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.     

Stable isotopes determination in some Romanian fruit juices

The characterisation of 45 Romanian single-strength fruit juices (apples, pears, plums and grapes) collected from different Transylvanian areas by means of stable isotope approach are presented and discussed in this study. We measured (2)H/(1)H, (18)O/(16)O ratios from water juice and (13)C/(12)C from pulp and compared these results with those already reported in the literature for single-strength juices, in order to see how the geographical and climatic conditions of Transylvania and the meteorological peculiarities of the year 2010 influence the isotopic composition of the investigated fruit juices. The δ(13)C mean values that we found for apple pulp picked up from different Transylvanian areas show slight differences, probably due to the environmental conditions of the plants. No significant correlation either between the variety of apple or the geographical origin and δ(13)C value was established.     

Stable isotope determination of ester and ether methyl moieties in plant methoxyl groups

Plant methoxyl groups of lignin and pectin have both distinct stable hydrogen isotope (δ²H) and carbon isotope (δ¹³C) values that can be used for studying environmental processes and for investigating the origin and authenticity of biomaterials. Up to now, the reported methods have been applied only to determine isotope values of the bulk plant methoxyl pool. In this work, we have applied several methods to distinguish between stable isotope ratios of methoxyl groups of pectin and the bulk plant methoxyl pool. Our results demonstrate that by applying alkaline hydrolysis to specifically cleave off the ester methyl moiety (pectin-like), we can distinguish δ²H and δ¹³C values of the pectin methoxyl pool from the bulk methoxyl pool. No measureable isotope discrimination was observed either during sample preparation or during analytical measurement. Furthermore, using this method, no major isotope difference in either the hydrogen or carbon isotope signature of the methoxyl groups of plant pectin and bulk matter from plant species such as leaves from trees, apples, carrots and potatoes was noted. We show the methanol released during alkaline hydrolysis of plant material and subsequently treated with hydriodic acid to be an excellent procedure to measure specifically and precisely the δ¹³C and δ²H isotope values of plant pectin-like methoxyl groups. This method is particularly advantageous when plant matter with a low methoxyl content has to be analysed.     

Stable isotopes determination in some Romanian wines

This paper presents a study concerning the isotopic fingerprint ((18)O and (13)C) 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 δ(18)O 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 δ(13)C values were very similar for all the samples with an average of about-26 ‰. The difference between the δ(18)O values was due to the different climatic zones, which have an influence on the δ(18)O 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 δ(18)O 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.     

Temporal and spatial distribution of isotopes in river water in Central Europe: 50 years experience with the Austrian network of isotopes in rivers

The Austrian network of isotopes in rivers comprises about 15 sampling locations and has been operated since 1976. The Danube isotope time series goes back to 1963. The isotopic composition of river water in Central Europe is mainly governed by the isotopic composition of precipitation in the catchment area; evaporation effects play only a minor role. Short-term and long-term isotope signals in precipitation are thus transmitted through the whole catchment. The influence of climatic changes has become observable in the long-term stable isotope time series of precipitation and surface waters. Environmental ³H values were around 8 TU in 2015, short-term ³H pulses up to about 80 TU in the rivers Danube and March were a consequence of releases from nuclear power plants. The complete isotope data series of this network will be included in the Global Network of Isotopes in Rivers database of the International Atomic Energy Agency (IAEA) in 2017. This article comprises a review of 50 years isotope monitoring on rivers and is also intended to provide base information on the (isotope-)hydrological conditions in Central Europe specifically for the end-users of these data, e.g. for modelling hydrological processes. Furthermore, this paper includes the 2006–2015 supplement adding to the Danube isotope set published earlier.     

