Geochemistry of regional aquifer systems hosted by carbonate-evaporite formations in Umbria and southern Tuscany (central Italy)

In central Italy Mesozoic carbonates represent the principal reservoir of freshwater of the region. The hydrogeological setting is linked to the geological evolution of the Apennine chain and is generally characterised by a lower aquifer and one or more shallower aquifers separated by thin aquicludes. In these systems, groundwater composition is the result of a complex array of regional and local geochemical processes. The main geochemical processes are the dissolution of calcite, the influx of deeply derived CO₂ related to a regional process of mantle degassing, dedolomitization and mixing with deep saline fluids. The occurrence of saline fluids, characterised by a Na–Cl(HCO₃) composition, is related to the presence of a deep regional aquifer at the base of Mesozoic carbonates. The extremely high pCO₂ values computed for the saline waters suggest that the deep aquifer is also a structural trap for the mantle derived CO₂ during its ascent towards the surface. In central Italy, geological and geophysical data highlight the presence of two different crustal sectors: the eastern sector, where the geometry of the Apennine thrust belt is still preserved, and the western sector, where the compressive structures are dislocated by important extensional deformations. In the western sector, the normal faults disrupting the compressive structures allow the mixing of the deep Na–Cl(HCO₃) fluids with the shallow groundwater causing a salinity increase and the natural deterioration of groundwater quality.     

Hydrochemical baseline condition of groundwater at the Mizunami underground research laboratory (MIU)

Hydrochemical conditions up to depths of 1000 m below ground level around the Mizunami Underground Research Laboratory were investigated to construct a “baseline condition model” describing the undisturbed hydrochemical environment prior to excavation of the underground facilities at Mizunami, Gifu, Japan. Groundwater chemistry in this area was classified into a Na–Ca–HCO₃ type of groundwater in the upper part of sedimentary rock sequence and a Na–(Ca)–Cl type of groundwater in the deeper part of the sedimentary rock sequence and basement granite. The residence time of the groundwaters was estimated from their ¹⁴C contents to be approximately 9.3 ka in the middle part of the sedimentary rock and older than 50 ka in the deep part of the granite. The evolution processes of these groundwaters were inferred to be water–rock interactions such as weathering of plagioclase, dissolution of marine sulphate/sulphide minerals and carbonate minerals in the Na–Ca–HCO₃ type of groundwater, and mixing between “low-salinity water” in the shallow part and “higher-salinity water” in the deeper part of the granite in the Na–(Ca)–Cl type of groundwater. The source of salinity in the deeper part of the granite was possibly a palaeo-hydrothermal water or a fossil seawater that recharged in the Miocene, subsequently being modified by long-term water–rock interaction. The Cl-depth trend in granitic groundwater changes at a depth of −400 m below sea level. The hydrogeological properties controlling the groundwater flow and/or mixing processes such as advection and diffusion were inferred to be different at this depth in the granite. This hydrochemical conceptual model is indispensable not only when constructing the numerical model for evaluating the hydrochemical disturbance during construction and operation of the MIU facility, but also when confirming a hydrogeological model.     

Geochemical distribution of arsenic,cadmium, lead and zinc in river sediments affected by tailings in Zimapán,a historical polymetalic mining zone of México

High arsenic (As) groundwater is widely distributed in northwestern Hetao Plain, an arid region with sluggish groundwater flow. Observed As concentration in groundwater from wells ranges from 76 to 1,093 μg/l. Most water samples have high total dissolved solids, with Cl and HCO₃ as the dominant anions and Na as the dominant cation. The major hydrochemical types of most saline groundwaters are Na–Mg–Cl–HCO₃ and Na–Mg–Cl. By contrast, fresh groundwaters generally belong to the Na–Mg–HCO₃ type. High concentrations of arsenic in shallow aquifers are associated with strongly reducing conditions, as evidenced by high concentrations of dissolved organic carbon, ammonium, as well as dissolved sulfide and Fe, dominance of arsenite, relatively low concentrations of nitrate and sulfate, and occasionally high content of dissolved methane (CH₄). High As groundwaters from different places at Hetao Plain experienced different redox processes. Fluoride is also present in high As groundwater, ranging between 0.40 and 3.36 mg/l. Although fluorosis poses an additional health problem in the region, it does not correlate well with As in spatial distribution. Geochemical analysis indicates that evapotranspiration is an important process controlling the enrichment of Na and Cl, as well as trace elements such as As, B, and Br in groundwater. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

