Mineralogy and texture of Fe-Ni sulfides in CI1 chondrites: Clues to the extent of aqueous alteration on the CI1 parent body

To better understand the role of aqueous alteration on the CI1 parent body, we have analyzed the texture, composition and mineral associations of iron nickel sulfides in four of the five known CI1 chondrites.The most commonly-occurring sulfide present in the CI1 chondrites is the iron-deficient Fe,Ni sulfide pyrrhotite ([Fe,Ni]_1−xS), that has a composition close to that of stoichiometric troilite (FeS). Three of the CI1s (Alais, Ivuna and Tonk) also contain pentlandite ([Fe,Ni]₉S₈), although pentlandite is a rare phase in Ivuna. Cubanite (CuFe₂S₃) was found in both Alais and Ivuna in this study, although it has also been reported in Orgueil (MacDougall and Kerridge, 1977). The pyrrhotite grains in all four chondrites form hexagonal, rectangular or irregular shapes, and show no evidence of Ni or Co zoning. The pyrrhotite grains in Orgueil and Ivuna are, in general, smaller, and show more “corrosions,” or “embayments,” than those in Alais or Tonk.We suggest that the precursor sulfide present in the CI1 chondrites was troilite which, during brecciation and oxidation on the parent body at a temperature of 100°C or less, converted the troilite to magnetite and pyrrhotite with pentlandite inclusions. Subsequently, continued alteration on the parent body removed pentlandite—partially from Alais, Tonk and Ivuna, completely from Orgueil—leaving behind pyrrhotite with spaces (“corrosions”) where the pentlandite had been. Ni derived from the pentlandite was incorporated into ferrihydrite, onto the surface of which the Ni,Na sulfate Ni-bloedite formed.Based on the size and abundant “corrosions” within pyrrhotite grains, combined with observations from other authors, we conclude that Orgueil and Ivuna have undergone a greater degree of alteration than Alais and Tonk. Further work is needed to assess the conditions under which pentlandite would be dissolved preferentially to pyrrhotite, as the study of terrestrial literature indicates that the latter mineral is preferentially removed.     

The distribution of platinum group elements (PGE) and other chalcophile elements among sulfides from the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada, and the origin of palladium in pentlandite

Concentrations of platinum group elements (PGE), Ag, As, Au, Bi, Cd, Co, Mo, Pb, Re, Sb, Se, Sn, Te, and Zn, have been determined in base metal sulfide (BMS) minerals from the western branch (402 Trough orebodies) of the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada. The sulfide assemblage is dominated by pyrrhotite, with minor pentlandite, chalcopyrite, and pyrite, and they represent monosulfide solid solution (MSS) cumulates. The aim of this study was to establish the distribution of the PGE among the BMS and platinum group minerals (PGM) in order to understand better the petrogenesis of the deposit. Mass balance calculations show that the BMS host all of the Co and Se, a significant proportion (40–90%) of Os, Pd, Ru, Cd, Sn, and Zn, but very little (<35%) of the Ag, Au, Bi, Ir, Mo, Pb, Pt, Rh, Re, Sb, and Te. Osmium and Ru are concentrated in equal proportions in pyrrhotite, pentlandite, and pyrite. Cobalt and Pd (∼1 ppm) are concentrated in pentlandite. Silver, Cd, Sn, Zn, and in rare cases Au and Te, are concentrated in chalcopyrite. Selenium is present in equal proportions in all three BMS. Iridium, Rh, and Pt are present in euhedrally zoned PGE sulfarsenides, which comprise irarsite (IrAsS), hollingworthite (RhAsS), PGE-Ni-rich cobaltite (CoAsS), and subordinate sperrylite (PtAs₂), all of which are hosted predominantly in pyrrhotite and pentlandite. Silver, Au, Bi, Mo, Pb, Re, Sb, and Te are found predominantly in discrete accessory minerals such as electrum (Au–Ag alloy), hessite (Ag₂Te), michenerite (PdBiTe), and rhenium sulfides. The enrichment of Os, Ru, Ni, and Co in pyrrhotite, pentlandite, and pyrite and Ag, Au, Cd, Sn, Te, and Zn in chalcopyrite can be explained by fractional crystallization of MSS from a sulfide liquid followed by exsolution of the sulfides. The early crystallization of the PGE sulfarsenides from the sulfide melt depleted the MSS in Ir and Rh. The bulk of Pd in pentlandite cannot be explained by sulfide fractionation alone because Pd should have partitioned into the residual Cu-rich liquid and be in chalcopyrite or in PGM around chalcopyrite. The variation of Pd among different pentlandite textures provides evidence that Pd diffuses into pentlandite during its exsolution from MSS. The source of Pd was from the small quantity of Pd that partitioned originally into the MSS and a larger quantity of Pd in the nearby Cu-rich portion (intermediate solid solution and/or Pd-bearing PGM). The source of Pd became depleted during the diffusion process, thus later-forming pentlandite (rims of coarse-granular, veinlets, and exsolution flames) contains less Pd than early-forming pentlandite (cores of coarse-granular).     

