Distribution and significance of novel low molecular weight sterenes in an immature evaporitic sediment from the Jinxian Sag,North China

An unusual series of C₂₂–C₂₇ monounsaturated sterenes and C₂₄–C₃₀ tetracyclic terpanes (17,21-secohopanes) were detected in relatively high concentrations in an immature evaporitic marl sediment of the Jinxian Sag, Bohai Bay Basin, North China. The site of unsaturation in these novel sterenes is assigned tentatively to the D ring on the basis of mass spectral interpretation, which also distinguishes them from reported unsaturated sterenes. Other hydrocarbon biomarker or stable isotope characteristics are indicative of microbial (e.g. methyl hopanes), phytoplankton or higher plant (depleted δ¹³C values of isoprenoids and hopanes) inputs and an anoxic carbonate depositional environment (hexacyclic hopanes; tetracyclic terpanes). The hydrocarbon composition showed no obvious biodegradation and the relatively high concentration of unsaturated terpenoids (e.g. gammacerene) and low values of other established maturity parameters (T_s/T_m = 0.23; R_o = 0.44%; T_max = 417 °C), are consistent with sediments of low maturity. The novel, low molecular weight sterenes and the tetracyclic terpanes may be early diagenetic products of microbial sources in a carbonate environment.     

Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems

A series of methane (CH₄) adsorption experiments on bulk organic rich shales and their isolated kerogens were conducted at 35 °C, 50 °C and 65 °C and CH₄ pressure of up to 15 MPa under dry conditions. Samples from the Eocene Green River Formation, Devonian–Mississippian Woodford Shale and Upper Cretaceous Cameo coal were studied to examine how differences in organic matter type affect natural gas adsorption. Vitrinite reflectance values of these samples ranged from 0.56–0.58 %R_o. In addition, thermal maturity effects were determined on three Mississippian Barnett Shale samples with measured vitrinite reflectance values of 0.58, 0.81 and 2.01 %R_o.For all bulk and isolated kerogen samples, the total amount of methane adsorbed was directly proportional to the total organic carbon (TOC) content of the sample and the average maximum amount of gas sorption was 1.36 mmol of methane per gram of TOC. These results indicate that sorption on organic matter plays a critical role in shale-gas storage. Under the experimental conditions, differences in thermal maturity showed no significant effect on the total amount of gas sorbed. Experimental sorption isotherms could be fitted with good accuracy by the Langmuir function by adjusting the Langmuir pressure (P_L) and maximum sorption capacity (Γ_max). The lowest maturity sample (%R_o = 0.56) displayed a Langmuir pressure (P_L) of 5.15 MPa, significantly larger than the 2.33 MPa observed for the highest maturity (%R_o > 2.01) sample at 50 °C.The value of the Langmuir pressure (P_L) changes with kerogen type in the following sequence: type I > type II > type III. The thermodynamic parameters of CH₄ adsorption on organic rich shales were determined based on the experimental CH₄ isotherms. For the adsorption of CH₄ on organic rich shales and their isolated kerogen, the heat of adsorption (q) and the standard entropy (Δs⁰) range from 7.3–28.0 kJ/mol and from −36.2 to −92.2 J/mol/K, respectively.     

Use of comprehensive two-dimensional gas chromatography for the characterization of ultra-deep condensate from the Bohai Bay Basin,China

A gas condensate from well ND1 in the Jizhong Depression of the Bohai Bay Basin, China is characterized by two-dimensional gas chromatography with flame ionization detector (GC × GC–FID) and time-of-flight mass spectrometry (GC × GC–TOFMS). This condensate is sourced from the fourth member of the Shahejie Formation (Es4) but reservoired in the Mesoproterozoic Wumishan Formation carbonate at a depth of 5641–6027 m and the reservoir temperature is 190–201 °C. It is the deepest and the highest temperature discovery in the basin to date. The API gravity of the condensate is 51° and the sulfur content is < 0.04%. A total of 4955 compounds were detected and quantified. Saturated hydrocarbons, aromatic hydrocarbons and non-hydrocarbon account for 94.8%, 5.1% and 0.02% of the condensate mass, respectively. Some long chain alkylated cyclic alkanes, decahydronaphthalenes and diamondoids are tentatively identified in this condensate. The C₆–C₉ light hydrocarbon parameters show that the gas condensate was generated at relatively high maturity but its generation temperature derived from the dimethylpentane isomer ratio seems far lower than the current reservoir temperature. Some light hydrocarbon parameters indicate evaporative fractionation may also be involved due to multiple-charging and mixing. The diamondoid concentrations and gas oil ratio (GOR) suggest that the ND1 condensate results from 53.3–55% cracking. Since significant liquids remain, the exploration potential of ultra-deep buried hill fields in the Bohai Bay Basin remains high.     

