A Reliable and Cost-Effective Method for Determination of Endocrine-Disrupting Compounds in Coastal Waters, Suspended Particulate Matter, and Sediments by Ultrafast Liquid Chromatography Coupled to Photodiode Array and Fluorescence Detectors

Souza, Gabriel C. de; Fahning, Cristiane S; Hatje, Vanessa; Rocha, Gisele O. da

doi:10.21577/0103-5053.20210108

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Article • J. Braz. Chem. Soc. 32 (12) • Dec 2021 • https://doi.org/10.21577/0103-5053.20210108 linkcopy

A Reliable and Cost-Effective Method for Determination of Endocrine-Disrupting Compounds in Coastal Waters, Suspended Particulate Matter, and Sediments by Ultrafast Liquid Chromatography Coupled to Photodiode Array and Fluorescence Detectors

Authorship SCIMAGO INSTITUTIONS RANKINGS

Abstract

Analytical methods for determining 14 endocrine-disrupting compounds (EDCs) in coastal waters, suspended particles, and sediment samples were successfully performed by ultrafast liquid chromatography with photodiode array and fluorescence detections (UFLC-PDA-FLD). Solid phase extraction (SPE) and ultrasound-assisted extraction (USE) were used for sample preparation. Two chromatographic methods have been developed. An isocratic separation method was used to separate bisphenol A (BPA) and steroids and another gradient elution method to separate phthalates and alkylphenols. The detection by fluorescence was used for alkylphenols, BPA, and steroids and photodiode array (PDA) for phthalates. Limits of detection (LOD) ranged from 0.41 (4-tert-octylphenol (4tOP)) to 63 ng L^-1 (dibutylphthalate (DBP)), 0.41 (4tOP) to 63.2 ng g^-1 dried weight (dw) coastal waters, and solid samples (suspended particulate matter (SPM) and sediment samples), respectively. Recoveries ranged from 52 (diethylphthalate (DEP)) to 116% (DBP) for water, from 54 (DEP) to 108% (estrone (E1)) for SPM, and from 62 (4-n-nonylphenol (4nNP)) to 117% (4-n-octylphenol (4nOP)) for sediment samples. Finally, with the minimization of reagents and energy, the proposed methods were applied to samples collected from Todos os Santos Bay (BTS), Bahia, Northeastern Brazil.

Keywords:
alkylphenols; steroid hormones; phthalates; bisphenol A; plasticizers

Compound	Recovery level ± one standard deviation / %
	Oasis HLB				C18
	i	ii	iii	iv	i	ii	iii	iv
E3	95 ± 4.9	111 ± 4.8	95 ± 3.8	nd	12 ± 1.5	86 ± 10	115 ± 1.1	11 ± 1.1
BPA	89 ± 6.6	99 ± 0.081	102 ± 3.0	nd	47 ± 4.0	97 ± 4.0	112 ± 1.4	47 ± 1.9
E2	87 ± 1.9	98 ± 9.0	108 ± 2.0	nd	105 ± 0.77	99 ± 7.6	112 ± 6.9	99 ± 6.4
EE2	101 ± 3.1	101 ± 4.0	103 ± 3.4	nd	96 ± 0.12	97 ± 2.3	104 ± 0.055	92 ± 3.1
E1	107 ± 3.7	84 ± 3.4	89 ± 4.6	nd	99 ± 1.0	97 ± 3.8	101 ± 0.091	94 ± 0.71
4tOP	78 ± 3.2	62 ± 4.3	88 ± 4.0	nd	85 ± 3.0	85 ± 2.0	72 ± 0.18	75 ± 9.9
4nOP	49 ± 1.3	nd	85 ± 4.7	nd	70 ± 0.078	92 ± 5.2	51 ± 3.3	57 ± 6.7
4nNP	nd	nd	53 ± 1.5	nd	25 ± 4.9	63 ± 3.2	26 ± 12.2	13 ± 1.3
DMP	114 ± 3.1	20 ± 0.76	67 ± 5.2	nd	41 ± 2.7	68 ± 4.7	49 ± 3.2	32 ± 1.4
DEP	102 ± 7.8	36 ± 1.6	81 ± 6.5	nd	71 ± 8.6	89 ± 5.2	70 ± 0.37	52 ± 6.3
BBP	75 ± 7.7	78 ± 0.70	89 ± 4.0	nd	82 ± 1.8	84 ± 3.6	87 ± 2.1	82 ± 2.2
DBP	89 ± 12	83 ± 3.1	96 ± 3.7	nd	90 ± 0.62	92 ± 4.8	90 ± 1.9	85 ± 6.2
DEHP	40 ± 3.5	36 ± 2.7	34 ± 3.4	nd	35 ± 0.53	86 ± 5.3	85 ± 2.4	40 ± 2.6
DnOP	33 ± 4.3	32 ± 3.6	29 ± 1.9	nd	35 ± 0.60	91 ± 3.5	84 ± 3.0	41 ± 2.8

