Evaluation of a Passive Sampling Method for Long-Term Continuous Monitoring of Volatile Organic Compounds in Urban Environments.

Environmental Protection Agency Method 325 was developed for continuous passive monitoring of volatile organic compounds (VOCs), particularly benzene, at petroleum refinery fencelines. In this work, a modified version of the method was evaluated at an Ontario near-road research station in winter to assess its suitability for urban air quality monitoring. Samples were collected at 24 hour and 14 day resolution to investigate accuracy for different exposure times. Tubes were analyzed by thermal desorption-gas chromatography-mass spectrometry, and 11 VOCs were quantified, including aromatic air toxics. The same VOCs were simultaneously monitored using traditional canister sampling for comparison, and a subset of four were also monitored using a novel miniature gas chromatograph. Good agreement (within 10%) was observed between the 14 day passive tube samples and the canister samples for benzene. However, field-calibrated uptake rates were required to correct passive tube concentrations for less volatile aromatics. Passive tube deployment and analysis is inexpensive; sampling does not require power, and accurate measurements of benzene are demonstrated here for an urban environment. The method is expected to be advantageous for the generation of long-term continuous benzene datasets suitable for epidemiological research with greater spatial coverage than is currently available using traditional monitoring techniques.

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.

Temporal variation in the deposition of polycyclic aromatic compounds in snow in the Athabasca Oil Sands area of Alberta.

Atmospheric deposition of polycyclic aromatic compounds (PACs) via and onto snow, and their releasing during spring snowmelt has been a concern in the Athabasca Oil Sands Region of Alberta. This study was designed to evaluate the concentrations, loadings, and distribution of PACs in springtime snowpack and how they have changed since the first study in 2008. Snowpack samples were collected in late winters 2011-2014 at varying distances from the main developments. PAC concentration and deposition declined exponentially with distance, with pyrenes, chrysenes, and dibenzothiophenes dominating the distribution within the first 50 km. The distribution of PACs was different between sites located close to upgraders and others located close to mining facilities. Overall, PAC loadings were correlated with priority pollutant elements and water chemistry parameters, while wind direction and speed were not strong contributors to the variability observed. Total PAC mass deposition during winter months and within the first 50 km was initially estimated by integrating the exponential decay function fitted through the data using a limited number of sites from 2011 to 2014: 1236 kg (2011), 1800 kg (2012), 814 kg (2013), and 1367 (2014). Total loadings were estimated to have a twofold increase between 2008 and 2014, although the increase observed was not constant. Finally, kriging interpolation is presented as an alternative and more robust approach to estimate PAC mass deposition in the area. After a more intensive sampling campaign in 2014, the PAC mass deposition was estimated to be 1968 kg.

The impact of a landfill fire on ambient air quality in the north: A case study in Iqaluit, Canada.

A large landfill fire occurred in Iqaluit, Canada in spring/summer 2014. Air quality data were collected to characterize emissions as well as potential threats to public health. Criteria pollutants were monitored (PM2.5, O3, NO2) along with dioxins/furans, polycyclic aromatic hydrocarbons, and volatile organic compounds. Median daily dioxin/furan concentrations were 66-times higher during active burning (0.2 pg/m(3) Toxic Equivalency Quotient (TEQ)) compared to after the fire was extinguished (0.003 pg/m(3) TEQ). Other pollutants changed less dramatically. Our findings suggest that airborne concentrations of potentially harmful substances may be elevated during landfill fires even when criteria air pollutants remain largely unchanged.

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.

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.

A global observational analysis to understand changes in air quality during exceptionally low anthropogenic emission conditions.

