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.     

Stratification and mixing of a post-glacial Neoproterozoic ocean: Evidence from carbon and sulfur isotopes in a cap dolostone from northwest China

To improve our knowledge about the geochemical and environmental aftermath of Neoproterozoic global glaciations, we analyzed stable isotopes (δ¹³C, δ¹⁸O, δ³⁴S) and elemental concentrations (Ca, Mg, S, Sr, Fe, and Mn) of the ～ 10-m-thick Zhamoketi cap dolostone atop the Tereeken diamictite in the Quruqtagh area, eastern Chinese Tianshan. Available chemostratigraphic data suggest that the Tereeken diamictite is probably equivalent to the Marinoan glaciation. Our new data indicate that organic and carbonate carbon isotopes of the Zhamoketi cap dolostone show little stratigraphic variations, averaging ? 28.2‰ and ? 4.6‰, respectively. In contrast, sulfur isotopes show significant stratigraphic variations. Carbonate associated sulfate (CAS) abundance decreases rapidly in the basal cap dolostone and δ³⁴S_CAS composition varies between + 9‰ and + 15‰ in the lower 2.5 m. In the overlying interval, CAS abundance remains low while δ³⁴S_CAS rises ～ 5‰ and varies more widely between + 10‰ and + 21‰. The range of δ³⁴S_py of the cap dolostone overlaps with that of δ³⁴S_CAS, but direct comparison shows that δ³⁴S_py is typically greater than δ³⁴S_CAS measured from the same samples. Hypotheses to explain the observations must account for both the remarkable sulfur isotope enrichment of pyrites and the inverse fractionation. We propose that CAS and pyrite were derived from two isotopically distinct reservoirs in a chemically stratified basin or a basin with a sulfate minimum zone. In this model, CAS was derived from shallow, oxic surface waters with moderate sulfate concentration and depleted in ³⁴S due to the post-glacial influx of sulfur from continental weathering. In contrast, pyrite was derived from anoxic bottom waters (or a sulfate minimum zone) with low sulfate concentration and ³⁴S enrichment due to long-term syn-glacial sulfate reduction. The rapid shift in CAS abundance and sulfur isotope composition within the cap dolostone is interpreted to reflect the mixing of the two reservoirs after initial deglaciation. Comparison with other post-Marinoan cap carbonates shows significant spatial heterogeneity in δ³⁴S_CAS, which together with strong temporal variation in δ³⁴S_CAS, points to generally low sulfate concentrations in post-Marinoan oceans.     

Natural gas leakage of Mizhi gas reservoir in Ordos Basin,recorded by natural gas fluid inclusion

Abundant natural gas inclusions were found in calcite veins filled in fractures of Central Fault Belt across the centre of Ordos Basin. Time of the calcite veins and characteristics of natural gas fluid inclusion were investigated by means of dating of thermolum luminescence (TL) and analyzing stable isotope of fluid inclusion. Results show that natural gas inclusion formed at 130–140°C with salinity of 5.5 wt%–6.0 wt% NaCl. It indicates that natural gas inclusion is a kind of thermal hydrocarbon fluid formed within the basin. Method of opening inclusion by heating was used to analyze composition of fluid inclusion online, of which the maximal hydrocarbon gas content of fluid inclusion contained in veins is 2.4219 m³/t rock and the maximal C₁/ΣC _i ratio is 91%. Laser Raman spectroscopy (LRS) was used to analyze chemistry of individual fluid inclusion in which the maximal hydrocarbon gas content is 91.6% compared with little inorganic composition. Isotope analysis results of calcite veins show that they were deposited in fresh water, in which the δ ¹³C_PDB of calcite veins is from ?5.75‰ to 15.23‰ and δ ¹⁸O_SMOW of calcite veins is from 21.33‰ to 21.67‰. Isotope results show that δ ¹³C_{1 PDB} of natural gas fluid inclusion is from ?21.36‰ to ?29.06‰ and δD_SMOW of that is from ?70.89‰ to ?111.03‰. It indicates that the gas of fluid inclusion formed from coal source rocks and it is the same as that of natural gas of Mizhi gas reservoir. Results of TL dating show that time of calcite vein is (32.4±3.42)×10⁴ a, which is thought to be formation time of gas inclusion. It indicated that natural gas inclusion contained in calcite veins recorded natural gas leakage from Mizhi gas reservoir through the Central Fault Belt due to Himalayan tectonic movement.     