Method	Analyte	t_R / min	Calibration curve	Linearity (R²)	Linear range / (µg L^-1)	LOD^a / (µg L^-1)	LOQ^a / (ng L^-1)	Seawater LODb / (ng L^-1)	Seawater LOQb / (ng L^-1)	Solid samples LODc / (ng g^-1 dw)	Solid samples LOQc / (ng g^-1 dw)
1	E3	1.45	y = 313x + 24.2	0.9973	1.36-50	1.36	4.52	0.678	2.26	0.678	2.26
	BPA	3.54	y = 210x - 149	0.9955	1.52-50	1.52	5.06	0.759	2.53	0.759	2.53
	E2	4.49	y = 386x - 72.3	0.9991	1.63-50	1.63	5.44	0.816	2.72	0.816	2.72
	EE2	5.76	y = 404x + 95.3	0.9992	1.30-50	1.30	4.34	0.652	2.17	0.652	2.17
	E1	6.17	y = 25.4x + 65.3	0.9971	7.98-250	7.98	26.6	3.99	13.3	3.99	13.3
2	4tOP	4.04	y = 190x - 161	0.9981	1.30-50	1.30	4.33	0.412	1.37	0.412	1.37
	4nOP	6.18	y = 139x - 13.3	0.9992	0.825-50	0.825	2.75	0.649	2.16	0.649	2.16
	4nNP	8.15	y = 145x - 251	0.9989	1.01-50	1.01	3.36	0.503	1.68	0.503	1.68
	DMP	1.21	y = 5.03x + 39	0.9998	81.6-10000	81.6	272	40.8	136	40.8	136
	DEP	1.65	y = 4.10x + 111	0.9997	90.5-10000	90.5	302	45.2	151	45.2	151
	BBP	4.19	y = 3.86x + 121	0.9995	117-10000	117	389	58.4	195	58.4	195
	DBP	4.72	y = 2.98x + 289	0.9994	126-10000	126	422	63.2	211	63.2	211
	DEHP	10.0	y = 2.30x + 807	0.9998	70.0-10000	70.0	233	35.0	117	35.0	117
	DnOP	10.2	y = 2.45x - 27.9	0.9998	64.0-10000	64.0	213	32.0	107	32.0	107

