Natural and anthropogenic factors affecting groundwater quality of an active volcano (Mt. Etna,Italy)

New geochemical data on dissolved major and minor constituents in 276 groundwater samples from Etna aquifers reveal the main processes responsible for their geochemical evolution and mineralisation. This topic is of particular interest in the light of the progressive depletion of water resources and groundwater quality in the area. Multivariate statistical analysis reveal 3 sources of solutes: (a) the leaching of the host basalt, driven by the dissolution of magma-derived CO₂; (b) mixing processes with saline brines rising from the sedimentary basement below Etna; (c) contamination from agricultural and urban wastewaters. The last process, highlighted by increased concentrations of SO₄, NO₃, Ca, F and PO₄, is more pronounced on the lower slopes of the volcanic edifice, associated with areas of high population and intensive agriculture. However, this study demonstrates that natural processes (a) and (b) are also very effective in producing highly mineralised waters, which in turn results in many constituents (B, V, Mg) exceeding maximum admissible concentrations for drinking water.     

The I.A.G.C. interlaboratory water analysis comparison programme

The I.A.G.C. international programme of interlaboratory comparison of water analysis quality involved seven waters, including surface waters, a ground water, an alkaline spring water, a sample ‘spiked’ with heavy metals, and a geothermal water. Forty-eight laboratories in eighteen countries participated.Sample stability was little problem for most major solutes and for minor elements at concentrations greater than tens of ppb. Iron analyses were erratic for some samples, and the stability of nitrogen species was suspect in unsterilized samples. For major constituents in surface waters the results were of reasonable quality but for waters of unusual composition e.g. the geothermal and alkaline spring water, the results were far from satisfactory. Of the common constituents, SO₄, NO₃, F, and SiO₂ showed the greatest range of results. The most consistent results for trace elements at the 10 ppb level were for Be, Cd, Cu, Hg, and Li. Lower quality results (coefficient of variation over 30) were obtained for Fe, As, Mn, Co, Ni, Pb and Zn.     

Major ion chemistry,weathering processes and water quality assessment in upper catchment of Damodar River basin,India

The chemical characteristics of surface, groundwater and mine water of the upper catchment of the Damodar River basin were studied to evaluate the major ion chemistry, geochemical processes controlling water composition and suitability of water for domestic, industrial and irrigation uses. Water samples from ponds, lakes, rivers, reservoirs and groundwater were collected and analysed for pH, EC, TDS, F, Cl, HCO₃, SO₄, NO_3, Ca, Mg, Na and K. In general, Ca, Na, Mg, HCO₃ and Cl dominate, except in samples from mining areas which have higher concentration of SO₄. Water chemistry of the area reflects continental weathering, aided by mining and other anthropogenic impacts. Limiting groundwater use for domestic purposes are contents of TDS, F, Cl, SO₄, NO₃ and TH that exceed the desirable limits in water collected from mining and urban areas. The calculated values of SAR, RSC and %Na indicate good to permissible use of water for irrigation. High salinity, %Na, Mg-hazard and RSC values at some sites limit use for agricultural purposes.     

Water-rock interaction and chemistry of groundwaters from the Canadian Shield

The chemical and isotopic compositions of groundwaters in the crystalline rocks of the Canadian Shield reflect different degrees of rock-water interactions. The chemistry of the shallow, geochemically immature groundwaters and especially of the major cations is controlled by local rock compositions, whereby dissolution reactions dominate. Conservative constituents, such as chloride and bromide, however, are not entirely a result of such reactions but appear to be readily added from leachable salts during the initial stages of the geochemical evolution of these waters. Their concentration changes little as major cations increase, until concentrations of Total Dissolved Solids (TDS) reach 3000 to 5000 mg 1^?1. The isotopic composition of these shallow waters reflects local, present day precipitations.In contrast to the shallow groundwaters, the isotopic and chemical compositions of the deep, saline waters and brines are determined by extensive, low-temperature rock-water interactions. This is documented in major ion chemistries, ¹⁸O contents and strontium isotopic compositions. These data indicate that the deep brines have been contained in hydrologically isolated “pockets”. The almost total loss of primary compositions make discussions on the origin of these brines very speculative. However, all brines from across the Canadian Shield have a very similar chemical composition, which probably reflects a common geochemical history. The concentrations of some major and most minor elements in these fluids appear to be governed by reactions with secondary mineral assemblages.     

