Multiple sulfur and oxygen isotope compositions in Beijing aerosol

Multiple sulfur isotopes(32S, 33 S, 34 S, 36S) and oxygen isotopes(16O, 18O) in Beijing aerosols were measured with MAT-253 isotope mass spectrometer. The δ34S values of Beijing aerosol samples range from 1.68‰ to 12.57‰ with an average value of 5.86‰, indicating that the major sulfur source is from direct emission during coal combustion. The δ18O values vary from 5.29‰ to 9.02‰ with an average value of 5.17‰, revealing that the sulfate in Beijing aerosols is mainly composed of the secondary sulfate. The main heterogeneous oxidation of SO2 in atmosphere is related to H2O2 in July and August, whereas H2O2 oxidation and Fe3+ catalytic oxidation with SO2 exist simultaneously in September and October. Remarkable sulfur isotope mass-independent fractionation effect is found in Beijing aerosols, which is commonly attributed to the photochemical oxidation of SO2 in the stratosphere. In addition, thermochemical reactions of sulfur-bearing compounds might be also a source of sulfur isotope anomalies based on the correlation between ?33S and CAPE.     

Fumarole/plume and diffuse CO2 emission from Sierra Negra caldera, Galapagos archipelago

Measurements of visible and diffuse gas emission were conducted in 2006 at the summit of Sierra Negra volcano, Galapagos, with the aim to better characterize degassing after the 2005 eruption. A total SO₂ emission of 11?±?2?t day^?1 was derived from miniature differential optical absorption spectrometer (mini-DOAS) ground-based measurements of the plume emanating from the Mini Azufral fumarolic area, the most important site of visible degassing at Sierra Negra volcano. Using a portable multigas system, the H₂S/SO₂, CO₂/SO₂, and H₂O/SO₂ molar ratios in the Mina Azufral plume emissions were found to be 0.41, 52.2, and 867.9, respectively. The corresponding H₂O, CO₂, and H₂S emission rates were 562, 394, and 3?t day^?1, respectively. The total output of diffuse CO₂ emissions from the summit of Sierra Negra volcano was 990?±?85?t day^?1, with 605?t day^?1 being released by a deep source. The diffuse-to-plume CO₂ emission ratio was about 1.5. Mina Azufral fumaroles released gasses containing 73.6?mol% of H₂O; the main noncondensable components amounted to 97.4?mol% CO₂, 1.5?mol% SO₂, 0.6?mol% H₂S, and 0.35?mol%?N₂. The higher H₂S/SO₂ ratio values found in 2006 as compared to those reported before the 2005 eruption reveal a significant hydrothermal contribution to the fumarolic emissions. ³He/⁴He ratios measured at Mina Azufral fumarolic discharges showed values of 17.88?±?0.25?R _A , indicating a mid-ocean ridge basalts (MORB) and a Galapagos plume contribution of 53 and 47?%, respectively.     

Sulfur isotopic effects in the disproportionation reaction of sulfur dioxide in hydrothermal fluids: implications for the δS variations of dissolved bisulfate and elemental sulfur from active crater lakes

Sulfur isotope effects during the SO₂ disproportionation reaction to form elemental sulfur (3SO₂+3H₂O→2HSO₄⁻+S+2H⁺) at 200–330°C and saturated water vapor pressures were experimentally determined. Initially, a large kinetic isotopic fractionation takes place between HSO₄⁻ and S, followed by a slow approach to equilibrium. The equilibrium fractionation factors, estimated from the longest run results, are expressed by 1000 ln α_HSO4⁻–S=6.21×10⁶/T²+3.62. The rates at which the initial kinetic fractionation factors approach the equilibrium ones were evaluated at the experimental conditions.δ³⁴S values of HSO₄⁻ and elemental sulfur were examined for active crater lakes including Noboribetsu and Niseko, (Hokkaido, Japan), Khloridnoe, Bannoe and Maly Semiachik (Kamchatka), Poás (Costa Rica), Ruapehu (New Zealand) and Kawah Ijen and Keli Mutu (Indonesia). Δ_HSO4⁻–S values are 28‰ for Keli Mutu, 26‰ for Kawah Ijen, 24‰ for Ruapehu, 23‰ for Poás, 22‰ for Maly Semiachik, 21‰ for Yugama, 13‰ for Bannoe, 9‰ for Niseko, 4‰ for Khloridonoe, and 0‰ for Noboribetsu, in the decreasing order. The SO₂ disproportionation reaction in the magmatic hydrothermal system below crater lakes where magmatic gases condense is responsible for high Δ_HSO4⁻–S values, whereas contribution of HSO₄⁻ produced through bacterial oxidation of reduced sulfur becomes progressively dominant for lakes with lower Δ_HSO4⁻–S values. Currently, Noboribetsu crater lake contains no HSO₄⁻ of magmatic origin. A 40-year period observation of δ³⁴S_HSO4⁻ and δ³⁴S_S values at Yugama indicated that the isotopic variations reflect changes in the supply rate of SO₂ to the magmatic hydrothermal system. This implies a possibility of volcano monitoring by continuous observation of δ³⁴S_HSO4⁻ values. The δ¹⁸O values of HSO₄⁻ and lake water from the studied lakes covary, indicating oxygen isotopic equilibration between them. The covariance gives strong evidence that lake water circulates through the sublimnic zone at temperatures of 140±30°C.     

