Sensitive Estrogens Determination in Wastewater Samples by HPLC and Fluorescence Detection

Liz, Marcus Vinicius de; Amaral, Bianca do; Stets, Sandra; Nagata, Noemi; Peralta-Zamora, Patricio

doi:10.21577/0103-5053.20160324

Acessibilidade / Reportar erro

Brasil

Journal of the Brazilian Chemical Society

Español English

Brasil

Español English

sumário « anterior atual seguinte »

Sumário

Articles • J. Braz. Chem. Soc. 28 (08) • Aug 2017 • https://doi.org/10.21577/0103-5053.20160324 copy

Sensitive Estrogens Determination in Wastewater Samples by HPLC and Fluorescence Detection

Authorship SCIMAGO INSTITUTIONS RANKINGS

A sensitive high-performance liquid chromatography-fluorescence detection method (HPLC-FLD) was developed and validated for 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) determination in wastewater samples. Sample preparation was performed by solid-phase extraction (SPE) on Hypersep C18 cartridges. Conditioning and elution solvents and sample volume were investigated by a 2³ factorial design for both analytes. The pre-concentration factor was 2500 times, allowing to quantify 5.0 ng L^-1 for both hormones. The SPE-HPLC-FLD method was successfully applied to detect and quantify trace amount of target compounds in raw and treated wastewater samples. E2 was found below limit of quantification in influent and effluent samples. Nevertheless, the recoveries of E2 in standard addition experiments were between 41 and 72%, with relative standard deviations between 4 and 16%. An important matrix effect was observed in the determination of EE2, with fluorescence signal suppression.

Keywords:
estrogens; SPE; HPLC; fluorescence; wastewater

Conditioning		Sample volume / mL		Elution
(-)^a a Adapted from Girotto et al.;39	(+)^b b adapted from López de Alda and Barceló.20	(-)	(+)	(-)^a a Adapted from Girotto et al.;39	(+)^b b adapted from López de Alda and Barceló.20
4 mL acetone 5 mL methanol 5 mL ultrapure water	7 mL acetonitrile 5 mL methanol 5 mL ultrapure water	100	500	2× 5 mL acetone	2× 5 mL acetonitrile

Concentration / (µg L^-1)	Sample volume / mL	Final volume / mL	Recovery ± RSD^a a RSD: relative standard deviation (n = 3). / %
Concentration / (µg L^-1)	Sample volume / mL	Final volume / mL	E2	EE2
20.00	100	1.00	99.2 ± 11.7	98.8 ± 10.5
10.00	100	1.00	98.0 ± 2.0	97.0 ± 5.6
0.50	100	1.00	93.0 ± 1.9	91.4 ± 3.9
0.50	200	1.00	96.6 ± 2.5	95.6 ± 2.3
0.10	100	1.00	74.9 ± 35.8	102 ± 19.8
0.10	200	1.00	91.7 ± 6.6	107 ± 3.0
0.10	500	1.00	89.0 ± 9.2	92.4 ± 2.2
0.01	200	0.10	86.5 ± 20.2	78.6 ± 36.6
0.01	300	0.15	99.1 ± 0.7	103 ± 3.1
0.01	500	0.20	98.4 ± 7.8	104 ± 2.0

	E2	EE2
Equation	Y = -0.342 + 74.94X	Y = -0.244 + 66.59X
R²	0.9998	0.9955
LCR^a a LCR: linear calibration range; / (µg L^-1)	10-200	10-200
n	10	10
LOD^b b LOD: limit of detection; / (ng L^-1)	2.5	2.5
LOQ^c c LOQ: limit of quantification; / (ng L^-1)	5	5
Recovery ± RSD^d d RSD: relative standard deviation (n = 3; 10 ng L-1). / %	99.1 ± 0.7	103 ± 3.1

Sample (n = 3)	Concentration found / (ng L^-1)	Recovery / %	RSD / %
Influent^a a Direct interpolation;	5.96	-	-
Spiked influent (10 ng L^-1)	7.16	71.7	4.06
Spiked influent (50 ng L^-1)	33.0	66.1	3.65
Spiked influent (75 ng L^-1)	47.8	63.8	11.4
Spiked influent (100 ng L^-1)	64.7	64.7	3.90
Influent^b b standard addition.	3.39	-	-
Effluent^a a Direct interpolation;	2.98	-	-
Spiked effluent (10 ng L^-1)	4.08	40.8	13.1
Spiked effluent (50 ng L^-1)	30.2	60.2	9.12
Spiked effluent (75 ng L^-1)	50.2	67.0	16.5
Spiked effluent (100 ng L^-1)	56.6	56.6	10.3
Effluent^b b standard addition.	0.61	-	-

Analyte	Matrix	Method	LOD / (ng L^-1)	Recovery / %	Sample volume / mL	Reference
E2, EE2	wastewater	SPE-HPLC-FLD	2.5	41-72	300	this study
E2, EE2	tap water, surface water, and wastewater	DLLME^a a DLLME: dispersive liquid-liquid microextraction; -HPLC-FLD	2-6.5	86-120	8	²⁶26 Lima, D. L. D.; Silva, C. P.; Otero, M.; Esteves, V. I.; Talanta 2013, 115, 980.
EE2	wastewater	in-tube-SPME^b b In-tube-SPME: in-tube solid phase microextraction; -HPLC-FLD	5-10	85.2-99.4	0.075-0.10	²⁵25 Aufartová, J.; Torres-Padrón, M. E.; Sosa-Ferrera, Z.; Solich, P.; Santana-Rodríguez, J. J.; Int. J. Environ. Anal. Chem. 2012, 92, 382.
E2, EE2	drinking water, river water, wastewater, and hospital effluent	FPSE^c c FPSE: fabric phase sorptive extraction. -HPLC-FLD	20-36	89.0-98.0	10	³⁴34 Kumar, R.; Gaurav; Heena; Malik, A. K.; Kabir, A.; Furton, K. G.; J. Chromatogr. A 2014, 1359, 16.
EE2	drinking and river water	SPE-HPLC-FLD	650	83	100	³⁷37 Melo, S. M.; Brito, N. M.; Water, Air, Soil Pollut. 2014, 225, 1783.
E2, EE2	surface water and wastewater	SPE-LC-MS/MS	0.2-1.0	103-109	1000	⁴⁷47 Sodré, F. F.; Pescara, I. C.; Montagner, C. C.; Jardim, W. F.; Microchem. J. 2010, 96, 92.

Sociedade Brasileira de Química Instituto de Química - UNICAMP, Caixa Postal 6154, 13083-970 Campinas SP - Brazil, Tel./FAX.: +55 19 3521-3151 - São Paulo - SP - Brazil
E-mail: office@jbcs.sbq.org.br

Acompanhe os números deste periódico no seu leitor de RSS

[1] *e-mail: zamora@ufpr.br