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Air quality management commonly aims to mitigate nitrogen oxide (NOx) emissions from combustion, reducing ozone (O3) and particulate matter (PM) pollution. Despite such ongoing efforts, regulations have recently proven ineffective in rural areas like the Salton Sea Air Basin of Southern California, which routinely violates O3 and PM air quality standards. With over $2 billion in annual agricultural sales and low population density, air quality in the region is likely influenced by the year-round farming activity. We conducted a source apportionment of NOx (an important precursor to both O3 and PM) using nitrogen stable isotopes of ambient NO2, which revealed a significant contribution from soil-emitted NOx to the regional budget. The soil source strength was estimated based on the mean δ15N-NOx from each emission category in the California Air Resources Board's NOx inventory. Our annual average soil emission estimate for the air basin was 11.4 ± 4 tons/d, representing ~ 30% of the extant NOx inventory, 10× larger than the state's inventory for soil emissions. Unconstrained environmental factors such as nutrient availability, soil moisture, and temperature have a first-order impact on soil NOx production in this agriculturally intensive region, with fertilization and irrigation practices likely driving most of the emissions variability. Without spatially and temporally accurate data on fertilizer application rates and irrigation schedules, it is difficult to determine the direct impacts that these variations have on our observations. Nevertheless, comparative analysis with previous studies indicates that soil NOx emissions in the Imperial Valley are likely underrepresented in current inventories, highlighting the need for more detailed and localized observational data to constrain the sizeable and variable emissions from these arid, agricultural soils.

Air quality management commonly aims to mitigate nitrogen oxide (NOx) emissions from combustion, reducing ozone (O3) and particulate matter (PM) pollution. Despite such ongoing efforts, regulations have recently proven ineffective in rural areas like the Salton Sea Air Basin of Southern California, which routinely violates O3 and PM air quality standards. With over $2 billion in annual agricultural sales and low population density, air quality in the region is likely influenced by the year-round farming activity. We conducted a source apportionment of NOx (an important precursor to both O3 and PM) using nitrogen stable isotopes of ambient NO2, which revealed a significant contribution from soil-emitted NOx to the regional budget. The soil source strength was estimated based on the mean δ15N-NOx from each emission category in the California Air Resources Board's NOx inventory. Our annual average soil emission estimate for the air basin was 11.4 ± 4 tons/d, representing ~ 30% of the extant NOx inventory, 10× larger than the state's inventory for soil emissions. Unconstrained environmental factors such as nutrient availability, soil moisture, and temperature have a first-order impact on soil NOx production in this agriculturally intensive region, with fertilization and irrigation practices likely driving most of the emissions variability. Without spatially and temporally accurate data on fertilizer application rates and irrigation schedules, it is difficult to determine the direct impacts that these variations have on our observations. Nevertheless, comparative analysis with previous studies indicates that soil NOx emissions in the Imperial Valley are likely underrepresented in current inventories, highlighting the need for more detailed and localized observational data to constrain the sizeable and variable emissions from these arid, agricultural soils. [ABSTRACT FROM AUTHOR]

The oxygen isotope anomaly (Δ17O = δ17O - 0.52 × δ18O > 0) has proven to be a robust tool for probing photochemical cycling and atmospheric formation pathways of oxidized reactive nitrogen (NOy). Several studies have developed modeling techniques to implicitly model Δ17O of NOy molecules based on numerous assumptions that may not always be valid. Thus, these models may be oversimplified and limit our ability to compare model Δ17O values of NOy with observations. In this work, we introduce a novel method for explicitly tracking Δ17O transfer and propagation into NOy and odd oxygen (Ox), integrated into the Regional Atmospheric Chemistry Mechanism, version 2 (RACM2). Termed ICOIN-RACM2 (InCorporating Oxygen Isotopes of NOy in RACM2), this new model includes the addition of 55 new species and 729 replicate reactions to represent the propagation of Δ17O derived from O3 into NOy and Ox. Employing this mechanism within a box model, we simulate Δ17O for various NOy and Ox molecules for chamber experiments with varying initial nitrogen oxides (NOx = NO + NO2) and α -pinene conditions, revealing response shifts in Δ17O linked to distinct oxidant conditions. Furthermore, diel cycles are simulated under two summertime scenarios, representative of an urban and rural site, revealing pronounced Δ17O diurnal patterns for several NOy components and substantial Δ17O differences associated with pollution levels (urban vs. rural). Overall, the proposed mechanism offers the potential to assess NOy oxidation chemistry in chamber studies and air quality campaigns through Δ17O model comparisons against observations. The integration of this mechanism into a 3-D atmospheric chemistry transport model is expected to notably enhance our capacity to model and anticipate Δ17O across landscapes, consequently refining model representations of atmospheric chemistry and tropospheric oxidation capacity. [ABSTRACT FROM AUTHOR]

