Development and Application of a United States wide correction for PM2.5 data collected with the PurpleAir sensor.

PurpleAir sensors, which measure particulate matter (PM), are widely used by individuals, community groups, and other organizations including state and local air monitoring agencies. PurpleAir sensors comprise a massive global network of more than 10,000 sensors. Previous performance evaluations have typically studied a limited number of PurpleAir sensors in small geographic areas or laboratory environments. While useful for determining sensor behavior and data normalization for these geographic areas, little work has been done to understand the broad applicability of these results outside these regions and conditions. Here, PurpleAir sensors operated by air quality monitoring agencies are evaluated in comparison to collocated ambient air quality regulatory instruments. In total, almost 12,000 24-hour averaged PM2.5 measurements from collocated PurpleAir sensors and Federal Reference Method (FRM) or Federal Equivalent Method (FEM) PM2.5 measurements were collected across diverse regions of the United States (U.S.), including 16 states. Consistent with previous evaluations, under typical ambient and smoke impacted conditions, the raw data from PurpleAir sensors overestimate PM2.5 concentrations by about 40% in most parts of the U.S. A simple linear regression reduces much of this bias across most U.S. regions, but adding a relative humidity term further reduces the bias and improves consistency in the biases between different regions. More complex multiplicative models did not substantially improve results when tested on an independent dataset. The final PurpleAir correction reduces the root mean square error (RMSE) of the raw data from 8 µg m-3 to 3 µg m-3 with an average FRM or FEM concentration of 9 µg m-3. This correction equation, along with proposed data cleaning criteria, has been applied to PurpleAir PM2.5 measurements across the U.S. in the AirNow Fire and Smoke Map (fire.airnow.gov) and has the potential to be successfully used in other air quality and public health applications.

Characterizing Nitrogen Oxides and Fine Particulate Matter near Major Highways in the United States Using the National Near-Road Monitoring Network.

As part of the United States Environmental Protection Agency's 2010 Nitrogen Dioxide (NO2) National Ambient Air Quality Standards (NAAQS) review, a national network of near-road sites was established to characterize pollutant behavior, interaction, and dispersion in the ambient near-road environment. Using spatial interpolation to estimate the near-road concentration increments of NO2 and particulate matter with an aerodynamic diameter of 2.5 µm and less (PM2.5) relative to nearby non-near-road monitors, we found that the 2013-2018 national average increment is 6.9 ppb and 1.0 µg m-3 for NO2 and PM2.5, respectively. Analyses of the hourly near-road NO2, nitric oxide (NO), and PM2.5 increments showed distinct diurnal cycles; the NO2 increment peaks at ∼9 ppb during the early afternoon (2-4 pm local time) while the NO and PM2.5 increments peak during the morning rush hour (5-8 am local time) at 25 ppb and 1.8 µg m-3 for NO and PM2.5, respectively. Although long-term trends are not yet available for this network of sites, a similar analysis of the NO2 and PM2.5 increment at a quasi-near-road site outside of the official network in Elizabeth, NJ showed gradual decreases in the increment over time since the mid-2000s.

Impact of dimethylsulfide chemistry on air quality over the Northern Hemisphere.

We implement oceanic dimethylsulfide (DMS) emissions and its atmospheric chemical reactions into the Community Multiscale Air Quality (CMAQv53) model and perform annual simulations without and with DMS chemistry to quantify its impact on tropospheric composition and air quality over the Northern Hemisphere. DMS chemistry enhances both sulfur dioxide (SO2) and sulfate ( S O 4 2 - ) over seawater and coastal areas. It enhances annual mean surface SO2 concentration by +46 pptv and S O 4 2 - by +0.33 µg/m3 and decreases aerosol nitrate concentration by -0.07 µg/m3 over seawater compared to the simulation without DMS chemistry. The changes decrease with altitude and are limited to the lower atmosphere. Impacts of DMS chemistry on S O 4 2 - are largest in the summer and lowest in the fall due to the seasonality of DMS emissions, atmospheric photochemistry and resultant oxidant levels. Hydroxyl and nitrate radical-initiated pathways oxidize 75% of the DMS while halogen-initiated pathways oxidize 25%. DMS chemistry leads to more acidic particles over seawater by decreasing aerosol pH. Increased S O 4 2 - from DMS enhances atmospheric extinction while lower aerosol nitrate reduces the extinction so that the net effect of DMS chemistry on visibility tends to remain unchanged over most of the seawater.

