Zeng-Hui Diao

Simultaneous removal of Cr(VI) and phenol by persulfate activated with bentonite-supported nanoscale zero-valent iron: Reactivity and mechanism

The applicability of bentonite-supported nanoscale zero-valent iron (B-nZVI) as a catalyst to activate persulfate (PS) for the simultaneous removal of Cr(VI) and phenol was systematically investigated in this study. Experimental results demonstrated that phenol degradation was significantly enhanced under acidic condition and with oxygen supply, whereas the Cr(VI) reduction was not obviously declined. The removal efficiencies of Cr(VI) and phenol in B-nZVI/PS combined system were 99.8 and 72.3%, respectively. Cr(VI) reduction and phenol oxidation was simultaneously achieved in B-nZVI/PS combined system, which provided a promising environmental treatment for industrial wastewater containing metal ions and organic compounds. An acidic condition was more favorable to the decomposition of persulfate for the production of sulfate radicals. Radical scavenging tests revealed that the predominant reactive oxygen species for phenol degradation was SO4(-), neither HO nor O2(-). A reaction mechanism, which involves the Cr(VI) removal mainly by the reduction of nZVI and the degradation of phenol mainly by the SO4(-) from the decomposition of persulfate, was proposed. These findings revealed that B-nZVI/PS combined system has a potential in the environmental remediation polluted jointly by organic compounds and/or heavy metals.

Brominated flame retardants in mangrove sediments of the Pearl River Estuary, South China: Spatial distribution, temporal trend and mass inventory

Sediments were collected from three mangrove wetlands in the Pearl River Estuary (PRE) of South China to investigate spatial and temporal distributions of polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE). Concentrations of ΣPBDEs, DBDPE and BTBPE in mangrove sediments of the PRE ranged from 1.25-206, 0.364-34.9, and not detected-0.794 ng g(-1) dry weight, respectively. The highest concentrations of ΣPBDEs, DBDPE and BTBPE were found at the mangrove wetland from Shenzhen, followed by Zhuhai and Guangzhou, showing the dependence on the proximity to urban areas. PBDEs were the predominant brominated flame retardants (BFRs) in mangrove sediments. The concentrations of ΣPBDEs, DBDPE and BTBPE in sediment cores showed an increasing trend from the bottom to top layers, reflecting the increasing usage of these BFRs. The inventories of ΣPBDEs, DBDPE and BTBPE in mangrove sediments were 1962, 245, and 4.10 ng cm(-2), respectively. This is the first study to report the occurrence of DBDPE and BTBPE in mangrove ecosystems.

Enhanced catalytic degradation of ciprofloxacin with FeS2/SiO2 microspheres as heterogeneous Fenton catalyst: Kinetics, reaction pathways and mechanism

In this study, the application of FeS2/SiO2 microspheres as a catalyst to activate H2O2 for the degradation of ciprofloxacin (CIP) was systematically investigated. Results demonstrated that the presence of SiO2 microspheres on the surface of FeS2 could effectively make the reaction of aqueous Fe2+ and H2O2 smoothly continuous by controlling the release of aqueous Fe2+ from FeS2. Nearly 100% of CIP was degraded after 60min under the optimum conditions. A superior performance on the CIP degradation and high reusability of the catalyst was obtained in FeS2/SiO2 microspheres activated H2O2 system. A low concentration of ethylene diamine tetraacetie acid (EDTA) did positively affect the degradation rate of CIP. A synergetic effect between adsorption and oxidation processes contributed to the significant enhancement of CIP degradation. Seven oxidation intermediates were identified during the CIP degradation process, and the direct HO oxidation proved to be a main CIP degradation pathway. For degradation pathway of CIP, oxidation of piperazine ring would be its first step, followed by cleavage of the heterocyclic ring. Subsequently, the substitution, hydroxylation and decarboxylation processes occurred. This is the first report on the feasibility of FeS2/SiO2 microspheres activated H2O2 system for the enhanced degradation of CIP.

