U.S. National PM2.5 Chemical Speciation Monitoring Networks—CSN and IMPROVE: Description of networks

The U.S. Environmental Protection Agency (EPA) initiated the national PM_2.5 Chemical Speciation Monitoring Network (CSN) in 2000 to support evaluation of long-term trends and to better quantify the impact of sources on particulate matter (PM) concentrations in the size range below 2.5 μm aerodynamic diameter (PM_2.5; fine particles). The network peaked at more than 260 sites in 2005. In response to the 1999 Regional Haze Rule and the need to better understand the regional transport of PM, EPA also augmented the long-existing Interagency Monitoring of Protected Visual Environments (IMPROVE) visibility monitoring network in 2000, adding nearly 100 additional IMPROVE sites in rural Class 1 Areas across the country. Both networks measure the major chemical components of PM_2.5 using historically accepted filter-based methods. Components measured by both networks include major anions, carbonaceous material, and a series of trace elements. CSN also measures ammonium and other cations directly, whereas IMPROVE estimates ammonium assuming complete neutralization of the measured sulfate and nitrate. IMPROVE also measures chloride and nitrite. In general, the field and laboratory approaches used in the two networks are similar; however, there are numerous, often subtle differences in sampling and chemical analysis methods, shipping, and quality control practices. These could potentially affect merging the two data sets when used to understand better the impact of sources on PM concentrations and the regional nature and long-range transport of PM_2.5. This paper describes, for the first time in the peer-reviewed literature, these networks as they have existed since 2000, outlines differences in field and laboratory approaches, provides a summary of the analytical parameters that address data uncertainty, and summarizes major network changes since the inception of CSN.

ImplicationsTwo long-term chemical speciation particle monitoring networks have operated simultaneously in the United States since 2001, when the EPA began regular operations of its PM_2.5 Chemical Speciation Monitoring Network (IMPROVE began in 1988). These networks use similar field sampling and analytical methods, but there are numerous, often subtle differences in equipment and methodologies that can affect the results. This paper describes these networks since 2000 (inception of CSN) and their differences, and summarizes the analytical parameters that address data uncertainty, providing researchers and policymakers with background information they may need (e.g., for 2018 PM_2.5 designation and State Implementation Plan process; McCarthy, 2013) to assess results from each network and decide how these data sets can be mutually employed for enhanced analyses. Changes in CSN and IMPROVE that have occurred over the years also are described.     

Revised algorithm for estimating light extinction from IMPROVE particle speciation data

The Interagency Monitoring of Protected Visual Environments (IMPROVE) particle monitoring network consists of approximately 160 sites at which fine particulate matter (PM2.5) mass and major species concentrations and course particulate matter (PM10) mass concentrations are determined by analysis of 24-hr duration sampling conducted on a 1-day-in-3 schedule A simple algorithm to estimate light extinction from the measured species concentrations was incorporated in the 1999 Regional Haze Rule as the basis for the haze metric used to track haze trends. A revised algorithm was developed that is more consistent with the recent atmospheric aerosol literature and reduces bias for high and low light extinction extremes. The revised algorithm differs from the original algorithm in having a term for estimating sea salt light scattering from Cl(-) ion data, using 1.8 instead of 1.4 for the mean ratio of organic mass to measured organic carbon, using site-specific Rayleigh scattering based on site elevation and mean temperature, employing a split component extinction efficiency associated with large and small size mode sulfate, nitrate and organic mass species, and adding a term for nitrogen dioxide (NO2) absorption for sites with NO2 concentration information. Light scattering estimates using the original and the revised algorithms are compared with nephelometer measurements at 21 IMPROVE monitoring sites. The revised algorithm reduces the underprediction of high haze periods and the overprediction of low haze periods compared with the performance of the original algorithm. This is most apparent at the hazier monitoring sites in the eastern United States. For each site, the PM10 composition for days selected as the best 20% and the worst 20% haze condition days are nearly identical regardless of whether the basis of selection was light scattering from the original or revised algorithms, or from nephelometer-measured light scattering.     

