Arsenopyrite Research Articles

Improvement of modes and circuits of bacterial leaching of sulfide concentrates

These studies are devoted to the effect of the feed circuit of a series of chemostats on the characteristics of bacterial leaching of sulfide concentrates. The parameters and modes of the process are investigated at a laboratory installation consisting of five operating reactors, each with an active volume of 1.5 l and a conditioning tank. The initial material was a gold-bearing arsenical pyrite flotation concentrate containing Au, Ag, and As, as well as a specially adapted bacterial strain, namely, Acidithiobacillus ferrooxidans. It is established that double-flow feeding of a series of chemostats makes it possible to increase the leaching yield up to a 70% excess of the critical rate of dilution under the single-flow feeding mode at the same degree of oxidation of output sulfide minerals.

Geochemical Evolution of a High Arsenic, Alkaline Pit-Lake in the Mother Lode Gold District, California

The Harvard orebody at the Jamestown gold mine, located along the Melones fault zone in the southern Mother Lode gold district, California, was mined in an open-pit operation from 1987 to 1994. Dewatering during mining produced a hydrologic cone of depression; recovery toward the premining ground-water configuration produced a monomictic pit lake with alkaline Ca-Mg-HCO3-SO4–type pit water, concentrations of As up to 1,200 μ g/L, and total dissolved solids (TDS) up to 2,000 mg/L. In this study, pit-wall rocks were mapped and chemically analyzed to provide a context for evaluating observed variability in the composition of the pit-lake waters in relationship to seasonal weather patterns. An integrated hydrogeochemical model of pit-lake evolution based on observations of pit-lake volume, water composition (samples collected between 1998–2000, 2004), and processes occurring on pit walls was developed in three stages using the computer code PHREEQC. Stage 1 takes account of seasonally variable water fluxes from precipitation, evaporation, springs, and ground water, as well as lake stratification and mixing processes. Stage 2 adds CO2 fluxes and wall-rock interactions, and stage 3 assesses the predictive capability of the model. Two major geologic units in fault contact comprise the pit walls. The hanging wall is composed of interlayered slate, metavolcanic and metavolcaniclastic rocks, and schists; the footwall rocks are chlorite-actinolite and talc-tremolite schists generated by metasomatism of greenschist-facies mafic and ultramafic igneous rocks. Alteration in the ore zone provides evidence for mineralizing fluids that introduced CO2, S, and K2O, and redistributed SiO2. Arsenian pyrite associated with the alteration weathers to produce goethite and jarosite on pit walls and in joints, as well as copiapite and hexahydrite efflorescences that accumulate on wall-rock faces during dry California summers. All of these pyrite weathering products incorporate arsenic at concentrations from <100 up to 1,200 ppm. In the pit lake, pH and TDS reach seasonal highs in the summer epilimnion; pH is lowest in the summer hypolimnion. Arsenic and bicarbonate covary in the hypolimnion, rising as stratification proceeds and declining during winter rains. The computational model suggests that water fluxes alone do not account for this seasonal variability. Loss of CO2 to the atmosphere, interaction with pit walls including washoff of efflorescent salts during the first flush and seasonal rainfall, and arsenic sorption appear to contribute to the observed pit-lake characteristics.

Invisible gold in arsenian pyrite and arsenopyrite from a multistage Archaean gold deposit: Sunrise Dam, Eastern Goldfields Province, Western Australia

Invisible gold in arsenian pyrite and arsenopyrite from a multistage Archaean gold deposit: Sunrise Dam, Eastern Goldfields Province, Western Australia

Invisible gold in arsenian pyrite and arsenopyrite from a multistage Archaean gold deposit: Sunrise Dam, Eastern Goldfields Province, Western Australia

The Sunrise Dam gold mine (11.1 Moz Au) is the largest deposit in the Archaean Laverton Greenstone Belt (Eastern Goldfields Province, Yilgarn Craton, Western Australia). The deposit is characterized by multiple events of fluid flow leading to repeated alteration and mineralization next to a major crustal-scale structure. The Au content of arsenian pyrite and arsenopyrite from four mineralizing stages (D1, D3, D4a, and D4b) and from different structural and lithostratigraphic environments was measured using in situ laser ablation inductively coupled plasma mass spectrometry. Pyrite contains up to 3,067 ppm Au (n = 224), whereas arsenopyrite contains up to 5,767 ppm (n = 19). Gold in arsenopyrite (D4a stage) was coprecipitated and remained as “invisible gold” (nanoparticles and/or lattice-bound) during subsequent deformation events. In contrast, gold in pyrite is present not only as “invisible gold” but also as micrometer-size inclusions of native gold, electrum, and Au(Ag)–tellurides. Pristine D1 and D3 arsenian pyrite contains relatively low Au concentrations (≤26 ppm). The highest Au concentrations occur in D4a arsenian-rich pyrite that has recrystallized from D3 pyrite. Textures show that this recrystallization proceeded via a coupled dissolution–reprecipitation process, and this process may have contributed to upgrading Au grades during D4a. In contrast, Au in D4b pyrite shows grain-scale redistribution of “invisible” gold resulting in the formation of micrometer-scale inclusions of Au minerals. The speciation of Au at Sunrise Dam and the exceptional size of the deposit at province scale result from multiple fluid flow and multiple Au-precipitating mechanisms within a single plumbing system.

