Bioremediation of 2,4,6-trichlorophenol by extracellular enzymes of white rot fungi immobilized with sodium alginate/hydroxyapatite/chitosan microspheres.

Hydroxyapatite, a calcium phosphate biomass material known for its excellent biocompatibility, holds promising applications in water, soil, and air treatment. Sodium alginate/hydroxyapatite/chitosan (SA-HA-CS) microspheres were synthesized by cross-linking sodium alginate with calcium chloride. These microspheres were carriers for immobilizing extracellular crude enzymes from white rot fungi through adsorption, facilitating the degradation of 2,4,6-trichlorophenol (2,4,6-TCP) in water and soil. At 50 °C, the immobilized enzyme retained 87.2% of its maximum activity, while the free enzyme activity dropped to 68.86%. Furthermore, the immobilized enzyme maintained 68.09% of its maximum activity at pH 7, surpassing the 51.16% observed for the free enzyme. Under optimal conditions (pH 5, 24 h), the immobilized enzymes demonstrated a remarkable 94.7% removal rate for 160 mg/L 2,4,6-TCP, outperforming the 62.1% achieved by free crude enzymes. The degradation of 2,4,6-TCP by immobilized and free enzymes adhered to quasi-first-order degradation kinetics. Based on LC-MS, the plausible biodegradation mechanism and reaction pathway of 2,4,6-TCP were proposed, with the primary degradation product identified as 1,2,4-trihydroxybenzene. The immobilized enzyme effectively removed 72.9% of 2,4,6-TCP from the soil within 24 h. The degradation efficiency of the immobilized enzyme varied among different soil types, exhibiting a negative correlation with soil organic matter content. These findings offer valuable insights for advancing the application of immobilized extracellular crude enzymes in 2,4,6-TCP remediation.

Weak static magnetic fields facilitated highly efficient 2,4,6-trichlorophenol removal by sulfurized nanoscale zero-valent iron supported on biochar (BC-SNZVI) at neutral pH.

Sulfurized nanoscale zero-valent iron supported on biochar (BC-SNZVI) has been successfully synthesized for 2,4,6-trichlorophenol (2,4,6-TCP) removal, while was only effectively under acidic conditions. To obtain highly efficient removal of 2,4,6-TCP within a broader pH range, weak static magnetic fields (WMF) was applied in BC-SNZVI/2,4,6-TCP aqueous systems. Results showed 30 mT WMF supported the most extensive 2,4,6-TCP removal, and 87.4% of 2,4,6-TCP (initial concentration of 30 mg/L) was removed by 0.5 g/L BC-SNZVI at neutral pH (pH = 6.8) within 180 min, which was increased by 54.4% compared to that without WMF. The observed rate constant (Kobs) under 30 mT WMF was 2.1-fold greater than that without WMF. Although three typical anions (NO3- (0.5-10.0 mM), H2PO4- (0.05-0.5 mM), and HCO3- (0.5-5.0 mM)) still inhibited 2,4,6-TCP removal, WMF could efficiently alleviate the inhibitory effects. Moreover, 73.1% of 2,4,6-TCP was successfully removed by BC-SNZVI under WMF in natural water. WMF remarkably boosted the dechlorination of 2,4,6-TCP, increasing the 2,4,6-TCP dechlorination efficiency from 45.2% (in the absence of WMF) to 83.8% (in the presence of WMF) by the end of 300 min. And the complete dechlorination product phenol appeared within 10 min. Force analysis confirmed the magnetic field gradient force (FB) moved paramagnetic Fe2+ at the SNZVI surface along the direction perpendicular to the external applied field, promoting the mass-transfer controlled SNZVI corrosion. Corrosion resistance analysis revealed WMF promoted the electron-transfer controlled SNZVI corrosion by decreasing its self-corrosion potential (Ecorr). With the introduction of sulfur, the magnitude of FB doubled and the Ecorr decreased comparing with NZVI. Our findings provide a facile and viable strategy for treating chlorinated phenols at neutral pH.

Sulfurized nano zero-valent iron prepared via different methods: Effect of stability and types of surface corrosion products on removal of 2,4,6-trichlorophenol.

