An experimental study of the mechanism of the replacement of magnetite by pyrite up to 300 °C

We present the results of an experimental study into the sulfidation of magnetite to form pyrite/marcasite under hydrothermal conditions (90-300 °C, vapor saturated pressures), a process associated with gold deposition in a number of ore deposits. The formation of pyrite/marcasite was studied as a function of reaction time, temperature, pH, sulfide concentration, solid-weight-to-fluid-volume ratio, and geometric surface area of magnetite in polytetrafluoroethylene-lined autoclaves (PTFE) and a titanium and stainless steel flow-through cell. Marcasite was formed only at pH_21°C <4 and was the dominant Fe disulfide at pH_21°C 1.11, while pyrite predominated at pH_21°C >2 and formed even under basic conditions (up to pH_21°C 12-13). Marcasite formation was favored at higher temperatures. Fine-grained pyrrhotite formed in the initial stage of the reaction together with pyrite in some experiments with large surface area of magnetite (grain size <125 μm). This pyrrhotite eventually gave way to pyrite. The transformation rate of magnetite to Fe disulfide increased with decreasing pH (at 120 °C; pH_120°C 0.96-4.42), and that rate of the transformation increased from 120 to 190 °C.Scanning electron microscope (SEM) imaging revealed that micro-pores (0.1-5 μm scale) existed at the reaction front between the parent magnetite and the product pyrite, and that the pyrite and/or marcasite were euhedral at pH_21°C <4 and anhedral at higher pH. The newly formed pyrite was micro-porous (0.1-5 μm); this micro-porosity facilitates fluid transport to the reaction interface between magnetite and pyrite, thus promoting the replacement reaction. The pyrite precipitated onto the parent magnetite was polycrystalline and did not preserve the crystallographic orientation of the magnetite. The pyrite precipitation was also observed on the PTFE liner, which is consistent with pyrite crystallizing from solution. The mechanism of the reaction is that of a dissolution-reprecipitation reaction with the precipitation of pyrite being the rate-limiting step relative to magnetite dissolution under mildly acidic conditions (e.g., pH_155°C 4.42).The experimental results are in good agreement with sulfide phase assemblage and textures reported from sulfidized Banded Iron Formations: pyrite, marcasite and pyrrhotite have been found to exist or co-exist in different sulfidized Banded Iron Formations, and the microtextures show no evidence of sub-μm-scale pseudomorphism of magnetite by pyrite.     

Alpine metamorphism of calcareous metasediments in the Western Hohe Tauern,tyrol: mineral equilibria in COHS fluids

During Tertiary regional metamorphism in the Western Hohe Tauern, reaching maximum P, T conditions around 6 kb, 550° C in calcareous metasediments, reaction of pyrite to pyrrhotite is suggested by regional distribution and textural relations. In rocks without graphite pyrite is common at all metamorphic grades. In graphite bearing rocks, however, the dominant Fe-sulfide is pyrite at lower grade and pyrrhotite at higher grade. Furthermore, in graphite bearing high grade rocks, pyrite is restricted to assemblages with Mg-rich silicates. Several factors control pyrite-pyrrhotite relations. Increase of temperature is most effective by increase of pyrrhotite vs. pyrite stability field, shift of silicate-sulfide reactions toward the stability field of pyrrhotite, creation of sulfur free fluids from devolatilization reactions, and increase in the proportions of sulfur bearing fluid species. Presence of graphite also favours progress of pyrite to pyrrhotite reaction, as shown by different -stabilities and changes in the amount of minerals and fluid during metamorphic heating of graphite bearing and graphite free assemblages. An opposite effect is shown by assemblages with low Fe-contents in Fe-Mg silicates, due to the enlarged stability field of such minerals with increasing Mg (and F) content. Another inhibition of pyrite to pyrrhotite reaction is suggested to be due to relatively high sulfur contents of H₂O rich infiltrating fluids.     

金属矿物的反应动力学与地球化学意义

概述了动力学实验的技术方法和金属矿物的反应动力学研究进展。动力学实验使用的三种基本化学反应装置是间歇反应器（ＢＲ）、活塞流反应器（ＰＦＲ）和混合流反应器（ＭＦＲ）,确定速率定律的数学方法包括积分法、微分法和混合法,以微分法中的初始速率法应用最广。目前主要研究了水溶液中黄铁矿氧化、黄铁矿和黄铜矿形成、晶质铀矿和磁铁矿溶解的速率定律和反应机理,发现：（１）酸性溶液中黄铁矿的氧化速率对Ｆｅ３＋和Ｏ２浓度呈分数依赖并受表面反应的控制;（２）低于３００℃时黄铁矿不能从溶液中直接成核,而需初始地通过ＦｅＳ先驱物的硫化生成,ＦｅＳ与Ｈ２Ｓ反应形成黄铁矿的速率方程为二级;（３）磁黄铁矿或黄铁矿与Ｃｕ２＋反应均可形成黄铜矿,前者经历了一系列准稳的Ｃｕ Ｆｅ硫化物的中间物,后者的速率方程为表观一级并受表面反应的控制;（４）酸性ｐＨ时磁铁矿的非线性溶解行为可采用表面反应扩散输运耦合的收缩核模型（ＳＣＭ）来描述。有关动力学实验成果完善和深化了对矿床中黄铁矿、黄铜矿的形成机理和风化壳中磁铁矿的稳定性等方面的认识。将来的实验研究将向更多的金属矿物和高温高压领域发展。     

