Photochemical decomposition of environmentally persistent short-chain perfluorocarboxylic acids in water mediated by iron(II)/(III) redox reactions

The photochemical decomposition of short-chain (C(3)-C(5)) perfluorocarboxylic acids (PFCAs) was investigated. Direct photolysis in water proceeded slowly with the 220- to 460-nm light emission from a xenon-mercury lamp to form F(-), CO(2), and shorter-chain PFCAs. Addition of a small amount of Fe(3+) to the aqueous solutions of the PFCAs dramatically enhanced their photochemical decomposition under an oxygen atmosphere: when the (initial PFCA)/(initial Fe(3+)) molar ratio was 13.5 (initial PFCA concentration=67.3mM), the pseudo-first-order rate constants for the PFCA decomposition were 3.6-5.3 times those with photolysis alone, and the turnover number for the catalytic PFCA decomposition [i.e., (moles of decomposed PFCA)/(moles of initial Fe(3+))] reached 6.71-8.68 after 24h of irradiation. The catalysis can be explained by photoredox reactions between PFCA, Fe(3+)/Fe(2+) and oxygen via photo-induced complexation of Fe(3+) with the PFCAs.     

Adsorption and desorption characteristics of several herbicides on sediment

The objective of this study was to clarify the adsorption and desorption characteristics of several herbicides in sediment. Five herbicides, esprocarb, thiobencarb, dimethametryn, pretilachlor, and simetryn were examined in this study. The adsorption ratio on the sediment increased in the following order: pretilachlor < dimethametryn < simetryn < thiobencarb < esprocarb. On the other hand, the adsorption ratio on the sediment without organic matter increased in the following order: thiobencarb < esprocarb < pretilachlor < dimethametryn < simetryn. Furthermore, the amounts of simetryn, dimethametryn, and pretilachlor adsorbed on the sediment without organic matter increased, while those of esprocarb and thiobencarb decreased in comparison to the original sediment. These results strongly suggested that the mineral surface in the sediment was very important as the adsorption site for the herbicide, especially in the case of simetryn, dimethametryn, and pretilachlor. All the adsorption and desorption data fitted well with the Freundlich equation. The hysteresis in the adsorption-desorption phenomena in the sediment was observed for all the herbicides, and it was affected by the organic matter in sediment, especially in the case of dimethametryn and pretilachlor.     

Influence of chemical characteristics of humic substances on the partition coefficient of a chlorinated dioxin

The partition coefficients (Koc) of 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) with respect to a variety of humic substances (HSs) were evaluated by a method involving solid-phase microextraction and gas chromatography-electron capture detection. The log Koc values for each of the HS samples were in the range of 6.4-7.7. The log Koc values for HAs from tropical peat, brown forest and ando soils were in the range of 7.3-7.6, similar to the calculated value for the octanol-water partition coefficient (log Koc=7.56). In contrast, the log Koc values for FAs and peat HAs were 0.5-1 unit lower than the calculated value. The parameters for the polarity of HSs, as calculated from (N+O)/C, O/C atomic ratios and the carboxyl group content, were numerically similar related to the log Koc for HpCDD. These results show that the Koc values for HpCDD are significantly influenced by the polarity of HSs.     

How do water striders, Aquarius paludum, react to brackish water simulated by NaCl solutions?

Several stages, from eggs to adults, of the water strider, Aquarius paludum (Fabricius), inhabiting fresh water are sometimes conveyed by heavy flow in the rainy or typhoon seasons in Japan to lotic brackish water in the mouth of rivers. The water striders might then respond to salinity either by remaining to wait for extensive rainfall to reduce osmotic pressure locally before reproducing (“breed here and later tactic”) or by flying away to reproduce in fresh waters elsewhere (“breed elsewhere and later tactic”). All first instars died before the first molt when they were exposed to 1.75 and 3.5% NaCl solutions in a laboratory experiment. Living on 0.5 and 0.9% solutions through larval and adult stages slowed down larval growth and suppressed female reproduction. When exposed to the 0.5 and 0.9% solutions, 90 and 92% of males, respectively, showed histolysis of their flight muscles. Therefore, in brackish natural habitats, larvae and adults seem to follow the strategy “breed here and later.” When water striders were exposed to 0.9% solution either just after emergence or 20 days later, females showed a higher flight propensity than those kept on fresh waters throughout, and they delayed the deposition of eggs. Therefore, when conveyed to brackish water after emergence by stream flow after heavy rain, adults seem to leave the area by flight, demonstrating the strategy “breed elsewhere and later” tactic. We conclude that water striders use alternative tactics for responding to salinity, depending on the stage of exposure.     

Metals leachability from medical waste incinerator fly ash: A case study on particle size comparison

This paper presents the results from a study of metals leachability of medical waste incinerator fly ash in Japan on the basis of particle size. Sequential extraction and Toxicity Characteristic Leaching Procedure (TCLP) analysis were carried out in order to quantify the leaching amount of metals in each categorized particle size. Sequential extraction was also subjected to identify the preference of binding matrix of metals. The results of sequential extraction showed an increase both exchangeable and carbonate associated chromium concentrations in the bigger particle size fractions. Likewise, concentrations of carbonate matrix of arsenic and tin tended to increase in the bigger particle size fractions. In contrast, exchangeable associated cadmium as well as both exchangeable and carbonate matrices of barium were found higher in the smaller particle size fractions. However, no correlation was found in Kendal-tau correlation analysis between particle size of the ash and metals leachability of the TCLP.     

Seasonal variations in 228Ra/226Ra ratio within coastal waters of the Sea of Japan: implications for water circulation patterns in coastal areas

In this study, low-background gamma-spectrometry was used to determine the (228)Ra/(226)Ra ratio of 131 coastal water samples from various environments around Honshu Island, Japan (mainly around Noto Peninsula) at 1-3 month intervals from April 2003 until September 2005. Spatial variation in (228)Ra/(226)Ra ratios was also assessed by analyzing 34 coastal water samples from five areas within the Sea of Japan during May and June 2004. The (228)Ra/(226)Ra ratio of coastal water from all sites around Noto Peninsula shows seasonal variation, with minimum values during summer ((228)Ra/(226)Ra=0.7) and maximum values during autumn-winter ((228)Ra/(226)Ra=1.7-2). This seasonal variation is similar to that recorded for coastal water between Tsushima Strait and Noto Peninsula. The measured lateral variation in (228)Ra/(226)Ra ratios within coastal water between Tsushima Strait and Noto Peninsula is only minor (0.5-0.7; May-June 2004). Coastal waters from two other sites (Pacific shore and Tsugaru Strait, north Honshu) show no clear seasonal variation in (228)Ra/(226)Ra ratio. These measured variations in (228)Ra/(226)Ra ratio, especially the temporal variations, have important implications for seasonal changes in patterns of coastal water circulation within the Sea of Japan.     

Microwave-assisted synthesis of biodegradable and antibacterial thiophene,furan and thiazole derivatives

Environmental Chemistry Letters - The rise of bacterial resistance to common clinical antibiotics is calling for alternative techniques to synthesize antibacterial drugs with high biodegradability....     

Why do municipalities accept disaster waste? Evidence from the great east Japan earthquake

Environmental Economics and Policy Studies - Municipalities’ cooperation is critical for successful policy interventions for disaster recovery. Using a spatial econometric model, we...