Analysis of multiple biomarkers revealed the size matters of Cu particles for barley response under foliar exposure.

The impact of particle size of engineered nanoparticles (ENPs) on plant response has marginally been investigated under the foliar application so far. Concerning the significance of particle diameter for their properties and interaction with plants, the effect of size should be considered in the analysis of the effect of micronutrient-based ENPs on plants. It is of particular importance for ENPs containing Cu due to plants needing a relatively low amount of this element, thus there is a risk of overdosing during application as a fertilizer or pesticide. Here, we examined the biochemical and transcriptional response of barley (Hordeum vulgare L.) to Cu nanoparticles (nano-Cu) with different diameters (25 nm, 50 nm, 70 nm), microparticles (micro-Cu), and chelated Cu (EDTA-Cu). The plants suffering from Cu deficiency were foliar sprayed with Cu compounds at 1000 mg/L during the tillering stage. 1- and 7-day plants were analyzed in terms of biomass, Cu content, the activity of enzymes involved with antioxidant response, the content of low molecular weight compounds, and the expression of genes regulated metal homeostasis, aquaporins, and defense. The results showed that the Cu leaf level was differentiated over time and after 7 days it was higher under exposure to the smallest nano-Cu than other particulate Cu. Regardless of the duration of exposure, the Cu content was highest in plants treated with Cu-EDTA. The cluster analysis of all markers revealed a clear distinct response to the smallest nano-Cu and other particulate and ionic treatments. The bigger nano-Cu, depending on the markers, caused the medium effects between the nano-Cu 25 nm and micro-Cu and Cu-EDTA. The found size thresholds at the nanoscale will be useful for the fabrication of safe-by-design agrochemicals to provide crop security and attenuate environmental impact.

Elevated CO2 differentially attenuates beryllium-induced oxidative stress in oat and alfalfa.

Elevated CO2 (eCO2 ) is one of the climate changes that may benefit plant growth under emerging soil contaminants such as heavy metals. In this regard, the morpho-physiological mechanisms underlying the mitigating impact of eCO2 on beryllium (Be) phytotoxicity are poorly known. Hence, we investigated eCO2 and Be interactive effects on the growth and metabolism of two species from different groups: cereal (oat) and legume (alfalfa). Be stress significantly reduced the growth and photosynthetic attributes in both species, but alfalfa was more susceptible to Be toxicity. Be stress induced reactive oxygen species (ROS) accumulation by increasing photorespiration, subsequently resulting in increased lipid and protein oxidation. However, the growth inhibition and oxidative stress induced by Be stress were mitigated by eCO2 . This could be explained, at least partially, by the increase in organic acids (e.g., citric acid) released into the soil, which subsequently reduced Be uptake. Additionally, eCO2 reduced cellular oxidative damage by reducing photorespiration, which was more significant in alfalfa plants. Furthermore, eCO2 improved the redox status and detoxification processes, including phytochelatins, total glutathione and metallothioneins levels, and glutathione-S-transferase activity in both species, but to a greater extend in alfalfa. In this context, eCO2 also stimulated anthocyanin biosynthesis by accumulating its precursors (phenylalanine, coumaric acid, cinnamic acid, and naringenin) and key biosynthetic enzymes (phenylalanine ammonia-lyase, cinnamate hydroxylase, and coumarate:CoA ligase) mainly in alfalfa plants. Overall, this study explored the mechanistic approach by which eCO2 alleviates the harmful effects of Be. Alfalfa was more sensitive to Be stress than oats; however, the alleviating impact of eCO2 on Be stress was more pronounced in alfalfa.

Transcriptional response of Cu-deficient barley (Hordeum vulgare L.) to foliar-applied nano-Cu: Molecular crosstalk between Cu loading into plants and changes in Cu homeostasis genes.

