Biodegradation of PAEs in contaminated soil by immobilized bacterial agent and the response of indigenous bacterial community.

Phthalic acid esters (PAEs) are common hazardous organic contaminants in agricultural soil. Microbial remediation is an effective and eco-friendly method for eliminating PAEs. Nevertheless, the operational mode and potential application of immobilized microorganisms in PAEs-contaminated soil are poorly understood. In this study, we prepared an immobilized bacterial agent (IBA) using a cedar biochar carrier to investigate the removal efficiency of PAEs by IBA in the soil. We found that IBA degraded 88.35% of six optimal-control PAEs, with 99.62% biodegradation of low-molecular-weight PAEs (DMP, DEP, and DBP). The findings demonstrated that the IBA achieved high efficiency and a broad-spectrum in degrading PAEs. High-throughput sequencing revealed that IBA application altered the composition of the soil bacterial community, leading to an increase in the relative abundance of PAEs-degrading bacteria (Rhodococcus). Furthermore, co-occurrence network analysis indicated that IBA promoted microbial interactions within the soil community. This study introduces an efficient method for the sustainable remediation of PAEs-contaminated soil.

From Waste to Water Purification: Textile-Derived Sorbents for Pharmaceutical Removal.

The presence of pharmaceuticals or their active metabolites in receiving waters is a sign of the inefficient removal of bioactive substrates from wastewater. Adsorption seems to be the most effective and inexpensive method of their removal. Waste management aimed at sorbents is a promising way to sustain several sustainable development goals. In the presented paper, the removal of the two most widely used drugs in the wastewater was examined. Diclofenac and carbamazepine were removed from water and wastewater using textile waste-derived sorbents. Their removal efficiency was verified by testing several process parameters such as the time of the sorption, the presence of interfering inorganic ions, the presence of dissolved organic matter, the initial pH and ionic strength of the solution, and various water matrices. The adsorption capacity was noted for diclofenac (57.1 mg/g) and carbamazepine (21.25 mg/g). The tested process parameters (pH, presence of inorganic ions, dissolved organic matter, ionic strength, water matrix) confirmed that the presented waste materials possessed a great potential for pharmaceutical removal from water matrices.

Increased oxygen content in biochar lowered bioavailability of polycyclic aromatic hydrocarbons-related toxicity to various organisms.

Agricultural or environmental application of biochar (BC) is connected with the introduction of biochar-derived components among which polycyclic aromatic hydrocarbons (PAHs) and heavy metals are the most toxic. Their presence and bioavailability are crucial considering biochar toxicity. The effect of feedstock and pyrolysis temperature on the physicochemical properties of produced biochar and contaminant content was established and combined with toxicity to a broad range of living organisms. The obtained data revealed that predicting the bioavailability of PAHs using the total content is misleading. The toxicity was influenced by factors in the following way: the bioavailable PAHs > ash > total PAHs content in BC stressing the role of BC physicochemical characteristics. Among tested BC properties, surface functionalization, e.g. presence of oxygen-containing functional groups was crucial in revealing the toxicity. The data clearly indicate that additional research is required to determine BC's impact on various organisms and performing one ecotoxicity test is not sufficient.

Biochar mitigates the postponed bioavailability and toxicity of phthalic acid esters in the soil.

Observed nowadays wide pollution of the environment with microplastic and phthalic acid esters (PAEs) (such as dimethyl phthalate, DMP; diethyl phthalate, DEP; dibutyl phthalate, DBP; benzyl butyl phthalate, BBP; di-(2-ethylhexyl) phthalate, DEHP and di-n-octyl phthalate, DNOP) is a result of their increased production and usage. Weak bonding with polymer matrix enables their easier mobilization in the environment and increased bioavailability. The aim of the presented studies was the estimation of the fate of six priority PAEs in the soil-vegetable system and the application of biochar to immobilize PAEs in the soil preventing their bioavailability to lettuce. Both the acute (one full lettuce development period) and prolongated effect (lettuce cultivated after 10 weeks from the first PAEs contamination) were estimated to examine the long-time exposure under crop rotation. The addition of 1 % of corn-derived biochar immobilized PAEs in the soil efficiently (up to 4 times increased concentration) with the following order: DBP < DEP < DMP < DEHP < DNOP < BBP. Bioavailable PAEs were determined in lettuce roots (DMP, BBP, DEHP), and lettuce leaves (DEP, DBP, DNOP) but the presence of biochar lowered their content. PAEs, although not available for lettuce, were available for other organisms, confirming that the bioavailability or lack of nutrients is of great importance in PAEs-polluted soil. In long-time experiments, without biochar amendment, all PAEs were 3-12 times more bioavailable and were mainly accumulated in lettuce roots. The biochar addition significantly reduces (1.5-11 times) PAEs bioavailability over time. However, the PAEs content in roots remained significantly higher in samples with crop rotation compared to samples where only lettuce was grown. The results confirmed that biochar addition to the soil reduces their bioavailability and mobility inside the plant, limiting their transport from roots to leaves and reducing the exposure risk but confirming that lettuce leaves may be a safe food when cultivated in PAEs-polluted soil.

