Degradation of organophosphoric esters in leachate from a sea-based solid waste disposal site

Degradation of organophosphoric esters (OPEs) in leachate from a sea-based solid waste disposal site was investigated by laboratory experiment. Aryl-phosphates, tricresyl phosphate and triphenyl phosphate, in leachate rapidly decreased to less than the detection limit within 20 days under aerobic condition, suggesting high biodegradability. These phosphates also decreased in sterilized leachate, which suggested a contribution to degradation by reactions (adsorption and chemical degradation) with chemicals in the leachate. Concerning alkyl-phosphates, tributyl phosphate decreased rapidly after one week, which is considered to have been caused by biodegradation. Tris-2-ethylhexyl phosphate and tris-2-butoxyethyl phosphate decreased slowly in all samples but that of sterilized distilled water. This however, suggested contribution of biodegradation because the velocity of decrease in the leachate was higher than in control samples. Among chloro alkylphosphates, decrease of tris-2-chloroethyl phosphate and tris-dichloropropyl phosphate were observed though it was not obvious whether by biodegradation or not. Decrease of tris-2-chloropropyl phosphate (TCPP) was not observed for 80 days suggesting that TCPP remains in the leachate over a long period of time. Except for aryl-phosphates decrease of OPEs was not observed under anaerobic condition. It was considered that the composition ratio and the behavior of OPEs in leachate in the field reflects the biological and chemical degradation as well as the chemical properties of OPEs.     

Sorption behavior of selenium on humic acid under increasing selenium concentration or increasing solid/liquid ratio

The sorption of selenium (Se) on humic acid (HA) was investigated in order to better understand the fate of stable and radioactive Se in soils and sediments. An ultrafiltration technique was used to determine size distributions of HA-sorbed-Se when increasing Se concentration and solid/liquid ratio. The results showed that the Se sorption onto HA followed the Freundlich isotherm. No solid/liquid ratio-dependence was observed especially when <3 kDa molecular size fraction was used from solid/liquid separation. The Freundlich isotherm parameters K(F) and n obtained using the <3 kDa molecular size fraction for solid/liquid separation were 3.7 x 10(2) and 0.82, respectively. In addition, since dissolved HA increased with decreased ionic strength in the HA suspension, ionic strength could promote aggregation of HA. The conformational change of HA could affect the sorption behavior of Se on HA.     

A global transport model of lead in the atmosphere

A global atmospheric transport model is used to calculate lead concentrations in the atmosphere. The model performance is evaluated through comparisons with observations in Europe. The model results of lead concentrations in surface air were compared with measurements in East Asia. The detailed comparisons showed generally good agreement for recent decades, although systematic underestimation was found in China. Anthropogenic lead emissions in China are estimated from economic statistics to be 56 000 t yr^?1, which is not small considering the economic scale of China. The underestimations suggest a hidden source of lead emissions. The emissions in Japan and Korea are derived from optimization by the model. The magnitude is about 2000 t yr^?1, which is much greater than that reported by the Pollutant Release and Transfer Register in Japan and Toxics Release Inventory in Korea.     

Evaluation of pressurized liquid extraction for the determination of neonicotinoid pesticides in green onion

Abstract

A pressurized liquid extraction (PLE) method was presented for the determination of six neonicotinoid pesticides, acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam in green onion. The critical parameters of PLE, e.g. extraction solvent, temperature, pressure, number of cycles, and static extraction time, were optimized by test on the spiked green onion with six neonicotinoids and the incurred green onion applied with four commercial neonicotinoid insecticide formulations (acetamiprid, dinotefuran, imidacloprid, and thiamethoxam). As a result, the recoveries of six neonicotinoids obtained by one cycle PLE with acetonitrile at 140?°C and 50?bar for 10?min were 94.7–99.5%. These results were acceptable according to the validation guideline for testing method of agricultural chemicals in food by Ministry of Health, Labour, and Welfare in Japan. PLE was also validated by the test on the incurred green onion. The analytical values of four neonicotinoids obtained by PLE were good agreement with those obtained by solid–liquid extraction with homogenizer, which is employed for Japanese official method for the analysis of pesticide residues in food (the ratios of analytical values obtained by PLE to those obtained by solid–liquid extraction were 99.7–101.2%). These results indicate that PLE is applicable for the determination of neonicotinoids in green onion.     

