Ammonia Dry Deposition in an Alpine Ecosystem Traced to Agricultural Emission Hotpots.

Elevated reactive nitrogen (Nr) deposition is a concern for alpine ecosystems, and dry NH3 deposition is a key contributor. Understanding how emission hotspots impact downwind ecosystems through dry NH3 deposition provides opportunities for effective mitigation. However, direct NH3 flux measurements with sufficient temporal resolution to quantify such events are rare. Here, we measured NH3 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 NH3 sensors on a mobile laboratory and an eddy covariance tower to measure NH3 concentrations and fluxes. Our spatial sampling illustrated an upslope event that transported NH3 emissions from the hotspot to RMNP. Observed NH3 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 NH3 fluxes were calculated using observed, bidirectional modeled, and gap-filled fluxes. More than 40% of the total dry NH3 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 NH3 hotspot, and more observations are needed to quantify the impacts of these hotspots on dry NH3 deposition in these regions.

Increasing importance of deposition of reduced nitrogen in the United States.

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.

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.

Coupling chemical transport model source attributions with positive matrix factorization: application to two IMPROVE sites impacted by wildfires.

Source contributions to total fine particle carbon predicted by a chemical transport model (CTM) were incorporated into the positive matrix factorization (PMF) receptor model to form a receptor-oriented hybrid model. The level of influence of the CTM versus traditional PMF was varied using a weighting parameter applied to an object function as implemented in the Multilinear Engine (ME-2). The methodology provides the ability to separate features that would not be identified using PMF alone, without sacrificing fit to observations. The hybrid model was applied to IMPROVE data taken from 2006 through 2008 at Monture and Sula Peak, Montana. It was able to separately identify major contributions of total carbon (TC) from wildfires and minor contributions from biogenic sources. The predictions of TC had a lower cross-validated RMSE than those from either PMF or CTM alone. Two unconstrained, minor features were identified at each site, a soil derived feature with elevated summer impacts and a feature enriched in sulfate and nitrate with significant, but sporadic contributions across the sampling period. The respective mean TC contributions from wildfires, biogenic emissions, and other sources were 1.18, 0.12, and 0.12 ugC/m(3) at Monture and 1.60, 0.44, and 0.06 ugC/m(3) at Sula Peak.

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.

Observations of ozone, acyl peroxy nitrates, and their precursors during summer 2019 at Carlsbad Caverns National Park, New Mexico.

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 (O3) at CAVE has frequently exceeded the 70 ppbv 8-hour National Ambient Air Quality Standard. We examine the influence of regional emissions on O3 formation using observations of O3, nitrogen oxides (NOx = NO + NO2), a suite of volatile organic compounds (VOCs), peroxyacetyl nitrate (PAN), and peroxypropionyl nitrate (PPN). Elevated O3 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) O3 exceeded 65 ppbv; MDA8 O3 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 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 O3 days, there is more contribution from factors associated with secondary photochemical processing of O&G emissions. The observed ratio of VOCs to NOx is consistently high throughout the study period, consistent with NOx-limited O3 production. Finally, all high O3 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 NOx-sensitive photochemistry at Carlsbad Caverns National Park indicating that reductions in NOx emissions should drive reductions in O3. However, the NOx-sensitivity is largely driven by emissions of NOx into a VOC-rich environment, and a high PPN:PAN ratio and its relationship to O3 indicate substantial influence from alkanes in the regional photochemistry. Thus, simultaneous reductions in emissions of NOx and non-methane VOCs from the oil and gas sector should be considered for reducing O3 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.

Source characterization of volatile organic compounds at Carlsbad Caverns National Park.

Carlsbad 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 O3 in the region.

A Global-Scale Mineral Dust Equation.

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 (K2O + MgO + Na2O)/Al2O3 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 PM2.5 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.

PM2.5 in Carlsbad Caverns National Park: Composition, sources, and visibility impacts.

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) PM2.5 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 (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 PM2.5 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.

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.

Uncertainties in PM2.5 gravimetric and speciation measurements and what we can learn from them.

The U.S. Environmental Protection Agency (EPA) and the federal land management community (National Park Service, United States Fish and Wildlife Service, United States Forest Service, and Bureau of Land Management) operate extensive particle speciation monitoring networks that are similar in design but are operated for different objectives. Compliance (mass only) monitoring is also carried out using federal reference method (FRM) criteria at approximately 1000 sites. The Chemical Speciation Network (CSN) consists of approximately 50 long-term-trend sites, with about another 250 sites that have been or are currently operated by state and local agencies. The sites are located in urban or suburban settings. The Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring network consists of about 181 sites, approximately 170 of which are in nonurban areas. Each monitoring approach has its own inherent monitoring limitations and biases. Determination of gravimetric mass has both negative and positive artifacts. Ammonium nitrate and other semivolatiles are lost during sampling, whereas, on the other hand, measured mass includes particle-bound water. Furthermore, some species may react with atmospheric gases, further increasing the positive mass artifact. Estimating aerosol species concentrations requires assumptions concerning the chemical form of various molecular compounds, such as nitrates and sulfates, and organic material and soil composition. Comparing data collected in the various monitoring networks allows for assessing uncertainties and biases associated with both negative and positive artifacts of gravimetric mass determinations, assumptions of chemical composition, and biases between different sampler technologies. All these biases are shown to have systematic seasonal characteristics. Unaccounted-for particle-bound water tends to be higher in the summer, as does nitrate volatilization. The ratio of particle organic mass divided by organic carbon mass (Roc) is higher during summer and lower during the winter seasons in both CSN and IMPROVE networks, and Roc is lower in urban than non-urban environments.

