武汉市区第四系含水层地下水有机污染敏感性研究

在详细调查武汉市水文地质条件和地下水污染现状的基础上，获得了高精度的武汉市水环境中微量有机污染物的组成数据。所检测出的有机组分达30余种，以苯及相关苯系物为主，污染程度较高的地下水主要分布在人口密集区和工业，商业区，应用改进的DRASTIC模型－地下水污染敏感性评价模型，在GIS平台上，编制了武汉市区地下水污染敏感性分区图。根据其评价结果，建议集中对那些敏感性相对较高的区域采取有效的环保措施，开发利用时应作出风险评价。     

Evaluation of intrinsic vulnerability to nitrate contamination of groundwater: appropriate fertilizer application management

In agricultural areas, fertilizer application is the main source of nitrate contamination of groundwater. To develop fertilizer management strategies to combat this problem, arable land in Hokkaido, Japan was evaluated using geographic information system techniques for intrinsic groundwater vulnerability to nitrate contamination. The DRASTIC method was modified to adapt it to the Hokkaido environment and used for the evaluation. Of the seven original DRASTIC factors, the depth to water (D), net recharge (R), soil media (S), topography (T), and impact of vadose zone media (I) were selected and used to explain the vertical movement of contaminants to the aquifer. The rating for the net recharge factor was also modified to a dilution factor for contaminants, rather than as a transporter. The frequency of wells with nitrate concentrations exceeding the Japanese environmental standard (10 mg/L) was reasonably explained by vulnerability evaluation results (GLM: logit-link, quasi-binomial distribution, Y = [1 + exp(6.873765 − 0.045988 × X)]⁻¹, p < 0.001). However, in the paddy fields and pastures, vulnerability did not exhibit a clear relationship with the frequency of wells exceeding the standard. This suggests that the modified DRASTIC method is applicable for fertilizer application management in upland fields. In addition, under the ongoing policy for acreage allotment for rice production, this method will be useful for deciding the arrangement of arable land and crop rotation taking into consideration the potential risk of fertilizer-induced nitrate contamination of groundwater.     

National scale evaluation of groundwater chemistry in Korea coastal aquifers: evidences of seawater intrusion

Pollution of groundwater by seawater intrusion poses a threat to sustainable agriculture in the coastal areas of Korea. Therefore, seawater intrusion monitoring stations were installed in eastern, western, and southern coastal areas and have been operated since 1998. In this study, groundwater chemistry data obtained from the seawater intrusion monitoring stations during the period from 2007 to 2009 were analyzed and evaluated. Groundwater was classified into fresh (<1,500 μS/cm), brackish (1,500–3,000 μS/cm), and saline (>3,000 μS/cm) according to EC levels. Among groundwater samples (n = 233), 56, 7, and 37% were classified as the fresh, brackish, and saline, respectively. The major dissolved components of the brackish and saline groundwaters were enriched compared with those of the fresh groundwater. The enrichment of Na⁺ and Cl⁻ was especially noticeable due to seawater intrusion. Thus, the brackish and saline groundwaters were classified as Ca–Cl and Na–Cl types, while the fresh groundwater was classified as Na–HCO₃ and Ca–HCO₃ types. The groundwater included in the Na–Cl types indicated the effects of seawater mixing. Ca²⁺, Mg²⁺, Na⁺, K⁺, SO₄ ²⁻, and Br⁻ showed good correlations with Cl⁻ of over r = 0.624. Of these components, the strong correlations of Mg²⁺, SO₄ ²⁻, and Br⁻ with Cl⁻ (r ≥ 0.823) indicated a distinct mixing between fresh groundwater and seawater. The Ca/Cl and HCO₃/Cl ratios of the groundwaters gradually decreased and approached those of seawater. The Mg/Cl, Na/Cl, K/Cl, SO₄/Cl, and Br/Cl ratios of the groundwaters gradually decreased, and were similar to or lower than those of seawater, indicating that Mg²⁺, Na⁺, K⁺, SO₄ ²⁻, and Br⁻, as well as Cl⁻ in the saline groundwater can be enriched by seawater mixing, while Ca²⁺ and HCO₃ ⁻ are mainly released by weathering processes. The influence of seawater intrusion was evaluated using threshold values of Cl⁻ and Br⁻, which were estimated as 80.5 and 0.54 mg/L, respectively. According to these criteria, 41–50% of the groundwaters were affected by seawater mixing.     

