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Human activities in modern life are contributing significantly to global environmental pollution. With the need for clean drinking water ever increasing, so does the need to find new water-cleaning technologies. The ability of nanoparticles (NPs) to remove persistent pollutants from aqueous solutions makes them very important for use in water treatment technology. Titanium dioxide (TiO2) is recognized as an NP with unique optical, thermal, electrical, and magnetic properties and is widely used as an adsorbent material. Due to the extensive use of pesticides, their removal from the aquatic environment has gained widespread attention from the scientific community. In the present work, the transport of pesticide thiophanate methyl (TM), as well as the cotransport of TM and TiO2 nanoparticles, in a water-saturated column packed with quartz sand under various water conditions were investigated. Several ionic strengths (1, 10, 50, and 100 mM) and pH values (3, 5, 7, and 10) were examined. The results from the transport experiments were fitted and analyzed with the use of the ColloidFit software, while the results from the cotransport experiments were fitted with a modified version of a recently developed mathematical cotransport model. The results of this study suggested that the lowest mass recovery rate was for the cotransport experiments with the addition of NaCl. Furthermore, it was shown that TM has a weak affinity for sand but a relatively strong affinity for TiO2 at high ionic strength and acidic pH, probably accounting for the reduced mass recovery of TM in cotransport experiments.

In compliance with Article 43 of Regulation (EC) No 396/2005, EFSA received from the European Commission in 2020 a mandate to provide its reasoned opinion on the toxicological properties and maximum residue levels (MRLs) for the benzimidazole substances carbendazim and thiophanate‐methyl. Specifically, EFSA was asked to assess whether thiophanate‐methyl or carbendazim has clastogenic potential and, in case clastogenic potential can be excluded, to derive toxicological reference values necessary for consumer risk assessment and assessment of maximum residue levels (MRLs). Although these active substances are no longer authorised within the European Union, MRLs were established by the Codex Alimentarius Commission (codex maximum residue limits; CXLs), and import tolerances are in place. Based on the assessment of the available data, toxicological reference values and MRL proposals were derived and a consumer risk assessment was carried out. Some information required by the regulatory framework was found to be missing and a possible acute risk to consumers was identified. Hence, the consumer risk assessment was considered indicative only and all MRL proposals derived by EFSA still require further consideration by risk managers. In October 2022, to ensure that MRLs derived by EFSA in its assessment of 2021 are safe for consumers also in view of endocrine‐disrupting properties, EFSA was requested to carry out a follow‐up assessment taking into account the scientific criteria for identifying endocrine disruptors (ED). Based on the outcome of the assessment, the experts agreed that the reference values are also covering the concern related to the identified hazards indicative of endocrine disruption for thiophanate‐methyl. No further considerations on the impact of the ED assessment on the current reference values were needed for carbendazim since the ED criteria are not met for this substance. Therefore, the risk assessment and the MRL recommendations derived in 2021 are confirmed.

In this study, the fungicidal activities of the fungicides azoxystrobin, difenoconazole + propiconazole, carbendazim, flutriafol, fluopyram + tebuconazole, mancozeb and thiophanate-methyl against rice blast and dirty panicle pathogens were evaluated under laboratory and field conditions. Mancozeb exhibited the highest level of fungicidal activity against the blast pathogen Pyricularia oryzae , with an EC 50 value of 0.25 parts per million (ppm). The combination of two fungicides, fluopyram + tebuconazole, showed the strongest fungicidal effect against Bipolaris oryzae and Curvularia lunata , with EC 50 values of 0.587 ppm and 0.435 ppm , respectively. Meanwhile, carbendazim and flutriafol demonstrated the best level of fungicidal activity against Fusarium incarnatum , with the lowest EC 50 values of 0.211 ppm and 0.214 ppm , respectively. The results showed that the fungicides, triazole and strobilurin, had significant effects against rice blast and dirty panicle diseases. The combination of fluopyram + tebuconazole, when applied twice, was the most effective in reducing dirty panicle disease by up to 60% and increasing rice yield by 29% more than the untreated control. Fluopyram + tebuconazole, difenoconazole + propiconazole, flutriafol and azoxystrobin achieved stronger fungicidal activity against rice blast disease, reducing its severity by 32–33% when applied twice by foliar spraying. However, carbendazim, mancozeb and thiophanate-methyl had low to moderate fungicidal activity against both rice diseases in this study.

