Soil gas composition above gas deposits and perspective structures of the Carpathian Foredeep,SE Poland     

Henryk Sechman  Marek Dzieniewicz  Bogusław Liszka 《Applied Geochemistry》2012

In 2001 a surface geochemical survey was carried out in the Carpathian Foredeep, in the area between Jaros?aw and Radymno (SE Poland) where multihorizon gas deposits were discovered. These deposits accumulate microbial CH₄ with small amounts of N₂ and higher molecular weight gaseous hydrocarbons. Soil–gas composition in the hydrocarbon fields in the study area is relatively different from the original composition of natural gas occurring in the subsurface reservoir. In 449 analyzed soil gas samples collected from 1.2 m depth relatively low concentrations were found for CH₄ (median value 2.2 ppm) and its homologues (median value of total alkanes C₂–C₄ – 0.02 ppm). Alkenes were encountered in 36.3% of the analyzed samples (mean value of total alkenes C₂–C₄ – 0.015 ppm) together with distinctly higher concentrations of H₂ (maximum value – 544 ppm, mean value – 42 ppm) and CO₂ (maximum value – 10.26 vol.%, mean value – 2.27 vol.%). Individual, very high concentrations of CH₄ (up to about 35 vol.%) resulted from sub-surface biochemical reactions whereas higher alkanes detected in soil gases (up to about 68 ppm) originated from deep gas accumulations. Both the H₂ and alkenes may be indirect indicators of deep hydrocarbon accumulations. Carbon dioxide may also be useful for hydrocarbon exploration, revealing increased concentrations in those sampling sites where CH₄ concentrations are strongly depleted, presumably due to bacterial oxidation. These relationships are valid only for the study area and should not be extended as an universal principle.  相似文献   

Origin and spatial distribution of gas at seismogenic depths of the San Andreas Fault from drill-mud gas analysis   总被引：1，自引：0，他引：1  

Thomas Wiersberg  Jörg Erzinger 《Applied Geochemistry》2008

Data are presented on the molecular composition of drill-mud gas from the lower sedimentary section (1800–3987 m) of the SAFOD (San Andreas Fault Observatory at Depth) Main Hole measured on-line during drilling, as well as C and H isotope data from off-line mud gas samples. Hydrocarbons, H₂ and CO₂ are the most abundant non-atmospheric gases in drill-mud when drilling seismogenic zones. Gas influx into the well at depth is related to the lithology and permeability of the drilled strata: larger formation gas influx was detected when drilling through organic-rich shales and permeable sandstones. The SAF (San Andreas Fault), encountered between approximately 3100 m and 3450 m borehole depth, is generally low in gas, but is encompassed by two gas-rich zones (2700–2900 m and below 3550 m) at the fault margins with enhanced ²²²Rn activities and distinct gas compositions. Within the fault, two interstratified gas-rich lenses (3150–3200 m and 3310–3340 m) consist of CO₂ and hydrocarbons (upper zone), but almost exclusively of hydrocarbons (lower zone).  相似文献   

Armouring of well cement in H₂S–CO₂ saturated brine by calcite coating – Experiments and numerical modelling     

Nicolas Jacquemet  Jacques Pironon  Vincent Lagneau  Jérémie Saint-Marc 《Applied Geochemistry》2012

The active acid gas (H₂S–CO₂ mixture) injection operations in North America provide practical experience for the operators in charge of industrial scale CO₂ geological storage sites. Potential leakage via wells and their environmental impacts make well construction durability an issue for efficiency/safety of gas geological storage. In such operations, the well cement is in contact with reservoir brines and the injected gas, meaning that gas–water–solid chemical reactions may change the physical properties of the cement and its ability to confine the gas downhole. The cement-forming Calcium silicate hydrates carbonation (by CO₂) and ferrite sulfidation (by H₂S) reactions are expected. The main objective of this study is to determine their consequences on cement mineralogy and transfer ability. Fifteen and 60 days duration batch experiments were performed in which well cement bars were immersed in brine itself caped by a H₂S–CO₂ phase at 500 bar–120 °C. Scanning electron microscopy including observations/analyses and elemental mapping, mineralogical mapping by micro-Raman spectroscopy, X-ray diffraction and water porosimetry were used to characterize the aged cement. Speciation by micro-Raman spectroscopy of brine trapped within synthetic fluid inclusions were also performed. The expected calcium silicate hydrates carbonation and ferrite sulfidation reactions were evidenced. Furthermore, armouring of the cement through the fast creation of a non-porous calcite coating, global porosity decrease of the cement (clogging) and mineral assemblage conservation were demonstrated. The low W/R ratio of the experimental system (allowing the cement to buffer the interstitial and external solution pH at basic values) and mixed species diffusion and chemical reactions are proposed to explain these features. This interpretation is confirmed by reactive transport modelling performed with the HYTEC code. The observed cement armouring, clogging and mineral assemblage conservation suggest that the tested cement has improved transfer properties in the experimental conditions. This work suggests that in both acid gas and CO₂ geological storage, clogging of cement or at least mineral assemblage conservation and slowing of carbonation progress could occur in near-well zones where slight water flow occurs e.g. in the vicinity of caprock shales.  相似文献   