Evidence for aqueous activity on comet 81P/Wild 2 from sulfide mineral assemblages in Stardust samples and CI chondrites

The discovery of nickel-, copper-, and zinc-bearing iron sulfides from comet 81P/Wild 2 (Wild 2) represents the strongest evidence, in the Stardust collection, of grains that formed in an aqueous environment. We investigated three microtomed TEM sections which contain crystalline sulfide assemblages from Wild 2 and twelve thin sections of the hydrothermally altered CI chondrite Orgueil. Detailed structural and compositional characterizations of the sulfide grains from both collections reveal striking similarities. The Stardust samples include a cubanite (CuFe₂S₃) grain, a pyrrhotite [(Fe,Ni)_1−xS]/pentlandite [(Fe,Ni)₉S₈] assemblage, and a pyrrhotite/sphalerite [(Fe,Zn)S] assemblage. Similarly, the CI-chondrite sulfides include individual cubanite and pyrrhotite grains, cubanite/pyrrhotite assemblages, pyrrhotite/pentlandite assemblages, as well as possible sphalerite inclusions within pyrrhotite grains. The cubanite is the low temperature orthorhombic form, which constrains temperature to a maximum of 210 °C. The Stardust and Orgueil pyrrhotites are the 4C monoclinic polytype, which is not stable above ∼250 °C. The combinations of cubanite and pyrrhotite, as well as pyrrhotite and pentlandite signify even lower temperatures. The crystal structures, compositions, and petrographic relationships of these sulfides constrain formation and alteration conditions. Taken together, these constraints attest to low-temperature hydrothermal processing.Our analyses of these minerals provide constraints on large scale issues such as: heat sources in the comet-forming region; aqueous activity on cometary bodies; and the extent and mechanisms of radial mixing of material in the early nebula. The sulfides in the Wild 2 collection are most likely the products of low-temperature aqueous alteration. They provide evidence of radial mixing of material (e.g. cubanite, troilite) from the inner solar system to the comet-forming region and possible secondary aqueous processing on the cometary body.     

A laser ablation ICP-MS study of platinum-group and chalcophile elements in base metal sulfide minerals of the Jinchuan Ni–Cu sulfide deposit,NW China

The paper presents concentrations of the platinum-group and chalcophile elements in the base metal sulfides (BMS) from the Jinchuan Ni–Cu sulfide deposit determined by laser ablation-inductively coupled plasma-mass spectrometry. Mass balance calculations reveal that pentlandite hosts a large proportion of Co, Ni and Pd (> 65%), and that pentlandite and pyrrhotite accommodate significant proportions of Re, Os, Ru, Rh, and Ag (~ 35–90%), whereas chalcopyrite contains a small amount of Ag (~ 10%) but negligible platinum-group elements. Iridium and Pt are not concentrated in the BMS and mostly occur in As-rich platinum-group minerals. The enrichments of Co, Ni, Re, Os, Ru, and Rh in pentlandite and pyrrhotite, and Cu in chalcopyrite are consistent with the fractionation of sulfide liquid and exsolution of pentlandite and pyrrhotite from the mono-sulfide solid solution (MSS). The Ir-bearing minerals exsolved from the MSS, depleting pentlandite and pyrrhotite in Ir, whereas sperrylite exsolved from the residual sulfide liquid on cooling. Diffusion of Pd from residual sulfide liquid into pentlandite during its exsolution from the MSS and crystallization of Pt-bearing minerals in the residual sulfide liquid resulted in the enrichment of Pd in pentlandite and decoupling between Pd and Pt in the Jinchuan net-textured and massive ores.     

Deformation,metamorphism, and mobilization of Ni–Cu–PGE sulfide ores at Garson Mine,Sudbury

