Origin and distribution of hydrogen sulfide in the Yuanba gas field,Sichuan Basin,Southwest China

The Yuanba gas field in the Permian Changxing Formation (P₂c), which exhibits wide variations in its hydrogen sulfide (H₂S) concentration (1.20–12.16%), is a typical sour gas field in the northern Sichuan Basin. The sulfur-rich reservoir's solid bitumen (atomic S/C ratios are 0.032–0.142), and late calcite cement δ¹³C values, which are smaller than the δ¹³C values of the host dolostone, indicate that the H₂S originated from thermal sulfate reduction (TSR) and oil was involved in TSR. The gas souring index (GSI) of P₂c's gases is generally lower than 0.1. The ethane δ¹³C values increase as the GSI increases, although no obvious increase was observed in the methane δ¹³C values. The calcite cements' δ¹³C values (−15.36 to +4.56‰) in dolostone are heavier than the typical reported values, which implies that only limited heavy hydrocarbon gases were involved in TSR. No anhydrites developed in P₂c's reservoirs, and dissolved sulfate anions (SO₄²⁻) were mainly enriched during dolomitization. Insufficient dissolved SO₄²⁻ most likely caused the lower H₂S concentrations in the Permian to Triassic reservoirs in the northeastern Sichuan Basin compared to the Permian Khuff Formation in Saudi Arabia and the Jurassic Smackover Formation in Mississippi. Except for the SO₄²⁻ in residual water in paleo-oil zones, SO₄²⁻ from bottom water may also be involved in TSR; therefore, oil reservoirs with bottom water have more SO₄²⁻ and can produce more H₂S than pure oil reservoirs. This phenomenon may be the main cause of the great difference in the H₂S concentrations between reservoirs, while gravitational differentiation during late uplift most likely creates differences in H₂S concentrations in a single reservoir. Carbon dioxide (CO₂), which has a relatively heavy δ¹³C value (−3.9 to −0.3‰), may be the combined result of TSR, the balance between CO₂ and inorganic fluid systems, and carbonate decomposition.     

Origin of the hydrocarbon gases carbon dioxide and hydrogen sulfide in Dodan Field (SE-Turkey)

Gas occurrences consisting of carbon dioxide (CO₂), hydrogen sulfide (H₂S), and hydrocarbon (HC) gases and oil within the Dodan Field in southeastern Turkey are located in Cretaceous carbonate reservoir rocks in the Garzan and Mardin Formations. The aim of this study was to determine gas composition and to define the origin of gases in Dodan Field. For this purpose, gas samples were analyzed for their molecular and isotopic composition. The isotopic composition of CO₂, with values of −1.5‰ and −2.8‰, suggested abiogenic origin from limestone. δ³⁴S values of H₂S ranged from +11.9 to +13.4‰. H₂S is most likely formed from thermochemical sulfate reduction (TSR) and bacterial sulfate reduction (BSR) within the Bakuk Formation. The Bakuk Formation is composed of a dolomite dominated carbonate succession also containing anhydrite. TSR may occur within an evaporitic environment at temperatures of approximately 120–145 °C. Basin modeling revealed that these temperatures were reached within the Bakuk Formation at 10 Ma. Furthermore, sulfate reducing bacteria were found in oil–water phase samples from Dodan Field. As a result, the H₂S in Dodan Field can be considered to have formed by BSR and TSR.As indicated by their isotopic composition, HC gases are of thermogenic origin and were generated within the Upper Permian Kas and Gomaniibrik Formations. As indicated by the heavier isotopic composition of methane and ethane, HC gases were later altered by TSR. Based on our results, the Dodan gas field may have formed as a result of the interaction of the following processes during the last 7–8 Ma: 1) thermogenic gas generation in Permian source rocks, 2) the formation of thrust faults, 3) the lateral-up dip migration of HC-gases due to thrust faults from the Kas Formation into the Bakuk Formation, 4) the formation of H₂S and CO₂ by TSR within the Bakuk Formation, 5) the vertical migration of gases into reservoirs through the thrust fault, and 6) lateral-up dip migration within reservoir rocks toward the Dodan structure.     

