Determining conventional and unconventional oil and gas well brines in natural sample II: Cation analyses with ICP-MS and ICP-OES.

Flowback and produced water generated by the hydraulic fracturing of unconventional oil and gas plays contain a suite of cations (e.g., metals) typically in a high salt (e.g., NaCl) matrix. Here, we analyzed the chemical (cation) composition of production fluids associated with natural gas and oil development (e.g., flowback, produced water, impoundment fluids), along with mine drainage, and surface and ground water samples using ICP-OES and ICP-MS. ICP-MS and ICP-OES analytical performance and interference effects were evaluated. Both platforms exhibited excellent analytical spike recoveries, detection limits for blank and spiked solutions, and accuracy for standard certified reference materials. Mass ratio analyses using Ca/Sr, Ca/Mg, Ba/Sr, Mg/Sr, and B and Li, were assessed for their efficacy in differentiation among brines from conventional oil wells, produced water from unconventional oil and gas wells and impoundments, mine drainage treatment pond water, groundwater, and surface water. Examination of Mg/Sr ratios when compared with Li concentrations provide clear separation among the different types of samples, while Ca/Mg versus Ca/Sr correlations were useful for distinguishing between conventional and unconventional oil and gas fluids.

Determining conventional and unconventional oil and gas well brines in natural samples I: Anion analysis with ion chromatography.

Unconventional natural gas extraction by hydraulic fracturing requires millions of gallons of water and generates flowback water, produced water and recycled fluids of varying chemical composition. Ion chromatography (IC) is a relatively low cost and efficient means to determine the anionic composition, however, the wide range in anionic content of these fluids poses a challenge to analytical methods developed for "natural" waters. We report here that the combination of UV and conductivity detectors increased detection sensitivity (e.g., 10-50 ppb) and expanded the number of anions detectable in a single sample run. Samples from four unconventional shale gas wells, two impoundments, nine conventional oil wells, two freshwater streams and mine drainage samples were analyzed in this study. All produced water samples and impoundment samples had high chloride (17,500-103,000 mg L-1, 93,900 to 134,000 mg L-1, 27,700 and 30,700 mg L-1), bromide (178-996 mg L-1, 183-439 mg L-1, 230 and 260 mg L-1) and conductivity (38,500-160,000 µS/cm3, 95,300 to 183,000 µS/cm3, 61,500 and 103,000 µS/cm3), respectively, relative to mine drainage and freshwater stream samples. Molar ratio analysis using Cl-/Br- to Cl- and SO42-/Cl- to Br- revealed significant differences between the samples, providing a simple means for distinguishing water impacted by different sources of contamination.

Determining conventional and unconventional oil and gas well brines in natural samples III: mass ratio analyses using both anions and cations.

Identifying the types of contamination and their sources in surface and groundwater is fundamental for effective protection of private and public source waters. Here we employed mass ratio analyses of a variety of anion and cation pairs to characterize flowback, produced water, and mine drainage. These endmembers were used to evaluate the source contributions of natural surface and ground water samples. A total of 1,177 ground water and surface water samples were analyzed including high-quality source waters and waters suspected of being impacted by drilling and mining activity. We found the following chemical ratios resolved different sources of contamination: Mg/Na vs SO4/Cl; SO4/Cl vs Mg/Li; Br/SO4 vs Ba/Cl; and Br vs Mg/Li. While no single parameter or mass ratio pairing by itself was definitive it was possible to converge on a likely source of contamination using multiple lines of analytical evidence. Further, this process clarified sources in impacted samples where one or more parameters commonly considered diagnostic of specific sources (e.g., Br, Ba), were below detection limits (e.g., too dilute) or not tested for. Ultimately, movement of sample values within the mass ratio space allows tracking of changes in water quality and contamination source dynamics as the water chemistry evolves.