AgF desalination procedure for the routine determination of oxygen and hydrogen isotopic composition of saline waters and brines

The routine methods for stable oxygen and hydrogen isotope analysis of water involve water–CO₂ gas equilibration and water reduction on hot metal (e.g. Zn, Cr, U) and subsequent mass spectrometric analysis of the evolved gases of CO₂ and H₂ for ¹⁸O/¹⁶O and ²H/¹H ratios, respectively. Precise determination of the isotopic composition of water in brines with application of these standard methods is still problematic and technically often impossible due to detrimental influence of dissolved salts. The new method of brine desalination presented in this study overcomes the problem of the isotope salt effects encountered during the application of the routine techniques for the determination of the isotopic composition of high saline waters. The procedure combines two technical steps: (i) the chemical precipitation of Mg and Ca ions as insoluble non-hydroscopic fluorides, and (ii) the vacuum distillation of water from solution–precipitate mixture. The application of simple vacuum distillation allows full extraction of water and dehydration of remaining salts in a temperature range from 300 to 350?°C without hydrogen and oxygen isotope fractionation. The precision and accuracy of δ¹⁸O and δ²H determination of saline waters and brines with prior application of AgF desalination procedure is comparable with that usually obtained for fresh waters.     

Comparison of pore water samplers and cryogenic distillation under laboratory and field conditions for soil water stable isotope analysis*

We used pore water samplers (PWS) to sample for isotope analysis (1) only water, (2) soil under laboratory conditions, and (3) soil in the field comparing the results with cryogenic extraction (CE). In (1) and (2), no significant differences between source and water extracted with PWS were detected with a mean absolute difference (MAD) always lower than 2?‰ for δ²H and 1?‰ for δ¹⁸O. In (2), CE water was more enriched than PWS-extracted water, with a MAD respect to source water of roughly 8?‰ for δ²H and 4?‰ for δ¹⁸O. In (3), PWS water was enriched relative to CE water by 3?‰ for δ²H and 0.9?‰ for δ¹⁸O. The latter result may be due to the distinct water portions sampled by the two methods. Large pores, easily sampled by PWS, likely retain recent, and enriched, summer precipitation while small pores, only sampled by CE, possibly retain isotopically depleted water from previous winter precipitation or irrigation inputs. Accuracy and precision were greater for PWS relative to CE. PWS is therefore suggested as viable tool to extract soil water for stable isotope analysis, particularly for soils used in this study (sandy and silty loams).     

Isotopic composition of atmospheric moisture from pan water evaporation measurements

A continuous and reliable time series data of the stable isotopic composition of atmospheric moisture is an important requirement for the wider applicability of isotope mass balance methods in atmospheric and water balance studies. This requires routine sampling of atmospheric moisture by an appropriate technique and analysis of moisture for its isotopic composition. We have, therefore, used a much simpler method based on an isotope mass balance approach to derive the isotopic composition of atmospheric moisture using a class-A drying evaporation pan. We have carried out the study by collecting water samples from a class-A drying evaporation pan and also by collecting atmospheric moisture using the cryogenic trap method at the National Institute of Hydrology, Roorkee, India, during a pre-monsoon period. We compared the isotopic composition of atmospheric moisture obtained by using the class-A drying evaporation pan method with the cryogenic trap method. The results obtained from the evaporation pan water compare well with the cryogenic based method. Thus, the study establishes a cost-effective means of maintaining time series data of the isotopic composition of atmospheric moisture at meteorological observatories. The conclusions drawn in the present study are based on experiments conducted at Roorkee, India, and may be examined at other regions for its general applicability.     

