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Geochemistry of germanium in thermal waters of the Jelenia Góra geothermal system (Sudetes, Poland) : solute relationships and aquifer mineralogy

Dobrzyński Dariusz, Tetfejer Klaudia, Stępień Marcin, Karasiński Jakub, Tupys Andrii, Słaby Ewa

Annales Societatis Geologorum Poloniae

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2023

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Vol. 93, No. 3

323--344

EN

A long-term (2004–2021) study of the chemical composition of thermal waters in the Jelenia Góra geothermal system provided information on a wide set of components. The subject of the present study is the geochemistry of germanium (Ge), which occurs in concentrations ranging from 2.7 to 6.3 μg/L in the waters studied. Interpretation of a set of 46 chemical analyses identified relationships between germanium and other elements in thermal waters from individual intakes. In the old thermal waters of Cieplice and Karpniki of deep circulation, germanium is derived from silicates and its concentration is controlled by the solubility of Ge-bearing quartz with an average Ge content of 1.5 μg/g. The source of germanium in the deep old thermal water at Staniszów is mainly sulphides, most likely arsenopyrite, but the secondary contribution of Ge from silicates (biotites, amphiboles) should not be ignored. The mineral phase, responsible for controlling Ge activity in this water, cannot yet be identified. The shallow thermal waters at Cieplice, which are a mixture of old thermal waters and modern waters, differ from the deep waters. Germanium in shallow waters probably is derived from silicates, but owing to mixing, there are no chemical equilibrium conditions; the concentration of Ge is determined by the dynamic equilibrium of the mixed water components. The modern water of intake no. 2 (Cieplice) differs from other shallow waters and also shows similarities to the Staniszów water. The germanium in the no. 2 water probably comes mainly from ferromagnesian minerals (biotite, amphiboles), although the influence of sulphides cannot be excluded. The relationships of germanium to other elements, including the Ge/Si ratio, appear to be effective indicators of hydrogeochemical conditions. Thermal waters from the different locations show both similarities and differences in chemical composition,especially of minor and trace components. At the present, still weak stage of recognition, the Jelenia Góra geothermal system can be treated as an area of occurrence of local systems responsible for the quantity and quality of thermal waters in individual intakes.

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Geochemical relationships in CO2-rich therapeutic waters of the Sudetes (Poland)

Dobrzyński Dariusz, Stępień Marcin, Szostakiewicz-Hołownia Marzena, Humnicki Włodzimierz

Acta Geologica Polonica

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2022

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Vol. 72, no. 4

479--493

EN

Geochemical studies of CO2-rich therapeutic waters in the Sudetes have provided new data on a wide range of trace elements, going beyond standard chemical analyses of such waters. A consistent set of physicochemical data obtained using the same analytical methods was subjected to statistical analyses, including hierarchical clustering, factor analysis and nonparametric tests (Kruskal-Wallis, Tau Kendall), to reveal geochemical relationships between physicochemical and chemical parameters in the waters, and their relationships with the aquifer lithology. Distinct differences in the composition of waters found in crystalline rocks (mainly gneisses and mica schists) and sedimentary rocks were identified. The wide range of elements can be associated with the hydrolysis of silicate minerals, including alkali and alkali earth metals (Li, Na, K, Rb, Cs, Be) and (mostly) transition elements (Fe, Mn, Zn, Co, W, Mg). Carbonate equilibria are the next important factor as it determines the aggressiveness of the water towards the minerals of aquifer rocks and affects the concentrations of numerous solutes. The probable common origin of chlorides, bromides and sulphates together with Li, Na, Sr may be related to the relict saline component of deep circulating waters, a hypothesis that requires further investigations.

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Geochemistry of trace elements in spring waters of the Lourdes area (France)

Dobrzyński D., Rossi D.

