Intercomparison of soil pore water extraction methods for stable isotope analysis and interpretation of hillslope runoff sources

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 and ¹⁸O 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.     

Bound and mobile soil water isotope ratios are affected by soil texture and mineralogy,whereas extraction method influences their measurement

Questions persist about interpreting isotope ratios of bound and mobile soil water pools, particularly relative to clay content and extraction conditions. Interactions between pools and resulting extracted water isotope composition are presumably related to soil texture, yet few studies have manipulated the bound pool to understand its influence on soil water processes. Using a series of drying and spiking experiments, we effectively labelled bound and mobile water pools in soils with varying clay content. Soils were first vacuum dried to remove residual water, which was then replaced with heavy isotope-enriched water prior to oven drying and spiking with heavy isotope-depleted water. Water was extracted via centrifugation or cryogenic vacuum distillation (at four temperatures) and analysed for oxygen and hydrogen isotope ratios via isotope ratio mass spectrometry. Water from centrifuged samples fell along a mixing line between the two added waters but was more enriched in heavy isotopes than the depleted label, demonstrating that despite oven drying, a residual pool remains and mixes with the mobile water. Soils with higher clay + silt content appeared to have a larger bound pool. Water from vacuum distillation samples have a significant temperature effect, with high temperature extractions yielding progressively more heavy isotope-enriched values, suggesting that Rayleigh fractionation occurred at low temperatures in the vacuum line. By distinctly labelling bound and mobile soil water pools, we detected interactions between the two that were dependent on soil texture. Although neither extraction method appeared to completely extract the combined bound and mobile (total water) pool, centrifugation and high temperature cryogenic vacuum distillations were comparable for both δ²H and δ¹⁸O of soil water isotope ratios.     

“Amount effect” of water isotopes and quantitative analysis of post‐condensation processes

A numerical model is proposed that describes the interaction between raindrops and water vapour near the planetary boundary layer to explain the “amount effect”. This model relates the intensity to the isotopic composition of precipitation. The model resolves raindrop sizes, and explicitly includes: (1) the isotopic equilibration time of raindrops that is drop‐size dependent; (2) raindrop transit times through the atmosphere; and (3) the evolution of the isotopic composition of vapour at various rain rates. At high rain rate, the precipitation through a layer is less equilibrated with the vapour because the isotopic equilibration time is long compared to the fast transit time, and there is a preponderance of large drops, which take longer to equilibrate. The δ¹⁸O of vapour in the lower atmosphere becomes lower as a result of the interaction with these raindrops of low δ¹⁸O, and the degree of depletion of ¹⁸O is higher when precipitation rates are high. The model reproduces time‐series observations of isotopic composition of precipitation in Japan, and a vapour replenishment rate is inferred by either advection or evaporation of about 5% of the precipitation rate. The results could be the basis for a new parameterization of the isotopic equilibration for different precipitation types and rates in General Circulation Models (GCMs). When the model is applied to a GCM, this parameterization is important for places where precipitation occurs at cold temperatures (<15 °C). Copyright © 2007 John Wiley & Sons, Ltd.     

Calibration method affects the measured δ2H and δ18O in soil water by direct H2Oliquid–H2Ovapour equilibration with laser spectroscopy

The direct H₂O_liquid–H₂O_vapour equilibration method utilizing laser spectroscopy (DVE-LS) is a way to measure soil pore water stable isotopes. Various equilibration times and calibration methods have been used in DVE-LS. Yet little is known about their effects on the accuracy of the obtained isotope values. The objective of this study was to evaluate how equilibration time and calibration methods affect the accuracy of DVE-LS. We did both spiking and field soil experiments. For the spiking experiment, we applied DVE-LS to four soils of different textures, each of which was subjected to five water contents and six equilibration times. For the field soil experiment, we applied three calibration methods for DVE-LS to two field soil profiles, and the results were compared with cryogenic vacuum distillation (CVD)-LS. Results showed that DVE-LS demonstrated higher δ²H and δ¹⁸O as equilibration time increased, but 12 to 24 hr could be used as optimal equilibration time. For field soil samples, DVE-LS with liquid waters as standards led to significantly higher δ²H and δ¹⁸O than CVD-LS, with root mean square error (RMSE) of 8.06‰ for δ²H and 0.98‰ for δ¹⁸O. Calibration with soil texture reduced RMSE to 3.53‰ and 0.72‰ for δ²H and δ¹⁸O, respectively. Further, calibration with both soil texture and water content decreased RMSE to 3.10‰ for δ²H and 0.73‰ for δ¹⁸O. Our findings conclude that the calibration method applied may affect the measured soil water isotope values from DVE-LS.     

