José M. Marín

Application of ultra-high-pressure liquid chromatography–tandem mass spectrometry to the determination of multi-class pesticides in environmental and wastewater samples: Study of matrix effects

An ultra-high-pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for the determination of 37 pesticides (herbicides, insecticides and fungicides) in environmental and wastewater has been developed. To efficiently combine UHPLC with MS/MS, a fast-acquisition triple quadrupole mass analyzer was used. This analyzer (minimum dwell time, 5 ms) allows acquiring up to three simultaneous transitions in the selected reaction monitoring mode for each compound assuring a reliable identification without resolution or sensitivity losses. A pre-concentration step based on solid-phase extraction using Waters Oasis HLB cartridges (0.2 g) was applied with a 100-fold pre-concentration factor along the whole analytical procedure. The method was validated based on European SANCO guidelines using surface, ground, drinking and treated water (from an urban solid residues treatment plant) spiked at two concentration levels (0.025 and 0.1 microg/L), the lowest having been established as the limit of quantification objective. The method showed excellent sensitivity, with instrumental limits of detection ranging from 0.1 to 7 pg. It was applied to environmental water samples (ground and surface water) as well as to samples of urban solid waste leachates (raw leachate and treated leachate after applying reversed osmosis) collected from a municipal treatment plant. Matrix effects have been studied in the different types of water samples analyzed, and several isotope-labelled internal standards have been evaluated as a way to compensate the signal suppression observed for most of the compounds studied, especially in wastewater samples. As a general remark, only those pesticides which response was corrected using their own isotope-labelled molecule, could be satisfactorily corrected in all type of samples, assuring in this way the accurate quantification in all matrix samples.

Determination of abamectin and azadirachtin residues in orange samples by liquid chromatography-electrospray tandem mass spectrometry

A rapid and sensitive LC-ESI-MS-MS method has been developed for the determination of azadirachtin and abamectin residues in orange samples. Samples were extracted with acetonitrile, in a high-speed blender. After the addition of sodium acetate, an aliquot of extract was directly injected into the LC-ESI-MS-MS system. The highest sensitivity of the method was achieved under MS-MS conditions using [M+Na]+ adducts as precursor ions. Recoveries for both compoundsfrom spiked orange samples at 0.01 and 0.1 mg/kg were above 80%, with good repeatability (<10%). Method detection limits achieved (<0.007 mg/kg) were adequate for the determination of these pesticides in this kind of sample from the regulatory point of view. The importance of the solvent used for extraction, as well as the addition of sodium acetate to the extracts and the selection of adequate chromatographic conditions are discussed.

Pesticide residues and transformation products in groundwater from a Spanish agricultural region on the Mediterranean Coast

An overview is given on the presence and changes over time of pesticide residues in groundwater from the Valencia region, one of the most important citrus cultivation sites of southern Europe. A multiresidue LC-MS/MS method was applied for the screening of around 50 pesticides in 75 water samples collected during 2000. The herbicides simazine, terbuthylazine, bromacil, terbumeton, and diuron were the most frequently detected compounds. On the basis of compounds detected in these samples, another method that focused on 30 herbicides and relevant transformation products (TPs) was developed and applied to around 80 water samples collected during 2003. Simazine was the most frequently found compound followed by several triazine metabolites. Data for this paper show the vulnerability of groundwater in this area to herbicide applications and illustrate the importance of including pesticide TPs in environmental monitoring programmes, as four out of the five compounds most frequently detected were pesticide TPs.

Quantification and confirmation of priority organic micropollutants in water by LC-tandem mass spectrometry

Liquid chromatography coupled to tandem mass spectrometry with a triple quadrupole analyser was used to determine selected (medium) polar organic pollutants—isoproturon, diuron and pentachlorophenol, as the herbicides simazine, atrazine, terbuthilazine, alachlor, and metolachlor—in treated water from urban solid-waste leachates. Two millilitres of water was preconcentrated by on-line trace enrichment (solid-phase extraction liquid chromatography) which allowed rapid analysis, but still with a satisfactory sensitivity, as the limits of quantification were 0.05 µg L−1, while the limits of detection were in the range of 0.001–0.01 µg L−1. Confirmation of the identity of compounds was ensured by the use of two tandem mass spectrometry transitions. Moreover, a study of matrix effects was thoroughly investigated by applying the developed procedure to different ground and surface waters. A simple dilution of the water sample with high-performance-liquid-chromatography-grade water was sufficient to minimize and/or remove this undesirable effect in all water samples tested, this approach being feasible due to the excellent sensitivity of the method.

