Vladislav Chrastný

Contamination of vineyard soils with fungicides: a review of environmental and toxicological aspects.

The contamination of agricultural soils with inorganic (Cu-based) and organic pesticides (including their residues) presents a major environmental and toxicological concern. This review summarizes available studies published on the contamination of vineyard soils throughout the world with Cu-based and synthetic organic fungicides. It focuses on the behavior of these contaminants in vineyard soils and the associated environmental and toxicological risks. The concentrations of Cu in soils exceed the legislative limits valid in the EU in the vast majority of the studied vineyards. Regarding the environmental and toxicological hazards associated with the extensive use of fungicides, the choice of fungicides should be performed carefully according to the physico-chemical properties of the soils and climatic and hydrogeological characteristics of the vine-growing regions.

Potential and drawbacks of EDDS-enhanced phytoextraction of copper from contaminated soils.

Incubation and pot experiments using poplar (Populus nigra L. cv. Wolterson) were performed in order to evaluate the questionable efficiency of EDDS-enhanced phytoextraction of Cu from contaminated soils. Despite the promising conditions of the experiment (low contamination of soils with a single metal with a high affinity for EDDS, metal tolerant poplar species capable of producing high biomass yields, root colonization by mycorrhizal fungi), the phytoextraction efficiency was not sufficient. The EDDS concentrations used in this study (3 and 6 mmol kg(-1)) enhanced the mobility (up to a 100-fold increase) and plant uptake of Cu (up to a 65-fold increase). However, despite EDDS degradation and the competition of Fe and Al for the chelant, Cu leaching cannot be omitted during the process. Due to the low efficiency, further research should be focused on other environment-friendly methods of soil remediation.

Retention of copper originating from different fungicides in contrasting soil types

This work described the retention of Cu from two different commonly used pesticides, the Bordeaux mixture (CuSO(4)+Ca(OH)(2)) and Cu-oxychloride (3Cu(OH)(2).CuCl(2)), and from Cu(NO(3))(2) in contrasting soil types (Leptosol, Chernozem, Cambisol). Thermodynamic modeling showed that Cu speciation was similar in all fungicide solutions. However, the retention of Cu differed with the fungicide used (maximum retention from the Bordeaux mixture) which indicates that different retention processes occurred in the studied soils. The suggested mechanisms include: specific and non-specific adsorption (especially on soil organic matter), precipitation of newly formed phases, such as CuO, Cu(OH)(2), Cu(2)(OH)(3)NO(3), CuCO(3)/Cu(2)(OH)(2)CO(3) and in the case of the Bordeaux mixture, precipitation of various Cu-hydroxysulfates. These phases were identified by the speciation model. The retention of fungicide-derived Cu in the studied soil types followed well the Freundlich isotherm and was directly controlled by the chemical form of Cu. This fact should be taken into account for both environmental and practical applications.

Competitive Adsorption of Cd(II), Cr(VI), and Pb(II) onto Nanomaghemite: A Spectroscopic and Modeling Approach

A combined modeling and spectroscopic approach is used to describe Cd(II), Cr(VI), and Pb(II) adsorption onto nanomaghemite and nanomaghemite coated quartz. A pseudo-second order kinetic model fitted the adsorption data well. The sorption capacity of nanomaghemite was evaluated using a Langmuir isotherm model, and a diffuse double layer surface complexation model (DLM) was developed to describe metal adsorption. Adsorption mechanisms were assessed using X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. Pb(II) adsorption occurs mainly via formation of inner-sphere complexes, whereas Cr(VI) likely adsorbs mainly as outer-sphere complexes and Cd(II) as a mixture of inner- and outer-sphere complexes. The simple DLM describes well the pH-dependence of single adsorption edges. However, it fails to adequately capture metal adsorption behavior over broad ranges of ionic strength or metal-loading on the sorbents. For systems with equimolar concentrations of Pb(II), Cd(II), and Cr(VI). Pb(II) adsorption was reasonably well predicted by the DLM, but predictions were poorer for Cr(VI) and Cd(II). This study demonstrates that a simple DLM can describe well the adsorption of the studied metals in mixed sorbate-sorbent systems, but only under narrow ranges of ionic strength or metal loading. The results also highlight the sorption potential of nanomaghemite for metals in complex systems.

Interactions of EDDS with Fe- and Al-(hydr)oxides.

The efficiency of EDDS ([S,S]-ethylenediaminedisuccinate) in metal (phyto) extraction has been discussed in many recent papers. This study demonstrated that the presence of Fe- and Al-(hydr)oxides in soils influences the speciation of EDDS and thus can decrease the extraction of the targeted metallic contaminants (e.g., Pb, Cu, Zn). Above all, amorphous and poorly crystalline oxides (e.g., ferrihydrite) seem to significantly control dissolved Fe and Al concentrations in soils in the presence of metal-EDDS complexes and especially uncomplexed EDDS. Metals released from these minerals compete for the chelating agent and the extraction efficiency of the targeted metals is lowered. The formation of stable Cu-EDDS complexes, which are preferentially formed in soils with high Cu concentrations, results into a lower dissolution of ferrihydrite and goethite compared to free EDDS and Al-EDDS. Information about the contents of amorphous and poorly crystalline oxides in the treated soils would thus be beneficial for choosing efficient EDDS dosages.

