Identification and quantification of ibuprofen, naproxen, ketoprofen and diclofenac present in waste-waters, as their trimethylsilyl derivatives, by gas chromatography mass spectrometry

Á Sebok, A. Vasanits-Zsigrai, Gy Palkó, G. Záray, I. Molnár-Perl

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69 Citations (Scopus)

Abstract

This paper reports a derivatization, mass fragmentation study relating to the most common, non-steroidal anti-inflammatory drugs (NSAIDs), such as ibuprofen, naproxen, ketoprofen and diclofenac, identified and quantified in the aquatic environment. Derivatizations have been performed with four silylation reagents in order to select the most proper one, taking into account analytical and financial points of view, equally. The tested reagents were N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA), N-methyl-N-tert-butyldimethylsilyl-trifluoroacetamide (MTBSTFA) and for this purpose at the first time, hexamethyldisilazan (HMDS) + trifluoroacetic acid (TFAA). Varying derivatization time and temperature, taking into consideration chemical and financial advantages, HMDS + TFAA proved to be the optimum selection. Responses of derivatives have been compared, as a function of the ionization technique (external/internal ionization), as well as on the treatment of compounds' selective fragment ions (SFIs): (i) extracting the corresponding, characteristic m/z masses from TIC elutions and (ii) from SIM elutions, in parallel. Reproducibilities of measurements, expressed in relative standard deviation percentages (R.S.D.%), including the nanogram and the low picogram levels of injected derivatives, provided an average between 0.93 R.S.D.% and 4.11 R.S.D.%. NSAIDs' enrichment was performed with solid-phase extraction (SPE), applying the Oasis HLB (Waters) cartridges: recoveries in the 1-6 μg L-1 range varied between 84% and 111%, with an average reproducibility of 6.4 R.S.D.%. The utility of the optimized derivatization method is presented, on monthly basis, by the identification and quantitation of the ibuprofen, naproxen, ketoprofen and diclofenac content of the influent and effluent waste-water samples obtained from a Hungarian waste-water treatment plant.

Original languageEnglish
Pages (from-to)642-650
Number of pages9
JournalTalanta
Volume76
Issue number3
DOIs
Publication statusPublished - Jul 30 2008

Fingerprint

Ketoprofen
Trifluoroacetic Acid
Naproxen
Diclofenac
Ibuprofen
Waste Water
Gas chromatography
Gas Chromatography-Mass Spectrometry
Ionization
Mass spectrometry
Wastewater
Anti-Inflammatory Agents
Derivatives
Water treatment plants
Water Purification
Solid Phase Extraction
Pharmaceutical Preparations
Effluents
Ions
Recovery

Keywords

  • GC-MS
  • Ionization technique
  • Mass fragmentation
  • Non-steroidal anti-inflammatory drugs
  • Trimethylsilylation
  • Waste-water

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy

Cite this

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title = "Identification and quantification of ibuprofen, naproxen, ketoprofen and diclofenac present in waste-waters, as their trimethylsilyl derivatives, by gas chromatography mass spectrometry",
abstract = "This paper reports a derivatization, mass fragmentation study relating to the most common, non-steroidal anti-inflammatory drugs (NSAIDs), such as ibuprofen, naproxen, ketoprofen and diclofenac, identified and quantified in the aquatic environment. Derivatizations have been performed with four silylation reagents in order to select the most proper one, taking into account analytical and financial points of view, equally. The tested reagents were N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA), N-methyl-N-tert-butyldimethylsilyl-trifluoroacetamide (MTBSTFA) and for this purpose at the first time, hexamethyldisilazan (HMDS) + trifluoroacetic acid (TFAA). Varying derivatization time and temperature, taking into consideration chemical and financial advantages, HMDS + TFAA proved to be the optimum selection. Responses of derivatives have been compared, as a function of the ionization technique (external/internal ionization), as well as on the treatment of compounds' selective fragment ions (SFIs): (i) extracting the corresponding, characteristic m/z masses from TIC elutions and (ii) from SIM elutions, in parallel. Reproducibilities of measurements, expressed in relative standard deviation percentages (R.S.D.{\%}), including the nanogram and the low picogram levels of injected derivatives, provided an average between 0.93 R.S.D.{\%} and 4.11 R.S.D.{\%}. NSAIDs' enrichment was performed with solid-phase extraction (SPE), applying the Oasis HLB (Waters) cartridges: recoveries in the 1-6 μg L-1 range varied between 84{\%} and 111{\%}, with an average reproducibility of 6.4 R.S.D.{\%}. The utility of the optimized derivatization method is presented, on monthly basis, by the identification and quantitation of the ibuprofen, naproxen, ketoprofen and diclofenac content of the influent and effluent waste-water samples obtained from a Hungarian waste-water treatment plant.",
keywords = "GC-MS, Ionization technique, Mass fragmentation, Non-steroidal anti-inflammatory drugs, Trimethylsilylation, Waste-water",
author = "{\'A} Sebok and A. Vasanits-Zsigrai and Gy Palk{\'o} and G. Z{\'a}ray and I. Moln{\'a}r-Perl",
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T1 - Identification and quantification of ibuprofen, naproxen, ketoprofen and diclofenac present in waste-waters, as their trimethylsilyl derivatives, by gas chromatography mass spectrometry

