Intercomparison of soil pore water extraction methods for stable isotope analysis has been a focus of recent studies in relation to plant source waters, which found a wide isotopic variance depending on the extraction method. Few studies have yet explored extraction effects for mobile pore waters that relate to hillslope runoff. This is because it is extremely difficult in natural systems to control the boundary conditions in order to assess and compare impacts of pore water extraction on resulting hillslope flow. With our new semicontrolled experiments on outdoor mini‐hillslopes, we studied mixing and runoff processes by means of stable isotopes of water and quantified relations between pore water extraction methods. We tested the null hypothesis that nondestructive and destructive pore water sampling methods sample the same soil water pool. Three hillslopes were mounted on load cells, filled with loamy sand textured soils from the Landscape Evolution Observatoryat Biosphere 2, equipped with soil moisture and temperature sensors, a bottom outflow, and a surface runoff gauge for isotope sampling. We followed the precipitation isotopic composition over and through the soil profile. One hillslope was instrumented with suction cups, on the second we installed sampling ports for in‐situ soil water vapour measurements, and the third hillslope was sampled destructively for applying the centrifugation and vapour equilibrium methods. All hillslopes were sampled at four depths (0–10, 10–20, 20–30, and 30–40 cm) at three different downslope positions.²H and¹⁸O analyses were performed via laser spectroscopy. We found no isotopic differences between rainfall, surface runoff, and bottom outflow. The in situ vapour ports' soil isotope data showed the widest spread over all hillslope positions and depths. Centrifugation's and suction cups' isotope results plotted closest to the local meteoric water line and within the range of hillslope runoff and bottom outflow data. Hillslope position did not influence the soil isotope results. These results suggest caution be used in the field when selecting an extraction technique for matching soil waters to runoff waters. Soil suction lysimeters and centrifugation appeared to be the most appropriate tools in this regard.

The development of in situ vapour sampling methods to measure δ²H and δ¹⁸O in pore water of deep, unsaturated soil profiles, including mine tailings and waste rock, is required to improve our ability to track water migration through these deposits. To develop appropriate field sampling methods, a laboratory study was first undertaken to evaluate potential materials and sampling methods to collect and analyse vapour samples from unsaturated mine waste. Field methods were developed based on these findings and tested at two mine sites using either on-site analyses with a portable isotope laser spectrometer or sample collection and storage prior to laboratory analyses. The field sites included a series of deep (>50 m) multiport profiles within a coal waste rock dump and open wells installed in a sand tailings dyke at an oil sands mine. Laboratory results show that memory effects in sample bags and tubing require 3–5 pore volumes of vapour flushing prior to sample collection and sample storage times are limited to 24 h. Field sampling highlighted a number of challenges including the need to correct for sample humidity and in situ temperature. Best results were obtained when a portable laser spectrometer was used to measure vapour samples in situ.