Natural organic matter in urban aerosols: Comparison between water and alkaline soluble components using excitation–emission matrix fluorescence spectroscopy and multiway data analysis

Matos, João Batista de; Freire, Sandra M.S.C.; Duarte, Regina M.B.O.; Duarte, Armando C.

doi:10.1016/j.atmosenv.2014.11.042

Cited by 85 publications

(78 citation statements)

References 43 publications

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“…As shown in Fig. S9, Musa and Hevea burning had a VK diagram similar to that of WSOC in straw burning and fog water (Schmitt-Kopplin et al, 2010;Mazzoleni et al, 2010). S-containing compounds in tunnel aerosol with high O / C and H / C ratios were similar to the aerosol-derived WSOC in New York and Virginia (Wozniak et al, 2008).…”

Section: Molecular Composition Detected By Ft-icr Msmentioning

confidence: 69%

Molecular compositions and optical properties of dissolved brown carbon in biomass burning, coal combustion, and vehicle emission aerosols illuminated by excitation–emission matrix spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry analysis

et al. 2020

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Abstract. Brown carbon (BrC) plays an essential impact on radiative forcing due to its ability to absorb sunlight. In this study, the optical properties and molecular characteristics of water-soluble and methanol-soluble organic carbon (OC; MSOC) emitted from the simulated combustion of biomass and coal fuels and vehicle emissions were investigated using ultraviolet–visible (UV–vis) spectroscopy, excitation–emission matrix (EEM) spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with electrospray ionization (ESI). The results showed that these smoke aerosol samples from biomass burning (BB) and coal combustion (CC) had a higher mass absorption efficiency at 365 nm (MAE365) than vehicle emission samples. A stronger MAE365 value was also found in MSOC than water-soluble organic carbon (WSOC), indicating low polar compounds would possess a higher light absorption capacity. Parallel factor (PARAFAC) analysis identified six types of fluorophores (P1–6) in WSOC including two humic-like substances (HULIS-1) (P1 and P6), three protein-like substances (PLOM) (P2, P3, and P5), and one undefined substance (P4). HULIS-1 was mainly from aging vehicle exhaust particles; P2 was only abundant in BB aerosols; P3 was ubiquitous in all tested aerosols; P4 was abundant in fossil burning aerosols; and P5 was more intense in fresh vehicle exhaust particles. The MSOC chromophores (six components; C1–6) exhibited consistent characteristics with WSOC, suggesting the method could be used to indicate the origins of chromophores. FT-ICR mass spectra showed that CHO and CHON were the most abundant components of WSOC, but S-containing compounds appeared in a higher abundance in CC aerosols and vehicle emissions than BB aerosols, while considerably fewer S-containing compounds largely with CHO and CHON were detected in MSOC. The unique formulas of different sources in the van Krevelen (VK) diagram presented different molecular distributions. To be specific, BB aerosols with largely CHO and CHON had a medium H ∕ C and low O ∕ C ratio, while CC aerosols and vehicle emissions largely with S-containing compounds had an opposite H ∕ C and O ∕ C ratio. Moreover, the light absorption capacity of WSOC and MSOC was positively associated with the unsaturation degree and molecular weight in the source aerosols. The above results are potentially applicable to further studies on the EEM-based or molecular-characteristic-based source apportionment of chromophores in atmospheric aerosols.

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Section: Molecular Composition Detected By Ft-icr Msmentioning

confidence: 69%

Molecular compositions and optical properties of dissolved brown carbon in biomass burning, coal combustion, and vehicle emission aerosols illuminated by excitation–emission matrix spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry analysis

et al. 2020

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“…In general, these four individual fluorophores can be attributed to long-wavelength humic-like chromophores (HULIS-1, C1), short-wavelength humic-like chromophores that are less oxygenated (HULIS-2, C2) and highly oxygenated (HULIS-3, C4) and protein-like or phenol-like organic matter (PLOM, C3), respectively (Chen et al, 2016a;Chen et al, 10 2016b;Huang et al, 2018;Huo et al, 2018;Jamieson et al, 2014). It is noted that HULIS-1, -2, and -3 are commonly found in the EEMs of HULIS and WSOM in atmospheric aerosols and rainwater (Chen et al, 2016b;Matos et al, 2015), which are expected to consist of fluorophores with strong aromaticity and large molecular sizes. PLOM is generally ascribed to protein-like fluorophores, and sometimes it is also related to 15 non-nitrogen-containing species (e.g., phenol-and naphthalene-like substances) (Chen et al, 2016a;Fan et al, 2016;Huo et al, 2018).…”

