NEXAFS and XPS characterisation of carbon functional groups of fresh and aged biochars

The oxidation of surface functional groups on biochar increases its reactivity and may contribute to the cation exchange capacity of soil. In this study, two Eucalyptus wood biochars, produced at 450 °C (B450) and 550 °C (B550), were incubated separately in each of the four contrasting soils for up to 2 years at 20 °C, 40 °C and 60 °C. Carbon functional groups of the light fraction (< 1.8 g/cm³) of the control and biochar amended soils (fresh and aged for 1 and 2 years at 20 °C, 40 °C and 60 °C) were investigated using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). The spectra of biochar and light fractions of the control and biochar amended soils showed two distinct peaks at ∼285.1 eV and 288.5 eV, which were attributed to the C1s-π¹_CC transitions of aromatic C and C1s-π¹_CO transitions of carboxylic C, carboxyamide C and carbonyl C. The proportion of aromatic C was substantially greater in the light fraction of the biochar amended soils than the corresponding light fraction of the control soils. Also, the proportion of aromatic C was much higher in the light fraction of the B550 amended soils than in the corresponding B450 amended soils. Neither NEXAFS nor XPS results show any consistent change in the proportion of aromatic C of biochar amended soils after 1 year ageing. However, XPS analysis of hand-picked biochar samples showed an increase in the proportion of carboxyl groups after ageing for 2 years, with an average value of 8.9% in the 2 year aged samples compared with 3.0% in the original biochar and 6.4% in the control soil. Our data suggest that much longer ageing time will be needed for the development of a significant amount of carboxyl groups on biochar surfaces.     

Variability of Indian monsoonal rainfall over the past 100 ka and its implication for C3–C4 vegetational change

Oxygen and carbon isotope ratios of soil carbonate and carbon isotope ratios of soil organic matter (SOM) separated from three cores, Kalpi, IITK and Firozpur, of the Ganga Plain, India are used to reconstruct past rainfall variations and their effect on ambient vegetation. The δ¹⁸O values of soil carbonate (δ¹⁸O_SC) analyzed from the cores range from ? 8.2 to ? 4.1‰. Using these variations in δ¹⁸O_SC values we are able, for the first time, to show periodic change in rainfall amount between 100 and 18 ka with three peaks of higher monsoon at about 100, 40 and 25 ka. The estimation of rainfall variations using δ¹⁸O value of rainwater-amount effect suggests maximum decrease in rainfall intensity (~ 20%) during the last glacial maximum. The δ¹³C values of soil carbonate (δ¹³C_SC) and SOM (δ¹³C_SOM) range from ? 6.3 to + 1.6‰ and ? 28.9 to ? 19.4‰, respectively, implying varying proportions of C₃ and C₄ vegetations over the Ganga Plain during the last 100 ka. The comparison between monsoonal rainfall and atmospheric CO₂ with vegetation for the time period 84 to 18 ka indicate that relative abundances of C₃ and C₄ vegetations were mainly driven by variations in monsoonal rainfall.     

The source and paleoclimatic implication of hydrogen isotopic composition of n-alkanes in sediments from the Yixian Formation,western Liaoning Province,NE China

