Analysis of polychlorodibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs) in baked-salt food additives in Korea

Thirty-one samples of baked-salt products used in commercial food additives were analyzed for the presence of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Dioxins were highly detected in 12 samples of baked salts. The amount of dioxins found in the samples ranged from 12.47 pg/g to 406.56 pg/g (0.71 pg TEQ/g to 23.51 pg TEQ/g, respectively). The most abundant congeners, as TEQ values, were 2,3,4,7,8-PeCDF; 1,2,3,7,8-PeCDF; and 1,2,3,4,7,8-HxCDF in PCDF congeners and 1,2,3,7,8-PeCDD; 1,2,3,6,7,8-HxCDD; and 1,2,3,7,8,9-HxCDD in PCDD congeners. Meanwhile, PCDDs/PCDFs were analyzed in high-temperature-treated samples of natural sea salt alone and natural sea salt to which di-(2-ethylhexyl)phthalate (DEHP) had been added. In the former case, PCDD/PCDF formation was most evident at temperatures near 450 degrees C, the total amount of dioxins was 90.07 pg/g (6.07 pg TEQ/g), and PCDD congeners comprised less than 50% of the total PCDDs/PCDFs. However, when the latter samples were heated, the total PCDD/PCDF concentration was 512.30 pg/g (21.53 pg TEQ/g), with PCDD congeners comprising over 87% of the total PCDDs/PCDFs.     

Bioavailability of PCDDs and PCDFs on fly ash after semi-chronic oral ingestion by guinea pig and syrian golden hamster

Groups of guinea pigs and syrian golden hamster (n = 5) were fed 2.5% HCL pre-treated fly ash from the electrostatic precipitator of a municipal incinerator during one, two and three months, respectively, in the diet. The livers were analyzed for tetra-, penta- and hexa-chlorinated dibenzo(p)dioxins (PCDDs) and dibenzofurans (PCDFs).In the livers of the hamsters 2,3,7,8-substituted PCDDs and PCDFs were the major isomers retained. In the livers of the guinea pigs 2,3,7,8 substituted PCDDs and PCDF congeners were retained, but also a number of otherwise substituted PCDFs. These other PCDF congeners included some having a 2,3,6,7 or alternate chlorine substitution pattern. Those congeners retained in the livers were generally below 5% of the group dose. The PCDF congener which had the highest retention in the livers of guinea pig was 1,2,3,7,8-PnCDF, 11.3% after 95 days. In the livers of the hamsters highest retention was found for 2,3,4,7,8-PnCDF, 8.4% after 95 days. For most 2,3,7,8-substituted PCDDs and PCDFs the retention in the livers of the guinea pigs and hamsters was not significantly different during the whole period, which could indicate a bioconcentration approaching a linear relationship to the administered dose. Constant relative concentrations in the livers were found for the 2,3,7,8- substituted penta- and hexa-chlorinated PCDDs and PCDFs in both species during the three time periods.     

Relevance of coplanar PCBs for TEQ emission of fluidized bed incineration and impact of emission control devices

Five fluidized bed incinerators combusting municipal solid waste were assessed for the impact of coplanar PCBs on total TEQ emission. In 17 stack measurements, the coplanar PCBs contributed on average less than 3% to total TEQ with a maximum contribution of 7.5% to total TEQ in one measurement. Differences in the design of the flue gas cooling section did not show an effect on the impact of coplanar PCBs on total TEQ. The effect of emission control devices on the impact of coplanar PCBs on the total TEQ was studied in more detail at one incinerator. The relative contribution of PCBs to total TEQ increased along the flue gas line. This was caused by a slightly higher removal efficiency for TEQ relevant PCDDs/PCDFs compared to coplanar PCBs by the bag filters and a higher destruction efficiency for PCDDs/PCDFs compared to PCBs by the SCR catalyst. Additionally, the removal efficiencies of the emission control devices (bag filters and catalyst) for other chlorinated aromatic compounds which have been proposed as TEQ indicator compounds (polychlorinated benzenes and polychlorinated phenols) were compared with those for PCDDs/PCDFs and coplanar PCBs. Removal efficiencies for polychlorinated benzenes or polychlorinated phenols considerably differed from those of PCDD/PCDF and coplanar PCBs. Implications for TEQ assessments using indicator compounds as proposed in the literature are discussed.     

