Zhang Yongli, Kong Xianglan, Yang Yu, Ran Yong
State Key Laboratory of Organic Geochemistry, Guangdong-Hong Kong-Macao Joint Laboratory for Environmental Pollution and Control, Guangdong Provincial Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China; CAS Center for Excellence in Deep Earth Science, Guangzhou 510640, China; University of Chinese Academy of Sciences, Beijing 100049, China.
State Key Laboratory of Organic Geochemistry, Guangdong-Hong Kong-Macao Joint Laboratory for Environmental Pollution and Control, Guangdong Provincial Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China; CAS Center for Excellence in Deep Earth Science, Guangzhou 510640, China.
Sci Total Environ. 2023 Dec 15;904:166754. doi: 10.1016/j.scitotenv.2023.166754. Epub 2023 Sep 6.
The structure and constituents of sedimentary organic matter (SOM) in the degradation of benzene ring-C labeled 4-nonylphenol (C-NP) by sodium persulfate (NaSO) were investigated. NaSO mineralized over 84 % of C-NP to CO, and no parent unlabeled 4-nonylphenol (NP) compounds were detected in the water-soluble/supernatant phase or extractable residues. Organic carbon (OC) was sequentially separated from six sediment samples collected from the Pearl River (BET), estuary (GSD), continental shelf (S11 and S21), and deep sea (M9 and M10). Demineralized OC (DM), unstable OC (USOC), nonhydrolyzable OC (NHC), and resistant OC (ROC) were obtained and characterized using solid-state C nuclear magnetic resonance (SS-NMR). The correlations among USOC, NHC, and the degradation kinetic constant of C-NP (k) were significant (R > 0.86, p < 0.01), indicating that USOC and NHC were the main factors controlling C-NP degradation. SOM structure and constituent analyses indicated that O-alkyl C + OCH/NCH C + COO/NC=O C and carbohydrate + protein were positively related to Ln(k) (R > 0.72, p < 0.05) because these structures were unstable. However, the stable structures (Alkyl C and Arom CC) and constituents (sporopollenin, algaenan, and char) hindered C-NP degradation because they were negatively related to Ln(k) (R > 0.81, p < 0.05). The OC removal rate was positively correlated with C-NP degradation (R > 0.86, p < 0.01), indicating that the NP was primarily degraded in parallel with the breakdown of SOM. Stoichiometric analysis showed that NaSO effectively oxidized over 58 % of the OC to CO, and the electron transfer efficiency was 17.2-69.5 %. This study is the first to emphasize the importance of SOM degradation, structure, and constituents in the degradation of NP by persulfate.
研究了过硫酸钠（NaSO）降解苯环-C标记的4-壬基酚（C-NP）过程中沉积有机质（SOM）的结构和成分。过硫酸钠将超过84%的C-NP矿化生成CO，在水溶性/上清液相或可提取残留物中未检测到未标记的母体4-壬基酚（NP）化合物。从珠江（BET）、河口（GSD）、大陆架（S11和S21）和深海（M9和M10）采集了六个沉积物样本，并依次分离出有机碳（OC）。通过固态碳核磁共振（SS-NMR）对脱矿质OC（DM）、不稳定OC（USOC）、不可水解OC（NHC）和抗性OC（ROC）进行了表征。USOC、NHC与C-NP降解动力学常数（k）之间存在显著相关性（R>0.86，p<0.01），表明USOC和NHC是控制C-NP降解的主要因素。SOM结构和成分分析表明，O-烷基C+OCH/NCH C+COO/NC=O C以及碳水化合物+蛋白质与Ln(k)呈正相关（R>0.72，p<0.05），因为这些结构不稳定。然而，稳定结构（烷基C和芳族CC）和成分（孢粉素、藻胆蛋白和炭）阻碍了C-NP降解，因为它们与Ln(k)呈负相关（R>0.81，p<0.05）。OC去除率与C-NP降解呈正相关（R>0.86，p<0.01），表明NP主要与SOM的分解同时降解。化学计量分析表明，过硫酸钠有效地将超过58%的OC氧化为CO，电子转移效率为17.2-69.5%。本研究首次强调了SOM降解、结构和成分在过硫酸盐降解NP过程中的重要性。
