Evaluation of the Sulfate Dynamics in Groundwater by Means of Environmental Isotopes

Abstract

Elevated sulfate concentrations and their heterogeneous distribution in the drinking water catchment area Torgau-Mockritz (Germany) were investigated by means of multiple isotope signatures such as δ³⁴S, δ¹⁸O-H₂O, δD, tritium, and ⁸⁵Kr. δ³⁴S values of the groundwater sulfate vary between -19…+ 37‰ CDT. No simple correlation exists between sulfate concentrations and δ³⁴S. Superimposition of different sulfur sources and mobilization processes combined with a complicated groundwater movement create a complex distribution pattern. The oxidation of reduced sedimentary sulfur has to be regarded as a main source of dissolved sulfate at least regionally. Tritium and ¹⁴C data revealed that old groundwater can be excluded as source for high sulfate contents. Correlated temporal variations in the concentrations of tritium and sulfate are observed in deeper sampling positions. Highly variable δ¹⁸O and δD, as detected in parts of the catchment area, indicate local influences of surface water infiltration into the aquifer. The spatial distribution of isotope signatures enables the identification of zones with descending younger water or hindered groundwater movement and hence provides useful hints for flow modeling.     

Soil water balance in the Lake Chad Basin using stable water isotopes and chloride of soil profiles

ABSTRACT

The Lake Chad Basin (LCB) is an endorheic transboundary catchment highly vulnerable to drought. For effective groundwater management, recharge areas need identification and replenishment quantification. At present, little research exploring unsaturated zone water flow processes and groundwater recharge are available. In this study, 12 vertical soil profiles were analysed for stable water isotopes and chloride concentration to estimate evaporation and groundwater renewal. Most δ¹⁸O and δ²H isotope profiles reveal typical arid environment patterns, with maximum enrichment at depths between 2.5 and 20?cm and depletion towards the surface (atmospheric influence) and depth (mixing and diffusion). Average annual dry season evaporation rates in Salamat and Waza Logone range from 5 to 30?mm, in Bahr el Ghazal and Northern Lake Chad from 14 to 23?mm. According to the chloride mass balance (CMB), the average annual recharge rate is estimated between 3 and 163?mm in Salamat and Waza Logone and less than 1 mm in Bahr el Ghazal and Northern Lake Chad. Based on the CMB results, potential recharge sites were identified, while estimated soil evaporation corresponds to plant water use at the initial growing stage, which is an important component in irrigation water management.     

Isotopic composition in precipitation and groundwater in the northern mountainous region of the Central Valley of Costa Rica

The linkage between precipitation and recharge is still poorly understood in the Central America region. This study focuses on stable isotopic composition in precipitation and groundwater in the northern mountainous region of the Central Valley of Costa Rica. During the dry season, rainfall samples corresponded to enriched events with high deuterium excess. By mid-May, the Intertropical Convergence Zone poses over Costa Rica resulting in a depletion of ¹⁸O/¹⁶O and ²H/H ratios. A parsimonious four-variable regression model (r^2?=?0.52) was able to predict daily δ¹⁸O in precipitation. Air mass back trajectories indicated a combination of Caribbean Sea and Pacific Ocean sources, which is clearly depicted in groundwater isoscape. Aquifers relying on Pacific-originated recharge exhibited a more depleted pattern, whereas recharge areas relying on Caribbean parental moisture showed an enrichment trend. These results can be used to enhance modelling efforts in Central America where scarcity of long-term data limits water resources management plans.     

Spatial and temporal characteristics of stable isotopes in the Tarim River Basin

By using 233 isotope samples, we investigated the spatial and temporal variations of δ¹⁸O and δ²H in precipitation and surface water, and the contribution of different water sources in the rivers within the Tarim River Basin (TRB), which receives snow/glacier meltwater, groundwater, and rainfall. Our study revealed a similar seasonal pattern of precipitation δ¹⁸O and δ²H at both the north and south edges of the basin, indicating the dominant effect of westerly air masses in the summer and the combined influence of westerly and polar air masses during the winter, although the southern part showed more complex precipitation processes in the summer. River water in the basin has relatively large temporal variations in both δ¹⁸O and δ²H showing a distinct seasonal pattern with lower isotope values in May than in September. Higher d-excess values throughout the year in the Aksu river and the Tizinafu river suggest that water may be intensively recycled in the mountains of the TRB. Based on isotopic hydrograph separation, we found that groundwater is the main water source that discharges the entire basin although individual rivers vary.     

