Combined effects of pentachlorophenol and nano-TiO2 with different sizes on antioxidant, digestive, and immune responses of the swimming crab Portunus trituberculatus.

Marine nano-titanium dioxide (nano-TiO2) and pentachlorophenol (PCP) pollution are escalating concerns in coastal areas. This study investigated the combined effects of continuous exposure to nano-TiO2 (25 nm, 100 nm) and PCP (0, 1, 10 µg/L) for 28 days on the antioxidant, digestive, and immune abilities of the swimming crab Portunus trituberculatus. Compared with the control group, the interaction between nano-TiO2 and PCP was significantly higher than exposure to a single stressor, with a pronounced decrease in amylase activity observed due to the reducing nano-TiO2 particle sizes. Resulting in increased MDA and SOD activity. The expression levels of Toll4, CSP3, and SER genes in crab hemolymph showed perturbations following exposure to nano-TiO2 and PCP. In summary, according to the results of CAT, GPX, PES and AMS enzyme activities, it was concluded that compared to the larger particle size (100 nm), the single stress of nano-TiO2 at a smaller particle size (25 nm) and co-stress with PCP have more significant impacts on P. trituberculatus. However, the potential physiological regulation mechanism of the interaction between these pollutants remains elusive and requires further study.

The metabolic activation of pentachlorophenol to chloranil as a potent inhibitor of human and rat placental 3ß-hydroxysteroid dehydrogenases.

Pentachlorophenol (PCP) is a widely used pesticide. However, whether PCP and its metabolite chloranil have endocrine-disrupting effects by inhibiting placental 3ß-hydroxysteroid dehydrogenase 1 (3ß-HSD1) remains unclear. The study used in vitro assays with human and rat placental microsomes to measure 3ß-HSD activity as well as human JAr cells to evaluate progesterone production. The results showed that PCP exhibited moderate inhibition of human 3ß-HSD1, with an IC50 value of 29.83 µM and displayed mixed inhibition in terms of mode of action. Conversely, chloranil proved to be a potent inhibitor, demonstrating an IC50 value of 147 nM, and displaying a mixed mode of action. PCP significantly decreased progesterone production by JAr cells at 50 µM, while chloranil markedly reduced progesterone production at ≥1 µM. Interestingly, PCP and chloranil moderately inhibited rat placental homolog 3ß-HSD4, with IC50 values of 27.94 and 23.42 µM, respectively. Dithiothreitol (DTT) alone significantly increased human 3ß-HSD1 activity. Chloranil not PCP mediated inhibition of human 3ß-HSD1 activity was completely reversed by DTT and that of rat 3ß-HSD4 was partially reversed by DTT. Docking analysis revealed that both PCP and chloranil can bind to the catalytic domain of 3ß-HSDs. The difference in the amino acid residue Cys83 in human 3ß-HSD1 may explain why chloranil is a potent inhibitor through its interaction with the cysteine residue of human 3ß-HSD1. In conclusion, PCP is metabolically activated to chloranil as a potent inhibitor of human 3ß-HSD1.

Occurrence of pentachlorophenol in surface water from the upper to lower reaches of the Yangtze River and treated water in Wuhan, China.

Pentachlorophenol (PCP), a persistent organic pollutant, has been banned in many countries, but it is still used in China as a wood preservative, molluscicide, or reagent for fish-pond cleaning, which may pose risks to the ecosystem and humans. However, data on the occurrence of PCP in the environment are scarce in the recent decade. The Yangtze River was regarded as a priority area of PCP pollution according to previous documents. This study aimed to examine the spatial distribution of PCP in the Yangtze River water, the differences in dry and wet seasons, the ecological risk for aquatic organisms, and its removal efficiency in tap water treatment plants. The river water samples (n = 144) were collected from the upper, middle, and lower reaches across ten provinces (or municipalities) in December 2020 and June 2021, respectively. PCP was detected in 88.9% of all the samples, ranging from

Co-exposure to pentachlorophenol (PCP) and cadmium (Cd) triggers apoptosis-like cell death in Eschericia coli.

