A comparative evaluation of minerals and trace elements in the ashes from lignite, coal refuse, and biomass fired power plants

Coal being a limited source of energy, extraction of energy from other sources like lignite, coal-refuse, and biomass is being attempted worldwide. The minerals and inorganic elements present in fuel feeds pose different technological and environmental concerns. Lignite ash, refuse ash, and biomass ash collected from Indian power plants burning lignite, coal-refuse, and mustard stalk, respectively, were analyzed for physico-chemical characteristics and trace elements. The lignite ash has high SiO₂, CaO, MgO, Al₂O_3, and SO₃; the refuse ash has high SiO₂ and Fe₂O₃, but low SO₃; the biomass ash has high SiO₂ (but low Al₂O₃), and high CaO, MgO, K₂O, Na₂O, SO₃, and P₂O₅. A substantial presence of chloride (2.1%) was observed in the biomass ash. Quartz is the most abundant mineral species. Other minerals are mullite, hematite, gehlenite, anhydrite, and calcite in the lignite ash; orthoclase in the refuse ash; albite, sanidine, gehlenite, anhydrite, and calcite in the biomass ash. Ashes with high concentrations (> 100 mg/kg) of trace elements are: lignite ash (V < La < Mn < Cr < Ni < Nd < Ba < Ce, Zn < Sr); refuse ash (Cr < Ce < V < Rb < Mn < Sr, Zn < Ba); biomass ash (Cu < Zn < Ba, Sr). Based on Earth crust normalization, Co, Ni, As, Se, Mo, Zn, Pb, U, and REEs (except Pr and Er) are enriched in the lignite ash; molybdenum, Zn, Cs, Pb, Th, U, La, Ce, and Lu in the refuse ash; and Mo, Zn, Sr, Cs, Pb, and Lu in the biomass ash. Elements As, Zn, Mo, Ni, Pb, Rb, Cr, V, Ba, Sr, and REEs are correlated with Al, indicating the possibilities of their association with aluminum silicates minerals. Similarly, barium, Cs, Th, and U are correlated with iron oxides; molybdenum and Sr may also be associated with sulfates and chlorides. Due to the alkaline nature of these ashes, the high concentrations of As and Se in the lignite ash; molybdenum in the biomass ash; and Se in the refuse ash may pose environmental concerns.     

Effect of oxygen fugacity on the H2O storage capacity of forsterite in the carbon-saturated systems

High pressure experiments have been performed in the systems Mg₂SiO₄-C-O-H and Mg₂SiO₄-K₂CO₃-C at 6.3 GPa and 1200 to 1600 °C using a split-sphere multi-anvil apparatus. In the Mg₂SiO₄-C-O-H system the composition of fluid was modeled by adding different amounts of water and stearic acid. The fO₂ was controlled by the Mo-MoO₂ or Fe-FeO oxygen buffers. Several experiments in the Mg₂SiO₄-C-O-H system and all experiments in the Mg₂SiO₄-K₂CO₃-C system have been conducted without buffering the fO₂. Forsterite in the system Mg₂SiO₄-K₂CO₃-C does not reveal OH absorption bands in the IR spectra, while forsterite coexisting with carbon-bearing fluid and silicate melt at logfO₂ from FMQ-2 to FMQ-5 (from 2 to 5 log units below fayalite-magnetite-quartz oxygen buffer) contains 800-1850 wt. ppm H₂O. The maximum concentrations were detected at 1400 °C and FMQ-3.5. We observed an increase in the solidus temperature in the system Mg₂SiO₄-C-O-H from 1200 to above 1600 °C with log fO₂ decreasing from FMQ-2 to FMQ-5. The increase of the solidus temperature and the broadening of the stability field of the H₂O-H₂-CH₄ subsolidus fluid phase at 1400-1600 °C explain the high H₂O storage capacity of forsterite relative to that crystallized from carbon-free, oxidized, hydrous, silicic melt. At temperatures above 1400 °C liquidus forsterite precipitated along with diamond from oxidized (FMQ-1) carbonate-silicate melt and from silicate melt dissolving the moderately reduced C-O-H fluid (from FMQ-2 to FMQ-3.5). Formation of diamond was not detected under ultra-reduced conditions (FMQ-5) at 1200-1600 °C. Olivine co-precipitating with diamond from dry carbonate-silicate or hydrous-silicic fluid/melt can provide information on the H₂O contents and speciation of the diamond-forming media in the mantle. The conditions for minimum post-crystallization alteration of olivine and its hydrogen content are discussed.     

