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.     

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.     

Arsenic and metal mobility from Au mine tailings in Rodalquilar (Almería,SE Spain)

In the old mining area of Rodalquilar, mine wastes, soil and sediments were characterized and the results revealed high concentration of Au, Ag, As, Bi, Cu, Fe, Mn, Pb, Se, Sb and Zn in tailings and sediments. The contaminant of greatest environmental concern is As. The mean concentration in the tailings was 679.9, and 345 mg/kg in the sediments of Playazo creek. The groundwater samples from the alluvial aquifer showed high concentration of Al, As, Cd, Fe, Hg, Mn, Ni, Pb, Se, Sb and Zn and very high concentration of chloride and sulfate, which were above the concentration defined in the European standards for drinking water. The presence of As in groundwater may be caused by the oxidation of arsenian pyrite, the possible As desorption from goethite and ferrihydrite and the jarosite dissolution. Groundwater concentrations of Cd, Fe, Mn, and possibly Cu, were associated with low values of Eh, indicating the possible dissolution of oxy-hydroxides of Fe and Mn. The mobility of metals in the column experiments show the release of Al, Fe, Mn, Cr, Cu, Ni, V and Zn in significant concentrations but below the detected values in groundwater. However, As, Cd, Sb, Se Pb and Au, are generally mobilized in concentrations above the detected values in groundwater. The possible mass transfer processes that could explain the presence of the contaminants in the aquifer and the leachates was simulated with the PHREEQC numerical code and revealed the possible dissolution of the following mineral phases: jarosite, natrojarosite, arsenian pyrite, alunite, chlorite, kaolinite and calcite.     

Source and distribution of naturally occurring arsenic in groundwater from Alberta’s Southern Oil Sands Regions

Arsenic (As) concentrations as high as 179 μg/L have been observed in shallow groundwater in the Alberta’s Southern Oil Sand Regions. The geology of this area of Alberta includes a thick cover (up to 200 m) of unconsolidated glacial deposits, with a number of regional interglacial sand and gravel aquifers, underlain by marine shale. Arsenic concentrations observed in 216 unconsolidated sediment samples ranged from 1 and 17 ppm. A survey of over 800 water wells sampled for As in the area found that 50% of the wells contained As concentrations exceeding drinking water guidelines of 10 μg/L. Higher As concentrations in groundwater were associated with reducing conditions. Measurements of As speciation from 175 groundwater samples indicate that As(III) was the dominant species in 74% of the wells. Speciation model calculations showed that the majority of groundwater samples were undersaturated with respect to ferrihydrite, suggesting that reductive dissolution of Fe-oxyhydroxides may be the source of some As in groundwater. Detailed mineralogical characterization of sediment samples collected from two formations revealed the presence of fresh framboidal pyrite in the deeper unoxidized sediments. Electron microprobe analysis employing wavelength dispersive spectrometry indicated that the framboidal pyrite had variable As content with an average As concentration of 530 ppm, reaching up to 1840 ppm. In contrast, the oxidized sediments did not contain framboidal pyrite, but exhibited spheroidal Fe-oxyhydroxide grains with elevated As concentrations. The habit and composition suggest that these Fe-oxyhydroxide grains in the oxidized sediment were an alteration product of former framboidal pyrite grains. X-ray absorption near edge spectroscopy (XANES) indicated that the oxidized sediments are dominated by As(V) species having spectral features similar to those of goethite or ferrihydrite with adsorbed As, suggesting that Fe-oxyhydroxides are the dominant As carriers. XANES spectra collected on unoxidized sediment samples, in contrast, indicated the presence of a reduced As species (As(−I)) characteristic of arsenopyrite and arsenian pyrite. The results of the mineralogical analyses indicate that the oxidation of framboidal pyrite during weathering may be the source of As released to shallow aquifers in this region.     

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.     

