Mechanochemical dechlorination of polyvinyl chloride with calcium sulfates

Polyvinyl chloride (PVC) was milled with hydrated or unhydrated calcium sulfates (CaSO₄·2H₂O or CaSO₄) in air by using a planetary mill to investigate mechanochemical dechlorination behavior. The milling process resulted in size reduction and in the breaking of bonds leading to mechanically induced solid state reaction, forming CaCl₂ and dechlorinated hydrocarbon with C=C double bonds in the product. Washing the milled mixtures with water at room temperature allowed removal of the chloride formed during milling, and more than 95% of the chlorine in PVC was removed from a mixture milled for 4 h. This process could offer a potential route for the handling and disposal of both PVC and gypsum wastes. H₂S gas was generated during milling; more H₂S was released from the unhydrated sample than from the hydrated sample.     

Effects of donor age and contamination level of dioxins and related chemicals on frequency of sister chromatid exchanges in human lymphocytes cultured in vitro

Frequencies of sister chromatid exchanges (SCEs) of human lymphocytes in control (DMSO treated) and 7,8-benzoflavone (ANF) treated cultures were measured in 39 healthy Japanese people and examined in connection with donor age. Both the control (baseline) and ANF induced SCE rates were significantly enhanced with age and highly positive correlation was observed between them. Therefore, in vivo aging seemed to have some effects on the frequencies of SCEs in human lymphocytes cultured in vitro. Concentrations of PCDDs, PCDFs and Co-PCBs in the blood and sebum of face were determined in the same Japanese subjects. Significantly positive correlation was observed between the blood and sebum in their total TEQ levels. Hence, PCDDs, PCDFs and Co-PCBs, which have been contaminating human bodies, are considered proportionally excreted from the sebum of face or body. Their total TEQ concentrations were also meaningfully increased with donor age in the sebum of face as well as in the blood. Either the baseline or ANF induced SCE frequencies was not enhanced with the total TEQ levels in the blood. Therefore, background levels of their contamination seem not to affect the SCE rates of the lymphocytes in the control and ANF treated cultures.     

Two-dimensional NMR Spectroscopy

The Science of Nature -     

PCDFs and related compounds in humans from Yusho and Yu-Cheng incidents

Mass food poisoning incidents, called Yusho and Yu-Cheng, were caused by the ingestion of rice oils which had been contaminated with polychlorinated biphenyls (PCBs), polychlorinated dibenzofurans (PCDFs) and polychlorinated quaterphenyls (PCQs). This paper reviews the formation of toxic PCDFs in the rice oil from PCBs, intakes of PCBs, PCDFs and PCQs by the patients and the behavior of PCBs, PCDFs and PCQs in the human body.     

Waste prevention for sustainable resource and waste management

Although the 2Rs (reduce and reuse) are considered high-priority approaches, there has not been enough quantitative research on effective 2R management. The purpose of this paper is to provide information obtained through the International Workshop in Kyoto, Japan, on 11–13 November 2015, which included invited experts and researchers in several countries who were in charge of 3R policies, and an additional review of 245 previous studies. It was found that, regarding policy development, the decoupling between environmental pressures and economy growth was recognized as an essential step towards a sustainable society. 3R and resource management policies, including waste prevention, will play a crucial role. Approaches using material/substance flow analyses have become sophisticated enough to describe the fate of resources and/or hazardous substances based on human activity and the environment, including the final sink. Life-cycle assessment has also been developed to evaluate waste prevention activities. Regarding target products for waste prevention, food loss is one of the waste fractions with the highest priority because its countermeasures have significant upstream and downstream effects. Persistent organic pollutants and hazardous compounds should also be taken into account in the situation where recycling activities are globally widespread for the promotion of a material-cycling society.     

Concentrations of organochlorine pollutants in mothers who gave birth to neonates with congenital hypothyroidism

We have investigated the effects of prenatal exposure to dioxin-like compounds (PCDDs, PCDFs and dioxin-like PCBs), PCBs and organochlorine pesticides (DDT, HCH, chlordane, HCB and their metabolites) on the incidence of congenital hypothyroidism and/or cretinism in Fukuoka, Japan from 2001 to 2004. Thirty-four positive neonates of the mass-screening for cretinism were classified into three groups by the pediatrician after the reevaluation of the serum TSH level, that is, negative in reevaluation group, hyper thyroid stimulating hormone (TSH) emia group and cretinism group. One-hundred and two negative neonates of the mass-screening were classified into the normal group. Concentrations of these organochlorine compounds in the breast milk of mothers, which were considered as the indicator of prenatal exposures to them, were gradually increased from the normal group to the cretinism group in the four groups and were around two times higher in the cretinism group than in the normal group. According to the case-control study adjusted for the parity and mother's age, odds ratios of PCBs, DDT and HCB were 10 (p=0.003), 10 (p=0.003) and 22 (p=0.004), respectively and in dioxin-like compounds, PCDFs showed the highest odds ratio, 9.8 (p=0.005). Based upon those findings, these compounds seemed play an important role in the incidence and/or causation of the cretinism.     

