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.     

APCA Financial Statements for FY 1979-80

The U.S. Environmental Protection Agency (EPA) has proposed a new secondary standard based on visibility in urban areas. The proposed standard will be based on light extinction, calculated from 24-hr averaged measurements. It would be desirable to base the standard on a shorter averaging time to better represent human perception of visibility. This could be accomplished by either an estimation of extinction from semicontinuous particulate matter (PM) data or direct measurement of scattering and absorption. To this end we have compared 1-hr measurements of fine plus coarse particulate scattering using a nephelometer, along with an estimate of absorption from aethalometer measurements. The study took place in Lindon, UT, during February and March 2012. The nephelometer measurements were corrected for coarse particle scattering and compared to the Filter Dynamic Measurement System (FDMS) tapered element oscillating microbalance monitor (TEOM) PM_2.5 measurements. The two measurements agreed with a mass scattering coefficient of 3.3 ± 0.3 m²/g at relative humidity below 80%. However, at higher humidity, the nephelometer gave higher scattering results due to water absorbed by ammonium nitrate and ammonium sulfate in the particles. This particle-associated water is not measured by the FDMS TEOM. The FDMS TEOM data could be corrected for this difference using appropriate IMPROVE protocols if the particle composition is known. However, a better approach may be to use a particle measurement system that allows for semicontinuous measurements but also measures particle bound water. Data are presented from a 2003 study in Rubidoux, CA, showing how this could be accomplished using a Grimm model 1100 aerosol spectrometer or comparable instrument.

Implications: Visibility is currently based on 24-hr averaged PM mass and composition. A metric that captures diurnal changes would better represent human perception. Furthermore, if the PM measurement included aerosol bound water, this would negate the need to know particulate composition and relative humidity (RH), which is currently used to estimate visibility. Methods are outlined that could accomplish both of these objectives based on use of a PM monitor that includes aerosol-bound water. It is recommended that these techniques, coupled with appropriate measurements of light scattering and absorption by aerosols, be evaluated for potential use in the visibility based secondary standard.     

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.     

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.     

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.     

Development of visibility forecasting modeling framework for the Lower Fraser Valley of British Columbia using Canada’s Regional Air Quality Deterministic Prediction System

Visibility degradation, one of the most noticeable indicators of poor air quality, can occur despite relatively low levels of particulate matter when the risk to human health is low. The availability of timely and reliable visibility forecasts can provide a more comprehensive understanding of the anticipated air quality conditions to better inform local jurisdictions and the public. This paper describes the development of a visibility forecasting modeling framework, which leverages the existing air quality and meteorological forecasts from Canada’s operational Regional Air Quality Deterministic Prediction System (RAQDPS) for the Lower Fraser Valley of British Columbia. A baseline model (GM-IMPROVE) was constructed using the revised IMPROVE algorithm based on unprocessed forecasts from the RAQDPS. Three additional prototypes (UMOS-HYB, GM-MLR, GM-RF) were also developed and assessed for forecast performance of up to 48 hr lead time during various air quality and meteorological conditions. Forecast performance was assessed by examining their ability to provide both numerical and categorical forecasts in the form of 1-hr total extinction and Visual Air Quality Ratings (VAQR), respectively. While GM-IMPROVE generally overestimated extinction more than twofold, it had skill in forecasting the relative species contribution to visibility impairment, including ammonium sulfate and ammonium nitrate. Both statistical prototypes, GM-MLR and GM-RF, performed well in forecasting 1-hr extinction during daylight hours, with correlation coefficients (R) ranging from 0.59 to 0.77. UMOS-HYB, a prototype based on postprocessed air quality forecasts without additional statistical modeling, provided reasonable forecasts during most daylight hours. In terms of categorical forecasts, the best prototype was approximately 75 to 87% correct, when forecasting for a condensed three-category VAQR. A case study, focusing on a poor visual air quality yet low Air Quality Health Index episode, illustrated that the statistical prototypes were able to provide timely and skillful visibility forecasts with lead time up to 48 hr.

Implications: This study describes the development of a visibility forecasting modeling framework, which leverages the existing air quality and meteorological forecasts from Canada’s operational Regional Air Quality Deterministic Prediction System. The main applications include tourism and recreation planning, input into air quality management programs, and educational outreach. Visibility forecasts, when supplemented with the existing air quality and health based forecasts, can assist jurisdictions to anticipate the visual air quality impacts as perceived by the public, which can potentially assist in formulating the appropriate air quality bulletins and recommendations.     

