Search

Data are presented from intercomparisons between two research aircraft, the FAAM BAe-146 and the NASA Lockheed P3, and between the BAe-146 and the surface-based DOE (Department of Energy) ARM (Atmospheric Radiation Measurement) Mobile Facility at Ascension Island (8∘ S, 14.5∘ W; a remote island in the mid-Atlantic). These took place from 17 August to 5 September 2017, during the African biomass burning (BB) season. The primary motivation was to give confidence in the use of data from multiple platforms with which to evaluate numerical climate models. The three platforms were involved in the CLouds–Aerosol–Radiation Interaction and Forcing for Year 2017 (CLARIFY-2017), ObseRvations of Aerosols above CLouds and their intEractionS (ORACLES), and Layered Atlantic Smoke and Interactions with Clouds (LASIC) field experiments. Comparisons from flight segments on 6 d where the BAe-146 flew alongside the ARM facility on Ascension Island are presented, along with comparisons from the wing-tip-to-wing-tip flight of the P3 and BAe-146 on 18 August 2017. The intercomparison flight sampled a relatively clean atmosphere overlying a moderately polluted boundary layer, while the six fly-bys of the ARM site sampled both clean and polluted conditions 2–4 km upwind. We compare and validate characterisations of aerosol physical, chemical and optical properties as well as atmospheric radiation and cloud microphysics between platforms. We assess the performance of measurement instrumentation in the field, under conditions where sampling conditions are not as tightly controlled as in laboratory measurements where calibrations are performed. Solar radiation measurements compared well enough to permit radiative closure studies. Optical absorption coefficient measurements from all three platforms were within uncertainty limits, although absolute magnitudes were too low ( Mm−1) to fully support a comparison of the absorption Ångström exponents. Aerosol optical absorption measurements from airborne platforms were more comparable than aircraft-to-ground observations. Scattering coefficient observations compared adequately between airborne platforms, but agreement with ground-based measurements was worse, potentially caused by small differences in sampling conditions or actual aerosol population differences over land. Chemical composition measurements followed a similar pattern, with better comparisons between the airborne platforms. Thermodynamics, aerosol and cloud microphysical properties generally agreed given uncertainties.

Seasonal biomass burning (BB) over West Africa is a globally significant source of carbonaceous particles in the atmosphere, which have important climate impacts but are poorly constrained. Here, the evolution of smoke aerosols emitted from flaming-controlled burning of agricultural waste and wooded savannah in the Senegal region was characterized over a timescale of half-day advection from the source during the MOYA-2017 (Methane Observation Yearly Assessment-2017) aircraft campaign. Plumes from such fire types are rich in black carbon (BC) emissions. Concurrent measurements of chemical composition, organic aerosol (OA) oxidation state, bulk aerosol size and BC mixing state reveal that emitted BB submicron aerosols changed dramatically with time. Various aerosol optical properties (e.g. absorption Ångström exponent – AAE – and mass absorption coefficients – MACs) also evolved with ageing. In this study, brown carbon (BrC) was a minor fractional component of the freshly emitted BB aerosols (< 0.5 h), but the increasing AAE with particle age indicates that BrC formation dominated over any loss process over the first ∼ 12 h of plume transport. Using different methods, the fractional contribution of BrC to total aerosol absorption showed an increasing trend with time and was ∼ 18 %–31 % at the optical wavelength of 405 nm after half-day transport. The generated BrC was found to be positively correlated with oxygenated and low-volatility OA, likely from the oxidation of evaporated primary OA and secondary OA formation. We found that the evolution of BrC with particle age was different in this region compared with previous BB field studies that mainly focused on emissions from smouldering fires, which have shown a high contribution from BrC at the source and BrC net loss upon ageing. This study suggests an initial stage of BrC absorption enhancement during the evolution of BB smoke. Secondary processing is the dominant contributor to BrC production in this BB region, in contrast to the primary emission of BrC previously reported in other BB studies. The total aerosol absorption normalized to BC mass (MACmeas-BC) was also enhanced with ageing due to the lensing effect of increasingly thick coatings on BC and the absorption by BrC. The effect of ageing on aerosol absorption, represented by the absorption enhancement (EAbs-MAC), was estimated over timescales of hours. MOYA-2017 provides novel field results. The comparisons between MOYA-2017 and previous field studies imply that the evolution of absorbing aerosols (BC and BrC) after emission varies with source combustion conditions. Different treatments of absorbing aerosol properties from different types of fires and their downwind evolution should be considered when modelling regional radiative forcing. These observational results will be very important for predicting climate effects of BB aerosol in regions controlled by flaming burning of agricultural waste and savannah-like biomass fuels.

The representations of clouds, aerosols, and cloud–aerosol–radiation impacts remain some of the largest uncertainties in climate change, limiting our ability to accurately reconstruct past climate and predict future climate. The south-east Atlantic is a region where high atmospheric aerosol loadings and semi-permanent stratocumulus clouds are co-located, providing an optimum region for studying the full range of aerosol–radiation and aerosol–cloud interactions and their perturbations of the Earth's radiation budget. While satellite measurements have provided some useful insights into aerosol–radiation and aerosol–cloud interactions over the region, these observations do not have the spatial and temporal resolution, nor the required level of precision to allow for a process-level assessment. Detailed measurements from high spatial and temporal resolution airborne atmospheric measurements in the region are very sparse, limiting their use in assessing the performance of aerosol modelling in numerical weather prediction and climate models. CLARIFY-2017 was a major consortium programme consisting of five principal UK universities with project partners from the UK Met Office and European- and USA-based universities and research centres involved in the complementary ORACLES, LASIC, and AEROCLO-sA projects. The aims of CLARIFY-2017 were fourfold: (1) to improve the representation and reduce uncertainty in model estimates of the direct, semi-direct, and indirect radiative effect of absorbing biomass burning aerosols; (2) to improve our knowledge and representation of the processes determining stratocumulus cloud microphysical and radiative properties and their transition to cumulus regimes; (3) to challenge, validate, and improve satellite retrievals of cloud and aerosol properties and their radiative impacts; (4) to improve the impacts of aerosols in weather and climate numerical models. This paper describes the modelling and measurement strategies central to the CLARIFY-2017 deployment of the FAAM BAe146 instrumented aircraft campaign, summarizes the flight objectives and flight patterns, and highlights some key results from our initial analyses.

Seasonal biomass burning (BB) from June to October in central and southern Africa leads to absorbing aerosols being transported over the South Atlantic Ocean every year and contributes significantly to the regional climate forcing. The vertical distribution of submicron aerosols and their properties were characterized over the remote southeast Atlantic, using airborne in situ measurements made during the CLoud-Aerosol-Radiation Interactions and Forcing for Year 2017 (CLARIFY-2017) campaign. BB aerosols emitted from flaming-controlled fires were intensively observed in the region surrounding Ascension Island, in the marine boundary layer (MBL) and free troposphere (FT) up to 5 km. We show that the aerosols had undergone a significant ageing process during > 7 d transit from source, as indicated by the highly oxidized organic aerosol. The highly aged BB aerosols in the far-field CLARIFY region were also especially rich in black carbon (BC), with relatively low single-scattering albedos (SSAs), compared with those from other BB transported regions. The column-weighted dry SSAs during CLARIFY were observed to be 0.85, 0.84 and 0.83 at 405, 550 and 658 nm respectively. We also found significant vertical variation in the dry SSA, as a function of relative chemical composition and size. The lowest SSA in the column was generally in the low FT layer around 2000 m altitude (averages: 0.82, 0.81 and 0.79 at 405, 550 and 658 nm). This finding is important since it means that BB aerosols across the southeast Atlantic region are more absorbing than currently represented in climate models, implying that the radiative forcing from BB may be more strongly positive than previously thought. Furthermore, in the FT, average SSAs at 405, 550 and 658 nm increased to 0.87, 0.86 and 0.85 with altitude up to 5 km. This was associated with an enhanced inorganic nitrate mass fraction and aerosol size, likely resulting from increased partitioning of ammonium nitrate to the existing particles at higher altitude with lower temperature and higher relative humidity. After entrainment into the boundary layer (BL), aerosols were generally smaller in dry size than in the FT and had a larger fraction of scattering material with resultant higher average dry SSA, mostly due to marine emissions and aerosol removal by drizzle. In the BL, the SSA decreased from the surface to the BL top, with the highest SSA in the column observed near the surface. Our results provide unique observational constraints on aerosol parameterizations used in modelling regional radiation interactions over this important region. We recommend that future work should consider the impact of this vertical variability on climate models.