Determination of the organic aerosol mass to organic carbon ratio in IMPROVE samples

The ratio of organic mass (OM) to organic carbon (OC) in PM(2.5) aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM(2.5) mass and chemical constituents other than OC (mass balance) in IMPROVE samples from 1988 to 2003. Archived IMPROVE filters from five IMPROVE sites were extracted with dichloromethane (DCM), acetone and water. The extract residues were weighed to determine OM and analyzed for OC by thermal optical reflectance (TOR). On average, successive extracts of DCM, acetone, and water contained 64%, 21%, and 15%, respectively, of the extractable OC, respectively. On average, the non-blank-corrected recovery of the OC initially measured in these samples by TOR was 115+/-42%. OM/OC ratios from the combined DCM and acetone extracts averaged 1.92 and ranged from 1.58 at Indian Gardens, AZ in the Grand Canyon to 2.58 at Mount Rainier, WA. The average OM/OC ratio determined by mass balance was 2.07 across the IMPROVE network. The sensitivity of this ratio to assumptions concerning sulfate neutralization, water uptake by hygroscopic species, soil mass, and nitrate volatilization were evaluated. These results suggest that the value of 1.4 for the OM/OC ratio commonly used for mass and light extinction reconstruction in IMPROVE is too low.     

Comparison of sulfate and nitrate particle mass concentrations measured by IMPROVE and the CDN

The 1977 and 1990 Amendments to the Clean Air Act call for visibility and atmospheric deposition monitoring throughout the United States. We compare sulfate and nitrate particle mass concentrations measured by two regional air quality networks, the Interagency Monitoring of PROtected Visual Environments (IMPROVE) network and the Clean Air Status and Trends Network (CASTNet), or CASTNet Deposition Network (CDN). The intent of this comparison is to quantify bias that may be introduced from differences in the respective network's sampling protocols. A number of sampling protocol differences exist between the two networks that may lead to sampling bias, particularly for particle NO₃⁻. Observed differences between particle SO₄²⁻ mass concentrations reported by the two monitoring networks are generally small, yet statistically significant at many comparison sites. Differences between particle NO₃⁻ mass concentrations are substantial, statistically significant at nearly all comparison sites, and the bias magnitude varies by geographic region. Differences in particle NO₃⁻, based on data from monitoring sites selected for this comparison, are 40% in the west, 56% in the interior desert/mountain region, and −9% in the east, expressed as the IMPROVE mean subtracted from the CDN mean, as a percent of the IMPROVE mean. Comparisons are made using data from 23 locations where monitoring sites from IMPROVE and CDN are within approximately 50 km.     

PM2.5 mass and light extinction reconstruction in IMPROVE

Compliance under the Regional Haze Rule of 1999 is based on Interagency Monitoring of Protected Visual Environments (IMPROVE) protocols for reconstructing aerosol mass and light extinction from aerosol chemical concentrations measured in the IMPROVE network. The accuracy, consistency, and potential biases in these formulations were examined using IMPROVE aerosol chemistry and light extinction data from 1988-1999. Underestimation of particulate matter with an aerodynamic diameter < 2.5 microm (PM2.5) by the IMPROVE mass reconstruction formula by 12%, on average, appears to be related to the exclusion of sodium, chlorine, and other elements and to artifacts associated with the measurement of organic carbon, but not to absorption of water by sulfates and nitrates on IMPROVE Teflon filters during weighing. Light scattering measured by transmissometry is not consistent with nephelometer scattering or single-scatter albedos expected for remote locations. Light scattering was systematically overestimated by 34%, on average, with the IMPROVE particle scattering (Bsp) reconstruction formula. The use of climatologically based hygroscopic growth factors f(RH) suggested for compliance with the Haze Rule contributes significantly to this overestimation and increases the amount of light extinction attributable to sulfates for IMPROVE samples between 1993 and 1999 by 5 percentage points.     

Continuous determination of fine particulate matter mass in the Salt Lake City Environmental Monitoring project: a comparison of real-time and conventional TEOM monitor results

Fine particulate matter (PM2.5) mass was determined on a continuous basis at the Salt Lake City Environmental Protection Agency Environmental Monitoring for Public Awareness and Community Tracking monitoring site in Salt Lake City, UT, using three different monitoring techniques. Hourly averaged PM2.5 mass data were collected during two sampling periods (summer 2000 and winter 2002) using a real-time total ambient mass sampler (RAMS), sample equilibration system (SES)-tapered element oscillating microbalance (TEOM), and conventional TEOM monitor. This paper compares the results obtained from the various monitoring systems, which differ in their treatment of semivolatile material (SVM; particle-bound water, semivolatile ammonium nitrate, and semivolatile organic compounds). PM2.5 mass results obtained by the RAMS were consistently higher than those obtained by the SES-TEOM and conventional TEOM monitors because of the RAMS ability to measure semivolatile ammonium nitrate and semivolatile organic material but not particle-bound water. The SES-TEOM monitoring system was able to account for an average of 28% of the SVM, whereas the conventional TEOM monitor loses essentially all of the SVM from the single filter during sampling. Occasional mass readings by the various TEOM monitors that are higher than RAMS results may reflect particle-bound water, which, under some conditions, is measured by the TEOM but not the RAMS.     

