Differential Transport of Escherichia coli Isolates Compared to Abiotic Tracers in a Karst Aquifer

Lack of filtration and rapid transport of groundwater and particulate matter make karst aquifers susceptible to bacterial contamination. This study utilized quantitative polymerase chain reaction (qPCR) to examine the transport and attenuation of two nonvirulent isolates of Escherichia coli (E. coli) in relation to traditional groundwater tracers (rhodamine WT dye and 1-µm diameter latex microspheres) in a karst-conduit aquifer in central Kentucky. Bacterial isolates were labeled with stable isotopes (¹⁵N and ¹³C). All tracers were detected more than 6 km downstream from the injection site and demonstrated overlapping breakthrough curves, with differential transport observed between the two bacterial strains. The E. coli isolate containing the kps gene (low attachment) arrived at sampling sites 1.25 to 36 h prior to the bacterial isolate containing the iha gene (high attachment) and was detected in samples collected following storm events in which the iha isolate was not detected. The storage potential of contaminants within karst systems was demonstrated by the remobilization of all tracers during storm events more than 1 month after injection. Bacteria-sized microspheres were more easily remobilized during periods of increased discharge compared to other tracers. The study demonstrated that molecular biology techniques such as qPCR can be utilized as a sensitive analysis of bacterial tracers in karst aquifers and may prove to be a more sensitive analytical technique than stable isotope analysis for field-scale traces.     

Combining isotopic tracers (222Rn and δ13C) for improved modelling of groundwater discharge to small rivers

In regions where aquifers sustain rivers, the location and quantification of groundwater discharge to surface water are important to prevent pollution hazards, to quantify and predict low flows and to manage water supplies. ²²²Rn is commonly used to determine groundwater discharge to rivers. However, using this isotopic tracer is challenging because of the high diffusion capacity of ²²²Rn in open water. This study illustrates how a combination of isotopic tracers can contribute to an enhanced understanding of groundwater discharge patterns in small rivers. The aim of this paper is to combine ²²²Rn and δ¹³C_DIC to better constrain the physical parameters related to the degassing process of these tracers in rivers. The Hallue River (northern France) was targeted for this study because it is sustained almost exclusively by a fractured chalk aquifer. The isotopes ²²²Rn, δ¹³C_DIC, δ²H and δ¹⁸O were analysed along with other natural geochemical tracers. A mass balance model was used to simulate ²²²Rn and δ¹³C_DIC. The results of δ²H and δ¹⁸O analyses prove that evaporation did not occur in the river. The calibration of a numerical model to reproduce ²²²Rn and δ¹³C_DIC provides a best‐fit diffusive layer thickness of 3.21 × 10^?5 m. This approach is particularly useful for small rivers flowing over carbonate aquifers with high groundwater DIC where the evolution of river DIC reflects the competing processes of groundwater inflow and CO₂ degassing. This approach provides a means to evaluate groundwater discharge in small ungauged rivers. Copyright © 2014 John Wiley & Sons, Ltd.     

Monte Carlo Simulations as a Decision Support to Interpret δ15N Values of Nitrate in Groundwater

Intense farming is often associated with the excessive use of manure or fertilizers and the subsequent deterioration of the groundwater quality in many aquifers worldwide. Stable isotopes of dissolved nitrate (δ¹⁵N and δ¹⁸O) are widely used to determine sources of nitrate contamination and denitrification processes in groundwater but are often difficult to interpret. Thus, Monte Carlo simulations were carried out for a site in lower Bavaria, Germany, in order to explain δ¹⁵N observations in a porous groundwater system with two aquifers, the main aquifer (MA) and several smaller perched aquifers (PA). For evaluating potential contributions, frequency distributions of δ¹⁵N were simulated deriving from (I) the mixing of different nitrate sources, related to land use, as input to groundwater, combined with (II) transport of nitrate in groundwater and (III) microbial denitrification. Simulation results indicate a source-driven isotopic shift to heavier δ¹⁵N values of nitrate in groundwater, which may be explained by land use changes toward a more intensified agriculture releasing high amounts of manure. Microbial denitrification may play a role in the PA, with simulated δ¹⁵N distributions close to the observations. Denitrification processes are however unlikely for the MA, as reasonable simulation curve fits for such a scenario were obtained predominantly for unrealistic portions of nitrate sources and related land use. The applied approach can be used to qualitatively and quantitatively evaluate the influence of different potential contributions, which might mask each other due to overlapping δ¹⁵N ranges, and it can support the estimation of nitrate input related to land use.     