Methane-dominated thermochemical sulphate reduction in the Triassic Feixianguan Formation East Sichuan Basin, China: towards prediction of fatal H2S concentrations

New sour pools have recently found in the Lower Triassic Feixianguan Fm carbonate reservoirs in the East Sichuan Basin in China with H₂S up to 17.4% by volume. A recent blowout from a well drilled into this formation killed hundreds of people as a result of the percentage concentrations of H₂S. In order to assess the origin of fatal H₂S as well as the cause of petroleum alteration, H₂S concentrations and the isotopes, δ³⁴S and δ¹³C have been collected and measured in gas samples from reservoirs. Anhydrite, pyrite and elemental sulphur δ³⁴S values have been measured for comparison. The high concentrations of H₂S gas are found to occur at depths >3000 m (temperature now at 100 °C) in evaporated platform facies oolitic dolomite or limestone that contains anhydrite nodule occurrence within the reservoirs. Where H₂S concentrations are greater than 10% its δ³⁴S values lie between +12.0 and +13.2‰ CDT. This is within the range of anhydrite δ³⁴S values found within the Feixianguan Fm (+11.0 to +21.7‰; average 15.5±3.5‰ CDT). Thus H₂S must have been generated by thermochemical sulphate reduction (TSR) locally within the reservoirs. Burial history analysis and fluid inclusion data reveal that the temperature at which TSR occurred was greater than about 130–140 °C, suggesting that the present depth-temperature minimum is an artifact of post-TSR uplift. Both methane and ethane were actively involved in TSR since the petroleum became almost totally dry (no alkanes except methane) and methane δ¹³C values become significantly heavier as TSR proceeded. Methane δ¹³C difference thus reflects the extent of TSR. While it is tempting to use a present-day depth control (>3000 m) to predict the distribution of H₂S in the Feixianguan Fm, this is an invalid approach since TSR occurred when the formation was buried some 1000–2000 m deeper than it is at present. The likelihood of differential uplift across the basin means that it is important to develop a basinal understanding of the thermal history of the Feixianguan Fm so that it is possible to determine which parts of the basin have been hotter than 130–140 °C.     

Sulphate-related equilibria in the hypersaline brines of the Tyro and Bannock Basins, eastern Mediterranean

The Tyro and Bannock Basins, which are depressions in the eastern Mediterranean, contain hypersaline anoxic brines. These brines are of different composition: Tyro brine is primarily an early-stage halite (NaCl) brine, whereas Bannock brine includes the more soluble ions of late-stage evaporite minerals. Accordingly, the Bannock brine contains a much greater sulphate concentration than the Tyro Brine. This difference in sulphate concentration is reflected in the concentrations of ions such as Ca, Sr and Ba, which form sparingly soluble sulphate minerals.Equilibrium calculations using the Pitzer specific ion interaction model indicate that the brines in both basins are saturated with respect to gypsum (CaSO₄-2H₂O) and supersaturated to saturated with respect to dolomite (CaMg(CO₃)₂). The degree of saturation with respect to dolomite is greater in the Bannock Basin than it is in the Tyro Basin. Correspondingly, recent gypsum crystals and dolomite hardgrounds have been found in the Bannock Basin but not in the Tyro Basin.The Tyro brine is homogeneous in composition, whereas the Bannock brine demonstrates a clear two-layer brine structure. At the interface of the upper and the lower brine distinct positive anomalies occur in the total alkalinity and the concentration of phosphate, and negative anomalies occur in the concentrations of Mn²⁺ and the rare earth elements (REE). These anomalies and the observed association of gypsum/dolomite in the sediments are all consistent with a recent precipitation of dolomite and gypsum in the Bannock Basin. The brines in both basins are also saturated with respect to barite (BaSO₄).The ⁸⁷Sr/⁸⁶Sr and δ³⁴S ratios of the Bannock brines are amazingly consistent but differ dramatically from the values for modern or Messinian-age seawater. The Sr concentration and Sr and S isotope ratios in the gypsum crystals indicate that most of these crystals have resulted from precipitation/recrystallization from the brine and not from seawater. The observed variations between crystals are thought to reflect the recrystallization of (sub-) outcropping Messinian gypsum with a low ⁸⁷Sr/⁸⁶Sr ratio in the presence of seawater or brine fluids and with different extents of diagenesis.     

