A multi-isotope (δD, δO,Sr/Sr,and δB) approach for identifying saltwater intrusion and resolving groundwater evolution along the Western Caprock Escarpment of the Southern High Plains,New Mexico

Declining water levels in arid and semi-arid regions increase an aquifer’s vulnerability to natural and anthropogenic influences. A multi-isotope (δD, δ¹⁸O, ⁸⁷Sr/⁸⁶Sr, and δ¹¹B) approach was used to resolve the geochemical evolution of groundwater in a declining aquifer in a semi-arid region of the southwestern USA as groundwater composition reacts to source-water mixing, cross-formational flow including saltwater intrusion, water–rock interaction, and likely agricultural recharge. Sub-aquifers or local flow systems are present in the Southern High Plains aquifer along the Western Caprock Escarpment in New Mexico, and the study site’s local flow system contains a Na–Cl, high dissolved-solids groundwater that flows from the escarpment until it mixes with a high quality regional aquifer or regional flow system. The local flow system contains water that is similar in composition to the underlying, upper Dockum Group aquifer. Saltwater found in the upper Dockum Group aquifer likely originates in the adjacent Pecos River Basin and crosses beneath or possibly through the hydrologic divide of the Western Caprock Escarpment. Strontium concentrations of 0.9–31 mg/L and a ⁸⁷Sr/⁸⁶Sr range of 0.70845–0.70906 were sufficient to estimate source-water fractions, mixing patterns, and contributions from chemical weathering through mass balance inverse calculations. Boron concentrations (59–1740 mg/L) and δ¹¹B values (+6.0–+46.0‰) were used to confirm source-water mixing, further evaluate water–rock interaction, and examine the influence of possible agricultural recharge. Alteration of B concentrations and δ¹¹B values in an area of likely agricultural recharge indicated the loss of B and decrease in δ¹¹B values likely from plant uptake, adsorption, and weathering contributions in the soil/vadose zone prior to recharge. The effectiveness of ⁸⁷Sr/⁸⁶Sr and δ¹¹B for resolving the geochemical influences in groundwater in the Southern High Plains along the Western Caprock Escarpment allowed for the reinterpretation of the isotopic composition of water that has been shown to be highly variable in the Southern High Plains. This study shows the utility of a multi-isotope approach for resolving the geochemical evolution of groundwater in an aquifer that has a complex relationship with underlying aquifers and the applicability of these isotopes as indicators of the alteration of source waters from natural or anthropogenic influences.     

Paleowaters in Silurian-Devonian carbonate aquifers: Geochemical evolution of groundwater in the Great Lakes region since the Late Pleistocene

