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Natural mineral waters (NMWs) emerge from the earth as springs and their beneficial therapeutic effect has been empirically recognized in different countries. Portugal has diverse NMW resources that are sought for the relief of different afflictions including dermatological complications. However, there is a lack of scientific validation supporting this empiric knowledge. In this study, we aimed to screen the in vitro bioactivity of Portuguese NMWs with different chemical profiles, namely sulfurous/bicarbonate/sodic (SBS), bicarbonate/magnesium, sulfated/calcic, sulfurous/chlorinated/sodic, sulfurous/bicarbonate/fluoridated/sodic, and chlorinated/sodic, focusing on aging-related skin alterations. Mouse skin fibroblasts and macrophages were exposed to culture medium prepared in different NMWs. Cellular viability was evaluated by MTT assay and etoposide-induced senescence was analyzed through the beta-galactosidase staining kit. Wound healing was investigated by the scratch assay, and phototoxicity/photoprotection after UVA irradiation was evaluated using a neutral red solution. ROS production was quantified using the 2′7′-dichlorofluorescin diacetate dye, and the activity of superoxide dismutase (SOD) was analyzed by a commercial kit after lipopolysaccharide exposure. NMWs within the SBS profile demonstrated anti-senescence activity in skin fibroblasts, along with a variable effect on cellular viability. Among the tested NMWs, two decreased cellular senescence and preserved cell viability and were therefore selected for subsequent studies, together with a SBS NMW with therapeutic indications for dermatologic diseases. Overall, the selected NMW promoted wound healing in skin fibroblasts and activated SOD in macrophages, thus suggesting an anti-oxidant effect. None of the NMWs prevented phototoxicity after UV irradiation. Our results shed a light on the anti-aging potential of Portuguese NMW, supporting their putative application in cosmetic or medical products. [ABSTRACT FROM AUTHOR]

Water and mineral components dissolved in it play an important role in nutrition. Fluoride in drinking water, besides arsenic and nitrate, is reported as chemical causing widespread health effects in humans as a consequence of exposure when present in excessive quantities. Due to significant impact of fluoride on human health and differentiation concentration in water depending on many chemical and geological factors, we decided to establish the fluoride content in Polish bottled waters. In this study, forty commercially available mineral and spring bottled waters, sold under various brand names in Poland have been analysed. The used ion chromatographic method was validated in the range 0.04–2.0 mg L−1 and verified with certified reference material. The obtained results were compared with contents declared by producer, some world standards and results reported by other investigators. Validation of the method showed a good within run repeatability, stability and accuracy. The limit of detection (LOD) in our research was found to be 0.016 mg L−1, while the limit of quantification amounts to 0.049 mg L−1. Content of fluoride in 40 studied bottled waters was higher in mineral (24 samples, 0.302 ± 0.291 mg L−1) than in spring waters (16 samples, 0.159 ± 0.072 mg L−1), but only in one tested mineral water (No 39, Java, with pH 9.16) slightly exceeded the permission level for infant consumption (1.5 mg L−1) and amounted to 1.566 ± 0.0188 mg L−1. No bottled water exceeded the permitted norm. The measured fluoride concentration was in line with these declared on product label, it means difference in less than ±20%, only in 47% of tested waters. The concentration of fluoride was negatively correlated with pH values of waters. In comparison to other countries, the Polish bottled waters characterized low content of fluoride (mean 0.240 ± 0.237 mg F− L−1). The measured value of fluoride contents [mg L−1] in mineral and spring Polish bottled waters with regard to possible health effects (adapted from (Abouleish, 2016)). Unlabelled Image • Fluoride content in forty mineral and spring waters originated from Poland • IC method was validated in range 0.04–2.00 mg L−1 and verified with CRM • Comparison between measured and declared by manufacturer contents • Survey of permission levels in other countries and organization • Review of literature date about fluoride content in worldwide waters [ABSTRACT FROM AUTHOR]

