Emission characteristics of PCDD/Fs, PCBs, chlorobenzenes, chlorophenols, and PAHs from polyvinylchloride combustion at various temperatures

The effect of temperature on polyvinylchloride (PVC) combustion using a downstream tubular furnace was investigated for the formation of polycylcic aromatic hydrocarbons (PAHs) and chlorinated compounds. As the temperature increased, higher levels of PAHs were generated. Chlorinated compounds reached a peak at 600 degrees C, with low emissions recorded at 300 and 900 degrees C. There was a close correlation (R2 = 0.97) among polychlorinated biphenyls (PCBs), hexachlorobenzene, pentachlorobenzene, and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). PAHs at all temperatures were analyzed in the gas phase. PCDD/Fs and PCBs were emitted as a solid phase at 300 and 600 degrees C and as a gas phase at 900 degrees C. For some PAHs, chlorobenzenes, and PCDD/Fs, a mathematical equation between the gas and solid phase and the reciprocal temperature in semilog proportion was derived. The proposed equation, which is log (amount in gas phase/amount in solid phase) = -A/T + B, where T is the temperature of the furnace and A and B are constants, for these species relating their gas/solid distributions showed a good relationship.     

Urea as a PCDD/F Inhibitor in Municipal Waste Incineration

ABSTRACT

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from municipal waste incineration have been widely studied because of their extensive toxicity, and many efforts have been made to restrict their emissions. Although a number of chemical compounds have been shown in laboratory-scale tests to inhibit the formation of PCDD/Fs, few have been tested in pilot- or full-scale plants. This work evaluates the effect of urea as a PCDD/F inhibitor in a pilot-scale incinerator that uses refuse-derived fuel (RDF). The decomposition of urea under the test conditions was also studied using detailed kinetic modeling. An aqueous solution of urea was injected into the flue gas stream after the furnace at ~730 °C, with varied urea concentrations and flue gas residence times used between the furnace and the sampling point. The results demonstrate that urea can successfully inhibit PCDD/F formation in waste incineration if concentrations and injection points are properly adjusted. The kinetic model showed that urea can be rapidly decomposed under appropriate flue gas conditions, indicating that in addition to the urea molecule itself, decomposition products of urea can also be responsible for the reduction of PCDD/F production during incineration.     

Simultaneous monitoring of PCDD/Fs and PCBs in contaminated air with semipermeable membrane devices and fresh spruce needles

The contaminated air with burning plastic floor and electronic scrap was monitored with semipermeable membrane devices (SPMDs) and fresh unpolluted spruce needles at the same time for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It was found that there were more polychlorinated dibenzofurans (PCDFs) than polychlorinated dibenzo-p-dioxins (PCDDs) collected from contaminated air. The total amounts of PCBs were much higher than that of PCDD/Fs, but the contribution of them to the WHO-TEQ was less than that of PCDD/Fs. Triolein-containing SPMDs can absorb much more PCDD/Fs and PCBs than spruce needles when they were exposed in contaminated air simultaneously. The logarithm of the concentrations of PCDD/Fs and PCBs in SPMDs and in spruce needles at the same sampling time exhibited a significant linear correlation, the correlation coefficients were larger than 0.86 for PCDD/Fs and 0.92 for PCBs. SPMDs and spruce needles are effective passive air sampler for PCDD/Fs and PCBs. SPMDs and spruce needles can complement each other in passive air sampling.     

Characterization of dioxin-like contamination in soil and sediments from the ��hot spot�� area of petrochemical plant in Pancevo (Serbia)

Purpose

Combinatorial bio/chemical approach was applied to investigate dioxin-like contamination of soil and sediment at the petrochemical and organochlorine plant in Pancevo, Serbia, after the destruction of manufacturing facilities that occurred in the spring of 1999 and subsequent remediation actions.

Materials and methods

Soil samples were analyzed for indicator polychlorinated biphenyls (PCBs) by gas chromatography/electron capture detection (GC/ECD). Prioritized soil sample and sediment samples from the waste water channel were analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). Microethoxyresorufin o-deethylase (Micro-EROD) and H4IIE?Cluciferase bioassays were used for monitoring of dioxin-like compounds (DLC) and for better characterization of dioxin-like activity of soil samples.

