悬浮固化-分散液液微萃取-液相色谱-串联质谱测定纺织废水中磷系阻燃剂

doi:10.3724/SP.J.1123.2019.10027

摘要/Abstract

摘要：

建立了悬浮固化-分散液液微萃取结合液相色谱-串联质谱测定纺织废水中5种痕量磷系阻燃剂的方法。通过对萃取过程中萃取剂、分散剂的种类与体积、盐浓度、溶液pH值等对萃取效率的影响因素优化，确立了最佳萃取条件。采用了密度小于水的十一烷醇（400 μL）为萃取剂，甲醇（300 μL）为分散剂，控制溶液pH值在6~9之间，NaCl添加量为2 g，萃取时间为涡旋2 min。在优化的萃取条件下，该方法在2~100 μg/L均有良好的线性关系，相关系数大于0.995，除二（2，3-二溴丙基）磷酸酯（BIS）的检出限为5 μg/L外，三（2-氯乙基）磷酸酯（TCEP）、三（1，3-二氯-异丙基）磷酸酯（TDCP）、三（1-氮丙啶基）氧化膦（TEPA）和三（2，3-二溴丙基）磷酸酯（TRIS）的检出限均为2 μg/L。后整理、染色和印花等实际废水样品加标试验表明，方法的平均回收率为71.6%~114.5%，RSD为2.7%~11.2%（n=6）。对11个样品进行检测，其中3个废水样品检出TCEP与TDCP化合物，含量为2.6~3.4 μg/L。本方法简单，快速，灵敏度好且环保绿色，能够对纺织废水中的5种痕量磷系阻燃剂进行准确的定性与定量检测。

关键词: 悬浮固化, 分散液液微萃取, 超高效液相色谱-串联质谱, 磷系阻燃剂, 纺织废水

Abstract:

A rapid method for the determination of five organophosphorus flame retardants (OPFRs) in textile wastewater was established by dispersive liquid-liquid microextraction (DLLME) based on solidification of floating organic drop (SFO) coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The analytes were extracted from the water samples by SFO-DLLME, which was performed using a mixture of an extraction solvent that was less dense than water, 1-undecanol, and a dispersive solvent, methanol. The influences of the SFO-DLLME parameters on the extraction efficiencies were studied. 1-Undecanol (extraction solvent, 400 μL) and methanol (dispersive solvent, 300 μL) were added to textile wastewater (containing 2 g NaCl) with pH between 6 and 9, and the solution was shaken for 2 min. Under optimum conditions, the linear ranges of the proposed method were from 2 μg/L to 100 μg/L with correlation coefficients (R²) above 0.99 for all the analytes. The limits of detection (S/N=3) ranged from 2 μg/L to 5 μg/L. The precision of the method was evaluated in terms of repeatability; the relative standard deviations varied from 2.7% to 11.2% (n=6). The relative recoveries ranged from 71.6% to 117.6% for all analytes. Only 3 of the 11 selected samples were tested positive for OPFRs, and the total concentrations of OPFRs in them were in the range of 2.6-3.4 μg/L. Hence, this method is accurate, environmentally friendly, fast, and convenient for the routine analysis of OPFRs in textile wastewater.

Key words: solidification of floating organic drop (SFO), dispersive liquid-liquid microextraction (DLLME), ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), organophosphorus flame retardants (OPFRs), textile wastewater

何静, 叶曦雯, 汤志旭, 牛增元, 罗忻, 邹立. 悬浮固化-分散液液微萃取-液相色谱-串联质谱测定纺织废水中磷系阻燃剂[J]. 色谱, 2020, 38(6): 679-686.

HE Jing, YE Xiwen, TANG Zhixu, NIU Zengyuan, LUO Xin, ZOU Li. Determination of organophosphorus flame retardants in textile wastewater by dispersive liquid-liquid microextraction based on solidification of floating organic drop followed by ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(6): 679-686.

图/表 11

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No.	Analyte and abbreviation	CAS number	Precursor ion (m/z)	Daughter ions (m/z)	Collision energies/eV	Fragmentor/V	Internal standard
* Quantitative ion.
1	tris(1-aziridinyl)phosphine oxide (TEPA)	545-55-1	174.0	131.0^*, 42.0	9, 25	86	TEPA-d₁₂
2	tris(2-chloroethyl)phosphate (TCEP)	115-96-8	284.9	99.0^*, 63.0	21, 25	97	TBP-d₂₇
3	tris(1, 3-dichloro-isopropyl)phosphate (TDCP)	13674-87-8	430.9	321.0^*, 99.0	5, 25	107	TBP-d₂₇
4	bis(2, 3-dibromopropyl)phosphate (BIS)	5412-25-9	498.7	298.9^*, 98.9	3, 16	130
5	tris(2, 3-dibromopropyl)phosphate (TRIS)	126-72-7	698.0	498.7^*, 99.0	4, 25	145	TBP-d₂₇
6	tri-n-butylphosphate-d₂₇(TBP-d₂₇)	61196-26-7	294.4	101.9^*	15	70
7	triethylenephosphoramide-d₁₂(TEPA-d₁₂)	1246816-29-4	186.1	139.1^*, 62.2	13, 9	110