This work focuses on drawing up the hydrochemical profile of water samples collected in five springs of the Tijuco stream. The evaluation was based on quantification of the elements Al, As, Ba, Be, B, Ca, Cd, Co, Cr, Li, Pb, Cu, Fe, Mg, Mn, Mo, Ni, Se, Si, Sb, U, V, and Zn; the anions F-, Cl-, NO2-, NO3- SO42-; the cations Na+, NH4+ e K+ and the parameters: turbidity, temperature, conductivity, total dissolved solids, oxidation-reduction potential, pH and dissolved oxygen. Alkalinity, hardness, Cr (VI) and dry weight (180° C) were also quantified. The analyzed parameters were compared with the Maximum Values (VMP) established by the resolutions n° 396/2008 of CONAMA and n° 2.914/2011 of the Ministry of Health. Most of the parameters presented a good agreement with the VMP, however, due to the parameters turbidity, pH, nitrate, and manganese exceed the VMP in some samples, these waters can only be used for human consumption after previous treatment. However, they can be used in animal watering, irrigation and recreation. The waters were classified into three groups: calcium-bicarbonate, sodium-bicarbonate and mixed-bicarbonate. [ABSTRACT FROM AUTHOR]

This study presents the results of the coupled hydrogeochemical modeling of the geochemical compositions of spring and borehole waters from the Ringelbach catchment, which is located in the Vosges Mountains (France). This site has been equipped with 150-m-deep boreholes, facilitating the sampling of both rock and groundwater in the granitic bedrock. The data point to very contrasting chemical compositions between spring and borehole waters, which are discussed and explained in this study by the application of the coupled hydrogeochemical code KIRMAT. Using hydrological and geochemical data, simulations were performed through two different water pathways, which crossed different types of rocks within the Ringelbach massif: a subsurface and fast (>2.5 m H2O .yr −1 ) water flow, which is more or less parallel to the slope, for waters supplying the springs, and a rather vertical and slower flow (0.5–0.1 m H2O .yr −1 ) for the borehole waters. The KIRMAT simulations make it possible to account for not only the geochemical differences between the spring and borehole waters but also the geochemical variations observed in waters in both contexts. For borehole waters, the model confirms the importance of the dissolution of minor mineralogical phases that are present in the granite (here, carbonates/dolomites) on the chemical budget of waters. It also shows that the chemical differences between the waters collected in the two studied boreholes result from differences in the water flow in the granitic bedrock, i.e., the difference between water flow in a regular porous medium and water flow in a porous medium crossed by a fracture. This result likely highlights the role of geological inheritance on the hydrodynamical rock properties and the chemical compositions of waters circulating within the granitic bedrock. For spring waters, this model enabled us to constrain the nature of the rock in the pathway, which is neither saprolite nor fresh granite but is instead weathered granite with a weathering age of several tens of thousands of years. Spatial and seasonal variations in the chemical compositions of spring water can be explained as the result of the same circulation pattern for which the water-rock interaction time is determined by the length of the pathway and the water velocity. Especially in cases in which this interaction time is long enough, the precipitation of clay phases is enabled, which plays a major role in determining the chemical composition of the water. Despite the only one-dimensional approach and the uncertainties linked to the geochemical complexity and the associated kinetic data, the results obtained in this study demonstrate the effectiveness of using coupled hydrogeochemical modeling to better understand and quantify the weathering processes and the coupling that exists between water circulation dynamics and water-rock interactions at the catchment scale. [ABSTRACT FROM AUTHOR]

This paper describes a hydrochemical study focusing spas groundwaters occurring at São Paulo and Minas Gerais states, Brazil, that are extensively used for drinking in public places, bottling and bathing purposes, among other. The water samples (75) for this study were taken from springs and pumped tubular wells drilled at different aquifer systems that are inserted in Paraná and Southeastern Shield hydrogeological provinces. The data acquisition for temperature, electrical conductivity (EC), pH, redox potential (Eh), dissolved gases (O 2 , CO 2 and H 2 S) and alkalinity was in situ performed for avoiding losses and modification due to transportation. The total dissolved solids (TDS) concentration was evaluated by gravimetry, the major cations and anions, iron and silica by colorimetry/atomic absorption spectrophotometry (AAS), and fluoride by potentiometry. The acquired database allowed establish the principal trends among the parameters analyzed after assuring its consistence from expected relationships found in hydrogeochemical surveys. The groundwaters are reducing (from pH and Eh data), there is a direct TDS-EC relationship, implying on a significant correlation between their ionic strength (IS) and EC. The major ions justifying such trends were sodium, (bi)carbonate, chloride, sulfate and phosphate that also correlated positively with the IS. The spas groundwaters were classified according to the guidelines of the Brazilian Code of Mineral Waters (BCMW) and EU directive for mineral waters. The major hydrochemical facies were also determined, as well the main sources influencing the groundwater composition and possible subsurface temperatures. [ABSTRACT FROM AUTHOR]