Pentachlorophenol (PCP) - cadmium (Cd) complex pollution has been identified as a form of persistent soil pollution in south China, exerting detrimental impacts on the indigenous soil bacterial communities. Hence, it is worthwhile to investigate whether and how bacterial populations alter in response to these pollutants. In this study, Escherichia coli was used as a model bacterium. Results showed that PCP exposure caused bacterial cell membrane permeability changes, intracellular ROS elevation, and DNA fragmentation, and triggered apoptosis-like cell death at low exposure concentration and necrosis at high exposure concentration. Cd exposure caused severe oxidative damage and cell necrosis in the tested bacterial strain. The co-exposure to PCP and Cd elevated the ROS level, stimulated the bacterial caspase activity, and induced DNA fragmentation, thereby leading to an apoptosis-like cell death. In conclusion, PCP-Cd complex pollution can cause bacterial population to decrease through apoptosis-like cell death pathway. However, it is worth noting that the subpopulation survives under the complex pollution stress.

Effects of nano-TiO2 and pentachlorophenol on the bioenergetics of mussels under predatory stress.

Organic and nanoparticle pollutants are the main environmental problems affecting marine species, which have received great attention. However, the combined effect of pollutants on marine life in the presence of predators needs to be clarified. In this study, the effects of pentachlorophenol (PCP) and titanium dioxide nanoparticles (nano-TiO2) on the energy metabolism of mussels (Mytilus coruscus) in the presence of predators were assessed through cellular energy allocation (CEA) approach. Mussels were exposed to PCP (0, 1, and 10 µg/L), nano-TiO2 (1 mg/L, 25 and 100 nm), and predators (Portunus trituberculatus presence/absence) for 14 days. Exposure to high concentrations of PCP (10 µg/L) with small particle size nano-TiO2 (25 nm) decreased cellular energy stores (carbohydrates, lipids, and proteins) and increased cellular energy demand (measured as the activity of the mitochondrial electron transport system, ETS). During the first 7 days, energy was supplied mainly through the consumption of carbohydrates, while lipids are mobilized to participate after 7 days. The presence of predators caused a further decrease in energy stores. These findings demonstrate that PCP, nano-TiO2 and predators have a negative impact on energy metabolism at the cellular level. Carbohydrates are not able to meet the metabolic demand, lipids need to be consumed, and energy metabolism was also mediated by the involvement of proteins. Overall, our results suggest that PCP, nano-TiO2 and predators disrupt the cellular energy metabolism of mussels through reduced cellular energy allocation, small particles and predators drive mussels to exert energetic metabolic adjustments for detoxification reactions when toxic contaminants are present.

[Exposure characteristics and health risk assessment of 97 typical chemical pollutants in human serum].

