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Methodological advancements have been made in in situ observations of water stable isotopes that have provided valuable insights into ecohydrological processes. The continuous measurement capabilities of laser-based analyzers allow for high temporal resolutions and non-destructive minimally invasive study designs of such in situ approaches. However, isotope analyzers are expensive, heavy, and require shelter and access to electrical power, which impedes many in situ assays. Therefore, we developed a new inexpensive technique to collect discrete water vapor samples in the field via diffusion-tight inflatable bags that can later be analyzed in the lab. In a series of structured experiments, we tested different procedural settings, bag materials, and closure types for diffusion tightness during storage as well as for practical handling during filling and extraction. To facilitate reuse of sampling bags, we present a conditioning procedure using ambient air as primer. In order to validate our method, direct measurements through hydrophobic in situ probes were compared to repeated measurements of vapor sampled with our bags from the same source. All steps are summarized in a detailed standard operating procedure (SOP). This procedure represents the preparation and measurement of calibration and validation vapor standards necessary for processing of unknown field-collected vapor samples in the foreseen application. By performing pertinent calibration procedures, accuracy was better than 0.4 ‰ for δ18O and 1.9 ‰ for δ2H after 1 d of storage. Our technique is particularly suitable when used in combination with minimally invasive water vapor sampling in situ probes that have already been employed for soils and tree xylem. It is an important step towards minimally invasive monitoring of stable isotope distributions and also time series in virtually undisturbed soils and trees without the need to have an analyzer in the field. It is therefore a promising tool for many applications in ecohydrology and meteorology.

Using water-stable isotopes to track plant water uptake or soil water processes has become an invaluable tool in ecohydrology and physiological ecology. Recent studies have shown that laser absorption spectroscopy can measure equilibrated water vapour well enough to support inference of liquid-stable isotope composition of plant or soil water, on-site and in real-time. However, current in situ systems require the presence of an instrument in the field. Here we tested, first in the lab and then in the field, a method for equilibrating, collecting, storing, and finally analysing water vapour for its isotopic composition that does not require an instrument in the field. We developed a vapour storage vial system (VSVS) that relies on in situ sampling into crimp neck vials with a double-coated cap using a pump and a flow metre powered through a small battery and measuring the samples in a laboratory. All components are inexpensive and commercially available. We tested the system's ability to store the isotopic composition of its contents by sampling a range of water vapour of known isotopic compositions (from −95 ‰ to +1700 ‰ for δ2H) and measuring the isotopic composition after different storage periods. Samples for the field trial were taken in a boreal forest in northern Sweden. The isotopic composition was maintained to within 0.6 ‰ to 4.4 ‰ for δ2H and 0.6 ‰ to 0.8 ‰ for δ18O for natural-abundance samples. Although 2H-enriched samples showed greater uncertainty, they were sufficient to quantify label amounts. We detected a small change in the isotopic composition of the sample after a long storage period, but it was correctable by linear regression models. We observed the same trend for the samples obtained in the field trial for δ18O but observed higher variation in δ2H than in the lab trial. Our method combines the best of two worlds, sampling many trees in situ while measuring at high precision in the laboratory. This provides the ecohydrology community with a tool that is not only cost efficient but also easy to use.