城市地下水污染敏感性分析

地下水污染敏感性分析与制图是目前国际上水文地质工作的热点.总结了过去所用的评价方法, 在GIS平台上根据我国城市的实际情况, 对原有的DRASTIC模型加以开发改进, 提出了DRAMIC模型并加以解释, 以作为我国统一的城市地下水污染敏感性分析的通用指标.最后介绍了如何用GIS来作地下水污染敏感性分区图.      

Conditioning DRASTIC model to simulate nitrate pollution case study: Hamadan–Bahar plain

One of the major causes of groundwater pollution in Hamadan–Bahar aquifer in western Iran is a non-point source pollution resulting from agricultural activities. Withdrawal of over 88% of drinking water from groundwater resources, adds urgency to the studies leading to a better management of water supplies in this region. In this study, the DRASTIC model was used to construct groundwater vulnerability maps based on the “intrinsic” (natural conditions) and “specific” (including management) concepts. As DRASTIC has drawbacks to simulate specific contaminants, we conditioned the rates on measured nitrate data and optimized the weights of the specific model to obtain a nitrate vulnerability map for the region. The performance of the conditioned DRASTIC model improved significantly (R ² = 0.52) over the intrinsic (R ² = 0.12) and specific (R ² = 0.19) models in predicting the groundwater nitrate concentration. Our study suggests that a locally conditioned DRASTIC model is an effective tool for predicting the region’s vulnerability to nitrate pollution. In addition, comparison of groundwater tables between two periods 30 years apart indicated a drawdown of around 50 m in the central plain of the Hamadan–Bahar region. Our interpretation of the vulnerability maps for the two periods showed a polluted zone developing in the central valley requiring careful evaluation and monitoring.     

Investigation of groundwater mineralization in the Hammamet–Nabeul unconfined aquifer,north-eastern Tunisia: geochemical and isotopic approach

Detailed hydrogeochemical and isotopic data of groundwaters from the Hammamet–Nabeul unconfined aquifer are used to provide a better understanding of the natural and anthropogenic processes that control the groundwater mineralization as well as the sources of different groundwater bodies. It has been demonstrated that groundwaters, which show Na–Cl and Ca–SO₄–Cl water facies, are mainly influenced by the dissolution of evaporates, the dedolomitization and the cation-exchange process; and supplementary by anthropogenic process in relation with return flow of irrigation waters. The isotopic signatures permit to classify the studied groundwaters into two different groups. Non-evaporated groundwaters that are characterized by depleted δ ¹⁸O and δ ²H contents highlighting the importance of modern recharge at higher altitude. Evaporated groundwaters with enriched contents reflecting the significance infiltration of return flow irrigation waters. Tritium data in the studied groundwaters lend support to the existence of pre-1950 and post-1960 recharge. Carbon-14 activities in shallow wells that provide evidence to the large contamination by organic ¹⁴C corroborate the recent origin of the groundwaters in the study area.     

