Estimation of aerosol mass scattering efficiencies under high mass loading: case study for the megacity of Shanghai, China.

Aerosol mass scattering efficiency (MSE), used for the scattering coefficient apportionment of aerosol species, is often studied under the condition of low aerosol mass loading in developed countries. Severe pollution episodes with high particle concentration frequently happened in eastern urban China in recent years. Based on synchronous measurement of aerosol physical, chemical, and optical properties at the megacity of Shanghai for two months during autumn 2012, we studied MSE characteristics at high aerosol mass loading. Their relationships with mass concentrations and size distributions were examined. It was found that MSE values from the original US IMPROVE algorithm could not represent the actual aerosol characteristics in eastern China. It results in an underestimation of the measured ambient scattering coefficient by 36%. MSE values in Shanghai were estimated to be 3.5 ± 0.55 m(2)/g for ammonia sulfate, 4.3 ± 0.63 m(2)/g for ammonia nitrate, and 4.5 ± 0.73 m(2)/g for organic matter, respectively. MSEs for three components increased rapidly with increasing mass concentration in low aerosol mass loading, then kept at a stable level after a threshold mass concentration of 12­24 µg/m(3). During severe pollution episodes, particle growth from an initial peak diameter of 200­300 nm to a peak diameter of 500­600 nm accounts for the rapid increase in MSEs at high aerosol mass loading, that is, particle diameter becomes closer to the wavelength of visible lights. This study provides insights of aerosol scattering properties at high aerosol concentrations and implies the necessity of MSE localization for extinction apportionment, especially for the polluted regions.

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

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

Characterization of the winter midwestern particulate nitrate bulge.

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

Critique of "Precipitation in light extinction reconstruction" by P.A. Ryan.

The goal of the Regional Haze Rule (RHR) is to return visibility in class I areas (CIAs) to natural levels, excluding weather-related events, by 2064. Whereas visibility, the seeing of scenic vistas, is a near instantaneous and sight-path-dependent phenomenon, reasonable progress toward the RHR goal is assessed by tracking the incremental changes in 5-yr average visibility. Visibility is assessed using a haze metric estimated from 24-hr average aerosol measurements that are made at one location representative of the CIA. It is assumed that, over the 5-yr average, the aerosol loadings and relative humidity along all of the site paths are the same and can be estimated from the 24-hr measurements. It is further assumed that any time a site path may be obscured by weather (e.g., clouds and precipitation), there are other site paths within the CIA that are not. Therefore, when calculating the haze metric, sampling days are not filtered for weather conditions. This assumption was tested by examining precipitation data from multiple monitors for four CIAs. It is shown that, in general, precipitation did not concurrently occur at all monitors for a CIA, and precipitation typically occurred 3-8 hr or less in a day. In a recent paper in this journal, Ryan asserts that the haze metric should include contributions from precipitation and conducted a quantitative assessment incorrectly based on the assumption that the Optec NGN-2 nephelometer measurements include the effects of precipitation. However, these instruments are programmed to shut down during rain events, and any data logged are in error. He further assumes that precipitation occurs as often on the haziest days as the clearest days and that precipitation light scattering (bprecip) is independent of geographic location and applied an average bprecip derived for Great Smoky Mountains to diverse locations including the Grand Canyon. Both of these assumptions are shown to be in error.

Reconciliation and interpretation of Big Bend National Park particulate sulfur source apportionment: results from the Big Bend Regional Aerosol and Visibility Observational Study--part I.

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) study was an intensive monitoring study from July through October 1999 followed by extensive assessments to determine the causes and sources of haze in Big Bend National Park, located in Southwestern Texas. Particulate sulfate compounds are the largest contributor of haze at Big Bend, and chemical transport models (CTMs) and receptor models were used to apportion the sulfate concentrations at Big Bend to North American source regions and the Carbón power plants, located 225 km southeast of Big Bend in Mexico. Initial source attribution methods had contributions that varied by a factor of > or =2. The evaluation and comparison of methods identified opposing biases between the CTMs and receptor models, indicating that the ensemble of results bounds the true source attribution results. The reconciliation of these differences led to the development of a hybrid receptor model merging the CTM results and air quality data, which allowed a nearly daily source apportionment of the sulfate at Big Bend during the BRAVO study. The best estimates from the reconciliation process resulted in sulfur dioxide (SO2) emissions from U.S. and Mexican sources contributing approximately 55% and 38%, respectively, of sulfate at Big Bend. The distribution among U.S. source regions was Texas, 16%; the Eastern United States, 30%; and the Western United States, 9%. The Carbón facilities contributed 19%, making them the largest single contributing facility. Sources in Mexico contributed to the sulfate at Big Bend on most days, whereas contributions from Texas and Eastern U.S. sources were episodic, with their largest contributions during Big Bend sulfate episodes. On the 20% of the days with the highest sulfate concentrations, U.S. and Mexican sources contributed approximately 71% and 26% of the sulfate, respectively. However, on the 20% of days with the lowest sulfate concentrations, Mexico contributed 48% compared with 40% for the United States.

Reconciliation and interpretation of the Big Bend National Park light extinction source apportionment: results from the Big Bend Regional Aerosol and Visibility Observational Study--part II.

The recently completed Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study focused on particulate sulfate source attribution for a 4-month period from July through October 1999. A companion paper in this issue by Schichtel et al. describes the methods evaluation and results reconciliation of the BRAVO Study sulfate attribution approaches. This paper summarizes the BRAVO Study extinction budget assessment and interprets the attribution results in the context of annual and multiyear causes of haze by drawing on long-term aerosol monitoring data and regional transport climatology, as well as results from other investigations. Particulate sulfates, organic carbon, and coarse mass are responsible for most of the haze at Big Bend National Park, whereas fine particles composed of light-absorbing carbon, fine soils, and nitrates are relatively minor contributors. Spring and late summer through fall are the two periods of high-haze levels at Big Bend. Particulate sulfate and carbonaceous compounds contribute in a similar magnitude to the spring haze period, whereas sulfates are the primary cause of haze during the late summer and fall period. Atmospheric transport patterns to Big Bend vary throughout the year, resulting in a seasonal cycle of different upwind source regions contributing to its haze levels. Important sources and source regions for haze at Big Bend include biomass smoke from Mexico and Central America in the spring and African dust during the summer. Sources of sulfur dioxide (SO2) emissions in Mexico, Texas, and in the Eastern United States all contribute to Big Bend haze in varying amounts over different times of the year, with a higher contribution from Mexican sources in the spring and early summer, and a higher contribution from U.S. sources during late summer and fall. Some multiple-day haze episodes result from the influence of several source regions, whereas others are primarily because of emissions from a single source region.