Dissolved organic matter influences the indigenous bacterial community and polycyclic aromatic hydrocarbons biodegradation in soils.

In polycyclic aromatic hydrocarbon (PAH) contaminated soils, bioremediation is superior to other strategies owing to its low cost and environmental friendliness. However, dissolved organic matter (DOM) and indigenous bacterial communities can affect the efficiency of PAH-degrading bacteria (PDB). This study found that exogenous PDB (C1) including the genera Acinetobacter, Stenotrophomonas, and Comamonas, decreased the bacterial diversity of Alfisol, Ultisol, Inceptisol, and Mollisol, and DOM enhanced the diffusion of PDB and the bioavailability of PAH. In addition, bacteria preferred to ingest low molecular weight DOM fractions, and the abundances of lipid-like and protein-like substances decreased by 0.12-3.03 % and 1.73-4.60 %. The DOM fractions had a more marked influence on the indigenous bacteria than the exogenous PDB, and PDB dominated the PAH biodegradation process in the soils. More COO functional groups promoted the utilization of higher molecular weight-related homologue fractions by bacteria, and lower molecular weight fractions carrying more CH2 functional groups declined during biodegradation. This study investigated the variations in bacterial communities during biodegradation and revealed the effects of DOM fractions on biodegradation in PAH-contaminated soils at the molecular level. These results will promote the development of bioremediation strategies for organics-contaminated soil and provide guidance for prediction models of soil biodegradation kinetics.

Formation and biotoxicity of environmentally persistent free radicals in steelworks soil under thermal treatment.

Thermal treatment are commonly used to address organic contaminated soils. In particular, the pyrolysis of organic substances can result in the creation of environmentally persistent free radicals (EPFRs). We investigated a steelworks site in Chongqing (China) to observe changes in EPFRs before and after thermal treatment. Our findings revealed that the EPFRs were carbon-centered radicals with a g-factor < 2.0030 and a spin density ranging from n.d.-5.23 × 1015 spins/mg. The formation of EPFRs was driving by polycyclic aromatic hydrocarbons (PAHs), Mn, Cu, and total organic carbon (TOC). Following the thermal treatment, the spin densities of EPFRs increased by a factor of 0.25 to 1.81, with maximum levels reached at 300 °C. High molecular weight PAHs exhibited high heat capacity, enabling the generation of more EPFRs. The thermal decay of EPFRs occurred in two stages, with the shortest 1/e lifetime lasting up to 16.8 h. Raising the temperature or prolonging time can significantly reduce EPFRs levels. Thermal treatment increased the generation of EPFRs, hydroxyl radicals (•OH) and superoxide radical (•O2-), leading to a decrease in bacterial luminescence. Specifically, •OH contributed to approximately 73% of the B. brilliantus inhibition. Our results highlight that the thermal treatment significantly enhance EPFRs concentrations, and the treated soil remained ecologically risky. The knowledge of the formation of EPFRs and their biotoxicity is shedding new light on the thermal treatment risk management.

Increased concentration of PAH derivatives in biochar-amended soil observed in a long-term experiment.