Changes in the climatic conditions during the Late Quaternary and Holocene greatly impacted the hydrology and geochemical evolution of groundwaters in the Great Lakes region. Increased hydraulic gradients from melting of kilometer-thick Pleistocene ice sheets reorganized regional-scale groundwater flow in Paleozoic aquifers in underlying intracratonic basins. Here, we present new elemental and isotopic analyses of 134 groundwaters from Silurian-Devonian carbonate and overlying glacial drift aquifers, along the margins of the Illinois and Michigan basins, to evaluate the paleohydrology, age distribution, and geochemical evolution of confined aquifer systems. This study significantly extends the spatial coverage of previously published groundwaters in carbonate and drift aquifers across the Midcontinent region, and extends into deeper portions of the Illinois and Michigan basins, focused on the freshwater-saline water mixing zones. In addition, the hydrogeochemical data from Silurian-Devonian aquifers were integrated with deeper basinal fluids, and brines in Upper Devonian black shales and underlying Cambrian-Ordovician aquifers to reveal a regionally extensive recharge system of Pleistocene-age waters in glaciated sedimentary basins. Elemental and isotope geochemistry of confined groundwaters in Silurian-Devonian carbonate and glacial drift aquifers show that they have been extensively altered by incongruent dissolution of carbonate minerals, dissolution of halite and anhydrite, cation exchange, microbial processes, and mixing with basinal brines. Carbon isotope values of dissolved inorganic carbon (DIC) range from −10 to −2‰, ⁸⁷Sr/⁸⁶Sr ratios range from 0.7080 to 0.7090, and δ³⁴S-SO₄ values range from +10 to 30‰. A few waters have elevated δ¹³C_DIC values (>15‰) from microbial methanogenesis in adjacent organic-rich Upper Devonian shales. Radiocarbon ages and δ¹⁸O and δD values of confined groundwaters indicate they originated as subglacial recharge beneath the Laurentide Ice Sheet (14-50 ka BP, −15 to −13‰ δ¹⁸O). These paleowaters are isolated from shallow flow systems in overlying glacial drift aquifers by lake-bed clays and/or shales. The presence of isotopically depleted waters in Paleozoic aquifers at relatively shallow depths illustrates the importance of continental glaciation on regional-scale groundwater flow. Modern groundwater flow in the Great Lakes region is primarily restricted to shallow unconfined glacial drift aquifers. Recharge waters in Silurian-Devonian and unconfined drift aquifers have δ¹⁸O values within the range of Holocene precipitation: −11 to −8‰ and −7 to −4.5‰ for northern Michigan and northern Indiana/Ohio, respectively. Carbon and Sr isotope systematics indicate shallow groundwaters evolved through congruent dissolution of carbonate minerals under open and closed system conditions (δ¹³C_DIC = −14.7 to−11.1‰ and ⁸⁷Sr/⁸⁶Sr = 0.7080-0.7103). The distinct elemental and isotope geochemistry of Pleistocene- versus Holocene-age waters further confirms that surficial flow systems are out of contact with the deeper basinal-scale flow systems. These results provide improved understanding of the effects of past climate change on groundwater flow and geochemical processes, which are important for determining the sustainability of present-day water resources and stability of saline fluids in sedimentary basins.     

The use of O,H, B,Sr and S isotopes for tracing the origin of dissolved boron in groundwater in Central Macedonia,Greece

The groundwater B concentration in Mesozoic karst, Neogene and alluvial aquifers in the West part of Chalkidiki province in Central Macedonia, Greece reaches 6.45 mg L⁻¹, which exceeds the limit of 1 mg L⁻¹, set by the European Union for drinking water. The high B contents have been detected in this area, not only near the shoreline, where seawater intrusion occurs, but also in the inland part of the basin. Multi isotope (²H, ¹⁸O, ³⁴S, ¹⁸O_(SO4), ¹¹B, ⁸⁷Sr/⁸⁶Sr) data from borehole and thermal water springs allow identification of the possible B sources. The B dissolved in groundwater in the Chalkidiki area is mainly geogenic. The low δ¹¹B values, 0–1‰, similar to those of thermal fluids from continental geothermal fields, and the low Cl/B ratio compared to seawater both indicate a geothermal origin for B and reflect deep circulation and interaction with igneous rocks. The ⁸⁷Sr/⁸⁶Sr ratio also indicates that the deep-aquifer granodiorite is the predominant rock source of Sr, while the shallow limestone unit has negligible effects on the dissolved Sr budget in these thermal karst waters which O and H isotopes show to be of meteoric origin. The main source of high B in borehole water is mainly mixing with B-rich geothermal water. The mixing between geothermal water and water from the Neogene aquifer is also reflected by isotopic contents of SO₄.     

