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The removal of copper (Cu) in soils by green technology is less treated with urgency, as it is a plant micronutrient. We examined the efficiency of Cu shoot accumulation by herbaceous plants in Cu-contaminated and non-contaminated soils in Trhové Dusniky and Podles, respectively, in the Czech Republic. The total soil Cu content of 81 mg kg -1 in Trhové Dusniky indicated a slight contamination level compared to 50 mg kg -1 , the permissible value by WHO, and < 35 in Podlesí, representing a clean environment. The Cu content was above the permissible value in plants (10 mg kg -1 by WHO) in herbaceous speciesat the control site without trees: Stachys palustris L. (10.8 mg kg -1 ), Cirsium arvense L. (11.3 mg kg -1 ), Achillea millefolium L. (12.1 mg kg -1 ), Anthemis arvense L. (13.2 mg kg -1 ), and Calamagrostis epigejos L. (13.7 mg kg -1 ). In addition, Hypericum maculatum Crantz (10.6 mg kg -1 ), Campanula patula L. (11.3 mg kg -1 ), C. arvense (15 mg kg -1 ), and the highest accumulation in shoot of Equisetum arvense L. (37.1 mg kg -1 ), all under the canopy of trees at the uncontaminated site, were above the WHO value. Leucanthemum Vulgare (Lam.) and Plantago lanceolata L. recorded 11.2 mg kg -1 and 11.5 mg kg -1 , respectively, in the soil of the Cu-contaminated site. These herbaceous species can support the phyto-management of Cu-contaminated soils, especially E. arvense. Critical attention is well-required in the medicinal application of herbaceous plants in treating human ailments due to their Cu accumulation potentials above the threshold. Spontaneous surveys and analysis of Cu speciation in herbaceous species can reveal suitable plants to decontaminate soils and provide caution on consumable products, especially bioactive compounds., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Two groups of invertebrates, terrestrial mollusks (Gastropoda) and Chrysomela populi leaf beetles (Coleoptera: Chrysomelidae), were sampled to estimate the suitability of these organisms as bioindicators of risk element pollution (predominantly Cd, Pb, and Zn) alongside the risk element concentration gradient in the contaminated area (former mining/smelting areas in the vicinity of Příbram city, Central Bohemia, Czech Republic). The individuals representing ten species of terrestrial snails and imagoes of C. populi were collected manually at five sampling sites, differing in the level of soil contamination with risk elements. The findings showed high variability of the results regardless of the element determined, animal species, and sampling location. Among the elements, higher accumulation ability was observed for Cd and Zn, given the higher bioaccessibility of these elements in soils compared to Pb, Cr, and Cu. Higher Cd and Zn accumulation in the soft tissues of gastropods (without any statistically significant differences among the species) compared to C. populi was also recorded. Medians of the bioaccumulation factors (BAFs) reached up to 33.2 for Cd and 5.8 for Zn, in gastropods while reaching up to 3.4 for Cd, and 2.3 for Zn, for C. populi. For both groups of organisms, paradoxically, a higher rate of accumulation of risk elements was observed in all analyzed organisms in sites with lower soil contamination compared to heavily contaminated sites. This indicated the ability of the organisms living in extreme conditions to avoid the uptake of these elements or to move among areas of different contamination levels. Thus, terrestrial gastropods and C. populi proved to be unsuitable bioindicators for assessing soil pollution., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The accuracy of environmental risk assessment depends upon selecting appropriate matrices to extract the most risk-relevant portion of contaminant(s) from the soil. Here, we applied the chelatants EDTA and tartaric acid to extract a metal-contaminated soil. Pistia stratiotes was applied as an indicator plant to measure accumulation from the metal-laden bulk solutions generated, in a hydroponic experiment lasting 15 days. Speciation modeling was used to elucidate key geo-chemical mechanisms impacting matrix and metal-specific uptake revealed by experimental work. The highest concentrations of soil-borne metals were extracted from soil by EDTA (7.4% for Cd), but their uptake and translocation to the plant were restricted due to the formation of stable metal complexes predominantly with DOC. Tartaric acid solubilized metals to a lesser extent (4.6% for Cd), but a higher proportion was plant available due to its presence mainly in the form of bivalent metal cations. The water extraction showed the lowest metal extraction (e.g., 3.9% for Cd), but the metal species behaved similarly to those extracted by tartaric acid. This study demonstrates that not all extractions are equal and that metal-specific speciation will impact accurate risk assessment in soil (water)-plant systems. In the case of EDTA, a deleterious impact on DOC leaching is an obvious drawback. As such, further work should now determine soil and not only metal-specific impacts of chelatants on the extraction of environmentally relevant portions of metal(loid)s., (© 2023. The Author(s).)

