PBDF and PBDD from the combustion of bromine containing flame retarded polymers: A survey

The formation of polybrominated dibenzofurans (PBDF) and dibenzodioxins (PBDD) during the pyrolysis of different polymers containing brominated organic flame retardants was investigated. The pyrolyses were conducted at two different temperatures (600°C and 800°C) using three different oven configurations. Both the pyrolysis gases and the solid residues were analysed for PBDF and PBDD.

PBDF were found in almost all samples, but both the concentration and the degree of bromination varied greatly. The largest yields of PBDF in the percent range were measured in the pyrolysis products of polymers containing brominated diphenyl ethers. The other flame retardants generally yielded only a few ppm of PBDF. PBDD are formed only in a few samples and related to the PBDF in very low concentrations.     

Recycling of flame retardants containing printed circuits: A study of the possible formation of polyhalogenated dibenzodioxins/-furans

The generation of halogenated dibenzo-p-dioxins/-furans could be expected during recycling of printed circuits containing flame retardants. The presence of precursor substances (e.g. flame retardants like tetrabromobis-phenol A or PCB), partly elevated temperatures, and catalytical effects of copper seem to represent typical formation conditions for “dioxins”. To control the possible contamination of granulated material and thus of work places, in a pilot plant a test run was carried out with a hammer mill and an impact grinder. The air samples examined did not contain PXDD/F residues and the shredded material was contaminated only with PBDD/F at very low concentrations (0.03 – 1.13 ng/g). A test with printed circuits under thermal stress up to 300 °C in an oven generated low amounts of PBDD/F (0.74 – 4.51 ng/g). These tests provide proof that printed circuits can be recycled.     

Post-combustion syntheses of PCDD/F and PBDD/F from halogen-rich fuel is suppressed by a pebble heater technology

GOAL, SCOPE AND BACKGROUND: Changes in German and European legislation shifted processing of polymer-rich shredding residues (SR) from landfill to thermal treatment. However, when waste of electric and electronic equipment (WEEE) is the source of SR, thermal treatment is complicated by halogens as well as the presence of polybrominated dioxins and furans (PBDD/F) and brominated flame retardants (BFR). Hence, WEEE requires high temperature incineration with sufficient residence times. Post-combustion synthesis of polyhalogenated dioxins and furans (PXDD/F) is dominant in the temperature range between 250-450 degrees C. Thus, a very rapid gas cooling from 450 degrees to 250 degrees C is important for proper raw gas treatment. The pebble heater technology developed by ATZ Entwicklungszentrum (Sulzbach-Rosenberg, Germany) might serve as an alternative to the state-of-the-art quench cooling. It is based on the application of a pebble bed of natural bulk material, which the exhaust gases flows through radially. It provides an excellent heat transfer and a temperature gradient in the range of 1,500-2,000 K/m. The paper presents data of a pilot application of the pebble heater technology for the treatment of raw gas derived from the incineration of polymeric materials from WEEE. METHODS: A liquid fuel was chosen in order to minimise technical modifications of the plant. It was analysed for halogens by x-ray fluorescence, for brominated flame retardants by HPLC-UV/MS and for PXDD/F by GC-HRMS. Combustion gases were rapidly cooled down to temperatures below 200 degrees C and emissions of PBDD/F and PCDD/ F were estimated without further off-gas treatment. PBDD/F emissions were computed as PCDD/F toxicity equivalents applying two different calculation approaches. RESULTS AND DISCUSSION: PCDD/F emissions accounted for 0.04 ng I-TEQ/Nm3 and are in compliance with European emission limits. Calculated PBDD/F toxicity equivalents exceeded the emission limit of 0.1 ng I-TEQ/Nm3 by factors of 75 and 208 depending on the calculation approach. A mass balance of PBDD/F and PCDD/F congeners revealed an efficient elimination of more than 95% in most cases. Lower reduction rates (76% for 2,3,7,8-TeBDF and 82% for 1,2,3,7,8-PeBDF) were attributed to incomplete combustion. An intended recovery of halogens by one-stage scrubbing downstream of the pebble heater was ineffective, recovering 28% of the applied chlorine and 9% of the bromine, only. CONCLUSIONS: Our pilot incineration test indicates that the pebble heater technology can effectively suppress a post-combustion synthesis of PCDD/F and PBDD/F, resulting in low PCDD/F emission levels without further off-gas treatment. The presented data state that WEEE is sensible to incomplete combustion, which will lead to increased PBDD/F emissions without increasing PCDD/F emission limits. This finding is especially relevant for small and low-technical incineration appliances, which have been reported to treat WEEE in developing countries and are considered to serve as a significant source of PXDD/F these days. RECOMMENDATIONS AND PERSPECTIVES: Monitoring of PCDD/F emissions only might considerably underestimate the total emission of dioxins and dioxin-like compounds. It is therefore an ineffective means for assessing resulting health risks, at least for those waste treatment plants which are considered to handle the increasing amounts of PBDD/ F-containing polymers from WEEE in future. Consequently, it is recommended to initiate a screening programme for PXDD/F emissions in large scale incineration facilities which are capable of treating WEEE shredder residues.     