Reactivity of dolomitizing fluids and Mg source evaluation of fault-controlled dolomitization at the Benicàssim outcrop analogue (Maestrat basin,E Spain)

The mechanisms responsible for the formation of huge volumes of dolomitized rocks associated with faults are not well understood. We present a case study for high-temperature dolomitization of an Early Cretaceous (Aptian–Albian) ramp in Benicàssim (Maestrat basin, E Spain). In this area, seismic-scale fault-controlled stratabound dolostone bodies extend over several kilometres away from large-scale faults. This work aims at evaluating different Mg sources for dolomitization, estimating the reactivity of dolomitizing fluids at variable temperature and quantifying the required versus available fluid volumes to account for the Benicàssim dolostones. Field relationships, stable ¹³C and ¹⁸O isotopes, as well as radiogenic ⁸⁷Sr/⁸⁶Sr isotopes, indicate that dolomitization at Benicàssim was produced by a high-temperature fluid (>80 °C). ¹³C and ¹⁸O isotopic compositions for dolomite vary from +0.5 to +2.9‰ V-PDB and from +21.1 to +24.3 V-SMOW, respectively. A Mg source analysis reveals that the most likely dolomitizing fluid was seawater-derived brine that interacted with underlying Triassic red beds and the Paleozoic basement. Geochemical models suggest that evolved seawater can be considerably more reactive than high-salinity brines, and the maximum reactivity occurs at about 100 °C. Mass-balance calculations indicate that interstitial fluids with high pressure and/or high temperature relative to the normal geothermal gradient cannot account for the volume of dolomite at Benicàssim. Instead a pervasive fluid circulation mechanism, like thermal convection, is required to provide a sufficient volume of dolomitizing fluid, which most likely occurred during the Late Cretaceous post-rift stage of the Maestrat basin. This study illustrates the importance of fluid budget quantification to critically evaluate genetic models for dolomitization and other diagenetic processes.     

TSR-altered oil with high-abundance thiaadamantanes of a deep-buried Cambrian gas condensate reservoir in Tarim Basin

The first exploratory well, the ZS1C well, with 158,545 m³ daily gas production was discovered in 6861–6944 m deep strata of the Cambrian gypsolyte layer of the Tarim Basin, China in 2014. The discovery opens a new target for the Cambrian-reservoired oil and gas exploration, and directly leads to large-scale oil and gas exploration of the deep-reservoired Cambrian oil and gas fields in the Basin. Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry and a comprehensive two-dimensional gas chromatography–flame ionization detector revealed the presence of abundant adamantane compounds, 2-thiaadamantanes and 2-thiadiamantanes, and a large amount of sulfur-containing compounds in the condensate oil. The formation of organic sulfur-containing compounds, such as 2-thiaadamantanes, is an indication of sulfur incorporation from the gypsum in the stratum into oil and gas in the course of TSR. This reservoir has apparently suffered severe TSR alteration because (1) High content of H₂S, (2) H₂S sulfur isotopes, (3) CO₂ carbon isotopes, and others abundant data to support this findings. Similar sulfur isotopic composition of H₂S, oil condensate and the gypsum in the Cambrian strata indicate that the produced condensate is experienced TSR alteration. Therefore, the deep-accumulated Cambrian oil reservoir has experienced severe TSR alteration, and accumulated natural gas and condensate contains high sulfur content.     

Saddle dolomite and calcite cements as records of fluid flow during basin evolution: Paleogene carbonates,United Arab Emirates

