High time-resolved measurements of fine aerosol (PM2.5) in a hot-spot area during wintertime: multi-wavelength optical absorption properties and source apportionment

Black Carbon (BC) is the main absorber of solar radiation among the aerosol components, it influences cloud processes, and alters the melting of snow and ice cover. Although it is one of the most important individual climate-warming components, uncertainties on the radiative forcing related to BC-radiation interaction still cover more than one order of magnitude. Moreover, weakly absorbing organic material (brown carbon, BrC) in the form of particle coating or as particle as-is can be considered a further important contributor to aerosol absorption. The peculiarity of BrC is that it is very effective in the absorption of short-\u3bb radiation whereas its contribution to aerosol absorption is negligible in the red or near-IR bands. It is noteworthy that BC and BrC can also be used for source apportionment purposes (e.g. they can be helpful for the discrimination between fossil fuels combustion vs. biomass burning). Thus, aerosol absorption properties possibly related to mixing and/or size information, and BC content are currently of great interest. Moving in this frame, a multi-\u3bb polar photometer (PP_UniMI) has been developed at the Department of Physics of the University of Milan in the last years. The instrument is based on the measurement on the scattering plane of the light transmitted and scattered in the forward and back hemispheres by unloaded and loaded samples using a rotating photodiode. Data reduction aiming at the determination of the sample absorbance follows Petzold et al. (2004) and therein cited literature. Currently, PP_UNIMI allows performing 4-\u3bb measurements (870, 633, 532, 405 nm) on aerosol collected on different substrates, including aerosol collected with high-time resolution using a streaker sampler. Such sampler collects aerosol segregated in two size-classes (fine and coarse) on a rotating frame with hourly resolution. The set-up of the instrument was validated against independent measurements carried out using a Multi-Angle Absorption Photometer for what concerns the red-light results, considering possible artefact effects shown in Vecchi et al. (2013). The results presented here are related to the analysis of the high time-resolved trends of multiwavelength aerosol absorption properties measured on the fine aerosol fraction during a field campaign performed in Milan (Italy) in November 2015 (see an example in Figure 1). Such data will be used to test the possibility of applying source apportionment models based on optical properties (es. Aethalometer model) using off-line hightime resolved data. It is also noteworthy that equivalent BC can be quantified from the polar photometer measurements at 635 nm using a suitable mass absorption coefficient. Such information will be joined to the elemental components (Na-Pb) detected by Particle-Induced X-ray Emission technique carried out at the INFN-LABEC in Florence to perform receptor modelling analysis (e.g. Positive Matrix Factorization). The results of the source apportionment using such data will be also presented

The effect of Brown Carbon on thermal-optical analysis: a correction based on optical multi-wavelength analysis

Carbonaceous aerosol (CA) plays an important role in environmental issues like air quality, human health and global climate change. It mainly consists of organic carbon (OC) and elemental carbon (EC) although a minor fraction of carbonate carbon could be also present. Thermal-optical methods are presently the most widespread approach to OC/EC speciation. Despite their popularity, there is still a disagreement among the results, especially for what concerns EC as differentthermal protocols can be currently used. The main hypothesis at the basis of the technique is that on their different optical properties: while EC is strongly light absorbing, OC is generally transparent in the visible range. However, another fraction of light-absorbing carbon exists which is not black and it is generally called brown carbon (BrC) (Andreae and Gelencs\ue9r, 2006). We introduced a new way to apportion the absorption coefficient (babs) of carbonaceous atmospheric aerosols starting from a multi-wavelength optical analysis (Massab\uf2 et al., 2015). This analysis was performed thanks to the MWAA, an instrument developed at the Physics Department of University of Genoa (Massab\uf2 et al., 2013). The method uses the information gathered at five different wavelengths in a renewed and upgraded version of the approach usually referred to as Aethalometer model (Sandradewi et al., 2008). Moreover, with some assumptions, also the quantification of OC coming from fossil fuels and wood burning can be obtained. Thermal-optical methods are presently the most widespread approach to OC/EC speciation. Despite their popularity, there is still a disagreement among the results, especially for what concerns EC as different thermal protocols can be used. In fact, the pyrolysis occurring during the analysis can heavily affect OC/EC separation, depending on PM composition in addition to the used protocol. Furthermore, the presence in the sample of BrC can shift the split point since it is light absorbing also @ 635nm, the typical laser wavelength used in this technique (Chen et al., 2015). We have recently introduced a new possibility, based on the apportionment of the absorption coefficient of particleloaded filters, for correcting the thermo-optical analysis of PM samples (Massab\uf2 et al, 2016). We present here the results of an apportionment study of carbonaceous aerosol sources performed in an Alpine area, validated against independent measurements of levoglucosan. We also present developments of the thermo-optical analysis correction (Massab\uf2 et al., 2016) which lead to a better homogeneity between the results obtained with different thermal protocols

