http://www.sciencedirect.com/science/article/pii/S1674987113001114

The Deccan Syneclise is considered to have significant hydrocarbon potential.However,significant hydrocarbon discoveries,particularly for Mesozoic sequences,have not been established through conventional exploration due to the thick basalt cover over Mesozoic sedimentary rocks.In this study,near-surface geochemical data are used to understand the petroleum system and also investigate type of source for hydrocarbons generation of the study area.Soil samples were collected from favorable areas identified by integrated geophysical studies.The compositional and isotopic signatures of adsorbed gaseous hydrocarbons(methane through butane) were used as surface indicators of petroleum micro-seepages.An analysis of 75 near-surface soil-gas samples was carried out for light hydrocarbons(C1-C4) and their carbon isotopes from the western part of Tapti graben,Deccan Syneclise,India.The geochemical results reveal sites or clusters of sites containing anomalously high concentrations of light hydrocarbon gases.High concentrations of adsorbed thermogenic methane(C_1 = 518 ppb) and ethane plus higher hydrocarbons(ΣC_(2+) = 977 ppb) were observed.Statistical analysis shows that samples from 13% of the samples contain anomalously high concentrations of light hydrocarbons in the soil-gas constituents.This seepage suggests largest magnitude of soil gas anomalies might be generated/source from Mesozoic sedimentary rocks,beneath Deccan Traps.The carbon isotopic composition of methane,ethane and propane ranges are from-22.5‰ to-30.2‰ PDB,-18.0‰to 27.1‰ PDB and 16.9‰-32.1‰ PDB respectively,which are in thermogenic source.Surface soil sample represents the intersection of a migration conduit from the deep subsurface to the surface connected to sub-trappean Mesozoic sedimentary rocks.Prominent hydrocarbon concentrations were associated with dykes,lineaments and presented on thinner basaltic cover in the study area,which probably acts as channel for the micro-seepage of hydrocarbons.     

Organic geochemistry of the Vindhyan sediments: Implications for hydrocarbons

The organic geochemical methods of hydrocarbon prospecting involve the characterization of sedimentary organic matter in terms of its abundance, source and thermal maturity, which are essential prerequisites for a hydrocarbon source rock. In the present study, evaluation of organic matter in the outcrop shale samples from the Semri and Kaimur Groups of Vindhyan basin was carried out using Rock Eval pyrolysis. Also, the adsorbed low molecular weight hydrocarbons, methane, ethane, propane and butane, were investigated in the near surface soils to infer the generation of hydrocarbons in the Vindhyan basin. The Total Organic Carbon (TOC) content in shales ranges between 0.04% and 1.43%. The S₁ (thermally liberated free hydrocarbons) values range between 0.01–0.09 mgHC/gRock (milligram hydrocarbon per gram of rock sample), whereas the S₂ (hydrocarbons from cracking of kerogen) show the values between 0.01 and 0.14 mgHC/gRock. Based on the T_max (temperature at highest yield of S₂) and the hydrogen index (HI) correlations, the organic matter is characterized by Type III kerogen. The adsorbed soil gas, CH₄ (C₁), C₂H₆ (C₂), C₃H₈ (C₃) and nC₄H₁₀, (nC4), concentrations measured in the soil samples from the eastern part of Vindhyan basin (Son Valley) vary from 0 to 186 ppb, 0 to 4 ppb, 0 to 5 ppb, and 0 to 1 ppb, respectively. The stable carbon isotope values for the desorbed methane (δ¹³C₁) and ethane (δ¹³C₂) range between −45.7‰ to −25.2‰ and −35.3‰ to −20.19‰ (VPDB), respectively suggesting a thermogenic source for these hydrocarbons. High concentrations of thermogenic hydrocarbons are characteristic of areas around Sagar, Narsinghpur, Katni and Satna in the Son Valley. The light hydrocarbon concentrations (C₁–C₄) in near surface soils of the western Vindhyan basin around Chambal Valley have been reported to vary between 1–2547 ppb, 1–558 ppb, 1–181 ppb, 1–37 ppb and 1–32 ppb, respectively with high concentrations around Baran-Jhalawar-Bhanpur-Garot regions (Kumar et al., 2006). The light gaseous hydrocarbon anomalies are coincident with the wrench faults (Kota – Dholpur, Ratlam – Shivpuri, Kannod – Damoh, Son Banspur – Rewa wrench) in the Vindhyan basin, which may provide conducive pathways for the migration of the hydrocarbons towards the near surface soils.     

