I/I ratios in Scottish coastal surface sea water: Geographical and temporal responses to changing emissions

This work constitutes the first survey of I isotope ratios for Scottish sea water including the first data for the west of Scotland. These data are of importance because of the proximity to the world’s second largest emission source of ¹²⁹I to the sea, the Sellafield nuclear reprocessing plant, because of the increasing importance of the sea to land transfer of ¹²⁹I and also as input data for dose estimates based on this pathway of ¹²⁹I. ¹²⁹I/¹²⁷I ratios in SW Scotland reached 3 × 10⁻⁶ in 2004. No strong variation of I isotope ratios was found from 2003 to 2005 in Scottish sea waters. Iodine isotope ratios increased by about a factor of 6 from 1992 to 2003 in NE Scotland, in agreement with the increase of liquid ¹²⁹I emissions from Sellafield over that time period. It is demonstrated that ¹²⁹I/¹²⁷I ratios agree better than ¹²⁹I concentrations for samples from similar locations taken in very close temporal proximity, indicating that this ratio is more appropriate to interpret than the radionuclide concentration.     

Circulation of water masses in the Baltic Proper revealed through iodine isotopes

Tracer technology has been used to understand water circulation in marine systems where the tracer dose is commonly injected into the marine waters through controlled experiments, accidental releases or waste discharges. Anthropogenic discharges of ¹²⁹I have been used to trace water circulation in the Arctic and North Atlantic Ocean. Here, ¹²⁹I, together with ¹²⁷I, is utilized as a tracer of water pathways and circulation in the Baltic Sea through collection of seawater depth profiles. The results indicate the presence of ¹²⁹I signatures which are distinct for each water mass and provide evidence for: (1) inflow water masses through the Drogden Sill that may reach as far as the SW of the Arkona Sea, (2) a portion of North Atlantic water in the bottom of Arkona basin, (3) cyclonic upwelling which breaks through the halocline in a pattern similar to the Baltic haline conveyor belt and (4) more influx of fresher water from the Gulf of Finland and Bothnian Sea in August relative to April. These findings provide advances in labeling and understanding water pathways in the Baltic Sea.     

Geochemistry of halogens in the Milk River aquifer,Alberta, Canada

Analytical data are presented for Cl, Br and I on a regional scale for the Milk River aquifer. The three halides show strikingly similar spatial distributions and are highly correlated. Concentrations are low in the freshwater portions of the aquifer but increase by as much as two orders of magnitude along the margins. However, halide ratios reach nearly constant values moving down-gradient, suggesting the dominance of a common subsurface source for these ions. Ratios of Cl/I and Cl/Br are less than those of seawater and fit an origin derived from the diagenesis of organic matter in the sediments. Halide ratios rule out leakage and/or diffusion from the underlying Colorado Group as a major influence on the chemistry; the favored hypothesis is altered connate seawater diffusing from low-permeability units within the Milk River Formation as the primary source of salts. This hypothesis of an internal source has important implications for solute sources in other aquifers affected by saline waters because it does not require the importation of a distant fluid.The¹²⁹I/I ratio has a meteoric value in groundwater collected near the recharge area, but ratios for downflow waters are only 8–70% of this value. Due to the 16 Ma half-life of¹²⁹I, these data indicate that most of the increase in dissolved I cannot derive from concentration of a meteoric source by ion filtration, but must have a subsurface origin. Concentrations of¹²⁹I producedin situ by spontaneous fission of²³⁸U attain measurable levels only in the oldest waters sampled (ages≥ 10⁵a), in which it may account for nearly 90% of the total dissolved¹²⁹I concentration.Water ages based upon³⁶Cl/Cl data range up to 2 Ma if uncorrected for any dilution by subsurface sources of dead Cl. If one assumes that the subsurface contributions of Cl contribute at least 90% of total Cl in the distal portion, then the³⁶Cl-based ages are reduced to ∼ 1Ma, somewhat greater than those estimated by hydrodynamic modeling.     

