Aerosol optical and physical properties during winter monsoon pollution transport in an urban environment

We analysed aerosol optical and physical properties in an urban environment (Kolkata) during winter monsoon pollution transport from nearby and far-off regions. Prevailing meteorological conditions, viz. low temperature and wind speed, and a strong downdraft of air mass, indicated weak dispersion and inhibition of vertical mixing of aerosols. Spectral features of WinMon aerosol optical depth (AOD) showed larger variability (0.68–1.13) in monthly mean AOD at short-wavelength (SW) channels (0.34–0.5 μm) compared to that (0.28–0.37) at long-wavelength (LW) channels (0.87–1.02 μm), thereby indicating sensitivity of WinMon AOD to fine aerosol constituents and the predominant contribution from fine aerosol constituents to WinMon AOD. WinMon AOD at 0.5 μm (AOD _{0. 5}) and Angstrom parameter ( α) were 0.68–0.82 and 1.14–1.32, respectively, with their highest value in December. Consistent with inference from spectral features of AOD, surface aerosol loading was primarily constituted of fine aerosols (size 0.23–3 μm) which was 60–70 % of aerosol 10- μm (size 0.23–10 μm) concentration. Three distinct modes of aerosol distribution were obtained, with the highest WinMon concentration at a mass median diameter (MMD) of 0.3 μm during December, thereby indicating characteristics of primary contribution related to anthropogenic pollutants that were inferred to be mostly due to contribution from air mass originating in nearby region having predominant emissions from biofuel and fossil fuel combustion. A relatively higher contribution from aerosols in the upper atmospheric layers than at the surface to WinMon AOD was inferred during February compared to other months and was attributed to predominant contribution from open burning emissions arising from nearby and far-off regions. A comparison of ground-based measurements with Moderate Resolution Imaging Spectroradiometer (MODIS) data showed an underestimation of MODIS AOD and α values for most of the days. Discrepancy in relative distribution of fine and coarse mode of MODIS AOD was also inferred.     

Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol

A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas–aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds generated from hydrocarbon–nitrogen oxide (HC/NO_x) mixtures irradiated in the presence of fine (<2.5 μm) particulate matter. The goal was to determine to what extent photochemical oxidation products of aromatic hydrocarbons contribute to secondary organic aerosol formation through uptake on pre-existing inorganic aerosols in the absence of liquid water films. Irradiations were conducted with toluene, p-xylene, and 1,3,5-trimethylbenzene in the presence of NO_x and ammonium sulfate aerosol, with propylene added to enhance the production of radicals in the system. The secondary organic aerosol yields were determined by dividing the mass concentration of organic fraction of the aerosol collected on quartz filters by the mass concentration of the aromatic hydrocarbon removed by reaction. The mass concentration of the organic fraction was obtained by multiplying the measured organic carbon concentration by 2.0, a correction factor that takes into account the presence of hydrogen, nitrogen, and oxygen atoms in the organic species. The mass concentrations of ammonium, nitrate, and sulfate concentrations as well as the total mass of the aerosols were measured. A reasonable mass balance was found for each of the aerosols. The largest secondary organic aerosol yield of 1.59±0.40% was found for toluene at an organic aerosol concentration of 8.2 μm⁻³, followed by 1.09±0.27% for p-xylene at 6.4 μg m⁻³, and 0.41±0.10% for 1,3,5-trimethylbenzene at 2.0 μg m⁻³. In general, these results agree with those reported by Odum et al. and appear to be consistent with the gas–aerosol partitioning theory developed by Pankow. The presence of organic in the aerosol did not affect significantly the hygroscopic properties of the aerosol.     

Effect of biomass burning and regional background aerosols on CCN activity derived from airborne in-situ measurements

Airborne in-situ measurements were analyzed to investigate the effects of biomass burning and regional background aerosols on cloud condensation nuclei (CCN) activity in the Pacific Dust Experiment (PACDEX) during April and May 2007. Airmass trajectories with both horizontal and vertical motions were provided to identify the aerosol sources. In the biomass burning cases, the elevated aerosol layers were clearly observed at dry conditions because of the convection of airmass in the source region. The relative aging of aerosols was supported by the ratios of BC to particles with size ranging from 0.1 to 1.0 μm (N_0.1–1.0) and BC to carbon monoxide. Compared to aerosols in the precedent plume of biomass burning, aged particles in the latter plume were more activated to CCN at 0.4% (CCN_0.4%) than 0.1% supersaturation (CCN_0.1%) due to aerosols chemical modification during the aging process. On the other hand, significant difference of CCN_0.4% and CCN_0.1% at regional background aerosols over the Pacific Ocean was due to the activated particles below 1 μm in diameter. Although higher concentrations of aged particles were observed over the eastern Pacific Ocean, activated aerosols to cloud droplet was comparatively similar in the western Pacific Ocean because of the similar concentrations of N_0.1–1.0 in both cases.     