Geochemical characterization of adsorbed light gaseous alkanes in near surface soils of the eastern Ganga basin for hydrocarbon prospecting

This study aims to assess the hydrocarbon potential of Ganga basin utilizing the near surface geochemical prospecting techniques. It is based on the concept that the light gaseous hydrocarbons from the oil and gas reservoirs reach the surface through micro seepage, gets adsorbed to soil matrix and leave their signatures in soils and sediments, which can be quantified. The study showed an increased occurrence of methane (C₁), ethane (C₂) and propane (C₃) in the soil samples. The concentrations of light gaseous hydrocarbons determined by Gas Chromatograph ranged (in ppb) as follows, C₁: 0–519, C₂: 0–7 and C₃: 0–2. The carbon isotopic (VPDB) values of methane varied between ?52.2 to ?27.1‰, indicating thermogenic origin of the desorbed hydrocarbons. High concentrations of hydrocarbon were found to be characteristic of the Muzaffarpur region and the Gandak depression in the basin, signifying the migration of light hydrocarbon gases from subsurface to the surface and the area’s potential for hydrocarbon resources.     

Application of trace metal anomalies for recognition of petroleum prospects in surface sediments of Kutch and Saurashtra Basins, India

Seepage of hydrocarbons, either as macroseepage or microseepage, can set up near-surface oxidation-reduction zones that favour the development of a diverse array of chemical and mineralogic changes. In this study trace metal alterations were mapped that appear to be associated with hydrocarbon microseepages in the oil/gas fields. A total of 210 soil samples were collected from near surface sediments of Kutch and Saurashtra Basins, India. The soil samples were collected from a depth of 2–2.5 m. The paper reports the chemical alterations associated with trace metals in soils that are related to hydrocarbon microseepages above the Kutch and Saurashtra Basins, India. The soil samples for trace metals; Scandium (Sc), Vanadium (V), Chromium (Cr), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Barium (Ba) and Strontium (Sr) were analyzed using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The concentrations of the trace elements ranged between for Sc (12.69 to 21.91 ppm), V (109.20 to 436.05 ppm), Cr (87.15 to 481.57 ppm), Co (18.25 to 64.31 ppm), Ni (57.55 to 263.15 ppm), Cu (44.88 to 143.96 ppm), Zn (137.60 to 502.31 ppm), Ba (149.27 to 921.46 ppm) and Sr (143.93 to 425.63 ppm) were obtained. It was observed that trace elements concentrations were tremendously increased when compared with normal concentration in the soils. The adsorbed soil gas analysis showed the presence of high concentrations of ΣC₂₊ (C₂H₆, C₃H₈ and n-C₄H₁₀) ranged between 1 to 121 ppb respectively. Integrated studies of trace elements over adsorbed light gaseous hydrocarbon (ΣC₂₊) anomalies showed good correlation. The carbon isotopic composition of δ¹³C₁ of the samples ranges between — 36.6 ‰ to ?22.7‰ (Pee Dee Belemnite) suggest thermogenic source for hydrocarbon gases. The increase in trace metal concentrations near oil/gas producing areas, suggests that soil chemical change to a reducing environment, presumably due to the influence of hydrocarbon microseepage, which could be applied with other geo-scientific data to identify areas of future hydrocarbon exploration in the frontier areas.     

