Photodegradation of Poly(lactic acid) Stereocomplex by UV-Irradiation

Neat poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) films and PLLA/PDLA blend films were prepared by solution casting, and their photodegradation by UV-irradiation was investigated using wide-angle X-ray scattering (WAXS), gel permeation chromatography, differential scanning calorimetry, tensile testing, and polarized optical microscopy. The PLLA/PDLA blend film was more photodegradation-resistant than the neat PLLA and PDLA films when photodegradation was monitored by molecular weight, melting temperature, and WAXS crystalline peak positions. This indicates that the chains in both amorphous and crystalline regions of the PLLA/PDLA blend film were photo-cleavage-resistant compared to those of the neat PLLA and PDLA films. The changes in melting temperature and WAXS crystalline peak positions before and after photodegradation respectively indicated the increased crystalline lattice disorder and the decreased crystalline lattice sizes of the neat PLLA and PDLA films, whereas these changes were insignificant for the blend films. Photodegradation caused no significant change in tensile properties, with the exception of significant decreases in the tensile strength and elongation at break of PLLA/PDLA blend film. However, the tensile strength and elongation at break of the PLLA/PDLA blend film retained higher values compared to those of the neat PLLA and PDLA films during photodegradation. In spite of the slower photodegradation of the PLLA/PDLA blend film traced by M _n, T _m, and WAXS crystalline peak positions than that of neat PLLA and PDLA films, the rapid decrease in tensile strength and elongation at break of the former than that of the latter should be due to the highly-ordered structural difference between them, i.e., the three dimensional dry gel of the former and the spherulites of the latter.     

Plutonium(VI) accumulation and reduction by lichen biomass: correlation with U(VI)

The uptake of plutonium(VI) and uranium(VI) by lichen biomass was studied in the foliose lichen Parmotrema tinctorum to elucidate the migration behavior of Pu and U in the terrestrial environment. Pu and U uptake by P. tinctorum averaged 0.040+/-0.010 and 0.055+/-0.015 g gdry (-1), respectively, after 96 h incubation with 4.0 x 10(14) mol 1(-1) Pu solutions of pH 3, 4 and 5. SEM observations showed that the accumulated Pu is evenly distributed on the upper and lower surfaces of P. tinctorum, in contrast to U(VI), which accumulated in both cortical and medullary layers. UV/VIS absorption spectroscopy demonstrates that a fraction of Pu(VI) in the solution is reduced to Pu(V) by the organic substances released from P. tinctorum, and the accumulated Pu on the surface is reduced to Pu(IV), while U(VI) keeps the oxidation state of VI. Since the solubility of Pu(IV) hydroxides is very low, reduced Pu(VI) does not penetrate to the medullary layers, but is probably precipitated as Pu(IV) hydroxides on the cortical lichen surface. It is concluded that the uptake and reduction of Pu(VI) by lichens is important to determine the mobilization and oxidation states of Pu in the terrestrial environment.     

Chlordane compounds residues in Weddell seals (Leptonychotesweddelli) from the Antarctic

Weddell seal samples taken from the Antarctic have been found to be contaminated with chlordane compounds. ΣChlordane ($\text{cis}\text{-chlordane}\text{+}\text{cis}\text{-nonachlor}\text{+}\text{trans}\text{-nonachlor}\text{+}\text{oxychlordane}$) was present in blubber of seals at the range of 12 - 62 ng/g fresh weight. The order of chlordane compound concentrations was $\text{trans}\text{-nonachlor}\text{>}\text{oxychlordane}\text{>}\text{cis}\text{-nonachlor}\text{>}\text{cis}\text{-chlordane}$. Relative aboundance of $\text{cis}$-chlordane in Σchlordane is higher than that in humans. A probable explanation for their occurrence in the Antarctic is an airborne transport.     