STRAS: a new high time resolution aerosol sampler for PIXE analysis

The joint use of hourly resolution sampling and analyses with accelerated ion beams such as Particle Induced X-ray Emission (PIXE) technique has allowed the measurement of hourly temporal patterns of particulate matter (PM) composition at many sites in different parts of the world. The demand within the scientific community for this type of analysis has been continuously increasing in recent years, but hourly resolution samplers suitable for PIXE analysis are now discontinued and/or suffer from some technical limitations. In this framework, a new hourly sampler, STRAS (Size and Time Resolved Aerosol Sampler), was developed for the collection of PM10, PM2.5 or PM1. It allows automatic sequential sampling of up to 168 hourly samples (1 week), it is mechanically robust, compact, and easily transportable. To increase PIXE sensitivity, each sample is concentrated on a small surface area on a polycarbonate membrane. The comparison between the elemental concentrations retrieved by STRAS samples and samples collected using a standard sequential sampler operated in parallel shows a very good agreement; indeed, if both the samplers use the same kind of membrane, the concentrations of all detected elements are in agreement within 10 %

Source apportionment of fine and coarse particles at a roadside and urban background site in London during the 2012 summer ClearfLo campaign

AbstractLondon, like many major cities, has a noted air pollution problem, and a better understanding of the sources of airborne particles in the different size fractions will facilitate the implementation and effectiveness of control strategies to reduce air pollution. Thus, the trace elemental composition of the fine and coarse fraction were analysed at hourly time resolution at urban background (North Kensington, NK) and roadside (Marylebone Road, MR) sites within central London. Unlike previous work, the current study focuses on measurements during the summer providing a snapshot of contributing sources, utilising the high time resolution to improve source identification. Roadside enrichment was observed for a large number of elements associated with traffic emissions (Al, S, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Rb and Zr), while those elements that are typically from more regional sources (e.g. Na, Cl, S and K) were not found to have an appreciable increment. Positive Matrix Factorization (PMF) was applied for the source apportionment of the particle mass at both sites with similar sources being identified, including sea salt, airborne soil, traffic emissions, secondary inorganic aerosols and a Zn-Pb source. In the fine fraction, traffic emissions was the largest contributing source at MR (31.9%), whereas it was incorporated within an “urban background” source at NK, which had contributions from wood smoke, vehicle emissions and secondary particles. Regional sources were the major contributors to the coarse fraction at both sites. Secondary inorganic aerosols (which contained influences from shipping emissions and coal combustion) source factors accounted for around 33% of the PM10 at NK and were found to have the highest contributions from regional sources, including from the European mainland. Exhaust and non-exhaust sources both contribute appreciably to PM10 levels at the MR site, highlighting the continuing importance of vehicle-related air pollutants at roadside

First Results of the “Carbonaceous Aerosol in Rome and Environs (CARE)” Experiment: Beyond Current Standards for PM10