Improved light extinction reconstruction in interagency monitoring of protected visual environments

The U.S. Environmental Protection Agency (EPA) published the Regional Haze Rule (RHR) in 1999. The RHR default goal is to reduce haze linearly from the baseline period of 2000 through 2004 to natural background in 2064. EPA-recommended method for estimating baseline and natural haze uses the Interagency Monitoring of Protected Visual Environments (IMPROVE) light extinction formula. The IMPROVE formula predicts light extinction from measured aerosol chemical concentrations and estimates of the relative humidity multiplier. On average, the IMPROVE formula overpredicts 6156 nephelometer days (24-hr average measured particle light scattering, bsp) of data by 25%. A new IMPROVED method that reconstructs light extinction using a concentration power law model overpredicts these nephelometer days of data by just 2%. Ignoring the 20% lowest light scattering days, this new IMPROVED formula has a 3% underprediction bias over the 4925 highest nephelometer days with light scattering > or =8 inverse megameters. For comparison, the IMPROVE formula has a 12% overprediction bias for the same days. The IMPROVE formula overprediction averages 77%, 27%, 17%, 9%, and -5% broken down by quintile from lowest to highest nephelometer measured light scattering days. The new IMPROVED formula average overprediction is 21%, -5%, -5%, -2%, and 0%. So, agreement between measured and predicted light scattering improves by modifying the current IMPROVE light extinction formula.     

Formaldehyde and carbon dioxide air concentrations and their relationship with indoor environmental factors in daycare centers

The aim of this study was to measure the air concentrations of carbon dioxide (CO₂) and formaldehyde (HCHO) in daycare centers to determine relevant influencing factors, including temperature, relative humidity (RH), type of facility, number of children, type of ventilation system, ventilation time, and air cleaning system. The authors measured HCHO, CO₂, temperature, and RH in the center of classrooms in 289 daycare centers. Spearman’s correlation and Mann–Whitney analyses were used to examine the relationships and differences in HCHO and CO₂ for varying temperatures, RH values, and categorical indoor environmental factors. There were no significant differences in the HCHO and CO₂ air concentrations with varying numbers of children, ventilation times, or ventilation and air cleaning system types. However, both the HCHO and CO₂ air concentrations were significantly different for varying RH values, which were divided into five categories (p < 0.001). Only the HCHO air concentrations were significantly different for varying temperatures, which were divided into five categories (p < 0.001). Significant correlations were found between HCHO air concentrations and the temperature (r = 0.35, p < 0.0001), RH (r = 0.51, p < 0.0001), and CO₂ (r = 0.36, p < 0.0001). The study results support maintaining an appropriate temperature and RH range for reducing airborne HCHO in daycare centers. Further research is needed to elucidate the precise mechanisms responsible for the relationships observed in this study.

Implications: Data from 289 daycare centers in Seoul, South Korea, indicate that HCHO concentrations show a positive correlation with indoor temperature and relative humidity. This indicates that keeping temperatures low will help keep HCHO concentrations low, by both a direct and an indirect effect, since low temperatures also cause low relative humidity.     

Air pollutant source characterization using the revised regional haze tracking metric and a photochemical grid model and implications for regional haze planning

The 2017 revisions to the Regional Haze Rule clarify that visibility progress at Class I national parks and wilderness areas should be tracked on days with the highest anthropogenic contributions to haze (impairment). We compare the natural and anthropogenic contributions to haze in the western United States in 2011 estimated using the Environmental Protection Agency (EPA) recommended method and using model projections from the Comprehensive Air Quality Model with Extensions (CAMx) and the Particulate Source Apportionment Tool (PSAT). We do so because these two methods will be used by states to demonstrate visibility progress by 2028. If the two methods assume different natural and anthropogenic contributions, the projected benefits of reducing U.S. anthropogenic emissions will differ. The EPA method assumes that episodic elevated carbonaceous aerosols greater than an annual 95th percentile threshold are natural events. For western U.S. IMPROVE monitoring sites reviewed in this paper, CAMx-PSAT confirms these episodes are impacted by carbon from wildfire or prescribed fire events. The EPA method assumes that most of the ammonium sulfate is anthropogenic in origin. At most western sites CAMx-PSAT apportions more of the ammonium sulfate on the most impaired days to global boundary conditions and anthropogenic Canadian, Mexican, and offshore shipping emissions than to U.S. anthropogenic sources. For ammonium nitrate and coarse mass, CAMx-PSAT apportions greater contributions to U.S. anthropogenic sources than the EPA method assigns to total anthropogenic contributions. We conclude that for western IMPROVE sites, the EPA method is effective in selecting days that are likely to be impacted by anthropogenic emissions and that CAMx-PSAT is an effective approach to estimate U.S. source contributions. Improved inventories, particularly international and natural emissions, and further evaluation of global and regional model performance and PSAT attribution methods are recommended to increase confidence in modeled source characterization.

