Solubility of Fe2(OH)3Cl (pure-iron end-member of hibbingite) in NaCl and Na2SO4 brines

Pure-iron end-member hibbingite, Fe₂(OH)₃Cl(s), may be important to geological repositories in salt formations, as it may be a dominant corrosion product of steel waste canisters in an anoxic environment in Na–Cl- and Na–Mg–Cl-dominated brines. In this study, the solubility of Fe₂(OH)₃Cl(s), the pure-iron end-member of hibbingite (Fe^II, Mg)₂(OH)₃Cl(s), and Fe(OH)₂(s) in 0.04 m to 6 m NaCl brines has been determined. For the reactionFe₂(OH)₃Cl(s) + 3H⁺ ? 3 H₂O + 2 Fe²⁺ + Cl^?,the solubility constant of Fe₂(OH)₃Cl(s) at infinite dilution and 25 °C has been found to be log₁₀ K = 17.12 ± 0.15 (95% confidence interval using F statistics for 36 data points and 3 parameters). For the reactionFe(OH)₂(s) + 2H⁺ ? 2 H₂O + Fe²⁺,the solubility constant of Fe(OH)₂ at infinite dilution and 25 °C has been found to be log₁₀ K = 12.95 ± 0.13 (95 % confidence interval using F statistics for 36 data points and 3 parameters). For the combined set of solubility data for Fe₂(OH)₃Cl(s) and Fe(OH)₂(s), the Na⁺–Fe²⁺ pair Pitzer interaction parameter θ_{Na⁺/Fe²⁺} has been found to be 0.08 ± 0.03 (95% confidence interval using F statistics for 36 data points and 3 parameters). In nearly saturated NaCl brine we observed evidence for the conversion of Fe(OH)₂(s) to Fe₂(OH)₃Cl(s). Additionally, when Fe₂(OH)₃Cl(s) was added to sodium sulfate brines, the formation of green rust(II) sulfate was observed, along with the generation of hydrogen gas. The results presented here provide insight into understanding and modeling the geochemistry and performance assessment of nuclear waste repositories in salt formations.     

Leaching of metals from copper smelter flue dust (Mufulira,Zambian Copperbelt)

The leaching behaviour of electrostatic precipitator dust from the Mufulira Cu smelter (Copperbelt, Zambia) was studied using a 48-h pH-static leaching experiment (CEN/TS 14997). The release of metals (Cd, Co, Cu, Ni, Pb and Zn) and changes in mineralogical composition using X-ray diffraction and PHREEQC-2 modelling were investigated in the pH range of 3–7. The highest concentrations of metals were released at pH 3–4.5, which encompasses the natural pH of the dust suspension (～4.3). About 40% of the total Cu was leached at pH 3, yielding 107 g/kg. Chalcanthite (CuSO₄·5H₂O), magnetite (Fe₃O₄) and delafossite (CuFeO₂) represented the principal phases of the studied dust. In contact with water, chalcanthite was dissolved and hydrated Cu sulphates precipitated at pH 4–7. Gypsum (CaSO₄·2H₂O) and secondary Fe or Al phases were observed in the leached residues. Serious environmental impact due to leaching may occur in dust-contaminated soil systems in the vicinity of the smelting plants.     

Synthesis and characterization of polycrystalline KAlSi3O8 hollandite [liebermannite]: Sound velocities vs. pressure to 13 GPa at room temperature

A polycrystalline specimen of liebermannite [KAlSi₃O₈ hollandite] was synthesized at 14.5 GPa and 1473 K using glass starting material in a uniaxial split-sphere apparatus. The recovered specimen is pure tetragonal hollandite [SG: I4/m] with bulk density of within 98% of the measured X-ray value. The specimen was also characterized by Raman spectroscopy and nuclear magnetic resonance spectroscopy. Sound velocities in this specimen were measured by ultrasonic interferometry to 13 GPa at room T in a uniaxial split-cylinder apparatus using Al₂O₃ as a pressure marker. Finite strain analysis of the ultrasonic data yielded K_S0 = 145(1) GPa, K₀′ = 4.9(2), G₀ = 92.3(3) GPa, G₀′ = 1.6(1) for the bulk and shear moduli and their pressure derivatives, corresponding to V_P0 = 8.4(1) km/s, V_S0 = 4.9(1) km/s for the sound wave velocities at room temperature. These elasticity data are compared to literature values obtained from static compression experiments and theoretical density functional calculations.     