Impact of clouds and aerosols on ozone production in Southeast Texas

A radiative transfer model and photochemical box model are used to examine the effects of clouds and aerosols on actinic flux and photolysis rates, and the impacts of changes in photolysis rates on ozone production and destruction rates in a polluted urban environment like Houston, Texas. During the TexAQS-II Radical and Aerosol Measurement Project the combined cloud and aerosol effects reduced j(NO₂) photolysis frequencies by nominally 17%, while aerosols reduced j(NO₂) by 3% on six clear sky days. Reductions in actinic flux due to attenuation by clouds and aerosols correspond to reduced net ozone formation rates with a nearly one-to-one relationship. The overall reduction in the net ozone production rate due to reductions in photolysis rates by clouds and aerosols was approximately 8 ppbv h^?1.     

Investigation of the time evolved spatial distribution of urban PM2.5 concentrations and aerosol composition during episodic high PM events in Yuma,AZ

An interdisciplinary field study designed to investigate the spatial and temporal variability of atmospheric aerosols during high particulate matter (PM) events along the US–Mexico border near Yuma, AZ was run during the week of March 18, 2007. The experiments were designed to quantify chemical composition and physical phenomena governing the transport of aerosols generated from episodic high PM events. The field study included two micrometeorological monitoring sites; one rural and one urban, equipped with sonic anemometers, continuous particulate concentration monitors and ambient aerosol collection equipment. In addition to the two main monitoring sites, five additional locations were equipped with optical particle counters to allow for the investigation of the spatial and temporal distribution of PM_2.5 in the urban environment. In this paper, the meteorological and turbulence parameters governing the distribution and concentration of PM_2.5 in the urban environment for two high-wind erosion events and one burning event are compared. The interaction between local atmospheric conditions and the particulate distribution is investigated. Results indicate that a single point measurement in the urban area of Yuma may not be sufficient for determining the ambient PM concentrations that the local population experiences; all three high PM events indicated PM_2.5 varied considerably with maximum urban concentrations 5–10 times greater than the measured minima. A comparison of inorganic and carbonaceous content of the aerosols for the three high PM events is presented. The comparison shows an increase in silicon during crustal dust events and an increase in elemental and organic carbon during the burn event. Additional surface chemistry analysis, using time-of-flight secondary ion mass spectrometry (ToF-SIMS), for aerosols collected at the urban and rural sites during the burn event are discussed. The surface chemistry analysis provides positive ion mass spectra of organic and inorganic species in the ambient aerosol, and can be used to determine the type of combustion process that contributed to an increase in PM concentration during the burn event.     

Cloud condensation nucleus activity of organic compounds: a laboratory study

Critical or activation diameters of laboratory generated organic aerosols composed of succinic acid, adipic acid and glucose were determined. Measurements of sodium chloride and ammonium sulfate aerosols were performed for comparison. Our experimental approach involved producing single component aerosol particles of a known size, and measuring the fraction of aerosol number concentrations (CN) that act as CCN at several supersaturations. The particle diameter (D₅₀) at which the CCN/CN ratio of 0.50 is reached is defined as the critical, or activation, diameter. These experimentally derived diameters are compared with the theoretical critical diameter (D_C). The results indicate that highly water-soluble organic compounds exhibit critical diameters that approach that of ammonium sulfate.     

