Stable isotope variations in a coral (Favia speciosa) from the Gulf of Kutch during 1948–1989 A.D.: Environmental implications

The stable isotopic analyses (δ¹⁸O and δ¹³C) of a coralFavia speciosa spanning forty two years (1948–89 A.D.), collected from the Pirotan island (22.6°N, 70°E) in the Gulf of Kutch have been carried out to assess its potential for retrieving past environmental changes in this region. It is seen that the summer (minima) δ¹⁸O variations in the coral CaCO₃ are negatively correlated with seasonal (summer) monsoon rainfall in the adjoining region of Kutch and Saurashtra and a qualitative reconstruction of historical rainfall variations in this region can be obtained by analyzing the δ¹⁸O in this species of coral. The observed mean seasonal range of δ¹⁸O variations is 0.34 ±0.17‰ (n = 42), whereas the expected range calculated (from available SST and measured δ¹⁸O of sea water) is ∼ 1.1 ±0.15‰ The difference is due to the coarse resolution of sampling, which can be corrected. The seasonal range in δ¹³C is ∼ l‰ and is explained by changes in: a) the light intensity related to the cloudiness during monsoons and b) phytoplankton productivity.     

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]     

Recent sedimentary records from the Arabian Sea

An attempt is made to understand the redox conditions that prevailed in the north eastern continental margins of the Arabian Sea and in the nearby deep water regions during the past few centuries using short undisturbed sediment cores. The geochronology is accomplished using²¹⁰Pb excess method and the proxy indicators chosen for productivity and associated redox changes are CaCO₃, organic matter (OM), Mn and U along with major elements Fe and Al. Such changes in principle are related to high productivity in the overlying waters which in turn depend on monsoonal intensity that causes upwelling responsible for increase in productivity. Alongwith the published data on gravity cores from the same region, our measurements suggest the following: At ∼ 300 m water depth, south of 21°N, the sediment-water interface at depths of ∼ 300 m had been anoxic during the time span represented by the presently studied cores for approximately ∼ 700y as evidenced by low Mn/Al (< 0.7 × 10⁻²) and high U/Al (> 10⁻⁴) weight ratios. In some adjacent deeper regions, however, the environment turned oxic around ∼ 200 y BP. Whereas both Mn and Ra were lost to the overlying waters in the anoxic regions (depth ∼340m), the Mn that diffused from deeper sections appears to have mineralized at the sediment-water-interface. Studies of this type on long undisturbed cores from the margins of the Arabian Sea and the Bay of Bengal, involving several proxies and geochronology by more than one method are needed to understand short term environmental (and monsoonal intensity) changes of the recent past with high resolution.     

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.     

Obtaining equilibrium oxygen isotope fractionations from rocks: theory and examples

A generalized approach for retrieving equilibrium isotope fractionations from natural rocks is proposed in which models of prograde reaction histories and retrograde diffusional exchange are used to identify coexisting minerals with similar isotope closure temperatures. Examples using literature data and new analyses from 32 natural amphibolite-facies schists demonstrate both the feasibility and limitations of obtaining equilibrium oxygen isotope fractionations from minerals in natural rocks. By screening samples according to the theoretical models, natural data are shown to have highly consistent mineral fractionations (±2σ reproducibilities of ±0.16 to 0.54‰) that within uncertainty reproduce experimental determinations among the minerals quartz, biotite, muscovite, and calcic amphibole. This correspondence indicates that the proposed theoretically-based selection criteria improve the likelihood of measuring equilibrium fractionations. The new data further corroborate the expected progressive enrichment of δ¹⁸O in the orthosilicates with increasing Al+Si relative to Fe+Mg: Δ(Ky-Grt) ∼1.05‰, Δ(St-Grt) ∼0.6‰, and Δ(St-Cld) ∼0.3‰ at 525–575 °C. In contrast, typical samples that fail to satisfy screening criteria exhibit fractionations involving quartz, biotite, and amphibole that are strongly disequilibrium because of exchange during cooling. Theoretical screening of samples prior to isotope analysis allows robust, independent assessment of theoretical and experimental determinations of equilibrium isotope fractionations. Received: 14 January 1997 / Accepted: 9 March 1998     

