[Show abstract][Hide abstract] ABSTRACT: The experiment presented in this paper was conducted at the Holme Moss site, which is located in the southern Pennines region in Northwestern England during November–December 2006. The strong southwesterly wind during the experimental period, which enhanced the transport of urban pollutants from the conurbations of Greater Manchester and Liverpool, in addition to the seasonally increased nearby residential heating activities, made this site a receptor for pollutants from a range of sources. A factor analysis is applied to the mass spectra of organic matter (OM) measured by the Aerodyne Aerosol Mass Spectrometer (AMS) to attribute the pollutant sources. Besides the oxygenated organic aerosol (OOA), this site was found to contain a considerable fraction of primary organic aerosols (POA, mass fraction 50–70% within total mass of OM), which are source attributed as traffic emission and solid fuel burning, and are identified as hydrocarbon-like organic aerosol (HOA) and solid fuel organic aerosol (SFOA) respectively. There were strongly combined emissions of black carbon (BC) particles from both sources, as the refractory BC component (rBC) was characterized by the single particle soot photometer. This site began to be influenced during the late morning by fresh traffic emissions, whereas solid fuel burning became dominant from late afternoon until night. A covariance analysis of rBC and POA was used to derive source specific emission factors of 1.61 μgHOA/μgrBC and 1.96 μgSFOA/μgrBC. The absorbing properties of aerosols were characterized at multiple wavelengths (λ), and a stronger spectral dependence of absorption was observed when this site was significantly influenced by solid fuel burning. The rBC was estimated to contribute 3–16% of submicron aerosol mass. The single scattering albedo at λ=550 nm (SSA550 nm) was significantly anti-correlated with the rBC mass fraction, but also associated with the BC mixing state. The BC incorporation/removal process therefore plays an important role on modulating the radiative properties of aerosols at the site under the influence of fresh sources. Given that traffic and residential combustion of solid fuels are significant contributors of carbonaceous aerosols over Europe, these results provide important source-specific information on modeling the anthropogenic carbonaceous aerosols.
Full-text · Article · Jan 2010 · Atmospheric Chemistry and Physics
[Show abstract][Hide abstract] ABSTRACT: Nanoparticles of iron oxide (crystalline and amorphous), silicon oxide and magnesium oxide were investigated for their propensity to nucleate ice over the temperature range 180–250 K, using the AIDA chamber in Karlsruhe, Germany. All samples were observed to initiate ice formation via the deposition mode at threshold ice super-saturations (RHi thresh) ranging from 105% to 140% for temperatures below 220 K. Approximately 10% of amorphous Fe2O3 particles (modal diameter = 30 nm) generated in situ from a photochemical aerosol reactor, led to ice nucleation at RHi thresh = 140% at an initial chamber temperature of 182 K. Quantitative analysis using a singular hypothesis treatment provided a fitted function [ns (190 K) = 10(3.33×sice)+8.16] for the variation in ice-active surface site density (ns: m−2) with ice saturation (sice) for Fe2O3 nanoparticles. This was implemented in an aerosol-cloud model to determine a predicted deposition (mass accommodation) coefficient for water vapour on ice of 0.1 at temperatures appropriate for the upper atmosphere. Classical nucleation theory was used to determine representative contact angles (θ) for the different particle compositions. For the in situ generated Fe2O3 particles, a slight inverse temperature dependence was observed with θ = 10.5° at 182 K, decreasing to 9.0° at 200 K (compared with 10.2° and 11.4°, respectively for the SiO2 and MgO particle samples at the higher temperature). These observations indicate that such refractory nanoparticles are relatively efficient materials for the nucleation of ice under the conditions studied in the chamber which correspond to cirrus cloud formation in the upper troposphere. The results also show that Fe2O3 particles do not act as ice nuclei under conditions pertinent for tropospheric mixed phase clouds, which necessarily form above ~233 K. At the lower temperatures (<150 K) where noctilucent clouds form during summer months in the high latitude mesosphere, higher contact angles would be expected, which may reduce the effectiveness of these particles as ice nuclei in this part of the atmosphere.
