Carbon isotope fractionation by the marine ammonia-oxidizing archaeon Nitrosopumilus maritimus

Ammonia-oxidizing archaea (AOA) are abundant and widely distributed microorganisms in aquatic and terrestrial habitats. By catalyzing the first and rate limiting step in nitrification, these chemolithoautotrophs play a significant role in the global nitrogen cycle and contribute to primary production. Here, the carbon isotopic fractionation relative to inorganic carbon source was determined for bulk biomass, biphytanes and polar lipid bound sugars of a marine AOA pure culture. Bulk biomass and biphytanes from Nitrosopumilus maritimus showed identical carbon isotope fractionation (ε_DIC/bulk and ε_{DIC/byphytanes}) of ca. −20‰. The glycoside head groups were mainly glucose, mannose and inositol, and exhibited different carbon isotopic composition. In general, these monosaccharides were enriched in ¹³C (ε −6.1‰ to −13.8‰) relative to bulk biomass and biphytanes. The fact that the carbon isotope composition of the biphytanes reflected that of the bulk biomass of N. maritimus suggests that the depletion of ¹³C in both biomass and biphytanes resulted mainly from the carbon isotope discrimination by the bicarbonate-fixing enzyme in the autotrophic hydroxypropionate/hydroxybutyrate cycle. Our results further revealed that lipid compounds represent suitable biomarkers for determining δ¹³C values of archaeal ammonia oxidizers without biosynthetic correction.     

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.     

Geochemistry and origins of natural gases in the central Junggar Basin,northwest China

The petroliferous central Junggar Basin in northwest China is predominantly an oil exploration region. However, its gas exploration also might have good prospects. Thus to assist in gas exploration, the geochemistry and origins of gases are discussed in this paper based on relatively comprehensive analyses of compositions, carbon isotopes and light hydrocarbons of gases. Based on the results, the gas genetic types are grouped into families and combined with the geological setting (e.g., biomarkers of retrograde condensates and source rock characteristics). We show that there are four representative genetic types of gases. The first consists of gases derived from Permian lacustrine mudstones with type I–II kerogen and type III kerogen sources in the Penyijingxi sag. Their representative geochemical feature is δ¹³C₂ ranging from −31.4‰ to −24.7‰. The second is gas sourced from Carboniferous tufaceous mudstones of type III kerogen in the Dishuiquan sag, whose representative geochemical feature is the heaviest values of δ¹³C₁ in the studied samples, ranging from −32.0‰ to −30.4‰. The third consists of gases sourced from Jurassic coals and mudstones in the Shawan–Fukang sag. The light hydrocarbon fingerprints of these gases are similar to those of gases and oils typically derived from Jurassic source rocks in the southern Junggar Basin. The fourth is gas most likely generated from the degradation of crude oil. It is mainly found in the Luliang area and has dryness values as much as 0.999 and δ¹³C₁ ranging from −54.8‰ to −43.2‰. Among these four types of gases, the first (mainly sourced from the Permian lacustrine mudstones in the Penyijingxi sag) is the predominant type.     

Archaeal lipids in Neogene dolomites (Monterey and Sisquoc Formations, California) - Planktic versus benthic archaeal sources

The distribution of archaeal lipids, including archaeol and glycerol dibiphytanyl glycerol tetraethers (GDGTs), in dolomite concretions and surrounding sediment from the Monterey Formation (Miocene) and the Sisquoc Formation (Miocene-Pliocene) were examined to distinguish planktic from benthic contributions. For this purpose, dolomites with positive δ¹³C values (+7‰ to +13‰) were chosen; such highly positive values point to pronounced methanogenesis of benthic archaea in the sedimentary column. At first glance, distributions and relative abundances of GDGTs in both dolomites and background sediment were similar, resembling patterns of marine planktic crenarchaea. A contribution of benthic euryarchaea to the GDGT pool became evident only from variations in the δ¹³C values of different biphytanes obtained after ether cleavage of GDGTs. Whereas bi- and tricyclic biphytanes had an isotopic signal typical of planktic archaea (δ¹³C −23.6‰ to −20.5‰ and −23.4‰ to −21.2‰, respectively) for both dolomite and background sediment, acyclic and monocyclic biphytanes showed lower values for dolomite samples (−25.1‰ to −22.6‰ and −27.6‰ to −24.7‰, respectively), indicating a contribution of lipids from benthic archaea. The isoprenoid diether archaeol (δ¹³C −23.9‰ to −22.9‰), assigned to euryarchaea, was only detected in dolomite samples, also reflecting additional input from sedimentary archaea, probably autotrophic methanogens. The occurrence of lipids derived from methanogenic archaea agrees with the strong ¹³C-enrichment of dolomites and with mineral formation taking place in the zone of archaeal methanogenesis. This implies that the lipid biomarker inventory of sedimentary strata needs to be interpreted carefully, as it is often not straightforward to discriminate between input from the water column and sedimentary microbial activity.     

