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.     

River channel dynamics following extirpation of wolves in northwestern Yellowstone National Park,USA

Historical records indicate that gray wolves (Canis lupus) were extirpated from the upper Gallatin River Basin in the early 1900s. Following the removal of these large carnivores, elk (Cervis elaphus) began to increasingly browse streamside vegetation in the winter range, causing widespread loss of formerly extensive willow (Salix spp.) communities. Historical aerial photographs and chronosequences of ground photographs were used to characterize general changes in vegetation and channel morphology over time. In August of 2004, riparian vegetation and channel cross‐sections were surveyed along three reaches of the upper Gallatin River. Reach A was located upstream of the elk winter range (control reach) whereas reaches B and C (treatment reaches) were located within the elk winter range. Willow cover on floodplains averaged 85 per cent for reach A, but only 26 per cent and 5 per cent for reaches B and C, respectively. The average return period of calculated bankfull discharges was 3·1 yrs for reach A but increased to 32·4 yrs and 10·6 yrs for reaches B and C, respectively. The long‐term loss of streamside vegetation allowed channels to generally increase in hydraulic capacity (via increases in width, incision or both) and decrease their hydrologic connectivity with adjacent floodplains. This study documents, perhaps for the first time, the resultant impacts to riparian vegetation functions and stream channel characteristics following the extirpation of a large mammalian carnivore. Copyright © 2006 John Wiley & Sons, Ltd.     

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.     

Eruptive activity at Mount St Helens,Washington, USA, 1984–1988: a gas geochemistry perspective

The results from two different types of gas measurement, telemetered in situ monitoring of reducing gases on the dome and airborne measurements of sulfur dioxide emission rates in the plume by correlation spectrometry, suggest that the combination of these two methods is particularly effective in detecting periods of enhanced degassing that intermittently punctuate the normal background leakage of gaseous effluent from Mount St Helens to the atmosphere. Gas events were recorded before lava extrusion for each of the four dome-building episodes at Mount St Helens since mid-1984. For two of the episodes, precursory reducing gas peaks were detected, whereas during three of the episodes, COSPEC measurements recorded precursory degassing of sulfur dioxide. During one episode (October 1986), both reducing gas monitoring and SO₂ emission rate measurements simultaneously detected a large gas release several hours before lava extrusion. Had both types of gas measurements been operational during each of the dome-building episodes, it is thought that both would have recorded precursory signals for all four episodes. Evidence from the data presented herein suggests that increased degassing at Mount St Helens becomes detectable when fresh upward-moving magma is between 2 km and a few hundred meters below the base of the dome and between about 60 and 12 hours before the surface extrusion of lava.     

Gas geochemistry of the Valles caldera region, New Mexico and comparisons with gases at Yellowstone, Long Valley and other geothermal systems

Noncondensible gases from hot springs, fumaroles, and deep wells within the Valles caldera geothermal system (210–300°C) consist of roughly 98.5 mol% CO₂, 0.5 mol% H₂S, and 1 mol% other components. ³He/⁴He ratios indicate a deep magmatic source (R/R_a up to 6) whereas δ¹³C–CO₂ values (−3 to −5‰) do not discriminate between a mantle/magmatic source and a source from subjacent, hydrothermally altered Paleozoic carbonate rocks. Regional gases from sites within a 50-km radius beyond Valles caldera are relatively enriched in CO₂ and He, but depleted in H₂S compared to Valles gases. Regional gases have R/R_a values ≤1.2 due to more interaction with the crust and/or less contribution from the mantle. Carbon sources for regional CO₂ are varied. During 1982–1998, repeat analyses of gases from intracaldera sites at Sulphur Springs showed relatively constant CH₄, H₂, and H₂S contents. The only exception was gas from Footbath Spring (1987–1993), which experienced increases in these three components during drilling and testing of scientific wells VC-2a and VC-2b. Present-day Valles gases contain substantially less N₂ than fluid inclusion gases trapped in deep, early-stage, post-caldera vein minerals. This suggests that the long-lived Valles hydrothermal system (ca. 1 Myr) has depleted subsurface Paleozoic sedimentary rocks of nitrogen. When compared with gases from many other geothermal systems, Valles caldera gases are relatively enriched in He but depleted in CH₄, N₂ and Ar. In this respect, Valles gases resemble end-member hydrothermal and magmatic gases discharged at hot spots (Galapagos, Kilauea, and Yellowstone).     