Hydrogeochemical analysis on Italian bottled mineral waters: Effects of geology

The use of bottled mineral waters use is increasingly becoming popular and the need for better knowledge of their chemical composition is a key issue for defining their quality, particularly for those elements that are not monitored on a regular basis. The link between geology and water chemistry is well known and can lead to extreme differences in element distribution and is an issue that needs to be addressed. Such an opportunity has been provided by a project of the EuroGeoSurvey Geochemistry Expert Group aimed at the characterization of groundwater geochemistry using bottled mineral waters purchased in supermarkets all over Europe. On these waters pH, conductivity and concentrations of 69 elements and ions were measured at the BGR geochemical laboratories. On a total of 1785 “samples”, 158 represent waters bottled in Italy in 126 different sites scattered throughout the country. Most of the purchased mineral water is packaged in PET bottles. In this paper, the dataset concerning Italy has been used to provide an overview on the relationship between natural concentration of the determined chemical elements in groundwater and geo-lithological features. These relationships have been investigated mostly taking into account the surface geology and other information available on water sources. Application of R-Mode factor analysis to the data set allowed the determination of the possible relationship between the distribution of individual elements and lithology or other surface enrichment phenomena. In particular waters draining through volcanic rocks are enriched in elements such as As, B, Br⁻, Cl⁻, Cs, I, K, Li, Na, NO₃⁻, PO₄³⁻, Rb, Sc, SiO₂, Sr, Te, Ti, and V up to 3 orders of magnitude higher than waters draining through other lithologies. REE and Y show significant difference in median concentration due to interaction of waters with plutonic rocks. Many elements have a large spread of concentrations, which reflects natural variations and interaction with particular lithologies. One of the five R-mode factor analysis associations, recognized as being representative of elements analysed shows high nitrate and V loadings along with As, PO₄³⁻ and Se. The latter association probably reflects a sign of anthropogenic contribution in some aquifers in volcano-sedimentary or silico-clastic deposits and in intensively cultivated areas.     

Water quality assessment in Akpabuyo, Cross River basin, South-Eastern Nigeria

 A baseline study involving analyses of surface and subsurface water samples from the Akpabuyo area was carried out in order to assess their suitability for drinking, domestic and agricultural purposes. Study results show that the waters are acidic (3.41≤pH≤6.28), soft (hardness 2.09–10.68 mg/l as CaCO₃), fresh (conductivity <1400 μs/cm) and characterised by low sodium adsorption ratio, SAR (0.08–0.59). In addition, the mean values of the major cations (Ca²⁺, Mg²⁺, Na⁺, K⁺) and anions (SO₄ ^2–, Cl^–, HCO₃ ^–) are all within the World Health Organisation (WHO) standards. Taking all this into consideration (except pH), the waters may be regarded as excellent for drinking, domestic and agricultural purposes. On the basis of regression equations, the major cations (K, Na, Ca, Mg) correlate well with conductivity. Finally, results also show that four chemical facies are delineated. These include Ca-Cl, Na-Cl, Ca-SO₄ and Ca-HCO₃. Received: 19 June 1996 / Accepted: 15 April 1997     

The mobility of radium-226 and trace metals in pre-oxidized subaqueous uranium mill tailings