Highly isotopically depleted isoprenoids: molecular markers for ancient methane venting

We propose that organic compounds found in a Miocene limestone from Marmorito (Northern Italy) are source markers for organic matter present in ancient methane vent systems (cold seeps). The limestone contains high concentrations of the tail-to-tail linked, acyclic C₂₀ isoprenoid 2,6,11,15-tetramethylhexadecane (crocetane), a C₂₅ homolog 2,6,10,15,19-pentamethylicosane (PME), and a distinctive glycerol ether lipid containing 3,7,11,15-tetramethylhexadecyl (phytanyl-) moieties. The chemical structures of these biomarkers indicate a common origin from archaea. Their extremely ¹³C-depleted isotope compositions (δ¹³C ≈ −108 to −115.6‰ PDB) suggest that the respective archaea have directly or indirectly introduced isotopically depleted, methane-derived carbon into their biomass. We postulate that a second major cluster of biomarkers showing heavier isotope values (δ¹³C ≈ −88‰) is derived from sulfate-reducing bacteria (SRB). The observed biomarkers sustain the idea that methanogenic bacteria, in a syntrophic community with SRB, are responsible for the anaerobic oxidation of methane in marine sediments. Marmorito may thus represent a conceivable ancient scenario for methane consumption performed by a defined, two-membered bacterial consortium: (1) archaea that perform reversed methanogenesis by oxidizing methane and producing CO₂ and H₂; and (2) SRB that consume the resulting H₂. Furthermore, the respective organic molecules are, unlike other compounds, tightly bound to the crystalline carbonate phase. The Marmorito carbonates can thus be regarded as “cold seep microbialites” rather than mere “authigenic” carbonates.     

Stable carbon isotope biogeochemistry of a shallow sand aquifer contaminated with fuel hydrocarbons

Ground-water chemistry and the stable C isotope composition (δ¹³C_DIC) of dissolved inorganic C (DIC) were measured in a sand aquifer contaminated with JP–4 fuel hydrocarbons. Results show that ground water in the upgradient zone was characterized by DIC content of 14–20 mg C/L and δ¹³C_DIC values of −11.3‰ to −13.0‰. The contaminant source zone was characterized by an increase in DIC content (12.5 mg C/L to 54 mg C/L), Ca, and alkalinity, with a significant depletion of ¹³C in δ¹³C_DIC (−11.9‰ to −19.2‰). The source zone of the contaminant plume was also characterized by elevated levels of aromatic hydrocarbons (0 μg/L to 1490 μg/L) and microbial metabolites (aromatic acids, 0 μg/L to 2277 μg/L), non-detectable dissolved O₂, NO₃ and SO₄. Phospholipid ester-linked fatty acid analyses suggest the presence of viable SO₄-reducing bacteria in ground water at the time of sampling. The ground-water chemistry and stable C isotope composition of ground-water DIC are interpreted using a chemical reaction model involving rainwater recharge, contributions of CO₂ from soil gas and biodegradation of hydrocarbons, and carbonate dissolution. The major-ion chemistry and δ¹³C_DIC were reconciled, and the model predictions were in good agreement with field measurements. It was concluded that stable C isotope measurements, combined with other biogeochemical measures can be a useful tool to monitor the dominant terminal electron-accepting processes in contaminated aquifers and to identify mineralogical, hydrological, and microbiological factors that affect δ¹³C of dissolved inorganic C.     

