Carbon and oxygen isotopic composition of car- bonate cements of different phases in terrigenous siliciclastic reservoirs and significance for their origin： A case study from sandstones of the Triassic Yanchang Formation, southwestern Ordos Basin, China

Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope （their δ^18O values range from -0.3‰- -0.1‰） and lighter oxygen isotope （their δ^18O values range from -22.1‰- -19.5‰）. Generally, they are closely related to the direct precipitation of oversaturated calcium carbonate from alkaline lake water. This kind of cementation plays an important role in enhancing the anti-compaction ability of sandstones, preserving intragranular volume and providing the mass basis for later disso- lution caused by acidic fluid flow to produce secondary porosity. Ferriferous calcites are characterized by relatively light carbon isotope with δ^13C values ranging from -8.02‰ to -3.23‰, and lighter oxygen isotope with δ^18O values ranging from -22.9‰ to -19.7‰, which is obviously related to the decarboxylation of organic matter during the late period of early diagenesis to the early period of late diagenesis. As the mid-late diagenetic products, ferriferous cal- cites in the study area are considered as the characteristic authigenic minerals for indicating large-scaled hydrocarbon influx and migration within the clastic reservoir. The late ankerite is relatively heavy in carbon isotope with δ^13C values ranging from -1.92‰ to -0.84‰, and shows a wide range of variations in oxygen isotopic composition, with δ^18O values ranging from -20.5‰ to -12.6‰. They are believed to have nothing to do with decarboxylation, but the previously formed marine carbonate rock fragments may serve as the chief carbon source for their precipitation, and the alkaline diagenetic environment at the mid-late stage would promote this process.     

Stable isotope geochemistry and diagenetic mineralization associated with the Tono sandstone-type uranium deposit in Japan

The Tono sandstone-type uranium mine area, middle Honsyu, Japan is composed of Miocene lacustrine sedimentary rocks in the lower part (18–22 Ma) and marine facies in the upper part (15–16 Ma). Calcite and pyrite occur as dominant diagenetic alteration products in these Neogene sedimentary rocks. The characteristics of calcite and pyrite differ significantly between lacustrine and marine facies. Abundant pyrite, calcite, organic matter, and small amounts of marcasite or pyrrhotite occur in the lacustrine facies, whereas small amounts of calcite and framboidal pyrite, organic matter and no marcasite or pyrrhotite are found within the marine units. The δ¹³C values of calcite in the lacustrine deposits are low (−19 to −6‰ PDB) but those in marine formation are high (−11 to +3‰). This implies that the contribution of marine carbonate is larger in upper marine sedimentary rocks, and carbon in calcite in the lower lacustrine formation was derived both from oxidation of organic matter and from dissolved marine inorganic carbon. The δ³⁴S values of framboidal pyrite in the upper marine formation are low (−14 to −8‰ CDT), indicating a small extent of bacterial seawater sulfate reduction, whereas those of euhedral-subhedral pyrite in the lower lignite-bearing arkose sandstone are high (+10 to +43‰), implying a large extent of closed-system bacterial seawater sulfate reduction. The δ³⁴S and δ¹³C data which deviate from a negative correlation line toward higher δ¹³C values suggest methanogenic CO₂ production. During diagenesis of the lacustrine unit, large amounts of euhedral-subhedral pyrite were formed, facilitated by extensive bacterial reduction of seawater sulfate with concomitant oxidation of organic matter, and by hydrolysis reactions of organic matter, producing CH₄ and CO₂. Uranium minerals (coffinite and uraninite) were also formed at this stage by the reduction of U⁶⁺ to U⁴⁺. The conditions of diagenetic alteration within the lacustrine deposits and uranium mineralization is characterized by low Eh in which nearly equal concentrations of CH₄ and HCO₃ ⁻ existed and reduced sulfur species (H₂S, HS⁻) are predominant among aqueous sulfur species, whereas diagenetic alteration of the marine formations was characterized by a predominance of SO₄ ²⁻ among dissolved sulfur species. Modern groundwater in the lacustrine formation has a low Eh value (−335 mV). Estimated and measured low Eh values of modern and ancient interstitial waters in lacustrine environments indicate that a reducing environment in which U⁴⁺ is stable has been maintained since precipitation of uranium minerals. Received: 9 February 1996 / Accepted: 11 April 1997     

Genesis of organic and carbonate carbon in sediments of the North and Middle Caspian basins inferred from the isotope data

Isotopic compositions of organic (δ¹³C-C_org) and carbonate (δ¹³C-C_carb) carbon were analyzed in the particulate matter (hereafter, particulates) and sediments from the North and Middle Caspian basins. Isotopic composition of C_org was used for assessing proportions of the allochthonous and autochthonous organic matter in the particulates. Difference between the δ¹³C-C_org values in surface sediments and particulates is explained by the aerobic and anaerobic diagenetic transformations. Isotopic composition of C_org in sediments may be used as a tool for reconstructing the Quaternary transgressive-regressive history of the Caspian Sea.     

