Isotope geochemistry and modelling of the multi-aquifer system in the eastern part of Lithuania

A steady-state groundwater flow model of three Quaternary intertill aquifers in the eastern part of Lithuania has been compiled. The distinction of separate modelled layers is based on hydraulic and isotope-hydrochemistry data criteria. ³H data were used to estimate the corrected groundwater age and were coupled with a groundwater-flow-dynamics model of the Quaternary aquifer system along a cross-section flow pathway from the Baltic Upland recharge area in eastern Lithuania towards the discharge area in the lowlands near the city of Kaunas in central Lithuania. The bicarbonate content in groundwater (214–462 mg/l) increases downgradient towards the lowland area. The other major constituents and total dissolved solids (TDS) have a trend analogous to the bicarbonate. The ¹⁴C activity of dissolved inorganic carbon (DIC) in the groundwater ranges from 41.4 to 85.7 pMC. With aquifer-system depth, active precipitation of aqueous solution takes place by dissolving minerals of calcite and dolomite and leakage of “old” groundwater from lower aquifers; the process is also traced by lower ¹⁴C and ³H activities and by more positive δ¹⁸O values in lowland areas.     

A reconnaissance study of stable isotope ratios in archaean rocks from the yilgarn block,Western Australia

Isotopic compositions of sulphur, carbon, and oxygen have been determined for constituents from a total of 103 samples of sedimentary rocks, mafic and ultramafic igneous rocks, nickel ores, and gold ores from the Archaean Yilgarn Block.

Sulphides in the bulk of the sedimentary rocks have δ³⁴S values close to 0‰ and appear to have precipitated from solutions which incorporated magmatic sulphur (either juvenile or derived from older rocks). There is no evidence for widespread sulphate reduction.

δ³⁴S values of sulphides in the nickel deposits and associated mafic/ultramafic igneous rocks are within the magmatic range. The small, high‐grade deposits of the Kambalda‐Nepean‐Scotia type have small positive δ³⁴S values, and the large, low‐to‐medium grade dunite‐associated deposits of the Mount Keith‐Perseverance type have small negative δ³⁴S values.

Sulphides in the Kalgoorlie gold ores are enriched in ³²S relative to those in their host dolerite, supporting an epigenetic origin for the gold, under moderately high fO₂ conditions.

The δ¹³C values do not provide unequivocal evidence for the source(s) of the reduced carbon (kerogen) in the sedimentary rocks. Whilst they are compatible with biogenic derivation, it is not possible to rule out contributions from pre‐biotic organic ‘soup’ or from hydrothermal solutions of deep‐seated origin.

Carbonate in the sedimentary rocks are predominantly in epigenetic, sulphide‐bearing veinlets. In many cases, their δ¹³C values suggest precipitation from hydro‐thermal solutions containing magmatically derived CO₂. In only two samples are the petrographic features and δ¹³C values compatible with marine carbonates. Talc‐carbonate altered ultramafic igneous rocks have δ¹³C values consistent with their incorporation of magmatically derived CO₂.

The ?δ¹³C (carbonate‐kerogen) values for most of the sedimentary rock studied fall in a narrow range around +10‰, suggesting isotopic exchange between oxidized and reduced carbon species at moderately high temperatures (>250°C).

δ¹⁸O values of carbonate from both sedimentary rocks and igneous rocks are mainly within the range +7.2‰ to +18.0‰. If the values are primary they are consistent with the formation of carbonate from hydrothermal solutions of magmatic and/or metamorphic origin. However, it is also possible the δ¹⁸O values are the result of post‐depositional equilibration with meteoric waters.     

Microbial carbon cycling in oligotrophic regional aquifers near the Tono Uranium Mine, Japan as inferred from δC and ΔC values of in situ phospholipid fatty acids and carbon sources

