Formation and transport of PCDD/Fs in the packed bed of soil containing organic chloride during a thermal remediation process

The authors previously proposed the concept of a new thermal remediation process for particulate/powder materials contaminated by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and experimentally verified its validity on the basis of process efficiency. However, contaminees such as soils and fly ashes from waste incinerators often contain a considerable amount of other chlorides, which may act as a main source of chlorine in the formation of PCDD/Fs via thermal processes. The present study aims to examine the formation and transport of PCDD/Fs in the packed bed of soil containing a chloride during the process. Polyvinyl chloride (PVC) polymer was mixed with soil sample as an organic chloride model. A laboratory-scale apparatus was employed as a process simulator. Further, a technique to quench the process was applied to observe the concentration distribution of PCDD/Fs in the solid bed in the vertical direction. The result shows that the PCDFs tend to form dominantly in the high temperature (calcination and/or combustion) zone and are successively trapped in the low temperature (wet) zone. Especially, TeCDF is the most dominant homologue contained in the wet zone and outlet gas. Although PCDD/Fs are once trapped at the wet zone, the concentration of the remediated materials gives fairly low value (1.9 pg/g-dry, 0.04 pg-TEQ/g-dry). It signifies that organic chlorides mingled in the solid contaminee not affect the removal efficiency of PCDD/Fs in the process. Nevertheless, attention should be paid to the potential emission of PCDD/Fs in the outlet gas due to the presence of organic chloride in the soil.     

Photodegradation of tetraphenyltin contained in polychlorinated biphenyl-based transformer oil simulants in alkaline 2-propanol solution

The photodegradation of tetraphenyltin (TePT) contained in polychlorinated biphenyl (PCB)-based transformer oil simulants by ultraviolet (UV) irradiation in alkaline 2-propanol solutions was examined. In the absence of PCBs, the TePT level fell to below 1% of the initial concentration within 30 min. In the absence of both PCBs and an alkali, the concentrations of tri-, di-, and monophenyltins initially increased to a few milligrams per liter, and then reduced to below the detection limits within 90 min. The addition of an alkali to the reaction solution slightly accelerated the photodecomposition of TePT. The decomposition of other phenyltins (PTs) was also accelerated. When PCBs with concentrations of approximately 80 times the initial TePT concentration were added, only a small fraction of the TePT decomposed within 100 min. Moreover, the levels of PTs did not change during irradiation. TePT and other PTs did decompose when the level of PCBs was reduced to the same concentration as that of TePT; however, the decomposition rates were slower than those in the absence of PCBs. In the actual treatment process, TePT and other PTs in PCB-based transformer oil are decomposed by catalytic reduction, which is used after UV irradiation. Therefore, in the actual treatment of PCB-based transformer oil wastes, pollution due to PTs can be prevented.     

Field monitoring of volatile organic compounds using passive air samplers in an industrial city in Japan

Highly portable, sensitive, and selective passive air samplers were used to investigate ambient volatile organic compound (VOC) levels at multiple sampling sites in an industrial city, Fuji, Japan. We determined the spatial distributions of 27 species of VOCs in three campaigns: Mar (cold season), May (warm season), and Nov (mild season) of 2004. In all campaigns, toluene (geometric mean concentration, 14.0microg/m3) was the most abundant VOC, followed by acetaldehyde (4.76microg/m3), and formaldehyde (2.58microg/m3). The spatial distributions for certain VOCs showed characteristic patterns: high concentrations of benzene and formaldehyde were typically found along major roads, whereas high concentrations of toluene and tetrachloroethylene (PCE) were usually found near factories. The spatial distribution of PCE observed was extremely consistent with the diffusion pattern calculated from Pollutant Release and Transfer Register data and meteorological data, indicated that passive air samplers are useful for determining the sources and distributions of ambient VOCs.     