Formation of dioxins from combustion of polyvinylidene chloride in a well-controlled incinerator

Polyvinylidene chloride (PVDC; polymer of 1,1-dichloroethylene) was combusted with paper in a well-controlled, small-scale incinerator at an average grate temperature of 700 °C, and then dioxins (PCDDs, PCDFs, and coplanar-PCBs) formed in the exhaust gases were analyzed by gas chromatography/mass spectrometry. PVDC lowered the combustion temperature due to its less flammable character. The amount of total dioxins (PCDDs + PCDFs + coplanar-PCBs) formed in the exhaust gas was 58.0 ng/g of a combustion sample and its toxicity equivalency quantity (TEQ) value was 0.64 ng-TEQ/g. The amount of PCDDs formed in the sample ranged from 2.33 ng/g (Cl₈-isomer) to 0.048 ng/g (Cl₁-isomer). The lower the number of chloride, the less production of PCDDs. On the other hand, there was no relation between the number of chloride and PCDF formation. The amount of PCDFs formed in the sample ranged from 8.02 ng/g (Cl₂-isomer) to 4.46 ng/g (Cl₈-isomer). A polyvinylchloride (PVC) sample produced 207 ng/g of total dioxins and a PVDC sample produced 57.4 ng/g of total dioxins when they were combusted under the same conditions. An approximately equal composition of dioxin isomers was formed from PVDC and PVC samples. Paper was found to contribute to PCDF formation when it was combusted with plastics.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in human adipose tissues of Japan

Thirteen samples of human adipose tissue from cancer patients in Japan were analyzed for tetra- to octa- chlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). These compounds were identified in all the samples analyzed. All isomers identified have a pattern of chlorine substitution in 2, 3, 7 and 8 positions with the only exception of 1,2,3,4,6,7,9-hepta-CDD. In the case of PCDFs, the relatively higher persistency was found in the isomers with chlorine atoms at 4- (or 6-) position as compared with 1- (or 9-) position. Total PCDD concentrations were in the range of 160 to 1400 pg/g on wet weight basis, in which increasing levels were found from tetra- to octa-CDD. Total PCDF concentrations were in the range of 7 to 120 pg/g and the levels of individual congeners are rather uniform.     

Development and validation of a method for analysis of "dioxin-like" PCBs in environmental samples from the steel industry

A method, previously used for determination of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), has been modified for quantitative analysis of "dioxin-like" polychlorobiphenyls (PCBs) in environmental samples from the steel industry. The existing sample clean-up procedure, involving liquid chromatography on multi-layered silica and Florisil columns, has been extended to include a third chromatography stage on a basic alumina stationary phase. The additional clean-up stage is required for PCB analysis in order to eliminate interferences from relatively large concentrations of saturated cyclic and aliphatic hydrocarbons. Samples were analysed for WHO-12 congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) and standard solutions of the method US EPA 1668A. Replicate analysis of method blanks revealed background contamination for PCBs 118, 105 and 77, which are generally abundant in ambient air. These contaminants were taken into account using a subtraction method. The entire procedure was validated by replicate analysis (N = 3) of a certified reference sediment. The RSD for each WHO-12 congener was below 15%, 13C12-labelled PCB internal standard recoveries were in the range 70-95%. A waste dust sample collected in the electrostatic precipitator of a UK sinter plant was analysed for determination of PCDD/Fs and WHO-12 PCBs and exhibited a PCDD/F I-TEQ of 148.5 +/- 21.2 ngkg(-1) and a WHO-TEQ of 7.2 +/- 1.5 ngkg(-1). WHO-12 congeners contributed only 4.6% to the overall TEQ and PCB 126 was the major congener contributing to the WHO-TEQ (96%). The contribution to the overall TEQ of the waste dust sample was mainly attributed to PCDF followed by PCDD, which accounted for 86.6% and 8.7% to the overall TEQ, respectively.     