Sampling soil water along the pF curve for δ2H and δ18O analysis

Soil water stable isotopes are widely used across disciplines (e.g., hydrology, ecology, soil science, and biogeochemistry). However, the full potential of stables isotopes as a tool for characterizing the origin, flow path, transport processes and residence times of water in different eco-, hydro-, and geological compartments has not yet been exploited. This is mainly due to the large variety of different methods for pore water extraction. While recent work has shown that matric potential affects the equilibrium fractionation, little work has examined how different water retention characteristics might affect the sampled water isotopic composition. Here, we present a simple laboratory experiment with two well-studied standard soils differing in their physico-chemical properties (e.g., clayey loam and silty sand). Samples were sieved, oven-dried and spiked with water of known isotopic composition to full saturation. For investigating the effect of water retention characteristics on the extracted water isotopic composition, we used pressure extractors to sample isotopically labelled soil water along the pF curve. After pressure extraction, we further extracted the soil samples via cryogenic vacuum extraction. The null hypothesis guiding our work was that water held at different tensions shows the same isotopic composition. Our results showed that the sampled soil water differed isotopically from the introduced isotopic label over time and sequentially along the pF curve. Our and previous studies suggest caution in interpreting isotope results of extracted soil water and a need to better characterize processes that govern isotope fractionation with respect to soil water retention characteristics. In the future, knowledge about soil water retention characteristics with respect to soil water isotopic composition could be applied to predict soil water fractionation effects under natural and non-stationary conditions. In this regard, isotope retention characteristics as an analog to water retention characteristics have been proposed as a way forward since matric potential affects the equilibrium fractionation between the bound water and the water vapour.     

Stable Isotopes (δ18O, δ2H) of Pore Waters in Clay-Rich Aquitards: A Comparison and Evaluation of Measurement Techniques

Pore water collected from piezometers installed in a thick clay-rich till were used to compare and evaluate four techniques for obtaining δD and δ¹⁸O values in these media. The techniques included mechanical squeezing, centrifugation, azeotropic distillation, and a direct soil-water equilibration technique. Direct CO₂-core equilibration yielded sufficiently accurate and reproducible δ¹⁸O results of pore water in clay-rich tills. In addition, this method eliminated the need for labor-intensive complete extraction of water from the geologic media. Mechanical squeezing and centrifugation produced results similar to direct equilibration. However, both of these methods exhibited a greater degree of variability and were laborious and more time consuming. Small differences in δ¹⁸O values between piezometer water and equilibrated, squeezed, and centhfuged samples suggested that each method collected different fractions of the clay-water reservoir. Although these subtle differences were not conclusive, they did suggest the presence of weakly bound water and highlighted the difference between these three techniques for determining the stable isotopic composition of pore water in clay-rich aquitards. Azeotropic distillation produced a high level of discrepancy in δD andδ¹⁸O results compared to the other methods. Incomplete extraction was considered the most probable cause of this error. The results of this study suggested that direct equilibration is the best method for determining detailed δD and δ¹⁸O values of pore water in clay-rich aquitards.     

Effects of ultrafiltration on salt migration and isotopic composition of pore water in groundwater depression area in Hengshui,NCP