Pleistocene age paleo-groundwater inferred from water-stable isotope values in the central part of the Baltic Artesian Basin

A new data set of δ²H and δ¹⁸O in the groundwater from the central part of the Baltic Artesian Basin is presented. The hydrogeological section is subdivided into stagnation, slow exchange and active exchange zones. Na–Ca–Cl brine found at the deepest part – the stagnation zone – is characterized by δ¹⁸O values above ?5?‰ and δ²H values approaching ?40?‰ with respect to Vienna Standard Mean Ocean Water. The slow exchange zone where waters of mostly intermediate salinity reside is characterized by δ¹⁸O values around ?11.7?‰ and δ²H values around ?85.3?‰. Mean δ¹⁸O and δ²H values of the fresh groundwater in the active water exchange zone are ?11.1 and ?79.9?‰, respectively. Characteristically, the groundwater in the active and slow exchange zone is isotopically more depleted compared with the precipitation values observed, and the depletion increases with depth down to the level where strongly enriched brines are encountered.     

Estimation of groundwater recharge via deuterium labelling in the semi-arid Cuvelai-Etosha Basin,Namibia

The stable water isotope deuterium (²H) was applied as an artificial tracer (²H₂O) in order to estimate groundwater recharge through the unsaturated zone and describe soil water movement in a semi-arid region of northern central Namibia. A particular focus of this study was to assess the spatiotemporal persistence of the tracer when applied in the field on a small scale under extreme climatic conditions and to propose a method to obtain estimates of recharge in data-scarce regions. At two natural sites that differ in vegetation cover, soil and geology, 500?ml of a 70?% ²H₂O solution was irrigated onto water saturated plots. The displacement of the ²H peak was analyzed 1 and 10 days after an artificial rain event of 20 mm as well as after the rainy season. Results show that it is possible to apply the peak displacement method for the estimation of groundwater recharge rates in semi-arid environments via deuterium labelling. Potential recharge for the rainy season 2013/2014 was calculated as 45 mm a^?1 at 5.6 m depth and 40 mm a^?1 at 0.9 m depth at the two studied sites, respectively. Under saturated conditions, the artificial rain events moved 2.1 and 0.5 m downwards, respectively. The tracer at the deep sand site (site 1) was found after the rainy season at 5.6 m depth, corresponding to a displacement of 3.2 m. This equals in an average travel velocity of 2.8 cm d^?1 during the rainy season at the first site. At the second location, the tracer peak was discovered at 0.9 m depth; displacement was found to be only 0.4 m equalling an average movement of 0.2 cm d^?1 through the unsaturated zone due to an underlying calcrete formation. Tracer recovery after one rainy season was found to be as low as 3.6?% at site 1 and 1.9?% at site 2. With an in situ measuring technique, a three-dimensional distribution of ²H after the rainy season could be measured and visualized. This study comprises the first application of the peak displacement method using a deuterium labelling technique for the estimation of groundwater recharge in semi-arid regions. Deuterium proved to be a suitable tracer for studies within the soil–vegetation–atmosphere interface. The results of this study are relevant for the design of labelling experiments in the unsaturated zone of dry areas using ²H₂O as a tracer and obtaining estimations of groundwater recharge on a local scale. The presented methodology is particularly beneficial in data-scarce environments, where recharge pathways and mechanisms are poorly understood.     

Stable H and O isotope variations reveal sources of recharge in Dhofar,Sultanate of Oman

Due to the ability of stable water isotopes to characterize the origin of water and connected processes of groundwater recharge, we used the isotope variations of hydrogen and oxygen in different water sources for assessing the recharge process in the Dhofar region. δ¹⁸O and δ²H of precipitation, spring water, and groundwater cover a range from ?10 to +2 and from ?70 to +7?‰ (vs Vienna Standard Mean Ocean Water), respectively, and correlate in a linear relationship close to the Global Meteoric Water Line. No obvious evaporation processes are detected. A clear signal of the recent precipitation is given by the annual monsoon. The monsoon signal is confirmed by several springs existing in the south at the foot of the Dhofar mountains and sources at Gogub above 450?m and Tawi Atir at 650?m above sea level. They occur here first in the form of water intercepted by trees as stemflow and throughflow. The isotope signature of groundwater in the Dhofar mountains reflects the climatic conditions at the time of recharge and the lithological features of the limestone matrix. To the north, the isotope patterns of the groundwater are continuously depleted from the monsoon signal along the outcropping aquifer D (Lower Umm Er Radhuma). Here, a more negative signature towards the wells in the Najd desert region was observed. Cyclone water that flooded wadis in the Dhofar region occasionally, as observed in November 2011, falls isotopically into the same range as we observed in the fossil groundwater. Taking into account the different sources of precipitation and groundwater and thus a clear distinction of the isotopic composition of the water sources, we conclude a recharge process divided into a southward and a northward component in the Dhofar region.     