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.

Contamination of groundwater by arsenic and other constituents in an industrial complex

This study examined the natural and anthropogenic pollution of groundwater at a national groundwater monitoring station (NGMS) in a dyeing industry complex, Korea. The arsenic contamination of a shallow well at the NGMS was noticed, starting from 22 months after the well installation. Possibilities of several mechanisms for As pollution of the groundwater were examined. The arsenical pyrite oxidation as a source mechanism in the shallow aquifer may be disregarded because of deficiency of pyrite in the shallow sediments, concomitant with depleted dissolved oxygen and very low levels of redox potentials of the As-polluted groundwater. The effect of wastewater from the general industrial area through a covered sewer stream was also considered as a possible source. Even though occurrence patterns of phenol and volatile organic hydrocarbons were very similar to those of the polluted shallow groundwater, As was not detected in the wastewater. One of the most plausible sources of the arsenic pollution was believed to be the reductive dissolution of Fe hydroxide. The As-polluted shallow groundwater had also very high levels of pH, HCO3, COD and very low levels of DO and NO3, which support the possibility of As pollution by the reductive dissolution. Consequently, the shallow groundwater in and around the NGMS has been polluted with various contaminants including As, phenol, chlorinated solvents, and petroleum hydrocarbons through multiple sources of contamination, such as natural reductive dissolution, dyeing wastewater, industrial wastewater, and municipal sewage.

Nanoscale "liquid" inclusions of As-Fe-S in arsenian pyrite

A new mode of arsenic incorporation into arsenian pyrite has been discovered. Electron microprobe analyses and elemental maps of arsenian pyrite from Pueblo Viejo, Dominican Republic, show that its chemical composition varies from (Fe0.998As0.003)1.001S2 to (Fe0.963As0.050Cu0.003Ag0.001)1.017S2 and that arsenic is inversely correlated with Fe. High-resolution transmission electron microscopy (HRTEM) images show that some arsenic in this pyrite is present as nanoscale inclusions of amorphous As- Fe-S in a matrix of arsenian pyrite. The amorphous inclusions display negative facets with a cubic or rectangular morphology, typical of negative inclusions of pyrite and arsenopyrite or marcarsite, respectively, and they are oriented parallel to the lattice fringes (100) of the arsenian pyrite matrix. Elemental maps collected by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) show that the inclusions have a higher content of arsenic than the surrounding pyrite, and TEM-EDX analyses indicate approximate atomic proportions of 62 at% S, 28 at% Fe, and 10 at% As for the inclusions, which are near the minimum melting temperature in the As-Fe-S ternary. These observations suggest that the inclusions were trapped as liquids during growth of the surrounding arsenian pyrite. Although not a new mineral, this constitutes a third form for arsenian pyrite, which has previously been shown to contain arsenic as either As1- or As3+.

Sediment-Hosted Gold Deposits in Guizhou, China: Products of Wall-Rock Sulfidation by Deep Crustal Fluids

