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

Reassessment of the factors controlling temporal profiles of nitrate in polar ice cores using evidence from snow and atmospheric measurements

International audienceNitrate is frequently measured in ice cores, but its interpretation remains immature. Using daily snow surface concentrations of nitrate at Halley (Antarctica) for 2004?2005, we show that sharp spikes (>factor 2) in nitrate concentration can occur from day to day. Some of these spikes will be preserved in ice cores. Many of them are associated with sharp increases in the concentration of sea salt in the snow. There is also a close association between the concentrations of aerosol nitrate and sea salt aerosol. This evidence is consistent with many of the spikes in deposited nitrate being due to the conversion or trapping of gas-phase nitrate, i.e. to enhanced deposition rather than enhanced atmospheric concentrations of NOy. Previously, sharp spikes in nitrate concentration (with concentration increases of up to a factor 4 seen in probably just one snowfall) have been assigned to sharp production events such as solar proton events (SPEs). We find that it is unlikely that SPEs can produce spikes of the kind seen. Taken together with our evidence that such spikes can be produced depositionally, we find that it is not possible to track past SPEs without carrying out a new multi-site and multi-analyte programme. Seasonal and interannual trends in nitrate concentration in cores from any single site cannot be interpreted in terms of production changes until the recycling of nitrate from central Antarctica to coastal Antarctica is better quantified. It might be possible to assess the interannual input of NOy to the Antarctic lower troposphere by using a network of cores to estimate variability in the total annual deposition across the continent (which we estimate to be 9±2×107 kg/a (as NO3?)), but it will first have to be established that the outflow across the coast can be ignored

Near-field emission profiling of Rainforest and Cerrado fires in Brazil during SAMBBA 2012

This discussion paper is a preprint. A revision of this manuscript was accepted for the journal Atmospheric Chemistry and Physics (ACP).We profile trace gas and particulate emissions from near-field airborne measurements of discrete smoke plumes in Brazil during the 2012 biomass burning season. The South American Biomass Burning Analysis (SAMBBA) Project conducted during September and October 2012 sampled across two distinct fire regimes prevalent in the Amazon Basin. Combined measurements from a Compact Time Of Flight Aerosol Mass Spectrometer (C-ToF-AMS) and a Single Particle Soot Photometer (SP2) are reported for the first time in a tropical biomass burning environment. Emissions from a mostly-smouldering rainforest wildfire in Rondonia state and numerous smaller flaming Cerrado fires in Tocantins state are presented. While the Cerrado fires appear to be representative of typical fire conditions in the existing literature, the rainforest wildfire likely represents a more extreme example of biomass burning with a bias towards mostly-smouldering emissions. We determined fire integrated modified combustion efficiencies, emission ratios and emission factors for trace gas and particulate components for these two fire types, alongside aerosol microphysical properties. Seven times more black carbon was emitted from the Cerrado fires per unit of fuel combustion (EFBC of 0.13 ± 0.04 g kg−1) compared to the rainforest fire (EFBC of 0.019 ± 0.006 g kg−1) and more than six times the amount of organic aerosol was emitted from the rainforest fire per unit of fuel combustion (EFOC of 5.00 ± 1.58 g kg−1) compared to the Cerrado fires (EFOC of 0.82 ± 0.26 g kg−1). Particulate phase species emitted from the fires sampled are generally lower than those reported in previous studies and in emission inventories, which is likely a combination of differences in fire combustion efficiency and fuel content, along with different measurement techniques. Previous modelling studies focussed on the biomass burning season in tropical South America have required significant scaling of emissions to reproduce in-situ and satellite aerosol concentrations over the region. Our results do not indicate that emission factors used in inventories are biased low, which could be one potential cause of the reported underestimates in modelling studies. This study supplements and updates trace gas and particulate emission factors for fire type specific biomass burning in Brazil for use in weather and climate models. The study illustrates that initial fire conditions can result in substantial differences in terms of their emitted chemical components, which can potentially perturb the Earth system.We would like to acknowledge the substantial efforts of the whole SAMBBA team before, during and after the project. Airborne data was obtained using the BAe-146-301 Atmospheric Research Aircraft (ARA) flown by Directflight Ltd and managed by the Facility for Airborne Atmospheric Measurements (FAAM), which is a joint entity of the Natural Environment Research Council (NERC) and the Met Office. Active fire data was produced by the University of Maryland and acquired from the online Fire Information for Resource Management System (FIRMS; https://earthdata.nasa.gov/data/near-real-time-data/firms/abouts; specific product: MCD14ML). E. Darbyshire was supported by NERC studentship NE/J500057/1 and NE/K500859/1. This work was supported by the NERC SAMBBA project NE/J010073/1

