Modeling of water–rock interactions in an aquitard of sandy clay in the coastal area near Beihai,China

Unconsolidated sand, gravel and clay deposits near Beihai and in the Leizhou Peninsula in southern China form an unconfined aquifer, aquitard and a confined aquifer. Water and soil samples were collected from the two aquifers in the coastal Beihai area for the determination of chemical compositions, minerals and soluble ions. Hydrogeochemical modeling of three flow paths through the aquitard are carried out using PHREEQC to determine water–rock interactions along the flow paths. The results indicate that the dissolution of anorthite, fluorite, halite, rhodochrosite and CO₂, and precipitation of potash feldspar and kaolinite may be occurring when groundwater leaks through the aquitard from the unconfined aquifer to the confined aquifer. Cation exchanges between Na and Ca can also happen along the flow paths.     

Hydrogeochemical evolution of groundwater in a Mediterranean coastal aquifer, Mersin-Erdemli basin (Turkey)

In this study, hydrogeologic and hydrochemical information from the Mersin-Erdemli groundwater system were integrated and used to determine the main factors and mechanisms controlling the chemistry of groundwaters in the area and anthropogenic factors presently affecting them. The PHREEQC geochemical modeling demonstrated that relatively few phases are required to derive water chemistry in the area. In a broad sense, the reactions responsible for the hydrochemical evolution in the area fall into four categories: (1) silicate weathering reactions; (2) dissolution of salts; (3) precipitation of calcite, amorphous silica and kaolinite; (4) ion exchange. As determined by multivariate statistical analysis, anthropogenic factors show seasonality in the area where most contaminated waters related to fertilizer and fungicide applications that occur during early summer season.     

The origin of fluoride-rich groundwater in Mizunami area, Japan — Mineralogy and geochemistry implications

The aim of this paper was to explore new factors that might be reasons for the occurrence of fluoride-rich groundwater in the area around a construction site. During the construction of two deep shafts of the Mizunami Underground Research Laboratory (MIU) in Mizunami city, central Japan, a large quantity of groundwater with high fluoride concentration was charged into the shafts. Chemical investigation carried out during the excavation revealed that fluoride concentrations in the area around the MIU site greatly exceeded those prescribed by Japanese standards. Therefore, the origin of fluoride ion was experimentally investigated. Samples were collected from the core of a deep borehole drilled in the study area. The weathering - and alteration levels of the collected granites varied greatly. Granitic powders were used to measure fluoride content in the granitic rock mass. The fluoride content ranged between 200 and 1300 mg/kg. The powders were reacted with purified water for 80 days. The results of water–rock interaction showed granitic rock to be one of the main sources of fluoride-rich groundwater in Mizunami area. Fluoride concentrations in these solutions that were shaken for 80 days varied between 2 and 7 mg/l. This change may have occurred as a result of the spatial distribution of fluoride ions in the granite mass as evidenced by mineralogical analysis of fluoride content in several specimens. X-ray powder diffraction analysis of the rock before- and after the water–rock interaction tests manifested that the presence of fluorite mineral was relatively small compared to other minerals. The degree of weathering and alteration might be an additional factor causing dissolution of fluoride-rich minerals. However, it was difficult to interpret the change in fluorite composition by X-ray diffraction analysis.     

Association of hydrogeological factors in temporal variations of fluoride concentration in a crystalline aquifer in India

The major part of groundwater in India is found in granitic aquifers. Fluoride in groundwater from a crystalline aquifer in a semi-arid region of granitic rocks in India, known as Maheshwaram watershed, was analyzed for spatial and temporal variability during 1999–2002 to assess the effect of hydrogeological factors on fluoride concentration. Samples were collected from 32 representative wells in the area for the pre- and post-monsoon seasons and analyzed for F content. The CHESS computer program was used to calculate ionic activities of aqueous species and the mineral saturation index (SI) for calcite and fluorite. The GARDENIA computer program was used to calculate the recharge values in the study area. The influences of dissolution kinetics of fluoride minerals and recharge from rainfall on fluoride concentration were of interest and results clearly indicate that fluoride content in groundwater depends on the interaction period of groundwater with host rock. Results could also be utilized for designing remedial measures particularly with dilution method in an optimal way.     

