Cryogenic water extraction is the most widely used method to facilitate the laboratory removal of soil pore water for isotopic analysis. However, recent studies have suggested that cryogenic extraction conditions (extraction time, temperature, vacuum threshold) and physicochemical soil properties can influence extracted water isotopic signatures. Here, we argue that new work is needed to analyse the full extent of these effects on the extracted water isotopic composition. We illustrate this need with a simple lab experiment and show that in addition to extraction times, soil organic matter and its exchangeable bonded hydrogen fraction influence the resulting isotope composition. We hope these comments stimulate discussion on the assumptions and limitations of cryogenic extraction for soil water and lead ultimately to a standardization of testing approaches.

Abstract. Stable isotopic analysis of water in plant, soil, and hydrological studies often requires the extraction of water from plant or soil samples. Cryogenic vacuum extraction is one of the most widely used and accurate extraction methods to obtain such water samples. Here, we present a new design of a cryogenic vacuum extraction system with 18 extraction slots and an innovative mechanism to aerate the vacuum system after extraction. This mobile and extendable multi-port extraction system overcomes the bottleneck of time required for capturing unfractionated extracted water samples by providing the possibility to extract a larger number of samples per day simultaneously. The aeration system prevents the loss or mixture of water vapor during defrosting by purging every sample with high-purity nitrogen gas. A set of system functionality tests revealed that the extraction device guarantees stable extraction conditions with no changes in the isotopic composition of the extracted water samples. Surprisingly, extractions of dried and rehydrated soils showed significant differences of the isotopic composition of the added water and the extracts. This observation challenges the assumption that cryogenic extraction systems to fully extract soil water. Furthermore, in a plant water uptake study different results for hydrogen and oxygen isotope data were obtained, raising problems in the definition from which depths plants really take up water. Results query whether the well-established and widely used cryogenic vacuum distillation method can be used in a standard unified method of fixed extraction times as it is often done.

[1] End member mixing analysis (EMMA) is a commonly applied method to identify and quantify the dominant runoff producing sources of water. It employs tracers to determine the dimensionality of the hydrologic system. Many EMMA studies have been conducted using two to six tracers, with some of the main tracers being Ca, Na, Cl À , water isotopes, and alkalinity. Few studies use larger tracer sets including minor trace elements such as Li, Rb, Sr, and Ba. None of the studies has addressed the question of the tracer set size and composition, despite the fact that these determine which and how many end members (EM) will be identified. We examine how tracer set size and composition affects the conceptual model that results from an EMMA. We developed an automatic procedure that conducts EMMA while iteratively changing tracer set size and composition. We used a set of 14 tracers and 9 EMs. The validity of the resulting conceptual models was investigated under the aspects of dimensionality, EM combinations, and contributions to stream water. From the 16,369 possibilities, 23 delivered plausible results. The resulting conceptual models are highly sensitive to the tracer set size and composition. The moderate reproducibility of EM contributions indicates a still missing EM. It also emphasizes that the major elements are not always the most useful tracers and that larger tracer sets have an enhanced capacity to avoid false conclusions about catchment functioning. The presented approach produces results that may not be apparent from the traditional approach and it is a first step to add the idea of statistical significance to the EMMA approach.

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Abstract. For more than two decades, research groups in hydrology, ecology, soil science, and biogeochemistry have performed cryogenic water extractions (CWEs) for the analysis of δ2H and δ18O of soil water. Recent studies have shown that extraction conditions (time, temperature, and vacuum) along with physicochemical soil properties may affect extracted soil water isotope composition. Here we present results from the first worldwide round robin laboratory intercomparison. We test the null hypothesis that, with identical soils, standards, extraction protocols, and isotope analyses, cryogenic extractions across all laboratories are identical. Two standard soils with different physicochemical characteristics along with deionized (DI) reference water of known isotopic composition were shipped to 16 participating laboratories. Participants oven-dried and rewetted the soils to 8 and 20 % gravimetric water content (WC), using the deionized reference water. One batch of soil samples was extracted via predefined extraction conditions (time, temperature, and vacuum) identical to all laboratories; the second batch was extracted via conditions considered routine in the respective laboratory. All extracted water samples were analyzed for δ18O and δ2H by the lead laboratory (Global Institute for Water Security, GIWS, Saskatoon, Canada) using both a laser and an isotope ratio mass spectrometer (OA-ICOS and IRMS, respectively). We rejected the null hypothesis. Our results showed large differences in retrieved isotopic signatures among participating laboratories linked to soil type and soil water content with mean differences compared to the reference water ranging from +18.1 to −108.4 ‰ for δ2H and +11.8 to −14.9 ‰ for δ18O across all laboratories. In addition, differences were observed between OA-ICOS and IRMS isotope data. These were related to spectral interferences during OA-ICOS analysis that are especially problematic for the clayey loam soils used. While the types of cryogenic extraction lab construction varied from manifold systems to single chambers, no clear trends between system construction, applied extraction conditions, and extraction results were found. Rather, observed differences in the isotope data were influenced by interactions between multiple factors (soil type and properties, soil water content, system setup, extraction efficiency, extraction system leaks, and each lab's internal accuracy). Our results question the usefulness of cryogenic extraction as a standard for water extraction since results are not comparable across laboratories. This suggests that defining any sort of standard extraction procedure applicable across laboratories is challenging. Laboratories might have to establish calibration functions for their specific extraction system for each natural soil type, individually.