夏季降雨事件对水库温室气体通量变化的影响:来自湖北官庄水库的高频观测

湖库淡水水域对温室气体排放的贡献不容小觑,然而观测时间的代表性不足以及缺乏对降雨因素的考虑制约了碳排放的准确估计.本研究以湖北宜昌境内官庄水库为例,选取强降雨多发的夏季时段,针对水气界面温室气体通量、水体表层和垂向剖面气体溶存浓度及环境因子开展了为期1周的原位高频观测,以探讨夏季降雨事件对水库温室气体通量变化的影响.结果表明,观测期内官庄水库水气界面CH₄通量变化范围为0.007~0.077 mg/（m²·h）,CO₂通量范围为5.48~57.57 mg/（m²·h）,白天和夜晚均表现为大气的碳源.小雨、中雨乃至暴雨天气条件下,CH₄和CO₂日均通量均较低,日通量倾向于受风速和温度调控.CH₄和CO₂通量变化趋势较为一致,观测期内日间排放量高于夜间排放量出现的次数更多,昼夜差异对降雨天气状况无明显响应,风速是CH₄和CO₂通量昼夜变化的主导因素.暴雨过程中,CH₄-k₆₀₀和CO₂-k₆₀₀与水气温差存在显著正相关,但水体垂向混合过程十分短暂.在平均雨强为3.8 mm/h的暴雨第I阶段,CH₄-k₆₀₀对风速和降雨的响应明显,而在雨强更大（8.5 mm/h）的第II阶段,CH₄-k₆₀₀与风速、降雨均未表现出相关性,通量箱在强降雨条件下的适用性可能存在雨强阈值.     

Probing the magma plumbing of Erebus volcano,Antarctica, by open-path FTIR spectroscopy of gas emissions

Gas emissions from Erebus volcano, Antarctica, were measured by open-path Fourier transform infrared spectroscopy to understand degassing of its magmatic system. Two degassing phonolite lava lakes were present in the summit crater during observation in December 2004. We report analyses of H₂O, CO₂, CO, SO₂, HF, HCl and OCS, (in order of molar abundance) in the plumes. Variations in the proportions of these species strongly reflect the dynamics of degassing, and sourcing of gas from different depths in the magmatic network. The highest observed ratios of CO₂ and H₂O are consistent with gas extracted from the melt at a depth of up to ∼ 2 km below the lava lakes. Magma degassing above this depth contributes to a higher H₂O/CO₂ proportion in the airborne plume. The ratio therefore reflects the balance of deeper vs. shallower contributions of volatiles and, possibly, a combination of closed- and open-system degassing. We observe a strong contrast in HF content in emissions from the two lava lakes, which we attribute to differing levels of magma ascent and/or cooling and crystallization of the magma supply. Fluxes of all gas species were determined using independent SO₂ flux determinations and measured gas ratios. In the case of CO₂ and water, ∼ 1 and ∼ 0.4 m³ s^− 1, respectively, of parental basanite magma are required to sustain the calculated output. The discrepancy between the two figures is readily explained by sequestration of part of the magma supply at depth such that it only partially degasses its complement of water.     

