Thermodynamic modeling of PCDD/Fs formation in thermal processes

Three thermodynamic databases of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), derived using the Group Additivity approach and two computational molecular modeling methods, Modified Neglect of Diatomic Overlap (MNDO) and Parametrized Model 3 (PM3), respectively, combined with the Scientific Group Thermodata Europe (SGTE) database have been used to model the formation of PCDD/Fs in thermal processes, such as iron ore sintering process. The predictions using the three different databases are compared, and similar thermodynamic conditions of PCDD/Fs formation are found. The comparison of the calculated values with measured results obtained from industrial iron ore sinter plant indicates that the PCDDs and PCDFs found in practice are not in equilibrium with each other. While within each dioxin and furan homologue equilibrium between the isomers appears to be established in industrial processes, reactions between dioxins and furans seem to be kinetically inhibited. This view has been supported by assuming no reaction at all between PCDFs and PCDDs in the simulation. With this assumption, both PCDFs and PCDDs reached partial pressures between 600 and 800 K in the order of magnitude actually found in practice. Taking this restriction into account, the conditions for PCDD/Fs formation were calculated as a function of oxygen partial pressure; temperature; concentrations of carbon, hydrogen, and chlorine; and C/H ratio.     

Amines compounds as inhibitors of PCDD/Fs de novo formation on sintering process fly ash

The polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are highly toxic compounds produced by some natural processes and different human activities. Waste incineration as well as steel and iron industries, in particular, the sintering process, are among the principal sources of these pollutants. In this paper, two inhibitors, triethanolamine (TEA) and monoethanolamine (MEA) are tested relating to their abilityto prevent the de novo formation of PCDD/Fs on sinter plant fly ash. The amounts of both PCDDs and PCDFs, formed by thermal treatment of the fly ash, decrease when inhibitors are added. The best results, up to 90% reduction of the PCDD/ Fs formation, are obtained when MEA is mixed with the fly ash at the highest concentration tested (2 wt %). The addition of inhibitors modifies the PCDFs/PCDDs ratios and, under some experimental conditions, the PCDD/Fs homologue distributions, suggesting that more than one pathway for the de novo formation of PCDD/Fs exist. On the other hand, no modification in the PCDD/Fs isomer distributions is observed as a result of the addition of inhibitors, in accordance with the possible thermodynamic control of these distributions. The temperature tested, 325 and 400 degrees C, does not affect the inhibition activity; however, longer reaction times (4 h instead of 2 h) give better percentages of PCDD/Fs reduction. The results suggest that the two inhibitors and especially MEA can reduce the PCDD/Fs formation on sinter plant fly ash under various conditions of temperature and reaction time, making them suitable for use in the real process. Tests performed in parallel at a real sinter plant are in good agreement with the laboratory experiments and confirm that the use of inhibitors is an appropriate technique for the prevention of PCDD/Fs emissions from sintering processes.     

Influence of metallic chlorides on the formation of PCDD/Fs during low-temperature oxidation of carbon

Experimental study was conducted to clarify the formation behavior of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from carbonaceous materials through a de novo synthesis route. Samples were prepared by changing mixing method and composite state of metallic chloride in graphite powder in order to simulate the texture of "unburned carbonaceous particles", i.e., soot, formed in thermal processes. Reagents of KCl, CaCl2. 2H2O, FeCl3 x 6H2O, and CuCl2 x 2H2O were used as chlorine sources and were added to graphite powder with different methods. The composite state of metallic chloride was varied by preliminary treatments: hand-mixing, mixed-grinding using a high-intensity ball mill, and preheating at different temperatures between 500 and 1100 degrees C. In the de novo experiment, reaction temperature and oxygen concentration of flowed gas were set at 300 degrees C and 2.5 mol %, respectively. During the experiment, formation rates of CO and CO2 and the formed amounts of organic chlorine and PCDD/Fs were measured. The results show a reasonable relation between the amount of formed organic chlorine and oxidation rate of carbon, and the order of the activity of metallic chlorines was obtained as KCl < CaCl2 < FeCl3 < CuCl2. Furthermore, it was found that the effect of the composite state of metallic chloride on the formation of PCDD/Fs significantly depends on the kind of metal. The results will give useful information to examine the formation mechanism of PCDD/Fs from unburned carbon particles in thermal processes.     

