Application of stable isotopes and hydrochemical analysis in groundwater aquifers of Argolis Peninsula (Greece)

The present study examines the isotopic and hydrochemical composition of 18 inland spring waters and 3 coastal karstic spring waters, covering the period between October 2005 and March 2008. The stable isotopes ((18)O, (2)H) processing has revealed the absence of significant evaporation phenomena and that the origin of fresh water samples is meteoric. Using (18)O values in rainfall waters, an average line of isotopic depletion with altitude has been constructed, extracting a rate of-0.45‰/100?m as typical for the study area. Furthermore, the mean altitude of recharge of the springs has been estimated by plotting the groundwater sampling points on a δ(18)O versus altitude diagram. Hydrochemistry results have shown that the dissolution of carbonate, flysch and ophiolitic formations defines the hydrochemical characteristics of groundwater. Moreover, seawater intrusion in the coastal area is significantly high, causing the water in the three karstic springs to be brackish.     

Seawater intrusion into groundwater aquifer through a coastal lake - complex interaction characterised by water isotopes 2H and 18O

The present study investigates the complex interactions among surface waters, groundwaters and a coastal lake in northeastern Greece, using their stable isotopic composition (δ¹⁸O, δ²H) in combination with hydrogeological and hydrochemical data. Seasonal and spatial trends of water isotopes were studied and revealed that all water bodies in the study area interact. It was also shown that the aquifer's increased salinity is not due to fossil water from past geological periods, but is attributed to brackish lake water intrusion into the aquifer induced by the extensive groundwater pumping for irrigation purposes. Quantification of the contribution of the lake to the aquifer was achieved using the simple dilution formula. The isotopic signatures of the seawater and the groundwaters are considerably different, so there is a very little possibility of direct seawater intrusion into the aquifer.     

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 ((18)O, (2)H), tritium ((3)H) 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 precipitation's isotopic signal in spring discharge provided information on the minimum transit time of the spring waters. Due to short observation time, (3)H 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.     

The isotope altitude effect reflected in groundwater: a case study from Slovenia

This paper presents the stable isotope data of oxygen (δ¹⁸O) and hydrogen (δ²H) in groundwater from 83 sampling locations in Slovenia and their interpretation. The isotopic composition of water was monitored over 3 years (2009–2011), and each location was sampled twice. New findings on the isotopic composition of sampled groundwater are presented, and the data are also compared to past studies regarding the isotopic composition of precipitation, surface water, and groundwater in Slovenia. This study comprises: (1) the general characteristics of the isotopic composition of oxygen and hydrogen in groundwater in Slovenia, (2) the spatial distribution of oxygen isotope composition (δ¹⁸O) and d-excess in groundwater, (3) the groundwater isotope altitude effect, (4) the correlation between groundwater d-excess and the recharge area altitude of the sampling location, (5) the relation between hydrogen and oxygen isotopes in groundwater in comparison to the global precipitation isotope data, (6) the groundwater isotope effect of distance from the sea, and (7) the estimated relation between the mean temperature of recharge area and δ¹⁸O in groundwater.     

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.     

Origin and Recharge Altitude of the Thermo-Mineral Waters of the Eastern Pyrenees

The thermo-mineral waters of the axial zone of the Eastern Pyrenees form a geochemically homogeneous group. They emerge in granite or orthogneiss and all have a sodium sulphide chemistry. Principal component analysis of their physico-chemical parameters has distinguished three types of fluid, 1) hot water that has evolved in a closed system and whose chemistry may reflect that of deep water, 2) water that is also of unmixed origin, but whose chemical composition has been modified during cooling by conduction, and 3) water cooled by mixing with surface water.

Stable isotope (¹⁸O, ²H) contents indicate that all the waters are of meteoric origin (from oceanic and/or Mediterranean precipitation). No heavy isotope enrichment has been found that would indicate evaporation or a geothermal effect between water and the host rock.

The differences in isotope contents between surface and thermo-mineral waters are attributed to a difference in recharge altitude; altitude gradients in ¹⁸O and ²H, estimated by two independent methods, are respectively 0.24‰ and 1.84° per 100m. They may, however, be lower when precipitation is in the form of snow. Applying these calculated gradients to thermo-mineral waters, taking mixing effects into account, has given an estimate of the minimum altitude of recharge of 110 springs in the Eastern Pyrenees.     

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.     

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.     

