Synthesis and biodegradation of poly(γ-butyrolactone-co-l-lactide)

Biodegradable polyesters were synthesized by ring-opening copolymerization of -butyrolactone (BL) and its derivatives withl-lactide (LLA). Although tetraphenyl tin was the main catalyst used, other organometallic catalysts were used as well.¹H and¹³C NMR spectra showed that poly(BL-co-LLA)s were statistical and that their number-average molecular weights were as high as 7×10⁴. The maximum BL content obtained from copolymerization BL/LLA was around 17%. TheT _m andT _g values of the copolymers showed a gradual depression with an increase in BL content. NoT _m was obtained for the copolymers containing more than 13 mol% BL. The biodegradability of the copolyesters was evaluated by enzymatic hydrolysis and nonenzymatic hydrolysis tests. The enzymatic hydrolysis was carried out at 37°C for 24 h using lipases fromRhizopus arrhizus andR. delemar. Hydrolyses by both lipases showed that an increase in BL content of the copolymer resulted in enhanced biodegradability. Nonenzymatic accelerated hydrolysis of copolymers at 70°C was found to increase proportionally to their exposure time. The hydrolysis rate of these copolymers was considerably faster than that of PLLA. The higher hydrolyzability was recorded for the BL-rich copolymers. The copolymerization of -methyl--butyrolactone (MBL) or -ethyl--butyrolactone (EBL) with LLA resulted in relatively LA-rich copolymers.     

Synthesis of Short-chain-length/Medium-chain-length Polyhydroxyalkanoate (PHA) Copolymers in Peroxisome of the Transgenic Arabidopsis Thaliana Harboring the PHA Synthase Gene from Pseudomonas sp. 61-3

In this paper, the photosynthetic production of short-chain-length/medium-chain-length polyhydroxyalkanoate (PHA) copolymers is reported. The wild-type and highly active doubly mutated PHA synthase 1 (S325T/Q481K, abbreviated ST/QK) genes from Pseudomonas sp. 61-3 were introduced into Arabidopsis thaliana. Peroxisome targeting signal 1 (PTS1) was used to target PHA synthases into the peroxisome to synthesize PHA from the intermediates of the β-oxidation pathway. The transgenic Arabidopsis produced PHA copolymers consisting of 40–57 mol% 3-hydroxybutyrate, 21–49 mol% 3-hydroxyvalerate, 8–18 mol% 3-hydroxyhexanoate, and 2–8 mol% 3-hydroxyoctanoate. The maximum PHA contents were 220μ g/g cell dry weight (cdw) in leaves, and 36μ g/g cdw in stems, respectively. The expression of the ST/QK mutated PHA synthase in leaves gene did not lead to significant difference in PHA content and monomer composition of PHAs, compared to the wild-type PHA synthase gene, suggesting that the supply of monomers may be a rate-determining step of PHA biosynthesis in the peroxisome. However, in stems, there were significant differences dependent on whether the wild-type or ST/QK mutated PHA synthase was expressed. These results suggest that tissue-specific monomer availability is important in determining the final mol% composition of PHA copolymers produced by the peroxisome in plants.     

Accumulation of endocrine disrupting chemicals (EDCs) in the polychaete Paraprionospio sp. from the Yodo River mouth,Osaka Bay,Japan

This study presents the levels of endocrine disrupting chemicals (EDCs) accumulated by Paraprionospio sp. from the Yodo River mouth, Osaka Bay. Since high concentrations of nonylphenol (NP), bisphenol A (BP), octylphenol (OP), 17β-estradiol (E2), and estrone (E1) have been measured in sediment from Osaka Bay, some bioaccumulation could be expected particularly in benthic animals. EDCs were analysed in Paraprionospio sp., a dominant benthic species in Osaka Bay. The results showed that Paraprionospio sp. had accumulated varying concentrations (wet weight; w.w.) of NP at 1,460–4,410 ng/g; BP at 22.5–39.6 ng/g; OP at 18.9–45.4 ng/g; E2 at 0.89–4.35 ng/g; and E1 at 0.06–2.50 ng/g. Accumulation of NP and OP were highest among the samples gathered in summer (July 2008), while concentrations of BP, E2, and E1 did not much differs within 3 years. EDC levels in Paraprionospio sp. were apparently greater than those in sediments showing bioaccumulation.     