Secondary effects of catalytic diesel particulate filters: copper-induced formation of PCDD/Fs

Potential risks of a secondary formation of polychlorinated dibenzodioxins/furans (PCDD/Fs) were assessed for two cordierite-based, wall-through diesel particulate filters (DPFs) for which soot combustion was either catalyzed with an iron- or a copper-based fuel additive. A heavy duty diesel engine was used as test platform, applying the eight-stage ISO 8178/4 C1 cycle. DPF applications neither affected the engine performance, nor did they increase NO, NO2, CO, and CO2 emissions. The latter is a metric for fuel consumption. THC emissions decreased by about 40% when deploying DPFs. PCDD/F emissions, with a focus on tetra- to octachlorinated congeners, were compared under standard and worst case conditions (enhanced chlorine uptake). The iron-catalyzed DPF neither increased PCDD/F emissions, nor did it change the congener pattern, even when traces of chlorine became available. In case of copper, PCDD/F emissions increased by up to 3 orders of magnitude from 22 to 200 to 12 700 pg I-TEQ/L with fuels of < 2, 14, and 110 microg/g chlorine, respectively. Mainly lower chlorinated DD/Fs were formed. Based on these substantial effects on PCDD/F emissions, the copper-catalyzed DPF system was not approved for workplace applications, whereas the iron system fulfilled all the specifications of the Swiss procedures for DPF approval (VERT).     

Characterization and inventory of PCDD/Fs and PBDD/Fs emissions from the incineration of waste printed circuit board

Many developing countries have not significantly changed their course with regard to electronic waste contamination, and they are still facing the specter of mountains of hazardous electronic waste, with serious consequences for both the environment and public health. An efficient and stable analytical method was developed to determine the inventory and emission factors of polybrominated dibenzo-p-dioxin and dibenzofurans (PBDD/Fs) and polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs) formed from the incineration of scrap printed circuit boards (PCBs). Both PBDD/Fs and PCDD/Fs have been found in all experimental sections with a maximum formation rate at temperatures between 250 and 400 °C. The amounts tended first to increase and then began to decrease as the temperature rose. When subjected to a heating temperature of 325 °C, the total content of twelve 2,3,7,8-substituted PBDD/Fs congeners (tetra- through octabromo-) gathered from three outputs was the largest, at 19?000, 160?000, and 57 ng TEQ/kg in solid, liquid, and gaseous fractions, respectively; the total content of seventeen 2,3,7,8-substituted PCDD/Fs congeners (tetra- through octachloro-) was 820, 550, and 1.4 ng TEQ/kg. The formation of PCDD/Fs was remarkably less than that of PBDD/Fs because bromine concentrations considerably exceeded chlorine concentrations. The ingredients and conditions necessary to form PCDD/Fs or PBDD/Fs were definitely present, such as products of incomplete combustion, halogenides, an oxidizing atmosphere, and a catalyst-Cu salts being the most effective, significantly increasing the yields of PCDD/Fs and PBDD/Fs and decreasing the optimum temperature range.     

Observations on historical, contemporary, and natural PCDD/Fs

PCDD/Fs were determined in samples of archived surface soils collected from different locations around the world in the early 1880s, in contemporary surface soils from around the world, in archived subsurface soils collected at Rothamsted Experimental Station in the 1870/1880s, and in sections of peat core deposited between 5000 BP and the present. PCDD/Fs were detected in most of the samples. The potential sources and implications of the levels and mixtures of PCDD/Fs present in the samples are discussed. The homologue and isomer patterns observed in most of the contemporary European surface soils are commonly observed for European air samples and soil samples. The homologue pattern in the Rothamsted surface soils collected in the 1800s was similar, suggesting that similar sources of atmospheric emissions of PCDD/ Fs were operating in the UK in the 1800s as currently. Very different patterns, dominated by OCDD and with contributions of HpCDD and HxCDD, were found in some other samples. It is proposed that the PCDD/Fs present in the subsurface Rothamsted soils, archived (1880s) surface soils from Illinois and the Congo, clay beneath the peat bog (deposited approximately 5000 BP), and possibly surface soil samples from Thailand and Australia are of a natural origin. The most abundant TeCDD/F congeners measured in the peat samples here were also those observed by previous workers who studied a Canadian peat bog and are consistent with the microbially mediated oxidative coupling of chlorophenols. The study provides evidence for the widespread occurrence of PCDD/Fs in the environment prior to 1900 and for a complex array of sources (including natural) and environmental transformation processes.     

