Intercomparison of soil pore water extraction methods for stable isotope analysis

Measurements of δ²H and δ¹⁸O composition of pore waters in saturated and unsaturated soil samples are routinely performed in hydrological studies. A variety of in‐situ and lab‐based pore water extraction methods for the analysis of the stable isotopes of water now exist. While some have been used for decades (e.g. cryogenic vacuum extraction) others are relatively new, such as direct vapour equilibration or the microwave extraction technique. Despite their broad range of application, a formal and comprehensive intercomparison of soil water extraction methods for stable isotope analysis is lacking and long overdue. Here we present an intercomparison among five commonly used lab‐based pore water extraction techniques (high pressure mechanical squeezing, centrifugation, direct vapour equilibration, microwave extraction, and cryogenic extraction). We applied these extraction methods to two physicochemically different soil types that were dried and rewetted with water of known isotopic composition at three different water contents. Our results showed that the extraction approach can have a significant effect on pore water isotopic composition as all methods exhibited significant deviations from the spiked reference water, depending secondarily on the soil type and soil water content. Most pronounced, cryogenic water extraction showed large deviations from the spiked reference water, whereas mechanical squeezing and centrifugation provided results closest to the spiked water for both soil types. We also compared results for each extraction method – where liquid water was obtained – on both an OA‐ICOS and IRMS. Differences between these two analytical instruments were negligible for these organic compound‐free waters. We suggest that users of soil water extraction approaches carefully choose an extraction technique that is suitable for the specific research question, adapted to the dominant soil type and water content of the study. Copyright © 2016 John Wiley & Sons, Ltd.     

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.     

Estimation of mean water transit time on a steep hillslope in South Korea using soil moisture measurements and deuterium excess

A method for estimating daily mean transit time (DMTT) within a soil layer was proposed using field measurements of soil moisture. Vertical profiles of soil moisture time series were used for storage estimation. Water fluxes were evaluated through matrix and bypass flow. Variations in soil moisture and soil thickness were used to evaluate matrix flow. Exponential decay in depth of macropores was also used for bypass flow approximation. DMTT evaluation was compared to results obtained from a stable water isotope model using two years of data acquired on a steep granite hillslope in the Sulmachun watershed, South Korea. Various uncertainties in transit time evaluation such as model structure, non‐stationary assumption and data acquisition of existing approaches can be accounted for in the proposed methodology, and the flowpath contribution can be further configured in conjunction with hydrometric measurements. Probability density functions of isotope analyses were partially explained by transit time distributions that were based on soil moisture measurements. Supplementary sensitivity analyses for uncertainty configurations indicate that matrix flow is the primary process in determining transit time distribution while the impact of bypass flow is minor. The feasibility of a DMTT approach over isotope‐based methodologies highlights not only the strength of this proposed method, both in cost and time, but also its further application potential for existing soil moisture measurements. Copyright © 2013 John Wiley & Sons, Ltd.     

Isotopic analysis of water sources of mountainous plant uptake in a karst plateau of southwest China

Ecosystem in the karst region of southwest China is very fragile due to a very limited amount of water storage for plant uptake in the thin and rocky soils underlain by rock fractures. Plants in these karst regions are thought to take water from the soils and shallow fractured rock zone (subcutaneous zone) as well. However, the role of subcutaneous water in maintaining karst vegetation remains unclear, and proportions of the water sources for plant uptake in different environment conditions are unknown. In this study, five typical species of plants at two sites were selected in a karst plateau of Qingzhen, central Guizhou Province of China. Proportions of the possible water sources contributed for the plant uptake from two soil layers and subcutaneous zone were determined on the basis of δD and δ¹⁸O values of plant stem water, soil water and subcutaneous water. The analysis reveals that most plants take water from the soil layers and the subcutaneous zone as well, but proportions of these water contributions for plant uptake vary seasonally and depend on site‐specific conditions and plant species. Plant uptake of the subcutaneous water for all species averages less than 30% of the total monthly amount in June and September, compared with more than 60% in dry December. Plants tend to take a larger proportion of water from the upper soil layer at the bush site than at the forest site in June and September (63 vs 28% in July; 66 vs 54% in September for all species in average). In December, however, 98% of water is taken from the subcutaneous zone at the bush site which is much greater than 68% at the forest site. Compared to deciduous arbor, evergreen shrub takes a greater proportion of subcutaneous water in the December drought. Copyright © 2011 John Wiley & Sons, Ltd.     

