Determination of Parabens in Breast Milk Samples by Dispersive Liquid-Liquid Microextraction (DLLME) and Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry

Grecco, Caroline F.; Souza, Israel D.; Acquaro, Vinicius R.; Queiroz, Maria E. C.

doi:10.21577/0103-5053.20180151

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Articles • J. Braz. Chem. Soc. 30 (1) • Jan 2019 • https://doi.org/10.21577/0103-5053.20180151 copy

Determination of Parabens in Breast Milk Samples by Dispersive Liquid-Liquid Microextraction (DLLME) and Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry

Authorship SCIMAGO INSTITUTIONS RANKINGS

A reliable method was developed and validated based on dispersive liquid-liquid microextraction (DLLME) and ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) to determine simultaneously methylparaben (MePB), ethylparaben (EtPB), propylparaben (PrPB), and butylparaben (BuPB) in breast milk samples. A central composite design 2⁴ with four independent variables and five levels of variance was used to optimize the DLLME conditions. The DLLME/UHPLC-MS/MS method was linear from 5 (lower limit of quantification, LLOQ) to 100 ng mL^-1 (upper limit of quantification, ULOQ). The inter-assay and intra-assay precision values presented coefficients of variation (CVs) lower than 15%, and the relative standard error of the inter- and intra-assay accuracy values was lower than 10.4%. The DLLME/UHPLC-MS/MS method was successfully applied to determine parabens in human milk samples obtained from sixteen volunteer lactating mothers.

Keywords:
parabens; breast milk sample; dispersive liquid-liquid microextraction; ultra-high-performance liquid chromatography tandem mass spectrometry

Analyte	Precursor ion (m/z)	Product ion (m/z)	DP / V	CE / eV	Qualifier ion (m/z)	RT / min
MePB	151.0	92/136	35	10/20	136.0	1.70
EtPB	165.0	91.9/136	33	23/14	136.0	2.23
PrPB	179.0	92/136	30	20/20	136.0	3.25
BuPB	193.0	92/136	30	20/20	136.0	5.14
Internal standard^a a Propyl 4-hydroxybenzoate-ring-13C6, dwell time = 0.027 s. MePB: methylparaben; EtPB: ethylparaben; PrPB: propylparaben; BuPB: butylparaben.	185.0	98/142	38	20/15		3.25

Independent variable	Variation levels
Independent variable	-2	-1	0	1	2
Extraction solvent volume / µL	200	350	500	650	800
Disperser solvent volume / mL	0.5	1.0	1.5	2.0	2.5
Ionic strength / (% m/v)	0	5	10	15	20
pH	4	5	6	7	8

Paraben	Linear regression [5.0(LLOQ) - 100 ng mL^-1]	R²	Lack-of-fit (p-value)
MePB	y = 0.0512x + 0.2058	0.9985	0.7904
EtPB	y = 0.0532x + 0.0412	0.9947	0.9394
PrPB	y = 0.0844x + 0.1046	0.9989	0.1476
BuPB	y = 0.0782x + 0.7543	0.9974	0.3237

Paraben	Concentration / (ng mL^-1)	Accuracy (RSE) / %		Precision (CV) / %
Paraben	Concentration / (ng mL^-1)	Intra-assay n = 5	Inter-assay n = 5	Intra-assay n = 5	Inter-assay n = 5
MePB	LLOQ (5.0)	-3.5	-3.5	14.7	2.4
	10	4.0	4.0	13.2	4.6
	50	-1.5	-1.5	8.2	2.3
	80	4.4	4,4	12.5	3.0
	100	0.7	0.7	6.4	0.4
EtPB	LLOQ (5.0)	10.4	10.4	16.6	6.4
	10	-1.2	-1.2	10.1	6.4
	50	0.5	1.1	5.5	2.4
	80	-0.8	1.8	2.4	1.5
	100	0.7	0.7	5.7	2.1
PrPB	LLOQ (5.0)	-19	-5.4	13.5	11.3
	10	-14.5	-8.2	7.3	7.7
	50	3.5	3.3	2.7	2.7
	80	-1.6	-1.6	10.6	3.0
	100	-2.8	-2.0	1.3	0.5
BuPB	LLOQ (5.0)	10.3	10.3	12.4	1.3
	10	5.3	1.7	13.1	2.7
	50	-2.3	-7.6	15.0	3.4
	80	1.6	1.6	5.6	5.2
	100	-5.0	-5.0	7.0	1.4

