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.

Polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) share similar toxicities and thermal origins, e.g., municipal solid waste incinerator (MSWI). Recently, PBDD/Fs from MSWI attracted rising concern because their important precursors, i.e., brominated flame retardants (BFRs), were frequently found in various wastes for landfill or MSWI feedstock. So far, however, little is known about PBDD/Fs and their associated risks in the vicinal environments of MSWI. Here we analyzed PBDD/Fs and PCDD/Fs in 29 soil samples collected around a multiyear large-scale MSWI, and compared their spatial distributions, sources and risks. PBDD/Fs demonstrated comparable concentrations and toxic equivalent quantities (TEQs) to PCDD/Fs in these samples. Spatially, both the concentrations of PBDD/Fs and PCDD/Fs decreased outwards from the MSWI, and exhibited significant linear correlations with the distances from the MSWI in the southeast downwind soil, suggesting the influence of the MSWI on its vicinal soil environment. However, the existence of other dioxin sources concealed its influence beyond 6 km. PBDD/Fs in the soils were characterized by highly-brominated PBDFs, especially Octa-BDF, and their sources were diagnosed as the MSWI and diesel exhaust; PCDD/Fs, however, were dominated by highly-chlorinated PCDDs, particularly Octa-CDD, and were contributed individually or jointly by the MSWI, automobile exhaust and pentachlorophenol (PCP)/Na-PCP. The non-carcinogenic risks of dioxins in all the soil samples were acceptable, but their carcinogenic risks in 17% of the samples were unacceptable. These samples were all located close to the MSWI and highways, therefore, the land use of these two high-risk zones should be cautiously planed.

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).

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.

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are highly toxic to humans and wildlife. In the present study, PCDD/Fs were analyzed in the eggs of whiskered terns (Chlidonias hybrida), and genetically identified eggs from black-crowned night herons (Nycticorax nycticorax) sampled from two lakes in the Yangtze River Delta area, China. The median toxic equivalent (TEQ) of PCDD/Fs were 280 (range: 95–1500) and 400 (range: 220–1100) pg TEQ g−1 lw (WHO, 1998 for birds) in the eggs of black-crowned night heron and whiskered tern, respectively.Compared to known sources, concentrations of PCDDs relative to the sum of PCDD/Fs in bird eggs, demonstrated high abundance of octachlorodibenzo-p-dioxin (OCDD), 1,2,3,4,6,7,8-heptaCDD and 1,2,3,6,7,8-hexaCDD indicating pentachlorophenol (PCP), and/or sodium pentachlorophenolate (Na-PCP) as significant sources of the PCDD/Fs. The presence of polychlorinated diphenyl ethers (PCDEs), hydroxylated and methoxylated polychlorinated diphenyl ethers (OH- and MeO-PCDEs, known impurities in PCP products), corroborates this hypothesis. Further, significant correlations were found between the predominant congener CDE-206, 3′-OH-CDE-207, 2′-MeO-CDE-206 and OCDD, indicating a common origin.Eggs from the two lakes are sometimes used for human consumption. The WHO health-based tolerable intake of PCDD/Fs is exceeded if eggs from the two lakes are consumed regularly on a weekly basis, particularly for children. The TEQs extensively exceed maximum levels for PCDD/Fs in hen eggs and egg products according to EU legislation (2.5 pg TEQ g−1lw). The results suggest immediate action should be taken to manage the contamination, and further studies evaluating the impacts of egg consumption from wild birds in China. Likewise, studies on dioxins and other POPs in common eggs need to be initiated around China.

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.

Levels and profiles of polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs) were analyzed for the first time in raw and treated water from five water treatment plants in Shenzhen, South China. The average PCDD/Fs concentrations were 32.93 pg/L (0.057 pg international toxic equivalent quantity (I-TEQ)/L) and 0.64 pg/L (0.021 pg I-TEQ/L) in raw and treated water, respectively. The removal rate of PCDD/Fs in terms of mass concentration varied from 93.4% to 98.8%, whereas a negative removal rate was observed in one plant in terms of TEQ concentration. The PCDD/Fs concentration in raw water was lower than most of the published data from other countries and regions, and the PCDD/Fs concentration in treated water was below the Maximum Contaminants Level (MCL) of 30 pg/L for dioxin in drinking water set by the US EPA. Historical pentachlorophenol usage, local waste incineration and industrial emissions, as well as surface runoff or even soil erosion, might be the main sources for PCDD/F pollution in water. The daily intake of PCDD/Fs for local residents from drinking water was estimated to be 0.69 fg I-TEQ/kg/day, which is negligible compared with that from food consumption (1.23 pg WHO-TEQ/kg/day) in the local area.

Natural soil montmorillonite and kaolinite nanoparticles (NPs) were tested as efficient sorbents for organic contaminant (OC) removal through mimicking their natural environmental dispersive states. Sorption of both mineral NPs decreased with increasing pH with ionizable pentachlorophenol (PCP), but increased with pH with non-ionizable phenanthrene (PHE), within the pH range of 4–10. In contrast, sorption decreased consistently for both PCP and PHE, as a function of increasing ion concentration (0.001–0.1 mol L−1). Sorption differences were likely caused by the electrolytic conditions dependent upon surface chemistry of OCs and mineral NPs. The results confirmed that the highly dispersive soil mineral NPs would prevail over both engineered NPs and their regular μm-sized colloids for OC removal, due to their ecological advantages and higher sorption properties. This finding provided a realistic assessment of the environmental function of soil natural minerals in water once they are released from soil into OC polluted aqueous systems.

Pentachlorophenol (PCP) dissipation occurs naturally in flooded soils and although dissipation half-lives vary between soil profiles at the millimeter-scale the reason is poorly understood. Vertical variations of PCP dissipation were investigated in three typical Chinese paddy soils; Soil 1 (Umbraqualf), Soil 2 (Plinthudult) and Soil 3 (Tropudult). The soil depth was divided into a surface and a deep layer based upon different PCP dissipations in the surface layer of 40–93, 42–88 and 16–100% for Soils 1–3 respectively. In the deep layer, PCP was greatly dissipated in Soil 2, but much less in Soil 1 and Soil 3. Correlation analysis indicated that SO42− and Fe(III) were negatively related to PCP dissipation. SO42− and Cl- were highly mobile in the flooded soil profiles. Fe(III) reduction increased with increasing soil depth, and was inhibited by high SO42− concentrations.