Identifying local and regional groundwater in basins: chemical and stable isotopic attributes of multivariate classification of hydrochemical data,the Lower Virgin River Basin,Nevada, Arizona and Utah,U.S.A

In the Basin and Range Province of the Southwestern U.S.A., deep carbonate groundwater has been suggested as a significant source to many overlying basin-fill alluvial aquifer systems. Notwithstanding, testing this hypothesis is limited by obtaining data from such considerable depths and complex geology.

This study uses δ²H and δ¹⁸O data from springs, rivers, and wells tapping shallow basin-fill groundwater to test the hydrochemical interpretation of deep regional carbonate groundwater flow into the basin-fill aquifers. Stable isotopic and major ion attributes of hydrochemical facies suggest basin-fill alluvial groundwater of the Lower Virgin River Basin is a mixture of precipitation recharge within the Lower Virgin River Basin or the Clover and Escalante Desert Basin northwards, and the deep carbonate flow. The data support the conclusions that in the Lower Virgin River Basin, deep carbonate groundwater is an important source to the alluvial aquifer system and likely accounts for approximately 50% of the alluvial aquifer groundwater. Na⁺, K⁺, and SO₄^2– increase in the basin-fill alluvial groundwaters outside the Virgin River floodplain appears to be related with upwelling of deep regional groundwater, and indicating that the chemical character of the basin-fill alluvial groundwaters are related to the deeper flow systems.     

Spring response to precipitation events using δ18O and δ2H in the Tanour catchment,NW Jordan

The Tanour spring is one of the several karst springs located in the northern part of Jordan. Water samples from the Tanour spring and precipitation were collected in the area of Ajloun in NW Jordan for the analysis of stable oxygen and hydrogen isotopes to evaluate the spring response to precipitation events. Rainwater and snow samples were collected from different elevations during winters of 2013–2014 and 2014–2015. In addition, spring samples were collected between December 2014 and March 2015. δ¹⁸O values in rainwater vary from ?3.26 to ?17.34?‰ (average: ?7.84?±?3.23?‰), while δ²H values range between ?4.4 and ?110.4?‰ (average: ?35.7?±?25.0?‰). Deuterium excess ranges from 17.8 to 34.1?‰ (average: 27.1?±?4.0?‰). The Local Meteoric Water Line for the study area was calculated to be δ²H?=?7.66*δ¹⁸O?+?24.43 (R²?=?0.98). Pre-event spring discharge showed variation in δ¹⁸O (range ?6.29 to ?7.17?‰; average ?6.58?±?0.19?‰) and δ²H values (range ?28.8 to ?32.7?‰; average: ?30.5?±?1.0?‰). In contrast, δ¹⁸O and δ²H rapidly changed to more negative values during rainfall and snowmelt events and persisted for several days before returning to background values. Spring water temperature, spring discharge, and turbidity followed the trend in isotopic composition during and after the precipitation events. The rapid change in the isotopic composition, spring discharge, water temperature, and turbidity in response to recharge events is related to fast water travel times and low storage capacity in the conduit system of the karst aquifer. Based on the changes in the isotopic composition of spring water after the precipitation events, the water travel time in the aquifer is in the order of 5–11 days.     

Hydrogeological responses in tropical mountainous springs

This study presents a hydrogeochemical analysis of spring responses (2013–2017) in the tropical mountainous region of the Central Valley of Costa Rica. The isotopic distribution of δ¹⁸O and δ²H in rainfall resulted in a highly significant meteoric water line: δ²H?=?7.93·δ¹⁸O?+?10.37 (r^2? =?0.97). Rainfall isotopic composition exhibited a strong amount-dependent seasonality. The isotopic variation (δ¹⁸O) of two springs within the Barva aquifer was simulated using the FlowPC program to determine mean transit times (MTTs). Exponential-piston and dispersion distribution functions provided the best-fit to the observed isotopic composition at Flores and Sacramento springs, respectively. MTTs corresponded to 1.23?±?0.03 (Sacramento) and 1.42?±?0.04 (Flores) years. The greater MTT was represented by a homogeneous geochemical composition at Flores, whereas the smaller MTT at Sacramento is reflected in a more variable geochemical response. The results may be used to enhance modelling efforts in central Costa Rica, whereby scarcity of long-term data limits water resources management plans.     

