Source apportionment of fine (PM1.8) and ultrafine (PM0.1) airborne particulate matter during a severe winter pollution episode.

Size-resolved samples of airborne particulate matter (PM) collected during a severe winter pollution episode at three sites in the San Joaquin Valley of California were extracted with organic solvents and analyzed for detailed organic compounds using GC-MS. Six particle size fractions were characterized with diameter (Dp) < 1.8 microm; the smallest size fraction was 0.056 < Dp < 0.1 microm which accounts for the majority of the mass in the ultrafine (PM0.1) size range. Source profiles for ultrafine particles developed during previous studies were applied to the measurements at each sampling site to calculate source contributions to organic carbon (OC) and elemental carbon (EC) concentrations. Ultrafine EC concentrations ranged from 0.03 microg m(-3) during the daytime to 0.18 microg m(-3) during the nighttime. Gasoline fuel, diesel fuel, and lubricating oil combustion products accounted for the majority of the ultrafine EC concentrations, with relatively minor contributions from biomass combustion and meat cooking. Ultrafine OC concentrations ranged from 0.2 microg m(-3) during the daytime to 0.8 microg m(-3) during the nighttime. Wood combustion was found to be the largest source of ultrafine OC. Meat cooking was also identified as a significant potential source of PM0.1 mass but further study is required to verify the contributions from this source. Gasoline fuel, diesel fuel, and lubricating oil combustion products made minor contributions to PM0.1 OC mass. Total ultrafine particulate matter concentrations were dominated by contributions from wood combustion and meat cooking during the current study. Future inhalation exposure studies may wish to target these sources as potential causes of adverse health effects.

Size distribution of particle-phase molecular markers during a severe winter pollution episode.

Airborne particulate matter was collected using filter samplers and cascade impactors in six size fractions below 1.8 microm during a severe winter air pollution event at three sites in the Central Valley of California. The smallest size fraction analyzed was 0.056 < Dp <0.1 microm particle diameter, which accounts for the majority of the mass in the ultrafine (PM0.1) size range. Separate samples were collected during the daytime (10 a.m. to 6 p.m. PST) and nighttime (8 p.m. to 8 a.m. PST) to characterize diurnal patterns. Each sample was extracted with organic solvents and analyzed using gas chromatography mass spectrometry for molecular markers that can be used for size-resolved source apportionment calculations. Colocated impactor and filter measurements were highly correlated (R8 > 0.8) for retene, benzo[ghi]flouranthene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, perylene, indeno[1,2,3-cd]pyrene, benzo[ghi]perylene, coronene, MW302 polycyclic aromatic hydrocarbon (PAHs), 17beta(H)-21alpha(H)-30-norhopane, 17alpha(H)-21beta(H)-hopane, alphabetabeta-20R-C29-ethylcholestane, levoglucosan, and cholesterol. Of these compounds, levoglucosan was present in the highest concentration (60-2080 ng m(-3)) followed by cholesterol (6-35 ng m(-3)), PAHs (2-38 ng m(-3)), and hopanes and steranes (0-2 ng m(-3)). Nighttime concentrations were higher than daytime concentrations in all cases. Organic compound size distributions were generally similar to the total carbon size distributions during the nighttime but showed greater variability during the daytime. This may reflect the dominance of fresh emission in the stagnant surface layer during the evening hours and the presence of aged organic aerosol at the surface during the daytime when the atmosphere is better mixed. All of the measured organic compound particle size distributions had a single mode that peaked somewhere between 0.18 and 0.56 microm, but the width of each distribution varied by compound. Cholesterol generally had the broadest particle size distribution, while benzo[ghi]perylene and 17alpha(H)-21beta(H)-29-norhopane generally had sharper peaks. The difference between the size distributions of the various particle-phase organic compounds reflects the fact that these compounds exist in particles emitted from different sources. The results of the current study will prove useful for size-resolved source apportionment exercises.

Size-resolved source apportionment of airborne particle mass in a roadside environment.