The chemical composition of the surface system of Peneos river, Thessaly/Central Greece

 Peneos is the mainstream for the drainage of Thessaly's basin. It contributes significantly in recharging the aquifers, as well as to the direct irrigation water, since there is intense agricultural activity in the basin of Thessaly. The investigation of the hydrochemical conditions of the surface water system of Peneos showed that the chemical composition is related to the lithology of the aquifers of the basin, the anthropogenic influence and the biological activity. The chemical composition of this system changes in time and space. The salinity decreases during the winter period, in contrast to the summer period when it increases drastically. The lower values of TDS appear in the upstream part of the river (95–124 mg/l) whereas downstream, the values of TDS increase significantly (400–632 mg/l). The hydrochemical type Ca-Mg-HCO₃ dominates the largest part of the river while it changes to NA-Cl in the estuary. The concentrations of the dissolved species in the main Peneos river are higher than in the spring waters. Peneos is the most polluted river in Greece. The concentration of the pollutants is higher at the downstream part of the river, but is lower than the accepted upper limits. The use of the surface water of the system of Peneos river for irrigation purposes based on the SAR factor is acceptable because the absorption ratio for Na and salinity are low and medium respectively. Received: 27 October 1997 · Accepted: 21 September 1998     

Hydrogeochemical modeling of the water seepages through Tannur Dam,southern Jordan

This paper reveals the geochemical processes of dissolution, precipitation and cation exchange that took place during water–rock interaction between water seepages through the Tannur Dam. The Schoeller diagram indicates that there are three major water types originating during water–rock interaction. The first water type is characterized by low salinity that ranges from 1,300 to 2,800 µs/cm, which represents the reservoir water and the water in the right side of the central gallery. The second water type is in the left side of the central gallery, which exhibits medium salinity that reaches about 4,400 µs/cm. The third water type is characterized by very high salinity that reaches a value of around 8,500 µs/cm and represents the water in the right existing adit. The increase of salinity can be explained due to the dissolution of carbonate and sulfate minerals that form the matrix of the foundation and the abutment rocks, and the dissolution of the grout curtain, which is composed of cement and bentonite. Hydrogeochemical modeling, using a computer code PHREEQC, was used to obtain the saturation indices of specific mineral phases, which might be related to interaction with water seepages, and to identify the chemical species of the dissolved ions. The thermodynamic calculations indicate that most of the water samples were undersaturated with respect to gypsum, anhydrite and halite, and were saturated and/or supersaturated with respect to calcite and dolomite. Ca(HCO₃)₂ is the primary water type, as a result of dissolution of carbonate minerals such as calcite and dolomite prevailing at the dam site. However, cation-exchange processes are responsible for the formation of the Na₂SO₄ water type from the CaSO₄ type that formed due to the dissolution of gypsum.     

Water–rock interaction during the process of steam stimulation exploitation of viscous crude oil in Liaohe Shuguang Oil Field, Liaoning, China

In the process of steam stimulation exploitation of viscous crude oil, the injected water, at high temperature and under high pressure, reacts intensively with the host rock. This kind of water–rock interaction in Liaohe Shuguang Oil Field was studied on the basis of analysis of water composition changes, laboratory experiments, mineral saturation indices analysis, and mass balance calculation. Compared with the injected water, the changes of the composition of discharged water are mainly the distinct decrease of pH, Na⁺, SiO₂ and Cl⁻, as well as the increase of K⁺, Ca²⁺, Mg²⁺, SO ₄ ²⁻ and HCO ₃ ⁻ . Laboratory experiments under field conditions showed: the dissolution sequence of minerals quantitatively is quartz>potassium feldspar>albite, and the main change of clay minerals is the conversion of kaolinite to analcime. Mass balance calculation indicated during the process of steam stimulation, large quantities of analcime are precipitated with the dissolution of large amounts of quartz, kaolinite, potassium feldspar, and CO₂. These results correlated very well with the experimental results. The calculated results of Liaohe Shuguang Oil Field showed that during the steam stimulation for viscous crude oil, the amounts of minerals dissolved (precipitated) are huge. To control the clogging of pore spaces of oil reservoirs, increased study of water–rock interaction is needed.     