Incorporation of Remote PM2.5 Concentrations into the Downscaler Model for Spatially Fused Air Quality Surfaces.

The United States Environmental Protection Agency (EPA) has implemented a Bayesian spatial data fusion model called the Downscaler (DS) model to generate daily air quality surfaces for PM2.5 across the contiguous U.S. Previous implementations of DS relied on monitoring data from EPA's Air Quality System (AQS) network, which is largely concentrated in urban areas. In this work, we introduce to the DS modeling framework an additional PM2.5 input dataset from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network located mainly in remote sites. In the western U.S. where IMPROVE sites are relatively dense (compared to the eastern U.S.), the inclusion of IMPROVE PM2.5 data to the DS model runs reduces predicted annual averages and 98th percentile concentrations by as much as 1.0 and 4 µg m-3, respectively. Some urban areas in the western U.S., such as Denver, Colorado, had moderate increases in the predicted annual average concentrations, which led to a sharpening of the gradient between urban and remote areas. Comparison of observed and DS-predicted concentrations for the grid cells containing IMPROVE and AQS sites revealed consistent improvement at the IMPROVE sites but some degradation at the AQS sites. Cross-validation results of common site-days withheld in both simulations show a slight reduction in the mean bias but a slight increase in the mean square error when the IMPROVE data is included. These results indicate that the output of the DS model (and presumably other Bayesian data fusion models) is sensitive to the addition of geographically distinct input data, and that the application of such models should consider the prediction domain (national or urban focused) when deciding to include new input data.

A System for Developing and Projecting PM2.5 Spatial Fields to Correspond to Just Meeting National Ambient Air Quality Standards.

PM2.5 concentration fields that correspond to just meeting national ambient air quality standards (NAAQS) are useful for characterizing exposure in regulatory assessments. Computationally efficient methods that incorporate predictions from photochemical grid models (PGM) are needed to realistically project baseline concentration fields for these assessments. Thorough cross validation (CV) of hybrid spatial prediction models is also needed to better assess their predictive capability in sparsely monitored areas. In this study, a system for generating, evaluating, and projecting PM2.5 spatial fields to correspond with just meeting the PM2.5 NAAQS is developed and demonstrated. Results of ten-fold CV based on standard and spatial cluster withholding approaches indicate that performance of three spatial prediction models improves with decreasing distance to the nearest neighboring monitor, improved PGM performance, and increasing distance from sources of PM2.5 heterogeneity (e.g., complex terrain and fire). An air quality projection tool developed here is demonstrated to be effective for quickly projecting PM2.5 spatial fields to just meet NAAQS using realistic spatial response patterns based on air quality modeling. PM2.5 tends to be most responsive to primary PM2.5 emissions in urban areas, whereas response patterns are relatively smooth for NOx and SO2 emission changes. On average, PM2.5 is more responsive to changes in anthropogenic primary PM2.5 emissions than NOx and SO2 emissions in the contiguous U.S.

Influence of bromine and iodine chemistry on annual, seasonal, diurnal, and background ozone: CMAQ simulations over the Northern Hemisphere.

Bromine and iodine chemistry has been updated in the Community Multiscale Air Quality (CMAQ) model to better capture the influence of natural emissions from the oceans on ozone concentrations. Annual simulations were performed using the hemispheric CMAQ model without and with bromine and iodine chemistry. Model results over the Northern Hemisphere show that including bromine and iodine chemistry in CMAQ not only reduces ozone concentrations within the marine boundary layer but also aloft and inland. Bromine and iodine chemistry reduces annual mean surface ozone over seawater by 25%, with lesser ozone reductions over land. The bromine and iodine chemistry decreases ozone concentration without changing the diurnal profile and is active throughout the year. However, it does not have a strong seasonal influence on ozone over the Northern Hemisphere. Model performance of CMAQ is improved by the bromine and iodine chemistry when compared to observations, especially at coastal sites and over seawater. Relative to bromine, iodine chemistry is approximately four times more effective in reducing ozone over seawater over the Northern Hemisphere (on an annual basis). Model results suggest that the chemistry modulates intercontinental transport and lowers the background ozone imported to the United States.

Impact of halogen chemistry on summertime air quality in coastal and continental Europe: application of the CMAQ model and implications for regulation.