For safe and effective nutrient management, the cutting-edge approaches to plant fertilization are continuously developed. The aim of the study was to analyze the transcriptional response of barley suffering from Cu deficiency to foliar application of nanoparticulate Cu (nano-Cu) and its ionic form (CuSO4) at 100 and 1000 mg L-1 for the examination of their supplementing effect. The initial interactions of Cu-compounds with barley leaves were analyzed with spectroscopic (ICP-OES) and microscopic (SEM-EDS) methods. To determine Cu cellular status, the impact of Cu-compounds on the expression of genes involved in regulating Cu homeostasis (PAA1, PAA2, RAN1, COPT5), aquaporins (NIP2.1, PIP1.1, TIP1.1, TIP1.2) and antioxidant defense response (SOD CuZn, SOD Fe, SOD Mn, CAT) after 1 and 7 days of exposure was analyzed. Although Cu accumulation in plant leaves was detected overtime, the Cu content in leaves exposed to nano-Cu for 7 days was 44.5% lower than in CuSO4 at 100 mg L-1. However, nano-Cu aggregates remaining on the leaf surface indicated a potential difference between measured Cu content and the real Cu pool present in the plant. Our study revealed significant changes in the pattern of gene expression overtime depending on Cu-compound type and dose. Despite the initial puzzling patterns of gene expression, after 7 days all Cu transporters showed significant down-regulation under Cu-compounds exposure to prevent Cu excess in plant cells. Conversely, aquaporin gene expression was induced after 7 days, especially by nano-Cu and CuSO4 at 100 mg L-1 due to the stimulatory effect of low Cu doses. Our study revealed that the gradual release of Cu ions from nano-Cu at a lower rate provided a milder molecular response than CuSO4. It might indicate that nano-Cu maintained better metal balance in plants than the conventional compounds, thus may be considered as a long-term supplier of Cu.

Uptake, accumulation, toxicity, and interaction of metallic-based nanoparticles with plants: current challenges and future perspectives.

The rapid development of industrialization is causing several fundamental problems in plants due to the interaction between plants and soil contaminated with metallic nanoparticles (NPs). Numerous investigations have been conducted to address the severe toxic effects caused by nanoparticles in the past few decades. Based on the composition, size, concentration, physical and chemical characteristics of metallic NPs, and plant types, it enhances or lessens the plant growth at various developmental stages. Metallic NPs are uptaken by plant roots and translocated toward shoots via vascular system based on composition, size, shape as well as plant anatomy and cause austere phytotoxicity. Herein, we tried to summarize the toxicity induced by the uptake and accumulation of NPs in plants and also we explored the detoxification mechanism of metallic NPs adopted by plants via using different phytohormones, signaling molecules, and phytochelatins. This study was intended to be an unambiguous assessment including current knowledge on NPs uptake, accumulation, and translocation in higher plants. Furthermore, it will also provide sufficient knowledge to the scientific community to understand the metallic NPs-induced inhibitory effects and mechanisms involved within plants.

The life cycle study revealed distinct impact of foliar-applied nano-Cu on antioxidant traits of barley grain comparing with conventional agents.

Despite that the applicability of Cu-based engineered nanoparticles (ENPs) as an antibacterial and antifungal agent for plant protection has been studied widely, little is known about their role in the improvement of crop yield and quality. Here, a full life study was performed to investigate the nutritional quality and bioactivity of barley grains under foliar application of nano-/microparticulate (nano-Cu, nano-CuO, micro-Cu) and ionic Cu compounds (CuSO4, CuEDTA). Hordeum vulgaris L. plants were sprayed with Cu compounds at 500 mg/L during the end of tillering and the beginning of heading. Yield, mineral composition, protein and dietary content, antioxidant (phenolic, anthocyanin, flavonoid, tannin, flavanol) content and antioxidant capacity of barley grain were evaluated. Grain yield was unaffected by all treatments. Only nano-Cu and ionic compounds enhanced Cu accumulation in grain: 2-fold increase was observed compared to the control (2.6 µg/kg). Nano-Cu also increased the dietary fiber content by 19.9 %, while no impact of the other treatments was determined. The content of phenolic compounds, the main group of antioxidants, remained unchanged after Cu supply. In general, for all Cu treatment, antiradical and reducing abilities were decreased or were at the similar level in relation to the control. On the other hand, chelating power in grain extracts was 2-4 times higher under nano-Cu/nano-CuO/micro-Cu than in the untreated sample, while the ionic compounds had no impact on the chelating indicator. Our results demonstrated that more favorable effects were triggered by nano-Cu than CuSO4 or CuEDTA on the tested indicators of barley grain, despite that both compounds resulted in similar superior Cu acquisition. It suggests that nano-Cu may be considered as an alternative agent to be used as economic and traditional fertilizers.