Thermodynamic properties of tooeleite,Fe63+(As3+O3)4(SO4)(OH)4·4H2O

Tooeleite, nominally Fe₆³⁺(As³⁺O₃)₄(SO₄)(OH)₄·4H₂O, is a relatively uncommon mineral of some acid-mine drainage systems. Yet, if it does occur, it does so in large quantities, indicating that some specific conditions favor the formation of this mineral in the system Fe-As-S-O-H. In this contribution, we report the thermodynamic properties of synthetic tooeleite. The sample was characterized by powder X-ray diffraction, scanning electron microscopy, extended X-ray absorption fine-structure spectroscopy, and Mössbauer spectroscopy. These methods confirmed that the sample is pure, devoid of amorphous impurities of iron oxides, and that the oxidation state of arsenic is 3+. Using acid-solution calorimetry, the enthalpy of formation of this mineral from the elements at the standard conditions was determined as −6196.6 ± 8.6 kJ mol⁻¹. The entropy of tooeleite, calculated from low-temperature heat capacity data measured by relaxation calorimetry, is 899.0 ± 10.8 J mol⁻¹ K⁻¹. The calculated standard Gibbs free energy of formation is −5396.3 ± 9.3 kJ mol⁻¹. The log K_sp value, calculated for the reaction Fe₆(AsO₃)₄(SO₄)(OH)₄·4H₂O + 16H⁺ = 6Fe³⁺ + 4H₃AsO₃ + SO₄²⁻ + 8H₂O, is −17.25 ± 1.80. Tooeleite has stability field only at very high activities of aqueous sulfate and arsenate. As such, it does not appear to be a good candidate for arsenic immobilization at polluted sites. An inspection of speciation diagrams shows that the predominance field of Fe³⁺ and As³⁺ overlap only at strongly basic conditions. The formation of tooeleite, therefore, requires strictly selective oxidation of Fe²⁺ to Fe³⁺ and, at the same time, firm conservation of the trivalent oxidation state of arsenic. Such conditions can be realized only by biological systems (microorganisms) which can selectively oxidize one redox-active element but leave the other ones untouched. Hence, tooeleite is the first example of an “obligatory” biomineral under the conditions prevailing at or near the Earth's surface because its formation under these conditions necessitates the action of microorganisms.     

Dielectric loss in ore-forming chromium spinel at temperatures from 20 to 800 °C

Physical, physicochemical, and mineralogical-petrographic methods have been applied to samples of ophiolite-hosted chromite ore from different deposits and occurrences in the Urals. Temperature dependences of dielectric loss obtained for nine chromite ore samples consisting of 95–98% Cr spinel show prominent peaks indicating a relaxation origin of the loss. The analyzed samples have the loss peaks at different temperatures depending mainly on H = (FeO/Fe₂O₃)^? : (FeO/Fe₂O₃)^??, where (FeO/Fe₂O₃)^? and (FeO/Fe₂O₃)^?? are, respectively, the ferrous/ferric oxide ratios in the samples before and after heating to 800 °C, and H is thus the heating-induced relative change in the FeO/Fe₂O₃ ratio. These peak temperatures vary from 550 °C (sample 1, high-Cr chromium spinel with more than 52% Cr₂O₃) to 750 °C (sample 2, aluminous and magnesian spinel with less than 30% Cr₂O₃), and H ranges correspondingly from 1.61 to 5.49. The temperature of the loss peaks is related with H as H = 34.30 ? 11.52N + 1.20N², with an error of σ = 0.19 (N = T · 10^?2, T is temperature in °C).     

Pressure-induced dehydration of dioptase: A single-crystal X-ray diffraction and Raman spectroscopy study

We present a synchrotron-based, single-crystal X-ray diffraction and Raman spectroscopy study of natural green dioptase (Cu₆Si₆O₁₈·6H₂O) up to ∼30 GPa at room temperature. The lattice parameters of dioptase exhibit continuous compression behavior up to ∼14.5 GPa, whereupon a structural transition is observed. Pressure–volume data below 14.5 GPa were fitted to a second-order Birch–Murnaghan equation of state with V₀ = 1440(2) ų and K₀ = 107(2) GPa, with K₀′ = 4(fixed). The low-pressure form of dioptase exhibits anisotropic compression with axial compressibility β_a > β_c in a ratio of 1.14:1.00. Based on the diffraction data and Raman spectroscopy, the new high-pressure phase could be regarded as a dehydrated form of dioptase in the same symmetry group. Pressure-induced dehydration of dioptase contributes broadly to our understanding of the high-pressure crystal chemistry of hydrous silicates containing molecular water groups.     

Electron probe microanalysis and microscopy: Principles and applications in characterization of mineral inclusions in chromite from diamond deposit