Adsorption of NO, SO2 and light hydrocarbons on activated Greek brown coals

Twenty-eight samples of peat, peaty lignites and lignites (of both matrix and xylite-rich lithotypes) and subbituminous coals have been physically activated by pyrolysis. The results show that the surface area of the activated coal samples increases substantially and the higher the carbon content of the samples the higher the surface area.The adsorption capacity of the activated coals for NO, SO₂, C₃H₆ and a mixture of light hydrocarbons (CH₄, C₂H₆, C₃H₈ and C₄H₁₀) at various temperatures was measured on selected samples. The result shows a positive correlation between the surface area and the gas adsorption. In contrast, the gas adsorption is inversely correlated with the temperature. The maximum recorded adsorption values are: NO = 8.22 × 10^− 5 mol/g at 35 °C; SO₂ = 38.65 × 10^− 5 mol/g at 60 °C; C₃H₆ = 38.9 × 10^− 5 mol/g at 35 °C; and light hydrocarbons = 19.24 × 10^− 5 mol/g at 35 °C. Adsorption of C₃H₆ cannot be correlated with either NO or SO₂. However, there is a significant positive correlation between NO and SO₂ adsorptions. The long chain hydrocarbons are preferentially adsorbed on activated lignites as compared to the short chain hydrocarbons.The results also suggest a positive correlation between surface area and the content of telohuminite maceral sub-group above the level of 45%.     

High pressure phase equilibria in the system CaTiO3-CaSiO3: stability of perovskite solid solutions

Phase relations in the system CaTiO₃-CaSiO₃ were experimentally examined at 5.3–14.7 GPa and 1200–1600 °C with a 6–8 type multianvil apparatus. As pressure increases, stability field of perovskite solid solution extends from CaTiO₃ to CaSiO₃, and the perovskite becomes stable for the entire composition range above about 12.3 GPa. The stability field of Ca(Ti_1?X, Si_X)₂O₅ (0.78<x≦1) titanite solid solution +Ca₂SiO₄ larnite exists in the CaSiO₃-rich composition range at 9.3–12.3 GPa and 1200 °C. Perovskite solid solutions containing CaSiO₃ component of 0 to 66 mol% could be quenched to 1 atm. The composition-molar volume relationship of perovskite solid solution showed that molar volume of perovskite solid solution linearly reduces from the value of CaTiO₃ to that of CaSiO₃.     

Evolution of optical properties of vitrinite, sporinite and semifusinite in response to heating under inert conditions

The objective of the study was to characterize changes of reflectance, reflectance anisotropy and reflectance indicating surface (RIS) shape of vitrinite, sporinite and semifusinite subjected to thermal treatment under inert conditions. Examination was performed on vitrinite, liptinite and inertinite concentrates prepared from channel samples of steam coal (R_r = 0.70%) and coking coal (R_r = 1.25%), collected from seam 405 of the Upper Silesian Coal Basin. The concentrates were heated at temperatures of 400–1200 °C for 1 h time in an argon atmosphere.All components examined in this study: vitrinite, sporinite and semifusinite as well as matrix of vitrinite and liptinite cokes, despite of rank of their parent coal, show, in general, the most important changes of reflectance value and optical anisotropy when heated at 500 °C, 800 °C (with the exception of bireflectance value of sporinite) and 1200 °C.After heating the steam coal at 1200 °C, the vitrinite and the semifusinite reveal similar reflectances, whereas the latter a slightly stronger anisotropy. Sporinite and matrix of liptinite coke have lower reflectances but anisotropy (R_bi and R_am values) similar to those observed for vitrinite and semifusinite. However, at 1000 °C sporinite and matrix of liptinite coke have the highest reflectivity of the studied components. The RIS at 1200 °C is the same for all components.The optical properties of the three macerals in the coking coal become similar after heating at 1000 °C. Coke obtained at 1200 °C did not contain distinguishable vitrinite grains. At 1200 °C semifusinite and vitrinite coke matrix have highest R_r values among the examined components. Maximum reflectance (R_max) reach similar values for vitrinite and sporinite, slightly lower for semifusinite. Matrix of liptinite coke and matrix of vitrinite coke have considerably stronger anisotropy (R_bi and R_am values) than other components. RIS at 1200 °C is also similar for all components.     

Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO₄ and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O₂) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O₂) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO₄ and water was observed over a pH range of 0–2 only at 50 °C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 °C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T  25 °C, pH  3) for decades.Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O₂ to pyrite surface sites. The sorption of molecular O₂ is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO₄. The calculated bulk contribution of atmospheric O₂ in the dissolved SO₄ reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O₂ in the early-formed sulfates, chemisorption and electron transfer of molecular O₂ on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction of hydroxyls from water with S at the anodic S pyrite surface site. Then, the role of molecular O₂ is as proposed in previous studies: acting as electron acceptor only at the cathodic Fe pyrite surface site for oxidation of Fe(II) to Fe(III).     

Influence of pH on mineral speciation in a bioreactor simulating acid mine drainage

Mineral precipitates formed under conditions representative of acid mine drainage were prepared by oxidizing 0.1 M FeS0₄ · 7H₂0 solutions at 24°C and pH 2.3, 2.6, 3.0, 3.3 and 3.6 using a bioreactor and a strain ofThiobacillus ferrooxidans. The oxidation of dissolved Fe²⁺ was monitored colorimetrically and was completed within 90 to 120 h at all pHs. Schwertmannite, Fe₈O₈(OH)₆SO₄, was a major component of the precipitates and was the only phase formed at pH 3.0. Jarosite, (H,Na,K)Fe₃(OH)₆(SO₄)₂, increased in abundance with decreasing pH whereas goethite, α-FeOOH, appeared at pH 3.3 and 3.6. A similar relationship between pH and mineralogy has been reported in natural specimens of mine drainage ochres.     

Formation of ferriolivine and magnesioferrite from Mg — Fe-olivine: Reactions and kinetics of oxidation

Olivine samples (Fa 11) have been oxidized in air (f _O2 = 0.2 atm) at temperatures ranging from 350–700 °C and examined by Mössbauer spectroscopy, transmission electron microscopy, X-ray powder diffraction and thermomagnetic analysis. Oxidation of olivine was found to result in ferriolivine, magnesioferrite (major oxide phase) and magnetite (minor oxide phase) formation. Ferriolivine forms planar (001) precipitates, 0.6 nm in thickness, in the olivine host; the composition is likely to be Mg_0.5 v _0.5(Fe³⁺)_1.0SiO₄. Magnesioferrite MgFe₂O₄ exsolves as fine-grained precipitates (5–6 nm in size) filling interstices between the ferriolivine planar precipitates. Oxidation kinetic data at 700 °C show two stages of oxidation corresponding to formation of ferriolivine in the first stage and magnesioferrite in the second stage. The linear rate law with a rate constant k _Fol = 1.23 · 10^-3 s^-1 was found for the first stage whereas a parabolic rate-law with a constant of k _oxi = 3.28 · 10^-3 s^-1 was determined for the second stage of oxidation. It was found that ferriolivine is not an intermediate metastable phase in the oxidation process, terminated by magnesioferrite formation. The ferriolivine and magnesioferrite are considered to have formed by independent reactions which do not necessarily proceed simultaneously.     