Full-text · Article · Nov 2009 · Atmospheric Chemistry and Physics
[Show abstract][Hide abstract] ABSTRACT: We present results of experiments at the aerosol interactions and dynamics in the atmosphere (AIDA) chamber facility looking at the freezing of water by three different types of mineral particles at temperatures between −12°C and −33°C. The three different dusts are Asia Dust-1 (AD1), Sahara Dust-2 (SD2) and Arizona test Dust (ATD). The dust samples used had particle concentrations of sizes that were log-normally distributed with mode diameters between 0.3 and 0.5 μm and standard deviations, σg, of 1.6–1.9. The results from the freezing experiments are consistent with the singular hypothesis of ice nucleation. The dusts showed different nucleation abilities, with ATD showing a rather sharp increase in ice-active surface site density at temperatures less than −24°C. AD1 was the next most efficient freezing nuclei and showed a more gradual increase in activity than the ATD sample. SD2 was the least active freezing nuclei. We used data taken with particle counting probes to derive the ice-active surface site density forming on the dust as a function of temperature for each of the three samples and polynomial curves are fitted to this data. The curve fits are then used independently within a bin microphysical model to simulate the ice formation rates from the experiments in order to test the validity of parameterising the data with smooth curves. Good agreement is found between the measurements and the model for AD1 and SD2; however, the curve for ATD does not yield results that agree well with the observations. The reason for this is that more experiments between −20 and −24°C are needed to quantify the rather sharp increase in ice-active surface site density on ATD in this temperature regime. The curves presented can be used as parameterisations in atmospheric cloud models where cooling rates of approximately 1°C min−1 or more are present to predict the concentration of ice crystals forming by the condensation-freezing mode of ice nucleation. Finally a polynomial is fitted to all three samples together in order to have a parameterisation describing the average ice-active surface site density vs. temperature for an equal mixture of the three dust samples.
[Show abstract][Hide abstract] ABSTRACT: Primary biogenic aerosols (PBA) are used by organisms as a means to propagate their genetic material, either by transport of the organisms themselves, such as bacterial clusters and viruses, or of their reproductive components in the case of fungi and plants that release spores and pollen. Many studies have suggested PBA might be important for initiation of cloud formation and subsequent precipitation evolution by acting as cloud condensation nuclei (CCN) or possibly as ice nuclei (IN). This link is inferred from laboratory studies demonstrating the high activation efficiency of PBA at warm temperatures, coupled with observations that biological particles are ubiquitous in the atmosphere. Despite more than two hundred years of research (e.g. Ehrenberg, 1830) information on the abundance, composition and more importantly the sources and heterogeneity of PBA on global scales is still lacking. The first estimates of global average PBA emission rates based on observations and budget calculations were provided by Elbert et al. (2007). They demonstrate that fungi contribute a major fraction of the observed coarse PBA PM10 mass (particles with diameters between 1-10 m), particularly Acomycota (AAM) and Basidiomycota (ABM) commonly seen in tropical regions. These species discharge their spores via so-called "active wet" mechanisms that eject spores inside liquid droplets. Elbert et al. (2007) estimate a global average spore emission rate for ABM of ~17-50 Tg yr-1, corresponding to a global average abundance of ~1 g m-3 and a net emission rate for all fungal spores of 50 Tg yr-1. Uncertainty in the latter estimate is significant compared to the result, placed at 50-1000 Tg yr-1. Nonetheless, these calculations demonstrate the potential importance of PBA and particularly fungal spores in the tropics, where up to half of the coarse mode particulate loading is PBA, and potentially in the global organic aerosol budget. Data was collected using the WIBS-3: a low-cost, portable single-particle dual channel UV fluorescence spectrometer (Kaye et al., 2008) capable of detecting PBA by inducing fluorescence in two so-called biofluorophores - one present during metabolism and the other an amino acid - in the particle size range 1 m < Dp 2 m. In qualitative agreement with measurements of culturable airborne material in a tropical forest's understory (Gilbert, 2005) a diurnal cycle of PBA number concentration is present, reaching a maximum of ~4000 l-1 at local midnight and falling to ~100 l-1 around midday. The role of the planetary boundary layer's collapse and re-establishment in dictating this variation in is also investigated using LIDAR data. Transient PBA concentration spikes lasting several minutes are superposed on the smooth underlying diurnal variation and occur at similar times each day. Nucleopore filter samples were also taken in-situ and analysed under an Environmental scanning electron microscope (ESEM) in Manchester. The images obtained showed the PBA fraction to be dominated by fungal spores of diameter 2-5 m, from various species including ABM. Since such species tend to release spores in bursts at regular times this appears to account for the PBA concentration spikes.