Electron probe microanalysis and microscopy is a widely used modern analytical technique primarily for quantifying chemical compositions of solid materials and for mapping or imaging elemental distributions or surface morphology of samples at micrometer or nanometer-scale. This technique uses an electromagnetic lens-focused electron beam, generated from an electron gun, to bombard a sample. When the electron beam interacts with the sample, signals such as secondary electron, backscattered electron and characteristic X-ray are generated from the interaction volume. These signals are then examined by detectors to acquire chemical and imaging information of the sample. A unique part of an electron probe is that it is equipped with multiple WDS spectrometers of X-ray and each spectrometer with multiple diffracting crystals in order to analyze multiple elements simultaneously. An electron probe is capable of analyzing almost all elements (from Be to U) with a spatial resolution at or below micrometer scale and a detection limit down to a few ppm.Mineral inclusions in chromite from the Wafangdian kimberlite, Liaoning Province, China were used to demonstrate the applications of electron probe microanalysis and microscopy technique in characterizing minerals associated with ore deposits, specifically, in this paper, minerals associated with diamond deposit. Chemical analysis and SE and BSE imaging show that mineral inclusions in chromite include anhydrous silicates, hydrous silicates, carbonates, and sulfides, occurring as discrete or single mineral inclusions or composite multiple mineral inclusions. The chromite–olivine pair poses a serious problem in analysis of Cr in olivine using electron probe. Secondary fluorescence of Cr in chromite by Fe in olivine drastically increases the apparent Cr₂O₃ content of an olivine inclusion in a chromite. From the chemical compositions obtained using electron probe, formation temperatures and pressures of chromite and its mineral inclusions calculated using applicable geothermobarometers are from 46 kbar and 980 °C to 53 kbar and 1130 °C, which are within the stability field of diamond, thus Cr-rich chromite is a useful indication mineral for exploration of kimberlite and diamond deposit. A composite inclusion in chromite composed of silicate and carbonate minerals has a bulk composition of 33.2 wt.% SiO₂, 2.5 wt.% Al₂O₃, 22.0 wt.% MgO, 7.5 wt.% CaO, 2.5 wt.% BaO, 0.8 wt.% K₂O, 25.5 wt.% CO₂, and 0.8 wt.% H₂O, similar to the chemical composition of the Wafangdian kimberlite, suggesting that it is trapped kimberlitic magma.     

Isotope and fluid inclusion geochemistry and genesis of the Qiangma gold deposit,Xiaoqinling gold field,Qinling Orogen,China

The Qiangma gold deposit is hosted in the > 1.9 Ga Taihua Supergroup metamorphic rocks in the Xiaoqinling terrane, Qinling Orogen, on the southern margin of the North China Craton. The mineralization can be divided as follows: quartz-pyrite veins early, quartz-polymetallic sulfide veinlets middle, and carbonate-quartz veinlets late stages, with gold being mainly introduced in the middle stage. Three types of fluid inclusions were identified based on petrography and laser Raman spectroscopy, i.e., pure carbonic, carbonic-aqueous (CO₂–H₂O) and aqueous inclusions.The early-stage quartz contains pure carbonic and CO₂–H₂O inclusions with salinities up to 12.7 wt.% NaCl equiv., bulk densities of 0.67 to 0.86 g/cm³, and homogenization temperatures of 280−365 °C. The early-stage is related to H₂O–CO₂ ± N₂ ± CH₄ fluids with isotopic signatures consistent with a metamorphic origin (δ¹⁸O_water = 3.1 to 5.2‰, δD = − 37 to − 73‰). The middle-stage quartz contains all three types of fluid inclusions, of which the CO₂–H₂O and aqueous inclusions yield homogenization temperatures of 249−346 °C and 230−345 °C, respectively. The CO₂–H₂O inclusions have salinities up to 10.9 wt.% NaCl equiv. and bulk densities of 0.70 to 0.98 g/cm³, with vapor bubbles composed of CO₂ and N₂. The isotopic ratios (δ¹⁸O_water = 2.2 to 3.6‰, δD = − 47 to − 79‰) suggest that the middle-stage fluids were mixed by metamorphic and meteoric fluids. In the late-stage quartz only the aqueous inclusions are observed, which have low salinities (0.9−9.9 wt.% NaCl equiv.) and low homogenization temperatures (145−223 °C). The isotopic composition (δ¹⁸O_water = − 1.9 to 0.5‰, δD = − 55 to − 66‰) indicates the late-stage fluids were mainly meteoric water.Trapping pressures estimated from CO₂–H₂O inclusions are 100−285 MPa for the middle stage, suggesting that gold mineralization mainly occurred at depths of 10 km. Fluid boiling and mixing caused rapid precipitation of sulfides and native Au. Through boiling and inflow of meteoric water, the ore-forming fluid system evolved from CO₂-rich to CO₂-poor in composition, and from metamorphic to meteoric, as indicated by decreasing δ¹⁸O_water values from early to late. The carbon, sulfur and lead isotope compositions suggest the hostrocks within the Taihua Supergroup to be a significant source of ore metals. Integrating the data obtained from the studies including regional geology, ore geology, and fluid inclusion and C–H–O–S–Pb isotope geochemistry, we conclude that the Qiangma gold deposit was an orogenic-type system formed in the tectonic transition from compression to extension during the Jurassic−Early Cretaceous continental collision between the North China and Yangtze cratons.     