The noble gas geochemistry of natural CO₂ gas reservoirs from the Colorado Plateau and Rocky Mountain provinces, USA     

Stuart M.V. Gilfillan  Chris J. Ballentine  Dave Blagburn  Scott Stevens  Martin Cassidy 《Geochimica et cosmochimica acta》2008,72(4):1174-1198

Identification of the source of CO₂ in natural reservoirs and development of physical models to account for the migration and interaction of this CO₂ with the groundwater is essential for developing a quantitative understanding of the long term storage potential of CO₂ in the subsurface. We present the results of 57 noble gas determinations in CO₂ rich fields (>82%) from three natural reservoirs to the east of the Colorado Plateau uplift province, USA (Bravo Dome, NM., Sheep Mountain, CO. and McCallum Dome, CO.), and from two reservoirs from within the uplift area (St. John’s Dome, AZ., and McElmo Dome, CO.). We demonstrate that all fields have CO₂/³He ratios consistent with a dominantly magmatic source. The most recent volcanics in the province date from 8 to 10 ka and are associated with the Bravo Dome field. The oldest magmatic activity dates from 42 to 70 Ma and is associated with the McElmo Dome field, located in the tectonically stable centre of the Colorado Plateau: CO₂ can be stored within the subsurface on a millennia timescale.The manner and extent of contact of the CO₂ phase with the groundwater system is a critical parameter in using these systems as natural analogues for geological storage of anthropogenic CO₂. We show that coherent fractionation of groundwater ²⁰Ne/³⁶Ar with crustal radiogenic noble gases (⁴He, ²¹Ne, ⁴⁰Ar) is explained by a two stage re-dissolution model: Stage 1: Magmatic CO₂ injection into the groundwater system strips dissolved air-derived noble gases (ASW) and accumulated crustal/radiogenic noble gas by CO₂/water phase partitioning. The CO₂ containing the groundwater stripped gases provides the first reservoir fluid charge. Subsequent charges of CO₂ provide no more ASW or crustal noble gases, and serve only to dilute the original ASW and crustal noble gas rich CO₂. Reservoir scale preservation of concentration gradients in ASW-derived noble gases thus provide CO₂ filling direction. This is seen in the Bravo Dome and St. John’s Dome fields. Stage 2: The noble gases re-dissolve into any available gas stripped groundwater. This is modeled as a Rayleigh distillation process and enables us to quantify for each sample: (1) the volume of groundwater originally ‘stripped’ on reservoir filling; and (2) the volume of groundwater involved in subsequent interaction. The original water volume that is gas stripped varies from as low as 0.0005 cm³ groundwater/cm³ gas (STP) in one Bravo Dome sample, to 2.56 cm³ groundwater/cm³ gas (STP) in a St. John’s Dome sample. Subsequent gas/groundwater equilibration varies within all fields, each showing a similar range, from zero to ∼100 cm³ water/cm³ gas (at reservoir pressure and temperature).  相似文献   

Potential environmental issues of CO₂ storage in deep saline aquifers: Geochemical results from the Frio-I Brine Pilot test,Texas, USA     

Yousif K. Kharaka  James J. Thordsen  Susan D. Hovorka  H. Seay Nance  David R. Cole  Tommy J. Phelps  Kevin G. Knauss 《Applied Geochemistry》2009