No.	Analyte and abbreviation	CAS number	Precursor ion (m/z)	Daughter ions (m/z)	Collision energies/eV	Fragmentor/V	Internal standard
* Quantitative ion.
1	tris(1-aziridinyl)phosphine oxide (TEPA)	545-55-1	174.0	131.0^*, 42.0	9, 25	86	TEPA-d₁₂
2	tris(2-chloroethyl)phosphate (TCEP)	115-96-8	284.9	99.0^*, 63.0	21, 25	97	TBP-d₂₇
3	tris(1, 3-dichloro-isopropyl)phosphate (TDCP)	13674-87-8	430.9	321.0^*, 99.0	5, 25	107	TBP-d₂₇
4	bis(2, 3-dibromopropyl)phosphate (BIS)	5412-25-9	498.7	298.9^*, 98.9	3, 16	130
5	tris(2, 3-dibromopropyl)phosphate (TRIS)	126-72-7	698.0	498.7^*, 99.0	4, 25	145	TBP-d₂₇
6	tri-n-butylphosphate-d₂₇(TBP-d₂₇)	61196-26-7	294.4	101.9^*	15	70
7	triethylenephosphoramide-d₁₂(TEPA-d₁₂)	1246816-29-4	186.1	139.1^*, 62.2	13, 9	110

Analyte	Linear range/(μg/L)	Regression equation	R²	LOD/(μg/L)
Y: peak area; X: mass concentration, μg/L. y: peak area ratio of analyte to internal standard; x: mass concentration of analyte, μg/L.
TEPA	2-100	y=341.3x+242.4	0.999	2
BIS	10-100	Y=152.6X-243.3	0.999	5
TCEP	2-100	y=13121.2x-12532.9	0.999	2
TDCP	2-100	y=12341.1x-1230.5	0.997	2
TRIS	2-100	y=1345.1x-524.6	0.999	2

Analyte	Linear range/(μg/L)	Regression equation	R²	LOD/(μg/L)
Y: peak area; X: mass concentration, μg/L. y: peak area ratio of analyte to internal standard; x: mass concentration of analyte, μg/L.
TEPA	2-100	y=341.3x+242.4	0.999	2
BIS	10-100	Y=152.6X-243.3	0.999	5
TCEP	2-100	y=13121.2x-12532.9	0.999	2
TDCP	2-100	y=12341.1x-1230.5	0.997	2
TRIS	2-100	y=1345.1x-524.6	0.999	2

Analyte	Spiked level/(μg/L)	Recoveries (RSDs)/%
Analyte	Spiked level/(μg/L)	Pure water	Printing wastewater 1	Post-treatment wastewater	Printing wastewater 2	Dyeing water
TEPA	10	87.4 (11.1)	80.8 (6.3)	85.2 (5.4)	82.1 (5.1)	84.6 (11.2)
	20	87.9 (9.1)	85.1 (10.1)	85.5 (6.1)	83.2 (7.4)	86.2 (8.1)
	50	91.5 (2.7)	88.5 (3.5)	89.2 (6.4)	85.5 (3.1)	87.2 (5.5)
TCEP	10	105.3 (7.9)	103.2 (7.1)	99.1 (6.5)	97.2 (5.9)	101.1 (4.2)
	20	117.6 (2.7)	105.2 (5.2)	101.6 (9.1)	95.1 (7.4)	102.6 (7.5)
	50	102.6 (8.5)	100.6 (9.2)	99.6 (7.4)	92.4 (6.9)	97.3 (7.2)
TDCP	10	97.2 (5.6)	95.2 (5.8)	94.7 (6.4)	89.4 (5.2)	90.5 (6.9)
	20	108.2 (4.6)	105.7 (5.1)	104.2 (4.5)	101.1 (5.6)	99.8 (7.2)
	50	117.6 (5.4)	87.4 (7.7)	112.3 (6.5)	114.5 (5.1)	109.2 (4.3)
BIS	20	71.6 (10.8)	71.6 (9.1)	78.2 (9.1)	78.9 (7.2)	79.5 (7.8)
	30	80.2 (8.3)	79.2 (3.5)	78.8 (6.2)	76.9 (9.0)	79.5 (3.1)
	50	85.3 (5.5)	83.2 (7.3)	82.9 (8.1)	81.5 (6.8)	84.3 (6.9)
TRIS	10	82.1 (7.6)	79.0 (2.7)	78.3 (2.7)	77.8 (3.1)	80.4 (2.9)
	20	86.8 (8.6)	85.6 (7.7)	86.2 (6.3)	83.2 (8.1)	84.9 (9.4)
	50	91.6 (4.9)	90.2 (5.2)	91.3 (4.7)	85.7 (4.9)	86.6 (6.1)