水环境样品中表面活性剂检测方法研究进展

doi:10.3969/j.issn.2097-2806.2023.08.009

Abstract

Abstract:

Surfactants have been widely used in detergents, emulsifiers and other daily chemicals, however, surfactants could cause risks to the ecological environment and human health when discharged with domestic sewage into the water environment if the surfactant concentration were too high. Therefore, it is important to monitor and quantify the surfactants in water environment. Due to the diversity in types and structures of surfactants present in the water environment, as well as the presence of matrix interference, pretreatment such as purification and enrichment is needed and should be combined with accurate instrumental analysis, thus to achieve effective identification and quantification. Herein, the commonly used pretreatment technology for water samples containing surfactants has been reviewed, including liquid-liquid extraction, solid phase extraction, solid phase micro extraction, magnetic solid-phase extraction and ultrasonic-assisted extraction, as well as the analysis methods including two-phase titration, electrochemical analysis, chromatography, spectroscopy, etc. By sorting out the applicable condition, range, and advantages and disadvantages of each method, it is suggested that the selection of pretreatment and detection method depends on the characteristics and concentration of surfactants. It is pointed out that, the technology of on-line extraction and enrichment, the automation and the portable on-site rapid real-time detection are the focuses of future research on surfactant detection. This paper could provide a reference basis for the monitoring and assessment of surfactants in water environment.

Key words: water environment, surfactant, pretreatment, high efficiency and sensitivity

CLC Number:

TQ423

Wang Jiarui,Wei Xiaocheng,Zhang Chunxue,Chen Peizhen,Zheng Xiangqun,Wang Qiang. Research progress on detection methods of surfactants in water samples from environment[J].China Surfactant Detergent & Cosmetics, 2023, 53(8): 925-934.

Figures/Tables 3

Tab. 1

Tab. 2

Extraction methods for surfactants"

方法	物质	萃取剂/物	回收率	优点	缺点
液液萃取法LLE	阴离子和阳离子表面活性剂	甲醇、甲酸铵、乙醇、乙腈、乙酸、戊烷、丙酮、氯仿、三氯甲烷	80%~99% ^[7]	操作简单、适用性广、无需复杂前处理设备	有机溶剂使用量较大，易造成环境污染
液液萃取法LLE	非离子表面活性剂	二氯甲烷、二氯乙烷、乙酸乙酯、甲基叔丁基醚	88% ^[19]	操作简单、适用性广、无需复杂前处理设备	有机溶剂使用量较大，易造成环境污染
固相萃取法SPE	阳离子表面活性剂	十八烷基二氧化硅、氧化铝、改性聚苯乙烯-二乙烯基苯、聚甲基丙烯酸	79%~93% ^[8]	简单、快速、溶剂用量少，制备阶段不需要氯仿等有毒试剂	对样品的透明度要求高
	阴离子表面活性剂	OASISMAX复合阴离子萃取小柱	85.7%~98.4% ^[20]
	非离子表面活性剂	GCB，C₁₈氧化铝，C18+SAXC18+ SCX+SAX	70%~107% ^[21]
固相微萃取法SPME	非离子表面活性剂	纤维如碳蜡-二乙烯基苯（CWAX-DVB）、碳蜡/模板树脂（CWAX-TR）、聚二甲基硅氧烷模板树脂（PDMS-TR）、聚二甲基硅氧烷-二乙烯基苯（PDMS-DVB）和聚丙烯酸酯（PA）		快速、简便、无溶剂，检测限低	定量检测精度不高、可重复性不高、商业可用负载聚合物品种少
磁性固相萃取法MSPE	含氟表面活性剂	磁性纳米复合材料	90.1%~106.7% ^[12]	简便、快速、高效、富集倍数高	广泛适用性较弱，难以大范围推广应用
超声辅助萃取法UAE	离子、非离子表面活性剂	超声波酸化/超声波	（81%±10%）~ （118%±11%） ^[22]	较好的选择性、灵敏度、准确性和精密度	超声有效作用区域为环形，作用不均匀
超滤法UF	离子、非离子表面活性剂	超滤膜		速度快、回收率高、装置简单、流程短	存在浓度极化现象，超滤速度会逐渐减慢
泡沫分离法FF	低浓度离子、非离子表面活性剂		95.99% ^[23]	速度快、回收率高、简单、流程短	不稳定、影响因素多
结晶与沉淀法CP	离子、非离子表面活性剂		>90% ^[18]	简单、流程短	用时较长、效率不高、不稳定、影响因素多

Tab. 2

Tab. 3

Detection methods for surfactants"