Botrytis cinerea is a high-risk pathogen for fungicide resistance development. Within the fungal populations, strains have developed multiple mutations in different target genes leading to multiple resistance (MLR) or mutations associated with overexpression of efflux transporters leading to multidrug resistance (MDR). These types of resistance are a major threat, and their successful management is a major challenge. The current study was initiated to a) determine frequencies of MLR/MDR strains in populations originating from several crops, b) identify the types of MDR that occur in Greece, and c) determine interactions between MLR and MDR at the level of sensitivity to botryticides. The frequencies of MLR/MDR phenotypes were determined in 515 isolates subjected to bioassays using discriminatory concentrations of thiophanate-methyl, iprodione, cyprodinil, fenhexamid, boscalid, fluopyram, fludioxonil, pyraclostrobin, and tolnaftate. Interestingly, 7.8% and 31.3% of isolates from strawberry and rootstock seedlings were resistant to every single fungicide class, while MDR phenotypes from strawberries, rootstocks, and tomatoes accounted for 26%, 87%, and 13.4%, respectively. The MLR and MDR isolates were further molecularly analyzed regarding genes erg27 , sdhB , Bcpos5 , and Mrr1 , responsible for resistance to fenhexamid, boscalid and fluopyram, cyprodinil, and MDR, respectively. The different mutations’ presence was determined along with a new mutation in Mrr1 leading to MDR. MDR isolates were characterized as MDR1 or MDR1h based on the presence of a 3-bp deletion in Mrr1 . MDR1h was predominant in isolates from rootstocks and MDR1 from tomatoes and strawberries, whereas the most frequent target-site mutations were F412S ( erg27 ), H272R ( sdhB ), and L412F ( Bcpos5 ). To determine whether the accumulation of target-site mutations along with MDR mutations exhibits an additive effect concerning fungicide resistance, the sensitivity of isolates possessing the predominant target-site mutations was calculated in both the presence and the absence of MDR-associated mutations. EC 50 in cyprodinil and boscalid increased to about twofold in the presence of MDR mutations, while there was no difference for fenhexamid. In conclusion, MLR/MDR frequencies are notably high in heavily treated crops in Greece, and the combination of MLR and MDR mutations leads to even higher fungicide resistance levels, highlighting the importance of resistance management.

Neofusicoccum parvum is an important opportunistic fungus causing Botryosphaeria dieback on grapevines. Because of its opportunistic nature, this pathogen spreads to many grape growing areas in a latent phase, and causes serious economic losses. The aims of the study were to examine hot-water treatments combined with fungicides in order to cure latent infections of artificially inoculated N. parvum in dormant grapevine canes and to assess the effects of these treatments on endophytic fungi. Artificially N. parvum-inoculated canes were dipped into cyprodinil + fludioxonil, tebuconazole or thiophanate-methyl suspensions under the following temperature-duration combinations; 30°C for 12 h, 35°C for 6 h, 40°C for 2 h or 50°C for 30 min (temperature at 50°C was not combined with fungicides). Treated canes were cooled in tap water (18°C) for 1 h, and pathogen re-isolations were immediately attempted from inner wood tissues. Extent to which these applications affected the presence of endophytic fungi were also determined by calculating pre- and post-treatment isolation rates. Hot-water treatments (without fungicides) below 52°C did not reduce N. parvum re-isolation rates, and were ineffective. However, these treatments combined with fungicides decreased pathogen incidence at 50°C and below. Maximum reduction (34%) was obtained with heated tebuconazole suspensions at 40°C for 2 h and 50°C for 30 min, and eradicative ability was superior to that of cyprodinil + fludioxonil or thiophanate-methyl. The hot-water treatments reduced incidence of endophytic fungi but greater reduction was observed with the hot-water and fungicide combinations. Fungicide penetration into wood tissues of propagation material could be enhanced by increasing water temperatures in hydration or hot-water treatment tanks, and this approach could be useful method for production of healthy grapevine plants in nurseries.

A dual-emission fluorescent (FL) probe was constructed by coordinating Cu 2+ of copper metal–organic frameworks (Cu-MOFs) with − COO − group of carbon dots (CDs) for pesticide thiophanate-methyl (TM) determination. TM was recognized by organic ligands (H 2 BDC and H 2 BDC-NH 2 ) of Cu-MOFs via π stacking. Due to the higher affinity of Cu 2+ to TM than ligands and CDs, TM chelated with Cu 2+ to form TM-Cu complex. Thus coordination of Cu-MOFs was damaged and the ligands were released resulting in the FL intensity increase of Cu-MOFs (F 430 ). And also CDs were released from CDs@Cu-MOFs hybrids and electron transfer from CDs to CuMOFs was inhibited, leading to the FL intensity increase of CDs (F 600 ). The FL intensity ratio (F 430 /F 600 ) showed a good linear relationship with TM concentrations of 0.0307–0.769 μmol L −1 with a limit of detection (LOD) of ~ 3.67 nmol L −1 . The probe was successfully applied to detect TM in spiked food samples with satisfactory recoveries of 93.1–113%. Additionally, visual detection of TM was achieved according to the fluorescence color variation from blue to carmine, indicating promising application of CDs@Cu-MOFs probe. Graphical abstract

In compliance with Article 43 of Regulation (EC) No 396/2005, EFSA received from the European Commission a mandate to provide its reasoned opinion on the toxicological properties and maximum residue levels (MRLs) for the benzimidazole substances carbendazim and thiophanate‐methyl. Specifically, EFSA was asked to assess whether thiophanate‐methyl or carbendazim have clastogenic potential and, in case clastogenic potential can be excluded, to derive toxicological reference values necessary for consumer risk assessment and assessment of maximum residue levels (MRLs). Although these active substances are no longer authorised within the European Union, MRLs were established by the Codex Alimentarius Commission (codex maximum residue limits; CXLs), and import tolerances are in place. Based on the assessment of the available data, toxicological reference values and MRL proposals were derived and a consumer risk assessment was carried out. Some information required by the regulatory framework was found to be missing and a possible acute risk to consumers was identified. Hence, the consumer risk assessment is considered indicative only, all MRL proposals derived by EFSA still require further consideration by risk managers and measures for reduction of the consumer exposure should also be considered.