The study used scattered literature to summarize the effects of excess Cd, As, and Pb from contaminated soils on plant secondary metabolites/bioactive compounds (non-nutrient organic substances). Hence, we provided a systematic overview involving the sources and forms of Cd, As, and Pb in soils, plant uptake, mechanisms governing the interaction of these risk elements during the formation of secondary metabolites, and subsequent effects. The biogeochemical characteristics of soils are directly responsible for the mobility and bioavailability of risk elements, which include pH, redox potential, dissolved organic carbon, clay content, Fe/Mn/Al oxides, and microbial transformations. The radial risk element flow in plant systems is restricted by the apoplastic barrier (e.g., Casparian strip) and chelation (phytochelatins and vacuole sequestration) in roots. However, bioaccumulation is primarily a function of risk element concentration and plant genotype. The translocation of risk elements to the shoot via the xylem and phloem is well-mediated by transporter proteins. Besides the dysfunction of growth, photosynthesis, and respiration, excess Cd, As, and Pb in plants trigger the production of secondary metabolites with antioxidant properties to counteract the toxic effects. Eventually, this affects the quantity and quality of secondary metabolites (including phenolics, flavonoids, and terpenes) and adversely influences their antioxidant, antiinflammatory, antidiabetic, anticoagulant, and lipid-lowering properties. The mechanisms governing the translocation of Cd, As, and Pb are vital for regulating risk element accumulation in plants and subsequent effects on secondary metabolites., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The North Bohemian Brown Coal Basin (Czech Republic) is suggested as a source of significant pollution in the surrounding environment with various pollutants, including risk elements. A total of 53 sampling points were selected within the North Bohemian region. The selected sampling points represented either the basin areas (affected by the coal mining and related activities) or the mountain areas (an area unaffected by the coal mining but characterized by the geogenic sources of the risk elements). At each of the sampling points, soils and respective dominant indigenous plant samples were collected. A suite of ecological indices, namely, individual pollution index (Ii), Nemerow index (PN), bioaccumulation factor (BAF), translocation factor (TF), and hazard quotient (HQ), were applied to estimate the environmental risk of As, Be, Cd, and Zn levels in soils, potential soil-plant transfer, and soil-plant-animal transport of these stated elements. The results from Ii showed that the maximum values of As, Be, Cd, and Zn in the investigated soils exceeded the preventive values, where the Ii value was up to 58 for As in the mountain areas, indicating severe pollution. At the same time, mild pollution was recorded in the case of Cd. For Be in the researched soils, its Ii assessment result was a wide range, varying between a clean environment and severe pollution. Whereas As and Be uptake by plants was limited and these elements were retained in the plant's roots, relatively high mobility and soil to plant shoots transport ability of Cd were recorded and documented by the TF values. The HQs calculated for selected herbivorous mammals in the area showed that the potential health risk of As and Be was limited to only plant roots in the hotspots with extreme As and Be contents. In comparison, substantial health risk of Cd was observed in the aboveground biomass of plants. Therefore, the potential remediation of the coal mining areas should be focused on (i) identification of the As and Be hotspots and (ii) to reduce the mobility and plant availability of Cd in the whole investigated area., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The phytoextraction potential of short-rotation field coppice plantations was investigated on soil historically contaminated with risk elements (REs), especially Cd, Pb and Zn. The main objective of the study was to assess the effect of biomass harvest time (summer harvest versus traditional winter one) on biomass yield, REs accumulation and removal in the long-term study. The precise field experiment with two Salix clones and two Populus clones was established in April 2009. Shoots of all clones were harvested in February 2012 for the first time, and then identical branches and leaves were harvested every two years in September (summer harvest = SH) and the branches every two years in February (winter harvest = WH). The first summer harvest seemed to be more promising compared to the winter one, but the yields in the second and third harvests were inconsistent. The total phytoextraction efficiency of the SH declined in second and third harvests due to a decrease of leaves/aboveground biomass ratio, and the RE concentrations in leaves. Clonal Salix smithiana was the most productive one in the SH, with a dry matter yield of 15.1 t ha -1 year -1 and showed promising extraction ability for Cd (11.65 %) and Zn (4.59 %) over a 6-year field experiment. A lower portion of Cd (6.97 %) and Zn (2.38 %) was removed by this clone in the WH (calculated from the total soil content of REs). SH was more reasonable for phytoextraction compared to WH. Higher RE concentrations were found in leaves of Salix compared to Populus. Populus accumulated the highest Pb content in the branches; unfortunately, the Pb extraction was low, due to extremely high soil Pb contamination. Locally bred willows and poplars performed substantially better than internationally recognised ones, indicating the importance of phytoremediation optimisation, including clone selection, for suitable climatic conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Long-term brown coal mining contributes to risk element contents in soils surrounding coal basins. However, there is a lack of bioaccessibility characterization of the risk elements in the soils at the impacted locations for estimation of the potential health risk, in relation to the effects of soil particle size and element origin. In this study, soils from different geological areas (geogenic vs. anthropogenic) were sampled around the Most brown coal basin, Czech Republic. These soils were passed through sieves to obtain seven aggregate size fractions. For an estimation of the oral bioaccessibility of As and Pb in the size fractions, the physiologically based extraction test was applied, whereas the potential pulmonary bioaccessibility of the elements was estimated by using both Gamble's and Hatch's tests. The results showed that the geochemical pattern of the investigated elements clearly separates the soil samples collected from the mountain region (mineralization from geogenic processes) from those of the basin region (extensive coal mining). For As, the results indicated that it poses higher risks in the anthropogenically affected basin region due to its higher gastro-intestinal and pulmonary bioaccessibility in soil samples in this area. A higher bioaccessibility of As in the soils was recorded in the finer grain size fractions, which are usually air-borne and can be easily ingested and/or inhaled, leading to potential health risks to humans and livestock. The opposite pattern, with a higher content on coarse particles, was recorded for Pb, indicating a potential risk of livestock in the non-forest mountainous areas., (© 2021. The Author(s), under exclusive licence to Springer Nature B.V.)

Biosolids were applied as a fertilizer after drying, torrefaction (220, 320 °C), and pyrolysis (420, 520, 620 °C). Lettuce was grown on contrasting soils, and the transfer of pharmaceuticals to aboveground biomass was assessed. Of 42 compounds detected in dried biosolids, 10 were found in lettuce. Their potency for translocation to aerial parts was in the order: ethenzamide > carbamazepine > mirtazapine~tramadol > N-desmethyltramadol~solifenacin > sertraline~trazodone~venlafaxine > propafenone. Application of dried biosolids resulted in the highest uptake of pharmaceuticals and the neutral soil further intensified the uptake due to prevalent neutral speciation of the ionizable basic molecules. Torrefaction reduced the total pharmaceutical content in biosolids by 92.2% and 99.5% at 220 and 320 °C, respectively. Torrefied biosolids significantly reduced the uptake of pharmaceuticals and led to the highest biomass on acidic soil but were phytotoxic on the neutral soil. Pyrolysed biosolids increased the biomass production of lettuce on both soils and blocked the uptake of pharmaceuticals. A minimum biosolids pyrolysis temperature of 420 °C should be ensured prior to soil application as it represents a good compromise between fertilization potential, pharmaceutical uptake, and homogeneity of plant response regardless of the soil characteristics., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The city of Litvínov (North Bohemia, Czech Republic) is seriously affected by coal mining, coal processing, and intensive industrial activities. Within the urban area, the potential environmental hazard of risk elements (in soil and vegetation) and polycyclic aromatic hydrocarbons (PAHs, in soils) was estimated using selected environmental and human health hazard indices. In total, 24 sites were sampled, including the city center, residential areas, industrialized zone, and areas close to operating and/or abandoned coal mines. The results showed elevated values of As, Cd, Cu, Ni, Pb, and Zn in soils (the maximum levels of individual pollution indices varied between 3 and 5 for As, Pb, and Zn); the risk assessment code (RAC) values indicated high bioaccessibility of Cd and Zn. The high mobility of Cd was confirmed by their bioaccumulation factors (BAF) in the aboveground biomass of Taraxacum sect. Ruderalia and Polygonum aviculare, reaching up to 1.9 and 2.9, respectively. The Cd content in plants presents a substantial health hazard for herbivores such as Oryctolagus cuniculus living within the urban area. The PAH levels in the soils also showed elevated values; the contents of benzo(a)pyrene exceeded more than 2-fold the indicative values for potential health risk for biota, especially near the abandoned coal mines. The incremental lifetime cancer risks (ILCR) for ingestion of the contaminated soil showed only low or negligible cancerogenic risk, varying between 6.7 × 10 -7 and 1.6 × 10 -5 for children, and between 9.9 × 10 -7 and 2.7 × 10 -6 for adults. However, the potential health impact of the inhalation of the contaminated particulate matter should be included in the further research. Although the contamination level in the investigated area does not represent an imminent environmental and health risk, the potential remediation measures should be considered in the future.

Metal-polluted soils represent hostile environments affecting the composition and functions of soil microbial communities. This study evaluated the implication of combining the mycoremediated dry olive residue (MDOR) amendment application with the inoculation of the arbuscular mycorrhizal fungi (AMF) Funneliformis mosseae in restoring the quality, composition, and functionality of soil microbial communities. To achieve this aim, a mesocosms experiment was set up that included three variations: i) with and without application of Penicillium chrysogenum-10-transformed MDOR (MDOR&#95;Pc), and Chondrosterum purpureum-transformed MDOR (MDOR&#95;Cp) amendments; ii) with and without F. mosseae inoculation; and iii) 30-day and 60-day soil treatment time. As a result of this combined treatment, changes in the soil labile organic C and N fractions were observed throughout the experiment. Increases in the abundance of phospholipid fatty acids (PLFAs) for bacteria, actinobacteria, and Gram- and Gram+ bacteria were also recorded at the end of the experiment. The addition of MDOR amendments boosted fungal and AM fungi communities. AM fungi root and soil colonization was also enhanced as the result of improvement nutrient turnover and spatial conditions caused by adding MDOR in combination with an inoculation of F. mosseae. The composition and functionality of microbial communities seemed to be an important ecological attribute indicating an apparently fully functional restoration of this metal-polluted soil and therefore suggesting the suitability of the combined MDOR and AM fungus treatment as a reclamation practice., (Copyright © 2019. Published by Elsevier Ltd.)

