硫化零价铁-微生物复合吸附剂对磷酸三(2-氯乙基)酯的吸附-降解机制

doi:10.16085/j.issn.1000-6613.2023-1247

化工进展 ›› 2024, Vol. 43 ›› Issue (8): 4704-4713.DOI: 10.16085/j.issn.1000-6613.2023-1247

• 资源与环境化工 • 上一篇

硫化零价铁-微生物复合吸附剂对磷酸三(2-氯乙基)酯的吸附-降解机制

黄鸿¹^,²(), 欧阳浩民¹^,², 杨依静¹, 李昌霖¹, 陈烁娜¹^,³()

^1.华南农业大学资源环境学院，广东广州 510642
^2.岭南现代农业科学与技术广东省实验室河源分中心，广东河源 517000
^3.华南农业大学广东省农业农村污染治理与环境安全重点实验室，广东广州 510642

收稿日期:2023-07-21 修回日期:2023-12-31 出版日期:2024-08-15 发布日期:2024-09-02
通讯作者: 陈烁娜
作者简介:黄鸿（1997—），男，硕士研究生，研究方向为微生物吸附剂材料的研制及应用。E-mail：huanghong_crazy@163.com。
基金资助:
岭南现代农业科学与技术广东省实验室河源分中心自主科研项目(DT20220016);河源市科技计划(河科2021001);广东省自然科学基金青年提升项目(2023A1515030284);岭南现代农业科学与技术广东省实验室河源分中心双聘团队项目(DT20220002)

Adsorption-degradation mechanism of tris(2-chloroethyl)phosphate by a composite adsorbent of zero-valent iron sulfide and microorganism

HUANG Hong¹^,²(), OUYANG Haomin¹^,², YANG Yijing¹, LI Changlin¹, CHEN Shuona¹^,³()

^1.College of Natural Resources and Environment, South China Agricultural University, Guangzhou 510642, Guangdong, China
^2.Heyuan Branch, Guangdong Laboratory for Lingnan Modern Agriculture, Heyuan 517000, Guangdong, China
^3.Guangdong Provincial Key Laboratory of Agricultural & Rural Pollution Abatement and Environmental Safety, South China Agricultural University, Guangzhou 510642, Guangdong, China

Received:2023-07-21 Revised:2023-12-31 Online:2024-08-15 Published:2024-09-02
Contact: CHEN Shuona

摘要/Abstract

摘要：

氯代有机磷阻燃剂（chlorinated organophosphate flame retardants，Cl-OPFRs）已在环境中被广泛检出，由于其稳定、易迁移及具有生物毒性，因此已成为不可忽视的新兴有机污染物。本文选择环境中检出率较高的磷酸三(2-氯乙基)酯[tris(2-chloroethyl) phosphate，TCEP]为研究对象，以硫化零价铁（S/ZVI）和TCEP耐受降解菌（缓生新鞘氨醇菌，Novosphingobium tardaugens，N₁）为研究材料，制备S/ZVI-微生物复合吸附剂（S/ZVI-N₁），并对其去除TCEP的性能和降解途径进行探究。结果显示，S/ZVI-N₁对TCEP的去除符合准一级动力学方程和Langmuir模型，表明该过程主要为单分子层的物理吸附作用，且根据准二级动力学方程的相关系数可知，在反应过程中同样存在化学吸附过程，S/ZVI-N₁作用于TCEP 12h，去除率达58.9%，显著高于仅依靠Novosphingobium tardaugens的去除率（32.9%）和仅依靠S/ZVI的去除率（31.2%）。产物分析表明，S/ZVI-N₁作用下TCEP较单独零价铁（zero-valent iron，ZVI）作用下降解更彻底，证明复合吸附剂中S/ZVI和Novosphingobium tardaugens之间存在协同作用，其最佳的反应条件为pH 5~7和30~35℃。微观分析显示，微生物和S/ZVI均参与了TCEP的降解。通过产物分析推导，S/ZVI-N₁对TCEP主要有2条降解途径，分别为S/ZVI主导的C—Cl键断裂和Novosphingobium tardaugens主导的O—P键断裂，最终生成磷酸三乙酯（triethyl phosphate，TEP）和磷酸（H₃PO₄）。

关键词: 氯代有机磷阻燃剂, 复合吸附剂, 微生物降解, 硫化零价铁, 降解途径, 磷酸三(2-氯乙基)酯

Abstract:

Chlorinated organophosphate flame retardants (Cl-OPFRs), a new type of pollutant, are widely detected in environment and has resistant to degradation, easy-migratory and biological toxicity. Tris(2-chloroethyl) phosphate (TCEP) with the highest detection rate in environment was chosen as the target pollutant in this study, and a composition adsorbent (named S/ZVI-N₁) that prepared by zero-valent iron sulfide and Novosphingobium tardaugens was used as research material, to explore the removal performance and degrading pathway of TCEP by the S/ZVI-N₁. The results showed that the removal of TCEP by S/ZVI-N₁ fitted to the quasi-first-order kinetic equation and Langmuir model, which indicated this process was a physical adsorption of monolayer primarily and the R² of quasi-second-order kinetic equation also proved the chemical adsorption. The removal rate of TCEP by S/ZVI-N₁ was 58.9% after 12h, which was higher significantly than that by Novosphingobium tardaugens or S/ZVI only (biodegradation rate was 32.95% and S/ZVI removal rate was 31.2%). The analysis of degradation products indicated that the decomposition of TCEP by S/ZVI-N₁was more thorough than that by ZVI alone. This proved there was synergistic reaction between the S/ZVI and Novosphingobium tardaugens to remove TCEP, and the optimal conditions of TCEP removal was pH 5—7 and 30—35℃. The intermediates analysis could deduce two degradation pathways of TCEP by S/ZVI-N₁, that one was the C—Cl bond broken down by S/ZVI and another was O—P bond broken down by Novosphingobium tardaugens, and the final products were triethyl phosphate (TEP) and H₃PO₄, which meant the completely degradation of TCEP.

Key words: chlorinated organophosphate flame retardants, composited adsorbent, bio-degradation, zero-valent iron sulfide, degradation pathway, tris(2-chloroethyl) phosphate

中图分类号:

X592

黄鸿, 欧阳浩民, 杨依静, 李昌霖, 陈烁娜. 硫化零价铁-微生物复合吸附剂对磷酸三(2-氯乙基)酯的吸附-降解机制[J]. 化工进展, 2024, 43(8): 4704-4713.

HUANG Hong, OUYANG Haomin, YANG Yijing, LI Changlin, CHEN Shuona. Adsorption-degradation mechanism of tris(2-chloroethyl)phosphate by a composite adsorbent of zero-valent iron sulfide and microorganism[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4704-4713.

图/表 11

图1 S/ZVI-N1对TCEP的吸附动力学

表1 TCEP吸附动力学方程拟合的相关参数

方程	R²	q_e	k
准一级动力学方程	0.9389	0.0110	0.2377
准二级动力学方程	0.8685	0.0121	27.7687

图2 S/ZVI-N1对TCEP的吸附等温式曲线

表2 TCEP的吸附等温式模型拟合的相关参数

Langmuir模型				Freundlich模型
R²	q_max/mg·g^-1	K_L		R²	K_F	1/n
0.9737	0.0832	0.16		0.9583	0.0116	0.7358

图3 不同温度下S/ZVI-N1对TCEP的去除效果

图4 不同pH下S/ZVI-N1对TCEP的去除效果

图5 降解前后S/ZVI-N1的铁元素价态变化（Fe 2p）

图6 降解前后S/ZVI-N1表面官能团的变化

图7 降解前后S/ZVI-N1表面铁的物相组成变化

表3 TCEP降解中间产物分析

产物	结构式（分子式）	质荷比（m/z）	停留时间/s
a	（C₆H₁₃O₄Cl₂P）	267.15	3.785
b	（C₆H₁₅O₄P）	182.98	3.686
c	（C₄H₉O₄Cl₂P）	221.13	5.134
d	（C₂H₆O₄ClP）	160.18	4.308
e	（H₃PO₄）	97.01	0.864
f	（C₂H₅OCl）	78.99	0.717