Enriched crustal and mantle components and the role of the lithosphere in generating Paleoproterozoic dyke swarms of the Ungava Peninsula,Canada

Paleoproterozoic mafic dyke swarms (2.5–2.0 Ga) of the Ungava Peninsula can be divided in three chemical groups. The main group has a wide range of Fe (10–18 wt.% Fe₂O₃) and Ti (0.8–2.0 wt.% TiO₂) contents, and the most magnesian samples have compositions consistent with melting of a fertile lherzolitic mantle at ~ 1.5 GPa. Dykes of a low-LREE (light rare earth element) subgroup (La/Yb ≤ 4) display decreasing Zr/Nb with increasing La/Yb ratios and positive εNd_2.0 Ga values (+ 3.9 to + 0.2) that trend from primitive mantle towards the composition of Paleoproterozoic alkaline rocks. In contrast, dykes of a high-LREE subgroup (La/Yb ≥4) display increasing Zr/Nb ratios and negative εNd_2.0 Ga values (? 2.3 to ? 6.4) that trend towards the composition of Archean crust. A low Fe–Ti group has low Fe (< 11 wt.% Fe₂O₃), Ti (< 0.8 wt.% TiO₂), high field strength elements (HFSE; < 6 ppm Nb) and heavy rare earth elements (HREE; < 2 ppm Yb) contents, but are enriched in large ion lithophile elements (LILE; K/Ti = 0.7–3) and LREE (La/Yb > 4). These dykes are interpreted as melts of a depleted harzburgitic mantle that has experienced metasomatic enrichment. A positive correlation of Zr/Nb ratio and La/Yb ratio, negative εNd_2.0 Ga values (? 14 to ? 6), and the presence of inherited Archean zircons further suggest the incorporation of a crustal component. A high Fe–Ti group has high Fe (> 14 wt.% Fe₂O₃) and Ti (> 1.4 wt.% TiO₂) contents, along with higher Na contents relative to the main group dykes. Dykes of a high-Al subgroup (> 12 wt.% Al₂O₃) share Fe contents, εNd_2.0 Ga values (? 2.3 to ? 3.4), La/Yb and Th/Nb ratios with Archean ferropicrites, and may represent evolved ferropicrite melts. A low-Al subgroup (< 12 wt.% Al₂O₃) has relatively lower Yb contents (< 2 ppm) and fractionated HREE patterns that indicate the presence of garnet in their melting residue. A comparison with ~ 5 GPa experimentally-derived melts suggests that these dykes may be derived from garnet-bearing pyroxenite or peridotite. The εNd_2.0 Ga values (? 0.3 to ? 2.0) of these dykes lie between the compositions of Archean granitoids and Paleoproterozoic alkaline rocks, signifying their petrogenesis involved both crustal and mantle components.Paleoproterozoic dykes containing a crustal component occur within, or close to, an isotopically enriched Archean terrane (T_DM 4.3–3.1 Ga), whereas dykes without this component occur in an isotopically juvenile terrane (T_DM < 3.1 Ga). The lack of a crustal component and the positive εNd_2.0 Ga values of dykes intruding the latter suggest that the crust they intruded was either too cold to be assimilated, or that its lower crust and/or lithosphere were Paleoproterozoic in age. In contrast, the ubiquitous presence of a crustal component and the diversity of mantle sources for dykes intruding the enriched terrane (lherzolite, harzburgite, pyroxenite) suggest a warmer crust with underlying heterogeneous lithospheric mantle.     

Geology and fluid characteristics of the Ulu Sokor gold deposit,Kelantan, Malaysia: Implications for ore genesis and classification of the deposit

