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.     

Water isotopic variability in Mallorca: a path to understanding past changes in hydroclimate

This paper reports the first results on δ¹⁸O and δ²H analysis of precipitations, cave drip waters, and groundwaters from sites in Mallorca (Balearic Islands, western Mediterranean), a key region for paleoclimate studies. Understanding the isotopic variability and the sources of moisture in modern climate systems is required to develop speleothem isotope‐based climate reconstructions. The stable isotopic composition of precipitation was analysed in samples collected between March 2012 and March 2013. The values are in the range reported by GNIP Palma station. Based on these results, the local meteoric water line (LMWL) δ²H = 7.9 (±0.3) δ¹⁸O + 10.8 (±2.5) was derived, with slightly lower slope than Global Meteoric Water Line. The results help tracking two main sources of air masses affecting the study sites: rain events with the highest δ¹⁸O values (> ?5‰) originate over the Mediterranean Sea, whereas the more depleted samples (< ?8‰) are sourced in the North Atlantic region. The back trajectory analysis and deuterium excess values, ranging from 0.4 to 18.4‰, further support our findings. To assess the isotopic variation across the island, water samples from eight caves were collected. The δ¹⁸O values range between ?6.9 and ?1.6‰. With one exception (Artà), the isotopic composition of waters in caves located along the coast (Drac, Vallgornera, Cala Varques, Tancada, and Son Sant Martí) indicates Mediterranean‐sourced moisture masses. By contrast, the drip water δ¹⁸O values for inland caves (Campanet, ses Rates Pinyades) or developed under a thick (>50 m) limestone cap (Artà) exhibit more negative values. A well‐homogenized aquifer supplied by rainwaters of both origins is clearly indicated by groundwater δ¹⁸O values, which show to be within 2.4‰ of the unweighted arithmetic mean of ?7.4‰. Although limited, the isotopic data presented here constitute the baseline for future studies using speleothem δ¹⁸O records for western Mediterranean paleoclimate reconstructions. Copyright © 2016 John Wiley & Sons, Ltd.     

Innovative Environmental Tracer Techniques for Evaluating Sources of Spring Discharge from a Carbonate Aquifer Bisected by a River

Littlefield Springs discharge about 1.6 m³/s along a 10‐km reach of the Virgin River in northwestern Arizona. Understanding their source is important for salinity control in the Colorado River Basin. Environmental tracers suggest that Littlefield Springs are a mixture of older groundwater from the regional Great Basin carbonate aquifer and modern (post‐1950s) seepage from the Virgin River. While corrected ¹⁴C apparent ages range from 1 to 9 ka, large amounts of nucleogenic ⁴He and low ³He/⁴He ratios suggest that the carbonate aquifer component is likely even older Pleistocene recharge. Modeled infiltration of precipitation, hydrogeologic cross sections, and hydraulic gradients all indicate recharge to the carbonate aquifer likely occurs in the Clover and Bull Valley Mountains along the northern part of the watershed, rather than in the nearby Virgin Mountains. This high‐altitude recharge is supported by relatively cool noble‐gas recharge temperatures and isotopically depleted δ²H and δ¹⁸O. Excess (crustal) SF₆ and ⁴He precluded dating of the modern component of water from Littlefield Springs using SF₆ and ³H/³He methods. Assuming a lumped‐parameter model with a binary mixture of two piston‐flow components, Cl^?/Br^?, Cl^?/F^?, δ²H, and CFCs indicate the mixture is about 60% Virgin River water and 40% groundwater from the carbonate aquifer, with an approximately 30‐year groundwater travel time for Virgin River seepage to re‐emerge at Littlefield Springs. This suggests that removal of high‐salinity sources upstream of the Virgin River Gorge would reduce the salinity of water discharging from Littlefield Springs into the Virgin River within a few decades.     

