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The Amazon basin is a vast continental area in which atmospheric composition is relatively unaffected by anthropogenic aerosol particles. Understanding the properties of the natural biogenic aerosol particles over the Amazon rainforest is key to understanding their influence on regional and global climate. While there have been a number of studies during the wet season, and of biomass burning particles in the dry season, there has been relatively little work on the transition period – the start of the dry season in the absence of biomass burning. As part of the Brazil–UK Network for Investigation of Amazonian Atmospheric Composition and Impacts on Climate (BUNIAACIC) project, aerosol measurements, focussing on unpolluted biogenic air masses, were conducted at a remote rainforest site in the central Amazon during the transition from wet to dry season in July 2013. This period marks the start of the dry season but before significant biomass burning occurs in the region. Median particle number concentrations were 266 cm−3, with size distributions dominated by an accumulation mode of 130–150 nm. During periods of low particle counts, a smaller Aitken mode could also be seen around 80 nm. While the concentrations were similar in magnitude to those seen during the wet season, the size distributions suggest an enhancement in the accumulation mode compared to the wet season, but not yet to the extent seen later in the dry season, when significant biomass burning takes place. Submicron nonrefractory aerosol composition, as measured by an aerosol chemical speciation monitor (ACSM), was dominated by organic material (around 81 %). Aerosol hygroscopicity was probed using measurements from a hygroscopicity tandem differential mobility analyser (HTDMA), and a quasi-monodisperse cloud condensation nuclei counter (CCNc). The hygroscopicity parameter, κ, was found to be low, ranging from 0.12 for Aitken-mode particles to 0.18 for accumulation-mode particles. This was consistent with previous studies in the region, but lower than similar measurements conducted in Borneo, where κ ranged 0.17–0.37. A wide issue bioaerosol sensor (WIBS-3M) was deployed at ground level to probe the coarse mode, detecting primary biological aerosol by fluorescence (fluorescent biological aerosol particles, or FBAPs). The mean FBAP number concentration was 400 ± 242 L−1; however, this ranged from around 200 L−1 during the day to as much as 1200 L−1 at night. FBAPs dominated the coarse-mode particles, comprising between 55 and 75 % of particles during the day to more than 90 % at night. Non-FBAPs did not show a strong diurnal pattern. Comparison with previous FBAP measurements above canopy at the same location suggests there is a strong vertical gradient in FBAP concentrations through the canopy. Cluster analysis of the data suggests that FBAPs were dominated (around 70 %) by fungal spores. Further, long-term measurements will be required in order to fully examine the seasonal variability and distribution of primary biological aerosol particles through the canopy. This is the first time that such a suite of measurements has been deployed at this site to investigate the chemical composition and properties of the biogenic contributions to Amazonian aerosol during the transition period from the wet to the dry season, and thus provides a unique comparison to the aerosol properties observed during the wet season in previous similar campaigns. This was also the first deployment of a WIBS in the Amazon rainforest to study coarse-mode particles, particularly primary biological aerosol particles, which are likely to play an important role as ice nuclei in the region.

Designs of "improved" stoves are introduced recently to benefit the solid fuel consumption of cooking activities in developing countries, but the uncertainties concerning the combustion processes and particulate emissions remain poorly characterized. To help understand this, combustion in three examples of "improved" African cookstoves was investigated in the laboratory. A typical European heating stove was included for comparison purpose. Detailed aerosol emissions were studied in real-time with an Aerosol Mass Spectrometer and Single Particle Soot Photometer, to explore interactions between black carbon (BC) and organic carbon aerosols, which were parametrized according to modified combustion efficiency (MCE), a common metric used within the atmospheric emission community. Greater than 50% of the total organic matter (OM) was found in BC-containing particles when MCE was >0.95 for dry oak and coal fuels, whereas at lower MCE, over 80% of the total OM for most of the fuels existed in particles without detectable BC. When the OM mass fraction of total particulate matter (PM 1) > 0.9, the mass ratio of OM to refractory BC in BC-containing particles was about 2-3, but only ∼0.8 when OM mass fraction

In the atmosphere nighttime removal of volatile organic compounds is initiated to a large extent by reaction with the nitrate radical (NO3) forming organic nitrates which partition between gas and particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model indicate that most of the measured particulate organic nitrates are formed by NO3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM1) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NOx emission control.

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.

Chemical modelling studies have been conducted over north-western Europe in summer conditions, showing that night-time dinitrogen pentoxide (N2O5) heterogeneous reactive uptake is important regionally in modulating particulate nitrate and has a~modest influence on oxidative chemistry. Results from Weather Research and Forecasting model with Chemistry (WRF-Chem) model simulations, run with a detailed volatile organic compound (VOC) gas-phase chemistry scheme and the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) sectional aerosol scheme, were compared with a series of airborne gas and particulate measurements made over the UK in July 2010. Modelled mixing ratios of key gas-phase species were reasonably accurate (correlations with measurements of 0.7–0.9 for NO2 and O3). However modelled loadings of particulate species were less accurate (correlation with measurements for particulate sulfate and ammonium were between 0.0 and 0.6). Sulfate mass loadings were particularly low (modelled means of 0.5–0.7 μg kg−1air, compared with measurements of 1.0–1.5 μg kg−1air). Two flights from the campaign were used as test cases – one with low relative humidity (RH) (60–70%), the other with high RH (80–90%). N2O5 heterogeneous chemistry was found to not be important in the low-RH test case; but in the high-RH test case it had a strong effect and significantly improved the agreement between modelled and measured NO3 and N2O5. When the model failed to capture atmospheric RH correctly, the modelled NO3 and N2O5 mixing ratios for these flights differed significantly from the measurements. This demonstrates that, for regional modelling which involves heterogeneous processes, it is essential to capture the ambient temperature and water vapour profiles. The night-time NO3 oxidation of VOCs across the whole region was found to be 100–300 times slower than the daytime OH oxidation of these compounds. The difference in contribution was less for alkenes (× 80) and comparable for dimethylsulfide (DMS). However the suppression of NO3 mixing ratios across the domain by N2O5 heterogeneous chemistry has only a very slight, negative, influence on this oxidative capacity. The influence on regional particulate nitrate mass loadings is stronger. Night-time N2O5 heterogeneous chemistry maintains the production of particulate nitrate within polluted regions: when this process is taken into consideration, the daytime peak (for the 95th percentile) of PM10 nitrate mass loadings remains around 5.6 μg kg−1air, but the night-time minimum increases from 3.5 to 4.6 μg kg−1air. The sustaining of higher particulate mass loadings through the night by this process improves model skill at matching measured aerosol nitrate diurnal cycles and will negatively impact on regional air quality, requiring this process to be included in regional models.

