液液萃取-分散液液微萃取-气相色谱-质谱联用测定纺织废水中痕量禁用偶氮染料

doi:10.3724/SP.J.1123.2019.07012

摘要/Abstract

摘要：

建立了液液萃取-分散液液微萃取-气相色谱-质谱联用技术测定纺织废水中痕量偶氮染料的方法。废水中的偶氮染料在碱性条件下经连二亚硫酸钠还原成芳香胺后，先用叔丁基甲醚液液萃取、盐酸反萃进行预浓缩及净化；再以乙腈-氯苯体系进行分散液液微萃取，气相色谱-质谱测定。对前处理条件进行了优化，考察了酸碱度及盐效应对芳香胺萃取效率的影响，结果表明：液液萃取过程中加入30 g NaCl，分散液液微萃取过程中加入1 mL 5 mol/L的NaOH调节体系至碱性才能达到较好的萃取效率。在优化的实验条件下，21种目标物均呈现良好的线性关系，其中13种芳香胺的线性范围为0.05~10 μg/L，7种芳香胺的线性范围为0.05~5 μg/L，2，4-二氨基苯甲醚的线性范围为20~100 μg/L，相关系数为0.996~0.999。20种芳香胺的检出限可达0.05 μg/L，2，4-二氨基苯甲醚检出限为20 μg/L。印染、机织、印花等实际废水加标试验表明，方法的回收率为75.6%~115.1%。该方法富集倍数高，检出限低，适用于纺织废水中痕量禁用偶氮染料的检测。

关键词: 分散液液微萃取, 气相色谱-质谱, 禁用偶氮染料, 芳香胺, 纺织废水

Abstract:

An efficient method based on liquid-liquid extraction and dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry was developed for the determination of trace azo dyes in textile wastewater. The azo dyes were reduced to aromatic amines by sodium dithionite under alkaline conditions. The main pretreatment conditions that affected the extraction efficiency were optimized. Under the optimized experimental conditions, the linear ranges of this method were as follows:0.05-10 μg/L for 13 aromatic amines; 0.05-5 μg/L for 7 aromatic amines; and 20-100 μg/L for 2, 4-diaminoanisole. The correlation coefficients were in the range of 0.996-0.999. The limits of detection reached 0.05 μg/L for all the 20 aromatic amines, and the detection limit of 2, 4-diaminoanisole was 20 μg/L. Actual wastewater-spiked experiments involving printing, dyeing, and weaving showed that the average recoveries of the amines were in the range of 75.6%-115.1%. The developed method has high enrichment multiples and low detection limits, and it is suitable for the detection of trace levels of banned azo dyes in textile wastewater.

Key words: dispersion liquid-liquid microextraction (DLLME), gas chromatography-mass spectrometry (GC-MS), azo dye, aromatic amine, textile wastewater

叶曦雯, 何静, 李莹, 牛增元, 张甜甜, 罗忻, 邹立, 连素梅. 液液萃取-分散液液微萃取-气相色谱-质谱联用测定纺织废水中痕量禁用偶氮染料[J]. 色谱, 2020, 38(2): 255-263.

YE Xiwen, HE Jing, LI Ying, NIU Zengyuan, ZHANG Tiantian, LUO Xin, ZOU Li, LIAN Sumei. Determination of trace azo dyes in textile wastewater by liquid-liquid extraction and dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(2): 255-263.

图/表 11

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No.	Compound	CAS No.	Retention time/min	Quantitative ion (m/z)	Qualitative ions (m/z)
1) The CAS Nos. 97-56-3 (No. 23) and 99-55-8 (No. 22) are further reduced to CAS Nos. 95-53-4 (No. 2) and 95-80-7 (No. 9). 2) AZO colorants that can form 4-aminoazobenzene generate aniline (CAS No. 62-53-3) and 1, 4-phenylenediamine (CAS No. 106-50-3) under the conditions used in this method. Due to the detection limit, only aniline can be detected.
1	aniline	62-53-3	5.360	93	66, 65
2	o-toluidine	95-53-4	7.349	106	77, 107
3	2, 4-xylidine/2, 6-xylidine	95-68-1/87-62-7	9.028	121	106, 120
4	o-anisidine/2-methoxyaniline	90-04-0	9.151	123	108, 80
5	4-chloroaniline	106-47-8	9.634	127	92, 129
6	6-methoxy-m-toluidine	120-71-8	10.863	137	122, 94
7	2, 4, 5-trimethylaniline	137-17-7	11.192	135	120, 134
8	4-chloro-o-toluidine	95-69-2	11.318	141	106, 143
9	2, 4-toluylendiamine	95-80-7	12.739	121	104, 122
10	2, 4-diaminoanisole	615-05-4	14.183	138	123, 95
11	2-naphthylamine	91-59-8	15.470	143	115, 144
12	4-aminobiphenyl	92-67-1	18.341	169	168, 141
13	4, 4′-oxydianiline	101-80-4	24.240	200	171, 108
14	benzidine	92-87-5	24.485	184	92, 185
15	4, 4′-methylenedianiline	101-77-9	24.685	198	182, 197
16	4, 4′-methylenedi-o-toluidine	838-88-0	28.394	226	211, 225
17	3, 3′-dimethylbenzidine	119-93-7	28.785	212	180, 211
18	4, 4′-thiodianiline	139-65-1	29.608	216	184, 215
19	3, 3′-dichlorobenzidine	91-94-1	30.804	252	254, 154
20	4, 4′-methylene-bis-(2-chloro-aniline)	101-14-4	30.896	266	231, 252
21	3, 3′-dimethoxybenzidine	119-90-4	30.932	244	229, 201
22¹⁾	5-nitro-o-toluidine	99-55-8		152	77, 106
23¹⁾	o-aminoazotoluene	97-56-3		123	108, 80
24²⁾	4-aminoazobenzene	60-09-3		197	92, 65

