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.     

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.     

Pleistocene age paleo-groundwater inferred from water-stable isotope values in the central part of the Baltic Artesian Basin

A new data set of δ²H and δ¹⁸O in the groundwater from the central part of the Baltic Artesian Basin is presented. The hydrogeological section is subdivided into stagnation, slow exchange and active exchange zones. Na–Ca–Cl brine found at the deepest part – the stagnation zone – is characterized by δ¹⁸O values above ?5?‰ and δ²H values approaching ?40?‰ with respect to Vienna Standard Mean Ocean Water. The slow exchange zone where waters of mostly intermediate salinity reside is characterized by δ¹⁸O values around ?11.7?‰ and δ²H values around ?85.3?‰. Mean δ¹⁸O and δ²H values of the fresh groundwater in the active water exchange zone are ?11.1 and ?79.9?‰, respectively. Characteristically, the groundwater in the active and slow exchange zone is isotopically more depleted compared with the precipitation values observed, and the depletion increases with depth down to the level where strongly enriched brines are encountered.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Isotopic composition of bottled water in Saudi Arabia

The ¹⁸O/¹⁶O and ²H/¹H ratios of 18 water brands representing the most popular bottled water brands in the Saudi market were measured using a system based on the latest advancements in tunable off-axis integrated cavity output diode laser spectroscopy (OA-ICOS) in the near-infrared spectral region. Utilizing δ¹⁸O and the δ²H values of locally produced water samples, a meteoric water line (δ²H?=?7.84 δ¹⁸O?+?2.11) was extracted and found to be consistent with the slope of the global meteoric water line (GMWL) and the geographic location of Saudi Arabia.     

Assessing the authenticity of commercial deep-sea drinking water by chemical and isotopic approaches

This study combines stable isotopes and chemical elements with statistical principal component analysis (PCA) to assess the authenticity of bottled commercial drinking water desalinized from deep seawater in the Taiwan market. Isotopic results indicate that true bottled deep-sea drinking water (DSDW) exhibits about 0?‰ for both δ²H and δ¹⁸O values, which are values similar to those of open seawater. By comparison, suspected counterfeit DSDW products display δ²H and δ¹⁸O values of around ?51?‰ and ?8?‰, respectively. These values are representative of terrestrial freshwater. In addition, suspected counterfeit DSDWs have δ and electrical conductivity values similar to a mixed water (MW) product that was manufactured by purifying terrestrial freshwater and adulterating this with small amounts of brine. Furthermore, PCA results indicate the chemical constitution of suspected DSDW products to be similar to the MW product which falls between purified terrestrial freshwater and desalinized open seawater. These similarities imply that suspected counterfeit DSDW products are manufactured in a similar manner to the declared MW product. This study demonstrates how combining knowledge of stable water isotopes and PCA can be used in assessing the authenticity of commercial DSDW products. The method should be of great interest to similar investigations elsewhere.     

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.     

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

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

In situ measurement of CO2 and water vapour isotopic compositions at a forest site using mid-infrared laser absorption spectroscopy

We conducted continuous, high time-resolution measurements of CO₂ and water vapour isotopologues (¹⁶O¹²C¹⁶O, ¹⁶O¹³C¹⁶O and ¹⁸O¹²C¹⁶O for CO₂, and H₂¹⁸O for water vapour) in a red pine forest at the foot of Mt. Fuji for 9 days from the end of July 2010 using in situ absorption laser spectroscopy. The δ¹⁸O values in water vapour were estimated using the δ²H–δ¹⁸O relationship. At a scale of several days, the temporal variations in δ¹⁸O-CO₂ and δ¹⁸O-H₂O are similar. The orders of the daily Keeling plots are almost identical. A possible reason for the similar behaviour of δ¹⁸O-CO₂ and δ¹⁸O-H₂O is considered to be that the air masses with different water vapour isotopic ratios moved into the forest, and changed the atmosphere of the forest. A significant correlation was observed between δ¹⁸O-CO₂ and δ¹³C-CO₂ values at nighttime (r²≈0.9) due to mixing between soil (and/or leaf) respiration and tropospheric CO₂. The ratios of the discrimination coefficients (Δ_a/Δ) for oxygen (Δ_a) and carbon (Δ) isotopes during photosynthesis were estimated in the range of 0.7–1.2 from the daytime correlations between δ¹⁸O-CO₂ and δ¹³C-CO₂ values.     

Isotopic fingerprints of the Lake Żabińskie (NE Poland) hydrological system on contemporary carbonates precipitated in the lake

An isotopic monitoring was undertaken in 2012–2014 at Lake ?abińskie (Mazurian Lakeland, NE Poland). The aim was to identify the factors and processes controlling an isotopic composition of the lake water and to explore the mechanism responsible for recording the climatic signal in stable isotope composition of deposited carbonates. δ¹⁸O and δ²H in the precipitation, lake water column, inflows and outflow, δ¹⁸O and δ¹³C in the carbonate fraction of sediments trapped in the water column were recorded with monthly resolution. A relationship between δ¹⁸O and δ²H in local precipitation was used to estimate the local meteoric water line. The dataset obtained for the water enabled to identify the modification of the water’s isotopic composition due to evaporation, connected with seasonal lake water stratification and mixing patterns. Statistically significant correlation coefficients suggest that the δ¹⁸O of the carbonate fraction in the sediment traps depends on the δ¹⁸O of rainfall water and on air temperature. The fractionation coefficient α shows that in summer months the carbonate precipitation process is closest to equilibrium. As expected for an exorheic lake, no significant correlation was observed between δ¹⁸O and δ¹³C in precipitated carbonate.