Widely used conazole fungicides (CFs) belong to the most frequently detected pesticides in Central European arable soils. However, data on their environmental behaviour and bioavailability to soil organisms are surprisingly scarce. In the present laboratory microcosm study prochloraz, tebuconazole, epoxiconazole and flusilazole were applied to 12 different agricultural soils at background levels. Bioaccumulation to earthworm E. andrei and lettuce L. sativa roots and leaves was evaluated in non-aged (biota exposure after addition of pesticides) and aged (exposure started three months later) systems. In contrast with expectations from ageing effect (decrease of bioavailability), bioaccumulation in E. andrei was both reduced and enhanced after ageing depending on soil properties. The reduction of bioaccumulation correlated positively to the percentage of clay but negatively to soil organic matter. The affinity of compost worm E. andrei towards organic matter where hydrophobic pesticide molecules are sorbed is discussed as a possible explanation. An apparent effect of ageing (reduction of bioavailability) was particularly observed in lettuce roots, where bioaccumulation was significantly reduced in time. However, bioaccumulation in leaves changed ambiguously in aged variants among CFs, possibly as a combined result of bioconcentration, dilution by plant growth and metabolism. This study brings first insights into how the bioaccumulation of conazole fungicides is affected by sequestration in agricultural soils. The results indicate that in complex systems, the ageing is not necessarily connected with decrease of bioaccumulation.
- MeSH
- bioakumulace MeSH
- biologická dostupnost MeSH
- epoxidové sloučeniny MeSH
- fungicidy průmyslové analýza metabolismus MeSH
- jíl MeSH
- látky znečišťující půdu analýza metabolismus MeSH
- Oligochaeta metabolismus MeSH
- pesticidy analýza MeSH
- půda chemie MeSH
- salát (hlávkový) metabolismus MeSH
- silany MeSH
- triazoly MeSH
- zemědělství MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
Conazole fungicides are currently used pesticides with considerable chronic toxicity and ecotoxicity that are also on EU list for substitution. They enter the soil forming short- or long-term residues. In this study two of their representatives, epoxiconazole (EPC) and tebuconazole (TBC), have been tested with 20 soils from the Czech Republic for their adsorption. Adsorption, by means of Kd coefficients, was compared to "basic" (TOC, pH, clay …) and "advanced" (surface area, minerals ..) soil properties. After doing multivariate analysis of the variables it was apparent that adsorption of both pesticides was highly associated with pH (negatively correlated), and less associated with soil organo-mineral complex (TOC, clay and surface area) and C and N in soil organic matter (OM). Particle sizes or cation exchange capacity (CEC) did not show correlation with adsorption, but showed an association in multidimensional space in factor analysis (FA). Some correlations were revealed between EPC adsorption and soil organic matter parameters. Recalculating Kd to Koc and to Gibb's free energy (ΔG) and its values indicated that the adsorption of EPC and TBC is mainly weak physical adsorption - partitioning. Also, ΔG values gave better correlation with pH(H2O) than Kd. Surface area impacted EPC adsorption. From the several soil minerals, kaolinite showed EPC and TBC adsorption. EPC adsorption was not highly influenced with pH changes compared to TBC. The number and types of H-bonds with molecular geometry govern the sorption, which might crucially affect leachibility in soil, and this may indicate that TBC is more leachable than EPC for the same soil.
- MeSH
- adsorpce MeSH
- epoxidové sloučeniny chemie MeSH
- jíl MeSH
- kationty MeSH
- látky znečišťující půdu chemie MeSH
- minerály chemie MeSH
- pesticidy chemie MeSH
- půda chemie MeSH
- triazoly chemie MeSH
- velikost částic MeSH
- zemědělství MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Česká republika MeSH
This study presents monitoring data on the spatial and temporal occurrence of pesticide residues in arable soils of the Czech Republic and relates it to soil properties, pesticide usage and data on application provided by farmers. In total, 34 soils were sampled during 2014-2017, amounting to 136 samples which were analyzed for 60 pesticides and four transformation products. Conazole fungicides were frequently present in soils above the limit of quantification and/or above the 0.01 mg/kg threshold. Of the other pesticide types, the herbicides diflufenican, chlorotoluron, metolachlor, pendimethalin and terbuthylazine, fungicides azoxystrobin, carbendazim, fenpropidin, fenpropimorph and prochloraz and the insecticide methoxyfenozide were found in ≥20% of soils in at least one sampling campaign. Soils typically (>50%) contained 2-7 residues with a maximum of 14. For the 136 samples, 116 different mixtures were identified. The occurrence of pesticides was driven by their annual usage, their half-lives in soil, and their hydrophobicity. A comparison of the monitoring data and pesticide application data provided by farmers revealed that 63% of the applied pesticides are not likely to persist until the following growing season while up to 69% of pesticide residues found in soils could be inherited from the previous growing season(s).