Nitrogen isotopic studies in the suboxic Arabian Sea

Measurements of¹⁵N/¹⁴N in dissolved molecular nitrogen (N₂), nitrate (NO ₃ ⁻ ) and nitrous oxide (N₂O) and¹⁸O/¹⁶O in N₂O [expressed as δ¹⁵N and δ¹⁸O, relative to atmospheric N₂ and oxygen (O₂), respectively] have been made in water column at several locations in the Arabian Sea, a region with one of the thickest and most intense O₂ minima observed in the open ocean. Microbially-mediated reduction of NO ₃ ⁻ to N₂ (denitrification) in the oxygen minimum zone (OMZ) appears to greatly affect the natural isotopic abundances. The δ¹⁵N of NO ₃ ⁻ increases from 6‰ in deep waters (2500 m) to 15‰ within the core of the denitrifying layer (250–350 m); the δ¹⁵N of N₂ concurrently decreases from 0.6‰ to 0.20‰ Values of the isotopic fractionation factor (ε) during denitrification estimated using simple advection-reaction and diffusion-reaction models are 22‰ and 25‰, respectively. A strong decrease in δ¹⁵N of NO ₃ ⁻ is observed from ∼ 200m (> 11‰) to 80m (∼ 6‰); this is attributed to the input of isotopically light nitrogen through nitrogen fixation. Isotopic analysis of N₂O reveals extremely large enrichments of both¹⁵N and¹⁸O within the OMZ, presumably due to the preferential reduction of lighter N₂O to N₂. However, isotopically light N₂O is observed to accumulate in high concentrations above the OMZ indicating that the N₂O emitted to the atmosphere from this region cannot be very heavy. The isotope data from the intense upwelling zone off the southwest coast of India, where some of the highest concentrations of N₂O ever found at the sea surface are observed, show moderate depletion of¹⁵N, but slight enrichment of¹⁸O relative to air. These results suggest that the ocean-atmosphere exchange cannot counter inputs of heavier isotopes (particularly¹⁸O) associated with the stratospheric back flux, as proposed by previous workers. This calls for additional sources and/or sinks of N₂O in the atmosphere. Also, the N₂O isotope data cannot be explained by production through either nitrification or denitrification, suggesting a possible coupling between the two processes as an important mechanism of N₂O production.     

Oxygen and hydrogen isotope study of high-pressure metagabbros and metabasalts (Cyclades, Greece): implications for the subduction of oceanic crust

Oxygen and hydrogen stable isotope ratios of eclogite-facies metagabbros and metabasalts from the Cycladic archipelago (Greece) document the scale and timing of fluid–rock interaction in subducted oceanic crust. Close similarities are found between the isotopic compositions of the high-pressure rocks and their ocean-floor equivalents. High-pressure minerals in metagabbros have low δ¹⁸O values: garnet 2.6 to 5.9‰, glaucophane 4.3 to 7.1‰; omphacite 3.5 to 6.2‰. Precursor actinolite that was formed during the hydrothermal alteration of the oceanic crust by seawater analyses at 3.7 to 6.3‰. These compositions are in the range of the δ¹⁸O values of unaltered igneous oceanic crust and high-temperature hydrothermally altered oceanic crust. In contrast, high-pressure metabasalts are characterised by ¹⁸O-enriched isotopic compositions (garnet 9.2 to 11.5‰, glaucophane 10.6 to 12.5‰, omphacite 10.2 to 12.8‰), which are consistent with the precursor basalts having undergone low-temperature alteration by seawater. D/H ratios of glaucophane and actinolite are also consistent with alteration by seawater. Remarkably constant oxygen isotope fractionations, compatible with isotopic equilibrium, are observed among high-pressure minerals, with Δ_{glaucophane−garnet} = 1.37 ± 0.24‰ and Δ_{omphacite−garnet} = 0.72 ± 0.24‰. For the estimated metamorphic temperature of 500 °C, these fractionations yield coefficients in the equation Δ = A * 10⁶/T ² (in Kelvin) of A_{glaucophane−garnet} = 0.87 ± 0.15 and A_{omphacite−garnet} = 0.72 ± 0.24. A fractionation of Δ_{glaucophane–actinolite} = 0.94 ± 0.21‰ is measured in metagabbros, and indicates that isotopic equilibrium was established during the metamorphic reaction in which glaucophane formed at the expense of actinolite. The preservation of the isotopic compositions of gabbroic and basaltic oceanic crust and the equilibrium fractionations among minerals shows that high-pressure metamorphism occurred at low water/rock ratios. The isotopic equilibrium is only observed at hand-specimen scale, at an outcrop scale isotopic compositional differences occur among adjacent rocks. This heterogeneity reflects metre-scale compositional variations that developed during hydrothermal alteration by seawater and were subsequently inherited by the high-pressure metamorphic rocks. Received: 4 January 1999 / Accepted: 7 July 1999     