Annales Societatis Geologorum Poloniae

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2017

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Vol. 87, No. 2

199--212

EN

Geochemical studies on the waters of four springs, including the Massabielle (MS) Spring, were carried out at Lourdes (France) following a long, rainless and warm period, with the aim of at least documenting the groundwater chemistry that was affected by the current meteoric input. The existence of anecdotal reports about anomalously elevated concentrations of trace constituents in the water of the MS Spring in the absence of any detailed studies inspired these first geochemical investigations of trace elements in the spring waters at Lourdes. The main common features of waters from the four springs studied in Lourdes are low total dissolved solids (255–318 mg/L), a slightly alkaline pH (7.50–7.68), oxidizing conditions (EH = 458–472 mV), similar temperatures (11.3–13.1 °C), and their Ca-HCO3 hydrochemical type, all of which are typical characteristics for an active zone within a hydrogeological system that is developed in carbonate-dominated bedrock. The spring waters, which represent an active turnover zone in the hydrogeological system, are only in partial chemical equilibrium with the minerals of the aquifer rocks. The enrichment of the MS Spring water with numerous elements (Li, Na, Cs, Ba, S, F, Br, REE, B, Sb and Bi), when compared with other springs studied and with the bedrock geochemistry, probably is caused by contributions from fluids (originating from the Pyrenees basement and/or from Triassic saliferous deposits) in the formation of the hydrogeochemical content of the zone under investigation. The germanium concentration in all of the waters studied was significantly lower than the concentrations typically found in fresh groundwater in the active zone; accordingly, the hypothesis concerning an anomalously high concentration of this element in the MS Spring water was invalidated. The preliminary geochemical research presented is part of an interdisciplinary geochemical-biological-tensiometric study of the spring waters at Lourdes.

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Mineralne wody lecznicze Wysowej w świetle badań wskaźników hydrochemicznych

Winid B., Lewkiewicz-Małysa A.

Wiertnictwo, Nafta, Gaz

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2010

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T. 27, z. 1--2

457-466

PL

Mineralne wody lecznicze są to wysoko zmineralizowane szczawy typu HCO3-Cl-Na, HCO3-Cl-Na-Ca, HCO3- Na-Ca, zawierające składniki swoiste takie jak: jod i żelazo oraz charakteryzujące się także większą niż zwykłe wody podziemne zawartością bromków i kwasu metaborowego. Na podstawie analiz chemicznych wykonywanych w ciągu ostatnich kilkunastu lat policzono proporcje między jonami i porównywano ich wzajemne zależności. Wskaźniki hydrochemiczne wskazują, że wody w różnym stopniu są zasilane dopływami ze stref aktywnej infiltracji. Wody wysoko zmineralizowane zawierają składową infiltracyjną, ale też wykazują cechy charakterystyczne dla wód diagenetycznych. Zmiany wartości wskaźników hydrochemicznych wód mineralnych mają charakter nieregularnych wahań, ale w przeciągu ostatnich kilkunastu lat dla wód niektórych ujęć obserwowane są też spadki mineralizacji. Obserwowane niewielkie wzrosty wartości poszczególnych wskaźników hydrochemicznych można interpretować jako stały dopływ wód infiltracyjnych.

EN

Medical-mineral waters are highly-mineralized waters are of HCO3-Cl-Na, HCO3-Cl-Na-Ca, HCO3-Na-Ca containing such specific components as iodine and ferrum. The amount of bromine and metabromine acid is bigger than in ground water. On the basis of chemical analyses carried out during the last ten years the proportion among the ions has been calculated and ions interrelations and variability during the examined period of time have been compared. Hydrochemical ratios speak out about supplying waters intakes partly from active zone of water exchange. Highly - mineralized water has infiltration and diagenetic component. Most changes of variability are irregular. Reductions of mineralization refer to the some waters. Observed minor increase of some ratios may speak about supplying water intakes with the infiltration component.

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Zależności między składnikami chemicznymi w wodach mineralnych antykliny iwonickiej

Lewkiewicz-Małysa A., Winid B.