The establishment of phytoextraction crops on highly contaminated soils can be limited by metal toxicity. A recent proposal has suggested establishing support crops during the critical initial phase by metal immobilization through soil amendments followed by subsequent mobilization using elemental sulphur to enhance phytoextraction efficiency. This 'combined phytoremediation' approach is tested for the first time in a pot experiment with a highly contaminated soil. During a 14-week period, relatively metal-tolerant maize was grown in a greenhouse under immobilization (before sulphur (S) application) and mobilization (after S application) conditions with soil containing Cd, Pb and Zn contaminants. Apart from the control (C) sample, the soil was amended with activated carbon (AC), lignite (Lig) or vermicompost (VC) all in two different doses (dose 1~45 g additive kg -1 soil and dose 2~90 g additive kg -1 soil). Elemental S was added as a mobilization agent in these samples after 9 weeks. Biomass production, nutrient and metal bioavailability in the soil were determined, along with their uptake by plants and the resulting remediation factors. Before S application, Cd and Zn mobility was reduced in all the AC, Lig and VC treatments, while Pb mobility was increased only in the Lig1 and VC1 treatments. Upon sulphur application, Fe, Mn, Cd, Pb and Zn mobility was not significantly affected in the C, AC and VC treatments, nor total Cd, Pb and Zn contents in maize shoots. Increased sulphate, Mn, Cd, Pb and Zn mobilities in soil together with related higher total S, Mn, Pb and Zn contents in shoots were observed in investigated treatments in the last sampling period. The highest biomass production and the lowest metal toxicity were seen in the VC treatments. These results were associated with effective metal immobilization and showed the trend of steady release of some nutrients. The highest remediation factors and total elemental content in maize shoots were recorded in the VC treatments. This increased phytoremediation efficiency by 400% for Cd and by 100% for Zn compared to the control. Considering the extreme metal load of the soil, it might be interesting to use highly metal-tolerant plants in future research. Future investigations could also explore the effect of carbonaceous additives on S oxidation, focusing on the specific microorganisms and redox reactions in the soil. In addition, the homogeneous distribution of the S rate in the soil should be considered, as well as longer observation times.

The risk element accumulation ability of two groups of epigeic species, insects from families Coleoptera and Hymenoptera (namely Formicidae), was determined and related to soil risk element content and bioaccessibility. The study was conducted in the district of Příbram, Czech Republic, which was characterised by extremely high aged pollution in the soils, including risk elements, especially As, Pb, Zn and Cd, due to the former mining and smelting activity. Four sampling sites differing in their pseudo-total risk element contents were selected and composite samples of individuals representing either Coleoptera or Formicidae were sampled at the individual sampling points. The results indicate the ability of Coleoptera and Formicidae organisms to accumulate risk elements, especially at the location with extremely high soil risk element content. In soil containing up to 841 mg As kg -1 , 84.6 mg Cd kg -1 , 4250 mg Pb kg -1 and 8542 mg Zn kg -1 , contents in insect bodies reached 239 mg As kg -1 As, 24.2 mg Cd kg -1 , 70.4 mg Pb kg -1 and 335 mg Zn kg -1 in beetles and up to 20.9 mg As kg -1 , 29.9 mg Cd kg -1 , 111 mg Pb kg -1 and 657 mg Zn kg -1 in ants. Therefore, bioaccumulation factors (BAFs) varied between 0.02 and 0.55. Increasing Cd content in Coleoptera bodies with increasing soil pseudo-total element content was observed only among the investigated elements. However, the results indicate increasing BAF values with decreasing soil element levels, especially for Cd, Pb and Zn, indicating limited uptake of elements by the organisms living in contact with extremely contaminated soil.

The potential environmental hazards of risk elements in the area affected by the opencast coal mine and/or coal combustion for plants and animals was assessed by using a suite of laboratory bioaccessibility tests. The chosen sampling area was in the vicinity of the largest coal mine spoil in the Sokolov coal basin (Czech Republic). For an estimation of the oral bioaccessibility of the risk elements in soils, the physiologically based extraction tests were applied. Among the available methods for estimating the pulmonary bioaccessibility of elements, the Gamble's and Hatch's tests were chosen. The results showed elevated pseudo-total soil contents of As, Be, Cd, Cu, Pb, V, and Zn. Among these elements, only Cd showed substantial bioaccessibility for plants, as documented by the high Risk Assessment Code, reaching up to 47%, and the highest plant-availability, where the maximum Bioaccumulation Factor in plants reached up to 4.5. The simulated body fluids showed the highest bioaccessibility of Cd, but also substantial bioaccessible pools of As and Be, the elements frequently found at the brown coal mining and processing areas. For better understanding of the risk element bioaccessibility under the specific conditions, the released element pools should be related to the particular soil physicochemical parameters.

The clones of fast-growing trees (FGTs) were investigated for phytoextraction of soil contaminated with risk elements (REs), especially Cd, Pb, and Zn. As a main experimental factor, the potential effect of biomass harvesting time was assessed. The field experiment with two Salix clones (S1 - (Salix schwerinii × Salix viminalis) × S. viminalis, S2 - S. × smithiana) and two Populus clones (P1 - Populus maximowiczii × Populus nigra, P2 - P. nigra) was established in April 2009. Shoots of all clones were first harvested in February 2012. After two further growing seasons, the first half of the trees was harvested in September 2013 before leaf fall (summer harvest) and the second half in February 2014 (winter harvest). Remediation factors (RFs) for all clones and all REs (except Pb for clone S1) were higher in the summer harvest. The highest annual RFs for Cd and for Zn (1.34 and 0.67%, respectively) were found for clone S2 and were significantly higher than other clones. Although no increased mortality of trees harvested in the summer was detected in the following season, the effect of summer harvesting on the phytoextraction potential of FGTs clones should be investigated in long-term studies.

Central Bohemia (Czech Republic) has highly developed industry and a dense rail network. Here, we aimed to determine the content of risk elements in dandelion plants (Taraxacum sect. Ruderalia) growing near train stations, industrial enterprises, and in the city parks of 16 cities in the Central Bohemian region. The highest element contents in the soils were found in industrial areas affected by the historical mining and smelting activities; contemporary industry showed no substantial effect on the soil element contents. The median values of element contents (As, Be, Cd, Co, Cr, Cu, Ni, Pb, and Zn) at the railway station sites were the highest among the monitored sites, where the differences between park and station sites were significant for Be, Co, and Zn. Although the intensity of the traffic at the individual stations differed, we found that long-term regular traffic enhanced the element contents in the soils and, subsequently, in the plants. For Cd, Co, Cr, Cu, Pb, V, and Zn, the highest median element contents were found in plant roots, regardless of the sampling site. For Cd and Zn, the contents in leaves were higher than in the inflorescences, and the opposite pattern was recorded for Co and Cu. As and Be were distributed equally among the plant parts. Among the sampling sites, the As, Be, Cd, Zn, and Pb contents in the plant roots tended to have higher median values at the station sites, confirming the results of our soil analyses. We detected a fairly good correlation between soil and plant content for cadmium, regardless of the sampling site, soil element content, or analyzed part of the plant. Thus, we propose that dandelion is a suitable bioindicator of cadmium pollution of soil.

Abandoned gold mines are often suggested as potential sources of environmental pollution. Thus, the soils within the area of a gold mine in Libčice, Czech Republic, were monitored. Elevated element contents were found of As, Cd, Cu, Hg, Pb, and Zn. The risk assessment codes (RACs) indicated high environmental risk from soil Cd, and moderate risk from Zn, whereas the risk of As, Cu, and Pb was low. It was supported by the analysis of 134 samples of aboveground biomass of plants, where the levels of As and Pb were below the detection limit. For Cd, the plant uptake reflected the high mobility of this element, where the bioaccumulation factors (BAFs) varied in range 0.032 (Fragaria vesca) and 1.97 (Circia arvensis). For 11% of samples the BAF values for Cd exceeded 1. For Hg, although the maximum BAF did not exceed 0.37 (Lotus corniculatus), the Hg contents in plants occasionally exceeded the threshold limits for Hg contents in raw feedstuffs. The investigated gold mine does not represent a direct environmental risk, but the fate of Cd and Hg in the soils and plants suggests the necessity of a deeper understanding of the penetration of these elements into the surrounding environment.