This global study, which has been coordinated by the World Meteorological Organization Global Atmospheric Watch (WMO/GAW) programme, aims to understand the behaviour of key air pollutant species during the COVID-19 pandemic period of exceptionally low emissions across the globe. We investigated the effects of the differences in both emissions and regional and local meteorology in 2020 compared with the period 2015-2019. By adopting a globally consistent approach, this comprehensive observational analysis focuses on changes in air quality in and around cities across the globe for the following air pollutants PM2.5, PM10, PMC (coarse fraction of PM), NO2, SO2, NOx, CO, O3 and the total gaseous oxidant (OX = NO2 + O3) during the pre-lockdown, partial lockdown, full lockdown and two relaxation periods spanning from January to September 2020. The analysis is based on in situ ground-based air quality observations at over 540 traffic, background and rural stations, from 63 cities and covering 25 countries over seven geographical regions of the world. Anomalies in the air pollutant concentrations (increases or decreases during 2020 periods compared to equivalent 2015-2019 periods) were calculated and the possible effects of meteorological conditions were analysed by computing anomalies from ERA5 reanalyses and local observations for these periods. We observed a positive correlation between the reductions in NO2 and NOx concentrations and peoples' mobility for most cities. A correlation between PMC and mobility changes was also seen for some Asian and South American cities. A clear signal was not observed for other pollutants, suggesting that sources besides vehicular emissions also substantially contributed to the change in air quality. As a global and regional overview of the changes in ambient concentrations of key air quality species, we observed decreases of up to about 70% in mean NO2 and between 30% and 40% in mean PM2.5 concentrations over 2020 full lockdown compared to the same period in 2015-2019. However, PM2.5 exhibited complex signals, even within the same region, with increases in some Spanish cities, attributed mainly to the long-range transport of African dust and/or biomass burning (corroborated with the analysis of NO2/CO ratio). Some Chinese cities showed similar increases in PM2.5 during the lockdown periods, but in this case, it was likely due to secondary PM formation. Changes in O3 concentrations were highly heterogeneous, with no overall change or small increases (as in the case of Europe), and positive anomalies of 25% and 30% in East Asia and South America, respectively, with Colombia showing the largest positive anomaly of ~70%. The SO2 anomalies were negative for 2020 compared to 2015-2019 (between ~25 to 60%) for all regions. For CO, negative anomalies were observed for all regions with the largest decrease for South America of up to ~40%. The NO2/CO ratio indicated that specific sites (such as those in Spanish cities) were affected by biomass burning plumes, which outweighed the NO2 decrease due to the general reduction in mobility (ratio of ~60%). Analysis of the total oxidant (OX = NO2 + O3) showed that primary NO2 emissions at urban locations were greater than the O3 production, whereas at background sites, OX was mostly driven by the regional contributions rather than local NO2 and O3 concentrations. The present study clearly highlights the importance of meteorology and episodic contributions (e.g., from dust, domestic, agricultural biomass burning and crop fertilizing) when analysing air quality in and around cities even during large emissions reductions. There is still the need to better understand how the chemical responses of secondary pollutants to emission change under complex meteorological conditions, along with climate change and socio-economic drivers may affect future air quality. The implications for regional and global policies are also significant, as our study clearly indicates that PM2.5 concentrations would not likely meet the World Health Organization guidelines in many parts of the world, despite the drastic reductions in mobility. Consequently, revisions of air quality regulation (e.g., the Gothenburg Protocol) with more ambitious targets that are specific to the different regions of the world may well be required.

Profiling quinones in ambient air samples collected from the Athabasca region (Canada).

This paper presents new findings on polycyclic aromatic hydrocarbon oxidation products-quinones that were collected in ambient air samples in the proximity of oil sands exploration. Quinones were characterized for their diurnal concentration variability, phase partitioning, and molecular size distribution. Gas-phase (GP) and particle-phase (PM) ambient air samples were collected separately in the summer; a lower quinone content was observed in the PM samples from continuous 24-h sampling than from combined 12-h sampling (day and night). The daytime/nocturnal samples demonstrated that nighttime conditions led to lower concentrations and some quinones not being detected. The highest quinone levels were associated with wind directions originating from oil sands exploration sites. The statistical correlation with primary pollutants directly emitted from oil sands industrial activities indicated that the bulk of the detected quinones did not originate directly from primary emission sources and that quinone formation paralleled a reduction in primary source NOx levels. This suggests a secondary chemical transformation of primary pollutants as the origin of the determined quinones. Measurements of 19 quinones included five that have not previously been reported in ambient air or in Standard Reference Material 1649a/1649b and seven that have not been previously measured in ambient air in the underivatized form. This is the first paper to report on quinone characterization in secondary organic aerosols originating from oil sands activities, to distinguish chrysenequinone and anthraquinone positional isomers in ambient air, and to report the requirement of daylight conditions for benzo[a]pyrenequinone and naphthacenequinone to be present in ambient air.

n-alkane profiles of engine lubricating oil and particulate matter by molecular sieve extraction.

As part of the Canadian Atmospheric Fine Particle Research Program to obtain reliable primary source emission profiles, a molecular sieve method was developed to reliably determine n-alkanes in lubricating oils, vehicle emissions, and mobile source dominated ambient particulate matter (PM). This work was also initiated to better calculate carbon preference index values (CPI: the ratio of the sums of odd over even n-alkanes), a parameter for estimating anthropogenic versus biogenic contributions in PM. n-Alkanes in lubricating oil and mobile source dominated PM are difficult to identify and quantify by gas chromatography due to the presence of similar components that cannot be fully resolved. This results in a hump, the unresolved complex mixture (UCM) that leads to incorrect n-alkane concentrations and CPI values. The sieve method yielded better chromatography, unambiguous identification of n-alkanes and allowed examination of differences between n-alkane profiles in light (LDV) and heavy duty vehicle (HDV) lubricating oils that would have been otherwise difficult. These profile differences made it possible to relate the LDV profile to that of the PM samples collected during a tunnel study in August 2001 near Vancouver (British Columbia, Canada). The n-alkane PM data revealed that longer sampling times result in a negative artifact, i.e., the desorption of the more volatile n-alkanes from the filters. Furthermore, the sieve procedure yielded n-alkane data that allowed calculation of accurate CPI values for lubricating oils and PM samples. Finally, this method may prove helpful in estimating the respective diesel and gasoline contributions to ambient PM.