The microdetermination of H2O,CO2, and SO2 in glass using a 1280°C microscope vacuum heating stage,cryopumping, and vapor pressure measurements from 77 to 273 K

A new microscope vacuum heating stage and gas analyzer has been developed for measurement of H₂O, CO₂, SO₂, and noncondensable gas (H₂, CO, N₂, Ar, CH₄, etc.) evolved from samples, particularly natural glass, at temperatures up to 1280°C. The gas evolved upon heating to 1280δC is collected in a liquid nitrogen cold trap. Gas components are identified by the characteristic vapor pressure and temperature ranges over which solid and vapor are in equilibrium during sublimation of individual components. The masses of CO₂, SO₂, and H₂O derived from samples and blanks are calculated using the ideal gas law, the molecular weights of the components, and the gauge constant (i.e. the ratio of the number of moles of a gas to its partial pressure in the constant volume). Results obtained by repeated determinations of H₂O, CO₂, and SO₂ evolved from a submarine basaltic glass from Kilauea volcano, Hawaii, (average sample mass = 3 × 10^?3 g) gave probable errors for the determinations of H₂O (0.23%), CO₂ (0.025%), and S (0.071%) equal to 4, 10, and 8% respectively, of the concentrations. Determinations of H₂O in smaller samples of H₂O-poor basaltic pumice show a linear proportionality (0.063%) between the measured H₂O and the sample mass over the range 0.1 × 10^?6 to 1.7 × 10^?6 g H₂O. Comparisons of H₂O determinations by this technique with those obtained by Penfield, gas chromatic, microcoulometric, and vacuum fusion techniques used elsewhere show reasonably good agreement. Determinations of SO₂ by this technique agree reasonably well X-ray fluorescence and electron microprobe determinations of sulfur. Determinations of CO₂ by the present technique are reproducible but cannot be compared directly to measurements made in other labs because of differences in samples analyzed. The principle advantages of this analytical technique are the very small sample required, the simultaneous determination of H₂O, CO₂, SO₂ and noncondensable gas, the avoidance of calibration procedures dependent on chemical standards, and the visual observations that can be made during sample outgassing.     

Melt inclusion constraints on volatile systematics and degassing history of the 2014–2015 Holuhraun eruption,Iceland

The mass of volatiles emitted during volcanic eruptions is often estimated by comparing the volatile contents of undegassed melt inclusions, trapped in crystals at an early stage of magmatic evolution, with that of the degassed matrix glass. Here we present detailed characterisation of magmatic volatiles (H₂O, CO₂, S, Fl and Cl) of crystal-hosted melt and fluid inclusions from the 2014–2015 Holuhraun eruption of the Bárðarbunga volcanic system, Iceland. Based on the ratios of magmatic volatiles to similarly incompatible trace elements, the undegassed primary volatile contents of the Holuhraun parental melt are estimated at 1500–1700 ppm CO₂, 0.13–0.16 wt% H₂O, 60–80 ppm Cl, 130–240 ppm F and 500–800 ppm S. High-density fluid inclusions indicate onset of crystallisation at pressures?≥?0.4 GPa (~?12 km depth) promoting deep degassing of CO₂. Prior to the onset of degassing, the melt CO₂ content may have reached 3000–4000 ppm, with the total magmatic CO₂ budget estimated at  23–55 Mt. SO₂ release commenced at 0.12 GPa (~?3.6 km depth), eventually leading to entrapment of SO₂ vapour in low-density fluid inclusions. We calculate the syn-eruptive volatile release as 22.2 Mt of magmatic H₂O, 5.9–7.7 Mt CO₂, and 11.3 Mt of SO₂ over the course of the eruption; F and Cl release were insignificant. Melt inclusion constraints on syn-eruptive volatile release are similar to estimates made during in situ field monitoring, with the exception of H₂O, where field measurements may be heavily biased by the incorporation of meteoric water.     

Why the atmosphere became oxygenated: A proposal

The increase in the oxidation state of the atmosphere during Earth history is well documented, but not the reasons for this process. The course of atmospheric evolution has been dominated by the effects of photosynthesis and by the composition of volcanic gases. The H₂/H₂O ratio of volcanic gases has remained essentially constant during most of Earth history. It is here proposed that their CO₂/H₂O and SO₂/H₂O ratios have increased with time. A simple model for the degassing and the recycling of CO₂, SO₂, and H₂O can account for many of the major steps in the oxygenation of the atmosphere.     