Source and origin of active and fossil thermal spring systems,northern Upper Rhine Graben,Germany

Thermal water samples and related young and fossil mineralization from a geothermal system at the northern margin of the Upper Rhine Graben have been investigated by combining hydrochemistry with stable and Sr isotope geochemistry. Actively discharging thermal springs and mineralization are present in a structural zone that extends over at least 60 km along strike, with two of the main centers of hydrothermal activity being Wiesbaden and Bad Nauheim. This setting provides the rare opportunity to link the chemistry and isotopic signatures of modern thermal waters directly with fossil mineralization dating back to at least 500–800 ka. The fossil thermal spring mineralization can be classified into two major types: barite-(pyrite) fracture filling associated with laterally-extensive silicification; and barite, goethite and silica impregnation mineralization in Tertiary sediments. Additionally, carbonatic sinters occur around active springs. Strontium isotope and trace element data suggest that mixing of a hot (>100 °C), deep-sourced thermal water with cooler groundwater from shallow aquifers is responsible for present-day thermal spring discharge and fossil mineralization. The correlation between both Sr and S isotope ratios and the elevation of the barite mineralization relative to the present-day water table in Wiesbaden is explained by mixing of deep-sourced thermal water having high ⁸⁷Sr/⁸⁶Sr and low δ³⁴S with shallow groundwater of lower ⁸⁷Sr/⁸⁶Sr and higher δ³⁴S. The Sr isotope data demonstrate that the hot thermal waters originate from an aquifer in the Variscan crystalline basement at depths of 3–5 km. The S isotope data show that impregnation-type mineralization is strongly influenced by mixing with SO₄ that has high δ³⁴S values. The fracture style mineralization formed by cooling of the thermal waters, whereas impregnation-type mineralization precipitated by mixing with SO₄-rich groundwater percolating through the sediments.     

The dynamics of central Main Ethiopian Rift waters: Evidence from δD, δO and Sr/Sr ratios

Water samples from cold and geothermal boreholes, hot springs, lakes and rivers were analyzed for δD, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr compositions in order to investigate lake water–groundwater mixing processes, water–rock interactions, and to evaluate groundwater flow paths in the central Main Ethiopian Rift (MER) of the Ziway–Shala basin. Different ranges of isotopic values were recorded for different water types: hot springs show δ¹⁸O −3.36 to +3.69 and δD −15.85 to +24.23, deep Aluto-Langano geothermal wells show δ¹⁸O −4.65 to −1.24 and δD −12.39 to −9.31, groundwater wells show δ¹⁸O −3.99 to +5.14 and δD −19.69 to +32.27, whereas the lakes show δ¹⁸O and δD in the range +3.98 to +7.92 and +26.19 to +45.71, respectively. The intersection of the Local Meteoric Water Line (LMWL: δD = 7 δ¹⁸O + 11.2, R² = 0.94, n = 42) and the Local Evaporation Line (LEL: δD = 5.63δ¹⁸O + 8, n = 14, R² = 0.82) was used to estimate the average isotopic composition of recharge water into the basin (δD = −5.15 and δ¹⁸O = −2.34). These values are depleted if compared with the modern-day average precipitation, presumably indicating paleo-groundwater components recharged during previous humid climatic phases. The measured stable isotope values indicate that the geothermal wells, some of the hot springs and groundwater wells mainly consist of meteoric water. The Sr isotopic signatures in all waters are within the range of the Sr isotopic composition of the rift basalts and rhyolites. The variability of Sr isotopic data also pinpoints complex water–rock interaction and mixing processes in groundwater and surface water. The ⁸⁷Sr/⁸⁶Sr ratio ranges from 0.70445 to 0.70756 in the hot springs, from 0.70426 to 0.70537 in two deep geothermal wells, and from 0.70673 to 0.70721 in the rift lakes Ziway, Langano, Shala and Awasa. The radiogenic composition recorded by the lakes indicates that the input water was predominantly affected by progressive interaction with rhyolitic volcanics and lacustrine sediments.     

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.     