Halogen (Cl, Br, and I) chemistry has been reported to influence the formation of secondary air pollutants. Previous studies mostly focused on the impact of chlorine species on air quality over large spatial scales. Very little attention has been paid to the effect of the combined halogen chemistry on air quality over Europe and its implications for control policy. In the present study, we apply a widely used regional model, the Community Multiscale Air Quality Modeling System (CMAQ), incorporated with the latest halogen sources and chemistry, to simulate the abundance of halogen species over Europe and to examine the role of halogens in the formation of secondary air pollution. The results suggest that the CMAQ model is able to reproduce the level of O3, NO2, and halogen species over Europe. Chlorine chemistry slightly increases the levels of OH, HO2, NO3, O3, and NO2 and substantially enhances the level of the Cl radical. Combined halogen chemistry induces complex effects on OH (ranging from -0.023 to 0.030 pptv) and HO2 (in the range of -3.7 to 0.73 pptv), significantly reduces the concentrations of NO3 (as much as 20 pptv) and O3 (as much as 10 ppbv), and decreases NO2 in highly polluted regions (as much as 1.7 ppbv); it increases NO2 (up to 0.20 ppbv) in other areas. The maximum effects of halogen chemistry occur over oceanic and coastal regions, but some noticeable impacts also occur over continental Europe. Halogen chemistry affects the number of days exceeding the European Union target threshold for the protection of human beings and vegetation from ambient O3. In light of the significant impact of halogen chemistry on air quality, we recommend that halogen chemistry be considered for inclusion in air quality policy assessments, particularly in coastal cities.

Recommended metric for tracking visibility progress in the Regional Haze Rule.

For many national parks and wilderness areas with special air quality protections (Class I areas) in the western United States (U.S.), wildfire smoke and dust events can have a large impact on visibility. The U.S. Environmental Protection Agency's (EPA) 1999 Regional Haze Rule used the 20% haziest days to track visibility changes over time even if they are dominated by smoke or dust. Visibility on the 20% haziest days has remained constant or degraded over the last 16 yr at some Class I areas despite widespread emission reductions from anthropogenic sources. To better track visibility changes specifically associated with anthropogenic pollution sources rather than natural sources, the EPA has revised the Regional Haze Rule to track visibility on the 20% most anthropogenically impaired (hereafter, most impaired) days rather than the haziest days. To support the implementation of this revised requirement, the EPA has proposed (but not finalized) a recommended metric for characterizing the anthropogenic and natural portions of the daily extinction budget at each site. This metric selects the 20% most impaired days based on these portions using a "delta deciview" approach to quantify the deciview scale impact of anthropogenic light extinction. Using this metric, sulfate and nitrate make up the majority of the anthropogenic extinction in 2015 on these days, with natural extinction largely made up of organic carbon mass in the eastern U.S. and a combination of organic carbon mass, dust components, and sea salt in the western U.S. For sites in the western U.S., the seasonality of days selected as the 20% most impaired is different than the seasonality of the 20% haziest days, with many more winter and spring days selected. Applying this new metric to the 2000-2015 period across sites representing Class I areas results in substantial changes in the calculated visibility trend for the northern Rockies and southwest U.S., but little change for the eastern U.S. IMPLICATIONS: Changing the approach for tracking visibility in the Regional Haze Rule allows the EPA, states, and the public to track visibility on days when reductions in anthropogenic emissions have the greatest potential to improve the view. The calculations involved with the recommended metric can be incorporated into the routine IMPROVE (Interagency Monitoring of Protected Visual Environments) data processing, enabling rapid analysis of current and future visibility trends. Natural visibility conditions are important in the calculations for the recommended metric, necessitating the need for additional analysis and potential refinement of their values.

The influence of ocean halogen and sulfur emissions in the air quality of a coastal megacity: The case of Los Angeles.