Rapid industrial and agricultural developments in China have led to the wide use and discharge of chemical products and pesticides, resulting in extensive residues in environmental media. These residues can enter the human body through various pathways, leading to high exposure risks and health hazards. Because the human body is exposed to a variety of chemical pollutants, accurately quantifying the exposure levels of these pollutants in the human body and evaluating their health risks are of great importance. In this study, the serum concentrations of 97 typical chemical pollutants of 60 adults in central China were simultaneously determined using solid-phase extraction coupled with gas chromatography-tandem mass spectrometry (SPE-GC-MS/MS). In this method, 200 µL of a serum sample was mixed with 10 µL of an isotope-labeled internal standard solution. The sample was vortexed and refrigerated overnight at 4 ℃. Each sample was then deproteinized by the addition of 200 µL of 15% formic acid aqueous solution and vortexed. The serum sample was loaded into a preconditioned Oasis® PRiME HLB SPE cartridge and rinsed with 3 mL of methanol-water (6∶1, v/v). The SPE cartridge was subsequently vacuumed. The analytes were eluted with 3 mL of dichloromethane followed by 3 mL of n-hexane. The eluent was concentrated to near dryness under a gentle nitrogen stream and reconstituted with 100 µL of acetone. The samples were determined by GC-MS/MS and separated on a DB-5MS capillary column (30 m×0.25 mm×0.25 µm) with temperature programming. The column temperature was maintained at 70 ℃ for 2 min, increased at a rate of 25 ℃/min to 150 ℃, increased at a rate of 3 ℃/min to 200 ℃, and then held for 2 min. Finally, the column temperature was increased at a rate of 8 ℃/min to 300 ℃ and maintained at this temperature for 8 min. The samples were detected in multiple-reaction monitoring (MRM) mode and quantitatively analyzed using the internal standard method. Multiple linear regression models were used to analyze the effects of demographic characteristics, lifestyle habits, and diet on the concentrations of the chemical pollutants in the serum samples, and known biomonitoring equivalents (BEs) and human biomonitoring (HBM) values were combined to compute hazard quotients (HQs) and hazard indices (HIs) and evaluate the health risks of single and cumulative exposures to the chemical pollutants. The results showed that the main pollutants detected in human serum were organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). The detection rates of eight pollutants, including hexachlorobenzene (HCB) (100%), pentachlorophenol (PCP) (100%), p,p'-dichlorodiphenylene (p,p'-DDE) (100%), PCB-138 (100%), PCB-153 (98.3%), ß-hexachlorocyclohexane (ß-HCH) (91.7%), fluorene (Flu) (85.0%), and anthracene (Ant) (75.0%), were greater than 70%. The serum levels of ß-HCH were higher in females than in males, and age was positively correlated with exposure to p,p'-DDE, PCB-138, PCB-153, and ß-HCH. Increased exposure levels to p,p'-DDE and ß-HCH may be associated with a high frequency of meat intake, whereas increased exposure level to PCP may be associated with a high frequency of vegetable intake. The serum HQ of PCP was greater than 1 in 6.7% of the samples, and no risk was observed for HCB and p,p'-DDE exposure in the study population. Approximately 28.3% of the study subjects had HI values greater than 1. Overall, the general adult population in this region is widely exposed to a wide range of chemical pollutants, and gender, age, and diet are likely to be the main factors influencing the concentration of chemical pollutants. The health risk of single and compound exposures to chemical pollutants should not be ignored.

Interpretable machine learning for predicting the fate and transport of pentachlorophenol in groundwater.

Pentachlorophenol (PCP) is a commonly found recalcitrant and toxic groundwater contaminant that resists degradation, bioaccumulates, and has a potential for long-range environmental transport. Taking proper actions to deal with the pollutant accounting for the life cycle consequences requires a better understanding of its behavior in the subsurface. We recognize the huge potential for enhancing decision-making at contaminated groundwater sites with the arrival of machine learning (ML) techniques in environmental applications. We used ML to enhance the understanding of the dynamics of PCP transport properties in the subsurface, and to determine key hydrochemical and hydrogeological drivers affecting its transport and fate. We demonstrate how this complementary knowledge, provided by data-driven methods, may enable a more targeted planning of monitoring and remediation at two highly contaminated Swedish groundwater sites, where the method was validated. We evaluated 6 interpretable ML methods, 3 linear regressors and 3 non-linear (i.e., tree-based) regressors, to predict PCP concentration in the groundwater. The modeling results indicate that simple linear ML models were found to be useful in the prediction of observations for datasets without any missing values, while tree-based regressors were more suitable for datasets containing missing values. Considering that missing values are common in datasets collected during contaminated site investigations, this could be of significant importance for contaminated site planners and managers, ultimately reducing site investigation and monitoring costs. Furthermore, we interpreted the proposed models using the SHAP (SHapley Additive exPlanations) approach to decipher the importance of different drivers in the prediction and simulation of critical hydrogeochemical variables. Among these, sum of chlorophenols is of highest significance in the analyses. Setting that aside from the model, tetra chlorophenols, dissolved organic carbon, and conductivity found to be of highest importance. Accordingly, ML methods could potentially be used to improve the understanding of groundwater contamination transport dynamics, filling gaps in knowledge that remain when using more sophisticated deterministic modeling approaches.

Exposure assessment of nitrate and phenol derivatives in Tehran's water distribution system.

