Other Test Method 33A (OTM 33A) is a near-source flux measurement method developed by the Environmental Protection Agency (EPA) primarily used to locate and estimate emission fluxes of methane from oil and gas (O&G) production facilities without requiring site access. A recent national estimate of methane emissions from O&G production included a large number of flux measurements of upstream O&G facilities made using OTM 33A and concluded the EPA National Emission Inventory underestimates this sector by a factor of ∼2.1 (Alvarez et al., 2018). The study presented here investigates the accuracy of OTM 33A through a series of test releases performed at the Methane Emissions Technology Evaluation Center (METEC), a facility designed to allow quantified amounts of natural gas to be released from decommissioned O&G equipment to simulate emissions from real facilities (Fig. 1). This study includes test releases from single and multiple points, from equipment locations at different heights, and spanned methane release rates ranging from 0.16 to 2.15 kg h−1. Approximately 95 % of individual measurements (N=45) fell within ±70 % of the known release rate. A simple linear regression of OTM 33A versus known release rates at the METEC site gives an average slope of 0.96 with 95 % CI (0.66,1.28), suggesting that an ensemble of OTM 33A measurements may have a small but statistically insignificant low bias.

Flux estimates of volatile organic compounds (VOCs) from oil and gas (O&G) production facilities are fundamental in understanding hazardous air pollutant concentrations and ozone formation. Previous off-site emission estimates derive fluxes by ratioing VOCs measured in canisters to methane fluxes measured in the field. This study uses the Environmental Protection Agency's Other Test Method 33A (OTM 33A) and a fast-response proton transfer reaction mass spectrometer to make direct measurements of VOC emissions from O&G facilities in the Upper Green River Basin, Wyoming. We report the first off-site direct flux estimates of benzene, toluene, ethylbenzene, and xylenes from upstream O&G production facilities and find that these estimates can vary significantly from flux estimates derived using both the canister ratio technique and from the emission inventory. The 32 OTM 33A flux estimates had arithmetic mean (and 95% CI) as follows: benzene 17.83 (0.22, 98.05) g/h, toluene 34.43 (1.01, 126.76) g/h, C8 aromatics 37.38 (1.06, 225.34) g/h, and methane 2.3 (1.7, 3.1) kg/h. A total of 20% of facilities measured accounted for ∼67% of total BTEX emissions. While this heavy tail is less dramatic than previous observations of methane in other basins, it is more prominent than that predicted by the emission inventory.

Atmospheric methane emissions from active natural gas production sites in normal operation were quantified using an inverse Gaussian method (EPA's OTM 33a) in four major U.S. basins/plays: Upper Green River (UGR, Wyoming), Denver-Julesburg (DJ, Colorado), Uintah (Utah), and Fayetteville (FV, Arkansas). In DJ, Uintah, and FV, 72-83% of total measured emissions were from 20% of the well pads, while in UGR the highest 20% of emitting well pads only contributed 54% of total emissions. The total mass of methane emitted as a percent of gross methane produced, termed throughput-normalized methane average (TNMA) and determined by bootstrapping measurements from each basin, varied widely between basins and was (95% CI): 0.09% (0.05-0.15%) in FV, 0.18% (0.12-0.29%) in UGR, 2.1% (1.1-3.9%) in DJ, and 2.8% (1.0-8.6%) in Uintah. Overall, wet-gas basins (UGR, DJ, Uintah) had higher TNMA emissions than the dry-gas FV at all ranges of production per well pad. Among wet basins, TNMA emissions had a strong negative correlation with average gas production per well pad, suggesting that consolidation of operations onto single pads may reduce normalized emissions (average number of wells per pad is 5.3 in UGR versus 1.3 in Uintah and 2.8 in DJ).

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 liquid 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.

Emissions from oil and natural gas development during winter in the Upper Green River basin of Wyoming are known to drive episodic ozone (O3) production. Contrasting O3 distributions were observed in the winters of 2011 and 2012, with numerous episodes (hourly O3 ≥ 85 ppbv) in 2011 compared to none in 2012. The lack of O3 episodes in 2012 coincided with a reduction in measured ambient levels of total non-methane hydrocarbons (NMHC). Measurements of speciated NMHC, and other air quality parameters, were performed to better understand emission sources and to determine which compounds are most active in promoting O3 formation. Positive matrix factorization (PMF) analyses of the data were carried out to help achieve these goals. PMF analyses revealed three contributing factors that were identified with different emission source types: factor 1, combustion/traffic; factor 2, fugitive natural gas; and factor 3, fugitive condensate. Compositional signatures of the three contributing factors were identified through comparison with independently derived emission source profiles. Fugitive emissions of natural gas and of condensate were the two principal emission source types for NMHC. A water treatment and recycling facility was found to be a significant source of NMHC that are abundant in condensate, in particular toluene and m+p-xylene. Emissions from water treatment have an influence upon peak O3 mixing ratios at downwind measurement sites.

