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Highlights: • Clay dehydration water expelled from buried sediments drives mud volcanism. • Rise of fluids mediated by crustal-scale strike-slip faults cross-cutting wedge. • On active accretionary wedge, petroleum accumulations were dismantled in Neogene. • 4He enrichment and δ13C-CH4 ~−50‰ in fluids reflect an open hydrocarbon system. • Petroleum pools remain on shallow margin. Microbial gas vented out of active wedge. Abstract: A geochemical study of the composition of hydrocarbon gases and helium isotopes (3He/4He) in fluids from Mud Volcanoes (MVs) located on and out of the active accretionary wedge of the Gulf of Cadiz (GoC) provides information on fluid sources and migrations in deeply buried sediments. The GoC is a tectonically active segment of the Africa-Iberia plate boundary occluded beneath the thick sediments of an accretionary wedge dissected by crustal-scale strike-slip faults. Initially built during the Miocene Gibraltar Arc subduction, the wedge has since developed toward the W-NW in an oblique convergent setting. Interstitial water expelled from clays undergoing diagenesis in buried sediments drives mud volcanism on the wedge, with MVs located along strike-slip faults mediating fluid ascent. The large excess of radiogenic helium (4He) in all GoC fluids agrees with a clay mineral dehydration source of water. Hydrocarbon gases from all deepwater MVs bear methane having similar stable carbon isotope compositions of ~−50‰VPDB whether fluids are highly enriched in methane relative to heavier homologues (C2+) or not (Methane / (Ethane + Propane) ~10 to 10,000). We suggest that methane with −50‰VPDB was largely diffused out of early generating source rocks, and became dissolved in the water expelled by the buried sediments. Consistently, low 3He/4He ratios suggest an open hydrocarbon system: Petroleum accumulations and 3He dissolved in the original sedimentary pore water have mostly escaped into the water column during the major Late Neogene compressional events. At present, some MVs vent CH4-rich fluids from dewatering sediments, while other structures located on active thrusts additionally vent C2+-rich gases generated by active Cretaceous source intervals. By contrast, evaporitic seals preserved petroleum accumulations on the shallow Moroccan Margin, while the westernmost MVs located out of the accretionary wedge vent microbial gas.

Highlights • Noble gas analysis of sediment porewater close to hydrothermal vent system. • Origin of porewater is solely Guaymas Basin bottom water. • Transport of hydrothermal fluids is limited to narrow pathways. • Temporal variability of He isotopic composition recorded in porewater. Abstract We present noble gas concentrations determined in pore water of deep-sea sediments close to a recently discovered hydrothermal vent site, consisting of a mound structure and several black smokers, located in the northern Guaymas Basin, Gulf of California. Noble gases were used as tracers to identify the origin of fluids within the sediment pore space and to gain insight into transport dynamics of hydrothermal fluids in this region. Our data suggest that Guaymas Basin bottom water is the only source of pore water in the pelagic sediment body close to the hydrothermal vent field. In particular, there is no evidence of any direct (diffusive or advective) transport of hydrothermal fluids through the deep-sea sediments surrounding the black smoker system. This finding implies that at this black smoker site hydrothermal fluids are transported upwards from the fluid source in very narrow pathways below the smokers. Thus, the fluids are only injected into the ocean directly through the chimneys of the black smokers and no additional emission from the surrounding sediment takes place. Helium isotope data show that during a more active phase of the vent field in the past (supposedly representing the early onset of the black smokers 5–6 kyrs ago), bottom water with a different isotopic signature was incorporated into the sediment column.

