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.     

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.     

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 (¹⁸O, ²H) processing has revealed the absence of significant evaporation phenomena and that the origin of fresh water samples is meteoric. Using ¹⁸O 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 δ¹⁸O 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.     

Defining a stable water isotope framework for isotope hydrology application in a large trans-boundary watershed (Russian Federation/Ukraine)

Stable isotopes of hydrogen (²H) and oxygen (¹⁸O) of the water molecule were used to assess the relationship between precipitation, surface water and groundwater in a large Russia/Ukraine trans-boundary river basin. Precipitation was sampled from November 2013 to February 2015, and surface water and groundwater were sampled during high and low flow in 2014. A local meteoric water line was defined for the Ukrainian part of the basin. The isotopic seasonality in precipitation was evident with depletion in heavy isotopes in November–March and an enrichment in April–October, indicating continental and temperature effects. Surface water was enriched in stable water isotopes from upstream to downstream sites due to progressive evaporation. Stable water isotopes in groundwater indicated that recharge occurs mainly during winter and spring. A one-year data set is probably not sufficient to report the seasonality of groundwater recharge, but this survey can be used to identify the stable water isotopes framework in a weakly gauged basin for further hydrological and geochemical studies.     

Identification of the nitrate contamination sources of the Brusselian sands groundwater body (Belgium) using a dual-isotope approach

Isotopic fingerprinting is an advanced technique allowing the classification of the nitrate source pollution of groundwater, but needs further development and validation. In this study, we performed measurements of natural stable isotopic composition of nitrate (¹⁵N and ¹⁸O) in the groundwater body of the Brussels sands (Belgium) and studied the spatial and temporal dynamics of the isotope signature of this aquifer. Potential nitrogen sources sampled in the region had isotopic signatures that fell within the corresponding typical ranges found in the literature. For a few monitoring stations, the isotopic data strongly suggest that the sources of nitrate are from mineral fertiliser origin, as used in agriculture and golf courses. Other stations suggest that manure leaching from unprotected stockpiles in farms, domestic gardening practices, septic tanks and probably cemeteries contribute to the nitrate pollution of this groundwater body. For most monitoring stations, nitrate originates from a mixing of several nitrogen sources. The isotopic signature of the groundwater body was poorly structured in space, but exhibited a clear temporal structure. This temporal structure could be explained by groundwater recharge dynamics and cycling process of nitrogen in the soil-nitrogen pool.     

Spatial and temporal variation of H and O isotopic compositions of the Xijiang River system,Southwest China

Ratios of stable isotopes of hydrogen and oxygen (²H/¹H and ¹⁸O/¹⁶O) in river waters were measured to investigate the hydrological pathway of the Xijiang River, Southwest China. The δ²H and δ¹⁸O values of river waters exhibit significant spatial and temporal variations and the isotopic compositions vary with elevation, temperature and precipitation of the recharge area. Spatially, δ¹⁸O values of river waters from high mountain areas are lower than those from the lower reaches of the Xijiang River due to lower temperature and higher elevation for the recharge area. However, both ²H and ¹⁸O are enriched differently in river waters from the middle reaches during the high flow season, depending on the season and degree of anthropogenic disturbances (e.g. water impoundments). In contrast, deuterium excess (d-excess) values of waters from the middle reaches are substantially lower than those from the upper and lower reaches, suggesting that river waters may be resided in the reservoir and evaporation increases in the middle reaches of the Xijiang River.     

Isotopic characteristics of meteoric waters in the Belgrade region

Abstract

The stable isotope composition of hydrogen (δ²H) and oxygen (δ¹⁸O) in monthly precipitation and river water (Sava River and Danube) samples in the Belgrade area gathered between 1992 and 2005 are determined. The local meteoric water line δ²H=7.8 (±0.2) δ¹⁸O+7.3(±1.6) (r ²=0.98, n=60, σ=0.52) for the whole period of observation is close to the global meteoric water line. The amount-weighted mean δ²H and δ¹⁸O values of precipitation were?65±27 ‰ and?9.4±3.4 ‰, respectively. Good correlation between δ¹⁸O values (r>rsim0.67) and ambient temperature and relative humidity was obtained. Stream-water data ranged from?94 to?60 ‰ for δ²H and from?11.0 to ～5.7 ‰ for δ¹⁸O with highly statistically significant difference (p>0.01) between the Sava River and the Danube. In addition, the isotopic compositions of local precipitation and adjacent river water at monitoring sites were compared. Obtained data will give an opportunity to improve the knowledge of mixing stream water and local groundwater, and assessment of potential groundwater risks and pressures in the Belgrade basin.     