The direct vapor equilibration laser spectrometry (DVE-LS) method has been developed for obtaining matrix-bound water stable isotope data in soils, the critical zone, and bedrock, deriving therefrom subsurface water flow and transport processes and, ultimately, characterizing, for example, groundwater recharge and vulnerability. Recently, DVE-LS has been increasingly adopted due to its possible high sample throughput, relative simplicity, and cost-efficiency. However, this has come at the cost of a non-unified standard operation protocol (SOP), and several contradictory suggestions regarding protocol details do exist which have not been resolved to date. Particularly, sample container material and equilibration times have not yet been agreed upon. Beside practical constraints, this often limits DVE-LS applicability to interpreting relative isotope dynamics instead of absolute values. It also prevents data comparability among studies or laboratories, and several previous comparisons of DVE-LS with other, more traditional approaches of water extraction and subsequent stable isotope analysis yielded significant discrepancies for various sample matrices and physical states. In a series of empirical tests, we scrutinized the controversial DVE-LS protocol details. Specifically, we tested 10 different easily available and cost-efficient inflatable bags previously employed or potentially suitable for DVE-LS sample collection and equilibration. In storage tests similar to the DVE-LS equilibration process but lasting several weeks, we quickly found heat-sealed bags made of laminated aluminum (Al) sheets to be superior by several orders of magnitude over more frequently used freezer bags in terms of evaporation safety and accompanying adverse isotope effects. For the first time, Al-laminated bags allow the applied equilibration time to be adapted exclusively to sample requirements instead of accepting reduced data quality in a trade-off with material shortcomings. Based on detailed physical considerations, we further describe how to calculate the minimum available container headspace and sample-contained liquid water volume and how their ratio affects analytical precision and accuracy. We are confident that these guidelines will expand DVE-LS applicability and improve data quality and comparability among studies and laboratories by contributing to a more unified, physically well-founded SOP based on more appropriate components.

The water isotopic composition of throughfall is affected by complex diffusive exchange with ambient water vapour, evaporative enrichment of heavy isotopes, and mixing processes in the tree canopy. All interception processes occur simultaneously in space and time, generating a complex pattern of throughfall depth and water isotopic composition. This pattern ultimately cascades through the entire hydrologic system and is therefore crucial for isotope studies in catchment hydrology, where recharge areas are often forested, while reference meteorological stations are generally in the open. For the quasi real-time observation of the water isotopic composition (δ18O and δ2H) of both gross precipitation and throughfall, we developed an approach combining a membrane contactor (Membrana) with a laser-based Cavity Ring-Down Spectrometer (CRDS, Picarro), obtaining isotope readings every 2 s. A setup with two CRDS instruments in parallel analysing gross precipitation and throughfall simultaneously was used for the continuous observation of the temporal effect of interception processes on the stable isotopes of water. All devices were kept small to minimize dead volume with time lags of only 4 min for water from the rainfall collectors to the isotope analysers to increase the temporal resolution of isotope observations. Complementarily, meteorological variables were recorded at high temporal resolution at the same location. The achieved evolution from discrete liquid or event-based bulk samples to continuous measurements allows for direct comparison of water stable isotope data with common meteorological measurements. Future improvements of the spatial representativeness will make our approach an even more powerful tool towards detailed insight into the dynamic processes contributing to interception during rainfall events.

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.

The length of streamflow observations is generally limited to the last 50 years even in data-rich countries like France. It therefore offers too small a sample of extreme low-flow events to properly explore the long-term evolution of their characteristics and associated impacts. To overcome this limit, this work first presents a daily 140-year ensemble reconstructed streamflow dataset for a reference network of near-natural catchments in France. This dataset, called SCOPE Hydro (Spatially COherent Probabilistic Extended Hydrological dataset), is based on (1) a probabilistic precipitation, temperature, and reference evapotranspiration downscaling of the Twentieth Century Reanalysis over France, called SCOPE Climate, and (2) continuous hydrological modelling using SCOPE Climate as forcings over the whole period. This work then introduces tools for defining spatio-temporal extreme low-flow events. Extreme low-flow events are first locally defined through the sequent peak algorithm using a novel combination of a fixed threshold and a daily variable threshold. A dedicated spatial matching procedure is then established to identify spatio-temporal events across France. This procedure is furthermore adapted to the SCOPE Hydro 25-member ensemble to characterize in a probabilistic way unrecorded historical events at the national scale. Extreme low-flow events are described and compared in a spatially and temporally homogeneous way over 140 years on a large set of catchments. Results highlight well-known recent events like 1976 or 1989–1990, but also older and relatively forgotten ones like the 1878 and 1893 events. These results contribute to improving our knowledge of historical events and provide a selection of benchmark events for climate change adaptation purposes. Moreover, this study allows for further detailed analyses of the effect of climate variability and anthropogenic climate change on low-flow hydrology at the scale of France.

