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Pressure effect on soot formation in turbulent diffusion flames.

Soot formation in a methane air turbulent jet diffusion flame is investigated numerically using a semi-empirical model. The temperature, density and species (the soot precursor C2H2) fields are calculated using detailed chemical kinetic mechanism based on the flamelet library approach. The influence of pressure on the soot formation and the behavior of the semi-empirical model in different flame situations are investigated. It is found that the flame shape and the flame temperature can be well predicted by the flamelet library approach. The calculated soot yield is mostly sensitive to the soot surface growth rate and the increase of pressure. The increase of pressure leads to the increase of soot surface growth rate and therefore to the increase of soot volume fraction. By adjusting a model constant in the soot surface growth rate, the soot emissions in both pressure p = 1 atm and p = 3 atm are properly simulated by the current semi-empirical soot model.

Journal Article↗

Absorption and adsorption of hydrophobic organic contaminants to diesel and hexane soot.

Soot particles vary in pore structure, surface properties, and content of authigenic (native) extractable organic chemicals. To better understand the effects of these properties on sorption, aqueous sorption isotherms for 14C-labeled phenanthrene and 1,2,4-trichlorobenzene were obtained for four soots of varying properties: two diesel reference soots, a hexane soot, and an ozonated hexane soot. Substantial isotherm nonlinearity was observed. In comparison to diesel soot SRM 2975, diesel soot SRM 1650b had a much higher content of extractable authigenic organic chemicals, showed less sorption of 14C-labeled sorbate at low relative concentrations (Ce/Sw), and showed higher sorption at high Ce/Sw. In comparison to normal hexane soot, the ozonated hexane soot had a higher surface O/C ratio and showed substantially less sorption at all concentrations studied. The sorption differences were attributed to the noted differences in properties, and results were interpreted through a dual-mode sorption model that included the possibility of both surface adsorption (modeled using a Polanyi-based approach) and simple phase partitioning (linear absorption). Generally, such modeling indicated that overall uptake at low concentrations in all four soots was dominated by surface adsorption but that sorption at higher sorbate concentrations in SRM 1650b was heavily influenced by linear absorption within the natively bound organic phase.

Absorption↗

Assessment of soot particle vaporization effects during laser-induced incandescence with time-resolved light scattering.

Although laser-induced incandescence (LII) has been successfully used for soot volume fraction and particle size measurements, uncertainties remain regarding issues of soot vaporization leading to mass loss and morphological changes occurring in soot due to intense heating. Prompt LII detection schemes are often based on the assumption that the associated time scale is shorter than the time scale of soot vaporization or sublimation. The validity of such assumptions is the focus of the current study. Time-resolved light-scattering measurements were made in combination with LII measurements to quantify soot particle vaporization effects resulting from the LII laser pulse. The light-scattering measurements revealed a sharp decrease in total soot particle mass during the time course of the 25 ns full-width LII laser pulse for fluences in the range of 0.5 J/cm2. Light-scattering theory was used to invert the scattering data, revealing approximately 80%-90% reductions in the soot particle volume for LII fluences of 0.47 and 0.61 J/cm2. In addition, the time-resolved scattering measurements show that the time scale of soot vaporization is completely confined to the LII laser pulse itself. Light scattering revealed no soot vaporization only for fluences of approximately 0.1 J/cm2, which is consistent with recent work on low-fluence LII. Possible mechanisms for soot vaporization are discussed, notably for near-threshold fluences.

Journal Article↗

Influence of soot on hydrophobic organic contaminant desorption and assimilation efficiency.

Soot, soot-amended sediment, and unamended sediment spiked with hydrophobic organic contaminants (HOC) were subjected to laboratory desorption and assimilation efficiency experiments in an effort to assess and compare the importance of soot in controlling HOC desorption and deposit-feeder assimilation efficiency. Three contaminants, naphthalene (NAP), benzo[a]pyrene (BaP), and hexachlorobenzene (HCB) were sorbed to sediments, sediments amended with soot (2-4% dry wt), and soot for a period of 34 d. Desorption of all three contaminants into seawater from the three prepared sorbates was then monitored, and Nereis succinea assimilation efficiency experiments on the BaP- and HCB-contaminated sorbates were conducted. Both NAP and BaP desorption rates for soot and soot-amended sediments were reduced by at least a factor of two relative to unamended sediment. Hexachlorobenzene desorption rates were similar for both the soot-amended and the unamended sediments. Results of N. succinea assimilation efficiency experiments indicate a trend similar to the desorption experiments: higher assimilation of BaP from unamended relative to soot-amended sediment and little difference in assimilation between treatments for HCB. However, soot was more effective in reducing BaP desorption than assimilation efficiency, which would be consistent with the hypothesis that the gut fluid dissolution by deposit feeders may partially decouple biological availability from chemical availability.

