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.

As part of the Gasoline/Diesel PM Split Study, relatively large fleets of gasoline vehicles 53 and diesel vehicles 34 were tested on a chassis dynamometer to develop chemical source profiles for source attribution of atmospheric particulate matter in California's South Coast Air Basin. Gasoline vehicles were tested in cold-start and warm-start conditions, and diesel vehicles were tested through several driving cycles. Tailpipe emissions of particulate matter were analyzed for organic tracer compounds, including hopanes, steranes, and polycyclic aromatic hydrocarbons. Large intervehicle variation was seen in emission rate and composition, and results were averaged to examine the impacts of vehicle ages, weight classes, and driving cycles on the variation. Average profiles, weighted by mass emission rate, had much lower uncertainty than that associated with intervehicle variation. Mass emission rates and elemental carbon/organic carbon (EC/OC) ratios for gasoline vehicle age classes were influenced most by use of cold-start or warm-start driving cycle (factor of 2-7). Individual smoker vehicles had a large range of mass and EC/OC (factors of 40 and 625, respectively). Gasoline vehicle age averages, data on vehicle ages and miles traveled in the area, and several assumptions about smoker contributions were used to create emissions profiles representative of on-road vehicle fleets in the Los Angeles area in 2001. In the representative gasoline fleet profiles, variation was further reduced, with coldstart or warm-start and the representation of smoker vehicles making a difference of approximately a factor of two in mass emission rate and EC/OC. Diesel vehicle profiles were created on the basis of vehicle age, weight class, and driving cycle. Mass emission rate and EC/OC for diesel averages were influenced by vehicle age (factor of 2-5), weight class (factor of 2-7), and driving cycle (factor of 10 -20). Absolute and relative emissions of molecular marker compounds showed levels of variation similar to those of mass and EC/OC.

[1] Atmospheric particulate matter samples were collected at two Maldives climate observatories from 30 August 2004 to 21 January 2005. This time period encompassed both wet and dry seasons, which correspond to low and high aerosol loadings. High aerosol loadings were observed in the northern sampling site in Hanimaadhoo, caused by long-range transport from south and Southeast Asia, whereas the southern sampling site, Gan, was not subject to as much continental inflow. The polluted period began in midNovember and lasted through the remainder of the sampling period. Fine particulate matter during this time was characterized by relatively high concentrations of aerosol mass and elemental carbon. Concentrations of water-soluble potassium, sulfate, levoglucosan, polyaromatic hydrocarbons, aliphatic diacids, aromatic diacids, and trace metals increased over the clean, transition, and polluted dry season. Organic speciation suggested that significant secondary organic aerosol formation occurred during the polluted dry season, meaning that traditional methods of source identification relying on fixed elemental and organic carbon ratios between source and receptors are not sufficient. Well-studied molecular markers for combustion sources were not adequate in fully attributing elemental carbon over the northern Indian Ocean to specific sources. Further source profiling of south and Southeast Asian biofuels and fossil fuels is recommended. A receptor-based positive matrix factorization model was applied to fine particulate matter trace metal measurements and showed that biofuel burning and fossil fuel combustion were equally important sources of elemental carbon during the polluted dry season.Citation: Stone, E. A., G. C. Lough, J. J. Schauer, P. S. Praveen, C. E. Corrigan, and V. Ramanathan (2007), Understanding the origin of black carbon in the atmospheric brown cloud over the Indian Ocean,

Gaseous elemental mercury (GEM), particulate mercury (PHg) and reactive gaseous mercury (RGM) were measured every other hour at a rural location in south central Wisconsin (Devil's Lake State Park, WI, USA) between April 2003 and March 2004, and at a predominantly downwind urban site in southeastern Wisconsin (Milwaukee, WI, USA) between June 2004 and May 2005. Annual averages of GEM, PHg, and RGM at the urban site were statistically higher than those measured at the rural site. Pollution roses of GEM and reactive mercury (RM; sum of PHg and RGM) at the rural and urban sites revealed the influences of point source emissions in surrounding counties that were consistent with the US EPA 1999 National Emission Inventory and the 2003-2005 US EPA Toxics Release Inventory. Source-receptor relationships at both sites were studied by quantifying the impacts of point sources on mercury concentrations. Time series of GEM, PHg, and RGM concentrations were sorted into two categories; time periods dominated by impacts from point sources, and time periods dominated by mercury from non-point sources. The analysis revealed average point source contributions to GEM, PHg, and RGM concentration measurements to be significant over the year long studies. At the rural site, contributions to annual average concentrations were: GEM (2%; 0.04 ng m(-3)); and, RM (48%; 5.7 pg m(-3)). At the urban site, contributions to annual average concentrations were: GEM (33%; 0.81 ng m(-3)); and, RM (64%; 13.8 pg m(-3)).

On-road vehicle emission rates of nonmethane hydrocarbons (NMHCs) were measured in two tunnels in Milwaukee Milwaukee area with tunnel emissions showed the impact of seasonal differences in fuels and emissions on the urban atmosphere. Composition of fuel samples collected from area gas stations in both seasons was correlated with vehicle emissions; the predominant difference was increased winter emissions of lighter hydrocarbons present in winter gasoline. A chemical mass balance model was used to determine the contributions of whole gasoline and gasoline headspace vapors to vehicle emissions in the tunnel and cold-start tests, which were found to vary with season. Results of the mass balance model also indicate that partially combusted components of gasoline are a major contributor to emissions of aromatic compounds and air toxic compounds, including benzene, toluene, xylenes, napthalene, and 1,3-butadiene, whereas air toxics hexane and 2,2,4-trimethylpentane are largely attributed to gasoline and headspace vapors.