Etude de la phase gazeuse occluse dans les laves de «l’Ardoukôba», volcan éphémère d’une dorsale émergée (Afar)

Gases trapped in lavas of three main flows of the Ardoukôba eruption (8 to 15 November, 1978) have been analysed by mass spectrometry. These analyses concern both plagioclase phenocrysts and microcrystalline mesostasis. Fluids are released between 500°C and 1200°C, and consist of H₂O, CO₂, CO, N₂, SO₂, HCl, H₂, CH₄ with traces of hydrocarbons and H₂S. The total content is less than 0.3–0.4 wt. % of samples with about 0.1–0.15 wt % of H₂O. No significant variation among the three flows is observed. Plagioclase phenocrysts are less abundant in fluids than the mesostasis (～2/3). The gases trapped in these phenocrysts are richer in CO and organic compounds, whereas mesostasis contain more H₂O, CO₂ and SO₂. CO is likely produced by reduction of CO₂ and H₂O with carbon during either analyses or eruption itself, or is of primary origin. In the latter case, gas composition suggests an entrapment temperature of about 1200°C ± 75°C. Kinetic study of the water and carbon dioxide release allows to calculate the diffusion characteristics of these fluids. Water and carbon dioxide behave rather similarly. Plagioclase gives a single activation energy value (8 Kcal/mole), while mesostasis gives two values (8 Kcal/mole, 15 Kcal/mole). Diffusion coefficients at 20°C are estimated to fall in the range 10^?13 · 10^?12 cm² · sec^?1.     

Photochemistry of Ions at D-region Altitudes of the Ionosphere: A Review

The current state of knowledge of the D-region ion photochemistry is reviewed. Equations determining production rates of electrons and positive ions by photoionization of atmospheric neutral species are presented and briefly discussed. Considerable attention is given to the progress in the chemistry of O⁺(⁴S), O⁺(²D), O⁺(²P), N⁺, N₂ ⁺, O₂ ⁺, NO⁺, N₄ ⁺, O₄ ⁺, NO⁺(N₂), NO⁺(CO₂), NO⁺(CO₂)₂, NO⁺(H₂O) _n for n = 1–3, NO⁺(H₂O)(N₂), NO⁺(H₂O)₂(N₂), NO⁺(H₂O)(CO₂), NO⁺(H₂O)₂(CO₂), O₂ ⁺(H₂O), H₃O⁺(OH), H⁺(H₂O) _n for n = 1–8, O^?, O₂ ^?, O₃ ^?, O₄ ^?, OH^?, CO₃ ^?, CO₄ ^?, NO₂ ^?, NO₃ ^?, ONOO^?, Cl^?, Cl^?(H₂O), Cl^?(CO₂), HCO₃ ^?, CO₃ ^?(H₂O), CO₃ ^?(H₂O)₂, NO₃ ^?(H₂O), NO₃ ^?(H₂O)₂, OH^?(H₂O), and OH^?(H₂O)₂ ions. The analysis of the D-region rocket ion mass spectrometer measurements shows that, among these ions, O₂ ⁺, NO⁺, NO⁺(H₂O), and H⁺(H₂O) _n for n = 1–7 can make the main contribution to the total positive ion number density, and O^?, O₂ ^?, Cl^?, OH^?(H₂O), CO₃ ^?, HCO₃ ^?, NO₃ ^?, ONOO^?, CO₄ ^?, NO₃ ^?(H₂O), NO₃ ^?(H₂O)₂, and ³⁵Cl^?(CO₂) ions can be responsible for the main contribution to the total negative ion number density. Photodetachment of electrons from O^?, Cl^?, O₂ ^?, O₃ ^?, OH^?, NO₂ ^?, and NO₃ ^?, dissociative electron photodetachment of O₄ ^? and OH^?(H₂O), and photodissociation of O₃ ^?, O₄ ^?, CO₃ ^?, CO₄ ^?, ONOO^?, HCO₃ ^?, CO₃ ^?(H₂O), NO₃ ^?(H₂O), O₂ ⁺(H₂O), O₄ ⁺, N₄ ⁺, NO⁺(H₂O), NO⁺(H₂O)₂, H⁺(H₂O) _n for n = 2–4, NO⁺(N₂), and NO⁺(CO₂) are studied, and the photodetachment and photodissociation rate coefficients are calculated using the current state of knowledge on the cross sections of these processes and fluxes of solar radiation.     

