Arsenic in groundwater from mineralised Proterozoic basement rocks of Burkina Faso

This study describes the hydrogeochemistry and distributions of As in groundwater from a newly investigated area of Burkina Faso. Groundwaters have been sampled from hand-pumped boreholes and dug wells close to the town of Ouahigouya in northern Burkina Faso. Although most analysed groundwaters have As concentrations of less than 10 μg L⁻¹, they have a large range from <0.5 to 1630 μg L⁻¹. The highest concentrations are found in borehole waters; all dug wells analysed in this study have As concentrations of <10 μg L⁻¹. Skin disorders (melanosis, keratosis and more rare skin tumour) have been identified among the populations in three villages in northern Burkina Faso, two within the study area. Although detailed epidemiological studies have not been carried out, similarities with documented symptoms in other parts of the world suggest that these are likely to be linked to high concentrations of As in drinking water. The high-As groundwaters observed derive from zones of Au mineralisation in Birimian (Lower Proterozoic) volcano-sedimentary rocks, the Au occurring in vein structures along with quartz and altered sulphide minerals (pyrite, chalcopyrite, arsenopyrite). However, the spatial variability in As concentrations in the mineralised zones is large and the degree of testing both laterally and with depth so far is limited. Hence, concentrations are difficult to predict on a local scale. From available data, the groundwater appears to be mainly oxic and the dissolved As occurs almost entirely as As(V) although concentrations are highest in groundwaters with dissolved-O₂ concentrations <2 mg L⁻¹. The source is likely to be the oxidised sulphide minerals and secondary Fe oxides in the mineralised zones. Positive correlations are observed between dissolved As and both Mo and W which are also believed to be derived from ore minerals and oxides in the mineralised zones. The discovery of high As concentrations in some groundwaters from the Birimian rocks of northern Burkina Faso reiterates the need for reconnaissance surveys in mineralised areas of crystalline basement.     

Br/Cl ratios and O, H, C, and B isotopic constraints on the origin of saline waters from eastern Canada

Saline groundwaters were recovered from undisturbed (Restigouche deposit) and active (Brunswick #12 mine) Zn-Pb volcanogenic massive sulfide deposits in the Bathurst Mining Camp (BMC), northern New Brunswick, Canada. These groundwaters, along with fresh to brackish meteoric ground and surface waters from the BMC, have been analyzed to determine their major, trace element and stable isotopic (O, H, C, and B) compositions. Saline groundwaters (total dissolved solids = 22-45 g/L) are characterized by relatively high Na/Ca ratios compared to brines from the Canadian Shield and low Na/Cl_molar and δ¹¹B isotopic compositions (−2.5‰ to 11.1‰) compared to seawater. Although saline waters from the Canadian Shield commonly have oxygen and hydrogen isotopic compositions that plot to the left of the global meteoric water line, those from the BMC fall close to the water line. Fracture and vein carbonate minerals at the Restigouche deposit have restricted carbon isotopic compositions of around −5‰ to −6‰. The carbon isotopic compositions of the saline waters at the Restigouche deposit (+12‰ δ¹³C_DIC) are the result of fractionation of dissolved inorganic carbon by methanogenesis. We suggest that, unlike previous models for shield brines, the composition of saline waters in the BMC is best explained by prolonged water-rock reaction, with no requirement of precursor seawater. We suggest that elevated Br/Cl ratios of saline waters compared to seawater may be explained by differential uptake of Br and Cl during groundwater evolution through water-rock reaction.     

