Lucie Bielská

Bioavailability and toxicity of pyrene in soils upon biochar and compost addition

The study investigates the role of biochar and/or compost in mitigating the toxic effects of pyrene in soils using reproduction of nematodes and porewater concentration as measures of pyrene toxicity and bioavailability, respectively. Two soils were spiked with increasing levels of pyrene to achieve a concentration-response relationship for the reproduction of Caenorhabditis elegans. The observed EC50 values (pyrene concentration causing 50% inhibition of reproduction) were 14mg/kg and 31mg/kg (dry mass) for these soils, corresponding to equilibrium porewater concentrations of 37μg/L and 47μg/L, respectively. Differences in organic carbon content were not sufficient to explain the variability in toxicity between the different soils. Soils causing a significant inhibition of reproduction were further amended with 10%-compost, 5%-biochar, or both, and the effects on reproduction and porewater concentration determined. Combined addition of compost and biochar was identified as the most effective strategy in reducing pyrene concentration in soil porewater, which was also partly reflected in soil toxicity. However, porewater concentrations predicted only 52% of pyrene toxicity to nematodes, pointing to particle-bound or dietary exposure pathways. Capsule: Amending pyrene-spiked soil with biochar and compost effectively reduced pyrene porewater concentrations and toxicity to nematodes, which were significantly related.

Occurrence of Chlorotriazine herbicides and their transformation products in arable soils

Chlorotriazine herbicides (CTs) are widely used pest control chemicals. In contrast to groundwater contamination, little attention has been given to the circumstances of residue formation of parent compounds and transformation products in soils. Seventy-five cultivated floodplain topsoils in the Czech Republic were sampled in early spring of 2015, corresponding to a minimum of six months (current-use terbuthylazine, TBA) and a up to a decade (banned atrazine, AT and simazine, SIM) after the last herbicide application. Soil residues of parent compounds and nine transformation products were quantified via multiple residue analysis using liquid chromatography - tandem mass spectrometry of acetonitrile partitioning extracts (QuEChERS). Using principal component analysis (PCA), their relation to soil chemistry, crops and environmental parameters was determined. Of the parent compounds, only TBA was present in more than one sample. In contrast, at least one CT transformation product, particularly hydroxylated CTs, was detected in 89% of the sites, or 54% for banned triazines. Deethylated and bi-dealkylated SIM or AT residues were not detectable. PCA suggests the formation and/or retention of CT hydroxy-metabolite residues to be related to low soil pH, and a direct relation between TBA and soil organic carbon, and between deethyl-TBA and clay or Ca contents, respectively, the latter pointing towards distinct sorption mechanisms. The low historic application of simazine contrasted by the high abundance of its residues, and the co-occurrence with AT residues suggests the post-ban application of AT and SIM banned triazines as a permitted impurity of TBA formulations as a recent, secondary source. The present data indicate that topsoils do not contain abundant extractable residues of banned parent chlorotriazines, and are thus likely not the current source for related ground- and surface water contamination. In contrast, topsoils might pose a long-term source of TBA and CT transformation products for ground and surface water contamination.

Assessment of the biological and chemical availability of the freshly spiked and aged DDE in soil

The study compared the ability of various chemical methods (XAD, β-hydroxypropylcyclodextrin - HPCD) and solid phase micro-extraction (SPME)) to mimic earthworm uptake from two similar soils containing either spiked or aged p,p´-DDE, thus representing two extreme scenarios with regard to the length of pollutant-soil contact time and the way of contamination. The extent of bioaccumulation was assessed at fixed exposure periods (10 and 21 days) and at equilibrium derived from uptake curves by multiple-point comparison or kinetic modeling. The decision on the best chemical predictor of biological uptake differed. The degree of bioaccumulation at equilibrium was best predicted by XAD while HPCD rather reflected the extent of accumulation derived after 21 days when, however, steady-state was not reached for spiked p,p´-DDE. SPME seemed to underestimate the uptake of aged p,p´-DDE, probably of the fraction taken up via soil particles. Thus, the degree of predictability seems to be associated with the capability of the chemical method to mimic the complex earthworm uptake via skin and intestinal tract as well as with the quality of biological data where the insufficient length of exposure period appears to be the major concern.

