Jianbiao Peng

Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H2O2 concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H2O2 concentration, while the optimal pH and H2O2 concentration were 7.0 and 8μM, respectively. 98% TCS was removed with only 0.1UmL(-1) SBP in 30min reaction time, while an HRP dose of 0.3UmL(-1) was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (KCAT) and catalytic efficiency (KCAT/KM) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via CC and CO coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water/wastewater treatment.

TPhP exposure disturbs carbohydrate metabolism, lipid metabolism, and the DNA damage repair system in zebrafish liver.

Triphenyl phosphate is a high production volume organophosphate flame retardant that has been detected in multiple environmental media at increasing concentrations. The environmental and health risks of triphenyl phosphate have drawn attention because of the multiplex toxicity of this chemical compound. However, few studies have paid close attention to the impacts of triphenyl phosphate on liver metabolism. We investigated hepatic histopathological, metabolomic and transcriptomic responses of zebrafish after exposure to 0.050 mg/L and 0.300 mg/L triphenyl phosphate for 7 days. Metabolomic analysis revealed significant changes in the contents of glucose, UDP-glucose, lactate, succinate, fumarate, choline, acetylcarnitine, and several fatty acids. Transcriptomic analysis revealed that related pathways, such as the glycosphingolipid biosynthesis, PPAR signaling pathway and fatty acid elongation, were significantly affected. These results suggest that triphenyl phosphate exposure markedly disturbs hepatic carbohydrate and lipid metabolism in zebrafish. Moreover, DNA replication, the cell cycle, and non-homologous end-joining and base excision repair were strongly affected, thus indicating that triphenyl phosphate hinders the DNA damage repair system in zebrafish liver cells. The present study provides a systematic analysis of the triphenyl phosphate-induced toxic effects in zebrafish liver and demonstrates that low concentrations of triphenyl phosphate affect normal metabolism and cell cycle.

Laccase-catalyzed removal of the antimicrobials chlorophene and dichlorophen from water: Reaction kinetics, pathway and toxicity evaluation

As active agents in cleaning and disinfecting products, antimicrobials have been widely spread in the environment and have drawn extensive attention as potential threats to the ecological system and human health. In this study, the laccase-catalyzed removal of two emerging antimicrobials, chlorophene (CP) and dichlorophen (DCP), was investigated under simulated environmental conditions. Intrinsic reaction kinetics showed that the removal of CP and DCP followed second-order reaction kinetics, first-order with respect to both the enzyme and the substrate concentration. It was also found that fulvic acid could suppress the transformation of CP and DCP by reversing the oxidation reactions through its action as a scavenger of the free radical intermediates produced from reactions between laccase and the substrates. Several reaction products were identified by a quadrupole time-of-flight mass spectrometer, and detailed reaction pathways were proposed. For both CP and DCP, direct polymerization was the principal pathway, and the coupling patterns were further corroborated based on molecular modeling. The nucleophilic substitution of chlorine by the hydroxyl group was observed, and further oxidation products capable of coupling with each other were also found. Additionally, toxicity evaluation tests using Scenedesmus obliquus confirmed that the toxicity of CP and DCP was effectively eliminated during the reaction processes.

Oxidation of disinfectants with Cl-substituted structure by a Fenton-like system Cu2+/H2O2 and analysis on their structure-reactivity relationship