Adsorption of phosphorus by calcium-flour biochar: Isotherm, kinetic and transformation studies

Discharging phosphorus (P)-contaminated water directly into the aquatic environment leads to resource loss and eutrophication. Thus, removing P from waste streams is imperative. In this study, calcium-decorated biochar (Ca-BC) in different mass ratios of Ca to BC was designed to effectively adsorb P from solution. Ca-BC was characterized through X-ray diffraction (XRD) analysis, followed by isotherm and kinetic adsorption experiments. The decorated Ca on the BC surface was found to have preferred P adsorption ability. A design of calcium hydroxide (Ca(OH)2) to flour in a mass ratio of 2:1 was found to have a maximum adsorption capacity of 314.22 mg g-1 for P. The Langmuir and pseudo-second-order models fit the sorption process adequately. XRD analysis indicated that the preferable adsorption ability to P was due to the reaction of Ca(OH)2 and PO43-, forming the hydroxylapatite (Ca5(PO4)3(OH)) crystal. The P in solution was transformed to the crystal. Thus, Ca-BC is an environmental friendly and low-cost sorbent for P removal.

Tissue distribution, bioaccumulation characteristics and health risk of antibiotics in cultured fish from a typical aquaculture area

The negative impacts of residual antibiotics in the environment on ecosystem and human health are big concerns. However, little information is available on the antibiotic bioaccumulation in aquaculture farms. In this study, the bioaccumulative potentials of 21 antibiotics in the plasma, bile, liver and muscle of cultured fish from a typical aquaculture area were systematically investigated. RESULTS indicated that antibiotic distribution in the cultured fish was mainly influenced by species and specific substances. The mean values of log bioaccumulation factors (Log BAFs) for the detected antibiotics were in the range of 0.43-3.70, 0.36-4.75, -0.31-4.48, and 0.23-4.33 in the fish plasma, bile, liver and muscle tissues, respectively. For grass carp, both ciprofloxacin and enrofloxacin showed high transportability from the plasma to the muscle and liver. The correlations of various antibiotic concentrations between the plasma and the other three tissues indicated that the concentrations of ciprofloxacin and enrofloxacin in the fish tissues could be predicted by their concentrations in the plasma. Based on the calculated hazard quotients, human health risk evaluation of antibiotic exposure by fish consumption indicated that the consumption of these cultured fish posed low risks to human health.

Simultaneous removal of Cu2+ and bisphenol A by a novel biochar-supported zero valent iron from aqueous solution: Synthesis, reactivity and mechanism

In this study, a novel biochar-supported zero valent iron (BC-nZVI) was synthesized through a green method. A high performance on the simultaneous removal of Cu2+ and bisphenol A (BPA) by a combination of BC-nZVI with persulfate (BC-nZVI/PS) system was successfully achieved. The simultaneous efficiencies of Cu2+ and BPA could reach 96 and 98% within 60 min, respectively. Both HO• and SO4•- were two major reactive species in BC-nZVI/PS system, and SO4•- was primary radical responsible for the degradation of BPA. Four kinds of Cu species, such as Cu(OH)2, CuO, Cu2O and Cu0 were generated via the adsorption and reduction of the BC-nZVI, whereas six kinds of products of BPA including p-isopropenyl phenol and 4-isopropylphenol were generated via the combined oxidation of SO4•- and HO•. The possible reaction mechanism for the simultaneous removal of Cu2+ and BPA by BC-nZVI/PS system contained a synergistic effect between the reduction of Cu2+ and the oxidation of BPA. This is the first report on the feasibility of the remediation of coexistence of heavy metal and organic compound in aquatic environment using the BC-nZVI/PS system.

Synthesis of FC-supported Fe through a carbothermal process for immobilizing uranium

The abundant generation of uranium (U), a radioactive nuclide, engenders a severe hazard to the environment. Iron based materials were used to immobilize U from water, however, the immobilization is limited by the agglomeration of nanoparticle Fe. In this study, a novel carbothermal process was proposed to synthesize flour carbon (FC) supported nano-flake Fe (Fe-FC). Scanning electron microscopy (SEM) and nitrogen isotherm adsorption-desorption analysis were conducted to characterize Fe-FC. The immobilization characteristics were investigated through batch sorption experiments. Results indicated that nano-flake was appropriately dispersed on the surface. The sorption capacity reached 19.12 mg/g when the initial concentration of U and the dosage of Fe-FC were 20 mg/L and 1 g/L, respectively. Langmuir isotherm sorption and pseudo-second-order models were fitted well to sorption experimental data. The sorption mechanism is ascribed to surface chemisorptions between U(VI) and Fe-FC. Subsequently, X-ray diffraction (XRD) analysis validated that formation of Fe2UO3 contributed to the favorable immobilization of U and that Fe2UO3 was the fate of U.