Airborne particulate hopanes, steranes, and polycyclic aromatic hydrocarbons (PAHs) were measured in six size fractions < 1.8 microm particle diameter at one site upwind and two sites downwind of the Interstate 5 freeway in San Diego, CA. The smallest size fraction collected was exclusively in the ultrafine size range (D(p) < 0.1 microm; PM0.1). Size distributions of hopanes, steranes, and PAHs peaked between 0.10-0.18 microm particle aerodynamic diameter with a tail extending into the PM0.1 size range. This pattern is similar to previous dynamometer studies of hopane, sterane, and PAH size distributions emitted from gasoline- and diesel-powered vehicles. Size-resolved source profiles were combined to form an "on-road" profile for motor oil, diesel, and gasoline contributions to EC and OC. The resulting equations were used to predict source contributions to the size distributions of EC and OC in the roadside environment. The method successfully accounted for the majority of the carbonaceous material in particles with diameter < 0.18 microm, with significant residual material in larger size fractions. The peak in both the measured and predicted EC size distribution occurred between 0.1-0.18 microm particle aerodynamic diameter. The predicted OC size distribution peaked between 0.1-0.18 microm particle diameter, butthe measured OC size distribution peaked between 0.56-1.0 microm particle diameter, possibly because of secondary organic aerosol formation. Predicted OC concentrations in particles with diameter < 0.18 microm were greater than measured values 18 m downwind of the roadway but showed good agreement 37 m downwind. The largest source contributions to the PM0.1 and PM0.18 size fractions were different. PM0.18 was dominated by diesel fuel and motor oil combustion products while PM0.1 was dominated by diesel fuel and gasoline fuel combustion products. Total source contributions to ultrafine (PM0.1) EC concentrations 37 m downwind of the roadway were 44 +/- 6% diesel fuel, 21 +/- 1% gasoline, 5 +/- 6% motor oil, and 30% unknown. Total source contributions to ultrafine (PM0.1) OC concentrations 37 m downwind of the roadway were 46 +/- 5% diesel fuel, 44 +/- 5% gasoline, 20 +/- 15% motor oil with a slight overprediction (11%). Diesel fuel appears to make the single largest contribution to ultrafine (PM0.1) particle mass given the fleet distribution during the current experiment.

Carbonyl emissions from gasoline and diesel motor vehicles.

Carbonyls from gasoline-powered light-duty vehicles (LDVs) and heavy-duty diesel-powered vehicles (HDDVs) operated on chassis dynamometers were measured by use of an annular denuder-quartz filter-polyurethane foam sampler with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization and chromatography-mass spectrometry analyses. Two internal standards were utilized based on carbonyl recovery: 4-fluorobenzaldehyde for < C8 carbonyls and 6-fluoro-4-chromanone for > or = C8 compounds. Gas- and particle-phase emissions for 39 aliphatic and 20 aromatic carbonyls ranged from 0.1 to 2000 microg/L of fuel for LDVs and from 1.8 to 27 000 microg/L of fuel for HDDVs. Gas-phase species accounted for 81-95% of the total carbonyls from LDVs and 86-88% from HDDVs. Particulate carbonyls emitted from a HDDV under realistic driving conditions were similar to concentrations measured in a diesel particulate matter (PM) standard reference material. Carbonyls accounted for 19% of particulate organic carbon (POC) emissions from low-emission LDVs and 37% of POC emissions from three-way catalyst-equipped LDVs. This identifies carbonyls as one of the largest classes of compounds in LDV PM emissions. The carbonyl fraction of HDDV POC was lower, 3.3-3.9% depending upon operational conditions. Partitioning analysis indicates the carbonyls had not achieved equilibrium between the gas and particle phases under the dilution factors of 126-584 used in the present study.

Lubricating oil and fuel contributions to particulate matter emissions from light-duty gasoline and heavy-duty diesel vehicles.