Sedimentary basins in general, and deep saline aquifers in particular, are being investigated as possible repositories for large volumes of anthropogenic CO₂ that must be sequestered to mitigate global warming and related climate changes. To investigate the potential for the long-term storage of CO₂ in such aquifers, 1600 t of CO₂ were injected at 1500 m depth into a 24-m-thick “C” sandstone unit of the Frio Formation, a regional aquifer in the US Gulf Coast. Fluid samples obtained before CO₂ injection from the injection well and an observation well 30 m updip showed a Na–Ca–Cl type brine with ∼93,000 mg/L TDS at saturation with CH₄ at reservoir conditions; gas analyses showed that CH₄ comprised ∼95% of dissolved gas, but CO₂ was low at 0.3%. Following CO₂ breakthrough, 51 h after injection, samples showed sharp drops in pH (6.5–5.7), pronounced increases in alkalinity (100–3000 mg/L as HCO₃) and in Fe (30–1100 mg/L), a slug of very high DOC values, and significant shifts in the isotopic compositions of H₂O, DIC, and CH₄. These data, coupled with geochemical modeling, indicate corrosion of pipe and well casing as well as rapid dissolution of minerals, especially calcite and iron oxyhydroxides, both caused by lowered pH (initially ∼3.0 at subsurface conditions) of the brine in contact with supercritical CO₂.  相似文献   

On the interaction of pure and impure supercritical CO₂ with rock forming minerals in saline aquifers: An experimental geochemical approach     

Franziska D.H. Wilke  Mónica Vásquez  Thomas Wiersberg  Rudolf Naumann  Jörg Erzinger 《Applied Geochemistry》2012

The aim of this experimental study was to evaluate and compare the geochemical impact of pure and impure CO₂ on rock forming minerals of possible CO₂ storage reservoirs. This geochemical approach takes into account the incomplete purification of industrial captured CO₂ and the related effects during injection, and provides relevant data for long-term storage simulations of this specific greenhouse gas. Batch experiments were conducted to investigate the interactions of supercritical CO₂, brine and rock-forming mineral concentrates (albite, microcline, kaolinite, biotite, muscovite, calcite, dolomite and anhydrite) using a newly developed experimental setup. After up to 42 day (1000 h) experiments using pure and impure supercritical CO₂ the dissolution and solution characteristics were examined by XRD, XRF, SEM and EDS for the solid, and ICP–MS and IC for the fluid reactants, respectively. Experiments with mixtures of supercritical CO₂ (99.5 vol.%) and SO₂ or NO₂ impurities (0.5 vol.%) suggest the formation of H₂SO₄ and HNO₃, reflected in pH values between 1 and 4 for experiments with silicates and anhydrite and between 5 and 6 for experiments with carbonates. These acids should be responsible for the general larger amount of cations dissolved from the mineral phases compared to experiments using pure CO₂. For pure CO₂ a pH of around 4 was obtained using silicates and anhydrite, and 7–8 for carbonates. Dissolution of carbonates was observed after both pure and impure CO₂ experiments. Anhydrite was corroded by approximately 50 wt.% and gypsum precipitated during experiments with supercritical CO₂ + NO₂. Silicates do not exhibit visible alterations during all experiments but released an increasing amount of cations in the reaction fluid during experiments with impure CO₂. Nonetheless, precipitated secondary carbonates could not be identified.  相似文献   

Chemical and isotopic evidence for secondary alteration of natural gases in the Hetianhe Field, Bachu Uplift of the Tarim Basin   总被引：2，自引：0，他引：2  

Chunfang Cai  Richard H Worden  Qinghua Wang  Tingsheng Xiang  Jingquan Zhu  Xuelei Chu 《Organic Geochemistry》2002,33(12)

