Fluoride hydrogeochemistry and bioavailability in groundwater and soil of an endemic fluorosis belt,central Iran

Presence of fluoride in groundwater is a public health problem in the so-called endemic fluorosis belt of the central Iran, where the groundwater is the major source of drinking water in most urban and rural areas. Therefore, an attempt has been made to determine the hydrogeochemical factors controlling fluoride enrichment in the groundwater resources at this belt. Fluoride concentrations ranged from 0.20 to 1.99 mg/L (1.02 ± 0.47) in groundwater samples. The presence of different F-bearing minerals and also clay minerals in the soils and aquifer materials was confirmed using XRD analysis. To identify probable sources of dissolved F^? and investigate groundwater quality, multivariate statistical analyses were carried out. Geochemical modeling indicated that all samples were undersaturated with respect to fluorite, halite, gypsum and anhydrite and mostly oversaturated with respect to calcite and dolomite. Contrary to most high-fluoride regions in the World, the high F^? content was dominated by Na–Cl- and Ca–SO₄-type groundwater in the study area. Besides, fluoride showed negative relationship with pH and HCO₃ ^? in groundwater. In order to assess the bioavailability of fluoride in soils, a two-step chemical fractionation method was applied. The results showed that fluoride in soils mostly accompanied with the residual and water-soluble fractions and was poorly associated with soil’s bonding sites. Calculated aqueous migration coefficient demonstrated that fluoride in the studied soils was mobile to easily leachable to the groundwater. Finally, the results demonstrated that combination of water–rock interaction and influence of clay minerals is geochemical mechanism responsible for controlling fluoride enrichment in groundwater.     

Controlling factors of fluoride in groundwater in a part of South India

Fluoride (F^?) is the most important element for human health. Hydrogeochemical survey was conducted to probe into the controlling factors of F^? in the groundwater of a semi-arid part of South India. The study area comprises of F^?-bearing minerals (hornblende, biotite, and apatite) in the Precambrian rocks, sandstones in the Upper Gondwana rocks, and clays in the Quaternary formations. Forty-seven percent of the total groundwater samples have the higher F^? content than its permissible limit of 1.50 mg/L prescribed for drinking purpose. The chemical data of the groundwater is analyzed to assess the geochemical processes dominating the F^?-bearing groundwater, using Piper and Gibbs diagrams, correlations, saturation indices, ionic ratios, and multivariate analysis. Piper diagram shows that the groundwater quality is characterized by Na⁺-HCO\( {}_3^{-} \) and Na⁺-Cl^?types, while the Gibbs diagrams suggest that the groundwater chemistry is mainly controlled by water-rock interactions and is subsequently modified by human activities. The F^? groundwater is positively correlated with pH, total dissolved solids, Mg²⁺, Na⁺, K⁺, HCO\( {}_3^{-} \), Cl^?, SO\( {}_4^{2-} \), and NO\( {}_3^{-} \) and negatively with Ca²⁺, representing the influences of geogenic and anthropogenic origins on the groundwater system. Geochemical ratios and saturation indices indicate that the processes of mineral dissolution, ion exchange, and evaporation mainly govern the high F^? groundwater, while the chemical fertilizers cause for the enrichment of F^?in the groundwater. Cluster and principal component analyses further support the above findings.     

Geochemical evaluation of nitrate and fluoride contamination in varied hydrogeological environs of Prakasam district,southern India