Analyte	ALA		CAB		MAT		SFC		TMA
Analyte	sw / (ng L^-1)	SPM / (ng g^-1 dw)	sw / (ng L^-1)	SPM / (ng g^-1 dw)	sw / (ng L^-1)	SPM / (ng g^-1 dw)	sw / (ng L^-1)	SPM / (ng g^-1 dw)	sw / (ng L^-1)	SPM / (ng g^-1 dw)
E3	< LOD	< LOD	< LOD	< LOD	< LOD	27.5 ± 1.3	< LOD	< LOD	< LOD	22.0 ± 1.8
BPA	139	126 ± 16	6.60	239 ± 21	8.90	185 ± 11	31.1	152 ± 18	78.5	338 ± 76
E2	< LOD	< LOD	< LOD	< LOD	0.95	< LOD	< LOD	< LOD	< LOD	< LOD
EE2	< LOD	< LOD	< LOD	< LOD	< LOD	< LOD	3.21	< LOD	< LOD	< LOD
E1	< LOD	< LOD	< LOD	< LOD	22.3	< LOD	< LOD	< LOD	< LOD	< LOD
4tOP	66.0	< LOD	2.10	< LOD	< LOD	< LOD	< LOD	< LOD	2.32	< LOD
4nOP	< LOD	< LOD	< LOD	< LOD	< LOD	< LOD	< LOD	< LOD	< LOD	< LOD
4nNP	< LOD	367 ± 18	2.00	418 ± 19	4.16	368 ± 25	3.34	402 ± 19	3.41	670 ± 90
DMP	< LOD	23260 ± 128	1244	9984 ± 63	851	18710 ± 1230	1795	21631 ± 3067	748	30251 ± 1543
DEP	< LOD	2539 ± 203	< LOD	5045 ± 46	< LOD	< LOD	< LOD	3846 ± 515	< LOD	2496 ± 515
BBP	420	3714 ± 267	< LOD	25703 ± 680	< LOD	25908 ± 3039	63.6	13990 ± 746	< LOD	23555 ± 3313
DBP	< LOD	917570 ± 9890	< LOD	< LOD	< LOD	51527 ± 4073	< LOD	30246 ± 4531	< LOD	1817 ± 321
DEHP	905	55786 ± 1830	< LOD	24030 ± 68	< LOD	33852 ± 5305	< LOD	11524 ± 642	< LOD	206986 ± 37415
DnOP	< LOD	49681 ± 4943	75.6	155927 ± 307	46	65115 ± 7624	85.7	17107 ± 667	54.5	628497 ± 66763
SPM / (mg L^-1 dw)	22		2.0		3.9		6.6		4.0

Analyte	Concentration / (ng g^-1 dw)
Analyte	1	2	3	4
E3	< LOD	< LOD	< LOD	< LOD
BPA	1.89 ± 1.0	< LOD	< LOD	1.08 ± 0.076
E2	< LOD	< LOD	< LOD	< LOD
EE2	< LOD	< LOD	< LOD	< LOD
E1	< LOD	< LOD	3.79 ± 0.26	4.37 ± 0.31
4tOP	40.0 ± 2.7	32.1 ± 4.2	62.7 ± 1.7	61.4 ± 5.1
4nOP	< LOD	< LOD	< LOD	< LOD
4nNP	3.18 ± 0.18	3.34 ± 0.12	2.54 ± 0.18	1.83 ± 0.13
DMP	1285 ± 65	3318 ± 186	1721 ± 31	1686 ± 90
DEP	< LOD	46.9 ± 3.3	< LOD	51.5 ± 4.1
BBP	< LOD	68.2 ± 1.5	339 ± 10	373 ± 29
DBP	267 ± 13	341 ± 11	265 ± 9.8	313 ± 27
DEHP	380 ± 18	688 ± 20	407 ± 9.7	321 ± 19
DnOP	494 ± 17	307 ± 6.5	637 ± 28	667 ± 63

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[TFN1] (i) 15 mL ACN/MeOH 1:1 (v v^-1); (ii) 15 mL ACN followed by 15 mL de MeOH; (iii) 15 mL acetone followed by 15 mL MeOH; (iv) 15 mL MeOH. E3: estriol; BPA: bisphenol A; E2: 17β-estradiol; EE2: ethynylestradiol; E1: estrone; 4tOP: 4-t-octylphenol; 4nOP: 4-n-octylphenol; 4nNP: 4-n-nonylphenol; DMP: dimethylphthalate; DEP: diethylphthalate; BBP: butylbenzylphthalate; DBP: di-n-butylphthalate; DEHP: di-(2-ethylhexyl)phthalate; DnOP: di-n-octylphthalate; nd: not detected.