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ABSTRACTCarlsbad Caverns National Park (CAVE), located in southeastern New Mexico, experiences elevated ground-level ozone (O3) exceeding the National Ambient Air Quality Standard (NAAQS) of 70 ppbv. It is situated adjacent to the Permian Basin, one of the largest oil and gas (O&G) producing regions in the US. In 2019, the Carlsbad Caverns Air Quality Study (CarCavAQS) was conducted to examine impacts of different sources on ozone precursors, including nitrogen oxides (NOx) and volatile organic compounds (VOCs). Here, we use positive matrix factorization (PMF) analysis of speciated VOCs to characterize VOC sources at CAVE during the study. Seven factors were identified. Three factors composed largely of alkanes and aromatics with different lifetimes were attributed to O&G development and production activities. VOCs in these factors were typical of those emitted by O&G operations. Associated residence time analyses (RTA) indicated their contributions increased in the park during periods of transport from the Permian Basin. These O&G factors were the largest contributor to VOC reactivity with hydroxyl radicals (62%). Two PMF factors were rich in photochemically generated secondary VOCs; one factor contained species with shorter atmospheric lifetimes and one with species with longer lifetimes. RTA of the secondary factors suggested impacts of O&G emissions from regions farther upwind, such as Eagle Ford Shale and Barnett Shale formations. The last two factors were attributed to alkenes likely emitted from vehicles or other combustion sources in the Permian Basin and regional background VOCs, respectively.Implications: Carlsbad Caverns National Park experiences ground-level ozone exceeding the National Ambient Air Quality Standard. Volatile organic compounds are critical precursors to ozone formation. Measurements in the Park identify oil and gas production and development activities as the major contributors to volatile organic compounds. Emissions from the adjacent Permian Basin contributed to increases in primary species that enhanced local ozone formation. Observations of photochemically generated compounds indicate that ozone was also transported from shale formations and basins farther upwind. Therefore, emission reductions of volatile organic compounds from oil and gas activities are important for mitigating elevated O3in the region.

ABSTRACTCarlsbad Caverns National Park (CAVE) is located in southeastern New Mexico and is adjacent to the Permian Basin, one of the most productive oil and natural gas (O&G) production regions in the United States. Since 2018, ozone (O3) at CAVE has frequently exceeded the 70 ppbv 8-hour National Ambient Air Quality Standard. We examine the influence of regional emissions on O3formation using observations of O3, nitrogen oxides (NOx = NO + NO2), a suite of volatile organic compounds (VOCs), peroxyacetyl nitrate (PAN), and peroxypropionyl nitrate (PPN). Elevated O3and its precursors are observed when the wind is from the southeast, the direction of the Permian Basin. We identify 13 days during the July 25 to September 5, 2019 study period when the maximum daily 8-hour average (MDA8) O3exceeded 65 ppbv; MDA8 O3exceeded 70 ppbv on 5 of these days. The results of a positive matrix factorization (PMF) analysis are used to identify and attribute source contributions of VOCs and NOx. On days when the winds are from the southeast, there are larger contributions from factors associated with primary O&G emissions; and, on high O3days, there is more contribution from factors associated with secondary photochemical processing of O&G emissions. The observed ratio of VOCs to NOxis consistently high throughout the study period, consistent with NOx-limited O3production. Finally, all high O3days coincide with elevated acyl peroxy nitrate abundances with PPN to PAN ratios > 0.15 ppbv ppbv−1indicating that anthropogenic VOC precursors, and often alkanes specifically, dominate the photochemistry.Implications: The results above strongly indicate NOx-sensitive photochemistry at Carlsbad Caverns National Park indicating that reductions in NOxemissions should drive reductions in O3. However, the NOx-sensitivity is largely driven by emissions of NOxinto a VOC-rich environment, and a high PPN:PAN ratio and its relationship to O3indicate substantial influence from alkanes in the regional photochemistry. Thus, simultaneous reductions in emissions of NOxand non-methane VOCs from the oil and gas sector should be considered for reducing O3at Carlsbad Caverns National Park. Reductions in non-methane VOCs will have the added benefit of reducing formation of other secondary pollutants and air toxics.