Acid production from sulfide minerals using hydrogen peroxide weathering

Sulfide mineral weathering is a major source of acid generation in mining environments. Oxidation and hydrolysis reactions in soil and geologic material under earth surface conditions causes weathering of reduced sulfide minerals resulting in liberation of weathering products including acid. Pyrite and marcasite are minerals common in mine environments that cause acid generation. Many other sulfide minerals are present in mining environments which may or may not form acid upon weathering. Characterization of complex mineral assemblages containing S compounds is therefore critically important to pre-mine planning and postmine waste characterization. Despite the importance of mineral weathering behavior, little is known about the acid generation characteristics of common sulfide and sulfate minerals. To assess the response of common sulfide and sulfate minerals to oxidizing conditions, 13 minerals were subjected to treatment with 10% H₂O₂. The resulting leachate was analyzed for pH, electrical conductivity, S and titratable acidity. The sulfide minerals arsenopyrite, pyrite, chalcopyrite, pyrrhotite, marcasite and sphalerite demonstrated significantly elevated levels of titratable acidity and are acid generating in contrast to galena, chalcocite and all the sulfates. The sulfate minerals barite, anhydrite, gypsum, anglesite and jarosite were included in experimentation and were found not to form acid under strongly oxidizing conditions. Remediation strategies for disturbed lands containing reduced S minerals must therefore consider not only the total quantity of sulfide minerals present, but the specific mineralogy of the S compounds.     

Chemical influences on trace metal-sulfide interactions in anoxic sediments

Interactions of trace metals with sulfide in anoxic environments are important in determining their chemical form and potential toxicity to organisms. In recent years, a considerable body of observational data has accumulated that indicates very different behavior for various trace metals in sulfidic sediments. These differences in behavior cannot be entirely attributed to thermodynamic relationships, but also reflect differences in ligand exchange reaction kinetics, and redox reaction pathways.Pb, Zn, and Cd, which are generally pyritized to only a few percent of the “reactive” fraction, have faster water exchange reaction kinetics than Fe²⁺, resulting in MeS phases precipitating prior to FeS formation and subsequent pyrite formation, whereas, Co and Ni, which have slower H₂O exchange kinetics than Fe²⁺, are incorporated into pyrite. Although Hg and Cu have faster reaction kinetics than Fe²⁺, both are incorporated into pyrite or leached from the pyrite fraction with nitric acid. Hg undergoes significant chloride complexation, which can retard reaction with sulfide, but can also replace Fe in FeS to form HgS, which can only be dissolved in the pyrite fraction. Cu²⁺ is reduced by sulfide and forms a variety of sulfides with and without Fe that can only be dissolved with nitric acid. Mn²⁺ does not form a MnS phase easily and is incorporated into pyrite at high iron degrees of pyritization (DOP).Oxyanions of Mo and As are first reduced by sulfide. These reduced forms may then react with sulfides resulting in incorporation into pyrite. However, the oxyanion of Cr is reduced to Cr³⁺, which is kinetically inert to reaction with sulfide and, therefore, not incorporated into pyrite.     

Sulfide Remobilisation from Sulfide Ore at High Temperatures and Differential Stresses: An Experimental Approach

We conducted experiments to simulate sulfide remobilisation from sulfide ore. The starting material was from the Hongtoushan massive sulfide deposit, NE China, and is composed of pyrite, pyrrhotite, chalcopyrite, sphalerite, quartz, and silicate minerals. The ore was immersed in a solution of 20 wt.% NaCl for 260 h, and then was mounted in a Changjiang 500 triaxial rock stress machine. After the experiments were performed for 13 h at temperatures of 362, 464, 556 and 682°C, with corresponding confining and axial pressures, the samples were cooled at room temperatures. Our results from all the runs indicate that sulfides can be remobilised both mechanically and chemically, and that remobilisation is enhanced at higher temperatures. Mechanical remobilisation can only take place over limited distances and results in minor differentiation between various sulfide minerals. Distant external remobilisation to form new orebodies is most likely caused by chemical remobilisation. In contrast to plastically deformed areas, space resulting from cataclastic deformation could provide conduits for fluid transport and space for metal precipitation. Remobilised iron sulfides will precipitate as pyrrhotite at high temperatures, but as pyrite when temperature decreases. Furthermore, chalcopyrite is more easily remobilised than sphalerite under the conditions of the present experiments. Remobilisation accompanying deformation and metamorphism may add epigenetic features to syngenetic deposits.     

