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Hydrochemistry and Isotopic Analysis of Deep (Partly Thermal) Wells and Springs in NW-Slovenia

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Hydrochemistry and Isotopic Analysis of Deep (Partly Thermal) Wells and Springs in NW-Slovenia Hydrochemistry and Isotopic Analysis of Deep (Partly Thermal) Wells and Springs in NW-Slovenia Master thesis by Sven Philipp, Matr.-Nr.: 1416062 Institute for Applied Geosciences Darmstadt, February 2015 Hydrochemistry and Isotopic Analysis of Deep (Partly Thermal) Wells and Springs in NW-Slovenia Master thesis submitted to the Department 11 Institute of Applied Geosciences TU Darmstadt by Sven Philipp Matriculation number: 1416062 Supervisors: Prof. Dr. Kempe Bojan Otoničar, PhD First reviewer: Prof. Dr. Kempe Second reviewers: Bojan Otoničar, PhD Prof. Dr. Schüth 12. Februar 2015 Zdravljica by France Prešeren Žive naj vsi narodi ki hrepene dočakat' dan, da koder sonce hodi, prepir iz sveta bo pregnan, da rojak prost bo vsak, ne vrag, le sosed bo mejak! Das Trinklied von France Prešeren übersetzt von Klaus Detlef Olof Es leben alle Völker, die sehnend warten auf den Tag, dass unter dieser Sonne die Welt dem alten Streit entsag! Frei sei dann jedermann, nicht Feind, nur Nachbar mehr fortan! A Toast by France Prešeren translated by Janko Lavrin God's blessing on all nations, Who long and work for that bright day, When o'er earth's habitations No war, no strife shall hold its sway; Who long to see That all men free No more shall foes, but neighbours be. IV Eidesstattliche Erklärung Hiermit erkläre ich, Sven Philipp (Matrikel-Nr. 1416062), dass ich die vorliegende Masterarbeit "Hydrochemistry and Isotopic Analysis of deep (partly thermal) wells and springs in NW-Slovenia" ohne Hilfe Dritter und ohne Benutzung anderer als der angegebenen Hilfsmittel angefertigt habe; die aus fremden Quellen direkt oder indirekt übernommenen Gedanken sind als solche kenntlich gemacht. Die Arbeit wurde bisher in gleicher oder ähnlicher Form keiner anderen Prüfungsbehörde vorgelegt und nicht veröffentlicht. …………………………... …..……………….…. Ort, Datum Unterschrift Erstberichterstatter: Prof. Dr. Stephan Kempe Zweitberichterstatter: Prof. Dr. Christoph Schüth V Declaration of Authorship Hereby I certify, Sven Philipp (Matrikel No. 1416062) that the complete work of this master thesis "Hydrochemistry and Isotopic Analysis of Deep (Partly Thermal) Wells and Springs in NW-Slovenia" was done by myself and only by using the referenced literature and the described methods. This thesis was not submitted in identical or similar form to another examination authority and it was not published before. …………………………... …..……………….…. Place, Date Signature First supervisor: Prof. Dr. Stephan Kempe Second supervisor: Prof. Dr. Christoph Schüth VI Zusammenfassung (German) Die Ziele dieser Masterarbeit sind zum einen abzuschätzen, ob Dedolo- mitisierung ein derzeit ablaufender Prozess im Untergrund von Rovte (W Slowenien) ist und zum anderen die Hydrochemie der Thermalbrunnen und subthermalen Quellen in NW-Slowenien zu charakterisieren. Um diese Ziele zu erreichen, wurden Wässer aus tiefen Brunnen und Quellen im Gebiet Rovte und Wässer aus Thermalbrunnen und subthermalen Quellen im Gebiet Cerkno/Kranj analysiert. Die hydrochemischen Analysen wurden mit Spektrophotometrie, Ionenchromatographie und Atomabsorptionsspektrometrie und die Isotopen-Analysen (δ2H und δ18O) mit dem automatischen Analysegerät Picarro L2130-i vorgenommen. Die Brunnen Z (Zavčan), R (Rodofov Mlin) und B (Bizjakov Mlin) durchteufen Schichten von Gips in einer Tiefe von mehreren hundert Metern. Daher zeigen die 2- Wasserproben der Brunnen Z und R hohe SO4 -Konzentrationen und molare Mg2+/Ca2+-Verhältnisse kleiner als 1. Die Wasserproben von den oberflächennahen 2- - - Quellen zeigen sehr geringe SO4 -, aber im Gegensatz dazu hohe NO3 - and Cl - Konzentrationen. Diese sind eindeutig durch anthropogene Einflüsse beeinflusst. Die Isotope (δ2H and δ18O) der Brunnen Z und R befinden sich im gleichen Bereich. Dies läßt darauf schließen, dass die Wässer von Z und R dem gleichen Aquifersystem entstammen. Berechnungen der Saturationsindizes mit PHREEQC zeigen, dass die meisten Proben der Brunnen mit Calcit übersättigt und meistens 2- mit Dolomit untersättigt sind. Außerdem zeigt das Diagramm pH vs. SO 4 - Konzentration eine negative Korrelation. Dies und die präferentielle Abfuhr von Mg2+ aufgrund der molaren Mg2+/Ca2+-Verhältnisse kleiner als 1, deutet auf eine derzeit ablaufende Dedolomitisierung hin. Hydrochemische Analysen der Wässer von den Thermalbrunnen und subthermalen Quellen zeigten, dass eine Tiefenzirkulationsmuster in NW- Slowenien existiert. Vermutlich werden die Bohrlöcher durch das tiefe Aquifersystem (nämlich die grau geschichteten Dolomite in der Oberen Trias, Norian) gespeist. VII Abstract (English) The purposees of this master thesis are on the one hand to assess if