Isotopic evidence of TSR origin for natural gas bearing high H<Subscript>2</Subscript>S contents within the Feixianguan Formation of the northeastern Sichuan Basin,southwestern China

The northeastern area of Sichuan Basin, southwestern China, is the area with the maximal reserve of natural gas containing higher hydrogen sulphide (H₂S) that has been found among the petroliferous basins of China, with the proven and controlled gas reserve of more than 200 billion cubic meters. These gas pools, with higher H₂S contents averaging 9%, some 17%, are mainly distributed on structural belts of Dukouhe, Tieshanpo, Luojiazhai, Puguang, etc., while the oolitic-shoal dolomite of the Triassic Feixianguan Fm. (T₁f) is the reservoir. Although many scholars regard the plentiful accumulation of H₂S within the deep carbonate reservoir as the result of Thermochemical Sulfate Reduction (TSR), however, the process of TSR as well as its residual geological and geochemical evidence is still not quite clear. Based on the carbon isotopic analysis of carbonate strata and secondary calcite, etc., together with the analysis of sulfur isotopes within H₂S, sulphur, gypsum, iron pyrites, etc., as well as other aspects including the natural gas composition, carbon isotopes of hydrocarbons reservoir petrology, etc., it has been proved that the above natural gas is a product of TSR. The H₂S, sulphur and calcite result from the participation of TSR reactions by hydrocarbon gas. During the process for hydrocarbons being consumed due to TSR, the carbons within the hydrocarbon gas participate in the reactions and finally are transferred into the secondary calcite, and become the carbon source of secondary calcite, consequently causing the carbon isotopes of the secondary calcite to be lower (−18.2‰). As for both the intermediate product of TSR, i.e. sulfur, and its final products, i.e. H₂S and iron pyrites, their sulfur elements are all sourced from the sulfate within the Feixianguan Fm. During the fractional processes of sulfur isotopes, the bond energy leads to the ³²S being released firstly, and the earlier it is released, the lower δ ³⁴S values for the generated sulphide (H₂S) or sulfur will be. However, for the anhydrite that participates in reactions, the higher the reaction degree, the more ³²S is released, while the less ³²S remains and the more δ ³⁴S is increased. The testing results have proved the process of the dynamic fractionation of sulfur isotopes.     

TSR promotes the formation of oil-cracking gases: Evidence from simulation experiments

TSR is an interaction between sulfate and hydrocarbons, occurring widely in carbonate reservoirs. Because this process can produce a large amount of noxious acidic gases like H2S, it has drawn seri- ous concern recently. This paper reports an experiment that simulated an interaction between different minerals and hydrocarbon fluids under different temperature and time using a confined gold-tube system. The results showed that the main mineral that initiates TSR is MgSO4, and adding a certain amount of NaCl into the reactive system can also promote TSR and yield more H2S. The H2S produced in TSR is an important incentive for the continuous oxidative degradation of crude oils. For instance, the yield of oil-cracking gases affected by TSR was twice of that not affected by TSR while the yield of TSR-affected methane was even higher, up to three times of that unaffected by TSR. The carbon iso- topes of wet gases also became heavier. All of the above illustrated that TSR obviously motivates the oxidative degradation of crude oils, which makes the gaseous hydrocarbon generation sooner and increases the gas dryness as well. The study on this process is important for understanding the TSR mechanism and the mechanism of natural gas generation in marine strata.     

Isotopic evidence of TSR origin for natural gas bearing high H_2S contents within the Feixianguan Formation of the northeastern Sichuan Basin, southwestern China

Isotopic evidence of TSR origin for natural gas bearing high H2S contents 1961 As the hazardous component of natural gas, the ex-istence of H2S, due to its extremely strong toxicity and corrosivity, not only decreases the percentage of hy-drocarbon gas within natural gas and reduces its in-dustrial value, it also threatens each aspect of drilling and exploitation. It frequently causes serious safety accidents[1] and leads to the E&P cost and risk of natural gas with higher H2S contents be…     

Basical characteristics of fluid geologic process of interlayer oxidation zone sandstone-typeuranium deposit