Carbon isotopic characteristics of hydrocarbon gases from coal-measure source rocks——A thermal simulation experiment

1 IntroductionThe compositional characteristics of natural gasesand their carbon isotopic composition are controlledmainly by the type of organic matter and the degree ofits thermal evolution in the source rocks (Song Yan,1995; Xu Yongchang et al., 1994; …     

Hydrochemistry,origin and evolution of sedimentary subsurface fluids: III. Early diagenetic mineralization reactions in high sedimentation—rate basins

The early diagenetic evolution of pore-water chemistry is closely linked to mineralization reactions which consume significant portions of the metabolites released by bacterial organic matter decomposition. These reactions are most intense in high-sedimentation rate basins and include the precipitation of iron-sulfides and various carbonates leading to concretion growth. Early diagenetic pyrite is typically framboidal attesting to its recrystallization from precursor mackinawite, greigite or amorphous FeS which are the favored phases at high supersaturation levels during the initial sulfate reduction stages. The sulfur isotopic composition of early diagnetic pyrite can be used to differentiate diffusion-controlled, open-system conditions with isotopically light sulfide (δ ³⁴S = − 35 to − 20‰) from closed system conditions, under which Raleigh distillation produces increasingly heaver sulfide (δ ³⁴ S = − 35 to + 18‰). Alabandite (Mn-sulfide) is a rare authigenic sulfide in Mn-rich environments such as certain restricted, semi-stagnant basins (Baltic Sea). pH-buffering by hydrogen sulfide and hydrogen ion uptake by the reduction of manganese and iron oxides and hydroxides in the nitrate and sulfate reduction zones raise the pH sufficiently to cause supersaturation of the porewaters with respect to Ca-, Mg-, Fe- and Mn-carbonates and complex solid solutions of them. Fe-carbonates cannot form in the sulfate reduction zone in the presence of dissolved sulfide which competes for the dissolved iron. Likewise, dolomite formation appears to be inhibited or slowed down in the presence of substantial dissolved sulfate. The appearance of siderite and ankerite therefore signals carbonate precipitation below the sulfate reduction zone. Supporting evidence for the early diagenetic origin of many carbonate concertions is provided by their high carbonate contents (70 to 90% reflecting the porosity existing at the time of precipitation, called “minus-cement porosity”), isotopic composition, clay fabrics, and preservation of original bedding features including the shapes of fossils and fecal pellets. In these environments increasing carbon isotope ratios (δ ¹³ C = − 20 to + 15‰) indicate concretion growth below the sulfate reduction zone, i.e., in the methane generation zones. Continuing concretion growth at greater burial depth explains pore water profiles with constantly low Ca and downward decreasing Mg concentrations. Dissolved ammonia and phosphate profiles reguire adsorption and ion-exchange reactions as additional removal machanisms (besides apatite precipitation) in order to explain their downward decrease after they have reached maximum concentrations below the alkalinity maximum. Classification of early diagnetic environments into oxic and anoxic and further subdivision of the latter into sulfidic and non-sulfidic (with suboxic or post-oxic and methanic as further subcategories of the non-sulfidic environment) according to Berner (1981) is preferred over the previous classification in terms of pH/Eh fields. The temperature range of the early diagenetic stage extends from O to about 75°C, at which temperature thermocatalytic organic matter decomposition replaces the earlier bacterially mediated reactions and causes a whole set of new diagenetic reactions (such as feldspar dissolution, smectite to illite transformation) to start.     

Hydrogeochemistry,environmental isotopes and the origin of the Hamamayagi-Ladik thermal spring (Samsun,Turkey)

Hamamayagi thermal spring (HTS) is located along the North Anatolian Fault Zone. The thermal spring has a temperature of 36°C, with total dissolved solids ranging from 485.6 to 508.5 mg/L. Hard, brittle, and gray limestones Permian aged are the reservoir rocks of the HTS. δ¹⁸O–δ²H isotope ratios clearly indicate a meteoric origin for the waters. The δ³⁴S value of sulfate in the thermal water is nearly 4.1‰ and implies a diagenetic environment characterized by reduced sulfur compounds. The δ¹³C ratio for dissolved inorganic carbonate in the HTS lies between −1.78 and −1.62‰, showing that it originates from the dissolution of fresh-water carbonates. Quartz geothermometry suggests a reservoir temperature of 52–85°C for the Hamamayagi geothermal field, but chalcedony geothermometers suggest reservoir temperatures between 30 and 53°C.     

