Hydrogen sulfide measurements in air by passive/diffusive samplers and high-frequency analyzer: A critical comparison

In this study, hydrogen sulfide (H₂S) measurements in air carried out using (a) passive/diffusive samplers (Radiello^® traps) and (b) a high-frequency (60 s) real-time analyzer (Thermo^® 450i) were compared in order to evaluate advantages and limitations of the two techniques. Four different sites in urban environments (Florence, Italy) and two volcanic areas characterized by intense degassing of H₂S-rich fluids (Campi Flegrei and Vulcano Island, Italy) were selected for such measurements. The concentrations of H₂S generally varied over 5 orders of magnitude (from 10⁻¹–10³ μg/m³), the H₂S values measured with the Radiello^® traps (H₂S_R) being significantly higher than the average values measured by the Thermo^® 450i during the trap exposure (H₂S_Ta), especially when H₂S was <30 μg/m³. To test the reproducibility of the Radiello^® traps, 8 passive/diffusive samplers were contemporaneously deployed within an 0.2 m² area in an H₂S-contaminated site at Mt. Amiata (Tuscany, Italy), revealing that the precision of the H₂S_R values was ±49%. This large uncertainty, whose cause was not recognizable, is to be added to that related to the environmental conditions (wind speed and direction, humidity, temperature), which are known to strongly affect passive measurements. The Thermo^® 450i analyzer measurements highlighted the occurrence of short-term temporal variations of the H₂S concentrations, with peak values (up to 5732 μg/m³) potentially harmful to the human health. The Radiello^® traps were not able to detect such temporal variability due to their large exposure time. The disagreement between the H₂S_R and H₂S_Ta values poses severe concerns for the selection of an appropriate methodological approach aimed to provide an accurate measurement of this highly toxic air pollutant in compliance with the WHO air quality guidelines. Although passive samplers may offer the opportunity to carry out low-cost preliminary surveys, the use of the high-frequency H₂S analyzer is preferred when an accurate assessment of air quality is required. In fact, the latter provides precise real-time measurements for a reliable estimation of the effective exposure to hazardous H₂S concentrations, giving insights into the mechanisms regulating the dispersion of this air pollutant in relation to the meteorological parameters.     

Modern sedimentation system of Lake Untersee, East Antarctica

The paper presents data on the geographic and geological conditions of modern sedimentation in Lake Untersee, the largest lake in East Antarctica. Geochemical and sedimentation data indicate that the leading mechanism providing Al-Si sedimentary material to the surface layer of the bottom sediments is the seasonal melting of the Anuchin glacier and the mountain glacier on the southeastern face of the valley hosting the lake. The strongly reduced conditions in the lowermost 25 m of the water column in the smaller of the two depressions at the lake bottom were favorable for the enrichment of the bottom sediments in bacteriogenic organic matter, Mo, Au, and Pd. The H₂S-contaminated water facilitates the significant enrichment of the sediments only in redox-sensitive elements able to migrate in the form of anionic complexes and precipitate (coprecipitate) as sulfides.     

Effects of F,B2O3 and P2O5 on the solubility of water in haplogranite melts compared to natural silicate melts

The effects of F, B₂O₃ and P₂O₅ on the H₂O solubility in a haplogranite liquid (36 wt. % SiO₂, 39 wt. % NaAlSi₃O₈, 25 wt. % KAlSi₃O₈) have been determined at 0.5, 1, 2, and 3 kb and 800, 850, and 900°C. The H₂O solubility increases with increasing F and B content of the melt. The H₂O solubility increase in more important at high pressure (2 and 3 kb) than at low pressure (0.5 kb). At 2 kb and 800°C, the H₂O solubility increases from 5.94 to 8.22 wt. % H₂O with increasing F content in the melt from 0 to 4.55 wt. %, corresponding to a linear H₂O solubility increase of 0.53 mol H₂O/mol F. With addition of 4.35 wt. % B₂O₃, the H₂O solubility increases up to 6.86 wt. % H₂O at 2 kb and 800°C, corresponding to a linear increase of 1.05 mol H₂O/mol B₂O₃. The results allow to define the individual effects of fluorine and boron on H₂O solubility in haplogranitic melts with compositions close to that of H₂O-saturated thermal minima (at 0.5–3 kb). Although P has a dramatic effect on the phase relations in the haplogranite system, its effect on the H₂O solubility was found to be negligible in natural melt compositions. The concominant increase in H₂O solubility and F can not be interpreted on the basis of the available spectroscopic data (existence of hydrated aluminofluoride complexes or not). In contrast, hydrated borates or more probably boroxol complexes have been demonstrated in B-bearing hydrous melts.     