Did an extensive forest ever develop on the Chinese Loess Plateau during the past 130 ka?: a test using soil carbon isotopic signatures

Pleistocene vegetation history on the Chinese Loess Plateau has been traditionally investigated using palynological methods, and questions remain regarding whether an extensive broadleaf deciduous forest ever developed on the loess table under favorable climatic conditions. The authors have employed a C isotope approach to address this question by comparing δ¹³C values in soil organic matter from different loess ecological domains with known source vegetation to the C isotope values obtained from a paleosol section that can be dated back to 130 ka. The C isotopic compositions of modern soils from the loess table and the loess–desert transition gave δ¹³C values of −24.5‰ to −18.2‰ and −25.7‰ to −20.7‰, respectively. These C isotopic ratios are consistent with the standing modern vegetation that is dominated by a mixture of C₃ and C₄ plants and can be distinguished from that in the patchy forest areas where exclusive C₃ trees yield a narrow δ¹³C value range from −26.9‰ to −25‰ (average −26.1‰). Obtained δ¹³C compositions from paleosols and loess sediments in the Lantian and the Luochuan profiles vary from −24‰ to −16.9‰, indicating a grass-dominated steppe with shifting C₃ and C₄ contributions controlled mainly by paleoclimatic changes during the late Pleistocene. The present results suggest no extensive forest coverage on the loess table during the past 130 ka even under the most suitable conditions for forest development. This conclusion supports the explanation of natural causes for the development of only patchy forests on the modern loess table and provides critical historical information toward the vegetation restoration project that is currently underway on the Chinese Loess Plateau.     

Application of sulfur and carbon isotopes to oil–source rock correlation: A case study from the Tazhong area,Tarim Basin,China

Up until now, it has been assumed that oil in the Palaeozoic reservoirs of the Tazhong Uplift was derived from Upper Ordovician source rocks. Oils recently produced from the Middle and Lower Cambrian in wells ZS1 and ZS5 provide clues concerning the source rocks of the oils in the Tazhong Uplift, Tarim Basin, China. For this study, molecular composition, bulk and individual n-alkane δ¹³C and individual alkyl-dibenzothiophene δ³⁴S values were determined for the potential source rocks and for oils from Cambrian and Ordovician reservoirs to determine the sources of the oils and to address whether δ¹³C and δ³⁴S values can be used effectively for oil–source rock correlation purposes. The ZS1 and ZS5 Cambrian oils, and six other oils from Ordovician reservoirs, were not significantly altered by TSR. The ZS1 oils and most of the other oils, have a “V” shape in the distribution of C₂₇–C₂₉ steranes, bulk and individual n-alkane δ¹³C values predominantly between −31‰ to −35‰ VPDB, and bulk and individual alkyldibenzothiophene δ³⁴S values between 15‰ to 23‰ VCDT. These characteristics are similar to those for some Cambrian source rocks with kerogen δ¹³C values between −34.1‰ and −35.3‰ and δ³⁴S values between 10.4‰ and 21.6‰. The oil produced from the Lower Ordovician in well YM2 has similar features to the ZS1 Cambrian oils. These new lines of evidence indicate that most of the oils in the Tazhong Uplift, contrary to previous interpretations, were probably derived from the Cambrian source rocks, and not from the Upper Ordovician. Conversely, the δ¹³C and δ³⁴S values of ZS1C Cambrian oils have been shown to shift to more positive values due to thermochemical sulfate reduction (TSR). Thus, δ¹³C and δ³⁴S values can be used as effective tools to demonstrate oil–source rock correlation, but only because there has been little or no TSR in this part of the section.     