The use of biotransformed dry olive residue (DOR) as organic soil amendment has recently been proposed due to its high contents of stabilized organic matter and nutrients. The potential of biotransformed DOR to immobilize risk elements in contaminated soils might qualify DOR as a potential risk element stabilization agent for in situ soil reclamation practices. In this experiment, the mobility of risk elements in response to Penicillium chrysogenum-10-transformed DOR, Funalia floccosa-transformed DOR, Bjerkandera adusta-transformed DOR, and Chondrostereum purpureum-transformed DOR as well as arbuscular mycorrhizal fungi (AMF), Funneliformis mosseae, inoculation was investigated. We evaluated the effect of these treatments on risk element uptake by wheat (Triticum aestivum L.) plants in a pot experiment with Cd, Pb, and Zn contaminated soil. The results showed a significant impact of the combined treatment (biotransformed DOR and AMF inoculation) on wheat plant growth and element mobility. The mobile proportions of elements in the treated soils were related to soil pH; with increasing pH levels, Cd, Cu, Fe, Mn, P, Pb, and Zn mobility decreased significantly (r values between -0.36 and -0.46), while Ca and Mg mobility increased (r = 0.63, and r = 0.51, respectively). The application of biotransformed DOR decreased risk element levels (Cd, Zn), and nutrient concentrations (Ca, Cu, Fe, Mg, Mn) in the aboveground biomass, where the elements were retained in the roots. Thus, biotransformed DOR in combination with AMF resulted in a higher capacity of wheat plants to grow under detrimental conditions, being able to accumulate high amounts of risk elements in the roots. However, risk element reduction was insufficient for safe crop production in the extremely contaminated soil., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Willows (Salix spp.) are considered to be effective for the phytoremediation of trace elements from contaminated soils, but their efficiency is limited in heavily polluted soils because of poor growth. Liming can be a desirable measure to decrease the plant availability of elements, resulting in improved plant development. Notably, large root area and maximum soil penetration are basic parameters that improve the efficiency of phytoremediation. The impact of soil chemical properties on willow root anatomy and the distribution of trace elements below-ground have rarely been studied. The effect of liming on root parameters, biomass allocation and trace element distribution in non-harvestable (coarse roots, fine roots, stumps) and harvestable plant parts (twigs and leaves) of Salix × smithiana was assessed at the end of a 4-year pot experiment with two trace element-polluted soils that differed in terms of soil pH. Stump biomass predominated in weakly acidic soil. In neutral soil, the majority of biomass was located in fine roots and stumps; the difference from other plant parts was minor. Trace elements were the most concentrated in fine roots. Translocation to above-ground biomass increased as follows: Pb < As < Zn~Cd. In contrast to Cd and Zn, great differences in As and Pb mobility in plants were recorded after measurements of individual below-ground biomass (stumps < coarse roots < fine roots). Lime application decreased the concentrations of mobile Cd and Zn and related levels in plants, improved biomass production and root parameters and increased the removal of all trace elements in weakly acidic soil. None or minimum differences in the monitored parameters were recorded for dolomite treatments in both soils. The dose and source of liming had crucial effects on root anatomy. Growing willows in limed trace element-polluted soils is a suitable measure for combination of two remediation strategies, i.e. phytoextraction of Cd and Zn and assisted phytostabilization of As and Pb.

Crop rotation long-term field experiments were established in 1955 and 1956 at three locations in the Czech Republic (Čáslav, Ivanovice, and Lukavec) differing in their climatic and soil physicochemical properties. The effect of long-term application of farmyard manure and farmyard manure + NPK treatments on plant-available, easily mobilizable, potentially mobilizable, and pseudo-total contents of arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) contents in soils (in 2013) as well as the uptake of these elements by winter wheat (Triticum aestivum L.) grain and straw were analyzed in the two following seasons: 2012 and 2013. The treatments resulted in increasing the soil pH level when compared to the control, but the cation exchange capacity remained unchanged. Although all fertilizers were applied for six decades, the pseudo-total concentration elements in both the soil and wheat plants stayed far below those of the Czech and European threshold limits for agricultural soils and cereals for human nutrition and feedstuff. Although the mobile pools of As, Cu, and Zn were slightly changed at the treated soils, these changes were not related to the element uptake by the wheat plants. Moreover, the effect of the location and growing season was more decisive for the differences in soil and plant element contents than for the individual treatments. Thus, the long-term application of farmyard manure did not result in any substantial change in risk element contents in both soils and winter wheat plants.

Olive oil production is one of the most relevant agroindustrial activities in the Mediterranean region and generates a huge amount of both solid and semi-solid wastes, the uncontrolled disposal of which might lead to serious environmental problems. Due to its organic matter and mineral nutrient content, the waste material can be applied to agricultural soil as a fertilizer. However, due to its high organic matter content, dry olive residue (DOR), commonly called "alperujo," has the potential to immobilize risk elements in contaminated soils. The main objective of this study was to assess the possible effect of DOR on sorption of risk elements such as cadmium (Cd), lead (Pb), and zinc (Zn) in the soil. A set of batch sorption experiments were carried out to assess the ability of DOR to adsorb Cd, Pb, and Zn where the effect of the preceding biotransformation of DOR by four species of fungi: Penicillium chrysogenum, Coriolopsis floccosa, Bjerkhandera adusta, and Chondrostereum purpureum was compared. The Freundlich and Langmuir sorption isotherms were calculated to assess the sorption characteristics of both transformed and non-transformed DOR. The results showed good potential sorption capacity of DOR, especially for Pb and to a lesser extent for Cd and Zn. Better sorption characteristics were reported for the biotransformed DOR samples, which are expected to show higher humification of the organic matter. However, the desorption experiments showed weakness and instability of the DOR-bound elements, especially in the case of Zn. Thus, future research should aim to verify the DOR sorption pattern in contaminated soil as well as the potential stabilization of the DOR element bounds where the increase of the pH levels of the DOR samples needs to be taken into account.

On the basis of a previous study performed in our laboratory, the use of organic and inorganic amendments can significantly modify the Hg mobility in soil. We have compared the effectiveness of organic and inorganic amendments such as digestate and fly ash, respectively, reducing the Hg mobility in Chernozem and Luvisol soils differing in their physicochemical properties. Hence, the aim of this work was to compare the impact of digestate and fly ash application on the chemical and biochemical parameters in these two mercury-contaminated soils in a model batch experiment. Chernozem and Luvisol soils were artificially contaminated with Hg and then incubated under controlled conditions for 21 days. Digestate and fly ash were applied to both soils in a dose of 10 and 1.5 %, respectively, and soil samples were collected after 1, 7, 14, and 21 days of incubation. The presence of Hg in both soils negatively affected to processes such as nitrification, provoked a decline in the soil microbial biomass C (soil microbial biomass C (MBC)), and the microbial activities (arylsulfatase, and β-glucosaminidase) in both soils. Meanwhile, the digestate addition to Chernozem and Luvisol soils contaminated with Hg improved the soil chemical properties (pH, dissolved organic carbon (DOC), N (Ntot), inorganic-N forms (N-NH4 (+) and N-NO3 (-))), as consequence of high content in C and N contained in digestate. Likewise, the soil MBC and soil microbial activities (dehydrogenase, arylsulfatase, and β-glucosaminidase) were greatly enhanced by the digestate application in both soils. In contrast, fly ash application did not have a remarkable positive effect when compared to digestate in Chernozem and Luvisol soil contaminated with mercury. These results may indicate that the use of organic amendments such as digestate considerably improved the soil health in Chernozem and Luvisol compared with fly ash, alleviating the detrimental impact of Hg. Probably, the chemical properties present in digestate may determine its use as a suitable amendment for the assisted-natural attenuation of mercury-polluted soils.