The aqueous geochemistry of Zr and the solubility of some Zr-bearing minerals

Literature data on the thermodynamics of complexation of Zr with inorganic species, at 25°C, have been critically reviewed. The preponderance of published complexation constants deal with F⁻ and OH⁻ ions. Stability constants for the complexation reactions are relatively independent of ionic strength and thus recomended values for each ligand type are averages of the most reliable data. Complexation constants under elevated conditions (T 250°C andP_v = P_H2O) have been predicted for various Zr complexes (F⁻, Cl⁻, SO₄²⁻ and OH⁻) using Helgeson's electrostatic approach. Predominance diagrams (calculated for simple systems with these constants) suggest that, over a wide range of pH conditions, Zr(OH)_4(aq) will dominate the aqueous geochemistry of Zr except under very high activities of competing ligands (e.g., F⁻, SO₄²⁻).The solubilities of vlasovite [Na₂ZrSi₄O₁₁] and weloganite [Sr₃Na₂Zr(CO₃)₆·3H₂O have been measured in KCI solutions (0.5–1.0 M) at 50°C. Weloganite dissolution is complicated by the predictable precipitation of strontianite (SrCO₃) whereas vlasovite dissolves incongruently. Solubility products for the dissolution of welonganite and vlasovite are determined to be −28.96±0.14 and −20.40±1.18, respectively. Concentrations of Zr up to 10⁻³ m were present in the experimental solutions; the presence of large amounts of Zr in aqueous solutions support the possibility of extensive remobilization of Zr during hydrothermal mineralization.     

Identification and implications of fight hydrocarbon fluid inclusions from the Proterozoic Bidjovagge gold-copper deposit, Finnmark, Norway

Carbonic fluid inclusions were observed in quartz-bearing veins at the Proterozoic Bidjovagge AuCu deposit within the Kautokeino greenstone belt in Norway, where mineralization occurred in oxidation zones of graphitic schists. A primary fluid inclusion zonation was observed with C0₂-rich fluid inclusions in the structural footwall of the deposit, and CH₄-rich inclusions within the ore zone in the oxidation zone. Microthermometry of the primary hydrocarbon inclusions revealed 2 groups; (1) a group which homogenized between −125°C and the critical temperature of CH₄ (−82.1°C), which indicated the presence of pure CH₄, and (2) a group which homogenized between the critical temperature of CH₄ and −42°C, which indicated the presence CH₄ and higher hydrocarbons (HHC). Raman microprobe analyses of the first group confirmed the presence of CH₄. The second inclusion group were fluorescent, and Raman spectra clearly displayed CH₄,C₂H₆, and rarer C₃H₈ peaks. A typical feature of the Raman spectra were elevated baselines at the hydrocarbon peaks. Carbon peaks were also usually detected in each inclusion by Raman analysis. Bulk gas chromatography analyses of samples containing the first group (CH₄) indicated the presence of CH₄ and low concentrations of C₂H₆ and C₃H₈. Gas chromatography analyses of samples containing the second group (CH₄ and higher hydrocarbons) confirmed the presence of CH₄, and higher hydrocarbons such as C₂H₆ and C₃H₈ and also butanes. Based on the spacial zonation of hydrocarbons and the estimated PT conditions of 300 to 375°C and 2 to 4 kbars, the authors suggest an abiotic origin for the hydrocarbons. It is suggested that the hydrothermal fluids oxidized the graphitic schist, precipitated Cu and Au and formed light gas hydrocarbons.     

