Effect of industrialization on the differences in sources and composition of ambient PM2.5 in two Southern Ontario locations.

PM2.5 was sampled over a seven-year period (2013-2019) at two locations ∼50 km apart in Southern Ontario (concurrently for five years: 2015-2019). One is a heavily industrialized site (Hamilton), while the other was a rural site (Simcoe). To assess the impact of industrialization on the composition and sources of PM affecting air quality in these two locations, positive matrix factorization coupled with dispersion normalization (DN-PMF) was used to identify six and eight factors at Simcoe and Hamilton, respectively. The Simcoe factors in order of diminishing PM mass contribution were: particulate sulphate (pSO4), secondary organic aerosol (SOA), crustal matter, particulate nitrate (pNO3), biomass burning, and vehicular emissions. At Hamilton, the effects of industrialization were observed by the ∼36% higher average ambient PM2.5 concentration for the study period as well as the presence of factors unique to metallurgy, i.e., coking and steelmaking, compared to Simcoe. The coking and steelmaking factors contributed ∼15% to the PM mass at Hamilton. Seasonal variants of appropriate nonparametric trend tests with the associated slopes (Sen's) were used to assess statistically significant changes in the factor contributions to PM2.5 over time. Specifically at Hamilton, a significant decline in PM contributions was noted for coking (-0.03 µg/m³/yr or -4.1%/yr) while steelmaking showed no statistically significant decline over the study period. Other factors at Hamilton that showed statistically significant declines over the study period were: pSO4 (-0.27 µg/m³/yr or -12.6%/yr), biomass burning (-0.05 µg/m³/yr or -9.02%/yr), crustal matter (-0.03 µg/m³/yr or -5.28%/yr). These factors mainly accounted for the significant decline in PM2.5 over the study period (-0.35 µg/m³/yr or -4.24%/yr). This work shows the importance of long-term monitoring in assessing the unique contributions and temporal changes of industrialization on air quality in Ontario and similarly affected locations.

Trace Metals in Global Air: First Results from the GAPS and GAPS Megacities Networks.

Trace metals, as constituents of ambient air, can have impacts on human and environmental health. The Global Atmospheric Passive Sampling (GAPS) and GAPS Megacities (GAPS-MC) networks investigated trace metals in the air at 51 global locations by deploying polyurethane foam disk passive air samplers (PUF-PAS) for periods of 3-12 months. Aluminum and iron exhibited the highest concentrations in air (x̅ = 3400 and 4630 ng/m3, respectively), with notably elevated values at a rural site in Argentina thought to be impacted by resuspended soil. Urban sites had the highest levels of toxic Pb and Cd, with enrichment factors suggesting primarily anthropogenic influences. High levels of As at rural sites were also observed. Elevated trace metal concentrations in cities are associated with local emissions and higher PM2.5 and PM10 concentrations. Brake and tire wear-associated metals Sb, Cu, and Zn are significantly correlated and elevated at urban locations relative to those at background sites. These data demonstrate the versatility of PUF-PAS for measuring trace metals and other particle-associated pollutants in ambient air in a cost-effective and simple manner. The data presented here will serve as a global baseline for assessing future changes in ambient air associated with industrialization, urbanization, and population growth.

Identification of decadal trends and associated causes for organic and elemental carbon in PM2.5 at Canadian urban sites.

Chemically resolved data for fine particulate matter (PM2.5) have been collected across Canada since 2003 through the National Air Pollution Surveillance (NAPS) network. Seven urban sites that have 10-17 years (2003-2019) of PM2.5 organic carbon (OC) and elemental carbon (EC) data were selected for analysis of decadal trends of OC, EC, and OC/EC ratio using the Ensemble Empirical Mode Decomposition method. Results showed that OC and EC decreased by 0.009-0.072 µg m-3 yr-1 and 0.028-0.049 µg m-3 yr-1, or 0.77-3.1 % yr-1 and 3.2-6.7 % yr-1, respectively, depending on the location. The more rapid decrease in EC than OC resulted in an increasing trend in the OC/EC ratio of 0.03-0.19 yr-1 across the sites. Macro-tracer approach was used to estimate source attributions of OC and EC from wood burning, fossil fuel combustion, and secondary aerosol formation. Using this approach, it was identified that the significant decrease in EC during the past decade was predominately caused by reduced on-road emissions. The decreased emissions from wood burning and transportation dominated the decline of OC, but such a decline was largely offset by the enhanced secondary organic aerosol (SOA) formation, resulting in much weaker decline of OC than EC. The enhanced SOA formation was due to the increased biogenic emissions fully offsetting the decreased anthropogenic emissions for volatile organic compounds. These findings highlight the need for quantifying biogenic sources of VOCs and other oxidants that are involved in OC formation at the national scale.