Field observations indicate that tectonic compression, anticline formation and concomitant uplift events of marine Paleogene carbonates in eastern United Arab Emirates, which are related to the Zagros Orogeny, have induced brecciation, karstification, and carbonate cementation in vugs and along faults and fractures. Structural analysis, stable isotopes and fluid inclusion microthermometry are used to constrain the origin and geochemical evolution of the fluids. Fluid flow was related to two tectonic deformation phases. Initially, the flux of moderately ⁸⁷Sr-rich basinal NaCl–MgCl₂–H₂O brines along reactivated deep-seated strike-slip faults have resulted in the precipitation of saddle dolomite in fractures and vugs and in dolomitization of host Eocene limestones (δ¹⁸O_V-PDB −15.8‰ to −6.2‰; homogenization temperatures of 80–115 °C and salinity of 18–25 wt.% eq. NaCl). Subsequently, compression and uplift of the anticline was associated with incursion of meteoric waters and mixing with the basinal brines, which resulted in the precipitation of blocky calcite cement (δ¹⁸O_V-PDB −22‰ to −12‰; homogenization temperatures of 60–90 °C and salinity of 4.5–9 wt.% eq. NaCl). Saddle dolomite and surrounding blocky calcite have precipitated along the pre- and syn-folding E–W fracture system and its conjugate fracture sets. The stable isotopes coupled with fluid-inclusion micro-thermometry (homogenization temperatures of ≤50 °C and salinity of <1.5 wt.% eq. NaCl) of later prismatic/dogtooth and fibrous calcites, which occurred primarily along the post-folding NNE–SSW fracture system and its conjugate fracture sets, suggest cementation by descending moderately ⁸⁷Sr-rich, cool meteoric waters. This carbonate cementation history explains the presence of two correlation trends between the δ¹⁸O_V-PDB and δ¹³C_V-PDB values: (i) a negative temperature-dependent oxygen isotope fractionation trend related to burial diagenesis and to the flux of basinal brines, and (ii) positive brine-meteoric mixing trend. This integrated study approach allows better understanding of changes in fluid composition and circulation pattern during evolution of foreland basins.     

Geochemical characteristics of tight gas and gas-source correlation in the Daniudi gas field,the Ordos Basin,China

The molecular composition, stable carbon and hydrogen isotopes and light hydrocarbons of the Upper Paleozoic tight gas in the Daniudi gas field in the Ordos Basin were investigated to study the geochemical characteristics. Tight gas in the Daniudi gas field displays a dryness coefficient (C₁/C_1–5) of 0.845–0.977 with generally positive carbon and hydrogen isotopic series, and the C₇ and C_5–7 light hydrocarbons of tight gas are dominated by methylcyclohexane and iso-alkanes, respectively. The identification of gas origin and gas-source correlation indicate that tight gas is coal-type gas, and the gases reservoired in the Lower Permian Shanxi Fm. (P₁s) and Lower Shihezi Fm. (P₁x) had a good affinity and were derived from the P₁s coal-measure source rocks, whereas the gas reservoired in the Upper Carboniferous Taiyuan Fm. (C₃t) was derived from the C₃t coal-measure source rocks. The molecular and methane carbon isotopic fractionations of natural gas support that the P₁x gas was derived from the P₁s source rocks. The differences of geochemical characteristics of the C₃t gas from different areas in the field suggest the effect of maturity difference of the source rocks rather than the diffusive migration, and the large-scale lateral migration of the C₃t gas seems unlikely. Comparative study indicates that the differences of the geochemical characteristics of the P₁s gases from the Yulin and Daniudi gas fields originated likely from the maturity difference of the in-situ source rocks, rather than the effect of large-scale lateral migration of the P₁s gases.     

Multiple dolomitization and later hydrothermal alteration on the Upper Cambrian-Lower Ordovician carbonates in the northern Tarim Basin,China

Thick Upper Cambrian-Lower Ordovician carbonates were deposited on a shallow marine platform in the northern Tarim Basin, which were extensively dolomitized, particularly for the Upper Cambrian carbonates. The resulting dolomite rocks are predominantly composed of matrix dolomites with minor cement dolomites. Based on petrographic textures, matrix dolomites consist of very finely to finely crystalline, nonplanar-a to planar-s dolomite (Md1), finely to medium crystalline, planar-e(s) dolomite (Md2), and finely to coarsely crystalline, nonplanar-a dolomite (Md3). Minor cement dolomites include finely to medium crystalline, planar-s(e) dolomite (Cd1) and coarsely crystalline, nonplanar saddle dolomite (Cd2), which partially or completely fill dissolution vugs and fractures; these cements postdate matrix dolomites but predate later quartz and calcite infills. Origins of matrix and cement dolomites and other diagenetic minerals are interpreted on the basis of petrography, isotopic geochemistry (O, C and Sr), and fluid inclusion microthermometry. Md1 dolomite was initially mediated by microbes and subsequently precipitated from slightly modified brines (e.g., evaporated seawater) in near-surface to very shallow burial settings, whereas Md2 dolomite was formed from connate seawater in association with burial dissolution and localized Mg concentration (or cannibalization) in shallow burial conditions. Md3 dolomite, however, was likely the result of intense recrystallization (or neomorphism) upon previously-formed dolomites (e.g., Md1 or Md2 dolomite) as the host carbonates were deeply buried, and influenced by later hydrothermal fluids. Subsequent cement dolomite and quartz crystals precipitated from higher-temperature, hydrothermal fluids, which were contributed more or less by the extensive Permian large igneous province (LIP) activity in Tarim Basin as evidenced by less radiogenic Sr in the cement and parts of matrix dolomites. This extensive abnormal hydrothermal activity could also have resulted in recrystallization (or neomorphism) on the previous matrix dolomites. Faults/fractures likely acted as important conduit networks which could have channeled the hydrothermal fluids from depths. However, the basin uplift triggered by the Late Hercynian Orogeny from the Late Permian would have facilitated downward infiltration of meteoric water and dilution of hydrothermal fluids, resulting in precipitation of later calcites in which lighter C and more radiogenic Sr components demonstrate such a switch of fluid properties. This study provides a useful analogue to understand the complicated dolomitizing processes and later hydrothermal alteration intimately related to the Permian LIP activity within Tarim Basin and elsewhere.     

