Paul Koeniger

Freshwater lenses as archive of climate, groundwater recharge, and hydrochemical evolution: Insights from depth‐specific water isotope analysis and age determination on the island of Langeoog, Germany

The age stratification of a freshwater lens on the island of Langeoog, Germany, was reconstructed through depth-specific sampling and groundwater dating using the tritium-helium method. The stratification is strongly affected by the land use and resulting differences in recharge rates. Infiltration at the dune tops is significantly lower than in the valleys, due to repellency of the dry sand. Dune valleys contribute up to four times more groundwater recharge per area than other areas. Housing development in dune areas might therefore significantly decrease the available fresh groundwater. The freshwater column shows a distinct increase of stable isotope values with decreasing depths. Hence, the freshwater lens contains a climate archive which reflects changing environmental conditions at the time of recharge. Combined with tritium-helium dating, this pattern could be matched to climate records which show an increase of the temperature at the time of recharge and rainfall rates during the last 50 years. The spatial and temporal developments of water chemistry during the passage through the lens follow a marked pattern from a sodium and chloride-dominated rainwater of low conductivity to a more mineralized sodium bicarbonate water type, caused by dissolution of carbonate shells close to the surface and subsequent ion exchange of calcium for sodium in the deeper parts.

Mineral mediated isotope fractionation of soil water

RATIONALE The ability to recover the isotopic signature of water added to soil samples that have previously been oven-dried decreases with the increasing presence of silt and clay. The effects on the isotopic signature of water associated with physicochemical soil properties are not yet fully understood, for either hydration or dehydration of soil samples. METHODS The soil sample chemistry and the crystallinity of minerals were measured by X-ray fluorescence and X-ray diffraction. The organic carbon and the cation-exchange capacity were also determined. Water of known isotopic signature was used to spike an oven-dried substrate and subsequently extracted by cryogenic vacuum extraction at a temperature of 105°C. In addition, the soils were oven-dried at 205°C and water extractions were also performed at 205°C. The isotopic signatures of the water samples were determined by cavity-ring-down spectrometry. RESULTS The isotope effects caused by the cryogenic vacuum extraction method applied to soils with elevated clay content were reduced. First, by increasing the extraction temperature to 205°C, we improved the precision of the cryogenic vacuum extraction method and the recovery of the known isotopic signature of the spike water. Secondly, the post-correction of data based on the physicochemical soil properties and a common extraction temperature of 105°C improved the measurement trueness. CONCLUSIONS The isotopic signature of soil water is influenced by mineral-water interaction. During the hydration of clay, different minerals deplete free water in heavy isotopes. The extracted soil water (dehydration water) gathered from clay-rich soils is generally more depleted in the heavy isotopes than the spike water, making results obtained for different soil types difficult to compare. Isotope effects observed at the mineral-water interface highlight potential explanations for eco-hydrological separation of water pools. Copyright

An Analysis of Precipitation Isotope Distributions across Namibia Using Historical Data.

Global precipitation isoscapes based on the Global Network for Isotopes in Precipitation (GNIP) network are an important toolset that aid our understanding of global hydrologic cycles. Although the GNIP database is instrumental in developing global isoscapes, data coverage in some regions of hydrological interest (e.g., drylands) is low or non-existent thus the accuracy and relevance of global isoscapes to these regions is debatable. Capitalizing on existing literature isotope data, we generated rainfall isoscapes for Namibia (dryland) using the cokriging method and compared it to a globally fitted isoscape (GFI) downscaled to country level. Results showed weak correlation between observed and predicted isotope values in the GFI model (r2 < 0.20) while the cokriging isoscape showed stronger correlation (r2 = 0.67). The general trend of the local cokriging isoscape is consistent with synoptic weather systems (i.e., influences from Atlantic Ocean maritime vapour, Indian Ocean maritime vapour, Zaire Air Boundary, the Intertropical Convergence Zone and Tropical Temperate Troughs) and topography affecting the region. However, because we used the unweighted approach in this method, due to data scarcity, the absolute values could be improved in future studies. A comparison of local meteoric water lines (LMWL) constructed from the cokriging and GFI suggested that the GFI model still reflects the global average even when downscaled. The cokriging LMWL was however more consistent with expectations for an arid environment. The results indicate that although not ideal, for data deficient regions such as many drylands, the unweighted cokriging approach using historical local data can be an alternative approach to modelling rainfall isoscapes that are more relevant to the local conditions compared to using downscaled global isoscapes.