Longitudinal distributions of two formation pathways of biogenic gases in continental deposits: A case study from Sebei 1 gas field in the Qaidam Basin, western China

The distribution of two formation pathways of biogenic methane, acetate fermentation and reduction of CO2, has been extensively studied. In general, CO2 reduction is the dominate pathway in marine envi- ronment where acetate is relatively depleted because of SRB consuming. While in terrestrial freshwater or brackish environment, acetate fermentation is initially significant, but decreases with increasing buried depth. In this paper, character of biogenic gases is profiled in the XS3-4 well of the Sebei 1 gas field in the Sanhu depression, Qaidam Basin. It indicates that those two pathways do not change strictly with increasing buried depth. CO2 reduction is important near the surface (between 50 m and 160 m), and at the mesozone (between 400 and 1650 m). While acetate fermentation is the primary pathway at two zones, from 160 to 400 m and from 1650 to 1700 m. δ 13C of methane generated in those two acetate fermentation zones varies greatly, owing to different sediment circumstances. At the sec- ond zone (160-400 m), δ 13C1 ranges from ?65‰ to ?30‰ (PDB), because the main deposit is mudstone and makes the circumstance confined. At the fourth zone of the well bottom (1650-1700 m), δ 13C1 is lighter than ?65‰ (PDB). Because the deposit is mainly composed of siltstone, it well connects with outer fertile groundwater and abundant nutrition has supplied into this open system. The high con- centration of acetate is a forceful proof. δ 13C of methane would not turn heavier during fermentation, owing to enough nutrition supply. In spite of multi-occurrence of acetate fermentation, the commercial gas accumulation is dominated by methane of CO2-reduction pathway. A certain content of alkene gases in the biogenic gases suggests that methanogensis is still active at present.     

Variations of electric resistance and H2 and Rn emissions of concrete blocks under increasing uniaxial compression

Electric resistance and emissions of hydrogen and radon isotopes of concrete (which is somewhat similar to fault-zone materials) under increasing uniaxial compression were continuously monitored to check whether they show any pre- and post-failure changes that may correspond to similar changes reported for earthquakes. The results show that all these parameters generally begin to increase when the applied stresses reach 20% to 90% of the corresponding failure stresses, probably due to the occurrence and growth of dilatant microcracks in the specimens. The prefailure changes have different patterns for different specimens, probably because of differences in spatial and temporal distributions of the microcracks. The resistance shows large co-failure increases, and the gas emissions show large post-failure increases. The post-failure increase of radon persists longer and stays at a higher level than that of hydrogen, suggesting a difference in the emission mechanisms for these two kinds of gases. The H₂ increase may be mainly due to chemical reaction at the crack surfaces while they are fresh, whereas the Rn increases may be mainly the result of the increased emanation area of such surfaces. The results suggest that monitoring of resistivity and gas emissions may be useful for predicting earthquakes and failures of concrete structures.     

Magnetic and mineralogical characteristics of hydrocarbon microseepage above oil/gas reservoirs of Tuoku region, northern Tarim Basin, China

The Tuoku region in northern Tarim Basin of China is a key area for studying oil/gas reservoir rocks. The magnetic and mineralogical parameters of well cuttings from two wells, well S₇, situated on oil/gas field, and well S₆, at an oil/water interface, were measured. The two wells are located in the same structure with similar strata and types of lithology, but well S₆ is a showing well of oil and gas 5 km northwest of well S₇. The purpose of this paper is to evaluate the possibility and distribution of secondary magnetic alteration that may have occurred due to hydrocarbon migration above an oil/gas accumulation. It is concluded that the magnetism of well cuttings from major strata in well S₇, including source rocks, oil reservoir rocks and cap rocks, and in Quaternary (Q) soil is higher than that from well S₆. The Cambrian oil-bearing strata and cap rocks have even higher magnetism in well S₇. The shape and parameters of magnetic hysteresis loops indicate that soft (H _c<20 mT,H _s<0.3 T) ferrimagnetic components dominate the magnetic carriers within the strongly magnetic strata of well S₇, whereas a mixed paramagnetic and ferrimagnetic distribution occurs in well S₆ (for example, low coecivityH _c and nonsaturating magnetized character). Analysis of heavy minerals shows that the contents of iron oxide (magnetite, maghemite and hematite) in well S₇ are often higher than those in well S₆. The magnetite content in samples of cuttings from Cambrian rocks can reach 9.7% in oil-bearing strata in well S₇, and in strata Ekm and N₁j are 1.215% and1.498%, respectively. Typical spherical magnetite grains are found within the main source rocks and the soils in well S₇. By analysis of surface microtexture and of trace element contents, we infer that the spherical magnetite is composed of aggregates of ultrafine particles that are probably authigenic magnetite formed in a hydrocarbon halo background. Project supported by the National Natural Science Foundation of China and the Geological Industry Foundation of China (Grant No. 49374216) and Foundation of the State Key Laboratory of Oil/Gas Reservoir Geology and Exploitation of China (Grant No. 9608).     