Insights into Elemental Composition and Sources of Fine and Coarse Particulate Matter in Dense Traffic Areas in Toronto and Vancouver, Canada.

Traffic is a significant pollution source in cities and has caused various health and environmental concerns worldwide. Therefore, an improved understanding of traffic impacts on particle concentrations and their components could help mitigate air pollution. In this study, the characteristics and sources of trace elements in PM2.5 (fine), and PM10-2.5 (coarse), were investigated in dense traffic areas in Toronto and Vancouver, Canada, from 2015-2017. At nearby urban background sites, 24-h integrated PM samples were also concurrently collected. The PM2.5 and PM10-2.5 masses, and a number of elements (i.e., Fe, Ba, Cu, Sb, Zn, Cr), showed clear increases at each near-road site, related to the traffic emissions resulting from resuspension and/or abrasion sources. The trace elements showed a clear partitioning trend between PM2.5 and PM10-2.5, thus reflecting the origin of some of these elements. The application of positive matrix factorization (PMF) to the combined fine and coarse metal data (86 total), with 24 observations at each site, was used to determine the contribution of different sources to the total metal concentrations in fine and coarse PM. Four major sources were identified by the PMF model, including two traffic non-exhaust (crustal/road dust, brake/tire wear) sources, along with regional and local industrial sources. Source apportionment indicated that the resuspended crustal/road dust factor was the dominant contributor to the total coarse-bound trace element (i.e., Fe, Ti, Ba, Cu, Zn, Sb, Cr) concentrations produced by vehicular exhaust and non-exhaust traffic-related processes that have been deposited onto the surface. The second non-exhaust factor related to brake/tire wear abrasion accounted for a considerable portion of the fine and coarse elemental (i.e., Ba, Fe, Cu, Zn, Sb) mass at both near-road sites. Regional and local industry contributed mostly to the fine elemental (i.e., S, As, Se, Cd, Pb) concentrations. Overall, the results show that non-exhaust traffic-related processes were major contributors to the various redox-active metal species (i.e., Fe, Cu) in both PM fractions. In addition, a substantial proportion of these metals in PM2.5 was water-soluble, which is an important contributor to the formation of reactive oxygen species and, thus, may lead to oxidative damage to cells in the human body. It appears that controlling traffic non-exhaust-related metals emissions, in the absence of significant point sources in the area, could have a pronounced effect on the redox activity of PM, with broad implications for the protection of public health.

Characterization and source apportionment of airborne particulate elements in the Athabasca oil sands region.

The oil sands industries in Alberta, Canada are potential sources of particulate-bound elements in the region. This study explored the ambient concentrations and size distributions, and conducted source apportionment of 48 particulate elements, based on samples collected in 2016-2017 at four air monitoring sites in the Athabasca oil sands region: Fort McKay (AMS1), Buffalo Viewpoint (AMS4), Wapasu Creek (AMS17), and Stoney Mountain (AMS18). Element concentrations in fine and coarse particulate matter (PM2.5 and PM2.5-10 respectively) at the four sites were generally lower than their typical concentrations at other urban and industrial sites in North America. Among all elements, S was the most abundant in PM2.5 with mean concentrations ranging from 189 ng/m3 (AMS18) to 284 ng/m3 (AMS1). Of the trace, toxic elements in PM2.5, Zn was the most abundant with mean concentrations ranging from 3.43 ng/m3 (AMS18) to 5.37 ng/m3 (AMS4). Positive Matrix Factorization (PMF) modeling of the element concentrations in PM2.5 was used for source apportionment for Zone1 (including AMS 1, 4, and 17, situated closer to industrial activities) and for Zone2 (including AMS18, a background site). The sources of elements for Zone1, included crustal dust, bitumen processing, haul road dust, and biomass burning that explained ~33%, ~43%, ~15%, and ~9% of the total resolved elemental mass, respectively. The sources of elements for Zone2, included Pb-rich source, biomass burning, fugitive oil sands, crustal dust, and bitumen processing explaining ~8%, ~7%, ~3%, ~22%, and ~60% of the total resolved elemental mass, respectively. Elemental mass concentrations of the bitumen processing source factor at Zone2 was two-thirds of that in Zone1. Overall, mass proportions of the bitumen processing source factor at all four sites were significant, suggesting that the oil sands industries played a key role in ambient element concentration levels in the region.

