Feedstock recycling of waste polymeric material

The first International Symposium on Feedstock Recycling of Polymeric Materials (ISFR) was hosted in 1999 in Sendai, Japan. Since then, the ISFR has been held five times in different places in Asia and Europe. Each of these conferences focused on special issues covered by the Journal of Material Cycles and Waste Management. The topics included thermal processes with and without catalysts, wet processes in various solvents, the dehydrochlorination of PVC, mechanical recycling and separation techniques, as well as the treatment of biomaterials. This review is a compilation of the most interesting and important developments discussed at the ISFR during the last decade.     

Developments in an industry-led R&D program for recycling PVC products in Japan

To facilitate recycling, not only R&D but also the creation of efficient recycling systems—collection and processing of recyclates as well as finding appropriate end-uses—is essentially important. PVC has a particular advantage in regards to mechanical recycling when compared to other major plastics. However, there is no one-size-fits-all approach to a solution. Specific situations of used or off-cut products and their applications need to be well studied. Vinyl industry in Japan has devoted itself for many years to the promotion of recycling of vinyl products. It started an R&D support program in 2007 and seven projects have been completed since then. Some of the new developments include mechanical recycling for products like wall covering and tarpaulin which were considered difficult to recycle in the past. Progress in chemical recycling has been made with a technology for the removal of chlorine from shredder dusts. Recovery of chlorine is a challenge for the future. Collaboration among the various players involved in the recycling of a specific product is essential for obtaining a successful result.     

Nucleophilic substitution of poly(vinyl chloride) with iminoacetic acid and n-dodecanethiol

The modification of poly(vinyl chloride) was carried out with iminodiacetic acid (IDA, C₄H₇NO₄) and iminodiacetic acid dimethylester (IDADM, C₆H₁₁NO₄), as well as with n-dodecanethiol (DT, C₁₂H₂₆S) in the presence of K₂CO₃. The reaction was carried out at different temperatures below 100 °C with dimethyl formamide (DMF) and cyclohexanone as solvents. IDA did not show any reactivity, probably due to the dipolar character of the molecule. IDADM caused the elimination of HCl, while only substitution ratios of about 3 % were observed. However, the modification of PVC with DT resulted in a substitution rate of 18 % without elimination. DT-PVC showed excellent thermal properties, comparable with those of the unmodified polymer.     

Distribution and binding pattern of benzo(a)pyrene in rat liver,lung and kidney constituents after oral administration

Orally administered ³H‐benzo(a)pyrene (BP) was persistent in protein fraction of liver, lung and kidney. The radioactivity in this fraction increased with time after administration and accounted for about 50%, 40% and 65% of total radioactivity in liver, lung and kidney, respectively at 48 hr. The BP metabolites binding proteins were located in cytosol and had molecular weights of 40,000–60,000 and 80,000–100,000 as determined by gel filtration and polyacrylamide gel disc electrophoresis. In addition, at 48hr after administration, about 80% of radioactivity in high molecular weight protein fraction was found to be precipitated by trichloroacetic acid treatment.

These results suggest that BP metabolites might be transported by and are persistent in these protein fractions of liver, lung and kidney if the intake of BP is continuous. These proteins, therefore, appeared to be closely related to cell toxicity or mutagenicity in these organs as well as DNA.     

Odd-numbered perfluorocarboxylates predominate over perfluorooctanoic acid in serum samples from Japan, Korea and Vietnam

Perfluorooctanoic acid (PFOA) has recently attracted attention as a potential health risk following environmental contamination. However, information detailing exposure to perfluorinated carboxylic acids (PFCAs) other than PFOA is limited. We measured the concentrations of PFCAs (from perfluorohexanoic acid to perfluorotetradecanoic acid) in serum samples obtained from patients in Japan (Sendai, Takayama, Kyoto and Osaka) between 2002 and 2009, Korea (Busan and Seoul) between 1994 and 2008 and Vietnam (Hanoi) in 2007/2008. Total PFCA levels (geometric mean) were increased from 8.9 ng mL(-1) to 10.3 ng mL(-1) in Japan; from 7.0 ng mL(-1) to 9.2 ng mL(-1) in Korea; and were estimated at 4.7 ng mL(-1) in Vietnam. PFCAs of greater length than PFOA were significantly increased in Sendai, Takayama and Kyoto, Japan, and levels of long-chain PFCAs exceeded PFOA levels in serum. Among these PFCAs, perfluoroundecanoic acid (PFUnDA) was the predominant component (28.5%), followed by perfluorononanoic acid (PFNA 17.5%), perfluorodecanoic acid (PFDA 7.9%), perfluorotridecanoic acid (PFTrDA 6.1%) and perfluorododecanoic acid (PFDoDA 1.8%). Odd-numbered PFCAs (PFNA, PFUnDA and PFTrDA) were also observed in Korea and Vietnam and their presence increased significantly in Korea between 1994 and 2007/2008. The proportion of long-chain PFCAs in serum was relatively high compared to reports in Western countries. Further investigations into the sources and exposure routes are needed to predict the future trajectory of these serum PFCA levels.     

