Arsenopyrite Research Articles

Concentrations of platinum-group elements (PGE), Re and Au in arsenian pyrite and millerite from Mo–Ni–PGE-Au black shales (Zunyi region, Guizhou Province, China): results from LA-ICPMS study

Lower Cambrian Mo–Ni sulphidic black shales from the Huangjiawan mine (Guizhou Province, south China) have anomalous platinum-group element (PGE) concentrations (up to ∼1 ppm in total). We used LA-ICPMS to study the distribution of PGE in pyrite and Ni-sulphide (millerite) and FE-SEM/EDS for determination of As in pyrite. A sulphide concentrate was produced by innovative hydroseparation techniques from one representative sample, which contained 162 ppb Pt, 309 ppb Pd, 12.2 ppb Ru, 11.3 ppb Rh, 1.5 ppb Ir, 11 212 ppb Re and 343 ppb Au. Mineralogical analysis revealed that pyrite forms ∼12 vol%, which corresponds to a calculated ∼18.4 wt% of all mineral phases in mineralized black shale. We found that pyrite contains on average (144 analyses) 0.10 ppm Pt, 0.11 ppm Re and 1.40 ppm Au (Ru, Rh, Pd, Os and Ir were below detection limit). It also contains from ∼0.5 to ∼1.8 wt% As and can be therefore classified as arsenian pyrite. Millerite (77 analyses) showed PGE, Re and Au values below detection limit. We suggest that pyrite represents a dominant Au carrier, containing between 64 and 83% Au of the total Au mineralised rock budget. Conversely, pyrite does not bear any significant amount of Re and Pt, contributing up to ∼0.2% and ∼12.5% to their whole rock budgets, respectively. Time resolved LA-ICPMS spectra in pyrite indicate that Pt, Re and Au behave as typical lattice-bound elements, with only Re locally forming micro-inclusions. Arsenic is heterogeneously distributed in pyrite and the Au/As ratio (much lower than 0.02) is in support of Au to be structurally bound in solid solution.

Determination of mineralization stages using correlation between geochemical fractal modeling and geological data in Arabshah sedimentary rock-hosted epithermal gold deposit, NW Iran

This research paper aims to delineate and recognize different gold mineralization stages based on surface lithogeochemical data using factor analysis and Spectrum-Area (S-A) modeling, as well as geological data in Arabshah sedimentary rock hosted epithermal gold deposit, NW Iran. Based on the factor analysis, Au and Mn were allocated to factor 2 (F2) and then classified by the S-A fractal modeling. In addition, Au and F2 values were transformed to spectrum data, which were categorized by the S-A log-log plots. Accordingly, the main mineralization phase contains Au and F2 (Au-Mn) values greater than 800 ppb and 0.3, respectively, and is associated with the occurrence of minerals such as pyrite, arsenian pyrite, realgar, orpiment and oxidized sulfides. The first phase of gold mineralization, where Au typically ranges between 80 and 350 ppb, is associated with base metal sulfides, arsenian pyrites and F2 values between 0.1 and 0.2. The second gold mineralization phase consists of Au values from 350 to 800 ppb and F2 values between 0.2 and 0.3. Combination of the S-A modeling, factor analysis and geological data outlined three gold mineralization stages in Arabshah gold deposit. The main mineralization stage showed a strong positive correlation with the NE-SW and NW-SE trending structures, the altered intrusive rocks such as microdiorite and granodiorite, and the altered subvolcanic dacitic domes.

Changes in the As solid speciation during weathering of volcanic ashes: A XAS study on Patagonian ashes and Chacopampean loess

X-ray absorption spectroscopy (XAS) was used to determine the oxidation state of As, local chemical coordination and the relative proportion of different As species in recent and ancient Andean volcanic ashes, as well as in Chaco Pampean loess. As K edge XANES analysis indicates that in loess sediments the dominant species is As(V) (i.e., >91%). Conversely, As(III) is dominant in all ash samples. In the Puyehue sample, only As(III) species were determined, while in both, the Chaitén and the ancient tephra samples, As(III) species accounts for 66% of the total As. The remaining 34% corresponds to As(−1) in the Chaitén sample and to As(V) in the weathered tephra. The proposed EXAFS models fit well with the experimental data, suggesting that in ancient and recent volcanic ashes, As(III) is likely related to As atoms present as impurities within the glass structure, forming hydroxide species bound to the Al-Si network. In addition, the identified As(−1) species is related to arsenian pyrite, while in the ancient volcanic ash, As(V) was likely a product of incipient weathering. In loess sediments, the identified As(V) species represents arsenate ions adsorbed onto Fe oxy(hydr)oxides, forming inner-sphere surface complexes, in a bidentate binuclear configuration.