Groundwater evolution and mean water age inferred from hydrochemical and isotopic tracers in a tropical confined aquifer

The coastal confined aquifer in the Gulf of Urabá (Colombia) is an important water source for the banana agro‐industry as well as for urban and rural communities. However, the main processes controlling recharge and mixing in the aquifer are still poorly understood. Hydrochemical analyses and stable isotope monitoring were conducted to (a) determine groundwater recharge origin, mean groundwater age, and the main processes governing groundwater chemistry and the potential mixing of marine water and the influence of diffusive processes from the two surrounding aquitard layers. Hydrochemical data indicate that the main processes affecting the dissolved chemical composition include cation exchange, dissolution of carbonated and CO₂, and silicate weathering. δ¹⁸O and δ²H compositions combined with ¹⁴C data highlight the differences in climatic conditions between the recharge zone and the confined section of the aquifer, which is close to the Atlantic Ocean. Groundwater samples with ¹⁴C ages from recent to 28,300 years BP show a depleted isotopic trend ranging from ?6.43‰ to ?9.14‰ in δ¹⁸O and from ?43.2‰ to ?65.7‰ in δ²H. The most depleted δ¹⁸O and δ²H compositions suggest a cooler recharge climate than the current conditions (corresponding to the last glacial period of the late Pleistocene). Depleted δ¹³C values in the total dissolved inorganic carbon indicate the existence of organic material oxidation processes within the geologic formation. These results can be used or transferred to enhance groundwater modelling efforts in other confined coastal aquifers of South America where scarcity of long‐term monitoring data limits water resources planification under a changing climate.     

Groundwater and surface water connectivity within the recharge area of Guarani aquifer system during El Niño 2014–2016

Recharge areas of the Guarani Aquifer System (GAS) are particularly sensitive and vulnerable to climate variability; therefore, the understanding of infiltration mechanisms for aquifer recharge and surface run‐off generation represent a relevant issue for water resources management in the southeastern portion of the Brazilian territory, particularly in the Jacaré‐Pepira River watershed. The main purpose of this study is to understand the interactions between precipitation, surface water, and groundwater using stable isotopes during the strong 2014–2016 El Niño Southern Oscillation event. The large variation in the isotopic composition of precipitation (from ?9.26‰ to +0.02‰ for δ¹⁸O and from ?63.3‰ to +17.6‰ for δ²H), mainly associated with regional climatic features, was not reflected in the isotopic composition of surface water (from ?7.84‰ to ?5.83‰ for δ¹⁸O and from ?49.7‰ to +33.6‰ for δ²H), mainly due to the monthly sampling frequency, and groundwater (from ?7.04‰ to ?7.76‰ for δ¹⁸O and from ?49.5‰ to ?44.7‰ for δ²H), which exhibited less variation throughout the year. However, variations in deuterium excess (d‐excess) in groundwater and surface water suggest the occurrence of strong secondary evaporation during the infiltration process, corresponding with groundwater level recovery. Similar isotopic composition in groundwater and surface water, as well as the same temporal variations in d‐excess and line‐conditioned excess denote the strong connectivity between these two reservoirs during baseflow recession periods. Isotopic mass balance modelling and hydrograph separation estimate that the groundwater contribution varied between 70% and 80%, however, during peak flows, the isotopic mass balance tends to overestimate the groundwater contribution when compared with the other hydrograph separation methods. Our findings indicate that the application of isotopic mass balance methods for ungauged rivers draining large groundwater reservoirs, such as the GAS outcrop, could provide a powerful tool for hydrological studies in the future, helping in the identification of flow contributions to river discharge draining these areas.     

Improved understanding of spring and stream water responses in headwaters of the Indian Lesser Himalaya using stable isotopes,conductivity and temperature as tracers

Stable isotope data are presented for precipitation, spring and stream water in a headwater catchments in the Indian Lesser Himalaya. Isotopic contents of phreatic groundwater followed the local meteoric water line and showed minimal alteration by evaporation, suggesting fast recharge. Mean isotopic values for springs and the stream were close to the weighted annual mean for precipitation, indicating recharge was in synchrony with seasonal rainfall distribution. Precipitation exhibited isotopic declines of ?0.6‰ and ?0.2‰ δ¹⁸O per 100 m rise in elevation in July and August (monsoon), respectively. The time lag of one month between rainfall and spring discharge, combined with the isotopic lapse rate indicated a recharge elevation of 70–165 m above the spring outflow point, implying the water originated within the catchment. Time series of electrical conductivity and temperature of spring, seepage and stream waters confirmed the rapid recharge and limited storage capacity of the shallow aquifers.     

