Skip to main content
Log in

An efficient resin for solid-phase extraction and determination by UPLCMS/MS of 44 pharmaceutical personal care products in environmental waters

  • Research Article
  • Published:
Frontiers of Environmental Science & Engineering Aims and scope Submit manuscript

Abstract

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Abdallah A E M, Nguyen K H, Ebele A J, Atia N N, Ali H R H, Harrad S (2019). A single run, rapid polarity switching method for determination of 30 pharmaceuticals and personal care products in waste water using Q-Exactive Orbitrap high resolution accurate mass spectrometry. Journal of Chromatography. A, 1588: 68–76

    Article  Google Scholar 

  • Althakafy J T, Kulsing C, Grace M R, Marriott P J (2018). Determination of selected emerging contaminants in freshwater invertebrates using a universal extraction technique and liquid chromatography accurate mass spectrometry. Journal of Separation Science, 41(19): 3706–3715

    Article  CAS  Google Scholar 

  • Bratkowska D, Marcé R M, Cormack P A G, Borrull F, Fontanals N (2011). Development and application of a polar coating for stir bar sorptive extraction of emerging pollutants from environmental water samples. Analytica Chimica Acta, 706(1): 135–142

    Article  CAS  Google Scholar 

  • Brousmiche D W, O’Gara J E, Walsh D P, Lee P J, Iraneta P C, Trammell B C, Xu Y, Mallet C R (2008). Functionalization of divinylbenzene/N-vinylpyrrolidone copolymer particles: Ion exchangers for solid phase extraction. Journal of Chromatography. A, 1191(1–2): 108–117

    Article  CAS  Google Scholar 

  • Chen R, Yang Y Y, Wang N, Hao L J, Li L, Guo X Y, Zhang J C, Hu Y Z, Shen W Y (2015). Application of packed porous nanofibers—Solid-phase extraction for the detection of sulfonamide residues from environmental water samples by ultra high performance liquid chromatography with mass spectrometry. Journal of Separation Science, 38(5): 749–756

    Article  CAS  Google Scholar 

  • Dias N C, Poole C F (2002). Mechanistic study of the sorption properties of OASIS-HLB and its use in solid-phase extraction. Chromatographia, 56(5–6): 269–275

    Article  CAS  Google Scholar 

  • Fontanals N, Galià M, Marcé R M, Borrull F (2004). Comparison of hydrophilic polymeric dorbents for on-line solid-phase extraction of polar compounds from aqueous samples. Chromatographia, 60(9): 511–515

    Article  CAS  Google Scholar 

  • Gómez M J, Petrovic M, Fernández-Alba A R, Barceló D (2006). Determination of pharmaceuticals of various therapeutic classes by solid-phase extraction and liquid chromatography-tandem mass spectrometry analysis in hospital effluent wastewaters. Journal of Chromatography. A, 1114(2): 224–233

    Article  Google Scholar 

  • Gros M, Petrovic M, Barceló D (2006). Development of a multi-residue analytical methodology based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters. Talanta, 70(4): 678–690

    Article  CAS  Google Scholar 

  • Hua Z C, Guo K H, Kong X J, Lin S K, Wu Z H, Wang L P, Huang H, Fang J Y (2019). PPCP degradation and DBP formation in the solar/free chlorine system: Effects of pH and dissolved oxygen. Water Research, 150: 77–85

    Article  CAS  Google Scholar 

  • Jeong Y, Schaffer A, Smith K (2017). Equilibrium partitioning of organic compounds to OASIS HLB((R)) as a function of compound concentration, pH, temperature and salinity. Chemosphere, 174: 297–305

    Article  CAS  Google Scholar 

  • Lee K J, Lee D K, Kim Y W, Choe W S, Kim J H (2007). Theoretical consideration on the glass transition behavior of polymer nanocomposites. Journal of Polymer Science. Part B, Polymer Physics, 45(16): 2232–2238

    Article  CAS  Google Scholar 

  • Li Q L, Lam M H W, Wu R S S, Jiang B W (2010). Rapid magnetic-mediated solid-phase extraction and pre-concentration of selected endocrine disrupting chemicals in natural waters by poly(divinyl-benzene-co-methacrylic acid) coated Fe3O4 core-shell magnetite microspheres for their liquid chromatography-tandem mass spectrometry determination. Journal of Chromatography. A, 1217(8): 1219–1226

    Article  Google Scholar 

  • Li Y, Xie X, Lee M L, Chen J (2011). Preparation and evaluation of hydrophilic C18 monolithic sorbents for enhanced polar compound retention in liquid chromatography and solid phase extraction. Journal of Chromatography. A, 1218(48): 8608–8616

    Article  Google Scholar 

  • Li Z, Xiang X, Li M, Ma Y P, Wang J H, Liu X (2015). Occurrence and risk assessment of pharmaceuticals and personal care products and endocrine disrupting chemicals in reclaimed water and receiving groundwater in China. Ecotoxicology and Environmental Safety, 119: 74–80

    Article  CAS  Google Scholar 

  • Liu W J, Zheng R, He Z C (2008). One-stage preparation of PSt/PNVP core/shell nanoparticles via interfacial-initiated microemulsion copolymerization. Polymer Bulletin, 61(1): 27–34

    Article  CAS  Google Scholar 

  • Luan S F, Zhao J, Yang H W, Shi H C, Jin J, Li X M, Liu J C, Wang J W, Yin J H, Stagnaro P (2012). Surface modification of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via UV-induced graft polymerization of N-vinyl pyrrolidone. Colloids and Surfaces. B, Biointerfaces, 93: 127–134

