Comparing airborne algorithms for greenhouse gas flux measurements over the Alberta oil sands

To combat global warming, Canada has committed to reducing greenhouse gases to be (GHGs) 40 %–45 % below 2005 emission levels by 2025. Monitoring emissions and deriving accurate inventories are essential to reaching these goals. Airborne methods can provide regional and area source measurements with small error if ideal conditions for sampling are met. In this study, two airborne mass-balance box-flight algorithms were compared to assess the extent of their agreement and their performance under various conditions. The Scientific Aviation’s (SciAv) Gaussian algorithm and the Environment and Climate Change Canada’s top-down emission rate retrieval algorithm (TERRA) were applied to data from five samples. Estimates were compared using standard procedures, by systematically testing other method fits, and by investigating the effects on the estimates when method assumptions were not met. Results indicate that in standard scenarios the SciAv and TERRA mass-balance box-flight methods produce similar estimates that agree (3%–25%) within algorithm uncertainties (4%– 34%). Implementing a sample-specific surface extrapolation procedure for the SciAv algorithm may improve emission estimation. Algorithms disagreed when non-ideal conditions occurred (i.e., under non-stationary atmospheric conditions). Overall, the results provide confidence in the box-flight methods and indicate that emissions estimates are not overly sensitive to the choice of algorithm but demonstrate that fundamental algorithm assumptions should be assessed for each flight. Using a different method, the Airborne Visible InfraRed Imaging Spectrometer – Next Generation (AVIRIS-NG) independently mapped individual plumes with emissions 5 times larger than the source SciAv sampled three days later. The range in estimates highlights the utility of increased sampling to get a more complete understanding of the temporal variability of emissions and to identify emission sources within facilities. In addition, hourly on-site activity data would provide insight to the observed temporal variability in emissions and make a comparison to reported emissions more straightforward

On the link between ocean biota emissions, aerosol, and maritime clouds: Airborne, ground, and satellite measurements off the coast of California

Surface, airborne, and satellite measurements over the eastern Pacific Ocean off the coast of California during the period between 2005 and 2007 are used to explore the relationship between ocean chlorophyll a, aerosol, and marine clouds. Periods of enhanced chlorophyll a and wind speed are coincident with increases in particulate diethylamine and methanesulfonate concentrations. The measurements indicate that amines are a source of secondary organic aerosol in the marine atmosphere. Subsaturated aerosol hygroscopic growth measurements indicate that the organic component during periods of high chlorophyll a and wind speed exhibit considerable water uptake ability. Increased average cloud condensation nucleus (CCN) activity during periods of increased chlorophyll a levels likely results from both size distribution and aerosol composition changes. The available data over the period of measurements indicate that the cloud microphysical response, as represented by either cloud droplet number concentration or cloud droplet effective radius, is likely influenced by a combination of atmospheric dynamics and aerosol perturbations during periods of high chlorophyll a concentrations

Reactive Uptake of Glyoxal by Particulate Matter

The uptake of gaseous glyoxal onto particulate matter has been studied in laboratory experiments under conditions relevant to the ambient atmosphere using an aerosol mass spectrometer. The growth rates and reactive uptake coefficients, γ, were derived by fitting a model of particle growth to the experimental data. Organic growth rates varied from 1.05 × 10−11 to 23.1 × 10−11 μg particle−1 min−1 in the presence of ∼5 ppb glyoxal. Uptake coefficients (γ) of glyoxal varied from 8.0 × 10−4 to 7.3 × 10−3 with a median γ = 2.9 × 10−3, observed for (NH4)2SO4 seed aerosols at 55% relative humidity. Increased γ values were related to increased particle acidity, indicating that acid catalysis played a role in the heterogeneous mechanism. Experiments conducted at very low relative humidity, with the potential to be highly acidic, resulted in very low reactive uptake. These uptake coefficients indicated that the heterogeneous loss of glyoxal in the atmosphere is at least as important as gas phase loss mechanisms, including photolysis and reaction with hydroxyl radicals. Glyoxal lifetime due to heterogeneous reactions under typical ambient conditions was estimated to be τhet = 5–287 min. In rural and remote areas the glyoxal uptake can lead to 5–257 ng m−3 of secondary organic aerosols in 8 hours, consistent with recent ambient measurements

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

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

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

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 cm³ 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