Isotopic constraints on fluid evolution and precipitation mechanisms for the Boléo Cu–Co–Zn district, Mexico

Stable and radiogenic isotope composition of stratiform Cu–Co–Zn mineralization and associated sedimentary rocks within the Boléo district of the Miocene Santa Rosalía basin, Baja California Sur, constrains the evolution of seawater and hydrothermal fluids and the mechanisms responsible for sulfide and oxide deposition. Stable isotope geochemistry of limestone and evaporite units indicates a strong paleogeographic influence on the chemistry of the water column. Near-shore limestone at the base of the Boléo Formation is characterized by modified marine carbon (δ ¹³C_PDB=−6.0 to +4.4‰) and oxygen (δ ¹⁸O_SMOW=+19.5 to +26.2‰) isotope composition due to the influx of ¹³C- and ¹⁸O-depleted fluvial water. Sulfate sulfur isotope composition (δ ³⁴S_CDT=+17.21 to +22.3‰ and δ ¹⁸O_SMOW=+10.7 to +13.1‰) for basal evaporite and claystone facies are similar to Miocene seawater. Strontium isotopes are less radiogenic than expected for Miocene seawater due to interaction with volcanic rocks. Low S/C ratios, high Mn contents and sedimentological evidence indicate the basin water column was oxidizing. The oxygenated basin restricted sulfide precipitation to within the sedimentary pile by replacement of early diagenetic framboidal pyrite and pore-space filling by Cu–Co–Zn sulfides to produce disseminated sulfides. Quartz–Mn oxide oxygen isotope geothermometry constrains mineralization temperature between 18 and 118°C. Sulfur isotopes indicate the following sources of sulfide: (1) bacterial sulfate reduction within the sedimentary pile produced negative δ ³⁴S values (<−20‰) in framboidal pyrite; and (2) bacterial sulfate reduction at high temperature (80–118°C) within the sedimentary pile during the infiltration of the metal-bearing brines produced Cu–Co–Zn sulfides with negative, but close to 0‰, δ ³⁴S values. Isotope modeling of fluid-rock reaction and fluid mixing indicates: (1) sedimentary and marine carbonates (δ ¹³C=−11.6 to −3.2‰ and δ ¹⁸O=+19.0 to +21.8‰) precipitated from basin seawater/pore water that variably mixed with isotopically depleted meteoric waters; and (2) hydrothermal calcite (δ ¹³C=−7.9 to +4.3‰ and δ ¹⁸O=+22.1 to +25.8‰) formed by dissolution and replacement of authigenic marine calcite by downward-infiltrating metalliferous brine and brine-sediment exchange, that prior to reaction with calcite, had mixed with isotopically depleted pore water. The downward infiltration of metalliferous brine is inferred from lateral and stratigraphic metal distributions and from the concentration of Cu sulfides along the upper contact of pyrite-bearing laminae. The co-existence and textural relationships among framboidal pyrite, base metal sulfides, carbonate and Mn–Fe oxides (including magnetite) within mineralized units are consistent with carbonate replacement and high-temperature bacterial reduction within the sedimentary pile occurring simultaneously below a seawater column under predominantly oxygenated conditions.     

The application of δ13C and C/N ratios as indicators of organic carbon sources and paleoenvironmental change of the mangrove ecosystem from Ba Lat Estuary, Red River, Vietnam

In this study, two sediment cores (~70 cm) were collected from separate mangrove forests straddling the Ba Lat Estuary, Red River of northern Vietnam, to examine the origins of sedimentary organic carbon (SOC) and reconstruct the paleoenvironment. In addition, mangrove leaves and particulate organic matter were collected and measured for δ¹³C to trace the origins of SOC. The cores were analyzed by high-resolution sections for δ¹³C, TOC, C/N ratios, sediment grain size, water content, and porosity, with values of δ¹³C, TOC, and C/N ratios ranging from −28.19 to −22.5‰, 2.14–30.94 mg/g, and 10.29–18.32, respectively. The δ¹³C and TOC relationship indicated that there were some small residual effects of diagenetic processes on TOC and δ¹³C values in mangrove sediments. However, the shifts of δ¹³C and C/N ratios from the bottom to the surface sediment of the cores explained the change in organic matter sources, with values of C/N > 12 and δ¹³C < −25‰, and C/N < 12 and δ¹³C > −25‰ indicated terrestrial (e.g., mangrove litter) and marine phytoplankton sources, respectively. The covarying δ¹³C, C/N ratios, and sediment grain sizes during the past 100 years in sediment cores showed that the paleoenvironment may be reconstructed into three environments (subtidal, tidal flat, and intertidal mangrove). General trends in δ¹³C and C/N followed a gradual increase in the C/N ratio and a concomitant decrease in δ¹³C from the subtidal, through to tidal flat, and to the intertidal mangrove. δ¹³C and C/N ratios are therefore effective in measuring the continuum of environmental change in mangrove ecosystem.     

