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Triazoles and aromatase: The impact of copper cocktails
2020
Jaklová Dytrtová, Jana | Bělonožníková, Kateřina | Jakl, Michal | Ryšlavá, Helena
Triazoles are used as antifungal agents, they mostly inhibit two enzymes: 14α-demethylase and aromatase. These enzymes are utilised also in other species and therefore the affection in non-target species in the environment is expected as well. Besides, triazoles are often being applied in a mixture and they can also interact with other substances present. This study clarifies how three selected representative triazoles (tebuconazole, penconazole and cyproconazole) interact with each other (group effect) and in mixtures (cocktail effect) with copper, essential/toxic for all organisms. Within the experiments on electrospray and collision-induced dissociations (both ESI-MS), it has been found that the fragments correspond to typical triazole metabolites. For their formation, the presence of copper ions is crucial. The inhibitory effect of Cu cocktails on aromatase enzymatic activity has been studied. The presence of Cu ions together with triazole(s) significantly increases the inhibitory effect on aromatase activity. The highest inhibitory effect (more than 60%) on aromatase activity is produced by cocktails containing penconazole and Cu ions, namely by penconazole/Cu and penconazole/tebuconazole/Cu. The reactivity of triazoles in groups is not significantly affected by the interactions among them. Additionally, the role of triazoles in copper Fenton reaction regulation has been observed and described. These changes may be attributed to the formation and stabilization of the complexes with the central Cu ion, with usually one, two or three triazolic ligands, depending on the mixture. The study demonstrates that the interaction of triazoles and Cu ions is a complex process; their impact on metabolism seems to be rather extensive and must be evaluated in the context of biochemical reactions.
显示更多 [+] 显示较少 [-]Enantioselective toxic effects of cyproconazole enantiomers against Rana nigromaculata
2018
Zhang, Wenjun | Cheng, Cheng | Chen, Li | Deng, Yue | Zhang, Luyao | Li, Yao | Qin, Yinan | Diao, Jinling | Zhou, Zhiqiang
The environmental contaminant, especially pesticides, threatened the amphibian population. In this assay, the enantioselective behavior of cyproconazole on Rana nigromaculata was studied. We found LC50 (lethal concentration causing 50% mortality) of 4-enantiomers was nearly twice as 3-enantiomers in 96 h acute toxicity test. Besides, the significant considerable variation of oxidative stress and LDH (lactic dehydrogenase) induced by the four enantiomers indicated that cyproconazole could enantioselectively affect enzymes in tadpoles. Bioaccumulation experiments showed the order of cyproconazole in the tadpoles was 4-enantiomers>3- enantiomers>2- enantiomers>1- enantiomers during the exposure for 28d. In tissue distribution test, cyproconazole was formed and accumulated in order of 4-enantiomers>2-enantiomers>3- enantiomers>1- enantiomers, except that in the gut. During the elimination experiment, cyproconazole was rapidly eliminated by 95% within the only 24 h. These results suggested that the influence of enantioselective behavior should consider when assessing ecological risk of chiral pesticides to amphibians.
显示更多 [+] 显示较少 [-]Occurrence and overlooked sources of the biocide carbendazim in wastewater and surface water
2018
Merel, Sylvain | Benzing, Saskia | Gleiser, Carolin | Di Napoli-Davis, Gina | Zwiener, Christian
Carbendazim is a fungicide commonly used as active substance in plant protection products and biocidal products, for instance to protect facades of buildings against fungi. However, the subsequent occurrence of this fungicide and potential endocrine disruptor in the aqueous environment is a major concern. In this study, high resolution mass spectrometry shows that carbendazim can be detected with an increasing abundance from the source to the mouth of the River Rhine. Unexpectedly, the abundance of carbendazim correlates poorly with that of other fungicides used as active ingredients in plant protection products (r² of 0.32 for cyproconazole and r² of 0.57 for propiconazole) but it correlates linearly with that of pharmaceuticals (r² of 0.86 for carbamazepine and r² of 0.89 for lamotrigine). These results suggest that the occurrence of carbendazim in surface water comes mainly from the discharge of treated domestic wastewater. This hypothesis is further confirmed by the detection of carbendazim in wastewater effluents (n = 22). In fact, bench-scale leaching tests of textiles and papers revealed that these materials commonly found in households could be a source of carbendazim in domestic wastewater. Moreover, additional river samples collected nearby two paper industries indicate that the discharge of their treated process effluents is also a source of carbendazim in the environment. While characterizing paper and textile as overlooked sources of carbendazim, this study also shows the biocide as a possible ubiquitous wastewater contaminant that would require further systematic and worldwide monitoring due to its toxicological properties.