Natural and anthropogenic variations in the Po river waters (northern Italy): insights from a multi-isotope approach

Po is the main Italian river and the δ¹⁸O and δ²H of its water reveal a similarity between the current meteoric fingerprint and that of the past represented by groundwater. As concerns the hydrochemisty, the Ca–HCO₃ facies remained constant over the last 50 year, and only nitrate significantly increased from less than 1?mg/L to more than 10?mg/L in the 1980s, and then attenuated to a value of 9?mg/L. Coherently, δ¹³C_DIC and δ³⁴S_SO4 are compatible with the weathering of the lithologies outcropping in the basin, while extremely variable δ¹⁵N_NO3 indicates contribution from pollutants released by urban, agricultural and zootechnical activities. This suggests that although the origin of the main constituents of the Po river water is geogenic, anthropogenic contributions are locally significant. Noteworthy, the associated aquifers have the same nitrogen isotopic signature of the Po river, but are characterized by significantly higher NO^– ₃ concentration. This implies that aquifers’ pollution is not ascribed to inflow of current river water, and that the attenuation of the nitrogen load recorded in the river is not occurring in the aquifers, due to their longer water residence time and delayed recovery from anthropogenic contamination.     

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.     

δ2H, δ13C and δ18O from whole wood, α-cellulose and lignin methoxyl groups in Pinus sylvestris: a multi-parameter approach

Novel tree ring parameters – δ¹³C and δ²H from methoxyl groups – have been developed to reconstruct palaeoclimate. Tests with δ¹³C and δ¹⁸O derived from whole wood and cellulose samples, however, indicated differences in the isotopic composition and climate signal, depending on the extracted wood component. We assess this signal dependency by analysing (i) δ¹³C and δ¹⁸O from whole wood and cellulose and (ii) δ¹³C and δ²H from methoxyl groups, using Pinus sylvestris L. growing near Altenkirchen (Germany). Results indicate significant correlations among the time series derived from whole wood, cellulose, and lignin methoxyl groups. Compared with the whole wood samples, δ¹³C from methoxyl groups showed a different and overall lower response to climate parameters. On the other hand, δ²H from methoxyl groups showed high correlations with temperature and was also correlated with ring width, indicating its potential as a temperature proxy. Isotope time series with the highest correlation with climatic parameter were: (i) whole wood and cellulose δ¹³C with growing season precipitation and summer temperature; (ii) methoxyl groups with spring precipitation; (iii) whole wood and cellulose δ¹⁸O correlates with annual evapotranspiration and water balance; and (iv) methoxyl group δ²H with spring temperatures. These findings reveal that multiple climate elements can be reconstructed from different wood components and that whole wood proxies perform comparably to cellulose time series.     

Hekla cold springs (Iceland): groundwater mixing with magmatic gases

We have analysed the chemical and stable isotope compositions of four spring waters situated just northwest of the Hekla volcano, where cold water emerges from the base of the lava flows. The stable isotope ratios of water (H, O), dissolved inorganic carbon (C) and sulphate (S) were used to determine whether magmatic gases are mixing with the groundwater. The waters can be characterised as Na-HCO₃ type. The results show that deep-seated gases mix with groundwater, substantially affecting the concentration of solutes and the isotopic composition of dissolved carbon and sulphate.     

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.     

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.     

Use of isotopes to study floodplain wetland and river flow interaction in the White Volta River basin,Ghana

Floodplain wetlands influence the timing and magnitude of stream responses to rainfall. In managing and sustaining the level of water resource usage in any river catchment as well as when modelling hydrological processes, it is essential that the role of floodplain wetlands in stream flows is recognised and understood. Existing studies on hydrology within the Volta River basin have not adequately represented the variability of wetland hydrological processes and their contribution to the sustenance of river flow. In order to quantify the extent of floodwater storage within riparian wetlands and their contribution to subsequent river discharges, a series of complementary studies were conducted by utilising stable isotopes, physical monitoring of groundwater levels and numerical modelling. The water samples were collected near Pwalugu on the White Volta River and at three wetland sites adjacent to the river using the grab sampling technique. These were analysed for ¹⁸O and ²H. The analysis provided an estimate of the contribution of pre-event water to overall stream flow. In addition, the variation in the isotopic composition in the river and wetland water samples, respectively, revealed the pattern of flow and exchange of water between the wetlands and the main river system.     