Thallium uptake by white mustard (Sinapis alba L.) grown on moderately contaminated soils—Agro-environmental implications

The work focused on Tl uptake by white mustard (Sinapis alba L.) grown on moderately contaminated soils with different characteristics. The data presented here clearly demonstrate the ability of white mustard to (hyper)accumulate Tl. Substantially higher Tl levels were was found in mustard grown on the Arenosol as compared to the carbonate-rich Leptosol; a relationship between the content of labile Tl (adsorbed, bound to carbonates etc.) in soil and its uptake by the plant is suggested. Approximately 3-fold lower concentrations of Tl in roots and stems of the mature mustard (compared to the young plant) indicate a decreasing trend of Tl uptake with the age of the plant. The exchangeable/acid-extractable and reducible Tl fractions were evaluated as the dominant fractions controlling Tl transfer from both contrasting soils. Thallium associated with the residual fraction (e.g., incorporated into silicates) was rather stable in the rhizosphere, proving a negligible influence of root exudates on Tl release from such an operationally defined fraction, despite the anthropogenic origin of Tl. Regarding our results, when mustard is cultivated for nutrition purposes and/or as green manure, it may pose an important source of Tl introduction into the food chain.

Effect of illite and birnessite on thallium retention and bioavailability in contaminated soils.

The influence of illite and birnessite (δ-MnO(2)) amendments on the retention and bioavailability of Tl in contaminated soils was investigated. The efficiency of both phases was evaluated using Tl uptake by white mustard (Sinapis alba L.), sequential extraction and sorption experiments. The obtained data demonstrate that the application of birnessite can effectively transform Tl from the labile (easily mobilizable) fraction to its reducible form, thus lowering Tl bioavailability in soil and subsequent accumulation by plants. The Mn oxide added to the soils reduced substantially Tl uptake; Tl levels in the plants decreased by up to 50%, compared to the non-amended soil. The effect of illite on the immobilization and uptake of Tl was less pronounced, and in the carbonate-rich Leptosol has not been proved at all, suggesting the importance of bulk soil mineralogy and nature of the soil sorption complex on the behavior of this amendment. Therefore, the general applicability of illite for Tl stabilization in soils seems to be limited and strongly dependent on soil composition. In contrast, the use of birnessite like soil additive might be an efficient and environment-friendly solution for soil systems contaminated with Tl.

Brewers draff as a new low-cost sorbent for chromium (VI): Comparison with other biosorbents

In this study, used brewers draff was investigated as a novel sorbent for Cr(VI) and compared with other biosorbents (grape waste, peat moss, and sawdust). FTIR-ATR, BET analysis, and pHPZC determination were used to characterize the sorbents. Kinetic and equilibrium experiments were performed, and two empirical models, Langmuir and Freundlich, were used to describe Cr adsorption. Additionally, packed bed column experiments were also performed. In order to identify possible reduction processes, ion exchange separation on the AG1-X8 resin was used to separate the anionic Cr(VI) and the reduced cationic Cr(III) from the aqueous phase after biosorption. Cr(VI) removal was pH-dependent and fitted well both the Langmuir and the Freundlich isotherm models. The ion exchange separation showed that Cr(VI) reduction had occurred in the solution during biosorption. The efficiency of draff as a biosorbent was comparable (or even higher) to highly organic materials (e.g., composted peat), showing its potential application for Cr(VI) decontamination.

Isotope fractionation and spectroscopic analysis as an evidence of Cr(VI) reduction during biosorption.

This work investigates the mechanisms behind Cr(VI) biosorption/reduction on three biomaterials (brewers draff, grape waste and synthetic humic acid). Coupled Cr isotope analysis with ICP-OES, XPS and SEM was tested as a novel approach to study the reduction of Cr(VI) by the biomaterials. The Cr(VI) biosorption process was accompanied with heavier Cr isotopes enrichment in the remaining Cr(VI) fraction. A significant fractionation of Cr stable isotopes was observed with no significant pH effect; δ(53)Cr of the remaining fraction ranged from 0.2‰ to 1.9‰ while δ(53)Cr of the product (sorbed Cr) ranged from -1.2‰ to -2.8‰. The Rayleigh fractionation model fitted well the measured data and Cr isotope analysis provides thus an efficient tool to quantify Cr(VI) reduction by different biomaterials. In general, the sorption/reduction potential of the three studied biomaterials decreased in the following order: grape waste>humic acids>brewers draff.

Thallium contamination of soils/vegetation as affected by sphalerite weathering: a model rhizospheric experiment.

The environmental stability of Tl-rich sphalerite in two contrasting soils was studied. Rhizospheric conditions were simulated to assess the risk associated with sulfide microparticles entering agricultural (top)soils. The data presented here clearly demonstrate a significant effect of 500 μM citric acid, a model rhizospheric solution, on ZnS alteration followed by enhanced Tl and Zn release. The relative ZnS mass loss after 28 days of citrate incubation reached 0.05 and 0.03 wt.% in Cambisol and Leptosol samples respectively, and was up to 4 times higher, compared to H2O treatments. Incongruent (i.e., substantially increased) mobilization of Tl from ZnS was observed during the incubation time. Generally higher (long-term) stability of ZnS with lower Tl release is predicted for soils enriched in carbonates. Furthermore, the important role of silicates (mainly illite) in the stabilization of mobilized Tl, linked with structural (inter)layer Tl-K exchange, is suggested. Thallium was highly bioavailable, as indicated by its uptake by white mustard; maximum Tl amounts were detected in biomass grown on the acidic Cambisol. Despite the fact that sulfides are thought as relatively stable phases in soil environments, enhanced sulfide dissolution and Tl/trace element release (and bioaccumulation) can be assumed in rhizosphere systems.