Uncertainties in source allocation of carbonaceous aerosols in a Mediterranean region.

Understanding the atmospheric processes involving carbonaceous aerosols (CAs) is crucial for assessing air pollution impacts on human health and climate. The sources and formation mechanisms of CAs are not well understood, making it challenging to quantify impacts in models. Studies suggest residential wood combustion (RWC) and traffic significantly contribute to CAs in Europe's urban and rural areas. Here, we used an atmospheric chemistry model (MONARCH) and three different emission inventories (two versions of the European-scale emission inventory CAMS-REG_v4 and the HERMESv3 detailed national inventory for Spain) to assess the uncertainties in CAs simulation and source allocation (from traffic, RWC, shipping, fires and others) in Northeast Spain. For this, black carbon (BC) and organic aerosol (OA) measurements performed at three supersites representing different environments (urban, regional and remote) were used. Our findings show the importance of model resolution and detailed emission input data in accurately reproducing BC/OA observations. Even though emissions of total particulate matter are rather consistent between inventories in Spain, we found discrepancies between them mainly related to the spatiotemporal disaggregation (particularly relevant for traffic and RWC) and the treatment of the condensable fraction of CAs in RWC (changes in the speciation of elemental/organic carbon). The main source contribution to BC concentrations in the urban site is traffic, accounting for 71.1%/65.2% (January/July) in close agreement with the fossil contribution derived from observations (78.8%/84.2%), followed by RWC (12.8%/3%) and shipping emissions (5.4%/13.8%). An over-representation of RWC (winter) and shipping (summer) is obtained with CAMS-REG_v4. Noteworthy uncertainties arise in OA results due to condensables in emissions and a limited secondary aerosol production in the model. These findings offer insights into MONARCH's effectiveness in simulating CAs concentrations and source contribution in Northeast Spain. The study highlights the benefits of combining new datasets and modeling techniques to refine emission inventories and better understand and mitigate air pollution impacts.

Towards a better understanding of fine PM sources: Online and offline datasets combination in a single PMF.

Source apportionment (SA) techniques allocate the measured ambient pollutants with their potential source origin; thus, they are a powerful tool for designing air pollution mitigation strategies. Positive Matrix Factorization (PMF) is one of the most widely used SA approaches, and its multi-time resolution (MTR) methodology, which enables mixing different instrument data in their original time resolution, was the focus of this study. One year of co-located measurements in Barcelona, Spain, of non-refractory submicronic particulate matter (NR-PM1), black carbon (BC) and metals were obtained by a Q-ACSM (Aerodyne Research Inc.), an aethalometer (Aerosol d.o.o.) and fine offline quartz-fibre filters, respectively. These data were combined in a MTR PMF analysis preserving the high time resolution (30 min for the NR-PM1 and BC, and 24 h every 4th day for the offline samples). The MTR-PMF outcomes were assessed varying the time resolution of the high-resolution data subset and exploring the error weightings of both subsets. The time resolution assessment revealed that averaging the high-resolution data was disadvantageous in terms of model residuals and environmental interpretability. The MTR-PMF resolved eight PM1 sources: ammonium sulphate + heavy oil combustion (25%), ammonium nitrate + ammonium chloride (17%), aged secondary organic aerosol (SOA) (16%), traffic (14%), biomass burning (9%), fresh SOA (8%), cooking-like organic aerosol (5%), and industry (4%). The MTR-PMF technique identified two more sources relative to the 24 h base case data subset using the same species and four more with respect to the pseudo-conventional approach mimicking offline PMF, indicating that the combination of both high and low TR data is significantly beneficial for SA. Besides the higher number of sources, the MTR-PMF technique has enabled some sources disentanglement compared to the pseudo-conventional and base case PMF as well as the characterisation of their intra-day patterns.

Characterizing the sources of ambient PM10 organic aerosol in urban and rural Catalonia, Spain.

Organic aerosols (OA) have recently been shown to be the dominant contributor to the oxidative potential of airborne particulate matter in northeastern Spain. We collected PM10 filter samples every fourth day from January 2017 to March 2018 at two sampling stations located in Barcelona city and Montseny Natural Park, representing urban and rural areas, respectively. The chemical composition of PM10 was analyzed offline using a broad set of analytical instruments, including high-resolution time-of-flight mass spectrometry (HR-ToF-AMS), a total organic carbon analyzer (TCA), inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS), ion chromatography (IC), and thermal-optical carbon analyzer. Source apportionment analysis of the water-soluble organic content of the samples measured via HR-ToF-AMS revealed two primary and two secondary sources of OA, which included biomass-burning OA (BBOA), sulfur-containing OA (SCOA), as well as summer- and winter­oxygenated OA (SOOA and WOOA). The presence of hydrocarbon-like water-insoluble OA was also identified based on concentration trends in black carbon and nitrogen oxides. The results from the source apportionment analysis of the inorganic composition were correlated with different OA factors to assess potential source contributors. Barcelona showed significantly higher average water-soluble OA concentrations (5.63 ± 0.56 µg m-3) than Montseny (3.27 ± 0.37 µg m-3) over the sampling period. WOOA accounted for nearly 27 % of the averaged OA in Barcelona compared to only 7 % in Montseny. In contrast, SOOA had a greater contribution to OA in Montseny (47 %) than in Barcelona (24 %). SCOA and BBOA were responsible for 15-28 % of the OA at both sites. There were also seasonal variations in the relative contributions of different OA sources. Our overall results showed that local anthropogenic sources were primarily responsible for up to 70 % of ambient soluble OA in Barcelona, and regulating local-scale emissions could significantly improve air quality in urban Spain.