Molecular fossils extracted from the Early Cambrian section in the Three Gorges area,South China

Environmental investigation of the Early Cambrian is assessed through molecular fossils based from three core samples drilled in the Three Gorges area, South China. The core samples record environmental information dating from the earliest part of the Early Cambrian to nearly the end of the Early Cambrian, making this investigation unique from previous investigations because a more far-reaching temporal record is assessed. This record includes unusually high abundance of longer chain n-alkanes (LCA) around _nC₂₇, having been recognized in the earliest Cambrian strata. Based on no odd–even preference of the LCA and comparisons to hydrocarbons in cultured cells of microorganisms, the LCA may be derived from hydrocarbons of sulfate reducing bacteria. On the other hand, a phototrophic origin of the SCA is supported by a clear positive correlation with pristane. The relative abundance of LCA to SCA increased in the earliest Cambrian, suggesting predominance of sulfate reducers against phototrophs. This LCA abundance with simultaneous decrease of pristane/phytane may indicate a euxinic condition, where sulfate reducers remineralize organic carbon in the water column. This is consistent with the concomitant decrease of the δ¹³C_carb value probably due to a massive reoxidation of organic carbon. The inferred reducing condition is further supported by the enhanced appearance of squalane that could be derived from an Archeal lipid. Our results suggest the euxinia of the Yangtze platform in the earliest Cambrian that may relate to the emergence of the large nektonic animals which require sufficient level of free oxygen.     

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.     

Development of microbial carbonates in the Lower Cretaceous Codó Formation (north‐east Brazil): Implications for interpretation of microbialite facies associations and palaeoenvironmental conditions

The study of microbial carbonates has acquired new significance with the recognition that they retain valuable information related to biomineralization processes associated with microbial activity throughout geological time. Additionally, microbialites have a demonstrated economic potential to serve as excellent hydrocarbon reservoirs. The Lower Cretaceous Codó Formation, located in the Parnaiba Basin of north‐east Brazil, comprises a unique stratigraphic sequence of up to 20 m thick, well‐preserved carbonate microbialites. Deposited in a continental basin during the initial break up and separation of South America from Africa in the Early Cretaceous, this lacustrine carbonate sequence provides an excellent example to investigate the palaeoenvironmental conditions controlling microbialite facies development. Based on macroscopic and microscopic observations of outcrop and drill core samples, four microbialite facies (stromatolite, lamina, massive and spherulite) were defined and distinguished by textures and microbial fossil content. Changes in facies type are related to alternating palaeo‐water depths, as reflected by ⁸⁷Sr/⁸⁶Sr cycles resulting from fluctuations in the sources of meteoric water. Clumped isotope measurements of stromatolitic fabrics yield precipitation palaeo‐temperatures with an average value of 35°C. The δ¹⁸O values of bulk carbonate (?6·8 to ?1·5‰ Vienna Pee Dee Belemnite) imply precipitation from water with calculated δ¹⁸O values between ?1·6‰ and 1·8‰ Vienna Standard Mean Ocean Water, reflecting precipitation from variably modified meteoric waters. The δ¹³C values of bulk carbonate (?15·5 to ?7·2‰ Vienna Pee Dee Belemnite) indicate a significant input of carbon derived from aerobic or anaerobic respiration of organic matter. Combined, the data indicate that the evolution of the Codó Formation occurred in a closed lacustrine palaeoenvironment with alternating episodes of contracting and expanding lake levels, which led to the development of specific microbialite facies associations. The results provide new insights into palaeoenvironmental settings, biogenicity and early diagenetic processes involved in the formation of ancient carbonate microbialites and, by extension, improve the knowledge of the reservoir geology of correlative units in deep waters offshore Brazil.     

Carbon and sulfur isotopic fluctuations associated with the end-Guadalupian mass extinction in South China