Analyte	Sample preparation	Sample volume / mL	Linear range / (ng mL^-1)	Concentration range of parabens in milk samples / (ng mL^-1)	Run time / min	Reference
MePB EtPB PrPB BuPB BzPB	online SPE	0.1	1.86-100 1.73-100 1.76-100 1.66-100 1.63-100	0.53-3.00 - 0.32-0.33 - -	15	Ye et al.¹⁰
MePB EtPB PrPB BuPB	PPT	0.2		1.0-8.0 1.0-1.5 1.0-2.0 -	3.7	Schlumpf et al.³²
MePB EtPB PrPB	MISPE	0.2	10-150 20-150 20-150	not mentioned	10.2	Melo and Queiroz¹¹
MePB EtPB PrPB BuPB	QuEChERS	9.9	0.09-25.0 0.09-25.0 0.09-25.0 0.1-25.0	0.4-3.5 0.2-3.4 0.1-7.5 0.2-1.3	13	Rodriguez-Gomez et al.⁷
MePB EtPB PrPB BuPB	SM-SLLME	1.0	0.5-100 0.5-100 0.4-100 0.5-100	0.9-11.3 0.5-13.2 0.5-37.0 0.6-11.3	10	Rodriguez-Gomez et al.⁸
MePB EtPB PrPB BuPB MePB EtPB PrPB BuPB	SBSE	9.9	0.4-100 0.4-100 0.3-100 0.3-100 0.2-100 0.3-100 0.7-100 0.2-100	0.7-7.2 0.7-13.8 0.8-43.5 0.6-14.5 0.8-7.8 0.7-15.0 0.7-41.2 0.7-13.4	26 15	Rodriguez-Gomez et al.³³
MePB EtPB PrPP BuPB	DLLME with back-extraction	1.0	700-100,000 300-100,000 300-100,000 300-100,000	300-600 300-6000 300-6000 300-6000	not mentioned	Alshana et al.³⁰
MePB EtPB PrPB BuPB	UAE	9.9	0.5-50 0.5-50 0.4-50 0.7-50	1.26-16.3 1.13-18.1 1.02-12.6 1.06-12.1	10	Rodriguez-Gomez et al.³⁴
MePB EtPB PrPB BuPB	online SPE	0.1	not mentioned	0.5-2.3	not mentioned	Hines et al.³⁵
MePB EtPB PrPB	online in-tube SPME	40	0.1-50 0.09-50 0.07-50	0.792-1.180	12	Asiabi et al.³⁶
MePB EtPB PrPB BuPB	in-tube SPME	0.2	10-400 10-400 10-400 3-400	10.8-39.8 11.5-29.6 - 3.0-8.1	10	Queiroz and co‑workers⁹
MePB EtPB PrPB BuPB	DLLME	1.75	0.5-80 0.5-80 0.5-80 0.5-80	1.8-18.6 5.3-6.7 0.7-3.77 -	8.5	Vela-Soria et al.³⁷
MePB EtPB iPrPB PrPB iBuPB BuPB BzPB	SPE	1.0	0.026-50 0.029-50 0.019-50 0.027-50 0.018-50 0.029-50 0.029-50	1.2-8.1 1.3-5.1 0.95-2.2 0.12-2.2 0.15-0.89 0.36 0.12-2.2	24.5	Azzouz et al.³⁸
MePB EtPB PrPB BuPB	QuEChERS	1.0	0.4-80 0.3-80 0.4-80 0.5-80	0.9-21 - 0.4-12 -	4	Vela-Soria et al.³⁹
MePB EtPB PrPB	MA-MSPD-DLLME	0.2	50-4000 50-4000 50-4000	116.2-3270.3 51.2-1498.8 100.4-1066.7	15	Fotouhi et al.⁴⁰
MePB EtPB PrPB BuPB BzPB iBuPB	LLE	not mentioned	0.013-50 0.1-50 0.087-50 0.078-50 0.074-50 0.81-50	0.22-16.325 0.0023-2.183 0.0277-4.588 - - -	15	Fisher et al.⁴¹
MePB EtPB PrPB BuPB	DLLME	1.0	5-100 5-100 5-100 5-100	7.5-87.5 8.7-18.1 8.2 -	6.0	present work

Sample	MePB		EtPB		PrPB		BuPB
Sample	Concentration / (ng mL^-1)	Standard deviation	Concentration / (ng mL^-1)	Standard deviation	Concentration / (ng mL^-1)	Standard deviation	Concentration / (ng mL^-1)	Standard deviation
1	31.2	1.2	8.7	0.2	< LLOQ	0.1	< LLOQ	-
2	16.2	2.6	9.5	0.2	8.2	0.1	< LLOQ	-
3	22.3	1.4	11	0.6	< LLOQ	0.1	ND	-
4	7.5	1.1	7.55	1.3	< LLOQ	-	ND	-
5^a a n = 2. MePB: methylparaben; EtPB: ethylparaben; PrPB: propylparaben; BuPB: butylparaben; LLOQ: lower limit of quantification; ND: not detected.	13.2	0.5	9.0	0.9	< LLOQ	-	ND	-
6^a a n = 2. MePB: methylparaben; EtPB: ethylparaben; PrPB: propylparaben; BuPB: butylparaben; LLOQ: lower limit of quantification; ND: not detected.	7.9	0.2	8.6	1.2	< LLOQ	-	ND	-
7^a a n = 2. MePB: methylparaben; EtPB: ethylparaben; PrPB: propylparaben; BuPB: butylparaben; LLOQ: lower limit of quantification; ND: not detected.	9.5	0.6	11.1	0.4	< LLOQ	-	ND	-
8^a a n = 2. MePB: methylparaben; EtPB: ethylparaben; PrPB: propylparaben; BuPB: butylparaben; LLOQ: lower limit of quantification; ND: not detected.	43.0	1.6	10.5	5.9	< LLOQ	0.1	< LLOQ	-
9	12.3	1.5	16.9	0.4	ND	-	ND	-
10	8.8	0.3	18.1	2.4	ND	-	ND	-
11^a a n = 2. MePB: methylparaben; EtPB: ethylparaben; PrPB: propylparaben; BuPB: butylparaben; LLOQ: lower limit of quantification; ND: not detected.	9.6	1.7	12.4	0.3	ND	-	ND	-
12	11.3	0.8	16.2	0.15	ND	-	ND	-
13	10.3	6.3	14.0	0.5	< LLOQ	0	ND	-
14	71.7	1.5	14.0	0.3	< LLOQ	0	ND	-
15^a a n = 2. MePB: methylparaben; EtPB: ethylparaben; PrPB: propylparaben; BuPB: butylparaben; LLOQ: lower limit of quantification; ND: not detected.	87.5	4.3	13.5	1.1	ND	-	ND	-

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