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.     

An anaerobic continuous-flow fixed-bed reactor sustaining a 3-chlorobenzoate-degrading denitrifying population utilizing versatile electron donors and acceptors

An anaerobic continuous-flow fixed-bed column reactor capable of degrading 3-chlorobenzoate (3-CBA) under denitrifying conditions was established, and its rate reached 2.26 mM d(-1). The denitrifying population completely degraded 3-CBA when supplied at 0.1-0.54 mM, but its activity was partly suppressed when 3-CBA was supplied at 0.89 mM. Nitrate was concomitantly consumed throughout the operation of the reactor, the amount of which was similar to or up to 35% higher than the theoretical stoichiometric value that was calculated by assuming that 3-CBA degradation is coupled with denitrification. Batch incubation experiments proved that nitrate is strictly required for 3-CBA degradation in the absence of molecular oxygen. The population also degraded 3-CBA aerobically. Benzoate and 4-CBA were degraded under denitrifying conditions as well as 3-CBA, but 2-CBA was not. Considering that the previously reported denitrifying 3-CBA-degrading cultures do not exhibit 4-CBA degradation under denitrifying conditions, nor aerobic 3-CBA degradation [FEMS Microbiol. Lett. 144 (1996) 213, Appl. Environ. Microbiol. 66 (2000) 3446], the microbial population developed in this experiment was physiologically versatile with respect to the utilization of both electron donors and electron acceptors.     

High seagrass diversity and canopy-height increase associated fish diversity and abundance

Seagrass species function as typical foundation species that unifies most ecosystem processes. This ecosystem role depends largely on the morphological characteristics and structural complexity of seagrass beds, including their ecological importance for fish species. This study examined relationships between seagrass bed characteristics and associated fish communities in mixed seagrass beds. Correspondence analysis (CA) and canonical correlation analysis (CCoA) were performed to estimate relationships for individual seagrass bed characteristics. The CCoA results revealed that species richness and three-dimensional structure of seagrass had great effect on the biomass and richness of the associated fish community. The CA results revealed that the relative importance of seagrass bed characteristics differed among fish functional groups including fishes appearing on the surface of, inside, and on the bottom of seagrass beds. The fishes found on the surface of the beds preferred beds with low seagrass biomass and high three-dimensional structure, those inside the beds preferred beds with high seagrass biomass and high three-dimensional structure, and those on the bottom of the beds preferred locations with low seagrass biomass and low three-dimensional structure. The results of this study provide compelling evidence that seagrass beds with high species diversity and high three-dimensional structure, but intermediate biomass, may provide the great benefit to the associated fish community. Such niche complementarity among fishes may be a process facilitated by seagrass diversity for secondary production as an ecosystem functioning.     

Large-scale evaluation of the current level of polybrominated diphenyl ethers (PBDEs) in breast milk from 13 regions of Japan

Polybrominated diphenyl ethers (PBDEs) were measured in 2004 in 105 breast milk samples collected from 13 regions of Japan (Hokkaido, Akita, Miyagi, Tokyo, Gifu, Fukui, Kyoto, Hyogo, Wakayama, Shimane, Yamaguchi, Kochi and Okinawa). Six congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154) were determined by gas chromatography /mass spectrometry (GC/MS). Total PBDE levels ranged from 0.01 to 23.0 ng/g lipid (geometric mean (GM), 1.34 ng/g lipid). BDE-47 (GM, 0.66 ng/g lipid, 59% of sigmaPBDE) was the most abundant congener present in breast milk and was detected in 99% of the samples. Total PBDE levels were higher in northern Japan than in other regions. We analyzed the effects of occupation, age, smoking status, alcohol consumption and number of deliveries on total PBDE levels. None of these factors were significantly associated with the level of PBDEs. The present study revealed that the current level of exposure to PBDEs in Japan is lower than that in the USA or Sweden. GMs (ng/g lipid) (GSD, geometric standard deviation) and medians (ng/g lipid) of PBDE levels in each district are as follows: Hokkaido 2.70 (1.70), 2.74; Akita 4.49 (2.19), 5.44; Miyagi 1.77 (4.37), 1.11; Tokyo 1.39 (2.09), 1.63, Gifu 2.83 (4.79), 2.23; Fukui 1.05 (2.34), 1.18; Kyoto 1.31 (2.95), 1.33; Hyogo 1.02 (2.69), 0.88; Wakayama 1.33 (3.80), 1.70; Shimane 0.83 (2.51), 0.66; Yamaguchi 1.74 (2.82), 1.76; Kochi 0.50 (2.69), 0.74 and Okinawa 1.91 (2.75), 1.22. This is the first large-scale study of current PBDE levels in breast milk in Japan.     