Section: Eem and Parafac Analysis 20mentioning

confidence: 99%

The evolutionary behavior of chromophoric brown carbon during ozone aging of fine particles from biomass burning

Fan¹,

Cao²,

Yu³

et al. 2019

Preprint

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Abstract. Biomass burning (BB) emits large amounts of brown carbon (BrC), however, little is known about the evolutionary behavior of BrC produced by BB (BB-BrC) in atmospheric processes. In this study, the transformation of levels and the chromophoric characteristics of BrC in smoke particles emitted by the burning of rice straw (RS), corn straw (CS) and pine wood (PW) under O3 aging are investigated. The O3 aging induced the reduction of light absorption and fluorescence for the BB-BrC, suggesting the decomposition of chromophores and fluorophores. These changes were accompanied by a decrease of aromaticity, average molecular weight and the light absorption capacity for the chromophores, and an increase of humification for the fluorophores. The excitation emission matrix combined with a parallel factor analysis revealed that protein-like components (C3) were predominantly decomposed by O3 aging, while the relative distribution of a humic-like component with highly oxygenated chromophores (C4) gradually increased. In general, the humic-like substances (C1+C2+C4) were transformed to be the most abundant fluorophores for all the BB-BrC samples, which accounted for 84&#8201;%&#8211;87&#8201;% of the total fluorophores in final O3-aged BB-BrC. Two dimensional correlation spectroscopy (2D-COS) was performed on the synchronous fluorescence, which suggested that the RS- and CS- BrC exhibits the same susceptible fluorophores changes upon O3 aging. It showed that O3 firstly reacted with protein-like fractions (263&#8211;289 nm), and then with fulvic-like fractions (333&#8211;340&#8201;nm). In comparison, the changing sequence of susceptible fluorophores in the PW-BrC to O3 were in the order of fulvic-like with shorter wavelengths (309&#8201;nm) > protein-like fluorophores (276&#8201;nm) > fulvic-like fluorophores with longer wavelengths (358&#8201;nm). The 2D-FTIR-COS analysis showed conjugated C=O and aromatic C=C and C=O groups were the most susceptible functional groups to O3 aging for all BB-BrC. Moreover, it also revealed a consistent sequential changes, which is in the order of aromatic OH, conjugated C=O groups and aromatic C=O, aromatic COO&#8722;, and finally lignin-derived C-C, C-H and C-O groups. Our results provide new insights into the evolutionary behavior of the chromophoric and fluorescent properties of BB-BrC during O3 aging. They have important implications for the heterogeneous oxidation of BB emission to form BrC, and are of great significance for improving the accuracy of climate models and source apportionment models parameterized by the optical properties of BrC.

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“…Similar characteristics were also found in many previous studies. For example, it has been found that the HULIS fraction in the colder season presented more aromatic structures than those in the warmer season, of which the BB might be an important contribution of the former one (Baduel et al, 2010;Matos et al, 2015a, b;Paula et al, 2016). Moreover, the E 250 / E 365 ratios were also investigated, which were found to be 5.8 ± 0.5, 4.5 ± 0.2, 4.4 ± 0.3, and 14.7 ± 0.7 for primary HULIS emitted from the combustion of rice straw, corn straw, pine branch, and coal, respectively.…”

