Ewa Rutkowska

Multi-residue methods for the determination of over four hundred pesticides in solid and liquid high sucrose content matrices by tandem mass spectrometry coupled with gas and liquid chromatograph.

For the first time three methods: matrix solid phase dispersion (MSPD), original and modified QuEChERS, with and without clean up step were studied in order to evaluate the extraction efficiency of various classes of pesticides from solid and liquid high sucrose content matrices. Determinations over four hundred pesticides were performed by gas and liquid chromatography with triple quadrupole mass spectrometry (GC/LC/MS/MS) using multiple reaction monitoring. The proposed methods were validated on sugar beets and their technological product beet molasses. In general, the recoveries obtained for the original QuEChERS and MSPD method were lower (<70%) than for the modified QuEChERS without clean up in sugar beet and with clean up in beet molasses. Among these methods, high extraction yields were achieved as recommended in SANCO/12571/2013, with repeatability of 4.4-19.2% and within-laboratory reproducibility of 7.1-18.4% for citrate QuEChERS, whereas greater ruggedness were observed for MSPD. The limit of quantification (LOQ) at (the lowest MRL=0.01mgkg(-1)e.g. for oxamyl()) or below (0.005mgkg(-1)) the regulatory maximum residue level for the pesticides were achieved. The expanded measurement uncertainty was not higher than 30% for all target analytes. Matrix effects were compared and observed for both matrices at both gas and liquid chromatography. The most compounds showed signal enhancement and it was compensated by using matrix-matched calibration and modified QuEChERS characterized lower matrix effects. The confirmation of suitability citrate QuEChERS optimized method was to use for routine testing of several dozen samples determination and residue of epoxiconazole and tebuconazole (both at 0.01mgkg(-1)) in the samples of beet molasses and cyfluthrin (0.06mgkg(-1)) in sugar beet were found.

Health risk analysis of pesticide residues in berry fruit from north-eastern Poland.

ABSTRACT The first aim of this paper was to evaluate pesticide residue levels of berry fruit samples. The second aim was to analyze health risks associated with pesticide levels. The monitoring was conducted on samples from producers in north-eastern Poland, during the time period 2005-2010. In total, 241 samples of berry fruit were analyzed using validated and accredited multi residue methods. The studies included 7 commodities (125 strawberry, 59 black currant, 25 raspberry, 23 chokeberry, 7 red currant samples and one sample of elderberry and wild strawberry), and the analysis of 128 pesticides. Residues, mainly insecticides, were found in 47.7% of samples while 40.7% of samples contained pesticide residues below MRLs and 7% above MRLs. The pesticides were found most often in red currant (100%) and black currant (63%) samples. The most frequently detected pesticides were fenazaquin and fenitrothion. Pesticide residues at levels exceeding legally binding MRLs occurred mostly in black currant samples (12 samples). Violations of the maximum residue limits (MRLs) (15 notifications) and use of a forbidden plant protection product (8 notifications) were found in twenty-three berry samples during the six-year study. For these cases, the RASFF system (rapid alert system for food and feed) procedures were initiated. The highest number of notifications was recorded in 2008 (11 notifications). Only one of the notifications was prepared for berry fruit from an integrated production system − black currant, the remaining were for conventional fruit. Among the RASFF notifications, 17 (74%) were for black currant samples. The estimated exposure to pesticide residues detected in the analyzed berry fruit samples was shown to be very low for the general population (adults) and for the critical population of small children. Acute and chronic exposure based on residue levels did not adversely affect consumer health. STRESZCZENIE Celem pracy była ocena poziomów pozostałości środków ochrony roślin w próbkach owoców jagodowych z obowiązującymi przepisami oraz analiza ryzyka dla zdrowia konsumentów. Badania obejmowały próbki pochodzące z północnowschodniej Polski, które wykonywano w ramach urzędowej kontroli w latach 2005- 2010. Przebadano 241 próbek owoców jagodowych (125 próbek truskawek, 59 − porzeczek czarnych, 25 − malin, 23 − aronii, 7 − porzeczek czerwonych i po jednej próbce bzu czarnego i poziomek). Pozostałości pestycydów, głównie insektycydów, wykryto w 47,7% próbek, z czego 40,7% z pozostałościami poniżej NDP, a 7% powyżej NDP. Najczęściej wykrywano fenazachinę i fenitrotion. Przekroczenia NDP dotyczyły głównie próbek porzeczki czarnej (12 próbek). Procedurę RASFF (Rapid Alert System for Food and Feed) w trakcie sześcioletnich badań wszczęto w dwudziestu trzech przypadkach, tylko raz dla próbek z produkcji integrowanej (flusilazol), w pozostałych przypadkach dotyczyły owoców wyprodukowanych w sadach konwencjonalnych. Nie stwierdzono niezgodności dla owoców ekologicznych. Powiadomienia przesłano ze względu na przekroczenia najwyższego dopuszczalnego poziomu pozostałości (NDP) (15 zgłoszeń) oraz stosowania niedozwolonych środków ochrony roślin (8 zgłoszeń). Największą liczbę powiadomień odnotowano w 2008 roku, w większości dla próbek porzeczki czarnej - 17 powiadomień (74% wszystkich zgłoszeń RASFF). Najczęściej zgłoszenia RASFF dotyczyły insektycydów (70%), to jest fenazachiny i fenitrotionu. Oszacowane ryzyko narażenia dla populacji generalnej (dorośli) i populacji krytycznej tzn. małych dzieci na pozostałości środków ochrony roślin wykazało, że jest ono stosunkowo niskie. W omawianym okresie nie stwierdzono produktów z owocami jagód, których spożycie mogło mieć negatywne skutki zdrowotne.