Geology and Genesis of the Cerro la Mina Porphyry-High Sulfidation Au (Cu-Mo) Prospect, Mexico

The Cerro la Mina Au (Cu-Mo) porphyry-high sulfidation prospect is located in Chiapas State, southeastern Mexico, outside of the major metallogenic provinces of Mexico. The prospect is hosted by Pleistocene alkaline volcanic rocks of the Chiapanecan volcanic arc that formed in a complex triple-junction tectonic setting. Cerro la Mina's stratigraphy comprises pyroclastic flows that were intruded by monzodiorites and diorites at 1.04 ± 0.04 Ma (U-Pb, zircon), and that were overlain by debris flows and synvolcanic trachyandesite domes. The volcanic stratigraphy of Cerro la Mina is dominated by pyroclastic flows and rare basalts that are cut by the Cerro la Mina breccia pipe, a matrix-rich granular, vertically oriented, downward-tapering, polymict lithic rock unit that is host to all of the significant alteration and mineralization. A NW-trending sinistral wrench fault, which was active throughout the history of Cerro la Mina, is responsible for dismembering the prospect after mineralization. The magmatic hydrothermal system was composed of early porphyry-style potassic veins (quartz + K-feldspar ± biotite) and stage 1 pyrite that are preserved in clasts within the breccia pipe, suggesting that brecciation disrupted an embryonic porphyry system. Late potassic alteration occurred after the formation of the breccia pipe, as its matrix is strongly K-feldspar altered. Hydrothermal fluids then produced phyllic alteration composed of quartz, muscovite, illite, illite-smectite, and chlorite that is associated with stage 2 pyrite ± chalcopyrite ± molybdenite ± quartz veins. An unusual zoned pattern of advanced argillic-argillic alteration overprinted potassic and phyllic alteration. This zoning included a low-temperature ( 120°C) quartz + dickite ± kaolinite ± pyrophyllite ± alunite that occurs from 250 m to the present-day surface. The advanced argillic-argillic altered rocks host the most significant Au-Cu mineralization, which is associated with stage 3 marcasite, sphalerite, galena, and barite, and stage 4 arsenian pyrite ± enargite ± covellite. The magmatic hydrothermal system at Cerro la Mina began sometime between monzodiorite emplacement (1.04 ± 0.04 Ma; zircon U-Pb) and the precipitation of porphyry stage 2 molybdenite at 780 ± 10 ka (Re-Os). 40Ar/39Ar dating of biotite (689 ± 13 ka) records the age at which the hydrothermal system cooled below the biotite closure temperature of ~300°C and provides a maximum estimate for the onset of advanced argillic-argillic alteration. Sulfur isotope results of sulfides (–2.5 to +4.9‰; mean +0.7‰; n = 20) and a sulfate (barite; +10.5‰; n = 1) suggest a magmatic source of sulfur for all four stages of mineralization. The lack of residual quartz, rare alunite, and anomalous halloysite-kaolinite alteration may be explained by the high acid-buffering capacity of alkaline volcanic host rocks, high CO2 contents of the alkaline magma, and/or potentially by a highly reduced magmatic hydrothermal fluid. At the regional metallogenic scale, the Cerro la Mina prospect along with the nearby Santa Fe mine and Campamento deposit represent parts of a porphyry copper system—specifically, a porphyry/high-sulfidation, proximal skarn and intermediate sulfidation deposit, respectively. The characteristics of Cerro la Mina (i.e., anomalous halloysite-kaolinite alteration) broaden the window for additional discoveries to be made in the porphyry-epithermal environment.

The Au-Hosting Minerals and Process of Formation of the Carlin-Type Bojitian Deposit, Southwestern China

The recently discovered middle-sized Bojitian Carlin-type Au deposit is located in southwestern Guizhou Province, China, near the well-known Shuiyindong super-large-sized deposit. To improve the understanding on this deposit, here we investigate the minerals that host Au and the occurrence of Au in the deposit, using a combination of microscopic work and electron probe microanalysis (EPMA). Based on the results, the formation of the deposit was addressed. Results indicate that the dominant minerals that host Au include arsenian pyrite and arsenopyrite. Au in the cores of zoned pyrite exists mainly as natural nanoscale Au (Au0), while Au in the rims exists mainly as solid solution Au (Au+), but it likely also exists in the rims as natural nanoscale Au. The framboidal, coarse-grained, and banded pyrite types contain both natural nanoscale Au0 and solid solution Au+. The arsenopyrite is of hydrothermal origin, and Au within the arsenopyrite exists as gold solution Au+. The Bojitian deposit was formed from As-bearing, H2S-rich, low-to-medium-temperature fluids that migrated along faults and other channels. Au that was already present in the strata or source beds migrated with the fluids in the form of Au(HS)− and ore-forming fluids were then formed in the reducing environment. The ore-forming fluids interacted with Fe-rich carbonates to form an abundance of Au-hosting arsenian sulfides.

Arsenic Incorporation in Pyrite at Ambient Temperature at Both Tetrahedral S-I and Octahedral FeII Sites: Evidence from EXAFS-DFT Analysis.