As widely used chemicals intended to protect human being from infection of microorganisms, disinfectants are ubiquitous in the environment. Among them chlorine-substituted phenol is a basic structure in many disinfectant molecules. Removal of these pollutants from wastewater is of great concern. The oxidative degradation of antimicrobial agents such as triclosan, chlorofene, and dichlorofene by a Fenton-like system Cu2+/H2O2 was examined. Reaction conditions such as temperature, initial concentrations of H2O2 and Cu2+, and pH were optimized using triclosan as a representative. The degradation kinetics of the above disinfectants followed pseudo-first-order kinetics under the investigated conditions. Fourteen chlorophenols (CPs) with different chlorine substitution were also studied to evaluate the influence of molecular structure on the degradation process in the Cu2+/H2O2 system. Fourteen structure-related parameters were calculated using Gaussian 09 program. A quantitative structure-activity relationship (QSAR) model was established using SPSS software with measured rate constant (k) as dependent variable and calculated molecular descriptors as independent variables. A three-parameter model including energy of HOMO (Ehomo), molar heat capacity at constant volume (Cvθ), and the most positive net charge of hydrogen atoms (qH+) was selected for k prediction, with correlation coefficient R2 = 0.878. Analyses of the model demonstrated that the Cvθ was the most significant factor affecting the k of chlorophenols. Variance analysis and standard t-value test were used to validate the model.

Bioaccumulation mechanism of organophosphate esters in adult zebrafish (Danio rerio)

Although organophosphate esters (OPEs) have been detected with growing frequency in water ecosystems, the underlying accumulation mechanisms of these compounds in fish are still unknown. Here, we investigated the tissue-specific accumulation and depuration of seven OPEs in adult zebrafish at three levels (0, 1/150 LC50 (environmentally relevant level), and 1/30 LC50 per OPE congener) in laboratory after 19 days exposure and 3 days depuration. The bioaccumulation of OPEs varied among tissues. Muscle contained the lowest level of OPEs and liver had the highest level of two (TPP and TCEP) of the seven OPEs at steady state. The high levels and slow depuration rates of TDCIPP, TPHP, and TCP observed in roe indicated that the accumulated OPEs were potentially stored in roe and transferred to the next generation. After examination of the major metabolites (organophosphate diesters) in selected tissues, a physiologically based toxicokinetic (PBTK) model used in fish was adopted to explore the key factors affecting the bioaccumulation of OPEs in zebrafish. Biotransformation of OPEs with polychlorinated alkyl moieties (i.e. TDCIPP) and aryl moieties (i.e. TPHP and TCP) has more significant impacts on the accumulation than those of OPEs with alkyl or short chain chlorinated alkyl moieties. Furthermore, the partition process between tissues and blood was also investigated, and was demonstrated to be the dominant process for OPEs accumulation in zebrafish. This study provides critical information on the bioaccumulation, tissue distribution, and metabolization of OPEs in relation with OPE structures in fish, as well as the underlying bioaccumulation mechanisms/pathways of OPEs in aquatic life.

Oxidative degradation of atenolol by heat-activated persulfate: Kinetics, degradation pathways and distribution of transformation intermediates

Atenolol (ATL) has been widely detected in wastewater and aquatic environment. Although satisfactory removal of ATL from wastewater could be achieved, the mineralization ratio is usually low, which may result in the accumulation of its transformation products in the effluent and cause additional ecological risk to the environment. The aim of this study is to explore the effectiveness of heat activated persulfate (PS) in the removal of ATL from wastewater. Influencing factors including temperature, PS dosage, solution pH, existence of NO3-, Cl-, HCO3- and Suwannee river fulvic acid (SRFA) were examined. Complete removal of ATL was achieved within 40 min at pH 7.0 and 70 °C by using 0.5 mM PS. Inhibitive effects of HCO3- and FA had been observed on ATL oxidation, which was increased with the increase of their concentration. Sulfate radical (SO4-) was determined as the main reactive species by quenching experiment. Eight intermediates produced in ATL degradation were identified, and four degradation pathways were proposed based on the analysis of mass spectrum and frontier electron densities. The distribution of major intermediates was influenced by reaction temperature. Hydroxylation intermediates and deamidation intermediate were the most prominent at 50 °C and 60 °C, respectively. All intermediates were completely degraded in 40 min except P134 at 70 °C. Effective removal of TOC (74.12%) was achieved with 0.5 mM PS, pH 7.0 and 70 °C after 240 min. The results proved that heat activation of PS is a promising method to remove organic pollutants in wastewater.