I/I ratios in surface waters of the English Lake District

Accelerator Mass Spectrometry (AMS) was used to measure ¹²⁹I/¹²⁷I ratios in surface sea, lake, and river water samples collected in 2004 and 2005 from the English Lake District and from SW Scotland, areas which are in relatively close proximity to the Sellafield nuclear fuel reprocessing plant in NW England. The ¹²⁹I/¹²⁷I ratios in surface water collected from the shore of the Irish Sea were in the range 2.8 × 10⁻⁶ to 8.2 × 10⁻⁶. These ratios are one order of magnitude higher than that of seawater collected from the Irish Sea in 1992, correlating with the increase in ¹²⁹I content of the Sellafield liquid effluent discharge over the last decade. The ¹²⁹I/¹²⁷I ratios in lakes in the Lake District were in the range 0.7 × 10⁻⁶ to 6.4 × 10⁻⁶ and decreased exponentially as a function of distance from Sellafield. Consideration of the relative variation of stable I concentrations and ¹²⁹I/¹²⁷I ratios suggests that Sellafield gaseous discharges may be the dominant source of ¹²⁹I to the lakes.     

A natural-gradient field tracer test for evaluation of pollutant-transport parameters in a porous-medium aquifer

This paper describes a natural-gradient field tracer test to characterise solute-transport properties in a sand and gravel aquifer in the Hebei Province, northern China. Some laboratory-scale column tests on aquifer material and a local-scale field borehole-dilution test have been conducted previously, but the field test reported herein represents the only large-scale tracer test in the aquifer, which is the sole water supply to the city of Shi Jiazhuang and which is threatened by urban pollution. The aim of the study was to quantify the transport behaviour of nonreactive pollutants in this aquifer. Little quantitative data are available concerning its solute-transport properties; thus, the results of the tracer test are significant and critical for understanding pollutant transport and fate. The in-situ tracer test was carried out in the aquifer using a slug injection of the geochemically conservative, radioactive iodine tracer ¹³¹I. The longitudinal (α _L ) and transverse (α _T ) hydrodynamic dispersivities for solute transport in the field are 1.72 and 0.0013 m, respectively. The ratio of longitudinal dispersivity α _L and the flow length at the field scale is 1:10. The ratio between α _L and α _T from the in-situ test (~1,300:1) demonstrates a dominant longitudinal dispersion in this fluvial sand and gravel aquifer. The tracer test further indicates a relatively short transit time for the aquifer (linear velocities ~13 m/d) under natural-gradient conditions. Electronic Publication     

The geochemistry and mixing of leakage in a semi-confined aquifer at a municipal well field,Memphis, Tennessee,USA

The Memphis aquifer in southwestern Tennessee is confined to a semi-confined unconsolidated sand aquifer and is the primary municipal water source in the Memphis metropolitan area. Past studies have identified regions in the metropolitan area in which the overlying upper Claiborne confining unit lacks significant clay and provides a hydraulic connection between the shallow aquifer and the Memphis aquifer. In this study, major solute chemistry, ³H, and ³H/³He groundwater dating are used to investigate the extent and chemical effects of leakage through the confining unit to the Memphis aquifer in the vicinity of a municipal well field. The ³H/³He dates and geochemical modeling of the chemical data are used to constrain mixing fractions and the timing of modern recharge. Tritium activities of as much as 2.8 TU are observed in shallow production wells, but deeper production wells have ³H activities that approach the detection limit. Trends in water chemistry indicate vertical mixing in the aquifer of shallow Na–SO₄–Cl-rich water and deeper Ca–Mg–HCO₃-rich water. Water chemistry does not vary consistently with seasonal pumping, but ³H activity generally decreases during low use periods. Stable O and H isotopes show little variation and are not useful groundwater tracers for this study. The ³H-bearing, Na–SO₄–Cl-rich water is interpreted to reflect recharge of modern water through the upper Claiborne confining unit. The ³H/³He dates from 5 production wells indicate modern recharge, that infiltrated 15–20 a ago, is present in the shallow production wells. Geologic data and hydrologic boundary conditions suggest that the most likely source for continued leakage is a nearby stream, Nonconnah Creek. Geochemical reaction modeling using the NETPATH computer code suggests that proportions of shallow aquifer water leaking into the Memphis aquifer range from 6 to 32%. The ³H/³He dating and NETPATH modeling results correlate well, suggesting that these complementary analytical tools provide an effective means to evaluate proportions of modern water leaking into semi-confined aquifers. These results also indicate a need to carefully consider connections between surface water and semi-confined groundwater resources in wellhead protection programs.     

