Annual variation of source contributions to PM10 and oxidative potential in a mountainous area with traffic, biomass burning, cement-plant and biogenic influences.

Toxicity of particulate matter (PM) depends on its sources, size and composition. We identified PM10 sources and determined their contribution to oxidative potential (OP) as a health proxy for PM exposure in an Alpine valley influenced by cement industry. PM10 filter sample chemical analysis and equivalent black carbon (eBC) were measured at an urban background site from November 2020 to November 2021. Using an optimized Positive Matrix Factorization (PMF) model, the source chemical fingerprints and contributions to PM10 were determined. The OP assessed through two assays, ascorbic acid (AA) and dithiothreitol (DTT), was attributed to the PM sources from the PMF model with a multiple linear regression (MLR) model. Ten factors were found at the site, including biomass burning (34, 40 and 38% contribution to annual PM10, OPAA and OPDDT, respectively), traffic (14, 19 and 7%), nitrate- and sulphate-rich (together: 16, 5 and 8%), aged sea salt (2, 2 and 0%) and mineral dust (10, 12 and 17%). The introduction of innovative organic tracers allowed the quantification of the PM primary and secondary biogenic fractions (together: 13, 8 and 21%). In addition, two unusual factors due to local features, a chloride-rich factor and a second mineral dust-rich factor (named the cement dust factor) were found, contributing together 10, 14 and 8%. We associate these two factors to different processes in the cement plant. Despite their rather low contribution to PM10 mass, these sources have one of the highest OPs per µg of source. The results of the study provide vital information about the influence of particular sources on PM10 and OP in complex environments and are thus useful for PM control strategies and actions.

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.

Aerosol optical properties in the Arctic: The role of aerosol chemistry and dust composition in a closure experiment between Lidar and tethered balloon vertical profiles.

A closure experiment was conducted over Svalbard by comparing Lidar measurements and optical aerosol properties calculated from aerosol vertical profiles measured using a tethered balloon. Arctic Haze was present together with Icelandic dust. Chemical analysis of filter samples, aerosol size distribution and a full set of meteorological parameters were determined at ground. Moreover, scanning electron microscopy coupled with energy-dispersive X-ray (SEM-EDS) data were at disposal showing the presence of several mineralogical phases (i.e., sheet silicates, gypsum, quartz, rutile, hematite). The closure experiment was set up by calculating the backscattering coefficients from tethered balloon data and comparing them with the corresponding lidar profiles. This was preformed in three subsequent steps aimed at determining the importance of a complete aerosol speciation: (i) a simple, columnar refractive index was obtained by the closest Aerosol Robotic Network (AERONET) station, (ii) the role of water-soluble components, elemental carbon and organic matter (EC/OM) was addressed, (iii) the dust composition was included. When considering the AERONET data, or only the ionic water-soluble components and the EC/OM fraction, results showed an underestimation of the backscattering lidar signal up to 76, 53 and 45% (355, 532 and 1064 nm). Instead, when the dust contribution was included, the underestimation disappeared and the vertically-averaged, backscattering coefficients (1.45 ±â€¯0.30, 0.69 ±â€¯0.15 and 0.34 ±â€¯0.08 Mm-1 sr-1, at 355, 532 and 1064 nm) were found in keeping with the lidar ones (1.60 ±â€¯0.22, 0.75 ±â€¯0.16 and 0.31 ±â€¯0.08 Mm-1 sr-1). Final results were characterized by low RMSE (0.36, 0.08 and 0.04 Mm-1 sr-1) and a high linear correlation (R2 of 0.992, 0.992 and 0.994) with slopes close to one (1.368, 0.931 and 0.977, respectively). This work highlighted the importance of all the aerosol components and of the synergy between single particle and bulk chemical analysis for the optical property characterization in the Arctic.

Quantification of source specific black carbon scavenging using an aethalometer and a disdrometer.

Aerosol black carbon (BC) is the second strongest contributor to global warming, after CO2, and it is linked to many adverse health effects. A sampling campaign of 15 months was carried out in León (Spain) in order to evaluate the scavenging of BC with an ensemble aethalometer-disdrometer. The aethalometer provides the concentration of equivalent black carbon (eBC), and the disdrometer, the raindrop size distribution. A total of seventy-five rain events were studied and in 73% of them there was an effective (eBCinitial > eBCfinal) scavenging, with a mean decrease of 48 ±â€¯37% in long rain events (>8 h) and 39 ±â€¯38% in short rain events. The scavenging of BC is strongly related to its source. Thus, the scavenging coefficient (SC) mean value of the BC from fossil fuel (eBCff) for short and long rain events was 5.1 10-5 and 1.3 10-5 s-1, respectively. For the BC from biomass burning (eBCbb), the SC values were 1.6 10-4 and 2.8 10-5 s-1 in short and long events, respectively. There was a significant positive correlation between the SC and the number of drops with diameters between 0.375 and 2.5 mm. Rain scavenging of eBC was analyzed depending on the air mass origin obtaining an effective scavenging for air masses from Atlantic, Arctic and Africa. A linear model (R2 = 0.72) was built to estimate the ΔeBC values with variables from an aethalometer, a disdrometer and a weather station: eBC concentration before rain, swept volume and precipitation accumulated. A Kolmogorov-Smirnov statistical test confirmed the goodness of fit of the model to the measured data.