First field-based observations of δ2H and δ18O values of event-based precipitation,rivers and other water bodies in the Dzungarian Gobi,SW Mongolia

For certain remote areas like Mongolia, field-based precipitation, surface and ground water isotopic data are scarce. So far no such data exist for the Mongolian Gobi desert, which hinders the understanding of isotopic fractionation processes in this extreme, arid region. We collected 26 event-based precipitation samples, 39 Bij river samples, and 75 samples from other water bodies in the Dzungarian Gobi in SW Mongolia over a period of 16 months for hydrogen and oxygen stable isotope analysis. δ²H and δ¹⁸O values in precipitation show high seasonal variation and cover an extreme range: 175?‰ for δ²H and 24?‰ for δ¹⁸O values. The calculated local meteoric water line (LMWL) shows the isotopic characteristics of precipitation in an arid region. Individual water samples fall into one of three groups: within, above or below the 95?% confidence interval of LMWL. Data presented provide a basis for future studies in this region.     

Distribution of stable isotopes in surface water along the Danube River in Serbia†

Stable hydrogen and oxygen isotopes were analysed in water samples from the River Danube and its tributaries during a longitudinal survey performed in August 2005 on Serbian territory. Danube river water data ranged from?80‰ to?66‰ for δ²H, and from?11.2‰ to?9.3‰ for δ¹⁸O with δ values increasing downstream. The isotopic signatures of the adjacent tributaries (the Tisza, the Sava and the Velika Morava) sampled at the locations close to their confluence with the Danube (Titel, Ostru?nica and Ljubi?evski most, respectively) just about the time of the campaign were enriched (?67‰ and?63‰ for δ²H, and?9.3‰ and?8.9‰ for δ¹⁸O) with respect to the Danube water because of their catchment effects. Hydrogen and oxygen stable isotope values were used in combination with measured physico-chemical and biological parameters to trace hydrological and transport processes in these river systems. The mixing relationships between the Danube main stream and its tributaries were estimated using the mass balance for isotopic composition and electrical conductivity as conservative parameters. Evidence of an incomplete mixing process at the ?enta location, 8 km below the confluence of the Tisza river, with its participation of 88% was shown by its oxygen-18 content. The correlations between river water isotope composition and physico-chemical and biological parameters are discussed.     

Groundwater of the Crimean peninsula: a first systematic study using stable isotopes

ABSTRACT

Karst springs in the Main Range of the Crimean Mountains and the Crimean Piedmont show a restricted range of values (δ¹⁸O?=?–10.5 to –8.0 ‰, δ²H?=?–72 to –58 ‰), somewhat more negative than the weighted mean of meteoric precipitation. This suggests preferential recharge at higher elevations during winter months. Groundwater tapped by boreholes splits in three groups. A first group has isotopic properties similar to those of the springs. The second group shows significantly lower values (δ¹⁸O?=?–13.3 to –12.0 ‰, δ²H?=?–95 to –82 ‰), suggesting recharge during colder Pleistocene times. The third group has high isotope values (δ¹⁸O?=?–2.5 to +1.0 ‰, δ²H?=?–24 to –22 ‰); the data points are shifted to the right of the Local Meteoric Water Line, suggesting water–rock exchange processes in the aquifer. These boreholes are located in the Crimean Plains and discharge mineralized (ca. 25 g L^?1) thermal (65°C) water from a depth of 1600–1800 m. Groundwater associated with mud volcanoes on the Kerch peninsula have distinct isotope characteristics (δ¹⁸O?=?–1.6 to +9.4 ‰, δ²H?=?–30 to –18 ‰). Restricted δ²H variability along with variable and high δ¹⁸O values suggest water–rock interactions at temperatures exceeding 95 °C.     

The use of stable isotopes to evaluate water mixing and water use by flood plain trees along the Garonne valley

Before the confluence of the Tarn, the Garonne valley was the driest area in the entire south-west of France, due to the relatively low rainfall and low summer discharge of the Garonne River and its tributaries. The natural abundance of the stable isotope of oxygen (¹⁸O) and ionic charge of surface and ground water were used to estimate the water source for the Garonne River and phreatic subsurface water. We also measured these constituents in the sap of trees at several flood plain sites to better understand the source of water used by these trees. ¹⁸O signatures and conductivity in the Garonne River indicated that the predominance of water was from high altitude surface runoff from the Pyrenees Mountains. Tributary inputs had little effect on isotopic identity, but had a small effect on the conductivity. The isotopic signature and ionic conductivity of river water (δ¹⁸O: ?9.1‰ to ?9.0‰, conductivity: 217–410?µS/cm) was distinctly different from groundwater (δ¹⁸O: ?7.1‰ to ?6.6‰, conductivity: 600–900?µS/cm). Isotopic signatures from the sap of trees on the flood plain showed that the water source was shallow subsurface water (<30?cm), whereas trees further from the river relied on deeper ground water (>1?m). Trees at both locations maintained sap with ionic charges much greater (2.3–3.7×) than that of source water. The combined use of ¹⁸O signatures and ionic conductivity appears to be a potent tool to determine water sources on geographic scales, and source and use patterns by trees at the local forest scale. These analyses also show promise for better understanding of the effects of anthropogenic land-use and water-use changes on flood plain forest dynamics.     