Size-resolved particulate matter emissions from heavy-duty diesel vehicles (HDDVs) and light-duty gasoline vehicles (LDGVs) operated under realistic driving cycles were analyzed for elemental carbon (EC), organic carbon (OC), hopanes, steranes, and polycyclic aromatic hydrocarbons. Measured hopane and sterane size distributions did not match the total carbon size distribution in most cases, suggesting that lubricating oil was not the dominant source of particulate carbon in the vehicle exhaust. A regression analysis using 17alpha(H)-21beta(H)-29-norhopane as a tracer for lubricating oil and benzo[ghi/perylene as a tracer for gasoline showed that gasoline fuel and lubricating oil both make significant contributions to particulate EC and OC emissions from LDGVs. A similar regression analysis performed using 17alpha(H)-21beta(H)-29-norhopane as a tracer for lubricating oil and flouranthene as a tracerfor diesel fuel was able to explain the size distribution of particulate EC and OC emissions from HDDVs. The analysis showed that EC emitted from all HDDVs operated under relatively high load conditions was dominated by diesel fuel contributions with little EC attributed to lubricating oil. Particulate OC emitted from HDDVs was more evenly apportioned between fuel and oil contributions. EC emitted from LDGVs operated underfuel-rich conditions was dominated by gasoline fuel contributions. OC emitted from visibly smoking LDGVs was mostly associated with lubricating oil, but OC emitted from all other categories of LDGVs was dominated by gasoline fuel. The current study clearly illustrates that fuel and lubricating oil make separate and distinct contributions to particulate matter emissions from motor vehicles. These particles should be tracked separately during ambient source apportionment studies since the atmospheric evolution and ultimate health effects of these particles may be different. The source profiles for fuel and lubricating oil contributions to EC and OC emissions derived in this study provide a foundation for future source apportionment calculations.

Size distribution of trace organic species emitted from light-duty gasoline vehicles.

Size distributions for particulate hopanes+steranes and nonvolatile polycyclic aromatic hydrocarbons (PAHs) emitted from five classes of light-duty gasoline-powered vehicles were measured using the federal test procedure (FTP), unified cycle (UC), and correction cycle (CC) driving cycles. 17alpha(H)-21beta(H)-29-norhopane, 17alpha(H)-21beta(H)-hopane, alpha beta beta-20R-stigmastane, and alpha beta beta-20S-stigmastane were highly correlated and behaved consistently across sampling methods. Coronene and benzo[ghi]perylene were the most ubiquitous heavy PAHs detected in the vehicle exhaust. The emission rates of hopanes, steranes, and PAHs contained in particles with aerodynamic diameters of less than 1.8 ,m varied by 2 orders of magnitude between the lowest- and highest-emitting vehicle classes. Hopane+sterane size distributions emitted from vehicles without an operating catalyst (including "cold-start" emissions from catalyst-equipped vehicles) were bimodal with one mode between 0.10 and 0.18 microm and the second mode >0.32 microm particle diameter. Hopane+sterane emissions released from vehicles with a catalyst at operating temperature had a single mode between 0.1 and 0.18 microm diameter. Hopane+sterane emissions from visibly smoking vehicles had a single mode between 0.18 and 0.32 microm diameter. Heavy PAH size distributions for all vehicle classes consistently had a single mode between 0.10 and 0.18 microm particle diameter (0.1-0.32 microm diameter for smoking vehicles). The geometric standard deviations for PAH size distributions were generally smaller than the corresponding hopane+sterane distributions. These trends suggest that hopanes+steranes and heavy PAHs act as tracers for separate processes of particulate organic carbon formation. PAH and hopane+sterane emissions shifted to smaller sizes during the more aggressive UC and CC driving cycles relative to the FTP. The fraction of PAH and hopane+sterane emissions in the ultrafine (Dp < 0.1 microm) range more than doubled during "warm-start" UC and CC cycles vs the FTP cycle. The enhancement of ultrafine PAHs during "cold-start" UC driving cycles was less pronounced.

Quinone emissions from gasoline and diesel motor vehicles.

