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1

German jako wskaźnik warunków hydrogeochemicznych w jeleniogórskim systemie geotermalnym

Dobrzyński D., Gruszczyński T., Birski Ł.

Przegląd Geologiczny

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2017

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Vol. 65, nr 11/1

946--950

EN

Geochemical studies on trace elements in thermal waters from Cieplice, Karpniki and Staniszów (Jelenia Góra Geothermal System, Sudetes, Poland) revealed a presumably regional relation between germanium and silicon. The Ge:Si ratios in waters of Cieplice are likely controlled by the chemical equilibrium process of silicate minerals transformation in granite aquifer-rocks. Geochemical inverse mass balance modelling using main rock-forming minerals of actual composition shows that incongruent dissolution ofprimary silicate minerals with forming secondary (clay minerals, silica forms) phases is responsible for thermal water chemistry in Cieplice. Available data on germanium in silicate minerals combined with the results of geochemical modelling give Ge:Si ratios close to real values. A chemical non-equilibrium, and a gradual decrease of both the germanium content and the Ge:Si ratio have been identified in the thermal waters from two new intakes (Karpniki, Staniszów).

2

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.

3

Research in abandoned well questions the practice or well representativity criteria used in selecting for groundwater monitoring sites

Dobrzyński D., Mitręga J.

Biuletyn Państwowego Instytutu Geologicznego

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2013

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nr 456 Hydrogeologia z. 14/1

105--111

EN

The object of research is well No. 5p (UE_ID: PL06G110_004) located in Sokołowsko (the Sudetes, SW Poland). Since completing the well in 1980, it has never been included in water services due to poor water quality, but simply abandoned. The abandonment, lasting already 32 years, has established an unintended long-term experiment in the well. Of the four screened water-bearing horizons, two lower ones run more pressurized sulphate mineral water, which has generated a permanent upward flow within the well and pollution of fresh water in upper ones. The consequences are much wider, as the combination of hydraulic and geochemical settings formed an in-hole natural laboratory in which bio-geochemical processes affect the water quality and the contamination by hydrocarbons enhanced by human activity. The well should ultimately be closed down. Because the well has been included in the national monitoring network for over 20 years, these results also impel to postulate for establishing: 1) a more strong procedure for testing the representativity of observation points in the monitoring network, 2) a revision programme for already existing points, and 3) amendments to the regulations to explicitly solve the case of “orphans” due to the risk they may cause.

PL

Przedmiotem badań jest otwór studzienny nr 5p (UE_ID: PL06G110_004) położony w Sokołowsku (Sudety). Od wykonania w 1980 roku, z uwagi na złą jakość wody, nigdy nie włączono go do sieci wodociągowej, i w konsekwencji porzucono. Brak eksploatacji przez 32 lata spowodował stworzenie się w nim warunków do niezamierzonego, długotrwałego eksperymentu. Z ujętych w otworze wspólnie czterech stref wodonośnych, dwie dolne prowadzą wody mineralne pod większym ciśnieniem, co powoduje ich stały pionowy przepływ w otworze i zanieczyszczenie wyżej ległych wód zwykłych. Hydrauliczne i geochemiczne warunki w studni sprzyjają procesom biogeochemicznym wpływającym na jakość wody i wzbudzone przez działalność człowieka zanieczyszczenie węglowodorami. Otwór powinien być niezwłocznie zlikwidowany. Z uwagi na to, że studnia od około 20 lat jest w sieci monitoringu krajowego, wyniki te skłaniają również do postulowania ustanowienia: 1) skutecznej procedury oceny reprezentatywności punktów obserwacyjnych w sieci monitoringu, 2) programu rewizji istniejących punktów, oraz 3) nowelizacji regulacji w celu rozwiązania problemu „osieroconych” otworów, ze względu na zagrożenia jakie one stwarzają.

4

„Na dole bez zmian”, czyli o konieczności podjęcia multidyscyplinarnych badań interakcji w systemie ciecze szczelinujące – łupki gazonośne – wody podziemne

Dobrzyński D., Wolicka D., Poszytek A., Borkowski A.

