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.     

Open-path,closed-path,and reconstructed aerosol extinction at a rural site

The Handix Scientific open-path cavity ringdown spectrometer (OPCRDS) was deployed during summer 2016 in Great Smoky Mountains National Park (GRSM). Extinction coefficients from the relatively new OPCRDS and from a more well-established extinction instrument agreed to within 7%. Aerosol hygroscopic growth (f(RH)) was calculated from the ratio of ambient extinction measured by the OPCRDS to dry extinction measured by a closed-path extinction monitor (Aerodyne’s cavity-attenuated phase shift particulate matter extinction monitor [CAPS PMex]). Derived hygroscopicity (relative humidity [RH] < 95%) from this campaign agreed with data from 1995 at the same site and time of year, which is noteworthy given the decreasing trend for organics and sulfate in the eastern United States. However, maximum f(RH) values in 1995 were less than half as large as those recorded in 2016—possibly due to nephelometer truncation losses in 1995. Two hygroscopicity parameterizations were investigated using high-time-resolution OPCRDS+CAPS PMex data, and the κ_ext model was more accurate than the gamma model. Data from the two ambient optical instruments, the OPCRDS and the open-path nephelometer, generally agreed; however, significant discrepancies between ambient scattering and extinction were observed, apparently driven by a combination of hygroscopic growth effects, which tend to increase nephelometer truncation losses and decrease sensitivity to the wavelength difference between the two instruments as a function of particle size. There was not a statistically significant difference in the mean reconstructed extinction values obtained from the original and the revised IMPROVE (Interagency Monitoring of Protected Visual Environments) equations. On average, IMPROVE reconstructed extinction was ~25% lower than extinction measured by the OPCRDS, which suggests that the IMPROVE equations and 24-hr aerosol data are moderately successful in estimating current haze levels at GRSM. However, this conclusion is limited by the coarse temporal resolution and the low dynamic range of the IMPROVE reconstructed extinction.

Implications: Although light extinction, which is directly related to visibility, is not directly measured in U.S. National Parks, existing IMPROVE protocols can be used to accurately infer visibility for average humidity conditions, but during the large fraction of the year when humidity is above or below average, accuracy is reduced substantially. Furthermore, nephelometers, which are used to assess the accuracy of IMPROVE visibility estimates, may themselves be biased low when humidity is very high. Despite reductions in organic and sulfate particles since the 1990s, hygroscopicity, particles’ affinity for water, appears unchanged, although this conclusion is weakened by the previously mentioned nephelometer limitations.     

Source apportionment of visibility degradation problems in Brisbane (Australia) using the multiple linear regression techniques

Different aspects of visibility degradation problems in Brisbane were investigated through concurrent visibility monitoring and aerosol sampling programs carried out in 1995. The relationship between the light extinction coefficients and aerosol mass/composition was derived by using multiple linear regression techniques. The visibility properties at different sites in Brisbane were found to be correlated with each other on a daily basis, but not correlated with each other hour by hour. The cause of scattering of light by moisture (b_sw) was due to sulphate particles which shift to a larger size under high-humidity conditions. The scattering of light by particulate matter (b_sp) was found to be highly correlated with the mass of fine aerosols, in particular the mass of fine soot, sulphate and non-soil K. For the period studied, on average, the total light extinction coefficient (b_ext) at five sites in Brisbane was 0.65×10⁻⁴ m⁻¹, considerably smaller than those values found in other Australian and overseas cities. On average, the major component of b_ext is b_sp (49% of b_ext), followed by b_ap (the absorption of light, mainly by fine soot particles, 28%), b_sg (Rayleigh scattering, 20%) and b_sw (3%). The absorption of light by NO₂ (b_ag) is expected to contribute less than 5% of b_ext. On average, the percentage contribution of the visibility degrading species to b_ext (excluding b_ag) were: soot (53%), sulphate (21%), Rayleigh scattering (20%), non-soil K (2%) and humidity (3%). In terms of visibility degrading sources, motor vehicles (including soot and the secondary products) are expected to contribute more than half of the b_ext (excluding b_ag) in Brisbane on average, followed by secondary sulphates (17%) and biomass burning (10%).     