淮南采煤沉陷区积水水文地球化学及氢氧稳定同位素特征

以安徽淮南采煤沉陷积水为研究对象,通过样品采集与测试,研究不同沉陷年限及类型积水水文地球化学和氢氧稳定同位素组成特征及影响因素.结果表明：（1）研究区水化学类型主要为Cl-Na、HCO₃·Cl-Na型,沉陷积水中常量离子主要来源于蒸发岩溶解和硅酸盐风化,受蒸发作用和人为活动的影响明显,水化学组成随沉陷时间和类型变化不大.（2）淮南大气降水线方程为：δD=8.85δ¹⁸O+18.73,沉陷区积水氢氧稳定同位素值在淮南大气降水线右下方依次分布并接近降水线,表明沉陷积水主要来源于大气降水.（3）在降水稀释、水体蒸发及地下水补给的作用下,随着沉陷年限的增加,积水中重同位素越来越贫化,同一年限不同类型的积水同位素值变化较小.     

A study of soil water movement combining soil water potential with stable isotopes at two sites of shallow groundwater areas in the North China Plain

In the shallow groundwater areas of the North China Plain (NCP), precipitation infiltration and evapotranspiration in the vertical direction are the main processes of the water cycle, in which the unsaturated zone plays an important role in the transformation process between precipitation and groundwater. In this paper, two typical sites in Cangzhou (CZ) and Hengshui (HS) of Hebei province with shallow water tables were selected to analyse the relationship among precipitation, soil water and groundwater. At each site, precipitation, soil water at depths 10, 20, 30, 50, 70, 100, 150, 200, 300 cm, and groundwater were sampled to analyse the stable isotope compositions of hydrogen and oxygen. The soil water potentials at the corresponding depths were observed. Although the climates at the two sites are similar, there are some differences in the infiltration process, soil water movement and groundwater recharge sources. Evaporation occurred at the upper depths, which led to the decrease of soil potential and the enrichment of heavy isotopes. At the CZ site, precipitation infiltrated with piston mode, and an obvious mixture effect existed during the infiltration process. Preferential flow may exist in the soil above 100 cm depth. However, at the HS site soil water moved in piston mode, and groundwater was mainly recharged by precipitation. When precipitation recharged the groundwater it experienced a strong evaporation effect. The results of the soil water movement mechanism provides the transformation relationship among precipitation, soil water and groundwater in the middle and eastern NCP. Copyright © 2009 John Wiley & Sons, Ltd.     

Estimating water fluxes in the critical zone using water stable isotope approaches in the Groundnut and Ferlo basins of Senegal