Sampling,occurrence and evaluation of PCDDs and PCDFs from incinerated solid urban waste

The sampling procedure of solid and gaseous pollutants, contained in flue gas emitted into the atmosphere by solid waste incinerating furnaces were investigated. Because of their extraordinary toxicological properties, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are taken into particular consideration. The analytical work is based on the use of high-resolution gas chromatography in combination with low-resolution mass spectrometry. Details of the extensive sample clean-up will follow the GC-MS separation and identification of the isomers detected for each group of PCDDs and PCDFs. Quantitative data of these pollutants distribution levels deriving from different investigated incinerators are also reported.     

Desorption of PCDD/PCDF from municipal solid waste incinerator flyash under post-combustion plant conditions

The influence of temperature on the levels of PCDD and PCDF remaining in, and desorbed from, a municipal solid waste incinerator flyash was investigated by heating the ash to between 200 and 400 degrees C under a simulated flue gas for four days reaction time. Considerable desorption of PCDD/PCDF from the flyash was seen at 275 degrees C and above. Maximum desorption occurred at 350 degrees C, with the equivalent of nearly eight times the total PCDD/PCDF concentration of the original flyash being lost to the vapour phase per unit mass of initial flyash. The I-TEQ value of the desorbed PCDD/PCDF was considerable, being over fourteen times that of the original flyash at 325 degrees C. The results indicate that formation of PCDD/PCDF on flyash deposits in the post-combustion plant of incinerators can result in the release of significant amounts of PCDD/PCDF to the flue gas stream.     

PCDD/PCDF emissions from small firing systems in households

This report presents results of emission measurements of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in the flue gas of seven oil, nine gas, and two wood firing systems under laboratory conditions. The burn rate of the combustion was in the range of the rated useful heat output. Two additional test series varied the amount of combustion air and thus the heat output. The PCDD/PCDF emissions for oil- and gas-fired boilers are in the range of 0.0020-0.0142 ng I-TEQ/m3 (referring to 3% O2 in the dry flue gas). No correlation between the combustion technique and the PCDD/PCDF emissions could be established. In the tests with the wood-fired furnaces PCDD/PCDF concentrations in the flue gas ranging from 0.014 to 0.076 ng I-TEQ/m3 (referring to 13% O2 in the dry flue gas) were found. A significant correlation between the firing rate of the heating insert and the measured PCDD/PCDF concentrations was found. On examination of three typical 2,3,7,8-CDD/CDF congener profiles, a comparable pattern could be observed with natural gas and light fuel oil. The congener distribution for wood combustion is considerably different.     

Comparative toxicities of the polychlorinated dibenzofuran (PCDF) and biphenyl (PCB) mixtures which persist in Yusho victims

The toxic Yusho oil contained a mixture of polychlorinated biphenyls (PCBs) which were contaminated by other halogenated aromatics including the highly toxic polychlorinated dibenzofurans (PCDFs). It has been reported that the PCBs and PCDFs which persist in the liver of victims still suffering from Yusho poisoning include the following compounds; 2,3′,4,4′,5-penta-,2,2′,4,4′,5,5′-,2,2′,3′,4,4′,5- and 2,3,3′,4,4′,5-hexa, 2,2′,3,4,4′,5,5′- and 2,2′,3,3′,4,4′,5-heptachlorobiphenyls and the 2,3,7,8-tetra-, 1,2,4,7,8-, 1,2,3,7,8- and 2,3,4,7,8-penta- and 1,2,3,4,7,8-hexachlorodibenzofurans. All of these PCBs and PCDFs have been synthesized and reconstituted to approximate their composition in human liver. A comparison of the dose-response effects of the reconstituted PCB and PCDF mixtures in causing weight loss, thymic atrophy and the induction of cytochrome P-448-dependent monooxygenases indicated that the PCDF mixture was at least 700 times more active than the PCBs. Since the ratio of PCBs/PCDFs persisting in Yusho patients' blood and liver was less than 600:1 and 5:1 respectively, the results suggest that the PCDFs are the major etiologic agent in Yusho poisoning.     