Features of acid–saline systems of Southern Australia

The discovery of layered, SO₄-rich sediments on the Meridiani Planum on Mars has focused attention on understanding the formation of acid–saline lakes. Many salt lakes have formed in southern Australia where regional groundwaters are characterized by acidity and high salinity and show features that might be expected in the Meridiani sediments. Many (but not all) of the acid–saline Australian groundwaters are found where underlying Tertiary sediments are sulfide-rich. When waters from the formations come to the surface or interact with oxidised meteoric water, acid groundwaters result. In this paper examples of such waters around Lake Tyrrell, Victoria, and Lake Dey-Dey, South Australia, are reviewed. The acid–saline groundwaters typically have dissolved solids of 30–60 g/L and pH commonly <4.5. Many contain high concentrations of Fe and other metals, leached from local sediments. The combination of acidity and salinity also releases Ra. Around salt-lakes, these acidic waters often emerge at the surface in marginal spring zones where the low density (ρ ∼ 1.04) regional water flows out over the denser (ρ ∼ 1.16) lake brines. In the spring zones examined, large amounts of Fe are commonly precipitated. In a few places minerals of the alunite-jarosite family are formed which can trap many other metals, including Ra. The studied groundwater systems were discovered by U exploration programs following up radiometric anomalies related to this Ra. Evaporation concentrates the lesser soluble salts (gypsum and some halite) on the surface of the lakes. The lake brines contain most of the more soluble salts and form a column within the porous sediments which is held in place by hydrostatic forces around the salt-lake. These brines are near-neutral in pH.     

Calcite dissolution kinetics in Na-Ca-Mg-Cl brines

Sedimentary basins can contain close to 20% by volume of pore fluids commonly classified as brines. These fluids can become undersaturated with respect to calcite as a result of migration, dispersive mixing, or anthropogenic injection of CO₂. This study measured calcite dissolution rates in geologically relevant Na-Ca-Mg-Cl synthetic brines (50-200 g L⁻¹ TDS). The dissolution rate dependency on brine composition, pCO₂ (0.1-1 bar), and temperature (25.0-82.5 °C) was modeled using the empirical rate equation

R=k(1-Ω)ⁿ     

On elevated fluoride and boron concentrations in groundwaters associated with the Lake Saint-Martin impact structure,Manitoba

Hydrogeological investigations conducted by the Geological Survey of Canada in the Lake Saint-Martin region of Manitoba have confirmed earlier reports of naturally elevated F⁻ and B concentrations in local groundwaters. Fluoride and B concentrations are highly correlated (r² = 0.905) and reach 15.1 mg/L and 8.5 mg/L, respectively. Virtually all groundwaters with F⁻ concentrations greater than the drinking water limit of 1.5 mg/L are from wells within the Lake Saint-Martin impact structure, a 208 Ma complex crater 23 km in diameter underlying a large part of the study area. The high-F⁻ groundwaters can be classified into two groups according to their anionic and isotopic compositions. Group I samples consist of Na-mixed anion groundwaters, with Cl greater than 100 mg/L and highly depleted ¹⁸O compositions indicative of recharge under much cooler climatic conditions than at present. Samples belonging to this group exhibit a striking relationship to crater morphology, and are found in an arcuate belt within the southern rim of the impact structure. Group II high-F⁻ samples consist of Na–HCO₃–SO₄ groundwaters, with little Cl, and less depleted ¹⁸O compositions. Samples belonging to this group are associated with groundwaters recharged locally, on a low ridge within the impact structure. This paper traces the probable source of high-F⁻ groundwaters to phosphatic pellets in shales of the Winnipeg Formation, a regional basal clastic unit which sub-crops at shallow depth beneath the crater rim as a result of more than 200 m of structural uplift associated with the impact event. This extensive aquifer is known elsewhere in southern Manitoba for its naturally-softened groundwaters and locally elevated F⁻ concentrations. Group I groundwaters are interpreted as discharge from the Winnipeg Formation where it abuts against crater-fill deposits. Group II high-F⁻ groundwaters are interpreted as modern recharge from within the impact structure, displacing Group I groundwaters. Thus, elevated F⁻ and B concentrations observed in groundwaters of the Lake Saint-Martin area represent the geochemical signature of upwelling from a deep regional aquifer. The previously unsuspected discharge zone occurs within an isolated sub-crop of the aquifer formed as a result of structural uplift caused by the impact event.     

Use of biomarkers indices in a sediment core to evaluate potential pollution sources in a subtropical reservoir in Brazil

The presence of PAHs, n-alkanes, pristane, and phytanes in core sediment from the Vossoroca reservoir (Parana, southern Brazil) was investigated. The total concentration of the 16 PAHs varied from 15.5 to 1646 μg kg⁻¹. Naphthalene was present in all layers (3.34–74.0 μg kg⁻¹). The most abundant and dominant n-alkanes were n-C₁₅ and n-C₃₆, with average concentrations of 198.1 ± 46.8 and 522.9 ± 167.7 μg kg⁻¹, respectively. Lighter n-alkanes were distributed more evenly through the layers and showed less variation, specially n-C₉, n-C₁₂, and n-C₁₈, with average concentrations of 14.6 ± 3.0, 31.6 ± 1.9, and 95.0 ± 5.2 μg kg⁻¹, respectively; heavier n-alkanes were more unevenly distributed.     

