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128 CHAPTER 4. AQUATIC SYSTEMS 4.1.8 Collecting dissolved gases in water by diffusion samplers Martin Wieser (participating scientists: Werner Aeschbach-Hertig) Abstract A new sampling method to extract dissolved noble gases from groundwater by in-situ equilibration with a small gas volume separated by a semi-permeable membrane (so-called diffusion sampler) has been established. Lab and field experiments were conducted to test the functionality and efficiency of the method. Figure 4.9: Adaptation curve of nitrogen saturated diffusion samplers in air saturated water. Shown is the curve for 40 Ar. Embedded is a schematic drawing of a diffusion sampler Background The dissolved noble gas content in groundwater is a significant palaeoclimatic tool for determination of the infiltration temperature. In order to measure the concentration of these noble gases, sampling of the water for later analysis is an important issue. Besides the original method to take water samples in copper tubes, a new method of diffusion samplers has been proposed [Sanford et al. , 1996]. Methods and results The conventional sampling method is to store a certain amount of water in copper tubes whose ends are clenched off by steel clamps. This water can be extracted on a high-vacuum line to receive the dissolved gases for mass spectrometrical analysis. In the new method of passive diffusion samplers gas containers with a diffusive membrane are used, which are introduced into the water and stay there for about two days. During this time the dissolved gas content of the water equilibrates with the gas volume in the container. This container is built by two copper tubes whose open sides are connected via a silicone tube, which represents the membrane (see fig. 4.9). After removing the sampler, the copper tube containing the sampled gas is clenched off by a hydraulic plier to make a gas-tight sample. The measurement of this gas sample in conjunction with the determination of the total dissolved gas pressure (TDGP) provides the same information as the analysis of water samples. A new multiprobe that inclueds a TDGP probe has been tested and applied. The determination of the sampler’s equilibration time was a major topic of the research. This time depends on the permeability of the membrane and therefore on the noble gas. By preparing diffusion samplers in a nitrogen atmosphere and equilibrating them in air saturated water for defined times, I could estimate the adaptation times of the exponential saturation curve for several wall thicknesses of the silicone tube. Other experiments with degassed or oversaturated water were carried out similarly. The noble gas with the longest adaptation time, according to their permeability in silicone rubber, was neon, xenon was the fastest. The samplers as well as the multiprobe were used for several field experiments including a groundwater well near Willersinnweiher in Ludwigshafen and a mining lake in Brandenburg. Also, comparisons with the conventional method both in the lab and the field have been carried out. Results show the usefulness of the new method as an addition to the conventional method. Outlook/Future work After having installed the infrastructure for measurements of gas samples and establishing the use diffusion samplers, the method can be incorporated in field campaigns to come. Furthermore, a study of the total gas composition could be conducted.
4.1. GROUNDWATER AND PALEOCLIMATE 129 References Aeschbach-Hertig, W. 2006a. Edelgase im Grundwasser als Tracer und Klimaindikatoren. Invited talk, Kolloquium Erdwissenschaften, University of Basel, Switzerland. Aeschbach-Hertig, W. 2006b. Edelgase und ”Excess Air” im Grundwasser. Invited talk, Hydrologisches Kolloquium, University of Freiburg, Germany. Aeschbach-Hertig, W. 2006c. Environmental tracers in groundwater studies - Case study North China Plain. Invited talk, School of Environmental Science and Engineering, Chang’an University, Xi’an, China. Aeschbach-Hertig, W. 2006d. Groundwater age dating with gas tracers: The role of gas partitioning. Invited key presentation, Annual Meeting of the Geological Society of America (GSA), Philadelphia, USA. Aeschbach-Hertig, W. 2006e. Rebuttal of ”On global forces of nature driving the Earth’s climate. Are humans involved?”. Env. Geol. DOI 10.1007/s00254-006-0519-3. Aeschbach-Hertig, W. 2006f. Spurenstoffmethoden zur Erforschung des Grundwassers. Invited talk, Rhein-Neckar Gesprächskreis, Heidelberg, Germany. Aeschbach-Hertig, W., Peeters, F., Beyerle, U., Beyerle, U., & R., Kipfer. 1999. Interpretation of dissolved atmospheric noble gases in natural waters. Water Resour. Res., 35, 2779–2792. Aeschbach-Hertig, W., Peeters, F., Beyerle, U., & R., Kipfer. 2000. Palaeotemperature reconstruction from noble gases in ground water taking into account equilibration with entrapped air. Nature, 405, 1040–1044. Aeschbach-Hertig, W., Holzner, C. P., Hofer, M., Simona, M., Barbieri, A., & Kipfer, R. 2007. A time series of environmental tracer data from deep meromictic Lake Lugano, Switzerland. Limnol. Oceanogr., 52, 257 – 273. Busenberg, E., & Plummer, N. L. 2000. Dating young groundwater with sulfur hexafluoride: Natural and anthropogenic sources of sulfur hexafluoride. Water Resour. Res., 36, 3011–3030. Edmunds, W. M., Ma, J.Z., Aeschbach-Hertig, W., Kipfer, R., & Darbyshire, D.P.F. 2006. Groundwater recharge history and hydrogeochemical evolution in the Minqin Basin, North West China. Appl. Geochem., 21, 2148–2170. Friedrich, R., Aeschbach-Hertig, W., Vero, G., & Leßmann, B. 2006. A multi tracer study to investigate the groundwater in the Odenwald region, Germany. In: Annual Meeting of the Geological Society of America (GSA), abstracts. Philadelphila: Geological Society of America (GSA). Kipfer, R., Aeschbach-Hertig, W., Peeters, F., & Stute, M. 2002. Noble gases in lakes and ground waters. Pages 615–700 of: Porcelli, D., Ballentine, C., & Wieler, R. (eds), Noble gases in geochemistry and cosmochemistry. Rev. Mineral. Geochem., vol. 47. Washington, DC: Mineralogical Society of America, Geochemical Society. Kreuzer, A. M., Zongyu, C., Kipfer, R., & Aeschbach-Hertig, W. 2006. Environmental Tracers in Groundwater of the North China Plain. Pages 136–139 of: IAEA (ed), Isotopes in Environmental Studies - Aquatic Forum 2004. Vienna: IAEA. Sanford, W. E., Shropshire, R. G., & Solomon, D. K. 1996. Dissolved gas tracers in groundwater: Simplified injection, sampling, and analysis. Water Resour. Res., 32, 1635–1642. von Rohden, C. L., Kreuzer, A. M., & Aeschbach-Hertig, W. 2006. Dating Young Groundwater in the North China Plain. In: Groundwater – Present Status and Future Task, Abstracts. Beijing: International Association of Hydrogeologists. Wieser, M. 2006. Entwicklung und Anwendung von Diffusionssamplern zur Beprobung gelöster Edelgase in Wasser. diploma thesis, <strong>Universität</strong> Heidelberg.
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