Artificial bacterial degradation and hydrous pyrolysis of suberin: Implications for hydrocarbon generation of suberinite

The organic maceral suberinite is widely believed to be a contributor to immature or low mature oils with R_o < 0.5% in some coal and terrigenous sequences. However, its evolution of hydrocarbon generation, especially in the relatively high maturation stage of R_o > 0.5%, has not been sufficiently characterized. This issue was addressed herein using periderm cork tissues of the modern angiosperm Quercus suber (suberin), which is a possible bio-precursor of suberinite, in artificial bacterial degradation and hydrous pyrolysis experiments. Integrated studies were conducted, including analyses on the compositions of hydrocarbon yields and the content variations that were generated during the experiments, gas chromatography (GC) analyses of generated oils and spectral fluorescence observations, and Rock-Eval and Fourier Transform Infrared (FTIR) microspectroscopic studies on solid residues. Analytical results indicate that suberin and suberinite have long and complex hydrocarbon generation histories. In general, the hydrocarbon that is generated during bacterial degradation is predominantly gas and present in relatively limited amounts, while the oils mainly are generated during hydrous pyrolysis. Furthermore, the oil generation has two peaks that correspond to R_o of approximately 0.35–0.50% and 0.80–1.10%. In composition, the early generated oil mainly consists of long chain waxy and oxygen containing compounds, while the late generated oil is relatively enriched in aromatic compounds. These features can be ascribed to the chemical nature (e.g., composition and structure) of suberin. It is a type of insoluble and high molecular weight polyester compound that contains large quantities of long chain structure dicarboxylic acids and alcohols. Consequently, the deoxygenization of these compounds can take place under relatively low thermodynamic conditions, generating liquid oil that is dominated by a long chain structure and oxygen-containing waxy compounds. In contrast, the degradation of the phenolic compounds results in the second oil generation peak. Therefore, suberinite has a two stage and relatively long oil generation history and is a good bio-precursor for coal-derived oil generation.     

Characterization of the CO2 fluid adsorption in coal as a function of pressure using neutron scattering techniques (SANS and USANS)

Small angle neutron scattering techniques have been applied to investigate the phase behavior of CO₂ injected into coal and possible changes in the coal pore structure that may result from this injection. Three coals were selected for this study: the Seelyville coal from the Illinois Basin (R_o = 0.53%), Baralaba coal from the Bowen Basin (R_o = 0.67%), and Bulli 4 coal from the Sydney Basin (R_o = 1.42%). The coals were selected from different depths to represent the range of the underground CO₂ conditions (from subcritical to supercritical) which may be realized in the deep subsurface environment. The experiments were conducted in a high pressure cell and CO₂ was injected under a range of pressure conditions, including those corresponding to in-situ hydrostatic subsurface conditions for each coal. Our experiments indicate that the porous matrix of all coals remains essentially unchanged after exposure to CO₂ at pressures up to 200 bar (1 bar = 10⁵ Pa). Each coal responds differently to the CO₂ exposure and this response appears to be different in pores of various sizes within the same coal. For the Seelyville coal at reservoir conditions (16 °C, 50 bar), CO₂ condenses from a gas into liquid, which leads to increased average fluid density in the pores (ρ_pore) with sizes (r) 1 × 10⁵ ≥ r ≥ 1 × 10⁴ Å (ρ_pore ≈ 0.489 g/cm³) as well as in small pores with size between 30 and 300 Å (ρ_pore ≈ 0.671 g/cm³). These values are by a factor of three to four higher than the density of bulk CO₂ (ρ_CO2) under similar thermodynamic conditions (ρ_CO2 ≈ 0.15 g/cm³). At the same time, in the intermediate size pores with r ≈ 1000 Å the average fluid density is similar to the density of bulk fluid, which indicates that adsorption does not occur in these pores. At in situ conditions for the Baralaba coal (35 ^OC, 100 bar), the average fluid density of CO₂ in all pores is lower than that of the bulk fluid (ρ_pore / ρ_CO2 ≈ 0.6). Neutron scattering from the Bulli 4 coal did not show any significant variation with pressure, a phenomenon which we assign to the extremely small amount of porosity of this coal in the pore size range between 35 and 100,000 Å.     

Radiolytic alteration of biopolymers in the Mulga Rock (Australia) uranium deposit

We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO₂/g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C₂₇–C₃₁) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are inconsistent with diagenetic degradation of terrigenous OM in oxic depositional environments and cannot be associated with thermal breakdown due to the relatively low thermal maturity of the deposits (R_r = 0.26%). It is assumed that the intimate spatial association of high U concentrations resulted in breakdown via radiolytic cracking of recalcitrant polyaliphatic macromolecules (spores, pollen, cuticles, or algal cysts) yielding medium chain length n-alkanes (C₁₃–C₂₄). Reactions of n-alkenes with OH⁻ radicals from water hydrolysis produced alcohols that dehydrogenated to alkanones or through carbonylation formed alkanones. Rapid reactions with hydroxyl radicals likely decreased the isomerization of n-alkenes and decreased alkanone diversity, such that the alkan-2-one isomer is predominant. This specific distribution of components generated by natural radiolysis enables their application as “radiolytic molecular markers”. Breaking of C–C bonds through radiolytic cracking at temperatures much lower than the oil window (<50 °C) can have profound implications on initiation of petroleum formation, paleoenvironmental reconstructions, mineral exploration and in tracking radiolysis of OM.     