Hydrogeochemical study in the Main Ethiopian Rift: new insights to the source and enrichment mechanism of fluoride

The central Main Ethiopian Rift suffers a severe water quality problem, characterized by an anomalously high fluoride (F) content that causes an endemic fluorosis disease. The current study, conducted in the Ziway–Shala lakes basin, indicates that the F content exceeds the permissible limit for drinking prescribed by the World Health Organization (WHO; 1.5 mg/l) in many important wells (up to 20 mg/l), with even more extreme F concentration in hot springs and alkaline lakes (up to 97 and 384 mg/l respectively). The groundwater and surface water from the highlands, typically characterized by low total dissolved solids (TDS) and Ca (Mg)–HCO₃ hydrochemical facies, do not show high F content. The subsequent interaction of these waters with the various rocks of the rift valley induces a general increase of the TDS, and a variation of the chemical signature towards Na–HCO₃ compositions, with a parallel enrichment of F. The interacting matrixes are mainly rhyolites consisting of volcanic glass and only rare F-bearing accessory minerals (such as alkali amphibole). Comparing the abundance and the composition of the glassy groundmass with other mineral phases, it appears that the former stores most of the total F budget. This glassy material is extremely reactive, and its weathering products (i.e. fluvio/volcano-lacustrine sediments) further concentrate the fluoride. The interaction of these “weathered/reworked” volcanic products with water and carbon dioxide at high pH causes the release of fluoride into the interacting water. This mainly occurs by a process of base-exchange softening with the neo-formed clay minerals (i.e. Ca–Mg uptake by the aquifer matrix, with release of Na into the groundwater). This is plausibly the main enrichment mechanism that explains the high F content of the local groundwater, as evidenced by positive correlation between F, pH, and Na, and inverse correlation between F and Ca (Mg). Saturation indices (SI) have been calculated (using PHREEQC-2) for the different water groups, highlighting that the studied waters are undersaturated in fluorite. In these conditions, fluoride cannot precipitate as CaF₂, and so mobilizes freely without forming other complexes. These results have important implications for the development of new exploitation strategies and accurate planning of new drilling sites. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Interstitial water and hydrochemistry of a mangrove forest and adjoining water system, south west coast of India

 Eh, pH, salinity, total alkalinity, dissolved O₂, NO₂ ^–, PO₄ ^–3, SiO₂ and NH₄ ⁺ of waters from a mangrove forest, an estuary and a creek connecting the mangrove forest and the estuary have been measured. Further, the chemistry of interstitial waters of surficial and core sediments from the mangrove forest have been analyzed for the above parameters, except dissolved oxygen. To understand the flux of nutrients from the mangrove forest to the adjoining estuary, creek waters were monitored during tidal phases. PO₄ ^–3, SiO₂ and NH₄ ⁺ were found to be at elevated levels in mangrove waters whereas NO₂ ^– shows no variation compared to the estuary. Dissolved O₂ is low in mangrove waters. PO₄ ^–3, NH₄ ⁺ and SiO₂ are several times higher in interstitial waters than in overlying waters. Several fold enrichment of PO₄ ^–3, NH₄ ⁺ and, to some extent, SiO₂ were measured in creek waters during ebbing relative to flooding, indicating that mangroves act as a perennial source for the above nutrients. Received: 26 May 1998 · Accepted: 21 July 1998     

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

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

Hydrochemical characteristics of Lastochka Spa (Primorye, Far East of Russia)

This study presents new data on major, trace and REE element concentration of groundwaters in Lastochka spa located in the northern part of Primorye, Far East of Russia. The studied area is characterized by two types of groundwaters issued from a spring and wells: fresh waters with low mineralization (Total Dissolved Solids is up to 400 mg/l) and high pCO₂ waters with high mineralization (TDS is up to 4700 mg/l). New data and previous δ¹³C_(TIC), oxygen (δ¹⁸O) and hydrogen (δ²H) isotope data indicate that these waters result from meteoric water infiltration in the Sikhote–Alin mountain, circulating at shallow depths in sedimentary rocks. CO₂ in groundwater is of mantle origin.     