H₂S and CO₂ are found in elevated concentrations in the reservoirs near the Carboniferous–Ordovician unconformity in the Hetianhe Field of the Tarim Basin, NW China. Chemical and isotopic analyses have been performed on produced gases, formation waters and reservoir rocks to determine the origin of CO₂ and H₂S and to explain the heterogeneous distribution of isotopic and geochemical characteristics of petroleum fluids. It is unlikely that H₂S and CO₂ had a mantle component since associated helium has an isotope ratio totally uncharacteristic of this source. Instead, H₂S and CO₂ are probably the result of sulphate reduction of the light hydrocarbon gases (LHG). Increasing H₂S concentrations and CO₂/(CO₂+ΣC_1–4) values to the west of the Hetianhe Field occur commensurately with increasingly heavy hydrocarbon gas δ¹³C values. However, thermochemical sulphate reduction is unlikely because the temperatures of the reservoirs are too low, no H₂S or rare pyrite was detected in deeper reservoirs (where more TSR should have occurred) and inferred δ³⁴S values of H₂S (from late-stage pyrite in the Carboniferous and Ordovician reservoirs) are as low as −24.9‰. Such low δ³⁴S values discount the decomposition of organic matter as a major source of H₂S and CO₂. Bacterial sulphate reduction of the light hydrocarbon gases in the reservoir, possibly coupled indirectly with the consumption of organic acids and anions is most likely. The result is the preferential oxidation of ¹²C-rich alkanes (due to the kinetic isotope effect) and decreasing concentration of organic acids and anions. Modern formation water stable isotope data reveal that it is possible that sulphate-reducing bacteria were introduced into the reservoir by an influx of meteoric water from the west by way of an inversion-related unconformity. This may account for the apparently stronger influence of bacterial sulphate reduction to the west of the Hetianhe Field, and the consequent greatest decrease of the δ¹³C-CO₂ values and the greatest increase in δ¹³C values of the alkane gases.  相似文献   

Was the lethal eruption of Lake Nyos related to a double CO₂/H₂O density inversion?     

Jacques Touret  Michel Grégoire  Merlin Teitchou 《Comptes Rendus Geoscience》2010,342(1):19-26

The 1986 lethal eruption of Lake Nyos (Cameroon) was caused by a sudden inversion between deep, CO₂-loaded bottom lake waters and denser, gas-free surface waters. A deep CO₂ source has been found in fluid inclusions which occur predominantly in clinopyroxenes from lherzolitic mantle xenoliths, brought to the surface by the last erupted alkali basalts. P–T conditions of CO₂ trapping correspond to a gas density equal (or higher) than that of liquid water. It is suggested that this dense CO₂, found in many ultrabasic mantle xenoliths worldwide, has accumulated at km depth, below a column of descending lake water. It may remain in a stable state for a long period, as long as the temperature is above the density inversion temperature for pure H₂O/CO₂ systems. At an estimated depth of about 3 km, cooling by descending waters (to about 30 °C) induces a density inversion for the upper part of the CO₂ reservoir. This causes a constant, regular upstream of low-density CO₂ which, in its turn, feeds the shallower lake density inversion.  相似文献   

Surface heat flow and CO₂ emissions within the Ohaaki hydrothermal field,Taupo Volcanic Zone,New Zealand     

Clinton Rissmann  Bruce Christenson  Cynthia Werner  Matthew Leybourne  Jim Cole  Darren Gravley 《Applied Geochemistry》2012

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW_e). Soil CO₂ degassing was quantified with 2663 CO₂ flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m⁻²) using published soil temperature heat flow functions. Both CO₂ flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO₂ gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO₂ emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO₂ emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they contributed little (<1%) to pre-production CO₂ emissions due to the loss of >99% of the original CO₂ content due to depressurisation and boiling as the fluids ascended to the surface. Consequently, the soil has persisted as the major (99%) pathway of CO₂ release to the atmosphere from the high temperature reservoir at Ohaaki. The CO₂ flux and heat flow surveys indicate that despite 20 a of production the variability in location, spatial extent and magnitude of CO₂ flux remains consistent with established geochemical and geophysical models of the Ohaaki Field. At both OHW and OHE carbon isotopic analyses of soil gas indicate a two-stage fractionation process for moderate-flux (>60 g m⁻² d⁻¹) sites; boiling during fluid ascent within the underlying reservoir and isotopic enrichment as CO₂ diffuses through porous media of the soil zone. For high-flux sites (>300 g m⁻² d⁻¹), the δ¹³CO₂ signature (−7.4 ± 0.3‰ OHW and −6.5 ± 0.6‰ OHE) is unaffected by near-surface (soil zone) fractionation processes and reflects the composition of the boiled magmatic CO₂ source for each respective upflow. Flux thresholds of <30 g m⁻² d⁻¹ for purely diffusive gas transport, between 30 and 300 g m⁻² d⁻¹ for combined diffusive–advective transport, and ?300 g m⁻² d⁻¹ for purely advective gas transport at Ohaaki were assigned. δ¹³CO₂ values and cumulative probability plots of CO₂ flux data both identified a threshold of ∼15 g m⁻² d⁻¹ by which background (atmospheric and soil respired) CO₂ may be differentiated from hydrothermal CO₂.  相似文献   