Thermochemical Sulfate Reduction in the Tazhong District,Tarim Basin,Northeast China: Evidence from Formation Water and Natural Gas Geochemistry

<正>Systematic analyses of the formation water and natural gas geochemistry in the Central Uplift of the Tarim Basin(CUTB) show that gas invasion at the late stage is accompanied by an increase of the contents of H_2S and CO_2 in natural gas,by the forming of the high total dissolved solids formation water,by an increase of the content of HCO_3~-,relative to Cl~-,by an increase of the 2nd family ions(Ca~(2+),Mg~(2+),Sr~(2+) and Ba~(2+)) and by a decrease of the content of SO_4~(2-),relative to Cl~-.The above phenomena can be explained only by way of thermochemical sulfate reduction(TSR).TSR often occurs in the transition zone of oil and water and is often described in the following reaction formula:ΣCH+CaSO_4+H-_2O→H_2S+CO_2+CaCO_3.(1) Dissolved SO_4~(2-) in the formation water is consumed in the above reaction,when H_2S and CO_2 are generated,resulting in a decrease of SO_4~(2-) in the formation water and an increase of both H_2S and CO_2 in the natural gas.If formation water exists, the generated CO_2 will go on reacting with the carbonate to form bicarbonate,which can be dissolved in the formation water,thus resulting in the enrichment of Ca~(2+) and HCO_3~-.The above reaction can be described by the following equation:CO_2+H_2O+CaCO_3→Ca~(2+)+2HCO_3~-.The stratigraphic temperatures of the Cambrian and lower Ordovician in CUTB exceeded 120℃,which is the minimum for TSR to occur.At the same time,dolomitization,which might be a direct result of TSR,has been found in both the Cambrian and the lower Ordovician.The above evidence indicates that TSR is in an active reaction,providing a novel way to reevaluate the exploration potentials of natural gas in this district.     

Measurements of carbon dioxide and heat fluxes during monsoon-2011 season over rural site of India by eddy covariance technique

An increase in carbon dioxide (CO₂) concentrations in the atmosphere due to anthropogenic activities is responsible for global warming and hence in recent years, CO₂ measurement network has expanded globally. In the monsoon season (July–September) of year 2011, we carried out measurements of CO₂ and water vapour (H₂O) concentrations along with wind and air temperature over a tropical site in south-east India having rural topography. To collect these observations, the instrumentations used were the sonic anemometer for wind and temperature, and the open path H₂O/CO₂ infrared gas analyzer for CO₂ and H₂O concentrations. Using these observations, we explored the diurnal variability of CO₂ flux along with sensible and latent heat. The CO₂ flux was positive during night-time and negative during daytime and in phase with convective instability. The CO₂ flux relationships with the meteorological parameters such as wind speed, temperature and heat fluxes have been analysed. The seasonal (monsoon) half hour mean of CO₂ flux which was ?3.55 μmol m^???2 s^???1 indicated the experimental site as a CO₂ sink region (net seasonal uptake). An increase in CO₂ concentrations during weekends was not observed due to unavailability of heavy vehicular traffic.     

Ore Genesis of the Kalatongke Cu–Ni Sulfide Deposits, Western China: Constraints from Volatile Chemical and Carbon Isotopic Compositions

The Kalatongke Cu–Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt (CAOB). The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200–400°C, 400–900°C and 900–1200°C. The released volatiles from silicate mineral separates at 400–900°C and 900–1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O (av. ~92 mol%) with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values (from ?20.86‰ to ?12.85‰) of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantle-derived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200–400°C are dominated by H2O with minor CO2, N2+CO and SO2, with δ13CCO2 values (?25.66‰ to ?22.98‰) within the crustal ranges, and are considered to be related to secondary tectonic– hydrothermal activities.     

