温度对氢自养还原去除水中锑酸盐的影响研究

doi:10.19965/j.cnki.iwt.2024-0989

摘要/Abstract

摘要：

氢自养生物还原已被证实可有效用于去除水中污染物锑酸盐，温度作为影响微生物生长与代谢的关键环境因素之一，其对氢自养还原锑酸盐的效能和菌群结构的影响仍需进一步明确。利用氢气（H₂）作为唯一电子供体对微生物进行驯化，在序批式实验模式下，探究了不同温度下氢自养还原过程对水中锑酸盐去除效能及微生物群落结构的变化情况，利用傅里叶红外光谱（FTIR）和X射线光电子能谱（XPS）分析表征反应产物并分析反应机理。实验结果表明，反应适宜温度为30 ℃，当温度从30 ℃降低到10 ℃，Sb（Ⅴ）的去除率下降了52.7%，总Sb（TSb）去除率下降了27.69%；H₂自养生物反硝化还原锑酸盐的过程符合Michaelis-Menten模型，动力学参数q _max为0.040~0.128 mg/（g·h），K_s 为0.004~0.334 mg/L，反应活化能为41.88 kJ/mol；表征分析结果表明，Sb（Ⅴ）被氢自养还原为Sb（Ⅲ），并进一步生成Sb₂O₃沉淀物；在30 ℃条件下，优势菌属为Acinetobacter、Chryseobacterium和Hydrogenophaga，在10 ℃条件下，Acinetobacter仍是最具优势的菌属，而Chryseobacterium和Hydrogenophaga对温度较为敏感，丰度分别降低了16.90%和4.55%。

关键词: 氢自养还原, 温度, 锑酸盐, 动力学分析, 微生物群落结构

Abstract:

Hydrogen autotrophic bioreduction has been proved to be effective for the removal of antimonate in water. As one of the key factors affecting the growth and metabolism of microorganisms, the impact of temperature on the efficacy of hydrogen autotrophic reduction of antimonates and the structure of the bacterial community needs to be further clarified. In this study, hydrogen(H₂) was used as the only electron donor to domesticate the microorganisms,and a sequencing batch bioreactor was established to investigate the effects of hydrogen autotrophic reduction on the removal efficiency of antimonate in water and the structure of microbial community at different temperatures. Fourier transform infrared spectroscopy(FTIR) and X-ray photoelectron spectroscopy(XPS) were used to characterize the reaction products and analyze the mechanism of the reaction. The experimental results showed that the suitable temperature for the reaction was 30 ℃. When the temperature was reduced from 30 ℃ to 10 ℃, the removal of Sb(Ⅴ) was decreased by 52.7%, and the removal of total Sb(TSb) was decreased by 27.69%. The process of H₂ autotrophic biological denitrification for antimonate reduction conformed to the Michaelis-Menten model, with the kinetic parameters were 0.040-0.128 mg/(g·h) for q _max, 0.004-0.334 mg/L for K_s, and the activation energy of the reaction was 41.88 kJ/mol. The results of characterization and analysis showed that Sb(Ⅴ) was autotrophically reduced to Sb(Ⅲ) by hydrogen and further produced Sb₂O₃ precipitates. At 30 ℃, the dominant genera were Acinetobacter, Chryseobacterium and Hydrogenophaga. At 10 ℃, Acinetobacter was still the most dominant genus, while Chryseobacterium and Hydrogenophaga were more sensitive to temperature, with abundance reduced by 16.90% and 4.55%, respectively.

Key words: hydrogen autotrophic reduction, temperature, antimonate, kinetic analysis, microbial community structure

中图分类号:

X703.1

张程炯, 陈相林, 王一朵, 吴斌, 郭东丽, 周全, 沙净, 万东锦. 温度对氢自养还原去除水中锑酸盐的影响研究[J]. 工业水处理, 2025, 45(12): 116-123.

Chengjiong ZHANG, Xianglin CHEN, Yiduo WANG, Bin WU, Dongli GUO, Quan ZHOU, Jing SHA, Dongjin WAN. Study on the effect of temperature on hydrogen autotrophic reduction for antimonate removal from water[J]. Industrial Water Treatment, 2025, 45(12): 116-123.

https://www.iwt.cn/CN/Y2025/V45/I12/116

图/表 12

图1 H₂驯化过程中Sb浓度的变化

Fig.1 Variations of Sb concentration during hydrogen autotrophic acclimation process

表1 驯化过程中锑酸盐去除速率的变化

Table 1 Variations of antimonate reduction rate during acclimation process

驯化周期	反应时间/d	生物量（以VSS计）/（g·L^-1）	平均去除速率/ （mg·g^-1·h^-1）
1	2	5.400	0.189
4	1	4.676	0.434
8	1	4.261	0.480
10	1	3.893	0.512
13	1	3.914	0.491
15	1	4.088	0.472

图2 不同温度下氢自养还原Sb（Ⅴ）动力学拟合

Fig.2 Dynamic fitting of hydrogen autotrophic reduction of Sb（Ⅴ） at different temperatures

表2 不同温度下氢自养还原Sb（Ⅴ）动力学参数

Table 2 Kinetic parameters of hydrogen autotrophic reduction of Sb（Ⅴ） at different temperatures

温度/℃	零级动力学模型		Michaelis-Menten 模型
温度/℃	k ₀/ （mg·g^-1·h^-1）	R ²	q _max/ （mg·g^-1·h^-1）	K_s / （mg·L^-1）	R ²
30	0.659	0.096	0.128	0.108	0.979
20	0.456	0.833	0.102	0.004	0.986
10	0.188	0.985	0.040	0.334	0.987

图3 不同温度下Sb质量浓度的变化

Fig.3 Changes in concentrations of Sb at different temperatures

图4 不同温度下出水pH变化

Fig.4 Changes in pH of effluent at different temperatures

图5 接种污泥和反应产物的FTIR谱图

Fig.5 FTIR spectra of inoculated sludge and reaction products

图6 接种污泥和反应产物的XPS谱图

Fig.6 XPS spectra of inoculated sludge and reaction products

表3 微生物样品的有效序列数及α-多样性评价指标

Table 3 Sample effective sequence number and α-diversity evaluation index

样品	归一化序列数	OTUs	Simpson	Shannon	Chao 1	Coverage
H0	29 201	6 539	0.004	6.5	12 187.0	0.93
H15	29 201	3 771	0.130	3.7	8 131.0	0.96
T30	29 201	1 509	0.940	7.1	2 082.0	0.99
T20	29 201	1 397	0.970	7.3	1 558.2	0.99
T10	29 201	1 755	0.920	7.0	1 536.4	0.98

图7 门水平的微生物群落结构变化

Fig.7 Changes in microbial community structure at phylum level

图8 接种和驯化阶段属水平的微生物群落结构变化

Fig.8 Changes in microbial community structure at genus level in the inoculation and acclimation phases

图9 不同温度下属水平的微生物群落结构变化

Fig.9 Changes in microbial community structure at genus level at different temperatures

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