Atmospheric aerosols often contain surface active organics. We study the influence of these surfactants on predictions of particle cloud activation potential and aerosol indirect climate effects, by implementing different parametrizations of surfactant effects in the global circulation model ECHAM5.5-HAM2. A parametrization based only on droplet surface tension reduction produces significantly larger effects on predicted cloud droplet numbers than novel parametrizations based on detailed considerations of organic surface activity. It seems better to disregard surfactant effects altogether than employing parametrizations accounting only for effects on surface tension. We strongly recommend not using only the surface tension reduction to represent the surfactant effects in climate models. Copyright 2012 by the American Geophysical Union.

Copyright @ 2011 Royal Meteorological Society. The Convective and Orographically-induced Precipitation Study (COPS) campaign was conducted during the summer of 2007. A suite of instruments housed at the top of the Hornisgrinde Mountain (1156 m) in the Black Forest region of south-west Germany provided datasets that allow an investigation into the physical, chemical and hygroscopic properties of the aerosol particles sampled during COPS. Organic mass loadings were found to dominate the aerosol composition for the majority of the project, exceeding 8 µg m−3 during a period of high pressure, high temperature, and low wind speed. The ratio of organic:sulphate sub-micron mass concentration exceeds 10:1 during the same time period. Back trajectories show air from this time-frame passing slowly over the local forest and not passing over any local anthropogenic sources. Occasional peaks in nitrate mass loadings were associated with changes in the typical wind direction from south-westerly to north-westerly where air had passed over the Stuttgart region. Size distribution data shows a dominant accumulation-mode when the measurement site was free from precipitation events. A sharp increase in ultrafine particle number concentration was seen during most days commencing around noon. The apparent growth of these particles is associated with an increase in organic mass loading, suggesting condensational growth. For the most part, with the exception of the high pressure period, the aerosol properties recorded during COPS were comparable to previous studies of continental aerosol properties. NERC

The effect of nanogel colloidal and dissolved organic matter The aerosol generated from seawater proxies enriched with marine exudate presented organic volume fractions on the order of 8–37%, as derived by applying a simple mixing rule. The hygroscopic growth and cloud condensation nuclei (CCN) activity of the marine organics-enriched particles where 9–17% and 5–24% lower, respectively, than those of the aerosol produced from artificial seawater devoid of exudate. Experiments in a companion paper indicated that the cloud nuclei formation could be enhanced in diatom bloom areas because of the increase in the primary particle production induced by marine organics. The experiments in the present study, however, indicate that the impacts of such an enhancement would be counteracted by the reduction in the CCN activity of the primary particles enriched in marine organics. The extent of the effect of the biogenic matter on the particle behaviour was dependent on the seawater organic concentration and type of algal exudate. Aerosol produced from seawater proxies containing diatomaceous exudate presented higher hydrophobicity and lower CCN activity than those enriched with nanoplankton exudate. The organic fraction of the particles was found to correlate with the seawater organic concentration, without observing saturation of the particle organic mass fraction even for unrealistically high organic matter concentration in seawater. These findings are indicative that discrepancies on the composition of the primary aerosol between different studies could partly be explained by the difference in the nature and concentration of the organic matter in the source seawater employed. Consistently across the experiments, theoretical analysis based on the Köhler model predicted a reduction in the primary marine aerosol CCN activity upon the incorporation of marine organics into the particle composition. This effect is consequence of the replacement of small inorganic sea salt molecules by large molar mass organic molecules, together with a moderate suppression of the surface tension at the point of activation of 5–0.5%, which leads to a dominance of the reduction in the dissolved solute in the Raoult term.

In April–July 2008, intensive measurements were made of atmospheric composition and chemistry in Sabah, Malaysia, as part of the "Oxidant and particle photochemical processes above a South-East Asian tropical rainforest" (OP3) project. Fluxes and concentrations of trace gases and particles were made from and above the rainforest canopy at the Bukit Atur Global Atmosphere Watch station and at the nearby Sabahmas oil palm plantation, using both ground-based and airborne measurements. Here, the measurement and modelling strategies used, the characteristics of the sites and an overview of data obtained are described. Composition measurements show that the rainforest site was not significantly impacted by anthropogenic pollution, and this is confirmed by satellite retrievals of NO2 and HCHO. The dominant modulators of atmospheric chemistry at the rainforest site were therefore emissions of BVOCs and soil emissions of reactive nitrogen oxides. At the observed BVOC:NOx volume mixing ratio (~100 pptv/pptv), current chemical models suggest that daytime maximum OH concentrations should be ca. 105 radicals cm−3, but observed OH concentrations were an order of magnitude greater than this. We confirm, therefore, previous measurements that suggest that an unexplained source of OH must exist above tropical rainforest and we continue to interrogate the data to find explanations for this.