Three Cd and Zn hyperaccumulating plant species Noccaea caerulescens Noccaea praecox and Arabidopsis halleri (Brassicacceae) were cultivated in seven subsequent vegetation seasons in both pot and field conditions in soil highly contaminated with Cd, Pb, and Zn. The results confirmed the hyperaccumulation ability of both plant species, although A. halleri showed lower Cd uptake compared to N. caerulescens. Conversely, Pb phytoextraction was negligible for both species in this case. Because of the high variability in plant yield and element contents in the aboveground biomass of plants, great variation in Cd and Zn accumulation was observed during the experiment. The extraction ability in field conditions varied in the case of Cd from 0.2 to 2.9 kg ha(-1) (N. caerulescens) and up to 0.15 kg ha(-1) (A. halleri), and in the case of Zn from 0.2 to 6.4 kg ha(-1) (N. caerulescens) and up to 13.8 kg.ha(-1) (A. halleri). Taking into account the 20 cm root zone of the soil, the plants were able to extract up to 4.1% Cd and 0.2% Zn in one season. However, cropping measures should be optimized to improve and stabilize the long-term phytoextraction potential of these plants.

The precise characterization of the behavior of individual microorganisms in the presence of increased mercury contents in soil is necessary for better elucidation of the fate of mercury in the soil environment. In our investigation, resistant bacterial strains isolated from two mercury contaminated soils, represented by Paenibacillus alginolyticus, Burkholderia glathei, Burkholderia sp., and Pseudomonas sp., were used. Two differently contaminated soils (0.5 and 7 mg kg(-1) total mercury) were chosen. Preliminary soil analysis showed the presence of methylmercury and phenylmercury with the higher soil mercury level. Modified rhizobox experiments were performed to assess the ability of mercury accumulating strains to deplete the mobile and mobilizable mercury portions in the soil by modification; microbial agar cultures were used rather than the plant root zone. A sequential extraction procedure was performed to release the following mercury fractions: water soluble, extracted in acidic conditions, bound to humic substances, elemental, and bound to complexes, HgS and residual. Inductively coupled plasma mass spectrometry (ICP-MS) and a single-purpose atomic absorption spectrometer (AMA-254) were applied for mercury determination in the samples and extracts. Gas chromatography coupled to atomic fluorescence spectrometry (GC-AFS) was used for the determination of organomercury compounds. The analysis of the microbial community at the end of the experiment showed a 42% abundance of Paenibacillus sp. followed by Acetivibrio sp., Brevibacillus sp., Cohnella sp., Lysinibacillus sp., and Clostridium sp. not exceeding 2% abundance. The results suggest importance of Paenibacillus sp. in Hg transformation processes. This genus should be tested for potential bioremediation use in further research.

Fast-growing clones of Salix and Populus have been studied for remediation of soils contaminated by risk elements (RE) using short-rotation coppice plantations. Our aim was to assess biomass yield and distributions of elements in wood and bark of highly productive willow (S1--[Salix schwerinii × Salix viminalis] × S. viminalis, S2--Salix × smithiana clone S-218) and poplar (P1--Populus maximowiczii × Populus nigra, P2--P. nigra) clones with respect to aging. The field experiment was established in April 2008 on moderately Cd-, Pb- and Zn- contaminated soil. Shoots were harvested after four seasons (February 2012) and separated into annual classes of wood and bark. All tested clones grew on contaminated soils, with highest biomass production and lowest mortality exhibited by P1 and S2. Concentrations of elements, with exception of Ca and Pb, decreased with age and were higher in bark than in wood. The Salix clones were characterised by higher removal of Cd, Mn and Zn compared to the Populus clones. Despite generally higher RE content in young shoots, partly due to lower wood/bark ratios and higher RE concentrations in bark, the overall removal of RE was higher in older wood classes due to higher biomass yield. Thus, longer rotations seem to be more effective when phytoextraction strategy is considered. Of the four selected clones, S1 exhibited the best removal of Cd and Zn and is a good candidate for phytoextraction.

Soil from Trhové Dušníky (Příbram, Czech Republic) is characterized by its high polymetallic accumulations in Pb-Ag-Zn due to mining and smelting activities. In previous studies performed in our research group, we have evaluated the potential use of amendments that would reduce the mobility and availability of metals such as Hg. We have observed that the application of digestate and fly ash in metal-polluted soil has an impact in immobilizing these metals. However, until now we have lacked information about the effect of these amendments on soil microbial functionality and communities. The multi-contaminated soil was used to grow wheat in a pot experiment to evaluate the impact of digestate and fly ash application in soil microbial communities. Soil samples were collected after 30 and 60 days of treatment. The digestate application improved chemical attributes such as the content in total organic carbon (TOC), water soluble carbon (WSOC), total soluble carbon (C), total soluble nitrogen (N), and inorganic N forms (NO3(-)) as consequence of high content in C and N which is contained in digestate. Likewise, microbial activity was greatly enhanced by digestate application, as was physiological diversity. Bacterial and fungal communities were increased, and the microbial biomass was highly enhanced. These effects were evident after 30 and 60 days of treatment. In contrast, fly ash did not have a remarkable effect when compared to digestate, but soil microbial biomass was positively affected as a consequence of macro- and micro-nutrient sources applied by the addition of fly ash. This study indicates that digestate can be used successfully in the remediation of metal-contaminated soil., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Potential changes in the mobility and bioavailability of risk and essential macro- and micro-elements achieved by adding various ameliorative materials were evaluated in a model pot experiment. Spring wheat (Triticum aestivum L.) was cultivated under controlled condition for 60 days in two soils, uncontaminated Chernozem and multi-element contaminated Fluvisol containing 4900 ± 200 mg/kg Zn, 35.4 ± 3.6 mg/kg Cd, and 3035 ± 26 mg/kg Pb. The treatments were all contained the same amount of sulfur and were as follows: (i) digestate from the anaerobic fermentation of biowaste, (ii) fly ash from wood chip combustion, and (iii) ammonium sulfate. Macro- and micro-nutrients Ca, Mg, K, Fe, Mn, Cu, P, and S, and risk elements Cd, Cr, Pb, and Zn were assayed in soil extracts with 0.11 mol/l solution of CH3COOH and in roots, shoots, and grain of wheat after 30 and 60 days of cultivation. Both digestate and fly ash increased levels of macro- and micro-nutrients as well as risk elements (especially Cd and Zn; the mobility of Pb decreased after 30 days of cultivation). The changes in element mobility in ammonium sulfate-treated soils appear to be due to both changes in soil pH level and inter-element interactions. Ammonium sulfate tended to be the most effective measure for increasing nutrient uptake by plants in Chernozem but with opposite pattern in Fluvisol. Changes in plant yield and element uptake in treated plants may have been associated with the higher proline content of wheat shoots cultivated in both soils compared to control. None of the treatments decreased uptake of risk elements by wheat plants in the extremely contaminated Fluvisol, and their accumulation in wheat grains significantly exceeded maximum permissible levels; these treatments cannot be used to enable cereal and other crop production in such soils. However, the combination of increased plant growth alongside unchanged element content in plant biomass in pots treated with digestate and fly ash suggests that these treatments have a beneficial impact on yield and may be effective treatments in crops grown for phytoremediation.

