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.     

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.     

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.     

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.     

Total OH reactivity and VOC analyses for gasoline vehicular exhaust with a chassis dynamometer

Total OH reactivity for the exhaust gas of gasoline vehicles was measured for the first time under nine different driving conditions with a chassis dynamometer at the National Institute for Environmental Studies (NIES). Along with the total OH reactivity measurements, analysis of trace species such as CH₄, CO, NO, NO₂, and 56 kinds of volatile organic compounds (VOCs), including two aldehydes, was carried out. The ratio of alkanes to alkenes in the exhaust gas turned out to depend on the condition of the driving cycles. There were a considerable number of unidentified peaks obtained during GC analysis. About 15–30% of the total carbon was unidentified species. The chemical compositions of vehicular exhaust were found to depend on the temperature of the engine or catalysts. The contribution of OH reactivity to the species obtained depended on the temperature condition for the engine. The calculated total OH reactivity for VOCs was compared with ozone formation potential (OFP) and it turned out that there are in good correlation, while the correlation for “Cold” start deviates from that for “Hot” start. The measured and calculated OH reactivities were compared with each other. For all driving cycles, the calculated OH reactivity was confirmed to be an underestimation, implying the existence of unknown species in the exhaust gas. The percentage contribution of OH reactivity to the unknown species during “Cold” start was about 17.5%, which was almost the same as that for “Hot” start at 17.0%. However, the absolute value of OH reactivity for “Cold” start was about ten times higher than that for “Hot” start.     

Dry and wet deposition of water-insoluble dust and water-soluble chemical species during spring 2007 in Tsukuba,Japan

Dry and wet depositions were sampled daily in Tsukuba, Japan, in spring 2007. Temporal variations in the dry and wet deposition fluxes of dust and water-soluble chemical species were controlled largely by air mass origin, the water vapor mixing ratio, and Asian dust events. The contribution of local sources to dry deposition of dust was large when the wind speed was high. Dry deposition fluxes of water-soluble chemical species were larger in humid air masses than in dry air masses. Wet deposition fluxes of dust and water-soluble chemical species indicated that air masses that passed over dust source regions and industrial regions became mixed with the maritime air masses over the coastal site of the Asian continent and western part of the Japanese islands. The total deposition of dust was 4220 mg m^?2 month^?1, and that of water-soluble chemical species ranged from 10 to 636 mg m^?2 month^?1. Wet deposition fluxes of the total deposition flux of dust accounted for 72% and those of water-soluble chemical species was for 72–96%. In particular, the largest wet deposition occurred during a single Asian dust event on 3 April. This event accounted for 23% (950 mg m^?2 month^?1) of the monthly dust deposition flux and for 2–28% (0.43–51 mg m^?2 month^?1) of the monthly deposition flux of water-soluble chemical species. This result implies that the wet deposition flux associated with even one sporadic Asian dust event can have extensive impacts on both terrestrial and oceanic ecosystems in East Asia.     

The relationship between seasonal variations of total-nitrogen and total-phosphorus in rainfall and air mass advection paths in Matsue,Japan

We collected rainwater samples from every rainfall in Matsue, Japan in order to study variations of nitrogen and phosphorus concentrations over time. The seasonal average concentration by magnitude order of Total Nitrogen (here after T-N) was highest in winter, then in spring, fall, and summer and that of Total Phosphorus (here after T-P) was highest in spring, then in winter, fall, and summer. These seasonal variations were examined in relation to the transportation paths of arrived air masses by using a backward trajectory and rainfall patterns from a surface synoptic weather chart. In winter, continental air masses frequently flow from China or Siberia and the resultant winter rainfall is on many occasions of a continental type. In summer, maritime air masses frequently arrive from the Pacific Ocean and this resultant rainfall therefore was often of maritime type. Looking at average concentrations of T-N and T-P for each rainfall type, continental types were high range and maritime types were low. It was therefore concluded that the monthly average concentration of T-N was affected by continental air masses from northern China in winter and by maritime ones from the Pacific Ocean in summer. The maximum deposition of T-N was caused by this concentration in winter and rainfall depth in summer. Seasonal variation of T-P showed a different fluctuation tendency from T-N, with a maximum concentration in spring, and minimum in summer and fall. T-P was susceptible to the yellow sand phenomenon which maximised T-P deposition in spring.