Copper–Gold Skarn Mineralization at the Karavansalija Ore Zone,Rogozna Mountain,Southwestern Serbia

Karavansalija ore zone is situated in the Serbian part of the Serbo‐Macedonian magmatic and metallogenic belt. The Cu–Au mineralization is hosted mainly by garnet–pyroxene–epidote skarns and shifts to lesser presence towards the nearby quartz–epidotized rocks and the overlying volcanic tuffs. Within the epidosites the sulfide mineralogy is represented by disseminated cobalt‐nickel sulfides from the gersdorfite‐krutovite mineral series and cobaltite, and pyrite–marcasite–chalcopyrite–base metal aggregates. The skarn sulfide mineralization is characterized by chalcopyrite, pyrite, pyrrhotite, bismuth‐phases (bismuthinite and cosalite), arsenopyrite, gersdorffite, and sphalerite. The sulfides can be observed in several types of massive aggregates, depending on the predominant sulfide phases: pyrrhotite‐chalcopyrite aggregates with lesser amount of arsenopyrite and traces of sphalerite, arsenopyrite–bismuthinite–cosalite aggregates with subordinate sphalerite and sphalerite veins with bismuthinite, pyrite and arsenopyrite. In the overlying volcanoclastics, the studied sulfide mineralization is represented mainly by arsenopyrite aggregates with subordinate amounts of pyrite and chalcopyrite. Gold is present rarely as visible aggregate of native gold and also as invisible element included in arsenopyrite. The fluid inclusion microthermometry data suggest homogenization temperature in the range of roughly 150–400°C. Salinities vary in the ranges of 0.5–8.5 wt% NaCl eq for two‐phase low density fluid inclusions and 15–41 wt% NaCl eq for two‐phase high‐salinity and three‐phase high‐salinity fluid inclusions. The broad range of salinity values and the different types of fluid inclusions co‐existing in the same crystals suggest that at least two fluids with different salinities contributed to the formation of the Cu–Au mineralization. Geothermometry, based on EPMA data of arsenopyrite co‐existing with pyrite and pyrrhotite, suggests a temperature range of 240–360°C for the formation of the arsenopyrite, which overlaps well with the data for the formation temperature obtained through fluid inclusion microthermometry. The sulfur isotope data on arsenopyrite, chalcopyrite, pyrite and marcasite from the different sulfide assemblages (ranging from 0.4‰ to +3.9‰ δ³⁴S_CDT with average of 2.29 δ³⁴S_CDT and standard deviation of 1.34 δ³⁴S_CDT) indicates a magmatic source of sulfur for all of the investigated phases. The narrow range of the data points to a common source for all of the investigated sulfides, regardless of the host rock and the paragenesis. The sulfur isotope data shows good overlap with that from nearby base‐metal deposits; therefore the Cu–Au mineralization and the emblematic base‐metal sulfide mineralization from this metallogenic belt likely share same fluid source.     

Oxide and sulphide minerals in highly oxidized, Rb-depleted, Archaean granulites of the Shevaroy Hills Massif, South India: Oxidation states and the role of metamorphic fluids

