Development of a Bayesian network for probabilistic risk assessment of pesticides.

Conventional environmental risk assessment of chemicals is based on a calculated risk quotient, representing the ratio of exposure to effects of the chemical, in combination with assessment factors to account for uncertainty. Probabilistic risk assessment approaches can offer more transparency by using probability distributions for exposure and/or effects to account for variability and uncertainty. In this study, a probabilistic approach using Bayesian network modeling is explored as an alternative to traditional risk calculation. Bayesian networks can serve as meta-models that link information from several sources and offer a transparent way of incorporating the required characterization of uncertainty for environmental risk assessment. To this end, a Bayesian network has been developed and parameterized for the pesticides azoxystrobin, metribuzin, and imidacloprid. We illustrate the development from deterministic (traditional) risk calculation, via intermediate versions, to fully probabilistic risk characterization using azoxystrobin as an example. We also demonstrate the seasonal risk calculation for the three pesticides. Integr Environ Assess Manag 2022;18:1072-1087. © 2021 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Degradation of difenoconazole in water and soil: Kinetics, degradation pathways, transformation products identification and ecotoxicity assessment.

Difenoconazole is a widely used triazole fungicide that has been frequently detected in the environment, but comprehensive study about its environmental fate and toxicity of potential transformation products (TPs) is still lacking. Here, laboratory experiments were conducted to investigate the degradation kinetics, pathways, and toxicity of transformation products of difenoconazole. 12, 4 and 4 TPs generated by photolysis, hydrolysis and soil degradation were identified via UHPLC-QTOF/MS and the UNIFI software. Four intermediates TP295, TP295A, TP354A and TP387A reported for the first time were confirmed by purchase or synthesis of their standards, and they were further quantified using UHPLC-MS/MS in all tested samples. The main transformation reactions observed for difenoconazole were oxidation, dechlorination and hydroxylation in the environment. ECOSAR prediction and laboratory tests showed that the acute toxicities of four novel TPs on Brachydanio rerio, Daphnia magna and Selenastrum capricornutum are substantially lower than that of difenoconazole, while all the TPs except for TP277C were predicted chronically very toxic to fish, which may pose a potential threat to aquatic ecosystems. The results are important for elucidating the environmental fate of difenoconazole and assessing the environmental risks, and further provide guidance for scientific and reasonable use.

The effect of freezing and thawing on water flow and MCPA leaching in partially frozen soil.

Limited knowledge and experimental data exist on pesticide leaching through partially frozen soil. The objective of this study was to better understand the complex processes of freezing and thawing and the effects these processes have on water flow and pesticide transport through soil. To achieve this we conducted a soil column irrigation experiment to quantify the transport of a non-reactive tracer and the herbicide MCPA in partially frozen soil. In total 40 intact topsoil and subsoil columns from two agricultural fields with contrasting soil types (silt and loam) in South-East Norway were used in this experiment. MCPA and bromide were applied on top of all columns. Half the columns were then frozen at -3 °C while the other half of the columns were stored at +4 °C. Columns were then subjected to repeated irrigation events at a rate of 5 mm artificial rainwater for 5 h at each event. Each irrigation was followed by 14-day periods of freezing or refrigeration. Percolate was collected and analysed for MCPA and bromide. The results show that nearly 100% more MCPA leached from frozen than unfrozen topsoil columns of Hov silt and Kroer loam soils. Leaching patterns of bromide and MCPA were very similar in frozen columns with high concentrations and clear peaks early in the irrigation process, and with lower concentrations leaching at later stages. Hardly any MCPA leached from unfrozen topsoil columns (0.4-0.5% of applied amount) and concentrations were very low. Bromide showed a different flow pattern indicating a more uniform advective-dispersive transport process in the unfrozen columns with higher concentrations leaching but without clear concentration peaks. This study documents that pesticides can be preferentially transported through soil macropores at relatively high concentrations in partially frozen soil. These findings indicate, that monitoring programs should include sampling during snow melt or early spring in areas were soil frost is common as this period could imply exposure peaks in groundwater or surface water.

Effects of picoxystrobin and 4-n-nonylphenol on soil microbial community structure and respiration activity.

There is widespread use of chemical amendments to meet the demands for increased productivity in agriculture. Potentially toxic compounds, single or in mixtures, are added to the soil medium on a regular basis, while the ecotoxicological risk assessment procedures mainly follow a chemical by chemical approach. Picoxystrobin is a fungicide that has caused concern due to studies showing potentially detrimental effects to soil fauna (earthworms), while negative effects on soil microbial activities (nitrification, respiration) are shown to be transient. Potential mixture situations with nonylphenol, a chemical frequently occurring as a contaminant in sewage sludge used for land application, infer a need to explore whether these chemicals in mixture could alter the potential effects of picoxystrobin on the soil microflora. The main objective of this study was to assess the effects of picoxystrobin and nonylphenol, as single chemicals and mixtures, on soil microbial community structure and respiration activity in an agricultural sandy loam. Effects of the chemicals were assessed through measurements of soil microbial respiration activity and soil bacterial and fungal community structure fingerprints, together with a degradation study of the chemicals, through a 70 d incubation period. Picoxystrobin caused a decrease in the respiration activity, while 4-n-nonylphenol caused an increase in respiration activity concurring with a rapid degradation of the substance. Community structure fingerprints were also affected, but these results could not be directly interpreted in terms of positive or negative effects, and were indicated to be transient. Treatment with the chemicals in mixture caused less evident changes and indicated antagonistic effects between the chemicals in soil. In conclusion, the results imply that the application of the fungicide picoxystrobin and nonylphenol from sewage sludge application to agricultural soil in environmentally relevant concentrations, as single chemicals or in mixture, will not cause irreversible effects on soil microbial respiration and community structure.

Effect of freezing and thawing on microbial activity and glyphosate degradation in two Norwegian soils.

Little research has been done on pesticide dissipation in cold climates and there is a need to focus on the influence of climate on pesticide degradation in soil. Glyphosate, N-(phosphonomethyl)glycine, is a herbicide frequently used for controlling perennial weeds through application after harvest and was used as a model compound for this study. The effect of freeze-thaw activity on the availability of glyphosate in soil, and consequently its mineralization by soil microorganisms, was studied through laboratory incubations of repacked soil cores treated with 14C-labelled glyphosate and subjected to different freeze-thaw treatments. Winter simulation regimes applied were constant thaw (+5 degrees C), constant freezing (-5 degrees C), unstable conditions with short fluctuations (24 h of -5 degrees C followed by 24 h of +5 degrees C), and long duration fluctuations (3 weeks of -5 degrees C followed by 3 weeks of +5 degrees C). Distribution of 14C-glyphosate was followed during the incubation through measurements of the mineralized fraction (14CO2), soil water fraction, KOH extractable fraction, and non-extractable fraction. Microbial parameters used to characterize the soils were estimates of size of microbial biomass, overall microbial activity and microbial diversity. The constant freezing treatment exhibited the lowest amount of glyphosate mineralization. The constant thawed treatment and the treatments with fluctuating temperature exhibited significantly increased mineralization. These results were in accordance with the observed concentration of glyphosate in soil water; the higher the activity, the lower the concentration. The amount of glyphosate extractable with KOH and the resulting non-extractable fraction, however, were not significantly affected by soil type or temperature regime. The glyphosate mineralization pattern was comparable with the overall microbial activity in the soils. Observed different levels of diversity might explain some of the difference in total glyphosate mineralization between soils.