Clay aquitards are semipermeable membranes that allow groundwater flow while retarding solute migration has been researched extensively but also subjected to much debate. At present, there is no evidence of whether the physical and chemical properties of clay soil and the isotopic composition of pore water affect the semipermeable membrane effect. In this study, we collected clay samples from drilling cores (30–90 m) in the Hengshui area located in the North China Plain (NCP), then extracted pore water using a high-pressure squeezing device. Vertical hydrochemical and isotopic profile variation trends for the pore water were revealed using hydrochemical (Cl⁻, Na⁺, Ca²⁺, K⁺, Mg²⁺, and SO₄²⁻) and stable isotopic measurements of H, O and Cl. The results showed that the hydrochemical clay interlayer pore water of the saline aquifer is Cl/SO₄-Na/Mg type and the average total dissolved solids (TDS) are 10.17 g/L. However, the hydrochemical clay aquitard pore water is of the Cl/SO₄-Na/Ca type with an average TDS of 1.90 g/L. The hydrochemical clay interlayer pore water of aquifer II is of Cl-Na/Ca type with an average TDS of 1.10 g/L. Our results showed that the water quality of the aquifer II is not affected by the upper part of the saline aquifer, thus the clay aquitard acts as a significant barrier to salt movement. A polarization layer concentrated in ions was formed between the upper part of the saline aquifer and the clay aquitard. The concentration polarization layer increases the salt-inhibition effect. H, O and Cl isotopic composition results showed significant fractionation. The pore water of aquifer II lacked heavy isotopes (²H, ¹⁸O, ³⁷Cl), but had significant heavy isotope enrichment in the concentrated polarized layer (the δ²H value was −76‰, the δ¹⁸O value was −8.4‰, and the δ³⁷Cl value was 1.59‰). Hyperfiltration thus played a significant role in isotope fractionation.     

Factors controlling diurnal variation in the isotopic composition of atmospheric water vapour observed in the taiga,eastern Siberia

Deciduous forest covers vast areas of permafrost under severe dry climate in eastern Siberia. Understanding the water cycle in this forest ecosystem is quite important for climate projection. In this study, diurnal variations in isotopic compositions of atmospheric water vapour were observed in eastern Siberia with isotope analyses of precipitation, sap water of larch trees, soil water, and water in surface organic layer during the late summer periods of 2006, 2007, and 2008. In these years, the soil moisture content was considerably high due to unusually large amounts of summer rainfall and winter snowfall. The observed sap water δ¹⁸O ranged from ?17.9‰ to ?13.3‰, which was close to that of summer precipitation and soil water in the shallow layer, and represents that of transpired water vapour. On sunny days, as the air temperature and mixing ratio rose from predawn to morning, the atmospheric water vapour δ¹⁸O increased by 1‰ to 5‰ and then decreased by about 2‰ from morning to afternoon with the mixing ratio. On cloudy days, by contrast, the afternoon decrease in δ¹⁸O and the mixing ratio was not observed. These results show that water vapour that transpired from plants, with higher δ¹⁸O than the atmospheric water vapour, contributes to the increase in δ¹⁸O in the morning, whereas water vapour in the free atmosphere, with lower δ¹⁸O, contributes to the decrease in the afternoon on sunny days. The observed results reveal the significance of transpired water vapour, with relatively high δ¹⁸O, in the water cycle on a short diurnal time scale and confirm the importance of the recycling of precipitation through transpiration in continental forest environments such as the eastern Siberian taiga. Copyright © 2012 John Wiley & Sons, Ltd.     

Stable isotopes of atmospheric water vapour and precipitation in the northeast Qinghai‐Tibetan Plateau

Stable water isotopes (δ¹⁸O and δ²H) are an important source signature for understanding the hydrological cycle and altered climate regimes. However, the mechanisms underlying atmospheric water vapour isotopes in the northeast Qinghai‐Tibetan Plateau of central Asia remain poorly understood. This study initially investigated water vapour isotopic composition and its controls during the premonsoon and monsoon seasons. Isotopic compositions of water vapour and precipitation exhibited high variability across seasons, with the most negative average δ¹⁸O values of precipitation and the most positive δ¹⁸O values of water vapour found during the premonsoon periods. Temperature effect was significant during the premonsoon period but not the monsoon period. Both a higher slope and intercept of the local meteoric water line were found during the monsoon period as compared with in the premonsoon period, suggesting that raindrops have been experienced a greater kinetic fractionation process such as reevaporation below the cloud during the premonsoon periods. The δ²H and δ¹⁸O signatures in atmospheric water vapour tended to be depleted with the occurrence of precipitation events especially during the monsoon period and probably as a result of rainout processes. The monthly average contribution of evaporation from the lake to local precipitation was 35.2%. High d‐excess values of water vapour were influenced by the high proportion of local moisture mixing, as indicated by the gradually increasing relative humidity along westerly and Asian monsoon trajectories. The daily observation (observed ε) showed deviations from the equilibrium fractionation factors (calculated ε), implying that raindrops experienced substantial evaporative enrichment during their descent. The average fraction of raindrops reevaporation was estimated to be 16.4± 12.9%. These findings provide useful insights for understanding the interaction between water vapour and precipitation, moisture sources, and help in reconstructing the paleoclimate in the alpine regions.     