High arsenic and boron concentrations in groundwaters related to mining activity in the Bigadiç borate deposits (Western Turkey)

This study documents the environmental impacts of borate mines in Bigadiç district, which are the largest colemanite and ulexite deposits in the world. Borate-bearing formations have affected the concentrations of some contaminants in groundwater. Groundwater quality is directly related to the borate zones in the mines as a result of water–rock interaction processes. Calcium is the dominant cation and waters are Ca–SO₄ and HCO₃ type in the mine (Tülü borate mine) from which colemanite is produced. However in the Simav and Acep Borate Mines, ulexite and colemanite minerals are produced and waters from these open pit mines are Na–HCO₃–SO₄ types. High SO₄ concentrations (reaching 519 mg/L) might be explained by the existence of anhydrite, gypsum and celestite minerals in the borate zone. Groundwater from tuff and borate strata showed relatively low pH values (7–8) compared to surface and mine waters (>8). EC values ranged from 270 to 2850 μS/cm. Boron and As were the two important contaminants determined in the groundwaters around the Bigadiç borate mines. Arsenic is the major pollutant and it ranged from 33 to 911 μg/L in the groundwater samples. The concentrations of B in the study area ranged from 0.05 to 391 mg/L. The highest B concentrations were detected at the mine areas. The extension of the borate zones in the aquifer systems is the essential factor in the enrichment of B and As, and some major and trace elements in groundwaters are directly related to the leaching of the host rock which are mainly composed of tuffs and limestones. According to drinking water standards, all of the samples exceed the tolerance limit for As. Copper, Mn, Zn and Li values are enriched but do not exceed the drinking water standards. Sulfate, Al and Fe concentrations are above the drinking water standard for the groundwater samples.     

Integrated hydrochemical assessment of the Quaternary alluvial aquifer of the Guadalquivir River, southern Spain

The alluvial aquifer of the Guadalquivir River comprises shallow Quaternary deposits located in the central-eastern part of the Province of Jaén in southern Spain, where groundwater resources are used mainly for crop irrigation in an important agricultural area. In order to establish the baseline hydrochemical conditions and processes determining the groundwater quality, groundwater and river water samples were collected as part of an integrated investigation that coupled multivariate statistical analysis with hydrochemical methods to identify and interpret the groundwater chemistry of the aquifer system. Three main hydrochemical types (Mg–Ca–HCO₃, Ca–Mg–SO₄–HCO₃–Cl and Na–Ca–Mg–Cl–SO₄) were identified. Further interpretation, using R-mode principal components analysis (PCA) conducted with 13 hydrochemical variables, identified two principal components which explain ⅔ of the variance in the original data. In combination with the hydrochemical interpretation, mineralogical analyses of the aquifer sediment together with inverse geochemical modelling using NETPATH showed that dedolomitization (calcite precipitation and dolomite dissolution driven by gypsum dissolution) is the principal hydrochemical process controlling the regional groundwater chemistry. Other processes such as silicate weathering, ion exchange, mixing between river water and groundwater, and agricultural practices also affect the groundwater chemistry.     

Hydrochemistry and isotope compositions of groundwater from the Shihongtan sandstone-hosted uranium deposit, Xinjiang, NW China

