@article{WilkeViethHillebrandNaumannetal.2015,
  author    = {Wilke, Franziska Daniela Helena and Vieth-Hillebrand, Andrea and Naumann, Rudolf and Erzinger, J{\"o}rg and Horsfield, Brian},
  title     = {Induced mobility of inorganic and organic solutes from black shales using water extraction: Implications for shale gas exploitation},
  series = {Applied geochemistry : journal of the International Association of Geochemistry and Cosmochemistry},
  volume    = {63},
  journal   = {Applied geochemistry : journal of the International Association of Geochemistry and Cosmochemistry},
  publisher = {Elsevier},
  address   = {Oxford},
  issn      = {0883-2927},
  doi       = {10.1016/j.apgeochem.2015.07.008},
  pages     = {158 -- 168},
  year      = {2015},
  abstract  = {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.},
  language  = {en}
}
@article{NitzscheKleebergHoffmannetal.2022,
  author    = {Nitzsche, Kai Nils and Kleeberg, Andreas and Hoffmann, Carsten and Merz, Christoph and Premke, Katrin and Gessler, Arthur and Sommer, Michael and Kayler, Zachary E.},
  title     = {Kettle holes reflect the biogeochemical characteristics of their catchment area and the intensity of the element-specific input},
  series = {Journal of soils and sediments : protection, risk assessment and remediation},
  volume    = {22},
  journal   = {Journal of soils and sediments : protection, risk assessment and remediation},
  number    = {3},
  publisher = {Springer},
  address   = {Heidelberg},
  issn      = {1439-0108},
  doi       = {10.1007/s11368-022-03145-8},
  pages     = {994 -- 1009},
  year      = {2022},
  abstract  = {Purpose Kettle holes are small inland water bodies known to be dominated by terrigenous material; however, the processes and structures that drive the enrichment and depletion of specific geochemical elements in the water column and kettle hole sediment remain unclear. We hypothesized that the mobile elements (Ca, Fe, K, P) behave different from each other in their transport, intermediate soil retention, and final accumulation in the kettle hole sediment. Methods Topsoils from transects spanning topographic positions from erosional to depositional areas, sediment cores, shallow groundwater, and kettle hole water of two glacial kettle holes in NE Germany (Rittgarten (RG) and Kraatz (KR)) were collected. The Fe, Ca, K, and total P (TP) concentrations were quantified and additionally the major anions in shallow groundwater and kettle hole water. The element-specific mobilization, relocation, and, finally, accumulation in the sediment were investigated by enrichment factors. Furthermore, a piper diagram was used to estimate groundwater flow directions and pond-internal processes. Results At KR only, the upper 10 cm of the kettle hole sediment reflected the relative element composition of the eroded terrestrial soils. The sediment from both kettle holes was enriched in Ca, Fe, K, and P compared to topsoils, indicating several possible processes including the input of clay and silt sized particles enriched in these elements, fertilizer input, and pond-internal processes including biogenic calcite and hydroxyapatite precipitation, Fe-P binding (KR), FeSx formation (RG), and elemental fixation and deposition via floating macrophytes (RG). High Ca concentrations in the kettle hole water indicated a high input of Ca from shallow groundwater inflow, while Ca precipitation in the kettle hole water led to lower Ca concentration in groundwater outflow. Conclusions The considerable element losses in the surrounding soils and the inputs into the kettle holes should be addressed by comprehensive soil and water protection measures, i.e., avoiding tillage, fertilizing conservatively, and creating buffer zones.},
  language  = {en}
}
@article{HalamaKonradSchmolke2015,
  author    = {Halama, Ralf and Konrad-Schmolke, Matthias},
  title     = {Retrograde metasomatic effects on phase assemblages in an interlayered blueschist-greenschist sequence (Coastal Cordillera, Chile)},
  series = {Lithos : an international journal of mineralogy, petrology, and geochemistry},
  volume    = {216},
  journal   = {Lithos : an international journal of mineralogy, petrology, and geochemistry},
  publisher = {Elsevier},
  address   = {Amsterdam},
  issn      = {0024-4937},
  doi       = {10.1016/j.lithos.2014.12.004},
  pages     = {31 -- 47},
  year      = {2015},
  abstract  = {Interlayered blueschists and greenschists of the Coastal Cordillera (Chile) are part of a Late Palaeozoic accretionary complex. They represent metavolcanic rocks with oceanic affinities based on predominantly 01B-type REE patterns and immobile trace element ratios. Both rock types have similar mineralogies, albeit with different mineral modal abundances. Amphibole is the major mafic mineral and varies compositionally from glaucophane to actinolite. The presence of glaucophane relicts as cores in zoned amphiboles in both blueschists and greenschists is evidence for a pervasive high-pressure metamorphic stage, indicating that tectonic juxtaposition is an unlikely explanation for the cm-dm scale interlayering. During exhumation, a retrograde greenschist-facies overprint stabilized chlorite + albite + winchitic/actinolitic amphibole + phengitic white mica +/- epidote +/- K-feldspar at 0.4 +/- 0.1 GPa. Geochemical variability can be partly ascribed to primary magmatic and partly to secondary metasomatic processes that occurred under greenschist-facies conditions. Isocon diagrams of several adjacent blueschist-greenschist pairs with similar protolith geochemistry were used to evaluate metasomatic changes due to retrograde fluid-rock interaction. The most important geochemical changes are depletion of Si and Na and addition of water in the greenschists compared to the blueschists. Transition metals and LILE are mobilized to varying degrees. The unsystematic deviations from magmatic fractionation trends suggest open system conditions and influx of an external fluid. Pseudosection and water isopleth calculations show that the rocks were dehydrating during most of their exhumation history and remained at water-saturated conditions. The mineralogical changes, in particular breakdown of blue amphibole and replacement by chlorite, albite and calcic/sodic-calcic amphibole, are the prime cause for the distinct coloring. Pseudo-binary phase diagrams were used as a means to link bulk rock geochemical variability to modal and chemical changes in the mineralogy. The geochemical changes induced by fluid-rock interaction are important in two ways: First, the bulk rock chemistry is altered, leading to the stabilization of higher modal proportions of chlorite in the greenschists. Second, the retrograde overprint is a selective, layer-parallel fluid infiltration process, causing more intense greenschist-facies recrystallization in greenschist layers and therefore preferential preservation of blue amphibole in blueschist layers. Hence, the distinct colors were acquired by a combination of compositional variability, both primary magmatic and secondary metasomatic, and the different intensity of retrograde fluid infiltration. (C) 2014 Elsevier B.V. All rights reserved.},
  language  = {en}
}