Journal of Chromatography A, 1343 (2014) 55–62
Contents lists available at ScienceDirect
Journal of Chromatography A journal homepage: www.elsevier.com/locate/chroma
Evaluation of strong cation-exchange polymers for the determination of drugs by solid-phase extraction–liquid chromatography–tandem mass spectrometry夽 Núria Fontanals a,∗ , Núria Miralles a , Norhayati Abdullah b , Arlene Davies b , Núria Gilart a , P.A.G. Cormack b a
Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Campus Sescelades Marcel lí Domingo, s/n, 43007 Tarragona, Spain WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow G1 1XL, Scotland, UK b
a r t i c l e
i n f o
Article history: Received 27 November 2013 Received in revised form 17 March 2014 Accepted 27 March 2014 Available online 4 April 2014 Keywords: Strong cation-exchange Solid-phase extraction Recovery Matrix effect Sewage
a b s t r a c t This paper presents eight distinct strong cation-exchange resins, all of which were derived from precursor resins that had been synthesised using either precipitation polymerisation or non-aqueous dispersion polymerisation. The precursor resins were transformed into the corresponding strong cation-exchange resins by hypercrosslinking followed by polymer analogous reactions, to yield materials with high specific surface areas and strong cation-exchange character. These novel resins were then evaluated as strong cation-exchange (SCX) sorbents in the solid-phase extraction (SPE) of a group of drugs from aqueous samples. Following preliminary experiments, the two best-performing resins were then evaluated in solid-phase extraction–liquid chromatography–tandem mass spectrometry (SPE/LC–MS/MS) to determine a group of drugs from sewage samples. In general, use of these sorbents led to excellent recovery values (75–100%) for most of the target drugs and negligible matrix effects (ME) ( 145.0)
A t e no lol 1
x10 2 + MRM (315.0-> 176.0)
R a n i tid ine
5
x10 2 + MRM (300.0-> 165.0)
Co d e i n e
2
0 x10 1 + MRM (328.0-> 165.0)
6 - a c et y lmo rp hin e
2 0 x10 4 + MRM (195.0 -> 138.0)
C a f f e ine
1
x10 3 + MRM (290.0 -> 168.0)
BE
1 0 x10 3 + MRM (304.0-> 182.0)
C o c a ine
2.5 0 x10 2 + MRM (189.0-> 145.0)
A n t ipy r ine
1 0 x10 3 + MRM (260.0-> 116.0) 4
P r o p r an olo l
2 0 1
2
3
4
5
6
7
8
9
10
11
Counts vs. Acquisition Time (min) Fig. 2. MRM chromatograms of an influent sewage sample. For experimental conditions, see the text.
Finally, the developed SPE/LC–MS/MS method was applied for the determination of drugs in influent and effluent samples from an urban STP with samples taken on different days. The presence of the analytes found was confirmed according to the Commission Decision 2002/657/EC [27]. All the analytes studied were found in the analysed samples, but some of them at levels below the LOQs. Table 4 presents the range of concentration for each analyte for both effluent and influent sewage samples. As an example, Fig. 2 shows representative MRM chromatograms from the analysis of one of the influent sewage samples. These values are in line with those reported at similar STPs [28–31]. We should note that the low concentration of trimethoprim found in all the samples analysed might be attributed to the low recoveries achieved with the present method. In addition, we should mention that some drugs are present at a higher concentration in effluent than in influent water. This might be due to the fact that the sampling of the influent and effluent sewage was not performed in the same time period, but also due to a possible conversion of their conjugated metabolite to the original substance after the treatment processes.