Characterisation of polymer fractions from waste electrical and electronic equipment (WEEE) and implications for waste management

There is an increasing interest in the end-of-life management of polymers present in waste electrical and electronic equipment (WEEE). This is mainly due to high recycling and recovery quotas set by the European WEEE directive, which can only be fulfilled by including the plastic fraction in recycling and recovery approaches. Previous studies identified a high material diversity and various contaminants in WEEE plastics, including heavy metals, polybrominated biphenyls (PBB), diphenyl ethers (PBDE), as well as polybrominated dibenzodioxins and dibenzofurans (PBDD/F). These substances are regulated by European directives that limit their levels in marketable products. Consequently, both material diversity and contaminants are strong arguments against material recycling and point to hazardous waste treatment. However, recent developments in the production of flame retardants and electrical and electronic goods aimed to reduce contaminants and material diversity. Thus, the present study summarises updated contaminant levels of plastic fractions of European WEEE, as well as data on materials in waste housing polymers. Material characterisation revealed housing fractions to be interesting sources for polymer recycling, which however has to implement potent material separation and/or bromine elimination techniques. With respect to contaminants, our data indicate an effective phase-out of PBB, but still high levels of PBDE and PBDD/F are found. Sources and implications for the material recycling and thermal recovery approaches are discussed in detail.     

Polybrominated, polychlorinated and monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans and dioxin-like polychlorinated biphenyls in marine surface sediments from Hong Kong and Korea

In this study we investigated occurrences and distribution patterns of dioxin-related compounds (DRCs) such as polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs), polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), monobromo-polychlorinated dibenzo-p-dioxins/dibenzofurans (MoBPCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in marine surface sediments collected from the coastal waters of Hong Kong and Korea. In most sampling sites, concentrations of PCDDs were the highest, followed by DL-PCBs, PCDFs, PBDFs, PBDDs, MoBPCDDs and MoBPCDFs in this order. Levels of PBDD/Fs were generally 1-2 orders of magnitude lower than chlorinated analogues. Levels of PCDDs are higher than PCDFs in Hong Kong while levels of PBDFs are higher than PBDDs in Korea (p < 0.05). Report of PBDD/Fs and MoBPCDD/Fs in sediments from East Asian countries is novel and original. Environmental levels of PBDD/Fs are supposed to start increasing in accordance with rising production, use and disposal of brominated flame retardants (BFRs) and recycling processes of e-waste in Asian developing countries.     

Formation of chlorinated and brominated dioxins and other organohalogen compounds at the pilot incineration plant VERONA

Experiments were conducted at the VERONA pilot plant, an incineration plant with stationary grate and separate post-combustion chamber, using wood and propane as basic combustible materials and with controlled dosage of various bromine-, chlorine- and copper-containing compounds. The behaviour of the following compounds was studied in the combustion chamber, after the post-combustion chamber and after the heat exchanger: polychlorinated phenols (PCPh), polybrominated phenols (PBrPh), polychlorinated benzenes (PCBz), polybrominated benzenes (PBrBz), polychlorinated dioxins and furans (PCDD/F) and polybrominated dioxins and furans (PBDD/F). The bromine co-incineration leaded to very high bromophenol concentrations after the post-combustion chamber. The formation of brominated and mixed-halogenated phenols and the further reaction to halogenated dioxins is apparently a relevant reaction mechanism for dioxin formation in processes involving bromine. This assumption is supported by the high formation rates of PBDD/F found in the heat exchanger, which were 4-20 times higher than those of PCDD/F. Moreover, the strong correlations found between the formation rates of PCPh, PCBz and PCDD/F in the heat exchanger indicate that in addition considerable new formation of dioxins takes place through de novo synthesis. Experiments involving the variation of primary operational parameters and fuel properties have shown that the quality of post-combustion plays a much greater role than the other parameters. Furthermore, it became apparent that the congeners of the chlorophenols and of the chlorobenzenes, measured in various incineration stages, do not correlate closely with the dioxin concentrations after the heat exchanger.     