The yield and isotopic composition of radiolytic H2, a potential energy source for the deep subsurface biosphere

The production rate and isotopic composition of H₂ derived from radiolytic reactions in H₂O were measured to assess the importance of radiolytic H₂ in subsurface environments and to determine whether its isotopic signature can be used as a diagnostic tool. Saline and pure, aerobic and anaerobic water samples with pH values of 4, 7, and 10 were irradiated in sealed vials at room temperature with an artificial γ source, and the H₂ abundance in the headspace and its isotopic composition were measured. The H₂ concentrations were observed to increase linearly with dosage at a rate of 0.40 ± 0.04 molecules (100 eV)⁻¹ within the dosage range of 900 to 3500 Gray (Gy; Gy = 1 J Kg⁻¹) with no indication of a maximum limit on H₂ concentration. At ∼2000 Gy, the H₂ concentration varied only by 16% across the experimental range of pH, salinity, and O₂. Based upon this measured yield and H₂ yields for α and β particles, a radiolytic H₂ production rate of 10⁻⁹ to 10⁻⁴ nM s⁻¹ was estimated for the range of radioactive element concentrations and porosities typical of crustal rocks. The δD of H₂ was independent of the dosage, pH (except for pH 4), salinity, and O₂ and yielded an αD_H2O-H2 of 2.05 ± 0.07 (αD_H2O-H2 = (D/H)_H2O to (D/H)_H2), slightly less than predicted radiolytic models. Although this radiolytic fractionation value is significantly heavier than that of equilibrium isotopic exchange between H₂ and H₂O, the isotopic exchange rate between H₂ and H₂O will erase the heavy δD of radiolytic H₂ if the age of the groundwater is greater than ∼10³ to 10⁴ yr. The millimolar concentrations of H₂ observed in the groundwater of several Precambrian Shields are consistent with radiolysis of water that has resided in the subsurface for a few million years. These concentrations are well above those required to support H₂-utilizing microorganisms and to inhibit H₂-producing, fermentative microorganisms.     

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

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

常用气体地热温度计的应用及效果评价

基于冰岛部分地热田的实际资料,选择有代表性的、不同温度的地热田,应用CO₂、H₂S、H₂、CO₂/H₂和H₂S/H₂气体地热温度计计算热储温度,深入探讨了影响温度计准确性的各种因素,提出CO₂和H₂S温度计具有良好的实用价值。在热储温度T<200℃时,CO₂温度计的预测温度略低;在200℃<T<300℃范围时,H₂S温度计标定不够准确。并对现有的其它气体地热温度计进行了简要评价。     

Theoretical and experimental investigation of nickel isotopic fractionation in species relevant to modern and ancient oceans

Nickel plays a central role as an enzyme co-factor in the metabolism of methanogenic Archaea. Methanogens can fractionate Ni isotopes during assimilation, opening the possibility of using the stable isotopic composition of Ni as a biomarker. However, other sources of Ni isotopic variations need to be evaluated before one can establish Ni isotopes as an unambiguous tracer of methanogenesis in the rock record. Equilibrium exchange of Ni between the different species present in the ocean is a potential source of isotopic fractionation. Through controlled laboratory experiments and theoretical calculations, we quantify equilibrium Ni isotope fractionation between different species relevant to the modern and ancient ocean: Ni(H₂O)₆²⁺, Ni(H₂O)₁₈²⁺, NiOH(H₂O)₅⁺, Ni(OH)₂(H₂O)₄, NiCl(H₂O)₅⁺, cis-NiCl₂(H₂O)₄, trans-NiCl₂(H₂O)₄, NiHS(H₂O)₅⁺, Ni(HS)₂(H₂O)₄, NiSO₄(H₂O)₄, NiHCO₃(H₂O)₄⁺, NiCO₃(H₂O)₄, and organic ligands (crown ether and oxalic acid). The magnitude of ligand-controlled Ni isotopic fractionation, approximately 1.25‰/amu (2.5‰ for the ⁶⁰Ni/⁵⁸Ni ratio), is similar to that previously measured in cultures of methanogenic Archaea.     