The Garson Ni–Cu–platinum group element deposit is a deformed, overturned, low Ni tenor contact-type deposit along the contact between the Sudbury Igneous Complex (SIC) and stratigraphically underlying rocks of the Huronian Supergroup in the South Range of the 1.85-Ga Sudbury structure. The ore bodies are coincident with steeply south-dipping, north-over-south D₁ shear zones, which imbricated the SIC, its ore zones, and underlying Huronian rocks during mid-amphibolite facies metamorphism. The shear zones were reactivated as south-over-north, reverse shear zones during D₂ at mid-greenschist facies metamorphism. Syn-D₂ metamorphic titanite yields an age of 1,849?±?6 Ma, suggesting that D₁ and D₂ occurred immediately after crystallization of the SIC during the Penokean Orogeny. The ore bodies plunge steeply to the south parallel to colinear L₁ and L₂ mineral lineations, indicating that the geometry of the ore bodies are strongly controlled by D₁ and D₂. Sulfide mineralization consists of breccia ores, with minor disseminated sulfides hosted in norite, and syn-D₂ quartz–calcite–sulfide veins. Mobilization by ductile plastic flow was the dominant mechanism of sulfide/metal mobilization during D₁ and D₂, with additional minor hydrothermal mobilization of Cu, Fe, and Ni by hydrothermal fluids during D₂. Metamorphic pentlandite overgrows a S₁ ferrotschermakite foliation in D₁ deformed ore zones. Pentlandite was exsolved from recrystallized polygonal pyrrhotite grains after cessation of D₁, which resulted in randomly distributed large pentlandite grains and randomly oriented pentlandite loops along the grain boundaries of polygonal pyrrhotite within the breccia ore. It also overgrows a S₂ chlorite foliation in D₂ shear zones. Pyrrhotite recrystallized and was flattened during D₂ deformation of breccia ore along narrow shear zones. Exsolution of pentlandite loops along the grain boundaries of these flattened grains produced a pyrrhotite–pentlandite layering that is not observed in D₁ deformed ore zones. The overprinting of the two foliations by pentlandite and exsolution of pentlandite along the grain boundaries of flattened pyrrhotite grains suggest that the Garson ores reverted to a metamorphic monosulfide solid solution at temperatures ranging between 550 and 600 °C during D₁ and continued to deform as a monosulfide solid solution during D₂.     

Temporal variability in terrestrially-derived sources of particulate organic carbon in the lower Mississippi River and its upper tributaries

In this study, we examined the temporal changes of terrestrially-derived particulate organic carbon (POC) in the lower Mississippi River (MR) and in a very limited account, the upper tributaries (Upper MR, Ohio River, and Missouri River). We used for the first time a combination of lignin-phenols, bulk stable carbon isotopes, and compound-specific isotope analyses (CSIA) to examine POC in the lower MR and upper tributaries.A lack of correlation between POC and lignin phenol abundances (Λ₈) was likely due to dilution effects from autochthonous production in the river, which has been shown to be considerably higher than previously expected. The range of δ¹³C values for p-hydroxycinnamic and ferulic acids in POC in the lower river do support that POM in the lower river does have a significant component of C₄ in addition to C₃ source materials. A strong correlation between δ¹³C values of p-hydroxycinnamic, ferulic, and vanillyl phenols suggests a consistent input of C₃ and C₄ carbon to POC lignin while a lack of correlation between these same phenols and POC bulk δ¹³C further indicates the considerable role of autochthonous carbon in the lower MR POC budget. Our estimates indicate an annual flux of POC of 9.3 × 10⁸ kg y⁻¹ to the Gulf of Mexico. Total lignin fluxes, based on Λ₈ values of POC, were estimated to be 1.2 × 10⁵ kg y⁻¹. If we include the total dissolved organic carbon (DOC) flux (3.1 × 10⁹ kg y⁻¹) reported by [Bianchi T. S., Filley T., Dria K. and Hatcher, P. (2004) Temporal variability in sources of dissolved organic carbon in the lower Mississippi River. Geochim. Cosmochim. Acta68, 959-967.], we get a total organic carbon flux of 4.0 × 10⁹ kg y⁻¹. This represents 0.82% of the annual total organic carbon supplied to the oceans by rivers (4.9 × 10¹¹ kg).     

Supergene alteration of the Mt Windarra nickel sulphide ore deposit,Western Australia

Three main zones of progressive oxidation, termed the transition, violaritepyrite and oxide zones, can be delineated in the supergene profile of the Mt Windarra massive/matrix ore deposit. In the broad transition zone from pure primary ore, pentlandite is progressively oxidised to an iron rich violarite of composition Co_0.02Fe_1.38Ni_1.60 S₄, releasing Fe²⁺ and Ni²⁺ ions into solution. Up to 43% of this Ni²⁺ moves to nearby pyrrhotite margins which are replaced firstly by nickeliferous smythite and then by a second lamellar-textured violarite with an even higher iron content but lacking in cobalt (approximately Fe_1.6Ni_1.4S₄). On completion of violaritisation of the pentlandite, violaritisation of the pyrrhotite also ceases and the remainder of the pyrrhotite is rapidly replaced by secondary pyrite/marcasite, siderite and void space, this reaction defining the top of transition zone. Both sulphur and nickel are extracted from solution and further Fe²⁺ ions are released into solution. The violarite-pyrite zone is characterised by the absence of pentlandite and pyrrhotite and continued stability of violarite and secondary iron disulphides. Most, if not all, of the iron generated by these oxidation reactions precipitates as magnesian siderite at the expense of magnesite, giving rise to solutions containing mainly Mg²⁺ and Ni²⁺ ions. At and just above the water table atmospheric oxygen is reduced while the sulphides are oxidised to sulphate and hydroxides. Much of the iron remains in situ as characteristic goethite relicts while nickel and copper are leached, producing the enrichment below the water table. The overall genetic model proposed is electrochemical and is analogous to the corrosion of a piece of metallic iron partially immersed in differentially aerated water.     

