Isotope parameters (δD, δ<Superscript>18</Superscript>O) and sources of freshwater input to Kara Sea

The isotope characteristics (δD, δ¹⁸О) of Kara Sea water were studied for quantitative estimation of freshwater runoff at stations located along transect from Yamal Peninsula to Blagopoluchiya Bay (Novaya Zemlya). Freshwater samples were studied for glaciers (Rose, Serp i Molot) and for Yenisei and Ob estuaries. As a whole, δD and δ¹⁸O are higher in glaciers than in river waters. isotope composition of estuarial water from Ob River is δD =–131.4 and δ18O =–17.6‰. Estuarial waters of Yenisei River are characterized by compositions close to those of Ob River (–134.4 and–17.7‰), as well as by isotopically “heavier” compositions (–120.7 and–15.8‰). Waters from studied section of Kara Sea can be product of mixing of freshwater (δD =–119.4, δ¹⁸O =–15.5) and seawater (S = 34.9, δD = +1.56, δ¹⁸O = +0.25) with a composition close to that of Barents Sea water. isotope parameters of water vary significantly with salinity in surface layer, and Kara Sea waters are desalinated along entire studied transect due to river runoff. concentration of freshwater is 5–10% in main part of water column, and <5% at a depth of >100 m. maximum contribution of freshwater (>65%) was recorded in surface layer of central part of sea.     

Carbon cycle and sea-water palaeotemperature evolution at the Middle–Late Jurassic transition,eastern Paris Basin (France)

A very high-resolution carbon and oxygen stable isotope analysis (bulk-carbonate) of a biostratigraphically well-constrained Callovian–Oxfordian series is provided here for the first time. The homogeneity of the clayey series and the weak diagenetic alteration allow the isotopic signal variations to be considered as primary in origin. A prominent and brief negative excursion in the δ¹³C curve (−2‰), occurring at the start of the Middle Callovian (Jason Zone – Obductum Subzone) and correlated regionally, suggests a possible methane release. The increasing δ¹³C values thereafter up to the Early Oxfordian, concomitant with a warming episode, highlight the burial of carbon in organic-rich layers which, in return, may have triggered a decrease in atmospheric pCO₂. At higher frequencies, observed fluctuations of the δ¹³C and δ¹⁸O values are orbitally driven (405-kyr and 100-kyr eccentricity cycles) and may correspond to the salinity and temperature variability recorded in sea water. The δ¹⁸O isotopic measurements from well-preserved diagenetically screened belemnites and bivalves along the series, compared to available data from Tethyan domains, agree with the scenario of a global cooling at the Middle-Late Jurassic transition. The well-dated δ¹⁸O isotopic curve suggests that the onset of this cooling event occurred at the end of the Coronatum Zone (Middle Callovian).     

Saddle dolomite and calcite cements as records of fluid flow during basin evolution: Paleogene carbonates,United Arab Emirates

Field observations indicate that tectonic compression, anticline formation and concomitant uplift events of marine Paleogene carbonates in eastern United Arab Emirates, which are related to the Zagros Orogeny, have induced brecciation, karstification, and carbonate cementation in vugs and along faults and fractures. Structural analysis, stable isotopes and fluid inclusion microthermometry are used to constrain the origin and geochemical evolution of the fluids. Fluid flow was related to two tectonic deformation phases. Initially, the flux of moderately ⁸⁷Sr-rich basinal NaCl–MgCl₂–H₂O brines along reactivated deep-seated strike-slip faults have resulted in the precipitation of saddle dolomite in fractures and vugs and in dolomitization of host Eocene limestones (δ¹⁸O_V-PDB −15.8‰ to −6.2‰; homogenization temperatures of 80–115 °C and salinity of 18–25 wt.% eq. NaCl). Subsequently, compression and uplift of the anticline was associated with incursion of meteoric waters and mixing with the basinal brines, which resulted in the precipitation of blocky calcite cement (δ¹⁸O_V-PDB −22‰ to −12‰; homogenization temperatures of 60–90 °C and salinity of 4.5–9 wt.% eq. NaCl). Saddle dolomite and surrounding blocky calcite have precipitated along the pre- and syn-folding E–W fracture system and its conjugate fracture sets. The stable isotopes coupled with fluid-inclusion micro-thermometry (homogenization temperatures of ≤50 °C and salinity of <1.5 wt.% eq. NaCl) of later prismatic/dogtooth and fibrous calcites, which occurred primarily along the post-folding NNE–SSW fracture system and its conjugate fracture sets, suggest cementation by descending moderately ⁸⁷Sr-rich, cool meteoric waters. This carbonate cementation history explains the presence of two correlation trends between the δ¹⁸O_V-PDB and δ¹³C_V-PDB values: (i) a negative temperature-dependent oxygen isotope fractionation trend related to burial diagenesis and to the flux of basinal brines, and (ii) positive brine-meteoric mixing trend. This integrated study approach allows better understanding of changes in fluid composition and circulation pattern during evolution of foreland basins.     

