Uncovering global-scale risks from commercial chemicals in air.

Commercial chemicals are used extensively across urban centres worldwide1, posing a potential exposure risk to 4.2 billion people2. Harmful chemicals are often assessed on the basis of their environmental persistence, accumulation in biological organisms and toxic properties, under international and national initiatives such as the Stockholm Convention3. However, existing regulatory frameworks rely largely upon knowledge of the properties of the parent chemicals, with minimal consideration given to the products of their transformation in the atmosphere. This is mainly due to a dearth of experimental data, as identifying transformation products in complex mixtures of airborne chemicals is an immense analytical challenge4. Here we develop a new framework-combining laboratory and field experiments, advanced techniques for screening suspect chemicals, and in silico modelling-to assess the risks of airborne chemicals, while accounting for atmospheric chemical reactions. By applying this framework to organophosphate flame retardants, as representative chemicals of emerging concern5, we find that their transformation products are globally distributed across 18 megacities, representing a previously unrecognized exposure risk for the world's urban populations. More importantly, individual transformation products can be more toxic and up to an order-of-magnitude more persistent than the parent chemicals, such that the overall risks associated with the mixture of transformation products are also higher than those of the parent flame retardants. Together our results highlight the need to consider atmospheric transformations when assessing the risks of commercial chemicals.

Chloramines as an important photochemical source of chlorine atoms in the urban atmosphere.

Monochloramine, dichloramine and trichloramine (NH2Cl, NHCl2, NCl3) are measured in the ambient atmosphere, in downtown Toronto in summer (median 39, 15 and 2.8 ppt) and winter (median 11, 7.3 and 0.7 ppt). NCl3 and NHCl2 were also measured in summer (median 1.3 and 14 ppt) from a suburban Toronto location. Measurements at two locations demonstrate prevalence of chloramines in an urban atmosphere. At both sites, NCl3 exhibits a strong diel pattern with maximum values during the night, and photolytic loss with sunrise. At the downtown site, a strong positive correlation between NH2Cl and NHCl2 in the summer night indicates a common source, with daily average peak mixing ratios approaching 500 and 250 ppt, respectively. As a previously unidentified source of chlorine (Cl) atoms, we demonstrate that NCl3 photolysis contributes 49 to 82% of the total local summertime Cl production rate at different times during the day with an average noontime peak of 3.8 × 105 atoms/cm3/s, with smaller contributions from ClNO2 and Cl2. Photolysis of NH2Cl and NHCl2 may augment this Cl production rate. Our measurements also demonstrate a daytime enhancement of chloroacetone in both the summer and winter, demonstrating the importance of Cl photochemistry. The results suggest that chloramines are an important source of Cl atoms in urban areas, with potential impacts on the abundance of organic compounds, ozone, nitrogen oxides, and particulate matter. Future studies should explore the vertical gradients of chloramines and their contribution to Cl production throughout the boundary layer.

Multiphase Ozonolysis of Bisphenol A: Chemical Transformations on Surfaces in the Environment.

High global plastic production volumes have led to the widespread presence of bisphenol compounds in human living and working environments. The most common bisphenol, bisphenol A (BPA), despite being endocrine disruptive and estrogenic, is still not fully banned worldwide, leading to continued human exposure via particles in air, dust, and surfaces in both outdoor and indoor environments. While its abundance is well documented, few studies have addressed the chemical transformations of BPA, the properties of its reactive products, and their toxicity. Here, the first gas-surface multiphase ozonolysis experiment of BPA thin films, at a constant ozone mixing ratio of 100 ppb, was performed in a flow tube for periods up to 24 h. Three transformation products involving the addition of 1, 2, and 3 oxygen atoms to the molecule were identified by LC-ESI-HRMS analyses. Exposure of indoor air to thin BPA surface films and BPA-containing thermal paper over periods of days validated the flow tube experiments, demonstrating the rapid nature of this multiphase ozonolysis reaction at atmospherically relevant ozone levels. Multiple transformation pathways are proposed that are likely applicable to not only BPA but also emerging commercial bisphenol products.

Quantification of Methane Emissions from Cold Heavy Oil Production with Sand Extraction in Alberta and Saskatchewan, Canada.