Adsorption↗

Influence of soot carbon on the bioaccumulation of sediment-bound polycyclic aromatic hydrocarbons by marine benthic invertebrates: an interspecies comparison.

The sorption of polycyclic aromatic hydrocarbons (PAHs) to soot carbon in marine sediments has been hypothesized to reduce PAH bioavailability. This hypothesis was tested for eight species of marine benthic invertebrates (four polychaete worms, Clymenella torquata, Nereis virens, Cirriformia grandis, and Pectinaria gouldii, and four bivalve mollusks, Macoma balthica, Mulinia lateralis, Yoldia limatula, and Mya arenaria) that span a wide range of feeding behavior, ability to metabolize PAHs, and gut chemistry. Organisms were exposed for 20 d to two PAH-spiked sediments, one with soot and one without soot. The soot treatment generally resulted in lower bioaccumulation than the no soot treatment, though the differences between treatments were not significant for all species. All but one species accumulated significant PAH concentrations in their tissues from the soot treatment, indicating that soot-bound PAH cannot be dismissed as unavailable to infaunal benthic biota. Bioaccumulation factors were correlated negatively to both the organisms' ability to metabolize PAHs and the gut fluid contact angle, supporting the hypotheses that high PAH metabolism results in lower bioaccumulation factors and bioavailability of PAHs may be limited partially by PAH solubilization in the gut lumen. The variability in bioaccumulation due to the soot treatment was much less than the variability between species and between PAH analytes. Comparatively low bioaccumulation was observed in Nereis virens, a species commonly used in bioaccumulation tests. These results suggest that more effort is needed in understanding the salient characteristics of species present in a threatened environment, rather than focusing solely on the sediment geochemistry (e.g., soot and organic carbon content) and contaminant characteristics when predicting ecological risk of PAH-contaminated sediments.

Animals↗

Polynuclear aromatic hydrocarbon and particulate emissions from two-stage combustion of polystyrene: the effects of the secondary furnace (afterburner) temperature and soot filtration.

Laboratory experiments were conducted in a two-stage horizontal muffle furnace in order to monitor emissions from batch combustion of polystyrene (PS) and identify conditions that minimize them. PS is a dominant component of municipal and hospital waste streams. Bench-scale combustion of small samples (0.5 g) of shredded styrofoam cups was conducted in air, using an electrically heated horizontal muffle furnace, kept at Tgas = 1000 degrees C. Upon devolatilization, combustion of the polymer took place in a diffusion flame over the sample. The gaseous combustion products were mixed with additional air in a venturi and were channeled to a secondary muffle furnace (afterburner) kept at Tgas = 900-1100 degrees C; residence time therein varied between 0.6 and 0.8 s. At the exits of the primary and the secondary furnace the emissions of CO, CO2, O2, NOx, particulates as well as volatile and semivolatile hydrocarbons, such as polycyclic aromatic hydrocarbons (PAH), were monitored. Online analyzers, gravimetric techniques, and gas chromatography coupled to mass spectrometry (GC-MS) were used. Experiments were also conducted with a high-temperature barrier filter, placed just before the exit of the primary furnace to prevent the particulates from entering into the secondary furnace. Results demonstrated the beneficial effect of the afterburner in reducing PAH concentrations, including those of mutagenic species such as benzo[a]pyrene. Concentrations of individual PAH exhibited a pronounced after burner temperature dependence, typically ranging from a small decrease at 900 degrees C to a larger degree of consumption at 1100 degrees C. Consumption of PAH was observed to be the dominant feature at 900 degrees C, while significant quantities of benzene and some of its derivatives, captured by means of carbosieve/Carbotrap adsorbents, were formed in the afterburner at a temperature of 1000 degrees C. In the primary furnace, about 30% of the mass of the initial polystyrene was converted into soot, while the total mass of PAH represented about 3% of the initial mass of combustible. The afterburner reduced the particulate (soot) emissions by only 20-30%, which indicates that once soot is formed its destruction is rather difficult because its oxidation kinetics are slow undertypical furnace conditions. Moreover, increasing the afterburnertemperature resulted in an increasing trend of soot emissions therefrom, which might indicate competition between soot oxidation and formation, with some additional formation occurring at the higher temperatures. Contrary to the limited effect of the afterburner, high-temperature filtration of the combustion effluent prior to the exit of the primary furnace allowed for effective soot oxidation inside of the ceramic filter. Filtration drastically reduced soot emissions, by more than 90%. Limited soot formation in the afterburner was again observed with increasing temperatures. The yields of both CO and CO2 were largely unaffected by the temperature of the afterburner but increased at the presence of the filter indicating oxidation therein. A previously developed kinetic model was used to identify major chemical reaction pathways involving PAH in the afterburner. The experimental data at the exit of the primary furnace was used as input to these model computations. A first evaluation of the predictive capability of the model was conducted for the case with ceramic filter and a temperature of 900 degrees C. The afterburner was approximated as a plug-flow reactor, and model predictions at a residence time of 0.8 s were compared to experimental data collected at its exit. In agreement with the experimental PAH concentration, only a minor impact of the afterburner treatment was observed for most species at 900 degrees C. OH was deduced to be the major reactant with a mole fraction about 4 orders of magnitudes higher than that of hydrogen radicals. Evidence for the need of further work on the quantitative assessment of oxidation of PAH and their radicals is given.

