Synthesis and biodegradation of poly(γ-butyrolactone-co-l-lactide)

Biodegradable polyesters were synthesized by ring-opening copolymerization of -butyrolactone (BL) and its derivatives withl-lactide (LLA). Although tetraphenyl tin was the main catalyst used, other organometallic catalysts were used as well.¹H and¹³C NMR spectra showed that poly(BL-co-LLA)s were statistical and that their number-average molecular weights were as high as 7×10⁴. The maximum BL content obtained from copolymerization BL/LLA was around 17%. TheT _m andT _g values of the copolymers showed a gradual depression with an increase in BL content. NoT _m was obtained for the copolymers containing more than 13 mol% BL. The biodegradability of the copolyesters was evaluated by enzymatic hydrolysis and nonenzymatic hydrolysis tests. The enzymatic hydrolysis was carried out at 37°C for 24 h using lipases fromRhizopus arrhizus andR. delemar. Hydrolyses by both lipases showed that an increase in BL content of the copolymer resulted in enhanced biodegradability. Nonenzymatic accelerated hydrolysis of copolymers at 70°C was found to increase proportionally to their exposure time. The hydrolysis rate of these copolymers was considerably faster than that of PLLA. The higher hydrolyzability was recorded for the BL-rich copolymers. The copolymerization of -methyl--butyrolactone (MBL) or -ethyl--butyrolactone (EBL) with LLA resulted in relatively LA-rich copolymers.     

Ionic composition of TSP and PM2.5 during dust storms and air pollution episodes at Xi'an,China

TSP and PM_2.5 samples were collected at Xi'an, China during dust storms (DSs) and several types of pollution events, including haze, biomass burning, and firework displays. Aerosol mass concentrations were up to 2 times higher during the particulate matter (PM) events than on normal days (NDs), and all types of PM led to decreased visibility. Water-soluble ions (Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, F^?, Cl^?, NO₃^?, and SO₄^2?). were major aerosol components during the pollution episodes, but their concentrations were lower during DSs. NH₄⁺, K⁺, F^?, Cl^?, NO₃^?, and SO₄^2? were more abundant in PM_2.5 than TSP but the opposite was true for Mg²⁺ and Ca²⁺. PM collected on hazy days was enriched with secondary species (NH₄⁺, NO₃^?, and SO₄²) while PM from straw combustion showed high K⁺ and Cl^?. Firework displays caused increases in K⁺ and also enrichments of NO₃^? relative to SO₄^2?. During DSs, the concentrations of secondary aerosol components were low, but Ca²⁺ was abundant. Ion balance calculations indicate that PM from haze and straw combustion was acidic while the DSs samples were alkaline and the fireworks' PM was close to neutral. Ion ratios (SO₄^2?/K⁺, NO₃^?/SO₄^2?, and Cl^?/K⁺) proved effective as indicators for different pollution episodes.     

Estrogen equivalent concentration of 13 branched para-nonylphenols in three technical mixtures by isomer-specific determination using their synthetic standards in SIM mode with GC-MS and two new diasteromeric isomers

Thirteen isomers of branched para-nonylphenols (para-NP) in three technical mixtures were isomer-specifically determined using their synthesized standards by SIM of structurally specific ions, m/z 135, 149 or 163 with GC–MS. Of the 13 isomers, four isomers, 4-(2,4-dimethylheptan-4-yl)phenol, 4-(4-methyloctan-4-yl)phenol, 4-(3-ethyl-2-methylhexan-2-yl)phenol (3E22NP) and 4-(2,3-dimethylheptan-2-yl)phenol synthesized for their determinations were first used as standard substances. The 13 isomers in the technical mixtures individually occurred at mass percent portion of more than 2%. The total mass percent portions in the mixtures from Tokyo Chemical Industry (TCI), Aldrich, and Fluka covered with 89 ± 2%, 75 ± 4% and 77 ± 2%, respectively. The abundance of 4-(3,6-dimethylheptan-3-yl)phenol in the three mixtures was the largest with 11.1 ± 2% to 9.9 ± 0.3%, while that of 4-(2-methyloctan-2-yl)phenol was the smallest with 2.9 ± 0.3% to 3.0 ± 0.2%. Additionally, structures of four new isomers of more than 1% portion present in a technical mixture were elucidated as two pairs of diastereomeric isomers: two types of 4-(3,4-dimethylheptan-4-yl)phenol (344NP) and those of 4-(3,4-dimethylheptan-3-yl)phenol (343NP). By estrogenic assay of 13 isomers with yeast estrogen screen system, the activity of 3E22NP was the highest, while that of 4-(3-methyloctan-3-yl)phenol was the least. Their relative activities to that of 3E22NP were individually calculated. Estrogenic equivalent concentrations of the three technical mixtures were predictively evaluated. The ratio of the EEC to the conventional concentration, total mass percent portions of the 13 isomers in technical mixtures were 0.208 for TCI, 0.206 for Aldrich and 0.205 for Fluka. The predicted estrogenic activity of measured concentration of para-NP in technical mixtures was approximately 5-fold greater than the measured estrogen agonist activity.     