Cold heavy oil production with sand (CHOPS) is an extraction process for heavy oil in Canada, with the potential to lead to higher CH4 venting than conventional oil sites, that have not been adequately characterized. In order to quantify CH4 emissions from CHOPS activities, a focused aerial measurement campaign was conducted in the Canadian provinces of Alberta and Saskatchewan in June 2018. Total CH4 emissions from each of 10 clusters of CHOPS wells (containing 22-167 well sites per cluster) were derived using a mass balance computation algorithm that uses in situ wind data measurement on board aircraft. Results show that there is no statistically significant difference in CH4 emissions from CHOPS wells between the two provinces. Cluster-aggregated emission factors (EF) were determined using correspondingly aggregated production volumes. The average CH4 EF was 70.4 ± 36.9 kg/m3 produced oil for the Alberta wells and 55.1 ± 13.7 kg/m3 produced oil for the Saskatchewan wells. Using these EF and heavy oil production volumes reported to provincial regulators, the annual CH4 emissions from CHOPS were estimated to be 121% larger than CHOPS emissions extracted from Canada's National Inventory Report (NIR) for Saskatchewan. The EF were found to be positively correlated with the percentage of nonpiped production volumes in each cluster, indicating higher emissions for nonpiped wells while suggesting an avenue for methane emission reductions. A comparison with recent measurements indicates relatively limited effectiveness of regulations for Saskatchewan compared to those in Alberta. The results of this study indicate the substantial contribution of CHOPS operations to the underreporting observed in the NIR and provide measurement-based EF that can be used to develop improved emissions inventories for this sector and mitigate CH4 emissions from CHOPS operations.

Oil sands operations as a large source of secondary organic aerosols.

Worldwide heavy oil and bitumen deposits amount to 9 trillion barrels of oil distributed in over 280 basins around the world, with Canada home to oil sands deposits of 1.7 trillion barrels. The global development of this resource and the increase in oil production from oil sands has caused environmental concerns over the presence of toxic compounds in nearby ecosystems and acid deposition. The contribution of oil sands exploration to secondary organic aerosol formation, an important component of atmospheric particulate matter that affects air quality and climate, remains poorly understood. Here we use data from airborne measurements over the Canadian oil sands, laboratory experiments and a box-model study to provide a quantitative assessment of the magnitude of secondary organic aerosol production from oil sands emissions. We find that the evaporation and atmospheric oxidation of low-volatility organic vapours from the mined oil sands material is directly responsible for the majority of the observed secondary organic aerosol mass. The resultant production rates of 45-84 tonnes per day make the oil sands one of the largest sources of anthropogenic secondary organic aerosols in North America. Heavy oil and bitumen account for over ten per cent of global oil production today, and this figure continues to grow. Our findings suggest that the production of the more viscous crude oils could be a large source of secondary organic aerosols in many production and refining regions worldwide, and that such production should be considered when assessing the environmental impacts of current and planned bitumen and heavy oil extraction projects globally.

Evolution of Atmospheric Total Organic Carbon from Petrochemical Mixtures.

Reactive organic compounds play a central role in the formation of ozone and secondary organic aerosols. The ability to accurately predict their fate, in part, relies upon quantitative knowledge of the chemical and physical parameters associated with the total organic carbon (TOC), which includes both precursors and oxidation products that evolve in the atmosphere over short to long time scales. However, such knowledge, obtained via limited carbon closure experiments, has not been attained for complex anthropogenic emissions. Here we present the first comprehensive characterization of TOC in the atmospheric oxidation of organic vapors from light and heavy oil mixtures associated with oil sand operations. Despite the complexity of the investigated oil mixtures, we are able to achieve carbon closure (83-116%) within the uncertainties (±20%), with the degree of the closure being dependent upon the vapor composition and NOx levels. In contrast to biogenic precursors (e.g., α-pinene), the photochemical time scale required for a largely complete oxidation and evolution of chemical parameters is very long for the petrochemical vapors (i.e., ∼7-10 days vs ∼1 day), likely due to the lower initial precursor reactivity. This suggests that petrochemical emissions and their impacts are likely to extend further spatially than biogenic emissions, and retain more of their complex composition and reactivity for many days. The results of this work provide key parameters to regional models for further improving the representation of the chemical evolution of petrochemical emissions.

Fugitive Emissions of Volatile Organic Compounds from a Tailings Pond in the Oil Sands Region of Alberta.