This paper reveals the physicochemical properties such as component, formulation, genesis, tem- perature, pH, Eh, salinity and pressure of all main alteration fluid of interlayer oxidation zone sand- stone-type uranium deposits after studying the geologic process and geochemistry of internal typical sandstone-type uranium deposits such as Shihongtan deposit in the Turpan-Hami basin, 512 deposit in the Yili basin, Dongsheng deposit in the Ordos basin. The composition of fluid can be divided into two parts based on the analysis of inclusion one can be affirmed as atmospheric water with ordinary temperature epigenesist according to the character of hydrogen and oxygen isotope of inclusion, the other is natural gas containing gaseous hydrocarbon like CH4, and CO2 as well as a little H2S, CO, H2, N2 and so on, it always contains a small quantity of hydrocarbon liquid in petroliferous basins. The fluid property of oxidation alteration zone is always oxidation alkaline, and neutrality or weak acid-weak alkaline and reducibility during the metallizing process, but at secondary reduction or deoxidization zone it becomes strong reduction alkaline. Oxygenic groundwater in the fluid is the activate and mig- ratory medium of uranium element, but the gaseous hydrocarbon like CH4 as well as H2, H2S, CO from natural gas is the important sedimentary reducer of uranium mineral; the transformation of pH,Eh in fluid environment is the main reason for the formation of uranium metallization.     

松辽盆地深部地壳构造特征与无机油气生成模式

松辽盆地中地壳有一低速-高导层(也称塑性层),中地壳的塑性层与松辽盆地的成因以及盆山耦合系统有关.盆地地幔流体活动有下列表现:(1)高热流、高地温场;(2)深大断裂与火山岩喷溢;(3)碱交代作用(如钠长石化、伊利石化);(4)Mg2 交代作用(如白云石化)等等.地球化学省与地球化学急变带控制了大油气田的分布并显示了盆地发生的壳-幔相互作用.中地壳的低速-高导层不是岩浆岩,而是一充满地幔流体的地质体,它们富含氢、碱金属(K 、Na )、卤素(F-、Cl-)、碳(甲烷、CO、CO2)、氮、硫等.在中地壳的温度压力条件下,在Fe、Ni等催化荆的参与下,H2与CO(CO2)可发生费-托合成烃的反应.实验表明:这个反应不仅可生成气态烃还可生成液态烃,并将发生碳同位素分馏作用.松辽盆地的U形运移模型受到质疑.按照石油无机生成的模型,松辽盆地的深部将会有更多的石油与天然气,庆深气田的发现便是一个明证.     

Origin of natural sulphur-bearing immiscible inclusions and H_2S in oolite gas reservoir, Eastern Sichuan

Fluid inclusions as captured in homogeneous fluids in rocks and minerals have been extensively studied and successfully applied to exploring the metalloge- netic temperature and pressure of metallic ore deposits and in investigating hydrocarbon generation, migra- tion, etc.[1―6]. In regard to multiple forms of immis- cible inclusions in rocks and minerals, a significant amount of research has already been conducted toward the immiscible inclusions and “boiling” inclusions in CO2-H2O system…     

Molecular characterization of sulfur compounds in some special sulfur-rich Chinese crude oils by FT-ICR MS

Routine GC/MS analysis may apply to the volatilized Low-Molecular-Weight compounds in saturate and aromatic hydrocarbon fractions;thus,relative studies using this technique inevitably bring about some limitations on distribution of miscellaneous sulfur atom.In this article,Fourier Transform Ion Cyclotron Resonance Mass Spectrometry(FT-ICR MS)with high resolution is employed to investigate the distribution of organic sulfur compounds(OSCs)in the crude oil typically derived from the Eogene carbonate-evaporite sediments with further chemical compositional characterization in molecular level by miscellaneous atomic type,carbon number,and double bond equivalent(DBE).A variety of miscellaneous atomic types with S1,S2,S3,OS,OS2,O2S,O2S2,NS,and NOS etc.(S1 means those OSCs with one sulfur atom in a molecule)were identified in OSCs in these oil samples.High levels of alkyl thioether series compounds with one ring structure were presented mainly in the crude oil in the Jianghan Basin whereas high amounts of benzothiophene,dibenzothiophene etc.compounds with higher values in DBE and carbon number range occurred in the sulfur-rich heavy oil in the Jinxian Sag.Although carbonate-evaporite sediments deposited in the saline lacustrine facies in the Eogene basin both occurred in the Jinxian Sag and Jianghan Basin,obviously,they possess different chemical diagenetic pathway of sulfur under various microbial reactions,leading to diverse distributional characteristics on biomarkers,OSCs,and even different hydrocarbon generation mechanism of immature crude oil.     