During biochar preparation or application some toxic substances may be formed. The established limitations of the content of polycyclic aromatic hydrocarbons (PAHs) aim to monitor the fate of PAHs in the life cycle of biochar. The latest studies have revealed that besides PAHs, some of their derivatives with confirmed toxicity are formed. There has been no policy regards PAH derivatives in biochar yet. The aim of the presented studies was the estimation the changes in the content of PAHs and their derivatives during the agricultural application of biochar. A pot experiment with grass revealed that in a short time, both the content of PAHs and their derivatives was reduced. Similarly, when biochar was added to soil in a long-term experiment, the content of determined derivatives was below the limit of detection, whereas interestingly, the content of pristine PAHs increased with time. Co-addition of biochar and sewage sludge increased the content of PAHs and their derivatives indicating potential environmental hazard due to their presence. However, the key point is the estimation of the bioavailability of PAHs and their derivatives as only the bioavailable fraction is revealing the environmental hazard.

Fast and reliable determination of phthalic acid esters in soil and lettuce samples based on QuEChERS GC-MS/MS.

Phthalates are commonly used as plasticizers, and solvents in industry and households. We propose an application of the QuEChERS method for the determination of six PAEs in the soil and lettuce (roots and leaves) by GC-MS/MS. The QuEChERS method validation procedure was performed and good linearity (>0.997), recovery (97.2-99.1 %), very low detection limits (0.09-0.43 ng/g), and satisfactory inter- and intraday precision (∼4%) were obtained confirming that QuEChERS GC-MS/MS applied for PAEs determination in the environmental samples is a cheap and environmentally friendly method. In general, the higher the number of carbon atoms in PAEs, the higher the percentage noted in the lettuce roots. At higher PAEs concentration (60 ng/g) the main bis(2-ethylhexyl) phthalate (DEHP) sink were roots whereas at lower concentrations (30 ng/g) most of DEHP was noted in lettuce leaves implying that the fate of PAEs was governed not by the chemical structure of PAEs but rather partitioning (logKow).

Plant-Waste-Derived Sorbents for Nitazoxanide Adsorption.

The increased application of drugs during the COVID-19 pandemic has resulted in their increased concentration in wastewater. Conventional wastewater treatment plants do not remove such pollutants effectively. Adsorption is a cheap, effective, and environmentally friendly method that can accomplish this. On the other hand, maintaining organic waste is required. Thus, in this study, plant waste-derived pelletized biochar obtained from different feedstock and pyrolyzed at 600 °C was applied for the adsorption of nitazoxanide, an antiparasitic drug used for the treatment of SARS-CoV-2. The adsorption was fast and enables one to remove the drug in one hour. The highest adsorption capacity was noted for biochar obtained from biogas production (14 mg/g). The process of NTZ adsorption was governed by chemisorption (k2 = 0.2371 g/mg min). The presence of inorganic ions had a detrimental effect on adsorption (Cl-, NO3- in 20-30%) and carbonates were the most effective in hindering the process (60%). The environmentally relevant concentration of DOM (10 mg/L) did not affect the process. The model studies were supported by the results with a real wastewater effluent (15% reduction). Depending on the applied feedstock, various models described nitazoxanide adsorption onto tested biochars. In summary, the application of carbonaceous adsorbents in the pelletized form is effective in nitazoxanide adsorption.

Estrogens and xenoestrogen residues in manure-based fertilizers and their potential ecological risks.

Optimal manure treatment aimed at usage as agricultural soil fertilizers is a prerequisite ecological pollution control strategy. In this work, livestock manure-based fertilizers were collected from 71 animal farms across 14 provinces in China. The contamination levels and potential ecotoxicological risks of residual steroid estrogens (SEs): estrone (E1), estriol (E3), 17α-estradiol (17α-E2), 17ß-estradiol (17ß-E2) and xenoestrogen (XE) bisphenol A (BPA), were investigated. The results showed that the occurrence frequencies for SEs and XE ranged from 66.67% to 100%, and the mean concentration varied considerably across the study locations. The total content of SEs and XE in Hebei province was the highest, and swine manure-based fertilizers concentrations were higher than the levels reported in other animal fertilizers. Compared with farm level manure, manure-based fertilizers are processed by composting, and the micropollutants quantities are significantly reduced (mean: 87.65 - 534.02 µg/kg). The total estradiol equivalent quantity (EEQ) that might migrate to the soil was estimated to be 1.23 µg/kg. Based on the estimated application rate of manure, 38% of the fertilizers risk quotients exceeded 0.1, indicating medium to high risks pressure on terrestrial organisms. Nonetheless, the estrogenic risk was lower in manure-based fertilizers than in manure. This study highlights the significance of proper treatment of livestock manure and designing an optimal manure fertilization strategy to mitigate the risks posed by SEs and XEs to the agroecosystems.