The oxygen-stable isotope mass-independent composition (Δ(17O) = d(17O) - 0.52×d(18O)) has proven to be a robust tool for probing photochemical cycling and atmospheric formation pathways of oxidized reactive nitrogen (NOy). Several studies have developed modeling techniques to implicitly model Δ(17O) based on numerous assumptions that may not always be valid. Thus, these models may be oversimplified and limit our ability to compare model Δ(17O) values of NOy with observations. In this work, we introduce a 5 novel method for explicit tracking of O3 transfer and propagation into NOy and odd oxygen (Ox), integrated into the Regional Atmospheric Chemistry Mechanism, version 2 (RACM2). Termed ICOIN-RACM2 (InCorporating Oxygen Isotopes of NOy in RACM2), this new model includes the addition of 55 new species and 727 replicate reactions to represent the oxygen isotopologues of NOy and Ox. Employing this mechanism within a box model, we simulate Δ(17O) for various NOy and Ox molecules for chamber experiments with varying initial nitrogen oxides (NOx = NO + NO2) and a-pinene conditions, revealing response shifts in Δ(17O) linked to distinct oxidant conditions. Furthermore, diel cycles are simulated under two summertime scenarios, representative of an urban and rural site, revealing pronounced Δ(17O) diurnal patterns for several NOy components and substantial Δ(17O) differences associated with pollution levels (urban vs. rural). Overall, the proposed mechanism offers the potential to assess NOy oxidation chemistry in chamber studies and air quality campaigns through Δ(17O) model comparisons against observations. The integration of this mechanism into a 3-D atmospheric chemistry transport model is expected to notably enhance our capacity to model and anticipate Δ(17O) across landscapes, consequently refining model representations of atmospheric chemistry and tropospheric oxidation capacity. [ABSTRACT FROM AUTHOR]

Despite significant precursor emission reductions in the US over recent decades, atmospheric nitrate deposition remains an important terrestrial stressor. Here, we utilized statistical air mass back trajectory analysis and nitrogen stable isotope deltas (δ (15 N)) to investigate atmospheric nitrate spatiotemporal trends in the northeastern US from samples collected at three US EPA Clean Air Status and Trends Network (CASTNET) sites from December 2016–2018. For the considered sites, similar seasonal patterns in nitric acid (HNO 3) and particulate nitrate (pNO 3) concentrations were observed with spatial differences attributed to nitrogen oxide (NO x) emission densities in source contributing regions that were typically ≤ 1000 km. Significant spatiotemporal δ (15 N) variabilities in HNO 3 and pNO 3 were observed with higher values during winter relative to summer, like previous reports from CASTNET samples collected in the early 2000s for our study region. In the early 2000s, δ (15 N) of atmospheric nitrate in the northeast US had been suggested to be driven by NO x emissions; however, we did not find significant spatiotemporal changes in the modeled NO x emissions by sector and fuel type or δ (15 N, NO x) for the source regions of the CASTNET sites. Instead, the seasonal and spatial differences in the observed δ (15 N) of atmospheric nitrate were driven by nitrate formation pathways (i.e., homogeneous reactions of NO 2 oxidation via hydroxyl radical or heterogeneous reactions of dinitrogen pentoxide on wetted aerosol surfaces) and their associated δ (15 N) fractionation. Under the field conditions of low NO x relative to O 3 concentrations and when δ (15 N, NO x) emission sources do not have significant variability, we demonstrate that δ (15 N) of atmospheric nitrate can be a robust tracer for diagnosing nitrate formation. [ABSTRACT FROM AUTHOR]

