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

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

Hydrological and reactive processes during rapid recharge to fracture zones: The Äspö large scale redox experiment

The hydrochemical response of fracture zones to enhanced recharge into the upper bedrock environment has been studied during a 3 a project at the Äspö Hard Rock Laboratory (HRL) in Southeastern Sweden. Hydrochemical data obtained during the experiment provides a basis for development of a model for the impact of accelerated recharge on groundwater composition and reactive processes during repository construction and operation. Tunnel construction at the HRL resulted in a 50-fold increase in recharge rates, and a 30-fold decrease in groundwater residence times in the fracture zone studied. Up to 80% dilution of the native groundwater created the greatest impact on groundwater composition. In addition, comparison of mass balances for solutes with known conservative behaviour, and reactive solutes, indicates a significant source of HCO⁻₃, SO²⁻₄ and Na⁺ ions and a significant sink for Ca²⁺ ions within the fracture zone. These trends are explained by ion-exchange processes and microbial degradation of organic C transported from the soil with recharge. The increased microbial activity helps maintain anoxic conditions within the fracture zone. The enhanced recharge favours the performance of the geological barrier since anoxic conditions help to protect against corrosion of engineered barriers, and because long-lived isotopes of Np, Tc and U are less soluble under reducing conditions. A secondary impact is the strong dilution which affects trace element speciation, and also the stability and possible transport of colloids, through ion strength effects. Results from this experiment are primarily significant for national radioactive waste disposal programs that consider potential repository sites in granite geology, and for other programs considering disposal in fractured rock.     

Minimal alteration of montmorillonite following long-term interaction with natural alkaline groundwater: Implications for geological disposal of radioactive waste

Bentonite is one of the more safety-critical components of the engineered barrier system in the disposal concepts developed for many types of radioactive waste. Bentonite is utilised because of its favourable properties which include plasticity, swelling capacity, colloid filtration, low hydraulic conductivity, high retardation of key radionuclides and stability in geological environments of relevance to waste disposal. However, bentonite is unstable under the highly alkaline conditions induced by Ordinary Portland Cement (OPC: initial porewater pH > 13) and this has driven interest in using low alkali cements (initial porewater pH9-11) as an alternative to OPC. To build a robust safety case for a repository for radioactive wastes, it is important to have supporting natural analogue data to confirm understanding of the likely long-term performance of bentonite in these lower alkali conditions. In Cyprus, the presence of natural bentonite in association with natural alkaline groundwater permits the zones of potential bentonite/alkaline water reaction to be studied as an analogy of the potential reaction between low alkali cement leachates and the bentonite buffer in the repository. Here, the results indicate that a cation diffusion front has moved some metres into the bentonite whereas the bentonite reaction front is restricted to a few millimetres into the clay. This reaction front shows minimal reaction of the bentonite (volumetrically, less than 1% of the bentonite), with production of a palygorskite secondary phase following reaction of the primary smectites over time periods of 10⁵–10⁶ years.     

Water circulation control on carbonate-δO records in a low permeability clay formation and surrounding limestones: The Upper Dogger–Oxfordian sequence from the eastern Paris basin, France

Upper Dogger to Oxfordian Formations in the eastern part of the Paris basin (France) are currently being investigated by the French nuclear waste management agency (Andra), testing the feasibility of long-term deep nuclear waste disposal in the Callovo-Oxfordian claystones. Characterising the hydrogeological behaviour of the Callovo-Oxfordian claystones is, therefore, essential in evaluating its potential as a geological barrier. In order to evaluate and quantify water/rock interactions experienced over geological time by these Formations, bulk carbonate δ¹³C and δ¹⁸O were measured and calculations of water-rock ratios were used to explain carbonate-δ¹⁸O changes. Meteoric porewater and a maximum temperature reached of about 40 °C were considered. The Jurassic marine carbonate δ¹³C was preserved in the Callovo-Oxfordian claystones and in the overlying limestones (−0.28‰ to 3.39‰/PDB), while the δ¹⁸O values are lower by 0-5‰ (−6.25‰ to −1.32‰/PDB). Calculations show that Upper Dogger and Oxfordian Limestone δ¹⁸O data:

(i)

have random-like distribution through theoretical δ¹⁸O-W/R curves and

(ii)

suggest that water/rock ratios (0.08-0.4) needed to explain δ¹⁸O changes are higher by a factor of about 2-20 compared to the present-day water/rock ratio.