Tailings ponds in the oil sands (OS) region in Alberta, Canada, have been associated with fugitive emissions of volatile organic compounds (VOCs) and other pollutants to the atmosphere. However, the contribution of tailings ponds to the total fugitive emissions of VOCs from OS operations remains uncertain. To address this knowledge gap, a field study was conducted in the summer of 2017 at Suncor's Pond 2/3 to estimate emissions of a suite of pollutants including 68 VOCs using a combination of micrometeorological methods and measurements from a flux tower. The results indicate that in 2017, Pond 2/3 was an emission source of 3322 ± 727 tons of VOCs including alkanes, aromatics, and oxygenated and sulfur-containing organics. While the total VOC emissions were approximately a factor of 2 higher than those reported by Suncor, the individual VOC species emissions varied by up to a factor of 12. A chemical mass balance (CMB) receptor model was used to estimate the contribution of the tailings pond to VOC pollution events in a nearby First Nations and Metis community in Fort McKay. CMB results indicate that Suncor Pond 2/3 contributed up to 57% to the total mass of VOCs measured at Fort McKay, reinforcing the importance of accurate VOC emission estimation methods for tailings ponds.

Top-Down Determination of Black Carbon Emissions from Oil Sand Facilities in Alberta, Canada Using Aircraft Measurements.

Black carbon (BC) emissions from the Canadian oil sand (OS) surface mining facilities in Alberta were investigated using aircraft measurements. BC emission rates were derived with a top-down mass balance approach and were found to be linearly related to the volume of oil sand ore mined at each facility. Two emission factors were determined from the measurements; production-based BC emission factors were in the range of 0.6-1.7 g/tonne mined OS ore, whereas fuel-based BC emission factors were between 95 and 190 mg/kg-fuel, depending upon the facility. The annual BC emission, at 707 ± 117 tonnes/year for the facilities, was determined using the production-based emission factors and annual production data. Although this annual emission is in reasonable agreement with the BC annual emissions reported in the latest version of the Canadian national BC inventory (within 16%), the relative split between off-road diesel and stack sources is significantly different between the measurements and the inventory. This measurement evidence highlights the fact that the stack sources of BC may be overestimated and the off-road diesel sources may be underestimated in the inventory and points to the need for improved BC emission data from diesel sources within facilities.

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

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate.

Differences between measured and reported volatile organic compound emissions from oil sands facilities in Alberta, Canada.

Large-scale oil production from oil sands deposits in Alberta, Canada has raised concerns about environmental impacts, such as the magnitude of air pollution emissions. This paper reports compound emission rates (E) for 69-89 nonbiogenic volatile organic compounds (VOCs) for each of four surface mining facilities, determined with a top-down approach using aircraft measurements in the summer of 2013. The aggregate emission rate (aE) of the nonbiogenic VOCs ranged from 50 ± 14 to 70 ± 22 t/d depending on the facility. In comparison, equivalent VOC emission rates reported to the Canadian National Pollutant Release Inventory (NPRI) using accepted estimation methods were lower than the aE values by factors of 2.0 ± 0.6, 3.1 ± 1.1, 4.5 ± 1.5, and 4.1 ± 1.6 for the four facilities, indicating underestimation in the reported VOC emissions. For 11 of the combined 93 VOC species reported by all four facilities, the reported emission rate and E were similar; but for the other 82 species, the reported emission rate was lower than E The median ratio of E to that reported for all species by a facility ranged from 4.5 to 375 depending on the facility. Moreover, between 9 and 53 VOCs, for which there are existing reporting requirements to the NPRI, were not included in the facility emission reports. The comparisons between the emission reports and measurement-based emission rates indicate that improvements to VOC emission estimation methods would enhance the accuracy and completeness of emission estimates and their applicability to environmental impact assessments of oil sands developments.

Understanding the Impact of Relative Humidity and Coexisting Soluble Iron on the OH-Initiated Heterogeneous Oxidation of Organophosphate Flame Retardants.