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.     

Comparison of rates of ureolysis between Sporosarcina pasteurii and an indigenous groundwater community under conditions required to precipitate large volumes of calcite

Ureolysis-driven calcite precipitation has potential to seal porosity and fracture networks in rocks thus preventing groundwater flow and contaminant transport. In this study urea hydrolysis and calcite precipitation rates for the model bacterium Sporosarcina pasteurii were compared with those of indigenous groundwater communities under conditions required to precipitate large volumes of calcite (up to 50 g L⁻¹). We conducted microcosm experiments in oxic artificial and anoxic natural groundwaters (collected from the Permo-Triassic sandstone aquifer at Birmingham, UK) that were inoculated with aerobically grown S. pasteurii. The rate constants for urea hydrolysis, k_urea, ranged between 0.06 and 3.29 d⁻¹ and were only affected by inoculum density. Higher Ca²⁺ concentration (50-500 mM Ca²⁺) as well as differences in fO₂ did not inhibit the ureolytic activity of S. pasteurii and did not significantly impact k_urea. These results demonstrate that S. pasteurii has potential to improve calcite precipitation in both oxic and anoxic groundwaters, especially if indigenous communities lack ureolytic activity. Urea hydrolysis by indigenous groundwater communities was investigated in anoxic, natural groundwaters amended with urea and CaCl₂. A notable increase in ureolysis rates was measured only when these communities were stimulated with dilute nutrients (with best results from blackstrap molasses). Furthermore, there was a considerable lag time (12-20 days) before ureolysis and calcite precipitation began. Calculated ureolysis rate constants, k_urea, ranged between 0.03 and 0.05 d⁻¹ and were similar to k_urea values produced by S. pasteurii at low inoculum densities. Overall, this comparative study revealed that the growth of ureolytic microorganisms present within groundwaters can easily be stimulated to enhance rates of urea hydrolysis in the subsurface, and thus can be used to induce calcite precipitation in these environments. The time required for urea hydrolysis to begin is almost instantaneous if an inoculum of S. pasteurii is included, while it may take several weeks for ureolytic groundwater communities to grow and become ureolytically active.     

Particulate air pollution in a small settlement: The effect of local heating

Mass concentrations of PM₁₀, PM_2.5, and black smoke (BS) were measured in April 2003 during a 3-week campaign in a small village and at a nearby background location in the central part of the Czech Republic. In a pilot analysis, concentrations of selected trace elements (Al, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Sr, Cd, Sb, Cs, Pb) in the collected aerosol were determined by means of ICP-MS. Average concentrations of both PM fractions and BS were higher in the village (37, 26 and 26 μg m⁻³) than at the background location (26, 19 and 11 μg m⁻³) for PM₁₀, PM_2.5 and BS, respectively. Both PM₁₀ and PM_2.5 were reasonably correlated in the village (r = 0.80) and also at the background location (r = 0.79). Correlation between same fractions from the village and from the background site were even higher (r = 0.97 and r = 0.95 for the PM₁₀ and PM_2.5, respectively) suggesting that most of the aerosol in both locations may be influenced by similar sources. The ratio between PM₁₀ and PM_2.5 showed that sources in the village contributed about 33% and 35% to local aerosol concentration for PM₁₀ and PM_2.5, respectively. When the data from the two rural locations were compared with corresponding 24-h averages of PM₁₀ concentrations obtained for the period of the campaign from fixed site monitors situated near larger towns, the highest concentration was found in Prague the Czech capital (49 μg m⁻³) followed by a district town Beroun (41 μg m⁻³) and the village (37 μg m⁻³). The lowest PM₁₀ concentration was found in the village background (26 μg m⁻³). Elemental analysis revealed higher concentrations for most of the elements characteristic of combustion aerosol (namely Zn, Pb, As, Mn and Ti) in the PM collected in the village. The results support the idea that traditional heating in villages may contribute a great extent to local air pollution and may represent an important problem.     