The carbonate system in hypersaline solutions: dead sea brines

Various investigators reported a decrease in pH as seawater is concentrated. A similar phenomenon was reported for Dead Sea waters which are about ten times more saline than seawater. The reasons for the low pH values of Dead Sea waters (pH 5.9–6.5), which precipitate CaCO₃, were investigated by determining the apparent dissociation constants of carbonic acid in these brines. A new method, based on alkalinity titration and least-squares fitting, was used to estimate the proton activity coefficient (γ_H+) and the first and second dissociation constants of carbonic acid (K₁′, K₂′) in natural and artificial Dead Sea waters. It was found that as the salt content increases, pK′₁ and pK′₂ values progressively decrease whereas γ_H+ sharply increase. At the highest salinity investigated (TDS = 330 gl^?1) γ_H+ pK′₁ and pK′₂ values are 24.5, 5.09 and 6.23, respectively, as compared to about 0.8, 5.9, 9.1 respectively for normal seawater (19‰ chlorinity) at the same temperature (30°C).The implication of the results of this study regarding solubility of CaCO₃ and the general behavior of the carbonate system in hypersaline solutions is discussed.     

Fluid inclusion and microfabric studies on Zechstein carbonates (Ca2) and related fracture mineralizations – New insights on gas migration in the Lower Saxony Basin (Germany)

New petrographic and fluid inclusion data from core samples of Upper Permian dolomitic limestone (Hauptdolomit, Zechstein group, Stassfurt carbonate sequence) from a gas field located at the northern border of the Lower Saxony Basin (LSB) essentially improve the understanding of the basin development. The gas production at the locality is characterized by very high CO₂ concentrations of 75–100% (with CH₄ and N₂).Samples consist of fine grained, mostly laminated and sometimes brecciated dolomitic limestone (mudstone/wackestone) from the transition zone between the shallow water zone (platform) and the upper slope. The study focuses on migration fluids, entrapped as fluid inclusions in diagenetic anhydrite, calcite, and fluorite, and in syn-diagenetic microfractures, as well as on the geochemistry of fluorite fracture mineralizations, obtained by LA-ICP-MS analysis. Fluid inclusion studies show that the diagenetic fluid was rich in H₂ONaClCaCl₂. Recrystallized anhydrite contains aqueous inclusions with homogenization temperatures (T_h) of ca. 123 °C, but somewhat higher T_h of ca. 142 °C was found for calcite cement followed by early Fluorite A with T_h of 147 °C. A later Fluorite B preserves gas inclusions and brines with maximum T_h of 156 °C. Fluorite B crystallized in fractures during the mobilization of CO₂-bearing brines. Crossing isochores for co-genetic aqueous-carbonic and carbonic inclusions indicate fluid trapping conditions of 180–200 °C and 900–1000 bars. δ¹³C-isotopic ratios of gas trapped in fluid inclusions suggest an organic origin for CH₄, while the CO₂ is likely of inorganic origin.Basin modelling (1D) shows that the fault block structure of the respective reservoir has experienced an uplift of >1000 m since Late Cretaceous times.The fluid inclusion study allows us to, 1) model the evolution of the LSB and fluid evolution by distinguishing different fluid systems, 2) determine the appearance of CO₂ in the geological record and, 3) more accurately estimate burial and uplift events in individual parts of the LSB.     