Mobilization of arsenic from mine tailings through reductive dissolution of goethite influenced by organic cover

Mine tailings at the former Delnite gold mine in northern Ontario were characterized to assess the impact of a biosolids cover on the stability of As species and evaluate options for long-term management of the tailings. Arsenic concentrations in the tailings range from 0.15 to 0.36 wt% distributed among goethite, pyrite and arsenopyrite. Pyrite and arsenopyrite occur as small and liberated particles that are enveloped by goethite in the uncovered tailings and the deeper portions of the biosolids-covered tailings. Sulfide particles in the shallower portions of the biosolids-covered tailings are free of goethite rims. Arsenic occurs predominantly as As⁵⁺ with minor amount of As¹⁻ in the uncovered tailings. Coinciding with the disappearence of goethite rims on sulfide particles, the biosolids-covered tailings have As³⁺ species gradually increasing in proportion towards the cover. Leaching tests indicated that the As concentrations in the leachate gradually increase from less than 0.085 to 13 mg/L and Fe from 28 to 179 mg/L towards the biosolids cover. These are in sheer contrast to the leachate concentrations of less than 0.085 mg/L As and 24–64 mg/L Fe obtained from the uncovered tailings confirming the role of biosolids-influenced reduction and mobilization of As in the form of As³⁺ species. The evidence suggests that reductive dissolution of goethite influenced by the biosolids-cover caused the mobilization of As as As³⁺ species.     

Arsenic in iron cements developed within tailings of a former metalliferous mine—Enguialès,Aveyron, France

Arsenopyrite-rich waste from a former metalliferous mine were spread out over the sloping side of a deep valley after processing. Over the past 30 a, they have been subjected to rainfall and acid water originating from the abandoned mine galleries. This intensive leaching has led to the formation of thin layers of As–Fe crusts on the tailings surface acting as a cement. X-ray diffraction and SEM coupled with EDS determined that jarosite was present in all mineral samples and could contain a small amount of As (∼5.7 wt.%). In addition EMPA and Raman microspectroscopy characterised the presence of amorphous As(V) Fe hydrates as well as rare arsenate minerals (e.g. scorodite). Raman microspectroscopy in particular identified a preponderance of goethite or hematite within the mineral framework of the tailings materials that is likely to sorb recalcitrant As species. The characterisation of the components of the tailings enable the identification of their evolution, shows the progressive decrease of their As-content and emphasises the consequences of the temporary trapping of As in the very acidic and oxidising conditions prevailing in such environments. Resinous amorphous material was identified as the richest in As with As ∼17.1 wt.%. This material evolved toward more crystallised phases (e.g. goethite, jarosite) which contained less As (3.2 wt.%<As <5.7 wt.%). Paragenesis showed the progressive release of As with the crystallisation evolution of the As-trapping material.     

Formation and composition of cemented layers in low-sulphide mine tailings, Laver, northern Sweden

Cemented layers (hardpans) are common in carbonate or sulphide-rich mine tailings and where pyrrhotite is the predominating Fe-sulphide. Laver, northern Sweden, is an abandoned Cu-mine where the tailings have low pyrrhotite content, almost no pyrite and no carbonates. Two cemented layers at different locations in the Laver tailings impoundment were investigated, with the aim to determine their effects on metal mobility. The cementing agents were mainly jarosite and Fe-oxyhydroxides in the layer formed where the tailings have a barren surface, whereas only Fe-oxyhydroxides were identified below grass-covered tailings surface. Arsenic was enriched in both layers which also exhibit high concentrations of Mo, V, Hg and Pb compared to unoxidised tailings. Sequential extraction indicates that these metals and As were mainly retained with crystalline Fe-oxides, and therefore potentially will be remobilised if the oxic conditions become more reducing, for instance as a result of remediation of the tailings impoundment.An erratum to this article can be found at     

Geochemical and mineralogical control on the mobility of arsenic in a waste rock pile at Dlouhá Ves,Czech Republic

A waste rock pile with initial high sulfide (10–20 wt.%) and low carbonate content (1–2 wt.%) located at Dlouhá Ves in the Czech Republic has been investigated in two profiles (excavation and outcrop) using powder X-ray diffraction, electron microprobe analysis, bulk composition analysis and Mössbauer spectroscopy. The mobility of arsenic and other contaminants was evaluated by leaching experiments. The primary source of the arsenic was arsenopyrite, which was significantly oxidized in both profiles. The principal As-bearing phase at the excavation profile was goethite, located at the top of the profile, and minerals of the jarosite group which were found down to its base. Melanterite, rich in copper and zinc, was found in a sulfide-rich, lower part of the profile together with anglesite. At the outcrop profile, minerals of the jarosite–beudantite group, scorodite and kaňkite prevail and no Fe(II)-minerals were found. The paste pH was lower at the excavation profile (minimum about 1.9) than at the outcrop profile (minimum of about 2.8). Processes in the pile are affected by the pyrite/arsenopyrite ratio, where high pyrite content decreases the As/S ratio and results in the formation of jarosite group minerals and low pH conditions. Where arsenopyrite predominates, sulphides are coated by scorodite and other Fe–As phases like schwertmannite, which limit their further oxidation.     