Groundwaters and surface water in the Shihongtan sandstone-hosted U ore district, Xinjiang, NW China, were sampled and analyzed for their major-, and trace element concentrations and oxygen, hydrogen, boron and strontium isotope compositions in order to assess the possible origins of the waters and water–rock interactions that occurred in the deep aquifer system. The waters in the study district have been grouped into three hydrochemical facies: Facies 1, potable spring-water, is a pH neutral (7.0), Na–Ca–HCO₃ type water with low total dissolved solids (TDS; 0.2 g/l, fresh) and has δ¹⁸O of − 8.3‰, δD of − 48.2‰,δ¹¹B of 1.5‰, and ⁸⁷Sr/⁸⁶Sr of 0.70627. Facies 2 groundwaters are mildly acidic to mildly alkaline (pH of 6.5–8.0, mean 7.3), Na–Ca–Mg–Cl–SO₄ type waters with moderate TDS (8.2 g/l–17.2 g/l, mean 9.3 g/l, brackish) and haveδ¹⁸O values in the − 5.8‰ to − 9.3‰ range (mean − 8.1‰), δD values in the − 20.8‰ to − 85.5‰ range (mean − 47.0‰),δ¹¹B values in the + 9.5‰ to + 39.1‰ range (mean + 17.1‰), and ⁸⁷Sr/⁸⁶Sr values in the 0.70595 to 0.70975 range (mean 0.70826). Facies 3, Aiting Lake water, is a mildly alkaline (pH = 7.4), Na–Ca–Mg–Cl–SO₄ type water with the highest TDS (249.1 g/l, brine) and has δ¹⁸O of − 2.8‰, δD of − 45.8‰,δ¹¹B of 21.2‰, and ⁸⁷Sr/⁸⁶Sr of 0.70840. The waters from the study district show a systematic increase in major, trace element and TDS concentrations and δ¹¹B values along the pathway of groundwater migration which can only be interpreted in terms of water–rock interaction at depth and strong surface evaporation. The hydrochemical and isotopic data presented here confirm that the groundwaters in the Shihongtan ore district are the combined result of migration, water–rock interaction and mixing of meteoric water with connate waters contained in sediments.     

The chemistry of bottled mineral and spring waters from Norway,Sweden, Finland and Iceland

Twenty-two bottled mineral and spring waters from Norway, Sweden, Finland and Iceland have been analysed for 71 inorganic chemical parameters with low detection limits as a subset of a large European survey of bottled groundwater chemistry (N = 884). The Nordic bottled groundwaters comprise mainly Ca–Na–HCO₃–Cl water types, but more distinct Ca–HCO₃, Na HCO₃ and Na–Cl water types are also offered. The distributions for most elements fall between groundwater from Fennoscandian Quaternary unconsolidated aquifers and groundwater from Norwegian crystalline bedrock boreholes. Treated tap waters have slightly lower median values for many parameters, but elements associated with plumbing have significantly higher concentrations in tap waters than in bottled waters. The small dataset is able to show that excessive fluoride and uranium contents are potential drinking water problems in Fennoscandia. Nitrate and arsenic displayed low to moderate concentrations, but the number of samples from Finland and Northern Sweden was too low to detect that elevated concentrations of arsenic occur in bedrock boreholes in some regions. The data shows clearly that water sold in plastic bottles is contaminated with antimony. Antimony is toxic and suspected to be carcinogenic, but the levels are well below the EU drinking water limit. The study does not provide any health-based arguments for buying bottled mineral and spring waters for those who are served with drinking water from public waterworks. Drinking water from crystalline bedrock aquifers should be analysed. In case of elevated concentrations of fluoride, uranium or arsenic, most bottled waters, but not all, will be better alternatives when treatment of the well water is not practicable.     

Chemistry and sulfur isotope investigation of industrial wastewater contamination into groundwater aquifers, Piteå County, N. Sweden

The possible contamination of a groundwater system with industrial wastewater originating from a paper mill factory has been investigated in Piteå, N. Sweden. Six samples were collected from the wastewater in the waste dump and twelve samples from the adjacent groundwater were analyzed for chemistry and sulfur isotopes. The industrial wastewater is a saline water consisting mainly of Na–HCO₃–SO₄, having a high pH and showing δ³⁴S values between 7‰ and 9‰ affected by bacterial sulfate reduction. The groundwaters are relatively dilute, dominated by Na⁺, Ca²⁺ and HCO₃⁻, but with varying concentrations as exemplified by sulfate with concentrations varying between 3 and 69 mg L^− 1 while the δ³⁴S values range from − 0.5‰ to 14.3‰. The data suggest that the main S sources in the waters are the bedrock sulfides and/or atmospheric deposition, which, sometimes, are overlapped by bacterial sulfate reduction. Contamination from the waste dump does not occur.     

