The treatment of contaminants from lignocellulosic biorefinery effluent has recently been identified as a unique challenge. This study focuses on removing phenolic contaminants and polycyclic aromatic hydrocarbons (PAHs) from lignocellulosic biorefinery wastewater (BRW) applying a laccase-assisted approach. Cassava waste was used as a substrate to produce the maximum yield of laccase enzyme (3.9 U/g) from Pleurotus ostreatus. Among the different inducers supplemented, CuSO₄ (0.5 mM) showed an eight-fold increase in enzyme production (30.8 U/g) after 240 h of incubation. The catalytic efficiency of laccase was observed as 128.7 ± 8.47 S⁻¹mM⁻¹ for syringaldazine oxidation at optimum pH 4.0 and 40 °C. Laccase activity was completely inhibited by lead (II) ion, mercury (II) ion, sodium dodecyl sulphate, sodium azide and 1,4 dithiothretiol and induced significantly by manganese (II) ion and rhamnolipid. After treating BRW with laccase, the concentrations of PAHs and phenolic contaminants of 1144 μg/L and 46160 μg/L were reduced to 96 μg/L and 16100 μg/L, respectively. The ability of laccase to effectively degrade PAHs in the presence of different phenolic compounds implies that phenolic contaminants may play a role in PAHs degradation. After 240 h, organic contaminants were removed from BRW in the following order: phenol >2,4-dinitrophenol > 2-methyl-4,6-dinitrophenol > 2,3,4,6-tetrachlorophenol > acenaphthene > fluorine > phenanthrene > fluoranthene > pyrene > anthracene > chrysene > naphthalene > benzo(a)anthracene > benzo(a)pyrene > benzo(b)fluoranthene > pentachlorophenol > indeno(1,2,3-cd)pyrene > benzo(j) fluoranthene > benzo[k]fluoranthène. The multiple contaminant remediation from the BRW by enzymatic method, clearly suggests that the laccase can be used as a bioremediation tool for the treatment of wastewater from various industries.

Tetrachlorobenzoquinone (TCBQ) is a common metabolite of persistent organic pollutants pentachlorophenol (PCP) and hexachlorobenzene (HCB). Current reports on the toxicity of TCBQmainly focused on its reproductive toxicity, neurotoxicity, carcinogenicity and cardiovascular toxicity. However, the possible immunotoxicity of TCBQ remains unclear. The release of neutrophil extracellular traps (NETs) is a recently discovered immune response mechanism, however, excess NETs play a pathogenic role in various immune diseases. In an attempt to address concerns regarding the immunotoxicity of TCBQ, we adopted primary mouse neutrophils as the research object, explored the influence of TCBQ on the formation of NETs. The results showed that TCBQ could induce NETs rapidly in a reactive oxygen species (ROS)-dependent manner. Moreover, TCBQ promoted the phosphorylation of c-Jun N-terminal kinase (JNK) mitogen activated protein kinase (MAPK), but not p38 or extracellular signal related kinase (ERK) in neutrophils. Mechanistically, JNK activation enhanced the expression of NADPH oxidase enzyme 2 (NOX2), which further accelerated the generation of ROS and thus amplified the formation of NETs. The pharmacologic blockage of JNK or NOX2 effectively ameliorated TCBQ-induced ROS and NETs, implying that ROS-JNK-NOX2 positive feedback loop was involved in TCBQ-induced NETs. In conclusion, we speculated that targeting NETs formation would be a promising therapeutic strategy in modulating the immunotoxicity of TCBQ.

Discharged carbon nanotubes (CNTs) likely interact with co-existing organic contaminants (OCs) and pose joint toxicity to environmental microbes. Herein, hydrophobic pentachlorophenol (PCP) and hydrophilic ciprofloxacin (CIP) were used as representative OCs and their joint toxicities with CNTs to Bacillus subtilis were systematically investigated at cellular, biochemical, and omics levels. The 3-h bacterial growth half inhibitory concentrations of CNTs, PCP, and CIP were 12.5 ± 2.6, 3.5 ± 0.5, and 0.46 ± 0.03 mg/L, respectively, and they all could damage cell membrane, increase intracellular oxidative stress, and alter bacterial metabolomics and transcriptomics; while CNTs-PCP and CNTs-CIP binary exposures exhibited distinct additive and synergistic toxicities, respectively. CNTs increased bacterial bioaccumulation of PCP and CIP via destabilizing and damaging cell membrane. PCP reduced the bioaccumulation of CNTs, while CIP had no significant effect; this difference could be owing to the different effects of the two OCs on cell-surface hydrophobicity and CNTs electronegativity. The additive toxicity outcome upon CNTs-PCP co-exposure could be a result of the balance between the increased toxicity from increased PCP bioaccumulation and the decreased toxicity from decreased CNTs bioaccumulation. The increased bioaccumulation of CIP contributed to the synergistic toxicity upon CNTs-CIP co-exposure, as confirmed by the increased inhibition of topoisomerase Ⅳ activity and interference in gene expressions regulating ABC transporters and lysine biosynthesis. The findings provide novel insights into environmental risks of CNTs.