Biuletyn Państwowego Instytutu Geologicznego

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2013

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nr 456 Hydrogeologia z. 14/1

113--118

PL

Po raz pierwszy w Polsce, przeprowadzono multidyscyplinarne badania cieczy szczelinujących i cieczy po szczelinowaniu hydraulicznym (cieczy zwrotnej) w celu oceny ich potencjału mikrobiologicznego oraz opisu interakcji ze skałami łupkowymi i wodami podziemnymi. W cieczy zwrotnej stwierdzono liczne mikroorganizmy tlenowe i beztlenowe mogące modyfikować jej skład i właściwości fizyczno-chemiczne. Wyniki wskazują, że podczas zabiegu szczelinowania ciecz szczelinująca szybko zmienia swój skład (wzrasta stężenie większości składników), co inicjuje różnorodne procesy geochemiczne, biogeochemiczne, minerałotwórcze. Zmieniający się skład cieczy wpływa na trwałość istniejących i tworzenie się nowych minerałów. Przedstawione wyniki badań mają między innymi znaczenie dla oceny żywotności otworów eksploatacyjnych i efektywności wydobycia gazu oraz oceny bezpieczeństwa wyżejległych poziomów wodonośnych.

EN

The first in Poland, multidisciplinary research on fracturing and flow-back fluids were carried out to the purpose of characterization of their microbiological potential and understanding interactions with shale rock and groundwater. Flow-back fluids contain abundant aerobic and anaerobic microorganisms, which can modify their properties and chemical composition. Results show that during and after hydraulic fracturing fluids quickly change their chemistry (increase of most solutes), what initiate various geochemical, biogeochemical, and mineralogical processes. The changing chemistry of fracturing fluids affects the stability of present minerals and the formation of new ones. Presented research are also important in terms of the gas borehole lifespan and the recovery of gas resource, and the safety assessment for overlying aquifers.

5

Analiza mikrobiologiczna i molekularna dla zrozumienia zjawisk w porzuconym otworze studziennym

Borkowski A., Dobrzyński D., Kowalczyk P., Wolicka D.

Biuletyn Państwowego Instytutu Geologicznego

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2013

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nr 456 Hydrogeologia z. 14/1

39--44

PL

W porzuconym otworze studziennym funkcjonującym w krajowej sieci monitoringu wód podziemnych przeprowadzono badania geomikrobiologiczne. Stwierdzono powszechne, rozległe zarośnięcie ścian otworu oraz wypełnienie światła otworu biomatą mikrobiologiczną na głębokości około 100 m. Przy pomocy analizy mikrobiologicznej wykryto znaczną ilość mikroorganizmów w wodzie, natomiast analiza molekularna próbek biomaty wykazała obecność współistniejących bakterii redukujących siarczany oraz bakterii cyklu żelazowo-siarkowego. Obecność tak rozwiniętych zespołów mikrobiologicznych może być oznaką dopływu wraz z wodą materii organicznej oraz jonów SO42- i Fe2+ niezbędnych do wzrostu mikroorganizmów stwierdzonych w biomacie, co z kolei może znacząco wpływać na chemizm wody.

EN

Geomicrobiological studies were performed in the abandoned water well which still function in the national groundwater monitoring network. Extensive biofouling of cases and screens, as well as microbial mat, which completely fill-up the well at the depth of about 100 m, have been found. The microbiological analysis documented abundant microorganisms in water, while the molecular analysis of microbial mat revealed the coexistence of sulphate reducing and iron-sulphur cycle bacteria. The presence of such developed microbiological communities might indicate organic matter and SO42- and Fe2+ ions supply necessary for the growth of microorganisms found in the mat, which in turn would significantly affect the water chemistry.

6

Badania potencjału redoks na przykładzie sudeckich wód leczniczych

Dobrzyński D.

