Consistent determination of the heating rate of light-absorbing aerosol using wavelength- and time-dependent Aethalometer multiple-scattering correction.

Accurate and temporally consistent measurements of light absorbing aerosol (LAA) heating rate (HR) and of its source apportionment (fossil-fuel, FF; biomass-burning, BB) and speciation (black and brown Carbon; BC, BrC) are needed to evaluate LAA short-term climate forcing. For this purpose, wavelength- and time-dependent accurate LAA absorption coefficients are required. HR was experimentally determined and apportioned (sources/species) in the EMEP/ACTRIS/COLOSSAL-2018 winter campaign in Milan (urban-background site). Two Aethalometers (AE31/AE33) were installed together with a MAAP, CPC, OPC, a low volume sampler (PM2.5) and radiation instruments. AE31/AE33 multiple-scattering correction factors (C) were determined using two reference systems for the absorption coefficient: 1) 5-wavelength PP_UniMI with low time resolution (12 h, applied to PM2.5 samples); 2) timely-resolved MAAP data at a single wavelength. Using wavelength- and time-independent C values for the AE31 and AE33 obtained with the same reference device, the total HR showed a consistency (i.e. reproducibility) with average values comparable at 95% probability. However, if different reference devices/approaches are used, i.e. MAAP is chosen as reference instead of a PP_UniMI, the HR can be overestimated by 23-30% factor (by both AE31/AE33). This became more evident focusing on HR apportionment: AE33 data (corrected by a wavelength- and time-independent C) showed higher HRFF (+24 ± 1%) and higher HRBC (+10 ± 1%) than that of AE31. Conversely, HRBB and HRBrC were -28 ± 1% and -29 ± 1% lower for AE33 compared to AE31. These inconsistencies were overcome by introducing a wavelength-dependent Cλ for both AE31 and AE33, or using multi-wavelength apportionment methods, highlighting the need for further studies on the influence of wavelength corrections for HR determination. Finally, the temporally-resolved determination of C resulted in a diurnal cycle of the HR not statistically different whatever the source- speciation- apportionment used.

Trace Metals in Soot and PM2.5 from Heavy-Fuel-Oil Combustion in a Marine Engine.

Heavy fuel oil (HFO) particulate matter (PM) emitted by marine engines is known to contain toxic heavy metals, including vanadium (V) and nickel (Ni). The toxicity of such metals will depend on the their chemical state, size distribution, and mixing state. Using online soot-particle aerosol mass spectrometry (SP-AMS), we quantified the mass of five metals (V, Ni, Fe, Na, and Ba) in HFO-PM soot particles produced by a marine diesel research engine. The in-soot metal concentrations were compared to in-PM2.5 measurements by inductively coupled plasma-optical emission spectroscopy (ICP-OES). We found that <3% of total PM2.5 metals was associated with soot particles, which may still be sufficient to influence in-cylinder soot burnout rates. Since these metals were most likely present as oxides, whereas studies on lower-temperature boilers report a predominance of sulfates, this result implies that the toxicity of HFO PM depends on its combustion conditions. Finally, we observed a 4-to-25-fold enhancement in the ratio V:Ni in soot particles versus PM2.5, indicating an enrichment of V in soot due to its lower nucleation/condensation temperature. As this enrichment mechanism is not dependent on soot formation, V is expected to be generally enriched within smaller HFO-PM particles from marine engines, enhancing its toxicity.