Abstract. Biomass burning (BB) emits large amounts of brown carbon (BrC); however, the evolutionary behavior of BrC in BB emissions (BB BrC) resulting from complex atmospheric processes is poorly understood. In this study, the transformation of contents and the chromophoric characteristics of BrC in smoke particles emitted by the burning of rice straw (RS), corn straw (CS), and pinewood (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 in aromaticity, average molecular weight, and the light absorption capacity for the chromophores, as well as an increase in 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 %–87 % 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 (263–289 nm) and then with fulvic-like fractions (333–340 nm). In comparison, the changing sequence of susceptible fluorophores in the PW BrC to O3 was in the order of fulvic-like fluorophores with shorter wavelengths (309 nm), protein-like fluorophores (276 nm), and fulvic-like fluorophores with longer wavelengths (358 nm). The 2D-FTIR-COS (2D-COS combined with FTIR) 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 change, which is in the order of aromatic OH; conjugated C=O groups and aromatic C=O; aromatic COO−; 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, which are of great significance for better understanding the heterogeneous oxidation pathways of BB-derived BrC in the atmospheric environment.

No abstract

The information on molecular weight (MW) characteristics of DOM and relevant evolution behaviors during composting are limited. In this study, DOM extracted from co-composting of chicken manure and rice husks were comprehensively analyzed by using high-performance size exclusion chromatography (HPSEC) combined with a two-dimensional correlation spectroscopy (2D COS) to explore the evolution characteristics of MW of compost DOM. The HPSEC detected at UV of 254 nm and at uorescence (FL) Ex/Em wavelengths (315/410, 270/455 nm) all showed a gradual increase in both weight-average and number-average MW for DOM, suggesting that the large MW fractions were continuously generated and polymerized during composting. The 2D COS applied on HPSEC-UV and -FL further identi ed the key active MW chromophoric (i.e., 0.5, 7.2. 9.5, 26.3, 30.7, and 83.9 kDa) and uorophoric (i.e., 0.55 and 3.5 kDa) molecules that mainly participated in the transformation processes of compost DOM. Moreover, these active MW species were preferentially formed by the order of small to large molecules. A hetero-2D COS analysis disclosed the change sequence in the order of 0.5 and 7.2 kDa chromophores → 3.5 kDa uorophores, and the 0.55 and 3.5 kDa uorophores → 26.3 and 83.9 kDa chromophores.

<p><strong>Abstract.</strong> 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 O<sub>3</sub> aging are investigated. The O<sub>3</sub> 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 O<sub>3</sub> 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 %–87 % of the total fluorophores in final O<sub>3</sub>-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 O<sub>3</sub> aging. It showed that O<sub>3</sub> firstly reacted with protein-like fractions (263–289 nm), and then with fulvic-like fractions (333–340 nm). In comparison, the changing sequence of susceptible fluorophores in the PW-BrC to O<sub>3</sub> were in the order of fulvic-like with shorter wavelengths (309 nm) > protein-like fluorophores (276 nm) > fulvic-like fluorophores with longer wavelengths (358 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 O<sub>3</sub> 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<sup>−</sup>, 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 O<sub>3</sub> 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.</p>

No abstract