Mechanism and kinetics of pseudomorphic mineral replacement reactions: A case study of the replacement of pentlandite by violarite

Although pseudomorphic mineral replacement reactions are common in all geological environments, and have long been considered important to many geological processes such as metamorphism, metasomatism, diagenesis, and chemical weathering, their mechanisms are still not well known. We present a combined textural and kinetic study of the replacement of pentlandite, (Fe,Ni)₉S₈, by violarite (NiFe)₃S₄, and describe the mechanisms and kinetic behavior of this reaction by considering the role of the fluid phase, the causes of coupling between pentlandite dissolution and violarite precipitation, the rate-limiting steps controlling the kinetic behavior, and the origin of the length scale of the features preserved during pseudomorphism.The experiments were conducted under mild hydrothermal conditions (80-210 °C, vapor saturated pressures). Reaction kinetics shows a complex behavior depending on various physical and chemical parameters including temperature, pH, concentrations of various reaction species, solid-weight-to-fluid-volume-ratio and specific surface area. The rate of replacement (i) increases with temperature from 80 to 125 °C, then decreases as temperature further increases to 210 °C, (ii) first increases then decreases with decreasing pH from pH 6 to 1, (iii) increases with increasing concentration of oxidants such as O_2(aq), H₂O₂, and KMnO₄, but decreases with increasing concentration of Ni²⁺ and Fe³⁺, and with increasing solid-weight-to-fluid-volume ratio, (iv) increases linearly with the specific surface area. This kinetic behavior as well as the resulting textures revealed a coupled dissolution-reprecipitation reaction mechanism.Nanometer-scale pseudomorphic replacement, through which the crystallographic orientation of pentlandite is inherited by violarite, occurs only between 1 < pH < 6, and spatial coupling between dissolution and reprecipitation is controlled by the local solution chemistry as well as by epitaxial nucleation mediated by the pentlandite substrate. The kinetic results show that pentlandite dissolution is rate-limiting under mild acidic to neutral conditions (1 < pH < 6), while violarite precipitation is rate-limiting under strong acidic conditions (pH 1). The difference in rate-limiting steps influences the coupling mechanism and causes the different degrees of preservation (length scale of pseudomorphism) and different morphologies observed at high and low pHs: pentlandite dissolution being rate-limiting results in nanoscale coupling between dissolution and precipitation and thus nanoscale pseudomorphism (length scale <20 nm), in which the replacement precisely preserves the morphology and internal details, resembling remarkably the natural pentlandite/violarite assemblages. In contrast, violarite precipitation being rate-limiting results in microscale pseudomorphism (length scale ∼10 μm): the morphology of the pentlandite grains is only roughly preserved and internal details are not preserved.This case study illustrates some general principles of replacement reactions proceeding via the coupled dissolution-reprecipitation mechanism: (i) primary mineral dissolution needs to be rate-limiting compared to the secondary mineral precipitation in order to achieve a high degree pseudomorphic replacement; (ii) the effects of solution composition on reaction kinetics can be qualitatively rationalized by considering the rate-limiting step reaction.     

Zelda and Company: Petrogenesis of sulfide-rich Fremdlinge and constraints on solar nebula processes

A detailed mineralogic and chemical study of Zelda, a gigantic (1mm diameter) Fremdling from the Allende CAI, Egg 6, was performed in an attempt to understand the mode of formation of sulfide-rich Fremdlinge and their relation to other types of Fremdlinge. Zelda is composed primarily of pentlandite, pyrrhotite and V-Cr-rich magnetite. Minor phases include NiFePt metal, molybdenite, whitiockite and refractory metal nuggets (RMN) of OsRu and PtIr. The refractory siderophile abundances in Zelda are about 20,000 to 70,000 times chondritic.NiFe grains are highly embayed and are surrounded by a mixture of pentlandite and PtIr RMN. PtIr RMN are found exclusively at the embayed boundaries of NiFe, while OsRu RMN are found distributed throughout the entire Fremdlinge. The texture and mineral and bulk chemistry of Zelda are consistent with closed system sulfidization of a metal-magnetite precursor, with the metal reacting to form a mixture of pentlandite and PtIr, and the magnetite reacting to form pyrrhotite. The evidence suggests that this sulfidization approached equilibrium at a temperature of 800–900°C.Examination of Egg 6 in the vicinity of Zelda indicates that the Fremdling underwent extensive reaction with its surroundings, losing perhaps 40% of its original mass. The reaction involved partial melting, breakdown of NiFe, magnetite and sulfide, formation of V-magnetite-rich veins, and diffusion of Fe, V and Cr into neighboring spinels. Compositional profiles measured in a large spinel near Zelda suggest a diffusion time of approximately 1 hour at a temperature of about 1150°C. Examination of other Fremdlinge indicates that the presence of V-fassaite rims around Fremdlinge helps to protect them from undergoing such types of reaction.The most likely formation of Fremdlinge appears to have involved relatively cold accretion of previously formed grains of magnetite, NiFe and RMN, followed by partial sintering and in some cases sulfidization before incorporation into proto-CAIs. Following incorporation, further sulfidization and reaction of some Fremdlinge with their surroundings occurred. The common coexistence of very high concentrations of refractory aderophiles and low-T metal-magnetite-sulfide assemblages, as well as the evidence that Fremdlinge were incorporated into proto-CAI as solid objects, underscore the complexity of early solar nebula processes and require local mixing of phases formed at considerably different T and fO₂. Many of the phase relations observed in Fremdlinge point to CAIs existing for reasonable periods of time at temperatures of about 850°C and cooler, but only for very short times at temperatures greater than 1000°C, although some of these phase assemblages may have been created by exsolution during lower temperature reequilibration.     