Hydrocarbon generation from coal,extracted coal and bitumen rich coal in confined pyrolysis experiments

Three sets of pyrolysis experiments were performed on extracted coal (R_o% 0.39), coal (initial bitumen 13.5 mg/g coal) and bitumen enriched coal (total bitumen 80.9 mg/g coal) at two heating rates of 2 °C/h and 20 °C/h in confined systems (gold capsules). For all three experiments, the yields of bitumen, Σn-C₈₊, aromatic components and ΣC_2–5 at first increase and then decrease with increasing EASY%R_o and reach the highest values within the EASY%R_o ranges of 0.67–1.08, 1.07–1.19, 1.46–1.79 and 1.46–1.68, respectively. In contrast, C₁/ΣC_1–5 ratio at first decreases and then increases with EASY%R_o and reaches a minimum value in EASY%R_o range of 0.86–1.08, closely corresponding to the maximum values of the yields of bitumen and Σn-C₈₊. Methane yields increase consistently with EASY%R_o. Nearly half of the maximum yield of methane from kerogen was generated at EASY%R_o > 2.2. The differences in methane yields among the three experiments at the same thermal stress are relatively minor at EASY%R_o < 2.2, but are greater with thermal stress at EASY%R_o > 2.2. This demonstrates that the kerogen always retained relatively more hydrogen and hydrocarbon generative potential at the postmature stage of bitumen rich coal than the extracted coal or coal.The maximum yield of ethane is 20–25% higher in the bitumen rich coal experiment than the extracted coal or coal, while the maximum yields of C₃, C₄ and C₅ in the former are double to triple those in the latter. This result demonstrates that the added bitumen in bitumen rich coal substantially increased the generation of these wet gases. However, the averaged values of activation energies (with the same frequency factors) for both the generation and cracking of individual wet gases are similar and do not show consistent trends among the three experiments. For all three experiments, activation energies for the generation and cracking of wet gases are significantly lower than those in previously published oil pyrolysis experiments with same frequency factors (Pan et al., 2012; Organic Geochemistry 45, 29–47). Methane δ¹³C values at the maximum temperature or EASY%R_o are close to those of initial wet gases, especially C₃, implying that the major part of methane shared a common initial precursor with wet gases, i.e., free and bound liquid alkanes.     

FTIR microspectroscopy of Ediacaran phosphatized microfossils from the Doushantuo Formation,Weng'an,South China

Phosphatized microfossils from ca. 580 Ma from the Doushantuo Formation in the Weng'an region of South China were analyzed by Fourier transform infrared (FTIR) microspectroscopy for their chemical characterization. Two morpho-types of phosphatized embryo-like fossils (Megasphaera and Megaclonophycus) were analyzed, together with algal fossils. Transmission IR spectra of the microfossils have absorption bands of around 2960 cm^− 1 and 2925 cm^− 1, indicating the presence of aliphatic hydrocarbon (anti-symmetric aliphatic CH₃ and aliphatic CH₂), and have an additional band of around 1595 cm^− 1, probably derived from aromatic moieties (aromatic CC). In addition, IR microscopic mapping shows that aliphatic hydrocarbon and aromatics are distributed inside the embryo-like fossils. The embryo-like fossils appear to show three types of CH₃/CH₂ peak height ratios (R_3/2) and aromatic CC/CH₂ peak height ratios (R_CC/2 values): (1) high-R_3/2/low-R_CC/2 type (R_3/2 = ~ 0.2–1.0 and R_CC/2 ~ 0–2), (2) low-R_3/2/medium-R_CC/2 type (R_3/2 = ~ 0.2–0.6 and R_CC/2 = ~ 1–4); and (3) low-R_3/2/high-R_CC/2 type (R_3/2 = ~ 0.2–0.6 and R_CC/2 ~ 1–8). All three types are contained in both Megasphaera and Megaclonophycus. Raman spectra for the carbonaceous matter within the rock sample show a similar degree of thermal alteration, indicating that the organics were embedded in situ prior to thermal maturation. The IR spectroscopic differences might reflect differences in original organic compositions of microorganisms, and/or immediate post-mortem alteration. This suggests that the origins of phosphatized embryo-like fossils are more diverse than was previously recognized on the basis of their morphology. A comparison of R_3/2 and R_CC/2 values in the embryo-like fossils with those of the algal fossils and the extant microorganisms indicates the possible interpretation that some of the embryo-like fossils belong to animal embryo, others are algae, but none of them originate from bacteria.     

