Brominated flame retardants and heavy metals in automobile shredder residue (ASR) and their behavior in the melting process

The End-of-life Vehicles Recycling Act went into effect on January 1, 2005, in Japan and requires the proper treatment of airbags, chlorofluorocarbons (CFCs), and automobile shredder residue (ASR). The need for optimal treatment and recycling of ASR, in particular, has been increasing year after year because ASR is regarded as being difficult to treat. Dioxin-related compounds, brominated flame retardants (BFRs), heavy metals, chlorine and organotin compounds are all present in high concentrations in ASR. The authors conducted ASR melting treatment tests using a 10-tons/day-scale direct melting system (DMS), which employs shaft-type gasification and melting technology. The results obtained showed that dioxin-related compounds and BFRs were decomposed by this melting treatment. The high-temperature reducing atmosphere in the melting furnace moved volatile heavy metals such as lead and zinc into the fly ash where they were distributed at a rate of more than 90% of the input amount. This treatment was also found to be effective in the decomposition of organotin, with a rate of decomposition higher than 99.996% of the input amount. Via the recovery of heavy metals concentrated in the fly ash, all the products discharged from this treatment system were utilized effectively for the complete realization of an ASR recycling system that requires no final disposal sites.     

Comprehensive modeling of HFC-23 incineration in a CDM incinerator

Considering that a significant part of used refrigerants have to be destroyed in an environmentally friendly manner together with the high global warming potential (GWP) of HFCs (hydrofluorocarbons), the development of a proper incineration method of HFCs becomes one of the viable methods in the refrigeration and air-conditioning industry. To this end, in this study, the development of a comprehensive modeling of CHF₃ (HFC-23 or R-23) incineration is made to assist in the proper design and determination of optimal operating condition of a practical HFCs incinerator, since the refrigerant of CHF₃ is one of typical HFCs. For this, numerical investigation was performed by the development of a predictive model for the thermal destruction of the CHF₃ using CH₄–air flames in an incinerator designed for CDM (clean development mechanism) project. First of all, comparison between calculation and operation data was made to evaluate the program developed in this study. Numerical calculation of CHF₃–CH₄–air flame predicts successfully the operation data of a CDM incinerator such as temperature, CHF₃ destruction rate more than 99.99 % and other species concentrations such as CO and NO at the exit of the incinerator. Further parametric study was performed also in terms of important variables such as excess air, amount of steam and incinerator size. In general, the results obtained appear physically acceptable and give a clear physical insight into the role of the important variables. Further work is strongly recommended for the development of a general turbulent reaction model for the thermal destruction of HFCs, especially for the condition of non-equilibrium turbulent reaction dominance.     

Effect of Poly(l-Lactide) and Poly(Butylene Succinate) on the Growth of Red Pepper and Tomato

Seeds of red pepper and tomato were sowed and cultivated in a soil blended with powdery poly(l-lactide) (PLLA), and poly(butylene succinate) (PBS). PBS depressed the growth of the two plants significantly even at a concentration as low as 5%, whereas PLLA up to 35% affected negligibly or even boosted the growth of the two plants. pH and number of microbial cells in the soil after 80 days of cultivation were almost the same independently whether the soil was blended with the two polymers or not. In contrast, the molecular weight of PBS decreased much faster than that of PLLA. Because succinic acid and 1,4-butane diol, from which PBS was synthesized, exhibited toxicity to both plant and animal cells to retard the germination rate of young radish seeds and to deform the morphology of HeLa cells significantly [1], the monomers and the oligomers produced from the PBS degradation should have a detrimental influence on the growth of the two plants.     

