Selective determination of pharmaceuticals and illicit drugs in wastewaters using a novel strong cation-exchange solid-phase extraction combined with liquid chromatography–tandem mass spectrometry

Núria Gilart, Peter Cormack, Rosa Maria Marcé, Nuria Fontanals Torroja, Francesc Borrull

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

In this study, two materials are presented with strong cation-exchange (SCX) behaviour synthesised by two different approaches and then crushed for their application as sorbents for solid-phase extraction (SPE) to extract a group of pharmaceuticals and illicit drugs selectively from wastewater samples. The first SCX polymer was obtained by copolymerisation of three monomers: 2-acrylamido-2-methylpropane sulphonic acid (AMPSA), 2-hydroxyethyl methacrylate (HEMA) and pentaerythritol triacrylate (PETRA), while the second was obtained by post-modification with sulphuric acid (H2SO4) of a copolymer based on HEMA and divinylbenzene (DVB). After their syntheses, both polymers were evaluated as SPE sorbents, with all parameters affecting SPE being optimised, such as sample pH, washing and elution solvents and volumes. Thanks to the sulphonic groups present in the structure of the polymers, all of the compounds with basic functionalities were retained on the sorbents after the washing step, removing the acidic analytes and other interfering compounds, providing successful results in terms of ion suppression/enhancement (-12% and 21%) when wastewater samples were analysed. However, AMPSA/HEMA/PETRA (20/60/20) failed to retain the analytes after loading wastewater samples (25 or 50 mL), decreasing analyte recovery values significantly, whereas the sulphonated HEMA/DVB (50/50) enabled good SPE performance with recovery values between 70% and 98%, except for ranitidine and EDDP (39% and 43%, respectively). Therefore, this polymer was selected for further method validation and quantification of wastewater samples, providing low method detection limits (MDLs) in this matrix (from 2 to 40 ng L−1). Finally, most of the studied compounds were detected and quantified in wastewater samples, especially atenolol, ranitidine, cocaine and its metabolite benzoylecgonine.
LanguageEnglish
Pages137-146
JournalJournal of Chromatography A
Volume1325
DOIs
Publication statusPublished - 17 Jan 2014

Fingerprint

Solid Phase Extraction
Liquid chromatography
Street Drugs
Waste Water
Tandem Mass Spectrometry
divinyl benzene
Liquid Chromatography
Mass spectrometry
Cations
Ion exchange
Wastewater
Polymers
Sorbents
Ranitidine
Pharmaceutical Preparations
Sulfonic Acids
Washing
Recovery
Atenolol
Metabolites

Keywords

  • selectivity
  • strong cation-exchange
  • mixed-mode solid-phase extraction
  • pharmaceuticals and illicit drugs
  • wastewaters

Cite this

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title = "Selective determination of pharmaceuticals and illicit drugs in wastewaters using a novel strong cation-exchange solid-phase extraction combined with liquid chromatography–tandem mass spectrometry",
abstract = "In this study, two materials are presented with strong cation-exchange (SCX) behaviour synthesised by two different approaches and then crushed for their application as sorbents for solid-phase extraction (SPE) to extract a group of pharmaceuticals and illicit drugs selectively from wastewater samples. The first SCX polymer was obtained by copolymerisation of three monomers: 2-acrylamido-2-methylpropane sulphonic acid (AMPSA), 2-hydroxyethyl methacrylate (HEMA) and pentaerythritol triacrylate (PETRA), while the second was obtained by post-modification with sulphuric acid (H2SO4) of a copolymer based on HEMA and divinylbenzene (DVB). After their syntheses, both polymers were evaluated as SPE sorbents, with all parameters affecting SPE being optimised, such as sample pH, washing and elution solvents and volumes. Thanks to the sulphonic groups present in the structure of the polymers, all of the compounds with basic functionalities were retained on the sorbents after the washing step, removing the acidic analytes and other interfering compounds, providing successful results in terms of ion suppression/enhancement (-12{\%} and 21{\%}) when wastewater samples were analysed. However, AMPSA/HEMA/PETRA (20/60/20) failed to retain the analytes after loading wastewater samples (25 or 50 mL), decreasing analyte recovery values significantly, whereas the sulphonated HEMA/DVB (50/50) enabled good SPE performance with recovery values between 70{\%} and 98{\%}, except for ranitidine and EDDP (39{\%} and 43{\%}, respectively). Therefore, this polymer was selected for further method validation and quantification of wastewater samples, providing low method detection limits (MDLs) in this matrix (from 2 to 40 ng L−1). Finally, most of the studied compounds were detected and quantified in wastewater samples, especially atenolol, ranitidine, cocaine and its metabolite benzoylecgonine.",
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Selective determination of pharmaceuticals and illicit drugs in wastewaters using a novel strong cation-exchange solid-phase extraction combined with liquid chromatography–tandem mass spectrometry. / Gilart, Núria; Cormack, Peter; Marcé, Rosa Maria; Fontanals Torroja, Nuria; Borrull, Francesc.