Evaluation of the petroleum composition and quality with increasing thermal maturity as simulated by hydrous pyrolysis: A case study using a Brazilian source rock with Type I kerogen

Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C₁₅₊ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C₁₅₊ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C₁₅₊ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m³/m³ during bitumen generation and remain essentially constant (81–84 m³/m³) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C₁₇ and phytane/n-C₁₈) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.     

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.     

Fluid inclusion geochemistry and Ar–Ar geochronology of the Cenozoic Bangbu orogenic gold deposit,southern Tibet,China

Located along the southern part of the Yarlung Zangbo suture zone in southern Tibet, Bangbu is one of the largest gold deposits in Tibet. Auriferous sulfide-bearing quartz veins are controlled by second- or third-order brittle fractures associated with the regional Qusong–Cuogu–Zhemulang brittle-ductile shear zone. Fluid inclusion studies show that the auriferous quartz contains aqueous inclusions, two-phase and three-phase CO₂-bearing inclusions, and pure gaseous hydrocarbon inclusions. The CO₂-bearing inclusions have salinities of 2.2–9.5% NaCl_eq, and homogenization temperatures (Th) of 167–336 °C. The δD, δ¹⁸O, and δ¹³C compositions of the Bangbu ore-forming fluids are − 105.5 to − 44.4‰, 4.7 to 9.0‰ and − 5.1 to − 2.2‰, respectively, indicating that the ore-forming fluid is mainly of metamorphic origin, with also a mantle-derived contribution. The ³He/⁴He ratio of the ore-forming fluids is 0.174 to 1.010 R_a, and ⁴⁰Ar/³⁶Ar ranges from 311.9 to 1724.9. Calculations indicate that the percentage of mantle-derived He in fluid inclusions from Bangbu is 2.7–16.7%. These geochemical features are similar to those of most orogenic gold deposits. Dating by ⁴⁰Ar/³⁹Ar of hydrothermal sericite collected from auriferous quartz veins at Bangbu yielded a plateau age of 44.8 ± 1.0 Ma, with normal and inverse isochronal ages of 43.6 ± 3.2 Ma and 44 ± 3 Ma, respectively. This indicates that the gold mineralization was contemporaneous with the main collisional stage between India and Eurasia along the Yarlung Zangbo suture, which resulted in the development of near-vertical lithospheric shear zones. A deep metamorphic fluid was channeled upward along the shear zone, mixing with a mantle fluid. The mixed fluids migrated into the brittle structures along the shear zone and precipitated gold, sulfides, and quartz because of declining temperature and pressure or fluid immiscibility. The Bangbu is a large-scale Cenozoic syn-collisional orogenic gold deposit     

Zircon U-Pb geochronology,Lu-Hf isotope systematics,and geochemistry of bimodal volcanic rocks and associated granitoids from Kotri Belt,Central India: Implications for Neoarchean–Paleoproterozoic crustal growth

The Bastar Craton of Central India has a thick sequence of volcano–sedimentary rocks preserved in Kotri–Dongargarh belt that developed on a tonalite-trondhjemite-granodiorite (TTG) basement followed upwards by the Amgaon, Bengpal, Bailadila, and Nandgaon Groups of rocks. Here, we report the U-Pb geochronology and Lu-Hf isotope systematics and whole rock geochemistry of volcanic rocks and associated granitoids belonging to the Pitepani basalts, Bijli rhyolites, and Dongargarh granite in the Nandgaon Group of the Kotri belt. The volcanic rocks of the Nandgaon Group are bimodal in nature in which the basalts exhibit intergranular, porphyritic to spherulitic texture composed of pyroxenes, plagioclase, tremolite, actinolite, and chlorite ± Fe oxides. The rhyolites display porphyritic texture consisting of K-feldspar, quartz, and plagioclase as phenocrysts. The associated porphyritic granitoids have K-feldspar, microcline, plagioclase, and biotite phenocrysts within a groundmass of similar composition. The bimodal suite displays LILE, LREE enrichment, and HFSE depletion with significant negative Nb-Ta anomalies combined with slightly fractionated REE patterns in the basalts and highly fractionated patterns and prominent negative Eu anomalies in the rhyolites endorsing their generation in an island-arc/back-arc tectonic setting. The geochemical features of the associated granitoids indicate that these are potassic and classify as within-plate A-type granites. Zircons from the basalts show clear oscillatory zoning in their CL images. They cluster as a coherent group with ²⁰⁷Pb/²⁰⁶Pb spot ages ranging from 2446 to 2522 Ma and weighted mean age of 2471 ± 7 Ma. Zircons from the rhyolite samples are subhedral to euhedral and show simple oscillatory zoning with some heterogeneous fractured domains. The data from two samples define upper intercept ages of 2479 ± 13 Ma and 2463 ± 14 Ma. Zircon grains in the granite show clear oscillatory zoning and their U-Pb data define an upper intercept age of 2506 ± 50 Ma. The Lu-Hf isotopic data on the zircons from the basalts show initial ¹⁷⁶Hf/¹⁷⁷Hf ratios from 0.280925 to 0.281018. Their ε_Hf(t) values are in the range of − 10.0 to − 6.7. The Hf-depleted model ages (T_DM) are between 3038 Ma and 3171 Ma, and Hf crustal model ages (T_DM^C) vary from 3387–3589 Ma. The zircons from the rhyolites show initial ¹⁷⁶Hf/¹⁷⁷Hf ratios from 0.280919 to 0.281020 and from 0.281000 to 0.281103, respectively, with ε_Hf(t) values varying from − 10 to − 6.4 and from − 7.5 to − 3.9. Among these, one sample shows T_DM between 3038 Ma and 3182 Ma, and T_DM^C varies from 3377 to 3596 Ma, whereas the other sample shows ages of 2925 Ma and 3072 Ma with T_DM^C varying from 3208 to 3432 Ma. The initial ¹⁷⁶Hf/¹⁷⁷Hf ratios of the granites range from 0.280937 to 0.281062 with ε_Hf(t) values of − 8.8 to − 4.3. The T_DM shows a range of 2979 Ma and 3170 Ma, and T_DM^C varies from 3269 to 3541 Ma. The predominant negative ε_Hf(t) values of zircons from these rocks suggest that the source material was evolved from the Paleoarchean crust. The geological, geochemical, and geochronological evidence suggests coeval tectonic and magmatic episodes of volcanic and plutonic activity in an island-arc setting where the arc migrated toward the continental margin and played a significant role in the Neoarchean–Paleoproterozoic crustal growth of the Kotri belt of Central India.     

