Multifamily Determination of Phytohormones and Acidic Herbicides in Fruits and Vegetables by Liquid Chromatography–Tandem Mass Spectrometry under Accredited Conditions

A 7-min multifamily residue method for the simultaneous quantification and confirmation of 8 phytohormones and 27 acidic herbicides in fruit and vegetables using ultra high-performance liquid chromatography (UHPLC) coupled to tandem mass spectrometry (MS/MS) was developed, validated according to SANTE 12682/2019, and accredited according to UNE-EN-ISO/IEC 17025:2017. Due to the special characteristics of these kinds of compounds, a previous step of alkaline hydrolysis was carried out for breaking conjugates that were potentially formed due to the interactions of the analytes with other components present in the matrix. Sample treatment was based on QuEChERS extraction and optimum detection conditions were individually optimized for each analyte. Cucumber (for high water content commodities) and orange (for high acid and high water content samples) were selected as representative matrices. Matrix-matched calibration was used, and all the validation criteria established in the SANTE guidelines were satisfied. Uncertainty estimation for each target compound was included in the validation process. The proposed method was applied to the analysis of more than 450 samples of cucumber, orange, tomato, watermelon, and zucchini during one year. Several compounds, such as 2,4-dichlorophenoxyacetic acid (2,4-D), 4-(3-indolyl)butyric acid (IBA), dichlorprop (2,4-DP), 2-methyl-4-chlorophenoxy acetic acid (MCPA), and triclopyr were found, but always at concentrations lower than the maximum residue level (MRL) regulated by the EU.

PTV In Situ Derivatization of Several Acidic Herbicides Using a Newly Developed GC-MS/MS Method

The uses of herbicides increased during the last decades. Because acid herbicides can be identified in environmental samples, specific analytical methods are required. In this work a new GC-MS/MS method was developed in order to detect some pyridinecarboxylic acids (clopyralid, triclopyr and fluroxypyr) and a methoxybenzoic acid (dicamba) from environmental water samples. Because these polar analytes involve a derivatization step, a Programmed Temperature Vaporizing injector (PTV) was used to shape the derivatization conditions and to minimize the working time. This process is called in port derivatization (IPD), a relative new technique which encourages greener practices in analytical laboratory. MtBSTFA was chosen to be the most suitable silylation agent due to generation of specific derivatized analyte structures, which can be further fragmented in the EI ionization source to produce specific ions for the targeted analytes, easily detectable with high sensitivity.Few studies analyzed the derivatization of above-mentioned herbicides with MtBSTFA, while no other paper work was identified in studying the in port derivatization of these compounds. The results revealed that the developed method is sensitive and robust to obtain quantitation limits below 10 ng/L.

Three-dimensional chitosan/graphene oxide aerogel for high-efficiency solid-phase extraction of acidic herbicides in vegetables

A simple, facile method was adopted to synthesize three-dimensional chitosan grafted graphene oxide aerogel modified silica (3D CS/GOA@Sil) as an eco-friendly, sustainable extraction material for the preconcentration of phenoxy acid herbicides.

The method of multicomponent determination of herbicides of various chemical classes in water

In the work there are considered results of the development of the multicomponent method of measurement of concentration of herbicides of various chemical nature under their joint presence in the water. There was justified the optimality of application of HPLC-DAD (the working wavelength of 240 nm) for the determination of levels of 10 active ingredients of herbicides of class of sulfonylurea (metsulfuron-methyl, nikosulfuron, sulfometuron-methyl, thifensulfuron-methyl, triflusulfuron-methyl), imidazolinone (imazapyr, imazethapyr), 2,6-Bis[(4,6-dimethoxy-2- pyrimidinyl)oxy]benzoic acid (bispyribac acid), triazol-pyrimidines (Penoxsulam), a benzoylpyrazole compound (Topramenzone). For the concentrating and cleaning of samples of water there were used cartridges for solid-phase extraction of Oasis HLB - the macro porous copolymer made on the basis of the balanced ratio of 2 monomers - lipophilic divinylbenzene and hydrophilic N-vinylpirrolidone. The range of the detected concentrations in water was volatile between 0.0005 and 0.005 mg/L, values of standard deviation vary in the range of 1.8-3.9%. Chlorine-containing acidic herbicides were analyzed by the method of GC-ECD and GC-MS (IE) after preliminary converting of compounds into flying derivatives with the use of diazomethane. Satisfactory extraction of substances from a water sample may be achieved by classical extraction in the system “liquid-liquid” with the application of Methyl tert-butyl ester. For cleaning of the derivatized sample there were used cartridges for solid-phase extraction on the basis of silica gel. The range of the determination of 9 active ingredients referring to classes of phenoxy-acetic acid (2,4- D, MCPA), pyridinecarboxylic (aminopyiralid, picloram, clopyralid), benzoic acids (dicamba), benzothiadiazinone (bentazone), biphenyl ester (acifluorfen) and a chloroacetamide (acetochlor) - 0.0001-0.001 mg/L, SD values vary in the range of 1.8-33%.