Chemical labeling (CL) in combination with liquid chromatography-mass spectrometry (LC-MS) analysis has been demonstrated to be a promising technology in metabolomic analysis. However, identification of chemically labeled metabolites remains to be challenging. Retention time (RT) is one of the most important parameters for the identification of metabolites, but it could vary greatly in LC-MS analysis. In this work, we developed a chemical labeling-based HPLC retention index (CL-HPLC RI) strategy to facilitate the identification of metabolites. In this CL-HPLC RI strategy, a series of 2-dimethylaminoethylamine (DMED)-labeled fatty acids were used as calibrants to establish RIs for DMED-labeled carboxylated compounds and a series of 4-( N, N-dimethylamino)phenyl isothiocyanate (DMAP)-labeled fatty amines were used as calibrants for DMAP-labeled amine compunds. To calculate the RIs, the whole LC chromatogram was divided into 24 time intervals by 23 DMED-labeled fatty acid standards or 15 time intervals by 14 DMAP-labeled fatty amine standards. Then, we established the RIs of 854 detected DMED-labeled carboxylated metabolites and 1057 DMAP-labeled amine metabolites in fecal samples and demonstrated that RIs were highly reproducible under different elution gradients, columns, and instrument systems. Finally, we applied this strategy to the identification of metabolites in human serum. Using RIs, 267 DMED-labeled carboxylated metabolites and 273 DMAP-labeled amine metabolites in human serum matched well with the fecal metabolome database. Taken together, the developed CL-HPLC RI strategy was demonstrated to be a promising method to facilitate the identification of metabolites in metabolomic analysis.

To understand the chemical evolution of dust in the current East Asian atmosphere, the chemistry of PM2.5 and size-resolved aerosols in Shanghai, China, during the 2019 dust storm event was investigated. Our results showed that concentrations of SO4 2– in the city during the event highly correlated with Ca2+ and Na+ due to the direct emissions of CaSO4 and Na2SO4 from the upwind deserts. In contrast, during the event, NO3 – linearly correlated with NH4 + at a molar ratio close to 1:1, and both almost entirely stayed in coarse particles, suggesting they accumulated on the dust surface as NH4NO3. Based on the field observations and laboratory smog chamber simulations, we found that NO2 and O3 in Shanghai during the dust period reacted to form N2O5, which subsequently hydrolyzed into HNO3 on the surface of saline mineral dusts (e.g., CaSO4 and Na2SO4) and was further neutralized by NH3 as NH4NO3. The relative abundances of NO3 – and NH4 + in Shanghai during the dust event were notably higher than those a decade ago, indicating that this heterogeneous formation of NH4NO3 on dust was enhanced by the abundantly coexisting NO x , O3, and NH3 in the current East Asian atmosphere, which should be considered in future modeling studies.

Hydrogen bonded complexes of heterocyclic compounds with methanol were studied using matrix isolation FTIR spectroscopy and theoretical calculations.

Abstract. Secondary organic aerosol (SOA) formation from a cyclohexene / NO x system with various SO 2 concentrations under UV light was investigated to study the effects of cyclic alkenes on the atmospheric environment in polluted urban areas. A clear decrease at first and then an increase in the SOA yield was found with increasing SO 2 concentrations. The lowest SOA yield was obtained when the initial SO 2 concentration was in the range of 30-40 ppb, while higher SOA yield compared to that without SO 2 could not be obtained until the initial SO 2 concentration was higher than 85 ppb. The decreasing SOA yield might be due to the fact that the promoting effect of acid-catalysed reactions on SOA formation was less important than the inhibiting effect of decreasing OH concentration at low initial SO 2 concentrations, caused by the competition reactions of OH with SO 2 and cyclohexene. The competitive reaction was an important factor for SOA yield and it should not be neglected in photooxidation reactions. The composition of organic compounds in SOA was measured using several complementary techniques including Fourier transform infrared (FTIR) spectroscopy, ion chromatography (IC), and Exactive Plus Orbitrap mass spectrometer equipped with electrospray interface (ESI). We present new evidence that organosulfates were produced from the photooxidation of cyclohexene in the presence of SO 2 .