Microorganisms are ubiquitous in deep subsurface environments, but their role in the global carbon cycle is not well-understood. The natural abundance δ¹³C and Δ¹⁴C values of microbial membrane phospholipid fatty acids (PLFAs) were measured and used to assess the carbon sources of bacteria in sedimentary and granitic groundwaters sampled from three boreholes in the vicinity of the Tono Uranium Mine, Gifu, Japan. Sample storage experiments were performed and drill waters analyzed to characterize potential sources of microbial contamination. The most abundant PLFA structures in all waters sampled were 16:0, 16:1ω7c, cy17:0, and 18:1ω7c. A PLFA biomarker for type II methanotrophs, 18:1ω8c, comprised 3% and 18% of total PLFAs in anoxic sedimentary and granitic waters, respectively, sampled from the KNA-6 borehole. The presence of this biomarker was unexpected given that type II methanotrophs are considered obligate aerobes. However, a bacterium that grows aerobically with CH₄ as the sole energy source and which also produces 56% of its total PLFAs as 18:1ω8c was isolated from both waters, providing additional evidence for the presence of type II methanotrophs. The Δ¹⁴C values determined for type II methanotroph PLFAs in the sedimentary (−861‰) and granite (−867‰) waters were very similar to the Δ¹⁴C values of dissolved inorganic carbon (DIC) in each water (∼−850‰). This suggests that type II methanotrophs ultimately derive all their carbon from inorganic sources, whether directly from DIC and/or from CH₄ produced by the reduction of DIC. In contrast, δ¹³C values of type II PLFAs in the sedimentary (−93‰) and granite (−60‰) waters indicate that these organisms use different carbon assimilation schemes in each environment despite very similar δ¹³C_CH4 values (∼−95‰) for each water. The δ¹³C_PLFA values (−28‰ to −45‰) of non-methanotrophic bacteria in the KNA-6 LTL water do not clearly distinguish between heterotrophic and autotrophic metabolisms, but Δ¹⁴C_PLFA values indicate that >65% of total bacteria filtered from the KNA-6 LTL water are heterotrophs. Ancient Δ¹⁴C values (∼−1000‰) of some PLFAs suggest that many heterotrophs utilize ancient organic matter, perhaps from lignite seams within the sedimentary rocks. The more negative range of δ¹³C_PLFA values determined for the KNA-6 granitic water (−42‰ to −66‰) are likely the result of a microbial ecosystem dominated by chemolithoautotrophy, perhaps fuelled by abiogenic H₂. Results of sample storage experiments showed substantial shifts in microbial community composition and δ¹³C_PLFA values (as much as 5‰) during 2-4 days of dark, refrigerated, aseptic storage. However, water samples collected and immediately filtered back in the lab from freshly drilled MSB-2 borehole appeared to maintain the same relative relationships between δ¹³C_PLFA values for sedimentary and granitic host rocks as observed for samples directly filtered under artesian flow from the KNA-6 borehole of the Tono Uranium Mine.     

A new correction model for C ages in aquifers with complex geochemistry – Application to the Neogene Aquifer,Belgium

The objective of this paper is to build a general correction model that takes into account all the different radiocarbon-dilution reactions and resolving the processes that are geochemically “aging” the groundwater in the Neogene Aquifer. For this, δ¹³C and radiocarbon in groundwater are investigated with their relationship to other chemical components in groundwater. The δ¹³C values in the Neogene Aquifer are influenced by various geochemical reactions like calcite dissolution, oxidation of organic matter and methanogenesis. Calcite dissolution and CH₄ production increase δ¹³C while the oxidation of organic matter decreases δ¹³C in the groundwater. The reactions that modify δ¹³C also influence the ¹⁴C activity. Due to the complex geochemical environment, existing correction models are not applicable to this situation. A correction model for initial ¹⁴C activity is formulated in which the different C sources that influence ¹⁴C activity are taken into account. It is observed that recent dissolved organic matter plays an important role in redox reactions. The corrected ¹⁴C ages lie between −0.792 and 6.425 ka representing the maximum age. If a part of the organic matter that oxidises is fossil, the determined age will represent an overestimated age.     

Groundwater flow dynamics in the complex aquifer system of Gidabo River Basin (Ethiopian Rift): a multi-proxy approach

