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     

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.     

Isotope hydrology and baseflow geochemistry in natural and human-altered watersheds in the Inland Pacific Northwest,USA

This study presents a stable isotope hydrology and geochemical analysis in the inland Pacific Northwest (PNW) of the USA. Isotope ratios were used to estimate mean transit times (MTTs) in natural and human-altered watersheds using the FLOWPC program. Isotope ratios in precipitation resulted in a regional meteoric water line of δ²H?=?7.42·δ¹⁸O?+?0.88 (n?=?316; r²?=?0.97). Isotope compositions exhibited a strong temperature-dependent seasonality. Despite this seasonal variation, the stream δ¹⁸O variation was small. A significant regression (τ?=?0.11D^?1.09; r²?=?0.83) between baseflow MTTs and the damping ratio was found. Baseflow MTTs ranged from 0.4 to 0.6 years (human-altered), 0.7 to 1.7 years (mining-altered), and 0.7 to 3.2 years (forested). Greater MTTs were represented by more homogenous aqueous chemistry whereas smaller MTTs resulted in more dynamic compositions. The isotope and geochemical data presented provide a baseline for future hydrological modelling in the inland PNW.     

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.     

Combined approach of isotope mass balance and hydrological water balance methods to constrain the sources of lake water as exemplified on the small dimictic lake Silbersee,northern Germany

Stable isotopes of hydrogen and oxygen are often used for water balance calculations of lakes. We present an approach combining the lake water balance with an isotope mass balance to constrain the sources and sinks of the water of a small dimictic lake subjected to eutrophication. Meteorological and hydraulic data in combination with measured isotope signatures of the different water compartments enabled to assess the degree of surface water/groundwater interaction and the amount of overland flow into the lake. Groundwater could be excluded as a lake water source, as its water level was always below the lake water level. In the absence of a channelled inflow, precipitation and overland flow were the remaining options, whereby the latter was only active during periods of exceptionally high rainfall. While the groundwater signatures adjacent to the lake showed an influence of lake water, the lake water balance itself indicated that the associated volumetric water loss to groundwater is rather negligible. In the present case, only a combined assessment of hydrological and isotopic data allowed for an accurate characterization of the studied lake and a quantification of its water sources and sinks, highlighting the importance of using more than one methodological approach for such a purpose.     

Controls over spatial and seasonal variations on isotopic composition of the precipitation along the central and eastern portion of Brazil

Based on Global Network Isotopes in Precipitation (GNIP) isotopic data set, a review of the spatial and temporal variability of δ¹⁸O and δ²H in precipitation was conducted throughout central and eastern Brazil, indicating that dynamic interactions between Intertropical and South Atlantic Convergence Zones, Amazon rainforest, and Atlantic Ocean determine the variations on the isotopic composition of precipitation over this area. Despite the seasonality and latitude effects observed, a fair correlation with precipitation amount was found. In addition, Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) air mass back trajectories were used to quantify the factors controlling daily variability in stable isotopes in precipitation. Through a linear multiple regression analysis, it was observed that temporal variations were consistent with the meteorological parameters derived from HYSPLIT, particularly precipitation amount along the trajectory and mix depth, but are not dependent on vapour residence time in the atmosphere. These findings also indicate the importance of convective systems to control the isotopic composition of precipitation in tropical and subtropical regions.     

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

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

A 6.5-year continuous record of sea surface salinity and seawater isotopic composition at Harbour of Ishigaki Island,southwest Japan

We produced continuous records of sea surface salinity and isotopic composition from 1998 to 2004 at Ishigaki Island, southwest Japan, and found clear seasonal variations in salinity and oxygen isotopic composition and increasing trends of them after 1999. These increasing trends could be principally due to the decreasing difference between local precipitation (P) and evaporation (E), as a result of the reduction of horizontal vapour transport from adjacent oceans. When samples collected in heavy rainfall events were excluded, the average Δδ¹⁸O/Δ salinity slope was obtained as 0.31, 0.35 in summer and 0.28 in winter. Estimated E/P ratios based on the isotopic box model are in good agreement with the ratios of independently estimated E to observed P.     

Hydrogeochemical and isotope study of perched aquifers in the Cuvelai-Etosha Basin,Namibia

A hydrogeochemical and stable isotope study (²H and ¹⁸O) was carried out in the Cuvelai-Etosha Basin in order to characterize available groundwater and to identify possible recharge mechanisms for the perched aquifers. Data were collected during seven field campaigns between 2013 and 2015 from a total of 24 shallow and deep groundwater hand-dug wells. In the investigated groundwaters, hydrogencarbonate is the dominating anion in both well types, whereas cations vary between calcium and magnesium in deep wells, and sodium and potassium in shallow wells. Groundwater chemistry is controlled by dissolution of carbonate minerals, silicate weathering and ion exchange. Stable isotopic composition suggests that deep groundwater is recharged by high-intensity/large rainfall events, whereas the shallow wells can even be recharged by less-intense/small rainfall events. Water in deep wells reflect a mixture of water influenced by evaporation during or before infiltration and water that infiltrated through fast preferential pathways, whereas shallow wells are strongly influenced by evaporation. The findings of this research contribute to improve the understanding of hydrogeochemistry, recharge paths and temporal variations of perched aquifers.     

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

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

Hydrology of the lakes in Central Wohlthat Massif,East Antarctica: new results

In 1983/1984, in the course of the 28th Soviet Antarctic Expedition, waterbody, ice cover, and surrounding glaciers of the lakes Untersee and Obersee were sampled along some depth profiles. The geochemical data of those samples, now available, show the homogeneity of both large lakes in vertical (down to the maximum depth) as well as in lateral directions. The comparison of isotope and chemical composition of lake water and adjoining glacier ice suggests strong differences in the long-term evolution between the lakes Untersee and Obersee. First data from a lakelet, embedded in the large morainic area to the west of Lake Untersee, are of special interest: the δ²H values of the lakelet water are lower than those of recent regional glacier ice by 50‰ SMOW. This fact indicates that the lakelet is fed episodically by Pleistocene dead ice, covered by the morainic material.     

