Determination of bisphenols in sediment by accelerated solvent extraction and solid-phase extraction purification coupled with ultra performance liquid chromatography-tandem mass spectrometry

doi:10.3724/SP.J.1123.2022.12015

Abstract

Abstract:

Bisphenols are endocrine disruptors that are characterized with bioaccumulation, persistence, and estrogenic activity. Even low contents of bisphenols can exert adverse effects on human health and the ecological environment. Herein, a method combining accelerated solvent extraction and solid-phase extraction purification with ultra performance liquid chromatography-tandem mass spectrometry was developed for the accurate detection of bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF), bisphenol S (BPS), bisphenol Z (BPZ), bisphenol AF (BPAF), and bisphenol AP (BPAP) in sediments. The mass spectrometric parameters of the seven bisphenols were optimized, and the response values, separation effects, and chromatographic peak shapes of the target compounds were compared under three different mobile phase conditions. The sediment samples were pretreated by accelerated solvent extraction, and orthogonal tests were used to optimize the extraction solvent, extraction temperature, and cycle number. The results showed that the use of 0.05% (v/v) ammonia and acetonitrile as the mobile phase for gradient elution could rapidly separate the seven bisphenols on an Acquity UPLC BEH C₁₈ column (100 mm×2.1 mm, 1.7 μm). The gradient program was as follows: 0-2 min, 60%A; 2-6 min, 60%A-40%A; 6-6.5 min, 40%A; 6.5-7 min, 40%A-60%A; 7-8 min, 60%A. Orthogonal experiments indicated that the optimal extraction conditions were as follows: extraction solvent of acetonitrile, extraction temperature of 100 ℃, and cycle number of three. The seven bisphenols showed good linearity in the range of 1.0-200 μg/L, with correlation coefficients (r²) greater than 0.999, and the limits of detection were 0.01-0.3 ng/g. The recoveries for the seven bisphenols ranged from 74.9% to 102.8% at three spiking levels (2.0, 10, 20 ng/g), with relative standard deviations ranging from 6.2% to 10.3%. The established method was applied to detect the seven bisphenols in sediment samples collected from Luoma Lake and its inflow rivers. BPA, BPB, BPF, BPS, and BPAF were detected in the sediments of the lake, and BPA, BPF, and BPS were detected in the sediments of its inflow rivers. The detection frequency of BPA and BPF was 100%, and the contents of these bisphenols in the sediment were 11.9-38.0 ng/g and 11.0-27.3 ng/g, respectively. The developed method is simple, rapid with high accuracy and precision, and is suitable for the determination of the seven bisphenols in sediment.

Key words: accelerated solvent extraction (ASE), solid-phase extraction (SPE), ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), bisphenols, sediment, orthogonal test

CLC Number:

O658

WANG Qiuxu, FENG Qiyan, ZHU Xueqiang. Determination of bisphenols in sediment by accelerated solvent extraction and solid-phase extraction purification coupled with ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2023, 41(7): 582-590.

Figures/Tables 9

Table 1 Formula, CAS No., lg Kow and structural formula of the seven bisphenols

Bisphenol	Formula	CAS No.	lg K_ow^*
BPA	C₁₅H₁₆O₂	80-05-7	3.64
BPB	C₁₆H₁₈O₂	77-40-7	4.13
BPF	C₁₃H₁₂O₂	620-92-8	3.06
BPS	C₁₂H₁₀O₄S	80-09-1	1.65
BPZ	C₁₈H₂₀O₂	843-55-0	5.48
BPAF	C₁₅H₁₀F₆O₂	1478-61-1	4.47
BPAP	C₂₀H₁₈O₂	1571-75-1	4.86

Table 2 MS parameters for the analysis of the target compounds

Bisphenol	Retention time/min	Parent ion (m/z)	Daughter ion (m/z)	DP/ V	CE/ eV
BPA	2.32	227.1	211.1^*	-136	-27
			133.0	-108	-32
BPA-d₄	2.33	231.0	135.1	-132	-34
			215.0	-134	-29
BPB	2.96	241.1	211.1^*	-123	-30
			225.9	-106	-23
BPF	1.87	199.1	105.0^*	-121	-27
			92.8	-121	-30
BPS	1.31	248.4	107.9^*	-129	-34
			92.1	-121	-38
BPZ	4.15	267.1	173.0^*	-142	-34
			145.0	-121	-48
BPAF	2.17	335.0	264.5^*	-130	-30
			197.0	-139	-50
BPAP	3.65	289.0	273.9^*	-117	-21
			195.1	-117	-35

Fig. 1 Total ion current (TIC) chromatogram of the seven bisphenols (50 μg/L) Column: Acquity UPLC BEH C18 (100 mm×2.1 mm, 1.7 μm); mobile phases: 0.05%(v/v) ammonia (A) and acetonitrile (B); gradient program: 0-2 min, 60%A; 2-6 min, 60%A-40%A; 6-6.5 min, 40%A; 6.5-7 min, 40%A-60%A; 7-8 min, 60%A; injection volume: 2 μL; flow rate: 0.3 mL/min; column temperature: 40 ℃.