Nitric oxide and brassinosteroids enhance chromium stress tolerance in Glycine max L. (Merr.) by modulating antioxidative defense and glyoxalase systems.

Chromium (Cr) contamination of agricultural soils is a major threat to human and plant health worldwide and causes reductions in plant growth and crop yields. 24-epibrassinolide (EBL) and nitric oxide (NO) have been shown to ameliorate the reductions in growth caused by the stresses induced by heavy metals; however, the interactions between EBL and NO on the alleviation of Cr-induced phytotoxicity have been poorly studied. Hence, this study was undertaken to examine any beneficial effects of EBL (0.01 µM) and NO (100 µM), applied alone or in combination, on the mitigation of stress induced by Cr (100 µM) in soybean seedlings. Although EBL and NO applied alone reduced the toxic effects of Cr, the combined treatment had the greatest effect. Mitigation of Cr intoxication occurred via reduced Cr uptake and translocation and by ameliorating reductions in water contents, light-harvesting pigments, and other photosynthetic parameters. In addition, the two hormones increased the activity of enzymatic and non-enzymatic defense mechanisms increasing the scavenging of reactive oxygen species, thereby reducing membrane damage and electrolyte leakage. Furthermore, the hormones reduced the accumulation of the toxic compound, methylglyoxal, by amplifying activities of glyoxalase I and glyoxalase II. Thus, applications of NO and EBL can significantly mitigate Cr-phytotoxicity when cultivating soybean plants in Cr-contaminated soils. However, further more-in depth studies including field investigations parallel with calculations of cost to profit ratios and yield losses are requested to validate the effectiveness of NO and/or EBL for remediation agents in Cr-contaminated soils with using key biomarkers (i.e., oxidative stress, antioxidant defense, and osmoprotectants) involved in the uptake, accumulation, and attenuation of Cr toxicity tested in our study.

Unveiling of interactions between foliar-applied Cu nanoparticles and barley suffering from Cu deficiency.

The objective of this study was to evaluate nano-Cu-plant interactions under Cu deficiency. Nano-Cu at rates of 100 and 1000 mg L-1 was applied as foliar spray to Hordeum vulgare L. during increased demand for nutrients at tillering stage. Corresponding treatment with CuSO4 was used to exam the nano-specific effects. Cu compounds-plant leaves interactions were analyzed with spectroscopic and microscopic methods (ICP-OES, FTIR/ATR, SEM-EDS). Moreover, the effect of Cu compounds on plants in terms of biomass, pigments content, lipid peroxidation, antiradical properties, the activity of enzymes involved in plant defense against stress (SOD, CAT, POD, GR, PAL, PPO) and the content of non-enzymatic antioxidants (GSH, GSSG, TPC) was determined after 1 and 7 days of exposure. Cu loading to plant leaves increased over time, but the content of Cu under treatment with nano-Cu at 100 mg L-1 was lower by 76% than CuSO4 at 7th day of exposure. The changes induced by applied Cu compounds in biochemical traits were mostly observed after 1 day. Our data showed that CuSO4 exposure induce oxidative stress (increased MDA level and GSSG content) when compared to control and nano-Cu treated plants. Noteworthy, nano Cu at 100 mg L-1 demonstrated enhanced stress tolerance as indicated by boosted GSH content. After 7 days, the antioxidant response was almost same compared to control sample. However, based on other indicators (pigment content, chlorosis sign, biomass), it should be noted that CuSO4 caused serve oxidative burst of plant which may resulted in damage of defense system. Nano-Cu, especially at 100 mg L-1, showed promising effect on plant health, and obtained results may be useful for optimizing of nano-Cu application as fertilizer agent.

