A fluid inclusion and stable isotope study of 200 Ma of fluid evolution in the Galway Granite, Connemara, Ireland

Fluid inclusions in granite quartz and three generations of veins indicate that three fluids have affected the Caledonian Galway Granite. These fluids were examined by petrography, microthermometry, chlorite thermometry, fluid chemistry and stable isotope studies. The earliest fluid was a H₂O-CO₂-NaCl fluid of moderate salinity (4–10 wt% NaCl eq.) that deposited late-magmatic molybdenite mineralised quartz veins (V₁) and formed the earliest secondary inclusions in granite quartz. This fluid is more abundant in the west of the batholith, corresponding to a decrease in emplacement depth. Within veins, and to the east, this fluid was trapped homogeneously, but in granite quartz in the west it unmixed at 305–390 °C and 0.7–1.8 kbar. Homogeneous quartz δ¹⁸O across the batholith (9.5 ± 0.4‰n = 12) suggests V₁ precipitation at high temperatures (perhaps 600 °C) and pressures (1–3 kbar) from magmatic fluids. Microthermometric data for V₁ indicate lower temperatures, suggesting inclusion volumes re-equilibrated during cooling. The second fluid was a H₂O-NaCl-KCl, low-moderate salinity (0–10 wt% NaCl eq.), moderate temperature (270–340 °C), high δD (−18 ± 2‰), low δ¹⁸O (0.5–2.0‰) fluid of meteoric origin. This fluid penetrated the batholith via quartz veins (V₂) which infill faults active during post-consolidation uplift of the batholith. It forms the most common inclusion type in granite quartz throughout the batholith and is responsible for widespread retrograde alteration involving chloritization of biotite and hornblende, sericitization and saussuritization of plagioclase, and reddening of K-feldspar. The salinity was generated by fluid-rock interactions within the granite. Within granite quartz this fluid was trapped at 0.5–2.3 kbar, having become overpressured. This fluid probably infiltrated the Granite in a meteoric-convection system during cooling after intrusion, but a later age cannot be ruled out. The final fluid to enter the Granite and its host rocks was a H₂O-NaCl-CaCl₂-KCl fluid with variable salinity (8–28 wt% NaCl eq.), temperature (125–205 °C), δD (−17 to −45‰), δ¹⁸O (−3 to + 1.2‰), δ¹³C_CO2 (−19 to 0‰) and δ³⁴S_sulphate (13–23‰) that deposited veins containing quartz, fluorite, calcite, barite, galena, chalcopyrite sphalerite and pyrite (V₃). Correlations of salinity, temperature, δD and δ¹⁸O are interpreted as the result of mixing of two fluid end-members, one a high-δD (−17 to −8‰), moderate-δ¹⁸O (1.2–2.5‰), high-δ¹³C_CO2 (> −4‰), low-δ³⁴S_sulphate (13‰), high-temperature (205–230 °C), moderate-salinity (8–12 wt% NaCl eq.) fluid, the other a low-δD (−61 to −45‰), low-δ¹⁸O (−5.4 to −3‰), low-δ¹³C (<−10‰), high-δ³⁴S_sulphate (20–23‰) low-temperature (80–125 °C), high-salinity (21–28 wt% NaCl eq.) fluid. Geochronological evidence suggests V₃ veins are late Triassic; the high-δD end-member is interpreted as a contemporaneous surface fluid, probably mixed meteoric water and evaporated seawater and/or dissolved evaporites, whereas the low-δD end-member is interpreted as a basinal brine derived from the adjacent Carboniferous sequence. This study demonstrates that the Galway Granite was a locus for repeated fluid events for a variety of reasons; from expulsion of magmatic fluids during the final stages of crystallisation, through a meteoric convection system, probably driven by waning magmatic heat, to much later mineralisation, concentrated in its vicinity due to thermal, tectonic and compositional properties of granite batholiths which encourage mineralisation long after magmatic heat has abated. Received: 3 April 1996 / Accepted: 5 May 1997     

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.     