Table 3 Parameters and recoveries of the orthogonal test

No.	Factors				Recoveries/%
No.	Extraction solvent		Extraction temperature/ ℃	Cycle number	BPA	BPB	BPF	BPS	BPZ	BPAF	BPAP
1		methanol	80	1	56.1	52.6	53.8	37.7	53.3	49.6	42.8
2		methanol	100	2	64.9	61.8	64.6	47.4	55.8	51.1	48.6
3		methanol	120	3	66.4	56.3	60.4	51.1	60.7	58.1	40.5
4		acetonitrile	80	3	97.9	90.6	101.6	64.3	76.2	88.4	75.2
5		acetonitrile	100	1	103.3	94.2	89.2	68.7	84.8	79.2	82.7
6		acetonitrile	120	2	91.4	87.9	94.5	71.7	78.7	82.1	72.2
7		ethyl acetate	80	2	41.4	43.2	45.4	26.5	37.7	31.4	38.5
8		ethyl acetate	100	3	54.4	40.6	51.5	38.3	45.4	37.5	31.5
9		ethyl acetate	120	1	44.9	37.4	39.2	31.4	41.3	44.6	26.2

Table 4 Results of the orthogonal test

Bisphenol	Item	Factors
Bisphenol	Item	Extraction solvent	Extraction temperature/℃	Cycle number
BPA	${\bar{K}}_{1}$	62.5	65.1	68.1
	${\bar{K}}_{2}$	97.5	74.2	65.9
	${\bar{K}}_{3}$	46.9	67.6	72.9
	R	50.6	9.1	7.0
BPB	${\bar{K}}_{1}$	56.9	62.1	61.4
	${\bar{K}}_{2}$	90.9	65.5	64.3
	${\bar{K}}_{3}$	40.4	60.5	62.5
	R	50.5	5.0	2.9
BPF	${\bar{K}}_{1}$	59.6	66.9	60.7
	${\bar{K}}_{2}$	95.1	68.4	68.2
	${\bar{K}}_{3}$	45.4	64.7	71.2
	R	49.7	3.7	10.4
BPS	${\bar{K}}_{1}$	45.4	42.8	45.9
	${\bar{K}}_{2}$	68.2	51.5	48.5
	${\bar{K}}_{3}$	32.1	51.4	51.2
	R	36.2	8.6	5.3
BPZ	${\bar{K}}_{1}$	56.6	55.7	59.8
	${\bar{K}}_{2}$	79.9	62.0	57.4
	${\bar{K}}_{3}$	41.5	60.2	60.8
	R	38.4	6.3	3.4
BPAF	${\bar{K}}_{1}$	52.9	56.5	57.8
	${\bar{K}}_{2}$	83.2	55.9	54.9
	${\bar{K}}_{3}$	37.8	61.6	61.3
	R	45.4	5.7	6.5
BPAP	${\bar{K}}_{1}$	44.0	52.2	50.6
	${\bar{K}}_{2}$	76.7	54.3	53.1
	${\bar{K}}_{3}$	32.1	46.3	49.1
	R	44.6	8.0	4.0