Fusarium wilt, the most serious soil-borne pathogen, is a serious problem for tomato production worldwide. The presented study evaluated the antifungal activity against Fusarium oxysporum f. sp. lycopersici in vitro and in vivo for nine fumigants. In addition, the research examined the possibility of enhancing the growth of tomato plants in order to increase resistance against this disease by using four chemical inducers. The results indicated that at 20 mg/L, the radial growth of the pathogen was inhibited 100% by formaldehyde and > 80% by phosphine. Among the essential oils investigated, neem oil was the most effective, however, it only achieved 40.54% at 500 mg/L. The values of EC 50 for all fumigants, except dimethyl disulfide (DMDS) and carbon disulfide (CS2), were lower than those for thiophanate-methyl. Phosphine was the highest efficient. The elicitors can be arranged based on their effectiveness, gibberellic acid (GA3) > sorbic acid > cytokinin (6-benzylaminopurine) > indole-3-butyric acid. The change in root length, fresh weight, and dry weight was greater with soil drench than with foliar application. The fumigant generators formaldehyde, phosphine and 1,4-dichlorobenzene and bio-fumigants citrus and neem oils as well as elicitors gibberellic and sorbic acid could be one of the promising alternatives to methyl bromide against Fusarium oxysporum as an important component of integrated management of Fusarium wilt.

Little is known about effective control strategies targeting the invasive ambrosia beetle Xylosandrus compactus . This fungus-farming beetle is highly dependent on its primary nutritional fungal mutualist Ambrosiella xylebori . Traditionally, insect pest control programs target the pest directly. Here, we tested the potential of synthetic and microbial based fungicides to suppress the fungal mutualist, consequently hampering the beetle development. Thiophanate-methyl application to bay laurel ( Laurus nobilis L.) stem sections proved to be effective in reducing the mutualist fungus occurrence in infested galleries, as well as to reduce the mean X. compactus brood size. Thiophanate-methyl and azoxystrobin significantly reduced the mean beetle brood size in extended laboratory conditions. Similarly, these two fungicides were the most effective in reducing the fungal lesion length, both when tested by soil or spray applications. Overall, thiophanate-methyl showed the highest reduction of the X. compactus brood size by spray application. No or low impact on X. compactus infestations was observed when testing the triazole mefentrifuconazole. Among tested microbial based fungicides, Trichoderma asperellum T34 was the only one causing a reduction of the fungal lesion length. To the best of our knowledge, this study provides, for the first time, baseline data on the potential of fungicides for disrupting the mutualistic interaction between X. compactus and its primary mutualist A. xylebori . These findings will help in developing novel and effective integrated pest management approaches based on the mycobiome alteration and targeting X. compactus in its invaded range.

A novel Ru-Fe 3 O 4 nanozyme with enhanced peroxidase-like (POD-like) activity was synthesized through a hydrothermal method. Ru-Fe 3 O 4 nanozyme was effectively utilized for the detection of thiophanate-methyl (TM) using a colorimetric technique. The POD-like activity of Ru-Fe 3 O 4 was found to be superior compared to Fe 3 O 4 , Rh-Fe 3 O 4 , and Pd-Fe 3 O 4 . Ru-Fe 3 O 4 provided excellent POD-like activity with Michaelis constants of 0.00645 mM and 0.66714 mM for substrates of 3,3’,5,5’-tetramethylbenzidine and H 2 O 2 , respectively. The density functional theory calculation showed that Ru-Fe 3 O 4 had better H 2 O 2 decomposition reactivity compared to Fe 3 O 4 . Compared with Fe 3 O 4 , the adsorbed H 2 O 2 molecules underwent decomposition more readily on the Ru-Fe 3 O 4 catalytic surface facilitating the occurrence of the H 2 O 2 catalytic reaction, further suggesting the excellent POD-like activity of Ru-Fe 3 O 4 . The coordination and electrostatic interactions of Ru-Fe 3 O 4 and TM promoted their binding, contributing to TM covering Ru-Fe 3 O 4 catalytic site and inhibiting the POD-like activity of Ru-Fe 3 O 4 . As a result, the sensitive and selective detection of TM using Ru-Fe 3 O 4 by a colorimetric method was achieved. The Ru-Fe 3 O 4 nanozyme displayed a good linear correlation, with a linear detection range and a detection limit of 0.1–100 and 0.03 μg/mL, respectively. The Ru-Fe 3 O 4 nanozyme was used for the determination of TM in soil and water samples with success. Graphical Abstract