ABSTRACTCarlsbad Caverns National Park in southeastern New Mexico is adjacent to the Permian Basin, one of the most productive oil and gas regions in the country. The 2019 Carlsbad Caverns Air Quality Study (CarCavAQS) was designed to examine the influence of regional sources, including urban emissions, oil and gas development, wildfires, and soil dust on air quality in the park. Field measurements of aerosols, trace gases, and deposition were conducted from 25 July through 5 September 2019. Here, we focus on observations of fine particles and key trace gas precursors to understand the important contributing species and their sources and associated impacts on haze. Key gases measured included aerosol precursors, nitric acid and ammonia, and oil and gas tracer, methane. High-time resolution (6-min) PM2.5mass ranged up to 31.8 µg m−3, with an average of 7.67 µg m−3. The main inorganic ion contributors were sulfate (avg 1.3 µg m−3), ammonium (0.30 µg m−3), calcium (Ca2+) (0.22 µg m−3), nitrate (0.16 µg m−3), and sodium (0.057 µg m−3). The WSOC concentration averaged 1.2 µg C m−3. Sharp spikes were observed in Ca2+, consistent with local dust generation and transport. Ion balance analysis and abundant nitric acid suggest PM2.5nitrate often reflected reaction between nitric acid and sea salt, forming sodium nitrate, and between nitric acid and soil dust containing calcium carbonate, forming calcium nitrate. Sulfate and soil dust are the major contributors to modeled light extinction in the 24-hr average daily IMPROVE observations. Higher time resolution data revealed a maximum 1-hr extinction value of 90 Mm−1(excluding coarse aerosol) and included periods of significant light extinction from BC as well as sulfate and soil dust. Residence time analysis indicated enrichment of sulfate, BC, and methane during periods of transport from the southeast, the direction of greatest abundance of oil and gas development.Implications:Rapid development of U.S. oil and gas resources raises concerns about potential impacts on air quality in National Parks. Measurements in Carlsbad Caverns National Park provide new insight into impacts of unconventional oil and gas development and other sources on visual air quality in the park. Major contributors to visibility impairment include sulfate, soil dust (often reacted with nitric acid), and black carbon. The worst periods of visibility and highest concentrations of many aerosol components were observed during transport from the southeast, a region of dense Permian Basin oil and gas development.

ABSTRACTDinosaur National Monument (DINO) is located near the northeastern edge of the Uinta Basin and often experiences elevated levels of wintertime ground-level ozone. Previous studies have shown that high ozone mixing ratios in the Uinta Basin are driven by elevated levels of volatile organic compounds (VOCs) and nitrogen oxides (NOx) from regional oil and gas development coupled with temperature inversions and enhanced photochemistry from persistent snow cover. Here, we show that persistent snow cover and temperature inversions, along with abundant ammonia, also lead to wintertime haze in this region. A study was conducted at DINO from November 2018 through May 2020 where ozone, speciated fine and coarse aerosols, inorganic gases, and VOCs were measured. Three National Ambient Air Quality Standards (NAAQS) ozone exceedances were observed in the first winter, and no exceedances were observed in the second winter. In contrast, elevated levels of particulate matter were observed both winters, with 24-h averaged particle light extinction exceeding 100 Mm−1. These haze events were dominated by ammonium nitrate, and particulate organics were highly correlated with ammonium nitrate. Ammonium nitrate formation was limited by nitric acid in winter. As such, reductions in regional NOxemissions should reduce haze levels and improve visibility at DINO in winter. Long-term measurements of particulate matter from nearby Vernal, Utah, suggest that visibility impairment is a persistent issue in the Uinta Basin in winter. From April through October 2019, relatively clean conditions occurred, with average particle extinction of ~10 Mm−1. During this period, ammonium nitrate concentrations were lower by more than an order of magnitude, and contributions from coarse mass and soil to haze levels increased. VOC markers indicated that the high levels of observed pollutants in winter were likely from local sources related to oil and gas extraction activities.Implications: Elevated ground-level ozone and haze levels were observed at Dinosaur National Monument in winter. Haze episodes were dominated by ammonium nitrate, with 24-h averaged particle light extinction exceeding 100 Mm−1, reducing visual range near the surface to ~35 km. Despite elevated ammonium nitrate concentrations, additional gas-phase ammonia was available, such that any increase in NOxemissions in the region is likely to lead to even greater haze levels.