Determination of polybrominated diphenyl ethers and PBDD/Fs during the recycling of high impact polystyrene containing decabromodiphenyl ether and antimony oxide

A high impact polystyrene (HIPS) plastic, flame retarded with decabromodiphenyl ether (DecaBDE) and antimony trioxide (Sb2O3) has been repeatedly processed and the amount of debromination of the flame retardant and possible formation of PBDD/F was monitored. No indications of debromination were found. The reprocessed (recycled) plastic was found to comply with the German Chemicals Banning Ordinance. The concentrations of relevant PBDD/F congeners were at least one order of magnitude below the regulated limit values for PBDD/F (1 ppb for the sum of four congeners, 5 ppb for the sum of all eight regulated congeners).     

Hydroxylated and methoxylated polybrominated diphenyl ethers and polybrominated dibenzo-p-dioxins in red alga and cyanobacteria living in the Baltic Sea

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) are present in the ecosystem of the Baltic Sea. OH-PBDEs are known to be both natural products from marine environments and metabolites of the anthropogenic polybrominated diphenyl ethers (PBDEs), whereas, MeO-PBDEs appear to be solely natural in origin. Polybrominated dibenzo-p-dioxins (PBDDs) are by-products formed in connection with the combustion of brominated flame retardants (BFRs), but are also indicated as natural products in a red alga (Ceramium tenuicorne) and blue mussels living in the Baltic Sea. The aims of the present investigation were to quantify the OH-PBDEs and MeO-PBDEs present in C. tenuicorne; to verify the identities of PBDDs detected previously in this species of red alga and to investigate whether cyanobacteria living in this same region of the Baltic Sea contain OH-PBDEs, MeO-PBDEs and/or PBDDs. The red alga was confirmed to contain tribromodibenzo-p-dioxins (triBDDs), by accurate mass determination and additional PBDD congeners were also detected in this sample. This is the first time that PBDDs have been identified in a red alga. The SigmaOH-PBDEs and SigmaMeO-PBDEs concentrations, present in C. tenuicorne were 150 and 4.6 ng g(-1) dry weight, respectively. In the cyanobacteria 6 OH-PBDEs, 6 MeO-PBDEs and 4 PBDDs were detected by mass spectrometry (electron capture negative ionization (ECNI)). The PBDDs and OH-PBDEs and MeO-PBDEs detected in the red alga and cyanobacteria are most likely of natural origin.     

The flame retardant tetrabromobisphenol-A and its metabolite found in river and marine sediments in Japan

Tetrabromobisphenol-A (TBBP), used as a flame retardant, was detected in river sediments collected in Osaka, Japan, at a concentration range from 22 to 140 μg/kg (ppb), as determined on a dry weight basis. TBBP was also found in marine sediments collected at Osaka Bay, though the TBBP levels of these samples were much lower than those from river sediments. Dimethyl ether derivative of TBBP (TBBP-DM), thought to be a decomposition product from microbial methylation, was found in the river sediments but in none of the marine sediments. TBBP-DM residues were about one-hundredth of the TBBP levels.     

PBDD/F impurities in some commercial deca-BDE

The study presented the concentrations and distributions of polybrominated dibenzo-p-dioxins and polybrominated dibenzofurans (PBDD/Fs) as impurities in some commercial decabromodiphenyl ether (DBDE) mixtures that were produced by several manufacturers. The total concentrations of 12 2,3,7,8-substituted tetra- to octa-BDD/F congeners were found to be in the range of 3.4-13.6 (mean 7.8) μg/g, averagely accounting for 99% of total PBDD/Fs. OBDF was the prevailing congener, followed by 1,2,3,4,6,7,8-HpBDF. In addition, OBDD and 1,2,3,4,7,8-HxBDF were also obviously detectable. The total concentrations of PBDD/Fs varied both between the manufacturers and between the lots. On the basis of the global demand for the commercial DBDE in 2001, the annual potential emissions of PBDD/Fs were calculated coarsely to be 0.43 (range: 0.21-0.78) tons. The major dioxin congeners, OBDF and 1,2,3,4,6,7,8-HpBDF, presenting in DBDE, were estimated to be formed from BDE-209, BDE-206, and/or BDE-207 via an intra-molecular elimination of Br₂/HBr.     

