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Coordinated dual-tracer, aircraft-based, and direct component-level measurements were made at midstream natural gas gathering and boosting stations in the Fayetteville shale (Arkansas, USA). On-site component-level measurements were combined with engineering estimates to generate comprehensive facility-level methane emission rate estimates ('study on-site estimates (SOE)') comparable to tracer and aircraft measurements. Combustion slip (unburned fuel entrained in compressor engine exhaust), which was calculated based on 111 recent measurements of representative compressor engines, accounts for an estimated 75% of cumulative SOEs at gathering stations included in comparisons. Measured methane emissions from regenerator vents on glycol dehydrator units were substantially larger than predicted bymore » modelling software; the contribution of dehydrator regenerator vents to the cumulative SOE would increase from 1% to 10% if based on direct measurements. Concurrent measurements at 14 normally-operating facilities show relative agreement between tracer and SOE, but indicate that tracer measurements estimate lower emissions (regression of tracer to SOE = 0.91 (95% CI = 0.83-0.99), R2 = 0.89). Tracer and SOE 95% confidence intervals overlap at 11/14 facilities. Contemporaneous measurements at six facilities suggest that aircraft measurements estimate higher emissions than SOE. Aircraft and study on-site estimate 95% confidence intervals overlap at 3/6 facilities. The average facility level emission rate (FLER) estimated by tracer measurements in this study is 17-73% higher than a prior national study by Marchese et al.« less

This study presents the results of a campaign that estimated methane emissions at 268 gas production facilities in the Fayetteville shale gas play using onsite measurements (261 facilities) and two downwind methods - the dual tracer flux ratio method (Tracer Facility Estimate - TFE, 17 facilities) and the EPA Other Test Method 33a (OTM33A Facility Estimate - OFE, 50 facilities). A study onsite estimate (SOE) for each facility was developed by combining direct measurements and simulation of unmeasured emission sources, using operator activity data and emission data from literature. The SOE spans 0-403 kg/h and simulated methane emissions from liquidmore » unloadings account for 88% of total emissions estimated by the SOE, with 76% (95% CI [51%-92%]) contributed by liquid unloading at two facilities. TFE and SOE show overlapping 95% CI between individual estimates at 15 of 16 (94%) facilities where the measurements were paired, while OFE and SOE show overlapping 95% CI between individual estimates at 28 of 43 (65%) facilities. However, variance-weighted least-squares (VWLS) regressions performed on sets of paired estimates indicate statistically significant differences between methods. The SOE represents a lower bound of emissions at facilities where onsite direct measurements of continuously emitting sources are the primary contributor to the SOE, a sub-selection of facilities which minimizes expected inter-method differences for intermittent pneumatic controllers and the impact of episodically-emitting unloadings. At 9 such facilities, VWLS indicates that TFE estimates systematically higher emissions than SOE (TFE-to-SOE ratio = 1.6, 95% CI [1.2 to 2.1]). At 20 such facilities, VWLS indicates that OFE estimates systematically lower emissions than SOE (OFE-to-SOE ratio of 0.41 [0.26 to 0.90]). Given that SOE at these facilities is a lower limit on emissions, these results indicate that OFE is likely a less accurate method than SOE or TFE for this type of facility.« less

We report infrared multiple photon dissociation (IRMPD) spectra of cryogenically-cooled H₂PO₄^-(H₂O)_n anions (n = 2–12) in the spectral range of the stretching and bending modes of the solute anion (600–1800 cm-1). The spectra cannot be fully understood using the standard technique of comparison to harmonic spectra of minimum-energy structures; a satisfactory assignment requires considering anharmonic effects as well as entropy-driven hydrogen bond network fluctuations. Aided by finite temperature ab initio molecular dynamics simulations, the observed changes in the position, width and intensity of the IRMPD bands with cluster size are related to the sequence of microsolvation. Due to stronger hydrogenmore » bonding to the two terminal P=O groups, these are hydrated before the two P–OH groups. By n = 6, all four end groups are involved in the hydrogen bond network and by n = 12, the cluster spectra show similarities to the condensed phase spectrum of H₂PO₄^-(aq). Our results reveal some of the microscopic details concerning the formation of the aqueous solvation environment around H₂PO₄^-, provide ample testing grounds for the design of model solvation potentials for this biologically relevant anion, and support a new paradigm for the interpretation of IRMPD spectra of microhydrated ions.« less