Formation of PCDD/Fs from the copper oxide-mediated pyrolysis and oxidation of 1,2-dichlorobenzene

Formation of polychorinated dibenzo-p-dioxins (PCDDs) has been demonstrated to occur via surface-mediated reactions of chlorinated phenols. However, polychlorinated dibenzofurans (PCDFs) are observed in much lower yields in laboratory studies than in full-scale combustors where PCDFs are in higher concentrations than PCDDs. This has led to the suggestion that at least PCDFs are formed from elemental carbon in the de novo process. However, the potential for PCDF formation from reactions of chlorinated benzenes has been largely overlooked. In this study, we investigated the potential contribution of chlorinated benzenes to formation of PCDD/Fs using 1,2-dichlorobenzene as a surrogate for reactions of other chlorinated benzenes and CuO/silica (3 wt % Cu) as a surrogate for fly ash. Results were similar for oxidative and pyrolytic conditions with a slight increase in more chlorinated products under oxidative conditions. Reaction products included chlorobenzene, polychlorinated benzenes, phenol, 2-monochlorophenol (2-MCP), dichlorophenols, and trichlorophenols with yields ranging from 0.01 to 2% for the phenols and from 0.01 to 10% for chlorinated benzenes. 4,6-Dichlorodibenzo furan (4,6-DCDF) and dibenzofuran (DF) were observed in maximum yields of 0.2% and 0.5%, respectively, under pyrolytic conditions and 0.1% and 0.3%, respectively, under oxidative conditions. In previous studies of the pyrolysis of 2-MCP under identical conditions, 4,6-DCDF and dibenzo-p-dioxin (DD) were observed with maximum yields of ～0.2% and ～0.1%, respectively, along with trace quantities of 1-monochlorodibenzo-p-dioxin (1-MCDD). Under oxidative conditions, 1-MCDD, DD, and 4,6-DCDF were observed with maximum yields of 0.3%, 0.07% and 0.1%, respectively. When combined with the fact that measured concentrations of chlorinated benzenes are 10-100× that of chlorinated phenols in full-scale combustion systems, the data suggest surface-mediated reactions of chlorinated benzenes can be a significant source of PCDD/F emissions.     

Mechanisms of dioxin formation from the high-temperature oxidation of 2-chlorophenol

The homogeneous, gas-phase oxidative thermal degradation of 2-chlorophenol was studied in a 1 cm i.d., fused silica flow reactor at a concentration of 88 ppm, reaction time of 2.0 s, over a temperature range of 300 to 1000 degrees C. Observed products in order of yield were as follows: 4,6-dichlorodibenzofuran (4,6-DCDF) > dibenzo-p-dioxin (DD) > 1-monochlorodibenzo-p-dioxin (1-MCDD), 4-chlorodibenzofuran (4-MCDF), dibenzofuran (DF), naphthalene, chloronaphthalene, 2,4-dichlorophenol, 2,6-dichlorophenol, phenol, chlorobenzene, and benzene. In contrast to pyrolysis, 4,6-DCDF is the major product rather than DD, and 1-MCDD and naphthalene are formed at temperatures as low as 400 degrees C. Under oxidative conditions, .OH and Cl. are the major carriers, which favors 4,6-DCDF formation over DD or 1-MCDD through abstraction of H. through diketo- and ether- intermediates. It is proposed that below 500 degrees C, unimolecular tautomerization/HCI elimination and CO elimination/isomerization reactions result in the formation of 1-MCDD and naphthalene, respectively.     

食品中PCDD/Fs和dlPCBs的检测方法研究进展

二恶英化合物是典型的高毒性持久性有机污染物,可在食物链中不断累积,最终引发食品安全问题,严重威胁人类健康。近年来,食品中二恶英类化合物的分析筛选和监测控制等问题一直是人们研究的重点。本文综述了二恶英类化合物的致毒机制和几种用于分析检测二恶英类化合物方法的基本原理和优缺点,以及国内外分析检测的最新研究进展,并对我国开展二恶英分析监测提出了建议和展望。     

Mechanism and direct kinetics study on the homogeneous gas-phase formation of PBDD/Fs from 2-BP, 2,4-DBP, and 2,4,6-TBP as precursors