Funneliformis constrictum modulates polyamine metabolism to enhance tolerance of Zea mays L. to salinity.

The mechanisms underlie increased stress tolerance in plants of salinity stress in plants by arbuscular mycorrhizal fungi (AMF) are poorly understood, particularly the role of polyamine metabolism. The current study was conducted to investigate how inoculation with the AMF, Funneliformis constrictum, affects maize plant tolerance to salt stress. To this end, we investigated the changes in photosynthesis, redox status, primary metabolites (amino acids) and secondary metabolism (phenolic and polyamine metabolism). Control and inoculated maize plants were grown using different concentrations of diluted seawater (0%, 10%, 20% and 40%). Results revealed that treatment with 10% seawater had a beneficial effect on AMF and its host growth. However, irrigation with 20% and 40% significantly reduced plant growth and biomass. As seawater concentration increased, the plants' reliance on mycorrhizal fungi increased resulting in enhanced growth and photosynthetic pigments contents. Under higher seawater concentrations, inoculation with AMF reduced salinity induced oxidative stress and supported redox homeostasis by reducing H2O2 and MDA levels as well as increasing antioxidant-related enzymes activities (e.g., CAT, SOD, APX, GPX, POX, GR, and GSH). AMF inoculation increased amino acid contents in shoots and roots under control and stress conditions. Amino acids availability provides a route for polyamines biosynthesis, where AMF increased polyamines contents (Put, Spd, Spm, total Pas) and their metabolic enzymes associated (ADC, SAMDC, Spd synthase, and Spm synthase), particularly under 40% seawater irrigation. Consistently, the transcription of genes, involved in polyamine metabolism was also up regulated in salinity-stressed plants. AMF further increased the expression in genes involved in polyamine biosynthesis (ODC, SAMDC, SPDS2 and decreased expression of those in catabolic biosynthesis (ADC and PAO). Overall, inoculation with Funneliformis constrictum could be adopted as a practical strategy to alleviate salinity stress.

Arbuscular Mycorrhizal Fungus "Rhizophagus irregularis" impacts on physiological and biochemical responses of ryegrass and chickpea plants under beryllium stress.

Heavy metals such as beryllium (Be) have been identified as toxic for plants with a negative impact on plant growth. Therefore, there is an urgent need for environmentally friendly techniques to reduce Be toxicity on plant growth and productivity. To this end, arbuscular mycorrhizal fungi (AMF) are widely applied to induce plant growth and stress tolerance. However, how AMF-plant symbiosis can support plants under Be stress has not been studied. Accordingly, we investigated the physiological and biochemical responses of AMF inoculated ryegrass and chickpea plants to Be stress. The associated changes in Be uptake and accumulation, photosynthesis, oxidative stress, carbon and nitrogen metabolism were studied. Soil contamination with Be induced higher Be accumulation, particularly in ryegrass, which consequentially reduced plant growth and photosynthesis. However, photorespiration and oxidative damage (H2O2 accumulation, lipid oxidation, and LOX activity) were increased, mainly in ryegrass. In both plant species, AMF inoculation reduced Be accumulation and mitigated growth inhibition and oxidative damage, but to a more extent in ryegrass. This could be explained by improved photosynthesis as well as the upregulation of osmoprotectants i.e., sucrose and proline biosynthesis pathways. The increase in proline level was consistent with higher nitrogen (N) metabolism as reflected by N level and nitrate reductase. Species-specific responses were recorded and supported by principal component analysis. This study provided insight into the mechanism of AMF's impact on Be-stressed ryegrass and chickpea plants. Hence, the current research suggested that AMF inoculation could be used as a viable strategy to mitigate Be phytotoxicity in ryegrass and chickpea plants.