Stable and radiogenic isotopes as tracers for the origin,mixing and subsurface history of fluids in submarine shallow-water hydrothermal systems

The shallow-water hydrothermal system in Tutum Bay on the west side of Ambitle Island, Papua New Guinea provides us with an exceptional opportunity to study isotope systematics in a near shore setting. Compared to seawater, the hydrothermal fluids in Tutum Bay have lower values for δD, δ¹⁸O, δ¹³C, and ⁸⁷Sr and higher values for ³H, δ³⁴S(SO₄) and δ¹⁸O(SO₄). The δ¹⁸O and δD records for vents 1 and 4 indicate that fluid compositions remained stable over an extended period. Interpretation of isotope data clearly demonstrates the predominantly meteoric origin of Tutum Bay hydrothermal fluids, despite their location in a marine environment. δ¹⁸O and δD values are identical to mean average annual precipitation in eastern Papua New Guinea. The hypothesis that these fluids are a simple product of mixing between seawater and onshore hydrothermal fluids from the Waramung (W-1) and Kapkai (W-2) thermal areas has been rejected, because the observed δ³⁷Cl, ³H, δ³⁴S(SO₄) and δ¹⁸O(SO₄) values cannot be explained by a simple mixing model. The application of δ¹⁸O(SO₄) and δ¹³C thermometers in combination with ³H values corroborates the three-step model of Pichler et al. [Pichler, T., Veizer, J., Hall, G.E.M., 1999. The chemical composition of shallow-water hydrothermal fluids in Tutum Bay, Ambitle Island, Papua New Guinea and their effect on ambient seawater. Marine Chemistry 64 (3) 229–252], where (1) phase separation in the deep reservoir beneath Ambitle Island produces a high temperature vapor that rises upward and subsequently reacts with cooler ground water to form a low pH, CO₂-rich water of approximately 150–160 °C, (2) caused by the steep topography, this CO₂-rich fluid moves laterally towards the margin of the hydrothermal system where it mixes with the marginal upflow of the deep reservoir fluid. This produces a dilute chloride water of approximately 165 °C, and (3) possibly the entrainment of minor amounts of ground or seawater during its final ascent.     

Hydrogarnet substitution in pyrope: a possible location for “water” in the mantle

Single-crystal spectra of pyropes, synthesized on the 3:1:3 composition of the system MgO-Al₂O₃-SiO₂ atp_H2O = p_total = 25kbar and 1000°C, show a broad band centered at around 3400 cm^?1 due toν_H2O of (H₂O)_n aggregates in fluid inclusions and a sharp intense band near 3600 cm^?1 due toν_OH of (HO)₄^4? clusters introduced by the hydrogarnet substitutionSi⁴⁺ = 4H⁺. The water contents in the synthetic pyrope, due to (HO)₄^4? clusters are estimated near 0.05 wt.% H₂O from spectroscopic data. Si deficits in microprobe analyses of the pyropes studied support the hydrogarnet substitution. These results show that the hydrogarnet substitution in pyrope may contribute to water contents in the mantle.     

