Unveiling New Arsenic Compounds in Plants via Tailored 2D-RP-HPLC Separation with ICP and ESI MS Detection.

Arsenic (As) speciation analysis is scientifically relevant due to the pivotal role the As chemical form plays in toxicity, which, in turn, directly influences the effect it has on the environment. The objective of this study was to develop and optimize a method tailored for studying As compounds in plant samples. Different extraction procedures and HPLC methods were explored to assess their efficiency, determine mass balance, and improve the resolution of compounds in the chromatograms. Conventionally applied anion-exchange chromatography facilitated the separation of well-documented As compounds in the extracts corresponding to 19 to 82% of As present in extracts. To gain insight into compounds which remain undetectable by anion chromatography (18 to 81% of As in the extracts), but still possibly metabolically relevant, we explored an alternative chromatographic approach. The procedure of sample purification and preconcentration through solid-phase extraction, facilitating the detection of those minor As compounds, was developed. The system was further refined to achieve an online 2D-RP-HPLC system, which was employed to analyze the extracts more comprehensively with ICP and ESI MS. Using this newly developed method, As(III)-phytochelatins, along with other arseno-thio-compounds, were detected and identified in extracts derived from the tree roots of seedlings grown in the presence of As(III) and As(V), and a group of arseno lipids was detected in the roots of plants exposed to As(V).

Dendroremediation of soil contaminated by mining sludge: A three-year study on the potential of Tilia cordata and Quercus robur in remediation of multi-element pollution.

The vast amounts of mining and metallurgical wastes containing unimaginable quantities of toxic metal(loid)s require searching for managed ways. The study aimed to long-term assess the growth, elements accumulation (As, Cd, Hg, In, Mn, Mo, Pb, Sb, Sn, Ti, Tl, Zn) and proline content in 2-year-old Tilia cordata Mill. and Quercus robur L. seedlings growing under 1 and 3% extremely polluted mining sludge (MS) after 1, 2 and 3 years. Both species were able to grow efficiently without significant differences resulting from the impact of MS. The overall rise was higher for T. cordata than for Q. robur. The accumulation ability for As, Hg, In, Mn, Mo, Pb, Ti, and Zn in the whole plant was significantly higher for T. cordata, while Cd, Sb, Sn and Tl did not differ considerably between species. The highest content was found for As, Mn and Zn (68.7, 158, and 157 mg per plant, respectively) for T. cordata after 3 years of growth. The calculated Bioconcentration Factors were the highest for Cu (1.23), In (6.86), and Zn (38.4) for Q. robur, as well as for As (1.55), Hg (3.24), Mn (32.8), Mo (1.64) and Ti (18.0) for T. cordata after 3 years. The highest Translocation Factors were observed for In (1.35) and Sn (1.25) after 3 years, as well as for Mn (2.72, 3.38, and 3.03 after 1, 2, and 3 years) for Q. robur seedlings. The proline content was higher for Q. robur, regardless of which organ was examined, and the differences increased with the time of the experiment and the amount of MS addition (possibly more sensitive to stress). Young T. cordata seedlings show much greater potential than Q. robur. This is the first time that a demonstration of the high potential of long-living trees in multi-element MS remediation has been described.

Comparative electrochemical study of veterinary drug danofloxacin at glassy carbon electrode and electrified liquid-liquid interface.

This work compares the electroanalytical performance of two electroanalytical systems based on (1) the glassy carbon electrode (GCE), and (2) the electrified liquid-liquid interface (eLLI), for the detection of fluoroquinolone antibiotic-danofloxacin (DANO). Our aim was to define the optimal conditions to detect the chosen analyte with two employed systems, extract a number of electroanalytical parameters, study the mechanism of the charge transfer reactions (oxidation at GCE and ion transfer across the eLLI), and to provide physicochemical constants for DANO. Detection of the chosen analyte was also performed in the spiked milk samples. To the best of our knowledge, this is the first work that directly compares the electroanalytical parameters obtained with solid electrode (in this case GCE) and eLLI. We have found that for DANO the latter provides better electroanalytical parameters (lower LOD and LOQ) as well as good selectivity when the milk was analyzed.

Mineral composition variation in Boletales mushrooms-indication of soil properties and taxonomic influence.