Isotope mixing models require individual isotopic tracer content for correct quantification of sediment source contributions

The use of isotopic tracers for sediment source apportionment is gaining interest with recent introduction of compound‐specific stable isotope tracers. The method relies on linear mixing of source isotopic tracers, and deconvolution of a sediment mixture initially quantifies the contribution of sources to the mixture's tracer signature. Therefore, a correction to obtain real sediment source proportions is subsequently required. As far as we are aware, all published studies to date have used total isotopic tracer content or a proxy (e.g., soil carbon content) for this post‐unmixing correction. However, as the relationship between the isotopic tracer mixture and the source mixture is different for each isotopic tracer, post‐unmixing corrections cannot be carried out with one single factor. This contribution presents an isotopic tracer model structure—the concentration‐dependent isotope mixing model (CD‐IMM)—to overcome this limitation. Herein, we aim to clarify why the “conventional” approach to converting isotopic tracer proportions to source proportions using a single factor is wrong. In an initial mathematical assessment, error incurred by not using CD‐IMM (NCD‐IMM) in unmixing two sources with two isotopic tracers showed a complex relation as a function of relative tracer contents. Next, three artificial mixtures with different proportions of three soil sources were prepared and deconvoluted using ¹³C of fatty acids using CD‐IMM and NCD‐IMM. Using NCD‐IMM affected both accuracy (mean average error increased up to a threefold compared with the CD‐IMM output) and precision (interquartile range was up to 2.5 times larger). Finally, as an illustrative example, the proportional source contribution reported in a published study was recalculated using CD‐IMM. This resulted in changes in estimated source proportions and associated uncertainties. Content of isotopic tracers is seldom reported in published work concerning use of isotopic tracers for sediment source partitioning. The magnitude of errors made by miscalculation in former studies is therefore difficult to assess. With this contribution, we hope the community will acknowledge the limitations of prior approaches and use a CD‐IMM in future studies.     

Density‐Driven Free‐Convection Model for Isotopically Fractionated Geogenic Nitrate in Sabkha Brine

Subsurface brines with high nitrate (NO₃^?) concentration are common in desert environments as atmospheric nitrogen is concentrated by the evaporation of precipitation and little nitrogen uptake. However, in addition to having an elevated mean concentration of ～525 mg/L (as N), NO₃^? in the coastal sabkhas of Abu Dhabi is enriched in ¹⁵N (mean δ¹⁵N ～17‰), which is an enigma. A NO₃^? solute mass balance analysis of the sabkha aquifer system suggests that more than 90% of the nitrogen is from local atmospheric deposition and the remainder from ascending brine. In contrast, isotopic mass balances based on Δ¹⁷O, δ¹⁵N, and δ¹⁸O data suggest approximately 80 to 90% of the NO₃^? could be from ascending brine. As the sabkha has essentially no soil, no vegetation, and no anthropogenic land or water use, we propose to resolve this apparent contradiction with a density‐driven free‐convection transport model. In this conceptual model, the density of rain is increased by solution of surface salts, transporting near‐surface oxygenated NO₃^? bearing water downward where it encounters reducing conditions and mixes with oxygen‐free ascending geologic brines. In this environment, NO₃^? is partially reduced to nitrogen gas (N₂), thus enriching the remaining NO₃^? in heavy isotopes. The isotopically fractionated NO₃^? and nitrogen gas return to the near‐surface oxidizing environment on the upward displacement leg of the free‐convection cycle, where the nitrogen gas is released to the atmosphere and new NO₃^? is added to the system from atmospheric deposition. This recharge/recycling process has operated over many cycles in the 8000‐year history of the shallow aquifer, progressively concentrating and isotopically fractionating the NO₃^?.     