Constraining groundwater flow,residence times,inter-aquifer mixing,and aquifer properties using environmental isotopes in the southeast Murray Basin,Australia

Environmental isotopes (particularly δ¹⁸O, δ²H, and δ¹³C values, ⁸⁷Sr/⁸⁶Sr ratios, and a¹⁴C) constrain geochemical processes, recharge distribution and rates, and inter-aquifer mixing in the Riverine Province of the southern Murray Basin. Due to methanogenesis and the variable δ¹³C values of matrix calcite, δ¹³C values are highly variable and it is difficult to correct ¹⁴C ages using δ¹³C values alone. In catchments where δ¹³C values, ⁸⁷Sr/⁸⁶Sr ratios, and major ion geochemistry yield similar a¹⁴C corrections, ∼15% of the C is derived from the aquifer matrix in the silicate-dominated aquifers, and this value may be used to correct ages in other catchments. Most groundwater has a¹⁴C above background (∼2 pMC) implying that residence times are <30 ka. Catchments containing saline groundwater generally record older ¹⁴C ages compared to catchments that contain lower salinity groundwater, which is consistent with evapotranspiration being the major hydrogeochemical process. However, some low salinity groundwater in the west of the Riverine Province has residence times of >30 ka probably resulting from episodic recharge during infrequent high rainfall episodes. Mixing between shallower and deeper groundwater results in ¹⁴C ages being poorly correlated with distance from the basin margins in many catchments; however, groundwater flow in palaeovalleys where the deeper Calivil–Renmark Formation is coarser grained and has high hydraulic conductivities is considerably more simple with little inter-aquifer mixing. Despite the range of ages, δ¹⁸O and δ²H values of groundwater in the Riverine Province do not preserve a record of changing climate; this is probably due to the absence of extreme climatic variations, such as glaciations, and the fact that the area is not significantly impacted by monsoonal systems.     

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.     

Controls of δS and δO in dissolved sulphate: Learning from a detailed survey in the Llobregat River (Spain)

The S and O isotopic composition of dissolved SO₄, used as a tracer for SO₄ sources, was applied to the water of the Llobregat River system (NE Spain). The survey was carried out at 30 sites where surface water was sampled on a monthly basis over a period of 2a. The concentration of dissolved SO₄ varied from 20 to 1575 mg L⁻¹. Sulphur isotopic compositions clustered in two populations: one – 93% of the samples – had positive values with a mode of +9‰; the other had negative values and a mode of −5‰. Data for δ¹⁸O_SO4 showed a mean value of +11‰, with no bi-modal distribution, though lower values of δ¹⁸O corresponded to samples with negative δ³⁴S. These values can not be explained solely by the contribution of bedrock SO₄ sources: that is, sulphide oxidation and the weathering of outcrops of sulphates, though numerous chemical sediments exist in the basin. Even in a river with a high concentration of natural sources of dissolved SO₄, such as the Llobregat River, the δ³⁴S values suggest that dissolved SO₄ is controlled by a complex mix of both natural and anthropogenic sources. The main anthropogenic sources in this basin are fertilizers, sewage, potash mine effluent and power plant emissions. Detailed river water sampling, together with the chemical and isotopic characterisation of the main anthropogenic inputs, allowed determination of the influence of redox processes, as well as identification of the contribution of natural and anthropogenic SO₄ sources and detection of spatial variations and seasonal changes among these sources. For instance, in the Llobregat River the input of fertilisers is well marked seasonally. Minimum values of δ³⁴S are reported during fertilization periods – from January to March – indicating a higher contribution of this source. The dual isotope approach, δ³⁴S and δ¹⁸O, is useful to better constrain the sources of SO₄. Moreover, in small-scale studies, where the inputs are well known and limited, the mixing models can be enhanced and the contribution of the different sources can be quantified to some extent.     

