Sequestration of prenylated benzoic acid and chromenes by Naupactus bipes (Coleoptera: Curculionidae) feeding on Piper gaudichaudianum (Piperaceae)

The curculionid beetle Naupactus bipes (Germar, 1824) (Coleoptera: Curculionidae: Brachycerinae) has shown feeding preference for leaves of Piper gaudichaudianum, demonstrating an unexpected specificity for an insect considered to be a generalist. The leaves of P. gaudichaudianum contain the prenylated chromenes gaudichaudianic acid (4, major compound) and its methyl ester (5) in addition to a chromene (3) lacking one prenyl residue. In addition to 4, roots contain the chromone methyl ester (1) and methyl taboganate (2, major compound). Feeding on roots, larvae of N. bipes sequester exclusively the root-specific compounds 1 and 2. Adult beetles sequester the leaf-specific chromenes 3 and 4, but were found to also contain compounds 1 and 2 that are absent in leaves. Therefore, it is suggested that 1 and 2 are sequestered by larvae and can be found in the body of adult insects after long-term storage. In addition, 3 and 4, the major compounds in leaves were found to be associated with the eggs.     

Exposure to carbonyl compounds in charcoal production plants in Bahia, Brazil

Studies have investigated the exposure levels of carbonyl compounds (CC) in the indoor and outdoor air of homes, vehicles, workplaces, urban and industrial areas, and rural sites. However, an investigation of these emissions and occupational exposure to CC in charcoal production facilities has not been previously conducted. The objective of this study was to measure the atmospheric concentrations of several CC to assess the exposure of workers of two charcoal plants located north of Salvador, Bahia, Brazil. Stationary and personal samples were collected using Sep-Pak® C18 cartridges that were coated with a 0.2 % acidic solution of 2,4-dinitrophenylhydrazine. The quantification of the resulting 2,4-dinitrophenylhydrazone derivatives was conducted using a high-performance liquid chromatography system with UV detection. In the personal samples, the concentrations of formaldehyde, acetaldehyde, propanone, furfural, and C4 isomers (n-butanal-isobutanal-butanone) ranged from 12 to 139, 38 to 165, 136 to 483, 39 to 114, and 63 to 132 μg?m^?3, respectively. In the stationary samples, the concentrations of these CC ranged from 20 to 160, 111 to 284, 328 to 644, 70 to 163, and 100 to 176 μg?m^?3, respectively. When compared to the occupational exposure limits for 8 h, the concentrations of formaldehyde were often greater than the levels recommended by the American National Institute for Occupational Safety and Health, which indicates a health risk for charcoal workers. These results are the first reported concerning the occupational exposure to CC in charcoal plants.     

Surface ozone and carbon monoxide levels observed at Oki, Japan: regional air pollution trends in East Asia

Simultaneous ground-based measurements of ozone and carbon monoxide were performed at Oki, Japan, from January 2001 to September 2002 in order to investigate the O(3) and CO characteristics and their distributions. The observations revealed that O(3) and CO concentrations were maximum in springtime and minimum in the summer. The monthly averaged concentrations of O(3) and CO were 60 and 234 ppb in spring and 23 and 106 ppb in summer, respectively. Based on direction, 5-day isentropic backward trajectory analysis was carried out to determine the transport path of air masses, preceding their arrival at Oki. Comparison between classified results from present work and results from the year 1994-1996 was carried out. The O(3) and CO concentration results of classified air masses in our analysis show similar concentration trends to previous findings; highest in the WNW/W, lowest in N/NE and medium levels in NW. Moreover, O(3) levels are higher and CO levels are lower in the present study in all categories.     