Contrasting stable isotope behavior between calcite and dolomite marbles,Lone Mountain,Nevada

 Late Proterozoic to Cambrian carbonate rocks from Lone Mountain, west central Nevada, record multiple post-depositional events including: (1) diagenesis, (2) Mesozoic regional metamorphism, (3) Late Cretaceous contact metamorphism, related to the emplacement of the Lone Mountain granitic pluton and (4) Tertiary hydrothermal alteration associated with extension, uplift and intrusion of silicic porphyry and lamprophyre dikes. Essentially pure calcite and dolomite marbles have stable isotopic compositions that can be divided into two groups, one with positive δ¹³C values from+3.1 to +1.4 ‰ (PDB) and high δ¹⁸O values from +21.5 to +15.8 ‰ (SMOW), and the other with negative δ¹³C values from –3.3 to –3.6‰ and low δ¹⁸O values from +16.9 to +11.1‰. Marbles also contain minor amounts of quartz, muscovite and phlogopite. Brown and blue luminescent, clear, smooth textured quartz grains from orange luminescent calcite marbles have high δ¹⁸O values from +23.9 to +18.1‰, while brown luminescent, opaque, rough textured quartz grains from red luminescent dolomite marbles typically have low δ¹⁸O values from +2.0 to +9.3‰. The δ¹⁸O values of muscovite and phlogopite from marbles are typical of micas in metamorphic rocks, with values between +10.4 and +14.4‰, whereas mica δD values are very depleted, varying from −102 to −156‰. No significant lowering of the δ¹⁸O values of Lone Mountain carbonates is inferred to have occurred during metamorphism as a result of devolatilization reactions because of the essentially pure nature of the marbles. Bright luminescence along the edges of fractures, quartz cements and quartz overgrowths in dolomite marbles, low δD values of micas, negative δ¹³C values and low δ¹⁸O values of calcite and dolomite, and depleted δ¹⁸O values of quartz from dolomite marbles all indicate that meteoric fluids interacted with Lone Mountain marbles during the Tertiary. Partial oxygen isotopic exchange between calcite and low ¹⁸O meteoric fluids lowered the δ¹⁸O values of calcite, resulting in uniform quartz-calcite fractionations that define an apparent pseudoisotherm. These quartz-calcite fractionations significantly underestimate both the temperature of metamorphism and the temperature of post-metamorphic alteration. Partial oxygen isotopic exchange between quartz and meteoric fluids also resulted in ¹⁸O depletion of quartz from dolomite marbles. This partial exchange was facilitated by an increase in the surface area of the quartz as a result of its dissolution by meteoric fluids. The negative δ¹³C values in carbonates result from the oxidation of organic material by meteoric fluids following metamorphism. Stable isotopic data from Lone Mountain marbles are consistent with the extensive circulation of meteoric hydrothermal fluids throughout western Nevada in Tertiary time. Received: 1 February 1994/Accepted: 12 September 1995     

Magmatic zircon oxygen isotopes of 1.88–1.87 Ga orogenic and 1.65–1.54 Ga anorogenic magmatism in Finland

Summary Oxygen isotope ratios of igneous zircon from magmatic rocks in Finland provide insights into the evolution and growth of the Precambrian crust during the Svecofennian orogeny. These data preserve magmatic δ¹⁸O values and correlate with major discontinuities in the lower crust. Oxygen isotope ratios of zircon across the 1.88–1.87 Ga Central Finland granitoid complex (CFGC) range from 5.50‰ to 6.84‰, except for three plutons in contact with the adjacent greenstone and metasedimentary belts (δ¹⁸O(Zrc) = 7.60‰–7.78‰). There is a systematic variation in δ¹⁸O(Zrc) with respect to geographic location in the CFGC, ranging from 6.60±0.23‰ (σ) in the northeast to 5.90±0.40‰ in the west-southwest. These values correlate with a change in crustal thickness and shift in geochemical composition. The oxygen isotope composition of the 1.65–1.54 Ga rapakivi granites and related rocks in southern Finland show a decreasing trend from north to south, independent of their emplacement age. The southern anorogenic granite group has an average δ¹⁸O in zircon of 6.14±0.07‰ and the northern anorogenic group has an average δ¹⁸O in zircon of 8.14±0.59‰. This difference reflects the boundary between island arc terrains accreted during the Paleoproterozoic. Deceased     