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.     

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.     

AgF desalination procedure for the routine determination of oxygen and hydrogen isotopic composition of saline waters and brines

The routine methods for stable oxygen and hydrogen isotope analysis of water involve water–CO₂ gas equilibration and water reduction on hot metal (e.g. Zn, Cr, U) and subsequent mass spectrometric analysis of the evolved gases of CO₂ and H₂ for ¹⁸O/¹⁶O and ²H/¹H ratios, respectively. Precise determination of the isotopic composition of water in brines with application of these standard methods is still problematic and technically often impossible due to detrimental influence of dissolved salts. The new method of brine desalination presented in this study overcomes the problem of the isotope salt effects encountered during the application of the routine techniques for the determination of the isotopic composition of high saline waters. The procedure combines two technical steps: (i) the chemical precipitation of Mg and Ca ions as insoluble non-hydroscopic fluorides, and (ii) the vacuum distillation of water from solution–precipitate mixture. The application of simple vacuum distillation allows full extraction of water and dehydration of remaining salts in a temperature range from 300 to 350?°C without hydrogen and oxygen isotope fractionation. The precision and accuracy of δ¹⁸O and δ²H determination of saline waters and brines with prior application of AgF desalination procedure is comparable with that usually obtained for fresh waters.     

Spatial distribution of electrical conductivity and stable isotopes in groundwater in large catchments: a geostatistical approach in the Quequén Grande River catchment,Argentina

Stable isotopes and electrical conductivity in groundwater were used as natural tracers to adjust the hydrogeological conceptual model in one of the largest catchments within the inter-mountainous Pampa plain, Argentina. Geostatistical tools were used to define the model that best fitted the spatial distribution of each tracer, and information was obtained in areas where there was a lack of data. The conventional isotopic analysis allowed the identification of three groundwater groups with different isotopic fingerprints. One group containing 56?% of the total groundwater samples suggested a well-mixed system and soil infiltration precipitation as the main recharge source to the aquifer. The other two groups included samples with depleted (25.5?%) and enriched (18.5?%) isotopic compositions, respectively. The combination of δ¹⁸O, δ²H and electrical conductivities maps suggested ascending regional flows and water transfer from the Quequén Grande River catchment to the Moro creek. The spatial interpretation of these tracers modified the conceptual hydrogeological model of the Quequén Grande River.     

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.     

Methane-Derived Carbonates in a Native Sulfur Deposit: Stable Isotope and Trace Element Discriminations Related to the Transformation of Aragonite to Calcite

Abstract

Stable isotope (¹³C, ¹⁸O, ³⁴S) and trace element (Sr²⁺, Mg²⁺, Mn²⁺, Ba²⁺, Na⁺) investigations of elemental sulfur, primary calcites and mixtures of aragonite with secondary, post-aragonitic calcite from sulfur-bearing limestones have provided new insights into the geochemistry of the mineral forming environment of the native sulfur deposit at Machów (SE-Poland). The carbon isotopic composition of carbonates (δ¹³C = ?41 to ?47‰ vs. PDB) associated with native sulfur (δ³⁴S = + 10 to + 15‰ vs. V-CDT) relates their formation to the microbiological anaerobic oxidation of methane and the reduction of sulfate derived from Miocene gypsum. From a comparison with experimentally derived fractionation factors the element ratios of the aqueous fluids responsible for carbonate formation are estimated. In agreement with field and laboratory observations, ratios near seawater composition are obtained for primary aragonite, whereas the fluids were relatively enriched in dissolved calcium during the formation of primary and secondary calcites. Based on the oxygen isotope composition of the carbonates (δ¹⁸O = ?3.9 to ?5.9‰ vs. PDB) and a secondary SrSO₄ (δ¹⁸O = + 20‰ vs. SMOW; δ³⁴S = + 59‰ vs. V-CDT), maximum formation temperatures of 35°C (carbonates) and 47°C (celestite) are obtained, in agreement with estimates for West Ukraine sulfur ores. The sulfur isotopic composition of elemental sulfur associated with carbonates points to intense microbial reduction of sulfate derived from Miocene gypsum (δ³⁴S ≈ + 23‰) prior to the re-oxidation of dissolved reduced sulfur species.     

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.     

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.