Major and trace element geochemistry in upper Ganga river in the Himalayas, India

Chemical weathering and resulting water compositions in the upper Ganga river in the Himalayas were studied. For the first time, temporal and spatial sampling for a 1 year period (monthly intervals) was carried out and analyzed for dissolved major elements, trace elements, Rare Earth Elements (REE), and strontium isotopic compositions. Amounts of physical and chemical loads show large seasonal variations and the overall physical load dominates over chemical load by a factor of more than three. The dominant physical weathering is also reflected in high quartz and illite/mica contents in suspended sediments. Large seasonal variations also occur in major elemental concentrations. The water type is categorized as HCO₃^––SO₄^2––Ca²⁺ dominant, which constitute >60% of the total water composition. On an average, only about 5–12% of HCO₃^– is derived from silicate lithology, indicating the predominance of carbonate lithology in water chemistry in the head waters of the Ganga river. More than 80% Na⁺ and K⁺ are derived from silicate lithology. The silicate lithology is responsible for the release of low Sr with extremely radiogenic Sr (⁸⁷Sr/⁸⁶ Sr>0.75) in Bhagirathi at Devprayag. However, there is evidence for other end-member lithologies for Sr other than carbonate and silicate lithology. Trace elements concentrations do not indicate any pollution, although presence of arsenic could be a cause for concern. High uranium mobilization from silicate rocks is also observed. The REE is much less compared to other major world rivers such as the Amazon, perhaps because in the present study, only samples filtered through <0.2 m were analysed. Negative Eu anomalies in suspended sediments is due to the excess carbonate rock weathering in the source area.     

Hydrochemical appraisal of groundwater and its suitability in the intensive agricultural area of Muzaffarnagar district,Uttar Pradesh,India

Muzaffarnagar is an economically rich district situated in the most fertile plains of two great rivers Ganga and Yamuna in the Indo-gangetic plains, with agricultural land irrigated by both surface water as well as groundwater. An investigation has been carried out to understand the hydrochemistry of the groundwater and its suitability for irrigation uses. Groundwater in the study area is neutral to moderately alkaline in nature. Chemistry of groundwater suggests that alkaline earths (Ca + Mg) significantly exceed the alkalis (Na + K) and weak acids exceed the strong acids (Cl + SO₄), suggesting the dominance of carbonate weathering followed by silicate weathering. Majority of the groundwater samples (62%) posses Ca–Mg–HCO₃ type of hydrochemical species, followed by Ca–Na–Mg–HCO₃, Na–Ca–Mg–HCO₃, Ca–Mg–Na–HCO₃–Cl and Na–Ca–HCO₃–SO₄ types. A positive high correlation (r ² = 0.928) between Na and Cl suggests that the salinity of groundwater is due to intermixing of two or more groundwater bodies with different hydrochemical compositions. Barring a few locations, most of the groundwater samples are suitable for irrigation uses. Chemical fertilizers, sugar factories and anthropogenic activities are contributing to the sulphate and chloride concentrations in the groundwater of the study area. Overexploitation of aquifers induced multi componential mixing of groundwater with agricultural return flow waters is responsible for generating groundwater of various compositions in its lateral extent.     

