The aim of this research was to prepare the basis for the certification of the apple orchard protection program by determining disappearance models for active ingredients (AIs) of plant protection products (PPPs) in fruits. Field trials were carried out in a conventional apple orchard protected with PPPs in accordance with the currently adopted program. Residues of their AIs were determined using Agilent GC-MS/MS 7000D and LC-MS/MS 6470 QQQ, and their decreases were expressed by the exponential formula: R _t = R ₀ × ^{e–k × t}. Of all the AIs found in mature fruits, captan disappeared at the fastest rate [t _(1/2) in the range of 9 to 13 days], followed by fluopyram [t _(1/2) = 13 days], tebuconazole [t _(1/2) = 14 days] and carbendazim [t _(1/2) in the range of 24 to 32 days]. With the exception of dithiocarbamates and some fungicides (e.g., Captan 80 WDG) based on captan and methyl thiophanate, other insecticides and fungicides currently recommended can be used up to 3 months before harvest practically with virtually no restrictions. From July 15 to August 15, the chemicals effective at application rates not exceeding 0.3 kg of AI per ha should be used. To protect apples against storage diseases, PPPs that are effective at a dose ≤ 0.1 kg AI per ha (e.g., certain triazoles or strobilurins) and applied not later than 1 month before harvest, should be used.

A field trial on the transfer of pyrimethanil, cyprodinil and cyflufenamid residues from apple trees of Idared cultivar to hives by honeybees Apis mellifera was carried out. Two days after spraying (Faban 500 SC and Kendo 50 EW), and on the day of spraying (Chorus 50 WG), the quantities of residues on leaves and flowers of apple trees and pollen were as follows: pyrimethanil: 1.45 μg per cm2 of leaves, 11.51 μg per single flower and 7.18 μg · g ⁻¹ of pollen, cyprodinil:1.35, 8.64 and 7.94 μg, and cyflufenamid: 0.064, 0.266 and 0.11 μg, respectively. All of them subsequently disappeared exponentially. Two days after, and on the day of spraying, pyrimethanil (1.81 μg · g ⁻¹), cyprodinil (up to 0.55 μg · g ⁻¹) and cyflufenamid (0.04 μg · g ⁻¹) were found in worker bees. Residues of all used chemicals were found in the brood, honey and wax samples. The residues of pyrimethanil, cyprodinil and cyflufenamid in worker bees exceeded the level of 0.2% of the LD50, which indicates that their application rates (doses) are safe for the honey bee.