Preparation of Chitin/Cellulose Films Compatibilized with Polymeric Ionic Liquids

This paper reports the preparation of chitin/cellulose films compatibilized with polymeric ionic liquids. In-situ (co)polymerization of polymerizable ionic liquids, 1-(3-methacryloyloxypropyl)-3-vinylimidazolium bromide (1) and 1-methyl-3-vinylbenzylimidazolium chloride (3), was carried out in the presence of a radical initiator, AIBN, in the chitin/cellulose solution with ionic liquid solvents (1-butyl-3-methylimidazolium acetate and chloride, BMIMOAc and BMIMCl, respectively), followed by the appropriate procedure to give the desired films. The presence of the polymeric ionic liquid in the film was confirmed by the IR measurement. The powder X-ray diffraction analysis suggested that crystalline structures of the polysaccharides were largely disrupted in the film, as same as that of a chitin/cellulose film prepared by the AMIMOAc/BMIMCl system. These results were different from the XRD result of a chitin/cellulose film prepared by the 1-allyl-3-methylimidazolium bromide/BMIMCl system reported in our previous study, in which some crystalline structures were still remained in the film. Furthermore, the mechanical properties of the present films were evaluated by tensile testing, which were affected by the molar ratios of the polymeric ionic liquids to the polysaccharides and the compositional ratios of the two units 1 and 3.     

Production of cement clinkers from municipal solid waste incineration (MSWI) fly ash

This communication reports the laboratory scale study on the production of cement clinkers from two types of municipal solid waste incineration fly ash (MSW ash) samples. XRD technique was used to monitor the phase formation during the burning of the raw mixes. The amount of trace elements volatilized during clinkerization and hydration, as well as leaching behaviours of the clinkers obtained from optimum compositions, were also evaluated. From the results it is observed that all of the major components of ordinary Portland cement (OPC) clinkers are present in the produced clinkers. Results also show the volatilization of considerable amounts of Na, K, Pb, Zn and Cd during the production of clinkers. However, major parts of the toxic elements remaining in the clinkers appear to be immobilized in the clinkers phases. Hydration studies of the clinkers obtained from optimum compositions show that the clinkers prepared from raw MSW ash are more reactive than the washed MSW ash based clinkers. TG/DTA analyses of the hydrated pastes show the formation of hydration products, which are generally found in OPC and OPC derived cements. The initial study, therefore, shows that more than 44% of MSW ash with the addition of very small amounts of silica and iron oxide can be used to produce cement clinkers. The amount of CaCO3 necessary to produce clinkers (approximately 50%) is also smaller than the same required for the conventional process (more than 70%).     

Biotransformation of 4-nerolidylcatechol by Heraclides brasiliensis (Lepidoptera: Papilionidae) reduces the toxicity of Piper umbellata (Piperaceae)

Heraclides brasiliensis (Lepidoptera: Papilionidae) larvae feed preferably on Piperaceae, foraging successfully on leaf tissues even though species of this contain high levels of secondary metabolites such as amides and lignans, associated with diverse biological activities including insecticidal properties. Studies examining the metabolism of chemical constituents in Piperaceae by insects are rare. In this study, we characterized the metabolites of 4-nerolidylcatechol (4-NC), the major constituent of Piper umbellata (Piperaceae), and E-2,3-dihydro-3-(3,4-dihydroxyphenyl)farnesoic acid, compounds from fecal material of H. brasiliensis larvae fed a diet containing only P. umbellata leaves. The biotransformed product was also detected in larval and pupal tissues. Moreover, we observed deactivation of the toxicity of P. umbellata leaves against brine shrimp after their metabolism in H. brasiliensis larvae from a LC₅₀ of 523.3 to 3,460.7 μg/mL. This deactivation is closely associated with the biotransformation of 4-NC to E-2,3-dihydro-3-(3,4-dihydroxyphenyl)farnesoic acid, which showed LC₅₀ of 8.0 and >1,000 μg/mL, respectively.     

Food webs are built up with nested subwebs

Nested structure, in which specialists interact with subsets of species with which generalists interact, has been repeatedly found in networks of mutualistic interactions and thus is considered a general feature of mutualistic communities. However, it is uncertain how exclusive nested structure is for mutualistic communities since few studies have evaluated nestedness in other types of networks. Here, we show that 31 published food webs consist of bipartite subwebs that are as highly nested as mutualistic networks, contradicting the hypothesis that antagonistic interactions disfavor nested structure. Our findings suggest that nested networks may be a common pattern of communities that include resource-consumer interactions. In contrast to the hypothesis that nested structure enhances biodiversity in mutualistic communities, we also suggest that nested food webs increase niche overlap among consumers and thus prevent their coexistence. We discuss potential mechanisms for the emergence of nested structure in food webs and other types of ecological networks.     

