The time that water takes to travel through the terrestrial hydrological cycle and the critical zone is of great interest in Earth system sciences with broad implications for water quality and quantity. Most water age studies to date have focused on individual compartments (or subdisciplines) of the hydrological cycle such as the unsaturated or saturated zone, vegetation, atmosphere, or rivers. However, recent studies have shown that processes at the interfaces between the hydrological compartments (e.g., soil‐atmosphere or soil‐groundwater) govern the age distribution of the water fluxes between these compartments and thus can greatly affect water travel times. The broad variation from complete to nearly absent mixing of water at these interfaces affects the water ages in the compartments. This is especially the case for the highly heterogeneous critical zone between the top of the vegetation and the bottom of the groundwater storage. Here, we review a wide variety of studies about water ages in the critical zone and provide (1) an overview of new prospects and challenges in the use of hydrological tracers to study water ages, (2) a discussion of the limiting assumptions linked to our lack of process understanding and methodological transfer of water age estimations to individual disciplines or compartments, and (3) a vision for how to improve future interdisciplinary efforts to better understand the feedbacks between the atmosphere, vegetation, soil, groundwater, and surface water that control water ages in the critical zone.

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. © 2016 The Authors. Ecohydrology published by John Wiley & Sons Ltd.

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.

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.

Ecohydrological isotope based field research is often constrained by a lack of temporally explicit soil water data, usually related to the choice of destructive sampling in the field and subsequent analysis in the laboratory. New techniques based on gas permeable membranes allow to sample soil water vapor in situ and infer soil liquid water isotopic signatures. Here, a membrane-based in situ soil water vapor sampling method was tested at a grassland site in Freiburg, Germany. It was further compared with two commonly used destructive sampling approaches for determination of soil liquid water isotopic signatures: cryogenic vacuum extraction and centrifugation. All methods were tested under semi-controlled field conditions, conducting an experiment with dry-wet cycling and two isotopically different labeling irrigation waters. We found mean absolute differences between cryogenic vacuum extraction and in situ vapor measurements of 0.3–14.2‰ (δ¹⁸O) and 0.4–152.2‰ (δ²H) for soil liquid water. The smallest differences were found under natural abundance conditions of ²H and ¹⁸O, the strongest differences were observed after irrigation with labeled waters. Labeling strongly increased the isotopic variation in soil water: Mean soil water isotopic signatures derived by cryogenic vacuum extraction were -11.6 ± 10.9‰ (δ¹⁸O) and +61.9 ± 266.3‰ (δ²H). The in situ soil water vapor method showed isotopic signatures of -12.5 ± 9.4‰ (δ¹⁸O) and +169.3 ± 261.5‰ (δ²H). Centrifugation was unsuccessful for soil samples due to low water recovery rates. It is therefore not recommended. Our study highlights that the in situ soil water vapor method captures the temporal dynamics in the isotopic signature of soil water well while the destructive approach also includes the natural lateral isotopic heterogeneity. The different advantages and limitations of the three methods regarding setup, handling and costs are discussed. The choice of method should not only consider prevailing environmental conditions but the experimental design and goal. We see a very promising tool in the in situ soil water vapor method, capturing both temporal developments and spatial variability of soil water processes.