The Ulu Sokor gold deposit is one of the most famous and largest gold deposits in Malaysia and is located in the Central Gold Belt. This deposit consists of three major orebodies that are related to NS- and NE-striking fractures within fault zones in Permian-Triassic meta-sedimentary and volcanic rocks of the East Malaya Block. The faulting events represent different episodes that are related to each orebody and are correlated well with the mineralogy and paragenesis. The gold mineralization consists of quartz-dominant vein systems with sulfides and carbonates. The hydrothermal alteration and mineralization occurred during three stages that were characterized by (I) silicification and brecciation; (II) carbonatization, sericitization, and chloritization; and (III) quartz–carbonate veins.Fluid inclusions in the hydrothermal quartz and calcite of the three stages were studied. The primary CO₂–CH₄–H₂O–NaCl fluid inclusions in stage I are mostly related to gold mineralization and display homogenization temperatures of 269–389 °C, salinities of 2.77–11.89 wt.% NaCl equivalent, variable CO₂ contents (typically 5–29 mol%), and up to 15 mol% CH₄. In stage II, gold was deposited at 235–398 °C from a CO₂ ± CH₄–H₂O–NaCl fluid with a salinity of 0.83–9.28 wt.% NaCl equivalent, variable CO₂ contents (typically 5–63 mol%), and up to 4 mol% CH₄. The δ¹⁸O_H2O and δD values of the ore-forming fluids from the stage II quartz veins are 4.5 to 4.8‰ and − 44 to − 42‰, respectively, and indicate a metamorphic–hydrothermal origin. Oxygen fugacities calculated for the entire range of T-P-X_CO2 conditions yielded log f_O2 values between − 28.95 and − 36.73 for stage I and between − 28.32 and − 39.18 for stage II. These values indicate reduced conditions for these fluids, which are consistent with the mineral paragenesis, fluid inclusion compositions, and isotope values.The presence of daughter mineral-bearing aqueous inclusions is interpreted to be a magmatic signature of stage IIIa. Combined with the oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O = 6.8 to 11.9‰, δD = − 77 to − 62‰), these inclusions indicate that the initial fluid was likely derived from a magmatic source. In stage IIIb, the gold was deposited at 263° to 347 °C from a CO₂–CH₄–H₂O–NaCl fluid with a salinity of 5.33 to 11.05 wt.% NaCl equivalent, variable CO₂ contents (typically 9–15 mol%), and little CH₄. The oxygen and hydrogen isotopic compositions of this fluid (δ¹⁸O_H2O = 8.1 to 8.8‰, δD = − 44 to − 32‰) indicate that it was mainly derived from a metamorphic–hydrothermal source. The CO₂–H₂O ± CH₄–NaCl fluids that were responsible for gold deposition in the stage IIIc veins had a wide range of temperatures (214–483 °C), salinities of 1.02 to 21.34 wt.% NaCl equivalent, variable CO₂ contents (typically 4–53 mol%), and up to 7 mol% CH₄. The oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O = 8.5 to 9.8‰, δD = − 70 to − 58‰) were probably acquired at the site of deposition by mixing of the metamorphic–hydrothermal fluid with deep-seated magmatic water and then evolved by degassing at the site of deposition during mineralization. The log f_O2 values from − 28.26 to − 35.51 also indicate reduced conditions for this fluid in stage IIIc. Moreover, this fluid had a near-neutral pH and δ³⁴S values of H₂S of − 2.32 to 0.83‰, which may reflect the derivation of sulfur from the subducted oceanic lithospheric materials.The three orebodies represent different gold transportation and precipitation models, and the conditions of ore formation are related to distinct events of hydrothermal alteration and gold mineralization. The gold mineralization of the Ulu Sokor deposit occurred in response to complex and concurrent processes involving fluid immiscibility, fluid–rock reactions, and fluid mixing. However, fluid immiscibility was the most important mechanism for gold deposition and occurred in these orebodies, which have corresponding fluid properties, structural controls, geologic characteristics, tectonic settings, and origins of the ore-forming matter. These characteristics of the Ulu Sokor deposit are consistent with its classification as an orogenic gold deposit, while some of the veins are genetically related to intrusions.     

Decarbonation of subducting slabs: Insight from petrological–thermomechanical modeling

Subduction of heterogeneous lithologies (sediments and altered basalts) carries a mixture of volatile components (H₂O ± CO₂) into the mantle, which are later mobilized during episodes of devolatilization and flux melting. Several petrologic and thermodynamic studies investigated CO₂ decarbonation to better understand carbon cycling at convergent margins. A paradox arose when investigations showed little to no decarbonation along present day subduction geotherms at subarc depths despite field based observations. Sediment diapirism is invoked as one of several methods for carbon transfer from the subducting slab. We employ high-resolution 2D petrological–thermomechanical modeling to elucidate the role subduction dynamics has with respect to slab decarbonation and the sediment diapirism hypothesis. Our thermodynamic database is modified to account for H₂O–CO₂ binary fluids via the following lithologies: GLOSS average sediments (H₂O: 7.29 wt.% & CO₂: 3.01 wt.%), carbonated altered basalts (H₂O: 2.63 wt.% & CO₂: 2.90 wt.%), and carbonated peridotites (H₂O: 1.98 wt.% & CO₂: 1.50 wt.%). We include a CO₂ solubility P–x[H₂O wt.%] parameterization for sediment melts. We parameterize our model by varying two components: slab age (20, 40, 60, 80 Ma) and convergence velocity (1, 2, 3, 4, 5, 6 cm year^− 1). 59 numerical models were run and show excellent agreement with the original code base. Three geodynamic regimes showed significant decarbonation. 1) Sedimentary diapirism acts as an efficient physical mechanism for CO₂ removal from the slab as it advects into the hotter mantle wedge. 2) If subduction rates are slow, frictional coupling between the subducting and overriding plate occurs. Mafic crust is mechanically incorporated into a section of the lower crust and undergoes decarbonation. 3) During extension and slab rollback, interaction between hot asthenosphere and sediments at shallow depths result in a small window (~ 12.5 Ma) of high integrated CO₂ fluxes (205 kg m^− 3 Ma^− 1).     

Ore-forming process of the Huijiabao gold district,southwestern Guizhou Province,China: Evidence from fluid inclusions and stable isotopes

The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO₂ inclusions, CO₂–H₂O inclusions, hydrocarbon inclusions, and hydrocarbon–H₂O inclusions. The ore-forming fluids are characterized by a H₂O + CO₂ + CH₄ ± N₂ system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H₂O + NaCl → H₂O + NaCl + CO₂ + CH₄ ± N₂ → H₂O + NaCl ± CH₄ ± CO₂ with a slight decrease in homogenization temperature and salinity. The δ¹⁸O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δD_H2O and calculated δ¹⁸O_H2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H₂O–NaCl–CO₂ fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold.     

