Assessing the role of anthropogenic and biogenic sources on PM₁ over southern West Africa using aircraft measurements

As part of the Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa (DACCIWA) project, an airborne campaign was designed to measure a large range of atmospheric constituents, focusing on the effect of anthropogenic emissions on regional climate. The presented study details results of the French ATR42 research aircraft, which aimed to characterize gas-phase, aerosol and cloud properties in the region during the field campaign carried out in June/July 2016 in combination with the German Falcon 20 and the British Twin Otter aircraft. The aircraft flight paths covered large areas of Benin, Togo, Ghana and Côte d\u27Ivoire, focusing on emissions from large urban conurbations such as Abidjan, Accra and Lomé, as well as remote continental areas and the Gulf of Guinea. This paper focuses on aerosol particle measurements within the boundary layer (<  2000 m), in particular their sources and chemical composition in view of the complex mix of both biogenic and anthropogenic emissions, based on measurements from a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS) and ancillary instrumentation. Background concentrations (i.e. outside urban plumes) observed from the ATR42 indicate a fairly polluted region during the time of the campaign, with average concentrations of carbon monoxide of 131 ppb, ozone of 32 ppb, and aerosol particle number concentration ( >  15 nm) of 735 cm−3 stp. Regarding submicron aerosol composition (considering non-refractory species and black carbon, BC), organic aerosol (OA) is the most abundant species contributing 53 %, followed by SO4 (27 %), NH4 (11 %), BC (6 %), NO3 (2 %) and minor contribution of Cl (<  0.5 %). Average background PM1 in the region was 5.9 µg m−3 stp. During measurements of urban pollution plumes, mainly focusing on the outflow of Abidjan, Accra and Lomé, pollutants are significantly enhanced (e.g. average concentration of CO of 176 ppb, and aerosol particle number concentration of 6500 cm−3 stp), as well as PM1 concentration (11.9 µg m−3 stp). Two classes of organic aerosols were estimated based on C-ToF-AMS: particulate organic nitrates (pONs) and isoprene epoxydiols secondary organic aerosols (IEPOX–SOA). Both classes are usually associated with the formation of particulate matter through complex interactions of anthropogenic and biogenic sources. During DACCIWA, pONs have a fairly small contribution to OA (around 5 %) and are more associated with long-range transport from central Africa than local formation. Conversely, IEPOX–SOA provides a significant contribution to OA (around 24 and 28 % under background and in-plume conditions). Furthermore, the fractional contribution of IEPOX–SOA is largely unaffected by changes in the aerosol composition (particularly the SO4 concentration), which suggests that IEPOX–SOA concentration is mainly driven by pre-existing aerosol surface, instead of aerosol chemical properties. At times of large in-plume SO4 enhancements (above 5 µg m−3), the fractional contribution of IEPOX–SOA to OA increases above 50 %, suggesting only then a change in the IEPOX–SOA-controlling mechanism. It is important to note that IEPOX–SOA constitutes a lower limit to the contribution of biogenic OA, given that other processes (e.g. non-IEPOX isoprene, monoterpene SOA) are likely in the region. Given the significant contribution to aerosol concentration, it is crucial that such complex biogenic–anthropogenic interactions are taken into account in both present-day and future scenario models of this fast-changing, highly sensitive region

Variation in chemical composition and volatility of oxygenated organic aerosol in different rural, urban, and mountain environments

The apparent volatility of atmospheric organic aerosol (OA) particles is determined by their chemical composition and environmental conditions (e.g., ambient temperature). A quantitative, experimental assessment of volatility and the respective importance of these two factors remains challenging, especially in ambient measurements. We present molecular composition and volatility of oxygenated OA (OOA) particles in different rural, urban, and mountain environments (including Chacaltaya, Bolivia; Alabama, US; Hyytiälä, Finland; Stuttgart and Karlsruhe, Germany; and Delhi, India) based on deployments of a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-CIMS). We find on average larger carbon numbers (nC) and lower oxygen-to-carbon (O : C) ratios at the urban sites (nC: 9.8 ± 0.7; O : C: 0.76 ± 0.03; average ±1 standard deviation) compared to the rural (nC: 8.8 ± 0.6; O : C: 0.80 ± 0.05) and mountain stations (nC: 8.1 ± 0.8; O : C: 0.91 ± 0.07), indicative of different emission sources and chemistry

