ALBERT

Description: We present an analysis of ozone (O3) photochemistry observed by aircraft measurements of boreal biomass burning plumes over eastern Canada in the summer of 2011. Measurements of O3 and a number of key chemical species associated with O3 photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the "quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS) experiment between 12 July and 3 August 2011. The location and timing of the aircraft measurements put BORTAS into a unique position to sample biomass burning plumes from the same source region in Northwestern Ontario with a range of ages. We found that O3 mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (= NOy-NOx) revealed that the potential for O3 production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 10 days. The BORTAS measurements provided a wide dynamic range of O3 production in the sampled biomass burning plumes with ΔO3/ΔCO enhancement ratios increasing from 0.020 ± 0.008 ppbv ppbv−1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbv ppbv−1 in plumes with photochemical ages greater than 5 days. We found that the main contributing factor to the variability in the ΔO3/ΔCO enhancement ratio was ΔCO in plumes with photochemical ages less than 4 days, and that was a transition to ΔO3 becoming the main contributing factor in plumes with ages greater than 4 days. In comparing O3 mixing ratios with components of the NOy budget, we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiency (OPE) of 7.7 ± 3.5 ppbv ppbv−1 relative to ΣAN and 1.6 ± 0.9 ppbv ppbv−1 relative to NOz. In plumes with ages greater than 4 days, OPE increased to 472 ± 28 ppbv ppbv−1 relative to ΣAN and 155 ± 5 ppbv ppbv−1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photostationary steady state and O3 production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to O3. The BORTAS measurements of O3 photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the Troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990.

Description: We describe the design and execution of the BORTAS (Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) experiment, which has the overarching objective of understanding the chemical aging of air masses that contain the emission products from seasonal boreal wildfires and how these air masses subsequently impact downwind atmospheric composition. The central focus of the experiment was a two-week deployment of the UK BAe-146-301 Atmospheric Research Aircraft (ARA) over eastern Canada, based out of Halifax, Nova Scotia. Atmospheric ground-based and sonde measurements over Canada and the Azores associated with the planned July 2010 deployment of the ARA, which was postponed by 12 months due to UK-based flights related to the dispersal of material emitted by the Eyjafjallajökull volcano, went ahead and constituted phase A of the experiment. Phase B of BORTAS in July 2011 involved the same atmospheric measurements, but included the ARA, special satellite observations and a more comprehensive ground-based measurement suite. The high-frequency aircraft data provided a comprehensive chemical snapshot of pyrogenic plumes from wildfires, corresponding to photochemical (and physical) ages ranging from 〈 1 day to ~

Description: We describe the design and execution of the BORTAS (Quantifying the impact of BOReal forest fires on Tropospheric oxidants using Aircraft and Satellites) experiment, which has the overarching objective of understanding the chemical aging of airmasses that contain the emission products from seasonal boreal wildfires and how these airmasses subsequently impact downwind atmospheric composition. The central focus of the experiment was a two-week deployment of the UK BAe-146-301 Atmospheric Research Aircraft (ARA) over eastern Canada. The planned July 2010 deployment of the ARA was postponed by 12 months because of activities related to the dispersal of material emitted by the Eyjafjallajökull volcano. However, most other planned model and measurement activities, including ground-based measurements at the Dalhousie University Ground Station (DGS), enhanced ozonesonde launches, and measurements at the Pico Atmospheric Observatory in the Azores, went ahead and constituted phase A of the experiment. Phase B of BORTAS in July 2011 included the same measurements, but included the ARA, special satellite observations and a more comprehensive measurement suite at the DGS. The high-frequency aircraft data provided a comprehensive snapshot of the pyrogenic plumes from wildfires. The coordinated ground-based and sonde data provided detailed but spatially-limited information that put the aircraft data into context of the longer burning season. We coordinated aircraft vertical profiles and overpasses of the NASA Tropospheric Emission Spectrometer and the Canadian Atmospheric Chemistry Experiment. These space-borne data, while less precise than other data, helped to relate the two-week measurement campaign to larger geographical and longer temporal scales. We interpret these data using a range of chemistry models: from a near-explicit gas-phase chemical mechanism, which tests out understanding of the underlying chemical mechanism, to regional and global 3-D models of atmospheric transport and lumped chemistry, which helps to assess the performance of the simplified chemical mechanism and effectively act as intermediaries between different measurement types. We also present an overview of some of the new science that has originated from this project from the mission planning and execution to the analysis of the ground-based, aircraft, and space-borne data.