Stable isotope characteristics and origin of ore-forming fluids in copper-gold-polymetallic deposits within strike-slip pull-apart basin of Weishan-Yongping continental collision orogenic belt, Yunnan Province, China

More than 140 middle-small sized deposits or minerals are present in the Weishan-Yongping ore concentration area which is located in the southern part of a typical Lanping strike-slip and pull-apart basin. It has plenty of mineral resources derived from the collision between the Indian and Asian plates. The ore-forming fluid system in the Weishan-Yongping ore concentration area can be divided into two subsystems, namely, the Zijinshan subsystem and Gonglang arc subsystem. The ore-forming fluids of Cu, Co deposits in the Gonglang arc fluid subsystem have δD values between −83.8‰ and −69‰, δ¹⁸O values between 4.17‰ and 10.45‰, and δ¹³C values between −13.6‰ and 3.7‰, suggesting that the ore-forming fluids of Cu, Co deposits were derived mainly from magmatic water and partly from formation water. The ore-forming fluids of Au, Pb, Zn, Fe deposits in the Zijinshan subsystem have δD values between −117.4‰ and −76‰, δ¹⁸O values between 5.32‰ and 9.56‰, and Δ¹³C values between −10.07‰ and −1.5‰. The ore-forming fluids of Sb deposits have δD values between −95‰ and −78‰, δ¹⁸O values between 4.5‰ and 32.3‰, and Δ¹³C values between −26.4‰ and −1.9‰. Hence, the ore-forming fluids of the Zijinshan subsystem must have been derived mainly from formation water and partly from magmatic water. Affected by the collision between the Indian and Asian plates, ore-forming fluids in Weishan-Yongping basin migrated considerably from southwest to northeast. At first, the Gonglang arc subsystem with high temperature and high salinity was formed. With the development of the ore-forming fluids, the Zijinshan subsystem with lower temperature and lower salinity was subsequently formed. Translated from Mineral Deposits, 2006, 25(1): 60–70 [译自: 矿床地质]     

S,Pb, C and O isotopic compositions and ore genesis of the strata-bound polymetallic sulfide deposits in central Inner Mongolia,China

The strata-bound Cu−Pb−Zn polymetallic sulfide deposits occur in metamorphic rocks of greenschist phase of the middle-upper Proterozoic Langshan Group in central Inner Mongolia. δ³⁴S values for sulfides range from −3.1‰ to +37.3‰, and an apparent difference is noticed between vein sulfides and those in bedded rocks. For example, δ³⁴S values for bedded pyrite range from +10.6‰ to +20.0‰, while those for vein pyrite vary from −3.1‰ to +14.1‰. δ³⁴S of bedded pyrrhotite is in the range +7.9‰–+23.5‰ in comparison with +6.5‰–+17.1‰ for vein pyrrhotite. The wide scatter of δ³⁴S and the enrichment of heavier sulfur indicate that sulfur may have been derived from H₂S as a result of bacterial reduction of sulfates in the sea water. Sulfur isotopic composition also differs from deposit to deposit in this area because of the difference in environment in which they were formed. The mobilization of bedded sulfides in response to regional metamorphism and magmatic intrusion led to the formation of vein sulfides. δ¹⁸O and δ¹³C of ore-bearing rocks and wall rocks are within the range typical of ordinary marine facies, with the exception of lower values for ore-bearing marble at Huogeqi probably due to diopsidization and tremalitization of carbonate rocks. Pb isotopic composition is relatively stable and characterized by lower radio-genetic lead. The age of basement rocks was calculated to be about 23.9 Ma and ore-forming age 7.8 Ma.²⁰⁷Pb/²⁰⁴Pb−²⁰⁶Pb/²⁰⁴Pb and²⁰⁸Pb/²⁰⁴Pb−²⁰⁶Pb/²⁰⁴Pb plots indicate that Pb may probably be derived from the lower crust or upper mantle. It is believed that the deposits in this region are related to submarine volcanic exhalation superimposed by later regional metamorphism and magmatic intrusion.     

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     

Contrasting fluids and reservoirs in the contiguous Marcona and Mina Justa iron oxide–Cu (–Ag–Au) deposits,south-central Perú