Total sulfur analysis of fine particulate mass on nylon filters by ICP-OES.

Sulfur (S) and sulfate (SO4 2- ) in fine particulate matter (PM2.5 ) are monitored by the Interagency Monitoring of Protected Visual Environments (IMPROVE) network at remote and rural sites across the United States. Within the IMPROVE network, S is determined from X-ray fluorescence (XRF) spectroscopy from a Teflon filter, and SO4 2- is determined via ion chromatography (IC) from a nylon filter. Differences in S and SO4 2- estimates may indicate the presence of organosulfur (OS) species or biases between sampling and analytical methods. To reduce potential biases, an inductively coupled plasma-optical emission spectroscopy (ICP-OES) method was developed to allow for analysis of SO4 2- and S from a single filter extract. Sulfur (ICP-OES) and SO4 2- (IC) estimates from 2016 IMPROVE filters correlated strongly, suggesting that, on average, ICP-OES accurately estimated S. However, observed differences between slopes suggested the presence of water-soluble OS species, especially during summer. Organosulfur species are important indicators of secondary organic aerosols formed through reactions of biogenic and anthropogenic pollutants and can be quantified through laboratory techniques such as reverse-phase liquid chromatography (RPLC) or hydrophilic liquid interaction chromatography (HILIC) coupled to electrospray ionization-high-resolution tandem mass spectrometry (RPLC/ESI-HR-MS/MS and HILIC/ESI-HR-MS/MS, respectively), and field techniques using Aerodyne aerosol mass spectrometry (AMS). However, these methods are costly and introduce relatively large uncertainties when scaled for large networks such as IMPROVE. The method described in this report provides an inexpensive complement to XRF, which measures total S (insoluble and water-soluble S) to estimate water-soluble S and OS concentrations in PM.

Large global variations in measured airborne metal concentrations driven by anthropogenic sources.

Globally consistent measurements of airborne metal concentrations in fine particulate matter (PM2.5) are important for understanding potential health impacts, prioritizing air pollution mitigation strategies, and enabling global chemical transport model development. PM2.5 filter samples (N ~ 800 from 19 locations) collected from a globally distributed surface particulate matter sampling network (SPARTAN) between January 2013 and April 2019 were analyzed for particulate mass and trace metals content. Metal concentrations exhibited pronounced spatial variation, primarily driven by anthropogenic activities. PM2.5 levels of lead, arsenic, chromium, and zinc were significantly enriched at some locations by factors of 100-3000 compared to crustal concentrations. Levels of metals in PM2.5 and PM10 exceeded health guidelines at multiple sites. For example, Dhaka and Kanpur sites exceeded the US National Ambient Air 3-month Quality Standard for lead (150 ng m-3). Kanpur, Hanoi, Beijing and Dhaka sites had annual mean arsenic concentrations that approached or exceeded the World Health Organization's risk level for arsenic (6.6 ng m-3). The high concentrations of several potentially harmful metals in densely populated cites worldwide motivates expanded measurements and analyses.

Characterization of the winter midwestern particulate nitrate bulge.

A previously unobserved multi-state region of elevated particulate nitrate concentration was detected as a result of the expansion of the Interagency Monitoring of Protected Visual Environments (IMPROVE) network of remote-area particulate matter (PM) speciation monitoring sites into the midwestern United States that began in 2002. Mean winter ammonium nitrate concentrations exceed 4 microg/m3 in a region centered in Iowa, which makes it responsible for as much as half of the particle light extinction. Before these observations, particulate nitrate in the United States was only observed to be a dominant component of the fine PM (PM2.5) in parts of California and some urban areas. Comparisons of the spatial patterns of particulate nitrate with spatial patterns of ammonia and nitrogen oxide emissions suggest that the nitrate bulge is the result of the high emissions of ammonia associated with animal agriculture in the Midwest. Nitrate episodes at several locations in the eastern United States are shown to be associated with transport pathways over the Midwest, suggesting long-range transport of either ammonia or ammonium nitrate. Thermodynamic equilibrium modeling conducted by others on data from the Midwest shows the relative importance of atmospheric ammonia and nitric acid in the production of PM2.5. This is a particular concern as the sulfur dioxide emissions in the United States are reduced, which increases the amount of ammonia available for ammonium nitrate production.

Which visibility indicators best represent a population's preference for a level of visual air quality?

Several 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.

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.

Space-time trends of PM2.5 constituents in the conterminous United States estimated by a machine learning approach, 2005-2015.

Particulate matter with aerodynamic diameter less than 2.5 µm (PM2.5) is a complex mixture of chemical constituents emitted from various emission sources or through secondary reactions/processes; however, PM2.5 is regulated mostly based on its total mass concentration. Studies to identify the impacts on climate change, visibility degradation and public health of different PM2.5 constituents are hindered by limited ground measurements of PM2.5 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 PM2.5 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) R2 values at the daily level, and the mean OOB R2 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 PM2.5 sulfate, nitrate, OC and EC predictions agreed well with their corresponding ground measurements. The annual mean of predicted PM2.5 sulfate and EC levels across the conterminous United States decreased substantially from 2005 to 2015; while concentrations of predicted PM2.5 nitrate and OC decreased and fluctuated during the study period. The annual prediction maps captured the characterized spatial patterns of the PM2.5 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 PM2.5 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 PM2.5 constituents with full time-space coverages in the conterminous United States, which could be beneficial to assess the impacts of PM2.5 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 PM2.5 constituents, and consequently provide scientific evidence for making targeted and effective regulations of PM2.5 pollution.