[Show abstract][Hide abstract] ABSTRACT: Licensed under a Creative Commons License and also available from http://www.copernicus.org/EGU/acp/acp.html, along with further discussion. Renewal of ultrafine aerosols in the marine boundary layer may lead to repopulation of the marine distribution and ultimately determine the concentration of cloud condensation nuclei (CCN). Thus the formation of nanometre-scale particles can lead to enhanced scattering of incoming radiation and a net cooling of the atmosphere. The recent demonstration of the chamber formation of new particles from the photolytic production of condensable iodine-containing compounds from diiodomethane (CH2I2), (O’Dowd et al., 2002; Kolb, 2002; Jimenez et al., 2003a; Burkholder and Ravishankara, 2003), provides an additional mechanism to the gas-to-particle conversion of sulphuric acid formed in the photo-oxidation of dimethylsulphide for marine aerosol repopulation. CH2I2 is emitted from seaweeds (Carpenter et al., 1999, 2000) and has been suggested as an initiator of particle formation. We demonstrate here for the first time that ultrafine iodine-containing particles are produced by intertidal macroalgae exposed to ambient levels of ozone. The particle composition is very similar both to those formed in the chamber photo-oxidation of diiodomethane and in the oxidation of molecular iodine by ozone. The particles formed in all three systems are similarly aspherical. When small, those formed in the molecular iodine system swell only moderately when exposed to increased humidity environments, and swell progressively less with increasing size; this behaviour occurs whether they are formed in dry or humid environments, in contrast to those in the CH2I2 system. Direct coastal boundary layer observations of molecular iodine, ultrafine particle production and iodocarbons are reported. Using a newly measured molecular iodine photolysis rate, it is shown that, if atomic iodine is involved in the observed particle bursts, it is of the order of at least 1000 times more likely to result from molecular iodine photolysis than diiodomethane photolysis. A hypothesis for molecular iodine release from intertidal macroalgae is presented and the potential importance of macroalgal iodine particles in their contribution to CCN and global radiative forcing are discussed.
Full-text · Article · May 2004 · ATMOSPHERIC CHEMISTRY AND PHYSICS
[Show abstract][Hide abstract] ABSTRACT: The primary and secondary air pollutant concentrations across the urban conurbations in the West Midlands region of England were predicted using a high spatial resolution mesoscale model. The ground- and air-based observations were used to validate the model in three dimensions. Aircraft were used to measure aerosols and trace gases in the troposphere of the conurbation surrounding Birmingham (UK). The net flux of pollutants from the Birmingham conurbation was estimated using mathematical models.
No preview · Article · Sep 2000 · Journal of Aerosol Science
[Show abstract][Hide abstract] ABSTRACT: The UMIST instrumented light aircraft (Cessna 182) was used during summer 1999 and winter 2000 to make measurements of aerosol and trace gases in the Boundary Layer (BL) and Free Troposphere (FT) both upwind and downwind of the city of Birmingham in the UK. These measurements were made as part of the NERC URGENT/ASURE program PUMA (Pollution of the Urban Midlands Atmosphere). Gradients in the concentrations of fine and accumulation mode aerosol and of the trace gases NOx and ozone were observed both in the vertical and horizontally across the conurbation. Examples are presented. These, and thermodynamic data have been made available to initialise and validate output from a high spatial resolution meso-scale model (coupled to dispersion and atmospheric chemistry modules) developed elsewhere in PUMA (in order to predict primary and secondary air pollutant concentrations at urban background locations across the West Midlands region of England).