Here we compare volatile organic compound (VOC) measurements using a standard proton-transfer-reaction quadrupole mass spectrometer (PTR-QMS) with a new proton-transfer-reaction time of flight mass spectrometer (PTR-TOF) during the Uintah Basin Winter Ozone Study 2013 (UBWOS2013) field experiment in an oil and gas field in the Uintah Basin, Utah. The PTR-QMS uses a quadrupole, which is a mass filter that lets one mass to charge ratio pass at a time, whereas the PTR-TOF uses a time of flight mass spectrometer, which takes full mass spectra with typical 0.1 s–1 min integrated acquisition times. The sensitivity of the PTR-QMS in units of counts per ppbv (parts per billion by volume) is about a factor of 10–35 times larger than the PTR-TOF, when only one VOC is measured. The sensitivity of the PTR-TOF is mass dependent because of the mass discrimination caused by the sampling duty cycle in the orthogonal-acceleration region of the TOF. For example, the PTR-QMS on mass 33 (methanol) is 35 times more sensitive than the PTR-TOF and for masses above 120 amu less than 10 times more. If more than 10–35 compounds are measured with PTR-QMS, the sampling time per ion decreases and the PTR-TOF has higher signals per unit measuring time for most masses. For UBWOS2013 the PTR-QMS measured 34 masses in 37 s and on that timescale the PTR-TOF is more sensitive for all masses. The high mass resolution of the TOF allows for the measurements of compounds that cannot be separately detected with the PTR-QMS, such as oxidation products from alkanes and cycloalkanes emitted by oil and gas extraction. PTR-TOF masses do not have to be preselected, allowing for identification of unanticipated compounds. The measured mixing ratios of the two instruments agreed very well (R2 ≥ 0.92 and within 20%) for all compounds and masses monitored with the PTR-QMS.

Diffusive sampler monitoring techniques were employed during wintertime studies from 2009 to 2012 to assess the spatial distribution of air pollutants associated with the Pinedale Anticline and Jonah Field oil and natural gas (O&NG) developments in the Upper Green River Basin, Wyoming. Diffusive sampling identified both the extent of wintertime ozone (O-3) episodes and the distributions of oxides of nitrogen (NOx), and a suite of 13 C-5+ volatile organic compounds (VOC), including BTEX (benzene, toluene, ethylbenzene and xylene isomers), allowing the influence of different O&NG emission sources to be determined. Concentration isopleth mapping of both diffusive sampler and continuous O-3 measurements show the importance of localized production and advective transport. As for O-3, BTEX and NOx mixing ratios within O&NG development areas were elevated compared to background levels, with localized hotspots also evident. One BTEX hotspot was related to an area with intensive production activities, while a second was located in an area influenced by emissions from a water treatment and recycling facility. Contrastingly, NOx hotspots were at major road intersections with relatively high traffic flows, indicating influence from vehicular emissions. Comparisons of observed selected VOC species ratios at a roadside site in the town of Pinedale with those measured in O&NG development areas show that traffic emissions contribute minimally to VOCs in these latter areas. The spatial distributions of pollutant concentrations identified by diffusive sampling techniques have potential utility for validation of emission inventories that are combined with air quality modeling.

Increased use of hydraulic fracturing ("fracking") in unconventional oil and natural gas (O & NG) development from coal, sandstone, and shale deposits in the United States (US) has created environmental concerns over water and air quality impacts. In this perspective we focus on how the production of unconventional O & NG affects air quality. We pay particular attention to shale gas as this type of development has transformed natural gas production in the US and is set to become important in the rest of the world. A variety of potential emission sources can be spread over tens of thousands of acres of a production area and this complicates assessment of local and regional air quality impacts. We outline upstream activities including drilling, completion and production. After contrasting the context for development activities in the US and Europe we explore the use of inventories for determining air emissions. Location and scale of analysis is important, as O & NG production emissions in some US basins account for nearly 100% of the pollution burden, whereas in other basins these activities make up less than 10% of total air emissions. While emission inventories are beneficial to quantifying air emissions from a particular source category, they do have limitations when determining air quality impacts from a large area. Air monitoring is essential, not only to validate inventories, but also to measure impacts. We describe the use of measurements, including ground-based mobile monitoring, network stations, airborne, and satellite platforms for measuring air quality impacts. We identify nitrogen oxides, volatile organic compounds (VOC), ozone, hazardous air pollutants (HAP), and methane as pollutants of concern related to O & NG activities. These pollutants can contribute to air quality concerns and they may be regulated in ambient air, due to human health or climate forcing concerns. Close to well pads, emissions are concentrated and exposure to a wide range of pollutants is possible. Public health protection is improved when emissions are controlled and facilities are located away from where people live. Based on lessons learned in the US we outline an approach for future unconventional O & NG development that includes regulation, assessment and monitoring.