Association of jasmonic acid priming with multiple defense mechanisms in wheat plants under high salt stress.

Salinity is a global conundrum that negatively affects various biometrics of agricultural crops. Jasmonic acid (JA) is a phytohormone that reinforces multilayered defense strategies against abiotic stress, including salinity. This study investigated the effect of JA (60 µM) on two wheat cultivars, namely ZM9 and YM25, exposed to NaCl (14.50 dSm-1) during two consecutive growing seasons. Morphologically, plants primed with JA enhanced the vegetative growth and yield components. The improvement of growth by JA priming is associated with increased photosynthetic pigments, stomatal conductance, intercellular CO2, maximal photosystem II efficiency, and transpiration rate of the stressed plants. Furthermore, wheat cultivars primed with JA showed a reduction in the swelling of the chloroplast, recovery of the disintegrated thylakoids grana, and increased plastoglobuli numbers compared to saline-treated plants. JA prevented dehydration of leaves by increasing relative water content and water use efficiency via reducing water and osmotic potential using proline as an osmoticum. There was a reduction in sodium (Na+) and increased potassium (K+) contents, indicating a significant role of JA priming in ionic homeostasis, which was associated with induction of the transporters, viz., SOS1, NHX2, and HVP1. Exogenously applied JA mitigated the inhibitory effect of salt stress in plants by increasing the endogenous levels of cytokinins and indole acetic acid, and reducing the abscisic acid (ABA) contents. In addition, the oxidative stress caused by increasing hydrogen peroxide in salt-stressed plants was restrained by JA, which was associated with increased α-tocopherol, phenolics, and flavonoids levels and triggered the activities of superoxide dismutase and ascorbate peroxidase activity. This increase in phenolics and flavonoids could be explained by the induction of phenylalanine ammonia-lyase activity. The results suggest that JA plays a key role at the morphological, biochemical, and genetic levels of stressed and non-stressed wheat plants which is reflected in yield attributes. Hierarchical cluster analysis and principal component analyses showed that salt sensitivity was associated with the increments of Na+, hydrogen peroxide, and ABA contents. The regulatory role of JA under salinity stress was interlinked with increased JA level which consequentially improved ion transporting, osmoregulation, and antioxidant defense.

Smoothies Reduce the "Bioaccessibility" of TiO2 (E 171) in the Model of the In Vitro Gastrointestinal Tract.

The food colorant E171 (TiO2) containing nano fractions can cause potential health problems. In the presented work, we used a "gastrointestinal tract" model (oral→large intestine) to "digest" a fruit smoothie in the presence of TiO2 nanoparticles and the Lactiplantibacillus plantarum B strain. The TiO2 migration was measured using the microfiltration membrane (0.2 µm; model of "TiO2 bioacessability"). We observed that the addition of the smoothie reduced the Ti content in the microfiltrate (reduced "bioacessability") at the "mouth", "stomach" and "large intestine" stages, probably due to the entrapment of Ti by the smoothie components. A significant decrease in Ti "bioaccessibility" at the "gastric" stage may have resulted from the agglomeration of nanoparticles at a low pH. Additionally, the presence of bacterial cells reduced the "bioaccessibility" at the "large intestine" stage. Microscopic imaging (SEM) revealed clear morphological changes to the bacterial cells in the presence of TiO2 (altered topography, shrunk-deformed cells with collapsed walls due to leakage of the content, indentations). Additionally, TiO2 significantly reduced the growth of the tested bacteria. It can be stated that the interactions (most probably entrapment) of TiO2 in the food matrix can occur during the digestion. This can influence the physicochemical properties, bioavailability and in vivo effect of TiO2. Research aimed at understanding the interactions between TiO2 and food components is in progress.

Ecotoxicity of sewage sludge- or sewage sludge/willow-derived biochar-amended soil.