Characterization and source presumption of wintertime submicron organic aerosols at Saitama,Japan, using the Aerodyne aerosol mass spectrometer

The chemical composition and size distribution of submicron aerosols were analyzed at a suburban site at Saitama, Japan, in the winter of 2004/2005, using an Aerodyne aerosol mass spectrometer. Although organics and nitrate were the dominant species during the sampling period, a large fraction of sulfate was observed at the accumulation mode when mass loading was low and wind speed was high. The size distributions of m/z 44 (mostly CO₂⁺) and sulfate aerosols during periods of high wind speed showed remarkable similarities in the accumulation mode, indicating that oxygenated organics were aged aerosols and internally mixed with sulfate. Ozone concentrations were also increased during these high wind speed periods although nighttime (e.g., 12/17 2004), indicating that the oxygenated compounds were strongly influenced by transported and aged air masses. The diurnal profiles of ultrafine-mode organics and hydrocarbon-like organic aerosols (HOA) were similar to NO_X derived from traffic and other combustion sources. The temporal variation of oxygenated organic aerosols (OOA) agreed well with that of nitrate as a secondary aerosol tracer, and the diurnal profile of the OOA fraction of organics increased during the day associated with higher UV light intensity. The result of time and size-resolved chemical composition of submicron particles indicated that the OOA is associated with both photochemical activity and transboundary pollution, and ultrafine-mode organic and HOA aerosols are mainly associated with combustion sources.     

Morphological and chemical composition characteristics of summertime atmospheric particles collected at Tokchok Island,Korea

Determination of the chemical compositions of atmospheric single particles in the Yellow Sea region is critical for evaluating the environmental impact caused by air pollutants emitted from mainland China and the Korean peninsula. After ambient aerosol particles were collected by the Dekati PM10 cascade impactor on July 17–23, 2007 at Tokchok Island (approximately 50 km west of the Korean coast nearby Seoul), Korea, overall 2000 particles (on stage 2 and 3 with cut-off diameters of 2.5–10 μm and 1.0–2.5 μm, respectively) in 10 samples were determined by using low-Z particle electron probe X-ray microanalysis. X-ray spectral and secondary electron image (SEI) data showed that soil-derived and sea-salt particles which had reacted or were mixed with SO₂ and NO_x (or their acidic products) outnumbered the primary and “genuine” ones (59.2% vs. 19.2% in the stage 2 fraction and 41.3% vs. 9.9% in the stage 3 fraction). Moreover, particles containing nitrate in the secondary soil-derived species greatly outnumbered those containing sulfate. Organic particles, mainly consisting of marine biogenic species, were more abundant in the stage 2 fraction than in the stage 3 fraction (11.6% vs. 5.1%). Their relative abundance was greater than the sum of carbon-rich, K-containing, Fe-containing, and fly ash particles, which exhibited low frequencies in all the samples. In addition, many droplets rich in C, N, O, and S were observed. They tended to be small, exhibiting a dark round shape on SEI, and generally included 8–20 at.% C, 0–12 at.% N, 60–80 at.% O, and 4–10 at.% S (sometimes with <3 at.% Mg and Na). They were attributed to be a mixture of carbonaceous matter, H₂SO₄, and NH₄HSO₄/(NH₄)₂SO₄, mostly from the reaction of atmospheric SO₂ with NH₃ under high relative humidity. The analysis of the relationship between the aerosol particle compositions and 72-h backward air-mass trajectories suggests that ambient aerosols at Tokchok Island are strongly affected not only by seawater from the Yellow Sea but also by anthropogenic pollutants emitted from China and the Seoul–Incheon metropolis, resulting in the dominance of complex secondary aerosol particles.     

Effect of composition on aerosol light scattering efficiencies

Forecasts of the impact of emissions changes on visibility use light scattering efficiencies—the change in the amount of light scattered with a change in mass of an aerosol constituent. This paper demonstrates how light scattering efficiencies depend on interactions between the aerosol constituents. Calculations are presented for two model aerosols: NH₄HSO₄ droplets and a ‘typical’ urban aerosol. These calculations demonstrate that the traditional means of predicting visibility impairment for increases in atmospheric emissions is not generally appropriate. Different light scattering efficiencies are needed for distinct meteorological conditions and aerosol compositions thus for typical high and low visibility events.     