Total selenium (Se) contents were determined in aboveground biomass of wild plant species growing in two uncultivated meadows at two different locations. The soils in these locations had pseudototal (Aqua Regia soluble) Se in concentration ranges of between 0.2 and 0.3 mg kg(-1) at the first location, and between 0.7 and 1.4 mg kg(-1) at the second location. The plant species represented 29 plant families where the most numerous ones were Poaceae, Rosaceae, Fabaceae , and Asteraceae. The selenium contents in the plants varied between undetectable levels (Aegopodium podagraria, Achillea millefolium, Lotus corniculatus) and 0.158 mg kg(-1) (Veronica arvensis, Veronicaceae). The Se levels were roughly one order of magnitude lower compared to other elements with similar soil content, such as cadmium and molybdenum. The transfer factors of Se, quantifying the element transfer from soil to plants, varied between <0.001 and 0.146 with no significant differences between the locations, confirming the limited soil-plant selenium transfer regardless of location, soil Se level, and plant species. Among the plant families, no unambiguous trend to potential elevated Se uptake was observed. Low Se content in the soil and its plant availability was comparable to other Se-deficient areas within Europe.

Aquatic weeds are widely used as animal feed in developing countries. However, information about element bioavailability from these plants is lacking. A combination of an in vitro method [physiologically based extraction test (PBET)] and an in vivo feeding trial was used in this study to investigate potential element bioaccessibility and estimated bioavailability of Pistia stratiotes (PS). Cu, Fe, Mn, Zn, and Pb concentrations in PS biomass, artificial gastrointestinal fluids, and rat tissues were determined using atomic absorption spectrometry with electrothermal atomization and inductively coupled plasma-atomic emission spectrometry. PS exhibited elevated Fe, Mn, and Pb levels. The PBET revealed high bioaccessibility of all monitored elements from PS biomass. The results of the in vivo trial were inconsistent with those of the PBET, because animals fed PS exhibited low levels of essential elements in the tissues. The consumption of a PS-supplemented diet significantly decreased total Fe levels and increased the total level of accumulation of Pb in exposed animals. Significantly reduced amounts of essential elements in the intestinal walls indicated a potential disruption in nutrient gastrointestinal absorption in animals fed PS.

To characterize the phytoextraction efficiency of two clones of willow trees (Salix x smithiana Willd., Salix rubens) and two clones of poplar trees (Populus nigra x maximowiczii, Populus nigra Wolterson) were planted in contaminated soil (0.4-2.0 mg Cd.kg(-1), 78-313 mg Zn.kg(-1), 21.3-118 mg Cu.kg(-1)). Field experiment was carried out in Czech Republic. The study investigated their ability to accumulate heavy metals (Cd, Zn, and Cu) in harvestable plant parts. The poplars produced higher amount of biomass than willows. Both Salix clones accumulated higher amount of Cd, Zn and Cu in their biomass (maximum 6.8 mg Cd.kg(-1), 909 mg Zn.kg(-1), and 17.7 mg Cu.kg(-1)) compared to Populus clones (maximum 2.06 mg Cd.kg(-1), 463 mg Zn.kg(-1), and 11.8 mg Cu.kg(-1)). There were no significant differences between clones of individual species. BCs for Cd and Zn were greater than 1 (the highest in willow leaves). BCs values of Cu were very low. These results indicate that Salix is more suitable plant for phytoextraction of Cd and Zn than Populus. The Cu phytoextraction potential of Salix and Populus trees was not confirmed in this experiment due to low soil availability of this element.

Increased endogenous plant cytokinin (CK) content through transformation with an isopentyl transferase (ipt) gene has been associated with improved plant stress tolerance. The objective of this study is to determine amino acid changes associated with elevated CK production in ipt transgenic tobacco (Nicotiana tabacum L., cv. Wisconsin 38). Nontransformed (WT) and transformed tobacco plants with ipt gene controlled by senescence-activated promoter (SAG) were exposed to zinc soil contamination (tested levels Zn1=250, Zn2=500, Zn3=750 mg kg(-1) soil). The Zn effect on plant stress metabolism resulted in changes in levels of selected free amino acids playing an important role in adaptation to stress and plant senescence (alanine, leucine, proline, methionine and γ-aminobutyrate) and differed for transformed and nontransformed tobacco plants. Analyses of amino acids confirmed that SAG tobacco plants had improved zinc tolerance compared with the WT plants. The enhanced Zn tolerance of SAG plants was associated with the maintenance of accumulation of proline, methionine and γ-aminobutyrate. The concentrations of leucine and alanine did not show significant differences between plant lines., (© 2013 Published by Elsevier Inc.)

Both soil organic matter and sulfur (S) can reduce or even suppress mercury (Hg) mobility and bioavailability in soil. A batch incubation experiment was conducted with a Chernozem and a Luvisol artificially contaminated by 440 mg · kg(-1) Hg showing wide differences in their physicochemical properties and available nutrients. The individual treatments were (i) digestate from the anaerobic fermentation of biowaste; (ii) fly ash from wood chip combustion; and (iii) ammonium sulfate, and every treatment was added with the same amount of S. The mobile Hg portion in Chernozem was highly reduced by adding digestate, even after 1 day of incubation, compared to control. Meanwhile, the outcome of these treatments was a decrease of mobile Hg forms as a function of incubation time whereas the contents of magnesium (Mg), potassium (K), iron (Fe), manganese (Mn), copper (Cu), zinc (Zn), and phosphorus (P) were stimulated by the addition of digestate in both soils. The available calcium (Ca) contents were not affected by the digestate addition. The experiment proved digestate application as the efficient measure for fast reduction of mobile Hg at extremely contaminated soils. Moreover, the decrease of the mobile mercury portion was followed by improvement of the nutrient status of the soils.

Background: Urban particulate matter (PM) can affect green plants either via deposition on the above-ground biomass, where the contaminants can penetrate the leaf surface, or indirectly via soil-root interaction. This experiment assessed the potential risk of PM-derived risk elements contained in vegetables. The bioavailable portions of arsenic (As), cadmium (Cd), iron (Fe), and zinc (Zn) in leafy vegetables amended by PM via soil and/or foliar application were investigated in a model pot experiment, in which lettuce and chard were cultivated., Results: By using the physiologically based extraction test simulating in vitro human digestive processes in the stomach and small intestine, the bioavailable portions of toxic elements from PM-amended plant biomass were extracted. Extractable portions of elements by a simulated gastric solution from biomass decreased for lettuce in the order Zn > Cd > As > Fe; while for chard, the order was As > Zn > Cd > Fe. No significant effects of PM physical fractions or soil were observed., Conclusions: Although the bioavailable element portions in the PM samples were lower compared to plants, the bioavailable element contents in foliar PM-amended plant leaves exceeded the control and soil PM amendment levels, even after biomass washing., (© 2012 Society of Chemical Industry.)

Enhanced phytoextraction using EDTA for the remediation of an agricultural soil contaminated with less mobile risk elements Cd and Pb originating from smelting activities in Príbram (Czech Republic) was assessed on the laboratory and the field scale. EDTA was applied to the first years crop Zea mays. Metal mobilization and metal uptake by the plants in the soil were monitored for two additional years when Triticum aestivum was planted. The application ofEDTA effectively increased water-soluble Cd and Pb concentrations in the soil. These concentrations decreased over time. Anyhow, increased concentrations could be still observed in the third experimental year indicating a low possibility of groundwater pollution after the addition of EDTA during and also after the enhanced phytoextraction process under prevailing climatic conditions. EDTA-applications caused phytotoxicity and thereby decreased biomass production and increased Cd and Pb uptake by the plants. Phytoextraction efficiency and phytoextraction potential were too low for Cd and Pb phytoextraction in the field in a reasonable time frame (as less than one-tenth of a percent of total Cd and Pb could be removed). This strongly indicates that EDTA-enhanced phytoextraction as implemented in this study is not a suitable remediation technique for risk metal contaminated soils.