An isotopic calibration study of precipitation,cave dripwater,and climate in west‐central Florida

A calibration study of oxygen and hydrogen isotopic composition from precipitation and cave dripwater was conducted in west‐central Florida at Legend Cave during 2007–2008. This study was performed to better understand how modern precipitation patterns can be discerned through examination of cave dripwater and speleothem calcite for paleoclimate reconstruction. The ‘amount effect’ was shown to be a dominant control on the oxygen isotopic composition of precipitation for the study area. A meteoric water line with a slope of 6·7 suggests evaporative effects occur either during precipitation or subsequent hydrological processes. However, δ¹⁸O values of cave dripwater averaged near the mean annual amount‐weighted average of precipitation, suggesting that the isotopic composition of dripwater tracks the long‐term average of rainfall. An observed weak seasonal influence occurred in the d‐excess values, with summer precipitation being more enriched due to increased evaporative effects. Comparison of precipitation δ¹⁸O values to synoptic weather data shows the dominant amount effect influence occurs due to strong convective storms producing highly ¹⁸O‐depleted rainfall at greater amounts during the year. Constant δ¹⁸O values of the dripwater indicate that paleoclimate reconstructions using speleothems from this area would record changes in annual to interannual shifts in precipitation amount above the cave. Copyright © 2011 John Wiley & Sons, Ltd.     

Hydrocarbon‐Rich Groundwater above Shale‐Gas Formations: A Karoo Basin Case Study

Horizontal drilling and hydraulic fracturing have enhanced unconventional hydrocarbon recovery but raised environmental concerns related to water quality. Because most basins targeted for shale‐gas development in the USA have histories of both active and legacy petroleum extraction, confusion about the hydrogeological context of naturally occurring methane in shallow aquifers overlying shales remains. The Karoo Basin, located in South Africa, provides a near‐pristine setting to evaluate these processes, without a history of conventional or unconventional energy extraction. We conducted a comprehensive pre‐industrial evaluation of water quality and gas geochemistry in 22 groundwater samples across the Karoo Basin, including dissolved ions, water isotopes, hydrocarbon molecular and isotopic composition, and noble gases. Methane‐rich samples were associated with high‐salinity, NaCl‐type groundwater and elevated levels of ethane, ⁴He, and other noble gases produced by radioactive decay. This endmember displayed less negative δ¹³C‐CH₄ and evidence of mixing between thermogenic natural gases and hydrogenotrophic methane. Atmospheric noble gases in the methane‐rich samples record a history of fractionation during gas‐phase migration from source rocks to shallow aquifers. Conversely, methane‐poor samples have a paucity of ethane and ⁴He, near saturation levels of atmospheric noble gases, and more negative δ¹³C‐CH₄; methane in these samples is biogenic and produced by a mixture of hydrogenotrophic and acetoclastic sources. These geochemical observations are consistent with other basins targeted for unconventional energy extraction in the USA and contribute to a growing data base of naturally occurring methane in shallow aquifers globally, which provide a framework for evaluating environmental concerns related to unconventional energy development (e.g., stray gas).     

Tracing groundwater nitrate sources in the Dakar suburban area: an isotopic multi‐tracer approach

The Dakar region is a mega city with multiple contaminant sources from urban expansion as well as industrial and agricultural activities. The major part of the region is underlain by unconfined sandy aquifer, which is vulnerable to contaminants derived from human land use. At present, the contaminated groundwater which extends over a large area in the suburban zone of Thiaroye poses a threat to the future of this valuable resource, and more specifically, a health threat. This study focuses on nitrate pollution occurrences and associated processes using nitrate isotope data (¹⁵N_NO3, ¹⁸O_NO3) combined with environmental isotopic tracers (¹⁸O, ²H, and ³H). Samples from 36 wells were collected to determine the level, distribution, and sources of contamination in relation to land use. Results indicate that shallow groundwater in the urbanized area of Thiaroye shows distinct evidence of surface contamination with nitrate as much as 300 mg/l NO₃^?. In rural area not serviced by water supply distribution network, much higher NO₃^? contents were found in few wells due to household and livestock feedlots. In most groundwater samples δ¹⁵N values ranged from + 10 to + 22‰, indicative of predominantly human and animal wastes. This was confirmed by environmental isotope data which suggest a mixture of polluted recharge waters. By using the dual δ¹⁵N vs δ¹⁸O as well as δ¹⁵N vs NO₃^? approach, denitrification may occur to some extent but it is blurred by mixing with new infiltrated nitrates and cycling derived from continuous leaky septic system. Results suggest that nitrate contamination of the aquifer is a consequence of unregulated urbanisation (homemade latrines), continuing contaminant transfer in shallow water depth where aerobic conditions prevail. Copyright © 2011 John Wiley & Sons, Ltd.     

