Antimony speciation in saline hydrothermal fluids: A combined X-ray absorption fine structure spectroscopy and solubility study

Solubility of senarmontite (Sb₂O₃, cubic) in pure water and NaCl-HCl aqueous solutions, and local atomic structure around antimony in these fluids were characterized using in situ X-ray absorption fine structure (XAFS) spectroscopy at temperatures to 450 °C and pressures to 600 bars. These experiments were performed using a new X-ray cell which allows simultaneous measurement of the absolute concentration of the absorbing element in the fluid, and atomic environment around the absorber. Results show that aqueous Sb(III) speciation is dominated by the complex in pure water, mixed Sb-hydroxide-chloride complexes in acidic NaCl-HCl solutions (2 m NaCl-0.1 m HCl), and by Sb-chloride species in concentrated HCl solutions (3.5 m HCl). Interatomic Sb-O and Sb-Cl distances in these complexes range from 1.96 to 1.97 Å and from 2.37 to 2.47 Å, respectively. These structural data, together with senarmontite solubility determined from XAFS spectra, were complemented by batch-reactor measurements of senarmontite and stibnite (Sb₂S₃, rhombic) solubilities over a wide range of HCl and NaCl concentrations from 300 to 400 °C. Analysis of the whole dataset shows that Sb(III) speciation in high-temperature moderately acid (pH > 2-3) Cl-rich fluids is dominated by mixed hydroxy-chloride species like Sb(OH)₂Cl° and Sb(OH)₃Cl⁻, but other species containing two or three Cl atoms appear at higher acidities and moderate temperatures (?300 °C). Calculations using stability constants retrieved in this study indicate that mixed hydroxy-chloride complexes control antimony transport in saline high-temperature ore fluids at acidic conditions. Such species allow for a more effective Sb partitioning into the vapor phase during boiling and vapor-brine separation processes occurring in magmatic-hydrothermal systems. Antimony hydroxy-chloride complexes are however minor in the neutral low- to moderate-temperature solutions (?250-300 °C) typical of Sb deposits formation; the antimony speciation in these systems is dominated by Sb(OH)₃ and potentially Sb-sulfide species.     

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

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

A study of speciation of Sb in bisulfide solutions by X-ray absorption spectroscopy.

Direct evidence of the structure of thioantimonide species in alkaline aqueous solutions is provided by X-ray absorption spectroscopy. Twenty solutions containing thioantimonide species were prepared by dissolving stibnite (Sb₂S₃) in deoxygenated aqueous NaHS solutions; the solution pH range was 8–14, the [Sb_tot] 1–100 mM and the [HS⁻] 0.009–2.5 M. The structural environment of the dissolved Sb was determined by EXAFS analysis of the Sb K-edge over the temperature range 80–473 K.Many of the solutions contain a species with Sb bonded to four S atoms at 2.34 Å, consistent with the presence of a [Sb(V)S₄³⁻] species, demonstrating that oxidation of Sb(III) to Sb(V) has occurred on dissolution. There is evidence that the complementary reduced phase is H₂. In three solutions, the Sb has three nearest neighbor S atoms and two of these solutions have an additional S shell of two atoms at 2.9Å, with one showing evidence of an Sb shell at 4.15 Å. This provides evidence of the presence of multimeric Sb(V) thioantimonide species. Analysis of several solutions reveals the presence of a species with three Sb–S interactions of 2.41–2.42 Å, supporting the presence of a Sb(III) species such as Sb₂S₂(SH)₂. Six solutions have S coordination numbers from 2.7–4 Å and Sb–S distances of 2.37–2.39 Å, and are likely to contain mixtures of at least two species in concentrations such that each make a significant contribution to the EXAFS. There was no clear relationship between either [Sb_tot] or [HS⁻] and the type of species present, but Sb(III) species were only present in the solutions with high pH. The effect of temperature was most significant in one solution, where at 423 K partial hydrolysis occurred and the presence of a species such as Sb₂S₂(OH)₂, with an Sb–O distance of 1.91 Å, is indicated.The study provides new information on the coordination environment of thioantimonide species, complementary to previous studies and provides a basis for a better understanding of Sb speciation in aqueous solutions found in hydrothermal systems, anoxic basins and man-made, high pH environments. In particular it demonstrates the need for Sb(V) to be considered in theoretical and experimental studies of such systems. However, more definitive interpretation of some of the data is inhibited by the presence of mixtures of species and the lack of information on the outer coordination shells that would confirm the presence of multimeric species.     