Diffuse gas emissions at the Ukinrek Maars,Alaska: Implications for magmatic degassing and volcanic monitoring     

William C. Evans  Deborah Bergfeld  Robert G. McGimsey  Andrew G. Hunt 《Applied Geochemistry》2009

Diffuse CO₂ efflux near the Ukinrek Maars, two small volcanic craters that formed in 1977 in a remote part of the Alaska Peninsula, was investigated using accumulation chamber measurements. High CO₂ efflux, in many places exceeding 1000 g m⁻² d⁻¹, was found in conspicuous zones of plant damage or kill that cover 30,000–50,000 m² in area. Total diffuse CO₂ emission was estimated at 21–44 t d⁻¹. Gas vents 3-km away at The Gas Rocks produce 0.5 t d⁻¹ of CO₂ that probably derives from the Ukinrek Maars basalt based on similar δ¹³C values (∼−6‰), ³He/⁴He ratios (5.9–7.2 R_A), and CO₂/³He ratios (1–2 × 10⁹) in the two areas. A lower ³He/⁴He ratio (2.7 R_A) and much higher CO₂/³He ratio (9 × 10¹⁰) in gas from the nearest arc-front volcanic center (Mount Peulik/Ugashik) provide a useful comparison. The large diffuse CO₂ emission at Ukinrek has important implications for magmatic degassing, subsurface gas transport, and local toxicity hazards. Gas–water–rock interactions play a major role in the location, magnitude and chemistry of the emissions.  相似文献   

川东宣汉地区天然气地球化学特征及成因   总被引：13，自引：1，他引：12       下载免费PDF全文

朱扬明  王积宝  郝芳  邹华耀  蔡勋育 《地质科学》2008,43(3):518-532

依据10余口探井60多个气样的化学成份和碳同位素组成数据,结合烃源岩和储层沥青分析资料,系统剖析了四川盆地东部宣汉地区普光、毛坝场等构造带天然气地球化学特征,并探讨了其成因及来源。研究结果表明:这些构造带中飞仙关组—长兴组天然气为高含硫化氢的干气,天然气化学成份表现出古油藏原油裂解气的特点。其烃类气体中以甲烷为主(高于99.5%);富含非烃气体,CO₂和H₂S平均含量分别达5.32%和11.95%。甲烷碳同位素较重(-33‰～-29‰),表征高热演化性质;乙烷δ¹³C值主要分布在-33‰至-28‰范围,属油型气。这些天然气与川东邻近气田的同层位天然气具有同源性,而与石炭系气藏天然气在化学成份、碳同位素组成上有所不同,意味着有不同的气源。硫化物硫同位素和沥青元素组成证实高含量的H₂S是气藏发生TSR作用所致。δ³⁴S值表征层状沉积成因的硬石膏是TSR作用的反应物,而脉状硬石膏则是其残余物。储层的孔隙类型可能与TSR作用强度和H₂S含量高低有联系,裂缝型气层中H₂S少,孔洞型储层中H₂S丰富。乙烷、沥青和各层系烃源岩干酪根碳同位素对比表明研究区飞仙关组—长兴组气藏天然气主要来自二叠系烃源层。  相似文献   

Gases in Taiwan mud volcanoes: Chemical composition,methane carbon isotopes,and gas fluxes     

Hung-Chun Chao  Chen-Feng You  Chih-Hsien Sun 《Applied Geochemistry》2010

Mud volcanoes are important pathways for CH₄ emission from deep buried sediments; however, the importance of gas fluxes have hitherto been neglected in atmospheric source budget considerations. In this study, gas fluxes have been monitored to examine the stability of their chemical compositions and fluxes spatially, and stable C isotopic ratios of CH₄ were determined, for several mud volcanoes on land in Taiwan. The major gas components are CH₄ (>90%), “air” (i.e. N₂ + O₂ + Ar, 1–5%) and CO₂ (1–5%) and these associated gas fluxes varied slightly at different mud volcanoes in southwestern Taiwan. The Hsiao-kun-shui (HKS) mud volcano emits the highest CH₄ concentration (CH₄ > 97%). On the other hand, the Chung-lun mud volcano (CL) shows CO₂ up to 85%, and much lower CH₄ content (<37%). High CH₄ content (>90%) with low CO₂ (<0.2%) are detected in the mud volcano gases collected in eastern Taiwan. It is suggestive that these gases are mostly of thermogenic origin based on C₁ (methane)/C₂ (ethane) + C₃ (propane) and δ¹³C_CH4 results, with the exception of mud volcanoes situated along the Gu-ting-keng (GTK) anticline axis showing unique biogenic characteristics. Only small CH₄ concentration variations, <2%, were detected in four on-site short term field-monitoring experiments, at Yue-shi-jie A, B, Kun-shui-ping and Lo-shan A. Preliminary estimation of CH₄ emission fluxes for mud volcanoes on land in Taiwan fall in a range between 980 and 2010 tons annually. If soil diffusion were taken into account, the total amount of mud volcano CH₄ could contribute up to 10% of total natural CH₄ emissions in Taiwan.  相似文献   