Multi-stage metamorphic evolution of retrograde eclogite with a granulite-facies overprint in the Zhaigen area of the North Qinling Belt,China

Retrograde eclogite from the central part of the Qinling Complex, Zhaigen area of the North Qinling Belt, was studied using integrated petrology, mineral chemistry, pseudosection modeling, and geochronology. Microstructures and mineral relationships reveal five metamorphic stages and associated mineral assemblages as follows: (1) pre-peak stage M₁, which is recorded by the inner cores of garnets together with mineral inclusions of clinopyroxene (Cpx₁) + amphibole (Am₁) + plagioclase (Pl₁) ± quartz ± rutile, occurred under conditions of 760–770 °C and 11.4–14.0 kbar; (2) eclogite-facies stage M₂, recorded by garnet cores + relic omphacite (with a high jadeite content up to 31%) + rutile + quartz under conditions of > 16.7 kbar and 679–765 °C; (3) high-pressure granulite-facies stage M₃, characterized by clinopyroxene (Cpx₂) + plagioclase (Pl₂) symplectites under conditions of 14.5–15.6 kbar and 800–850 °C; (4) medium-pressure granulite-facies stage M₄, characterized by the growth of plagioclase + orthopyroxene coronas around garnet under conditions of 8.3–10 kbar and 795–855 °C; and (5) retrogressive amphibolite-facies stage M₅, which is represented by amphibole (Am₃) + plagioclase (Pl₃) kelyphitic rims around garnet at conditions of < 4 kbar and < 620 °C. Based on Laser Raman analysis of mineral inclusions, cathodoluminescence images, in situ trace element concentrations from different domains within zircon grains, and LA-ICP-MS and SHRIMP U–Pb dating, the protolith age of the Zhaigen retrograde eclogite is suggested at 786 ± 10 Ma and the eclogite-facies metamorphic age recorded by metamorphic zircon cores is limited within 501–497 Ma. The retrograde zircon rims display ages of 476–447 Ma and 425 Ma that probably reflect the timing of two stages of retrograde metamorphism, respectively. The mineral assemblages, P–T conditions, and zircon U–Pb data define a clockwise P–T–t path for the retrograde eclogite, suggesting that the Neoproterozoic protolith of the retrograde eclogite might evolved into continental subduction and eclogite-facies metamorphism during 501–497 Ma before undergoing retrograde metamorphism during an initial stage of exhumation to middle–upper crust level at 474–447 Ma and subsequent exhumation to shallow upper crust at ~ 420 Ma.     

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.     