This study investigated the homogeneous gas-phase formation of polybrominated dibenzo-p-dioxin/dibenzofurans (PBDD/Fs) from 2-BP, 2,4-DBP, and 2,4,6-TBP as precursors. First, density functional theory (DFT) calculations were carried out for the formation mechanism. The geometries and frequencies of the stationary points were calculated at the MPWB1K/6-31+G(d,p) level, and the energetic parameters were further refined by the MPWB1K/6-311+G(3df,2p) method. Then, the formation mechanism of PBDD/Fs was compared and contrasted with the PCDD/F formation mechanism from 2-CP, 2,4-DCP, and 2,4,6-TCP as precursors. Finally, the rate constants of the crucial elementary reactions were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) correction over a wide temperature range of 600-1200 K. Present results indicate that only BPs with bromine at the ortho position are capable of forming PBDDs. The study, together with works already published from our group, clearly shows an increased propensity for the dioxin formations from BPs over the analogous CPs. Multibromine substitutions suppress the PBDD/F formations.     

Experimental study on the effect of SO2 on PCDD/F emissions: determination of the importance of gas-phase versus solid-phase reactions in PCDD/F formation

Cofiring coal in municipal solid waste incinerators (MSWls) has previously been reported to reduce polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs) emissions due to increasing the flue gas SO2 concentration. The present study was focused on understanding the primary mechanism responsible for the suppressant effect of SO2 on total PCDD/F formation and toxic equivalent (TEQ) emissions. The addition of SO2, simulating the effect of coal addition on the flue gas composition, resulted in significant reductions in the TEQ emissions due to reactions involving SO2 in the postcombustion zone. However, emissions of total PCDDs/Fs, unlike the TEQ value, were dependent upon the Cl2 and SO2 injection temperatures due to increases in non-TEQ correlated isomers. The conversion of metal chlorides in the fly ash to sulfates, thus reducing the sites responsible for chlorination/oxidation reactions, was concluded to be the main suppressant mechanism; proposed reactions for copper and iron are presented. This mechanism was found to be independent of combustion conditions and could have prolonged effects on PCDD/F emissions from deposits formed with high flue gas S/Cl ratios.     

基于GC-MS/MS法测定鱼肉中二噁英和二噁英类多氯联苯

建立基于GC-MS/MS方法,采用稳定性同位素稀释法测定鱼肉中二噁英及二噁英类多氯联苯。样品经快速溶剂萃取仪提取3次,以酸化硅胶除脂,经多层硅胶柱、碱性氧化铝柱和活性炭柱净化,分别收集含PCDD/Fs和DL-PCBs组分,经浓缩复溶后供GC-MS/MS测定。结果表明:在净化步骤中,PCDD/Fs和DL-PCBs受洗脱液的体积以及收集步骤的影响较大,分开收集PCDD/Fs和DL-PCBs,先对PCDD/Fs的收集液进行测定,然后将其和DL-PCBs的收集液合并完成DL-PCBs的测定,从而对DL-PCBs进行准确定量。采用鱼肉为样品基质时,该方法PCDD/Fs和DL-PCBs的内标回收率为63.3%～106.8%,RSD为0.4%～9.6%;目标物的回收率为93.6%～114.5%,RSD为0.9%～9.2%,方法线性和检出限达到国家标准GB 5009.205的要求,适用于鱼肉样品中PCDD/Fs和DL-PCBs的测定。     

Distribution of mono to octa-chlorinated PCDD/Fs in fly ash from a municipal solid-waste incinerator

We have estimated the concentration and distribution of the mono to octa-chlorinated congeners of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in fly ashes at various sampling points in a large-scale municipal solid waste incinerator at Ume?, Sweden, as they cooled from 700 to 170 degrees C. Differences between the ashes were observed, the PCDD homologue profile was found to vary with temperature. The total amount of PCDD and PCDF increased as the temperature decreased in the postcombustion zone. The increase was due to both adsorption to the fly ash and formation of PCDD and PCDF. Mono-to trichlorinated PCDD predominated at high temperatures, whereas hepta- and octachlorinated PCDD predominated at temperatures below 400 degrees C. PCDF predominated over PCDD in the whole temperature range. However,the changes in homologue profile for PCDFwere minor. The isomer distribution within the homologue groups was not changed asthetemperature decreased in the postcombustion zone.     

