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Water-insoluble organic carbon (WIOC) constitutes a substantial portion of organic carbon (OC) and contributes significantly to light absorption by brown carbon (BrC), playing pivotal roles in climate forcing. China is a hotspot region with high levels of OC and BrC, but information regarding the sources and light-absorbing properties of WIOC on a national scale remains scarce. Here, we investigated the light-absorbing properties and sources of WIOC in 10 representative urban cities in China. On average, WIOC made up 33.4 ± 7.66 % and 40.5 ± 9.73 % of concentrations and light absorption at 365 nm (Abs 365) of extractable OC (EX-OC), which includes relatively hydrophobic OC (WIOC and humic-like substances, HULIS-C) and hydrophilic OC (non-humic-like substances, non-HULIS-C). The mass absorption efficiency of WIOC at 365 nm (MAE 365) was (1.59 ± 0.55 m2(gC)-1) comparable to that of HULIS (1.54 ± 0.57 m2(gC)-1) but significantly higher than non-HULIS (0.71 ± 0.28 m2(gC)-1), indicating that hydrophobic OC possesses a stronger light-absorbing capacity than hydrophilic OC. Biomass burning (31.0 %) and coal combustion (31.1 %) were the dominant sources of WIOC, with coal combustion sources exhibiting the strongest light-absorbing capacity. Moreover, employing the simple forcing efficiency (SFE 300–700nm) method, we observed that WIOC exhibited the highest SFE 300–700nm (6.57 ± 5.37 Wg-1) among the EX-OC fractions. The radiative forcing of EX-OC was predominantly contributed by hydrophobic OC (WIOC – 39.4 ± 15.5 % and HULIS – 39.5 ± 12.1 %). Considering the aromaticity, sources, and atmospheric processes of different carbonaceous components, we propose a light-absorbing carbonaceous continuum, revealing that components enriched with fossil sources tend to possess stronger light-absorbing capacity, higher aromatic levels, increased molecular weights, and greater recalcitrance in the atmosphere. Reducing fossil fuel emissions emerges as an effective means of mitigating both gaseous (CO2) and particulate light-absorbing carbonaceous warming components. [ABSTRACT FROM AUTHOR]

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. Plain Language Summary: 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. Key Points: A fluorescence‐based method was developed to investigate secondary sources of water‐soluble brown carbon in five cities in ChinaThe contribution of secondary sources to water‐soluble brown carbon in the summer is approximately twice as high as during the winterThis secondary water‐soluble brown carbon was more associated with aging biomass burning in winter and biogenic emissions in summer [ABSTRACT FROM AUTHOR]

Water-insoluble carbon (WIOC) constitutes a substantial portion of organic carbon (OC) and contributes significantly to light absorption by brown carbon (BrC), playing pivotal roles in climate forcing and human health. China as hotspots regions with high level of OC and BrC, information regarding the sources and light-absorbing properties of WIOC on national scale remains scarce. Here, we investigated the light-absorbing properties and sources of WIOC in ten representative urban cities across China. On average, WIOC accounted for 33.4 ± 7.66 % and 40.5 ± 9.73 % of the concentrations and light-absorbing efficiency at 365 nm (Abs365) of extractable OC (EX-OC, comprising relatively hydrophobic OC [WIOC and humic-like substances: HULIS-C], and hydrophilic OC [non-humic-like substances: non-HULIS-C]). The mass absorption efficiency of WIOC at 365 nm (MAE365) was (1.59 ± 0.55 m2/gC) comparable to that of HULIS (1.54 ± 0.57 m2/gC) but significantly higher than non-HULIS (0.71 ± 0.28 m2/gC), indicating that hydrophobic OC possesses a stronger light-absorbing capacity than hydrophilic OC. Biomass burning (31.0 %) and coal combustion (31.1 %) were the dominant sources of WIOC, with coal combustion sources exhibited the strongest light-absorbing capacity. Moreover, employing the simple forcing efficiency (SFE300–700nm) method, we observed that WIOC exhibited the highest SFE300–700nm (6.57 ± 5.37 W/g) among the EX-OC fractions. The radiative forcing of EX-OC was predominantly contributed by hydrophobic OC (WIOC: 39.4 ± 15.5 % and HULIS: 39.5 ± 12.1 %). Considering the aromaticity, sources, and atmospheric processes of different carbonaceous components, we propose a light-absorbing carbonaceous continuum, revealing that components enriched with fossil sources tend to possess stronger light-absorbing capacity, higher aromatic levels, increased molecular weights, and greater recalcitrance in the atmosphere. Reducing fossil fuel emissions emerges as an effective means of mitigating both gaseous (CO2) and particulate light-absorbing carbonaceous warming components. [ABSTRACT FROM AUTHOR]