Dioxin like compounds from municipal waste incinerator emissions: assessment of the presence of polychlorinated naphthalenes

Polychloronaphthalenes (PCN) were identified and quantified in emission samples collected from five different municipal waste incinerators (MWI). Polychlorodibenzo-p-dioxins (PCDD) and polychlorodibenzofurans (PCDF) were also determined to find a possible relationship between these classes of organochlorinated compounds. The analyses of PCDD/PCDF and PCN were carried out by high resolution gas chromatography coupled with high resolution mass spectrometry using a positive electron ionization source and operating in the selected ion monitoring analyzer mode (HRGC-HRMS/EI(+)-SIM). The total levels of PCN varied from 1.08 up to 21.36 ng/Nm3 (mono- to octachlorinated) and 0.33 to 5.72 ng/Nm3 (tetra- to octachlorinated), whereas the levels of PCDD/PCDF ranged between 1.14 and 276.26 ng/Nm3 (0.01 and 5 ng I-TEQ/Nm3), depending on the type of the MWI. These findings do not corroborate a PCN and PCDD/PCDF correlation.     

Mechanism of the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans from chlorophenols in gas phase reactions

The pyrolysis of chlorinated phenates at a temperature of about 280 degrees C results in the formation of definite chlorinated dibenzodioxin (PCDD) congeners [1-3]. It is shown that in gas phase reactions chlorophenols react in the presence of oxygen above 340 degrees C not only to PCDD but also to chlorinated dibenzofurans (PCDF). The mechanism of this reaction of chlorophenols to PCDD and PCDF was elucidated. In a first step phenoxyradicals are formed which are capable of forming PCDDs and PCDFs. This is confirmed by the oxygen dependency of the reaction. In an argon atmosphere no dimerization of chlorophenols could be observed at 420 degrees C. By the identification of intermediates and by analyzing the PCDF isomers formed from individual chlorophenols the reaction pathway is elucidated. As intermediates in the formation of PCDFs polychlorinated dihydroxybiphenyls (DOHB) were identified. These are most likely formed by the dimerization of two phenoxy radicals at the hydrogen substituted carbons in ortho-positions under simultaneous movement of the hydrogen atoms to the phenolic oxygen PCDDs are formed in the gas phase via ortho-phenoxyphenols (POP) analogous to the pyrolysis of phenates, but due to the radical mechanism in the first condensation step to POPs not only a chlorine atom is capable for substitution but also the hydrogen atoms. The formation of the DOHBs and their condensation to PCDFs and hydroxylated PCDFs as well as the ratio of PCDD to PCDF formed show a strong dependency on the reaction temperature, the substitution pattern of the chlorophenols and the oxygen concentration.     

Use of the metastable atom bombardment (MAB) ion source for the elimination of PCDE interference in PCDD/PCDF analysis

The analysis of polychlorinated dioxins and furans (PCDDs/PCDFs) can produce erroneous results when polychloro diphenyl ethers (PCDEs) are present because they fragment and rearrange under electron ionization to give isobaric ions with PCDFs. Mass information must be generated to indicate the occurrence of possible PCDEs but uncertainty still exists if a PCDE congener has the same retention time as a PCDF congener. The metastable atom bombardment (MAB) ion source does not transfer enough energy to PCDE upon ionization to fragment the molecular ion, thus eliminating the need for PCDE tracking in PCDF analysis. Experiments were conducted with different gases, representing different ionization energies, to demonstrate that PCDE interference can be eliminated from PCDF analysis.     

Rapid PCDD/PCDF screening method for fly ash with ion trap MS/MS

A rapid screening method for the polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) in fly ash has been developed. The screening is done in two steps: (a) the extraction by the accelerated solvent extraction and (b) the quantitative measurement by ion trap tandem mass spectrometer (MS/MS). Anhydrous sodium sulfate was added to the fly ash containing activated carbon in order to increase the extraction efficiency. The selectivity of the ion trap MS/MS was confirmed with 13C-labelled internal standard. Then the results of the screening method were compared with those obtained by the conventional analytical method using high-resolution mass spectrometer (HRMS).     