Sulfurization improves the stability and activity of nano zero-valent iron (nZVI). The sulfurized nZVI (S-nZVI) were prepared with ball milling, vacuum chemical vapor deposition (CVD) and liquid-phase reduction techniques and the corresponding products were the mixture of FeS2 and nZVI (nZVI/FeS2), well-defined core-shell structure (FeSx@Fe) or seriously oxidized (S-nZVI(aq)), respectively. All these materials were applied to eliminate 2,4,6-trichlorophenol (TCP) from water. The removal of TCP was irrelevant with the structure of S-nZVI. Both nZVI/FeS2 and FeSx@Fe showed remarkable performance for the degradation of TCP. S-nZVI(aq) possessed poor mineralization efficiency to TCP due to its bad crystallinity degree and severe leaching of Fe ions, which retarded the affinity of TCP. Desorption and quenching experiments suggested that TCP removal by nZVI and S-nZVI was based on surface adsorption and subsequent direct reduction by Fe0, oxidation by in-situ produced ROS and polymerization on the surface of these materials. In the reaction process, the corrosion products of these materials transformed into crystalline Fe3O4 and α/ß-FeOOH, which enhanced the stability of nZVI and S-nZVI materials and was conductive to the electron transferring from Fe0 to TCP and strong affinity of TCP onto Fe or FeSx phases. All these were contributed to high performance of nZVI and sulfurized nZVI in removal and minerazilation of TCP in continuous recycle test.

Synthesis and characterisation of acid/basic modified adsorbents. Application for chlorophenols removal.

A commercial activated carbon was modified with acid and basic reagents -an acidic one via treatment with sulphuric acid and a basic via treatment with pentaethylenehexamine- to yield adsorbents with different surface acid/base character. These modified adsorbents were characterised by elemental and immediate analysis, N2 adsorption, XPS and point zero charge measurements. The new adsorbents were tested for chlorophenols removal in water (4-chlorophenol, 3,5-dichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol) at different temperatures. Although the calculated process enthalpy was positive for all cases, indicating an endothermic process, the entropy was positive, resulting in a negative Gibbs free energy and spontaneous process. The adsorption capacity increases with temperature and decreases when the phenols' number of substituents increases. The modified acid-activated carbon demonstrated an exciting higher adsorbing capacity from 426.9 to 742.3 mg g-1 for 2,4,6-trichlorophenol, whereas the adsorption capacity for the basic ranged between 142.9 and 238.0 mg g-1. The Langmuir model satisfactorily fitted the adsorption equilibrium data for all chlorophenol contaminants.

Modification of glassy carbon electrode with manganese cobalt oxide-cubic like structures incorporated graphitic carbon nitride sheets for the voltammetric determination of 2,4,6 -trichlorophenol.

Novel cube-like transition metal oxide embedded on graphitic carbon nitride (MCO@GCN) formed a hybrid composite via hydrothermal assisted sonochemical synthesis. The synthesized composite was examined with various physical characterizations such as morphological SEM, EDX, XRD, and FT-IR spectroscopy. The electrocatalytic activity of MCO@GCN composite was further investigated when used  to modify a glassy carbon electrode (GCE). The electrochemical sensor was investigated using modified MCO@GCN/GCE towards environmental pollutant 2,4,6-trichlorophenol (2,4,6-TCP) detection with at a potential of (+ 0.654 V vs Ag/AgCl) in pH-7. The structural features have favored a high charge transfer ratio with excellent conductivity which showed a low detection limit (LOD) of 0.0068 µM and sensitivity of 23.57 µA·µM-1·cm-2 comprising a wide linear working range of 0.01-1720 µM by using differential pulse voltammetry. Besides, the MCO@GCN/GCE displayed excellent selectivity , repeatability, reproducibility, storage, and operational stability. Notably, the proposed MCO@GCN/GCE was validated with different environmental samples (tap, river, and industrial water) with RSD 0.62-2.86% and 96.51-99.66% (n = 3) recovery.

Phytoremediation of multiple persistent pollutants co-contaminated soil by HhSSB transformed plant.

