Magdalena Jankowska

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.

Rapid determination of acid herbicides in soil by liquid chromatography with tandem mass spectrometric detection based on dispersive solid phase extraction.

This study determined twenty six the highly sensitive phenoxy, pyridines, aliphatic and aromatic acid compounds in soil with a liquid chromatography tandem mass spectrometry. The samples were prepared by modified quick, easy, cheap, effective, rugged and safe (QuEChERS) analytical procedure in solid samples. Herbicides extraction effectiveness was evaluated at three different spiking levels (0.01, 0.1 and 1.0 mg kg(-1)). Fourteen different dispersive solid-phase extraction (d-SPE) sorbents in clean-up step were tested. The QuEChERS protocol with acidic alumina provided the highest number of pesticides with recoveries in the 70-120% range. The soil matrix effect was evaluated and for the majority of compounds were not significant, showing suppression or enhancement (±81-123%). The precision calculated as relative standard deviation (RSD) was below 22%. The linear relation was observed in the range 0.01-2.0 mg kg(-1) and the correlation coefficient R>0.999. The expanded measurement uncertainty was estimated as being on average, and was between 9% and 33%. The validated method was employed in the analysis of 309 real soil samples.

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.

Toxicological studies for adults and children of insecticide residues with common mode of action (MoA) in pome, stone, berries and other small fruit

The presence of pesticide residues in fruit is a serious health concern. This paper for the first time demonstrated the Hazard Index (HI) method to carry out acute, chronic and cumulative health risk assessment to the 14 groups of insecticides for three subpopulations. The challenge of this study was to present results from a long period of research (years 2005-2014) with toxicological aspects, especially in multiresidue samples. Near 1000 fresh pome, stone, berries and small fruit were prepared by two accredited MSPD and QuEChERS methods followed by liquid and gas chromatography analyses with various systems of detection ECD/NPD/MS/MS. Twenty percent of the fruit samples contained 16 insecticide residues in the range of 0.01-0.81mg/kg and 3% over MRL. The class of pesticide with the highest contribution to the ADI was found to be OPPs: dimethoate and diazinon for adults 48% and 66% of the ADI whereas for infants 144% and 294% of the ADI. The highest contributions of the cHQ to common MoA pesticides were AChE inhibitors: 135% for adults and 528% for infants, sodium channel modulators 4.9% and 20%, nicotic acetylocholine receptor <2.9% and <10.6% for adults and infants, respectively. The fruit with the highest contribution to the ADI were found to be apples (316%, 58%), cherries (96%, 37%) and pears (129%, 33%) for infants and adults. The study findings indicated that dietary exposures to insecticide residues in fruit would be unlikely to pose unacceptable health risks for the infants, toddlers and adults.

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.

Comprehensive toxicological study over 160 processing factors of pesticides in selected fruit and vegetables after water, mechanical and thermal processing treatments and their application to human health risk assessment

The challenge of the present comprehensive toxicological study was to evaluate water, mechanical and thermal processing factors (PFs) of twenty four pesticides (acetamiprid, alpha‑cypermethrin, azoxystrobin, boscalid, bupyrimate, chlorpyrifos, chlorothalonil, cyprodinil, deltamethrin, difenoconazole, fenazaquin, fenhexamid, fludioxonil, folpet, iprodione, lambda‑cyhlothrin, metalaxyl, pirymicarb, propargite, pyraclostrobin, tetraconazole, tiophanate methyl, thiram, trifloxystrobin) in different fruit and vegetables and estimate health risk for adults and children. The water (PF = 0,09-0,94), mechanical (PF = 0,13-0,32) and thermal (PF = 0,02-0,57) technology significantly or completely reduced concentrations of twenty one active substances in broccoli, tomatoes, strawberries and black currants. Pyrethroid insecticides (alpha‑cypermethrin, deltamethrin and lambda‑cyhalothrin) exhibited PF above one in berries influenced by high temperatures. Comprehensive processing factor database technology/pesticide/matrix (over 160 PFs) for 24 pesticides in selected fruit and vegetable species after different processing treatments was created. This paper for the first time compares health risk assessments of acute and chronic of two subpopulations of adults and the most critical group of small children using two mathematical models, without (I) and with including (II) calculated PF values. More realistic estimation of the dietary intakes of the pesticides was achieved using PFs. The hazard quotients (HQs) estimated from chronic and acute dietary exposure (Model l) were above 20% and after intake correction (Model II) were reduced to HQs = 11.5% after water, 3% mechanical and 9.5% thermal treatment.

Behaviour of selected pesticide residues in blackcurrants (Ribes nigrum) during technological processing monitored by liquid-chromatography tandem mass spectrometry

In this experiment, the behaviour of ten pesticides on field-sprayed blackcurrants (Ribes nigrum) after washing, juicing and cooking was investigated. The concentration level changes in two acaricides (fenazaquin, propargite), three insecticides (alpha-cypermethrin, deltamethrin and lambdacyhalothrin) and five fungicides (boscalid, bupirimate, difenoconazole, pyraclostrobin, thiophanate-methyl) were quantified. Analysis was carried out using the QuEChERS method followed by chromatographic analysis based on LC-MS/MS. The matrix effects ranged from —(17.4 ± 8.1) % to (15.9 ± 7.8) %. The limits of detection and limits of quantification were 0.003 mg kg−1 and 0.01 mg kg−1, respectively. The mean recoveries of the analytes ranged between 71 % and 109 %. The processing factors of all the blackcurrant products were determined. Washing reduced the pesticide residues up to 71 %. Juicing significantly reduced all the pesticide residues (processing factors (PFs) ranged 0.14–0.47). Cooking resulted in a decrease in residues up to 82 %. The residue levels of alpha-cypermethrin, deltamethrin and lambda-cyhalothrin in blackcurrant jam increased, and PFs > 1 were noted as PF = 1.38, 1.66 and 1.04, respectively. Cluster analysis was performed to find any similarity in the behaviour of pesticides after processing. The results confirmed that solubility, polarity and mode of action could be used to explain differences in the behaviour of pesticides.

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.