图8 S/ZVI-N1对TCEP的降解途径（圆圈标注的物质为未检出，但是根据结构式推导存在的中间产物）

参考文献 42

1	ZHENG Xiaobo, XU Fuchao, LUO Xiaojun, et al. Phosphate flame retardants and novel brominated flame retardants in home-produced eggs from an e-waste recycling region in China[J]. Chemosphere, 2016,150: 545-550.
2	ALVES Andreia, COVACI Adrian, VOORSPOELS Stefan. Method development for assessing the human exposure to organophosphate flame retardants in hair and nails[J]. Chemosphere, 2017, 168: 692-698.
3	屈子涵, 唐玉霖, 秦晓, 等. 我国水环境中主要阻燃剂及其处理[J]. 化工进展, 2020, 39(S1): 250-255.
	QU Zihan, TANG Yulin, QIN Xiao, et al. Main flame retardants in China's water environment and their treatment[J]. Chemical Industry and Engineering Progress, 2020, 39(S1): 250-255.
4	WANG Xin, ZHU Qingqing, YAN Xueting, et al. A review of organophosphate flame retardants and plasticizers in the environment: Analysis, occurrence and risk assessment[J]. The Science of the Total Environment, 2020, 731: 139071.
5	LI Jun, YU Nanyang, ZHANG Beibei, et al. Occurrence of organophosphate flame retardants in drinking water from China[J]. Water Research, 2014, 54: 53-61.
6	VAN DER VEEN Ike, DE BOER Jacob. Phosphorus flame retardants: Properties, production, environmental occurrence, toxicity and analysis[J]. Chemosphere, 2012, 88(10): 1119-1153.
7	LAI Nelson L S, KWOK Karen Y, WANG Xinhong, et al. Assessment of organophosphorus flame retardants and plasticizers in aquatic environments of China (Pearl River Delta, South China Sea, Yellow River Estuary) and Japan (Tokyo Bay)[J]. Journal of Hazardous Materials, 2019, 371: 288-294.
8	CAO Shuxia, ZENG Xiangying, SONG Han, et al. Levels and distributions of organophosphate flame retardants and plasticizers in sediment from Taihu Lake, China[J]. Environmental Toxicology and Chemistry, 2012, 31(7): 1478-1484.
9	高小中, 许宜平, 王子健. 有机磷酸酯阻燃剂的环境暴露与迁移转化研究进展[J]. 生态毒理学报, 2015, 10(2): 56-68.
	GAO Xiaozhong, XU Yiping, WANG Zijian. Progress in environment exposure, transport and transform of organophosphorus flame retardants[J]. Asian Journal of Ecotoxicology, 2015, 10(2): 56-68.
10	BAI Xueyuan, LU Shaoyou, XIE Lei, et al. A pilot study of metabolites of organophosphorus flame retardants in paired maternal urine and amniotic fluid samples: Potential exposure risks of tributyl phosphate to pregnant women[J]. Environmental Science: Processes & Impacts, 2019, 21(1): 124-132.
11	MSER Virginia C, PHILLIPS Pamela M, HEDGE Joan M, et al. Neurotoxicological and thyroid evaluations of rats developmentally exposed to tris(1,3-dichloro-2-propyl)phosphate (TDCIPP) and tris(2-chloro-2-ethyl)phosphate (TCEP)[J]. Neurotoxicology and Teratology, 2015, 52: 236-247.
12	DU Zhongkun, WANG Guowei, GAO Shixiang, et al. Aryl organophosphate flame retardants induced cardiotoxicity during zebrafish embryogenesis: By disturbing expression of the transcriptional regulators[J]. Aquatic Toxicology, 2015, 161: 25-32.
13	CRUMP Doug, CHIU Suzanne, KENNEDY Sean W. Effects of tris(1,3-dichloro-2-propyl) phosphate and tris(1-chloropropyl) phosphate on cytotoxicity and mRNA expression in primary cultures of avian hepatocytes and neuronal cells[J]. Toxicological Sciences, 2012, 126(1): 140-148.
14	FARHAT Amani, BUICK Julie K, WILLIAMS Andrew, et al. Tris(1,3-dichloro-2-propyl) phosphate perturbs the expression of genes involved in immune response and lipid and steroid metabolism in chicken embryos[J]. Toxicology and Applied Pharmacology, 2014, 275(2): 104-112.
15	HONG Xiangsheng, CHEN Rui, HOU Rui, et al. Triphenyl phosphate (TPHP)-induced neurotoxicity in adult male Chinese rare minnows (Gobiocypris rarus)[J]. Environmental Science & Technology, 2018, 52(20): 11895-11903.
16	YANG Liansheng, HUANG Chuyi, YIN Ze, et al. Rapid electrochemical reduction of a typical chlorinated organophosphorus flame retardant on copper foam: Degradation kinetics and mechanisms[J]. Chemosphere, 2021, 264: 128515.
17	YU Xiaolong, YIN Hua, YE Jinshao, et al. Degradation of tris-(2-chloroisopropyl) phosphate via UV/TiO₂ photocatalysis: Kinetic, pathway, and security risk assessment of degradation intermediates using proteomic analyses[J]. Chemical Engineering Journal, 2019, 374: 263-273.
18	SONG Qingyun, FENG Yiping, LIU Guoguang, et al. Degradation of the flame retardant triphenyl phosphate by ferrous ion-activated hydrogen peroxide and persulfate: Kinetics, pathways, and mechanisms[J]. Chemical Engineering Journal, 2019, 361: 929-936.
19	QIN Pan, LU Shaoyong, LIU Xiaohui, et al. Removal of tri-(2-chloroisopropyl) phosphate (TCPP) by three types of constructed wetlands[J]. Science of the Total Environment, 2020, 749: 141668.
20	LIU Ying, YIN Hua, WEI Kun, et al. Biodegradation of tricresyl phosphate isomers by Brevibacillus brevis: Degradation pathway and metabolic mechanism[J]. Chemosphere, 2019, 232: 195-203.