Characterising the intermediate depth waters of the Pacific Ocean using δ13C and other geochemical tracers

Evidence from geochemical tracers (salinity, oxygen, silicate, nutrients, alkalinity, dissolved inorganic carbon (DIC), carbon isotopes (δ¹³C_DIC) and radiocarbon (Δ¹⁴C)) collected during the Pacific Ocean World Ocean Circulation Experiment (WOCE) voyages (P10, P15, P17 and P19) indicate there are three main water types at intermediate depths in the Pacific Ocean; North Pacific Intermediate Water (NPIW), Antarctic Intermediate Water (AAIW) and Equatorial Pacific Intermediate Waters (EqPIW). We support previous suggestions of EqPIW as a separate equatorial intermediate depth water as it displays a distinct geochemical signature characterised by low salinity, low oxygen, high nutrients and low Δ¹⁴C (older radiocarbon). Using the geochemical properties of the different intermediate depth waters, we have mapped out their distribution in the main Pacific Basin.From the calculated pre-formed δ¹³C_air–sea conservative tracer, it is evident that EqPIW is a combination of AAIW parental waters, while quasi-conservative geochemical tracers, such as radiocarbon, also indicate mixing with old upwelling Pacific Deep Waters (PDW). The EqPIW also displays a latitudinal asymmetry in non-conservative geochemical tracers and can be further split into North (NEqPIW) and South (SEqPIW) separated at ～2°N. The reason for this asymmetry is caused by higher surface diatom production in the north driven by higher silicate concentrations.The δ¹³C signature measured in benthic foraminifera, Cibicidoides spp. (δ¹³C_Cib), from four core tops bathed in AAIW, SEqPIW and NPIW, reflects that of the overlying intermediate depth waters. The δ¹³C_Cib from these cores show similarities and variations down-core that highlight changes in mixing over the last 30,000 yr BP. The reduced offset between the δ¹³C_Cib of AAIW and SEqPIW during the last glacial indicates that AAIW might have had an increased influence in the eastern equatorial Pacific (EEP) region at this time. Additional intermediate depth cores and other paleo-geochemical proxies such as Cd/Ca and radiocarbon are required from the broader Pacific Ocean to further understand changes in intermediate depth water formation, circulation and mixing over glacial/interglacial cycles.     

The impact of organic fluids on the carbon isotopic compositions of carbonate-rich reservoirs: Case study of the Lucaogou Formation in the Jimusaer Sag,Junggar Basin,NW China

The processes involved in the interaction between organic fluids and carbonates, and the resulting effect on reservoir quality during the evolution and maturation of organic matter remain unclear despite the fact that these processes influence the carbon and oxygen isotopic compositions of carbonates. Here, we provide new insights into these processes using data obtained from a detailed analysis of a mixed dolomitic–clastic and organic-rich sedimentary sequence within the middle Permian Lucaogou Formation in the Junggar Basin of NW China. The techniques used during this study include drillcore observations, thin section petrography, scanning electron microscopy (SEM) and electron probe microanalysis, and carbon and oxygen isotope analyses. Oil grades and total organic carbon (TOC) contents represent the amount of oil charging and the abundance of organic fluids within a reservoir, respectively, and both negatively correlate with the whole-rock δ¹³C and δ¹⁸O of the carbonates in the study area, indicating that organic fluids have affected the reservoir rocks. Secondary carbonates, including sparry calcite and dolomite overgrowths and cements, are common within the Lucaogou Formation. Well-developed sparry calcite is present within dark mudstone whereas the other two forms of secondary carbonates are present within the dolomite-rich reservoir rocks in this formation. Comparing thin section petrology with δ¹³C compositions suggests that the carbon isotopic composition of matrix carbonates varies little over small distances within a given horizon but varies significantly with stratigraphic height as a result of the development of secondary carbonates. The net change in whole-rock δ¹³C as a result of these secondary carbonates ranges from 1.8‰ to 4.6‰, with the secondary carbonates having calculated δ¹³C compositions from −18.6‰ to −8.5‰ that are indicative of an organic origin. The positive correlation between the concentration of Fe within matrix and secondary carbonates within one of the samples suggests that the diagenetic system within the Lucaogou Formation was relatively closed. The correlation between δ¹³C and δ¹⁸O in carbonates is commonly thought to be strengthened by the influence of meteoric water as well as organic fluids. However, good initial correlation between δ¹³C and δ¹⁸O of whole rock carbonates within the Lucaogou Formation (resulted from the evaporitic sedimentary environment) was reduced by organic fluids to some extent. Consequently, the δ¹³C–δ¹⁸O covariations within these sediments are not always reliable indicators of diagenetic alteration by organic fluids or meteoric water.The characteristics and δ¹³C compositions of the sparry calcite within the formation is indicative of a genetic relationship with organic acids as a result of the addition of organic CO₂ to the reservoir. Further analysis suggests that both carbonate and feldspar were dissolved by interaction with organic CO₂. However, dissolved carbonate reprecipitated as secondary carbonates, meaning that the interaction between organic fluids and dolomites did not directly improve reservoir quality, although this process did enhance the dissolution of feldspar and increase porosity. This indicates that the δ¹³C and δ¹⁸O of secondary carbonates and their influence on whole-rock carbonate isotopic values can be used to geochemically identify the effect of organic fluids on closed carbonate-rich reservoir systems.     

