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.     

Stable isotope composition of the meteoric precipitation in Croatia

The precipitation is the input into the water system. Its stable isotope composition has to be known for the proper use and management of water resources. Croatia is not well represented in the Global Network of Isotopes in Precipitation (GNIP) database, and the geomorphology of the country causes specific local conditions. Therefore, at the Stable Isotope Laboratory (SILab), Rijeka, we monitor the stable isotope composition (δ¹⁸O, δ²H) of precipitation. Since δ¹⁸O and δ²H are well correlated, we concentrate the discussion on the δ¹⁸O distribution. Together with GNIP, our database contains 40 stations in Croatia and in the neighbouring countries. Their different latitudes, longitudes and altitudes give information of great detail, including the influence of the topographic structure on the precipitation in the south-eastern part of Europe, as well as the complex interplay of the different climate conditions in the area. Within a few hundred kilometres, the stable isotope values display a significant change from the maritime character in the south (mean δ¹⁸O around?6 to?8%‰) to the continental behaviour in the north (mean δ¹⁸O around?8 to?11%‰). Depending on the location, the mean δ¹⁸O values vary with altitude at a rate of approximately?0.2%‰/100 m and?0.4%‰/100 m, respectively. Also the deuterium excess has been found to depend on location and altitude. The data are being used to construct a δ¹⁸O map for the entire area.     

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.     

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.     

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.     

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.     

USGS48 Puerto Rico precipitation – a new isotopic reference material for δ2H and δ18O measurements of water

A new secondary isotopic reference material has been prepared from Puerto Rico precipitation, which was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material, designated as USGS48, is intended to be one of two isotopic reference waters for daily normalisation of stable hydrogen (δ²H) and stable oxygen (δ¹⁸O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The δ²H and δ¹⁸O values of this reference water are?2.0±0.4 and?2.224±0.012 ‰, respectively, relative to Vienna Standard Mean Ocean Water on scales normalised such that the δ²H and δ¹⁸O values of Standard Light Antarctic Precipitation reference water are?428 and?55.5 ‰, respectively. Each uncertainty is an estimated expanded uncertainty (U=2u_c) about the reference value that provides an interval that has about a 95 % probability of encompassing the true value. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule.     

Studies on stable isotopic composition of daily rainfall from Kozhikode,Kerala, India

The stable isotopic compositions of all major daily rain fall samples (n?=?113) collected from Kozhikode station in Kerala, India, for the year 2010 representing the pre-monsoon, southwest and northeast monsoon seasons are examined. The isotopic variations δ¹⁸O, δ²H and d-excess in daily rainfall ranged from δ¹⁸O: ?4.4 to 2?‰, δ²H: ?25.3 to 13.8?‰, and d-excess: ?2.4 to 15.3?‰; δ¹⁸O: ?9.7 to ?0.6?‰, δ²H: ?61.7 to 5.3?‰, and d-excess 5.8 to 17.4?‰; δ¹⁸O ?11.3 to ?1.4?‰, δ²H: ?75.3 to 0.9?‰, and d-excess: 8.8 to 21.3?‰ during the pre-, southwest and northeast monsoon periods, respectively. Thus, daily rainfall events during two monsoon periods had a distinct range of isotopic variations. The daily rain events within the two monsoon seasons also exhibited periodic variations. The isotopic composition of rain events during pre-monsoon and a few low-intensity events during the southwest monsoon period had imprints of secondary evaporation. This study analysing the stable isotopic characteristics of individual rain events in southern India, which is influenced by dual monsoon rainfall, will aid in a better understanding of its mechanism.     

C and O stable isotopic signatures of fast-growing dripstones on alkaline substrates: reflection of growth mechanism,carbonate sources and environmental conditions

Secondary carbonate precipitates (dripstones) formed on concrete surfaces in four different environments – Mediterranean and continental open-space and indoor environments (inside a building and in a karstic cave) – were studied. The fabric of dripstones depends upon water supply, pH of mother solution and carbonate-resulting precipitation rate. Very low δ¹³C (average?28.2‰) and δ¹⁸O (average?18.4‰) values showed a strong positive correlation, typical for carbonate precipitated by rapid dissolution of CO₂ in a highly alkaline solution and consequent disequilibrium precipitation of CaCO₃. The main source of carbon is atmospheric or biogenic CO₂ in the poorly ventilated karstic cave, which is reflected in even lower δ¹³C values. Statistical analysis of δ¹³C and δ¹⁸O values of the four groups of samples showed that the governing factor of isotope fractionation is not the temperature, but rather the precipitation rate.     

