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: We developed a portable mass spectrometric system (“miniRuedi”) for quantificaton of the partial pressures of He, Ne (in dry gas), Ar, Kr, N2, O2, CO2, and CH4 in gaseous and aqueous matrices in environmental systems with an analytical uncertainty of 1−3%. The miniRuedi does not require any purification or other preparation of the sampled gases and therefore allows maintenance- free and autonomous operation. The apparatus is most suitable for on-site gas analysis during field work and at remote locations due to its small size (60 cm × 40 cm × 14 cm), low weight (13 kg), and low power consumption (50 W). The gases are continuously sampled and transferred through a capillary pressure reduction system into a vacuum chamber, where they are analyzed using a quadrupole mass spectrometer with a time resolution of ≲1 min. The low gas consumption rate (〈0.1 mL/min) minimizes interference with the natural mass balance of gases in environmental systems, and allows the unbiased quantification of dissolved-gas concentrations in water by gas/water equilibration using membrane contractors (gasequilibrium membrane-inlet mass spectrometry, GE-MIMS). The performance of the miniRuedi is demonstrated in laboratory and field tests, and its utility is illustrated in field applications related to soil-gas formation, lake/atmosphere gas exchange, and seafloor gas emanations.

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: Global estimates see river deltas and estuaries contributing about equally to CO2 and CH4 emissions as lakes and reservoirs, despite a factor 6 smaller surface area. Assessing the horizontal gradients in dissolved gas concentrations from large river reaches to connecting canals and wetland lakes remains a challenge in many deltaic systems. To elucidate the processes affecting local CO2 and CH4 concentrations in the Romanian part of the Danube Delta, we mapped dissolved O2, N2, He and Ar using a portable gas-equilibration membrane-inlet mass spectrometer (GE-MIMS), along with CO2, CH4, water temperature and conductivity. We measured the concentrations along the aquatic continuum from a small houseboat during two campaigns, in spring and autumn, to capture different hydrological and plant growth conditions. Delta-scale concentration patterns were comparably stable across seasons. Small connecting channels were highly influenced by the riparian wetland, which was strongest in the eastern part of the biosphere reserve. These sites represented the delta’s CO2 and CH4 hotspots and showed clear signs of excess air, i.e., supersaturation of dissolved noble gases with respect to air-saturated water. As the adjacent wetland was permanently inundated, this signal was likely caused by root aeration of Phragmites australis, as opposed to traditional excess air formation via water table fluctuations in the unsaturated zone. The special vegetation setting with reed growing on floating peat coincided with the highest CO2 and CH4 concentrations (〉700 μmol/L CO2 and 13 μmol/L CH4, respectively) observed in an adjacent channel. Shallow lakes, on the other hand, were major sites of photosynthetic production with O2 oversaturation reaching up to 150% in spring. The observed deficit in non-reactive gases (He, Ar and N2) indicated that the lakes were affected by O2 ebullition from macrophytes. According to our estimations, this ebullitive flux decreased O2 concentrations by up to 2 mg/L. This study highlights the effect of plant-mediated gas transfer on dissolved gas concentrations and supports recent studies stressing the need to account for ebullitive gas exchange when assessing metabolism parameters from O2 in shallow, productive settings.