Persistent organochlorines in minke whale (Balaenoptera acutorostrata) and their prey species from the Antarctic and the North Pacific

Persistent organochlorines such as polychlorinated biphenyls (PCBs), DDTs, chlordane compounds (CHLs), hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) were determined in the blubber of minke whale and its diet collected from the Antarctic and the North Pacific Oceans. Residue levels of these compounds (except HCB) in minke whale from the Antarctic were apparently lower than those from the North Pacific. This is due to the lower levels of these pollutants in the southern hemisphere than in the northern hemisphere and the specific feeding habit of the minke whale from the Antarctic which feeds on lower trophic organisms, primarily euphausiids. The north-south difference for HCB residue levels was small, reflecting its dispersible nature through long-range atmospheric transport. Compositions of DDT and CHL compounds in minke whale from the Antarctic were similar to those from the North Pacific. However, the composition of HCH isomers was different between the Antarctic and the North Pacific as was observed in their diet, suggesting a larger or on-going usage of lindane in the southern hemisphere countries. In minke whale from the Antarctic, the elevated level of PCBs residues was noted during a period of 1984 to 1993, implying a continuous discharge of PCBs in the southern hemisphere. A similar discharge was also suggested in the North Pacific, while a decreasing contamination by DDTs was apparent.     

Reduction of serum thyroxine concentrations by methylsulfonyl metabolites of tetra-, penta- and hexachlorinated biphenyls in male Sprague-Dawley rats

Male Sprague-Dawley rats received four consecutive intraperitoneal doses of nine methylsulfonyl (MeSO2) metabolites of tetra-, penta- and hexachlorinated biphenyls (tetra-, penta- and hexaCBs) to determine their effects on thyroid hormone levels. Nine MeSO2 metabolites, major MeSO2-PCBs detected in human milk, liver and adipose tissue, were 3-MeSO2-2,2',4',5-tetraCB (3-MeSO2-CB49), 3-MeSO2-2,3',4',5-tetraCB (3-MeSO2-CB70), 3-MeSO2-2,2',3',4',5-pentaCB (3-MeSO2-CB87), 3-MeSO2-2,2',4',5,5'-pentaCB (3-MeSO2-CB101), 4-MeSO2-2,2',4',5,5'-pentaCB (4-MeSO2-CB101), 3-MeSO2-2,2',3',4',5,6-hexaCB (3-MeSO2-CB132), 3-MeSO2-2,2',3',4',5,5'-hexaCB (3-MeSO2-CB141), 3-MeSO2-2,2',4',5,5',6-hexaCB (3-MeSO2-CB149) and 4-MeSO2-2,2',4',5,5',6-hexaCB (4-MeSO2-CB149). All nine MeSO2 metabolites (20 micromol/kg once daily for four days) reduced serum total thyroxine levels (16-44%) at a much lower dose than phenobarbital (431 micromol/kg once daily for four days) on days 2, 3, 4 and 7 after the last dosage. Total triiodothyronine level was reduced 37% by treatments with 3-MeSO2-CB49 and 3-MeSO2-CB149 at day 7, but increased 35% and 38% by 3-MeSO2-CB70 and 4-MeSO2-CB101 at days 3 and 4, respectively. The reductions in thyroxine levels led to an increase in thyroid-stimulating hormone levels by 3-MeSO2-CB49, 3-MeSO2-CB87, 3-MeSO2-CB101, 3-MeSO2-CB132, 3-MeSO2-CB141, 3-MeSO2-CB149 and 4-MeSO2-CB149. A 30% increase in thyroid weight was produced by 3-MeSO2-CB101 and 3-MeSO2-CB141 treatments. Total cytochrome P450 content and the activity of 7-pentoxyrosorufin O-dealkylase were increased by all seven 3-MeSO2-PCBs. 3-MeSO2-CB49, 3-MeSO2-CB87, 3-MeSO2-CB101 and 3-MeSO2-CB132 also increased the activity of 7-ethoxyresorufin O-dealkylase. Thus, it is likely that all nine tested MeSO2 metabolites could influence thyroid hormone metabolism. The results show that tested 3- and 4-MeSO2 metabolites of tetra-, penta- and hexaCBs reduce thyroid hormone levels in rats, suggesting that the metabolites may act as endocrine-disrupters.