Using environmental isotopes to investigate the groundwater recharge mechanisms and dynamics in the North-eastern Basin,Palestine

ABSTRACT

This study aims to differentiate the potential recharge areas and flow mechanisms in the North-eastern Basin, Palestine. The results differentiate the recharge into three main groups. The first is related to springs and some of the deep wells close to the Anabta Anticline, through the Upper Aquifer (Turonian) formation, with depleted δ¹⁸O and δ²H. The second is through the Upper Cenomanian formation surrounding the Rujeib Monocline in the southeast, where the lineament of the Faria Fault plays an important role, with relatively enriched δ¹³C_DIC values of about ?4‰ (VPDB). The third is the Jenin Sub-series, which shows higher δ¹³C_DIC values, with enriched δ¹⁸O and δ²H and more saline content. The deep wells from the Nablus area in the south of the basin indicate low δ¹³C_DIC values due to their proximity to freshwater infiltrating faults. The deep wells located to the northwest of the basin have δ¹³C_DIC values from ?8 to ?9‰ (VPDB), with enriched δ¹⁸O signatures, indicating slow recharge through thick soil.     

Variation of δ18O, δD and 3H in karst springs of south Kashmir,western Himalayas (India)

Water samples were collected from cold and warm karst springs for stable isotopes (δ¹⁸O and δD) and ³H from SE of Kashmir valley (western Himalayas) to distinguish the sources of recharge and infer their recharge areas. The spring water samples were most depleted in heavier isotopes in May (average δ¹⁸O: ?8.87‰ and δD: ?50.3‰) and enriched in September (average δ¹⁸O: ?7.58‰ and δD: ?48.1‰). The depleted ¹⁸O and ²H of spring waters bear the signatures of winter precipitation while as the enriched ¹⁸O and ²H of spring waters bear the signature of summer rainfall. D‐excess and ³H corroborate with the stable isotope results that the spring flow in spring season (May) and autumn (September) is dominantly controlled by the melting of winter snowmelt and summer rainfall, respectively. The results showed that unlike δD, the δ¹⁸O value in the karst spring waters decreases in January suggesting δ¹⁸O shift. The spring water samples also fall above the Local Meteoric Water Line and Global Meteoric Water Line indicating the δ¹⁸O shift due to interaction of groundwater with the host carbonate rocks during its traverse. The mean elevation of the recharge areas of the springs using δ¹⁸O and δD tracers was also estimated. Copyright © 2014 John Wiley & Sons, Ltd.     

Using stable isotopes of surface water and groundwater to quantify moisture sources across the Yellow River source region

Characterization of stable isotope compositions (δ²H and δ¹⁸O) of surface water and groundwater in a catchment is critical for refining moisture sources and establishing modern isotope–elevation relationships for paleoelevation reconstructions. There is no consensus on the moisture sources of precipitation in the Yellow River source region during summer season. This study presents δ²H and δ¹⁸O data from 111 water samples collected from tributaries, mainstream, lakes, and groundwater across the Yellow River source region during summertime. Measured δ¹⁸O values of the tributaries range from ?13.5‰ to ?5.8‰ with an average of ?11.0‰. Measured δ¹⁸O values of the groundwater samples range from ?12.7‰ to ?10.5‰ with an average of ?11.9‰. The δ¹⁸O data of tributary waters display a northward increase of 1.66‰ per degree latitude. The δ¹⁸O data and d‐excess values imply that moisture sources of the Yellow River source region during summertime are mainly from the mixing of the Indian Summer Monsoon and the Westerlies, local water recycling, and subcloud evaporation. Analysis of tributary δ¹⁸O data from the Yellow River source region and streamwater and precipitation δ¹⁸O data from its surrounding areas leads to a best‐fit second‐order polynomial relationship between δ¹⁸O and elevation over a 4,600 m elevation range. A δ¹⁸O elevation gradient of ?1.6‰/km is also established using these data, and the gradient is in consistence with the δ¹⁸O elevation gradient of north and eastern plateau. Such relationships can be used for paleoelevation reconstructions in the Yellow River source region.     

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.     