Bioavailability of arsenic in the soil horizon: a laboratory column study

Groundwater contaminated with arsenic (As), when extensively used for irrigation, causes potentially long-term detrimental effects to surface soils. Such contamination can also directly affect human health when irrigated crops, such as rice, vegetable and fruits, are used for human consumption. Therefore, an understanding of the leaching behavior of As in surface soils is of high importance, because such behavior may increase the bioavailability of As in the soil horizon. In this study, we have investigated the role of phosphate ions in leaching and bioavailability of As in the soil horizon, where drinking groundwater contains elevated levels of As (≥50 μg/L). Soil and groundwater samples were characterized in the laboratory and measured for physical and chemical constituents. The soils are generally neutral to slightly alkaline in character (pH range 7.5–8.1) with low to moderate levels of free Fe₂O₃, Al₂O₃, CaCO₃, organic carbon, and clay content. The measured electrical conductivity (mean 599 μS/cm) of the soils demonstrates their non-saline nature. The Eh values (range −37 to −151 mV) of the groundwater indicate anoxic condition with low to moderate levels of bicarbonate (range 100–630 mg/L) and phosphate (range 0.002–4.0 mg/L). The arsenic content (range 50–690 μg/L; mean 321 μg/L) in groundwater has exceeded both WHO recommended guideline values (10 μg/L) and the National safe drinking water limit (50 μg/L). Regression analyses demonstrate that the bioavailability of As in the soil horizon is mainly controlled by the composition of free Fe₂O₃ and CaCO₃ content of the soils. However, application of P could increase bioavailability of As in the soil horizon and become available to plants for uptake.     

Interrelationship of TOC,As, Fe,Mn, Al and Si in shallow alluvial aquifers in Chapai-Nawabganj,Northwestern Bangladesh: implication for potential source of organic carbon

Two boreholes and ten piezometers in the Ganges flood plain were drilled and installed for collecting As-rich sediments and groundwater. Groundwater samples from the Ganges flood plain were collected for the analysis of cations (Ca²⁺, Mg²⁺, K⁺, Na⁺), anions (Cl⁻, NO₃ ⁻, SO₄ ²⁻), total organic carbon (TOC), and trace elements (As, Mn, Fe, Sr, Se, Ni, Co, Cu, Mo, Sb, Pb). X-ray powder diffraction was performed to characterize the major mineral contents of aquifer sediments and X-ray fluorescence (XRF) to analyze the major chemical composition of alluvial sediments. Results of XRF analysis clearly show that fine-grained sediments contain higher amounts of trace element because of their high surface area for adsorption. Relative fluorescence index (15–38 QSU) of humic substance in groundwater was measured using spectrofluorometer, the results revealed that groundwater in the Ganges flood plain contains less organic matter (OM). Arsenic concentration in water ranges from 2.8 to 170 μg/L (mean 50 μg/L) in the Ganges flood plain. Arsenic content in sediments ranges from 2.1 to 14 mg/kg (mean 4.58 mg/kg) in the flood plains. TOC ranges from 0.49 to 3.53 g/kg (mean 1.64 g/kg) in the Ganges flood plain. Arsenic is positively correlated with TOC (R ² = 0.55) in sediments of this plain. Humic substances were extracted from the sediments from the Ganges flood plain. Fourier transform infrared analysis of the sediments revealed that the plain contains less humic substances. The source of organic carbon was assigned from δ¹³C values obtained using elemental analysis-isotope ratio mass spectrometry (EA-IRMS); the values (−10 to −29.44‰) strongly support the hypothesis that the OM of the Ganges flood plain is of terrestrial origin.     

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.     

Hydrochemistry of urban groundwater in Seoul, South Korea: effects of land-use and pollutant recharge

The ionic and isotopic compositions (δD, δ¹⁸O, and ³H) of urban groundwaters have been monitored in Seoul to examine the water quality in relation to land-use. High tritium contents (6.1–12.0 TU) and the absence of spatial/seasonal change of O–H isotope data indicate that groundwaters are well mixed within aquifers with recently recharged waters of high contamination susceptibility. Statistical analyses show a spatial variation of major ions in relation to land-use type. The major ion concentrations tend to increase with anthropogenic contamination, due to the local pollutants recharge. The TDS concentration appears to be a useful contamination indicator, as it generally increases by the order of forested green zone (average 151 mg/l), agricultural area, residential area, traffic area, and industrialized area (average 585 mg/l). With the increased anthropogenic contamination, the groundwater chemistry changes from a Ca–HCO₃ type toward a Ca–Cl(+NO₃) type. The source and behavior of major ions are discussed and the hydrochemical backgrounds are proposed as the basis of a groundwater management plan.     