Sulfur and carbon isotopic systematics of Guadalupian‐Lopingian (Permian) mid‐Panthalassa: δ34S and δ13C profiles in accreted paleo‐atoll carbonates in Japan

Immediately before the extinction of the end‐Guadalupian (Middle Permian; ca 260 Ma), a significant change to the global carbon cycle occurred in the superocean Panthalassa, as indicated by a prominent positive δ¹³C excursion called the Kamura event. However, the causes of this event and its connection to the major extinction of marine invertebrates remain unclear. To understand the mutual relationships between these changes, we analyzed the sulfur isotope ratio of the carbonate‐associated sulfate (CAS) and HCl‐insoluble residue, as well as the carbon isotope ratio of bulk organic matter, for the Middle‐Upper Permian carbonates of an accreted mid‐oceanic paleo‐atoll complex from Japan, where the Kamura event was first documented. We detected the following unique aspects of the stable carbon and sulfur isotope records. First, the extremely high δ¹³C values of carbonate (δ¹³C_carb) over +5 ‰ during the Capitanian (late Guadalupian) were associated with large isotopic differences between carbonate and organic matter (Δ¹³C = δ¹³C_carb ? δ¹³C_org). We infer that the Capitanian Kamura event reflected an unusually large amount of dissolved organic matter in the expanded oxygen minimum zone at mid‐depth. Second, the δ³⁴S values of CAS (δ³⁴S_CAS) were inversely correlated with the δ¹³C_carb values during the Capitanian to early Wuchiapingian (early Late Permian) interval. The Capitanian trend may have appeared under increased oceanic sulfate conditions, which were accelerated by intense volcanic outgassing. Bacterial sulfate reduction with increased sulfate concentrations in seawater may have stimulated the production of pyrite that may have incorporated iron in pre‐existing iron hydroxide/oxide. This stimulated phosphorus release, which enhanced organic matter production and resulted in high δ¹³C_carb. Low δ³⁴S_CAS values under high sulfate concentrations were maintained and the continuous supply of sulfate cannot by explained only by the volcanic eruption of the Emeishan Trap, which has been proposed as a cause of the extinction. The Wuchiapingian δ³⁴S_CAS–δ¹³C_carb correlation, likely related to low sulfate concentration, may have been caused by the removal of oceanic sulfate through the massive evaporite deposition.     

Geochemical constraints on the depositional environment of the 1.84 Ga Embury Lake Formation,Flin Flon Belt,Canada

The Flin Flon Belt of Canada contains Paleoproterozoic volcanic–sedimentary sequences that are related to the Trans‐Hudson Orogeny. The sequences include island arc volcanic and volcaniclastic rocks (Amisk Group) that are unconformably overlain by subaerial sedimentary rocks (Missi Group), and younger deep facies sediments. In the Flin Flon area, several north–south trending faults divide the sequences into blocks and obscure the depositional environment of the deep facies sediments. Locally, within the Flin Flon area, the Embury Lake Formation is in fault contact with island arc volcanic–sedimentary sequences of the Amisk and Missi Groups. To identify the depositional environment of the Embury Lake Formation, we used lithologic and geochemical approaches. Here, we report carbon isotopic values in organic matter (δ¹³C_org) and sulfur isotopes (δ³⁴S), as well as total organic carbon and total sulfur measurements for the black shale in the formation. Samples were taken from a drill core that contains alternating bands of sandstone and black shale. Pyrite in the black shale is divided into four textural types: euhedral, vein‐type, elliptical, and microcrystalline. Microcrystalline pyrite is typically generated by microbially mediated sulfate reduction. An extremely low S/C ratio (avg. = 0.04) is consistent with lacustrine deposition. The ranges of δ¹³C_org (?36 ‰ to ?27 ‰) and δ³⁴S (+3.0 ‰ to +7.7 ‰) values can be explained by bacterial photosynthesis that involved Calvin cycle and acetyl CoA pathways, and sulfate reduction in a low‐sulfate environment. Considering the depositional age reported in a previous study of < 1.84 Ga, the Embury Lake Formation was likely emplaced in a lacustrine setting during the Trans‐Hudson Orogeny.     