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park, Wyoming, USA. II. Formation and decomposition of thiosulfate and polythionate in Cinder Pool

Cinder Pool is an acid-sulfate-chloride boiling spring in Norris Geyser Basin, Yellowstone National Park. The pool is unique in that its surface is partially covered with mm-size, black, hollow sulfur spherules, while a layer of molten sulfur resides at the bottom of the pool (18 m depth). The sulfur speciation in the pool was determined on four different days over a period of two years. Samples were taken to evaluate changes with depth and to evaluate the importance of the sulfur spherules on sulfur redox chemistry. All analyses were conducted on site using a combination of ion chromatography and colorimetric techniques.Dissolved sulfide (H₂S), thiosulfate (S₂O₃²⁻), polythionates (S_xO₆²⁻), and sulfate were detected. The polythionate concentration was highly variable in time and space. The highest concentrations were found in surficial samples taken from among the sulfur spherules. With depth, the polythionate concentrations dropped off. The maximum observed polythionate concentration was 8 μM. Thiosulfate was rather uniformly distributed throughout the pool and concentrations ranged from 35 to 45 μM. Total dissolved sulfide concentrations varied with time, concentrations ranged from 16 to 48 μM. Sulfate was relatively constant, with concentrations ranging from 1150 to 1300 μM. The sulfur speciation of Cinder Pool is unique in that the thiosulfate and polythionate concentrations are significantly higher than for any other acid-sulfate spring yet sampled in Yellowstone National Park. Complementary laboratory experiments show that thiosulfate is the intermediate sulfoxyanion formed from sulfur hydrolysis under conditions similar to those found in Cinder Pool and that polythionates are formed via the oxidation of thiosulfate by dissolved oxygen. This last reaction is catalyzed by pyrite that occurs as a minor constituent in the sulfur spherules floating on the pool's surface. Polythionate decomposition proceeds via two pathways: (1) a reaction with H₂S, yielding thiosulfate and elemental sulfur; and (2) by disproportionation to sulfate and thiosulfate.This study demonstrates that the presence of a subaqueous molten sulfur pool and sulfur spherules in Cinder Pool is of importance in controlling the pathways of aqueous sulfur redox reactions. Some of the insights gained at Cinder Pool may be relevant to acid crater lakes where sulfur spherules are observed and variations in polythionate concentrations are used to monitor and predict volcanic activity.     

On the development mechanism of the lacustrine high-grade hydrocarbon source rocks of Chang 9<Subscript>1</Subscript> member in Ordos Basin

As revealed from recent drilling and organic geochemical testing and research, a series of lacustrine high-grade hydrocarbon source rocks was discovered in the upper section of the Chang 9 oil reservoir member of upper Triassic in Ordos Basin. The hydrocarbon source rocks show average TOC content as high as 5.03%, average bitumen “A” content as high as 0.8603%, and good quality organic precursors, which are of the sapropelic type mainly derived from lower aquatic plants and have reached the thermal evolution stage featured by oil-producing climax. Generally the lacustrine high-grade hydrocarbon source rocks were developed in local depressions of a lake basin, and the Chang 9₁ member was particularly formed in a depositional environment characterized by fresh water to weakly saline water, weakly oxidizing to weakly reducing setting and semi-deep lake facies, as was demonstrated by a variety of organic to inorganic geochemical parameters. As a result, high productivity constitutes the principal controlling force for generation of this series of high-grade hydrocarbon source rocks. Deposition of thinly-bedded and laminated tuffs as well as positive Eu anomaly corroborate the possible occurrence of anoxic geological event closely related to contemporaneous volcanic eruption, which would play a key part in development of the Chang 9₁ member of high-grade hydrocarbon source rocks.     

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.     

Statistical estimation of the relative efficiency of natural attenuation mechanisms in contaminated aquifers

Using monitored natural attenuation is an increasingly popular strategy for dealing with contaminated aquifers. This paper provides a statistical methodology for the estimation of the relative efficiency of natural attenuation mechanisms. The methodology provides estimates, with associated measures of uncertainty, of the relative efficiency of four types of bio-degradation (oxidation using oxygen as the electron-acceptor, denitrification, iron reduction and sulfate reduction). A data set from Trecate, Italy, is analysed using the methodology. The analysis shows that sulfate is the main cause of hydrocarbon removal on this site. It is also seen that oxidation using oxygen seems to be more preferential than the other reactions, in the sense that this reaction is relatively more efficient than other reactions at locations where the hydrocarbon concentration is low.     