Sorption of methane on lignite from Polish deposits

Coal samples from Miocene lignite deposits (ortholignite—ECE-UN 2002) in Belchatow, Adamow, Konin and Turow (Poland) were analyzed to determine the relationships between coal properties and gas capacity.Investigations presented here addressed the occurrence of methane sorbet in lignite deposits within Poland's largest penetrated lignite deposits (e.g., Belchatow, Adamow, Turow and Konin).Lignite samples collected from surface mines were detritic coal with variable contents of xylites. The highest level of xylites (up to 25 vol.%) was found in carbon samples taken from the Belchatow deposit. Samples from other mines contained no more than 10 vol.% xylites. Petrographic compositions were dominated by huminite group macerals (73-88 vol.%) with atrinite, densinite and texto-ulminite, a porous form of ulminite; inertinite groups were less important components (4-8 vol.%).Isotherms were determined for methane sorption at 298 K with test pressure ranges below 1.2 MPa. At a pressure of 1.0 MPa, the largest gas capacity of approximately 1.7 [dm³ STP/kg] was found in the sample from Belchatow. This result may have been attributable to differences in the porosity of the samples; the porosity of the sample from Belchatow was twice as high as the porosities of the other coal samples. This variation in porosity resulted from the lithologic and maceral composition of the coal sample that contained substantial quantities of porous textinite and texto-ulminite.The thermal sorption equation was used to determine the limiting values of isosteric enthalpy of sorption, which suggested weak interactions between methane and the lignite matrix. The residual gas capacity of the tested samples was also determined.All samples exhibited a high residual methane-bearing capacity, which may not only cause methane to be released from coal at a pressure of 1 bar but also may pose a gas risk during mining operations.     

The MgCr2O4–MgFe2O4 solid solution series: effects of octahedrally coordinated Fe3+ on T–O bond lengths

The influence on the spinel structure of Fe³⁺ → Cr substitution was studied in flux-grown synthetic single crystals of the magnesiochromite–magnesioferrite (MgCr₂O₄–MgFe₂O₄) solid solution series. Samples were analysed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption and Mössbauer spectroscopy. With the exception of iron-poor samples (3–12 mol-% MgFe₂O₄), optical absorption and Mössbauer spectra show that iron occurs almost exclusively as trivalent Fe in the present samples. A very intense and broad absorption band at ca 7,800 cm^?1 dominates the optical absorption spectra of samples with higher Fe-contents. The appearance of this band is related to a distinct structural disorder of Fe³⁺ and a development of magnetic ordering as demonstrated by Mössbauer spectra. Profound composition-related changes are observed in the Mössbauer spectra, which are magnetically unsplit in the range 2–41 mol-% magnesioferrite, but become magnetically split in the range 59–100 mol-% magnesioferrite. Structural parameters a ₀ and M–O increase with magnesioferrite content and inversion degree, while u and T–O decrease. Our study confirms the previously reported (Lavina et al. 2002) influence of Fe³⁺ at the M site on T–O bond lengths in the spinel structure.     

Solution mechanisms of silicate in aqueous fluid and H2O in coexisting silicate melts determined in-situ at high pressure and high temperature

The structure of H₂O-saturated silicate melts, coexisting silicate-saturated aqueous solutions, and supercritical silicate liquids in the system Na₂O·4SiO₂–H₂O has been characterized with the sample at high temperature and pressure in a hydrothermal diamond anvil cell (HDAC). Structural information was obtained with confocal microRaman and with FTIR microscopy. Fluids and melts were examined along pressure-temperature trajectories defined by the isochores of H₂O at nominal densities, ρ_fluid, (from EOS of pure H₂O) of 0.90 and 0.78 g/cm³. With ρ_fluid = 0.78 g/cm³, water-saturated melt and silicate-saturated aqueous fluid coexist to the highest temperature (800 °C) and pressure (677 MPa), whereas with ρ_fluid = 0.90 g/cm³, a homogeneous single-phase liquid phase exists through the temperature and pressure range (25–800 °C, 0.1–1033 MPa). Less than 5 vol% quartz precipitates near 650 °C in both experimental series, thus driving Na/Si-ratios of melt + fluid phase assemblages to higher values than that of the Na₂O·4SiO₂ starting material.Molecular H₂O (H₂O°) and structurally bonded OH groups were observed in coexisting melts and fluids as well as in supercritical liquids. Their OH/(H₂O)-ratio is positively correlated with temperature. The OH/(H₂O)° in melts is greater than in coexisting fluids. Structural units of Q³, Q², Q¹, and Q⁰ type are observed in all phases under all conditions. An expression of the form, 12Q³ + 13H₂O2Q² + 6Q¹ + 4Q⁰, describes the equilibrium among those structural units. This equilibrium shifts to the right with increasing pressure and temperature with a ΔH of the reaction near 425 kJ/mol.     

