Laser Induced Fluorescence for In Situ Detection of Typical Heavy Metals in Groundwater
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摘要:
对地下水重金属污染进行现场检测，是快速识别重金属种类和评价污染程度的重要手段。激光诱导荧光技术(LIF)利用特定荧光探针，在目标重金属存在下，通过激光诱导荧光探针产生/猝灭荧光，从而完成对重金属的识别和检测，具有快速甄别地下水重金属污染特性和无损获取其价态的优势。本文在简述LIF检测重金属原理和LIF原位检测地下水重金属装备基础上，重点从荧光探针合成及其在重金属传感检测方法的构建上总结了基于不同荧光探针的LIF现场检测重金属的研究进展。目前可用于重金属检测的荧光探针包括以小分子探针、有机大分子和聚集诱导发光为主的有机荧光探针和以金纳米簇、量子点和金属有机框架材料为代表的纳米荧光探针。这些探针的合成及其对应的传感检测方法的构建表明LIF技术在地下水重金属检测中具有巨大优势。而针对地下水重金属检测的LIF设备研发方面的成果虽不如荧光传感检测方法丰富，但已研制出部分重金属的传感器和检测装备，表现出良好的应用前景。未来研究将会聚焦在地下水重金属主控因子识别和抗干扰技术研发、荧光探针合成与LIF检测方法构建、重金属传感部件和检测装备集成研制，以及检测技术标准化，为后续场地地下水典型重金属LIF检测技术的研究提供参考。
Abstract:On-site detection of heavy metals in groundwater is important to quickly evaluate pollution. Laser induced fluorescence (LIF) utilizes specific fluorescent probes to generate/quench fluorescence in the presence of heavy metals, thereby achieving heavy metals detection, which can quickly identify heavy metals and non-destructively obtain their valence states. This work summarizes the principle and equipment of, and its application for, in situ detection of typical heavy metals in groundwater. At present, LIF probes used for heavy metal detection include organic fluorescent probes mainly composed of small molecule probes, macromolecules, and AIE probes, as well as nanomaterial probes represented by gold nanoclusters, QDs, and MOFs. These synthesized probes and the corresponding constructed sensors indicate that LIF holds significant advantages in heavy metal detection in groundwater. Although the achievements in the development of LIF equipment for heavy metal detection in groundwater are not as rich as those in sensing methods, LIF equipment for several heavy metals have been developed, demonstrating good application prospects. Future research will focus on identifying the controlling factors of heavy metals in groundwater and developing anti-interference techniques, synthesizing novel fluorescent probes for LIF sensor, integrating sensing components into LIF equipment, and standardizing the LIF detection process. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202402230018 .-
Key words:
- groundwater /
- heavy metals /
- laser induced fluorescence /
- fluorescent probe /
- on-site detection
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表 1 荧光探针检测重金属离子(有机荧光探针和纳米荧光探针)
Table 1. Fluorescent probes (organic and nanomaterial fluorescent probes) for the detection of heavy metals
荧光探针
材料类型荧光探针 识别元件 靶标 检出限 线性范围 样品 优点 缺点 参考
文献有机
荧光探针
材料罗丹明衍生物 螺旋内酰胺 Pb2+ 0.56μg/L 0.21～210μg/L 海产品 可视化，检测范围宽 合成复杂 ［25］ 喹啉类 羰基 Cd2+ 132μg/L / 活细胞 荧光稳定 低灵敏度 ［26］ 香豆素类 硫代碳酸盐 Hg2+ 1678.3μg/L / 河水 高特异性 低灵敏度 ［27］ 适配体基 三螺旋核酸分子 As(Ⅲ) 5ng/L 10ng/L～10mg/L 湖水 高特异性，高灵敏度和
检测范围宽修饰复杂 ［28］ Pb2+适配体 Pb2+ 12.22μg/L 20.7～518.0μg/L 茶叶 高特异性，合成简单 成本较高 ［29］ AIE分子 萘酰亚胺 Hg2+ 4.35μg/L 20.7～103.6μg/L 湖水 重复性好，特异性强 线性范围窄 ［30］ 偶氮四唑 Hg2+ 0.394μg/L 79.665μg/L～2.072mg/L 地下水 荧光稳定，特异性强 抗干扰能力弱 ［31］ 改性壳聚糖 氨基、羟基 Hg2+/Hg+ 126.4/97.4μg/L / / 有机可溶，抗干扰能力和
高重复性好合成复杂，成本高 ［32］ 纳米
荧光探针
材料碳量子点 羟基、羧基 Cr6+ 3.7mg/L 5～200mg/L 井水和湖水 环境友好 低灵敏度，线性范围窄 ［33］ Cu@AuNCs 胸腺嘧啶 Hg2+ 1.385μg/L 140.8～1971.3μg/L 水产品 特异性强，稳定性好 / ［34］ AuNCs 胸腺嘧啶 Hg2+ 0.59μg/L 2.8～84.486μg/L 河水和湖水 高灵敏度，高选择性 线性范围窄 ［35］ UCNPs-AuNCs UCNPs Pb2+ 0.216μg/L 0～2.63μg/L 污水 高选择性(可检测复合
金属离子中的Pb2+)/ ［36］ AuNCs 适配体 Pb2+ 14.99ng/L 26.3～52595.8 ng/L 自来水 高灵敏度 检测时间长 ［37］ N-GQDs 羟基 Fe3+ 72.99μg/L 0～81102μg/L 水溶液 量子产率高，检测时间短 灵敏度低 ［38］ CQDs-AgNPs AgNPs Hg2+ 0.02816μg/L 0.14081～140.810μg/L 湖水和废水 量子产率高，重复性好 / ［39］ ZnSe QDs 四乙氧基硅烷 Pb2+ 0.335μg/L 1～60μg/L 海水和湖水 重复性好，多通道检测 合成复杂 ［40］ N-CQDs 羟基、羧基 Pb2+ 0.507μg/L 0～10.52μg/L 自来水和池塘水 高灵敏度，抗干扰能力强 / ［41］ ZIF-8 适配体 Cd2+ 0.018ng/L 0.02364～28.37ng/L 自来水 超高灵敏度 / ［42］ 2D-MOF 适配体 Pb2+ 0.174μg/L 0.263～52.6μg/L 自来水 高选择性，检测时间短 / ［43］ ZnMOF-74 酚羟基 Fe3+ 2.22μg/L 5.55～5554.34μg/L 河水 高选择性 灵敏度低 ［44］ Eu3+@UIO-66 2，6-二羧基吡啶 Hg2+ 2.326μg/L 2.816～70.4μg/L 水溶液 稳定性好，特异性强 / ［45］ 
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