Nature of ore-forming fluid and formation conditions of BIF-hosted gold mineralization in the Archean Amalia Greenstone Belt,South Africa: Constraints from fluid inclusion and stable isotope studies

Orogenic gold mineralization in the Amalia greenstone belt is hosted by oxide facies banded iron-formation (BIF). Hydrothermal alteration of the BIF layers is characterized by chloritization, carbonatization, hematization and pyritization, and quartz-carbonate veins that cut across the layers. The alteration mineral assemblages consist of ankerite-ferroan dolomite minerals, siderite, chlorite, hematite, pyrite and subordinate amounts of arsenopyrite and chalcopyrite. Information on the physico-chemical properties of the ore-forming fluids and ambient conditions that promoted gold mineralization at Amalia were deduced from sulfur, oxygen and carbon isotopic ratios, and fluid inclusions from quartz-carbonate samples associated with the gold mineralization.Microthermometric and laser Raman analyses indicated that the ore-forming fluid was composed of low salinity H₂O-CO₂ composition (~3 wt% NaCl equiv.). The combination of microthermometric data and arsenopyrite-pyrite geothermometry suggest that quartz-carbonate vein formation, gold mineralization and associated alteration of the proximal BIF wall rock occurred at temperature-pressure conditions of 300 ± 30 °C and ∼2 kbar. Thermodynamic calculations at 300 °C suggest an increase in fO₂ (10⁻³²–10⁻³⁰ bars) and corresponding decrease in total sulfur concentration (0.002–0.001 m) that overlapped the pyrite-hematite-magnetite boundary during gold mineralization. Although hematite in the alteration assemblage indicate oxidizing conditions at the deposit site, the calculated low fO₂ values are consistent with previously determined high Fe/Fe + Mg ratios (>0.7) in associated chlorite, absence of sulfates and restricted positive δ³⁴S values in associated pyrite. Based on the fluid composition, metal association and physico-chemical conditions reported in the current study, it is confirmed that gold in the Amalia fluid was transported as reduced bisulfide complexes (e.g., Au(HS)₂⁻). At Amalia, gold deposition was most likely a combined effect of increase in fO₂ corresponding to the magnetite-hematite buffer, and reduction in total sulfur contents due to sulfide precipitation during progressive fluid-rock interaction.The epigenetic features coupled with the isotopic compositions of the ore-forming fluid (δ³⁴S_ΣS = +1.8 to +2.3‰, δ¹⁸O_H2O = +6.6 to +7.9‰, and δ¹³C_ΣC = −6.0 to −7.7‰ at 300–330 °C) are consistent with an externally deep-sourced fluid of igneous signature or/and prograde metamorphism of mantle-derived rocks.     

Nano-mineralogy and -geochemistry of high-grade diasporic karst-type bauxite from Parnassos-Ghiona mines,Greece

In the present work, a combination of various techniques is utilized for the study of nano-mineralogy and -geochemistry of high-grade karst-type bauxite (Al-rich and Fe-depleted samples; Al₂O₃ ca. 80 wt.%) from the Parnassos-Ghiona mines located in Greece. Initial characterization using PXRD and electron microscopy in microscale and mesoscale (SEM-EDS including STEM mode), proved the presence of “Fe-Cr-Ti-containing diaspore”, anatase and minor rutile. The study by means of ⁵⁷Fe Mössbauer spectroscopy, in correlation with magnetic susceptibility measurements and, complemented, with Synchrotron-based spectroscopies at the microscale (SR micro-XRF and micro-XANES/-EXAFS), indicated that Fe³⁺, in contrast to ^[6]Cr³⁺, is not exclusively a component of the diaspore structure. While Cr^3 + substitutes Al^3 + in octahedral sites of diaspore (^[6]Cr³⁺ ↔ ^[6]Al³⁺), the electron microscopy in nanoscale (TEM-EDS & EELS) revealed that Fe exists in the form of peculiar Fe³⁺-bearing nanominerals (most likely maghemite-type phases) between 25 and 45 nm in size, in addition to the Fe³⁺ ions substituting Al³⁺ in the diaspore structure. Moreover, it was proven that TiO₂ polymorph mineral nanoparticles, particularly rounded anatase mesocrystals and nanocrystals and individual needle-shaped rutiles, are dispersed into the diaspore matrix. Thus, diaspore in the studied bauxite concerns -in fact- a distinct Fe³⁺-Cr³⁺-AlOOH low-T authigenic phase, demonstrated for the first time in literature. On the other hand, the observed TiO₂ mineral nanoparticles (formed, together with diaspore, during diagenesis) and Fe nanominerals (formed during epigenesis) were hitherto unknown not only for the allochthonous karst-type bauxite deposits of Greece, but also for the overall bauxite deposits, worldwide.     