Rare-earth and trace elements and hydrogen and oxygen isotopic compositions of Cretaceous kaolinitic sediments from the Lower Benue Trough,Nigeria: provenance and paleoclimatic significance

This study evaluated the Cretaceous (Campanian–Maastrichtian) kaolinitic sediments of the Ajali/Mamu and Enugu/Nkporo Formations from the Lower Benue Trough of Nigeria. A combined method of inductively coupled plasma–mass spectrometry and isotope ratio mass spectrometry was used to investigate trace and rare-earth element geochemistry and hydrogen and oxygen isotopic compositions. These data were then used to infer the sediments’ provenance and paleoclimatic conditions during their deposition. The sediments contained low concentrations of most trace elements, with the exceptions of Zr (651–1352 ppm), Ba (56–157 ppm), V (38–90 ppm), and Sr (15.1–59.6 ppm). Average values of Co and Ni were 1.5 and 0.7 ppm, respectively. Trace and rare earth element values were lower than corresponding values for upper continental crust and Post-Archean Australian Shale, with the exception of Zr. The samples showed only slight light rare-earth enrichment and nearly flat heavy rare-earth depletion patterns, with negative Eu and Tm anomalies, typical of felsic sources. Geochemical parameters such as La/Sc, Th/Sc, and Th/Co ratios support that the kaolinitic sediments were derived from a felsic rock source, likely deposited in an oxic environment. ¹⁸O values ranged from + 15.4 to + 21.2‰ for the investigated samples, consistent with a residual material derived from chemical weathering of felsic rock and redeposited in a sedimentary basin (typical values of + 19 to + 21.2‰). While in the basin, the sediments experienced extended interactions with meteoric water enriched in δD and δ¹⁶O. However, the variation in δD and δ¹⁶O values for the investigated samples is attributed to the high temperature of formation (54–91 °C). The δD and δ¹⁸O values suggest that the sediments, although obtained from different localities within the Lower Benue Trough, formed under similar hot, tropical climatic conditions.

     

Geo-microbial prospecting studies of surface sediments from petroliferous region of the Mehsana Block,North Cambay Basin

Surface adsorbed gas surveys and geo-microbiological surveys are well known techniques of petroleum exploration and aim towards risk reduction in exploration by way of identifying the areas warm with hydrocarbons and to establish inter-se exploration priorities amongst the identified warm areas. The thermogenic surface adsorbed gaseous hydrocarbons distribution patterns in petroliferous areas are considered to be a credible evidence for the upward migration of hydrocarbons. The present investigation aims to explore correlation between the adsorbed gas distribution pattern and microbial oxidizers in identifying the upward migration of hydrocarbons especially in the tropical black soil terrain of known petroliferous Mehsana Block of North Cambay Basin, India. A set of 135 sub-soil samples collected, were analyzed for indicator hydrocarbon oxidizing bacteria, adsorbed light gaseous hydrocarbons and carbon isotope ratios (¹³C_methane and δ¹³C_ethane). The microbial prospecting studies showed the presence of high bacterial population for methane (5.4 × 10⁶ cfu/gm), ethane (5.5 × 10⁶ cfu/gm), propane (4.6 × 10⁶ cfu/gm) and butane oxidizing bacteria (4.6 × 10⁶ cfu/gm) in soil samples. The light gaseous hydrocarbon analysis showed that the concentration ranges of C₁, C₂, C₃, iC₄ and nC₄ are 402 ppb, 135 ppb, 70 ppb, 9 ppb and 18 ppb, respectively, and the value of carbon isotope ranges of methane ?29.5 to ?43.0‰ (V-PDB) and ethane ?19.1 to ?20.9‰ (V-PDB). The existence of un-altered petroliferous microseep (δ¹³C, ?43‰) of catagenetic origin is observed in the study area. Geo-microbial prospecting method and adsorbed soil gas and carbon isotope studies have shown good correlation with existing oil/gas fields of Mehsana. Microbial surveys can independently precede other geochemical and geophysical surveys to delineate area warm with hydrocarbons, and mapped microbiological anomalies may provide focus for locales of hydrocarbon accumulation in the Mehsana Block of Cambay Basin.     