The current uncertainties in the reactivity and atmospheric persistence of particle-associated chemicals present a challenge for the prediction of long-range transport and deposition of emerging chemicals such as organophosphate flame retardants, which are ubiquitous in the global environment. Here, the OH-initiated heterogeneous oxidation kinetics of organophosphate flame retardants (OPFRs) coated on inert (NH4)2SO4 and redox-active FeSO4 particles were systematically determined as a function of relative humidity (RH). The derived reaction rate constants for the heterogeneous loss of tricresyl phosphate (TCP; kTCP) and tris(2-butoxyethyl) phosphate (TBEP; kTBEP) were in the range of (2.69-3.57) × 10-12 and (3.06-5.55) × 10-12 cm3 molecules-1 s-1, respectively, depending on the RH and coexisting Fe(II) content. The kTCP (coated on (NH4)2SO4) was relatively constant over the investigated RH range while kTBEP was enhanced by up to 19% with increasing RH. For both OPFRs, the presence of Fe(II) enhanced their k by up to 53% over inert (NH4)2SO4. These enhancement effects (RH and Fe(II)) were attributed to fundamental changes in the organic phase state (higher RH lowered particle viscosity) and Fenton-type chemistry which resulted in the formation of reactive oxygen species, respectively. Such findings serve to emphasize the importance of ambient RH, the phase state of particle-bound organics in general, and the presence of coexisting metallic species for an accurate description of the degradation kinetics and aging of particulate OPFRs in models used to evaluate their atmospheric persistence.

Understanding the Impact of High-NOx Conditions on the Formation of Secondary Organic Aerosol in the Photooxidation of Oil Sand-Related Precursors.

Oil sands (OS) are an important type of heavy oil deposit, for which operations in Alberta, Canada, were recently found to be a large source of secondary organic aerosol (SOA). However, SOA formation from the OS mining, processing, and subsequent tailings, especially in the presence of NOx, remains unclear. Here, photooxidation experiments for OS-related precursors under high-NOx conditions were performed using an oxidation flow reactor, in which ∼95% of peroxy radicals (RO2) react with NO. The SOA yields under high-NOx conditions were found to be lower than yields under low-NOx conditions for all precursors, which is likely due to the higher volatilities of the products from the RO2 + NO pathway compared with RO2 + HO2. The SOA yields under high-NOx conditions show a strong dependence on pre-existing surface area (not observed in previous low-NOx experiments), again attributed to the higher product volatilities. Comparing the mass spectra of SOA formed from different precursors, we conclude that the fraction of m/z > 80 (F80) can be used as a parameter to separate different types of SOA in the region. In addition, particle-phase organic nitrate was found to be an important component (9-23%) of OS SOA formed under high-NOx conditions. These results have implications for better understanding the atmospheric processing of OS emissions.

Oxidative and Toxicological Evolution of Engineered Nanoparticles with Atmospherically Relevant Coatings.

The health impacts associated with engineered nanoparticles (ENPs) released into the atmosphere have not been adequately assessed. Such impacts could potentially arise from the toxicity associated with condensable atmospheric secondary organic material (SOM), or changes in the SOM composition induced by ENPs. Here, these possibilities are evaluated by investigating the oxidative and toxicological evolution of TiO2 and SiO2 nanoparticles which have been coated with SOM from the O3 or OH initiated oxidation of α-pinene. It was found that pristine SiO2 particles were significantly more cytotoxic compared to pristine TiO2 particles. TiO2 in the dark or under UV irradiation catalytically reacted with the SOM, increasing its O/C by up to 55% over photochemically inert SiO2 while having negligible effects on the overall cytotoxicity. Conversely, the cytotoxicity associated with SiO2 coated with SOM was markedly suppressed (by a factor of 9, at the highest exposure dose) with both increased SOM coating thickness and increased photochemical aging. These suppressing effects (organic coating and photo-oxidation of organics) were attributed to a physical hindrance of SiO2-cell interactions by the SOM and enhanced SOM viscosity and hydrophilicity with continued photo-oxidation, respectively. These findings highlight the importance of atmospheric processes in altering the cytotoxicity of ENPs.

Experimental Study of OH-Initiated Heterogeneous Oxidation of Organophosphate Flame Retardants: Kinetics, Mechanism, and Toxicity.