Concentrations of total organic matter (TOC), carbon isotopic compositions of carbonate and organic matter (δ¹³C_carb, δ¹³C_org), and sulfur isotopic compositions of carbonate associated sulfate (δ³⁴S_sulfate) across the Guadalupian–Lopingian (G–L) boundary were analyzed from identical samples of Tieqiao section, Laibin, Guangxi province, South China. The δ¹³C_carb values show a positive excursion from − 0.45‰ to the peak of 3.80‰ in the Laibin limestone member of the Maokou Formation, followed by a drastic drop to − 2.60‰ in the lowest Heshan formation, then returned to about 1.58‰. Similar to the trends of the δ¹³C_carb values, Δ¹³C_carb–org values also show a positive excursion followed by a sharp negative shift. The onset of a major negative carbon isotope excursion postdates the end Guadalupian extinction that indicates subsequent severe disturbance of the ocean–atmosphere carbon cycle. The first biostratigraphic δ³⁴S_sulfate values during the G–L transition exhibit a remarkable fluctuation: a dramatic negative shift followed by a rapid positive shift, ranging from 36.88‰ to − 37.41‰. These sulfate isotopic records suggest that the ocean during the G–L transition was strongly stratified, forming an unstable chemocline separating oxic shallow water from anoxic/euxinic deep water. Chemocline excursions, together with subsequent rapid transgression and oceanic anoxia, were likely responsible for the massive diversity decline of the G–L biotic crisis.     

High-resolution carbon isotope changes in the Permian–Triassic boundary interval, Chongqing, South China; implications for control and growth of earliest Triassic microbialites

High-resolution δ¹³C_CARB analysis of the Permian–Triassic boundary (PTB) interval at the Laolongdong section, Beibei, near the city of Chongqing, south China, encompasses the latest Permian and earliest Triassic major facies changes in the South China Block (SCB). Microbialites form a distinctive unit in the lowermost 190 cm above the top of the Changhsing Formation (latest Permian) at Laolongdong, comparable to a range of earliest Triassic sites in low latitudes in the Tethyan area. The data show that declining values of δ¹³C_CARB, well-known globally, began at the base of the microbialite. High positive values (+3 to 4 ppt) of δ¹³C_CARB in the Late Permian are interpreted to indicate storage of ¹²C in the deep waters of a stratified ocean, that was released during ocean overturn in the earliest Triassic, contributing to the distinctive fall in isotope values; this interpretation has been stated by other authors and is followed here. The δ¹³C_CARB curve shows fluctuations within the microbialite unit, which are not reflected in the microbialite structure. Comparisons between microbialite branches and adjacent micritic sediment show little difference in δ¹³C_CARB, demonstrating that the microbialite grew in equilibrium with surrounding seawater. The Early Triassic microbialites are interpreted to be a response to upwelling of bicarbonate-rich poorly oxygenated water in low latitudes of Tethys Ocean, consistent with current ocean models for the PTB interval. However, the decline of δ¹³C_CARB may be due to a combination of processes, including productivity collapse resulting from mass extinction, return of deep water to ocean surface, oxidation of methane released from methane hydrate destabilisation, and atmospheric deterioration. Nevertheless, build-up of bicarbonate-rich anoxic deep waters may be expected as a result of the partial isolation of Tethys, due to continental geography; release of bicarbonate-rich deep water, by ocean upwelling, in the earliest Triassic may have been an inevitable consequence of this combination of circumstances.     

Stable hydrogen isotope measurement of archaeal ether-bound hydrocarbons

Compound-specific hydrogen isotope analysis of ether-bound isoprenoid hydrocarbons from archaeal membranes has been developed using chemical degradation and gas chromatography/pyrolysis/isotope ratio mass spectrometry. The ether-bound hydrocarbons are quantitatively converted to saturated hydrocarbons by cleavage of ether bonds with HI followed by H₂ reduction in the presence of PtO₂. The δD value of ether-bound hydrocarbon moieties are corrected by way of isotopic mass balance calculation for the hydrogen incorporated during the hydrogenation. The method was successfully applied to determination of the δD values of biphytane moieties in glycerol dialkyl glycerol tetraethers (GDGTs) from a Sulfolobus sp. culture and a marine sediment.     

