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).     

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.     

Separation of plastic mixtures using liquid-fluidized bed technology

Separation of heavier-than-water plastic mixtures had been investigated via the fluidization of their packed beds induced by an upward flow of water. The samples examined were resin pellets and crushed plastic products including PVC, PET and PBT. On the onset of a flow, a mixed bed was swelled to the state of fluidization and separated into layers of respective resins depending on their density. The effects of the flow rate, an amount of the samples and their density difference were examined on the separation of resin pellets. Under an appropriate condition, the process was completed within a few minutes, and satisfactory separation was attained when the density difference of the samples exceeded 0.05 g cm-3. By using a column equipped with several sample outlets sorted resins could be recovered with their purity intact by withdrawing each layer successively from above through a suitable outlet. Multi-stage separation was also found to be effective in treating close-density samples. Compared with uniform-sized resin pellets, size distribution of crushed plastic samples deteriorated the separation to some extent.     

Structural characterization and visible light activated photocatalytic ability of glass–ceramics prepared from municipal solid waste

Journal of Material Cycles and Waste Management - The relationship between local structure and visible-light-activated photocatalytic ability of glass–ceramics prepared from Municipal Solid...     

Diel feeding behavior of neritic copepods during spring and fall blooms in Akkeshi Bay,eastern coast of Hokkaido,Japan

In situ diel feeding behavior of neritic copepods was investigated using the gut fluorescence method, during spring and fall bloom periods in Akkeshi Bay, on the eastern coast of Hokkaido, Japan. Acartia omorii and Paracalanus sp. were the dominant species during the fall, and Pseudocalanus spp. and A. longiremis during the spring. During both bloom periods, diel rhythms were always observed for the gut pigment contents of these dominant copepods, although there were interspecific differences in the pattern. The maximum gut pigment content was always observed during the night and the minimum during the day. For all species, except Paracalanus sp., the average gut pigment content during the night was significantly higher (p<0.05) than during daytime by factors of between 1.5 and 2.7. There were no significant differences between the gut evacuation rate constants determined during the day and the night, and initial gut pigment content had no effect on the value of gut evacuation rate constants. The instantaneous ingestion rates of individual copepods calculated from gut pigment and the mean value of gut evacuation rate constants followed the same diel rhythms as gut pigment contents. Copepod daily ingestion rates were higher than the daily requirements for respiration during both bloom periods. Estimated daily ration was 40 to 91% of body carbon during the fall bloom, and 17 to 28% during the spring bloom. The higher daily rations during fall were probably due to the difference in in situ temperature (ca. 14°C).     

Development of a accelerated solvent extraction and gel permeation chromatography analytical method for measuring persistent organohalogen compounds in adipose and organ tissue analysis

A new analytical method has been developed for the quantification of 59 different persistent organohalogen compounds, such as polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), PCB metabolites, organochlorine pesticides (OCPs) in biological organ tissues. The optimum extraction and cleanup procedures were examined using accelerated solvent extraction (ASE), automated gel permeation chromatography (GPC) on Biobeads S-X3 and automated solid phase extraction (SPE) on silica-gel. The target compounds were divided into two fractions, non-polar compounds and more polar compounds, which in the latter fraction was subsequently methylated using diazomethane. Detection can be achieved by GC/MS in negative chemical ionization (NCI) mode. The average recoveries of the compounds spiked in swine liver, heart, kidney, and cattle adipose tissues were considered satisfactory, and it was confirmed that the method could be used in routine analysis.