Chemical weathering in the Krishna Basin and Western Ghats of the Deccan Traps, India: Rates of basalt weathering and their controls

Rates of chemical and silicate weathering of the Deccan Trap basalts, India, have been determined through major ion measurements in the headwaters of the Krishna and the Bhima rivers, their tributaries, and the west flowing streams of the Western Ghats, all of which flow almost entirely through the Deccan basalts.Samples (n = 63) for this study were collected from 23 rivers during two consecutive monsoon seasons of 2001 and 2002. The Total dissolved solid (TDS) in the samples range from 27 to 640 mg l⁻¹. The rivers draining the Western Ghats that flow through patches of cation deficient lateritic soils have lower TDS (average: 74 mg l⁻¹), whereas the Bhima (except at origin) and its tributaries that seem to receive Na, Cl, and SO₄ from saline soils and anthropogenic inputs have values in excess of 170 mg l⁻¹. Many of the rivers sampled are supersaturated with respect to calcite. The chemical weathering rates (CWR) of “selected” basins, which exclude rivers supersaturated in calcite and which have high Cl and SO₄, are in range of ∼3 to ∼60 t km⁻² y⁻¹. This yields an area-weighted average CWR of ∼16 t km⁻² y⁻¹ for the Deccan Traps. This is a factor of ∼2 lower than that reported for the Narmada-Tapti-Wainganga (NTW) systems draining the more northern regions of the Deccan. The difference can be because of (i) natural variations in CWR among the different basins of the Deccan, (ii) “selection” of river basin for CWR calculation in this study, and (iii) possible contribution of major ions from sources, in addition to basalts, to rivers of the northern Deccan Traps.Silicate weathering rates (SWR) in the selected basins calculated using dissolved Mg as an index varies between ∼3 to ∼60 t km⁻² y⁻¹, nearly identical to their CWR. The Ca/Mg and Na/Mg in these rivers, after correcting for rain input, are quite similar to those in average basalts of the region, suggesting near congruent release of Ca, Mg, and Na from basalts to rivers. Comparison of calculated and measured silicate-Ca in these rivers indicates that at most ∼30% of Ca can be of nonsilicate origin, a likely source being carbonates in basalts and sediments.The chemical and silicate weathering rates of the west flowing rivers of the Deccan are ∼4 times higher than the east flowing rivers. This difference is due to the correspondingly higher rainfall and runoff in the western region and thus reemphasises the dominant role of runoff in regulating weathering rates. The silicon weathering rate (SWR) in the Krishna Basin is ∼15 t km⁻² y⁻¹, within a factor of ∼2 to those in the Yamuna, Bhagirathi, and Alaknanda basins of the Himalaya, suggesting that under favourable conditions (intense physical weathering, high runoff) granites and the other silicates in the Himalaya weather at rates similar to those of Deccan basalts. The CO₂ consumption rate for the Deccan is deduced to be ∼3.6 × 10⁵ moles km⁻² y⁻¹ based on the SWR. The rate, though, is two to three times lower than reported for the NTW rivers system; it still reinforces the earlier findings that, in general, basalts weather more rapidly than other silicates and that they significantly influence the atmospheric CO₂ budget on long-term scales.     

Solubility and near-equilibrium dissolution rates of quartz in dilute NaCl solutions at 398-473 K under alkaline conditions

The dissolution-precipitation of quartz controls porosity and permeability in many lithologies and may be the best studied mineral-water reaction. However, the rate of quartz-water reaction is relatively well characterized far from equilibrium but relatively unexplored near equilibrium. We present kinetic data for quartz as equilibrium is approached from undersaturation and more limited data on the approach from supersaturated conditions in 0.1 molal NaCl + NaOH + NaSiO(OH)₃ solutions with pH 8.2-9.7 at 398, 423, 448, and 473 K. We employed a potentiometric technique that allows precise determination of solution speciation within 2 kJ mol⁻¹ of equilibrium without the need for to perturb the system through physical sampling and chemical analysis. Slightly higher equilibrium solubilities between 423 and 473 K were found than reported in recent compilations. Apparent activation energies of 29 and 37 kJ mol⁻¹ are inferred for rates of dissolution at two surface sites with different values of connectedness: dissolution at Q¹ or Q² silicon sites, respectively. The dissolution mechanism varies with ΔG such that reactions at both sites control dissolution up until a critical free energy value above which only reactions at Q¹ sites are important. When our near-equilibrium dissolution rates are extrapolated far from equilibrium, they agree within propagated uncertainty at 398 K with a recently published model by Bickmore et al. (2008). However, our extrapolated rates become progressively slower than model predictions with increasing temperature. Furthermore, we see no dependence of the postulated Q¹ reaction rate on pH, and a poorly-constrained pH dependence of the postulated Q² rate. Our slow extrapolated rates are presumably related to the increasing contribution of dissolution at Q³ sites far from equilibrium. The use of the potentiometric technique for rate measurement will yield both rate data and insights into the mechanisms of dissolution over a range of chemical affinity. Such measurements are needed to model the evolution of many natural systems quantitatively.     