Distribution of PCDDs and PCDFs in Soils Collected from the Denver Front Range - Principal Components Analysis of Diffuse Dioxin Sources (10 pp)

Background, Aims and Scope The Rocky Mountain Arsenal (RMA) is a US Army facility located northeast of Denver, Colorado that has been listed on the National Priorities List (NPL). It is currently being re-mediated under the authority of the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) and the Superfund Amendments and Reauthorization Act of 1986 (SARA). As part of the remediation activities at RMA, indications were found that a source of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) had existed on the RMA. As a result, investigations were undertaken to assess the possible nature and extent of any potential sources of PCDDs and PCDFs on the RMA site. In addition, other studies were conducted that examined PCDD/PCDF contamination in the Denver area. The goal of these studies was to examine nature and extent of PCDD/PCDF contamination both on the RMA as well as in the surrounding Denver area. The intent of this study was to characterize sources of dioxins (PCDDs) and dibenzofurans (PCDFs) at low environmental concentrations which might have originated from diffuse sources in the Denver Colorado area and in particular, the Rocky Mountain Arsenal (RMA) using Principal Component Analysis (PCA). Methods Over 200 soil samples were collected from the RMA and the Denver area. From the RMA, soil was collected as part of three studies that included a (1) random site-wide sampling of the RMA, (2) soils from the Western Tier Parcel (WTP), and (3) soils from Historic Use areas. Denver area soil samples were collected from five different land use categories: Residential, Agricultural, Open Space, Commercial, and Industrial. PCA was conducted on concentrations of 17 2,3,7,8-substuituted PCDD and PCDF congeners in 220 soil samples collected from the RMA and the Denver Front Range region. Results and Discussion PCA demonstrated the presence of possible minor sources of dioxins on the RMA. Current remediation efforts on RMA will result in the removal of these sources. Samples from the RMA were identified by the presence of a congener profile containing higher chlorinated PCDFs while the Denver Front Range areas were characterized by the presence of higher chlorinated PCDD congeners. The presence of a PCDF signature for the RMA samples does not necessarily indicate a major source of these contaminants on-site. Indeed, the relatively diffuse nature of the sample clusters would argue strongly against the presence of a single large source. Instead, the predominance of the PCDF congeners probably indicates the mixed industrial activities that took place on and near the site. Conclusion PCA results indicate that PCDD/PCDF profiles in soils collected from the RMA differed from those collected from the outlying Denver areas but that a major source of these contaminants was not present. Rather, the diffuse nature of sample clusters from the PCA indicated that the congener profile of RMA samples was most likely a result of the mixed industrial activities that historically have taken place on and near the site. PCA also indicated that many of the 'open area' (peripheral site-wide) RMA soils samples did not differ from Denver are reference congener profiles. This finding was also true for samples collected from the WTP that were essentially indistinguishable from Off-RMA reference samples. In addition, total TEQ concentrations in soils collected from WTP were similar to those measured in soils collected from the Denver Front Range areas indicating that lack of a major source of PCDD/PCDF within the WTP zones of the RMA. Recommendation and Outlook Analytical as well as statistical results of the soil congener data indicate that the WTP soils are indistinguishable from soils collected from non-industrial areas in the Denver area. This finding would support the recent 'de-listing' of the WTP from the other RMA areas and its' transfer to other authorities in the Denver area.     

A comparison of TEQ contributions from PCDDs,PCDFs and dioxin-like PCBs in sewage sludges from Catalonia,Spain

Eight sewage sludges from rural, urban and industrial wastewater treatment plants (WWTPs) in Catalonia (Spain) were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) to determine the present levels of contamination. A method based on an automated cleanup system followed by an isotope-dilution high-resolution mass spectrometric analysis was employed. Total toxicity equivalent (WHO-TEQ) values were calculated using the toxicity equivalent factors (WHO-TEFs) proposed by WHO for dioxin-like PCBs, PCDDs and PCDFs. The WHO-TEQ(PCDD/F) values for these samples ranged from 4.9 to 20.8 pg/g dry weight (d.w.), with a mean value of 9.3 pg/g d.w., whereas WHO-TEQ(PCB) levels ranged between 1.9 and 6.6 pg/g d.w., with a mean value of 4.2 pg/g d.w. The WHO-TEQ(PCB) contribution varied from 13% to 50%, suggesting that PCB contribution on the toxicity of the samples must be taken into account. Moreover, these contemporary PCDD, PCDF and PCB concentrations were compared with previous data obtained from sewage sludge samples collected during the 80s. Our findings show that contemporary PCDD, PCDF and PCB levels have declined since the 80s.     