Observations and modelling of aerosol growth in marine stratocumulus—case study

Airborne measurements of the growth of the marine accumulation mode after multiple cycles through stratocumulus cloud are presented. The nss-sulphate cloud residual mode was log-normal in spectral shape and it’s mode radius was observed to progressively increase in size from 0.78 to 0.94 μm over 155 min of air parcel evolution through the cloudy marine boundary layer. The primary reason for this observed growth was thought to result from aqueous phase oxidation of SO₂ to aerosol sulphate in activated cloud drops. An aqueous phase aerosol–cloud-chemistry model was used to simulate this case study of aerosol growth and was able to closely reproduce the observed growth. The model simulations illustrate that aqueous phase oxidation of SO₂ in cloud droplets was able to provide enough additional sulphate mass to increase the size of activated aerosol. During a typical cloud cycle simulation, ≈4.6 nmoles kg^-1_air (0.44 μg m^-3) of sulphate mass was produced with ≈70% of sulphate production occurring in cloud droplets activated upon sea-salt nuclei and ≈30% occurring upon nss-sulphate nuclei, even though sea-salt nuclei contributed less than 15% to the activated droplet population. The high fraction of nss-sulphate mass internally mixed with sea-salt aerosol suggests that aqueous phase oxidation of SO₂ in cloud droplets activated upon sea-salt nuclei is the dominant nss-sulphate formation mechanism and that sea-salt aerosol provides the primary chemical sink for SO₂ in the cloudy marine boundary layer.     

Aerosols formed from the chemical reaction of monoterpenes and ozone

Chamber experiments were conducted to study the aerosol products from the ozonolysis of the major atmospheric monoterpenes; α-pinene, β-pinene and limonene. It was found that the α-pinend–O₃ reaction produced mainly 2′. 2′-dimethyl-3′-acetyl cyclobutyl ethanal (pinonaldehyde), the β-pinene–O₃ reaction, mainly 6,6-dimethyl-bicyclo [3.1.1] heptan-2-one and the limonene–O₃ reaction, several unidentified products. These products were sought in forest aerosols and pinonaldehyde was detected in the atmosphere.     

Aerosol formation from the gas-phase reaction of hydroxyl radical with the natural hydrocarbon bornyl acetate

The gas-phase reaction of bornyl acetate (1,7,7-trimethyl-bicyclo[2,2,1]-heptan-2-ol-acetate) with hydroxyl radical has been studied in a smog chamber. It was found that the reaction of bornyl acetate with OH radicals leads to organic aerosols. The chemical composition of the aerosol was studied. On the basis of mass spectral data 1,7,7-trimethyl-6-acetyloxy-bicyclo[2.2.1]-heptan-2,3-dione has been tentatively identified in irradiated CH₃ONO–NO–air–bornyl acetate mixtures. The aerosol carbon yield, the fraction of the carbon initially present that is converted to aerosol, has been estimated to be ≅5%.     

Extensive aerosol optical properties and aerosol mass related measurements during TRAMP/TexAQS 2006 – Implications for PM compliance and planning

Extensive aerosol optical properties, particle size distributions, and Aerodyne quadrupole aerosol mass spectrometer measurements collected during TRAMP/TexAQS 2006 were examined in light of collocated meteorological and chemical measurements. Much of the evident variability in the observed aerosol-related air quality is due to changing synoptic meteorological situations that direct emissions from various sources to the TRAMP site near the center of the Houston-Galveston-Brazoria (HGB) metropolitan area. In this study, five distinct long-term periods have been identified. During each of these periods, observed aerosol properties have implications that are of interest to environmental quality management agencies. During three of the periods, long range transport (LRT), both intra-continental and intercontinental, appears to have played an important role in producing the observed aerosol. During late August 2006, southerly winds brought super-micron Saharan dust and sea salt to the HGB area, adding mass to fine particulate matter (PM_2.5) measurements, but apparently not affecting secondary particle growth or gas-phase air pollution. A second type of LRT was associated with northerly winds in early September 2006 and with increased ozone and sub-micron particulate matter in the HGB area. Later in the study, LRT of emissions from wildfires appeared to increase the abundance of absorbing aerosols (and carbon monoxide and other chemical tracers) in the HGB area. However, the greatest impacts on Houston PM_2.5 air quality are caused by periods with low-wind-speed sea breeze circulation or winds that directly transport pollutants from major industrial areas, i.e., the Houston Ship Channel, into the city center.     