Deterioration of Polyamideamine–Epichlorohydrin (PAE) in Aqueous Solutions During Storage: Structural Changes of PAE

Structural changes of polyamideamine–epichlorohydrin (PAE) in solution during storage at 4 °C and pH 4.2–4.5 for up to 8.9 years were studied by ¹H- and ¹³C-NMR analyses, colloidal titration and others. NMR signals due to 3-hydroxy-azetidinium groups of PAE decreased during storage, and correspondingly 2, 3-dihydroxypropyl groups were formed by the ring opening. The content of 3-hydroxy-azetidinium groups in PAE determined by ¹H-NMR were similar to that determined by the colloidal titration, although the former was higher than the latter. About 50% of the 3-hydroxy-azetidinium groups present in the fresh PAE were lost during storage for 8.9 years. Furthermore, ¹³C-NMR analysis revealed that significant depolymerization of polyamideamine chains occurred by hydrolysis of the amide linkages during storage. Rough evaluation of number average degree of polymerization (DPn) of the amideamine repeating unit showed that the DPn decreased from 12 to 2 during storage for 8.9 years.     

Pulverization of waste printed circuit boards

A new pulverization method to reduce the volume of waste printed circuit boards is reported. About 50% of printed circuit boards with integrate circuits (ICs) could be pulverized by our method in one 20-min batch, but boards without ICs could not be pulverized. By repeating the process three times, about 95% of printed circuit boards with ICs could be made into a fine powder with particles less than 106µm. A weight-drop test was also performed to examine the strength of the printed circuit boards and clarify the mechanism of pulverization. When a weight was dropped on the solder-welding side of the board ruptures occurred more easily than when the weight was dropped on the IC-mounted side. With a heavy weight, the IC was fractured more easily when the potential energy was low. Where the stress was concentrated, two types of rupture location were found on printed circuit boards with ICs. One was where the IC was connected to the printed circuit board. The other was where the surface had undulations. It also became clear that the fracture of printed circuit boards depends on the impacting weight rather than on the potential energy.     

Two lactones in the androconial scent of the lycaenid butterfly Celastrina argiolus ladonides

Male adult butterflies of many species have characteristic odors originating from the disseminating organs known as androconia. Despite the fact that androconia exist in several species, there have been few investigations on adult scents from the lycaenid species. Celastrina argiolus ladonides (Lycaenidae) is a common species in Eurasia. We have reported that male adults of this species emit a faint odor, and the major components causing this odor have been newly found in the Insecta. By using field-caught individuals, we determined the chemical nature and location of this odor in the butterfly. Gas chromatography–mass spectrometry (GC–MS) analyses revealed that two lactone compounds, lavender lactone and δ-decalactone, are present in the extracts of males but absent in those of the females. On an average, approximately 50 ng of each compound was found per male. Chiral GC analyses performed using enantiomerically pure standards revealed that the natural lavender lactone was a mixture of two enantiomers with an R/S ratio of 32:68, whereas the natural δ-decalactone contained only the R-enantiomer. When the analyses were conducted using different parts—forewings, hindwings, and body—of three males, the lactones were more abundantly found on the forewings and hindwings than on the body. Microscopic observation of the wings demonstrated that battledore scales known as androconia are scattered on the upper surface of both the wings of C. argiolus ladonides males. These results indicate that the specialized scales on the wings of males serve as scent-disseminating organs.