Reliability of stable carbon and oxygen isotope compositions of pedogenic needle fibre calcite as environmental indicators: examples from Western Europe

Stable carbon and oxygen isotope analyses were conducted on pedogenic needle fibre calcite (NFC) from seven sites in areas with roughly similar temperate climates in Western Europe, including the Swiss Jura Mountains, eastern and southern France, northern Wales, and north-eastern Spain. The δ¹³C values (?12.5 to?6.8 ‰ Vienna Pee Dee Belemnite (VPDB)) record the predominant C₃ vegetation cover at the sites. A good correlation was found between mean monthly climatic parameters (air temperature, number of frost days, humidity, and precipitation) and δ¹⁸O values (?7.8 to?3.4‰ VPDB) of all the NFC. Similar seasonal variations of δ¹⁸O values for monthly NFC samples from the Swiss sites and those of mean monthly δ¹⁸O values of local precipitation and meteorological data point out precipitation and preferential growth/or recrystallisation of the pedogenic needle calcite during dry seasons. These covariations indicate the potential of stable isotope compositions of preserved NFC in fossil soil horizons as a promising tool for palaeoenvironmental reconstructions.     

Spatial and seasonal variations in the stable C isotope composition of dissolved inorganic carbon and in physico-chemical water parameters in the Plitvice Lakes system

Plitvice Lakes waters were collected at 14 sampling points, including springs, tributaries and lakes, for the period 2002-2007. The results of the physical and chemical conditions of calcite precipitation as well as the δ(13)C values of dissolved inorganic carbon (DIC) were used to study the processes influencing calcite precipitation. Significant differences between spring, lake and stream waters as well as changes in the downstream direction were observed. The correlation between δ(13)C(DIC) values and physico-chemical conditions for calcite precipitation showed that calcite precipitates in lake waters which are oversaturated with respect to CaCO(3) (I (sat) values 4-10) and with δ(13)C(DIC) values between-11.5 and-8.5 ‰. In spring waters, the δ(13)C(DIC) values were more negative, from-14 to-12 ‰, and I (sat) values of 1-2 indicated that equilibrium conditions for calcite precipitation were not attained. The downstream increase in δ(13)C(DIC) correlated with the increase in the δ(13)C values of calcite in the lake sediments, suggesting that the freshwater calcite was mainly of autochthonous origin and precipitated within the water column in isotopic equilibrium with DIC.     

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.     

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.     

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.     

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 δ(13)C (average-28.2‰) and δ(18)O (average-18.4‰) values showed a strong positive correlation, typical for carbonate precipitated by rapid dissolution of CO(2) in a highly alkaline solution and consequent disequilibrium precipitation of CaCO(3). The main source of carbon is atmospheric or biogenic CO(2) in the poorly ventilated karstic cave, which is reflected in even lower δ(13)C values. Statistical analysis of δ(13)C and δ(18)O values of the four groups of samples showed that the governing factor of isotope fractionation is not the temperature, but rather the precipitation rate.     

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 isotope geochemistry of calcrete nodules and septarian concretions in a Quaternary 'red clay' paleovertisol from Hungary

Calcrete nodules and concretions in unusually large amounts are embedded in the Quaternary clay-rich (Vertisol-type) 'red clay' soil-sedimentary complex at the pediment of the Mátra Mountains (Hungary). Stable isotope signatures were studied in nodules and septarian concretions, uncommon due to their several millimeter sized calcite crystals filling voids and fractures, to reveal their origin. The isotope composition of calcrete covers a wide range: delta18O=-5.9 to-10.4 per thousand and delta13C=-8.9 to-12.3 per thousand (vs. V-PDB). Isotope compositions support pedogenic (sensu stricto) and/or shallow groundwater origin for the calcrete nodules and concretions, the role of 'evolved' (isotopically modified) groundwaters in the formation of secondary carbonate was possibly subordinate. Late-stage, large, Mn-rich euhedral calcite crystals in concretions have the lowest delta13C values, which are interpreted as a result of larger contribution of isotopically light organic carbon due to decomposition of organic matter under reducing conditions. Precipitation of late calcite crystals in concretions occurred in early diagenetic environment after shallow burial of the 'red clay' paleovertisol.     

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.     

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.     

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).     

Regime Shift Signatures from Stable Oxygen Isotopic Records of Otoliths of Atlantic Cod (Gadus morhua)

Abstract

The sudden collapse of Atlantic cod (Gadus morhua) may relate to ocean climate, or regime shifts as demonstrated in production of Pacific salmon. This paper reports the results of stable oxygen isotope ratio analyses (¹⁸O/¹⁶O or δ¹⁸O_A) from 91 otoliths of cod over a period of about 20 years. Seasonal δ¹⁸O_A variations of individual otoliths started at an initial value of about ?0.5 to 0‰ VPDB, and then reached a stable level in the range of +2.5 to +3.5‰ VPDB after 4–5 years. The initial low values correspond to the natal sources of mature cod, while the higher δ¹⁸O_A values represent the water conditions before the cod was caught. This pattern of δ¹⁸O_A variation was observed over the life history of all cod examined. Furthermore, the calculated isotopic temperatures agreed with those obtained from summer bottom trawl survey, indicating that δ¹⁸O_A of otoliths could be used as a thermometer in determining the ambient seawater temperature where the cod lived. Comparison of long-term δ¹⁸O_A records and biological and meteorological observations suggested that decadal-scale ecosystem changes did occur in the late 1970s and early 1990s in Atlantic Canada, comparable to regime shifts occurred in the North Pacific.     