Table 4 Concentrations of analytes found in influent and effluent wastewater samples (n = 5) when the samples were analysed by SPE/LC-MS/MS using the HXLNAD-SCXb sorbent. Concentration (ng/L)
Morphine Atenolol Ranitidine Dihydrocodeine Codeine 6-Acetylmorphine Trimethoprim Caffeine Metoprolol BE Cocaine Antipyrine Propanolol EDDP Methadone
Effluent
Influent
Contents lists available at ScienceDirect
Journal of Chromatography A journal homepage: www.elsevier.com/locate/chroma
Evaluation of strong cation-exchange polymers for the determination of drugs by solid-phase extraction–liquid chromatography–tandem mass spectrometry夽 Núria Fontanals a,∗ , Núria Miralles a , Norhayati Abdullah b , Arlene Davies b , Núria Gilart a , P.A.G. Cormack b a
Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Campus Sescelades Marcel lí Domingo, s/n, 43007 Tarragona, Spain WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow G1 1XL, Scotland, UK b
a r t i c l e
i n f o
Article history: Received 27 November 2013 Received in revised form 17 March 2014 Accepted 27 March 2014 Available online 4 April 2014 Keywords: Strong cation-exchange Solid-phase extraction Recovery Matrix effect Sewage
a b s t r a c t This paper presents eight distinct strong cation-exchange resins, all of which were derived from precursor resins that had been synthesised using either precipitation polymerisation or non-aqueous dispersion polymerisation. The precursor resins were transformed into the corresponding strong cation-exchange resins by hypercrosslinking followed by polymer analogous reactions, to yield materials with high specific surface areas and strong cation-exchange character. These novel resins were then evaluated as strong cation-exchange (SCX) sorbents in the solid-phase extraction (SPE) of a group of drugs from aqueous samples. Following preliminary experiments, the two best-performing resins were then evaluated in solid-phase extraction–liquid chromatography–tandem mass spectrometry (SPE/LC–MS/MS) to determine a group of drugs from sewage samples. In general, use of these sorbents led to excellent recovery values (75–100%) for most of the target drugs and negligible matrix effects (ME) ( 145.0)
A t e no lol 1
x10 2 + MRM (315.0-> 176.0)
R a n i tid ine
5
x10 2 + MRM (300.0-> 165.0)
Co d e i n e
2
0 x10 1 + MRM (328.0-> 165.0)
6 - a c et y lmo rp hin e
2 0 x10 4 + MRM (195.0 -> 138.0)
C a f f e ine
1
x10 3 + MRM (290.0 -> 168.0)
BE
1 0 x10 3 + MRM (304.0-> 182.0)
C o c a ine
2.5 0 x10 2 + MRM (189.0-> 145.0)
A n t ipy r ine
1 0 x10 3 + MRM (260.0-> 116.0) 4
P r o p r an olo l
2 0 1
2
3
4
5
6
7
8
9
10
11
Counts vs. Acquisition Time (min) Fig. 2. MRM chromatograms of an influent sewage sample. For experimental conditions, see the text.
Finally, the developed SPE/LC–MS/MS method was applied for the determination of drugs in influent and effluent samples from an urban STP with samples taken on different days. The presence of the analytes found was confirmed according to the Commission Decision 2002/657/EC [27]. All the analytes studied were found in the analysed samples, but some of them at levels below the LOQs. Table 4 presents the range of concentration for each analyte for both effluent and influent sewage samples. As an example, Fig. 2 shows representative MRM chromatograms from the analysis of one of the influent sewage samples. These values are in line with those reported at similar STPs [28–31]. We should note that the low concentration of trimethoprim found in all the samples analysed might be attributed to the low recoveries achieved with the present method. In addition, we should mention that some drugs are present at a higher concentration in effluent than in influent water. This might be due to the fact that the sampling of the influent and effluent sewage was not performed in the same time period, but also due to a possible conversion of their conjugated metabolite to the original substance after the treatment processes.
Table 4 Concentrations of analytes found in influent and effluent wastewater samples (n = 5) when the samples were analysed by SPE/LC-MS/MS using the HXLNAD-SCXb sorbent. Concentration (ng/L)
Morphine Atenolol Ranitidine Dihydrocodeine Codeine 6-Acetylmorphine Trimethoprim Caffeine Metoprolol BE Cocaine Antipyrine Propanolol EDDP Methadone
Effluent
Influent
