Sorption and transformation of biocides from hydraulic fracturing in the Marcellus Shale: a review

Biocides are applied as chemical additives in hydraulic fracturing fluids to control subsurface microbial activity. When biocides are released into the subsurface, their fate is controlled by sorption to solids and heterogeneous electron transfer (redox) reactions at the mineral-fluid interface. The ability to predict whether produced water may contain unreacted biocides, or biocide-mineral transformation products, is relevant for defining optimal produced water treatment and beneficial use approaches. This article reviews major minerals that may impact biocide sorption and reactivity in the Marcellus Shale, with a specific focus on biocide-mineral interactions. The chemical and physical properties of quartz, illite, chlorite, pyrite, calcite and dolomite are presented and their reactions with organic compounds structurally similar to biocides are identified. Oxygen-containing functional groups are common among organic biocides, where the carbonyl (-C=O) substructure is integrated into many biocides. Cationic surfactant biocides are expected to sorb to every mineral. Clays, because of their negative surface charge and comparatively high surface area, make excellent sorbents of positively charged biocides. Sorption to organic matter is expected to be limited due to the very polar groups found in biocides. Pyrite is most likely to cause transformation of biocides due to its ability to reduce halogenated organic compounds and initiate Fenton-like reactions, which generate non-specific hydroxyl radicals that react with biocides. Carbonate minerals may act as potential chemisorption sites for biocides possessing a carbonyl group adjacent to another electronegative group. However, the rapid dissolution of this mineral limits its persistence at the mineral-fluid interface. These potential sorption versus transformation reactions can be applied to predict biocide fate in unconventional oil and gas reservoirs and, where appropriate, other subsurface reservoirs used for energy resource extraction or storage.