Isotopic tracers for water masses in the coastal region of eastern Hokkaido

In this study we used two stable isotopes, δ¹³C and δ¹⁸O, for water mass classification in the coastal region off eastern Hokkaido. δ¹³C* values, which were corrected for the biological effect, and δ ¹⁸O values up to 300 m depth suggested that the isotopic character of the onshore and offshore water in the southern Okhotsk Sea, the Nemuro Strait and the western North Pacific could be explained by the mixing of three source waters: the Oyashio water (OYW), Soya Warm Current water (SWCW) and East Sakhalin Current water (ESCW). In summer, δ ¹³C*-δ ¹⁸O plots indicated mixing between SWCW from the southern Okhotsk Sea and OYW in the Pacific coast of southeastern Hokkaido, while temperature-salinity plots of the onshore water showed minimal difference from the offshore OYW. In winter, on the other hand, the mixed water of ESCW and OYW (or SWCW) appeared in the Pacific coastal region, distributed as cold, low salinity onshore water. Finally, we estimated mixing ratios of OYW, SWCW and ESCW in the coastal region of western North Pacific using their mean values of δ ¹³C* and δ ¹⁸O as endmembers. These results suggest seasonal and yearly changes of water mass combination en route from the southern Okhotsk Sea to the western North Pacific.     

Sequentially sampled gas hydrate water,coupled with pore water and bottom water isotopic and ionic signatures at the Kukuy mud volcano,Lake Baikal: ambiguous deep-rooted source of hydrate-forming water

The isotopic and ionic composition of pure gas hydrate (GH) water was examined for GHs recovered in three gravity cores (165–193 cm length) from the Kukuy K-9 mud volcano (MV) in Lake Baikal. A massive GH sample from core St6GC4 (143–165 cm core depth interval) was dissociated progressively over 6 h in a closed glass chamber, and 11 sequentially collected fractions of dissociated GH water analyzed. Their hydrogen and oxygen isotopic compositions, and the concentrations of Cl^– and HCO₃ ^– remained essentially constant over time, except that the fraction collected during the first 50 minutes deviated partly from this pattern. Fraction #1 had a substantially higher Cl^– concentration, similar to that of pore water sampled immediately above (135–142 cm core depth) the main GH-bearing interval in that core. Like the subsequent fractions, however, the HCO₃ ^– concentration was markedly lower than that of pore water. For the GH water fractions #2 to #11, an essentially constant HCO₃ ^–/Cl^– ratio of 305 differed markedly from downcore pore water HCO₃ ^–/Cl^– ratios of 63–99. Evidently, contamination of the extracted GH water by ambient pore water probably adhered to the massive GH sample was satisfactorily restricted to the initial phase of GH dissociation. The hydrogen and oxygen isotopic composition of hydrate-forming water was estimated using the measured isotopic composition of extracted GH water combined with known isotopic fractionation factors between GH and GH-forming water. Estimated δD of ?126 to ?133‰ and δ¹⁸O of ?15.7 to ?16.7‰ differed partly from the corresponding signatures of ambient pore water (δD of ?123‰, δ¹⁸O of ?15.6‰) and of lake bottom water (δD of ?121‰, δ¹⁸O of ?15.8‰) at the St6GC4 coring site, suggesting that the GH was not formed from those waters. Observations of breccias in that core point to a possible deep-rooted water source, consistent with published thermal measurements for the neighboring Kukuy K-2 MV. By contrast, the pore waters of core St6GC4 and also of the neighboring cores GC2 and GC3 from the Kukuy K-9 MV show neither isotopic nor ionic evidence of such a source (e.g., elevated sulfate concentration). These findings constrain GH formation to earlier times, but a deep-rooted source of hydrate-forming water remains ambiguous. A possible long-term dampening of key deep-water source signatures deserves further attention, notably in terms of diffusion and/or advection, as well as anaerobic oxidation of methane.     

Hydrochemistry of the Tumen River Estuary,Sea of Japan

The hydrological and hydrochemical parameters of the Tumen River estuary were collected at 13 stations in May and October 2015. Vertical temperature, conductivity, dissolved oxygen, chlorophyll fluorescence, and turbidity profiles were obtained. Water was sampled from the surface and bottom layer. The water samples were analyzed for major ions, pH, salinity, concentrations of dissolved oxygen, major nutrients, dissolved organic carbon, humic matter, and δ¹⁸О and δD isotopes. This estuary is attributed to microtidal type with a flushing time of about 10 h. A phytoplakton bloom occurred in the top layer of the estuary. For surface horizons, the hydrochemical parameters show a linear correlation with salinity. In the bottom horizons, all these parameters, except for major ions and δ¹⁸О and δD isotopes, reveal substantial nonconservative behavior. The nonconservative behavior of the hydrochemical parameters in the bottom waters was mainly caused by degradation of the phytoplankton biomass at the water/sediment interface. Hypoxic conditions were established in the bottom waters of the estuary in May.     