The Marcona–Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide–copper–gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3–4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite–biotite–calcic amphibole assemblages are inferred to have crystallized from a 700–800°C Fe oxide melt with a δ¹⁸O value from +5.2‰ to +7.7‰. Stage M-IV magnetite–phlogopite–calcic amphibole–sulphide assemblages were subsequently precipitated from 430–600°C aqueous fluids with dominantly magmatic isotopic compositions (δ³⁴S = +0.8‰ to +5.9‰; δ¹⁸O = +9.6‰ to +12.2‰; δD = −73‰ to −43‰; and δ¹³C = −3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide–calcite–amphibole assemblages (stage M-V) were deposited from fluids with similar δ³⁴S (+1.8‰ to +5.0‰), δ¹⁸O (+10.1‰ to +12.5‰) and δ¹³C (−3.4‰), but higher δD values (average −8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite–pyrite assemblages precipitated from a magmatic fluid (δ³⁴S = +0.8‰ to +3.9‰; δ¹⁸O = +9.5‰ to +11.5‰) at 540–600°C, whereas ensuing chalcopyrite–bornite–digenite–chalcocite–hematite–calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ³⁴S ≥ +29‰, δ¹⁸O = 0.1‰ and δ¹³C = −8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (–K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite–pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.     

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.     

Origin and transport of sedimentary organic matter in the Yalujiang estuary,North China

The biogeochemistry of organic matter (OM) in a macrotidal estuary, the Yalujiang River, was studied during two cruises: the flood season in August 1994 and the dry season in April 1996. Surface sediments were collected in the riverine zone (RZ), the turbidity maximum zone (TMZ), and the marine zone (MZ). The molecular distribution of the n-alkanes and fatty acid series and bulk sediment characteristics, such as C:N and δ¹³C, were used to assess differences in OM source and transport from the river upstream to the marine end member. Higher C:N values typical for terrestrial sources were observed at the upper reach for both seasons. The δ¹³C of OM in surface sediments varied from −27.3‰ to −21.6‰ in the flood season and from −26.8‰ to −31‰ in the dry season. The concentrations of n-alkanes varied between 0.3–21.4 μg g⁻¹ and the variation of fatty acids was 4.8–32.9 μg g⁻¹. The data showed mixing of terrestrial and autochthonous OM in the middle and lower reaches. The distribution of lipids (n-alkanes and Carbon Preference Index) encountered in this study confirmed the importance of terrestrial OM in the sediment samples from degraded soil material. The distribution of fatty acids suggested important phytoplankton, zooplankton, and microbial signals (short-chain and unsaturated acids; ≤C₂₀). Branched fatty acids, such as the iso- and anteiso-C₁₅ and C₁₇ compounds, relfect bacterial contributions. All samples were characterized by a high proportion of mixture inputs in both seasons. A slight decreasing trend was observed with increasing salinity except for the highest percentage of mixed fatty acids in the TMZ of the flood season. Terrestrial fatty acids were approximately 20% in the flood season and 27–46% in the dry season. Differences in hydrological conditions and primary production between the TMZ, RZ, and MZ resulted in different OM distributions, which are reflected in the sources and degree of diagenesis of the sedimentary OM. Seasonal variation may be strongly influenced by hydrological characteristics rather than primary productivity and anthropogenic activities in the Yalujiang region.     

Temporal and spatial differences in salinity and water chemistry in SW Florida estuaries: Effects of human-impacted watersheds

Three estuaries near Naples, Florida with variably modified watersheds have been investigated to understand the chemical consequences of altering drainage patterns. Blackwater River (near natural drainage, control site), Henderson Creek (moderately modified watershed), and Faka-Union Canal (severe channelization) were sampled for temperature, salinity, δ¹⁸O, δ¹³C of dissolved inorganic carbon (DIC), molality of CO₂ (ΣCO₂), and Mg:Ca and Sr:Ca ratios between freshwater and marine water end members over a 17-mo period. Carbon isotope composition followed similar seasonal patterns as salinity. Freshwater and seawater end members are more negative than the global average, likely reflecting equilibration with local carbon sources derived from mangrove leaf litter and groundwater. δ¹³C responds to differences in primary productivity between estuaries. Henderson Creek has higher primary productivity than Blackwater River (probable due to higher sewage input and agricultural runoff) and has more positive δ¹³C and lower ΣCO₂. δ¹⁸O is affected by seasonal input of freshwater from atmospheric precipitation, evaporation, and groundwater. Late summer and fall rains lower the δ¹⁸O of estuarine water, whereas evaporative conditions in the dry season elevate δ¹⁸O to values that can be more positive upstream than those from the Gulf of Mexico (estuarine inversion). Evaporation produces water in the Gulf of Mexico that is >1‰ more positive than the global sea surface average most of the year. The very negative δ¹⁸O values in Blackwater River and Henderson Creek likely reflect atmospheric and groundwater contribution. Mg:Ca and Sr:Ca ratios of Gulf water from all three estuaries are similar to global averages at low latitudes. Freshwater end members among estuaries are different in that Blackwater River has higher ratios, suggesting a groundwater contribution. Dolomitic rocks in the subsurface likely provide a source of Mg ions.     

