Laboratory and field evaluation of crystallized DOW 704 oil on the performance of the Well Impactor Ninety-Six fFine particulate matter fractionator

Subsequent to the 1997 promulgation of the Federal Reference Method (FRM) for monitoring fine particulate matter (PM2.5) in ambient air, U.S. Environmental Protection Agency (EPA) received reports that the DOW 704 diffusion oil used in the method's Well Impactor Ninety-Six (WINS) fractionator would occasionally crystallize during field use, particularly under wintertime conditions. Although the frequency of occurrence on a nationwide basis was low, uncertainties existed as to whether crystallization of the DOW 704 oil may adversely affect a sampling event's data quality. In response to these concerns, EPA and the State of Connecticut Department of Environmental Protection jointly conducted a series of specialized tests to determine whether crystallized oil adversely affected the performance of the WINS fractionator. In the laboratory, an experimental setup used dry ice to artificially induce crystallization of the diffusion oil under controlled conditions. Using primary polystyrene latex calibration aerosols, standard size-selective performance tests of the WINS fractionator showed that neither the position nor the shape of the WINS particle size fractionation curve was substantially influenced by the crystallization of the DOW 704 oil. No large particle bounce from the crystallized impaction surface was observed. During wintertime field tests, crystallization of the DOW 704 oil did not adversely affect measured PM2.5 concentrations. Regression of measurements with crystallized DOW 704 versus liquid dioctyl sebacate (DOS) oil produced slope, intercept, and R2 values of 0.98, 0.1, and 0.997 microg/m3, respectively. Additional field tests validated the use of DOS as an effective impaction substrate. As a result of these laboratory and field tests, DOS oil has been approved by EPA as a substitute for DOW 704 oil. Since the field deployment of DOS oil in 2001, users of this alternative oil have not reported any operational problems associated with its use in the PM2.5 FRM. Limited field evaluation of the BGI very sharp cut cyclone indicates that it provides a viable alternative to the WINS fractionator.     

Source apportionment of fine particulate matter in the southeastern United States

Particulate matter (PM) less than 2.5 microm in size (PM2.5) source apportionment by chemical mass balance receptor modeling was performed to enhance regional characterization of source impacts in the southeastern United States. Secondary particles, such as NH4HSO4, (NH4)2SO4, NH4NO3, and secondary organic carbon (OC) (SOC), formed by atmospheric photochemical reactions, contribute the majority (>50%) of ambient PM2.5 with strong seasonality. Source apportionment results indicate that motor vehicle and biomass burning are the two main primary sources in the southeast, showing relatively more motor vehicle source impacts rather than biomass burning source impacts in populated urban areas and vice versa in less urbanized areas. Spatial distributions of primary source impacts show that each primary source has distinctively different spatial source impacts. Results also find impacts from shipping activities along the coast. Spatiotemporal correlations indicate that secondary particles are more regionally distributed, as are biomass burning and dust, whereas impacts of other primary sources are more local.     

Size and composition distributions of particulate matter emissions: part 1--light-duty gasoline vehicles

Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965-2003; odometer readings 1264-207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM0.1 (0.056- to 0.1-microm aerodynamic diameter) and fine PM1.8 (< or =1.8-microm aerodynamic diameter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM0.1 and PM1.8 emissions of 51 microg/km and 371 microg/km, respectively. Light duty trucks and sport utility vehicles had PM0.1 and PM1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1- and 0.18-microm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 microm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.     

Short-term effects of gaseous pollutants on cause-specific mortality in Wuhan, China

In Asia, limited studies have been published on the association between daily mortality and gaseous pollutants of nitrogen dioxide (NO2), ozone (O3), and sulfur dioxide (SO2). Our previous studies in Wuhan, China, demonstrated long-term air pollution effects. However, no study has been conducted to determine mortality effects of air pollution in this region. This study was to determine the acute mortality effects of the gaseous pollutants in Wuhan, a city with 7.5 million permanent residents during the period from 2000 to 2004. There are approximately 4.5 million residents in Wuhan who live in the city's core area of 201 km2, where air pollution levels are highest, and pollution ranges are wider than the majority of the cities in the published literature. We used the generalized additive model to analyze pollution, mortality, and covariate data. We found consistent NO2 effects on mortality with the strongest effects on the same day. Every 10-microg/m3 increase in NO2 daily concentration on the same day was associated with an increase in nonaccidental (1.43%; 95% confidence interval [CI]: 0.87-1.99%), cardiovascular (1.65%; 95% CI: 0.87-2.45%), stroke (1.49%; 95% CI: 0.56-2.43%), cardiac (1.77%; 95% CI: 0.44-3.12%), respiratory (2.23%; 95% CI: 0.52-3.96%), and cardiopulmonary mortality (1.60%; 95% CI: 0.85-2.35%). These effects were stronger among the elderly than among the young. Formal examination of exposure-response curves suggests no-threshold linear relationships between daily mortality and NO2, where the NO2 concentrations ranged from 19.2 to 127.4 microg/m3. SO2 and O3 were not associated with daily mortality. The exposure-response relationships demonstrated heterogeneity, with some curves showing nonlinear relationships for SO2 and O3. We conclude that there is consistent evidence of acute effects of NO2 on mortality and suggest that a no-threshold linear relationship exists between NO2 and mortality.     