Wiertnictwo, Nafta, Gaz

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2009

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T. 26, z. 1--2

221-229

PL

Wody mineralne antykliny iwonickiej występują głównie w II i III poziomie piaskowca ciężkowickiego. Są to wody typu CI-HCO3-Na i HCO3-Cl-Na wykorzystywane do kuracji pitnej, kąpieli mineralnych i produkcji soli jodobromowej. Na podstawie analiz chemicznych wykonywanych w ciągu ostatnich kilkunastu lat policzono proporcje między jonami i porównywano ich wzajemne zależności. Wskaźniki hydrochemiczne wód mineralnych Iwonicza i Rymanowa wskazują, że wody te są zasilane dopływami ze stref aktywnej infiltracji, ale też wykazują cechy charakterystyczne dla wód stref występowania bituminów. Większość zmian wartości wskaźników hydro-chemicznych wód mineralnych ma charakter nieregularnych wahań, a obserwowane niewielkie wzrosty wartości można interpretować jako stały dopływ wód infiltracyjnych, co przy braku zmian mineralizacji wód ujęć jest zjawiskiem korzystnym.

EN

The Iwonicz Anticline mineral waters are connected with the second and the third level of Ciężkowice sandstones. These are Cl-HCO3-Na and HCO3-Cl-Na type and are used for water treatment, curative bath and iodine bromide salt production. On the basis of chemical analysis carried out over last ten years, the proportion among the ions has been calculated and variability during the examined period of time have been compared. Iwonicz and Rymanów hydrochemical ratios speak about supplying water intakes from active zone of water exchange but also prove the co-existence of mineral waters and bitumin deposits. Most changes of variability are irregular. Observed minor increase of some ratios may speak about supplying water intakes with the infiltration component, what is beneficial, if there are no changes in mineralization of water.

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Geochemistry and age of groundwater in a hydrochemically diversified aquifer (Permo-Carboniferous, the Intra-Sudetic Synclinorium, SWPoland) derived from geochemical modelling and isotopic studies

Dobrzyński D.

Acta Geologica Polonica

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2009

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Vol. 59, no. 3

371-411

EN

Comprehensive investigations of groundwater were performed in a sedimentary aquifer of Permo-Carboniferous, Intra-Sudetic Synclinorium, in SWPoland. The investigation included aqueous chemical and isotopic composition, chemistry of mineral phases, geochemical modelling, and tritium and radiocarbon groundwater dating. Chemical diversity in the groundwater system is created by the mixing of modern fresh water and older sulphate water with higher dissolved solids. The system is treated as a system of flows of two end-member water types. Geochemical modelling is used for: (1) explaining the origin of the chemistry of both water components, (2) quantifying the groundwater mixing, (3) correcting the radiocarbon age of the groundwater for the effects of chemical water-rock interactions, and (4) calculating reaction rates. Study of stable (C, S, O, H) and unstable ([^3H], [^14]C) isotopes allowed the inverse mass balance geochemical models to be verified and specified, and the groundwater to be dated. The chemistry of the modern, tritium-bearing, fresh water is a result of dissolution of limestones, dolomites and gypsum. The mean tritium-age of this water, based on the lumped-parameter approach, varies between 10 and 200 years. The sulphate mineral water owes its chemistry to the process of dedolomitization driven by gypsum dissolution. Its radiocarbon age is about 5.9 ka BP, i.e., during theMid-Holocene Climatic Optimum. Rates of chemical reactions responsible for the formation of sulphate type water are estimated to be: dissolution of gypsum (2.85 [mi]mol/L/year) and dolomite (0.21 [mi]mol/L/year), calcite precipitation (0.20 [mi]mol/L/year), organic matter decomposition (0.08 [mi]mol/L/year).

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Zależności między składnikami chemicznymi w wodach słabo zmineralizowanych Rymanowa-Zdroju

Lewkiewicz-Małysa A., Winid B.