Food Web Structure of the Alaskan Nearshore Shelf and Estuarine Lagoons of the Beaufort Sea

The eastern Alaska Beaufort Sea coast is characterized by numerous shallow (2–5 m) estuarine lagoons, fed by streams and small rivers that drain northward from the Brooks Range through the arctic coastal plain, and bounded seaward by barrier islands and shoals. Millions of birds from six continents nest and forage during the summer period in this region using the river deltas, lagoons, and shoreline along with several species of anadromous and marine fish. We examined biogeochemical processes linking the benthic community to the overall food web structure of these poorly studied but pristine estuaries, which are largely covered by 1.8 m of ice for 10 months annually. In summer, these lagoons are relatively warm with brackish salinities (5–10°C, S = 10–25) compared to more open coastal waters (0–5°C, S > 27). The stable isotopic composition of organic materials in sediments (i.e., benthic particulate organic matter) and water column suspended particulate organic matter from both streams and lagoons are largely indistinguishable and reflect strong terrestrial contributions, based upon δ¹³C and δ¹⁵N values (−25.6‰ to −27.4‰ and 1.4‰ to 3.3‰, respectively). By comparison, shifts toward more heavy isotope-enriched organic materials reflecting marine influence are observed on the adjacent coastal shelf (−24.8‰ to −25.4‰ and 3.4‰ to 5.3‰, respectively). The isotopic composition of lagoon fauna is consistent with a food web dominated by omnivorous detritovores strongly dependent on microbial processing of terrestrial sources of carbon. Biomagnification of ¹⁵N in benthic organisms indicate that the benthic food web in lagoons support up to four trophic levels, with carnivorous gastropod predators and benthic fishes (δ¹⁵N values up to 14.4‰) at the apex.     

Genetic identification of natural gases from shallow reservoirs in some oil- and gas-bearing basins of China

Natural gases of shallow reservoirs with the carbon isotopic compositions of methane ranging from -50‰ to -60‰ (PDB) were considered as mixed gases of biogenic and thermogenic origins previously and some of them were considered as low-mature (or low temperature thermogenic) gases lately. In this paper natural gases with the carbon isotopic compositions of methane in the above range were identified using the molecular and stable carbon isotopic compositions of methane, ethane and propane. The mixed gases of biogenic and mature thermogenic origins display the characteristics of δ 13 C1 ranging from -50‰to -60‰,δ13C2 ＞ -35‰,Δvalues (δ13C3 -δ13C2) ＜ 5‰ and C1/∑C2 ratios ＜ 40. Immature to low-mature gases display the characteristics of δ 13 C1 ranging from - 50‰ to - 60‰, δ13 C2 ＜- 40‰,Δ values (δ13C3 -δ13C2) ＞7‰, and C1/∑C 2 ratios ＞60.     

Geochemical and stable isotopic evolution of the Guarani Aquifer System in the state of São Paulo, Brazil

The purpose of this report is to explain geochemical and stable isotopes trends in the Brazilian unit of the Guarani Aquifer System (Botucatu and Piramboia aquifers) in S?o Paulo State, Brazil. Trends of dissolved species concentrations and geochemical modeling indicated a significant role of cation exchange and dissolution of carbonates in downgradient evolution of groundwater chemistry. Loss of calcium by the exchange for sodium drives dissolution of carbonates and results in Na–HCO₃ type of groundwater. The cation-exchange front moves downgradient at probably much slower rate compared to the velocity of groundwater flow and at present is located near to the cities of Sert?ozinho and águas de Santa Barbara (wells PZ-34 and PZ-148, respectively) in a shallow confined area, 50–70 km from the recharge zone. Part of the sodium probably enters the Guarani Aquifer System. together with chloride and sulfate from the underlying Piramboia Formation by diffusion related to the dissolution of evaporates like halite and gypsum. High concentrations of fluorine (up to 13.3 mg/L) can be explained by dissolution of mineral fluoride also driven by cation exchange. However, it is unclear if the dissolution takes place directly in the Guarani Aquifer System or in the overlying basaltic Serra Geral Formation. There is depletion in δ ²H and δ ¹⁸O values in groundwater downgradient. Values of δ ¹³C(DIC) are enriched downgradient, indicating dissolution of calcite under closed system conditions. Values of δ ¹³C(DIC) in deep geothermal wells are very high (>–6.0‰) and probably indicate isotopic exchange with carbonates with δ ¹³C about –3.0‰. Future work should be based on evaluation of vertical fluxes and potential for penetration of contamination to the Guarani Aquifer System. Electronic Publication     