Geochemical exploration for hydrocarbons in the soils of southeast of Krishna-Godavari Basin, Andhra Pradesh

Surface adsorbed gas surveys and geo-microbiological surveys are known techniques of petroleum exploration and aim towards risk reduction in exploration by way of identifying the areas warm with hydrocarbons and to establish intense exploration priorities amongst the identified warm areas. The present investigation aims to explore correlation between the adsorbed gas distribution pattern with the distribution of the counts of methane, ethane, propane and butane microbial oxidizers in the sub soil samples to establish the role of the latter in identifying the upward migration of hydrocarbons especially in the known petroliferous Krishna-Godavari Basin, India. A total of 135 soil samples were collected near oil and gas fields of Tatipaka, Pasarlapudi areas of Krishna Godavari Basin, Andhra Pradesh. The soil samples were collected from a depth of 2?C2.5 m. The samples collected, were analyzed for indicator hydrocarbon oxidizing bacteria, adsorbed light gaseous hydrocarbons and carbon isotopes (??¹³C_methane). The microbial prospecting studies showed the presence of high bacterial population for methane (3.94 × 10⁵ cfu/gm), ethane (3.85 × 10⁵ cfu/gm), propane (4.85 × 10⁵ cfu/gm) and butane oxidizing bacteria (3.63 × 10⁵ cfu/gm) in soil samples indicating microseepage of hydrocarbons. The light gaseous hydrocarbon analysis showed 83 ppb, 92 ppb, 134 ppb, 187 ppb and 316 ppb of C₁, C₂, C₃, nC₄ and nC₅, respectively, and the carbon isotopic composition of ??¹³C₁ of the samples ranged between ? 36.6 ?? to ?22.7?? (Pee Dee Belemnite) values, which presents convincing evidence that the adsorbed soil gases collected from these sediments are of thermogenic origin. Geo-microbial prospecting method and adsorbed soil gas and carbon isotope studies have shown good correlation with existing oil/ gas fields of K.G basin. Microbial surveys indicating microseepage of hydrocarbons can, therefore, independently precede other geochemical and geophysical surveys to delineate areas warm with hydrocarbons and mapped microbiological anomalies may provide focus for locales of hydrocarbon accumulation in the K.G basin.     

Light hydrocarbons geochemistry of surface sediment from petroliferous region of the Mehsana block,North Cambay Basin

A study was carried out to test the usefulness of surface geochemical methods as regional evaluation tools in petroliferous region of the Mehsana block, North Cambay Basin. A suite of 135 soil samples collected from the depth of 2.5 m, were analyzed for adsorbed light gaseous hydrocarbons and carbon isotopes (δ¹³C_methane and δ¹³C_ethane). The light gaseous hydrocarbon analysis show that the concentration ranges 402 ppb, 135 ppb, 70 ppb, 9 ppb and 18 ppb of C₁, C₂, C₃, iC₄ and nC₄, respectively. The value of carbon isotopic ranges of methane −29.5 to −43.0‰ (PDB) and ethane −19.1 to −20.9‰ (PDB). This data, when mapped, indicates patterns coinciding with major known oil and/or gas field of Sobhasan/Linch in this study area. The existence of un-altered petroliferous microseeps of catagenetic origin is observed in the study area. A regional study, such as the one described here, can provide important exploration facts concerning the regional hydrocarbon potential in a block. This method has been confirmed and can be applied successfully in frontier basins.     

Integrated geo-microbial and trace metal anomalies for detection of hydrocarbon microseepage in Ahmedabad block of Cambay basin,India

The aim of the present work is to define the geo-microbial signatures along with trace metals, and to investigate whether the geo-microbial anomalies have correlation with trace metal anomalies in Ahmedabad block of Cambay basin. The surface geochemical techniques are based on seepage of light hydrocarbon gases from the oil and gas pools to the shallow surface and can bring up near-surface oxidation reduction zones that favor the development of a diverse array of chemical and mineralogical changes. The paper reports the role of hydrocarbon microseepage in surface alterations of trace metal concentrations and hydrocarbon oxidizing bacteria and its interrelationship. For the purpose a total of 90 soil samples are collected in grid pattern of 2 x 2 km interval. The paper reports the chemical alterations associated with trace metals in soils that are related to hydrocarbon microseepages above some of the major oil and gas fields of this petroliferous region. The concentrations of V (0 to149 ppm), Cr (2 to 192 ppm), Cu (4 to 171 ppm), Se (98 to 440 ppm), Zn (56 to 1215 ppm) are obtained. It is observed that the concentrations of trace elements are tremendously increased when they are compared with their normal concentrations in soils. In this study the hydrocarbon oxidizing bacterial counts ranged between 1.0 x 10³ and 1.59 x 10⁶ cfu/g of soil sample respectively. The attempt has made for the first time, which revealed good correlation as both these anomalies are found as apical in relation. Integrated studies between trace elements and hydrocarbon oxidizing bacterial anomalies showed positive correlation with existing oil and gas wells in the study area.     

