Miroslav Fér

An analysis of the dissipation of pharmaceuticals under thirteen different soil conditions.

The presence of human and veterinary pharmaceuticals in the environment is recognized as a potential threat. Pharmaceuticals have the potential to contaminate soils and consequently surface and groundwater. Knowledge of contaminant behavior (e.g., sorption onto soil particles and degradation) is essential when assessing contaminant migration in the soil and groundwater environment. We evaluated the dissipation half-lives of 7 pharmaceuticals in 13 soils. The data were evaluated relative to the soil properties and the Freundlich sorption coefficients reported in our previous study. Of the tested pharmaceuticals, carbamazepine had the greatest persistence (which was mostly stable), followed by clarithromycin, trimethoprim, metoprolol, clindamycin, sulfamethoxazole and atenolol. Pharmaceutical persistence in soils was mostly dependent on the soil-type conditions. In general, lower average dissipation half-lives and variability (i.e., trimethoprim, sulfamethoxazole, clindamycin, metoprolol and atenolol) were found in soils of better quality (well-developed structure, high nutrition content etc.), and thus, probably better microbial conditions (i.e., Chernozems), than in lower quality soil (Cambisols). The impact of the compound sorption affinity onto soil particles on their dissipation rate was mostly negligible. Although there was a positive correlation between compound dissipation half-life and Freundlich sorption coefficient for clindamycin (R=0.604, p<0.05) and sulfamethoxazole (R=0.822, p<0.01), the half-life of sulfamethoxazole also decreased under better soil-type conditions. Based on the calculated dissipation and sorption data, carbamazepine would be expected to have the greatest potential to migrate in the soil water environment, followed by sulfamethoxazole, trimethoprim and metoprolol. The transport of clindamycin, clarithromycin and atenolol through the vadose zone seems less probable.

Antibiotics degradation in soil: A case of clindamycin, trimethoprim, sulfamethoxazole and their transformation products.

Twelve different soil types that represent the soil compartments of the Czech Republic were fortified with three antibiotics (clindamycin (CLI), sulfamethoxazole (SUL), and trimethoprim (TRI)) to investigate their fate. Five metabolites (clindamycin sulfoxide (CSO), hydroxy clindamycin sulfoxide (HCSO), S-(SDC) and N-demethyl clindamycin (NDC), N4-acetyl sulfamethoxazole (N4AS), and hydroxy trimethoprim (HTR)) were detected and identified using HPLC/HRMS and HRPS in the soil matrix in this study. The identities of CSO and N4AS were confirmed using commercially available reference standards. The parent compounds degraded in all soils. Almost all of the metabolites have been shown to be persistent in soils, with the exception of N4AS, which was formed and degraded completely within 23 days of exposure. The rate of degradation mainly depended on the soil properties. The PCA results showed a high dependence between the soil type and behaviour of the pharmaceutical metabolites. The mentioned metabolites can be formed in soils, and the most persistent ones may be transported to the ground water and environmental water bodies. Because no information on the effects of those metabolites on living organism are available, more studies should be performed in the future to predict the risk to the environment.

Using dye tracer for visualizing roots impact on soil structure and soil porous system

Abstract Plants influence the water regime in soil by both water uptake and an uneven distribution of water infiltration at the soil surface. The latter process is more poorly studied, but it is well known that roots modify soil structure by enhancing aggregation and biopore production. This study used a dye tracer to visualize the impact of plants on water flow in the topsoil of a Greyic Phaeozem. Brilliant blue was ponded to 10 cm height in a 1 m × 1 m frame in the field immediately after harvest of winter wheat (Triticum aestivum L.). After complete infiltration, the staining patterns within the vertical and horizontal field-scale sections were studied. In addition, soil thin sections were made and micromorphological images were used to study soil structure and dye distribution at the microscale. The field-scale sections clearly documented uneven dye penetration into the soil surface, which was influenced by plant presence and in some cases by mechanical compaction of the soil surface. The micromorphological images showed that root activities compress soil and increases the bulk density near the roots (which could be also result of root water uptake and consequent soil adhesion). On the other hand in few cases a preferential flow along the roots was observed.

Simultaneous sorption of four ionizable pharmaceuticals in different horizons of three soil types

Soils may be contaminated by human or veterinary pharmaceuticals. Their behaviour in soil environment is largely controlled by sorption of different compounds in a soil solution onto soil constituents. Here we studied the sorption affinities of 4 pharmaceuticals (atenolol, trimethoprim, carbamazepine and sulfamethoxazole) applied in solute mixtures to soils taken from different horizons of 3 soil types (Greyic Phaeozem on loess, Haplic Luvisol on loess and Haplic Cambisol on gneiss). In the case of the carbamazepine (neutral form) and sulfamethoxazole (partly negatively charged and neutral), sorption affinity of compounds decreased with soil depth, i.e. decreased with soil organic matter content. On the other hand, in the case of atenolol (positively charged) and trimethoprim (partly positively charged and neutral) compound sorption affinity was not depth dependent. Compound sorption affinities in the four-solute systems were compared with those experimentally assessed in topsoils, and were estimated using the pedotransfer rules proposed in our previous study for single-solute systems. While sorption affinities of trimethoprim and carbamazepine in topsoils decreased slightly, sorption affinity of sulfamethoxazole increased. Decreases in sorption of the two compounds could be attributed to their competition between each other and competition with atenolol. Differences between carbamazepine and atenolol behaviour in the one- and four-solute systems could also be explained by the slightly different soil properties in this and our previous study. A great increase of sulfamethoxazole sorption in the Greyic Phaeozem and Haplic Luvisol was observed, which was attributed to elimination of repulsion between negatively charged molecules and particle surfaces due to cation sorption (atenolol and trimethoprim) on soil particles. Thus, our results proved not only an antagonistic but also a synergic affect of differently charged organic molecules on their sorption to soil constituents.