Microorganisms and their metabolites affect the content of polycyclic aromatic hydrocarbons and their derivatives in pyrolyzed material.

Toxic polycyclic aromatic hydrocarbons (PAHs) and more toxic N- and O-containing derivatives can be determined in biochar. However, their fate in the environment and bioavailability depends on many parameters and was not studied yet. In the presented studies a set of biochars obtained from various feedstock at the same pyrolysis temperature (600 °C) subjected to environmental pressure e.g. soil microorganisms and enzymes was described. Presented study aimed to determine the effect of biological agents on the physicochemical characteristic and the content of PAHs and their derivatives in biochars after long-term treatment (6 months). The results indicated that enzymatic aging usually lowered (up to 94 %) the content of PAHs and their derivatives in biochar. Simultaneously, biological aging reduced the bioavailability of tested compounds. Considering the total fraction of PAHs and their derivatives, biochars treated with nutrients and microbial inoculum were characterized by the lowest content of analytes (even in comparison to biochars treated with nutrients alone). To complement the obtained results, the content of C, H, N, O, and ash as well as specific surface area, aromaticity, polarity, and hydrophilicity in biochar before and after modifications were determined. In general, enzymatic aging increased, and biological aging decreased the content of C% and H% in biochar. Both aging processes lowered the H/C ratio which indicated the decrease of the aromatization degree for artificially altered biochar.

The Visible-Light-Driven Activity of Biochar-Doped TiO2 Photocatalysts in ß-Blockers Removal from Water.

Water is the most important life-giving resource on earth. Nowadays, intensive growth of the world population has resulted in increased water consumption and the production of wastewater. Additionally, the presence of pharmaceuticals in treated conventional wastewater or even in the environment is strictly indicating that present techniques of wastewater treatment are not efficient enough and are not designed to remove such pollutants. Scarce water resources in the world are the main driving force for the innovation of novel techniques of water and wastewater treatment. Photocatalysis, as one of the advanced oxidation processes, enables the transformation of recalcitrant and toxic pollutants into CO2, water, and inorganic salts. In the present paper, the photocatalytic oxidation of ß-blockers-metoprolol and propranolol-are described. For photocatalytic oxidation, novel TiO2 photocatalysts modified with biochar were used. Photocatalysts were prepared by sol-gel method and the effect of photocatalysts type, presence of inorganic ions, dissolved organic matter, and different water matrix was established. The results indicate that using only the decrease in the tested pollutant concentration is not effective enough in establishing the treatment method's safety. There is a need to use additional testing such as ecotoxicity tests; however, the key parameter is the properly chosen tested organism.

Radially aligned hierarchical N-doped porous carbon beads derived from oil-sand asphaltene for long-life water filtration and wastewater treatment.

The application of waste-derived highly efficient adsorbent for organic pollutants removal from water and wastewater is presented. Highly porous carbon beads with radially aligned macrochannels were prepared from asphaltene. Well-ordered inwardly aligned macrovoids favored solute diffusion and maximized the liquid accommodation capacity. A further N-doping could modulate the sorbent hydrophilicity leading to an outstanding absorption performance for a range of organic solvents and oily chemicals. N-doped carbon beads were effective sorbents of lopinavir (LNV) and ritonavir (RNV) from water and wastewater. The process of sorption was fast, and the highest removal was noted for RNV than LPV. N-doping favored LNV and RNV adsorption due to the increased porous structure of N-doped asphaltene beads. The chemisorption of both LPV and RTV was a rate-limiting step. The presence of co-pollutants in treated wastewater enhanced LPV and RNV removal and an up to 470 % increase was noted. The presence of LPV or RTV in distilled water was not toxic to Aliivibrio fischeri or even can stimulate their growth. However, after the adsorption process, the solution of RTV reduced its toxicity significantly and the final solution was not toxic. The opposite effect was noted for LPV. Given the repeatability, high removal performance, and cost-effectiveness of the asphaltene-based carbon microtubes when compared to other well-known sorbents such as carbon nanotubes, they demonstrated great potential as a low-cost and effective agent for long-life water filtration and wastewater treatment.