Spatial and temporal variability of stable isotopes (δ18O and δ2H) in surface waters of arid,mountainous Central Asia

Characterization of spatial and temporal variability of stable isotopes (δ¹⁸O and δ²H) of surface waters is essential to interpret hydrological processes and establish modern isotope–elevation gradients across mountainous terrains. Here, we present stable isotope data for river waters across Kyrgyzstan. River water isotopes exhibit substantial spatial heterogeneity among different watersheds in Kyrgyzstan. Higher river water isotope values were found mainly in the Issyk‐Kul Lake watershed, whereas waters in the Son‐Kul Lake watershed display lower values. Results show a close δ¹⁸O–δ²H relation between river water and the local meteoric water line, implying that river water experiences little evaporative enrichment. River water from the high‐elevation regions (e.g., Naryn and Son‐Kul Lake watershed) had the most negative isotope values, implying that river water is dominated by snowmelt. Higher deuterium excess (average d = 13.9‰) in river water probably represents the isotopic signature of combined contributions from direct precipitation and glacier melt in stream discharge across Kyrgyzstan. A significant relationship between river water δ¹⁸O and elevation was observed with a vertical lapse rate of 0.13‰/100 m. These findings provide crucial information about hydrological processes across Kyrgyzstan and contribute to a better understanding of the paleoclimate/elevation reconstruction of this region.     

Oxygen isotope geochemistry of cherts from the Onverwacht Group (3.4 billion years), Transvaal,South Africa,with implications for secular variations in the isotopic composition of cherts

δ¹⁸O values for 87 chert samples from the 3.4-b.y.-old Onverwacht Group, South Africa, range from +9.4 to +22.1‰. δ-values for cherts representing early silicified carbonates and evaporites, and possible primary precipitates range from +16 to +22‰ and are distinctly richer in¹⁸O than silicified volcaniclastic debris and cherts of problematical origin. The lower δ-values for the latter two chert types are caused by isotopic impurities such as sericite and feldspar, and/or late silicification at elevated temperature during burial. Cherts with δ-values below +16‰ are thus not likely to yield geochemical data relevant to earth surface conditions.Fine-grained chert is less than 0.7‰ depleted in¹⁸O relative to coexisting coarse drusy quartz. Because coarse quartz preserves its isotopic composition with time, the maximum amount of post-depositional lowering of the δ-values of cherts by long-term isotopic exchange with meteoric groundwaters does not exceed 0.7‰ in 3.4 b.y. In response to metamorphism the δ-values of Onverwacht cherts appear to remain unchanged or to have increased by as much as 4‰. Neither metamorphism nor long-term isotopic exchange with groundwaters can explain why Onverwacht cherts are depleted in¹⁸O relative to their Phanerozoic counterparts.Meteoric waters with a δ¹⁸O range of at least 3‰ appear to have been involved in Onverwacht chert diagenesis. δ-values for possible primary cherts or cherts representing silicified carbonates and evaporites are compatible with the depositional and diagenetic environments deduced from field and petrographic evidence. Onverwacht cherts appear to have formed with δ-values at least 8‰ lower than Phanerozoic cherts.The new Onverwacht data combined with all published oxygen isotope data for cherts suggest a secular trend similar to that initially suggested by Perry (1967) in which younger cherts are progressively enriched in¹⁸O. However, Precambrian cherts appear to be richer in¹⁸O than Perry's original samples and can be reasonably interpreted in terms of declining climatic temperatures from ～70°C at 3.4 b.y. to present-day values, as initially suggested by Knauth and Epstein (1976). This surface temperature history is compatible with existing geological, geochemical, and paleontological evidence.     

Geochemistry and Provenance of Springs in a Baja California Sur Mountain Catchment

Fractured rock aquifers cover much of Earth's surface and are important mountain sites for groundwater recharge but are poorly understood. To investigate groundwater systematics of a fractured-dominated aquifer in Baja California Sur, Mexico, we examined the spatial patterns of aquifer recharge and connectivity using the geochemistry of springs. We evaluate a range of geochemical data within the context of two endmember hypotheses describing spatial recharge patterns and fracture connectivity. Hypothesis 1 is that the aquifer system is segmented, and springs are fed by local recharge. Hypothesis 2 is that the aquifer system is well connected, with dominant recharge occurring in the higher elevations. The study site is a small <15 km² catchment. Thirty-four distinct springs and two wells were identified in the study area, and 24 of these sites were sampled for geochemical analyses along an elevation gradient and canyon transect. These analyses included major ion composition, trace element and strontium isotopes, δ¹⁸O and δ²H isotopes, radiocarbon, and tritium. δ¹⁸O and δ²H isotopes suggest that the precipitation feeding the groundwater system has at least two distinct sources. Carbon isotopes showed a change along the canyon transect, suggesting that shorter flowpaths feed springs in the top of the transect, and longer flowpaths discharge near the bottom. Geochemical interpretations support a combination of the two proposed hypotheses. Understanding of the connectivity and provenance of these springs is significant as they are the primary source of water for the communities that inhabit this region and may be impacted by changes in recharge and use.     