Formation of PCDD/Fs in the sintering process: influence of the raw materials

The sintering process is among the major sources of PCDD/Fs in the environment. This research studies the influence of the raw materials in this type of industrial plant on the amounts of PCDD/Fs generated. Particular interest is given to coke, which constitutes the principal source of carbon for the de novo synthesis of PCDD/Fs, and to the dust collected in the electrostatic precipitator (E.S.P. dust), usually recycled in the raw materials. The de novo synthesis of PCDD/Fs is simulated at the laboratory scale by thermal treatments of the samples. The use of a particular coke as a fuel does not drastically reduce the formation of PCDD/Fs. Actually, the global amounts of PCDD/Fs generated from the graphite and the two cokes tested are very similar. Only modifications in the fingerprint are observed. On the other hand, the addition of 10 wt % dust collected in the electrostatic precipitator leads to the formation of amounts of PCDD/Fs multiplied by a factor larger than 10(3). These results imply caution against the recycling of this E.S.P. dust in the raw materials.     

Further evidence for the existence of PCDD/Fs in the environment prior to 1900

PCDD/Fs and PCBs have been analyzed in a series of archived soil samples collected from various depths during the 1800s and early 1900s. PCBs were not found in soil samples collected before 1900, whereas PCDD/Fs were present in concentrations between 43 and 110 pg/g in surface soils, and between 9 and 150 pg/g in soils collected from below the surface. The PCDD/F homologue patterns of all surface soils were consistent with each other. The homologue pattern of deeper soils altered with depth to one that was dominated by highly chlorinated PCDDs. The highest sigma(4-8)PCDD/F concentration (150 pg/g) was found in the deepest soil analyzed (230-250 cm below the surface). The cork from one of the storage bottles contained considerable quantities of both PCBs and PCDD/Fs. However, contamination of the soils, either by diffusion through the cork or by cork particles, was discounted on the basis that no PCBs were evident in the soil, and that the PCDD/F homologue pattern in the cork was very different to that found in the soil. Similar arguments were used to discount contamination of the soil by dust. A sample of ashed vegetation from the archive, that had no cork stopper, contained high concentrations of PCBs (78 ng/g), concentrations of mono- to tri-CDFs that were higher than in any of the soils (190 pg/g), but very low concentrations of sigma(4-8)PCDD/F (12 pg/g). This pattern of analytes was considered to be representative of contamination from store room air and was completely different from the pattern observed in the soils. Taken together these observations indicate that contamination during storage, or subsequent handling, is unlikely to have occurred in archived soil samples that were stored with cork and wax seal intact. The results imply surface soil sigma(4-8)PCDD/F concentrations of around 60 pg/g at Rothamsted (southeast England) in the late 1800s, compared with approximately 300 pg/g reported for rural UK soils in the 1990s.     

Soot-carbon influenced distribution of PCDD/Fs in the marine environment of the Grenlandsfjords,Norway

The particle associations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) were studied in both the water column and the surface sediments of a marine fiord system and were found to poorly obey expectations from the organic matter partitioning (OMP) paradigm. The field observations were instead consistent with the presence of a stronger sorbent subdomain such as pyrogenic soot-carbon (SC) playing an important role in affecting the environmental distribution and fate of PCDD/Fs. Solid-water distribution coefficients (Kd) of PCDD/ Fs actually observed in the water column were several orders of magnitude above predictions from a commonly used OMP model. Even when these elevated Kd values were normalized to the particulate organic carbon (POC) content (i.e., K(OC)), the variability in K(OC) for individual PCDD/ Fs at different fjord locations and seasons of factors 100-1,000 suggested that bulk organic matter was not the governing sorbent domain of the suspended particles. Further, POC-normalized particle concentrations of PCDD/ Fs (C(OC)) in a vertical profile (surface water-bottom water-surface sediment) revealed a strong increasing trend with depth. Factors of about 100 higher Coc for all PCDD/Fs in the sediment than in the surface water could not be explained by higher fugacity in the surrounding deep water nor with C:N or delta13C indexes of selective aging of the bulk organic matter. Instead this was hypothesized to reflect selective preservation of a more recalcitrant and highly sorbing, but minor, subdomain such as soot. The extent of enhanced PCDD/F sorption, above the OMP predictions, was positively correlated with the SC:POC ratio of the suspended particles in surface and deep waters. Finally, the geographical distribution of sedimentary PCDD/F concentrations were better explained by the SC content than by the bulk OC content of the sediment. Altogether, these field-based findings add to recent laboratory-based sorption studies to suggest that we need to consider both amorphous OC partitioning domains and SC particles as carriers of planar aromatic contaminants if we are to explain the environmental distribution and fate of pollutants such as PCDD/Fs.     