Accuracy and precision of a laser-spectroscopy approach to the analysis of δ2H and δ18O in human urine

The isotope ratio analysis of body water often involves large sample numbers and lengthy sample processing. Here we demonstrate the ability of isotope ratio infrared spectroscopy (IRIS) to rapidly and accurately analyse the isotope ratios of water in urine. We analysed water extracted from human urine using traditional isotope ratio mass spectrometry (IRMS) and compared those values with IRIS-analysed extracted water and un-extracted urine. Regression analyses for δ²H and δ¹⁸O values between (1) extracted water analysed via IRMS and IRIS and (2) urine and extracted water analysed via IRIS were significant (R ²=0.99). These results indicate that cryogenic distillation of urine was not required for an accurate estimate of the isotopic composition of urine when using IRIS.     

Isotope fractionation of sandy-soil water during evaporation – an experimental study

Soil samples containing water with known stable isotopic compositions were prepared. The soil water was recovered by using vacuum/heat distillation. The experiments were held under different conditions to control rates of water evaporation and water recovery. Recoveries, δ¹⁸O and δ²H values of the soil water were determined. Analyses of the data using a Rayleigh distillation model indicate that under the experimental conditions only loosely bound water is extractable in cases where the recovery is smaller than 100?%. Due to isotopic exchange between vapour and remaining water in the micro channels or capillaries of the soil matrix, isotopic fractionation may take place under near-equilibrium conditions. This causes the observed relationship between δ²H and δ¹⁸O of the extracted water samples to have a slope close to 8. The results of this study may indicate that, in arid zones when soil that initially contains water dries out, the slope of the relationship between δ²H and δ¹⁸O values should be close to 8. Thus, a smaller slope, as observed by some groundwater and soil water samples in arid zones, may be caused by evaporation of water before the water has entered the unsaturated zone.     

Online induction heating for determination of isotope composition of woody stem water with laser spectrometry: a methods assessment

Application of stable isotopes of water to studies of plant–soil interactions often requires a substantial preparatory step of extracting water from samples without fractionating isotopes. Online heating is an emerging approach for this need, but is relatively untested and major questions of how to best deliver standards and assess interference by organics have not been evaluated. We examined these issues in our application of measuring woody stem xylem of sagebrush using a Picarro laser spectrometer with online induction heating. We determined (1) effects of cryogenic compared to induction-heating extraction, (2) effects of delivery of standards on filter media compared to on woody stem sections, and (3) spectral interference from organic compounds for these approaches (and developed a technique to do so). Our results suggest that matching sample and standard media improves accuracy, but that isotopic values differ with the extraction method in ways that are not due to spectral interference from organics.     

Stable water isotope patterns in a climate change hotspot: the isotope hydrology framework of Corsica (western Mediterranean)

The Mediterranean is regarded as a region of intense climate change. To better understand future climate change, this area has been the target of several palaeoclimate studies which also studied stable isotope proxies that are directly linked to the stable isotope composition of water, such as tree rings, tooth enamel or speleothems. For such work, it is also essential to establish an isotope hydrology framework of the region of interest. Surface waters from streams and lakes as well as groundwater from springs on the island of Corsica were sampled between 2003 and 2009 for their oxygen and hydrogen isotope compositions. Isotope values from lake waters were enriched in heavier isotopes and define a local evaporation line (LEL). On the other hand, stream and spring waters reflect the isotope composition of local precipitation in the catchment. The intersection of the LEL and the linear fit of the spring and stream waters reflect the mean isotope composition of the annual precipitation (δ_P) with values of?8.6(±0.2) ‰ for δ¹⁸O and?58(±2) ‰ for δ²H. This value is also a good indicator of the average isotope composition of the local groundwater in the island. Surface water samples reflect the altitude isotope effect with a value of?0.17(±0.02) ‰ per 100 m elevation for oxygen isotopes. At Vizzavona Pass in central Corsica, water samples from two catchments within a lateral distance of only a few hundred metres showed unexpected but systematic differences in their stable isotope composition. At this specific location, the direction of exposure seems to be an important factor. The differences were likely caused by isotopic enrichment during recharge in warm weather conditions in south-exposed valley flanks compared to the opposite, north-exposed valley flanks.     

