Lingyan Zhu

Degradation and mineralization of bisphenol A by mesoporous Bi2WO6 under simulated solar light irradiation.

Bismuth tungstate (Bi2WO6) catalysts of different morphology were synthesized with a hydrothermal method by controlling the pH of the reaction solution. The properties of the synthesized catalysts were characterized and all catalysts presented high photoabsorption capacity in the range of UV light to visible light around 450 nm. The surface area of the catalysts decreased but the crystallinity increased with the pH of the hydrothermal reaction solution in the range of 4-11. It was found that the crystallinity of the catalysts played an important role on their degradation capacity to Bisphenol A (BPA). Bi2WO6 catalyst prepared at pH 11 displayed a mesoporous structure and it showed the highest photocatalytic activity to degrade BPA under simulated solar light irradiation. Nearly 100% of BPA with original concentration at 20 ppm was removed after 30 min irradiation in a solution with pH 10 and Bi2WO6 amount of 1.0 g L(-1). Furthermore, 86.6 and 99.1% of the total organic carbon was eliminated after 60 and 120 min irradiation, respectively. Only one intermediate at m/z 133 was observed by LC/MS and a simple pathway of BPA degradation by Bi2WO6 was proposed.

Novel Mesoporous Graphite Carbon Nitride/BiOI Heterojunction for Enhancing Photocatalytic Performance Under Visible-Light Irradiation

A novel organic-inorganic three-dimensional (3D) mesoporous graphite carbon nitride/BiOI (MCN/BiOI) heterojunction photocatalyst with excellent visible-light-driven photocatalytic performance was synthesized by a facile solvothermal method and used for degradation of bisphenol A (BPA) in water. After hybridization with MCN, a heterojunction was formed and the photogenerated carriers could be effectively separated by the internal electric field built at the heterojunction interface. The photocatalytic and photoelectrochemical performance of BiOI were improved and much higher than pure BiOI and MCN. The best photocatalytic performance was achieved with MCN proportion of 10%, and the kobs was approximately 1.6 times of pure BiOI and 3.4 times of MCN under simulated solar light irradiation, respectively. The photocurrent intensity generated by 10%-MCN/BiOI electrode was about 1.5 and 2.0 times of those induced by BiOI and MCN under visible-light irradiation, respectively. The superoxide radical species were predominant in the reaction system.

Occurrence and partition of perfluorinated compounds in water and sediment from Liao River and Taihu Lake, China

The concentrations of four perfluorinated sulfonate acids (PFSAs) and 10 perfluorinated carboxylate acids (PFCAs) were measured in water and sediment samples from Liao River and Taihu Lake, China. In the water samples from Taihu Lake, PFOA and PFOS were the most detected perfluorinated compounds (PFCs); in Liao River, PFHxS was the predominant PFC followed by PFOA, while PFOS was only detected in two of the samples. This suggests that different PFC products are used in the two regions. PFOS and PFOA in both watersheds are at similar level as in the rivers of Japan, but significantly lower than in Great Lakes. The contributions of PFOS and long chain PFCAs in sediments were much higher than in water samples of both watersheds, indicating preferential partition of these PFCs in sediment. The concentrations of PFOS and PFOA were three orders of magnitude of lower than that of polycyclic aromatic hydrocarbons in the same sediments. The average sediment-water partition coefficients (log K(oc)) of PFHxS, PFOS and PFOA were determined to be 2.16, 2.88 and 2.28 respectively.

Biomonitoring of Perfluoroalkyl Acids in Human Urine and Estimates of Biological Half-Life