Air Pollutants↗

In situ formed soot deposit as a carbon source for polychlorinated dibenzo-p-dioxins and dibenzofurans.

The aim of this study was to investigate the role of in situ formed soot deposits generated during a combustion process for the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs). In situ formed soot deposits were generated in an entrained flow reactor by using a sooting methane (CH4) flame (sooting phase), with or without chlorine doped into the flame, and fly ash added into the gas phase. The presence of fly ash in the soot deposit was found to be critical, as a catalyst for formation and/or a chlorinating agent. The presence of chlorinated aromatic structures in the soot matrix was not enough to promote de novo formation of PCDDs/Fs without the presence of fly ash. PCDFs were formed via direct release of the molecule backbone structure from the soot. PCDDs were formed via a similar mechanism as well as an equally important formation pathway of condensation reactions of C6 compounds. The formation rate of the soot/ash depositwas still at half its original activity 34 h after the deposits were formed, suggesting a persistent de novo formation occurring for a long time after the sooting incidences (memory effect).

Benzofurans↗

Understanding the difference in oxidative properties between flame and diesel soot nanoparticles: the role of metals.

The purpose of this paper is to address the differences observed in the oxidative kinetics between flame and diesel derived soots. In particular, it has been observed that flame soot has a significantly higher activation energy for oxidation than does diesel soot. The hypothesis tested in this paper is that metals, possibly coming from lubricating oils, within diesel generated soot particles may be responsible for this effect. This is supported by the fact that addition of metal additives to diesel fuel is shown to have no effect on the activation energy of soot oxidation. The subject of this paper lies in testing the hypothesis by adding metal directly to a flame and extracting oxidation kinetics. Using a high temperature oxidation tandem differential mobility analyzer (HTO-TDMA) we extract particle size dependent kinetics for the oxidation of flame-derived soot doped with and without iron. We found that indeed addition of iron to a flame reduced the activation energy significantly from approximately 162 +/- 3 kJ/mol to approximately 116 +/- 3 kJ/mol, comparable with diesel engine generated soot with an activation energy approximately 110 kJ/mol. These results are consistent with the idea that small quantities of metals during diesel combustion may play an important role in soot abatement.

Air Pollutants↗

Diesel engine exhaust emission: oxidative behavior and microstructure of black smoke soot particulate.

Soot particulate collected from a Euro III heavy duty diesel engine run under black smoke conditions was investigated using thermogravimetry, transmission electron microscopy, electron energy loss spectroscopy, and X-ray photoelectron spectroscopy. The characterization results are compared with those of commercial carbon black. The onset temperature toward oxidation of the diesel engine soot in 5% O2 is 150 degrees C lower than that for carbon black. The burn out temperature for the diesel engine soot is 60 degrees C lower than that of the carbon black. The soot primary particles exhibit a core-shell structure. The shell of the soot particles consists of homogeneously stacked basic structure units. The commercial carbon lamp black is more graphitized than the diesel engine soot, whereas the diesel engine soot contains more carbon in aromatic nature than the carbon black and is highly surface-functionalized. Our findings reveal that technical carbon black is not a suitable model for the chemistry of the diesel engine soot.

Air Pollutants↗

Carbon black and soot: two different substances.