Oxygen and carbon stable isotope tracers of Weddell Sea water masses: new data and some paleoceanographic implications

Stable oxygen isotopic composition of sea water and stable carbon isotopes of dissolved inorganic carbon (DIC) on the continental shelf in the southern Weddell Sea are presented. Using the stations sampled during the summer 1995 two sections can be constructed, one closely parallel to the ice shelf edge and the other perpendicular to the upper continental slope. Generally, δ¹⁸O values clearly separate between different shelf water masses depending on the content of meteoric meltwater added during melting of glacial ice. Extrapolation of the mixing line between the cores of High Salinity Shelf Water (HSSW) and supercooled Ice Shelf Water (ISW) reveals δ¹⁸O values of the glacial ice of −27‰, whereas extrapolation of the mixing line between the δ¹⁸O values of the most-saline HSSW and lowest temperature ISW results in δ¹⁸O values of −34‰ for glacial ice. These values point to an origin of meltwater from below the ice shelf, where ice is less depleted in ¹⁸O, since deep beneath the ice shelf close to the grounding line, values may reach −40‰. If values between −34 and −27‰ are used as δ¹⁸O end member values for glacial ice, the amount of meltwater from the ice shelf that adds to the formation of ISW off the Filchner–Ronne Ice Shelf ranges from 0.2 to 0.8%, in agreement with previous studies based on δ¹⁸O and ⁴He. Carbon isotopic fractionation due to gas exchange between the atmosphere and the ocean at cold temperatures results in Δδ¹³C_DIC values of 0.20±0.17‰ for Weddell Sea Deep Water, the water mass that ventilates the global abyssal ocean, typically defined as Antarctic Bottom Water (AABW). This confirms the low end of the range estimated previously (0.2–0.4‰), and thus corroborates the dominance of biology in shaping the deep and bottom water δ¹³C signal. It has been hypothesized that different modes of glacial/interglacial Antarctic bottom water formation may be separated by different stable isotopic compositions of deep-sea foraminiferal calcite. Here I show that differences between Δδ¹³C and δ¹⁸O values of HSSW and ISW, both of which contribute to bottom water formation today, are too small to be resolved in deep and bottom water masses. Therefore, glacial/interglacial changes in relative proportions of these water masses in Antarctic deep and bottom water cannot be separated by stable isotopes of fossil benthic foraminiferal calcite.     

Food-web structure and trophodynamics of mesopelagic–suprabenthic bathyal macrofauna of the Algerian Basin based on stable isotopes of carbon and nitrogen

The trophodynamics of mesopelagic (macrozooplankton/micronekton) and benthic boundary layer (suprabenthos=hyperbenthos) faunas from the Algerian Basin were characterized on a seasonal scale through stable carbon and nitrogen isotopic analyses of a total of 34 species and two broad taxa (Copepoda and Cumacea). This is the first study simultaneously focused on trophodynamics of deep-sea zooplankton and suprabenthos. Samples were collected southeast of Mallorca (Algerian Basin, Western Mediterranean), on the continental slope close to Cabrera Archipelago, at 650–780 m depths, ca. bi-monthly between August 2003 and June 2004. Mean δ¹³C values of suprabenthos ranged from ?21.1‰ (Munnopsurus atlanticus) to ?16.7‰ (Cyclaspis longicaudata). Values of δ¹⁵N ranged from 2.8‰ (Lepechinella manco) to 9.9‰ (larvae of Gnathia sp.). The stable isotope ratios of suprabenthic fauna displayed a continuum of values, confirming a wide spectrum of feeding guilds (from filter feeders/surface deposit feeders to predators). According to the available information on diets for suprabenthic species, the highest annual mean δ¹⁵N values were found for the hematophagous isopod Gnathia sp. parasite on fish (represented by Praniza larvae) and carnivorous amphipods (e.g. Rhachotropis spp., Nicippe tumida) consuming copepods, and the lowest δ¹⁵N values were found for two cumaceans (Cyclaspis longicaudata and Platysympus typicus) feeding on detritus. Assuming a ¹⁵N-enrichment factor of 2.5‰ and deposit feeders as baseline, we found three trophic levels in suprabenthic food webs. δ¹³C ranges were particularly wide among deposit feeders (ranging from ?21.8% to ?17.3‰) and omnivores (from ?20.5% to ?18.8‰), suggesting exploitation of particulate organic matter (POM) of different characteristics. Our isotopic analyses revealed lower ranges of δ¹³C and δ¹⁵N for macrozooplankton/micronekton, compared with suprabenthos. δ¹³C values of zooplankton taxa ranged from ?21.1‰ (the hyperiid Phrosina semilunata) to ?19.9‰ (the decapod Pasiphaea multidentata), while δ¹⁵N values ranged from 3.9‰ (P. semilunata) to 7.5‰ (P. multidentata). Among zooplankton, more enriched δ¹⁵N values were found among carnivores (e.g. the fish Cyclothone spp. and Pasiphaea multidentata) preying on copepods, hyperiids, euphausiids and small fish. The lowest δ¹⁵N values were found for hyperiids that feed on the mucus nets of salps (e.g. Vibilia armata). After contrasting isotope analysis with dietary data, we conclude there were two trophic levels among zooplankton/micronekton. Strong correlation between the mean annual δ¹⁵N and δ¹³C values was found for zooplankton (R²=0.7), but not for suprabenthos, which suggests a single source of carbon for plankton. We found a general seasonal trend for δ¹³C enrichment from late autumn (November) to late winter–spring (February–April) for both suprabenthos and zooplankton. The δ¹³C enrichment in February–April was correlated in zooplankton with higher surface chlorophyll a concentration 1 month before sampling. As evidenced by δ¹³C–δ¹⁵N correlations, the response of zooplankton to the peak of surface primary production was almost immediate (an increase of δ¹³C–δ¹⁵N correlations in February), and stronger than for suprabenthos. The response among suprabenthos was weak, with slight increase in δ¹³C–δ¹⁵N relationships in April–June.     