Source analysis of particulate-phase polycyclic aromatic hydrocarbons in an urban atmosphere of a northern city in China

Particle-associated polycyclic aromatic hydrocarbon (PAH) concentrations were investigated at six sampling sites in the heating (February to March 2001) and nonheating (August to September 2001) periods in an industrial city in Northern China. Thirteen PAHs were measured. The total average concentrations (nanograms per meter cubed) of PAHs ranged between 78.93 and 214.63 during the heating period and from 31.48 to 102.26 in the nonheating period. Benzo(a)pyrene occurred at the highest level at a site near an industrial area but occurred at low concentrations far from the city center and industrial areas. In addition, ambient PAH profiles were studied. The five and six-ring species occurred in high fractions at the sampling site. By diagnostic ratio analysis, the major source at each sampling site in the city was coal combustion in the heating period; in the nonheating period, the major sources were relatively complex. Finally, the similarities among the six regions were assessed by principal component analysis, cluster analysis, and coefficient of divergence. These multivariate statistical analyses produced similar results, which agreed with the results from the diagnostic ratio analysis.     

Extended geometric method: a simple approach to derive adsorption rate constants of Langmuir-Freundlich kinetics

A new and simple equation has been presented here for calculation of adsorption and desorption rate constants of Langmuir-Freundlich kinetic equation. The derivation of new equation is on the basis of extension and correction to the geometric method which has been presented by Kuan et al. [Kuan, W.-H., Lo, S.-L., Chang, C.M., Wang, M.K., 2000. A geometric approach to determine adsorption and desorption kinetic constants. Chemosphere 41, 1741-1747] for the kinetics of adsorption/desorption in aqueous solutions. The correction is to consider that the concentration of solute is not constant and changes as adsorption proceeds. The extension is that we applied Langmuir-Freundlich kinetic model instead of Langmuir kinetic model to consider the heterogeneity and therefore it is more applicable to the real systems. For solving Langmuir-Freundlich kinetic model, some geometric methods and also Taylor expansion were used and finally a simple and novel equation was derived (Eq. (20)) for calculation of adsorption rate constant. This new method was named "extended geometric method". The input data of the obtained equation can be simply derived from initial data of adsorption kinetics. Finally the adsorption of methyl orange onto granular activated carbon was carried out at dynamic and equilibrium conditions and the capabilities of extended geometric method were examined by the experimental data.     

Assessment of pesticide contamination in three Mississippi Delta oxbow lakes using Hyalella azteca

Three oxbow lakes in northwestern Mississippi, USA, an area of intensive agriculture, were assessed for biological impairment from historic and current-use pesticide contamination using the amphipod, Hyalella azteca. Surface water and sediment samples from three sites in each lake were collected from Deep Hollow, Beasley, and Thighman Lakes from September 2000 to February 2001. Samples were analyzed for 17 historic and current-use pesticides and selected metabolites. Ten-day H. azteca survival and growth (as length and dry weight) were measured to determine the degree of biological impairment. Maximum number of detectable pesticides in surface water from Deep Hollow, Beasley and Thighman Lakes was 10, 11, and 17, respectively. Maximum number of detectable pesticides in lake sediments was 17, 17, and 15, respectively. Bioassay results indicated no observable survival effects on H. azteca exposed to surface water or sediment from any lake examined and no growth impairment in animals exposed to lake sediments. However, growth was significantly impaired in surface water exposures from Deep Hollow Lake (2 sites) and Beasley Lake (1 site). Statistically significant relationships between growth impairment (length) and cyanazine, methyl parathion, λ-cyhalothrin, chlorfenapyr, and pp′DDE surface water concentrations in Deep Hollow Lake as well as trifluralin, atrazine, and methyl parathion in Beasley Lake were observed. Although pesticide frequency and concentrations were typically greater in sediment than surface water, bioassay results indicated decreased availability of these pesticides in sediment due to the presence of clay and organic carbon. Growth impairment observed in surface water exposures was likely due to complex interaction of pesticide mixtures that were present.     

Background levels and dietary intake of PCDD/Fs in domestic and imported meat in South Korea

A survey was conducted in South Korea to determine residual levels and dietary intake of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from meat. Altogether 119 domestic and 164 imported samples of beef, pork, and chicken were examined. The mean levels of PCDD/Fs in upper bound were 0.21, 0.22, and 0.04pg WHO-TEQ/g fat for beef, pork, and chicken, respectively. The low level of PCDD/Fs in chicken probably resulted from the low fat content in the samples used. The samples were separated into domestic and imported products in order to investigate the sources of contamination. PCDFs were the more dominant congeners in domestic beef and were similar to those found from emission of incineration. However, the congener profiles of domestic beef and incineration were difficult to compare because the environmental fate and animal metabolism were involved. The upper bound dietary intake of PCDD/Fs from beef, pork and chicken was calculated to be 0.04pg/WHO-TEQ/kgbw/day. The combined consumption of beef, pork, and chicken was found to be 84.8g per day for a person weighing 60kg and represented 5.7% of their total daily food intake.     

Enhanced phytoremediation of arsenic contaminated land

In an attempt to clean up arsenic (As) contaminated soil, the effects of phosphorus (P) fertilizer and rhizosphere microbes on arsenic accumulation by the silverback fern, Pityrogramma calomelanos, were investigated in both greenhouse and field experiments. Field experiments were conducted in Ron Phibun District, an As-contaminated area in Thailand. Soil (136-269 microg As g(-1)) was collected there and used in the greenhouse experiment. Rhizosphere microbes (bacteria and fungi) were isolated from roots of P. calomelanos growing in Ron Phibun District. The results showed that P-fertilizer significantly increased plant biomass and As accumulation of the experimental P. calomelanos. Rhizobacteria increased significantly the biomass and As content of the test plants. Thus, P-fertilizer and rhizosphere bacteria enhanced As-phytoextraction. In contrast, rhizofungi reduced significantly As concentration in plants but increased plant biomass. Therefore, rhizosphere fungi exerted their effects on phytostabilization.