Arsenic Removal from Dilute Solutions by High Surface Area Mesoporous Iron Oxyhydroxide

Mesostructured iron oxyhydroxide (FeO _x ) and iron oxyhydroxide–phosphate (FeO _x P) composites were organized using dodecylsulfate surfactant as a template. X-ray diffraction studies depicted a lamellar structure of the product. Ion exchange and solvent extraction methods were employed for the removal of the surfactant. Carboxylate ions exchanged lamellar type mesostructured material reorganized to a wormhole-like mesoporous material when heated under N₂ atmosphere. Surfactant was completely removed by carboxylate ions as observed by the Fourier transform infrared spectra. High surface area acetate-exchanged FeO _x (230 m² g^?1) was obtained after the surfactant removal from the composite (2.8 m² g^?1). Surface area of acetate-exchanged FeO _x P was the highest (240 m²g^?1) after the removal of the surfactant. Local structure of iron species of FeO _x was investigated by X-ray absorption fine structure spectroscopy. Further, Fe···Fe bond appeared at 3.21–3.25 Å with coordination number 2–3, showing a high degree of un-saturation of Fe···Fe bonds. As compared with bulk iron oxyhydroxide and iron-intercalated montmorillonite, the mesoporous iron materials were highly effective for arsenic removal from low concentrations of aqueous solutions. Furthermore, mesoporous iron materials were stable in aqueous phase.     

Synergistic increase in cell lethality by dieldrin and H2O2 in rat thymocytes: Effect of dieldrin on the cells exposed to oxidative stress

Dieldrin, one of persistent pesticides, is highly resistant to biotic and abiotic degradation. It is accumulated in organisms. Recent studies suggest that dieldrin exerts a potent cytotoxic action on cells exposed to oxidative stress. In this study, the effect of dieldrin on rat thymocytes exposed to hydrogen peroxide (H₂O₂)-induced oxidative stress was examined. Dieldrin at 5 μM and H₂O₂ at 300 μM slightly increased cell lethality from a control value of 5.4 ± 0.5% (mean ± standard deviation of four experiments) to 7.8 ± 1.3% and 9.0 ± 0.3%, respectively. Simultaneous application of dieldrin and H₂O₂ significantly increased cell lethality to 46.2 ± 1.8%. The synergistic increase in cell lethality was dependent on dieldrin concentration (0.3–5 μM) but not on H₂O₂ concentration (30–300 μM). Dieldrin accelerated H₂O₂-induced cell death, which was estimated with the help of annexin V-FITC and propidium iodide. Presence of either dieldrin or H₂O₂ decreased the cellular content of nonprotein thiol and increased intracellular Zn²⁺ concentration. The combination of dieldrin and H₂O₂ further pronounced these effects. TPEN, a chelator of intracellular Zn²⁺, significantly attenuated the synergistic increase in cell lethality induced by dieldrin and H₂O₂. It is, therefore, suggested that dieldrin augments the cytotoxicity of H₂O₂ in a Zn²⁺-dependent manner.     

温度分化对APBR反应器性能及产甲烷菌群落的影响

为了研究温度分化对固定床厌氧反应器(anaerobic packed bed reactor,APBR)牛粪发酵处理效果及产甲烷菌群落的影响,反应器发酵温度从室温(22℃±1℃)阶梯式分化到低温(15℃±1℃)、中温(37℃±1℃)和高温(55℃±1℃).温度变化的过程中,温度越高COD(chemical oxygen demand)去除率和日总产气量越高,分化后COD去除率分别为25%、45%、60%,相应的日产气量为2.3、4.0、8.5 L·d-1,但是甲烷含量基本保持不变(~60%);温度突然变化造成挥发性脂肪酸含量骤然增加,并处于波动状态.16S r RNA基因克隆文库法分析表明,室温时包含广古菌门中的常见重要产甲烷菌MBT(甲烷杆菌目)、Mst(甲烷鬃菌科)、Msc(甲烷八叠球菌科)和MMB(甲烷微菌目),以及嗜热菌,也有少部分泉古生菌门,发酵温度分化后,产甲烷菌多样性减少,中温条件下产甲烷菌种类相对较少.定量PCR表明Mst、MMB和Msc总基因浓度都有所减少,并且温度越高减少越多,各菌数量相对比例变化较大,但Mst仍为优势产甲烷菌.     

Accumulation and Chemical Fractionation of Heavy Metals in Andisols after a Different, 6-year Fertilization Management (8 pp)