Controls on stable isotopic characteristics of water vapour over Thailand

This study examined the weekly water vapour isotopic composition (δ¹⁸O_v) in Thailand. The water vapour was cryogenically collected from eight sites across the country. Two observational samples were collected over one 24-h period each week (a daytime and a night-time sample), from September 2013 to September 2014. The primary aim was to investigate the environmental factors influencing water vapour isotopes. The results revealed differences in water vapour isotopic values between day and night samples. Three periods of depleted δ¹⁸O_v were associated with large-scale convective systems in September, December, and May. The statistical relationship between the climate variables and water vapour isotopes indicated that the amount of precipitation and relative humidity were the primary controls on both diurnal and seasonal isotopic variability. The temperature did not affect the δ¹⁸O_v, mainly because the atmospheric processes are a function of vertical convection rather than temperature in tropical regions. The water vapour deuterium excess (d-excess) showed greater variability in 2013 than in 2014. The d-excess variation reflected the differences in convection occurring in the day and night. In addition, the vapour phase data were combined with the local meteoric water line to identify the local water vapour line and the interaction between the isotopic composition of water vapour and liquid water. The water vapour isotopic patterns paralleled the precipitation isotopes on rainy days because of equilibrium isotopic exchange. Water vapour and precipitation were isotopically similar under low humidity but showed greater differences from each other under wetter conditions. The study results provide insight into water vapour isotopic characteristics in tropical regions and constrain the role of large-scale atmospheric processes relative to isotopic variability of water vapour in Thailand and nearby countries.     

Storage,mixing, and fluxes of water in the critical zone across northern environments inferred by stable isotopes of soil water

Quantifying soil water storage, mixing, and release via recharge, transpiration, and evaporation is essential for a better understanding of critical zone processes. Here, we integrate stable isotope (²H and ¹⁸O of soil water, precipitation, and groundwater) and hydrometric (soil moisture) data from 5 long‐term experimental catchments along a hydroclimatic gradient across northern latitudes: Dry Creek (USA), Bruntland Burn (Scotland), Dorset (Canada), Krycklan (Sweden), and Wolf Creek (Canada). Within each catchment, 6 to 11 isotope sampling campaigns occurred at 2 to 4 sampling locations over at least 1 year. Analysis for ²H and ¹⁸O in the bulk pore water was done for >2,500 soil samples either by cryogenic extraction (Dry Creek) or by direct equilibration (other sites). The results showed a similar general pattern that soil water isotope variability reflected the seasonality of the precipitation input signal. However, pronounced differences among sampling locations occurred regarding the isotopic fractionation due to evaporation. We found that antecedent precipitation volumes mainly governed the fractionation signal, temperature and evaporation rates were of secondary importance, and soil moisture played only a minor role in the variability of soil water evaporation fractionation across the hydroclimatic gradient. We further observed that soil waters beneath conifer trees were more fractionated than beneath heather shrubs or red oak trees, indicating higher soil evaporation rates in coniferous forests. Sampling locations closer to streams were more damped and depleted in their stable isotopic composition than hillslope sites, revealing increased subsurface mixing towards the saturated zone and a preferential recharge of winter precipitation. Bulk soil waters generally comprised a high share of waters older than 14 days, which indicates that the water in soil pores are usually not fully replaced by recent infiltration events. The presented stable isotope data of soil water were, thus, a useful tool to track the spatial variability of water fluxes within and from the critical zone. Such data provide invaluable information to improve the representation of critical zone processes in spatially distributed hydrological models.     

Groundwater and surface water connectivity within the recharge area of Guarani aquifer system during El Niño 2014–2016