Isotopic fingerprint of the middle Olt River basin,Romania

One of the most important tributaries of the Danube River in Romania, the Olt River, was characterized in its middle catchment in terms of the isotopic composition using continuous flow–isotope ratio mass spectrometry (CF–IRMS). Throughout a period of 10 months, from November 2010 to August 2011, water samples from the Olt River and its more important tributaries were collected in order to investigate the seasonal and spatial isotope patterns of the basin waters. The results revealed a significant difference between the Olt River and its tributaries, by the fact that the Olt River waters show smaller seasonal variations in the stable isotopic composition and are more depleted in ¹⁸O and ²H. The waters present an overall enrichment in heavy isotopes during the warm seasons.     

Temporal and spatial distribution of isotopes in river water in Central Europe: 50 years experience with the Austrian network of isotopes in rivers

The Austrian network of isotopes in rivers comprises about 15 sampling locations and has been operated since 1976. The Danube isotope time series goes back to 1963. The isotopic composition of river water in Central Europe is mainly governed by the isotopic composition of precipitation in the catchment area; evaporation effects play only a minor role. Short-term and long-term isotope signals in precipitation are thus transmitted through the whole catchment. The influence of climatic changes has become observable in the long-term stable isotope time series of precipitation and surface waters. Environmental ³H values were around 8 TU in 2015, short-term ³H pulses up to about 80 TU in the rivers Danube and March were a consequence of releases from nuclear power plants. The complete isotope data series of this network will be included in the Global Network of Isotopes in Rivers database of the International Atomic Energy Agency (IAEA) in 2017. This article comprises a review of 50 years isotope monitoring on rivers and is also intended to provide base information on the (isotope-)hydrological conditions in Central Europe specifically for the end-users of these data, e.g. for modelling hydrological processes. Furthermore, this paper includes the 2006–2015 supplement adding to the Danube isotope set published earlier.     

Accuracy and precision of a laser-spectroscopy approach to the analysis of δ²H and δ¹⁸O in human urine

The isotope ratio analysis of body water often involves large sample numbers and lengthy sample processing. Here we demonstrate the ability of isotope ratio infrared spectroscopy (IRIS) to rapidly and accurately analyse the isotope ratios of water in urine. We analysed water extracted from human urine using traditional isotope ratio mass spectrometry (IRMS) and compared those values with IRIS-analysed extracted water and un-extracted urine. Regression analyses for δ2H and δ1?O values between (1) extracted water analysed via IRMS and IRIS and (2) urine and extracted water analysed via IRIS were significant (R2=0.99). These results indicate that cryogenic distillation of urine was not required for an accurate estimate of the isotopic composition of urine when using IRIS.     

Determination of delta2H and delta18O in saline oil-associated waters: the question of simple vacuum distillation of water samples prior to isotopic analyses

The paper deals with analytical and procedural aspects of delta18O and delta2H determination in saline oil-associated waters. The main objective of the study was to show experimentally the qualitative and quantitative applicability of the simple vacuum distillation of saline oil-associated waters while routine procedures of water isotopic analyses are applied. Additionally, two standard off-line techniques of delta2H determination in water - the zinc and the chromium method - have been compared. Each time a typical isotope salt effect has been tracked on the Dead Sea water. The results clearly show that application of the simple vacuum distillation improve the accuracy and reproducibility of delta2H determinations, especially in chromium off-line technique which appeared to be more sensitive to water salinity. The simple vacuum distillation does not improve the quality of delta18O determinations in the range of water salinities studied. Its application to high concentrated brines (for example, Dead Sea water) decreases the time of equilibration but still propagate the isotopic error connected with low water activity (in the case of 18O/16O ratio) and the incomplete water extraction from the remaining salts (in the case of 2H/1H ratio); in consequence, its time-consuming application seems to be baseless.     