The exchange of ²²⁶Ra and trace metals across the tailings-water interface and the mechanisms governing their mobility were assessed via sub-centimetre resolution profiling of dissolved constituents across the tailings–water interface in Cell 14 of the Quirke Waste Management Area at Rio Algom's Quirke Mine, near Elliot Lake, Ontario, Canada. Shallow zones (<1.5 m water depth) are characterized by sparse filamentous vegetation, well-mixed water columns and fully oxygenated bottom waters. Profiles of dissolved O₂, Fe and Mn indicate that the tailings deposits in these areas are sub-oxic below tailings depths of ∼3 cm. These zones exhibit minor remobilization of Ra in the upper 5 cm of the tailings deposit; ²²⁶Ra fluxes at these sites are relatively small, and contribute negligibly to the water column activity of ²²⁶Ra. The shallow areas also exhibit minor remobilization of Ni, As, Mo and U. The release of these elements to the water cover is, however, limited by scavenging mechanisms in the interfacial oxic horizons. The presence of thick vegetation (Chara sp.) in the deeper areas (>2 m water depth) fosters stagnant bottom waters and permits the development of anoxia above the benthic boundary. These anoxic tailings are characterized by substantial remobilization of ²²⁶Ra, resulting in a relatively large flux of ²²⁶Ra from the tailings to the water column. The strong correlation between the porewater profiles of ²²⁶Ra and Ba (r²=0.99), as well as solubility calculations, indicate that the mobility of Ra is controlled by saturation with respect to a poorly ordered and/or impure barite phase [(Ra,Ba)SO₄]. In the anoxic zones, severe undersaturation with respect to barite is sustained by microbial SO₄ reduction. Flux calculations suggest that the increase in ²²⁶Ra activity in the water cover since 1995 (from <0.5 to 2.5 Bq l⁻¹) can be attributed to an increase in the spatial distribution of anoxic bottom waters caused by increased density of benthic flora. The anoxic, vegetated areas also exhibit minor remobilization with respect to dissolved As, Ni and Zn. The removal of trace metals in the anoxic bottom waters appears to be limited by the availability of free sulphide. Collectively, the data demonstrate that while the water cover over the U mill tailings minimizes sulphide oxidation and metal mobility, anoxic conditions which have developed in deeper areas have led to increased mobility of ²²⁶Ra.     

An integrated approach to assess the quality of groundwater in a coastal aquifer of Andhra Pradesh, India

The Narava basin in Visakhapatnam district situated on the east coast is a productive agricultural area, and is also one of the fastest growing urban areas in India. The agricultural and urban-industrialization activities have a lot of impact on this coastal aquifer water quality. The hydrochemistry of the groundwater was analyzed in the basin area with reference to drinking and agricultural purposes. The area is underlain by Precambrian rocks like khondalites, charnockites and migmatites. The water samples were collected from shallow wells for the year 2008. Physical and chemical parameters of groundwater such as pH, total alkalinity (TA), electrical conductivity (EC), total dissolved solids (TDS), total hardness (TH), Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, Cl^?, SO₄ ^2?, NO₃ ^?, F^? were determined. The analytical results revealed that the most of the groundwater found to be in polluted category. Geographical information system (GIS) was utilized to generate different spatial distribution maps of various chemical constituents in the study area. The analytical data were used to compute certain parameters such as salinity hazard, percent sodium (Na%), sodium adsorption ratio (SAR), residual sodium carbonate (RSC), permeability index (PI), Kelley??s ratio (KR) and corrosivity ratio (CR) to determine the quality of water for agricultural purposes. The abundance of the major ions in the basin area was found to be in the following sequence: Na⁺?>?Ca²⁺?>?Mg²⁺?>?K⁺:Cl^??>?HCO₃ ^??>?SO₄ ^2??>?NO₃ ^??>?F^?. According to Gibbs?? diagram most of the samples fall under rock dominance. As per Wilcox and USSL classification most of the groundwater samples are suitable for irrigation except few samples which are unsuitable due to the presence of high salinity and high sodium hazard. From the obtained data, it can be concluded that the water quality profile was good and useful for normal irrigation agriculture.     

Chemical mass transfer in the Rio Tanama system,west-central Puerto Rico

Equilibrium relationships are defined between stream waters and weathering products, kaolinite and calcium montmorillonite, for the Rio Tanama system, west-central Puerto Rico. The major element composition of 46 water samples of springs and streams define a reaction path in the system CaO-Na₂O-MgO-Al₂O₃-SiO₂-H₂O between acid waters containing low concentrations of alkali cations and detrital reactant minerals. The principal reactant phases appear to be chlorite, plagioclase and orthoclase and occasionally anhydrite or calcite. Headward erosion by the Rio Tanama supplies the reactant phases to the stream silt load.The chemical denudation rate calculated for the Rio Tanama system is about 30 m/million yr. The chemical stream load appears to be buffered by the product phases in the main river over the 15–20 km river length sampled in this study.The silt and soil mineralogy and water compositions are used to define a log K for the hydrolysis of Ca-montmorillonite at 25°C of 35.0 ± 0.8. This value is in reasonable agreement with the value of 37.1 ± 1.0 defined by Garrels and Mackenzie (1967) in a similar manner for spring waters in the Sierra Nevada.     

