Hydrochemical Groundwater Evolution in the Bunter Sandstone Sequence of the Odenwald Mountain Range,Germany: A Laboratory and Field Study

Field and laboratory investigations were performed to identify the principal mechanisms of the hydrochemical groundwater evolution among low mineralised groundwater in the Triassic Bunter sandstone aquifer of the Odenwald low mountain range, central Germany. Hydrochemical composition comprises low pH, SO₄-rich shallow groundwaters issued by springs (Ca-Mg-SO₄-type) grading to SO₄-poor deep groundwaters with near-neutral pH (Ca-HCO₃-type). Batch experiments of the original rock were run to determine primary mineral alteration reactions and the origin of dissolved ions. Principal experimental reactions comprise the decomposition of anorthite, K-feldspar, biotite and jarosite as mineral components of the original sandstone rock and the formation of clay minerals of the smectite group (Ca-montmorillonite, beidellite), and iron hydroxides as secondary minerals. Mobilisation of fluid inclusion in quartz grains contributes to Na and Cl concentrations in the leachates. The evolution of deep groundwater circulation proceeds by mineral alteration reactions calculated by the inverse modelling of both primary and secondary minerals to produce low-T mineral phases. The dissolution of K-feldspar converts Ca-montmorillonite to illite (illitisation). The formation of Na-beidellite correlates with decreasing concentration of Na in solution. Mineral reactions further proceed to the formation of kaolinite as stable mineral phase. As indicated by modelled adsorption curves, the decrease of SO₄ concentrations during groundwater evolution relates to the adsorption of SO₄ on iron hydroxides. The leaching of calcite indicated for individual groundwaters relates to the distribution of loess in the appropriate catchment areas.     

Hydrogeochemistry of mine, surface and groundwaters from the Sanggok mine creek in the upper Chungju Lake, Republic of Korea

 The Sanggok mine used to be one of the largest lead-zinc mines in the Hwanggangri mining district, Republic of Korea. The present study characterizes the heavy metal contamination in the abandoned Sanggok mine creek on the basis of physico-chemical properties of various kinds of water samples (mine, surface and groundwater). Hydrochemistry of the water samples is characterized by the relatively significant enrichment of Ca²⁺, HCO₃ ^–, NO₃ ^– and Cl^– in the surface and groundwaters, whereas the mine water is relatively enriched in Ca²⁺, Mg²⁺, heavy metals, and HCO₃ ^– and SO₄ ^2–. The more polluted mine water has a lower pH and higher Eh, conductivity and TDS values. The concentrations of some toxic elements (Al, As, Cd, Cu, Fe, Mn, Pb, Se, Sr, Pb and Zn) are tens to hundreds of times higher in the mine water than in the unpolluted surface and groundwaters. However, most immobile toxic pollutants from the mine drainage were quickly removed from the surface water by the precipitation of Al and Fe oxyhydroxides. Geochemical modeling showed that potentially toxic heavy metals might exist largely in the forms of MSO₄ ^2– and M²⁺ in the mine water. These metals in the surface and groundwaters could form M²⁺, CO₃ ^2– and OH^– complex ions. Computer simulation indicates that the saturation indices of albite, alunite, anhydrite, chlorite, fluorite, gypsum, halloysite and strontianite in the water samples are undersaturated and have progressively evolved toward the saturation condition. However, barite, calcite, chalcedony, dolomite, gibbsite, illite and quartz were in equilibrium, and only clay minerals were supersaturated. Ground and mine waters seemed to be in equilibrium with kaolinite field, but some surface water were in equilibrium with gibbsite and seceded from the stability field of quartz. This indicates that surface water samples in reaction with carbonate rocks would first equilibrate with carbonate minerals, then gibbsite to kaolinite. Investigations on water quality and environmental improvement of the severely polluted Sanggok creek, as well as remediation methods on the possible future pollution of the groundwater by the acid mine drainage from the abandoned metal mines, are urgently required. Received: 4 February 2000 · Accepted: 9 May 2000     

Volcanic degassing at Somma–Vesuvio (Italy) inferred by chemical and isotopic signatures of groundwater

