Insecticide and fungicide effect on thermal and olfactory behavior of bees and their disappearance in bees' tissues.

Plant protection products may affect the behavior of organisms which are not a target of control. The effect of Karate Zeon 050 CS (λ-Cyhalothrin -based insecticide; λ-CBI) and Amistar 250 SC (Azoxystrobin-based fungicide; ABF) was determined on Apis mellifera worker attraction towards their own colony odour, along with temperature preferences. Bees exposed to pesticides prefer the environment with the odour of their nest less often than the control group, and that insecticide-treated bees chose warmer environments than the control insects. The observed differences in the bees, especially with attraction towards their own colony, were dependent on the time of day. Chromatographic analyses indicated that λ-Cyhalothrin elimination was half that of Azoxystrobin in bee organisms, and both agents retarded each other's clearance. Mathematical modeling estimated that despite a relatively high disappearance rate, both compounds might have been bio-accumulated at relatively high level.

Assessment of risk to honey bees and honey consumers resulting from the insect exposure to captan, thiacloprid, penthiopyrad, and λ-cyhalothrin used in a commercial apple orchard.

Samples of leaves, flowers, soil, pollen, bee workers, bee brood, honey, and beeswax were collected to assess the possibility of a transfer of captan, thiacloprid, penthiopyrad, and λ-cyhalothrin from apple trees of Idared variety to honey bee (Apis mellifera) hives. Chemical analyses were performed using the Agilent 7890 Gas Chromatograph equipped with the Micro-cell Electron Capture Detector. It was found that significant amounts of penthiopyrad, the active ingredient of Fontelis 200 SC, were present in leaves, flowers, pollen, bee workers, and beeswax. Simultaneously, captan was present in the brood, worker bees, and honey samples. Significant levels of the captan residues were also detected on the soil surface. In honey samples, captan residue levels exceeded the acceptable standard, reaching 160% of its maximum residue level. However, in no case the amounts of captan, thiacloprid, penthiopyrad, and λ-cyhalothrin ingested with honey by an adult consumer exceeded the level of 0.02% of the acceptable daily intake. Despite the trace amounts of pesticide residues in honey samples collected during the field trial, bee honey consumption can be considered safe. An adult consumer can safely consume about 16 kg of honey.

Treating honey bees with an extremely low frequency electromagnetic field and pesticides: Impact on the rate of disappearance of azoxystrobin and λ-cyhalothrin and the structure of some functional groups of the probabilistic molecules.

The purpose of these laboratory tests was to assess the impact of 50 Hz EMF (electromagnetic field) on the disappearance of azoxystrobin (active ingredient (AI) of Amistar 250 SC) and λ-cyhalothrin (AI of Karate Zeon 050 CS) in the body of honey bees (Apis mellifera) and the structure of some functional groups of the probabilistic molecules in their organisms. Amistar 250 SC (an azoxystrobin-based fungicide; ABF) and Karate Zeon 050 CS (a λ-cyhalothrin-based insecticide; CBI) are plant protection products (PPPs) applied to bee-pollinated-crops. Chromatographic methods were used to assess the rate of AI disappearance. EMF affected the rate of disappearance of azoxystrobin and λ-cyhalothrin in bees within 6 h of intoxication. When these substances were used separately their disappearance in the presence of EMF slowed from 12.6% to 10.5% h-1 and from 9.2% to 4.8% h-1, respectively, and accelerated when used in a mixture, from 14.1% to 14.7% h-1 and from 9.3% to 11.5% h-1 respectively. Fourier Transform Infrared (FTIR) spectroscopy was used to analyze changes in the functional groups of the probabilistic molecules of the tested bees. To obtain the information about the spectra variations we used the Principal Component Analysis. It has been shown, that EMF statistically significantly interferes with amide I and II, symmetric PO32- group from DNA, RNA and phospholipids vibrations. It also increased the number of changes of functional groups of the probabilistic molecules caused by ABF, but at the same time limited the changes in the functional groups studied in bees treated with CBI and a mixture containing both of them. In addition, exposure to EMF in bees treated with fungicide or insecticide, separately, and with both preparations caused differences (p < 0.05) in the secondary structure of proteins compared to controls. The obtained results indicate that EMF may affect the rate of metabolism and the detoxification process of pesticides in bees, depending on the AI of PPPs, applied individually or together. However, further detailed research is required to explain the mechanism of EMF as a detoxification modulator.