Monitoring of a methane-seeping pockmark by cabled benthic observatory (Patras Gulf, Greece)

A new seafloor observatory, the gas monitoring module (GMM), has been developed for continuous and long-term measurements of methane and hydrogen sulphide concentrations in seawater, integrated with temperature (T), pressure (P) and conductivity data at the seafloor. GMM was deployed in April 2004 within an active gas-bearing pockmark in the Gulf of Patras (Greece), at a water depth of 42 m. Through a submarine cable linked to an onshore station, it was possible to remotely check, via direct phone connection, GMM functioning and to receive data in near-real time. Recordings were carried out in two consecutive campaigns over the periods April–July 2004, and September 2004–January 2005, amounting to a combined dataset of ca. 6.5 months. This represents the first long-term monitoring ever done on gas leakage from pockmarks by means of CH₄+H₂S+T+P sensors. The results show frequent T and P drops associated with gas peaks, more than 60 events in 6.5 months, likely due to intermittent, pulsation-like seepage. Decreases in temperature in the order of 0.1–1°C (up to 1.7°C) below an ambient T of ca. 17°C (annual average) were associated with short-lived pulses (10–60 min) of increased CH₄+H₂S concentrations. This seepage “pulsation” can either be an active process driven by pressure build-up in the pockmark sediments, or a passive fluid release due to hydrostatic pressure drops induced by bottom currents cascading into the pockmark depression. Redundancy and comparison of data from different sensors were fundamental to interpret subtle proxy signals of temperature and pressure which would not be understood using only one sensor.     

Methane hydrate dissolution rates in undersaturated seawater under controlled hydrodynamic forcing

The dissolution of in-situ generated methane hydrate in undersaturated, synthetic seawater (S = 35) was investigated in a series of laboratory-based experiments at P-/T-conditions within the hydrate stability field. A controlled flow field was generated across the smooth hydrate surface to test if, in addition to thermodynamic variables, the dissolution rate is influenced by changing hydrodynamic conditions. The dissolution rate was found to be strongly dependent on the friction velocity, showing that hydrate dissolution in undersaturated seawater is a diffusion-controlled process. The experimental data was used to obtain diffusional mass transfer coefficients k_d, which were found to correlate linearly with the friction velocity, u. The resulting k_d/u-correlation allows predicting the flux of methane from natural gas hydrate exposures at the sediment/seawater interface into the bulk water for a variety of natural P, T and flow conditions. It also is a tool for estimating the rate of hydrate regrowth at locations where natural hydrate outcrops at the seafloor persist in contact with undersaturated seawater.     

The effect of pressure on the chemical potentials of seawater components,on ionic species in seawater,and on calcite saturation levels

The activities of most of the major seawater components at 1,001 bars have been estimated, and values for the ions deduced. Equations giving the effect of pressure on the activities of ionic species in seawater ($\text{S = 35‰}$) have been developed. The species covered are: NaSO₄^?, MgSO₄⁰, CaSO₄⁰, H⁺, the free base (NH₃), the HCO₃^?/CO₃² activity ratio and the ion activity product of calcium carbonate. Comparison of the latter with the “ideal” solubility of calcite (pure solid in equilibrium with a mixed electrolyte solution) indicates a degree of saturation compatible with the trends indicated by in situ measurements.     

Geochemical characteristics and isotopic reversal of natural gases in eastern Kopeh-Dagh,NE Iran

Natural gas samples from two gas fields located in Eastern Kopeh-Dagh area were analyzed for molecular and stable isotope compositions. The gaseous hydrocarbons in both Lower Cretaceous clastic reservoir and Upper Jurassic carbonate reservoir are coal-type gases mainly derived from type III kerogen, however enriched δD values of methane implies presence of type II kerogen related material in the source rock. In comparison Upper Jurassic carbonate reservoir gases show higher dryness coefficient resulted through TSR, while presence of C₁C₅ gases in Lower Cretaceous clastic reservoir exhibit no TSR phenomenon. Carbon isotopic values indicate gas to gas cracking and TSR occurrence in the Upper Jurassic carbonate reservoir, as the result of elevated temperature experienced, prior to the following uplifts in last 33–37 million years. The δ¹³C of carbon dioxide and δ³⁴S of hydrogen sulfide in Upper Jurassic carbonate reservoir do not primarily reflect TSR, as uplift related carbonate rock dissolution by acidic gases and reaction/precipitation of light H₂S have changed these values severely. Gaseous hydrocarbons in both reservoirs exhibit enrichment in C₂ gas member, with the carbonate reservoir having higher values resulted through mixing with highly-mature-completely-reversed shale gases. It is likely that the uplifts have lifted off the pressure on shale gases, therefore facilitated the migration of the gases into overlying horizons. However it appears that the released gases during the first major uplift (33–37 million years ago) have migrated to both reservoirs, while the second migrated gases have only mixed with Upper Jurassic carbonate reservoir gases. The studied data suggesting that economic accumulations of natural gas/shale gases deeper than Upper Jurassic carbonate reservoir would be unlikely.     

