Synthetic Chemicals as Potential Tracers of Impacts of Fracturing Fluids on Groundwater

Application of hydraulic fracturing to produce “unconventional” oil and gas from shale formations and other low-permeability geological units has raised concerns about the potential environmental impacts, including potential adverse effects of fracturing fluids (FF) on groundwater. In this study, laboratory batch test experiments and new analytical methods were developed to analyze FF chemicals as potential indicators (tracers) to detect impacts of fracturing fluids on groundwater. The tests, conducted over 101–196 days, included FF with synthetic chemicals (~40,000–4,000,000 µg/L), placed in batches with groundwater and sediment at 5° and 25 °C, along with sterile controls. Using the new methods, measurable concentrations of the FF chemicals were many orders in magnitude lower (~3000 to 3,000,000 X) compared to their concentrations in synthetic fracturing fluids, indicating that these chemicals are excellent candidates as indicators of FF contamination in groundwater, if they are relatively persistent, and not prone to extensive loss by sorption during migration in the subsurface. Variable sorption and degradation of the chemicals was observed in both batch and column tests. Sorption was negligible (sorption coefficient, Kd~0.0) for some synthetic chemicals (polyethylene glycol, ethanolamines, isopropanol, and ethyl hexanol) in some tests. At the other extreme, strong sorption was observed for some of the higher molecular weight cocamido propyl betaine (max Kd = 1.17) and polyethylene glycol (max Kd = 1.12) components, and triethanolamine (max Kd = 0.47) in other tests. Apparent loss by degradation was observed for each chemical in some tests, but negligible in others. The shortest apparent half-lives were for isopropanol and ethyl hexanol at 25 °C (t½ < 11 days), and the most persistent synthetic chemicals were polyethylene glycols (t½ ≥ 182 d) and the ethanolamines (t½ ≥ 212 d). Of the potentially diagnostic FF chemicals investigated, the relatively hydrophilic and persistent lower molecular weight polyethylene glycols are some of the most promising as potential indicators of contamination of groundwater by FF.