Rapid physical and chemical transformation of traffic-related atmospheric particles near a highway

The health of a substantial portion of urban populations is potentially being impacted by exposure to traffic–related atmospheric pollutants. To better understand the rapid physical and chemical transformation of these pollutants, the number size distributions of non–volatile traffic–related particles were investigated at different distances from a major highway. Particle volatility measurements were performed upwind and downwind of the highway using a fast mobility particle sizing spectrometer with a thermodenuder on a mobile laboratory. The number concentration of non–denuded ultrafine particles decreased exponentially with distance from the highway, whereas a more gradual gradient was observed for non–volatile particles. The non–volatile number concentration at 27 m was higher than that at 280 m by a factor of approximately 3, and the concentration at 280 m was still higher than that upwind of the highway. The proportion of non–volatile particles increased away from the highway, representing 36% of the total particle number at 27 m, 62% at 280 m, and 81% at the upwind site. A slight decrease in the geometric mean diameter of the non–volatile particle size distributions from approximately 35 nm to 30 nm was found between 27 m and 280 m, in contrast to the growth of non–denuded particles with increasing distance from the highway. Single particle analysis results show that the contribution of elemental carbon (EC)–rich particle types at 27 m was higher than the contribution at 280 m by a factor of approximately 2. The findings suggest that people living or spending time near major roadways could be exposed to elevated number concentrations of nucleation–mode volatile particles (100 nm). The impact of the highway emissions on air quality was observable up to 300 m.This work was supported by Environment Canada, Canada Foundation for Innovation, the Ontario Innovation Trust, and the Ontario Research Fund

Sources of Dimethyl Sulfide in the Canadian Arctic Archipelago and Baffin Bay

International audienceDimethyl sulfide plays a major role in the global sulfur cycle, meaning that it is important to the formation of sulfate aerosol and thus to cloud condensation nuclei populations and cloud formation. The summertime Arctic atmosphere sometimes resides in a cloud condensation nuclei limited regime, making it very susceptible to changes in their number. Despite the interest generated by this situation, dimethyl sulfide has only rarely been measured in the summertime Arctic. This work presents the first high time resolution (10 Hz) DMS mixing ratio measurements for the Eastern Canadian Archipelago and Baffin Bay in summer performed on an icebreaker cruise as one component of the Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments (NETCARE). Measured mixing ratios ranged from below the detection limit of 4 pptv to 1155 pptv with a median value of 186 pptv. We used transfer velocity parameterizations from the literature to generate the first flux estimates for this region in summer, which ranged from 0.02-12 μmol m-2 d-1. DMS has a lifetime against OH oxidation of 1-2 days, allowing both local sources and transport to play roles in its atmospheric mixing ratio. Through air mass trajectory analysis using FLEXPART-WRF and chemical transport modeling using GEOS-Chem, we have identified the relative contributions of local sources (Lancaster Sound and Baffin Bay) as well as transport from further afield (the Hudson Bay System and the Beaufort Sea) and find that the local sources dominate. GEOS-Chem is able to reproduce the major features of the measured time series, but is biased low overall (median 72 pptv). We discuss non-marine sources that could account for this low bias and estimate the possible contributions to DMS mixing ratios from lakes, biomass burning, melt ponds and coastal tundra. Our results show that local marine sources of DMS dominate the summer Arctic atmosphere, but that non-local and possibly non-marine contributions have a detectable influence

Ice nucleating particles in the marine boundary layer in the Canadian Arctic during summer 2014