A geochemical model is proposed for water evolution at Somma–Vesuvio, based on the chemical and isotopic composition of groundwaters, submarine gas emission and chemical composition of the dissolved gases. The active degassing processes, present in the highest part of the volcano edifice, strongly influence the groundwater evolution. The geological–volcanological setting of the volcano forces the waters infiltrating at Somma–Vesuvio caldera, enriched in volcanic gases, to flow towards the southern sector to an area of high pCO₂ groundwaters. Reaction path modelling applied to this conceptual model, involving gas–water–rock interaction, highlights an intense degassing process in the aquifer controlling the chemical and isotopic composition of dissolved gases, total dissolved inorganic C (TDIC) and submarine gas emission. Mapping of TDIC shows a unique area of high values situated SSE of Vesuvio volcano with an average TDIC value of 0.039 mol/L, i.e., one order of magnitude higher than groundwaters from other sectors of the volcano. On the basis of TDIC values, the amount of CO₂ transported by Vesuvio groundwaters was estimated at about 150 t/d. This estimate does not take into account the fraction of gas loss by degassing, however, it represents a relevant part of the CO₂ emitted in this quiescent period by the Vesuvio volcanic system, being of the same order of magnitude as the CO₂ diffusely degassed from the crater area.     

Metal release from dolomites at high partial-pressures of CO2

The potential for metal release associated with CO₂ leakage from underground storage formations into shallow aquifers is an important consideration in assessment of risk associated with CO₂ sequestration. Metal release can be driven by acidification of groundwaters caused by dissolution of CO₂ and subsequent dissociation of carbonic acid. Thus, acidity is considered one of the main drivers for water quality degradation when evaluating potential impacts of CO₂ leakage. Dissolution of carbonate minerals buffers the increased acidity. Thus, it is generally thought that carbonate aquifers will be less impacted by CO₂ leakage than non-carbonate aquifers due to their high buffering potential. However, dissolution of carbonate minerals can also release trace metals, often present as impurities in the carbonate crystal structure, into solution. The impact of the release of trace metals through this mechanism on water quality remains relatively unknown. In a previous study we demonstrated that calcite dissolution contributed more metal release into solution than sulfide dissolution or desorption when limestone samples were dissolved in elevated CO₂ conditions. The study presented in this paper expanded our work to dolomite formations and details a thorough investigation on the role of mineral composition and mechanisms on trace element release in the presence of CO₂. Detailed characterization of samples from dolomite formations demonstrated stronger associations of metal releases with dissolution of carbonate mineral phases relative to sulfide minerals or surface sorption sites. Aqueous concentrations of Sr²⁺, CO²⁺, Mn²⁺, Ni²⁺, Tl⁺, and Zn²⁺ increased when these dolomite rocks were exposed to elevated concentrations of CO₂. The aqueous concentrations of these metals correlate to aqueous concentrations of Ca²⁺ throughout the experiments. All of the experimental evidence points to carbonate minerals as the dominant source of metals from these dolomite rocks to solution under experimental CO₂ leakage conditions. Aqueous concentrations of Ca²⁺ and Mg²⁺ predicted from numerical simulation of kinetic dolomite dissolution match those observed in the experiments when the surface area is three to five orders of magnitude lower than the surface area of the samples measured by gas adsorption.     

Coal seam gas distribution and hydrodynamics of the Sydney Basin,NSW, Australia

This paper reviews various coal seam gas (CSG) models that have been developed for the Sydney Basin, and provides an alternative interpretation for gas composition layering and deep-seated CO₂ origins. Open file CSG wells, supplemented by mine-scale information, were used to examine trends in gas content and composition at locations from the margin to the centre of the basin. Regionally available hydrochemistry data and interpretations of hydrodynamics were incorporated with conventional petroleum well data on porosity and permeability. The synthesised gas and groundwater model presented in this paper suggests that meteoric water flow under hydrostatic pressure transports methanogenic consortia into the subsurface and that water chemistry evolves during migration from calcium-rich freshwaters in inland recharge areas towards sodium-rich brackish water down-gradient and with depth. Groundwater chemistry changes result in the dissolution and precipitation of minerals as well as affecting the behaviour of dissolved gases such as CO₂. Mixing of carbonate-rich waters with waters of significantly different chemistries at depth causes the liberation of CO₂ gas from the solution that is adsorbed into the coal matrix in hydrodynamically closed terrains. In more open systems, excess CO₂ in the groundwater (carried as bicarbonate) may lead to precipitation of calcite in the host strata. As a result, areas in the central and eastern parts of the basin do not host spatially extensive CO₂ gas accumulations but experience more widespread calcite mineralisation, with gas compositions dominated by hydrocarbons, including wet gases. Basin boundary areas (commonly topographic and/or structural highs) in the northern, western and southern parts of the basin commonly contain CO₂-rich gases at depth. This deep-seated CO₂-rich gas is generally thought to derive from local to continental scale magmatic intrusions, but could also be the product of carbonate dissolution or acetate fermentation.     