Droplet infiltration dynamics and soil wettability related to soil organic matter of soil aggregate coatings and interiors

Abstract The organo-mineral coatings of soil aggregates, cracks, and biopores control sorption and macropore-matrix exchange during preferential flow, in particular in the clay-illuvial Bt-horizon of Luvisols. The soil organic matter (SOM) composition has been hypothesized to explain temporal changes in the hydraulic properties of aggregate surfaces. The objective of this research was to find relations between the temporal change in wettability, in terms of droplet infiltration dynamics, and the SOM composition of coated and uncoated aggregate surfaces. We used 20 to 40 mm sized soil aggregates from the Bt2 horizon of a Haplic Luvisol from loess that were (i) coated, (ii) not coated (both intact), and (iii) aggregates from which coatings were removed (cut). The SOM composition of the aggregate surfaces was characterized by infrared spectroscopy in the diffuse reflection mode (DRIFT). A potential wettability index (PWI) was calculated from the ratio of hydrophobic and hydrophilic functional groups in SOM. The water drop penetration times (WDPT) and contact angles (CA) during droplet infiltration experiments were determined on dry and moist aggregate samples of the three types. The decrease in the CA with time was described using the power function (CA(t) = at−b). For dry aggregates, the WDPT values were larger for coated as compared to uncoated regions on the aggregate surfaces, and increased with increasing PWI value (R2 = 0.75). The a parameter was significantly related to the WDPT (R2 = 0.84) and to the PWI (R2 = 0.64). The relations between the b parameter and the WDPT (R2 = 0.61) and the PWI (R2 = 0.53) were also significant. The WDPT values of wet soil aggregates were higher than those of dry aggregates due to high water contents, which limited the droplet infiltration potential. At the wet aggregate surfaces, the WDPT values increased with the PWI of the SOM (R2 = 0.64). In contrast to dry samples, no significant relationships were found between parameters a or b of CA(t) and WDPT or PWI for wet aggregate surfaces. The results suggest that the effect of the SOM composition of coatings on surface wettability decreases with increasing soil moisture. In addition to the dominant impact of SOM, the wettability of aggregate surfaces could be affected by different mineralogical compositions of clay in coatings and interiors of aggregates. Particularly, wettability of coatings could be decreased by illite which was the dominant clay type in coatings. However, the influence of different clay mineral fractions on surface wettability was not due to small number of measurements (2 and 1 samples from coatings and interiors, respectively) quantified.

Using magnetic susceptibility mapping for assessing soil degradation due to water erosion.

Jaksik O., Kodesova R., Kapicka A., Klement A., Fer M., Nikodem A. (2016): Using magnetic susceptibility mapping for assessing soil degradation due to water erosion. Soil & Water Res., 11: 105–113. This study focused on developing a method for estimating topsoil organic carbon content from measured massspecific magnetic susceptibility in Chernozems heavily affected by water erosion. The study was performed on a 100 ha area, whereby 202 soil samples were taken. A set of soil samples was divided into 3 subsets: A (32 samples), B (67 samples), and C (103 samples). The mass-specific magnetic susceptibility using low ( χ lf ) and high ( χ hf ) frequency, and organic carbon content were measured at all soil samples. The contents of iron and manganese, extracted with a dithionite-citrate solution (Fe d , Mn d ) and ammonium oxalate (Fe o , Mn o ), were quantified in A and B samples. Models for predicting organic carbon content from magnetic susceptibilities were designed as follows: (1) subset A was used as the training set for calibration, and subsets B and C were used as the test sets for model validation, either separately (subset B only), or together (merged subsets B and C); (2) merged subsets A and B were used as the training set and subset C was used as the test set. Results showed very close correlations between organic carbon content and all measured soil properties. Obtained models relating organic carbon content to mass-specific magnetic susceptibility successfully predicted soil organic carbon contents.

Earthworm responses to different reclamation processes in post opencast mining lands during succession

This study provides earthworm population data obtained from localities with a substantial anthropogenic impact spoils. The spoil heaps were reclaimed at the end of an opencast brown coal mining period. We studied spoils reclaimed by the two most commonly used reclamation processes: forestry and agricultural. The results show the significance of the locality age and the utilized reclamation process and treatment and their effect on earthworm communities. Our data indicate that apart from soil physical and chemical properties, the reclamation process itself may also induce viability and distribution of earthworm communities. Under standardized soil properties, the changes in earthworm populations during the succession were larger within the agricultural reclamation process as opposed to the forestry reclamation process for earthworm ecological groups and individual species.