The optical properties of black carbon (BC) are a major source of uncertainty in regional and global climate studies. In the past, detailed investigation of BC absorption has been hampered by systematic biases in the measurement instrumentation. We present airborne measurements of aerosol absorption and black carbon microphysical properties in highly aged biomass burning plumes measured 4–8 d from their source over the southeast Atlantic Ocean during CLARIFY-2017, using a suite of novel photoacoustic spectrometers to measure aerosol absorption at 405, 514, and 655 nm and a single-particle soot photometer to measure the BC mass concentration, size, and mixing state. These measurements are of sufficient quality and detail to provide constraint on optical schemes used in climate models for the first time in biomass burning plumes far from their source – an aerosol environment that is one of the most important climatically. The average absorption Ångström exponents (AAE) were 1.38 over the wavelength range from 405 to 514 nm and 0.88 over the range from 514 to 655 nm, suggesting that brown carbon (BrC) contributed to 11±2 % of absorption at 405 nm. The effective organic aerosol (OA) mass absorption coefficient (MAC) was 0.31±0.09 m2 g−1 at 405 nm. The BC particles were universally thickly coated, and almost no externally mixed BC particles were detected. The average MAC of BC was 20±4, 15±3, and 12±2 m2g−1 at wavelengths of 405, 514, and 655 nm respectively, with equivalent absorption enhancements of around 1.85±0.45 at all three wavelengths, suggesting that the thick coatings acted as a lens that enhanced light absorption by the BC. We compared the measured MAC and AAE values with those calculated using several optical models and absorption parameterisations that took the measured BC mass and mixing state as inputs. Homogeneous grey-sphere Mie models were only able to replicate MAC for some low (real and imaginary) values of the complex BC refractive index (mBC) at the shortest wavelength, but they would have to use unrealistically low values of mBC to accurately replicate the AAE. A core–shell Mie model was able to generate good agreement for MAC in the green–red end of the visible spectrum for most values of mBC. However, there are no possible values of mBC that produce MAC values that agree with our observations at all three wavelengths, due to a wavelength-dependent underestimation of the MAC of the underlying BC core. Four semiempirical parameterisations from the literature were also tested, linking the BC mixing state to either the MAC or absorption enhancement. Two of these schemes produced results that agreed within a few percent with the measured MAC at all three wavelengths, and the AAE agreed well when discounting the effects of BrC. Our results uniquely demonstrate the validity of absorption parameterisations, as well as the failings of Mie calculations, in this highly aged environment. We recommend that future work should conduct similar analyses in environments where BC has different properties; future studies should also investigate the impact of implementing these types of schemes within climate models as well as the impact of developing equivalent schemes for light scattering by soot particles at visible wavelengths.

This work presents synergistic satellite, airborne and surface-based observations of a pocket of open cells (POC) in the remote south-east Atlantic. The observations were obtained over and upwind of Ascension Island during the CLouds and Aerosol Radiative Impacts and Forcing (CLARIFY) and the Layered Smoke Interacting with Clouds (LASIC) field experiments. A novel aspect of this case study is that an extensive free-tropospheric biomass burning aerosol plume that had been transported from the African continent was observed to be in contact with the boundary layer inversion over the POC and the surrounding closed cellular cloud regime. The in situ measurements show marked contrasts in the boundary layer thermodynamic structure, cloud properties, precipitation and aerosol conditions between the open cells and surrounding overcast cloud field. The data demonstrate that the overlying biomass burning aerosol was mixing down into the boundary layer in the stratocumulus cloud downwind of the POC, with elevated carbon monoxide, black carbon mass loadings and accumulation-mode aerosol concentrations measured beneath the trade-wind inversion. The stratocumulus cloud in this region was moderately polluted and exhibited very little precipitation falling below cloud base. A rapid transition to actively precipitating cumulus clouds and detrained stratiform remnants in the form of thin quiescent veil clouds was observed across the boundary into and deep within the POC. The subcloud layer in the POC was much cleaner than that in the stratocumulus region. The clouds in the POC formed within an ultra-clean layer (accumulation-mode aerosol concentrations of approximately a few cm−3) in the upper region of the boundary layer, which was likely to have been formed via efficient collision–coalescence and sedimentation processes. Enhanced Aitken-mode aerosol concentrations were also observed intermittently in this ultra-clean layer, suggesting that new particle formation was taking place. Across the boundary layer inversion and immediately above the ultra-clean layer, accumulation-mode aerosol concentrations were ∼ 1000 cm−3. Importantly, the air mass in the POC showed no evidence of elevated carbon monoxide over and above typical background conditions at this location and time of year. As carbon monoxide is a good tracer for biomass burning aerosol that is not readily removed by cloud processing and precipitation, it demonstrates that the open cellular convection in the POC is not able to entrain large quantities of the free-tropospheric aerosol that was sitting directly on top of the boundary layer inversion. This suggests that the structure of the mesoscale cellular convection may play an important role in regulating the transport of aerosol from the free troposphere down into the marine boundary layer. We then develop a climatology of open cellular cloud conditions in the south-east Atlantic from 19 years of September Moderate Resolution Imaging Spectroradiometer (MODIS) Terra imagery. This shows that the maxima in open cell frequency (> 0.25) occurs far offshore and in a region where subsiding biomass burning aerosol plumes may often come into contact with the underlying boundary layer cloud. If the results from the observational case study applied more broadly, then the apparent low susceptibility of open cells to free-tropospheric intrusions of additional cloud condensation nuclei could have some important consequences for aerosol–cloud interactions in the region.

In this paper we show that the origin of the ice phase in tropical cumulus clouds over the sea may occur by primary ice nucleation of small crystals at temperatures just between 0 and −5 ∘C. This was made possible through use of a holographic instrument able to image cloud particles at very high resolution and small size (6 µm). The environment in which the observations were conducted was notable for the presence of desert dust advected over the ocean from the Sahara. However, there is no laboratory evidence to suggest that these dust particles can act as ice nuclei at temperatures warmer than about −10 ∘C, the zone in which the first ice was observed in these clouds. The small ice particles were observed to grow rapidly by vapour diffusion, riming, and possibly through collisions with supercooled raindrops, causing these to freeze and potentially shatter. This in turn leads to the further production of secondary ice in these clouds. Hence, although the numbers of primary ice particles are small, they are very effective in initiating the rapid glaciation of the cloud, altering the dynamics and precipitation production processes.