Groundwater flow system as an archive of palaeotemperature: Noble gas, radiocarbon, stable isotope and geochemical study in the Pannonian Basin, Hungary

To establish the increase in temperature and the time span of the transition between the Late Glacial Maximum (LGM) and the Holocene, the noble gas content, ¹⁸O, ²H, ¹³C δ values, ³H and ¹⁴C activity and chemistry were studied in a groundwater flow system in Quaternary sediments in Hungary. The study area is a sub-basin of the Pannonian Basin, where the C isotope ratios are not influenced by carbonate reactions along the flow path, because the only water-rock interaction is ion exchange. The δ¹⁸O and δ²H values indicate a cold infiltration period, followed by warming, and, finally, warm temperature conditions. The noble gas data show that the average infiltration temperature was 3.3 °C in the cold, 12.9 °C in the warm, and intermediate in the transitional stage. Using the noble gas temperatures, geochemical batch modelling was performed to simulate the chemical processes. Based on the geochemical model, δ¹³C and ¹⁴C₀ (initial radiocarbon activity) in the recharging water were calculated. Transport modelling was used to simulate the distribution of chemical components, δ¹⁸O, δ²H and ¹⁴C₀, along the flow path. It was found that the main processes determining the chemical composition of the groundwater were dissolution/precipitation of calcite and dolomite during infiltration near the surface, and ion exchange along the flow path. In the recharge area the δ¹³C and ¹⁴C₀ were controlled by dissolution and precipitation of carbonate minerals, C speciation, and fractionation processes. All these processes were influenced by the recharge temperature. NGTs calculated from the dissolved noble gas concentrations showed an average of 3.3 °C for cold, and 12.9 °C for warm infiltration, i.e. for the LGM and for the Holocene. The temperature difference was thus 9.1 ± 0.8 °C, which is one of the largest degree of warming detected by noble gases so far. The alkalinity indicates that carbonate reactions were unimportant along the flow path. Owing to the temperature dependence of the equilibrium constants, temperature conditions during infiltration have to be taken into consideration in radiocarbon age calculation. Dispersive transport along the flow path modified the chemical and isotopic composition of infiltrated water. The contribution of the old pore water, which was free of the ¹⁴C isotope, resulted in uncertainties in radiocarbon age determination. It was concluded that determination of the radiocarbon age or mean residence time requires detailed knowledge of the hydraulic conditions of groundwater.     

Application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed

Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, δ⁵⁶Fe and δ⁶⁶Zn isotopic signatures of filtered stream water samples varied by ∼3.5‰ and 0.4‰, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in δ⁵⁶Fe were linked to redox and precipitation reactions occurring in the stream, while changes in δ⁶⁶Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<−2.0‰) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4‰). Acidic drainage from mine wastes contributed heavier dissolved Fe (∼+0.5‰) and lighter Zn (∼+0.2‰) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe (δ⁵⁶Fe ∼ 0‰) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds.     

Hydrochemistry and isotopic studies to identify Ganges River and riverbank groundwater interaction, southern Bangladesh

The Ganges River water and riverbank shallow groundwater were studied during a single wet season using the hydrochemical and isotopic composition of its dissolved load. The dissolved concentrations of major ions (Cl^?, SO₄ ^2?, NO₃ ^?, HCO₃ ^?, Ca²⁺, Na⁺, Mg²⁺, and K⁺), trace elements (barium (Ba) and strontium (Sr)) and stable isotopes (O and D) were determined on samples collected from the Ganges River and its riverbank shallow aquifers. In the present study, the shallow groundwater differs significantly from the Ganges River water; it shows distinct high concentrations of Ca²⁺, Mg²⁺, HCO₃ ^?, Ba, and Sr due to water–rock interaction and this in particular suggests that the Ganges River may not contribute significantly to the riverbank shallow aquifers during wet season. Besides, the sum of the total cationic charge (∑⁺, in milliequivalents per liter) in the groundwater shows high values (2.48 to 13.91 meq/L, average 9.12 meq/L), which is much higher than the sum of the cations observed in the Ganges water (1.36 to 3.10 meq/L, average 1.94 meq/L). Finally, the more depleted stable isotopic (δ ¹⁸O and δ ²H) compositions of the Ganges River water are in contrast to those of the riverbank aquifer having enriched stable isotopic values during the wet season and the riverbank groundwater thus has a purely local origin from precipitation.     