Goal, Scope and Background Andisols are widespread in Japan and have some special properties such as high anion exchange capacity, low bulk density, and high organic matter content, which might influence the accumulation or chemical fractionation of heavy metals. However, few such data exist in Japanese andisols. The primary objective of this study was to investigate the distribution and chemical fractions of Cu, Zn, Ni, and Cr in the soil profiles and subsequently to assess their potential environmental hazard. Materials and Methods Soil samples were taken from a field experiment conducted on Japanese andisols, which had received either swine compost or chemical fertilizers for 6 years. Concentrations of Cu, Zn, Ni, and Cr were determined for all of the obtained extract solutions by ICP-AES. Results and Discussion Considerably higher total concentrations of Cu and Zn were observed in the top 20 cm layer of the compost-amended soil, relative to the unfertilized soil, while chemical fertilizers had little effect. Application of the swine compost increased the concentrations of Cu and Zn, but not Ni and Cr, in all fractions in the top 20 cm layer. The greatest increase in the organically bound fraction (OM) Cu and dilute acid-exchangeable fraction (DAEXCH) Zn was observed. This suggests that Cu and Zn are potentially bioavailable and mobile in the andisol profiles after 6-year consecutive applications of the swine compost. On the other hand, distribution of Cu, Zn, Ni and Cr among various soil fractions was generally unaffected by chemical fertilizers. Conclusions We observed that 6-year consecutive applications of the swine compost led to an increase in total metals of Cu and Zn, as well as their all-chemical fractions, in the top 20 cm soil layers. Potential hazard of heavy metals, especially of Cu and Zn, as a result of the use of swine compost on andisols, must be taken into account. Recommendations and Outlook The long-term effect of the accumulation of heavy metals, particularly Cu and Zn, in various plant tissues and soils, as well as their potential risk to surface water via runoff and groundwater via leaching, needs to be carefully considered. Further investigations in the long-term experiments are therefore necessary. - Abbreviations. EXCH, exchangeable fraction of metals; DAEXCH, dilute acid-exchangeable fraction of metals; FeMnOX, iron and manganese-oxide-bound fraction; OM, organically-bound fraction; RESD, residual fraction. COMPOST, SRNF, RANF, and CONTROL stand for compost (from swine wastes), slow-release nitrogen fertilizer (coated urea), readily available nitrogen fertilizer (including NH4-N, P, and K fertilizers), and no fertilizer application, respectively.     

Metabolism of 3-hydroxybenzo (a) pyrene in rat,isolated hepatocytes and kidney

After intravenous injection of 3-hydroxybenzo (a) pyrene into rat, benzo (a) pyrene-diols were detected in urine, and $\text{in vitro}$ experiment using isolated hepatocytes and sliced kidney also indicated the metabolism of 3-hydroxybenzo (a) pyrene to diol derivatives. THese results suggested the presence of unknown metabolic pathway of benzo (a) pyrene-phenols such as 3-hydroxybenzo (a) pyrene to diol derivatives both $\text{in vivo}$ and $\text{in vitro}$.     

Variation in estrogenic activity among fractions of a commercial nonylphenol by high performance liquid chromatography

Estrogenic activity by recombinant yeast screen assay of the commercial NP was considerably higher when compared with that of n-nonylphenol (n-NP). Fractionation of the commercial NP by high performance liquid chromatography (HPLC) afforded seven isomers: 4-(1,3-dimethyl-1-propyl-butyl)-phenol, 4-(1,1,3-trimethyl-hexyl)-phenol, 4-(1,1-dimethyl-3-ethyl-pentyl)-phenol, 4-(1,1,4-trimethyl-hexyl)-phenol, 4-(1-methyl-1-propyl-pentyl)-phenol, 4-(1,1,2-trimethyl-hexyl)-phenol and 4-(1-ethyl-1-methyl-hexyl)-phenol. The structures of these isomers were determined by GC-MS and nuclear magnetic resonance spectroscopy (NMR). All of these isomers possessed tertiary alpha-carbon in their chemical structures. Another tertiary NP, 4-(1,1-dimethyl-heptyl)-phenol was synthesized in the present study and this synthetic NP also exhibited the estrogenic activity. One fractionated compound was identified as one of decylphenol, 4-(1-ethyl-1,4,4-trimethyl-pentyl)-phenol. The isomer, 4-(1,1,4-trimethyl-hexyl)-phenol exhibited the highest estrogenic activity corresponding to 1/10000 that of 17beta-estradiol (E2). The activity of n-NP was the least. This suggests that it may be possible to develop a technical NP mixture with relatively low estrogenic activity.     

Photodegradation mechanism for bisphenol A at the TiO2/H2O interfaces

Bisphenol A (BPA) can be decomposed photocatalytically under UV-illumination in aqueous TiO2 dispersion. The two methyl groups in BPA were initially attacked with .OH and/or .OOH radicals having strong oxidizing power, followed by the cleavage of the two phenyl moieties. Finally, the photomineralization to CO2 gas occurred via oxidative processes involving carboxylic acids and aldehydes. The decomposition of structurally similar substances of 4,4'-ethylidenebisphenol (EBP) and 4,4'-methylenebisphenol (MBP) was compared. The decomposition of BPA gave more kinds of intermediates such as 4-isopropylphenol, 4-ethylphenol, etc. On the other hand, that of EBP gave mainly 4-isopropylphenol and that of MBP gave a predominant product of 4-hydroxybenzaldehyde. These photooxidative pathways were proposed on the base of the evidence of oxidative intermediate formation.     

Experiments and numerical simulation on methane flame quenching by water mist

The study of extinguishment using water mist has been motivated due to the phase-out of the use of halens and the search for alternative means that preserve all of the benefits of a clean total flooding agent without adverse environmental impact. With the numerical simulation, we analyzed a gas–liquid two-phase problem including water (liquid), air and methane (gas) using Eulerian equations for the liquid phase and the full Navier–Stokes equations for the gas phase. Gaseous mass, momentum and energy equations are integrated simultaneously by a Harten–Yee explicit non-MUSCL modified-flux type TVD scheme for the convective terms and a central difference scheme for the viscous terms. Liquid phase conservation equations are solved with an application of a flux-vector-splitting scheme. In the experiments in an open room (500×500×500 mm) we observed an interaction of the diffusion flame with the water mists. The results show remarkable flame quenching and a good agreement between the numerical and experimental results.