These features indicate advection in both aquifers. According to the history of the Paris basin, this hydrogeological behaviour could have been effective since Jurassic/Cretaceous transition times. Inversely, the carbonate-δ¹⁸O content trends observed for the Callovo-Oxfordian data show that changes were controlled by post-depositional fluid-rock interaction with water/rock ratio (0.02-0.15) similar to the present-day porewater/rock ratio. The 130 m thick Callovo-Oxfordian claystone appears remarkably homogenous regarding its hydrogeological properties. This study suggests an initial marine porewater replacement by meteoric water only after porosity was reduced to its present value, thus demonstrating that the Callovo-Oxfordian clay has mainly been isolated from advective meteoric water circulation. Only the upper 20 m of the Callovo-Oxfordian claystone Formation underwent heterogeneous water-rock exchange (W/R from 0.01 to 0.3), probably as a result of its mineralogical heterogeneity and proximity to the advective Oxfordian Limestone aquifer.This study of carbonate-δ¹⁸O confirms the hydrogeological barrier properties of the Callovo-Oxfordian clay and suggests that it has been a natural hydrological barrier since the earliest times of its diagenesis.     

Hydrogeochemical characterization of major factors affecting the quality of shallow groundwater in the coastal area at Kimje in South Korea

This study has evaluated the main hydrogeochemical characteristics that affect the quality of shallow groundwater in the coastal area at Kimje in South Korea. In this area, the chemical composition of groundwater is mostly classified into Na⁺?Cl^? and Ca²⁺+Mg²⁺?NO₃^-+Cl^? types. These types are affected by three major factors: seawater intrusion, fertilizers and redox processes. The Na⁺?Cl^? type, which is generally localized in the coastal area, shows typical characteristics of groundwater affected not only by modern seawater but also by old seawater residing in the reclaimed land. In contrast, the Ca²⁺+Mg²⁺?NO₃^-+Cl^? type, which is usually found inland, is very contaminated by fertilizers. As groundwater flows from the inland area to the coast, the redox condition changes from an oxic condition to a suboxic/anoxic condition. In addition, the reclamation has caused a large amount of underlying organic matter. These effects provide optimum conditions for the occurrence of redox processes in the coastal area.     

Hydrochemistry, mineralogy and chemical fractionation of mine and processing wastes associated with porphyry copper mines: A case study from the Sarcheshmeh mine, SE Iran

The Sarcheshmeh is one of the largest Oligo-Miocene porphyry Cu deposits in the world. Comparative hydrochemical, mineralogical and chemical fractionation associated with mining efflorescence salts and processing wastes of this mine are discussed. Hydrochemical results showed that rock waste dumps, reject wastes and old impoundments of tailings are the main sources of acid mine drainage waters (AMD) that contain potentially toxic metals such as Cd, Co, Cu, Mn, Ni and Zn as well as Al. Episodic fluxes of highly contaminated acidic waters were produced in a tailings dam over a short period of time. Secondary soluble minerals provide important controls on the quality of AMD produced, especially in old, dry tailings impoundments. Secondary sulfate minerals such as gypsum, magnesiocopiapite, hydronium jarosite, kornelite and coquimbite were found in rock waste drainages and in old weathered reject wastes. Highly soluble secondary minerals such as gypsum, eriochalcite, and bonattite are also observed in an evaporative layer on old tailings impoundments. Chemical fractionation patterns of potentially toxic elements showed that the geochemical behavior of metals is primarily controlled by the mineralogical composition of waste samples. Elements such as Co, Cr, Cu, Mn, Ni and Zn are readily released into the water soluble fraction from efflorescence salts associated with rock waste drainages, as well as from the evaporative layer of old tailings. Potentially toxic elements, such as As, Mo and Pb, are principally adsorbed or co-precipitated with amorphous and crystalline Fe oxides, but they may also be associated with oxidizing, primary sulfides and residual fractions. Following the development of the dammed tailings pond, the secondary minerals were dissolved, producing acidic waters contaminated by Al (154 mg L⁻¹), Cu (150 mg L⁻¹), Cd (0.31 m gL⁻¹), Co (2.13 mg L⁻¹), Mn (73.7 mg L⁻¹), Ni (1.74 mg L⁻¹), Zn (20.3 mg L⁻¹) and Cl (1690 mg L⁻¹). Therefore, the potential use of recycled water from the Sarcheshmenh dammed tailings pond is diminished by the presence of corrosive ions like Cl⁻ in highly acidic fluids that promote corrosion of pipes and pumps in the water recycling system.     