Influence of Bacillus subtilis and Trichoderma harzianum on Penthiopyrad Degradation under Laboratory and Field Studies.

In plant protection, biological preparations are used alternately with chemical pesticides. The applied microorganism can influence the concentration of chemical substances. Laboratory and field studies were conducted to assess the influence of Bacillus subtilis and Trichoderma harzianum on the penthiopyrad concentration. In laboratory studies, the effectiveness of penthiopyrad degradation by B. subtilis was approximately 5% during 14 days of the experiment. For penthiopyrad treated with T. harzianum strains, the degradation effectiveness ranged from 34.2% on Day 3 to 56.9% on Day 14. In experiments testing the effects of mixed culture of microorganisms, the effectiveness of penthiopyrad degradation ranged from 23.7% on Day 3 to 29.1% on Day 14. After treatment of apple trees of Gala and Golden Delicious varieties with a biological preparation, a maximum degradation of penthiopyrad of 20% was found in both varieties. Samples of apples were prepared by the quick, easy, cheap, effective, rugged and safe (QuEChERS) method, and penthiopyrad was analyzed by gas chromatography with a mass detector. A determined value of the chronic exposure to penthiopirad was 1.02% of the acceptable daily intake, both for children and for adults. The acute exposure amounted to 7.2% and 1.9% of the acute reference dose for children and adults, respectively. These values were considered to be acceptable and not threatening to health.

Assessment of boscalid and pyraclostrobin disappearance and behavior following application of effective microorganisms on apples.

The aim of this study is to assess the disappearance of boscalid (IUPAC name: 2-chloro-N-[2-(4-chlorophenyl)phenyl]pyridine-3-carboxamide) and pyraclostrobin (IUPAC name: methyl N-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]phenyl]-N-methoxycarbamate) residues in apple fruit, and to verify whether an organic fertilizer enriched with strains of antagonistic microorganisms can reduce pesticide residue levels. Field trials were conducted in a commercial orchard on apples of the Gloster variety, during 21 days after the treatment with Bellis 38 WG and the subsequent application of Zumba Plant formulation containing Bacillus spp., Trichoderma spp. and Glomus spp. In control samples, the decrease rate of boscalid and pyraclostrobin residue levels followed an exponential function, described by formulae Rt = 0.2824e-0.071t and Rt = 0.1176e-0.060t, with the coefficient of determination of r2 = 0.8692 and r2 = 0.9268, respectively. These levels dropped to half (t1/2) of their initial values after 9.8 and 11.5 days, respectively. The treatment with Zumba Plant resulted in a reduction in boscalid and pyraclostrobin residue levels by 52% and 41%, respectively. The results of this study are of importance for horticulture sciences and for producers of apples using plant protection products (PPPs).

A study on residue levels of fungicides and insecticides applied according to the program of raspberry protection.

This paper presents surveys on residue levels of fungicides and insecticides applied according to the raspberry protection program. The field trials were conducted in 2013-2014 on a plantation of raspberry of the Laszka variety dessert raspberry very popular in Poland. Laboratory samples were collected starting from a day of the first fruit picking to the end of harvest. The highest mean residue levels were found for boscalid and pyraclostrobin (2.395 mg/kg and 0.732 mg/kg, respectively), in both cases they were at a level of about 24% of their maximum residue levels (MRLs); and for cypermethrin (0.235 mg/kg; i.e. close to 50% of its MRL). The long-term dietary intakes of those substances by Polish adult consumers were also at low levels of 0.52, 0.22, and 0.04% of acceptable daily intake (ADI), respectively. Therefore, the results obtained indicated that even on day zero of picking ripe raspberries, the pesticide residues not only were well below their corresponding MRLs, but also their daily intakes did not even approach 1% of the ADI. In 2013, pesticide residues in ripe fruit evolved according to a pattern different than in a subsequent year; while in 2014 they changed at a constant exponential rate.

Behavior of fluopyram and tebuconazole and some selected pesticides in ripe apples and consumer exposure assessment in the applied crop protection framework.