The state of gold in phases of the Cu-Fe-S system: In situ X-ray absorption spectroscopy study

Chalcopyrite and bornite are the main Au-bearing minerals at Cu porphyry deposits, volcanogenic massive sulfide (VMS) deposits, Cu-Ni deposits of the mafic magmatic complexes, and ores of submarine sulfide edifices. Bornite and intermediate solid solutions with wide compositional variations (bnss and iss – high-temperature chalcopyrite, correspondingly), which can scavenge economic concentrations of Au, appear in the Cu-Fe-S system at ore-forming conditions. However, the state of Au in bnss and iss is yet unknown. To solve this conundrum, we synthesized samples with net chemical composition of bnss and iss, studied them by in situ X–ray absorption spectroscopy (XAS), and used the experimental data to explain the Au distribution among natural ore-forming minerals. The sulfide samples were obtained at 495–700 °C in Au-saturated system by means of salt flux method. The bnss contained ～1.2–1.6 log units more Au than iss: up to 18 wt.% Au in bnss vs 0.4 wt.% Au in iss at 700 °C. An increase of temperature resulted in the sharp increase of Au concentration in both phases, ～1 log unit per 100 °C at f(S₂) close to S_(l) saturation. Analysis of Au L₃-edge spectra recorded at 25–675 °C revealed that at 25 °C Au exists mainly in the metallic state. At t > 500 °C the spectral features of Au° disappear, and “chemically bound” Au predominates. The Au form of occurrence in the iss field is interpreted as Au-bearing clusters with a stromeyerite-like (CuAgS) structure. Digenite Cu_2–xS and bnss contain Au in a mixture of stromeyerite-like and petrovskaite-like (Au_0.8Ag_1.2S) clusters. The chemical composition of both forms is close to CuAuS, where the nearest Au neighbors are two S atoms at R_Au-S = 2.34–2.36 Å. Results of the present study allow to determine the state of Au and its concentration in the main Cu-bearing minerals of sulfide ores as a function of the T-f(S₂)-compositional parameters. Due to the sharp increase of the CuAuS clusters stability with increasing temperature, in high-temperature ores formed at t > 350 °C Au enriches Cu-bearing minerals in comparison with Cu-free or Cu-deficient ones. As a result, in these ores native gold, being a product of decomposition of the Au-bearing clusters, is associated with Cu-rich minerals – chalcopyrite, bornite, digenite, chalcocite.     

Bi-melt formation and gold scavenging from hydrothermal fluids: An experimental study

The role of polymetallic melts in scavenging ore components has recently been highlighted in the context of fluid-poor metamorphosed ore deposits. In contrast, the role of polymetallic melts in systems dominated by hydrothermal fluids remains poorly understood. Using a simple Au-Bi model system, we explored experimentally whether such polymetallic melts can precipitate directly from a hydrothermal fluid, and investigated the ability of these melts to scavenge Au from the solution. The experiments were conducted in custom-built flow-through reactors, designed to reproduce a hydrothermal system where melt components are dissolved at one stage along the flow path (e.g., Bi was dissolved by placing Bi-minerals along the fluid path), whereas melt precipitation was caused further along the flow path by fluid-rock interaction. Bi-rich melts were readily obtained by reaction with pyrrhotite, graphite or amorphous FeS. When Au was added to the system, Bi-Au melts with compositions consistent with the Au-Bi phase diagram were obtained. In the case of fluid reaction with pyrrhotite, epitaxial replacement of pyrrhotite by magnetite was observed, with textures consistent with an interface-coupled dissolution-reprecipitation reaction (ICDRR). In this case, the metallic melt precipitated as blebs that were localized at the replacement front or within the porous magnetite.Direct fractionation of Bi-Au melts from a hydrothermal fluid, or precipitation of a Bi-melt followed by partitioning of Au from ambient fluid, offer new pathways to the enrichment of minor ore components such as Au, without requiring fluid saturation with respect to a Au mineral. This mechanism can explain the strong geochemical affinity recognized between Au and low-melting point chalcophile elements such as Bi in many gold deposits. Examples of deposits where such a model may be applicable include orogenic gold deposits and gold skarns. Contrary to models involving migration of polymetallic melts to explain element remobilization, only small quantities (ppm) of polymetallic melts are required to affect the Au endowment of a deposit via interaction with a hydrothermal fluid. The experiments also show that micro-environments can play a critical role in controlling melt occurrences. For example, reaction fronts developing via ICDR reactions can promote melt formation as observed during the replacement of pyrrhotite by magnetite. The associated transient porosity creates space for the melt and promotes melt-fluid exchanges whereas the reaction front provides local geochemical conditions favorable to melt precipitation (e.g., reduced, low aH₂S(aq), and catalytic surface).     