Vast stretches of agricultural land in southern and central Africa are burnt between June and September each year, which releases large quantities of aerosol into the atmosphere. The resulting smoke plumes are carried west over the Atlantic Ocean at altitudes between 2 and 4 km. As only limited observational data in West Africa have existed until now, whether this pollution has an impact at lower altitudes has remained unclear. The Dynamics-aerosol-chemistry-cloud interactions in West Africa (DACCIWA) aircraft campaign took place in southern West Africa during June and July 2016, with the aim of observing gas and aerosol properties in the region in order to assess anthropogenic and other influences on the atmosphere. Results presented here show that a significant mass of aged accumulation mode aerosol was present in the southern West African monsoon layer, over both the ocean and the continent. A median dry aerosol concentration of 6.2 µg m−3 (standard temperature and pressure, STP) was observed over the Atlantic Ocean upwind of the major cities, with an interquartile range from 5.3 to 8.0 µg m−3. This concentration increased to a median of 11.1 µg m−3 (8.6 to 15.7 µg m−3) in the immediate outflow from cities. In the continental air mass away from the cities, the median aerosol loading was 7.5 µg m−3 (5.9 to 10.5 µg m−3). The accumulation mode aerosol population over land displayed similar chemical properties to the upstream population, which implies that upstream aerosol is a significant source of aerosol pollution over the continent. The upstream aerosol is found to have most likely originated from central and southern African biomass burning. This demonstrates that biomass burning plumes are being advected northwards, after being entrained into the monsoon layer over the eastern tropical Atlantic Ocean. It is shown observationally for the first time that they contribute up to 80 % to the regional aerosol loading in the monsoon layer over southern West Africa. Results from the COSMO-ART (Consortium for Small-scale Modeling – Aerosol and Reactive Trace gases) and GEOS-Chem models support this conclusion, showing that observed aerosol concentrations over the northern Atlantic Ocean can only be reproduced when the contribution of transported biomass burning aerosol is taken into account. As a result, the large and growing emissions from the coastal cities are overlaid on an already substantial aerosol background. Simulations using COSMO-ART show that cloud droplet number concentrations can increase by up to 27 % as a result of transported biomass burning aerosol. On a regional scale this renders cloud properties and precipitation less sensitive to future increases in anthropogenic emissions. In addition, such high background loadings will lead to greater pollution exposure for the large and growing population in southern West Africa. These results emphasise the importance of including aerosol from across country borders in the development of air pollution policies and interventions in regions such as West Africa.

Low-level clouds (LLCs) cover a wide area of southern West Africa (SWA) during the summer monsoon months and have an important cooling effect on the regional climate. Previous studies of these clouds have focused on modelling and remote sensing via satellite. We present the first comprehensive set of in situ measurements of cloud microphysics from the region, taken during June–July 2016, as part of the DACCIWA (Dynamics–aerosol–chemistry–cloud interactions in West Africa) campaign. This novel dataset allows us to assess spatial, diurnal, and day-to-day variation in the properties of these clouds over the region. LLCs developed overnight and mean cloud cover peaked a few hundred kilometres inland around 10:00 local solar time (LST), before clouds began to dissipate and convection intensified in the afternoon. Regional variation in LLC cover was largely orographic, and no lasting impacts in cloud cover related to pollution plumes were observed downwind of major population centres. The boundary layer cloud drop number concentration (CDNC) was locally variable inland, ranging from 200 to 840 cm−3 (10th and 90th percentiles at standard temperature and pressure), but showed no systematic regional variations. Enhancements were seen in pollution plumes from the coastal cities but were not statistically significant across the region. A significant fraction of accumulation mode aerosols, and therefore cloud condensation nuclei, were from ubiquitous biomass burning smoke transported from the Southern Hemisphere. To assess the relative importance of local and transported aerosol on the cloud field, we isolated the local contribution to the aerosol population by comparing inland and offshore size and composition measurements. A parcel model sensitivity analysis showed that doubling or halving local emissions only changed the calculated cloud drop number concentration by 13 %–22 %, as the high background meant local emissions were a small fraction of total aerosol. As the population of SWA grows, local emissions are expected to rise. Biomass burning smoke transported from the Southern Hemisphere is likely to dampen any effect of these increased local emissions on cloud–aerosol interactions. An integrative analysis between local pollution and Central African biomass burning emissions must be considered when predicting anthropogenic impacts on the regional cloud field during the West African summer monsoon.

Biases in absorption coefficients measured using a filter-based absorption photometer (Tricolor Absorption Photometer, or TAP) at wavelengths of 467, 528 and 652 nm are evaluated by comparing to measurements made using photoacoustic spectroscopy (PAS). We report comparisons for ambient sampling covering a range of aerosol types including urban, fresh biomass burning and aged biomass burning. Data are also used to evaluate the performance of three different TAP correction schemes. We found that photoacoustic and filter-based measurements were well correlated, but filter-based measurements generally overestimated absorption by up to 45 %. Biases varied with wavelength and depended on the correction scheme applied. Optimal agreement to PAS data was achieved by processing the filter-based measurements using the recently developed correction scheme of Müller et al. (2014), which consistently reduced biases to 0 %–18 % at all wavelengths. The biases were found to be a function of the ratio of organic aerosol mass to light-absorbing carbon mass, although applying the Müller et al. (2014) correction scheme to filter-based absorption measurements reduced the biases and the strength of this correlation significantly. Filter-based absorption measurement biases led to aerosol single-scattering albedos that were biased low by values in the range 0.00–0.07 and absorption Ångström exponents (AAEs) that were in error by ± (0.03–0.54). The discrepancy between the filter-based and PAS absorption measurements is lower than reported in some earlier studies and points to a strong dependence of filter-based measurement accuracy on aerosol source type.

Water in the atmosphere can exist in the solid, liquid or gas phase. At high humidities, if the aerosol population remains constant, more water vapour will condense onto the particles and cause them to swell, sometimes up to several times their original size. This significant change in size and chemical composition is termed hygroscopic growth and alters a particle's optical properties. Even in unsaturated conditions, this can change the aerosol direct effect, for example by increasing the extinction of incoming sunlight. This can have an impact on a region's energy balance and affect visibility. Here, aerosol and relative humidity measurements collected from aircraft and radiosondes during the Dynamics–Aerosol–Chemistry–Cloud Interactions in West Africa (DACCIWA) campaign were used to estimate the effect of highly humid layers of air on aerosol optical properties during the monsoon season in southern West Africa. The effects of hygroscopic growth in this region are of particular interest due to the regular occurrence of high humidity and the high levels of pollution in the region. The Zdanovskii, Stokes and Robinson (ZSR) mixing rule is used to estimate the hygroscopic growth of particles under different conditions based on chemical composition. These results are used to estimate the aerosol optical depth (AOD) at λ=525 nm for 63 relative humidity profiles. The median AOD in the region from these calculations was 0.36, the same as that measured by sun photometers at the ground site. The spread in the calculated AODs was less than the spread from the sun photometer measurements. In both cases, values above 0.5 were seen predominantly in the mornings and corresponded with high humidities. Observations of modest variations in aerosol load and composition are unable to explain the high and variable AODs observed using sun photometers, which can only be recreated by accounting for the very elevated and variable relative humidities (RHs) in the boundary layer. Most importantly, the highest AODs present in the mornings are not possible without the presence of high RH in excess of 95 %. Humid layers are found to have the most significant impact on AOD when they reach RH greater than 98 %, which can result in a wet AOD more than 1.8 times the dry AOD. Unsaturated humid layers were found to reach these high levels of RH in 37 % of observed cases. It can therefore be concluded that the high AODs present across the region are driven by the high humidities and are then moderated by changes in aerosol abundance. Aerosol concentrations in southern West Africa are projected to increase substantially in the coming years; results presented here show that the presence of highly humid layers in the region is likely to enhance the consequent effect on AOD significantly.