Spatiotemporal trends of PM2.5 and its major chemical components at urban sites in Canada.

To evaluate the effectiveness of emission control regulations designed for reducing air pollution, chemically resolved PM2.5 data have been collected across Canada through the National Air Pollution Surveillance network in the past decade. 24-hr time integrated PM2.5 collected at seven urban and two rural sites during 2010-2016 were analyzed to characterize geographical and seasonal patterns and associated potential causes. Site-specific seven-year mean gravimetric PM2.5 mass concentrations ranged from 5.7 to 9.6 µg/m3. Seven-year mean concentrations of SO42-, NO3-, NH4+, organic carbon (OC), and elemental carbon (EC) were in the range of 0.68 to 1.6, 0.21 to 1.5, 0.27 to 0.71, 1.1 to 1.9, and 0.37 to 0.71 µg /m3, accounting for 10.8%-18.1%, 3.7%-16.7%, 4.7%-7.4%, 18.4%-21.0%, and 6.4%-10.6%, respectively, of gravimetric PM2.5 mass. PM2.5 and its five major chemical components showed higher concentrations in southeastern Canada and lower values in Atlantic Canada, with the seven-year mean ratios between the two regions being on the order of 1.7 for PM2.5 and 1.8-7.1 for its chemical components. When comparing the concentrations between urban and rural sites within the same region, those of SO42- and NH4+ were comparable, while those of NO3-, OC, and EC were around 20%, 40%-50%, and 70%-80%, respectively, higher at urban than rural sites, indicating the regional scale impacts of SO42- and NH4+ and effects of local sources on OC and EC. Monthly variations generally showed summertime peaks for SO42- and wintertime peaks for NO3-, but those of NH4+, OC, and EC exhibited different seasonality at different locations.

The influence of chemical composition, aerosol acidity, and metal dissolution on the oxidative potential of fine particulate matter and redox potential of the lung lining fluid.

Air pollution is a major environmental health risk and it contributes to respiratory and cardiovascular diseases and excess mortality worldwide. The adverse health effects have been associated with the inhalation of fine particulate matter (PM2.5) and induction of respiratory oxidative stress. In this work, we quantified the oxidative potential (OP) of PM2.5 from several Canadian cities (Toronto, Hamilton, Montreal, Vancouver) using a recently developed bioanalytical method which measures the oxidation of lung antioxidants, glutathione, cysteine, and ascorbic acid, the formation of glutathione disulfide and cystine, and the related redox potential (RP) in a simulated epithelial lining fluid (SELF). We evaluated the application of empirical SELF RP as a new metric for aerosol OP. We further investigated how PM2.5 chemical composition and OP are related across various emission source sectors and whether these features are linked to specific properties of aerosol aqueous phase, such as pH and metal-ligand complexation. The OP indicators including SELF RP were strongly correlated among each other, indicating that the empirical RP could be used as a reliable metric in future studies. OP based on ascorbic acid showed dependency on the emission source sectors, most likely due to variation in the solubility of Fe. Traffic emissions resulted in the highest OP, followed by industrial emissions and resuspended crustal matter. OP presented low correlation with PM2.5 concentrations, low-moderate correlation with the aerosol organic matter, and moderate-strong association with black carbon and transition metals across the sites. We did not find strong association between the concentration of biomass burning tracers and OP. Copper was the only metal that showed high association with OP across all sites, whereas the correlation with other metals, such as iron, manganese, and titanium, showed clear dependency on the source sectors. The aerosol pH correlated negatively with ambient temperature and positively with biomass burning tracers and the levels of nitrate, ammonium, and aerosol liquid water content. The solubility of Fe was associated with sulfate and aerosol pH at most sites, suggesting the involvement of proton-mediated dissolution pathway, while this was not visible at the site influenced by industrial emission, most likely due to the abundance of pyrogenic Fe. The effect of metal-ligand complexation on the solubility of transition metals, in particular Fe, was clearly observed at all sites, whereas a combined effect with aerosol pH, and a subsequent impact on OP, was only seen at the traffic site in Toronto. The enhanced solubility of Fe due to proton- and ligand-mediated dissolution pathways and subsequent formation of reactive oxygen species may in part explain the health effects of PM2.5 seen in previous epidemiological studies.