Geothermal gas equilibria

Comparison of theoretical and analytical equilibrium constants based on the reactions CH₄ + 2H₂O = CO₂ + 4H₂, 2NH₃ = N₂ + 3H₂ and iron(II)-aluminium-silicate + 2H₂S = FeS₂ + H₂ + aluminium-silicate, shows that the composition of fluids discharged from geothermal areas in New Zealand (Wairakei, Kawerau, Broadlands) reflects close to complete attainment of chemical equilibrium within the system H₂O, CO₂, H₂S, NH₃, H₂, N₂ and CH₄. Under conditions prevailing in explored geothermal systems in New Zealand, the minerals graphite (elemental carbon), anhydrite, pyrrhotite, magnetite do not appear to take part in the overall equilibrium system. The three physical parameters required to evaluate geothermal gas reactions are temperature, pressure and vapor-liquid ratios within the gas equilibration zone.     

Chemical geothermometry in geothermal systems

The application of chemical and isotopic geothermometry to geothermal systems is reviewed, pointing out the uses and limitations of specific reactions in estimating deep temperatures from well, hot-spring and fumarole discharges.At present the most reliable indicators are: the silica-water equilibria; the Na/K ratio; the isotopic distributions Δ²H(H₂“H₂O), Δ²H(H₂“CH₄), Δ¹⁸O(H₂O“HSO^?₄); and the gas reactions CO₂ + 4H₂ ? CH₄ + 2H₂O, and 2NH₃ ? N₂ + 3H₂. Many other qualitative chemical indicators exist.     

车载小型气体质谱仪现场地气分析应用

OmniStar小型气体质谱仪用于车载实验室,可根据野外情况采取灵活的采样方式,实现对H2、He、CH4、N2、O2、Ar、CO2以及C3H8、C4H10的现场分析。对浓度为100×10-6的H2、He、CH4、N2、O2、Ar、CO2混合标气进行100次连续测定,得到的各组分的精密度(RSD)均优于1%,H2、He、Ar、CO2准确度(RE)分别为3.74、0.94、1.83、10.5;对室内空气进行连续3 500次测定,得到的H2、He、CO2的精密度分别为2.25%、5.55%、4.06%,N2、O2、Ar的精密度优于1%;对CH4、C2H6、C3H8、C4H10混合标准气体进行连续13次测量,得到的C3H8、C4H10的精密度(RSD)优于1%,测量的平均值与标准值完全吻合,能够满足野外现场分析需求。在内蒙古西乌旗及新疆金窝子地区应用该仪器,采用采样袋取气、螺旋钻及井孔原位在线测定等方式得到样品数据,并发现两区域内部分采样点的CO2、H2及He异常。     

Electrochemistry of reduced sulfur species in natural waters—I. The H2S-H2O system

Careful measurements of rest potentials of platinum electrodes (Eh) in the H₂S-H₂O system were made together with measurements of the pH and the potentials of Ag-Ag₂S electrodes (E_s^2?). The potentials of the platinum electrode are characteristic of H₂S chemisorption followed by H₂S discharge on the platinum. The relations between Eh, E_s^2? and pH are characteristic of the H₂S-H₂O system and of the hydrogen sulfide concentration. Thus these parameters can be employed to distinguish H₂S-H₂O systems from H₂S-S₈-H₂O systems. Field measurements on hot sulfurous springs are in agreement with laboratory data.     

Factors Controlling Precipitation of Barite and Witherite and Genesis of the Ankang–Xunyang Barium Deposits, Shaanxi, China

The barium deposits in Ankang and Xunyang counties,Shaanxi Province,China,occur in the northernmost part of the world-class barium metallogenic belt in south Qinling.The deposits are hosted by the Lower Silurian carbonaceous siliceous rocks,with a unique combination of barite and witherite.The homogenization temperatures of fluid inclusions in the barite are mainly concentrated between 135 and 155 ℃,whereas those from the witherite have two peaks of 165-175 ℃,and 215-225℃,respectively.Laser Raman analysis of fluid inclusions indicates that the vapor phase of fluid inclusions in barite is dominated by H_2O,although some contains N_2,H_2S,and CH_4.The compositions of the vapor and liquid phases of fluid inclusions in witherite can be divided into two end-members,one dominated by H_2O without other volatiles,and the other containing CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6 in addition to H_2O.CO_2,H_2S,and some CH_4 are interpreted as products of chemical reactions during mineralization.Organic gases(CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6) in the fluids were critical in the formation of barium sulfate versus carbonate.The δ~(34)S values of barite range from 38.26‰ to54.23‰(CDT),the δ~(34)S values of sulfides coexisting with barium minerals vary from 22.44‰ to25.11‰(CDT),and those in the wall rock from 11.60‰ to 19.06‰(CDT).We propose that the SO_4~(2-)generally experienced bacterial sulfate reduction in seawater before mineralization,and some SO_4~(2-)also experienced thermochemical sulfate reduction in hydrothermal system during mineralization.The δ~(13)C values of witherite range from-27.30‰ to-11.80‰(PDB),suggesting that carbon was sourced from organic substances(like CH_4,C_2H_4,and C_2H_6).The formation of witherite was possibly associated with thermochemical sulfate reduction,which caused the consumption of the organic gases and SO_4~(2-) in the hydrothermal solutions,consequently inhibiting barite formation.The important conditions for forming witherite include high fluid temperatures,high Ba~(2+) concentrations,CO_2 in the fluids,low HS~- concentrations,and the subsequent rapid diffusion of H_2S during thermochemical sulfate reduction of the fluids.     