Southeastern New Mexico's Carlsbad Caverns National Park (CAVE) has increasingly experienced summertime ozone (O3) exceeding an 8‐hr average of 70 parts per billion by volume (ppbv). The park is located in the western part of the Permian oil and natural gas (O&G) basin, where production rates have increased fivefold in the last decade. We investigate O3–precursor relationships by constraining the F0AM box model to observations of nitrogen oxides (NOx= NO + NO2) and a suite of volatile organic compounds (VOCs) collected at CAVE during summer 2019. O&G‐related VOCs dominated the calculated VOC reactivity with hydroxyl radicals (OH) on days when O3concentrations were primarily controlled by local photochemistry. Radical budget analysis showed that NOxlevels were high enough to impose VOC sensitivity on O3production in the morning hours, while subsequent NOxloss through photochemical consumption led to NOx‐sensitive conditions in the afternoon. Maximum daily O3was responsive to both NOxand O&G‐related VOC reductions, with NOxreductions proving most effective. The model underestimated observed O3during a 5‐day high O3episode that was influenced by photochemically aged O&G emissions, as indicated by back‐trajectory analysis, low i‐/n‐pentane ratios, enhanced secondary VOCs, and low ratios of NOxto total reactive oxidized nitrogen (NOy). Model‐observation agreement was improved by constraining model NOxwith observed NOy, which approximates NOxat the time of emission, indicating that a large fraction of O3during this episode was formed nonlocally. New Mexico's Carlsbad Caverns National Park has faced an increase in ground‐level ozone pollution. Summertime southeasterly winds place the park directly downwind of the Permian basin, one of the largest and most productive oil and natural gas (O&G) basins in the US. Our study, conducted using measurements collected in the park during summer 2019 and an air quality model, investigates how emissions from O&G activities affect ozone production. We find that local ozone production is sensitive to changes in both nitrogen oxides and volatile organic compound levels, but more significant reductions in ozone can be achieved by preferentially lowering nitrogen oxides. While the Permian is the closest O&G basin to the park, controlling ozone pollution may require emission reductions from other basins and shale plays in the region, as the park is sometimes impacted by aged air masses that transport ozone from farther upwind. 8‐hr ozone concentrations frequently exceed 70 parts per billion by volume at Carlsbad Caverns National ParkA box modeling analysis indicates that local ozone production is most sensitive to nitrogen oxide levelsA subset of high ozone days was influenced by photochemically aged air masses carrying ozone from upwind oil and gas production regions 8‐hr ozone concentrations frequently exceed 70 parts per billion by volume at Carlsbad Caverns National Park A box modeling analysis indicates that local ozone production is most sensitive to nitrogen oxide levels A subset of high ozone days was influenced by photochemically aged air masses carrying ozone from upwind oil and gas production regions