Characterization of benzene polycarboxylic acids and polar nitroaromatic compounds in atmospheric aerosols using UPLC-MS/MS.

The molecular characterization of water-soluble organic compounds (WSOC), a large fraction of the organic mass found in the atmospheric aerosols, is important to better understand emissions and atmospheric processes influencing the particulate pollution in most urban areas. This study deals with the development of a routine method using ultrahigh pressure liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (UPLC-ESI-MS/MS) for rapid analysis of primary and secondary organic compounds distributed among three classes: (i) benzene polycarboxylic acids; (ii) nitroaromatic acids and (iii) nitrophenols in ambient particles. Using an UPLC HSS T3 column with a mobile phase consisting of formic acid/acetonitrile under gradient elution, all target analytes were eluted within a total time of 12 min. Although some targeted analytes with different m/z were not resolved, a quantitation of these compounds was carried by distinct multiple reaction monitoring (MRM) transitions. Quality parameters of the method were established. The method was proven to be sensitive with limits of detection ranged from 0.02 to 0.89 ng/mL. Together with a simple sample preparation and the use of labeled internal standards, the method was confirmed to be robust and reliable to determine a large number of organic tracers in atmospheric particulate matter samples. The analytical procedure was also applied to assess the abundance and characteristics of target analytes in PM2.5 emitted from diesel and gasoline-powered engines, and Urban Dust and Diesel Particulate Matter Standard Reference Materials (SRM 1649b and SRM 1650b, respectively). The obtained results suggest that trimellitic, 4-hydroxyphthalic and 4-nitrophthalic acids may be used as potential tracers for diesel engine emissions. Clear differences in distribution of target species were observed between urban PM2.5 affected by the traffic and biomass burning emissions.

Investigation of isomeric structures in a commercial mixture of naphthenic acids using ultrahigh pressure liquid chromatography coupled to hybrid traveling wave ion mobility-time of flight mass spectrometry.

The separation of isomeric naphthenic acids (NAs) is of high importance to obtain more detailed and therefore useful information to understand their fate, transport, toxicity and potential removal treatment methodologies. In the current study, the capabilities of the ultrahigh pressure liquid chromatography/traveling wave ion mobility-time of flight mass spectrometry (UPLC/TWIM-TOF-MS) to separate and study different isomeric structures of NAs were investigated. Fifty seven standard compounds belonging to different chemical families of classical NAs were analyzed to obtain their experimental drift times in addition to chromatographic retention time and mass-to-charge information (m/z). These acyclic and cyclic molecules yielded ions with collision cross section (CCS) values ranging from 110 to 210 Å2. The feasibility of the UPLC/TWIM-TOF-MS method to provide a higher degree of confidence in the identification of isomeric structures was evaluated by analyzing the commercial (Sigma-Aldrich) NAs mixture. Identification and structure confirmation of several alicyclic compounds of similar m/z in the NAs mixture were possible by this method. For instance, the presence of previously tentatively identified compounds by the ultrahigh pressure liquid chromatography/quadrupole time of flight mass spectrometry (UPLC/QTOF-MS), such as 4-tert-butylcyclohexanoic acid, 4-dicyclohexylacetic acid or 3,5-dimethyladamantane-1-carboxylic acid, was confirmed. Combining ion mobility separation with UPLC/TOF-MS gives a higher level of selectivity to the overall method by selective interrogation of specific retention time, mass-to-charge and mobility regions. However, there are cases where it is not possible to resolve many similar molecules such as acyclic isomeric compounds in commercial NAs mixture by this technique. This was likely due to the very small CCS area differences among the structural isomeric species. Considerable improvements in the ion mobility resolution and separation will be required for this technique to be able to resolve isomeric species with slight differences in physicochemical properties (e.g., size and structure).

Application of ultrahigh-performance liquid chromatography-quadrupole time-of-flight mass spectrometry for the characterization of organic aerosol: Searching for naphthenic acids.