Diffuse CO2 efflux from Iwojima volcano,Izu-Ogasawara arc,Japan

Iwojima volcano, located on the southernmost part of the Izu-Ogasawara arc, is characterized by the extrusion of trachyte or trachy andesite lavas and pyroclastic rocks of Holocene and surface thermal manifestations. Small phreatic explosions have been recorded frequently during the last 100 years with the most recent in 1999 and 2001. In order to elucidate the behavior of volcanic volatiles and to assess the potential activity of this volcano, diffuse CO₂ efflux, CO₂ content and δ¹³C–CO₂ in soil gas, and soil temperature at 30 cm depth were measured at 272 sites in March 2000, 112 sites in December 2000 and 40 sites in December 2001. We found that high CO₂ efflux values, of more than 100 g m⁻² day⁻¹, occurred at several locations on Motoyama volcano corresponding with high soil temperatures (more than 60 °C at 30 cm depth) region and with areas where CO₂ with magmatic δ¹³C was observed. Here, the magmatic δ¹³C determined for fumarolic CO₂ data ranged from −2‰ to +3‰, which is clearly higher than magmatic gas values (−8‰ to −2‰) typically found in island arc settings around the world. However, this can be explained in terms of carbon-isotope fractionation between calcite and CO₂ under subsurface temperature and pressure conditions at Iwojima. A total efflux of CO₂ for Iwojima volcano is estimated to be 760 t day⁻¹, with a magmatic contribution of about 450 t day⁻¹. This value is rather high compared with other volcanoes in island arc settings. Since Iwojima has no visible plume, almost all volcanic CO₂ is released as diffuse efflux through the volcanic edifice.     

The stable isotope geochemistry of volcanic lakes, with examples from Indonesia

Stable isotope compositions (δD, δ¹⁸O and δ³⁴S) of volcanic lake waters, gas condensates and spring waters from Indonesia, Italy, Japan, and Russia were measured. The spring fluids and gas samples plot in a broad array between meteoric waters and local high-temperature volcanic gas compositions. The δD and δ¹⁸O data from volcanic lakes in East Indonesia plot in a concave band ranging from local meteoric waters to evaporated fluids to waters heavier than local high-temperature volcanic gases. We investigated isotopic fractionation processes in volcanic lakes at elevated temperatures with simultaneous mixing of meteoric waters and volcanic gases. An elevated lake water temperature gives enhanced kinetic isotope fractionation and changes in equilibrium fractionation factors, providing relatively flat isotope evolution curves in δ¹⁸O–δD diagrams. A numerical simulation model is used to derive the timescales of isotopic evolution of crater lakes as a function of atmospheric parameters, lake water temperature and fluxes of meteoric water, volcanic gas input, evaporation, and seepage losses. The same model is used to derive the flux magnitude of the Keli Mutu lakes in Indonesia. The calculated volcanic gas fluxes are of the same order as those derived from energy budget models or direct gas flux measurements in open craters (several 100 m³ volcanic water/day) and indicate a water residence time of 1–2 decades. The δ³⁴S data from the Keli Mutu lakes show a much wider range than those from gases and springs, which is probably related to the precipitation of sulfur in these acid brine lakes. The isotopic mass balance and S/Cl values suggest that about half of the sulfur input in the hottest Keli Mutu lake is converted into native sulfur.     

Natural gas leakage of Mizhi gas reservoir in Ordos Basin,recorded by natural gas fluid inclusion

Abundant natural gas inclusions were found in calcite veins filled in fractures of Central Fault Belt across the centre of Ordos Basin. Time of the calcite veins and characteristics of natural gas fluid inclusion were investigated by means of dating of thermolum luminescence (TL) and analyzing stable isotope of fluid inclusion. Results show that natural gas inclusion formed at 130–140°C with salinity of 5.5 wt%–6.0 wt% NaCl. It indicates that natural gas inclusion is a kind of thermal hydrocarbon fluid formed within the basin. Method of opening inclusion by heating was used to analyze composition of fluid inclusion online, of which the maximal hydrocarbon gas content of fluid inclusion contained in veins is 2.4219 m³/t rock and the maximal C₁/ΣC _i ratio is 91%. Laser Raman spectroscopy (LRS) was used to analyze chemistry of individual fluid inclusion in which the maximal hydrocarbon gas content is 91.6% compared with little inorganic composition. Isotope analysis results of calcite veins show that they were deposited in fresh water, in which the δ ¹³C_PDB of calcite veins is from −5.75‰ to 15.23‰ and δ ¹⁸O_SMOW of calcite veins is from 21.33‰ to 21.67‰. Isotope results show that δ ¹³C_{1 PDB} of natural gas fluid inclusion is from −21.36‰ to −29.06‰ and δD_SMOW of that is from −70.89‰ to −111.03‰. It indicates that the gas of fluid inclusion formed from coal source rocks and it is the same as that of natural gas of Mizhi gas reservoir. Results of TL dating show that time of calcite vein is (32.4±3.42)×10⁴ a, which is thought to be formation time of gas inclusion. It indicated that natural gas inclusion contained in calcite veins recorded natural gas leakage from Mizhi gas reservoir through the Central Fault Belt due to Himalayan tectonic movement.

