ALBERT

Description: In early spring the Baltic region is frequently affected by high pollution events due to biomass burning in that area. Here we present a comprehensive study to investigate the impact of biomass/grass burning (BB) on the evolution and composition of aerosol in Preila, Lithuania, during springtime open fires. Non-refractory submicron particulate matter (NR-PM1) was measured by an Aerodyne aerosol chemical speciation monitor (ACSM) and a source apportionment with the multilinear engine (ME-2) running the positive matrix factorization (PMF) model was applied to the organic aerosol fraction to investigate the impact of biomass/grass burning. Satellite observations over regions of biomass burning activity supported the results and identification of air mass transport to the area of investigation. Sharp increases in biomass burning tracers, such as levoglucosan up to 683 ng m−3 and black carbon (BC) up to 17 μg m−3 were observed during this period. A further separation between fossil and non-fossil primary and secondary contributions was obtained by coupling ACSM PMF results and radiocarbon (14C) measurements of the elemental (EC) and organic (OC) carbon fractions. Non-fossil organic carbon (OCnf) was the dominant fraction of PM1, with the primary (POCnf) and secondary (SOCnf) fractions contributing 26–44 % and 13–23 % to the TC, respectively. 5–8 % of the TC had a primary fossil origin (POCf), whereas the contribution of fossil secondary organic carbon (SOCf) was 4–13 %. Non-fossil EC (ECnf) and fossil EC (ECf) ranged from 13–24 % and 7–12 %, respectively. Isotope ratio of stable carbon and nitrogen isotopes were used to distinguish aerosol particles associated with solid and liquid fossil fuel burning.

Description: We report simultaneous measurements of volatile organic compound (VOC) mixing ratios including C6 to C8 aromatics, isoprene, monoterpenes, acetone and organic aerosol mass loadings at a rural location in Southwestern Ontario, Canada by Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) and Aerosol Mass Spectrometry (AMS), respectively. During the three-week-long Border Air Quality and Meteorology Study in June–July 2007, air was sampled from a range of sources, including aged air from the polluted US Midwest, direct outflow from Detroit 50 km away, and clean air with higher biogenic input. After normalization to the diurnal profile of CO, a long-lived tracer, diurnal analyses show clear photochemical loss of reactive aromatics and production of oxygenated VOCs and secondary organic aerosol (SOA) during the daytime. Biogenic VOC mixing ratios increase during the daytime in accord with their light- and temperature-dependent sources. Long-lived species, such as hydrocarbon-like organic aerosol and benzene show little to no photochemical reactivity on this timescale. From the normalized diurnal profiles of VOCs, an estimate of OH concentrations during the daytime, measured O3 concentrations, and laboratory SOA yields, we calculate integrated organic aerosol production amounts associated with each measured SOA precursor. Depending on whether the SOA formation is occurring in a low- or high-NOx regime, we estimate that the biogenic gases contribute between 10 to 36 times as much SOA as do the aromatic precursors, making this a highly biogenically dominated region for SOA formation. The conclusion that biogenic SOA formation is of significance to air quality in this region is supported by detailed air quality modeling during this period (Stroud et al., 2010).

Description: During the winter component of the SPORT (Seasonal Particle Observations in the Region of Toronto) field campaign, particulate non-refractory chemical composition and concentration of selected volatile organic compounds (VOCs) were measured by an Aerodyne time-of-flight aerosol mass spectrometer (AMS) and a proton transfer reaction-mass spectrometer (PTR-MS), respectively. Sampling was performed in downtown Toronto ~15 m from a major road. The mass spectra from the AMS and PTR-MS were combined into a unified dataset, which was analyzed using positive matrix factorization (PMF). The two instruments were given equal weight in the PMF analysis by application of a scaling factor to the uncertainties of each instrument. A residual based metric, Δesc, was used to evaluate the relative weight. The PMF analysis yielded a 5-factor solution that included factors characteristic of regional transport, local traffic emissions, charbroiling, and oxidative processing. The unified dataset provides information on particle and VOC sources and atmospheric processing that cannot be obtained from the datasets of the individual instruments, such as apportionment of oxygenated VOCs to direct emission sources vs. secondary reaction products, improved correlation of oxygenated aerosol factors with photochemical age, and increased detail regarding the composition of oxygenated organic aerosol factors. This analysis represents the first application of PMF to a unified AMS/PTR-MS dataset.