Deep pre-eruptive storage of silicic magmas feeding Plinian and dome-forming eruptions of central and northern Dominica (Lesser Antilles) inferred from volatile contents of melt inclusions

Volatiles contribute to magma ascent through the sub-volcanic plumbing system. Here, we investigate melt inclusion compositions in terms of major and trace elements, as well as volatiles (H₂O, CO₂, SO₂, F, Cl, Br, S) for Quaternary Plinian and dome-forming dacite and andesite eruptions in the central and the northern part of Dominica (Lesser Antilles arc). Melt inclusions, hosted in orthopyroxene, clinopyroxene and plagioclase are consistently rhyolitic. Post-entrapment crystallisation effects are limited, and negligible in orthopyroxene-hosted inclusions. Melt inclusions are among the most water-rich yet recorded (≤?8 wt% H₂O). CO₂ contents are generally low (<?650 ppm), although in general the highest pressure melt inclusion contain the highest CO₂. Some low-pressure (<?3 kbars) inclusions have elevated CO₂ (up to 1100–1150 ppm), suggestive of fluxing of shallow magmas with CO₂-rich fluids. CO₂-trace element systematics indicate that melts were volatile-saturated at the time of entrapment and can be used for volatile-saturation barometry. The calculated pressure range (0.8–7.5 kbars) indicates that magmas originate from a vertically-extensive (3–27 km depth) storage zone within the crust that may extend to the sub-Dominica Moho (28 km). The vertically-extensive crustal system is consistent with mush models for sub-volcanic arc crust wherein mantle-derived mafic magmas undergo differentiation over a range of crustal depths. The other volatile range of composition for melt inclusions from the central part is F (75–557 ppm), Cl (1525–3137 ppm), Br (6.1–15.4 ppm) and SO₂ (<?140 ppm), and for the northern part it’s F (92–798 ppm), Cl (1506–4428 ppm), Br (not determined) and SO₂ (<?569; one value at 1015 ppm). All MIs, regardless of provenance, describe the same Cl/F correlation (8.3?±?2.7), indicating that the magma source at depth is similar. The high H₂O content of Dominica magmas has implications for hazard assessment.     

Sulfides,oxides and sphene in high-pressure schists from New Caledonia

In the New Caledonia high-pressure schists pyrite, pyrrhotite, chalcopyrite, rutile and sphene are common phases while hematite and ilmenite are rare and magnetite is absent. The parageneses of these minerals were clarified from their occurrence as inclusions in garnet, from phase relations in the Cu-Fe-S and Fe-Ti-O-S systems, and from phase rule considerations for the multi-component system. The sulfur fugacity estimated for pelites and basites containing pyrrhotite, pyrite and rutile increased with increasing metamorphic grade; the oxygen fugacity in these schists was less than 10^–27.6 bars at 400° C, 10 kb and 10^–22.3 bars at 500° C, 11 kb. Among the other components of the metamorphic fluid in pelites, H₂O was major, CH₄, CO₂ and H₂S minor, and H₂, CO, COS and SO₂ rare. The fluid composition altered with advancing metamorphic grade, such that H₂O decreased while CO₂, CH₄ and H₂S increased, and this change was linked to concurrent massive decarbonization in the rock matrices.     

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.     

Ammonia emission from CO<Subscript>2</Subscript> capture pilot plant using aminoethylethanolamine

Amine post-combustion carbon capture technology is based on washing the flue gas with a solvent that captures CO₂. Thus, a small fraction of this solvent can be released together with the cleaned flue gas. This release may cause environmental concerns, both directly and indirectly through subsequent solvent degradation into other substances in the atmosphere. The paper presents the ammonia emission from CO₂ capture pilot plant (1 tonne CO₂ per day) using 40 wt% aminoethylethanolamine solvent, along with the efficiency of the water wash unit. In addition, the temperature effect of lean amine entering the absorber on ammonia emission was studied. Furthermore, the concentrations of other compounds such as SO₂, SO₃, NO₂, CS₂ and formaldehyde were monitored. The literature review on the NH₃ emission from a pilot plant using aminoethylethanolamine solvent has not been published. The results show that the main source of ammonia emission is the absorber and that emission (in the range 27–50 ppm) corresponds to typical NH₃ release from CO₂ capture pilot plant using an amine solvent. The emission of amines and amine degradation products is a complex phenomenon which is difficult to predict in novel solvents, and for this reason the significance of new solvents testing in a pilot scale has been highlighted.     