Natural iodine-129 as an environmental tracer

Iodine-129 ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, 16 My) is a naturally-occurring tracer which can be used to study hydrologic and geologic processes on time scales up to 100 My. The pre-bomb atmospheric ratio ${}^{129}\text{I}\text{I}$ should have been constant in time and space and is the starting value in ground-water recharge. Subsequent ratio changes in ground water should be determined by isotope contributions from three sources: recharge water, iodine leached from the formation, and in situ uranium fission. The mathematical expression of these time-dependent processes forms the basis for dating and tracing applications.The expected behavior of natural ¹²⁹I in ground water is compared to results from field studies. Ground-water samples from the Great Artesian Basin, Australia, provide an estimate of the atmospheric equilibrium ratio, 6 × 10^?13. Down-gradient changes in water up to 1 My old suggest that subsurface production can be significant. The usefulness of ¹²⁹I as an indicator of brine source and age is verified in brines collected in and around Louisiana salt domes. The method leads to ages of 7 and 9 My for two brine pockets trapped within Jurassic salt, and 32 to >40 My for oil-field brines in Miocene sands adjacent to the domes.The results demonstrate the capability of tandem accelerator mass spectrometry to measure as few as 10⁷ atoms of ¹²⁹I in 10 mg I with 10% precision. Although such atom sensitivity can be achieved otherwise, the accelerator technique is necessary to measure naturally low pre-1945 cosmogenic isotope ratios.     

Evaluation of the origin and fate of nitrate in the Abbotsford Aquifer using the isotopes of15N and18O in NO3−

Extensive NO₃⁻ contamination of groundwater in the Abbotsford aquifer to levels above drinking water limits is a major problem in the Fraser Lowlands of southwestern British Columbia, Canada. Nitrate concentrations in the aquifer ranged from 0 to 151 mg/l NO₃⁻, with a median concentration of 46 mg/l NO₃⁻. Of 117 wells sampled, 54% had NO₃⁻ concentrations exceeding the drinking water limit of 45 mg/1. Approximately 80% of the study area had groundwater NO₃⁻ concentrations exceeding 40 mg/1 NO₃⁻. Potential NO₃⁻ source materials were poultry manure N and synthetic NH₄ based fertilizers. Theδ¹⁵N of solid poultry manure samples ranged between + 7.9 and + 8.6‰ (AIR). Four brands of synthetic fertilizers commonly used hadδ¹⁵N values between −1.5 and −0.6‰. Ammonia volatilization caused theδ¹⁵N of groundwater NO₃⁻ produced from poultry manure N to range between +8 and +16‰. Theδ¹⁸O values of groundwater NO₃⁻, by contrast, mostly ranged between +2 and +5‰ (SMOW). This narrow range ofδ¹⁸O values fell within the expected range of NO₃⁻ produced by nitrification of reduced N forms such as poultry manure N and NH₄ fertilizers, and had a similar range ofδ¹⁸O values as NO₃⁻ in the upper part of the unsaturated zone below raspberry fields and beneath former manure piles. Theδ¹⁵N-NO₃⁻ andδ¹⁸O-NO₃⁻ data confirmed that NO₃⁻ in the aquifer was predominantly derived from poultry manure and to a lesser extent from synthetic fertilizers. Theδ¹⁸O-NO₃⁻ data further suggested the nitrification process occurred mainly in the summer months, with the soil NO₃⁻ produced subsequently flushed into the aquifer during fall recharge. Theδ¹⁵N-NO₃⁻andδ¹⁸O-NO₃⁻ data conclusively indicated that no significant bacterial denitrification is taking place in the Abbotsford aquifer.     

Is soil natural organic matter a sink or source for mobile radioiodine (I) at the Savannah River Site?

