Evaluation of pressurized liquid extraction for the analysis of four pesticides in unpolished rice

The aim of to evaluate efficiency of this study was extraction pressurized liquid extraction (PLE) for the analysis of four pesticides, fthalide, etofenprox, fenitrothion, and isoprothiolane, in unpolished rice by comparing with homogenization as a reference technique. The concentrations of four selected pesticides obtained by PLE with acetonitrile at 130 degrees C for 10 min x 2 cycles were comparable to those by homogenization with water-soaking. The repeatability of the analysis, represented as relative standard deviations (RSDs), were 1.4-3.6% (n = 3) for PLE at 130 degrees C and 1.2-3.8% (n = 3) for homogenization with water-soaking. Recovery yields of surrogates were 75-88% and 87-109% for PLE at 130 degrees C and homogenization with water-soaking, respectively, and these were satisfactory according to the method of positive list. This study suggested that PLE can be applied for the analysis of selected four pesticides in unpolished rice as well as homogenization with water-soaking.     

Decomposition of organochlorine compounds in flue gas from municipal solid waste incinerators using natural and activated acid clays

High-temperature particle control (HTPC) using a ceramic filter is a dust collection method without inefficient cooling and reheating of flue gas treatment; thus, its use is expected to improve the energy recovery efficiency of municipal solid waste incinerators (MSWIs). However, there are concerns regarding de novo synthesis and a decrease in the adsorptive removal efficiency of dioxins (DXNs) at approximately 300°C. In this study, the effect of natural and activated acid clays on the decomposition of monochlorobenzene (MCB), one of the organochlorine compounds in MSW flue gas, was investigated. From the results of MCB removal tests at 30–300°C, the clays were classified as adsorption, decomposition, and low removal types. More than half of the clays (four kinds of natural acid clays and two kinds of activated acid clays) were of the decomposition type. In addition, the presence of Cl atoms detached from MCB was confirmed by washing the clay used in the MCB removal test at 300°C. Activated acid clay was expected to have high dechlorination performance because of its proton-rich-composition, but only two clays were classed as decomposition type. Conversely, all the natural acid clays used in this work were of the decomposition type, which contained relatively higher di- and trivalent metal oxides such as Al₂O₃, Fe₂O₃, MgO, and CaO. These metal oxides might contribute to the catalytic dechlorination of MCB at 300°C. Therefore, natural and activated acid clays can be used as alternatives for activated carbon at 300°C to remove organochloride compounds such as DXNs. Their utilization is expected to mitigate the latent risks related to the adoption of HTPC, and also to contribute to the improvement of energy recovery efficiency of MSWI.

ImplicationsThe effect of natural and activated acid clays on MCB decomposition was investigated to evaluate their suitability as materials for the removal of organochlorine compounds, such as DXNs, from MSWI flue gas at approximately 300°C. More than half of the clays used in this study showed the decomposition characteristics of MCB. The presence of Cl atoms in the clay used in the MCB removal test at 300°C proved the occurrence of MCB decomposition. The results of this study suggest a novel flue gas treatment method to establish high-energy efficient MSWI systems.     

Partitioning between soluble and insoluble fractions of major and trace elements in size-classified airborne particulate matter collected in Tokyo

Airborne particulate matter (APM) is a major air pollutant, and the effect on human health of fine APM (PM2.5) deposited deep inside the lungs has recently become a serious concern. Moreover, soluble constituents may leach from APM, and intensify some health disorders. To identify the soluble chemical constituents of APM, size-classified APM was sampled in central Tokyo, and the elemental compositions of the water-soluble, acid-soluble and insoluble fractions were investigated. The extraction procedure was validated by calculating the mass balance of soluble and insoluble fractions of a standard APM reference material (NIST SRM 1648). Among the major elements, Fe and Ti in APM of all size classes and K in coarse APM were distributed primarily in the insoluble fraction and were inferred to be present as oxides or silicates, whereas Na and Mg in all size classes and K in fine APM were primarily in the water-soluble fraction and were inferred to be have originated mainly from sea salt. Among the trace elements, Zn and Cd in the fine APM (d < 2 microm) had large enrichment factors, indicating an anthropogenic origin, and were distributed primarily in the water-soluble fraction. When fine anthropogenic APM enters into the lungs, leached toxic elements, such as Cd, may adversely affect health. The higher the bonding energy of the monoxide molecule of the element was, the higher its distribution ratio was in the water-soluble fraction. Therefore, many metallic elements in APM were inferred to be present as oxygen-bonded compounds.     