Naphthenic acids (NAs) are naturally occurring constituents of hydrocarbon deposits (petroleum, oil sands bitumen, and crude oils), and present in any facilities that extract, process or use crude oil or bitumen for manufacturing. In the Athabasca oil sands region (AOSR) of Alberta, Canada, this diverse group of saturated acyclic, monocyclic, and polycyclic carboxylic acids is present in bitumen and in tailing ponds. Little is known about the occurrence of residual oil sands derived organic material, including NAs, in atmospheric particulate matter (PM). This work describes the optimization of an ultrahigh-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC/QTOF-MS) method to characterize and identify classical NAs in atmospheric PM. Under the optimum conditions, analysis of the Sigma-Aldrich technical NA STD Mix showed the absence of saturated fatty acids, while branched and cyclic NAs isomers with carbon number ranged between 10 and 30, and Z families between 0 and -12 were detected. Higher molecular weight NAs representing compounds with carbon number ranging between 30 and 40 were identified in the analyzed PM samples collected in AOSR. In contrast, isomeric branched acyclic NAs were not detected in the background (PM-R) samples collected far from AOSR. Except for fatty acids (Z=0), other Z homologues were also not detectable or present at very low concentration in the analysed PM-R samples. Preliminary examination of NA profiles showed that the composition of NAs in PM collected in close proximity to surface mining operations is predominantly "refractory" high molecular weight branched NAs, differing from that collected closer to upgraders and tailings ponds. It is suspected that dust released from the mine faces and dry tailings in the AOSR are sources of NAs to atmosphere. Further samples should be examined to confirm findings. This preliminary study presents, to our knowledge, the first direct identification of branched acyclic and cyclic NAs in atmospheric PM.

Contrasting biological potency of particulate matter collected at sites impacted by distinct industrial sources.

BACKGROUND: Industrial sources contribute a significant proportion of anthropogenic particulate matter (PM) emissions, producing particles of varying composition that may differentially impact health. This study investigated the in vitro toxicity of ambient PM collected near industrial sites in relation to particle size and composition. METHODS: Size-fractionated particles (ultrafine, PM0.1-2.5, PM2.5-10, PM>10) were collected in the vicinity of steel, copper, aluminium, and petrochemical industrial sites. Human lung epithelial-like A549 and murine macrophage-like J774A.1 cells were exposed for 24 h to particle suspensions (0, 30, 100, 300 µg/cm2). Particle potency was assessed using cytotoxic (resazurin reduction, lactate dehydrogenase (LDH) release) and inflammatory (cytokine release) assays, and regressed against composition (metals, polycyclic aromatic hydrocarbons (PAHs), endotoxin). RESULTS: Coarse (PM2.5-10, PM>10) particle fractions were composed primarily of iron and aluminium; in contrast, ultrafine and fine (PM0.1-2.5) fractions displayed considerable variability in metal composition (especially water-soluble metals) across collection sites consistent with source contributions. Semi-volatile and PM-associated PAHs were enriched in the fine and coarse fractions collected near metal industry. Cell responses to exposure at equivalent mass concentrations displayed striking differences among sites (SITE x SIZE and SITE x DOSE interactions, p < 0.05), suggesting that particle composition, in addition to size, impacted particle toxicity. While both J774A.1 and A549 cells exhibited clear particle size-dependent effects, site-dependent differences were more pronounced in J774A.1 cells, suggesting greater sensitivity to particle composition. Plotting particle potency according to cytotoxic and inflammatory response grouped particles by size and site, and showed that particles of similar composition tended to cluster together. Cytotoxic effects in J774A.1 cells correlated with metal and PAH content, while inflammatory responses were associated primarily with endotoxin content in coarse particles. CONCLUSIONS: Industrial sources produce particulate emissions with varying chemical composition that differ in their in vitro potency in relation to particle size and the levels of specific constituents.

Air toxics in Canada measured by the National Air Pollution Surveillance (NAPS) program and their relation to ambient air quality guidelines.

UNLABELLED: This study reports ambient concentrations of 63 air toxics that were measured in Canada by the National Air Pollution Surveillance (NAPS) program over the period 2009-2013. Measured concentrations are compared with ambient air quality guidelines from Canadian jurisdictions, and compounds that exceeded guidelines are identified and discussed. Although this study does not assess risk or cumulative effects, air toxics that approached guidelines are also identified so that their potential contribution to ambient air toxics pollution can be considered. Eleven air toxics exceeded at least one guideline, and an additional 16 approached guidelines during the study period. Four compounds were measured using methods whose detection limits exceeded a guideline value, three of which could not be compared with guidelines, since they were not detected in any samples. The assessment of several metal(loid) concentrations is tentative, since they were measured only in fine particulate matter (PM) but compared with guidelines based on coarse or total PM. Improvements to sampling and analysis techniques for the latter compounds as well as for those whose methods are subject to known uncertainties would improve confidence in reported concentrations and their relation to applicable guidelines. Analysis of sampling strategies for all compounds found to exceed or approach guidelines would contribute to ensuring that their spatiotemporal coverage is adequate. Examination of the air toxics not measured by NAPS but having guidelines in Canadian jurisdictions or being included in other programs such as the U.S. National-Scale Air Toxics Assessment (NATA) would contribute to ensuring that the full suite of pollutants relevant to ambient air quality in Canada is subject to adequate study. The results of this study can be applied to evaluating the effectiveness of toxic substances management in Canada. IMPLICATIONS: Recent measurements of 63 air toxics in Canada by the National Air Pollution Surveillance (NAPS) program showed that 11 compounds exceeded daily or annual ambient air quality guidelines and that an additional 16 compounds approached such guidelines within an order of magnitude. The results of this study can be applied to evaluating the effectiveness of toxic substances management in Canada and to identifying compounds that merit further investigation.