The presence of organic and inorganic contaminants in drinking water is a global concern. Nitrate and phenol derivatives are examples of pollutants that could be of anthropogenic origin. They are associated with numerous health risks, underscoring the importance of monitoring their presence in drinking water. This study aimed to measure nitrate and phenol derivatives, including 2,4-Dichlorophenol (2,4-DCP), Pentachlorophenol (PCP), 2,4,5-Trichlorophenol (2,4,5-TCP), 2-Chlorophenol (2-CP), 4-Chlorophenol (4-CP), and phenol, in Tehran's water distribution system (WDS). The pollutants in Tehran's WDS were significantly and positively correlated with precipitation. The Hazard Quotient (HQ) and the Excess Lifetime Cancer Risk (ELCR) of the detected pollutants were estimated. The results showed that the regional mean of nitrate and PCP in Tehran's WDS were 35.58±8.71mg L-1 and 76.14±16.93 ng L-1 lower than the guideline values of 50 mg L-1 and 1000 ng L-1, respectively. Some districts exhibited nitrate concentration exceeding the allowable limit by a factor of 1.2 to 2.3. Consequently, the nitrate intake in some districts constituted approximately 50% of the reference dose. While PCP as a phenol derivative with more health concerns was identified in Tehran's WDS, the likelihood of its health effects was determined to be negligible.

Pentachlorophenol affects doxycycline and tetracycline resistance genes in soil by altering microbial structure.

Tetracycline antibiotics play a vital role in animal husbandry, primarily employed to uphold the health of livestock and poultry. Consequently, when manure is reintegrated into farmland, tetracycline antibiotics can persist in the soil. Simultaneously, to ensure optimal crop production, organochlorine pesticides (OCPs) are frequently applied to farmland. The coexistence of tetracycline antibiotics and OCPs in soil may lead to an increased risk of transmission of tetracycline resistance genes (TRGs). Nevertheless, the precise mechanism underlying the effects of OCPs on tetracycline antibiotics and TRGs remains elusive. In this study, we aimed to investigate the effects of OCPs on soil tetracycline antibiotics and TRGs using different concentrations of doxycycline (DOX) and pentachlorophenol (PCP). The findings indicate that PCP and DOX mutually impede their degradation in soil. Furthermore, our investigation identifies Sphingomonas and Bacillus as potential pivotal microorganisms influencing the reciprocal inhibition of PCP and DOX. Additionally, it is observed that the concurrent presence of PCP and DOX could impede each other's degradation by elevating soil conductivity. Furthermore, we observed that a high concentration of PCP (10.7 mg/kg) reduced the content of efflux pump tetA, ribosome protective protein tetM, tetQ, and passivating enzyme tetX. In contrast, a low PCP concentration (6.4 mg/kg) only reduced the content of ribosome protective protein tetQ. This suggests that PCP may reduce the relative abundance of TRGs by altering the soil microbial community structure and inhibiting the potential host bacteria of TRGs. These findings have significant implications in understanding the combined pollution of veterinary antibiotics and OCPs. By shedding light on the interactions between these compounds and their impact on microbial communities, this study provides a theoretical basis for developing strategies to manage and mitigate their environmental impact, and may give some information regarding the sustainable use of antibiotics and pesticides to ensure the long-term health and productivity of agricultural systems.

Effects and mechanisms of nZVI on CO2 and CH4 emissions in uncontaminated and pentachlorophenol-contaminated soils.

With the increasing application of nanoscale zero-valent iron (nZVI) for in situ soil remediation, its effects on soil functionality and ecosystem need to be thoroughly evaluated. Herein, we investigated the effects of nZVI on CO2 and CH4 emissions from uncontaminated and pentachlorophenol (PCP)-contaminated soils and the underlying microbial mechanisms by designing a 68-day anaerobic soil culture experiment; thereafter, the effects of above aged nZVI on soil CO2 and CH4 emissions in the following 20 days were further studied. In the uncontaminated soil, 1-10 g/kg nZVI treatments reduced soil CO2 emission by 17.4-82.6% and increased soil CH4 emission by 10.8%-119.7%, but these effects disappeared after the nZVI was aged. The emissions of soil CO2 and CH4 were significantly inhibited by the PCP contamination (100 mg/kg) mainly due to the toxicity to related soil microorganisms. The applications of 1-10 g/kg nZVI significantly reduced CO2 emissions from the PCP-contaminated soil by 24.0-86.7%, while 10 g/kg nZVI markedly increased soil CH4 emission by 1875.4% and restored the methanogenic activity to the control level after the nZVI was aged. The 10 g/kg nZVI treatment enriched hydrogenotrophic methanogen (Methanobacterium) and organics-degrading bacteria by releasing H2, increasing soil pH, and decreasing soil Eh; the abundance of genes encoding key enzymes (Mcr, Mtr, Hdr, Mta, and Mtb) in all methanogenic pathways significantly increased after the nZVI treatment, indicating that nZVI could have a broad promoting effects on soil methanogenic processes. The findings demonstrate that the addition of nZVI for in situ remediation of organochlorines-contaminated soils will affect soil greenhouse gas emissions and provide basic data for safe nZVI applications.