Visibility degradation across Hong Kong: its components and their relative contributions

Daily average levels of nitrogen dioxide (NO₂) and the time-matched, relative humidity-corrected airborne respirable suspended particulate (RSP^*) data from four air quality monitoring stations of the Environmental Protection Department (EPD) Network were subjected to analysis employing a linear multivariate model for visibility in Hong Kong. The respective NO₂ and RSP^* contributions to the extinction coefficient for Hong Kong Observatory, σ_ext(HKO) are estimated to be between 6–31% (mean: 17%) and 58–68% (mean: 62.5%), with a remainder of 11–30% (mean: 21%). The latter includes a small contribution due to Rayleigh scatter. The observed σ_ext agrees reasonably well with model prediction. During the July–October 1999 period, the particle scattering coefficient, σ_sp was determined at City University (CityU) in Kowloon with the aid of an integrated nepthelometer employing 3, 1-h sampling periods. This daily average value of σ_sp(CityU) is well correlated with the corresponding σ_ext(HKO). It is provisionally estimated that the fractional contribution by particulate absorption to σ_ext(HKO) is likely to be less than that by particulate scattering. A reasonable apportionment for σ_ext(HKO) is ∼39% particulate scattering, 19–29% particulate absorption, 17% gaseous absorption, and an estimated mean Rayleigh scatter of ∼4.3%. The unaccounted 16% is due to a negative bias assigned to deficiencies in sampling and in the various assumptions made. Results of continuous, 8-h daytime nephelometric measurements of σ_sp at the CityU, and the water-soluble ambient RSP constituents sampled in tandem at the same site during the February–April 2000 period suggest that SO₄^*, NH₄^* and K are apparently associated with light scattering at CityU. However, only the SO₄^* at this sampling site is related to time-matched σ_ext(HKO). Based on these and other results from a previous study, it is concluded that (i) σ_ext(HKO) is proportional to σ_sp, measured elsewhere in Hong Kong at distances between several to ∼10 km from the HKO headquarters and (ii) most of the fine SO₄ aerosol in Hong Kong is apparently advected into the territory.     

Visibility impairment during Yellow Sand periods in the urban atmosphere of Kwangju,Korea

For continuous monitoring of atmospheric visibility in the city of Kwangju, Korea, a transmissometer system consisting of a transmitter and a receiver was installed at a distance of 1.91 km across the downtown Kwangju, Korea. At the transmitter site a nephelometer and an aethalometer were also installed to measure the scattering and absorption coefficients of the atmosphere, respectively. Unusually high number of Yellow Sand events had occurred in the Northeast Asia during the spring of 2000. Visibility in Kwangju under such conditions was greatly impaired over large area for a few days. In order to investigate the effects of Yellow Sand on visibility impairment, chemical and elemental analyses of aerosol samples were performed along with the optical measurement of visibility. Hourly averaged visual range decreased from 61.7 to 1.9 km when hourly averaged concentration of PM10 varied from 32.9 to 601.8 μg/m³ during Yellow Sand periods. Fine particulate (<2.5 μm) concentrations were relatively lower than coarse particulate matters. Results of the data analyses show that mineral dusts originated from continental sources were simultaneously transported along with anthropogenic sulfate aerosols and marine aerosols. Total light extinction coefficient, b_ext, proposed by the IMPROVE network showed poor correlation with b_ext measured by transmissometer. Coarse mass scattering efficiency was classified into three categories; E_NHSOc, E_mineral, and E_sea-salt, which were determined as ammonium sulfate combined with nss-sulfate of 1.0, sea-salt of 0.4, and mineral of 0.77 m²/g, respectively. Mass fraction of NHSOc, sea-salt, and mineral dust was 0.20, 0.14, and 0.66, respectively.     