Stable isotope‐based mean catchment altitudes of springs in the Lebanon Mountains

Stable isotopes of water are known to provide information on mean altitudes of spring recharge areas, which is an important parameter for groundwater resources management especially in karstic environments. Very often, a lack of precipitation input data limits the possibility for an appropriate estimation of mean catchment altitudes. In the Jeita spring catchment, Lebanon, a characterization of precipitation input was possible with samples collected at six stations at varying altitudes (88 amount‐weighted monthly samples). A local meteoric water line for the Jeita spring catchment was characterized as δ²H = 6.04 * δ¹⁸O + 8.45 (R ² = .92) for a 2‐year observation period between October 2012 and September 2014. Integral samples from the snow layer were collected at 22 sites at altitudes ranging from 1,000 to 2,300 m above sea level at the end of February 2012 and February 2013, when snow height reached a maximum of more than 6 m at the highest peak in the catchment. Water samples were continuously collected from six springs (Jeita, Kashkoush, Labbane, Assal, Afqa, and Rouaiss). Jeita spring water samples were collected additionally in daily time steps during the snowmelt season in 2012. Mean isotope values of the sampled springs range from ?6.8‰ to ?8.2‰, and from ?33‰ to ?44‰, for δ¹⁸O and δ²H, respectively. The stable isotope data show that input variability (space and time, snow cover, and rainfall) has direct impacts on mean altitude estimates of spring catchments. A more profound interpretation of spring response to rainfall for six local springs in the Lebanon Mountains was possible in comparison to four earlier described springs collected in the Anti‐Lebanon Mountains in Syria.     

Recharge and mineralization of groundwater of the Upper Cretaceous aquifer in Orontes basin,Syria

Abstract

Chemical and isotopic data of groundwater of the Upper Cretaceous aquifer in the Orontes basin, Syria, have been used to assess the groundwater geochemistry, the origin of groundwater recharge and groundwater residence time. The chemical data indicate that dissolution of evaporite minerals is the main process controlling groundwater mineralization. The composition of stable isotopes δ¹⁸O and δ²H, together with ¹⁴C activity, reflect the existence of three different groups: (a) groundwater in the Coastal Mountains with δ¹⁸O of –6.65‰, quite similar to modern-day precipitation, and high ¹⁴C (>50 pmC); (b) groundwater in the unconfined aquifer of the Hama Uplift, which has δ¹⁸O of –5.52‰ and ¹⁴C near 20 pmC, and is recharged locally; and (c) groundwater from the confined aquifer of the Homs Depression, which is characterized by more depleted δ¹⁸O,, –8.01‰, and low ¹⁴C (<7 pmC), and might be recharged in the northern piedmont of the Anti-Lebanon Mountains. The distinctive isotope signatures of the latter two groups indicate different recharge elevations and palaeoclimatic effects. The low recharge rate of the groundwater in the Hama Uplift aquifer, and the even slower recharge rate in the Homs Depression aquifer, are reflected by groundwater ¹⁴C residence times of 5 and over 22 Ka BP, respectively.

Editor D. Koutsoyiannis

Citation Al-Charideh, A., 2013. Recharge and mineralization of groundwater of the Upper Cretaceous aquifer in Orontes basin (Syria). Hydrological Sciences Journal, 58 (2), 452–467.     

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.     

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.     

Groundwater recharge in the Akaki catchment,central Ethiopia: evidence from environmental isotopes (δ18O, δ2H and 3H) and chloride mass balance

Recharge patterns, possible flow paths and the relative age of groundwater in the Akaki catchment in central Ethiopia have been investigated using stable environmental isotopes δ¹⁸O and δ²H and radioactive tritium (³H) coupled with conservative chloride measurements. Stable isotopic signatures are encoded in the groundwater solely from summer rainfall. Thus, groundwater recharge occurs predominantly in the summer months from late June to early September during the major Ethiopian rainy season. Winter recharge is lost through high evaporation–evapotranspiration within the unsaturated zone after relatively long dry periods of high accumulated soil moisture deficits. Chloride mass balance coupled with the isotope results demonstrates the presence of both preferential and piston flow groundwater recharge mechanisms. The stable and radioactive isotope measurements further revealed that groundwater in the Akaki catchment is found to be compartmentalized into zones. Groundwater mixing following the flow paths and topography is complicated by the lithologic complexity. An uncommon, highly depleted stable isotope and zero‐³H groundwater, observed in a nearly east–west stretch through the central sector of the catchment, is coincident with the Filwoha Fault zone. Here, deep circulating meteoric water has lost its isotopic content through exchange reactions with CO₂ originating at deeper sources or it has been recharged with precipitation from a different rainfall regime with a depleted isotopic content. Copyright © 2006 John Wiley & Sons, Ltd.     