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.     

Basical characteristics of fluid geologic process of interlayer oxidation zone sandstone-type uranium deposit

This paper reveals the physicochemical properties such as component, formulation, genesis, tem-perature, pH, Eh, salinity and pressure of all main alteration fluid of interlayer oxidation zone sand-stone-type uranium deposits after studying the geologic process and geochemistry of internal typical sandstone-type uranium deposits such as Shihongtan deposit in the Turpan-Hami basin, 512 deposit in the Yili basin, Dongsheng deposit in the Ordos basin. The composition of fluid can be divided into two parts based on the analysis of inclusion: one can be affirmed as atmospheric water with ordinary temperature epigenesist according to the character of hydrogen and oxygen isotope of inclusion, the other is natural gas containing gaseous hydrocarbon like CH₄, and CO₂ as well as a little H₂S, CO, H₂, N₂ and so on, it always contains a small quantity of hydrocarbon liquid in petroliferous basins. The fluid property of oxidation alteration zone is always oxidation alkaline, and neutrality or weak acid-weak alkaline and reducibility during the metallizing process, but at secondary reduction or deoxidization zone it becomes strong reduction alkaline. Oxygenic groundwater in the fluid is the activate and mig-ratory medium of uranium element, but the gaseous hydrocarbon like CH₄ as well as H₂, H₂S, CO from natural gas is the important sedimentary reducer of uranium mineral; the transformation of pH,Eh in fluid environment is the main reason for the formation of uranium metallization.     

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.     

Verringerung der Schwermetall‐ und Sulfatbelastung in sauren bergbaubelasteten Gewässern durch Aluminiumpräzipitate

Attenuation of Heavy Metals and Sulfate by Aluminium Precipitates in Acid Mine Drainage During the mixing of acid mine waters with nearly neutral tributaries, often precipitates are formed which are high in iron or aluminium. These precipitates cover the river bed for many kilometres. Near the town of Lehesten (Thuringian slate mining area), leachates of slate quarries and waste rock dumps contain high amounts of aluminium, sulfate, copper, nickel, zinc, manganese, and H⁺ ions as a result of the oxidation of incorporated pyrite. These leachates enter the brooks Loquitz, Kleine Sormitz, and Rehbach leading to the phenomenon named above. The contribution of the forming aluminium‐rich precipitates on the attenuation of sulfate and heavy metals by sorption or coprecipitation was studied by analysing the composition of water and sediment samples as well as samples of suspended matter. Sulfate is often considered as conservative tracer in acid mine drainage. However, sulfate does not behave conservatively in this system what might be explained by the adsorption of sulfate to the aluminium precipitates. Instead, conservative behaviour was found for calcium, potassium, chloride, zinc, manganese, and nickel. A formation of jurbanite can be excluded because of the low sulfate contents. The sulfate content of the sediment depends on the pH. At low pH values (4.8) the S/Al ratio corresponds to the theoretical ratio in basaluminite and decreases with rising pH. Sulfate is weakly bound to the solid phase and can easily be replaced by OH^– ions. A formation of basaluminite is possible at low pH values with a fluent transition to aluminium hydroxide. Therefore the precipitates are assumed to consist predominantly of aluminium hydroxide with sulfate being adsorbed to the surface.     

Sediment Thicknesses and Q<Subscript>s</Subscript> vs. Q<Subscript>p</Subscript> Relations in the Kachchh Rift Basin,Gujarat, India Using Sp Converted Phases