- MeSH
- aniliny MeSH
- fungicidy průmyslové analýza MeSH
- herbicidy analýza MeSH
- insekticidy analýza MeSH
- látky znečišťující půdu analýza MeSH
- monitorování životního prostředí * MeSH
- pesticidy analýza MeSH
- půda chemie MeSH
- rezidua pesticidů analýza MeSH
- triaziny MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Česká republika MeSH
Currently used pesticides (CUPs) represent one of the largest intentional inputs of potentially hazardous compounds into agricultural soils. Subsequently, pesticide residues (PRs) and their transformation products (TPs) persist in agricultural soils, occurring in diverse mixtures of compounds in various concentrations. In this study, measured environmental concentrations (MECs) of CUP residues and TPs, originated from previous growing seasons in agricultural soils of the Czech Republic, were used to characterize the environmental risk for agroecosystems. Toxicity exposure ratios (TERs) were calculated using predicted no-effect concentrations (PNECs) and MECs in order to identify single pesticide residues risk to in-soil invertebrates and microorganisms. Ecological risk assessment (ERA) for the mixtures of pesticide residues at each monitored site was assessed using a risk quotient (RQ) method and considering concentration addition among components in the mixtures. The compilation of ecotoxicity data to derived PNECs for in-soil organisms clearly showed data gaps mainly for triazine and chloroacetanilide TPs. In addition, chronic toxicity data for in-soil invertebrates at different trophic levels are not available for 30% of monitored CUPs. The ERA revealed that pesticide residues in soil pose a risk at 35% of the sites (RQ ≥ 1). Among measured pesticides, epoxiconazole, atrazine-2-hydroxy, carbendazim, dimoxystrobin, terbuthylazine and difenoconazole were the main contributors to the overall pesticide mixture toxicity. The measured levels of epoxiconazole together with the frequent presence in soils represent a risk for the agroecosystems. Further assessment of higher tiers of ERA should be considered and prioritized in the pesticides risk management.
- MeSH
- hodnocení rizik MeSH
- pesticidy analýza chemie MeSH
- půda chemie MeSH
- rezidua pesticidů analýza chemie MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Česká republika MeSH
The objective of this study is to characterize changes in the fate, behaviour and bioavailability of four conazole fungicides - CFs (prochloraz - PRO, tebuconazole - TEB, epoxiconazole - EPO, flusilazole - FLU) in 12 diverse agricultural soils in complex microcosm systems consisting of agriculturally-used fluvisols, plants (Lactuca sativa), earthworms (Eisenia fetida) and passive samplers (SPME, Empore™ discs, silicone rubber). Due to great variability of the data and other methodological problems, the in-matrix passive samplers failed to be indicators of pore-water concentration and (bio)availability/(bio)accessibility of CFs. A dissipation of all CFs followed the first order kinetics (usually after initial lag phase) with large span of resulting half-lives (7-670 d) depending on soils and compounds. In many soils, the model revealed the ending plateau, which indicates the non-degradable or slowly-degradable residues. The half-lives and the residues were generally higher for EPO and FLU, than for PRO and TEB. Greater but slower total dissipation of CFs was observed in soils with higher percentage of organic matter. Earthworm concentrations were highest at first sampling time (14 days) and considerably decreased afterwards often resulting in PRO concentration below LOQ. Earthworm uptake was influenced by amount of organic matter and soil texture. Accumulation to lettuce roots was generally higher than to leaves and differed greatly among CFs. Concentration shoot to root ratios were generally the lowest for FLU (0.04) and highest for TEB (0.37). PRO was not detected in lettuce leaves during experiment. The study brings new results on fate and bioavailability of CFs in soils.
The contact assay measuring the inhibition of Arthrobacter globiformis dehydrogenase activity as an endpoint to evaluate the toxicity of solid samples was tested in an international ring-test to validate its performance for ISO standardization (ISO/CD 18187). This work reports the results of the ring-test involving 9 laboratories from six countries. At least 8 valid data sets were obtained for each sample and more than three quarters of the participants attained the validity criteria defined in the standard. The coefficient of variation within (CVr) and between (CVR) laboratories was generally on average <15% and <30% for negative and positive controls, respectively. Regarding solid samples, the laboratories provided a similar ranking of the samples based on their toxicity, despite some variation in the LOEC values. The logarithmic within-lab standard deviation <0.50 for soils and <0.25 for wastes evidenced a good repeatability. The between-lab variability assessed by a CVR <30%, minimum-maximum factor <4 and a reproducibility standard deviation (SDR) <0.13 for a great part of the solid samples, confirmed the test reproducibility. Overall, this assay proved to be robust, sensitive and feasible for routine use towards the quality assessment of soils and wastes.
- MeSH
- Arthrobacter enzymologie MeSH
- biotest * MeSH
- dřevo analýza MeSH
- geologické sedimenty analýza MeSH
- hornictví MeSH
- hydrolasy metabolismus MeSH
- laboratoře MeSH
- látky znečišťující půdu analýza MeSH
- monitorování životního prostředí MeSH
- popel uhelný analýza MeSH
- průmyslový odpad analýza MeSH
- reprodukovatelnost výsledků MeSH
- sklo analýza MeSH
- těžké kovy analýza MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