Long-term physical and chemical aging of biochar affected the amount and bioavailability of PAHs and their derivatives.

Biochar applied into the soil is recommended as an effective tool for increasing its properties and crop productivity. However, biochar can contain some potentially toxic compounds such as polycyclic aromatic hydrocarbons (PAHs). Moreover, during biochar production or environmental application (e.g. as soil fertilizer), more toxic PAHs derivatives containing nitrogen, oxygen or sulfur can be formed. There is a lack of information on how the environmental factors affect the bioavailability of such compounds during the long-term application of BC into the soil. In the presented studies the effects of physical (freeze-thaw cycles) and chemical aging (temperatures 60 °C and 90 °C) on the total and bioavailable content of PAHs and their derivatives were estimated. The results indicate that long-term (6 months) aging affected the physicochemical characteristic of biochars promoting the formation of new C and O-containing species on the BC surface increasing their polarity and hydrophilicity. Physical and chemical aging promoted the formation of compounds with higher molecular weight and a significant (up to 550 %) increase in the bioavailability of PAHs and their derivatives. The results of this study highlight the importance of the bioavailable fraction of PAHs and their derivatives for evaluation of the toxicity of aged biochar.

Digestion of plastics using in vitro human gastrointestinal tract and their potential to adsorb emerging organic pollutants.

Excessive plastic use has inevitably led to its consumption by organisms, including humans. It is estimated that humans consume 20 kg of plastic during their lifetime. The presence of microplastics in the human body can carry serious health risks, such as biological reactions e.g. inflammation, genotoxicity, oxidative stress, apoptosis, as well toxic compounds leaching of unbound chemicals/monomers, free radicals or adsorbed organic pollutants, which mainly depend on the properties of the ingested plastic. Plastics are exposed to different substances (e.g., enzymes and acids) in the digestive system, which potentially affects their properties and structure. By stimulating the human digestive system and applying a set of advanced analytical tools, we showed that the surface of polystyrene and high-density polyethylene plastics frequently in contact with food undergoes fundamental changes during digestion. This results in the appearance of additional functional groups, and consequent increase in the plastic adsorption capacity for hydrophobic ionic compounds (such as triclosan and diclofenac) while reducing its adsorption capacity for hydrophobic non-ionic compounds (such as phenanthrene). Micro- and nanostructures that formed on the flat surface of the plastics after digestion were identified using scanning electron microscopy. These structures became defragmented and detached due to mechanical action, increasing micro- and nanoplastics in the environment. Due to their size, the release of plastic nanostructures after digestion can become an "accidental food source" for a wider group of aquatic organisms and ultimately for humans as the last link in the food chain. This, combined with improved adsorption capacity of digested plastics to hydrophobic ionic pollutants, can pose a serious threat to the environment including human health and safety.

Low bioavailability of derivatives of polycyclic aromatic hydrocarbons in biochar obtained from different feedstock.

