生物质燃烧排放PM<sub>2.5</sub>颗粒萃取的水溶性有机碳液相光化学氧化

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摘要为探究生物质燃烧排放的PM_2.5中水溶性有机碳（WSOC）的液相氧化特征，探索了两种生物质（小麦秸秆和水稻秸秆）燃烧排放的WSOC在紫外光（UV）和紫外光+H₂O₂体系（UV+OH）液相氧化产物的吸光特性、荧光特性及氧化特性.总有机碳分析仪的分析结果表明两个体系中WSOC去除率相当，增加H₂O₂并未明显改善去除率，推测直接光解是WSOC降解的主要途径；两种生物质燃烧PM_2.5中WSOC降解速率均较快，光照17h后WSOC去除率均在70%左右.两种生物质WSOC液相光化学氧化产物变化规律没有显著差别.随着光解进行，WSOC的降解导致吸光度不断下降，三维荧光（EEM）光谱图中的荧光峰Ex/Em=255~260nm/330~340nm强度也不断下降，但Ex/Em=230/400~500nm出现了新的荧光峰，说明可能生成了类腐殖质（HULIS）.高分辨气溶胶质谱仪（HR-AMS）分析的aqSOA生成潜势及其氧化特性，结果表明，随反应进行，尽管两种体系中aqSOA不断降低，但由于产物中含氧官能比例增加，aqSOA比反应前更具氧化性.产物的氧化潜势变化规律与HULIS变化规律相似，在UV+OH体系中先升高后下降，归因于反应初期含氧官能团物质的生成及随后的降解.结合以上研究结果，推测燃烧排放WSOC液相氧化经历了官能团化生成高一代产物后，碎片化和开环反应形成二代、三代氧化性更强的小分子产物，从而可能间接影响气候变化和空气质量.本文揭示生物质燃烧排放WSOC老化行为对于理解液相氧化反应对吸光性、SOA形成及健康影响等方面具有重要意义.

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关键词 ：生物质燃烧, 水溶性有机碳, 液相氧化, 荧光特性, 氧化潜势

Abstract：To explore aqueous-phase oxidation characteristics of extracted water soluble organic carbon (WSOC) in PM_2.5 emitted from biomass burning, this study investigated the absorption, fluorescence and the oxidation properties of WSOC from two types of biomass burning (wheat and rice straws) under ultraviolet (UV) and UV+H₂O₂ (UV+OH) conditions. The results from total organic carbon (TOC) analyzer showed that WSOC removal rates were almost the same in the two conditions. Extra H₂O₂ adding didn't improve the removal rates of WSOC, indicating direct photolysis was the major degradation pathway of WSOC. The removal rates of WSOC for wheat straw in two types of biomass burning samples were relatively fast, reducing about 70% in 17hours. No significant differences were found in aqueous-phase photochemical oxidation products between rice straw and wheat straw burning samples. With the photolysis process, absorbance decreased gradually due to WSOC degradation, and fluorescence intensity at excitation/emission (Ex/Em)255~260nm/330~340nm also declined. However, new fluorescent peaks at Ex/Em=230/(400~500) nm appeared, which could might be ascribed to the formation of humic-like substance (HULIS). Besides, high-resolution aerosol mass spectra (HR-AMS) was used to investigate aqSOA formation potential and its oxidation characteristics. The results showed that the mass of aqSOA decreased while aqSOA became more oxidative owing to the content of O-containing functional groups increasing as aging. The variation of oxidative potential (OPs) was similar to that of HULIS, with rose at first and then declined in UV+OH condition, which could be attributed to the formation of O-containing functional groups at first stage and subsequent degradation. Based on the above analysis results, we infer that the process of aqueous-phase oxidation of WSOC undergo functionalization to form the first generation products, then to more oxidized second-and third-generation smaller species formed by fragmentation and ring-opening reactions, which in turn indirectly impact climate change and air quality. The study revealed the aging behaviors of WSOC emitted from biomass burning, providing insights into understanding the light absorption, SOA formation and health effects caused by aqueous-phase oxidation reaction.

Key words： biomass burning WSOC aqueous-phase oxidation fluorescence characteristics oxidative potential

收稿日期: 2022-07-28

PACS:

X513

基金资助:江苏省自然科学基金项目（BK20221405）；江苏省普通高校专业学位研究生实践创新计划项目（SJCX21_1332）；江苏理工学院研究生实践创新计划项目（XSJCX21_64）

通讯作者: 叶招莲,教授,bess_ye@jsut.edu.cn;赵竹子,讲师,zhaozz@jsut.edu.cn E-mail: bess_ye@jsut.edu.cn;zhaozz@jsut.edu.cn

作者简介: 朱龙伟(1997-),男,江苏兴化人,江苏理工学院硕士研究生,主要研究方向为大气化学及污染控制.

引用本文:

朱龙伟, 崔尧嘉, 盖鑫磊, 叶招莲, 赵竹子. 生物质燃烧排放PM_2.5颗粒萃取的水溶性有机碳液相光化学氧化[J]. 中国环境科学, 2023, 43(3): 1014-1025. ZHU Long-wei, CUI Yao-jia, GE Xin-lei, YE Zhao-lian, ZHAO Zhu-zi. Aqueous-phase photochemical oxidation of extracted WSOC in PM_2.5 from biomass burning. CHINA ENVIRONMENTAL SCIENCECE, 2023, 43(3): 1014-1025.

链接本文:

http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2023/V43/I3/1014

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