Chemistry and sulfur isotopic composition of precipitation at Bologna, Italy

Individual and monthly precipitation samples from the polluted atmosphere of Bologna (Emilia-Romagna province) were collected during March 1996 to May 1997 and analyzed for major ions in solution and S isotopes in dissolved SO₄.Weighted mean enrichment factors relative to seawater are found to be 1.0 for Na, 15.2 for K, 105 for Ca, 3.3 for Mg, 17.3 for SO₄ and 663 for HCO⁻₃. Very good positive correlations are observed for the Ca²⁺–Mg²⁺–HCO⁻₃–SO²⁻₄–NO⁻₃ system, indicating that dissolution of Ca (±Mg)-carbonate particles by H₂SO₄ and HNO₃ from combustion of oil and gas is a major process controlling the chemical composition of rain and snow. Na⁺ and Cl⁻ in monthly precipitation derive essentially from sea spray, but the contribution of Na⁺ from continental sources is appreciable in a number of individual rains. NH⁺₄ appears to be on average more abundant in spring and summer precipitation, its main sources being microbial activity in soils and application of fertilizers. K⁺ is probably of continental origin from soil dust.The S isotopic composition of SO₄ is systematically positive, with mean δ³⁴S values of +3.2±1.6‰ (n=40) in individual precipitation and +2.8±1.4‰ (n=12) in monthly precipitation. These isotopic compositions are interpreted in terms of a dominant contribution of S from anthropogenic emissions and subordinate contributions from biogenic and marine sources. Pollutant SO₄ is estimated to have a δ³⁴S value in the range +2.5 to +4.5‰, whereas a distinctive δ³⁴S of −4.5‰ or lower indicates SO₄ from oxidation of biogenic gases.The isotopic and chemical compositions of SO₄ do not depend on wind direction, thus testifying to a mostly local source for pollutant S in the Bologna atmosphere.     

Gas genetic type and origin of hydrogen sulfide in the Zhongba gas field of the western Sichuan Basin, China

Natural gases and associated condensate oils from the Zhongba gas field in the western Sichuan Basin, China were investigated for gas genetic types and origin of H₂S by integrating gaseous and light hydrocarbon geochemistry, formation water compositions, S isotopes (δ³⁴S) and geological data. There are two types of natural gas accumulations in the studied area. Gases from the third member of the Middle Triassic Leikoupo Formation (T₂l³) are reservoired in a marine carbonate sequence and are characterized by high gas dryness, high H₂S and CO₂ contents, slightly heavy C isotopic values of CH₄ and widely variable C isotopic values of wet gases. They are highly mature thermogenic gases mainly derived from the Permian type II kerogens mixed with a small proportion of the Triassic coal-type gases. Gases from the second member of the Upper Triassic Xujiahe Formation (T₃x²) are reservoired in continental sandstones and characterized by low gas dryness, free of H₂S, slightly light C isotopic values of CH₄, and heavy and less variable C isotopic values of wet gases. They are coal-type gases derived from coal in the Triassic Xujiahe Formation.The H₂S from the Leikoupo Formation is most likely formed by thermochemical SO₄ reduction (TSR) even though other possibilities cannot be fully ruled out. The proposed TSR origin of H₂S is supported by geochemical compositions and geological interpretations. The reservoir in the Leikoupo Formation is dolomite dominated carbonate that contains gypsum and anhydrite. Petroleum compounds dissolved in water react with aqueous SO₄ species, which are derived from the dissolution of anhydrite. Burial history analysis reveals that from the temperature at which TSR occurred it was in the Late Jurassic to Early Cretaceous and TSR ceased due to uplift and cooling thereafter. TSR alteration is incomplete and mainly occurs in wet gas components as indicated by near constant CH₄ δ¹³C values, wide range variations of ethane, propane and butane δ¹³C values, and moderately high gas dryness. The δ³⁴S values in SO₄, elemental S and H₂S fall within the fractionation scope of TSR-derived H₂S. High organo-S compound concentrations together with the occurrence of 2-thiaadamantanes in the T₂l reservoir provide supplementary evidence for TSR related alteration.     

Production of CO2 and H2 by Diking-Eruptive Events at Mid-Ocean Ridges: Implications for Abiotic Organic Synthesis and Global Geochemical Cycling

We have calculated the amounts of CO₂ and H₂ produced by complete degassing of mid-ocean ridge basalt (MORB) magma, and by degassing during transient diking-eruptive events. Our CO₂ calculations are based on a model estimate of an initial CO₂ content of 1800 ppm in MORB magma, which is equivalent to 2.2 × 10¹² mol CO₂ per year for magma production at worldwide ocean ridges. Observations indicate that many MORB magmas are emplaced in numerous small pulses of dikes and associated lava flows with very short emplacement times, which would result in release of relatively large amounts of CO₂ over short intervals. For example, a dike injected into the oceanic crust that extends from the top of its magma chamber at 2 km depth to the seafloor would degas 2.3 × 10⁴ mol CO₂ per m² surface area of dike, and produce another 4.0 × 10⁴ mol CO₂ per m² on complete crystallization.