Magmatic hydrothermal origin of the Hadamengou-Liubagou Au-Mo deposit,Inner Mongolia,China: Constrains on geology,stable and Re-Os isotopes

The Hadamengou-Liubagou Au-Mo deposit is the largest gold deposit in Inner Mongolia of North China. It is hosted by amphibolite to granulite facies metamorphic rocks of the Archean Wulashan Group. To the west and north of the deposit, there occur three alkaline intrusions, including the Devonian-Carboniferous Dahuabei granitoid batholith, the Triassic Shadegai granite and the Xishadegai porphyritic granite with molybdenum mineralization. Over one hundred subparallel, sheet-like ore veins are confined to the nearly EW-trending faults in the deposit. They typically dip 40° to 80° to the south, with strike lengths from hundreds to thousands of meters. Wall rock alterations include potassic, phyllic, and propylitic alteration. Four distinct mineralization stages were identified at the deposit, including K-feldspar-quartz-molybdenite stage (I), quartz-pyrite-epidote/chlorite stage (II), quartz-polymetallic sulfide-gold stage (III), and carbonate-sulfate-quartz stage (IV). Gold precipitated mainly during stage III, while Mo mineralization occurred predominantly in stage I. The δD_H2O and δ¹⁸O_H2O values of the ore-forming fluids range from −125‰ to −62‰ and from 1.4‰ to 7.5‰, respectively, indicating that the fluids were dominated by magmatic water with a minor contribution of meteoric water. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal carbonate minerals vary from −10.3‰ to −3.2‰ and from 3.7‰ to 15.3‰, respectively, suggesting a magmatic carbon origin. The δ³⁴S_CDT values of sulfides from the ores vary from −21.7‰ to 5.4‰ and are typically negative (mostly −20‰ to 0‰). The wide variation of the δ³⁴S_CDT values, the relatively uniform δ¹³C values of carbonates (typically −5.5‰ to −3.2‰), as well as the common association of barite with sulfides suggest that the minerals were precipitated under relatively high fo₂ conditions, probably in a magmatic fluid with δ³⁴S_ƩS ≈ 0‰. The Re-Os isotopic dating on molybdenite from Hadamengou yielded a weighted average age of 381.6 ± 4.3 Ma, indicating that the Mo mineralization occurred in Late Devonian. Collectively, previous ⁴⁰Ar-³⁹Ar and Re-Os isotopic dates roughly outlined two ranges of mineralizing events of 382–323 Ma and 240–218 Ma that correspond to the Variscan and the Indosinian epochs, respectively. The Variscan event is approximately consistent with the Mo mineralization at Hadamengou-Liubagou and the emplacement of the Dahuabei Batholith, whereas the Indosinian event roughly corresponds to the possible peak Au mineralization of the Hadamengou-Liubagou deposit, as well as the magmatic activity and associated Mo mineralization at Xishadegai and Shadegai. Geologic, petrographic and isotopic evidence presented in this study suggest that both gold and molybdenum mineralization at Hadamengou-Liubagou is of magmatic hydrothermal origin. The molybdenum mineralization is suggested to be associated with the magmatic activity during the southward subduction of the Paleo-Asian Ocean beneath the North China Craton (NCC) in Late Devonian. The gold mineralization is most probably related to the magma-derived hydrothermal fluids during the post-collisional extension in Triassic, after the final suturing between the Siberian and NCC in Late Permian.     

Origin and depositional environments of source rocks and crude oils from Niger Delta Basin: Carbon isotopic evidence

Thirty-nine crude oils and twenty-one rock samples from Niger Delta Basin, Nigeria have been characterized based on their isotope compositions by elemental analysis-isotope ratio mass spectrometry and gas chromatography-isotope ratio mass spectrometry. The bulk carbon isotopic values of the whole rock extracts, saturate and aromatic fractions range from –28.7‰ to –26.8‰, –29.2‰ to –27.2 ‰ and –28.5 ‰ to –26.7 ‰, respectively while the bulk carbon isotopic values of the whole oils, saturate and aromatic fractions range from –25.4 ‰ to –27.8 ‰, –25.9 ‰ to –28.4 ‰ and –23.5 ‰ to –26.9 ‰, respectively. The average carbon isotopic compositions of individual alkanes (nC₁₂-nC₃₃) in the rock samples range from –34.9‰ to –28.2‰ whereas the average isotopic values of individual n-alkanes in the oils range from –31.1‰ to –23.8‰. The δ¹³C isotope ratios of pristane and phytane in the rock samples range from –29.2 ‰ to –28.2 ‰ and –30.2 ‰ to –27.4 ‰ respectively while the pristane and phytane isotopic values range from –32.1‰ to –21.9‰ and –30.5‰ to –26.9‰, respectively. The isotopic values recorded for the samples indicated that the crude oils were formed from the mixed input of terrigenous and marine organic matter and deposited under oxic to sub-oxic condition in lacustrine-fluvial/deltaic environments. The stable carbon isotopic compositions were found to be effective in assessing the origin and depositional environments of crude oils in the Niger Delta Basin.     