Near-field emission profiling of tropical forest and Cerrado fires in Brazil during SAMBBA 2012

This is the final version. Available from European Geosciences Union (EGU) / Copernicus Publications via the DOI in this record. Data availability: All raw time series data used to derive the emission ratios and factors from the FAAM research aircraft are publicly available from the Centre for Environmental Data Analysis website (http://www.ceda.ac.uk/, last access: 12 March 2018). Direct links to the flight data records are given in the reference list (Facility for Airborne Atmospheric Measurements, Natural Environment Research Council, and Met Office, 2014a, b).We profile trace gas and particulate emissions from near-field airborne measurements of discrete smoke plumes in Brazil during the 2012 biomass burning season. The South American Biomass Burning Analysis (SAMBBA) Project conducted during September and October 2012 sampled across two distinct fire regimes prevalent in the Amazon Basin. Combined measurements from a Compact Time-of-Flight Aerosol Mass Spectrometer (C-ToF-AMS) and a Single Particle Soot Photometer (SP2) are reported for the first time in a tropical biomass burning environment. Emissions from a mostly smouldering tropical forest wildfire in Rondônia state and numerous smaller flaming Cerrado fires in Tocantins state are presented. While the Cerrado fires appear to be representative of typical fire conditions in the existing literature, the tropical forest wildfire likely represents a more extreme example of biomass burning with a bias towards mostly smouldering emissions. We determined fire-integrated modified combustion efficiencies, emission ratios and emission factors for trace gas and particulate components for these two fire types, alongside aerosol microphysical properties. Seven times more black carbon was emitted from the Cerrado fires per unit of fuel combustion (EFBC of 0.13±0.04ĝ€†gĝ€†kg-1) compared to the tropical forest fire (EFBC of 0.019±0.006gĝ€†kg-1), and more than 6 times the amount of organic aerosol was emitted from the tropical forest fire per unit of fuel combustion (EFOM of 8.00±2.53gĝ€†kg-1, EFOC of 5.00±1.58gĝ€†kg-1) compared to the Cerrado fires (EFOM of 1.31±0.42gĝ€†kg-1, EFOC of 0.82±0.26gĝ€†kg-1). Particulate-phase species emitted from the fires sampled are generally lower than those reported in previous studies and in emission inventories, which is likely a combination of differences in fire combustion efficiency and fuel mixture, along with different measurement techniques. Previous modelling studies focussed on the biomass burning season in tropical South America have required significant scaling up of emissions to reproduce in situ and satellite aerosol concentrations over the region. Our results do not indicate that emission factors used in inventories are biased low, which could be one potential cause of the reported underestimates in modelling studies. This study supplements and updates trace gas and particulate emission factors for fire-type-specific biomass burning in Brazil for use in weather and climate models. The study illustrates that initial fire conditions can result in substantial differences in terms of their emitted chemical components, which can potentially perturb the Earth system.NERCMet Offic

Constraints on oceanic methane emissions west of Svalbard from atmospheric in situ measurements and Lagrangian transport modeling