Energy is an integral part of society. The major US energy sources of fossil fuels (coal, oil, natural gas); biofuels (ethanol); and wind are concentrated in grassland ecosystems of the Great Plains. As energy demand continues to increase, mounting pressures will be placed on North American grassland systems. In this review, we present the ecological effects of energy development and production on grassland systems. We then identify opportunities to mitigate these effects during the planning, construction, and production phases by using informed methodology and improved technology. Primary effects during energy development include small- and large-scale soil disturbance and vegetation removal as small patches of grasslands are used to host oil or gas wells, wind turbine pads, associated roadways, and pipelines or through the conversion of large grassland areas to biofuel croplands. Direct habitat loss or habitat fragmentation can affect wildlife directly through increased mortality or indirectly through reduction in habitat quantity and quality. During energy production, air and water quality can be affected through regular emissions or unplanned spills. Energy development can also affect the economy and health of local communities. During planning, energy development and production effects can be reduced by carefully considering effects on grasslands during siting and even by selecting different energy source types. During construction, effects on soil and plant systems can be minimized by eliminating weed populations before disturbance, salvaging and stockpiling topsoil for future revegetation, and harvesting native local seed for postsite restoration. During energy production operations, noise and road traffic reduction plans and atmospheric monitoring will enable more informed mitigation measures. Continued research on energy development effects and mitigation measures is necessary to establish best management practices beneficial to grassland health while providing needed energy for the United States.

ABSTRACTSeveral studies have been carried out over the past 20 or so years to assess the level of visual air quality that is judged to be acceptable in urban settings. Groups of individuals were shown slides or computer-projected scenes under a variety of haze conditions and asked to judge whether each image represented acceptable visual air quality. The goal was to assess the level of haziness found to be acceptable for purposes of setting an urban visibility regulatory standard. More recently, similar studies were carried out in Beijing, China, and the more pristine Grand Canyon National Park and Great Gulf Wilderness. The studies clearly showed that when preference ratings were compared to measures of atmospheric haze such as atmospheric extinction, visual range, or deciview (dv), there was not a single indicator that represented acceptable levels of visual air quality for the varied urban or more remote settings. For instance, using a Washington, D.C., setting, 50% of the observers rated the landscape feature as not having acceptable visual air quality at an extinction of 0.19 km−1(21 km visual range, 29 dv), while the 50% acceptability point for a Denver, Colorado, setting was 0.075 km−1(52 km visual range, 20 dv) and for the Grand Canyon it was 0.023 km−1(170 km visual range, 7 dv). Over the past three or four decades, many scene-specific visibility indices have been put forth as potential indicators of visibility levels as perceived by human observers. They include, but are not limited to, color and achromatic contrast of single landscape features, average and equivalent contrast of the entire image, edge detection algorithms such as the Sobel index, and just-noticeable difference or change indexes. This paper explores various scene-specific visual air quality indices and examines their applicability for use in quantifying visibility preference levels and judgments of visual air quality.Implications: Visibility acceptability studies clearly show that visibility become more unacceptable as haze increases. However, there are large variations in the preference levels for different scenes when universal haze indicators, such as atmospheric extinction, are used. This variability is significantly reduced when the sky–landscape contrast of the more distant landscape features in the observed scene is used. Analysis suggest that about 50% of individuals would find the visibility unacceptable if at any time the more distant landscape features nearly disappear, that is, they are at the visual range. This common metric could form the basis for setting an urban visibility standard.