Stable isotopic compositions of Recent freshwater cyanobacterial carbonates from the British Isles: local and regional environmental controls

Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ¹⁸O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ¹⁸O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO₂ and aqueous HCO^?₃. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ¹⁸O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate.     

Stable carbon isotope geochemistry of adsorbed alkane gases in near-surface soils of the Saurashtra Basin,India

The stable carbon isotopic compositions of light hydrocarbon gases adsorbed in near-surface soil and sediments from the Saurashtra basin were characterized for their origin and maturity. Saurashtra is considered geologically prospective for oil and gas reserves; however, a major part of the basin is covered by the Deccan Traps, hindering the exploration of Mesozoic hydrocarbon targets. Surface geochemical prospecting, based on micro-seepage of hydrocarbons from subsurface accumulations, could be advantageous in such areas. In light of this, 150 soil samples were collected from the northwestern part of Saurashtra, around the Jamnagar area, where a thick sedimentary sequence of about 2–3 km exists under 1–1.5 km of Deccan basalt. The concentration of acid desorbed alkane gases from soil samples was found to vary (in ppb) as: methane (C₁) = 3–518; ethane (C₂) = 0–430; propane (C₃) = 0–331; i-butane (iC₄) = 0–297; n-butane (nC₄) = 2–116; i-pentane (iC₅) = 0–31 and n-pentane (nC₅) = 0–23, respectively.Fifteen samples with high concentrations of alkane gases were measured for their δ¹³C₁; δ¹³C₂ and δ¹³C₃ compositions using gas chromatography–combustion-isotope ratio mass spectrometry (GC–C-IRMS). The values for methane varied from ? 27 to ? 45.4‰, ethane from ? 20.9 to ? 27.6‰, and propane from ? 20.4 to ? 29.1‰ versus the Vienna PeeDee Belemnite (VPDB). The carbon isotope ratio distribution pattern represents isotopic characteristics pertaining to hydrocarbon gases derived from thermogenic sources. Comparisons of carbon isotopic signatures and compositional variations with the standard carbon isotopic models suggest that hydrocarbon gases found in the shallow depths of the study area are not of bacterial origin but are formed thermally from deeply buried organic matter, likely to be mainly a terrestrial source rock with a partial contribution from a marine source. These gases may have migrated to the near-surface environment, where they represent an admixture of thermally generated hydrocarbon gases from mixed sources and maturity. The maturity scale (δ¹³C versus Log Ro %) applied to the surface sediment samples of the Jamnagar area indicated the source material to be capable of generating oil and gas. The detection of thermogenic alkane gases in near-surface sediments offers the possibility of hydrocarbons at depth in Saurashtra.     

Carbon isotope and REE characteristics of the Paleocene–Eocene shallow marine Subathu formation from the NW Himalaya (India) and their paleo-environmental implications

Carbon isotope (δ¹³C) and rare earth element (REE) concentrations in representative samples of the shallow marine Subathu Formation, explored from the Neelkanth and Dogadda sections of Northwestern Himalaya (India) were determined to infer the palaeo-environmental condition during the late Paleocene and middle Eocene. δ¹³C values show variation of ～5.0‰ with maximum excursion (?27.34‰) in calcareous sandstone at the basal part and minimum (?22‰) in red shale towards the terminal end. Total REE concentration varies (due to lithology) from 27.23?ppm to 564.35?ppm with an average of 187.60?ppm. The chondrite and PAAS normalized patterns exhibit positive Ce anomaly (0.95–4.45), enriched LREE, and depleted HREE, medium Y/Ho ratio (～30–45) along with positive correlation between Y/Dy and Y/Ho ratio. In addition, calcite veins present in some shale samples indicate redox sensitive trace elements. The overall REE abundance and distribution suggests highly oxygenated environment under the shallow marine regressive phase of deposition. The depositional setting, biostratigraphical constrained age along with δ¹³C values and lower TOC suggested an intense warm period, that might be coeval with the Paleocene-Eocene Thermal Maxima event (PETM).     