Evolution of water chemistry in natural acidic environments in Yangmingshan,Taiwan

In Yangmingshan National Park, located in the northern part of the Taiwan Island, there is a very rare area where fish (Channa asiatica) live in spite of acid environments. The origin of the acid in local acid ponds and rivers and the evolution of the water chemistry are discussed on the basis of sulfur stable isotope ratios and chemical equilibria. One of the sources of the acid is sulfuric acid, which is derived from the oxidation of hydrogen sulfide in volcanic gas gushing out from fumaroles around the area and from acid deposition supplied from Taipei City. It is also derived from the oxidation of pyrite: the sulfur stable isotope ratios of delta 34S of +1@1000 to +4@1000 (relative to CDT) of sulfate in acid pond waters (pH 3-4) could be related to those of hydrogen sulfide in volcanic gas, pyrite in local pond sediments and soils, and sulfate in rain water. One acid source is sulfuric and hydrochloric acids arising in springs from geothermal activity: the delta 34S values were characterised by +13@1000 to +17@1000 sulfate-S, which was provided by a disproportionation reaction of sulfur dioxide in the depths. Another acid source could be the oxidation of iron(II). Under acidic conditions, the water-rock reaction gives rise to high concentrations of aluminium and iron. While flowing down surface streams, iron(II) is oxidised to iron(III) and then hydrolysed to cause further acidification under oxic conditions. The concentrations of iron and aluminium are controlled by redox and dissolution equilibria.     

Sonochemical degradation of 2,3,7,8-tetrachlorodibenzo-p-dioxins in aqueous solution with Fe(III)/UV system

2,3,7,8-Tetrachlorodibenzo-p-dioxin (2,3,7,8-TeCDD) was rapidly decreased by sonication in aqueous solution. The degradation efficiency was strongly influenced by ultrasonic power and reaction temperature. An initial 2,3,7,8-TeCDD concentration of 20 ng l(-1) was completely degraded within 60 min under sonochemical conditions using a 20 kHz frequency with a 150 W ultrasound power. The activation energy is 21.9 kJ/mol in the temperature range of 10-40 degrees C, suggesting a diffusion-controlled reaction. To increase the efficiency of 2,3,7,8-TeCDD treatment, degradation system combined ultrasound with Fe(III) (2 x 10(-4)mol l(-1)) and UV irradiation. Both UV and Fe(III) induced Fenton, Fenton-like and photo-Fenton reactions, leading to additional OH radicals and rapid 2,3,7,8-TeCDD removal.     

Experimental study on CO2 monitoring and quantification of stored CO2 in saline formations using resistivity measurements

This paper reports CO₂ saturation estimations based on resistivity data obtained from laboratory measurements and induction logging results at the Nagaoka pilot CO₂ injection site. The laboratory experiments put in evidence that the presence of clay content tends to reduce the increase of resistivity caused by the displacement of brine by less conductive CO₂. As a result, CO₂ saturations estimated from resistivity measurements without any correction for the clay effect are considerably lower than the actual saturations. The resistivity index (RI) provides better estimates of CO₂ saturations than the Archie's equation because it requires the determination or assumption of only one rock parameter: the saturation exponent. CO₂ saturations estimated from the induction logging data acquired at Nagaoka are considerably lower than the neutron porosity changes due to displacement between brine and CO₂ in the reservoir. Even in the case of considering the De Witte's equation and the Poupon's to account for the clay effect, it was still difficult to get a good agreement with the neutron logging results. New relations based on the resistivity index with correction factors for the clay effect are developed and implemented in this study. One of these relations has proved to be effective to estimate CO₂ saturations in saline formations with high clay content.     

Determination of an acceptable assimilable organic carbon (AOC) level for biological stability in water distribution systems with minimized chlorine residual

There is considerable interest in minimizing the chlorine residual in Japan because of increasing complaints about a chlorinous odor in drinking water. However, minimizing the chlorine residual causes the microbiological water quality to deteriorate, and stricter control of biodegradable organics in finished water is thus needed to maintain biological stability during water distribution. In this investigation, an acceptable level of assimilable organic carbon (AOC) for biologically stable water with minimized chlorine residual was determined based on the relationship between AOC, the chlorine residual, and bacterial regrowth. In order to prepare water samples containing lower AOC, the fractions of AOC and biodegradable organic matter (BOM) in tap water samples were reduced by converting into biomass after thermal hydrolysis of BOM at alkaline conditions. The batch-mode incubations at different conditions of AOC and chlorine residual were carried out at 20°C, and the presence or absence of bacterial regrowth was determined. The determined curve for biologically stable water indicated that the acceptable AOC was 10.9 μg C/L at a minimized chlorine residual (0.05 mg Cl₂/L). This result indicated that AOC removal during current water treatment processes in Japan should be significantly enhanced prior to minimization of the chlorine residual in water distribution.     

