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.

Long-term trends of wet inorganic nitrogen deposition in Rocky Mountain National Park: Influence of missing data imputation methods and associated uncertainty.

Excess reactive nitrogen (Nr) deposition is occurring in Rocky Mountain National Park and impacting sensitive ecosystems. In 2006, the National Park Service, State of Colorado, and Environmental Protection Agency established the goal to reduce Nr deposition to below the ecosystem critical load by 2032. Progress is tracked using 5-year averages of annual wet inorganic nitrogen (IN) deposition measured at Loch Vale, Colorado, by the National Atmospheric Deposition Program (NADP). This remote high alpine site is challenging to operate, and large fractions of the annual precipitation, at times >40%, had invalid IN concentrations. Annual wet IN deposition is calculated using the NADP protocol, which replaces missing concentrations with the annual precipitation-weighted mean (PWM) concentration of valid samples. This protocol does not account for seasonal variations in IN concentrations and the inverse relationship between concentration and precipitation amounts. Invalid samples occurred more frequently in the winter and at high and low precipitation amounts, and the NADP protocol generally overestimated annual deposition rates, by as much as 20%. Here, a new method for imputing missing weekly IN concentrations that accounts for their seasonal and precipitation dependence is introduced. Using a bootstrapping analysis shows that the new method reduced the errors in the annual deposition rates by about 30% compared to the NADP protocol and the biases were near zero. The overall trend in the wet IN deposition rates was found to be flat from 1990 to 2017, but the nitrate contribution decreased about 33%, which was offset by a nearly equal increase in ammonium wet deposition. These trends are consistent with known changes in nitrate and ammonium precursor emissions. The long-term trends in the annual IN deposition rates were similar using both data imputation methods, but the 2013-2017 average was about 10% smaller using the new method.

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.

Origin of Fine Particulate Carbon in the Rural United States.

Carbonaceous compounds are a significant component of fine particulate matter and haze in national parks and wilderness areas where visibility is protected, i.e., class I areas (CIAs). The Regional Haze Rule set the goal of returning visibility in CIAs on the most anthropogenically impaired days to natural by 2064. To achieve this goal, we need to understand contributions of natural and anthropogenic sources to the total fine particulate carbon (TC). A Lagrangian chemical transport model was used to simulate the 2006-2008 contributions from various source types to measured TC in CIAs and other rural lands. These initial results were incorporated into a hybrid model to reduce systematic biases. During summer months, fires and vegetation-derived secondary organic carbon together often accounted for >75% of TC. Smaller contributions, <20%, from area and mobile sources also occurred. During the winter, contributions from area and mobile sources increased, with area sources accounting for half or more of the TC in many regions. The area emissions were likely primarily from residential and industrial wood combustion. Different fire seasons were evident, with the largest contributions during the summer when wildfires occur and smaller contributions during the spring and fall when prescribed and agricultural fires regularly occur.

Aerosol species concentrations and source apportionment of ammonia at Rocky Mountain National Park.

Changes in ecosystem function at Rocky Mountain National Park (RMNP) are occurring because of emissions of nitrogen and sulfate species along the Front Range of the Colorado Rocky Mountains, as well as sources farther east and west. The nitrogen compounds include both oxidized and reduced nitrogen. A year-long monitoring program of various oxidized and reduced nitrogen species was initiated to better understand their origins as well as the complex chemistry occurring during transport from source to receptor. Specifically the goals of the study were to characterize the atmospheric concentrations of nitrogen species in gaseous, particulate, and aqueous phases (precipitation and clouds) along the east and west sides of the Continental Divide; identify the relative contributions to atmospheric nitrogen species in RMNP from within and outside of the state of Colorado; identify the relative contributions to atmospheric nitrogen species in RMNP from emission sources along the Colorado Front Range versus other areas within Colorado; and identify the relative contributions to atmospheric nitrogen species from mobile sources, agricultural activities, and large and small point sources within the state of Colorado. Measured ammonia concentrations are combined with modeled releases of conservative tracers from ammonia source regions around the United States to apportion ammonia to its respective sources, using receptor modeling tools.

Spatial, temporal, and interspecies patterns in fine particulate matter in Texas.

