Catalyzed Gasoline Particulate Filters Reduce Secondary Organic Aerosol Production from Gasoline Direct Injection Vehicles

The effects of photochemical aging on exhaust emissions from two light-duty vehicles with gasoline direct injection (GDI) engines equipped with and without catalyzed gasoline particle filters (GPFs) were investigated using a mobile environmental chamber. Both vehicles with and without the GPFs were exercised over the LA92 drive cycle using a chassis dynamometer. Diluted exhaust emissions from the entire LA92 cycle were introduced to the mobile chamber and subsequently photochemically reacted. It was found that the addition of catalyzed GPFs will significantly reduce tailpipe particulate emissions and also provide benefits in gaseous emissions, including nonmethane hydrocarbons (NMHC). Tailpipe emissions composition showed important changes with the use of GPFs by practically eliminating black carbon and increasing the fractional contribution of organic mass. Production of secondary organic aerosol (SOA) was reduced with GPF addition, but was also dependent on engine design which determined the amount of SOA precursors at the tailpipe. Our findings indicate that SOA production from GDI vehicles will be reduced with the application of catalyzed GPFs through the mitigation of reactive hydrocarbon precursors

Estimate of global atmospheric organic aerosol from oxidation of biogenic hydrocarbons

The results from a series of outdoor chamber experiments establishing the atmospheric aerosol-forming potential of fourteen terpenoid hydrocarbons have been used to estimate the annual amount of secondary organic aerosol formed globally from compounds emitted by vegetation. Hydroxyl radical, ozone, and nitrate radical oxidation each contribute to aerosol formation in full-photooxidation experiments; because oxidation by nitrate radical under ambient, remote conditions is likely to be negligible, parameters describing aerosol formation from hydroxyl radical and ozone reaction only are developed. Chamber results, temporally and spatially resolved, compound-specific estimates of biogenic hydrocarbon emissions, and hydroxyl radical and ozone fields are combined to lead to an estimate for atmospheric secondary organic aerosol formed annually from biogenic precursors of 18.5 Tg, a number smaller than the previously published estimate of 30–270 Tg [Andreae and Crutzen, 1997]

Organic aerosol formation from the oxidation of biogenic hydrocarbons

A series of outdoor chamber experiments has been used to establish and characterize the significant atmospheric aerosol-forming potentials of the most prevalent biogenic hydrocarbons emitted by vegetation. These compounds were also studied to elucidate the effect of structure on aerosol yield for these types of compounds. Because oxidation products partition between the gas and aerosol phases, the aerosol yields of the parent biogenic hydrocarbons depend on the concentration of organic aerosol into which these products can be absorbed. For organic mass concentrations between 5 and 40 µg m^(-3), mass-based yields in photooxidation experiments range from 17 to 67% for sesquiterpenes, from 2 to 23% for cyclic diolefins, from 2 to 15% for bicyclic olefins, and from 2 to 6% for the acyclic triolefin ocimene. In these photooxidation experiments, hydroxyl and nitrate radicals and ozone can contribute to consumption of the parent hydrocarbon. For bicyclic olefins (α-pinene, β-pinene, Δ^3-carene, and sabinene), experiments were also carried out at daytime temperatures in a dark system in the presence of ozone or nitrate radicals alone. For ozonolysis experiments, resulting aerosol yields are less dependent on organic mass concentration, when compared to full, sunlight-driven photooxidation. Nitrate radical experiments exhibit extremely high conversion to aerosol for β-pinene, sabinene, and Δ^3-carene. The relative importance of aerosol formation from each type of reaction for bicyclic olefin photooxidation is elucidated

Platinum-group element geochemistry of the Forest Reef Volcanics, southeastern Australia: Implications for porphyry Au-Cu mineralisation