Chemical mass balance source apportionment for combined PM2.5 measurements from U.S. non-urban and urban long-term networks

The Minnesota Particulate Matter 2.5 (PM_2.5) Source Apportionment Study was undertaken to explore the utility of PM_2.5 mass, element, ion, and carbon measurements from long-term speciation networks for pollution source attribution. Ambient monitoring data at eight sites across the state were retrieved from the archives of the Interagency Monitoring of Protected Visual Environments (IMPROVE) and the Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]) and analyzed by an Effective Variance – Chemical Mass Balance (EV-CMB) receptor model with region-specific geological source profiles developed in this study. PM_2.5 was apportioned into contributions of fugitive soil dust, calcium-rich dust, taconite (low grade iron ore) dust, road salt, motor vehicle exhaust, biomass burning, coal-fired utility, and secondary aerosol. Secondary sulfate and nitrate contributed strongly (49–71% of PM_2.5) across all sites and was dominant (≥60%) at IMPROVE sites. Vehicle exhausts accounted for 20–70% of the primary PM_2.5 contribution, largely exceeding the proportion in the primary PM_2.5 emission inventory. The diesel exhaust contribution was separable from the gasoline engine exhaust contribution at the STN sites. Higher detection limits for several marker elements in the STN resulted in non-detectable coal-fired boiler contributions which were detected in the IMPROVE data. Despite the different measured variables, analytical methods, and detection limits, EV-CMB results from a nearby IMPROVE-STN non-urban/urban sites showed similar contributions from regional sources – including fugitive dust and secondary aerosol. Seasonal variations of source contributions were examined and extreme PM_2.5 episodes were explained by both local and regional pollution events.     

An examination of the physical and optical properties of aerosols collected in the IMPROVE program

The Interagency Monitoring of Protected Visual Environments (IMPROVE) protocols for reconstructing the ambient light extinction coefficient (b_ext) from measured aerosol species are the basis for evaluating compliance under the Regional Haze Rule. Aerosol mass composition and optical properties have been measured as part of the IMPROVE program since 1988, providing a long-term data set of aerosol properties at 38 sites around the US. This data set is used to evaluate assumptions made in calculating reconstructed mass and b_ext by applying statistical analysis techniques. In particular, the molecular weight to carbon weight ratio used to compute particulate organic matter is investigated. An annual average value of 1.7±0.2 for the IMPROVE sites, compared to the value of 1.4 currently assumed in the IMPROVE algorithm, is derived. Regression analysis also indicates that fine soil mass concentrations are underestimated by roughly 20% on average. Finally, aerosol mass scattering and extinction efficiencies assumed in the IMPROVE reconstructed b_ext protocol are examined. Fine mode (D_p<2.5 μm) mass scattering efficiencies have a functional dependence on mass concentrations at many sites, and use of a mass-concentration-dependent adjustment factor to refine the assumed efficiencies provides for closer agreement between measured and reconstructed b_ext.     

Evaluation of the IMPROVE Equation for estimating aerosol light extinction

The [revised] IMPROVE Equation for estimating light extinction from aerosol chemical composition was evaluated considering new measurements at U.S. national parks. Compared with light scattering (Bsp) measured at seven IMPROVE sites with nephelometer data from 2003–2012, the [revised] IMPROVE Equation over- and underestimated Bsp in the lower and upper quintiles, respectively, of measured Bsp. Underestimation of the worst visibility cases (upper quintile) was reduced by assuming an organic mass (OM)/organic carbon (OC) ratio of 2.1 and hygroscopic growth of OM, based on results from previous field studies. This assumption, however, tended to overestimate low Bsp even more. Assuming that sulfate was present as ammonium bisulfate rather than as ammonium sulfate uniformly reduced estimated Bsp. The split-mode model of concentration- and size-dependent dry mass scattering efficiencies in the [revised] IMPROVE Equation does not eliminate systematic biases in estimated Bsp. While the new measurements of OM/OC and OM hygroscopicity should be incorporated into future iterations of the IMPROVE Equation, the problem is not well constrained due to a lack of routine measurements of sulfate neutralization and the water-soluble fraction of OM in the IMPROVE network.