Major ion geochemistry of shallow groundwater in the Qinghai Lake catchment, NE Qinghai-Tibet Plateau

Conventional hydrochemical techniques and statistical analyses were applied to better understand the solute geochemistry and the hydrochemical process of shallow groundwater in the Qinghai Lake catchment. Shallow groundwater in the Qinghai Lake catchment is slightly alkaline, and is characterized by a high ion concentrations and low water temperature. The total dissolved solids (TDS) in most of the samples are <1,000?mg/L, i.e. fresh water and depend mainly on the concentration of SO₄ ^2?, Cl^? and Na⁺. Groundwater table is influenced directly by the residents?? groundwater consumption. Most of the groundwaters in the Qinghai Lake catchment belong to the Ca²⁺(Na⁺) ?CHCO₃ ^? type, while the Qinghai Lake, part of the Buha (BHR) and the Lake Side (LS) samples belong to the Na⁺?CCl^? type. The groundwater is oversaturated with respect to aragonite, calcite and dolomite, but not to magnesite and gypsum. Solutes are mainly derived from strong evaporite dissolution in Daotang, BHR and LS samples and from strong carbonate weathering in Hargai and Shaliu samples. Carbonate weathering is stronger than evaporite dissolution with weak silicate weathering in the Qinghai Lake catchment. Carbonate weathering, ion exchange reaction and precipitation are the major hydrogeochemical processes responsible for the solutes in the groundwater in the Qinghai Lake catchment. Most of the shallow groundwaters are suitable for drinking. More attention should be paid to the potential pollution of nitrate, chloride and sulfide in shallow groundwater in the future.     

Geochemical characterization of arsenic-affected alluvial aquifers of the Bengal Delta (West Bengal and Bangladesh) and Chianan Plains (SW Taiwan): Implications for human health

Major ion and trace element analyses were performed on groundwater samples collected from the Bengal Delta (Chakdaha municipality, West Bengal and Manikgonj town, Bangladesh) and Chianan Plains (SW Taiwan) to compare geochemical characteristics. Results showed that concentrations of Na, K, Mg, Cl and SO₄ were generally higher in Chianan Plain (CNP) groundwaters, while high Ca was observed in Bengal Delta Plain (BDP) groundwater. Measured As concentrations in groundwaters of BDP and CNP showed large variations, with mean As concentrations of 221 μg/L (range: 1.1-476 μg/L) in Chakdaha, 60 μg/L (range: 0.30-202 μg/L) in Manikgonj, and 208 μg/L (range: 1.3-575 μg/L) in CNP groundwater. The Fe-reduction mechanism was found to be the dominant geochemical process in releasing As from sediment to groundwater in Chakdaha, West Bengal, however the Mn-reduction process was dominant in groundwaters of Manikgonj, Bangladesh. In Chianan Plain groundwater, a combination of geochemical processes (e.g., bacterial Fe-reduction, mineral precipitation and dissolution reactions) controlled release of As. Fluorescence spectral patterns of the groundwater showed low relative fluorescence intensity (RFI) of dissolved humic substances in BDP groundwater (mean: 63 and 72 QSU, Chakdaha and Manikgonj, respectively), while high RFI was observed in CNP groundwater (mean: 393 QSU). The FT-IR spectra of the extracted humic acid fractions from sediments of Chianan Plain showed a stronger aliphatic band at 2850-3000 cm⁻¹ and a higher resolved fingerprint area (from 1700 to 900 cm⁻¹) compared with BDP sediments. The geochemical differences between the study areas may play a crucial role in the clinical manifestation of Blackfoot disease observed only in Chianan Plain, SW Taiwan.     

Groundwater contamination in parts of Nalgonda district,Telangana, India as revealed by trace elemental studies