Deuterium,Oxygen-18 and Salt Content of Drinking Water Sources in Cairo

The contineous increase of population in Cairo exceeding 10 millions inhabitants lead to the search for supplementary potable water resources in addition to the Nile River which is the principle drinking water source. Groundwater represents the main supplementary source. Evaluation of the groundwater feeding the so-called El-America Water Treatment Station which is one of the biggest potable water supplies at the northern of Cairo was carried out. Chemical and isotopic techniques were applied to estimate the suitability of this groundwater for drinking purposes. The chemical analysis includes the determination of sodium, potasium, calcium and magnesium concentrations in addition to those of chlorides, sulphates, bicarbonates and silicates, while the isotopic analysis includes oxygen-18 and deuterium. The overall chemical- and isotopic investigations determined the conditions at which the examined groundwater is suitable for drinking purposes.     

Erfahrungen und Ergebnisse der Isotopenanwendung im Industriezweig Braunkohle

This paper presents results of a study carried out in order to assess the applicability of ³²Si for groundwater dating. Measurements of ³²Si in soil samples of the unsaturated zone, of drainage waters and plant material give a basis for estimating the ³²Si initial concentration in groundwater. Different aquifers with groundwater of young and moderate ages have been selected for groundwater studies. For obtaining independent age information tritium was found to be a suitable reference isotope. A quantitative interpretation of the ³²Si data is generally complicated by geochemical processes, preferably in the unsaturated zone. Favourable conditions concerning the use of ³²Si in hydrogeology seem to exist in phreatic sandy aquifers, in limestone aquifers, and, depending on the thickness and composition of the unsaturated zone, in sandstone aquifers. Further improvements of the ³²Si method needs a better understanding of the geochemical processes affecting this isotope.     

Hydrogeochemical and isotope study of perched aquifers in the Cuvelai-Etosha Basin,Namibia

A hydrogeochemical and stable isotope study (²H and ¹⁸O) was carried out in the Cuvelai-Etosha Basin in order to characterize available groundwater and to identify possible recharge mechanisms for the perched aquifers. Data were collected during seven field campaigns between 2013 and 2015 from a total of 24 shallow and deep groundwater hand-dug wells. In the investigated groundwaters, hydrogencarbonate is the dominating anion in both well types, whereas cations vary between calcium and magnesium in deep wells, and sodium and potassium in shallow wells. Groundwater chemistry is controlled by dissolution of carbonate minerals, silicate weathering and ion exchange. Stable isotopic composition suggests that deep groundwater is recharged by high-intensity/large rainfall events, whereas the shallow wells can even be recharged by less-intense/small rainfall events. Water in deep wells reflect a mixture of water influenced by evaporation during or before infiltration and water that infiltrated through fast preferential pathways, whereas shallow wells are strongly influenced by evaporation. The findings of this research contribute to improve the understanding of hydrogeochemistry, recharge paths and temporal variations of perched aquifers.     

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.     

Use of Isotope Methods for the Development of a New Structural-Geological Model in the Finne Region

Abstract

Since the 1960s intensive isotope hydrogeological studies have been carried out in the Finne mountain range between Herrengosserstedt in Thuringia and the River Unstrut near Karsdorf in Saxony-Anhalt. The new railway line Erfurt-Leipzig/Halle, a part of the traffic projects German Union - Railway-No. 8-, will cross this area with two tunnels, each of which is 6 km long. The tunnelling of the Middle Bunter rocks on the west side involves the crossing of an area with deep wells used for drinking water supply.

To clarify the hydrodynamic situation in this area, the planning company for railway construction German Union (PB DE) contracted Trischler und Partner to carry out an extensive exploration programme. This programme included not only investigations using the isotopes ²H, ¹⁸O, ³H, ¹³C and ¹⁴C, but also single measurements of chlorofluorocarbons (CFC) and a multitude of hydrochemical analyses.

Because of stratum related ground water sampling, an aquifer related evaluation of the investigation results was possible. Based on these results a fundamentally new structural-geological model for the investigation area was developed. In addition to its great importance for the tunnel planning, with the new model it will be possible to solve urgent questions concerning the drinking water supply in this region.     