Fluid elemental and stable isotope composition of the Nibelungen hydrothermal field (8°18′S,Mid-Atlantic Ridge): Constraints on fluid–rock interaction in heterogeneous lithosphere

Depending on the geological setting, the interaction of submarine hydrothermal fluids with the host rock leads to distinct energy and mass transfers between the lithosphere and the hydrosphere. The Nibelungen hydrothermal field is located at 8°18′S, about 9 km off-axis of the Mid-Atlantic Ridge (MAR). At 3000 m water depth, 372 °C hot, acidic fluids emanate directly from the bottom, without visible sulfide chimney formation. Hydrothermal fluids obtained in 2009 are characterized by low H₂S concentrations (1.1 mM), a depletion of B (192 μM) relative to seawater, lower Si (13.7 mM) and Li (391 μM) concentrations relative to basaltic-hosted hydrothermal systems and a large positive Eu anomaly, and display a distinct stable isotope signature of hydrogen (?²H_H2O = 7.6–8.7‰) and of oxygen (?¹⁸O_H2O = 2.2–2.4‰).The heavy hydrogen isotopic signature of the Nibelungen fluids is a specific feature of ultramafic-hosted hydrothermal systems and is mainly controlled by the formation of OH-bearing alteration minerals like serpentine, brucite, and tremolite during pervasive serpentinization. New isotopic data obtained for the ultramafic-hosted Logatchev I field at 14°45′N, MAR (?²H_H2O = 3.8–4.2‰) display a similar trend, being clearly distinguished from other, mafic-hosted hydrothermal systems at the MAR.The fluid geochemistry at Nibelungen kept stable since the first sampling campaign in 2006 and is evident for a hybrid alteration of mafic and ultramafic rocks in the subseafloor. Whereas the ultramafic-fingerprint parameters Si, Li, B, Eu anomaly and ?²H_H2O distinguish the Nibelungen field from other hydrothermal systems venting in basaltic settings at similar physico-chemical conditions and are related to the interaction with mantle rocks, the relatively high concentrations of trace alkali elements, Pb, and Tl can only be attributed to the alteration of melt-derived gabbroic rocks. The elemental and isotopic composition of the fluid suggest a multi-step alteration sequence: (1) low- to medium-temperature alteration of gabbroic rocks, (2) pervasive serpentinization at moderate to high temperatures, and (3) limited high-temperature interaction with basaltic rocks during final ascent of the fluid. The integrated water/rock ratio for the Nibelungen hydrothermal system is about 0.5.The fluid compositional fingerprint at Nibelungen is similar to the ultramafic-hosted Logatchev I fluids with respect to key parameters. Some compositional differences can be ascribed to different alteration temperatures and other fluid pathways involving a variety of source rocks, higher water/rock ratios, and sulfide precipitation in the sub-seafloor at Logatchev I.     

Iron isotope fractionation during skarn-type alteration: Implications for metal source in the Han-Xing iron skarn deposit

The Han-Xing iron mineralization in the central North China Craton is a typical Fe skarn deposit associated with altered diorites. Here we report the Fe isotopic compositions of whole rocks and mineral separates from this deposit with a view to evaluate the Fe isotope fractionation during the formation of Fe skarn deposit, and to constrain the metal source. The Fe isotopes show a large variation both in whole rocks and mineral separates. Altered diorites show a wide range in δ⁵⁶Fe values (− 0.07‰ to + 0.21‰ relative to the Fe isotope standard IRMM-014) which positively correlate with their TFe₂O₃/TiO₂ ratios (Fe₂O₃ and FeO calculated as TFe₂O₃). The positive correlation indicates that heavy Fe isotopes were preferentially leached from diorites during the skarn-type alteration. Among the metallic minerals, pyrite and pyrrhotite are isotopically heavier (+ 0.12‰ to + 0.48‰) than the magnetite (+ 0.07‰ to + 0.21‰). Fe isotope fractionation between mineral pairs demonstrates that magnetite did not attain Fe isotopic equilibrium with pyrite and pyrrhotite, whereas pyrite and pyrrhotite might have attained isotopic equilibrium. Petrological observations and major element data also suggest that iron was leached from the diorites during the skarn-type alteration. If the leached iron provides the main Fe budget of the Han-Xing Fe skarn deposit, magnetite in ores would be isotopically heavier than the unaltered diorite. However, our results are in contrast with the magnetite being isotopically lighter than the unaltered diorite. This suggests that the major Fe source of the Han-Xing Fe skarn deposit is not from the leaching of diorites, and might be from magmatic fluid which is isotopically lighter than the silicate melt. Our data demonstrate that Fe isotopes can be used as important tracers in deciphering the metal source of Fe skarn deposits.     