[Show abstract][Hide abstract] ABSTRACT: Detailed studies have been made of the behaviour of gases and radicals involved in the production of oxidants at the Weybourne Atmospheric Observatory in both summertime and wintertime conditions. In June 1995 the range of meteorological conditions experienced varied such that ozone destruction was observed in clean northerly air flows reaching Weybourne down the North Sea from the Arctic, and ozone production was observed in varying degrees in air with different loadings of nitrogen oxides and other precursors. The transition point for ozone destruction to ozone production occurred at a nitric oxide concentration of the order of 50 pptv. Plumes of polluted air from various urban areas in the U.K. were experienced in the June campaign at Weybourne. Quantitative studies of ozone production in a plume from the Birmingham conurbation on 18 June 1995 showed that the measurement of ozone production agreed well with calculated production rates from the product of the nitric oxide and peroxy radical concentrations (r2=0.9). In wintertime conditions (October–November 1994) evidence was also found for oxidant production, defined as the sum of O3+NO2. At this time of year the peroxy radical concentrations (RO2) were much lower than observed in the summertime and the nitric oxide (NO) was much higher. There was still sufficient RO2 during the day, however, for a slow accumulation of oxidant. Confirmatory evidence for this comes from the diurnal co-variance of (O3+NO2) with PAN, an excellent tracer of tropospheric photochemistry. The same type of covariance occurs in summer between PAN and ozone. The results obtained in these series of measurements are pertinent to understanding the measures necessary to control production of regional photochemical air pollution, and to the production of ozone throughout the northern hemisphere in winter.
No preview · Article · May 1999 · Journal of Atmospheric Chemistry
[Show abstract][Hide abstract] ABSTRACT: Daily variations of the hydroxyl radical concentration have been measured during a campaign at the Weybourne Atmospheric Observatory (WAO) in June 1995. These measurements are compared with box model calculations, based on a slightly modified, second generation Regional Acid Deposition Model (RADM2). Results from eight days of the comparison are presented. A detailed analysis and discussion of the different source and sink terms is given for two days: Julian Day (JD) 170 (19 June, and 178 (27 June). In both cases excellent agreement between the measurements and the calculation is obtained, indicating that the model describes the OH chemistry sufficiently well. Furthermore, the analysis of these days demonstrate that JD 170 is dominated by the NOx catalysed OH production, whereas JD 178 is influenced by OH formation via ozone photolysis.
No preview · Article · May 1999 · Journal of Atmospheric Chemistry
[Show abstract][Hide abstract] ABSTRACT: Calculated and observed hydroxyl (OH) fields are presented. Calculated OH was obtained in three ways using (1) a photochemical box-model (2) a simple OH steady state approach and (3) a variant on (2) – the multiple equation steady state approach which assumes steady state for OH, HO2 and RO2 and hence obtains three simultaneous, non linear, equations. All three methods used data collected in June 1995 during the Weybourne Atmospheric Observatory Summer Experiment (WAOSE'95). Julian Days 169, 178, 179 and 180 displayed especially good data capture and were consequently chosen for study. The two steady state methods are essentially driven purely by observations and derive OH from the ratio of the relevant source and sink terms. The box-model was constrained where possible to observations; remaining unmeasured volatile organic compounds (VOCs) were initialised to an arbitrary low value of 10 ppt. Agreement between theory and experiment was usually around 50% and often better than this value, especially on J169, though discrepancies of up to a factor of 3 were occasionally apparent. Despite the inherent scatter, neither the box-model nor the simple steady state method were found to consistently over-estimate OH (a common feature of many numerical approaches) although this did occur to a certain extent using the multiple equation steady state approach, probably due to breakdowns in the steady state approximation. More data spread was evident in the box-model approach compared with the other methods. An analysis of the major sources and sinks of OH is presented for the three methods of calculation. Calculated and observed peroxy radicals are also presented. Calculated peroxy radicals were generally lower than that observed at night yet higher, sometimes by up to a factor of 7, during the day. Possible explanations for this result are explored.