Influence of soil-water content on CO2 efflux within the elevation transect heavily impacted by erosion: Influence of Soil-Water Content on CO2 Efflux

Faculty of Agrobiology, Food and Natural, Resources, Dept. of Soil Science and Soil Protection, Czech University of Life Sciences Prague, Kamýcká 129, CZ‐16500 Prague 6, Czech Republic Correspondence Miroslav Fér, Faculty of Agrobiology, Food and Natural, Resources, Dept. of Soil Science and Soil Protection, Czech University of Life Sciences Prague, Kamýcká 129, CZ‐16500 Prague 6, Czech Republic. Email: mfer@af.czu.cz Funding information Czech Science Foundation, Grant/Award Number: 17‐08937S; Ministry of Agriculture of the Czech Republic, Grant/Award Number: QJ1230319

Sorption of citalopram, irbesartan and fexofenadine in soils: Estimation of sorption coefficients from soil properties

The sorption of 3 pharmaceuticals, which may exist in 4 different forms depending on the solution pH (irbesartan in cationic, neutral and anionic, fexofenadine in cationic, zwitter-ionic and anionic, and citalopram cationic and neutral), in seven different soils was studied. The measured sorption isotherms were described by Freundlich equations, and the sorption coefficients, KF (for the fixed n exponent for each compound), were related to the soil properties to derive relationships for estimating the sorption coefficients from the soil properties (i.e., pedotransfer rules). The largest sorption was obtained for citalopram (average KF value for n = 1 was 1838 cm3 g-1) followed by fexofenadine (KF = 35.1 cm3/n μg1-1/n g-1, n = 1.19) and irbesartan (KF = 3.96 cm3/n μg1-1/n g-1, n = 1.10). The behavior of citalopram (CIT) in soils was different than the behaviors of irbesartan (IRB) and fexofenadine (FEX). Different trends were documented according to the correlation coefficients between the KF values for different compounds (RIRB,FEX = 0.895, p-value<0.01; RIRB,CIT = -0.835, p-value<0.05; RFEX,CIT = -0.759, p-value<0.05) and by the reverse relationships between the KF values and soil properties in the pedotransfer functions. While the KF value for citalopram was positively related to base cation saturation (BCS) or sorption complex saturation (SCS) and negatively correlated to the organic carbon content (Cox), the KF values of irbesartan and fexofenadine were negatively related to BCS, SCS or the clay content and positively related to Cox. The best estimates were obtained by combining BCS and Cox for citalopram (R2 = 93.4), SCS and Cox for irbesartan (R2 = 96.3), and clay content and Cox for fexofenadine (R2 = 82.9).

Root distributions in a laboratory box evaluated using two different techniques (gravimetric and image processing) and their impact on root water uptake simulated with HYDRUS

Abstract Knowledge of the distribution of plant roots in a soil profile (i.e. root density) is needed when simulating root water uptake from soil. Therefore, this study focused on evaluating barley and wheat root densities in a sand-vermiculite substrate. Barley and wheat were planted in a flat laboratory box under greenhouse conditions. The box was always divided into two parts, where a single plant row and rows cross section (respectively) was simulated. Roots were excavated at the end of the experiment and root densities were assessed using root zone image processing and by weighing. For this purpose, the entire area (width of 40 and height of 50 cm) of each scenario was divided into 80 segments (area of 5×5 cm). Root density in each segment was expressed as a root percentage of the entire root cluster. Vertical root distributions (i.e. root density with respect to depth) were also calculated as a sum of root densities in each 5 cm layer. Resulting vertical root densities, measured evaporation from the water table (used as the potential root water uptake), and the Feddes stress response function model were used for simulating substrate water regime and actual root water uptake for all scenarios using HYDRUS-1D. All scenarios were also simulated using HYDRUS-2D. One scenario (areal root density of barley sown in a single row, obtained using image analysis) is presented in this paper (because most scenarios showed root water uptakes similar to results of 1D scenarios). The application of two root detecting techniques resulted in noticeably different root density distributions. Differences were mainly attributed to the fact that fine roots of high density (located mostly at the deeper part of the box) had lower weights in comparison to the weight of few large roots (at the box top). Thus, at the deeper part, higher root density (with respect to the entire root zone) was obtained using the image analysis in comparison to that from the gravimetric analysis. Conversely, lower root density was obtained using the image analysis at the upper part in comparison to that from the gravimetric analysis. On the other hand, fine roots overlapped each other and therefore were not visible in the image, which resulted in lower root density values from image analysis. Root water uptakes simulated with HYDRUS-1D using diverse root densities obtained for each cereal declined differently from the potential root water uptake values depending on water scarcity at depths of higher root density. Usually, an earlier downtrend associated with gradual root water up-take decreases and vice versa. Similar root water uptakes were simulated for the presented scenario using the HYDRUS-1D and HYDRUS-2D models. The impact of the horizontal root density distribution on root water uptake was, in this case, less important than the impact of the vertical root distribution resulting from different techniques and sowing scenarios.