Table 4 Results of the orthogonal test

Bisphenol	Item	Factors
Bisphenol	Item	Extraction solvent	Extraction temperature/℃	Cycle number
BPA	${\bar{K}}_{1}$	62.5	65.1	68.1
	${\bar{K}}_{2}$	97.5	74.2	65.9
	${\bar{K}}_{3}$	46.9	67.6	72.9
	R	50.6	9.1	7.0
BPB	${\bar{K}}_{1}$	56.9	62.1	61.4
	${\bar{K}}_{2}$	90.9	65.5	64.3
	${\bar{K}}_{3}$	40.4	60.5	62.5
	R	50.5	5.0	2.9
BPF	${\bar{K}}_{1}$	59.6	66.9	60.7
	${\bar{K}}_{2}$	95.1	68.4	68.2
	${\bar{K}}_{3}$	45.4	64.7	71.2
	R	49.7	3.7	10.4
BPS	${\bar{K}}_{1}$	45.4	42.8	45.9
	${\bar{K}}_{2}$	68.2	51.5	48.5
	${\bar{K}}_{3}$	32.1	51.4	51.2
	R	36.2	8.6	5.3
BPZ	${\bar{K}}_{1}$	56.6	55.7	59.8
	${\bar{K}}_{2}$	79.9	62.0	57.4
	${\bar{K}}_{3}$	41.5	60.2	60.8
	R	38.4	6.3	3.4
BPAF	${\bar{K}}_{1}$	52.9	56.5	57.8
	${\bar{K}}_{2}$	83.2	55.9	54.9
	${\bar{K}}_{3}$	37.8	61.6	61.3
	R	45.4	5.7	6.5
BPAP	${\bar{K}}_{1}$	44.0	52.2	50.6
	${\bar{K}}_{2}$	76.7	54.3	53.1
	${\bar{K}}_{3}$	32.1	46.3	49.1
	R	44.6	8.0	4.0

Table 5 Linear relationships, LODs, LOQs, matrix effects (MEs), and recoveries of the seven bisphenols in sediment (n=3)

Bisphenol	Regression equation	r²	LOD/(ng/g)	LOQ/(ng/g)	Spiked/(ng/g)	Recovery/%	RSD/%	ME/%
BPA	y=3344.8x-3055.1	0.9992	0.3	1.2	2.0	92.6	8.4	112.4
					10	102.8	9.2
					20	97.7	7.8
BPB	y=43092x-38319	0.9995	0.1	0.4	2.0	80.7	7.7	89.3
					10	85.1	8.3
					20	90.4	8.5
BPF	y=52079x-54265	0.9993	0.2	0.8	2.0	82.8	6.2	102.5
					10	84.3	9.4
					20	93.7	10.3
BPS	y=359131x-363426	0.9994	0.02	0.08	2.0	74.9	9.2	82.7
					10	78.4	8.5
					20	77.9	7.6
BPZ	y=59535x-45969	0.9991	0.04	0.16	2.0	78.2	8.7	93.4
					10	82.3	9.7
					20	86.8	7.4
BPAF	y=488005x-454159	0.9993	0.01	0.04	2.0	78.9	9.7	106.3
					10	80.2	8.6
					20	83.7	9.4
BPAP	y=307737x-304950	0.9992	0.05	0.2	2.0	75.4	8.2	87.2
					10	79.1	9.1
					20	81.9	8.7

Table 6 Comparison with similar analytical methods

Sample	Bisphenols	Analytical methods	Linear range/ (μg/L)	LOD/ (ng/g)	Recovery/ %	Ref.
Sediment	BPS, BPF, BPA, BPB, BPZ, BPAF, BPAP	ASE-SPE-LC-MS/MS	1.0-200	0.01-0.3	74.9-102.8	this study
Sediment	BPS, BPF, BPA, BPB, BPZ, BPAF, BPAP	ultrasound-assisted-SPE-GC-MS	-	0.03-0.32	89.3-105	[17]
Soil	BPS, BPF, BPA, BPB, BPZ, BPAF, BPAP	ASE-rotary evaporator-LC-MS/MS	1.0-200	0.03-0.39	80-110	[19]
Sediment	BPS, BPF, BPA, BPB, BPAF	ultrasonic-SPE-LC-MS/MS	-	0.02-0.2	66.1-103.2	[15]
Sediment	BPA	oscillatory-SPE-LC-MS/MS	1.0-200	0.05	103.5-119.7	[18]
	BPS		1.0-100	0.01	86.1-98.0

Table 7 Detection frequencies and content ranges of the seven bisphenols in sediment of Luoma Lake and its inflow rivers

Bisphenol	Luoma Lake (n=14)		Inflow rivers (n=17)
Bisphenol	Detection frequency/ %	Content range/ (ng/g)	Detection frequency/ %	Content range/ (ng/g)
BPA	100	11.9-27.7	100	14.0-38.0
BPB	14.3	ND-0.6	0	ND
BPF	100	11.0-19.5	100	11.3-27.3
BPS	42.9	ND-0.2	17.6	ND-0.2
BPZ	0	ND	0	ND
BPAF	7.1	ND-0.1	0	ND
BPAP	0	ND	0	ND

Fig. 2 Chromatogram of the bisphenols in actual samples

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