Cordierite as a sensor of fluid conditions in high-grade metamorphism and crustal anatexis

Cordierite H₂O and CO₂ volatile saturation surfaces derived from recent experimental studies are presented for P–T conditions relevant to high‐grade metamorphism and used to evaluate fluid conditions attending partial melting and granulite formation. The volatile saturation surfaces and saturation isopleths for both H₂O and CO₂ in cordierite are strongly pressure dependent. In contrast, the uptake of H₂O by cordierite in equilibrium with melts formed through biotite dehydration melting, controlled by the distribution of H₂O between granitic melt and cordierite, D_w[D_w = wt% H₂O (melt)/wt% H₂O(Crd)], is mainly temperature dependent. D_w = 2.5–6.0 for the H₂O contents (0.4–1.6 wt percentage) typical of cordierite formed through biotite dehydration melting at 3–7 kbar and 725–900 °C. This range in D_w causes a 15–30% relative decrease in the total wt% of melt produced from pelites. Cordierite in S‐type granites are H₂O‐rich (1.3–1.9 wt%) and close to or saturated in total volatiles, signifying equilibration with crystallizing melts that achieved saturation in H₂O. In contrast, the lower H₂O contents (0.6–1.2 wt percentage) preserved in cordierite from many granulite and contact migmatite terranes are consistent with fluid‐absent conditions during anatexis. In several cases, including the Cooma migmatites and Broken Hill granulites, the cordierite volatile compositions yield a_H2O values (0.15–0.4) and melt H₂O contents (2.2–4.4 wt%) compatible with model dehydration melting reactions. In contrast, H₂O leakage is indicated for cordierite from Prydz Bay, Antarctica that preserve H₂O contents (0.5–0.3 wt%) which are significantly less than those required (1.0–0.8 wt%) for equilibrium with melt at conditions of 6 kbar and 860 °C. The CO₂ contents of cordierite in migmatites range from negligible (< 0.1 wt%) to high (0.5–1.0 wt%), and bear no simple relationship to preserved cordierite H₂O contents and a_H2O. In most cases the cordierite volatile contents yield total calculated fluid activities (a_H2O + a_CO2) that are significantly less than those required for fluid saturation at the P–T conditions of their formation. Whether this reflects fluid absence, dilution of H₂O and CO₂ by other components, or leakage of H₂O from cordierite is an issue that must be evaluated on a case‐by‐case basis.     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores. X. thermal stability and dehydration features of synthetic analogs of the cobaltomenite–ahlfeldite solid solution series

The aim of this study is the experimental investigation of the synthetic analogs of cobaltomenite, CoSeO₃ ? 2H₂O, ahlfeldite, NiSeO₃ ? 2H₂O, members of the cobaltomenite–ahlfeldite solid solution series (Ni _x Co_1–x )SeO₃ ? 2H₂O, and singularities of their dehydration and dissociation. The intermediate members of the cobaltomenite (CoSeO₃ ? 2H₂O)–ahlfeldite (NiSeO₃ ? 2H₂O) series have been synthesized and studied with a combination of X-ray diffraction, scanning electron microscopy, and the simultaneous application of thermogravimetry (TG) and differential scanning calorimetry (DSC) within the temperature range from 25 to 640°C. The complete solid solution series corresponds to the monoclinic space group P2₁/n. Unit-cell dimensions decrease in all crystallographic directions as the amount of Ni increases. The angle β increases from 98.82(1) (cobaltomenite) to 99.05(1)° (ahlfeldite). It has been established that CoSeO₃ ? 2H₂O and NiSeO₃ ? 2H₂O dehydrate at 120–340°C through two stages apparently corresponding, to the formation of intermediate hydrated species CoSeO₃ ? H₂O and NiSeO₃ ? 1/3H₂O. The reaction enthalpies for each dehydration stage of CoSeO₃ ? 2H₂O and NiSeO₃ ? 2H₂O have been determined. Changes of the unit-cell dimensions and dehydration temperatures are rationalized in terms of the Co and Ni site occupancy in the structure of the cobaltomenite–ahlfeldite solid-solution series members.     