¹²⁹I is one of the three major radiation risk contributors to the public as a consequence of past nuclear processing activities at Department of Energy (DOE) facilities. Elevated levels of ¹²⁹I are present in the surface soils of F-Area of Savannah River Site, which used to be an isotope separation facility for the production of nuclear weapons components. The ¹²⁹I in soils is thought to be bound predominantly to soil organic matter (SOM). Measurements of stable ¹²⁷I and radioactive ¹²⁹I in humic acids (HAs) and fulvic acids (FAs) obtained by five successive alkaline, two glycerol and one citric acid-alkaline extraction, demonstrated that these extractable humic substances (HS) together account for 54-56% and 46% of the total ¹²⁷I and ¹²⁹I in the soil, respectively. The remainder was likely bound to residual SOM. The iodine content (μg-I/g-C) generally decreased with each subsequent extract, while ¹²⁹I/¹²⁷I increased concurrently. The coincident variations in chemical compositions, aromaticity (estimated by UV spectroscopy), functional groups (e.g., aliphatic), degree of humification, relative migration in the hydrophobic interaction column, and molecular weight indicated that: (1) iodine in different HAs was bound to a small-size aromatic subunit (∼10 kDa); (2) the large-size subunit (∼90 kDa), which likely linked the small-size unit through some weak chemical forces (hydrogen bonds, hydrophobic or electrostatic interactions), determined the relative mobility of iodine bound to organic matter; (3) from the strong correlation between iodine content and aromaticity in the HAs, we suggested that iodine incorporation into the SOM via covalent aromatic C-I bond is the key mechanism controlling iodine behavior in this system. However, this relationship is not universal for all fractions of organic matter as evidenced from the different slopes of this relationship at the two sampling sites, as well as from the different relationships for HAs and FAs, respectively. These differences in iodination are due to different SOM molecular sizes, compositions, and availability of preferred iodination sites. ¹²⁹I in the soil downstream from the contaminated site and near a wetland abruptly dropped below our detection limit (0.5 pCi-¹²⁹I/g-soil), which suggests that the high SOM in the plume soil around the ¹²⁹I-contaminated F-Area might be a natural barrier to scavenge radioiodine released from the nuclear waste repository by forming organo-iodine compounds. Soil resuspension experiments showed that mobile ¹²⁹I was mostly associated with a low average molecular weight amphiphilic organic carrier (13.5-15 kDa). SOM clearly behaves as a sink for iodine at the Savannah River Site F-Area. However, this work demonstrates that a small fraction of the SOM can also behave as a source, namely that a small fraction that may be readily dispersible under some environmental conditions and presumably release iodine in the organic-colloidal form. This radioiodinated organo-colloid likely can get into the groundwater through infiltration or surface runoff where it might migrate further into the wetlands. Results from this study provide the geochemical basis for future ¹²⁹I migration controls, remediation, and/or land-groundwater management strategies.     

Field tracer test for denitrification in a pyrite-bearing schist aquifer

A small-scale artificial tracer test performed on a schist aquifer in Brittany has helped clarify mechanisms and kinetics of in situ autotrophic denitrification. NO₃ was injected as a pulse simultaneously with a conservative tracer -Br⁻. During the test, which lasted 210 h, 73% of the injected Br⁻ was recovered, as against only 47% of the NO₃. The 26% difference in the recovery of the two injected species is interpreted as being the result of denitrification, in part due to the direct oxidation of pyrite present in the solid aquifer according to the reaction: 5FeS₂+14NO₃⁻+4H⁺→7N₂+10SO₄²⁻+5Fe²⁺+2H₂O, and in part due to subsequent iron oxidation according to the reaction: NO₃⁻+5Fe²⁺+6H⁺→1/2N₂+5Fe³⁺+3H₂O. Despite the potential increase in SO₄ and Fe resulting from denitrification through pyrite oxidation, the concentrations of these elements in the groundwater remain moderate due to the precipitation of minerals such as jarosite and/or natroalunite. Tracer transfer takes place in a heterogeneous medium which, according to the breakthrough curves, can be simplified to a dual-porosity aquifer comprising a high-permeability (fractures or large fissures) medium of low porosity from which only minor denitrification of circulating NO₃-bearing water was observed and a low-permeability (small fissures) medium of high porosity which induces a higher denitrification rate in the circulating NO₃-bearing water. The kinetics of the denitrification reaction are high compared with results obtained for other environments and can be described by a first-order model with a half life of 7.9 days for the low-porosity medium and only 2.1 days for the high-porosity medium.     