Oxygen isotope fractionation factors between anhydrite and water from 100 to 550°C

Oxygen isotope exchange between anhydrite and water was studied from 100 to 550°C, using the partial equilibrium method. The exchange rate was extremely low in NaCl solution. In the lower-temperature range, acid solutions were used to produce sufficient reaction to determine the oxygen isotope fractionation factors. The fractionation factors obtained in the present study are definitely different from those given by Lloyd [8]. They are similar to those for the HSO₄^?-water system studied by Mizutani and Rafter [19], and are consistently 2‰ higher than those of the barite-water system by Kusakabe and Robinson [5]. The temperature dependence of the oxygen isotope fractionation factors was calculated by the least squares method in which the weight was taken to be inversely proportional to the experimental error. The fractionation is given by:10³lnαanhydrite-water=3.21×(10³/T)²?4.72Available δ¹⁸O values of natural anhydrite were used to test the validity of this expression. It is shown that this newly revised geothermometer can be successfully applied to natural hydrothermal anhydrite.     

Influence of Atmospheric Solar Radiation Absorption on Photodestruction of Ions at D-Region Altitudes of the Ionosphere

The influence of atmospheric solar radiation absorption on the photodetachment, dissociative photodetachment, and photodissociation rate coefficients (photodestruction rate coefficients) of O^?, Cl^?, O₂ ^?, O₃ ^?, OH^?, NO₂ ^?, NO₃ ^?, O₄ ^?, OH^?(H₂O), CO₃ ^?, CO₄ ^?, ONOO^?, HCO₃ ^?, CO₃ ^?(H₂O), NO₃ ^?(H₂O), O₂ ⁺(H₂O), O₄ ⁺, N₄ ⁺, NO⁺(H₂O), NO⁺(H₂O)₂, H⁺(H₂O) _n for n = 2–4, NO⁺(N₂), and NO⁺(CO₂) at D-region altitudes of the ionosphere is studied. A numerical one-dimensional time-dependent neutral atmospheric composition model has been developed to estimate this influence. The model simulations are carried out for the geomagnetically quiet time period of 15 October 1998 at moderate solar activity over the Boulder ozonesonde. If the solar zenith angle is not more than 90° then the strongest influence of atmospheric solar radiation absorption on photodestruction of ions is found for photodissociation of CO₄ ^? ions when CO₃ ^? ions are formed. It follows from the calculations that decreases in the photodestruction rate coefficients of ions under consideration caused by this influence are less than 2 % at 70 km altitude and above this altitude if the solar zenith angle does not exceed 90°.     

Ion microprobe studies of water in silicate melts: Temperature-dependent water diffusion in obsidian

The temperature dependence of water diffusivity in rhyolite melts over the range 650–950°C and [P_T(H₂O] = 700 bars is evaluated from water concentration-distance profiles measured in glass with an ion microprobe. Diffusivities are exponentially dependent on concentration over this temperature range and vary from about 10^?8 cm²/s at 650°C to about 10^?7 cm²/s at 950°C at 2 wt.% water. Water solubility also varies with temperature at a rate of ?0.14 wt. per 100°C increase. The avtivation energy (E_a) appears to be constant at 19 ± 1kal/mole for 1, 2,and 3 wt.% H₂O. Comparison of these data with results for cation diffusion indicates that this value is a minimum E_a for diffusion of any species in a rhyolite melt.Compensation plots of log₁₀D₀ (the frequency factor) versus E_a indicate that hydrous rhyolite melts follow the same trend as anhydrous basalts. D₀ increases for H₂O and Ca²⁺ [1] as E_a decreases. This suggests that these molecules may diffuse by different mechanisms than do monovalent cations, and that hydration of the melt affects diffusion of Ca²⁺ and H₂O differently than it does monovalent cation diffusion. The results imply that dramatic increases in cation diffusivities by hydration [1] may occur with additions of less than 1 wt.% H₂O.     

