Observations of VOC emissions and photochemical products over US oil- and gas-producing regions using high-resolution H₃O⁺ CIMS (PTR-ToF-MS)

Abstract. VOCs related to oil and gas extraction operations in the United States were measured by H₃O⁺ chemical ionization time-of-flight mass spectrometry (H₃O⁺ ToF-CIMS/PTR-ToF-MS) from aircraft during the Shale Oil and Natural Gas Nexus (SONGNEX) campaign in March–April 2015. This work presents an overview of major VOC species measured in nine oil- and gas-producing regions, and a more detailed analysis of H₃O⁺ ToF-CIMS measurements in the Permian Basin within Texas and New Mexico. Mass spectra are dominated by small photochemically produced oxygenates and compounds typically found in crude oil: aromatics, cyclic alkanes, and alkanes. Mixing ratios of aromatics were frequently as high as those measured downwind of large urban areas. In the Permian, the H₃O⁺ ToF-CIMS measured a number of underexplored or previously unreported species, including aromatic and cycloalkane oxidation products, nitrogen heterocycles including pyrrole (C₄H₅N) and pyrroline (C₄H₇N), H₂S, and a diamondoid (adamantane) or unusual monoterpene. We additionally assess the specificity of a number of ion masses resulting from H₃O⁺ ion chemistry previously reported in the literature, including several new or alternate interpretations.