The Evolution of Visibility Deterioration and Aerosol Spectra in the St. Louis Urban Plume

Under the auspices of Project METROMEX, studies of visibility de-teoration downwind of St. Louis were conducted during July-August 1974-1975. Estimates of horizontal visual range, standard meteorological data, and aerosol characteristics within the mixing layer were acquired upwind, over, and downwind of the metropolitan area by means of airborne transects. Aerosol number, surface, and volume distributions for particles between 0.025-2.5 µm were generated from the airborne measurement of Aitken nucleus concentrations, cloud condensation nuclei, and aerosols detected in situ with optical probes. Visibility reduction amounting to 50% of prevailing regional upwind visibilities consistently occurs at a distance corresponding to 2-3 hours travel time downwind for an air parcel moving with the mean transport wind. The regions of visibility minimum do not coincide with locations of maximum Aitken nucleus concentrations, but rather correspond in space and time to increased values of cloud condensation nuclei and increased numbers of particles in the 0.1-2.5 µm diameter range. Comparisons of observed aerosol evolution with similar laboratory studies suggest that most of the light scattering aerosols are of secondary origin.     

Role of ammonia chemistry and coarse mode aerosols in global climatological inorganic aerosol distributions

We use an inorganic aerosol thermodynamic equilibrium model in a three-dimensional chemical transport model to understand the roles of ammonia chemistry and natural aerosols on the global distribution of aerosols. The thermodynamic equilibrium model partitions gas-phase precursors among modeled aerosol species self-consistently with ambient relative humidity and natural and anthropogenic aerosol emissions during the 1990s.Model simulations show that accounting for aerosol inorganic thermodynamic equilibrium, ammonia chemistry and dust and sea-salt aerosols improve agreement with observed SO₄, NO₃, and NH₄ aerosols especially at North American sites. This study shows that the presence of sea salt, dust aerosol and ammonia chemistry significantly increases sulfate over polluted continental regions. In all regions and seasons, representation of ammonia chemistry is required to obtain reasonable agreement between modeled and observed sulfate and nitrate concentrations. Observed and modeled correlations of sulfate and nitrate with ammonium confirm that the sulfate and nitrate are strongly coupled with ammonium. SO₄ concentrations over East China peak in winter, while North American SO₄ peaks in summer. Seasonal variations of NO₃ and SO₄ are the same in East China. In North America, the seasonal variation is much stronger for NO₃ than SO₄ and peaks in winter.Natural sea salt and dust aerosol significantly alter the regional distributions of other aerosols in three main ways. First, they increase sulfate formation by 10–70% in polluted areas. Second, they increase modeled nitrate over oceans and reduce nitrate over Northern hemisphere continents. Third, they reduce ammonium formation over oceans and increase ammonium over Northern Hemisphere continents. Comparisons of SO₄, NO₃ and NH₄ deposition between pre-industrial, present, and year 2100 scenarios show that the present NO₃ and NH₄ deposition are twice pre-industrial deposition and present SO₄ deposition is almost five times pre-industrial deposition.     

Seasonal distribution of polar organic compounds in the urban atmosphere of two large cities from the North and South of Europe

Polar organic species, including n-alkanols, sterols, anhydrosugars, n-alkanoic acids, n-alkenoic acids and dicarboxylic acids were quantified to typify the composition of fine (PM_2.5) and coarse (PM_10–2.5) aerosols collected simultaneously at roadside and background sites in Oporto (Portugal) and Copenhagen (Denmark) during separate month-long intensive summer and winter campaigns. As a general trend, both cities exhibit roadside average concentrations higher than their correspondent urban background levels. The polar organics are more abundant in the fine fraction, exhibiting a seasonal pattern with high winter concentrations and low summer loads. Aerosols from both cities showed typical distributions of n-alkanols and n-alkanoic acids in the ranges C₁₂–C₂₈ and C₈–C₂₈, respectively. The <C₂₀ homologues, usually attributed to kitchen emissions, vehicular exhausts and microbial origins, dominated the fatty acid fraction. Linear alcohols were mainly represented by higher molecular weight homologues from vegetation waxes. Molecular tracer species for wood smoke (e.g. levoglucosan, mannosan and resinic acids) were found to contribute significantly to the urban aerosol, especially in winter. Ratios between these tracers indicated different biofuel contributions to the atmospheric particles of the two cities. Secondary constituents from both biogenic (e.g. pinonic acid) and anthropogenic precursors (e.g. phthalic and benzoic acids) were detected in both cities and seasons.     

