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Despite being drastically restricted in the 1970s, polychlorinated biphenyls (PCBs) still belong among the most hazardous contaminants. The chemical stability and dielectric properties of PCBs made them suitable for a number of applications, which then lead to their ubiquitous presence in the environment. PCBs are highly bioaccumulative and persistent, and their teratogenic, carcinogenic, and endocrine-disrupting features have been widely reported in the literature. This review discusses recent advances in different techniques and approaches to remediate historically contaminated matrices, which are one of the most problematic in regard to decontamination feasibility and efficiency. The current knowledge published in the literature shows that PCBs are not sufficiently removed from the environment by natural processes, and thus, the suitability of some approaches (e.g., natural attenuation) is limited. Physicochemical processes are still the most effective; however, their extensive use is constrained by their high cost and often their destructiveness toward the matrices. Despite their limited reliability, biological methods and their application in combinations with other techniques could be promising. The literature reviewed in this paper documents that a combination of techniques differing in their principles should be a future research direction. Other aspects discussed in this work include the incompleteness of some studies. More attention should be given to the evaluation of toxicity during these processes, particularly in terms of monitoring different modes of toxic action. In addition, decomposition mechanisms and products need to be sufficiently clarified before combined, tailor-made approaches can be employed.

Nano-scale zero-valent iron (nZVI) began attracting research attention in remediation practice in recent decades as a prospective nanomaterial applicable to various contaminated matrices. Despite concerns about the negative effects of nanomaterials on ecosystems, the number of reliable toxicity tests is limited. We have developed a test based on the evaluation of oxidative stress (OS). The test employed the analysis of a typical OS marker (malondialdehyde, MDA), after exposure of six bacterial strains to the tested nanomaterial. We also attempted to use other OS and cell membrane damage assays, including the determination of glutathione and lactate dehydrogenase, respectively. However, we found that the components of these assays interfered with nZVI; therefore, these tests were not applicable. The MDA assay was tested using nZVI and three newly engineered oxide shell nZVI materials with different oxide thicknesses. Six different bacterial species were employed, and the results showed that the test was fully applicable for the concentrations of nanomaterials used in remediation practice (0.1–10 g/L). MDA was produced in a dose-response manner, and the bacteria showed a similar response toward pure pyrophoric nZVI, reaching EC50 values of 0.3–1.1 g/L. We observed different responses in the absolute production of MDA; however, the MDA concentrations were correlated with the cell membrane surfaces of the individual strains (R > 0.75; P 0.95; P

Abiotic and biotic remediation of chlorinated ethenes (CEs) in groundwater from a real contaminated site was studied using biochar-based composites containing nanoscale zero-valent iron (nZVI/BC) and natural resident microbes/specific CE degraders supported by a whey addition. The material represented by the biochar matrix decorated by isolated iron nanoparticles or their aggregates, along with the added whey, was capable of a stepwise dechlorination of CEs. The tested materials (nZVI/BC and BC) were able to decrease the original TCE concentration by 99% in 30 days. Nevertheless, regarding the transformation products, it was clear that biotic as well as abiotic transformation mechanisms were involved in the transformation process when nonchlorinated volatiles (i.e., methane, ethane, ethene, and acetylene) were detected after the application of nZVI/BC and nZVI/BC with whey. The whey addition caused a massive increase in bacterial biomass in the groundwater samples (monitored by 16S rRNA sequencing and qPCR) that corresponded with the transformation of trichloro- and dichloro-CEs, and this process was accompanied by the formation of less chlorinated products. Moreover, the biostimulation step also eliminated the adverse effect caused by nZVI/BC (decrease in microbial biomass after nZVI/BC addition). The nZVI/BC material or its aging products, and probably together with vinyl chloride-respiring bacteria, were able to continue the further reductive dechlorination of dichlorinated CEs into nonhalogenated volatiles. Overall, the results of the present study demonstrate the potential, feasibility, and environmental safety of this nanobioremediation approach.