Processes affecting groundwater chemistry in a zone of saline intrusion into an urban sandstone aquifer

Samples have been collected from inflows into railway tunnels in the Triassic sandstone aquifer beneath Liverpool and the Mersey Estuary, England, U.K. These provide a profile through a saline–freshwater mixing zone. Analyses were made of major anions and cations, δ³⁴S and δ¹⁸O in SO₄, δ¹³C in dissolved inorganic C and ⁸⁷Sr/⁸⁶Sr. The data demonstrate that the presence of a low permeability fault exerts a strong control on the local groundwater chemistry. On the estuary side of the fault, groundwater chemistry is dominated by mixing of intruding estuary water, which is modified by SO₄ reduction and calcite dissolution, with fresh groundwater. The environment of SO₄ reduction in the tidal estuary is one of repeated reduction and re-oxidation of S in an open system and has resulted in virtually no change in S isotopic composition, but an enrichment in residual SO₄ δ¹⁸O of 1.5‰. Groundwater chemistry on the landward side of the fault is primarily the result of recharge in an urban environment. There is also evidence that saline water has been present in this region of the aquifer in the past and that this has now been flushed by fresh groundwaters. This saline water was either transported along the landward side of the fault from nearer the estuary or more probably transmitted across the fault. Both mechanisms would have been driven by large landward head gradients caused by heavy industrial abstraction earlier this century. This has produced a zone of groundwaters depleted in Ca and radiogenic Sr and enriched in Na as a result of ion exchange between the fresh groundwaters and the aquifer previously occupied by more saline water. Sulphur isotopic composition, however, shows no variation since SO₄ does not undergo significant ion exchange. A tracer test from a borehole to the tunnels showed multiple breakthroughs to some locations indicating a number of different flow paths through the aquifer. The maximum flow velocity recorded in this test was 140 m/d suggesting flow along fractures.     

36Cl in modern groundwater dated by a multi-tracer approach (3H/3He,SF6, CFC-12 and 85Kr): a case study in quaternary sand aquifers in the Odense Pilot River Basin,Denmark

³⁶Cl produced by thermonuclear bomb testing has been proposed as an additional tool to date or at least to identify recent groundwater components. In order to investigate the behaviour of ³⁶Cl in shallow groundwater a multi-tracer approach (³H/³He, SF₆, CFC-12 and ⁸⁵Kr) was used to characterise and date the groundwater of a quaternary sands aquifer which is located on the Island of Funen near the city of Odense, Denmark. Recharge to the semi-confined shallow aquifer occurs through permeable sand windows and fractured tills at the surface. Locally, however, mixing with older pre-bomb water from the underlying limestone aquifer may occur. The integrated analyses of the available tracer data allowed a well constrained age structure determination of the investigated water system.The ³⁶Cl/Cl ratios measured in groundwater were used to reconstruct the fallout rates for radioactive ³⁶Cl at Odense. The calculated fallout values exceeded the fallout estimated based on data from the Dye-3 ice core in Greenland. Recycling of the bomb peak fallout seems to be the most probable reason of the high values measured. The local extent of this process is difficult to quantify, which impedes the use of ³⁶Cl for dating.     

Radionuclide migration at experimental polygon at Red Forest waste site in Chernobyl zone. Part 2: Hydrogeological characterization and groundwater transport modeling

This article represents the second of two articles, which review the main results of the international radioecological projects: Chernobyl Pilot Site Project (1999–2003) and Experimental Platform in Chernobyl (2004–2008). These projects studied radionuclide migration from the near-surface radioactive waste trench at the Red Forest waste dump in the Chernobyl zone, which contained nuclear fuel particles. This article presents results from the comprehensive hydrogeological site characterization program including the following issues: geological structure of the study site, hydraulic properties of the deposits, tracer tests in the aquifer, results of groundwater monitoring and unsaturated zone regime studies, as well as data on the ⁹⁰Sr distribution in the unsaturated zone and aquifer, and analyses of ⁹⁰Sr sorption behavior. The derived parameters were used to develop and calibrate 1D (flow tube) and 2D (cross-section) models describing the migration of ⁹⁰Sr from the studied waste trench to the unsaturated zone and aquifer over a 16-a period (1986–2002). The models involved the following sub-models: (1) the geostatistical (structural) model for radioactivity distribution in the trench (using GSLIB); and (2) the radionuclide source term model (STERM1D) describing dissolution of fuel particles and a 1D of radionuclide redistribution in the trench body and unsaturated zone. The MODFLOW – MT3D codes were used to model the 2D ⁹⁰Sr transport in the aquifer cross-section. Calibration of the 1D model with respect to K_ds and dispersivities allowed quite accurate reproduction of ⁹⁰Sr migration behavior for the early period (1995–1998). The less perfect fit between the 1D and 2D modeling results and monitoring data for the later period (1999–2002) suggests the need to improve the conceptual radionuclide migration model (i.e. to account for transient hydraulic and geochemical regimes of the waste site).     

