Multi-component behavior of fixed-bed adsorption of dioxins by activated carbon fiber

The multi-component behavior of fixed-bed adsorption of dioxins (DXNs) was examined through detailed analyses of the concentration profiles of isomers in fixed-bed activated carbon fiber (ACF). Regularities in both adsorption rates and strengths were clarified. (1) The rate of transfer in the adsorption of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCCDs/DFs) tends to increase with decreasing number of chlorine substituents. Axial dispersion also tends to increase with a decreasing number of chlorine substituents under our experimental conditions. (2) Homologues with the same number of chlorine substituents in PCDDs/DFs have similar adsorption strengths. The adsorption strength of PCDD/DF isomers is probably greater than that of co-planar polychlorinated biphenyls (co-PCB) isomers when the number of chlorine substituents is identical. (3) The adsorption strength of isomers depends on their molecular structure. In PCDDs/DFs the toxic isomers, all of which have vicinal chlorine substituents at the 2, 3, 7 and 8 positions, are relatively strong. It is clear, especially in TeCDDs, that isomers with vicinal chlorine substituents are stronger than isomers without. In co-PCBs, isomers without chlorine substituents at ortho positions are stronger than those with, and (4) A close analogy exists between the adsorption strength order for ACF and the elution order in gas chromatography (GC).     

Improvement of an efficient separation method for chemicals in diesel exhaust particles: analysis for nitrophenols

GOAL, SCOPE, AND BACKGROUND: Diesel exhaust is believed to consist of thousands of organic constituents and is a major cause of urban pollution. We recently reported that a systematic separation procedure involving successive solvent extractions, followed by repeated column chromatography, resulted in the isolation of vasodilatory active nitrophenols. These findings indicated that the estimation of the amount of nitrophenols in the environment is important to evaluate their effect on human health. The isolation procedure, however, involved successive solvent extractions followed by tedious, repeated chromatography, resulting in poor fractionation and in a significant loss of accuracy and reliability. Therefore, it was crucial to develop an alternative, efficient, and reliable analytical method. Here, we describe a facile and efficient acid-base extraction procedure for the analysis of nitrophenols. MATERIALS AND METHODS: Diesel exhaust particles (DEP) were collected from the exhaust of a 4JB1-type engine (ISUZU Automobile Co., Tokyo, Japan). Gas chromatography-mass spectrometry (GC-MS) analysis was performed with a GCMS-QP2010 instrument (Shimadzu, Kyoto, Japan). RESULTS: A solution of DEP in 1-butanol was extracted with aqueous NaOH to afford a nitrophenol-rich oily extract. The resulting oil was methylated with trimethylsilyldiazomethane and subsequently subjected to GC-MS analysis, revealing that 4-nitrophenol, 3-methyl-4-nitrophenol, 2-methyl-4-nitrophenol, and 4-nitro-3-phenylphenol were present in significantly higher concentrations than those reported previously. DISCUSSION: Simple acid-base extraction followed by the direct analysis of the resulting extract by GC-MS gave only broad peaks of nitrophenols with a poor detection limit, while the GC-MS analysis of the sample pretreated with (trimethylsilyl)diazomethane gave satisfactorily clear chromatograms with sharp peaks and with a significantly lowered detection limit (0.5 ng/ml, approximately 100 times). CONCLUSION: The present method involving an acid-base extraction, in situ derivatization, and GC-MS analysis has shown to be a simple, efficient, and reliable method for the isolation and identification of the chemical substances in DEP.     

Isolation and characterization of 3-nitrophenol-degrading bacteria associated with rhizosphere of Spirodela polyrrhiza

Introduction

The accelerated biodegradation of 3-nitrophenol (3-NP) in the rhizosphere of giant duckweed (Spirodela polyrrhiza) was investigated.

Materials and methods

Biodegradation of 3-nitrophenol in the rhizosphere of a floating aquatic plant, S. polyrrhiza, was investigated by using three river water samples supplemented with 10?mg?l^?1 of 3-NP. Isolation and enrichment culture of 3-NP-degrading bacteria were performed in basal salts medium containing 3-NP (50?mg?l^?1). The isolated strains were physiologically and phylogenetically characterized by using an API20NE kit and 16S rRNA gene sequencing.