Stable carbon and hydrogen isotopes of gases from the large tight gas fields in China

By the end of the year 2010,a total of 15 large tight gas fields have been found in China,located in the Ordos,Sichuan,and Tarim basins.The annual production and total reserves of these fields in 2010 were 222.5×108and 28657×108m3,respectively,accounting for 23.5%and 37.3%,respectively,of the total annual production and reserves of natural gases in China.They took a major part of all natural gas production and reserves in China.According to the analyses of 81 gas samples,the stable carbon and hydrogen isotopic compositions of tight gases in China have following characteristics:(1)Plots of 13C1-13C2-13C3,13C1-C1/C2+3and 13C1-13C2demonstrate the coal-derived origin of tight gases in China;(2)For the primary alkane gases,both carbon and hydrogen isotopic values increase with increasing molecular mass,i.e.,13C113C213C313C4and2H12H22H3;(3)The isotopic differences of 13C2-13C1,13C3-13C1,2H2-2H1and 2H3-2H1decrease with increasing Ro(%)and C1/C1–4;(4)There are seven causes for the carbon and hydrogen isotopic reversal,however,the carbon and hydrogen isotopic reversal of tight gases in China is caused mainly by multiple stages of gas charge and accumulation.     

Effects of soil compaction,rain exposure and their interaction on soil carbon dioxide emission

Soils release more carbon, primarily as carbon dioxide (CO₂), per annum than current global anthropogenic emissions. Soils emit CO₂ through mineralization and decomposition of organic matter and respiration of roots and soil organisms. Given this, the evaluation of the effects of abiotic factors on microbial activity is of major importance when considering the mitigation of greenhouse gases emissions. Previous studies demonstrate that soil CO₂ emission is significantly affected by temperature and soil water content. A limited number of studies have illustrated the importance of bulk density and soil surface characteristics as a result of exposure to rain on CO₂ emission, however, none examine their relative importance. Therefore, this study investigated the effects of soil compaction and exposure of the soil surface to rainfall and their interaction on CO₂ release. We conducted a factorial laboratory experiment with three soil types after sieving (clay, silt and sand soil), three different bulk densities (1·1 g cm^–3, 1·3 g cm^–3, 1·5 g cm^–3) and three different exposures to rainfall (no rain, 30 minutes and 90 minutes of rainfall). The results demonstrated CO₂ release varied significantly with bulk density, exposure to rain and time. The relationship between rain exposure and CO₂ is positive: CO₂ emission was 53% and 42% greater for the 90 minutes and 30 minutes rainfall exposure, respectively, compared to those not exposed to rain. Bulk density exhibited a negative relationship with CO₂ emission: soil compacted to a bulk density of 1·1 g cm^–3 emitted 32% more CO₂ than soil compacted to 1·5 g cm^–3. Furthermore we found that the magnitude of CO₂ effluxes depended on the interaction of these two abiotic factors. Given these results, understanding the influence of soil compaction and raindrop impact on CO₂ emission could lead to modified soil management practices which promote carbon sequestration. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of mining and related activities on the sediment trace element geochemistry of Lake Coeur D'Alene,Idaho, USA part II: Subsurface sediments

