含硅水铁矿对没食子酸和铜绿假单胞菌还原地下水中Cr(VI)动力学影响

doi:10.13745/j.esf.sf.2025.10.13

摘要/Abstract

摘要：

多酚和铜绿假单胞菌是还原和固定Cr(VI)常用的不易产生二次污染的修复剂。这一过程的动力学受各种环境因素的控制,但这些因素对Cr(VI)修复转化的影响尚不清楚。本研究聚焦于在地下水环境中其表面受硅离子掺杂与改造的水铁矿颗粒,对多酚和细菌还原Cr(VI)的动力学影响。通过构建不同还原六价铬体系(包括二元、三元、四元)的室内对比批实验,探究水铁矿表面的硅离子掺杂程度对该过程的作用。三元体系(含硅水铁矿-多酚或细菌- Cr(VI))显示,多酚与Cr(VI)的快速络合还原显著提升了初期去除效率(最高可达 87%),但后期依赖含硅水铁矿的持续吸附能力;细菌通过分泌胞外代谢产物(EPS)促进 Cr(VI)的还原与稳定化,降低了硅掺杂影响水铁矿对Cr(VI) 吸附的敏感性。四元体系(含硅水铁矿-多酚-细菌- Cr(VI))中,多酚-细菌协同抵消部分硅掺杂的抑制作用,维持更高 Cr(VI) 去除效率,多酚发生降解或被氧化,含硅水铁矿为细菌提供栖息环境。

关键词: 含硅水铁矿, 地下水修复, 六价铬, 多酚和细菌

Abstract:

Polyphenols and Pseudomonas aeruginosa are commonly used remediation agents for reducing and immobilizing Cr(VI) with minimal risk of secondary pollution. The kinetics of this process are influenced by various environmental factors, yet the impact of these factors on the remediation and transformation of Cr(VI) remains poorly understood. This study focuses on the effect of silicon-doped ferrihydrite particles-ubiquitous in groundwater environments-on the kinetics of Cr(VI) reduction by polyphenols and bacteria. Through a series of controlled laboratory batch experiments involving binary, ternary, and quaternary reaction systems, we investigated the influence of the extent of silicon incorporation in ferrihydrite on this process. In ternary systems (comprising silicon-doped ferrihydrite, either polyphenols or bacteria, and Cr(VI)), rapid complexation and reduction of Cr(VI) by polyphenols significantly enhanced the initial removal efficiency (up to 87%), though sustained removal subsequently relied on the adsorption capacity of silicon-doped ferrihydrite. Bacteria facilitated Cr(VI) reduction and stabilization through the secretion of extracellular polymeric substances (EPS), thereby mitigating the inhibitory effect of silicon doping on Cr(VI) adsorption by ferrihydrite. In the quaternary system (silicon-doped ferrihydrite-polyphenols-bacteria-Cr(VI)), the synergistic interaction between polyphenols and bacteria partially counteracted the suppression caused by silicon doping, maintaining a higher Cr(VI) removal efficiency. Within this system, polyphenols were degraded or oxidized, while silicon-doped ferrihydrite provided a habitat for bacterial colonization.

Key words: silicon-doped ferrihydrite, groundwater remediation, hexavalent chromium, polyphenols and bacteria

中图分类号:

X523

张梦凡, 蔡绪贻. 含硅水铁矿对没食子酸和铜绿假单胞菌还原地下水中Cr(VI)动力学影响[J]. 地学前缘, 2026, 33(1): 236-249.

ZHANG Mengfan, CAI Xuyi. Effect of silicon-doped ferrihydrite on the kinetics of Cr(VI) reduction by gallic acid and Pseudomonas aeruginosa in groundwater[J]. Earth Science Frontiers, 2026, 33(1): 236-249.

图/表 12

图1 矿物-有机物-生物协同还原Cr(VI)反应机制

Fig.1 Synergistic Cr(VI) reduction mechanism driven by the mineral-organic-microbial consortium

图2 含硅水铁矿的SEM表征 (a)选定水铁矿的X射线图;(b)红外光谱图;(c)BET和Zeta电位(pH=6)。

Fig.2 SEM characterization of Si-containing ferrihydrite

图3 选定水铁矿样品的SEM图像

Fig.3 SEM images of selected ferrihydrite samples (a)0-SiFh;(b)0.1-SiFh;(c)0.50-SiFh。

图4 含硅水铁矿-GA-Cr(VI)体系Cr(VI)、GA浓度随时间变化

Fig.4 Variations in Cr(VI) and GA concentrations over time in the Si-containing ferrihydrite-GA-Cr(VI) system

表1 不同体系Cr(VI)去除率

Table 1 Cr(VI) removal efficiencies in different systems

体系组成	Si/Fe物质的量之比
体系组成	0	0.1	0.25	0.50
Si-Fh-Cr(VI)	80%	53%	0%	0%
GA-Cr(VI)	52%
Si-Fh-GA-Cr(VI)	87%	54%	46%	42%

图5 含硅水铁矿-细菌-Cr(VI)体系Cr(VI)浓度随时间变化

Fig.5 Cr(VI) concentration versus time in the Si-containing ferrihydrite-bacteria-Cr(VI) system