Hematite nanoparticles (NPs) exist naturally and ubiquitously in soil, and they are always associated with soil organic matter by forming organic-inorganic complexes. In this work, hematite NPs coated with peat humic acid (HAₚₑₐₜ) and soil humic acid (HAₛₒᵢₗ) were chosen as sorbents for hydrophobic organic contaminants (HOCs) to simulate the sorption processes in soil. Ionizable pentachlorophenol (PCP) and non-ionizable phenanthrene (PHE) were selected as representative HOCs. Compared with sorption isotherms of uncoated hematite NPs, the coating of HA onto the surface of hematite NPs substantially increased its sorption affinity for PCP and PHE by about 1-2 orders of magnitude, and the increasing degree was positively correlated to the HA content. These phenomena emphasized the dominant role of HA in the sorption process. The reduced polarity and the introduction of functional groups contributed to the enhanced sorption of HOCs on HA-coated hematite NPs. Furthermore, HAₚₑₐₜ-hematite NPs showed higher sorption affinity for both PCP and PHE than HAₛₒᵢₗ-hematite NPs, which was mainly due to the lower polarity and higher hydrophobicity of HAₚₑₐₜ-hematite NPs. The sorption of PCP and PHE on HA-coated hematite NPs was inhibited obviously with increasing pH values and the pH effect on PCP sorption was more significant than that of PHE, due to the deprotonation of functional groups within adsorbed HA, the loose structure of adsorbed HA and the dissociation of PCP. Our findings elucidated the mechanisms involved in HOCs sorption processes by HA-hematite NPs and provided a theoretical basis for environmental remediation with natural NPs (e.g., hematite NPs).

Chlorophenols (CPs) are used in the production of pesticides and preservatives. Although human exposure to CPs has been known for years, current exposure levels to these chemicals in Asian countries are not known. In this study, we analyzed concentrations of eight CPs in 300 human urine samples collected from nine countries. Of these CPs, 2,5-dichlorophenol and 2,4-dichlorophenol were found at the highest median concentrations (median for all nine countries: 1.78 and 0.34 ng/mL, respectively). Pentachlorophenol was found in 59% of the samples analyzed at a median concentration of 0.07 ng/mL. Urine samples from Japan had the highest concentration of total CPs (median: 16.7 ng/mL) with 2,5-dichlorophenol accounting for 93.1% of the total concentration. The estimated daily intake (DI) for precursors of dichlorophenols varied widely, but several samples showed values higher than the acceptable DI recommended by the United States Environmental Protection Agency (EPA). These results suggest that CP exposure, especially to dichlorophenols, is prevalent in several countries, particularly in Asia, suggesting a pressing need for further assessment of the global sources and potential health effects of these chemicals.

Pentachlorophenol (PCP) was used in large quantities, and mainly for killing the intermediate host snails of schistosome in China, thereby resulting in ubiquitous PCP residue in the environment. However, studies considering the carcinogenicity of PCP for humans mainly focused on occupational workers, and the actual carcinogenicity of PCP for general population is uncertain. To investigate the association between cancer risks and PCP exposure in a community population, an ecological study was conducted in three contaminated areas along the Yangtze River. Standardized rate ratio (SRR) was calculated to represent the risk of cancer incidence, by using incidence in the low PCP exposure category as the reference group. A total of 15,962 cancer records were collected, and 76 water samples and 213 urine samples in three areas were examined. Our findings suggested that compared with the low PCP group, the high PCP group had significantly excessive incidences of various cancers related to different organs including lymph (SRR = 19.44, 95% CI = 15.00–25.19), blood (SRR = 17.24, 95% CI = 12.92–23.01), nasopharynx (SRR = 3.97, 95% CI = 3.75–4.21), gallbladder (SRR = 3.46, 95% CI = 3.09–3.87), pancreas (SRR = 3.41, 95% CI = 3.07–3.79), respiratory system (SRR = 3.41, 95% CI = 3.27–3.57) and liver (SRR = 3.31, 95% CI = 3.09–3.56). Taken together, our present study provides evidence that general community population exposed to high level of PCP exhibits a broader spectrum of increased cancer risks as compared to occupational groups.