Sulphur, carbon and oxygen isotope studies of early Variscan mineralisation and Pb-Sb vein deposits in the Cornubian orefield: implications for the scale of fluid movements during Variscan deformation

The strongly deformed Middle Devonian-Lower Carboniferous metasedimentary-volcanic successions of the Trevone Basin (SW England) contain stratiform and Pb-Sb vein deposits that reveal a wide variation in δ³⁴S and δ¹³C, reflecting mineral deposition during diagenesis, regional metamorphism and basin inversion. Pre-Variscan metasedimentary sulphide (δ³⁴S=−33.7 to −26.7‰) and metabasite sulphide (δ³⁴S=+4.0 to +10.8‰) suggest two accessible source reservoirs for sulphur which were available for Sb-As-(Au) and Pb-Zn-(Ag) mineralisation (δ³⁴S=−3.3 to −15.0‰) during late Variscan semiductile-brittle shear. On the basis of pressure-corrected fluid inclusion temperatures, the calculated composition of fluid sulphur reveals an enrichment in δ³⁴S_H2S in the individual vein parageneses and depletion of the fluid sulphur reservoir during evolution of the vein systems. Carbonates in the same veins are partly contemporaneous with Pb-Sb mineralisation and late tensional deformation; their isotopic composition (δ¹³C=−3.2 and −13.4‰) appears strongly influenced by the host formation. Fluid inclusions in post-tensional quartz show a marked reduction in CO₂, suggesting that episodes of CO₂ degassing in response to punctuated reductions in pressure during uplift and brittle deformation was an important mechanism for vein carbonation. An origin for the Pb-Sb mineralisation involving local remobilisation of sulphur from the mixed metasedimentary-volcanic succession is probably inseparable from processes connected with Variscan metamorphism and deformation. Although the N Cornish Variscan deformation is part of a spatially large-scale event, the isotopic evidence suggests compartmentalisation of sulphur and carbon isotope features and short distances between sources and sinks. Received: 15 August 1998 / Accepted: 8 October 1999     

Can the nitrogen and carbon stable isotopes of the pygmy mussel,Xenostrobus securis, indicate catchment disturbance for estuaries in northern New South Wales, Australia?

The nitrogen and carbon stable isotope ratios (δ¹⁵N and δ¹³C) of the pygmy mussel,Xenostrobus securis, were determined for three estuaries with varying levels of catchment disturbance in northern New South Wales, Australia. The lower Manning River catchment supported the highest human population densities with 3% residential development and some livestock agriculture (41%); the Wallamba River catchment was mostly livestock agriculture (56%) while the Wallingat River catchment was mostly vegetated (79%). Mussels, estuarine particulate organic matter (POM), and livestock and human-derived waste were collected in two stages during the austral summers of 2001–2002 and 2002–2003 for dual carbon-nitrogen stable isotope analysis. The disturbed Manning and Wallamba River catchment mussels were enriched in¹⁵N by an average of 3.2‰ and 1.5‰, respectively, compared to the vegetated Wallingat River mussels. Mussel δ¹³C values ranged from −24.8‰ to −30.3‰ and showed an estuarine gradient becoming enriched with distance downstream within estuaries, but were unable to distinguish patterns in catchment disturbance between estuaries. The δ¹⁵N and δ¹³C values of POM showed a similar pattern to mussels, indicating a direct link between them within each estuary. A multiple regression model of mussel δ¹⁵N using the fractions of land used for livestock agriculture and residential development within 5 km zones from river networks to a distance equivalent to a tidal ellipse from sites explained 67% of the variation in mussel δ¹⁵N with 95% of the differences lying within 1.6‰ of observed values. Increasing fractions of land used for livestock agriculture depleted mussel δ¹⁵N values estimated by the regression equation, indicating the use of cow manure as a nutrient source with a value of 2.0‰. Increasing fractions of land used for residential development enriched estimated mussel δ¹⁵N, indicating the use of human-derived waste with a value of 20.8‰. Pygmy mussels are a useful long-term bio-indicator for the effects of anthropogenic catchment disturbance and nutrient enrichment in estuaries.     