Multi-year hourly PM2.5 carbon measurements in New York: Diurnal,day of week and seasonal patterns

Multi-year hourly measurements of PM_2.5 elemental carbon (EC) and organic carbon (OC) from a site in the South Bronx, New York were used to examine diurnal, day of week and seasonal patterns. The hourly carbon measurements also provided temporally resolved information on sporadic EC spikes observed predominantly in winter. Furthermore, hourly EC and OC data were used to provide information on secondary organic aerosol formation. Average monthly EC concentrations ranged from 0.5 to 1.4 μg m^?3 with peak hourly values of several μg m^?3 typically observed from November to March. Mean EC concentrations were lower on weekends (approximately 27% lower on Saturday and 38% lower on Sunday) than on weekdays (Monday to Friday). The weekday/weekend difference was more pronounced during summer months and less noticeable during winter. Throughout the year EC exhibited a similar diurnal pattern to NO_x showing a pronounced peak during the morning commute period (7–10 AM EST). These patterns suggest that EC was impacted by local mobile emissions and in addition by emissions from space heating sources during winter months. Although EC was highly correlated with black carbon (BC) there was a pronounced seasonal BC/EC gradient with summer BC concentrations approximately a factor of 2 higher than EC. Average monthly OC concentrations ranged from 1.0 to 4.1 μg m^?3 with maximum hourly concentrations of 7–11 μg m^?3 predominantly in summer or winter months. OC concentrations generally correlated with PM_2.5 total mass and aerosol sulfate and with NO_x during winter months. OC showed no particular day of week pattern. The OC diurnal pattern was typically different than EC except in winter when OC tracked EC and NO_x indicating local primary emissions contributed significantly to OC during winter at the urban location. On average secondary organic aerosol was estimated to account for 40–50% of OC during winter and up to 63–73% during summer months.     

Relationship of extinction coefficient, air pollution, and meteorological parameters in an urban area during 2007 to 2009

Light extinction, which is the extent of attenuation of light signal for every distance traveled by light in the absence of special weather conditions (e.g., fog and rain), can be expressed as the sum of scattering and absorption effects of aerosols. In this paper, diurnal and seasonal variations of the extinction coefficient are investigated for the urban areas of Tehran from 2007 to 2009. Cases of visibility impairment that were concurrent with reports of fog, mist, precipitation, or relative humidity above 90 % are filtered. The mean value and standard deviation of daily extinction are 0.49 and 0.39 km^?1, respectively. The average is much higher than that in many other large cities in the world, indicating the rather poor air quality over Tehran. The extinction coefficient shows obvious diurnal variations in each season, with a peak in the morning that is more pronounced in the wintertime. Also, there is a very slight increasing trend in the annual variations of atmospheric extinction coefficient, which suggests that air quality has regressed since 2007. The horizontal extinction coefficient decreased from January to July in each year and then increased between July and December, with the maximum value in the winter. Diurnal variation of extinction is often associated with small values for low relative humidity (RH), but increases significantly at higher RH. Annual correlation analysis shows that there is a positive correlation between the extinction coefficient and RH, CO, PM₁₀, SO₂, and NO₂ concentration, while negative correlation exists between the extinction and T, WS, and O₃, implying their unfavorable impact on extinction variation. The extinction budget was derived from multiple regression equations using the regression coefficients. On average, 44 % of the extinction is from suspended particles, 3 % is from air molecules, about 5 % is from NO₂ absorption, 0.35 % is from RH, and approximately 48 % is unaccounted for, which may represent errors in the data as well as contribution of other atmospheric constituents omitted from the analysis. Stronger regression equation is achieved in the summer, meaning that the extinction is more predictable in this season using pollutant concentrations.     

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.     