Sewage sludge was excluded from the list of component materials for the production of EU fertilizing products and it was banned as feedstock to produce pyrolysis & gasification materials in European Commission’s technical proposals for selected new fertilizing materials under the Regulation 2019/1009 (STRUBIAS report). This exclusion of pyrolysis as a viable way to treat sewage sludge was mainly due to the lack of data on the fate of organic pollutants at pyrolysis conditions. In this work, we are addressing this knowledge gap. We studied slow pyrolysis as a potential process to efficiently treat organic pollutants present in stabilized sewage sludge. Sewage sludge was pyrolyzed in a quartz fixed bed reactor at temperatures of 400–800 °C for 2 h and the sludge and resulting sludge-chars were analyzed for the presence of four groups of organic pollutants, namely (i) polychlorinated biphenyls (PCBs), (ii) polycyclic aromatic hydrocarbons (PAHs), (iii) pharmaceuticals, and (iv) endocrine-disrupting and hormonal compounds. Pyrolysis at ≥ 400 °C effectively removed pharmaceuticals (group iii) to below detection limits, whereas pyrolysis at temperatures higher than 600 °C was required to remove more than 99.8% of the compounds from groups i, ii and iv. Based on these findings, we propose, that high temperature (>600 °C) slow pyrolysis can satisfactory remove organic pollutants from the resulting sludge-char, which could be safely applied as soil improver.

Highly persistent, toxic and bioaccumulative per - and polyfluoroalkyl substances (PFAS) represents a serious problem for the environment and their concentrations and fate remain largely unknown. The present study consists of a PFAS screening in sludges originating from 43 wastewater treatment plants (WWTPs) in the Czech Republic. To analyze an extended group of PFAS consisting of 32 PFAS, including GenX and other new replacements of older and restricted PFAS in sludge, a new method was optimized and validated using pressurized solvent extraction, followed by the SPE clean-up step to eliminate the observed matrix effects and LC-MS/MS. The results revealed high PFAS contamination of sewage sludge, reaching values from 5.6 to 963.2 ng g−1. The results showed that in the majority of the samples (about 60%), PFOS was the most abundant among the targeted PFAS, reaching 932.9 ng g−1. Approximately 20% of the analyzed samples contained more short-chain PFAS, suggesting the replacement of long-chain PFAS (especially restricted PFOA and PFOS). GenX was detected in 9 samples, confirming the trend in the use of new PFAS. The results revealed that significantly higher contamination was detected in the samples from large WWTPs (population equivalent > 50,000; p-value

A considerable amount of scientific evidence indicates that a number of pharmaceuticals that could be detected in the environment can contribute towards the development of problems associated with human reproductive systems, as well as those of wildlife. We investigated the estrogenic and androgenic effects of select pharmaceuticals with high production volume and environmental relevance. We examined the receptor-binding activities of these pharmaceuticals in the T47D human cell line using altered secretion of cytokine CXCL12. Functional yeast-luciferase reporter gene assays were also employed to confirm the mechanism of receptor binding by estrogen and androgen. Non-steroidal anti-inflammatory drugs, namely ibuprofen, diclofenac and antiarrhythmic agent amiodarone showed strong anti-estrogenic effects in the T47D cell line. In the yeast-luciferase assay, these anti-inflammatory drugs also demonstrated anti-estrogenic potency and inhibited the E2 response in a concentration-dependent manner. Amiodarone did not exhibit any response in the yeast-luciferase assay; therefore, the endocrine disruption presumably occurred at a different level without directly involving the receptor. All the anti-inflammatory drugs considered in this study, including ketoprofen, naproxen and clofibrate, exhibited a dose-dependent antagonism towards the androgen receptor in the yeast-luciferase assays. Several other drugs, including the stimulant caffeine, did not show any response in the tests that were employed. A risk assessment analysis using 'Hazard Quotient' suggested a potential risk, especially in the cases of ibuprofen, ketoprofen, diclofenac and clofibrate. The results reveal the intrinsic endocrine disrupting nature of several pharmaceuticals and thus could contribute towards explaining a number of adverse health effects on humans and wildlife.

After the phase-out of two commercial mixtures of brominated flame retardants, an increasing number of alternative flame retardants have been introduced in commercial applications. None of them, however, has been thoroughly tested for its hormonal activity. We used two yeast reporter-gene assays to determine the potential of eleven compounds to interfere with estrogenic and androgenic pathways. Our data demonstrate the ability of 2,4,6-tribromophenol to lower the transcriptional activity of human estrogen and androgen receptors. A nominal IC 50 value of 14.1 μM for anti-estrogenic and 3.9 μM for anti-androgenic activity was obtained using the luciferase reporter. An IC 50 value of 9.2 μM was calculated for the anti-estrogenic activity measured by the β-galactosidase assay. Of the tested chemicals, this study highlights the endocrine disrupting effects of 2,4,6-tribromophenol whose occurrence in the environment should be monitored.