Sustainable water management in semi-arid agriculture practices requires quantitative knowledge of water fluxes within the soil-vegetation-atmosphere system. Therefore, we used stable-isotope approaches to evaluate evaporation (E_a), transpiration (T_a), and groundwater recharge (R) at sites in Senegal's Groundnut basin and Ferlo Valley pasture region during the pre-monsoon, monsoon, and post-monsoon seasons of 2021. The approaches were based upon (i) the isothermal evaporation model (for quantifying E_a); (ii) water and isotope mass balances (to partition E_a and T_a for groundnut and pasture); and (iii) the piston displacement method (for estimating R). E_a losses derived from the isothermal evaporation model corresponded primarily to Stage II evaporation, and ranged from 0.02 to 0.09 mm d⁻¹ in the Groundnut basin, versus 0.02–0.11 mm d⁻¹ in Ferlo. At the groundnut site, E_a rates ranged from 0.01 to 0.69 mm d⁻¹; T_a was in the range 0.55–2.29 mm d⁻¹; and the T_a/ET_a ratio was 74%–90%. At the pasture site, the ranges were 0.02–0.39 mm d⁻¹ for E_a; 0.9–1.69 mm d⁻¹ for T_a; and 62–90% for T_a/ET_a. The ET_a value derived for the groundnut site via the isotope approach was similar to those from eddy covariance measurements, and also to the results from the previous validated HYDRUS-1D model. However, the HYDRUS-1D model gave a lower T_a/ET_a ratio (23.2%). The computed groundwater recharge for the groundnut site amounted to less than 2% of the local annual precipitation. Recommendations are made regarding protocols for preventing changes to isotopic compositions of water in samples that are collected in remote arid regions, but must be analysed days later. The article ends with suggestions for studies to follow up on evidence that local aquifers are being recharged via preferential pathways.     

Evidence for variations in cryogenic extraction deuterium biases of plant xylem water across foundational northeastern US trees

Measurements of oxygen and hydrogen isotopes in plant xylem water (²H, ¹⁸O) have helped to redefine conceptual and numerical models of the hydrological cycle and understand how plants compete for subsurface water. Recent experiments have shown that Cryogenic Vacuum Extraction (CVE) of plant xylem water can result in a δ²H bias. We tested if CVE δ²H-biases varied significantly across seven foundational northeastern US forest trees with a series of tree core rehydration experiments. Our analysis demonstrated that CVE δ²H-biases were well predicted by sample gravimetric water content and varied significantly with tree species identity. We show that species-level δ²H-bias corrections can result in substantially different understandings of plant water uptake and transpiration versus uncorrected data or generic bias corrections. This research demonstrates an urgent need for the critical evaluation of CVE for plant water extraction. In the absence of a stronger understanding of CVE δ²H-biases, we recommend that xylem water δ²H observations should not be used in plant water uptake studies.     

Use of stable water isotopes to assess sources and influences of slope groundwater on slope failure

This study employs stable oxygen and hydrogen isotopes as natural tracers to assess the headwater of a landslide next to a drainage divide and the importance of the slope's headwater in the study area. The study is undertaken near Wu‐She Township in the mountains of central Taiwan. Because a reservoir is located on the other side of the divide, this study evaluates the relationship between the reservoir water and headwater of the landslide as well. Over a 1‐year period, water samples from September 2008 to September 2009, including local precipitation (LP), Wu‐She Reservoir's water (WSRW), slope groundwater (SGW), upper‐reach stream water (USTW), and down‐reach stream water (DSTW), were analysed for deuterium (δD) and oxygen (δ¹⁸O) stable isotopes. Results indicate that WSRW is the predominant component in SGW: approximately 70% of SGW originates from WSRW and 30% from LP based on a two end‐member mass‐balance mixing model for δ¹⁸O. The similar two end‐member mixing model is also employed to assess the contributions of USTW and SGW to DSTW. Model results indicate that SGW is the major source of DSTW with a contribution of about 67%. Accordingly, about 47% of DSTW sources from the WSRW. In short, owing to reservoir leakage, WSRW contributes the greater part of both SGW and DSTW. Plentiful WSRW in SGW threatens the stability of the slope in the divide area. To avoid subsequent continuous slope failure, necessary mitigation steps are required. Copyright © 2011 John Wiley & Sons, Ltd.     