The Shevaroy Hills of northern Tamil Nadu, southern India, expose the highest-grade granulites of a prograde amphibolite facies to granulite facies deep-crustal section of Late Archaean age. These highly oxidized quartzofeldspathic garnet charnockites generally show minor high-TiO₂ biotite and amphibole as the only hydrous minerals and are greatly depleted in the incompatible elements Rb and Th. Peak metamorphic temperatures (garnet–orthopyroxene) and pressures (garnet–orthopyroxene–plagioclase–quartz) are near 750 °C and 8 kbar, respectively. Pervasive veinlets of K-feldspar exist throughout dominant plagioclase in each sample and show clean contact with orthopyroxene. They are suggested to have been produced by a low H₂O activity, migrating fluid phase under granulite facies conditions, most likely a concentrated chloride/carbonate brine with high alkali mobility accompanied by an immiscible CO₂-rich fluid. Silicate, oxide and sulphide mineral assemblages record high oxygen fugacity. Pyroxenes in the felsic rocks have high Mg/(Mg+Fe) (0.5–0.7). The major oxide mineral is ilmenite with up to 60 mole per cent exsolved hematite. Utilizing three independent oxygen barometers (ferrosilite–magnetite–quartz, ferrosilite–hematite–quartz and magnetite–hematite) in conjunction with garnet–orthopyroxene exchange temperatures, samples with XIlmHm>0.1 yield a consistent oxygen fugacity about two log units above fayalite stability. Less oxidized samples (XIlmHm<0.1) show some scatter with indications of having equilibrated under more reducing conditions. Temperature-f (O₂ ) arrays result in self consistent conditions ranging from 660 °C and 10^?16 bar to 820 °C and 10^?11.5 bar. These trends are confirmed by calculations based on the assemblage clinopyroxene–orthopyroxene–magnetite–ilmenite using the QUIlF program. In the most oxidized granulite samples (XIlmHm>0.4) pyrite is the dominant sulphide and pyrrhotite is absent. Pyrite grains in these samples have marginal alteration to magnetite along the rims, signifying a high-temperature oxidation event. Moderately oxidized samples (0.1no coexisting magnetite. Chalcopyrite is a common accessory mineral of pyrite and pyrrhotite in all the samples. Textures in some samples suggest that it formed as an exsolution product from pyrrhotite. Extensive vein networks of magnetite and pyrite, associated principally with the pyroxene and amphibole, give evidence for a pervasive, highly oxidizing fluid phase. Thermodynamic analysis of the assemblage pyrrhotite, pyrite and magnetite yields consistent high oxidation states at 700–800 °C and 8 kbar. The oxygen fugacity in our most oxidized pyrrhotite-bearing sample is 10^?12.65 bar at 770 °C. There are strong indications that the Shevaroy Hills granulites recrystallized in the presence of an alkali-rich, low H₂O-activity fluid, probably a concentrated brine. It cannot be demonstrated at present whether the high oxidation states were set by initially oxidized protoliths or effected by the postulated fluids. The high correspondence of maximally Rb-depleted samples with the highest recorded oxidation states suggests that the Rb depletion event coincided with the oxidation event, probably during breakdown of biotite to orthopyroxene+K-feldspar. We speculate that these alterations were effected by exhalations from deep-seated alkali basalts, which provided both heat and high oxygen fugacity, low a_H2O fluids. It will be of interest to determine whether greatly Rb-depleted granulites in other Precambrian terranes show similar highly-oxidizing signatures.     

Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

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

Geochemical effects of oxidation products and framboidal pyrite oxidation in acid mine drainage prediction techniques

Acid mine drainage predictive testwork associated with the Australian Mineral Industries Research Association (AMIRA) P387A Project: Prediction and Kinetic Control of Acid Mine Drainage (AMD) has critically examined static acid assessment and kinetic information from acid–base accounting techniques, including net acid production potential (NAPP), net acid generation (NAG) and column leach tests. This paper compares results on two waste rock samples that were obtained from the Kaltim Prima Coal mine (KPC) containing significant quantities of fine-grained framboidal pyrite. In agreement with other research, the authors' results indicated that framboidal pyrite is more reactive than euhedral forms due to the greater specific surface area of framboidal pyrite. This is evidenced by optical microscopy of reacted samples. Importantly, the results showed that NAPP testing is biased by the rapid acid generating oxidation of framboidal pyrite prior to, and during the acid neutralisation capacity (ANC) test. This can result in negative ANC values for samples containing significant framboidal pyrite (often “corrected” to zero kg H₂SO₄/t) when significant ANC is actually present in the sample. NAG testing using H₂O₂ indicated that samples containing a significant quantity of framboidal pyrite can result in the catalytic decomposition of the H₂O₂ prior to complete oxidation of the sulfide minerals present, requiring sequential addition of H₂O₂ for completion. A benefit of the NAG test, however, is that it assesses the net acid generation capacity of the sample without bias towards acid generation as is observed using NAPP methods. The kinetic NAG test also gives information on the reaction sequence of framboidal and euhedral pyrite. Periodic (kinetic) analysis of sub-samples from column leach tests indicated rapid oxidation of the framboidal pyrite compared to the euhedral pyrite, which was correlated with the greater framboidal pyrite surface area.Calculations to determine the sulfide/sulfate acidity derived from the oxidation of framboidal pyrite prior to; and during the ANC test have been developed to provide a better indication of the actual ANC (ANC_Actual) of the sample. Paste pH values of <pH 4–5 may be one suitable trigger mechanism for the implementation of this new method. This has led to an improved NAPP estimation of total acid production. Together with NAG and column leach testing this improved methodology has resulted in accurate AMD characterisation of samples containing acidic oxidation products and framboidal pyrite.     