Iron local structure in tektites and impact glasses by extended X-ray absorption fine structure and high-resolution X-ray absorption near-edge structure spectroscopy

The local structure of iron in three tektites has been studied by means of Fe K-edge extended X-ray absorption fine structure (EXAFS) and high-resolution X-ray absorption near-edge structure (XANES) spectroscopy in order to provide quantitative data on <Fe-O> distance and Fe coordination number. The samples studied are a moldavite and two australasian tektites. Fe model compounds with known Fe oxidation state and coordination number were used as standards in order to extract structural information from the XANES pre-edge peak. EXAFS-derived grand mean <Fe-O> distances and Fe coordination numbers for the three tektite samples are constant within the estimated error (<Fe-O > =2.00 Å ± 0.02 Å, CN = 4.0 ± 0.4). In contrast to other data from the literature on Fe-bearing silicate glasses, the tektites spectra could not be fitted with a single Fe-O distance, but rather were fit with two independent distances (2 × 1.92 Å and 2 × 2.08 Å). High-resolution XANES spectra of the three tektites display a pre-edge peak whose intensity is intermediate between those of staurolite and grandidierite, thus suggesting a mean coordination number intermediate between 4 and 5. Combining the EXAFS and XANES data for Fe, we infer the mean coordination number to be close to 4.5.Comparison of the tektites XANES spectra with those of a suite of different impact glasses clearly shows that tektites display a relatively narrow range of Fe oxidation state and coordination numbers, whereas impact glasses data span a much wider range of Fe oxidation states (from divalent to trivalent) and coordination numbers (from tetra-coordinated to esa-coordinated). These data suggest that the tektite production process is very similar for all the known strewn fields, whereas impact glasses can experience a wide variety of different temperature-pressure-oxygen fugacity conditions, leading to different Fe local structure in the resulting glasses. These data could be of aid in discriminating between tektite-like impact glasses and impact glasses sensu strictu.     

Molecular environment of iodine in naturally iodinated humic substances: Insight from X-ray absorption spectroscopy

The molecular environment of iodine in reference inorganic and organic compounds, and in dry humic and fulvic acids (HAs and FAs) extracted from subsurface and deep aquifers was probed by iodine L₃-edge X-ray absorption spectroscopy. The X-ray absorption near-edge structure (XANES) of iodine spectra from HAs and FAs resembled those of organic references and displayed structural features consistent with iodine forming covalent bonds with organic molecules. Simulation of XANES spectra by linear combination of reference spectra suggested the predominance of iodine forming covalent bonds to aromatic rings (aromatic-bound iodine). Comparison of extended X-ray absorption fine structure (EXAFS) spectra of reference and samples further showed that iodine was surrounded by carbon shells at distances comparables to those for references containing aromatic-bound iodine. Quantitative analysis of EXAFS spectra indicated that iodine was bound to about one carbon at a distance d (I-C) of 2.01(4)-2.04(9) Å, which was comparable to the distances observed for aromatic-bound iodine in references (1.99(1)-2.07(6) Å), and significantly shorter than that observed for aliphatic-bound iodine (2.15(2)-2.16(2) Å). These results are in agreement with previous conclusions from X-ray photoelectron spectroscopy and from electrospray ionization mass spectrometry. These results collectively suggest that the aromatic-bound iodine is stable in the various aquifers of this study.     

