In situ and ex situ bioassays with Cantareus aspersus for environmental risk assessment of metal(loid) and PAH-contaminated soils.

Environmental risk assessment of contaminated soils requires bioindicators that allow the assessment of bioavailability and toxicity of chemicals. Although many bioassays can determine the ecotoxicity of soil samples in the laboratory, few are available and standardized for on-site application. Bioassays based on specific threshold values that assess the in situ and ex situ bioavailability and risk of metal(loid)s and polycyclic aromatic hydrocarbons (PAHs) in soils to the land snail Cantareus aspersus have never been simultaneously applied to the same soils. The aims of this study were to compare the results provided by in situ and ex situ bioassays and to determine their respective importance for environmental risk assessment. The feasibility and reproducibility of the in situ bioassay were assessed using an international ring test. This study used five plots located at a former industrial site and six laboratories participated in the ring test. The results revealed the impact of environmental parameters on the bioavailability of metal(loid)s and PAHs to snails exposed in the field to structured soils and vegetation compared to those exposed under laboratory conditions to soil collected from the same field site (excavated soils). The risk coefficients were generally higher ex situ than in situ, with some exceptions (mainly due to Cd and Mo), which might be explained by the in situ contribution of plants and humus layer as sources of exposure of snails to contaminants and by climatic parameters. The ring test showed good agreement among laboratories, which determined the same levels of risk in most of the plots. Comparison of the bioavailability to land snails and the subsequent risk estimated in situ or ex situ highlighted the complementarity between both approaches in the environmental risk assessment of contaminated soils, namely, to guide decisions on the fate and future use of the sites (e.g., excavation, embankments, and land restoration). Integr Environ Assess Manag 2022;18:539-554. © 2021 SETAC.

Fate and bioavailability of four conazole fungicides in twelve different arable soils - Effects of soil and pesticide properties.

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.

Concentration/time-dependent dissipation, partitioning and plant accumulation of hazardous current-used pesticides and 2-hydroxyatrazine in sand and soil.

The dissipation, partitioning dynamics and biouptake was measured for selected hazardous current-used pesticides (conazole fungicides: epoxiconazole, flusilazole, tebuconazole; prochloraz, chlorpyrifos, pendimethalin) and for a transformation product (2-hydroxyatrazine) in agricultural soil and quartz sand as representatives of a real and a worst-case scenario. Dissipation, uptake to Lactuca sativa and the freely dissolved concentration along with the organic carbon-normalized sorption coefficients (Koc) were determined on days 12, 40, and 90 following the application of compounds at three fortification levels (0.1-1.0-10 mg/kg). Conazole fungicides showed similar dissipation patterns and were more persistent in soil than prochloraz, chlorpyrifos and pendimethalin. 2-Hydroxyatrazine showed a concentration-depended decrease in persistency in soil. Lettuce roots were shown to accumulate higher amounts than shoots where the extent of root uptake was driven by compound partitioning. This was evidenced by the ability of freely dissolved concentration (Cfree) to reliably (r2 = 0.94) predict root uptake. Concentration in leaves did not exceed the maximum residue levels (MRLs) for lettuce, which was likely given by the low root-to-shoot translocation factors (TFs) of the tested compounds varying between 0.007 and 0.14. Koc values were in the range of literature values. Sorption to soil was higher than to sand for all compounds, yet following the Koc dynamics compounds did not appear to be sequestered in soil with increasing residence time. From these results, it follows that the tested compounds may persist in soil but since they did not accumulate in lettuce above MRLs, contamination of the food web is unlikely.

Currently and recently used pesticides in Central European arable soils.

Although large amounts of pesticides are used annually and a majority enters the soil to form short- or long-term residues, extensive soil surveys for currently used pesticides (CUPs) are scarce. To determine the status of CUPs' occurrence in arable land in Central Europe, 51 CUPs and 9 transformation products (TPs) were analysed in 75 arable soils in the Czech Republic (CR) several months after the last pesticide application. Moreover, two banned triazines (simazine and atrazine) and their TPs were analysed because of their frequent detection in CR waters. Multi-residue pesticide analysis on LC-MS/MS after soil QuEChERS extraction was used. The soils contained multiple pesticide residues frequently (e.g. 51% soils with ≥5 pesticides). The levels were also noticeable (e.g. 36% soils with ≥3 pesticides exceeding the threshold of 0.01mg/kg). After triazine herbicides (89% soils), conazole fungicides showed the second most frequent occurrence (73% soils) and also high levels (53% soils with total conazoles above 0.01mg/kg). Frequent occurrence was found also for chloroacetanilide TPs (25% of soils), fenpropidin (20%) and diflufenican (17%). With the exception of triazines' negative correlation to soil pH, no clear relationships were found between pesticide occurrence and soil properties. Association of simazine TPs with terbuthylazine and its target crops proved the frequent residues of this banned compound originate from terbuthylazine impurities. In contrast, frequent atrazine-2-hydroxy residue is probably a legacy of high atrazine usage in the past. The occurrence and levels of compounds were closely associated with their solubility, hydrophobicity and half-life. The results showed links to CR water-monitoring findings. This study represents the first extensive survey of multiple pesticide residues in Central European arable soils, including an insight into their relationships to site and pesticide properties.

Sorption, bioavailability and ecotoxic effects of hydrophobic organic compounds in biochar amended soils.

This work addresses the effect of biochar amendment to soil on contaminant sorption, bioavailability, and ecotoxicity. A distinction between positive primary amendment effects caused by reduced toxicity resulting from contaminant sorption, and negative secondary amendment effects of the biochars themselves was seen. Two biochars (one from high technology and one from low technology production processes) representing real world biochars were tested for the adsorption of pyrene, polychlorinated biphenyl (PCB) 52), and dichlorodiphenyldichloroethylene (p,p'-DDE). Sorption by both biochars was similar, both for compounds in single and mixed isotherms, in the presence and absence of soil. p,p'-DDE natively contaminated and spiked soils were amended with biochar (0, 1, 5, and 10%) and bioavailability, operationally defined bioaccessibility and ecotoxicity were assessed using polyethylene (PE), polymeric resin (XAD) and Folsomia candida, respectively. At the highest biochar dose (10%), bioavailability and bioaccessibility decreased by >37% and >41%, respectively, compared to unamended soils. Mortality of F. candida was not observed at any biochar dose, while reproductive effects were dose dependent. F. candida benefited from the reduction of p,p'-DDE bioavailability upon 1% and 5% biochar addition to contaminated soils while at 10% dose, these positive effects were nullified by biochar-induced toxicity. p,p'-DDE toxicity corrected for such secondary effects was predicted well by both PE uptake and XAD extraction.