Results

Bioanalytical results indicated high dioxin-like activity in one localized soil sample, while the chemical analysis confirmed the presence of large quantities of DLC: 3.0?×?10⁵ ng/g d.w. of seven-key PCBs, 8.2 ng/g d.w. of PCDD/Fs, and 3.0?×?10⁵ ng/g d.w. of planar and mono-ortho PCBs. In the sediment, contaminant concentrations were in the range 2?C8 ng/g d.w. of PCDD/Fs and 9?C20 ng/g d.w. of PCBs.

Conclusions

This study demonstrates the utility of combined application of bioassays and instrumental analysis, especially for developing and transition country which do not have capacity of the expensive instrumental analysis. The results indicate the high contamination of soil in the area of petrochemical plant, and PCDD/Fs contamination of the sediment from the waste water channel originating from the ethylene dichloride production.     

Generation of PCDD/F in Fly Ash from Municipal Solid Waste Incinerators

Abstract

Fly ash from municipal solid waste incinerators (MSWIs) has been characterized in terms of polychlorinated dibenzyl-p-dioxin and polychlorinated dibenzofuran (PCDD/F) content. Increasing values of PCDD/Fs have been found to correlate with decreasing temperatures of sampling points in flue gas treatment lines of the plants, confirming other researchers’ findings about temperature as the major controlling parameter for the PCDD/F formation. Measured PCDD/F ratios show that de novo synthesis is the dominant formation mechanism. The increasing trends of particulate-bound PCDD/Fs can be explained not only through the dominant de novo synthesis process but also considering the adsorption of gaseous PCDD/Fs on fly ash deposits, even outside the typical de novo synthesis temperature ranges. The effective role of a post-combustor unit, imposed by Italian law to destroy PCDD/Fs, also needs to be carefully reconsidered.     

Air concentrations of PCDD/Fs, PCBs and PCNs using active and passive air samplers

The concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) were determined in air samples collected at four sampling sites located in two zones of Barcelona (Spain): near a municipal solid waste incinerator (MSWI) and a combined cycle power plant (3 sites), and at a background/control site. Samples were collected using high-volume active samplers. Moreover, 4 PUF passive samplers were deployed at the same sampling points during three months. For PCDD/Fs, total WHO-TEQ values were 27.3 and 10.9 fg WHO-TEQm(-3) at the urban/industrial and the background sites, respectively. The sum of 7 PCB congeners and the Sigma PCN levels were also higher at the industrial site than at the background site. In order to compare active and passive sampling, the accumulated amounts of PCDD/Fs, PCBs and PCNs in the four passive air samplers, as well as the total toxic equivalents in each sampling site were also determined. To assess the use of PUF passive samplers as a complementary tool for PCDD/F, PCB and PCN monitoring, sampling rates were calculated in accordance with the theory of passive air samplers. PUF disks allowed establishing differences among zones for the POP levels, showing that they can be a suitable method to determine POP concentrations in air in areas with various potential emission sources. Although both particle and gas phase were sorbed by the PUFs, data of gas phase congeners are more reproducible.     

Characteristics of PAHs, PCDD/Fs and PCBs in sediment following forest fires in northern Alberta

Extensive forest fires occurred in northern Alberta, Canada, in 1998. Polynuclear aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were studied following these forest fires in order to explore natural and anthropogenic influences on the affected forest fire area. Specifically, concentrations and profiles of these compounds were determined in sediment samples. A predominance of alkylated PAH derivatives over parent PAHs were observed at the burned and reference sites. Naturally dervied PAHs were abundant at all sites. A high proportion and concentration of retene was observed at the totally burned site and indicates some inputs from forest fires. Very low concentrations of PCDD/Fs and PCBs were observed at all sites, and the profiles were very similar. This likely reflects common atmospheric contributing sources to the study area.     

Effect of copper chloride on the emissions of PCDD/Fs and PAHs from PVC combustion

The influences of temperature, air flow and the amount of copper chloride upon the types and amount of the toxic emissions such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) during combustion of polyvinyl chloride (PVC) were investigated. The mechanism concerning the effect of temperature and copper chloride on the PCDD/Fs and PAHs formation was discussed. The results shown that without copper chloride, trace amounts of PCDD/Fs and large amounts of PAHs were found in the emissions from the pure PVC combustion under various combustion conditions. The addition of copper chloride enhanced PCDD/Fs formation, but it seems that the formation of PAHs decreased with increasing amount of copper chloride, and greater total amount of PAHs were produced at the higher temperature under our experimental conditions.     

