Distribution of copper,silver and gold during thermal treatment with brominated flame retardants

The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition.In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000 °C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is resistant to HBr and remains unchanged in the residue.     

Reproductive transfer of organochlorines in viviparous surfperch, Ditrema temmincki

To discuss the maternal-fetal transfer of persistent organic pollutants (POPs) in viviparous fish, the whole-body burdens of POPs were determined in gravid surfperches from Otsuchi Bay, Japan, and in their fetuses. The concentrations were 2.75-15.5 times higher in the maternal tissue. To compare the characteristics of the maternal-fetal transfer between species with different gestation systems, reports on the striped dolphin and long-finned pilot whales were studied. The transfer rates of POPs in surfperches were 0.6-6.0%, while in marine mammals they were 3.0-9.4%. The difference in transfer rates may derive from the difference in their reproductive systems. On the other hand, as in marine mammals, selective transfer of POPs was seen in surfperches. The transfer rates were higher in less hydrophobic compounds such as dieldrin, and lower in more hydrophobic compounds such as DDTs. A new transfer factor is also discussed which instantly indicates the difference in the concentrations between mother and fetus.     

Horizontal distribution of steroid estrogens in surface sediments in Tokyo Bay

A monitoring survey was conducted to investigate the distribution of steroid estrogens and their conjugates in surface sediments of Tokyo Bay for the first time, which is known as one of the most heavily polluted marine embayments in the world. The surface sediment samples were collected at 20 locations covering the whole area of Tokyo Bay and analyzed for steroid estrogens and their conjugates using liquid chromatography-tandem mass spectrometry. The concentrations of 17beta-estradiol (beta-E2) and estrone (E1) ranged from ND (below the detection limit; <0.07) to 0.59 and from 0.05 to 3.60 ng g-1 dry, respectively. Those concentrations were higher in the northern part of the bay, which is directly receiving huge quantities of pollutants from adjacent rivers containing a large amount of municipal and industrial wastewater. 17alpha-Estradiol (alpha-E2) and estrone-3-sulfate (E1-3S) were detected in some of the samples, whereas neither of the other conjugates, estriol (E3) or 17alpha-ethynylestradiol (EE2), was found.     

Time trends of perfluorinated compounds from the sediment core of Tokyo Bay, Japan (1950s-2004)

Perfluorinated compounds (PFCs) were detected in sediment core samples collected in Tokyo Bay to reveal their time trends. The core sample deposited during 1950s-2004 was divided into two- to three-year intervals and the concentrations of 24 types of PFCs were determined. Perfluorooctane sulfonate (PFOS) decreased gradually from the early 1990s and its precursor decreased rapidly in the late 1990s, whereas perfluorooctanoic acid (PFOA) increased rapidly. The observed trends were regarded as a reflection of the shift from perfluorooctyl sulfonyl fluoride (PFOSF)-based products to telomer-based products after the phaseout of PFOSF-based products in 2001. The branched isomers of perfluoroundecanoic acid (PFUnDA) and perfluorotridecanoic acid (PFTrDA) were detected in the sample with its ratio of linear-isomer/branched-isomer concentrations decreasing. In this study, we revealed that the sediment core can serve as a tool for reconstructing the past pollution trend of PFCs and can provide interesting evidence concerning their environmental dynamics and time trend.     

Relationship between growth and biochemical indices in laboratory-reared juvenile Japanese flounder (Paralichthys olivaceus), and its application to wild fish

In order to estimate growth rates based on biochemical indices of the liver of wild Japanese flounder (Paralichthys olivaceus), juveniles were reared at six ration levels (0, 0.5, 2, 4, 6 and 8% body weight day⁻¹) in the laboratory for 14 days, and the relationship between their growth rates and biochemical indices (RNA/DNA, protein/DNA, triglyceride/DNA, phospholipid/DNA and cathepsin D activities) were determined. Positive and approximately linear relationships were seen between growth rates and the indices of RNA/DNA, protein/DNA and phospholipid/DNA. The triglyceride/DNA ratio decreased with increasing growth rates up to approximately 1% body weight day⁻¹, then increased linearly with increasing growth rates. There was no significant correlation between growth rates and cathepsin D activity, and the highest values were obtained in the starved fish. Compared with laboratory-reared specimens, wild specimens of similar sizes were found to have significantly larger livers. The RNA/DNA, protein/DNA and phospholipid/DNA ratios of wild specimens fell in a broad range between ration groups of reared juveniles. The protein/DNA ratios of wild specimens were low and outside the range of the reared juveniles at six ration levels. In contrast, the levels of cathepsin D activity of wild fish were highest compared to the reared fish. Estimated growth rates of wild fish from the RNA/DNA, protein/DNA and phospholipid/DNA regressions obtained from the rearing experiment were 1.66, −1.74 and 0.10% day⁻¹, respectively. Based on our results, the RNA/DNA index may be regarded as the most valid and reliable growth estimator. It is noted that the larger liver size, the lower liver protein/DNA ratio and the unexpectedly high level of cathepsin D activities of wild specimens found in this study may reflect the different metabolic conditions of fish reared in the laboratory compared to those collected in the field. Received: 29 February 2000 / Accepted: 26 August 2000     