Light hydrocarbons geochemistry of surface sediments from Pranhita-Godavari Basin,Andhra Pradesh

A geochemical study of surface sediments from Pranhita-Godavari Basin, Andhra Pradesh, India was carried out using light hydrocarbon compounds to assess the hydrocarbon potential of the basin. Suite of 80 soil samples were collected from the depth of 2.5 m and analyzed for adsorbed light gaseous hydrocarbons namely methane (CH₄), ethane (C₂H₆) and propane (C₃H₈) in Gas chromatograph. Compound specific Carbon isotope ratios for CH₄ and C₂H₆ were also determined using GC-C IRMS (Gas Chromatograph Combustion Isotope Mass Spectrometer). The presence of moderate to low concentrations of methane (C_CH4 C_{CH_4 } : 1 to 138 ppb), ethane (H₄{H_4 }: 1 to 35 ppb) and propane (C_{C3 H8} C_{C_3 H_8 } : 1 to 20 ppb) was measured in the soil samples. Carbon isotopic composition of d¹³ C_CH4 \delta ^{13} C_{CH_4 } ranges between −27.9 to −47.1 ‰ and d¹³ C_{C2 H6} \delta ^{13} C_{C_2 H_6 } ranged between −36.9 to −37.2 ‰ (V-PDB) indicating that these gases are of thermogenic origin. Study of soil samples suggests the area has good potential for hydrocarbon.     

Near surface manifestation of hydrocarbons in Proterozoic Bhima and Kaladgi Basins: Implications to hydrocarbon resource potential

Reconnaissance surface geochemical survey for adsorbed soil gas analysis conducted in Proterozoic Bhima and Kaladgi Basins, have revealed occurrence of anomalous concentrations of light gaseous hydrocarbons i.e. C₁ to C₄ (CH₄, C₂H₆, C₃H₈, i-C₄H₁₀ and n-C₄H₁₀) in the near surface soils. The concentrations of C₁ and ΣC₂₊(C₂H₆+C₃H₈+ i-C₄H₁₀+ n-C₄H₁₀) in Bhima and Kaladgi Basins are in the range of 1–2594 ppb and 1 to 57 ppb and 1–1142 ppb and 1–490 ppb, respectively. The carbon isotopic data of adsorbed soil gas methane in few selected samples are in the range of −29.9 to −39‰ (PDB). The evaluation of adsorbed soil gas data indicates that all the gas components are cogenetic and hydrocarbon ratios of C₁/(C₂+C₃) < 10 and C₃/C₁*1000 between 60–500 and 20–60 suggest that the adsorbed gases are derived from oil and gas-condensate zones. The carbon isotopic values of methane further support thermogenic origin of these migrated gases. The concentration distribution of C₁ and ΣC₂₊ in the study areas illustrate C₁ and ΣC₂₊ anomalies near Katamadevarhalli, Andola and Talikota in Bhima Basin and near Kaladgi, Lokapur and north of Mudhol in Kaladgi Basin. The hydrocarbon anomalies near the surface coincide with the favourable subsurface structural features and correlate with existing geochemical and geophysical data in these basins suggesting seepage related anomalies.     