Carbon isotopes and geochemical processes in CO2-rich cold mineral water,N-Portugal

This paper summarizes a new outlook on the conceptual model of Melgaço–Messegães CO₂-rich cold (≈18 °C) mineral water systems, issuing in N of Portugal, based on their isotopic (²H, ³H, ¹³C, ¹⁴C and ¹⁸O) and geochemical features. Stable isotopes indicate the meteoric origin of these CO₂-rich mineral waters. Based on the isotopic fractionation with the altitude, a recharge altitude between 513 up to 740 m a.s.l. was estimated, corroborating the tritium results. The lowest ³H content (0 TU) is found in the groundwater samples with the highest mineralization. The mineral waters circulation are mainly related to a granitic and granodioritic environment inducing two different groundwater types (Ca/Na–HCO₃ and Na/Ca–HCO₃), indicating different underground flow paths. Calcium dissolution is controlled by hydrolysis of rock-matrix silicate minerals (e.g. Ca-plagioclases) and not associated to anthropogenic sources. The shallow dilute groundwaters exhibit signatures of anthropogenic origins (e.g. NO₃) and higher Na/Ca ratios. The stable isotopes together with the geochemistry provided no indication of mixing between the regional shallow cold dilute groundwater and mineral water systems. The heavy isotopic signatures identified in the δ¹³C data (δ¹³C = 4.7 ‰, performed on the total dissolved inorganic carbon (TDIC) of CO₂-rich mineral waters) could be derived from a deep-seated (upper mantle) source or associated to methanogenesis (CH₄ source). The negligible ¹⁴C content (≈2 pmC) determined in the TDIC of the mineral waters, corroborates the hypothesis of a mantle-derived carbon source to the mineral groundwater systems or dissolution of carbonate layers at depth.     

Water–Rock Interactions: An Investigation of the Relationships Between Mineralogy and Groundwater Composition and Flow in a Subtropical Basalt Aquifer

A holistic study of the composition of the basalt groundwaters of the Atherton Tablelands region in Queensland, Australia was undertaken to elucidate possible mechanisms for the evolution of these very low salinity, silica- and bicarbonate-rich groundwaters. It is proposed that aluminosilicate mineral weathering is the major contributing process to the overall composition of the basalt groundwaters. The groundwaters approach equilibrium with respect to the primary minerals with increasing pH and are mostly in equilibrium with the major secondary minerals (kaolinite and smectite), and other secondary phases such as goethite, hematite, and gibbsite, which are common accessory minerals in the Atherton basalts. The mineralogy of the basalt rocks, which has been examined using X-ray diffraction and whole rock geochemistry methods, supports the proposed model for the hydrogeochemical evolution of these groundwaters: precipitation + CO₂ (atmospheric + soil) + pyroxene + feldspars + olivine yields H₄SiO₄, HCO₃ ⁻, Mg²⁺, Na⁺, Ca²⁺ + kaolinite and smectite clays + amorphous or crystalline silica + accessory minerals (hematite, goethite, gibbsite, carbonates, zeolites, and pyrite). The variations in the mineralogical content of these basalts also provide insights into the controls on groundwater storage and movement in this aquifer system. The fresh and weathered vesicular basalts are considered to be important in terms of zones of groundwater occurrence, while the fractures in the massive basalt are important pathways for groundwater movement.     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.     

Trace metals in recharge and discharge ground waters at two sites at the Baltic coast of Sweden

The distribution and controls of trace elements (Cd, Cr, Cu, Ni, Pb, Zn and U) in shallow groundwater in discharge and recharge zones were analysed at two sites on the Baltic coast of Sweden; one granite-dominated and one with a significant addition of calcite. Although the study sites differ in overburden geochemistry and groundwater trace metal concentrations, which were well reflected in the general groundwater composition, the relative hydrochemical differences between recharge and discharge ground waters were similar at both sites, and temporally stable. The concentrations of Cd, Cu, Ni and U were higher in soil tubes in recharge areas, but Cr was higher in discharge zones. Also concentrations of HS, Fe, Mn and NH₄ were higher in discharge samples, which in combination with increased ³⁴S values provide strong evidence of a transition from oxidizing to more reducing conditions along the groundwater flow gradient. In terms of trace metals, this might mean either mobilisation due to dissolution of trace-metal carrying Fe(III) and Mn(IV) phases, or immobilisation caused by precipitation of discrete trace-metal sulfides or co-precipitation with Fe sulfides. The results from this study show that the latter is dominant in both the carbonate and granite environments for the metals Cd, Cu and Ni. Chromium concentrations were likely coupled to organic complexation and were higher in discharge groundwater, where DOC was also more abundant. As the concentration of several potentially toxic trace metals were found to differ between recharge and discharge areas, a climate driven change in hydrology might have a substantial impact on the distribution of these metals.     