Recharge areas of the Guarani Aquifer System (GAS) are particularly sensitive and vulnerable to climate variability; therefore, the understanding of infiltration mechanisms for aquifer recharge and surface run‐off generation represent a relevant issue for water resources management in the southeastern portion of the Brazilian territory, particularly in the Jacaré‐Pepira River watershed. The main purpose of this study is to understand the interactions between precipitation, surface water, and groundwater using stable isotopes during the strong 2014–2016 El Niño Southern Oscillation event. The large variation in the isotopic composition of precipitation (from ?9.26‰ to +0.02‰ for δ¹⁸O and from ?63.3‰ to +17.6‰ for δ²H), mainly associated with regional climatic features, was not reflected in the isotopic composition of surface water (from ?7.84‰ to ?5.83‰ for δ¹⁸O and from ?49.7‰ to +33.6‰ for δ²H), mainly due to the monthly sampling frequency, and groundwater (from ?7.04‰ to ?7.76‰ for δ¹⁸O and from ?49.5‰ to ?44.7‰ for δ²H), which exhibited less variation throughout the year. However, variations in deuterium excess (d‐excess) in groundwater and surface water suggest the occurrence of strong secondary evaporation during the infiltration process, corresponding with groundwater level recovery. Similar isotopic composition in groundwater and surface water, as well as the same temporal variations in d‐excess and line‐conditioned excess denote the strong connectivity between these two reservoirs during baseflow recession periods. Isotopic mass balance modelling and hydrograph separation estimate that the groundwater contribution varied between 70% and 80%, however, during peak flows, the isotopic mass balance tends to overestimate the groundwater contribution when compared with the other hydrograph separation methods. Our findings indicate that the application of isotopic mass balance methods for ungauged rivers draining large groundwater reservoirs, such as the GAS outcrop, could provide a powerful tool for hydrological studies in the future, helping in the identification of flow contributions to river discharge draining these areas.     

Spatio‐temporal heterogeneity in soil water stable isotopic composition and its ecohydrologic implications in semiarid ecosystems

Spatio‐temporal heterogeneity in soil water content is recognized as a common phenomenon, but heterogeneity in the hydrogen and oxygen isotope composition of soil water, which can reveal processes of water cycling within soils, has not been well studied. New advances are being driven by measurement approaches allowing sampling with high density in both space and time. Using in situ soil water vapour probe techniques, combined with conventional soil and plant water vacuum distillation extraction, we monitored the hydrogen and oxygen stable isotopic composition of soil and plant waters at paired sites dominated by grasses and Gambel's oak (Quercus gambelii) within a semiarid montane ecosystem over the course of a growing season. We found that sites spaced only 20 m apart had profoundly different soil water isotopic and volumetric conditions. We document patterns of depth‐ and time‐explicit variation in soil water isotopic conditions at these sites and consider mechanisms for the observed heterogeneity. We found that soil water content and isotopic variability were damped under Q. gambelii, perhaps due in part to hydraulic redistribution of deep soil water or groundwater by Q. gambelii in these soils relative to the grass‐dominated site. We also found some support for H isotope discrimination effects during water uptake by Q. gambelii. In this ecosystem, the soil water content was higher than that at the neighbouring Grass site, and thus, 25% more water was available for transpiration by Q. gambelii compared with the Grass site. This work highlights the role of plants in governing soil water variation and demonstrates that they can also strongly influence the isotope ratios of soil water. The resulting fine‐scale heterogeneity has implications for the use of isotope tracers to study soil hydrology and evaporation and transpiration fluxes to improve understanding of water cycling through the soil–plant–atmosphere continuum.     

Hydrologic characteristics of lake‐ and stream‐side riparian wetted margins in the McMurdo Dry Valleys,Antarctica

Water is a limiting factor for life in the McMurdo Dry Valleys (MDV), Antarctica. The active layer (seasonally thawed soil overlying permafrost) accommodates dynamic hydrological and biological processes for 10–16 weeks per year. Wetted margins (visually wetted areas with high moisture content) adjacent to lakes and streams are potential locations of great importance in the MDV because of the regular presence of liquid water, compared with the rest of the landscape where liquid water is rare. At 11 plots (four adjacent to lakes, seven adjacent to streams), soil particle size distribution, soil electrical conductivity, soil water content and isotopic signature, width of the wetted margin, and active layer thaw depth were characterised to determine how these gradients influence physicochemical properties that determine microbial habitat and biogeochemical cycling. Sediments were generally coarse‐grained in wetted margins adjacent to both lakes and streams. Wetted margins ranged from 1·04 to 11·01 m in average length and were found to be longer at lakeside sites than streamside. Average thaw depths ranged from 0·12 to 0·85 m, and were found to be deepest under lake margins. Lake margins also had much higher soil electrical conductivity, steeper topographic gradients, but more gradual soil moisture gradients than stream margins. Patterns of soil water δ¹⁸O and δD distribution indicate capillary action and evaporation from wetted margins; margin pore waters generally demonstrated isotopic enrichment with distance from the shore, indicating evaporation of soil water. Lake margin pore waters were significantly more negative in D_XS (D_XS = δD‐8δ¹⁸O) than streamside pore waters, indicating a longer history of evaporation there. Differences between lake and stream margins can be explained by the more consistent availability of water to lake margins than stream margins. Differences in margin characteristics between lakes and streams have important consequences for the microbial habitat of these margins and their functional role in biogeochemical cycling at these terrestrial–aquatic interfaces. Copyright © 2009 John Wiley & Sons, Ltd.     

