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.     

A comparison of concentration ratios for technetium and nutrient uptake by three plant species

Technetium (Tc) is a non-essential element for which accumulation mechanisms in plants have recently been discussed, but only from the viewpoint of existence of anion transport proteins in plant cells. In this study, using three kinds of plants (Cucumis sativus L., Raphanus sativus L., and Brassica chinensis L.), uptake of Tc and Re (a chemical analogue of Tc) were observed. The results showed that Tc and Re uptake occurred not only with water mass flow or active nutrient uptake, but also with uptake of nutrient cations such as K+. It is suggested here that most stable chemical form under aerobic conditions, TcO4-, is used in cation transport as a substitute ions, such as Cl-. After TcO4- passes through a root surface, it moves through the xylem together with cations. Due to these uptake mechanisms, Tc is highly accumulated in plants.     

Isoprene emission from tropical trees in Okinawa Island, Japan

This study surveyed isoprene emission from 42 indigenous and exotic tropical trees in subtropic Okinawa, Japan. Of the 42 trees studied, 4 emitted isoprene at a rate in excess of 20 μg g⁻¹ h⁻¹, and 28 showed the rates of 1–10 μg g⁻¹ h⁻¹. The remainder emitted less than 1 μg g⁻¹ h⁻¹. The majority of trees in this study may therefore fall within the lower emitting species. However, species in Moraceae that is indigenous in Okinawa emitted isoprene at relatively higher rates with an average of 14.2 μg g⁻¹ h⁻¹. The highest emission rate of 107.1 μg g⁻¹ h⁻¹ for Ficus virgata yielded the area basis rate of 47.4 nmol m⁻² s⁻¹, which is almost equivalent to the rate of high emitting species. Furthermore, a linear relationship between light intensity and isoprene emission was noted with Ficus virgata up to 1700 μmol m⁻² s⁻¹. These findings may show the potential importance of subtropical areas as sources of isoprene to the atmosphere.     

Effect of phosphate addition on the sorption-desorption reaction of selenium in Japanese agricultural soils

Desorption levels of soil-sorbed selenium (Se) were studied by adding phosphate to 22 typical Japanese agricultural soils. Soil-soil solution distribution coefficients of Se (Kd-Se) were measured using a batch process as an index of Se sorption level, adding 75Se as a tracer. After the Kd measurement, extraction of soil-sorbed 75Se with a 0.1 M or 1 M Na2HPO4 solution followed to determine the amount of 75Se desorbed by the phosphate. When the 0.1 M Na2HPO4 solution was used, 18-70% of soil-sorbed Se was extracted (average: 47%). However, when the 1 M Na2HPO4 solution was used, 27-83% of soil-sorbed Se was extracted (average: 57%). The observed 75Se desorption percentage indicated the maximum Se removability by phosphate addition. The desorption percentage of Se with 1 M Na2HPO4 correlated with Kd-Se values, suggesting that the soil sample with higher Kd-Se contained more reactive components for phosphate-sorption than the soil sample with lower Kd-Se. To evaluate the effect of phosphate concentration on the Se sorption, the Kd-Se was measured for two typical soils under different levels of phosphate (0.1-10 mM PO4). The Kd values were decreased by phosphate addition for both soils. The Kd decrease was observed even for just 1 mM PO4. The phosphate addition with 1 mM PO4 is the same level as in P fertilizer applied to paddy fields in Japan. Therefore, it was suggested that Se desorption should occur in Japanese soils due to the phosphate input.     

Diet-induced chemical phytomimesis by twig-like caterpillars of Biston robustum Butler (Lepidoptera: Geometridae)

Summary. Polyphagous caterpillars of the giant geometer Biston robustum resemble the twigs of their respective food sources in color and shape. Common predatory ants, including Lasius and Formica, were often observed to freely prowl directly on caterpillars bodies, even after antennal contact. This suggests that the cuticular chemicals of the caterpillars resemble those of the twigs of the foodplants, so we analyzed both by GC and GC-MS. The chemical compositions differed among caterpillars fed on a cherry, Prunus yedoensis, a chinquapin Castanopsis cuspidata, and a camellia Camellia japonica. The cuticular chemicals of the caterpillars resembled those of their corresponding food sources. When the caterpillar diets were switched from the cherry to camellia or chinquapin at the 4^th instars, the caterpillars cuticular chemicals changed after molting to resemble those of their respective foods. Caterpillars also changed their cuticular chemicals when they perched on cherry twigs and fed on camellia or chinquapin leaves, but not when they perched on camellia or chinquapin twigs and fed on cherry leaves. The chemical similarities between the caterpillars and the twigs were due to the digestion of host leaves, which indicates that this is a diet-induced adaptation.     