The present paper deals with major and trace elements geochemistry of the groundwater from Nalgonda district, Telangana. The study area is very important in terms of anthropogenic activity like rapid industrial, urban development, pesticides, pharmaceutical, granite polishing and agro based industries. Inductively coupled plasma mass spectrometer (ICPMS) was employed to determine the concentration of trace elements in collected groundwater samples (bore well). These probe elements were further categorized as toxic elements (Pb, As, Cd, and V), alkaline earths (Sr and Ba), alkali metals (Li, Rb), transition metals (Cr, Mo and Ni), metallic elements (Cu, Fe, Zn, Al, Co), and other non-metallic elements (Se and Si). The groundwater quality was examined in perspective of Indian as well as World Health Organization drinking water standards. Based on the analytical results, groundwater in the study area is found to be slightly alkaline in nature and very hard, the average abundance of the major cations and anions is in the order of Ca⁺<Na⁺<Mg⁺<K⁺ and Cl^-<HCO₃ ^?<CO₃ ^?<SO₄ ^?<NO₃ ^?<F^– respectively. The dominant hydro chemical facies of groundwater is Na⁺ - HCO ₃ ^– – Cl^– and Na⁺ - Cl^– – HCO^– ₃ types.The results of trace elements shows that concentration of Pb, As, Cd, V in collected samples exceeding the desirable limits, and in the case of alkaline, alkali, transition, non-metallic elements, seventy per cent of the samples crossed the desirable limits, but all metallic elements viz. Cu, Fe, Zn, Al, Co is within the limits as per Indian as well as World Health Organizations drinking water standards. Factor analysis results shows that seven factors emerged as a significant contributor to the groundwater contamination is about 65.32 per cent. The spatial variation maps decipher trace elemental concentrations both geogenic and anthropogenic origin, by three zones i.e. ‘low’, ‘moderate’ and ‘high’ of the study area based on environment using Arc-GIS. High concentrations of trace elements are indicative of phenomenal rise in chemical composition and likely to have its origin from silicate weathering reactions and dissolution/precipitation processes supported by rainfall and anthropogenic activities, indiscriminate use of fertilizers/pesticides, and disposal of waste and sewage, release of reactive pollutants into the atmosphere by industries. Hence, this work is of immense societal benefit in terms of prevailing human health hazards in the study area with a direct relevance to such industrially populated regions elsewhere.     

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.     

Groundwater chemical and fecal contamination assessment of the Jerba unconfined aquifer,southeast of Tunisia

Located in the southeast of Tunisia, on the Mediterranean Sea, Jerba Island has a semiarid climate condition. The surface water scarcity has made groundwater the main source to supply the domestic, touristic, and agricultural water demand. Unconfined aquifer is a vulnerable costal aquifer system that undergoes several phenomena. This work aims at assessing the geochemical and bacteriological groundwater quality, defining groundwater pollution sources and promoting sustainable development and effective management of groundwater resources in Jerba Island. Data were collected after the wet season in 2014 from 79 wells. Electric conductivity, pH, TDS, and major and fecal tracers (total coliforms, thermotolerant coliforms, Escherichia coli, and Salmonella) were analyzed. Geochemical modeling including the relationships between geochemical tracers Na⁺ vs. Cl^?, Ca²⁺ vs. Cl^?, K⁺ vs. Cl^?, representative ionic ratios (Br^?/Cl^?, Na⁺/Cl^?, Mg²⁺/Ca²⁺), and statistical analysis were used to specify major process contributing to groundwater pollution and main factors controlling groundwater mineralization in the island. Groundwater varieties were hydrochemically classified into three types in terms of salinity values: group 1 (8.86%) to fresh water, group 2 (27.84%) to brackish water, and group 3 (63.29%) belongs to saline water. In addition, groundwater quality revealed high concentrations in chemical pollution tracers (Na⁺, Cl^?, SO₄ ^2?, and NO₃ ^?) and fecal tracers. Besides, most of the sampled wells were contaminated with nitrate (50.63%). Also, thermotolerant coliforms and E. coli were detected in all groundwater samples (96.2% of wells). Results indicated that the Jerba shallow aquifer was under serious threat from both natural and anthropogenic contamination. However, the wild discharge of domestic effluents, septic tanks, and sewage were the main origins of underground water contamination in Jerba Island. The reduction of fecal sources, through constructing normalized latrines is thus recommended.     

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.     

Evaluation of hydrogeochemical characteristics of phreatic alluvial aquifers in southeastern coastal belt of Prakasam district, South India