Perfluoroalkyl acids (PFAAs) are persistent and bioaccumulative compounds that have been associated with adverse health outcomes. In human blood, PFAAs exist as both linear and branched isomers, yet for most linear homologues, and for all branched isomers, elimination rates are unknown. Paired blood and urine samples (n = 86) were collected from adults in China. They were analyzed by a sensitive isomer-specific method that permitted the detection of many PFAAs in human urine for the first time. For all PFAAs except perfluoroundecanoate (PFUnA), levels in urine correlated positively with levels in blood. Perfluoroalkyl carboxylates (PFCAs) were excreted more efficiently than perfluoroalkane sulfonates (PFSAs) of the same carbon chain-length. In general, shorter PFCAs were excreted more efficiently than longer ones, but for PFSAs, perfluorooctanesulfonate (PFOS, a C8 compound) was excreted more efficiently than perfluorohexanesulfonate (PFHxS, a C6 compound). Among PFOS and perfluorooctanoate (PFOA) isomers, major branched isomers were more efficiently excreted than the corresponding linear isomer. A one-compartment model was used to estimate the biological elimination half-lives of PFAAs. Among all PFAAs, the estimated arithmetic mean elimination half-lives ranged from 0.5 ± 0.1 years (for one branched PFOA isomer, 5m-PFOA) to 90 ± 11 years (for one branched PFOS isomer, 1m-PFOS). Urinary excretion was the major elimination route for short PFCAs (C ≤ 8), but for longer PFCAs, PFOS and PFHxS, other routes of excretion likely contribute to overall elimination. Urinary concentrations are good biomarkers of the internal dose, and this less invasive strategy can therefore be used in future epidemiological and biomonitoring studies. The very long half-lives of long-chain PFCAs, PFHxS, and PFOS isomers in humans stress the importance of global and domestic exposure mitigation strategies.

Immobilization of lead and cadmium from aqueous solution and contaminated sediment using nano-hydroxyapatite

The effectiveness and mechanism of nano-hydroxyapatite particles (nHAp) in immobilizing Pb and Cd from aqueous solutions and contaminated sediment were investigated. The maximum sorption amount (Q(max)) of Pb and Cd in aqueous solution was 1.17 and 0.57 mmol/g. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) surface and depth analysis indicated that dissolution-precipitation is the primary immobilization mechanism for Pb, while surface complexation and intraparticle diffusion account for Cd sequestration. Different amounts of nHAp (0-10% nHAp/dry weight) were added to the contaminated sediment. Sequential extraction showed that nHAp could effectively reduce the exchangeable fraction of Pb and Cd in the sediment and significantly reduce the concentration in porewater. The results in this study showed that nHAp can immobilize Pb and Cd in sediment effectively.

Photolytic reaction mechanism and impacts of coexisting substances on photodegradation of bisphenol A by Bi2WO6 in water

Bi(2)WO(6) displayed great photolytic degradation efficiency to bisphenol A (BPA) under simulated solar light irradiation but its reaction mechanism and the impacts of coexisting substances on the degradation remain unclear. In present study, the reaction mechanism was investigated using DMPO spin-trapping ESR spectra and experiments with scavengers of hydroxyl radicals (*OH) and holes. The results supported that hole oxidation mainly governed the photodegradation process. As a common humic substance in natural water, humic acid accelerated the degradation of BPA when its concentration was 1mg/L, while the photodegradation was impeded with the increase of humic acid concentration in the range of 5-20mg/L. Almost all anions, including NO(3)(-), HCO(3)(-), Cl(-), SO(4)(2-) inhibited the degradation of BPA by Bi(2)WO(6) and their inhibition effects followed the order of SO(4)(2-)>Cl(-)>HCO(3)(-)>NO(3)(-). Cations of Na(+), K(+), Ca(2+) and Mg(2+) displayed slight suppressing effect on BPA degradation mainly due to the impact of Cl(-) coexisting in the solution. However, Cu(2+) hindered the BPA photodegradation heavily. Fe(3+) and H(2)O(2) affected the photodegradation in a complicated way: they suppressed or promoted the photodegradation depending on their concentrations. This could be the result of competition between photolyitc hole generated by Bi(2)WO(6) and OH produced by Fe(3+) or H(2)O(2.).