Mineral dust is an important component of the climate system, affecting the radiation balance, cloud properties, biogeochemical cycles, regional circulation and precipitation, as well as having negative effects on aviation, solar energy generation and human health. Dust size and composition has an impact on all these processes. However, changes in dust size distribution and composition during transport, particularly for coarse particles, are poorly understood and poorly represented in climate models. Here we present new in situ airborne observations of dust in the Saharan Air Layer (SAL) and the marine boundary layer (MBL) at the beginning of its transatlantic transport pathway, from the AERosol Properties – Dust (AER-D) fieldwork in August 2015, within the peak season of North African dust export. This study focuses on coarse-mode dust properties, including size distribution, mass loading, shape, composition, refractive indices and optical properties. Size distributions from 0.1 to 100 µm diameter (d) are presented, fully incorporating the coarse and giant modes of dust. Within the MBL, mean effective diameter (deff) and volume median diameter (VMD) were 4.6 and 6.0 µm respectively, giant particles with a mode at 20–30 µm were observed, and composition was dominated by quartz and alumino-silicates at d > 1 µm. Within the SAL, particles larger than 20 µm diameter were always present up to 5 km altitude, in concentrations over 10−5 cm−3, constituting up to 40 % of total dust mass. Mean deff and VMD were 4.0 and 5.5 µm respectively. Larger particles were detected in the SAL than can be explained by sedimentation theory alone. Coarse-mode composition was dominated by quartz and alumino-silicates; the accumulation mode showed a strong contribution from sulfate-rich and sea salt particles. In the SAL, measured single scattering albedos (SSAs) at 550 nm representing d d 2 g−1 (mean 0.32 m2 g−1). Variability in SSA was mainly controlled by variability in dust composition (principally iron) rather than by variations in the size distribution, in contrast with previous observations over the Sahara where size is the dominant influence. It is important that models are able to capture the variability and evolution of both dust composition and size distribution with transport in order to accurately represent the impacts of dust on climate. These results provide a new SAL dust dataset, fully representing coarse and giant particles, to aid model validation and development.

During the summertime, dust from the Sahara can be efficiently transported westwards within the Saharan air layer (SAL). This can lead to high aerosol loadings being observed above a relatively clean marine boundary layer (MBL) in the tropical Atlantic Ocean. These dust layers can impart significant radiative effects through strong visible and IR light absorption and scattering, and can also have indirect impacts by altering cloud properties. The processing of the dust aerosol can result in changes in both direct and indirect radiative effects, leading to significant uncertainty in climate prediction in this region. During August 2015, measurements of aerosol and cloud properties were conducted off the coast of west Africa as part of the Ice in Cloud Experiment – Dust (ICE-D) and AERosol properties – Dust (AER-D) campaigns. Observations were obtained over a 4-week period using the UK Facility for Atmospheric Airborne Measurements (FAAM) BAe 146 aircraft based on Santiago Island, Cabo Verde. Ground-based observations were collected from Praia (14°57′ N, 23°29′ W; 100 m a.s.l.), also located on Santiago Island. The dust in the SAL was mostly sampled in situ at altitudes of 2–4 km, and the potential dust age was estimated by backward trajectory analysis. The particle mass concentration (at diameter d = 0.1–20 µm) decreased with transport time. Mean effective diameter (Deff) for supermicron SAL dust (d = 1–20 µm) was found to be 5–6 µm regardless of dust age, whereas submicron Deff (d = 0.1–1 µm) showed a decreasing trend with longer transport. For the first time, an airborne laser-induced incandescence instrument (the single particle soot photometer – SP2) was deployed to measure the hematite content of dust. For the Sahel-influenced dust in the SAL, the observed hematite mass fraction of dust (FHm) was found to be anti-correlated with the single scattering albedo (SSA, λ = 550 nm, for particles d FHm increased from 2.5 to 4.5 %, SSA decreased from 0.97 to 0.93 and the derived imaginary part (k) of the refractive index at 550 nm increased from 0.0015 to 0.0035. However, the optical properties of Sahara-influenced plumes (not influenced by the Sahel) were independent of dust age and hematite content with SSA ∼ 0.95 and k ∼ 0.0028. This indicates that the absorbing component of dust may be source dependent, or that gravitational settling of larger particles may lead to a higher fraction of more absorbing clay–iron aggregates at smaller sizes. Mie calculation using the measured size distribution and size-resolved refractive indices of the absorbing components (black carbon and hematite) reproduces the measured SSA to within ±0.02 for SAL dust by assuming a goethite ∕ hematite mass ratio of 2. Overall, hematite and goethite constituted 40–80 % of the absorption for particles d

Coupling compartmentalisation and molecular replication is essential for the development of evolving chemical systems. Here the authors show an oil-in-water droplet containing a self-replicating amphiphilic imine that can undergo repeated droplet division.

Single-particle mass spectrometry (SPMS) is a useful tool for the online study of aerosols with the ability to measure size-resolved chemical composition with a temporal resolution relevant to atmospheric processes. In SPMS, optical particle detection is used for the effective temporal alignment of an ablation laser pulse with the presence of a particle in the ion source, and it gives the option of aerodynamic sizing by measuring the offset of particle arrival times between two detection stages. The efficiency of the optical detection stage has a strong influence on the overall instrument performance. A custom detection laser system consisting of a high-powered fibre-coupled Nd:YAG solid-state laser with a collimated beam was implemented in the detection stage of a laser ablation aerosol particle time-of-flight (LAAP-TOF) single-particle mass spectrometer without major modifications to instrument geometry. The use of a collimated laser beam permitted the construction of a numerical model that predicts the effects of detection laser wavelength, output power, beam focussing characteristics, light collection angle, particle size, and refractive index on the effective detection radius (R) of the detection laser beam. We compare the model predictions with an ambient data set acquired during the Ice in Clouds Experiment – Dust (ICE-D) project. The new laser system resulted in an order-of-magnitude improvement in instrument sensitivity to spherical particles in the size range 500–800 nm compared to a focussed 405 nm laser diode system. The model demonstrates that the limit of detection in terms of particle size is determined by the scattering cross section (Csca) as predicted by Mie theory. In addition, if light is collected over a narrow collection angle, oscillations in the magnitude of Csca with respect to particle diameter result in a variation in R, resulting in large particle-size-dependent variation in detection efficiency across the particle transmission range. This detection bias is imposed on the aerodynamic size distributions measured by the instrument and accounts for some of the detection bias towards sea salt particles in the ambient data set.

In situ airborne observations of cloud microphysics, aerosol properties, and thermodynamic structure over the transition from sea ice to ocean are presented from the Aerosol-Cloud Coupling And Climate Interactions in the Arctic (ACCACIA) campaign. A case study from 23 March 2013 provides a unique view of the cloud microphysical changes over this transition under cold-air outbreak conditions. Cloud base lifted and cloud depth increased over the transition from sea ice to ocean. Mean droplet number concentrations, Ndrop, also increased from 110 ± 36 cm−3 over the sea ice to 145 ± 54 cm−3 over the marginal ice zone (MIZ). Downstream over the ocean, Ndrop decreased to 63 ± 30 cm−3. This reduction was attributed to enhanced collision-coalescence of droplets within the deep ocean cloud layer. The liquid water content increased almost four fold over the transition and this, in conjunction with the deeper cloud layer, allowed rimed snowflakes to develop and precipitate out of cloud base downstream over the ocean. The ice properties of the cloud remained approximately constant over the transition. Observed ice crystal number concentrations averaged approximately 0.5–1.5 L−1, suggesting only primary ice nucleation was active; however, there was evidence of crystal fragmentation at cloud base over the ocean. Little variation in aerosol particle number concentrations was observed between the different surface conditions; however, some variability with altitude was observed, with notably greater concentrations measured at higher altitudes ( > 800 m) over the sea ice. Near-surface boundary layer temperatures increased by 13 °C from sea ice to ocean, with corresponding increases in surface heat fluxes and turbulent kinetic energy. These significant thermodynamic changes were concluded to be the primary driver of the microphysical evolution of the cloud. This study represents the first investigation, using in situ airborne observations, of cloud microphysical changes with changing sea ice cover and addresses the question of how the microphysics of Arctic stratiform clouds may change as the region warms and sea ice extent reduces.