Implications: The western states intend to use the CAMx model to project visibility progress by 2028. Modeled visibility response to changes in U.S. anthropogenic emissions may be less than estimated using the EPA assumptions based on total U.S. and international anthropogenic contributions to visibility impairment. Additional model improvements are needed to better account for contributions to haze from natural and international emissions in current and future modeling years. These improvements will allow more direct comparison of model and EPA estimates of natural and anthropogenic contributions to haze and future visibility progress.     

Precipitation in Light Extinction Reconstruction

Abstract

The U.S. Environmental Protection Agency (EPA) published the Regional Haze Rule (RHR) in 1999.¹ The RHR default goal is to reduce haze linearly to natural background in 2064 from the baseline period of 2000–2004. The EPA default method^2,3 for estimating natural and baseline visibility uses the Interagency Monitoring of Protected Visual Environments (IMPROVE) formula. The IMPROVE formula predicts the light extinction coefficient from aerosol chemical concentrations measured by the IMPROVE network. The IMPROVE light scattering coefficient formula using data from 1994–2002 underestimated the measured light scattering coefficient by 700 Mm^?1, on average, on days with precipitation. Also, precipitation occurred as often on the clearest as haziest days. This led to estimating the light extinction coefficient of precipitation, averaged over all days, as the light scattering coefficient on days with precipitation (700 Mm^?1) multiplied by the percent of precipitation days in a year. This estimate added to the IMPROVE formula light extinction estimate gives a real world estimate of visibility for the 20% clearest, 20% haziest, and all days. For example, in 1993, the EPAs Report to Congress projected visibility in Class I areas would improve by 3 deciviews by 2010 across the haziest portions of the eastern United States because of the 1990 Clean Air Act Amendments. Omitted was the light extinction coefficient of precipitation. Adding in the estimated light extinction coefficient of precipitation, the estimated visibility improvement declines to <1 deci-view.     

Impacts of prescribed fires and benefits from their reduction for air quality,health, and visibility in the Pacific Northwest of the United States

Using a WRF-SMOKE-CMAQ modeling framework, we investigate the impacts of smoke from prescribed fires on model performance, regional and loc al air quality, health impacts, and visibility in protected natural environments using three different prescribed fire emission scenarios: 100% fire, no fire, and 30% fire. The 30% fire case reflects a 70% reduction in fire activities due to harvesting of logging residues for use as a feedstock for a potential aviation biofuel supply chain. Overall model performance improves for several performance metrics when fire emissions are included, especially for organic carbon, irrespective of the model goals and criteria used. This effect on model performance is more pronounced for the rural and remote IMPROVE sites for organic carbon and total PM_2.5. A reduction in prescribed fire emissions (30% fire case) results in significant improvement in air quality in areas in western Oregon, northern Idaho, and western Montana, where most prescribed fires occur. Prescribed burning contributes to visibility impairment, and a relatively large portion of protected class I areas will benefit from a reduced emission scenario. For the haziest 20% days, prescribed burning is an important source of visibility impairment, and approximately 50% of IMPROVE sites in the model domain show a significant improvement in visibility for the reduced fire case. Using BenMAP, a health impact assessment tool, we show that several hundred additional deaths, several thousand upper and lower respiratory symptom cases, several hundred bronchitis cases, and more than 35,000 workday losses can be attributed to prescribed fires, and these health impacts decrease by 25–30% when a 30% fire emission scenario is considered.

Implications: This study assesses the potential regional and local air quality, public health, and visibility impacts from prescribed burning activities, as well as benefits that can be achieved by a potential reduction in emissions for a scenario where biomass is harvested for conversion to biofuel. As prescribed burning activities become more frequent, they can be more detrimental for air quality and health. Forest residue-based biofuel industry can be source of cleaner fuel with co-benefits of improved air quality, reduction in health impacts, and improved visibility.     

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.     