Cytotoxic and inflammatory potential of size-fractionated particulate matter collected repeatedly within a small urban area.

BACKGROUND: Exposure to coarse, fine, and ultrafine particles is associated with adverse population health impacts. We investigated whether size-fractionated particles collected repeatedly in the vicinity of industrial (steel mills and associated coking operations, wastewater treatment), high traffic, and residential areas display systematic differences in biological potency. METHODS: Particulate matter (PM<0.1, PM0.1-0.5, PM0.5-2.5, PM2.5-10, PM>10) samples collected at sites within Windsor, Ontario, were screened for biological potency in human A549 lung epithelial and murine J774A.1 macrophage-like cells using cytotoxicity bioassays (cellular ATP, resazurin reduction, lactate dehydrogenase (LDH) release), cytokine production, and transcript profiles. Potency was determined from the slope of each dose-effect relationship. RESULTS: Cytotoxic potency varied across size fractions and within a fraction across sites and sampling periods, suggesting that particle composition, in addition to size and mass, affected particle toxicity. While ATP and LDH profiles showed some similarity, resazurin reduction (a measure of metabolic activity) exhibited a unique pattern of response, indicating that the cytotoxicity assays were sensitive to distinct particle characteristics. Chemical speciation varied in relation to prevailing winds, consistent with enrichment of source emissions (e.g. higher metal and polycyclic aromatic hydrocarbon content downwind of the industrial site). Notwithstanding this variability, site-dependent differences in particle toxicity were evident, including greater potency of coarse fractions at the industrial site and of ultrafine particles at the traffic site (Site × Size interactions, p < 0.05). Regression of potency against particle constituents revealed correlations between resazurin reduction, induction of metal-responsive genes, and metal content, which were particularly strong for the coarse fraction, and between cytokine release and endotoxin, suggesting that these factors were important drivers of biological effects that explain, at least in part, the contrasting potencies of particles compared on an equivalent mass basis. CONCLUSIONS: The data show that 1) particle potency and composition can exhibit significant temporal variation in relation to source contributions; 2) sources may differentially impact the potency of specific size fractions; and 3) particle constituents, notably metals and endotoxin, may elicit distinct biological responses. Together, the data are consistent with the notion that sources and composition, in addition to size and mass concentration, are relevant to particle toxicity.

Chemical characterization of exhaust emissions from selected canadian marine vessels: the case of trace metals and lanthanoids.

This paper reports the chemical composition of exhaust emissions from the main engines of five ocean going cargo vessels, as they traveled in Canadian waters. The emission factors (EFs) of PM2.5 and SO2 for vessels tested on various intermediate fuel oils (IFO), ranged from 0.4 to 2.2 g kW(-1) hr(-1) and 4.7 to 10.3 g kW(-1) hr(-1), respectively, and were mainly dependent on the content of sulfur in the fuel. Average NOx, CO, and CO2 EFs for these tests were 12.7, 0.45, and 618 g kW(-1) hr(-1), respectively and were generally below benchmark values commonly used by regulatory agencies. The composition of PM2.5 was dominated by hydrated sulfates, organic carbon and trace metals which accounted for 80-97% of total PM2.5 mass. A substantial decrease of measured emission factors for PM2.5 and SO2 was observed when the fuel was changed from IFO to marine diesel oil (MDO), in one of the tested vessels. The main component of PM2.5 in this case was organic carbon accounting for 65% of PM2.5 mass. In addition to commonly reported pollutants, this study presents EFs of the lanthanoid elements and showed that their distribution patterns in ship-exhaust PM2.5 were very similar to the PM2.5 emitted by oil refining facilities. Hence, using La:Ce:V tertiary diagrams and La/V ratios is necessary to distinguish ship plumes from primary emissions related to accidental and/or routine operation of oil-refining industry.