Geochemical and hydrogeological contrasts between shallow and deeper aquifers in two villages of Araihazar, Bangladesh: Implications for deeper aquifers as drinking water sources

Sediment and groundwater profiles were compared in two villages of Bangladesh to understand the geochemical and hydrogeological factors that regulate dissolved As concentrations in groundwater. In both villages, fine-grained sediment layers separate shallow aquifers (< 28 m) high in As from deeper aquifers (40-90 m) containing < 10 μg/L As. In one village (Dari), radiocarbon dating indicates deposition of the deeper aquifer sediments > 50 ka ago and a groundwater age of thousands of years. In the other village (Bay), the sediment is < 20 ka old down to 90 m and the deeper aquifer groundwater is younger, on the order of hundreds of years. The shallow aquifers in both villages that are high in As contain bomb-³H and bomb-¹⁴C, indicating recent recharge. The major and minor ion compositions of the shallow and deeper aquifers also differ significantly. Deeper aquifer water is of the Na⁺-HCO₃^- type, with relatively little dissolved NH₄⁺ (76 ± 192 μmol/L), Fe (27 ± 43 μmol/L) and Mn (3 ± 2 μmol/L). In contrast, shallow aquifer water is of the Ca²⁺-Mg²⁺-HCO₃^- type, with elevated concentrations of dissolved NH₄⁺ (306 ± 355 μmol/L), Fe (191 ± 73 μmol/L), and Mn (27 ± 43 μmol/L). In both villages, the quantity of As extractable from deeper aquifer sands with a 1 mol/L phosphate solution (0.2 ± 0.3 mg/kg, n = 12; 0.1 ± 0.1 mg/kg, n = 5) is 1 order of magnitude lower than P-extractable As from shallow deposits (1.7 ± 1.2 mg/kg, n = 9; 1.4 ± 2.0 mg/kg, n = 11). The differences suggest that the concentration of P-extractable As in the sediment is a factor controlling the concentration of As in groundwater. Low P-extractable As levels are observed in both deeper aquifers that are low in As, even though there is a large difference in the time of deposition of these aquifers in the two villages. The geochemical data and hydrographs presented in this study suggest that both Holocene and Pleistocene deeper aquifers that are low in As should be a viable source of drinking water as long as withdrawals do not exceed recharge rates of ∼1 cm/yr.     

Hydrogeochemistry and quality of groundwater of coastal unconfined aquifer in Amol–Ghaemshahr plain,Mazandaran Province,Northern Iran

Groundwater of the unconfined aquifer (1,100 sq. km) of a two-tier coastal aquifer located in the Amol–Ghaemshahr plain, Mazandaran Province, Northern Iran, is classified into fresh and brackish water types. Fresh groundwater (FGW) samples (n = 36) are characterized by Ca²⁺ > Na⁺ > Mg²⁺ > K⁺ and HCO₃ ^? > Cl^? > SO₄ ^2? > NO₃ ^?. Spearman’s rank correlation coefficient matrices, factor analysis data, values of the C-ratio (av. = 0.89) and CAI and values of the molar ratios of Ca²⁺/HCO₃ ^?, Ca²⁺/SO₄ ^2?, Mg²⁺/HCO₃ ^? and Mg²⁺/SO₄ ^2? indicate that the ionic load in the FGW is derived essentially from carbonic acid-aided weathering of carbonates and aluminosilicates, saline/sea water trapped in the aquifer sediments (now admixed with the groundwater) and ion exchange reactions. Values of the CAI and Na⁺/Cl^? molar ratio suggest that the part of the Ca²⁺ (±Mg²⁺) content in 23 FGW samples is derived from clay minerals of the aquifer matrix, and part of the Na⁺ content in 20, 12, and 3 FGW samples is derived, respectively, from alkali feldspar weathering, clay minerals of the aquifer matrix and rain water and/or halite. Brackish groundwater (BGW) samples (n = 4) contain Cl^? as the dominant anion and their average total ionic concentration (38.65 meq/L) is 1.79 times higher than that of the FGW samples (21.50 meq/L). BGW pockets were generated by non-conservative mixing of FGW with the upconed saline water from the underlying saline groundwater zone of the semi-confined aquifer along bore wells involved in excessive extraction of groundwater from the unconfined aquifer. Groundwater belongs essentially to “high salinity, low sodium” irrigation water class.     