Evaporation, precipitation, and associated salinity changes at a humid, subtropical estuary

The distilling effect of evaporation and the diluting effect of precipitation on salinity at two estuarine sites in the humid subtropical setting of the Indian River Lagoon, Florida, were evaluated based on daily evaporation computed with an energy-budget method and measured precipitation. Despite the larger magnitude of evaporation (about 1,58 mm yr⁻¹) compared to precipitation (about 1,180 mm yr⁻¹) between February 2002 and January 2004, the variability of monthly precipitation induced salinity changes was more than twice the variability of evaporation induced changes. Use of a constant, mean value of evaporation, along with measured values of daily precipitation, were sufficient to produce simulated salinity changes that contained little monthly (root-mean-square error = 0.33‰ mo⁻¹ and 0.52‰ mo⁻¹ at the two sites) or cumulative error (<1‰ yr⁻¹) compared to simulations that used computed daily values of evaporation. This result indicates that measuring the temporal variability in evaporation may not be critical to simulation of salinity within the lagoon. Comparison of evaporation and precipitation induced salinity changes with measured salinity changes indicates that evaporation and precipitation explained only 4% of the changes in salinity within a flow-through area of the lagoon; surface water and ocean inflows probably accounted for most of the variability in salinity at this site. Evaporation and precipitation induced salinity changes explained 61% of the variability in salinity at a flow-restricted part of the lagoon.     

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.     

Sulfur isotopic composition of sulfides at the Mangazeya silver deposit,Eastern Sakha-Yakutia,Russia

The succession of the formation of ore zones and sulfur isotope ratio of sulfides at the Mangazeya Ag deposit have been studied. The deposit is located in the Nyuektame Fault Zone in the eastern limb of the Endybal Anticline. The ore zones are hosted in the Middle Carboniferous to Middle Jurassic terrigenous sequences of the Verkhoyansk Complex intruded by the Endybal subvolcanic stock and felsic and mafic dikes. Three ore stages are distinguished: (I) gold-rare metal, (II) cassiterite-sulfide, and (III) silver-base-metal. Products of these stages are spatially isolated. The δ³⁴S of sulfides ranges from −6.4 to +8.0‰. In the sulfides of the gold-rare metal assemblage, this value varies from −1.8 to +4.7‰; in the sulfides of the cassiterite-sulfide stage, −6.4 to +6.6‰; and in the sulfides of the silver-base-metal assemblage, -5.6 to +8.0‰. A sulfur isotope thermometer indicates the temperature of mineral deposition at 315–415°C for the first stage and 125–280°C for the third stage. Possible causes of variable sulfur isotopic composition in sulfides are discussed. The data on the sulfur isotope ratio is interpreted in terms of involvement of magmatic fluid (δ³⁴S ∼ 0) in the mineralizing process along with low-temperature fluid taking sulfur from host rocks (δ³⁴S ≫ 0). Boiling and mixing of magmatic fluid with heated meteoric water were important at the last stage of the deposit formation.     

Detrital,metamorphic and metasomatic tourmaline in high-pressure metasediments from Syros (Greece): intra-grain boron isotope patterns determined by secondary-ion mass spectrometry

The boron isotopic composition of zoned tourmaline in two metasediments from the island of Syros, determined by secondary-ion mass spectrometry (SIMS), reflects the sedimentary and metamorphic record of the rocks. Tourmaline from a silicate-bearing marble contains small (≤20 μm) detrital cores with highly variable δ ¹¹B values (−10.7 to +3.6‰), pointing to a heterogeneous protolith derived from multiple sources. The sedimentary B isotopic record survived the entire metamorphic cycle with peak temperatures of ∼500°C. Prograde to peak metamorphic rims are homogeneous and similar among all analysed grains (δ ¹¹B ≈ +0.9‰). The varying δ ¹¹B values of detrital cores in the siliceous marble demonstrate that in situ B isotope analysis of tourmaline by SIMS is a potentially powerful tool for provenance studies not only in sediments but also in metasediments. A meta-tuffitic blueschist bears abundant tourmaline with dravitic cores of detrital or authigenic origin (δ ¹¹B ≈ −3.3‰), and prograde to peak metamorphic overgrowth zones (−1.6‰). Fe-rich rims, formed during influx of B-bearing fluids under retrograde conditions, show strongly increasing δ ¹¹B values (up to +7.7‰) towards the margins of the grains. The δ ¹¹B values of metamorphic tourmaline from Syros, formed in mixed terrigenous–marine sediments, reflect the B signal blended from these two different sources, and was probably not altered by dehydration during subduction.     

