Liang-Feng Han

Residence times and age distributions of spring waters at the Semmering catchment area, Eastern Austria, as inferred from tritium, CFCs and stable isotopes

The groundwater system in the mountainous area of Semmering, Austria, was studied by environmental tracers in several karst springs. The tracers used included stable isotopes (18O, 2H), tritium (3H) and chlorofluorocarbons (CFCs). The tracers provided valuable information in regard to (1) the mean altitude of the spring catchment areas; (2) the residence time and age distribution of the spring waters; and (3) the interconnection of the springs to a sinkhole. The combination of the stable isotopic data and the topography/geology provided the estimates of the mean altitudes of the catchment areas. Based on the stable isotopic data the recharge temperature of the spring waters was estimated. The smoothing of precipitations isotopic signal in spring discharge provided information on the minimum transit time of the spring waters. Due to short observation time, 3H data alone cannot be used for describing the mean residence time of the karst waters. CFCs, though useful in recognizing the co-existence of young (post-1993) water with old (CFC-free) water, could not be used to resolve age distribution models. It is shown in this article, however, that the combined use of tritium and CFCs can provide a better assessment of models to account for different groundwater age distributions. In Appendix A, a simplified method for collecting groundwater samples for the analysis of CFCs is described. The method provides a real facilitation for fieldwork. Test data are given for this sampling method in regard to potential contamination by atmospheric CFCs.

Reduction of Microliter Amounts of Water with Manganese for D/H Isotope Ratio Measurement by Mass Spectrometry

Abstract For the measurement of deuterium content in natural waters, a rapid and precise analytical technique has been developed for the quantitative conversion of water to hydrogen with manganese as reducing agent. It was found that 8μl of water, 0.8 g of Mn, and a reaction time of 40 minutes at 520°C are the optimal conditions for the conversion reaction. Each sample is reduced individually in a high vacuum reaction vessel with a Teflon stopcock. A set of six samples can be prepared at one time. Analyses of standard water samples gave a reproducibility of ±1%(1[sgrave]).

A Modified Technique for the Preparation of SO2 from Sulphates and Sulphides for Sulphur Isotope Analyses

Abstract A modified technique for the conversion of sulphates and sulphides to SO2 with the mixture of V2O5—SiO2 for sulphur isotopic analyses is described. This technique is more suitable for routine analysis of large number of samples. Modification of the reaction vessel and using manifold inlet system allows to analyse up to 24 samples every day. The modified technique assures the complete yield of SO2, consistent oxygen isotope composition of the SO2 gas and reproducibility of δ34S measurements being within 0.10‰. It is observed, however, oxygen in SO2 produced from sulphides differs in δ18O with respect to that produced from sulphates.

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

ABSTRACT 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.

A compact tritium enrichment unit for large sample volumes with automated re-filling and higher enrichment factor

Tritium (3H) in natural waters is a powerful tracer of hydrological processes, but its low concentrations require electrolytic enrichment before precise measurements can be made with a liquid scintillation counter. Here, we describe a newly developed, compact tritium enrichment unit which can be used to enrich up to 2L of a water sample. This allows a high enrichment factor (>100) for measuring low 3H contents of <0.05TU. The TEU uses a small cell (250mL) with automated re-filling and a CO2 bubbling technique to neutralize the high alkalinity of enriched samples. The enriched residual sample is retrieved from the cell under vacuum by cryogenic distillation at -20°C and the tritium enrichment factor for each sample is accurately determined by measuring pre- and post- enrichment 2H concentrations with laser spectrometry.

A portable membrane contactor sampler for analysis of noble gases in groundwater.

To enable a wider use of dissolved noble gas concentrations and isotope ratios in groundwater studies, we have developed an efficient and portable sampling device using a commercially available membrane contactor. The device separates dissolved gases from a stream of water and collects them in a small copper tube (6 mm in diameter and 100 mm in length with two pinch-off clamps) for noble gas analysis by mass spectrometry. We have examined the performance of the sampler using a tank of homogeneous water prepared in the laboratory and by field testing. We find that our sampling device can extract heavier noble gases (Ar, Kr, and Xe) more efficiently than the lighter ones (He and Ne). An extraction time of about 60 min at a flow rate of 3 L/min is sufficient for all noble gases extracted in the sampler to attain equilibrium with the dissolved phase. The extracted gas sample did not indicate fractionation of helium ((3) He/(4) He) isotopes or other noble gas isotopes. Field performance of the sampling device was tested using a groundwater well in Vienna and results were in excellent agreement with those obtained from the conventional copper tube sampling method.

A simple polymer electrolyte membrane system for enrichment of low-level tritium (3H) in environmental water samples

ABSTRACT Tritium (3H) is an essential tracer of the Earths water cycle; yet widespread adoption of tritium in hydrologic studies remains a challenge because of analytical barriers to quantification and detection of 3H by electrolytic pre-concentration. Here, we propose a simple tritium electrolytic enrichment system based on the use of solid polymer electrolyte membranes (PEMs) that can be used to enrich 3H in 250–3000 mL environmental water samples to a 10-mL final volume. The IAEA PEM-3H system reported here can produce high enrichment factors (>70-fold) and, importantly, removes some of the deterrents to conventional 3H enrichments methods, including the use of toxic electrolysis and neutralization chemicals, spike standards, a complex electrolysis apparatus that requires extensive cooling and temperature controls, and improves precision by eliminating the need for tracking recovery gravimetrics. Preliminary results with varying operating conditions show 3H enrichments to 70-fold and higher are feasible, spanning a wide range of tritium activities from 5 to 150 TU with a precision of ∼4.5 %. Further work is needed to quantify inter-sample memory and to establish lower 3H detection limits. The IAEA PEM-3H system is open source, with 3-D CAD and design files made freely available for adoption and improvement by others.