Lithium isotopes in global mid-ocean ridge basalts

The lithium isotope compositions of 30 well-characterized samples of glassy lavas from the three major mid-ocean ridge segments of the world, spanning a wide range in radiogenic isotope and elemental content and sea floor physical parameters, have been measured. The overall data set shows a significant range in δ⁷Li (+1.6 to +5.6), with no global correlation between Li isotopes and other geochemical or tectonic parameters. The samples with the greatest lithophile element depletion (N-MORB: K₂O/TiO₂ < 0.09) display an isotopic range consistent with the extant database. Samples with greater trace element enrichment display a greater degree of isotopic variability and trend toward heavier compositions (δ⁷Li = +2.4 to +5.6), but are not distinct on average from N-MORB. Together with published data, N-MORB is estimated to have mean δ⁷Li = +3.4 ± 1.4‰ (2σ), consistent with the estimate for an uncontaminated MORB source based on pristine peridotite xenoliths. Locally, where sampling density permits, sources of Li isotope heterogeneity may be evaluated. Sample sets from the East Pacific Rise show correlation of δ⁷Li with halogen concentration ratios. This is interpreted at 15.5°N latitude to represent incorporation of <5 weight percent recycled subduction-modified mantle in the MORB source. At 9.5°N latitude the data are more consistent with shallow level magma chamber contamination by seawater-derived components (<0.5 wt.%).     

Use of B isotopes as a tracer of anthropogenic emissions in the atmosphere of Paris,France

In order to test the potential of B isotopes as a tracer of contamination of the atmosphere, the B isotopic composition of rainwater samples monitored over a year in the centre of Paris, France were determined. Boron concentrations range from 19 nmol/L to 500 nmol/L and δ¹¹B range from 0‰ to +38‰. Mean annual values are 148 nmol/L and +25‰, respectively. The results suggest that variability in B isotopic compositions is mainly caused by mixing of two main sources, although isotopic fractionation during the evaporation–condensation processes may also be important. One source is a marine component, which exhibits a heavy B isotopic composition. The decrease of δ¹¹B in rainwater with increasing NO₃/B and SO₄/B molar ratios suggests that a second source may be anthropogenic emissions. To constrain this end-member, B was determined in urban particulates, which were enriched in the light isotope and the lowest values were consistent with a B-rich fossil fuel composition. These results confirm the great sensitivity of B to anthropogenic sources and the ability of B isotopic ratios to decipher the origin of B in the atmosphere.     

Carbon isotope effects in the open-system Fischer-Tropsch synthesis

Carbon isotopic composition was measured for products of the Fischer-Tropsch synthesis: catalytic reaction between CO and H₂ to produce CO, CO₂, light hydrocarbons C1-C4 and “oil” fraction. Hydrogen isotopes were also measured in the oil fraction and the produced water. Experimental runs were conducted in the flow-through reactor at 260-310 °C and 30 bar using the synthesis gas composed of 5N₂ + 3H₂ + 2CO, on Fe-catalyst mixed with ZSM-5 synthetic zeolite. In the two of seven runs a Fe + Co-catalyst was used that gives a lower yield of unsaturated hydrocarbons in reaction products. The isotopic effects depended on the conversion of the carbon monoxide. Under steady-state conditions (CO conversion more than 90%) a strong kinetic fractionation was observed between CO and CO₂ (∼−10‰) and CO and hydrocarbons (∼+38‰). At low conversion a clear “inverse” isotopic trend of the depletion in ¹³C of longer hydrocarbon chains was observed. On average, Δ₁₂ = δ¹³C(CH₄) − δ¹³C(C₂H₆) correlates well with the CO conversion: the C₂H₆ is ∼6‰ isotopically lighter than CH₄ at low conversion and ∼2‰ heavier at steady-state regime. Under steady-state conditions there almost no difference was observed in the isotopic composition of methane and ethane and higher hydrocarbons. The chemical composition of light hydrocarbons in the products of flow-through, dynamic FTS is different from that found in the static FTS-type experiments with Fe-catalyst, but isotopic effects are similar. Our results suggest that the isotopic distribution of carbon found in so-called “abiogenic” hydrocarbons from some natural gases (δ¹³C1 > δ¹³C2 > δ¹³C3  >?) is somewhat similar to that at low conversion of CO, but do not resemble the distribution characteristic for the high conversion products, at least, on Fe-catalyst. Other processes (a simple mixing of two or more endmembers) or other P-T conditions of the carbon reduction could be responsible for the “inverse” isotopic trend found in meteorites and some natural gases.     