Heavy metal fractionation in roof run off in Ile-Ife, Nigeria

Runoff was collected from three different roofing materials that are commonly used for roofing in Ile-Ife, Nigeria, between the months of June to August, 2004. The samples were collected in four geographical locations in the town. The run offs were analysed for pH, Temp, TDS, CI?, S0₄ ^2?, PO₄ ^3? N0₃ ^2?, EC and some heavy metals both as regards total, dissolved and particulate fractions. Analysis of the heavy metals was done using flame Atomic Absorption Spectrophotometer. The quantity of these parameters varies with the different roofing materials. In terms of dissolved metals, Fe is the most predominant metal with mean values 0.59 ± 0.29, 0.82 ± 0.14, and 1.04 ± 0.27 mg/L for asbestos, ceramic tiles and metal sheets respectively. The tendency of the roofing materials to release dissolved metals is arranged as follows: Zn, Cr and Fe (metal sheet > Ceramic > asbestos); Cd and Pb (asbestos > ceramic > metal sheet). In terms of particulate metals, the concentration of Cd and Pb are higher in the asbestos than other roofing stuffs. The sequence of their predominance in asbestos is as follows: Pb (0.83±0.55 mg/L) > Cd (0.29 ± 0.07 mg/L). In all the roofs, both particulate and dissolved metals except Zn exceeded WHO permissible limits for drinking water. The high levels of the metals obtained in this study may likely result in consumer complaints since some of the metals are not only carcinogenic but are also liable of impacting bad taste in water.     

Correlations, partitioning and bioaccumulation of trace metals between different segments of Taylor Creek, southern Nigeria

Correlations between trace metals in dissolved and particulate phases, B. bayad and sediments were investigated in five selected sites along Taylor Creek, which lies between longitude 006°17^I to 006°21^I E and latitude 05°01^I to 05°05^I N. The degree of correlation between the various metals was different in each of the investigated segments. Between segments, not many significant correlations were recognized. Only Ni and Cd, Mn and Cd, Mn and Ni, and Mn and Pb are correlated in the sediments and in the particulate phase, Fe and Cr, Pb and Cd, and Zn and Ni are correlated, which suggests that the sources are not common for both compartments. Partitioning coefficients (K_d) of trace metals between dissolved and particulate phases are generally low, which is typical for fresh water ecosystems and fairly stable over Taylor Creek all through the seasons. Furthermore, the bio-concentration factors (BCF) of B. bayad were low unlike those of other natural waters. Cluster analysis showed that metal accumulation in the particulate phase differed from those observed in sediments, which also confirms that the pollution of the Creek might be from different sources.     

Temporal variability of trace metals in new jersey pinelands streams: relationships to discharge and pH

Dissolved and particulate trace metal (Al, Cd, Cu, Pb, and Zn) concentrations were determined over a 21 month time period at four streamwater sites in the Pinelands (New Jersey, USA), a coastal plain region characterized by low-pH waters and highly weathered soils. Al and Zn were also determined at two sites over a 5 day period following a major precipitation event. In the Batsto River (pH 4.4–6.3), a representative Pinelands stream draining a largely forested watershed moderately impacted by agriculture, discharge-weighted mean concentrations of dissolved metals were (in nM): Al = 4610; Cd = 0.39; Cu = 4.6; Pb = 1.0; and Zn = 149. Dissolved Cd, Cu, and Zn in the undeveloped Bass River (pH 4.1–4.8) are in a similar range, but Pb concentration is 2–3 times greater. Dissolved metals show highly significant positive correlations to discharge, and weaker inverse relationships to pH over both the long- and short-term time series. Overall, seasonal and short-term variability in dissolved metal concentrations is most consistent with control by hydrologic flow path changes during high discharge, when shallow groundwaters mobilize anthropogenic metals stored in near-surface soil horizons and bypass potential metal removal processes in bordering wetlands. The data also suggest that in-stream metal removal driven by summertime biological productivity may further reduce low-discharge metal concentrations, as a secondary effect. For these metals, the particulate fraction is generally minor, and variations in solution/particle partitioning are unimportant to spatial/temporal variations dissolved concentrations, except for Pb. Estimates of atmospheric input can account for riverine fluxes of these metals, and suggest that Zn retention is minimal in this system, while Pb, Cu and Cd are more strongly retained. The positive relationship between discharge and metals concentration, and the unusually high concentrations in Pinelands streams compared to other world rivers, suggest that riverine effects on metals distributions in the estuary and nearby coastal ocean will be measurable and strongly seasonal.     