A comparison of the dissolution behavior of troilite with other iron(II) sulfides; implications of structure

Further knowledge as to the nature of the structure of a terrestrial sample of troilite, FeS [stoichiometric iron(II) sulfide] is revealed by a combination of XPS studies and dissolution studies in acid. The XPS analysis of a pristine troilite surface (the sample being cleaved under high vacuum) is compared to that of a surface polished in an inert atmosphere and a surface after reaction in deoxygenated acid. Further comparison is made with polished and acid-reacted surfaces of pyrrhotite (Fe_1-xS) and pyrite (FeS₂). The pristine troilite S2p spectrum comprises mainly monosulfide 161.1 eV, within the reported range of monosulfide, together with evidence of an unsatisfied monosulfide surface state arising from S-Fe bond rupture. Small, higher oxidation state sulfur contributions, including a disulfide-like state are also present, which suggest the presence of defects due to some nonstoichiometry. The dissolution studies showed that the troilite, in addition to dissolving in acid as an ionic solid to produce H₂S, also exhibits some oxidation of sulfur in the surface layers. In addition, a study of the dissolution behavior of troilite under the influence of cathodic applied potential supported the existence of a proportion of the sulfur within troilite needing reduction before dissolution forming HS⁻ or H₂S can occur. A significant increase in the dissolution rate was observed with application of −105 mV (SHE), but further stepped decreases in potential to −405 mV and −705 mV resulted in a decreased rate of dissolution, a response typical of an ionic solid. The results of the studies emphasise the viewing of iron(II) sulfides as a continuum. Pyrrhotite has been reported previously to dissolve in acid both oxidatively (like pyrite) and nonoxidatively (like troilite) on the same surface. Dissolution studies using troilite, in Ar-purged acid, indicate that dissolution of this material may not be uniformly nonoxidative. XPS evidence of restructuring of the surface of troilite to pyrrhotite and the surface of pyrrhotite towards a FeS₂ type structure, after exposure to Ar-purged acid, is presented.     

Chalcophile and platinum-group element (PGE) concentrations in the sulfide minerals from the McCreedy East deposit,Sudbury, Canada,and the origin of PGE in pyrite

Magmatic sulfide deposits consist of pyrrhotite, pentlandite, chalcopyrite (± pyrite), and platinum-group minerals (PGM). Understanding the distribution of the chalcophile and platinum-group element (PGE) concentrations among the base metal sulfide phases and PGM is important both for the petrogenetic models of the ores and for the efficient extraction of the PGE. Typically, pyrrhotite and pentlandite host much of the PGE, except Pt which forms Pt minerals. Chalcopyrite does not host PGE and the role of pyrite has not been closely investigated. The Ni–Cu–PGE ores from the South Range of Sudbury are unusual in that sulfarsenide PGM, rather than pyrrhotite and pentlandite, are the main carrier of PGE, probably as the result of arsenic contribution to the sulfide liquid by the As-bearing metasedimentary footwall rocks. In comparison, the North Range deposits of Sudbury, such as the McCreedy East deposit, have As-poor granites in the footwall, and the ores commonly contain pyrite. Our results show that in the pyrrhotite-rich ores of the McCreedy East deposit Os, Ir, Ru, Rh (IPGE), and Re are concentrated in pyrrhotite, pentlandite, and surprisingly in pyrite. This indicates that sulfarsenides, which are not present in the ores, were not important in concentrating PGE in the North Range of Sudbury. Palladium is present in pentlandite and, together with Pt, form PGM such as (PtPd)(TeBi)₂. Platinum is also found in pyrite. Two generations of pyrite are present. One pyrite is primary and locally exsolved from monosulfide solid solution (MSS) in small amounts (<2 wt.%) together with pyrrhotite and pentlandite. This pyrite is unexpectedly enriched in IPGE, As (± Pt) and the concentrations of these elements are oscillatory zoned. The other pyrite is secondary and formed by alteration of the MSS cumulates by late magmatic/hydrothermal fluids. This pyrite is unzoned and has inherited the low concentrations of IPGE and Re from the pyrrhotite and pentlandite that it has replaced.     

Kinetics of H2-O2-H2O redox equilibria and formation of metastable H2O2 under low temperature hydrothermal conditions