Magnetite geochemistry of the Longqiao and Tieshan Fe–(Cu) deposits in the Middle-Lower Yangtze River Belt: Implications for deposit type and ore genesis

Magnetite is a common mineral in many ore deposits and their host rocks, and contains a wide range of trace elements (e.g., Ti, V, Mg, Cr, Mn, Ca, Al, Ni, Ga, Sn) that can be used for deposit type fingerprinting. In this study, we present new magnetite geochemical data for the Longqiao Fe deposit (Luzong ore district) and Tieshan Fe–(Cu) deposit (Edong ore district), which are important magmatic-hydrothermal deposits in eastern China.Textural features, mineral assemblages and paragenesis of the Longqiao and Tieshan ore samples have suggested the presence of two main mineralization periods (sedimentary and hydrothermal) at Longqiao, among which the hydrothermal period comprises four stages (skarn, magnetite, sulfide and carbonate); whilst the Tieshan Fe–(Cu) deposit comprises four mineralization stages (skarn, magnetite, quartz-sulfide and carbonate).Magnetite from the Longqiao and Tieshan deposits has different geochemistry, and can be clearly discriminated by the Sn vs. Ga, Ni vs. Cr, Ga vs. Al, Ni vs. Al, V vs. Ti, and Al vs. Mg diagrams. Such difference may be applied to distinguish other typical skarn (Tieshan) and multi-origin hydrothermal (Longqiao) deposits in the MLYRB. The fluid–rock interactions, influence of the co-crystallizing minerals and other physicochemical parameters, such as temperature and fO₂, may have altogether controlled the magnetite trace element contents of both deposits. The Tieshan deposit may have had higher degree of fO₂, but lower fluid–rock interactions and ore-forming temperature than the Longqiao deposit. The TiO₂–Al₂O₃–(MgO + MnO) and (Ca + Al + Mn) vs. (Ti + V) magnetite discrimination diagrams show that the Longqiao Fe deposit has both sedimentary and hydrothermal features, whereas the Tieshan Fe–(Cu) deposit is skarn-type and was likely formed via hydrothermal metasomatism, consistent with the ore characteristics observed.     

Laboratory charring conditions affect black carbon properties: A case study from Quebec black spruce forests

Black carbon (BC) is an important residue of wildfires in boreal forests, but its characteristics depend on its formation conditions. The objective of this study was to characterize the chemical and physical properties of BC produced under controlled laboratory conditions, while mimicking a gradient of wildfire severity. We used fuels originating from mosses, ericaceous shrubs and spruce trees, as they constitute the major types available in boreal forests. We varied the maximum temperature (MT) from 75 to 800 °C, the duration of charring from 0.5 to 24 h and the abundance of O₂. BC properties were analyzed using elemental analysis and proximate analysis, solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy, scanning electron microscopy (SEM) and surface area (SA) analysis. MT was the most significant factor affecting both chemical and physical changes. Results from ¹³C NMR spectroscopy indicated that 350 °C was a threshold temperature, above which spectra became dominated by aromatic structures for all fuels. Charring duration affected BC composition at both low (250 °C for 12 h vs. 24 h) and high (600 °C for 0.5 h vs. 6 h) MT. The presence of O₂ influenced BC composition mainly at low MT (250 °C) and resulted in accelerated alkyl C degradation, accompanied with a distinct decrease in yield. Results from the SA analysis and the SEM micrographs showed that fuel type influenced BC physical properties, with moss-derived BC presenting higher surface area and microporosity than BC of woody origin.     

The influence of Al2O3 on the H2O content in periclase and ferropericlase at 25 GPa

In this paper I present results of IR spectroscopic measurements of water solubility in Al-bearing periclase and ferropericlase (Mg# = 88) synthesized at 25 GPa and 1400–2000 °C. The IR spectra of their crystals show narrow absorption peaks at 3299, 3308, and 3474 cm^?1. The calculated H₂O contents are 11–25 ppm in periclase (Al₂O₃ = 0.9–1.2 wt.%) and 14–79 ppm in ferropericlase (Al₂O₃ = 0.9–2.9 wt.%). Ferropericlase contains more H₂O and Al₂O₃ than periclase at 1800–2000 °C. I suggest that addition of Al₂O₃ does not influence the solubility of water in ferropericlase but can favor the additional incorporation of Fe₂O₃ into the structure. The incorporation of Fe³⁺ into ferropericlase increases water solubility as a result of iron reduction to Fe²⁺. It is shown that water has limited solubility in ferropericlase from mantle peridotite; therefore, ferropericlase cannot be considered an important hydrogen-bearing mineral in the lower mantle.     

Miscibility in the CaSO4·2H2O–CaSeO4·2H2O system: Implications for the crystallisation and dehydration behaviour

SeO₄²⁻ ions can substitute for sulphate in the gypsum structure. In this work crystals of different Ca(SO₄,SeO₄)·2H₂O solid solutions were precipitated by mixing a CaCl₂ solution with solutions containing different ratios of Na₂SO₄ and Na₂SeO₄. The compositions of the precipitates were analysed by EDS and the cell parameters were determined by X-ray powder diffraction. Moreover, a comparative study on dehydration behaviour of selenate rich and sulfate rich Ca(SO₄,SeO₄)·2H₂O solid solutions was carried out by thermogravimetry.The experimental results show that the Ca(SO₄,SeO₄)·2H₂O solid solution presents a symmetric miscibility gap for compositions ranging from X_CaSO4·2H2O = 0.23 to X_CaSO4·2H2O = 0.77. By considering a regular solution model a Guggenheim parameter a₀ = 2.238 was calculated. The solid phase activity coefficients obtained with this parameter were used to calculate a Lippmann diagram for the system Ca(SO₄,SeO₄)·2H₂O–H₂O.