显示更多 [+] 显示较少 [-]Quality of the surface water of a basin affected by the expansion of the agricultural frontier over the native forest in the Argentine Espinal region
2022
Van Opstal, Natalia Verónica | Seehaus, Mariela Soledad | Gabioud, Emmanuel Adrian | Wilson, Marcelo German | Galizzi, Flavio José | Pighini, Ramiro Joaquin | Repetti, Maria Rosa | Regaldo, Luciana María | Gagneten, Ana María | Sasal, María Carolina
Land use changes have led to the degradation of multiple ecosystem services and affected the quality of aquatic ecosystems. The aims of this study were (i) to assess the expansion of the agricultural border over the native forest of an Argentinean stream basin and (ii) to characterize the surface water quality, considering physicochemical parameters, and pesticide concentrations. The agricultural frontier expansion was estimated through the analysis of satellite image coverage. Samples of surface water were taken bimonthly for 2 years. The native forest cover decreased from 72% in 1987 to 60% in 2017 due to the sustained increase in agricultural activities. In surface water, the concentrations of cations decreased: Na > Ca > K > Mg, whereas those of anions decreased: HCO₃ > > Cl > SO₄ > PO₄. The 84 surface water samples analyzed revealed 25 pesticides, including herbicides (44%), insecticides (28%), and fungicides (28%). Herbicides were detected in more than 60% of the samples. 2,4-D, atrazine, cyproconazole, diazinon, glyphosate, AMPA, and metolachlor were detected in all the study sites and sometimes, 2,4-D, atrazine, dicamba, and metolachlor concentrations exceeded the guideline levels. The high sampling frequency of this study and the two annual cycles of crops in the basin enabled sensing of pesticide molecules and concentrations that had not been previously detected, indicating diffuse contamination. These findings signal an emergent challenge on the Espinal agro-ecosystem integrity due to changes in land use.
显示更多 [+] 显示较少 [-]Estimation of residue levels and dietary risk assessment of cyproconazole and azoxystrobin in cucumber after field application in China
2022
Cheng, Chuanying | Liang, Yiran | Hu, Jiye
Residue field trials in cucumber were conducted for the safe use of a commercial formulation of cyproconazole·azoxystrobin 28% suspension concentrate (SC 294 g a.i. ha⁻¹, three applications at a 7-day interval) in the year 2018, in China. To determine the residues of cyproconazole and azoxystrobin in cucumber, a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was developed using high-performance liquid chromatography coupled with tandem mass spectrometry. This validated method was applied to analyze cucumber samples collected from 12 specified regions. At the 3-day interval to harvest, the highest residue (HR) of azoxystrobin was 0.150 mg kg⁻¹, which was lower than the maximum residue limit (MRL; 0.5 mg kg⁻¹) permitted in China, and the HR of cyproconazole was 0.084 mg kg⁻¹, for which no MRL value has been set in China. The chronic risk quotient values of cyproconazole and azoxystrobin for Chinese adults at a 3-day interval to harvest were 2.56% and 13.72%, respectively. The acute risk quotient values of cyproconazole in cucumber were specified as 5.52% for children (1–6 years old) and 2.83% for the adults (> 18 years old) in China. These results indicate that cyproconazole·azoxystrobin 28% SC sprayed on cucumber at the pre-harvest interval of 3 days has no significant potential risk for Chinese consumers.
显示更多 [+] 显示较少 [-]Assessment of Pesticide Residues in Soils Using a QuEChERS Extraction Procedure and LC-MS/MS
2021
Mahdavi, Vahideh | Heris, Mir-Ebrahim Solhi | Dastranj, Mehdi | Farimani, Mahdi Moridi | Eslami, Zahra | Aboul-Enein, Hassan Y.