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans in atmosphere; evaluation of predicting models

The gas/particle partitioning of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) was measured at three sites for a year in order to monitor the variation of PCDD/Fs levels and describe their partitioning. The air concentrations of PCDD/Fs ranged from 71 to 1161 fg I-TEQ/m³ and large changes in these levels did not correlate with seasonal changes during this study. Different homolog patterns were observed in the gas/particle phase. High chlorinated dioxin/furans dominated the particle phase while low chlorinated dioxin/furans dominated the gas phase. The high correlation coefficient between log [(PCDD/Fs_vap)(TSP)/(PCDD/Fs_pat)] and 1/T was observed in lower chlorinated dioxin/furans unlike in OCDD/F. The slope of homolog ranged from −0.410 to −1.025 and that of 2,3,7,8-substituted isomers ranged from −0.379 to −0.772 in plots of the log partition coefficient (K_p) versus the log subcooled vapor pressure (P_L°).The octanol/air partition coefficient (K_oa)-based model of PCDD/Fs is more compatible with experimental data than those of the Junge–Pankow model that tends to overestimate results, even though both models include some level of uncertainty. However, both models can underestimate the particle phase of PCDD/Fs, especially when the ambient air temperature is extremely low in winter.     

Catalytic decomposition of dioxins and other unintentional POPs in flue gas from a municipal waste incinerator (MWI) in China: a pilot testing

Unintentionally produced persistent organic pollutants (UPOPs) include polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), pentachlorobenzene (PeCBz), and hexachlorobenzene (HxCBz). With the booming of municipal waste incinerators (MWIs) in China, the emission of UPOPs has generated great concern. As an alternative technology of dioxin control, catalytic decomposition has not been used in China, mainly due to the absence of national demonstration projects. Also, the simultaneous removal of various UPOPs has not been well investigated.In this study, a pilot-scale selective catalytic oxidative (SCO) system using a self-developed honeycomb catalyst was built and tested in a typical municipal waste incinerator (MWI) of China. The original concentration of PCDD/Fs in flue gas after the treatment of activated carbon injection (ACI) still exceeded the national emission standard (0.1 ng I-TEQ/Nm³), while the concentrations of PeCBz and HxCBz were one order of magnitude higher than that of PCDD/Fs. For the testing temperature varying from 300 to 200 °C, the removal efficiency of PCDD/Fs range from 39 to 95 %, followed by dl-PCBs with the range of 56–89 %. PeCBz and HxCBz were also removed, though their removal efficiencies were lower than those of PCDD/Fs and dl-PCBs. Both temperature and degree of chlorination influence the removal efficiencies.     

PCDD/Fs and PCBs in airborne particulate matter of the greater Thessaloniki area, N. Greece

Particle-bound polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were monitored at two sites in northern Greece for an eight-month period in 1999. PCDD/F concentrations were close to the lower end of reported values worldwide. Excepting a few cases, the PCDD/Fs homologue profile was stable. The gaseous PCDD/F fractions calculated were found to account for a small percentage of the total concentrations (<2% for OCDD/Fs and HpCDD/Fs, while 30-35% for TCDFs). Particle-bound PCBs were also found at low concentrations which, however, were higher at the urban site. Calculations of the dry deposition of particulate PCDD/ Fs and PCBs gave mean values of 0.52 and 0.59 pg I-TEQ/m2/day of PCDD/Fs, while 242 and 74 pg/m2/day of sigmaPCBs for the urban and the semirural areas respectively. An anticorrelation of PCDD/F concentrations with ambient temperature was derived particularly for the lower chlorinated congeners. A weak association with winds of western and southern origin was also observed. Factor analysis and literature source profiles were employed to identify possible emission sources. It was appeared that the PCDD/F compositional pattern of TSP is influenced by mixed sources the most prominent being uncontrolled fires and car exhausts.     