Co-pyrolysis of sewage sludge (SL) with plant biomass gains attention as a way to minimize SL-derived biochar drawbacks, such as high amount of toxic substances, low specific surface area and carbon content. The toxicity of soil amended with SL- (BCSL) or SL/biomass (BCSLW)-derived biochar was evaluated in long-term pot experiment (180 days). The results were compared to SL-amended soil. Biochars produced at 500, 600, or 700 °C were added to the soil (podzolic loamy sand) at a 2% (w/w) dose. Samples were collected at four different time points (at the beginning, after 30, 90 and 180 days) to assess the potential toxicity of SL-, BCSL- or BCSLW-amended soil. The bacteria Aliivibrio fischeri (luminescence inhibition - Microtox), the plant Lepidium sativum (root growth and germination inhibition test - Phytotoxkit F), and the invertebrate Folsomia candida (mortality and reproduction inhibition test - Collembolan test) were used as the test organisms. Depending on the organism tested and the sample collection time point variable results were observed. In general, SL-amended soil was more toxic than soil with biochars. The leachates from BCSLW-amended soil were more toxic to A. fischeri than leachate from BCSL-amended soil. A different tendency was observed in the case of phytotoxicity. Leachate from BCSL-amended soil was more toxic to L. sativum compared to BCSLW-amended soil. The effect of biochars on F. candida was very diversified, which did not allow a clear trend to be observed. The toxic effect of SL-, BCSL- or BCSW-amended soil to particular organisms was observed in different time, point's periods, which may suggest the different factors affecting this toxicity.

Revealing the toxicity of lopinavir- and ritonavir-containing water and wastewater treated by photo-induced processes to Danio rerio and Allivibrio fischeri.

In coronavirus disease 2019 (COVID-19), among many protocols, lopinavir and ritonavir in individual or combined forms with other drugs have been used, causing an increase in the concentration of antiviral drugs in the wastewater and hospital effluents. In conventional wastewater treatment plants, the removal efficiency of various antiviral drugs is estimated to be low (<20%). The high values of predicted no-effect concentration (PNEC) for lopinavir and ritonavir (in ng∙L-1) reveal their high chronic toxicity to aquatic organisms. This indicates that lopinavir and ritonavir are current priority antiviral drugs that need to be thoroughly monitored and effectively removed from any water and wastewater samples. In this study, we attempt to explore the impacts of two photo-induced processes (photolysis and photocatalysis) on the toxicity of treated water and wastewater samples containing lopinavir and ritonavir to zebrafish (Danio rerio) and marine bacteria (Allivibrio fischeri). The obtained results reveal that traces of lopinavir in water under photo-induced processes may cause severe problems for Danio rerio, including pericardial edema and shortening of the tail, affecting its behavior, and for Allivibrio fischeri as a result of the oxygen-depleted environment, inflammation, and oxidative stress. Hence, lopinavir must be removed from water and wastewater before being in contact with light. In contrast, the photo-induced processes of ritonavir-containing water and wastewater reduce the toxicity significantly. This shows that even if the physicochemical parameters of water and wastewater are within the standard requirements/limits, the presence of traces of antiviral drugs and their intermediates can affect the survival and behavior of Danio rerio and Allivibrio fischeri. Therefore, the photo-induced processes and additional treatment of water and wastewater containing ritonavir can minimize its toxic effect.

The co-occurrence of Zn-and Cu-based engineered nanoparticles in soils: The metal extractability vs. toxicity to Folsomia candida.