The kinetics of solid-phase microextraction measured for freshly added and aged hydrophobic compounds in two different soils

The proper choice of exposure times is critical if the freely dissolved concentration of chemicals in soil porewater is to be measured via the equilibrium solid-phase microextraction (SPME) as the times to equilibrium may vary depending on compound and soil properties. To reveal the effects of compound hydrophobicity, ageing and soil organic matter content on times to equilibrium, the SPME uptake was measured for five freshly added and aged hydrophobic organic compounds (phenanthrene, pyrene, lindane, p,p′-DDT and polychlorinated biphenyl (PCB) 153) in two contrasted soils (arable and forest soil). The tested compound-soil systems behaved kinetically different. Longer equilibrium times were observed with increasing hydrophobicity of compounds for aged compared to freshly added chemicals and for the forest soil in comparison to the arable soil. The calculated soil–porewater partition coefficients (i.e. sorption coefficients, Kd) of chemicals differed between soil types mainly due to various organic carbon (OC) contents as evidenced by the comparable Koc values (i.e. Kd values normalised to soil OC content). Similar Koc values were also found with the various extent of ageing, indicating that both the freshly added and aged compounds linearly partitioned between the soil organic matter and porewater. Our results suggest that, for a respective compound, variations in equilibrium times may be expected depending upon the residence time and the organic matter content in soil where the longest equilibrium times seems to appear for a combination of aged compounds and high organic soils. With regard to this outcome, the effect of the level of sample depletion due to the SPME extraction (LDSPME) on equilibrium times was assessed. At LDsSPME of up to 10%, equilibrium times increases linearly with LDsSPME for p,p′-DDT and PCB 153. For phenanthrene (LDSPME<10%), and for lindane and pyrene (1.2% < LDSPME > 40%), no clear relationships were observed.

The variability of standard artificial soils: cadmium and phenanthrene sorption measured by a batch equilibrium method

Artificial soil (AS) is used in soil ecotoxicology as a test medium or reference matrix. AS is prepared according to standard OECD/ISO protocols and components of local sources are usually used by laboratories. This may result in significant inter-laboratory variations in AS properties and, consequently, in the fate and bioavailability of tested chemicals. In order to reveal the extent and sources of variations, the batch equilibrium method was applied to measure the sorption of 2 model compounds (phenanthrene and cadmium) to 21 artificial soils from different laboratories. The distribution coefficients (Kd) of phenanthrene and cadmium varied over one order of magnitude: from 5.3 to 61.5L/kg for phenanthrene and from 17.9 to 190L/kg for cadmium. Variations in phenanthrene sorption could not be reliably explained by measured soil properties; not even by the total organic carbon (TOC) content which was expected. Cadmium logKd values significantly correlated with cation exchange capacity (CEC), pHH2O and pHKCl, with Pearson correlation coefficients of 0.62, 0.80, and 0.79, respectively. CEC and pHH2O together were able to explain 72% of cadmium logKd variability in the following model: logKd=0.29pHH2O+0.0032 CEC -0.53. Similarly, 66% of cadmium logKd variability could be explained by CEC and pHKCl in the model: logKd=0.27pHKCl+0.0028 CEC -0.23. Variable cadmium sorption in differing ASs could be partially treated with these models. However, considering the unpredictable variability of phenanthrene sorption, a more reliable solution for reducing the variability of ASs from different laboratories would be better harmonization of AS preparation and composition.

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.

Sorption to soil, biochar and compost: is prediction to multicomponent mixtures possible based on single sorbent measurements?

Amendment with biochar and/or compost has been proposed as a strategy to remediate soil contaminated with low levels of polycyclic aromatic hydrocarbons. The strong sorption potential of biochar can help sequestering contaminants while the compost may promote their degradation. An improved understanding of how sorption evolves upon soil amendment is an essential step towards the implementation of the approach. The present study reports on the sorption of pyrene to two soils, four biochars and one compost. Detailed isotherm analyzes across a wide range of concentration confirmed that soil amendments can significantly increase the sorption of pyrene. Comparisons of data obtained by a classical batch and a passive sampling method suggest that dissolved organic matter did not play a significant role on the sorption of pyrene. The addition of 10% compost to soil led to a moderate increase in sorption (<2-fold), which could be well predicted based on measurements of sorption to the individual components. Hence, our result suggest that the sorption of pyrene to soil and compost can be relatively well approximated by an additive process. The addition of 5% biochar to soil (with or without compost) led to a major increase in the sorption of pyrene (2.5–4.7-fold), which was, however, much smaller than that suggested based on the sorption measured on the three individual components. Results suggest that the strong sorption to the biochar was attenuated by up to 80% in the presence of soil and compost, much likely due to surface and pore blockage. Results were very similar in the two soils considered, and collectively suggest that combined amendments with compost and biochar may be a useful approach to remediate soils with low levels of contamination. Further studies carried out in more realistic settings and over longer periods of time are the next step to evaluate the long term viability of remediation approaches based on biochar amendments.