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.     

Petrography and stable isotope geochemistry of the cretaceous El Abra Limestones (Actopan), Mexico: Implication on diagenesis

Petrography and stable isotopes (carbon and oxygen) geochemistry of limestones from the El Abra Formation, Actopan, were studied to identify their digenetic environments. The major petrographic types identified are mudstone, wackestone, grainstone, and boundstone. Most of the studied samples show positive δ¹³C values, except two samples (2 and 28), which are slightly negative values (−0.27‰ and −0.02‰). The organic remains identified in foraminiferal wackestone type can be responsible for the negative δ¹³C values. The δ¹⁸O values range from −12.41‰ to −4.02‰ and indicate meteoric diagenesis.     

The Sarylakh and Sentachan gold-antimony deposits,Sakha-Yakutia: A case of combined mesothermal gold-quartz and epithermal stibnite ores

New mineralogical, thermobarometric, isotopic, and geochemical data provide evidence for long and complex formation history of the Sarylakh and Sentachan Au-Sb deposits conditioned by regional geodynamics and various types of ore mineralization, differing in age and source of ore matter combined in the same ore-localizing structural units. The deposits are situated in the Taryn metallogenic zone of the East Yakutian metallogenic belt in the central Verkhoyansk-Kolyma Fold Region. They are controlled by the regional Adycha-Taryn Fault Zone that separates the Kular-Nera Terrane and the western part of the Verkhoyansk Fold-Thrust Belt. The fault extends along the strike of the northwest-trending linear folds and is deep-rooted and repeatedly reactivated. The orebodies are mineralized crush zones accompanied by sulfidated (up to 100 m wide) quartz-sericite metasomatic rocks and replacing dickite-pyrophyllite alteration near stibnite veinlets. Two stages of low-sulfide gold-quartz and stibnite mineralization are distinguished. The formation conditions of the early milk white quartz in orebodies with stibnite mineralization at the Sarylakh and Sentachan deposits are similar: temperature interval 340–280°C, salt concentration in fluids 6.8–1.6 wt % NaCl equiv, fluid pressure 3430–1050 bar, and sodic bicarbonate fluid composition. The ranges of fluid salinity overlapped at both deposits. In the late regenerated quartz that attends stibnite mineralization, fluid inclusions contain an aqueous solution with salinity of 3.2 wt % NaCl equiv and are homogenized into liquid at 304–189°C. Syngenetic gas inclusions contain nitrogen 0.19 g/cm³ in density. The pressure of 300 bar is estimated at 189°C. The composition of the captured fluid is characterized as K-Ca bicarbonatesulfate. The sulfur isotopic composition has been analyzed in pyrite and arsenopyrite from ore and metasomatic zones, as well as in coarse-, medium-, and fine-grained stibnite varieties subjected to dynamometamorphism. The following δ³⁴S values, ‰ have been established at the Sarylakh deposit: −2.0 to −0.9 in arsenopyrite, −5.5 to −1.1 in pyrite, and −5.5 to −3.6 in stibnite. At the Sentachan deposit: −0.8 to +1.0 in arsenopyrite, +0.5 to +2.6 in pyrite, and −3.9 to +0.6 in stibnite. Sulfides from the Sentachan deposit is somewhat enriched in ³⁴S. The ¹⁸O of milk white quartz at the Sarylakh deposit varies from +14.8 to 17.0‰ and from +16.4 to + 19.3‰ at the Sentachan. The δ¹⁸O of regenerated quartz is +16.5‰ at the Sarylakh and +17.6 to +19.8‰ at the Sentachan. The δ¹⁸O of carbonates varies from +15.0 to 16.3% at the Sarylakh and from +16.7 to +18.2‰ at the Sentachan. The δ¹³C of carbonates ranges from −9.5 to −12.1‰ and −7.8 to −8.5‰, respectively. The calculated $ \delta ^{18} O_{H_2 O} $ \delta ^{18} O_{H_2 O} of the early fluid in equilibrium with quartz and dolomite at 300δC are +7.9 to +10.1‰ for the Sarylakh deposit and +9.5 to +12.4‰ for the Sentachan deposit (+4.9 and 6.0‰ at 200°C for the late fluid, respectively). Most estimates fall into the interval characteristic of magmatic water (°¹⁸O = +5.5 to +9.5‰).     