During the summer of 1990, 12 gravity cores were collected in Lake Coeur d'Alene, Idaho at various depths and in a variety of depositional environments. All core subsamples were analysed to determine the bulk sediment chemistry; selected subsamples were analysed for trace element partitioning and ¹³⁷Cs activity. The purpose of these analyses was to determine the trace element concentrations and distributions in the sediment column and to try to establish a trace element geochemical history of the lake in relation to mining and mining-related discharge operations in the area. Substantial portions of the near-surface sediments in Lake Coeur d'Alene are markedly enriched in Ag, As, Cd, Hg, Pb, Sb and Zn, and slightly enriched in Cu, Fe and Mn. Variations in the thickness of the trace element-rich sediments, which range from more than 119 cm to as little as 17 cm, indicate that the source of much of this material is the Coeur d'Alene River. An estimated 75 million tonnes of trace element-rich sediments have been deposited on or in the lake bed. Estimated trace element masses in excess of those considered representative of background conditions range from a high of 468 000 tonnes of Pb to a low of 260 tonnes of Hg. The similarity between the trace element-rich surface and subsurface sediments with respect to their location, their bulk chemistry, their interelement relations and their trace element partitioning indicate that the sources and/or concentrating mechanisms causing the trace element enrichment in the lake sediments have probably been the same through-out their depositional history. Based on a Mt St Helens'ash layer from the 1980 eruption, ages estimated from ¹³⁷Cs activity and the presence of 80 discernible and presumably annual layers in a core collected near the Coeur d'Alene River delta indicate that deposition rates for the trace element-rich sediments have ranges from 2.1 to 1.3 cm/year. These data also indicate that the deposition of trace element-rich sediments began, at least in the Coeur d'Alene River delta, some time between 1895 and 1910, dates consistent with the onset of mining and ore processing activities that began in the area in the 1880s.     

Organic and inorganic geochemistry of low temperature gas discharges at the Baia di Levante beach, Vulcano Island, Italy

Discharge from subaereal and submarine gas vents of the Baia di Levante beach gases from the Vulcano Island were sampled for major and trace gas components in May and November 1995.Chemical compositions and equilibrium calculations suggest three different groups of CO₂-rich gas emissions depending on their distance from the La Fossa crater: (1) gas vents close to the Faraglione area are characterised by high H₂S contents, high calculated equilibrium temperatures based on inorganic species and relatively high proportion of alkene compounds; (2) gas vents close to Vulcanello are characterised by low calculated equilibrium temperatures and low amounts of alkenes; and (3) Pontile sample has the highest equilibrium CO₂ pressure (up to 68 bars) which may account for the observed absence of benzene. The relative large variability of H₂S in the Baia di Levante beach gas discharge may be attributed to either different interactions between iron sulphides and weakly acid waters or catalytic effect of elemental sulphur on the de-hydrogenation of cyclo-hexane. Thermodynamic calculations suggest that the main inorganic species and CH₄ may have re-equilibrated at relatively shallow depth (10–200 m b.s.l. and 30–600 m b.s.l. for a lithostatic and hydrostatic pressure, respectively). The slow kinetics of reactions in the C_nH_2n/C_nH_2n+2 systems, with respect to that of CH₄–CO–CO₂, may explain the observed propene/propane ratios, which can only be reached at reaction temperatures of 300–350°C. This low speed of reactions can also explain the observed disequilibrium of C1–C4 alkanes.     