Description: Chemically resolved atmospheric aerosol data sets from the largest intercomparison of the Aerodyne aerosol chemical speciation monitors (ACSM) performed to date were collected at the French atmospheric supersite SIRTA. In total 13 quadrupole ACSMs (Q-ACSM) from the European ACTRIS ACSM network, one time-of-flight ACSM (ToF-ACSM), and one high-resolution ToF aerosol mass spectrometer (AMS) were operated in parallel for about three weeks in November and December 2013. Part 1 of this study reports on the accuracy and precision of the instruments for all the measured species. In this work we report on the intercomparison of organic components and the results from factor analysis source apportionment by positive matrix factorisation (PMF) utilising the multilinear engine 2 (ME-2). Except for the organic contribution of m/z 44 to the total organics (f44), which varied by factors between 0.6 and 1.3 compared to the mean, the peaks in the organic mass spectra were similar among instruments. The m/z 44 differences in the spectra resulted in a variable f44 in the source profiles extracted by ME-2, but had only a minor influence on the extracted mass contributions of the sources. The presented source apportionment yielded four factors for all 15 instruments: hydrocarbon-like organic aerosol (HOA), cooking-related organic aerosol (COA), biomass burning-related organic aerosol (BBOA) and secondary oxygenated organic aerosol (OOA). Individual application and optimisation of the ME-2 boundary conditions (profile constraints) are discussed together with the investigation of the influence of alternative anchors (reference profiles). A comparison of the ME-2 source apportionment output of all 15 instruments resulted in relative SD from the mean between 13.7 and 22.7% of the source's average mass contribution depending on the factors (HOA: 14.3 ± 2.2%, COA: 15.0 ± 3.4%, OOA: 41.5 ± 5.7%, BBOA: 29.3 ± 5.0%). Factors which tend to be subject to minor factor mixing (in this case COA) have higher relative uncertainties than factors which are recognised more readily like the OOA. Averaged over all factors and instruments the relative first SD from the mean of a source extracted with ME-2 was 17.2%.

Description: Mass concentrations of sulphate, nitrate, ammonium, organic carbon (OC), elemental carbon (EC) were determined from real time single particle data in the size range 0.1–3.0 μm measured by an Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) at urban and rural sites in Canada. To quantify chemical species within individual particles measured by an ATOFMS, ion peak intensity of m/z −97 for sulphate, −62 for nitrate, +18 for ammonium, +43 for OC, and +36 for EC were scaled using the number and size distribution data by an Aerodynamic Particle Sizer (APS) and a Fast Mobility Particle Sizer (FMPS). Hourly quantified chemical species from ATOFMS single-particle analysis were compared with collocated fine particulate matter (aerodynamic diameter 〈 2.5 μm, PM2.5) chemical composition measurements by an Aerosol Mass Spectrometer (AMS) at a rural site, a Gas-Particle Ion Chromatograph (GPIC) at an urban site, and a Sunset Lab field OCEC analyzer at both sites. The highest correlation was found for nitrate, with correlation coefficients (Pearson r) of 0.89 (ATOFMS vs. GPIC) and 0.85 (ATOFMS vs. AMS). ATOFMS mass calibration factors, determined for the urban site, were used to calculate mass concentrations of the major PM2.5 chemical components at the rural site near the US border in southern Ontario. Mass reconstruction using the ATOFMS mass calibration factors agreed very well with the PM2.5 mass concentrations measured by a Tapered Element Oscillating Microbalance (TEOM, r = 0.86) at the urban site and a light scattering monitor (DustTrak, r = 0.87) at the rural site. In the urban area nitrate was the largest contributor to PM2.5 mass in the winter, while organics and sulphate contributed ~64 % of the summer PM2.5 in the rural area, suggesting a strong influence of regional/trans-boundary pollution. The mass concentrations of five major species in ten size-resolved particle-types and aerosol acidity of each particle-type were determined for the rural site. On a mass basis sulphate and OC rich particle-types (OC-S and OC-S-N) accounted for up to 59 % of the particles characterized and aerosols were weakly acidic in the rural area. This is the first study to estimate hourly quantitative data of sulphate, nitrate, ammonium, OC and EC in ambient particles from scaled ATOFMS single particle analysis; these were closely comparable with collocated high time resolution data of sulphate, nitrate and ammonium detected by AMS and GPIC.

