Determination of Sulfonylurea Herbicides in Water and Food Samples Using Sol−Gel Glass-Based Immunoaffinity Extraction and Liquid Chromatography−Ultraviolet/Diode Array Detection or Liquid Chromatography-Tandem Mass Spectrometry

Abstract

Immunoaffinity supports (IAS) were prepared using broad specific polyclonal anti-sulfonylurea (SU) antibodies immobilized in sol-gel glass. Two different kinds of supports were applied, crushed sol-gel monoliths and sol-gel-coated highly porous silica particles. Both were used for the quantitative enrichment of SUs in natural water and food samples followed by high-performance liquid chromatography-ultraviolet/diode array detection (HPLC-UV/DAD) and tandem mass spectrometry (LC-MS/MS), respectively. Loading, washing, and elution conditions of IAS were optimized. The capacity of supports was determined for 30 SUs and compared with the cross-reactivity pattern of the direct competitive enzyme-linked immunosorbent assay. The capacities correlated well with the affinity to individual SU compounds. Even analytes to which the polyclonal antibodies showed only a lower cross-reactivity could be enriched to a certain degree, if a sufficient capacity of IAS was provided. The IAS could be reused at least 10 times without a loss of effectiveness. Recovery of 16 selected SUs extracted from spiked water and food samples was dependent on the affinity of both immobilized antibodies to single compounds and matrix interferences. In water, 13 SUs showed recoveries higher than 80% when immunoaffinity extraction was used in combination with LC-UV/DAD. On the basis of the enrichment of 200 mL of aqueous sample, corresponding limit of detection (LOD) values ranged between 20 and 100 ng/L. The recoveries of 10 SUs, which were extracted from 10 g of potato spiked at a 10 microg/kg level, were higher than 75%. For grain samples, recoveries were at the same order for at least five SU herbicides. The LOD of LC-MS/MS measurements was about 1 order of magnitude higher, i.e., gave LODs between 1.1 and 6.9 microg/kg of food sample, depending on the compound and extraction procedure. These LODs provide evidence that the main advantage of the prepared IAS is their high selectivity for group specific recognition of SUs as compared to other nonspecific solid phase extraction materials.

One-Step QuEChERS-Based Approach to Extraction and Cleanup in Multiresidue Analysis of Sulfonylurea Herbicides in Cereals by Liquid Chromatography–Tandem Mass Spectrometry

“…These co-extracts can interfere with chromatographic analysis (Łozowicka et al 2012a, 2014Walorczyk and Drożdżyński 2012). Several analytical procedures have been developed for determination of sulfonylurea residues in cereals, mainly based on enzyme-linked immunosorbent assays (Degelmann et al 2006), capillary electrophoresis with ultraviolet-diode array detection (Springer and Lista 2010), and highperformance liquid chromatography with diode array detection (Chao et al 2002;Zhou et al 2006;Gallitzendorfer et al 2011). Although various gas chromatography (GC) and GC-mass spectrometry (MS) methods have been developed, they require chemical derivatization of polar sulfonylureas due to their low volatility.…”

Bioaffinity chromatography on monolithic supports

“…In both studies, the affinity column was coupled to an LC-MS/MS system. Polyclonal antibodies against sulfonylurea (SU) herbicides were entrapped in crushed sol-gel monoliths or sol-gel coated highly porous silica particles [132]. The enrichment efficiency of these affinity sol-gel columns using real samples (food samples, tap water and surface water samples) was compared with commercial SPE columns (Lichrolut and Oasis HLB).…”

A direct method for the polarographic determination of herbicide triasulfuron and application to natural samples and agrochemical formulation

“…A wide range of analytical methods has been applied to the analysis of sulfonylurea pesticides and most of them are based on chromatographic techniques [6][7][8][9]. High performance liquid chromatography (HPLC) with ultraviolet detector or diode array detector was the most common approaches [10,11], other methods such as liquid chromatography with mass spectrometry [12], capillary electrophoresis [13], supercritical fluid chromatography [14], bioassay [15] and enzyme immunoassay [16] are often found in the published reports.…”