There is no Temperature Dependence of Net Biochemical Fractionation of Hydrogen and Oxygen Isotopes in Tree-Ring Cellulose

Abstract

The isotopic composition of tree-ring cellulose was obtained over a two-year period from small diameter, riparian zone trees along an elevational transect in Big Cottonwood Canyon, Utah, USA to test for a possible temperature dependence of net biological fractionation during cellulose synthesis. The isotope ratios of stream water varied by only 3.6‰ and 0.2‰ in δD and δ¹⁸O, respectively, over an elevation change of 810m. The similarity in stream water and macroenvironment over the short (13km) transect produced nearly constant stem and leaf water δD and δ¹⁸O values. In addition, what few seasonal variations observed in the isotopic composition of source water and atmospheric water vapor or in leaf water evaporative enrichment were experienced equally by all sites along the elevational transect. The temperature at each site along the transect spanned a range of ≥ 5°C as calculated using the adiabatic lapse rate. Since the δD and δ¹⁸O values of stem and leaf water varied little for these trees over this elevation/ temperature transect, any differences in tree-ring cellulose δD and δ¹⁸O values should have been associated with temperature effects on net biological fractionation. However, the slopes of the regressions of elevation versus the δD and δ¹⁸O values of tree-ring cellulose were not significantly different from zero indicating little or no temperature dependence of net biological fractionation. Therefore, cross-site climatic reconstruction studies using the isotope ratios of cellulose need not be concerned that temperatures during the growing season have influenced results.     

Spatial and seasonal variations in the stable C isotope composition of dissolved inorganic carbon and in physico-chemical water parameters in the Plitvice Lakes system

Plitvice Lakes waters were collected at 14 sampling points, including springs, tributaries and lakes, for the period 2002–2007. The results of the physical and chemical conditions of calcite precipitation as well as the δ¹³C values of dissolved inorganic carbon (DIC) were used to study the processes influencing calcite precipitation. Significant differences between spring, lake and stream waters as well as changes in the downstream direction were observed. The correlation between δ¹³C_DIC values and physico-chemical conditions for calcite precipitation showed that calcite precipitates in lake waters which are oversaturated with respect to CaCO₃ (I _sat values 4–10) and with δ¹³C_DIC values between?11.5 and?8.5 ‰. In spring waters, the δ¹³C_DIC values were more negative, from?14 to?12 ‰, and I _sat values of 1–2 indicated that equilibrium conditions for calcite precipitation were not attained. The downstream increase in δ¹³C_DIC correlated with the increase in the δ¹³C values of calcite in the lake sediments, suggesting that the freshwater calcite was mainly of autochthonous origin and precipitated within the water column in isotopic equilibrium with DIC.     

Isotopic characteristics of meteoric waters in the Belgrade region

The stable isotope composition of hydrogen (delta(2)H) and oxygen (delta(18)O) 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 delta(2)H=7.8 (+/-0.2) delta(18)O+7.3(+/-1.6) (r(2)=0.98, n=60, sigma=0.52) for the whole period of observation is close to the global meteoric water line. The amount-weighted mean delta(2)H and delta(18)O values of precipitation were-65+/-27 per thousand and-9.4+/-3.4 per thousand, respectively. Good correlation between delta(18)O values (r approximately >0.67) and ambient temperature and relative humidity was obtained. Stream-water data ranged from-94 to-60 per thousand for delta(2)H and from-11.0 to approximately 5.7 per thousand for delta(18)O 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.     

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.     

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.     

Comparison of sample preparation methods for stable isotope analysis of dissolved sulphate in forested watersheds

Pretreatment methods for measuring stable sulphur (δ(34)S) and oxygen (δ(18)O) isotope ratios of dissolved sulphate from watersheds have evolved throughout the last few decades. The current study evaluated if there are differences in the measured stable S and O isotope values of dissolved sulphate from forested watersheds when pretreated using three different methods: Method 1 (M1): adsorb sulphate on anion exchange resins and send directly to isotope facility; Method 2 (M2): adsorb sulphate on anion exchange resins, extract sulphate from anion exchange resins, and send the produced BaSO(4) to the isotope facility; and Method 3 (M3): directly precipitate BaSO(4) without anion exchange resins with the precipitates being sent to the isotope facility. We found an excellent agreement of the δ(34)S(sulphate) values among all the three methods. However, some differences were observed in the δ(18)O(sulphate) values (M1 versus M2:-1.5 ‰; M1 versus M3:-1.2 ‰) associated with possible O contamination before isotope measurement. Several approaches are recommended to improve the pretreatment procedures for δ(18)O(sulphate) analysis.     

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.