Stable isotope geochemistry of ground and surface waters associated with undisturbed massive sulfide deposits; constraints on origin of waters and water-rock reactions

Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ¹⁸O_VSMOW and δ²H_VSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ¹⁸O_VSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ¹⁸O_VSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ¹³C_VPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO₂ and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ¹³C_VPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ¹³C_VPDB), indicating carbon isotopic fractionation from methanogenesis via CO₂ reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH₄-degassing during sampling.     

The aquatic geochemistry of arsenic in volcanic groundwaters from southern Italy

This paper discusses the abundance, speciation and mobility of As in groundwater systems from active volcanic areas in Italy. Using literature data and new additional determinations, the main geochemical processes controlling the fate of As during gas–water–rock interaction in these systems are examined. Arsenic concentrations in the fluids range from 0.1 to 6940 μg/l, with wide differences observed among the different volcanoes and within each area. The dependence of As content on water temperature, pH, redox potential and major ions is investigated. Results demonstrate that As concentrations are highest where active hydrothermal circulation takes place at shallow levels, i.e. at Vulcano Island and the Phlegrean Fields. In both areas the dissolution of As-bearing sulphides is likely to be the main source of As. Mature Cl-rich groundwaters, representative of the discharge from the deep thermal reservoirs, are typically enriched in As with respect to SO₄-rich “steam heated groundwaters”. In the HCO₃⁻ groundwaters recovered at Vesuvius and Etna, aqueous As cycling is limited by the absence of high-temperature interactions and by high-Fe content of the host rocks, resulting in oxidative As adsorption. Thermodynamic modelling suggests that reducing H₂S-rich groundwaters are in equilibrium with realgar, whereas in oxidising environments over-saturation with respect to Fe oxy-hydroxides is indicated. Under these oxidising conditions, As solubility decreases controlled by As co-precipitation with, or adsorption on, Fe oxy-hydroxides. Consistent with thermodynamic considerations, As mobility in the studied areas is enhanced in intermediate redox environments, where both sulphides and Fe hydroxides are unstable.     

Sr isotopic evidence for a multi-source origin of the potassic magmas in the neapolitan area (S. Italy)

New Sr isotopic data on lavas and xenoliths from Somma-Vesuvius and other nearby volcanic areas (Phlegrean Fields and Ischia) are presented. Chemical and isotopic evidences show that not all the Phlegrean Fields rocks belong to the low K series, but some of them may be interpreted as low pressure differentiates of Somma magmas, i.e. as a part of the high K series. Two rock groups are defined in the Ischia low K series, which are well identified both in time and in chemical and isotopic features, and cannot be derived from the same magma source. The low K series in the studied area generally has lower Sr isotopic values than the high K series.Historical Vesuvian lavas show two distinct linear trends with negative slopes when⁸⁷Sr/⁸⁶Sr ratios are plotted against their ages of eruption. Such trends are interpreted to result from mixing of magmas in two separate reservoirs. Evidence from the Vesuvian ejecta shows that Somma-Vesuvius magmas underwent high or low pressure fractionation, in connection with different events of the Vesuvian activity. Distinct magma reservoirs developed episodically at different depths. Isotopic and geochemical evidences do not favour large scale assimilation of crustal materials by Somma-Vesuvius magmas, but instead appear to reflect mantle characteristics.A minimum of three different (inhomogeneous) source regions is necessary to account for the isotopic features of the studied rocks.     

Gold solubility in oxidized and reduced, water-saturated mafic melt

We have performed experiments to evaluate Au solubility in natural, water-saturated basaltic melts as a function of oxygen fugacity. Experiments were carried out at 1000 °C and 200 MPa, and oxygen fugacity was controlled at the fayalite-magnetite-quartz (FMQ) oxygen fugacity buffer and FMQ + 4. All experiments were saturated with a metal-chloride aqueous solution loaded initially as a 10 wt% NaCl eq. fluid. The stable phase assemblage at FMQ consists of basalt melt, olivine, clinopyroxene, a single-phase aqueous fluid, and metallic Au. The stable phase assemblage at FMQ + 4 consists of basalt melt, clinopyroxene, magnetite-spinel solid solution, a single-phase aqueous fluid, and metallic Au. Silicate glasses (i.e., quenched melt) and their contained crystalline material were analyzed by using both electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Measured Au concentrations in the quenched melt range from 4.8 μg g⁻¹ to 0.64 μg g⁻¹ at FMQ + 4, and 0.54 μg g⁻¹ to 0.1 μg g⁻¹ at FMQ. The measured solubility of Au in olivine and clinopyroxene was consistently below the LA-ICP-MS limit of detection (i.e., 0.1 μg g⁻¹). These melt solubility data place important limitations on the dissolved Au content of water-saturated, Cl- and S-bearing basaltic liquids at geologically relevant fO₂ values. The new data are compared to published, experimentally-determined values for Au solubility in dry and hydrous silicate liquids spanning the compositional range from basalt to rhyolite, and the effects of melt composition, oxygen fugacity, pressure and temperature are discussed.     