Aerosol influences on low-level clouds in the West African monsoon

Low-level clouds (LLC) 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 regional, in situ measurements of cloud microphysics, taken during June – July 2016, as part of the DACCIWA (Dynamics-Aerosol-Chemistry-Clouds Interactions in West Africa) campaign, assessing spatial and temporal variation in the properties of these clouds. LLC 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. Additional sea breeze clouds developed near the coast in the late morning, reaching a maximum extent around 12:00 LST. Regional variation in LLC cover was largely determined by the modulation of the cool maritime inflow by the local orography, with peaks on the upwind side of hills and minima on the leeward sides. In the broad-scale cloud field, no lasting impacts related to anthropogenic aerosol 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. The majority of accumulation mode aerosols, and therefore cloud condensation nuclei, were from ubiquitous biomass burning smoke transported from the southern hemisphere. Consequently, all clouds measured (inland and offshore) had significantly higher CDNC and lower effective radius than clouds over the remote south Atlantic from literature. A parcel model sensitivity analysis showed that doubling or halving local emissions only changed the calculated CDNC 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 monsoon

Highly time-resolved chemical speciation and source apportionment of organic aerosol components in Delhi, India, using extractive electrospray ionization mass spectrometry

In recent years, the Indian capital city of Delhi has been impacted by very high levels of air pollution, especially during winter. Comprehensive knowledge of the composition and sources of the organic aerosol (OA), which constitutes a substantial fraction of total particulate mass (PM) in Delhi, is central to formulating effective public health policies. Previous source apportionment studies in Delhi identified key sources of primary OA (POA) and showed that secondary OA (SOA) played a major role but were unable to resolve specific SOA sources. We address the latter through the first field deployment of an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) in Delhi, together with a high-resolution aerosol mass spectrometer (AMS). Measurements were conducted during the winter of 2018/19, and positive matrix factorization (PMF) was used separately on AMS and EESI-TOF datasets to apportion the sources of OA. AMS PMF analysis yielded three primary and two secondary factors which were attributed to hydrocarbon-like OA (HOA), biomass burning OA (BBOA-1 and BBOA-2), more oxidized oxygenated OA (MO-OOA), and less oxidized oxygenated OA (LO-OOA). On average, 40 % of the total OA mass was apportioned to the secondary factors. The SOA contribution to total OA mass varied greatly between the daytime (76.8 %, 10:00–16:00 local time (LT)) and nighttime (31.0 %, 21:00–04:00 LT). The higher chemical resolution of EESI-TOF data allowed identification of individual SOA sources. The EESI-TOF PMF analysis in total yielded six factors, two of which were primary factors (primary biomass burning and cooking-related OA). The remaining four factors were predominantly of secondary origin: aromatic SOA, biogenic SOA, aged biomass burning SOA, and mixed urban SOA. Due to the uncertainties in the EESI-TOF ion sensitivities, mass concentrations of EESI-TOF SOA-dominated factors were related to the total AMS SOA (i.e. MO-OOA + LO-OOA) by multiple linear regression (MLR). Aromatic SOA was the major SOA component during the daytime, with a 55.2 % contribution to total SOA mass (42.4 % contribution to total OA). Its contribution to total SOA, however, decreased to 25.4 % (7.9 % of total OA) during the nighttime. This factor was attributed to the oxidation of light aromatic compounds emitted mostly from traffic. Biogenic SOA accounted for 18.4 % of total SOA mass (14.2 % of total OA) during the daytime and 36.1 % of total SOA mass (11.2 % of total OA) during the nighttime. Aged biomass burning and mixed urban SOA accounted for 15.2 % and 11.0 % of total SOA mass (11.7 % and 8.5 % of total OA mass), respectively, during the daytime and 15.4 % and 22.9 % of total SOA mass (4.8 % and 7.1 % of total OA mass), respectively, during the nighttime. A simple dilution–partitioning model was applied on all EESI-TOF factors to estimate the fraction of observed daytime concentrations resulting from local photochemical production (SOA) or emissions (POA). Aromatic SOA, aged biomass burning, and mixed urban SOA were all found to be dominated by local photochemical production, likely from the oxidation of locally emitted volatile organic compounds (VOCs). In contrast, biogenic SOA was related to the oxidation of diffuse regional emissions of isoprene and monoterpenes. The findings of this study show that in Delhi, the nighttime high concentrations are caused by POA emissions led by traffic and biomass burning and the daytime OA is dominated by SOA, with aromatic SOA accounting for the largest fraction. Because aromatic SOA is possibly more toxic than biogenic SOA and primary OA, its dominance during the daytime suggests an increased OA toxicity and health-related consequences for the general public.</p

