微生物作用下炼厂外排水溶解性有机物的转化行为

doi:10.19965/j.cnki.iwt.2025-0118

摘要/Abstract

摘要：

石油炼化企业的外排水中含有大量组成极其复杂的溶解性有机物（DOM），其进入天然水体后的转化行为与其环境风险息息相关。然而目前关于微生物作用对炼厂外排水DOM在天然水体中转化行为的影响尚不清晰。因此，通过紫外-可见吸收光谱（UV-vis），三维荧光激发发射光谱（3D-EEM）以及静电场轨道阱质谱（Orbitrap MS）等表征方法，从DOM含量、光学特征和分子组成等方面分析了炼厂外排水DOM进入天然水体后在微生物作用下的转化行为。研究发现受纳水中DOM的修正性芳香指数（AI_mod）、氧碳比加权平均值（O/C_wa）经微生物作用后上升，氢碳比加权平均值（H/C_wa）经微生物作用后下降；微生物作用于受纳水中DOM时具有偏好性，CHO类的脂肪族DOM最易转化，转化后最易生成CHNO类的高不饱和类及酚类DOM，而耐微生物转化DOM中CHO和CHNO类的高含氧化合物相对丰度较高。微生物主要通过加氧反应、羧化反应、脱/增氮反应等使得DOM转化。此外，门水平和属水平的微生物群落分析表明，变形菌门（Proteobacteria）、放线菌门（Actinobacteriota）及LD29菌属微生物在炼厂外排水芳香族DOM的转化过程中发挥重要作用。

关键词: 溶解性有机物, 微生物转化, 炼厂外排水, 受纳水

Abstract:

Petroleum refinery effluents contain a large quantity of dissolved organic matter(DOM) with highly complex compositions. The subsequent transformation of DOM after entering water bodies was closely associated with its environmental risks. However, the influence of microbial activity on the transformation of DOM from refinery effluent in natural water bodies remains poorly understood. Therefore, this study comprehensively analyzed the transformation behavior of refinery effluent DOM in natural water bodies under microbial influence using ultraviolet-visible spectroscopy(UV-vis), three-dimensional excitation-emission matrix fluorescence spectroscopy (3D-EEM), and electrostatic field Orbitrap mass spectrometry(Orbitrap MS). The analysis covered DOM content, optical characteristics, and molecular composition. The results revealed that the modified aromaticity index(AI_mod) and O/C weighted average(O/C_wa) of DOM in the receiving water increased, whereas H/C weighted average(H/C_wa) decreased after microbial transformation. Microbial exhibited selectivity for the transformation of DOM. Fatty DOM of the CHO class was the most easily transformed and highly unsaturated and phenolic DOM of the CHNO class were more likely to form after transformation. Whereas DOM resistant to microbial degradation exhibited a higher relative abundance of oxygen-rich compounds of the CHO and CHNO classes. The transformation of DOM by microbes was mainly through oxidation reactions, carboxylation reactions, and denitrification/nitrogenation reactions. Moreover, phylum- and genus-level microbial community analysis indicated that Proteobacteria, Actinobacteriota, and the genusLD29 played key roles in the transformation of aromatic DOM in refinery effluent.

Key words: dissolved organic matter, microbial transformation, refinery effluent, receiving water

中图分类号:

TE991.2

王乐琪, 牛泽琳, 翁艺斌, 朱怡霏, 何蕾, 王庆宏, 陈春茂. 微生物作用下炼厂外排水溶解性有机物的转化行为[J]. 工业水处理, 2025, 45(6): 18-27.

Leqi WANG, Zelin NIU, Yibin WENG, Yifei ZHU, Lei HE, Qinghong WANG, Chunmao CHEN. Transformation behavior of dissolved organic matter in refinery effluent under microbial activity[J]. Industrial Water Treatment, 2025, 45(6): 18-27.

https://www.iwt.cn/CN/Y2025/V45/I6/18

图/表 8

图1 为期28天微生物作用下受纳水DOC和SUVA₂₅₄的变化（a），以及反应之初（b）和反应5 d（c）、28 d（d）后DOM的3D-EEM光谱

Fig.1 Changes of DOC content and SUVA₂₅₄ under microbial action for 28 days（a）， and 3D-EEM spectra of DOM at the beginning of the reaction（b），after 5 days（c） and 28 days（d）

表1 DOM的分子指标

Table 1 Molecular indicators of DOM

	MW_wa	DBE_wa	AI_mod	O/C_wa	H/C_wa	NOSC_wa
外排水	294.001	5.972	0.273	0.426	1.238	-0.281
湖水	408.785	8.250	0.261	0.468	1.197	-0.167
转化前受纳水	303.714	6.130	0.273	0.416	1.252	-0.332
转化后受纳水	305.151	6.263	0.276	0.438	1.223	-0.241

图2 微生物作用下易转化和新产生DOM的碳数和DBE分布

Fig.2 Carbon number and DBE distribution of microbial-labile microbial-produce DOM

图3 易微生物转化和新产生DOM的分子组成及其范克莱夫伦图

Fig.3 Molecular compositions of microbial-labile and microbial-produce DOM， and the Van Krevelen plot

图4 耐微生物转化DOM的碳数和DBE分布（a），含氧量情况（b）及不同类型杂原子化合物占比（c）

Fig.4 DBE and carbon number distribution（a）， oxygen contents（b）， and proportion of different types of compounds containing heteroatom（c） of microbial-resistant DOM

图5 微生物转化过程中DOM发生的主要反应

Fig.5 Main reactions in DOM microbial transformation

表2 微生物反应过程中Alpha多样性变化

Table 2 Changes of alpha diversity during microbial reactions

时间	物种丰富度			群落多样性		物种均匀度
时间	Chao	Sobs	Ace	Shannon	Simpson	Pielou
第0天	1 180.91	1 175	1 191.22	5.54	0.011	0.784
第5天	1 546.89	1 518	1 562.56	5.75	0.010	0.786
第28天	1 322.13	1 322	1 323.52	5.89	0.008	0.819

图6 微生物转化过程中微生物群落结构在门水平和属水平的变化情况

Fig.6 Changes of microbial community at phylum level and genus level during DOM microbial transformation

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