In the last years, there is great progress in the field of studies on the thermal transformation of wastes into valuable materials such as biochar. High-temperature processes, however, are connected with the formation of polycyclic aromatic hydrocarbons (PAHs) with confirmed toxicity. However, during pyrolysis, some derivatives containing oxygen, nitrogen, or sulfur can also be formed. Their toxicity is expected to be higher than parent PAHs. However, the key parameter in the agricultural application of carbonaceous materials is PAHs' bioavailability. The aim of the presented studies was the determination of the effect of various feedstock (wheat straw (Triticum L.), willow (Salix viminalis), sunflower, residues from softwood and hardwood, sewage sludges, and residues from biogas production) on the formation of PAHs and their derivatives (O-, N-PAHs) in biochar and their bioavailability. The results indicated that the content of total and bioavailable PAHs in obtained biochar was rather low. The concentration of total PAHs in plant-derived biochar reached 57 ± 3 ng g-1 - 181 ± 8 ng g-1, whereas sewage sludge-derived biochar contained from 121 ± 6 ng g-1 to 188 ± 9 ng g-1 of PAHs. The highest concentration of PAHs was noted in biochar obtained from residues from biochar production - up to 202 ± 9 ng g-1. The total concentration of bioavailable PAHs was lower and reached 2-4.45 ng L-1 for plant-derived biochar, 3-40 ng L-1 for sewage sludge-derived biochar. The highest content of bioavailable PAHs was noted in biochar obtained from residues from biogas production: 9-42 ng L-1 indicating that increased attention should be paid to using this type of biochar. Among PAHs derivatives, nitronaphthalene, 1-methyl-5-nitronaphthalene, 1-methyl-6-nitronaphthalene, 9,10-anthracenedione, 4H-cyclopenta(def)phenanthrene, nitropyrene were determined at various levels and their concentrations were from below the limit of detection (LOD) to 28 ng L-1 for plant-derived biochar, 3-16 ng L-1 for biochar obtained from residues from biogas production, and 5-45 ng L-1 for sewage sludge-derived biochar. The content of bioavailable PAHs derivatives was, generally, one order of magnitude lower than parent PAHs derivatives, and reached from below LOD up to almost 1 ng L-1 for plant-derived biochar, from 0.5 to 2 ng L-1 for biochar obtained from residues from biogas production, and from 0.2 to almost 5 ng L-1 for sewage sludge-derived biochar confirming the safety of agricultural usage of biochar.

Screen-Printed Voltammetric Sensors-Tools for Environmental Water Monitoring of Painkillers.

The dynamic production and usage of pharmaceuticals, mainly painkillers, indicates the growing problem of environmental contamination. Therefore, the monitoring of pharmaceutical concentrations in environmental samples, mostly aquatic, is necessary. This article focuses on applying screen-printed voltammetric sensors for the voltammetric determination of painkillers residues, including non-steroidal anti-inflammatory drugs, paracetamol, and tramadol in environmental water samples. The main advantages of these electrodes are simplicity, reliability, portability, small instrumental setups comprising the three electrodes, and modest cost. Moreover, the electroconductivity, catalytic activity, and surface area can be easily improved by modifying the electrode surface with carbon nanomaterials, polymer films, or electrochemical activation.

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.

Detoxifying SARS-CoV-2 antiviral drugs from model and real wastewaters by industrial waste-derived multiphase photocatalysts.

The use of antiviral drugs has surged as a result of the COVID-19 pandemic, resulting in higher concentrations of these pharmaceuticals in wastewater. The degradation efficiency of antiviral drugs in wastewater treatment plants has been reported to be too low due to their hydrophilic nature, and an additional procedure is usually necessary to degrade them completely. Photocatalysis is regarded as one of the most effective processes to degrade antiviral drugs. The present study aims at synthesizing multiphase photocatalysts by a simple calcination of industrial waste from ammonium molybdate production (WU photocatalysts) and its combination with WO3 (WW photocatalysts). The X-ray diffraction (XRD) results confirm that the presence of multiple crystalline phases in the synthesized photocatalysts. UV-Vis diffuse reflectance spectra reveal that the synthesized multiphase photocatalysts absorb visible light up to 620 nm. Effects of calcination temperature of industrial waste (550-950 °C) and WO3 content (0-100%) on photocatalytic activity of multiphase photocatalysts (WU and WW) for efficient removal of SARS-CoV-2 antiviral drugs (lopinavir and ritonavir) in model and real wastewaters are studied. The highest k1 value is observed for the photocatalytic removal of ritonavir from model wastewater using WW4 (35.64 ×10-2 min-1). The multiphase photocatalysts exhibit 95% efficiency in the photocatalytic removal of ritonavir within 15 of visible light irradiation. In contrast, 60 min of visible light irradiation is necessary to achieve 95% efficiency in the photocatalytic removal of lopinavir. The ecotoxicity test using zebrafish (Danio rerio) embryos shows no toxicity for photocatalytically treated ritonavir-containing wastewater, and the contrary trend is observed for photocatalytically treated lopinavir-containing wastewater. The synthesized multiphase photocatalysts can be tested and applied for efficient degradation of other SARS-CoV-2 antiviral drugs in wastewater in the future.

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.