ABSTRACTThe Handix Scientific open-path cavity ringdown spectrometer (OPCRDS) was deployed during summer 2016 in Great Smoky Mountains National Park (GRSM). Extinction coefficients from the relatively new OPCRDS and from a more well-established extinction instrument agreed to within 7%. Aerosol hygroscopic growth (f(RH)) was calculated from the ratio of ambient extinction measured by the OPCRDS to dry extinction measured by a closed-path extinction monitor (Aerodyne’s cavity-attenuated phase shift particulate matter extinction monitor [CAPS PMex]). Derived hygroscopicity (relative humidity [RH] < 95%) from this campaign agreed with data from 1995 at the same site and time of year, which is noteworthy given the decreasing trend for organics and sulfate in the eastern United States. However, maximum f(RH) values in 1995 were less than half as large as those recorded in 2016—possibly due to nephelometer truncation losses in 1995. Two hygroscopicity parameterizations were investigated using high-time-resolution OPCRDS+CAPS PMex data, and the κextmodel was more accurate than the gamma model. Data from the two ambient optical instruments, the OPCRDS and the open-path nephelometer, generally agreed; however, significant discrepancies between ambient scattering and extinction were observed, apparently driven by a combination of hygroscopic growth effects, which tend to increase nephelometer truncation losses and decrease sensitivity to the wavelength difference between the two instruments as a function of particle size. There was not a statistically significant difference in the mean reconstructed extinction values obtained from the original and the revised IMPROVE (Interagency Monitoring of Protected Visual Environments) equations. On average, IMPROVE reconstructed extinction was ~25% lower than extinction measured by the OPCRDS, which suggests that the IMPROVE equations and 24-hr aerosol data are moderately successful in estimating current haze levels at GRSM. However, this conclusion is limited by the coarse temporal resolution and the low dynamic range of the IMPROVE reconstructed extinction.Implications: Although light extinction, which is directly related to visibility, is not directly measured in U.S. National Parks, existing IMPROVE protocols can be used to accurately infer visibility for average humidity conditions, but during the large fraction of the year when humidity is above or below average, accuracy is reduced substantially. Furthermore, nephelometers, which are used to assess the accuracy of IMPROVE visibility estimates, may themselves be biased low when humidity is very high. Despite reductions in organic and sulfate particles since the 1990s, hygroscopicity, particles’ affinity for water, appears unchanged, although this conclusion is weakened by the previously mentioned nephelometer limitations.

ABSTRACTOil and gas activities have occurred in the Bakken region of North Dakota and nearby states and provinces since the 1950s but began increasing rapidly around 2008 due to new extraction methods. Three receptor-based techniques were used to examine the potential impacts of oil and gas extraction activities on airborne particulate concentrations in Class I areas in and around the Bakken. This work was based on long-term measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring network. Spatial and temporal patterns in measured concentrations were examined before and after 2008 to better characterize the influence of these activities. A multisite back-trajectory analysis and a receptor-based source apportionment model were used to estimate impacts. Findings suggest that recent Bakken oil and gas activities have led to an increase in regional fine (PM2.5—particles with aerodynamic diameters <2.5 µm) soil and elemental carbon (EC) concentrations, as well as coarse mass (CM = PM10–PM2.5). Influences on sulfate and nitrate concentrations were harder to discern due to the concurrent decline in regional emissions of precursors to these species from coal-fired electric generating stations. Impacts were largest at sites in North Dakota and Montana that are closest to the most recent drilling activity.Implications: The increase in oil and gas activities in the Bakken region of North Dakota and surrounding areas has had a discernible impact on airborne particulate concentrations that impact visibility at protected sites in the region. However, the impact has been at least partially offset by a concurrent reduction in emissions from coal-fired electric generating stations. Continuing the recent reductions in flaring would likely be beneficial for the regional visual air quality.

A procedure for the size-selective extraction of polycyclic aromatic hydrocarbons (PAHs) from an oil-in-water microemulsion system is reported. This extraction is achieved through a precipitation/extraction process involving cyclodextrins (CDs) and select PAHs in the microemulsion. Results are confirmed by fluorescence analysis of supernatant and precipitate. The size relationship between the PAH and CD cavity appears to be a major factor in the selectivity of the process. For example, after extraction with β-CD, the fluorescence intensity of naphthalene in the microemulsion is reduced to 3.7% of its original value, whereas with α- or γ-CD the intensity remains unchanged. In studies of a model system, the microemulsion involves a three-component mixture of PAHs; α-, β-, and γ-CD are investigated for their extraction capabilities for these three PAHs. Copyright 1993, 1999 Academic Press