Iron (III)-silica interactions in aqueous solution: insights from X-ray absorption fine structure spectroscopy

The influence of aqueous silica on the hydrolysis of iron(III) nitrate and chloride salts in dilute aqueous solutions (m_Fe ∼ 0.01 mol/kg) was studied at ambient temperature using X-ray absorption fine structure (XAFS) spectroscopy at the Fe K-edge. Results show that in Si-free iron nitrate and chloride solutions at acid pH (pH < 2.5), Fe is hexa-coordinated with 6 oxygens of H₂O- and/or OH-groups in the first coordination sphere of the metal, at an Fe-O distance of 2.00 ± 0.01 Å. With increasing pH (2.7 < pH < 13), these groups are rapidly replaced by bridging hydroxyls (-OH-) or oxygens (-O-), and polymerized Fe hydroxide complexes form via Fe-(O/OH)-Fe bonds. In these polymers, the first atomic shell of iron represents a distorted octahedron with six O/OH groups and Fe-O distances ranging from 1.92 to 2.07 Å. The Fe octahedra are linked together by their edges (Fe-Fe distance 2.92-3.12 Å) and corners (Fe-Fe distance ∼3.47 ± 0.03 Å). The Fe-Fe coordination numbers (N_edge = 1-2; N_corner = 0.5-0.7) are consistent with the dominant presence of iron dimers, trimers and tetramers at pH 2.5 to 2.9, and of higher-polymerized species at pH > 3.At pH > 2.5 in the presence of aqueous silica, important changes in Fe(III) hydrolysis are detected. In 0.05-m Si solutions (pH ∼ 2.7-3.0), the corner linkages between Fe octahedra in the polymeric complexes disappear, and the Fe-Fe distances corresponding to the edge linkages slightly increase (Fe-Fe_edge ∼ 3.12-3.14 Å). The presence of 1 to 2 silicons at 3.18 ± 0.03 Å is detected in the second atomic shell around iron. At basic pH (∼12.7), similar structural changes are observed for the iron second shell. The Fe-Si and Fe-Fe distances and coordination numbers derived in this study are consistent with (1) Fe-Si complex stoichiometries Fe₂Si_1-2 and Fe₃Si_2-3 at pH < 3; (2) structures composed of Fe-Fe dimers and trimers sharing one or two edges of FeO₆-octahedra; and (3) silicon tetrahedra linked to two neighboring Fe octahedra via corners. At higher Si concentration (0.16 m, polymerized silica solution) and pH ∼ 3, the signal of the Fe second shell vanishes indicating the destruction of the Fe-Fe bonds and the formation of different Fe-Si linkages. Moreover, ∼20 mol.% of Fe is found to be tetrahedrally coordinated with oxygens in the first coordination shell (R_Fe-O = 1.84 Å). This new finding implies that Fe may partially substitute for Si in the tetrahedral network of the silica polymers in Si-rich solutions.The results of this study demonstrate that aqueous silica can significantly inhibit iron polymerization and solid-phase formation, and thus increase the stability and mobility of Fe(III) in natural waters. The silica “poisoning” of the free corner sites of iron-hydroxide colloids should reduce the adsorption and incorporation of trace elements by these colloids in Si-rich natural waters.     

Structure and specification of iron complexes in aqueous solutions determined by X-ray absorption spectroscopy

X-ray absorption spectroscopy, including extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) techniques, have been used to determine the structure and speciation of complexes for Fe²⁺ and Fe³⁺ chloride solutions at a variety of pH's, ionic strengths, and chloride/iron ratios.Low intensity K-edge transition features and analysis of modified pair correlation functions, derived from Fourier transformation of EXAFS spectra, show a regular octahedral coordination of Fe(II) by water molecules with a first-shell Fe²⁺-O bond distance, closely matching octahedral Fe²⁺-O bonds obtained from solid oxide model compounds. Solution Fe²⁺-O bond distances decrease with chloride/iron ratio, pH, and total FeCl₂ concentration. A slight intensification of the $\text{1s → 3d}$ transition with increasing FeCl₂ concentration suggests that chloride may begin to mix with water as a nearest-neighbor octahedral ligand. Fe³⁺ solutions show a pronounced increase in the $\text{1s → 3d}$ transition intensities between 1.0 M FeCl₃/7.8 M Cl^? to 1.0 M FeCl₃/ 15 M Cl^?, indicating a coordination change from octahedral to tetrahedral complexes. EXAFS analyses of these solutions show an increase in first-shell Fe³⁺-ligand distances despite this apparent reduction in coordination number. This can be best explained by a change from regular octahedral complexes of ferric iron (either Fe(H₂O)₆³⁺ or trans-Fe(H₂O)₄Cl₂ or both; Fe³⁺-O bond distances of 2.10 Å) to tetra-chloro complexes [Fe³⁺-Cl bond distances of 2.25 Å].     

