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Molecules 2014, 19(12), 20627-20649; doi:10.3390/molecules191220627

Determination and Occurrence of Phenoxyacetic Acid Herbicides and Their Transformation Products in Groundwater Using Ultra High Performance Liquid Chromatography Coupled to Tandem Mass Spectrometry

1
Teagasc Environmental Research Centre, Johnstown Castle, Wexford, Ireland
2
Department of Geology, Trinity College Dublin, Dublin 2, Ireland
3
Food Safety Department, Teagasc Food Research Centre, Ashtown, Dublin 15, Ireland
*
Author to whom correspondence should be addressed.
Received: 29 October 2014 / Revised: 26 November 2014 / Accepted: 27 November 2014 / Published: 10 December 2014
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Abstract

A sensitive method was developed and validated for ten phenoxyacetic acid herbicides, six of their main transformation products (TPs) and two benzonitrile TPs in groundwater. The parent compounds mecoprop, mecoprop-p, 2,4-D, dicamba, MCPA, triclopyr, fluroxypr, bromoxynil, bentazone, and 2,3,6-trichlorobenzoic acid (TBA) are included and a selection of their main TPs: phenoxyacetic acid (PAC), 2,4,5-trichloro-phenol (TCP), 4-chloro-2-methylphenol (4C2MP), 2,4-dichlorophenol (DCP), 3,5,6-trichloro-2-pyridinol (T2P), and 3,5-dibromo-4-hydroxybenzoic acid (BrAC), as well as the dichlobenil TPs 2,6-dichlorobenzamide (BAM) and 3,5-dichlorobenzoic acid (DBA) which have never before been determined in Irish groundwater. Water samples were analysed using an efficient ultra-high performance liquid chromatography (UHPLC) method in an 11.9 min separation time prior to detection by tandem mass spectrometry (MS/MS). The limit of detection (LOD) of the method ranged between 0.00008 and 0.0047 µg·L−1 for the 18 analytes. All compounds could be detected below the permitted limits of 0.1 µg·L−1 allowed in the European Union (EU) drinking water legislation [1]. The method was validated according to EU protocols laid out in SANCO/10232/2006 with recoveries ranging between 71% and 118% at the spiked concentration level of 0.06 µg·L−1. The method was successfully applied to 42 groundwater samples collected across several locations in Ireland in March 2012 to reveal that the TPs PAC and 4C2MP were detected just as often as their parent active ingredients (a.i.) in groundwater. View Full-Text
Keywords: phenoxyacetic acid herbicides; chlorophenols; benzonitriles; water; UHPLC-MS/MS phenoxyacetic acid herbicides; chlorophenols; benzonitriles; water; UHPLC-MS/MS
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

McManus, S.-L.; Moloney, M.; Richards, K.G.; Coxon, C.E.; Danaher, M. Determination and Occurrence of Phenoxyacetic Acid Herbicides and Their Transformation Products in Groundwater Using Ultra High Performance Liquid Chromatography Coupled to Tandem Mass Spectrometry. Molecules 2014, 19, 20627-20649.

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