Mineralogical and stable isotope studies of gold–arsenic mineralisation in the Sams Creek peralkaline porphyritic granite, South Island, New Zealand

At Sams Creek, a gold-bearing, peralkaline granite porphyry dyke, which has a 7 km strike length and is up to 60 m in thickness, intrudes camptonite lamprophyre dykes and lower greenschist facies metapelites and quartzites of the Late Ordovician Wangapeka formation. The lamprophyre dykes occur as thin (< 3 m) slivers along the contacts of the granite dyke. δ¹⁸O_magma values (+5 to +8‰, VSMOW) of the A-type granite suggest derivation from a primitive source, with an insignificant mature crustal contribution. Hydrothermal gold–sulphide mineralisation is confined to the granite and adjacent lamprophyre; metapelite country rocks have only weak hydrothermal alteration. Three stages of hydrothermal alteration have been identified in the granite: Stage I alteration (high fO₂) consisting of magnetite–siderite±biotite; Stage II consisting of thin quartz–pyrite veinlets; and Stage III (low fO₂) consisting of sulphides, quartz and siderite veins, and pervasive silicification. The lamprophyre is altered to an ankerite–chlorite–sericite assemblage. Stage III sulphide veins are composed of arsenopyrite + pyrite ± galena ± sphalerite ± gold ± chalcopyrite ± pyrrhotite ± rutile ± graphite. Three phases of deformation have affected the area, and the mineralised veins and the granite and lamprophyre dykes have been deformed by two phases of folding, the youngest of which is Early Cretaceous. Locally preserved early-formed fluid inclusions are either carbonic, showing two- or three-phases at room temperature (liquid CO₂-CH₄ + liquid H₂O ± CO₂ vapour) or two-phase liquid-rich aqueous inclusions, some of which contain clathrates. Salinities of the aqueous inclusions are in the range of 1.4 to 7.6 wt% NaCl equiv. Final homogenisation temperatures (Th) of the carbonic inclusions indicate minimum trapping temperatures of 320 to 355°C, which are not too different from vein formation temperatures of 340–380°C estimated from quartz–albite stable isotope thermometry. δ¹⁸O values of Stage II and III vein quartz range from +12 and +17‰ and have a bimodal distribution (+14.5 and +16‰) with Stage II vein quartz accounting for the lower values. Siderite in Stage III veins have δ¹⁸O (+12 to +16‰) and δ¹³C values (−5‰, relative to VPDB), unlike those from Wangapeka Formation metasediments (δ¹³C_{bulk carbon} values of −24 to −19‰) and underlying Arthur Marble marine carbonates (δ¹⁸O = +25‰ and δ¹³C = 0‰). Calculated δ¹⁸O_water (+8 to +11‰, at 340°C) and (−5‰) values from vein quartz and siderite are consistent with a magmatic hydrothermal source, but a metamorphic hydrothermal origin cannot be excluded. δ³⁴S values of sulphides range from +5 to +10‰ (relative to CDT) and also have a bimodal distribution (modes at +6 and +9‰, correlated with Stage II and Stage III mineralisation, respectively). The δ³⁴S values of pyrite from the Arthur Marble marine carbonates (range from +3 to +13‰) and Wangapeka Formation (range from −4 to +9.5‰) indicate that they are potential sources of sulphur for sulphides in the Sams Creek veins. Another possible source of the sulphur is the lithospheric mantle which has positive values up to +14‰. Ages of the granite, lamprophyre, alteration/mineralisation, and deformation in the region are not well constrained, which makes it difficult to identify sources of mineralisation with respect to timing. Our mineralogical and stable isotope data does not exclude a metamorphic source, but we consider that the source of the mineralisation can best be explained by a magmatic hydrothermal source. Assuming that the hydrothermal fluids were sourced from crystallisation of the Sams Creek granite or an underlying magma chamber, then the Sams Creek gold deposit appears to be a hybrid between those described as reduced granite Au–Bi deposits and alkaline intrusive-hosted Au–Mo–Cu deposits.     

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.