Hydrocarbons in 60 northeast Gulf of Mexico shelf sediments: a preliminary survey

Hydrocarbon results from gas chromatography of 60 recent sediment and 10 benthic algae samples delineate two distinct shelf environments in the northeastern Gulf of Mexico.Sediments off Florida (shell hashes and sands) have moderate amounts of lipids/total sediment (average 113ppm ± 80%) but low hydrocarbon levels (average 3.06 ppm ± 41%). Aliphatic hydrocarbons are dominated by a series of branched or cyclic, unsaturated C₂₅ isomers. The major n-alkane is n-C₁₇. The n-alkane and isoprenoid patterns are consistent with a marine hydrocarbon source.Sediments closer to the Mississippi River (silts and clays) contain large amounts of lipids (average 232 ppm ± 53%) and hydrocarbons (average 11.7 ppm ± 55%) to total sediment. Aliphatic hydrocarbons are mainly odd carbon number high molecular weight n-alkanes, indicating a terrigenous hydrocarbon source. Isoprenoids are present in greater abundance than in sediments off Florida (n-C₁₇/ pristane and n-C₁₈/phytane ratios ~2to 3). Relatively large amounts of n-C₁₆, together with an even distribution of n-alkanes in the range C₁₄–C₂₀ and a substantial unresolved envelope all point to a fossil fuel input to the Mississippi samples.Samples off the Alabama coast show intermediate characteristics.     

Isotopic and geochemical evolution of ground and surface waters in a karst dominated geological setting: a case study from Belize,Central America

Analysis of stable isotopes and major ions in groundwater and surface waters in Belize, Central America was carried out to identify processes that may affect drinking water quality. Belize has a subtropical rainforest/savannah climate with a varied landscape composed predominantly of carbonate rocks and clastic sediments. Stable oxygen (δ¹⁸O) and hydrogen (δD) isotope ratios for surface and groundwater have a similar range and show high d-excess (10–40.8‰). The high d-excess in water samples suggest secondary continental vapor flux mixing with incoming vapor from the Caribbean Sea. Model calculations indicate that moisture derived from continental evaporation contributes 13% to overhead vapor load. In surface and groundwater, concentrations of dissolved inorganic carbon (DIC) ranged from 5.4 to 112.9 mg C/l and δ¹³C_DIC ranged from −7.4 to −17.4‰. SO₄², Ca²⁺ and Mg²⁺ in the water samples ranged from 2–163, 2–6593 and 2–90 mg/l, respectively. The DIC and δ¹³C_DIC indicate both open and closed system carbonate evolution. Combined δ¹³C_DIC and Ca²⁺, Mg²⁺, and SO₄²⁻ suggest additional groundwater evolution by gypsum dissolution and calcite precipitation. The high SO₄²⁻content of some water samples indicates regional geologic control on water quality. Similarity in the range of δ¹⁸O, δD and δ¹³C_DIC for surface waters and groundwater used for drinking water supply is probably due to high hydraulic conductivities of the karstic aquifers. The results of this study indicate rapid recharge of groundwater aquifers, groundwater influence on surface water chemistry and the potential of surface water to impact groundwater quality and vise versa.     