Assays of dioxins and dioxin-like compounds in actually contaminated soils using transgenic tobacco plants carrying a recombinant mouse aryl hydrocarbon receptor-mediated β-glucuronidase reporter gene expression system

The transgenic tobacco plant XD4V-26 carrying the recombinant mouse aryl hydrocarbon receptor XD4V-mediated β-glucuronidase (GUS) reporter gene expression system was used for assay of dioxins and dioxin-like compounds consisting of polychlorinated dibenzeno-p-dioxins, polychlorinated dibenzofurans, and coplanar polychlorinated biphenyls (Co-PCBs) in actually contaminated soils. The transgenic tobacco plant XD4V-26 showed a significant dose-dependent induced GUS activity when cultured on MS medium containing PCB126 [toxic equivalency factor (TEF) = 0.1]. In contrast, PCB169 and PCB180, which have 0.03 of TEF and unassigned TEF values, respectively, did not significantly induce GUS activity under the same conditions as with PCB126. When the tobacco plants were cultivated for up to 5 weeks on actually contaminated soils with dioxins and dioxin-like compounds collected from the periphery of an incinerator used for disposal of residential and industrial wastes, GUS activity in the leaves was dose-dependently increased. The plants clearly detected 360 pg-TEQ g(-1) of dioxins and dioxin-like compounds in this assay. There was a positive correlation between GUS activity and TEQ value of dioxins and dioxin-like compounds in the plants. This assay does not require any extraction and purification processes for the actually contaminated soil samples.     

Novel enzymatic activity of cell free extract from thermophilic Geobacillus sp. UZO 3 catalyzes reductive cleavage of diaryl ether bonds of 2,7-dichlorodibenzo-p-dioxin

We characterized the ability of the cell free extract from polychlorinated dibenzo-p-dioxins degrading bacterium Geobacillus sp. UZO 3 to reduce even highly chlorinated dibenzo-p-dioxins such as octachlorodibenzo-p-dioxins in incineration fly ash. The degradation of 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) as a model dioxin catalyzed by the cell free extract from this strain implicates that the ether bonds of 2,7-DCDD molecule undergo reductive cleavage, since 4′,5-dichloro-2-hydroxydiphenyl ether and 4-chlorophenol were detected as intermediate products of 2,7-DCDD degradation.     

Formation of chlorinated estrones via hypochlorous disinfection of wastewater effluent containing estrone

Chlorinated derivatives of estrone (E1) in the effluent of a municipal sewage treatment plant located in Shizuoka prefecture, Japan were detected by gas chromatography/mass spectrometry using electron impact in selected ion monitoring (GC/MS-EI-SIM) analysis. The concentrations of E1, 2-chloroestrone, 4-chloroestrone and 2,4-dichloroestrone in the effluent sample collected in December 2005 were 60.0 ng l(-1), 4.0 ng l(-1), 14.5 ng l(-1), and 9.8 ng l(-1), respectively. In the effluent sample taken in June 2005, 2,4-dichloroestrone was detected at 5.6 ng l(-1) along with 17.6 ng l(-1) of E1. However, only E1 was detected at 5.9 ng l(-1) in the sample in May 2005. To elucidate the behavior of E1 during the disinfection process with sodium hypochlorite in the sewage treatment plant, we carried out a reaction of E1 with sodium hypochlorite in buffer solutions at pH 7 and 9. As E1 was consumed rapidly, chlorinated estrones were produced and relatively fast formation of 2-chloroestrone, 4-chloroestrone, and 2,4-dichloroestrone was observed. Furthermore, 1,4-estradiene-3,17-dione derivatives were formed from the reaction between 2,4-dichloroestrone and sodium hypochlorite.     