Carbon monoxide on the primitive earth

The reaction of CO + OH^? in aqueous solution to give formate was studied as a carbon monoxide sink on the primitive earth and in the present ocean. The reaction is first order in OH^? and first order in the molar CO concentration. The second order rate constant is given by log k(M^?1hr^?1) = 15.83?4886/T between 25°C and 60°C. Using the solubility of CO in sea water, and assuming a pH of 8 for a primitive ocean of the present size, the halflife of CO in the atmosphere is calculated to be 12 × 10⁶ yr at 0°C and 5.5 × 10⁴ yr at 25°C.Three other CO sinks would have been important in the primitive atmosphere: CO + H₂ → H₂CO driven by various energy sources, CO + OH → CO₂ + H, and the Fischer-Tropsch reaction of CO + H₂ → hydrocarbons, etc. It is concluded that the lifetime of a CO atmosphere would have been very short on the geological time scale although the relative importance of these four CO sinks is difficult to estimate.The CO + OH^? reaction to give formate is a very minor CO sink on the earth at the present time.     

The role of the SO2 oxidation for the background stratospheric sulfate layer in the light of new reaction rate data

Presently available data on the reaction of SO₂ with OH radicals (OH + SO₂ + \(M\xrightarrow[{k_1 }]{}\) HSO₃ +M) are critically reviewed in light of recent stratospheric sulfur budget calculations. These calculations impose that the net oxidation ratek of SO₂ within the stratosphere should fall within the range 10^?7≤k≤10^?9, if the SO₂ oxidation model for the stratospheric sulfate layer is assumed to be correct. The effective reaction rate constantk ₁ ^* =k ₁[M] at the stratospheric temperature is estimated as $$k_1^* = \frac{{(8.2 \pm 2.2) \times 10^{ - 13} \times [M]}}{{(0.79 \mp 0.34) \times 10^{ - 13} + [M]}}cm^3 /molecules sec$$ where [M] refers to the total number density (molecules/cm³). Using the above limiting values ofk ₁ ^* , and the estimated OH density concentrations, the net oxidation rate is calculated as 3.6×10^?7≤k≤1.3×10^?8 at 17 km altitude. This indicates that the upper limit of thesek values exceeds the tolerable range imposed by the model by a factor of about four. Obviously the uncertainty of thek ₁ ^* values and of the OH concentrations in the stratosphere is still too large to make definite conclusions on the validity of the SO₂ model.     

Response of surface water chemistry to reduced levels of acid precipitation: comparison of trends in two regions of New York,USA

In light of recent reductions in sulphur (S) and nitrogen (N) emissions mandated by Title IV of the Clean Air Act Amendments of 1990, temporal trends and trend coherence in precipitation (1984–2001 and 1992–2001) and surface water chemistry (1992–2001) were determined in two of the most acid‐sensitive regions of North America, i.e. the Catskill and Adirondack Mountains of New York. Precipitation chemistry data from six sites located near these regions showed decreasing sulphate (SO₄^2?), nitrate (NO₃^?), and base cation (C_B) concentrations and increasing pH during 1984–2001, but few significant trends during 1992–2001. Data from five Catskill streams and 12 Adirondack lakes showed decreasing trends in SO₄^2? concentrations at all sites, and decreasing trends in NO₃^?, C_B, and H⁺ concentrations and increasing trends in dissolved organic carbon at most sites. In contrast, acid‐neutralizing capacity (ANC) increased significantly at only about half the Adirondack lakes and in one of the Catskill streams. Flow correction prior to trend analysis did not change any trend directions and had little effect on SO₄^2? trends, but it caused several significant non‐flow‐corrected trends in NO₃^? and ANC to become non‐significant, suggesting that trend results for flow‐sensitive constituents are affected by flow‐related climate variation. SO₄^2? concentrations showed high temporal coherence in precipitation, surface waters, and in precipitation–surface water comparisons, reflecting a strong link between S emissions, precipitation SO₄^2? concentrations, and the processes that affect S cycling within these regions. NO₃^? and H⁺ concentrations and ANC generally showed weak coherence, especially in surface waters and in precipitation–surface water comparisons, indicating that variation in local‐scale processes driven by factors such as climate are affecting trends in acid–base chemistry in these two regions. Copyright © 2005 John Wiley & Sons, Ltd.     