The presence of organic pollutants in the aquatic environment, usually found at trace concentrations (i.e., between ng L−1 and μg L−1 or even lower, known as micropollutants), has been highlighted in recent decades as a worldwide environmental concern due to their difficult elimination by conventional water and wastewater treatment processes. The relevant information on constructed wetlands (CWs) and their application for the removal of a specific group of pollutants, 41 organic priority substances/classes of substances (PSs) and 8 certain other substances with environmental quality standards (EQS) listed in Directive 2013/39/EU as well as 17 contaminants of emerging concern (CECs) of the Watch List of Decision 2015/495/EU, is herein reviewed. Studies were found for 24 PSs and 2 other substances with EQS: octylphenol, nonylphenol, perfluorooctane sulfonic acid, di(2-ethylhexyl)phthalate, trichloromethane, dichloromethane, 1,2-dichloroethane, pentachlorobenzene, benzene, polychlorinated dibenzo-p-dioxins, naphthalene, fluoranthene, trifluralin, alachlor, isoproturon, diuron, tributyltin compounds, simazine, atrazine, chlorpyrifos (chlorpyrifos-ethyl), chlorfenvinphos, hexachlorobenzene, pentachlorophenol, endosulfan, dichlorodiphenyltrichloroethane (or DDT) and dieldrin. A few reports were also published for 8 CECs: imidacloprid, erythromycin, clarithromycin, azithromycin, diclofenac, estrone, 17-beta-estradiol and 17-alpha-ethinylestradiol. No references were found for the other 17 PSs, 6 certain other substances with EQS and 9 CECs listed in EU legislation.

High levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were detected in free-range eggs, and these levels reached a concentration of 29.84 ± 7.45 pg of WHO-TEQ/g of fat. This value exceeded the EU maximum permitted level of 2.5 pg of WHO-TEQ/g of fat for PCDD/F congeners by twelve-fold. A chemical analysis (HRGC-HRMS) revealed elevated amounts of OCDD, OCDF, HxCDD, HpCDD and HpCDF. During the investigation, samples of feed, soil, wall scrapings, wooden ceiling of the henhouse and tissues from laying hens were examined for dioxin contents (30 samples altogether). The long and complicated investigation found that the source of dioxins in the poultry farm was pentachlorophenol-treated wood, which was used as structural components in the 40-year-old farm building adapted to a henhouse. The wooden building material contained PCDD/Fs at a concentration of 3922.60 ± 560.93 pg of WHO-TEQ/g and 11.0 ± 2.8 μg/kg of PCP. The potential risk associated with dioxin intake was characterized by comparing the theoretically calculated weekly and monthly intakes with the toxicological reference values (TRVs), namely the Tolerable Weekly Intake (TWI) and Provisional Tolerable Monthly Intake (PTMI) values of 14 pg of WHO-TEQ/kg of bw and 70 pg of WHO-TEQ/kg of bw, respectively. The intake of dioxins estimated for high egg consumers (approximately 5–6 eggs/week) exceeded the TWI and PTMI values, which may pose a risk of delayed adverse health effects. The estimated dose of PCDD/Fs and DL-PCBs for children consuming 5 eggs per week exceeded the TWI by as much as 450% because of their nearly 5-fold-lower body weight. Although the dioxin intake estimated for the average consumption of eggs in the general population did not exceed any of the TRVs applied (58.7% TWI and 51.1% PTMI), such a situation should be considered unacceptable from a public health perspective because eggs are not the only source of these contaminants.

Homologue and congener profiles of PCDD/Fs in eels, passive sampler and sediment extracts from the Burrishoole, a rural upland catchment on the western Irish seaboard were compared with potential PCDD sources. ΣPCDD/F levels in eels ranged from 2.9 to 25.9 pg g−1 wet weight, which are elevated compared to other Irish locations. The OCDD congener dominated the pattern of ΣPCDD/Fs in all matrices from Burrishoole. Passive samplers were successfully deployed to identify for the first time the presence in the water column of PCDD/Fs and dimethoxylated octachlorodiphenyl ether (diMeOoctaCDE), impurities found in pentachlorophenol (PCP) production. Principal component analysis (PCA) identified similarities between PCDD/F profiles in technical PCP mixtures and environmental samples from the Burrishoole region. Results strongly suggest residual PCDD contamination associated with historic local use of a dioxin contaminated product in the catchment area, with pentachlorophenol a strong candidate.

Air, soils and sediments surrounding an abandoned pentachlorophenol (PCP) factory were sampled to determine the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), unintentionally formed during PCP production. The mean concentration of PCDD/Fs in ambient air was one order of magnitude higher than that of the reference site. A trend of decreasing concentrations with increasing distance from the factory was observed, suggesting this site has a significant influence on the regional ambient air. As for soil samples collected within 3 km from the factory and sediment samples from the adjacent rivers, high levels of contamination were found with WHO-TEQ concentrations of 193 ± 211 pg/g and 667 ± 978 pg/g, respectively. The PCDD/F homologue profiles of all samples were consistent with those found in the technical product of PCP, with OCDD as the dominant congener. These results indicate PCDD/Fs in the historical contaminated site pose a long-term impact on surrounding environment.