Immunologic effects of perinatal exposure to dioxins, PCBs and organochlorine pesticides in Japanese infants

Effects of perinatal exposure to dioxins, PCBs and organochlorine pesticides on lymphocyte subsets were investigated in the peripheral blood from 101 Japanese infants with approximately 10 months of age. Perinatal exposure to these organochlorine compounds were estimated by their contamination levels in the breast milk of the mothers. Lymphocyte subsets such as CD16+, HLA-DR+, CD4+, CD4+8+, CD8+, CD3+ and CD20+ cells in peripheral venous blood were assessed in a subgroup of 92 infants. Greater exposures to HCE, chlordane and dioxins were significantly associated with the increase in the percentages of CD8+ and CD3+ T lymphocytes and CD4+/CD8+ T cell ratios, respectively. In addition, higher HCH exposure was also associated with a decrease in the percentage of HLA-DR+ T lymphocytes. Furthermore effects of dioxins, DDT and PCBs on the percentage of CD16+ T lymphocyte were more pronounced by the combined exposure of dioxins and PCBs or by the combined exposure of DDT and PCBs. Effects of HCE on the percentages of CD8+ T lymphocyte were also more pronounced by the combined exposure of HCE and chlordane. In conclusion, our study suggests that greater exposures to dioxins, PCBs and organochlorine pesticides determined in this study (except dieldrin) influence the immune system of Japanese infant, although the clinical significance of these changes is uncertain.     

Correlation of PCDD/PCDF and CO values in a MSW incinerator--indication of memory effects in the high temperature/cooling section

The correlation of PCDD/PCDF levels with the CO emissions in a full-scale municipal waste incinerator was assessed during a four-week measurement effort. PCDD/PCDF concentrations in fly ashes-containing more than 99% of the total PCDD/PCDF burden of the fluidized bed incinerator (FBI)-were measured and compared with the emitted CO concentrations. The CO concentration during the sampling time showed no significant correlation to the PCDD/ PCDF amount in fly ash (R2 = 0.078). However, a comparison of the time integrated CO concentration several hours before sampling lead to a correlation with the PCDD/PCDF burden. Maximum correlation was found for the time integrated CO values of 3 and 4 h before sampling (R2 = 0.467 and R2 = 0.457 respectively). This indicates a memory effect in the high temperature cooling section of several hours. Possible mechanisms leading to the memory effect are discussed. The correlation of PCDD/PCDF with CO concentration demonstrate that the combustion conditions play an important role for PCDD/PCDF formation in FBIs. However the variability in the correlation of CO to PCDD/PCDF levels show that other factors have a significant influence on PCDD/PCDF formation.     

Impact of FEBRA (fermented brown rice with Aspergillus oryzae) intake and concentrations of PCDDs, PCDFs and PCBs in blood of humans from Japan

Impact of FEBRA (fermented brown rice with Aspergillus oryzae, a rich dietary fiber) intake on the concentrations of polychlorinated-biphenyls (PCBs), -dioxin-like polychlorinated biphenyls (DLPCBs), -dibenzo-p-dioxins (PCDDs), and -dibenzofurans (PCDFs) in blood of nine married Japanese were studied for 2 years. Concentrations of total PCBs (average+/-standard deviation) were greater 326,000+/-263,000 and 207,000+/-89,000 in FEBRA-intake and non-FEBRA-intake groups, respectively, on pg/g lipid (from now onwards data expressed on pg/g lipid). DLPCBs were second major contaminants 94,000+/-77,000 and 60,000+/-28,000, orderly in FEBRA-intake and non-FEBRA-intake groups. The concentrations of PCDD/DFs were several orders of magnitude lower than those of PCBs, whereas PCDDs were greater (433+/-233 and 512+/-511, in FEBRA-intake and non-FEBRA-intake groups, respectively) than PCDFs (56+/-50 and 43+/-35). Calculated toxic equivalency (TEQ) concentrations were 34+/-24 and 23+/-10 in FEBRA-intake and non-FEBRA-intake groups, respectively. In order to corroborate the impact of FEBRA, the changes of PCDD/DFs and PCB concentrations for 0.5-year, 1-year, 1.5-year, and 2-year samples were estimated from average concentration of 1-day before study commences and 1-week study samples. The results explicit FEBRA-intake group eliminated 7%, 33%, 45%, 36%, and 26% and non-FEBRA-intake group eliminated 8%, 28%, 36%, 31%, and 20% of DLPCBs, PCDDs, PCDFs, PCDD/DF TEQ and total TEQ, respectively. This study is the first of its kind showing the possible elimination of PCDDs, PCDFs and their TEQ in humans from Japan after the consumption of FEBRA.