The variations in strontium (Sr) isotope ratios in river waters at a regional scale are usually discussed in terms of lithological diversity constituting the watershed bedrock. To discuss the origin of the spatiotemporal variations in Sr concentrations and isotopic compositions of spring waters at the headwater watershed scale, we analyzed the 87Sr/86Sr and 143Nd/144Nd isotopic ratios of the main constitutive minerals of the granitic bedrock of the Strengbach Critical Zone Observatory (CZO) and developed coupled hydrogeochemical modeling integrating the Sr concentration and isotopic composition. The simulation results show that the long-term (1990–2010) decrease in Sr concentrations in the CS springs of the Strengbach catchment can be explained by the response of mineral weathering along the water pathway to the pH increase that affected the incoming solutions to the weathering system during the same period. This pH increase reduces the water path proportion marked by a high flux of apatite and biotite dissolution. Thus, it reduces the Sr concentration of the outgoing spring waters. The different responses of the various CS springs to the incoming solutions' pH increase can be explained by the more or less long residence time of the water in the bedrock for the different springs. The analytical data also confirm that the 87Sr/86Sr isotope ratios of the CS springs varied little or not at all on average from 1990 to 2010. In contrast, they varied significantly during a hydrological cycle and from one spring to another. The constancy of the average 87Sr/86Sr isotope ratios over several years is explained by a granitic bedrock water path sufficiently long for soil solution pH variations to no longer influence the emergence of the spring. The simulation results also show that the isotopic variations observed in the CS springs during a hydrological cycle can be explained by differences in the transit time of the water in the substratum between high and low waters and the modifications that they entail on the degree of saturation of the water with respect to biotite and apatite. These differences do not need to be explained by differences in the mineralogy of the rocks drained by waters between high and low discharge periods. Similarly, the different average isotope ratios from one spring to another can be explained by the more or less long transit times in the bedrock of the waters feeding these different springs. Again, it is not necessary to explain them by local lithological differences from one spring to another. These different results highlight that at the scale of an upstream basin such as the Strengbach, the Sr isotopic variations observed in the CS springs should not systematically indicate lithological differences in the rock. The development of coupled isotope modeling approaches should help to disentangle the part of this process relating to hydrological processes in the isotopic variability of the spring waters. [ABSTRACT FROM AUTHOR]

Abstract: Major element concentrations and U and Sr isotope ratios were determined in waters collected from the main springs located in the small (0.36km2) Ringelbach catchment (Vosges, France), which has a basement consisting of Hercynian granite capped in its upper part by a residual cover of Triassic sandstones. The spring waters were sampled from 2001 to 2004 during highly contrasting hydrological conditions and monthly over two hydrological years October 2004–September 2006. Deep-water samples were also collected from three boreholes (two drilled down to a 150m depth and one down to a depth of 70m) and analyzed. The data indicate systematic geochemical differences between the waters from sandstone and granite and important spatial variations in the chemical and isotopic compositions (Sr and U) between the spring waters on granitic lithology. For the granitic spring waters, the alkalinity, the cationic concentrations and the pH values increase with decreasing spring elevation. The (234U/238U) activity ratios of the granitic spring waters also increase with decreasing spring elevation, from approximately 1 in the upslope springs to 1.3 in the downslope springs. Waters of each spring have significant temporal variations in the elemental concentrations and elemental ratios but much less variations in their Sr isotopic ratios and U activity ratios. These spatial and temporal geochemical variations are unrelated to both the mixing scenarios between weathering and rainwater end-members and between granitic and sandstone weathering fluxes. Moreover, the comparison of the geochemical and isotopic compositions of Sr and U of the granitic spring waters with those of deep waters collected from boreholes demonstrates that the geochemical variations in the granitic spring waters cannot be explained by mixing between the surface water and these deep groundwaters. The spring waters are supplied by subsurface waters flowing through water paths disconnected from those of the borehole waters. Furthermore, the geochemical and Sr isotopic characteristics of the granitic spring waters suggest that the different granitic springs are most likely supplied by waters with relatively independent water pathways that are controlled by the geometry of the fracture network structure in the Ringelbach regolith. The increase in the alkalinity, the major element (Na+, Ca2+, Mg2+) concentrations and the U activity ratios of the granitic spring waters with decreasing spring elevation indicate that the main parameter that must be considered to explain the geochemical characteristics of these waters is the length of the water pathway within the bedrock, which controls the duration of the water–rock interactions. Based on this interpretation, the (234U/238U) activity ratios in the spring waters were modeled using a simple 1D reactive transport model that considers dissolution, precipitation and alpha recoil. By estimating the alpha recoil factor and the length of the water path for each spring, both the dissolution rate of the bedrock and the water residence time within the slope can be estimated. [Copyright &y& Elsevier]