Pyrite is a ubiquitous mineral in reducing environments and is well-known to incorporate trace elements such as Co, Ni, Se, Au, and commonly As. Indeed, As-bearing pyrite is observed in a wide variety of sedimentary environments, making it a major sink for this toxic metalloid. Based on the observation of natural hydrothermal pyrites, As-I is usually assigned to the occupation of tetrahedral S-I sites, with the same oxidation state as in arsenopyrite (FeAsS), although rare occurrences of AsIII and AsII have been reported. However, the modes of As incorporation into pyrite during its crystallization under low-temperature diagenetic conditions have not yet been elucidated because arsenic acts as an inhibitor for pyrite nucleation at ambient temperature. Here, we provide evidence from X-ray absorption spectroscopy for AsII,III incorporation into pyrite at octahedral FeII sites and for As-I at tetrahedral S-I sites during crystallization at ambient temperature. Extended X-ray absorption fine structure (EXAFS) spectra of these As-bearing pyrites are explained by local structure models obtained using density functional theory (DFT), assuming incorporation of As at the Fe and S sites, as well as local clustering of arsenic. Such observations of As-I incorporation at ambient temperature can aid in the understanding of the early formation of authigenic arsenian pyrite in subsurface sediments. Moreover, evidence for substitution of AsII,III for Fe in our synthetic samples raises questions about both the possible occurrence and the geochemical reactivity of such As-bearing pyrites in low-temperature subsurface environments.

Trace elements in fluid inclusions of sediment-hosted gold deposits indicate a magmatic-hydrothermal origin of the Carlin ore trend

Abstract The Carlin-type deposits in Nevada (western USA) constitute the world’s second-largest gold ore province. These structurally and stratigraphically controlled, sediment-hosted ore bodies are characterized by carbonate dissolution attending hydrothermal precipitation of gold-rich arsenian pyrite. The origin of the mineralizing fluids and the source of the gold remain debated. Conceptual models, favoring either sedimentary, metamorphic, or magmatic fluid sources, are based on isotopic tracers, giving ambiguous results. Here we use the trace element compositions of fluid inclusions to separate geochemical signals of the large-scale fluid source from effects of deposit-scale fluid interaction with the sedimentary host rocks. Specifically, we compare the ratios of Rb, K, B, As, Sr, and Ba between clearly magmatic-hydrothermal Cu-Au ores at Copper Canyon in the Battle Mountain–Eureka trend with the Gold Quarry and Chukar Footwall deposits on the Carlin trend that contain high-grade gold in similar sedimentary host rocks. Results indicate that both ore districts can be related to upper crustal hydrous magmatic intrusions, but are now exposed at different levels of erosion and formed at different distances from their magmatic fluid source. Fluid compositions are best explained by separation of a deep magmatic fluid into Rb-K–enriched brine and B-As-Au–enriched vapor, followed by cooling and contraction of the magmatic vapor phase to an epithermal liquid, which reacted with Sr-Ba–bearing sedimentary rocks during ascent and eventual precipitation of Au-rich arsenian pyrite.

Hydrothermal Evolution of the Çöpler Porphyry-Epithermal Au Deposit, Erzincan Province, Central Eastern Turkey