Description: During the winter component of the SPORT (Seasonal Particle Observations in the Region of Toronto) field campaign, particulate non-refractory chemical composition and concentration of selected volatile organic compounds (VOCs) were measured by an Aerodyne time-of-flight aerosol mass spectrometer (AMS) and a proton transfer reaction-mass spectrometer (PTR-MS), respectively. Sampling was performed in downtown Toronto ~15 m from a major road. The mass spectra from the AMS and PTR-MS were combined into a unified dataset, which was analysed using positive matrix factorization (PMF). The two instruments were given balanced weight in the PMF analysis by the application of a scaling factor to the uncertainties of each instrument. A residual based metric, Δesc, was used to evaluate the instrument relative weight within each solution. The PMF analysis yielded a 6-factor solution that included factors characteristic of regional transport, local traffic emissions, charbroiling and oxidative processing. The unified dataset provides information on emission sources (particle and VOC) and atmospheric processing that cannot be obtained from the datasets of the individual instruments: (1) apportionment of oxygenated VOCs to either direct emission sources or secondary reaction products; (2) improved correlation of oxygenated aerosol factors with photochemical age; and (3) increased detail regarding the composition of oxygenated organic aerosol factors. This analysis represents the first application of PMF to a unified AMS/PTR-MS dataset.

Description: Regional-scale chemical transport model predictions of urban organic aerosol to date tend to be biased low relative to observations, a limitation with important implications for applying such models to human exposure health studies. We used a nested version of Environment Canada's AURAMS model (42- to- 15- to- 2.5-km nested grid spacing) to predict organic aerosol concentrations for a temporal and spatial domain corresponding to the Border Air Quality and Meteorology Study (BAQS-Met), an air-quality field study that took place in the southern Great Lakes region in the summer of 2007. The use of three different horizontal grid spacings allowed the influence of this parameter to be examined. A domain-wide average for the 2.5-km domain and a matching 15-km subdomain yielded very similar organic aerosol averages (4.8 vs. 4.3 μg m−3, respectively). On regional scales, secondary organic aerosol dominated the organic aerosol composition and was adequately resolved by the 15-km model simulation. However, the shape of the organic aerosol concentration histogram for the Windsor urban station improved for the 2.5-km simulation relative to those from the 42- and 15-km simulations. The model histograms for the Bear Creek and Harrow rural stations were also improved in the high concentration "tail" region. As well the highest-resolution model results captured the midday 4 July organic-aerosol plume at Bear Creek with very good temporal correlation. These results suggest that accurate simulation of urban and large industrial plumes in the Great Lakes region requires the use of a high-resolution model in order to represent urban primary organic aerosol emissions, urban VOC emissions, and the secondary organic aerosol production rates properly. The positive feedback between the secondary organic aerosol production rate and existing organic mass concentration is also represented more accurately with the highest-resolution model. Not being able to capture these finer-scale features may partly explain the consistent negative bias reported in the literature when urban-scale organic aerosol evaluations are made using coarser-scale chemical transport models.

Description: As part of the BAQS-Met 2007 field campaign, Aerodyne time-of-flight aerosol mass spectrometers (ToF-AMS) were deployed at two sites in southwestern Ontario from 17 June to 11 July 2007. One instrument was located at Harrow, ON, a rural, agriculture-dominated area approximately 40 km southeast of the Detroit/Windsor/Windsor urban area and 5 km north of Lake Erie. The second instrument was located at Bear Creek, ON, a rural site approximately 70 km northeast of the Harrow site and 50 km east of Detroit/Windsor. Positive matrix factorization analysis of the combined organic mass spectral dataset yields factors related to secondary organic aerosol (SOA), direct emissions, and a factor tentatively attributed to the reactive uptake of isoprene and/or condensation of its early generation reaction products. This is the first application of PMF to simultaneous AMS measurements at different sites, an approach which allows for self-consistent, direct comparison of the datasets. Case studies are utilized to investigate processing of SOA from (1) fresh emissions from Detroit/Windsor and (2) regional aerosol during periods of inter-site flow. A strong correlation is observed between SOA/excess CO and photochemical age as represented by the NOx/NOy ratio for Detroit/Windsor outflow. Although this correlation is not evident for more aged air, measurements at the two sites during inter-site transport nevertheless show evidence of continued atmospheric processing by SOA production. However, the rate of SOA production decreases with airmass age from an initial value of ~10.1 μg m−3 ppmvCO−1 h−1 for the first ~10 h of plume processing to near-zero in an aged airmass (i.e. after several days). The initial SOA production rate is comparable to the observed rate in Mexico City over similar timescales.