The presence of engineered nanoparticles (ENPs) in soil gradually increases, among others due to the nano-agrochemicals application. So far, the co-existence of different ENPs in soil is poorly examined. Here, the metal extractability and toxicity of soils spiked (300 mg kg-1) singly and jointly with Zn- and Cu-based ENPs or metal salts were tested. The samples were aged for 1 and 90 days. The predicting available metal component of ENPs concentrations were determined by different methods including soil pore water collection and batch extractions with H2O, CaCl2 or DTPA. Survival and reproduction of Folsomia candida were also evaluated. The combined effect of ENPs on the extractability of metals was mainly found with DTPA characterized by the highest leaching capacity among the used extractants. In fresh soil, the mixtures of ENPs differentiated only DTPA-extractable Cu level, while aging resulted in changes in both Zn and Cu concentrations leached by CaCl2 or DTPA. However, the character of the combined effect was an ENPs- and soil type-dependent, whereas the mixtures of metal salts mostly provided higher Zn and Cu recovery than the individual compounds. The pattern of co-toxicity of metal-oxide ENPs was also time-dependent: the antagonistic and synergistic effect was observed in the samples after 1 and 90 days, respectively. However, the toxicity was weakly related with extractable concentrations in both single and joint treatment of metal compounds. The distinct joint effect patterns of ENPs imply the need for more in-depth investigation of mechanisms of activity of ENPs mixtures in soil.

Cross-examination of engineered nanomaterials in crop production: Application and related implications.

The review presents the current knowledge on the development and implementation of nanotechnology in crop production, giving particular attention to potential opportunities and challenges of the use of nano-sensors, nano-pesticides, and nano-fertilizers. Due to the size-dependent properties, e.g. high reactivity, targeted and controlled delivery of active ingredients, engineered nanomaterials (ENMs) are expected to be more efficient agrochemicals than conventional agents. Growing production and usage of ENMs result in the spread of ENMs in the environment. Because plants constitute an important component of the agri-ecosystem, they are subjected to the ENMs activity. A number of studies have confirmed the uptake and translocation of ENMs by plants as well as their positive/negative effects on plants. Here, these endpoints are briefly summarized to show the diversity of plant responses to ENMs. The review includes a detailed molecular analysis of ENMs-plant interactions. The transcriptomics, proteomics and metabolomics tools have been very recently employed to explore ENMs-induced effects in planta. The omics approach allows a comprehensive understanding of the specific machinery of ENMs occurring at the molecular level. The summary of data will be valuable in defining future studies on the ENMs-plant system, which is crucial for developing a suitable strategy for the ENMs usage.

The antioxidant defense responses of Hordeum vulgare L. to polycyclic aromatic hydrocarbons and their derivatives in biochar-amended soil.

The recent studies indicated that the biochar (BC) may be a source of polycyclic aromatic hydrocarbons (PAHs) as well as their oxygen, nitrogen, or sulfur-containing derivatives that are considered as more toxic pollutants than their parent compounds. Here, the assessment of the impact of various biochars addition (1% wt.) to soil on barley Hordeum vulgare L. growth was presented. The concentrations of bioavailable PAHs and their derivatives in biochar were determined. PAHs increased reactive oxygen species generation resulting in oxidative stress in organisms. In this study, the response of soil-grown plants was examined in terms of the activity of the antioxidative enzymes (superoxide dismutase, catalase, peroxidase), lipid peroxidation, and the expression of genes related to oxidative stress. The results indicate that despite low content of a bioavailable fraction of parent compounds and their derivatives (up to 4.45 ± 0.24 ng gbiochar-1 and 0.83 ± 0.03 ng L-1, respectively) the biochemical response of plant was present, the activity of superoxide dismutase increased up to 2 times, but the activity of the other enzymes was lowered. The transcript level values support the studies on enzymatic activity. The presence of PAHs and their derivatives induced oxidative stress slightly but the plant was able to mitigate it.

Combined effect of nano-CuO and nano-ZnO in plant-related system: From bioavailability in soil to transcriptional regulation of metal homeostasis in barley.