Secondary organic aerosols (SOAs) are important components of fine particulates in the atmosphere. However, the sources of SOA precursor and atmospheric processes affecting SOAs are poorly understood. This limits our abilities to improve air quality and model aerosol-mediated climate forcing. Here, we use novel compound-specific dual-carbon isotope fingerprints (Δ14 C and δ13 C) for individual SOA tracer molecules (i.e., oxalic acid) to investigate the fates of SOAs in the atmosphere at five emission hotspots in China. Coal combustion and vehicle exhaust accounted for ∼ 55 % of the sources of carbon in oxalic acid in Beijing and Shanghai, but biomass burning and biogenic emissions accounted for ∼ 70 % of the sources of carbon in oxalic acid in Chengdu, Guangzhou, and Wuhan during the sampling period. The dual-carbon isotope signatures of oxalic acid and bulk organic carbon pools (e.g., water-soluble organic carbon) were compared to investigate the fates of SOAs in the atmosphere. Photochemical aging and aqueous-phase chemical processes dominate the formation of oxalic acid in summer and in winter, respectively. The results indicated that SOA carbon sources and chemical processes producing SOAs vary spatially and seasonally, and these variations need to be included in Chinese climate projection models and air quality management practices. [ABSTRACT FROM AUTHOR]

Incomplete understanding of the sources of secondary organic aerosol (SOA) leads to large uncertainty in both air quality management and in climate change assessment. Chemical reactions occurring in the atmospheric aqueous phase represent an important source of SOA mass, yet, the effects of anthropogenic emissions on the aqueous SOA (aqSOA) are not well constrained. Here we use compound-specific dual-carbon isotopic fingerprints (δ13C and Δ14C) of dominant aqSOA molecules, such as oxalic acid, to track the precursor sources and formation mechanisms of aqSOA. Substantial stable carbon isotope fractionation of aqSOA molecules provides robust evidence for extensive aqueous-phase processing. Contrary to the paradigm that these aqSOA compounds are largely biogenic, radiocarbon-based source apportionments show that fossil precursors produced over one-half of the aqSOA molecules. Large fractions of fossil-derived aqSOA contribute substantially to the total water-soluble organic aerosol load and hence impact projections of both air quality and anthropogenic radiative forcing. Our findings reveal the importance of fossil emissions for aqSOA with effects on climate and air quality. Isotope fingerprinting is used to track precursor sources and formation pathways of aqueous SOA, such as oxalic acid, finding that fossil fuel precursors contributions have largely been underestimated. [ABSTRACT FROM AUTHOR]

Organosulfur compounds (OrgSs), especially organosulfates, have been widely reported to be present in large quantities in particulate organic matter found in various atmospheric environments. Despite hundreds of organosulfates and their formation mechanisms being previously identified, a large fraction of OrgSs remain unexplained at the molecular level, and a better understanding of their formation pathways and critical environmental parameters is required to explain the variations in their concentrations. In this study, the abundance and molecular composition of OrgSs in fine particulate samples collected in Guangzhou were reported. The results revealed that the ratio of the annual average mass of organic sulfur to total particulate sulfur was 33 ± 12 %, and organic sulfur had positive correlations with SO 2 (r=0.37 , p<0.05) and oxidant (NO x + O 3 , r=0.40 , p<0.01). A Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis revealed that more than 80 % of the sulfur-containing formulas detected in the samples had the elemental composition of o/(4s+3n)≥1 , indicating that they were largely in the form of oxidized organosulfates or nitrooxy organosulfates. Many OrgSs that were previously tentatively identified as having biogenic or anthropogenic origins were also present in freshly emitted aerosols derived from combustion sources. The results indicated that the formation of OrgSs through an epoxide intermediate pathway could account for up to 46 % of OrgSs from an upper bound estimation, and the oxidant levels could explain 20 % of the variation in the mass of organic sulfur. The analysis of our large dataset of FT-ICR MS results suggested that relative humidity, oxidation of biogenic volatile organic compounds via ozonolysis, and NO x -related nitrooxy organosulfate formation were the major reasons for the molecular variation of OrgSs, possibly highlighting the importance of the acid-catalyzed ring-opening of epoxides, oxidation processes, and heterogeneous reactions involving either the uptake of SO 2 or the heterogeneous oxidation of particulate organosulfates into additional unrecognized OrgSs. [ABSTRACT FROM AUTHOR]

