Aircraft based four-channel thermal dissociation laser induced fluorescence instrument for simultaneous measurements of NO2, total peroxy nitrate, total alkyl nitrate, and HNO3

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

Analysis of Summer Ozone Observations at a High Mountain Site in Central Italy (Campo Imperatore, 2388 m a.s.l.)

Tropospheric ozone (O3) is an important atmospheric pollutant and climate forcer. The Mediterranean basin is a hot-spot region in terms of short-term O3 distribution, with frequent episodes of high tropospheric O3, especially during summer. To improve the characterisation of summer O3 variability in the Mediterranean area, during the period 6–27 August 2009 an experimental campaign was conducted at Campo Imperatore, Mt Portella (CMP), a high mountain site (2,388 m a.s.l.) located in the central Italian Apennines. As deduced from analysis of atmospheric circulation, the measurement site was significantly affected by air masses originating over the Mediterranean basin, which affected the measurement site for 32 % of the time. Analysis of average values and diurnal and day-to-day variability revealed that CMP O3 observations (average value 60.0 ± 5.1 ppbv) were comparable with measurements at other European mountain stations, indicating a prevalent effect of meteorological conditions and atmospheric transport on the synoptic scale. In fact, only a small "reverse" diurnal variation typically characterises diurnal O3 variability because of local thermal wind circulation, which sporadically favours transport of air masses rich in O3 from the foothill regions. Statistical analysis of five-day back-trajectory ensembles indicates that synoptic-scale air-mass transport from the Mediterranean Sea usually results in decreasing O3 concentrations at CMP, whereas the highest hourly O3 values are mostly associated with air masses from central continental Europe, eastern Europe, and northern Italy. High O3 concentrations are also related to downward air-mass transport from higher altitudes. Comparison of in-situ O3 variability with tropospheric O3 satellite-based measurements reveals similar features of the two data sets. Together with the results from back-trajectory analysis, this indicates that CMP measurements might usefully improve characterisation of broad-scale O3 variability over the central Mediterranean basin

Production of peroxy nitrates in boreal biomass burning plumes over Canada during the BORTAS campaign

The observations collected during the BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites (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 ∑PNs, ∑ROONO₂). The suite of measurements on board the BAe-146 aircraft, deployed in this campaign, allows us to calculate the production of O₃ and of  ∑PNs, a long-lived NO_<i>x</i> 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 concentrations of ∑PNs, whereas minimal increase of the concentrations of O₃ and NO₂ is observed. The ∑PN and O₃ productions have been calculated using the rate constants of the first- and second-order reactions of volatile organic compound (VOC) oxidation. The ∑PN and O₃ productions have also been quantified by 0-D model simulation based on the Master Chemical Mechanism. Both methods show that in fire plumes the average production of ∑PNs and O₃ are greater than in the background plumes, but the increase of ∑PN production is more pronounced than the O₃ production. The average ∑PN production in fire plumes is from 7 to 12 times greater than in the background, whereas the average O₃ production in fire plumes is from 2 to 5 times greater than in the background. 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 NO_<i>y</i> and O_3, but (1 ∑PN production is amplified significantly more than O₃ production and (2) in the forest fire plumes the ratio between the O₃ production and the ∑PN production is lower than the ratio evaluated in the background air masses, thus confirming that the role played by the ∑PNs produced during biomass burning is significant in the O₃ budget. 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

Impact of Biomass Burning emission on total peroxy nitrates: fire plume identification during the BORTAS campaign

Total peroxy nitrate (Sigma PN) concentrations have been measured using a thermal dissociation laser-induced fluorescence (TD-LIF) instrument during the BORTAS campaign, which focused on the impact of boreal biomass burning (BB) emissions on air quality in the Northern Hemisphere. The strong correlation observed between the Sigma PN concentrations and those of carbon monoxide (CO), a well-known pyrogenic tracer, suggests the possible use of the Sigma PN concentrations as marker of the BB plumes. Two methods for the identification of BB plumes have been applied: (1) Sigma PN concentrations higher than 6 times the standard deviation above the background and (2) Sigma PN concentrations higher than the 99th percentile of the Sigma PNs measured during a background flight (B625); then we compared the percentage of BB plume selected using these methods with the percentage evaluated, applying the approaches usually used in literature. Moreover, adding the pressure threshold (similar to 750 hPa) as ancillary parameter to Sigma PNs, hydrogen cyanide (HCN) and CO, the BB plume identification is improved. A recurrent artificial neural network (ANN) model was adapted to simulate the concentrations of Sigma PNs and HCN, including nitrogen oxide (NO), acetonitrile (CH3CN), CO, ozone (O-3) and atmospheric pressure as input parameters, to verify the specific role of these input data to better identify BB plumes