Isotopic composition of precipitation in a topographically steep,seasonally snow‐dominated watershed and implications of variations from the global meteoric water line

The local meteoric water line (LMWL), the functional relationship between locally measured values of δ¹⁸O and δ²H in precipitation, represents the isotopic composition of water entering hydrologic systems. The degree to which the LMWL departs from the global meteoric water line (GMWL), moreover, can reveal important information about meteoric sources of water (e.g. oceanic or terrestrial) and atmospheric conditions during transport. Here we characterize the isotopic composition of precipitation within an experimental watershed in the Western US that is subject to large topographic and seasonal gradients in precipitation. Interpreting the hydrometeorologic and spatial controls on precipitation, we constructed a seasonally weighted LMWL for southwestern Idaho that is expressed by the equation δ²H = 7.40 × δ¹⁸O ? 2.17. A seasonally weighted LMWL that is based on weighting isotopic concentrations by climatic precipitation volumes is novel, and we argue better represents the significant seasonality of precipitation in the region. The developed LMWL is considerably influenced by the semiarid climate experienced in southwest Idaho, yielding a slope and y‐intercept lower than the GMWL (δ²H = 8 × δ¹⁸O + 10). Moderate to strong correlations exist between the isotopic composition of precipitation from individual events and surface meteorologic variables, specifically surface air temperature, relative humidity, and precipitation amount. A strong negative correlation exists between the annual average isotopic composition of precipitation and elevation at individual collection sites, with a lapse rate of ?0.22‰/100 m. Copyright © 2016 John Wiley & Sons, Ltd.     

Land-air boundary environment as recorded by the18O/16O and13C/12C isotope ratios in the shells of land snails

A yearly cycle of carbon and oxygen isotope composition of shells of the Israeli land snailXeropicta vestalis is presented. The¹⁸O/¹⁶O values indicate that the snails use water from the land-air boundary zone. The¹⁸O/¹⁶O ratio of the shells is in isotopic equilibrium with the water condensate from the vapour during the winter months. During the summer months a contribution to the above water from soil water migrating upwards due to evaporation is noticeable. The δ¹³C values indicate that as in marine molluscs, the carbon isotopic composition in land snails is controlled mainly by the aqueous carbonate compound which is in equilibrium with the land-air boundary CO₂.     

A tale of two isotopes: differences in hydrograph separation for a runoff event when using δD versus δ18O

It is often assumed that stable water isotopes (δD and δ¹⁸O) provide redundant information for a given sample of water. In this note we illustrate that the choice of isotope used may influence the resultant hydrograph separation. This is especially true in light of the spatial and temporal variability in the isotopic composition of rainfall water at the catchment scale. We present several possible hydrograph separations based on both δD and δ¹⁸O observed in rainfall for a single runoff event occurring in the southwest USA. This study demonstrates the potential of using both stable water isotopes by showing that δD and δ¹⁸O may provide unique information for catchment hydrologists. We also report on the utility of new technology capable of simultaneous measurements of both δD and δ¹⁸O using off‐axis integrated cavity output spectroscopy (OA‐ICOS) methods. This may be of interest to catchment hydrologists seeking to incorporate this type of equipment into their laboratory. Copyright © 2009 John Wiley & Sons, Ltd.     