Delineation of the top sedimentary structure and its Q_s vs. Q_p relationship using the travel-time difference of direct S and converted Sp phase is key to understanding the seismic hazard of any sedimentary basin area. We constructed filtered displacement waveforms from local ETNA Episensor acceleration recordings as well as local velocity recordings of aftershocks of the 2001 Bhuj earthquake recorded by the Kachchh seismological network of the National Geophysical Research Institute (NGRI), Hyderabad, India during 2001–2004. Stations are within 15–70km of epicenters, and the resulting displacement waveforms are generally simple, displaying prominent P, Sp, and S wave pulses. Particle motion of P and S waves suggest near-vertical raypaths consistent with preliminary depth estimates. The direct S wave on the horizontal component is characterized by lower frequency content than the converted Sp phase on the vertical component. This difference in frequency content between S and Sp phases can be explained in terms of different attenuation effects for P and S waves in the unconsolidated sediments. The Sp phase is generated by S-to-P phase conversion at the base of Mesozoic sediments of the Kachchh basin. Travel-time inversion (VELEST) of 2565 P and 2380 S arrivals from 658 well located aftershocks recorded at 8–14 three-component local seismic stations led to 1 D velocity models indicated very slow sediments in the upper 0–2 km depth range (Vp: 2.92 km/s and Vs: 0.90 km/s) and an increasing trend of velocities with depth at 2–40 km depth. The estimated sediment thicknesses beneath 12 accelerograph and 6 seismograph sites from the estimated velocity model and the travel-time difference between S and converted Sp phases reaches a maximum of (1.534 ± 0.117) km beneath Bandri (near the location of 2001 Bhuj mainshock) and attains a minimum sediment thickness of (0.858 ± 0.104) km beneath Ramvav and Burudia. The spectral ratios between Sp and S from 159 three-component accelerograms have been used to study seismic wave attenuation in the Kachchh rift basin. The estimated Q_s vs. Q_p relations for 12 accelerograph sites vary from Q_s = 0.184 Q_p (at Chobari) to Q_s = 0.505 Q_p (at Dudhai). For stations Chobari, Chopdwa, Jahawarnagar, Vondh and Tapar, the spectral ratio slopes and hence the calculated Q_s vs. Q_p relations are effectively the same, and the correlation coefficients are quite high (0.91–0.93). Stations Adhoi, Manfara, New Dudhai, Dudhai and Sikara have similar Q_s vs. Q_p relationships to each other and also have high correlation coefficients (0.78–0.87). The spectral ratios for stations Anjar and Ramvav are small and poorly constrained, resulting in less reliable Q_s vs. Q_p relations. This could be due to noisy data, fewer available waveforms, or scattering due to velocity heterogeneities and/or interface irregularities.     

Functioning of intertidal flats inferred from temporal and spatial dynamics of O<Subscript>2</Subscript>, H<Subscript>2</Subscript>S and pH in their surface sediment

In this article, we describe the dynamics of pH, O₂ and H₂S in the top 5–10 cm of an intertidal flat consisting of permeable sand. These dynamics were measured at the low water line and higher up the flat and during several seasons. Together with pore water nutrient data, the dynamics confirm that two types of transport act as driving forces for the cycling of elements (Billerbeck et al. 2006b): Fast surface dynamics of pore water chemistry occur only during inundation. Thus, they must be driven by hydraulics (tidal and wave action) and are highly dependent on weather conditions. This was demonstrated clearly by quick variation in oxygen penetration depth: Seeps are active at low tide only, indicating that the pore water flow in them is driven by a pressure head developing at low tide. The seeps are fed by slow transport of pore water over long distances in the deeper sediment. In the seeps, high concentrations of degradation products such as nutrients and sulphide were found, showing them to be the outlets of deep-seated degradation processes. The degradation products appear toxic for bioturbating/bioirrigating organisms, as a consequence of which, these were absent in the wider seep areas. These two mechanisms driving advection determine oxygen dynamics in these flats, whereas bioirrigation plays a minor role. The deep circulation causes a characteristic distribution of strongly reduced pore water near the low water line and rather more oxidised sediments in the centre of the flats. The two combined transport phenomena determine the fluxes of solutes and gases from the sediment to the surface water and in this way create specific niches for various types of microorganisms.     

Impact-induced perturbations of atmospheric sulfur

Asteroids and comets that are vaporized during hypervelocity impact events can inject large masses of S into the stratosphere where it can potentially affect the radiation budget of the Earth, alter the chemistry of the ozone layer, and eventually be converted to sulfuric acid rain. Relatively small carbonaceous asteroids, 0.3 km in diameter, contain 5 times more S than the entire modern stratosphere and these objects hit the Earth at an average rate of 1 per 10,000 years. Larger impact events, capable of injecting 10¹⁵ g of S into the stratosphere, occur at an average rate of 1 per 1 million years. Calculations indicate there is sufficient O and H in the vapor plumes of most impact events to convert the S to sulfuric acid aerosols. If this conversion occurs, then the larger impact events could depress mean surface temperatures by more than 2°C for 3 years or longer.     