北塔山金矿床成矿流体成因及金沉淀机制的探讨

北塔山地区金矿床及矿点的含金石英脉与闪长玢岩、闪长岩及斜闪煌斑岩等岩脉及小岩体有密切的空间关系,其一般产于岩脉内部及其接触带附近。石英中流体包裹体研究表明成矿流体为近中性低盐度和富ＣＯ２的Ｋ＾＋￣Ｎ＾＋（Ｃａ＾２＋）－Ｃｌ＾－型热液,推测主要属于来自深部的变质流体。金的成矿具多阶段特征。早期中－高温阶段减压引起ＣＯ２和Ｈ２Ｓ等组分溶解度减小和强烈挥发应是金沉淀的主要机制。晚期中－低温阶段,降温引起     

Hydrocarbons and oxidized organic compounds in hydrothermal fluids from Rainbow and Lost City ultramafic-hosted vents

The first building blocks of life could be produced in ultramafic-hosted hydrothermal systems considering the large amounts of hydrogen and methane generated by serpentinisation and Fischer–Tropsch-Type synthesis, respectively, in those systems. The purpose of this study was to detect and characterise organic molecules in hydrothermal fluids from ultramafic-hosted hydrothermal systems in the Mid-Atlantic Ridge (MAR) region. During the EXOMAR cruise 2005, fluids from the Rainbow (36°14′N) and the Lost City (30°N) hydrothermal fields were collected and treated by Stir Bar Sorptive Extraction (SBSE) and Solid Phase Extraction (SPE). The extracts were analysed by Thermal Desorption–Gas Chromatography–Mass Spectrometry (TD–GC–MS) and GC–MS, respectively. Compared to nearby deep seawater, hydrothermal fluids were clearly enriched in organic compounds, with a more diverse spectrum of molecules. We observed a very similar range of organic compounds in fluids from both sites, with a dominance of aliphatic hydrocarbons (C9–C14), aromatic compounds (C6–C16) and carboxylic acids (C8–C18). The occurrence of these compounds is supported by other field studies on serpentinites and sulfide deposits. Literature on thermodynamic data and experimental work has suggested the possible abiogenic origin of hydrocarbons and organic acids. In addition, it has been shown elsewhere that catalytic reactions producing hydrocarbons likely occur at both Lost City and Rainbow hydrothermal fields as suggested by the evolution of δ¹³C with increasing C number for methane, ethane, propane and butane. In order to investigate the origin of the organic molecules in the fluids, compound-specific carbon isotope ratio measurements were performed on n-alkanes and carboxylic acids, for which the δ¹³C values were in the range of ? 46 to ? 20‰ (vs. V-PDB). These preliminary data did not allow conclusive support or rejection of an abiogenic origin of the compounds. Indeed, predicting δ¹³C signatures in hydrothermal systems is likely to be complicated, due to differences in source δ¹³C signatures (i.e., of the C building blocks), and a variety of, mostly unknown, fractionation steps which may occur along the synthesis pathways. In addition, even though a fraction of the compounds detected in the fluids is likely abiotically produced, a dominance of biogenic sources and/or processes might hide their characteristic signature.     

The oxidation state of sulfur in synthetic and natural glasses determined by X-ray absorption spectroscopy