Analytical protocol for the analysis of polybrominated dibenzo-dioxins and dibenzofurans: Data quality objectives and single-laboratory evaluation

An analytical protocol for the measurement of part per billion and sub-part per billion levels of PBDDs and PBDFs in selected flame retardant chemicals (polybrominated diphenyloxides; PBDPO) was developed. The fractionation/enrichment procedures were optimized to minimize the effects of the PBDPOs upon the ability to recover and measure the PBDD/PBDFs. Results from the method validation show that the current methodology is capable of accuracies ranging from 70% to 150% at the 0.1 to 10 ppb levels while larger sample sizes (from 20–200 mg to 4 g) are necessary in order to meet the EPA target Test Rule limit of quantification (LOQ) requirements.     

Modified clean-up for PBDD,PBDF and PBDE with an active carbon column--its application to sediments

A clean-up method for polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs) and diphenyl ethers (PBDEs) was modified using combinations of multi-layered silica gel, Florisil and active carbon columns. By using active carbon column chromatography in the final procedure, PBDEs were well separated from PBDD/Fs in an elution test with reference standards. We report the application of this method to sediment samples taken from industrialized areas in Japan. These sediments contained PBDEs ranging in concentration from 13 to 2394 pg/g, dry wt. PBDEs did not interfere with the quantification of PBDD/Fs. In addition, PBDEs found in the PBDD/F fraction did not interfere with the identification of PBDFs using the HRGC/HRMS separation method. Some 2,3,7,8-tetra- to hexabrominated dioxins and furans were also detected in the sediment samples.     

Distribution of polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in municipal solid waste incinerators

The stack flue gases and the ashes in different units of two municipal solid waste incinerators (MSWIs) are sampled to investigate the characteristics of polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Bottom ashes (BA) exhibited much higher PBDD/F (8.11-52.2 pg TEQ/g) and PBDE contents (20.4-186 ng/g) than those of fly ashes (0.0932-2.02 pg TEQ/g and 0.332-25.5 ng/g), revealing that the PBDD/Fs and PBDEs in the feeding waste may not be completely destroyed. The PBDE concentrations/contents in the stack flue gases (26.1-109 ng/Nm³) and in the BA (20.4-186 ng/g) of the MSWIs could reach three orders higher than those in the atmosphere and reference soils. PBDE contributions to the environment from the stack flue gases or the reutilization of BA of MSWIs should not be ignored from the developing PBDE inventory.     

Transfer of brominated flame retardants from components into dust inside television cabinets

Television (TV) set components are highly flame resistant, with their added brominated compounds such as polybrominated diphenyl ethers (PBDEs). These compounds might be released indoors via dust, which presents a potential exposure pathway for humans in the home environment. In this study, we collected dust from inside TV sets and TV set component samples (parts of housing front cabinets, rear cabinets and circuit boards) of five sets used in Japan. We measured BFRs (i.e., PBDEs, tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs)) and polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/DFs). Analytical results of the TV components showed that the concentrations of PBDEs, TBBPA and PBDFs (48,000mug/g, 19,000mug/g and 9600ng/g as mean values, respectively) were all highest in the rear cabinets. The SigmaPBDD concentrations (460ng/g as a mean value) detected were highest in the circuit board samples. The respective SigmaPBDE and SigmaPBDF concentrations in the dust samples were 67-500mug/g (mean 300mug/g) and 180-650ng/g (mean 410ng/g). Such concentrations were 2-3 orders of magnitude higher than those previously reported for house dust samples, which suggests that the brominated compounds are transferred from TV components into dust. Comparison of congener patterns of the brominated compounds in the dust identified the components as the source of these BFRs.     