Hydrogen isotopic composition of n-alkanes was measured in sediments from an excavated profile of the Early Cretaceous Yixian Formation in Liaoning Province, NE China, aiming to assess the significance of the δD value of n-alkanes in ancient lacustrine sediments as the indicator for determining the source inputs of organic matters and paleoclimatic conditions. The δD values of n-alkanes are in the range of − 250‰ to − 85‰ and display an obvious three-stage variation pattern through the profile, which is consistent with the distribution of the dominated n-alkanes and the profile of their δ¹³C values. The δD and δ¹³C values of n-alkanes suggest that short-chain n-alkanes are primarily derived from photosynthetic bacteria and algae; n-C₂₉ and n-C₃₁ are mainly originated from terrestrial higher plants; n-C₂₈ and n-C₃₀ may be derived from the same precursor but via the different biological mechanism of hydrogen isotopic fractionation; while the source inputs of medium-chain n-alkanes are more complicated, with n-C₂₃ being derived from some specific algae or biosynthesized by various aquatic organisms. The paleoclimatic conditions are reconstructed via two approaches. The reconstructed hydrogen isotopic values of lake water and meteoric water (expressed as δD_LW and δD_MW, respectively) were at the intervals of − 51.8‰ to 17.0‰ and − 118.1‰ to − 43.5‰, respectively, indicating a general climate transition from semi-arid to arid. The calculated ΔδD_LW-MW values vary from 37.0‰ to 89.1‰ and display a similar but a significant large-scale variation trend with the ΔδD_{C23 ‐ long} (− 28.8‰ to 85.0‰; long represents long-chain n-alkanes) and ΔδD_mid-long (− 15.4‰ to 43.4‰; mid represents medium-chain n-alkanes) values. The discrepancy may be attributed to the source input overlap for n-alkanes and the uncertainties of ε_water/lipid values. The coupling of ΔδD_{C23 ‐ long}, ΔδD_mid-long and ΔδD_LW-MW values with the paleoclimatic evidence indicates that the δD values of n-alkanes could be more sensitive to the change of paleoclimatic conditions.     

Isotope (C and O) composition of auriferous quartz carbonate veins,central lode system,Gadag Gold Field,Dharwar Craton,India: Implications to source of ore fluids

Carbon (δ¹³C_PDB) and oxygen (δ¹⁸O_SMOW) isotopic compositions of auriferous quartz-carbonate veins (QCVs) of gold deposits from Sangli, Kabuliyatkatti, Nagavi, Nabapur and Mysore mining areas developed on the Central Lode system of the Gadag Gold Field (GGF) in the Neoarchaean Gadag schist belt of the Dharwar Craton, southern India have been examined for the first time to understand the origin of the mineralising fluids. In majority of the samples (46 out of 49), δ¹³C_pdb of carbonates of the QCVs fall in the range from − 2.2‰ to − 9.7‰ and the δ¹⁸O values range from 12.0‰ to 30.5‰ SMOW. The calculated fluid δ¹³C_∑ C compositions for these deposits range from − 2.1‰ to − 9.6‰ and δ¹⁸O_H2O from 6.8‰ to 25.9‰, respectively. Carbonate δ¹³C and fluid δ¹³C_∑ C compositions of the carbonates of the QCVs of the GGF are not only distinct from the carbon isotope range of marine carbonates or meta-sedimentary carbonates of the Chitradurga schist belt, but are consistent with C-isotope values of magmatic (− 5 ± 3‰, Burrows et al., 1986) and/or mantle (− 6 ± 2‰, Ohmoto, 1986) carbonates. As dissolution/decarbonation reactions during metamorphism of pre-existing carbonate/carbonated rocks produce CO₂ with δ¹³C values similar to or more enriched than parent rock, the carbonate or fluid δ¹³C ratios of the QCVs (which fall in the compositional range of mantle/magmatic derived CO₂ or carbonates) obtained in this work cannot be the result of metamorphism. The present study corroborates our previous reports from Ajjanahalli and G.R. Halli gold deposits (Sarangi et al., 2012) occurring in the vicinity of the southern extension of the same crustal scale shear zone on which all the GGF deposits are located.The age of gold mineralisation in this area has been reported to be 2522 ± 6 Ma by Sarma et al., 2011. Chardon et al. (2011) have proposed large-scale remobilization of the older gneissic basement, as well as, emplacement of juvenile granites between 2559 Ma and 2507 Ma, close to the crustal scale shear zone along the eastern margin of the Chitradurga schist belt. Based on these observations and our isotope studies, it is proposed that gold mineralising fluids were derived from mantle/juvenile magmatic melts and were channelled through crustal scale shear zones to give rise to the gold deposits in the GGF.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

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.     

