Enzymatic degradation of poly([R,S] β-hydroxybutyrate)

The synthetic analogue of a bacterially produced polyester, poly(-hydroxybutyrate) (PHB) was synthesized from racemic -butyrolactone using anin situ trimethyl aluminum-water catalyst. The polymer was fractionated into samples differing in molecular weight and isotactic diad content. The latter was closely related to degree of crystallinity. The biodegradation of these fractions were examined by monitoring mass loss over time in the presence of anAlcaligenes faecalis T1 extracellular bacterial poly(-hydroxybutyrate) depolymerase. The fraction with high isotactic diad tacticity content showed little or no degradation over a 50 hour incubation period, whereas the fraction of intermediate isotactic diad content degraded in a continuous steady fashion at a rate that was less than that for bacterial PHB. The low isotactic diad fraction underwent a rapid initial degradation, followed by no further mass loss. The presence of stereoblocks in the polymer structure of the various fractions was an influence on the degree of susceptibility towards degradation and is related to sample crystallinity.     

沈阳市降雪中PFOS和PFOA污染现状调查

通过调查降雪中PFOS和PFOA的浓度,阐明了沈阳市大气中PFOS和PFOA的污染状况和污染规律.2006-02-06采集沈阳市区和郊区共计36个采样点的降雪样品,2006-02-25在其中5个采样点再次采集降雪样品.固相萃取融雪水中的PFOS和PFOA,利用LC-MS-SIM法测定样品中PFOS和PFOA浓度.全部样品中均检出PFOS和PFOA.2006-02-06降雪中PFOS和PFOA的浓度几何平均值分别为2.0 ng·L^-1（范围：0.4～46.2 ng·L^-1）和3.6 ng·L^-1（范围：1.6～22.4 ng·L^-1）,95%置信区间分别为1.5～2.8 ng·L^-1和3.1～4.2 ng·L^-1.PFOS和PFOA的最高浓度同时出现在郊区采样点朱尔屯,市中心区2种物质的浓度呈显著正相关.2006-02-25的5个采样点降雪中PFOS和PFOA的浓度几何平均值均为2.2 ng·L^-1.2次降雪中PFOS浓度差异不显著,2006-02-25降雪中PFOA浓度高于2006-02-06.结果表明,沈阳市区和郊区降雪中广泛存在PFOS和PFOA污染,局部区域可能存在共同的PFOS和PFOA污染来源;沈阳地区有较稳定的PFOS来源持续向大气中输送该类物质;PFOS和PFOA的环境行为可能不同.     

Identification of methyl chloride-emitting plants and atmospheric measurements on a subtropical island

A survey of methyl chloride (CH3Cl)-emitting plants was performed at a subtropical island in Japan (Iriomote Island). Among the 187 species of tropical/subtropical plants investigated, 33 species from a variety of families were identified as CH3Cl-emitting plants. The strongest emitters were Osmunda banksiifolia, Cibotium balometz, Angiopteris palmiformis, Vitex rotundifolia, Vitex trifolia, and Excoecaria agalloch, each with CH3Cl emission rates exceeding 1microg (gdrywt)(-1)h(-1). The first three species are ferns, and the last three are halophilous plants. Based on our results, the character of CH3Cl emission is likely to be shared at the genus level but not always at the family level. The atmospheric CH3Cl distribution measured on Iriomote Island showed significant enhancement in forested sites (up to 2750 ppt) and a higher concentration on the downwind shore than on the upwind shore. As previously reported, our findings provide strong evidence for the high emission of CH3Cl from tropical/subtropical forests.     