The Copler Au deposit (measured and indicated resource of 122.8 million tonnes at 1.7 g/t Au, 4.8 g/t Ag, and 0.1 wt % Cu) is centered around shallow-level dioritic to granodioritic intrusive rocks of the middle Eocene Copler-Kabatas magmatic complex, which have been emplaced into a succession of regionally metamorphosed late Paleozoic-Mesozoic sedimentary and carbonate rocks. The deposit comprises a centrally located subeconomic porphyry Cu-Au system characterized by a potassically altered (biotite-K-feldspar-magnetite) core overprinted by a more extensive phyllic (quartz-sericite) alteration zone. The potassic alteration zone is associated with early M-type hairline magnetite and crosscutting B-type quartz ± magnetite ± sulfide veinlets, whereas the enveloping phyllic-altered rocks contain abundant D-type quartz-pyrite and lesser polymetallic quartz-sulfide veinlets. Intermediate-sulfidation epithermal Au mineralization that overprints the porphyry occurred in two stages. Main-stage epithermal mineralization is characterized by carbonate sulfide veinlets consisting of manganocalcite, arsenical pyrite, arsenopyrite, marcasite, chalcopyrite, tennantite/tetrahedrite, galena, and sphalerite. Late-stage sooty pyrite veinlets contain some realgar and orpiment and are associated with zones of extensive carbonate alteration. In the carbonate sulfide veinlets, invisible gold is primarily hosted within arsenical pyrite and, to a lesser extent, by arsenopyrite, tetrahedrite, and tennantite. In sooty pyrite veinlets, invisible gold is associated with fine-grained arsenical pyrite. Manto-type carbonate-replacement zones occur in the distal portions of the porphyry system and constitute a significant gold resource. These carbonate-replacement bodies display a mineral paragenesis similar to that of the epithermal carbonate sulfide veinlets in that they contain abundant arsenical pyrite together with lesser chalcopyrite, arsenopyrite, and marcasite, and sparse sphalerite, galena, tennantite, and tetrahedrite. Invisible gold in these ores is contained mainly within pyrite and chalcopyrite and, to a lesser extent, in arsenopyrite, tetrahedrite, and tennantite. Polyphase brine inclusions (~47–62 wt % NaCl equiv) in early B-type quartz ± magnetite ± sulfide veinlets were trapped together with low-salinity (~3–5.5 wt % NaCl equiv), vapor-rich inclusions at temperatures ~390°C and at a depth of ~1.5 km under lithostatic conditions. Fluids associated with the overprinting phyllic alteration were slightly cooler (~370°C) and less saline (37–42 wt % NaCl equiv). Fluid inclusions in manganocalcite and sphalerite from epithermal carbonate sulfide veinlets trapped moderate-salinity (4–15 wt % NaCl equiv) fluids at ~290°C, whereas fluid inclusions hosted in barite and realgar from sooty pyrite veinlets were formed from low-temperature (~100°C) and low- to moderate-salinity (1–14 wt % NaCl equiv) fluids. These data indicate that the Au-mineralizing system at Copler progressed from a high-temperature porphyry system to a relatively low temperature, intermediate-sulfidation epithermal system. Deposition of gold in the early stages of epithermal mineralization resulted from cooling, sulfidation, and neutralization of predominantly magmatic sourced hydrothermal fluids, whereas a meteoric water component is evident in the latest stage of mineralization. Deposit-scale geologic observations combined with fluid inclusion and stable isotope evidence suggest that mineralization at Copler records activity of a relatively deep epithermal system and that its formation was structurally and lithologically controlled. Specifically, the thick, premineralization carbonate sequence once overlying the deposit acted as a pressure seal and also as a neutralizing agent during the build up of the magmatic-hydrothermal system. The weakening of this carbonate cover by igneous intrusion and subsequent hydrothermal activity may have contributed to later selective erosion of the alteration zone, thereby telescoping the intermediate-sulfidation epithermal system onto the earlier porphyry system and creating the Copler window.

Mineralogy and genetic characteristics of the Rudnik Pb-Zn/Cu,Ag,Bi,W polymetallic deposit (Central Serbia) - New occurrence of Pb(Ag)Bi sulfosalts

The mineral aschamalmite, of heyrovskyite-like composition, but different in structure, from the Rudnik Pb–Zn/Cu,Ag,Bi,W polymetallic deposit in the central part of Serbia has been investigated. This polymetallic deposit includes over 90 hydrothermal and skarn-replacement orebody types, primarily hosted by Cretaceous sediments and occassionally by Oligocene dykes and sills of dacitic composition, and contact-metamorphic-metasomatic rocks. These rocks are host to an assemblage of pyrrhotite, colloform pyrite, chalcopyrite, galena, arsenopyrite, native bismuth and scheelite as well as minor pyrite, sphalerite, bismuthinite, argentopentlandite, and native silver. The chemical composition of the ore is very complex, where weight contents of valuable metals range as follows (%): Zn 0.49–4.49; Pb 0.90–5.66; Cu 0.08–2.18; WO 3 0.05–1.18; Ag 0.005–0.030; Bi 0.005–0.081; and Cd 0.002–0.016. In reflected light, aschamalmite is optically anisotropic, with moderately high bireflectance ranging from slightly greenish to slightly gray. Electron-microprobe analysis gave an average crystallochemical formulae of (Pb 5.82 Ag 0.20 ) Σ6.02 Bi 2.03 (S 8.93 Te 0.02 Se 0.01 ) Σ8.96 . The strongest diffraction maximums of the X-ray powder pattern [ d (in A)(I)] are 3.419(100), 3.382(92), and 3.334(66). Monoclinic unit cell parameters are a =13.727(7); b =4.122(3); c =31.32(2) A; β =90.72(5) o ; and V =1771.8(1) A 3 . Mineral assemblages and genesis of the Rudnik polymetallic deposit are discussed in detail and the sulfobismuthite mineralization has been compared with similar well-known global deposits.