Optical properties of the San Joaquin Valley aerosol collected during the 1995 integrated monitoring study

Optical, filter chemistry, and cascade impactor data collected during the winter intensive of the IMS95 Study in the San Joaquin Valley (SJV) of California were analyzed to determine the light-extinction efficiency of aerosol species. Regression of light scattering by particles (b_sp) measured by a heated nephelometer without a size selective inlet against PM_2.5 front filter mass gave a scattering efficiency of 3.67±0.05 m²/g with an R² (fraction of variance explained) of 0.94. Division of the aerosol into two components and applying two different corrections to the filter data for nitrate and organic carbon on the backup filter gave scattering efficiencies of 3.7±0.3 or 4.1±0.2 m²/g for the salts composed of sulfate, nitrate, and ammonium and 2.9±0.2 or 3.1±0.2 m²/g for all other species with R² of 0.985 and 0.986. The ambient b_sp measured by an open nephelometer was a simple function of PM_2.5 mass and relative humidity (RH), giving R² of 0.90 and 0.88 for two different RH sensors. Variations in PM_2.5 size distribution and composition did not have an important effect on ambient b_sp. The RH data from each sensor were repeatable enough to show the existence of a simple dependence of aerosol water uptake on RH, but RH sensor calibration uncertainties prevented determining this dependence. Inversion of MOUDI cascade impactor data gave sulfate and nitrate mass median diameters (MMD) between 0.4 and 0.8 μm. Mie scattering calculations based on MOUDI data provided humidity-dependent extinction efficiencies for the principal aerosol chemical species. These efficiencies combined with particle filter data showed that ammonium nitrate was the dominant contributor to wintertime light extinction. Source apportionment showed that light extinction was dominated by emissions sources contributing to the formation of secondary species, especially nitrate. These wintertime data are not expected to apply to summertime in the SJV.     

Precipitation in light extinction reconstruction

The U.S. Environmental Protection Agency (EPA) published the Regional Haze Rule (RHR) in 1999. The RHR default goal is to reduce haze linearly to natural background in 2064 from the baseline period of 2000-2004. The EPA default method for estimating natural and baseline visibility uses the Interagency Monitoring of Protected Visual Environments (IMPROVE) formula. The IMPROVE formula predicts the light extinction coefficient from aerosol chemical concentrations measured by the IMPROVE network. The IMPROVE light scattering coefficient formula using data from 1994-2002 underestimated the measured light scattering coefficient by 700 Mm(-1), on average, on days with precipitation. Also, precipitation occurred as often on the clearest as haziest days. This led to estimating the light extinction coefficient of precipitation, averaged over all days, as the light scattering coefficient on days with precipitation (700 Mm(-1)) multiplied by the percent of precipitation days in a year. This estimate added to the IMPROVE formula light extinction estimate gives a real world estimate of visibility for the 20% clearest, 20% haziest, and all days. For example, in 1993, the EPAs Report to Congress projected visibility in Class I areas would improve by 3 deciviews by 2010 across the haziest portions of the eastern United States because of the 1990 Clean Air Act Amendments. Omitted was the light extinction coefficient of precipitation. Adding in the estimated light extinction coefficient of precipitation, the estimated visibility improvement declines to <1 deciview.     

South Philadelphia passive sampler and sensor study

From June 2013 to March 2015, in total 41 passive sampler deployments of 2 wk duration each were conducted at 17 sites in South Philadelphia, PA, with results for benzene discussed here. Complementary time-resolved measurements with lower cost prototype fenceline sensors and an open-path ultraviolet differential optical absorption spectrometer were also conducted. Minimum passive sampler benzene concentrations for each sampling period ranged from 0.08 ppbv to 0.65 ppbv, with a mean of 0.25 ppbv, and were negatively correlated with ambient temperature (–0.01 ppbv/°C, R² = 0.68). Co-deployed duplicate passive sampler pairs (N = 609) demonstrated good precision with an average and maximum percent difference of 1.5% and 34%, respectively. A group of passive samplers located within 50 m of a refinery fenceline had a study mean benzene concentration of 1.22 ppbv, whereas a group of samplers located in communities >1 km distant from facilities had a mean of 0.29 ppbv. The difference in the means of these groups was statistically significant at the 95% confidence level (p < 0.001). A decreasing gradient in benzene concentrations moving away from the facilities was observed, as was a significant period-to-period variation. The highest recorded 2-wk average benzene concentration for the fenceline group was 3.11 ppbv. During this period, time-resolved data from the prototype sensors and the open-path spectrometer detected a benzene signal from the west on one day in particular, with the highest 5-min path-averaged benzene concentration measured at 24 ppbv.

Implications: Using a variation of EPA’s passive sampler refinery fenceline monitoring method, coupled with time-resolved measurements, a multiyear study in South Philadelphia informed benzene concentrations near facilities and in communities. The combination of measurement strategies can assist facilities in identification and mitigation of emissions from fugitive sources and improve information on air quality complex air sheds.     