A simple and rapid analytical methodology based on liquid chromatography-tandem mass spectrometry for monitoring pesticide residues in soils from Argentina

A rapid analytical methodology has been developed for multi-residue determination of pesticides in soils using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) with a triple quadrupole analyzer. Soil samples were collected from 12 representative agricultural areas in Argentina, and 18 pesticides were selected on the basis of their use. Special attention was paid to minimize sample preparation, making easier the method application to routine analysis. Several extraction procedures were tested, performing a careful study on matrix effects. The method finally proposed (extraction with acetonitrile and a subsequent 2-fold dilution with water without any clean-up step) was fully validated at 0.05 and 0.5 mg kg−1 on the basis of European SANCO 12571/2013 and 825/00 guidelines. The method applicability and robustness were demonstrated by analysis of quality control (QC) samples, consisting of eleven soils spiked at 0.5 mg kg−1. These soil samples were collected from different experimental plots, and were very diverse in their physico-chemical characteristics. The methodology developed is of easy application, there is low consumption of solvents and reagents, and no clean-up is required despite the complexity of the soil matrix. In the near future, the method developed will be used to monitor the presence of pesticides in large agricultural areas of Argentina.

Determination of sub‐ppb epichlorohydrin levels in water by on‐line solid‐phase extraction liquid chromatography/tandem mass spectrometry

A new sensitive and selective method based on on-line solid-phase extraction (SPE) coupled to liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) using a triple quadrupole mass spectrometer has been developed for the determination of epichlorohydrin (ECH) in different types of water samples. ECH is not easily determined directly by ESI-MS as it is not readily ionized, and it has a low molecular mass and high polarity. Thus, prior derivatization of ECH was necessary, employing 3,5-difluorobenzylamine as a derivatizing agent with Fe(III) as a catalyst. In order to achieve accurate quantification, correcting for matrix effects, losses in the derivatization process and instrumental deviations, isotope labelled ECH (ECH-d(5)) was added as an internal standard (IS) to the water samples. The method was validated based on European SANCO guidelines using drinking and other types of treated water spiked at two concentration levels (0.1 and 1.0 microg/L), the lower level having been established as the limit of quantification (LOQ) of the method. Satisfactory accuracy (recoveries between 70 and 103%), precision (RSD <20%) and linearity (from 0.05 to 50 microg/L, r >0.99) were obtained. The limit of detection (LOD) was set up at 0.03 microg/L. The method was applied to different water samples (drinking water and water samples collected from a municipal treatment water plant). In order to enhance confidence, five selected reaction monitoring (SRM) transitions were acquired, thus obtaining a simultaneous reliable quantification and identification of ECH in water, even at sub-ppb levels.

Analytical study on ethephon residue determination in water by ion-pairing liquid chromatography/tandem mass spectrometry

A detailed analytical study on ethephon residue determination in water, making use of ion-pairing liquid chromatography coupled to electrospray tandem mass spectrometry (LC/MS/MS), has been carried out. Ethephon is a plant growth regulator, highly polar, which is typically present in aqueous solution in anionic form due to its acid character. Both its extraction and pre-concentration from water samples and its chromatographic retention are difficult. Several approaches for sample pretreatment have been tested including direct injection into the chromatographic system, on-line solid phase extraction (SPE) and off-line SPE, with the best results being obtained after off-line SPE, using Oasis MAX cartridges (mixed-mode strong anion-exchange). After testing several ion-pairing reagents, tetrabuthylammonium acetate (TBA) was selected. This was added to the samples before LC/MS/MS analysis to facilitate ethephon chromatographic retention. The acquisition of several specific MS/MS transitions together with the evaluation of their relative intensity ratios allowed the reliable confirmation of the analyte in samples. The optimised approach was tested in low-salinity water spiked at 0.1 µg L−1 level with satisfactory recovery, and a limit of detection of 0.02 µg L−1. To this purpose, the water sample was partially de-ionised in an initial stage, in order to remove major ions that would have interfered in analyses. The application of this methodology to more saline/complex water samples, as surface or wastewater, was problematic and a thorough optimisation of the de-ionisation conditions would be required.