     

Isotopic geochemistry of acid thermal waters and volcanic gases from Zaō volcano in Japan

The chemical composition and D/H, and ratios have been determined for the acid hot waters and volcanic gases discharging from Zaō volcano in Japan. The thermal springs in Zaō volcano issue acid sulfate-chloride type waters (Zaō) and acid sulfate type waters (Kamoshika). Gases emitted at Kamoshika fumaroles are rich in CO₂, SO₂ and N₂, exclusive of H₂O. Chloride concentrations and oxygen isotope data indicate that the Zaō thermal waters issue a fluid mixture from an acid thermal reservoir and meteoric waters from shallow aquifers. The waters in the Zaō volcanic system have slight isotopic shifts from the respective local meteoric values. The isotopic evidence indicates that most of the water in the system is meteoric in origin. Sulfates in Zaō acid sulfate-chloride waters with δ³⁴S values of around +15‰, are enriched in ³⁴S compared to Zaō H₂S, while the acid sulfate waters at Kamoshika contain supergene light sulfate (δ³⁴S = + 4‰) derived from volcanic sulfur dioxide from the volcanic exhalations. The sulfur species in Zaō acid waters are lighter in δ³⁴S than those of other volcanic areas, reflecting the difference in total pressure.     

Isotopic Characterization of Sulfate in a Shallow Aquifer Impacted by Agricultural Fertilizer

The stable isotope ratios of groundwater sulfate (³⁴S/³²S, ¹⁸O/¹⁶O) are often used as tracers to help determine the origin of groundwater or groundwater contaminants. In agricultural watersheds, little is known about how the increased use of sulfur as a soil amendment to optimize crop production is affecting the isotopic composition of groundwater sulfate, especially in shallow aquifers. We investigated the isotopic composition of synthetic agricultural fertilizers and groundwater sulfate in an area of intensive agricultural activity, in Ontario, Canada. Groundwater samples from an unconfined surficial sand aquifer (Lake Algonquin Sand Aquifer) were analyzed from multi-level monitoring wells, riverbank seeps, and private domestic wells. Fertilizers used in the area were analyzed for sulfur/sulfate content and stable isotopic composition (δ¹⁸O and/or δ³⁴S). Fertilizers were isotopically distinct from geological sources of groundwater sulfate in the watershed and groundwater sulfate exhibited a wide range of δ³⁴S (−6.9 to +20.0‰) and δ¹⁸O (−5.0 to +13.7‰) values. Quantitative apportionment of sulfate sources based on stable isotope data alone was not possible, largely because two of the potential fertilizer sulfate sources had an isotopic composition on the mixing line between two natural geological sources of sulfate in the aquifer. This study demonstrates that, when sulfate isotope analysis is being used as a tracer or co-tracer of the origin of groundwater or of contaminants in groundwater, sulfate derived from synthetic fertilizer needs to be considered as a potential source, especially when other parameters such as nitrate independently indicate fertilizer impacts to groundwater quality.     