Sulfur dioxide emissions from Popocatépetl volcano (Mexico): case study of a high-emission rate, passively degassing erupting volcano

Popocatépetl volcano in central Mexico has been erupting explosively and effusively for almost 4 years. SO₂ emission rates from this volcano have been the largest ever measured using a COSPEC. Pre-eruptive average SO₂ emission rates (2–3 kt/d) were similar to the emission rates measured during the first part of the eruption (up to August 1995) in contrast with the effusive–explosive periods (March 1996–January 1998) during which SO₂ emission rates were higher by a factor of four (9–13 kt/d). Based on a chronology of the eruption and the average SO₂ emission rates per period, the total SO₂ emissions (up to 1 January 1998) are estimated to be about 9 Mt, roughly half as much as the SO₂ emissions from Mount Pinatubo in a shorter period. Popocatépetl volcano is thus considered as a high-emission rate, passively degassing eruptive volcano. SO₂ emission rates and SO₂ emissions are used here to make a mass balance of the erupted magma and related gases. Identified excess SO₂ is explained in terms of continuous degassing of unerupted magma and magma mixing. Fluctuations in SO₂ emission rate may be a result of convection and crystallization in the chamber or the conduits, cleaning and sealing of the plumbing system, and/or SO₂ scrubbing by the hydrothermal system.     

Effect of mining and related activities on the sediment trace element geochemistry of lake coeur D'Alene,idaho, USA. Part I: Surface sediments

During the summer of 1989 surface sediment samples were collected in Lake Coeur d'Alene, the Coeur d'Alene River and the St Joe River, Idaho, at a density of approximately one sample per square kilometre. Additional samples were collected from the banks of the South Fork of the Coeur d'Alene and the Coeur d'Alene Rivers in 1991. All the samples were collected to determine trace element concentrations, partitioning and distribution patterns, and to relate them to mining, mining related and discharge operations that have occurred in the Coeur d'Alene district since the 1880s, some of which are ongoing. Most of the surface sediments in Lake Coeur d'Alene north of Conkling Point and Carey Bay are substantially enriched in Ag, As, Cu, Cd, Hg, Pb, Sb and Zn relative to unaffected sediments in the southern portion of the lake near the St Joe River. All the trace element enriched sediments are extremely fine grained (mean grain sizes « 63 μm). Most of the enriched trace elements, based on both the chemical analyses of separated heavy and light mineral fractions and a two step sequential extraction procedure, are associated with an operationally defined Fe oxide phase; much smaller percentages are associated either with operationally defined organics/sulphides or refractory phases. The presence, concentration and distribution of the Fe oxides and heavy minerals indicates that a substantial portion of the enriched trace elements are probably coming from the Coeur d'Alene River, which is serving as a point source. Within the lake, this relatively simple point source pattern is complicated by a combination of (1) the formation of trace element rich authigenic Fe oxides that appear to have reprecipitated from material solubilized from anoxic bed sediments and (2) physical remobilization by currents and wind driven waves. The processes that have caused the trace element enrichment in the surface sediments of Lake Coeur d'Alene are likely to continue for the foreseeable future.     

Molecular and carbon isotopic compositions of gas inclusions of deep carbonate rocks in the Tarim Basin

Gaseous components of gas inclusions in deep carbonate rocks (>5700 m) from the Tacan 1 well were analyzed by online mass spectrometry by means of either the stepwise heating technique or vacuum electromagnetism crushing. The carbon isotopic compositions of gases released by vacuum electromagnetism crushing were also measured. Although the molecular compositions of gas inclusions show differences between the two methods, the overall characteristics are that gas inclusions mainly contain CO2, whilst hydrocarbon gases, such as CH4, C2H6 and C3H8, are less abundant. The content of CO is higher in the stepwise heating experiment than that in the method of vacuum electromagnetism crushing, and there are only minor amounts of N2, H2 and O2 in gas inclusions. Methane δ13C values of gas inclusions in Lower Ordovician and Upper Cambrian rocks (from 5713.7 to 6422 m; -52‰-63‰) are similar to those of bacterial methane, but their chemical compositions do not exhibit the dry character in comparison with biogenic gases. These characteristics of deep gas inclusions may be related to the migration fractionation. Some deep natural gases with light carbon isotopic characteristics in the Tazhong Uplift may have a similar origin. The δ13C1 values of gas inclusions in Lower Cambrian rocks (7117-7124 m) are heavier (-39‰), consistent with highly mature natural gases. Carbon isotopic compositions of CO2 in the gas inclusions of deep carbonate rocks are similar (from -4‰ to -13‰) to those of deep natural gases, indicating predominantly an inorganic origin.     