Constraints on the solid solubility of Hg, Tl, and Cd in arsenian pyrite

Arsenic-rich (arsenian) pyrite can contain up to tens of thousands of parts per million (ppm) of toxic heavy metals such as Hg, Tl, and Cd, although few data are available on their solid solubility behavior. When a compilation of Hg, Tl, and Cd analyses from different environments are plotted along with As in a M(Hg, Tl, and Cd)-As log-log space, the resulting wedge-shaped distribution of data points suggests that the solid solubility of the aforementioned metals is strongly dependent on the As concentration of pyrite. The solid solubility limits of Hg in arsenian pyrite—i.e., the upper limit of the wedge-shaped zone in compositional space—are similar to the one previously defined for Au by Reich et al. (2005) (CHg,Au = 0.02CAs+ 4 × 10–5), whereas the solubility limit of Tl in arsenian pyrite is approximated by a ratio of Tl/As = 1. In contrast, and despite a wedge-shaped distribution of Cd-As data points for pyrite in Cd-As log-log space, the majority of Cd analyses reflect the presence of mineral particles of Cd-rich sphalerite and/or CdS. Based on these data, we show that arsenian pyrite with M/As ratios above the solubility limit of Hg and Tl contain nanoparticles of HgS, and multimetallic Tl-Hg mineral nanoparticles. These results indicate that the uptake of Hg and Tl in pyrite is strongly dependent on As contents, as it has been previously documented for metals such as Au and Cu. Cadmium, on the other hand, follows a different behavior and its incorporation into the pyrite structure is most likely limited by the precipitation of Cd-rich nanoparticulate sphalerite. The distribution of metal concentrations below the solubility limit suggests that hydrothermal fluids from which pyrite precipitate are dominantly undersaturated with respect to species of Hg and Tl, favoring the incorporation of these metals into the pyrite structure as solid solution. In contrast, the formation of metallic aggregates of Hg and Tl or mineral nanoparticles in the pyrite matrix occurs when Hg and Tl locally oversaturate with respect to their solid phases at constant temperature. This process can be kinetically enhanced by high-to-medium temperature metamorphism and thermal processing or combustion, which demonstrates a retrograde solubility for these metals in pyrite.

Comparison of the native antimony-bearing Paiting gold deposit, Guizhou Province, China, with Carlin-type gold deposits, Nevada, USA

The Paiting gold deposit, Guizhou Province, China, has been regarded as a Carlin-type gold deposit by several researchers. Alteration and ore-related minerals from the Paiting deposit were examined, and results were compared with the Cortez Hills Carlin-type gold deposit, Nevada, USA. Similarities include the structural and stratigraphic controls on the orebodies in both deposits and the occurrence of invisible gold ionically bound in arsenian pyrite. Significant differences include the following: (1) The gold-bearing mineral in Nevada is arsenian pyrite. However, gold-bearing minerals in the Paiting deposit include arsenopyrite, arsenian pyrite, and trace pyrrhotite. Also, euhedral or subhedral gold-bearing arsenian pyrite at Paiting contains significantly less As, Cu, and Hg than gold-bearing pyrite from Nevada. (2) Alteration in the Paiting deposit displays significantly less decarbonatization. Instead, dolomite precipitation, which has not been described in Nevada deposits, is associated with deposition of gold-bearing sulfide minerals. (3) Stibnite and minor native antimony typify Paiting late-ore-stage minerals, whereas in Nevada, realgar, orpiment, and calcite are common late-ore-stage minerals. Precipitation of native antimony in the Paiting deposit reflects the evolution of a late-ore fluid with unusually low sulfur and oxygen fugacities. Some characteristics of the Paiting gold deposit, including formation of ore-stage dolomite and precipitation from CO2-rich ore fluids at temperatures in excess of 250 °C, are more typical of orogenic deposits than Nevada Carlin deposits. The presence of similarities in the Paiting deposit to both Carlin type and orogenic deposits is consistent with formation conditions intermediate to those typical of Carlin type and orogenic systems.

Mineralogical control on arsenic release during sediment–water interaction in abandoned mine wastes from the Argentina Puna

The sulfide-rich residues of La Concordia mine, Argentina Puna, are accumulated in tailing dams that remained exposed to the weathering agents for almost 30years. In such period of time, a complex sequence of redox and dissolution/precipitation reactions occurred, leading to the gradual oxidation of the wastes and the formation of weathering profiles. The sources of arsenic in the wastes were analyzed by XRD and SEM/EDS analysis while a standardized sequential extraction procedure was followed to define solid As associations. In addition, the release of As during sediment–water interaction was analyzed in a period of 10months. The results indicate that primary As-bearing minerals are arsenian pyrite and polymetallic sulfides. As-jarosite and scarce arsenates are the only secondary As-bearing minerals identified by XRD and SEM/EDS. However, the rapid release (i.e., <1h) of arsenic from suspensions of the studied sediments in water, seems to be associated to the dissolution of highly soluble (hydrous)sulfates, as it was determined in samples of the efflorescences that cover the entire site. Contributions from the more abundant As-jarosite are also expected in longer periods of sediment–water interaction, due to its low rate of dissolution in acid and oxic conditions. Finally, near 30% of As remains adsorbed onto Fe (hydr)oxides thus representing a hazardous reservoir with the potential of mobilizing As into porewaters and streamwaters if the acidic and oxidizing conditions that predominate in the region are altered.