The environmental risks and health impacts associated with particulate organophosphate flame retardants (OPFRs), which are ubiquitous in the global atmosphere, have not been adequately assessed due to the lack of data on the reaction kinetics, products, and toxicity associated with their atmospheric transformations. Here, the importance of such transformations for OPFRs are explored by investigating the reaction kinetics, degradation chemical mechanisms, and toxicological evolution of two OPFRs (2-ethylhexyl diphenyl phosphate (EHDP) and diphenyl phosphate (DPhP)) coated on (NH4)2SO4 particles upon heterogeneous OH oxidation. The derived reaction rate constants for the heterogeneous loss of EHDP and DPhP are (1.12 ± 0.22) × 10-12 and (2.33 ± 0.14) × 10-12 cm3 molecules-1 s-1, respectively. Using recently developed real-time particle chemical composition measurements, particulate products from heterogeneous photooxidation and the associated degradation mechanisms for particulate OPFRs are reported for the first time. Subsequent cytotoxicity analysis of the unreacted and oxidized OPFR particles indicated that the overall particle cytotoxicity was reduced by up to 94% with heterogeneous photooxidation, likely due to a significantly lower cytotoxicity associated with the oxidized OPFR products relative to the parent OPFRs. The present work not only provides guidance for future field sampling for the detection of transformation products of OPFRs, but also strongly supports the ongoing risk assessment of these emerging chemicals and most critically, their products.

Enhanced Light Scattering of Secondary Organic Aerosols by Multiphase Reactions.

Secondary organic aerosol (SOA) plays a pivotal role in visibility and radiative forcing, both of which are intrinsically linked to the refractive index (RI). While previous studies have focused on the RI of SOA from traditional formation processes, the effect of multiphase reactions on the RI has not been considered. Here, we investigate the effects of multiphase processes on the RI and light-extinction of m-xylene-derived SOA, a common type of anthropogenic SOA. We find that multiphase reactions in the presence of liquid water lead to the formation of oligomers from intermediate products such as glyoxal and methylglyoxal, resulting in a large enhancement in the RI and light-scattering of this SOA. These reactions will result in increases in light-scattering efficiency and direct radiative forcing of approximately 20%-90%. These findings improve our understanding of SOA optical properties and have significant implications for evaluating the impacts of SOA on the rapid formation of regional haze, global radiative balance, and climate change.

Quantifying the Primary Emissions and Photochemical Formation of Isocyanic Acid Downwind of Oil Sands Operations.

Isocyanic acid (HNCO) is a known toxic species and yet the relative importance of primary and secondary sources to regional HNCO and population exposure remains unclear. Off-road diesel fuel combustion has previously been suggested to be an important regional source of HNCO, which implies that major industrial facilities such as the oil sands (OS), which consume large quantities of diesel fuel, can be sources of HNCO. The OS emissions of nontraditional toxic species such as HNCO have not been assessed. Here, airborne measurements of HNCO were used to estimate primary and secondary HNCO for the oil sands. Approximately 6.2 ± 1.1 kg hr-1 was emitted from off-road diesel activities within oil sands facilities, and an additional 116-186 kg hr-1 formed from the photochemical oxidation of diesel exhaust. Together, the primary and secondary HNCO from OS operations represent a significant anthropogenic HNCO source in Canada. The secondary HNCO downwind of the OS was enhanced by up to a factor of 20 relative to its primary emission, an enhancement factor significantly greater than previously estimated from laboratory studies. Incorporating HNCO emissions and formation into a regional model demonstrated that the HNCO levels in Fort McMurray (∼10-70 km downwind of the OS) are controlled by OS emissions; > 50% of the monthly mean HNCO arose from the OS. While the mean HNCO levels in Fort McMurray are predicted to be below the 1000 pptv level associated with potential negative health impacts, (∼25 pptv in August-September), an order of magnitude increase in concentration is predicted (250-600 pptv) when the town is directly impacted by OS plumes. The results here highlight the importance of obtaining at-source HNCO emission factors and advancing the understanding of secondary HNCO formation mechanisms, to assess and improve HNCO population exposure predictions.

Chemical and toxicological evolution of carbon nanotubes during atmospherically relevant aging processes.

The toxicity of carbon nanotubes (CNTs) has received significant attention due to their usage in a wide range of commercial applications. While numerous studies exist on their impacts in water and soil ecosystems, there is a lack of information on the exposure to CNTs from the atmosphere. The transformation of CNTs in the atmosphere, resulting in their functionalization, may significantly alter their toxicity. In the current study, the chemical modification of single wall carbon nanotubes (SWCNTs) via ozone and OH radical oxidation is investigated through studies that simulate a range of expected tropospheric particulate matter (PM) lifetimes, in order to link their chemical evolution to toxicological changes. The results indicate that the oxidation favors carboxylic acid functionalization, but significantly less than other studies performed under nonatmospheric conditions. Despite evidence of functionalization, neither O3 nor OH radical oxidation resulted in a change in redox activity (potentially giving rise to oxidative stress) or in cytotoxic end points. Conversely, both the redox activity and cytotoxicity of SWCNTs significantly decreased when exposed to ambient urban air, likely due to the adsorption of organic carbon vapors. These results suggest that the effect of gas-particle partitioning of organics in the atmosphere on the toxicity of SWCNTs should be investigated further.

