Modelling the attenuation of flowback chemicals for a soil-groundwater pathway from a hypothetical spill accident.

Flowback water from shale gas operations contains formation-derived compounds, including trace metals, radionuclides, and organics. While accidental releases from storage tanks with flowback water are low-probability events if multiple containment barriers are put in place, they cannot be entirely excluded. Here the natural attenuation potential of deep unsaturated zones and groundwater was explored using predictive modelling involving a hypothetical leak from a storage tank. Actual chemical concentrations from flowback water at two shale gas wells with contrasting salinity (12,300 and 105,000 ppm TDS) in the Beetaloo Sub-basin (Northern Territory, Australia) served as input to the one-dimensional HYDRUS model for simulating chemical transport through the unsaturated zone, with groundwater at 50 and 100 m depth, respectively. Subsequent chemical transport in groundwater involved the use of a three-dimensional analytical transport model. For a total of 63 chemicals the long-term attenuation from dilution and dispersion in unsaturated sediments and groundwater was calculated. Predicted environmental concentrations for aquatic receptors were compared with no-effect levels of individual chemicals to derive risk quotients (RQ) and identify chemicals of no concern to ecosystem health (i.e. RQ <1). Except for salinity and radium-228 in one of the two wells, RQ < 1 for all other chemicals. The initial approach considered testing of toxicity to individual chemicals only. When direct toxicity assessments (DTAs) were used to account for effects of chemical mixtures, the required DTA-derived safe dilution factor for 95% species protection was 1.8 to 2.5 times higher than the dilution factor accounting for dispersion and dilution only. Accounting for biodegradation, sorption and radioactive decay decreased chemical concentrations in unsaturated sediments to safe levels using the DTA for all chemicals. The study highlighted the importance of incorporating DTA in chemical risk assessments involving complex chemical mixtures. Improved understanding of fate and transport of flowback chemicals will help effectively manage water-quality risks associated with shale gas extraction.