Dioxins,furans and polycyclic aromatic hydrocarbons emissions from a hospital and cemetery waste incinerator

An experimental campaign was carried out on a hospital and cemetery waste incineration plant in order to assess the emissions of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polycyclic aromatic hydrocarbons (PAHs). Raw gases were sampled in the afterburning chamber, using a specifically designed device, after the heat recovery section and at the stack. Samples of slags from the combustion chamber and fly ashes from the bag filter were also collected and analyzed. PCDD/Fs and PAHs concentrations in exhaust gas after the heat exchanger (200–350 °C) decreased in comparison with the values detected in the afterburning chamber. Pollutant mass balance regarding the heat exchanger did not confirm literature findings about the de novo synthesis of PCDD/Fs in the heat exchange process. In spite of a consistent reduction of PCDD/Fs in the flue gas treatment system (from 77% up to 98%), the limit of 0.1 ng ITEQ Nm⁻³ at the stack was not accomplished. PCDD/Fs emission factors for air spanned from 2.3 up to 44 μg ITEQ t⁻¹ of burned waste, whereas those through solid residues (mainly fly ashes) were in the range 41–3700 μg ITEQ t⁻¹. Tests run with cemetery wastes generally showed lower PCDD/F emission factors than those with hospital wastes. PAH total emission factors (91–414 μg kg⁻¹ of burned waste) were in the range of values reported for incineration of municipal and industrial wastes. In spite of the observed release from the scrubber, carcinogenic PAHs concentrations at the stack (0.018–0.5 μg Nm⁻³) were below the Italian limit of 10 μg Nm⁻³.     

Long-term environmental monitoring of persistent organic pollutants and metals in a chemical/petrochemical area: human health risks

Organic pollutants such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polycyclic aromatic hydrocarbons (PAHs), as well as some metals are periodically monitored in soil and vegetation samples collected in Tarragona County (Spain). We here report the temporal trends of the concentrations of the above pollutants between the initial survey (2002) and that recently (2009) performed. The area under evaluation was divided into 4 sections (chemical, petrochemical, urban/residential and unpolluted). In general terms, urban soils presented the highest concentrations of PCDD/Fs, PCNs and PAHs, confirming that traffic is a very important emission source of these pollutants. In addition, substantially higher levels of PAHs and some metals were found in vegetation samples from the petrochemical complex. The assessment of health risks of these contaminants indicated that the current concentrations of micropollutants did not mean additional non-carcinogenic or cancer risks for the population living in the zone.     

Monitoring of polychlorinated dibenzo-p-dioxins and dibenzofurans, dioxin-like PCBs and polycyclic aromatic hydrocarbons in food and feed samples from Ismailia city, Egypt

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyl (PCBs) and polycyclic aromatic hydrocarbons (PAHs) have been determined using GC/HRMS in food (butter, seafood and meat) and feed samples (chicken, cattle and fish) purchased from Ismailia city, Egypt. PCDD/F concentrations in food samples ranged between 0.12 and 3.35 pg WHO TEQ/g wet w, while those in feed samples were between 0.08 and 0.2 pg WHO TEQ/g dry w. Levels of PCB TEQ ranged from 0.14 to 3.2 pg/g wet w in the food samples. The feed samples have an average of 0.35 pg PCB TEQ /g dry w. In this study, butter samples showed the highest contamination levels of PCDD/Fs and PCBs. The PCBs contribution to the total TEQ was on average 63% in seafood and on average 49% for meat and butter. The highest contamination levels of PCDD/Fs and PCBs were found in butter samples. The butter TEQ content is several times higher than that reported in all EU countries and exceeded the EU limits, while the PCDD/F levels in seafood and the feed samples is far below the current EU limit. Generally, congener profiles in the food samples reflect the non-industrialized nature of the city and suggest solid waste burning as a significant source of emission. Nevertheless, the profiles for butter suggest an impact from various sources. In the case of the sum of 16 PAH contamination levels in food samples were in the range of 11.7-154.3 ng/g wet w and feed samples had a range of 116-393 ng/g dry w. Benzo(a)pyrene (BaP) has been detected in the range of 0.05-3.29 ng/g wet w in the food samples; butter showed the highest contamination which exceeded the EU standard set for fats and oil. Fingerprints of PAHs suggested both petrogenic and pyrolytic sources of contamination.     