Soil and groundwater pollution of an urban catchment by trace metals: case study of the Addis Ababa region, central Ethiopia

Analysis of the total heavy metal (Cr, Cd, Pb, As, Cu, Ni, Zn, Co) concentration was performed on 33 soil samples taken from different profiles and soil types in a highly urbanized and industrial sector of Addis Ababa, central Ethiopia. They were analyzed using aqua regia extraction coupled with a four-stage sequential extraction (SE) procedure. The objectives of the analysis were to investigate the degree of soil heavy metal contamination, its binding forms, mobility and the implications for the groundwater resource. The results show a relatively high content of the analyzed trace metals in the soil attributed to anthropogenic and geogenic sources. Although most of the trace metals are found in the upper few centimeters of the residual soils, because of churning processes within the black cotton soils, vertical distribution of the trace metals is complex. According to the heavy metal SE analysis, the major heavy metal contribution is from the residual followed by the hydroxide phases. Groundwater heavy metal contamination is present with more than 90 and 50% of the analyzed groundwater samples exceeding WHO guidelines for Cr and Cd, respectively. Since the degree of soil heavy metal contamination has apparently not surpassed the soil’s buffering capacity, it appears that the transport path of these toxic metals to the groundwater is through fractures, joints, and related preferential flow paths.     

The impact of CO<Subscript>2</Subscript> on shallow groundwater chemistry: observations at a natural analog site and implications for carbon sequestration

In a natural analog study of risks associated with carbon sequestration, impacts of CO₂ on shallow groundwater quality have been measured in a sandstone aquifer in New Mexico, USA. Despite relatively high levels of dissolved CO₂, originating from depth and producing geysering at one well, pH depression and consequent trace element mobility are relatively minor effects due to the buffering capacity of the aquifer. However, local contamination due to influx of brackish waters in a subset of wells is significant. Geochemical modeling of major ion concentrations suggests that high alkalinity and carbonate mineral dissolution buffers pH changes due to CO₂ influx. Analysis of trends in dissolved trace elements, chloride, and CO₂ reveal no evidence of in situ trace element mobilization. There is clear evidence, however, that As, U, and Pb are locally co-transported into the aquifer with CO₂-rich brackish water. This study illustrates the role that local geochemical conditions will play in determining the effectiveness of monitoring strategies for CO₂ leakage. For example, if buffering is significant, pH monitoring may not effectively detect CO₂ leakage. This study also highlights potential complications that CO₂ carrier fluids, such as brackish waters, pose in monitoring impacts of geologic sequestration.     

Metal binding capacity of northern European surface waters for Cd,Cu, and Pb

Total concentrations of and binding capacities for Cd, Cu, and Pb were measured in selected surface waters from northwestern Europe. Linear multiple regression predictive models explained 97, 93, and 96% of the observed variation in Cd, Cu and Pb binding capacities, respectively. The models constructed used (CO₂^3?) and (SO₂^2?) to predict Cd binding capacity, (OH^?) and (SO₄^2?) to predict Cu binding capacity and (OH^?), (CO₃^2?) and (SO₄^2?) to predict Pb binding capacity. Organic carbon was not significantly correlated with binding capacities for Cd, Cu, and Pb and was unimportant in explaining a significant amount of the variability in binding capacities for the metals of northern European surface waters. Thus, the effects of these organics on trace metal speciation can be ignored and predictive models of trace metal speciation constructed, using inorganic solubility equilibria only. Ratios of total Cd, Cu, and Pb concentrations to their respective binding capacities were much less than unity for all waters studied. Copper exhibited the greatest metal concentrations: binding capacity ratio in all waters investigated.     