Concentrations and their ratio of (222)Rn decay products in rainwater measured by gamma-ray spectrometry using a low-background Ge detector

The concentrations and the concentration ratios of individual short-lived (222)Rn decay products ((214)Pb and (214)Bi) in rainwater were measured at Kumatori village (34.39 degrees N, 135.35 degrees E, approximately 70 m above sea level) in Osaka, Japan, by gamma-ray spectrometry using a low-background Ge detector. The dependence of the time variations of the concentrations and their ratios on rainfall rate was investigated. It was observed that the concentrations were negatively correlated with the rainfall rate in some rainfall events, and that there was no clear correlation in other rainfall events. The changes in the dependence of the concentration on the rainfall rate occurred after the passage of a cold front during a single rainfall event. The concentration ratios showed a weak negative correlation with the rainfall rate for most of the observed rainfall events. A scavenging model was designed in this study in order to explain the observation results. Based on the relationship between the concentrations of (214)Pb and (214)Bi in the rainwater and the rainfall rate for an individual rainfall event, the increase in the environmental gamma-ray dose rate from (214)Pb and (214)Bi deposited on the ground was calculated, and the calculated increase agreed well with that observed by the in situ measurement on flat ground.     

Degradation of polychlorinated dibenzo-p-dioxins in aqueous solution by Fe(II)/H2O2/UV system

The photodegradation of polychlorinated dibenzo-p-dioxins (PCDDs), which include tetra- to octa-CDDs (TeCDD, PeCDD, HxCDD, HpCDD and OCDD), was carried out in the presence of Fe(II) and H2O2 mixed reagent. The degradation efficiency was strongly influenced by UV irradiation, and the initial concentrations of H2O2 and Fe(II). An initial TeCDD concentration of 10 ng l(-1) was completely degraded within 20 min under the optimum conditions. All PCDDs tested were successfully degraded by Fe(II)/H2O2/UV treatment and complete degradation of TeCDD, PeCDD and HxCDD was achieved within 120 min. PCDD photodegradation rates decreased with the number of chlorine atoms. The degradation process of TeCDD by this system seems to be initiated by an oxidative reaction (OH* radical attack) because less chlorinated DDs as intermediate products were not detected. From the Frontier electron density calculation, the first OH* radical attack positions on TeCDD were found to be four C atoms neighboring two O atoms. The decomposition of TeCDD gave 4,5-dichlorocatechol as an intermediate product. A TeCDD degradation scheme was proposed based on the identified intermediate and the values of Frontier electron density. Based on these results, Fe(II)/H2O2/UV system could be useful technology for the treatment of wastewater containing persistent pollutants such as dioxins and polychlorinated biphenyls.     

Postembryonic development of the bone-eating worm Osedax japonicus

Bone-eating worms of the genus Osedax exclusively inhabit sunken vertebrate bones on the seafloor. The unique lifestyle and morphology of Osedax spp. have received much scientific attention, but the whole process of their development has not been observed. We herein report the postembryonic development and settlement of Osedax japonicus Fujikura et al. (Zool Sci 23:733–740, 2006). Fertilised eggs were spawned into the mucus of a female, and the larvae swam out from the mucus at the trochophore stage. Larvae survived for 10 days under laboratory conditions. The larvae settled on bones, elongated their bodies and crawled around on the bones. Then they secreted mucus to create a tube and the palps started to develop. The palps of O. japonicus arose from the prostomium, whereas the anterior appendages of other siboglinids arose from the peristomium. The recruitment of dwarf males was induced by rearing larvae with adult females. Females started to spawn eggs 6 weeks after settlement.