Carbon blacks are manufactured under controlled conditions for commercial use primarily in the rubber, painting, and printing industries. In contrast, soots are unwanted byproducts from the combustion of carbon-based materials for the generation of energy or heat, or for the disposal of waste. Unfortunately, the terms carbon black and soot often have been used interchangeably; however, carbon black is physically and chemically distinct from soot. Greater than 97% of carbon black consists of elemental carbon arranged as aciniform particulate. Depending on the type of soot, the relative amount of carbon (< 60% of the total particle mass), the type of particulate carbon, and particle characteristics (size, shape, and heterogeneity) can vary considerably. For both carbon black and soot, other elements and chemical compounds are associated with the particulate carbon. Total inorganics (ash) represent < 1% of the carbon black particle mass. Organic compounds can be extracted from particle surfaces (solvent extractable fraction [SOF]), and for carbon black, also are < 1% of the particle mass. Soots have much greater percentages of ash, SOF, or both, than carbon black. There has been concern about the adsorbed organic compounds because of potential biologic activity. For carbon black, the SOF is strongly adherent to carbon surfaces and is not released by biological fluids. The types of organic compounds consist primarily of unsubstituted polycyclic aromatic hydrocarbons and are not as biologically potent as those compounds present in soot. Thus, carbon black is distinctly different from soot, and when discussing potential health effects, care must be taken to differentiate between the two types of carbon-based particles.

Air Pollutants↗

The rapid alveolar absorption of diesel soot-adsorbed benzo[a]pyrene: bioavailability, metabolism and dosimetry of an inhaled particle-borne carcinogen.

Exposure to diesel exhaust may contribute to lung cancer in humans. It remains unclear whether the carbonaceous core of the soot particle or its coat of adsorbed/condensed organics contributes most to cancer risk. Equally unclear are the extent and rate at which organic procarcinogens desorb from soot particles in the lungs following inhalation exposure and the extent of their metabolic activation in the lungs. To explore the basic relationship between a model polycyclic aromatic hydrocarbon (PAH) and a typical carrier particle, we investigated the rate and extent of release and metabolic fate of benzo[a]pyrene (BaP) adsorbed on the carbonaceous core of diesel soot. The native organic content of the soot had been denuded by toluene extraction. Exogenous BaP was adsorbed onto the denuded soot as a surface coating corresponding to 25% of a monomolecular layer. Dogs were exposed by inhalation to an aerosol bolus of the soot-adsorbed BAP: Following deposition in the alveolar region a fraction of BaP was rapidly desorbed from the soot and quickly absorbed into the circulation. Release rates then decreased drastically. When coatings reached approximately 16% of a monolayer the remaining BaP was not bioavailable and was retained on the particles after 5.6 months in the lung. However, the bioavailability of particles transported to the lymph nodes was markedly higher; after 5.6 months the surface coating of BaP was reduced to 10%. BaP that remained adsorbed on the soot surface after this period was approximately 30% parent compound. In contrast, the rapidly released pulse of BaP, which was quickly absorbed through the alveolar epithelium after inhalation, appeared mostly unmetabolized in the circulation, along with low concentrations of phase I and phase II BaP metabolites. However, within approximately 1 h this rapidly absorbed fraction of BaP was systemically metabolized into mostly conjugated phase II metabolites. The results indicate that absorption through the alveolar epithelium is an important route of entry to the circulation of unmetabolized PAHS:

Adsorption↗

Carcinogenicity studies of Estonian oil shale soots.

Several series of chronic experiments in white mice and white rats were carried out in order to determine the carcinogenicity of Estonian oil shale soot as well as the soot from oil shale fuel oil. All the investigated samples of soot showed a relatively low (from 14 to 1200 ppm) benzo(a)pyrene content. The benzene extract of oil shale soot, painted on the skin of white mice, proved to be strongly carcinogenic: in most of the animals skin tumors developed. The benzene extract of shale fuel oil exerted a considerably weaker carcinogenic action than the extract of soot of solid shale. The effect of oil shale soots as well as of tars extracted from oil shale soot on the bronchial mucosa and lung respiratory tissue was studied in white rats. Lung tumors were induced in a considerable number of cases in a series of experiments, where the tarry material from solid fuel soot, containing 1070 ppm benzo(a)pyrene, as a suspension in an aqueous solution of Tween 40, was administered by repeated intratracheal instillation. Lung tumor incidence among various control and experimental groups of rats is presented. The peculiarities of oil shale combustion are described.