Ah Receptor Agonists in UV-exposed Toluene Solutions of Decabromodiphenyl Ether (decaBDE) and in Soils Contaminated with Polybrominated Diphenyl Ethers (PBDEs) (9 pp)

Goal, Scope and Background The use of polybrominated diphenyl ethers (PBDEs) as flame retardants increases the risk for emissions of other brominated compounds, such as polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). The large homology in structure of PBDD/Fs and mechanism of toxic action, i.e. the capacity to activate the Ah receptor (AhR) pathway, compared to their well-studied chlorinated analogues, justifies a raised concern to study the environmental levels and fate of these compounds. Decabromodiphenyl ether (decaBDE) is the most widely used PBDE today. Studies on photolytic debromination of decaBDE in organic solvents have shown debromination of decaBDE, as well as formation of PBDFs. However, little is known about the transformation mechanisms and there are only scarce data on photoproducts and PBDE transformation in environmentally relevant matrices. In this study, mechanism-specific dioxin bioassays were used to study photolytic formation of AhR agonists in toluene solutions of decaBDE. In addition, the influence of irradiation time and UV-light wavelength on the formation was studied. PBDE congener patterns and presence of PBDD/Fs were analysed. Further, AhR agonists were analysed in agricultural soils contaminated with PBDEs. Soils were also exposed to UV-light to study changes in AhR agonist levels. Methods Toluene solutions of decaBDE were irradiated using three different spectra of UV-light, simulating UV-A (320-400 nm), UV-AB (280-400 nm), and UV-ABC (250-400 nm). Additionally, decaBDE solutions were exposed to narrow wavelength intervals (10 nm bandwidth) with the central wavelengths 280, 290, 300, 310, 320, 330, 340, 350, 360 nm. AhR agonists in decaBDE solutions were analysed with two different bioassays, the chick embryo liver-cell assay for dioxins (Celcad) and the dioxin responsive, chemically activated luciferase expression assay (DR-Calux). Also, the decaBDE solutions were analysed with LRGC-LRMS to obtain PBDE congener patterns for breakdown of decaBDE, and with HRGC-HRMS, for presence of PBDD/Fs. Four soils were exposed to UV-AB light, under both dry and moist conditions. Levels of AhR agonists in soil extract fractions, before and after UV-exposure, were analysed with the DR-Calux. Results and Discussion Significant levels of photoproducts able to activate the AhR pathway, up to 31 ng bio-TEQ/ml, were formed in UV-exposed decaBDE solutions. The transformation yield of decaBDE into AhR agonists was estimated to be at the 0.1%-level, on a molar basis. The net formation was highly dependent on wavelength, with the sample irradiated at 330 nm showing the highest level of dioxin-like activity. No activity was detected in controls. PBDE analysis confirmed decaBDE degradation and a clear time-dependent pattern for debromination of PBDE congeners. AhR agonist effect in the recalcitrant fractions of the soils corresponded to the levels of chemically derived TEQs, based only on chlorinated dioxin-like compounds in an earlier study. It was concluded that no significant levels of other AhR agonists, e.g. PBDFs, were accumulated in the soil. UV-light caused changes in AhR-mediated activity in the more polar and less persistent fractions of the soils, but it is not known which compounds are responsible for this. Recommendations and Perspective . The laboratory experiments in this study show that high levels of AhR agonists can be formed as photoproducts of decaBDE and it is important to elucidate if and under which conditions this might occur in nature. However, soil analysis indicates that photoproducts of PBDE do not contribute to the accumulated levels of persistent dioxin-like compounds in agricultural soil. Still, more data is needed to fully estimate the environmental importance of PBDE photolysis and occurrence of its photoproducts in other environmental compartments. Analysis with dioxin bioassays enabled us to gather information about photoproducts formed from decaBDE even though the exact identities of these compounds were not known. Conclusion Bioassays are valuable for studying environmental transformation processes like this, where chemical analysis and subsequent toxicological evaluation requires available standard compounds and information on toxicological potency. The use of bioassays allows a rapid evaluation of toxicological relevance.     

Quantum chemical and direct dynamic study on homogeneous gas-phase formation of PBDD/Fs from 2,4,5-tribromophenol and 3,4-dibromophenol

2,4,5-Tribromophenol (2,4,5-TBP) and 3,4-dibromophenol (3,4-DBP) have the minimum number of Br atoms needed to form 2,3,7,8-PBDD/Fs, which are the most toxic among all 210 PBDD/F isomers. A mechanistic understanding of the formation of PBDD/Fs is a prerequisite for minimizing their emissions. In this paper, the homogeneous gas-phase formation of PBDD/Fs from 2,4,5-TBP and 3,4-DBP as precursors was investigated theoretically by using the density functional theory (DFT) method. The mathematical model to predict the formation of PBDD/Fs places a high demand on accurate kinetic parameters. So, the rate constants of key elementary steps involved in the formation of PBDD/Fs were calculated by using canonical variational transition-state (CVT) theory with small curvature tunneling (SCT) contribution over a wide temperature range of 600–1200 K. The pre-exponential factors and the activation energies are also reported. This might be the first to investigate the formation of 2,3,7,8-PBDD/Fs. The present study shows that the formation of PBDDs dominates over the formation of PBDFs. The meta bromine facilitates the dimerization of bromophenoxy radicals (BPRs), whereas the para and ortho bromines suppress the dimerization of BPRs.     

