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

Devleena Mani  D.J. Patil  A.M. Dayal 《Chemical Geology》2011,280(1-2):144-153

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.  相似文献   

The evolution of the Arabian lower crust and lithospheric mantle — Geochemical constraints from southern Syrian mafic and ultramafic xenoliths     

Marc-Sebastian Krienitz  Karsten M. Haase 《Chemical Geology》2011,280(3-4):271-283

Geochemical compositions of lower crustal and lithospheric mantle xenoliths found in alkali basaltic lavas from the Harrat Ash Shamah volcanic field in southern Syria place constraints on the formation of the Arabian–Nubian Shield in northern Arabia. Compositions of lower crustal granulites are compatible with a cumulate formation from mafic melts and indicate that they are not genetically related to their host rocks. Instead, their depletion in Nb relative to other incompatible elements points to an origin in a Neoproterozoic subduction zone as recorded by an average depleted mantle Sm–Nd model age of 630 Ma.Lithospheric spinel peridotites typically represent relatively low degree (< 10%) partial melting residues of spinel lherzolite with primitive mantle compositions as indicated by major and trace element modelling of clinopyroxene and spinel. The primary compositions of the xenoliths were subsequently altered by metasomatic reactions with low degree silicate melts and possibly carbonatites. Because host lavas lack these signatures any recent reaction of the lherzolites with their host magma can be ruled out. Sm–Nd data of clinopyroxene from Arabian lithospheric mantle lherzolites yield an average age of 640 Ma suggesting that the lithosphere was not replaced since its formation and supporting a common origin of the Arabian lower crustal and lithospheric mantle sections.The new data along with published Arabian mantle xenolith compositions are consistent with a model in which the lithospheric precursor was depleted oceanic lithosphere that was overprinted by metasomatic processes related to subduction and arc accretion during the generation of the Arabian–Nubian Shield. The less refractory nature of the northern Arabian lithosphere as indicated by higher Al, Na and lower Si and Mg contents of clinopyroxenes compared to the more depleted nature of the south Arabian lithospheric mantle, and the comparable low extent of melt extraction suggest that the northern Arabian lithosphere formed in a continental arc system, whereas the lithosphere in the southern part of Arabia appears to be of oceanic arc origin.  相似文献   

Geochemistry of lower Jurassic shales of the Shemshak Formation, Kerman Province, Central Iran: Provenance, source weathering and tectonic setting     

S.M. Moosavirad  M.R. Janardhana  M.S. Sethumadhav  M.R. Moghadam  M. Shankara 《Chemie der Erde / Geochemistry》2011,71(3):279-288

Lower Jurassic shales of the Shemshak Formation of Kerman Province, Central Iran, were analyzed for major and selected trace elements to infer their provenance, intensity of palaeoweathering of the source rocks and tectonic setting. Plots of shales on Al₂O₃ wt.% versus TiO₂ wt.% diagram and Cr (ppm) versus Ni (ppm) diagram indicate that acidic (granitic) rocks constitute the source rocks in the provenance. Average CIA, PIA and CIW values (84%, 92%, 93%, respectively) imply intense weathering of the source material. Plots of shales on bivariate discriminant function diagram reveal an active continental margin setting for the provenance. The inferred tectonic setting for the Lower Jurassic shales of the Shemshak Formation of Kerman Province is in agreement with the tectonic evolutionary history of the Central Iran during the Jurassic period.  相似文献   

Catabolic and anabolic energy for chemolithoautotrophs in deep-sea hydrothermal systems hosted in different rock types     

Jan P. Amend  Thomas M. McCollom  Wolfgang Bach 《Geochimica et cosmochimica acta》2011,75(19):5736-5748