离子色谱法测定海水中氯离子和硫酸根离子

氯离子和硫酸根离子是海水中重要的无机阴离子,在研究海洋生态变化、海洋循环作用过程与海洋全球气候变化等领域具有重要的指示意义。其测定方法较多,但缺少相应的测试方法。本文对测定海水中Cl^-,SO₄^2-的离子色谱方法进行了优化,选用IonPacAS14碳酸盐选择性离子色谱柱,以3.5 mmol/L Na₂CO₃+1 mmol/L NaHCO₃为流动相,可消除海水样品中碳酸盐及其他阴离子的干扰。该方法对Cl^-检出限为0.29 mg/L,线性相关系数r²=0.999 2,对SO₄^2-检出限为0.42 mg/L,线性相关系数r²=0.997 9。样品的加标回收率在95%~102%,Cl^-和SO₄^2-的相对标准偏差分别为1.92%和4.18%。该方法简便、迅速、灵敏、准确度高,可满足批量海水样品中Cl^-与SO₄^2-的准确测试。     

The role of pHT measurements in marine CO2-system characterizations

Spectrophotometric pH_T measurements can routinely be obtained with an imprecision on the order of ±0.0005 pH_T units. This level of imprecision is equivalent to an imprecision in total hydrogen ion concentration of ±0.1% (where pH_T=−log[H⁺]_T and [H⁺]_T≅[H⁺]+[HSO₄⁻]). At this level of precision, pH_T measurements provide an important tool in quality control assessments of other CO₂-system parameters (CO₂ fugacity, total inorganic carbon, total alkalinity). CO₂ fugacities and total alkalinities calculated using measured pH_T and total inorganic carbon, for the large data set considered in this work, have relative precisions on the order of 0.15 and 0.1%, respectively. The precision of total inorganic carbon calculated via pH_T and salinity-normalized-alkalinity is on the order of 0.02% or better. In this work, using the NOAA 1992 boreal autumn Equatorial Pacific (EqPac) dataset, it is shown that CO₂-system variables calculated via pH_T can be used to enhance both the precision and accuracy of directly measured parameters. Through the procedures described in this work significant problems were revealed in the initial version of the 1992 NOAA dataset, and the dataset was greatly improved. Additionally, in this work, we revisit CO₂-system thermodynamic consistency issues in view of changes in the pH_T values assigned to tris seawater buffers and consequential changes in the calibration of sulfonephthalein pH_T indicators. As the principal result of a +0.0047 increase in the pK of meta cresol purple, CO₂ fugacity calculations and measurements are in very good agreement for the NOAA 1992 boreal autumn EqPac dataset. We note, as well, that due to a reassignment of the titrant acid concentration used in the NOAA 1992 boreal autumn dataset, measured total alkalinities are in good agreement with total alkalinities calculated from total carbon and pH_T.     

Estimation of the upwelling rate of deep waters in the Black Sea from the H2S vertical distribution

The expression for the bottom convection intensity is derived from the equality of the advective vertical flux of H₂S within 1000–2000 m to the diffusion turbulent flow close to the H₂S zone upper boundary. The upwelling rate, which is expressed via the H₂S concentration in deep waters and the gradient of the H₂S concentration near the upper boundary, is 10^–4 cm/s. It is shown that the H₂S diffusion flux in deep waters is an order less than the advective one. The conclusion that below 1000 m the age of H₂S does not exceed 30 years and H₂S reaches the upper boundary in approximately 150 years is derived.Translated by Mikhail M. Trufanov.