Fluid sources and stable isotope signatures in authigenic carbonates from the Northern Apennines,Italy

Authigenic carbonates are frequently associated with methane cold-seep systems, which extensively occur in various geologic settings worldwide. Of interest is the relation between the fluids involved in their formation and the isotopic signals recorded in the carbonate cements. Along the Northern Apennines foothills (Italy), hydrocarbons and connate waters still seeping nowadays are believed to be the primary sources for the formation of fossil authigenic carbonate found in Plio-Pleistocene marine sediments. Four selected outcrops of dolomitic authigenic carbonates were analysed to compare signature of seeping fluids with fractionation of stable carbon and oxygen isotopes recorded in the carbonate.Along the foothills, deep methane-rich fluids spontaneously rise to the surface through mud volcanoes or are exploited in wells drilled nearby to the fossil Plio-Pleistocene authigenic carbonates. The plumbing system providing fluids to present-day cold seeps was structurally achieved in Late Miocene and Plio-Pleistocene. δ¹³C values of methane, which vary from −51.9 to −43.0‰ VPDB, indicate that gas composition from the deep hydrocarbon reservoirs is relatively uniform along the foothills. On the contrary, δ¹³C in fossil authigenic carbonates strongly varies among different areas and also within the same outcrop.The different carbon sources that fed the investigated carbonates were identified and include: thermogenic methane from the deep Miocene reservoirs, ¹³C-enriched CO₂ derived from secondary methanogenesis and microbial methane from Pliocene successions buried in the Po Plain. The δ¹³C variability documented among samples from a single outcrop testifies that the authigenic carbonates might represent a record of varying biogeochemical processes in the hydrocarbon reservoirs. The sources of stable oxygen isotopes in authigenic carbonates are often ascribed to marine water. Oxygen isotopic fractionation in the dolomite cements indicates that marine pore water couldn't be the sole source of oxygen. δ¹⁸O values provide a preliminary evidence that connate waters had a role in the carbonates precipitation. The concomitant occurrence of active cold seepages and fossil record of former plumbing systems suggests that generation and migration of hydrocarbons are long-lasting and very effective processes along the Northern Apennines foothills.     

Abrupt changes of intermediate-water oxygen in the northwestern Pacific during the last 27 kyr

An oxygen minimum zone (OMZ) currently exists at intermediate water depths on the northern Japanese margin in the northwestern Pacific. The OMZ results largely from a combination of high surface–water productivity and poor ventilation of intermediate waters. We investigated the late Quaternary history (last 27 kyr) of the intensity of this OMZ using changes in benthic foraminiferal carbon isotopes and assemblages in a sediment core taken on the continental slope off Shimokita Peninsula, northern Japan, at a water depth of 975 m. The core was located well within the region of the present-day OMZ and high surface–water productivity. The benthic foraminiferal δ¹³C values, which indicate millennial-scale fluctuations of nutrient contents at the sediment–water interface, were 0.48‰ lower during the last glacial maximum (LGM) than during the late Holocene. These results do not indicate the formation of glacial intermediate waters of subarctic Pacific origin, but rather the large contribution of high-nutrient water masses such as the Antarctic Intermediate Water, implying that the regional circulation pattern during the LGM was similar to that of modern times. Benthic foraminiferal assemblages underwent major changes in response to changes in dissolved oxygen concentrations in ocean floor sediments. The lowest oxygen and highest nutrient conditions, marked by dysoxic taxa and negative values of benthic foraminiferal δ¹³C, occurred during the Bølling/Allerød (B/A) and Pre-Boreal warming events. Dysoxic conditions in this region during these intervals were possibly caused by high surface–water productivity at times of reduced intermediate–water ventilation in the northwestern Pacific. The benthic assemblages show dysoxic events on approx. 100- to 200-year cycles during the B/A, reflecting centennial-scale productivity changes related to freshwater cycles and surface–water circulation in the North Pacific.     