Abstract: Weathering of outcrops of ultramafic rocks (remnants of ancient oceanic crust) is a source of biologically toxic trace elements, particularly first row transition elements. The Cr and Ni concentrations of serpentinite and metabasite outcrops in the northern sector of the Pollino massif (Lucanian Apennines, southern Italy) are hundreds of orders of magnitude higher than those of the upper continental crust. In this region, exposed intermediate to lower crustal rocks are significantly enriched in Ni, Cr, and V relative to the average upper continental crust. We evaluate the levels and distributions of trace elements of environmental concern, including Cr (as total dissolved Cr and Cr(VI)), V, Mn, Fe, Ni, Cu, Zn, As, Pb, and U, in spring waters from the northern sector of the Pollino massif. The major solutes in the spring waters from this region are Mg-HCO3 and Ca-HCO3. The Mg-HCO3 type waters are produced mainly through the interaction of meteoric waters with serpentinites, whereas the Ca-HCO3 type waters are produced through the interaction of meteoric waters with Ca-rich rocks (i.e., carbonate rocks, calc-schists, and metabasites). Thermodynamic evaluation indicates that in the MgO–SiO2–Al2O3–H2O system, waters flowing in serpentinites fall in the kaolinite field, close to the kaolinite–Mg-vermiculite phase boundary. This result arises because kaolinite is a relatively early reaction product, which is consumed to produce Mg-vermiculite and further Mg-saponite. In the CaO–SiO2–Al2O3–H2O system, Ca-HCO3 type waters fall either in the field of gibbsite or kaolinite, depending on dissolved silica. Chromium (VI) contamination associated with local mineralogy and with maximum admissible concentration >5μgL−1 was observed for nine springs (both Mg-HCO3 and Ca-HCO3 type waters). The Cr(VI)-rich Ca-HCO3 springs are not located in serpentinites. However, some of these waters likely acquire their high Cr levels from interacting with serpentinite clasts, as in the case of springs flowing through conglomerates. In addition, Cr(VI) contamination is not limited to waters interacting with serpentinites or serpentinite clasts, because in one case weathering of garnet-rich gneiss is responsible for the release of significant amounts of Cr(VI) in solution. Finally, studies are needed to address the potential health risks associated with the observed high concentrations of Cr(VI) in waters from the Pollino massif area. A mode-of-action analysis is needed to evaluate adverse health risks associated with exposure to Cr(VI) in drinking water, especially as Cr contamination is not limited to springs flowing through serpentinites. [Copyright &y& Elsevier]

Abstract: An up-to-date inventory of natural mineral and spring waters in Algeria is here presented. First, the legislation regarding exploitation, production and marketing of the latter is compared to the EU and international ones. Then, a physicochemical characterization and classification of the water types are proposed as well as a tentative establishment of a database for natural mineral and spring waters in Algeria. [Copyright &y& Elsevier]

Abstract: Within the framework of the Pan-European project about the geochemistry of bottled mineral waters in Europe launched in 2007 by the European Geological Surveys (EGS) Geochemistry Expert Group fourteen brands of bottled natural waters from Croatia of both mineral and spring types were evaluated for getting more coherent spatial information about the natural variation of element concentration in bottled waters found at the European market. Results of chemical analysis show that not a single one out of fourteen analyzed bottled waters from Croatia exceeds the Croatian water standards sanctioning thereby their suitability for human consumption. Also, statistical tests performed for 41 analytes (including pH and EC) clearly show that the water chemistry is in a high degree of conformity with regional geology, depending on structural, stratigraphic and, above all, lithological diversity of aquifers. Thus Dinaric and Pannonian parts of Croatia differ largely with regard to their water types: Dinaric region is completely lacking mineral water types while, on the other side, in the Pannonian region even the spring waters show stronger mineralization in comparison with their Dinaric counterparts. Typically, all natural waters from Croatia bear the bicarbonate (HCO3) signature. However, Ca–Mg cation pair combination is characteristic of spring waters while Na–K dominates in the mineral waters. [ABSTRACT FROM AUTHOR]