成煤母质形成环境对热成因煤层气氢碳同位素的影响:不同气候环境的草本沼泽泥炭热模拟实验

煤层气的成因研究可以为煤层气勘探与开发提供科学依据,然而,煤层气的氢碳同位素组成受多种因素的影响,以前较多的研究是成气母质性质和成熟度对煤层气氢碳同位素的影响,对于成煤物质形成的气候环境对热解煤层气同位素的影响尚不清楚.热解模拟了高纬度寒冷干旱和低纬度热带湿润环境的草本泥炭,对热解烃类气体的氢碳同位素组成及其差异性进行了研究.研究结果表明:与低纬度热带湿润环境中形成的草本泥炭相比较,高纬度寒冷干旱环境的草本泥炭热解甲烷、乙烷和丙烷具有轻的氢同位素组成和重的碳同位素组成,并且从泥炭连续热解至R_o分别为2.5%、3.5%和5.5%时,甲烷、乙烷和丙烷δD值分别平均降低-17‰~-10‰、-32‰~-28‰和-25‰~-17‰,甲烷和乙烷δ13C值分别平均升高2.9‰~3.6‰和0.9‰~1.1‰.认为这种同位素差异起因于气候环境对形成泥炭的植物氢碳同位素组成的影响.建立了高纬度寒冷干旱和低纬度热带湿润环境中形成的成煤有机质热解烃类气体氢碳同位素组成与R_o之间的关系式,同时也建立了烃类气体的碳和氢同位素之间的关系式.这些研究成果为不同气候环境下形成的成煤有机质生成的煤层气成因研究提供了科学依据.      

Geochemistry of peridotite and granite xenoliths during the early stage of weathering in the Nyos volcanic region (NW Cameroon): Implications for PGE exploration

Peridotite and granite xenoliths, in the early stage of weathering, occur in the Nyos volcanic region (NW Cameroon). Geochemical data shows that peridotites are marked by high concentrations of MgO (42.30 wt.%, with SiO₂/MgO ∼ 1), chromium (2100 ppm), nickel (2100 ppm) and cobalt (104 ppm), as well as by low lanthanide contents (ΣREE: 7.41 ppm). Granites display SiO₂ contents (70–73 wt.%), and are mostly peraluminous (1.40 > A/CNK < 1.6). They are also characterized by low contents in chromium (<24 ppm), nickel (ranging from 6 to 15 ppm) and cobalt (ranging from 3 to 6 ppm). Granites possess high lanthanide contents (ΣREE varying between 248.00 and 463.00 ppm), particularly in light lanthanides (LREE/HREE ratios ranging from 21 to 32). The chondrite-normalized patterns of the studied xenoliths are characterized by: (i) LREE enrichments in both rock types; (ii) negative Eu anomalies ([Eu/Eu*] ranging from 0.45 to 0.64) and weak positive Ce anomalies ([Ce/Ce*] ranging from 1.06 to 1.46) in granites. The weathering process provokes a remobilization of several trace elements notably light lanthanides.The geochemical survey of Platinum-Group Elements (PGE) done in these rocks in the early stage of weathering shows that PGE contents are less than 7 ppb in the peridotites. The highly concentrated elements are ruthenium (6.26 ppb) and platinum (5.53 ppb). The total PGE content is 14.57 ppb. These concentrations normalized with respect to chondrites display a flat spectrum from iridium to platinum. PGE contents in the granites are below detection limit except for two samples (LNY01 and LNY02) whose platinum content is close to 0.23 ppb.     

Petrographic and Geochemicial Characteristics of the K?z?loren Formation (Upper Triassic-Lower Jurassic) in the Akp?nar (Konya, Turkey) Area

This paper describes the occurrence of dolomite and the mechanism of dolomitization of the Upper Triassic-Lower Jurassic K?z?loren Formation in the autochthonous Bolkardag? unit of the middle Taurus Mountains in south western Turkey. Dolomites were analyzed for geochemical, isotopic and crystallographic variation. Dolomites occur as a replacement of precursor carbonate and cement. The dolomite crystals range from <10 to ~1000 μm existing as both replacements and cements. Sr concentrations range between 84 and 156 ppm, and the molar Sr/Ca ratios of dolomitizing fluids are estimated to range between 0.0066 to 0.013 ratios. Dolomites are Ca-rich (with average CaCO3 and MgCO3 equal to 56.43 and 43.57 mol%, respectively) and they are non-stoichiometric, with an average Sr=116 ppm, Na=286 ppm, Mn=81 ppm, Fe=1329 ppm, and δ18O and δ13C ranges from –0.6‰ to –6.1‰ Pee Dee Belemnite [PDB], and +1.2 to +3.9‰ PDB. The North American Shale Composition [NASC]-normalized rare earth element (REE) values of the both limestone and dolomite sample groups show very similar REE patterns characterized by small positive Eu (mean=1.32 and mean=1.42, respectively) and slightly or considerably negative Ce (mean=0.61 and mean=0.72, respectively) anomalies and a clear depletion in all REE species. The K?z?loren Formation dolomites have been formed as early diagenetic from mixing zone fluids at the tidal-subtidal environment and at the late diagenetic from basinal brines at the shallow-deep burial depths.     