Active deep-sea hydrothermal vents are hosted by a range of different rock types, including basalt, peridotite, and felsic rocks. The associated hydrothermal fluids exhibit substantial chemical variability, which is largely attributable to compositional differences among the underlying host rocks. Numerical models were used to evaluate the energetics of seven inorganic redox reactions (potential catabolisms of chemolithoautotrophs) and numerous biomolecule synthesis reactions (anabolism) in a representative sampling of these systems, where chemical gradients are established by mixing hydrothermal fluid with seawater. The wide ranging fluid compositions dictate demonstrable differences in Gibbs energies (ΔG_r) of these catabolic and anabolic reactions in three peridotite-hosted, six basalt-hosted, one troctolite-basalt hybrid, and two felsic rock-hosted systems. In peridotite-hosted systems at low to moderate temperatures (<∼45 °C) and high seawater:hydrothermal fluid (SW:HF) mixing ratios (>10), hydrogen oxidation yields the most catabolic energy, but the oxidation of methane, ferrous iron, and sulfide can also be moderately exergonic. At higher temperatures, and consequent SW:HF mixing ratios <10, anaerobic processes dominate the energy landscape; sulfate reduction and methanogenesis are more exergonic than any of the aerobic respiration reactions. By comparison, in the basalt-hosted and felsic rock-hosted systems, sulfide oxidation was the predominant catabolic energy source at all temperatures (and SW:HF ratios) considered. The energetics of catabolism at the troctolite-basalt hybrid system were intermediate to these extremes. Reaction energetics for anabolism in chemolithoautotrophs—represented here by the synthesis of amino acids, nucleotides, fatty acids, saccharides, and amines—were generally most favorable at moderate temperatures (22-32 °C) and corresponding SW:HF mixing ratios (∼15). In peridotite-hosted and the troctolite-basalt hybrid systems, ΔG_r for primary biomass synthesis yielded up to ∼900 J per g dry cell mass. The energetics of anabolism in basalt- and felsic rock-hosted systems were far less favorable. The results suggest that in peridotite-hosted (and troctolite-basalt hybrid) systems, compared with their basalt (and felsic rock) counterparts, microbial catabolic strategies—and consequently variations in microbial phylotypes—may be far more diverse and some biomass synthesis may yield energy rather than imposing a high energetic cost.  相似文献   

Uranium speciation and stability after reductive immobilization in aquifer sediments     

Jonathan O. Sharp  Juan S. Lezama-Pacheco  Pilar Junier  Kai-Uwe Ulrich  Satya Chinni  Camille Margot-Roquier  Bradley M. Tebo  John R. Bargar 《Geochimica et cosmochimica acta》2011,75(21):6497-6510

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO₂). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron release. Despite initial augmentation with Shewanella oneidensis, bacteria belonging to the phylum Firmicutes dominated the biostimulated columns. The immobilization of uranium (∼1 mmol U per kg sediment) enabled analysis by X-ray absorption spectroscopy (XAS). Tetravalent uranium associated with these sediments did not have spectroscopic signatures representative of U-U shells or crystalline UO₂. Analysis by microfocused XAS revealed concentrated micrometer regions of solid U(IV) that had spectroscopic signatures consistent with bulk analyses and a poor proximal correlation (μm scale resolution) between U and Fe. A plausible explanation, supported by biogeochemical conditions and spectral interpretations, is uranium association with phosphoryl moieties found in biomass; hence implicating direct enzymatic uranium reduction. After the immobilization phase, two months of in situ exposure to oxic influent did not result in substantial uranium remobilization. Ex situ flow-through experiments demonstrated more rapid uranium mobilization than observed in column oxidation studies and indicated that sediment-associated U(IV) is more mobile than biogenic UO₂. This work suggests that in situ uranium bioimmobilization studies and subsurface modeling parameters should be expanded to account for non-uraninite U(IV) species associated with biomass.  相似文献   

Fossil brines preserved in the St-Lawrence Lowlands, Québec, Canada as revealed by their chemistry and noble gas isotopes     

Daniele L. Pinti  Catherine Béland-Otis  Alain Tremblay  Chris M. Hall  Jean-Yves Lavoie 《Geochimica et cosmochimica acta》2011,75(15):4228-4243