The high toxicity of persistent pollutants limits the phytoremediation of pollutants-contaminated soil. In this study, heterologous expressing Halorhodospira halophila single-stranded DNA binding protein gene (HhSSB) improves tolerance to 2,4,6-trinitrotoluene (TNT), 2,4,6-trichlorophenol (2,4,6-TCP), and thiocyanate (SCN-) in A. thaliana and tall fescue (Festuca arundinacea). The HhSSB transformed Arabidopsis, and tall fescue also exhibited enhanced phytoremediation of TNT, 2,4,6-TCP, and SCN- separately contaminated soil and co-contaminated soil compared to control plants. TNT assay was selected to explore the mechanism of how HhSSB enhances the phytoremediation of persistent pollutants. Our result indicates that HhSSB enhances the phytoremediation of TNT by enhancing the transformation of TNT in Arabidopsis. Moreover, transcriptomics and comet analysis revealed that HhSSB improves TNT tolerance through three pathways: strengthening the defense system, enhancing the ROS scavenging system, and reducing DNA damage. These results presented here would be particularly useful for further studies in the remediation of soil contaminated by organic and inorganic pollutants.

Novel fluorescent sensor using molecularly imprinted silica microsphere-coated CdSe@CdS quantum dots and its application in the detection of 2,4,6-trichlorophenol from environmental water samples.

In this study, a high fluorescence sensitivity and selectivity, molecularly imprinted nanofluorescent polymer sensor (MIP@SiO2 @QDs) was prepared using a reverse microemulsion method. 2,4,6-Trichlorophenol (2,4,6-TCP) was detected using fluorescence quenching. Tetraethyl orthosilicate (TEOS), quantum dots (QDs) and 3-aminopropyltriethoxysilane (APTS) were used as cross-linker, signal sources and functional monomer respectively. The sensor (MIP@SiO2 @QDs) and the non-imprinted polymer sensor (NIP@SiO2 @QDs) were characterized using infra-red (IR) analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The selectivity of MIP@SiO2 @QDs was examined by comparing 2,4,6-TCP with other similar functional substances including 2,4-dichlorophenol (2,4-DCP), 2,6-dichlorophenol (2,6-DCP) and 4-chlorophenol (4-CP). Results showed that MIP@SiO2 @QDs had better selectivity for 2,4,6-TCP than the other compounds. Fluorescence quenching efficiency displayed a good linear response at the 2,4,6-TCP concentration range 5-1000 µmol/L. The limit of detection (LOD) was 0.9 µmol/L (3σ, n = 9). This method was equally applicable for testing actual samples with a recovery rate of 98.0-105.8%. The sensor had advantages of simple pretreatment, good sensitivity and selectivity, and wide linear range and could be applied for the rapid detection of 2,4,6-TCP in actual samples.

Residue Dynamics and Risk Assessment of Prochloraz and Its Metabolite 2,4,6-Trichlorophenol in Apple.

The residue dynamics and risk assessment of prochloraz and its metabolite 2,4,6-trichlorophenol (2,4,6-TCP) in apple under different treatment concentrations were investigated using a GC-ECD method. The derivatization percent of prochloraz to 2,4,6-TCP was stable and complete. The recoveries of prochloraz and 2,4,6-TCP were 82.9%-114.4%, and the coefficients of variation (CV) were 0.7%-8.6% for the whole fruit, apple pulp, and apple peel samples. Under the application of 2 °C 2.0 g/L, 2 °C 1.0 g/L, 20 °C 2.0 g/L, and 20 °C 1.0 g/L treatment, the half-life for the degradation of prochloraz was 57.8-86.6 d in the whole fruit and apple peel, and the prochloraz concentration in the apple pulp increased gradually until a peak (0.72 mg·kg-1) was reached. The concentration of 2,4,6-TCP was below 0.1 mg·kg-1 in four treatment conditions and not detected (

Response of selenium-dependent glutathione peroxidase in the freshwater bivalve Anodonta woodiana exposed to 2,4-dichlorophenol,2,4,6-trichlorophenol and pentachlorophenol.