Association of hair polychlorinated biphenyls and multiclass pesticides with obesity, diabetes, hypertension and dyslipidemia in NESCAV study.

Obesity, diabetes, hypertension and dyslipidemia are well-established risk factors for cardiovascular diseases (CVDs), and have been associated with exposure to persistent organic pollutants. However, studies have been lacking as regards effects of non-persistent pesticides on CVD risk factors. Here, we investigated whether background chronic exposure to polychlorinated biphenyls (PCBs) and multiclass pesticides were associated with the prevalence of these CVD risk factors in 502 Belgian and 487 Luxembourgish adults aged 18-69 years from the Nutrition, environment and cardiovascular health (NESCAV) study 2007-2013. We used hair analysis to evaluate the chronic internal exposure to three PCBs, seven organochlorine pesticides (OCs) and 18 non-persistent pesticides. We found positive associations of obesity with hexachlorobenzene (HCB), ß-hexachlorocyclohexane (ß-HCH) and chlorpyrifos, diabetes with pentachlorophenol (PCP), fipronil and fipronil sulfone, hypertension with PCB180 and chlorpyrifos, and dyslipidemia with diflufenican and oxadiazon, among others. However, we also found some inverse associations, such as obesity with PCP, diabetes with γ-HCH, hypertension with diflufenican, and dyslipidemia with chlorpyrifos. These results add to the existing evidence that OC exposure may contribute to the development of CVDs. Additionally, the present study revealed associations between CVD risk factors and chronic environmental exposure to currently used pesticides such as organophosphorus and pyrethroid pesticides.

Toxicity assessment and detoxification metabolism of sodium pentachlorophenol (PCP-Na) on marine economic species: a case study of Moerella iridescens and Exopalaemon carinicauda.

Sodium pentachlorophenol (PCP-Na) is widespread in the marine environment; however, its impact on marine organisms remains under-researched. Moerella iridescens and Exopalaemon carinicauda are marine species of economic importance in China and under threat from PCP-Na pollution. Thus, this study aimed to assess the toxicity and detoxification metabolism of PCP-Na on M. iridescens and E. carinicauda. The study revealed that the 96 h median lethal concentration (LC50) of PCP-Na for M. iridescens and E. carinicauda were 9.895 mg/L and 14.143 mg/L, respectively. A species sensitivity distribution (SSD) for PCP-Na was developed specifically for marine organisms, determining a hazardous concentration to 5% of the species (HC5) of 0.047 mg/L. During the sub-chronic exposure period, PCP-Na accumulated significantly in M. iridescens and E. carinicauda, with highest concentrations of 41.22 mg/kg in the soft tissues of M. iridescens, 42.58 mg/kg in the hepatopancreas of E. carinicauda, and only 0.85 mg/kg in the muscle of E. carinicauda. Furthermore, the study demonstrated that detoxifying metabolic enzymes and antioxidant defense system enzymes of E. carinicauda responded stronger to PCP-Na compared to M. iridescens, suggesting that E. carinicauda may possess a stronger detoxification capacity. Notably, five biomarkers were identified and proposed for monitoring and evaluating PCP-Na contamination. Overall, the results indicated that M. iridescens and E. carinicauda exhibit greater tolerance to PCP-Na than other marine species, but they are susceptible to accumulating PCP-Na in their tissues, posing a significant health risk. Consequently, conducting aquatic health risk assessments in areas with potential PCP-Na contamination is strongly recommended.

Pentachlorophenol exposure induced neurotoxicity by disrupting citrulline metabolism in larvae and adult zebrafish.