A new model (DRARCH) for assessing groundwater vulnerability to arsenic contamination at basin scale: a case study in Taiyuan basin,northern China

A modified DRASTIC model for groundwater vulnerability assessment (abbreviated as DRARCH model by combining the first letters of its six assessment indices) was proposed. It is essentially the specific application of DRASTIC model rather than a new model. Both natural hydrogeological conditions that prevent groundwater from contamination and important intrinsic hydrogeochemical properties of sediments in vadose zone that are related to the retardation of contaminants were considered as vulnerability indices. The DRARCH model consists of six indices: (1) Depth to the water table, (2) net Recharge, (3) Aquifer thickness, (4) Ratio of cumulative thickness of clay layers to total thickness of vadose zone, (5) Contaminant adsorption coefficient of sediment in vadose zone, and (6) Hydraulic conductivity of aquifer. The rating values and the weights of these vulnerability indices were obtained by contaminant transport simulation and factor analysis method respectively. Furthermore, the DRARCH model was applied to evaluate the groundwater vulnerability to arsenic contamination in Taiyuan basin, northern China, where groundwaters with high arsenic concentration occur in some localities. GIS-based mapping of groundwater vulnerability using this model indicates that the distribution of very high and high-vulnerability areas corresponds well to that of high-arsenic groundwaters. The DRARCH model is therefore reliable and useful for guiding groundwater environment management.     

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

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

Hydrochemical and isotopic evidence of recharge,apparent age,and flow direction of groundwater in Mayo Tsanaga River Basin,Cameroon: bearings on contamination

Unplanned exploitation of groundwater constitutes emerging water-related threats to MayoTsanaga River Basin. Shallow groundwater from crystalline and detrital sediment aquifers, together with rain, dams, springs, and rivers were chemically and isotopically investigated to appraise its evolution, recharge source and mechanisms, flow direction, and age which were used to evaluate the groundwater susceptibility to contamination and the basin’s stage of salinization. The groundwater which is Ca–Na–HCO₃ type is a chemically evolved equivalent of surface waters and rain water with Ca–Mg–Cl–SO₄ chemistry. The monsoon rain recharged the groundwater preferentially at an average rate of 74 mm/year, while surface waters recharge upon evaporation. Altitude effect of rain and springs show a similar variation of −0.4‰ for δ¹⁸O/100 m, but the springs which were recharged at 452, 679, and 773 m asl show enrichment of δ¹⁸O through evaporation by 0.8‰ corresponding to 3% of water loss during recharge. The groundwater which shows both local and regional flow regimes gets older towards the basins` margin with coeval enrichment in F⁻ and depletion in NO₃ ⁻. Incidentally, younger groundwaters are susceptible to anthropogenic contamination and older groundwaters are sinks of lithologenic fluoride. The basins salinization is still at an early stage.     

Environmental geochemistry of high arsenic groundwater at western Hetao plain, Inner Mongolia

Environmental geochemistry of high arsenic groundwater at Hetao plain was studied on the basis of geochemical survey of the groundwater and a core sediment. Arsenic concentration in groundwater samples varies from 76 to 1093 μg/L. The high arsenic groundwater mostly appears to be weakly alkaline. The concentrations of NO₃⁻ and SO₄²⁻ are relatively low, while the concentrations of DOC, NH₄⁺, dissolved Fe and sulfide are relatively great. Analysis of arsenic speciation in 21 samples shows that arsenic is present in the solution predominantly as As(III), while particulate arsenic constitutes about 10% of the total arsenic. Methane is detected in five samples with the greatest content being 5107 μg/L. The shallow aquifer in Hangjinhouqi of western Hetao plain is of strongly reducing condition. The arsenic content in 23 core sediment samples varies from 7.7 to 34.6 mg/kg, with great value in clay and mild clay layer. The obvious positive relationship in content between Fe₂O₃, Mn, Sb, B, V and As indicates that the distribution of arsenic in the sediments may be related to Fe and Mn oxides, and the mobilization of Sb, B and V may be affected by similar geochemical processes as that of As.     

