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

doi:10.3724/SP.J.1123.2019.10027

Abstract

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

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.

Figures/Tables 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)