非生物改性对厌氧微生物产物光化学活性影响

doi:10.16085/j.issn.1000-6613.2022-1180

摘要/Abstract

摘要：

厌氧溶解性微生物产物（soluble microbial products，SMP）广泛存在于天然深层水体，经水体扰动可迁移至表层水域。在此过程中厌氧SMP将受到一系列非生物转化过程的影响，如自然光及氧化还原介质，进而导致其理化性质发生改变，最终影响其光化学活性。本研究分别从厌氧微生物菌群（anaerobic microorganisms，An）和希瓦氏菌（Shewanella oneidensis，S）中提取了An-SMP和S-SMP，在模拟自然光和氧化还原的条件下改性48h，并评估非生物改性对厌氧SMP光化学活性的影响。结果表明：原始An-SMP的芳香度、腐殖化程度和分子量均高于S-SMP。自然光改性后，两种SMP的紫外吸光度和芳香度降低，芳香C $̿$ C结构被破坏，腐殖化程度降低，生成了更多的亲水性含氧官能团。氧化还原改性后，两种SMP吸光度出现增色效应，腐殖化程度升高，更多的蛋白类物质向腐殖质类物质转化，使氧化还原改性对SMP光化学性质的影响更为显著。SMP对17α-乙炔基雌二醇（EE2）光转化起促进作用，且经氧化还原改性后的SMP对EE2光解的介导作用明显优于经光改性的SMP。其中对EE2光解过程起主要作用的活性氧物质包括激发三线态SMP（³SMP^*）和羟基自由基（·OH）。本研究为明确自然水体中SMP介导有机污染物光转化的影响提供了理论研究基础。

关键词: 厌氧溶解性微生物产物, 光改性, 氧化还原改性, 光化学, 活性氧物质

Abstract:

Anaerobic soluble microbial products (SMP) are widespread in the deep-water environment and could migrate to the upper water by water disturbance processes. The physicochemical properties of anaerobic SMP would be altered during migration by various abiotic transformation processes, such as photo irradiation and redox processes, which would further change its photochemical activity. Herein, anaerobic SMP extracted from anaerobic microorganisms (An-SMP) and that from Shewanella oneidensis (S-SMP) were modified by photo irradiation and redox processes for 48h to evaluate the effects of these abiotic modifications on the photochemical activity of anaerobic SMP. The results of the characterization showed that the aromaticity, humification degree, and molecular weight of the original An-SMP were higher than those of S-SMP. The UV absorbance, aromaticity, degree of humification, and aromatic C $̿$ C structure of both of SMP decreased after the photo-modification, while hydrophilic oxygen-containing functional groups increased. After the redox-modification process, the hyperchromic effect of both of SMP absorbance was observed, as well as the increase of humification degree and the conversion of protein-like substances to humic substances. Compared to photo-modification, redox-modification showed more significant effects on the photochemical properties of SMP. Furthermore, the photo-transformation of 17α-ethinylestradiol (EE2) was promoted by the SMP, and the redox-modified SMP exhibited superior photochemical properties than that of photo-modified SMP. The mechanism study indicated that the active oxygen substances were responsible for the photolysis of EE2, especially the ³SMP^* and ·OH. This study provided a theoretical basis to clarify the effect of abiotic transformation processes on the photo-transformation of organic pollutants mediated by SMP in natural water.

Key words: anaerobic soluble microbial products, photo-modification, redox-modification, photochemistry, reactive oxygen species

中图分类号:

X131.2

范思涵, 于国熙, 来超超, 何欢, 黄斌, 潘学军. 非生物改性对厌氧微生物产物光化学活性影响[J]. 化工进展, 2023, 42(4): 2180-2189.

FAN Sihan, YU Guoxi, LAI Chaochao, HE Huan, HUANG Bin, PAN Xuejun. Effect of abiotic modification on photochemical activity of anaerobic microbial products[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2180-2189.