Congener-specific analysis of non-dioxin-like polychlorinated biphenyls in blood collected from 127 elderly residents in Nakagawa Town, Fukuoka Prefecture, Japan

We conducted congener-specific analysis of non-dioxin-like polychlorinated biphenyls (non-dioxin-like PCBs) in blood collected in February 2004 from 127 elderly residents living in Nakagawa Town, Fukuoka Prefecture, Japan. The present study is one of the few studies in which 56 non-dioxin-like PCBs congeners were measured in human blood. Of the 127 elderly residents, 51 were men (mean: 68.1 years) and 76 were women (mean: 68.1 years). Among 197 non-dioxin-like PCB congeners, 56 were identified in the blood of elderly residents. The arithmetic mean total concentrations of 56 non-dioxin-like PCBs congeners in the blood of elderly men and women in Nakagawa Town were 419 (median: 378) and 363 (median: 323)ngg(-1)lipid, respectively, and the concentrations were in the range of 172-1102 and 119-1226ngg(-1)lipid, respectively, indicating that the total concentrations in elderly men are significantly higher than those in elderly women. The contamination of non-dioxin-like PCBs in the blood of elderly men and women in Fukuoka Prefecture was found to have decreased compared to past levels. The ratios of hexachlorinated biphenyls (hexaCBs) to the total concentrations of 56 non-dioxin-like PCBs congeners in the blood of elderly men and women were 44.6% and 45.6%, respectively, which was particularly high compared with those of other congeners. 2,2',4,4',5,5'-HexaCB (#153) among hexaCBs congeners, the most abundant congener in the blood of elderly men and women, contributed approximately 23.0% and 23.5% to the total concentrations of 56 non-dioxin-like PCBs congeners, respectively. Furthermore, 2,2',3,4,4',5'-hexaCB (#138), 2,3,3',4',5,6-hexaCB (#163)/2,3,3',4',5',6-hexaCB (#164), 2,2',3,4,4',5,5'-heptaCB (#180), and 2,2',3,4,4',5,6'-heptaCB (#182)/2,2',3,4',5,5',6-heptaCB (#187) also showed high ratios to the total concentrations of 56 non-dioxin-like PCBs congeners detected in the blood of elderly men and women. A statistical examination of the relationship between the total concentrations of 56 non-dioxin-like PCBs congeners in blood and the age of elderly residents who were over 60 years indicated statistically significant correlations between the total concentrations of these PCBs congeners and the age of elderly women. However, similar correlations were not observed in elderly men. The results of the present study have indicated the current levels of non-dioxin-like PCBs in the blood of elderly men and women in Fukuoka Prefecture, Japan and can be used as baseline data for those over age 60.     

Application of a Larval Medaka Assay to Evaluate the Fish Safety Level in Sagami River, Japan

Physico-chemical characteristics of some river and hand-dug well waters used for drinking and domestic purposes in the oil rich Niger Delta area of Nigeria were assessed using standard methods. The concentrations of the parameters in the river water samples ranged in the following order: pH (5.6–6.9), temperature (26.90–28.60°C), turbidity (23–63 NTU), electrical conductivity (52–184 μs/cm), DO (5.4–7.2 mg/l), BOD (21–57 mg/l), TDS (6.0–217 mg/l), PO₄ ³⁻ (0.19–1.72 mg/l), SO₄ ²⁻ (25–36.8 mg/l), NO₃ ⁻ (20.3–28 mg/l), Fe (6.07–15.71 mg/l), Zn (0.04–0.24 mg/l), Pb (0.01–0.17 mg/l), Ni (0.01–0.13 mg/l), Vn (0.01–0.20 mg/l) and Hg (0.001–0.002 mg/l). The concentrations of these parameters in the hand-dug well water ranged in the following order: pH (5.7–6.8) temperature (26–30°C), turbidity (134–171 NTU), electrical conductivity (160–340 μs/cm), DO (5.4–6.4 mg/l), BOD (13–34 mg/l), TDS (110–190 mg/l), PO₄ ³⁻ (0.84–1.84 mg/l), SO₄ ²⁻ (10.6–28.1 mg/l), NO₃ ⁻ (11.3–23 mg/l), Fe (13.17–16.31 mg/l), Ni (0.01–0.02 mg/l), Vn (0.01–0.04 mg/l) and Hg (0.001–0.004 mg/l). The concentrations of BOD, turbidity, NO₃ ⁻ and Fe in the water samples were above WHO and FMENV permissible limits for safe drinking water. The results suggest that the use of such waters for drinking and domestic purposes pose a serious threat to the health of the users and calls for the intervention of government agencies.     