Spatial and temporal variability of carbonaceous aerosols: Assessing the impact of biomass burning in the urban environment.

Biomass burning (BB) is a significant source of atmospheric particles in many parts of the world. Whereas many studies have demonstrated the importance of BB emissions in central and northern Europe, especially in rural areas, its impact in urban air quality of southern European countries has been sparsely investigated. In this study, highly time resolved multi-wavelength absorption coefficients together with levoglucosan (BB tracer) mass concentrations were combined to apportion carbonaceous aerosol sources. The Aethalometer model takes advantage of the different spectral behavior of BB and fossil fuel (FF) combustion aerosols. The model was found to be more sensitive to the assumed value of the aerosol Ångström exponent (AAE) for FF (AAEff) than to the AAE for BB (AAEbb). As result of various sensitivity tests the model was optimized with AAEff=1.1 and AAEbb=2. The Aethalometer model and levoglucosan tracer estimates were in good agreement. The Aethalometer model was further applied to data from three sites in Granada urban area to evaluate the spatial variation of CMff and CMbb (carbonaceous matter from FF or BB origin, respectively) concentrations within the city. The results showed that CMbb was lower in the city centre while it has an unexpected profound impact on the CM levels measured in the suburbs (about 40%). Analysis of BB tracers with respect to wind speed suggested that BB was dominated by sources outside the city, to the west in a rural area. Distinguishing whether it corresponds to agricultural waste burning or with biomass burning for domestic heating was not possible. This study also shows that although traffic restrictions measures contribute to reduce carbonaceous concentrations, the extent of the reduction is very local. Other sources such as BB, which can contribute to CM as much as traffic emissions, should be targeted to reduce air pollution.

Vertical profiles of aerosol absorption coefficient from micro-Aethalometer data and Mie calculation over Milan.

Vertical profiles of aerosol number-size distribution and black carbon (BC) concentration were measured between ground-level and 500m AGL over Milan. A tethered balloon was fitted with an instrumentation package consisting of the newly-developed micro-Aethalometer (microAeth® Model AE51, Magee Scientific, USA), an optical particle counter, and a portable meteorological station. At the same time, PM(2.5) samples were collected both at ground-level and at a high altitude sampling site, enabling particle chemical composition to be determined. Vertical profiles and PM(2.5) data were collected both within and above the mixing layer. Absorption coefficient (b(abs)) profiles were calculated from the Aethalometer data: in order to do so, an optical enhancement factor (C), accounting for multiple light-scattering within the filter of the new microAeth® Model AE51, was determined for the first time. The value of this parameter C (2.05±0.03 at λ=880nm) was calculated by comparing the Aethalometer attenuation coefficient and aerosol optical properties determined from OPC data along vertical profiles. Mie calculations were applied to the OPC number-size distribution data, and the aerosol refractive index was calculated using the effective medium approximation applied to aerosol chemical composition. The results compare well with AERONET data. The BC and b(abs) profiles showed a sharp decrease at the mixing height (MH), and fairly constant values of b(abs) and BC were found above the MH, representing 17±2% of those values measured within the mixing layer. The BC fraction of aerosol volume was found to be lower above the MH: 48±8% of the corresponding ground-level values. A statistical mean profile was calculated, both for BC and b(abs), to better describe their behaviour; the model enabled us to compute their average behaviour as a function of height, thus laying the foundations for valid parametrizations of vertical profile data which can be useful in both remote sensing and climatic studies.

Experimental considerations of simultaneous thermal lens and beam deflection phenomena.

A theoretical model, believed to be novel, that describes simultaneous thermal lens and beam deflection phenomena was experimentally tested. The effect of beam deflection on thermal lens measurements and the effect of the thermal lens on beam deflection measurements were investigated. The experiment confirmed the validity of theoretical predictions for measurements of strongly absorbing samples for which the assumption of an unchanged pump beam in the sample is still valid.