四氮杂杯[2]芳烃[2]三嗪键合硅胶固相萃取-高效液相色谱法测定河水中硝基苯酚和己烯雌酚

doi:10.3724/SP.J.1123.2019.06022

摘要/Abstract

摘要：

基于四氮杂杯[2]芳烃[2]三嗪键合硅胶吸附剂（NC-Si），构建了固相萃取-高效液相色谱法同时测定河水中3种硝基苯酚和己烯雌酚的新方法。考察并获得了固相萃取和液相色谱分离的优化条件：将样品溶液pH调至5，以5 mL/min上样，经自制固相萃取柱净化，2 mL氨水-甲醇（2：98，v/v）洗脱；在C8柱上以甲醇-0.1%磷酸溶液为流动相进行梯度洗脱。4种目标分析物的检出限（LOD，S/N=3）为0.03~0.3 μg/L，定量限（LOQ，S/N=10）为0.1~1.0 μg/L；加标回收率为75.5%~104.2%，相对标准偏差（RSD，n=5）小于6.3%。该方法准确、可靠，可用于河水中硝基苯酚及己烯雌酚的灵敏检测。

关键词: 四氮杂杯[2]芳烃[2]三嗪, 固相萃取, 高效液相色谱, 硝基苯酚, 己烯雌酚, 河水

Abstract:

A novel method based on solid phase extraction (SPE)-high performance liquid chromatography (HPLC) was developed for the simultaneous determination of nitrophenols and diethylstilbestrol in river water. Tetraaza[2]arene[2]triazine-bonded silica gel, a homemade SPE adsorbent, was used to enrich the nitrophenols and diethylstilbestrol, and the optimal SPE and HPLC conditions were established. The sample solution was adjusted to pH 5, purified with a lab-made solid phase extraction column, and then eluted with 2 mL ammonia-methanol (2:98, v/v). The enriched sample was separated on a C8 column with methanol and 0.1% phosphoric acid solution as mobile phases in a gradient elution. Under the optimized conditions, the limits of detection (LOD, S/N=3) for the four target analytes were 0.03-0.3 μg/L, and the limits of quantification (LOQ, S/N=10) were 0.1-1.0 μg/L. The recoveries were 75.5%-104.2%, and the relative standard deviations (RSD, n=5) were less than 6.3%. The proposed method is accurate and reliable, and it has been successfully used for determining nitrophenols and diethylstilbestrol in river water.

Key words: tetraaza[2]arene[2]triazine, solid phase extraction(SPE), high performance liquid chromatography (HPLC), nitrophenol, diethylstilbestrol, river water

彭子芳, 李琴, 张光瑞, 赵无垛, 练鸿振, 张书胜. 四氮杂杯[2]芳烃[2]三嗪键合硅胶固相萃取-高效液相色谱法测定河水中硝基苯酚和己烯雌酚[J]. 色谱, 2020, 38(1): 143-148.

PENG Zifang, LI Qin, ZHANG Guangrui, ZHAO Wuduo, LIAN Hongzhen, ZHANG Shusheng. Solid phase extraction and high performance liquid chromatography with tetraaza[2]arene[2]triazine-bonded silica gel adsorbent for determination of nitrophenols and diethylstilbestrol in river water[J]. Chinese Journal of Chromatography, 2020, 38(1): 143-148.

图/表 5

图1 4种酚类物质的HPLC图

Fig. 1 Chromatogram of the mixture of four phenolic substances Conditions: C8 column (250 mm×4.6 mm, 5 μm); mobile phase A, methanol; mobile phase B, 0.1% (v/v) phosphoric acid solution; the elution program: 0-11 min, 40%B; 11-15 min, 40%B-80%B; 15-20 min, 80%B; flow rate, 1.0 mL/min; detection wavelength, 254 nm; injection volume, 20 μL; column temperature, 30 ℃.Peaks: 1. 2, 4, 6-trinitrophenol; 2. p-nitrophenol; 3. 2, 4-dinitrophenol; 4. diethylstilbestrol.

图2 (a) 洗脱剂用量、(b)上样体积、(c)样品pH、(d)上样速率和(e)重复利用次数对4种酚类物质回收率的影响

Fig. 2 Effects of (a) eluent dosage, (b)loading volume, (c) sample pH, (d) loading rate, and (e) reusable time on the recoveries of the four phenolic substances

表1 方法的线性方程、相关系数(R2)、检出限和定量限

Table 1 Linear regression equations, correlation coe- fficients (R2), limits of detection(LODs) and limits of quantification (LOQs)

Analyte	Regression equation	R²	LOD/ (μg/L)	LOQ/ (μg/L)
y: peak area; x: mass concentration, μ g/L.
p-Nitrophenol	y=55.995x-0.5002	0.9993	0.300	1.00
2, 4-Dinitrophenol	y=369.96x+1.4519	0.9995	0.100	0.300
2, 4, 6-Trinitrophenol	y=22.786x+4.1287	0.9999	0.030	0.100
Diethylstilbestrol	y=51.349x+0.2886	0.9998	0.030	0.100

表2 水样中4种酚的加标回收率和相对标准偏差(n=5)

Table 2 Recoveries and RSDs of the four phenols in different environmental water samples(n=5)

Sample	Analyte	Background/ (μg/L)	Spiked level/ (μg/L)	Found/ (μg/L)	Recovery/ %	RSD/ %
-: not detected
Yellow River water	p-nitrophenol	1.50	1.00	2.28	78.0	5.60
			2.00	3.01	75.5	5.40
			10.00	9.07	75.7	6.30
	2, 4-dinitrophenol	-	2.00	1.69	84.5	3.61
			5.00	4.25	85.0	2.20
			10.00	8.84	88.4	4.83
	2, 4, 6-trinitrophenol	1.40	1.00	2.28	88.0	2.43
			2.00	3.08	84.3	1.90
			10.00	9.36	79.6	3.42
	diethylstilbestrol	0.24	0.50	0.68	88.0	3.40
			2.00	2.32	104.2	5.20
			10.0	9.59	93.4	4.11
Jinshui River water	p-nitrophenol	1.20	1.00	2.01	81.2	3.11
			2.00	2.56	80.1	5.10
			5.00	4.80	77.4	2.00
	2, 4-dinitrophenol	2.30	2.00	2.95	86.2	3.67
			4.00	5.65	83.8	3.40
			10.00	10.75	84.5	5.52
	2, 4, 6-trinitrophenol	2.60	2.00	4.31	85.5	2.43
			4.00	5.84	81.0	2.80
			10.00	11.80	92.0	4.30
	diethylstilbestrol	1.60	0.50	2.04	87.7	4.22
			2.00	3.42	91.1	3.08
			10.00	10.58	89.8	2.82

图3 实际河水样品和加标样品经过SPE处理后的色谱图

Fig. 3 Chromatograms of the real river water samples and spiked samples treated with SPE a. Yellow River water sample; b. the spiked Yellow River water sample; c. Jinshui River water sample; d. the spiked Jinshui River water sample.Conditions are the same as in Fig. 1.

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