2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) pose a health risk to aquatic organism and humans, and are recognized as persistent priority pollutants. Selenium dependent glutathione peroxidase (Se-GPx) belongs to the family of selenoprotein, which acts mainly as an antioxidant role in the cellular defense system. In the current study, a Se-GPx full length cDNA was cloned from Anodonta woodiana and named as AwSeGPx. It had a characteristic codon at 165TGA167 that corresponds to selenocysteine(Sec) amino acid as U44. The full length cDNA consists of 870 bp, an open reading frame (ORF) of 585 bp encoded a polypeptide of 195 amino in which conserved domain (68LGFPCNQF75) and a glutathione peroxide-1 GPx active site (32GKVILVENVASLUGTT47) were observed. Additionally, the eukaryotic selenocysteine insertion sequence (SECIS) was conserved in the 3'UTR. The AwSeGPx amino acid sequence exhibited a high similarity with that of other Se-GPx. Real-time PCR analysis revealed that AwSeGPx mRNA had a widely distribution, but the highest level was observed in hepatopancreas. AwSeGPx mRNA expression was significantly up-regulated in hepatopancreas, gill and hemocytes after 2,4-DCP, 2,4,6-TCP and PCP exposure. Under similar environment, clams A. woodiana showed a more sensitive to PCP than that of 2,4-DCP and 2,4,6-TCP. These results indicate that AwSeGPx plays a protective role in eliminating oxidative stress derived from 2,4-DCP, 2,4,6-TCP and PCP treatment.

Simultaneous dispersive liquid-liquid microextraction based on a low-density solvent and derivatization followed by gas chromatography for the simultaneous determination of chloroanisoles and the precursor 2,4,6-trichlorophenol in water samples.

Chloroanisoles, particularly 2,4,6-trichloroanisole, are commonly identified as major taste and odor compounds in water. In the present study, a simple and efficient method was established for the simultaneous determination of chloroanisoles and the precursor 2,4,6-trichlorophenol in water by using low-density-solvent-based simultaneous dispersive liquid-liquid microextraction and derivatization followed by gas chromatography with electron capture detection. 2,4-Dichloroanisole, 2,6-dichloroanisole, 2,4,6-trichloroanisole, 2,3,4-trichloroanisole, and 2,3,6-trichloroanisole were the chloroanisoles evaluated. Several important parameters of the extraction-derivatization procedures, including the types and volumes of extraction solvent and disperser solvent, concentrations of derivatization agent and base, salt addition, extraction-derivatization time, and temperature were optimized. Under the optimized conditions (80 µL of isooctane as extraction solvent, 500 µL of methanol as disperser solvent, 60 µL of acetic anhydride as derivatization agent, 0.75% of Na2 CO3 addition w/v, extraction-derivatization temperature of 25°C, without salt addition), a good linearity of the calibration curve was observed by the square of correlation coefficients (R(2) ) ranging from 0.9936 to 0.9992. Repeatability and reproducibility of the method were < 4.5% and <7.3%, respectively. Recovery rates ranged from 85.2 to 101.4%, and limits of detection ranged from 3.0 to 8.7 ng/L. The proposed method was applied successfully for the determination of chloroanisoles and 2,4,6-trichlorophenol in water samples.

UV photolysis for enhanced phenol biodegradation in the presence of 2,4,6-trichlorophenol (TCP).

A bacterial strain isolated from activated sludge and identified as Bacillus amyloliquefaciens could biodegrade phenol, but 2,4,6-trichlorophenol (TCP) inhibited phenol biodegradation and biomass growth. UV photolysis converted TCP into dichlorocatechol, monochlorophenol, and dichlorophenol, and this relieved inhibition by TCP. Phenol-removal and biomass-growth rates were significantly accelerated after UV photolysis: the monod maximum specific growth rate (µ(max)) increased by 9% after TCP photolysis, and the half-maximum-rate concentration (K(S)) decreased by 36%. Thus, the major benefit of UV photolysis in this case was to transform TCP into a set of much-less-inhibitory products.

The role of exogenous electron donors for accelerating 2,4,6-trichlorophenol biotransformation and mineralization.

2,4,6-Trichlorophenol (TCP) is a biologically recalcitrant compound, but its biodegradation via reductive dechlorination can be accelerated by adding an exogenous electron donor. In this work, acetate and formate were evaluated for their ability to accelerate TCP reductive dechlorination, as well to accelerate mono-oxygenation of TCP's reduction product, phenol. Acetate and formate accelerated TCP reductive dechlorination, and the impact was proportional to the number of electron equivalents released by oxidation of the donor: 8 e(-) equivalents per mol for acetate, compared to 2 e(-) eq per mol for formate. The acceleration phenomenon was similar for phenol mono-oxygenation, and this increased the rate of TCP mineralization. Compared to endogenous electron equivalents generated by phenol mineralization, the impact of exogenous electron donor was stronger on a per-equivalent basis.