A study on the impact of weathering in groundwater chemistry of a hard rock aquifer

Hydrogeochemistry of groundwater in hard rock terrain are mainly governed by lithology and land use practices. A study area near Madurai region of central Tamil Nadu was selected with various litho-units and a hard rock sedimentary contact with an unconformity. Land use practices in these regions are also varied with lithology. The study was conducted by collecting 54 groundwater samples spatially covering the major litho-units. Collected samples were analyzed for electrical conductivity, pH, total dissolved solids (TDS), temperature, Ca, Mg, Na, K, Cl, HCO₃, NO₃, H₄SiO₄, PO₄, and SO₄. The results of the samples analyzed found to vary spatially. Dominance of ion shows that the alkalies are predominant and HCO₃ is the dominant anion. Piper facies show that the samples are alkali-carbonate type indicating the predominance of weathering. Most of the parameters exceed the drinking water permissible limit. Standard plots and statistical analysis also indicate weathering as the major process governing the hydrogeochemistry of the groundwater in the region. Relative mobility of cations indicates that the rate of liberation of alkalies from the lithology is more prominent.     

Effect of the depositional environment on the compositional variations among the phosphorite deposits in Egypt

Late Cretaceous economic phosphorites from the Red Sea, Nile Valley, and Abu Tartur areas, Egypt, show distinct variations in the lithology of associated sediments, mineralogy of nonphosphatic constituents, and distributions of major and trace elements. In the Red Sea area, the phosphorite beds are intercalated with laminated black shales, and the nonphosphatic constituents are detrital quartz and calcite, ankerite, and pyrite cements. In the Nile Valley, the phosphorite beds are intercalated with chert, marl, and sandstone and the nonphosphatic constituents are detrital quartz and calcite and chalcedony cements. In the Abu Tartur Plateau, the phosphorite beds are intercalated with laminated black shales, and the nonphosphatic constituents are detrital quartz and ankerite and pyrite cements. The phosphorites studied also show distinct variations in major- and trace-element concentrations. The Abu Tartur phosphorites have higher contents of TiO₂, Al₂O₃, Fe₂O₃, K₂O, Co, Nb, Pb, Sr, Th, Y, and Zr and lower SiO₂, Ba, and U contents as compared to those in the Red Sea and Nile Valley areas. The positive correlations between Al₂O₃ and TiO₂, K₂O, Nb, Y, and Zr suggest the detrital origin of these constituents.Similarity in the phosphatic constituents, which were derived from outside the depositional sites, and variations in the lithology of associated sediments and the mineralogy and geochemistry of the nonphosphatic constituents, which reflect the conditions at the depositional sites, suggest that the variations in the depositional environment of the phosphorites are the potential controlling factor of the compositional variations among these phosphorites. The abundance of black shales in the Red Sea and Abu Tartur areas, as well as the occurrence of ankerite and pyrite as cementing materials for the phosphatic constituents, might reflect reducing conditions in these areas, while the abundance of siliciclastic sediments and calcite and chalcedony cements suggests oxidizing conditions in the Nile Valley. The reducing conditions in the Red Sea and Abu Tartur areas were probably developed within the pre-existing depressions in a shelf environment. These depressions might have formed as a result of a change in the movements of the North Atlantic, Eurasian, and African Plates during the late Santonian, which led to transgressive inversion of rifts along northern Egypt and consequent folding in the continental interior. The higher contents of detrital components in the Abu Tartur phosphorites compared to the Red Sea and Nile Valley areas suggest more detrital inputs during the deposition of the phosphorites in Abu Tartur. The products of the diagenesis and weathering of these deposits also reflect the variations in the depositional conditions.     