Sediment-hosted gold deposits in Guizhou, China, are hosted in late Paleozoic and early Mesozoic sedimentary rocks along the southwest margin of the Precambrian Yangtze craton. They have characteristics similar to Carlin-type gold deposits in Nevada and are notably enriched in As, Sb, Hg, and Tl. The Shuiyindong and Yata deposits consist of disseminated, strata-bound sulfides in Permian bioclastic limestone and fault-controlled mineralization in Middle Triassic calcareous clastic rocks, respectively. Mineralization in both deposits consists of barren milky quartz veins, disseminated gold-bearing arsenian pyrite and arsenopyrite, stibnite, realgar, and orpiment. The barren milky quartz veins occur in the ore-controlling structures with an envelope of gold mineralization in the host rock consisting of disseminated gold-bearing arsenian pyrite and arsenopyrite and replacement-style quartz veinlets. Later drusy quartz, stibnite, realgar, and orpiment fill fractures and vugs on the periphery of gold mineralization. Petrography, microthermometry, laser Raman spectroscopy, and laser ablation inductively coupled plasma mass spectrometric (LA-ICP-MS) analyses of fluid inclusions are used to characterize the chemical evolution of ore fluids at Shuiyindong and Yata. Early barren milky quartz veins trapped aqueous fluid with moderate salinity (6.0 wt % NaCl equiv) and minor CO2 (<2.4 mol %) at a temperature of 230° ± 30°C. This fluid contains measurable B, Na, K, Cs, Sr, As, Sb, and Au (3.8 ± 0.5–5.7 ± 2.3 μ g/g) determined by LA-ICP-MS and is interpreted to approximate the mineralizing fluid responsible for precipitation of early barren quartz veins. Low-salinity (0.9–2.3 wt % NaCl equiv), CO2-bearing (6.3–8.4 mol %), aqueous fluids are recorded in replacement-style quartz veinlets. They formed gold-bearing arsenian pyrite and arsenopyrite and quartz veinlets at a temperature of 210° ± 20°C and pressures of 450 to 1,150 bars, corresponding to depths between 1.7 and 4.3 km under lithostatic conditions. Fluid inclusions in late stibnite-orpiment-realgar-quartz veins contain high CO2 (58–64 mol %) and N2 (19.2–23.7 mol %) with trace CH4 (up to 1.6 mol %). The increasing content of CO2 and decrease in the concentrations of Au and As in aqueous-carbonic inclusions are interpreted to result from carbonate dissolution at the level of the deposits during gold mineralization. Covariance of Au, As, Sb, and Sr concentrations in the fluids is interpreted to reflect deposition of As and Sb sulfides and gold concurrent with carbonate crystallization. Iron is below detection limit (~400 μ g/g) in all fluid inclusion types, suggesting that the ore fluids were Fe poor but possibly sulfur rich, possibly explaining their exceptionally high gold contents. Iron in sulfide minerals was probably derived from dissolution of ferroan minerals in the host rocks, sulfidized by H2S-rich fluids to precipitate arsenian pyrite, arsenopyrite, and gold. Pressure fluctuation induced by faulting resulted in local fluid immiscibility and led to late deposition of realgar, orpiment, stibnite, and calcite. Hydrogen and oxygen isotope compositions of ore fluids ( δ D(H2O) = −35 to −68‰, δ 18O(H2O) = 4–16.5‰) indicate a metamorphic origin, possibly related to crustal thickening and prograde metamorphism during the late Yanshanian orogeny.

THE URANINITE-PYRITE ASSOCIATION, A SENSITIVE INDICATOR OF CHANGES IN PALEOFLUID COMPOSITION: AN EXAMPLE FROM THE OHRE (EGER) GRABEN, BOHEMIAN MASSIF, CZECH REPUBLIC

Trace-element variations in uraninite were employed to decipher its chemical age and to evaluate the As-rich nature of fluids during its formation at Jenikov, Teplice area, in the central part of the Cenozoic Ohře Graben, Bohemian Massif, Czech Republic. Cretaceous sandstones of the graben fill show two distinctive stages of young mineralization (less than 18 Ma), most probably related to topography-driven flow of epithermal fluid along the northwestern boundary-fault of the graben (the Krusne hory Fault). The older stage is dominated by pervasive precipitation of silica accompanied by pyrite, sphalerite, galena, uraninite and kaolinite, whereas the younger stage is represented by barite with pyrite inclusions and fluorite. The uraninite formed together with microcrystalline quartz (Qtz–4) at the end of the first stage. Uraninite of subgroup A shows high As/Pb values (14.6–69.9), higher Ca (1.02–1.99 wt.%), lower Ti (0.27–0.44 wt.%), and other trace elements compatible with the structure of uraninite. Uraninite of subgroup B shows low As/Pb values (2.5–8.4), lower Ca (0.39–0.90 wt.%), higher Ti (0.43–8.94 wt.%), and the presence of elements incompatible with the structure (Ti, Fe). A significant correlation between As and Pb was found in both subgroups. The calculated apparent radiometric age of the uraninite samples shows a broad dispersal, suggesting the presence of common lead, which was corrected using the correlation between the contents of As and Pb tot (Pb common + Pb radiogenic ). This procedure allowed us to assign an age of uraninite formation of about 0.5 Ma (± 0.6 Ma), which fits the geological data, and to demonstrate its formation during a single episode of mineralization. An approximately five-fold increase in As content of the fluid phase during uraninite and pyrite formation can be inferred from the correlation between the intragroup As/Pb values and the observed intragrain As max /As min values in the associated arsenian pyrite. If amounts of common lead are introduced into uraninite in conjunction with another conservative element, a correlation between the conservative element and total lead can be used to decipher the age of the mineralization and to track element variations in the parent fluid phase.

Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO 4 to stimulate metabolism of indigenous SO 4 -reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO 4 , and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO 4 reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS 2 . By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO 4 reduction commenced but increased to pre-experiment level once SO 4 reduction ended. In the ongoing experiment, both SO 4 and Fe(II) were amended to groundwater to evaluate if FeS/FeS 2 formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions. In summary, when anaerobic bacterial metabolism is optimized by providing both electron donors and acceptors, As is mobile under Fe-reducing conditions, immobile under SO 4 -reducing conditions, and arsenian pyrite is the likely stable mineral phase formed under SO 4 -reducing conditions, instead of pure As–S phases such as realgar or orpiment.

Influence of groundwater recharge and well characteristics on dissolved arsenic concentrations in southeastern Michigan groundwater

Arsenic concentrations exceeding 10 microg/l, the United States maximum contaminant level and the World Health Organization guideline value, are frequently reported in groundwater from bedrock and unconsolidated aquifers of southeastern Michigan. Although arsenic-bearing minerals (including arsenian pyrite and oxide/hydroxide phases) have been identified in Marshall Sandstone bedrock of the Mississippian aquifer system and in tills of the unconsolidated aquifer system, mechanisms responsible for arsenic mobilization and subsequent transport in groundwater are equivocal. Recent evidence has begun to suggest that groundwater recharge and characteristics of well construction may affect arsenic mobilization and transport. Therefore, we investigated the relationship between dissolved arsenic concentrations, reported groundwater recharge rates, well construction characteristics, and geology in unconsolidated and bedrock aquifers. Results of multiple linear regression analyses indicate that arsenic contamination is more prevalent in bedrock wells that are cased in proximity to the bedrock-unconsolidated interface; no other factors were associated with arsenic contamination in water drawn from bedrock or unconsolidated aquifers. Conditions appropriate for arsenic mobilization may be found along the bedrock-unconsolidated interface, including changes in reduction/oxidation potential and enhanced biogeochemical activity because of differences between geologic strata. These results are valuable for understanding arsenic mobilization and guiding well construction practices in southeastern Michigan, and may also provide insights for other regions faced with groundwater arsenic contamination.

Invisible gold and arsenic in pyrite from the high-grade Hishikari gold deposit, Japan

Gold occurs as both electrum (a natural alloy of gold and silver) and invisible gold in arsenian pyrite in the Hishikari epithermal gold deposit in Japan. Microanalyses of arsenian pyrite from the deposit using secondary ion mass spectrometry (SIMS) and electron probe microanalysis (EPMA) revealed that Au concentrations (0.1–2600 ppm) are positively correlated with As concentrations (0.0–6.1%). A small (3 μm) area of pyrite was analyzed because the sample textures were fine and complicated. The Au/As ratio is high in the Sanjin ore zone, which has very high-grade veins, while the ratio is low in the Yamada ore zone, which has average-grade veins.

Arsenic in groundwaters in the Northern Appalachian Mountain belt: A review of patterns and processes

Naturally occurring arsenic in the bedrock of the Northern Appalachian Mountain belt was first recognized in the late 19th century. The knowledge of the behavior of arsenic in groundwater in this region has lagged behind nearly a century, with the popular press reporting on local studies in the early 1980s, and most peer-reviewed research articles on regional patterns conducted and written in the late 1990s and early 2000s. Research reports have shown that within this high arsenic region, between 6% and 22% of households using private drinking water wells contain arsenic in excess of 10 µg/L, the United States Environmental Protection Agency's maximum contaminant level. In nearly all reports, arsenic in drinking water was derived from naturally occurring geologic sources, typically arsenopyrite, substituted sulfides such as arsenian pyrite, and nanoscale minerals such as westerveldite. In most studies, arsenic concentrations in groundwater were controlled by pH dependent adsorption to mineral surfaces, most commonly iron oxide minerals. In some cases, reductive dissolution of iron minerals has been shown to increase arsenic concentrations in groundwater, more commonly associated with anthropogenic activities such as landfills. Evidence of nitrate reduction promoting the presence of arsenic(V) and iron(III) minerals in anoxic environments has been shown to occur in surface waters, and in this manuscript we show this process perhaps applies to groundwater. The geologic explanation for the high arsenic region in the Northern Appalachian Mountain belt is most likely the crustal recycling of arsenic as an incompatible element during tectonic activity. Accretion of multiple terranes, in particular Avalonia and the Central Maine Terrane of New England appear to be connected to the presence of high concentrations of arsenic. Continued tectonic activity and recycling of these older terranes may also be responsible for the high arsenic observed in the Triassic rift basins, e.g. the Newark Basin. There are only two well-known cases of anthropogenic contamination of the environment in the northern Appalachian Mountain belt, both of which are industrial sites with surface contamination at that infiltrated the local groundwater.