Enhanced photocatalytic performance of boron doped Bi2WO6 nanosheets under simulated solar light irradiation

Bi₂WO6 doped with different amounts of boron atoms (0.1, 0.5, 1.0, 5.0 and 10% B) were synthesized using hydrothermal method and their photocatalytic activities to degrade rhodamine B (RhB) under simulated solar light was investigated. The successful incorporation of B atoms in Bi₂WO₆ was proved by FT-IR, Raman spectra and XPS. Doping with B could affect the pore structure and volume. 0.5% B/Bi₂WO₆ displayed more mesopores with higher total pore volume than pure Bi₂W₆; while the pores of 10% B/Bi₂WO₆ mainly distributed in microporous range with much less total pore volume. As a result, 0.5% B/Bi₂WO₆ displayed stronger adsorption capacity to RhB, favoring the photodegradation. In addition, the doped B atoms could act as electron traps and facilitate the separation of photogenerated electron-hole pairs due to its electron deficient and oxytropic characteristics. 0.5% B/Bi₂WO₆ displayed the highest photocatalytic activity under simulated solar light with rate constant (kobs) 8.8 times of that using pure Bi₂WO₆. Its photoactivity was affected by solution pH and the optimum was achieved at pH 7. At this condition, around 100% of RhB (10(-5)mol/L) was degraded in 180 min. The photogenerated holes were the main active species responsible for the photodegradation of RhB by B/Bi₂WO₆.

Simultaneous adsorption and degradation of γ-HCH by nZVI/Cu bimetallic nanoparticles with activated carbon support.

Cu amended zero valent iron bimetallic nanoparticles were synthesized by doping Cu on the surface of iron. They were incorporated with granular activated carbon (AC) to prepare supported particles (AC-Fe(0)-Cu), which were used to remove γ-HCH. Cu on the surface of iron enhanced the dechlorination activity of Fe(0). The dechlorination rate constant (k(obs)) increased with the Cu loading on the surface of iron and the maximum was achieved with 6.073% Cu. AC as a support was effective for increasing the dispersion of the nanoparticles and avoiding the agglomeration of the metallic nanoparticles. The simultaneous adsorption of γ-HCH on AC accelerated the degradation rate of γ-HCH by the bimetals. After reaction for 165 min, around 99% of γ-HCH was removed by the solids of AC-Fe(0)-Cu. In addition, AC could adsorb the degradation products. The degradation of γ-HCH was mainly through dehydrochlorination and dichloroelmination based on the intermediate products detected by GC/MS.

Biochars derived from various crop straws: Characterization and Cd(II) removal potential

Five types of biochars prepared from four crop straws and one wood shaving at 600 °C were characterized, and their sorption to Cd(II) were determined to investigate the differences in capacity to function as sorbents to heavy metals. Surface areas and pore volumes of the biochars were inversely correlated to the lignin content of raw biomass. The biochars derived from crop straws displayed more developed pore structure than wood char due to the higher lignin content of wood. Sorption capacity of the biochars to Cd(II) followed the order of corn straw>cotton straw>wheat straw>rice straw>poplar shaving, which was not strictly consistent with the surface area of the chars. The surface characteristics of chars before and after Cd(II) sorption were investigated with scanning electron microscopy equipped with an energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy, which suggested that the higher sorption of Cd(II) on corn straw chars was mainly attributed to cation exchange, surface precipitation of carbonate, and surface complexation with oxygen-containing groups. This study indicated that crop straw biochars exhibit distinct sorption capacities to heavy metals due to various surface characteristics, and thus the sorption efficiency should be carefully evaluated specific to target contaminant.

Biosorption of divalent Pb, Cd and Zn on aragonite and calcite mollusk shells

The potential of using mollusk shell powder in aragonite (razor clam shells, RCS) and calcite phase (oyster shells, OS) to remove Pb(2+), Cd(2+) and Zn(2+) from contaminated water was investigated. Both biogenic sorbents displayed very high sorption capacities for the three metals except for Cd on OS. XRD, SEM and XPS results demonstrated that surface precipitation leading to crystal growth took place during sorption. Calcite OS displayed a remarkably higher sorption capacity to Pb than aragonite RCS, while the opposite was observed for Cd. However, both sorbents displayed similar sorption capacities to Zn. These could be due to the different extent of matching in crystal lattice between the metal bearing precipitate and the substrates. The initial pH of the solution, sorbents dosage and grain size affected the removal efficiency of the heavy meals significantly, while the organic matter in mollusk shells affected the removal efficiency to a lesser extent.