The components and carbon isotope of the gases in inclusions in reservoir layers of Upper Paleozoic gas pools in the Ordos Basin,China

The components and carbon isotope of gases in inclusions are one of the most important geochemical indexes for gas pools.The analysis results of the components and carbon isotope of gases from inclusions in reservoir layers of Upper Palaeozoic gas pools in the Ordos Basin show that most inclusions grown in reservoir sandstone are primary inclusions.There is only a little difference about the components and carbon isotope between the well gases and the secondary inclusions gases.This indicated that the epigenetic change of gas pools is little.This difference between the well gases and the secondary inclusions gases is caused by two reasons:(i)The well gases come from several disconnected sand bodies buried in a segment of depth,while the inclusion gases come from a point of depth.(ii)The secondary inclusions trapped the gases generated in the former stage of source rock gas generation,and the well gases are the mixed gases generated in all the stages.It is irresponsible to reconstruct the palaeo-temperature and palaeo-pressure under which the gas pool formed using carbon dioxide inclusions.     

Characteristics,genesis and accumulation history of natural gas in Hetianhe gasfield,Tarim Basin,China

Hetianhe gasfield in Bachu region of the Tarim Basin is mainly composed of three reservoir-caprock assembly,namely regional caprock of upper mudstone,middle mudstone and lower mudstone of the Carboniferous and reservoir of Bachu bioclastic limestone,glutenite and the Ordovician carbonate buried hill.Natural gas in Hetianhe gasfield sourced from the Cambrian source rock.It is thought that gases in Ma4 well block in the east of Hetianhe gasfield are mainly crude-oil cracked gases,while those in Ma3 and Ma8 well blocks in the west are the mixture gases of kerogen cracked gases and crude-oil cracked gases.Natural gas is rich in H2S and accumulated in multiply stages as the result of TSR.The accumulation history is divided into three stages,namely accumulation and breakage in the late Caledonian-early Hercynian,migration and dissipation in the late Hercynian and accumulation in Himalayan. The main accumulation of reformed gas reservoir is in Himalayan.     

Geochemical characteristics of pyrolysis gas from epimetamorphic rocks in the northern basement of Songliao Basin,Northeast China

The Xushen gas field,located in the north of Songliao Basin,is a potential giant gas area for China in the future.Its proved reserves have exceeded 1000×10 8 m 3 by the end of 2005.But,the origin of natural gases from the deep strata is still in debating.Epimetamorphic rocks as a potential gas source are widely spreading in the northern basement of Songliao Basin.According to pyrolysis experiments for these rocks in the semi-confined system,gas production and geochemistry of alkane gases are discussed in this paper.The Carboniferous-Permian epimetamorphic rocks were heated from 300℃to 550℃,with temperature interval of 50℃.The gas production was quantified and measured for chemical and carbon isotopic compositions.Results show thatδ13C 1 is less than?20‰,carbon isotope trend of alkane gas isδ13C 1 <δ13C 2 <δ13C 3 orδ13C 1 <δ13C 2 >δ13C 3 ,these features suggest that the gas would be coal-type gas at high-over maturity,not be inorganic gas with reversal trend of gaseous alkanes (δ13C 1 >δ13C 2 >δ13C 3 ).These characteristics of carbon isotopes are similar with the natural gas from the basin basement,but disagree with gas from the Xingcheng reservoir.Thus,the mixing gases from the pyrolysis gas with coal-typed gases at high-over maturity or oil-typed gases do not cause the reversal trend of carbon isotopes.The gas generation intensity for epimetamorphic rocks is 3.0×10 8 ―23.8×10 8 m 3 /km 2 ,corresponding to Ro from 2.0%to 3.5%for organic matter.