Methane stored in seabed reservoirs such as methane hydrates can reach the atmosphere in the form of bubbles or dissolved in water. Hydrates could destabilize with rising temperature further increasing greenhouse gas emissions in a warming climate. To assess the impact of oceanic emissions from the area west of Svalbard, where methane hydrates are abundant, we used measurements collected with a research aircraft (Facility for Airborne Atmospheric Measurements) and a ship (Helmer Hansen) during the Summer 2014 and for Zeppelin Observatory for the full year. We present a model-supported analysis of the atmospheric CH$_{4}$mixing ratios measured by the different platforms. To address uncertainty about where CH$_{4}$ emissions actually occur, we explored three scenarios: areas with known seeps, a hydrate stability model, and an ocean depth criterion. We then used a budget analysis and a Lagrangian particle dispersion model to compare measurements taken upwind and downwind of the potential CH$_{4}$ emission areas. We found small differences between the CH$_{4}$ mixing ratios measured upwind and downwind of the potential emission areas during the campaign. By taking into account measurement and sampling uncertainties and by determining the sensitivity of the measured mixing ratios to potential oceanic emissions, we provide upper limits for the CH$_{4}$ fluxes. The CH$_{4}$ flux during the campaign was small, with an upper limit of 2.5 nmol m$^{-2}$ s$^{-1}$ in the stability model scenario. The Zeppelin Observatory data for 2014 suggest CH$_{4}$ fluxes from the Svalbard continental platform below 0.2 Tg yr$^{-1}$. All estimates are in the lower range of values previously reported.MOCA—Methane Emissions from the Arctic OCean to the Atmosphere: Present and Future Climate Effects is funded by the Research Council of Norway, grant 225814. CAGE—Centre for Arctic Gas Hydrate, Environment and Climate research work was supported by the Research Council of Norway through its Centres of Excellence funding scheme grant 223259. eSTICC—eScience Tools for Investigating Climate Change in northern high latitudes is supported by Nordforsk as Nordic Center of Excellence grant 57001. NERC grants NE/I029293/1 (PI. H. Coe) and NE/I02916/1 (PI J. Pyle) and Methane & Other Greenhouse Gases in the Arctic—Measurements, Process Studies and Modelling (MAMM). The ERC through the ACCI project, project number 267760. The biogenic methane emission data from the LPX-Bern v1.2 model were provided by Renato Spahni. The methane emission data from the GAINS model were provided by IIASA. GFED data are available from http://www.globalfiredata.org/index.html. Airborne data were obtained using the BAe-146-301 Atmospheric Research Aircraft (ARA) flown by Directflight Ltd. and managed by the Facility for Airborne Atmospheric Measurements (FAAM), which is a joint entity of the Natural Environment Research Council (NERC) and the Met Office. Zeppelin and Helmer Hansen atmospheric measurement data are archived in EBAS (http://ebas.nilu.no/) for long-term preservation, access and use. All Zeppelin data for 2014: http://ebas.nilu.no/DataSets.aspx?stations=NO0042G&fromDate=2014-01-01&toDate=2014-12-31. All atmospheric data from RV Helmer Hanssen: http://ebas.nilu.no/DataSets.aspx?stations=NO1000R&fromDate=2014-01-01&toDate=2014-12-31 (password is required until the end of 2017)

The multi-seasonal NO_y budget in coastal Antarctica and its link with surface snow and ice core nitrate: results from the CHABLIS campaign

International audienceMeasurements of individual NOy components were carried out at Halley station in coastal Antarctica. The measurements were made as part of the CHABLIS campaign (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) and cover over half a year, from austral winter 2004 through to austral summer 2005. They are the longest duration and most extensive NOy budget study carried out to date in polar regions. Results show clear dominance of organic NOy compounds (PAN and MeONO2) during the winter months, with low concentrations of inorganic NOy, but a reversal of this situation towards summer when the balance shifts in favour of inorganic NOy. Multi-seasonal measurements of surface snow nitrate correlate strongly with inorganic NOy species. One case study in August suggested that particulate nitrate was the dominant source of nitrate to the snowpack, but this was not the consistent picture throughout the measurement period. An analysis of NOx production rates showed that emissions of NOx from the snowpack dominate over gas-phase sources of "new NOx", suggesting that, for certain periods in the past, the flux of NOx into the boundary layer can be calculated from ice core nitrate data