Major active faults determine the location of the Tongonan geothermal field: Evidence provided by rock alteration and stable isotope geochemistry

Abstract The influence of major active faults on rock alteration and stable isotope geochemistry is described for the Tongonan geothermal field, Leyte, the Philippines. In the Pliocene, acid alteration with characteristic iron enrichment (3 g/100 g) and calcium depletion (2 g/100 g) occurred along a Riedel shear fault in the Malitbog sector, and initial minor acid alteration also occurred along a similar shear in the Mahiao sector. Later, sodium metasomatism (5 g/100 g) coincided with the highest aquifer chloride (10 000 mg/kg) as a result of dissociation of saline magmatic fluids discharging through the reservoir rocks in the Upper Mahiao. The incursion of magmatic fluids (possibly δD 35‰, δ¹⁸O +7‰) set up a vigorous convection cell of meteoric water, which focused around low‐angle (L) shears centered in the Sambaloran sector. Meteoric water (δD ?35 to ?40‰, δ¹⁸O ?6 ± 1‰) depleted the reservoir in silica (6 g/100 g) and potassium (1–2 g/100 g). It also completely exchanged oxygen isotopes rapidly (within months) at high temperatures (300–400°C), and now does so continuously with fractured isotopically fresh or incompletely altered rock at small scales (centimeters or less) exposed by a 2 cm/year creep around the L shears to form a new component called geothermal water. Geothermal water mixes with meteoric water at lower temperatures (<300°C) to create the characteristic shift in δ¹⁸O of 6‰ at near constant δD (?35 ± 5‰). The 10‰ variation in δD is due to groundwater recharge derived from rain falling on steep terrain (5‰) and to enrichment of deuterium in boiling saline solutions (5‰); it is not due to two‐component mixing of meteoric with magmatic water. The low (～1) isotopic water/rock (W/R) ratios calculated from oxygen isotopes in previously published reports are meaningless, because the water contains four components (predominantly geothermal and meteoric water; <10% magmatic and rock water). W/R ratios of up to 1500 calculated from spring and rock chemistry are more realistic and, with a flow rate of approximately 50 L/s through a 30 km³ reservoir, can account for the estimated 3 My age of the system.     

Orographic distillation and spatio‐temporal variations of stable isotopes in precipitation in the North Atlantic

Little is known about the spatial and temporal variability of the stable isotopic composition of precipitation in the North Atlantic and its relationship to the North Atlantic Oscillation (NAO) and anthropogenic climate change. The islands of the Azores archipelago are uniquely positioned in the middle of the North Atlantic Ocean to address this knowledge gap. A survey of spatial and temporal variability of the stable isotope composition of precipitation in Azores is discussed using newly presented analyses along with Global Network of Isotopes in Precipitation data. The collected precipitation samples yield a new local meteoric water line (δ²H = 7.1 * δ¹⁸O + 8.46) for the Azores region and the North Atlantic Ocean. The annual isotopic mean of precipitation shows a small range for the unweighted and precipitation mass‐weighted δ¹⁸O‐H₂O values. Results show an inverse relation between the monthly δ¹⁸O‐H₂O and the amount of precipitation, which increases in elevation and into the interior of the island. Higher amounts of precipitation (from convective storm systems) do not correspond to the most depleted values of stable isotopes in precipitation. Precipitation shows an orographic effect with depleted δ¹⁸O‐H₂O values related to the Rayleigh effect. Monthly δ¹⁸O‐H₂O values for individual precipitation sampling stations show little relationship to air temperature. Results show a local source of moisture during the summer with the characteristics of the first vapour condensate. The stable isotope composition of precipitation is strongly correlated to the NAO index, and δ¹⁸O‐H₂O values show a statistically significantly trend towards enrichment since 1962 coincident with the increased air temperature and relative humidity due to climate change. Results are in line with observations of increasing sea surface temperature and relative humidity.