Mineralogy and geochemistry of alluvium contaminated by metal mining in the Rio Tinto area, southwest Spain

The Rio Tinto in SW Spain drains Cu and pyrite mines which have been in operation since at least the Bronze Age. Extensive metal mining, especially from 1873 to 1954, has resulted in contamination of the Rio Tinto alluvium with As, Cu, Pb, Ag and Zn. X-ray diffraction (XRD), wavelength-dispersive X-ray mapping, scanning electron microscope petrography and X-ray energy-dispersive (EDX) analysis has revealed that 4 major groups of contaminant metal and As-bearing minerals, including sulphides, Fe-As oxides, Fe oxides/hydroxides/oxyhydroxides, and Fe oxyhydroxysulphates, occur in the alluvium. Sulphide minerals, including pyrite, chalcopyrite, arsenopyrite and sphalerite, occur in alluvium near the mining areas. Iron hydroxides and oxyhydroxides such as goethite and possibly ferrihydrite occur in cements in both the mining areas and alluvium downstream, and carry minor amounts of As, Cu and Zn. Iron oxyhydroxysulphates, including jarosite, plumbojarosite and possibly schwertmannite, are the most common minerals in alluvium downstream of the mining areas, and are major hosts of Cu, Pb, Zn and of As, next to the Fe-As minerals. This work, and other field observations, suggest that (1) the extreme acidity and elevated metal concentrations of the river water will probably be maintained for some time due to oxidation of pyrite and other sulphides in the alluvium and mine-waste tips, and from formation of secondary oxide and oxyhydroxysulphates; (2) soluble Fe oxyhydroxysulphates such as copiapite, which form on the alluvium, are a temporary store of contaminant metals, but are dissolved during periods of high rainfall or flooding, releasing contaminants to the aqueous system; (3) relatively insoluble Fe oxyhydroxysulphates and hydroxides such as jarosite and goethite may be the major long-term store of alluvial contaminant metals; and (4) raising river pH will probably cause precipitation of Fe oxyhydroxides and oxides/hydroxides/oxyhydroxides and thus have a positive effect on water quality, but this action may destabilise some of these contaminant metal-bearing minerals, releasing metals back to the aqueous system.     

Arsenic and iron speciation in uranium mine tailings using X-ray absorption spectroscopy

In northern Saskatchewan, Canada, high-grade U ores and the resulting tailings can contain high levels of As. An environmental concern in the U mining industry is the long-term stability of As within tailings management facilities (TMFs) and its potential transfer to the surrounding groundwater. To mitigate this problem, U mill effluents are neutralized with lime to reduce the aqueous concentration of As. This results in the formation of predominantly Fe³⁺–As⁵⁺ secondary mineral phases, which act as solubility controls on the As in the tailings discharged to the TMF. Because the speciation of As in natural systems is critical for determining its long-term environmental fate, characterization of As-bearing mineral phases and complexes within the deposited tailings is required to evaluate its potential transformation, solubility, and long-term stability within the tailings mass. In this study, synchrotron-based bulk X-ray absorption spectroscopy (XAS) was used to study the speciation of As and Fe in mine tailings samples obtained from the Deilmann TMF at Key Lake, Saskatchewan. Comparisons of K-edge X-ray absorption spectra of tailings samples and reference compounds indicate the dominant oxidation states of As and Fe in the mine tailings samples are +5 and +3, respectively, largely reflecting their generation in a highly oxic mill process, deposition in an oxidized environment, and complexation within stable oxic phases. Linear combination fit analyses of the K-edges for the Fe X-ray absorption near edge spectra (XANES) to reference compounds suggest Fe is predominantly present as ferrihydrite with some amount of the primary minerals pyrite (8–15% in some samples) and chalcopyrite (5–15% in some samples). Extended X-ray absorption fine structure (EXAFS) analysis of As K-edge spectra indicates that As⁵⁺ (arsenate) present in tailings samples is adsorbed to the ferrihydrite though an inner-sphere bidentate linkage.     