Description: A four-channel thermal dissociation laser induced fluorescence (TD-LIF) instrument has been developed for simultaneous measurements of nitrogen dioxide (NO2), total peroxy nitrate (∑PNs), total alkyl nitrate (∑ANs) and nitric acid (HNO3). NO2 is measured directly by LIF at 532 nm, whereas organic nitrates and nitric acid are thermally dissociated at distinct temperatures in the inlet to form NO2, which is then measured by LIF. The concentrations of each dissociated species are derived by the differences in measured NO2 relative to the reference colder inlet channel. The TD-LIF was adapted to fly on board the UK Facility for Airborne Atmospheric Measurements (FAAM) BAe 146-301 atmospheric research aircraft in summer 2010, and to date has successfully flown in five field campaigns. This paper reports novel improvements in the TD-LIF instrumentations including: (1) the use of a single wavelength laser, which makes the system compact and relatively cheap; (2) the use of a single beam laser that allows easy alignment and optical stability against the vibrational aircraft environment and (3) the optical assembly of four detection cells that allow simultaneous and fast (time resolution up to 0.1 s) measurements of NO2, ∑PNs, ∑ANs and HNO3. Laboratory-generated mixtures of PNs, ANs and HNO3 in zero air are converted into NO2 and used to fix the dissociation temperatures of each heated inlet, to test the selectivity of the instrument and potential interferences due to recombination reactions of the dissociated products. The effectiveness of the TD-LIF was demonstrated during the RONOCO aircraft campaign (summer 2010). A chemiluminescence system that was measuring NO2 and a broadband cavity enhanced absorption spectrometer (BBCEAS) that was measuring one of the PNs (N2O5) were installed on the same aircraft during the campaign. The in-flight intercomparison of the new TD-LIF with the chemiluminescence system for NO2 measurements and the intercomparison between ∑PNs measured by the TD-LIF and N2O5 by the BBCEAS are used to assess the performance of the TD-LIF.

Description: The RONOCO aircraft campaign during July 2010 and January 2011 made observations of OH, HO2, NO3, N2O5 and a number of supporting measurements at night over the UK, and reflects the first simultaneous airborne measurement of these species. We compare the observed concentrations of these short-lived species with those calculated by a box model, constrained by the concentrations of the longer lived species, using a detailed chemical scheme. OH concentrations were below the limit of detection, consistent with the model predictions. The model systematically underpredicts HO2 by a factor of ~2 and overpredicts NO3 and N2O5 by factors of around 75% and 50%, respectively. Cycling between NO3 and N2O5 is fast and thus we define the NO3x (NO3x = NO3 + N2O5) family. Production of NO3x is overwhelmingly dominated by the reaction of NO2 with O3, whereas its loss is dominated by aerosol uptake of N2O5, with NO3 + VOCs and NO3 + RO2 playing smaller roles. The production of HOx and ROx radicals is mainly due to the reaction of NO3 with VOCs. The loss of these radicals occurs through a combination of HO2 + RO2 reactions, heterogeneous processes and production of HNO3 from OH + NO2, with radical propagation primarily achieved through reactions of NO3 with peroxy radicals. Thus NO3 at night plays a similar role to both OH and NO during the day in that it both initiates ROx radical production and acts to propagate the oxidation chain. Model sensitivity to the N2O5 aerosol uptake coefficient (γN2O5) is discussed, and we find that a value of γN2O5 = 0.05 improves model simulations for NO3 and N2O5, but that these improvements are at the expense of model success for HO2. Improvements to model simulations for HO2, NO3 and N2O5 can be realised simultaneously on inclusion of additional unsaturated volatile organic compounds, however the nature of these compounds is extremely uncertain.

Description: Chemical modelling studies have been conducted over north-western Europe in summer conditions, showing that night-time dinitrogen pentoxide (N2O5) heterogeneous reactive uptake is important regionally in modulating particulate nitrate and has a modest influence on oxidative chemistry. Results from WRF-Chem model simulations, run with a detailed volatile organic compound (VOC) gas-phase chemistry scheme and the MOSAIC sectional aerosol scheme, were compared with a series of airborne gas and particulate measurements made over the UK in July 2010. Modelled mixing ratios of key gas-phase species were reasonably accurate (correlations with measurements of 0.7–0.9 for NO2 and O3). However modelled loadings of particulate species were less accurate (correlation with measurements for particulate sulphate and ammonium were between 0.0–0.6). Sulphate mass loadings were particularly low (modelled means of 0.5–0.7 μg kg−1air, compared with measurements of 1.0–1.5 μg kg−1air). Two flights from the campaign were used as testcases – one with low relative humidity (RH) (60–70%), the other with high RH (80–90%). N2O5 heterogeneous chemistry was found to not important in the low RH testcase; but in the high RH testcase it had a strong effect, and significantly improved the agreement between modelled and measured NO3 and N2O5. When the model failed to capture atmospheric RH correctly, the modelled NO3 and N2O5 mixing ratios for these flights differed significantly from the measurements. This demonstrates that, for regional modelling which involves heterogeneous processes, it is essential to capture the ambient temperature and water vapour profiles. The night-time NO3 oxidation of VOCs across the whole region was found to be × 100–300 slower than the daytime OH oxidation of these compounds. The difference in contribution was less for alkenes (× 80), and comparable for DMS. However the suppression of NO3 mixing ratios across the domain by N2O5 heterogeneous chemistry has only a very slight, negative, influence on this oxidative capacity. The influence on regional particulate nitrate mass loadings is stronger. Night-time N2O5 heterogeneous chemistry maintains the production of particulate nitrate within polluted regions: when this process is taken into consideration, the daytime peak (for the 95th percentile) of PM10 nitrate mass loadings remains around 5.6 μg kg−1air, but the nighttime minimum increases from 3.5 to 4.6 μg kg−1air. The sustaining of higher particulate mass loadings through the night by this process improves model skill at matching measured aerosol nitrate diurnal cycles, and will negatively impact on regional air quality, requiring this process to be included in regional models.