Penta- and 2,4,6-tri-chlorophenol biodegradation during municipal solid waste anaerobic digestion.

In this study isotopic tracing using (13)C labelled pentachlorophenol (PCP) and 2,4,6-trichlorophenol (2,4,6-TCP) is proposed as a tool to distinguish the loss of PCP and 2,4,6-TCP due to biodegradation from other physical processes. This isotopic approach was applied to accurately assess in situ PCP and 2,4,6-TCP degradation under methanogenic conditions in several microcosms made up of household waste. These microcosms were incubated in anaerobic conditions at 35°C (mesophilic) and 55°C (thermophilic) without agitation. The volume of biogas produced (CH4 and CO2), was followed for a period of 130 days. At this stage of stable methanogenesis, (13)C6-PCP and (13)C6-2,4,6-TCP were introduced anaerobically in microcosms and its monitoring at mesophilic and thermophilic conditions was performed in parallel by gas chromatography mass spectrometry (GC-MS) and gas chromatography isotope-ratio mass spectrometry (GC-IRMS). This study proved the almost total dechlorination of bioavailable PCP and 2,4,6-TCP into 4-CP at 35°C. Nevertheless, high rate adsorption in particular materials of the two compounds was observed. Furthermore, Carbon-13 Nuclear Magnetic Resonance ((13)C-NMR) Spectroscopy analysis of (13)C labelled 2,4,6-TCP mesophilic incubations showed the partial mineralization of 4-CP at 35°C to acetate and then to HCO(3-). Consequently, NMR results confirm the biogas isotopic results indicating the mineralization of (13)C labelled 2,4,6-TCP into (13)C (CH4 and CO2). Concerning (13)C labelled PCP mesophilic incubations, the isotopic composition of the biogas still natural until the day 262. In contrast, no dechlorination was observed at 55°C. Thus PCP and 2,4,6-TCP were persistent in thermophilic conditions.

Characterization and evaluation of the efficiency of SiO2/tetra-α-(2,4-di-tert-butylphenoxy)-phthalocyaninato zinc nanocomposite as photosensitizers for oxidation of 2,4,6-trichlorophenol.

A photosensitizer tetra-α-(2,4-di-tert-butylphenoxy)-phthalocyaninato zinc [ZnPc(OAr)4] was successfully encapsulated in SiO2 nanoparticle by the microemulsion method. The photosensitized composite nanoparticle was able to degrade 2,4,6-trichlorophenol (TCP) in aqueous solution. Under visible light irradiation, the nanoparticles efficiently generated reactive oxygen species; 95.4% of TCP was degraded after 270 min of reaction. Some aromatic compounds and aliphatic carboxylic acids were detected by mass spectrometry as the reaction intermediates. The results were different from those of previously reported photocatalytic reactions, in which valence band holes or hydroxyl radicals functioned as the main oxidants. The photosensitizing composite nanoparticle is potentially applicable to the oxidation of phenol.

The role of T56 in controlling the flexibility of the distal histidine in dehaloperoxidase-hemoglobin from Amphitrite ornata.

The activation of dehaloperoxidase-hemoglobin (DHP) to form a ferryl intermediate requires the distal histidine, H55, to act as an acid base catalyst. The lack of ancillary amino acids in the distal pocket to assist in this process makes H55 even more important to the formation of active intermediates than in conventional peroxidases. Therefore, one can infer that the precise conformation H55 may greatly affect the enzymatic activity. Using site-direct mutagenesis at position T56, immediately adjacent to H55, we have confirmed that subtle changes in the conformation of H55 affect the catalytic efficiency of DHP. Mutating T56 to a smaller amino acid appears to permit H55 to rotate with relatively low barriers between conformations in the distal pocket, which may lead to an increase in catalytic activity. On the other hand, larger amino acids in the neighboring site appear to restrict the rotation of H55 due to the steric hindrance. In the case of T56V, which is an isosteric mutation, H55 appears less mobile, but forced to be closer to the heme iron than in wild type. Both proximity to the heme iron and flexibility of motion in some of the mutants can result in an increased catalytic rate, but can also lead to protein inactivation due to ligation of H55 to the heme iron, which is known as hemichrome formation. A balance of enzymatic rate and protein stability with respect to hemichrome formation appears to be optimum in wild type DHP (WT-DHP).