Controlling the Behaviors of Biodegradable/Bioabsorbable Polymers with Cyclodextrins

The cyclic six, seven, and eight-membered oligosaccharides -, -, and -cyclodextrins (CDs) can serve as hosts for a variety of polymer guests to form crystalline inclusion compounds (ICs), wherein the guest polymers are included in the continuous narrow channels (0.5–1.0 nm in diameter) formed by the host CD stacks. Polymers included as guests in CD-ICs are highly extended and segregated from neighboring chains by the walls of the host CD bracelets. As a consequence, when polymer-CD-ICs are treated with solvents for CDs that are non-solvents for the included polymers or with amylase enzymes, the CDs are removed and the guest polymers are coalesced into bulk samples whose structures, morphologies, and even chain conformations are different from those achieved by consolidation from their randomly coiling, entangled solutions and melts. Often these CD-IC coalesced and consequently reorganized polymer samples exhibit properties that are distinct from their normally processed bulk samples. Here we describe the CD-IC processing of several biodegradable/bioabsorbable homopolymers, copolymers, and blends made from poly (L-lactic acid), poly (-caprolactone), and poly (-hydroxybutyrate)s, with special emphasis placed on their improved and controllable properties. For example, the phase segregation and consequent crystallinities of their normally incompatible homopolymer blends and their block copolymers may be controlled and thus improved. In addition, co-inclusion of small molecule guests, such as drugs or anti-bacterials, in their common CD-ICs, and subsequent coalescence, yields well-mixed blends of these biodegradable/bioabsorbable polymers and the small molecule co-guests, which may lead, for example, to the improved delivery of drugs.     

An international comparative study of end-of-life vehicle (ELV) recycling systems

End-of-life vehicles (ELV) have become a global concern as automobiles have become popular worldwide. An international workshop was held to gather data and to discuss 3R policies and ELV recycling systems, their background and present situation, outcomes of related policies and programs, the framework of recycling and waste management, and case studies on related topics in several countries and regions, as well as the essential points of the comparison. Legislative ELV recycling systems are established in the EU, Japan, Korea, and China, while in the US, ELV recycling is managed under existing laws on environmental protection. Since automobile shredding residue (ASR) has a high calorific value and ash content, and includes heavy metals as well as a mass of unclassified fine particles, recycling ASR is considered highly difficult. Countries with a legislative ELV system commonly set a target for recovery rates, with many aiming for more than 95 % recovery. In order to reach this target, higher efficiency in ASR recovery is needed, in addition to material recycling of collectable components and metals. Environmentally friendly design was considered necessary at the planning and manufacturing stages, and the development of recycling systems and techniques in line with these changes are required for sound ELV management.     

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron (NZVI) was evaluated to assess the feasibility of employing NZVI in the biological nitrate treatment. Nitrate was completely reduced within 3 d in a nanoscale Fe(0)-cell reactor, while only 50% of the nitrate was abiotically reduced over 7 d at 25 °C. The removal rate of nitrate in the integrated NZVI-cell system was unaffected by the presence of high amounts of sulfate. Efficient removal of nitrate by Fe(II)-supported anaerobic culture in 14 d indicated that Fe(II), which is produced during anaerobic iron corrosion in the Fe(0)-cell system, might act as an electron donor for nitrate. Unlike abiotic reduction, microbial reduction of nitrate was not significantly affected by low temperature conditions. This study demonstrated the potential applicability of employing NZVI iron as a source of electrons for biological nitrate reduction. Use of NZVI for microbial nitrate reduction can obviate the disadvantages associated with traditional biological denitrification, that relies on the use of organic substrates or explosive hydrogen gas, and maintain the advantages offered by nano-particle technology such as higher surface reactivity and functionality in suspensions.     

A numerical study on the seasonal variability of polychlorinated biphenyls from the atmosphere in the East China Sea