Gene expression profiles in the testis associated with testis-ova in adult Japanese medaka (Oryziaslatipes) exposed to 17α-ethinylestradiol

The occurrence of oocytes in the testis (testis-ova) of several fish species is often associated with exposure of estrogenic chemicals. However, induction mechanisms of the testis-ova remain to be elucidated. To develop marker genes for detecting testis-ova in the testis, adult male medaka were exposed to nominal concentration of 100 ng L⁻¹ of 17α-ethinylestradiol (EE2) for 3-5 weeks, and 800 ng estradiol benzoate (EB) for 3 weeks (experiment I), and a measured concentration of 20 ng L⁻¹ EE2 for 1-6 weeks (experiment II). Histological analysis was performed for the testis, and microarray analyses were performed for the testis, liver and brain. Microarray analysis in the estrogen-exposed medaka liver showed vitellogenin and choriogenin as estrogen responsive genes. Testis-ova were induced in the testis after 4 weeks of exposure to 100 ng L⁻¹ EE2, 3 weeks of exposure to 800 ng EB, and 6 weeks of exposure to 20 ng L⁻¹ EE2. Microarray analysis of estrogen-exposed testes revealed up-regulation of genes related to zona pellucida (ZP) and the oocytes marker gene, 42Sp50. Using quantitative RT-PCR we confirmed that Zpc5 gene can be used as a marker for the detection of testis-ova in male medaka.     

Evaluating the fish safety level of river water and wastewater with a larval medaka assay

A larval medaka (Oryzias latipes) assay was proposed to evaluate the fish safety level of river waters and wastewaters. Organic toxicants were 10-100 times concentrated with adsorption cartridges from 4 l of river water or 1-10 times concentrated from 400 ml of wastewater. Toxicity of these concentrated solutions was determined by exposing 48-72 h post-hatch age larvae for 48 h. The method effectively revealed a variation of the median lethal concentration ratio (LCR50) from 13 to >100 in 125 river water samples, and from <1 to >10 in five typical wastewater samples. Ayase River, which takes water mostly from agricultural or household discharge, showed significantly (P<0.001) lower LCR50 than Sagami River that takes natural water as the source. Safety Levels in both Sagami River and Ayase River were influenced by the irrigation activity, LCR50 at some sites showing a seasonal-specific decrease in winter. Pollution from pulp and paper industries contributed to the low LCR50 in several tributaries of Ayase River. Required little manpower in sampling, pretreatment and testing, the proposed larval medaka assay was proved as an efficient tool for screening those high risk sites for priority management.     

Development of supercritical carbon dioxide extraction with a solid phase trap for dioxins in soils and sediments

A method involving supercritical fluid extraction (SFE) with a solid phase trap containing activated alumina was investigated for the rapid analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin like polychlorinated biphenyls (DL-PCBs) in soils and sediments. The samples were extracted by using supercritical carbon dioxide with water (2% versus CO(2) flow velocity) being used as an entrainer at a pressure of 30 MPa and a temperature of 130 degrees C for 50 min. The extracts were adsorbed on an activated alumina trap that was maintained at a temperature of 150 degrees C, and then, PCDD/DFs and DL-PCBs were eluted with 20 ml of hexane at 60 degrees C. After concentration, they were measured with a high-resolution gas chromatograph interfaced to a high-resolution mass spectrometric detector. The average concentrations of PCDD/DFs and DL-PCBs corresponded to the results obtained by the conventional method, and the reproducibility of this SFE method was below 21% of the relative standard deviations for all samples. The total time required for the analysis of the pretreatment of this method was only 2 h.