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Secondary inorganic aerosols play an important role in air pollution and climate change, and their formation modulates the atmospheric deposition of reactive nitrogen (including oxidized and reduced nitrogen), thus impacting the nitrogen cycle. Large-scale and long-term analyses of secondary inorganic aerosol formation based on model simulations have substantial uncertainties. Here we improve constraints on secondary inorganic aerosol formation using decade-long in situ observations of aerosol composition and gaseous precursors from multiple monitoring networks across the United States. We reveal a shift in the secondary inorganic aerosol formation regime in the rural United States between 2011 and 2020, making rural areas less sensitive to changes in ammonia concentrations and shortening the effective atmospheric lifetime of reduced forms of reactive nitrogen. This leads to potential increases in reactive nitrogen deposition near ammonia emission hotspots, with ecosystem impacts warranting further investigation. Ammonia (NH 3 ), a critical but not directly regulated precursor of fine particulate matter in the United States, has been increasingly scrutinized to improve air quality. Our findings, however, show that controlling NH 3 became significantly less effective for mitigating fine particulate matter in the rural United States. We highlight the need for more collocated aerosol and precursor observations for better characterization of secondary inorganic aerosols formation in urban areas., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2024.)

Carlsbad 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 (O 3 ) at CAVE has frequently exceeded the 70 ppbv 8-hour National Ambient Air Quality Standard. We examine the influence of regional emissions on O 3 formation using observations of O 3 , nitrogen oxides (NO x  = NO + NO 2 ), a suite of volatile organic compounds (VOCs), peroxyacetyl nitrate (PAN), and peroxypropionyl nitrate (PPN). Elevated O 3 and 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) O 3 exceeded 65 ppbv; MDA8 O 3 exceeded 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 NO x . On days when the winds are from the southeast, there are larger contributions from factors associated with primary O&G emissions; and, on high O 3 days, there is more contribution from factors associated with secondary photochemical processing of O&G emissions. The observed ratio of VOCs to NO x is consistently high throughout the study period, consistent with NO x -limited O 3 production. Finally, all high O 3 days coincide with elevated acyl peroxy nitrate abundances with PPN to PAN ratios > 0.15 ppbv ppbv -1 indicating that anthropogenic VOC precursors, and often alkanes specifically, dominate the photochemistry. Implications : The results above strongly indicate NO x -sensitive photochemistry at Carlsbad Caverns National Park indicating that reductions in NO x emissions should drive reductions in O 3 . However, the NO x -sensitivity is largely driven by emissions of NO x into a VOC-rich environment, and a high PPN:PAN ratio and its relationship to O 3 indicate substantial influence from alkanes in the regional photochemistry. Thus, simultaneous reductions in emissions of NO x and non-methane VOCs from the oil and gas sector should be considered for reducing O 3 at Carlsbad Caverns National Park. Reductions in non-methane VOCs will have the added benefit of reducing formation of other secondary pollutants and air toxics.

Carlsbad Caverns National Park (CAVE), located in southeastern New Mexico, experiences elevated ground-level ozone (O 3 ) 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 (NO x ) 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 O 3 in the region.

Carlsbad 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) PM 2.5 mass 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 (Ca 2+ ) (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 Ca 2+ , consistent with local dust generation and transport. Ion balance analysis and abundant nitric acid suggest PM 2.5 nitrate 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.

A robust method to estimate mineral dust mass in ambient particulate matter (PM) is essential, as the dust fraction cannot be directly measured but is needed to understand dust impacts on the environment and human health. In this study, a global-scale dust equation is developed that builds on the widely used Interagency Monitoring of Protected Visual Environments (IMPROVE) network's "soil" formula that is based on five measured elements (Al, Si, Ca, Fe, and Ti). We incorporate K, Mg, and Na into the equation using the mineral-to-aluminum (MAL) mass ratio of (K 2 O + MgO + Na 2 O)/Al 2 O 3 and apply a correction factor (CF) to account for other missing compounds. We obtain region-specific MAL ratios and CFs by investigating the variation in dust composition across desert regions. To calculate reference dust mass for equation evaluation, we use total-mineral-mass (summing all oxides of crustal elements) and residual-mass (subtracting non-dust species from total PM) approaches. For desert dust in source regions, the normalized mean bias (NMB) of the global equation (within ±1%) is significantly smaller than the NMB of the IMPROVE equation (-6% to 10%). For PM 2.5 with high dust content measured by the IMPROVE network, the global equation estimates dust mass well (NMB within ±5%) at most sites. For desert dust transported to non-source regions, the global equation still performs well (NMB within ±2%). The global equation can also represent paved road, unpaved road, and agricultural soil dust (NMB within ±5%). This global equation provides a promising approach for calculating dust mass based on elemental analysis of dust., (© 2022 The Authors. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.)

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 (NO x ) 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 NO x 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 NO x emissions in the region is likely to lead to even greater haze levels.