Hydrogeochemical controlling factors for high rate of groundwater contamination in stressed aquifer of fractured, consolidated rocks belonging to semi-arid watershed are examined. The groundwater in mid-eastern part of Prakasam district confining to Musi-Gundlakamma sub-basins is heavily contaminated with nitrate and fluoride. Distinct water chemistry is noticed among each group of samples segregated based on concentration of these contaminants. The nitrate is as high as 594 mg/l and 57 % of the samples have it in toxic level as per BIS drinking water standards, so also the fluoride which has reached a maximum of 8.96 mq/l and 43 % of samples are not fit for human consumption. Nitrate contamination is high in shallow aquifers and granitic terrains, whereas fluoride is in excess concentration in deeper zones and meta-sediments among the tested wells, and 25 % of samples suffer from both NO₃ ^? and F^? contamination. Na⁺ among cations and HCO₃ ^? among anions are the dominant species followed by Mg²⁺ and Cl^?. The NO₃ ^?-rich groundwater is of Ca²⁺–Mg²⁺–HCO₃ ^?, Ca²⁺–Mg²⁺–Cl^? and Na⁺–HCO₃ ^? type. The F^?-rich groundwater is dominantly of Na⁺–HCO₃ ^? type and few are of Na⁺–SO₄ ^2? type, whereas the safe waters (without any contaminants) are of Ca²⁺–Mg²⁺–HCO₃ ^?– and Na⁺–HCO₃ ^? types. High molecular percentage of Na⁺, Cl^?, SO₄ ^2? and K^? in NO₃ ^? rich groundwater indicates simultaneous contribution of many elements through domestic sewerage and agriculture activity. It is further confirmed by analogous ratios of commonly associated ions viz NO₃ ^?:Cl^?:SO₄ ^2? and NO₃ ^?:K⁺:Cl^? which are 22:56:22 and 42:10:48, respectively. The F^? rich groundwater is unique by having higher content of Na⁺ (183 %) and HCO₃ ^? (28 %) than safe waters. The K⁺:F^?:Ca²⁺ ratio of 10:5:85 and K⁺:F^?: SO₄ ^2? of 16:7:77 support lithological origin of F^? facilitated by precipitation of CaCO₃ which removes Ca²⁺ from solution. The high concentrations of Na⁺, CO₃ ^? and HCO₃ ^? in these waters act as catalyst allowing more fluorite to dissolve into the groundwater. The indices, ratios and scatter plots indicate that the NO₃ ^? rich groundwater has evolved through silicate weathering-anthropogenic activity-evapotranspiration processes, whereas F^? rich groundwater attained its unique chemistry from mineral dissolution-water–rock interaction-ion exchange. Both the waters are subjected to external infusion of certain elements such as Na⁺, Cl^?, NO₃ ^? which are further aggravated by evaporation processes leading to heavy accumulation of contaminants by raising the water density. Presence of NO₃ ^? rich samples within F^? rich groundwater Group and vice versa authenticates the proposed evolution processes.     

Geochemical characteristics and controlling factors of chemical composition of groundwater in a part of Guntur district,Andhra Pradesh,India

A survey on quality of groundwater was carried out for assessing the geochemical characteristics and controlling factors of chemical composition of groundwater in a part of Guntur district, Andhra Pradesh, India, where the area is underlain by Peninsular Gneissic Complex. The results of the groundwater chemistry show a variation in pH, EC, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, Cl^?, SO₄ ^2?, NO₃ ^? and F^?. The chemical composition of groundwater is mainly characterized by Na⁺?HCO₃ ^? facies. Hydrogeochemical type transits from Na⁺–Cl^?–HCO₃ ^? to Na⁺–HCO₃ ^?–Cl^? along the flow path. Graphical and binary diagrams, correlation coefficients and saturation indices clearly explain that the chemical composition of groundwater is mainly controlled by geogenic processes (rock weathering, mineral dissolution, ion exchange and evaporation) and anthropogenic sources (irrigation return flow, wastewater, agrochemicals and constructional activities). The principal component (PC) analysis transforms the chemical variables into four PCs, which account for 87% of the total variance of the groundwater chemistry. The PC I has high positive loadings of pH, HCO₃ ^?, NO₃ ^?, K⁺, Mg²⁺ and F^?, attributing to mineral weathering and dissolution, and agrochemicals (nitrogen, phosphate and potash fertilizers). The PC II loadings are highly positive for Na⁺, TDS, Cl^? and F^?, representing the rock weathering, mineral dissolution, ion exchange, evaporation, irrigation return flow and phosphate fertilizers. The PC III shows high loading of Ca²⁺, which is caused by mineral weathering and dissolution, and constructional activities. The PC IV has high positive loading of Mg²⁺ and SO₄ ^2?, measuring the mineral weathering and dissolution, and soil amendments. The spatial distribution of PC scores explains that the geogenic processes are the primary contributors and man-made activities are the secondary factors responsible for modifications of groundwater chemistry. Further, geochemical modeling of groundwater also clearly confirms the water–rock interactions with respect to the phases of calcite, dolomite, fluorite, halite, gypsum, K-feldspar, albite and CO₂, which are the prime factors controlling the chemistry of groundwater, while the rate of reaction and intensity are influenced by climate and anthropogenic activities. The study helps as baseline information to assess the sources of factors controlling the chemical composition of groundwater and also in enhancing the groundwater quality management.     