Groundwater chemistry within a plateau neighboring Matsumoto city,Japan

The change in groundwater chemistry along the groundwater flow path in the Matsumoto tunnel vicinity was studied, and the origin of the groundwater and dissoluted substances was determined. The relationship between the concentration of HCO₃ ^–, Ca²⁺, and Na⁺, and CO₂ gas pressure in the groundwater indicated that the HCO₃ ^–, Ca²⁺, and Na⁺ were produced by the reaction of the CO₂ gas in the groundwater and feldspar in the rocks. The relationship between the concentration of NO₃ ^– and the Eh and pH values in the groundwater indicated that in an oxidative condition, ammonia-oxidizing and nitriteoxidizing bacteria used NH₄ ⁺ and produced NO₃ ^– and H⁺, and in a reductive condition, denitrifying bacteria used NO₃ ^– and produced N₂ gas and OH^–. The stable hydrogen and oxygen isotopic ratio in the groundwater and precipitation indicated that the groundwater originated from precipitation that had fallen on the area. The concentration of³H and the stable hydrogen and oxygen isotopic ratios in the groundwater suggested that it has been getting warmer climatically for more than 60 years. The stable carbon isotopic ratio indicated that the HCO₃ ^– in the groundwater, excluding deep well water, originated from CO₂ gas produced by organic matter in the soil. The deep well water, which had a higher concentration of HCO₃ ^– than the other groundwater sampled, was thought to have acquired HCO₃ ^– though contact with rocks. The³⁶Cl/Cl ratio indicated the recharge age of the deep well water sampled at a depth of 760 m at the foot of the plateau was recent.     

Geochemistry and stable isotopic composition of tufa waters and precipitates from the Interlake Region, Manitoba, Canada: Constraints on groundwater origin, calcitization, and tufa formation

New major, trace and isotopic geochemical results from a regional study of springs discharging from the major carbonate rock aquifer in the Interlake Region of Manitoba, Canada, are used to understand water–rock reactions, timing of recharge/discharge, tufa formation processes, and as baseline data. Spring waters are fresh with total dissolved solids (TDS) concentrations ranging from 150 to 880 mg/L. Waters discharging in the northern part of the study area have lower TDS, are dominantly Ca–Mg–HCO₃ waters with low SO₄ concentrations (<< 50 mg/L), and appear to have interacted primarily with Silurian carbonate lithologies. In contrast, waters in the southeastern part of the study area have higher TDS and have elevated SO₄ concentrations (up to 210 mg/L). Spring waters have elevated Mg/Ca_molar (1.23 ± 0.23), typically greater than congruent dissolution of dolomite. Ca and Mg concentrations and Mg/Ca_molar indicate that groundwater residence times were sufficient to allow equilibration with bedrock dolomite lithologies; elevated tritium in northern waters indicates a significant recharge component in the 1960's and 1970's. Tufa precipitates that have formed from many of the spring waters are low-Mg calcite (MgO = 1.70 to 5.80 wt.%). Sr concentrations are variable (57 to 657 ppm) and tufa Sr/Ca_molar ratios appear to be entirely controlled by spring water Sr/Ca_molar. Empirically determined Sr distribution coefficients (D_Sr = 0.389 ± 0.083) indicate rapid crystallization following CO₂ degassing, consistent with heavier δ¹³C_VPDB compared to spring waters. Sulfate concentrations are generally too low for calcitization (dedolomitization) reactions driven by anhydrite dissolution to be the dominant control on the elevated groundwater Mg/Ca_molar, implying either extensive sulfate reduction along the flow paths (however, δ¹³C_DIC suggests the elevated SO₄ is more consistent with Fe-sulfide oxidation), or that other processes are involved. Major ion ratios suggest that the waters in the southern part of the study area are more consistent with interaction with siliciclastic rocks than with anhydrite dissolution. We suggest that calcitization (dedolomitization) reactions driven by anhydrite dissolution may not dominate all carbonate aquifers and that mixing of waters in karst conduits combined with ion exchange reactions are important controls on water chemistry in these systems.     

The role of “excess” CO2 in the formation of trona deposits

The prevailing theory for the formation of trona [Na₃(CO₃)(HCO₃) · 2(H₂O)] relies on evaporative concentration of water produced by silicate hydrolysis of volcanic rock or volcaniclastic sediments. Given the abundance of closed drainage basins dominated by volcanics, it is puzzling that there are so few trona deposits and present-day lakes that would yield dominantly Na–CO₃ minerals upon evaporation. Groundwater in the San Bernardino Basin (southeastern Arizona, USA and northeastern Sonora, Mexico) would yield mainly Na–CO₃ minerals upon evaporation, but waters in the surrounding basins would not. Analysis of the chemical evolution of this groundwater shows that the critical difference from the surrounding basins is not lithology, but the injection of magmatic CO₂. Many major deposits of trona and Na–CO₃-type lakes appear to have had “excess” CO₂ input, either from magmatic sources or from the decay of organic matter. It is proposed that, along with the presence of volcanics, addition of “excess” CO₂ is an important pre-condition for the formation of trona deposits.     

