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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

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2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2020, Vol. 14 Issue (3) : 51    https://doi.org/10.1007/s11783-020-1228-y
RESEARCH ARTICLE
An efficient resin for solid-phase extraction and determination by UPLCMS/MS of 44 pharmaceutical personal care products in environmental waters
Feng Zhu1, Zhijian Yao2,3, Wenliang Ji1, Deye Liu1, Hao Zhang1, Aimin Li2, Zongli Huo1(), Qing Zhou2,3()
1. Jiangsu Provincial Center for Disease Control and Prevention, Nanjing 210009, China
2. State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023, China
3. Jiangsu Guochuang Enviro-protection Technology Co. Ltd., No.19 Changqing Avenue, Nanjing 211100, China
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Abstract

• A hydrophilic resin (GCHM) was facile synthesis and characterized.

• Average absolute recovery of GCHM (75.6%) performs better than Oasis® HLB.

• Detection limits of method (SPE-UPLC-MS/MS) ranged between 0.03 and 0.6 ng/L.

• 22 PPCPs were determined in environmental waters ranging from 0.5 to 1590 ng/L.

In this study, a hydrophilic resin named GCHM was fabricated based on poly(N-vinyl pyrrolidone-co-divinylbenzene), characterized, and applied as a solid-phase extraction (SPE) material. Up to 44 pharmaceuticals and personal care products (PPCPs) belonging to 10 classes were recovered in environmental water samples. Different variables affecting extraction, such as adsorbent amount, sample pH, and loading speed, were optimized. Under optimal conditions, the average absolute recovery of 44 PPCPs was 75.6% using GCHM, indicating a better performance than the commercial Oasis® HLB. SPE with home-made hydrophilic polymeric sorbent followed by ultra-performance liquid chromatography and tandem mass spectrometry was validated, and the method achieved good linearity (r2>0.991, for all analytes). In addition, the method detection limits of target compounds ranged from 0.03 to 0.6 ng/L. The developed method was applied to determine PPCPs in 10 environmental water samples taken from the Yangtze River, Huaihe River, and Taihu Lake, 1 groundwater sample from Changzhou in Jiangsu Province, 1 wastewater sample from Xiamen and 2 seawater samples from the Jiulong River in Fujian Province, China. In these samples, 22 compounds were determined at levels ranging from 0.5 to 1590 ng/L.

