Wintertime haze and ozone at Dinosaur National Monument.

Dinosaur 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 NOx emissions 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 NOx emissions in the region is likely to lead to even greater haze levels.

Using high time resolution aerosol and number size distribution measurements to estimate atmospheric extinction.

Rocky Mountain National Park is experiencing reduced visibility and changes in ecosystem function due to increasing levels of oxidized and reduced nitrogen. The Rocky Mountain Atmospheric Nitrogen and Sulfur (RoMANS) study was initiated to better understand the origins of sulfur and nitrogen species as well as the complex chemistry occurring during transport from source to receptor. As part of the study, a monitoring program was initiated for two 1-month time periods--one during the spring and the other during late summer/fall. The monitoring program included intensive high time resolution concentration measurements of aerosol number size distribution, inorganic anions, and cations, and 24-hr time resolution of PM2.5 and PM10 mass, sulfate, nitrate, carbon, and soil-related elements concentrations. These data are combined to estimate high time resolution concentrations of PM2.5 and PM10 aerosol mass and fine mass species estimates of ammoniated sulfate, nitrate, and organic and elemental carbon. Hour-by-hour extinction budgets are calculated by using these species concentration estimates and measurements of size distribution and assuming internal and external particle mixtures. Summer extinction was on average about 3 times higher than spring extinction. During spring months, sulfates, nitrates, carbon mass, and PM10 - PM2.5 mass contributed approximately equal amounts of extinction, whereas during the summer months, carbonaceous material extinction was 2-3 times higher than other species.

Visibility impacts at Class I areas near the Bakken oil and gas development.

Oil 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.

Light Scattering Characteristics of Aerosols as a Function of Relative Humidity: Part I-A Comparison of Measured Scattering and Aerosol Concentrations Using the Theoretical Models.

The Southeastern Aerosol and Visibility Study (SEAVS) was undertaken to characterize the size-dependent composition, thermodynamic properties, and optical characteristics of the ambient atmospheric particles in the southeastern United States. The field portion of the study was carried out from July 15 to August 25, 1995. As part of the study a relative humidity controlled inlet was built to raise or lower the relative humidity to predetermined levels before the aerosol was passed into an integrating nephelometer or particle-sizing device. Five other integrating nephelometers were operated in various configurations, two of which were fitted with a 2.5 µm inlet. Fine particle (<2.5 µm) samplers were operated to measure concentrations of sulfate, nitrate, and ammonium ions, organic and elemental carbon, and fine soil. Mass size distributions were measured with an eight-stage, single orifice cascade impactor.

Light Scattering Characteristics of Aerosols at Ambient and as a Function of Relative Humidity: Part II-A Comparison of Measured Scattering and Aerosol Concentrations Using Statistical Models.

The eastern United States national parks experience some of the worst visibility conditions in the nation. To study these conditions, the Southeastern Aerosol and Visibility Study (SEAVS) was undertaken to characterize the size-dependent composition, thermodynamic properties, and optical characteristics of the ambient atmospheric particles. It is a cooperative three-year study that is sponsored by the National Park Service and the Electric Power Research Institute and its member utilities. The field portion of the study was carried out from July 15 to August 25, 1995. The study design, instrumental configuration, and estimation of aerosol types from particle measurements is presented in a companion paper. In the companion paper, we compare measurements of scattering at ambient conditions and as functions of relative humidity to theoretical predictions of scattering. In this paper, we make similar comparisons, but using statistical techniques. Statistically derived specific scattering associated with sulfates suggest that a reasonable estimate of sulfate scattering can be arrived at by assuming nominal dry specific scattering and treating the aerosols as an external mixture with ammoniation of sulfate accounted for and by the use of Tang's growth curves to predict water absorption. However, the regressions suggest that the sulfate scattering may be underestimated by about 10%. Regression coefficients on organics, to within the statistical uncertainty of the model, suggest that a reasonable estimate of organic scattering is about 4.0 m2/g. A new analysis technique is presented, which does not rely on comparing measured to model estimates of scattering to evoke an understanding of ambient aerosol growth properties, but rather relies on measurements of scattering as a function of relative humidity to develop actual estimates of f(RH) curves. The estimates of the study average f(RH) curve for sulfates compares favorably with the theoretical f(RH) curve for ammonium bisulfate, which is in turn consistent with the study average sulfate am-moniation corresponding to a molar ratio of NH4/SO4 of approximately one. The f(RH) curve for organics is not significantly different from one, suggesting that organics are weakly to nonhygroscopic.

Seasonal Variations in Aerosol Composition and Acidity at Shenandoah and Great Smoky Mountains National Parks.

The concentration of elements Na through Pb, select ions, and organic carbon from fine (<2.5 µm) particles has been monitored at Shenandoah and Great Smoky Mountains National Parks from 1988 through 1995. The data obtained from 1988 through 1994 show that significant changes in the concentrations of many aerosol constituents occur on a seasonal basis. Particulate sulfate and organic carbon are shown to exhibit substantially higher concentrations during the summer, while sulfur dioxide and nitrate concentrations are highest during the winter. A method for estimating the degree of neutralization of particulate sulfate is given. This method uses routinely measured aerosol elemental compositions because ammonium ion, the primary neutralizing species for sulfate, is not measured on a routine basis. Application of this method to the selected data set shows that sulfate aerosol is most acidic during summer with an average molar Hs (moles of hydrogen associated with sulfur) to S (moles of sulfur) ratio of approximately 4. This suggests the average sulfate particle during the summer has a molar coon slightly more acidic than ammonium bisulfate (NH4HSO4) which has a molar hydrogen to sulfur ratio of 5. Winter Hs to S ratios, however, are approximately 8, suggesting the aerosol is on average fully neutralized ammonium sulfate [(NH4)2SO4].