Canadian Shield brine from the Con Mine, Yellowknife, NT, Canada: Noble gas evidence for an evaporated Palaeozoic seawater origin mixed with glacial meltwater and Holocene recharge

Dissolved noble gas concentrations were measured in high salinity (270 g/L) Ca(Na)-Cl groundwaters from the Con Mine, Yellowknife, Canada in an effort to discriminate between two possible origins, as either a brine generated by evaporative enrichment in a Paleozoic inland sea, or marine water concentrated by freezing during glacial times. Major ion and isotope geochemistry indicate that brines from the deepest level remain relatively undisturbed by mixing with modern water introduced by mining. Mixing calculations are used to quantify fractions of brine, glacial meltwater and modern water. From this, noble gas concentrations were corrected for excess air with Ne and normalized to 100% brine solution. Over-pressuring of helium and argon in the brine provide age constraints based on the accumulation of geogenic ⁴He and ⁴⁰Ar. Radiogenic age calculations together with the local geological history suggest brine emplacement during early Palaeozoic time, likely during the Devonian when evaporitic inland seas existed in this region. The concentrations of the atmospherically derived noble gases in the brine fraction (Kr = 1.4E-8, Xe = 8.5E-10 cc_STP/cc_H2O) are close to atmospheric equilibrium for brine at 25 °C (Kr = 7.3E-9, Xe = 8.0E-10 cc_STP/cc_H2O), but are far lower than would be expected for closed-system concentration of seawater by freezing (Kr = 2.8E-6, Xe = 4.2E-7 cc_STP/cc_H2O). Thus, despite the complicated mixing history of the brine, the atmospheric and geogenic noble gases provide strong evidence for an origin as air-equilibrated brine from evaporated Paleozoic seawater, which infiltrated via density displacement through existing fractures and faults into the Canadian Shield.     

Natural background levels for some ions in groundwater of the Campania region (southern Italy)

The aim of the study was the determination of the natural background levels (NBLs) for the ions Na⁺, Cl^?, SO₄ ^2?, As³⁺, F^?, Fe²⁺, and Mn²⁺, in some groundwater bodies of the Campania region (southern Italy). The ??Protocol to evaluate the natural background concentrations?? proposed in 2009 by ISPRA (Italian Institute for Environmental Protection and Research) has been applied to the chemical data set of groundwater of the examined groundwater bodies. These analyses have also been examined following the guidelines of the BRIDGE project (Background cRiteria for the IDentification of Groundwater thrEshold). These approaches to evaluate the Threshold Values (TVs) and the NBLs, based on probability distribution functions, have been applied in many countries by various authors during the last 5?years. Changes applied to ISPRA Protocol in this study concern mainly the preselection criteria, in particular threshold values of specific ions, deriving from the aquifers geochemical features. The preselection criteria of the ISPRA Protocol have been merged with those of the BRIDGE Project in order to define a procedure suitable for the definition of the NBLs in the examined aquifers. The NBL of fluoride for the ??Phlegrean Fields?? and the ??eastern Plain of Naples?? groundwater bodies shows values deeply exceeding the reference value (REF) of 1,500???g/L, ranging between 3,600 and 15,000???g/L. The cause of this very high fluoride content is in the natural features of the aquifers constituted by volcanic and pyroclastic rocks. The volcanic origin of the aquifers is also the reason for the high arsenic content in ??Phlegrean Fields?? groundwater. Here the NBL calculated was about 47???g/L against the drinking water standard value of 10???g/L. The widespread high content of manganese and iron for the groundwater body of the ??eastern Plain of Naples?? is due to the reducing conditions related to the extensive marshlands present in the past. The very high NBL of all the examined ions for the groundwater body of ??Ischia Island?? depends on the existence of a geothermal system.     

