ALBERT

Description: Nitrogen Dioxide is both a primary pollutant with direct health effects and a key precursor of the secondary pollutant ozone. This paper reports on the development, characterisation and test flight of the Atmospheric Nitrogen Dioxide Imager (ANDI) remote sensing system. The ANDI system includes an imaging (UV)-vis grating spectrometer able to capture scattered sunlight spectra for the determination of tropospheric nitrogen dioxide (NO2) concentrations by way of DOAS slant column density and vertical column density measurements. Results are shown for an ANDI test flight over Leicester City in the UK. Retrieved NO2 columns at a surface resolution of 80 m x 20 m revealed hot spots in a series of locations around Leicester City, including road junctions, the train station, major car parks, areas of heavy industry, a nearby airport (East Midlands) and a power station (Ratcliffe-on-Soar). In the city centre the dominant source of NO2 emissions was identified as road traffic, contributing to a background concentration as well as producing localised hot spots. Quantitative analysis revealed a significant urban increment over the city centre which increased throughout the flight.

Description: Air quality and heat are strong health drivers, and their accurate assessment and forecast are important in densely populated urban areas. However, the sources and processes leading to high concentrations of main pollutants, such as ozone, nitrogen dioxide, and fine and coarse particulate matter, in complex urban areas are not fully understood, limiting our ability to forecast air quality accurately. This paper introduces the Clean Air for London (ClearfLo; www.clearflo.ac.uk) project’s interdisciplinary approach to investigate the processes leading to poor air quality and elevated temperatures. Within ClearfLo, a large multi-institutional project funded by the U.K. Natural Environment Research Council (NERC), integrated measurements of meteorology and gaseous, and particulate composition/loading within the atmosphere of London, United Kingdom, were undertaken to understand the processes underlying poor air quality. Long-term measurement infrastructure installed at multiple levels (street and elevated), and at urban background, curbside, and rural locations were complemented with high-resolution numerical atmospheric simulations. Combining these (measurement–modeling) enhances understanding of seasonal variations in meteorology and composition together with the controlling processes. Two intensive observation periods (winter 2012 and the Summer Olympics of 2012) focus upon the vertical structure and evolution of the urban boundary layer; chemical controls on nitrogen dioxide and ozone production—in particular, the role of volatile organic compounds; and processes controlling the evolution, size, distribution, and composition of particulate matter. The paper shows that mixing heights are deeper over London than in the rural surroundings and that the seasonality of the urban boundary layer evolution controls when concentrations peak. The composition also reflects the seasonality of sources such as domestic burning and biogenic emissions.

Description: Highly non-linear dynamical systems, such as those found in atmospheric chemistry, necessitate hierarchical approaches to both experiment and modeling in order, ultimately, to identify and achieve fundamental process-understanding in the full open system. Atmospheric simulation chambers comprise an intermediate in complexity, between a classical laboratory experiment and the full, ambient system. As such, they can generate large volumes of difficult-to-interpret data. Here we describe and implement a chemometric dimension reduction methodology for the deconvolution and interpretation of complex gas- and particle-phase composition spectra. The methodology comprises principal component analysis (PCA), hierarchical cluster analysis (HCA) and positive least squares-discriminant analysis (PLS-DA). These methods are, for the first time, applied to simultaneous gas- and particle-phase composition data obtained from a comprehensive series of environmental simulation chamber experiments focused on biogenic volatile organic compound (BVOC) photooxidation and associated secondary organic aerosol (SOA) formation. We primarily investigated the biogenic SOA precursors isoprene, α-pinene, limonene, myrcene, linalool and β-caryophyllene. The chemometric analysis is used to classify the oxidation systems and resultant SOA according to the controlling chemistry and the products formed. Furthermore, a holistic view of results across both the gas- and particle-phases shows the different SOA formation chemistry, initiating in the gas-phase, proceeding to govern the differences between the various BVOC SOA compositions. The results obtained are used to describe the particle composition in the context of the oxidized gas-phase matrix. An extension of the technique, which incorporates into the statistical models data from anthropogenic (i.e. toluene) oxidation and "more realistic" plant mesocosm systems, demonstrates that such an ensemble of chemometric mapping has the potential to be used for the classification of more complex spectra of unknown origin. The potential to extend the methodology to the analysis of ambient air is discussed using results obtained from a zero-dimensional box model incorporating mechanistic data obtained from the Master Chemical Mechanism (MCMv3.2). Such an extension to analysing ambient air would prove a powerful asset in assisting with the identification of SOA sources and the elucidation of the underlying chemical mechanisms involved.

