Martin Kočárek

Impact of varying soil structure on transport processes in different diagnostic horizons of three soil types

When soil structure varies in different soil types and the horizons of these soil types, it has a significant impact on water flow and contaminant transport in soils. This paper focuses on the effect of soil structure variations on the transport of pesticides in the soil above the water table. Transport of a pesticide (chlorotoluron) initially applied on soil columns taken from various horizons of three different soil types (Haplic Luvisol, Greyic Phaeozem and Haplic Cambisol) was studied using two scenarios of ponding infiltration. The highest infiltration rate and pesticide mobility were observed for the Bt(1) horizon of Haplic Luvisol that exhibited a well-developed prismatic structure. The lowest infiltration rate was measured for the Bw horizon of Haplic Cambisol, which had a poorly developed soil structure and a low fraction of large capillary pores and gravitational pores. Water infiltration rates were reduced during the experiments by a soil structure breakdown, swelling of clay and/or air entrapped in soil samples. The largest soil structure breakdown and infiltration decrease was observed for the Ap horizon of Haplic Luvisol due to the low aggregate stability of the initially well-aggregated soil. Single-porosity and dual-permeability (with matrix and macropore domains) flow models in HYDRUS-1D were used to estimate soil hydraulic parameters via numerical inversion using data from the first infiltration experiment. A fraction of the macropore domain in the dual-permeability model was estimated using the micro-morphological images. Final soil hydraulic parameters determined using the single-porosity and dual-permeability models were subsequently used to optimize solute transport parameters. To improve numerical inversion results, the two-site sorption model was also applied. Although structural changes observed during the experiment affected water flow and solute transport, the dual-permeability model together with the two-site sorption model proved to be able to approximate experimental data.

Pesticide adsorption in relation to soil properties and soil type distribution in regional scale.

Study was focused on the evaluation of pesticide adsorption in soils, as one of the parameters, which are necessary to know when assessing possible groundwater contamination caused by pesticides commonly used in agriculture. Batch sorption tests were performed for 11 selected pesticides and 13 representative soils. The Freundlich equations were used to describe adsorption isotherms. Multiple-linear regressions were used to predict the Freundlich adsorption coefficients from measured soil properties. Resulting functions and a soil map of the Czech Republic were used to generate maps of the coefficient distribution. The multiple linear regressions showed that the K(F) coefficient depended on: (a) combination of OM (organic matter content), pH(KCl) and CEC (cation exchange capacity), or OM, SCS (sorption complex saturation) and salinity (terbuthylazine), (b) combination of OM and pH(KCl), or OM, SCS and salinity (prometryne), (c) combination of OM and pH(KCl), or OM and ρ(z) (metribuzin), (d) combination of OM, CEC and clay content, or clay content, CEC and salinity (hexazinone), (e) combination of OM and pH(KCl), or OM and SCS (metolachlor), (f) OM or combination of OM and CaCO(3) (chlorotoluron), (g) OM (azoxystrobin), (h) combination of OM and pH(KCl) (trifluralin), (i) combination of OM and clay content (fipronil), (j) combination of OM and pH(KCl), or OM, pH(KCl) and CaCO(3) (thiacloprid), (k) combination of OM, pH(KCl) and CEC, or sand content, pH(KCl) and salinity (chlormequat chloride).

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.

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.

Influence of temperature on soil water content measured by ECH2O-TE sensors

Influence of temperature on soil water content measured by ECH2O-TE sensors The aim of this study was to investigate the influence of temperature on water content value measured by ECH2O-TE sensors. The influence of temperature on measured soil water content values was clearly demonstrated. Soil water content values measured during the day apparently oscillated with oscillating soil temperatures. Average daily temperature and soil water content were calculated for selected periods. Regression relationships between deviations of soil temperature and soil water content from their daily average values were evaluated. Correlation between the soil water content and temperature deviations increase with the soil depth due to the lower influence of rainfall and evaporation at the soil surface on measured soil water content values in deeper soil layers eg soil water content oscillation was controlled mostly by oscillating temperature. The guideline values of linear regression equations (R2>0.8) were very similar, close to value 0.002 and the intercept values were equal to zero. The equation for recalculation of measured soil water content values at given temperature to reference soil water content for reference soil temperature, was propozed on the basis of this analysis.

Pendimethalin degradation in soil and its interaction with soil microorganisms

Kočárek M., Artikov H., Voříšek K., Borůvka L. (2016): Pendimethalin degradation in soil and its interaction with soil microorganisms. Soil & Water Res., 11: 213−219. Pendimethalin [N-(1-ethylpropyl)-3,4-dimethyl-2, 6-dinitrobenzenamine] is a herbicide used worldwide to control most annual grasses and common weeds in cereals, fruit, and vegetables. Its degradation in Haplic Chernozem under controlled greenhouse conditions was studied in this paper. The effect of recommended and doubled pendimethalin doses, as well as the effect of the biopreparate EM-EKO ProBio Plus on pendimethalin degradation in soil and on soil microorganisms was investigated. Pendimethalin half-life ranged from 24.4 to 34.4 days and the double dose did not increase the pendimethalin half-life. Thirty-eight days after pendimethalin application there was no statistical difference between the pendimethalin concentration in soil when applied at the recommended and doubled dose. No effect of pendimethalin on the amount or the activity of soil microorganisms was observed. The effect of EM-EKO ProBio Plus was apparent only on the first sampling of double-dose pendimethalin, however, this bio-preparate had no significant effect on the half-life of pendimethalin, as observed at the end of the experiment.