Formation of PCDD/PCDF

One option of recycling used contaminated packaging is to recover its high energy content. This can be performed in a normal multi-fuel power plant by co-combustion of packaging-derived fuel (PDF) or refuse-derived fuel (RDF) with fossil fuels, such as coal or peat. This work includes the results of 17 co-combustion tests and an evaluation of the results by the Principal Component Analysis (PCA) and the Partial Least Squares Projections to Latent Structures (PLS). PCA and PLS calculations showed that especially Pb, but also Cr, and Cu correlated with lower chlorinated furans (PCDFs) in the fly ash. Correlation between Sn and lower chlorinated dioxins (PCDDs) in the fly ash was also noticed. CO and PAH emission in the flue gas correlated with total PCDD/Fs in the flue gas. In a real full-scale combustion process, a single parameter in fuel, flue gas or a combustion parameter did not provide a guide to PCDD/F formation or to a level of the total PCDD/F emission, but correlations between different parameters and PCDD/Fs could be found. Although PDFs and RDF had catalytic heavy metals and chlorine, the co-combustion results showed that they can be co-combusted with peat and coal in a fluidized-bed boiler at least up to 26 % with very low total PCDD and PCDF emissions.     

A simplified clean-up procedure for the rapid determination of PCDDs and PCDFs based on retention on activated carbon AX-21

Different 2,3,7,8-substituted polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs) were investigated for their retention behaviour on a disposable minicolumn containing activated carbon AX-21. Elution behaviour and recovery were examined, using native and radiolabelled PCDD and PCDF isomers.

A comparison of the total mass chromatograms of PCDDs and PCDFs in an extract from animal adipose tissue, before and after activated carbon treatment, demonstrates the efficiency of this cleanup step with respect to the elimination of interfering compounds.     

Formation of chlorinated phenols, dibenzo-p-dioxins, dibenzofurans, benzenes, benzoquinnones and perchloroethylenes from phenols in oxidative and copper (II) chloride-catalyzed thermal process

Formation of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and chlorinated phenols on CuCl(2) from unsubstituted phenol and three monochlorophenols was studied in a flow reactor over a temperature range of 100-425 degrees C. Heated nitrogen gas streams containing 8.0% oxygen were used as carrier gas. The 0.00024mol of unsubstituted phenol and 0.00039mol of each monochlorophenol were passed through a 1g and 1cm SiO(2) particle containing 0.5% (Cu by mass) CuCl(2). Chlorination preferentially occurred on ortho-(2, 6) and para-(4) positions. Chlorination increased up to 200 degrees C, and thereafter decreased as temperature increased. Chlorination of phenols plays an important role in the formation of the more chlorinated PCDD/Fs. Chlorinated benzenes are formed possibly from both chlorination of benzene and chlorodehydroxylation of phenols. Chlorinated phenols with ortho chlorine formed PCDD products, and major PCDD products were produced via loss of one chlorine. For PCDF formation, at least one unchlorinated ortho carbon was required.     

Interlaboratory sampling and analysis of PCDDS and PCDFS in emissions from urban incinerators

Three laboratories participated in a PCDD and PCDF sampling experiment on the stack of a municipal waste incinerator and six laboratories examined a fly ash sample for PCDD_S and PCDF_S in order to assess analytical precision.

The flue gas sampling results are in agreement for the three laboratories and show that the PCDD_S and PCDF_S are predominantly in the gas phase, whereas emitted particulate account for 20% of the total PCDD/PCDF concentration.