Ethylene Oxide in Southeastern Louisiana's Petrochemical Corridor: High Spatial Resolution Mobile Monitoring during HAP-MAP.

Ethylene oxide ("EtO") is an industrially made volatile organic compound and a known human carcinogen. There are few reliable reports of ambient EtO concentrations around production and end-use facilities, however, despite major exposure concerns. We present in situ, fast (1 Hz), sensitive EtO measurements made during February 2023 across the southeastern Louisiana industrial corridor. We aggregated mobile data at 500 m spatial resolution and reported average mixing ratios for 75 km of the corridor. Mean and median aggregated values were 31.4 and 23.3 ppt, respectively, and a majority (75%) of 500 m grid cells were above 10.9 ppt, the lifetime exposure concentration corresponding to 100-in-one million excess cancer risk (1 × 10-4). A small subset (3.3%) were above 109 ppt (1000-in-one million cancer risk, 1 × 10-3); these tended to be near EtO-emitting facilities, though we observed plumes over 10 km from the nearest facilities. Many plumes were highly correlated with other measured gases, indicating potential emission sources, and a subset was measured simultaneously with a second commercial analyzer, showing good agreement. We estimated EtO for 13 census tracts, all of which were higher than EPA estimates (median difference of 21.3 ppt). Our findings provide important information about EtO concentrations and potential exposure risks in a key industrial region and advance the application of EtO analytical methods for ambient sampling and mobile monitoring for air toxics.

Methane Emissions from Offshore Oil and Gas Platforms in the Gulf of Mexico.

Shipboard measurements of offshore oil and gas facilities were conducted in the Gulf of Mexico in February 2018. Species measured at 1 s include methane, ethane, carbon-13 (13C) and deuterium (D) isotopes of methane, and several combustion tracers. Significant variability in the emission composition is observed between individual sites, with typical ethane/methane ratios around 5.3% and 13C and D methane isotopic compositions around -40 and -240‰, respectively. Offshore plumes were spatially narrower than expectations of the plume width based on terrestrial atmospheric stability classes; a modified Gaussian dispersion methodology using empirically measured horizontal plume widths was used to estimate the emission rates. A total of 103 sites were studied, including shallow and deepwater offshore platforms and drillships. Methane emission rates range from 0 to 190 kg/h with 95% confidence limits estimated at a factor of 10. The observed distribution is skewed with the top two emitters accounting for 20% of the total methane emissions of all sampled sites. Despite the greater throughput of the deepwater facilities, they had moderate emission rates compared to shallow-water sites. Analysis of background ethane enhancements also suggests a source region in shallow waters. A complete 1 s measurement database is published for use in future studies of offshore dispersion.

Quantification of natural gas and other hydrocarbons from production sites in northern West Virginia using tracer flux ratio methodology.

Tracer flux ratio (TFR) methodology performed downwind of 15 active oil and natural gas production sites in Ohio County, West Virginia sought to quantify air pollutant emissions over two weeks in April 2018. In coordination with a production company, sites were randomly selected depending on wind forecasts and nearby road access. Methane (CH4), ethane (C2H6), and tracer gas compounds (acetylene and nitrous oxide) were measured via tunable infrared direct absorption spectroscopy. Ion signals attributed to benzene (C6H6) and other volatile gases (e.g., C7 - C9 aromatics) were measured via proton-transfer reaction time-of-flight mass spectrometry. Short-term whole facility emission rates for 12 sites are reported. Results from TFR were systematically higher than the sum of concurrent on-site full flow sampler measurements, though not all sources were assessed on-site in most cases. In downwind plumes, the mode of the C2H6:CH4 molar ratio distribution for all sites was 0.2, which agreed with spot sample analysis from the site operator. Distribution of C6H6:CH4 ratios was skew but values between 1 and 5 pptv ppbv-1 were common. Additionally, the aromatic profile has been attributed to condensate storage tank emissions. Average ratios of C7 - C9 to C6H6 were similar to other literature values reported for natural gas wells.

Reconciling Methane Emission Measurements for Offshore Oil and Gas Platforms with Detailed Emission Inventories: Accounting for Emission Intermittency.