Dioxins in human milk and smoking of mothers

BACKGROUND: The relation between the levels of dioxins in human breast milk and the smoking habits of the mothers is controversial. To clarify this relationship, we analyzed data from the human milk survey in Japan. METHODS: The human milk survey has been conducted in Japan since 1997. Healthy pregnant women aged 20-39 years were recruited and 50 ml of breast milk was collected from them at 30 days after delivery. PCDDs, PCDFs, and dioxin-like PCBs were measured by using GC/MS. The smoking habits of the mothers were established by interviewing them soon after delivery and were classified into four categories: current smokers, ever smokers who quit smoking at the pregnancy, ever smokers who quit smoking before the pregnancy, and never smokers. The levels of dioxins in breast milk were compared in the four categories of smoking among 853 primiparas. In addition, we analyzed the association between dioxin levels and passive smoking among never smokers. The geometric means of the dioxin concentrations were calculated in order to compare the differences between dioxins. RESULTS: The geometric means of dioxin-like PCBs in milk of never smokers was the highest (9.2 pg TEQ/g fat); followed by ever smokers who quit smoking before the pregnancy, ever smokers who quit smoking at the pregnancy, and current smokers (7.5, 7.2, and 6.6 pg TEQ/g fat, respectively). The differences between these levels were statistically significant (ANOVA, p<0.001). No significant difference was observed between the level of dioxins in milk from never smokers subjected to passive smoking status and those who had not experienced passive smoking. CONCLUSION: The levels of dioxin-like PCBs in human milk were negatively related to the smoking habits of mothers.     

Ontogenetic shift in foraging habit of ocean sunfish Mola mola from dietary and behavioral studies

The ocean sunfish (Mola mola) is typically considered to feed on gelatinous zooplankton, but reports in the literature describe various benthic organisms being found in their stomachs. This might reflect ontogenetic dietary shift, as little was known about the foraging habit of this species. We examined their foraging habits using dietary analyses in combination with a behavioral study in Iwate, Japan (39°22′N, 141°58′E) from 2009 to 2010. Our stomach content analyses (n = 17, 31–250 cm total length) suggested that small sunfish (<50 cm) feed on benthic crustaceans, but large sunfish (>200 cm) feed on jellyfish. Larger sunfish showed higher values of both carbon and nitrogen stable isotope ratios. Deployment of accelerometers and animal-borne cameras on small sunfish in July (49–58 cm, n = 5) suggested their possibility of feeding, while they stayed near the seabed. This indicates that small sunfish might feed on benthic preys. Deployment of accelero-magnetometers on large sunfish in July (84–164 cm, n = 4) clarified that the large sunfish in July swam back and forth between the surface and deep water (>100 m). Temporary decelerations, which were considered to be associated with feeding of planktonic prey, were observed in deep water. Whereas deployment of accelero-magnetometers on large sunfish in November (105 cm, n = 3) showed several bursts, they swam within the mixed layer (0–100 m), which might be associated with chasing of rapid prey. These results suggest that ocean sunfish have heterogeneous diets depending on their body size and possibly season.     

Metabolism and excretion of orally and intraperitoneally administered trimethylarsine oxide in the hamster

When trimethylarsine oxide (TMAO) was administered orally to hamsters once only, 86.9±11.1% of the administered dose of the compound was exreted in the urine during the following 24 hours: TMAO proved to be an arsenic compound eliminated extremely rapidly. The unchanged form of TMAO was the one and only trimethylarsenic compound (TMA) detected in the urine: in othe words, TMAO proved neither to be demethylated nor to be converted to arsenobetaine. It was shown, on the other hand, that TMAO is partly reduced in vivo and that only trimethylarsine was detected in expired air.