Description: Observations from the 2007 Border Air Quality and Meteorology Study (BAQS-Met 2007) in Southern Ontario, Canada, were used to evaluate predictions of primary organic aerosol (POA) and two other carbonaceous species, black carbon (BC) and carbon monoxide (CO), made for this summertime period by Environment Canada's AURAMS regional chemical transport model. Particle component-based factor analysis was applied to aerosol mass spectrometer measurements made at one urban site (Windsor, ON) and two rural sites (Harrow and Bear Creek, ON) to derive hydrocarbon-like organic aerosol (HOA) factors. A novel diagnostic model evaluation was performed by investigating model POA bias as a function of HOA mass concentration and indicator ratios (e.g. BC/HOA). Eight case studies were selected based on factor analysis and back trajectories to help classify model bias for certain POA source types. By considering model POA bias in relation to co-located BC and CO biases, a plausible story is developed that explains the model biases for all three species. At the rural sites, daytime mean PM1 POA mass concentrations were under-predicted compared to observed HOA concentrations. POA under-predictions were accentuated when the transport arriving at the rural sites was from the Detroit/Windsor urban complex and for short-term periods of biomass burning influence. Interestingly, the daytime CO concentrations were only slightly under-predicted at both rural sites, whereas CO was over-predicted at the urban Windsor site with a normalized mean bias of 134%, while good agreement was observed at Windsor for the comparison of daytime PM1 POA and HOA mean values, 1.1 μg m−3 and 1.2 μg m−3, respectively. Biases in model POA predictions also trended from positive to negative with increasing HOA values. Periods of POA over-prediction were most evident at the urban site on calm nights due to an overly-stable model surface layer. This model behaviour can be explained by a combination of model under-estimation of vertical mixing at the urban location, under-representation of PM emissions for on-road traffic exhaust along major urban roads and highways, and a more structured allocation of area POA sources such as food cooking and dust emissions to urban locations. A downward trend in POA bias was also observed at the urban site as a function of the BC/HOA indicator ratio, suggesting a possible association of POA under-prediction with under-representation of diesel combustion sources. An investigation of the emission inventories for the province of Ontario and the nearby US state of Indiana also suggested that the top POA area emission sources (food cooking, organic-bound to dust, waste disposal burning) dominated over mobile and point sources, again consistent with a mobile under-estimation. We conclude that more effort should be placed at reducing uncertainties in the treatment of several large POA emission sources, in particular food cooking, fugitive dust, waste disposal burning, and on-road traffic sources, and especially their spatial surrogates and temporal profiles. This includes using higher spatial resolution model grids to better resolve the urban road network and urban food cooking locations. We also recommend that additional sources of urban-scale vertical mixing in the model, such as a stronger urban heat island effect and vehicle-induced turbulence, would help model predictions at urban locations, especially at night time.

Description: Measurements of aerosol composition, volatile organic compounds, and CO are used to determine biogenic secondary organic aerosol (SOA) concentrations at a rural site 70 km north of Toronto. These biogenic SOA levels are many times higher than past observations and occur during a period of increasing temperatures and outflow from Northern Ontario and Quebec forests in early summer. A regional chemical transport model approximately predicts the event timing and accurately predicts the aerosol loading, identifying the precursors as monoterpene emissions from the coniferous forest. The agreement between the measured and modeled biogenic aerosol concentrations contrasts with model underpredictions for polluted regions. Correlations of the oxygenated organic aerosol mass with tracers such as CO support a secondary aerosol source and distinguish biogenic, pollution, and biomass burning periods during the field campaign. Using the Master Chemical Mechanism, it is shown that the levels of CO observed during the biogenic event are consistent with a photochemical source arising from monoterpene oxidation. The biogenic aerosol mass correlates with satellite measurements of regional aerosol optical depth, indicating that the event extends across the eastern Canadian forest. This regional event correlates with increased temperatures, indicating that temperature-dependent forest emissions can significantly affect climate through enhanced direct optical scattering and higher cloud condensation nuclei numbers.