Heavy rainfall from convective clouds can lead to devastating flash flooding, and observations of aerosols and clouds are required to improve cloud parameterisations used in precipitation forecasts. We present measurements of boundary layer aerosol concentration, size, and composition from a series of research flights performed over the southwest peninsula of the UK during the COnvective Precipitation Experiment (COPE) of summer 2013. We place emphasis on periods of southwesterly winds, which locally are most conducive to convective cloud formation, when marine air from the Atlantic reached the peninsula. Accumulation-mode aerosol mass loadings were typically 2–3 µg m−3 (corrected to standard cubic metres at 1013.25 hPa and 273.15 K), the majority of which was sulfuric acid over the sea, or ammonium sulfate inland, as terrestrial ammonia sources neutralised the aerosol. The cloud condensation nuclei (CCN) concentrations in these conditions were ∼ 150–280 cm−3 at 0.1 % and 400–500 cm−3 at 0.9 % supersaturation (SST), which are in good agreement with previous Atlantic measurements, and the cloud drop concentrations at cloud base ranged from 100 to 500 cm−3. The concentration of CCN at 0.1 % SST was well correlated with non-sea-salt sulfate, meaning marine sulfate formation was likely the main source of CCN. Marine organic aerosol (OA) had a similar mass spectrum to previous measurements of sea spray OA and was poorly correlated with CCN. In one case study that was significantly different to the rest, polluted anthropogenic emissions from the southern and central UK advected to the peninsula, with significant enhancements of OA, ammonium nitrate and sulfate, and black carbon. The CCN concentrations here were around 6 times higher than in the clean cases, and the cloud drop number concentrations were 3–4 times higher. Sources of ice-nucleating particles (INPs) were assessed by comparing different parameterisations used to predict INP concentrations, using measured aerosol concentrations as input. The parameterisations based on total aerosol produced INP concentrations that agreed within an order of magnitude with measured first ice concentrations at cloud temperatures as low as −12 °C. Composition-specific parameterisations for mineral dust, fluorescent particles, and sea spray OA were 3–4 orders of magnitude lower than the measured first ice concentrations, meaning a source of INPs was present that was not characterised by our measurements and/or one or more of the composition-specific parameterisations greatly underestimated INPs in this environment.

We present microphysical observations of cumulus clouds measured over the southwest peninsula of the UK during the COnvective Precipitation Experiment (COPE) in August 2013, which are framed into a wider context using ground-based and airborne radar measurements. Two lines of cumulus clouds formed in the early afternoon along convergence lines aligned with the peninsula. The lines became longer and broader during the afternoon due to new cell formation and stratiform regions forming downwind of the convective cells. Ice concentrations up to 350 L−1, well in excess of the expected ice nuclei (IN) concentrations, were measured in the mature stratiform regions, suggesting that secondary ice production was active. Detailed sampling focused on an isolated liquid cloud that glaciated as it matured to merge with a band of cloud downwind. In the initial cell, drizzle concentrations increased from ∼ 0.5 to ∼ 20 L−1 in around 20 min. Ice concentrations developed up to a few per litre, which is around the level expected of primary IN. The ice images were most consistent with freezing drizzle, rather than smaller cloud drops or interstitial IN forming the first ice. As new cells emerged in and around the cloud, ice concentrations up to 2 orders of magnitude higher than the predicted IN concentrations developed, and the cloud glaciated over a period of 12–15 min. Almost all of the first ice particles to be observed were frozen drops, while vapour-grown ice crystals were dominant in the latter stages. Our observations are consistent with the production of large numbers of small secondary ice crystals/fragments, by a mechanism such as Hallett–Mossop or droplets shattering upon freezing. Some of the small ice froze drizzle drops on contact, while others grew more slowly by vapour deposition. Graupel and columns were seen in cloud penetrations up to the −12 °C level, though many ice particles were mixed habit due to riming and growth by vapour deposition at multiple temperatures. Our observations demonstrate that the freezing of drizzle/raindrops is an important process that dominates the formation of large ice in the intermediate stages of cloud development. As these frozen drops were the first precipitation observed, interactions between the warm-rain and secondary ice production processes appear to be key to determining the timing and location of precipitation.

Black carbon aerosol (BC) deposited to the Arctic sea ice or present in the free troposphere can significantly affect the Earth's radiation budget at high latitudes yet the BC burden in these regions and the regional source contributions are poorly constrained. Aircraft measurements of aerosol composition in the European Arctic were conducted during the Aerosol–Cloud Coupling And Climate Interactions in the Arctic (ACCACIA) campaign in March 2013. Pollutant plumes were encountered throughout the lower to upper Arctic troposphere featuring enhancements in CO and aerosol mass loadings, which were chemically speciated into BC and non-refractory sulphate and organic matter. FLEXPART-WRF simulations have been performed to evaluate the likely contribution to the pollutants from regional ground sources. By combining up-to-date anthropogenic and open fire biomass burning (OBB) inventories, we have been able to compare the contributions made to the observed pollution layers from the sources of eastern/northern Asia (AS), Europe (EU) and North America (NA). Over 90 % of the contribution to the BC was shown to arise from non-OBB anthropogenic sources. AS sources were found to be the major contributor to the BC burden, increasing background BC loadings by a factor of 3–5 to 100.8 ± 48.4 ng sm−3 (in standard air m3 at 273.15 K and 1013.25 mbar) and 55.8 ± 22.4 ng sm−3 in the middle and upper troposphere respectively. AS plumes close to the tropopause (about 7.5–8 km) were also observed, with BC concentrations ranging from 55 to 73 ng sm−3, which will potentially have a significant radiative impact. EU sources influenced the middle troposphere with a BC mean concentration of 70.8 ± 39.1 ng sm−3 but made a minor contribution to the upper troposphere due to the relatively high latitude of the source region. The contribution of NA was shown to be much lower at all altitudes with BC mean concentration of 20 ng sm−3. The BC transported to the Arctic is mixed with a non-BC volume fraction representing between 90–95 % of the mass, and has a relatively uniform core size distribution with mass median diameter 190–210 nm and geometric standard deviation σg = 1.55–1.65 and this varied little across all source regions. It is estimated that 60–95 % of BC is scavenged between emission and receptor based on BC / ΔCO comparisons between source inventories and measurement. We show that during the springtime of 2013, the anthropogenic pollution particularly from sources in Asia, contributed significantly to BC across the European Arctic free troposphere. In contrast to previous studies, the contribution from open wildfires was minimal. Given that Asian pollution is likely to continue to rise over the coming years, it is likely that the radiative forcing in the Arctic will also continue to increase.