The concentration levels of some important pesticides were evaluated in soil samples from different areas of the North of Iran (Golestan province) and to indicate the possible sources and risks of contamination. A multiresidue analytical procedure using the QuEChERS approach was developed to extract and measure 12 pesticide residues from ten different classes in 145 soil samples including agricultural, garden, forestal, and residential areas. The analysis was performed using reversed-phase liquid chromatography equipped with an ESI mass spectrometry instrument by multiple reaction monitoring (MRM) in positive-ion modes. Retention times and occurrence of two conventional transitions were used as identification criteria. Three pesticide residues including malathion, propargite, and butachlor were observed in soil samples. Malathion residue was found in ˃ 51% of soil samples, and its levels in approximately 35% of the cases were more than the residue limit (50 μg kg⁻¹). Propargite residue was observed in 49% of the samples and its levels in 11% of the cases were more than the residue limit. The most frequently observed levels of malathion and propargite were found in forestal and residential areas. The amount of butachlor residue in one of the residential soil samples was at least 10 times more than the residue limit. Some of the pesticides including imidacloprid, cyproconazole, diazinon, and chlorpyrifos displayed residue levels below 50 μg kg⁻¹. The other pesticides, namely carbaryl, thiophanate-methyl, fenpropathrin, krezoxim-methyl, and pinoxaden, were not detected in any soil samples. These findings might be useful for implementing programs to monitor the presence of pesticides in soils and the related crops, to carry out more precise risk assessment studies.
显示更多 [+] 显示较少 [-]Developmental toxicity of the triazole fungicide cyproconazole in embryo-larval stages of zebrafish (Danio rerio)
2019
Cao, Fangjie | Souders, Christopher L. II | Li, Pengfei | Pang, Sen | Qiu, Lihong | Martyniuk, Christopher J.
Cyproconazole is a triazole fungicide used to protect a diverse range of fruits, vegetables, and grain crops. As such, it has the potential to enter aquatic environments and affect non-target organisms. The objective of this study was to assess the acute toxicity of the triazole fungicide cyproconazole to zebrafish embryos by assessing mortality, developmental defects, morphological abnormality, oxidative respiration, and locomotor activity following a 96-h exposure. Zebrafish embryos at 6-h post-fertilization (hpf) were exposed to either a solvent control (0.1% DMSO, v/v), or one dose of 10, 25, 50, 100, 250, and 500 μM cyproconazole for 96 h. Data indicated that cyproconazole exhibited low toxicity to zebrafish embryos, with a 96-h LC₅₀ value of 90.6 μM (~ 26.4 mg/L). Zebrafish embryos/larvae displayed a significant decrease in spontaneous movement, hatching rate, and heartbeats/20 s with 50, 100, and 250 μM cyproconazole exposure. Malformations (i.e., pericardial edema, yolk sac edema, tail deformation, and spine deformation) were also detected in zebrafish exposed to ≥ 50 μM cyproconazole, with significant increases in cumulative deformity rate at 48, 72, and 96 hpf. In addition, a 20–30% decrease in basal and oligomycin-induced ATP respiration was observed after 24-h exposure to 500 μM cyproconazole in embryos. To determine if cyproconazole affected locomotor activity, a dark photokinesis assay was conducted in larvae following 7-day exposure to 1, 10, and 25 μM cyproconazole in two independent trials. Activity in the dark period was decreased for zebrafish exposed to 25 μM cyproconazole in the first trial, and hypoactivity was also observed in zebrafish exposed to 1 μM cyproconazole in a second trial, suggesting that cyproconazole can affect locomotor activity. These data improve understanding of the toxicity of cyproconazole in developing zebrafish and contribute to environmental risk assessments for the triazole fungicides on aquatic organisms. We report that, based on the overall endpoints assessed, cyproconazole exhibits low risk for developing fish embryos, as many effects were observed above environmentally-relevant levels.
显示更多 [+] 显示较少 [-]Residues of plant protection products in grey partridge eggs in French cereal ecosystems
2016
Bro, Elisabeth | Devillers, James | Millot, Florian | Decors, Anouk
The contamination of the eggs of farmland birds by currently used plant protection products (PPPs) is poorly documented despite a potential to adversely impact their breeding performance. In this context, 139 eggs of 52 grey partridge Perdix perdix clutches, collected on 12 intensively cultivated farmlands in France in 2010–2011, were analysed. Given the great diversity of PPPs applied on agricultural fields, we used exploratory GC/MS-MS and LC/MS-MS screenings measuring ca. 500 compounds. The limit of quantification was 0.01 mg/kg, a statutory reference. A total of 15 different compounds were detected in 24 clutches. Nine of them have been used by farmers to protect crops against fungi (difenoconazole, tebuconazole, cyproconazole, fenpropidin and prochloraz), insects (lambda-cyhalothrin and thiamethoxam/clothianidin) and weeds (bromoxynil and diflufenican). Some old PPPs were also detected (fipronil(+sulfone), HCH(α,β,δ isomers), diphenylamine, heptachlor(+epoxyde), DDT(Σisomers)), as well as PCBs(153, 180). Concentrations ranged between <0.01 and 0.05 mg/kg but reached 0.067 (thiamethoxam/clothianidin), 0.11 (heptachlor + epoxyde) and 0.34 (fenpropidin) mg/kg in some cases. These results testify an actual exposure of females and/or their eggs to PPPs in operational conditions, as well as to organochlorine pollutants or their residues, banned in France since several years if not several decades, that persistently contaminate the environment.Routes of exposure, probability to detect a contamination in the eggs, and effects on egg/embryo characteristics are discussed with regard to the scientific literature.