The efficiency of element accumulation depends on numerous factors, where the physico-chemical characteristics of the soil seem to be very important, and the role of taxonomic rank in the accumulation of elements by mushrooms seems to be important. The aim of the study was to compare the mineral composition of 7 species belonging to Leccinum and Suillus genera, collected between 2019 and 2021 from localizations in the west-central part of Poland. The research aimed to indicate the role of selected soil parameters in stimulating/inhibiting the accumulation of elements by selected Boletales mushroom species and to answer the question about the role of species belonging to the genus as an indicator determining the specific mineral composition of fruiting bodies. Soil pH and other soil properties (granulometric composition, organic carbon, degree of organic matter decomposition) may significantly affect mushrooms' mineral composition. Mushroom species belonging to Leccinum genus exhibited the higher amount of essential major and trace elements than species of Suillus genus). It suggests that the affiliation of the studied mushroom species to a specific genus may affect their mineral composition, and the physicochemical properties of the soil may be responsible for the lack of a clear division in the efficiency of element(s) accumulation. Selected species contain high amounts of K, Cu, Fe, and Zn, while others, such as selected Suillus gravellei fruiting bodies, also contain As and Cd. The results described serve as an introduction to a broader scientific discussion and require many further studies to confirm the role of taxonomic ranks and the influence of soil characteristics on the accumulation of elements by fruiting bodies.

Can the concentration of elements in wild-growing mushrooms be deduced from the taxonomic rank?

The mineral composition of wild-growing mushroom species is influenced by various environmental factors, particularly the chemical properties of the soil/substrate. We hypothesised that element uptake might also correlate with taxonomic classification, potentially allowing us to predict contamination levels based on mushrooms within the same taxonomic rank. This study compared the mineral composition (Ag, As, Ba, Ca, Cd, Co, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, Se, and Zn) of 16 saprotrophic mushroom species from 11 genera across 4 families and 2 orders. Among these were 13 edible and 3 inedible mushrooms, all collected from natural, wild stands in a forest in central-western Poland between 2017 and 2020. Phallus impudicus exhibited the highest mean content of Ba (together with Phallus hadriani) (6.63 and 8.61 mg kg-1, respectively), Ca (with Paralepista gilva and Stropharia rugosoannulata) (803, 735 and 768 mg kg-1, respectively), Cd (with Lycoperdon perlatum) (3.59 and 3.12 mg kg-1, respectively), Co (0.635 mg kg-1), and Fe (with P. hadriani and S. rugosoannulata) (476, 427 and 477 mg kg-1, respectively), while Macrolepiota mastoidea showed the highest content of Ag (1.96 mg kg-1), As (with Coprinus comatus) (1.56 and 1.62 mg kg-1, respectively) and Cu (with Macrolepiota procera and Chlorophyllum rhacodes) (192, 175 and 180 mg kg-1, respectively). Comparing the content of the analysed elements in the genera represented by at least two species, a similarity was observed, the same as the mean concentration in soil under these species. Soil characteristics could be a superior factor that overshadows the impact of the mushroom genus on the elements accumulation, obscuring its role as a determinant in this process. The results are not definitive evidence that belonging to a particular taxonomic rank is a prerequisite condition affecting the accumulation of all elements. A closer focus on this issue is needed.

Temporal arsenic form changes dynamics and accumulation patterns in Tilia cordata Mill. seedlings: Insights into metalloid transformation and tolerance mechanisms in trees.

Arsenic (As) remediation is challenging due to the complex nature and the persistence of these metalloid compounds. While it may seem that differences between As forms influence have been extensively described, new findings challenge the previously accepted knowledge, particularly for woody plants. Therefore, this study focused on 2-year-old Tilia cordata Mill. seedlings early (0, 2, 4, 12, 24 h) and late (3, 7, 12, 18, 25, 33 days) responses during growth under: As(III), As(V) or dimethylarsinic acid (DMA) (0.3 mM). Time-dependent transformations of As forms, distribution in plants, and microbiological characteristics (actinobacteria, bacteria, fungi, enzyme activity) were investigated. The highest increase in total As content was observed in plants exposed to As(V) and As(III). Dynamic metalloid form changes in the solution and tree organs were indicated. The most phytotoxic was DMA. This form was the main factor limiting the growth and effective accumulation of As. Despite experimenting in hydroponics, microorganisms played an important role in As form transformations, suggesting the potential for microbial-assisted dendroremediation strategies. The study confirmed that trees can convert more toxic forms into less toxic ones (e.g. As(III) to phytochelatins - As(III)-(PC3)), whose presence in roots seedlings exposed to As(III) and As(V) has been identified. The formation of hydrophobic forms (e.g. dimethylarsinoyl lipid) in the roots of seedlings grown under As(V) was confirmed. It is the first discovery for trees, previously observed only in bacteria and algae. The dynamics of metalloid form changes indicated that T. cordata transforms As forms according to their needs, which may give tree species an advantage in phytoremediation techniques. It holds great promise for the potential of dendroremediation.

