Chenggang Gu

Visible Light-Driven Photocatalytic Degradation of Rhodamine B over NaBiO3: Pathways and Mechanism

The photocatalytic degradation of rhodamine B (RhB) over NaBiO3 under visible light irradiation was investigated in this study. RhB (20 mg/L) was almost completely decolorized in 30 min in given conditions. It was found that catalyst heating temperature significantly influenced the photocatalytic activity of the catalyst in which crystal water may played an important role, and the original sample exhibited higher activity than the heated samples did. To scrutinize the mechanistic details of the dye photodegradation, several critical analytical methods including UV-vis spectroscopy, HPLC, LC/MS/MS, and GC/MS were utilized to monitor the temporal course of the reaction. All N-deethylation intermediates and several small molecular products were separated and identified. The yield distinctness between two isomer intermediates (DR and EER) was considered to be correlated with the changes in the electron density of the dye molecule. Then two possible competitive photodegradation pathways of RhB over NaBiO3 were proposed: Chromophore cleavage and N-deethylation. Yet, cleavage of dye chromophore structure predominated over the N-deethylation.

Photolytic destruction of endocrine disruptor atrazine in aqueous solution under UV irradiation: Products and pathways

The ultraviolet (UV) photolysis of atrazine in aqueous solution was investigated at wavelength of 254 nm in this study. This paper was mainly focused on the identification of atrazine degradation intermediates by HPLC-MS/MS and its degradation mechanisms. The photodegradation products included the following seven classes: dechloro-hydroxylated products, chloro-dealkylated products, dechloro-dealkylated products, alkylic-oxidated products, delamination-hydroxylated products, olefinic products, and dechloro-hydrogenated products which were never reported in direct photolytic process, 4-isopropylamino-6-ethylamino-s-triazine (IEST), 4,6-dihydroxy-s-triazine (OOST). The main degradation products were 2-hydroxy-4-acetamido-6-ethylamino-s-triazine (OIET), 2-chloro-4-isopropyl-amino-6-methylamino-s-triazine (CIMT), 2-chloro-4,6-divinylamino-s-triazine (CVVT), 2-chloro-4-ethylamino-6-amino-s-triazine(CEAT), 2-methoxy-4-isopropyl-amino-6-methylamino-s-triazine (OIMT), 2-hydroxy-4-acetamindo-6-ethylamino-s-triazine (ODET), etc. Finally, the possible degradation mechanism was also proposed here.

Microwave-enhanced H2O2-based process for treating aqueous malachite green solutions: intermediates and degradation mechanism.

This work was originally performed to compare H(2)O(2)-based degradation of aqueous malachite green (MG) under microwave (MW)-enhanced and conventional heating (CH)-enhanced conditions, with the whole reaction courses traced by UV-vis spectrophotometer. The results showed that the higher discoloration rates of MG were available during MW-enhanced process, implying that the special heating way of MW might be more benefit for the generation of hydroxyl radicals than that of CH. Furthermore, major intermediates were separated and identified by HPLC-ESI-MS and GC-MS techniques. On the basis of 53 intermediates, degradation mechanism was deduced as follows: firstly, N-de-methylation reactions. Secondly, adduction reactions. Thirdly, decomposition of conjugated structure reactions of MG. Fourthly, removal of benzene reactions. Finally, open-ring reactions. Additionally, results revealed that microwave-enhanced H(2)O(2)-based treatment had more advantages, such as higher degradation efficiency, and no removal of catalyst after treatment.

