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 - TY - JOUR A1 - Wilke, Franziska Daniela Helena A1 - Vasquez, Monica A1 - Wiersberg, Thomas A1 - Naumann, Rudolf A1 - Erzinger, Jörg T1 - On the interaction of pure and impure supercritical CO2 with rock forming minerals in saline aquifers: An experimental geochemical approach JF - Applied geochemistry : journal of the International Association of Geochemistry and Cosmochemistry N2 - The aim of this experimental study was to evaluate and compare the geochemical impact of pure and impure CO2 on rock forming minerals of possible CO2 storage reservoirs. This geochemical approach takes into account the incomplete purification of industrial captured CO2 and the related effects during injection, and provides relevant data for long-term storage simulations of this specific greenhouse gas. Batch experiments were conducted to investigate the interactions of supercritical CO2, brine and rock-forming mineral concentrates (albite, microcline, kaolinite, biotite, muscovite, calcite, dolomite and anhydrite) using a newly developed experimental setup. After up to 42 day (1000 h) experiments using pure and impure supercritical CO2 the dissolution and solution characteristics were examined by XRD, XRF, SEM and EDS for the solid, and ICP-MS and IC for the fluid reactants, respectively. Experiments with mixtures of supercritical CO2 (99.5 vol.%) and SO2 or NO2 impurities (0.5 vol.%) suggest the formation of H2SO4 and HNO3, reflected in pH values between 1 and 4 for experiments with silicates and anhydrite and between 5 and 6 for experiments with carbonates. These acids should be responsible for the general larger amount of cations dissolved from the mineral phases compared to experiments using pure CO2. For pure CO2 a pH of around 4 was obtained using silicates and anhydrite, and 7-8 for carbonates. Dissolution of carbonates was observed after both pure and impure CO2 experiments. Anhydrite was corroded by approximately 50 wt.% and gypsum precipitated during experiments with supercritical CO2 + NO2. Silicates do not exhibit visible alterations during all experiments but released an increasing amount of cations in the reaction fluid during experiments with impure CO2. Nonetheless, precipitated secondary carbonates could not be identified. Y1 - 2012 U6 - https://doi.org/10.1016/j.apgeochem.2012.04.012 SN - 0883-2927 VL - 27 IS - 8 SP - 1615 EP - 1622 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Schicks, Judith Maria A1 - Erzinger, Jörg A1 - Ziemann, Martin Andreas T1 - Raman spectra of gas hydrates : differences and analogies to ice 1h and (gas saturated) water N2 - It is generally accepted that Raman spectroscopic investigations of gas hydrates provide vital information regarding the structure of the hydrate, hydrate composition and cage occupancies, but most research is focused on the vibrational spectra of the guest molecules. We show that the shape and position of the Raman signals of the host molecules (H2O) also contain useful additional information. In this study, Raman spectra (200-4000cm(-1)) of (mixed) gas hydrates with variable compositions and different structures are presented. The bands in the O-H stretching region (3000- 3800cm(-1)), the O-H bending region (1600-1700cm(-1)) and the O-O hydrogen bonded stretching region (100-400cm(-1)) are compared with the corresponding bands in Raman spectra of ice Ih and liquid water. The interpretation of the differences and similarities with respect to the crystal structure and possible interactions between guest and host molecules are presented. (c) 2005 Elsevier B.V. All rights reserved Y1 - 2005 UR - http://www.sciencedirect.com/science/journal/13861425 U6 - https://doi.org/10.1016/j.saa.2005.02.019 SN - 1386-1425 ER -