Biogeochemistry of the Russian Arctic. Kara Sea: Research results under the SIRRO project, 1995–2003

The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions aboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO₂ were examined throughout the whole sea area at more than 200 sites. The δ¹³C varies from −22 and −24‰ where Atlantic waters enter the Kara Sea and in the North-eastern part of the water area to −27‰ in the Yenisei and Ob estuaries. The value of δ¹³C of the plankton is only weakly correlated with the δ¹³C of the organic matter from the sediments and is lower by as much as 3–4‰. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the riverwaters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the off-shore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from −29 to −35‰ in the riverine part, from −28 to −27‰ in the estuaries, and from −27.0 to −25% in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO₂ concentrations, and long-distance CO₂ supply to the sea with riverwaters. The data obtained on the isotopic composition of CO₂ in the surface waters of the Kara Sea were used to map the distribution of δ¹³C_{CO 2}. The complex of hydrocarbon gases extracted from the waters included methane, C₂–C₅, and unsaturated C₂₌–C₄₌ hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3–5 μl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with δ¹³C from −105 to −90‰ first occurs in the sediments at depths of 40–200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the δ¹³C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (δ¹³C from −25 to −60‰) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea. Original Russian Text ? E.M. Galimov, L.A. Kodina, O.V. Stepanets, G.S. Korobeinik, 2006, published in Geokhimiya, 2006, No. 11, pp. 1139–1191.     

Mineralogy, geochemistry and geological significance of tourmaline-rich rocks from the Paleozoic Cinco Villas massif (western Pyrenees, Spain)

Tourmaline-rich rocks associated with clastic metasedimentary rocks of Carboniferous age occur in the Cinco Villas massif, western Pyrenees. Three types of tourmaline-rich rocks were distinguished: (1) Fine-grained stratiform tourmaline-rich rocks, which are associated with carbonaceous metapelites (TR1); (2) stratabound tourmaline-rich rocks, associated with metapelites in the contact aureole of the Aya granitoid pluton (TR2); (3) stratabound to massive tourmaline-rich rocks, associated with psammopelites in contact with granites and pegmatites (TR3). Tourmalines belong to the schorl–dravite solid solution series and have a wide compositional range, from nearly end-member dravite for TR1 tourmalines to schorl for TR3 tourmalines; TR2 tourmalines have intermediate compositions. The Fe/(Fe+Mg) typically varies between 0.02 and ≈0.55, increasing from TR1 to TR3. The TR1 tourmalines commonly display a discontinuous chemical zoning with Fe-rich green cores (8–8.5% FeO) and Mg-rich colorless rims (10–11% MgO). In contrast, crystals that exhibit fine growth lamellae appear to lack significant chemical zoning. Oxygen and hydrogen isotope compositions also reveal major differences between TR1 and TR3 tourmalines, the former displaying heavier δ¹⁸O values (17.7–19‰) and δD values (−35 to −42‰) than TR3 tourmalines 11 to 13‰ and −47 to −76‰, respectively. The TR2 tourmalines show intermediate values of 11.3 to 14.6‰ for δ¹⁸O and −40 to −55‰ for δD. Linear and continuous chemical variations obtained for major and trace elements of the whole rocks reflect mixing between clay-rich and quartz-rich end-members, indicative that some tourmaline-rich rocks contain a significant detrital component. Chondrite normalized REE (rare earth element) patterns of tourmaline-rich rocks are similar to those of surrounding unaltered clastic metasediments, except for some TR1 rocks which are characterized by low contents of ΣREE. Mass-balance calculations show that tourmaline-forming processes plus metamorphism led to mass and volume changes at mesoscopic scales (≈10% for the TR1 tourmalinites). Silicon, Fe, Mn, and REE elements were partially lost from sedimentary rocks, whereas Mg and particularly B were added to pelitic sediments. Available data, nevertheless, do not allow an assessment of the boron source. Formation of the TR1 tourmaline-rich rocks probably was the net result of several processes, including direct precipitation from B-rich hydrothermal fluids or colloids, early diagenetic reactions of carbonaceous pelitic sediments with these fluids, and subsequent recrystallization during regional metamorphism. The TR2 tourmaline-rich rocks mainly developed by metamorphic recrystallization of TR1. Tourmaline-rich rocks and veins adjacent to pegmatites and granitic rocks (TR3) are the result of boron metasomatism; the primary boron having been recycled from stratiform tourmalinites during regional metamorphism and magmatism. Received: 18 November 1996 / Accepted: 25 April 1997     

The Transfiguration continental red-bed Cu–Pb–Zn–Ag deposit,Quebec Appalachians,Canada

