similar; pile 1 slag overall contains the highest Fe₂O₃, K₂O and MnO, and the lowest MgO concentrations. Pile 3 slag is high in Al₂O₃, CaO and S, and low in Fe₂O₃, K₂O and SiO₂ compared to the other piles. In general, piles 1 and 2 are chemically similar to each other, whereas pile 3 is distinct – a conclusion that reflects their mineralogy. The similarities and differences among piles in terms of mineralogy and major element chemistry result from the different smelting conditions under which the slag formed and include the fuel source, the composition of the ore and flux, the type of blast (cold versus hot), which affects the furnace temperature, and other beneficiation methods.     

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop—Zones A–C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite–smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.     

Legacy of the California Gold Rush: Environmental Geochemistry of Arsenic in the Southern Mother Lode Gold District

Gold mining activity in the Sierra Nevada foothills, both recently and during the California Gold Rush, has exposed arsenic-rich pyritic rocks to weathering and erosion. This study describes arsenic concentration and speciation in three hydrogeologic settings in the southern Mother Lode Gold District: mineralized outcrops and mine waste rock (overburden); mill tailings submerged in a water reservoir; and lake waters in this monomictic reservoir and in a monomictic lake developing within a recent open-pit mine. These environments are characterized by distinct modes of rock-water interaction that influence the local transport and fate of arsenic. Arsenic in outcrops and waste rock occurs in arsenian pyrite containing an average of 2 wt% arsenic. Arsenic is concentrated up to 1300 ppm in fine-grained, friable, iron-rich weathering products of the arsenian pyrite (goethite, jarosite, copiapite), which develop as efflorescences and crusts on weathering outcrops. Arsenic is sorbed as a bidentate complex on goethite, and substitutes for sulfate in jarosite.

Submerged mill tailings obtained by gravity core at Don Pedro Reservoir contain arsenic up to 300 ppm in coarse sand layers. Overlying surface muds have less arsenic in the solid fraction but higher concentrations in porewaters (up to 500 μg/L) than the sands. Fine quartz tailings also contain up to 3.5 ppm mercury related to the ore processing. The pH values in sediment porewaters range from 3.7 in buried gypsum-bearing sands and tailings to 7 in the overlying lake sediments. Reservoir waters immediately above the cores contain up to 3.5 μg/L arsenic; lake waters away from the submerged tailings typically contain less than 1 μg/L arsenic.

Dewatering during excavation of the Harvard open-pit mine produced a hydrologic cone of depression that has been recovering toward the pre-mining groundwater configuration since mining ended in 1994. Aqueous arsenic concentrations in the 80 m deep pit lake are up to 1000 μg/L. Redistribution of the arsenic occurs during summer stratification, with highest concentrations at middle depths. The total mass of arsenic in the pit lake increases coinciding with early winter rains that erode, partially dissolve, and transport arsenic-bearing salts into the pit lake.

Arsenic concentration, speciation, and distribution in the Sierra Nevada foothills depend on many factors, including the lithologic sources of arsenic, climatic influences on weathering of host minerals, and geochemical characteristics of waters with which source and secondary minerals react. Oxidation of arsenian pyrite to goethite, jarosite, and copiapite causes temporary attenuation of arsenic during summer, when these secondary minerals accumulate; subsequent rapid dissemination of arsenic into the aqueous environment is caused by annual winter storms. As the population of the Mother Lode area grows, it is increasingly important to consider these effects during planning and development of land and groundwater resources.     

Lithogeochemical localisation of disseminated gold in the White River area, Yukon, Canada

Gold mineralisation in the White River area, 80 km south of the highly productive Klondike alluvial goldfield, is hosted in amphibolite facies gneisses in the same Permian metamorphic pile as the basement for the Klondike goldfield. Hydrothermal fluid which introduced the gold was controlled by fracture systems associated with middle Cretaceous to early Tertiary extensional faults. Gold deposition occurred where highly fractured and chemically reactive rocks allowed intense water–rock interaction and hydrothermal alteration, with only minor development of quartz veins. Felsic gneisses were sericitised with recrystallisation of hematite and minor arsenic mobility, and extensively pyritised zones contain gold and minor arsenic (ca 10 ppm). Graphitic quartzites (up to 5 wt.% carbon) caused chemical reduction of mineralising fluids, with associated recrystallisation of metamorphic minerals (graphite, pyrrhotite, pyrite, chalcopyrite) in host rocks and veins, and introduction of arsenic (up to 1 wt.%) to form arsenopyrite in veins and disseminated through host rock. Veins have little or no hydrothermal quartz, and up to 19 wt.% carbon as graphite. Late-stage oxidation of arsenopyrite in some graphitic veins has formed pharmacosiderite. Gold is closely associated with disseminated and vein sulphides in these two rock types, with grades of up to 3 ppm on the metre scale. Other rock types in the White River basement rocks, including biotite gneiss, hornblende gneiss, pyroxenite, and serpentinite, have not developed through-going fracture systems because of their individual mineralogical and rheological characteristics, and hence have been little hydrothermally altered themselves, have little hydrothermal gold, and have restricted flow of fluids through the rock mass. Some small post-metamorphic quartz veins (metre scale) have been intensely fractured and contain abundant gold on fractures (up to 40 ppm), but these are volumetrically minor. The style of gold mineralisation in the White River area is younger than, and distinctly different from, that of the Klondike area. Some of the mineralised zones in the White River area resemble, mineralogically and geochemically, nearby coeval igneous-hosted gold deposits, but this resemblance is superficial only. The White River mineralisation is an entirely new style of Yukon gold deposit, in which host rocks control the mineralogy and geochemistry of disseminated gold, without quartz veins.     

