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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]

Wearing of vehicle parts could release many chemical additives into the environment, such as benzotriazoles (BTRs), benzothiazoles (BTHs), and p -phenylenediamines (PPDs), which are potentially toxic to wildlife and humans. This study investigated the occurrence, source, and risks of BTRs, BTHs, and PPDs in a source catchment providing water to Guangzhou, a megacity in South China, covering groundwater, surface water, and stormwater. The results showed that BTRs and BTHs were predominant in surface water and groundwater. Unexpectedly, the BTR and BTH concentrations were lower in surface water than groundwater in a third of the paired samples. For the first time, 6PPD-quinone, a toxic ozonation product of N -(1,3-dimethylbutyl)- N′ -phenyl-1,4-phenylenediamine (6PPD), was extensively detected in source waters. Stormwater decreased the BTR concentrations but increased the 6PPD-quinone concentrations in surface water owing to their affiliation to suspended particles. From natural to urban segments of Liuxi river, a downstream increasing trend in BTR and BTH concentrations was observed, confirming that they are indicative of urban anthropogenic activities. Strong correlations between industrial activities and BTR or BTH concentrations in surface water indicated that industrial activities were their main sources. Six compounds were prioritized as potentially persistent, mobile, and toxic (PMT) chemicals, combing our monitoring results and REACH criterion. This study improves our understanding of the environmental fates and risks of water-soluble tire-wear chemicals, which provides important information for chemical management, and indicates attention should be paid to the risk posed by 6PPD-quinone in the source water. [Display omitted] • For the first time, 6PPD-Q was widely detected in source water, and could pose high risks via drinking water. • Six compounds, including 6PPD-quinone, were identified as potentially persistent, mobile and toxic (PMT) substances. • BTRs and BTHs are demonstrated to be indicators of urban anthropogenic activities. [ABSTRACT FROM AUTHOR]