Geochemical characteristics of the giant Nibao Carlin-type gold deposit (Guizhou, China) and their geological implications

A large gold orebody controlled by Fault F1 was newly discovered in the giant Nibao Carlin-type gold deposit from southwestern Guizhou, China. Ore or rock samples were collected and studied to reveal the relationship among various orebodies which distributed in Fault F1 and its upper and lower plates, and to figure out the possible origin of ore-forming material. Tuff or tufaceous material was considered to be basic volcanic rocks in terms of their characteristic values of Al2O3/TiO2. Positive correlation was found between Au and As, and the correlation coefficient is particularly high within the fault fracture zone of the F1. Analysis shows that As can be regarded as a preferentially indicative element in gold prospection, while minerals of hydrothermal origin such as pyrite and arsenopyrite can be used as mineralogical indicative for gold prospection. Geochemical characteristics of trace elements and rare earth elements (REE) show that mantle source materials might have been involved in gold mineralization of different ore bodies. Large-scale Emei mantle plume eruption in the Early Permian resulted in thick volcanic sedimentary rock positioned between the karst unconformity surface at the top of the Maokou Formation and the bottom of the Longtan Formation. The Yanshanian tectonic activities played a significant role in driving gold-rich fluids to pressure-release spaces such as fault fracture zone and structure-controlling alteration zone (abbreviated to Sbt, according to Chinese). Those fluids reacted with ore-hosting rocks through water–rock interactions and resulted in the formation of gold-rich arsenian pyrite and arsenopyrite. Gold mineralization might have resulted from reactions between Fe-poor and gold-rich ore-forming fluids and tuffs which was relatively rich in iron, during which Fault F1 was considered to be the key to the formation of this giant gold orebody.

Mineralization and trace element distribution in pyrite using EMPA in exploration drill holes from Cheshmeh Zard gold district, Khorasan Razavi Province, Iran

ناحیه مطالعاتی در شمال استان خراسان رضوی و 45 کیلومتری جنوب نیشابور قرار دارد. رگه های طلادار درون سنگهای گرانیت، گرانودیوریت، گرانودیوریت پورفیری، آندزیت، برش و توف نفوذ کرده اند. رگه ها از جنس کوارتز و کلسیت هستند. مناطق اصلی دگرسانی شامل منطقه سرسیتیک، سیلیسی، پروپلیتیک و منطقه کربنات است. کانی زایی به‌طور نزدیکی با دگرسانیهای سیلیسی و سرسیتیک به شکل رگه‌چه و با منطقه پروپلیتیک به شکل افشان همراه است. کانی شناسی کانیهای باطله کوارتز، کلسدونی، سرسیت، آدولاریا، کلسیت، دولومیت، ایلیت، دیکیت، آلبیت، کائولینیت و کلریت است. کانی زایی رگه ای عمدتا با رگه‌چه ها، برش، افشان و استوک ورک همراه هستند. رگه‌چه ها از پیریت، مارکازیت، آرسنوپیریت و کمتر کالکوپیریت، اسفالریت، گالن، مگنتیت و هماتیت تشکیل شده اند. بیشترین عیار طلا در رگه های سیلیسی دیده می شود. پیریت کانی سولفیدی اصلی در کانی سازی اولیه است. سه نوع پیریت بر اساس ترکیب شیمیایی شناسایی شده است: پیریت خالص، پیریت غنی از آرسنیک و پیریت تیتانیوم- وانادیوم دار. تجزیه های ریزکاوشگر الکترونی بیشترین غلظت آرسنیک، تیتانیوم و وانادیوم را به ترتیب 62/3، 91/3 و 53/0 درصد وزنی در پیریتهای رگه های طلادار نشان می دهند. طلا معمولا همراه با پیریت آرسنیک دار و پیریت تیتانیوم- وانادیوم دار است. براساس مطالعه بافت و ترکیب پیریتها، رگه‌چه‌های پیریت آرسنیک دار همراه با کانیهای سولفیدی آرسنوپیریت، کالکوپیریت، گالن، اسفالریت در دمای بالا و با کاهش دما و فشار، پیریتهای فرامبوئیدال با حاشیه حاوی آرسنیک و طلا شکل گرفته اند و در ادامه پیریتهای درشت تیتان دار به‌وجود آمده اند. پیریتهای خالص و تأخیری درشت بلور آخرین فاز کانی ساز در منطقه هستند.