Compositional Variation of Hydrothermally Altered Volcanic Rocks in Hishikari Gold Epithermal System: A Useful Geochemical Indicator of Gold–Silver Epithermal Mineralization

The hydrothermally altered andesite hosting the Hishikari gold-silver vein deposits in southern Kyushu, Japan, is analyzed with respect to the spatial variation in chemical composition. The (CaO + Na₂O) content is found to be inversely correlated with the K₂O content as it progresses away from the site of mineralization. It was found that analytical data plotted on a (CaO + Na₂O) − K₂O diagram cannot be explained only by addition of K⁺ from the hydrothermal solution to the original rock and release of Ca²⁺ and Na⁺ from the original rock (K- alteration). Addition of Ca²⁺ and Na⁺ from the hydrothermal solution to the rock and release of K⁺ from the rock but release of K⁺, Ca²⁺, and Na⁺ to the hydrothermal solution (advanced argillic alteration) is important for causing the wide variations in K₂O, CaO, and Na₂O contents on the (CaO + Na₂O) − K₂O diagram. These variations can be explained by superimposed potassic, advanced argillic and calcium alterations. The altered rocks in the Honko-Sanjin area, Yamada area, and Masaki area analyzed by this study are characterized by their intermediate K₂O content and variable CaO content, high K₂O content and low CaO content, and low K₂O content and low CaO content, respectively. The K₂O, Na₂O and CaO contents and oxygen isotopic composition of altered andesite, in conjunction with the solubility of gold as a thio complex, suggest that both gold deposition and the observed compositional variation of altered andesite are the result of mixing between acidic groundwater and neutral gold-bearing hydrothermal solution. The present results indicate that the compositional variation of hydrothermally altered rocks may represent a useful geochemical indicator of epithermal gold–silver mineralization.     

Mechanism of fluoride enrichment in groundwater of hard rock aquifers in Medak,Telangana State,South India

A total of 194 groundwater samples were collected from wells in hard rock aquifers of the Medak district, South India, to assess the distribution of fluoride in groundwater and to determine whether this chemical constituent was likely to be causing adverse health effects on groundwater user in the region. The study revealed that the fluoride concentration in groundwater ranged between 0.2 and 7.4 mg/L with an average concentration of 2.7 mg/L. About 57% of groundwater tested has fluoride concentrations more than the maximum permissible limit of 1.5 mg/L. The highest concentrations of fluoride were measured in groundwater in the north-eastern part of the Medak region especially in the Siddipeta, Chinnakodur, Nanganoor and Dubhaka regions. The areas are underlain by granites which contain fluoride-bearing minerals like apatite and biotite. Due to water–rock interactions, the fluoride has become enriched in groundwater due to the weathering and leaching of fluoride-bearing minerals. The pH and bicarbonate concentrations of the groundwater are varied from 6.6 to 8.8 and 18 to 527 mg/L, respectively. High fluoride concentration in the groundwater of the study area is observed when pH and the bicarbonate concentration are high. Data plotted in Gibbs diagram show that all groundwater samples fall under rock weathering dominance group with a trend towards the evaporation dominance category. An assessment of the chemical composition of groundwater reveals that most of the groundwater samples have compositions of Ca²⁺–Mg²⁺–Cl^? > Ca²⁺–Na⁺–HCO₃ ^? > Ca²⁺–HCO₃ ^? > Na⁺–HCO₃ ^?. This suggests that the characteristics of the groundwater flow regime, long residence time and the extent of groundwater interaction with rocks are the major factors that influence the concentration of fluoride. It is advised not to utilize the groundwater for drinking purpose in the areas delineated, and they should depend on alternate safe source.     

Groundwater solute chemistry,hydrogeochemical processes and fluoride contamination in phreatic aquifer of Odisha,India