Estimation and characterization of unintentionally produced persistent organic pollutant emission from converter steelmaking processes

Unintentionally produced persistent organic pollutants (UP-POPs) including polychlorinated dibenzo-p-dioxins, and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) were characterized and quantified in stack gas and fly ash from the second ventilation systems in five typical converters in five different steelmaking plants. The 2378-substituted PCDD/Fs (2378-PCDD/Fs) and dioxin-like PCB (dl-PCBs) toxic equivalents (TEQs) were 1.84–10.3 pg WHO-TEQ Nm^?3 in the stack gas and 5.59–87.6 pg WHO-TEQ g^?1 in the fly ash, and the PCN TEQs were 0.06–0.56 pg TEQ Nm^?3 in the stack gas and 0.03–0.08 pg TEQ g^?1 in the fly ash. The concentrations of UP-POPs in the present study were generally lower than those in other metallurgical processes, such as electric arc furnaces, iron ore sintering, and secondary metallurgical processes. Adding scrap metal might increase UP-POP emissions, indicating that raw material composition was a key influence on emissions. HxCDF, HpCDF, OCDF, HpCDD, and OCDD were the dominant PCDD/Fs in the stack gas and fly ash. TeCB and PeCB were dominant in the stack gas, but HxCB provided more to the total PCB concentrations in the fly ash. The lower chlorinated PCNs were dominant in all of the samples. The 2378-PCDD/F, dl-PCB, and PCN emission factors in stack gases from the steelmaking converter processes (per ton of steel produced) were 1.88–2.89, 0.14–0.76_, and 229–759 μg t^?1, respectively.     

Atmospheric particle size distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) and their implications for wet and dry deposition

Concurrent measurements of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) in different size fractions of atmospheric particulate matter are presented for a winter and a summer sampling period. The PCDD/Fs and PAHs were primarily associated with particles of <1.35 μm aerodynamic diameter. The particle size distributions were similar for the compounds within each substance group and, surprisingly, also between the PCDD/Fs and PAHs. Changes in the particle size distribution of particle mass were reflected in the particle size distributions of the PCDD/Fs and PAHs.The data were employed to identify those particle size fractions dominating the wet and dry particle bound deposition of PCDD/Fs and PAHs and, furthermore, to assess the relative contributions of wet and dry deposition to the total particle bound deposition fluxes. The calculations indicate that coarse particles contribute most to the dry deposition while, in contrast, the wet deposition of the PCDD/Fs and PAHs is dominated by fine particles. Furthermore, it is estimated that in Bayreuth wet deposition dominates the total particle bound deposition of PCDD/Fs and PAHs.     

Atmospheric pollution by PAHs, PCDD/Fs and PCBs simultaneously collected at a regional background site in central Italy and at an urban site in Rome

Concentrations of PAHs and PCDD/Fs were measured throughout one year, and PCBs during the second semester, at a rural site in a natural park representative of background pollution in central Italy; results were compared with simultaneous measurements performed at an urban site in Rome 60km away. Twenty-four daily samples were collected at each site by a high-volume PM(10) sampler from February 2000 to January 2001. After ultrasonic extraction and clean-up by TLC, samples were analysed by GC-MS. Mean concentrations of benzo[a]pyrene (BaP, as a marker of carcinogenic PAHs), summation operatorPCDD/Fs and summation operator64 PCBs in Rome were, respectively: 1.1ngm(-3), 65fgWHO-TEQm(-3), 553pgm(-3). The background concentrations were, respectively: 0.016ngm(-3), 3fgWHO-TEQm(-3), and 94pgm(-3). Hence, BaP, and the other PAHs, showed the highest urban-background gradient (two orders of magnitude) and PCBs the lowest. The background pollution levels of BaP and PCDD/Fs were in agreement with the few available background/remote measurements in Europe. In Rome PAHs and PCBs, but not PCDD/Fs, were clearly seasonal; the PCDD/F TEQ was moderately correlated with BaP (P<0.001). At the background site, the seasonality of PAHs was less marked, while it could not be assessed for PCDD/Fs and PCBs. The PCB TEQ accounted for 4% and 15% of total (PCDD/Fs+PCBs) TEQ at the urban and background site, respectively. Mean PM(10) concentration was 54microgm(-3) in Rome and 15microgm(-3) at the background site.     