Predicting C aromaticity of biochars based on their elemental composition

Three models were examined to predict C aromaticity (f_a) of biochars based on either their elemental composition (C, H, N and O) or fixed C (FC) content. Values of f_a from solid state ¹³C nuclear magnetic resonance (NMR) analysis with Bloch-decay (BD) or direct polarisation (DP) techniques, concentrations of total C, H, N, and organic O, and contents of FC of 60 biochars were either compiled from the literature (dataset 1, n = 52) or generated in this study (dataset 2, n = 8). Models were first calibrated with dataset 1 and then validated with dataset 2. All models were able to fit dataset 1 when atomic H to C ratio (H/C) < 1 (except two ash rich biochars) and to estimate f_a of HF treated biochars (H/C < 1). Model 1, which was based on values of H/C only and calibrated with a root mean square of error (RMSE) of 0.04 f_a-unit (n = 41), could predict the experimental data with a RMSE = 0.02 f_a-unit (n = 6). Model 2, which was based on biochar elemental composition data, showed the most accurate prediction, with a RMSE of 0.03 f_a-unit (n = 41) for the calibration data, and of 0.02 f_a-unit (n = 6, H/C < 1) for the validation data. Model 3, which was based on contents of FC and C, and modified with a correction factor of 0.96, displayed the highest RMSE (0.06 f_a-unit, n = 19) among the three models. Models 1 and 2 did not work properly for samples having either an H/C ratio > 1, high concentrations of carbonate or high inorganic H. These models need to be further tested with a wider range of biochars before they can be recommended for classification of biochar stability.     

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.     

Nature of ore-forming fluid and formation conditions of BIF-hosted gold mineralization in the Archean Amalia Greenstone Belt,South Africa: Constraints from fluid inclusion and stable isotope studies

Orogenic gold mineralization in the Amalia greenstone belt is hosted by oxide facies banded iron-formation (BIF). Hydrothermal alteration of the BIF layers is characterized by chloritization, carbonatization, hematization and pyritization, and quartz-carbonate veins that cut across the layers. The alteration mineral assemblages consist of ankerite-ferroan dolomite minerals, siderite, chlorite, hematite, pyrite and subordinate amounts of arsenopyrite and chalcopyrite. Information on the physico-chemical properties of the ore-forming fluids and ambient conditions that promoted gold mineralization at Amalia were deduced from sulfur, oxygen and carbon isotopic ratios, and fluid inclusions from quartz-carbonate samples associated with the gold mineralization.Microthermometric and laser Raman analyses indicated that the ore-forming fluid was composed of low salinity H₂O-CO₂ composition (~3 wt% NaCl equiv.). The combination of microthermometric data and arsenopyrite-pyrite geothermometry suggest that quartz-carbonate vein formation, gold mineralization and associated alteration of the proximal BIF wall rock occurred at temperature-pressure conditions of 300 ± 30 °C and ∼2 kbar. Thermodynamic calculations at 300 °C suggest an increase in fO₂ (10⁻³²–10⁻³⁰ bars) and corresponding decrease in total sulfur concentration (0.002–0.001 m) that overlapped the pyrite-hematite-magnetite boundary during gold mineralization. Although hematite in the alteration assemblage indicate oxidizing conditions at the deposit site, the calculated low fO₂ values are consistent with previously determined high Fe/Fe + Mg ratios (>0.7) in associated chlorite, absence of sulfates and restricted positive δ³⁴S values in associated pyrite. Based on the fluid composition, metal association and physico-chemical conditions reported in the current study, it is confirmed that gold in the Amalia fluid was transported as reduced bisulfide complexes (e.g., Au(HS)₂⁻). At Amalia, gold deposition was most likely a combined effect of increase in fO₂ corresponding to the magnetite-hematite buffer, and reduction in total sulfur contents due to sulfide precipitation during progressive fluid-rock interaction.The epigenetic features coupled with the isotopic compositions of the ore-forming fluid (δ³⁴S_ΣS = +1.8 to +2.3‰, δ¹⁸O_H2O = +6.6 to +7.9‰, and δ¹³C_ΣC = −6.0 to −7.7‰ at 300–330 °C) are consistent with an externally deep-sourced fluid of igneous signature or/and prograde metamorphism of mantle-derived rocks.     