Oxygen‐18 dynamics in precipitation and streamflow in a semi‐arid agricultural watershed,Eastern Washington,USA

Understanding flow pathways and mechanisms that generate streamflow is important to understanding agrochemical contamination in surface waters in agricultural watersheds. Two environmental tracers, δ¹⁸O and electrical conductivity (EC), were monitored in tile drainage (draining 12 ha) and stream water (draining nested catchments of 6‐5700 ha) from 2000 to 2008 in the semi‐arid agricultural Missouri Flat Creek (MFC) watershed, near Pullman Washington, USA. Tile drainage and streamflow generated in the watershed were found to have baseline δ¹⁸O value of ?14·7‰ (VSMOW) year round. Winter precipitation accounted for 67% of total annual precipitation and was found to dominate streamflow, tile drainage, and groundwater recharge. ‘Old’ and ‘new’ water partitioning in streamflow were not identifiable using δ¹⁸O, but seasonal shifts of nitrate‐corrected EC suggest that deep soil pathways primarily generated summer streamflow (mean EC 250 µS/cm) while shallow soil pathways dominated streamflow generation during winter (EC declining as low as 100 µS/cm). Using summer isotopic and EC excursions from tile drainage in larger catchment (4700‐5700 ha) stream waters, summer in‐stream evaporation fractions were estimated to be from 20% to 40%, with the greatest evaporation occurring from August to October. Seasonal watershed and environmental tracer dynamics in the MFC watershed appeared to be similar to those at larger watershed scales in the Palouse River basin. A 0·9‰ enrichment, in shallow groundwater drained to streams (tile drainage and soil seepage), of δ¹⁸O values from 2000 to 2008 may be evidence of altered precipitation conditions due to the Pacific Decadal Oscillation (PDO) in the Inland Northwest. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of runoff components using path analysis and isotopic measurements in a glacier‐covered alpine catchment (upper Hailuogou Valley) in southwest China

Monitoring of stable water isotopes (δ¹⁸O and δ²H) at the watershed scales can improve our understanding of complex hydrology and hydroclimatology of the watershed, especially in remote regions. Previous studies that used tracers for hydrograph separation are largely based on end‐member mixing approach (EMMA), but one drawback of this approach is that at least two independent tracers are required for multi‐component separation. Here we introduce a new approach—path analysis, in combination with isotopic measurements to investigate the runoff generation in a glacier‐covered alpine catchment (upper Hailuogou Valley) in southwest China. This newly developed method can not only provide a multi‐component hydrograph separation with the aid of only one tracer but also determine the direct and indirect influence of sources on streamflow. Path analysis show that the majority of streamflow is dominated by ice/snow meltwater that represents about 63–78% of the total discharge, whereas precipitation and groundwater contribute approximately 19–39% and 2–4% of the streamflow discharge, respectively. These results are in good agreement with those derived from EMMA (using ¹⁸O and Cl^? as tracers), corroborating that our proposed approach is successful in hydrograph separation of the catchment. This approach may provide new opportunities for the hydrograph separation of catchment with sparse data and be of interest to catchment hydrologists who seek to understand the behaviour of hydrologic systems. Copyright © 2015 John Wiley & Sons, Ltd.     