Mineralogy and geochemistry of gold-bearing arsenian pyrite from the Shuiyindong Carlin-type gold deposit, Guizhou, China: implications for gold depositional processes

Arsenian pyrite in the Shuiyindong Carlin-type gold deposit in Guizhou, China, is the major host for gold with 300 to 4,000 ppm Au and 0.65 to 14.1 wt.% As. Electron miroprobe data show a negative correlation of As and S in arsenian pyrite, which is consistent with the substitution of As for S in the pyrite structure. The relatively homogeneous distribution of gold in arsenian pyrite and a positive correlation of As and Au, with Au/As ratios below the solubility limit of gold in arsenian pyrite, suggest that invisible gold is likely present as Au¹⁺ in a structurally bound Au complex in arsenian pyrite. Geochemical modeling using the laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis of fluid inclusions for the major ore forming stage shows that the dominant Au species were Au(HS)₂⁻ (77%) and AuHS_(aq)⁰ (23%). Gold-hydroxyl and Gold-chloride complexes were negligible. The ore fluid was undersaturated with respect to native Au, with a saturation index of −3.8. The predominant As species was H₃AsO₃⁰ _(aq). Pyrite in the Shuiyindong deposit shows chemical zonation with rims richer in As and Au than cores, reflecting the chemical evolution of the ore-bearing fluids. The early ore fluids had relatively high activities of As and Au, to deposit unzoned and zoned arsenian pyrite that host most gold in the deposit. The ore fluids then became depleted in Au and As and formed As-poor pyrite overgrowth rims on gold-bearing arsenian pyrite. Arsenopyrite overgrowth aggregates on arsenian pyrite indicate a late fluid with relatively high activity of As. The lack of evidence of boiling and the low iron content of fluid inclusions in quartz, suggest that iron in arsenian pyrite was most likely derived from dissolution of ferroan minerals in the host rocks, with sulfidation of the dissolved iron by H₂S-rich ore fluids being the most important mechanism of gold deposition in the Shuiyindong Carlin-type deposit.     

Mobilization and attenuation of heavy metals within a nickel mine tailings impoundment near Sudbury, Ontario, Canada

 The oxidation and the subsequent dissolution of sulfide minerals within the Copper Cliff tailings area have led to the release of heavy metals such as Fe, Ni, and Co to the tailings pore water. Dissolved concentrations in excess of 10 g/l Fe and 2.2 g/l Ni have been detected within the shallow pore water of the tailings, with increasing depth these concentrations decrease to or near analytical detection limits. Geochemical modelling of the pore-water chemistry suggests that pH-buffering reactions are occurring within the shallow oxidized zones, and that secondary phases are precipitating at or near the underlying hardpan and transition zones. Mineralogical study of the tailings confirmed the presence of goethite, jarosite, gypsum, native sulfur, and a vermiculite-type clay mineral. Goethite, jarosite, and native sulfur form alteration rims and pseudo-morphs of the sulfide minerals. Interstitial cements, composed of goethite, jarosite, and gypsum, locally bind the tailings particles, forming hardpan layers. Microprobe analyses of the goethite indicate that it contains up to 0.6 weight % Ni, suggesting that the goethite is a repository for Ni. Other sinks detected for heavy metals include jarosite and a vemiculite-type clay mineral which locally contains up to 1.6 weight % Ni. To estimate the mass and distribution of heavy metals associated with the secondary phases within the shallow tailings, a series of chemical extractions was completed. The experimental design permitted four fractions of the tailings to be evaluated independently. These four fractions consisted of a water-soluble, an acid-leachable, and a reducible fraction, as well as the whole-rock total. Twenty-five percent of the total mass of heavy metals was removed in the acid-leaching experiments, and 100% of the same components were removed in the reduction experiments. The data suggest that precipitation/coprecipitation reactions are providing an effective sink for most of the heavy metals released by sulfide mineral oxidation. In light of these results, potential decommissioning strategies should be evaluated with the recognition that changing the geochemical conditions may alter the stability of the secondary phases within the shallow tailings. Received: 9 April 1997 · Accepted: 21 July 1997     

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.     

