High-Resolution Mass Spectrometry Identification of Novel Surfactant-Derived Sulfur-Containing Disinfection Byproducts from Gas Extraction Wastewater.

Introduction of oil and gas extraction wastewaters (OGWs) to surface water leads to elevated halide levels from geogenic bromide and iodide, as well as enhanced formation of brominated and iodinated disinfection byproducts (DBPs) when treated. OGWs contain high levels of chemical additives used to optimize extraction activities, such as surfactants, which have the potential to serve as organic DBP precursors in OGW-impacted water sources. We report the first identification of olefin sulfonate surfactant-derived DBPs from laboratory-disinfected gas extraction wastewater. Over 300 sulfur-containing DBPs, with 43 unique molecular formulas, were found by high-resolution mass spectrometry, following bench-scale chlor(am)ination. DBPs consisted of mostly brominated species, including bromohydrin sulfonates, dihalo-bromosulfonates, and bromosultone sulfonates, with chlorinated/iodinated analogues formed to a lesser extent. Disinfection of a commercial C12-olefin sulfonate surfactant mixture revealed dodecene sulfonate as a likely precursor for most detected DBPs; disulfur-containing DBPs, like bromosultone sulfonate and bromohydrin disulfonate, originated from olefin disulfonate species, present as side-products of olefin sulfonate production. Disinfection of wastewaters increased mammalian cytotoxicity several orders of magnitude, with chloraminated water being more toxic. This finding is important to OGW-impacted source waters because drinking water plants with high-bromide source waters may switch to chloramination to meet DBP regulations.

Impacts of hydraulic fracturing wastewater from oil and gas industries on drinking water: Quantification of 69 disinfection by-products and calculated toxicity.

Oil and gas production generates large amounts of brine wastewater called "produced water" with various geogenic and synthetic contaminants. These brines are generally used in hydraulic fracturing operations to stimulate production. They are characterized by elevated halide levels, particularly geogenic bromide and iodide. Such salt concentrations in produced water may be as high as thousands of mg/L of bromide and tens of mg/L of iodide. Large volumes of produced water are stored, transported, reused in production operations, and ultimately disposed of by deep well injection into saline aquifers. Improper disposal may potentially contaminate shallow freshwater aquifers and impact drinking water sources. Because conventional produced water treatment typically does not remove halides, produced water contamination of groundwater aquifers may cause the formation of brominated and iodinated disinfection by-products (I-DBPs) at municipal water treatment plants. These compounds are of interest because of their higher toxicity relative to their chlorinated counterparts. This study reports a comprehensive analysis of 69 regulated and priority unregulated DBPs in simulated drinking waters fortified with 1 % (v/v) oil and gas wastewater. Impacted waters produced 1.3×-5× higher levels of total DBPs compared to river water after chlorination and chloramination. Individual DBP levels ranged from (<0.1-122 µg/L). Overall, chlorinated waters formed highest levels, including trihalomethanes that would exceed the U.S. EPA regulatory limit of 80 µg/L. Chloraminated waters had more I-DBP formation and highest levels of haloacetamides (23 µg/L) in impacted water. Calculated cytotoxicity and genotoxicity were higher for impacted waters treated with chlorine and chloramine than corresponding treated river waters. Chloraminated impacted waters had the highest calculated cytotoxicity, likely due to higher levels of more toxic I-DBPs and haloacetamides. These findings demonstrate that oil and gas wastewater if discharged to surface waters could adversely impact downstream drinking water supplies and potentially affect public health.