Sulfur K-edge X-ray absorption near edge structure (XANES) spectra were recorded for experimental glasses of various compositions prepared at different oxygen fugacities (fO₂) in one-atmosphere gas-mixing experiments at 1400 °C. This sample preparation method only results in measurable S concentrations under either relatively reduced (log fO₂ < −9) or oxidised (log fO₂ > −2) conditions. The XANES spectra of the reduced samples are characterised by an absorption edge crest at 2476.4 eV, typical of S²⁻. In addition, spectra of Fe-bearing compositions exhibit a pronounced absorption edge shoulder. Spectra for all the Fe-free samples are essentially identical, as are the spectra for the Fe-bearing compositions, despite significant compositional variability within each group. The presence of a sulfide phase, such as might exsolve on cooling, can be inferred from a pre-edge feature at 2470.5 eV.The XANES spectra of the oxidised samples are characterised by an intense transition at 2482.1 eV, typical of the sulfate anion SO₄²⁻. Sulfite (SO₃²⁻) has negligible solubility in silicate melts at low pressures. The previous identification of sulfite species in natural glass samples is attributed to an artefact of the analysis (photoreduction of S⁶⁺). S⁴⁺ does, however, occur unambiguously with S⁶⁺ in Fe-free and Fe-poor compositions prepared in equilibrium with CaSO₄ at 4-16 kbar, and when buffered with Re/ReO₂ at 10 kbar. Solubility of S⁴⁺ thus requires partial pressures of SO₂ considerably in excess of 1 bar. A number of experiments were undertaken in an attempt to access intermediate fO₂s more applicable to terrestrial volcanism. Although these were largely unsuccessful, S²⁻ and S⁶⁺ were found to coexist in some samples that were not in equilibrium with the imposed fO₂.The XANES spectra of natural olivine-hosted melt inclusions and submarine glasses representative of basalts at, or close to, sulfide saturation show mainly dissolved S²⁻, but with minor sulfate, and additionally a peak at 2469.5 eV, which, although presumably due to immiscible sulfide, is 1 eV lower than that typical of FeS. These sulfate and sulfide-related peaks disappear with homogenisation of the inclusions by heating to 1200 °C followed by rapid quenching, suggesting that both these features are a result of cooling under natural conditions. The presence of small amounts of sulfate in otherwise reduced basaltic magmas may be explained by the electron exchange reaction: S²⁻ + 8Fe³⁺ = S⁶⁺ + 8Fe²⁺, which is expected to proceed strongly to the right with decreasing temperature. This reaction would explain why S²⁻ and S⁶⁺ are frequently found together despite the very limited fO₂ range over which they are thermodynamically predicted to coexist. The S XANES spectra of water-rich, highly oxidised, basaltic inclusions hosted in olivine from Etna and Stromboli confirm that nearly all S is dissolved as sulfate, explaining their relatively high S contents.     

Occurrence of arsenic (V) in forearc mantle serpentinites based on X-ray absorption spectroscopy study

We examined As concentration, mineralogical site, and oxidation state in the serpentinites associated with the Tso Morari eclogitic rocks in the Indus suture zone, northwest Himalaya, to examine how highly fluid-soluble elements like As are transferred from slabs to arc magmas in subduction zones. The serpentinite samples represent hydrated peridotites at the base of the mantle wedge beneath Eurasia, and were exhumed from a depth of ∼100 km during subduction of the Indian continental margin. The bulk serpentinite samples contain total As concentrations ranging from 6 to 275 ppm. Arsenic in the samples is most likely present with magnetite and antigorite, since electron probe analysis yielded up to 90 ppm As in these minerals. X-ray absorption near-edge structure spectra indicate that As in serpentinites is mostly As(V) and that the neighboring atoms of As are O, although there are minute grains of sulfides and arsenides. The ratio of As(V) to total As is greater in samples with higher As contents, suggesting that the major source of As was oxidized As(V), introduced to the mantle wedge. Arsenic(V), originally adsorbed on Fe-oxides in slabs and overlying sediments, was most likely liberated during their subduction and incorporated subsequently in the overlying mantle wedge. Our data constrain the introduction of As into the mantle wedge at relatively shallow levels, much shallower than 25 km. Arsenic incorporated in the serpentinites was transported to deeper levels by mantle flow downward along the subduction zone, to be subsequently exhumed together with eclogitic rocks.     