Heterogeneous OH initiated oxidation: a possible explanation for the persistence of organophosphate flame retardants in air.

Heterogeneous reactions between OH radicals and emerging flame retardant compounds coated on inert particles have been investigated. Organophosphate esters (OPEs) including triphenyl phosphate (TPhP), tris-2-ethylhexyl phosphate (TEHP), and tris-1,3-dichloro-2-propyl phosphate (TDCPP) were coated on (NH4)2SO4 particles and exposed to OH radicals in a photochemical flow tube at 298 K and (38.0 ± 2.0) % RH. The degradation of these particle-bound OPEs was observed as a result of OH exposure, as measured using a Time-of-Flight Aerosol Mass Spectrometer. The derived second-order rate constants for the heterogeneous loss of TPhP, TEHP, and TDCPP were (2.1 ± 0.19) × 10(-12), (2.7 ± 0.63) × 10(-12), and (9.2 ± 0.92) × 10(-13) cm(3) molecule(-1) s(-1), respectively, from which approximate atmospheric lifetimes are estimated to be 5.6 (5.2-6.0), 4.3 (3.5-5.6), and 13 (11-14) days. Additional coating of the OPE coated particles with an OH radical active species further increased the lifetimes of these OPEs. These results represent the first reported estimates of heterogeneous reaction rate constants for these species. The results demonstrate that particle bound OPEs are highly persistent in the atmosphere with regard to OH radical oxidation, consistent with the assumption that OPEs can undergo medium or long-range transport, as previously proposed on the basis of field measurements. Finally, these results indicate that future risk assessment and transport modeling of emerging priority chemicals with semi- to low-volatility must consider particle phase heterogeneous loss processes when evaluating environmental persistence.

Total organic carbon measurements reveal major gaps in petrochemical emissions reporting.

Anthropogenic organic carbon emissions reporting has been largely limited to subsets of chemically speciated volatile organic compounds. However, new aircraft-based measurements revealed total gas-phase organic carbon emissions that exceed oil sands industry-reported values by 1900% to over 6300%, the bulk of which was due to unaccounted-for intermediate-volatility and semivolatile organic compounds. Measured facility-wide emissions represented approximately 1% of extracted petroleum, resulting in total organic carbon emissions equivalent to that from all other sources across Canada combined. These real-world observations demonstrate total organic carbon measurements as a means of detecting unknown or underreported carbon emissions regardless of chemical features. Because reporting gaps may include hazardous, reactive, or secondary air pollutants, fully constraining the impact of anthropogenic emissions necessitates routine, comprehensive total organic carbon monitoring as an inherent check on mass closure.

Filterable redox cycling activity: a comparison between diesel exhaust particles and secondary organic aerosol constituents.

The redox activity of diesel exhaust particles (DEP) collected from a light-duty diesel passenger car engine was examined using the dithiothreitol (DTT) assay. DEP was highly redox-active, causing DTT to decay at a rate of 23-61 pmol min(-1) µg(-1) of particle used in the assay, which was an order of magnitude higher than ambient coarse and fine particulate matter (PM) collected from downtown Toronto. Only 2-11% of the redox activity was in the water-soluble portion, while the remainder occurred at the black carbon surface. This is in contrast to redox-active secondary organic aerosol constituents, in which upward of 90% of the activity occurs in the water-soluble fraction. The redox activity of DEP is not extractable by moderately polar (methanol) and nonpolar (dichloromethane) organic solvents, and is hypothesized to arise from redox-active moieties contiguous with the black carbon portion of the particles. These measurements illustrate that "Filterable Redox Cycling Activity" may therefore be useful to distinguish black carbon-based oxidative capacity from water-soluble organic-based activity. The difference in chemical environment leading to redox activity highlights the need to further examine the relationship between activity in the DTT assay and toxicology measurements across particles of different origins and composition.