Implications: Studies in U.S. national parks showed that aerosol organics contain more mass and absorb more water as a function of relative humidity than is currently assumed by the IMPROVE Equation for calculating chemical light extinction. Consideration of these results could significantly shift the apportionment of light extinction to water-soluble organic aerosols and therefore better inform pollution control strategies under the U.S. Environmental Protection Agency Regional Haze Rule.     

PM2.5 source apportionment: reconciling receptor models for U.S. nonurban and urban long-term networks

Chemical mass balance (CMB) and trajectory receptor models were applied to speciated particulate matter with aerodynamic diameter < or =2.5 microm (PM2.5) measurements from Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]) and Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring network across the state of Minnesota as part of the Minnesota PM2.5 Source Apportionment Study (MPSAS). CMB equations were solved by the Unmix, positive matrix factorization (PMF), and effective variance (EV) methods, giving collective source contribution and uncertainty estimates. Geological source profiles developed from local dust materials were either incorporated into the EV-CMB model or used to verify factors derived from Unmix and PMF. Common sources include soil dust, calcium (Ca)-rich dust, diesel and gasoline vehicle exhausts, biomass burning, secondary sulfate, and secondary nitrate. Secondary sulfate and nitrate aerosols dominate PM2.5 mass (50-69%). Mobile sources outweigh area sources at urban sites, and vice versa at rural sites due to traffic emissions. Gasoline and diesel contributions can be separated using data from the STN, despite significant uncertainties. Major differences between MPSAS and earlier studies on similar environments appear to be the type and magnitude of stationary sources, but these sources are generally minor (<7%) in this and other studies. Ensemble back-trajectory analysis shows that the lower Midwestern states are the predominant source region for secondary ammoniated sulfate in Minnesota. It also suggests substantial contributions of biomass burning and soil dust from out-of-state on occasions, although a quantitative separation of local and regional contributions was not achieved in the current study. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for a summary of input data, Unmix and PMF factor profiles, and additional maps.     

Spatial and temporal characterization of PM2.5 mass concentrations in California, 1980-2007

Systematic measurement of fine particulate matter (aerodynamic diameter less than 2.5 microm [PM2.5]) mass concentrations began nationally with implementation of the Federal Reference Method (FRM) network in 1998 and 1999. In California, additional monitoring of fine particulate matter (PM) occurred via a dichotomous sampler network and several special studies carried out between 1982 and 2002. The authors evaluate the comparability of FRM and non-FRM measurements of PM2.5 mass concentrations and establish conversion factors to standardize fine mass measurements from different methods to FRM-equivalent concentrations. The authors also identify measurements of PM2.5 mass concentrations that do not agree with FRM or other independent PM2.5 mass measurements. The authors show that PM2.5 mass can be reconstructed to a high degree of accuracy (r2 > 0.9; mean absolute error approximately 2 microg m(-3)) from PM with an aerodynamic diameter < or =10 microm (PM10) mass and species concentrations when site-specific and season-specific conversion factors are used and a statewide record of fine PM mass concentrations by combining the FRM PM2.5 measurements, non-FRM PM2.5 measurements, and reconstructions of PM2.5 mass concentrations. Trends and spatial variations are evaluated using the integrated data. The rates of change of annual fine PM mass were negative (downward trends) at all 22 urban and 6 nonurban (Interagency Monitoring of Protected Visual Environments [IMPROVE]) monitoring locations having at least 15 yr of data during the period 1980-2007. The trends at the IMPROVE sites ranged from -0.05 to -0.25 microg m(-3) yr(-1) (median -0.11 microg m(-3) yr(-1)), whereas urban-site trends ranged from -0.13 to -1.29 microg m(-3) yr(-1) (median -0.59 microg m(-3) yr(-1)). The urban concentrations declined by a factor of 2 over the period of record, and these decreases were qualitatively consistent with changes in emissions of primary PM2.5 and gas-phase precursors of secondary PM. Mean PM2.5 mass concentrations ranged from 3.3 to 7.4 microg m(-3) at IMPROVE sites and from 9.3 to 37.1 microg m(-3) at urban sites.     