The co-existence of engineered nanoparticles (ENPs) in the environment is an emerging issue remaining poorly investigated. The present study aimed at analyzing the fate of binary mixtures of CuO and ZnO ENPs in a soil-plant system. The ENPs were singly or jointly dosed into soil at 300 mg kg-1 and aged for 7 and 30 days. To evaluate nano-specific effects, individual and combined treatments of metal salts were also applied. Interactions between ENPs and soil-grown barley Hordeum vulgare were determined in terms of biomass, plant mineral composition as well as expression of genes regulating metal homeostasis (ZIP1,3,6,8,10,14, RAN1, PAA1,2, MTP1, COPT5) and detoxification (MT1-3). The bioavailability of Zn and Cu in bulk soil and in the rooting zone was determined using the 0.01 mol L-1 CaCl2 extraction. After combined treatment of ENPs, the extractable concentrations of Cu and Zn were lower than upon individual exposure in bulk soil. The opposite tendency was noted for metal salts. Genes related to metal uptake (ZIP) and cellular compartment (PAA2, RAN1) were mostly up-regulated by single rather than combined application of ENPs. The single and joint exposure to metals salts induced the down-regulation of these genes.

The chronic effects of CuO and ZnO nanoparticles on Eisenia fetida in relation to the bioavailability in aged soils.

The bioavailability and bioaccumulation of metal-based engineered nanoparticles (ENPs) in soils need to be evaluated in environmentally relevant scenarios. The aim of this study was an analysis of potentially available metal-component ENPs (nano-ZnO and nano-CuO) in soils. Earthworms (Eisenia fetida) were used to examine the bioaccumulation potential of ENPs. Micro-particles (micro-ZnO and micro-CuO) and metal salts (ZnCl2 and CuCl2) were used to evaluate the nano-effect and the activity of dissolved ions, respectively. Zn- and Cu-compounds were added to sandy loam and silt loam at a concentration of 10 mg kg-1. The bioavailable fractions of metals were extracted from soil using H2O, MgCl2 with CH3COONa or EDTA. EDTA was the most effective extractant of Zn and Cu (10.06-11.65 mg Zn kg-1 and 2.69-3.52 mg Cu kg-1), whereas the H2O-extractable metal concentration was at the lowest level (1.98-2.12 mg Zn kg-1 and 0.54-0.82 Cu mg kg-1). The bioavailable metal concentrations were significantly higher in silt loam than sandy loam soil, which was related to the higher pH value of silt. There were no significant differences between the Zn content in the earthworms incubated in the two soils, which may confirm the auto-regulation of the Zn content by earthworms. However, the bioaccumulation of Cu was strongly correlated with the extractable Cu concentrations. The juvenile earthworms accumulated Cu and Zn more than adults. Based on our results, aging neutralized the differences between the ionic and particulate effects of metal-compounds.

The effect of pH and ageing on the fate of CuO and ZnO nanoparticles in soils.

The objective of this study was to evaluate the fractionation of ZnO and CuO engineered nanoparticles (ENPs) in soils with a pH adjusted to 4.0, 6.5, and 9.0 after 1 day and 30 days of incubation. Based on the multi-stage extraction, 5 fractions of metals were determined. Moreover, the effect of ENPs on the activity of acid, neutral and alkaline phosphatase was determined. The results of the study revealed that pH had a dominant effect on the metal participation in soils. The levels of those fractions of metals differed between nano-ZnO and nano-CuO, which could have resulted from differences in the dissolution of the ENPs. After 1 day, the concentration of Zn2+ (0.02-7.4 mg L-1) was 10 times higher than that of Cu2+. The metal fractionation in soil treated with ENPs and metal salts may also confirm the role of ENP dissolution. The concentration of potentially bioavailable fraction of Zn increased with a drop in pH. At a 4 pH concentration of Zn in the treatment with nano-ZnO and ZnCl2 was at a similar level (42.1-45 mg kg-1), whereas the addition of nano-CuO resulted in a lower content of Cu (24.7 mg kg-1) than CuCl2 (36.5 mg kg-1). On the other hand, the concentration of fraction exchangeable of both metals in the alkaline soil did not exceed the level of 5.0 mg kg-1. Sample incubation time was especially important for metal participation in samples with a pH of 6.5. The greatest differentiation of metal fractionation between the soils was also noted at a pH of 6.5, which could also have been a result of other properties of the soils. The strong effect of pH on the lability of ENPs in soils confirmed a need to trace the fate of ENPs in extreme soil conditions as well as in changing environment.