The Transfiguration Cu–Pb–Zn–Ag deposit, enclosed within reduced grey sandstone, is associated with continental red beds of the Lower Silurian Robitaille Formation in the Quebec Appalachians, Canada. The Robitaille Formation rests unconformably on foliated Cambro-Ordovician rocks. The unconformity is locally cut by barite veins. The basal unit of the Robitaille Formation comprises green wacke and pebble conglomerate, which locally contain calcite nodules. The latter have microstructures characteristic of alpha-type calcretes, such as “floating” fabrics, calcite-filled fractures (crystallaria) and circumgranular cracks. Massive, grey sandstone overlies the basal green wacke and pebble conglomerate unit, which is overlain, in turn, by red, fine-grained sandstone. Mineralisation occurred underneath the red sandstone unit, chiefly in the grey sandstone unit, as disseminated and veinlet sulphides. Chalcopyrite, the most abundant Cu sulphide, replaced early pyrite. Calcrete, disseminated carbonate and vein carbonate have stable isotope ratios varying from −7.5‰ to −1.1‰ δ¹³C and from 14.7‰ to 21.3‰ δ¹⁸O. The negative δ¹³C values indicate the oxidation of organic matter in a continental environment. Sulphur isotope ratios for pyrite, chalcopyrite and galena vary from −19‰ to 25‰ δ³⁴S, as measured on mineral concentrates by a conventional SO₂ technique. Laser-assisted microanalyses (by fluorination) of S isotopes in pyrite show an analogous range in δ³⁴S values, from −21‰ to 25‰. Negative and positive δ³⁴S values are compatible with bacterial sulphate reduction (BSR) in systems open and closed with respect to sulphate. We interpret similarly high δ³⁴S values for sulphide concentrates (25.1‰) and for vein barite (26.2‰) to result from rapid and complete thermochemical reduction of pore-water sulphate. Two early to late diagenetic stages of mineralisation best explain the origin of the Transfiguration deposit. The first stage was characterised by the ponding of groundwater over the Taconian unconformity, recorded by calcrete and early pyrite formation via BSR in grey sandstone. Early pyrite contains up to 2 wt.% Pb, which is consistent with Pb fixation by sulphate-reducing bacteria. The second stage (II) is defined by the replacement of early pyrite by chalcopyrite, as well as by sulphide precipitation via either BSR or thermochemical sulphate reduction (TSR) in grey sandstone. This event resulted from the synsedimentary fault-controlled percolation and mixing of (1) an oxidising, sulphate-bearing cupriferous fluid migrating per descensum from the red-bed sequence and (2) a hydrocarbon-bearing fluid migrating per ascensum from the Cambro-Ordovician basement. Mixing between the two fluids led to sulphate reduction, causing Cu sulphide precipitation. The positive correlation between Cu and Fe³⁺/Fe²⁺ bulk rock values suggests that Fe acted as a redox agent during sulphate reduction. Stage II diagenetic fluid migration is tentatively attributed to the Late Silurian Salinic extensional event.     

Study on Modern Plant C－13 in Western China and Its Significance

Organic carbon isotopic composition(δ^13C) is one of the important proxies in paleoenvironment studies.In this paper modern plant δ^13C in the arid areas of China and Tibetan Plateau is studied.It is found that most terrestrial plant species in western China are C3 plants with δ^13C values ranging from -32.6‰ to -23.2‰ and only few species are C4 plants with δ^13C values from -16.8‰ to -13.3‰.The δ^13C is closely related to precipitation (or humidity),i.e., light δ^13C is related to high precipitation(or humid climate),while heavy δ^13C to low precipitation (or dry climate),but there is almost no relation between plant δ^13C and temperature.Submerged plants have δ^13C values ranging from -22.0‰ to -12.7‰,like C4 plants,while merged plants have δ^13C values ranging from -28.1‰ to -24.5‰，like C3 C4 plants,while marged plants have δ^13C values ranging from -28.1‰ to -24.5‰,like C3 plants.It can then be concluded that organic δ^13C variations in terrestrial sediments such as loeas and soil in western China can indicate precipitation changes,but those in lake sediments can reflect organic sources and the productivity of different types of aquatic plants.     