In February 2017 the “Carbonaceous Aerosol in Rome and Environs (CARE)” experiment was carried out in downtown Rome to address the following specific questions: what is the color, size, composition, and toxicity of the carbonaceous aerosol in the Mediterranean urban background area of Rome? The motivation of this experiment is the lack of understanding of what aerosol types are responsible for the severe risks to human health posed by particulate matter (PM) pollution, and how carbonaceous aerosols influence radiative balance. Physicochemical properties of the carbonaceous aerosol were characterised, and relevant toxicological variables assessed. The aerosol characterisation includes: (i) measurements with high time resolution (min to 1–2 h) at a fixed location of black carbon (eBC), elemental carbon (EC), organic carbon (OC), particle number size distribution (0.008–10 μ m), major non refractory PM1 components, elemental composition, wavelength-dependent optical properties, and atmospheric turbulence; (ii) 24-h measurements of PM10 and PM2.5 mass concentration, water soluble OC and brown carbon (BrC), and levoglucosan; (iii) mobile measurements of eBC and size distribution around the study area, with computational fluid dynamics modeling; (iv) characterisation of road dust emissions and their EC and OC content. The toxicological assessment includes: (i) preliminary evaluation of the potential impact of ultrafine particles on lung epithelia cells (cultured at the air liquid interface and directly exposed to particles); (ii) assessment of the oxidative stress induced by carbonaceous aerosols; (iii) assessment of particle size dependent number doses deposited in different regions of the human body; (iv) PAHs biomonitoring (from the participants into the mobile measurements). The first experimental results of the CARE experiment are presented in this paper. The objective here is to provide baseline levels of carbonaceous aerosols for Rome, and to address future research directions. First, we found that BC and EC mass concentration in Rome are larger than those measured in similar urban areas across Europe (the urban background mass concentration of eBC in Rome in winter being on average 2.6 ± 2.5 μ g · m − 3 , mean eBC at the peak level hour being 5.2 (95% CI = 5.0–5.5) μ g · m − 3 ). Then, we discussed significant variations of carbonaceous aerosol properties occurring with time scales of minutes, and questioned on the data averaging period used in current air quality standard for PM 10 (24-h). Third, we showed that the oxidative potential induced by aerosol depends on particle size and composition, the effects of toxicity being higher with lower mass concentrations and smaller particle size. Albeit this is a preliminary analysis, findings reinforce the need for an urgent update of existing air quality standards for PM 10 and PM 2.5 with regard to particle composition and size distribution, and data averaging period. Our results reinforce existing concerns about the toxicity of carbonaceous aerosols, support the existing evidence indicating that particle size distribution and composition may play a role in the generation of this toxicity, and remark the need to consider a shorter averaging period (<1 h) in these new standards

Results of the first European Source Apportionment intercomparison for Receptor and Chemical Transport Models

In this study, the performance of the source apportionment model applications were evaluated by comparing the model results provided by 44 participants adopting a methodology based on performance indicators: z-scores and RMSEu, with pre-established acceptability criteria. Involving models based on completely different and independent input data, such as receptor models (RMs) and chemical transport models (CTMs), provided a unique opportunity to cross-validate them. In addition, comparing the modelled source chemical profiles, with those measured directly at the source contributed to corroborate the chemical profile of the tested model results. The most used RM was EPA- PMF5. RMs showed very good performance for the overall dataset (91% of z-scores accepted) and more difficulties are observed with SCE time series (72% of RMSEu accepted). Industry resulted the most problematic source for RMs due to the high variability among participants. Also the results obtained with CTMs were quite comparable to their ensemble reference using all models for the overall average (>92% of successful z-scores) while the comparability of the time series is more problematic (between 58% and 77% of the candidates’ RMSEu are accepted). In the CTM models a gap was observed between the sum of source contributions and the gravimetric PM10 mass likely due to PM underestimation in the base case. Interestingly, when only the tagged species CTM results were used in the reference, the differences between the two CTM approaches (brute force and tagged species) were evident. In this case the percentage of candidates passing the z-score and RMSEu tests were only 50% and 86%, respectively. CTMs showed good comparability with RMs for the overall dataset (83% of the z-scores accepted), more differences were observed when dealing with the time series of the single source categories. In this case the share of successful RMSEu was in the range 25% - 34%.JRC.C.5-Air and Climat