Cultures of the ligninolytic fungus Irpex lacteus incubated in a nutrient liquid medium degraded more than 70% of the initially applied benz[a]anthracene within 14 days. At the first step of metabolization, benz[a]anthracene was transformed via a typical pathway of ligninolytic fungi to benz[a]anthracene-7,12-dione (BaAQ). The product was further transformed by at least two ways, whereas one is complied with the anthracene metabolic pathway of I. lacteus. Benz[a]anthracene-7,12-dione was degraded to 1,2-naphthalenedicarboxylic acid and phthalic acid that was followed with production of 2-hydroxymethyl benzoic acid or monomethyl and dimethylesters of phthalic acid. Another degradation product of BaAQ was identified as 1-tetralone. Its transformation via 1,4-naphthalenedione, 1,4-naphthalenediol and 1,2,3,4-tetrahydro-1-hydroxynaphthalene resulted again in phthalic acid. None of the intermediates were identified as dead-end metabolites. Metabolites produced by ring cleavage of benz[a]anthracene using the ligninolytic fungus are firstly presented in this work.

A group of white rot fungi (Irpex lacteus, Panus tigrinus, Dichomitus squalens, Trametes versicolor and Pleurotus ostreatus) was investigated for the biodegradation of norfloxacin (NOR), ofloxacin (OF) and ciprofloxacin (CIP). The selected fluoroquinolones were readily degraded almost completely by I. lacteus and T. versicolor within 10 and 14 d of incubation in liquid medium, respectively. The biodegradation products were identified by liquid chromatography-mass spectrometry. The analyses indicated that the fungi use similar mechanisms to degrade structurally related antibiotics. The piperazine ring of the molecules is preferably attacked via either substitution or/and decomposition. In addition to the degradation efficiency, attention was devoted to the residual antibiotic activities estimated using Gram-positive and Gram-negative bacteria. Only I. lacteus was able to remove the antibiotic activity during the course of the degradation of NOR and OF. The product-effect correlations evaluated by Principal Component Analysis (PCA) enabled elucidation of the participation of the individual metabolites in the residual antibacterial activity. Most of the metabolites correlated with the antibacterial activity, explaining the rather high residual activity remaining after the biodegradation. PCA of ligninolytic enzyme activities indicated that manganese peroxidase might participate in the degradation.

The aim of the present study was to compare the degrading capabilities of eight ligninolytic fungal representatives towards a technical mixture of polychlorinated biphenyls (Delor 103). Axenic cultures of the fungi, either in complex or N-limited liquid media, were spiked with the technical mixture of Delor 103. All of the fungal strains were able to degrade the pollutant significantly after 6weeks of incubation in both media. Outstanding results were achieved by the treatment with Pleurotus ostreatus, which removed 98.4% and 99.6% of the PCB mixture in complex and mineral media, respectively. This fungus was the only one capable of breaking down penta- and hexachlorinated biphenyls in the complex medium. Ecotoxicological assays performed with the luminescent bacterium Vibrio fischeri demonstrated that all of the fungal strains employed in this study were able to remove the toxicity only temporarily (e.g., after 28d of incubation), while P. ostreatus was capable of suppressing the toxicity associated to PCBs along the whole incubation period in both media. We also performed an extensive set of qualitative GC/MS analyses and chlorinated derivatives of hydroxy- and methoxy-biphenyls were detected along with monoaromatic structures, i.e. chlorobenzoic acids, chlorobenzaldehydes and chlorobenzyl alcohols. This results indicate that both intracellular (cytochrome P-450 monooxigenase, aryl-alcohol dehydrogenase and aryl-aldehyde dehydrogenase) and extracellular (ligninolytic enzymes) enzymatic systems could be involved in the biotransformation of PCB by ligninolytic fungi. The data from this work also document that the fungi are able to degrade further the main metabolites on the PCB pathway (i.e. chlorobenzoic acids) simultaneously with PCBs.

The objective of the study was to investigate the impact of chopped wheat straw (CWS), ground corn cobs (GCC) and commercial pellets (CP), as inoculum carriers, on both growth and polycyclic aromatic hydrocarbons (PAH) degradation performances of Dichomitus squalens, Pleurotus ostreatus and Coprinus comatus. A historically-contaminated soil (HCS) and creosote-treated shavings (CTS) from the Sobeslav wood preservation plant, characterized by different relative abundances of the PAH bioavailable fractions, were used to assess the contaminated matrix effect and its interaction with both carrier and fungal strain. In HCS, best results were obtained with CP-immobilized P. ostreatus, which was able to deplete benzo[a]anthracene, chrysene, benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF) and benzo[a]pyrene (BaP) by 69.1%, 29.7%, 39.7%, 32.8% and 85.2%, respectively. Only few high-molecular mass PAHs such as BbF, BkF and BaP were degraded beyond their respective bioavailable fractions and this effect was confined to a limited number of inoculants. In CTS, only phenanthrene degradation exceeded its respective bioavailability from 1.42 to 1.86-fold. Regardless of both inoculum carrier and fungal species, degradation was positively and significantly (P