The supervised field trials were conducted in a commercial apple orchard in 2016. The trials were an attempt to determine a model for dissipation and toxicological evaluation of fluopyram, tebuconazole, captan, tetrahydrophthalimide (THPI), pirimicarb, spirodiclofen, and boscalid residues detected in fruit of Red Jonaprince, Lobo, and Gala varieties immediately before harvest. The analysis also covered amounts of pesticides still present in remnants of calyx in Lobo and Gala varieties immediately before harvest. Laboratory samples of ripe apples were collected within 14 days of the treatment. Levels of pesticide residues detected in the samples changed at a constant exponential rate, and the residue levels found in ripe apples of Red Jonaprince, Gala, and Lobo varieties immediately before harvest were below maximum residue levels (MRL). Overall, captan residues in remnants of calyx were at a level of 22.3% for the Gala variety and 9.3% for the Lobo variety. Likewise, the long-term daily intake of the detected substances by a Polish adult consumer was low, ranging from 0.02% ADI for pirimicarb to 0.72% ADI for captan.

A case study on toxicological aspects of the pest and disease control in the production of the high-quality raspberry (Rubus idaeus L.).

The field studies on the residue levels of the fungicides and insecticides used in commercial raspberry (Rubus idaeus L.) plantation have been performed. Starting on the first day of harvesting (on June 19), 20 laboratory samples of fruit, 10 laboratory samples of leaves and 4 samples of soil were analyzed and the residue levels were compared to the Maximum Residue Limits (MRL) and Acceptable Daily Intakes (ADI). All analyses were carried out using extraction method and gas chromatography technique. Esfenwalerate (Sumi-alpha 050 EC) and beta-cyfluthrin (Bulldock 025 EC), the insecticides belonging to the group of synthetic pyrethroids, were not found in harvested ripe fruits, while cypermethrin residues (Cyperkill 25 EC) applied on May 24, 25 days later was still found on low levels in fruits (0.026 mg kg(-1)) and in leaves (2.58 mg kg(-1)). In turn, residues of chlorpyrifos (Dursban 480 EC), applied to the soil on May 15 against the cockchafers Melolontha melolontha and Otiorhynchus sp., were found at the level 0.004 mg kg(-1). The content of pesticides in ripe fruits depended mainly on the dose and on the time that has elapsed from the date of their application and were as follows: boscalid -0.950, pyrimethanil -0.917, pyraclostrobin -0.253 cypermethrin -0.026 and chlorpyrifos -0.004 mg kg(-1) while in leaves: boscalid -30.64, pyrimethanil -8.13, pyraclostrobin -15.82, cypermethrin -2.58 and chlorpyrifos -0.15 mg kg(-1). The highest average daily intake was in the case of boscalid, and in fruits and leaves reached the levels 0.205 and 6.63, in total 0.33% and 12.18% of ADI, respectively.

Behavior of pyrimethanil, pyraclostrobin, boscalid, cypermethrin and chlorpyrifos residues on raspberry fruit and leaves of Laszka variety.

The purpose of the research conducted was to investigate and evaluate the behavior of pyrimethanil, pyraclostrobin, boscalid, cypermethrin and chlorpyrifos, the active ingredients of selected fungicides and insecticides, on ripe fruit and in fully developed leaves of raspberry of the Laszka variety. The field trial was carried out in the period of one month starting from the first fruit picking. The results obtained indicated that residue levels on the day of the first crop picking did not even approximate the corresponding EU-MRLs (http://ec.europa.eu/sanco_pesticides). Individual substances in raspberry fruits and leaves disappeared at a similar rate. As a result of chlorpyrifos application to the soil, its residue in fruits and leaves occurred for the whole period of fruit bearing, though in fruit they dropped successively. To produce raspberries with residues below or equal to 0.01 µg g(-1), the application of pesticides should be stopped at least 2-3 weeks before the first crop picking, and on condition that an appropriate preparation (active in low doses) is applied to the last treatments.

Potential of ozone utilization for reduction of pesticide residue in food of plant origin. A review.

Residues of plant protection products can be nowadays found in almost all samples of fruits as even if their application was carried out with respect to standards of Good Agricultural Practice. The intake of these compounds with food of plant origin may result in various disorders and diseases. Since the use of plant protection agents seems unavoidable, it is necessary to treat contaminated food material to eliminate or reduce residues content within food products. Ozone is utilized for elimination of biological and chemical contaminants in various environmental matrixes. Since its utilization in food industry has been permitted many experiments were conducted in order to determine its efficiency and side effects on food quality. The goal of this paper is to contribute to a discussion on the ozonization as a process leading to reduction of pesticide residues on plant surface.