No preview · Article · May 1999 · Journal of Atmospheric Chemistry
[Show abstract][Hide abstract] ABSTRACT: A study of the nitrate radical (NO3) has been conducted through a series of campaigns held at the Weybourne Atmospheric Observatory, located on the coast of north Norfolk, England. The NO3 concentration was measured in the lower boundary layer by the technique of differential optical absorption spectroscopy (DOAS). Although the set of observations is limited, seasonal patterns are apparent. In winter, the NO3 concentration in semi-polluted continental air masses was found to be of the order of 10 ppt, with an average turnover lifetime of 2.4 minutes. During summer in clean northerly air flows, the concentration was about 6 ppt with a lifetime of 7.2 minutes. The major loss mechanisms for the radical were investigated in some detail by employing a chemical box model, constrained by a suite of ancillary measurements. The model indicates that during the semi-polluted conditions experienced in winter, the major loss of NO3 occurred indirectly through reactions of N2O5, either in the gas-phase with H2O, or through uptake on aerosols. The most important direct loss was via reactions of NO3 with a number of unsaturated nonmethane hydrocarbons. The cleaner air masses observed during the summer were of marine origin and contained elevated concentrations of dimethyl sulfide (DMS), which provided the major loss route for NO3. The box model was then used to investigate the conditions in the remote marine boundary layer under which DMS will be oxidised more rapidly at night (by NO3) than during the day (by OH). This should occur if the concentration of NO2 is more than about 60% that of DMS.
No preview · Article · Jan 1999 · Journal of Atmospheric Chemistry
[Show abstract][Hide abstract] ABSTRACT: Measurements of O3, NO, NO2, the photodissociation rate coefficient of NO2 (j(NO2)), and temperature made during the WAOWE’93 and ’94 (Weybourne Atmospheric Observatory Winter Experiment) campaigns on the north Norfolk coast were used to evaluate the photochemical steady state (PSS) as a method of deriving peroxy radical (HO2+RO2) concentrations. Highly polluted air masses containing elevated levels of NOx (NO+NO2) were encountered during WAOWE’93. The PSS ratio, (j(NO2)[NO2])/(kNO+O3 [NO] [O3]), was found to equal unity within experimental error which resulted in good agreement between predicted and measured O3 concentrations and, in addition, implied the absence of peroxy radicals. Small deviations from the PSS ratio in the apparent absence of peroxy radicals indicated the presence of a temperature-dependent perturbation. Such a process could lead to artefact or enhanced PSS-derived peroxy radical concentrations at temperatures above 2°C. During the WAOWE’94 campaign, the PSS ratio reached values of up to two and calculated peroxy radical concentrations were found to be positively correlated with [O3] and negatively correlated with NOx, indicating that the observed perturbations from the PSS were at least partly caused by peroxy radicals. However, the levels of peroxy radicals predicted by the PSS were up to two orders of magnitude higher than those calculated using a simple zero-dimensional model. Previous studies of the NOx/O3 PSS are evaluated in conjunction with the results obtained in this study. It is suggested that the PSS method may be used as a text-book case in limited conditions to estimate levels of O3, NO2, NO or j(NO2), but is subject to a variety of potential interferences which invalidate its widespread use as a method for deriving atmospheric peroxy radical concentrations.
No preview · Article · Oct 1998 · Atmospheric Environment
[Show abstract][Hide abstract] ABSTRACT: Measurements of carbon monoxide and other pollutants were performed in a study of polluted air masses during winter at a time when atmospheric reactivity is low. Data collected during the Weybourne atmospheric observatory winter experiment in 1993 on the North Norfolk Coast, U.K. showed that CO is correlated with other atmospheric species and these correlations are influenced by both chemical and dynamical processes in the lower troposphere. A high pollution event occurred at the beginning of the campaign with freshly polluted air masses high in CO and nitrogen oxides coming from continental Europe via London. Very low concentrations were experienced towards the end of the period when maritime Atlantic air was reaching the site. CO showed strong positive correlation with NOy and non-methane hydrocarbons (NMHCs) as a result of common sources. Correlations between CO and ozone were strong and consistently negative due to titration of ozone by NO. CO in the background atmosphere in winter was estimated to be 122 ppbv, at a corresponding O3 concentration of 33 ppbv. Detailed analysis of the pollution event revealed that the polluted airmass originated in London some 9 h before reaching Weybourne. Differential decomposition of specific hydrocarbons en route is indicative of daytime hydroxyl radical concentrations of the order of 3×105 cm-3.