Atmospheric nitrogen‐containing organic compounds (NOCs) are critical components of global nitrogen deposition and light‐absorption species. The sources and compositions of NOCs are complex and remain largely unknown. Here, NOCs in 55 ambient aerosol samples collected in Guangzhou, South China, were analyzed via ultrahigh‐resolution Fourier transform ion cyclotron resonance mass spectrometry in negative‐ion and positive‐ion electrospray ionization (ESI) modes. The molecular compositions of NOCs measured via ESI– and ESI+ exhibited considerable differences. NOCs detected in the negative mode were mainly composed of highly oxygenated organic nitrates (O/N = 6), whereas NOCs detected in the positive mode were mainly composed of reduced nitrogen‐containing compounds (e.g., amides and amino acids). CHN compounds potentially corresponding to amines and alkaloids showed low abundance in the detection modes. Non‐metric multidimensional scaling and individual compound correlation analyses showed that the molecular compositions of NOCs were mainly affected by anthropogenic activities and meteorological parameters. For example, anthropogenic activities such as biomass burning and secondary nitrogen‐chemistry processes led to the accumulation of aromatic and highly oxygenated NOCs during winter. During summer, higher OH radical concentrations and temperatures will result in more prevalent or persistent reduced aliphatic NOCs, particularly lipid‐like amines. Some variables (e.g., relative humidity) have distinct effects on the variation of different types of NOCs. More research is needed to reveal the influencing mechanisms. This study clarifies the molecular compositions of NOCs and the mechanisms by which various factors influence the molecular variations. The findings can guide the assessment of NOCs evolution and deposition. Plain Language Summary: Negative and positive electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI‐FT‐ICR‐MS) was used to characterize the molecular composition of nitrogen‐containing organic compounds (NOCs) from aerosol samples in Guangzhou. It was determined that a large amount of various NOCs are present in the samples, with NOCs in highly oxidative and reduced states can be roughly identified by distinct ionization modes. By combining the ESI‐FT‐ICR‐MS results and statistical analysis, the factors that associated with the distribution of NOCs and how these factors worked were identified. Anthropogenic activities and meteorological parameters (e.g., temperature and oxidation levels) are the two important drivers that led to the variations of NOCs, resulting to inverse molecular patterns with different response to aromatic/highly unsaturated and saturated structures, respectively. This study provides a useful clue for studying NOCs in complex system, bridges the links between the filed observation and knowledge about sources and formation pathways of NOCs that derived from controlled laboratory studies. Key Points: Most of identified CHON− species had O/N ≥ 3 and showed higher O/C ratios than CHON+ species; CHN only constituted small fraction of nitrogen‐containing organic compounds (NOCs)Biomass burning and secondary inorganic‐nitrogen processes lead to the accumulation of aromatic and phenolic NOCs during winterHigher OH radical concentrations and temperatures result in more prevalent or persistent reduced aliphatic NOCs in summer [ABSTRACT FROM AUTHOR]