Przegląd Geologiczny

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2010

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Vol. 58, nr 1

46-53

EN

In Poland, the redox potential (EH) is seldomly measured in groundwater. Since the year 2006 determination of redox potential is required for documenting properties of curative mineral waters. Investigations of redox conditions in groundwater need both proper measurement and interpretation. In the paper, crucial questions of: 1) redox equilibrium in groundwater, 2) field measurement, 3) correction methods, and 4) EH interpretation are presented. Some aspects of applying the redox potential for interpreting groundwater chemistry and using geochemical modelling are illustrated by hydrochemical data of curative waters from spas in the Sudetes Mts., SW Poland. Main reasons of the common redox non-equilibrium found in groundwater are co-existence of numerous aqueous redox pairs and usually non-equilibrium in particular redox pairs. Redox determinations have to be done in the field, and require extreme cleanness and precision, e.g., measuring without contact with the atmospheric air. Field measurements must be corrected to the standard hydrogen electrode, considering: type of reference electrode, concentration of electrode filling solution, type of standard redox solution, and water temperature. The redox potential has been measured in water at first from all the Sudetic spas, totally in 33 water intakes. In curative waters from the Sudetes corrected EH ranges between –159 mV and +343 mV. Usually, thermal waters show lower EH values than cold, CO2-rich waters. The lowest redox potential was found in the hottest thermal waters, i.e., in water from Zdzisław intake (in Lądek Zdrój) and C-2 intake (in Cieplice Śląskie Zdrój). Generally, the higher the pH, the lower the EH in groundwater. Methods of geochemical modelling, which are often and often applied in groundwater research, also require the EH determination. Information about EH are used in the calculation of speciation models of water, and affect the results of whole geochemical modelling as well as evaluations of the saturation state. The speciation-solubility modelling for the Sudetic curative waters, presented in the paper, shows that the proper correction of field EH measurement determines the quality of calculations. Improperly corrected EH values might lead to species activity errors, even up to several order of magnitudes, and erroneous interpretation of the mineral phases stability in the hydrogeochemical system.

7

Rola częściowych równowag chemicznych w kontrolowaniu aktywności krzemu w sudeckich wodach leczniczych

Dobrzyński D.

Biuletyn Państwowego Instytutu Geologicznego

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2009

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nr 436, z. 9/1

87-94

PL

Skład chemiczny sudeckich wód leczniczych został poddany interpretacji z punktu widzenia kontroli rozpuszczalności krzemu. W termalnych wodach leczniczych Lądka-Zdroju i Cieplic Śląskich-Zdroju istnieją warunki sprzyjające trwałości koloidu glinokrzemianowego HASB. Aktywność krzemu w zarówno chłodnych, jak i termalnych wodach leczniczych może być kontrolowana przez częściowe równowagi chemiczne reakcji inkongruentnego rozpuszczania faz glinokrzemianowych z utworzeniem Al(OH)3.

EN

Chemical composition of curative mineral waters from the Sudetic spas was interpreted in terms of silicon solubility control. In thermal waters from Lądek-Zdrój and Cieplice Śląskie-Zdrój, conditions for stability of hydroxyaluminosilicate HASB are maintained. In both cold and thermal waters, silicon might be controlled by partial chemical

8

Ocena dystrybucji arsenu w wybranych wodach leczniczych Sudetów na podstawie filtracji membranowej i modelowania specjacyjnego

Dobrzyński D., Stępień M.

Biuletyn Państwowego Instytutu Geologicznego

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2009

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nr 436, z. 9/1

95-101

PL

Filtracja membranowa wybranych sudeckich wód leczniczych przez filtry o różnych rozmiarach porów (od 0,1 do 180 micro/m) pozwoliła zilustrować dystrybucję arsenu w wodzie wywołaną obecnością faz (roztwór, koloidy, zawiesiny) o różnych rozmiarach cząstek. Modelowanie specjacyjne wskazuje, że w większości wód specjacje arsenu (V) przeważają nad specjacjami arsenu (III). Badane wody lecznicze są zwykle w widocznej równowadze redoks dla pary As(V) / As(III).

EN

Membrane filtration of selected curative mineral waters (Sudetes Mts., S W Poland) by filters of various (from 0.1 to 180 micro/m) pore size allowed illustrating distribution of arsenic in water which is related to size of forms (solutes, colloids, particulate matter) occurred. Speciation geochemical modelling showed that in most of curative waters, species of As(~ prevails over As(III) species. Studied curative waters are usually in apparent redox equilibrium in terms of As(V) / As(III) redox species pair.

9

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).

10

Znaczenie częściowych równowag chemicznych w kształtowaniu chemizmu wód podziemnych w systemach krzemianowych strefy wietrzenia

Dobrzyński D.