dedolomitisation is still an ongoing process in the underground of the Rovte area (W Slovenia) and on the other hand to characterise the hydrochemistry of thermal wells and subthermal springs in NW-Slovenia. To achieve these purposes, waters from deep wells and springs in the Rovte area and waters from thermal wells and subthermal springs in the Cerkno/Kranj area were analysed. Hydrochemical analysis was done by spectrophotometry, ion chromatography and atom absorption spectrometry. Isotope analysis (δ2H and δ18O) was done with the automated Picarro L2130-i analyser. The wells Z (Zavčan), R (Rodofov Mlin) and B (Bizjakov Mlin) penetrate gypsum strata at a depth of several hundred meters. Thus, samples from wells Z and R 2- 2+ 2+ show high SO4 concentrations and molar-Mg /Ca -ratios lower than 1. In 2- - contrast, water samples from surface springs show very low SO4 but high NO3 and Cl- concentrations. These samples are clearly impacted anthropogenically. The isotopes (δ2H and δ18O) of the wells Z and R are in the same range suggesting that the waters from Z and R derive from the same aquifer system. The Calculation of saturation indices with PHREEQC shows that most samples from the wells were supersaturated with respect to calcite and mostly undersaturated with respect to dolomite. Furthermore, the diagram of pH vs. 2- SO4 concentration from Z and R show a negative correlation. This and the preferential removal of Mg2+, as suggested by the molar-Mg2+/Ca2+-ratios lower than 1, indicates that dedolomitisation might still be occurring. The hydrochemical analysis of the waters from thermal wells and subthermal springs revealed that a deep flow pattern exists in NW-Slovenia. The boreholes probably drain the deep aquifer system (namely the Upper Triassic Norian stage grey stratified dolomite). VIII Table of contents Eidesstattliche Erklärung......................................................................................IV Declaration of Authorship......................................................................................V Zusammenfassung (German)...............................................................................VI Abstract (English)................................................................................................VII Table of contents................................................................................................VIII 1. Introduction........................................................................................................ 1 1.1. Geography of Slovenia and areas of interest............................................2 1.2. Paleogeography of Slovenia.....................................................................4 1.3. Geology of NW-Slovenia...........................................................................9 1.3.1. Structural units of NW-Slovenia....................................................10 1.3.2. Geology at Rovte area..................................................................11 1.3.3. Three caves in the Rovte area......................................................17 1.3.4. Geology at the (thermal) springs and wells .................................22 1.4. Thermal heat flow and temperatures in Slovenia...................................31 1.5. Theoretical background..........................................................................34 1.5.1. Hydrochemistry............................................................................34 1.5.2. Dolomitisation and dedolomitisation............................................36 1.5.3. Speleogenesis and deep flow in karst aquifers.............................48 1.5.4. Stable Isotopes (δ18O, oxygen and δ2H, hydrogen)....................52 2. Methods............................................................................................................ 56 2.1. Field Measurements (T, pH, EC, discharge)............................................56 2.2. Discharge...............................................................................................56 2.3. Titration..................................................................................................56 2.4. Spectrophotometry.................................................................................58 2.5. Ion chromatography (IC).........................................................................58 2.6. Atomic adsorption spectrometry (AAS)..................................................59 2.7. Picarro L2130-i Analyser (isotopes)........................................................60 2.8. PHREEQC (Wateq4f.dat).........................................................................61 2.9. Possible errors........................................................................................64 3. Results.............................................................................................................
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