Investigation of fluoride contamination and its mobility in groundwater of Simlapal block of Bankura district,West Bengal,India

The occurrence of dental/skeletal fluorosis among the people in the study area provided the motivation to assess the distribution, severity and impact of fluoride contamination in groundwater of Bankura district at Simlapal block, West Bengal, India. To meet the desired objective, groundwater samples were collected from different locations of Laxmisagar, Machatora and Kusumkanali regions of Simlapal block at different depths of tube wells in both pre- and post-monsoon seasons. Geochemical results reveal that the groundwaters are mostly moderate- to hard-water type. Of total groundwater samples, 37% are situated mainly in relatively higher elevated region containing fluoride above 1.5 mg/L, indicating that host aquifers are severely affected by fluoride contamination. Machatora region is highly affected by fluoride contamination with maximum elevated concentration of 12.2 mg/L. Several symptoms of fluorosis among the different age-groups of people in Laxmisagar and Machatora areas are indicating consumption of fluoridated water for prolonged period. The groundwater samples were mainly Na–Ca–HCO₃ type and rock dominance indicating the dissolution of minerals taking place. Ion exchange between OH^? ion and F^? ion present in fluoride-bearing mineral is the most dominant mechanism of fluoride leaching. High concentration of Na⁺ and HCO₃ ^? increases the alkalinity of the water, providing a favorable condition for fluoride to leach into groundwater from its host rocks and minerals.     

Groundwater nitrate contamination and risk assessment in an agricultural area,South Korea

The nitrate of groundwater in the Gimpo agricultural area, South Korea, was characterized by means of nitrate concentration, nitrogen-isotope analysis, and the risk assessment of nitrogen. The groundwaters belonging to Ca–(Cl + NO₃) and Na–(Cl + NO₃) types displayed a higher average NO₃ ⁻ concentration (79.4 mg/L), exceeding the Korean drinking water standard (<44.3 mg/L NO₃ ⁻). The relationship between δ¹⁸O–NO₃ ⁻ values and δ¹⁵N–NO₃ ⁻ values revealed that nearly all groundwater samples with δ¹⁵N–NO₃ ⁻ of +7.57 to +13.5‰ were affected by nitrate from manure/sewage as well as microbial nitrification and negligible denitrification. The risk assessment of nitrate for groundwater in the study area was carried out using the risk-based corrective action model since it was recognized that there is a necessity of a quantitative assessment of health hazard, as well as a simple estimation of nitrate concentration. All the groundwaters of higher nitrate concentration than the Korean drinking water standard (<44.3 mg/L NO₃ ⁻) belonged to the domain of the hazard index <1, indicating no health hazard by nitrate in groundwater in the study area. Further, the human exposure to the nitrate-contaminated soil was below the critical limit of non-carcinogenic risk.     

Evaluation of aquifers vulnerability to contamination in the Yarmouk River basin, Jordan, based on DRASTIC method

The existing different human activities and planned land uses put the groundwater resources in Jordan at considerable risk. There are evidences suggesting that the quality of groundwater supplies in north Jordan is under threat from a wide variety of point and non-point sources including agricultural, domestic, and industrial. Vulnerability maps are designed to show areas of greatest potential for groundwater contamination on the basis of hydrogeological conditions and human impacts. DRASTIC method incorporates the major geological and hydrogeological factors that affect and control groundwater movement: depth to groundwater (D), net recharge (R), lithology of the aquifer (A), soil texture (S), topography (T), lithology of vadose zone (I), and hydraulic conductivity (C). The main goal of this study is to produce vulnerability maps of groundwater resources in the Yarmouk River basin by applying the DRASTIC method to determine areas where groundwater protection or monitoring is critical. ArcGIS 9.2 was used to create the groundwater vulnerability maps by overlaying the available hydrogeological data. The resulting vulnerability maps were then integrated with lineament and land use maps as additional parameters in the DRASTIC model to assess more accurately the potential risk of groundwater to pollution. The general DRASTIC index indicates that the potential for polluting groundwater is low in the whole basin, whereas the resulting pesticide DRASTIC vulnerability map indicates that about 31% of the basin is classified as having moderate vulnerability, which may be attributed to agricultural activities in the area. Although high nitrate concentrations were found in areas of moderate vulnerability, DRASTIC method did not depict accurately the nitrate distribution in the area.     