Preliminary attempt to distinguish the domesticated pigs from wild boars by the methods of carbon and nitrogen stable isotope analysis

Despite great achievements in the origins of domestic pigs made by the methods of zooarchaeology and molecular biology, how to scientifically distinguish the domesticated pigs from wild boars during the early stage of pig domestication is still poorly understood. Compared to wild boar’s diets which come from the natural environment, the diets of domestic pigs are more easily influenced by human feeding activities. Therefore, in principle, exploration of the dietary differences among pigs and under-standing the impact on pig diets fed by humans can have great potential to differentiate between wild boars and domesticated pigs. To reveal dietary differences among pigs and distinguish the domesticated pigs from wild boars based on comparison with the diets of humans and other animals, we analyzed the carbon and nitrogen stable isotopes of human bones from Xiaojingshan Site and animal bones from Yuezhuang Site, both of which belong to Houli Culture in Shandong Province and date to about 8500-7500 years ago. The mean δ¹³C value ((−17.8 ± 0.3)‰) and δ¹⁵N value ((9.0±0.6)‰) in human collagen indicate that although millet agriculture began it was not the main subsistence strategy as millets are typical of C₄ plants and that humans made a living mainly by gathering, hunting or raising some domesticated animals. The δ¹³C value (−16.1‰) and δ¹⁵N value (6.9‰) in the bovine suggest that C₃ plants were dominant in its diet with some C₄ plants complemented. The fish has lower δ¹³C value (−24.9‰) and higher δ¹⁵N value (8.8‰) than the bovine, which is the characteristic of the isotopic values from Eurasian freshwater fish. Based on the differences in carbon and nitrogen isotope values, the pigs can be divided into three groups. A group, composed of two pigs, has low δ¹³C values (−18.1‰, −20.0‰) and low δ¹⁵N values (4.7‰, 6.0‰). B group, only one pig, has the highest δ¹³C value (−10.6‰) and mediate δ¹⁵N value (6.4‰). As for the C group, also only one pig, low δ¹³C value (−19.0‰) and the highest δ¹⁵N value (9.1‰) are observed. Previous studies on the stable isotopes from modern or ancient wild boars’ bones have suggested that C₃ plants are predominated in their diets and that their δ¹⁵N values are close to those in herbivores and far from those in carnivores. Based on the comparison with the isotope values from humans, the wild boars and the domestic pigs from Xipo Site in Henan 6000-5500 years ago and Kangjia Site in Shaanxi 4500-4000 years ago, we conclude that A pig group belongs to wild boars while B and C groups can be attributed to domesticated pigs. Supported by Max-Planck Society and Chinese Academy of Sciences, Knowledge Innovation Program of the Chinese Academy of Sciences (Grant No. KJCX3.SYW.N12), National Natural Science Foundation of China (Grant No. 40702003) and President Funding of Graduate University of Chinese Academy of Sciences     

C and N stable isotope analysis of human and animal bones at the Beiqian site

The Beiqian site, located in Jimo city, Qingdao, went through three archaeological excavations, and a large number of human and animal bones in the Dawenkou culture and the Zhou Dynasty period were unearthed. By carbon and nitrogen stable isotope analysis, the diet of ancestors is expected to be recovered, and the domesticated plants and animals will be discussed. The investigated results showed that the food structure of ancestors in both periods included food crops, mainly C4 foods, and meat, mainly marine shellfish and livestock. For domestic pigs, they mainly eat C3 plants, and were affected by the lifestyle of ancestors. This study also showed that the diet of ancestors is the shellfish rather than marine fish despite the Beiqian site is located near the shoreline. We can conclude that the diet of ancestors in Dawenkou culture period included millet crops (C4 plants), shellfish, marine food, and livestock, representing the lifestyle of farming, domestication, and fishing, supplemented by hunting. In the Zhou dynasty period the meat resource was enriched by domesticated animals and marine fisheries, and the living conditions were significantly improved.     