Salinity variations in the northern Coorong Lagoon,South Australia: Significant changes in the ecosystem following human alteration to the natural water regime

European settlement and drought have significantly impacted the hydrology of the Coorong, a shallow coastal lagoon complex in South Australia, which is part of a terminal wetland at the mouth of the River Murray. An increased salinity associated with lower water levels and progressive isolation from ocean flushes contributed to a severe decline in ecological diversity over the past decades. Here we have conducted a molecular and stable isotopic study of a sedimentary core from the northern Coorong Lagoon spanning more than 5000 years to investigate the recent palaeoenvironmental history of the ecosystem. Major alterations were evident in many biogeochemical parameters in sediments deposited after the 1950s coinciding with the beginning of intensified water regulations. The most prominent shift occurred in δ¹³C profiles of C₂₁–C₃₃ n-alkanes from average values of −23.5‰ to an average of −28.2‰. Further changes included decreases in carbon preference index (CPI) and average chain length (ACL) of the n-alkane series as well as significant increases in algal (e.g. C₂₀ HBI, long chain alkenes and C₂₉-alkadiene) and bacterial (e.g. ¹³C depleted short chain n-alkanes and hopanoids, δ¹³C: −35.9‰ to −30.1‰) derived hydrocarbons. Long chain n-alkanes with a strong odd/even predominance as observed here are typically attributed to terrigenous plants. In the Coorong however, terrigenous input to sedimentary OM is only minor. Therefore changes in the before mentioned parameters were attributed to a source transition from a major contribution of macrophytes towards predominantly microalgae and bacteria.δD values of C₂₁–C₃₃ n-alkanes showed a general trend towards more enriched values in younger sediments, indicating an overall rising salinity. However, the most pronounced positive shift in these profiles again occurred after the 1950s. Altogether this study demonstrates that the recent human induced changes of the Coorong hydrology, compounded by a severe drought led to an increase in salinity and alterations of primary production which have been much more significant than natural variations occurring throughout the Holocene over several thousands of years.     

Geology and Isotope Geochemistry of the Dongzhongla Pb–Zn Deposit in Tibet: Implications for the Origin of the Ore‐Forming Fluids and Storage Condition of Certain Metals

As a newly discovered medium‐sized deposit (proven Pb + Zn resources of 0.23 Mt, 9.43% Pb and 8.73% Zn), the Dongzhongla skarn Pb–Zn deposit is located in the northern margin of the eastern Gangdese, central Lhasa block. Based on the geological conditions in this deposit of ore‐forming fluids, H, O, C, S, Pb, Sr, and noble gas isotopic compositions were analyzed. Results show that δ¹⁸O_SMOW of quartz and calcite ranged from −9.85 to 4.17‰, and δD_SMOW ranged from −124.7 to −99.6‰ (where SMOW is the standard mean ocean water), indicating magma fluids mixed with meteoric water in ore‐forming fluids. The δ¹³C_PDB and δ¹⁸O_SMOW values of calcite range from −1.4 to −1.1‰ and from 5.3 to 15.90‰, respectively, show compositions consistent with the carbonate limestone in the surrounding rocks, implying that the carbon was primarily sourced from the dissolution of carbonate strata in the Luobadui Formation. The ore δ³⁴S composition varied in a narrow range of 2.8 to 5.7‰, mostly between 4‰ and 5‰. The total sulfur isotopic value δ³⁴S was 4.7‰ with characteristics of magmatic sulfur. The ³He/⁴He values of pyrite and galena ranged from 0.101 to 5.7 Ra, lower than those of mantle‐derived fluids (6 ± 1 Ra), but higher than those of the crust (0.01–0.05 Ra), and therefore classified as a crust–mantle mixed source. The Pb isotopic composition for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb values of the ores were in the ranges of 18.628–18.746, 15.698–15.802, and 39.077–39.430, respectively, consistent with the Pb isotopic composition of magmatic rocks in the deposit, classified as upper‐crust lead. The ore lead was likely sourced partially from the crustal basement of the Lhasa Terrane. The initial (⁸⁷Sr/⁸⁶Sr)_i value from five sulfide samples ranged from 0.71732 to 0.72767, and associated ore‐forming fluids were mainly sourced from the partial melting of the upper‐crust materials. Pb isotopic compositions of ore sulfides from the Dongzhongla deposit are similar to that of the Yuiguila and Mengya'a deposit, indicating that they have similar sources of metal‐rich ore‐forming solution. According to basic skarn mineralogy, the economic metals, and the origin of the ore‐forming fluids, the Dongzhongla deposit was classified as a skarn‐type Pb–Zn deposit.