Correction methods for organic carbon artifacts when using quartz-fiber filters in large particulate matter monitoring networks: the regression method and other options

Sampling and handling artifacts can bias filter-based measurements of particulate organic carbon (OC). Several measurement-based methods for OC artifact reduction and/or estimation are currently used in research-grade field studies. OC frequently is not artifact-corrected in large routine sampling networks (e.g., U.S. Environmental Protection Agency (EPA)'s Chemical Speciation Network). In some cases, the OC artifact has been corrected using a regression method (RM) for artifact estimation. In this method, the gamma-intercept of the regression of the OC concentration on the fine particle (PM2.5) mass concentration is taken to be an estimate of the average OC sampling artifact (net of positive and negative artifacts). This paper discusses options for artifact correction in large routine sampling networks. Specifically, the goals are to (1) articulate the assumptions and limitations inherent to the RM, (2) describe other artifact correction approaches, and (3) suggest a cost-effective method for artifact correction in large monitoring networks. The RM assumes a linear relationship between measured OC and PM mass: a constant slope (OC mass fraction) and a constant intercept (RM artifact estimate). These assumptions are not always valid. Additionally, outliers and other individual data points can have a large influence on the RM artifact estimates. The RM yields results within the range of measurement-based methods for some datasets and not for others. Given that the adsorption of organic gases increases with atmospheric concentrations of organics, subtraction of an average artifact from all samples (e.g., across multiple sites) will underestimate OC for lower-concentration samples (e.g., clean sites) and overestimate OC for higher-concentration samples (e.g., polluted sites). For relatively accurate, simple, and cost-effective artifact OC estimation in large networks, the authors suggest backup filter sampling on at least 10% of sampling days at all sites with artifact correction on a sample-by-sample basis as described herein.     

Interpretation of trends of PM2.5 and reconstructed visibility from the IMPROVE network

Under the IMPROVE visibility monitoring network, federal land managers have monitored visibility and fine particle concentrations at 29 Class I area sites (mostly national parks and wilderness areas) and Washington, DC since 1988. This paper evaluates trends in reconstructed visibility and fine particles for the 10th (best visibility days), 50th (average visibility days), and 90th (worst visibility days) percentiles over the nine-year period from 1988-96. Data from these sites provides an indication of regional trends in air quality and visibility resulting from implementation of various emission reduction strategies.     

Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.     

Interpretation of Trends of PM25 and Reconstructed Visibility from the IMPROVE Network

ABSTRACT

Under the IMPROVE visibility monitoring network, federal land managers have monitored visibility and fine particle concentrations at 29 Class I area sites (mostly national parks and wilderness areas) and Washington, DC since 1988. This paper evaluates trends in reconstructed visibility and fine particles for the 10th (best visibility days), 50th (average visibility days), and 90th (worst visibility days) percentiles over the nine-year period from 1988-96. Data from these sites provides an indication of regional trends in air quality and visibility resulting from implementation of various emission reduction strategies.     

Model evidence for a significant source of secondary organic aerosol from isoprene

We investigate how a recently suggested pathway for production of secondary organic aerosol (SOA) affects the consistency of simulated organic aerosol (OA) mass in a global three-dimensional model of oxidant-aerosol chemistry (GEOS-Chem) versus surface measurements from the interagency monitoring of protected visual environments (IMPROVE) network. Simulations in which isoprene oxidation products contribute to SOA formation, with a yield of 2.0% by mass reduce a model bias versus measured OA surface mass concentrations. The resultant increase in simulated OA mass concentrations during summer of 0.6–1.0 μg m⁻³ in the southeastern United States reduces the regional RMSE to 0.88 μg m⁻³ from 1.26 μg m⁻³. Spring and fall biases are also reduced, with little change in winter when isoprene emissions are negligible.     

Particulate nitrate measurement using nylon filters

Nylon filters are a popular medium to collect atmospheric fine particles in different aerosol monitoring networks, including those operated by the U.S. Environmental Protection Agency and the Interagency Monitoring of Protected Visual Environments (IMPROVE) program. Extraction of the filters by deionized water or by a basic aqueous solution (typically a mixture of sodium carbonate and sodium bicarbonate) is often performed to permit measurement of the inorganic ion content of the collected particles. Whereas previous studies have demonstrated the importance of using a basic solution to efficiently extract gaseous nitric acid collected using nylon filters, there has been a recent movement to the use of deionized water for extraction of particles collected on nylon filters to eliminate interference from sodium ion (Na+) during ion chromatographic analysis of inorganic aerosol cations. Results are reported here from a study designed to investigate the efficiency of deionized water extraction of aerosol nitrate (NO3-) and sulfate from nylon filters. Data were obtained through the conduct of five field experiments at selected IMPROVE sites. Results indicate that the nylon filters provide superior retention of collected fine particle NO3-, relative to Teflon filters, and that deionized water extraction (with ultrasonication) of collected NO3- and sulfate is as efficient, for the situations studied, as extraction using a basic solution of 1.7 mM sodium bicarbonate and 1.8 mM sodium carbonate.     