Psychological effects upon exposure to polyhalogenated dibenzodioxins and dibenzofurans

Thirty workers who had been exposed to combustion products for several years due to testing of flame retarding qualities of building materials and 30 controls from the same facility were investigated. Concentrations found in samples taken from different places of the facility were up to 14,660 microg/kg for polybrominated dibenzofurans and up to 67.1 microg/kg for polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs). Physical examination, routine laboratory parameters, and blood fat concentrations of PCDDs and PCDFs revealed normal findings. Neurotoxic symptoms showed a weak tendency of overrepresentation among the exposed workers. The frequency of neurobehavioural symptoms increased significantly with trait anxiety independent of exposure to combustion products.     

Measuring emissions of organophosphate flame retardants using a passive flux sampler

Flame retardants are used in polymers to reduce the flammability of building materials, electric appliances, fabric and papers. In recent years, organophosphate flame retardants have been used as substitutes for polybrominated flame retardants (BFRs). In Japan, the amount of organophosphate flame retardants used in 2001 was about five times more than in 2000. Recently, several studies have shown the health concerns for some organophosphate flame retardants. Little research has been performed on the emission of organophosphate flame retardants, especially the relationship between content and emissions. In this study, a new type of passive sampler was developed to measure emissions of organophosphate flame retardants from plastic materials. With this sampler, emissions from polyvinyl chloride wallpaper samples with different content of tris(2-chloroisopropyl)phosphate (TCPP) at different temperatures were examined. The observed maximum emissions of TCPP from 1, 3, 5, 10 and 20 w/w% content wallpaper materials were 262.3, 452.6, 644.8, 1119.1 and 2166.8 μg m⁻² h⁻¹, respectively. Emissions from 5% TCPP content materials at 40 and 60 °C were 1135.7 and 2841.2 μg m⁻² h⁻¹, respectively. A significantly positive correlation between the flux of TCPP and the TCPP content of the wallpaper samples was observed. A linear relationship was found between the inverse of temperature and the logarithm of TCPP emission. The results imply that the use of materials with a high organophosphate flame retardant content can lead to high emission rates in high-temperature indoor environments.     

Soot Control During the Combustion of Polystyrene

This paper describes an experimental study on the control of soot formation during the combustion of polystyrene (PS). A stable, twodimensional flame generated by using a Wolfhard-Parker type diffusion flame burner was used to simulate practical combustion situations. The combustion characteristics, effects of operating conditions on soot formation, and the effectiveness of various metallic additives as soot suppressants were investigated. It was found that soot yield could not be significantly reduced by controlling the oxidizer (air) flow rate. Increasing the O₂ mole fraction of the oxidlzer increased soot yield under typical operating conditions. However, soot yield could be greatly reduced by adding small amounts of air into the pyrolysis zone of the flame. The additional air would probably increase the combustion reaction rate while decreasing the soot precursor formation rate, thereby causing the observed effect. It was thus suggested that effective soot control could be accomplished by improving mixing between air and the PS devolatilizatlon products In practical combustion situations. The metallic additives tested in this study were the salts of Na, K, Ca, and Ba. Among these salts, Ca was the least effective in reducing soot, and K and Na were nearly equally effective. Ba was much more effective than all the others, and Its effectiveness was strongly dependent on its addition rate.     

Prediction of the retentions of polybrominated dibenzo-p-dioxins (PBDDs) by using the retentions of polychlorinated dibenzo-p-dioxins (PCDDs)

The retention equations In k' = A + B/T of 49 polychlorinated dibenzo-p-dioxins (PCDDs) and 4 polybrominated dibenzo-p-dioxins (PBDDs) in gas chromatography (GC) have been investigated to evaluate the properties of regression coefficients A and B. The quantitative relationships between A and B values of PCDDs and those of PBDDs are found. The regression equations derived have correlation coefficients greater than 0.997. The A, B values of any PBDD can be predicted by using the A, B values of the PCDD according to these relationships. Using these predicted A and B values, the retention times of all PBDDs can be predicted at any temperature program. It is very useful to identify the peak position of any PBDD because at present there are only a few standards of PBDDs available.