Temporal trends in motor vehicle and secondary organic tracers using in situ methylation thermal desorption GCMS.

Organic aerosol measurements with high temporal resolution can differentiate primary organic carbon (POC) from secondary organic carbon (SOC) and can be used to distinguish morning rush hour traffic emissions and subsequent photo-oxidation. In the current study, five hour filter samples were collected during the Summer Study for Organic Aerosols at Riverside (SOAR-1 in CA, USA) for analysis of organic molecular markers. To achieve the low detection limits required for the high temporal resolution data, a laboratory-based in situ methylation thermal desorption gas chromatography-mass spectrometry method was developed. This enabled the measurement of potential markers of SOC, including phthalic acid, along with markers for traffic emissions, including norhopane. The aromatic acids correlated well with unapportioned OC from a molecular marker chemical mass balance model (SOC-cmb; r(2) = 0.46-0.70) and SOC from the elemental carbon tracer method (SOC-ec; r(2) = 0.40-0.56). The aromatic acid/norhopane ratio increased substantially over the course of each day. The average mid-day phthalic acid ratio compared to previously published roadway emissions was a factor of 4 times higher, while the average 1,2,3-benzenetricarboxylic acid ratio was a factor of 40 times higher than roadway emissions. Using correlation plots of SOC-cmb and phthalic acid, it was estimated that 2.9 ± 0.6 µg m(-3) SOC was associated with mid-day aromatic acid production in Riverside.

Improved source apportionment and speciation of low-volume particulate matter samples.

New chemical analysis methods for the characterization of atmospheric particulate matter (PM)* samples were developed and demonstrated in order to expand the number of such methods for use in future health studies involving PM. Three sets of methods were, developed, for the analysis (1) of organic tracer compounds in low-volume personal exposure samples (for source apportionment), (2) of trace metals and other trace elements in low-volume personal exposure samples, and (3) of the speciation of the oxidation states of water-soluble iron (Fe), manganese (Mn), and chromium (Cr) in PM samples. The development of the second set of methods built on previous work by the project team, which had in the past used similar methods in atmospheric source apportionment studies. The principal challenges in adapting these methods to the analysis of personal exposure samples were the improvement of detection limits (DLs) and control of the low-level contamination that can compromise personal exposure samples. A secondary goal of our development efforts was to reduce the cost and complexity of the three sets of methods in order to help facilitate their broader use in future health studies. The goals of the project were achieved, and the ability to integrate the methods into existing health studies was demonstrated by way of conducting two pilot studies. The first study involved analysis of trace elements in size-resolved PM samples that had been collected to represent study subjects' personal exposures along with simultaneous measures of indoor and outdoor PM concentrations. The second study involved analysis of the speciation of organic tracer compounds in personal exposure samples, indoor samples, and outdoor samples in order to understand the diesel PM exposure of study subjects in various job classifications in an occupational setting. Both pilot studies used existing samples from. large multi-year health studies and were intended to demonstrate the feasibility and value of using the new chemical analysis methods to better characterize the personal exposure samples. Analysis of the health data and the broader implications of the exposure assessments were not evaluated as part of the present study, but our pilot-study measurements are expected to contribute to investigators' future analyses in the large multi-year health studies. The methods we developed for the low-cost measurement of the oxidation states of Fe, Mn, and Cr in atmospheric PM samples are extremely sensitive and well suited for use in health studies. To demonstrate the utility of these methods, small-scale studies were conducted to characterize the redox cycling of Fe in PM on the time scale of atmospheric transport from source to personal exposure and to provide preliminary data on the atmospheric concentrations of soluble forms of the target metals in selected urban environments (in order to help focus future research seeking to understand the role of metals in human exposure to PM and its adverse health effects). The present report summarizes the methods that were developed and demonstrated to be suitable for use in health studies and provides pilot-scale data that can be used to develop hypotheses and experimental strategies to further enhance the ability of future health studies to elucidate the role of PM, PM sources, and PM components in the observed associations between atmospheric PM and adverse human health outcomes.

Tracking personal exposure to particulate diesel exhaust in a diesel freight terminal using organic tracer analysis.