No preview · Article · Oct 1998 · Atmospheric Environment
[Show abstract][Hide abstract] ABSTRACT: This paper describes the most extensive set of simultaneous measurements of the concentrations of nitrate (NO3) and peroxy (sum of HO2 + RO2, R = alkyl and acyl) radicals to date. The measurements were made in the coastal marine boundary layer over the North Sea, at the Weybourne Atmospheric Observatory on the North Norfolk coast during the spring and autumn of 1994. In spring the average nighttime concentration of NO3 measured by differential optical absorption spectroscopy, was about 10 parts per trillion (ppt) (maximum 25 ppt). The corresponding peroxy radical concentration, measured by the chemical amplifier technique, averaged about 2 ppt (maximum 6 ppt), although this is likely to be an underestimate of the total radical concentration. There is a significant positive correlation between the two sets of radicals, which has not been reported previously. A box model of the marine boundary layer is used to show that this correlation arises from the processing of reactive organic species by NO3. During spring the relatively long lifetime of NO3 (up to 18 min) at night is controlled by reaction with dimethyl sulfide (DMS), and the model predicts significant production of HNO3, methyl tiomethylen (CH3SCH2O2) and other peroxy radicals, HCHO, and eventually sulfate. A nighttime production rate for the hydroxyl (OH) of about 2 x 10(4) molecules cm(-3) s(-1) is estimated. During one night in autumn the NO3 lifetime of about 3 min is too short to be explained by reaction with unsaturated hydrocarbons, but is satisfactorily accounted for by the heterogeneous loss of N2O5 on deliquesced aerosols in relatively polluted conditions.
[Show abstract][Hide abstract] ABSTRACT: Four case studies are described, from a three-site field experiment in October/November 1991 using the Great Dun Fell flow-through reactor hill cap cloud in rural Northern England. Measurements of total odd-nitrogen nitrogen oxides (NO
) made on either side of the hill, before and after the air flowed through the cloud, showed that 10 to 50% of the NO
, called NO
, was neither NO nor NO2. This NO
failed to exhibit a diurnal variation and was often higher after passage through cloud than before. No evidence of conversion of NO
- in cloud was found. A simple box model of gas-phase chemistry in air before it reached the cloud, including scavenging of NO3 and N2O5 by aerosol of surface area proportional to the NO2 mixing ratio, shows that NO3 and N2O5 may build up in the boundary layer by night only if stable stratification insulates the air from emissions of NO. This may explain the lack of evidence for N2O5 forming NO3
- in cloud under well-mixed conditions in 1991, in contrast with observations under stably stratified conditions during previous experiments when evidence of N2O5 was found. Inside the cloud, some variations in the calculated total atmospheric loading of HNO2 and the cloud liquid water content were related to each other. Also, indications of conversion of NO
were found. To explain these observations, scavenging of NO
and HNO2 by cloud droplets and/or aqueous-phase oxidation of NO2
- by nitrate radicals are considered. When cloud acidity was being produced by aqueous-phase oxidation of NO
or SO2, NO3
- which had entered the cloud as aerosol particles was liberated as HNO3 vapour. When no aqueous-phase production of acidity was occurring, the reverse, conversion of scavenged HNO3 to particulate NO3
-, was observed.
No preview · Article · Jan 1996 · Journal of Atmospheric Chemistry
[Show abstract][Hide abstract] ABSTRACT: Two field experiments to investigate the formation of nitrate as an airstream passes through a hill cap cloud have been performed at the UMIST field station on Great Dun Fell. Techniques chosen for the measurement of various nitrogen species are described. The results of the second field experiment are discussed and compared with those of the first. Evidence is found in support of the hypothesis that under the range of conditions studied, the dominant pathway for nitrate production is the solution of N2O5 formed from the reaction of NOx with O3 upwind. The effectiveness of this pathway by night and by day is observed to be a function of the NOx mixing ratio. A surface reaction rate constant of around 300 cm3 cm−2 s−1 for the hydration of N2O5 is inferred from the observations. These results are shown to be consistent with recent laboratory measurements of the rates of reaction of nitrogen species. It is suggested that pathways other than via N2O5 may be significant sources of nitrate under certain conditions that merit further investigation.
No preview · Article · Feb 1994 · Atmospheric Environment