Isotopic composition of gas hydrates in subsurface sediments from offshore Sakhalin Island, Sea of Okhotsk

Hydrate-bearing sediment cores were retrieved from recently discovered seepage sites located offshore Sakhalin Island in the Sea of Okhotsk. We obtained samples of natural gas hydrates and dissolved gas in pore water using a headspace gas method for determining their molecular and isotopic compositions. Molecular composition ratios C₁/_C2+ from all the seepage sites were in the range of 1,500–50,000, while δ¹³C and δD values of methane ranged from ?66.0 to ?63.2‰ VPDB and ?204.6 to ?196.7‰ VSMOW, respectively. These results indicate that the methane was produced by microbial reduction of CO₂. δ¹³C values of ethane and propane (i.e., ?40.8 to ?27.4‰ VPDB and ?41.3 to ?30.6‰ VPDB, respectively) showed that small amounts of thermogenic gas were mixed with microbial methane. We also analyzed the isotopic difference between hydrate-bound and dissolved gases, and discovered that the magnitude by which the δD hydrate gas was smaller than that of dissolved gas was in the range 4.3–16.6‰, while there were no differences in δ¹³C values. Based on isotopic fractionation of guest gas during the formation of gas hydrate, we conclude that the current gas in the pore water is the source of the gas hydrate at the VNIIOkeangeologia and Giselle Flare sites, but not the source of the gas hydrate at the Hieroglyph and KOPRI sites.     

Stable isotopes in deep-sea living (stained) foraminifera from the Mozambique Channel (eastern Africa): multispecies signatures and paleoenvironmental application

Oxygen and carbon isotopes (δ¹⁸O and δ¹³C) have been investigated in carbonate tests of deep-sea foraminifera living in the Mozambique Channel (eastern Africa) to understand how environmental constraints (e.g., organic matter, oxygenation) control the intra- and interspecific variability of isotopic signatures. 197 living individuals, including eight different species, from various microhabitats within the sediment were sorted from sediment samples gathered at two stations on the Malagasy upper slope. Results show that the δ¹⁸O values of foraminiferal taxa were not controlled by microhabitat pattern. They presented tremendous and intriguing intraspecific variability that is not explained by the classical ontogenetic effect. The δ¹³C values of infaunal foraminiferal taxa do not show a 1:1 relationship with the bottom water δ¹³C DIC and do not present a constant offset from it; instead, they appear to be mainly controlled by a microhabitat effect. The lower δ¹³C values of shallow, intermediate, and deep infaunal taxa at the deeper station compared to those seen at the shallower station reflect the enhanced exportation of sedimentary organic matter at the sediment–water interface, and its related mineralization within the upper sediments. The ?δ¹³C between shallow/very shallow infaunal species (i.e., Hoeglundina elegans, Uvigerina hispida) and intermediate/deep infaunal species (i.e., Melonis barleeanus, Globobulimina barbata) permits insight into (1) the exportation of organic matter to the seafloor and (2) the various degradation pathways for organic detritus in the benthic environments off NW Madagascar.     

Assessing waterbird habitat use in coastal evaporative systems using stable isotopes (δC, δN and δD) as environmental tracers

Isotopic patterns of biota across salinity gradients in man-made evaporative systems could assist in determining the use of these habitats by animals. Here we report δ¹³C, δ¹⁵N and δD measurements of a euryhaline fish, the Mediterranean toothcarp (Aphanius fasciatus), inhabiting a range of salinities in the Thyna saltworks near Sfax (Tunisia). The contribution of these salinity niches to egg formation of two typically piscivorous bird species breeding in the area and feeding within saltworks, Little Tern (Sternula albifrons) and Little Egret (Egretta garzetta), was inferred trough a triple-isotope (δ¹³C, δ¹⁵N and δD) Bayesian mixing model. Isotopic trends for fish δ¹⁵N and δD across the salinity gradient followed the equations: δ¹⁵N = e^{(1.1 + 47.68/Salinity)} and δD = −175.74 + Salinity + Salinity²; whereas fish δ¹³C increased as salinity rose (δ¹³C = −10.83 + 0.02·Salinity), after a sudden drop in fish isotopic values for salinities >60 (Practical Salinity Scale) (average fish δ¹³C for salinities <60 = −5.92‰). Both bird species fed largely on low hypersalinity ponds (salinity = 43; average contribution = 37% and 22% for Little Egrets and Little Terns, respectively), although the use of intermediate hypersalinities (salinities 63 and 70) by Little Terns also occurred (16% and 21%, respectively). Isotopic patterns across salinity gradients allow the use of isotopic measurements to inform studies of habitat occupancy within evaporative systems and provide further insights into how wildlife communities interact with them.     