Night-time measurements of HO<inf>x</inf> during the RONOCO project and analysis of the sources of HO<inf>2</inf>

Abstract. Measurements of the radical species OH and HO2 were made using the fluorescence assay by gas expansion (FAGE) technique during a series of night-time and daytime flights over the UK in summer 2010 and winter 2011. OH was not detected above the instrument's 1σ limit of detection during any of the night-time flights or during the winter daytime flights, placing upper limits on [OH] of 1.8 × 106 molecule cm−3 and 6.4 × 105 molecule cm−3 for the summer and winter flights, respectively. HO2 reached a maximum concentration of 3.2 × 108 molecule cm−3 (13.6 pptv) during a night-time flight on 20 July 2010, when the highest concentrations of NO3 and O3 were also recorded. An analysis of the rates of reaction of OH, O3, and the NO3 radical with measured alkenes indicates that the summer night-time troposphere can be as important for the processing of volatile organic compounds (VOCs) as the winter daytime troposphere. An analysis of the instantaneous rate of production of HO2 from the reactions of O3 and NO3 with alkenes has shown that, on average, reactions of NO3 dominated the night-time production of HO2 during summer and reactions of O3 dominated the night-time HO2 production during winter. This work was funded by the UK Natural Environment Research Council (NE/F004664/1). The authors would like to thank ground staff, engineers, scientists, and pilots involved in RONOCO for making this project a success. Airborne data were obtained using the BAe 146-301 Atmospheric Research Aircraft (ARA) flown by Directflight Ltd. and managed by the Facility for Airborne Atmospheric Measurements (FAAM), which is a joint entity of the Natural Environment Research Council (NERC) and the Met Office.This is the final version of the article. It first appeared from Copernicus Publications via http://dx.doi.org/10.5194/acp-15-8179-201

Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS) experiment: design, execution and science overview

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 45 sr 10 days, largely by virtue of widespread fires over Northwestern Ontario. Airborne measurements reported a large number of emitted gases including semi-volatile species, some of which have not been been previously reported in pyrogenic plumes, with the corresponding emission ratios agreeing with previous work for common gases. Analysis of the NOy data shows evidence of net ozone production in pyrogenic plumes, controlled by aerosol abundance, which increases as a function of photochemical age. 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 in the boundary layer. Ground-based measurements of particulate matter smaller than 2.5 μm (PM2.5) over Halifax show that forest fires can on an episodic basis represent a substantial contribution to total surface PM2.5

Night-time measurements of HOx during the RONOCO project and analysis of the sources of HO2

Measurements of the radical species OH and HO2 were made using the fluorescence assay by gas expansion (FAGE) technique during a series of night-time and daytime flights over the UK in summer 2010 and winter 2011. OH was not detected above the instrument's 1σ limit of detection during any of the night-time flights or during the winter daytime flights, placing upper limits on [OH] of 1.8 × 106 molecule cm−3 and 6.4 × 105 molecule cm−3 for the summer and winter flights, respectively. HO2 reached a maximum concentration of 3.2 × 108 molecule cm−3 (13.6 pptv) during a night-time flight on 20 July 2010, when the highest concentrations of NO3 and O3 were also recorded. An analysis of the rates of reaction of OH, O3, and the NO3 radical with measured alkenes indicates that the summer night-time troposphere can be as important for the processing of volatile organic compounds (VOCs) as the winter daytime troposphere. An analysis of the instantaneous rate of production of HO2 from the reactions of O3 and NO3 with alkenes has shown that, on average, reactions of NO3 dominated the night-time production of HO2 during summer and reactions of O3 dominated the night-time HO2 production during winter