TEMPO-Mediated Oxidation of Norway Spruce and Eucalyptus Pulps: Preparation and Characterization of Nanofibers and Nanofiber Dispersions

This study deals with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation of cellulose. Softwood and hardwood pulp fibers were suspended in water and oxidized to various extents at pH 10 and 22 °C using sodium hypochlorite in the presence of TEMPO radical and sodium bromide. This reaction system is known to be the most efficient one for the introduction of both surface carboxyl and aldehyde groups. Important relationships between formation of these functional groups and the fibrillation yield, light transmittance of the water dispersions and degree of polymerization of the oxidized softwood and hardwood pulps were established in the present study. A birefringence test confirmed the presence of nanofibers which according to atomic force microscopy analyses had diameters in the 1.6–3.8 nm range.     

Historical and geographical aspects of the increasing perfluorooctanoate and perfluorooctane sulfonate contamination in human serum in Japan

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have recently received attention due to their widespread contamination in the environment, as well as in wildlife and humans. We measured the PFOS and PFOA concentrations in historically recorded human serum samples at an age range between 20 and 59 years collected in Kyoto, 20 persons per each time point (n=100), and also the PFOS and PFOA concentrations in human serum samples at an age range between 20 and 59 years from 10 locations throughout Japan (n=200). The historical samples collected from 1983 to 1999 demonstrated that the PFOA concentrations in males and females from Kyoto have increased 4.4-fold and 4.3-fold at a rate of increase of 0.49 ng/ml/year and 0.42 ng/ml/year, respectively. In contrast, serum concentrations of PFOS reached a plateau in the late 1980s. There are also regional differences in both the PFOS and PFOA serum concentrations. The concentrations in serum [geometric mean (geometric standard deviation)] (ng/ml) in 2003-2004 ranged from 7.6(1.6) in the town of Matsuoka in Fukui prefecture to 27.8(1.6) in Kyoto city, and ranged from 2.3(1.5) in Matsuoka to 14.5(1.3) in Osaka city for PFOS and PFOA, respectively.     

Separation, synthesis and estrogenic activity of 4-nonylphenols: two sets of new diastereomeric isomers in a commercial mixture

Two sets of new diastereomeric 4-nonylphenol (NP) isomers [4-(3,4-dimethylheptan-4-yl)phenol (344NP, NP-J, L) and 4-(3,4-dimethylheptan-3-yl)phenol (343NP, NP-K, P)] were separated from a commercial NP mixture. The mixture of these diastereomers was synthesized at the same time by a single Friedel-Crafts reaction of 3,4-dimethyl-4-heptanol and phenol, and the mixture was separated into individual NPs by HPLC equipped with Hypercarb column. For the first time, in this study the stereostructure-estrogenic activity relationship of NP diastereomers was investigated. The NP isomers (NP-L and NP-P) having the beta-methyl group over the benzene ring were found to be 2-4 times more estrogenic than their diastereomers (NP-J and NP-K). In the case of the other set of diastereomer [4-(3,5-dimethylheptan-3-yl)phenol, (353NP, NP-E, G)] containing gamma-methyl group in the molecule, the gamma-methyl proton signal (delta 0.49) in the more estrogenic isomer (NP-G) also appeared in a higher field than the corresponding methyl signal (delta 0.76) of the less estrogenic isomer (NP-E).     

Monitoring PCDD/Fs, PCBs and metals in the ambient air of an industrial area of Catalonia, Spain

In 2005 and 2006, the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and metals (As, Be, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sn, Tl and V) were measured in air samples collected in an industrial area of Sant Adrià del Besòs (Barcelona, Catalonia, Spain) where a municipal solid waste incinerator (MSWI) is placed, and in a background/control area. In general terms, concentrations of all environmental pollutants were higher at the industrial site. No significant seasonal/temporal variations were observed in any of the areas. No Pearson correlation was found between the PCDD/F concentrations and the environmental conditions of the two sampling periods considered. Principal component analyses (PCA) were performed to get information on the relationship among samples, pollutants, and emission sources. The results indicate that the MSWI of S. Adrià de Besòs is not a significant emission source of the above compounds for the area under its direct influence. Moreover, a notable difference in the PCDD/F congener profiles was found between ambient air and stack gas emissions, indicating that the current levels of PCDD/Fs are more related to other potential emissions sources rather than to those from the MSWI.     

Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds

Formation of N-nitrosodimethylamine (NDMA) by ozonation of commercially available dyes and related compounds was investigated. Ozonation was conducted using a semi-batch type reactor, and ozone concentration in gas phase and the ozone gas flow were 10 mg L(-1) and 1.0 L min(-1), respectively. NDMA was formed by 15 min of ozonation of seven out of eight selected target compounds (0.05 mM) at pH 7. All the target compounds with N,N-dimethylamino functions were NDMA precursors in ozonation. The lowest and highest NDMA concentrations after ozonation of the target compounds were 13 ng L(-1) for N,N-dimethylformamide (DMF) and 1600 ng L(-1) for N,N-dimethyl-p-phenylenediamine (DMPD), respectively. NDMA concentrations after 15 min of ozonation of 0.05 mM methylene blue (MB) and DMPD increased with an increase in pH in its range of 6-8. The effects of coexisting compounds on NDMA concentrations after 15 min of ozonation of 0.05 mM MB and DMPD were examined at pH 7. NDMA concentrations after ozonation of MB and DMPD increased by the presence of 0.05 mM (0.7 mg L(-1) as N) nitrite (NO(2)(-)); 5000 ng L(-1) for MB and 4000 ng L(-1) for DMPD. NDMA concentration after MB ozonation decreased by the presence of 5mM tertiary butyl alcohol (TBA), a hydroxyl radical (HO.) scavenger, but that after DMPD ozonation was increased by the presence of TBA. NDMA concentrations after ozonation of MB and DMPD were not affected by the presence of 0.16 mM (5.3 mg L(-1)) hydrogen peroxide (H(2)O(2)). When 0.05 mM MB and DMPD were added to the Yodo and Tone river water samples, NDMA concentrations after 15 min of their ozonation at pH 7 increased compared with those in the case of addition to ultrapure water samples.     

Identification of 2,6-diisopropylnaphthalene metabolites in carp part 1. In vivo experiment

The metabolism of diisopropylnaphthalene (DIPN) in fish was studied from an ecotoxicological viewpoint to clarify the environmental fate of DIPN, a solvent of carbonless paper which is widely used as a substitute for PCB. This study identified the following metabolites in carp by in vivo experiment; 2-(1-hydroxy-1-methyl) ethyl-6-isopropylnaphthalene, 2-(1-methyl-2-hydroxyethyl)-6-isopropyl-naphthalene, 2,6-(1-hydroxy-1-methyl) ethyl-naphthalene, 2-(1-hydroxy-1-hydroxymethyl) ethyl-6-isopropylnaphthalene and α-[2-(6-isopropylnaphthyl)] propionic acid. Identification was based on UV, IR, MS, and NMR analyses. The metabolism of 2,6-DIPN in carp was concluded to mainly through oxidation of the isopropyl chain.     

Metabolism of potassium bromate in rats II. In vitro studies

To learn more about the biodegradation of potassium bromate, the decomposition of bromate in various tissues of rats was studied. Bromate was degraded very slowly in human saliva and plasma of rat. However, nearly all tissue homogenates and red blood cells could degrade bromate by a mechanism which exhibited some stability to heat. Furthermore, it was suggested that the bromate degradation active component in the supernatant fraction of a liver homogenate was in part glutathione.     

Prenatal diagnosis of Fukuyama congenital muscular dystrophy

Fukuyama congenital muscular dystrophy (FCMD) is characterized by infantile hypotonia, symmetrical generalized muscle weakness, and neuronal migration disturbances that result in changes consistent with cobblestone lissencephaly with cerebral and cerebellar cortical dysplasia. FCMD is recognized as an autosomal recessive genetic defect. Genetic counselling is recommended for parents at risk of having a child with FCMD. Given the high risk and overwhelming prospect of having another child with this incurable devastating condition leads many couples to consider prenatal diagnosis. In Japanese families, haplotype analysis using microsatellite markers is available. In non-Japanese families, DNA sequence analysis is available. Both disease-causing alleles of an affected family member must be identified before prenatal testing can be performed. Copyright © 2006 John Wiley & Sons, Ltd.     

A method for determination of methyl chloride concentration in air trapped in ice cores

A method for measuring the concentration of methyl chloride (CH3Cl) in air trapped in an ice core was developed. The method combines the air extraction by milling the ice core samples under vacuum and the analysis of the extracted air with a cryogenic preconcentration/gas chromatograph/mass spectrometry system. The method was applied to air from Antarctic ice core samples estimated to have been formed in the pre-industrial and/or early industrial periods. The overall precision of the method deduced from duplicate ice core analyses was estimated to be better than +/-20 pptv. The measured CH3Cl concentration of 528+/-26 pptv was similar to the present-day concentration in the remote atmosphere as well as the CH3Cl concentration over the past 300 years obtained from Antarctic firn air and ice core analyses.