Distinguishing Iron-Reducing from Sulfate-Reducing Conditions

Ground water systems dominated by iron‐ or sulfate‐reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe²⁺) and sulfide (sum of H₂S, HS^?, and S⁼ species and denoted here as “H₂S”). This approach is based on the observation that concentrations of Fe²⁺ and H₂S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe²⁺ concentrations are high, H₂S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe²⁺ with H₂S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron‐ and the sulfate‐reducing microorganisms that catalyze the production of Fe²⁺ and H₂S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe²⁺ and H₂S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H₂) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe²⁺/H₂S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H₂～0.2 to 0.8 nM). Conversely, if the Fe²⁺/H₂S ratio was less than 0.30, consistent sulfate‐reducing (H₂～1 to 5 nM) conditions were observed over time. Concomitantly high Fe²⁺ and H₂S concentrations were associated with H₂ concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron‐ and sulfate‐reducing zones or concomitant iron and sulfate reduction under nonelectron donor–limited conditions. These observations suggest that Fe²⁺/H₂S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems.     

UV camera measurements of fumarole field degassing (La Fossa crater,Vulcano Island)

The UV camera is becoming an important new tool in the armory of volcano geochemists to derive high time resolution SO₂ flux measurements. Furthermore, the high camera spatial resolution is particularly useful for exploring multiple-source SO₂ gas emissions, for instance the composite fumarolic systems topping most quiescent volcanoes. Here, we report on the first SO₂ flux measurements from individual fumaroles of the fumarolic field of La Fossa crater (Vulcano Island, Aeolian Island), which we performed using a UV camera in two field campaigns: in November 12, 2009 and February 4, 2010. We derived ~ 0.5 Hz SO₂ flux time-series finding fluxes from individual fumaroles, ranging from 2 to 8.7 t d^?1, with a total emission from the entire system of ~ 20 t d^?1 and ~ 13 t d^?1, in November 2009 and February 2010 respectively. These data were augmented with molar H₂S/SO₂, CO₂/SO₂ and H₂O/SO₂ ratios, measured using a portable MultiGAS analyzer, for the individual fumaroles. Using the SO₂ flux data in tandem with the molar ratios, we calculated the flux of volcanic species from individual fumaroles, and the crater as a whole: CO₂ (684 t d^?1 and 293 t d^?1), H₂S (8 t d^?1 and 7.5 t d^?1) and H₂O (580 t d^?1 and 225 t d^?1).     

Salt fretting in the valley cliff of the Asama volcano region,Japan

On the pumice flow deposits of the Asama volcano, Japan, many salts such as halite (NaCl), gypsum (CaSO₄·2H₂O), hexahydrite (MgSO₄·6H₂O) and mirabilite (Na₂SO₄·10H₂O) crystallize at the base of south-facing valley cliffs. The zone of salt efflorescence and of resulting polygonal rind correspond to the zones of notch formation and high water content. The main conditions for salt crystallization and polygonal rind formation are: (1) the existence of groundwater containing a high concentration of Cl^?, SO, Ca²⁺, Mg²⁺, and Na⁺; (2) a valley cliff material with a high capillary action and small tensile strength; and (3) low humidity and a high ground-surface temperature derived from the direct incidence of sunshine. Given the right conditions, salt weathering can occur not only in the arid regions but also in humid, temperate inland regions.     

Volcanic gases and sublimates from Showashinzan

Volcanic gases from Showashinzan are qualitatively the same as those liberated from igneous rocks when they are heated in vacuum. Their main components are H₂O, CO₂, and H₂. Then follow HCl, HF, N₂, SO₂, H₂S, S, CH₄, CO, Ar, Si, B, Mg, Na, K, Ca, Al, Fe, P, Br, NH₃, As, Zn, Sr, Ba, Cu, Pb, Sn, Sb, Bi, Ge, Ag, Cr, Ni, Mo, Rn, Ra, etc. They come through fumaroles of high temperature (～750°C.). Metallic compounds deposit as sublimates around the outlet of fumaroles. They are fractionated there according to their thermodynamic properties. When the temperature of gases falls, heavy metal elements deposit before reaching the surface of the earth. Ra is among them. Owing to the contribution of Ra thus depositted, Rn content of vapor is larger in low temperature fumaroles than in high temperature ones. Chemical compounds of H, C, N, O, and S vary their composition according to the condition of temperature and pressure. Sulfur exists as SO₂ more than H₂S. As the temperature of gases falls, SO₂ and H₂ decrease and H₂S increases. Mutual relation among them is ruled by the chemical equilibrium: SO₂+3H₂=H₂S+2H₂O. The structure of Showashinzan is not simple. Some deviations from the general rule are explained in connection with ground water.     