Comparative study on disappearance trends of captan and trifloxystrobin residues on fruit and apple tree leaves using internal normalisation method.

Supervised field trials were carried out in a commercial orchard in 2011. The purpose of the study was to assess the usefulness of the comparative method to examine the mechanism of disappearance of pesticide residues. Captan and trifloxystrobin residues were determined with the use of gas chromatograph equipped with a micro-electron capture detector. Disappearance trends of captan and trifloxystrobin residues in fruit and leaves were estimated using the method of internal normalisation, and based on that, the courses of concentration changes of these substances on fruit and leaves and the amount of these substances in one apple were established. The initial deposits of trifloxystrobin on leaves and fruits dropped by 50% within 8 and 4 days after treatment, respectively, in both varieties, whereas captan residues dropped by 50% within 29 days in leaves and 7 days in apples of the Olive Yellow varieties.

[Occurrence of plant protection product residues in apples in 2007]. / Wystepowanie pozostalosci srodków ochrony roslin w jablkach w roku 2007.

The aim of this paper was to present occurrence of plant protection product residues in apples in 2007. Gas chromatographic and spectroscopy methods were used. The most frequently found were fungicides: dithiocarbamate residues (18% of the analysed samples), captan residues (13%), pyrimethanil residues (6%) and insecticides: chlorpiryfos residues (6%), diazinon residues (6%) and pirimicarb residues (5%). 5.6% of analysed samples exceeded the national Maximum Residue Level established for apples. Violations were found for: flusilazole (n = 2), propiconazole (n = 2), cyprodinil (n = 1), dimethoate (n = 1), fenitrothion (n = 1).

[Occurrence of pesticide residues in raspberries in 2000-2005]. / Wystepowanie pozostalosci pestycydów w malinach w latach 2000-2005.

The aim of this paper was to present occurrence of pesticide residues in raspberries in 2000-2005. Gas chromatographic and spectroscopy methods were used. The most frequently found were tolylfluanid residues (43% of the analysed samples), procymidone residues (33%), pyrimethanil residues (15%), ethylenebisdithiocarbamates (EBDC) residues (8%) and iprodione residues (5%), while insecticides (mainly synthetic pyrethroids) cypermethrin residues (6%) and bifenthrin (4%). In 8 % of analysed samples EBDC residues exceeded the national Maximum Residue Level established for raspberries. On relatively the highest level EBDC occurred.

[Occurrence of some pesticides residues in peppermint Mentha piperita L. in 2003-2005]. / Wystepowanie pozostalosci niektórych pestycydów w miecie pieprzowej Mentha piperita L. w latach 2003-2005.

The aim of this paper was to present occurrence of pesticides residues in peppermint Mentha Piperita in 2003-2005 and to estimate of their intakes by consumer. Gas chromatographic and spectroscopy methods were used. The most frequently found were chlorpyrifos residues (16% analysed samples) followed by terbacil (11%), dithiocarbamates (10%) and diazinon (5%). Residues in 14% analysed samples exceeded the European Union Maximum Residue Levels established for tea. Assuming consumption of peppermint on the level of 4.5 g (three bags) per day, short-term intake by adult and child consumer was a few times lower then Acceptable Daily Intake.

Disappearance of pyrimethanil residues on tomato plants.

The objective of this work was to estimate the disappearance of pyrimethanil, the active ingredient of Mythos 300 SC, at present, commonly used for the protection of greenhouse vegetables against diseases of fungal origin. Disappearance trends of the chemical deposits were studied on tomato plants grown in commercial greenhouses sprayed with a homogeneous 0.15% aqueous solution of the plant protection product. It was found that, on average, pyrimethanil residues on ripening fruits dropped by half and reached detection limit level in 5.7 and 13.7 days after Mythos 300 SC application, respectively. Pyrimethanil residues on tomato leaves dropped by half within 4.0 days and reached detection limit level in the first 10.5 days. Therefore, in conditions of high infection pressure, there is a need to repeat the fungicide application as early as after 3 or 4 days after previous application of Mythos 300 SC.