New SHRIMP,Rb/Sr and Sm/Nd isotope and whole rock chemical data from central Mozambique and western Dronning Maud Land,Antarctica: Implications for the nature of the eastern margin of the Kalahari Craton and the amalgamation of Gondwana

Whole rock major and trace element data from granitoids adjacent to the Kalahari Craton–Mozambique–Maud Belt boundary are described. The data from ～1140 Ma old granodioritic and ～1110 Ma old granitic bodies in the Mozambique Belt show that they are typical of calc-alkaline and A-type granitoids respectively. Radiogenic Rb/Sr and Sm/Nd isotope data from the two granitoid bodies suggest significant older crustal contributions during their genesis. The granodioritic gneisses show T_DM model ages of ～2100–3500 Ma whereas megacrystic granitic gneisses have T_DM model ages of ～1600–3100 Ma. Granite from the Archaean-age Kalahari Craton has T_DM model ages of ～3000–3500 Ma.The data from Mozambique are compared with whole rock major and trace element chemistry and U/Pb zircon SHRIMP data from the Maud Belt in western Dronning Maud Land. These show that ～1140 Ma old granodioritic gneisses in Sverdrupfjella and Kirwanveggan have similar ages and chemical compositions to similar rocks in central Mozambique. Radiogenic isotope characteristics of the gneisses from central Mozambique and Sverdrupfjella are similar and suggest older crustal contributions in contrast to the juvenile nature of the gneisses from Kirwanveggan.Similarly, ～1090 Ma old granitic gneisses from central Mozambique, Sverdrupfjella and Kirwanveggan have similar ages and A-type chemical compositions. In contrast the radiogenic isotope compositions from Kirwanveggan are juvenile whereas those from central Mozambique show a significant older crustal contribution.The whole rock radiogenic isotope data can be interpreted to suggest that the Mesoproterozoic Mozambique Belt rocks were generated by partial melting which probably involved mixing of Archaean/Paleoproterozoic crust and younger Mesoproterozoic juvenile magma at ～1100 Ma and suggest that the Kalahari Craton probably extends eastwards at depths for more than 30 km from its exposure at surface.The data support correlations between the Mozambique Belt and the Maud Belt in Antarctica in general and more specifically show similarities between the Kalahari Craton boundary and the Mozambique–Maud Belt in lithologies immediately adjacent to that boundary.Two episodes of anatectic migmatisation are recognized in rocks from the Mozambique Belt in central Mozambique. These show an earlier migmatitic vein phase oriented parallel to the planar foliation in the granitic and tonalitic gneisses and a later discordant vein phase which is oriented parallel to localized but intense N–S oriented shearing along the Kalahari Craton/Mozambique Belt boundary zone. SHRIMP zircon data from the younger migmatitic vein phase suggests a crystallization age of 997 ± 4 Ma. Small numbers of inherited zircons have ages of ～2700 Ma and ～1100–1200 Ma. Younger discordant analyses suggesting metamorphic disturbance between ～400 Ma and 550 Ma are seen. The data imply the high strain along the eastern margin of the Kalahari Craton in the Manica area, occurred at ～1000 Ma and not at ～450 Ma as was previously thought. The data suggest the Pan African deformation and metamorphism in the area involved minor reworking. The undeformed to weakly deformed Tchinadzandze Granodiorite intruded into the Kalahari Craton has an age of 2617 ± 16 Ma.     

Geology and geochemistry of the Triassic Wenquan Mo deposit and Mo-mineralized granite in the Western Qinling Orogen,China

The recently-discovered Wenquan porphyry Mo deposit hosted in the Wenquan granite of the West Qinling Orogen has been recognized as a product of the Indosinian metallogenesis. Three generations of mineral assemblage for the deposit are identified as follows: (1) quartz–biotite–K-feldspar; (2) quartz–sulfide and (3) sulfide–calcite. Geochemical study shows that the mafic microgranular enclaves (MMEs) in the ore-bearing Wenquan granite have lower SiO₂, and higher Mg# and Nb/Ta ratios than the host granite itself. Different from the granite which have zircon ε_Hf(t) values of − 3.6–3.0 and T_DM2 of 1234–890 Ma, the MMEs are characterized by the ε_Hf(t) values of − 10.1–10.8 and T_DM1 of 865–441 Ma. This can be interpreted to indicate a mixture origin of the Meso- and Neoproterozoic crust-derived component and Neoproterozoic SCLM-derived materials for the formation of the Wenquan granite, which played an essential role in the Mo mineralization. Comparative Pb isotopic data between ores and K-feldspar suggest that the Wenquan granitic magma originated from the middle-lower crust of the South China Block and the ore-forming materials were incorporated by hydrothermal fluid differentiated from the Triassic magmatic system, with minor contribution of sedimentary rocks. The δ³⁴S values of 5.0–11.7‰ with a pronounced mode at 5.0 to 6.1‰ for the ores probably represent the sulfur incorporation of a typical magmatic hydrothermal fluid contaminated by heavy sulfur of Devonian sediments. The granite yielded the zircon U–Pb ages of 218 ± 2.4 Ma and 221 ± 1.3 Ma, as the same as the ages of 217 ± 2.0 Ma and 218 ± 2.5 Ma obtained for the MMEs. These ages are indistinguishable with the molybdenite Re–Os isochron age of 219 ± 5.2 Ma which is the timing for the Mo mineralization. Tectonically, the magmatic mixture processes of the Wenquan granite and the Mo mineralization to form the Wenquan Mo deposit contemporaneously occurred during the transition of tectonic regime from syn- to post-collision orogeny in the Qinling Orogen in the Late Triassic.     