Description: State of the art techniques allow for rapid measurements of total OH reactivity. Unknown sinks of OH and oxidation processes in the atmosphere have been attributed to what has been termed "missing" OH reactivity. Often overlooked are the differences in timescales over which the diverse measurement techniques operate. Volatile organic compounds (VOC) acting as sinks of OH are often measured by gas chromatography (GC) methods which provide low frequency measurements on a timescale of hours, while sampling times are generally only a few minutes. Here, the effect of the sampling time and thus the contribution of unmeasured VOC variability on OH reactivity is investigated. Measurements of VOC mixing ratios by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) conducted during two field campaigns (ClearfLo and PARADE) in an urban and a semi-rural environment were used to calculate OH reactivity. VOC were selected to represent variability for different compound classes. Data were averaged over different time intervals to simulate lower time resolutions and were then compared to the mean hourly OH reactivity. The results show deviations in the range of 1 to 25%. The observed impact of VOC variability is found to be greater for the semi-rural site. The selected compounds were scaled by the contribution of their compound class to the total OH reactivity from VOC based on concurrent gas chromatography measurements conducted during the ClearfLo campaign. Prior to being scaled, the variable signal of aromatic compounds results in larger deviations in OH reactivity for short sampling intervals compared to oxygenated VOC (OVOC). However, once scaled with their lower share during the ClearfLo campaign this effect was reduced. No seasonal effect on the OH reactivity distribution across different VOC was observed at the urban site.

Description: A novel tropospheric NO2 DOAS retrieval algorithm optimised for a nadir-viewing satellite instrument imaging polluted areas is proposed in this work. Current satellite DOAS retrievals have relied on using a solar reference spectrum to derive a total slant column, then using either model assimilation or spatial filtering to derive the tropospheric component. In the ERrs-DOAS (Earth radiance reference sector DOAS) algorithm, tropospheric NO2 slant columns are derived using spectra averaged from measurements over unpolluted regions, thus removing the need for post-hoc separation techniques, though some residual stratospheric biases may still remain. To validate the ERrs-DOAS algorithm, DOAS retrievals were performed on modelled spectra created by the radiative transfer model SCIATRAN, as well as L1B Earth radiance data measured by the NASA/KNMI Ozone Monitoring Instrument (OMI). It was found that retrievals using an Earth radiance reference produce spatial distributions of tropospheric NO2 over eastern China during June 2005 that highly correlate with those derived using existing retrieval algorithms. Comparisons with slant columns retrieved by the operational NO2 retrieval algorithm for OMI (OMNO2A) show that the ERrs-DOAS algorithm greatly reduces the presence of artificial across-track biases (stripes) caused by calibration errors, as well as the removal of path length enhancement in off-nadir pixels. Analysis of Pacific SCDs suggests that the algorithm also produces a 27% reduction in retrieval uncertainty, though this may be partially due to biases introduced by differences in the retrieval algorithm settings. The ERrs-DOAS technique also reveals absorption features over the Sahara and similar regions characteristic of sand and liquid H2O absorption, as first discovered in the analysis of GOME-2 NO2 retrievals.

Description: The α-dicarbonyl compounds glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO) are produced in the atmosphere by the oxidation of hydrocarbons and emitted directly from pyrogenic sources. Measurements of ambient concentrations inform about the rate of hydrocarbon oxidation, oxidative capacity, and secondary organic aerosol (SOA) formation. We present results from a comprehensive instrument comparison effort at two simulation chamber facilities in the US and Europe that included nine instruments, and seven different measurement techniques: broadband cavity enhanced absorption spectroscopy (BBCEAS), cavity-enhanced differential optical absorption spectroscopy (CE-DOAS), white-cell DOAS, Fourier transform infrared spectroscopy (FTIR, two separate instruments), laser-induced phosphorescence (LIP), solid-phase micro extraction (SPME), and proton transfer reaction mass spectrometry (PTR-ToF-MS, two separate instruments; for methyl glyoxal only because no significant response was observed for glyoxal). Experiments at the National Center for Atmospheric Research (NCAR) compare three independent sources of calibration as a function of temperature (293–330 K). Calibrations from absorption cross-section spectra at UV-visible and IR wavelengths are found to agree within 2% for glyoxal, and 4% for methyl glyoxal at all temperatures; further calibrations based on ion–molecule rate constant calculations agreed within 5% for methyl glyoxal at all temperatures. At the European Photoreactor (EUPHORE) all measurements are calibrated from the same UV-visible spectra (either directly or indirectly), thus minimizing potential systematic bias. We find excellent linearity under idealized conditions (pure glyoxal or methyl glyoxal, R2 〉 0.96), and in complex gas mixtures characteristic of dry photochemical smog systems (o-xylene/NOx and isoprene/NOx, R2 〉 0.95; R2 ∼ 0.65 for offline SPME measurements of methyl glyoxal). The correlations are more variable in humid ambient air mixtures (RH 〉 45%) for methyl glyoxal (0.58 〈 R2 〈 0.68) than for glyoxal (0.79 〈 R2 〈 0.99). The intercepts of correlations were insignificant for the most part (below the instruments' experimentally determined detection limits); slopes further varied by less than 5% for instruments that could also simultaneously measure NO2. For glyoxal and methyl glyoxal the slopes varied by less than 12 and 17% (both 3-σ) between direct absorption techniques (i.e., calibration from knowledge of the absorption cross section). We find a larger variability among in situ techniques that employ external calibration sources (75–90%, 3-σ), and/or techniques that employ offline analysis. Our intercomparison reveals existing differences in reports about precision and detection limits in the literature, and enables comparison on a common basis by observing a common air mass. Finally, we evaluate the influence of interfering species (e.g., NO2, O3 and H2O) of relevance in field and laboratory applications. Techniques now exist to conduct fast and accurate measurements of glyoxal at ambient concentrations, and methyl glyoxal under simulated conditions. However, techniques to measure methyl glyoxal at ambient concentrations remain a challenge, and would be desirable.