Geochemistry of mud volcano fluids in the Taiwan accretionary prism

Taiwan is located at the collision boundary between the Philippine Sea Plate and the Asian Continental Plate and is one of the most active orogenic belts in the world. Fluids sampled from 9 sub-aerial mud volcanoes distributed along two major geological structures in southwestern Taiwan, the Chishan fault and the Gutingkeng anticline, were analyzed to evaluate possible sources of water and the degree of fluid-sediment interaction at depth in an accretionary prism. Overall, the Taiwanese mud volcano fluids are characterized by high Cl contents, up to 347 mM, suggesting a marine origin from actively de-watering sedimentary pore waters along major structures on land. The fluids obtained from the Gutingkeng anticline, as well as from the Coastal Plain area, show high Cl, Na, K, Ca, Mg and NH₄, but low SO₄ and B concentrations. In contrast, the Chishan fault fluids are much less saline (1/4 seawater value), but show much heavier O isotope compositions (δ¹⁸O=5.1–6.5 ‰). A simplified scenario of mixing between sedimentary pore fluids and waters affected by clay dehydration released at depth can explain several crucial observations including heavy O isotopes, radiogenic Sr contents (⁸⁷Sr/⁸⁶Sr=0.71136–0.71283), and relatively low salinities in the Chishan fluids. Gases isolated from the mud volcanoes are predominantly CH₄ and CO₂, where the CH₄–C isotopic compositions show a thermogenic component of δ¹³C=−38 ‰. These results demonstrate that active mud volcano de-watering in Taiwan is a direct product of intense sediment accretion and plate collision in the region.     

Evaluation of soil salinization in a Mediterranean site (Agoulinitsa district—West Greece)

Soil salinization is an environmental problem having significant impacts on the soil–water–plant system. This problem is more frequent in coastal areas due to seawater intrusion into the land. Assessing the soil salinization is a critical issue for the agricultural areas situated in the Mediterranean basin. This paper examines the deterioration of soil quality in the cultivated land of a Mediterranean site (Agoulinitsa district—West Greece). Soil samples were collected in both pre-irrigation and post-irrigation seasons. Electrical conductivity (EC), pH and the ions Br^?, Ca²⁺, Cl^?, F^?, K⁺, Li⁺, Mg²⁺, Na⁺, NH₄ ⁺, NO₂ ^?, NO₃ ^?, PO₄ ^3? and SO₄ ^2? were determined by the 1:2 (soil/water ratio on weight basis) method. The salts which were present in both seasons in the soils of the area studied are KCl, MgCl₂, NaCl, CaSO₄ and K₂SO₄. The wide spatiotemporal variation of EC in the cultivated land in both seasons demonstrates that soil salinity is controlled mainly by seawater intrusion and anthropogenic factors such as the application of salt-rich water which is directly pumped from the drainage ditches. Seawater intrusion provides the affected soil with elevated contents of Ca²⁺, Cl^?, K⁺, Mg²⁺, Na⁺ and SO₄ ^2?. Classification of the soils by using criteria given by the literature is discussed. Practices to prevent, or at least ameliorate, salinization in the cultivated land of Agoulinitsa district are proposed.     

Chemical equilibria in the thermal spring waters of Virginia

The composition of waters from 10 thermal springs located in western Virginia near the 38th parallel lineament have been analysed for major dissolved components and for Sr, Fe, Cu, Zn and Cd; from these analyses, free ion activities have been calculated. The temperatures of the springs range from 17° to 39°C, the heat apparently being derived simply from deep circulation along synclinal, Middle Ordovician limestones. More than 95 per cent of the dissolved solids consist of Ca²⁺, Mg²⁺ HCO₃^?, and SO₄^2?. The concentrations of these components, as well as the spring temperatures, have not changed appreciably in 140 yr in some springs. The waters that have temperatures below 25° are all undersaturated with respect to calcite and dolomite, possibly because they have been contaminated by shallow ground waters. The waters with temperatures above 25° are in equilibrium with calcite and dolomite. Furthermore, in this latter group, the calcium-sulfate activity product and the sulfate-carbonate activity ratio are nearly constant, even though the waters are under saturated with respect to gypsum, anhydrite, celestite and strontianite. This can be explained if CaSO⁴ is coprecipitated in a mineral such as aragonite. The waters have absorbed some dissolved oxygen near the surface, but at depth they may be anoxic with Eh controlled by the oxidation of pyrite to goethite. The extremely low chloride concentrations of these waters clearly distinguish them from the brines which deposited Mississippi Valley and Appalachian type epithermal ore deposits.     