Diurnal and seasonal patterns in light scattering,extinction, and relative humidity

Since 1988, several federal and state governmental agencies in the US have coordinated efforts to operate the interagency monitoring of protected visual environments (IMPROVE) network at sites in remote areas. Most IMPROVE sites are equipped with either a transmissometer to measure light extinction (B_ext) or a nephelometer to measure particle scattering (B_sp). Optical, temperature, and relative humidity (RH) measurements are made hourly at these sites. The diurnal and seasonal patterns in these data are examined and discussed here. At many IMPROVE sites the diurnal patterns in RH and therefore B_ext or B_sp are as expected based on average temperature. On average, RH is higher at night and during the winter than during warmer times of the day and year. Also as expected, based on RH alone, at many sites hourly mean B_ext or B_sp values are either in phase with RH or weakly dependent on time of day. Usually, the diurnal differences are not as large as the seasonal differences. Another group of IMPROVE sites have mean RH patterns similar to those described above but have a different diurnal pattern in measured scattering or extinction. At these sites, the highest mean B_sp or B_ext occurs during mid-day rather than at night. At several of these sites, especially those on ridge tops, it is hypothesized that this is because the diurnal shifts in mixing height only allow the surface layer of the atmosphere to reach the monitor during mid-day. Several other sites have unique diurnal or seasonal patterns in average B_sp or B_ext that can usually be linked to emissions in nearby source regions or local meteorology and terrain.     

Light scattering from sea-salt aerosols at Interagency Monitoring of Protected Visual Environments (IMPROVE) sites

A method is described to estimate light scattering (Bsp) by sea-salt aerosols at coastal locations in the Interagency Monitoring of Protected Visual Environments (IMPROVE) network. Dry mass scattering efficiencies for fine and coarse sea-salt particles were based on previously measured dry sea-salt size distributions. Enhancement of sea-salt particle scattering by hygroscopic growth was based on NaCl water activity data. Sea-salt aerosol mass at the IMPROVE site in the Virgin Islands (VIIS) was estimated from strontium (Sr) concentrations in IMPROVE aerosol samples. Estimated Bsp, including contributions from sea-salt mass based on Sr, agreed well with measured Bsp at the VIIS IMPROVE site. On average, sea salt accounted for 52% of estimated Bsp at this site. Sea-salt aerosol mass cannot be reliably estimated from Sr unless its crustal enrichment factor exceeds 10. Sodium (Na) concentrations are not accurately determined by X-ray fluorescence analysis in IMPROVE samples. It is recommended that Na be measured in the fine and coarse modes by a more appropriate method, such as atomic absorption spectroscopy or ion chromatography, to account for scattering by sea-salt particles at IMPROVE sites where such contributions may be significant.     

Evaluation of multisectional and two-section particulate matter photochemical grid models in the Western United States

Version 4.10s of the comprehensive air-quality model with extensions (CAMx) photochemical grid model has been developed, which includes two options for representing particulate matter (PM) size distribution: (1) a two-section representation that consists of fine (PM2.5) and coarse (PM2.5-10) modes that has no interactions between the sections and assumes all of the secondary PM is fine; and (2) a multisectional representation that divides the PM size distribution into N sections (e.g., N = 10) and simulates the mass transfer between sections because of coagulation, accumulation, evaporation, and other processes. The model was applied to Southern California using the two-section and multisection representation of PM size distribution, and we found that allowing secondary PM to grow into the coarse mode had a substantial effect on PM concentration estimates. CAMx was then applied to the Western United States for the 1996 annual period with a 36-km grid resolution using both the two-section and multisection PM representation. The Community Multiscale Air Quality (CMAQ) and Regional Modeling for Aerosol and Deposition (REMSAD) models were also applied to the 1996 annual period. Similar model performance was exhibited by the four models across the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Clean Air Status and Trends Network monitoring networks. All four of the models exhibited fairly low annual bias for secondary PM sulfate and nitrate but with a winter overestimation and summer underestimation bias. The CAMx multisectional model estimated that coarse mode secondary sulfate and nitrate typically contribute <10% of the total sulfate and nitrate when averaged across the more rural IMPROVE monitoring network.