Indirect identification of an unstable intermediate in γ-HCH degradation by Pseudomonas paucimobilis UT26

While a postulated intermediate, 1,3,4,5-tetrachlorocyclohexa-1,4-diene(1,4-TCDN), is one of the key-compounds in γ-hexachlorocyclohexane(γ-HCH) degradation by Pseudomonas paucimobilis UT26(UT26), it has neither been isolated nor identified yet. Thus, an indirect identification was attempted to demonstrate its existence by a chemical oxidation of the microbial degradation products in situ.

1,2,4,5-Tetrachlorobenzene(1,2,4,5-TeCB) was newly produced by the chemical oxidation with hydrogen peroxide under iron(II) of W medium containing degradation products in situ of γ-1,3,4,5,6-pentachlorocyclohexene(γ-PCCH) by Escherichia coli MV1184(E. coli) which possesses the dehydrochlorinating activity of UT26. The chemical oxidation required the preceding enzymatic reactions to γ-PCCH by E. coli for the production of 1,2,4,5-TeCB. In facts, 1,2,4,5-TeCB was not produced from γ-PCCH by either of the chemical or enzymatic reaction alone.

Considering these results and the fact that hydrogen peroxide is known to dehydrogenate chemical compounds, it was concluded that 1,2,4,5-TeCB was produced directly from the unstable intermediate, 1,4-TCDN, on yielded from γ-PCCH by an enzymatic dehydrochlorination.     

Preparation of Natural Rubber/Condensed Tannin Semi-interpenetrating Polymer Network Composites by Hematin-Catalyzed Cross-Linking

In this study, the preparation of semi-interpenetrating polymer network (semi-IPN) composites composed of natural rubber and condensed tannin was performed by means of the enzyme-mimetic cross-linking of condensed tannin catalyzed by hematin. Prior to the preparation of the composites, the hematin-catalyzed cross-linking behavior of condensed tannin was evaluated by the TGA measurement. The TGA results indicated that condensed tannin was sufficiently cross-linked by the hematin-catalyzed reaction in the presence of appropriate amounts of 30% (w/v) H₂O₂ aq. to give the relatively thermostable materials. For the preparation of the composites, a solution of condensed tannin and hematin, and subsequently 30% (w/v) H₂O₂ aq. were added to natural rubber latex and the mixture was stirred at room temperature for 10 min to perform the cross-linking of condensed tannin, followed by drying of the reaction mixture at 50 °C for 5 h, which was subsequently put into a heat device and hot-pressed at 100 °C and 20 MPa for 20 min to give the semi-IPN composite. The tensile stress?Cstrain measurement of the composites was conducted to evaluate the mechanical properties, which were changeable depending on the weight ratios of natural rubber to condensed tannin and the amounts of 30% (w/v) H₂O₂ aq. Moreover, the miscibility of the cross-linked tannin with natural rubber in the composite was evaluated by the SEM measurement.     

Oxidation of antimony (III) in soil by manganese (IV) oxide using X-ray absorption fine structure

The oxidation of antimony (III) in soils was studied using X-ray absorption fine structure (XAFS) spectra. An andosol soil sample and artificial soil samples (SiO₂ blended with iron (III) hydroxide and manganese (IV) oxide) were used herein. After adding antimony (III) oxide to all soil samples, the oxidation process was observed by recording the XAFS spectra of Sb K-edge, Fe K-edge, and Mn K-edge. The results indicated that manganese (IV) oxide played an important role in the oxidation of Sb(III); however iron (III) hydroxide was not directly related to the reaction. During a 2-hr continuous Sb K-edge X-ray absorption near edge structure (XANES) measurement with an interval of 1 min of one of the artificial soil samples (SiO₂ + MnO₂ + Sb₂O₃), a pseudo-first-order reaction was determined with an average estimated rate of 0.52 ± 0.04 hr^? 1. Compared to the lower oxidation rate of andosol, it is suggested that because of the low concentration of Mn(IV) in natural soils, the oxidation process of Sb(III) might be relatively slow and require more time to convert Sb(III) to Sb(V).     