Immobilization of Chlorobenzenes in Soil Using Wheat Straw Biochar

Biochar has shown great potential for immobilizing organic contaminants in soil. In this study, pentachlorobenzene (PeCB), 1,2,4,5-tetrachlorobenzene (1,2,4,5-TeCB), and 1,2,4-trichlorobenzene (1,2,4-TCB) artificially spiked soil was amended with wheat straw biochar at 0.1%, 0.5%, 1%, and 2% application rates, respectively. The sorption, dissipation, and bioavailability of chlorobenzenes (CBs) in soil were investigated. The sorption of PeCB by biochar was significantly higher than that of its sorption by both biochar-amended and unamended soil (p < 0.05). The dissipation and volatilization of CBs from biochar-amended soil significantly decreased relative to unamended soil (p < 0.05). Bioavailability of CBs, expressed as butanol extraction efficiency and earthworm (Eisenia fetida) bioaccumulation factor, significantly decreased with increasing aging time and biochar application rate. The effect of biochar content in soil on the bioavailability of CBs was more pronounced for 1,2,4-TCB relative to other CBs. This study suggested that wheat straw biochar, even at low application rates, could effectively immobilize the semivolatile CBs in soil and thus reduce their volatilization and bioavailability.

Tenax TA extraction to assess the bioavailability of DDTs in cotton field soils.

The rapid-desorbing fraction plays an important role in the bioavailability of organic pollutants in soil. In the present study, DDTs desorption from the cotton field soils was investigated by Tenax extraction. The results of the Tenax consecutive extraction (400 h) indicated that the rate constants were in the order of 10(-1), 10(-2), and 10(-4) h(-1) for the rapid, slow and very-slow desorption, respectively. The rapid-desorbing fraction was about 0.3 times the total soil DDTs, and about 2 times the Tenax 6 h-extracted fraction (single-point extraction). The rapid-desorbing fraction correlated well with the 6 h-extracted fraction (p<0.05), implying the feasibility of measuring the rapid-desorbing fraction with Tenax 6 h-extration. The strong correlation with the carrot accumulation suggested that Tenax 6 h-extrated fraction could serve as a good predictor of DDTs bioavailability to carrot roots. Risk assessment demonstrated that when based on the rapid-desorbing concentration and 6 h-extracted concentration, about 60.7% and 17.9% of the soil samples were moderately polluted, however, up to 78.5% were moderately polluted when based on the total soil DDTs concentration. The risk assessment might be more representative when based on Tenax extraction because of the strong correlation with the carrot accumulation. Our results provided implications for site risk assessment and cleanup strategies.

Extracellular polymeric substances enhanced mass transfer of polycyclic aromatic hydrocarbons in the two-liquid-phase system for biodegradation

The objective was to elucidate the role of extracellular polymeric substances (EPS) in biodegradation of polycyclic aromatic hydrocarbons in two-liquid-phase system (TLPs). Therefore, biodegradation of phenanthrene (PHE) was conducted in a typical TLPs—silicone oil–water—with PHE-degrading bacteria capable of producing EPS, Sphingobium sp. PHE3 and Micrococcus sp. PHE9. The results showed that the presence of both strains enhanced mass transfer of PHE from silicone oil to water, and that biodegradation of PHE mainly occurred at the interfaces. The ratios of tightly bound (TB) proteins to TB polysaccharides kept almost constant, whereas the ratios of loosely bound (LB) proteins to LB polysaccharides increased during the biodegradation. Furthermore, polysaccharides led to increased PHE solubility in the bulk water, which resulted in an increased PHE mass transfer. Both LB-EPS and TB-EPS (proteins and polysaccharides) correlated with PHE mass transfer in silicone oil, indicating that both proteins and polysaccharides favored bacterial uptake of PHE at the interfaces. It could be concluded that EPS could facilitate microbial degradation of PHE in the TLPs.

Improved 3D-QSAR analyzes for the predictive toxicology of polybrominated diphenyl ethers with CoMFA/CoMSIA and DFT.