X-ray absorption spectroscopy study on the effect of hydroxybenzoic acids on the formation and structure of ferrihydrite

Organic ligands are known to interfere with the polymerization of Fe(III), but the extent of interference has not been systematically studied as a function of structural ligand properties. This study examines how the number and position of phenol groups in hydroxybenzoic acids affect both ferrihydrite formation and its local (<5 Å) Fe coordination. To this end, acid Fe(III) nitrate solutions were neutralized up to pH 6.0 in the presence of 4-hydroxybenzoic acid (4HB), 2,4-dihydroxybenzoic acid (2,4DHB), and the hydroquinone 3,4-dihydroxybenzoic acid (3,4DHB). The initial molar ligand/Fe ratios ranged from 0 to 0.6. The precipitates were dialyzed, lyophilized, and subsequently studied by X-ray absorption spectroscopy and synchrotron X-ray diffraction. The solids contained up to 32 wt.% organic C (4HB ∼ 2,4DHB < 3,4DHB). Only precipitates formed in 3,4DHB solutions comprised considerable amounts of Fe(II) (Fe(II)/Fe_tot ≤ 6 mol%), implying the abiotic mineralization of the catechol-group bearing ligand during Fe(III) hydrolysis under oxic conditions. Hydroxybenzoic acids decreased ferrihydrite formation in the order 4HB ∼ 2,4DHB ? 3,4DHB, which documents that phenol group position rather than the number of phenol groups controls the ligand’s interaction with Fe(III). The coordination numbers of edge- and double corner-sharing Fe in the precipitates decreased by up to 100%. Linear combination fitting (LCF) of Fe K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra revealed that this decrease was due to increasing amounts of organic Fe(III) complexes in the precipitates. Although EXAFS derived coordination numbers of Fe in ferrihydrite remained constant within error, all organic ligands decreased the coherently scattering domain (CSD) size of ferrihydrite as indicated by synchrotron X-ray diffraction analysis (4HB < 2,4DHB ? 3,4DHB). With decreasing particle size of ferrihydrite its Fe(O,OH)₆ octahedra became progressively distorted as evidenced by an increasing loss of centrosymmetry of the Fe sites. Pre-edge peak analysis of the Fe K-edge XANES spectra in conjunction with LCF results implied that ferrihydrite contains on an average 13 ± 3% tetrahedral Fe(III), which is in very good agreement with the revised single-phase structural model of ferrihydrite (Michel, F. M., Barron, V., Torrent, J., Morales, M. P. et al. (2010) Ordered ferrimagnetic form of ferrihydrite reveals links among structure, composition, and magnetism. Proc. Natl. Acad. Sci. USA107, 2787-2792). The results suggest that hydroxybenzoic acid moieties of natural organic matter (NOM) effectively suppress ferrihydrite precipitation as they kinetically control the availability of inorganic Fe(III) species for nucleation and/or polymerization reactions. As a consequence, NOM can trigger the formation of small ferrihydrite nanoparticles with increased structural strain. These factors may eventually enhance the biogeochemical reactivity of ferrihydrite formed in NOM-rich environments. This study highlights the role of hydroquinone structures of NOM for Fe complexation, polymerization, and redox speciation.     

贵州泥堡金矿床热液方解石地球化学特征及地质意义

已有研究表明,右江盆地卡林型金矿成矿期方解石具有独特的中稀土元素富集特点,但其成因还存在诸多争议。贵州泥堡金矿存在成矿期和非成矿期2种热液方解石脉,其中成矿期方解石脉多出现在矿化凝灰质细砾岩与凝灰质（粉）砂岩中,矿物组合为含砷黄铁矿+毒砂+石英+方解石;非成矿期方解石脉在未蚀变灰岩、矿化凝灰质细砾岩与凝灰质（粉）砂岩中均发育,且常穿切成矿期含硫化物方解石脉。文章通过对2种类型方解石脉开展稀土元素与碳、氧同位素、成矿期方解石脉内金属硫化物电子探针与微区原位LA-ICP-MS元素分析,发现与成矿期方解石脉共生的黄铁矿具典型的环带结构,黄铁矿环带和毒砂富Au、As、Sb、Hg、Cu、Co、Ni等元素。成矿期方解石脉显示中稀土元素富集模式和Eu正异常特征,表明金成矿流体为还原性流体,明显不同于非成矿期方解石脉的轻稀土元素富集模式和Eu负异常特征。泥堡金矿成矿期热液方解石的中稀土元素富集模式,与中国西南低温Au-Sb矿床成矿期方解石、萤石、磷灰石等矿物的稀土元素组成特征一致,酸性成矿流体的稀土元素组成可能是导致该金矿区成矿期方解石富集中稀土元素的主要原因。该区热液方解石特有的地球化学特征,使其在低温热液金矿床成矿年代学研究及深部找矿应用方面具有重要前景。