Hydrochemical and isotope data in conjunction with hydraulic head and spring discharge observations were used to characterize the regional groundwater flow dynamics and the role of the tectonic setting in the Gidabo River Basin, Ethiopian Rift. Both groundwater levels and hydrochemical and isotopic data indicate groundwater flow from the major recharge area in the highland and escarpment into deep rift floor aquifers, suggesting a deep regional flow system can be distinguished from the shallow local aquifers. The δ¹⁸O and δ²H values of deep thermal (≥30 °C) groundwater are depleted relative to the shallow (<60 m below ground level) groundwater in the rift floor. Based on the δ¹⁸O values, the thermal groundwater is found to be recharged in the highland around 2,600 m a.s.l. and on average mixed with a proportion of 30 % shallow groundwater. While most groundwater samples display diluted solutions, δ¹³C data of dissolved inorganic carbon reveal that locally the thermal groundwater near fault zones is loaded with mantle CO₂, which enhances silicate weathering and leads to anomalously high total dissolved solids (2,000–2,320 mg/l) and fluoride concentrations (6–15 mg/l) exceeding the recommended guideline value. The faults are generally found to act as complex conduit leaky barrier systems favoring vertical mixing processes. Normal faults dipping to the west appear to facilitate movement of groundwater into deeper aquifers and towards the rift floor, whereas those dipping to the east tend to act as leaky barriers perpendicular to the fault but enable preferential flow parallel to the fault plane.     

The groundwater age in the Middle-Upper Devonian aquifer system, Lithuania

³H, δ¹³C and hydrochemical data were used to estimate the corrected groundwater age derived from conventional ¹⁴C age of dissolved inorganic carbon (DIC). The Middle-Upper Devonian aquifer system from the Baltic upland recharge area in eastern Lithuania towards the discharge area on the Baltic Sea coast in the west was considered. The concentration of total dissolved solids (TDS) in groundwater changes from 300 to 24,000  mg/L and increases downgradient towards the coast. The other major constituents have the same trend as the TDS. The hydrochemical facies of groundwater vary from an alkali-earth carbonates facies at the eastern upland area to an alkali-earth carbonate-sulfate and chloride facies at transit and discharge areas. Meteoric water percolating through the Quaternary and Devonian aquifers regulate the initial ¹⁴C activities of groundwater involving two main members of DIC: soil CO₂ with modern ¹⁴C activity uptake and dissolution of ¹⁴C-free aquifer carbonates. Other sources of DIC are less common. ¹⁴C activity of DIC in the groundwater ranged from 60 to 108 pMC at the shallow depths. With an increase of the aquifers depth the dolomitization of aqueous solution and leakage of the “old” groundwater from lower aquifers take place, traced by lower activities (7–30 pMC).     

Carbon and oxygen stable isotopes in the middle-upper miocene and lower pliocene carbonates of the Eastern Paratethys (Kerch-Taman Region): Palaeoenvironments and post-sedimentation changes

C and O isotope composition of Middle-Upper Miocene and Lower Pliocene carbonates from Kerch-Taman Region (Eastern Paratethys) have been studied in order to reconstruct palaeoenvironmental variability and post-sedimentation changes. The δ¹³C and δ¹⁸О values of the Upper Sarmatian to Lower Pliocene organogenic carbonates reflect the desalinization of paleobasins, global Late Miocene Cooling, and increase in seasonal temperature fluctuations. Isotopic composition of the Middle Sarmatian organogenic carbonates was strongly influenced by evaporation processes, high bioproductivity, and local submarine methane emissions. Warm climate and low bioproductivity together with unstable hydrological regime during the Late Chokrakian and the Karaganian times influenced the isotope composition of primary carbonates. Calcite shell of Spiratella sp. (δ¹³C =–0.4‰ and δ¹⁸О =–0.4‰) from Tarkhanian sediments was formed in warm marine environment. Dolomitization prevails over other secondary mineralization in the studied carbonate rocks. Two groups of secondary dolomites that are characterized by negative and positive δ¹³C values have been recognized. Lowe δ¹³C values (up to–31.4‰) in dolomites indicate the influence of both dissolved inorganic carbon (DIC) from oxidized organic matter (С_org) and methane. Dolomites with positive δ¹³C values (7.0 and 7.8‰) associat with migration of CO₂- and CH₄-containing saline groundwater.     

