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Characterization of water-soluble organic matter in urban aerosol by 1H-NMR spectroscopy.

ABSTRACT: The functional and 13C isotopic compositions of water-soluble organic carbon (WSOC) in atmospheric aerosol were determined by nuclear magnetic resonance (1H-NMR) and isotope ratio mass spectrometry (IRMS) in an urban location in the Southern Mississippi Valley. The origin of WSOC was resolved using the functional distribution of organic hydrogen, ?13C ratio, and positive matrix factorization (PMF). Three factors were retained based on NMR spectral bins loadings. Two factors (factors 1 and 3) demonstrated strong associations with the aliphatic region in the NMR spectra and levoglucosan resonances. Differences between the two factors included the abundance of the aromatic functional group for factor 1, indicating fresh emissions and, for factor 3, the presence of resonances attributed to secondary ammonium nitrate and low ?13C ratio values that are indicative of secondary organic aerosol. Factors 1 and 3 added 0.89 and 1.08 ?gC m-3, respectively, with the highest contribution in the summer and fall. Factor 2 retained resonances consistent with saccharides and was attributed to pollen particles. Its contribution to WSOC varied from 0.22 ?gC m-3 in winter to 1.04 ?gC m-3 in spring.

SUBMITTER: Chalbot MG

PROVIDER: S-EPMC4905722 | biostudies-literature | 2016 Mar

REPOSITORIES: biostudies-literature

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Characterization of water-soluble organic matter in urban aerosol by 1H-NMR spectroscopy.

Chalbot Marie-Cecile G MG Chitranshi Priyanka P da Costa Gonçalo Gamboa GG Pollock Erik E Kavouras Ilias G IG

Atmospheric environment (Oxford, England : 1994) 20160301 March 2016

The functional and 13C isotopic compositions of water-soluble organic carbon (WSOC) in atmospheric aerosol were determined by nuclear magnetic resonance (1H-NMR) and isotope ratio mass spectrometry (IRMS) in an urban location in the Southern Mississippi Valley. The origin of WSOC was resolved using the functional distribution of organic hydrogen, δ13C ratio, and positive matrix factorization (PMF). Three factors were retained based on NMR spectral bins loadings. ...[more]

PMID: 27313488

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Project description:The chemical content of water-soluble organic carbon (WSOC) as a function of particle size was characterized in Little Rock, Arkansas in winter and spring 2013. The objectives of this study were to (i) compare the functional characteristics of coarse, fine and ultrafine WSOC and (ii) reconcile the sources of WSOC for periods when carbonaceous aerosol was the most abundant particulate component. The WSOC accounted for 5 % of particle mass for particles with ?p > 0.96 ?m and 10 % of particle mass for particles with ?p < 0.96 ?m. Non-exchangeable aliphatic (H-C), unsaturated aliphatic (H-C-C=), oxygenated saturated aliphatic (H-C-O), acetalic (O-CH-O) and aromatic (Ar-H) protons were determined by proton nuclear magnetic resonance ((1)H-NMR). The total non-exchangeable organic hydrogen concentrations varied from 4.1 ± 0.1 nmol m(-3) for particles with 1.5 < ?p < 3.0 ?m to 73.9 ± 12.3 nmol m(-3) for particles with ?p < 0.49 ?m. The molar H/C ratios varied from 0.48 ± 0.05 to 0.92 ± 0.09, which were comparable to those observed for combustion-related organic aerosol. The R-H was the most abundant group, representing about 45 % of measured total non-exchangeable organic hydrogen concentrations, followed by H-C-O (27 %) and H-C-C= (26 %). Levoglucosan, amines, ammonium and methanesulfonate were identified in NMR fingerprints of fine particles. Sucrose, fructose, glucose, formate and acetate were associated with coarse particles. These qualitative differences of (1)H-NMR profiles for different particle sizes indicated the possible contribution of biological aerosols and a mixture of aliphatic and oxygenated compounds from biomass burning and traffic exhausts. The concurrent presence of ammonium and amines also suggested the presence of ammonium/aminium nitrate and sulfate secondary aerosol. The size-dependent origin of WSOC was further corroborated by the increasing ?(13)C abundance from -26.81 ± 0.18 ‰ for the smallest particles to -25.93 ± 0.31 ‰ for the largest particles and the relative distribution of the functional groups as compared to those previously observed for marine, biomass burning and secondary organic aerosol. The latter also allowed for the differentiation of urban combustion-related aerosol and biological particles. The five types of organic hydrogen accounted for the majority of WSOC for particles with ?p > 3.0 ?m and ?p < 0.96 ?m.

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Characterization of water-soluble organic matter in urban aerosol by 1H-NMR spectroscopy.

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Characterization of water-soluble organic matter in urban aerosol by <sup>1</sup>H-NMR spectroscopy.

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Characterization of water-soluble organic matter in urban aerosol by 1H-NMR spectroscopy.

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Characterization of water-soluble organic matter in urban aerosol by &lt;sup&gt;1&lt;/sup&gt;H-NMR spectroscopy.

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Characterization of water-soluble organic matter in urban aerosol by <sup>1</sup>H-NMR spectroscopy.