A proposed new type of arsenian pyrite: Composition, nanostructure and geological significance

This report describes a new form of arsenian pyrite, called As3+-pyrite, in which As substitutes for Fe [(Fe,As)S2], in contrast to the more common form of arsenian pyrite, As1−-pyrite, in which As1− substitutes for S [Fe(As,S)2]. As3+-pyrite has been observed as colloformic overgrowths on As-free pyrite in a hydrothermal gold deposit at Yanacocha, Peru. XPS analyses of the As3+-pyrite confirm that As is present largely as As3+. EMPA analyses show that As3+-pyrite incorporates up to 3.05 at % of As and 0.53at. %, 0.1at. %, 0.27at. %, 0.22at. %, 0.08at. % and 0.04at. % of Pb, Au, Cu, Zn, Ni, and Co, respectively. Incorporation of As3+ in the pyrite could be written like: As3++yAu++1-y(□)⇔2Fe2+; where Au+ and vacancy (□) help to maintain the excess charge. HRTEM observations reveal a sharp boundary between As-free pyrite and the first overgrowth of As3+-pyrite (20–40nm thick) and co-linear lattice fringes indicating epitaxial growth of As3+-pyrite on As-free pyrite. Overgrowths of As3+-pyrite onto As-free pyrite can be divided into three groups on the basis of crystal size, 8–20nm, 100–300nm and 400–900nm, and the smaller the crystal size the higher the concentration of toxic arsenic and trace metals. The Yanacocha deposit, in which As3+-pyrite was found, formed under relatively oxidizing conditions in which the dominant form of dissolved As in the stability field of pyrite is As3+; in contrast, reducing conditions are typical of most environments that host As1−-pyrite. As3+-pyrite will likely be found in other oxidizing hydrothermal and diagenetic environments, including high-sulfidation epithermal deposits and shallow groundwater systems, where probably kinetically controlled formation of nanoscale crystals such as observed here would be a major control on incorporation and release of As3+ and toxic heavy metals in oxidizing natural systems.

Anthropogenic and natural lead isotopes in Fe-hydroxides and Fe-sulphates in a watershed associated with arsenic-enriched groundwater, Maine, USA

A survey of the natural and anthropogenic sources of lead contributing to secondary minerals in sulphidic schists associated with arsenic-enriched groundwater in Coastal Maine shows that the most likely source is natural Pb, particularly from coexisting sulphide minerals. The secondary minerals also reflect notable contributions from anthropogenic Pb. The Pb isotopes establish pathways by which Pb, and by inference As, could have been transported from As-bearing minerals (arsenian pyrite, arsenopyrite, lollingite, orpiment, arsenic oxide and others), via sulphide oxidation or carbonation reactions into multiple generations of secondary minerals (goethite, hematite, jarosite, natrojarosite and others). Lead isotopic compositions of the sulphides and secondary minerals determined by thermal ionization mass spectrometry ( n =53) range widely. Lead and As contents of the sulphides and secondary minerals overlap, and are generally positively correlated. Pyrite, the dominant sulphide in sulphidic schists associated with As-enriched groundwater in Coastal Maine, has values of 206 Pb/ 204 Pb from 18.186 to 18.391, 207 Pb/ 204 Pb from 15.617 to 15.657, 208 Pb/ 204 Pb from 38.052 to 38.210, 206 Pb/ 207 Pb from c . 1.1625 to 1.1760 and 208 Pb/ 207 Pb from c . 2.4276 to 2.4394. Mixtures of Fe-hydroxide and oxide minerals (predominantly goethite and hematite) and secondary Fe-sulphate minerals (jarosite, natrojarosite, rozenite and melanterite) in the sulphidic schists have overlapping but generally higher values of 206 Pb/ 204 Pb from 18.495 to 19.747 (one sample at 21.495), 207 Pb/ 204 Pb from 15.595 to 15.722 (one sample at 15.839), 208 Pb/ 204 Pb from 38.186 to 39.162, 206 Pb/ 207 Pb from c. 1.1860 to 1.2575 (one sample at 1.3855) and 208 Pb/ 207 Pb from c . 2.4441 to 2.4865 than the sulphides. Sulphides from Zn-Pb metal mines are somewhat less radiogenic than sulphides from the schists. Other sulphides (mostly pyrite) associated with pegmatites and granitic rocks are heterogeneous and more radiogenic than the pyrite-rich sulphidic schists. Sulphides from other regional bedrock units also have heterogeneous isotope values. Lead isotopic compositions of the sulphides from the sulphidic schists and coexisting Fe-oxides and Fe-sulphates produced by weathering and alteration overlap, but the secondary minerals extend toward more radiogenic values that broadly indicate the addition of Pb from anthropogenic origin. As a component of Pb from extensively used arsenical pesticides may also be present in the secondary minerals, the range in Pb isotope values is consistent with multiple sources: natural Pb from the schists and anthropogenic Pb (industrial and possibly from agricultural activities). Contributions from past mining activities or from other bedrock sources are not implicated.