The northeastern US represents a mostly urban corridor impacted by high population density, high emissions density and degraded air quality and acid rain that has been a focus of regulatory-driven emissions reductions. Detailing the chemistry of atmospheric nitrate formation is critical for improving model representation of atmospheric chemistry and air quality. The oxygen isotope deltas (δ(18O) and Δ(17O)) of atmospheric nitrate are useful indicators in tracking nitrate formation pathways. Here, we measured Δ(17O) and δ(18O) for nitric acid (HNO3) and particulate nitrate (pNO3) from three US EPA Clean Air Status and Trends Network (CASTNET) sites in the northeastern US from December 2016 to 2018. The Δ(17O, HNO3) and δ(18O, HNO3) values ranged from 12.9 ‰ to 30.9 ‰ and from 46.9 ‰ to 82.1 ‰, and the Δ(17O, pNO3) and δ(18O, pNO) ranged from 16.6 ‰ to 33.7 ‰ and from 43.6 ‰ to 85.3 ‰, respectively. There was distinct seasonality of δ(18O) and Δ(17O) with higher values observed during winter compared to summer, suggesting a shift in O3 to HOx radical chemistry, as expected. Unexpectedly, there was a statistical difference in Δ(17O) between HNO3 and pNO3, with higher values observed for pNO3 (27.1±3.8) ‰ relative to HNO3 (22.7±3.6) ‰, and significant differences in the relationship between δ(18O) and Δ(17O). This difference suggests atmospheric nitrate phase-dependent 29 oxidation chemistry that is not predicted in models. Based on output from GEOS-Chem, and both the δ(18O) and Δ(17O) observations, we quantify the production pathways of atmospheric nitrate. The model significantly overestimated the heterogeneous N2O5 hydrolysis production for both HNO3 and pNO3, a finding consistent with observed seasonal changes in δ(18O), Δ(17O) and δ(15N) of HNO3 and pNO3, though large uncertainties remain in the quantitative transfer of δ(18O) from major atmospheric oxidants. This comparison provides important insight into the role of oxidation chemistry in reconciling a commonly observed positive bias for model atmospheric nitrate concentrations in the northeastern US. [ABSTRACT FROM AUTHOR]

Despite significant precursor emission reductions in the US over recent decades, atmospheric nitrate deposition remains an important terrestrial stressor. Here we utilized statistical air mass back trajectory analysis and nitrogen stable isotope deltas (δ(15N)) to investigate atmospheric nitrate spatiotemporal trends in the northeastern US from samples collected at three US EPA Clean Air Status and Trends Network (CASTNET) sites from December 2016–2018. For the considered sites, similar seasonal patterns in nitric acid (HNO3) and particulate nitrate (pNO3) concentrations were observed with spatial differences attributed to nitrogen oxide (NOx) emission densities in source contributing regions that were typically ≤1000 km. Significant spatiotemporal δ(15N) variabilities in HNO3 and pNO3 were observed with higher values during winter relative to summer, like previous reports from CASTNET samples collected in the early 2000s for our study region. In the early 2000s, δ(15N) of atmospheric nitrate in the Northeast US had been suggested to be driven by NOx emissions; however, we did not find significant spatiotemporal changes in the modeled NOx emissions by sector and fuel type or δ(15N, NOx) for the source regions of the CASTNET sites. Instead, the spatiotemporal trends were driven by δ(15N) fractionation associated with nitrate formation. Under the field conditions of low NOx relative to O3 concentrations and when δ(15N, NOx) emission sources do not have significant variability, we demonstrate that δ(15N) of atmospheric nitrate can be a robust tracer for diagnosing nitrate formation. [ABSTRACT FROM AUTHOR]

Atmospheric ammonia (NH3) is a critical component of our atmosphere that contributes to air quality degradation and reactive nitrogen deposition; however, our knowledge of NH3 in urban environments remains limited. Year-long ambient NH3 and related species were measured for concentrations and the nitrogen isotopic compositions (δ15N) of NH3 and particulate ammonium (pNH4+) to understand the temporal sources and chemistry of NH3 in a northeastern US urban environment. We found that urban NH3 and pNH4+ concentrations were elevated compared to regional rural background monitoring stations, with seasonally significant variations. Local and transported sources of NHx (NH3 + pNH4+) were identified using polar bivariate and statistical back trajectory analysis, which suggested the importance of vehicles, volatilization, industry, fuel combustion, and biomass burning emissions. Utilizing a uniquely positive δ15N(NH3) emission source signature from vehicles, a Bayesian stable isotope mixing model indicates that vehicles contribute 30.7±11.6 % (mean±1σ) to the annual background level of urban NHx, with a strong seasonal pattern with higher relative contribution during winter (45.8±13.0 %) compared to summer (20.8±9.7 %). The decrease in the relative importance of vehicle emissions during the summer was suggested to be driven by temperature-dependent NH3 emissions from volatilization sources based on wind direction, back trajectory, and NH3 emission inventory analysis. This work highlights that reducing vehicle NH3 emissions should be considered to improve wintertime air quality in this region. [ABSTRACT FROM AUTHOR]