In this work we report tritium concentrations determined in seawater samples collected offshore of Fukushima in the northwestern Pacific Ocean, immediately after the Fukushima Dai-ichi Nuclear Power Plant (F1-NPP) accident. We found surface seawater to have high concentrations of tritium (3H) and cesium-137 (137Cs) with respect to the concentrations expected for the investigated region. Tritium concentrations were up to six times the pre-accident level. However, these concentrations were found to be relatively low compared to those of 137Cs and 129I. This is most likely because of the very low production ratio of tritium to 137Cs in the F1-NPP, and the inherently high background concentration of tritium in these environmental waters (mainly ascribed to global fallout from nuclear weapons tests conducted during the 1960s). The tritium distribution in surface seawater showed higher concentrations close to the shore and lower concentrations offshore. Higher tritium concentration areas had spread both northward and southward from the F1-NPP along the coast, indicating that large amounts of tritium were carried by coastal currents. A positive correlation was found to exist between 3H and 137Cs concentrations in the seawater. The calculated 3H/137Cs ratio was similar to the production ratio of these isotopes reported for the broken reactors in the F1-NPP, which indicates that both radionuclides might have originated from the F1-NPP. Direct emission of tritium to the ocean from the F1-NPP was estimated to be approximately 0.05 PBq immediately after the accident, which is much smaller than the total inventory in the environment.

The commonly observed heterogeneous and erratic emissions of methane from lacustrine sediments are difficult to quantify. The combined analysis of methane and noble gas concentrations in the pore water opens a novel route to analyse and quantify such emissions and was used in this work to explore the gas dynamics in the sediments of two lakes with different hydro-geochemical settings. In the hypertrophic Lake Rot the microbial activity in the sediment pore water results in a virtually continuous gas bubble formation and emission. By determining noble gas concentration gradients and the maximum methane supersaturation, the minimum methane emission from the sediment was quantified. The gas evolution in the pore water of the sediments of artificial Lake Lungern is strongly affected by annual lake level variations of up to 20 m. Noble gas concentrations allow past gas dynamics at different lake levels to be traced back. At “hot spots” of bubble emission microbial methane from deeper sediments was released in response to the decreasing hydrostatic pressure, i.e. man-induced lake level drop. Within zones of the sediment that seasonally fall dry, the air supply to the sediment was inferred from the noble gas excess observed in the pore water, which is due to dissolving air bubbles which entered the sediment during the dry period. These case studies demonstrate the potential of the combined analysis of noble gas and CH4 concentrations for exploring the gas dynamics in lacustrine sediments. The feasibility of this method under different conditions calls for an application in other aquatic environments, such as wetlands and oceans.

This report describes spatial and temporal variations of helium, carbon, and nitrogen isotopes measured in CO2-rich bubbling gases from natural springs associated with Mt. Ontake (central Honshu, Japan) from November 1981 through September 2015. During the entire period, the 3He/4He ratio decreased concomitantly with increasing distance of the sampling site from the central cone. In contrast, the CO2/3He ratios and the δ13C values of CO2 increased with distance. These spatial trends became more pronounced after the September 27, 2014 Ontake eruption, suggesting reactivation of the volcano plumbing system with enhanced emission of magmatic volatiles, although the spatial trend of nitrogen isotopes disappeared. The 3He/4He ratios of the most proximal site to the central cone remained constant until 2000, apparently increasing from June 2003 through October 2014. They became constant soon after the eruption until September 2015. The ten-year 3He enhancement might have been a precursor of the 2014 Ontake eruption. In contrast, δ13C values of CO2 at the same site remained constant through this period. The lack of δ13C anomaly might be attributable to 1) negligibly small amounts of magmatic CO2 introduced into the source of hot springs compared to ambient CO2 in the air-saturated aquifer, or 2) close resemblance of the carbon signature of magmatic CO2 to that of ambient CO2. Therefore its addition cannot change the overall δ13C value of the sampled hot springs. At distal sampling sites, no measurable change of helium, carbon, or nitrogen isotopes was observed in relation to the 2014 Ontake eruption, suggesting that the effect of this eruption on the Ontake hydrothermal system was geographically localized.