Regional Variations in Sulfate and Nitrate on Annual,Seasonal, and Synoptic Time Scales

ABSTRACT

Ambient data from Interagency Monitoring of Protected Visual Environments (IMPROVE) monitors are analyzed to evaluate the spatial structure of SO₄ and NO₃ aerosols in the mid-Atlantic region. Sub-weekly, seasonal, and annual data values are compared between the IMPROVE Washington, DC, site and three rural sites. Synoptic perturbations are compared between sites to quantify similarities in short-term temporal perturbations of SO₄ and NO₃. Based on these comparisons between the rural and urban IMPROVE monitors, the spatial structure of SO₄ shows broad regional homogeneity that is recognizable from both the long-term average values and the short-term variations.

NO₃ data on a seasonal and annual basis show much larger spatial gradients between the urban Washington monitor and the three rural monitors than do SO₄ data. Short-term NO₃ perturbations at the three rural monitors also differ significantly from those at the Washington site. These dissimilarities in NO₃ levels between the rural and urban IMPROVE monitors on both short-term and longer-term time scales indicate little homogeneity of NO₃ aerosols in the mid-Atlantic region considered here. The volatility of NO₃ aerosols and the removal rate of HNO₃ via dry deposition could contribute to the spatial variability differences shown here between SO₄ and NO₃.     

Continuous gaseous and total ammonia measurements from the southeastern aerosol research and characterization (SEARCH) study

Continuous ammonia (NH₃) measurements with a temporal resolution of 5 min were implemented at selected SEARCH sites in the southeastern U. S. during 2007. The SEARCH continuous NH₃ instrument uses a citric acid denuder difference technique employing a dual-channel nitric oxide-ozone chemiluminescence analyzer. Data from two SEARCH sites are presented, Jefferson Street, Atlanta (JST) (urban), and Yorkville, Georgia (YRK) (rural), for the period July–December, 2007. Highest NH_x (total ammonia = gaseous NH₃ + PM_2.5 NH₄⁺) values were observed in August and September at both JST and YRK. Highest NH₃ values occurred in August and September at JST, but in August through October at YRK. Lowest NH₃ and NH_x values occurred in December at both sites. YRK is significantly impacted by nearby poultry sources, routinely experiencing hourly average NH₃ mixing ratios above 20 ppbv. Wind sector analysis clearly implicates the nearby poultry operations as the source of the high NH₃ values. Weekday versus weekend differences in composite hourly mean diurnal profiles of NH₃ at JST indicate that mobile sources have a measurable but relatively small impact on NH₃ observed at that site, and little or no impact on NH₃ observed at YRK. A distinctive composite mean hourly diurnal variation was observed at both JST and YRK, exhibiting maxima in the morning and evening with a broad minimum during midday. Analysis of observed NH₃ diurnal variations from the literature suggests a hypothesized mechanism for the observed behavior based on interaction of local emissions and dry deposition with the formation and collapse of the dynamically mixed atmospheric boundary layer during the day and shallow nocturnal layer at night. Simple mixed layer concentration box model simulations confirm the plausibility of the suggested mechanism.     

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.     

PM10 Levels in the Lower Fraser Valley,British Columbia,Canada: An Overview of Spatiotemporal Variations and Meteorological Controls

ABSTRACT

Three years of hourly averaged PM₁₀ (particulate matter less than 10 Lrm in diameter) tapered element oscillating microbalance (TEOM) data from 10 sites in the large coastal valley incorporating Greater Vancouver were used to investigate the spatiotemporal dimensions and air pollution meteorology of particulate pollution. During the period studied, the provincial “acceptable” objective daily concentration of 50 μg m^-3 was exceeded at 7 of the 10 sites. The highest annual, seasonal, and maximum hourly concentrations were recorded at Abbotsford in the central valley. Mean seasonal PM₁₀ concentrations were highest in the wintertime in the western Lower Fraser Valley (LFV) and in the summertime at the central and eastern valley locations. Within the network, interstation correlations of daily average concentrations exceed 0.8 at interstation distances less than 20 km and decrease thereafter. For daily maximum concentrations (hourly), interstation correlations decrease sharply with distance. Meteorological conditions responsible for elevated par-ticulate concentrations in the LFV are associated with (1) short periods (1- to 3-hr duration) of reduced dispersion during summer nights at sites close to primary sources, (2) summer anticyclonic conditions when photochemical pollutant concentrations build up across the entire valley, and (3) occasional wintertime “gap wind” events in the eastern valley.     