Isotopic composition (δ18O and δD) of precipitation and groundwater in a semi‐arid,mountainous area (Guadiana Menor basin,Southeast Spain)

We characterize the precipitation and groundwater in a mountainous (peaks slightly above 3000 m a.s.l.), semi‐arid river basin in SE Spain in terms of the isotopes ¹⁸O and ²H. This basin, with an extension of about 7000 km², is an ideal site for such a study because fronts from the Atlantic and the Mediterranean converge here. Much of the land is farmed and irrigated both by groundwater and runoff water collected in reservoirs. A total of approximately 100 water samples from precipitation and 300 from groundwater have been analysed. To sample precipitation we set up a network of 39 stations at different altitudes (800–1700 m a.s.l.), with which we were able to collect the rain and snowfall from 29 separate events between July 2005 and April 2007 and take monthly samples during the periods of maximum recharge of the aquifers. To characterize the groundwater we set up a control network of 43 points (23 springs and 20 wells) to sample every 3 months the main aquifers and both the thermal and non‐thermal groundwater. We also sampled two shallow‐water sites (a reservoir and a river). The isotope composition of the precipitation forms a local meteoric water line (LMWL) characterized by the equation δD = 7·72δ¹⁸O + 9·90, with mean values for δ¹⁸O and δD of − 10·28‰ and − 69·33‰, respectively, and 12·9‰ for the d‐excess value. To correlate the isotope composition of the rainfall water with groundwater we calculated the weighted local meteoric water line (WLMWL), characterized by the equation δD = 7·40δ¹⁸O + 7·24, which takes into account the quantity of water precipitated during each event. These values of (dδD/dδ¹⁸O)< 8 and d‐excess (δD–8δ¹⁸O)< 10 in each curve bear witness to the ‘amount effect’, an effect which is more manifest between May and September, when the ground temperature is higher. Other effects noted in the basin were those of altitude and the continental influence. The isotopic compositions of the groundwater are represented by the equation δD = 4·79δ¹⁸O − 18·64. The groundwater is richer in heavy isotopes than the rainfall, with mean values of − 8·48‰ for δ¹⁸O and − 59·27‰ for δD. The isotope enrichment processes detected include a higher rate of evaporation from detrital aquifers than from carbonate ones, the effects of recharging aquifers from irrigation return flow and/or from reservoirs' leakage and enrichment in δ¹⁸O from thermal water. Copyright © 2010 John Wiley & Sons, Ltd.     

Deuterium‐excess determination of evaporation to inflow ratios of an alpine lake: Implications for water balance and modeling

The numerous lakes on the Tibetan Plateau play an important role in the regional hydrological cycle and water resources, but systematic observations of the lake water balance are scarce on the Tibetan Plateau. Here, we present a detailed study on the water cycle of Cona Lake, at the headwaters of the Nujiang‐Salween River, based on 3 years (2011–2013) of observations of δ¹⁸O and δ²H, including samples from precipitation, lake water, and outlet surface water. Short‐term atmospheric water vapor was also sampled for isotope analyses. The δ²H–δ¹⁸O relationship in lake water (δ²H = 6.67δ¹⁸O ? 20.37) differed from that of local precipitation (δ²H = 8.29δ¹⁸O + 12.50), and the deuterium excess (d‐excess) in the lake water (?7.5‰) was significantly lower than in local precipitation (10.7‰), indicating an evaporative isotope enrichment in lake water. The ratio of evaporation to inflow (E /I ) of the lake water was calculated using both d‐excess and δ¹⁸O. The E /I ratios of Cona lake ranged from 0.24 to 0.27 during the 3 years. Observations of atmospheric water vapor isotopic composition (δ _A ) improved the accuracy in E /I ratio estimate over a simple precipitation equilibrium model, though a correction factor method provided nearly identical estimates of E /I ratio. The work demonstrates the feasibility of d‐excess in the study of the water cycle for lakes in other regions of the world and provides recommendations on sampling strategies for accurate calculations of E /I ratio.     

Isotopic Characterization of Sulfate in a Shallow Aquifer Impacted by Agricultural Fertilizer