图/表 10

图1 自然光和氧化还原改性对厌氧SMP总有机碳含量的影响

图2 自然光和氧化还原改性的An-P、S-P、An-E和S-E的紫外-可见光谱图

表1 自然光和氧化还原改性厌氧SMP的光谱参数表

样品	SUVA₂₅₄	ΔlgK	E₂/E₃	S_275-295	S_350-400	S_R	FI	HIX
An-0	1.73	0.324	2.27	0.00575	0.00142	4.05	1.84	2.30
An-P48	1.10	0.301	3.69	0.00520	0.00070	7.43	1.99	1.23
An-E48	3.59	0.436	4.45	0.01400	0.00258	5.43	1.65	3.15
S-0	1.03	0.366	4.32	0.00535	0.00046	11.63	1.81	1.33
S-P48	0.84	0.263	5.23	0.00420	0.00042	10.00	2.08	1.20
S-E48	3.70	0.704	5.99	0.0180	0.00244	7.36	1.51	2.99

图3 自然光和氧化还原改性厌氧SMP的3D-EEM光谱图

图4 自然光和氧化还原改性厌氧SMP的红外光谱图

表2 自然光和氧化还原改性厌氧SMP的元素分析结果

样品	质量分数/%					摩尔比
样品	N	C	H	O	S	H/C	O/C	(N+O)/C
An-0	0.129	10.43	1.89	21.39	0.094	2.17	1.54	1.55
An-P48	0.135	9.70	2.48	24.05	0.326	3.07	1.86	1.87
An-E48	0.093	9.66	1.60	22.22	0.402	1.99	1.73	1.73
S-0	0.208	9.83	1.63	22.59	0.570	1.99	1.72	1.74
S-P48	0.087	7.84	2.30	21.45	0.562	3.52	2.05	2.06
S-E48	0.034	8.84	0.89	22.77	0.554	1.20	1.93	1.94

图5 自然光和氧化还原改性厌氧SMP的C 1s、O 1s X射线光电子能谱图

图6 改性SMP介导EE2自然光降解和探针化合物TMP、FFA的光降解曲线、2h-TPA的生成

图7 各参数相关性分析

表3 改性前后厌氧SMP的光生ROS产量

样品	f_TMP/10^-14L·mol^-1	AQY $S M P 3$ ^*/10^-4	[¹O₂]_SS/10^-14mol·L^-1	QY¹O₂/10^-4	[·OH]_SS/10^-18mol·L^-1
An-0	4.99±1.06	15.61±3.30	2.46±0.18	11.30±0.81	12.33±0.22
An-P48	22.99±0.91	71.97±2.86	10.75±0.50	49.30±2.29	99.69±2.78
An-E48	24.82±0.69	77.69±2.16	13.23±0.55	60.68±2.51	89.02±2.44
S-0	14.91±0.80	46.65±2.50	7.07±0.13	32.42±0.58	46.13±0.40
S-P48	20.30±0.32	63.55±1.00	14.82±0.39	68.01±1.79	14.85±0.22
S-E48	47.89±0.47	149.90±1.48	17.62±0.55	80.83±2.53	283.43±1.92

表3 改性前后厌氧SMP的光生ROS产量

样品	f_TMP/10^-14L·mol^-1	AQY $S M P 3$ ^*/10^-4	[¹O₂]_SS/10^-14mol·L^-1	QY¹O₂/10^-4	[·OH]_SS/10^-18mol·L^-1
An-0	4.99±1.06	15.61±3.30	2.46±0.18	11.30±0.81	12.33±0.22
An-P48	22.99±0.91	71.97±2.86	10.75±0.50	49.30±2.29	99.69±2.78
An-E48	24.82±0.69	77.69±2.16	13.23±0.55	60.68±2.51	89.02±2.44
S-0	14.91±0.80	46.65±2.50	7.07±0.13	32.42±0.58	46.13±0.40
S-P48	20.30±0.32	63.55±1.00	14.82±0.39	68.01±1.79	14.85±0.22
S-E48	47.89±0.47	149.90±1.48	17.62±0.55	80.83±2.53	283.43±1.92

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