Geochronological and geochemical constraints on the petrogenesis of the early Paleoproterozoic potassic granite in the Lushan area,southern margin of the North China Craton

We conducted a geochronological and geochemical study on the Paleoproterozoic potassic granites in the Lushan area, southern margin of the North China Craton (NCC) to understand the tectonic regime of the NCC at 2.2–2.1 Ga. This rock suite formed at 2194 ± 29 Ma. The rocks are rich in SiO₂ (76.10–77.73 wt.%), and K₂O (5.94–6.90 wt.%) with high K₂O + Na₂O contents from 7.56 wt.% to 8.48 wt.%, but poor in CaO (0.10–0.28 wt.%), P₂O₅ (0.02–0.05 wt.%) and MgO (0.01–0.30 wt.%, Mg# = 1.08–27.3), indicating they experienced fractional crystallization. Major element compositions suggest the potassic granites share an affinity with high K calc-alkaline granite. Even though the Lushan potassic granitic rocks have high A/CNK ratios (1.11–1.25), which can reach peraluminous feature, the very low P₂O₅ contents and negative correlation of P₂O₅ and SiO₂ ruling out they are S-type granites. Different from peralkaline A-type granites, the Lushan potassic granites have variable Zr concentrations (160–344 ppm, 226 ppm on average) and 10,000 Ga/Al ratios (1.76–3.00), together with high zircon saturation temperatures (T_Zr = 826–885 °C), indicating they are fractionated aluminous A-type granites. Enriched LREE ((La/Yb)_N = 9.72–81.8), negative Eu anomalies, and low Sr/Y with no correlations in Sr/Y and Sr/Zr versus CaO suggest the possible presence of Ca-rich plagioclase and absence of garnet in the residual. Magmatic zircon grains have variable ε_Hf(t) values (−2.4 to +7.3) with zircon two-stage Hf model ages (T_DM^C) varying from 2848 Ma to 2306 Ma (mostly around ca. 2.5 Ga), and are plotted in the evolution line of crustal felsic rock. We propose that the rocks mainly formed by partial melting of ca. 2.50 Ga tonalitic–granodioritic crust as a result of upwelling mantle-derived magmas which provided thermal flux and source materials in an intra-continent rifting. The ca. 2.2 Ga magmatism suggests that intra-continental rifting occurred at 2.35–1.97 Ga at least in the southern margin of the NCC after its final cratonization in the late Neoarchean.     

Geochronology of the Birim Supergroup of the West African craton in the Wa-Bolé region of west-central Ghana: Implications for the stratigraphic framework

The Birim rocks of the West African craton comprise belts of greenschist- to amphibolite-grade gneiss and schist, and subparallel basins of greenschist-grade phyllite of volcaniclastic and epiclastic origin, which were intruded by igneous rocks. The granitoids intruded between 2213 and 2060 Ma and overlap with the volcaniclastic units dated between 2211 and 2064 Ma. The simultaneous occurrence of the magmatic events and irregular distribution of the rock ages hamper the formulation of a stratigraphic succession. SHRIMP spot analyses were done on older cores, crystals and rims from 23 rocks from the Bolé-Wa region in west-central Ghana. The crystallization ages range from 2195 to 2118 Ma, the inherited ages from 2876 to 2130 Ma, and metamorphic ages from 2114 to 2090 Ma. Aided by metamorphic, structural and chemical studies an older geotectonic cycle (2195–2150 Ma), containing the Dole and Guropie Suite and Bolé Group, was established. These units were subjected to several orthogonal and shear deformation events. These events were followed by the contemporaneous Sawla calc-alkaline monzonitic plutonism (2132–2126 Ma) and deposition of the epiclastic Maluwe Group (2137–2125 Ma) of calc-alkaline felsic to tholeiitic volcanic origin. Deformation of the basin beds was succeeded by the intrusion of the Tanina Suite granitoids of 2122–2120 Ma, which, themselves, were deformed prior to 2119 Ma. At 2118 Ma syenite and gabbro intruded along conjugate extension fractures. The gabbro and syenite of the Wakawaka Suite were only affected by three events of brittle strike-slip faulting. The first had significant displacement along NNE- to NE-directed shear zones, while the latter only formed conjugate joint systems with limited transport. Palaeo- to Neoarchaean cores, the oldest yet reported in the Baoulé Mossi domain, are restricted to the gneissic Dole Suite biotite granites. The presence of Dole-, Guropie-, Sawla-, and Tanina-aged older cores and grains in younger rocks reflects continuous reworking of the developing crust during successive magmatic episodes. Zircon rim growth between 2105 and 2090 Ma indicates posttectonic crustal thickening. The low Rb/Sr R_o of ～0.7032 of gabbro and monzonite, and the recycling of the Birim-age crust confirm the primary and juvenile nature of the West African craton after ～2195 Ma. With the various ages obtained, it was possible to link deposition, magmatism and deformation to crustal processes, and establish the cyclic geotectonic evolution in the West Africa craton (individual basin opening and closure) over time as part of an intraoceanic arc–back-arc basin system.     