Experimental determination of the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions to 400°C

The solubility of silver sulphide (acanthite/argentite) has been measured in aqueous sulphide solutions between 25 and 400°C at saturated water vapour pressure and 500 bar to determine the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave, connected to a high-performance liquid chromatographic pump, titanium sampling loop, and a back-pressure regulator on line. Samples for silver determination were collected via the titanium sampling loop at experimental temperatures and pressures. The solubilities, measured as total dissolved silver, were in the range 1.0 × 10⁻⁷ to 1.30 × 10⁻⁴ mol kg⁻¹ (0.01 to 14.0 ppm), in solutions of total reduced sulphur between 0.007 and 0.176 mol kg⁻¹ and pH_T,p of 3.7 to 12.7. A nonlinear least squares treatment of the data demonstrates that the solubility of silver sulphide in aqueous sulphide solutions of acidic to alkaline pH is accurately described by the reactions0.5Ag₂S(s) + 0.5H₂S(aq) = AgHS(aq) K_s,1110.5Ag₂S(s) + 0.5H₂S(aq) + HS⁻ = Ag(HS)2− K_s,122Ag₂S(s) + 2HS⁻ = Ag₂S(HS)22− K_s,232where AgHS(aq) is the dominant species in acidic solutions, Ag(HS)2− under neutral pH conditions and Ag₂S(HS)22− in alkaline solutions. With increasing temperature the stability field of Ag(HS)2− increases and shifts to more alkaline pH in accordance with the change in the first ionisation constant of H₂S(aq). Consequently, Ag₂S(HS)22− is not an important species above 200°C. The solubility constant for the first reaction is independent of temperature to 300°C, with values in the range logK_s,111 = −5.79 (±0.07) to −5.59 (±0.09), and decreases to −5.92 (±0.16) at 400°C. The solubility constant for the second reaction increases almost linearly with inverse temperature from logK_s,122 = −3.97 (±0.04) at 25°C to −1.89 (±0.03) at 400°C. The solubility constant for the third reaction increases with temperature from logK_s,232 = −4.78 (±0.04) at 25°C to −4.57 (±0.18) at 200°C. All solubility constants were found to be independent of pressure within experimental uncertainties. The interaction between Ag⁺ and HS⁻ at 25°C and 1 bar to form AgHS(aq) has appreciable covalent character, as reflected in the exothermic enthalpy and small entropy of formation. With increasing temperature, the stepwise formation reactions become progressively more endothermic and are accompanied by large positive entropies, indicating greater electrostatic interaction. The aqueous speciation of silver is very sensitive to fluid composition and temperature. Below 100°C silver(I) sulphide complexes predominate in reduced sulphide solutions, whereas Ag⁺ and AgClOH⁻ are the dominant species in oxidised waters. In high-temperature hydrothermal solutions of seawater salinity, chloride complexes of silver(I) are most important, whereas in dilute hydrothermal fluids of meteoric origin typically found in active geothermal systems, sulphide complexes predominate. Adiabatic boiling of dilute and saline geothermal waters leads to precipitation of silver sulphide and removal of silver from solution. Conductive cooling has insignificant effects on silver mobility in dilute fluids, whereas it leads to quantitative loss of silver for geothermal fluids of seawater salinity.     

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.     

Chemical erosion in the eastern Himalaya: Major ion composition of the Brahmaputra and δC of dissolved inorganic carbon

