The optical properties of secondary brown carbon (BrC) aerosols are poorly understood, hampering quantitative assessments of their impact. We propose a new method for estimating secondary source of BrC using excitation-emission matrix (EEM) fluorescence spectroscopy, combined with parallel factor analysis (PARAFAC) and partial least squares regression (PLSR). Experiments were conducted on a collection of PM2.5 samples from urban areas in five Chinese cities during winter and summer. The humic-like component with long-emission wavelengths (L-HULIS) was identified as a secondary source tracer of BrC. This was confirmed by correlating PARAFAC components with secondary organic aerosol tracers and molecular oxidation indices obtained from Fourier transform ion cyclotron resonance mass spectrometry analysis. Using L-HULIS as a secondary tracer of BrC, it was determined that the contribution of secondary sources to water-soluble BrC (WS-BrC) in source emission samples is significantly smaller than in PM2.5 from five Chinese cities, supporting our method. In the five cities, secondary source derived via L-HULIS contributes a dominant potion (80% +/- 3.5%) of WS-BrC at 365 nm during the summer, which is approximately twice as high as during the winter (45% +/- 4.9%). Radiocarbon isotope (14C) analysis provides additional constraints to the sources of L-HULIS-derived secondary WS-BrC in urban PM2.5, suggesting that aged biomass burning is the dominant contributor to secondary WS-BrC in winter, and biogenic emission is dominant during summer. This study is the first report on identification of secondary sources of BrC using the fluorescence technique. It demonstrates the potential of this method in characterizing non-fossil source secondary BrC in the atmosphere. Brown carbon (BrC) originates from primary combustion emissions and secondary formation, with large source-dependent uncertainties of radiative forcing. Direct measurements to separate the primary and secondary BrC are challenging due to the chemical complexity. Recent online studies have shown that excitation-emission matrix fluorescence spectroscopy coupled with parallel factor (PARAFAC) analysis identified some fluorescent components that may be linked to secondary sources. However, there is a knowledge gap on whether PARAFAC components correlate closely with atmospheric secondary chemical components, particularly biogenic and anthropogenic secondary organic aerosol, as their precursors can also form secondary BrC chromophores. We established the correlations between PARAFAC components and secondary organic aerosol tracers and compound oxidations to identify the long-emission-wavelength humic-like component as a secondary source tracer of BrC. Then, we estimated non-fossil source secondary BrC in urban aerosols during the winter and summer. Our studies provide references for quantifying secondary sources of BrC in the atmosphere. A fluorescence-based method was developed to investigate secondary sources of water-soluble brown carbon in five cities in China The contribution of secondary sources to water-soluble brown carbon in the summer is approximately twice as high as during the winter This secondary water-soluble brown carbon was more associated with aging biomass burning in winter and biogenic emissions in summer

Light-absorbing carbonaceous aerosols primarily comprise black carbon (BC) and brown carbon (BrC), and they play a key role in atmospheric radiative forcing and global climate. Here, we present the light absorption, potential sources, and health risks of BC and BrC during the prescribed burning season at an urban background site in Brisbane based on the measurements with a seven-wavelength aethalometer. The enhancements in light absorption at 880 nm were potentially governed by the transport of prescribed burning emissions. Source apportionment results revealed that fossil-fuel (FF) combustion contributed more to the total equivalent BC (eBC) (67%) over the entire measurement period as compared to biomass burning (BB). The percentages of secondary BrC to BrC for BB- and FF-dominated periods were 60% and 21%, respectively, indicating the greater potential of BB emissions to form secondary BrC compared to FF emissions. The diurnal trend showed that the peaks of secondary BrC occurred at nighttime with high relative humidity, implying that the formation of secondary BrC was potentially associated with aqueous reactions. Potential source contribution function (PSCF) results suggested that air masses originating from southern and northern Brisbane were the potential pollution sources, where BB and traffic emissions were dominant. In addition, the health risks of eBC (based on equivalent numbers of passively smoked cigarettes) remarkably increased for periods with elevated eBC emissions, potentially originating from prescribed burns. These findings contribute to our understanding of the impact of BB on the light absorption properties of BC and BrC and could serve as a reference for government officials when performing prescribed burns with reduced environmental and health effects.

To investigate the seasonal variation of black carbon (BC) and brown carbon (BrC) light absorption at an urban site in Xi'an, China, an annual measurement was conducted by using a 7-wavelengths Aethalometer (model AE33). The results showed the aerosol absorptions were observed approximately 5-8 times greater in winter (395 Mm(-1) at 370 nm and 99 Mm(-1) at 880 nm, respectively) than those in autumn (49 Mm(-1) at 370 nm and 18 Mm(-1) at 880 nm, respectively). BC was the dominant light absorbing carbonaceous component at all wavelengths (from 370 nm to 950 nm). BrC absorption (370 nm) maximized during winter with 41% of the total aerosol absorption, and was lower in autumn (16%). The light absorption contributions of primary BrC (BrCpri) were higher than that of secondary BrC (BrCsec) in four seasons, with more than 67% of total BrC light absorption. The seasonal absorption Angstrom exponents (AAEs) of BrC, BrCpri, and BrCsec were directly derived with the highest values (3.91, 3.69, and 4.94, respectively) in wintertime. The BrCpri contributed much higher solar absorptions percentage to BC than BrCsec. The results underlined the primary emissions of urban BrCpri and BC, implying that the strategies of energy efficiency enhancement and energy structure reformation will be very important in reducing primary emissions in China. Such investigations should be conducted in other developing countries with severe air pollution. (c) 2020 Published by Elsevier B.V. on behalf of International Association for Gondwana Research.