Sm and Gd isotopic shifts of Apollo 16 and 17 drill stem samples and their implications for regolith history

The isotopic compositions of Sm and Gd in lunar regolith samples from the Apollo 16 and 17 deep drill stems showed clear isotopic shifts in ¹⁵⁰Sm /¹⁴⁹Sm (ε = +124 to +191 for A-16, and +37 to +111 for A-17) and ¹⁵⁸Gd/¹⁵⁷Gd (ε = +107 to +169 for A-16, and +31 to +84 for A-17) corresponding to neutron fluences of (5.68-9.03) × 10¹⁶ n cm⁻² for A-16 and (1.85-5.04) × 10¹⁶ n cm⁻² for A-17. The depth profiles of neutron fluences suggest that the regoliths at both sites were due to incomplete mixing of three different slabs which experienced individual two-stage irradiation before and after deposition of the upper slabs. The variations in REE compositions provide chemical evidence for incompletely vertical mixing of regoliths especially at upper layers of the two sites. The thermal neutron energy index estimated from the combination of Sm and Gd isotopic shifts, defined as ε_Sm/ε_Gd, shows a small variation (0.61-0.64) in the A-16 core except for the surface layer. On the other hand, a large variation in ε_Sm/ε_Gd = 0.67 to 0.83 in the A-17 core may result from complicated history such as two-stage irradiation and incomplete mixing during the gardening processes. Isotopic enrichments of ¹⁵²Gd and ¹⁵⁴Gd correlated with Eu/Gd elemental abundances and neutron fluences were also observed in almost all of 15 samples, showing evidence of neutron-capture from ¹⁵¹Eu and ¹⁵³Eu, respectively.     

Deciphering interaction of regional aquifers in Southern Tunisia using hydrochemistry and isotopic tools

Groundwater is the most important source of water supply in southern Tunisia. Previous hydrogeologic and isotopic studies carried out in this region revealed the existence of two major aquifer systems: the “Complex Terminal” (CT) and the “Continental Intercalaire” (CI). Turonian carbonates constitute one of the major aquifer levels of the CT multilayered aquifer. It extends over most of southern Tunisia, and its hydrodynamic regime is largely influenced by tectonics, lithology and recharge conditions. Forty-eight groundwater samples from the CI and Turonian aquifers were collected between January and April 2004 for chemical and isotopic analyses. Hydrochemistry and isotopic tools were combined to get an insight into the processes controlling chemical composition of groundwater and wide-scale interaction of these two aquifer systems. Analysis of the dissolved constituents revealed that several processes control the observed chemical composition: (i) incongruent dissolution of carbonate minerals, (ii) dissolution of evaporitic minerals, and (iii) cation exchange. Dissolution alone cannot account for the observed high supersaturation states of groundwater with respect to calcite and dolomite. The observed supersaturation is most probably linked to geogenic CO₂ entering water-bearing horizons of the CT and CI aquifers via deep tectonic faults and discontinuities and subsequent degassing in the exploitation wells. Presence of geogenic CO₂ in the investigated region was confirmed by C isotope data of the DIC reservoir. The radiocarbon content of the Turonian samples varied between 9.5 and 43 pmc. For CI samples generally lower values were recorded, between 3.8 and 22.5 pmc. Stable isotope composition of Turonian groundwater samples varied from −8.3 to −5.3‰ for δ¹⁸O and from −60 to −25‰ for δ²H. The corresponding ranges of δ values for the Continental Intercalaire samples were from −8.9‰ to −6.9‰ for δ¹⁸O and from −68.2‰ to −45.7‰ for δ²H. Stable isotope composition of groundwater representing CT and CI aquifers provide strong evidence for regional interaction between both systems.     