With the popular methods of CoMFA and CoMSIA, three-dimensional quantitative structure-activity relationships (QSARs) were newly developed for the toxicity of polybrominated diphenyl ethers (PBDEs). The choice of optimized geometries by density functional theory (DFT) as molecular template and the RMSD-based molecular alignment strategy might mostly contribute to the QSAR improvement, which was highlighted specifically by the increased q2 of 0.870 for CoMFA, 0.887 for CoMSIA, respectively. QSARs analyzes indicated that the steric effects from ortho- and meta-substitution and the correlated hydrophobicities have the greatest impact on the binding affinities of aryl hydrocarbon receptor (AhR) to PBDEs. Though the effects of electrostatics were comparatively inferior in the AhR binding, the aromatic interaction and possible charge transfer proved to be indispensable for toxicity mediation. Consistent with that proposed previously for other structurally similar compounds, such as dioxins and polychlorinated biphenyls, the predictive toxicology was helpful to understand the congener-specificity of toxicity of PBDEs.

DFT study on the structure-toxicity relationship of dioxin compounds using PLS analysis

Density functional theory (DFT) at B3LYP/6-311G** level was employed to optimise the dioxin compounds, i.e., 25 polychlorinated or brominated dibenzo-p-dioxins (PCDDs or PBDDs) and 34 polychlorinated dibenzofurans (PCDFs) involved in this investigation. Three groups of descriptors mainly related to chemical reactivity, molecular overall charge distribution and thermochemical property were calculated. With partial least squares (PLS) analysis and variable importance in the projection (VIP), the least significant descriptors were removed from the quantitative structure-activity relationship (QSAR), which was focused on exploring the influential factors responsible for the variance of binding affinities of dioxins to aryl hydrocarbon receptor (AhR). With better-improved and predictive QSAR (  = 0.827), further understanding of the nature of toxicity was available. Both dispersion interaction and electrostatic interaction were considered to be important and together capable of accounting for the most part of the total binding affinities, though the former could make more contribution than the latter. Comparatively, the long-range dispersion interaction should be very small.

QSARs for congener-specific toxicity of polyhalogenated dibenzo-p-dioxins with DFT and WHIM theory.

Polyhalogenated dibenzo-p-dioxins (PHDDs) have become the most notorious pollutants in the environment. However, the origin of their congener-specific toxicity is not well understood. For explaining the difference in toxicity between PHDDs as well as their potencies of aryl hydrocarbon hydroxylase (AHH) and 7-ethoxyresorufin O-deethylase (EROD) induction, quantitative structure-activity relationships (QSARs) were constructed through the combined application of DFT (density functional theory) and WHIM (weighted holistic invariant molecular) theory. Results from the QSAR analyses suggest that dispersion interaction along the lateral sites of PHDDs should interpret the vast majority of variance of binding affinities as well as the consequent toxicity. Although electrostatic interaction is comparatively less influential, it should not be negligible. Long-range dispersion interaction is also described in QSARs with minute influence. Quadrupole moment tensor perpendicular to the ring plane, i.e., Q(zz) and its implicated electrostatic interaction plays an important role in the contribution to induction potencies.

Enhanced desorption of humin-bound phenanthrene by attached phenanthrene-degrading bacteria

The objective of the study was to test the hypothesis that the attachment of polycyclic aromatic hydrocarbons (PAHs)-degrading bacteria can promote desorption of PAHs from humin, thereby increasing their bioavailability. Biodegradation of humin-bound phenanthrene (PHE) - a model compound for PAHs - was investigated using two PHE-degrading bacteria, Sphingobium sp. PHE3 and Micrococcus sp. PHE9, respectively. Sorption data of PHE to humin fitted well into the modified Freundlich equation. Further, a new sorption band appeared at 1262cm(-1), demonstrating intermolecular interactions between PHE and humin. Interestingly, approximately 65.3% of humin-bound PHE was degraded by both strains, although only about 17.8% of PHE could be desorbed from humin by Tenax extraction. Furthermore, both strains grew well in mineral medium and also attached to humin surfaces for substrate uptake. It is proposed that the attached bacteria could possibly consume PHE on the humin via interactions between bacterial surfaces and humin, thereby overcoming the low PHE bioavailability and resulting in enhanced degradation.