The work investigates the major solute chemistry of groundwater and fluoride enrichment(F~-) in the shallow phreatic aquifer of Odisha.The study also interprets the hydrogeochemical processes of solute acquisition and the genetic behavior of groundwater F~-contamination.A total of 1105 groundwater samples collected from across the state from different hydro-geomorphic settings have been analyzed for the major solutes and F~-content.Groundwater is alkaline in nature(range of pH: 6.6–8.7; ave.: 7.9) predominated by moderately hard to very hard types.Average cation and anion chemistry stand in the orders of Ca~(2+) Na~+ Mg~(2+) K~+and HCO_3~- Cl~- SO_4~(2-) CO_3~(2-)respectively.The average mineralization is low(319 mg/L).The primary water types are Ca-Mg-HCO_3 and Ca-Mg-Cl~-HCO_3, followed by Na-Cl, Ca-Mg-Cl, and Na-Ca-Mg-HCO_3~-Cl.Silicate-halite dissolution and reverse ion exchange are the significant processes of solute acquisition.Both the geogenic as well as the anthropogenic sources contribute to the groundwater fluoride contamination,etc.The ratio of Na~+/Ca~(2+) 1.0 comprises Na-HCO_3(Cl) water types with F~- 1.0 mg/L(range 1.0–3.5 mg/L)where the F~-bears geogenic source.Positive relations exist between F~-and pH, Na~+, TDS, and HCO_3~-.It also reflects a perfect Na-TDS correlation(0.85).The ratio of Na~+/Ca~(2+) 1.0 segregates the sample population(F~- range: 1.0–4.0 mg/L) with the F derived from anthropogenic sources.Such water types include Ca-Mg-HCO_3(Cl) varieties which are recently recharged meteoritic water types.The F~-levels exhibit poor and negative correlations with the solutes in groundwater.The Na-TDS relation remains poor(0.12).In contrast, the TDS levels show strong correlations with Ca~(2+)(0.91), Mg~(2+)(0.80) and even Cl~-(0.91).The majority of the monitoring points with the anthropogenic sources of groundwater F~-are clustered in the Hirakud Canal Command area in the western parts of the state, indicating the role of irrigation return flow in the F~-contamination.     

Investigation of the hydrogeochemical processes in an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa

An investigation was conducted to assess the hydrogeochemical processes of an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa. The investigation was aimed at identifying and describing the groundwater chemistry evolution and its contribution to the overall groundwater quality. X-ray fluorescent spectrometry (XRF) and X-ray diffractometry (XRD) analyses were performed on geological samples to identify and quantify the major element oxides and minerals. The study utilises the conventional Piper diagram, bivariate plots and PHREEQC hydrogeochemical model to analyse groundwater chemistry data obtained during the wet (February and May) and dry seasons (August and December) of 2011. The XRF and XRD results show that the channel deposits are dominated by SiO₂ element oxides and quartz minerals, thus elevated concentrations of silicon (Si⁴⁺) were found in the groundwater. Dolomite and calcite minerals were also detected in the unconsolidated aquifer sediments. The detailed study of the alluvial aquifer system has shown that dissolution of dolomite and calcite minerals and ion exchange are the dominant hydrogeochemical processes influencing the groundwater quality. The groundwater evolves from Ca²⁺–Mg²⁺–HCO₃ ^? recharge water that goes through ion exchange with Na⁺ in the clay-silt sediment to give a Na⁺–HCO₃ ^? water type. The groundwater is supersaturated with respect to quartz, dolomite and calcite minerals. The study shows the potential usefulness of simple bivariate plots as a complimentary tool to the conventional methods for analyzing groundwater hydrogeochemical processes.     

Hydrochemistry of groundwater (GW) and surface water (SW) for assessment of fluoride in Chinnaeru river basin,Nalgonda district, (AP) India

Hydrochemical studies were conducted in Chinnaeru river basin of Nalgonda district, Andhra Pradesh, India, to explore the causes of high fluorides in groundwater and surface water causing a widespread incidence of fluorosis in local population. The concentration of fluoride in groundwater ranges from 0.4 to 2.9 and 0.6 to 3.6 mg/l, stream water ranges from 0.9 to 3.5 and 1.4 to 3.2 mg/l, tank water ranges from 0.4 to 2.8 and 0.9 to 2.3 mg/l, for pre- and post-monsoon periods, respectively. The modified Piper diagram reflects that the water belongs to Ca²⁺–Mg²⁺–HCO₃ ^? to Na⁺–HCO₃ ^? facies. Negative chloroalkali indices in both the seasons prove that ion exchange between Na⁺ and K⁺ in aquatic solution took place with Ca²⁺ and Mg²⁺ of host rock. The interpretation of plots for different major ions and molar ratios suggest that weathering of silicate rocks and water–rock interaction is responsible for major ion chemistry of groundwater/surface water. High fluoride content in groundwater was attributed to continuous water–rock interaction during the process of percolation with fluorite bearing country rocks under arid, low precipitation, and high evaporation conditions. The low calcium content in rocks and soils, and the presence of high levels of sodium bicarbonate are important factors favouring high levels of fluoride in waters. The basement rocks provide abundant mineral sources of fluoride in the form of amphibole, biotite, fluorite, mica and apatite.     