Origin of natural sulphur-bearing immiscible inclusions and H2S in oolite gas reservoir, Eastern Sichuan

Based on results of microscopic observation and laser Raman analysis about fluid inclusions, multiple special forms of immiscible inclusions that contain sulphur, liquid hydrocarbon, bitumen, etc. were discovered in samples collected from the H₂S gas reservoir-containing carbonates in the Lower Triassic Feixianguan Formation in the Jinzhu-Luojia area, Kai County, Sichuan Province. Based on the lithology and burial history of the strata involved as well as measurement results of homogenization temperature of fluid inclusions, bitumen reflectivity, etc., it is concluded that the H₂S in the gas reservoir resulted from the thermal reaction between hydrocarbons in reservoir and CaSO₄ in the gypsum-bearing dolostone section at the high temperature (140°C–17°C) oil-cracked gas formation stage in Late Cretaceous. Thereafter, research on a great number of immiscible inclusions in the reservoir reveals that elemental sulphur resulted from oxidation of part of the earlier-formed H₂S and further reaction between sulphates, hydrocarbons and H₂S in geological fluids in H₂S-bearing gas reservoir at a temperature of 86°C–89°C and a pressure of 340×10⁵Pa and during the regional uplift stage as characterized by temperature decrease and pressure decrease in Tertiary. Meanwhile, gypsum, anhydrite and calcite formed at this stage would trap particles like elemental sulphur and result in a variety of special forms of immiscible inclusions, and these inclusions would contain information concerning the complexity of the fluids in the reservoir and the origin of H₂S and natural sulphur in the gas reservoir.     

Estimating thermal inflow to El Chichón crater lake using the energy-budget,chemical and isotope balance approaches

El Chichón crater lake appeared immediately after the 1982 catastrophic eruption in a newly formed, 1-km wide, explosive crater. During the first 2 years after the eruption the lake transformed from hot and ultra-acidic caused by dissolution of magmatic gases, to a warm and less acidic lake due to a rapid “magmatic-to-hydrothermal transition” — input of hydrothermal fluids and oxidation of H₂S to sulfate. Chemical composition of the lake water and other thermal fluids discharging in the crater, stable isotope composition (δD and δ¹⁸O) of lake water, gas condensates and thermal waters collected in 1995–2006 were used for the mass-balance calculations (Cl, SO₄ and isotopic composition) of the thermal flux from the crater floor. The calculated fluxes of thermal fluid by different mass-balance approaches become of the same order of magnitude as those derived from the energy-budget model if values of 1.9 and 2 mmol/mol are taken for the catchment coefficient and the average H₂S concentration in the hydrothermal vapors, respectively. The total heat power from the crater is estimated to be between 35 and 60 MW and the CO₂ flux is not higher than 150 t/day or ~ 200 gm^− 2 day^− 1.     

Hydrological and isotopic characterization of river water,groundwater, and groundwater recharge in the Heihe River basin,northwestern China

We used hydrochemistry and environmental isotope data (δ¹⁸O, δD, tritium, and ¹⁴C) to investigate the characteristics of river water, groundwater, and groundwater recharge in China's Heihe River basin. The river water and groundwater could be characterized as Ca²⁺? Mg²⁺? HCO₃^?? SO₄^2? and Na⁺? Mg²⁺? SO₄^2?? Cl^? types, respectively. Hydrogeochemical modelling using PHREEQC software revealed that the main hydrogeochemical processes are dissolution (except for gypsum and anhydrite) along groundwater flow paths from the upper to middle Heihe reaches. Towards the lower reaches, dolomite and calcite tend to precipitate. The isotopic data for most of the river water and groundwater lie on the global meteoric water line (GMWL) or between the GMWL and the meteoric water line in northwestern China, indicating weak evaporation. No direct relationship existed between recharge and discharge of groundwater in the middle and lower reaches based on the isotope ratios, d‐excess, and ¹⁴C values. On the basis of tritium in precipitation and by adopting an exponential piston‐flow model, we evaluated the mean residence time of shallow groundwater with high tritium activities, which was around 50 years (a). Furthermore, based on the several popular models, it is calculated that the deep groundwaters in piedmont alluvial fan zone of the middle reaches and in southern part of the lower reaches are modern water, whereas the deep groundwaters in the edge of the middle reaches and around Juyan Lake in the lower reaches of Heihe river basin are old water. Copyright © 2010 John Wiley & Sons, Ltd.