TY - JOUR A1 - Wilke, Franziska Daniela Helena A1 - Schettler, Georg A1 - Vieth-Hillebrand, Andrea A1 - Kühn, Michael A1 - Rothe, Heike T1 - Activity concentrations of U-238 and Ra-226 in two European black shales and their experimentally-derived leachates JF - Journal of Environmental Radioactivity N2 - We performed leaching tests at elevated temperatures and pressures with an Alum black shale from Bomholm, Denmark and a Posidonia black shale from Lower Saxony, Germany. The Alum shale is a carbonate free black shale with pyrite and barite, containing 74.4 mu g/g U. The Posidonia shales is a calcareous shale with pyrite but without detectable amounts of barite containing 3.6 mu g/g U. Pyrite oxidized during the tests forming sulfuric acid which lowered the pH on values between 2 and 3 of the extraction fluid from the Alum shale favoring a release of U from the Alum shale to the fluid during the short-term and in the beginning of the long-term experiments. The activity concentration of U-238 is as high as 23.9 mBq/ml in the fluid for those experiments. The release of U and Th into the fluid is almost independent of pressure. The amount of uranium in the European shales is similar to that of the Marcellus Shale in the United States but the daughter product of U-238, the Ra-226 activity concentrations in the experimentally derived leachates from the European shales are quite low in comparison to that found in industrially derived flowback fluids from the Marcellus shale. This difference could mainly be due to missing Cl in the reaction fluid used in our experiments and a lower fluid to solid ratio in the industrial plays than in the experiments due to subsequent fracking and minute cracks from which Ra can easily be released. KW - Unconventional gas production KW - Black shales KW - Flowback KW - Radioactivity KW - NOR KW - Batch experiments Y1 - 2018 U6 - https://doi.org/10.1016/j.jenvrad.2018.05.005 SN - 0265-931X SN - 1879-1700 VL - 190 SP - 122 EP - 129 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Wilke, Franziska Daniela Helena A1 - Vieth-Hillebrand, Andrea A1 - Naumann, Rudolf A1 - Erzinger, Jörg A1 - Horsfield, Brian T1 - Induced mobility of inorganic and organic solutes from black shales using water extraction: Implications for shale gas exploitation JF - Applied geochemistry : journal of the International Association of Geochemistry and Cosmochemistry N2 - The study reported here evaluates the degree to which metals, salt anions and organic compounds are released from shales by exposure to water, either in its pure form or mixed with additives commonly employed during shale gas exploitation. The experimental conditions used here were not intended to simulate the exploitation process itself, but nevertheless provided important insights into the effects additives have on solute partition behaviour under oxic to sub-oxic redox conditions. In order to investigate the mobility of major (e.g. Ca, Fe) and trace (e.g. As, Cd, Co, Mo, Pb, U) elements and selected organic compounds, we performed leaching tests with black shale samples from Bornholm, Denmark and Lower Saxony, Germany. Short-term experiments (24 h) were carried out at ambient pressure and temperatures of 100 degrees C using five different lab-made stimulation fluids. Two long-term experiments under elevated pressure and temperature conditions at 100 degrees C/100 bar were performed lasting 6 and 2 months, respectively, using a stimulation fluid containing commercially-available biocide, surfactant, friction reducer and clay stabilizer. Our results show that the amount of dissolved constituents at the end of the experiment is independent of the pH of the stimulation fluid but highly dependent on the composition of the black shale and the buffering capacity of specific components, namely pyrite and carbonates. Shales containing carbonates buffer the solution at pH 7-8. Sulphide minerals (e.g. pyrite) become oxidized and generate sulphuric acid leading to a pH of 2-3. This low pH is responsible for the overall much larger amount of cations dissolved from shales containing pyrite but little to no carbonate. The amount of elements released into the fluid is also dependent on the residence time, since as much as half of the measured 23 elements show highest concentrations within four days. Afterwards, the concentration of most of the elemental species decreased pointing to secondary precipitations. Generally, in our experiments less than 15% of each analysed element contained in the black shale was mobilised into the fluid. (C) 2015 Elsevier Ltd. All rights reserved. KW - Unconventional gas KW - Black shales KW - Stimulation fluids KW - Element mobility KW - Batch experiments Y1 - 2015 U6 - https://doi.org/10.1016/j.apgeochem.2015.07.008 SN - 0883-2927 VL - 63 SP - 158 EP - 168 PB - Elsevier CY - Oxford ER -