Mineral-forming and diagenetic processes related to Tertiary hydrocarbon seepage at the Bohemian Massif/Outer Western Carpathians interface: Evidence from the Hrabůvka quarry,Moravia, Czech Republic

Ancient hydrocarbon seepage occurred in the Hrabůvka quarry at the boundary between the basement of the Bohemian Massif (represented by folded Lower Carboniferous siliciclastics of the Culm facies) and Tertiary sedimentary cover of the Carpathian Foredeep (formed by Lower Badenian siliciclastics and calcareous clays). The unconsolidated Lower Badenian sediments contain lithified domains composed of limestone and breccias with limestone cement, whereas the basement rocks are cut by subvertical neptunic dykes filled up by limestone and calcite-marcasite-pyrite veinlets representing sealed fluid conduits. The deeply negative δ¹³C values of both vein calcite and limestone (down to −38.1‰ V-PDB) indicate that oxidation of hydrocarbons was the major source of carbon for authigenic mineralization. A fluid inclusion study suggests low fluid temperatures (<50 °C) and low and variable salinities of aqueous fluids associated with hydrocarbons (0.7–6.7 wt. % NaCl eq.). The variability of δ¹⁸O values of authigenic carbonates (−1.7 to −8.2‰ V-PDB) could reflect either slight changes in temperature of escaping fluids (mostly within 15 °C), and/or some mixing with meteoric waters. The low δ³⁴S values of vein marcasite (∼–20‰ V-CDT) are consistent with bacterial reduction of sulfate in the hydrothermal system. Low C₁/(C₂+C₃) ratios in hydrocarbon gas extracted from authigenic carbonates (9.9 and 5.8) as well as the high δ¹³C values of methane (−31.8 and −32.4‰ V-PDB) are compatible with a thermogenic source of hydrocarbons. REE data indicate sequestration of REE from finely dispersed detrital material in the apical part of the hydrothermal system. The available data are compatible with two possible scenarios of fluid origin. The hydrocarbons could have been leached from underlying Paleozoic sedimentary sequence by aqueous fluids that infiltrated into the basement after Tertiary tectonic reactivation. Alternatively, an external source of hydrocarbon-bearing fluids can be found in the adjacent Outer Western Carpathians flysch nappes containing petroleum-producing lithologies. Nevertheless, a regional flow of hydrocarbon-bearing fluids is evidenced by the occurrence of very similar hydrocarbon-bearing vein mineralizations in a wider area.     

An isotopic perspective on the correlation of surface ocean carbon dynamics and sea ice melting in Prydz Bay (Antarctica) during austral summer

The stable carbon isotope composition of particulate organic carbon (δ¹³C_POC) and naturally occurring long-lived radionuclide ²²⁶Ra (T_1/2=1600 a) were applied to study the variations of upper ocean (<100 m) carbon dynamics in response to sea ice melting in Prydz Bay, East Antarctica during austral summer 2006. Surface δ¹³C_POC values ranged from −27.4‰ to −19.0‰ and generally decreased from inner bay (south of 67°S) toward the Antarctic Divergence. Surface water ²²⁶Ra activity concentration ranged from 0.92 to 2.09 Bq/m³ (average 1.65±0.32 Bq/m³, n=20) and increased toward the Antarctic Divergence, probably reflecting the influence of ²²⁶Ra-depleted meltwater and upwelled ²²⁶Ra-replete deep water. The fraction of meltwater, f_i, was estimated from ²²⁶Ra activity concentration and salinity using a three-component (along with Antarctic Summer Surface Water, and Prydz Bay Deep Water) mixing model. Although the fraction of meltwater is relatively minor (1.6–11.9%, average 4.1±2.7%, n=20) for the surface waters (sampled at ~6 m), a positive correlation between surface δ¹³C_POC and f_i (δ¹³C_POC=0.94×f_i−28.44, n=20, r²=0.66, p<0.0001) was found, implying that sea ice melting may have contributed to elevated δ¹³C_POC values in the inner Prydz Bay compared to the open oceanic waters. This is the first time for a relationship between δ¹³C_POC and meltwater fraction to be reported in polar oceans to our knowledge. We propose that sea ice melting may have affected surface ocean δ¹³C_POC by enhancing water column stability and providing a more favorable light environment for phytoplankton photosynthesis, resulting in drawdown of seawater CO₂ availability, likely reducing the magnitude of isotope fractionation during biological carbon fixation. Our results highlight the linkage of ice melting and δ¹³C_POC, providing insights into understanding the carbon cycling in the highly productive Antarctic waters.     