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV Acid–sulfate waters     

D. Kirk Nordstrom  R. Blaine McCleskeyJames W. Ball 《Applied Geochemistry》2009

Many waters sampled in Yellowstone National Park, both high-temperature (30–94 °C) and low-temperature (0–30 °C), are acid–sulfate type with pH values of 1–5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H₂S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH < 2.7. Field pH measurements were predominantly used because the charge imbalance was <±10%. When the charge imbalance was generally >±10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H₂S or S₂O₃ oxidation, CO₂ degassing, and the temperature-dependence of pK₂ for H₂SO₄. Charge imbalances are shown to be dependent on a speciation model for pH values <3. The highest SO₄ concentrations, in the thousands of mg/L, result from evaporative concentration at elevated temperatures as shown by the consistently high δ¹⁸O values (−10‰ to −3‰) and a δD vs. δ¹⁸O slope of 3, reflecting kinetic fractionation. Low SO₄ concentrations (<100 mg/L) for thermal waters (>350 mg/L Cl) decrease as the Cl⁻ concentration increases from boiling which appears inconsistent with the hypothesis of H₂S oxidation as a source of hydrothermal SO₄. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid–sulfate water analyses are occasionally high in As, Hg, and NH₃ concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO₄, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone’s acid waters but have not been observed in acid rock drainage of the same pH.  相似文献   

A geochemical study on mud volcanoes in the Junggar Basin, China     

Ryoichi Nakada  Yoshio TakahashiUrumu Tsunogai  Guodong ZhengHiroshi Shimizu  Keiko H. Hattori 《Applied Geochemistry》2011,26(7):1065-1076

A comprehensive study was performed to characterize, for the first time, the mud, water, and gases released from onshore mud volcanoes located in the southern margin of the Junggar Basin, northwestern China. Chemical compositions of mud, along with the geology of the basin, suggest that a source of the mud is Mesozoic or Cenozoic shale. Oxygen and H isotope compositions of the released water suggest a local meteoric origin. Combined with the positive Eu anomalies of the water, a large ¹⁸O shift of the water suggests extensive interaction with rocks. Gases discharged from the mud volcanoes are predominantly thermogenic hydrocarbons, and the high δ¹³C values (>+20‰ VPDB) for CO₂ gases and dissolved carbonate in muddy water suggest secondary methanogenesis with CO₂ reduction after oil biodegradation.The enrichments of Eu and ¹⁸O in water and the low thermal gradient of the area suggest that the water-rock interactions possibly occur deeper than 3670 ± 200 m. On the other hand, considering the relationship to the petroleum reservoir around the mud volcanoes, the depth of the gases can be derived from about 3600 m, a depth that is greater than that generally estimated for reservoirs whose gas is characterized by ¹³C-enriched CO₂. Oil biodegradation with CO₂ reduction likely occurs at a shallower depth along the seepage system of the mud volcano. The results contribute to the worldwide data set of gas genesis in mud volcanoes. Moreover, they further support the concept that most terrestrial mud volcanoes release thermogenic gas produced in very deep sediments and may be early indicators of oil biodegradation, an important problem in the petroleum industry.  相似文献   

Geochemical characterization of secondary microbial gas occurrence in the Songliao Basin, NE China     

Shuichang Zhang  Haiping Huang  Zihui FengYanhua Shuai 《Organic Geochemistry》2011,42(7):781-790