Applications of a hydro-biogeochemical model and long-term simulations of the effects of logging in forested watersheds

We simulated hydrological and biogeochemical responses to logging in a forested watershed to determine the vulnerability and/or resiliency of the forest ecosystems in the Lake Shumarinai Basin in northern Hokkaido, Japan. We used a biogeochemical model (PnET-CN) and a rainfall–runoff model (HYCYMODEL) to predict ecosystem responses. The PnET-CN model simulated well the observed NO₃ ⁻ concentrations in streamwater, particularly at high concentrations during snowmelt; however, the model could not simulate small increases in NO₃ ⁻ during the summer. By considering hydrological processes within the watershed and combining the model with the HYCYMODEL (PnET + HYCYMODEL), the seasonality of streamwater NO₃ ⁻ concentrations was better simulated. Using these models, the long-term effects of logging were simulated for coniferous, deciduous, and mixed forests. NO₃ ⁻ concentrations in streamwater increased in response to the logging disturbance in both coniferous and deciduous forests. In the coniferous forest, NO₃ ⁻ concentrations reached a maximum 10 years after logging, and high concentrations persisted for 30 years. In contrast, NO₃ ⁻ concentrations in the deciduous forest reached a maximum within 3–4 years and recovered to pre-disturbance levels after 15 years. We also used the models to determine the effects of different sizes and types (coniferous, deciduous, and mixed forest) of logging areas on Lake Shumarinai. The model results indicated that large areas of cutting require more than 100 years for complete lake recovery. Whereas the annual discharge to the lake minimally increased, the annual NO₃ ⁻ load greatly increased. Our simulation results elucidate the vulnerability and resiliency of forest ecosystems and provide valuable information for ecosystem management.     

Use of handheld X-ray fluorescence spectrometry units for identification of arsenic in treated wood

The objective of this study was to evaluate the performance of handheld XRF analyzers on wood that has been treated with a preservative containing arsenic. Experiments were designed to evaluate precision, detection limit, effective depth of analysis, and accuracy of the XRF arsenic readings. Results showed that the precision of the XRF improved with increased sample concentration and longer analysis times. Reported detection limits decreased with longer analysis times to values of less than 1mg/kg or 18 mg/kg, depending on the model used. The effective depth of analysis was within the top 1.2 cm and 2.0 cm of sample for wood containing natural gradients of chemical preservative and concentration extremes, respectively. XRF results were found to be 1.5-2.3 times higher than measurements from traditional laboratory analysis. Equations can be developed to convert XRF values to results which are consistent with traditional laboratory testing.     

Carbon Sequestration by Carbonization of Biomass and Forestation: Three Case Studies

We proposed the carbon sink project called “Carbon Sequestration by Forestation and Carbonization (CFC),” which involves biomass utilization and land conservation by incorporating the products of biomass carbonization into the agents for soil improvement, water purification, etc. Our purpose was to demonstrate the potential of the CFC scheme for carbon sequestration, particularly carbon storage in soil. Case studies were conducted in both developing and developed countries. 1. In southern Sumatra, Indonesia, 88,369 Mg-C year⁻¹ of wood residue from a plantation forest and excess bark from a pulp mill would be converted into 15,571 Mg-C year⁻¹ of the net carbon sink by biochar for soil improvement. The fixed carbon recovery of the system is 21.0%. 2. In a semiarid region in western Australia, the carbonization of wood residue was incorporated with multipurpose projects of a mallee eucalyptus plantation that involved the function of salinity prevention. During the project period of 35 years, the total carbon sink would reach 1,035,450 Mg-C with 14.0% by aboveground biomass, 33.1% by belowground biomass and 52.8% by biochar in soil. 3. In southern Kyushu, Japan, the study was focused on the effective use of surplus heat from a garbage incinerator for carbonizing woody materials. Sawdust of 936.0 Mg-C year⁻¹ would be converted into the net carbon sink of 298.5 Mg-C year⁻¹ by carbonization, with the fixed carbon recovery of the system being 31.9%. Consequently, the CFC project could encourage the creation of a carbon sink in soil. However, we recognize that the quality standard of biochar, the stability of biochar in soil, and the methods for monitoring biochar utilization must be clarified before incorporating biochar carbon into the carbon credit system. Throughout this article (except for diagrams and in citation details) carbonized biomass is, with the authors'agreement, called ‘biochar’ in lieu of the commonly used but misleading word ‘charcoal’ (Editor).     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in invertebrate animals from a rural beach in Japan

PCDDs and PCDFs were analyzed by high resolution GC MS in several invertebrate animals collected from a rural beach in Japan. PCDDs and PCDFs were detected in all samples. Total concentration of PCDDs and PCDFs ranged 8.8–120 pg g⁻¹ wet and 3.5–38 pg g⁻¹ wet, respectively. TEQs of invertebrate animals examined ranged from 0.048 pg g⁻¹ wet in sea slug to 0.91 pg g⁻¹ wet in mussel. Isomer profiles in all samples were similar to each other despite of variety of species. Their major sources are estimated to be herbicides such as CNP and PCP, and combustion by using a statistical analysis of isomer profiles.