Authigenic carbonates from active methane seeps offshore southwest Africa

The southwest African continental margin is well known for occurrences of active methane-rich fluid seeps associated with seafloor pockmarks at water depths ranging broadly from the shelf to the deep basins, as well as with high gas flares in the water column, gas hydrate accumulations, diagenetic carbonate crusts and highly diverse benthic faunal communities. During the M76/3a expedition of R/V METEOR in 2008, gravity cores recovered abundant authigenic carbonate concretions from three known pockmark sites—Hydrate Hole, Worm Hole, the Regab pockmark—and two sites newly discovered during that cruise, the so-called Deep Hole and Baboon Cluster. The carbonate concretions were commonly associated with seep-benthic macrofauna and occurred within sediments bearing shallow gas hydrates. This study presents selected results from a comprehensive analysis of the mineralogy and isotope geochemistry of diagenetic carbonates sampled at these five pockmark sites. The oxygen isotope stratigraphy obtained from three cores of 2–5?m length indicates a maximum age of about 60,000–80,000?years for these sediments. The authigenic carbonates comprise mostly magnesian calcite and aragonite, associated occasionally with dolomite. Their very low carbon isotopic compositions (–61.0?<?δ¹³C ‰ V-PDB?<?–40.1) suggest anaerobic oxidation of methane (AOM) as the main process controlling carbonate precipitation. The oxygen isotopic signatures (+2.4?<?δ¹⁸O ‰ V-PDB?<?+6.2) lie within the range in equilibrium under present-day/interglacial to glacial conditions of bottom seawater; alternatively, the most positive δ¹⁸O values might reflect the contribution of ¹⁸O-rich water from gas hydrate decomposition. The frequent occurrence of diagenetic gypsum crystals suggests that reduced sulphur (hydrogen sulphide, pyrite) from sub-seafloor sediments has been oxidized by oxygenated bottom water. The acidity released during this process can potentially induce the dissolution of carbonate, thereby providing enough Ca²⁺ ions for pore solutions to reach gypsum saturation; this is thought to be promoted by the bio-irrigation and burrowing activity of benthic fauna. The δ¹⁸O–δ¹³C patterns identified in the authigenic carbonates are interpreted to reflect variations in the rate of AOM during the last glacial–interglacial cycle, in turn controlled by variably strong methane fluxes through the pockmarks. These results complement the conclusions of Kasten et al. in this special issue, based on authigenic barite trends at the Hydrate Hole and Worm Hole pockmarks which were interpreted to reflect spatiotemporal variations in AOM related to subsurface gas hydrate formation–decomposition.     

Molecular and isotopic constraints on the sources of suspended particulate organic carbon on the northwestern Atlantic margin

The abundance, carbon isotopic composition (Δ¹⁴C and δ¹³C), and lipid biomarker (alkenones and saturated fatty acids) distributions of suspended particulate organic matter were investigated at three stations centered on the 2000, 3000, and 3500 m isobaths over the New England slope in order to assess particulate carbon sources and dynamics in this highly productive and energetic region. Transmissometry profiles reveal that particle abundances exhibit considerable fine structure, with several distinct layers of elevated suspended particulate matter concentration at intermediate water depths in addition to the presence of a thick bottom nepheloid layer at each station. Excluding surface water samples, the Δ¹⁴C values of particulate organic carbon (POC) indicated the presence of a pre-aged component in the suspended POC pool (Δ¹⁴C<+38‰). The Δ¹⁴C values at the 3000 m station exhibited greater variability and generally were lower than those at the other two stations where the values decreased in a more systematic matter with increasing sampling depth. These lower Δ¹⁴C values were consistent with higher relative abundances of terrigenous long-chain fatty acids at this station than at the other two stations. Two scenarios were considered regarding the potential provenances of laterally transported POC: cross-shelf transport of shelf sediment (Δ¹⁴C=?140‰) and along-slope transport of the slope sediment proximal to the sampling locations (Δ¹⁴C=?260‰). Depending on the scenario, isotopic mass balance calculations indicate allochthonous POC contributions ranging between 15% and 54% in the meso- and bathy-pelagic zone, with the highest proportions at the 3000 m station. Alkenone-derived temperatures recorded on suspended particles from surface waters closely matched in-situ temperatures at each station. However, alkenone-derived temperatures recorded on particles from the subsurface layer down to 250 m were lower than those of overlying surface waters, especially at the 3000 m station, implying supply of phytoplankton organic matter originally produced in cooler surface waters. AVHRR images and temperature profiles indicate that the stations were under the influence of a warm-core ring during the sampling period. The low alkenone-derived temperatures in the subsurface layer coupled with the lower Δ¹⁴C values for the corresponding POC suggests supply of OC on resuspended sediments underlying cooler surface waters distal to the study area, possibly further north or west. Taken together, variations in Δ¹⁴C values, terrigenous fatty acid abundances, and alkenone-derived temperatures among the stations suggest that input of laterally advected OC is a prominent feature of POC dynamics on the NW Atlantic margin, and is spatially heterogeneous on a scale smaller than the distance between the stations (<150 km).     

Molecular and isotopic characteristics of gas hydrate-bound hydrocarbons in southern and central Lake Baikal

We investigated the molecular composition (methane, ethane, and propane) and stable isotope composition (methane and ethane) of hydrate-bound gas in sediments of Lake Baikal. Hydrate-bearing sediment cores were retrieved from eight gas seep sites, located in the southern and central Baikal basins. Empirical classification of the methane stable isotopes (δ¹³C and δD) for all the seep sites indicated the dominant microbial origin of methane via methyl-type fermentation; however, a mixture of thermogenic and microbial gases resulted in relatively high methane δ¹³C signatures at two sites where ethane δ¹³C indicated a typical thermogenic origin. At one of the sites in the southern Baikal basin, we found gas hydrates of enclathrated microbial ethane in which ¹³C and deuterium were both highly depleted (mean δ¹³C and δD of –61.6‰ V-PDB and –285.4‰ V-SMOW, respectively). To the best of our knowledge, this is the first report of C₂ δ¹³C–δD classification for hydrate-bound gas in either freshwater or marine environments.