The assessment of hydrogeochemical processes that govern the water quality of inland freshwater aquifers in coastal environment, especially in Indian sub-continent, is occasionally attempted. To bridge the gap, a detail hydrochemical evaluation of groundwater occurring in coastal alluvium is attempted. Single set of high-density water sampling is done from a limited area to gain an in-depth knowledge of the processes that govern the water chemistry of the sandy aquifers. The water is of weak alkaline nature and less mineralized, EC being < 1,000 μS/cm in many samples. Major ion composition indicates that water is contaminated with excess concentration of nitrates. Ionic abundance is in the order of Cl^? > Na⁺  > Ca²⁺ > HCO₃ ^? > SO₄ ^2? > Mg²⁺  > NO₃ ^?. Na⁺ and Cl^? are almost in similar proportions implying the influence of coastal climate on water quality. The water shows modest variation in their ionic assemblage among different sample points as evident from Schoeller scheme. Groundwater can be classified into three distinct facies viz. Cl^?–Ca²⁺–Mg²⁺, Na⁺–Cl^? and Ca²⁺–Mg²⁺–HCO₃ ^? types. The ionic assemblages, their indices, ratios and cross-plots substantiate that multiple processes were involved in the evolution of the water chemistry. Among them, silicate weathering, halite dissolution, ion exchange and base exchange played prominent role in the ion enrichment of groundwater. The aquatic chemistry is further influenced and modified by marine environment, evapotranspiration and anthropogenic inputs which is authenticated by good correlation (r ² = 1) among the Na⁺–Cl^?, EC–Mg²⁺, Na⁺ and Cl^?. Gibbs plots established that evaporation is more responsible for contribution of minerals to the groundwater than aquifer material. Nitrate contamination can be attributed for poor sewerage disposal mechanism which is aggravated by fertilizer inputs, irrigation practices and agriculture activity. A contrasting correlation (r ² ≥90 to <0.40) among select pairs of ions reassures dissimilar source of those ions, involvement of multiple processes and limited interaction of formation water with aquifer material.     

The importance of unsaturated zone biogeochemical processes in determining groundwater composition, southeastern Australia

Analysis of soil, soil water and groundwater in the Mount William Creek catchment, southeastern Australia, shows that Mg²⁺ and Ca²⁺ within infiltrating rainfall are rapidly depleted by plant uptake and adsorption on clay minerals. Na⁺ and K⁺ may exhibit minor enrichment at shallow depths but are quickly readsorbed, so that cation/Cl^– ratios typical of groundwater are observed in soil water within the upper 200 cm of the soil profile for all species. The concentrations of K⁺ and Ca²⁺ in soil and groundwater are more depleted than Na⁺ and Mg²⁺ due to preferential uptake by vegetation. Removal of organic matter results in a continuing, long-term export of all major cations from the soil profiles. The processes of biogeochemical fractionation within the unsaturated zone rapidly modify the cation/Cl^– ratios of infiltrating rainfall to values characteristic of seawater. These mechanisms may have reached steady state, because groundwaters with seawater ion/Cl^– ratios are thousands of years old; the exchange sites on the soil clays are probably saturated, so cations supplied in rainfall are exported in organic matter and incorporated into recharge infiltrating into the groundwater. Much of the chemical evolution of groundwater traditionally attributed to processes within the aquifer is complete by the time recharge occurs; this evolutionary model may have broad application.     

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.     

Hydrogeochemical investigation and groundwater quality assessment of Pratapgarh district,Uttar Pradesh

Hydogrochemical investigation of groundwater resources of Paragraph district has been carried out to assess the solute acquisition processes and water quality for domestic and irrigation uses. Fifty-five groundwater samples were collected and analyzed for pH, electrical conductivity, total dissolved solids, hardness, major anions (F^?, Cl^?, NO₃, HCO₃ ^?, SO₄ ^2?) and cations (Ca²⁺, Mg²⁺, Na⁺, K⁺). Study results reveal that groundwater of the area is alkaline in nature and HCO₃ ^?, Cl^?, Mg²⁺, Na⁺ and Ca²⁺ are the major contributing ions to the dissolved solids. The hydrogeochemical data suggest that weathering of rock forming minerals along with secondary contributions from agricultural and anthropogenic sources are mainly controlling the groundwater composition of Pratapgarh district. Alkaline earth metals (Ca²⁺+Mg²⁺) exceed alkalis (Na⁺+K⁺) and weak acid (HCO₃ ^?) dominate over strong acids (Cl^?+SO₄ ^2?) in majority of the groundwater samples. Ca-Mg-HCO₃ and Ca-Mg-Cl-HCO₃ are the dominant hydrogeochemical facies in the groundwater of the area. The computed saturation indices demonstrate oversaturated condition with respect to dolomite and calcite and undersaturated with gypsum and fluorite. A comparison of groundwater quality parameters in relation to specified limits for drinking water shows that concentrations of TDS, F^?, NO₃ ^? and total hardness exceed the desirable limits in many water samples. Quality assessment for irrigation uses reveal that the groundwater is good for irrigation. However, values of salinity, sodium adsorption ratio (SAR), residual sodium carbonate (RSC), %Na and Kelley index are exceeding the prescribed limit at some sites, demanding adequate drainage and water management plan for the area.     

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.