Black-carbon absorption enhancement in the atmosphere determined by particle mixing state

Atmospheric black carbon makes an important but poorly quantified contribution to the warming of the global atmosphere. Laboratory and modelling studies have shown that the addition of non-black-carbon materials to black-carbon particles may enhance the particles’ light absorption by 50 to 60% by refracting and reflecting light. Real-world experimental evidence for this ‘lensing’ effect is scant and conflicting, showing that absorption enhancements can be less than 5% or as large as 140%. Here we present simultaneous quantifications of the composition and optical properties of individual atmospheric black-carbon particles. We show that particles with a mass ratio of non-black carbon to black carbon of less than 1.5, which is typical of fresh traffic sources, are best represented as having no absorption enhancement. In contrast, black-carbon particles with a ratio greater than 3, which is typical of biomass-burning emissions, are best described assuming optical lensing leading to an absorption enhancement. We introduce a generalized hybrid model approach for estimating scattering and absorption enhancements based on laboratory and atmospheric observations. We conclude that the occurrence of the absorption enhancement of black-carbon particles is determined by the particles’ mass ratio of non-black carbon to black carbon

Particle and VOC emission factor measurements for anthropogenic sources in West Africa

A number of campaigns have been carried out to establish the emission factors of pollutants from fuel combustion in West Africa, as part of work package 2 ("Air Pollution and Health") of the DACCIWA (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa) FP7 program. Emission sources considered here include wood (hevea and iroko) and charcoal burning, charcoal making, open trash burning, and vehicle emissions, including trucks, cars, buses and two-wheeled vehicles. Emission factors of total particulate matter (TPM), elemental carbon (EC), primary organic carbon (OC) and volatile organic compounds (VOCs) have been established. In addition, emission factor measurements were performed in combustion chambers in order to reproduce field burning conditions for a tropical hardwood (hevea), and obtain particulate emission factors by size (PM0.25, PM1, PM2.5 and PM10). Particle samples were collected on quartz fiber filters and analyzed using gravimetric method for TPM and thermal methods for EC and OC. The emission factors of 58 VOC species were determined using offline sampling on a sorbent tube. Emission factor results for two species of tropical hardwood burning of EC, OC and TPM are 0.98 ± 0.46 g kg-1 of fuel burned (g kg-1), 11.05 ± 4.55 and 41.12 ± 24.62 g kg-1, respectively. For traffic sources, the highest emission factors among particulate species are found for the two-wheeled vehicles with two-stroke engines (2.74 g kg-1 fuel for EC, 65.11 g kg-1 fuel for OC and 496 g kg-1 fuel for TPM). The largest VOC emissions are observed for two-stroke two-wheeled vehicles, which are up to 3 times higher than emissions from light-duty and heavy-duty vehicles. Isoprene and monoterpenes, which are usually associated with biogenic emissions, are present in almost all anthropogenic sources investigated during this work and could be as significant as aromatic emissions in wood burning (1 g kg-1 fuel). EC is primarily emitted in the ultrafine fraction, with 77 % of the total mass being emitted as particles smaller than 0.25 μm. The particles and VOC emission factors obtained in this study are generally higher than those in the literature whose values are discussed in this paper. This study underlines the important role of in situ measurements in deriving realistic and representative emission factors