    Article  CAS  Google Scholar 

  • Ma Y X, Han D D, Lei Y J, Zhu T (2018). Dispersion solid-phase extraction of flavonoid with amphiphilic monomers N-vinyl pyrrolidone and 1H,1H,7H-dodecafluoroheptyl methacrylate based poly(styrene-divinylbenzene) and silica. Analytical Methods, 10(38): 4680–4688

    Article  CAS  Google Scholar 

  • Pailler J Y, Krein A, Pfister L, Hoffmann L, Guignard C (2009). Solid phase extraction coupled to liquid chromatography-tandem mass spectrometry analysis of sulfonamides, tetracyclines, analgesics and hormones in surface water and wastewater in Luxembourg. Science of the Total Environment, 407(16): 4736–4743

    Article  CAS  Google Scholar 

  • Pathak A K, Kumar V, Sharma S, Yokozeki T, Dhakate S R (2019). Improved thermomechanical and electrical properties of reduced graphene oxide reinforced polyaniline-dodecylbenzene sulfonic acid/divinylbenzene nanocomposites. Journal of Colloid and Interface Science, 533: 548–560

    Article  CAS  Google Scholar 

  • Shi P, Zhou S C, Xiao H X, Qiu J F, Li A M, Zhou Q, Pan Y, Hollert H (2018). Toxicological and chemical insights into representative source and drinking water in eastern China. Environmental Pollution, 233: 35–44

    Article  CAS  Google Scholar 

  • Spongberg A L, Witter J D, Acuna J, Vargas J, Murillo M, Umana G, Gomez E, Perez G (2011). Reconnaissance of selected PPCP compounds in Costa Rican surface waters. Water Research, 45(20): 6709–6717

    Article  CAS  Google Scholar 

  • Stasinakis A S (2012). Review on the fate of emerging contaminants during sludge anaerobic digestion. Bioresource Technology, 121: 432–440

    Article  CAS  Google Scholar 

  • Sun Q, Li M Y, Ma C, Chen X Q, Xie X Q, Yu C P (2016a). Seasonal and spatial variations of PPCP occurrence, removal and mass loading in three wastewater treatment plants located in different urbanization areas in Xiamen, China. Environmental Pollution, 208: 371–381

    Article  CAS  Google Scholar 

  • Sun Q, Li Y, Li M Y, Ashfaq M, Lv M, Wang H J, Hu A Y, Yu C P (2016b). PPCPs in Jiulong River estuary (China): Spatiotemporal distributions, fate, and their use as chemical markers of wastewater. Chemosphere, 150: 596–604

    Article  CAS  Google Scholar 

  • Vijaykumar S, Prasannkumar S, Sherigara B S, Shelke N B, Aminabhavi T M, Reddy B S R (2009). Copolymerization of N-vinyl pyrrolidone with functionalized vinyl monomers: synthesis, characterization and reactivity relationships. Macromolecular Research, 17(12): 1003–1009

    Article  CAS  Google Scholar 

  • Xu C, Chen L, You L H, Xu Z, Ren L F, Yew-Hoong Gin K, He Y L, Kai W Z (2018). Occurrence, impact variables and potential risk of PPCPs and pesticides in a drinking water reservoir and related drinking water treatment plants in the Yangtze Estuary. Environmental Science. Processes & Impacts, 20(7): 1030–1045

    Article  CAS  Google Scholar 

  • Yang Y, Ok Y S, Kim K H, Kwon E E, Tsang Y F (2017). Occurrences and removal of pharmaceuticals and personal care products (PPCPs) in drinking water and water/sewage treatment plants: A review. Science of the Total Environment, 596–597: 303–320

    Article  Google Scholar 

  • Yu H J, Cao W P (2016). Assessment of pharmaceutical and personal care products (PPCPs) of Dalong Lake in Xuzhou by concentration monitoring and bio-effects monitoring process. Environmental Toxicology and Pharmacology, 43: 209–215

    Article  CAS  Google Scholar 

  • Zhang Q Q, Ying G G, Pan C G, Liu Y S, Zhao J L (2015). Comprehensive evaluation of antibiotics emission and fate in the river basins of China: Source analysis, multimedia modeling, and linkage to bacterial resistance. Environmental Science & Technology, 49(11): 6772–6782

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Authors gratefully acknowledge the generous support provided by the National Key R&D Program of China (Grant No. 2016YFE0112300), the National Natural Science Foundation of China (Grant Nos. 51678290, 51438008 and 51778281), Jiangsu Natural Science Fund, China (No. BK20171342), Jiangsu Provincial Key Medical Discipline (Laboratory) of China (No. ZDXKA2016008), Jiangsu Preventive Medicine Project of China (No. Y2018081). The authors also thank Dr. Zhe Wang from Nanyang Technological University (Singapore) for his support on this project.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Zongli Huo or Qing Zhou.

Additional information

Highlights

• 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.

Supporting information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhu, F., Yao, Z., Ji, W. et al. An efficient resin for solid-phase extraction and determination by UPLCMS/MS of 44 pharmaceutical personal care products in environmental waters. Front. Environ. Sci. Eng. 14, 51 (2020). https://doi.org/10.1007/s11783-020-1228-y

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11783-020-1228-y

Keywords

Navigation