Molding and Stretched Evolution of Optical Solitons in Cumulative Nonlinearities

The observation of initial time dynamics of self-trapping in photorefractive media indicates that optical spatial solitons supported by intense cumulative nonlinearities manifest temporally nonlocal signatures in the form of stretched exponential behavior. This general result, supported also by numerical predictions, is triggered by wave shaping in a time-constant buildup map, a consequence of the spatially resolved inertial response intrinsic to the geometrical transition from a diffracting to a self-focused beam, inherent to soliton appearance

Observations of total peroxy nitrates and total alkyl nitrates during the OP3 campaign: isoprene nitrate chemistry above a south-east Asian tropical rain forest

Measurements of total peroxy nitrates (ΣRO2NO2, ΣPNs), total alkyl nitrates (ΣRONO2, ΣANs) and nitrogen dioxide (NO2) were made above the surface of a Malaysian tropical rain forest in Borneo, using a laser-induced fluorescence instrument developed at the University of L'Aquila (Italy). This new instrument uses the direct excitation of NO2 at 532 nm in order to measure its concentrations detecting by the NO2 fluorescence at wavelengths longer than 610 nm. ΣPNs and ΣANs are indirectly measured after their thermal dissociation into NO2. Observations showed enhanced levels of NO2 during nighttime, an increase of ΣPNs during the afternoon and almost no evident diurnal cycle of ΣANs. The diurnal maximums of 200 pptv for ΣPNs and ΣANs are well below the peaks reported in other forest sites. A box model constrained with measured species, reproduces well the observed ΣPNs, but overestimates ΣANs concentrations. The reason of this model-observation discrepancy could be a wrong parameterization in the isoprene nitrates (INs) chemistry mechanism. Sensitivity tests show that: (1) reducing the yield of INs from the reaction of peroxy nitrates with NO to almost the lowest values reported in literature (5%), (2) reducing the INs recycling to 70% and (3) keeping the INs dry deposition at 4 cm s−1, improve the agreement between modelled and measured ΣANs of 20% on average. These results imply that in the tropical rain forest, even if ΣPNs and ΣANs concentrations are lower than those observed in other North American forests, the yield and dry deposition of INs are similar. Another comparable result is that in the INs oxidation its recycling dominates with only a 30% release of NO2, which has implications on tropospheric ozone production and aerosol budget

Radical chemistry at night:Comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project

The RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity of the AtmOsphere) 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 measurements 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 model predictions. The model systematically underpredicts HO2 by ∼200% and overpredicts NO3 and N2O5 by around 80 and 50%, respectively. Cycling between NO3 and N2O5 is fast and thus we define the NO3x (NO3xCombining double low lineNO3+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 (volatile organic compounds) 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 tropospheric oxidation chain. Model sensitivity to the N2O5 aerosol uptake coefficient (γN2O5) is discussed and we find that a value of γN2O5Combining double low line0.05 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

Effects of land use on surface–atmosphere exchanges of trace gases and energy in Borneo: comparing fluxes over oil palm plantations and a rainforest

This paper reports measurements of land–atmosphere fluxes of sensible and latent heat, momentum, CO2, volatile organic compounds (VOCs), NO, NO2, N2O and O3 over a 30 m high rainforest canopy and a 12 m high oil palm plantation in the same region of Sabah in Borneo between April and July 2008. The daytime maximum CO2 flux to the two canopies differs by approximately a factor of 2, 1200 mg C m−2 h−1 for the oil palm and 700 mg C m−2 h−1 for the rainforest, with the oil palm plantation showing a substantially greater quantum efficiency. Total VOC emissions are also larger over the oil palm than over the rainforest by a factor of 3. Emissions of isoprene from the oil palm canopy represented 80 per cent of the VOC emissions and exceeded those over the rainforest in similar light and temperature conditions by on average a factor of 5. Substantial emissions of estragole (1-allyl-4-methoxybenzene) from the oil palm plantation were detected and no trace of this VOC was detected in or above the rainforest. Deposition velocities for O3 to the rainforest were a factor of 2 larger than over oil palm. Emissions of nitrous oxide were larger from the soils of the oil palm plantation than from the soils of the rainforest by approximately 25 per cent. It is clear from the measurements that the large change in the species composition generated by replacing rainforest with oil palm leads to profound changes in the net exchange of most of the trace gases measured, and thus on the chemical composition of the boundary layer over these surfaces