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.     

Breath water-based doubly labelled water method for the noninvasive determination of CO2 production and energy expenditure in mice

ABSTRACT

We explored a novel doubly labelled water (DLW) method based on breath water (BW-DLW) in mice to determine whole body CO₂ production and energy expenditure noninvasively. The BW-DLW method was compared to the DLW based on blood plasma. Mice (n?=?11, 43.5?±?4.6?g body mass (BM)) were administered orally a single bolus of doubly labelled water (1.2?g H₂¹⁸O kg BM^?1 and 0.4?g ²H₂O kg BM^?1, 99 atom% (AP) ¹⁸O or ²H). To sample breath water, the mice were placed into a respiration vessel. The exhaled water vapour was condensed in a cold-trap. The isotope enrichments of breath water were compared with plasma samples. The ²H/¹H and ¹⁸O/¹⁶O isotope ratios were measured by means of isotope ratio mass spectrometry. The CO₂ production (RCO₂) was calculated from the ²H and ¹⁸O enrichments in breath water and plasma over 5 days. The isotope enrichments of breath water vs. plasma were correlated (R²?=?0.89 for ²H and 0.95 for ¹⁸O) linearly. The RCO₂ determined based on breath water and plasma was not different (113.2?±?12.7 vs. 111.4?±?11.0?mmol?d^–1), respectively. In conclusion, the novel BW-DLW method is appropriate to obtain reliable estimates of RCO₂ avoiding blood sampling.     

Hydrology of the North Klondike River: carbon export,water balance and inter-annual climate influences within a sub-alpine permafrost catchment

Arctic and sub-arctic watersheds are undergoing significant changes due to recent climate warming and degrading permafrost, engendering enhanced monitoring of arctic rivers. Smaller catchments provide understanding of discharge, solute flux and groundwater recharge at the process level that contributes to an understanding of how larger arctic watersheds are responding to climate change. The North Klondike River, located in west central Yukon, is a sub-alpine permafrost catchment, which maintains an active hydrological monitoring station with a record of >40 years. In addition to being able to monitor intra-annual variability, this data set allows for more complex analysis of streamflow records. Streamflow data, geochemistry and stable isotope data for 2014 show a groundwater-dominated system, predominantly recharged during periods of snowmelt. Radiocarbon is shown to be a valuable tracer of soil zone recharge processes and carbon sources. Winter groundwater baseflow contributes 20?% of total annual discharge, and accounts for up to 50?% of total river discharge during the spring and summer months. Although total stream discharge remains unchanged, mean annual groundwater baseflow has increased over the 40-year monitoring period. Wavelet analysis reveals a catchment that responds to El Niño and longer solar cycles, as well as climatic shifts such as the Pacific Decadal Oscillation.

Dedicated to Professor Peter Fritz on the occasion of his 80th birthday     

Defining near-surface groundwater flow regimes in the semi-arid glaciated plains of North America

The dominant transport mechanisms controlling the migration of contaminants in geologic media are advection and molecular diffusion. To date, defining which transport mechanism dominates in saturated, non-lithified sediments has been difficult. Here, we illustrate the value of using detailed profiles of the conservative stable isotope values of water (δ²H and δ¹⁸O) to identify the dominant processes of contaminant transport (i.e. diffusion- or advection-dominated transport) in near-surface, non-lithified, saturated sediments of the Interior Plains of North America (IPNA). The approach presented uses detailed δ¹⁸O analyses of glacial till, glaciolacustrine clay, and fluvial sand core samples taken to depths of 11–50 m below ground at 22 sites across the IPNA to show whether transport in the fractured and oxidized sediments is dominated by advection or diffusion. Diffusion is by far the dominant transport mechanism in fine-textured lacustrine and glacial till sediments, but lateral advection dominates transport in sand-rich sediments and some oxidized, fine-textured lacustrine and glacial till sediments. The approach presented has a number of applications, including identifying dominant transport mechanisms in geomedia and potential protective barriers for underlying aquifers or surface waters, constraining groundwater transport models, and selecting optimum locations for monitoring wells. These findings should be applicable to most glaciated regions of the world that are composed of similar hydrogeologic units (i.e. low K clay till layers overlain by higher K coarse-textured aquifers or weathered clay till layers) and may also be applicable to non-glaciated regions exhibiting similar hydrogeologic characteristics.     