A three-dimensional/high-resolution transport model for persistent organic pollutants (POPs) has been developed for the East China Sea (ECS). The POPs model has four compartments (gaseous, dissolved, phytoplankton-bound, and detritus-bound phases) and includes processes for diffusive air-water exchange, phytoplankton uptake/depuration to POPs, decomposition of dissolved phase, vertical sinking of phytoplankton, detritus production by phytoplankton mortality, and vertical sinking and decomposition of detritus. The POPs model is coupled with an ocean circulation model that can reproduce the seasonal variation in physical variables to represent the advection and diffusion of POPs. We applied the POPs model to the polychlorinated biphenyl congener 153 (PCB 153) from the atmosphere and examined the behavior of PCB 153 in the ocean. The model showed a remarkable seasonal variability of PCB 153. Concentrations in the dissolved and particulate phases are high in winter (January-March) and low in summer (July-September). In coastal regions, where chlorophyll a concentration is high, horizontal and vertical distributions in the dissolved and particulate PCB 153 concentrations are strongly affected by phytoplankton uptake. The sensitivity experiments on the dynamics of PCB 153 suggested that a change of Henry’s law constant associated with water temperature is the major factor controlling the seasonal variability of PCB 153. The model-based yearly mass balance of PCB 153 in the ECS indicated that most of the atmospheric input (35.5 kg year⁻¹) is removed by the horizontal advection outside the ECS (19.0 kg year⁻¹) and accumulates to the sea bottom by vertical sinking (15.7 kg year⁻¹). For comparison with PCB 153, we also conducted simulations for PCB 52, 101, and 180. The seasonal variations are similar to that of PCB 153. The mass balance of PCB 52 that has short half-life time and less hydrophobic property shows the different results compared with PCB 101, 153, and 180.     

Persistent organochlorines in human breast milk from major metropolitan cities in India

The present study was carried out to understand the current contamination status of organochlorine compounds (OCs) in human breast milk from three metropolitan cities in India (New Delhi, Mumbai and Kolkata). Among the OCs analyzed, DDTs were predominant followed by HCHs and PCBs. CHLs and HCB levels were much lower. Contamination patterns were different in human milk found in our previous study in Chennai, a metropolitan city in southern India, indicating region specific exposure routes and variable sources. In comparison with previous data, levels of DDTs and HCHs generally declined with time, implying the effect of various bans and restrictions on their usage. No association between concentrations of OCs and demographic characteristics such as parity and age of mothers was observed which might be due to narrow range of mother's age. Estimated daily intake shows that some infants are exposed to OCs to a greater extent, particularly HCHs than the guideline standard.     

Removal mechanism of elemental mercury by using non-thermal plasma

The removal mechanism of elementary mercury (Hg(0)) by non-thermal plasma (NTP) has been investigated, where dielectric barrier discharge and O(3) injection methods as oxidation techniques are employed, together with the analysis of mercury species deposited on the reactor surface using temperature-programmed desorption and dissociation (TPDD) and scanning electron microscopy-energy dispersive spectroscopy. The removal of Hg(0) by NTP is found to be time-dependent and proceed through three domains; the Hg(0) concentration just slightly decreases as soon as NTP is initiated and then becomes constant for several minutes (Region 1), thereafter starts to decrease rapidly for 1h (Region 2) and, after passing fall-off region, very slowly decreases for about 4h (Region 3). The deposited mercury species on the reactor surface were conglomerated like islands, rather than dispersed uniformly, and their ratio of Hg(0) to O composition is observed to be 1:2. Additionally, the new peak in TPDD spectra observed in the region of 260-380°C is proposed as HgO(3). These results lead us to conclude that the deposited mercury species by NTP have extra O atoms to oxidize the adsorbed Hg(0), resulting in the acceleration of removal rate as the oxidation of Hg(0) proceeds.     

Levels and body distribution of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in freshwater fishes from the Yangtze River, China

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) were determined in muscle, liver and eggs of freshwater fishes from the lower reach of the Yangtze River, China. The present study is the first to report HBCD concentrations in the environment of China. The concentrations of PBDEs and HBCDs in muscle of freshwater fishes from the Yangtze River ranged from 18 to 1100ng/g and 12 to 330ng/g lipid weight (wt.), respectively. When compared with other regions of the world, the contamination of PBDEs in biota could be regarded as moderate, whereas contamination of HBCDs in biota was relatively high. The PBDE congener profiles in fishes of the present study were markedly different from those observed in freshwater and marine fishes from other regions of the world. In the present study, BDE-15, BDE-28 and BDE-47 were the predominant congeners in the fishes. This particular congener profile in fishes from the Yangtze River revealed that a specific commercial PBDE formulation (probably made in China) might have been used in the Yangtze River Delta region.