Structural signatures of water-soluble organic aerosols in contrasting environments in South America and Western Europe

This study describes and compares the key structural units present in water-soluble organic carbon (WSOC) fraction of atmospheric aerosols collected in different South American (Colombia – Medellín and Bogotá, Peru – Lima, Argentina – Buenos Aires, and Brazil – Rio de Janeiro, São Paulo, and Porto Velho, during moderate (MBB) and intense (IBB) biomass burning) and Western European (Portugal – Aveiro and Lisbon) locations. Proton nuclear magnetic resonance (1H NMR) spectroscopy was employed to assess the relative distribution of non-exchangeable proton functional groups in aerosol WSOC of diverse origin, for the first time to the authors’ knowledge in South America. The relative contribution of the proton functional groups was in the order H-C > H–C–C= > H-C-O > Ar-H, except in Porto Velho during MBB, Medellín, Bogotá, and Buenos Aires, for which the relative contribution of H-C-O was higher than that of H-C-C=. The 1H NMR source attribution confirmed differences in aging processes or regional sources between the two geographic regions, allowing the differentiation between urban combustion-related aerosol and biological particles. The aerosol WSOC in Aveiro, Lisbon, and Rio de Janeiro during summer are more oxidized than those from the remaining locations, indicating the predominance of secondary organic aerosols. Fresh emissions, namely of smoke particles, becomes important during winter in Aveiro and São Paulo, and in Porto Velho during IBB. The biosphere is an important source altering the chemical composition of aerosol WSOC in South America locations. The source attribution in Medellín, Bogotá, Buenos Aires, and Lima confirmed the mixed contributions of biological material, secondary formation, as well as urban and biomass burning emissions. Overall, the information and knowledge acquired in this study provide important diagnostic tools for future studies aiming at understanding the water-soluble organic aerosol problem, their sources and impact at a wider geographic scale.Fil: Duarte, Regina M.B.O.. Universidade de Aveiro; PortugalFil: Matos, João T.V.. Universidade de Aveiro; PortugalFil: Paula, Andreia S.. Universidade de Aveiro; PortugalFil: Lopes, Sónia P.. Universidade de Aveiro; PortugalFil: Pereira, Guilherme. Universidade de Sao Paulo; BrasilFil: Vasconcellos, Pérola. Universidade de Sao Paulo; BrasilFil: Gioda, Adriana. Universidade Federal do Rio de Janeiro; BrasilFil: Carreira, Renato. Universidade Federal do Rio de Janeiro; BrasilFil: Silva, Artur M.S.. Universidade de Aveiro; PortugalFil: Duarte, Armando C.. Universidade de Aveiro; PortugalFil: Smichowski, Patricia Nora. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Rojas, Nestor. Universidad Nacional de Colombia; ColombiaFil: Sanchez Ccoyllo, Odon. No especifíca

Comparative study of atmospheric water-soluble organic aerosols composition in contrasting suburban environments in the Iberian Peninsula Coast

This study investigates the structural composition and major sources of water-soluble organic matter (WSOM) from PM2.5 collected, in parallel, during summer and winter, in two contrasting suburban sites at Iberian Peninsula Coast: Aveiro (Portugal) and Coruña (Spain). PM10 samples were also collected at Coruña for comparison. Ambient concentrations of PM2.5, total nitrogen (TN), and WSOM were higher in Aveiro than in Coruña, with the highest levels found in winter at both locations. In Coruña, concentrations of PM10, TN, and WSOM were higher than those from PM2.5. Regardless of the season, stable isotopic δ13C and δ15N in PM2.5 suggested important contributions of anthropogenic fresh organic aerosols (OAs) at Aveiro. In Coruña, δ13C and δ15N of PM2.5 and PM10 suggests decreased anthropogenic input during summer. Although excitation-emission fluorescence profiles were similar for all WSOM samples, multi-dimensional nuclear magnetic resonance (NMR) spectroscopy confirmed differences in their structural composition, reflecting differences in aging processes and/or local sources between the two locations. In PM2.5 WSOM in Aveiro, the relative distribution of non-exchangeable proton functional groups was in the order: H-C (40-43%) > H-C-C= (31-39%) > H-C-O (12-15%) > Ar-H (5.0-13%). However, in PM2.5 and PM10 WSOM in Coruña, the relative contribution of H-C-O groups (24-30% and 23-29%, respectively) equals and/or surpasses that of H-C-C= (25-26% and 25-29%, respectively), being also higher than those of Aveiro. In both locations, the highest aromatic contents were observed during winter due to biomass burning emissions. The structural composition of PM2.5 and PM10 WSOM in Coruña is dominated by oxygenated aliphatic compounds, reflecting the contribution of secondary OAs from biogenic, soil dust, and minor influence of anthropogenic emissions. In contrast, the composition of PM2.5 WSOM in Aveiro appears to be significantly impacted by fresh and secondary anthropogenic OAs. Marine and biomass burning OAs are important contributors, common to both sites.Xunta de Galicia ( Programa de Consolidación y Estructuración de Unidades de Investigación Competitivas Refs. GRC2013-047 and ED431C 2017/28)publishe