Elevated reactive nitrogen (N r ) deposition is a concern for alpine ecosystems, and dry NH 3 deposition is a key contributor. Understanding how emission hotspots impact downwind ecosystems through dry NH 3 deposition provides opportunities for effective mitigation. However, direct NH 3 flux measurements with sufficient temporal resolution to quantify such events are rare. Here, we measured NH 3 fluxes 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 NH 3 sensors on a mobile laboratory and an eddy covariance tower to measure NH 3 concentrations and fluxes. Our spatial sampling illustrated an upslope event that transported NH 3 emissions from the hotspot to RMNP. Observed NH 3 deposition was significantly higher when backtrajectories passed through only the agricultural region (7.9 ng m -2 s -1 ) versus only the urban area (1.0 ng m -2 s -1 ) and both urban and agricultural areas (2.7 ng m -2 s -1 ). Cumulative NH 3 fluxes were calculated using observed, bidirectional modeled, and gap-filled fluxes. More than 40% of the total dry NH 3 deposition 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 NH 3 hotspot, and more observations are needed to quantify the impacts of these hotspots on dry NH 3 deposition in these regions.

Frameworks for limiting ecosystem exposure to excess nutrients and acidity require accurate and complete deposition budgets of reactive nitrogen (Nr). While much progress has been made in developing total Nr deposition budgets for the U.S., current budgets remain limited by key data and knowledge gaps. Analysis of National Atmospheric Deposition Program Total Deposition (NADP/TDep) data illustrates several aspects of current Nr deposition that motivate additional research. Averaged across the continental U.S., dry deposition contributes slightly more (55%) to total deposition than wet deposition and is the dominant process (>90%) over broad areas of the Southwest and other arid regions of the West. Lack of dry deposition measurements imposes a reliance on models, resulting in a much higher degree of uncertainty relative to wet deposition which is routinely measured. As nitrogen oxide (NO x ) emissions continue to decline, reduced forms of inorganic nitrogen (NH x  = NH 3  + NH 4 + ) now contribute >50% of total Nr deposition over large areas of the U.S. Expanded monitoring and additional process-level research are needed to better understand NH x deposition, its contribution to total Nr deposition budgets, and the processes by which reduced N deposits to ecosystems. Urban and suburban areas are hotspots where routine monitoring of oxidized and reduced Nr deposition is needed. Finally, deposition budgets have incomplete information about the speciation of atmospheric nitrogen; monitoring networks do not capture important forms of Nr such as organic nitrogen. Building on these themes, we detail the state of the science of Nr deposition budgets in the U.S. and highlight research priorities to improve deposition budgets in terms of monitoring and flux measurements, leaf- to regional-scale modeling, source apportionment, and characterization of deposition trends and patterns., (Published by Elsevier B.V.)

Excess reactive nitrogen (N r ) 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 N r 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., (Published by Elsevier B.V.)

Particulate matter with aerodynamic diameter less than 2.5 μm (PM 2.5 ) is a complex mixture of chemical constituents emitted from various emission sources or through secondary reactions/processes; however, PM 2.5 is regulated mostly based on its total mass concentration. Studies to identify the impacts on climate change, visibility degradation and public health of different PM 2.5 constituents are hindered by limited ground measurements of PM 2.5 constituents. In this study, national models were developed based on random forest algorithm, one of machine learning methods that is of high predictive capacity and able to provide interpretable results, to predict concentrations of PM 2.5 sulfate, nitrate, organic carbon (OC) and elemental carbon (EC) across the conterminous United States from 2005 to 2015 at the daily level. The random forest models achieved high out-of-bag (OOB) R 2 values at the daily level, and the mean OOB R 2 values were 0.86, 0.82, 0.71 and 0.75 for sulfate, nitrate, OC and EC, respectively, over 2005-2015. The long-term temporal trends of PM 2.5 sulfate, nitrate, OC and EC predictions agreed well with their corresponding ground measurements. The annual mean of predicted PM 2.5 sulfate and EC levels across the conterminous United States decreased substantially from 2005 to 2015; while concentrations of predicted PM 2.5 nitrate and OC decreased and fluctuated during the study period. The annual prediction maps captured the characterized spatial patterns of the PM 2.5 constituents. The distributions of annual mean concentrations of sulfate and nitrate were generally regional in the extent that sulfate decreased from east to west smoothly with enhancement in California and nitrate had higher concentration in Midwest, Metro New York area, and California. OC and EC had regional high concentrations in the Southeast and Northwest as well as localized high levels around urban centers. The spatial patterns of PM 2.5 constituents were consistent with the distributions of their emission sources and secondary processes and transportation. Hence, the national models developed in this study could provide supplementary evaluations of spatio-temporal distributions of PM 2.5 constituents with full time-space coverages in the conterminous United States, which could be beneficial to assess the impacts of PM 2.5 constituents on radiation budgets and visibility degradation, and support exposure assessment for regional to national health studies at county or city levels to understand the acute and chronic toxicity and health impacts of PM 2.5 constituents, and consequently provide scientific evidence for making targeted and effective regulations of PM 2.5 pollution., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Human influenced atmospheric reactive nitrogen (RN) is impacting ecosystems in Rocky Mountain National Park (ROMO). Due to ROMO's protected status as a Class 1 area, these changes are concerning, and improving our understanding of the contributions of different types of RN and their sources is important for reducing impacts in ROMO. In July-August 2014 the most comprehensive measurements (to date) of RN were made in ROMO during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ). Measurements included peroxyacetyl nitrate (PAN), C 1 -C 5 alkyl nitrates, and high-time resolution NO x , NO y , and ammonia. A limited set of measurements was extended through October. Co-located measurements of a suite of volatile organic compounds provide information on source types impacting ROMO. Specifically, we use ethane as a tracer of oil and gas operations and tetrachloroethylene (C 2 Cl 4 ) as an urban tracer to investigate their relationship with RN species and transport patterns. Results of this analysis suggest elevated RN concentrations are associated with emissions from oil and gas operations, which are frequently co-located with agricultural production and livestock feeding areas in the region, and from urban areas. There also are periods where RN at ROMO is impacted by long-range transport. We present an atmospheric RN budget and a nitrogen deposition budget with dry and wet components. Total deposition for the period (7/1-9/30) was estimated at 1.58 kg N/ha, with 87% from wet deposition during this period of above average precipitation. Ammonium wet deposition was the dominant contributor to total nitrogen deposition followed by nitrate wet deposition and total dry deposition. Ammonia was estimated to be the largest contributor to dry deposition followed by nitric acid and PAN (other species included alkyl nitrates, ammonium and nitrate). All three species are challenging to measure routinely, especially at high time resolution., Competing Interests: Jeffrey L. Collett Jr is an Academic Editor for PeerJ.