A geochemical study of the impact of irrigation and aquifer lithology on groundwater in the Upper Yakima River Basin,Washington, USA

The Yakima River, a major tributary of the Columbia River, is currently overallocated in its surface water usage in part because of large agricultural water use. As a result, groundwater availability and surface water/groundwater interactions have become an important issue in this area. In several sub-basins, the Yakima River water is diverted and applied liberally to fields in the summer creating artificial recharge of shallow groundwater. Major ion, trace element, and stable isotope geochemistry of samples from 26 groundwater wells from a transect across the Yakima River and 24 surface waters in the Kittitas sub-basin were used to delineate waters with similar geochemical signatures and to identify surface water influence on groundwater. Major ion chemistry and stable isotope signatures combined with principal component analysis revealed four major hydrochemical groups. One of these groups, collected from shallow wells within the sedimentary basin fill, displays temporal variations in NO₃ and SO₄ along with high δ¹⁸O and δD values, indicating significant contribution from Yakima River and/or irrigation water. Two other major hydrochemical groups reflect interaction with the main aquifer lithologies in the basin: the Columbia River basalts (high-Na groundwaters), and the volcaniclastic rocks of the Ellensburg Formation (Ca–Mg–HCO₃ type waters). The fourth major group has interacted with the volcaniclastic rocks and is influenced to a lesser degree by surface waters. The geochemical groupings constrain a conceptual model for groundwater flow that includes movement of water between underlying Columbia River basalt and deeper sedimentary basin fill and seasonal input of irrigation water.     

Nitrates as indicators of aquifer interconnection. Application to the Campo de Dalías (SE – Spain)

 Relatively high concentrations of NO₃ usually have their origin in processes of organic pollution and excessive use of inorganic fertilizers. In the case of agricultural areas, these activities may generate great quantities of nitrates. This fact has enabled us to use the nitrate ion to characterize an exploited aquifer unit of a very complex aquifer system, as is the case for the Campo de Dalías aquifer system (SE Spain). The shallow boreholes, which draw water from intensively cultivated superficial formations, yield waters with a high NO₃ content. When the boreholes are deeper and penetrate low-permeability formations in the superficial layers, the waters contain little NO₃; similar to what happens in areas of recharge where agricultural activities are absent. In addition, using longitudinal sections, it is possible to demonstrate the possible existence of connections between superficial and deep aquifers using NO₃ as a tracer. Similarly one can locate those sectors responsible for contamination caused by the poorly lined boreholes themselves, when they perforate more than one aquifer in a multiple aquifer formation. Received: 22 December 1998 · Accepted: 20 March 1999     

Origin of Cenomanian nodular phosphorites in the Dnieper-Donets Depression: Geochemical aspect of the problem

The results of the study of bioecological and geochemical sedimentation conditions in the Cenomanian basin are presented. Close relation between phosphogenesis and formation of organic-rich clays and black shales is demonstrated. It is shown that phosphorite nodules and phosphate plates in Cenomanian sands formed at acid-base barriers related to the squeezing of acid phosphorus-containing interstitial waters from the sand-underlying clays and the conservation of alkaline marine bottom waters in sands. The proposed new phosphorite formation model reflects the input of large amounts of P₂O₅ from land, its precipitation by planktonic organisms and concentration in black shales and clays, the mobilization and accumulation of phosphorus in interstitial waters, and its postdiagenetic redistribution in sands and their erosion zones. It is emphasized that phosphogenesis is associated with synsedimentary folding in the Cenomanian basin.     

Acidification processes and soil leaching influenced by agricultural practices revealed by strontium isotopic ratios