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.     

Geological characteristics and genesis of the Laoshankou Fe–Cu–Au deposit in Junggar,Xinjiang, Central Asian Orogenic Belt

The Laoshankou Fe–Cu–Au deposit is located at the northern margin of Junggar Terrane, Xinjiang, China. This deposit is hosted in Middle Devonian andesitic volcanic breccias, basalts, and conglomerate-bearing basaltic volcanic breccias of the Beitashan Formation. Veined and lenticular Fe–Cu–Au orebodies are spatially and temporally related to diorite porphyries in the ore district. Wall–rock alteration is dominated by skarn (epidote, chlorite, garnet, diopside, actinolite, and tremolite), with K–feldspar, carbonate, albite, sericite, and minor quartz. On the basis of field evidence and petrographic observations, three stages of mineralization can be distinguished: (1) a prograde skarn stage; (2) a retrograde stage associated with the development of Fe mineralization; and (3) a quartz–sulfide–carbonate stage associated with Cu–Au mineralization. Electron microprobe analysis shows that garnets and pyroxenes are andradite and diopside-dominated, respectively. Fluid inclusions in garnet yield homogenization temperatures (T_h) of 205–588 °C, and salinities of 8.95–17.96 wt.% NaCl equiv. In comparison, fluid inclusions in epidote and calcite yield T_h of 212–498 and 150–380 °C, and salinities of 7.02–27.04 and 13.4–18.47 wt.% NaCl equiv., respectively. Garnets yield values of 6.4‰ to 8.9‰ δ¹⁸O_fluid, whereas calcites yield values of − 2.4‰ and 4.2‰ δ¹⁸O_fluid, and − 0.9‰ to 2.4‰ δ¹³C_PDB, indicating that the ore-forming fluids were dominantly magmatic fluids in the early stage and meteoric water in the late stage. The δ³⁴S values of sulfides range from − 2.6‰ to 5.4‰, indicating that the sulfur in the deposit was probably derived from deep-seated magmas. The diorite porphyry yields LA–MC–ICP–MS zircon U–Pb age of 379.7 ± 3.0 Ma, whereas molybdenites give Re–Os weighted mean age of 383.2 ± 4.5 Ma (MSWD = 0.06). These ages suggest that the mineralization-related diorite porphyry was emplaced during the Late Devonian, coincident with the timing of mineralization within the Laoshankou Fe–Cu–Au deposit. The geological and geochemical evidence presented here suggest that the Laoshankou Fe–Cu–Au deposit is a skarn deposit.     

Geochemical comparison between gas in fluid inclusions and gas produced from the Upper Triassic Xujiahe Formation,Sichuan Basin,SW China