Weathering profile of non-welded ignimbrite and the water infiltration behavior within it in relation to the generation of shallow landslides

The mechanism underlying rain-induced shallow landslides of non-welded ignimbrite is found to be a special type of weathering profile and the behavior of water infiltrating through that profile, according to our study of Ito ignimbrite in southern Kyushu, Japan. Rhyolitic volcanic glass, the primary component of ignimbrite, is first hydrated and dissolved, forming halloysite. Halloysite near ground surface is then transported through the ignimbrite by infiltrating water and becomes clogged in interstices to form clay bands. Suction monitoring across a weathering profile indicated that downward infiltration of water is disrupted once by a zone of less-permeable clay bands and again at the weathering front. This disruption at the front is caused by a capillary barrier effect caused by the structure where finer, weathered material overlies coarser, fresh material. This results in a well-defined weathering front, particularly beneath a slope where water flux is parallel to the front, whereas the front is transitional beneath a ridge top where the front is nearly horizontal and the water flux is normal to the front. Infiltrating water from rain increases the weight of weathered material and decreases the suction within the material, which is the final trigger of a shallow landslide of non-welded ignimbrite; long-term weathering, which proceeds on the order of years, provides slide material.     

Mechanism for the rapid motion of the Qianjiangping landslide during reactivation by the first impoundment of the Three Gorges Dam reservoir, China

The first impoundment of the Three Gorges Dam reservoir in China started from a water surface elevation of 95 m on June 1, 2003 and reached 135 m on June 15, 2003. Shortly after the water level reached 135 m, many slopes began to deform and some landslides occurred. The Qianjiangping landslide is the largest one; it occurred on the early morning of July 14, 2003 and caused great loss of lives and property. Field investigation revealed that, although failure occurred after the reservoir reached 135 m, the stability of the slope was already reduced by preexisting sheared bedding planes. To study the mechanism of the rapid motion of this reactivated landslide, two soil samples were taken from a yellow clay layer and a black silt layer in the sliding zone, respectively, and a series of ring shear tests were conducted on the samples. One series of ring shear tests simulates the creep deformation behavior, while the other series simulates different shear rates. Conclusions drawn from analysis of the ring shear tests indicate that the mechanism of the rapid motion of the reactivated landslide was caused by the rate effect of the black silt layer during the motion phase after the creep failure. The yellow clay layer did not play any important role in the rapid motion in the 2003 event.     

Extraction of water and solutes from argillaceous rocks for geochemical characterisation: Methods, processes and current understanding

This paper summarises the results of a comprehensive critical review, initiated by the OECD/NEA "Clay Club," of the extraction techniques available to obtain water and solutes from argillaceous rocks. The paper focuses on the mechanisms involved in the extraction processes, the consequences on the isotopic and chemical composition of the extracted pore water and the attempts made to reconstruct its original composition. Finally, it provides some examples of reliable techniques and information, as a function of the purpose of the geochemical study. Electronic Publication     

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

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

天星河、文峰河流域岩溶水化学及影响因素

重庆东北部地区巫溪天星河、文峰河的岩溶流域水化学特征研究结果表明:研究区泉水样品的p H值为6.47~8.28,平均值为7.79;流域河水饱和指数(SIc)的平均值为0.14,表明其变化受到流域碳酸盐岩分布的控制。水化学类型以HCO3-Ca型水为主,Ca2+和HCO-3平均分别占阳、阴离子的75%和82%。通过分析Gibbs图,发现泉水的主要组分属于"岩石风化类型",主要反映了岩石的溶解作用对泉水水化学的影响。流域内部分水样NO-3和SO2-4较高,可能是受工农业生产等人类活动的影响引起,此外硫酸也参与了碳酸盐矿物的溶解。     

The double solid reactant method: II. An application to the shallow groundwaters of the Porto Plain,Vulcano Island (Italy)