Pentachlorophenol (PCP) is a ubiquitous environmental toxicant with various adverse effects. Although its neurotoxicity has been reported, the underlying mechanism and subsequent detoxification remain unclear. In this study, embryos and adult zebrafish were exposed to PCP to determine its potential neurotoxic mechanism and protective indicators. The survival rate, heart rate, mobility time, active status and moving distance were significantly decreased in larvae after 30 µg/L PCP exposure. Likewise, the mobile time, latency to the first movement, velocity and moving distance of adult zebrafish were significantly reduced by PCP exposure. Untargeted metabolomics analysis of larvae revealed that arginine and proline metabolism was the primary pathway affected by PCP exposure, reflected by increased proline and decreased citrulline (CIT) contents, which were confirmed by quantitative data. PCP exposure suppressed the conversion from arginine to CIT in larvae by downregulating the expression of nos1 and nos2a. Ornithine content was increased in the brains and intestines of adult zebrafish after PCP exposure, which inhibited ornithine catabolism to CIT by downregulating otc, resulting in reduced CIT. Intriguingly, CIT supplementation significantly restored the neurobehavioral defects induced by PCP in larvae and adult zebrafish. CIT supplementation upregulated the expression of ef1α and tuba1 in larvae and inhibited the downregulation of ef1α in the brains of adult zebrafish. Taken together, these results indicated that CIT supplementation could protect against PCP-induced neurotoxicity by upregulating the expression of genes involved in neuronal development and function.

Determination of Pentachlorophenol in Seafood Samples from Zhejiang Province Using Pass-Through SPE-UPLC-MS/MS: Occurrence and Human Dietary Exposure Risk.

Pentachlorophenol (PCP) has attracted wide attention due to its high toxicity, persistence, and bioaccumulation. In this study, a sensitive UPLC-MS/MS method for the determination of PCP in seafood samples was developed and validated. The samples were ultrasonic extracted with acetonitrile containing 1% acetic acid-acetonitrile and followed by using a pass-through solid-phase extraction (SPE) cleanup on Captiva EMR-Lipid cartridges. The linearity of this method ranged from 1 to 1000 µg/L, with regression coefficients of >0.99. The detection limit and quantitation limit were 0.5 µg/kg and 1.0 µg/kg, respectively. The recoveries in different types of seafood samples ranged from 86.4% to 102.5%, and the intra-day and inter-day relative standard deviations (RSDs) were 3.7% to 11.2% and 2.9% to 12.1%, respectively (n = 6). Finally, the method has been successfully utilized for the screening of PCP in 760 seafood samples from Zhejiang Province. PCP was detected in 5.8% of all seafood samples, with the largest portion of detections found in shellfish, accounting for approximately 60% of the total. The average concentrations detected ranged from 1.08 to 21.49 µg/kg. The non-carcinogenic risk indices for adults and children who consume PCP ranged from 10-4 to 10-3 magnitudes. All of these indices stayed significantly below 1, implying that the health risk from PCP in marine organisms to humans is minimal.

Fungal Biotransformation of Hazardous Organic Compounds in Wood Waste.

A diverse spectrum of organisms, such as fungi, bacteria, and actinomycetes, can degrade and transform organic matter, including wood, into valuable nutrients. A sustainable economy has the goal of efficiently using waste as raw materials, and in this optic, it uses biological preparations more and more often, supporting the decomposition of lignocellulosic waste. With reference to wood wastes, which are produced in a substantial amount by the forest and wood industry, one of the possibilities to biodegrade such lignocellulosic material is the composting process. In particular, microbiological inoculum containing dedicated fungi can contribute to the biodegradation of wood waste, as well as the biotransformation of substances from the protection of wood, such as pentachlorophenol (PCP), lindane (hexachlorobenzene) and polycyclic aromatic hydrocarbons (PAHs). The purpose of this research was to produce a literature review in terms of the selection of decay fungi that could potentially be used in toxic biotransformation unions. The findings of the literature review highlighted how fungi such as Bjerkandera adusta, Phanerochaete chrysosporium, and Trametes versicolor might be ingredients of biological consortia that can be effectively applied in composting wood waste containing substances such as pentachlorophenol, lindane, and polycyclic aromatic hydrocarbons (PAHs).