Hydrogeochemical and isotopic characterisation of groundwater in a sand-dune phreatic aquifer on the northeastern coast of the province of Buenos Aires,Argentina

This contribution presents the hydrochemical and isotopic characterisation of the phreatic aquifer located in the Partido de la Costa, province of Buenos Aires, Argentina. In the sand-dune barrier geomorphological environment, groundwater is mainly a low-salinity Ca-HCO₃ and Na-HCO₃-type, being in general suitable for drinking, whereas in the continental plain (silty clay sediments), groundwater is a Na-Cl type with high salinity and unsuitable for human consumption. The general isotopic composition of the area ranges from?6.8 to?4.3 ‰ for δ¹⁸O and from?39 to?21 ‰ for δ²H, showing that rainwater rapidly infiltrates into the sandy substrate and reaches the water table almost without significant modification in its isotopic composition. These analyses, combined with other chemical parameters, made it possible to corroborate that in the eastern area of the phreatic aquifer, there is no contamination from marine salt water.     

Use of isotopes to study floodplain wetland and river flow interaction in the White Volta River basin,Ghana

Floodplain wetlands influence the timing and magnitude of stream responses to rainfall. In managing and sustaining the level of water resource usage in any river catchment as well as when modelling hydrological processes, it is essential that the role of floodplain wetlands in stream flows is recognised and understood. Existing studies on hydrology within the Volta River basin have not adequately represented the variability of wetland hydrological processes and their contribution to the sustenance of river flow. In order to quantify the extent of floodwater storage within riparian wetlands and their contribution to subsequent river discharges, a series of complementary studies were conducted by utilising stable isotopes, physical monitoring of groundwater levels and numerical modelling. The water samples were collected near Pwalugu on the White Volta River and at three wetland sites adjacent to the river using the grab sampling technique. These were analysed for ¹⁸O and ²H. The analysis provided an estimate of the contribution of pre-event water to overall stream flow. In addition, the variation in the isotopic composition in the river and wetland water samples, respectively, revealed the pattern of flow and exchange of water between the wetlands and the main river system.     

Carbon isotopic analyses for source apportionment studies of the greenhouse gases carbon dioxide and methane

We investigated the environmental water sources used in mid-summer by three Sonoran Desert phreatophytic riparian tree species, Salix gooddingii, Populus fremontii, and the exotic Tamarix spp., at sites that differed in water table depth. Salix gooddingii was most sensitive to water table decline, as evidenced by lower predawn water potentials. Although P. fremontii was less sensitive to water table decline than S. gooddingii, its leaf gas exchange was the most responsive to atmospheric water stress imposed by high leaf-to-air vapor pressure deficit. Tamarix spp. was least sensitive to water table decline and showed no reduction of predawn water potential over the measured range of depth to groundwater. Comparison between D/H of xylem and sampled environmental water sources suggest that S. gooddingii and P. fremontii used groundwater at most sites with no change in water source as depth to groundwater varied. In contrast, xylem D/H of Tamarix spp. was depleted in deuterium compared to groundwater at most sites, suggesting use of water from an unsampled source, or discrimination against deuterium during water uptake. This study highlights the difficulty in sampling all water sources in large-scale studies of riparian ecosystems with complex subsurface hydrogeology.     

Electrodialytic desalination of brackish water: effect of process parameters and water characteristics

The aim of this work is to study the desalination of brackish water using a laboratory scale electrodialysis cell. The influence of several parameters, such as flow rates, initial feed concentration, applied voltage and circulation mode on process efficiency were studied. This efficiency is evaluated by the demineralization rate, ionic flux transport and current efficiency. In this study, experiments were carried out on synthetic brackish water solutions prepared from sodium chloride salts. The concentrations of these solutions are varying from 0.5 to 3 g L^?1. The process was applied for the treatment of real brackish water sample with total dissolved salts ～5 g L^?1. The concentrations of different species in the obtained treated water are below the amounts recommended by World Health Organization for drinking water.     