Geology and characterisation of the Pecket coal deposit, Magellan Region, Chile

The geology, petrography and chemical variation of the Pecket coal sequence, Magellan Region (52°57′S, 71°10′W), the only Chilean coal used for electricity generation on a large scale, has been studied in order to predict their combustion behaviour, especially in coal blends. The depositional environment of formation of the coal seams was a swamp rarely exposed to subaerial conditions and was associated with the development of the folded foreland of the Magellan basin during the Tertiary (Oligo–Miocene). The general tectonic regime of the collision of the Antarctic and South American plates is reflected by a system of joints with 40°N–50°W strike. The maceral composition of all six seams studied indicates high contents of vitrinite (>90%), minor content of liptinite (4.7%) and inertinite (<2%). Occurrence of tonstein horizons altered to kaolinite indicates a distal volcanism during peat accumulation. Coal rank varies between lignite and subbituminous (Ro=0.28–0.42%) with an average dry basis calorific value of 5450 kcal/kg, 17 wt.% moisture, 41 wt.% volatile matter, and sulphur content below 0.5 wt.%. The mineral matter (LTA) associated with the coal shows a dominance of kaolinite with quartz, smectite, and minor basanite. SiO₂/Al₂O₃ and Fe₂O₃/CaO ratios of the ashes diminish towards the lower seams. With respect to the utilisation of Pecket coals in combustion, base/acid ratios (B/A) and silica ratios (SR) indicate potential fouling for seams 1, 2, 5, and 6i, with high fouling indexes (Rf) for seams 2 and 5. Pecket coal is excellent for blend combustion due to its low sulphur content.     

Sn-polymetallic greisen-type deposits associated with late-stage rapakivi granites, Brazil: fluid inclusion and stable isotope characteristics

Tin-polymetallic greisen-type deposits in the Itu Rapakivi Province and Rondônia Tin Province, Brazil are associated with late-stage rapakivi fluorine-rich peraluminous alkali-feldspar granites. These granites contain topaz and/or muscovite or zinnwaldite and have geochemical characteristics comparable to the low-P sub-type topaz-bearing granites. Stockworks and veins are common in Oriente Novo (Rondônia Tin Province) and Correas (Itu Rapakivi Province) deposits, but in the Santa Bárbara deposit (Rondônia Tin Province) a preserved cupola with associated bed-like greisen is predominant. The contrasting mineralization styles reflect different depths of formation, spatial relationship to tin granites, and different wall rock/fluid proportions. The deposits contain a similar rare-metal suite that includes Sn (±W, ±Ta, ±Nb), and base-metal suite (Zn–Cu–Pb) is present only in Correas deposit. The early fluid inclusions of the Correas and Oriente Novo deposits are (1) low to moderate-salinity (0–19 wt.% NaCl eq.) CO₂-bearing aqueous fluids homogenizing at 245–450 °C, and (2) aqueous solutions with low CO₂, low to moderate salinity (0–14 wt.% NaCl eq.), which homogenize between 100 and 340 °C. In the Santa Bárbara deposit, the early inclusions are represented by (1) low-salinity (5–12 wt.% NaCl eq.) aqueous fluids with variable CO₂ contents, homogenizing at 340 to 390 °C, and (2) low-salinity (0–3 wt.% NaCl eq.) aqueous fluid inclusions, which homogenize at 320–380 °C. Cassiterite, wolframite, columbite–tantalite, scheelite, and sulfide assemblages accompany these fluids. The late fluid in the Oriente Novo and Correas deposit was a low-salinity (0–6 wt.% NaCl eq.) CO₂-free aqueous solution, which homogenizes at (100–260 °C) and characterizes the sulfide–fluorite–sericite association in the Correas deposit. The late fluid in the Santa Bárbara deposit has lower salinity (0–3 wt.% NaCl eq.) and characterizes the late-barren-quartz, muscovite and kaolinite veins. Oxygen isotope thermometry coupled with fluid inclusion data suggest hydrothermal activity at 240–450 °C, and 1.0–2.6 kbar fluid pressure at Correas and Oriente Novo. The hydrogen isotope composition of breccia-greisen, stockwork, and vein fluids (δ¹⁸O_quartz from 9.9‰ to 10.9‰, δD_H2O from 4.13‰ to 6.95‰) is consistent with a fluid that was in equilibrium with granite at temperatures from 450 to 240 °C. In the Santa Bárbara deposit, the inferred temperatures for quartz-pods and bed-like greisens are much higher (570 and 500 °C, respectively), and that for the cassiterite-quartz-veins is 415 °C. The oxygen and hydrogen isotope composition of greisen and quartz-pods fluids (δ¹⁸O_qtz-H2O=5.5–6.1‰) indicate that the fluid equilibrated with the albite granite, consistent with a magmatic origin. The values for mica (δ¹⁸O_mica-H2O=3.3–9.8‰) suggest mixing with meteoric water. Late muscovite veins (δ¹⁸O_qtz-H2O=−6.4‰) and late quartz (δ¹⁸O_mica-H2O=−3.8‰) indicate involvement of a meteoric fluid. Overall, the stable isotope and fluid inclusion data imply three fluid types: (1) an early orthomagmatic fluid, which equilibrated with granite; (2) a mixed orthomagmatic-meteoric fluid; and (3) a late hydrothermal meteoric fluid. The first two were responsible for cassiterite, wolframite, and minor columbite–tantalite precipitation. Change in the redox conditions related to mixing of magmatic and meteoric fluids favored important sulfide mineralization in the Correas deposit.     