Brines in Cambrian sandstones and Ordovician dolostones of the St-Lawrence Lowlands at Bécancour, Québec, Canada were sampled for analysis of all stable noble gases in order to trace their origin and migration path, in addition to quantifying their residence time. Major ion chemistry indicates that the brines are of Na-Ca-Cl type, possibly derived from halite dissolution. ⁸⁷Sr/⁸⁶Sr ratios and Ca excess indicate prolonged interactions with silicate rocks of the Proterozoic Grenville basement or the Cambrian Potsdam sandstone. The brines constrain a 2-3% contribution of mantle ³He and large amounts of nucleogenic ²¹Ne^∗ and ³⁸Ar^∗ and radiogenic ⁴He and ⁴⁰Ar^∗. ⁴He/⁴⁰Ar^∗ and ²¹Ne^∗/⁴⁰Ar^∗ ratios, corrected for mass fractionation during incomplete brine degassing, are identical to their production ratios in rocks. The source of salinity (halite dissolution), plus the occurrence of large amounts of ⁴⁰Ar^∗ in brines constrain the residence time of Bécancour brines as being older than the Cretaceous. Evaporites in the St-Lawrence Lowlands likely existed only during Devonian-Silurian time. Brines might result from infiltration of Devonian water leaching halite, penetrating into or below the deeper Cambrian-Ordovician aquifers. During the Devonian, the basin reached temperatures higher than 250 °C, allowing for thermal maturation of local gas-prone source rocks (Utica shales) and possibly facilitating the release of radiogenic ⁴⁰Ar^∗ into the brines. The last thermal event that could have facilitated the liberation of ⁴⁰Ar^∗ into fluids and contributed to mantle ³He is the Cretaceous Monteregian Hills magmatic episode. For residence times younger than the Cretaceous, it is difficult to find an appropriate source of salinity and of nucleogenic/radiogenic gases to the Bécancour brines.  相似文献   

Relationship among titanium,rare earth elements,U–Pb ages and deformation microstructures in zircon: Implications for Ti-in-zircon thermometry     

Nick E. Timms  Peter D. Kinny  Steven M. Reddy  Katy Evans  Chris Clark  Dave Healy 《Chemical Geology》2011,280(1-2):33-46

A zircon grain in an orthopyroxene–garnet–phlogopite–zircon–rutile-bearing xenolith from Udachnaya, Siberia, preserves a pattern of crystallographic misorientation and subgrain microstructure associated with crystal–plastic deformation. The zircon grain records significant variations in titanium (Ti) from 2.6 to 30 ppm that corresponds to a difference in calculated Ti-in-zircon temperatures of over several hundred degrees Celsius. The highest Ti concentration is measured at subgrain centres (30 ppm), and Ti is variably depleted at low-angle boundaries (down to 2.6 ppm). Variations in cathodoluminescence coincide with the deformation microstructure and indicate localised, differential enrichment of rare earth elements (REE) at low-angle boundaries. Variable enrichment of U and Th and systematic increase of Th/U from 1.61 to 3.52 occurs at low-angle boundaries. Individual SHRIMP-derived U–Pb ages from more deformed zones (mean age of 1799 ± 40, n = 22) are systematically younger than subgrain cores (mean age of 1851 ± 65 Ma, n = 7), and indicate that open system behaviour of Ti–Th–U occurred shortly after zircon growth, prior to the accumulation of significant radiogenic Pb. Modelling of trace-element diffusion distances for geologically reasonable thermal histories indicates that the observed variations are ~ 5 orders of magnitude greater than can be accounted for by volume diffusion. The data are best explained by enhanced diffusion of U, Th and Ti along deformation-related fast-diffusion pathways, such as dislocations and low-angle (< 5°) boundaries. These results indicate chemical exchange between zircon and the surrounding matrix and show that Ti-in-zircon thermometry and U–Pb geochronology from deformed zircon may not yield information relating to the conditions and timing of primary crystallisation.  相似文献   