Section: Uv-vis Propertiesmentioning

confidence: 99%

Comprehensive characterization of humic-like substances in smoke PM2.5 emitted from the combustion of biomass materials and fossil fuels

et al. 2016

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Abstract. Humic-like substances (HULIS) in smoke fine particulate matter (PM 2.5 ) emitted from the combustion of biomass materials (rice straw, corn straw, and pine branch) and fossil fuels (lignite coal and diesel fuel) were comprehensively studied in this work. The HULIS fractions were first isolated with a one-step solid-phase extraction method, and were then investigated with a series of analytical techniques: elemental analysis, total organic carbon analysis, UV-vis (ultraviolet-visible) spectroscopy, excitationemission matrix (EEM) fluorescence spectroscopy, Fourier transform infrared spectroscopy, and 1 H-nuclear magnetic resonance spectroscopy. The results show that HULIS account for 11.2-23.4 and 5.3 % of PM 2.5 emitted from biomass burning (BB) and coal combustion, respectively. In addition, contributions of HULIS-C to total carbon and water-soluble carbon in smoke PM 2.5 emitted from BB are 8.0-21.7 and 56.9-66.1 %, respectively. The corresponding contributions in smoke PM 2.5 from coal combustion are 5.2 and 45.5 %, respectively. These results suggest that BB and coal combustion are both important sources of HULIS in atmospheric aerosols. However, HULIS in diesel soot only accounted for ∼ 0.8 % of the soot particles, suggesting that vehicular exhaust may not be a significant primary source of HULIS. Primary HULIS and atmospheric HULIS display many similar chemical characteristics, as indicated by the instrumental analytical characterization, while some distinct features were also apparent. A high spectral absorbance in the UV-vis spectra, a distinct band at λ ex /λ em ≈ 280/350 nm in EEM spectra, lower H / C and O / C molar ratios, and a high content of [Ar-H] were observed for primary HULIS. These results suggest that primary HULIS contain more aromatic structures, and have a lower content of aliphatic and oxygen-containing groups than atmospheric HULIS. Among the four primary sources of HULIS, HULIS from BB had the highest O / C molar ratios (0.43-0.54) and [H-C-O] content (10-19 %), indicating that HULIS from this source mainly consisted of carbohydrate-and phenolic-like structures. HULIS from coal combustion had a lower O / C molar ratio (0.27) and a higher content of [Ar-H] (31 %), suggesting that aromatic compounds were extremely abundant in HULIS from this source. Moreover, the absorption Ångström exponents of primary HULIS from BB and coal combustion were 6.7-8.2 and 13.6, respectively. The mass absorption efficiencies of primary HULIS from BB and coal combustion at 365 nm (MAE 365 ) were 0.97-2.09 and 0.63 m 2 gC −1 , respectively. Noticeably higher MAE 365 values for primary HULIS from BB than coal combustion indicate that the former has a stronger contribution to the light-absorbing properties of aerosols in the atmospheric environment.

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Natural organic matter in urban aerosols: Comparison between water and alkaline soluble components using excitation–emission matrix fluorescence spectroscopy and multiway data analysis

Cited by 85 publications

References 43 publications

Molecular compositions and optical properties of dissolved brown carbon in biomass burning, coal combustion, and vehicle emission aerosols illuminated by excitation–emission matrix spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry analysis

Molecular compositions and optical properties of dissolved brown carbon in biomass burning, coal combustion, and vehicle emission aerosols illuminated by excitation–emission matrix spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry analysis

The evolutionary behavior of chromophoric brown carbon during ozone aging of fine particles from biomass burning

Comprehensive characterization of humic-like substances in smoke PM<sub>2.5</sub> emitted from the combustion of biomass materials and fossil fuels

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Natural organic matter in urban aerosols: Comparison between water and alkaline soluble components using excitation–emission matrix fluorescence spectroscopy and multiway data analysis

Cited by 85 publications

References 43 publications

Molecular compositions and optical properties of dissolved brown carbon in biomass burning, coal combustion, and vehicle emission aerosols illuminated by excitation–emission matrix spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry analysis

Molecular compositions and optical properties of dissolved brown carbon in biomass burning, coal combustion, and vehicle emission aerosols illuminated by excitation–emission matrix spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry analysis

The evolutionary behavior of chromophoric brown carbon during ozone aging of fine particles from biomass burning

Comprehensive characterization of humic-like substances in smoke PM&lt;sub&gt;2.5&lt;/sub&gt; emitted from the combustion of biomass materials and fossil fuels

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Comprehensive characterization of humic-like substances in smoke PM<sub>2.5</sub> emitted from the combustion of biomass materials and fossil fuels