Hydrogeochemical genesis of groundwaters with abnormal fluoride concentrations from Zhongxiang City,Hubei Province,central China

The groundwaters from Zhongxiang City, Hubei Province of central China, have high fluoride concentration up to 3.67 mg/L, and cases of dental fluorosis have been found in this region. To delineate the nature and extent of high fluoride groundwaters and to assess the major geochemical factors controlling the fluoride enrichment in groundwater, 14 groundwater samples and 5 Quaternary sediment samples were collected and their chemistry were determined in this study. Some water samples from fissured hard rock aquifers and Quaternary aquifers have high fluoride concentrations, whereas all karst water samples contain fluoride less than 1.5 mg/L due to their high Ca/Na ratios. For the high fluoride groundwaters in the fissured hard rocks, high HCO₃ ⁻ concentration and alkaline condition favor dissolution of fluorite and anion exchange between OH⁻ in groundwater and exchangeable F⁻ in some fluoride-bearing minerals. For fluoride enrichment in groundwaters of Quaternary aquifers, high contents of fluoride in the aquifer sediments and evapotranspiration are important controls.     

Hydrogeochemistry of the Sarada river basin,Visakhapatnam district,Andhra Pradesh,India

Systematic hydrogeochemical survey has been carried out for understanding the sources of dissolved ions in the groundwaters of the area occupied by Sarada river basin, Visakhapatnam district, Andhra Pradesh, India. Khondalites, charnockites and granite gneisses and calc-granulites of Precambrians and alluvial deposits of Quaternaries underlie the study area. Groundwaters are both fresh and brackish; the latter waters being a dominant. Most groundwaters are characterized by Na⁺:HCO₃⁻ facies due to chemical weathering of the rocks. Enrichment of Na⁺, K⁺, Cl⁻, SO₄²⁻, NO₃⁻ and F⁻ in some groundwater samples is caused by seawater intrusion, locally accompanied by ion-exchange, and anthropogenic activities, resulting in an increase of brackish in the groundwaters. Based on the results of this hydrogeochemical study, suitable management measures are recommended to solve the water quality problems.     

Groundwater Evolution and Mineral Alteration Reactions in the Basaltic Rock Sequence of Mt. Wasserkuppe, Germany: A Case Study

Groundwater sampling was accomplished in the basaltic sequence of the Rh?n mountain range, Germany, in order to investigate hydrochemical groundwater evolution and to delineate mineral alteration reactions involved in natural weathering. The hydrochemical compositions of near-surface groundwaters indicate a Ca/Mg–HCO₃ type with near-neutral pH and evolve to a Na–HCO₃ type with high pH at greater depth. Column experiments were performed with basaltic and phonolitic rock samples to determine individual mineral alteration reactions. The basic reactions could be related to the alteration of olivine, Ca-pyroxene, plagioclase, pyrrhotite, and feldspathoids under formation of secondary clay minerals (smectites, illite) and goethite. The mineral alteration reactions deduced from the leaching experiments by inverse modelling were found to be consistent with the mineral reactions associated with the natural groundwaters. The reactions calculated for groundwater evolution involve the alteration of primary and secondary minerals to produce low-T mineral phase. The conversion of secondary Na-beidellite to illite occurs at a later stage of groundwater evolution, reducing the concentrations of K⁺ and Mg²⁺. Near-surface groundwaters do not indicate significant cation exchange. Initial cation exchange requires elevated pH values, with Mg²⁺ removed from solution preferred to Ca²⁺. Na-alkalisation of the groundwaters at greater depth suggests the exchange of Na⁺ for Mg²⁺ and Ca²⁺ on Na-beidellite, supported by cation exchange on coatings of iron hydroxides as alteration products. Among the mature high-pH groundwater at greater depth, the dissolution of anorthite and albite has significant effect on groundwater composition.