Histopathological alterations in gill, liver and kidney of common carp exposed to chlorpyrifos

Histopathological alterations in gill, liver and kidney of common carp, Cyprinus carpio, intoxicated with sub-lethal concentrations of chlorpyrifos (O,O,-diethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate) pesticide (1 and 100 μg/L) for a period of 14 days were analyzed under light microscope. Gill exhibited hyperplasia and hypertrophy of gill epithelium, blood congestion, dilation of marginal channel, epithelial lifting, lamellar fusion, lamellar disorganization, lamellar aneurysm, rupture of the lamellar epithelium, rupture of pillar cells and necrosis. Alterations in hepatocytes were more pronounced, including nuclear and cellular hypertrophy, cellular atrophy, irregular contour of cells and nucleus, cytoplasmic vacuolation, cytoplasmic and nuclear degeneration, cellular rupture, pyknotic nucleus, necrosis and melanomacrophages aggregations. Histopathological lesions in kidney were cellular and nuclear hypertrophy, narrowing of tubular lumen, cytoplasmic vacuolation, hyaline droplet degeneration, nuclear degeneration, occlusion of tubular lumen, tubular regeneration, dilation of glomerular capillaries, degeneration of glomerulus and hemorrhage in Bowman's space. The most significant conclusion drawn from this study was that with the increased concentration and duration the toxicosis of chlorpyrifos would be enhanced as shown through the analysis of mean assessment value (MAV) and degree of tissue changes (DTC) also.     

Assessment of pesticide residues in freshwater areas affected by rice paddy effluents in Southern Japan

Pesticide residues in five freshwater areas that are directly affected by rice paddy effluents in southern Japan were measured to determine their maximum concentrations and temporal variations. Water samples were collected every week during the 2005 rice planting season in Kagoshima Prefecture and stations were established in Amori River, Sudo River, Nagaida River (that drains into the bigger Kotsuki River), rice paddy drainage canal, and wastewater reservoir (that collects effluents from rice paddy fields). Of the 14 target pesticides examined, a total of 11 were detected in all stations. Mefenacet, fenobucarb, and flutolanil were the three pesticides with the highest maximum concentrations and were also detected frequently. Analysis of temporal variations of pesticides showed that herbicides had relatively higher concentrations in the earlier stages of the rice planting season, while insecticides and fungicides had relatively higher concentrations at the later stages. There was no significant difference among stations with regards to the temporal patterns of the top three pesticides. The calculated toxic units were less than 1 in all stations, implying low or negligible environmental risk of pesticides detected to freshwater organisms.     

Theoretical study of the dechlorination reaction pathways of octachlorodibenzo-p-dioxin

The dechlorination reaction pathways of 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin (OCDD) by the hydrogen atom are investigated by the density-functional theory B3PW91 method. The dechlorination reactions have large exothermicity and small activation energies. The activation energies (approximately 5 kcal/mol) of the sigma-complex formation due to the hydrogen addition are lower than those (approximately 9 kcal/mol) of the direct chlorine abstraction. It is suggested that the sigma-complex plays an important role in the reactions, although it has scarcely been shown in previous studies of the dechlorination of dioxins. The sigma-complex formation is favored at low temperatures and the chlorine abstraction is favored at high temperatures. Furthermore, it is found that the lateral positions have a marginal preference over the longitudinal positions. The dechlorination of OCDD by the hydrogen atom is thus not likely to result in a dominant formation of the laterally substituted toxic congeners.     