Sulfur speciation in natural hydrothermal waters, Iceland

The speciation of aqueous dissolved sulfur was determined in hydrothermal waters in Iceland. The waters sampled included hot springs, acid-sulfate pools and mud pots, sub-boiling well discharges and two-phase wells. The water temperatures ranged from 4 to 210 °C, the pH_T was between 2.20 and 9.30 at the discharge temperature and the SO₄ and Cl concentrations were 0.020-52.7 and <0.01-10.0 mmol kg⁻¹, respectively. The analyses were carried out on-site within ∼10 min of sampling using ion chromatography (IC) for sulfate (SO₄²⁻), thiosulfate (S₂O₃²⁻) and polythionates (S_xO₆²⁻) and titration and/or colorimetry for total dissolved sulfide (S²⁻). Sulfite (SO₃²⁻) could also be determined in a few cases using IC. Alternatively, for few samples in remote locations the sulfur oxyanions were stabilized on a resin on site following elution and analysis by IC in the laboratory. Dissolved sulfate and with few exceptions also S²⁻ were detected in all samples with concentrations of 0.02-52.7 mmol kg⁻¹ and <1-4100 μmol kg⁻¹, respectively. Thiosulfate was detected in 49 samples of the 73 analyzed with concentrations in the range of <1-394 μmol kg⁻¹ (S-equivalents). Sulfite was detected in few samples with concentrations in the range of <1-3 μmol kg⁻¹. Thiosulfate and SO₃²⁻ were not detected in <100 °C well waters and S₂O₃²⁻ was observed only at low concentrations (<1-8 μmol kg⁻¹) in ∼200 °C well waters. In alkaline and neutral pH hot springs, S₂O₃²⁻ was present in significant concentrations sometimes corresponding to up to 23% of total dissolved sulfur (S_TOT). In steam-heated acid-sulfate waters, S₂O₃²⁻ was not a significant sulfur species. The results demonstrate that S₂O₃²⁻ and SO₃²⁻ do not occur in the deeper parts of <150 °C hydrothermal systems and only in trace concentrations in ∼200-300 °C systems. Upon ascent to the surface and mixing with oxygenated ground and surface waters and/or dissolution of atmospheric O₂, S²⁻ is degassed and oxidized to SO₃²⁻ and S₂O₃²⁻ and eventually to SO₄²⁻ at pH >8. In near-neutral hydrothermal waters the oxidation of S²⁻ and the interaction of S²⁻ and S⁰ resulting in the formation of S_x²⁻ are considered important. At lower pH values the reactions seemed to proceed relatively rapidly to SO₄²⁻ and the sulfur chemistry of acid-sulfate pools was dominated by SO₄²⁻, which corresponded to >99% of S_TOT. The results suggest that the aqueous speciation of sulfur in natural hydrothermal waters is dynamic and both kinetically and source-controlled and cannot be estimated from thermodynamic speciation calculations.     