Isotopic fractionation induced by a surface effect influences the estimation of the hydrological process of topsoil

Isotopic heterogeneity in soil water has hindered the application of isotope compositions (δ¹⁸O and δ²H) in soil water dynamics. This heterogeneity has been suggested to be caused by soil properties such as organic matter (OM) and clay content. However, this is yet to be verified in field soil. We sampled the organic layer (O-horizon soil) with highly decomposed organic material and the A-horizon soil in western Sichuan, China, and equilibrated these samples with vapour created by unconfined labelling water. The relationship between soil properties and isotopic fractionation (ε_T/U) between unconfined water and the total soil water was used to determine the line-conditioned excess (lc-excess) and source rain of A-horizon field soil by removing the influence of confined water. Equilibration experiments demonstrated a significant isotopic difference between the ε_T/U levels in the A-horizon and O-horizon soils, indicating that OM plays an important role in isotopic fractionation. In field samples, the lc-excess of the unconfined A-horizon water was, on an average, 2.5‰ higher than that of bulk soil water. The average offsets between the annual rain and the estimated source rain of soil water decreased by 5.0 and 0.5‰ for hydrogen and oxygen after removing the influence of confined water. Isotopic heterogeneity should not be ignored while examining the evaporation of soil water, soil source rain, and hence the recent ‘two water worlds’ hypothesis, which is especially true for cases in which the soils contain high levels of OM.     

Characteristics of soil moisture in permafrost observed in East Siberian taiga with stable isotopes of water

Soil moisture and its isotopic composition were observed at Spasskaya Pad experimental forest near Yakutsk, Russia, during summer in 1998, 1999, and 2000. The amount of soil water (plus ice) was estimated from volumetric soil water content obtained with time domain reflectometry. Soil moisture and its δ¹⁸O showed large interannual variation depending on the amount of summer rainfall. The soil water δ¹⁸O decreased with soil moisture during a dry summer (1998), indicating that ice meltwater from a deeper soil layer was transported upward. On the other hand, during a wet summer (1999), the δ¹⁸O of soil water increased due to percolation of summer rain with high δ¹⁸O values. Infiltration after spring snowmelt can be traced down to 15 cm by the increase in the amount of soil water and decrease in the δ¹⁸O because of the low δ¹⁸O of deposited snow. About half of the snow water equivalent (about 50 mm) recharged the surface soil. The pulse of the snow meltwater was, however, less important than the amount of summer rainfall for intra‐annual variation of soil moisture. Excess water at the time just before soil freezing, which is controlled by the amount of summer rainfall, was stored as ice during winter. This water storage stabilizes the rate of evapotranspiration. Soil water stored in the upper part of the active layer (surface to about 120 cm) can be a water source for transpiration in the following summer. On the other hand, once water was stored in the lower part of the active layer (deeper than about 120 cm), it would not be used by plants in the following summer, because the lower part of the active layer thaws in late summer after the plant growing season is over. Copyright © 2002 John Wiley & Sons, Ltd.     

Seasonal connections between meteoric water and streamflow generation along a mountain headwater stream

In snowmelt-driven mountain watersheds, the hydrologic connectivity between meteoric waters and stream flow generation varies strongly with the season, reflecting variable connection to soil and groundwater storage within the watershed. This variable connectivity regulates how streamflow generation mechanisms transform the seasonal and elevational variation in oxygen and hydrogen isotopic composition (δ¹⁸O and δD) of meteoric precipitation. Thus, water isotopes in stream flow can signal immediate connectivity or more prolonged mixing, especially in high-relief mountainous catchments. We characterized δ¹⁸O and δD values in stream water along an elevational gradient in a mountain headwater catchment in southwestern Montana. Stream water isotopic compositions related most strongly to elevation between February and March, exhibiting higher δ¹⁸O and δD values with decreasing elevation. These elevational isotopic lapse rates likely reflect increased connection between stream flow and proximal snow-derived water sources heavily subject to elevational isotopic effects. These patterns disappeared during summer sampling, when consistently lower δ¹⁸O and δD values of stream water reflected contributions from snowmelt or colder rainfall, despite much higher δ¹⁸O and δD values expected in warmer seasonal rainfall. The consistently low isotopic values and absence of a trend with elevation during summer suggest lower connectivity between summer precipitation and stream flow generation as a consequence of drier soils and greater transpiration. As further evidence of intermittent seasonal connectivity between the stream and adjacent groundwaters, we observed a late-winter flush of nitrate into the stream at higher elevations, consistent with increased connection to accumulating mineralized nitrogen in riparian wetlands. This pattern was distinct from mid-summer patterns of nitrate loading at lower elevations that suggested heightened human recreational activity along the stream corridor. These observations provide insights linking stream flow generation and seasonal water storage in high elevation mountainous watersheds. Greater understanding of the connections between surface water, soil water and groundwater in these environments will help predict how the quality and quantity of mountain runoff will respond to changing climate and allow better informed water management decisions.