Fluid Inclusion Studies of Gold Deposits in the Gezhen Shear Zone,Hainan Province,China

The Tuwaishan, Baoban, Erjia, Bumo and other gold deposits in western Hainan occur in Precambrian metamorphic clastic rocks and are structurally controlled by the Gezhen shear zone. Fluid inclusion studies have been carried out of the gold deposits mentioned above. The homogenization temperatures of the whole fluid inclusion population range from 140°C to 370°C, indicating that gold was precipitated mainly at 240–250°C. The salinities are within the range of 2.0–9.2 wt% NaCl equiv. and the pressure of formation of the deposits was estimated at about 270×10⁵−500×10⁵Pa, corresponding to a depth of about 1.1–2.0 km under lithostatic confinement. Chemical studies show that the ore fluid is of the Na⁺(K⁺)-Ca²⁺-Cl⁻(F⁻) type. Theδ ¹⁸O andδD values of the fluid vary from −2.7‰- +4.4‰ and −50‰–−87‰ Evidence developed from fluid inclusions and geological setting indicates that the ore fluid was a mixture of magmatic and meteoric-hydrothermal waters. Changes in chemical composition andδ ¹⁸O andδD of fluid inclusions from one ore field to another seem to be related with regional tectonism, metamorphism and magmatism.     

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     

Young orogenic gold mineralisation in active collisional mountains, Taiwan

Gold-bearing vein systems in the high mountains of Taiwan are part of the youngest tectonic-hydrothermal system on Earth. Tectonic collision initiated in the Pliocene has stacked Eocene–Miocene marine sedimentary rocks to form steep mountains nearly 4 km high. Thinner portions of the sedimentary pile (∼5 km) are currently producing hydrocarbons in a fold and thrust belt, and orogenic gold occurs in quartz veins in thicker parts of the pile (∼10 km) in the Slate Belt that underlies the mountains. Metamorphic fluids (2–5 wt.% NaCl equivalent) are rising from the active greenschist facies metamorphic zone and transporting gold released during rock recrystallisation. Metamorphic fluid flow at the Pingfengshan historic gold mine was focussed in well-defined (4 km³) fracture zones with networks of quartz veins, whereas large surrounding volumes of rock are largely unveined. Gold and arsenopyrite occur in several superimposed vein generations, with ankeritic alteration of host rocks superimposed on chlorite–calcite alteration zones as fluids cooled and became out of equilibrium with the host rocks. Mineralising fluids had δ¹⁸O near +10‰, δ¹³C was between −1‰ and −6‰ and these fluids were in isotopic equilibrium with host rocks at ∼350°C. Ankeritic veins were emplaced in extensional sites in kink fold axial surfaces, formed as the rock mass was transported laterally from compressional to extensional regimes in the orogen. Rapid exhumation (>2 mm/year) of the Slate Belt is causing a widespread shallow conductive thermal anomaly without igneous intrusions. Meteoric water is penetrating into the conductive thermal anomaly to contribute to crustal fluid flow and generate shallow boiling fluids (∼250°C) with fluid temperature greater than rock temperature. The meteoric-hydrothermal system impinges on, but causes only minor dilution of, the gold mineralisation system at depth.     

10Be meltwater signal in Orca basin sediments,Gulf of Mexico

An increase in the cosmogenic beryllium-10 content of the Orca basin sediments due to the flooding of the Gulf of Mexico (GM) by meltwaters during the late Wisconsin interglacial is reported. A strong negative correlation (γ =-0.99) betweenδ ¹⁸ O (in the range o f-1.5‰ to +0.5‰) and¹⁰Be/Al ratio is seen. During intense flooding reflected by a decrease in δ¹⁸O by ∼ 2‰, this correlation may not hold as some of the sediments with low¹⁰Be/Al ratio and deposited on the shelf and slope regions of the GM during the earlier glacial period would also be washed into the basin. The deposited sediment would then be a mixture with a¹⁰Be/Al ratio lower than expected from the correlation     

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‰).     

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.     

Do we have enough pieces of the jigsaw to integrate CO2 fluxes in the coastal ocean?