Copper, lead and zinc interactions during phytoextraction using Acer platanoides L.-a pot trial.

Of the many environmental factors that modulate the phytoextraction of elements, little has been learnt about the role of metal interactions. The study aimed to show how different concentrations of Cu, Pb and Zn in the cultivation medium influenced the biomass, plant development and phytoextraction abilities of Acer platanoides L. seedlings. Additionally, the impact on the content and distribution of Ca, K, Mg and Na in plant parts was studied with an analysis of phenols. Plants treated with a mixture of two metals were characterised by lower biomass of leaves and higher major elements content jointly than those grown in the salt of one element. Leaves of A. platanoides cultivated in Pb5 + Zn1, Pb1 + Zn1 and Pb1 + Zn5 experimental systems were characterised by specific browning of their edges. The obtained results suggest higher toxicity to leaves of Pb and Zn present simultaneously in Knop solution than Cu and Pb or Cu and Zn, irrespective of the mutual ratio of the concentrations of these elements. Antagonism of Cu and Zn concerning Pb was clearly shown in whole plant biomass when one of these elements was in higher concentration (5 mmol L-1) in solution. In the lowest concentrations (1 mmol L-1), there was a synergism between Cu and Zn in plant roots. Plants exposed to Zn5, Cu1 + Pb5, Pb5 + Zn1 and Cu1 + Zn1 were characterised by higher total phenolic content than the rest plants. Both the presence and the concentration of other elements in the soil are significant factors that modulate element uptake, total phenolic content, and plant development.

Mycoremediation of Flotation Tailings with Agaricus bisporus.

Due to their enzymatic and bioaccumulation faculties the use of macromycetes for the decontamination of polluted matrices seems reasonable for bioremediation. For this reason, the aim of our study was to evaluate the mycoremediation ability of Agaricus bisporus cultivated on compost mixed with flotation tailings in different quantities (1, 5, 10, 15, and 20% addition). The biomass of the fruit bodies and the content of 51 major and trace elements were determined. Cultivation of A. bisporus in compost moderately polluted with flotation tailings yielded significantly lower (the first flush) and higher (the second flush) biomass of fruit bodies, compared with the control treatment. The presence of toxic trace elements did not cause any visible adverse symptoms for A. bisporus. Increasing the addition of flotation tailings to the compost induced an elevated level of most determined elements. A significant increase in rare earth elements (both flushes) and platinum group elements (first flush only) was observed. The opposite situation was recorded for major essential elements, except for Na and Mg in A. bisporus from the second flush under the most enriched compost (20%). Nevertheless, calculated bioaccumulation factor values showed a selective accumulation capacity-limited for toxic elements (except for Ag, As, and Cd) and the effective accumulation of B, Cu, K, and Se. The obtained results confirmed that A. bisporus can be used for practical application in mycoremediation in the industry although this must be preceded by larger-scale tests. This application seems to be the most favorable for media contaminated with selected elements, whose absorption by fruiting bodies is the most efficient.

Road traffic and abiotic parameters of underlying soils determine the mineral composition and nutritive value of the mushroom Macrolepiota procera (Scop.) Singer.

