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 Ivory Coast, 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 manuscript 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 from C-ToF-AMS: particulate organic nitrates (pON) 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, pON 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 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.