Results and discussion

Accelerated removal of 3-NP (100%) was observed in river water samples with S. polyrrhiza compared with their removal in plant-free river water. Also, 3-NP persisted in an autoclaved solution with aseptic plants, suggesting that the accelerated 3-NP removal resulted largely from degradation by bacteria inhabiting the plant rather than from adsorption and uptake by the plant. We successfully isolated six and four strains of 3-NP-degrading bacteria from the roots of S. polyrrhiza and plant-free river water, respectively. Phylogenetic analysis based on 16S rRNA gene divided the 3-NP-degrading bacteria into two taxonomic groups: the genera Pseudomonas and Cupriavidus. The strains belonging to the genus Cupriavidus were only isolated from the roots of duckweed. All strains isolated from the roots utilized 3-NP (0.5?mM) as a sole carbon and energy source, indicating that they could have contributed to the accelerated degradation of 3-NP in the rhizosphere of S. polyrrhiza.

Conclusions

The rhizoremediation using S. polyrrhiza and its rhizosphere bacteria can be an effective strategy for cleaning up the 3-NP-contaminated surface waters.     

Confirmation of polychlorinated biphenyl (PCB) distribution in the blood and verification of simple quantitative method for PCBs based on specific congeners

We measured the concentration of each polychlorinated biphenyl (PCB) congener in whole blood, plasma and blood cells, and investigated the distribution of PCBs in human blood using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). The PCB concentrations in plasma and whole blood in terms of lipid concentrations were almost equal, with a correlation coefficient of r = 0.972. In the blood, the ratio of PCBs in blood cells to those in plasma was generally about 1:9 and the congener distribution patterns in blood cells and plasma were similar.We performed verification of a simple mass screening method by obtaining information on the main PCB congeners for investigations on human accumulation and exposure. The total concentration of the seven PCB congeners (UNEP-7) proposed to the United Nations Environment Programme (UNEP) by Muir and Morita was about 50% of the total concentration of all PCB congeners, and UNEP-30 was about 80%. The seven main congeners in the blood (MCB-7) showed a value that was about 60%, and MCB-30 showed a value that was about 90%. Determinations with the main congeners in the blood showed a correlation of r = 0.990 or more between the main eight congeners (MCB-7 plus #74) and the total PCB concentration for all congeners. The results suggest that, although total PCB concentration can be effectively estimated from the main seven congeners, the main eight congeners would be preferable, and that the use of these congeners in the simple mass screening method would be effective for populations in areas uncontaminated by PCBs.     

Synthesis and structure-activity relationship of diene modified analogs of<Emphasis Type="Italic"> Matsucoccus</Emphasis> sex pheromones

The biological activity of the Matsucoccus spp. sex pheromones and diene modified analogs has been tested in forests of Israel and Portugal in order to explore the structure-activity relationship of the pine bast scale pheromone/kairomone system. The response of the adult predatory bugs, Elatophilus hebraicus and E. crassicornis and of the brown lacewing, Hemerobius stigma is more selective than that of the conspecific Matsucoccus males. The removal of the terminal methyl group from the diene terminus of both pheromones 1 and 2 eliminates all kairomonal activity but retains moderate pheromonal activity. Addition of a methyl group to the diene terminus of pheromones 1 and 2 sustains full pheromonal and kairomonal activities of the Elatophilus spp. but eliminates entirely the kairomonal activity of H. stigma. Subtle designed alterations in the structure of the diene group, typical of all Matsucoccus pheromones, change the mode of the kairomonal activity markedly.     

Removal of Cr(VI) from contaminated soil by electrokinetic remediation

A new process for the removal of hexavalent chromium [Cr(VI)] contaminated soil is described. The process provides for an efficient removal of anionic chemicals from contaminated soils. Chromate anions were removed from the soil to the anodic reservoir by the moving force of electromigration. In this process, the chromate anions that accumulate in the anodic reservoir are simultaneously eliminated by using a column packed adsorbent. The adsorbent (immobilized tannin) used was chemically incorporated into cellulose. Cr(VI) was found to be adsorbed to this adsorbent efficiently. In the electrokinetic process, the pH of the aqueous solution in the anodic reservoir was decreased by the electrolysis of water. In the present study, the pH of the solution in the anodic reservoir is maintained at pH 6 by the addition of an aqueous alkaline solution during the electrokinetic process. The advantage of pH control is that it promotes the release of Cr(VI) from the soil by electromigration, thus permitting the maximum adsorption of Cr(VI) on the immobilized tannin. Simultaneous collection of Cr(VI) from the anodic reservoir leads to the protection from secondary contamination with Cr(VI).