Mineral sources and transport pathways for arsenic release in a coastal watershed, USA

Metasedimentary bedrock of coastal Maine contains a diverse suite of As-bearing minerals that act as significant sources of elements found in ground and surface waters in the region. Arsenic sources in the Penobscot Formation include, in order of decreasing As content by weight: löllingite and realgar ( c. 70%), arsenopyrite, cobaltite, glaucodot, and gersdorffite (in the range of 34–45%), arsenian pyrite (&lt;4%), and pyrrhotite (&lt;0.15%). In the Penobscot Formation, the relative stability of primary As-bearing minerals follows a pattern where the most commonly observed highly altered minerals are pyrrhotite, realgar, niccolite, löllingite &gt; glaucodot, arsenopyrite-cobaltian &gt; arsenopyrite, cobaltite, gersdorffite, fine-grained pyrite, Ni-pyrite &gt; coarse-grained pyrite. Reactions illustrate that oxidation of Fe-As disulphide group and As-sulphide minerals is the primary release process for As. Liberation of As by carbonation of realgar and orpiment in contact with high-pH groundwaters may contribute locally to elevated contents of As in groundwater, especially where As is decoupled from Fe. Released metals are sequestered in secondary minerals by sorption or by incorporation in crystal structures. Secondary minerals acting as intermediate As reservoirs include claudetite ( c. 75%), orpiment (61%), scorodite ( c. 45%), secondary arsenopyrite ( c. 46%), goethite (&lt;4490 ppm), natrojarosite (&lt;42 ppm), rosenite, melanterite, ferrihydrite, and Mn-hydroxide coatings. Some soils also contain Fe-Co-Ni-arsenate, Ca-arsenate, and carbonate minerals. Reductive dissolution of Fe-oxide minerals may govern the ultimate release of iron and arsenic – especially As(V) – to groundwater; however, dissolution of claudetite (arsenic trioxide) may directly contribute As(III). Processes thought to explain the release of As from minerals in bedrock include oxidation of arsenian pyrite or arsenopyrite, or carbonation of As-sulphides, and most models based on these generally rely on discrete minerals or on a fairly limited series of minerals. In contrast, in the Penobscot Formation and other metasedimentary rocks of coastal Maine, oxidation of As-bearing Fe-cobalt-nickel-sulphide minerals, dissolution (by reduction) of As-bearing secondary As and Fe hydroxide and sulphate minerals, carbonation and/or oxidation of As-sulphide minerals, and desorption of As from Fe-hydroxide mineral surfaces are all thought to be involved. All of these processes contribute to the occurrence of As in groundwaters in coastal Maine, as a result of variability in composition and in stability of the As source minerals. Arsenic contents of soils and groundwater thus reflect the predominant influence and integration of a spectrum of primary mineral reservoirs (instead of single or unique mineral reservoirs). Cycling of As through metasedimentary bedrock aquifers may therefore depend on consecutive stages of carbonation, oxidation and reductive dissolution of primary and secondary As host minerals.