The oceans are the main source of natural halogen and sulfur compounds, which have a significant influence on the oxidizing capacity of the marine atmosphere; however, their impact on the air quality of coastal cities is currently unknown. We explore the effect of marine halogens (Cl, Br and I) and dimethyl sulfide (DMS) on the air quality of a large coastal city through a set of high-resolution (4-km) air quality simulations for the urban area of Los Angeles, US, using the Community Multiscale Air Quality (CMAQ model). The results indicate that marine halogen emissions decrease ozone and nitrogen dioxide levels up to 5ppbv and 2.5ppbv, respectively, in the city of Los Angeles. Previous studies suggested that the inclusion of chlorine in air quality models leads to the generation of ozone in urban areas through photolysis of nitryl chloride (ClNO2). However, we find that when considering the chemistry of Cl, Br and I together the net effect is a reduction of surface ozone concentrations. Furthermore, combined ocean emissions of halogens and DMS cause substantial changes in the levels of key urban atmospheric oxidants such as OH, HO2 and NO3, and in the composition and mass of fine particles. Although the levels of ozone, NO3 and HOx are reduced, we find a 10% increase in secondary organic aerosol (SOA) mean concentration, attributed to the increase in aerosol acidity and sulfate aerosol formation when combining DMS and bromine. Therefore, this new pathway for enhanced SOA formation may potentially help with current model under predictions of urban SOA. Although further observations and research are needed to establish these preliminary conclusions, this first city-scale investigation suggests that the inclusion of oceanic halogens and DMS in air quality models may improve regional air quality predictions over coastal cities around the world.

The Impact of Iodide-Mediated Ozone Deposition and Halogen Chemistry on Surface Ozone Concentrations Across the Continental United States.

The air quality of many large coastal areas in the United States is affected by the confluence of polluted urban and relatively clean marine airmasses, each with distinct atmospheric chemistry. In this context, the role of iodide-mediated ozone (O3) deposition over seawater and marine halogen chemistry accounted for in both the lateral boundary conditions and coastal waters surrounding the continental U.S. is examined using the Community Multiscale Air Quality (CMAQ) model. Several nested simulations are conducted in which these halogen processes are implemented separately in the continental U.S. and hemispheric CMAQ domains, the latter providing lateral boundary conditions for the former. Overall, it is the combination of these processes within both the continental U.S. domain and from lateral boundary conditions that lead to the largest reductions in modeled surface O3 concentrations. Predicted reductions in surface O3 concentrations occur mainly along the coast where CMAQ typically has large overpredictions. These results suggest that a realistic representation of halogen processes in marine regions can improve model prediction of O3 concentrations near the coast.

Description and evaluation of the Community Multiscale Air Quality (CMAQ) modeling system version 5.1.

The Community Multiscale Air Quality (CMAQ) model is a comprehensive multipollutant air quality modeling system developed and maintained by the US Environmental Protection Agency's (EPA) Office of Research and Development (ORD). Recently, version 5.1 of the CMAQ model (v5.1) was released to the public, incorporating a large number of science updates and extended capabilities over the previous release version of the model (v5.0.2). These updates include the following: improvements in the meteorological calculations in both CMAQ and the Weather Research and Forecast (WRF) model used to provide meteorological fields to CMAQ, updates to the gas and aerosol chemistry, revisions to the calculations of clouds and photolysis, and improvements to the dry and wet deposition in the model. Sensitivity simulations isolating several of the major updates to the modeling system show that changes to the meteorological calculations result in enhanced afternoon and early evening mixing in the model, periods when the model historically underestimates mixing. This enhanced mixing results in higher ozone (O3) mixing ratios on average due to reduced NO titration, and lower fine particulate matter (PM2.5) concentrations due to greater dilution of primary pollutants (e.g., elemental and organic carbon). Updates to the clouds and photolysis calculations greatly improve consistency between the WRF and CMAQ models and result in generally higher O3 mixing ratios, primarily due to reduced cloudiness and attenuation of photolysis in the model. Updates to the aerosol chemistry result in higher secondary organic aerosol (SOA) concentrations in the summer, thereby reducing summertime PM2.5 bias (PM2.5 is typically underestimated by CMAQ in the summer), while updates to the gas chemistry result in slightly higher O3 and PM2.5 on average in January and July. Overall, the seasonal variation in simulated PM2.5 generally improves in CMAQv5.1 (when considering all model updates), as simulated PM2.5 concentrations decrease in the winter (when PM2.5 is generally overestimated by CMAQ) and increase in the summer (when PM2.5 is generally underestimated by CMAQ). Ozone mixing ratios are higher on average with v5.1 vs. v5.0.2, resulting in higher O3 mean bias, as O3 tends to be overestimated by CMAQ throughout most of the year (especially at locations where the observed O3 is low); however, O3 correlation is largely improved with v5.1. Sensitivity simulations for several hypothetical emission reduction scenarios show that v5.1 tends to be slightly more responsive to reductions in NO x (NO + NO2), VOC and SO x (SO2 + SO4) emissions than v5.0.2, representing an improvement as previous studies have shown CMAQ to underestimate the observed reduction in O3 due to large, widespread reductions in observed emissions.