21	WANG Junhuan, KHOKHAR Ibatsam, REN Chao, et al. Characterization and 16S metagenomic analysis of organophosphorus flame retardants degrading consortia[J]. Journal of Hazardous Materials, 2019, 380: 120881.
22	WANG Junhuan, HLAING Thet Su, May Thet NWE, et al. Primary biodegradation and mineralization of aryl organophosphate flame retardants by Rhodococcus-Sphingopyxis consortium[J]. Journal of Hazardous Materials, 2021, 412: 125238.
23	NASIRI Jaber, MOTAMEDI Elaheh, NAGHAVI Mohammad Reza, et al. Removal of crystal violet from water using β-cyclodextrin functionalized biogenic zero-valent iron nanoadsorbents synthesized via aqueous root extracts of Ferula persica [J]. Journal of Hazardous Materials, 2019, 367: 325-338.
24	Sungjun BAE, COLLINS Richard N, David WAITE T, et al. Advances in surface passivation of nanoscale zerovalent iron: A critical review[J]. Environmental Science & Technology, 2018, 52(21): 12010-12025.
25	LI Xi, LIU Ling. Recent advances in nanoscale zero-valent iron/oxidant system as a treatment for contaminated water and soil[J]. Journal of Environmental Chemical Engineering, 2021, 9(5): 106276.
26	LI Yaru, ZHAO Heping, ZHU Lizhong. Remediation of soil contaminated with organic compounds by nanoscale zero-valent iron: A review[J]. Science of the Total Environment, 2021, 760: 143413.
27	LI Dan, ZHONG Yin, ZHU Xifen, et al. Reductive degradation of chlorinated organophosphate esters by nanoscale zerovalent iron/cetyltrimethylammonium bromide composites: Reactivity, mechanism and new pathways[J]. Water Research, 2021, 188: 116447.
28	LI Dan, ZHONG Yin, ZHU Xifen, et al. Enhanced reactivity of iron monosulfide towards reductive transformation of tris(2-chloroethyl) phosphate in the presence of cetyltrimethylammonium bromide[J]. Environmental Pollution, 2020, 262: 114282.
29	WANG Wei, ZHOU Shuangxi, LI Rui, et al. Preparation of magnetic powdered carbon/nano-Fe₃O₄ composite for efficient adsorption and degradation of trichloropropyl phosphate from water[J]. Journal of Hazardous Materials, 2021, 416: 125765.
30	韩文亮, 陈海明, 陈兴童. 改性零价铁降解多溴二苯醚的研究进展[J]. 环境化学, 2017, 36(7): 1474-1483.
	HAN Wenliang, CHEN Haiming, CHEN Xingtong. Research progress on the degradation of polybrominated diphenyl ethers by modified zero valent iron[J]. Environmental Chemistry, 2017, 36(7): 1474-1483.
31	LIU Nuo, LIU Jing, WANG Hong, et al. Microbes team with nanoscale zero-valent iron: A robust route for degradation of recalcitrant pollutants[J]. Journal of Environmental Sciences, 2022, 118: 140-146.
32	XU Guiying, WANG Jiangbo, LU Mang. Complete debromination of decabromodiphenyl ether using the integration of Dehalococcoides sp. strain CBDB1 and zero-valent iron[J]. Chemosphere, 2014, 117: 455-461.
33	LIAN Wenjie, YI Xiaoyun, HUANG Kaibo, et al. Degradation of tris(2-chloroethyl) phosphate (TCEP) in aqueous solution by using pyrite activating persulfate to produce radicals[J]. Ecotoxicology and Environmental Safety, 2019, 174: 667-674.
34	LING Chen, WU Shuai, DONG Tailu, et al. Sulfadiazine removal by peroxymonosulfate activation with sulfide-modified microscale zero-valent iron: Major radicals, the role of sulfur species, and particle size effect[J]. Journal of Hazardous Materials. 2022, 423: 127082.
35	XU Hao, GAO Mengxi, HU Xi, et al. A novel preparation of S-nZVI and its high efficient removal of Cr(Ⅵ) in aqueous solution[J]. Journal of Hazardous Materials, 2021, 416: 125924.
36	TANG Chenliu, WANG Xingyu, ZHANG Yufei, et al. Corrosion behaviors and kinetics of nanoscale zero-valent iron in water: A review[J]. Journal of Environmental Sciences, 2024, 135: 391-406.
37	HAO Mengjie, GAO Pan, YANG Dian, et al. Highly efficient adsorption behavior and mechanism of urea-Fe₃O₄@LDH for triphenyl phosphate[J]. Environmental Pollution, 2020, 267: 114142.
38	LIU Biming, LIU Zhenxue, YU Peng, et al. Enhanced removal of tris(2-chloroethyl) phosphate using a resin-based nanocomposite hydrated iron oxide through a Fenton-like process: Capacity evaluation and pathways[J]. Water Research, 2020, 175: 115655.
39	TAKAHASHI Shouji, OBANA Yuki, OKADA Shohei, et al. Complete detoxification of tris(1,3-dichloro-2-propyl) phosphate by mixed two bacteria, Sphingobium sp. strain TCM1 and Arthrobacter sp. strain PY1[J]. Journal of Bioscience and Bioengineering, 2012, 113(1): 79-83.
40	JI Qiuyi, HE Huan, GAO Zhanqi, et al. UV/H₂O₂ oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation[J]. Journal of Environmental Sciences, 2020, 98: 55-61.
41	CAO Zhen, LIU Xue, XU Jiang, et al. Removal of antibiotic florfenicol by sulfide-modified nanoscale zero-valent iron[J]. Environmental Science & Technology, 2017, 51(19): 11269-11277.
42	LI Qian, CHEN Zhongshan, WANG Huihui, et al. Removal of organic compounds by nanoscale zero-valent iron and its composites[J]. Science of the Total Environment, 2021, 792: 148546.