No.	Compound	CAS No.	Retention time/min	Quantitative ion (m/z)	Qualitative ions (m/z)
1) The CAS Nos. 97-56-3 (No. 23) and 99-55-8 (No. 22) are further reduced to CAS Nos. 95-53-4 (No. 2) and 95-80-7 (No. 9). 2) AZO colorants that can form 4-aminoazobenzene generate aniline (CAS No. 62-53-3) and 1, 4-phenylenediamine (CAS No. 106-50-3) under the conditions used in this method. Due to the detection limit, only aniline can be detected.
1	aniline	62-53-3	5.360	93	66, 65
2	o-toluidine	95-53-4	7.349	106	77, 107
3	2, 4-xylidine/2, 6-xylidine	95-68-1/87-62-7	9.028	121	106, 120
4	o-anisidine/2-methoxyaniline	90-04-0	9.151	123	108, 80
5	4-chloroaniline	106-47-8	9.634	127	92, 129
6	6-methoxy-m-toluidine	120-71-8	10.863	137	122, 94
7	2, 4, 5-trimethylaniline	137-17-7	11.192	135	120, 134
8	4-chloro-o-toluidine	95-69-2	11.318	141	106, 143
9	2, 4-toluylendiamine	95-80-7	12.739	121	104, 122
10	2, 4-diaminoanisole	615-05-4	14.183	138	123, 95
11	2-naphthylamine	91-59-8	15.470	143	115, 144
12	4-aminobiphenyl	92-67-1	18.341	169	168, 141
13	4, 4′-oxydianiline	101-80-4	24.240	200	171, 108
14	benzidine	92-87-5	24.485	184	92, 185
15	4, 4′-methylenedianiline	101-77-9	24.685	198	182, 197
16	4, 4′-methylenedi-o-toluidine	838-88-0	28.394	226	211, 225
17	3, 3′-dimethylbenzidine	119-93-7	28.785	212	180, 211
18	4, 4′-thiodianiline	139-65-1	29.608	216	184, 215
19	3, 3′-dichlorobenzidine	91-94-1	30.804	252	254, 154
20	4, 4′-methylene-bis-(2-chloro-aniline)	101-14-4	30.896	266	231, 252
21	3, 3′-dimethoxybenzidine	119-90-4	30.932	244	229, 201
22¹⁾	5-nitro-o-toluidine	99-55-8		152	77, 106
23¹⁾	o-aminoazotoluene	97-56-3		123	108, 80
24²⁾	4-aminoazobenzene	60-09-3		197	92, 65

Sample No.	Compound	pH 1		pH 7		pH 14
Sample No.	Compound	Average/(mg/L)	RSD/%(n=3)	Average/(mg/L)	RSD/%(n=3)	Average/(mg/L)	RSD/%(n=3)
ND: not detected.
1	aniline	0.03	1.5	2.54	1.5	2.87	1.5
	4-chloroaniline	0.36	5.1	0.35	12.2	0.42	13.1
	2, 4-diaminoanisole	ND	ND	0.85	11.2	1.14	10.2
	benzidine	0.82	8.2	2.13	12.2	4.51	2.2
2	o-toluidine	0.55	9.1	14.77	2.1	20.15	2.1
	2-naphthylamine	0.05	2.3	0.48	8.2	0.50	12.2

Sample No.	Compound	pH 1		pH 7		pH 14
Sample No.	Compound	Average/(mg/L)	RSD/%(n=3)	Average/(mg/L)	RSD/%(n=3)	Average/(mg/L)	RSD/%(n=3)
ND: not detected.
1	aniline	0.03	1.5	2.54	1.5	2.87	1.5
	4-chloroaniline	0.36	5.1	0.35	12.2	0.42	13.1
	2, 4-diaminoanisole	ND	ND	0.85	11.2	1.14	10.2
	benzidine	0.82	8.2	2.13	12.2	4.51	2.2
2	o-toluidine	0.55	9.1	14.77	2.1	20.15	2.1
	2-naphthylamine	0.05	2.3	0.48	8.2	0.50	12.2