Description: The observations collected during the BORTAS campaign in summer 2011 over Canada are analysed to study the impact of forest fire emissions on the formation of ozone (O3) and total peroxy nitrates (ΣPNs, ΣROONO2). The suite of measurements on board the BAe-146 aircraft, deployed in this campaign, allows us to calculate the production of O3 and of ΣPNs, a long lived O3 reservoir whose concentration is supposed to be impacted by biomass burning emissions. In fire plumes, profiles of carbon monoxide (CO), which is a well-established tracer of pyrogenic emission, show concentration enhancements that are in strong correspondence with a significant increase of ΣPNs concentrations, whereas minimal increase of the concentrations of O3 and NO2 are observed. In those fire plumes the average ΣPNs production is 12 times greater than in the background plumes, by contrast the average O3 production is only 5 times greater. These results suggest that, at least for boreal forest fires and for the measurements recorded during the BORTAS campaign, fire emissions impact both the oxidized NOy and O3, but: (1) ΣPNs production is affected significantly respect to the O3 production and (2) in the forest fire plumes the ratio between the ΣPNs production and the O3 production is lower than the ratio evaluated in the background air masses, thus confirming that the role played by the ΣPNs produced during biomass burning is significant in the O3 budget. These observations are consistent with elevated production of PAN and concurrent low production (or sometimes loss) of O3 observed in some another campaigns (i.e. ARCTAS-B) focused on forest fire emissions. Moreover our observations extend ARCTAS-B results since PAN is one of the compounds included in the ΣPNs family detected during BORTAS. The implication of these observations is that fire emissions in some cases, for example Boreal forest fires and in the conditions reported here, may influence more long lived precursors of O3 than short lived pollutants, which in turn can be transported and eventually diluted in a wide area. These observations provide additional indirect evidence that O3 production may be enhanced as plumes from forest fires age.

Description: We present an analysis of ozone photochemistry observed by aircraft measurements of boreal biomass burning plumes over Eastern Canada in the summer of 2011. Measurements of ozone and a number of key chemical species associated with ozone photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the quantifying the impact of BOReal forest fires on tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS) experiment between 12 July and 3 August 2011. We found that ozone mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (=NOy - NOx) revealed that the potential for ozone production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 15 days. Ozone production, calculated from ΔO3/ΔCO enhancement ratios, increased from 0.020 ± 0.008 ppbv ppbv−1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbv ppbv−1 in plumes with photochemical ages greater than 5 days. In comparing ozone mixing ratios with components of the NOy budget we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiencies of 8 ppbv ppbv−1 relative to ΣAN and 2 ppbv ppbv−1 relative to NOz. In plumes with ages greater than 4 days, ozone production efficiency increased to 473 ppbv ppbv−1 relative to ΣAN and 155 ppbv ppbv−1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photostationary steady state and ozone production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to ozone. The BORTAS measurements of ozone photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990.

Description: Airborne measurements of biomass burning organic aerosol (BBOA) from boreal forest fires reveal highly contrasting properties for plumes of different ages. These measurements, performed using an Aerodyne Research Inc. compact time-of-flight aerosol mass spectrometer (C-ToF-AMS) during the BORTAS (quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) experiment in the summer of 2011, have been used to derive normalised excess organic aerosol (OA) mass concentrations (ΔOA/ΔCO), with higher average ratios observed closer to source (0.190 ± 0.010) than in the far-field (0.097 ± 0.002). The difference in ΔOA/ΔCO between fresh and aged plumes is influenced by a change in dominant combustion conditions throughout the campaign. Measurements at source sampled largely smouldering fires, while plumes encountered in the far-field originated from fires occurring earlier in the campaign when fire activity had been more intense. Changing combustion conditions also affect the vertical distribution of biomass burning emissions, as aged plumes from more flaming-dominated fires are injected to higher altitudes of up to 6000 m. Proportional contributions of the mass-to-charge ratio (m/z) 60 and 44 peaks in the AMS mass spectra to the total OA mass (denoted f60 and f44) are used as tracers for primary and oxidized BBOA, respectively. Given the shorter aging times associated with near-field plumes, f44 is lower on average than in more aged, transported plumes. However, high levels of ΔO3/ΔCO and -log(NOx/NOy) close to source indicate that emissions can be subject to very rapid oxidation over short timescales. Conversely, the lofting of plumes into the upper troposphere can lead to the retention of source profiles after transportation over extensive temporal and spatial scales, with f60 also higher on average in aged plumes. Evolution of OA composition with aging is comparable to observations of BB tracers in previous studies, revealing a consistent progression from f60 to f44. The elevated levels of oxygenation in aged plumes, and their association with lower average ΔOA/ΔCO, highlight the influence of OA losses during aging, although there remain considerable uncertainties regarding the role of combustion processes on BBOA production and composition.