Historical and geographical aspects of the increasing perfluorooctanoate and perfluorooctane sulfonate contamination in human serum in Japan

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have recently received attention due to their widespread contamination in the environment, as well as in wildlife and humans. We measured the PFOS and PFOA concentrations in historically recorded human serum samples at an age range between 20 and 59 years collected in Kyoto, 20 persons per each time point (n=100), and also the PFOS and PFOA concentrations in human serum samples at an age range between 20 and 59 years from 10 locations throughout Japan (n=200). The historical samples collected from 1983 to 1999 demonstrated that the PFOA concentrations in males and females from Kyoto have increased 4.4-fold and 4.3-fold at a rate of increase of 0.49 ng/ml/year and 0.42 ng/ml/year, respectively. In contrast, serum concentrations of PFOS reached a plateau in the late 1980s. There are also regional differences in both the PFOS and PFOA serum concentrations. The concentrations in serum [geometric mean (geometric standard deviation)] (ng/ml) in 2003-2004 ranged from 7.6(1.6) in the town of Matsuoka in Fukui prefecture to 27.8(1.6) in Kyoto city, and ranged from 2.3(1.5) in Matsuoka to 14.5(1.3) in Osaka city for PFOS and PFOA, respectively.     

Photodegradation of gaseous acetaldehyde and methylene blue in aqueous solution with titanium dioxide-loaded activated carbon fiber polymer materials and aquatic plant ecotoxicity tests

TiO₂-supported activated carbon felts (TiO₂–ACFTs) were prepared by dip coating of felts composed of activated carbon fibers (ACFs) with either polyester fibers (PS-A20) and/or a polyethylene pulp (PE-W15) in a TiO₂ aqueous suspension followed by calcination at 250 °C for 1 h. The as-prepared TiO₂–ACFTs with 29–35 wt.% TiO₂ were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and N₂ adsorption. The TiO₂–ACFT(PS-A20) samples with 0 and 29 wt.% TiO₂ were microporous with specific surface areas (S _BET) of 996 and 738 m²/g, respectively, whereas the TiO₂–ACFT(PE-W15) samples with 0 and 35 wt.% TiO₂ were mesoporous with S _BET of 826 and 586 m²/g, respectively. Adsorption and photocatalytic activity of the as-prepared samples were evaluated by measuring adsorption in the dark and photodegradation of gaseous acetaldehyde (AcH) and methylene blue (MB) in aqueous solution under UV light. The TiO₂ loading caused a considerable decrease in the S _BET and MB adsorption capacity along with an increase in MB photodegradation and AcH mineralization. Lemna minor was chosen as a representative aquatic plant for ecotoxicity tests measuring detoxification of water obtained from the MB photodegradation reaction with the TiO₂–ACFT samples under UV light.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in rice straw smoke and their origins in Japan

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) contained in the smoke generated from rice straw burning in post-harvest paddy fields in Japan were analyzed to determine their congener profiles. Both the apportionment of toxic equivalent (TEQ) by using indicative congeners and the comparison of the homolog profiles showed that the PCDDs/PCDFs/DL-PCBs present in the rice-straw smoke were greatly influenced by those present as impurities in pentachlorophenol (PCP) and chlornitrofen (CNP, 4-nitrophenyl-2,4,6-trichlorophenyl ether) formulations that had been widely used as herbicides in paddy fields in Japan. Further, in order to investigate the effects of paddy-field soil on the PCDDs/PCDFs/DL-PCBs present in rice-straw smoke, PCDD/PCDF/DL-PCB homolog profiles of rice straw, rice-straw smoke and paddy-field soil were compared. Rice-straw smoke was generated by burning rice straw on a stainless-steel tray in a laboratory. The results suggested that the herbicides-originated PCDDs/PCDFs/DL-PCBs and the atmospheric PCDDs/PCDFs/DL-PCBs contributed predominantly to the presence of PCDDs/PCDFs/DL-PCBs in the rice-straw smoke while the contribution of PCDDs/PCDFs/DL-PCBs formed during rice straw burning was relatively minimal. The major sources of the PCDDs/PCDFs/DL-PCBs found in the rice-straw smoke were attributed primarily to the paddy-field soil adhered to the rice straw surface and secondarily to the air taken by the rice straw. The principal component analysis supported these conclusions. It is concluded that rice straw burning at paddy fields acts as a driving force in the transfer of PCDDs/PCDFs/DL-PCBs from paddy-field soil to the atmosphere.     