Przegląd Geologiczny

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2007

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Vol. 55, nr 6

460-466

EN

Partial chemical equilibrium plays an important role in geochemical systems. In the short turn-over time zone of hydrogeological systems, the conditions for the full chemical equilibrium amongst groundwaters, mineral phases and gases are rarely fulfilled. In these systems, partial chemical equilibrium is often responsible for controlling activity of solutes. Examples of partial chemical equilibrium with secondary phases in silicate systems of the weathered zone are given, and the role of metastable and stable secondary silicate solids is discussed.

11

Chemical diversity of groundwater in the Carboniferous-Permian aquifer in the Unisław Śląski - Sokołowsko area (the Sudetes, Poland); a geochemical modelling approach

Dobrzyński D.

Acta Geologica Polonica

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2007

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Vol. 57, no. 1

97-112

EN

Groundwater in the Carboniferous.Permian sedimentary aquifer in the vicinity of Unisław Śląski - Sokołowsko (Intra-Sudetic Basin, the Sudetes, SW Poland) manifests spatial chemical diversity. The water chemistry varies from fresh calcium-magnesium-bicarbonate groundwater at the recharge area to calciumsodium-sulphate mineral water downwards the basin. Geochemical mass balance modelling confirms that the main chemistry features of the sulphate mineral water are controlled by dedolomitization and calcium common-ion effects. Congruent dissolution of gypsum promotes incongruent dissolution of dolomite with calcite precipitation. Cation exchange between Ca[^2+] (and Mg[^2+]) solutes and Na[^+] (and K[^+]) also takes place. The sulphate mineral water shows elevated concentrations of numerous trace elements. Iron, zinc and manganese originate from dissolution of carbonates (dolomite and/or siderite) and/or sulphides. The hydrogeological system studied should be considered as a series of individual flow systems. The results of preliminary geochemical modelling corroborate the role of mixing in the formation of the spatial pattern of the aqueous chemistry in the system. The main factor that controls groundwater chemistry is the mixing of two components: modern (tritium-bearing) fresh water and older (pre-bomb Holocene) sulphate mineral water.

12

Modelowanie geochemiczne narzędziem poznania geochemii systemów wód podziemnych. Przykłady zastosowań, aktualny stan w Polsce

Dobrzyński D.

Przegląd Geologiczny

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2006

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Vol. 54, nr 11

976-976, 981

EN

Potential of geochemical modelling for groundwater systems, with the most important up-to-date literature was concisely described. Case studies considering different methods of geochemical modelling used for understanding of groundwater systems geochemistry are presented. Most of case studies concern modelling of groundwater in short turn-over time zone in the Sudetes Mts. (SW Poland). Present-day geochemical modelling state-of-art in Poland was discussed and evaluated.

13

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.

14

Silica solubility in groundwater from Permian volcanogenic rocks (the Sudetes Mts., SW Poland) : the role of reversible aluminosilicate solids

Dobrzyński D.

Geological Quarterly

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2006

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Vol. 50, No. 4

407-417

EN

The chemistry of groundwater in Permian volcanic rocks (rhyolitic tuffs, trachyandesites) in two small headwater catchments (the SudetesMts., SW Poland) has been investigated. The calculated transfer of silica released during weathering is greater than the real concentration in groundwater, and indicates that part of the silica is immobilized in secondary aluminosilicates. Silica solubility is interpreted in terms of the solubility of reversible secondary aluminosilicates (allophanes, hydroxyaluminosilicates). Partial chemical equilibrium of these phases is sometimes locally achieved. In groundwaters with pH above 6.7 from trachyandesites of the BukowiecMt. type, chemical equilibrium with respect to the hydroxyaluminosilicate HASB is probably maintained. Its solubility constant, calculated accordingly to the method given by Schneider et al. (2004), is lgK HASB = –44.74 (۪.52), and indicates that this "field" HASB has a solubility lower than the published experimental value (lgK HASB = –40.6 ۪.15) for synthetic HASB (op.cit.). Non-equilibrium with respect to aluminosilicates in groundwaters from rhyolitic tuffs and from trachyandesites of the Stożek Wielki Mt. type is caused by the short turn-over time of groundwater in the systemand by the poor neutralisation capacity of the bedrock. The silica concentration in these groundwaters results from steady-state conditions achieved between weathering release, hydrological removal and precipitation of secondary phases. The hydrogeochemical data are conducive to the presence of allophane minerals in the weathered rhyolitic tuffs.

15

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.