Effect of a non-woven fabric covering on the residual activity of pendimethalin in lettuce and soil.

BACKGROUND Lettuce (Lactuca sativa L.) is a crop that is very sensitive to herbicide contamination owing to its short growing season. The use of long-residual herbicides and non-woven fabric coverings could therefore influence pendimethalin concentrations in soil and lettuce. RESULTS The pendimethalin half-life in soil ranged between 18 and 85 days and was mainly affected by season (i.e. weather), and especially by soil moisture. Pendimethalin degradation in soil was slowest under dry conditions. A longer pendimethalin half-life was observed under the non-woven fabric treatment, but the effect of varying application rate was not significant. Pendimethalin residue concentrations in lettuce heads were significantly influenced by pendimethalin application rate and by non-woven fabric cover, especially at the lettuces early growth stages. The highest pendimethalin concentration at final harvest was determined in lettuce grown on uncovered plots treated with pendimethalin at an application rate of 1200 g ha-1 (7-38 µg kg-1 ). Depending on growing season duration and weather conditions, pendimethalin concentrations in lettuce grown under non-woven fabric ranged from 0 to 21 µg kg-1 . CONCLUSION Use of transparent non-woven fabric cover with lettuce can help to reduce application rates of soil herbicides and diminish the risk of herbicide contamination in the harvested vegetables.

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).

Numerical Simulation of Fly-Ash Transport in Three Sands of Different Particle-Size Distributions Using Hydrus-1d

Numerical Simulation of Fly-Ash Transport in Three Sands of Different Particle-Size Distributions Using Hydrus-1d Study is focused on the numerical modeling of fly-ash transport in three sands, which was experimentally studied in the laboratory. Sands were packed in glass cylinders with diameter of 5.52 cm and height of 18 cm. Sands were also packed in plastic cylinders with diameter of 30 cm and height of 40 cm. The fly-ash and pulse infiltrations were applied on the top of all cylinders. Visually observed and gravimetrically evaluated fly-ash migration in small cylinders corresponded to fly-ash mobility in large columns detected using the SM400 Kappameter. The HYDRUS-1D code was used to simulate observed fly-ash transport. Parameters of soil hydraulic functions were either obtained using the Tempe cells and the RETC program or estimated using numerical inversion of transient water flow data measured in both types of columns using HYDRUS-1D. Parameters characterizing colloid transport in sands were then estimated from the final fly-ash distribution in sandy columns using attachment/detachment concept in HYDRUS-1D. Fly-ash mobility increased with increasing sand particle sizes, e.g. pore sizes. Particle sizes and pore water velocity influenced the attachment coefficient, which was calculated assuming filtration theory. The same longitudinal dispersivity, sticking efficiency and detachment coefficient sufficiently characterized fly-ash behavior in all sands. Numerická Simulace Transportu Úletového Popílku VE Třech Píscích Různého Zrnitostního Složení Pomocí Hydrus-1D. Studie je zaměřena na numerické modelování transportu úletového popílku ve třech píscích, který by1 experimentálně studován v laboratoři. Písky byly nahutněny ve skleněných válcích o průměru 5,52 cm a výŠce 18 cm. Písky byly také nahutněny v plastových válcích o průměru 30 cm a výŠce 40 cm. Na povrchu válců byly aplikovány jednorázové infiltrace vody s popílkem. Migrace úletového popílku pozorovaná vizuálně a zjiŠtěná gravimetricky v malých válcích odpovídala mobilitě úletového popílku detekované Kappametrem SM400 ve velkých válcích. Pozorovaný transport úletového popílku byl simulován programem HYDRUS-1D. Parametry hydraulických funkcí byly získány buď pomocí Tempských cel a programu RETC nebo odhadovány numerickou inverzí transientních data měřených na obou typech válců programem HYDRUS-1D. Parametry charakterizující transport koloidů v píscích byly potom odhadovány z konečné distribuce úletového popílku v písčitých sloupcích užitím konceptu attachment/detachment (připojení/odpojení) v programu HYDRUS-1D. Mobilita úletového popílku se zvyŠovala se zvyŠující se velikostí písčitých zrn, tj. s velikostí pórů. Velikost zrn a pórová rychlost ovlivnila depoziční (attachment) koeficient, který byl počítán na základě filtrační teorie. Stejné hodnoty podélné disperze, efektivity blokování (sticking efficiency) a mobilizačního (detachement) koeficientu charakterizovaly chování úletového popílku ve vŠech píscích.

Field Study and Modeled Transport of Chlortoluron in Different Soil Types of the Czech Republic

Chlortoluron transport was studied in five different soil types in five locations in the Czech Republic. There were considerable differences in herbicide transport with varying soil types and locations. The BPS mathematical model (Kozak and Vacek, 1996) was used to simulate chlortoluron transport. The chlortoluron concentrations that were predicted by the model were similar to the measured data except in the Greyic Phaozem, where preferential flow may have greatly influenced solution transport.