显示更多 [+] 显示较少 [-]Lethal and sub-lethal effects of cyproconazole on freshwater organisms: a case study with Chironomus riparius and Dugesia tigrina
2018
Saraiva, AlthiérisS. | Sarmento, RenatoA. | Golovko, Oksana | Randak, Tomas | Pestana, JoãoL. T. | Soares, AmadeuM. V. M.
The fungicide cyproconazole (CPZ) inhibits the biosynthesis of ergosterol, an essential sterol component in fungal cell membrane and can also affect non-target organisms by its inhibitory effects on P450 monooxygenases. The predicted environmental concentration of CPZ is up to 49.05 μg/L and 145.89 μg/kg in surface waters and sediments, respectively, and information about CPZ toxicity towards non-target aquatic organisms is still limited. This study aimed to address the lack of ecotoxicological data for CPZ, and thus, an evaluation of the lethal and sub-lethal effects of CPZ was performed using two freshwater invertebrates (the midge Chironomus riparius and the planarian Dugesia tigrina). The estimated CPZ 48 h LC₅₀ (95% CI) was 17.46 mg/L for C. riparius and 47.38 mg/L for D. tigrina. The emergence time (EmT₅₀) of C. riparius was delayed by CPZ exposure from 0.76 mg/L. On the other hand, planarians showed higher tolerance to CPZ exposure. Sub-lethal effects of CPZ on planarians included reductions in locomotion (1.8 mg/L), delayed photoreceptors regeneration (from 0.45 mg/L), and feeding inhibition (5.6 mg/L). Our results confirm the moderate toxicity of CPZ towards aquatic invertebrates but sub-lethal effects observed also suggest potential chronic effects of CPZ with consequences for population dynamics.
显示更多 [+] 显示较少 [-]Is pesticide sorption by constructed wetland sediments governed by water level and water dynamics?
2018
Gaullier, Céline | Dousset, Sylvie | Billet, David | Baran, Nicole
Constructed wetlands (CWs) are used to reduce the pesticide inputs from tile drainage or run-off to surface water. Their effectiveness appears variable and remains to be better characterized and understood. The aim of this study was to assess the influences of two hydraulic parameters (i.e., dynamics and water level) on the sorption process occurring in CWs. Then, two solid/liquid ratios were studied (1/1 and 1/5) to mimic the water level variation in the field, and two agitation speeds were used (none and gentle agitation) to simulate different water dynamics (stagnation and flow pass, respectively). Sorption kinetics and isotherms were obtained for four pesticides with contrasting properties. The pesticide adsorption coefficients were classified as follows: boscalid (BSC) > cyproconazole (CYP) > isoproturon (IPU) ∼ dimethachlor (DMT) at any ratio or agitation, in agreement with their water solubilities and K ₒw values. The effect of the solid/liquid ratio was evidenced for all conditions. Indeed, the adsorption equilibrium time was reached more quickly for the 1/1 ratio (24–72 h) than for the 1/5 ratio (96–120 h). In addition, the adsorption coefficients (K f ᵃᵈˢ) were larger for the 1/1 ratio (1.8–11.2 L kg⁻¹) than for the 1/5 ratio (1.0–5.9 L kg⁻¹). The agitation effect was more evidenced for the 1/5 ratio and for the more hydrophobic molecules, such as BSC and CYP, for which adsorption equilibrium time was never reached with agitation (>120 h), while it was reached at 96 h without agitation. Moreover, the K f ᵃᵈˢ values were larger with agitation than without agitation for BSC and CYP, whereas they were similar for the two agitations for IPU and DMT. Our results demonstrated that the hydrodynamic function of CWs could influence pesticide sorption with variable effects according to the molecular properties and consequently influence the mitigation effect of CWs throughout the year.
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