Kinetics of acid-catalyzed aldol condensation reactions of aliphatic aldehydes

Field observations of atmospheric aerosols have established that organic compounds compose a large fraction of the atmospheric aerosol mass. However, the physical/chemical pathway by which organic compounds are incorporated into atmospheric aerosols remains unclear. The potential role of acid-catalyzed reactions of organic compounds on acidic aerosols has been explored as a possible chemical pathway for the incorporation of organic material into aerosols. In the present study, ultraviolet–visible (UV–vis) spectroscopy was used to monitor the kinetics of formation of the products of the acid-catalyzed aldol condensation reaction of a range of aliphatic aldehydes (C₂–C₈). The experiments were carried out at various sulfuric acid concentrations and a range of temperatures in order to estimate the rate constants of such reactions on sulfuric acid aerosols under tropospheric conditions. The rate constants were generally found to decrease as the chain length of the aliphatic aldehyde increased (except for acetaldehyde, which had an unusually small rate constant), increase as a function of sulfuric acid concentration as predicted by excess acidity theory, and showed normal Arrhenius behavior as a function of temperature. While the kinetic data are generally consistent with previous laboratory reports of aldehyde reactivity in various sulfuric acid media, the aldol condensation reactions involving aliphatic aldehydes do not appear fast enough to be responsible for significant transfer of organic material into atmospheric aerosols.     

Contribution of transboundary air pollution to ionic concentrations in fog in the Kinki Region of Japan

To estimate the contribution of transboundary transported air pollutants from other Asian countries to Japan in ionic concentrations in fog water in March 2005, the Community Multiscale Air Quality (CMAQ) modeling system was utilized with meteorological fields produced by the 5th generation Mesoscale Model (MM5). For meteorological predictions, the model well reproduced the surface meteorological variables, particularly temperature and humidity, and generally captured fog occurrence. For chemical predictions, most of the model-predicted monthly mean concentrations were approximately within a factor of 2 of the observations, indicating that the model well simulated the long-range atmospheric transport from the Asian Continent to Japan. For SO₄^2?, NO₃^? and NH₄⁺, the contribution rates of the transboundary air pollution in the Kinki Region of Japan ranged from 69 to 82% for aerosols, from 47 to 87% for ionic concentrations in rain, and from 55 to 79% for ionic concentrations in fog. The study found that the transboundary air pollution also affected ionic concentrations in fog as well as aerosol concentrations and ionic concentrations in rain.     

Scavenging of electrified radioactive aerosol

Scavenging by water droplets is a mechanism for aerosol removal near clouds. Numerical methods are developed to quantify the removal of charged radioactive aerosols, including the electrical image force's contribution, attractive at small separations. Charging of radioactive aerosols is found to have significant effects on their collision efficiency and scavenging coefficient. The effect depends on the aerosol charge, and therefore, on the radioactive aerosol's decay rate and number concentration, but it does not depend significantly on the charge carried by the water drops. Scavenging coefficients are calculated for radioactive aerosols. For small particles at low aerosol concentrations (Z∼10–100 cm⁻³), charging can increase the scavenging coefficients by up to an order of magnitude. Electrification will, therefore, encourage the removal of small radioactive aerosols from the atmosphere, more rapidly than equivalent non-radioactive aerosols. The increase in removal at low radioactive-aerosol concentration may account for underpredictions of surface concentrations and will contribute to spatial variations in aerosol removal.     

Temperature dependence of PCBs in the UK atmosphere

A thermodynamic approach was taken to assess the state of equilibrium between air and the Earth’s surface for PCBs at a variety of sites located in urban and rural areas. The Clausius–Clapeyron equation was applied to atmospheric PCB data, relating PCB partial vapour pressure (ln P) to inverse temperature (1/K); essentially representing the temperature controlled transition between condensed phases and the atmospheric gas phase. The slopes of the resulting plots ranged from −3100 to −8272 for a range of congeners at two city sites, significantly steeper than those generated at two rural locations, where there was little or no correlation between ln P and temperature. It was inferred that advection and variable meteorological conditions mask any localised, temperature dependent, air–surface exchange at these rural locations when weekly or two weekly integrated samples were taken. At a third rural site, close to Lancaster University, an intensive highly time-resolved sampling regime, carried out during very stable meteorological conditions resulted in highly correlated plots (r²>0.6), with slopes ranging from −7151 to −14 148 for different congeners. By reducing meteorological variables in this manner localised temperature controlled air–surface exchange became evident. Enthalpies of phase change generated from the temperature coefficients were similar to literature values for the enthalpy of vapourisation and the enthalpy of phase change from octanol to air. This suggests that, under these stable conditions, equilibrium was achieved as a function of either vapour pressure (P^°_L) or the octanol–air partition coefficient (K_OA).