Keywords Hydrophilic resin      Solid phase extraction      Pharmaceuticals and personal care product      Ultra-performance liquid chromatography and tandem mass spectrometry      Environmental water     
Corresponding Author(s): Zongli Huo,Qing Zhou   
Issue Date: 11 March 2020
 Cite this article:   
Feng Zhu,Zhijian Yao,Wenliang Ji, et al. An efficient resin for solid-phase extraction and determination by UPLCMS/MS of 44 pharmaceutical personal care products in environmental waters[J]. Front. Environ. Sci. Eng., 2020, 14(3): 51.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-020-1228-y
https://academic.hep.com.cn/fese/EN/Y2020/V14/I3/51
Sampling sites No. Sampling sites Geographic location
East longitude (°E) North latitude (°N)
Y-1 Yangtze River 118.72725 32.04772
Y-2 119.44608 32.21735
Y-3 120.31262 31.94313
Y-4 120.08854 31.91776
H-1 Huaihe River 119.03798 33.58755
H-2 119.93281 32.49077
T-1 Taihu Lake 120.35733 31.54395
T-2 120.28888 31.69576
T-3 120.48317 31.54395
T-4 120.55176 31.53500
W-1 Xiamen 118.13529 24.48.327
S-1 Jiulong River 118.03227 24.44446
S-2 118.04147 24.44156
G-1 Changzhou 119.59089 31.74097
Tab.1  Geographical information of the 14 sampling sites from seven typical surface watersheds in China
Fig.1  Scheme 1 Reaction formula of GCHM polymerization with NVP and DVB as monomers.
Fig.2  MRM chromatograms for [M+ CH3OH+ H]+ ions and [M+ H]+ ions of five β-lactams in one injection.
Fig.3  (A) Low-magnification and (B) high-magnification SEM images of GCHM.IR spectra (C) of the GCHM & HLB material, XPS (D) and contact angles (E) of the GCHM.
Fig.4  Number of PPCPs extracted at varying efficiencies by (A) increasing the amount of GCHM at pH 7, (B) 200 mg of GCHM as a function of pH and (C) 200 mg of GCHM at five loading speeds.
Fig.5  Absolute recoveries of PPCPs for GCHMand Oasis® HLB (200 mg, loading at pH 7, recovery with 5 mL methanol). Error bars represent one standard deviation of six duplicates.
Chemical Surface water (ng/L) Wastewater (ng/L) Seawater (ng/L) Groundwater (ng/L)
Y-1 Y-2 Y-3 Y-4 H-1 H-2 T-1 T-2 T-3 T-4 W-1 S-1 S-2 G-1
Ampicillin 25.1±0.8 18.3±1.2 23.2±2.3 N.D. 26.7±1.5 25.9±1.6 N.D. 19.9±1.6 N.D. N.D. N.D. N.D. N.D. N.D.
Penicillin V 28.5±2.2 N.D. 20.6±1.1 24.5±1.4 22.3±1.9 12.9±1.2 N.D. N.D. N.D. 25.0±0.5 N.D. N.D. N.D. N.D.
Cinoxacin N.D.a) N.D. N.D. N.D. 4.6±0.3 N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D.
Flumequine N.D. N.D. N.D. N.D. 0.6±0.03 N.D. N.D. 0.5±0.04 N.D. N.D. N.D. N.D. N.D. N.D.
Oxolinic acid N.D. N.D. N.D. N.D. 4.5±0.4 0.9±0.08 2.1±0.2 N.D. 0.7±0.05 N.D. N.D. N.D. N.D. N.D.
Sulfachloropyridazine 2.9±0.1 N.D. 2.3±0.05 1.9±0.1 3.3±0.3 2.6±0.2 N.D. N.D. 2.3±0.2 1.9±0.09 N.D. N.D. N.D. N.D.
Sulfadiazine 1.9±0.07 N.D. 1.9±0.1 1.7±0.09 N.D. 1.4±0.07 N.D. 1.5±0.1 N.D. 1.5±0.07 N.D. N.D. N.D. N.D.
Sulfamethazine 3.2±0.3 N.D. 1.2±0.1 2.2±0.2 5.5±0.05 N.D. N.D. N.D. N.D. 2.1±0.1 N.D. N.D. N.D. N.D.
Sulfamethoxazole 10.2±0.4 8.8±1.0 16.9±1.1 16.7±1.2 15.5±1.4 13.5±1.0 2.3±0.1 17.4±1.4 15.8±1.6 16.9±1.5 11.4±0.5 2.1±0.2 1.1±0.1 N.D.
Sulfapyridine 0.6±0.04 N.D. 0.6±0.07 N.D. N.D. N.D. N.D. 0.5±0.04 N.D. N.D. 10.5±0.3 1.1±0.08 N.D. N.D.
Sulfaphenazole N.D. N.D. N.D. N.D. N.D. 0.5±0.03 N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D.
Clarithromycin N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. 1. 2±0.09 13.2±0.6 1.9±0.1 N.D. N.D.
Erythromycin 33.5±0.9 N.D. N.D. N.D. N.D. 3.6±0.1 1.5±0.1 N.D. N.D. N.D. 1588.9±159.2 54.3±3.4 39.7±3.1 N.D.
Lincomycin 4.8±0.06 1.2±0.08 6.8±0.4 5.3±0.2 6.6±0.4 5.7±0.5 3.2±0.2 2.1±0.2 2.1±0.07 4.4±0.2 N.D. N.D. N.D. N.D.
Trimethoprim N.D. N.D. N.D. N.D. N.D. N.D. N.D. 2.6±0.2 N.D. N.D. N.D. 43.1±2.9 21.1±1.8 N.D.
Caffeine 26.5±1.3 22.1±1.7 44.9±4.1 39.8±3.2 27.5±1.0 28.6±1.0 24.5±0.03 44.5±2.3 32.5±2.4 65.2±3.8 85.1±6.2 69.9±4.2 56.7±3.8 N.D.
Carbamazepine N.D. N.D. N.D. N.D. 3.1±0.1 N.D. 0.9±0.05 2.1±0.2 2.9±0.2 N.D. 10.3±0.5 2.8±0.3 1.9±0.3 N.D.
Codeine 178.8±23.4 25.5±1.6 118.3±13.2 99.8±4.4 53.5±4.2 18.8±1.5 46.6±2.3 65.6±6.0 55.6±2.2 63.5±3.1 N.D. 0.4±0.02 N.D. N.D.
1,7-Dimethylxanthine 12.3±0.8 11.3±1.0 23.9±1.1 23.9±1.4 15.6±1.4 15.9±1.4 1.9±0.04 21.2±0.9 14.9±0.6 22.5±1.6 N.D. N.D. N.D. N.D.
Enrofloxacin N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. 1.7±0.1 N.D. N.D.
Ofloxacin N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. 98.2±4.8 21.9±0.9 12.1±0.7 N.D.
Sarafloxacin N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. 0.3±0.02 N.D. 0.5±0.04 N.D.
Tab.2  Concentrations of analytes in surface water, wastewater, seawater and groundwater samples as determined using the in-house GCHM sorbent for SPEfollowed by UPLC–MS/MS
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