Effects of Nitrogen Supply on the Sensitivity to O3 of Growth and Photosynthesis of Japanese Beech (Fagus crenata) Seedlings

To obtain basic information for evaluating critical levels of O₃ under different nitrogen loads for protecting Japanese beech forests, two-year-old seedlings of Fagus crenata Blume were grown in potted andisol supplied with N as NH₄NO₃ solution at 0, 20 or 50 kg ha⁻¹ year⁻¹ and exposed to charcoal-filtered air or O₃ at 1.0, 1.5 and 2.0 times the ambient concentration from 16 April to 22 September 2004. The O₃ induced significant reductions in the whole-plant dry mass, net photosynthetic rate at 380 μmol mol⁻¹ CO₂ (A ₃₈₀), carboxylation efficiency (CE) and concentrations of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) and total soluble protein (TSP) in the leaves. The concentrations of Rubisco and TSP were negatively correlated with the concentration of leaf acidic amino acid, suggesting that O₃ enhanced the degradation of protein such as Rubisco. The N supply to the soil did not significantly change the whole-plant dry mass and A ₃₈₀, whereas it significantly increased the CE and concentrations of Rubisco and total amino acid. No significant interactive effects of O₃ and N supply to the soil were detected on the growth, photosynthetic parameters and concentrations of protein and amino acid in the leaves. In conclusion, N supply to the soil at ≤50 kg ha⁻¹ year⁻¹ does not significantly change the sensitivity to O₃ of growth and net photosynthesis of Fagus crenata seedlings.     

Inundation Analysis in the Coastal Area Considering Climate Change Due to Global Warming

This paper describes the possible inundation scenarios under sea level rise conditions due to global climate change with particular reference to Nagoya, Japan. The study was carried out by using a two-dimensional sea model integrated with one-dimensional river flow model and two-dimensional overland flow model. For the connections of models, the upstream discharge or downstream water level in each grid is considered as the boundary conditions. The governing equations used for the analysis have been solved by finite volume method. The analysis results implicate that some parts of densely populated coastal area of Nagoya city will be vulnerable to inundation if the sea level rise due to global warming by 1 m. Moreover, the performances of existing sewer system and inundation scenario under various conditions have been analyzed.     

A Predictive Mechanism for Mercury Oxidation on Selective Catalytic Reduction Catalysts under Coal-Derived Flue Gas

Abstract

This paper introduces a predictive mechanism for elemental mercury (Hg⁰) oxidation on selective catalytic reduction (SCR) catalysts in coal-fired utility gas cleaning systems, given the ammonia (NH₃)/nitric oxide (NO) ratio and concentrations of Hg⁰ and HCl at the monolith inlet, the monolith pitch and channel shape, and the SCR temperature and space velocity. A simple premise connects the established mechanism for catalytic NO reduction to the Hg⁰ oxidation behavior on SCRs: that hydrochloric acid (HCl) competes for surface sites with NH₃ and that Hg⁰ contacts these chlorinated sites either from the gas phase or as a weakly adsorbed species. This mechanism explicitly accounts for the inhibition of Hg⁰ oxidation by NH₃, so that the monolith sustains two chemically distinct regions. In the inlet region, strong NH₃ adsorption minimizes the coverage of chlorinated surface sites, so NO reduction inhibits Hg⁰ oxidation. But once NH₃ has been consumed, the Hg⁰ oxidation rate rapidly accelerates, even while the HCl concentration in the gas phase is uniform. Factors that shorten the length of the NO reduction region, such as smaller channel pitches and converting from square to circular channels, and factors that enhance surface chlorination, such as higher inlet HCl concentrations and lower NH₃/NO ratios, promote Hg⁰ oxidation.

This mechanism accurately interprets the reported tendencies for greater extents of Hg⁰ oxidation on honeycomb monoliths with smaller channel pitches and hotter temperatures and the tendency for lower extents of Hg⁰ oxidation for hotter temperatures on plate monoliths. The mechanism also depicts the inhibition of Hg⁰ oxidation by NH₃ for NH₃/NO ratios from zero to 0.9. Perhaps most important for practical applications, the mechanism reproduces the reported extents of Hg⁰ oxidation on a single catalyst for four coals that generated HCl concentrations from 8 to 241 ppm, which covers the entire range encountered in the U.S. utility industry. Similar performance is also demonstrated for full-scale SCRs with diverse coal types and operating conditions.