Comparison of Selenium and Sulfur at Remote Sites

Abstract

The Interagency Monitoring of Protected Visual Environments (IMPROVE) particulate monitoring network has been collecting aerosols for visibility apportionment at remote sites in the United States since 1988. The measurements include the major PM_2.5 components, such as sulfur, carbon, and nitrate, and trace elements, such as selenium. This paper will examine the relationship between the sulfurs and selenium concentrations at 61 sites for samples collected in the seasonal year 1993. Maps of mean sulfur and selenium measurements in summer 1993 and winter 1993-1994 indicate that there are well-defined regional patterns for both elements, with concentrations in the Appalachian region that are ten times those in areas of the Pacific Northwest. The S/Se ratios of means are relatively uniform across the United States, at around 2000 in summer and 1000 in winter, indicating a strong sulfur-selenium relationship. The role of conversion of S0₂ to sulfate can also be deduced from the means. For individual samples taken during summer 1993, there is a high correlation between the two variables in the East, especially at sites in the Northeast, where the correlation coefficients (r²) are around 0.9. In the West, the correlation is much lower. This is attributed to fewer sources and differing emission factors.     

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.     

Seasonal and diurnal variations of ambient PM2.5 concentration in urban and rural environments in Beijing

Three years of measurement of PM_2.5 with 5-min time resolution was conducted from 2005 to 2007 in urban and rural environments in Beijing to study the seasonal and diurnal variations in PM_2.5 concentration. Pronounced seasonal variation was observed in the urban area, with the highest concentrations typically observed in the winter and the lowest concentrations generally found in the summer. In the rural area, the maximum in PM_2.5 concentration usually appeared during the spring, followed by a second maximum in the summer, while the minimum generally occurred in the winter. Significant diurnal variations in PM_2.5 concentration were observed in both urban and rural areas. In the urban area, the PM_2.5 concentration displays a bimodal pattern, with peaks between 7:00 and 8:00 a.m. and between 7:00 and 11:00 p.m. The minimum generally appears around noon. The morning peak is attributed to enhanced anthropogenic activity during rush hours. The decreases of boundary layer height and wind speed in the afternoon companying with increased source activity during the afternoon rush hour result in the highest PM_2.5 concentration during evening hours. In the rural area, the PM_2.5 concentration shows a unimodal pattern with a significant peak between 5:00 and 11:00 p.m.The seasonal and diurnal variations in PM_2.5 concentration in the urban area are mostly dominated by the seasonal and diurnal variability of boundary layer and source emissions. The year-to-year variability of rainfall also has an important influence on the seasonal variation of PM_2.5 in the urban area. The seasonal and diurnal wind patterns are more important factors for PM_2.5 variation in the rural area. Southerly winds carry pollutants emitted in southern urban areas northward and significantly enhance the PM_2.5 concentration level in the rural area.     