Unlike CO₂, which is not strictly governed by crystallization-alteration processes, H₂ is produced from MORB by the reduction of H₂O by ferrous iron in the magma to form magnetite and H₂ as the magma cools and crystallizes. From published paired analyses of MORB glass and crystalline rock, we estimate that the amount of H₂ produced from one cubic meter of rock averages 301 mol. We suggest that the oxidizing agent is H₂O dissolved in the magma, which results in rapid generation of H₂. The amount of pre-alteration oxidation may be limited by the amount of H₂O dissolved in the magma; thus relatively water-rich magmas will undergo greater oxidation. For the case of the two-kilometer-high dike reaching the seafloor, the amount of H₂ released is 6.2 × 10⁵ moles H₂ per m² surface area of the dike. This is 10 times greater than the total CO₂ released by degassing and crystallization of the dike. Assuming that the H₂ generation rate for the entire basaltic layer of the oceanic crust is the same as for MORB lavas (312 mol/m³), then the annual global H₂ production rate is 6.3 × 10¹² mol H₂ per year. This amount is about three times greater than our calculated annual CO₂ production from MORBs. Given that the annual CO₂ production rate from MORBs over 3.3 Ga can account for all CO₂ found in the Earth's crust, hydrosphere, and atmosphere, it is likely that the H₂ produced at mid-ocean ridges plays a significant role as a reducing agent in the global redox state of the Earth's surface.

In contrast to time-averaged global production rates, the rapid release of CO₂ and H₂ in diking-eruptive events may locally result in formation of a separate gas phase containing H₂-CO₂-H₂O in that order of abundance. The amounts of CO₂ and H₂ produced could provide a significant energy source for autotrophic microorganisms. It has been demonstrated that such a CO₂-H₂-H₂O gas mixture yields methanol in magnetite-surface catalyzed reactions at seafloor hydrothermal conditions. Such abiotic synthesis reactions could have been important in early Earth processes.     

Hydrochemical indications of human impact on karst groundwater in a subtropical karst area,Chongqing, China

The application of combined isotopic and hydrochemical compositions may be useful for evaluating water quality problems in karst aquifers in which it is difficult to distinguish the sources of solutes from the natural background of those due to human activities. Multiple isotopes (δ¹³C–DIC, δ³⁴S–SO₄ ^2?) and chemical parameters were measured in rainwater, groundwater and sewage in order to elucidate the solute sources and impacts from human activities and natural background in the Laolongdong karst catchment in Chongqing Municipality, SW China. Overall, the dissolution of carbonate rock controls Ca²⁺, Mg²⁺ and HCO₃ ^? content in rainwater and karst groundwater. SO₄ ^2? originated mainly from gypsum dissolution in karst groundwater. Carbonate rocks in the studied site could be dissolved jointly by H₂CO₃ from the natural CO₂–H₂O reaction and other acids (organic acids and HNO₃) from sewage and soils. Sewage discharge from urban areas and agriculture activities lead to the increase of NO₃ ^?, PO₄ ^3? and Cl^? in karst groundwater. To protect and sustainably utilize the karst aquifer, sewage originating from urban areas must be controlled and treated and the use of fertilizer should be limited.     

Phase Chemistry Study of the Zabuye Salt Lake Brine: Isothermal Evaporation at 15°C and 25°C

Zabuye Salt Lake in Tibet, China is a carbonate-type salt lake, which has some unique characteristics that make it different from other types of salt lakes. The lake is at the latter period in its evolution and contains liquid and solid resources. Its brine is rich in Li, B, K and other useful minor elements that are of great economic value. We studied the concentration behavior of these elements and the crystallization paths of salts during isothermal evaporation of brine at 15°C and 25°C. The crystallization sequence of the primary salts from the brine at 25°C is halite (NaCl) → aphthitalite (3K2SO4·Na2SO4) → zabuyelite (Li2CO3)→ trona (Na2CO3·NaHCO3·2H2O) → thermonatrite (Na2CO3·H2O) → sylvite (KCl), while the sequence is halite (NaCl) → sylvite (KCl) → trona (Na2CO3·NaHCO3·2H2O) → zabuyelite (Li2CO3) → thermonatrite (Na2CO3·H2O) → aphthitalite (3K2SO4·Na2SO4) at 15°C. They are in accordance with the metastable phase diagram of the Na+, K+-Cl?, CO32?, SO42?-H2O quinary system at 25°C, except for Na2CO3·7H2O which is replaced by trona and thermonatrite. In the 25°C experiment, zabuyelite (Li2CO3) was precipitated in the early stage because Li2CO3 is supersaturated in the brine at 25°C, in contrast with that at 15°C, it precipitated in the later stage. Potash was precipitated in the middle and late stages in both experiments, while boron was concentrated in the early and middle stages and precipitated in the late stage.     