Description: Nitrogen dioxide is both a primary pollutant with direct health effects and a key precursor of the secondary pollutant ozone. This paper reports on the development, characterisation and test flight of the Atmospheric Nitrogen Dioxide Imager (ANDI) remote sensing system. The ANDI system includes an imaging UV/Vis grating spectrometer able to capture scattered sunlight spectra for the determination of tropospheric nitrogen dioxide (NO2) concentrations by way of DOAS slant column density and vertical column density measurements. Results are shown for an ANDI test flight over Leicester City in the UK on a cloud-free winter day in February 2013. Retrieved NO2 columns gridded to a surface resolution of 80 m × 20 m revealed hotspots in a series of locations around Leicester City, including road junctions, the train station, major car parks, areas of heavy industry, a nearby airport (East Midlands) and a power station (Ratcliffe-on-Soar). In the city centre the dominant source of NO2 emissions was identified as road traffic, contributing to a background concentration as well as producing localised hotspots. Quantitative analysis revealed a significant urban increment over the city centre which increased throughout the flight.

Description: Ozone holds a certain fascination in atmospheric science. It is ubiquitous in the atmosphere, central to tropospheric oxidation chemistry, yet harmful to human and ecosystem health as well as being an important greenhouse gas. It is not emitted into the atmosphere but is a byproduct of the very oxidation chemistry it largely initiates. Much effort is focused on the reduction of surface levels of ozone owing to its health and vegetation impacts, but recent efforts to achieve reductions in exposure at a country scale have proved difficult to achieve owing to increases in background ozone at the zonal hemispheric scale. There is also a growing realisation that the role of ozone as a short-lived climate pollutant could be important in integrated air quality climate change mitigation. This review examines current understanding of the processes regulating tropospheric ozone at global to local scales from both measurements and models. It takes the view that knowledge across the scales is important for dealing with air quality and climate change in a synergistic manner. The review shows that there remain a number of clear challenges for ozone such as explaining surface trends, incorporating new chemical understanding, ozone–climate coupling, and a better assessment of impacts. There is a clear and present need to treat ozone across the range of scales, a transboundary issue, but with an emphasis on the hemispheric scales. New observational opportunities are offered both by satellites and small sensors that bridge the scales.

Description: Highly non-linear dynamical systems, such as those found in atmospheric chemistry, necessitate hierarchical approaches to both experiment and modelling in order to ultimately identify and achieve fundamental process-understanding in the full open system. Atmospheric simulation chambers comprise an intermediate in complexity, between a classical laboratory experiment and the full, ambient system. As such, they can generate large volumes of difficult-to-interpret data. Here we describe and implement a chemometric dimension reduction methodology for the deconvolution and interpretation of complex gas- and particle-phase composition spectra. The methodology comprises principal component analysis (PCA), hierarchical cluster analysis (HCA) and positive least-squares discriminant analysis (PLS-DA). These methods are, for the first time, applied to simultaneous gas- and particle-phase composition data obtained from a comprehensive series of environmental simulation chamber experiments focused on biogenic volatile organic compound (BVOC) photooxidation and associated secondary organic aerosol (SOA) formation. We primarily investigated the biogenic SOA precursors isoprene, α-pinene, limonene, myrcene, linalool and β-caryophyllene. The chemometric analysis is used to classify the oxidation systems and resultant SOA according to the controlling chemistry and the products formed. Results show that "model" biogenic oxidative systems can be successfully separated and classified according to their oxidation products. Furthermore, a holistic view of results obtained across both the gas- and particle-phases shows the different SOA formation chemistry, initiating in the gas-phase, proceeding to govern the differences between the various BVOC SOA compositions. The results obtained are used to describe the particle composition in the context of the oxidised gas-phase matrix. An extension of the technique, which incorporates into the statistical models data from anthropogenic (i.e. toluene) oxidation and "more realistic" plant mesocosm systems, demonstrates that such an ensemble of chemometric mapping has the potential to be used for the classification of more complex spectra of unknown origin. More specifically, the addition of mesocosm data from fig and birch tree experiments shows that isoprene and monoterpene emitting sources, respectively, can be mapped onto the statistical model structure and their positional vectors can provide insight into their biological sources and controlling oxidative chemistry. The potential to extend the methodology to the analysis of ambient air is discussed using results obtained from a zero-dimensional box model incorporating mechanistic data obtained from the Master Chemical Mechanism (MCMv3.2). Such an extension to analysing ambient air would prove a powerful asset in assisting with the identification of SOA sources and the elucidation of the underlying chemical mechanisms involved.