[1]	刘君, 胥志祥, 朱春游, 岳中秋, 潘学军. 典型环境微塑料的微生物降解途径及分子机制[J]. 化工进展, 2024, 43(7): 4059-4071.
[2]	董晓涵, 田月, 苏毅. 含钛高炉渣制备复合吸附剂及其铬吸附性能[J]. 化工进展, 2024, 43(3): 1552-1564.
[3]	王胜楠, 郑旭. 空气取水用活性炭纤维复合吸附剂的研究[J]. 化工进展, 2023, 42(10): 5567-5573.
[4]	付佳, 谌伦建, 徐冰, 华绍烽, 李从强, 杨明坤, 邢宝林, 仪桂云. 模拟煤炭气化废水中苯酚的微生物降解[J]. 化工进展, 2023, 42(1): 526-537.
[5]	刘雅娟. 浸没式PAC-AMBRs系统中PAC缓解膜污染的研究进展[J]. 化工进展, 2023, 42(1): 457-468.
[6]	王晶, 倪金荧, 王利群, 卿青, 严生虎, 张跃. 一株木质素降解细菌的筛选及其降解途径[J]. 化工进展, 2021, 40(7): 4021-4026.
[7]	孙荣岳, 彭超, 陈宇皇, 朱洪亮. 镁负载CaO基吸附剂捕集CO₂性能及抗烧结机理[J]. 化工进展, 2021, 40(11): 6385-6392.
[8]	王令宝1，张刚2，卜宪标1，李华山1，3. 制冷用木屑基质复合吸附剂的制备及性能测试[J]. 化工进展, 2013, 32(06): 1357-1362.

硫化零价铁-微生物复合吸附剂对磷酸三(2-氯乙基)酯的吸附-降解机制

Adsorption-degradation mechanism of tris(2-chloroethyl)phosphate by a composite adsorbent of zero-valent iron sulfide and microorganism

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 42

相关文章 8

编辑推荐

Metrics

本文评价