Is groundwater in the Tarkwa gold mining district of Ghana potable?

Hand-pump wells in the Tarkwa gold mining district and the geologically similar Bui area were chemically analysed and compared in an effort to determine whether groundwaters in the Tarkwa area have been affected by mining. Significant chemical differences attributed to mine water discharges have been observed in streams in the Tarkwa area. Groundwater chemistry from hand-pump wells in Tarkwa and Bui areas reveal similar hydrochemical facies, predominantly Ca–Na–Mg–HCO₃–Cl. However, except for SO₄^2–, ionic concentrations of groundwaters from Bui are greater than those from Tarkwa probably due to differences in (1) water availability during sedimentation (2) water-rock interactions and/or residence times for water. No demonstrable impact of mining on groundwaters from hand-pumped wells in the Tarkwa area has been noted. Hydrogeological inference suggests that the main streams which receive mine water discharges are both gaining and are groundwater divides. The overwhelming majority of population centres and mining operations are located on opposite sides of these groundwater divides, therefore, it is unlikely aquifers tapped for drinking by these communities would be affected by mining.     

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.     

Rare earth elements and yttrium geochemistry of dolomite from post-Variscan vein-type mineralization of the Nízký Jeseník and Upper Silesian Basins, Czech Republic

Rare earth elements and yttrium geochemistry of dolomite from post-Variscan vein-type Zn–Pb–Cu mineralization was studied in the Nízký Jeseník and Upper Silesian Basins. Combined with crush–leach analyses of fluid inclusions, the study provided important information on fluid–rock interaction, physico-chemical and redox conditions during crystallization of the dolomite. The mineralization is hosted by Carboniferous siliciclastic rocks, representing Variscan flysch and molasse sedimentation. Dolomite samples contain highly variable contents of REE (between 18 and 295 ppm) and Y (between 17 and 95 ppm). REY patterns are divided into four different groups which differ in regional provenance, LREE vs. HREE enrichment/depletion and significance of Eu, Gd and Y anomalies. These patterns can be the result of 1) precipitation of dolomite from near neutral fluids with important concentrations of complexing ligands as a main factor for the REY partitioning, 2) interaction of migrating fluids with host or basement rocks, or, most probably, 3) a combination of both.Regarding the importance of complexing ligands, it is proposed that in all samples fluoride and chloride complexes prevailed over sulphate, bicarbonate and hydroxide complexes. Interaction of fluids with rocks was strongly affected by the fluid temperature. Dolomites which precipitated from fluids with homogenization temperature higher than 110 °C are mostly REY-enriched while fluids colder than 110 °C produced REY-depleted dolomite. The REY-enrichment may indicate higher effectiveness of leaching of REE-bearing minerals (probably monazite, allanite and biotite) at higher temperatures. The preferential loss of LREE can be caused by the recrystallization or remobilization of dolomite. Generally, an increase in salinity and contents of Cl and F in the fluids is mostly accompanied by a higher REY content in dolomite. Positive Eu anomalies and small negative Gd and Y anomalies are typical for most of the chondrite-normalized patterns. Positive Eu_CN anomalies in dolomites are most probably the result of an increase of Eh in the parent fluid. Distribution of Y is expected to be predominantly controlled by solution complexation.     