Seasonal change of PCDDs/PCDFs/DL-PCBs in the water of Ayase River, Japan: pollution sources and their contributions to TEQ

In Japan, Ayase River is one of the most polluted rivers by PCDDs, PCDFs and dioxin-like PCBs, which are referred to as dioxins in this paper. The water samples of the river were collected once per month for a year, and dioxins were analyzed to examine the dioxin sources and their contributions to toxic equivalent (TEQ). The WHO-2006 TEQs ranged from 0.26 to 7.0 pg-TEQ L⁻¹ and the average was 2.7 pg-TEQ L⁻¹; eight of 12 samples exceeded the environmental quality standard in Japan (1.0 pg-TEQ L⁻¹). The TEQ value was high during the irrigation period from May to August. The most part of the dioxins in the river water existed in suspended solids (SS) and it seemed that the river received water with highly-dioxin-contaminated SS in the irrigation period. The homologue profiles of the water samples suggested that the dioxins were influenced by pentachlorophenol (PCP) and chlornitrofen (CNP) formulations which were widely used as herbicides for the paddy fields in Japan. According to TEQ apportionment estimated by using indicative congeners, the TEQ was mainly contributed by PCP. Moreover, it was also shown that the TEQ contributions of PCP and CNP formulations increased along with the increase of the total TEQ and the TEQ contribution was dominated by these herbicides during the irrigation period. Therefore, it was concluded that the herbicides-originated dioxins run off from the paddy fields into the river during the irrigation period and increased the dioxins level in the river water. The result from the principal component analysis was consistent with these conclusions.     

Perfluorosulfonates and perfluorocarboxylates in snow and rain in Dalian,China

Samples of precipitation events (snow and rain) in Dalian, a typical coastal town in China, were analyzed for perfluorosulfonates (PFSAs) and perfluorocarboxylates (PFCAs) to investigate atmospheric contamination by these compounds. In the snow event on December 16, 2006, samples were collected from 21 different sites and in another 6 precipitation events, samples were collected from a single location. Four PFSAs (C4, C6, C8, C10) and seven PFCAs (C6–12) were analyzed. Among the homologues, perfluorooctane sulfonate (PFOS) concentrations were the highest with a geometric mean (GM) of 145 ng/L (n = 21) during the snow event on December 16, 2006, followed by perfluorooctanoate (PFOA) with a GM of 24.7 ng/L (n = 21). Concentrations of perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS) and perfluoroheptanoate (PFHpA) were more than two orders of magnitude lower than that of PFOS. Other PFSAs and PFCAs were found to be below the limit of detection in all the samples. In other 6 precipitation events, PFSAs and PFCAs were detected approximately in the same order of magnitude in both snow and rain. The results indicate that wet deposition may be a potential transport mechanism of perfluorinated chemicals in the environment.     

Liquefaction process for a hydrothermally treated waste mixture containing plastics

Most landfilled plastic waste is a mixture or is in the form of composites with incombustible wastes such as glass, metals, and ceramics. After hydrothermal treatment, including a steam-explosion process, the separation of mixed waste (MW) into organic and inorganic substances becomes easy. However, the effect of hydrothermal pretreatment on the subsequent liquefaction of organic substances from MW is not obvious. In this study, the effects on the liquefaction of polystyrene and high-density polyethylene are discussed. Moreover, optimum conditions for the liquefaction of organic substances from hydrothermally treated MW are identified. By means of this hydrothermal pretreatment, including the steam-explosion process, polystyrene and high-density polyethylene can be significantly converted to oil by liquefaction at 300°–400°C. In comparison with liquefaction of hydrothermally pretreated mixed waste (HMW) at 300°–400°C with a batch type reactor, the yield of oil increases significantly on liquefaction using a semi-batch type reactor. It is considered that the radical chain and termination reactions among the radicals from HMW were inhibited in the semi-batch type reactor. On liquefaction of HMW in a semi-batch reactor, the conversion of HMW to oil was enhanced on increasing the liquefaction temperature to 350°C and the holding time to 60 min. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6