An attempt to use LA-ICP-SMS to quantify enrichment of trace elements on pyrite surfaces in oxidizing mine tailings

Metals released from oxidation and weathering of sulphide minerals in mine tailings are to a high degree retained at deeper levels within the tailings themselves. To be able to predict what could happen in the future with these secondarily retained metals, it is important to understand the retention mechanisms. In this study an attempt to use laser ablation high-resolution ICP-MS (LA-ICP-SMS) to quantify enrichment of trace elements on pyrite surfaces in mine tailings was performed. Pyrite grains were collected from a profile through the pyrite-rich tailings at the Kristineberg mine in northern Sweden. At each spot hit by the laser, the surface layer was analyzed in the first shot, and a second shot on the same spot gave the chemical composition of the pyrite immediately below. The crater diameter for a laser shot was known, and by estimating the crater depth and total pyrite surface, the total enrichment on pyrite grains was calculated. Results are presented for As, Cd, Co, Cu, Ni and Zn. The results clearly show that there was an enrichment of As, Cd, Cu and Zn on the pyrite surfaces below the oxidation front in the tailings, but not of Co and Ni. Arsenic was also enriched on the pyrite grains that survived in the oxidized zone. Copper has been enriched on pyrite surfaces in unoxidized tailings in the largest amount, followed by Zn and As. However, only 1.4 to 3.1% of the Cd and Zn released by sulphide oxidation in the oxidized zone have been enriched on the pyrite surfaces in the unoxidized tailings, but for As and Cu corresponding figures are about 64 and 43%, respectively. There were many uncertainties in these calculations, and the results shall not be taken too literally but allowed the conclusion that enrichment on pyrite surfaces is an important process for retention of As and Cu below the oxidation front in pyrite rich tailings. Laser ablation is not a surface analysis technique, but more of a thin layer method, and gives no information on the type of processes resulting in enrichment on the pyrite surfaces. Although only pyrite grains that appeared to be fresh and without surface coatings were used in this study, the possibility that a thin layer of Fe-hydroxides occurred must be considered. Both adsorption to the pyrite directly or to Fe-oxyhydroxides may explain the enrichment of As, Cd, Cu and Zn on the pyrite surfaces, and, in the case of Cu, also the replacement of Fe(II) by Cu(II) in pyrite.     

Mineralogical profiling of alluvial sediments from arsenic-affected Ganges-Brahmaputra floodplain in central Bangladesh

Mineral assemblages (heavy and light fractions) and sedimentological characteristics of the Quaternary alluvial aquifers were examined in the central Bengal Basin where As concentrations in groundwater are highly variable in space but generally decrease downward. Chemical compositions of sediment samples from two vertical core profiles (2-150 m below ground level, bgl) were analyzed along with groundwater in moderately As-enriched aquifers in central Bangladesh (Manikganj district), and the As mobilization process in the alluvial aquifer is described. Heavy minerals such as biotite, magnetite, amphibole, apatite and authigenic goethite are abundant at shallow (<100 m below ground level (mbgl)) depths but less abundant at greater depths. It is interpreted that principal As-bearing minerals were derived from multiple sources, primarily from ophiolitic belts in the Indus-Tsangpo suture in the northeastern Himalayan and Indo-Burman Mountain ranges. Authigenic and amorphous Fe-(oxy)hydroxide minerals that are generally formed in river channels in the aerobic environment are the major secondary As-carriers in alluvial sediments. Reductive dissolution (mediated by Fe-reducing bacteria) of Fe-(oxy)hydroxide minerals under anoxic chemical conditions is the primary mechanism responsible for releasing As into groundwater. Authigenic siderite that precipitates under reducing environment at greater depths decreases Fe and possibly As concentrations in groundwater. Presence of Fe(III) minerals in aquifers shows that reduction of these minerals is incomplete and this can release more As if further Fe-reduction takes place with increased supplies of organic matter (reactive C). Absence of authigenic pyrite suggests that SO₄ reduction (mediated by SO₄-reducing bacteria) in Manikganj groundwater is limited in contrast to the southeastern Bengal Basin where precipitation of arsenian pyrite is thought to sequester As from groundwater.     