Annually integrated air-water CO₂ flux data in 44 coastal environments were compiled from literature. Data were gathered in 8 major ecosystems (inner estuaries, outer estuaries, whole estuarine systems, mangroves, salt marshes, coral reefs, upwelling systems, and open continental shelves), and up-scaled in the first attempt to integrate air-water CO₂ fluxes over the coastal ocean (26×10⁶ km²), taking into account its geographical and ecological diversity. Air-water CO₂ fluxes were then up-scaled in global ocean (362×10⁶ km²) using the present estimates for the coastal ocean and those from Takahashi et al. (2002) for the open ocean (336×10⁶ km²). If estuaries and salt marshes are not taken into consideration in the up-scaling, the coastal ocean behaves as a sink for atmospheric CO₂(−1.17 mol C m⁻² yr⁻¹) and the uptake of atmospheric CO₂ by the global ocean increases by 24% (−1.93 versus −1.56 Pg C yr⁻¹). The inclusion of the coastal ocean increases the estimates of CO₂ uptake by the global ocean by 57% for high latitude areas (−0.44 versus −0.28 Pg C yr⁻¹) and by 15% for temperate latitude areas (−2.36 versus −2.06 Pg C yr⁻¹) At subtropical and tropical latitudes, the contribution from the coastal ocean increases the CO₂ emission to the atmosphere from the global oceam by 13% (0.87 versus 0.77 Pg C yr⁻¹). If estuaries and salt marshes are taken into consideration in the upscaling, the coastal ocean behaves as a source for atmospheric CO₂ (0.38 mol C m⁻² yr⁻¹) and the uptake of atmospheric CO₂ from the global ocean decreases by 12% (−1.44 versus −1.56 Pg C yr⁻¹) At high and subtropical and tropical latitudes, the coastal ocean behaves as a source for atmospheric CO₂ but at temperate latitudes, it still behaves as a moderate CO₂ sink. A rigorous up-scaling of air-water CO₂ fluxes in the coastal ocean is hampered by the poorly constrained estimate of the surface area of inner estuaries. The present estimates clearly indicate the significance of this biogeochemically, highly active region of the biosphere in the global CO₂ cycle.     

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.     

Genesis of the Assif El Mal Zn–Pb (Cu,Ag) vein deposit. An extension-related Mesozoic vein system in the High Atlas of Morocco. Structural,mineralogical, and geochemical evidence

The Assif El Mal Zn–Pb (Cu–Ag) vein system, located in the northern flank of the High Atlas of Marrakech (Morocco), is hosted in a Cambro-Ordovician volcaniclastic and metasedimentary sequence composed of graywacke, siltstone, pelite, and shale interlayered with minor tuff and mudstone. Intrusion of synorogenic to postorogenic Late Hercynian peraluminous granitoids has contact metamorphosed the host rocks giving rise to a metamorphic assemblage of quartz, plagioclase, biotite, muscovite, chlorite, amphibole, chloritoid, and garnet. The Assif El Mal Zn–Pb (Cu–Ag) mineralization forms subvertical veins with ribbon, fault breccia, cockade, comb, and crack and seal textures. Two-phase liquid–vapor fluid inclusions that were trapped during several stages occur in quartz and sphalerite. Primary inclusion fluids exhibit T _h mean values ranging from 104°C to 198°C. Final ice-melting temperatures range from −8.1°C to −12.8°C, corresponding to salinities of ∼15 wt.% NaCl equiv. Halogen data suggest that the salinity of the ore fluids was largely due to evaporation of seawater. Late secondary fluid inclusions have either Ca-rich, saline (26 wt.% NaCl equiv.), or very dilute (3.5 wt.% NaCl equiv.) compositions and homogenization temperatures ranging from 75°C to 150°C. The δ¹⁸O and δD fluid values suggest an isotopically heterogeneous fluid source involving mixing between connate seawater and black-shale-derived organic waters. Low δ¹³C_VPDB values ranging from −7.5‰ to −7.7‰ indicate a homogeneous carbon source, possibly organic matter disseminated in black shale hosting the Zn–Pb (Cu–Ag) veins. The calculated δ³⁴S_H2S values for reduced sulfur (22.5‰ to 24.3‰) are most likely from reduction of SO₄ ²⁻ in trapped seawater sulfate or evaporite in the host rocks. Reduction of sulfate probably occurred through thermochemical sulfate reduction in which organic matter was oxidized to produce CO₂ which ultimately led to precipitation of saddle dolomite with isotopically light carbon. Lead isotope compositions are consistent with fluid–rock interaction that leached metals from the immediate Cambro-Ordovician volcaniclastic and metasedimentary sequence or from the underlying Paleo-Neoproterozoic crustal basement. Geological constraints suggest that the vein system of Assif El Mal formed during the Jurassic opening of the central Atlantic Ocean.