Research progress on pretreatment techniques for alkylphenols in environmental water
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摘要:
烷基酚化合物作为一类典型的环境内分泌干扰物,可在水环境中长期稳定存在,已成为国内外众多学者研究的焦点之一。通过调研近年来国内外环境水体中烷基酚污染状况,针对其前处理技术进行了综述,重点介绍了环境水体中烷基酚分析检测过程中常用的液液萃取、固相萃取、固相微萃取等前处理技术的原理、特点、影响因素及应用范围等。经梳理和分析相关文献,得出以下结论:1)烷基酚在国内外各类水环境介质中被广泛检出,浓度范围一般为未检出(ND)~几千ng/L,易吸附在水中悬浮物或胶体颗粒上,亟须建立可靠、高效、快速的前处理技术,为其在水体中的准确定性和定量分析奠定良好的基础;2)与固相微萃取和搅拌棒吸附萃取相比,液液萃取技术和固相萃取技术在回收率、精密度和稳定性方面更具优势,已被多个国家应用于水质烷基酚的标准分析方法中。未来应加强填料萃取容量和选择性、涂层耐用性、多种萃取技术联用等方面研究,以建立快速高效、微型化、无溶剂或少溶剂化、对环境友好、自动化的前处理技术;加强烷基酚化合物的管理,建议将其纳入水质质量标准、排放标准等。
Abstract:As a kind of typical environmental endocrine-disrupting chemicals, alkylphenols can exist stably in the water environment for a long time, and have become great-concern substances by environmental scholars at home and abroad. On the basis of recent literature on the pollution of alkylphenols in environmental water, the principal pretreatment techniques were reviewed, of which commonly used in the analysis and detection of alkylphenol in environmental water were emphatically expounded, including liquid-liquid extraction (LLE), solid-phase extraction (SPE), solid phase micro-extraction (SPME), and so on. The principle, characteristics, influencing factors and practical application of the above methods were introduced. The results showed: 1) Alkylphenols were widely detected in various environmental water at home and abroad, and concentrations were generally between undetected (ND) and several thousand ng/L, which were easy to be adsorbed on suspended solids or colloidal particles in water. It was urgent to establish reliable, efficient and fast pretreatment techniques to lay a good foundation for the accurate determination and quantitative analysis of alkylphenols in water. 2) Compared with SPME and stir bar adsorption extraction, LLE and SPE were superior in the aspect of recovery rate, precision and stability, and both had been applied in the national standard analysis methods of alkylphenols in environmental water in many countries. In the future, research should be strengthened on the extraction capacity and selectivity of fillers, the durability of coatings, and the combination of multiple extraction techniques, to establish rapid, efficient, miniaturized, solvent-free or less solvation, environmentally friendly and automated pretreatment techniques. Also, the management of alkylphenols should be strengthened, being integrated into the water quality standards, discharge standards, etc.
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Key words:
- alkylphenols /
- water /
- pretreatment techniques /
- liquid-liquid extraction /
- solid-phase extraction
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表 1 环境水体中烷基酚检出浓度
Table 1. Contents of alkylphenols detected in environmental water
ng/L 采样区域 壬基酚浓度 辛基酚浓度 国内 长江口[3] 14.09~173.09 珠江河网[6] 27.20~824.18 1.11~57.19 东江[7] 14.5~2 908.4 1.60~10.54 太湖[8] 0~121 0~8.14 贾鲁河[9] 75.2~1 520 20.9~63.2 溪流河[10] ND~6 804.13 ND~487.6 南四湖[11] 6.9~1 825.1 20.29~381.05 墨水湖[12] 343 9.3 石老人海[13] 130 130 海河[14] 47.80~358.40 5. 06~23. 60 胶州湾[3] 20.2~268.7 国外 美国San Francisco Estuary[15] 4 韩国Saemangeum Bay[16] 4.5~246.7 匈牙利 Balato Lake[17] 17~41 西班牙Llobregat River[18] ND~644 000 希腊Thessaloniki Coast [19] 181~915 8~29 表 2 环境水体中烷基酚常用前处理技术优缺点
Table 2. Advantages and disadvantages of principal pretreatment techniques for alkylphenols in environmental water
前处理技术 优点 缺点 液液萃取(LLE)[22-31] 回收率高,重现性好,操作简便,成本低廉;可萃取水样的烷基酚浓度范围较宽,对基质复杂的生活污水萃取效果好 萃取水样体积一般≤500 mL,有机溶剂使用量≥60 mL;费时,易乳化 固相萃取(SPE)[32-47] 具有富集和净化的双重功效;商品化程度高,选择性强,操作简单;溶剂使用量10 mL左右,可富集痕量样品,可消除乳化现象;易于自动化,可浓缩体积为2 L的水样 操作步骤繁琐,富集效率波动较大,成本较高;高浓度样品易穿透固相萃取柱 固相微萃取
(SPME)[48-51]具有固相萃取技术所有的优点,且分析时间短,无溶剂化,对环境友好 商品化装置成本较高,纤维涂层种类不够丰富 搅拌棒吸附萃取(SBSE)[52-54] 分析时间短,无溶剂化;灵敏度高,检测限可达到ng/L水平 商品化装置成本较高,纤维涂层种类不够丰富 表 3 SPE在水体中烷基酚前处理过程中的应用
Table 3. Application of SPE for alkylphenols pretreatment in environmental water
烷基酚种类 萃取柱类型 洗脱剂(体积比) 仪器方法 数据来源 4-叔辛基酚、4-壬基酚、4-正辛基酚 ENVI ChromP 丙酮-二氯甲烷
(4∶1)UPLC-MS/MS 文献[25] 4-叔丁基酚、4-正丁基酚、壬基酚、4-叔辛基酚、4-己基酚、2,4-二叔戊基苯酚 HLB 甲醇 HPLC-MS/MS 文献[28] 辛基酚、壬基酚 HLB 乙酸乙酯 GC-MS/MS 文献[37] 4-仲丁基酚、2,4-二叔丁基酚、2,6-二叔丁基-4-甲基酚、
4-叔辛基酚、4 -正壬基酚HLB 10%甲醇-甲基
叔丁基醚GC/MS 文献[38] 壬基酚、辛基酚 HLB 甲醇、二氯甲烷 GC-MS(NCI) 文献[39] 4-叔辛基酚、4-正辛基酚、4-正壬基酚 HLB 甲醇-二氯甲烷(1∶4) HPLC/FLD 文献[40] 4-正辛基酚、壬基酚、4-叔辛基酚 HLB 甲醇 HPLC-MS/MS 文献[41] 壬基酚 Cleanert PEP 甲醇-二氯甲烷
(1∶1)HPLC-MS/MS 文献[42] 壬基酚、辛基酚 C18 甲醇 HPLC-MS 文献[43] 4-叔丁基酚、4-正丁基酚、4-正戊基酚、4-正己基酚、
4-叔辛基酚、4-正庚基酚、4-正辛基酚、4-正壬基酚PSD 甲醇、二氯甲烷 HPLC/UV 文献[44] 4-叔丁基酚、4-正丁基酚、4-正戊基酚、4-正己基酚、
4-叔辛基酚、4-正庚基酚、4-正辛基酚、4-正壬基酚PSD 甲醇、二氯甲烷 HPLC/FLD 文献[44] 壬基酚、4-叔辛基酚、4-正辛基酚 HLB 正己烷-乙醚(3∶2) HPLC/DAD 文献[45] 4-叔辛基酚、4-正壬基酚 HLB、弗罗里硅土 甲醇 HPLC-MS/MS 文献[46] -
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