The effectiveness of accumulating mineral elements by wild-growing mushrooms depends mainly on species, their growth place, and the underlying soil's chemical characteristics. The aim of the study was to determine the effect of road traffic and the role of chemical characteristics of soil on the mineral composition of Macrolepiota procera fruit bodies growing in close proximity to a road and an adjacent forest during a four-year period. The concentrations of the majority elements (mainly Al, Cd, Co, Cr, Cu, Pb, Ti, and Zn) in the soil near the road were significantly higher than those in the forest soil, which was reflected in the fruit bodies which contained a higher amount of these elements. While the accumulation of heavy metals and other elements in the M. procera fruit bodies did not depend on the total soil organic carbon content, the degree of their decomposition determined by the C:N ratio and the individual fractions of organic carbon had a significant influence. Our studies show that soil properties are highly variable in the natural habitats of M. procera, which affects the efficiency of element accumulation. Macrolepiota procera fruit bodies growing in soil with similar chemical properties were characterized by different mineral compositions. Moreover, the obtained results indicate that the fruit bodies of edible M. procera, not only those close to roads but also at a greater distance, may contain significant amounts of toxic As and Cd, which could pose a health risk if consumed. Although most studies describing the mineral composition of M. procera fruit bodies have found no evidence to question the safety of their consumption, this species can effectively accumulate selected elements when growing immediately beside roads or in their close proximity.

Biofortification of Three Cultivated Mushroom Species with Three Iron Salts-Potential for a New Iron-Rich Superfood.

Mushrooms fortified with iron (Fe) can offer a promising alternative to counter the worldwide deficiency problem. However, the factors that may influence the efficiency of fortification have not yet been fully investigated. The aim of this study was to compare the effects of three Fe forms (FeCl3 6H2O, FeSO4 7H2O, or FeHBED) in three concentrations (5, 10, or 50 mM) for three mushroom species (Pleurotus eryngii, P. ostreatus, or Pholiota nameko) on their chemical composition, phenolic compounds, and organic acid production. The most effective metal accumulation of all the investigated species was for the 50 mM addition. FeCl3 6H2O was the most favorable additive for P. eryngii and P. nameko (up to 145 and 185% Fe more than in the control, respectively) and FeHBED for P. ostreatus (up to 108% Fe more than in control). Additionally, P. nameko showed the highest Fe accumulation among studied species (89.2 ± 7.51 mg kg-1 DW). The creation of phenolic acids was generally inhibited by Fe salt supplementation. However, an increasing effect on phenolic acid concentration was observed for P. ostreatus cultivated at 5 mM FeCl3 6H2O and for P. eryngii cultivated at 5 mM FeCl3 6H2O and 5 mM FeSO4 7H2O. In the case of organic acids, a similar situation was observed. For P. ostreatus, FeSO4 7H2O and FeHBED salts increased the formation of the determined organic acids in fruiting bodies. P. eryngii and P. nameko were characterized by a much lower content of organic acids in the systems supplemented with Fe. Based on the obtained results, we recommend starting fortification by preliminarily indicating which form of the element is preferred for the species of interest for supplementation. It also seems that using an additive concentration of 50 mM or higher is most effective.

Anthropogenic contamination leads to changes in mineral composition of soil- and tree-growing mushroom species: A case study of urban vs. rural environments and dietary implications.

Because wild-growing edible mushroom species are frequently consumed, a knowledge of their mineral composition is essential. The content of elements in mushrooms and their possible beneficial or harmful effect may be influenced by the human-impacted environment. Thus, the aim of the study was to analyse the mineral composition of the soil, trees, and especially soil- and tree-growing mushroom species collected from within a city and from rural areas. Due to potentially higher pollution in urban areas, we assumed that mushrooms from a city environment will contain higher levels of mineral elements than those from rural areas and that the high content will be attributed to greater contamination of city soils. Significantly higher concentrations of several elements in soils (Ca, Ba, Bi, Hg, Pb, Sb, Sr, W and Zr) and trees (Ag, Bi, Ce, Co, Mn, Mo, Nd, Pr, Ta, Tm and W) were observed from the samples collected in the city. Additionally, significantly higher contents of Ag, Fe, Hg, Mn, Mo, Sr, Y and Zn in soil-growing, and Al, As, Ba, Cr, Fe, Hg, Ni, Pb, Sr, Ta and Zn in tree-growing mushroom species were recorded from the urban area. These differences formed the basis for the observation that the content of elements in urban mushrooms is generally higher than in those from rural areas. However, a higher content of several soil elements does not necessarily mean that there will be a significantly higher content in fruit bodies. There was also no real risk of consuming soil-growing mushroom species collected in recent years from the city, suggesting that this practice may still be continued.

Trees and shrubs from a post-industrial area high in calcium and trace elements: the potential of dendroremediation.