Effect of contaminant concentration on in situ bacterial sulfate reduction and methanogenesis in phenol-contaminated groundwater

The availability of dissolved O₂ can limit biodegradation of organic compounds in aquifers. Where O₂ is depleted, biodegradation proceeds via anaerobic processes, including NO₃-, Mn(IV)-, Fe(III)- and SO₄-reduction and fermentation/methanogenesis. The environmental controls on these anaerobic processes must be understood to support implementation of management strategies such as monitored natural attenuation (MNA). In this study stable isotope analysis is used to show that the relative significance of two key anaerobic biodegradation processes (bacterial SO₄ reduction (BSR) and methanogenesis) in a phenol-contaminated sandstone aquifer is sensitive to spatial and temporal changes in total dissolved phenols concentration (TPC) (= phenol + cresols + dimethylphenols) over a 5-a period. In general, ³⁴SO₄-enrichment (characteristic of bacterial SO₄ reduction) is restricted spatially to locations where TPC < 2000 mg L⁻¹. In contrast, ¹³C-depleted CH₄ and ¹³C-enriched CO₂ isotope compositions (characteristic of methanogenesis) were measured at TPC up to 8000 mg L⁻¹. This is consistent with previous studies that demonstrate suppression of BSR at TPC of >500 mg L⁻¹, and suggests that methanogenic microorganisms may have a higher tolerance for TPC in this contaminant plume. It is concluded that isotopic enrichment trends can be used to identify conditions under which in situ biodegradation may be limited by the properties of the biodegradation substrate (in this case TPC). Such data may be used to deduce the performance of MNA for contaminated groundwater in similar settings.     

Origin and evolution of formation water at the Jujo–Tecominoacán oil reservoir,Gulf of Mexico. Part 2: Isotopic and field-production evidence for fluid connectivity

The chemical and isotopic characterization of formation water from 18 oil production wells, extracted from 5200 to 6100 m b.s.l. at the Jujo–Tecominoacán carbonate reservoir in SE-Mexico, and interpretations of historical production records, were undertaken to determine the origin and hydraulic behavior of deep groundwater systems. The infiltration of surface water during Late Pleistocene to Early Holocene time is suggested by ¹⁴C-concentrations from 2.15 to 31.86 pmC, and by ⁸⁷Sr/⁸⁶Sr-ratios for high-salinity formation water (0.70923–0.70927) that are close to the composition of Holocene to modern seawater. Prior to infiltration, the super-evaporation of seawater reached maximum TDS concentrations of 385 g/L, with lowest δ¹⁸O values characterizing the most hypersaline samples. Minor deviations of formation water and dolomite host rocks from modern and Jurassic ⁸⁷Sr/⁸⁶Sr-seawater composition, respectively, suggest ongoing water–rock interaction, and partial isotopic equilibration between both phases. The abundance of ¹⁴C in all sampled formation water, ⁸⁷Sr/⁸⁶Sr-ratios for high-salinity water close to Holocene – present seawater composition, a water salinity distribution that is independent of historic water-cut, and a total water extraction volume of 2.037 MMm³ (1/83–4/07) excludes a connate, oil-leg origin for the produced water of the Jurassic–Cretaceous mudstone-dolomite sequence. Temporal fluctuations of water chemistry in production intervals, the accelerated migration of water fronts from the reservoir flanks, and isotopic mixing trends between sampled wells confirms the existence of free aquifer water below oil horizons. Vertical and lateral hydraulic mobility has probably been accelerated by petroleum extraction.