Fraction of young water as an indicator of aquifer vulnerability along two regional flow paths in the Mississippi embayment aquifer system,southeastern USA

Wells along two regional flow paths were sampled to characterize changes in water quality and the vulnerability to contamination of the Memphis aquifer across a range of hydrologic and land-use conditions in the southeastern United States. The flow paths begin in the aquifer outcrop area and end at public supply wells in the confined parts of the aquifer at Memphis, Tennessee. Age-date tracer (e.g. SF₆, ³H, ¹⁴C) data indicate that a component of young water is present in the aquifer at most locations along both flow paths, which is consistent with previous studies at Memphis that documented leakage of shallow water into the Memphis aquifer locally where the overlying confining unit is thin or absent. Mixtures of young and old water were most prevalent where long-term pumping for public supply has lowered groundwater levels and induced downward movement of young water. The occurrence of nitrate, chloride and synthetic organic compounds was correlated to the fraction of young water along the flow paths. Oxic conditions persisted for 10 km or more down dip of the confining unit, and the presence of young water in confined parts of the aquifer suggest that contaminants such as nitrate-N have the potential for transport. Long-term monitoring data for one of the flow-path wells screened in the confined part of the aquifer suggest that the vulnerability of the aquifer as indicated by the fraction of young water is increasing over time.     

Resolving the source and mixing proportions of modern leakage to the Memphis aquifer in a municipal well field using geochemical and 3H/3He data, Memphis, Tennessee, USA

The Memphis aquifer in southwestern Tennessee is a confined to semi-confined unconsolidated sand aquifer and is the primary municipal water source for the Memphis metropolitan area. Leakage of modern water from shallow unconfined aquifers through the upper Claiborne confining unit locally degrades water quality in the Memphis aquifer and makes the aquifer more vulnerable to contamination. Major solute chemistry, tritium, and ³H/³He data were used to investigate the source and mixing proportions of modern water in the Memphis aquifer in the Davis well field, Memphis, Tennessee. Water quality in several production wells in the Davis well field has declined over the past 30 years, mainly through increased total dissolved solids, iron, alkalinity, and hardness. Trends in chemical data, tritium, and other hydrogeologic data support a source for the leakage from the Mississippi River Valley Alluvial aquifer. Mixing proportions of alluvial water in production well water obtained by inverse chemical modeling with PHREEQCi range from 7 to 45%. For two of the production wells, MLGW 414 and 432, ³H/³He data yield mixing ratios similar to those obtained from PHREEQCi in three of four cases; the dissimilar ratio is likely due to a poor solution from the PHREEQCi inverse modeling. Modeling of the age distribution obtained from MLGW 414 and 432 using an exponential-piston flow model (EPM) with an inverse solution computer code yielded mixed results. The EPM solution obtained for MLGW 414 converged with difficulty only for a 5-year transit time in the shallow aquifer and is consistent with a source from the Mississippi River Valley Alluvial aquifer; however, the modeled age of the water is greater than that observed. In comparison, the EPM solution for MLGW 432 converged for the 5- and 7-year transit periods in the shallow aquifer and yielded model ages consistent with observed ³H/³He ages; however, the extent of the maximum radii for infiltration source is not consistent with a Mississippi River Valley Alluvial aquifer source. Other potential sources for leakage to MLGW 432 include water from the Fluvial-terrace aquifer migrating along a fault east of the well field or infiltration of water from a lake south of the well field.     

Characterization of flow and transport dynamics in karst aquifers by analyzing tracer test results in conduits and recharge areas (the Egino Massif,Basque Country,Spain): environmental and management implications

