Določanje neonikotinoidnih pesticidov v propolisu

Tomšič, Rok (author), Prosen, Helena (mentor), Heath, Ester (co-mentor)

Namen magistrskega dela je bil razviti metodo za določevanje petih neonikotinoidnih pesticidov (acetamiprid, klotianidin, imidakloprid, tiakloprid, tiametoksam) v vzorcih propolisa. Preizkusil sem dva načina priprave vzorca: ekstrakcijo na trdno fazo (angl. SPE – Solid Phase Extraction) in QuEChERS ekstrakcijo (angl. Quick, Easy, Cheap, Effective, Rugged, Safe). Ekstrakte sem analiziral z LC-MS/MS instrumentom, ki je deloval v SRM načinu (angl. Selected Reaction Monitoring). Čistejše ekstrakte in boljše izkoristke sem dosegel z ekstrakcijo na trdno fazo, zato sem metodo SPE-HPLC-MS/MS tudi validiral. Validiral sem jo na dveh koncentracijskih nivojih (10 µg/L in 50 µg/L) s tremi ponovitvami na vsakem nivoju. Rezultati so pokazali, da daje metoda zadovoljive izkoristke (61 – 101 %) za vse analite razen za klotianidin, katerega izkoristek znaša 10 % v spodnjem in 20 % v zgornjem koncentracijskem nivoju. Ponovljivost metode je zadovoljiva, saj se relativni standardni odmiki gibljejo med 5 % in 29 % (spodnji koncentracijski nivo) ter med 3 % in 13 % (zgornji koncentracijski nivo). Za vse analite sem dosegel nizke meje zaznave (0,2 -4,4 µg/L) in meje določitve (0,8 – 14,7 µg/L). Zaradi kompleksne matrice vzorca sem za oceno matričnega efekta pripravil umeritveno premico z matričnimi raztopinami (angl. MM – Matrix Matched) in jo uporabil tudi za določitev linearnega območja in točnosti metode. Metoda je točna (relativna standardna napaka: 1,9 % – 10,4 %) ter linearna v širokem koncentracijskem območju (R2 > 0,991) za vse analite. SPE-HPLC-MS/MS metodo sem uporabil za analizo 30 realnih vzorcev propolisa (18 surovih vzorcev in 12 alkoholnih tinktur). V 7 vzorcih sem potrdil prisotnost acetamiprida, imidakloprida in tiakloprida nad mejo zaznave, vendar je bila njihova vsebnost pod mejo določitve optimizirane metode.

• Language: Slovenian
• Keywords: neonikotinoidi, SPE, QuEChERS, propolis, LC-MS/MS
• Work type: Master's thesis/paper
• Typology: 2.09 - Master's Thesis
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Year: 2019
• PID: 20.500.12556/RUL-113183
• COBISS.SI-ID: 1538507459
• Publication date in RUL: 11.12.2019

Secondary language

• Language: English
• Title: Analysis of neonicotinoid pesticides in propolis

Abstract

This study aimed to develop a method for the determination of five neonicotinoid pesticides (acetamiprid, clothianidin, imidacloprid, thiacloprid, and thiamethoxam) in propolis samples. Two sample preparation methods were tested: solid-phase extraction (SPE) and quick, easy, cheap, effective, rugged, and safe (QuEChERS). The extracts were then analysed with liquid chromatography-tandem mass spectrometry (LC-MS/MS) in selected reaction monitoring (SRM) mode. Because solid-phase extraction resulted in cleaner extracts and better recoveries, only the SPE-HPLC-MS/MS method was validated. The method was validated at two spiking levels (10 µg/L and 50 µg/L) in triplicate at each level. Except for clothianidin, we obtained satisfactory recoveries the other four pesticides (61 % – 101 %). Recoveries of clothianidin were 10 % at the lower and 20 % at the higher spiking level, respectively. Method repeatability was also good with a relative standard deviation from 5 % to 29 % at the lower spiking level and from 3 % to 13 % at the higher spiking level. The method also showed low limits of detection (0.2 – 4.4 µg/L) and quantification (0.8 – 14.7 µg/L). In order to compensate for the matrix effect, matrix-matched calibration was used. Based on matrix-matched calibration curves, good accuracy (relative error: 1.9 % – 10.4 %) and linearity were determined (R2 > 0.991) for all of the neonicotinoids tested. The validated SPE-HPLC-MS/MS method was used to analyse 30 propolis samples (18 raw propolis and 12 alcohol tinctures). The presence of some analytes (acetamiprid, imidacloprid and thiacloprid) were above limits of detection in 7 samples, however their conectrations were lower than limits of quantification for optimised analytical method.

• Keywords: neonicotinoids, SPE, QuEChERS, propolis, LC-MS/MS