Natural gas in the Xujiahe Formation of the Sichuan Basin is dominated by hydrocarbon (HC) gas, with 78–79% methane and 2–19% C₂₊ HC. Its dryness coefficient (C₁/C_1–5) is mostly < 0.95. The gas in fluid inclusions, which has low contents of CH₄ and heavy hydrocarbons (C₂₊) and higher contents of non-hydrocarbons (e.g. CO₂), is a typical wet gas produced by thermal degradation of kerogen. Gas produced from the Upper Triassic Xujiahe Formation (here denoted field gas) has light carbon isotope values for methane (δ¹³C₁: −45‰ to −36‰) and heavier values for ethane (δ¹³C₂: −30‰ to −25‰). The case is similar for gas in fluid inclusions, but δ¹³C₁ = −36‰ to −45‰ and δ¹³C₂ = −24.8‰ to −28.1‰, suggesting that the gas experienced weak isotopic fractionation due to migration and water washing. The field gas has δ¹³C_CO2 values of −15.6‰ to −5.6‰, while the gas in fluid inclusions has δ¹³C_CO2 values of −16.6‰ to −9‰, indicating its organic origin. Geochemical comparison shows that CO₂ captured in fluid inclusions mainly originated from source rock organic matter, with little contribution from abiogenic CO₂. Fluid inclusions originate in a relatively closed system without fluid exchange with the outside following the gas capture process, so that there is no isotopic fractionation. They thus present the original state of gas generated from the source rocks. These research results can provide a theoretical basis for gas generation, evolution, migration and accumulation in the basin.     

Elastic constants of single-crystal Pt measured up to 20 GPa based on inelastic X-ray scattering: Implication for the establishment of an equation of state

Phonon velocities and densities for Pt were measured based on inelastic X-ray scattering from ambient pressure to 20 GPa in order to independently determine its equation of state (EOS). Phonon velocities were determined with sine dispersion relations. C_ij values were obtained by fitting phonon velocities and densities to the Christoffel equation. We found that the obtained C_ijs were in good agreement with previously reported C_ijs at ambient condition. Based on the C_ij values in various conditions, experimental pressures were calculated. The EOS of Pt as a primary pressure scale was determined based on the experimental pressures. We report K’ = 5.17 with fixed K_T = 274.1 GPa and V₀ = 60.360 ų for Vinet EOS. Our scale is in good agreement with several previously published scales based on shock experiments and XRD.     

Tracking the fate of dung-derived carbohydrates in a temperate grassland soil using compound-specific stable isotope analysis

Carbohydrates are major organic components of dung and are likely to contribute substantially to increased carbon stocks in manured soils. To investigate this hypothesis, a field-scale experiment was conducted on a temperate grassland site in Devon, UK. C₄ dung (bulk δ¹³C value ?12.6‰) was applied to a temperate grassland C₃ soil (bulk δ¹³C value ?30.3‰) in April and the surface soil beneath cow pats sampled at seven dates over a year. Total carbohydrates were extracted as their monosaccharide components and analysed as the alditol acetates using gas chromatography. The δ¹³C values of the major monosaccharides glucose (?11.5 ±0.6‰), xylose (?10.4 ±0.4‰), arabinose (?10.4 ±0.5‰) and galactose (?8.3 ±1.6‰) extracted from the C₄ dung via acid hydrolysis were indicative of their source. Their weighted mean δ¹³C value was ?10.8‰, 1.8‰ more ¹³C-enriched than the bulk dung value. The δ¹³C values of individual monosaccharides recovered by acid hydrolysis in the 0–1 cm and 1–5 cm soil horizons beneath C₄ cow pats, compared with control soils determined over 372 days, allowed assessment of the extent of incorporation and fluxes of dung-derived monosaccharides. A maximum of 60% of the dung C in soil was derived from carbohydrates after 56 days, declining to around 20% after 372 days. Incorporation dynamics varied between monosaccharide species. Glucose, xylose and arabinose behaved in a similar manner because of their predominantly plant cell wall derived provenance in the dung, whilst dung-derived galactose and mannose appeared to have a microbial source in the soil. The dynamics of total dung-derived monosaccharides in the top 5 cm was comparable to incorporation and flux of bulk dung C, previously estimated using bulk δ¹³C values. The movement of dung-derived carbohydrates into the soil was inequivalent between the 0–1 cm and 1–5 cm horizons. The lack of a significant difference in concentration, but the evidence for the persistence of dung-derived monosaccharides in soil based on δ¹³C values, indicated replacement of existing pools in the soil, suggesting that the ability of this particular soil to sequester further C derived from carbohydrates was limited.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