Isotopic and morphological features of fracture calcite from granitic rocks of the Tono area,Japan: a promising palaeohydrogeological tool

This study aimed to develop a methodology for assessing the hydrochemical evolution of a groundwater system, using fracture-filling and fracture-lining calcite. Fracture calcite in deep (to ca. 1000 m) granitic rocks of the Tono area, central Japan, was investigated by optical and electron microscopy, and chemical and isotopic analysis. Coupled with geological evidence, these new data imply 3 main origins for the waters that precipitated calcite: (1) relatively high-temperature hydrothermal solutions, precipitating calcite distinguished by δ¹⁸O_SMOW from −3 to ca. 10‰, and with δ¹³C_PDB from ca. −18 to −7‰; (2) seawater, probably partly of Miocene age, which precipitated calcite distinguished by δ¹³C_PDB of ca. 0‰ and δ¹⁸O_SMOW > ca. 20‰; (3) fresh water, with a variable δ¹³C_PDB composition, but which precipitated calcite distinguished by δ¹³C_PDB that was significantly < 0‰ and as low as ca. −29‰ and δ¹⁸O_SMOW > ca. 17‰. Data for ¹⁴C suggest that at least some of the fresh-water calcite formed within the last 50 ka. The present day hydrogeological regime in the Tono area is also dominated by fresh groundwater. However, the marine calcite of probable Miocene age found at depth has shown no evidence for dissolution and many different calcite crystal forms have been preserved. Studies of other groundwater systems have correlated similar crystallographic variations with variations in the salinity of coexisting groundwaters. When this correlation is applied to the Tono observations, the calcite crystal forms imply a similar range of groundwater salinity to that inferred from the isotopic data. Thus, the present study suggests that even in presently low-salinity groundwater systems, calcite morphological variations may record the changing salinity of coexisting groundwaters. It is suggested that calcite morphological data, coupled with isotopic data, could provide a powerful palaeohydrogeological tool in such circumstances.     

Using 3H and 14C to constrain the degree of closed-system dissolution of calcite in groundwater

This study uses ³H concentrations, ¹⁴C activities (a¹⁴C), ⁸⁷Sr/⁸⁶Sr ratios, and δ¹³C values to constrain calcite dissolution in groundwater from the Ovens catchment SE Australia. Taken in isolation, the δ¹³C values of dissolved organic C (DIC) and ⁸⁷Sr/⁸⁶Sr ratios in the Ovens groundwater imply that there has been significant calcite dissolution. However, the covariance of ³H and ¹⁴C and the calculated initial ¹⁴C activities (a₀¹⁴C) imply that most groundwater cannot have dissolved more than 20% of ¹⁴C-free calcite under closed-system conditions. Rather, calcite dissolution must have been partially an open-system process allowing ¹³C and ¹⁴C to re-equilibrate with CO₂ in the unsaturated zone. Recognising that open-system calcite dissolution has occurred is important for dating deeper groundwater that is removed from its recharge area in this and other basins. The study is one of the first to use ¹⁴C and ³H to constrain the degree of calcite dissolution and illustrates that it is a valuable tool for assessing geochemical processes in recharge areas.     

Isotope hydrology of deep groundwater in Syria: renewable and non-renewable groundwater and paleoclimate impact

The Regional Deep Cretaceous Aquifer (RDCA) is the principal groundwater resource in Syria. Isotope and hydrochemical data have been used to evaluate the geographic zones in terms of renewable and non-renewable groundwater and the inter-relation between current and past recharge. The chemical and isotopic character of groundwater together with radiometric ¹⁴C data reflect the existence of three different groundwater groups: (1) renewable groundwater, in RDCA outcropping areas, in western Syria along the Coastal and Anti-Lebanon mountains. The mean δ¹⁸O value (?7.2 ‰) is similar to modern precipitation with higher ¹⁴C values (up to 60–80 pmc), implying younger groundwater (recent recharge); (2) semi-renewable groundwater, which is located in the unconfined section of the RDCA and parallel to the first zone. The mean δ¹⁸O value (?7.0 ‰) is also similar to modern precipitation with a ¹⁴C range of 15–45 pmc; (3) non-renewable groundwater found in most of the Syrian interior, where the RDCA becomes confined. A considerable depletion in δ¹⁸O (?8.0 ‰) relative to the modern rainfall and low values of ¹⁴C (<15 pmc) suggest that the large masses of deep groundwater are non-renewable and related to an older recharge period. The wide scatter of all data points around the two meteoric lines in the δ¹⁸O-δ²H diagram indicates considerable variation in recharge conditions. There is limited renewable groundwater in the mountain area, and most of the stored deep groundwater in the RDCA is non-renewable, with corrected ¹⁴C ages varying between 10 and 35 Kyr BP.     