Elevated reactive nitrogen (Nr) deposition is a concern for alpine ecosystems, and dry NH3deposition is a key contributor. Understanding how emission hotspots impact downwind ecosystems through dry NH3deposition provides opportunities for effective mitigation. However, direct NH3flux measurements with sufficient temporal resolution to quantify such events are rare. Here, we measured NH3fluxes at Rocky Mountain National Park (RMNP) during two summers and analyzed transport events from upwind agricultural and urban sources in northeastern Colorado. We deployed open-path NH3sensors on a mobile laboratory and an eddy covariance tower to measure NH3concentrations and fluxes. Our spatial sampling illustrated an upslope event that transported NH3emissions from the hotspot to RMNP. Observed NH3deposition was significantly higher when backtrajectories passed through only the agricultural region (7.9 ng m–2s–1) versus only the urban area (1.0 ng m–2s–1) and both urban and agricultural areas (2.7 ng m–2s–1). Cumulative NH3fluxes were calculated using observed, bidirectional modeled, and gap-filled fluxes. More than 40% of the total dry NH3deposition occurred when air masses were traced back to agricultural source regions. More generally, we identified that 10 (25) more national parks in the U.S. are within 100 (200) km of an NH3hotspot, and more observations are needed to quantify the impacts of these hotspots on dry NH3deposition in these regions.

Measurements of hygroscopicity and cloud condensation nuclei (CCN) activity were conducted on secondary organic aerosol (SOA) formed in a smog chamber. SOA precursors included α‐pinene, β‐pinene, Δ3‐carene, and toluene, representative of both naturally and anthropogenically emitted organic species. Measured CCN activation was comparable for all of the species studied and occurred at humidity conditions which are readily attained in the atmosphere. Further, there was little variation in hygroscopic growth between compounds. However, measured droplet activation conditions were inconsistent with hygroscopicity measured below water saturation and Köhler theory expressions based on Raoult’s law for several parameterizations for water activity. In the atmosphere, SOA may compose a large fraction of atmospheric particulate matter and will often exist internally mixed with inorganic species. Using the current results, we compare SOA to insoluble organic species to calculate CCN activation from mixed organic‐sulfate particles for a range of atmospheric conditions. We find that droplet activation behavior of mixed particles containing SOA is the same as that of mixed particles for which the organic component is nonhygroscopic, except for cases in which there are low particle concentrations, low updraft velocities, and the aerosol composition is dominated by organics.

A continuous flow diffusion chamber (CFDC) was used to measure ice formation by cloud particle residuals during the Cirrus Regional Study of Tropical Anvils and Cirrus Layers‐Florida Area Cirrus Experiment. These measurements were directed toward determining the relative contributions of homogeneous nucleation, heterogeneous nucleation, and secondary ice formation processes to the concentrations of ice crystals in anvil cirrus formed from convection. The CFDC sampled residual particles remaining after evaporation of cloud particles initially collected by a counterflow virtual impactor. This allowed, for the first time, determination of the ice nucleation ability of particles that included the presumed nuclei for cloud‐ice formation. The approach proved successful for estimating concentrations of heterogeneous ice nuclei (IN) transported into anvil clouds, but experimental issues limited measurements of homogeneous freezing and, consequently, in determining the role of secondary ice formation. Results suggest agreement within a factor of 2–3 between CFDC heterogeneous IN concentrations and anvil ice crystal concentrations in the size range above ∼30 μm. IN concentrations also correlated with ice concentrations inferred from measurements by the FSSP (Forward Scattering Spectrometer Probe). However, measured IN concentrations were nearly two orders of magnitude lower than FSSP concentrations. This difference may have resulted from homogeneous freezing, secondary ice formation, or other unidentified ice formation processes that were not fully captured by the CFDC. The data suggest that heterogeneous nucleation played a smaller role than homogeneous nucleation in determining anvil ice crystal concentrations, except during periods of strong desert dust ingestion by cumuli. Nevertheless, heterogeneous nucleation may provide the source for larger ice crystals present in anvil regions.

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