Hydrogeochemical processes and contaminants enrichment with special emphasis on fluoride in groundwater of Birbhum district,West Bengal,India

The hydrogeochemistry of groundwater in rural parts of Birbhum district, West Bengal, India, has been studied to understand the contaminants and prime processes involved in their enrichment with a focus on F^? concentration. The lithological units consist of Quaternary alluviums with underlying Rajmahal basaltic rocks of Middle Jurassic age. Groundwater occurs in the alluviums, weathered residuum and fracture zone of Rajmahal rocks. Studies show elevated concentration of Cl^?, SiO₂, Fe and F^?; excess Cl^? is attributed to anthropogenic inputs, SiO₂ is ascribed to high degree of weathering of silica rich host rocks, and high Fe is due to the interaction of water with Fe-rich sediments under reducing condition. The F^? concentration is found high (>1.20 mg/L) mainly in water from Rajmahal rocks revealing a lithological control on F^? enrichment. The weathering of silicates and ion exchange are the leading controlling processes for major ions in groundwater. The F^? enrichment is due to the dissolution of F^?-bearing minerals and perhaps also through anion exchange (OH^? for F^?) on clay minerals at high alkaline conditions; precipitation of CaCO₃ favours CaF₂ dissolution leading to elevated F^? concentration. CaHCO₃, the dominant water type, contains low F^? while NaHCO₃ and NaCl types exhibit high F^? concentrations. Among the three spatial associations, Cluster-1 and Cluster-2 are CaHCO₃ type; Cluster-3 shows NaHCO₃ and NaCl waters with low Ca²⁺ and Mg²⁺ and high Na⁺ contents. Cluster-1 and Cluster-2 waters are, in general, drinkable barring the elevated Fe content, while Cluster-3 water is unsafe for drinking due to the high F^? concentration.     

Evaluation of hydrogeochemistry and water quality in Bist-Doab region,Punjab, India

Agricultural activities act as dominant polluter of groundwater due to increased fertilizers and pesticides usage. Bist-Doab region, Punjab, India, is one such region facing deterioration of groundwater quality due to usage of fertilizers. This study aims in delineating and evaluating the groundwater quality in the region. Water samples are collected from canals, reservoir, and shallow and deep groundwater. Water types in canal and reservoir in Kandi region are Mg²⁺HCO₃ ^? and Mg²⁺Ca²⁺Na⁺HCO₃ ^?, respectively. While water types of shallow and deep groundwaters are found to be of two types: Na⁺Mg²⁺Ca²⁺HCO₃ ^? and Ca²⁺Mg²⁺Na⁺HCO₃ ^?. Presence of Mg²⁺ in groundwater at locations adjoining canals indicates recharge due to canal. The major ion (Na⁺, Mg²⁺, Ca²⁺, HCO₃ ^?) chemistry of the region is due to weathering of rocks that are rich in sodic minerals and kankar. Deep groundwater quality in the region meets BIS and WHO standards for drinking purpose, unlike shallow groundwater which is of poor quality at many locations. Both shallow and deep groundwater with high sodium concentration (>1.5 meq/l) affect cropping yield and permeability of soil matrix. High concentration of SO₄ ^2? and NO₃ ^2? (>1 meq/l) in shallow groundwater at few locations indicates influence of anthropogenic (fertilizer) activity. Factor analysis indicates that the major cations, bicarbonate and chloride are derived from weathering/dissolution of source rocks. Higher concentration of nitrate and presence of sulphate in shallow groundwater at few locations is due to usage of fertilizers and pesticides.     