Evaluation of OC/EC Speciation by Thermal Manganese Dioxide Oxidation and the IMPROVE Method

Abstract

Ambient particulate samples are routinely analyzed for organic and elemental carbon (OC/EC) using either thermal manganese dioxide oxidation (TMO) or thermal volatil-ization-pyrolysis correction methods, such as the Inter-agency Monitoring of PROtected Visual Environments (IMPROVE) method with correction by reflectance, or a variation of the National Institute of Occupational Safety and Health (NIOSH) Method 5040 using thermal optical transmittance (TOT). With TMO, EC is modeled after the oxidation properties of submicron graphite and needle coke by MnO₂, and is the fraction of total carbon (TC) that is not oxidized at >525 °C. In thermal volatilization methods, EC is the fraction of TC that accounts for the light extinction properties of the sample at the start of analysis. Chow et al. (2001) compared IMPROVE and NIOSH methods implemented on the same instrument using 60 samples of various types and found that NIOSH EC was lower than IMPROVE. This study compares total, organic, and elemental carbon measurements from the TMO and IMPROVE thermal optical reflectance (TOR) methods using a sample set consisting of 60 IMPROVE nonurban, 16 Korean urban, 10 Hong Kong urban, and 14 synthetic carbon black samples.     

Measurements of aerosol optical properties in central Tokyo during summertime using cavity ring-down spectroscopy: Comparison with conventional techniques

A highly sensitive cavity ring-down spectrometer (CRDS) was used to monitor the aerosol extinction coefficient at 532 nm. The performance of the spectrometer was evaluated using measurements of nearly monodisperse polystyrene particles with diameters between 150 and 500 nm. By comparing the observed results with those determined using Mie theory, the accuracy of the CRDS instrument was determined to be >97%, while the upper limit for the precision of the instrument was estimated to be 0.6–3.5% (typically 2%), depending on the particle number concentration, which was in the range of 30–2300 particles cm^?3. Simultaneous measurements of the extinction (b_ext), scattering (b_sca) and absorption (b_abs) coefficients of ambient aerosols were performed in central Tokyo from 14 August to 2 September 2007 using the CRDS instrument, two nephelometers and a particle/soot absorption photometer (PSAP), respectively. The value of b_ext measured using the CRDS instrument was compared with the sum of the b_sca and b_abs values measured with a nephelometer and a PSAP, respectively. Good agreement between the b_ext and b_sca + b_abs values was obtained except for data on days when high ozone mixing ratios (>130 ppbv) were observed. During the high-O₃ days, the values for b_sca + b_abs were ～7% larger than the value for b_ext, possibly because the value for b_abs measured by the PSAP was overestimated due to interference from coexisting non-absorbing aerosols such as secondary organic aerosols.     

Temporal Variations of PM2.5, PM10, and Gaseous Precursors during the 1995 Integrated Monitoring Study in Central California

ABSTRACT

The spatial and temporal distributions of particle mass and its chemical constituents are essential for understanding the source-receptor relationships as well as the chemical, physical, and meteorological processes that result in elevated particulate concentrations in California’s San Joaquin Valley (SJV). Fine particulate matter ₍PM_2.5), coarse particulate matter (PM₁₀), and aerosol precursor gases were sampled on a 3-hr time base at two urban (Bakersfield and Fresno) and two non-urban (Kern Wildlife Refuge and Chowchilla) core sites in the SJV during the winter of 1995–1996.

Day-to-day variations of PM_2.5 and PM₁₀ and their chemical constituents were influenced by the synoptic-scale meteorology and were coherent among the four core sites. Under non-rainy conditions, similar diurnal variations of PM_2.5 and coarse aerosol were found at the two urban sites, with concentrations peaking during the nighttime hours. Conversely, PM_2.5 and coarse aerosol peaked during the morning and afternoon hours at the two non-urban sites. Under rainy and foggy conditions, these diurnal patterns were absent or greatly suppressed.

In the urban areas, elevated concentrations of primary pollutants (e.g., organic and elemental carbons) during the late afternoon and nighttime hours reflected the impact from residential wood combustion and motor vehicle exhaust. During the daytime, these concentrations decreased as the mixed layer deepened. Increases of secondary nitrate and sulfate concentrations were found during the daylight hours as a result of photochemical reactions. At the non-urban sites, the same increases in secondary aerosol concentrations occurred during the daylight hours but with a discernable lag time. Concentrations of the primary pollutants also increased at the non-urban sites during the daytime. These observations are attributed to mixing aloft of primary aerosols and secondary precursor gases in urban areas followed by rapid transport aloft to non-urban areas coupled with photochemical conversion.     