238U and total radioactivity in drinking waters in Van province,Turkey

As part of the national survey to evaluate natural radioactivity in the environment, concentration levels of total radioactivity and natural uranium have been analysed in drinking water samples. A survey to study natural radioactivity in drinking waters was carried out in the Van province, East Turkey. Twenty-three samples of drinking water were collected in the Van province and analysed for total α, total β and ²³⁸U activity. The total α and total β activities were counted by using the α/β counter of the multi-detector low background system (PIC MPC-9604), and the ²³⁸U concentrations were determined by inductively coupled plasma-mass spectrometry (Thermo Scientific Element 2). The samples were categorised according to origin: tap, spring or mineral supply. The activity concentrations for total α were found to range from 0.002 to 0.030 Bq L^?1 and for total β from 0.023 to 1.351 Bq L^?1. Uranium concentrations ranging from 0.562 to 14.710 μg L^?1 were observed in drinking waters. Following the World Health Organisation rules, all investigated waters can be used as drinking water.     

Paleoclimatology

The Lamas Basin is an area covering ～4400 km² situated on the eastern Mediterranean coast of Turkey covered with highly karstified limestone and dolomitic limestone from the Miocene and Mesozoic age, respectively. Owing to the area’s low karstification basement, groundwater in the karst aquifer circulates deep from the surface towards the springs along the coast as well as to the submarine springs. This study aims working out the salinization level and recharge characteristics of the Lamas Basin using environmental isotopes techniques. In the study, the data collected previously to discover, in general terms, the groundwater characteristics within the area are reanalyzed to fulfil the purpose of the study. In conclusion, it is found that the down gradient karst springs discharging along the Mediterranean coast mostly contain groundwater contributions from higher altitudes with depleted δ¹⁸O and δ²H compositions. The δ¹⁸O-altitude effect was determined as approximately?0.12 ‰/100 m which may indicate sea-spray intrusion towards inland. As a result, the salinization level of coastal springs changes ranging between 1.2 % and 17.0 %. Owing to the seawater encroachment, Ca–HCO₃ water type changes to Na–HCO₃ or Na-Cl water by the cation exchange during the dry period. As the unique freshwater potential extends along the coastal area, the groundwater production should be exploited in a way that seawater encroachment is kept at minimum.     

Helicobacter pylori determination in non-municipal drinking water and epidemiological findings

Background.?Studies conducted in Europe as well as in North and South America have tried to link Helicobacter pylori colonization with the drinking water supply, especially since H. pylori is known to survive quite well in water.

Methods.?In 2000, a cohort of 1884 grade-two children from two rural counties surrounding the city of Leipzig, Germany (77.4% of the 1991/1992 birth cohort) were tested for H. pylori colonization using the [¹³C]urea breath test. A parent-completed questionnaire elicited details on living conditions and lifestyle habits including questions on the children's drinking water from sources other than public water supplies, swimming in natural waters, etc.

In a second independent study, samples of well water, taken from 157 private wells still used in the two counties, were being tested for the presence of H. pylori, using polymerase chain reaction (PCR) method to determine relevant target DNA fragments of H. pylori.

Results.?In county I, 5.7% of the children and in county II 6.6% tested H. pylori-positive. Cluster analyses of the questionnaire data in both counties pointed to ‘drinking water from other than municipal sources’, as the closest H. pylori-associated cluster variable. The cluster estimations were supported by odds ratio (OR) calculations with an OR?=?16.4 (95% confidence interval (CI) 3.1,…,88.5) for county I and OR?=?4.0 (95% CI 1.3,…,12.4) for county II.

The PCR analyses showed H. pylori DNA fragments in 10.8% of the wells in county I and 9.2% in county II. The detection limit was set at 10 DNA copies corresponding to 125?bacteria/L, the average infestation of these wells was 931?bacteria/L.

Conclusion.?Despite the fact that the microbiological and epidemiological data do not correspond except that both studies were conducted in the same geographical areas, the independent findings of H. pylori in well water in the same general areas where children do seem to drink water other than from the public water supply suggests that water may be an important source of H. pylori infection.     

Environmental Isotopes as a Useful Tool for Studies at Mixed Uranium Mill Tailings Sites

Abstract

Groundwaters in the area of a mixed landfill (domestic waste above uranium mill tailings) in Dresden (Saxony, Germany) were investigated for their isotope signatures to distinguish between different groundwater types. To determine between the two contamination sources (waste and uranium mill tailings) a multi parameter interpretation was done using both, the main hydrochemical parameters the radionuclides ²³⁴U, ²³⁸U, ²²⁶Ra and ²²²Rn as well as the environmental isotopes of the elements hydrogen, oxygen, sulphur and carbon.

The seepage water from the landfill shows higher δ³⁴S, δ¹⁸O and tritium values as the inflow. The tritium values give an idea about water movement in the dump and mean residence time of the groundwater. The water in the dump shows varying δ¹³C values which indicate different processes occurring in the dump.