Reactivity and speciation of mineral-associated arsenic in seasonal and permanent wetlands of the Mekong Delta

Millions of people in the deltaic regions of S/SE Asia regularly consume As contaminated groundwater. Arsenic persists within these groundwaters despite being flushed by several pore volumes of recharge, indicative of an in situ solid phase source. Despite the importance of this solid phase source, the identity and reactivity of the minerals hosting and releasing As in the deltaic aquifers remain poorly constrained. Here we seek to define the chemistry and reactivity of As and its host minerals in aquifer sediments recharged by both seasonally saturated and permanent wetlands in the Mekong Delta of Cambodia.Sediment cores were retrieved to depths of up to 30m. Selective extractions on near-surface sediments (to depths of 4–6m) indicate that more than a third (27–50%) of the Fe in the profile is “reducible” (citrate–bicarbonate–dithionite–extractable) – nominally consisting of Fe(III) oxides. The Fe(III) oxide fraction was approximately the same under seasonal wetlands (mean=39%) compared with sediments from beneath permanent wetlands (mean=37%). Correspondingly, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectra analysis indicates that the Fe mineral phases are predominantly goethite and hematite (30–50%).Analysis of solid phase As speciation by X-ray absorption near edge structure (XANES) spectroscopy showed arsenate in the shallowest sediments (upper 1 and 4m of seasonal and permanent wetlands), and arsenite and/or As sulfides as the dominant phases in the deeper sediments. The reducible As fraction ranged from 17% to 42% of the total As at both sites. The exception was found in a peat layer at 6m beneath the seasonal wetland, in which only 1% of the total As was reducible. Arsenian pyrite was the predominant form of As in the peat. Thus, a pool of As hosted by reducible mineral phases persists in sediments below both the seasonal and permanently saturated wetland sites.

Evaluación de la movilización del As procedente de los residuos mineros abandonados de una zona semiárida (Rodalquilar, Almería)

Navarro, A., Martin, A. 2015. Evaluation of As mobilization from abandoned mine wastes of a semi-arid area (Rodalquilar, Almeria). Ecosistemas 24(2): 76-89. Doi.: 10.7818/ECOS.2014.24-2.12 Field and laboratory studies and mathematical modeling were used in order to assess the long-term mobilization of As from an uncontrolled tailings deposit, located next to the old mine of Rodalquilar (Almeria). Leaching mine wastes by column experiments indicates the possible movement of As at concentrations ranging between 30.9 and 1.2 mg /L, and pH values between 8.24 and 7.9, in a saline leachate character and showed electrical conductivities of 425-22 100 µS/cm. The mobility of some metalloids such as arsenic may be produced by the weathering of arsenian pyrite, present in the mine wastes in appreciable amounts, and jarosite and Fe oxy-hydroxides, where the arsenic appears in appreciable amounts. In this area groundwater showed high concentrations of Al, As, Cd, Fe, Hg , Mn, Ni, Pb, Se, Sb and Zn, which exceed water quality criteria for human consumption. Highlights the extent reached by As contamination detected throughout the aquifer and with concentrations reaching 0.2 mg /L. The dissolution of Fe oxy- hydroxides in areas of low redox potential could explain the existence of appreciable amounts of As, Fe and other metals dissolved in groundwater. MODFLOW modeling code simulated the transport of As in the aquifer of Rodalquilar and indicated that the main pollutant control mechanism, in addition to the hydrodynamic dispersion is adsorption on Fe oxy- hydroxides. The results suggest a progressive increase in the concentrations of As in groundwater for years.

Synthesis, characterization, and thermodynamics of arsenates forming in the Ca-Fe(III)-As(V)-NO3system: Implications for the stability of Ca-Fe arsenates

Arseniosiderite and yukonite are among the important arsenate minerals occurring as secondary alteration products in relation to the oxidation of arsenopyrite and arsenian pyrite and as discrete grains in some gold ores, mine tailings, and contaminated soils. Characteristics of these Ca-Fe arsenate species are not well known and our understanding of the conditions promoting their formation and dissolution is limited. Long- and short-range structural characteristics and thermodynamic properties of the Ca-Fe arsenates forming in the Ca-Fe(III)-As(V)-NO3 system were determined to better predict the mineralogical transformations taking place in neutralized sludge and tailings environments, and their influence on arsenic mobilization. Yukonite and arseniosiderite readily form from solutions with highly variable compositions at a wide pH range from slightly acidic to alkaline conditions. Calcium concentrations corresponding to molar Ca/(Ca+Fe+As) ratios as low as 0.1 appear to be adequate for their formation. Our experimental results confirm observations in natural settings and mine tailings where scorodite is progressively replaced by yukonite and arseniosiderite. The initial amorphous precipitates made of small oligomeric units of edge-sharing FeO6 octahedra with bridging arsenate evolve to yukonite through the establishment of corner linkages between the FeO6 chains. Yukonite represents a nanocrystalline precursor and Ca-deficient variety of arseniosiderite. Formation of arseniosiderite is kinetically controlled with faster development of crystallinity at neutral to slightly acidic pH and slower kinetics under alkaline conditions. Calorimetric measurements provided an enthalpy of formation value of −1950.3 ± 3.1 kJ/mol and standard entropy of 237.4 ± 4.4 J/(mol·K) for arseniosiderite [with composition Ca0.663Fe1.093(AsO4)(OH)1.605·0.827H2O], the corresponding Gibbs free energy of formation is −1733 ± 3.4 kJ/mol. A rough estimate of the thermodynamic properties of yukonite is also provided. Arseniosiderite is a stable arsenate between pH 3.5 and 7.5 in solutions saturated with respect to soluble Ca minerals such as calcite, gypsum, anorthite, or Ca-montmorillonite. Arsenic release from mine wastes and contaminated soils can be effectively controlled by arseniosiderite and the conditions promoting its formation such as lime-treatment leading to gypsum saturation in ferric arsenate solutions would prove to be desirable for stabilizing arsenic in the form of arseniosiderite in mine wastes.