Experimental determination of the rate and equilibrium fractionation factors of sulfur isotope exchange between sulfate and sulfide in slightly acid solutions at 300°C and 1000 bars

A sulfur isotope fractionation of 20.0 ± 0.2‰ was measured between aqueous sulfide and sulfate at 300°C and 1000 bars using gold-cell hydrothermal solution equipment. The value is 2‰ smaller than previously published values. Rates of exchange were determined as a function of pH and total sulfur content. Initial mean ³⁴S concentration was changed to approach equilibrium from two directions. Half-times ranged from 3.4 to 8.2 days, with shorter times obtained for more acid and more concentrated solutions.The sulfate-sulfide isotope temperature scale based on theory should be revised according to this new fractionation factor. The rate data permit assessment of the extent to which equilibrium may be attained in some natural systems. For example, the lack of agreement between temperatures based on sulfide mineral pairs and sulfide-sulfate mineral pairs from Kuroko ore deposits of Japan might imply that the residence time of sulfate and sulfide in Kuroko solutions was not longer than 1000 years, if the present kinetic data are correct. Geothermal systems such as the Wairakei system of New Zealand may reach sulfur isotope equilibrium between sulfate and sulfide in 300 years at 300°C, but would be increasingly removed from equilibrium at lower temperatures if residence times were 300 years or less.     

Elemental fractionation in lavas during post-eruptive degassing: Evidence from trachytic lavas,Rishiri Volcano,Japan

Trachytic lavas of Rishiri Volcano, northern Japan, show a peculiar geochemical variation across lava flow units. Samples collected systematically in a vertical cross section from a lava flow unit with a thickness of about 20 m are nearly homogeneous in major element compositions. However, some trace elements, including Li, B and Cs, are considerably depleted in samples collected from the main part of the flow unit, compared to those obtained from the surface of the lava flow (clinker layer). In particular, Cs content of the main flow unit is as low as ∼30% of the clinker layer. ¹¹B / ¹⁰B ratios of samples from the main flow unit are also slightly lower than those of the clinker samples, and the isotope compositions positively correlate with boron concentrations. These geochemical variations cannot be explained by magmatic processes in magma chambers, post-eruptive weathering, or alteration process. Rather, we infer these systematics resulted from escape of these elements from the lava flow unit during post-eruptive degassing. Vapor phases in which Li, B and Cs dissolved are suggested to have been transported through veins formed in the main flow unit as fractures due to slight shearing along the flow planes after lava emplacement. In the Tanetomi lava, only rocks of the clinker layer preserve original composition of magmas, although they are porous and brownish due to extensive oxidization. On the other hand, rocks of the main flow unit do not retain original magma compositions, although they are dense and grayish, and seem to be much fresher compared to the clinkers. A similar geochemical modification of lavas can occur in other volcanic systems, especially for lavas consisting of relatively thick flow units.     

The isotopic composition of oxygen and carbon in the hyaloclastites from the Mt. Iblei volcanic area,Eastern Sicily: A preliminary study

Oxygen and carbon isotopic analyses were carried out for some typical submarine volcanic products (a lava flow, a pillow fragment and four hyaloclastite breccias) from the northwestern zone of the Mt. Iblei volcanic complex, eastern Sicily. The δ¹⁸O value of the perental basaltic magma (6.0 ± 0.2‰), estimated from the analyses of some fresh unaltered glassy samples of various type, lies in the values range of primary basalts. Appreciably higher δ¹⁸O values, probably due to low-temperature exchanges with sea water, have been found for lava samples and the interior of the pillow fragment. The δ¹⁸O and δ¹³C of the calcites of the groundmass of the hyaloclastite samples, ranging from 30.59 to 33.65 and from ?2.99 to 0.46‰ respectively, are typical of low-temperature marine carbonates. Because calcite is one of the last minerals to form. these results suggest that the hyaloclastites studied formed entirely in a submarine environment. The¹⁸O/¹⁶O ratios recorded in the silicate portions of the matrices of the hyaloclasites (δ¹⁸O=13.99 to 16.61) are interpreted as the result of halmyrolytic processes occurring at temperatures somewhat higher than that of the sea floor.     

Incrustations and fumarolic condensates at kilauea volcano, Hawaii: field, drill-hole and laboratory observations

Hawaiian volcanoes characteristically have but few of the many types of minerals found in incrustations of other volcanic areas. In Hawaii sulfates resulting from air oxidation of volatiles predominate, and fluorides produced during rock alteration by fumarolic gases are prominent. Halides are generally found where reducing conditions exist in fumaroles and lava lake drill holes. The most common mineral types are sulfur, opaline silica, gypsum, ralstonite, and thenardite. Minerals from the same deposit are found to vary markedly in the content of the less abundant components. Condensates from vapor issuing from fumaroles show little quantitative relationship in component content to incrustations deposited at the same fumaroles. It is believed that an energetically favorable isomorphic substitution of some elements in the crystal lattice of a depositing mineral may lead to the build-up of a high concentration of an element from a lean vapor. Equilibrium calculations applied to condensate studies give a good quantitative approximation to the concentrations of the elements found in natural systems, but when applied to incrustations they serve only to indicate general compositional relations. Laboratory studies have shown the important role of chlorides in metal transfer in the gas phase in high-temperature aqueous systems, but only in the absence of oxygen. These studies also demonstrated the important role of HF in rock alteration and in the transfer of silica.     