The carbonate rock-hosted epithermal gold deposit of Agdarreh, Takab geothermal field, NW Iran—hydrothermal alteration and mineralisation

The disseminated gold deposit of Agdarreh (24.5 t at 3.7 g/t Au) is hosted in hydrothermally leached Miocene reefal limestone in the Takab geothermal field, which is part of the Cenozoic Urumieh–Dokhtar volcanic arc of NW Iran. Alteration and mineralisation are largely bedding controlled blanket-like and include: (1) pre-ore decalcification; (2) first-stage silicification associated with pyrite (early pyrite with 3–4 wt% As, late pyrite with <1–3 wt% As) and sphalerite; (3) second-stage silicification with precipitation of galena, Pb–Sb–As sulphides, sulphosalts, tellurides and native bismuth; (4) late-stage cinnabar and barite in vugs; (5) oxide ore stage and carbonate alteration (complex Mn–Fe-rich oxyhydroxides, arsenates, sulphates, APS minerals and rutile in residual leached rock and infill of karstic cavities). Gold occurs invisibly in the jasperoids and is enriched in the Mn–Fe oxyhydroxide surface cap of the jasperoids. Gold mineralisation is associated with the hydrothermal metal suite of As, Sb, Hg, Te, Se, Tl, Ba, Zn, Ag, Cd, Bi and Pb, and is characterised by very low Cu contents. Arsenian pyrite probably carried most of the primary (invisible) gold. Native gold occurs in association with the late-stage cinnabar and the oxide ore. The Agdarreh deposit shows many similarities with Carlin-type ore and is interpreted to have resulted from near-surface hydrothermal activity related to the Cenozoic arc volcanism that developed within the extensional Takab graben. The extensive oxidation at Agdarreh may be partly due to the waning stages of hydrothermal activity. Active H2S-bearing thermal springs are locally depositing extremely high contents of Au and Ag, and travertine is present over large areas, suggesting that ore-forming hydrothermal activity occurred periodically from the Miocene to Recent in the Takab geothermal field.

Visible gold in arsenian pyrite at the Shuiyindong Carlin-type gold deposit, Guizhou, China: Implications for the environment and processes of ore formation

Carlin-type gold deposits are best known for the scarcity of visible gold in their ores. It has long been recognized that the majority of gold is “invisible”, such that it cannot be resolved by conventional microscopy, and resides in arsenian pyrite. Shuiyindong differs in that sub-μm to μm-sized native gold is present in arsenian pyrite veinlets and disseminations. It is also the largest (55 tonnes) and highest grade (7 to 18 ppm), stratabound, Carlin-type gold deposit in Guizhou, China and has produced 5 tonnes of gold from sulfide refractory ores extracted by underground mining methods. In this study, an electron microprobe analyzer (EMPA) was used to map the spatial distribution of “invisible” gold and sub-μm to μm-size visible gold particles in arsenian pyrite in high-grade ore samples from the Shuiyindong. The samples studied are hosted in Permian bioclastic ferroan limestone of the Longtan Formation and exhibit evidence of decarbonation, silicification and sulfidation. Arsenian pyrite with detectable Au (> 400 to 3800 ppm) is disseminated in altered limestone and was deposited in two stages separated by an episode of corrosion in a veinlet. The results show that there are two populations of native gold in arsenian pyrite. One is comprised of sub-μm size gold particles (0.1 to 0.2 μm) that are occasionally present in the gold-bearing arsenian pyrite disseminated in the host rocks. This arsenian pyrite is interpreted to have been formed by sulfidation of ferroan calcite and dolomite. Another is comprised of coarser (1 to 6 μm) native gold grains present in the arsenian pyrite veinlet, either on the first stage where it has been corroded or on the second stage. The lack of fluid inclusion or other evidence of boiling and the low iron content of fluid inclusions in quartz, suggest the veinlet formed by sulfidation of another fluid containing Fe. The Fe-bearing fluid may be a depleted ore fluid that gained Fe by dissolution of ferroan limestone after H 2S had been consumed. The association of the largest visible gold grains with an episode of corrosion suggests that fluids episodically became undersaturated with arsenian pyrite while remaining saturated with gold (e.g., pH decrease or an increase in the oxidation state). This may have resulted from incursion of relatively acidic or oxidized fluids that were able to dissolve arsenian pyrite and remain saturated with gold. In this case, sulfidation of iron from the host rock, was the most important depositional mechanism for Au-bearing arsenian pyrite with, or without, grains of native gold.