The stable isotope ratios of groundwater sulfate (³⁴S/³²S, ¹⁸O/¹⁶O) are often used as tracers to help determine the origin of groundwater or groundwater contaminants. In agricultural watersheds, little is known about how the increased use of sulfur as a soil amendment to optimize crop production is affecting the isotopic composition of groundwater sulfate, especially in shallow aquifers. We investigated the isotopic composition of synthetic agricultural fertilizers and groundwater sulfate in an area of intensive agricultural activity, in Ontario, Canada. Groundwater samples from an unconfined surficial sand aquifer (Lake Algonquin Sand Aquifer) were analyzed from multi-level monitoring wells, riverbank seeps, and private domestic wells. Fertilizers used in the area were analyzed for sulfur/sulfate content and stable isotopic composition (δ¹⁸O and/or δ³⁴S). Fertilizers were isotopically distinct from geological sources of groundwater sulfate in the watershed and groundwater sulfate exhibited a wide range of δ³⁴S (−6.9 to +20.0‰) and δ¹⁸O (−5.0 to +13.7‰) values. Quantitative apportionment of sulfate sources based on stable isotope data alone was not possible, largely because two of the potential fertilizer sulfate sources had an isotopic composition on the mixing line between two natural geological sources of sulfate in the aquifer. This study demonstrates that, when sulfate isotope analysis is being used as a tracer or co-tracer of the origin of groundwater or of contaminants in groundwater, sulfate derived from synthetic fertilizer needs to be considered as a potential source, especially when other parameters such as nitrate independently indicate fertilizer impacts to groundwater quality.     

Spatiotemporal variation of stable isotopic composition in precipitation: Post‐condensational effects in a humid area

In the present study, a 2‐year dataset on δ¹⁸O and δ²H in precipitation is used to investigate hydrometeorologic controls on the isotopic compositions in a temperate maritime climate. Data was collected in Denmark along a transect of Six sampling stations across a landscape with a small topographic gradient and predominant westerly winds. Data showed the local meteoric water line for this region is expressed by the equation δ²H = 7.4δ¹⁸O + 5.4‰. A significant trend correlating enriched isotopic values to humidities around 70% during dry season and more depleted isotopic values to humidities around 90% during wet season was derived from the dataset. Temperature was found to only influence the isotopic composition in a secondary way, whereas no significant relationship was obtained for precipitation amount and evapotranspiration. It is suggested that subcloud post‐condensation exchange strongly influences the isotopic composition at the study site. A simple model of evaporation on falling rain was applied with the aim to reproduce observational data and show the potential influence of changing humidity conditions on precipitation compositions. The rather simple model approach did not fully explain the observational data, but it highlights the drastic isotopic changes from a falling raindrop that potentially can occur due to its release into a dryer atmosphere. This study shows that regional conditions and especially humidity can alter the isotopic composition in precipitation substantially even in regions without major topographic and hydrometeorologic gradients.     

Bias of Apparent Tracer Ages in Heterogeneous Environments

The interpretation of apparent ages often assumes that a water sample is composed of a single age. In heterogeneous aquifers, apparent ages estimated with environmental tracer methods do not reflect mean water ages because of the mixing of waters from many flow paths with different ages. This is due to nonlinear variations in atmospheric concentrations of the tracer with time resulting in biases of mixed concentrations used to determine apparent ages. The bias of these methods is rarely reported and has not been systematically evaluated in heterogeneous settings. We simulate residence time distributions (RTDs) and environmental tracers CFCs, SF₆, ⁸⁵Kr, and ³⁹Ar in synthetic heterogeneous confined aquifers and compare apparent ages to mean ages. Heterogeneity was simulated as both K‐field variance (σ²) and structure. We demonstrate that an increase in heterogeneity (increase in σ² or structure) results in an increase in the width of the RTD. In low heterogeneity cases, widths were generally on the order of 10 years and biases generally less than 10%. In high heterogeneity cases, widths can reach 100 s of years and biases can reach up to 100%. In cases where the temporal variations of atmospheric concentration of individual tracers vary, different patterns of bias are observed for the same mean age. We show that CFC‐12 and CFC‐113 ages may be used to correct for the mean age if analytical errors are small.     