Sulphur and Oxygen Isotopic Composition of Sulphates in Springs Feeding the Wieprz River and Other Springs of Lublin Upland and Roztocze

Abstract

Springs on Roztocze and Lublin Upland have been studied. Isotopic data are compared with data of chemical analyses. The results of studies allow us to distinguish five types of groundwaters. The differentiation is based upon different lithology; opokas, gaizes, sandy-silty-clay deposits, sands with shell sandstones, marly opokas, marly limestones and soft limestones of chalk type. A correlation can be observed between δ³⁴S and the concentration of Ca or Mg ions also a correlation between HCO₃ ^? ion concentration and δ¹⁸O in sulphates. Probably these correlations are the result of some simultaneous processes, which occur in groundwater. The seasonal variations of the isotopic composition and sulphate concentration were observed in four springs feeding the upper Wieprz. The variations were simultaneous and often similar in these springs. Probably, these variations are caused by the admixture of sulphates coming from shallow water layers (or leached from soil); however the variations of the groundwater level may also change chemical and isotopic composition in groundwater.     

Stable isotopic and geochemical variability within shallow groundwater beneath a hardwood hammock and surface water in an adjoining slough (Everglades National Park,Florida, USA)

Data from a 10-month monitoring study during 2007 in the Everglades ecosystem provide insight into the variation of δ¹⁸O, δD, and ion chemistry in surface water and shallow groundwater. Surface waters are sensitive to dilution from rainfall and input from external sources. Shallow groundwater, on the other hand, remains geochemically stable during the year. Surface water input from canals derived from draining agricultural areas to the north and east of the Everglades is evident in the ion data. δ¹⁸O and δD values in shallow groundwater remain near the mean of?2.4 and?12 ‰, respectively. ¹⁸O and D values are enriched in surface water compared with shallow groundwater and fluctuate in sync with those measured in rainfall. The local meteoric water line (LMWL) for precipitation is in close agreement with the global meteoric water line; however, the local evaporation line (LEL) for surface water and shallow groundwater is δ D=5.6 δ¹⁸O+1.5, a sign that these waters have experienced evaporation. The intercept of the LMWL and LEL indicates that the primary recharge to the Everglades is tropical cyclones or fronts. δ deuterium to δ¹⁸O excess (D_ex values) generally reveal two moisture sources for precipitation, a maritime source during the fall and winter (D _ex>10 ‰) and a continental-influenced source (D _ex<10 ‰) in the spring and summer.     

Nachruf Prof. Hübner

Abstract

Representative water samples were collected from different oases in the western desert of Egypt to examine characteristics of Egyptian groundwater. Chemical data recognized two basic groundwater types; alkali bicarbonate and alkali chloride, where sodium has the highest concentration. For each region the median SD, δ¹⁸ 0 and ionic strength of water calculated from their chemical analyses are recorded and plotted.

Generally, the results of isotopic content measurements of the groundwaters from the different oases in the western desert indicate the fossile origin of these waters. The values of δD and δ¹⁸ 0 of the western desert oases' waters are characteristic of old paleowaters from the Nubian sand aquifer. Modern sparse rainfall data suggest that any precipitation will exhibit moderate to large positive isotopic content enrichments and cannot be a source for these waters. They have been in no connection with the Nile water, moreover the change in isotopic composition is due to evaporation which is now ineffective at deeper levels.     

Deuterium and Oxygen-18 in Surface Waters of GDR draining to the Baltic Sea

A general view is presented of deuterium and ¹⁸O measurements of water samples collected at running and standing surface waters in German Democratic Republic. The values confirm earlier observations that the surface waters are influenced by evaporation with respect to the isotopic composition of groundwater. Nevertheless, stronger evaporation effects are restricted to larger lakes. The amount of surface water discharge from GDR to the Baltic Sea and the δD and δ¹⁸O values are discussed. The river Oder provides about 90% of the whole surface run-off. The other watercourses to the coast are unimportand. The mean heavy isotope content of surface run-off was calculated to be ?8.3‰ for δ¹⁸O and ?61‰ for δD (vs. SMOW), respectively.     