A sediment core has been sampled at a spatial resolution of about two centimeters for noble-gas analysis of the sediment pore water. This high-resolution sampling allowed an excess of dissolved atmospheric gases to be identified in the pore water at a sediment depth of 40 cm. Sedimentological evidence indicates that the observed gas excess is related to a past mass movement that trapped and conserved the gas surplus for more than a century. The measured noble-gas concentrations support the hypothesis that, depending on the sediment texture or particular structures in the sediment, the transport of noble gases in the pore space can be significantly attenuated compared to molecular diffusion in bulk water. The atmospheric noble-gas abundance in the pore water allows the deposition of sediments originally located near the air/water interface to be identified. Although the nature of the physical processes that limit the fluid transport in the pore space could not be fully assessed, our observations indicate that noble-gas concentration profiles can be archived for unexpectedly long times in specific sedimentary sequences. This finding represents a significant step forward in the interpretation of noble-gas concentrations in sediment pore waters in terms of past environmental conditions.

In closed-basin lakes, sediment porewater salinity can potentially be used as a conservative tracer to reconstruct past fluctuations in lake level. However, until now, porewater salinity profiles did not allow quantitative estimates of past lake-level changes because, in contrast to the oceans, significant salinity changes (e.g., local concentration minima and maxima) had never been observed in lacustrine sediments. Here we show that the salinity measured in the sediment pore water of Lake Van (Turkey) allows straightforward reconstruction of two major transgressions and a major regression that occurred during the last 250 ka. We observed strong changes in the vertical salinity profiles of the pore water of the uppermost 100 m of the sediments in Lake Van. As the salinity balance of Lake Van is almost at steady-state, these salinity changes indicate major lake-level changes in the past. In line with previous studies on lake terraces and with seismic and sedimentological surveys, we identify two major transgressions of up to +105 m with respect to the current lake level at about 135 ka BP and 248 ka BP starting at the onset of the two previous interglacials (MIS5e and MIS7), and a major regression of about −200 m at about 30 ka BP during the last ice age.

Methane emission from the geosphere is generally characterized by a radiocarbon-free signature and might preserve information on the deep carbon cycle on Earth. Here we report a clear relationship between the origin of methane-rich natural gases and the geodynamic setting of the West Pacific convergent plate boundary. Natural gases in the frontal arc basin (South Kanto gas fields, Northeast Japan) show a typical microbial signature with light carbon isotopes, high CH4/C2H6 and CH4/3He ratios. In the Akita-Niigata region – which corresponds to the slope stretching from the volcanic-arc to the back-arc –a thermogenic signature characterize the gases, with prevalence of heavy carbon isotopes, low CH4/C2H6 and CH4/3He ratios. Natural gases from mud volcanoes in South Taiwan at the collision zone show heavy carbon isotopes, middle CH4/C2H6 ratios and low CH4/3He ratios. On the other hand, those from the Tokara Islands situated on the volcanic front of Southwest Japan show the heaviest carbon isotopes, middle CH4/C2H6 ratios and the lowest CH4/3He ratios. The observed geochemical signatures of natural gases are clearly explained by a mixing of microbial, thermogenic and abiotic methane. An increasing contribution of abiotic methane towards more tectonically active regions of the plate boundary is suggested., 論文

The structural evolution of Lake Van Basin, eastern Turkey, was reconstructed based on seismic reflection profiles through the sedimentary fill as well as from newly acquired multibeam echosounder data. The major sub-basins (Tatvan Basin and Northern Basin) of Lake Van, bound by NE-trending faults with normal components, formed during the past similar to 600 ka probably due to extensional tectonics resulting from lithospheric thinning and mantle upwelling related to the westward escape of Anatolia. Rapid extension and subsidence during early lake formation led to the opening of the two sub-basins. Two major, still active volcanoes (Nemrut and Suphan) grew close to the lake basins approximately synchronously, their explosive deposits making up > 20 % of the drilled upper 220 m of the ca. 550-m-thick sedimentary fill. During basin development, extension and subsidence alternated with compressional periods, particularly between similar to 340 and 290 ka and sometime before similar to 14 ka, when normal fault movements reversed and gentle anticlines formed as a result of inversion. The similar to 14 ka event was accompanied by widespread uplift and erosion along the northeastern margin of the lake, and substantial erosion took place on the crests of the folds. A series of closely spaced eruptions of Suphan volcano occurred synchronously suggesting a causal relationship. Compression is still prevalent inside and around Lake Van as evidenced by recent faults offsetting the lake floor and by recent devastating earthquakes along their onshore continuations. New, high-resolution bathymetry data from Lake Van reveal the morphology of the Northern Ridge and provide strong evidence for ongoing transpression on a dextral strike-slip fault as documented by the occurrence of several pop-up structures along the ridge.

