Nitrate (NO3−), one of the most important inorganic aerosols in the atmosphere, is mainly formed by oxidation of NOx by the hydroxyl radical (OH) and ozone (O3) in urban atmospheres. However, the fractional contributions of its various oxidation pathways remain unclear. Here, we collected particulate matter with aerodynamic diameter less than 2.5 μm (PM2.5) samples in a second‐tier city in southeast China from 1 September to 31 December 2017 and measured the NO3− and nitrate isotopic compositions (δ15N and δ18O). The average concentration of NO3−, δ15N, and δ18O values were 14.7 ± 11.6 μg/m3, (+4.3 ± 4.3)‰, and (+71.8 ± 14.7)‰ with the ranges from 0.8 to 57.7 μg/m3, −10.5‰ to +12.5‰ and +34.5‰ to +91.9‰, respectively. All three species were significantly higher in winter than in summer. Based on a Bayesian mixing model with a dual isotope array for NO3−, contributions of (37.1 ± 33.4)%, (60.3 ± 32.2)%, and (2.6 ± 2.7)% to NO3− could be attributed to OH oxidation, N2O5 hydrolysis, and NO3 + hydrocarbon (HC) pathways, respectively. Higher OH radical concentrations with higher ratios of OH to O3 led to lower NO3− concentrations, while lower OH radical concentrations with higher ratios of O3 to OH led to higher contributions of N2O5 hydrolysis, forming higher NO3− concentrations in winter. Under low OH, an increased O3 to NOx ratio increased the contribution of the NO3 + HC pathway. The comprehensive analysis of the isotopic compositions of nitrate helped identify the importance of major oxidation pathways of NOx in this city.
A multi-residue method for determination of pesticide residues in vegetables, using ethyl acetate extraction and determination by means of GC–MSD, is presented. The method includes as many as 27 pesticides such as organophosphorous, organohalogen, organonitrogen and pyrethroids pesticides, which are in common use or forbidden on vegetables in China. After extraction with ethyl acetate, the extract is concentrated and evaporated to dryness and redissolved in ethyl acetate before injection on GC–MSD. The recoveries were obtained in the range 70–100% with 5 exceptions in lettuce and 7 exceptions in cucumber, relative standard deviations between 1.92% and25.39% by means of standard addition to the vegetables blank extracts. The degradation of some pesticides in the 27 was studied by the method developed, the mixture of the pesticides commercial formulations was sparged on the vegetables, then the residues of samples obtained in different time were determined by the developed method. The determination indicated that (all pesticides were used as the instruction): 1.a pesticide, used on different plants, the quantity of the pesticide on the part for people’s dietary differs greatly; 2. some pesticides, degradating slowly and with a large dose, are inappropriate used on vegetables which remain on cropland for a short time. This research does not develop models for pesticides degradation, but provides some data on the safe intervals of the pesticides and a potential method for the study of multi-class pesticides safe intervals on a plant simultaneously.
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