基于贻贝指示的海洋微塑料污染生物监测前处理技术评估与优化

黄辉; 吴桢; 宋凯

基于贻贝指示的海洋微塑料污染生物监测前处理技术评估与优化

浙江省海洋水产研究所，浙江省海洋渔业资源可持续利用技术研究重点实验室，浙江舟山 316021

基金项目: 浙江省科学技术厅院所项目（HYS-CZ-202321）。

详细信息

作者简介:
黄辉（1991—），男，工程师，从事海洋渔业环境监测和修复研究。E-mail：352477568@qq.com

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出版历程
- 收稿日期: 2024-08-21
- 修回日期: 2024-12-18
- 网络出版日期: 2025-01-23

Evaluation and optimization of pretreatment technology for biological monitoring of marine microplastic pollution based on mussel indicator

Zhejiang Marine Fisheries Research Institute, Key Laboratory of Sustainable Utilization of Technology Research for Fishery Resource of Zhejiang Province, Zhoushan 316021, China

摘要

摘要: 基于贻贝指示的海洋微塑料污染生物监测是一种具有广阔应用前景的监测方法，然而目前该法前处理技术包含贻贝组织消解和微塑料密度分离操作多样，且各操作方案的科学性有待验证，导致利用该法得到的海洋微塑料污染监测结果准确性难以保证且数据不易对比。为全面评估多种贻贝组织消解和微塑料密度分离操作的准确性，并获得一种高效经济和可靠的前处理技术方案，本研究开展4种常见消解法（混合酸消解法、氢氧化钾消解法、芬顿消解法和蛋白酶K消解法）对比试验和3种浮选液（氯化钠饱和溶液、碘化钠饱和溶液和甲酸钾饱和溶液）微塑料密度分离试验，评估不同消解法对贻贝组织消解效率和对海洋中常见微塑料的形貌、光谱特征和回收率的影响及不同浮选液的微塑料分离效果，并通过单因素和响应面试验对消解条件进行优化。结果表明，芬顿消解法兼具对贻贝组织的高消解性和对微塑料的低破坏性，可作为优选消解方法，且经优化后，该法在H₂O₂（30%）体积40 mL，Fe²⁺浓度0.020 mol/L，温度59℃，pH 3.7和消解时间24 h条件下，对10 g贻贝组织的消解率达96.7%。同时本研究证实甲酸钾饱和溶液可替代氯化钠和碘化钠饱和溶液，用于高效分离提取消解液中的微塑料。以上研究的开展为基于贻贝指示的海洋微塑料污染生物监测前处理技术完善和标准化提供参考。
- 海洋微塑料 /
- 生物监测 /
- 前处理技术 /
- 芬顿消解法 /
- 甲酸钾
Abstract: Biological monitoring of marine microplastic pollution based on mussel indicator is a monitoring method with broad application prospects. However, the current pretreatment process includes a variety of mussel tissue digestion and microplastic density separation technologies, and the scientific nature of pretreatment technology has yet to be verified, which makes it difficult to guarantee the accuracy of marine microplastic pollution monitoring results obtained by this method and the data are difficult to compare. In order to comprehensively evaluate the accuracy of multiple mussel tissue digestion and microplastic density separation operations and to obtain a cost-effective and reliable pretreatment technology, comparison tests of 4 common digestion methods (mixed acid digestion, potassium hydroxide digestion, Fenton digestion and protease K digestion) and density separation tests of 3 microplastic flotation fluids (sodium chloride saturated solution, sodium iodide saturated solution and potassium formate saturated solution) were carried out. The effects of different digestion methods on the digestion efficiency of mussel tissue and on the morphology, spectral characteristics and recovery rate of common microplastic in the ocean, as well as the separation effect of microplastic in different flotation fluids were evaluated, and the digestion conditions were optimized by single factor and response surface tests. The results showed that the Fenton digestion method had both efficient digestion of mussel tissue and low destructive effect on microplastic, and could be used as the optimal method for digestion of mussel tissue. After optimization, under the conditions of H₂O₂ (30%) volume 40 mL, Fe²⁺ concentration 0.020 mol/L, temperature 59℃, pH 3.7 and digestion time 24 h, the digestion rate of 10 g mussel tissue reached 96.7%. At the same time, this study confirmed that potassium formate saturated solution could replace sodium chloride and sodium iodide saturated solution as the flotation fluid with high efficiency. The development of the above research provides a reference for the improvement and standardization of the pretreatment technology for biological monitoring of marine microplastic pollution based on mussel indicator.
- biological monitoring /
- marine microplastic /
- pretreatment technology /
- Fenton digestion /
- potassium formate

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图 1 贻贝体内微塑料的分析流程

Fig. 1 Analytical process of microplastic in mussels

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图 2 不同消解法的贻贝组织消解效率

Fig. 2 Digestion efficiency of mussel tissue by different digestion treatments

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图 3 PC，PET和PS 颗粒消解前后扫描电镜图

注：1-3分别为PC，PET和PS；A-E分别为消解前，硝酸-高氯酸消解，10%KOH消解，芬顿消解和蛋白酶K消解

Fig. 3 Scanning electron microscope of PC, PET and PS particles before and after digestion

Note: 1-3 are respectively PC, PET and PS; A-E refer to pre digestion, nitric acid-perchloric acid digestion, 10%KOH digestion, Fenton digestion and protease K digestion, respectively

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图 4 PC颗粒消解前后红外光谱图

Fig. 4 Fourier infrared spectroscopy of PC before and after digestion

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图 5 不同因素对芬顿消解效果的影响

Fig. 5 Effects of different factors on Fenton digestion

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图 6 各因素交互作用对芬顿消解效率的影响

Fig. 6 Influence of interactions of independent variables on digestion rate of Fenton

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图 7 不同饱和溶液的微塑料提取率

Fig. 7 Extraction efficiency of microplastic using different saturated solutions

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表 1 单因素试验因子水平

Tab. 1 Different factor levels in single factor experiments

水平	因素
水平	温度/℃	pH	Fe²⁺浓度/mol·L⁻¹	时间/h
1	45	2.5	0.005	6
2	50	3.5	0.010	12
3	55	4.5	0.015	24
4	60	5.5	0.020	36
5	65	6.5	0.025	48

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表 2 响应面优化试验因素与水平设计

Tab. 2 Experimental factors and level design of response surface optimization

水平	因素
水平	A 温度/℃	B pH	C Fe²⁺浓度/mol·L⁻¹
−1	55	2.5	0.010
0	60	3.5	0.015
1	65	4.5	0.020

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表 3 不同消解法对6种微塑料回收率（%）的影响

Tab. 3 Effect of different digestion treatments on recovery rates (%) of 6 kinds of microplastic

消解方法	PC	PE	PET	PP	PS	PVC
硝酸-高氯酸	91.7±3.1	93.2±1.8	83.8±3.0	94.2±1.3	94.3±2.5	92.5±1.3
10%KOH	63.0±5.3	89.3±1.6	77.7±3.5	91.7±1.5	93.7±2.1	92.6±3.6
芬顿	92.0±1.7	93.7±2.5	92.3±2.3	92.0±1.7	93.0±2.0	91.3±3.2
蛋白酶K	93.3±2.1	94.3±2.1	94.1±0.1	92.7±1.5	94.7±2.3	93.7±3.1

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