Fossil long-chain alkenones have been used for several decades to reconstruct past ocean surface water temperatures and gained recent interest as a paleotemperature proxy for continental lake settings. However, factors besides temperature can affect alkenone distributions in haptophyte algae, and alkenone compositions can differ between haptophyte species. Alkenone-biosynthesizing haptophyte algae are genetically much more diverse in lakes than in the marine realm, and species-level variations in alkenone compositions could have implications for alkenone paleothermometry. Here, we performed a paired analysis of alkenone distributions and haptophyte species compositions using ancient DNA in up to 270 ka-old sediments of Lake Van in Turkey to reveal a possible species-effect on fossil alkenone distributions and paleotemperature estimates. The same predominant haptophyte in Lake Van today prevailed also since the last similar to 100 ka. However, a calibration of alkenone paleotemperature especially in the oldest analyzed intervals is complicated due to a more complex haptophyte species composition predominated by a haptophyte (LVHap_6), which is phylogenetically different from sequences recovered from currently existing lakes including Lake Van and from haptophyte species existing in culture. The predominance of LVHap_6 coincided with the presence of alkenone MeC38:3 and relatively high MeC37:3/4 (2.4) and Me08:4/5 ratios (3.0). Uk37 index values in the sediment core over the last 270 ka reflect relative changes in past temperature and are additionally linked to haptophyte species composition. A sustained period of high salinity, as indicated by pore-water salinity measurements, could potentially have triggered the succession of haptophytes as sources of alkenones in Lake Van. 0 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

Shallow submarine volcanoes have been newly discovered near the Tokara Islands, which are situated at the volcanic front of the northern Ryukyu Arc in southern Japan. Here, we report for the first time the volatile geochemistry of shallow hydrothermal plumes, which were sampled using a CTD-RMS system after analyzing water column images collected by multi-beam echo sounder surveys. These surveys were performed during the research cruise KS-14-10 of the R/V Shinsei Maru in a region stretching from the Wakamiko Crater to the Tokara Islands. The 3He flux and methane flux in the investigated area are estimated to be (0.99–2.6) × 104 atoms/cm2/sec and 6–60 t/yr, respectively. The methane in the region of the Tokara Islands is a mix between abiotic methane similar to that found in the East Pacific Rise and thermogenic one. Methane at the Wakamiko Crater is of abiotic origin but affected by isotopic fractionation through rapid microbial oxidation. The helium isotopes suggest the presence of subduction-type mantle helium at the Wakamiko Crater, while a larger crustal component is found close to the Tokara Islands. This suggests that the Tokara Islands submarine volcanoes are a key feature of the transition zone between the volcanic front and the spreading back-arc basin.

There is conclusive evidence that the methods most commonly used to sample methane (CH4) dissolved in the pore water of lake sediments produce results that are likely to be affected by gas loss or gas exchange with the atmosphere. To determine the in situ amount of CH4 per unit mass of pore water in sediments, we developed and validated a new method that combines techniques developed for noble-gas analysis in pore waters with a standard headspace technique to quantify the CH4 present in the pore space in dissolved and gaseous form. The method was tested at two sites: Lake Lungern, where CH4 concentrations were close to saturation; and Lake Rotsee, where CH4 concentrations are known to exceed saturation and where CH4 bubble formation and gas ebullition are commonly observed. We demonstrate that the new method, in contrast to the available methods, more reliably captures the total amount of CH4 per unit mass of pore water consisting of both dissolved and free CH4 (i.e., gas bubbles) in the pore space of the sediment.