牛乳中二噁英类化合物标准物质的研制

研制乳粉中非添加二噁英类化合物的标准物质,加强我国二噁英类化合物实验室检测质控能力建设。方法 选择满足侯选物筛选原则和要求的牛乳样品作为候选物,经混匀、分装、冻干后,以高分辨气相色谱-高分辨质谱法同位素稀释技术测定多氯代苯并二噁英、多氯代苯并呋喃(PCDD/Fs)和二噁英样多氯联苯(dl-PCBs),经均匀性和稳定性试验后,采用多家实验室联合定值方法对样品中二噁英类化合物含量进行定值及不确定度分析。结果 经单因素方差分析和F检验,瓶间均匀性试验的检验值F均小于临界值F0.01(9,40)。室温下1年的稳定性试验结果显示,定值化合物一元线性拟合方程中斜率|b₁|均小于t(0.95,3)×s(b₁),表明特征值变化趋势无统计学意义。结论 本研究提出了二噁英类化合物定值结果,为二噁英检测提供质控参考和能力评价。     

An isomer prediction model for PCNs, PCDD/Fs, and PCBs from municipal waste incinerators

Isomer patterns of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated biphenyls (PCBs), and polychlorinated dibenzofurans (PCDFs) from municipal waste incinerators (MWIs) were predicted by a model based on symmetry numbers and preferential chlorination positions. Fly ash isomer patterns from five stoker and seven fluidized bed incinerators were compared to validate the prediction model. The isomer patterns of the highly chlorinated PCN homologues from stoker type incinerators were successfully predicted. The relative equilibrium concentrations of tetrachloronaphthalenes (TeCNs), calculated by an ab initio method, cannot explain the field isomer patterns. Formation pathways involving chlorophenol precursor condensation reactions should be examined to see whether these isomer patterns provide a better fit to the field PCDD data. The PCB isomer patterns were fit reasonably well, but this finding could merely be an artifact of the limited data and the large number of isomers. The prediction equations of PCDFs, revised from prior work to include a symmetry number for each isomer, represented the field data patterns for the higher chlorinated isomers very well. Successful prediction of isomer patterns for partial homologue ranges suggests that these patterns are determined by a mechanism governed by Cl-position-specific preferences.     

Removal of PCDD/Fs from flue gas by a fixed-bed activated carbon filter in a hazardous waste incinerator

The adsorption of polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) by activated carbon (AC) was examined in a fixed-bed AC unit in a hazardous waste incinerator (IZAYDAS) in Turkey. Results showed that the removal efficiencies of PCDD/Fs decrease as the chlorination level increases, which was explained by the difference in gas/particle partitioning of the compounds. Since dioxins are tightly adsorbed by activated carbon, other flue gas constituents showed no clear effect on the dioxin removal. Adsorption kinetics indicated that the adsorption of volatile congeners and homologues fits well with Henry's law, possibly due to the higher gaseous fractions, while the correlation was lower for lowly volatile ones. PCDD/F congeners and homologues had a concentration value up to which no adsorption occurred, which could be attributed to the insufficient contact times at the low concentrations.     

Source identification of PCDD/Fs for various atmospheric environments in a highly industrialized city

This study set out to identify possible PCDD/F emission sources for different atmospheric environments in a highly industrialized city located in southern Taiwan. We collected stack flue gas samples from five main stationary emission sources of the municipal solid waste incinerators (MSWIs), medical waste incinerators (MWIs), electric arc furnaces (EAFs), secondary aluminum smelters (ALSs), and sinter plants to assess the characteristics of their PCDD/F emissions. For mobile sources, congener profiles reported in U.S. EPA's database for unleaded gas-fueled vehicles (UGFV) and diesel-fueled vehicles (DFV) were directly adopted owing to lack of local data. The congener profiles of the 2,3,7,8-substituted PCDD/Fs were selected as the signatures of these PCDD/F emission sources. We conducted PCDD/F samplings on atmospheric environments of four categories, including background, residential area, traffic area, and industrial area. Through PCA and cluster analyses, we found that traffic areas were most influenced by PCDD/F emissions from UGFV and DFV, while those of industrial areas were mainly influenced by metallurgical facilities and MWIs. The above results were further examined by using the methodology of the indicatory PCDD/Fs. We confirmed that traffic areas were contributed by traffic sources, but industrial areas were simply affected by metallurgical facilities rather than MWIs. In conclusion, besides the use of PCA and cluster analyses, the methodology of the indicatory PCDD/Fs should be conducted for further validation in order to prevent misjudgment.