The isotopic composition (d 2 H, d 18 O) of pore water is an invaluable tracer for the minimally invasive study of subsurface water flow and transport processes. Here, we evaluated a method for pore water isotope analysis that combines laser-based isotope analyzers and water-vapor isotope equilibration using evaporation-proof metalized sample bags. We tested inflation atmospheres (dry air vs. pure N 2 ) and the impact of biogenic gas (CO 2 , CH 4 ) accumulation for storage times of up to 4 wk. Samples were analyzed with a water isotope analyzer (Picarro L2120-i) and a gas chromatograph. Air-inflated water vapor samples showed a greater range of gas matrix effects (d 18 O: 9.63‰; d 2 H: 21.7‰) than N 2 -inflated samples (d 18 O: 7.49‰; d 2 H: 10.6‰) induced by nonuniform buildup of biogenic CO 2 , starting immediately after sample preparation. However, only air-inflated samples could be reliably corrected using instrument-specific sensitivity factors that were empirically determined by interpretation of periodically repeated isotope measurements. Corrected water isotope data were confirmed by similarity with local precipitation and suction cup isotope data. Residual uncertainties were well below the natural variations of soil water isotope values and independent of storage time, thus allowing for consistently reliable interpretations of soil water isotope profiles. We conclude that, especially for pore water sampling that requires small sample volumes and/or long storage times, metalized sample bags should be used to prevent evaporation notwithstanding the enhanced buildup of biogenic gases. Further, if gas matrix effects cannot be excluded, air inflation is preferred over pure N 2 , as only in that case can reliable postcorrections be performed by using internal data only.Abbreviations: CRDS, cavity ring-down spectrometry; DVE-LS, direct vapor equilibration laser spectrometry; GC, gas chromatography; GMWL, global meteoric water line; lc-excess, line-conditioned excess; LMWL, local meteoric water line; LWV, analyzerrecorded line width variable; OA-ICOS, off-axis integrated cavity output spectrometry.
Environmental tracers like the isotopic composition of water (d 2 H, d 18 O) haveproven to be valuable tools in hydrology covering all parts of the water cycle. In subsurface hydrology, stable isotopes of water have been successfully applied to determine soil evaporation (Allison, 1982;Braud et al., 2009), groundwater recharge rates and sources (Adomako et al., 2010;Blasch and Bryson, 2007;Koeniger et al., 2016), flow paths (Garvelmann et al., 2012;Stumpp and Hendry, 2012;Uchida et al., 2006), mixing processes (Thomas et al., 2013), transit times (Stumpp et al., 2009;Timbe et al., 2014), root water uptake patterns (Rothfuss and Javaux, 2017), and hydraulic lift (Meunier et al., 2018). Kendall and McDonnell (1998) and Vitvar et al. (2005) presented extensive summaries of stable isotope applications in catchment hydrology. Sprenger et al. (2016) placed special emphasis on pore water isotope applications.In traditional ...