NOVELTY STATEMENT: That is probably the first study to date of trees and shrubs differing in age and growing on post-industrial soil contaminated with calcium (Ca) and selected toxic metals/metalloids. The obtained results show that an alkaline reaction (less than 9) of soil and an unusually high Ca concentration may help the studied tree species to adapt/survive in unfavorable habitat conditions (high concentration of toxic elements). The efficiency of phytoextraction of toxic elements was so high that, especially for forest animals (roe-deer) that consume, e.g., willow shoots, it could pose a serious threat to health and life, both for them and potentially for humans.

Influence of Iron Addition (Alone or with Calcium) to Elements Biofortification and Antioxidants in Pholiota nameko.

Mushrooms supplementation with iron (Fe) is usually limited, and therefore it would be beneficial to search for other vital elements able to improve the process. The aim of this study was to verify a possible interaction between Fe and calcium (Ca) to estimate the role of the addition of the latter metal to stimulate Fe accumulation in Pholiota nameko. Additionally, an analysis of phenolic compounds and low molecular weight organic acids (LMWOAs) was performed. The increase of Fe concentration in the substrate caused a significantly higher accumulation of this metal in P. nameko. The addition of Ca (5 or 10 mM) stimulated Fe accumulation, just as Fe concentration in the substrate stimulated Ca accumulation, which pointed to a synergism between these metals. The obtained results show that the presence of Fe in the substrate may also promote K, Mg, Mn, Na, P, and S accumulation. In contrast, the addition of Ca stimulates and/or inhibits their content in fruit bodies. The phenolic and organic acids profile was poor. Only gallic, 4-hydroxybenzoic, sinapic and syringic acids (phenolics), as well as citric and succinic acids (LMWOAs), were quantified in some combinations in P. nameko fruiting bodies.

A Possibility to Use Selected Crop Post-Extraction Wastes to Improve the Composition of Cultivated Mushroom Pleurotus citrinopileatus.

A cultivated mushroom species, Pleurotus citrinopileatus, is becoming increasingly popular thanks to its attractive colour and medicinal properties. In this study, P. citrinopileatus was grown in a cultivation medium enriched with wheat bran (WB), thymus post-extraction waste (TPEW) and pumpkin post-extraction waste (PPEW) products. The study showed that the post-extraction wastes are a crucial factor determining the accumulation of minerals, the content/profile of low-molecular-weight organic acids (LMWOAs) and phenolic compounds in fruit bodies, thereby increasing their nutritional value. The use of the waste materials significantly increased LMWOAs contents. The sum of LMWOAs under all cultivation mediums increased, especially quinic, malic and citric acids under the 20% PPEW, 25 and 50% TPEW addition. Total phenolic content, phenolic content, as well as the composition and scavenging effect on DPPH radicals, were strongly dependent on the used substrate. The control variant was poor in phenolic compounds, while the supplementation increased the contents and diversity of these metabolites. In the control, only four phenolic compounds were quantified (chlorogenic, gallic, syringic and vanillic acids), while in the supplemented substrates up to 14 different phenolic compounds (caffeic, chlorogenic, p-coumaric, 2,5-dihydroxybenzoic acid, ferulic, gallic, protocatechuic, salicylic, sinapic, syringic, trans-cinnamic and vanillic acids, catechin and rutin).

The Possibility of Using Paulownia elongata S. Y. Hu × Paulownia fortunei Hybrid for Phytoextraction of Toxic Elements from Post-Industrial Wastes with Biochar.

The potential of the Paulownia hybrid for the uptake and transport of 67 elements along with the physiological response of plants cultivated in highly contaminated post-industrial wastes (flotation tailings-FT, and mining sludge-MS) was investigated. Biochar (BR) was added to substrates to limit metal mobility and facilitate plant survival. Paulownia could effectively uptake and translocate B, Ca, K, P, Rb, Re and Ta. Despite severe growth retardation, chlorophyll biosynthesis was not depleted, while an increased carotenoid content was noted for plants cultivated in waste materials. In Paulownia leaves and roots hydroxybenzoic acids (C6-C1) were dominant phenolics, and hydroxycinnamic acids/phenylpropanoids (C6-C3) and flavonoids (C6-C3-C6) were also detected. Plant cultivation in wastes resulted in quantitative changes in the phenolic fraction, and a significant drop or total inhibition of particular phenolics. Cultivation in waste materials resulted in increased biosynthesis of malic and succinic acids in the roots of FT-cultivated plants, and malic and acetic acids in the case of MS/BR substrate. The obtained results indicate that the addition of biochar can support the adaptation of Paulownia seedlings growing on MS, however, in order to limit unfavorable changes in the plant, an optimal addition of waste is necessary.