Arsenic uptake by natural calcite: An XAS study     

F. Bardelli  P. Costagliola  F. Di Benedetto  P. Lattanzi  M. Romanelli 《Geochimica et cosmochimica acta》2011,75(11):3011-3023

As-bearing travertine rocks from Tuscany (Italy), where previous studies suggested the existence of a CO₃²⁻ ⇔ AsO₃³⁻ substitution in the calcite lattice, were investigated with X-ray Absorption Spectroscopy (XAS) at the As K-edge (11,867 eV). In two of the studied samples, XANES indicates that As is in the 5+ oxidation state only, and EXAFS analysis reveals a local environment typical of arsenate species. For these samples, the lack of detectable second shell signals suggests a poorly ordered environment, possibly corresponding to an adsorption onto oxide and/or silicate phases. On the other hand, in the third sample XANES reveals a mixed As oxidation state (III and V). This sample also presents evident next nearest neighbor coordination shells, attributed to As-Ca and As-As contributions. The occurrence of next neighbor shells is evidence that part of As is incorporated in an ordered lattice. Furthermore, the local structure revealed by EXAFS is compatible with As incorporation in the calcite phase, as further supported by DFT simulations. The observation of next neighbors shells only in the As(III)-rich sample suggests the substitution of the arsenite group in place of the carbonate one (CO₃²⁻ ⇔ AsO₃³⁻). The conclusion of this work is that uptake of As by calcite is in general less favored than adsorption onto iron oxhydroxides, but could become environmentally important wherever the latter phenomenon is hindered.  相似文献   

The significance of isotope specific diffusion coefficients for reaction-transport models of sulfate reduction in marine sediments     

Ulrich G. Wortmann  Boris M. Chernyavsky 《Geochimica et cosmochimica acta》2011,75(11):3046-3056

Modeling isotopic signatures in systems affected by diffusion, advection, and a reaction which modifies the isotopic abundance of a given species, is a discipline in its infancy. Traditionally, much emphasis has been placed on kinetic isotope effects during biochemical reactions, while isotope effects caused by isotope specific diffusion coefficients have been neglected. A recent study by Donahue et al. (2008) suggested that transport related isotope effects may be of similar magnitude as microbially mediated isotope effects. Although it was later shown that the assumed differences in the isotope specific diffusion coefficients were probably overstated by one or two orders of magnitude (Bourg, 2008), this study raises several important issues: (1) Is it possible to directly calculate isotopic enrichment factors from measured concentration data without modeling the respective system? (2) Do changes in porosity and advection velocity modulate the influence of isotope specific diffusion coefficients on the fractionation factor α? (3) If one has no a priori knowledge whether diffusion coefficients are isotope specific or not, what is the nature and magnitude of the error introduced by either assumption? Here we argue (A) That the direct substitution of measured data into a differential equation is problematic and cannot be used as a replacement for a reaction-transport model; (B) That the transport related fractionation scales linearly with the difference between the respective diffusion coefficients of a given isotope system, but depends in a complex non-linear way on the interplay between advection velocity, and downcore changes of temperature and porosity. Last but not least, we argue that the influence of isotope specific diffusion coefficients on microbially mediated sulfate reduction in typical marine sediments is considerably smaller than the error associated with the determination of the fractionation factor.  相似文献   

Copper isotope fractionation during surface adsorption and intracellular incorporation by bacteria   总被引：1，自引：0，他引：1  

Navarrete JU  Borrok DM  Viveros M  Ellzey JT 《Geochimica et cosmochimica acta》2011,75(3):784-799

Copper isotopes may prove to be a useful tool for investigating bacteria-metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ⁶⁵Cu) to investigate Cu-bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5-6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ⁶⁵Cu_{solution-solid} = δ⁶⁵Cu_solution − δ⁶⁵Cu_solid) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to −0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ⁶⁵Cu_{solution-solid} ranging from ∼+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is shared by fungi, plants, and higher organisms, the influence of biological processes on the δ⁶⁵Cu of natural waters and soils is probably considerable.  相似文献