In situ arsenic speciation and the release kinetics in coastal sediments: A case study in Daya Bay, South China Sea

In-situ study on arsenic speciation and the release kinetics in marine sediments was scarce. In this study, the distributions of labile As and their speciation in coastal sediments of Daya Bay were obtained by separate diffusive gradients in thin films (DGT) probes. Results showed that the DGT-labile As(V) was the main speciation in surface sediments (from -20 to 0 mm) with a concentration range of 0.07-3.05 μg·L-1, while the labile As(III) was the main speciation in deep layers of sediments (from -100 to -20 mm). In coastal areas, mariculture farms was the most dominated contributor to As(V) contamination in surface sediments. Both the apparent diffusion flux estimation and the DGT induced flux in sediments (DIFS) simulation indicated that As(V) contamination in surface sediments of mariculture, harbor and petrochemical areas suffered the potential risk of As(V) release into the overlying water from sediments. DIFS modeling also found that the sediments of mariculture farms were the main sediment As pools. Linear regression analysis indicated that the mobility of As mainly attributed to the As(V) in sediments.

Solvent-free hydrothermal synthesis of gamma-aluminum oxide nanoparticles with selective adsorption of Congo red

Aluminum hydroxide and oxide have been widely used for decontamination due to their environmentally friendly nature and cost effectiveness. Aluminum (hydro) oxides are the main phases of aluminum-derived environment materials. Herein, the solvent-free hydrothermal synthesis of gamma-aluminum oxide (γ-Al2O3) nanoparticles and phase transformation of AlOOH into γ-Al2O3 are reported. Hydrothermal treatment of NH3·H2O-induced aluminum precipitate resulted in the formation of AlOOH, which was an intermediate product of γ-Al2O3. AlOOH was transformed into highly crystalline 20-nm γ-Al2O3 particles through calcination at 500 °C due to dehydration. The transformation was confirmed through X-ray diffraction (XRD) and thermogravimetric (TG) analyses. The resulting γ-Al2O3 had superior adsorption ability for the anionic Congo red (CR) dye than for the cationic methylene blue (MB) and malachite green (MG) dyes. The selective adsorption ability of CR instead of MB was attributed to the electrostatic attraction and hydrogen bonds between the amino group and azo double bond of CR, and between the amino group and hydroxyl group in γ-Al2O3. Thus, this study investigated crystalline phase transformation into γ-Al2O3 and selective adsorption capacity of CR, which provides important information regarding the synthesis of crystalline γ-Al2O3 adsorbent, with selective adsorption ability for decontamination applications.

Sorption and desorption of phenanthrene on biodegradable poly(butylene adipate co-terephtalate) microplastics

Biodegradable plastics, as alternatives to conventional plastics, are increasingly used, but their interactions with organic pollutants are still unknown. In this study, the sorption and desorption behaviors on a type of biodegradable plastic-poly(butylene adipate co-terephtalate) (PBAT) were investigated, and at the same time two types of conventional plastics-polyethylene (PEc and PEv) and polystyrene (PS) were used for comparison. Phenanthrene (PHEN) was chosen as one of representative organic pollutants. Results indicated that the sorption and desorption capacities of PBAT were not only higher than those of the other types of microplastics, but also higher than those of carbonaceous geosorbents. The surface area normalized results illustrated that sorption and desorption of the microplastics were positively correlated with their abundance of rubbery subfraction. The sorption kinetic results showed that the sorption rates of PBAT and PEc were higher than PEv and PS. The effects of water chemistry factors including salinity, dissolved organic matter and Cu2+ ion on the sorption process displayed the same trend, but the degrees of influence on the four microplastics differed. The degrees of influence were mainly dependent on the abundance of rubbery subfraction for microplastics. These findings indicate that the biodegradable poly(butylene adipate co-terephtalate) microplastics are actually stronger vectors than the conventional microplastics, and crystallization characteristics of the microplastics have great influences on the vector effect.