In: Journal of Chromatography A , Vol. 1325, 17.01.2014, p. 137-146.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Selective determination of pharmaceuticals and illicit drugs in wastewaters using a novel strong cation-exchange solid-phase extraction combined with liquid chromatography–tandem mass spectrometry

AU - Gilart, Núria

AU - Cormack, Peter

AU - Marcé, Rosa Maria

AU - Fontanals Torroja, Nuria

AU - Borrull, Francesc

PY - 2014/1/17

Y1 - 2014/1/17

N2 - In this study, two materials are presented with strong cation-exchange (SCX) behaviour synthesised by two different approaches and then crushed for their application as sorbents for solid-phase extraction (SPE) to extract a group of pharmaceuticals and illicit drugs selectively from wastewater samples. The first SCX polymer was obtained by copolymerisation of three monomers: 2-acrylamido-2-methylpropane sulphonic acid (AMPSA), 2-hydroxyethyl methacrylate (HEMA) and pentaerythritol triacrylate (PETRA), while the second was obtained by post-modification with sulphuric acid (H2SO4) of a copolymer based on HEMA and divinylbenzene (DVB). After their syntheses, both polymers were evaluated as SPE sorbents, with all parameters affecting SPE being optimised, such as sample pH, washing and elution solvents and volumes. Thanks to the sulphonic groups present in the structure of the polymers, all of the compounds with basic functionalities were retained on the sorbents after the washing step, removing the acidic analytes and other interfering compounds, providing successful results in terms of ion suppression/enhancement (-12% and 21%) when wastewater samples were analysed. However, AMPSA/HEMA/PETRA (20/60/20) failed to retain the analytes after loading wastewater samples (25 or 50 mL), decreasing analyte recovery values significantly, whereas the sulphonated HEMA/DVB (50/50) enabled good SPE performance with recovery values between 70% and 98%, except for ranitidine and EDDP (39% and 43%, respectively). Therefore, this polymer was selected for further method validation and quantification of wastewater samples, providing low method detection limits (MDLs) in this matrix (from 2 to 40 ng L−1). Finally, most of the studied compounds were detected and quantified in wastewater samples, especially atenolol, ranitidine, cocaine and its metabolite benzoylecgonine.

AB - In this study, two materials are presented with strong cation-exchange (SCX) behaviour synthesised by two different approaches and then crushed for their application as sorbents for solid-phase extraction (SPE) to extract a group of pharmaceuticals and illicit drugs selectively from wastewater samples. The first SCX polymer was obtained by copolymerisation of three monomers: 2-acrylamido-2-methylpropane sulphonic acid (AMPSA), 2-hydroxyethyl methacrylate (HEMA) and pentaerythritol triacrylate (PETRA), while the second was obtained by post-modification with sulphuric acid (H2SO4) of a copolymer based on HEMA and divinylbenzene (DVB). After their syntheses, both polymers were evaluated as SPE sorbents, with all parameters affecting SPE being optimised, such as sample pH, washing and elution solvents and volumes. Thanks to the sulphonic groups present in the structure of the polymers, all of the compounds with basic functionalities were retained on the sorbents after the washing step, removing the acidic analytes and other interfering compounds, providing successful results in terms of ion suppression/enhancement (-12% and 21%) when wastewater samples were analysed. However, AMPSA/HEMA/PETRA (20/60/20) failed to retain the analytes after loading wastewater samples (25 or 50 mL), decreasing analyte recovery values significantly, whereas the sulphonated HEMA/DVB (50/50) enabled good SPE performance with recovery values between 70% and 98%, except for ranitidine and EDDP (39% and 43%, respectively). Therefore, this polymer was selected for further method validation and quantification of wastewater samples, providing low method detection limits (MDLs) in this matrix (from 2 to 40 ng L−1). Finally, most of the studied compounds were detected and quantified in wastewater samples, especially atenolol, ranitidine, cocaine and its metabolite benzoylecgonine.

KW - selectivity

KW - strong cation-exchange

KW - mixed-mode solid-phase extraction

KW - pharmaceuticals and illicit drugs

KW - wastewaters

U2 - 10.1016/j.chroma.2013.12.012

DO - 10.1016/j.chroma.2013.12.012

M3 - Article

VL - 1325

SP - 137

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JO - Journal of Chromatography A

T2 - Journal of Chromatography A

JF - Journal of Chromatography A

SN - 0021-9673

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