Within minutes after emission, complex photochemistry in biomass burning smoke plumes can cause large changes in the concentrations of ozone (O3) and organic aerosol (OA). Being able to understand and simulate this rapid chemical evolution under a wide variety of conditions is a critical part of forecasting the impact of these fires on air quality, atmospheric composition, and climate. Here we use version 2.1 of the Aerosol Simulation Program (ASP) to simulate the evolution of O3 and secondary organic aerosol (SOA) within a young biomass burning smoke plume from the Williams prescribed fire in chaparral, which was sampled over California in November 2009. We demonstrate the use of a method for simultaneously accounting for the impact of the unidentified intermediate volatility, semi-volatile, and extremely low volatility organic compounds (here collectively called "SVOCs") on the formation of OA (using the Volatility Basis Set – VBS) and O3 (using the concept of mechanistic reactivity). We show that this method can successfully simulate the observations of O3, OA, NOx, ethylene (C2H4), and OH to within measurement uncertainty using reasonable assumptions about the average chemistry of the unidentified SVOCs. These assumptions were (1) a reaction rate constant with OH of ~ 10-11 cm3 s−1; (2) a significant fraction (up to ~ 50 %) of the RO2 + NO reaction resulted in fragmentation, rather than functionalization, of the parent SVOC; (3) ~ 1.1 molecules of O3 were formed for every molecule of SVOC that reacted; (4) ~ 60 % of the OH that reacted with the unidentified non-methane organic compounds (NMOC) was regenerated as HO2; and (5) that ~ 50 % of the NO that reacted with the SVOC peroxy radicals was lost, presumably to organic nitrate formation. Additional evidence for the fragmentation pathway is provided by the observed rate of formation of acetic acid (CH3COOH), which is consistent with our assumed fragmentation rate. However, the model overestimates peroxyacetyl nitrate (PAN) formation downwind by about 50 %, suggesting the need for further refinements to the chemistry. This method could provide a way for classifying different smoke plume observations in terms of the average chemistry of their SVOCs, and could be used to study how the chemistry of these compounds (and the O3 and OA they form) varies between plumes.

Accurately accounting for new particle formation (NPF) is crucial to our ability to predict aerosol number concentrations in many environments and thus cloud properties, which is in turn vital in simulating radiative transfer and climate. Here we present an analysis of NPF events observed in the Greenland Sea during the summertime as part of the Aerosol-Cloud Coupling And Climate Interactions in the Arctic (ACCACIA) project. While NPF events have been reported in the Arctic before, we were able, for the first time, to detect iodine in the growing particles using an Aerosol Mass Spectrometer (AMS) during a persistent event in the region of the coastal sea-ice near Greenland. Given the potency of iodine as a nucleation precursor, the results imply that iodine was responsible for the initial NPF, a phenomenon that has been reported at lower latitudes and associated with molecular iodine emissions from coastal macroalgae. The initial source of iodine in this instance is not clear, but it was associated with air originating approximately 1 day previously over melting coastal sea-ice. These results show that atmospheric models must consider iodine as a source of new particles in addition to established precursors such as sulfur compounds.

Black carbon (BC) is the dominant absorbing aerosol in the atmosphere, and plays an important role in climate and human health. The optical properties and cloud condensation nuclei (CCN) activity of soot depend on the amounts (both relative and absolute) of BC and non-refractory material in the particles. Mixing between these two components is often represented in models by a core / shell coated sphere. The single-particle soot photometer (SP2) is one of, if not the only, instrument capable of reporting distributions of both core size and coating thickness. Most studies combine the SP2's incandescence and 1064 nm scattering data to report coating properties, but to date there is no consistency in the assumed values of density and refractive index of the core that are used in these calculations, which can greatly affect the reported parameters such as coating thickness. Given that such data are providing an important constraint for model comparisons and comparison between large data sets, it is important that this lack of consistency is addressed. In this study we explore the sensitivity of the reported coatings to these parameters. An assessment of the coating properties of freshly emitted, thermodenuded ambient particles demonstrated that a core density of 1.8 g cm−3 and refractive index of (2.26–1.26i) were the most appropriate to use with ambient soot in the Los Angeles area. Using these parameters generated a distribution with median shell / core ratio of 1.02 ± 0.11, corresponding to a median absolute coating thickness of 2 ± 8 nm. The main source of statistical error in the single-particle data was random variation in the incandescence signals. Other than the sensitivity to core refractive index, the incandescence calibration was the main source of uncertainty when optically determining the average coatings. The refractive index of coatings was found to have only a minor influence. This work demonstrates that using this technique the SP2 can accurately determine the average mixing state (externally or internally mixed) of ambient soot within the precision of the instrument calibration. Ambient coatings were measured up to a median shell / core ratio of 1.50 ± 0.11, meaning that this technique is able to resolve absolute changes in mixing state. However, when different core parameters were used, the core / shell ratio and the coating thickness were shown to be offset by amounts that could be larger than the atmospheric variability in these parameters, though the results have a similar precision. For comparison, using the core parameters that resulted in the thickest coatings, on the same thermodenuded fresh particles as before, generated a median shell / core ratio of 1.39 ± 0.11, corresponding to a median absolute coating thickness of 30 ± 8 nm. These results must be taken into account when comparing BC coatings measured using this technique, or if using these data for optical or CCN calculations. We have determined the most appropriate values of BC density and refractive index to use to measure mixing state at 1064 nm where particle morphology has only a minor effect, but appropriate values to use for optical calculations of nonspherical particles at visible wavelengths will also be subject to similar, significant uncertainties. Without similar constraints as those provided here, constraining the behaviour of BC particles in models using field data will be subject to large systematic measurement uncertainties.

Airborne measurements of biomass burning organic aerosol (BBOA) from boreal forest fires reveal highly contrasting properties for plumes of different ages. These measurements, performed using an Aerodyne Research Inc. compact time-of-flight aerosol mass spectrometer (C-ToF-AMS) during the BORTAS (quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) experiment in the summer of 2011, have been used to derive normalised excess organic aerosol (OA) mass concentrations (ΔOA / ΔCO), with higher average ratios observed closer to source (0.190±0.010) than in the far-field (0.097±0.002). The difference in ΔOA / ΔCO between fresh and aged plumes is influenced by a change in dominant combustion conditions throughout the campaign. Measurements at source comprised 3 plume interceptions during a single research flight and sampled largely smouldering fires. Twenty-three interceptions were made across four flights in the far-field, with plumes originating from fires occurring earlier in the campaign when fire activity had been more intense, creating an underlying contrast in emissions prior to any transformations associated with aging. Changing combustion conditions also affect the vertical distribution of biomass burning emissions, as aged plumes from more flaming-dominated fires are injected to higher altitudes of up to 6000 m. Proportional contributions of the mass-to-charge ratio (m/z) 60 and 44 peaks in the AMS mass spectra to the total OA mass (denoted f60 and f44) are used as tracers for primary and oxidised BBOA, respectively. f44 is lower on average in near-field plumes than those sampled in the far-field, in accordance with longer aging times as plumes are transported a greater distance from source. However, high levels of ΔO3 / ΔCO and −log(NOx / NOy) close to source indicate that emissions can be subject to very rapid oxidation over short timescales. Conversely, the lofting of plumes into the upper troposphere can lead to the retention of source profiles after transportation over extensive temporal and spatial scales, with f60 also higher on average in aged plumes. Evolution of OA composition with aging is comparable to observations of BB tracers in previous studies, revealing a consistent progression from f60 to f44. The elevated levels of oxygenation in aged plumes, and their association with lower average ΔOA / ΔCO, are consistent with OA loss through evaporation during aging due to a combination of dilution and chemical processing, while differences in combustion conditions throughout the campaign also have a significant influence on BBOA production and composition.