方法		适应性	物质	检测限	检测范围	优点	缺点
两相滴定法TT		适合分子结构已知且具备指示剂、显色剂的测试	阴离子表面活性剂、阳离子表面活性剂			操作简单，抗干扰性好，容易识别，费用低廉	需要有毒试剂，单一指示剂易造成结果偏低
电化学分析法 EA	电位滴定法PT	适合样品少、需要在线测定的测试	十二烷基硫酸钠	2.4 μmol/dm³	3~10 000 μmol/dm^{3 [25]}	精密度和准确度高，重复性好、操作简单、快速	电极选择性较差、受沉淀影响大
	电位滴定法PT		十二烷基苯磺酸钠	3.4 μmol/L	5~20 000 μmol/L ^[25]	精密度和准确度高，重复性好、操作简单、快速	电极选择性较差、受沉淀影响大
	离子选择电极法ISE		十二烷基硫酸钠	1.3×10^-6~6.8× 10^-6 mol/L	6.0×10^-7 mol/L ^[28]	处理简单、速度快，耗样少，范围广和灵敏度高，可实现在线监测	只能检测同一类官能团物质，无法定量分析其组分，易受干扰，仪器成本高
	吸附溶出伏安法ASV		十二烷基硫酸钠	1.2 mg/L	0.05~17.5 mg/L ^[29]	灵敏度高、设备简单	选择性较差
	示波极谱法OP		氯化十六烷基吡啶	0.01 mg/L	0~0.6 mg/L ^[31]	终点敏锐，精确度好	仪器价格相对较高
	传感器法SS		十二烷基硫酸盐	3×10^-6 mol/L	10^-3~10^-6 mol/L ^[33]	快速、稳定	选择性较差
色谱法 CA	高效液相色谱法HPLC	适合对检测速度、环保有较高要求的测试	阴离子表面活性剂	5.0 μg/L	20.0~300.0 μg/L ^[35]	选择性、效率高，二次污染少，检出限低	仪器成本高，固有毒性和可燃性
色谱法 CA	气相色谱法GC	适合气体和易挥发且稳定性好的化合物（多种酚类化合物除外）	脂肪烷基二甲基叔胺	0.001~0.002 g/L	0.005~1.0 g/L ^[39]	耗时较少，结果准	需要预处理
	液相色谱-质谱联用法 HPLC-MS	混合表面活性剂	阴离子表面活性剂	2 ng/mL	2~400 ng/mL ^[40]	所需样品量少，快速、灵敏度高	定性能力较差
	气相色谱-质谱联用法GC-MS	适宜测定挥发性较强的非离子表面活性剂（EO 链较短）	油脂化学的非离子、阴离子与部分阳离子表面活性剂			分离能力强，能提供有关烷基链长度、同分异构体分布的信息	成本相对较高
	超临界流体色谱法SFC	阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂	非离子表面活性剂			效率和灵敏度高，规避固有毒性和可燃性	成本相对较高
	薄层层析法TLC	适合多种样品一次性快速测试	阴离子、阳离子和非离子表面活性剂			简便、快速，用样量少	分析成本高
光谱法SA	分光光度法SM	适合分子结构已知且具备络合剂、显色剂的测试	阴离子表面活性剂	1.7×10^-3mg/L	0.2~1.7 mg/L ^[44]	灵敏度高、操作简单、仪器易得、费用较低	方法繁琐耗时，萃取剂毒性大，实际用量大，且只能检测总含量，检测限高
	紫外光谱法UV	适合含有苯环结构等已知化合物中存在发色团分子的表面活性剂	含芳香烃结构表面活性剂			操作简单，灵敏度高	依赖于化合物中存在发色团分子
	荧光分析法FA	适合具有荧光特性的表面活性剂	十二烷基苯磺酸钠	3.5×10^-7mol/L	2.5×10^-7~9.6× 10^-5 mol/L ^[47]	操作简便、快速、精确度高、灵敏度高	适用范围较差
	红外光谱法IR	阴离子、阳离子、非离子表面活性剂	阴离子、阳离子、非离子表面活性剂			简便快速，灵敏度高	缺乏分析微量化合物的适用性，成本高，用水作为溶剂干扰大
	毛细管电泳法CE	适用不同类型表面活性剂分离、分别测试	十二烷基硫酸钠	2.5×10^-6 mol/L	5.0×10^-6~8.0× 10^-3 mol/L ^[54]	操作简单，试样量少，分离效率高，成本较低	分离能力较弱，重现性较差，不能同时检测不同离子类型，不适用于痕量检测
	毛细管电泳法CE	适用不同类型表面活性剂分离、分别测试	十二烷基苯磺酸钠	3.0×10^-6 mol/L	5.0×10^-6~5.0× 10^-3 mol/L ^[54]	操作简单，试样量少，分离效率高，成本较低	分离能力较弱，重现性较差，不能同时检测不同离子类型，不适用于痕量检测
光谱法SA	流动注射分析法FIA	适合分子结构已知且具备络合剂、显色剂的测试	阴离子表面活性剂	0.003 mg/L	0.012~2.000 mg/L ^[53]	灵敏度高、分析快、耗样少	仪器及流路的要求较高，不利于实时现场测定
光谱法SA	共振光散射法RLS	适用多组分产品分析测试	阴离子、阳离子和非离子表面活性剂			选择性良好、操作简单、安全无毒、耗样少	受pH干扰影响较大、仪器成本较高