Contributions of the different water sources to the Elqui river runoff (northern Chile) evaluated by H/O isotopes

We present the results of an isotope (2H and 18O) and hydrogeochemical study in order to constrain the origin, recharge, and evolution of the surface and groundwater in the arid Andean realm of the Elqui watershed. The results of 2H and18O analyses of water samples obtained during our summer and winter campaigns indicate a generally meteoric origin of the river and spring waters of the watershed. The isotope signature of water of the Elqui river and its tributaries as well as that of groundwater in the coastal region fits the 2H-18O relation of delta2H =7.61delta18O+6.1. A relatively fast discharge and a quasi-closed catchment area can be asserted for water along the river flow path. The tributaries from the more arid coastal area, north of the Elqui river, differ in their isotopic signature due to evaporation and hydrochemically due to interactions with the strongly altered and fractured volcanic rocks of the basement. In the Andean zone, the18O-enriched hydrothermal spring of Ba?os del Toro exhibits the influence of water-rock interaction processes. The chemistry of the river water changes from sulphate- to chloride-rich along the river course from the high Andean mountains to the coast. The sulphate-rich character of these Andean waters reflects their passage through sulphide-rich rock massifs that were subjected to strong oxidation processes in the near superficial environment. This sulphate signature is enforced by past and present mining of precious metal epithermal deposits (e.g. those of El Indio-Tambo Au-Cu-As district), in which mineralised zones were developed during a series of Miocene magmatic-hydrothermal episodes in the Andean realm. Owing to the proximity of the lower Elqui river waters and its tributaries to the Pacific coast, the chloride character may be induced by agricultural and marine (sea spray, fog) sources. Generally, the main source of the Elqui river water is mainly attributed to surface runoff and less to contributions from the basement fractured aquifer.     

Note on the spring region of Gacka River (Croatia)†

We present the first results of a study of the Gacka River spring area, an important Croatian drinking water resource. Stable isotope data (obtained at the Stable Isotope Laboratory SILab in Rijeka) are used in combination with hydrological and meteorological data. The δ¹⁸O values give information on the mean catchment altitudes of the three main springs of Gacka River (Majerovo vrelo, Tonkovi?a vrelo and Pe?ina). Hydrological, meteorological and stable isotope data indicate good mixing of infiltrated and ground waters. The precipitation d-excess shows a seasonally varying influence of continental and maritime air masses.     

Deuterium as Natural Tracer in Groundwater from Neighbouring Area of Danube Delta Biosphere Reserve

Abstract

Measurements of deuterium content of the groundwater from neighbouring area of Danube Delta Biosphere Reserve show that the waters are meteoric in origin, but at the same time the results showed that the water for three sampling points could not originate from local groundwater and have their recharge area at high altitude and a considerable distance.

According to the δD values the following categories of waters were delineated:

• (1) waters that belong to an confined aquifer in limestone and have their recharge in high altitude region, higher than 1000m (δD < -80‰)

  (2) waters tributary to the Danube river that have a small variability in time of δD values (δD > - 75‰)
  (3) local infiltration waters, situated in the West of the investigated area towards the continental platform of the Dobroudja, with high variability in time of δD values, due to seasonal effect (δD > - 70‰)
  (4) waters originated in mixing processes between the waters with different isotopic content. The one endmember is heavier isotopic water that belongs to local recharged waters (local infiltration waters and waters tributary to Danube river) and the other endmember is the isotopically light water.

     

Determination of δ2H and δ18O 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 δ¹⁸O and δ²H 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 δ²H 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 δ²H 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 δ¹⁸O 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.     

Geochemical and isotopic evidences from groundwater and surface water for understanding of natural contamination in chronic kidney disease of unknown etiology (CKDu) endemic zones in Sri Lanka

Chronic kidney disease of unknown etiology (CKDu) is the main health issue in the dry zone of Sri Lanka. Despite many studies carried out, causative factors have not been identified yet clearly. According to the multidisciplinary researches carried out so far, potable water is considered as the main causative factor for CKDu. Hence, the present study was carried out with combined isotopic and chemical methods to understand possible relationships between groundwater; the main drinking water source, and CKDu in four endemic areas in the dry zone. Different water sources were evaluated isotopically (²H, ³H and ¹⁸O) and chemically from 2013 to 2015. Results revealed that prevalence of CKDu is significantly low with the groundwater replenished by surface water inputs. It is significantly high with the groundwater stagnated as well as groundwater recharged from regional flow paths. Thus, the origin, recharge mechanism and flow pattern of groundwater, as well as geological conditions which would be responsible for natural contamination of groundwater appear as the main causative factors for CKDu. Therefore, detailed investigations should be made in order to identify the element(s) in groundwater contributing to CKDu. The study recommends providing drinking water to the affected zones using water sources associated with surface waters.