AU - Sebok, Á

AU - Vasanits-Zsigrai, A.

AU - Palkó, Gy

AU - Záray, G.

AU - Molnár-Perl, I.

PY - 2008/7/30

Y1 - 2008/7/30

N2 - This paper reports a derivatization, mass fragmentation study relating to the most common, non-steroidal anti-inflammatory drugs (NSAIDs), such as ibuprofen, naproxen, ketoprofen and diclofenac, identified and quantified in the aquatic environment. Derivatizations have been performed with four silylation reagents in order to select the most proper one, taking into account analytical and financial points of view, equally. The tested reagents were N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA), N-methyl-N-tert-butyldimethylsilyl-trifluoroacetamide (MTBSTFA) and for this purpose at the first time, hexamethyldisilazan (HMDS) + trifluoroacetic acid (TFAA). Varying derivatization time and temperature, taking into consideration chemical and financial advantages, HMDS + TFAA proved to be the optimum selection. Responses of derivatives have been compared, as a function of the ionization technique (external/internal ionization), as well as on the treatment of compounds' selective fragment ions (SFIs): (i) extracting the corresponding, characteristic m/z masses from TIC elutions and (ii) from SIM elutions, in parallel. Reproducibilities of measurements, expressed in relative standard deviation percentages (R.S.D.%), including the nanogram and the low picogram levels of injected derivatives, provided an average between 0.93 R.S.D.% and 4.11 R.S.D.%. NSAIDs' enrichment was performed with solid-phase extraction (SPE), applying the Oasis HLB (Waters) cartridges: recoveries in the 1-6 μg L-1 range varied between 84% and 111%, with an average reproducibility of 6.4 R.S.D.%. The utility of the optimized derivatization method is presented, on monthly basis, by the identification and quantitation of the ibuprofen, naproxen, ketoprofen and diclofenac content of the influent and effluent waste-water samples obtained from a Hungarian waste-water treatment plant.

AB - This paper reports a derivatization, mass fragmentation study relating to the most common, non-steroidal anti-inflammatory drugs (NSAIDs), such as ibuprofen, naproxen, ketoprofen and diclofenac, identified and quantified in the aquatic environment. Derivatizations have been performed with four silylation reagents in order to select the most proper one, taking into account analytical and financial points of view, equally. The tested reagents were N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA), N-methyl-N-tert-butyldimethylsilyl-trifluoroacetamide (MTBSTFA) and for this purpose at the first time, hexamethyldisilazan (HMDS) + trifluoroacetic acid (TFAA). Varying derivatization time and temperature, taking into consideration chemical and financial advantages, HMDS + TFAA proved to be the optimum selection. Responses of derivatives have been compared, as a function of the ionization technique (external/internal ionization), as well as on the treatment of compounds' selective fragment ions (SFIs): (i) extracting the corresponding, characteristic m/z masses from TIC elutions and (ii) from SIM elutions, in parallel. Reproducibilities of measurements, expressed in relative standard deviation percentages (R.S.D.%), including the nanogram and the low picogram levels of injected derivatives, provided an average between 0.93 R.S.D.% and 4.11 R.S.D.%. NSAIDs' enrichment was performed with solid-phase extraction (SPE), applying the Oasis HLB (Waters) cartridges: recoveries in the 1-6 μg L-1 range varied between 84% and 111%, with an average reproducibility of 6.4 R.S.D.%. The utility of the optimized derivatization method is presented, on monthly basis, by the identification and quantitation of the ibuprofen, naproxen, ketoprofen and diclofenac content of the influent and effluent waste-water samples obtained from a Hungarian waste-water treatment plant.

KW - GC-MS

KW - Ionization technique

KW - Mass fragmentation

KW - Non-steroidal anti-inflammatory drugs

KW - Trimethylsilylation

KW - Waste-water

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