Biomass-burning aerosols contribute to aerosol radiative forcing on the climate system. The magnitude of this effect is partially determined by aerosol size distributions, which are functions of source fire characteristics (e.g. fuel type, MCE) and in-plume microphysical processing. The uncertainties in biomass-burning emission number–size distributions in climate model inventories lead to uncertainties in the CCN (cloud condensation nuclei) concentrations and forcing estimates derived from these models. The BORTAS-B (Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellite) measurement campaign was designed to sample boreal biomass-burning outflow over eastern Canada in the summer of 2011. Using these BORTAS-B data, we implement plume criteria to isolate the characteristic size distribution of aged biomass-burning emissions (aged ~ 1–2 days) from boreal wildfires in northwestern Ontario. The composite median size distribution yields a single dominant accumulation mode with Dpm = 230 nm (number-median diameter) and σ = 1.5, which are comparable to literature values of other aged plumes of a similar type. The organic aerosol enhancement ratios (ΔOA / ΔCO) along the path of Flight b622 show values of 0.09–0.17 μg m−3 ppbv−1 (parts per billion by volume) with no significant trend with distance from the source. This lack of enhancement ratio increase/decrease with distance suggests no detectable net OA (organic aerosol) production/evaporation within the aged plume over the sampling period (plume age: 1–2 days), though it does not preclude OA production/loss at earlier stages. A Lagrangian microphysical model was used to determine an estimate of the freshly emitted size distribution corresponding to the BORTAS-B aged size distributions. The model was restricted to coagulation and dilution processes based on the insignificant net OA production/evaporation derived from the ΔOA / ΔCO enhancement ratios. We estimate that the young-plume median diameter was in the range of 59–94 nm with modal widths in the range of 1.7–2.8 (the ranges are due to uncertainty in the entrainment rate). Thus, the size of the freshly emitted particles is relatively unconstrained due to the uncertainties in the plume dilution rates.

Wet deposition is the dominant mechanism for removing black carbon (BC) from the atmosphere and is key in determining its atmospheric lifetime, vertical gradient and global transport. Despite the importance of BC in the climate system, especially in terms of its ability to modulate the radiative energy budget, there are few quantitative case studies of wet removal in ambient environments. We present a case study of BC wet removal by examining aerosol size distributions and BC coating properties sampled in three Canadian boreal biomass burning plumes, one of which passed through a precipitating cloud. This depleted the majority of the plume's BC mass, and the largest and most coated BC-containing particles were found to be preferentially removed, suggesting that nucleation scavenging was likely the dominant mechanism. Calculated single-scattering albedo (SSA) showed little variation, as a large number of non-BC particles were also present in the precipitation-affected plume. The remaining BC cores were smaller than those observed in previous studies of BC in post-precipitation outflow over Asia, possibly due to the thick coating by hydrophilic compounds associated with the Canadian biomass burning particles. This study provides measurements of BC size, mixing state and removal efficiency to constrain model parameterisations of BC wet removal in biomass burning regions, which will help to reduce uncertainty in radiative forcing calculations.

The performance of the Weather Research and Forecasting regional model with chemistry (WRF-Chem) in simulating the spatial and temporal variations in aerosol mass, composition, and size over California is quantified using the extensive meteorological, trace gas, and aerosol measurements collected during the California Nexus of Air Quality and Climate Experiment (CalNex) and the Carbonaceous Aerosol and Radiative Effects Study (CARES) conducted during May and June of 2010. The overall objective of the field campaigns was to obtain data needed to better understand processes that affect both climate and air quality, including emission assessments, transport and chemical aging of aerosols, aerosol radiative effects. Simulations were performed that examined the sensitivity of aerosol concentrations to anthropogenic emissions and to long-range transport of aerosols into the domain obtained from a global model. The configuration of WRF-Chem used in this study is shown to reproduce the overall synoptic conditions, thermally driven circulations, and boundary layer structure observed in region that controls the transport and mixing of trace gases and aerosols. Reducing the default emissions inventory by 50% led to an overall improvement in many simulated trace gases and black carbon aerosol at most sites and along most aircraft flight paths; however, simulated organic aerosol was closer to observed when there were no adjustments to the primary organic aerosol emissions. We found that sulfate was better simulated over northern California whereas nitrate was better simulated over southern California. While the overall spatial and temporal variability of aerosols and their precursors were simulated reasonably well, we show cases where the local transport of some aerosol plumes were either too slow or too fast, which adversely affects the statistics quantifying the differences between observed and simulated quantities. Comparisons with lidar and in situ measurements indicate that long-range transport of aerosols from the global model was likely too high in the free troposphere even though their concentrations were relatively low. This bias led to an over-prediction in aerosol optical depth by as much as a factor of 2 that offset the under-predictions of boundary-layer extinction resulting primarily from local emissions. Lowering the boundary conditions of aerosol concentrations by 50% greatly reduced the bias in simulated aerosol optical depth for all regions of California. This study shows that quantifying regional-scale variations in aerosol radiative forcing and determining the relative role of emissions from local and distant sources is challenging during `clean' conditions and that a wide array of measurements are needed to ensure model predictions are correct for the right reasons. In this regard, the combined CalNex and CARES data sets are an ideal test bed that can be used to evaluate aerosol models in great detail and develop improved treatments for aerosol processes.

Black carbon aerosols (BC) at a London urban site were characterised in both winter- and summertime 2012 during the Clean Air for London (ClearfLo) project. Positive matrix factorisation (PMF) factors of organic aerosol mass spectra measured by a high-resolution aerosol mass spectrometer (HR-AMS) showed traffic-dominant sources in summer but in winter the influence of additional non-traffic sources became more important, mainly from solid fuel sources (SF). Measurements using a single particle soot photometer (SP2, DMT), showed the traffic-dominant BC exhibited an almost uniform BC core size (Dc) distribution with very thin coating thickness throughout the detectable range of Dc. However, the size distribution of sf (project average mass median Dc = 149 ± 22 nm in winter, and 120 ± 6 nm in summer) and BC coating thickness varied significantly in winter. A novel methodology was developed to attribute the BC number concentrations and mass abundances from traffic (BCtr) and from SF (BCsf), by using a 2-D histogram of the particle optical properties as a function of BC core size, as measured by the SP2. The BCtr and BCsf showed distinctly different sf distributions and coating thicknesses, with BCsf displaying larger Dc and larger coating thickness compared to BCtr. BC particles from different sources were also apportioned by applying a multiple linear regression between the total BC mass and each AMS-PMF factor (BC–AMS–PMF method), and also attributed by applying the absorption spectral dependence of carbonaceous aerosols to 7-wavelength Aethalometer measurements (Aethalometer method). Air masses that originated from westerly (W), southeasterly (SE), and easterly (E) sectors showed BCsf fractions that ranged from low to high, and whose mass median Dc values were 137 ± 10 nm, 143 ± 11 nm and 169 ± 29 nm, respectively. The corresponding bulk relative coating thickness of BC (coated particle size/BC core – Dp/Dc) for these same sectors was 1.28 ± 0.07, 1.45 ± 0.16 and 1.65 ± 0.19. For W, SE and E air masses, the number fraction of BCsf ranged from 6 ± 2% to 11 ± 5% to 18 ± 10%, respectively, but importantly the larger BC core sizes lead to an increased fraction of BCsf in terms of mass than number (for W, SE and E air masses, the BCsf mass fractions ranged from 16 ± 6%, 24 ± 10% and 39 ± 14%, respectively). An increased fraction of non-BC particles (particles that did not contain a BC core) was also observed when SF sources were more significant. The BC mass attribution by the SP2 method agreed well with the BC–AMS–PMF multiple linear regression method (BC–AMS–PMF : SP2 ratio = 1.05, r2 = 0.80) over the entire experimental period. Good agreement was found between BCsf attributed with the Aethalometer model and the SP2. However, the assumed absorption Ångström exponent (αwb) had to be changed according to the different air mass sectors to yield the best comparison with the SP2. This could be due to influences of fuel type or burn phase.