A Geochemical Approach to Determine Sources and Movement of Saline Groundwater in a Coastal Aquifer

Geochemical evaluation of the sources and movement of saline groundwater in coastal aquifers can aid in the initial mapping of the subsurface when geological information is unavailable. Chloride concentrations of groundwater in a coastal aquifer near San Diego, California, range from about 57 to 39,400 mg/L. On the basis of relative proportions of major‐ions, the chemical composition is classified as Na‐Ca‐Cl‐SO₄, Na‐Cl, or Na‐Ca‐Cl type water. δ²H and δ¹⁸O values range from ?47.7‰ to ?12.8‰ and from ?7.0‰ to ?1.2‰, respectively. The isotopically depleted groundwater occurs in the deeper part of the coastal aquifer, and the isotopically enriched groundwater occurs in zones of sea water intrusion. ⁸⁷Sr/⁸⁶Sr ratios range from about 0.7050 to 0.7090, and differ between shallower and deeper flow paths in the coastal aquifer. ³H and ¹⁴C analyses indicate that most of the groundwater was recharged many thousands of years ago. The analysis of multiple chemical and isotopic tracers indicates that the sources and movement of saline groundwater in the San Diego coastal aquifer are dominated by: (1) recharge of local precipitation in relatively shallow parts of the flow system; (2) regional flow of recharge of higher‐elevation precipitation along deep flow paths that freshen a previously saline aquifer; and (3) intrusion of sea water that entered the aquifer primarily during premodern times. Two northwest‐to‐southeast trending sections show the spatial distribution of the different geochemical groups and suggest the subsurface in the coastal aquifer can be separated into two predominant hydrostratigraphic layers.     

Stable isotope tracers as diagnostic tools in upscaling flow path understanding and residence time estimates in a mountainous mesoscale catchment

δ¹⁸O measurements of precipitation and stream waters were used as a natural tracer to investigate hydrological pathways and residence times in the River Feshie, a complex mesoscale (231 km²) catchment in the Cairngorm Mountains of Scotland. Precipitation δ¹⁸O exhibited strong seasonal variation over the 2001–02 hydrological year, ranging from −6·9‰ in the summer, to −12·0‰ during winter snowfalls (mean δ¹⁸O −9·59‰). Although damped, this seasonality was reflected in stream water outputs at seven sampling sites in the catchment, allowing δ¹⁸O variations to be used to infer hydrological source areas. Thus, stream water δ¹⁸O was generally controlled by a seasonally variable storm flow end member, mixing with groundwater of more constant isotopic composition. Periodic regression analysis allowed the differences in this mixing process between monitoring subcatchments to be assessed more quantitatively to provide a preliminary estimate of mean stream water residence time. This demonstrated the importance of responsive hydrological pathways associated with peat and shallow alpine soils in the headwater subcatchments in producing seasonally variable runoff with short mean residence times (33–113 days). In contrast, other tributaries with more freely draining soils and larger groundwater storage in shallow aquifers provided more effective mixing of variable precipitation inputs, resulting in longer residence time estimates (178–445 days). The mean residence time of runoff leaving the Feshie catchment reflected an integration of these contrasting influences (110–200 days). These insights from δ¹⁸O measurements extend the hydrological understanding of the Feshie catchment gained from other hydrochemical tracers, and demonstrate the utility of isotope tracers in investigating hydrological processes at the mesoscale. Copyright © 2005 John Wiley & Sons, Ltd.     

Isotope hydrology of a tropical coffee agroforestry watershed: Seasonal and event‐based analyses

Stable isotope variations are extremely useful for flow partitioning within the hydrologic cycle but remain poorly understood throughout the tropics, particularly in watersheds with rapidly infiltrating soils, such as Andisols in Central America. This study examines the fluctuations of stable isotope ratios (δ¹⁸O and δ²H) in the hydrologic components of a tropical coffee agroforestry watershed (~1 km²) with Andisol soils in Costa Rica. Samples were collected in precipitation, groundwater, springs, and stream water over 2 years. The local meteoric water line for the study site was δ²H = 8.5 δ¹⁸O + 18.02 (r² = 0.97, n = 198). The isotope ratios in precipitation exhibited an enriched trend during the dry season and a notable depletion at the beginning of the wet season. The δ¹⁸O compositions in groundwater (average = ?6.4‰, σ = 0.7) and stream water (average = ?6.7‰, σ = 0.6) were relatively stable over time, and both components exhibited more enriched values in 2013, which was the drier year. No strong correlation was observed between the isotope ratios and the precipitation amount at the event or daily time‐step, but a correlation was observed on a monthly scale. Stream water and base flow hydrograph separations based on isotope end‐member estimations showed that pre‐event water originating from base flow was prevalent. However, isotope data indicate that event water originating from springs appears to have been the primary driver of initial rises in stream flow and peak flows. These results indicate that isotope sampling improves the understanding of water balance components, even in a tropical humid location, where significant variations in rainfall challenge current modelling efforts. Further research using fine‐scale hydrometric and isotopic data would enhance understanding the processes driving spring flow generation in watersheds.     