Isotopic Assessment of Sources and Processes Affecting Sulfate and Nitrate in Surface Water and Groundwater of Luxembourg

Abstract

Surface water and deep and shallow groundwater samples were taken from selected parts of the Grand-Duchy of Luxembourg to determine the isotopic composition of nitrate and sulfate, in order to identify sources and/or processes affecting these solutes. Deep groundwater had sulfate concentrations between 20 and 40mg/L, δ³⁴S_sulfate values between ?3.0 and ?20.0‰, and δ¹⁸O_sulfate values between +1.5 and +5.0‰ nitrate was characterized by concentrations varying between <0.5 and 10mg/L, δ¹⁵N_nitrate values of ～?0.5‰, and δ¹⁸O_nitrate values ～+3.0‰. In the shallow groundwater, sulfate concentrations ranged from 25 to 30mg/L, δ³⁴S_sulfate values from ?20.0 to +4.5‰, and δ¹⁸O_sulfate values from ～+0.5 to +4.5‰ nitrate concentrations varied between ～10 and 75mg/L, δ¹⁵N_nitrate values between +2.5 and +10.0‰, and δ¹⁸O_nitrate values between +1.0 and +3.0‰. In surface water, sulfate concentrations ranged from 10 to 210mg/L, δ³⁴S_sulfate values varied between ?9.3 and +10.9‰, and δ¹⁸O_sulfate values between +3.0 and +10.7‰ were observed. Nitrate concentrations ranged from 10 to 40mg/L, δ¹⁵N_nitrate values from +6.5 to +12.0‰, and δ¹⁸O_nitrate values from ?0.4 to +4.0‰. Based on these data, three sulfate sources were identified controlling the riverine sulfate load. These are soil sulfate, dissolution of evaporites, and oxidation of reduced S minerals in the bedrock. Both groundwater types were predominantly influenced by sulfate from the two latter lithogenic S sources. The deep groundwater and a couple shallow groundwater samples had nitrate derived mainly from soil nitrification. All other sampling sites were influenced by nitrate originating from sewage and/or manure. A decrease in nitrate concentration observed along one of the rivers was attributed to denitrification. It appears that sulfate within Luxembourg's aquatic ecosystem is mainly of lithogenic origin, whereas nitrate is often derived from anthropogenic activities.     

Stable isotopes in river waters in the Tajik Pamirs: regional and temporal characteristics

The Gunt River catchment in the Central Pamirs is a representative of the headwater catchments of the Aral Sea Basin. It covers 14,000 km², spanning altitudes between 2000 and 6700 m a.s.l. In a monitoring network, water samples were taken at 30 sampling points every month and analysed for the stable water isotopes (¹⁸O and ²H). Our first results show δ²H values in the range from?131.2 to?94.9 ‰ and δ¹⁸O values from?18.0 to?14.0 ‰. The stable isotope patterns in the catchment seem to follow a systematic way, dominated by an altitude effect with a mean Δ δ²H=?3.6 ‰/100 m. The observed seasonal variations can be explained by geographical aspects such as the influence of different wind systems as well as melting processes.     

Analysis of isotopic signals in the Danube River water at Tulln,Austria, based on daily grab samples in 2012

Results of stable isotope measurements (δ²H, δ¹⁸O) of daily grab samples, taken from the Danube River at Tulln (river km 1963) during 2012, show seasonal and short-term variations depending on the climatic/hydrological conditions and changes in the catchment area (temperature changes, heavy rains and snow melt processes). Isotope ratios in river water clearly reflect the isotopic composition of precipitation water in the catchment area since evaporation influences play a minor role. Average δ²H and δ¹⁸O values in 2012 are?78‰ and?11.0‰, respectively, deuterium excess averages 10‰. The entire variation amounts to 1.8‰ in δ¹⁸O and 15‰ in δ²H. Quick changes of the isotopic composition within a few days emphasise the necessity of daily sampling for the investigation of hydrological events, while monthly grab sampling seems sufficient for the investigation of long-term hydro-climatic trends. ³H results show peaks (half-width 1–2 days, up to about 150 TU) exceeding the regional environmental level of about 9 TU, probably due to releases from nuclear power plants.     

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.     

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.     

Spatial and temporal variability of stable isotopes and biological parameters for the Danube River in Serbia

This paper presents the results of hydrological, physicochemical, biological, and isotopic investigations of the Danube River along the stretch through Serbian territory conducted during four campaigns in September and November 2007, September 2008 and April 2009. The stable isotope values exhibited significant changes both in the Danube (?10.7 to?9.5‰ for δ¹⁸O and?73.7 to?67.1 ‰ for δ²H) and in its tributaries (?9.1 to?8.5‰ for δ¹⁸O and?69.4 to?59.4‰ for δ²H) depending on the time of survey, which could be partly attributed to the influences of seasonal effects. Results emphasise the dominant role of tributaries inflows from aquifers along the Danube. The very narrow range of δ¹³C_POC (from?28.9 to?27.4 ‰) was associated with relatively high C/N ratios (C/N>9), and together with δ¹⁵N_TPN values, the date suggested that, in early spring, a major fraction of particulate organic matter was derived from allochthonous matter. An orthogonal varimax rotation of the principal components analysis identified four latent factors (‘mineral related’, ‘biological’, ‘hardness’, and ‘soil inlets’) which are responsible for the data structure covering 79% of the observed variations among the variables studied. A reliable grouping of samples with respect to the season was found.     