The paper presents an experiment demonstrating a novel and successful application of delay- and disruption-tolerant networking (DTN) technology for automatic data transfer in a karst cave early warning and measuring system. The experiment took place inside the Postojna Cave in Slovenia, which is open to tourists. Several automatic meteorological measuring stations are set up inside the cave, as an adjunct to the surveillance infrastructure; the regular data transfer provided by the DTN technology allows the surveillance system to take on the role of an early warning system (EWS). One of the stations is set up alongside the railway tracks, which allows the tourist to travel inside the cave by train. The experiment was carried out by placing a DTN "data mule" (a DTN-enabled computer with WiFi connection) on the train and by upgrading the meteorological station with a DTN-enabled WiFi transmission system. When the data mule is in the wireless drive-by mode, it collects measurement data from the station over a period of several seconds as the train without stopping passes the stationary equipment, and delivers data at the final train station by the cave entrance. This paper describes an overview of the experimental equipment and organization allowing the use of a DTN system for data collection and an EWS inside karst caves where there is regular traffic of tourists and researchers.

Most of the hydrological and hydraulic studies refer to the notion of a return period to quantify design variables. When dealing with multiple design variables, the well-known univariate statistical analysis is no longer satisfactory, and several issues challenge the practitioner. How should one incorporate the dependence between variables? How should a multivariate return period be defined and applied in order to yield a proper design event? In this study an overview of the state of the art for estimating multivariate design events is given and the different approaches are compared. The construction of multivariate distribution functions is done through the use of copulas, given their practicality in multivariate frequency analyses and their ability to model numerous types of dependence structures in a flexible way. A synthetic case study is used to generate a large data set of simulated discharges that is used for illustrating the effect of different modelling choices on the design events. Based on different uni- and multivariate approaches, the design hydrograph characteristics of a 3-D phenomenon composed of annual maximum peak discharge, its volume, and duration are derived. These approaches are based on regression analysis, bivariate conditional distributions, bivariate joint distributions and Kendall distribution functions, highlighting theoretical and practical issues of multivariate frequency analysis. Also an ensemble-based approach is presented. For a given design return period, the approach chosen clearly affects the calculated design event, and much attention should be given to the choice of the approach used as this depends on the real-world problem at hand.

Changes to streamflows caused by climate change may have major impacts on the management of water for hydro-electricity generation and agriculture in Tasmania, Australia. We describe changes to Tasmanian surface water availability from 1961–1990 to 2070–2099 using high-resolution simulations. Six fine-scale (∼10 km2) simulations of daily rainfall and potential evapotranspiration are generated with the CSIRO Conformal Cubic Atmospheric Model (CCAM), a variable-resolution regional climate model (RCM). These variables are bias-corrected with quantile mapping and used as direct inputs to the hydrological models AWBM, IHACRES, Sacramento, SIMHYD and SMAR-G to project streamflows. The performance of the hydrological models is assessed against 86 streamflow gauges across Tasmania. The SIMHYD model is the least biased (median bias = −3%) while IHACRES has the largest bias (median bias = −22%). We find the hydrological models that best simulate observed streamflows produce similar streamflow projections. There is much greater variation in projections between RCM simulations than between hydrological models. Marked decreases of up to 30% are projected for annual runoff in central Tasmania, while runoff is generally projected to increase in the east. Daily streamflow variability is projected to increase for most of Tasmania, consistent with increases in rainfall intensity. Inter-annual variability of streamflows is projected to increase across most of Tasmania. This is the first major Australian study to use high-resolution bias-corrected rainfall and potential evapotranspiration projections as direct inputs to hydrological models. Our study shows that these simulations are capable of producing realistic streamflows, allowing for increased confidence in assessing future changes to surface water variability.