An empirical model of soil chemical properties that regulate methane production in Japanese rice paddy soils

To understand which soil chemical properties are the best predictors of CH4 production in rice paddy soils, a model was developed with empirical data from nine types of rice soils collected around Japan and anaerobically incubated at 30 degrees C for 16 wk in laboratory conditions. After 1, 2, 4, 8, and 16 wk of incubation, CO2, CH4, and Fe(II) were measured to understand soil organic matter decomposition and iron (Fe) reduction. Available N (N ava) was also measured at the end of incubation. The results showed that decomposable C and reducible Fe are two key parameters that regulate soil CH(4) production (P CH4). There was a significant relationship between decomposable C and available N (N ava) (r2 = 0.975**). Except for a sandy soil sample, a significant relationship between total Fe (Fe total) and reducible Fe was found. From this experiment, a simple model of soil CH4 production was developed: P CH4 = 1.593N(ava) - 2.460Fe total/1000 (each unit was mg kg(-1) soil). After simulated CH4 production by two soil chemical properties as above, there was a significant consistency between model simulation and actual measurement (r2 = 0.831**).     

Polychlorinated-dibenzo-p-dioxins, -dibenzofurans and -dioxin-like polychlorinated biphenyls in aquatic organisms from lake Kasumigaura,Japan

Polychlorinated-dibenzo-p-dioxins (PCDDs), -dibenzofurans (PCDFs) and -dioxin-like polychlorinated biphenyls (DLPCBs) were determined in aquatic wildlife of Kasumigaura Lake (KUL), Japan from 1978 to 2001. Two plankton species elucidated several fold greater concentrations (2400–7800) than small tiger fish (310–6500), shrimp (160–1100), and three large fish namely, black bass (120–240), carp (94–120) and mullet (54) on pg/g fat. PCDD homologues were predominant accumulants with >68–<95% contribution and remaining was shared by PCDFs. Accumulation, non-ortho DLPCBs in plankton (3500–9200), shrimp (1600–8600) and small fish (2000–8800) and large fish (1300–3900) on ng/g fat basis were several orders magnitude greater than PCDD/DFs. The mono-ortho DLPCBs in large fish species were 23?000–83?000?ng/g fat and which it is accounted 94.3–95.9% the total dioxin-like PCBs accumulation. Temporal trends of PCDDs, PCDFs, non-ortho PCBs and TEQ in shrimp and small tiger fish were varied. The mullet had minimum toxic equivalency “TEQ” (14?pg?TEQ/g) followed by plankton Neomysis intermedia (25?pg?TEQ/g), small tiger fish (mean: 33, ranges 14–66?pg?TEQ/g), plankton Cyclopus vicinus (34?pg?TEQ/g), carp (mean: 35, ranges 32–38?pg?TEQ/g), shrimp (mean: 38, ranges 11–68?pg?TEQ/g) and black bass (mean: 59, ranges 38–79?pg?TEQ/g) on fat basis. In all the samples, PCDD was predominant TEQ contributor followed by PCDFs and DLPCBs. The contribution of mono-ortho DLPCBs to the total TEQ was 0.52–0.92 in large fish.     

Feasibility study of a centralized biogas plant performance in a dairy farming area

Journal of Material Cycles and Waste Management - In this feasibility study, the anaerobic co-digestion of different organic wastes obtained from a dairy farming area in Hokkaido prefecture, Japan...     

Genotoxicity of oxy-PAHs to Japanese medaka (Oryzias latipes) embryos assessed using the comet assay

Polycyclic aromatic hydrocarbons (PAHs) have long been recognized as important environmental toxicants. Despite a plethora of information on the fate and effects of parent PAHs, relatively little is known about the environmental fate and toxicity of ketone- and quinone-substituted PAH oxidation products (termed oxy-PAHs), particularly in the aquatic environment. This study begins to fill that gap using embryos of the Japanese medaka (Oryzias latipes) as a model species. The genotoxic potential of two environmentally relevant oxy-PAHs, acenaphthenequinone and 7,12-benz[a]anthracenquinone, was assessed using the comet assay. We found that both oxy-PAHs could cause significant increases in DNA damage after only 48 h of exposure at the lowest concentrations tested (5 μg/L). Comparisons of the genotoxic potential between these oxy-PAHs and their corresponding parent PAHs (acenaphthene and benz[a]anthracene) and a well-known mutagenic PAH, benzo[a]pyrene, indicated similar potencies among all five of these compounds, particularly after longer (7 day) exposures. This study demonstrates the mutagenic potential of oxy-PAHs to an in vivo fish embryo model and points out the need for further study of their environmental occurrence and biologic effects.