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. 2017 Feb;409(4):871-879.
doi: 10.1007/s00216-016-0060-5. Epub 2016 Nov 10.

Rapid ion-exchange matrix removal for a decrease of detection limits in the analysis of salt-rich reservoir waters for fluorobenzoic acids by liquid chromatography coupled with tandem mass spectrometry

Paweł Kubica  1 , Véronique Vacchina  2 , Tomasz Wasilewski  3 , Stéphanie Reynaud  4 , Joanna Szpunar  5 , Ryszard Lobinski  5   6
Affiliations

Rapid ion-exchange matrix removal for a decrease of detection limits in the analysis of salt-rich reservoir waters for fluorobenzoic acids by liquid chromatography coupled with tandem mass spectrometry

Paweł Kubica et al. Anal Bioanal Chem. 2017 Feb.

Abstract

A matrix removal procedure with ion-exchange resin prior to analysis for 18 fluorinated benzoic acids (FBAs) tracers in saline (>25% salt) reservoir water was optimized. The elimination of >98% of salt and the simultaneous matrix sample cleanup allowed the direct analysis using the supernatant by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). This resulted in a gain in detection limits for most of the tracers in comparison with the reference method (direct analysis after minimum required dilution). The limits of detection (LODs) were in the range of 0.01-0.15 ng/ml and compared to other studies the developed method provided comparable limits of detection and advantage of simplified and shorter sample preparation. The presented method offers a considerable gain in simplicity and analysis time. Recoveries for all the tracers reached 80-100%, except for 2-FBA and 2,6-dFBA for which they were ca. 60%. The low recoveries were corrected by the use of five isotopically labeled internal standards. The method was validated by the analysis of spiked samples and by an independent comparison of the results with those obtained by solid-phase extraction LC-MS/MS method.

Keywords: Fluorinated benzoic acids; Ion exchange; LC MS/MS; Matrix removal.

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Conflict of interest statement

The authors declare that they have no conflict of interest.

Figures

Fig. 1
Fig. 1
Chromatograms for samples obtained by adding a mixture of standards (at the level of 5 ng/mL) to the reservoir water matrix and analyzed by the developed method. a 139 > 95: (1) 2-fluorobenzoic acid, (2) 3-fluorobenzoic acid, (3) 4-fluorobenzoic acid. b 157 > 113: (4) 2,6-difluorobenzoic acid, (5) 2,5-difluorobenzoic acid, (6) 2,3-difluorobenzoic acid, (7) 2,4-difluorobenzoic acid, (8) 3,5-difluorobenzoic acid, (9) 3,4-difluorobenzoic acid. c 175 > 113: (10) 2,3,6-trifluorobenzoic acid, (11) 2,4,6-trifluorobenzoic acid, (12) 2,4,5-trifluorobenzoic acid, (13) 2,3,4-trifluorobenzoic acid, (14) 3,4,5-trifluorobenzoic acid. d 189 > 145: (15) 2-(trifluoromethyl)benzoic acid, (16) 3-(trifluoromethyl)benzoic acid, (17) 4-(trifluoromethyl)benzoic acid. e 257 > 213: (18) 3,5-bis(trifluoromethyl)benzoic acid
Fig. 2
Fig. 2
Analytes recoveries obtained during optimization of the matrix removal for a mono-FBAs, b di-FBAs, c tri-FBAs, and d triF-methyl-FBAs at 10 ng/mL concentration level for each compound in spiked sample (standard deviation values calculated for 3 measurements were between 3.1 and 5.1%)
Fig. 3
Fig. 3
Validation with SPE-LC MS/MS; the points on the graph (with error bars) correspond to concentration values obtained by the proposed method and according to the literature method [7] for 10 reservoir water samples
See this image and copyright information in PMC

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