Natural gas production is associated with emissions of several trace gases, some of them classified as air toxics. While volatile organic compounds (VOCs) have received much attention, hydrogen sulfide (H2S) can also be of concern due to the known health impacts of exposure to this hazardous air pollutant. Here, we present quantitative, fast time-response measurements of H2S using proton-transfer-reaction mass-spectrometry (PTR-MS) instruments. An ultra-light-weight PTR-MS (ULW-PTR-MS) in a mobile laboratory was operated for measurements of VOCs and H2S in a gas and oil field during the Uintah Basin Winter Ozone Study (UBWOS) 2012 campaign. Measurements of VOCs and H2S by a PTR-MS were also made at the Horse Pool ground site in the Uintah Basin during UBWOS 2013. The H2S measurement by PTR-MS is strongly humidity dependent because the proton affinity of H2S is only slightly higher than that of water. The H2S sensitivity of PTR-MS ranged between 0.6–1.4 ncps ppbv−1 during UBWOS 2013. We compare the humidity dependence determined in the laboratory with in-field calibrations and determine the H2S mixing ratios for the mobile and ground measurements. The PTR-MS measurements at Horse Pool are evaluated by comparison with simultaneous H2S measurements using a PTR time-of-flight MS (PTR-ToF-MS) and a Picarro cavity ring down spectroscopy (CRDS) instrument for H2S / CH4. On average 0.6 ± 0.3 ppbv H2S was present at Horse Pool during UBWOS 2013. The correlation between H2S and methane enhancements suggests that the source of H2S is associated with oil and gas extraction in the basin. Significant H2S mixing ratios of up to 9 ppmv downwind of storage tanks were observed during the mobile measurements. This study suggests that H2S emissions associated with oil and gas production can lead to short-term high levels close to point sources, and elevated background levels away from those sources. In addition, our work has demonstrated that PTR-MS can make reliable measurements of H2S at levels below 1 ppbv.

During recent years, elevated ozone (O3) values have been observed repeatedly in the Upper Green River basin (UGRB), Wyoming, during wintertime. This paper presents an analysis of high ozone days in late winter 2011 (1 h average up to 166 ppbv – parts per billion by volume). Intensive operational periods (IOPs) of ambient monitoring were performed, which included comprehensive surface and boundary layer measurements. On IOP days, maximum O3 values are restricted to a very shallow surface layer. Low wind speeds in combination with low mixing layer heights (~ 50 m above ground level around noontime) are essential for accumulation of pollutants within the UGRB. Air masses contain substantial amounts of reactive nitrogen (NOx) and non-methane hydrocarbons (NMHC) emitted from fossil fuel exploration activities in the Pinedale Anticline. On IOP days particularly in the morning hours, reactive nitrogen (up to 69%), aromatics and alkanes (~ 10–15%; mostly ethane and propane) are major contributors to the hydroxyl (OH) reactivity. Measurements at the Boulder monitoring site during these time periods under SW wind flow conditions show the lowest NMHC / NOx ratios (~ 50), reflecting a relatively low reactive NMHC mixture, and a change from a NOx-limited regime towards a NMHC-limited regime as indicated by photochemical indicators, e.g., O3 /NOy, O3 /NOz, and O3 / HNO3 and the EOR (extent of reaction). OH production on IOP days is mainly due to nitrous acid (HONO). On a 24 h basis and as determined for a measurement height of 1.80 m above the surface HONO photolysis on IOP days can contribute ~ 83% to OH production on average, followed by alkene ozonolysis (~ 9%). Photolysis by ozone and HCHO photolysis contribute about 4% each to hydroxyl formation. High HONO levels (maximum hourly median on IOP days: 1096 pptv – parts per trillion by volume) are favored by a combination of shallow boundary layer conditions and enhanced photolysis rates due to the high albedo of the snow surface. HONO is most likely formed through (i) abundant nitric acid (HNO3) produced in atmospheric oxidation of NOx, deposited onto the snow surface and undergoing photo-enhanced heterogeneous conversion to HONO (estimated HONO production: 10.2 ± 40% ppbv h−1) and (ii) combustion-related emission of HONO (estimated HONO production: ~ 0.1 ± 30% ppbv h−1). HONO production is confined to the lowermost 10 m of the boundary layer. HONO, serves as the most important precursor for OH, strongly enhanced due to the high albedo of the snow cover (HONO photolysis rate 10.7 ± 30% ppbv h−1). OH radicals will oxidize NMHCs, mostly aromatics (toluene, xylenes) and alkanes (ethane, propane), eventually leading to an increase in ozone.