Gas- and particle-phase emissions from gasoline and diesel vehicles operated on chassis dynamometers were collected using annular denuders, quartz filters, and PUF substrates. Quinone species were measured using O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization in conjunction with gas chromatography-mass spectrometry and high-performance liquid chromatography-mass spectrometry. Nine quinones were observed, ranging from C6 to C16. New species identified in motor vehicle exhaust include methyl-1,4-benzoquinone, 2-methyl-1,4-naphthoquinone (MNQN), and aceanthrenequinone. Gas-phase motor vehicle emissions of quinones are also reported for the first time. Six gas-phase quinones were quantified with emission rates of 2-28 000 microg L(-1) fuel consumed. The most abundant gas-phase quinones were 1,4-benzoquinone (BON) and MNQN. The gas-phase fraction was > or = 69% of quinone mass for light-duty gasoline emissions, and > or = 84% for heavy-duty diesel emissions. Eight particle-phase quinones were observed between 2 and 1600 microg L(-1), with BQN the most abundant species followed by 9,10-phenanthrenequinone and 1,2-naphthoquinone. Current particle-phase quinone measurements agree well with the few available previous results. Further research is needed concerning the gas-particle partitioning behavior of quinones in ambient and combustion source conditions.

Size distribution of trace organic species emitted from heavy-duty diesel vehicles.

Size distributions of particulate hopanes, steranes, and polycyclic aromatic hydrocarbons (PAHs) were measured in the exhaust from four heavy-duty diesel vehicles (HDDVs) operated under idle, creep, transient, and two high-speed driving modes. Particulate matter was collected using a chassis dynamometer and a dilution sampling system equipped with cascade impactors and filter samplers. Samples were extracted using organic solvents and analyzed using gas chromatography-mass spectrometry. Size distributions of hopanes and steranes were functions of engine load conditions and vehicle technology. Hopanes and steranes peaked in size ranges larger than 0.18 microm aerodynamic particle diameter under light load conditions and less than 0.10 microm aerodynamic particle diameter under heavier load conditions. The eight hopane size distributions emitted from newertechnology (> 1998) vehicles were unimodal while the four hopane size distributions emitted from older technology vehicles (< 1992) were bimodal. Similar trends between older and newer vehicles were not observed for sterane size distributions. The PAH composition emitted from HDDVs was a function of driving cycle and vehicle technology. Light driving cycles produced quantifiable emissions of 3, 4, 5, and 6 ring PAHs (including coronene). Heavier driving cycles produced only the 3 and 4 ring PAHs in quantifiable amounts. PM1.8 and PM0.1 source profiles constructed using the relative abundance of hopanes and steranes to total organic carbon were functions of vehicle load condition. Increasing load reduced the relative abundance of motor oil tracers in the PM1.8 size fraction and increased the abundance of these tracers in the PM0.1 size fraction. The relative abundances of PAHs in the PM0.1 and PM1.8 size fractions emitted from the oldest vehicle tested (1985 HDDV) were significantly higher than for any other vehicle tested.

Field, laboratory, and X-ray absorption spectroscopic studies of mercury accumulation by water hyacinths.

We have studied water hyacinth (Eichhornia crassipes), a non-native nuisance plant found in the in San Francisco Bay Delta region, for its potential to phytoremediate mercury. Mercury is a common contaminant in San Francisco Bay Area waters because of gold mining activities. In this study, speciation of mercury in hyacinth roots and shoots, rates of mercury uptake by hyacinths in the laboratory, and mercury levels near the Big Break Region in the Delta were studied. In the speciation studies, Hg L3 edge X-ray absorption spectroscopic analysis of Hg model compounds and water hyacinth roots and shoots revealed that Hg was initially bound ionically to oxygen ligands in roots, most likely to carboxylate groups, and was bound covalently to sulfur groups in shoots. In laboratory uptake studies, we found that water hyacinths grown in 1 ppm Hg and one-quarter strength Hoagland's solution accumulated a maximum of 0.20 ppm in shoots and 16.0 ppm in roots, both reaching maximum concentrations after approximately 16 days. Mercury concentrations were found to be 0.26 +/- 0.20 ppm in the water and 0.86 +/- 1.70 ppm in sediment at Big Break. It was proposed that water hyacinths have the potential to phytoremediate mercury in the water at Big Break if the current herbicide treatments are replaced by physical removal.