Preferential dissolution of SiO<Subscript>2</Subscript> from enstatite to H<Subscript>2</Subscript> fluid under high pressure and temperature

Stability and phase relations of coexisting enstatite and H₂ fluid were investigated in the pressure and temperature regions of 3.1–13.9 GPa and 1500–2000 K using laser-heated diamond-anvil cells. XRD measurements showed decomposition of enstatite upon heating to form forsterite, periclase, and coesite/stishovite. In the recovered samples, SiO₂ grains were found at the margin of the heating hot spot, suggesting that the SiO₂ component dissolved in the H₂ fluid during heating, then precipitated when its solubility decreased with decreasing temperature. Raman and infrared spectra of the coexisting fluid phase revealed that SiH₄ and H₂O molecules formed through the reaction between dissolved SiO₂ and H₂. In contrast, forsterite and periclase crystals were found within the hot spot, which were assumed to have replaced the initial orthoenstatite crystals without dissolution. Preferential dissolution of SiO₂ components of enstatite in H₂ fluid, as well as that observed in the forsterite H₂ system and the quartz H₂ system, implies that H₂-rich fluid enhances Mg/Si fractionation between the fluid and solid phases of mantle minerals.     

Experimental determination of the activity-composition relations and phase equilibria of H2O-CO2-NaCl fluids at 500°C, 500 bars

An understanding of the activity-composition (a-X) relations and phase equilibria of halite-bearing, mixed-species supercritical fluids is critically important in many geological and industrial applications. We have performed experiments on H₂O-CO₂-NaCl fluids at 500°C, 500 bar, to obtain accurate and precise data on their a-X relations and phase equilibria. Two kinds of experiments were performed. First, H₂O-CO₂-NaCl samples were reacted at fixed activities of H₂O = 0.078, 0.350, 0.425, 0.448, 0.553, 0.560, 0.606, 0.678, 0.798, 0.841, and 0.935 to define the tie lines of known H₂O activity in the halite-vapor and vapor-brine fields. Results indicate that fluids with all but the last of these H₂O activities lie in the vapor-halite two-phase region and that a fluid with a_H2O = 0.841 has a composition close to the three-phase (vapor + brine + halite) field. A second set of experiments was performed to determine the solubility of NaCl in parts of the system in equilibrium with halite. Data from these experiments suggest that the vapor corner of the three-phase field lies at H₂O contents above X_H2O = 0.58 and X_NaCl = 0.06, and below X_H2O = 0.75 and X_NaCl = 0.06, which is a significantly more H₂O-rich composition than indicated by existing thermodynamic models.     

The thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores. XI. Solubility of synthetic chalcomenite analog and zinc selenite at 25°C

The aim of this study is the synthesis of CuSeO₃·2H₂O (chalcomenite analog), ZnSeO₃·2H₂O, and ZnSeO₃·H₂O and the investigation of their solubility in water. CuSeO₃·2H₂O has been synthesized from solutions of Cu nitrate and Na selenite, while Zn selenites were synthesized from solutions of Zn nitrate and Na selenite. The samples obtained have been examined with X-ray diffraction and infrared and Raman spectroscopy. The solubility has been determined using the isothermal saturation method in ampoules at 25°C. The solubility has been calculated using the Geochemist’s Workbench (GMB 9.0) software package. Solubility products have been calculated for CuSeO₃·2H₂O (10^–10.63), ZnSeO₃·2H₂O (10^–8.35), and ZnSeO₃·H₂O (10^–7.96). The database used comprises thermodynamic characteristics of 46 elements, 47 base particles, 48 redox pairs, 551 particles in solution, and 624 solid phases. The Eh–pH diagrams of the Zn–Se–H₂O and Cu–Se–H₂O systems were plotted for the average contents of these elements in underground water in oxidation zones of sulfide deposits.     