A suite of natural gases from the northern Songliao Basin in NE China were characterized for their molecular and carbon isotopic composition. Gases from shallow reservoirs display clear geochemical evidence of alteration by biodegradation, with very high dryness (C₁/C₂₊ > 100), high C₂/C₃ and i-C₄/n-C₄ ratios, high nitrogen content and variable carbon dioxide content. Isotopic values show wide range variations (δ¹³C_CH4 from −79.5‰ to −45.0‰, δ¹³C_C2H6 from −53.7‰ to −32.2‰, δ¹³C_C3H8 from −36.5‰ to −20.1‰, δ¹³C_nC4H10 from −32.7‰ to −24.5‰, and δ¹³C_CO2 from −21.6‰ to +10.5‰). A variety of genetic types can be recognized on the basis of chemical and isotopic composition together with their geological occurrence. Secondary microbial gas generation was masked by primary microbial gas and the mixing of newly generated methane with thermogenic methane already in place in the reservoir can cause very complicated isotopic signatures. System openness also was considered for shallow biodegraded gas accumulations. Gases from the Daqing Anticline are relatively wet with ¹³C enriched methane and ¹³C depleted CO₂, representing typically thermogenic origin. Gases within the Longhupao-Da’an Terrace have variable dryness, ¹³C enriched methane and variable δ¹³C of CO₂, suggesting dominant thermogenic origin and minor secondary microbial methane augment. The Puqian-Ao’nan Uplift contains relatively dry gas with ¹³C depleted methane and ¹³C enriched CO₂, typical for secondary microbial gas with a minor part of thermogenic methane. Gas accumulations in the Western Slope are very dry with low carbon dioxide concentrations. Some gases contain ¹³C depleted methane, ethane and propane, indicating low maturity/primary microbial origin. Recognition of varying genetic gas types in the Songliao Basin helps explain the observed dominance of gas in the shallow reservoir and could serve as an analogue for other similar shallow gas systems.  相似文献   

常用气体地热温度计的应用及效果评价   总被引：1，自引：0，他引：1       下载免费PDF全文

赵平 《地质科学》1993,28(2):167-176

基于冰岛部分地热田的实际资料,选择有代表性的、不同温度的地热田,应用CO₂、H₂S、H₂、CO₂/H₂和H₂S/H₂气体地热温度计计算热储温度,深入探讨了影响温度计准确性的各种因素,提出CO₂和H₂S温度计具有良好的实用价值。在热储温度T<200℃时,CO₂温度计的预测温度略低;在200℃<T<300℃范围时,H₂S温度计标定不够准确。并对现有的其它气体地热温度计进行了简要评价。  相似文献   

An automatic system for continuous monitoring of CO2, H2S, SO2 and meteorological parameters in the atmosphere of volcanic areas     

B Badalamenti  M Liotta  M Valenza 《Geochemical transactions》2001,2(1):30-5

An automatic system for the continuous monitoring of CO₂, H₂S, SO₂ and meteorological parameters in atmosphere has been developed. The system has been tested in the laboratory in order to verify the stability and reliability of each sensor and of the whole system. A field test for a period of one month, at the Solfatara of Pozzuoli has also been carried out. The acquired data during the field test reveal a correlation between the wind speed and the concentrations of CO₂, H₂S, and SO₂ in the atmosphere. With a wind speed of over 4 ms^-1 the concentration of the three gases reached constant background values of 600 ppm for CO₂ and about 2 ppm vol. for H₂S and SO₂. The different ratios of H₂S/SO₂ measured in the fumaroles (~100) and in the atmosphere (1–0.1) clearly indicate that H₂S is oxidized to SO₂ during the transport.  相似文献   

Relationship between CO₂-dominated fluids,hydrothermal alterations and gold mineralization in the Red Lake greenstone belt,Canada   总被引：1，自引：0，他引：1  