Geochemical and isotopic studies of groundwater conditions in the Densu River Basin of Ghana

The Densu River Basin (DRB) is an important agricultural area in Ghana and has a high population density. Water shortages have occurred in the basin due to drying out of surface water, heavy pollution and low yield in most of the production wells, which are crucial factors restricting sustainable socioeconomic development. This study was carried out to investigate the geochemical characteristics and evolution, as well as recharge processes in the DRB system with regard to the tectonics, geomorphology, lithology and flow system. It mainly used hydrochemistry, environmental isotopes and a series of comprehensive data interpretation, e.g., statistics, ionic ratios and Piper diagram to obtain a better understanding of the functioning of the system. The following hydrochemical processes were identified as the main factors controlling the water quality of the groundwater system: weathering of silicate minerals, dissolution, ion exchange and, to a lesser extent, evaporation, which seems to be more pronounced downgradient of the flow system. As groundwater flows from the recharge to discharge areas, chemical patterns evolve in the order of Ca²⁺–HCO₃ ^?, Ca²⁺/Mg²⁺–HCO₃ ^? to Ca²⁺/Na⁺–Cl^?, Ca²⁺–Na⁺–HCO₃ ^? and Na⁺–Cl^? according to lithology. The environmental isotope (δ¹⁸O, δ²H, ³H) measurements further revealed that groundwater in the DRB was a relatively well-mixed system as evidenced by the encoded narrow range of values. However, deviation from the rainwater signature indicates combined local processes such as direct percolation through preferential channels, evaporation, and probable surface water and anthropogenic contribution to the system.     

Assessment of groundwater suitability for irrigation in a gold mine surrounding area,NE Iran

The Kouh-e Zar mining area with iron oxide-rich types of Cu–Au (IOCG)-type gold mineralization is located in a fractured zone between two main “Darouneh” and “Taknar” faults in 35 km northwest of Torbat-e Heydarieh. In this study, the hydrogeochemistry and water quality of groundwater were examined for irrigation uses. Totally, 11 groundwater samples were collected in semi-arid area surrounding the mine. According to the irrigation water quality indices such as sodium absorption ratio, sodium percentage, residual sodium carbonate, residual sodium bicarbonate, potential salinity, salinity index, salinity hazard, permeability index and magnesium hazard, the water resources were appraised suitable to unsuitable. Na⁺ was a dominant cation and HCO₃^? was a dominant anion in the water samples. Fortunately, SO₄^2? content is low (<?250 mg/L) in the water samples because of low-sulfide content mineralization in this mine. Water–rock interaction was defined as the controlling process on groundwater chemistry based on the Gibbs diagram. Calculated saturation indices revealed that the anion and cations in groundwater originated from dissolution of minerals and evaporation process. In the case of dominant Ca²⁺ and Mg²⁺, they were originated by dissolution of carbonate minerals such as calcite, dolomite and aragonite. Na⁺ was likely originated by plagioclase weathering in the brecciated volcanic rocks. Though the sulfidic mineralization is not so high in the Kouh-e Zar area, however, considering the existence of metalogenic mineralization in the Kouh-e Zar area, there is also a risk potential of release of toxic elements into the groundwater on which further deep investigation is ongoing in the area.     

Regional groundwater flow and geochemical evolution in the Amacuzac River Basin,Mexico

An approach is presented to investigate the regional evolution of groundwater in the basin of the Amacuzac River in Central Mexico. The approach is based on groundwater flow cross-sectional modeling in combination with major ion chemistry and geochemical modeling, complemented with principal component and cluster analyses. The hydrogeologic units composing the basin, which combine aquifers and aquitards both in granular, fractured and karstic rocks, were represented in sections parallel to the regional groundwater flow. Steady-state cross-section numerical simulations aided in the conceptualization of the groundwater flow system through the basin and permitted estimation of bulk hydraulic conductivity values, recharge rates and residence times. Forty-five water locations (springs, groundwater wells and rivers) were sampled throughout the basin for chemical analysis of major ions. The modeled gravity-driven groundwater flow system satisfactorily reproduced field observations, whereas the main geochemical processes of groundwater in the basin are associated to the order and reactions in which the igneous and sedimentary rocks are encountered along the groundwater flow. Recharge water in the volcanic and volcano-sedimentary aquifers increases the concentration of HCO₃ ^–, Mg²⁺ and Ca²⁺ from dissolution of plagioclase and olivine. Deeper groundwater flow encounters carbonate rocks, under closed CO₂ conditions, and dissolves calcite and dolomite. When groundwater encounters gypsum lenses in the shallow Balsas Group or the deeper Huitzuco anhydrite, gypsum dissolution produces proportional increased concentration of Ca²⁺ and SO₄ ^2–; two samples reflected the influence of hydrothermal fluids and probably halite dissolution. These geochemical trends are consistent with the principal component and cluster analyses.     