Equilibrium calculations in volcanic gaseous systems

Equilibria calculations of high-temperature volcanic gases from lava lakes are carried out on the basis of best volcanic gas samples. The equilibrium gas composition at temperatures from 800° to 1400°K and pressures up to 25 kilobars (in ideal gas system) was calculated using the free energy minimization model as well as the Newton-Raphson methods. It is shown that the juvenile «magmatic gas » of basaltic magma consists of three components: H₂O, SO₂, CO₂; the water vapor being about 60%. The increase of temperature under constant pressure results in the increase of the SO₂ concentration and in the simultaneous decrease of H₂S. Under the same conditions the ratios CO/CO₂ and H₂/H₂O are found to increase. Methane cannot be a component of «magmatic gas» corresponding to the elemental composition of basaltic lava gases. The calculated values of \(P_{O_2 } \) are in good agreement with the experimental data obtained from direct measurements of \(P_{O_2 } \) in lava lakes and experiments with basaltic melts.     

Preliminary study on the origin identification of natural gas by the parameters of light hydrocarbon

The light hydrocarbon composition of 209 natural gas samples and individual light hydrocarbon carbon isotopes of 53 natural gas samples from typical humic-sourced gas and sapropelic-sourced gas in the four basins of China have been determined and analyzed. Some identification parameters for humic-sourced gas and sapropelic-sourced gas are proposed or corrected. The differences of compound-specific δ ¹³C value of individual light hydrocarbon between humic-sourced gas and sapropelic-sourced gas have been founded. The humic-sourced gas has the distribution of δ ¹³C_benzene> ?24‰, δ ¹³C_toluene >?23‰, δ ¹³C_cyclohexane > ?24‰ and δ ¹³C_{methyl cyclohexane}> ?24‰, while the sapropelic-sourced gas has the distribution of δ ¹³C_benzene <?24‰, δ ¹³C_toluene< ?24‰, δ ¹³C_cyclohexane< ?24‰ and δ ¹³C_{methyl cyclohexane}< ?24‰. Among the components of C₇ light hydrocarbon compound, such as normal heptane (nC₇), methyl cyclohexane (MCH) and dimethyl cyclopentane (ΣDMCP), etc, relative contents of nC₇ and MCH are influenced mainly by the source organic matter type of natural gas. Therefore, it is suggested that the gas with relative content of nC₇ of more than 30% and relative content of MCH of less than 70% is sapropelic-sourced gas, while gas with relative content of nC₇ of less than 35% and relative content of MCH of more than 50% is humic-sourced gas. Among components of C_5–7 aliphatics, the gas with relative content of C_5–7 normal alkane of more than 30% is sapropelic-sourced gas, while the gas with relative content of C_5–7 normal alkane of less than 30% is humic-sourced gas. These paremeters have been suggested to identify humic-sourced gas and sapropelic-sourced gas.     

Erta'ale lava lake: heat and gas transfer to the atmosphere

Data on uncontaminated samples of volcanic gases can be counted on the fingers of one hand, yet estimation of total volcanic gas flow cannot be made without such data. In this paper the flux of gas from the lava lake to the atmosphere is calculated by a heat budget based on the excess heat loss caused by combustion of H₂ and CO and by the mass rate of loss of other gases on the basis of their ratios to H₂ and CO in the unoxidized gas samples. The estimated rates of loss of H₂O, CO₂, SO₂ and HCl are consistent with the rate of loss of heat if this heat is generated by crystallization and if the initial magma contains concentrations of gas appropriate for submarine basalt from oceanic ridges. The moderate activity of permanent degassing from the two active lava ponds studied gives a lower flux than that of other volcanoes.     