Polyaromatic organic matter (POM) is an important group of pollutants and light absorbers in ambient aerosols, which consists of a wide range of chemicals with fused benzene rings. POM in ambient aerosols is mainly derived from the incomplete combustion of fossil fuel and biomass. Source apportionment of POM is crucial for advising efficient mitigation of anthropogenic emissions, but that is a challenge due to the complicated composition of POM and ambient aerosols. Benzene polycarboxylic acids (BPCAs) have recently been introduced as molecular markers of atmospheric POM. Compound-specific radiocarbon analysis of BPCAs is expected to be a powerful tool for apportioning fossil sources and contemporary (i.e., biomass burning) sources of POM in ambient aerosols, yet this application is still lacking. We developed a method for radiocarbon analysis of BPCAs substituted with 3–6 carboxylic groups (B6CA, B5CA, B4CAs and B3CAs). BPCAs were isolated with preparative liquid chromatography with high recoveries (≥85%). The method is validated with reference materials with fossil and contemporary radiocarbon signatures. Successful radiocarbon analysis of BPCAs was achieved for these reference materials after correcting for the presence of average blanks (B6CA: 1.2 ± 0.2 μg, B5CA: 2.3 ± 0.6 μg, individual B4CAs: 2.7 ± 0.2 μg and individual B3CAs: 6.9 ± 0.7 μg). Source apportionment of POM based on radiocarbon analysis of BPCAs was performed for an urban dust reference material, as well as bulk aerosols and water-soluble, methanol-soluble fractions of ambient aerosols from a megacity of southern China. The results show varied contributions of fossil and contemporary sources among different POM fractions. [Display omitted] • Benzene polycarboxylic acids (BPCAs) are used to track polyaromatic organic matter (POM). • A method of compound-specific radiocarbon analysis (CSRA) of BPCAs is developed. • Successful CSRA of BPCAs is achieved for reference and ambient materials. • Sources of POM in ambient aerosols are apportioned by CSRA of BPCAs. • Fossil-contemporary source patterns vary between different POM fractions. [ABSTRACT FROM AUTHOR]

Black carbon (BC) is an important component of the brown clouds, contributing to climate and health effects of air pollution. In this work, we developed a new method for measuring BC concentrations and its radiocarbon isotope (14C) using quartz wool disk passive air samplers (Pas-QW). A field calibration study was conducted at two sampling sites (Guangzhou and Yantai), using an improved thermal/optical method to measure BC. Uptake profiles of Pas-QW were linear over the 77 days that the samplers were deployed, and the average sampling rate of BC measured was 1.1 ± 0.2 m3/day. The method was found to be reproducible with coefficients of variation as low as 17% for BC measured in ambient passive samples. Furthermore, passive sampling was carried out at six sites in the Indo-China Peninsula (ICP) from January to April and June to September of 2016. The high BC concentrations and the high fraction of modern carbon (f M) values emphasizes that ICP is still dominated by biomass burning emissions (residential cooking and agricultural burning), both in dry and wet seasons. This study provides a proof concept and methodology for the application of Pas-QW to cost-effectively expand measurements of BC at the global scale. [Display omitted] • A new method for measuring BC and its 14C using quartz wool disk passive samplers. • The method requires no sample processing and have good reproducibility for BC. • The relative contribution of biomass burning to BC can reach 67 ± 13% in ICP, with obvious spatiotemporal heterogeneity. [ABSTRACT FROM AUTHOR]

[Display omitted] Field-based sampling can provide more accurate evaluation than MODIS in regional biomass burning (BB) emissions given the limitations of MODIS on unresolved fires. Polyurethane foam-based passive air samplers (PUF-PASs) are a promising tool for collecting atmospheric monosaccharides. Here, we deployed PUF-PASs to monitor monosaccharides and other BB-related biomarkers and presented a dataset of 31 atmospheric BB-related biomarkers in the Indo-China Peninsula (ICP) and Southwest China. The peak concentrations of monosaccharides in the ICP occurred before monsoon season. The highest concentrations were in the eastern Mekong plain, while the lowest were along the eastern coast. BB-related biomarkers displayed elevated concentrations after April, particularly in the monsoon season; however, fewer active fires were recorded by MODIS. This revealed the importance of MODIS unresolved fires (e.g., indoor biofuel combustion, small-scale BB incidents, and charcoal fires) to the regional atmosphere. The PAS derived levoglucosan concentrations indicated that, with the inclusion of MODIS unresolved fires, the estimated top-down emissions of PM (4194–4974 Gg/yr), OC (1234–1719 Gg/yr) and EC (52–384 Gg/yr) would be higher than previous bottom-up estimations in the ICP. Future studies on these MODIS unresolved fires and regional monitoring data of BB are vital for improving the modeling of regional BB emissions. [ABSTRACT FROM AUTHOR]