Structural characterization of organic aerosol using Fourier transform ion cyclotron resonance mass spectrometry: aromaticity equivalent approach.

RATIONALE: A challenge of atmospheric particulate matter (PM) analysis is the understanding of the sources and chemistry of complex organic aerosols, especially the water-soluble organic compounds (WSOC) fraction, a key component of atmospheric fine PM (PM(2.5)). The sources of WSOC are not well understood and, thus, the molecular characterization of WSOC is important because it provides insight into aerosol sources and the underlying mechanisms of secondary organic aerosols formation and transformation. METHODS: In this study, molecular characterization of WSOC was achieved using Fourier transform ion cyclotron resonance mass spectrometry. The aromaticity equivalent (X(c)), a new parameter calculated from the assigned molecular formula, is introduced to improve the identification and characterization of aromatic and condensed aromatic compounds in WSOC. Diesel PM (DPM) and atmospheric PM samples were used to study the applicability of the proposed method. RESULTS: Threshold values of X(c) ≥2.5000 and X(c) ≥2.7143 are proposed as unambiguous minimum criteria for the presence of aromatics and condensed aromatics, respectively. By using these criteria, 36% of precursors were defined as aromatics and condensed aromatics in the DPM. For comparison, 21% of aromatic and condensed aromatic compounds were defined using the Aromaticity Index (AI) classification. The lower estimates by the AI approach are probably due to the failure to recognize aromatics and condensed aromatics with longer alkyl chains. The estimated aromatic and condensed aromatic fractions in the atmospheric aerosol samples collected in an industrial area affected by biomass burning events were 51.2 and 50.0%, respectively. CONCLUSIONS: The advantage of employing this parameter is that X(c) would have a constant value for each proposed core structure regardless of the degree of alkylation, and thus visual representation and structural interpretations of the spectra become advantageous for characterizing and comparing complex samples. In addition, the proposed parameter complements the AI classification and identification of aromatic and condensed aromatic structures in complex matrices.

Impacts of air cleaners on indoor air quality in residences impacted by wood smoke.

Residential wood combustion is an important source of ambient air pollution, accounting for over 25% of fine particulate matter (PM2.5) emissions in Canada. In addition to these ambient contributions, wood smoke pollutants can enter the indoor environment directly when loading or stoking stoves, resulting in a high potential for human exposure. A study of the effectiveness of air cleaners at reducing wood smoke-associated PM2.5 of indoor and outdoor origin was conducted in 31 homes during winter 2009-10. Day 1, the residents' wood burning appliance operated as usual with no air cleaner. Days 2 and 3, the wood burning appliance was not operational and the air cleaner was randomly chosen to operate in "filtration" or "placebo filtration" mode. When the air cleaner was operating, total indoor PM2.5 levels were significantly lower than on placebo filtration days (p = 0.0001) resulting in a median reduction of 52%. There was also a reduction in the median PM2.5 infiltration factor from 0.56 to 0.26 between these 2 days, suggesting the air cleaner was responsible for increased PM2.5 deposition on filtration days. Our findings suggest that the use of an air cleaner reduces exposure to indoor PM2.5 resulting from both indoor and ambient wood smoke sources.

Identification of the sources and geographic origins of black carbon using factor analysis at paired rural and urban sites.

Black carbon particles, composed of forms of elemental carbon (EC), contribute significantly to regional and global warming. The origins of EC were examined in southeastern Canada as part of a source apportionment study using positive matrix factorization (PMF), performed on long-term PM2.5 chemical speciation data collected at two paired rural and urban sites. Comparisons of the urban and rural sites revealed a previously unrecognized EC-rich factor that accounted for 41-56% of the total EC in this region. This factor was characterized by the more thermally stable EC fractions that exhibit strong light absorption characteristics. While these EC fractions are often attributed to local diesel emissions, this interpretation was rejected for several reasons. The EC-rich factor was present in similar temporal patterns at both the high-traffic urban and low-traffic rural sites across this 600 km region. The geographic origins of the EC-rich factor were found to be Ohio and Western Pennsylvania regions with heavy industry and multiple coal-based electrical generating stations. The direct radiative forcing due to this EC-rich factor was roughly estimated to be +0.2 W m(-2), which represented a substantial portion of the aerosol induced warming in the region. Thus, this region was impacted by an important unidentified source of EC associated with long-range transport.

