消解和电化学检测饮用水二氧化锰颗粒的方法

doi:10.61558/2993-074X.3572

摘要/Abstract

摘要：

开发饮用水中污染物的检测方法对于确保向消费者提供安全的饮用水至关重要。尽管锰（Mn）过去仅被认为是影响外观的问题，但近年来的流行病学数据表明，锰对人体神经系统具有负面影响，尤其是对儿童的。这一发现促使加拿大卫生部和世界卫生组织（WHO）制定了新的健康风险的管理指南。在饮用水中，锰主要以二价锰（Mn(II)）和四价锰（Mn(IV)）的形式存在，并通常依据总锰含量进行监管。目前尚无文献报道使用电分析方法对颗粒态锰进行检测。在这份研究中，我们优化了一种使用亚铁离子（Fe²⁺）消解不溶性二氧化锰（MnO₂）颗粒的程序，以便使用循环伏安法（CV）进行锰的检测。研究并优化了Fe²⁺浓度、pH值及消解时间等条件。研究发现，在化学计量比理想与非理想的条件下均可实现MnO₂的消解，但在化学计量比恰当时效果最佳。循环伏安法在使用玻碳电极的条件下，能良好的检测不同浓度的颗粒态锰。经过4.5小时消解后，CV的检出限为0.3 mmol·L^-1；而在24小时消解后，检出限达到0.1 mmol·L^-1。Cu²⁺和Fe³⁺离子的存在会影响该消解和检测方法的效果，表明该方法可能具有多重检测的潜力。同时发现Mn²⁺的存在会增强锰检测信号，说明这个方法具有同时检测可溶性与不溶性锰的潜力。该消解及检测方法简便，为饮用水中总锰的检测提供了新的方法。

关键词: 锰, 饮用水, 循环伏安法, 消解, 二氧化锰

Abstract:

Developing methods for detection contaminants in drinking water is essential to ensuring that safe and acceptable quality drinking water is delivered to consumers. While manganese (Mn) was previously known only as a mere aesthetic issue, recent epidemiological data has shown to have negative neurological effects on humans, especially on children, prompting new health-based guidelines by Health Canada and the World Health Organization. In drinking water, Mn exists predominantly as Mn(II) and Mn(IV), and is regulated based on total Mn levels. Interestingly, measurement of Mn particulate using electroanalytical methods has not yet been reported in the literature. Herein, a digestion procedure for insoluble manganese dioxide (MnO₂) using ferrous (Fe²⁺) ions was optimized in preparation for Mn detection by cyclic voltammetry (CV). Digestion conditions including concentration of Fe²⁺ ions, pH and digestion time were explored and optimized. Digestion of MnO₂ was found to be successful in both perfect and imperfect stoichiometric ratios; however, digestion was shown to be most effective in perfect stoichiometric conditions. CV proved to be an effective technique for the detection of different particulate Mn concentrations with good reproducibility using glassy carbon electrodes. According to the CV data, the detection limits of 0.3 mmol·L^-1 and 0.1 mmol·L^-1 for MnO₂ were determined after the digestion time of 4.5 h and 24 h, respectively. The digestion method, in addition to CV detection, was found to be impacted by the presences of Cu²⁺ and Fe³⁺ ions.This interference suggests that this method may offer value as a multi-plexed technique. The Mn reduction signal was found to be enhanced in the presence of Mn²⁺, indicating that this method has the potential to be used to detect soluble and insoluble Mn species simultaneously. These digestion and detection methods are simple and reproducible methods which introduce the opportunity for total Mn detection in drinking water.

Key words: Manganese, Drinking water, Cyclic voltammetry, Digestion, Manganese dioxide

Kayla Elliott, Sarah Jane Payne, Zhe She. 消解和电化学检测饮用水二氧化锰颗粒的方法[J]. 电化学（中英文）, 2025, 31(11): 2417004.

Kayla Elliott, Sarah Jane Payne, Zhe She. Development of a Digestion Procedure Using Fe²⁺ ions for Electrochemical Detection of MnO₂ Particles in Drinking Water[J]. Journal of Electrochemistry, 2025, 31(11): 2417004.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3572

https://electrochem.xmu.edu.cn/CN/Y2025/V31/I11/2417004

图/表 10

参考文献 56

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Reducing Agent (RA)	MnO₂: RA	MnO₂ Source	Acid	[Acid] (mol·L^–1)	Temperature (^oC)	Time (mins)	Detection Method	Reference
Fe²⁺	1:2	Mn Nodule	H₂SO₄	0.1	25 ^oC	30	AAS	[11]
Fe²⁺	1:2	Mn Nodule	H₂SO₄	Excess	90 ^oC	180	AAS	[12]
Fe⁰	1:2	Mn Nodule	H₂SO₄	1	25 ^oC	30	AAS	[13]
Fe₂O₃	1:2	Mn Nodule	H₂SO₄	1	25 ^oC	40	AAS	[14]
Fe²⁺	1:2	MnO₂ Particles	H₂SO₄	0.016	25 ^oC	1440	CV	This study

[Fe²⁺] (mmol·L^-1)	[MnO₂] (mmol·L^-1)	Current (i) after 4.5-h digestion (μA)	Current (i) after 24-h digestion (μA)
5	2	$6.7\pm 3.2$	$10.9\pm 1.7$
5	4	$15.93\pm 0.54$	$16.00\pm 0.83$
8	2	$2.2\pm 2.1$	$1.6\pm 1.2$
8	4	$13.2\pm 3.0$	$18.03\pm 0.54$
10	2	$1.9\pm 2.0$	$2.5\pm 2.6$
10	4	$3.84\pm 0.83$	$9.5\pm 4.0$
16	2	$0.3\pm 2.6$	$2.0\pm 6.9$
16	4	$6.8\pm 4.2$	$4.41\pm 0.51$

[MnO₂] (mol·L^-1)	[MnO₂] (mg·L^-1)	Current (i) after 4.5-h digestion (μA)	Current (i) after 24-h digestion (μA)
0	0	$0.08\pm 0.13$	$0.113\pm 0.069$
1	87	$0.9\pm 1.2$	$4.8\pm 2.8$
2	174	$6.7\pm 3.2$	$10.9\pm 1.7$
2.5	217	$11.1\pm 1.8$	$14.1\pm 1.4$
3	261	$8.6\pm 2.1$	$11.07\pm 0.53$
4	347	$15.93\pm 0.54$	$16.00\pm 0.83$