Wiertnictwo, Nafta, Gaz

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2008

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T. 25, z. 2

461-467

PL

Wody słabo zmineralizowane Rymanowa Zdroju występują w I i II poziomie piaskowca ciężkowickiego oraz w warstwach krośnieńskich. Są to wody typu HCO3-Ca i HCO3-Ca-Mg. Na podstawie analiz chemicznych wykonanych w ciągu kilku ostatnich lat policzono proporcje między jonami i porównywano ich wzajemne zależności. Wzajemne proporcje między jonami są odzwierciedleniem procesów kształtujących chemizm wód i reakcji zachodzących na drodze przepływu.

EN

Low-mineralized waters of Rymanów Zdrój occur in I and II Ciężkowice sandstone horizon and in the Krosno Beds. These are waters of HCO3-Ca and HCO3-Ca-Mg type. Ion ratios were calculated on the basis of chemical analyses made over the last few years and the results were calculated. The proportions between ions illustrate processes shaping the chemistry of water and reactions following the flows.

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Silicon and aluminium in groundwater of the Kłodzko Region (the Sudetes, )land) - partial geochemical equilibrium with secondary solid phases

Dobrzyński D.

Geological Quarterly

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2006

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Vol. 50, No. 3

369-382

EN

The chemistry of shallow, cold groundwater in the eastern part of the Kłodzko Region (the Sudetes, SW Poland) was investigated, Groundwaters occur in the short turn-over time zone of the hydrogeological systems. The aquifers are composed of various bedrock types (metamorphic, igneous and sedimentary). Silicon and aluminium concentrations in the waters of particular aquifers are documented. The aqueous chemistry is interpreted in terms of the solubility of solid phases to indicate phases that are responsible for silicon and/or aluminium solubility control. Locally and/or periodically (seasonally) partial geochemical equilibrium between the groundwater and the secondary solid phases might be reached and maintained. In groundwater with a pH below 6.7, aluminium activity is usually controlled by the reversible congruent dissolution of A1(OH)3 forms, whereas silicon activity is probably controlled by the solubility the SiO2 form (chalcedony). At pHs above 6.7, the incongruent reaction between the hydroxyaluminosilicate colloid (HASB) and forms of Al(OH), controls both silicon and aluminium activities.

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Silica origin and solubility in groundwater from the weathered zone of sedimentary rocks of the Intra-Sudetic Basin, SW Poland

Dobrzyński D.

Acta Geologica Polonica

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2005

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Vol. 55, no. 4

445-462

EN

The groundwaters studied in the Intra-Sudetic Basin, SW Poland, occur in the regolith and in the fissured bedrock. Silica concentration in groundwaters ranges from 0,7 to 24,1 mg/L SiO2. Mineral phases that are the source of silica solute were pointed out on bedrock mineralogy and saturation state analysis. Interpretation of aqueous chemistry in terms of mineral stability confirms that partial geochemical equilibrium is maintained. In groundwater with pH values below 4.8 from the fissured aquifer in Carboniferous siliciclastic rocks, kaolinite controls silica solubility. Congruent dissolution of the allophane phase and/or incongruent reaction between the Al(OH)3 form and kaolinite/ halloysite or allophane can be responsible for silica activity in groundwater, with pH values between 5,5 and 6,7, from the regolith on Carboniferous rocks and from the fissured aquifer in Cretaceous mudstones.Groundwaters with pH values above 6,7 occur in the Permian and Cretaceous fissured aquifers which contain calcite/dolomite minerals. Silica and aluminium concentrations in these aquifers are clearly maintained by equilibrium with the hydroxyaluminosilicate HASB. The solubility constant of HASB estimated on groundwater chemistry is lgK HASB = -44,88 (± 0,48), which is lower than the recently published experimental value (SCHNEIDER and al. 2004). In groundwater with pH values between 4,8 and 5,5 from the regolith sampled during snow melt, equilibrium, even with reversible secondary aluminosilicates, is not maintained. Silicon and aluminium concentrations result from kinetics or steady-state between weathering release and hydrological removal.