Personal exposure to particle-phase molecular markers was measured at a trucking terminal in St Louis, MO, as part of a larger epidemiologic project aimed at assessing carbonaceous fine particulate matter (PM) exposure in this occupational setting. The integration of parallel personal exposure, ambient worksite area and ambient urban background (St Louis Supersite) measurements provided a unique opportunity to track the work-related exposure to carbonaceous fine PM in a freight terminal. The data were used to test the proposed personal exposure model in this occupational setting: To accurately assess the impact of PM emission sources, particularly motor vehicle exhaust, and organic elemental carbon (OCEC) analysis and nonpolar organic molecular marker analysis by thermal desorption-gas chromatography/mass spectrometry (TD-GCMS) were conducted on all of the PM samples. EC has been used as a tracer for diesel exhaust in urban areas, however, the emission profile for diesel exhaust is dependent upon the operating conditions of the vehicle and can vary considerably within a fleet. Hopanes, steranes, polycyclic aromatic hydrocarbons and alkanes were measured by TD-GCMS. Hopanes are source-specific organic molecular markers for lubricating oil present in motor vehicle exhaust. The concentrations of OC, EC and the organic tracers were averaged to obtain average profiles to assess differences in the personal, worksite area and urban background samples, and were also correlated individually by sample time to evaluate the exposure model presented above. Finally, a chemical mass balance model was used to apportion the motor vehicle and cigarette-smoke components of the measured OC and EC for the average personal exposure, worksite area and urban background samples.

Characterization of metals emitted from motor vehicles.

A systematic approach was used to quantify the metals present in particulate matter emissions associated with on-road motor vehicles. Consistent sampling and chemical analysis techniques were used to determine the chemical composition of particulate matter less than 10 microm in aerodynamic diameter (PM10*) and particulate matter less than 2.5 microm in aerodynamic diameter (PM2.5), including analysis of trace metals by inductively coupled plasma mass spectrometry (ICP-MS). Four sources of metals were analyzed in emissions associated with motor vehicles: tailpipe emissions from gasoline- and diesel-powered vehicles, brake wear, tire wear, and resuspended road dust. Profiles for these sources were used in a chemical mass balance (CMB) model to quantify their relative contributions to the metal emissions measured in roadway tunnel tests in Milwaukee, Wisconsin. Roadway tunnel measurements were supplemented by parallel measurements of atmospheric particulate matter and associated metals at three urban locations: Milwaukee and Waukesha, Wisconsin, and Denver, Colorado. Ambient aerosol samples were collected every sixth day for one year and analyzed by the same chemical analysis techniques used for the source samples. The two Wisconsin sites were studied to assess the spatial differences, within one urban airshed, of trace metals present in atmospheric particulate matter. The measurements were evaluated to help understand source and seasonal trends in atmospheric concentrations of trace metals. ICP-MS methods have not been widely used in analyses of ambient aerosols for metals despite demonstrated advantages over traditional techniques. In a preliminary study, ICP-MS techniques were used to assess the leachability of trace metals present in atmospheric particulate matter samples and motor vehicle source samples in a synthetic lung fluid.

Emissions of metals associated with motor vehicle roadways.

Emissions of metals and other particle-phase species from on-road motor vehicles were measured in two tunnels in Milwaukee, WI during the summer of 2000 and winter of 2001. Emission factors were calculated from measurements of fine (PM2.5) and coarse (PM10) particulate matter at tunnel entrances and exits, and effects of fleet composition and season were investigated. Cascade impactors (MOUDI) were used to obtain size-resolved metal emission rates. Metals were quantified with inductively-coupled plasma mass spectrometry (ICP-MS) and X-ray fluorescence (XRF). PM10 emission rates ranged from 38.7 to 201 mg km(-1) and were composed mainly of organic carbon (OC, 30%), inorganic ions (sulfate, chloride, nitrate, ammonium, 20%), metals (19%), and elemental carbon (EC, 9.3%). PM10 metal emissions were dominated by crustal elements Si, Fe, Ca, Na, Mg, Al, and K, and elements associated with tailpipe emissions and brake and tire wear, including Cu, Zn, Sb, Ba, Pb, and S. Metals emitted in PM2.5 were lower (11.6% of mass). Resuspension of roadway dust was dependent on weather and road surface conditions, and increased emissions were related to higher traffic volumes and fractions of heavy trucks. Emission of noble metals from catalytic converters appeared to be impacted by the presence of older vehicles. Elements related to brake wear were impacted by enriched road dust resuspension, but correlations between these elements in PM2.5 indicate that direct brake wear emissions are also important. A submicrometer particle mode was observed in the emissions of Pb, Ca, Fe, and Cu.