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 (PM 2.5 -particles with aerodynamic diameters <2.5 µm) soil and elemental carbon (EC) concentrations, as well as coarse mass (CM = PM 10 -PM 2.5 ). 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.

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.

Oil and gas production in the Western United States has increased considerably over the past 10 years. While many of the still limited oil and gas impact assessments have focused on potential human health impacts, the typically remote locations of production in the Intermountain West suggests that the impacts of oil and gas production on national parks and wilderness areas (Class I and II areas) could also be important. To evaluate this, we utilize the Comprehensive Air quality Model with Extensions (CAMx) with a year-long modeling episode representing the best available representation of 2011 meteorology and emissions for the Western United States. The model inputs for the 2011 episodes were generated as part of the Three State Air Quality Study (3SAQS). The study includes a detailed assessment of oil and gas (O&G) emissions in Western States. The year-long modeling episode was run both with and without emissions from O&G production. The difference between these two runs provides an estimate of the contribution of the O&G production to air quality. These data were used to assess the contribution of O&G to the 8 hour average ozone concentrations, daily and annual fine particulate concentrations, annual nitrogen deposition totals and visibility in the modeling domain. We present the results for the Class I and II areas in the Western United States. Modeling results suggest that emissions from O&G activity are having a negative impact on air quality and ecosystem health in our National Parks and Class I areas., Implications: In this research, we use a modeling framework developed for oil and gas evaluation in the western United States to determine the modeled impacts of emissions associated with oil and gas production on air pollution metrics. We show that oil and gas production may have a significant negative impact on air quality and ecosystem health in some national parks and other Class I areas in the western United States. Our findings are of particular interest to federal land managers as well as regulators in states heavy in oil and gas production as they consider control strategies to reduce the impact of development.

Rapid development of agriculture and fossil fuel combustion greatly increased US reactive nitrogen emissions to the atmosphere in the second half of the 20th century, resulting in excess nitrogen deposition to natural ecosystems. Recent efforts to lower nitrogen oxides emissions have substantially decreased nitrate wet deposition. Levels of wet ammonium deposition, by contrast, have increased in many regions. Together these changes have altered the balance between oxidized and reduced nitrogen deposition. Across most of the United States, wet deposition has transitioned from being nitrate-dominated in the 1980s to ammonium-dominated in recent years. Ammonia has historically not been routinely measured because there are no specific regulatory requirements for its measurement. Recent expansion in ammonia observations, however, along with ongoing measurements of nitric acid and fine particle ammonium and nitrate, permit new insight into the balance of oxidized and reduced nitrogen in the total (wet + dry) US nitrogen deposition budget. Observations from 37 sites reveal that reduced nitrogen contributes, on average, ∼65% of the total inorganic nitrogen deposition budget. Dry deposition of ammonia plays an especially key role in nitrogen deposition, contributing from 19% to 65% in different regions. Future progress toward reducing US nitrogen deposition will be increasingly difficult without a reduction in ammonia emissions.