Historical trends in human dietary intakes of endosulfan and toxaphene in China, Korea and Japan

Recently, the Stockholm Convention prohibited the use of toxaphene and has been reviewing endosulfan. The historical use of these pesticides may contaminate food and tend to accumulate in the food chain. In this study, to evaluate the spatial and temporal trends of food contamination, the endosulfan and toxaphene levels were measured in pooled 24-h food composite samples from Chinese (n = 10), Korean (n = 10) and Japanese (n = 40) adults in the 1990s and 2007-2009. Endosulfan was detected in 32 of 40 samples from Japan, but its levels (sum of α- and β-isomers) were low in both the 1990s and 2009 (range as geometric mean (geometric standard deviation) [GM (GSD)]: 0.96 (1.6)-1.42 (1.4) ng kg⁻¹ d⁻¹). The dietary intakes of endosulfan in Seoul as GM (GSD) were 38.68 (1.3) ng kg bw⁻¹ d⁻¹ in 1994 and 92.17 (4.4) ng kg bw⁻¹ d⁻¹ in 2007, and significantly higher than those in Japan (p < 0.05). The samples from Beijing showed a 50-fold increase in the endosulfan levels from 1993 (GM: 0.58 ng kg⁻¹ d⁻¹) to 2009 (GM: 24.91 ng kg bw⁻¹ d⁻¹) (p < 0.05). Toxaphene was detected in 33 of 40 samples from Japan. The dietary intake of toxaphene in Japan (sum of Parlars #26, #50 and #62) was 0.32-1.21 ng kg bw⁻¹ d⁻¹ (range as geometric mean) and no temporal trend was observed. The dietary intake of toxaphene in Seoul increased significantly from 0.2 ng kg bw⁻¹ d⁻¹ (GM) in 1994 to 3.6 ng kg bw⁻¹ d⁻¹ (GM) in 2007 (p < 0.05). Only one of 10 pooled samples from Beijing contained a detectable level of toxaphene (0.3 ng kg bw⁻¹ d⁻¹). For the entire population, the risk of adverse health effects from dietary intakes of endosulfan and toxaphene is unlikely. However, the concentrations of endosulfan in several samples exceeded 10% of the acceptable daily intake limit value of 6 μg kg bw⁻¹ d⁻¹ set by the World Health Organization (WHO). It appears important to refine dietary intake estimates targeting food types and source identification to ensure safe food for consumers.     

依据经济水平建立的华中-华南粮食运输模型

从中国土地利用现状出发,根据目前的中国粮食生产、粮食需求关系和地区经济水平差异等因素,建立了粮食调拨运输模型--计划经济型(非市场原理型)和市场原理型(自由购买型)。并将这两种模型分别应用到中国华中-华南地区,讨论了中国华中-华南地区的粮食储备变化特点。模拟结果显示:非市场原理型运输模型中,随着粮食运输强度系数的增大,城市地区的粮食不足现象逐步得到缓解;而粮食产地的粮食储量也将相应减少,粮食分布的区域不平衡不会长期存在。依据市场原理型运输模型,随着粮食吸收系数的增大,粮食储备迅速集中到沿海城市,此后粮食生产地区的粮食储备开始减少,内陆地区会出现大范围的粮食短缺现象。这种粮食分布的区域不平衡现象越来越大。     

Removal of chloride from ethylene glycol solution using alumina/zeolite membrane as a physical boundary between the organic and aqueous phases

The permeation of Cl^? ions from a NaCl/ethylene glycol (EG) solution during electrodialysis was investigated using alumina and alumina/zeolite membranes. Voltage changes had very little effect on Cl^? permeation through the alumina membrane, suggesting that the driving force for the permeation was concentration-gradient-induced diffusion, and not the electric field. Solvation of the Na⁺ ions by EG resulted in EG migration through the membrane. Replacement of the deionized water (electrolyte) in the anodic cell with NaOH resulted in increased Cl^? permeation, although a greater amount of EG migrated into the NaOH solution as well. No notable difference was observed in Cl^? permeation through the alumina and alumina/zeolite membranes, but EG migration decreased when using the latter membrane, suggesting that EG migration was prevented by the zeolite layer. The proposed alumina/zeolite membrane is, hence, useful for solvent recovery by electrodialysis, but its mechanical stability must be improved for industrial applications.