Major ion composition of waters, δ¹³C of its DIC (dissolved inorganic carbon), and the clay mineral composition of bank sediments in the Brahmaputra River System (draining India and Bangladesh) have been measured to understand chemical weathering and erosion and the factors controlling these processes in the eastern Himalaya. The time-series samples, collected biweekly at Guwahati, from the Brahmaputra mainstream, were also analyzed for the major ion composition. Clay mineralogy and chemical index of alteration (CIA) of sediments suggest that weathering intensity is relatively poor in comparison to that in the Ganga basin. This is attributed to higher runoff and associated physical erosion occurring in the Brahmaputra basin. The results of this study show, for the first time, spatial and temporal variations in chemical and silicate erosion rates in the Brahmaputra basin. The subbasins of the Brahmaputra watershed exhibit chemical erosion rates varying by about an order of magnitude. The Eastern Syntaxis basin dominates the erosion with a rate of ∼300 t km⁻² y⁻¹, one of the highest among the world river basins and comparable to those reported for some of the basaltic terrains. In contrast, the flat, cold, and relatively more arid Tibetan basin undergoes much slower chemical erosion (∼40 t km⁻² y⁻¹). The abundance of total dissolved solids (TDS, 102-203 mg/L) in the time-series samples collected over a period of one year shows variations in accordance with the annual discharge, except one of them, cause for which is attributable to flash floods. Na* (Na corrected for cyclic component) shows a strong positive correlation with Si, indicating their common source: silicate weathering. Estimates of silicate cations (Na_sil+K_sil+Ca_sil+Mg_sil) suggest that about half of the dissolved cations in the Brahmaputra are derived from silicates, a proportion higher than that for the Ganga system. The CO₂ consumption rate due to silicate weathering in the Brahmaputra watershed is ∼6 × 10⁵ moles km⁻² y⁻¹; whereas that in the Eastern Syntaxis subbasin is ∼19 × 10⁵ moles km⁻² y⁻¹, similar to the estimates for some of the basaltic terrains. This study suggests that the Eastern Syntaxis basin of the Brahmaputra is one of most intensely chemically eroding regions of the globe; and that runoff and physical erosion are the controlling factors of chemical erosion in the eastern Himalaya.     

The experimental calibration of the iron isotope fractionation factor between pyrrhotite and peralkaline rhyolitic melt

A first experimental study was conducted to determine the equilibrium iron isotope fractionation between pyrrhotite and silicate melt at magmatic conditions. Experiments were performed in an internally heated gas pressure vessel at 500 MPa and temperatures between 840 and 1000 °C for 120-168 h. Three different types of experiments were conducted and after phase separation the iron isotope composition of the run products was measured by MC-ICP-MS. (i) Kinetic experiments using ⁵⁷Fe-enriched glass and natural pyrrhotite revealed that a close approach to equilibrium is attained already after 48 h. (ii) Isotope exchange experiments—using mixtures of hydrous peralkaline rhyolitic glass powder (∼4 wt% H₂O) and natural pyrrhotites (Fe_1 − xS) as starting materials— and (iii) crystallisation experiments, in which pyrrhotite was formed by reaction between elemental sulphur and rhyolitic melt, consistently showed that pyrrhotite preferentially incorporates light iron. No temperature dependence of the fractionation factor was found between 840 and 1000 °C, within experimental and analytical precision. An average fractionation factor of Δ ⁵⁶Fe/⁵⁴Fe_{pyrrhotite-melt} = −0. 35 ± 0.04‰ (2SE, n = 13) was determined for this temperature range. Predictions of Fe isotope fractionation between FeS and ferric iron-dominated silicate minerals are consistent with our experimental results, indicating that the marked contrast in both ligand and redox state of iron control the isotope fractionation between pyrrhotite and silicate melt. Consequently, the fractionation factor determined in this study is representative for the specific Fe²⁺/ΣFe ratio of our peralkaline rhyolitic melt of 0.38 ± 0.02. At higher Fe²⁺/ΣFe ratios a smaller fractionation factor is expected. Further investigation on Fe isotope fractionation between other mineral phases and silicate melts is needed, but the presented experimental results already suggest that even at high temperatures resolvable variations in the Fe isotope composition can be generated by equilibrium isotope fractionation in natural magmatic systems.     

Cadmium deposition and mobility in the sediments of an acidic oligotrophic lake

A dated core from the profoundal zone in a pristine oligotrophic acidic lake was analyzed for Cd as well as for Al, Ca, Fe, Mg, Mn, Pb, Ti and total carbon and nitrogen. Overlying water and porewater samples were also obtained on six occasions at the same site, and yielded vertical profiles of pH and dissolved Cd, Ca, Fe, Mg, Mn, sulfide, SO₄⁻², organic and inorganic carbon concentrations. These extensive porewater and sediment geochemical data were used, together with information on infaunal benthos, to decipher the sedimentary record of Cd contamination. Depth variation of sediment Ca concentrations indicate that the lake suffered from progressive acidification starting about 1950. The present-day accumulation rate of Cd (J_acc^Cd = 5.4 ± 0.4 × 10⁻¹¹ mol cm⁻² yr⁻¹) in the sediments is the sum of the flux of Cd deposited with settling particles (J_S^Cd = 3.3 ± 0.2 × 10⁻¹¹ mol cm⁻² yr⁻¹) and the fluxes of dissolved Cd across the sediment-water interface due to molecular diffusion (J_D^Cd = 1.8 ± 0.3 × 10⁻¹¹ mol cm⁻² yr⁻¹), bioturbation (J_B^Cd = 1.1 ± 0.2 × 10⁻¹⁴ mol cm⁻² yr⁻¹) and bioirrigation (J_I^Cd = 0.27 ± 0.05 × 10⁻¹¹ mol cm⁻² yr⁻¹). Biological mixing of the sediments was negligible. The shape of the vertical profile of total Cd concentration with depth in the sediment appears to be determined more by its input history than by post-depositional mobilization and redistribution in the sediment column.     