Hydrothermal experiments were conducted to evaluate the kinetics of H_2(aq) oxidation in the homogeneous H₂-O₂-H₂O system at conditions reflecting subsurface/near-seafloor hydrothermal environments (55-250 °C and 242-497 bar). The kinetics of the water-forming reaction that controls the fundamental equilibrium between dissolved H_2(aq) and O_2(aq), are expected to impose significant constraints on the redox gradients that develop when mixing occurs between oxygenated seawater and high-temperature anoxic vent fluid at near-seafloor conditions. Experimental data indicate that, indeed, the kinetics of H_2(aq)-O_2(aq) equilibrium become slower with decreasing temperature, allowing excess H_2(aq) to remain in solution. Sluggish reaction rates of H_2(aq) oxidation suggest that active microbial populations in near-seafloor and subsurface environments could potentially utilize both H_2(aq) and O_2(aq), even at temperatures lower than 40 °C due to H_2(aq) persistence in the seawater/vent fluid mixtures. For these H₂-O₂ disequilibrium conditions, redox gradients along the seawater/hydrothermal fluid mixing interface are not sharp and microbially-mediated H_2(aq) oxidation coupled with a lack of other electron acceptors (e.g. nitrate) could provide an important energy source available at low-temperature diffuse flow vent sites.More importantly, when H_2(aq)-O_2(aq) disequilibrium conditions apply, formation of metastable hydrogen peroxide is observed. The yield of H₂O_2(aq) synthesis appears to be enhanced under conditions of elevated H_2(aq)/O_2(aq) molar ratios that correspond to abundant H_2(aq) concentrations. Formation of metastable H₂O₂ is expected to affect the distribution of dissolved organic carbon (DOC) owing to the existence of an additional strong oxidizing agent. Oxidation of magnetite and/or Fe⁺⁺ by hydrogen peroxide could also induce formation of metastable hydroxyl radicals (•OH) through Fenton-type reactions, further broadening the implications of hydrogen peroxide in hydrothermal environments.     

安徽铜陵冬瓜山铜矿床的叠加改造成矿机制：来自矿石结构的证据

长江中、下游地区块状硫化物矿床普遍受到燕山期岩浆及其热液的改造与叠加.本文以铜陵冬瓜山矿床为例,探讨这类矿床的成矿机制.该矿床主要由层状硫化物矿体组成,伴有矽卡岩型和斑岩型矿体.野外地质观察及室内矿相学的研究表明,冬瓜山层状矿体中矿石遭受了强烈的热变质作用及热液交代作用.进变质过程中形成的结构主要为黄铁矿受燕山期岩浆侵...     

Petrology,Geochemistry, and Fluid Inclusion Microthermometry of Sphalerite from the Laloki and Federal Flag Strata‐Bound Massive Sulfide Deposits,Papua New Guinea: Implications for Gold Mineralization

The Laloki and Federal Flag deposits are two of the many (over 45) polymetallic massive sulfide deposits that occur in the Astrolabe Mineral Field, Papua New Guinea. New data of the mineralogical compositions, mineral textures, and fluid inclusion studies on sphalerite from Laloki and Federal Flag deposits were investigated to clarify physiochemical conditions of the mineralization at both deposits. The two deposits are located about 2 km apart and they are stratigraphically hosted by siliceous to carbonaceous claystone and rare gray chert of Paleocene–Eocene age. Massive sulfide ore and host rock samples were collected from each deposit for mineralogical, geochemical, and fluid inclusion studies. Mineralization at the Laloki deposit consists of early‐stage massive sulfide mineralization (sphalerite‐barite, chalcopyrite, and pyrite–marcasite) and late‐stage brecciation and remobilization of early‐stage massive sulfides that was accompanied by late‐stage sphalerite mineralization. Occurrence of native gold blebs in early‐stage massive pyrite–marcasite‐chalcopyrite ore with the association of pyrrhotite‐hematite and abundant planktonic foraminifera remnants was due to reduction of hydrothermal fluids by the reaction with organic‐rich sediments and seawater mixing. Precipitation of fine‐grained gold blebs in late‐stage Fe‐rich sphalerite resulted from low temperature and higher salinity ore fluids in sulfur reducing conditions. In contrast, the massive sulfide ores from the Federal Flag deposit contain Fe‐rich sphalerite and subordinate sulfarsenides. Native gold blebs occur as inclusions in Fe‐rich sphalerite, along sphalerite grain boundaries, and in the siliceous‐hematitic matrix. Such occurrences of native gold suggest that gold was initially precipitated from high‐temperature, moderate to highly reduced, low‐sulfur ore fluids. Concentrations of Au and Ag from both Laloki and Federal Flag deposits were within the range (<10 ppm Au and <100 ppm Ag) of massive sulfides at a mid‐ocean ridge setting rather than typical arc‐type massive sulfides. The complex relationship between FeS contents in sphalerite and gold grades of both deposits is probably due to the initial deposition of gold on the seafloor that may have been controlled by factors such as Au complexes, pH, and fO₂ in combination with temperature and sulfur fugacity.     

