Analysis of parabens in environmental water samples by covalent organic framework-based magnetic solid-phase extraction-high performance liquid chromatography

doi:10.3724/SP.J.1123.2022.06006

Abstract

Abstract:

Parabens are a class of antimicrobial preservatives that are widely used in cosmetics, pharmaceuticals, and food products because of their ease of production, antimicrobial effect, and low price. The widespread use of these parabens, poses potential risks to human health. Therefore, it is necessary to establish a simple and rapid method for the detection of parabens. The large number of substrate interferences in complex samples is an important factor affecting the sensitivity of analytical methods. Magnetic solid-phase extraction (MSPE) has received much attention because of its advantages of easy operation, short extraction time, small sample amount, low cost, and environmental friendliness. Covalent organic frameworks (COFs) with high crystallinity, high specific surface area, adjustable pore size, regular porosity, as well as high chemical and thermal stability are now widely used in separation and analysis. Therefore, a sample pretreatment method combining MSPE and COF for the analysis of parabens in complex matrices is very promising. A magnetic covalent organic framework, Fe₃O₄@TbBd, was successfully synthesized by the Schiff base reaction of 1,3,5-triformylbenzene (Tb) and benzidine (Bd) at room temperature using Fe₃O₄ nanoparticles as magnetic cores. Characterization by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), vibrating sample magnetometer (VSM) measurements, etc. revealed that the magnetic COF has high magnetic responsiveness, as well as good thermal and chemical stability, which make it an ideal adsorbent for the MSPE of parabens. Some factors related to the extraction efficiency, including the amount of adsorbent, extraction time, pH, desorption solvent, desorption time, and number of desorption were systematically investigated. A method involving MSPE and high performance liquid chromatography-ultraviolet detection (HPLC-UV) based on the Fe₃O₄@TbBd was developed for the determination of four parabens (ethylparaben, propylparaben, butylparaben, and benzylparaben) in environmental water samples. Under the optimal extraction conditions, the method showed good linearities. The limits of detection and limits of quantification were 0.2-0.4 μg/L and 0.7-1.4 μg/L for the four analytes, respectively. The recoveries at three spiked levels were in the range of 86.1%-110.8% with intra-day and inter-day RSDs of less than 5.5% and 4.9%, respectively. The method was successfully applied to the determination of parabens in East Lake water, Yangtze water, and domestic wastewater. Ethyl paraben and propyl paraben were detected in domestic wastewater at the levels of 1.8 μg/L and 0.4 μg/L, respectively. The recoveries of the parabens at different spiked levels ranged from 80.7% to 117.5%, with RSDs of 0.2%-8.8%. The method has good potential for the determination of parabens in environmental water samples because of its operational simplicity, short extraction time, high sensitivity, and environmental friendliness.

Key words: covalent organic framework (COF), magnetic solid-phase extraction (MSPE), high performance liquid chromatographic (HPLC), parabens, environment water

CLC Number:

O658

BAO Yue, ZHAI Yixin, NING Tao, CHEN Pin, ZHU Shukui. Analysis of parabens in environmental water samples by covalent organic framework-based magnetic solid-phase extraction-high performance liquid chromatography[J]. Chinese Journal of Chromatography, 2022, 40(11): 1005-1013.

Figures/Tables 8

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Analyte	Linear range/(μg/L)	Regression equation	r	LOD/(μg/L)	LOQ/(μg/L)
EtP	1-100	y=5637.9x+65309	0.9912	0.2	0.7
PrP	1-100	y=7932.2x+8160.3	0.9991	0.3	0.9
BuP	1-300	y=6882.2x+39552	0.9982	0.4	1.4
BzP	1-500	y=7608.3x+42246	0.9998	0.3	1.1

Analyte	Linear range/(μg/L)	Regression equation	r	LOD/(μg/L)	LOQ/(μg/L)
EtP	1-100	y=5637.9x+65309	0.9912	0.2	0.7
PrP	1-100	y=7932.2x+8160.3	0.9991	0.3	0.9
BuP	1-300	y=6882.2x+39552	0.9982	0.4	1.4
BzP	1-500	y=7608.3x+42246	0.9998	0.3	1.1

Analyte	Recoveries/%			Intra-day RSDs (n=5)/%			Inter-day RSDs (n=3)/%
Analyte	10 μg/L	50 μg/L	100 μg/L	10 μg/L	50 μg/L	100 μg/L	10 μg/L	50 μg/L	100 μg/L
EtP	107.9	94.5	93.2	4.1	3.4	4.8	2.2	2.5	3.9
PrP	97.8	103.1	97.7	2.9	5.5	1.0	2.2	3.8	0.1
BuP	92.8	110.8	103.8	3.0	2.5	1.6	1.2	0.7	4.6
BzP	86.1	102.8	103.9	3.4	2.8	2.1	1.2	3.5	4.9

Analyte	Recoveries/%			Intra-day RSDs (n=5)/%			Inter-day RSDs (n=3)/%
Analyte	10 μg/L	50 μg/L	100 μg/L	10 μg/L	50 μg/L	100 μg/L	10 μg/L	50 μg/L	100 μg/L
EtP	107.9	94.5	93.2	4.1	3.4	4.8	2.2	2.5	3.9
PrP	97.8	103.1	97.7	2.9	5.5	1.0	2.2	3.8	0.1
BuP	92.8	110.8	103.8	3.0	2.5	1.6	1.2	0.7	4.6
BzP	86.1	102.8	103.9	3.4	2.8	2.1	1.2	3.5	4.9

Analysis method	Analytes	Samples	Extraction method	Extraction time/min	LOD/ (μg/L)		Recovery/ %		Ref.
HPLC-UV	5 PBs	hand cream	MSPE	30	0.25-	0.34	85.8-	112.6	[29]
HPLC-PDA	4 PBs	cream, sunscreen, etc.	SPE	-	5-	20	85.95-	142.72	[30]
HPLC-DAD	4 PBs	mouthwash, handwash	multi-stir-rod	25	0.63-	0.8	83-	103	[31]
HPLC-DAD	4 PBs	water-based skin toners	MSPE	2	10-	25	98-	106	[32]
HPLC-DAD	4 PBs	scream, lotions	SPME	20	120-	150	90.2-	97.7	[33]
HPLC-UV	4 PBs	beverage, food	MSPE	10	0.51-	1.89	59.2-	109	[34]
HPLC-UV	4 PBs	water, urine	MSPE-DES	8	0.1-	0.3	81.8-	118.2	[35]
HPLC-UV	4 PBs	environment samples	MSPE	10	0.2-	0.4	86.1-	110.8	this work