秦岭卡林型金矿床金、砷地球化学探讨

讨论了秦岭卡林型金矿床中Ａｕ 、Ａｓ 的元素地球化学、矿物学特征。在含矿岩系中获得的Ａｕ、Ａｓ 等成矿元素初始含量较高,且主要集中在成岩黄铁矿中。在矿石样品中对含砷硫化物矿物的研究表明,Ａｕ 、Ａｓ 在矿物显微结构中具有强的正相关性。在大量金进入到硫化物结构之前,就已有［ＡｓＳ］３ － 的存在。在含砷硫化物矿物中,金多半以一种带电类型（Ａｕ３ ＋） 存在, 它很可能替代铁位置上的过剩砷, 以固溶体方式沉淀于硫化物矿物中。此时, 黄铁矿构成（Ａｕ３ ＋ ,Ｆｅ２ ＋）（［ＡｓＳ］３ － ［Ｓ２］２ － ）,毒砂构成（Ａｕ３ ＋ ,Ｆｅ２ ＋）（［ＡｓＳ］３ － ［ＡｓＳ］３ －） 。通过电子探针（ＥＭＰ） 和透射电镜（ＴＥＭ） 对秦岭卡林型金矿含砷硫化物矿物中金的赋存状态的研究表明,在金的成矿作用早期阶段, 金主要以固溶体形式优先富集于含砷黄铁矿和毒砂及砷黝铜矿之中,并且认为是以金的氧化和砷的还原的共沉淀方式发生的。在此之后的金成矿作用晚期阶段,由于热液蚀变和结晶作用程度的增高,寄主矿物耐熔性质相对降低,加之金本身的聚集能力,和因过量砷加入而造成的含砷硫化物矿物的晶格缺陷,致使已形成的固溶体金以“出溶”形式发生再分布,赋存于硫化物矿物晶粒     

Aggregation and Differentiation of Gold and Silver during the Formation of the Gold-Bearing Weathering Crusts (on the Example of Kazakhstan Deposits)

The supergene Au in weathering crusts of both the Suzdal and Raygorodok deposits is characterized by enhanced fineness, grain size, crystallinity, and the appearance of botryoidal aggregates of crystals. In the weathering crust of the Suzdal deposit, the exogenous Au is associated primarily with scorodite and carbonates; for Raygorodok, with chalcocite, bornite, hydrocarbonates and Cu hydrosulfates. The difference in the mineral associations of supergene Au at the deposits is determined by the occurrence of various mineral concentrators of Au in the primary endogenous substrate: arsenopyrite and pyrite at the Suzdal deposit and chalcopyrite with pyrite at the Raygorodok deposit. Due to the much greater mobility of Ag in the supergene zone, the weathering crusts are likely to contain submicron microinclusions of Ag minerals beyond the zones of Au concentration.     

Kinetics of arsenopyrite oxidative dissolution by oxygen

We used a mixed flow reactor system to determine the rate and infer a mechanism for arsenopyrite (FeAsS) oxidation by dissolved oxygen (DO) at 25 °C and circumneutral pH. Results indicate that under circumneutral pH (6.3-6.7), the rate of arsenopyrite oxidation, 10^{−10.14±0.03} mol m⁻² s⁻¹, is essentially independent of DO over the geologically significant range of 0.3-17 mg L⁻¹. Arsenic and sulfur are released from arsenopyrite in an approximate 1:1 molar ratio, suggesting that oxidative dissolution by oxygen under circumneutral pH is congruent. Slower rates of iron release from the reactor indicate that some of the iron is lost from the effluent by oxidation to Fe(III) which subsequently hydrolyzes and precipitates. Using the electrochemical cell model for understanding sulfide oxidation, our results suggest that the rate-determining step in arsenopyrite oxidation is the reduction of water at the anodic site rather than the transfer of electrons from the cathodic site to oxygen as has been suggested for other sulfide minerals such as pyrite.