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.     

Identifying local and regional groundwater in basins: chemical and stable isotopic attributes of multivariate classification of hydrochemical data,the Lower Virgin River Basin,Nevada, Arizona and Utah,U.S.A

In the Basin and Range Province of the Southwestern U.S.A., deep carbonate groundwater has been suggested as a significant source to many overlying basin-fill alluvial aquifer systems. Notwithstanding, testing this hypothesis is limited by obtaining data from such considerable depths and complex geology.

This study uses δ²H and δ¹⁸O data from springs, rivers, and wells tapping shallow basin-fill groundwater to test the hydrochemical interpretation of deep regional carbonate groundwater flow into the basin-fill aquifers. Stable isotopic and major ion attributes of hydrochemical facies suggest basin-fill alluvial groundwater of the Lower Virgin River Basin is a mixture of precipitation recharge within the Lower Virgin River Basin or the Clover and Escalante Desert Basin northwards, and the deep carbonate flow. The data support the conclusions that in the Lower Virgin River Basin, deep carbonate groundwater is an important source to the alluvial aquifer system and likely accounts for approximately 50% of the alluvial aquifer groundwater. Na⁺, K⁺, and SO₄^2– increase in the basin-fill alluvial groundwaters outside the Virgin River floodplain appears to be related with upwelling of deep regional groundwater, and indicating that the chemical character of the basin-fill alluvial groundwaters are related to the deeper flow systems.     

Isotopic fingerprint of the middle Olt River basin,Romania

One of the most important tributaries of the Danube River in Romania, the Olt River, was characterized in its middle catchment in terms of the isotopic composition using continuous flow–isotope ratio mass spectrometry (CF–IRMS). Throughout a period of 10 months, from November 2010 to August 2011, water samples from the Olt River and its more important tributaries were collected in order to investigate the seasonal and spatial isotope patterns of the basin waters. The results revealed a significant difference between the Olt River and its tributaries, by the fact that the Olt River waters show smaller seasonal variations in the stable isotopic composition and are more depleted in ¹⁸O and ²H. The waters present an overall enrichment in heavy isotopes during the warm seasons.     

Insights from stable isotopes of water and hydrochemistry to the evolutionary processes of groundwater in the Subei lake basin,Ordos energy base,Northwestern China

ABSTRACT

Changes in groundwater evolutionary processes due to aquifer overexploitation show a world-wide increase and have been of growing concern in recent years. The study aimed to improve the knowledge of groundwater evolutionary processes by means of stable water isotopes and hydrochemistry in a representative lake basin, Ordos energy base. Groundwater, precipitation, and lake water collected during four campaigns were analysed by stable isotopes and chemical compositions. Results showed that temperature effect predominated the isotope fractionation in precipitation, while evaporation and inadequate groundwater recharge were the key factors explaining high salinity and isotopic enrichment in lake water. Additionally, the Kuisheng Lake was a preferential area of groundwater recharge, while the Subei Lake received less sources from underlying aquifer due to the combined effects of low permeable zone and upstream groundwater captured by the production wells. The homogeneous isotope signatures of groundwater may be ascribed to the closely vertical hydraulic connectivity between the unconfined and the confined aquifers. Isotopically enriched groundwater pumping from well field probably promoted isotopic depletion in groundwater depression cone. These findings not only provide the conceptual framework for the inland basin, but also have important implications for sustainable groundwater management in other groundwater discharge basins with arid climate.     

Estimation of snow and glacier melt contribution to Liddar stream in a mountainous catchment,western Himalaya: an isotopic approach

Snow- and glacier-dominated catchments in the Himalayas are important sources of fresh water to more than one billion people. However, the contribution of snowmelt and glacier melt to stream flow remains largely unquantified in most parts of the Himalayas. We used environmental isotopes and geochemical tracers to determine the source water and flow paths of stream flow draining the snow- and glacier-dominated mountainous catchment of the western Himalaya. The study suggested that the stream flow in the spring season is dominated by the snowmelt released from low altitudes and becomes isotopically depleted as the melt season progressed. The tracer-based mixing models suggested that snowmelt contributed a significant proportion (5–66?%) to stream flow throughout the year with the maximum contribution in spring and summer seasons (from March to July). In 2013 a large and persistent snowpack contributed significantly (～51?%) to stream flow in autumn (September and October) as well. The average annual contribution of glacier melt to stream flow is little (5?%). However, the monthly contribution of glacier melt to stream flow reaches up to 19?% in September during years of less persistent snow pack.     

Application of stable isotopes and hydrochemical analysis in groundwater aquifers of Argolis Peninsula (Greece)

The present study examines the isotopic and hydrochemical composition of 18 inland spring waters and 3 coastal karstic spring waters, covering the period between October 2005 and March 2008. The stable isotopes (¹⁸O, ²H) processing has revealed the absence of significant evaporation phenomena and that the origin of fresh water samples is meteoric. Using ¹⁸O values in rainfall waters, an average line of isotopic depletion with altitude has been constructed, extracting a rate of?0.45‰/100 m as typical for the study area. Furthermore, the mean altitude of recharge of the springs has been estimated by plotting the groundwater sampling points on a δ¹⁸O versus altitude diagram. Hydrochemistry results have shown that the dissolution of carbonate, flysch and ophiolitic formations defines the hydrochemical characteristics of groundwater. Moreover, seawater intrusion in the coastal area is significantly high, causing the water in the three karstic springs to be brackish.