Extension of Methane Emission Rate Distribution for Permian Basin Oil and Gas Production Infrastructure by Aerial LiDAR.

Aerial LiDAR measurements at 7474 oil and gas production facilities in the Permian Basin yield a measured methane emission rate distribution extending to the detection sensitivity of the method, 2 kg/h at 90% probability of detection (POD). Emissions are found at 38.3% of facilities scanned, a significantly higher proportion than reported in lower-sensitivity campaigns. LiDAR measurements are analyzed in combination with measurements of the heavy tail portion of the distribution (>600 kg/h) obtained from an airborne solar infrared imaging spectrometry campaign by Carbon Mapper (CM). A joint distribution is found by fitting the aligned LiDAR and CM data. By comparing the aerial samples to the joint distribution, the practical detection sensitivity of the CM 2019 campaign is found to be 280 kg/h [256, 309] (95% confidence) at 50% POD for facility-sized emission sources. With respect to the joint model distribution and its confidence interval, the LiDAR campaign is found to have measured 103.6% [93.5, 114.2%] of the total emission rate predicted by the model for equipment-sized emission sources (∼2 m diameter) with emission rates above 3 kg/h, whereas the CM 2019 campaign is found to have measured 39.7% [34.6, 45.1%] of the same quantity for facility-sized sources (150 m diameter) above 10 kg/h. The analysis is repeated with data from CM 2020-21 campaigns with similar results. The combined distributions represent a more comprehensive view of the emission rate distribution in the survey area, revealing the significance of previously underreported emission sources at rates below the detection sensitivity of some emissions monitoring campaigns.

Role of Explicit Hydration in Predicting the Aqueous Standard Reduction Potential of Sulfate Radical Anion by DFT and Insight into the Influence of pH on the Reduction Potential.

Sulfate radical anion (SO4•-) is a potent oxidant capable of destroying recalcitrant environmental contaminants such as perfluoroalkyl carboxylic acids. In addition, it is thought to participate in important atmospheric reactions. Its standard reduction potential (E°) is fundamental to its reactivity. Using theoretical methods to accurately predict the aqueous phase E° requires solvation with explicit water molecules. Herein, using density functional theory, we calculated the aqueous E° of SO4•- and evaluated sensitivity to explicit water count. The E° increased considerably with more waters until ca. 24 were included, after which change in E° was small. When a proton was added to these systems, the E° was similar regardless of the explicit water count and this value was similar to the E° for systems with a large number of explicit waters but no proton. This result agrees with literature evidence that the E° is pH independent. Natural Bond Orbital natural population analysis indicated that in the case of both SO42- and SO4•-, considerable charge was donated from the SO4 center to the explicit solvation shells.

Role of pH in the Transformation of Perfluoroalkyl Carboxylic Acids by Activated Persulfate: Implications from the Determination of Absolute Electron-Transfer Rates and Chemical Computations.

Perfluoroalkyl carboxylic acids (PFCAs) are ubiquitous contaminants known for their bioaccumulation, toxicological harm, and resistance to degradation. Remediating PFCAs in water is an ongoing challenge with existing technologies being insufficient or requiring additional disposal. An emergent approach is using activated persulfate, which degrades PFCAs through sequential scission of CF2 equivalents yielding shorter-chain homologues, CO2 and F-. This transformation is thought to be initiated by single electron transfer (SET) from the PFCA to the activate oxidant, SO4•-. A pronounced pH effect has been observed for thermally activated persulfate PFCA transformation. To evaluate the role of pH during SET, we directly determined absolute rate constants for perfluorobutanoic acid and trifluoroacetic acid oxidation by SO4•- in the pH range of 0.5-4.0 using laser flash photolysis. The average of the rate constants for both substrates across all pH values was 9 ± 2 × 103 M-1 s-1 (±2σ), implying that acid catalysis of thermal persulfate activation may be the primary culprit of the observed pH effect, instead of pH influencing the SET step. In addition, density functional theory was used to investigate if SO4•-protonation might enhance PFCA transformation kinetics. We found that when calculations include explicit water molecules, direct SO4•- protonation does not occur.