Comparison of pore water samplers and cryogenic distillation under laboratory and field conditions for soil water stable isotope analysis*

We used pore water samplers (PWS) to sample for isotope analysis (1) only water, (2) soil under laboratory conditions, and (3) soil in the field comparing the results with cryogenic extraction (CE). In (1) and (2), no significant differences between source and water extracted with PWS were detected with a mean absolute difference (MAD) always lower than 2?‰ for δ²H and 1?‰ for δ¹⁸O. In (2), CE water was more enriched than PWS-extracted water, with a MAD respect to source water of roughly 8?‰ for δ²H and 4?‰ for δ¹⁸O. In (3), PWS water was enriched relative to CE water by 3?‰ for δ²H and 0.9?‰ for δ¹⁸O. The latter result may be due to the distinct water portions sampled by the two methods. Large pores, easily sampled by PWS, likely retain recent, and enriched, summer precipitation while small pores, only sampled by CE, possibly retain isotopically depleted water from previous winter precipitation or irrigation inputs. Accuracy and precision were greater for PWS relative to CE. PWS is therefore suggested as viable tool to extract soil water for stable isotope analysis, particularly for soils used in this study (sandy and silty loams).     

Stable isotopes determination in some Romanian wines

This paper presents a study concerning the isotopic fingerprint (¹⁸O and ¹³C) of some wines prepared from relevant Romanian grape varieties (e.g. Feteasca Alba (FA), Feteasca Regala (FR) and Cabernet Sauvignon (CS)) obtained in different vintage years (2002, 2003, 2004, 2007 and 2008). These wines were obtained from different vineyards having a significant role in the wine market: Cotesti, Tohani, Stefanesti, Aiud, Cotnari, Bucium, Murfatlar, Bujoru, Dragasani and Valea Calugareasca. Several observations related to the dependence of isotope ratios on geographical origin and climatic conditions were drawn. The authentic wines obtained from the FA grape variety from six different vineyards showed δ¹⁸O values in the range of+3.28 (Cotesti region – 45 °38′N/27 °04′E) to?2.60 ‰ (Aiud region – 46 °19′N/23 °45′E). The δ¹³C values were very similar for all the samples with an average of about?26 ‰. The difference between the δ¹⁸O values was due to the different climatic zones, which have an influence on the δ¹⁸O values of wine water. For the wine variety CS obtained from the Dealu Mare–Tohani vineyard, production years 2003 and 2004, a greater difference in the δ¹⁸O values of wine water ranging from 1.89 (in 2004) to 5.35 ‰ (in 2003) was noted. This difference is explained by the different mean annual temperatures in 2003 and 2004.     

Influence of the balance of the intertropical front on seasonal variations of the isotopic composition in rainfall at Kisiba Masoko (Rungwe Volcanic Province,SW, Tanzania)

Tropical rainfall isotopic composition results from complex processes. The climatological and environmental variability in East Africa increases this complexity. Long rainfall isotope datasets are needed to fill the lack of observations in this region. At Kisiba Masoko, Tanzania, rainfall and rain isotopic composition have been monitored during 6 years. Mean year profiles allow to analyse the seasonal variations. The mean annual rainfall is 2099?mm with a rain-weighted mean composition of ?3.2?‰ for δ¹⁸O and ?11.7?‰ for δ²H. The results are consistent with available data although they present their own specificity. Thus, if the local meteoric water line is δ²H?=?8.6 δ¹⁸O?+?14.8, two seasonal lines are observed. The seasonality of the isotopic composition in rain and deuterium excess has been compared with precipitating air masses backtracking trajectories to characterize a simple scheme of vapour histories. The three major oceanic sources have two moisture signatures with their own trajectory histories: one originated from the tropical Indian Ocean at the beginning of the rainy season and one from the Austral Ocean at its end. The presented isotopic seasonality depends on the balance of the intertropical front and provides a useful dataset to improve the knowledge about local processes.     

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.     

Comparison of δ13C and δ18O from cellulose,whole wood,and resin-free whole wood from an old high elevation Pinus uncinata in the Spanish central Pyrenees*

δ¹³C and δ¹⁸O values from sapwood of a single Pinus uncinata tree, from a high elevation site in the Spanish Pyrenees, were determined to evaluate the differences between whole wood and resin-free whole wood. This issue is addressed for the first time with P. uncinata over a 38-year long period. Results are also compared with published isotope values of α-cellulose samples from the same tree. The differences in δ¹³C and δ¹⁸O between whole wood and resin-free whole wood vary within the analytical uncertainty of 0.3 and 0.5?‰, respectively, indicating that resin extraction is not necessary for sapwood of P. uncinata. Mean differences between cellulose and whole wood are 0.9?‰ (δ¹³C) and 5.0?‰ (δ¹⁸O), respectively. However, further analyses of different species and other sites are needed to evaluate whether the findings reported here are coherent more generally.