Isotopic composition of atmospheric moisture from pan water evaporation measurements

A continuous and reliable time series data of the stable isotopic composition of atmospheric moisture is an important requirement for the wider applicability of isotope mass balance methods in atmospheric and water balance studies. This requires routine sampling of atmospheric moisture by an appropriate technique and analysis of moisture for its isotopic composition. We have, therefore, used a much simpler method based on an isotope mass balance approach to derive the isotopic composition of atmospheric moisture using a class-A drying evaporation pan. We have carried out the study by collecting water samples from a class-A drying evaporation pan and also by collecting atmospheric moisture using the cryogenic trap method at the National Institute of Hydrology, Roorkee, India, during a pre-monsoon period. We compared the isotopic composition of atmospheric moisture obtained by using the class-A drying evaporation pan method with the cryogenic trap method. The results obtained from the evaporation pan water compare well with the cryogenic based method. Thus, the study establishes a cost-effective means of maintaining time series data of the isotopic composition of atmospheric moisture at meteorological observatories. The conclusions drawn in the present study are based on experiments conducted at Roorkee, India, and may be examined at other regions for its general applicability.     

Isotopic and multielemental fingerprinting of organically and conventionally grown potatoes

Two marker combinations were used for the differentiation of organically produced from conventionally produced potatoes and also for the geographical origin identification. Fifty-seven samples (from Romanian local producers or imported) were analysed from the stable isotopic (isotope ratio mass spectrometry) and elemental profile (inductively coupled plasma mass spectrometry) point of view. In order to assess the best marker combination, both isotopic and elemental experimental results were subject to chemometric analysis. The statistical tests performed were ANOVA test, Pearson correlation, principal component analysis and linear discriminant analysis (LDA). For a more comprehensive differentiation between organic vs. conventional potato samples, LDA was applied, and 94.7?% of original cases were correctly classified and the percentage obtained in cross-validation procedure was 91.2?%. Regarding the geographic origin classification, LDA provided an initial classification of 96.5?%, while for cross-validation the percentage was 87.7. LDA found δ¹⁵N, Cd, Ca, Cu and Zn as best discrimination markers between organically and conventionally grown potatoes. The strongest predictors for Romania vs. foreign geographical areas along LDA were seen to be Ca, P, Co, Ni and δ¹³C.     

Delineating sources of groundwater recharge and carbon in Holocene aquifers of the central Gangetic basin using stable isotopic signatures

Stable isotopes of water (δ²H, δ¹⁸O) and δ¹³C_TIC were used as a tool to trace the recharge processes, natural carbon (organic and inorganic) source and dynamics in the aquifers of the central Gangetic basin, India. Stable isotope (δ²H, δ¹⁸O) record of groundwater (n?=?105) revealed that the groundwater of Piedmont was recharged by meteoric origin before evaporation, while aquifers of the older and younger alluvium were recharged by water that had undergone evaporation loss. River Ganges and its tributaries passing through this area have very little contribution in recharging while ponds play no role in the recharging of adjacent aquifers. The connectivity of shallow aquifers of aquitard formation (comprised of clay/sandy clay with thin patches of fine grey sand), i.e. 25–60?m below ground level (bgl) with the main upper aquifer (at a depth of >120?m?bgl) was found to be higher in older and younger alluvium. Negative values of δ¹³C_TIC (median ?9.6 ‰; range ?13.2 to ?5.4 ‰) and high TIC (median 35?mM; range 31–46?mM) coupled with low TOC (median 1.35?mg/L; range 0.99–1.77?mg/L) indicated acceleration in microbial activity in the younger alluvium, especially in the active floodplain of river Ganges and its proximity.