Industries such as unconventional natural gas have seen increased global expansion to meet the increasing energy needs of our increasing global population. Unconventional gas uses hydraulic fracturing that produces significant volumes of produced waters, which can be highly saline and pose a toxic threat to freshwater invertebrates if exposure via discharges, spills, leaks, or runoff were to occur. The primary aim of the present review was to determine the sodium (Na + ) and chloride (Cl − ) content of these waters as an approximate measure of salinity and how these values compare to the NaCl or synthetic marine salt acute toxicity values of freshwater invertebrate taxa. Shale gas produced waters are much more saline with 78 900 ± 10 200 NaCl mg/L and total dissolved solids (TDS) of 83 200 ± 12 200 mg/L compared to coal bed methane (CBM) produced waters with 4300 ± 1100 NaCl mg/L and TDS of 5900 ± 1300 mg/L and pose a far greater toxicity risk from NaCl to freshwater invertebrates. In addition, the toxicity of other major ions (Ca 2+ , K + , Mg 2+ , CO 3 2− , HCO 3 − , and SO 4 2−) and their influence on the toxicity of Na + and Cl − were evaluated. Exposure of untreated and undiluted shale gas produced waters to freshwater invertebrates is likely to result in significant or complete mortality. Shale gas produced waters have higher concentrations of various metals compared with CBM produced waters and are more acidic. We recommend future research to increase the reporting and consistency of water quality parameters, metals, and particularly organics of produced waters to provide a better baseline and help in further investigations.

The 96-h acute toxicity of barium (Ba 2+ ), o-cresol, and sodium chloride (NaCl) to Paratya australiensis was assessed in single, binary, and ternary combinations in addition to three biochemical assays: glutathione S-transferase, acetylcholinesterase, and sodium-potassium adenosine triphosphatase. The 96-h lethal concentrations that expressed 50% mortality (LC50) in the single-toxicant exposures were Ba 2+ = 23.4 mg/L, o-cresol = 12.2 mg/L, and NaCl = 4198 mg/L. Mortality from ocresol exposure occurred between 11 and 22 mg/L, whereas Ba 2+ was more gradual across 10-105 mg/L, and most of the NaCl mortality occurred between 2050 and 4100 mg/L. Toxic units were used to assess the binary and ternary interactions of the toxicants. A more than additive effect was observed for most combinations in the binary chemical exposures, with the ternary combinations yielding highly synergistic interactions. Greater synergism was observed with the 96-h LC50 of o-cresol in combination with the three concentrations of NaCl (1025, 2050, and 3075 mg/L) compared with Ba 2+ , with toxic units of 0.38, 0.48, and 0.10 (o-cresol) and 0.71, 0.67, and 0.50 (Ba 2+ ). No notable enzyme activity trends were observed in the enzyme biomarker responses from both individual and mixture exposures. Although acute single-species toxicity tests tend to underestimate the effects of Ba 2+ , o-cresol, and NaCl on populations, communities, and ecosystems in seminatural (e.g., mesocosms) and natural systems, there are currently no published acute toxicity data available for P. australiensis and the three toxicants used in the present study. The present study shows that chemicals with different toxicity mechanisms can potentially lead to more synergistic responses.

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