Description: Recently developed analytical techniques to determine the abundances of noble gases in sediment pore water allow noble-gas concentrations and isotope ratios to be measured easily and routinely in lacustrine sediments. We applied these techniques for the first time to ocean sediments to investigate an active cold methane seepage system located in the South Pacific off the coast of the North Island of New Zealand using 3He/4He ratios determined in the sediment pore water. The results show that more 3He-rich fluids are released in the vicinity of the Pacific–Australian subduction zone than at the forearc stations located closer to the New Zealand coast. However, the He isotope signature in the sediment column indicates that only a minor part of the He emanating from deeper strata originates from a depleted mantle source. Hence, most He in the pore water is produced locally by the radioactive decay of U and Th in the sediment minerals or in the underlying crustal rocks. Such an occurrence of isotopically heavy crustal He also suggests that the source of the largest fraction of methane is a near-surface geochemical reservoir. This finding is in line with a previous δ13C study in the water column which concluded that the emanating methane is most likely of biological origin and is formed in the upper few meters of the sediment column. Moreover, the prevalence of isotopically heavy He agrees well with the outcome of other previous studies on island arc systems which indicate that the forearc regions are characterized by crustal He emission, whereas the volcanic arc region is characterized by the presence of mantle He associated with rising magma.

Description: In this study, the largest ever carried out to measure noble gases in the pore water of unconsolidated sediments in lakes, the emission of terrigenic He through the sediment column of Lake Van was successfully mapped on the local scale. The main input of He to the water body occurs at the borders of a deep basin within the lake, which is probably the remains of a collapsed caldera. The 3He/4He3He/4He ratio identifies the He injected into the sedimentary column of Lake Van as a mixture of He released from a mantle source and radiogenic He of crustal origin (3He/4He∼2.6-4.1×10-6)(3He/4He∼2.6-4.1×10-6). During passage through the pore space, terrigenic He seems to be further enriched in radiogenic He that is most likely produced in the sediment column. In fact, two distinct trends in isotopic composition can be distinguished in the He injected from the lake basement into the sediments. One of these characterizes samples from the shallow water, the other characterizes samples from the deep basin. However, both of these trends are related to the same source of terrigenic He. The He fluxes determined seem to be characteristic of each sampling location and might be considered as a proxy for the fluid permeability of the deep sediment column. These new findings provide insight into the process of fluid transport within the sediments and into the process of formation of the lake basin. Moreover, the isotopic signature of the He that emanates into the water column of Lake Van is strongly affected by the mixing conditions prevailing in the overlying water body. This fact misled previous studies to interpret the terrigenic He in Lake Van as being solely of mantle origin (3He/4He∼10-5)(3He/4He∼10-5).

Description: Lake Van is the fourth largest terminal lake in the world (volume 607 km(3), area 3570 km(2), maximum depth 460 m), extending for 130 km WSW-ENE on the Eastern Anatolian High Plateau, Turkey. The sedimentary record of Lake Van, partly laminated, has the potential to obtain a long and continuous continental sequence that covers several glacial-interglacial cycles (ca 500 kyr). Therefore, Lake Van is a key site within the International Continental Scientific Drilling Program (ICDP) for the investigation of the Quaternary climate evolution in the Near East ('PALEOVAN'). As preparation for an ICDP drilling campaign, a site survey was carried out during the past years. We collected 50 seismic profiles with a total length of similar to 850 km to identify continuous undisturbed sedimentary sequences for potential ICDP locations. Based on the seismic results, we cored 10 different locations to water depths of up to 420 m. Multidisciplinary scientific work at positions of a proposed ICDP drill site included measurements of magnetic susceptibility, physical properties, stable isotopes, XRF scans, and pollen and spores. This core extends back to the Last Glacial Maximum (LGM), a more extended record than all the other Lake Van cores obtained to date. Both coring and seismic data do not show any indication that the deepest part of the lake (Tatvan Basin, Ahlat Ridge) was dry or almost dry during past times. These results show potential for obtaining a continuous undisturbed, long continental palaeoclimate record. In addition, this paper discusses the potential of 'PALEOVAN' to establish new results on the dynamics of lake level fluctuations, noble gas concentration in pore water of the lake sediment, history of volcanism and volcanic activities based on tephrostratigraphy, and paleoseismic and earthquake activities. (C) 2009 Elsevier Ltd. All rights reserved.

Description: The spatiotemporal dynamics of denitrification in groundwater are still not well-understood because of a lack of efficient methods to quantify this biogeochemical reaction pathway. Previous research used the ratio of N2 to argon (Ar) to quantify net production of N2 via denitrification by separating the biologically generated N2 component from the atmospheric-generated components. However, this method does not allow the quantification of the atmospheric components accurately because the differences in gas partitioning between N2 and Ar are being neglected. Moreover, conventional (noble) gas analysis in water is both expensive and labor-intensive. We overcome these limitations by using a portable mass spectrometer system, which enables a fast and efficient in situ analysis of dissolved (noble) gases in groundwater. By analyzing a larger set of (noble) gases (N2, He, Ar, and Kr) combined with a physically meaningful excess air model, we quantified N2 originating from denitrification. Consequently, we were able to study the spatiotemporal dynamics of N2 production due to denitrification in riparian groundwater over a six-month period. Our results show that denitrification is highly variable in space and time, emphasizing the need for spatially and temporally resolved data to accurately account for denitrification dynamics in groundwater.

Description: 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.

Description: The concentration and carbon isotope values of dissolved methane were measured in the water column at Rock Garden, Omakere Ridge and Wairarapa areas in the first dedicated cold seep investigation along the Hikurangi Margin of New Zealand. These measurements provide a high resolution impression of the methane distribution in the water column and show that these seep sites are actively venting methane with varying intensity. The highest concentrations (up to 3500 nM) measured in water samples obtained from Conductivity–Temperature–Depth (CTD) operations were at Faure Site of Rock Garden. Here, seafloor bubble release was observed by ROV. The Omakere Ridge area is actively venting over almost its entire length (not, vert, similar 25 km), in particular at Bear's Paw, a newly discovered seep site. In the Wairarapa area another new seep site called Tui was discovered, where methane measurements often exceeded 500 nM. No evidence was obtained from water column or sea surface measurements along the Hikurangi Margin to indicate that methane from seeps is reaching the sea surface. In fact, a consistent upper boundary was observed at a density of 26.85 kg/m3, which occurs at about 500 m below sea surface, above which methane decreased to background concentrations. No obvious oceanographic feature is associated with this 500 m CH4 boundary. Bubble dissolution calculations show that about 500 m was also the model-derived maximum bubble rise height. A wide range of δ13CCH4 values from − 71 to − 19‰ (VPDB) were measured, with the highest CH4 concentrations having the lowest δ13CCH4 values of about − 71 to − 68‰. Simple mixing and isotope fractionation calculations show that changes of δ13CCH4 values are predominantly caused by the dilution of seep fluids with the seawater, with some anaerobic oxidation also occurring.