Determining the stable isotope composition of pore water from saturated and unsaturated zone core: improvements to the direct vapour equilibration laser spectrometry method

Abstract. A method to measure the δ²H and δ¹⁸O composition of pore waters in saturated and unsaturated geologic core samples using direct vapour equilibration and laser spectrometry (DVE–LS) was first described in 2008, and has since been rapidly adopted. Here, we describe a number of important methodological improvements and limitations encountered in routine application of DVE–LS over several years. Generally, good comparative agreement, as well as accuracy, is obtained between core pore water isotopic data obtained using DVE–LS and that measured on water squeezed from the same core. In complex hydrogeologic settings, high-resolution DVE–LS depth profiles provide greater spatial resolution of isotopic profiles compared to long-screened or nested piezometers. When fluid is used during drilling and coring (e.g. water rotary or wet sonic drill methods), spiking the drill fluid with ²H can be conducted to identify core contamination. DVE–LS analyses yield accurate formational isotopic data for fine-textured core (e.g. clay, shale) samples, but are less effective for cores obtained from saturated permeable (e.g. sand, gravels) geologic media or on chip samples that are easily contaminated by wet rotary drilling fluid. Data obtained from DVE–LS analyses of core samples collected using wet (contamination by drill water) and dry sonic (water loss by heating) methods were also problematic. Accurate DVE–LS results can be obtained on core samples with gravimetric water contents > 5 % by increasing the sample size tested. Inexpensive Ziploc™ gas-sampling bags were determined to be as good as, if not better than, other, more expensive specialty bags. Sample storage in sample bags provides acceptable results for up to 10 days of storage; however, measurable water loss, as well as evaporitic isotopic enrichment, occurs for samples stored for up to 6 months. With appropriate care taken during sample collection and storage, the DVE–LS approach for obtaining high-resolution pore water isotopic data is a promising alternative to study the hydrogeology of saturated and unsaturated sediments. Eliminating analytical interferences from volatile organics remains a challenge.