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) field study was conducted from July to October 1999 and was followed by several years of modeling and data analyses to examine the causes of haze at Big Bend National Park TX (BBNP). During BRAVO, daily speciated fine (diameter <2.5 microm) particulate concentrations were measured at 37 sites throughout Texas. At the primary receptor site, K-Bar Ranch, there were many additional measurements including a "high-sensitivity" version of the 24-hr fine particulate elemental data. The spatial, temporal, and interspecies patterns in these data are examined here to qualitatively investigate source regions and source types influencing the fine particulate concentrations in Texas with an emphasis on sources of sulfates, the largest contributor to fine mass and light extinction. Peak values of particulate sulfur (S) varied spatially and seasonally. Maximum S was in Northeast Texas during the summer, whereas peak S at BBNP was in the fall. Sulfate acidity at BBNP also varied by month. Sources of Se were evident in Northeast Texas and from the Carbón I and II plants. High S episodes at BBNP during BRAVO had several different trace element characteristics. Carbon concentrations at BBNP during BRAVO were probably mostly urban-related, with arrival from the Houston area likely. The Houston artificial tracer released during the second half of BRAVO was highly correlated with some carbon fractions. There was evidence of the influence of African dust at sites throughout Texas during the summer. Patterns in several trace elements were also examined. Vanadium was associated with air masses from Mexico. Lead concentrations in southern Texas have dropped dramatically over the past several years.

Directional biases in back trajectories caused by model and input data.

Back trajectory analyses are often used for source attribution estimates in visibility and other air quality studies. Several models and gridded meteorological datasets are readily available for generation of trajectories. The Big Bend Regional Aerosol and Visibility Observational (BRAVO) tracer study of July to October 1999 provided an opportunity to evaluate trajectory methods and input data against tracer concentrations, particulate data, and other source attribution techniques. Results showed evidence of systematic biases between the results of different back trajectory model and meteorological input data combinations at Big Bend National Park during the BRAVO. Most of the differences were because of the choice of meteorological data used as input to the trajectory models. Different back trajectories also resulted from the choice of trajectory model, primarily because of the different mechanisms used for vertical placement of the trajectories. No single model or single meteorological data set was found to be superior to the others, although rawinsonde data alone are too sparse in this region to be used as the only input data, and some combinations of model and input data could not be used to reproduce known attributions of tracers and simulated sulfate.

Reconciliation and interpretation of Big Bend National Park particulate sulfur source apportionment: results from the Big Bend Regional Aerosol and Visibility Observational Study--part I.

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) study was an intensive monitoring study from July through October 1999 followed by extensive assessments to determine the causes and sources of haze in Big Bend National Park, located in Southwestern Texas. Particulate sulfate compounds are the largest contributor of haze at Big Bend, and chemical transport models (CTMs) and receptor models were used to apportion the sulfate concentrations at Big Bend to North American source regions and the Carbón power plants, located 225 km southeast of Big Bend in Mexico. Initial source attribution methods had contributions that varied by a factor of > or =2. The evaluation and comparison of methods identified opposing biases between the CTMs and receptor models, indicating that the ensemble of results bounds the true source attribution results. The reconciliation of these differences led to the development of a hybrid receptor model merging the CTM results and air quality data, which allowed a nearly daily source apportionment of the sulfate at Big Bend during the BRAVO study. The best estimates from the reconciliation process resulted in sulfur dioxide (SO2) emissions from U.S. and Mexican sources contributing approximately 55% and 38%, respectively, of sulfate at Big Bend. The distribution among U.S. source regions was Texas, 16%; the Eastern United States, 30%; and the Western United States, 9%. The Carbón facilities contributed 19%, making them the largest single contributing facility. Sources in Mexico contributed to the sulfate at Big Bend on most days, whereas contributions from Texas and Eastern U.S. sources were episodic, with their largest contributions during Big Bend sulfate episodes. On the 20% of the days with the highest sulfate concentrations, U.S. and Mexican sources contributed approximately 71% and 26% of the sulfate, respectively. However, on the 20% of days with the lowest sulfate concentrations, Mexico contributed 48% compared with 40% for the United States.

Reconciliation and interpretation of the Big Bend National Park light extinction source apportionment: results from the Big Bend Regional Aerosol and Visibility Observational Study--part II.