Tab. 3

References 53

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标准	项目	最大允许质量浓度/（mg/L）
标准	项目	Ⅰ类	Ⅱ类	Ⅲ类	Ⅳ类	Ⅴ类
地下水质量标准 GB/T 14848—2017	阴离子表面活性剂	不得检出	0.1	0.3	0.3	>0.3
地表水环境质量标准 GB 3838—2002	阴离子表面活性剂	0.2	0.2	0.2	0.3	0.3
海水水质标准 GB 3097—1997	阴离子表面活性剂	0.03	0.1	0.1	0.1
生活饮用水卫生标准 GB 5749—2022	阴离子合成洗涤剂	0.3
污水综合排放标准 GB 8978—1996	阴离子表面活性剂	5（一级）	10（二级）	20（三级）
农田灌溉水质标准 GB 5084—2021	阴离子表面活性剂	5（水作）	8（旱作）	5（蔬菜）

Research progress on detection methods of surfactants in water samples from environment

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[2]	Guofeng Li, Kainan Liu, Wenlong Mo, Teng Ma. Performance evaluation of a system of imbibition oil displacement agent in shale reservoir [J]. China Surfactant Detergent & Cosmetics, 2024, 54(3): 250-258.
[3]	Hongmei Zhang, Yongmin Zhang. Synthesis and properties of a choline-fatty-acid-based ionic liquid surfactant [J]. China Surfactant Detergent & Cosmetics, 2024, 54(2): 149-155.
[4]	Pei Liu, Ting Pan, Xiaomei Pei, Binglei Song, Jianzhong Jiang, Zhenggang Cui, Bernard P. Binks. Dual-responsive oil-in-water emulsions co-stabilized by a nonionic-anionic Bola surfactant and silica nanoparticles [J]. China Surfactant Detergent & Cosmetics, 2024, 54(1): 1-15.
[5]	Haokang Ai, Yajie Jiang, Yakui Wang, Lu Zhang, Tao Geng. Synthesis and properties of Gemini quaternary ammonium surfactant based on stearate [J]. China Surfactant Detergent & Cosmetics, 2024, 54(1): 16-23.
[6]	Wanping Zhang, Yanzhong Lin, Qianjie Zhang, Dongmei Zhang, Wen Jiang. Study on the phase behavior of sodium lauroyl methyltaurate mediated by Ca²⁺ [J]. China Surfactant Detergent & Cosmetics, 2024, 54(1): 32-37.
[7]	Chang Shiteng, Cai Xiaojun, Zheng Yancheng, Liu Xuejin, Yi Xiao, Jiang Zhuyang. Physicochemical properties of ethoxylated sulfosuccinate surfactants and their interfacial properties when mixed with a betaine surfactant [J]. China Surfactant Detergent & Cosmetics, 2023, 53(9): 989-998.
[8]	Xu Derong,Lian Wei,Xiong Jinzhao,Kang Wanli. Research on the influence factors of surfactant imbibition in tight reservoirs [J]. China Surfactant Detergent & Cosmetics, 2023, 53(8): 857-864.
[9]	Niu Qiqi,Lv Qichao,Dong Zhaoxia,Zhang Fengfan,Wang Hongbo. Research progress on the properties of foam systems containing wormlike micelles [J]. China Surfactant Detergent & Cosmetics, 2023, 53(8): 915-924.
[10]	Qiang Xuefeng, Zhang Li, Zheng Bin, Hou Qianqian, Yan Kun. Study on the inf luence of KCl on the evolution of foam of an anionic surfactant [J]. China Surfactant Detergent & Cosmetics, 2023, 53(7): 733-741.
[11]	Xing Huanyu, Jia Lihua, Zhao Zhenlong, Yang Rui, Guo Xiangfeng. Synthesis and properties of novel surfactants containing naphthalimide and alkyl segments [J]. China Surfactant Detergent & Cosmetics, 2023, 53(7): 742-747.
[12]	Fu Jiangpeng, Du Jinmei, Miao Dagang, Xiao Guowei, Jiang Yang, Xu Changhai. Effects of surfactants on removing colored stains from textiles when using activated peroxide systems [J]. China Surfactant Detergent & Cosmetics, 2023, 53(5): 511-516.
[13]	Yongkang Zhang, Mengmeng Liu, Zhiwei Wan, Yaocong Wang, Mimi Tian, Liewei Qiu. Effect of spacer on the performance of Gemini betaine surfactant in clean fracturing fluid [J]. China Surfactant Detergent & Cosmetics, 2023, 53(12): 1398-1404.
[14]	Ting Pan, Junhui Wu, Xiaomei Pei, Zhenggang Cui. Temperature and pH responsive behavior of wormlike micelles formed by novel pseudo-gemini surfactant [J]. China Surfactant Detergent & Cosmetics, 2023, 53(12): 1361-1368.
[15]	Zhang Xin, Zhang Guanghua, Sun Qi, Li Hui, Tang Mingxuan, Guo Zehua. Study on the synthesis and performance of a responsive surfactant of tertiary amine type [J]. China Surfactant Detergent & Cosmetics, 2023, 53(11): 1250-1256.