We present measurements of a long-range smoke transport event recorded on 20–21 July 2011 over Halifax, Nova Scotia, Canada, during the Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS-B) campaign. Ground-based Fourier transform spectrometers and photometers detected air masses associated with large wildland fires burning in eastern Manitoba and western Ontario. We investigate a plume with high trace gas amounts but low amounts of particles that preceded and overlapped at the Halifax site with a second plume with high trace gas loadings and significant amounts of particulate material. We show that the first plume experienced a meteorological scavenging event, but the second plume had not been similarly scavenged. This points to the necessity to account carefully for the plume history when considering long-range transport since simultaneous or near-simultaneous times of arrival are not necessarily indicative of either similar trajectories or meteorological history. We investigate the origin of the scavenged plume, and the possibility of an aerosol wet deposition event occurring in the plume ~ 24 h prior to the measurements over Halifax. The region of lofting and scavenging is only monitored on an intermittent basis by the present observing network, and thus we must consider many different pieces of evidence in an effort to understand the early dynamics of the plume. Through this discussion we also demonstrate the value of having many simultaneous remote-sensing measurements in order to understand the physical and chemical behaviour of biomass burning plumes.

We present an analysis of ozone (O3) photochemistry observed by aircraft measurements of boreal biomass burning plumes over eastern Canada in the summer of 2011. Measurements of O3 and a number of key chemical species associated with O3 photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the "quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS) experiment between 12 July and 3 August 2011. The location and timing of the aircraft measurements put BORTAS into a unique position to sample biomass burning plumes from the same source region in Northwestern Ontario with a range of ages. We found that O3 mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (= NOy-NOx) revealed that the potential for O3 production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 10 days. The BORTAS measurements provided a wide dynamic range of O3 production in the sampled biomass burning plumes with ΔO3/ΔCO enhancement ratios increasing from 0.020 ± 0.008 ppbv ppbv−1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbv ppbv−1 in plumes with photochemical ages greater than 5 days. We found that the main contributing factor to the variability in the ΔO3/ΔCO enhancement ratio was ΔCO in plumes with photochemical ages less than 4 days, and that was a transition to ΔO3 becoming the main contributing factor in plumes with ages greater than 4 days. In comparing O3 mixing ratios with components of the NOy budget, we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiency (OPE) of 7.7 ± 3.5 ppbv ppbv−1 relative to ΣAN and 1.6 ± 0.9 ppbv ppbv−1 relative to NOz. In plumes with ages greater than 4 days, OPE increased to 472 ± 28 ppbv ppbv−1 relative to ΣAN and 155 ± 5 ppbv ppbv−1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photostationary steady state and O3 production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to O3. The BORTAS measurements of O3 photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the Troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990.

Soot particles, consisting of black carbon (BC), organic carbon (OC), inorganic salts, and trace elements, are emitted into the atmosphere during incomplete combustion. Accurate measurements of atmospheric BC are important as BC particles cause adverse health effects and impact the climate. Unfortunately, the accurate measurement of the properties and mass concentrations of BC particles remains difficult. The Single Particle Soot Photometer (SP2) can contribute to improving this situation by measuring the mass of refractory BC in individual particles as well as its mixing state. Here, the results of the first detailed SP2 intercomparison, involving 6 SP2s from 6 different research groups, are presented, including the most evolved data products that can presently be calculated from SP2 measurements. It was shown that a detection efficiency of almost 100% down to 1 fg BC per particle can readily be achieved, and that this limit can be pushed down to ∼0.2 fg BC with optimal SP2 setup. Number and mass size distributions of BC cores agreed within ±5% and ±10%, respectively, in between the SP2s, with larger deviations in the range below 1 fg BC. The accuracy of the SP2's mass concentration measurement depends on the calibration material chosen. The SP2 has previously been shown to be equally sensitive to fullerene soot and ambient BC from sources where fossil fuel was dominant and less sensitive to fullerene soot than to Aquadag. Fullerene soot was therefore chosen as the standard calibration material by the SP2 user community; however, many data sets rely solely on Aquadag calibration measurements. The difference in SP2 sensitivity was found to be almost equal (fullerene soot to Aquadag response ratio of ∼0.75 at 8.9 fg BC) for all SP2s. This allows the calculation of a fullerene soot equivalent calibration curve from a measured Aquadag calibration, when no fullerene soot calibration is available. It could be shown that this approach works well for all SP2s over the mass range of 1–10 fg. This range is suitable for typical BC mass size distributions in the ambient air far from sources. The number size distribution of purely scattering particles optically measured by the 6 SP2s also agreed within 15%. Measurements of the thickness of non-refractory coatings (i.e. product from α-pinene ozonolysis) on the BC particles, relying on BC mass optical size and on an additional particle position measurement, also compared well (within ±17%). The estimated coating thickness values were consistent with thermo-optical analysis of OC and elemental carbon (EC) content, though absolutely accurate values cannot be expected given all the assumptions that have to be made regarding refractive index, particle morphology, etc. This study showed that the SP2 provides accurate and reproducible data, but also that high data quality is only achieved if the SP2 is carefully tuned and calibrated. It has to be noted that the agreement observed here does not account for additional variability in output data that could result from the differences in the potentially subjective assumptions made by different SP2 users in the data processing.

Biomass burning (BB) is a major global source of trace gases and particles. Accurately representing the production and evolution of these emissions is an important goal for atmospheric chemical transport models. We measured a suite of gases and aerosols emitted from an 81 hectare prescribed fire in chaparral fuels on the central coast of California, US on 17 November 2009. We also measured physical and chemical changes that occurred in the isolated downwind plume in the first ~4 h after emission. The measurements were carried out onboard a Twin Otter aircraft outfitted with an airborne Fourier transform infrared spectrometer (AFTIR), aerosol mass spectrometer (AMS), single particle soot photometer (SP2), nephelometer, LiCor CO2 analyzer, a chemiluminescence ozone instrument, and a wing-mounted meteorological probe. Our measurements included: CO2; CO; NOx; NH3; non-methane organic compounds; organic aerosol (OA); inorganic aerosol (nitrate, ammonium, sulfate, and chloride); aerosol light scattering; refractory black carbon (rBC); and ambient temperature, relative humidity, barometric pressure, and three-dimensional wind velocity. The molar ratio of excess O3 to excess CO in the plume (ΔO3/ΔCO) increased from −5.13 (±1.13) × 10−3 to 10.2 (±2.16) × 10−2 in ~4.5 h following smoke emission. Excess acetic and formic acid (normalized to excess CO) increased by factors of 1.73 ± 0.43 and 7.34 ± 3.03 (respectively) over the same time since emission. Based on the rapid decay of C2H4 we infer an in-plume average OH concentration of 5.27 (±0.97) × 106 molec cm−3, consistent with previous studies showing elevated OH concentrations in biomass burning plumes. Ammonium, nitrate, and sulfate all increased over the course of 4 h. The observed ammonium increase was a factor of 3.90 ± 2.93 in about 4 h, but accounted for just ~36% of the gaseous ammonia lost on a molar basis. Some of the gas phase NH3 loss may have been due to condensation on, or formation of, particles below the AMS detection range. NOx was converted to PAN and particle nitrate with PAN production being about two times greater than production of observable nitrate in the first ~4 h following emission. The excess aerosol light scattering in the plume (normalized to excess CO2) increased by a factor of 2.50 ± 0.74 over 4 h. The increase in light scattering was similar to that observed in an earlier study of a biomass burning plume in Mexico where significant secondary formation of OA closely tracked the increase in scattering. In the California plume, however, ΔOA/ΔCO2 decreased sharply for the first hour and then increased slowly with a net decrease of ~20% over 4 h. The fraction of thickly coated rBC particles increased up to ~85% over the 4 h aging period. Decreasing OA accompanied by increased scattering/particle coating in initial aging may be due to a combination of particle coagulation and evaporation processes. Recondensation of species initially evaporated from the particles may have contributed to the subsequent slow rise in OA. We compare our results to observations from other plume aging studies and suggest that differences in environmental factors such as smoke concentration, oxidant concentration, actinic flux, and RH contribute significantly to the variation in plume evolution observations.