Genesis of the Maanqiao gold deposit in the western Qinling orogen,central China: Constraints from fluid inclusions and in-situ sulfur isotopes

The western Qinling orogen (WQO) is one of the most important prospective gold provinces in China. The Maanqiao gold deposit, located on the southern margin of the Shangdan suture, is a representative gold deposit in the WQO. The Maanqiao deposit is hosted by the metasedimentary rocks of the Upper Devonian Tongyusi Formation. The EW-trending brittle-ductile shear zone controls the orebodies; they occur as disseminated, and auriferous quartz–sulfide vein. The ore-related hydrothermal alteration comprises silicification, sulfidation, sericitization, chloritization, and carbonatization. Native gold is visible and mainly associated with pyrite and pyrrhotite. Mineralization can be classified into the following three stages: bedding-parallel barren quartz–pyrite–(pyrrhotite) (early-stage), auriferous quartz–polymetallic (middle-stage), and carbonate–(quartz)–sulfide (late-stage).Detailed fluid inclusion (FI) studies revealed three types of inclusions in quartz and calcite: aqueous (W-type), CO₂–H₂O (C-type), and pure carbonic (PC-type) FIs. The primary FIs in the early-stage quartz are C- and PC-type, in the middle-stage quartz are mainly W- and C-type, and in the late-stage calcite are only W-type. During gold mineralization, the total FI homogeneous temperatures evolved from 189–375 °C (mostly 260–300 °C) to 132–295 °C (mostly 180–240 °C) to 123–231 °C (mostly 130–150 °C), and the salinities varied among 2.2–9.1 wt.% NaCl equiv. (mostly 5–8 wt.%) to 0.2–9.0 wt.% NaCl equiv. (mostly 3–6 wt.%) to 0.3–3.6 wt.% NaCl equiv. (mostly 2–4 wt.%). The ore-forming fluid was characterized as an H₂O–NaCl−CO₂−CH₄–(N₂) system with medium-low temperature and low salinity. The fluid immiscibility and fluid-rock interaction may be responsible for the precipitation of the sulfides and gold at the Maanqiao gold deposit. Three types of pyrite corresponding to the three mineralization stages, as well as pyrrhotite and arsenopyrite in the middle stage, are micro-analyzed for in-situ sulfur isotopic composition by LA-ICP-MS. Py1 yield near-zero δ³⁴S values of −2.5‰ to 3.0‰, which are somewhat lower than that of the granite hosted pyrites (Py-g, 4.8‰ to 6.6‰). The result suggests a mixed sulfur source from magmatic-hydrothermal fluids and the metamorphism of diagenetic pyrite. Pyrite + pyrrhotite + arsenopyrite assemblages in the middle-stage have relatively higher δ³⁴S values (6.6‰ to 12.3‰) and are mainly developed due to the metamorphism of the ore-host and underlying Devonian sedimentary sequences. The low δ³⁴S values of the late-stage fracture-filled Py3 (−21.9‰ to −17.0‰) resulted from an increasing oxygen fugacity, which was caused by the inflow of oxidized meteoric waters.Based on our studies, the Maanqiao gold deposit is considered to be an orogenic type and closely related to the Indosinian Qinling orogeny.     

Mine drainage from the weathering of sulfide minerals and magnetite

Pyrite and pyrrhotite are the principal minerals that generate acid drainage in mine wastes. Low-pH conditions derived from Fe-sulfide oxidation result in the mobilization of contaminant metals (such as Zn, Cd, Ni and Cr) and metalloids (such as As) which are of environmental concern. This paper uses data from detailed mineralogical and geochemical studies conducted at two Canadian tailings impoundments to examine the mineralogical changes that pyrite, pyrrhotite, sphalerite and magnetite undergo during and after sulfide oxidation, and the subsequent release and attenuation of associated trace elements. The stability of sphalerite in tailings impoundments generally is greater than that of pyrrhotite, but less than pyrite. Dissolved Ni and Co derived from Fe sulfides, and to a lesser extent, dissolved Zn and Cd from sphalerite, are commonly attenuated by early-formed Fe oxyhydroxides. As oxidation progresses, a recycling occurs due to continued leaching from low-pH pore waters and because the crystallinity of Fe oxyhydroxides gradually increases which decreases their sorptive capacity. Unlike many other elements, such as Cu, Pb and Cr, which form secondary minerals or remain incorporated into mature Fe oxyhydroxides, Zn and Ni become mobile. Magnetite, which is a potential source of Cr, is relatively stable except under extremely low-pH conditions. A conceptual model for the sequence of events that typically occurs in an oxidizing tailings impoundment is developed outlining the progressive oxidation of a unit of mine waste containing a mixed assemblage of pyrrhotite and pyrite.     