Solubility of plutonium(VI) carbonate in saline solutions

Among the plutonium oxidation states found to form in the environment, mobile plutonium(VI) can exist under oxidizing conditions and in waters with high chloride content due to radiolysis effects. We are investigating the solubility and speciation of plutonium(VI) carbonate under conditions relevant to natural waters and brines such as those found near some geologic radioactive waste repositories. The solid Pu(VI) phase PuO₂CO₃(s) was prepared and its solubility was measured in NaCl and NaClO₄ solutions in a CO₂ atmosphere as a function of pH and ionic strength (0.1-5.6 m). The concentration of soluble plutonium in solution was calculated from spectroscopic data and liquid scintillation counting. Spectroscopic measurements also revealed the plutonium oxidation state. The apparent solubility product of PuO₂CO₃(s) was determined at selected electrolyte concentrations to be, log K_s,0 = −13.95 ± 0.07 (0.1 m NaCl), log K_s,0 = −14.07 ± 0.13 (5.6 m NaCl), and log K_s,0 = −15.26 ± 0.11 (5.6 m NaClO₄). Specific ion interaction theory was used to calculate the solubility product at zero ionic strength, .     

Irrigation produces elevated arsenic in the underlying groundwater of a semi-arid basin in Southwestern Idaho

The shallow aquifer beneath the Western Snake River Plain (Idaho, USA) exhibits widespread elevated arsenic concentrations (up to 120 μg L⁻¹). While semi-arid, crop irrigation has increased annual recharge to the aquifer from approximately 1 cm prior to a current rate of >50 cm year⁻¹. The highest aqueous arsenic concentrations are found in proximity to the water table (all values >50 μg L⁻¹ within 50 m) and concentrations decline with depth. Despite strong vertical redox stratification within the aquifer, spatial distribution of aqueous species indicates that redox processes are not primary drivers of arsenic mobilization. Arsenic release and transport occur under oxidizing conditions; groundwater wells containing dissolved arsenic at >50 μg L⁻¹ exhibit elevated concentrations of O₂ (average 4 mg L⁻¹) and NO₃ (average 8 mg L⁻¹) and low concentrations of dissolved Fe (<20 μg L⁻¹). Sequential extractions and spectroscopic analysis of surficial soils and sediments indicate solid phase arsenic is primarily arsenate and is present at elevated concentrations (4–45 mg kg⁻¹, average: 17 mg kg⁻¹) relative to global sedimentary abundances. The highest concentrations of easily mobilized arsenic (up to 7 mg kg⁻¹) are associated with surficial soils and sediments visibly stained with iron oxides. Batch leaching experiments on these materials using irrigation waters produce pore water arsenic concentrations approximating those observed in the shallow aquifer (up to 152 μg L⁻¹). While As:Cl aqueous phase relationships suggest minor evaporative enrichment, this appears to be a relic of the pre-irrigation environment. Collectively, these data indicate that infiltrating irrigation waters leach arsenic from surficial sediments to the underlying aquifer.     

Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field,Taupo Volcanic Zone,New Zealand

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW_e). Soil CO₂ degassing was quantified with 2663 CO₂ flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m⁻²) using published soil temperature heat flow functions. Both CO₂ flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO₂ gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO₂ emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO₂ emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they contributed little (<1%) to pre-production CO₂ emissions due to the loss of >99% of the original CO₂ content due to depressurisation and boiling as the fluids ascended to the surface. Consequently, the soil has persisted as the major (99%) pathway of CO₂ release to the atmosphere from the high temperature reservoir at Ohaaki. The CO₂ flux and heat flow surveys indicate that despite 20 a of production the variability in location, spatial extent and magnitude of CO₂ flux remains consistent with established geochemical and geophysical models of the Ohaaki Field. At both OHW and OHE carbon isotopic analyses of soil gas indicate a two-stage fractionation process for moderate-flux (>60 g m⁻² d⁻¹) sites; boiling during fluid ascent within the underlying reservoir and isotopic enrichment as CO₂ diffuses through porous media of the soil zone. For high-flux sites (>300 g m⁻² d⁻¹), the δ¹³CO₂ signature (−7.4 ± 0.3‰ OHW and −6.5 ± 0.6‰ OHE) is unaffected by near-surface (soil zone) fractionation processes and reflects the composition of the boiled magmatic CO₂ source for each respective upflow. Flux thresholds of <30 g m⁻² d⁻¹ for purely diffusive gas transport, between 30 and 300 g m⁻² d⁻¹ for combined diffusive–advective transport, and ?300 g m⁻² d⁻¹ for purely advective gas transport at Ohaaki were assigned. δ¹³CO₂ values and cumulative probability plots of CO₂ flux data both identified a threshold of ∼15 g m⁻² d⁻¹ by which background (atmospheric and soil respired) CO₂ may be differentiated from hydrothermal CO₂.     