In natural river systems, the chemical and isotopic composition of stream- and ground waters are mainly controlled by the geology and water-rock interactions. The leaching of major cations from soils has been recognized as a possible consequence of acidic deposition from atmosphere for over 30 years. Moreover, in agricultural areas, the application of physiological acid fertilizers and nitrogen fertilizers in the ammonia form may enhance the cation leaching through the soil profile into ground- and surface waters. This origin of leached cations has been studied on two small and adjacent agricultural catchments in Brittany, western France. The study catchments are drained by two first-order streams, and mainly covered with cambisoils, issued from the alteration and weathering of a granodiorite basement. Precipitations, soil water- and NH₄ acetate-leachates, separated minerals, and stream waters have been investigated. Chemical element ratios, such as Ba/Sr, Na/Sr and Ca/Sr ratios, as well as Sr isotopic ratios are used to constrain the relative contribution from potential sources of stream water elements.Based on Sr isotopic ratio and element concentration, soil water- and NH₄ acetate leaching indicates (1) a dominant manure/slurry contribution in the top soil, representing a cation concentrated pool, with low ⁸⁷Sr/⁸⁶Sr ratios; (2) in subsoils, mineral dissolution is enhanced by fertilizer application, becoming the unique source of cations in the saprolite. The relatively high weathering rates encountered implies significant sources of cations which are not accessory minerals, but rather plagioclase and biotite dissolution.Stream water has a very different isotopic and chemical composition compared to soil water leaching suggesting that stream water chemistry is dominated by elements issued from mineral and rock weathering. Agriculture, by applications of chemical and organic fertilizers, can influence the export of major base cations, such as Na⁺. Plagioclase dissolution, rather than anthropogenically controlled soil water, seems to be the dominant source of Na⁺ in streams. However, Ca²⁺ in streams is mostly derived from slurries and manures deposited on top soils, and transferred into the soil ion-exchange pool and stream waters. Less than 10% of Na⁺, 5-40% of Sr²⁺ and 20-100% of Ca²⁺ found in streams can be directly derived from the application of organic fertilizers.     

Geochemical behavior and speciation modeling of rare earth elements in acid drainages at Sarcheshmeh porphyry copper deposit,Kerman Province,Iran

Acid mine drainage is a major source of water pollution in the Sarcheshmeh porphyry copper mine area. The concentrations of heavy metals and rare earth elements (REEs) in the host rocks, natural waters and acid mine drainage (AMD) associated with mining and tailing impoundments are determined. Contrary to the solid samples, AMDs and impacted stream waters are enriched in middle rare earth elements (MREEs) and heavy rare earth elements (HREEs) relative to light rare earth elements (LREEs). This behavior suggests that REE probably fractionate during sulfide oxidation and acid generation and subsequent transport, so that MREE and HREE are preferentially enriched. Speciation modeling predict that the dominant dissolved REE inorganic species are Ln³⁺, Ln(SO₄)₂⁻, LnSO₄⁺, LnHCO₃²⁺, Ln(CO₃)₂⁻ and LnCO₃⁺. Compared to natural waters, Sarcheshmeh AMD is enriched in REEs and SO₄²⁻. High concentrations of SO₄²⁻ lead to the formation of stable LnSO₄⁺, thereby resulting in higher concentrations of REEs in AMD samples. The model indicates that LnSO₄⁺ is the dissolved form of REE in acid waters, while carbonate and dicarbonate complexes are the most abundant dissolved REE species in alkaline waters. The speciation calculations indicate that other factors besides complexation of the REE's, such as release of MREE from dissolution and/or desorption processes in soluble salts and poorly crystalline iron oxyhydroxy sulfates as well as dissolution of host rock MREE-bearing minerals control the dissolved REE concentrations and, hence, the MREE-enriched patterns of acid mine waters.     

Hydrogeochemistry of the groundwater flow system in a crystalline terrain: a study from the Kurunegala district,Sri Lanka

Water samples collected from dug wells and tube wells from the Kurunegala District of Sri Lanka have been studied for their major hydrogeochemical parameters to understand the chemical quality of water in the terrain. The region is composed of Precambrian metamorphic rocks where groundwater is only available in the regolith and along weak structural discontinuities. The study of the major chemical constituents of groundwater revealed several relationships with the aquifer lithology. Groundwater from mafic rocks have high dissolved solids, while quartzose metaclastic rocks yield water with low dissolved solids. The study area displays very low SO₄ ²⁻ contents of the groundwater. The chloride content is higher in the dry regions and in terrains underlain by pink granite and marble/calc gneiss while areas with marble, as expected, show high concentrations of Ca and Mg ions. The waters in the region can be classified into non-dominant cations to Na + K dominant and Cl⁻ and HCO₃ ⁻ dominant types. Water from charnockite-bearing areas tends to have non-dominant cations and more CO₃ ²⁻ + HCO₃ ⁻ types. Effects such as soluble salts in the regolith, fracture intensity and climatic variations play a significant role in the behavior of the hydrogeochemistry in the area.