Nano-TiO2 aggravates the adverse effect of pentachlorophenol on antioxidant and immune response in anti-predatory mussels.

Nano-TiO2 can act as a vector to organic compounds, such as pentachlorophenol (PCP) posing a potential threat to the marine ecosystems. Studies showed that nano pollutant toxicity can be modulated by abiotic factors, but little is known about the potential influence of biotic stressors (such as predators) on the physiological responses to pollutants in marine organisms. We explored the effects of n-TiO2 and PCP on the mussel Mytilus coruscus in the presence of its natural predator, the swimming crab Portunus trituberculatus. Exposure to n-TiO2, PCP, and predation risk showed interactive effects on antioxidant and immune parameters of the mussels. Elevated activities of catalase (CAT), glutathione peroxidase (GPX), acid phosphatase (ACP) and alkaline phosphatase (AKP), suppressed activity of superoxide dismutase (SOD), lower levels of glutathione (GSH) and increased malondialdehyde (MDA) levels indicated dysregulation of the antioxidant system and immune stress induced by single PCP or n-TiO2 exposure. Integrated biomarker (IBR) response values showed the effect of PCP was concentration dependent. Of the two used n-TiO2 sizes (25 and 100 nm), larger particles induced higher antioxidant and immune disturbances indicating higher toxicity possibly due to higher bioavailability. Compared to single PCP exposure, the combination of n-TiO2 and PCP enhanced the imbalance of SOD/CAT and GSH/GPX and led to elevated oxidative lesions and activation of immune-related enzymes. Overall, the combined impacts of pollutants and biotic stress exhibited a greater magnitude of adverse effects on antioxidant defense and immune parameters in mussels. The toxicological effects of PCP were exacerbated in the presence of n-TiO2, and the deleterious impact of these stressors was further amplified under predator-induced risk after prolonged (28 days) exposure. However, the underlying physiological regulatory mechanisms governing the interplay of these stressors and predatory cues on mussels remain elusive, warranting further investigation.

Functionalized chitosan and sodium alginate for the effective removal of recalcitrant organic pollutants.

In this work, the study of an oxidative-coupling reaction by immobilization of laccase or horseradish peroxidase (HRP) onto chitosan and sodium alginate was reported. The oxidative-coupling reaction of three recalcitrant organic pollutants (ROPs) such as chlorophenol compounds including 2,4-dichlorophenol (DCP), 2,4,6- trichlorophenol (TCP), pentachlorophenol (PCP) was studied. The results showed that the systems with immobilized laccase or horseradish peroxidase had broader range of optimum pH and temperature when compared to that of free laccase and horseradish peroxidase. The removal efficiencies of DCP, TCP and PCP within 6 h were found to be 77 %, 90 % and 83 %, respectively. The rate constants of the first order reactions for laccase were arranged as 0.30 h-1 (TCP) > 0.13 h-1 (DCP) > 0.11 h-1 (PCP) and the rate constants for HRP were arranged as 0.42 h-1 (TCP) > 0.32 h-1 (PCP) > 0.25 h-1 (DCP). The removal rate of TCP was found to be the highest among all and the removal efficiency of ROPs by HRP was always better than that of laccase. The major products of the reaction were identified by LC-MS and confirmed as humic-like polymers.

Oral administration of curcumin and gallic acid alleviates pentachlorophenol-induced oxidative damage in rat intestine.

INTRODUCTION: Pentachlorophenol (PCP) is used as pesticide and wood preservative. We have previously shown that PCP causes oxidative damage in rat intestine. AIM: This study aimed to delineate the possible therapeutic potential of curcumin (CUR) and gallic acid (GA) against PCP-induced damage in rat intestine. METHODS: PCP alone group received 125 mg PCP/kg body weight/day orally for 4 days. Animals in combination groups received CUR or GA (100 mg/kg bw) for 18 days and PCP (125 mg/kg bw) for the last four days. Rats were sacrificed and intestinal preparations were analyzed for various parameters. RESULTS: Administration of PCP alone altered the activities of metabolic, antioxidant and brush border membrane enzymes. It also increased DNA-protein crosslinking and DNA-strand scission. Animals in combinations groups showed significant amelioration against PCP-induced oxidative damage. Histological abrasions were seen in PCP alone group which were reduced in the intestines of combination groups. CUR was more effective protectant than GA. CONCLUSIONS: CUR and GA protected rat intestine from PCP-mediated changes in the activities of metabolic, antioxidant and brush border membrane enzymes. They also prevented DNA damage and histological abrasions. The antioxidant character of CUR and GA may be responsible for the diminution of PCP-mediated oxidative damage.