Carbon-oxygen isotopic geochemistry of the Yangla Cu skarn deposit,SW China: Implications for the source and evolution of hydrothermal fluids

The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ¹³C_PDB (−7.0‰ to −5.0‰) and δ¹⁸O_SMOW (7.2‰ to 12.7‰) than Calcite II (δ¹³C_PDB = −4.5‰ to −2.3‰; δ¹⁸O_SMOW = 10.7‰ to 19.4‰). In the δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ¹³C_PDB = −4.8‰ to −0.3‰; δ¹⁸O_SMOW = 10.2‰ to 23.9‰) also shows a positive δ¹³C_PDB vs. δ¹⁸O_SMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO₂ degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.     

Strontium and carbon isotope stratigraphy of the Late Jurassic shallow marine limestone in western Palaeo-Pacific,northwest Borneo

Strontium and carbon isotope stratigraphy was applied to a 202 m-thick shallow marine carbonate section within the Late Jurassic Bau Limestone at the SSF quarry in northwest Borneo, Malaysia, which was deposited in the western Palaeo-Pacific. Strontium isotopic ratios of rudist specimens suggest that the SSF section was formed between the latest Oxfordian (155.95 Ma) and the Late Kimmeridgian (152.70 Ma), which is consistent with previous biostratigraphy. The δ¹³C_carb values of bulk carbonate range from −0.10 to +2.28‰ and generally show an increasing upward trend in the lower part of the section and a decreasing upward trend in the upper part of the section. A comparable pattern is preserved in the δ¹³C_org isotope record. Limestone samples of the SSF section mainly preserve the initial δ¹³C_carb values, except for the interval 84–92 m, where an apparent negative anomaly likely developed as a result of meteoric diagenesis. Comparing with the Tethyan δ¹³C_carb profile, a negative anomaly in the lower SSF section can be correlated with the lowered δ¹³C values around the Oxfordian/Kimmeridgian boundary. In addition, δ¹³C_carb values of the Bau Limestone are generally ∼1‰ lower than the Tethyan values, but comparable with the values reported from Scotland and Russia, located in Boreal realm during the Late Jurassic. This suggests that either the Tethyan record or the other records have been affected by the δ¹³C values of regionally variable dissolved inorganic carbon (DIC). The Late Jurassic δ¹³C_DIC values are thought to have been regionally variable as a result of their palaeoceanographic settings. This study shows that δ¹³C chemostratigraphy of the Palaeo-Pacific region contributes to an improved understanding of global carbon cycling and oceanography during this time period.     

Origin,distribution and hydrogeochemical controls on methane occurrences in shallow aquifers,southwestern Ontario,Canada