Comparisons of observation-based emission estimates with emission inventories for oil and gas production operations have demonstrated that intermittency in emissions is an important factor to be accounted for in reconciling inventories with observations. Most emission inventories do not directly report data on durations of active emissions, and the variability in emissions over time must be inferred from other measurements or engineering calculations. This work examines a unique emission inventory, assembled for offshore oil and gas production platforms in federal waters of the Outer Continental Shelf (OCS) of the United States, which reports production-related sources on individual platforms, along with estimates of emission duration for individual sources. Platform specific emission rates, derived from the inventory, were compared to shipboard measurements made at 72 platforms. The reconciliation demonstrates that emission duration reporting, by source, can lead to predicted ranges in emissions that are much broader than those based on annual average emission rates. For platforms in federal waters, total emissions reported in the inventory for the matched platforms were within ∼10% of emissions estimated based on observations, depending on emission rates assumed for nondetects in the observational data set. The distributions of emissions were similar, with 75% of platform total emission rates falling between 0 and 49 kg/h for the observations and between 0.59 and 54 kg/h for the inventory.

Shortwave absorption by wildfire smoke dominated by dark brown carbon.

Wildfires emit large amounts of black carbon and light-absorbing organic carbon, known as brown carbon, into the atmosphere. These particles perturb Earth's radiation budget through absorption of incoming shortwave radiation. It is generally thought that brown carbon loses its absorptivity after emission in the atmosphere due to sunlight-driven photochemical bleaching. Consequently, the atmospheric warming effect exerted by brown carbon remains highly variable and poorly represented in climate models compared with that of the relatively nonreactive black carbon. Given that wildfires are predicted to increase globally in the coming decades, it is increasingly important to quantify these radiative impacts. Here we present measurements of ensemble-scale and particle-scale shortwave absorption in smoke plumes from wildfires in the western United States. We find that a type of dark brown carbon contributes three-quarters of the short visible light absorption and half of the long visible light absorption. This strongly absorbing organic aerosol species is water insoluble, resists daytime photobleaching and increases in absorptivity with night-time atmospheric processing. Our findings suggest that parameterizations of brown carbon in climate models need to be revised to improve the estimation of smoke aerosol radiative forcing and associated warming.

Traffic, transport, and vegetation drive VOC concentrations in a major urban area in Texas.

The population of Texas has increased rapidly in the past decade. The San Antonio Field Study (SAFS) was designed to investigate ozone (O3) production and precursors in this rapidly changing, sprawling metropolitan area. There are still many questions regarding the sources and chemistry of volatile organic compounds (VOCs) in urban areas like San Antonio which are affected by a complex mixture of industry, traffic, biogenic sources and transported pollutants. The goal of the SAFS campaign in May 2017 was to measure inorganic trace gases, VOCs, methane (CH4), and ethane (C2H6). The SAFS field design included two sites to better assess air quality across the metro area: an urban site (Traveler's World; TW) and a downwind/suburban site (University of Texas at San Antonio; UTSA). The results indicated that acetone (2.52 ± 1.17 and 2.39 ± 1.27 ppbv), acetaldehyde (1.45 ± 1.02 and 0.93 ± 0.45 ppbv) and isoprene (0.64 ± 0.49 and 1.21 ± 0.85 ppbv; TW and UTSA, respectively) were the VOCs with the highest concentrations. Additionally, positive matrix factorization showed three dominant factors of VOC emissions: biogenic, aged urban mixed source, and acetone. Methyl vinyl ketone and methacrolein (MVK + MACR) exhibited contributions from both secondary photooxidation of isoprene and direct emissions from traffic. The C2H6:CH4 demonstrated potential influence of oil and gas activities in San Antonio. Moreover, the high O3 days during the campaign were in the NOx-limited O3 formation regime and were preceded by evening peaks in select VOCs, NOx and CO. Overall, quantification of the concentration and trends of VOCs and trace gases in a major city in Texas offers vital information for general air quality management and supports strategies for reducing O3 pollution. The SAFS campaign VOC results will also add to the growing body of literature on urban sources and concentrations of VOCs in major urban areas.

Chemical Emissions from Cured and Uncured 3D-Printed Ventilator Patient Circuit Medical Parts.

Medical shortages during the COVID-19 pandemic saw numerous efforts to 3D print personal protective equipment and treatment supplies. There is, however, little research on the potential biocompatibility of 3D-printed parts using typical polymeric resins as pertaining to volatile organic compounds (VOCs), which have specific relevance for respiratory circuit equipment. Here, we measured VOCs emitted from freshly printed stereolithography (SLA) replacement medical parts using proton transfer reaction mass spectrometry and infrared differential absorption spectroscopy, and particulates using a scanning mobility particle sizer. We observed emission factors for individual VOCs ranging from ∼0.001 to ∼10 ng cm-3 min-1. Emissions were heavily dependent on postprint curing and mildly dependent on the type of SLA resin. Curing reduced the emission of all observed chemicals, and no compounds exceeded the recommended dose of 360 µg/d. VOC emissions steadily decreased for all parts over time, with an average e-folding time scale (time to decrease to 1/e of the starting value) of 2.6 ± 0.9 h.