The paper reports ultraviolet matrix-assisted laser desorption/ionization mass spectroscopy (UVMALDI-MS) protocol for determination of complex heterogeneous emulsion or suspension formulations. The active agents and surfactants are morpholine fungicide fenpropimorph (1), amorolfine (2), tridemorph (mixture of 2,6-dimethyl-4-alkylmorpholins 3–6), 2,6-dimethyl-4-[2-methyl-3-(6-methyl-decahydro-naphthalen-2-yl)-propyl]-morpholine (7), dodemorph (8), main metabolite of 1 fenpropimorph acid (9), sodium dodecyl sulfate (10), and stearate (11). The full method and techniques validation as well as method performance parameters are discussed in terms of their maximal representativeness toward real environmental and foodstuff assay problems. These are additionally complicated by heterogeneous laterally, vertically, and time distribution of pesticide contaminants and their major metabolites in environmental samples. The real environmental heterogeneous distribution is elucidated, studying sterilized soil fractions with particle size 2.0 μm, clay content 11.5 %, silt 23.0 %, sand 8.1 %, and pH ∈ 6.0–8.1. A statistical sampling cluster approach is used. The method performance parameters are concentration LODs of 0.026 mg kg⁻¹(res. LOQs 0.08666 mg kg⁻¹). Concentration linear dynamic ranges are ∈ 0.025–7.3 mg kg⁻¹(r² = 0.99822 and 0.99421) and ∈ 2.3–7.4 mg kg⁻¹(level of confidence of 99.33₁ %) for complex spiked heterogeneous soil samples. The data illustrates the great capability of method and its promising application for environmental contamination monitoring and controlling programs for assessment.

The saprotrophic fungus Alternaria alternata is widespread in the agro-environment and produces more than ten allergenic proteins, mostly protein Alt a 1. The frequency of the Alt a 1 gene was analyzed in a group of A. alternata isolates from winter wheat kernels obtained in Poland, and the effectiveness of various fungicides targeting the pathogen was evaluated. The Alt a 1 gene was identified in four of the seven tested isolates. A. alternata colonized 35.67% kernels on average, but its frequency increased in stored grain where the presence of epiphytes was noted on 23.09 to 51.38% kernels, and endophytes—in 26.21 to 42.01% of kernels. The efficacy of field-applied fungicides did not exceed 50%, despite the fact that A. alternata is highly sensitive to propiconazole, fenpropimorph, and tebuconazole under in vitro conditions. The analyzed isolates were characterized by limited sensitivity to azoxystrobin (EC₅₀ ranged from 0.505 to 1.350 μg cm⁻³) due to a mutation at codon 143 of the CYT b gene, responsible for resistance to quinone outside inhibitor fungicides, which was noted in all isolates. The spread of A. alternata can be effectively controlled with suitable fungicides and by monitoring the prevalence of pathogenic isolates in the environment.

Background, aim and scope The ergosterol biosynthesis-inhibiting (EBI) fungicide prochloraz can enhance the effect of other pesticides in a range of animal species. Approximately 50% of the fungicides used in Denmark are EBI fungicides. Hence, if they all have synergising potential, a risk assessment of pesticide mixtures based on additivity might not suffice. This study investigates the synergising potential of six different EBI fungicides representing the imidazoles (prochloraz), the triazoles (epoxiconazole, propiconazole and tebuconazole), the piperidines (fenpropidin) and the morpholines (fenpropimorph) together with the pyrethroid insecticide alpha-cypermethrin. Materials and methods Tests were made on the aquatic crustacean Daphnia magna. Mixtures of each of the fungicides were tested together with the insecticide both at a 50:50% effect mixture ratio and, subsequently, in a ray design including five mixture ratios. The results were tested against the concentration addition reference model using dose-response surface analyses. Results The results of the binary dose-response surface studies showed that mixtures with prochloraz increased toxicity up to 12-fold compared with what was expected using the reference model concentration addition (CA). Epoxiconazole and propiconazole enhanced toxicity up to six and sevenfold, respectively. Fenpropimorph showed antagonism, whilst mixtures with tebuconazole and fenpropidin did not deviate statistically from CA. Conclusions Hence, it can be concluded that both imidazoles and some, but not all, triazoles can enhance the effect of a pyrethroid insecticide towards D. magna substantially. Epoxiconazole and propiconazole are often sprayed out together with pyrethroids in tank mixtures. The extent to which this might create unforeseen ecological problems is discussed.