表2 含硅水铁矿-多酚/细菌-Cr(VI)体系对Cr(VI)还原动力学拟合参数

Table 2 Kinetic fitting parameters for Cr(VI) reduction in the Si-containing ferrihydrite-polyphenol/bacteria-Cr(VI) systems

			第一阶段			第二阶段
动力学模型		体系组成	k₁/h^-1		R²	k₁/h^-1	R²
			k₂/(L·mg^-1·h^-1)		R²	k₂/(L·mg^-1·h^-1)	R²
一级动力学	Si/Fe=0-GA			0.080 6	0.164 9	0.032 2	0.969 4
	Si/Fe=0.1-GA			-0.019 3	0.015 5	0.003 8	0.598 5
	Si/Fe=0.25-GA			-0.015 6	0.011 2	0.001 7	0.112 0
	Si/Fe=0.50-GA			0.008 4	0.003 3	-0.008 4	0.894 0
一级动力学	Si/Fe=0-细菌			0.008 5	0.940 2	0.030 3	0.979 9
	Si/Fe=0.1-细菌			0.008 5	0.986 7	0.026 3	0.990 7
	Si/Fe=0.25-细菌			0.008 6	0.989 9	0.018 9	0.975 8
	Si/Fe=0.50-细菌			0.008 8	0.983 3	0.018 3	0.944 8
二级动力学	Si/Fe=0-GA			0.004 3	0.221 1	0.005 0	0.990 2
	Si/Fe=0.1-GA			-0.001 9	0.100 5	0.000 2	0.485 5
	Si/Fe=0.25-GA			-0.001 6	0.089 0	0.000 1	0.261 4
	Si/Fe=0.50-GA			-0.000 7	0.016 0	-0.000 4	0.894 2
二级动力学	Si/Fe=0-细菌			0.000 5	0.955 6	0.006 0	0.922 7
	Si/Fe=0.1-细菌			0.000 4	0.967 8	0.006 0	0.918 3
	Si/Fe=0.25-细菌			0.000 4	0.991 5	0.003 0	0.904 0
	Si/Fe=0.50-细菌			0.000 4	0.993 3	0.002 7	0.860 8

图6 含硅水铁矿-GA-细菌-Cr(VI)体系Cr(VI)浓度随时间变化

Fig.6 Cr(VI) concentration versus time in the Si-containing ferrihydrite-GA-bacteria-Cr(VI) system

表3 平衡50 h不同体系Cr(VI)去除率

Table 3 Cr(VI) removal efficiency in different systems after 50 h of equilibrium

体系组成	Si/Fe物质的量之比
体系组成	0	0.1	0.25	0.50
Si-Fh-GA- Cr(VI)	88%	53%	48%	43%
Si-Fh-细菌- Cr(VI)	51%	42%	43%	44%
GA-细菌- Cr(VI)	96%
Si-Fh-GA-细菌- Cr(VI)	99%	99%	97%	98%

图7 Si/Fe为0.1或0.50的Si-Fh四元体系反应体系表征结果 (a)反应后紫外谱图;(b)反应后固相Cr元素XPS表征谱图;(c)Si/Fe=0.1反应后固相SEM图;(d)Si/Fe=0.50反应后固相SEM图;(e)体系多酚浓度随时间变化图。

Fig.7 Characterization results of the quaternary Si-Fh systems with Si/Fe ratios of 0.1 and 0.50

表4 含硅水铁矿-GA-细菌-Cr(VI)体系对Cr(VI)还原动力学拟合参数

Table 4 Kinetic-fitting parameters for Cr(VI) reduction in the Si-containing ferrihydrite-GA-bacteria-Cr(VI) system

动力学模型	体系组成	第一阶段		第二阶段
		k₁/h^-1	R²	k₁/h^-1	R²
		k₂/(L·mg^-1·h^-1)	R²	k₂/(L·mg^-1·h^-1)	R²
一级动力学	Si/Fe=0-GA-细菌	0.096 7	0.899 8	0.011 6	0.750 0
	Si/Fe=0.1-GA-细菌	0.077 5	0.870 6	0.017 8	0.939 3
	Si/Fe=0.25-GA-细菌	0.073 7	0.874 5	0.009 8	0.750 0
	Si/Fe=0.50-GA-细菌	0.089 7	0.899 2	—	—
二级动力学	Si/Fe=0-GA-细菌	0.023 3	0.949 0	0.031 6	0.853 3
	Si/Fe=0.1-GA-细菌	0.010 4	0.940 2	0.028 9	0.963 1
	Si/Fe=0.25-GA-细菌	0.009 7	0.943 3	0.013 9	0.805 0
	Si/Fe=0.50-GA-细菌	0.014 1	0.925 8	0.014 9	0.333 0

图8 含硅水铁矿对多酚-细菌协同还原Cr(VI)动力学影响机制

Fig.8 Mechanism by which Si-containing ferrihydrite influences the kinetics of polyphenol-bacteria synergistic Cr(VI) reduction

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