Iron(III) accumulations in inland saline waterways,Hunter Valley,Australia: Mineralogy,micromorphology and pore-water geochemistry

Discharge of Fe(II)-rich groundwaters into surface-waters results in the accumulation of Fe(III)-minerals in salinized sand-bed waterways of the Hunter Valley, Australia. The objective of this study was to characterise the mineralogy, micromorphology and pore-water geochemistry of these Fe(III) accumulations. Pore-waters had a circumneutral pH (6.2–7.2), were sub-oxic to oxic (Eh 59–453 mV), and had dissolved Fe(II) concentrations up to 81.6 mg L⁻¹. X-ray diffraction (XRD) on natural and acid-ammonium-oxalate (AAO) extracted samples indicated a dominance of 2-line ferrihydrite in most samples, with lesser amounts of goethite, lepidocrocite, quartz, and alumino-silicate clays. The majority of Fe in the samples was bound in the AAO extractable fraction (Fe^Ox) relative to the Na-dithionite extractable fraction (Fe^Di), with generally high Fe^Ox:Fe^Di ratios (0.52–0.92). The presence of nano-crystalline 2-line ferrihydrite (Fe₅HO₃·4H₂O) with lesser amounts of goethite (α-FeOOH) was confirmed by scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX), and transmission electron microscopy (TEM) coupled with selected area electron diffraction (SAED). In addition, it was found that lepidocrocite (γ-FeOOH), which occurred as nanoparticles as little as ∼5 lattice spacings thick perpendicular to the (0 2 0) lattice plane, was also present in the studied Fe(III) deposits. Overall, the results highlight the complex variability in the crystallinity and particle-size of Fe(III)-minerals which form via oxidation of Fe(II)-rich groundwaters in sand-bed streams. This variability may be attributed to: (1) divergent precipitation conditions influencing the Fe(II) oxidation rate and the associated supply and hydrolysis of the Fe(III) ion, (2) the effect of interfering compounds, and (3) the influence of bacteria, especially Leptothrix ochracea.     

Changes in fish mercury concentrations over 20 years in an acidified lake subject to experimental liming

Lake Iso Valkjärvi (southern Finland, Europe) was divided in two with a plastic curtain in 1991. One half was neutralized with CaCO₃, and the other acted as a control. Mercury concentrations of perch (Perca fluviatilis) and northern pike (Esox lucius) in the limed and control side of the lake were studied both before and after the treatment. Average Hg concentrations of perch and pike were 0.40 and 1.2 μg g⁻¹ (ww) in the early 1980s and 0.25 and 0.72 μg g⁻¹ (ww) a decade later at the time of liming. Ten years after the liming the Hg concentrations of perch in the limed and control sides of the lake were 0.21 and 0.28 μg g⁻¹ (ww) and those of pike were 0.69 and 0.43 μg g⁻¹ (ww), respectively. Nitrogen isotope ratios (δ¹⁵N) for perch in the sampling period 2002–2004 showed wide variation suggesting variable trophic positions for individual fish. Pike formed two groups according to their δ¹⁵N-values, suggesting that zoobenthos dominated the diet of pike around 20 cm in length and fish that of the larger pikes. Because the δ¹⁵N-values of fish were at similar levels in the limed and control sides of L. Iso Valkjärvi, differences in food web structure cannot account for the different fish Hg concentrations. A more likely explanation is water quality induced differences in the dynamics and bioavailability of Hg, leading to decreased formation of methyl Hg.