Identification of weak and strong organic acids in atmospheric aerosols by capillary electrophoresis/mass spectrometry and ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry.

A novel approach using a combination of capillary electrophoresis/mass spectrometry (CE/MS) and off-line Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) revealed the structural details of acidic constituents of atmospheric organic aerosol. Both techniques utilized electrospray ionization (ESI), a soft ionization method, to facilitate the analysis of complex mixtures of organic compounds. CE/ESI-MS using an UltraTrol LN-precoated capillary and acidic background electrolytes at different pH values (2.5 and 4.7) was used to differentiate between weak (carboxylic) and strong (sulfonic) organic acids. On the basis of the electrophoretic mobility, m/z constraints from CE/ESI(-)-MS, and elemental composition information retrieved from off-line FTICR-MS, a variety of aliphatic and aromatic carboxylic acids (CHO-bearing molecules), nitrogen-containing carboxylic acids (CHON-bearing molecules), organosulfates (CHOS-bearing molecules), and (nitrooxy)organosulfates (CHONS-bearing molecules) were tentatively identified in the Oasis-HLB-extracted urban PM(2.5) (particulate matter with an aerodynamic diameter of <2.5 µm). The chemical known/unknown structures of detected compounds were confirmed by the semiempirical Offord model (effective mobility linearly correlated to Z/M(2/3)). The majorities of the identified compounds are products of atmospheric reactions and are known contributors to secondary organic aerosols.

Development of a hydrophilic interaction liquid chromatography-mass spectrometry method for detection and quantification of urea thermal decomposition by-products in emission from diesel engine employing selective catalytic reduction technology.

The use of urea based selective catalytic reduction (SCR) technology for the reduction of NOx from the exhaust of diesel-powered vehicles has the potential to emit at least six thermal decomposition by-products, ammonia, and unreacted urea from the tailpipe. These compounds may include: biuret, dicyandiamine, cyanuric acid, ammelide, ammeline and melamine. In the present study, a simple, sensitive and reliable hydrophilic interaction liquid chromatography (HILIC)-electrospray ionization (ESI)/mass spectrometry (MS) method without complex sample pre-treatment was developed for identification and determination of urea decomposition by-products in diesel exhaust. Gradient separation was performed on a SeQuant ZIC-HILIC column with a highly polar zwitterionic stationary phase, and using a mobile phase consisting of acetonitrile (eluent A) and 15 mM ammonium formate (pH 6; eluent B). Detection and quantification were performed using a quadrupole ESI/MS operated simultaneously in negative and positive mode. With 10 µL injection volume, LODs for all target analytes were in the range of 0.2-3 µg/L. The method showed a good inter-day precision of retention time (RSD<0.5%) and peak area (RSD<3%). Satisfactory extraction recoveries from spiked blanks ranged between 96 and 98%. Analyses of samples collected during transient chassis dynamometer tests of a bus engine equipped with a diesel particulate filter (DPF) and urea based SCR technology showed the presence of five target analytes with cyanuric acid and ammelide the most abundant compounds in the exhaust.

An improved method for determination of lanthanoids in environmental samples by inductively coupled plasma mass spectrometry with high matrix introduction system.

The capability of ICP-MS equipped with the high matrix introduction system (HMI) for accurate analysis of lanthanoids in environmental samples was investigated. Compared to the conventional operation, the amounts of oxide and hydroxide molecular species formed in the plasma were reduced by up to 5 times. The relative yields of oxides did not exceed 0.02% for BaO(+) species and were as low as 0.3% for lanthanoids with the highest oxide-formation rates (LaO(+), CeO(+), PrO(+) and NdO(+)). Hydroxide formation was less than 0.02% when HMI system was used. In addition, two digestion procedures were evaluated by the analysis of standard reference materials (SRMs) of different matrices. The digestion efficiency and limits of detection (LOD) were improved when samples were digested with a mixture of HNO(3)/H(2)O(2)/HCl/HF, and HF was removed by evaporation in presence of concentrated HCl. Using this procedure and HMI-ICP-MS analysis, LOD ranged from 0.1 µg kg(-1) to 6 µg kg(-1). Recoveries ranged from 85 to 115% for La to Ho and from 75 to 85% for the other lanthanoids. Relative standard deviations for replicate analysis of SRMs were less than 10%.