Ionic and stable isotope chemistry as indicators of water sources to the Upper Mendoza River basin,Central Andes of Argentina

The Mendoza River is mainly dependent on the melting of snow and ice in the Upper Andes. Since predicted changes in climate would modify snow accumulation and glacial melting, it is important to understand the relative contributions of various water sources to river discharge. The two main mountain ranges in the basin, Cordillera Principal and Cordillera Frontal, present differences in geology and receive differing proportions of precipitation from Atlantic and Pacific moisture sources. We propose that differences in the origin of precipitation, geology and sediment contact times across the basin generate ionic and stable isotopic signatures in the water, allowing the differentiation of water sources. Waters from the Cordillera Principal had higher salinity and were more isotopically depleted than those from the Cordillera Frontal. Stable isotope composition and salinity differed among different water sources. The chemical temporal evolution of rivers and streams indicated changes in the relative contributions of different sources, pointing to the importance of glacier melting and groundwater in the river discharge.     

洱海悬浮颗粒物和表层沉积物有机碳氮同位素来源特征及水质指示意义

为探究湖泊水体悬浮颗粒物和沉积物有机碳、氮来源及水质指示意义,分析了2013-2014年洱海悬浮颗粒物和表层沉积物有机碳同位素(δ13C)、氮同位素(δ15N)和C/N比值时空变化特征及与水质的关系.结果 表明:①洱海悬浮颗粒物δ13C、C/N、δ15N在旱、雨季差异显著(P＜0.05),旱季变化范围分别为-31.75...     

Spatial and temporal variations of actual soil water repellency and their influence on surface runoff

The increase of surface runoff at the plot scale caused by soil water repellency is a generally accepted phenomenon. However, to improve the understanding of the effect of water repellency on runoff at the catchment scale, spatio‐temporal dynamics of water repellency have to be analysed in more detail. The experimental setup of this study allowed the investigation of the relationship between water repellency and runoff generation on Quaternary and Tertiary sandy substrates while ensuring similar conditions in terms of terrain characteristics, meteorological and vegetation‐free conditions on both areas. Measurements of water drop penetration time and contact angle were carried out over a period from September 2003 to December 2005. Spatial variability of actual soil water repellency was related to heterogeneity of substrate and geomorphologic units, variations in time were related with the seasons and their meteorological conditions. To relate variable degrees of actual water repellency to surface runoff generation, both variables were measured in parallel at the plot scale (1 m × 1 m) and at the hillslope scale from September 2004 to December 2005. Soil water repellency of the Tertiary sands showed a temporal variability depending on the season, with the highest degree during summer and autumn. Variation of hydrophobicity between the seasons caused higher runoff coefficients in summer and autumn. Spatial heterogeneity of the soil water repellency revealed lower values in fine‐textured erosion rills and higher values for interrills and top areas. The measured runoff coefficients decreased from the scale of microplots to the hillslope scale due to infiltration in hydrophilic rills on the hillslope. The results suggest that improved hydrological modelling approaches on water‐repellent soils can be based on a geomorphological subdivision of the catchment area and seasonally varying infiltration parameters. Copyright © 2007 John Wiley & Sons, Ltd.     

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.     

Flow dynamics of groundwater and soil water in the former heap Gessenhalde at the uranium mining area of Ronneburg: a stable isotope approach

Stable isotopes, ²H_water, ¹⁸O_water as well as ¹⁸O_sulphate and ³⁴S_sulphate, were used to study the flow system of shallow groundwater and soil water at the base area of a former leaching heap at the uranium mining area of Ronneburg, Germany. The flow paths and water‐retention times were estimated by comparison of δ²H and δ¹⁸O values in groundwater and soil water to the δ²H and δ¹⁸O signature of precipitation, giving distinctive inputs of summer or winter precipitation. The points of measuring the groundwater were divided into three categories with different flow conditions: rapid flow, stagnant conditions and a transition zone by hierarchical cluster analysis of δ²H and δ¹⁸O values of groundwater. The transit time of groundwater in the rapid flow area is less than 6 months, whereas water in the stagnant zone is stored for at least 1 year. In soil water, a clear response to different input signals is detectable only in the 30‐cm horizon (retention time is about 6 months), whereas at deeper levels a mixing with older water is taking place. The isotopic composition of the dissolved sulphate was used to identify oxidation of sulphides as the source of sulphate. Copyright © 2010 John Wiley & Sons, Ltd.