The recently completed Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study focused on particulate sulfate source attribution for a 4-month period from July through October 1999. A companion paper in this issue by Schichtel et al. describes the methods evaluation and results reconciliation of the BRAVO Study sulfate attribution approaches. This paper summarizes the BRAVO Study extinction budget assessment and interprets the attribution results in the context of annual and multiyear causes of haze by drawing on long-term aerosol monitoring data and regional transport climatology, as well as results from other investigations. Particulate sulfates, organic carbon, and coarse mass are responsible for most of the haze at Big Bend National Park, whereas fine particles composed of light-absorbing carbon, fine soils, and nitrates are relatively minor contributors. Spring and late summer through fall are the two periods of high-haze levels at Big Bend. Particulate sulfate and carbonaceous compounds contribute in a similar magnitude to the spring haze period, whereas sulfates are the primary cause of haze during the late summer and fall period. Atmospheric transport patterns to Big Bend vary throughout the year, resulting in a seasonal cycle of different upwind source regions contributing to its haze levels. Important sources and source regions for haze at Big Bend include biomass smoke from Mexico and Central America in the spring and African dust during the summer. Sources of sulfur dioxide (SO2) emissions in Mexico, Texas, and in the Eastern United States all contribute to Big Bend haze in varying amounts over different times of the year, with a higher contribution from Mexican sources in the spring and early summer, and a higher contribution from U.S. sources during late summer and fall. Some multiple-day haze episodes result from the influence of several source regions, whereas others are primarily because of emissions from a single source region.

Clean Air Corridors: A Geographic and.

Meteorological factors, pollutant emissions, and geographic regions related to transport of low optical extinction coefficient air to Grand Canyon National Park were examined. Back trajectories were generated by two models, the Atmospheric Transport and Dispersion Model (ATAD) and an approach using the Nested Grid Model output for a Lagrangian particle transport model (NGM/ CAPITA). Meteorological information along the trajectories was analyzed for its relationship to visibility at the Grand Canyon. Case studies considered days with anomalously clean air from the southwest and dirty air from the northwest. Clean air was most frequently from the north and northwest, rarely from the south. Low emissions, high ventilation and washout by precipitation was associated with clean air. All clean days with transport from the Los Angeles area had upper-level low pressure over the region with high ventilation and usually abundant precipitation. The dirtiest days with transport from the northwest were affected by forest fires.

Source Apportionment of Sulfur and Light Extinction Using Receptor Modeling Techniques.

Most visibility impairment is associated with sulfates, carbonaceous material, and soil-related material.1 Therefore, any visibility source apportionment scheme must address both secondary and primary aerosols. The chemical mass balance (CMB) formalism is usually used to apportion primary particles. It relies on known physical and chemical characteristic aerosols, such as ratios of tracer species, natural or man-made, at the receptors and sources to attribute aerosols to single sources or source types. CMB modeling apportions aerosol species on a sampling-period- by-sampling-period basis. However, if the data set contains an adequate number of samples, regressional techniques, along with less restrictive assumptions, can be used to estimate apportionment of secondary as well as primary species. In a regressional approach, the secondary species is the dependent variable, while the independent variables are tracers that are unique to a single source or group of sources. A key assumption associated with this approach is that the chemical species used as tracers must be uniquely emitted by non-overlapping groups of sources. These techniques were successfully used to develop a semiquantitative apportionment of particulate sulfur, total sulfur (particle plus gaseous sulfur), absorption, and extinction to source categories at receptor sites near the Grand Canyon using data gathered in a special study called Project MOHAVE (Measurement of Haze and Visual Effects). Regression models were used to develop links between trace elements and visibility variables and then to link the trace elements to source categories using CMB analysis. As part of the CMB analysis, a new technique was developed for verifying and/or extracting source profiles from the ambient data set. About 50% of the measured particle sulfur is attributable to coal-fired power plants during summer and winter months, while in the winter months, about 50% of the particle sulfur may be associated with primary sulfur emissions from burning activity and urban emissions during the summer. A variable that is responsible for over 30% of the extinction, babs, is predominately associated with burning activity during the winter and to burning, transportation, and suspended soil during the summer months.