The aim of our study was to compare the sorption properties of a contaminated soil before and after two types of phytoremediation (natural phytoextraction vs. phytostabilization with dolomite limestone (DL) application). Soil from a pot experiment in controlled greenhouse conditions performed for two vegetation periods was used for the study. Lead, as the main contaminant in the studied soil, was easily desorbed by Cu, especially due to the increased affinity of Cu for soil organic matter; hence input of Cu to the studied soil can present another environmental risk in soils contaminated with other metals (such as Pb). In addition, the sorption behavior of chosen metals from single-element solutions differed from multielement solutions. The obtained results proved the different sorption behavior of metals in the single-element solution compared to the multi-element ones. Soil sorption behavior of Cd, Cu, and Zn decreased with the presence of the competitive metals; nevertheless, Pb sorption potential was not influenced by other competitive metals. Natural phytoextraction showed no significant effect on the sorption of Cd, Cu, Pb, and Zn onto the soil On the other hand, phytostabilization associated with DL application improved the soil sorption efficiency of all chosen metals, especially of Cu.

The use of natural chelates to enhance risk element mobility combined with rhizofiltration by free floating macrophytes have not been thoroughly studied in recent years. The aim of this study was to investigate the efficiency of organic acids in soil by conducting flushing experiments to enhance the mobility of Cd, Pb, and Zn from soil to solution. In addition, the bioaccumulation of Cd, Pb, and Zn, in water lettuce (Pistia stratiotes L.) will be studied as they affect the biomass in the rhizofiltration process. The results revealed that citric and tartaric acids mobilised the highest amount of all risk elements. In comparison to control, citric acid mobilised 71%, 181%, and 112% of Cd, Pb, and Zn while tartaric acid mobilised 70%, 155%, and 135% of Cd, Pb, and Zn respectively. The bioconcentration factor was approximately 2-5 times higher for juvenile plants than mature plants for all treatments as well as for both parts (leaves and roots). The risk element translocation into aerial parts decreased with increased time. Juvenile and mature plants proved a high accumulation potential and a 3 week growth period was observed as a sufficient time period to remove more than 80% of Cd, Pb, and Zn.

This study evaluates the long-term behavior of metals in soils treated with ethylenediaminedisuccinate for remediation purposes. The addition of the chelant led to a significant increase of water-extractable copper, iron, aluminum contents and their uptake by poplar. Increased concentrations of the metals were present in the soil solution even after the 2 years of the experiment (up to a 30-, 170- and 270-fold increase for copper, iron and aluminum, respectively). Therefore, soils treated with chelants must be monitored not only for the targeted metal concentrations but also for major soil cations originating from chelant-induced dissolution of soil oxides., (© Springer Science+Business Media, LLC 2011)

Changes of amino acid concentrations (proline, glutamate, asparagine, aspartate, alanine) and glutamate kinase activity (GKA) in plants under arsenic chronic stress reported here reveal their role in plant arsenic stress adaptation. Results of the pot experiment confirmed the toxic effect of arsenic at tested levels (As1=25 mg As kg(-1) soil, As2=50 mg As kg(-1) soil, As3=75 mg As kg(-1) soil) for spinach. Growing available arsenic contents in soil were associated with the strong inhibition of above-ground biomass and with the enhancement of As plant content. The changes of glutamate, asparagine, aspartate and proline levels in the plants showed strong linear dependences on arsenic concentration in plants (R2=0.60-0.90). Compared to the untreated control, concentrations of free proline and aspartate of As3 treatment were enhanced up to 381% and 162%, respectively. The significant changes of glutamate were observed on As2 and As3 treatments (increased level up to 188, i.e. 617%). Arsenic in plants was shown to be an inhibitor of glutamase kinase activity (R2=0.91). Inhibition of GKA resulted in an increase in the content of glutamate that is used in synthesis of phytochelatins in plant cells. Concentration of alanine did not have a confirmed linear dependence on arsenic concentration in plant (R2=0.05). The changes of its concentrations could be affected by changes of pH in plant cell or induction of alanine aminotransferase by hypoxia., (Copyright (c) 2010 Elsevier Inc. All rights reserved.)

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., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

The Rengen Grassland Experiment in Germany, established in 1941, consists of the following fertilizer treatments applied under a two cut management: control, Ca, CaN, CaNP, CaNP-KCl, and CaNP-K(2)SO(4). The aim of this study was (1) to identify effects of fertilizer application on biomass and species composition of bryophytes and (2) to investigate the impact of fertilizer application on macro- (N, P, K, Ca, Mg), micro- (Cu, Fe, Mn, Zn), and toxic (As, Cd, Cr, Pb, Ni) element concentrations in bryophyte biomass. In June 2006, Rhytidiadelphus squarrosus was the only bryophyte species recorded in the control. In treatment Ca, R. squarrosus was the dominant bryophyte species whereas Brachythecium rutabulum occurred sporadically only in a single plot of that treatment. The latter was the only bryophyte species collected in CaN, CaNP, CaNP-KCl, and CaNP-K(2)SO(4) treatments. Dry matter accumulation of bryophytes was highest in the control (180 g m(-2)) followed by Ca (46 g m(-2)), CaNP (25 g m(-2)), CaNP-KCl (15 g m(-2)), CaNP-K(2)SO(4) (9 g m(-2)), and CaN (2 g m(-2)) treatments. A negative correlation between biomass production of bryophytes and dry matter production of vascular plants was revealed up to a threshold value of 400 g m(-2). Above this limit, biomass production of bryophytes remained obviously unaffected by further increase in biomass production of vascular plants. A significant effect of treatment on As, Cd, Cr, Fe, Mn, Ni, Pb, P, Ca, Mg, K, and N concentrations was revealed. Concentrations of these elements were a function of amount of elements supplied with fertilizers. Bryophytes seem to be promising bio-indicators not only for airborne deposition of toxic element but also for fertilizer introduced as well.

The effect of soil extraction procedures and/or sample pretreatment (drying, freezing of the soil sample) on the extractability of arsenic and its compounds was tested. In the first part, five extraction procedures were compared with following order of extractable arsenic portions: 2M HNO(3)>>0.43 M CH(3)COOH>or=0.05 M EDTA>or=Mehlich III (0.2M CH(3)COOH+0.25 M NH(4)NO(3)+0.013 M HNO(3)+0.015 M NH(4)F+0.001 M EDTA) extraction>>water). Additionally, two methods of soil solution sampling were compared, centrifugation of saturated soil and the use of suction cups. The results showed that different sample pretreatments including soil solution sampling could lead to different absolute values of mobile arsenic content in soils. However, the interpretation of the data can lead to similar conclusions as apparent from the comparison of the soil solution sampling methods (r=0.79). For determination of arsenic compounds mild extraction procedures (0.05 M (NH(4))(2)SO(4), 0.01 M CaCl(2), and water) and soil solution sampling using suction cups were compared. Regarding the real soil conditions the extraction of fresh samples and/or in situ collection of soil solution are preferred among the sample pretreatments and/or soil extraction procedures. However, chemical stabilization of the solutions should be allowed and included in the analytical procedures for determination of individual arsenic compounds.

