Activity concentrations of 238U and 226Ra in two European black shales and their experimentally-derived leachates.

The production of gas from unconventional resources became an important position in the world energy economics. In 2012, the European Commission's Joint Research Centre estimate 16 trillion cubic meters (Tcm) of technically recoverable shale gas in Europe. Taking into account that the exploitation of unconventional gas can be accompanied by serious health risks due to the release of toxic chemical components and natural occurring radionuclides into the return flow water and their near-surface accumulation in secondary precipitates, we investigated the release of U, Th and Ra from black shales by interaction with drilling fluids containing additives that are commonly employed for shale gas exploitation. We performed leaching tests at elevated temperatures and pressures with an Alum black shale from Bornholm, 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 µg/g U. The Posidonia shales is a calcareous shale with pyrite but without detectable amounts of barite containing 3.6 µg/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 238U 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 238U, the 226Ra 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.

Mineral dissolution and reprecipitation mediated by an amorphous phase.

Fluid-mediated mineral dissolution and reprecipitation processes are the most common mineral reaction mechanism in the solid Earth and are fundamental for the Earth's internal dynamics. Element exchange during such mineral reactions is commonly thought to occur via aqueous solutions with the mineral solubility in the coexisting fluid being a rate limiting factor. Here we show in high-pressure/low temperature rocks that element transfer during mineral dissolution and reprecipitation can occur in an alkali-Al-Si-rich amorphous material that forms directly by depolymerization of the crystal lattice and is thermodynamically decoupled from aqueous solutions. Depolymerization starts along grain boundaries and crystal lattice defects that serve as element exchange pathways and are sites of porosity formation. The resulting amorphous material occupies large volumes in an interconnected porosity network. Precipitation of product minerals occurs directly by repolymerization of the amorphous material at the product surface. This mechanism allows for significantly higher element transport and mineral reaction rates than aqueous solutions with major implications for the role of mineral reactions in the dynamic Earth.

Groundwater fluoride enrichment in an active rift setting: Central Kenya Rift case study.

Groundwater is used extensively in the Central Kenya Rift for domestic and agricultural demands. In these active rift settings groundwater can exhibit high fluoride levels. In order to address water security and reduce human exposure to high fluoride in drinking water, knowledge of the source and geochemical processes of enrichment are required. A study was therefore carried out within the Naivasha catchment (Kenya) to understand the genesis, enrichment and seasonal variations of fluoride in the groundwater. Rocks, rain, surface and groundwater sources were sampled for hydrogeochemical and isotopic investigations, the data was statistically and geospatially analyzed. Water sources have variable fluoride concentrations between 0.02-75 mg/L. 73% exceed the health limit (1.5mg/L) in both dry and wet seasons. F(-) concentrations in rivers are lower (0.2-9.2mg/L) than groundwater (0.09 to 43.6 mg/L) while saline lake waters have the highest concentrations (0.27-75 mg/L). The higher values are confined to elevations below 2000 masl. Oxygen (δ(18)O) and hydrogen (δD) isotopic values range from -6.2 to +5.8‰ and -31.3 to +33.3‰, respectively, they are also highly variable in the rift floor where they attain maximum values. Fluoride base levels in the precursor vitreous volcanic rocks are higher (between 3750-6000 ppm) in minerals such as cordierite and muscovite while secondary minerals like illite and kaolinite have lower remnant fluoride (<1000 ppm). Thus, geochemical F(-) enrichment in regional groundwater is mainly due to a) rock alteration, i.e. through long residence times and natural discharge and/or enhanced leakages of deep seated geothermal water reservoirs, b) secondary concentration fortification of natural reservoirs through evaporation, through reduced recharge and/or enhanced abstraction and c) through additional enrichment of fluoride after volcanic emissions. The findings are useful to help improve water management in Naivasha as well as similar active rift setting environments.