The Nature of Ore‐forming Fluids of the Carlin‐type Gold Deposit in Southwest China: A Case from the Zimudang Gold Deposit

AbstractThe Zimudang gold deposit is a large Carlin‐type gold deposit in the Southwest Guizhou Province, China, with an average Au content of 6.2 g/t. Gold is mainly hosted in the fault zone and surrounding strata of the F1 fault and Permian Longtan Formation, and the ore bodies are strictly controlled by both the faults and strata. Detailed mineralogy and geochemistry studies are conducted to help judge the nature of ore‐forming fluids. The results indicate that the Au is generally rich in the sulfides of both ores and wall rocks in the deposit, and the arsenian pyrite and arsenopyrite are the main gold‐bearing sulfides. Four subtypes of arsenian pyrite are found in the deposit, including the euhedral and subhedral pyrite, framboidal pyrite, pyrite aggregates and pyrite veins. The euhedral and subhedral pyrite, which can take up about 80% of total pyrite grains, is the dominant type. Au distributed unevenly in the euhedral and subhedral pyrite, and the content of the Au in the rim is relatively higher than in the core. Au in the pyrite veins and pyrite aggregates is lower than the euhedral and subhedral pyrite. No Au has been detected in the points of framboidal pyrites in this study. An obvious highly enriched As rim exists in the X‐ray images of euhedral pyrites, implying the ore‐forming fluids may be rich in As. The relationship between Au and As reveals that the Au may host as a solid solution (Au+) and nanoparticles of native gold (Au0) in the sulfides. The high Co/Ni ratio (&gt;1) of sulfides and the enrichment of W in the ores all reflect that the gold‐bearing minerals and ore‐forming process were mainly related to the hydrothermal fluids, but the magmatic and volcanic activities cannot be neglected. The general existence of Au and As in the sulfides of both ores and wall rocks and the REE results suggest that the ore‐forming fluids may mainly be derived from the basin itself. The enrichment of Tl suggests that the ore‐forming fluids may be enriched in Cl. The Ce and Eu show slightly or apparently negative anomalies, which means the ore fluids were probably formed under reducing environment. The Y/Ho ratios of ore samples fluctuate around 28, implying the bicarbonate complexation and fluorine were both involved in the ore‐forming process. Combined with the previous studies and our results, we infer that the ore‐forming fluids enriched Au, As, HS− and halogen (F, Cl) were derived from the mixture of reducing basinal fluids and magmatic or volcanic hydrothermal fluids.

Geology and geochemistry of listwaenite-related gold mineralization in the Sayi gold deposit, Xinjiang, NW China

The Sayi gold deposit is part of the Sartohay ophiolitic mélange in west Junggar, Xinjiang, China, and is hosted by listwaenite, which was transformed from serpentinite in a shear zone via fluid–rock reaction. Gold mineralization is hosted by mylonitized listwaenites and quartz veins within listwaenite lenses, formed during shearing. Our study demonstrates that fluid concentrated Au, Ag, As, Sb, Cu, Cr, Ni, and Co during transformation from serpentinite to listwaenite and ductile deformation. Deformation due to shearing played an important role in focusing ore-forming fluid along the shear zone. Gold mineralization accompanied formation of hydrothermal minerals in the following stages: carbonate–quartz–pyrite (CQP, stage I), mariposite–gersdorffite–gold (MGG, II), quartz–carbonate–pyrite (QCP, III), gold-bearing quartz (IV) and dolomite–calcite stage (V). Geological characteristics of MGG in mylonitized listwaenite demonstrate that gold mineralization formed during the transition from ductile to brittle deformation, which was followed by gold-bearing quartz veins filling brittle fractures. The Au contents show a positive correlation with Ag, As, Cu, and Sb contents in mylonitized listwaenite samples, consistent with the coexistence of native gold, gersdorffite, arsenian pyrite, and chalcopyrite in mylonitized listwaenite. Pressure decrease due to hydraulic fracturing during the transition from ductile to brittle deformation induced gold deposition in the Sayi deposit.

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

Arsenic (As) concentrations as high as 179μg/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 200m) 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 17ppm. 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 10μg/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 530ppm, reaching up to 1840ppm. 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.