<Superscript>10</Superscript>Be, <Superscript>18</Superscript>O and radiogenic isotopic constraints on the origin of adakitic signatures: a case study from Solander and Little Solander Islands,New Zealand

Subduction-related Quaternary volcanic rocks from Solander and Little Solander Islands, south of mainland New Zealand, are porphyritic trachyandesites and andesites (58.20–62.19 wt% SiO₂) with phenocrysts of amphibole, plagioclase and biotite. The Solander and Little Solander rocks are incompatible element enriched (e.g. Sr ~931–2,270 ppm, Ba ~619–798 ppm, Th ~8.7–21.4 ppm and La ~24.3–97.2 ppm) with MORB-like Sr and Nd isotopic signatures. Isotopically similar quench-textured enclaves reflect mixing with intermediate (basaltic-andesite) magmas. The Solander rocks have geochemical affinities with adakites (e.g. high Sr/Y and low Y), whose origin is often attributed to partial melting of subducted oceanic crust. Solander sits on isotopically distinct continental crust, thus excluding partial melting of the lower crust in the genesis of the magmas. Furthermore, the incompatible element enrichments of the Solander rocks are inconsistent with partial melting of newly underplated mafic lower crust; reproduction of their major element compositions would require unrealistically high degrees of partial melting. A similar argument precludes partial melting of the subducting oceanic crust and the inability to match the observed trace element patterns in the presence of residual garnet or plagioclase. Alternatively, an enriched end member of depleted MORB mantle source is inferred from Sr, Nd and Pb isotopic compositions, trace element enrichments and εHf ? 0 CHUR in detrital zircons, sourced from the volcanics. ¹⁰Be and Sr, Nd and Pb isotopic systematics are inconsistent with significant sediment involvement in the source region. The trace element enrichments and MORB-like Sr and Nd isotopic characteristics of the Solander rocks require a strong fractionation mechanism to impart the high incompatible element concentrations and subduction-related (e.g. high LILE/HFSE) geochemical signatures of the Solander magmas. Trace element modelling shows that this can be achieved by very low degrees of melting of a peridotitic source enriched by the addition of a slab-derived melt. Subsequent open-system fractionation, involving a key role for mafic magma recharge, resulted in the evolved andesitic adakites.     

Origin and Accumulation of Natural Gases in the Upper Paleozoic Strata of the Ordos Basin in Central China

The natural gases in the Upper Paleozoic strata of the Ordos basin are characterized by relatively heavy C isotope of gaseous alkanes with δ 13C1 and δ13C2 values ranging mainly from ?35‰ to ?30‰ and ?27‰ to ?22‰, respectively, high δ13C excursions (round 10) between ethane and methane and predominant methane in hydrocarbon gases with most C1/(C1-C5) ratios in excess of 0.95, suggesting an origin of coal-derived gas. The gases exhibit different carbon isotopic profiles for C1-C4 alkanes with those of the natural gases found in the Lower Paleozoic of this basin, and believed to be originated from Carboniferous-Permian coal measures. The occurrence of regionally pervasive gas accumulation is distinct in the gently southward-dipping Shanbei slope of the central basin. It is noted that molecular and isotopic composition changes of the gases in various gas reservoirs are associated with the thermal maturities of gas source rocks. The abundances and δ13C values of methane generally decline northwards and from the basin center to its margins, and the effects of hydrocarbon migration on compositional modification seem insignificant. However, C isotopes of autogenetic calcites in the vertical and lateral section of reservoirs show a regular variation, and are as a whole depleted upwards and towards basin margins. Combination with gas maturity gradient, the analysis could be considered to be a useful tool for gas migration.     

Origins of non-equilibrium lithium isotopic fractionation in xenolithic peridotite minerals: Examples from Tanzania

Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ⁷Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ⁷Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ⁷Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ⁷Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ⁷Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ⁷Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ⁷Li), while non mantle-like, low δ⁷Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.