The water cycles of water-soluble organic salts of atmospheric importance

In this study, the water cycles of nine water-soluble organic salts of atmospheric interest were studied using an electrodynamic balance (EDB) at 25°C. Sodium formate, sodium acetate, sodium succinate, sodium pyruvate and sodium methanesulfonate (Na-MSA) particles crystallize as the relative humidity (RH) decreases and they deliquesce as the RH increases. Sodium oxalate and ammonium oxalate form supersaturated particles at low RH before crystallization but they do not deliquesce even at RH=90%. Sodium malonate and sodium maleate particles neither crystallize nor deliquesce. These two salts absorb and evaporate water reversibly without hysteresis. In most cases, the solid states of single particles resulting from the crystallization of supersaturated droplets do not form the most thermodynamically stable state found in bulk studies. Sodium formate, sodium oxalate, ammonium oxalate, sodium succinate, sodium pyruvate and Na-MSA form anhydrous particles after crystallization. Sodium acetate forms particles with a water/salt molar ratio of 0.5 after crystallization. In salts with several hydrated states including sodium formate and sodium acetate, the particles deliquesce at the lowest deliquescence relative humidity (DRH) of the hydrates. Except sodium oxalate and ammonium oxalate, all the salts studied here are as hygroscopic as typical inorganic hygroscopic aerosols. The hygroscopic organic salts have a growth factor of 1.76–2.18 from RH=10–90%, comparable to that of typical hygroscopic inorganic salts such as NaCl and (NH₄)₂SO₄. Further study of other atmospheric water-soluble organic compounds and their mixtures with inorganic salts is needed to explain the field observations of the hygroscopic growth of ambient aerosols.     

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.     

杭州城市大气消光系数和能见度的影响因子研究

为了解杭州市能见度下降与大气污染之间的关系，在2001年5月至2002年5月对不同粒径的颗粒物（PM10、PM2.5）的质量浓度进行了观测，结合晴天天气条件下的大气能见度，推算污染物和水汽分子对大气的消光散射，发现细微颗粒物的散射消光特性对杭州市能见度下降起主要作用，并得到能见度与细微颗粒物浓度比值（PM2．5／PM10）的关系；分析了大气能见度和消光系数与PM2．5／PM10和相对湿度的相关系数。     

Estimates of particle hygroscopicity during the Southeastern Aerosol and Visibility Study

Aerosol water content was determined from relative humidity controlled optical particle counter (ASASP-X) size distribution measurements made during the Southeastern Aerosol and Visibility Study (SEAVS) in the Great Smoky Mountains National Park during summer 1995. Since the scattering response function of the ASASP-X is sensitive to particle refractive index, a technique for calibrating the ASASP-X for any real refractive index was developed. A new iterative process was employed to calculate water mass concentration and wet refractive index as functions of relative humidity. Experimental water mass concentrations were compared to theoretically predicted values assuming only ammonium sulfate compounds were hygroscopic. These comparisons agreed within experimental uncertainty. Estimates of particle hygroscopicity using a rural aerosol model of refractive index as a function of relative humidity demonstrated no significant differences from those made with daily varying refractive index estimates. Although aerosol size parameters were affected by the assumed chemical composition, forming ratios of these parameters nearly canceled these effects.     

Water-soluble aerosol and visibility degradation in Hong Kong during autumn and early winter, 1998.

During the October-December 1998 period, 30 daily samples of size-separated airborne respirable suspended particulates (RSP) were collected at the quasi-rural Kadoorie Agricultural Research Centre (KARC) in central New Territories (NT), Hong Kong, Special Administrative Region (SAR). Results of analysis indicate that sulphate is the predominant water-soluble species, and that sulphate, nitrate and ammonium together contribute to most of the total water-soluble fine aerosol mass. An interesting result obtained through principal component analysis (PCA) following varimax rotation of the bivariate correlation matrix for water-soluble species is that the first component (PCl) is made up exclusively of SO4 and NH4 ions. The stoichiometric ratio and correlation coefficient between the two ions suggest that ammoniated sulphate compounds are the probable species responsible for the PCI. Further, the use of a linear multivariate visibility model which accommodates the effect of relative humidity (RH) shows that SO4 and NH4 are the only anions important in visibility degradation. It is found that SO4 in aerosol at the KARC can be used to predict the visual range (or extinction coefficient) recorded from Kings Park, Kowloon, approximately 10 km away. This result suggests that SO4 (and possibly NH4) is, generally, likely to be of regional rather than of local origin. Further observations suggest that the model is most applicable to a moderate visual range, 10 km < R(v) < or = 20 km under a rather broad range of ambient relative humidity, 40% < RH < or = 80. However, this inference does not preclude the contributions to visibility degradation--mostly by absorption--by some of the water-insoluble aerosol constituents, including carbon, or the pollutant gas, NO2.