A study on the hydrogeology and hydrogeochemistry of groundwater from different depths in a coastal aquifer: Annamalai Nagar,Tamilnadu, India

Chemical characterization of groundwater is essential to bring out its nature and utility. Samples from shallow and deep ground water of the same location were collected and studied for their geochemical characteristics following standard procedures (APHA 1998). Sediment samples from different depths were collected and analysed for minerals using FTIR and SEM. Resisitivity logging was carried out in the bore well to understand the variations in depth to fresh water potential. The shallow ground water is dominated by Na–Cl–HCO₃–SO₄ and deeper groundwater by Na–HCO₃–SO₄–Cl types. It is observed that there is a significant ionic variation with depth. The ionic strength of the deeper samples is lesser than in the shallower samples. Wide pH variations in the shallow water samples are due to ion exchange process. Thermodynamic stability plot was used to identify the state of stability. It is inferred that there is no major significant difference in the thermodynamic state of stability in the shallow and the deeper aquifers as the aquifer matrix for the shallow and deeper aquifers are almost similar. Saturation index of Gibbsite, Kaolinite, Calcite, Dolomite and anhydrite, were studied for shallow and deep aquifers, to identify the difference in hydro chemical signatures. The Si/Al ratios of shallow samples are less when compared with the deeper samples. Leaching of secondary salts was the chief mechanism controlling the ground water chemistry of the region.     

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO₃ (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca–HCO₃ spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (³H), helium-3 (³He_trit), sulfur hexafluoride (SF₆)—for four Ca–HCO₃ spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.The online version of the original article can be found at     

Mineralogy and geochemistry of boehmite-rich coals: New insights from the Haerwusu Surface Mine, Jungar Coalfield, Inner Mongolia, China

Boehmite-rich coal of Pennsylvanian age was discovered earlier at the Heidaigou Surface Mine, Jungar Coalfield, Inner Mongolia, China. This paper reports new results on 29 bench samples of the no. 6 coal from a drill core from the adjacent Haerwusu Surface Mine, and provides new insights into the origin of the minerals and elements present. The results show that the proportion of inertinite in the no. 6 coal is higher than in other Late Paleozoic coals in northern China. Based on mineral proportions (boehmite to kaolinite ratio) and major element concentrations in the coal benches of the drill core, the no. 6 coal may be divided into five sections (I to V). Major minerals in Sections I and V are kaolinite. Sections II and IV are mainly kaolinite with a trace of boehmite, and Section III is high in boehmite. The boehmite is derived from bauxite in the weathered surface (Benxi Formation) in the sediment-source region. The no. 6 coal is rich in Al₂O₃ (8.89%), TiO₂ (0.47%), Li (116 μg/g), F (286 μg/g), Ga (18 μg/g), Se (6.1 μg/g), Sr (350 μg/g), Zr (268 μg/g), REEs (172 μg/g), Pb (30 μg/g), and Th (17 μg/g). The elements are classified into five associations by cluster analysis, i.e. Groups A, B, C, D, and E. Group A (ash–SiO₂–Al₂O₃–Na₂O–Li) and Group B (REE–Sc–In–Y–K₂O–Rb–Zr–Hf–Cs–U–P₂O₅–Sr–Ba–Ge) are strongly correlated with ash yield and mainly have an inorganic affinity. The elements that are negatively or less strongly correlated with ash yield (with exceptions of Fe₂O₃, Be, V, and Ni) are grouped in the remaining three associations: Group C, Se–Pb–Hg–Th–TiO₂–Bi–Nb–Ta–Cd–Sn; Group D, Co–Mo–Tl–Be–Ni–Sb–MgO–Re–Ga–W–Zn–V–Cr–F–Cu; and Group E, S–As–CaO–MnO–Fe₂O₃. Aluminum is mainly distributed in boehmite, followed by kaolinite. The high correlation coefficients of the Li–ash, Li–Al₂O₃, and Li–SiO₂ pairs indicate that Li is related to the aluminosilicates in the coal. The boehmite-rich coal is high in gallium and F, which occur in boehmite and the organic matter. Selenium and Pb are mainly in epigenetic clausthalite fillings in fractures. The abundant rare earth elements in the coal benches were supplied from two sources: the bauxite on the weathered surface of the Benxi Formation and from adjacent partings by groundwater leaching during diagenesis. The light rare earth elements (LREEs) are more easily leached from the partings and incorporated into the organic matter than the heavy REEs, leading to a higher ratio of LREEs to HREEs in the coal benches than in the overlying partings.