Isotopic composition of precipitation during strong El Niño–Southern Oscillation events in the Southeast Region of Brazil

Equatorial Pacific sea surface temperature variations interact with processes of atmospheric circulation, creating conditions for the occurrence of El Niño–Southern Oscillation (ENSO). ENSO events represent the most important interannual phenomena affecting climate patterns worldwide and causing significant socio‐economic impacts. In the Brazilian territory, ENSO leads to an increase in drought episodes in the north‐eastern region and an increase in precipitation in the southern region, whereas the effects over the south‐east region are yet not well understood. The main goal of this study is to compare variations of isotopic composition in precipitation across the south‐east portion of the Brazilian territory during two very strong ENSO events: 1997–1998 (ENSO 1) and 2014–2016 (ENSO 2). Daily isotopic records, available from the Global Network of Isotopes in Precipitation database for ENSO 1, and samples collected during ENSO 2 were used to compare the influence of both events on the isotopic composition of precipitation. Seasonal variations indicated more depleted precipitation during the wet seasons (δ¹⁸O = ?5.4 ± 4.0‰) and enriched precipitation during the dry seasons (δ¹⁸O = ?2.8 ± 2.3‰). Observed rainfall variations were associated with atmospheric large‐scale processes and moisture transport from the Amazon region, whereas extreme values (enriched or depleted) appear to be associated with particular convective and stratiform precipitation events. Overall, more depleted isotopic composition of precipitation (δ¹⁸O = ?4.60‰) and higher d‐excess (up to +15‰) were observed during the dry season of ENSO 1 when compared with ENSO 2 dry season (δ¹⁸O‰ = ?2.80‰, d‐excess lower than +14‰). The latter is explained by greater atmospheric moisture content, particularly associated with recycling of transpiration fluxes from the Amazon region, during dry season of ENSO 1. No significant differences for δ¹⁸O and δ²H were observed during the wet season; however, d‐excess from ENSO 2 was greater than ENSO 1, due to the slightly greater atmospheric moisture content and very strong upward motion observed. Our findings highlight the opportunity that environmental isotopes offer towards understanding hydrometeorological processes, particularly, the evolution of extreme climatic events of global resonance such as ENSO.     

Influences of forest canopy on snowpack accumulation and isotope ratios

The stable water isotopes, ²H and ¹⁸O, can be useful environmental tracers for quantifying snow contributions to streams and aquifers, but characterizing the isotopic signatures of bulk snowpacks is challenging because they can be highly variable across the catchment landscape. In this study, we investigate one major source of isotopic heterogeneity in snowpacks: the influence of canopy cover. We measured amounts and isotopic compositions of bulk snowpack, throughfall, and open precipitation during seven campaigns in mid-winter 2018 along forest-grassland transects at three different elevations (1196, 1297, and 1434 m above sea level) in a pre-Alpine catchment in Switzerland. Snowpack storages under forest canopies were 67 to 93% less than in adjacent open grasslands. On average, the water isotope ratios were higher in the snowpacks under forest canopy than in open grasslands (by 13.4 ‰ in δ²H and 2.3 ‰ in δ¹⁸O). This isotopic difference mirrored the higher isotope values in throughfall compared with open snowfall (by 13.5 ‰ in δ²H and 2.2 ‰ in δ¹⁸O). Although this may suggest that most of the isotopic differences in snowpacks under forests versus in open grasslands were attributable to canopy interception effects, the temporal evolution of snowpack isotope ratios indicated preferential effluxes of lighter isotopes as energy inputs increased and the snowpack ripened and melted. Understanding these effects of forest canopy on bulk snowpack snow water equivalent and isotopic composition are useful when using isotopes to infer snowmelt processes in landscapes with varying forest cover.