Environmental isotopic study on the recharge and residence time of groundwater in the Heihe River Basin, northwestern China

The recharge and origin of groundwater and its residence time were studied using environmental isotopic measurements in samples from the Heihe River Basin, China. δ¹⁸O and δD values of both river water and groundwater were within the same ranges as those found in the alluvial fan zone, and lay slightly above the local meteoric water line (δD=6.87δ¹⁸O+3.54). This finding indicated that mountain rivers substantially and rapidly contribute to the water resources in the southern and northern sub-basins. δ¹⁸O and δD values of groundwater in the unconfined aquifers of these sub-basins were close to each other. There was evidence of enrichment of heavy isotopes in groundwater due to evaporation. The most pronounced increase in the δ¹⁸O value occurred in agricultural areas, reflecting the admixture of irrigation return flow. Tritium results in groundwater samples from the unconfined aquifers gave evidence for ongoing recharge, with mean residence times of: less than 36 years in the alluvial fan zone; about 12–16 years in agricultural areas; and about 26 years in the Ejina oasis. In contrast, groundwater in the confined aquifers had ¹⁴C ages between 0 and 10 ka BP.     

Using environmental isotopes to evaluate the renewable capacity of a typical karst groundwater system in northern China

The karst groundwater in northern China is an important source of water supply. Its capacity for self-renewal is a key factor affecting its sustainable use. The Pingyi–Feixian karst aquifer in central and southern Shandong Province is a typical karst water source, contributing 54% to the total groundwater taken from the region. In this study, 25 groups of water samples were collected from the Pingyi–Feixian karst aquifer in November 2013. The compositions of isotopes of tritium (³H), carbon-13 (¹³C), and carbon-14 (¹⁴C) were measured. As indicated by the tritium values between 7.1 and 12.2 TU, the Pingyi–Feixian karst groundwater is primarily originated from both historical atmospheric precipitation and modern precipitation. The ¹⁴C ages corrected by δ¹³C were between 146 and 5403 years. Specifically, the shallow groundwater is younger than deep groundwater. Groundwater age tends to increase along the flow path. The ages of the groundwater in recharge area were between 146 and 1348 years, while the ages of deep groundwater in flowing area were generally between 2000 and 4000 years. The ages of the groundwater in discharge area with little anthropic exploitation were larger than 4500 years, whereas these with large amounts of exploitation were less than 1500 years. The shallower the groundwater, the stronger its capacity for renewal. The renewable capacity of karst groundwater in discharge area was significantly affected by anthropic exploitation. The karst groundwater in the areas with less exploitation showed the weakest capacity, whereas that in the area with intensive exploitation was much older and had a stronger renewable capacity.     

Mixing processes in hydrothermal spring systems and implications for interpreting geochemical data: a case study in the Cappadocia region of Turkey

Mixing is a dominant hydrogeological process in the hydrothermal spring system in the Cappadocia region of Turkey. All springs emerge along faults, which have the potential to transmit waters rapidly from great depths. However, mixing with shallow meteoric waters within the flow system results in uncertainty in the interpretation of geochemical results. The chemical compositions of cold and warm springs and geothermal waters are varied, but overall there is a trend from Ca–HCO₃ dominated to Na–Cl dominated. There is little difference in the seasonal ionic compositions of the hot springs, suggesting the waters are sourced from a well-mixed reservoir. Based on δ¹⁸O and δ²H concentrations, all waters are of meteoric origin with evidence of temperature equilibration with carbonate rocks and evaporation. Seasonal isotopic variability indicates that only a small proportion of late spring and summer precipitation forms recharge and that fresh meteoric waters move rapidly into the flow system and mix with thermal waters at depth. ³H and percent modern carbon (pmC) values reflect progressively longer groundwater pathways from cold to geothermal waters; however, mixing processes and the very high dissolved inorganic carbon (DIC) of the water samples preclude the use of either isotope to gain any insight on actual groundwater ages.     