Challenges in the identification and characterization of free amino acids and proteinaceous compounds in atmospheric aerosols: a critical review

In the last decades, there has been an increasing interest in the presence of amino acids in atmospheric aerosols, either free or in combination (e.g., proteinaceous compounds). The fact that these compounds play an important role in the chemistry and physics of air particles and atmosphere, in atmosphere/biosphere nutrient cycling, and have a direct impact in human health has encouraged further studies. The diversity in origin, type, and ambient concentrations of these amino compounds considerably complicates, thus indicating their environmental impact. Studies for the determination of amino acids in the atmosphere are extremely diverse, encompassing an array of different analytical methodologies; however, it is not possible to conduct a comparative study of these methods. In this critical review, we evaluate and compare the procedures involved in the analytical methods and studies developed thus far for the identification and quantification of amino acids in different ambient particle sizes and in different atmospheric environments (i.e., background/pristine, rural, and urban environments)

Source apportionment for indoor air pollution: Current challenges and future directions

Source apportionment (SA) for indoor air pollution is challenging due to the multiplicity and high variability of indoor sources, the complex physical and chemical processes that act as primary sources, sinks and sources of precursors that lead to secondary formation, and the interconnection with the outdoor environment. While the major indoor sources have been recognized, there is still a need for understanding the contribution of indoor versus outdoor-generated pollutants penetrating indoors, and how SA is influenced by the complex processes that occur in indoor environments. This paper reviews our current understanding of SA, through reviewing information on the SA techniques used, the targeted pollutants that have been studied to date, and their source apportionment, along with limitations or knowledge gaps in this research field. The majority (78 %) of SA studies to date focused on PM chemical composition/size distribution, with fewer studies covering organic compounds such as ketones, carbonyls and aldehydes. Regarding the SA method used, the majority of studies have used Positive Matrix Factorization (31 %), Principal Component Analysis (26 %) and Chemical Mass Balance (7 %) receptor models. The indoor PM sources identified to date include building materials and furniture emissions, indoor combustion-related sources, cooking-related sources, resuspension, cleaning and consumer products emissions, secondary-generated pollutants indoors and other products and activity-related emissions. The outdoor environment contribution to the measured pollutant indoors varies considerably (<10 %- 90 %) among the studies. Future challenges for this research area include the need for optimization of indoor air quality monitoring and data selection as well as the incorporation of physical and chemical processes in indoor air into source apportionment methodology

Trends in data processing of comprehensive two-dimensional chromatography: state of the art

The operation of advanced chromatographic systems, namely comprehensive two-dimensional (2D) chromatography coupled to multidimensional detectors, allows achieving a great deal of data that need special care to be processed in order to characterize and quantify as much as possible the analytes under study. The aim of this review is to identify the main trends, research needs and gaps on the techniques for data processing of multidimensional data sets obtained from comprehensive 2D chromatography. The following topics have been identified as the most promising for new developments in the near future: data acquisition and handling, peak detection and quantification, measurement of overlapping of 2D peaks, and data analysis software for 2D chromatography. The rational supporting most of the data processing techniques is based on the generalization of one-dimensional (1D) chromatography although algorithms, such as the inverted watershed algorithm, use the 2D chromatographic data as such. However, for processing more complex N-way data there is a need for using more sophisticated techniques. Apart from using other concepts from 1D chromatography, which have not been tested for 2D chromatography, there is still room for new improvements and developments in algorithms and software for dealing with 2D comprehensive chromatographic data.publishe