Comprehensive geochemical identification of highly evolved marine hydrocarbon source rocks： Organic matter, paleoenvironment and development of effective hydrocarbon source rocks

1 Introduction China’s widespread marine carbonate rock series are mostly characterized by intensive thermal evolution and low abundance of organic matter, especially the Lower Paleozoic carbonate rocks have experienced multi-episodes of tectonics and ap…     

Sulfur isotopic systematics of granitoids from southwestern New Brunswick, Canada: implications for magmatic-hydrothermal processes, redox conditions, and gold mineralization

Bulk δ ³⁴S_rock values, sulfur contents, and magnetic susceptibility were determined for 12 gold-related granitoid intrusions in southwestern New Brunswick, the Canadian Appalachians. The sulfur isotope compositions of sulfide minerals in some of the granitoid samples were also analyzed. This new dataset was used to characterize two distinctive groups of granitoids: (1) a Late Devonian granitic series (GS) and (2) a Late Silurian to Early Devonian granodioritic to monzogranitic series (GMS). The GS rocks have a large range in δ ³⁴S values of −7.1‰ to +13‰ with an average of 2.2 ± 5.0‰ (1σ), low bulk-S contents (33 to 7,710 ppm) and low magnetic susceptibility values (<10⁻⁴ SI), consistent with reduced ilmenite-series granites. The GMS rocks have a relatively narrower variation in δ ³⁴S values of −4.4‰ to +7.3‰ with an average 1.2 ± 2.9‰ but with larger ranges in bulk-S contents (45 to 11,100 ppm) and high magnetic susceptibility values (>10⁻³ SI), indicative of oxidized magnetite-series granites. The exceptions for the GMS rocks are the Lake George granodiorite and Tower Hill granite that display reduced characteristics, which may have resulted from interaction of the magmas forming these intrusions with graphite- or organic carbon-bearing sedimentary rocks. The bulk δ ³⁴S values and S contents of the GMS rocks are interpreted in terms of selective assimilation–fractional crystallization (SAFC) processes. Degassing processes may account for the δ ³⁴S values and S contents of some GS rocks. The characteristics of our sulfur isotope and abundance data suggest that mineralizing components S and Au in intrusion-related gold systems are dominantly derived from magmatic sources, although minor contaminants derived from country rocks are evident. In addition, the molar sulfate to sulfide ratio in a granitic rock sample can be calculated from the δ ³⁴S_rock value of the whole-rock sample and the δ ³⁴S_sulfide (or δ ³⁴S_sulfate) value of sulfide and/or sulfate mineral in the sample on the basis of S-isotope fractionation and mass balance under the condition of magmatic equilibrium. This may be used to predict the speciation of sulfur in granitic rocks, which can be a potential exploration tool for intrusion-related gold systems.     

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

The Sekarna Zn–Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn–Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation–inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000–20,000 ppm) and galena (12–189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80–130°C. The final ice melting temperatures range from −22°C to −11°C, which correspond to salinities of 15–24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (−11.2‰ to −9.3‰) and galena (−16‰ to −12.3‰). The δ³⁴S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.     

The trophic structure of the pipefish community (Pisces: Syngnathidae) from a western Mediterranean seagrass meadow based on stable isotope analysis

Syngnathus abaster andSyngnathus typhle (Pisces: Syngnathidae) from a dense Cymodocea nodesa meadow in the western Mediterranean Stagnone di Marsala (Italy) were studied using δ¹³N and δ¹⁵N analysis. Because of the presence of these two species in the same habitat and the specialized parental care by the male, the effect of species and sex on the isotopic composition was also studied to investigate the different feeding strategies between and within species.S. abaster andS. typhle exhibited enriched¹³C and¹⁵N values throughout the sampling period (mean ±SE, δ¹³C =−10.5±1.8‰ and−10.8±2.0‰, δ¹⁵N=11.9±0.7‰ and 10.6±1.0%., respectively), suggesting that these species receive their energy mainly from mixed sources, particularly from sedimentary and particulate organic matter and the seagrassC. nodosa as ultimate organic matter sources. ANOVA results demonstrated that the interaction between season, species, and sex significantly affected the isotopic composition of the pipefish (p<0.001 for both δ¹³C and δ¹⁵N). Differences between species and sex, although significant, were smaller than the values generally reported for trophic level differences (≈1‰ and ≈3.5‰ for δ¹⁵N, respectively) and change in foraging habitat, Slight isotopic differences may mirror small differences in resource exploitation and resource partitioning. Evidence from stomach content analysis from the literature coupled with stable isotope measurements, while disagreeing somewhat, provide additional knowledge of pipefish feeding strategies.     