A geochemical study of the impact of irrigation and aquifer lithology on groundwater in the Upper Yakima River Basin,Washington, USA

The Yakima River, a major tributary of the Columbia River, is currently overallocated in its surface water usage in part because of large agricultural water use. As a result, groundwater availability and surface water/groundwater interactions have become an important issue in this area. In several sub-basins, the Yakima River water is diverted and applied liberally to fields in the summer creating artificial recharge of shallow groundwater. Major ion, trace element, and stable isotope geochemistry of samples from 26 groundwater wells from a transect across the Yakima River and 24 surface waters in the Kittitas sub-basin were used to delineate waters with similar geochemical signatures and to identify surface water influence on groundwater. Major ion chemistry and stable isotope signatures combined with principal component analysis revealed four major hydrochemical groups. One of these groups, collected from shallow wells within the sedimentary basin fill, displays temporal variations in NO₃ and SO₄ along with high δ¹⁸O and δD values, indicating significant contribution from Yakima River and/or irrigation water. Two other major hydrochemical groups reflect interaction with the main aquifer lithologies in the basin: the Columbia River basalts (high-Na groundwaters), and the volcaniclastic rocks of the Ellensburg Formation (Ca–Mg–HCO₃ type waters). The fourth major group has interacted with the volcaniclastic rocks and is influenced to a lesser degree by surface waters. The geochemical groupings constrain a conceptual model for groundwater flow that includes movement of water between underlying Columbia River basalt and deeper sedimentary basin fill and seasonal input of irrigation water.     

Carbon isotope systematics of the Cambrian–Vendian aquifer system in the northern Baltic Basin: Implications to the age and evolution of groundwater

Groundwater in the Cambrian–Vendian aquifer system has a strongly depleted stable isotope composition (δ¹⁸O values of about −22‰) and a low radiocarbon concentration, which suggests that the water is of glacial origin from the last Ice Age. The aim of this paper was to elucidate the timing of infiltration of glacial waters and to understand the geochemical evolution of this groundwater. The composition of the dissolved inorganic C (DIC) in Cambrian–Vendian groundwater is influenced by complex reactions and isotope exchange processes between water, organic materials and rock matrix. The δ¹³C composition of dissolved inorganic C in Cambrian–Vendian water also indicates a bacterial modification of the isotope system. The corrected radiocarbon ages of groundwater are between 14,000 and 27,000 radiocarbon years, which is coeval with the advance of the Weichselian Glacier in the area.     

Testing the 14C ages and conservative behavior of dissolved 14C in a carbonate aquifer in Yucca Flat,Nevada (USA), using 36Cl from groundwater and packrat middens

Corrected groundwater ¹⁴C ages from the carbonate aquifer in Yucca Flat at the former Nevada Test Site (now the Nevada National Security Site), USA, were evaluated by comparing temporal variations of groundwater ³⁶Cl/Cl estimated with these ¹⁴C ages with published records of meteoric ³⁶Cl/Cl variations preserved in packrat middens (piles of plant fragments, fecal matter and urine). Good agreement between these records indicates that the groundwater ¹⁴C ages are reasonable and that ¹⁴C is moving with chloride without sorbing to the carbonate rock matrix or fracture coatings, despite opposing evidence from laboratory experiments. The groundwater ¹⁴C ages are consistent with other hydrologic evidence that indicates significant basin infiltration ceased 8,000 to 10,000 years ago, and that recharge to the carbonate aquifer is from paleowater draining through overlying tuff confining units along major faults. This interpretation is supported by the relative age differences as well as hydraulic head differences between the alluvial and volcanic aquifers and the carbonate aquifer. The carbonate aquifer ¹⁴C ages suggest that groundwater velocities throughout much of Yucca Flat are about 2 m/yr, consistent with the long-held conceptual model that blocking ridges of low-permeability rock hydrologically isolate the carbonate aquifer in Yucca Flat from the outlying regional carbonate flow system.     

Intra-annual perturbations of stable isotopes in tufas: Effects of hydrological processes

Tufas, which are freshwater carbonates, are potential archives of terrestrial paleoclimate. Time series of stable isotopic compositions commonly show regular seasonal patterns controlled by temperature-dependent processes, and some perturbation intrinsic to the locality. We examined three tufa-depositing sites in southwestern Japan with similar temperate climates, to understand the origin of local characteristics in the isotopic records. Seasonal change in the oxygen isotope is principally reflected by temperature-dependent fractionation between water and calcite but was perturbed after heavy rainfalls overwhelming the stability of the δ¹⁸O value of the groundwater at one site. Isotopic mass balance indicates an undersaturated and relatively small aquifer at this locality. Water δ¹⁸O values at the other two sites were stable, reflecting a regular seasonal change in the δ¹⁸O value of tufa. Perturbation of the δ¹³C values in tufa is largely due to CO₂ degassing from the stream, which significantly increases the δ¹³C values of dissolved inorganic carbon (DIC). At a site with remarkably high pCO₂ in springwater and a sensitive response of flow rate to rainfall, the amount of CO₂ degassing changed distinctly with flow rate. In contrast, the other two sites having low pCO₂ springwater reflect a regular seasonal pattern of δ¹³C in DIC and tufa specimens.     

