Stable isotope patterns of German rivers with aspects on scales, continuity and network status.

In Germany, river monitoring for tritium started in the early 1970s. Today this monitoring network consists of 50 stations and includes stable isotopes. The stable isotope time series to the end of 2021 are at least four years and for some stations up to 30 years long. Daily river water samples were collected during an extraordinary dry season from October 2018 until end of January 2019 from six selected stations of the Rhine and five stations of the Elbe basin. The most dominating stable isotope effects in river water are the seasonal and altitude effects, but also a continental effect is visible. The isotopes indicate snow and ice melt contributions in the Rhine and Danube during the summer months and a consecutive dilution of these signals by mixing with tributary rivers. Close to the coasts in northern Germany, stable isotope patterns reflect influence of seawater and tides. Daily patterns during the dry season 2018/2019 surprisingly do not exhibit extreme changes but rather trends of enhanced groundwater contribution. Long-term continual data across scales are important for comparing and identifying hydrological processes in German river basins of different size and mean catchment altitudes, and highlight the benefits of a co-organized national network.

Evaporation loss along the Calueque-Oshakati Canal in the Cuvelai-Etosha Basin (Northern Namibia): evidence from stable isotopes and hydrochemistry.

Since 1973, Kunene River water has been carried from the Calueque reservoir in Angola along a 160 km open concrete canal to the town of Oshakati in the central part of the Cuvelai-Etosha Basin and has been supplying drinking water to the most densely populated rural area of Namibia. Despite its importance for the region, intra-seasonal water quality and the technical condition of the canal are not routinely checked. Water samples were collected during four field campaigns right before the onset of the rainy season (November 2013 and 2014), and after the rainy season (June 2014 and May 2015), at 16 sites along the canal for stable water isotopes (deuterium, oxygen-17 and oxygen-18) and hydrochemical analyses. The isotope patterns and chemical composition of the canal water is discussed in comparison to local rain, Kunene source water, surface water and groundwater. Clear isotope enrichment indicates evaporative loss of water. A Craig-Gordon model was used to estimate water loss. The loss increases with distance from the source with a maximum of up to 10 %, depending on the season. The results are discussed in context of water availability, vulnerability and water resources management in this water-scarce area.

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

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.

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

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.

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.

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 ((2)H) was applied as an artificial tracer ((2)H2O) 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% (2)H2O solution was irrigated onto water saturated plots. The displacement of the (2)H 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 (2)H 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 (2)H2O 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 km(2)) 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 δ(2)H=6.8 δ(18)O+10.1; R(2)=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 δ(18)O and δ(2)H, 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.

An inexpensive, fast, and reliable method for vacuum extraction of soil and plant water for stable isotope analyses by mass spectrometry.

The stable isotopes of water (hydrogen and oxygen isotopes) are of utmost interest in ecology and the geosciences. In many cases water has to be extracted directly from a matrix such as soil or plant tissue before isotopes can be analyzed by mass spectrometry. Currently, the most widely used technique for water is cryogenic vacuum extraction. We present a simple and inexpensive modification of this method and document tests conducted with soils of various grain size and tree core replicates taken on four occasions during 2010. The accuracies for sandy soils are between 0.4‰ and 3‰ over a range of 21‰ and 165‰ for δ(18)O and δ(2)H, respectively. Spiking tests with water of known isotope composition were conducted with soil and tree core samples; they indicate reliable precision after an extraction time of 15 min for sandy soils. For clayey soils and tree cores, the deviations were up to 0.63‰ and 4.7‰ for δ(18)O and δ(2)H, respectively. This indicates either that the extraction time should be extended or that mechanisms different from Rayleigh fractionation play a role. The modified protocol allows a fast and reliable extraction of large numbers of water samples from soil and plant material in preparation for stable isotope analyses.

Spatial and temporal characterisation of stable isotopes in river water as indicators of groundwater contribution and confirmation of modelling results; a study of the Weser river, Germany.

River water samples were analysed for stable isotopes (deuterium and oxygen-18) collected from 46 sites during spring 2008, and from monthly samples at the outlets of seven sub-basins of the River Weser (46,200 km(2) basin area in total) over a five year period from 2003 to 2007, to characterise temporal and spatial isotope patterns of river water. Results indicate a pronounced elevation effect (0.2 per thousand and 1 to 2 per thousand per 100 m for delta(18)O and delta(2)H, respectively) as well as influence of seawater mixing for a few coastal locations. A lumped parameter modelling approach was used to compare residence times and relative amounts of direct flow, fast and slow groundwater with those derived from a combined water balance and tritium balance modelling approach. Residence times of direct runoff were estimated to be between one and three and a half months. Much longer groundwater residence times are necessary to explain tritium recession in river water. The modelling fits for stable isotope data in river water, derived with residence times and base flow amounts combined from a water and tritium balance approach, emphasise that beneath a characterisation of a direct flow component, seasonal variations of stable isotope values in river water carry information on groundwater contribution.

Assessing environmental and physiological controls over water relations in a Scots pine (Pinus sylvestris L.) stand through analyses of stable isotope composition of water and organic matter.

This study investigated the influence of meteorological, pedospheric and physiological factors on the water relations of Scots pine, as characterized by the origin of water taken up, by xylem transport as well as by carbon isotope discrimination (Delta13C) and oxygen isotope enrichment (Delta18O) of newly assimilated organic matter. For more than 1 year, we quantified delta2H and delta18O of potential water sources and xylem water as well as Delta13C and Delta18O in twig and trunk phloem organic matter biweekly, and related these values to continuously measured or modelled meteorological parameters, soil water content, stand transpiration (ST) and canopy stomatal conductance (G(s)). During the growing season, delta18O and delta2H of xylem water were generally in a range comparable to soil water from a depth of 2-20 cm. Long residence time of water in the tracheids uncoupled the isotopic signals of xylem and soil water in winter. Delta18O but not Delta13C in phloem organic matter was directly indicative of recent environmental conditions during the whole year. Delta18O could be described applying a model that included 18O fractionation associated with water exchange between leaf and atmosphere, and with the production of organic matter as well as the influence of transpiration. Phloem Delta13C was assumed to be concertedly influenced by G(s) and photosynthetically active radiation (PAR) (as a proxy for photosynthetic capacity). We conclude that isotope signatures can be used as effective tools (1) to characterize the seasonal dynamics in source and xylem water, and (2) to assess environmental effects on transpiration and G(s) of Scots pine, thus helping to understand and predict potential impacts of climate change on trees and forest ecosystems.