Platinum-group element concentrations in felsic to intermediate rocks from the Forest Reef Volcanics, Cadia-Neville region, southeastern Australia have been analysed by the Ni-S fire assay-isotope dilution method. The Forest Reef Volcanics are shoshonitic to calc-alkaline in composition and fractionated to produce a wide range of compositions, with MgO varying between 9.7 and 1.8 wt.%. The interest in this suite is that it is coeval with Au-Cu porphyry-style mineralisation in the Cadia mineral district. This study uses PGE geochemistry to determine the timing of sulfide saturation, relative to volatile (ore-fluid) saturation, in the magma that gave rise to the Forest Reef Volcanics and, in turn, to assess how this timing affected the mineralisation potential of the evolving magmatic system. The Forest Reef Volcanics can be subdivided, on the basis of their contrasting PGE geochemistry, into high-Mg (>6.8 wt.% MgO) and low-Mg suites (≤6.8 wt.% MgO). Platinum, Pd and Re concentrations increase in the high-Mg samples, whereas Ir and Ru decrease and Rh concentrations remain steady, with decreasing MgO. The coupled Ir, Ru and Rh depletion is attributed to the partitioning of these elements into magnetite. The rate of Pt and Pd enrichment is not possible by closed-system fractional crystallisation alone, which suggests that the parent magma was replenished by a Pt-Pd-rich melt. In contrast, the PGE concentrations in the low-Mg samples decrease with decreasing MgO indicating the onset of sulfide saturation at 6.8 wt.% MgO, which is confirmed by the presence of spheroidal sulfide inclusions in liquidus crystals (i.e. clinopyroxene, plagioclase, magnetite). The rate of Pd depletion is appreciably less than for any other sulfide saturated felsic system for which data are available. This requires either that the amount of sulfide melt to have precipitated was unusually low, or that the rate of Pd depletion was limited by the mass of silicate melt the sulfide melt reached equilibrium with, or both. In any event, the fraction of sulfide melt that precipitated was too small to have had a significant effect on the Cu and Au content of the magma so that both Cu and Au were available to enter the ore-forming fluid when the magma became volatile saturated at, or shortly after, it reached ca. 2.9 wt.% MgO.This research was funded by a Newcrest Mining LTD Grant to Ian Campbell

Observation of gaseous and particulate products of monoterpene oxidation in forest atmospheres

Atmospheric oxidation of biogenic hydrocarbons, such as monoterpenes, is estimated to be a significant source of global aerosol. Whereas laboratory studies have established that photochemical oxidation of monoterpenes leads to aerosol formation, there are limited field studies detecting such oxidation products in ambient aerosols. Drawing on prior results of monoterpene product analysis under controlled smog chamber conditions, we have identified organic aerosol components attributable to monoterpene oxidation in two forest atmospheres, Kejimkujik National Park, Nova Scotia, Canada, and Big Bear, San Bernardino National Forest, California, U.S.A. The major identified aerosol products derived from α-pinene and β-pinene oxidation include pinic acid, pinonic acid, norpinonic acid and its isomers, hydroxy pinonaldehydes, and pinonaldehyde, concentrations of which in the aerosol phase are in the sub ng m^(−3) range. Identification of oxidation products in atmospheric aerosol samples serves as direct evidence for aerosol formation from monoterpenes under ambient conditions

Comprehensive Simultaneous Shipboard and Airborne Characterization of Exhaust from a Modern Container Ship at Sea

We report the first joint shipboard and airborne study focused on the chemical composition and water-uptake behavior of particulate ship emissions. The study focuses on emissions from the main propulsion engine of a Post-Panamax class container ship cruising off the central coast of California and burning heavy fuel oil. Shipboard sampling included micro-orifice uniform deposit impactors (MOUDI) with subsequent off-line analysis, whereas airborne measurements involved a number of real-time analyzers to characterize the plume aerosol, aged from a few seconds to over an hour. The mass ratio of particulate organic carbon to sulfate at the base of the ship stack was 0.23 ± 0.03, and increased to 0.30 ± 0.01 in the airborne exhaust plume, with the additional organic mass in the airborne plume being concentrated largely in particles below 100 nm in diameter. The organic to sulfate mass ratio in the exhaust aerosol remained constant during the first hour of plume dilution into the marine boundary layer. The mass spectrum of the organic fraction of the exhaust aerosol strongly resembles that of emissions from other diesel sources and appears to be predominantly hydrocarbon-like organic (HOA) material. Background aerosol which, based on air mass back trajectories, probably consisted of aged ship emissions and marine aerosol, contained a lower organic mass fraction than the fresh plume and had a much more oxidized organic component. A volume-weighted mixing rule is able to accurately predict hygroscopic growth factors in the background aerosol but measured and calculated growth factors do not agree for aerosols in the ship exhaust plume. Calculated CCN concentrations, at supersaturations ranging from 0.1 to 0.33%, agree well with measurements in the ship-exhaust plume. Using size-resolved chemical composition instead of bulk submicrometer composition has little effect on the predicted CCN concentrations because the cutoff diameter for CCN activation is larger than the diameter where the mass fraction of organic aerosol begins to increase significantly. The particle number emission factor estimated from this study is 1.3 × 10^(16) (kg fuel)^(−1), with less than 1/10 of the particles having diameters above 100 nm; 24% of particles (>10 nm in diameter) activate into cloud droplets at 0.3% supersaturation