Carbon isotopic disequilibrium in the shell of the freshwater mussel Elliptio complanata

Isotopic analyses of shell material from the freshwater mussel Elliptio complanata produced mean C concentrations that were depleted in ¹⁴C and ¹³C relative to the lake water DIC. Depleted C isotope values were attributed to the incorporation of ¹²C-enriched metabolic C into the shell. Microsampling of longitudinal sections of shell revealed a seasonal pattern in the δ¹³C values. The seasonal pattern matched predictions that DIC δ¹³C and metabolic rate determine the final shell δ¹³C concentration. The greatest depletion of δ¹³C occurred in the summer. Similar δ¹³C patterns in marine and freshwater mollusks probably record not only temperature fluctuations, upwelling events, and phytoplankton blooms as reported, but also the changes in metabolic activity brought on by such events.     

Groundwater age dating and recharge mechanism of Arusha aquifer,northern Tanzania: application of radioisotope and stable isotope techniques

The continuous abstraction of groundwater from Arusha aquifers in northern Tanzania has resulted in a decline in water levels and subsequent yield reduction in most production wells. The situation is threatening sustainability of the aquifers and concise knowledge on the existing groundwater challenge is of utmost importance. To gain such knowledge, stable isotopes of hydrogen and oxygen, and radiocarbon dating on dissolved inorganic carbon (DIC), were employed to establish groundwater mean residence time and recharge mechanism.¹⁴C activity of DIC was measured in groundwater samples and corrected using a δ¹³C mixing method prior to groundwater age dating. The results indicated that groundwater ranging from 1,400 years BP to modern is being abstracted from deeper aquifers that are under intensive development. This implies that the groundwater system is continuously depleted due to over-pumping, as most of the sampled wells and springs revealed recently recharged groundwater. High ¹⁴C activities observed in spring water (98.1?±?7.9 pMC) correspond with modern groundwater in the study area. The presence of modern groundwater suggests that shallow aquifers are actively recharged and respond positively to seasonal variations.     

Characterisation of recharge processes and groundwater flow mechanisms in weathered-fractured granites of Hyderabad (India) using isotopes

In order to address the problem of realistic assessment of groundwater potential and its sustainability, it is vital to study the recharge processes and mechanism of groundwater flow in fractured hard rocks, where inhomogeneties and discontinuities have a dominant role to play. Wide variations in chloride, δ¹⁸O and ¹⁴C concentrations of the studied groundwaters observed in space and time could only reflect the heterogeneous hydrogeological setting in the fractured granites of Hyderabad (India). This paper, based on the observed isotopic and environmental chloride variations of the groundwater system, puts forth two broad types of groundwaters involving various recharge processes and flow mechanisms in the studied granitic hard rock aquifers. Relatively high ¹⁴C ages (1300 to ～6000 yr B.P.), δ¹⁸O content (?3.2 to ?1.5‰) and chloride concentration (<100 mg/l) are the signatures that identified one broad set of groundwaters resulting from recharge through weathered zone and subsequent movement through extensive sheet joints. The second set of groundwaters possessed an age range Modern to ～1000 yr B.P., chloride in the range 100 to ～350 mg/l and δ¹⁸O from ?3.2 to +1.7‰. The δ¹⁸O enrichment and chloride concentration, further helped in the segregation of the second set of groundwaters into three sub-sets characterized by different recharge processes and sources. Based on these processes and mechanisms, a conceptual hydrogeologic model has evolved suggesting that the fracture network is connected either to a distant recharge source or to a surface reservoir (evaporating water bodies) apart from overlying weathered zone, explaining various resultant groundwaters having varying ¹⁴C ages, chloride and δ¹⁸O concentrations. The surface reservoir contribution to groundwater is evaluated to be significant (40 to 70%) in one subset of groundwaters. The conceptual hydrogeologic model, thus evolved, can aid in understanding the mechanism of groundwater flow as well as migration of contaminants to deep groundwater in other fractured granitic areas.