2,4,6-Trichlorophenol cytotoxicity involves oxidative stress, endoplasmic reticulum stress, and apoptosis.

This study aims to evaluate the cytotoxicity and potential mechanisms of 2,4,6-trichlorophenol (2,4,6-TCP) in mouse embryonic fibroblasts. Our results show that 2,4,6-TCP causes morphological changes and reduces cell viability. The overproduction of reactive oxygen species, the upregulation of nuclear factor-E2-related factor 2 (Nrf2) and heme oxygenase 1 (HMOX1) messenger RNA (mRNA) expressions, and the nuclear translocation of Nrf2 protein demonstrate that 2,4,6-TCP induces oxidative stress, and the Nrf2/HMOX1 pathway might be involved in 2,4,6-TCP-induced antioxidative response. Simultaneously, our data also demonstrate that 2,4,6-TCP upregulates the expressions of binding immunoglobulin protein, inositol-requiring enzyme/endonuclease 1α, and C/EBP homologous protein; stimulates α subunit of eukaryotic translation initiation factor 2 phosphorylation; and induces the splicing of Xbp1 mRNA, suggesting that endoplasmic reticulum (ER) stress is triggered. Moreover, 2,4,6-TCP alters the mitochondrial membrane potential and increases the apoptosis rate, the caspase 3 activity, and the Bax/Bcl-2 ratio, demonstrating that the mitochondrial pathway is involved in the 2,4,6-TCP-induced apoptosis. Thus, these results show that 2,4,6-TCP induces oxidative stress, ER stress, and apoptosis, which together contribute to its cytotoxicity in vitro.

Performance evaluation and metagenomic analysis of sequencing batch reactor under transient 2,4,6-trichlorophenol shock.

The transient chlorophenol shock under some emergency conditions might directly affect the pollutant removal of bioreactor. Therefore, the recovery of bioreactor performance after transient chlorophenol shock is a noteworthy issue. In the present research, the performance, antioxidant response, microbial succession and functional genes of sequencing batch reactor (SBR) were evaluated under transient 2,4,6-trichlorophenol (2,4,6-TCP) shock. The chemical oxygen demand (COD) and ammonia nitrogen (NH4+-N) removal efficiencies decreased sharply in the first 4 days after 60 mg/L 2,4,6-TCP shock for 24 h and gradually recovered to normal in the subsequent 8 days. The nitrogen removal rates and their corresponding enzymatic activities rapidly decreased after transient 2,4,6-TCP shock and then gradually increased to normal. The increase of antioxidant enzymatic activity, Cu-Zn SOD genes and Fe-Mn SOD genes contributed to the recovery of SBR performance. The abundance of genes encoding ammonia monooxygenase and hydroxylamine dehydrogenase decreased after transient 2,4,6-TCP shock, including amoA, amoC and nxrA. Thauera, Dechloromonas and Candidatus_Competibacter played key roles in the restorative process, which provided stable abundances of narG, norB , norC and nosZ. The results will deeply understand into the effect of transient 2,4,6-TCP shock on bioreactor performance and provide theoretical basis to build promising recoveries strategy of bioreactor performance.

Pollution and risk assessment of phenolic compounds in drinking water sources from South-Western Nigeria.