Simultaneous determination of 223 pesticides in tobacco by GC with simultaneous electron capture and nitrogen-phosphorous detection and mass spectrometric confirmation

Abstract LSE (liquid-solid extraction), MSPD (matrix solid phase dispersion) and QuEChERS (quick, easy, cheap, effective, rugged and safe) extractions followed by GC-μECD/NPD to determine 223 pesticide residues in tobacco simultaneously were developed and compared. The identities of ten model pesticides were confirmed by GC-MS/MS. The type and amount of dispersant (Florisil, silica gel and alumina), sample mass, cleanup adsorbent, and the eluent (hexane, acetone and acetonitrile) were optimized. Linearity, recovery, LOQ, LOD, and matrix effect were compared. Most recoveries were 71−120% (RSD < 18%). LOD and LOQ were much lower than the CORESTA GRLs. The best method was QuEChERS: acetonitrile extraction and dispersive solid-phase extraction using primary-secondary amine and graphitized carbon. Graphical Abstract

Toxicological evaluation of multi-class pesticide residues in vegetables and associated human health risk study for adults and children

ABSTRACT This article describes, for the first time in 10 years, the toxicological evaluation of pesticide residues in highly consumed vegetables (35 commodities) and health risk studies. Among 1075 vegetable samples consisting mainly of tuber, root, fruiting, and Brassica, 20% of samples contained 38 pesticides in the range of 0.005–18.7 mg/kg and 1% > maximum residue limits (MRLs). Organophosphates and chloronitrile were most frequently found (20%) in the pesticide class. The highest concentration of 18.7 mg/kg was noted for dichlofluanid. Fruiting vegetables (8%), especially tomatoes (5%), were the most contaminated, while multi-residues were determined in 5% of the samples. Risk assessment was performed by analytical results and consumption on the 97.5 percentile expressed as hazard index (HI) and hazard quotient (HQ). The highest chronic HI was calculated for diazinon in lettuce (32% Acceptable Daily Intake (ADI) adults and 36% children) and for forbidden dieldrin in carrots (26%, 62% ADI). The highest acute HI was estimated for dichlofluanid in lettuce (69% Acute Reference Dose (ARfD)) for adults, whereas for children it was above the acceptance values of ARfD (168%). Organophosphate insecticides with common mode of action showed the greatest HQ (108% ADI). Vegetables may not be a serious problem for consumers, but investigations on pesticide residues are necessary to ensure food safety and the protection of human health, especially toward children who are more highly exposed to pesticides than adults.

Pesticide residues in crops produced in the north-eastern Poland (2013)Pozostałości środków ochrony roślin w płodach rolnych wyprodukowanych w północno-wschodniej Polsce (2013)

This paper presents results of official control of pesticide residues in the crops from the north-eastern Poland. In total 260 samples were analysed in the year 2013 (45% fruit, 44.2% vegetables and 10.8% cereals and oilseeds). Among 188 pesticides, 36 active substances were detected, including 57.3% fungicides. Pesticide residues most often were determined in the samples of fruit (74.4%), mainly in currants (28.2%) and apples (25.6%). Pesticide residues below the maximum residue levels (MRLs), contained 45.4% (118) samples, while 5.4% (14) of tested sample exceeding MRLs. The use of non-approved pesticides was stated in 5% of tested samples. In 2013, 17 reports within the Rapid Alert System for Food and Feed (RASFF) were issued.

PESTICIDE RESIDUES IN FRUITS AND VEGETABLES PRODUCED IN ORGANIC, INTEGRATED AND CONVENTIONAL SYSTEMS

Presented research concerns the evaluation of residues of synthetic pesticides in crops, depending on the system of production: conventional, integrated and organic. The study was conducted in 2005-2009 on 1134 samples of plant material derived from the four provinces: Lubelskie, Podlaskie, Warminsko-Mazurskie and Mazowieckie. The 123 active substances of pesticides were searched in the plant material. This research has been shown that in the samples of fruit produced in the integrated system percentage of samples with residues below the maximum residue levels (MRL) is larger (55 %) than in the samples from conventional production (28 %), and less with above MRL (3 %). The pesticide residues were also detected in 8 % in samples of fruits and vegetables from organic production.