Assessment of emissions and removal of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) at start-up periods in a hazardous waste incinerator

A study was conducted to observe the changes in polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) levels and congener profiles in the flue gas of a hazardous waste incinerator during two start-up periods. Flue gas samplings were performed simultaneously through Air Pollution Control Devices (APCDs) (including boiler outlet, electrostatic precipitator (ESP) outlet, wet scrubbers (WS) outlet, and activated carbon (AC) filter outlet) in different combustion temperatures during a planned cold (long) start-up and an unplanned warm (short) start-up. The results showed that PCDD/F concentrations could be elevated during the start-up periods up to levels 3–4 times higher than those observed in the normal operation. Especially lower combustion temperatures in the short start-ups may cause high PCDD/F concentrations in the raw flue gas. Assessment of combustion temperatures and Furans/Dioxins values indicated that surface-catalyzed de novo synthesis was the dominant pathway in the formation of PCDD/Fs in the combustion units. PCDD/F removal efficiencies of Air Pollution Control Devices suggested that formation by de novo synthesis existed in ESP also when in operation, leading to increase of gaseous phase PCDD/Fs in ESP. Particle-bound PCDD/Fs were removed mainly by ESP and WS, while gaseous phase PCDD/Fs were removed by WS, and more efficiently by AC filter.

Implications: This paper evaluates PCDD/F emissions and removal performances of APCDs (ESP, wet scrubbers, and activated carbon) during two start-up periods in an incinerator. The main implications are the following: (1) start-up periods increase PCDD/F emissions up to 2–3 times in the incinerator; (2) low combustion temperatures in start-ups cause high PCDD/F emissions in raw gas; (3) formation of PCDD/Fs by de novo synthesis occurs in ESP; (4) AC is efficient in removing gaseous PCDD/Fs, but may increase particle-bound ones; and (5) scrubbers remove both gaseous and particle-bound PCDD/Fs efficiently.     

PCDD/F formation from oxy-PAH precursors in waste incinerator flyash

The yield of PCDD/F in relation to the presence of oxygenated PAH in model waste incinerator flyash has been investigated in a fixed bed laboratory scale reactor. Experiments were undertaken by thermal treatment of the model flyash at 250 and 350 °C under a simulated flue gas stream for 2 h. After reaction, the PCDD/F content of the reacted flyash and the PCDD/F released into the exhaust gas, and subsequently trapped by XAD-II resin in a down-stream condensation system were analyzed. The PAHs investigated were, dibenzofuran and benzo[b]naphtho[2,3-d]furan and were spiked onto the model flyash as reactant precursors for PCDD/F formation. The results showed significant formation of furans from both of the PAH investigated, however except from some highly chlorinated dioxin congeners, the formation of dioxins was not so common. Benzonaphthofuran was significantly more reactive than dibenzofuran in PCDD/F formation, in spite of the fact that dibenzofuran is structurally more similar to that of PCDD/F. Thus, there was no clear attribution between the chemical structure of PAH used and the formation of PCDD/F. There were considerable differences between the yields of PCDD/F congeners in the gaseous species and those in the reacted flyash under the same operational conditions. The concentration of PCDD/Fs was reduced at the higher reaction temperature of 350 °C; however, the higher temperature resulted in the majority of the PCDD/F formed on the flyash being released into the gas phase.     

PCBs,PCNs, PCDD/Fs,PAHs and Cl-PAHs in air and water particulate samples--patterns and variations

Methodology for the determination of biologically active polychlorinated biphenyls (PCBs), non-ortho PCBs, polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polycyclic aromatic hydrocarbons (PAHs) was used to investigate concentrations and patterns of certain chlorinated PAH (Cl-PAH) in source related samples using synthetic reference mixtures. Thus, in addition to the above mentioned compounds, mono-heptachlorosubstituted fluorenes, phenanthrenes/anthracenes and pyrenes/fluoranthenes (Cl-PAHs) were measured in vapour and particulate air samples from urban road tunnels, samples of settling particulate matter (SPM), and in bottom sediment samples from two point source locations (pulp and paper, and Mg-plant/Fe-Mn-smelter/chlor-alkali) and in the Baltic Sea. Concentrations in air samples followed: PAHs>PCBs>PCNs>non-ortho PCBs or Cl-PAHs>PCDD/Fs. SPM samples collected at increasing distance to the urban area of Stockholm showed: PAHs>PCBs>PCNs>PCDD/Fs>non-ortho PCBs or Cl-PAHs. For all compound groups there was a tenfold (Cl-PAHs fivefold) concentration decrease in SPM samples from highest levels in the urban water area to lowest levels at a distance of 26 km from city centre. PCB profiles of SPM showed similarities with combined profiles of Aroclor 1242 and 1254. PCN profiles of SPM showed similarities with combined profiles of Halowax 1099 and 1014. A correlation with concentration of all tested Cl-PAH and their corresponding parent PAH was found only for Cl-fluorene.