Analyte No.	Spiked level/ (μg/L)	Recoveries (RSDs)/%
Analyte No.	Spiked level/ (μg/L)	Printing water	Weaving water	Dyeing water
The Nos. are the same as those in Table 1.
1	0.5	75.9 (5.4)	94.7 (7.8)	94.0 (5.2)
	1	85.5 (6.1)	92.8 (13.7)	92.6 (9.6)
	5	89.2 (6.4)	93.9 (11.5)	98.7 (4.5)
2	0.5	76.8 (6.5)	98.9 (8.4)	82.8 (11.2)
	1	81.6 (9.1)	96.4 (10.7)	87.0 (8.0)
	5	89.6 (7.4)	96.5 (11.7)	88.9 (13.8)
3	0.5	94.7 (6.4)	96.1 (7.1)	94.1 (10.3)
	1	84.2 (4.5)	98.0 (10.9)	90.7 (7.3)
	5	82.3 (6.5)	97.1 (12.2)	88.9 (8.1)
4	0.5	78.2 (9.1)	97.9 (7.7)	77.1 (8.3)
	1	78.8 (6.2)	100.6 (10.2)	99.6 (11.4)
	5	82.9 (8.1)	98.1 (10.0)	78.5 (5.6)
5	0.5	78.3 (2.7)	95.0 (6.5)	91.4 (6.1)
	1	86.2 (6.3)	95.6 (13.3)	105.4 (10.6)
	5	91.3 (4.7)	99.7 (10.1)	106.7 (11.8)
6	0.5	82.1 (5.1)	95.1 (8.0)	89.2 (4.4)
	1	83.2 (7.4)	110.2 (9.8)	79.5 (9.2)
	5	85.5 (3.1)	99.4 (13.5)	75.9 (8.1)
7	0.5	77.2 (5.9)	97.1 (5.5)	79.7 (6.6)
	1	85.1 (7.4)	103.6 (13.7)	88.3 (5.4)
	5	92.4 (6.9)	100.2 (11.0)	97.5 (6.2)
8	0.5	79.4 (5.2)	91.7 (9.0)	100.9 (7.3)
	1	81.1 (5.6)	85.2 (7.5)	82.1 (4.7)
	5	84.5 (5.1)	107.7 (13.1)	93.8 (11.1)
9	0.5	78.9 (7.2)	93.2 (6.8)	105.2 (10.3)
	1	76.9 (9.0)	104.1 (12.0)	93.9 (6.0)
	5	81.5 (6.8)	100.1 (12.7)	104.4 (12.2)
10	50	85.7 (4.9)	87.7 (4.9)	85.0 (5.7)
11	0.5	84.6 (11.2)	94.2 (9.9)	96.3 (4.5)
	1	76.2 (8.1)	115.1 (4.6)	99.0 (11.2)
	5	87.2 (5.5)	99.4 (10.7)	81.3 (9.4)
12	0.5	81.1 (4.2)	82.0 (5.7)	76.5 (13.3)
	1	82.6 (7.5)	101.0 (9.8)	96.0 (5.6)
	5	90.3 (7.2)	94.1 (11.6)	87.2 (9.3)
13	0.5	80.5 (6.9)	102.9 (12.5)	82.3 (5.2)
	1	89.8 (7.2)	99.8 (7.2)	99.1 (9.0)
	5	89.2 (4.3)	97.8 (12.6)	95.9 (9.7)
14	0.5	75.6 (7.8)	84.2 (7.8)	79.4 (11.4)
	1	79.5 (3.1)	105.8 (10.3)	104.9 (6.4)
	5	84.3 (6.9)	91.3 (12.7)	77.1 (6.8)
15	0.5	80.4 (2.7)	85.5 (7.4)	79.1 (8.9)
	1	84.9 (9.4)	110.4 (5.1)	86.5 (7.8)
	5	86.6 (6.1)	99.0 (7.8)	88.5 (7.4)
16	0.5	86.5 (4.2)	96.7 (5.7)	82.4 (6.5)
	1	83.4 (11.5)	103.4 (13.9)	99.9 (11.2)
	5	94.7 (10.9)	105.8 (11.9)	82.6 (10.5)
17	0.5	92.1 (6.2)	99.1 (6.5)	78.5 (5.8)
	1	81.6 (8.7)	101.6 (9.1)	87.9 (9.2)
	5	90.6 (9.2)	99.6 (7.4)	93.8 (9.9)
18	0.5	91.8 (11.5)	95.8 (12.0)	84.5 (11.0)
	1	89.2 (10.5)	109.2 (3.4)	84.7 (12.3)
	5	92.0 (9.4)	99.0 (10.3)	80.0 (11.7)
19	0.5	94.1 (9.4)	94.1 (12.2)	79.1 (8.2)
	1	76.0 (8.4)	86.0 (9.1)	83.3 (9.4)
	5	79.6 (7.9)	99.6 (9.5)	100.6 (9.1)
20	0.5	85.4 (8.6)	95.4 (5.1)	76.7 (8.5)
	1	88.8 (8.9)	98.8 (9.4)	105.7 (8.8)
	5	84.8 (7.9)	104.8 (12.2)	105.4 (7.6)
21	0.5	91.5 (11.9)	99.5 (5.9)	81.7 (12.1)
	1	90.8 (12.1)	101.8 (12.0)	90.8 (8.9)
	5	90.8 (7.9)	97.8 (9.7)	107.5 (6.5)