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.

Changes of glutamate kinase activity (GKA) in plants under cadmium and zinc chronic stress reported here reveal a regulatory role of this enzyme in plant heavy metal stress adaptation and indicate its potential use as a stress biomarker. Results of the first experimental series confirmed the toxic effects of cadmium and zinc at tested levels (30, 60, 90 mg Cd kg(-1) and 250, 500, 750 mg Zn kg(-1) soil) for spinach. A significant decrease of GKA in plants grown on contaminated treatments was found. Changes of GKA of plants grown on the highest contaminated treatments in the second series of experiments showed a similar course as a curve of plant stress response indicating the process of plant adaptation to chronic stresses--the decline of GKA in period of damage of cell activities, increase of its activity in period of maximum resistance and its following decrease in period of the plant metabolism depletion.

The efficiency of poplar (Populus nigra L.xPopulus maximowiczii Henry.) was assessed during a two-year chemically enhanced phytoextraction of metals from contaminated soils. The tested metal mobilizing agents were EDTA (ethylenediaminetetraacetic acid) and NH4Cl. EDTA was more efficient than chlorides in solubilizing metals (especially Pb) from the soil matrix. The application of chlorides only increased the solubility of Cd and Zn. However, the increased uptake of metals after the application of higher concentrations of mobilizing agents was associated with low biomass yields of the poplar plants and the extraction efficiencies after the two vegetation periods were thus comparable to the untreated plants. Additionally, the application of mobilizing agents led to phytotoxicity effects and increased mobility of metals. Higher phytoextraction efficiencies were observed for Cd and Zn compared to Pb and Cu. Poplars are therefore not suitable for chemically enhanced phytoextraction of metals from severely contaminated agricultural soils.

Chelant-enhanced phytoextraction of heavy metals is an emerging technological approach for a non-destructive remediation of contaminated soils. The main objectives of this study were (i) to assess the extraction efficiency of two different synthetic chelating agents (ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedisuccinic acid (EDDS)) for desorbing Pb from two contaminated agricultural soils originating from a mining and smelting district and (ii) to assess the phytoextraction efficiency of maize (Zea mays) and poplar (Populus sp.) after EDTA application. EDTA was more efficient than EDDS in desorbing and complexing Pb from both soils, removing as much as 60% of Pb. Maize exhibited better results than poplar when extracting Pb from the more acidic (pH approximately 4) and more contaminated (up to 1360 mg Pb kg(-1)) agricultural soil originating from the smelting area. On the other hand, poplars proved to be more efficient when grown on the near-neutral (pH approximately 6) and less contaminated (up to 200 mg Pb kg(-1)) agricultural soil originating from the mining area. Furthermore, the addition of EDTA led to a significant increase of Pb content especially in poplar leaves, proving a strong translocation rate within the poplar plants.

The influence of soil contamination by inorganic and organic arsenic compounds on uptake, accumulation, and transformation of arsenic in pepper (Capsicum annum L.) was investigated in greenhouse pot experiments under controlled conditions. Pepper plants were cultivated in substrate amended by aqueous solutions of arsenite, arsenate, methylarsonic acid (MA), and dimethylarsinic acid (DMA) applied individually into cultivation substrate at concentrations of 15 mg As per kg of substrate. The plant availability of the arsenicals increased in the order arsenite = arsenate < MA < DMA. The highest arsenic concentrations were found in roots followed by stems, leaves, and fruits regardless of arsenic compound applied. In the control samples of pepper fruits, As(III), As(V), and DMA were present (25%, 37%, and 39% of the water-extractable arsenic). In control stems + leaves and roots, As(V) was the major compound (63% and 53% in a phosphate buffer extract) followed by As(III) representing 33% and 42%. Additionally, low concentrations (not exceeding 5%) of DMA and MA were detected as well. In all the soils analyzed after the first harvest of pepper fruits, arsenate was the dominating compound followed by arsenite. Methylarsonic acid, methylarsonous acid, and DMA were present at varying concentrations depending on the individual soil treatments. In the treated plants, the arsenic compounds in plant tissues reflected predominantly the extractable portions of arsenic compounds present in soil after amendment, and this pattern was more significant in the first part of vegetation period. The results confirmed the ability of generative parts of plants to accumulate preferably organic arsenic compounds, whereas in the roots and aboveground biomass, mainly inorganic arsenic species are present. Evidently, the source of soil arsenic contamination affects significantly the extractable portions of arsenic compounds in soil and subsequently the distribution of arsenic compounds within the plants.

Heterezygous tobacco (Nicotiana tabacum var. xanthi) and potato (Solanum tuberosum var. Korela) plants were cultivated on soil from the site Strimice which is highly polluted with heavy metals and on nonpolluted soil from the recreational site Jezerí, both in North Bohemia, Czech Republic. The total content, the content of bioavailable, easily mobile, and potentially mobile components of heavy metals (Cd, Cu, Pb, and Zn) in the tested soils, and the accumulation of these metals in the above-ground biomass and roots of tested plants were analyzed by flame atomic absorption spectrometry or flameless atomic absorption spectrometry. The average tobacco leaf area and potato plant height were significantly reduced in plants growing on the polluted soil. We have measured the DNA damage in nuclei of leaves of both plant species using the Comet assay. A small but significant increase in DNA damage was noted in plants growing on the polluted soil versus controls. As the tobacco and potato plants with increased DNA damage were severely injured (inhibited growth, distorted leaves), this increase may be associated with necrotic or apoptotic DNA fragmentation. No increase in the frequency of somatic mutation was detected in tobacco plants growing on the polluted soil. Thus, the polluted soil probably induced toxic but not genotoxic effects on tobacco and potato plants.

In this work three mild extraction agents for determination of plant-available fractions of elements in soil were evaluated for arsenic speciation in soil samples. Pepper (Capsicum annum, L.) var. California Wonder was cultivated in pots, and aqueous solutions of arsenite, arsenate, methylarsonic acid, and dimethylarsinic acid, at a concentration of 15 mg As kg(-1) soil, were added at the beginning of the experiment. Control pots (untreated) were also included. Deionized water, 0.01 mol L(-1) CaCl2, and 0.05 mol L(-1) (NH4)2SO4 were used to extract the plant-available fraction of the arsenic compounds in soil samples collected during the vegetation period of the plants. Whereas in control samples the extractable arsenic fraction did not exceed 1% of total arsenic content, soil amendment by arsenic compounds resulted in extraction of larger amounts, which varied between 1.4 and 8.1% of total arsenic content, depending on soil treatment and on the extracting agent applied. Among arsenic compounds determined by HPLC-ICPMS arsenate was predominant, followed by small amounts of arsenite, methylarsonic acid, and dimethylarsinic acid, depending on the individual soil treatment. In all the experiments in which methylarsonic acid was added to the soil methylarsonous acid was detected in the extracts, suggesting that the soil bacteria are capable of reducing methylarsonic acid before a further methylation occurs. No significant differences were observed between analytical data obtained by using different extraction procedures.

The preparation of internal reference material NSC-21 Compost Vitahum, including its stabilization, homogeneity testing, and evaluation of an interlaboratory comparison in which 19 laboratories took part using several analytical methods is described. From the results of the intercomparison, consensus values were derived for the contents of Cd, Cu, Ni, Pb, and Zn, whereas for As, Co, Cr, Fe, Hg and Mn, information values were derived. Bimodal distribution of the As and Cr results was obtained, presumably because of incomplete dissolution of the elements from the matrix if insufficiently aggressive decomposition procedures were employed. Some problems encountered were elucidated by application of neutron activation analysis (NAA) in its nondestructive and destructive (radiochemical) modes.