H2S fluxes from Mt. Etna, Stromboli, and Vulcano (Italy) and implications for the sulfur budget at volcanoes

We present here new measurements of sulfur dioxide and hydrogen sulfide emissions from Vulcano, Etna, and Stromboli (Italy), made by direct sampling at vents and by filter pack and ultraviolet spectroscopy in downwind plumes. Measurements at the F0 and FA fumaroles on Vulcano yielded SO₂/H₂S molar ratios of ≈0.38 and ≈1.4, respectively, from which we estimate an H₂S flux of 6 to 9 t · d⁻¹ for the summit crater. For Mt. Etna and Stromboli, we found SO₂/H₂S molar ratios of ≈20 and ≈15, respectively, which combined with SO₂ flux measurements, suggest H₂S emission rates of 50 to 113 t · d⁻¹ and 4 to 8 t · d⁻¹, respectively. We observe that “source” and plume SO₂/H₂S ratios at Vulcano are similar, suggesting that hydrogen sulfide is essentially inert on timescales of seconds to minutes. This finding has important implications for estimates of volcanic total sulfur budget at volcanoes since most existing measurements do not account for H₂S emission.     

Aquifer disposal of acid gases: modelling of water–rock reactions for trapping of acid wastes

The pore space of deep saline aquifers in the Alberta (sedimentary) Basin offers a significant volume for waste storage by “hydrodynamic trapping”. Furthermore, given the slow regional fluid flow in these deep saline aquifers, ample time exists for waste-water/rock chemical reactions to take place. A geochemical computer model (PATHARC) was used to compute the interaction of industrial waste streams comprising CO₂, H₂SO₄ and H₂S with the minerals in typical carbonate and sandstone aquifers from the Alberta Basin. The results support the idea that these acids can be neutralized by such reactions and that new mineral products are formed, such as calcite, siderite, anhydrite/gypsum and pyrrhotite, thereby trapping the CO₃, SO₄ and S ions that are formed when the acid gases dissolve in the formation water. Siliciclastic aquifers appear to be a better host for “mineral trapping” than carbonate aquifers, especially with regard to CO₂. Carbonate aquifers may be more prone to leakage due to high CO₂ pressures generated by reaction with H₂SO₄ and H₂S. Even though permeability decreases are expected due to this “mineral trapping”, they can be partially controlled so that plugging of the aquifer does not occur.     

Sources, degassing, and contamination of CO2, H2O, He, Ne, and Ar in basaltic glasses from Kolbeinsey Ridge, North Atlantic

New volatile data (CO₂, H₂O, He, Ne, and Ar) are presented for 24 submarine basaltic glasses from the Kolbeinsey Ridge, Tjörnes Fracture Zone and Mohns Ridge, North Atlantic. Low CO₂ and He contents indicate that magmas were strongly outgassed with the extent of degassing increasing toward the south, as expected from shallower ridge depths. Ne and Ar are significantly more abundant in the southernmost glasses than predicted for degassed melt. The strong atmospheric isotopic signal associated with this excess Ne and Ar suggests syn- or posteruptive contamination by air. Degassing, by itself, cannot generate the large variations in δ¹³C values of dissolved CO₂ or coupled CO₂-Ar variations. This suggests that δ¹³C values were also affected by some other processes, most probably melt-crust interaction. Modelling indicates that degassing had a negligible influence on water owing to its higher solubility in basaltic melt than the other volatiles. Low H₂O contents in the glasses reflect melting of a mantle source that is not water-rich relative to the source of N-MORB.Before eruption, Kolbeinsey Ridge melts contained ∼400 ppm CO₂ with δ¹³C of −6‰, 0.1 to 0.35 wt.% H₂O, ³He/⁴He ∼11 R_A, and CO₂/³He of ∼2 × 10⁹. We model restored volatile characteristics and find homogeneous compositions in the source of Kolbeinsey Ridge magmas. Relative to the MORB-source, He and Ne are mildly fractionated while the ⁴⁰Ar/³⁶Ar may be low. The ³He/⁴He ratios in Tjörnes Fracture Zone glasses are slightly higher (13.6 R_A) than on Kolbeinsey Ridge, suggesting a greater contribution of Icelandic mantle from the south, but the lack of ³He/⁴He variation along the Kolbeinsey Ridge is inconsistent with active dispersal of Icelandic mantle beyond the Tjörnes Fracture Zone.     