T cell-derived IL-5 production is a sensitive target of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)

The immune system is one of the organs most vulnerable to the toxicity of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). Among the various immunotoxic effects of TCDD, the thymus involution and suppression of IgM antibody production are well known sensitive reactions of the thymocytes and B cells affected by TCDD. Recently, we reported that TCDD greatly inhibits the production of type-2 helper T (Th2) cell-derived cytokines, especially IL-5, by the splenocytes in mice immunized with ovalbumin (OVA). In the present study, we investigated the dose-dependency of these TCDD immunotoxic effects in OVA-immunized mice to identify the most sensitive target. Mice of two age groups, 6 weeks old and 3 weeks old, were dosed with 0.3, 1.0, or 3.0 microg TCDD/kg and immunized with OVA using alum as an adjuvant. Seven days later, the thymus weight, thymocyte population, antigen-specific IgM in the plasma, and IL-5 production by the splenocytes were examined. Among them, IL-5 production was significantly suppressed by all three doses of TCDD and reduced to about 30% by even a small dose of 0.3 microg TCDD/kg in both age groups. The thymus weight was significantly reduced by 1.0 microg or 3.0 microg TCDD/kg, but IgM production was not affected by up to 3.0 microg/kg of TCDD in both age groups. Taken together, the Th2 cell-derived IL-5 production was the most sensitive endpoint detecting TCDD toxicity among those examined. Our results also suggest that effector T cells are targets more vulnerable to TCDD toxicity than thymocytes or antibody-producing B cells in the OVA-immunized mice.     

Behavior of dioxin during thermal remediation in the zone combustion process

In the previous study, a new process concept for the thermal remediation of particulate/powder materials contaminated by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) has been verified. It leads to removal efficiencies of more than 99.9% in the soil contaminated by PCDD/Fs in terms of toxicity equivalent quantity (TEQ). However, details of the reactions and phenomena during the process, i.e., decomposition, vaporization, reformation and trap of PCDD/Fs and their relating compounds, have not sufficiently been clarified yet. The present study aims to examine experimentally the transport and fate of PCDD/Fs in the process. In the experiment, a laboratory-scale process simulator and a soil sample preliminary mixed with octachlorinated dibenzo-p-dioxin spiked by carbon-13 isotope (13C-OCDD) were used. The distribution of 13C-OCDD in the soil bed during the process was measured by applying a quench technique that rapidly cools-down the bed. Further, the total amount of 13C-OCDD discharged with outlet gas was measured. Using the obtained data, mass balance of 13C-OCDD in the process was estimated. The results show that about 99% of 13C-OCDD preliminary admixed with the soil was decomposed rather than released to the outlet gas. Only a trace amount of 13C-OCDD remained in the treated soil. In addition, a very small amount of other congeners having the 13C-cycles was detected in the treated soil and outlet gas although its TEQ values are not significant. These were probably formed by dechlorination reactions occurring in the process.     

Formation behavior of PCDD/Fs in PVC pyrolysis with copper oxide

Formation and decomposition behaviors of PCDD/Fs during pyrolysis of polyvinyl chloride (PVC) with CuO have been investigated. These reactions proceed simultaneously, and the rate of decomposition exceeds that of formation with further retention. More 2,3,7,8-TCDD is formed when the dechlorination of PCDD/Fs proceeds significantly. Homologue profile patterns of PCDD/Fs show that the fractions of O8CDD and H6CDFs are relatively larger within PCDDs and PCDFs, respectively. Extremely large amounts of PCDD/Fs are obtained with the long retention time at 200 degrees C. The formation of PCDD/Fs decreases drastically with increase in the molar ratio of CuO/PVC. The acceptability of thermodynamic calculations on the formation of PCDD/Fs is also investigated. The thermodynamic calculated tendency of the effect of oxygen on the formation of PCDD/Fs agrees well with the experimental results, although absolute values of the amount of PCDD/Fs are much different.