This study reports the occurrence and risk assessment of 2,4-dinitrophenol (2,4-DNP), phenol (PHE), and 2,4,6-trichlorophenol (2,4,6-TCP) in drinking water sources in three south-western States in Nigeria (Osun, Oyo, and Lagos). Groundwater (GW) and surface water (SW) were collected during dry and rainy seasons of a year. The detection frequency of the phenolic compounds followed the trend Phenol > 2,4-DNP > 2,4,6-TCP. The mean concentrations of 2,4-DNP, Phenol, and 2,4,6-TCP in GW/SW samples from Osun State were 639/553 µg L-1, 261/262 µg L-1, and 169/131 µg L-1 during the rainy season and 154/7 µg L-1, 78/37 µg L-1, and 123/15 µg L-1 during the dry season, respectively. In Oyo State, the mean concentrations were 165/391 µg L-1 for 2,4-DNP and 71/231 µg L-1 for Phenol in GW/SW samples, respectively, during the rainy season. Generally, in the dry season, these values decreased. In any case, these concentrations are higher than those previously reported in water from other countries. The concentration of 2,4-DNP in water posed serious ecological risks to Daphnia on the acute scale while it was algae on the chronic scale. Estimated daily intake and hazard quotient calculations suggest that 2,4-DNP and 2,4,6-TCP in water pose serious toxicity concerns to humans. Additionally, the concentration of 2,4,6-TCP in water from Osun State in both seasons of the year and in both groundwater and surface water poses significant carcinogenic risks to persons ingesting water from these sources in the State. Every exposure group studied were at risk from ingesting these phenolic compounds in water. However, this risk decreased with increasing age of the exposure group. Results from the principal component analysis indicate that 2,4-DNP in water samples is from an anthropogenic source different from that for Phenol and 2,4,6-TCP. There is a strong need to treat water from GW and SW systems in these States before ingesting while assessing their quality regularly.

Cathode potential regulates the microbiome assembly and function in electrostimulated bio- dechlorination system.

Mechanism of microbiome assembly and function driven by cathode potential in electro-stimulated microbial reductive dechlorination system remain poorly understood. Here, core microbiome structure, interaction, function and assembly regulating by cathode potential were investigated in a 2,4,6-trichlorophenol bio-dechlorination system. The highest dechlorination rate (24.30 µM/d) was observed under - 0.36 V with phenol as a major end metabolite, while, lower (-0.56 V) or higher (0.04 V or -0.16 V) potentials resulted in 1.3-3.8 times decreased of dechlorination kinetic constant. The lower the cathode potential, the higher the generated CH4, revealing cathode participated in hydrogenotrophic methanogenesis. Taxonomic and functional structure of core microbiome significantly shifted within groups of - 0.36 V and - 0.56 V, with dechlorinators (Desulfitobacterium, Dehalobacter), fermenters (norank_f_Propionibacteriaceae, Dysgonomonas) and methanogen (Methanosarcina) highly enriched, and the more positive interactions between functional genera were found. The lowest number of nodes and links and the highest positive correlations were observed among constructed sub-networks classified by function, revealing simplified and strengthened cooperation of functional genera driven by group of - 0.36 V. Cathode potential plays one important driver controlling core microbiome assembly, and the low potentials drove the assembly of major dechlorinating, methanogenic and electro-active genera to be more deterministic, while, the major fermenting genera were mostly governed by stochastic processes.

Polypyrrole-induced active-edge-S and high-valence-Mo reinforced composites with boosted electrochemical performance for the determination of 2,4,6-trichlorophenol in the aquatic environment.

With the extensive application of halogenated aromatic compounds, including 2,4,6-Trichlorophenol (2,4,6-TCP), improper treatment or discharge contribute to persistently harmful effects on humans and the ecosystem, rendering the identification and monitoring of 2,4,6-TCP in the aquatic environment urgently required. In this study, a highly sensitive electrochemical platform was developed using active-edge-S and high-valence-Mo rich MoS2/polypyrrole composites. MoS2/PPy illustrates superior electrochemical performance and catalytic activity and has not been explored for detecting chlorinated phenols previously. The local environment of polypyrrole induces the richness of active edge S and a high oxidation state of Mo species in the composites, both of which endorse a sensitive anodic current response due to the favored oxidation of 2,4,6-TCP through nucleophilic substitution. Also, the higher complementarity between pyrrole and 2,4,6-TCP with respective electron-rich and electron-poor features through π-π stacking interactions enhances the specific detection capability of 2,4,6-TCP by the MoS2/polypyrrole-modified electrode. The MoS2/polypyrrole-modified electrode achieved a linear range of 0.1-260 µM with an ultralow limit of detection of 0.009 µM. Additionally, the structural stability boosted by the linkage of polypyrrole and MoS2 results in good resistance and satisfactory recovery in real water samples. The compiled results demonstrate that the proposed MoS2/polypyrrole composite opens up a new potential to advance a sensitive, selective, facile fabrication, and low-cost platform for the on-site determination of 2,4,6-TCP in aquatic systems. The sensing of 2,4,6-TCP is important to monitor its occurrence and transport, and can also serve to track the effectiveness and adjust subsequent remediation treatments applied to contaminated sites.