Time-dependent changes of arsenic and its selected forms in a hydroponic experiment with Quercus robur L.

Mutual transformations of particular As forms are dynamic. Therefore hydroponic experiments need to account for this variation. For this reason, the aim of the study was to determine the time-dependent changes of Astotal and selected forms of this metalloid (As(III), As(V), DMA or the sum of other organic forms) in modified Knop's solution and organs (root, low and high stem) of 2-year-old Quercus robur L. seedlings within a 33-day long hydroponic experiment. The results indicate the varying speed of As uptake and transport to aerial plant parts. A decrease in contents of As forms in organs of seedlings exposed to individual As forms varied, which indicates simultaneous transformations of As forms both in Knop's solution and plant organs. The obtained results indicate the need to analyse the main forms of As both in the nutrient solution and plant organs to assess the actual effectiveness of As phytoextraction by plants. It is necessary because, as demonstrated in this work, the addition of a specific As form does not mean that the capacity of a given plant relative to this form specifically is assessed. Capsule: The form of arsenic added to the medium undergoes dynamic changes affecting the phytoextraction of this metalloid in Quercus robur L. organs.

Mineral composition of elements in wood-growing mushroom species collected from of two regions of Poland.

The study monitored the content of 55 elements in 21 wood-growing mushroom species collected between 2013 and 2019 from Lower and Upper Silesia in Poland. Only 27 of the elements (Ag, Al, Ba, Ca, Cd, Cu, Fe, In, K, La, Mg, Mn, Na, Nd, Ni, P, Pb, Pr, Pt, Rh, Sr, Ti, Tm, V, Y, Zn, and Zr) were detected in all mushroom species, while others (As, Au, B, Be, Bi, Ce, Co, Cr, Dy, Er, Eu, Ga, Gd, Ge, Hf, Ho, Ir, Li, Lu, Mo, Os, Pb, Rb, Re, Ru, Sb, Sc, Se, Sm, Tb, Te, Th, Tl, Tm, U, and Yb) were below the limit of detection in the fruit bodies of at least one species. Wide ranges for major elements in the whole population of all the mushroom species were as follows: 15.4-470 (Ca), 6580-44,600 (K), 314-2150 (Mg), 38.0-319 (Na), and 1100-15,500 (P) mg kg-1 dm, respectively. The rank sum revealed that M. giganteus fruit bodies were the most enriched with all detectable elements, while A. mellea had the lowest content of the majority of elements. Mushrooms belonging to the Hymenochaetaceae family were characterized as some of the most enriched with the studied elements, while mushrooms of the Fomitopsidaceae family had the lowest content of elements. Similarities as well as differences between the obtained results and the available literature data confirm the important role of both mushroom species and the tree on which the fungus has grown.

Arsenic uptake, speciation and physiological response of tree species (Acer pseudoplatanus, Betula pendula and Quercus robur) treated with dimethylarsinic acid.

The aim of the study was to evaluate the effect of dimethylarsinic acid (DMA) on growth parameters and levels of stress-related metabolites in Acer pseudoplatanus, Betula pendula and Quercus robur. The increase of DMA concentration in the solution led to a notable growth retardation of trees. An intense As accumulation (mainly As(III) and As(V)) expressed as BCF and TF > 1 was recorded only for Q. robur. Generally a decrease in contents of cellulose, hemicellulose and holocellulose with a simultaneous increase in lignin content were recorded. Phenolic composition of leaf extracts was modified by DMA, while root and rhizosphere extracts were poor in phenolics. Toxicity of DMA leads to a significant drop in salicylic acid content in leaves observed at lower doses. Higher DMA levels caused a second, probably ROS-derived depletion of the metabolite accompanied with a severe growth retardation, most pronounced in the case of B. pendula. DMA caused the inhibition of LMWOA biosynthesis in roots of A. pseudoplatanus, B. pendula and their exudation into the rhizosphere, while in Q. robur roots and leaves a stimulation of their accumulation was observed. Disturbances in the activity of enzymatic antioxidants were observed for all the species following the increasing level of DMA.