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.

Spatiotemporal patterns of stable isotopes and hydrochemistry in springs and river flow of the upper Karkheh River Basin, Iran

Karst springs of the Zagros Mountains contribute a significant amount to agricultural and human water demands of western and south-western Iran. For an adequate management of available water resources in semi-arid and arid regions, sufficient hydrological monitoring is needed, and hydro-chemical and isotope hydrological data provide important additional information. About 350 water samples were collected from precipitation, river water, and karst springs of the upper part of the Karkheh River Basin (20,895 km2) located between 33°35′ and 34°55′ North and 46°22′ and 49°10′ East with elevations ranging from 928 to 3563 m above sea level. Sampling was conducted in monthly time resolution from August 2011 to July 2012. All samples were analysed for hydro-chemical parameters (pH, electrical conductivity, and major ions) and stable isotopes (deuterium, oxygen-18). Isotope values of precipitation indicate a local meteoric water line (Zagros MWL δ2H=6.8 δ18O+10.1; R2=0.99) situated between the Mediterranean MWL and Global MWL. Spring and river water isotope values vary between−7.1 and−4.1 ‰, and−38 and−25 ‰ for δ18O and δ2H, respectively, responding to winter snowmelt and evaporation. This work implements stable isotopes and hydro-chemical information of springs and river water to understand hydrological and hydro-geological interrelations in karstic semi-arid areas and helps to improve the current water resources management practices of western Iran.

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

ABSTRACT 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.

Stable isotope signatures of meteoric water in the Cuvelai-Etosha Basin, Namibia: Seasonal characteristics, trends and relations to southern African patterns

ABSTRACT The study area is the Namibian part of the Cuvelai-Etosha Basin (CEB), located in central northern Namibia. The CEB is home to 40 % of Namibia’s population, and most of the people live in rural areas. These people depend on both surface and groundwater resources which are limited in this dryland (mean annual rainfall ranging from 250 to 550 mm/a). The isotopic signatures of δ18O and δ2H from water samples (n = 61) collected over a course of 9 years from various research projects and existing (but mainly unpublished) data of meteoric water of the CEB (10 sites) were evaluated and local meteoric water lines (LMWLs) developed. Further, the data is discussed in the context of seasonal characteristics and trends and compared to available data from the Global Network of Isotopes in Precipitation (GNIP) for the southern African region. Our results extend the portfolio of previously published LMWLs for southern Africa and provide a more precise baseline for any isotope-based study in that region. The slope of the LMWL from the GNIP stations correlates with latitude. This correlation cannot be found within the CEB. The dominant control on the isotopic signature of the CEB of precipitation is seasonal.

Stable isotope based mean catchment altitudes of springs in the Lebanon Mountains

Stable isotopes of water are known to provide information on mean altitudes of spring recharge areas which is an important parameter for groundwater resources management especially in karstic environments. Very often a lack of precipitation input data is limiting the possibility for an appropriate estimation of mean catchment altitudes. In the Jeita spring catchment, Lebanon, a characterization of precipitation input was possible with samples collected at six stations at varying altitudes (88 amount weighed monthly samples). A local meteoric water line for the Jeita spring catchment (Jeita-LMWL) was characterized as δ2H = 6.04 * δ18O + 8.45 (R2 = 0.92) for a two year observation period between October 2012 and September 2014. Integral samples from the snow layer were collected at 22 sites at altitudes ranging from 1,000 to 2,300 m above sea level at the end of February 2012 and February 2013, when snow height reached a maximum of more than 6 m at the highest peak in the catchment. Water samples were continuously collected from six springs (Jeita, Kashkoush, Labbane, Assal, Afqa, and Rouaiss). Jeita spring water samples were collected additionally in daily time steps during the snowmelt season in 2012. Mean isotope values of the sampled springs range from -6.8 ‰ to -8.2 ‰, and from -33 ‰ to -44 ‰, for δ18O and δ2H, respectively. The stable isotope data shows that input variability (space and time, snow cover and rainfall) has direct impacts on mean altitude estimates of spring catchments. A more profound interpretation of spring response to rainfall for six local springs in the Lebanon Mountains was possible in comparison to four earlier described springs collected in the Anti-Lebanon Mountains in Syria.