C2–C10 nonmethane hydrocarbons measured in Dallas,USA—Seasonal trends and diurnal characteristics

Nonmethane hydrocarbons (NMHCs) are important precursors of ozone and other photo oxidants. We presented continuous hourly average concentrations of 45 C₂–C₁₀ NMHCs measured in urban area of Dallas, USA from 1996 to 2004. Most of the selected compounds are good variables with less noise. The top 10 species with high ozone-generating potential were identified according to their concentrations and reactivities. The ambient concentrations of abundant anthropogenic emission hydrocarbons measured in Dallas were about 2–4 times of the background values measured in the remote areas with adjacent latitude. The time series for anthropogenic emission hydrocarbons showed an obvious seasonal cycle with relatively high concentration in winter and low concentration in summer. The sinusoidal function with a linearly decreasing factor could well fit the time series of NMHCs. The phase of seasonal cycle for the aromatic hydrocarbons of toluene, m/p xylene and o-xylene that might come from both vehicle emission and solvent utilities evaporation was about 1 month earlier than that for alkanes and alkenes that mainly came from vehicle emission. Ambient NMHCs in Dallas decreased with a stable rate during 1996–2004. For most of compounds with high ozone-generating potential, the rate of ambient concentration decrease was higher or much higher than the rate of volatile organic compounds (VOCs) source emission reduction estimated by EPA's National Emission Inventory. On weekdays, the morning hydrocarbon concentration peak was coincident with morning traffic rush time in Dallas. Another concentration peak was delayed to afternoon traffic rush time. The characteristics of VOCs sources, photochemical removal processes and atmospheric dilution could be interpreted by the diurnal variations of benzene/ethylbenzene (B/E), toluene/ethylbenzene (T/E) and xylene/ethylbenzene (X/E). The ratio of VOC/NO_x measured in Dallas was substantially smaller than that calculated for USA cities. Ozone formation in Dallas was VOC sensitive.     

Ten years of atmospheric methane observations at a high elevation site in Western China

In this paper, the continuous (1994–2001) and discrete air sample (1991–2001) measurements of atmospheric CH₄ from the Waliguan Baseline Observatory located in western China (36°17′N, 100°54′E, 3816 m asl) are presented and characterized. The CH₄ time series show large episodic events on the order of 100 ppb throughout the year. During spring, a diurnal cycle with average amplitude of 7 ppb and a morning maximum and late afternoon minimum is observed. In winter, a diurnal cycle with average amplitude of 14 ppb is observed with an afternoon maximum and morning minimum. Unlike most terrestrial observational sites, no obvious diurnal patterns are present during the summer or autumn. A background data selection procedure was developed based on local horizontal and vertical winds. A selected hourly data set representative of “baseline” conditions was derived with approximately 50% of the valid hourly data. The range of CH₄ mixing ratios, annual means, annual increases and mean annual cycle at Waliguan during the 1992–2001 were derived from discrete and continuous data representative of “baseline” conditions and compared to air samples collected at other Northern Hemisphere sites. The range of CH₄ monthly means of 1746–1822 ppb, average annual means of 1786.7±10.8 ppb and mean annual increase of 4.5±4.2 ppb yr⁻¹ at Waliguan were inline with measurements from sites located between 30° and 60°N. There were variations observed in the CH₄ annual increase patterns at Waliguan that were slightly different from the global pattern. The mean CH₄ annual cycle at Waliguan shows an unusual pattern of two gentle peaks in summer and February along with two small valleys in early winter and spring and a mean peak-to-peak amplitude of 11 ppb, much smaller than amplitudes observed at most other mid- and high-northern latitude sites. The Waliguan CH₄ data are strongly influenced by continental Asian CH₄ emissions and provide key information for global atmospheric CH₄ models.