Sulfide remobilization during low temperature alteration of seafloor basalt

The behavior of sulfide minerals during the physical and chemical changes accompanying seafloor alteration was studied in three basalt flows from the bottom of D.S.D.P. Hole 418A, Leg 53. The rocks are mildly altered, and contain primary, authigenic, and vein sulfide minerals. Sulfide habit, mineralogy, and trace element content are inter-related and are correlated with the extent and type of silicate and oxide alteration. Incipient alteration at > 90°–100°C was accompanied by low temperature reequilibration of pyrrhotite, and locally, by the oxidation of pyrrhotite to pyrite plus magnetite. The dominant stage of alteration, at ≤90°C, is characterized by dissolution and local redistribution of pyrite and chalcopyrite, whose precipitation appears to be controlled by the water/rock ratio and the extent to which the water has been modified by reaction with the basalt. Chalcopyrite was concentrated relative to pyrite by slight changes in fluid composition caused by reaction with other minerals. Concurrent precipitation of smectite causes a net increase in rock volume, tending to restrict seawater access. Calculations of rock cooling rate through time suggest that the most prolonged hydrothermal circulation occurs at low temperatures, giving rise to pervasive low temperature alteration assemblages.     

Carbon–sulfur–iron relationships in sedimentary rocks from southwestern Taiwan: influence of geochemical environment on greigite and pyrrhotite formation

The importance of the magnetic iron sulfide minerals, greigite (Fe₃S₄) and pyrrhotite (Fe₇S₈), is often underappreciated in geochemical studies because they are metastable with respect to pyrite (FeS₂). Based on magnetic properties and X-ray diffraction analysis, previous studies have reported widespread occurrences of these magnetic minerals along with magnetite (Fe₃O₄) in two thick Plio-Pleistocene marine sedimentary sequences from southwestern Taiwan. Different stratigraphic zones were classified according to the dominant magnetic mineral assemblages (greigite-, pyrrhotite-, and magnetite-dominated zones). Greigite and pyrrhotite are intimately associated with fine-grained sediments, whereas magnetite is more abundant in coarse-grained sediments. We measured total organic carbon (TOC), total sulfur (TS), total iron (Fe_T), 1N HCl extractable iron (Fe_A), and bulk sediment grain size for different stratigraphic zones in order to understand the factors governing the formation and preservation of the two magnetic iron sulfide minerals. The studied sediments have low TS/Fe_A weight ratios (0.03–0.2), far below that of pyrite (1.15), which indicates that an excess of reactive iron was available for pyritization. Observed low TS (0.05–0.27%) is attributed to the low organic carbon contents (TOC=0.25–0.55%), which resulted from dilution by rapid terrigenous sedimentation. The fine-grained sediments also have the highest Fe_T and Fe_A values. We suggest that under conditions of low organic carbon provision, the high iron activity in the fine-grained sediments may have removed reduced sulfur so effectively that pyritization was arrested or retarded, which, in turn, favored preservation of the intermediate magnetic iron sulfides. The relative abundances of reactive iron and labile organic carbon appear to have controlled the transformation pathway of amorphous FeS into greigite or into pyrrhotite. Compared to pyrrhotite-dominated sediments, greigite-dominated sediments are finer-grained and have higher Fe_A but lower TS. We suggest that diagenetic environments with higher supply of reactive iron, lower supply of labile organic matter, and, consequently, lower sulfide concentration result in relatively high Eh conditions, which favor formation of greigite relative to pyrrhotite.     

Sulfide mineralogy and sulfur isotope geochemistry of layered sills in the Deer Lake Complex,Minnesota

The Deer Lake Complex, located in north-central Minnesota, consists of a series of layered peridotite-pyroxenite-gabbro sills. Sulfide minerals occur as fine disseminations throughout pyroxenite and gabbro units, and occur more sporadically in peridotite and basal chilled margin units. Sulfide volume percentage rarely exceeds 0.5. A distinct zonation in sulfide mineralogy and sulfur isotopic composition characterizes the sills. Cobaltian pentlandite is the dominant sulfide mineral in peridotite (pd) units, with Ni-enrichment most likely linked to the serpentinization process. δ³⁴Spd values are variable, ranging from ?3.5 to +2.8‰. Sulfide assemblages in pyroxenite (px) and lower gabbro units consist of chalcopyrite, pyrrhotite, and minor pentlandite. δ³⁴S_px values range from ?1 to +1 ‰. Pyrite is the principal sulfide mineral in upper gabbro (μg) units. Its origin may be related to increased f0₂ conditions of the remaining melt and to reaction between a S-bearing volatile phase and mafic silicates. δ³⁴S_ug values range from 1 to 3.5 ‰. Sulfur isotopic values of chilled margin (2–9 ‰) and peridotite units, together with the erratic spatial distribution of sulfide minerals in these zones, suggests that the parent magma was not initially saturated with sulfur, and that local sulfide concentrations are the result of incorporation of sulfur derived from metasedimentary country rocks. Sulfide saturation was more uniformly reached during pyroxenite formation, with contained sulfur being of magmatic origin. Enrichment in ³⁴S of pyrite from upper gabbro may be explained by buildup of isotopically heavy sulfur following a Rayleigh process, coupled with possible involvement of a SO₂-rich fluid phase during hydrothermal alteration.