Structural modifications of vitrinite and alginite concentrates during pyrolitic maturation at different heating rates. A combined infrared, C NMR and microscopical study

Immature vitrinite samples from a Miocene lignite seam of western Germany (H/C = 1.14, O/C = 0.41) and alginite concentrates from a Tasmanite deposit of Australia (H/C = 1.60, O/C = 0.10) were pyrolyzed in a stream of argon at heating rates of 0.1 and 2.0°C/min up to temperatures varying from 200 to 670°C. The solid maceral residues were subjected to elemental and microscopical analysis and studied by IR and ¹³C CP/MAS NMR spectroscopy with respect to structural modifications.The maximum pyrolytic weight loss amounts to 60% of the initial organic matter in the case of vitrinite and to 85% for alginite, the onset of degradation reactions being shifted to higher temperatures with increasing rate of heating. Both infrared and NMR spectra of the vitrinite samples indicate a rapid decomposition of the cellulose component upon heating whereas lignin related structures such as aromatic ether linkages remain remarkably stable. The main hydrocarbon release from vitrinite occurs at very early evolution stages (T_max = 296°C, R_m = 0.20% at 0.1°C/min; T_max = 337°C, R_m = 0.23 at 2.0°C/min). Hydrocarbon generation from alginite requires higher temperatures (T_max = 388 and 438°C) and is completed within a distinctly narrower temperature range.The pronounced increase of vitrinite reflectance between 350 and 670°C seems to be associated with a rather time-consuming reorganization of the residual organic material. The concomitant growth of polyaromatic units is illustrated by the increasing intensity ratio of the aromatic ring stretching vibration bands at 1600 and 1500 cm⁻¹. These reactions are moreover marked by increasing loss of phenolic oxygen and by increasing conversion of aliphatic carbon into fixed aromatic carbon.     

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.     

Phase equilibria for the Fe2SiO4–Fe3O4 system under high pressure

High pressure phase relation of the system Fe₂SiO₄–Fe₃O₄ was investigated by synthesis experiments using multi-anvil high pressure apparatus. A complete solid solution with spinel structure along Fe₂SiO₄–Fe₃O₄ join occurs above 9 GPa at 1200 °C. Lattice constants of the solid solution show almost linear variation with composition. A spinelloid phase is stable for intermediate compositions in the pressure range from 3 to 9 GPa. the synthesized spinelloid phase is successfully indexed assuming nickel aluminosilicate V type structure. Received: October 16, 1995 / Revised, accepted: March 19, 1997     

A study on the preparation of fine and low soda alumina

A simple process to produce fine and low soda α-alumina (α-Al₂O₃) from a commercial grade aluminium trihydroxide (gibbsite, Al(OH)₃) produced by KC Corporation Ltd was developed. There are two options for this process with the first one producing low soda α-alumina (< 0.05% Na₂O) having a mean particle size of 50 μm. The second option yields a fine product with a mean size of less than 10 μm. In the first option, a plant aluminium trihydroxide containing 0.20% Na₂O was first fluidized with nitrogen at 400–600 °C to yield an amorphous activated alumina. This intermediate product was then treated with acetic or oxalic acid, washed with water and heated to 1200 °C to form calcined α-alumina, having a Na₂O content of less than 0.05%. A 20 min leaching using 0.2 M acetic or oxalic acid could yield an alumina product containing 0.04% Na₂O. In the second option, a new technique for the preparation of fine and low soda α-alumina was evaluated using an attrition mill working also as a leaching vessel at 80 °C. Fine (< 10 μm in mean particle size) and low soda (< 0.04% Na₂O) alumina was produced by a 20 min leaching step with 0.2 M acetic acid and concurrent attrition milling.