International audienceIce nucleating particles (INPs) in the Arctic can influence climate and precipitation in the region; yet our understanding of the concentrations and sources of INPs in this region remain uncertain. In the following, we (1) measured concentrations of INPs in the immersion mode in the Cana-dian Arctic marine boundary layer during summer 2014 on board the CCGS Amundsen, (2) determined ratios of surface areas of mineral dust aerosol to sea spray aerosol, and (3) investigated the source region of the INPs using particle dispersion modelling. Average concentrations of INPs at − 15, −20, and −25 • C were 0.005, 0.044, and 0.154 L −1 , respectively. These concentrations fall within the range of INP concentrations measured in other marine environments. For the samples investigated the ratio of mineral dust surface area to sea spray surface area ranged from 0.03 to 0.09. Based on these ratios and the ice active surface site densities of mineral dust and sea spray aerosol determined in previous laboratory studies, our results suggest that mineral dust is a more important contributor to the INP population than sea spray aerosol for the samples analysed. Based on particle dispersion modelling , the highest concentrations of INPs were often associated with lower-latitude source regions such as the Hudson Bay area, eastern Greenland, or northwestern continental Canada. On the other hand, the lowest concentrations were often associated with regions further north of the sampling sites and over Baffin Bay. A weak correlation was observed between INP concentrations and the time the air mass spent over bare land, and a weak negative correlation was observed between INP concentrations and the time the air mass spent over ice and open water. These combined results suggest that mineral dust from local sources is an important contributor to the INP population in the Canadian Arctic marine boundary layer during summer 2014

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer

International audienceA biogeochemical connection between the atmosphere and the ocean is demonstrated whereby a marine source of oxygenated volatile organic compounds is identified. Compounds of this type are involved in the formation of secondary organic aerosol, which remains one of the most poorly understood components of Earth’s climate system due in part to the diverse sources of its volatile organic compound precursors. This is especially the case for marine environments, where there are more oxygenated volatile organic compounds than can be accounted for by known sources. Although it was observed in the summertime Arctic, this connection may be widespread and important to our understanding of secondary organic aerosol in other remote marine environments, with implications for our understanding of global climate

Measurements of Gas phase Acids in Diesel Exhaust: A Relevant Source of HNCO?

Gas-phase acids in light duty diesel (LDD) vehicle exhaust were measured using chemical ionization mass spectrometry (CIMS). Fuel based emission factors (EF) and NO_<i>x</i> ratios for these species were determined under differing steady state engine operating conditions. The derived HONO and HNO₃ EFs agree well with literature values, with HONO being the single most important acidic emission. Of particular importance is the quantification of the EF for the toxic species, isocyanic acid (HNCO). The emission factors for HNCO ranged from 0.69 to 3.96 mg kg_fuel^–1, and were significantly higher than previous biomass burning emission estimates. Further ambient urban measurements of HNCO demonstrated a clear relationship with the known traffic markers of benzene and toluene, demonstrating for the first time that urban commuter traffic is a source of HNCO. Estimates based upon the HNCO-benzene relationship indicate that upward of 23 tonnes of HNCO are released annually from commuter traffic in the Greater Toronto Area, far exceeding the amount possible from LDD alone. Nationally, 250 to 770 tonnes of HNCO may be emitted annually from on-road vehicles, likely representing the dominant source of exposure in urban areas, and with emissions comparable to that of biomass burning

Secondary formation of nitrated phenols: insights from observations during the Uintah Basin Winter Ozone Study (UBWOS) 2014

We describe the results from online measurements of nitrated phenols using a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) with acetate as reagent ion in an oil and gas production region in January and February of 2014. Strong diurnal profiles were observed for nitrated phenols, with concentration maxima at night. Based on known markers (CH4, NOx, CO2), primary emissions of nitrated phenols were not important in this study. A box model was used to simulate secondary formation of phenol, nitrophenol (NP), and dinitrophenols (DNP). The box model results indicate that oxidation of aromatics in the gas phase can explain the observed concentrations of NP and DNP in this study. Photolysis was the most efficient loss pathway for NP in the gas phase. We show that aqueous-phase reactions and heterogeneous reactions were minor sources of nitrated phenols in our study. This study demonstrates that the emergence of new ToF-CIMS (including PTR-TOF) techniques allows for the measurement of intermediate oxygenates at low levels and these measurements improve our understanding on the evolution of primary VOCs in the atmosphere.</p