滇黔桂“金三角”卡林型金矿含砷黄铁矿和毒砂的矿物学研究

滇黔桂"金三角"卡林型金矿不同矿床亚类的典型矿床硫化物显微镜下观察和电子探针显微分析(EP-MA)表明,含砷黄铁矿和毒砂是主要的载金矿物.载金黄铁矿主要以环带状含砷黄铁矿、细粒自形含砷黄铁矿为主.环带状黄铁矿核部贫As、Au,富S、Fe,而环带则相反,且Au与As具有正相关关系.核部贫As的黄铁矿成因复杂,既有成矿早阶段的热液成因,又有受热液蚀变交代的沉积成因.核部和环带是不同成矿阶段的产物.元素的相关关系表明环带中As主要取代S的位置.多环带的特点还表明,热液活动是脉动式的,含矿流体化学成分也是在不断变化的.不论是核部还是环带,均有Au含量高出检出限的测点,但环带是主要的载金部位.细粒含砷黄铁矿为均质结构,具有高As、Au,低S、Fe的特点,类似环带状黄铁矿的环带特征,推测与富砷环带是同期热液活动形成的.毒砂-黄铁矿集合体中的黄铁矿分为环带结构和均质结构2种,并分别具有上述2种黄铁矿的特点.载金毒砂可以细分为3个世代,具均质结构,热液成因.各世代毒砂Au含量均有高出检出限的测点,同时Au、As、S、Fe的含量变化不大,均为主成矿阶段的产物.载金矿物的结晶顺序为:贫砷的沉积成因或早阶段热液成因黄铁矿→富砷的细粒黄铁矿颗粒和富砷黄铁矿环带→毒砂.黄铁矿和毒砂中的Au在EPMA微束的分辨率下均显示分布是不均匀的,环带状黄铁矿中Au元素图出现的均匀结构可能为一种假象,说明金主要以"不可见"的纳米级超显微包裹金形式存在,少量为"不可见"晶格金和微米级显微"可见金".整个滇黔桂"金三角"卡林型金矿不同亚类矿床之间的载金矿物特征和金的赋存状态没有本质区别,说明它们具有相同的成矿作用过程和成矿背景.     

Invisible Gold from the Hishikari Epithermal Gold Deposit, Japan: Implication for Gold Distribution and Deposition

Abstract. The presence of invisible gold was confirmed in arsenian pyrite from the Hishikari epithermal gold deposit, Kagoshima, Japan, by means of EPMA and SIMS analyses. The relative concentration of invisible gold may be positively correlated with As contents (0.01 to 10.37 wt%) of fine-grained arsenian pyrite which commonly occurs in the auriferous quartz veins. Although arsenian pyrite occurs widely in any mineralization stage with electrum and other sulfide, sulfosalts, selenide or telluride minerals, arsenian pyrites having higher As contents accompanied by invisible gold occur dominantly in the middle stage of fine-adularia-quartz and in the late stage of coarse-quartz rather than in the early stage of columnar-adularia.     

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.     

甘肃阳山金矿田载金矿物特征及金赋存状态研究

采用电子探针分析,详细研究了甘肃阳山类卡林型金矿田原生矿石中不同成矿阶段载金矿物的Au、As、S、Fe等元素含量及其分布规律,确定含砷黄铁矿和毒砂是最重要的载金矿物,发现不同成矿阶段的黄铁矿具有不同的成分特点;沉积成岩期黄铁矿为草莓状、胶状,砷和金含量最低,分别为0.10%和0.08%;热液成矿期早阶段黄铁矿粒度较粗(0.40～1.00mm),是较高温度(270～300℃)下缓慢结晶的产物,其砷和金含量较低,分别为0.27%和0.09%;热液成矿期主阶段(包括M1,M2和M3亚阶段)黄铁矿粒度微细(0.05～0.20mm),是210～270℃条件下快速结晶的产物,砷和金含量最高,M1亚阶段分别为3.45%As和0.11%Au,M2亚阶段分别为3.88%As和0.14%Au.在含砷黄铁矿中,金可能有自然金和离子金两种存在方式.沉积成岩期和热液成矿期早阶段低砷黄铁矿中金主要以纳米级自然金(Au~0)颗粒形式分布,而在热液成矿期主阶段含砷黄铁矿中金主要以Au+的形式存在.当热液中As活度高时,含砷黄铁矿在快速生长条件下,其生长面的空穴和缺陷较多,有利于热液中Au(HS)~0络合物通过吸附反应直接进入含砷黄铁矿生长表面.此外,主阶段流体的硫化和沸腾作用均可导致H_2S的减少,有利于形成砷黄铁矿和Au沉淀富集.