Neoproterozoic magmatic events in the South Qinling Belt,China: Implications for amalgamation and breakup of the Rodinia supercontinent

Neoproterozoic magmatic rocks in the South Qinling Belt of China provide important clues for understanding the mechanism and timing of the amalgamation and breakup of the Rodinia supercontinent. Here we report new geochemical and high-precision LA-ICP-MS zircon U–Pb–Hf isotopic analyses on magmatic suites from the Liuba and Zhashui areas in the South Qinling Belt. Our data show that the crystallization ages of the granitic intrusions from Tiefodian and Tangjiagou in the Liuba area are 863 ± 22 Ma and 794 ± 11 Ma, respectively, whereas those of the dioritic and gabbroic intrusions at Chishuigou in the Zhashui area are 925 ± 28 Ma and 832.6 ± 4.0 Ma, respectively. The diorites at Chishuigou display arc-related geochemical affinity, characterized by strong depletion in Nb, Ta, P and Ti, and enrichment in large-ion lithophile elements (i.e., Rb, Ba, Th and U), indicating a subduction-related arc setting at ca. 925 Ma. The Tiefodian granitic rocks have high SiO₂ (68.46–70.98 wt.%), Na₂O (3.87–4.51 wt.%), and low K₂O (1.34–2.61 wt.%) contents with TTG affinity. However, their Cr, and Ni contents and Cr/Ni, Nb/Ta ratios are similar to those of continental crust, and together with high negative ε_Hf(t) values (− 4.87 to − 14.84), suggesting a continental margin arc at ca. 863 Ma. The gabbros at Chishuigou have high TiO₂ content (2.74–3.14 wt.%), Zr/Y (3.93–4.24), Ta/Yb (0.19–0.25) ratios and low Zr/Nb ratios (11.37–13.17), similar to the features of within-plate basalts, indicating an intra-continental rift setting at ca. 833 Ma. The granitoids at Tangjiagou exhibit enrichment of LREE, K and Pb, and depletion of Nb, Ta, P and Ti, suggesting an extensional tectonic environment at ca. 794 Ma.The results indicate that Neoproterozoic magmatic rocks in the South Qinling Belt formed before ca. 833 Ma and might represent the amalgamation of the Rodinia supercontinent in an arc-related subduction environment, whereas the magmatic events with the peak ages at ~ 740 Ma during ca. 833–680 Ma represent the breakup of Rodinia. Integrating our new data with those from previous works, we propose a new tectonic model for the evolutionary history of the South Qinling Belt in the Neoproterozoic, including four key stages: 1) an ocean that separated the South Qinling Belt and the Yangtze Block in the Early Neoproterozoic (ca.1000–956 Ma); 2) bidirectional subduction of the oceanic lithosphere during ca. 956–870 Ma; 3) subduction and collision between the South Qinling Belt and the Yangtze Block during ca. 870–833 Ma, thus suggesting that the South Qinling Belt was as a part of the Yangtze Block from this period; and 4) intra-continental rifting during ca. 833–680 Ma, although the blocks were not entirely rifted apart.     

Early Mesozoic metamorphism and tectonic significance of the eastern segment of the Lhasa terrane,south Tibet

The metamorphic belt in the Basongco area, the eastern segment of Lhasa terrane, south Tibet, occurs as the tectonic blocks in Paleozoic sedimentary rocks. The Basongco metamorphic rocks are mainly composed of paragneiss and schist, with minor marble and orthogneiss, and considered previously to be the Precambrian basement of the Lhasa terrane. This study shows that the Basongco metamorphic belt experienced medium-pressure amphibolite-facies metamorphism under the conditions of T = 640–705 °C and P = 6.0–8.0 kbar. The inherited detrital zircon of the metasedimentary rocks yielded widely variable ²⁰⁶Pb/²³⁸U ages ranging from 3105 Ma to 500 Ma, with two main age populations at 1150 Ma and 580 Ma. The magmatic cores of zircons from the orthogneiss constrain the protolith age as ca. 203 Ma. The metamorphic zircons from all rocks yielded the consistent metamorphic ages of 192–204 Ma. The magmatic cores of zircons in the orthogneiss yielded old Hf model ages (T_DM2 = 1.5–2.1 Ga). The magmatic zircons from the mylonitized granite yielded a crystallization age of ca. 198 Ma. These results indicate that the high-grade metamorphic rocks from the Basongco area were formed at early Jurassic and associated with coeval magmatism derived from the thickening crust. The Basongco metamorphic belt, together with the western and coeval Sumdo and Nyainqentanglha metamorphic belts, formed a 400-km-long tectonic unit, indicating that the central segment of the Lhasa terrane experienced the late Paleozoic to early Mesozoic collisional orogeny.