This paper presents an example of application of the double solid reactant method (DSRM) of Accornero and Marini (Environmental Geology, 2007a), an effective way for modeling the fate of several dissolved trace elements during water–rock interaction. The EQ3/6 software package was used for simulating the irreversible water–rock mass transfer accompanying the generation of the groundwaters of the Porto Plain shallow aquifer, starting from a degassed diluted crateric steam condensate. Reaction path modeling was performed in reaction progress mode and under closed-system conditions. The simulations assumed: (1) bulk dissolution (i.e., without any constraint on the kinetics of dissolution/precipitation reactions) of a single solid phase, a leucite-latitic glass, and (2) precipitation of amorphous silica, barite, alunite, jarosite, anhydrite, kaolinite, a solid mixture of smectites, fluorite, a solid mixture of hydroxides, illite-K, a solid mixture of saponites, a solid mixture of trigonal carbonates and a solid mixture of orthorhombic carbonates. Analytical concentrations of major chemical elements and several trace elements (Cr, Mn, Fe, Ni, Cu, Zn, As, Sr and Ba) in groundwaters were satisfactorily reproduced. In addition to these simulations, similar runs for a rhyolite, a latite and a trachyte permitted to calculate major oxide contents for the authigenic paragenesis which are comparable, to a first approximation, with the corresponding data measured for local altered rocks belonging to the silicic, advanced argillic and intermediate argillic alteration facies. The important role played by both the solid mixture of trigonal carbonates as sequestrator of Mn, Zn, Cu and Ni and the solid mixture of orthorhombic carbonates as scavenger of Sr and Ba is emphasized.

Groundwater geochemistry of Ain Azel area,Algeria

Hydrogeochemical data for 18 groundwater samples and 11 hydrochemical parameters were subjected to Q- and R-mode cluster analysis and inverse geochemical modeling. Q-mode cluster analysis resulted in three distinct water types (brackish water type, saline water type and highly saline water type). R-mode cluster analysis led to the conclusion that the water–rock interaction is the major source of contamination for the groundwater in the area. Geochemical modeling results show that carbonates, gypsum, halite, carbon dioxide (gas), and chlorite are dissolving, whereas Ca-montmorillonite, gibbsite, illite, K-mica, kaolinite, and quartz are mostly precipitating along different flow paths in the groundwater system of the area.     

Groundwater flow and geochemistry in the lower reaches of the Yellow River: a case study in Shandang Province, China

Water samples were collected from the Yellow River and from wells for chemical and isotopic measurement in the counties of Yucheng and Qihe, to which 6–9×10⁸ m³ of water is diverted annually from the Yellow River. A zone of high electrical conductivity (EC) in groundwater corresponds well on the regional scale with a ridge in groundwater level, which is the main flow path through the region, but has a low gradient. The zone of highest EC along this ridge occurs at a position with the lowest ground altitude in the study area. The unique characteristic of the groundwater is the linear relationship among the principal anions as the result of mixing. The mixing effect is confirmed by its isotopic signature, which was then used to calculate the contributions from three sources: rainfall, old water, and diverted water with an average mixing rate of 18, 17, and 65%, respectively. As an indicator of water movement, Cl^– content varies across a wide range in the profile from 30–10 m with a maximum concentration at about 1.2 m depth. Concentrations are relatively stable at about 2 m, which is the average boundary of the saturated and unsaturated zone. The water from the Yellow River has proved to be dominant in mixing in the aquifer in terms of groundwater flow and geochemistry. Electronic Publication     

Influence of volcanic activity on spring water chemistry at Popocatepetl Volcano, Mexico

The results of the 7 years (1994–2000) of monthly monitoring of spring water before and during eruptions show response to volcanic activity. Low salinity and temperature characterize most of the springs, which are located on the flanks of Popocatepetl Volcano. The pH ranges from 5.8 to 7.8 and temperature from 3 to 36 °C. Oxygen and hydrogen isotopic data show that the water is of meteoric origin, but SO₄²⁻, Cl⁻, F⁻, HCO₃⁻, B, and SO₄²⁻/Cl⁻ variations precede main eruptive activity, which is considered linked to influx of magmatic gases and acid fluids that react with sublimates and host rock and mix with the large water system. Na⁺, Ca²⁺, SiO₂ and Mg²⁺ concentrations in the water also increased before eruptive activity. The computed partial pressure of CO₂ in equilibrium with spring waters shows values higher than air-saturated water (ASW), with the highest values up to 0.73 bar of pCO₂. Boron is detected in the water only preceding the larger eruptions. When present, boron concentration is normally under health standard limits, but in two cases the concentration was slightly above. Other components are within health standard limits, except for F⁻ in one spring.