The hydrothermal system of Mendeleev Volcano,Kunashir Island,Kuril Islands: The geochemistry and the transport of magmatic components

This paper reports a detailed geochemical study of thermal occurrences as observed in the edifice and on the flanks of Mendeleev Volcano, Kunashir Island in August and September 2015. We showed that three main types of thermal water are discharged there (neutral chloride sodium, acid chloride sulfate, and acid sulfate types); these waters exhibit a zonality that is typical of volcano-hydrothermal island arc systems. Spontaneous and solfataric gases have relatively low ³He/⁴He ratios, ranging between 5.4Ra and 5.6Ra, and δ¹³C-CO₂ between –4.8‰ and –3.1‰, and contain a light isotope of carbon in methane (δ¹³C ≈ –40‰). Gas and isotope geothermometers yield relatively low temperatures around 200°C. The isotope compositions in all types of water are similar to that of local meteoric water. The distribution of microcomponents varies among different types. The isotope composition of dissolved Sr varies considerably, from 0.7034 as observed in Kunashir rocks on an average to 0.7052 in coastal springs, which may have resulted from admixtures of seawater. The total hydrothermal transport rates of magmatic Cl and SO₄, as observed for Mendeleev Volcano, are 7.8 t/d and 11.6 t/d, respectively. The natural outward transport of heat by the volcano’s hydrothermal system is estimated as 21 MW.     

Cenozoic evolution of the sulfur cycle: Insight from oxygen isotopes in marine sulfate

We report new data on oxygen isotopes in marine sulfate (δ¹⁸O_SO4), measured in marine barite (BaSO₄), over the Cenozoic. The δ¹⁸O_SO4 varies by 6‰ over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The δ¹⁸O_SO4 does not co-vary with the δ³⁴S_SO4, emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the δ¹⁸O_SO4 over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The δ¹⁸O_SO4 also does not co-vary with the δ¹⁸O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the δ¹⁸O_SO4 to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the δ¹⁸O_SO4. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.     

Carbon isotope composition and comparison of Lower Triassic marine carbonate rocks from Southern Longmenxia section in Guang’an,Sichuan Basin

The Early Triassic was a period of ecological restoration for the earth's system after the end-Permian mass extinction.Geochemical records linked to the variations in marine ecosystems during this period have attracted the interest of geologists for many years.Based on petrographic analysis of samples and evaluations of their reliability as proxies for original seawater,this study investigated the carbon and oxygen isotopic compositions of 350 carbonate rock samples from the Lower Triassic(and adjacent strata)in the southern Longmenxia section of Guang'an,eastern Sichuan Basin.The results indicate that the Triassic carbonate rocks from the southern Longmenxia section favorably preserved the original seawater'sδ~(13)C signal.Furthermore,carbon and oxygen isotopic compositions are found to be poorly correlated,with a determination coefficient as low as 0.0205 and only 44 rock samples show results of Mn/Sr2 and/orδ~(18)0-6.5‰.The complete carbon isotopic curve for the Lower Triassic is established using the data from the remaining 306 samples with Mn/Sr2 and/orδ~(18)O-6.5‰.This curve presents favorable comparability on a global scale,specifically in theδ~(13)C minima near the Permian-Triassic boundary,at the top of the Jia1 and within the the Jia3,as well as in theδ~(13)C maxima at the tops of the Ye1 and Ye4,at the base of the Jia2 and at the top of the Ye3.The peaks and troughs corresponding to these maxima and minima all reflect global signals.By comparing these results to previous research on coeval carbon isotopic curves established within the chronostratigraphic framework,the ages of these critical evolution points are determined.The results show that the Ye1 roughly corresponds to the Griesbachian substage;the Ye2 through Ye4 correspond to the Dienerian substage;Jial corresponds to the Smithian substage;from the Jia2 to the lower part of the Jia4 correspond to the Spathian substage;and the middle and upper parts of the Jia4 belongs to the Aegean Substage of the Middle Triassic.Around the boundary between the Jial and Jia2(which represents the Smithian-Spathian boundary(SSB)),the value ofδ~(13)C increases rapidly from-0.911‰to 3.679‰.The span during which the seawater's carbon isotope experiences this drastic change may be less than36 kyr.The oxygen isotope,which is more sensitive to sedimentary environmental changes,exhibits changes prior to the carbon isotope near the SSB,indicating a significant increase in the salinity of the seawater before a sharp rise in the carbon isotope;this event leads to the formation of evaporites and dolomites.