Multistage Sedimentary and Metamorphic Origin of Pyrite and Gold in the Giant Sukhoi Log Deposit, Lena Gold Province, Russia

Gold mineralization at Sukhoi Log in eastern Siberia is hosted in a deformed Neoproterozoic organic-bearing and pyritic black shale and siltstone sequence that is folded into a tight overturned anticline. The deposit contains about 30 million ounces of gold at an average grade of 2.0 g/t Au and is one of the largest known undeveloped gold resources. The high-grade gold zone forms a gently dipping tabular body in the core of the anticline. The best gold grades occur in narrow, bedding-parallel pyrite-quartz veinlets that have been folded during the main deformation event. Lower grade gold is associated with disseminated pyrite developed in and around the high-grade core of the deposit. Detailed paragenetic studies of the mineralization and host rocks have defined six stages of pyrite development in the carbonaceous sediments. The two earliest forms of pyrite, termed py1 and py2, are commonly developed in stratiform layers of micron-sized crystals, framboids and fine euhedra, which are interpreted as synsedimentary to early diagenetic in origin. Coarser grained, bedding-parallel aggregates of inclusion-rich pyrite, termed py3, contain inclusions of arsenopyrite, native gold and gold tellurides and are interpreted to form during late diagenesis and earliest deformation. Coarse euhedral pyrite, py4, overgrows the earlier pyrite (py1, py2, and py3), and the slaty cleavage developed in the host rocks, indicating a syndeformation timing. Late- stage, inclusion-free pyrite, py5, overgrows and replaces earlier sulfides and is considered to be syn- to late deformation. Laser-ablation inductively coupled plasma mass spectrometry (LA-ICPMS) analyses of the various pyrite types indicate that the synsedimentary py1 contains the highest levels of invisible gold, varying from 0.4 to 12.1 ppm, with a mean of 3.22 ppm Au, and 1,900 ppm As. Py1 is also enriched in a suite of trace elements (Mo, Sb, Ni, Co, Se, Te, Ag, Cu, Pb, Zn, Mn, Ba, Cr, U, V), which are similar to those concentrated by organic processes in euxinic sedimentary environments. Later generations of pyrite, from py2 to py5, including pyrite in bedding- parallel pyrite-quartz veinlets, contain progressively lower contents of invisible gold and most other trace elements. However, this metamorphic and postmetamorphic pyrite contains microinclusions of free gold, arsenopyrite, pyrrhotite, sphalerite, and chalcopyrite. The paragenetic, textural, and chemical relationships at Sukhoi Log suggest that gold was clearly initially introduced prior to cleavage development, accompanying sedimentation of the organic-rich shales and fixed during diagenesis within the structure of diagenetic arsenian pyrite. Subsequently, accompanying deformation, gold was liberated from recrystallized diagenetic pyrite to become concentrated as free gold and gold tellurides within metamorphic pyrite and folded bedding-parallel pyrite-quartz veinlets. Two key processes are considered vital to the formation of the Sukhoi Log deposit: original synsedimentary and early diagenetic concentration of gold, dissolved within arsenian pyrite in organic-rich black shales, and metamorphic processes that liberated gold from the early forms of arsenian pyrite, to be concentrated as free gold, and gold tellurides within late diagenetic and metamorphic pyrite and associated pyrite-quartz veinlets in the core of an overturned anticline. These ore-forming processes are unlikely to be unique to Sukhoi Log; other black-shale and turbidite-hosted deposits that occur in rifted continental margin environments, which have undergone collision and basin inversion, may form by similar processes.

Impurities and heterogeneity in pyrite: Influences on electrical properties and oxidation products

Macroscopic pyrite crystals originating from a variety of geologic settings were made into thick sections. Electrical properties were measured with a Hall system, and minor element composition was analyzed with laser ablation inductively coupled plasma mass spectroscopy (LA-ICPMS). Selected thick sections were oxidized in a moist air environment inside a glove chamber. The relative metal content of surface products formed during oxidation was analyzed by LA-ICP-MS. Natural pyrite exhibits a range of electrical properties corresponding to the content of the common minor elements Co, As and Ni. These properties are similar to those of synthetic pyrite doped with single elements. Pyrite enriched in Co is an n-type semiconductor with low resistivity and high carrier mobility, while arsenian pyrite tends to be p-type and have higher resistivity. The effect of Ni is weaker and tends to be obscured by Co and As in samples of mixed composition. Cobalt demonstrates the strongest effect on electrical properties. Enrichment of Co at oxidized pyrite surfaces is inversely correlated with its concentration in the underlying pyrite. Cobalt enrichment in oxidation products is also more pronounced along crystal defects such as fractures, and in crystals with heterogeneous distribution of trace elements. These observations might be explained by differences in the electronic structure of pyrite arising from the presence of impurities, and by the distribution of domains with different impurity compositions, facilitating electron transfer.