Water diffusion in dacitic melt

H₂O diffusion in dacitic melt was investigated at 0.48-0.95 GPa and 786-893 K in a piston-cylinder apparatus. The diffusion couple design was used, in which a nominally dry dacitic glass makes one half and is juxtaposed with a hydrous dacitic glass containing up to ∼8 wt.% total water (H₂O_t). H₂O concentration profiles were measured on quenched glasses with infrared microspectroscopy. The H₂O diffusivity in dacite increases rapidly with water content under experimental conditions, similar to previous measurements at the same temperature but at pressure <0.15 GPa. However, compared with the low-pressure data, H₂O diffusion at high pressure is systematically slower. H₂O diffusion profiles in dacite can be modeled by assuming molecular H₂O (H₂O_m) is the diffusing species. Total H₂O diffusivity D_H2Ot within 786-1798 K, 0-1 GPa, and 0-8 wt.% H₂O_t can be expressed as: where D_H2Ot is in m²/s, T is temperature in K, P is pressure in GPa, K = exp(1.49 − 2634/T) is the equilibrium constant of speciation reaction (H₂O_m+O?2OH) in the melt, X = C/18.015/[C/18.015 + (100 − C)/33.82], C is wt.% of H₂O_t, and 18.015 and 33.82 g/mol correspond to the molar masses of H₂O and anhydrous dacite on a single oxygen basis. Compared to H₂O diffusion in rhyolite, diffusivity in dacite is lower at intermediate temperatures but higher at superliquidus temperatures. This general H₂O diffusivity expression can be applied to a broad range of geological conditions, including both magma chamber processes and volcanic eruption dynamics from conduit to the surface.     

Crystal chemistry of selenates with mineral-like structures: V. Crystal structures of (H3O)2[(UO2)(SeO4)2(H2O)](H2O)2 and (H3O)2[(UO2)(SeO4)2(H2O)](H2O), new compounds with rhomboclase and goldichite topology

The crystal structures of two new compounds (H₃O)₂[(UO₂)(SeO₄)₂(H₂O)](H₂O)₂ (1, orthorhombic, Pnma, a = 14.0328(18), b = 11.6412(13), c = 8.2146(13) Å, V = 134.9(3) ų) and (H₃O)₂[(UO₂)(SeO₄)₂(H₂O)](H₂O) (2, monoclinic, P2₁/c, a = 7.8670(12), b = 7.5357(7), c = 21.386(3) Å, β = 101.484(12)°, V = 1242.5(3) ų) have been solved by direct methods and refined to R ₁ = 0.076 and 0.080, respectively. The structures of both compounds contain sheet complexes [(UO₂)(SeO₄)₂]^2? formed by cornershared [(UO₂)O₄(H₂O)] bipyramids and SeO₄ tetrahedrons. The sheets are parallel to the (100) plane in structure 1 and to (?102) in structure 2. The [(UO₂)(SeO₄)₂(H₂O)]^2? layers are linked by hydrogen bonds via interlayer groups H₂O and H₃O⁺. The sheet topologies in structures 1 and 2 are different and correspond to the topologies of octahedral and tetrahedral complexes in rhomboclase (H₂O₂)⁺[Fe(SO₄)₂(H₂O)₂] and goldichite K[Fe(SO₄)₂(H₂O)₂](H₂O)₂, respectively.     

Water speciation and diffusion in haploandesitic melts at 743-873 K and 100 MPa

Water is an important volatile component in andesitic eruptions and deep-seated andesitic magma chambers. We report an investigation of H₂O speciation and diffusion by dehydrating haploandesitic melts containing ?2.5 wt.% water at 743-873 K and 100 MPa in cold-seal pressure vessels. FTIR microspectroscopy was utilized to measure species [molecular H₂O (H₂O_m) and hydroxyl group (OH)] and total H₂O (H₂O_t) concentration profiles on the quenched glasses from the dehydration experiments. The equilibrium constant of the H₂O speciation reaction H₂O_m+O?2OH, K = (X_OH)²/(X_H2OmX_O) where X means mole fraction on a single oxygen basis, in this Fe-free andesite varies with temperature as ln K = 1.547-2453/T where T is in K. Comparison with previous speciation data on rhyolitic and dacitic melts indicates that, for a given water concentration, Fe-free andesitic melt contains more hydroxyl groups. Water diffusivity at the experimental conditions increases rapidly with H₂O concentration, contrary to previous H₂O diffusion data in an andesitic melt at 1608-1848 K. The diffusion profiles are consistent with the model that molecular H₂O is the diffusion species. Based on the above speciation model, H₂O_m and H₂O_t diffusivity (in m²/s) in haploandesite at 743-873 K, 100 MPa, and H₂O_t ? 2.5 wt.% can be formulated as