Geochemistry and quality of groundwater of Gummanampadu sub-basin, Guntur District, Andhra Pradesh, India

Groundwater survey has been carried out in the area of Gummanampadu sub-basin located in Guntur District, Andhra Pradesh, India for assessing the factors that are responsible for changing of groundwater chemistry and consequent deterioration of groundwater quality, where the groundwater is a prime source for drinking and irrigation due to non-availability of surface water in time. The area is underlain by the Archaean Gneissic Complex, over which the Proterozoic Cumbhum rocks occur. The results of the plotting of Ca²⁺ + Mg²⁺ versus HCO₃ ^? + CO₃ ^2?, Ca²⁺ + Mg²⁺ versus total cations, Na⁺ + K⁺ versus total cations, Cl^? + SO₄ ^2? versus Na⁺ + K⁺, Na⁺ versus Cl^?, Na⁺ versus HCO₃ ^? + CO₃ ^2?, Na⁺ versus Ca²⁺ and Na⁺: Cl^? versus EC indicate that the rock–water interaction under alkaline condition is the main mechanism in activating mineral dissociation and dissolution, causing the release of Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, CO₃ ^2?, SO₄ ^2? and F^? ions into the groundwater. The ionic relations also suggest that the higher concentrations of Na⁺ and Cl^? ions are the results of ion exchange and evaporation. The influences of anthropogenic sources are the other cause for increasing of Mg²⁺, Na⁺, Cl^?, SO₄ ^2? and NO₃ ^? ions. Further, the excess alkaline condition in water accelerates more effective dissolution of F^?-bearing minerals. Moreover, the chemical data plotted in the Piper’s, Gibbs’s and Langelier–Ludwig’s diagrams, computed for the chloro-alkaline and saturation indices, and analyzed in the principal component analysis, support the above hypothesis. The groundwater quality is, thus, characterized by Na⁺ > Ca²⁺ > Mg²⁺ > K⁺: HCO₃ ^? + CO₃ ^2? > Cl^? > SO₄ ^2? > NO₃ ^? > F^? facies. On the other hand, majority of groundwater samples are not suitable for drinking with reference to the concentrations of TDS, TH, Mg²⁺ and F^?, while those are not good for irrigation with respect to USSL’s and Wilcox’s diagrams, residual sodium carbonate, and magnesium hazard, but they are safe for irrigation with respect to permeability index. Thus, the study recommends suitable management measures to improve health conditions as well as to increase agricultural output.     

Distinct groundwater recharge sources and geochemical evolution of two adjacent sub-basins in the lower Shule River Basin,northwest China

Based on analysis of groundwater hydrogeochemical and isotopic data, this study aims to identify the recharge sources and understand geochemical evolution of groundwater along the downstream section of the Shule River, northwest China, including two sub-basins. Groundwater samples from the Tashi sub-basin show markedly depleted stable isotopes compared to those in the Guazhou sub-basin. This difference suggests that groundwater in the Tashi sub-basin mainly originates from meltwater in the Qilian Mountains, while the groundwater in the Guazhou sub-basin may be recharged by seepage of the Shule River water. During the groundwater flow process in the Tashi sub-basin, minerals within the aquifer material (e.g., halite, calcite, dolomite, gypsum) dissolve in groundwater. Mineral dissolution leads to strongly linear relationships between Na⁺ and Cl^? and between Mg²⁺+ Ca²⁺ and SO₄ ^2??+?HCO₃ ^?, with stoichiometry ratios of approximately 1:1 in both cases. The ion-exchange reaction plays a dominant role in hydrogeochemical evolution of groundwater in the Guazhou sub-basin and causes a good linear relationship between (Mg²⁺+ Ca²⁺)–(SO₄ ^2??+?HCO₃ ^?) and (Na⁺+ K⁺)–Cl^? with a slope of ?0.89 and also results in positive chloroalkaline indices CAI 1 and CAI 2. The scientific results have implications for groundwater management in the downstream section of Shule River. As an important irrigation district in Hexi Corridor, groundwater in the Guazhou sub-basin should be used sustainably and rationally because its recharge source is not as abundant as expected. It is recommended that the surface water should be used efficiently and routinely, while groundwater exploitation should be limited as much as possible.     