Analysis of biomagnification of persistent organic pollutants in the aquatic food web of the Mekong Delta, South Vietnam using stable carbon and nitrogen isotopes

The present study elucidated the biomagnification profiles of persistent organic pollutants (POPs) through a tropical aquatic food web of Vietnam based on trophic characterization using stable nitrogen analysis. Various biological samples collected from the main stream of the Mekong Delta were provided for the analysis for both POPs, and stable nitrogen and carbon isotope ratios. Of the POPs analyzed, dichlorodiphenyltrichloroethane and its metabolites (DDTs) were the predominant contaminants with concentrations ranging from 0.058 to 12 ng/g wet weight, followed by polychlorinated biphenyls (PCBs) at 0.017-8.9 ng/g, chlordane compounds (CHLs) at 0.0043-0.76 ng/g, tris-4-chlorophenyl methane (TCPMe) at N.D.-0.26 ng/g, hexachlorocyclohexane isomers (HCHs) at N.D.-0.20 ng/g and hexachlorobenzene (HCB) at 0.0021-0.096 ng/g. Significant positive increases of concentrations in DDTs, CHLs, and TCPMe against the stable nitrogen ratio (delta(15)N) were detected, while, concentrations of HCHs and HCB showed no significant increase. The slopes of the regression equations between the log-transformed concentrations of these POPs and delta(15)N were used as indices of biomagnification. The slopes of the POPs for which positive biomagnification was detected ranged from 0.149 to 0.177 on a wet weight basis. The slopes of DDTs and CHLs were less than those reported for a marine food web of the Arctic Ocean, indicating that less biomagnification had occurred in the tropical food web. Of the isomers of CHLs, unlike the studies of the Arctic Ocean, oxychlordane did not undergo significant biomagnification through the food web of the Mekong Delta. This difference is considered to be due to a lack of marine mammals, which might metabolize cis- and trans-chlordane to oxychlordane, in the Mekong Delta ecosystem. The biomagnification profile of TCPMe is reported for the first time in the present study.     

An Integrated Assessment by Models for Energy Systems Analysis and Life-Cycle Assessment with a Case Study of Advanced Fossil-Fired Power Plants in China

We developed an integrated assessment (IA) using models for energy systems analysis and life-cycle assessment (LCA). Based on this assessment framework, we developed cost-benefit analysis (CBA) case studies for a hypothetical project designed to introduce advanced fossil-fired power generation technologies in China. Our MARKAL model for Japan confirmed that radical reductions (i.e., 80 % by 2050) of carbon dioxide (CO₂) could be attained from energy systems alone and that credit for emission allowances was required. We evaluated life-cycle costs and emissions of carbon dioxide, sulfur oxide, and nitrogen oxide gases for the energy technologies using an LCA model. Further, we applied a power generation planning model for six Chinese grids to provide a power mix structure, potentially producing credit by installing fossil-fired power generation technology and by using baseline grid emission factors with an average cost of electricity. Finally, by using dynamic emission reductions and additional costs from the two models, we conducted case studies of CBA for a hypothetical project to install the technologies in China. This was accomplished by evaluating emission reductions in monetary terms and by applying a life-cycle impact assessment model. A unique feature of our IA is its dynamic (time-varying) assessment of costs and benefits.     

Utilization of Triacetylcellulose Waste for the Production of Carbonaceous Adsorbents

Triacetylcellulose(TAC)-based globular activated carbons having the adsorption capacity comparable with commercial ones have been derived using a carbonization system developed for this purpose. The carbonization of TAC proceeds through a liquid phase causing bubbling due to the emission of the decomposition gases. The phosphorus compounds resulting from the starting material of TAC waste promote the activation reactions to produce micro-pores.     