The origin of thermal waters in the northeastern part of the Eger Rift,Czech Republic

An investigation of the thermal waters in the Ústí nad Labem area in the northeastern part of the Eger Rift has been carried out, with the principal objective of determining their origin. Waters from geothermal reservoirs in the aquifers of the Bohemian Cretaceous Basin (BCB) from depths of 240 to 616 m are exploited here. For comparison, thermal waters of the adjacent Teplice Spa area were also incorporated into the study. Results based on water chemistry and isotopes indicate mixing of groundwater from aquifers of the BCB with groundwater derived from underlying crystalline rocks of the Erzgebirge Mts. Unlike thermal waters in Dě?ín, which are of Ca–HCO₃ type, there are two types of thermal waters in Ústí nad Labem, Na–HCO₃–Cl–SO₄ type with high TDS values and Na–Ca–HCO₃–SO₄ type with low TDS values. Carbon isotope data, speciation calculations, and inverse geochemical modeling suggest a significant input of endogenous CO₂ at Ústí nad Labem in the case of high TDS groundwaters. Besides CO₂ input, both silicate dissolution and cation exchange coupled with dissolution of carbonates may explain the origin of high TDS thermal waters equally well. This is a consequence of similar δ¹³C and ¹⁴C values in endogenous CO₂ and carbonates (both sources have ¹⁴C of 0 pmc, endogenous CO₂ δ¹³C around −3‰, carbonates in the range from −5‰ to +3‰ V-PDB). The source of Cl⁻ seems to be relict brine formed in Tertiary lakes, which infiltrated into the deep rift zone and is being flushed out. The difference between high and low TDS groundwaters in Ústí nad Labem is caused by location of the high mineralization groundwater wells in CO₂ emanation centers linked to channel-like conduits. This results in high dissolution rates of minerals and in different δ¹³C(DIC) and ¹⁴C(DIC) fingerprints. A combined δ³⁴S and δ¹⁸O study of dissolved SO₄ indicates multiple SO₄ sources, involving SO₄ from relict brines and oxidation of H₂S. The study clearly demonstrates potential problems encountered at sites with multiple sources of C, where several evolutionary groundwater scenarios are possible.     

Controls on the geochemistry of rare earth elements along a groundwater flow path in the Carrizo Sand aquifer,Texas, USA

Groundwater samples were collected along a groundwater flow path in the Carrizo Sand aquifer in south Texas, USA. Field measurements that included pH, specific conductivity, temperature, dissolved oxygen (DO), oxidation–reduction potentials (Eh in mV), alkalinity, iron speciation, and H₂S concentrations were also conducted on site. The geochemistry (i.e., concentrations, shale-normalized patterns, and speciation) of dissolved rare element elements (REEs) in the Carrizo groundwaters are described as a function of distance along a flow path. Eh and other redox indicators (i.e., DO, Fe speciation, H₂S, U, and Re) indicate that redox conditions change along the flow path in the Carrizo Sand aquifer. Within the region of the aquifer proximal to the recharge zone, groundwaters exhibit both highly oxidizing and localized mildly reducing conditions. However, from roughly 10 km to the discharge zone, groundwaters are reducing and exhibit a progressive decrease in redox conditions. Dissolved REE geochemical behavior exhibits regular variations along the groundwater flow path in the Carrizo Sand aquifer. The changes in REE concentrations, shale-normalized patterns, and speciation indicate that REEs are not conservative tracers. With flow down-gradient, redox conditions, pH and solution composite, and adsorption modify groundwater REE concentrations, fractionation patterns, and speciation.     

Post-depositional redistribution of trace metals in reservoir sediments of a mining/smelting-impacted watershed (the Lot River,SW France)