Laccase-immobilized on superparamagnetic iron oxide nanoparticles incorporated polymeric ultrafiltration membrane for the removal of toxic pentachlorophenol.

A biocatalytic membrane offers an ideal alternative to the conventional treatment process for the removal of toxic pentachlorophenol (PCP). The limelight of the study is to utilize superparamagnetic iron oxide nanoparticles (SPIONs) incorporated (poly (methyl vinyl ether-alt-maleic acid) (PMVEAMA) and poly (ether - ether) sulfone (PEES)) membrane for immobilization of laccase and its application towards the removal of PCP. In regard to immobilization of Tramates versicolor laccase onto membranes, 5 mM glutaraldehyde with 10 h cross-linking time was employed, yielding 76.92% and 77.96% activity recovery for PEES/PMVEAMA/La and PEES/PMVEAMA/SPIONs/Lac, respectively. In the context of kinetics and stability studies, the immobilized laccase on PEES/PMVEAMA/Lac membrane outperforms the free and PEES/PMVEAMA laccases. At pH 7.0, the free enzyme loses half of its activity, while the immobilized laccases maintained more than 87% of their initial activity even after 480 min. With regard to PCP removal, the removal efficiency of immobilized laccase on the membrane was more than free enzyme. With 100 ppm of PCP, immobilized laccase on PEES/PMVEAMA/SPIONs membrane at pH 4.0 and 50 °C had a removal efficacy of 61.65% in 24 h. Furthermore, to perk up the removal of PCP, the laccase-aided system with mediators was investigated. Amongst, veratryl alcohol displayed 71.04% of PCP removal using immobilized laccase. The reusability of the laccase heightened after immobilization on PEES/PMVEAMA/SPIONs portraying 62.44% of the residual activity with 39.4% of PCP removal even after five cycles. The current investigation reveals the efficacy of the mediator-aided PEES/PMVEAMA/lac membrane system towards removing PCP from the aqueous solution, which can also be proposed for a membrane bioreactor.

Removal of pentachlorophenol and phenanthrene from lignocellulosic biorefinery wastewater by a biocatalytic/biosurfactant system comprising cross-linked laccase aggregates and rhamnolipid.

Synthesis and characterization of highly active cross-linked laccase aggregates (CLLAs) were performed and evaluated for removal of pentachlorophenol and phenanthrene from lignocellulosic biorefinery wastewater. Laccase from Tramates versicolor MTCC 138 was insolubilized as CLLAs via precipitation with 70% ammonium sulphate and simultaneous cross-linking with 5 mM glutaraldehyde to obtain activity recovery of 89.1%. Compared to the free laccase, the pH and thermal stability of the prepared CLLAs were significantly higher. At a high temperature of 60 °C, free laccase had a half-life of 0.25 h, while CLLAs had a half-life of 6.2 h. In biorefinery wastewater (pH 7.0), the free and CLLAs were stored for 3 day at a temperature of 30 °C. Free laccase completely lost their initial activity after 60 h; however, the CLLAs retained 39% activity till 72 h. Due to its excellent stability, free laccase and CLLAs were assessed for removing pentachlorophenol and phenanthrene in wastewater. CLLAs could remove 51-58% of pentachlorophenol (PCP) and phenanthrene (PHE) in 24 h. Biosurfactants, including surfactin, sophorolipid, and rhamnolipid, were assessed for their aptitude to improve the removal of organic contaminants in wastewater. Biorefinery wastewater incubated with all surfactants enhanced PCP and PHE removal compared to the no-surfactant controls. Further, 1 µM rhamnolipid significantly amplified pentachlorophenol and phenanthrene removal to 81-93% for free laccase and CLLAs, respectively.