A geochemical and stable isotope investigation of groundwater/surface-water interactions in the Velenje Basin,Slovenia

The geochemical and isotopic composition of surface waters and groundwater in the Velenje Basin, Slovenia, was investigated seasonally to determine the relationship between major aquifers and surface waters, water–rock reactions, relative ages of groundwater, and biogeochemical processes. Groundwater in the Triassic aquifer is dominated by HCO₃ ^–, Ca²⁺, Mg²⁺ and δ¹³C_DIC indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has δ¹⁸O and δD values that plot near surface waters on the local and global meteoric water lines, and detectable tritium, likely reflecting recent (<50 years) recharge. In contrast, groundwater in the Pliocene aquifers is enriched in Mg²⁺, Na⁺, Ca²⁺, K⁺, and Si, and has high alkalinity and δ¹³C_DIC values, with low SO₄ ^2– and NO₃ ^– concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and Mg-rich clay minerals. Pliocene aquifer waters are also depleted in ¹⁸O and ²H, and have ³H concentrations near the detection limit, suggesting these waters are older, had a different recharge source, and have not mixed extensively with groundwater in the Triassic aquifer.     

Statistical analysis of the hydrogeochemical evolution of groundwater in hard rock coastal aquifers of Thoothukudi district in Tamil Nadu, India

The study of groundwater hydrogeochemistry of a hard rock aquifer system in Thoothukudi district has resulted in a large geochemical data set. A total of 100 water samples representing various lithologies like Hornblende Biotite Gneiss, Alluvium Marine, alluvium Fluvial, Quartzite, Charnockite, Granite and Sandstone were collected for two different seasons and analyzed for major ions like Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, Cl^?, SO₄ ^2?, NO₃ ^?, PO₄ ^?, F^? and H₄SiO₄. Statistical analysis of the data has been attempted to unravel the hidden relationship between ions. Correlation analyses and factor analyses were applied to classify the groundwater samples and to identify the geochemical processes controlling groundwater geochemistry. Factor analysis indicates that sea water intrusion followed by leaching of secondary salts, weathering and anthropogenic impacts are the dominant factors controlling hydrogeochemistry of groundwater in the study area. Factor score overlay indicate major active hydrogeochemical regimes are spread throughout the Eastern, Northwestern and Southeastern parts of the study area. The dominant ions controlling the groundwater chemistry irrespective of season are Cl^?, Na⁺, Mg²⁺, Ca²⁺, SO₄ ^2?, K⁺ and NO₃ ^?. An attempt has also been made to note the seasonal variation of the factor representations in the study area. This study also illustrates the usefulness of statistical analysis to improve the understanding of groundwater systems and estimates of the extent of salinity/salt water intrusion.     

Geochemistry and assessment of hydrogeochemical processes in groundwater in the southern part of Bathinda district of Punjab, northwest India

Hydrogeochemistry of groundwater is important for sustainable development and effective management of the groundwater resource. Fifty-six groundwater samples were collected from shallow tube wells of the intensively cultivated southern part of district Bathinda of Punjab, India, during pre- and post-monsoon seasons. Conventional graphical plots were used to define the geochemical evaluation of aquifer system based on the ionic constituents, water types, hydrochemical facies and factors controlling groundwater quality. Negative values of chloroalkaline indices suggest the prevalence of reverse ion exchange process irrespective of the seasons. A significant effect of monsoon is observed in terms chemical facies as a considerable amount of area with temporary hardness of Ca²⁺–Mg²⁺–HCO₃ ^? type in the pre-monsoon switched to Ca²⁺–Mg²⁺–Cl^? type (18%) followed by Na⁺–HCO₃ ^? type (14%) in the post-monsoon. Evaporation is the major geochemical process controlling the chemistry of groundwater process in pre-monsoon; however, in post-monsoon ion exchange reaction dominates over evaporation. Carbonate weathering is the major hydrogeochemical process operating in this part of the district, irrespective of the season. The abundance of Ca²⁺ + Mg²⁺ in groundwater of Bathinda can be attributed mainly to gypsum and carbonate weathering. Silicate weathering also occurs in a few samples in the post-monsoon in addition to the carbonate dissolution. Water chemistry is deteriorated by land-use activities, especially irrigation return flow and synthetic fertilisers (urea, gypsum, etc.) as indicted by concentrations of nitrate, sulphate and chlorides. Overall, results indicate that different natural hydrogeochemical processes such as simple dissolution, mixing, weathering of carbonate minerals locally known as ‘‘kankar’’ and silicate weathering are the key factors in both seasons.