Endocrine-disrupting compounds (EDCs) represent a large group of substances of natural and anthropogenic origin. They are widely distributed in the environment and can pose serious risks to aquatic organisms and to public health. In this study, 4-n-nonylphenol, technical 4-nonylphenol, bisphenol A, 17α-ethinylestradiol, and triclosan were biodegraded by eight ligninolytic fungal strains ( Irpex lacteus 617/93, Bjerkandera adusta 606/93, Phanerochaete chrysosporium ME 446, Phanerochaete magnoliae CCBAS 134/I, Pleurotus ostreatus 3004 CCBAS 278, Trametes versicolor 167/93, Pycnoporus cinnabarinus CCBAS 595, Dichomitus squalens CCBAS 750). The results show that under the used conditions the fungi were able to degrade the EDCs within 14 d of cultivation with exception of B. adusta and P. chrysosporium in the case of triclosane and bisphenol A, respectively. I. lacteus and P. ostreatus were found to be most efficient EDC degraders with their degradation efficiency exceeding 90% or 80%, respectively, in 7 d. Both fungi degraded technical 4-nonylphenol, bisphenol-A, and 17α-ethinylestradiol below the detection limit within first 3 d of cultivation. In general, estrogenic activities assayed with a recombinant yeast test decreased with advanced degradation. However, in case of I. lacteus , P. ostreatus , and P. chrysosporium the yeast assay showed a residual estrogenic activity (28-85% of initial) in 17α-ethinylestradiol cultures. Estrogenic activity in B. adusta cultures temporally increased during degradation of technical 4-nonylphenol, suggesting a production of endocrine-active intermediates. Attention was paid also to the effects of EDCs on the ligninolytic enzyme activities of the different fungi strains to evaluate their possible stimulation or suppression of activities during the biodegradation processes.

The high hydrophobicity of polycyclic aromatic hydrocarbons (PAHs) greatly hamper their degradation in liquid media. The use of an organic solvent can assist the degradative action of ligninolytic enzymes from white rot fungi. The enzymatic action of the enzyme manganese peroxidase (MnP) in media containing a miscible organic solvent, acetone (36% v/v), was evaluated as a feasible system for the in vitro degradation of three PAHs: anthracene, dibenzothiophene and pyrene. These compounds were degraded to a large extent after a short period of time (7, 24 and 24h, respectively), at conditions maximizing the MnP-oxidative system. The initial amount of enzyme present in the reaction medium was determinant for the kinetics of the process. The order of degradability, in terms of degradation rates was as follows: anthracene>dibenzothiophene>pyrene. The intermediate compounds were determined using gas chromatography-mass spectrometry and the degradation mechanisms were proposed. Anthracene was degraded to phthalic acid. A ring cleavage product of the oxidation of dibenzothiophene, 4-methoxybenzoic acid, was also observed.

The biodegradation of polychlorinated biphenyls (PCBs), formerly applied in technical mixtures called Delor 103, was realized by the white rot fungus Pleurotus ostreatus. Besides the efficiency of degradation the translocation of PCBs into the fruit bodies grown during cultivation on straw were of special interest. The selectivity of PCBs degradation is discussed on the basis of structural features of the individual congeners. The most important structural factors affecting the degradation efficiency are indicated with molecular descriptors. Basic dependences of the degradation efficiency of congeners on their chlorination grade and ortho chlorosubstitution could be proved. Additionally, other structural parameters such as the number and position of non-substituted carbon in the biphenyl molecule also affect the degradation results. Apart from the removal of Delor 103 the translocation of PCB isomers into the fruit bodies growing up during cultivation was observed. The structural features assisting the transport of PCB congeners from the straw substrate colonized with mushroom mycelium (straw/mycelium) to the mushroom fruit bodies are also relevant for the degradation mechanism but act reversely. Among the chlorination grade, structural parameters such as the number of para and adversely positioned chlorines or the number of occupied para and meta positions contribute to an accumulation of individual PCB congeners in the mushrooms. In total, only few PCB amounts (below 0.1% of the initially present PCBs in straw) were transported into the fruit bodies and a dangerous PCB contamination was never reached while the experiment. A combination of accelerated solvent extraction and GC-MS analysis was the analytical basis for the investigation presented.