Improvement of thermal hydrolysis rate of dichloroacetic acid using alcohol

Dichloroacetic acid (DCAA) is produced during the oxidation of trichloroethylene. It is also produced in drinking water treatment as a disinfection by-product. DCAA is a problem material, because of its toxicity. The objective of this research is to find the final products and the reaction pathway of the DCAA decomposition by hydrolysis, and to increase the hydrolysis rate. The removal of both chlorine atoms in DCAA structure was achieved with hydrolysis at around 75 degrees C, and the final products were oxalic acid and glycolic acid. The reaction pathway was the production of oxalic acid and glycolic acid from two glyoxylic acid molecules by Cannizzaro reaction after the glyoxylic acid production from dechlorination of DCAA with hydrolysis. The hydrolysis rate of DCAA was increased with the use of 90% ethanol solution as solvent. The activation energy of DCAA was about 80 kJ/mol in it, while it was around 105 kJ/mol in water.     

Regionalization of Municipal Solid Waste Management in Japan: Balancing the Proximity Principle with Economic Efficiency

The proximity principle—disposing of waste close to its origin—has been a central value in municipal solid waste (MSW) management in Japan for the last 30 years and its widespread adoption has helped resolve numerous “Not in My Backyard” issues related to MSW management. However, MSW management costs have soared, in large part because of aggressive recycling efforts and because most MSW is incinerated in a country that has scarce landfill capacity. In addition, smaller, less sophisticated incinerators have been closed because of high dioxin emissions. Rising costs combined with the closure of smaller incinerators have shifted MSW management policy toward regionalization, which is the sharing of waste management facilities across municipalities. Despite the increased use of regionalized MSW facilities, the proximity principle remains the central value in Japanese MSW management. Municipal solid waste management has become increasingly regionalized in the United States, too, but different driving forces are at work in these two countries. The transition to regionalized MSW management in Japan results from strong governmental control at all levels, with the central government providing funds and policy direction and prefectures and municipalities being the primary implementing authorities. By contrast, market forces are a much stronger force with US MSW management, where local governments—with state government oversight—have primary responsibility for MSW management. We describe recent changes in Japan’s MSW programs. We examine the connections between MSW facility regionalization, on the one hand, and, on the other hand, the proximity principle, coordination among local governments, central government control, and financing mechanisms.     

Polycyclic aromatic hydrocarbons (PAHs) in the aerosol in Beijing, China, measured by aminopropylsilane chemically-bonded stationary-phase column chromatography and HPLC/fluorescence detection

We developed a useful analytical method for the determination of polycyclic aromatic hydrocarbons (PAH) concentrations in the aerosol of China. We used an accelerated solvent extraction (ASE) method for the extraction of PAHs from the aerosol samples, in order to reduce the extraction time and the solvent volume used. The optimum purification method was developed, with aminopropylsilane chemically-bonded stationary-phase column chromatography, in order to remove many co-extractives which cannot be removed by conventional purification methods using silica-gel column chromatography. HPLC/fluorescence detection (FLD) was adopted as the analytical method, because it has very high sensitivity to PAH and it is easy to install, operate, and maintain as compared with GC/MS. With the analytical method developed in this study, the recovery and precision (RSD) for most of the PAHs ranged from 75% to 129% and from 2.8% to 22.7%, respectively. The concentrations of PAHs in the aerosol samples collected from October 2003 to April 2005 in Beijing, China were determined using the newly developed method. SigmaPAHs, which is the sum of the concentrations of all detected PAHs, was 177.8 +/- 239.9 ng m(-3) (n = 64). The SigmaPAHs concentration in the heating season (305.1 +/- 279.0 ng m(-3), n = 33) was 7.2 times higher than that in the non-heating season (42.3 +/- 32.0 ng m(-3), n = 31). These strong seasonal variations in atmospheric PAH concentration are possibly due to coal combustion for residential heating in winter.     

Microwave enhanced stabilization of copper in artificially contaminated soil

Microwave processing was used to stabilize copper ions in soil samples. Its effects on the stabilization efficiency were studied as a function of additive, microwave power, process time, and reaction atmosphere. The stabilization efficiency of the microwave process was evaluated based on the results of the toxicity characteristic leaching procedure (TCLP) test. The results showed that the optimal experimental condition contained a 700W microwave power, 20 min process time and 3 iron wires as the additive, and that the highest stabilization efficiency level was more than 70%. In addition, the different reaction atmospheres showed no apparent effect on the stabilization efficiency of copper in the artificially contaminated soil. According to the result of the Tessier sequential extraction, the partial species of copper in the contaminated soil was deduced to transform from unstable species to stable states after the microwave process.