Sustainable management and protection of spring waters must be based on reliable predictions of flow and transport phenomena. Process-based models are frequently applied to accomplish this task. The provision of adequate model parameters is a prerequisite for predictive modelling. Frequently, this involves the use of inverse modelling, i.e. model parameters are adjusted until model results match field observations. Thus, process-based models are employed not only for prediction (predictive models) but also to support the aquifer characterisation (interpretative models). This work provides an overview of modelling techniques that can be applied to spring catchments for the aquifer characterisation or predictive purposes. The selection of an appropriate model must account for the type of aquifer: Continuum models describing flow through porous media are based on effective macroscopic properties of a representative elementary volume. Yet spring catchments are often composed of fractured or karstified hard rocks. The length scale of the discontinuities in these rocks may be so large that continuum approaches are found to be inadequate. Therefore, other distributed parameter models, such as discrete fracture networks or hybrid models that combine continuum and discrete approaches have been developed. All these models have in common that they require spatial parameter distributions. From a practical point of view, the application of distributed parameter models poses great challenges to the hydrogeological characterisation of spring catchments, in particular, in alpine terrain. These practical issues suggest the use of parsimonious global modelling approaches (lumped parameter models), in which the spring catchment is represented by only few global parameters rather than by spatial parameter distributions. Some of these approaches are empirical, i.e. they do not account for the physics of flow. Others are based on solving the flow equations for certain scenarios. Recently, process-based global approaches have emerged that incorporate the spatial heterogeneity of the spring catchment in the model equation. It is suggested that this type of approach is more appropriate than empirical models if predictions are required in a changing environment. [ABSTRACT FROM AUTHOR]

Abstract: An optimized model of multivariate classification for the monitoring of eighteen spring waters in the land of Serra St. Bruno, Calabria, Italy, has been developed. Thirty analytical parameters for each water source were investigated and reduced to eight by means of Principal Component Analysis (PCA). Water springs were grouped in five distinct classes by cluster techniques (CA) and a model for their classification was built by a Partial Least Squares–Discriminant Analysis (PLS–DA) procedure. The model was optimized and validated and then applied to new data matrices, containing the analytical parameters carried out on the same sources during the successive years. This model proved to be able to notice deviations of the global analytical characteristics, by pointing out in the course of time a different distribution of the samples within the classes. The variation of nitrate concentration was demonstrated to be the major responsible for the observed class shifts. The shifting sources were localized in areas used as sowable lands and high variability of nitrate content was ascribed to the practice of crop rotation, involving a varying use of the nitrogenous chemical fertilizers. [Copyright &y& Elsevier]

The purpose of this study was to monitor and evaluate the specific characteristics and properties of the most important water resources in Dalmatia, located in Southern Croatia, for a period of five years (1999-2003). The paper presents a detailed account of the water's chemical content, classification and concentration of salts. The bacteriological pollution levels are indicated by the total coliform bacterial levels (MPN coli/100 ml). The water characteristics are expressed by coefficients which represent the ratios between water ingredients. The Ca/Mg eq ratio, SO4/Cl eq ratio and K1, K2 for bicarbonate hardness were calculated. The hygienic characteristics of the water samples were expressed by the total coliforin bacteria estimation (MPN coli/100 ml), the permanganate consumption (KMnO4) and biological oxygen demand (BOD5). Karst waters, i.e. rain waters, in Dalmatia are moderately hard, the SO4/Cl ratio is 0.38-1.6, non corrosive (K1 lower than 0.2) and not significantly mineralised (<500 mg/L minerals). Sulfate waters are generally hard, the SO4/Cl ratio is higher than 1.6, K1 is 0.2-0.65. Marine waters are quite hard or hard, particularly at the river estuaries, the SO4/Cl ratio is lower than 0.38, and K1 is higher than 0.65. Rain water direction equation, marine direction equation and sulfate direction equation are calculated on the base of SO/Cl ratio. The groundwater and springs in Dalmatia are less polluted than surface waters. A majority of the water observed, 24 of 42 locations, have geometric average values of MPN coli<150/100 ml of water. This group includes the majority of springs in Dalmatia, as well as some sections of rivers studied. The highest bacteriological pollution was found at nine locations where MPN coli>1000/100 ml. Moderate pollution was found at nine locations where MPN coli is between 150-1000/100 ml of water The water in Dalmatia is quite safe and mainly preserves its natural properties. [ABSTRACT FROM AUTHOR]