Influence of air pollution and site conditions on trends of carbon and oxygen isotope ratios in tree ring cellulose

Oxygen and carbon isotopic compositions of tree ring cellulose (delta13Ccell and delta18Ocell) were measured for pines growing at four sites in east Germany. Three sites differed markedly in soil water availability within a short distance and the fourth site served as a reference. The choice of the sites was guided by the desire to detect effects of air pollution on the long-term trend of isotopic compositions and to examine the influence of soil water availability on the relationship between the carbon and oxygen isotope ratios. Locations in east Germany are particularly well suited for the study of pollution effects because there was a steady increase in environmental contamination until the German Reunification in 1990, followed by a sharp decline due to the implementation of stricter environmental standards. The long-term trend of delta13Ccell showed an extraordinary increase in the period 1945-1990 and a rapid decrease after 1990, whereas delta18Ocell remained nearly constant. The increase of delta13Ccell is explained by secondary fractionation caused by phytotoxicity of SO2. Two effects are mainly responsible for the secondary fractionation under SO2 exposure: increase of dark respiration, and changes in photosynthate allocation and partitioning. Both effects do not influence delta18Ocell. Furthermore, a significant positive correlation between the year-to-year variations of carbon and oxygen isotope ratios (delta13Cresid and delta18Oresid) has been found for all sites. The slopes of the relationship between delta13Cresid and delta18Oresid differ insignificantly. It is concluded that this relationship is not influenced by soil water availability but by climatic variables.     

Isotopic fingerprints of the Lake Żabińskie (NE Poland) hydrological system on contemporary carbonates precipitated in the lake

An isotopic monitoring was undertaken in 2012–2014 at Lake ?abińskie (Mazurian Lakeland, NE Poland). The aim was to identify the factors and processes controlling an isotopic composition of the lake water and to explore the mechanism responsible for recording the climatic signal in stable isotope composition of deposited carbonates. δ¹⁸O and δ²H in the precipitation, lake water column, inflows and outflow, δ¹⁸O and δ¹³C in the carbonate fraction of sediments trapped in the water column were recorded with monthly resolution. A relationship between δ¹⁸O and δ²H in local precipitation was used to estimate the local meteoric water line. The dataset obtained for the water enabled to identify the modification of the water’s isotopic composition due to evaporation, connected with seasonal lake water stratification and mixing patterns. Statistically significant correlation coefficients suggest that the δ¹⁸O of the carbonate fraction in the sediment traps depends on the δ¹⁸O of rainfall water and on air temperature. The fractionation coefficient α shows that in summer months the carbonate precipitation process is closest to equilibrium. As expected for an exorheic lake, no significant correlation was observed between δ¹⁸O and δ¹³C in precipitated carbonate.     

Direct equilibration of soil water for delta(18)O analysis and its application to tracer studies

Current methods for stable oxygen isotopic (delta (18)O) analysis of soil water rely on separation of water from the soil matrix before analysis. These separation procedures are not only time consuming and require relatively large samples of soil, but also have been shown to introduce a large potential source of error. Current research at Queen's University Belfast is focused on using direct equilibration of CO(2) with the pore water to eliminate this extraction step using the automated Multiprep system and a Micromass Prism III isotope ratio mass spectrometer (IRMS). The findings of this research indicate the method is less time consuming, more reliable, and reproducible to within accepted limits (+/-0.1% per thousand delta (18)O). In this study the direct equilibration method is used to analyse delta (18)O tracer profiles in the unsaturated zone of field soils, concurrently with chloride tracer profiles, which can be used to assess infiltration rates and mechanisms through the unsaturated zone. Copyright 1999 John Wiley & Sons, Ltd.     

Influence of earthworms on the sulfur turnover in the soil

Abstract The effects of earthworm activity on the concentration and isotopic composition of total sulfur in soils was investigated using batch experiments. Two ecologically different lumbricid species, the anecic Lumbricus terrestris and the endogeic Aporrectodea caliginosa, were used. The earthworms were fed birch leaves, beech leaves, cattle manure or mixed plant litter. All food sources differed isotopically (δ(34)S) from the soil (Parabraunerde). As a reference, one experiment was carried out without additional food. The experimental results show, that both earthworm species influence the total S-content and the δ(34)S-values in the soil by digestion of the different food sources. The differences in the total S-content of the earthworm tissues and in the S-isotopic composition of the casts can be attributed to the ecological differences between the earthworm species.     