Guoxiang Chi  Yongxing Liu  Benoît Dubé 《Applied Geochemistry》2009

The Red Lake greenstone belt is one of the foremost Au mining camps in Canada and hosts the world-class Campbell-Red Lake Au deposit. Belt-scale hydrothermal alteration is characterized by proximal ferroan dolomite zones associated with Au mineralization surrounded by distal calcite zones, both being accompanied by potassic alterations (sericite, muscovite, and biotite). At the Campbell-Red Lake and Cochenour deposits Au mineralization (in particular high-grade ore) is associated with silica and sulfides (especially arsenopyrite) that replace carbonate ± quartz veins and the host rocks. The prevalence of carbonic fluid inclusions and rare occurrence of aqueous-bearing inclusions in carbonate–quartz–Au veins in the Campbell-Red Lake deposit, and the consistency of homogenization temperatures of carbonic inclusions within individual fluid inclusion assemblages (FIA), have been interpreted to indicate that H₂O-poor, CO₂-dominated fluids were responsible for the carbonate veining and Au mineralization. Further studies of fluid inclusions in carbonate–quartz veins within and outside the deformation zone hosting the Campbell-Red Lake deposit (the Red Lake Mine trend) including the Cochenour Au deposit, the Redcon Au prospect, and outcrops in the distal calcite zone also reveal the dominance of carbonic fluid inclusions in vein minerals. These studies indicate that CO₂-dominated fluids were flowing through fractures during carbonate vein formation and Au mineralization both within and outside major structures. The carbonic fluid may have been initially undersaturated with water, or it may have resulted from phase separation of an H₂O–CO₂–NaCl fluid. In the latter case, phase separation modeling indicates that the initial fluid likely had XCO₂${\text{X}}_{{\text{CO}}_2}$ values larger than 0.8. Calculations based on hydrothermal mineral assemblages indicate XCO₂${\text{X}}_{{\text{CO}}_2}$ values in the host rocks from 0.025 to 0.85, reflecting a change from CO₂-dominated fluids in the fractures (veins) to H₂O-dominated fluids in the host rocks away from the fractures. The CO₂-dominated fluids were likely advected from granulite facies in the deeper crust, whereas the H₂O-dominated fluids were derived from the ambient host rocks of amphibole to greenschist facies. Calculations based on CO₂ requirements and source constraints indicate that the mineralizing fluids were likely two orders of magnitude more enriched in Au than the commonly assumed values of a few μg/L, which may explain why the Campbell-Red Lake deposit has a very high-grade of Au (average 21 g/t for the whole deposit and 81 g/t for the Goldcorp High-Grade zone). Fluid inclusion data suggest that the carbonate veining and Au mineralization likely took place at depths from 7 to 14 km. The development of crustiform–colloform structures in the carbonate ± quartz veins, which was previously interpreted to indicate relatively shallow environments, may alternatively have been related to extremely high fluid pressures and the CO₂-dominated nature of the fluids, which could have enhanced the brittle properties of the rocks due to their high wetting angles.  相似文献   

Gas genetic type and origin of hydrogen sulfide in the Zhongba gas field of the western Sichuan Basin, China   总被引：7，自引：0，他引：7  

Guangyou Zhu  Shuichang Zhang  Haiping Huang  Yingbo LiangShucui Meng  Yuegang Li 《Applied Geochemistry》2011,26(7):1261-1273

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

Experimental investigations of the reaction path in the MgO–CO₂–H₂O system in solutions with various ionic strengths,and their applications to nuclear waste isolation     

Yongliang Xiong  Anna Snider Lord 《Applied Geochemistry》2008

The reaction path in the MgO–CO₂–H₂O system at ambient temperatures and atmospheric CO₂ partial pressure(s), especially in high-ionic-strength brines, is of both geological interest and practical significance. Its practical importance lies mainly in the field of nuclear waste isolation. In the USA, industrial-grade MgO, consisting mainly of the mineral periclase, is the only engineered barrier certified by the Environmental Protection Agency (EPA) for emplacement in the Waste Isolation Pilot Plant (WIPP) for defense-related transuranic waste. The German Asse repository will employ a Mg(OH)₂-based engineered barrier consisting mainly of the mineral brucite. Therefore, the reaction of periclase or brucite with carbonated brines with high-ionic-strength is an important process likely to occur in nuclear waste repositories in salt formations where bulk MgO or Mg(OH)₂ will be employed as an engineered barrier. The reaction path in the system MgO–CO₂–H₂O in solutions with a wide range of ionic strengths was investigated experimentally in this study. The experimental results at ambient laboratory temperature and ambient laboratory atmospheric CO₂ partial pressure demonstrate that hydromagnesite (5424) (Mg₅(CO₃)₄(OH)₂ · 4H₂O) forms during the carbonation of brucite in a series of solutions with different ionic strengths. In Na–Mg–Cl-dominated brines such as Generic Weep Brine (GWB), a synthetic WIPP Salado Formation brine, Mg chloride hydroxide hydrate (Mg₃(OH)₅Cl · 4H₂O) also forms in addition to hydromagnesite (5424).  相似文献