Geochemistry of C,O, and Sr isotopes and chemostratigraphy of neoproterozoic rocks in the northern Yenisei Ridge

Isotopic compositions of C, O, and Sr in carbonates, as well as Rb-Sr systems in the silicate material from Upper Precambrian and Lower Cambrian rocks exposed by the Chapa River in the northern Yenisei Ridge, are studied. The Late Precambrian part of the section includes the following formations (from the bottom to top): Lopatinskaya (hereafter, Lopatino), Vandadykskaya (hereafter, Vandadyk) or Kar’ernaya, Chivida, Suvorovskaya (hereafter, Suvorovo), Pod”emskaya (hereafter, Podyom), and Nemchanka. They are characterized by alternation of horizons with anomalously high and low δ¹³C values (such alternation is typical of the ∼700–550 Ma interval). The lower, relatively thin (20 m), positive excursion (δ¹³C up to 4.3‰) was established in dolomites from the lower subformation of the Vandadyk (Kar’ernaya) Formation (hereafter, lower Vandadyk subformation). The upper positive excursion (δ¹³C = 2.2 ± 0.6‰) was recorded in the 3-km-thick Nemchanka Formation enriched in terrigenous rocks. The lower negative excursion stands out as uniform, moderately low δ¹³C values (−2 ± 1‰) and significant thickness. It comprises the upper part of the Vandadyk Formation, as well as Chivida and Podyom formations. The upper negative excursion is related to a thin (∼20 m) marker carbonate horizon of the upper Nemchanka subformation, in which δ¹³C values fall down to −8.3‰. The lower part of the Lebyazhinskaya (hereafter, Lebyazhino) Formation, which overlies the Nemchanka Formation, shows a step-by-step increase in δ¹³C from −2.2 to 2.5‰ typical of the Vendianto-Cambrian (Nemakit-Daldyn Horizon/Stage) transitional sequences. The absence of relationships between the carbon and oxygen isotope compositions and other parameters of postsedimentary alterations suggests that the excursions characterized above could form at the sedimentation stage and coincide in general with δ¹³C fluctuations in seawater. The value of ⁸⁷Sr/⁸⁶Sr = 0.7076−0.7078 in limestones of the Podyom Formation points to their early Ediacaran age. Values of ⁸⁷Sr/⁸⁶Sr = 0.70841 and 0.70845 in dolomites of the lower Lebyazhino subformation correspond to the Early Cambrian. The Rb-Sr systems of the clay material from the Vandadyk and Chivida formations are approximated by a straight line, parameters of which correspond to the age of 695 ± 20 Ma (⁸⁷Sr/⁸⁶Sr₀ = 0.7200 ± 0.0013) and probably characterize the epigenetic stage of older sedimentary rocks, which were subjected to very rapid exhumation and “polar” sulfuric acid weathering in the course of glacioeustatic regression.     

Biogeochemistry and paleoclimate variability during the Holocene: a record from Mansar Lake,Lesser Himalaya

Investigation of biogeochemistry and amino acids on a 30-m-long core from Mansar Lake has thrown light on palaeoclimate variability during the Holocene period. The C/N ratio between 6 and 10 with some deviations and δ13C mostly between −20 and −22‰ in the shallow core, as well as a C/N ratio greater than 13 reaching from 19 to 20 and correspondingly lower δ13C of –28‰ in the deeper core suggest an aquatic source of carbon in the former and a cellulose-rich land plant source in the latter. This is supported by the abrupt increase in organic carbon content in the deeper core compared to the shallow core, which indicates a hot and wet climatic regime during the early Holocene and dry and cold during the late Holocene period. The amino acid data AA-C/C% and AA-N/N% are higher in shallow sediments compared to deeper sediments, indicating an aquatic plant source in the shallow core and greater supply of land plant sources in the deeper core. The lower percentage of the non-protein amino acids β-alanine (ALA) and γ-amino-butyric acid in the shallow core compared to the deeper core indicates different sources of organic matter in the lake basin. The higher amino acid ratio Asp/β-Ala (16.99 av.) and Glu/γ-Aba (18.18 av.) in the shallow core and lower ratios (10.32 and 12.41 av.) in the deeper core, and Asp/Glu (1.52 av.) and β-Ala/γ-Aba (1.61 av.) ratios in the former, which are potential indicators of the nature of the organic matter, are higher in the shallow core relative to the deeper core (1.33 and 1.23 av.), indicating relative biodegradation of organic matter in deeper sediments. It has been observed that the organic matter associated with the dry season is relatively less biodegraded, as evidenced from their higher ratios, and is more biodegraded in the wet season as their ratios are lower in the river sediments. In the absence of a bacterial contribution of organic matter from the soil source in this lake, since Mansar Lake is a non-drainage type, it is envisaged that the climatic variation may be responsible for biodegradation in the deeper core sediments. Therefore, the C/N ratio and δ13C values supported by amino acid data, the latter being significant in revealing primary productivity and a terrestrial source of organic matter, suggest a hot and wet climatic regime during the early Holocene (ca. 7580 bp) and a dry and cold in the late Holocene period (ca. 4050 bp).