Hekla cold springs (Iceland): groundwater mixing with magmatic gases

We have analysed the chemical and stable isotope compositions of four spring waters situated just northwest of the Hekla volcano, where cold water emerges from the base of the lava flows. The stable isotope ratios of water (H, O), dissolved inorganic carbon (C) and sulphate (S) were used to determine whether magmatic gases are mixing with the groundwater. The waters can be characterised as Na-HCO₃ type. The results show that deep-seated gases mix with groundwater, substantially affecting the concentration of solutes and the isotopic composition of dissolved carbon and sulphate.     

Carbon stable isotope composition of modern and archaeological Cornelian cherry fruit stones: a pilot study

The carbon stable isotope content of Cornelian cherry stones collected from wild tree stands in Serbia, SE Europe, was measured using elemental analyser-isotope ratio mass spectrometry, with the aim of recording natural carbon isotope composition of the fruit stones and its possible variation. The results show a significant variation in the carbon isotope values; we identified several environmental factors that, along with a number of other possible determinants, likely contributed to this variation. The obtained data are compared with the measurement of carbon isotope content of an archaeological specimen of Cornelian cherry stone discovered at the Neolithic site of Vin?a (ca. 5600–4500 BC) in Serbia. Notwithstanding the limitedness of the data and the complexity surrounding carbon fractionation and the isotopic variation, it is suggested that the differences/similarities in carbon isotope ratios between modern and archaeological Cornelian cherry stones, when measured for much larger assemblages, could potentially offer a glimpse into growing conditions of Cornelian cherry trees in the past.     

Tree species of the Central Amazon and soil moisture alter stable isotope composition of nitrogen and oxygen in nitrous oxide evolved from soil

The use of stable isotopes of N and O in N2O has been proposed as a way to better constrain the global budget of atmospheric N2O and to better understand the relative contributions of the main microbial processes (nitrification and denitrification) responsible for N2O formation in soil. This study compared the isotopic composition of N2O emitted from soils under different tree species in the Brazilian Amazon. We also compared the effect of tree species with that of soil moisture, as we expected the latter to be the main factor regulating the proportion of nitrifier- and denitrifier-derived N2O and, consequently, isotopic signatures of N2O. Tree species significantly affected delta15N in nitrous oxide. However, there was no evidence that the observed variation in delta15N in N2O was determined by varying proportions of nitrifier- vs. denitrifier-derived N2O. We submit that the large variation in delta15N-N2O is the result of competition between denitrifying and immobilizing microorganisms for NO3(-). In addition to altering delta15N-N2O, tree species affected net rates of N2O emission from soil in laboratory incubations. These results suggest that tree species contribute to the large isotopic variation in N2O observed in a range tropical forest soils. We found that soil water affects both 15N and 18O in N2O, with wetter soils leading to more depleted N2O in both 15N and 18O. This is likely caused by a shift in biological processes for 15N and possible direct exchange of 18O between H2O and N2O.     

Fractionation of Oxygen and Hydrogen Isotopes at the Hydrate Gas forming in the Sea Sediments

The paper gives data on isotope composition of interstitial and near-bottom waters sampled in a region of gas-hydrate formation in the Sea of Okhotsk. The studies shows that heavy isotope of oxygen and hydrogen is used in gas-hydrate formation, with the result that isotope composition of its constitution water constitutes δ¹⁸O = +1.99‰, δD = +23‰ relatively to SMOW. Formation of autogenic carbonates leads to isotope exchange with interstitial water wich, in turn, changes its primary isotope composition in the direction of increasing of O-18 content. The near-bottom waters are isotope-light relatively to the SMOW standard and to the mean isotope composition of interstitial water in the studied region of gas-hydrate spreading.