Karst aquifers contribute to supplying drinking water to almost a quarter of the world´s population. Their complex dynamics requires specific approaches aimed at recognizing their singularities, analyzing its vulnerability, and ensuring water resources quality. In this paper, the results of processing and modeling five breakthrough tracer curves obtained under different hydrodynamic conditions in the main conduit of Egino karst aquifer (Basque Country, Spain) are analyzed together with those involving pressure injections of the tracer in the saturated zone of the karst massif recharge area. In the conduit, transport is immediate and highly efficient (recovery rates above 84% and dispersion coefficients from 15.04 to 84.35 m²/min); tracer retentions increase as flow rates decrease and no significant contributions to its surroundings are observed. In contrast, tracer transport from the massif recharge area is more complex: after injection at a pressure of 1 MPa, most tracer remains in the surrounding of the injection borehole, retained in a saturated medium of low effective fracture porosity (? _f ?=?1.02?×?10^?4, assuming a radial divergent flow model); subsequently, the main tracer mobilization to the spring was registered with the first rains, with 0.088 m/min mean velocity and high concentrations per unit mass being injected (C _p /M₀?=?0.03 mg/L/kg), which is evidence that the tracer reaches soon the karst conduit network. In any case, a decreasing tracer presence is registered at the injection zone during a hydrological cycle. In both cases, the observed non-linearity of transport processes should be considered in the development of vulnerability approaches, modeling efforts, and mapping. Furthermore, in the case of karst massif recharge areas, as the presence of pollutants may have a significant impact on the springs and persist over time, their management and protection needs must be revised in each specific site. Simultaneously, quality-monitoring programs at the springs must be adapted to the aquifers recognized dynamics.     

Hydrochemical and isotopic characterisation of the Bathonian and Bajocian coastal aquifer of the Caen area (northern France)

This paper describes the geochemical evolution of groundwater in the Bathonian and Bajocian aquifer along its flowpath. Since this aquifer represents one of the main sources of fresh water supply in the Caen area and has been subjected to a Holocene marine intrusion, its management requires a sound knowledge of (1) the primary conditions and (2) the potential influence of either natural or anthropogenic pressures. Groundwater vertical sampling validity is discussed with the contribution of high resolution temperature logging. The main processes of geochemical evolution along a groundwater flow line and the sea-water intrusion characteristics are discussed using ionic concentrations (Br⁻, F⁻ and major elements) and isotopes (water δ²H and δ¹⁸O, TDIC δ¹³C and A¹⁴C, sulphate δ¹⁸O and δ³⁴S). As the ¹³C content of TDIC is used as a tracer of water-rock interaction, it shows evidence of specific chemical and isotopic evolutions of groundwater within the aquifer, both related to water-rock interaction and mineral equilibria in groundwater. All the above-mentioned tracers evolve downflow: cation concentrations are modified by exchange with clay minerals allowing a high F⁻ concentration in groundwater, whereas Br⁻ and SO²⁻₄ concentrations appear to be redox condition dependant. Superimposed on these geochemical patterns, δ¹⁸O and δ²H compositions indicate that aquifer recharge has varied significantly through time. The chemical evolution of groundwater is locally affected by a salty water intrusion that is characterised by mixing between Flandrian fresh water and sea-water which has interacted with peat as evidenced by a high Br⁻/Cl⁻ ratio and SO²⁻₄ reduction.     

Hydrochemical evidence for mixing of river water and groundwater during high-flow conditions, lower Suwannee River basin, Florida, USA

 Karstic aquifers are highly susceptible to rapid infiltration of river water, particularly during periods of high flow. Following a period of sustained rainfall in the Suwannee River basin, Florida, USA, the stage of the Suwannee River rose from 3.0 to 5.88 m above mean sea level in April 1996 and discharge peaked at 360 m³/s. During these high-flow conditions, water from the Suwannee River migrated directly into the karstic Upper Floridan aquifer, the main source of water supply for the area. Changes in the chemical composition of groundwater were quantified using naturally occurring geochemical tracers and mass-balance modeling techniques. Mixing of river water with groundwater was indicated by a decrease in the concentrations of calcium, silica, and ²²²Rn; and by an increase in dissolved organic carbon (DOC), tannic acid, and chloride, compared to low-flow conditions in water from a nearby monitoring well, Wingate Sink, and Little River Springs. The proportion (fraction) of river water in groundwater ranged from 0.13 to 0.65 at Wingate Sink and from 0.5 to 0.99 at well W-17258, based on binary mixing models using various tracers. The effectiveness of a natural tracer in quantifying mixing of river water and groundwater was related to differences in tracer concentration of the two end members and how conservatively the tracer reacted in the mixed water. Solutes with similar concentrations in the two end-member waters (Na, Mg, K, Cl, SO₄, SiO₂) were not as effective tracers for quantifying mixing of river water and groundwater as those with larger differences in end-member concentrations (Ca, tannic acid, DOC, ²²²Rn, HCO₃). Received, March 1999 / Revised, July 1999 / Accepted, July 1999