Surface soil samples were collected near the Open Pit Bor (S1) and Open Pit Cerovo (S2), a grassland along the Borska Reka River (S3) and an unpolluted garden near Slatina village (reference site). Spontaneous plants (dandelion, nettle, coltsfoot, and creeping buttercup) and vegetables (onion, garlic, carrot, parsley, celery, potatoes, dill, and sorrel) were obtained from the former three sites and the reference site, respectively. The samples were analyzed for Zn, Cu, Fe, Mn, and Pb via FAAS. Pollution indices indicated low-to-moderate soil contamination at sites S1, S2, and S3. Cu was the main contaminant of environmental concern, being above the maximum admitted concentration at site S1. Metal levels in spontaneous plants were below phytotoxic levels. Cu content of leafy vegetables and celery roots and Pb content of most vegetables were not safe for human consumption. Metal concentrations tended to be significantly lower in plants than in soils, with only Cu occurring at significantly elevated levels in celery roots and sorrel leaves. Non-carcinogenic risk assessment showed that consumption of carrot roots and especially celery roots grown on unpolluted soils from the Bor area might pose long-term health risks for females and males, with the main contributors being Cu and Fe.
Herbicides are being used more and more to increase productivity in agriculture, but their excessive has been shown to lead to adverse effects on the environment, especially on the soil. Within this study the effect of the herbicide S-metolachlor on the activity of several enzymes (dehydrogenase, protease, phosphatase and urease) found in the loamy-clayey soil has been analyzed. There were seven experimental variants corresponding to the untreated soil and to the application of six distinct doses of S-metolachlor on soil samples maintained in laboratory conditions. Biochemical analyzes have been performed to assess the activities of the investigated enzymes at 7, 14 and 21 days, respectively, and several physiochemical parameters of the soil have been also monitored during these experiments. The data obtained in the experimental determinations were subjected to statistical analysis such as to evaluate if the changes in the activities of enzymes are significant and to establish if there are correlations between the evolution of analyzed enzymatic activities and the physicochemical parameters of the soil. Molecular docking approach has been also used to assess the interactions between the herbicide and investigated enzymes. The activities of studied enzymes decreased in a dose-dependent manner when the herbicide was applied. More than 21 days were necessary to recover the activities of dehydrogenase and protease in the soil treated with S-metolachlor, the activity of protease was recovered after 14 days and the activity of urease was recuperated after 7 days of incubation. This study also emphasized significant correlations between the enzymatic activities and some physicochemical parameters of the soil: pH, moisture, organic matter, nitrogen level and available phosphorus.
Aclonifen is an herbicide with a global market that is expected to grow in the period 2021–2027. This study focuses on revealing the effects of both aclonifen and of its soil metabolites on aqueous and soil environments. The soil’s physicochemical parameters and activities of enzymes found in the soil (urease, dehydrogenase, catalase, alkaline phosphatase) were evaluated in laboratory conditions for soil treated with various doses of aclonifen (from half of a normal dose, 2.1 g/ha, to three times the normal dose) every 7 days for a period of 28 days. A computational approach was used to calculate the acute toxicity of aclonifen and of its soil metabolites on aqueous organisms and to evaluate the possible interactions of these compounds with soil enzymes. The results obtained in the experimental study showed a significant inhibitory effect of the herbicide aclonifen on the investigated enzymes; those activities were not recovered after 28 days in the presence of high doses of aclonifen. Statistically significant effects of the herbicide dose and exposure duration on enzymes’ activities were observed using post hoc analysis at the p < 0.001 level. Pearson’s correlations revealed that the investigated enzyme activities were usually strongly (p < 0.001) influenced by the organic matter, available phosphorus content, and nitrogen level. The outcomes of the computational study revealed moderate acute aqueous toxicity of aclonifen and of its metabolites. All metabolites were also able to bind to the investigated enzymes and may have an inhibitory effect on their activities.
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