Although the naturally occurring atmospheric noble gases He, Ne, Ar, Kr, and Xe possess great potential as tracers for studying gas exchange in living beings, no direct analytical technique exists for simultaneously determining the absolute concentrations of these noble gases in body fluids in vivo. In this study, using human blood as an example, the absolute concentrations of all stable atmospheric noble gases were measured simultaneously by combining and adapting two analytical methods recently developed for geochemical research purposes. The partition coefficients determined between blood and air, and between blood plasma and red blood cells, agree with values from the literature. While the noble-gas concentrations in the plasma agree rather well with the expected solubility equilibrium concentrations for air-saturated water, the red blood cells are characterized by a distinct supersaturation pattern, in which the gas excess increases in proportion to the atomic mass of the noble-gas species, indicating adsorption on to the red blood cells. This study shows that the absolute concentrations of noble gases in body fluids can be easily measured using geochemical techniques that rely only on standard materials and equipment, and for which the underlying concepts are already well established in the field of noble-gas geochemistry. ISSN:1932-6203

[1] Changes in the hydrological regime of the saline closed basin Lake Van, a large, deep lake in eastern Turkey, resulted in a lake level increase by about 2 m between 1988 and 1995, followed by a 1.5 m decrease until 2003 and a relatively constant lake level thereafter. Based on measurements of transient tracers (sulfur hexafluoride, CFC-12, 3H, 3He, 4He, Ne), dissolved oxygen, light transmission, conductivity-temperature-depth profiles, and thermistor data, we investigate the implications associated with lake level fluctuations for deep-water renewal and oxygenation. Our data suggest that deep-water renewal was significantly reduced in Lake Van between 1990 and 2005. This change in mixing conditions resulted in the formation of a more than 100 m thick anoxic deep-water body below 325 m depth. Apparently, the freshwater inflows responsible for the lake level rise between 1988 and 1995 decreased the salinity of the surface water sufficiently that the generation of density plumes during winter cooling was substantially reduced compared to that in the years before the lake level rise. Significant renewal and oxygenation of the deep water did not occur until at least 2005, although by 2003 the lake level was back to almost the same level as in 1988. This study suggests that short-term changes in the hydrological regime, resulting in lake level changes of a couple of meters, can lead to significant and long-lasting changes in deep-water renewal and oxic conditions in deep saline lakes.

Sediments of Lake Van, Turkey, preserve one of the most complete records of continental climate change in the Near East since the Middle Pleistocene. We used seismic reflection profiles to infer past changes in lake level and discuss potential causes related to changes in climate, volcanism, and regional tectonics since the formation of the lake ca. 600 ka ago. Lake Van's water level ranged by as much as 600 m during the past 600 ka. Five major lowstands occurred, at 600, 365-340, 290-230, 150-130 and 30-14 ka. During Stage A, between about 600 and 230 ka, lake level changed dramatically, by hundreds of meters, but phases of low and high stands were separated by long time intervals. Changes in the lake level were more frequent during the past 230 ka, but less dramatic, on the order of a few tens of meters. We identified period B1 as a time of stepwise transgressions between 230 and 150 ka, followed by a short regression between ca. 150 and 130 ka. Lake level rose stepwise during period B2, until 30 ka. During the past 30 ka, a regression and a final transgression occurred, each lasting about 15 ka. The major lowstand periods in Lake Van occurred during glacial periods, suggesting climatic control on water level changes (i.e. greatly reduced precipitation led to lower lake levels). Although climate forcing was the dominant cause for dramatic water level changes in Lake Van, volcanic and tectonic forcing factors may have contributed as well. For instance, the number of distinct tephra layers, some several meters thick, increases dramatically in the uppermost 100 m of the sediment record (i.e. the past 230 ka), an interval that coincides largely with low-magnitude lake level fluctuations. Tectonic activity, highlighted by extensional and/or compressional faults across the basin margins, probably also affected the lake level of Lake Van in the past.