Fluid inclusion and isotope geochemistry of the Yangla copper deposit,Yunnan, China

The Yangla copper deposit, with Cu reserves of 1.2 Mt, is located between a series of thrust faults in the Jinshajiang–Lancangjiang–Nujiang region, Yunnan, China, and has been mined since 2007. Fluid inclusion trapping conditions ranged from 1.32 to 2.10 kbar at 373–409 °C. Laser Raman spectroscopy confirms that the vapour phase in these inclusions consists of CO₂, CH₄, N₂ and H₂O. The gas phases in the inclusions are H₂O and CO₂, with minor amounts of N₂, O₂, CO, CH₄, C₂H₂, C₂H₄, and C₂H₆. Within the liquid phase, the main cations are Ca²⁺ and Na⁺ while the main anions are SO₄ ^2? and Cl^?. The oxygen and hydrogen isotope compositions of the ore-forming fluids (?3.05‰?≤?δ¹⁸O_H2O?≤?2.5‰; ?100‰?≤?δD?≤??120‰) indicate that they were derived from magma and evolved by mixing with local meteoric water. The δ³⁴S values of sulfides range from ?4.20‰ to 1.85‰(average on ?0.85‰), supporting a magmatic origin. Five molybdenite samples taken from the copper deposit yield a well-constrained ¹⁸⁷Re–¹⁸⁷Os isochron age of 232.8?±?2.4 Ma. Given that the Yangla granodiorite formed between 235.6?±?1.2 Ma and 234.1?±?1.2 Ma, the Cu metallogenesis is slightly younger than the crystallization age of the parent magma. A tectonic model that combines hydrothermal fluid flow and isotope compositions is proposed to explain the formation of the Yangla copper deposit. At first, westward subduction of the Jinshajiang Oceanic Plate in the Early Permian resulted in the development of a series of thrust faults. This was accompanied by fractional melting beneath the overriding plate, triggering magma ascent and extensive volcanism. The thrust faults, which were then placed under tension during a change in tectonic mode from compression to extension in the Late Triassic, formed favorable pathways for the magmatic ore-forming fluids. These fluids precipitated copper-sulfides to form the Yangla deposit.     

A Chemical Equilibrium Model for Natural Waters

This paper reviews the present status of the Pitzer chemical equilibrium model, which can be used to characterize the one-atmosphere activity coefficients of ionic and non-ionic solutes in natural waters as a function of temperature and ionic strength. The model considers the ionic interactions of the major seasalt ions (H, Na, K, Mg, Ca, Sr, Cl, Br, OH, HCO₃, B(OH)₄, HSO₄, SO₄, CO₃, CO₂, B(OH)₃, H₂O) and is based on the 25 °C model of Weare and co-workers. The model has been extended by a number of workers so that reasonable estimates can be made of the activity coefficients of most of the major seasalt ions from 0 to 250 °C. Recently coefficients for a number of solutes that are needed to determine the dissociation constants of the acids from 0 to 50 °C (H₃CO₃, B(OH)₃, H₂O, HF, HSO ₄ ^- , H₃PO₄, H₂S, NH ₄ ⁺ etc.) have been added to the model. These results have been used to examine the carbonate system in natural waters and determine the activity of inorganic anions that can complex trace metals. The activity and osmotic coefficients determined from the model are shown to be in good agreement with measured values in seawater. This model can serve as the foundation for future expansions that can examine the activity coefficient and speciation of trace metals in natural waters. At present this is only possible from 0 to 50 °C over a limited range of ionic strengths (<1.0) due to the limited stability constants for the formation of the metal complexes. The future work needed to extend the Pitzer model to trace metals is discussed.