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.     

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.     

Variations in Os isotope ratios of pyrrhotite as a result of water-rock and magma-rock interaction: Constraints from Virginia Formation-Duluth Complex contact zones

Os isotope ratios in pyrrhotite-bearing pelitic rocks of the ∼1.85 Ga Virginia Formation are variable, with perturbations linked to the emplacement of the ∼1.1 Ga Duluth Complex. Pyrrhotite in footwall rocks of the contact aureole show evidence for a mixing event at 1.1 Ga involving a low ¹⁸⁷Os/¹⁸⁸Os fluid. However, because rocks with perturbed pyrrhotite Os isotope ratios occur 1½ km or more from the Duluth Complex, the fluid is unlikely to have been of magmatic origin. Fluid inclusions in layer-parallel quartz veins provide evidence of the involvement of a boiling fluid at temperatures between ∼300 and 400 °C. Analyses of fluid inclusions via LA-ICP-MS show that the fluids contain up to 1.7 wt% Na, 1.1 wt% K, 4330 ppm Fe, 2275 ppm Zn, and 415 ppm Mg. The veins also contain pyrite or pyrrhotite, plus minor amounts of chalcopyrite, bornite, pentlandite, and sphalerite. The Re-Os isotopic ratios of pyrite from the veins indicate that they crystallized from low ¹⁸⁷Os/¹⁸⁸Os fluids (<0.2). δ¹⁸O values of vein quartz range from 7.7‰ to 9.5‰, consistent with an origin involving fluid with a relatively low δ¹⁸O value between 2‰ and 5‰. Meteoric water with such a low δ¹⁸O value could have interacted with the igneous rocks of the Complex and would have acquired Os with a low ¹⁸⁷Os/¹⁸⁸Os ratio. Strongly serpentinized olivine-rich rocks of the Complex are commonly characterized by such low δ¹⁸O values and we propose that the fluid involved in serpentinization was also responsible for the perturbation of the Os isotopic system recorded by pyrrhotite in the Virginia Formation. Two important observations are that only pyrrhotite-bearing assemblages in the contact aureole show isotopic perturbation and that intervals showing Os exchange are spatially restricted, and not uniformly distributed. Os exchange and mixing has occurred only where temperatures were sufficient to convert pyrite to pyrrhotite, and where time-integrated water-rock ratios in the aureole were high enough to provide a supply of Os.Troctolitic and gabbroic rocks of the Partridge River Intrusion, Duluth Complex, are characterized by Os isotope ratios that are indicative of variable degrees of crustal contamination (γ_Os values of ∼0-543). Xenoliths of carbonaceous and sulfidic pelitic rocks of the Virginia Formation found in the igneous rocks provide evidence that Os was released by organic matter and pyrite in the sedimentary rocks and assimilated by mantle-derived magma. However, residual pyrrhotite produced as a result of pyrite breakdown in the xenoliths is characterized by ¹⁸⁷Os/¹⁸⁸Os ratios that are much lower than anticipated and similar to those of pyrrhotite in the contact aureole. The Os exchange and addition shown by pyrrhotite in the xenoliths highlight an unusual cycle of Re-Os liberation during devolatilization, kerogen maturation, and pyrite to pyrrhotite conversion (processes that contribute to magma contamination), followed by Os uptake by pyrrhotite during back reaction involving magma and/or fluid characterized by a relatively low ¹⁸⁷Os/¹⁸⁸Os ratio. The extreme Os uptake recorded by pyrrhotite in the xenoliths, as well as the lesser degree of uptake recorded by pyrrhotite in the contact aureole, is in line with the high Os diffusivity in pyrrhotite experimentally determined by Brenan et al. (2000). Our data confirm that Os isotope ratios in pyrrhotite-bearing rocks may be readily perturbed. For this reason caution should be exercised in the interpretation of Os isotope ratios in rocks where pyrrhotite may be the primary host of Os.     

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

The kinetics of iodide (I⁻) and molecular iodine (I₂) oxidation by the manganese oxide mineral birnessite (δ-MnO₂) was investigated over the pH range 4.5-6.25. I⁻ oxidation to iodate proceeded as a two-step reaction through an I₂ intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I⁻ from solution was first order with respect to I⁻ concentration, pH, and birnessite concentration, such that −d[I⁻]/dt = k[I⁻][H⁺][MnO₂], where k, the third order rate constant, is equal to 1.08 ± 0.06 × 10⁷ M⁻² h⁻¹. The data are consistent with the formation of an inner sphere I⁻ surface complex as the first step of the reaction, and the adsorption of I⁻ exhibited significant pH dependence. Both I₂, and to a lesser extent, sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I₂ and , as well as the biophilic nature of I₂, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.