Mining/smelting wastes and reservoir sediment cores from the Lot River watershed were studied using mineralogical (XRD, SEM–EDS, EMPA) and geochemical (redox dynamics, selective extractions) approaches to characterize the main carrier phases of trace metals. These two approaches permitted determining the role of post-depositional redistribution processes in sediments and their effects on the fate and mobility of trace metals. The mining/smelting wastes showed heterogeneous mineral compositions with highly variable contents of trace metals. The main trace metal-bearing phases include spinels affected by secondary processes, silicates and sulfates. The results indicate a clear change in the chemical partitioning of trace metals between the reservoir sediments upstream and downstream of the mining/smelting activities, with the downstream sediments showing a 2-fold to 5-fold greater contribution of the oxidizable fraction. This increase was ascribed to stronger post-depositional redistribution of trace metals related to intense early diagenetic processes, including dissolution of trace metal-bearing phases and precipitation of authigenic sulfide phases through organic matter (OM) mineralization. This redistribution is due to high inputs (derived from mining/smelting waste weathering) at the water–sediment interface of (i) dissolved SO₄ promoting more efficient OM mineralization, and (ii) highly reactive trace metal-bearing particles. As a result, the main trace metal-bearing phases in the downstream sediments are represented by Zn- and Fe-sulfides, with minor occurrence of detrital zincian spinels, sulfates and Fe-oxyhydroxides. Sequestration of trace metals in sulfides at depth in reservoir sediments does not represent long term sequestration owing to possible resuspension of anoxic sediments by natural (floods) and/or anthropogenic (dredging, dam flush) events that might promote trace metal mobilization through sulfide oxidation. It is estimated that, during a major flood event, about 870 t of Zn, 18 t of Cd, 25 t of Pb and 17 t of Cu could be mobilized from the downstream reservoir sediments along the Lot River by resuspension-induced oxidation of sulfide phases. These amounts are equivalent to 13-fold (Cd), ∼6-fold (Zn), 4-fold (Pb) the mean annual inputs of the respective dissolved trace metals into the Gironde estuary.     

Multivariate statistics and hydrogeochemical modeling for source identification of major elements and heavy metals in the groundwater of Qareh-Ziaeddin plain,NW Iran

The present study aims to evaluate the possible source of major and some minor elements and heavy metals in the groundwater of Qareh-Ziaeddin plain, NW Iran with respect to chemical elements, saturation index, and multivariate statistics including correlation coefficient, cluster analysis, and factor analysis. Groundwater samples were collected in Jun 2016 and measured with respect to EC, pH, major and some minor elements and heavy metals including Fe, Mn, Zn, Cr, Pb, Cd, Al, and As. Among all the measured parameters, some of the samples exceed the World Health Organization (WHO) guideline value for EC, Na, Mg, HCO₃, SO₄, Cl, NO₃, F, As, Zn, and Pb. The results of correlation analysis show that weathering and dissolution of minerals especially evaporites and silicates, water-rock interaction, and cation exchange are dominant occurred processes in the groundwater of the study area. Also, denitrification process is occurred in the groundwater system. Cluster analysis categorizes the samples into three distinct groups which are different based on their EC and dependent variables, e.g., Na, Ca, Cl, SO₄ and pH, Pb, Cd, and As. It can be found that volcanic, evaporite, and clay formations have the least impact on the chemistry of the cluster 1 samples while clay and evaporite formations have the highest impact on the cluster 3 and also calcareous formations on cluster 2. Factor analysis shows that five factors, with total variance of 83%, are effective in the release of heavy metals and groundwater chemistry which are mostly geogenic.     

Evaluation of heavy metal contamination in groundwater samples from Kapas Island,Terengganu, Malaysia

An attempt has been made to delineate the hydrochemistry for a small island based on the major ions and heavy metal concentrations. In this investigation, six sampling campaigns were conducted to measure the concentrations of major ions (Ca, Mg, Na, K, HCO₃, Cl, and SO₄) and heavy metals (Zn, Cr, Pb, Mn, As, and Cu) in groundwater samples collected from seven sampling stations (boreholes) located on Kapas Island, Terengganu, Malaysia. The distribution of major ions is illustrated by a piper plot where Ca–HCO₃ is the dominant type. In addition, the concentrations of heavy metals demonstrate that Mn shows as being the highest concentrated heavy metal in the groundwater sampled in the sampling campaigns; the average Mn content in groundwater sampled was 54.05 μg/L. However, a comparison of the heavy metal (Mn, Cr, Zn, As, Pb, and Cu) concentrations in groundwater samples with the Drinking Water Quality Standard prescribed by World Health Organization reveals that none of these heavy metals exceeded the recommended threshold limits. The principal component analyses (PCA) extracted four components that control the groundwater chemistry. Components 1 and 2 from the PCA analyses extracted approximately 52.11 % of the total variance, which represent the heavy metals (As and Mn) and physical parameters (pH, redox potential, electrical conductivity, temperature, and total dissolved solids). Based on the output of the PHREEQC hydrogeochemical software, several species of heavy metals exist, in which the dominant species found are Mn²⁺, PbCO₃, Cu(OH)₂, and Zn⁺.