Differentation of magmatic emanation

Chemical properties of magmatic emanation can be estimated roughly by i) volatiles from rocks by heating at various temperatures, ii) volcanic emanations, iii) residual magmatic emanations, iv) calculation from chemical equilibrium between volatile matters and magmas. Magmatic emanation is assumed to consist all of the volatile matters in magmas such asH ₂ O, HCl, HF, SO ₂ H ₂ S, H ₂,CO 2,N ₂ and others (halides, etc.) at about 1200°C, although various kinds of magmatic emanations can be formed at different conditions. Magmatic emanation separated from magmas will change their chemical properties by many factors such as changes of temperature and pressure (displacement of chemical equilibrium), and reactions with other substances and it will differentiate into volcanic gases, volcanic waters, volcanic sublimates, and hydrothermal deposits (hot spring deposits). At temperatures above the critical point of water, separation of solid phase (sublimates), liquid phase, and displacement of chemical equilibrium may take place, and gaseous phase will gradually change their chemical properties as will be seen at many fumaroles. Chloride, hydrogen, andSO ₂ contents will gradually decrease along with lowering temperature. Once aqueous liquid phase appears below the critical point of water, all the soluble materials may dissolve into this hydrothermal solution. Consequently, the gaseous phase at this stage must have usually a little hydrogen chloride as is observed at many fumaroles. Aqueous solutions must be of acidic nature by dissolution of acid forming components, and by hydrolysis (Chloride type). When a self-reduction-oxidation reaction of sulfurous acid takes place, an aqueous solution of sulfate type will be formed. At this stage, solid phases consist of the remained sublimates which are difficultly soluble in aqueous solution, and deposits formed by reaction in the hydrothermal solutions. The gaseous phases below the boiling point of water, have usually a little water, and consist mainly ofCO ₂ type,H ₂ S type,N ₂ type, and mixed type owing to elimination or addition of components by reactions with waters or wall rocks according to their geological conditions. Aqueous solutions which was of acidic nature must be changed into alkaline solutions by reaction with wall rocks for a long time. When the oxidation of sulfur compounds takes place, an aqueous solution of sulfate type will be formed. Hydrogen sulfide type of water will be formed by reaction of sulfides with acid waters or absorption of hydrogen sulfide. Carbonate type of water will be formed whenCO ₂ is absorbed. Solid phases at this stage consist usually of hydrothermal deposits except for that at solfatara or mofette. The course of differentiation of magmatic emanation could take place in more complicated ways than that of magmatic differentiation.     

Improved method to determine the molar volume and compositions of the NaCl-H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript> system inclusion

On the basis of Parry’s method (1986), an improved method was established to determine the molar volume (Vm) and compositions (X) of the NaCl-H2O-CO2 (NHC) system inclusion. To use this method, the determination of Vm-X only requires three microthermometric data of a NHC inclusion: partial homog-enization temperature (Th ,CO2), salinity (S) and total homogenization temperature (Th). Theoretically, four associated equations are needed containing four unknown parameters: X CO2, XNaCl, Vm and F (volume fraction of CO2 phase in total inclusion when occurring partial homogenization). When they are released, the Vm-X are determined. The former three equations, only correlated with Th ,CO2, S and F, have simplified expressions:XCO2=f1(Th,CO2,S,F),XNaCl=f2(Th,CO2,S,F),Vm=f3(Th,CO2,S,F). The last one is the thermodynamic relationship of X CO2, XNaCl, Vm and Th:f4(XCO2,XNaCl,Vm,Th)=0.Since the above four associated equations are complicated, it is necessary to adopt iterative technique to release them. The technique can be described by:(i) Freely input a F value (0≤F≤1),with Th ,CO2 and S, into the former three equations. As a result,X CO 2,XNaCl and the molar volume value recorded as Vm1 are derived. (ii) Input the X CO2 and XNaCl gotten in the step above into the last equation, and another molar volume value recorded as Vm2 is determined. (iii) If Vm1 is unequal to Vm2, the calculation will be restarted from “(i)”. The iteration is completed until Vm1 is equal to Vm2, which means that the four associated equations are released. Compared to Parry’s (1986) solution method, the improved method is more convenient to use, as well as more accurate to determine X CO 2. It is available for a NHC inlusion whose partial homogenization temperature is higher than clatherate melting temperature and there are no solid salt crystals in the inclusion at parital homogenization.