Natural gas reservoirs in organic-rich shales in the Appalachian and Michigan basins in the United States are currently being produced via hydraulic fracturing. Stratigraphically-equivalent shales occur in the Canadian portion of the basins in southwestern Ontario with anecdotal evidence of gas shows, yet there has been no commercial shale gas production to date. To provide baseline data in the case of future environmental issues related to hydraulic fracturing and shale gas production, such as leakage of natural gas, saline water, and/or hydraulic fracturing fluids, and to evaluate hydrogeochemical controls on natural gas accumulations in shallow groundwater in general, this study investigates the origin and distribution of natural gas and brine in shallow aquifers across southwestern Ontario. An extensive geochemical database of major ion and trace metal chemistry and methane concentrations of 1010 groundwater samples from shallow, domestic wells in bedrock and overburden aquifers throughout southwestern Ontario was utilized. In addition, select wells (n = 36) were resampled for detailed dissolved gas composition, δ¹³C of CH₄, C₂, C₃, and CO₂, and δD of CH₄. Dissolved gases in groundwater from bedrock and overburden wells were composed primarily of CH₄ (29.7–98.6 mol% of total gas volume), N₂ (0.8–66.2 mol%), Ar + O₂ (0.2–3.4 mol%), and CO₂ (0–1.2 mol%). Ethane was detected, but only in low concentrations (<0.041 mol%), and no other higher chain hydrocarbons were present, except for one well in overburden overlying the Dundee Formation, which contained 0.81 mol% ethane and 0.21 mol% propane. The highest methane concentrations (30 to >100 in situ % saturation) were found in bedrock wells completed in the Upper Devonian Kettle Point Formation, Middle Devonian Hamilton Group and Dundee Formation, and in surficial aquifers overlying these organic-rich shale-bearing formations, indicating that bedrock geology is the primary control on methane occurrences. A few (n = 40) samples showed Na–Cl–Br evidence of brine mixing with dilute groundwater, however only one of these samples contained high (>60 in situ % saturation) CH₄. The relatively low δ¹³C values of CH₄ (−89.9‰ to −57.3‰), covariance of δD values of CH₄ and H₂O, positive correlation between δ¹³C values of CH₄ and CO₂, and lack of higher chain hydrocarbons (C₃₊) in all but one dissolved gas sample indicates that the methane in groundwater throughout the study area is primarily microbial in origin. The presence or absence of alternative electron acceptors (e.g. dissolved oxygen, Fe, NO₃, SO₄), in addition to organic substrates, controls the occurrence of microbial CH₄ in shallow aquifers. Microbial methane has likely been accumulating in the study area, since at least the Late Pleistocene to the present, as indicated by the co-variance and range of δD values of CH₄ (−314‰ to −263‰) and associated groundwater (−19‰ to −6‰ δD-H₂O).     

Late-glacial to Holocene transition in northern Spain deduced from land-snail shelly accumulations

Shells of the helicid Cepaea nemoralis were studied using taphonomic, isotopic and morphometric measurements to estimate late glacial–Holocene (~ 12.1–6.3 cal ka BP) environmental conditions in northern Spain. Higher taphonomic alteration among Holocene shells suggests lower sedimentation rates or higher shell-destruction rates than during glacial conditions. Shells preserved the aragonitic composition despite differing degree of skeleton damage. Shell δ¹³C values were ? 10.3 ± 1.1‰, ? 8.2 ± 2.3‰, and ? 7.3 ± 1.6‰ for modern, Holocene and late-glacial individuals, respectively. Higher δ¹³C values during the late-glacial and some Holocene periods imply higher water stress of C₃ plants and/or higher limestone contribution than today. Intrashell δ¹³C values were higher during juvenile stages suggesting higher limestone ingestion to promote shell growth. Shell δ¹⁸O values were ? 1.1 ± 0.7‰, ? 0.9 ± 0.8‰ and ? 0.1 ± 0.7‰ for modern, Holocene and late-glacial specimens, respectively. A snail flux-balance model suggests that during ~ 12.1 ? 10.9 cal ka BP conditions were drier and became wetter at ~ 8.4 ? 6.3 cal ka BP and today. Intrashell δ¹⁸O profiles reveal that glacial individuals experienced more extreme seasonality than interglacial shells, despite possible larger hibernation periods. Shell size correlated positively with δ¹⁸O values, suggesting that growth rates and ultimate adult size of C. nemoralis may respond to climate fluctuation in northern Spain.     

Geochemical and isotopic approach to maturity/source/mixing estimations for natural gas and associated condensates in the Thrace Basin,NW Turkey

The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH₄, thermogenic C₂₊ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH₄ is bacteriogenic (Calculated δ¹³C_C1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH₄. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ¹³C_C1–C = −35.80‰; Hamitabat Field) and Group-3 (δ¹³C_1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C₂₊ gases. The Group-2 C₂₊ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ¹³C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C₂₊ gases, produced from one field, were generated from isotopically light marine kerogen (δ¹³C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C₂₊ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ¹³C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (R_eq = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.