The reduction of summer sulfate and switch from summertime to wintertime PM2.5 concentration maxima in the United States.

Exposure to particulate matter air pollution with a nominal mean aerodynamic diameter less than or equal to 2.5 µm (PM2.5) has been associated with health effects including cardiovascular disease and death. Here, we add to the understanding of urban and rural PM2.5 concentrations over large spatial and temporal scales in recent years. We used high-quality, publicly-available air quality monitoring data to evaluate PM2.5 concentration patterns and changes during the years 2000-2015. Compiling and averaging measurements collected across the U.S. revealed that PM2.5 concentrations from urban sites experienced seasonal maxima in both winter and summer. Within each year from 2000 to 2008, the maxima of urban summer peaks were greater than winter peaks. However, from 2012 to 2015, the maxima of urban summertime PM2.5 peaks were smaller than the urban wintertime PM2.5 maxima, due to a decrease in the magnitude of summertime maxima with no corresponding decrease in the magnitude of winter maxima. PM2.5 measurements at rural sites displayed summer peaks with magnitudes relatively similar to those of urban sites, and negligible to no winter peaks through the time period analyzed. Seasonal variations of urban and rural PM2.5 sulfate, PM2.5 nitrate, and PM2.5 organic carbon (OC) were also assessed. Summer peaks in PM2.5 sulfate decreased dramatically between 2000 and 2015, whereas seasonal PM2.5 OC and winter PM2.5 nitrate concentration maxima remained fairly consistent. These findings demonstrate that PM2.5 concentrations, especially those occurring in the summertime, have declined in the U.S. from 2000 to 2015. In addition, reduction strategies targeting sulfate have been successful and the decrease in PM2.5 sulfate contributed to the decline in total PM2.5.

Impact of Enhanced Ozone Deposition and Halogen Chemistry on Tropospheric Ozone over the Northern Hemisphere.

Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen chemistry in a comprehensive atmospheric modeling system. The enhanced ozone deposition treatment accounts for the interaction of iodide in seawater with ozone and increases deposition velocities by 1 order of magnitude. Halogen chemistry includes detailed chemical reactions of organic and inorganic bromine and iodine species. Two different simulations are completed with the halogen chemistry: without and with photochemical reactions of higher iodine oxides. Enhanced deposition reduces mean summer-time surface ozone by ∼3% over marine regions in the Northern Hemisphere. Halogen chemistry without the photochemical reactions of higher iodine oxides reduces surface ozone by ∼15% whereas simulations with the photochemical reactions of higher iodine oxides indicate ozone reductions of ∼48%. The model without these processes overpredicts ozone compared to observations whereas the inclusion of these processes improves predictions. The inclusion of photochemical reactions for higher iodine oxides leads to ozone predictions that are lower than observations, underscoring the need for further refinement of the halogen emissions and chemistry scheme in the model.

Near-road modeling and measurement of cerium-containing particles generated by nanoparticle diesel fuel additive use.

Cerium oxide nanoparticles (nCe) are used as a fuel-borne catalyst in diesel engines to reduce particulate emissions, yet the environmental and human health impacts of the exhaust particles are not well understood. To bridge the gap between emission measurements and ambient impacts, size-resolved measurements of particle composition and mass concentration have been performed in Newcastle-upon-Tyne, United Kingdom, where buses have used an nCe additive since 2005. These observations show that the noncrustal cerium fraction thought to be associated with the use of nCe has a mass concentration ∼ 0.3 ng m(-3) with a size distribution peaking at 100-320 nm in aerodynamic diameter. Simulations with a near-roadway multicomponent sectional aerosol dynamic model predict that the use of nCe additives increases the number concentration of nuclei mode particles (<50 nm in diameter) while decreasing the total mass concentration. The near-road model predicts a downwind mass size distribution of cerium-containing particles peaking at 150 nm in aerodynamic diameter, a value similar to that measured for noncrustal cerium in Newcastle. This work shows that both the emission and atmospheric transformation of cerium-containing particles needs to be taken into account by regional modelers, exposure scientists, and policymakers when determining potential environmental and human health impacts.