Animals↗

A calibration-independent laser-induced incandescence technique for soot measurement by detecting absolute light intensity.

Laser-induced incandescence (LII) has proved to be a useful diagnostic tool for spatially and temporally resolved measurement of particulate (soot) volume fraction and primary particle size in a wide range of applications, such as steady flames, flickering flames, and Diesel engine exhausts. We present a novel LII technique for the determination of soot volume fraction by measuring the absolute incandescence intensity, avoiding the need for ex situ calibration that typically uses a source of particles with known soot volume fraction. The technique developed in this study further extends the capabilities of existing LII for making practical quantitative measurements of soot. The spectral sensitivity of the detection system is determined by calibrating with an extended source of known radiance, and this sensitivity is then used to interpret the measured LII signals. Although it requires knowledge of the soot temperature, either from a numerical model of soot particle heating or experimentally determined by detecting LII signals at two different wavelengths, this technique offers a calibration-independent procedure for measuring soot volume fraction. Application of this technique to soot concentration measurements is demonstrated in a laminar diffusion flame.

Journal Article↗

Marine air promotes structural compaction and coating growth of soot aerosols after long-range transport from East Asia.

Soot aerosol, a key global warming contributor, undergoes morphological and chemical transformations during atmospheric transport, particularly in humidified marine environments. This study investigates morphology, mixing state, and aging mechanisms of soot particles collected in the Bohai Sea and Yellow Sea. Transmission electron microscopy analyses reveal that coated soot particles dominate the marine atmosphere, accounting for over 98 % of soot-containing particles, with a mean mixing state index (&#x3c7;) of 0.83. The fractal dimension (Df) of soot particles is 1.84 &#xb1; 0.05 in the Northern Yellow Sea, 1.90 &#xb1; 0.08 in the Bohai Sea, and 1.96 &#xb1; 0.07 in the Southern Yellow Sea, indicating structural compaction during long-range transport. Correspondingly, the average Dp/Dcore ratios (particle to core size ratio) are 5.3 in the Bohai Sea, 4.2 in the Northern Yellow Sea, and 3.9 in the Southern Yellow Sea. Notably, those ratios are higher in marine environments compared to those observed during continental regional transport from northern to southern China (3.54), suggesting enhanced coating growth in humid marine air. The results highlight the important role of marine atmospheres in accelerating soot aging, which in turn leads to significantly stronger light absorption compared to soot in continental air. Our results highlight the necessity of incorporating compact morphologies, uniform mixing states, and thick coatings into optical models for accurate radiative forcing simulations.

Aerosols↗

Knudsen cell construction, validation and studies of the uptake of oxygenated fuel additives on soot.

INTENTION, GOAL, SCOPE, BACKGROUND: The properties of atmospheric particles are important to public health, radiative forcing of the atmosphere and to elucidating the chemical reactivity of atmospheric particles. We have constructed a Knudsen cell to study the uptake of organic compounds on soot. This article describes the construction and validation of the instrument, and our results on commercial soot concerning the uptake coefficient of ethanol, acetone, 1-butanol and diethoxymethane. OBJECTIVES: First, a technical description of the instrument is presented. Next, its performance is validated by measuring the uptake of NO2 on hexane soot. Finally, the uptake coefficients of four oxygenated hydrocarbons on commercial soot are presented. The objective is to contribute to the understanding of the formation of particles in motor vehicle exhaust. METHODS: A Knudsen cell is used to measure the uptake of specific gas-surface systems. A quadrupole mass spectrometer is used to determine the decay rate of a pulse of reagent gas in the reaction chamber. RESULTS AND DISCUSSION: The BET surface area of the commercial soot was 12.6 m2/g. The uptake coefficient (gamma) has been determined for ethanol (gamma0,BET = 7.7 +/- 4.8 x 10(-8)), 1-butanol 1.4 +/- 0.54 x 10(-7)), acetone (gamma0BET = 1.5 +/- 0.15 x 10(-7)) and diethoxymethane (gamma0,BET = 2.6 +/- 0.61 x 10(-7). These results are characteristic of the specific soot sample used. The ordering of the uptake coefficients, ethanol < 1-butanol approximately acetone < diethoxymethane, can be ascribed to a combination of physical (size and mass) and chemical effects. In addition, the initial uptake coefficient for NO2 on fresh hexane soot was determined to be gamma0,BET = 1.7 +/- 1.1 x 10(-4). CONCLUSIONS: In conclusion, we demonstrate that this instrument is able to measure uptake coefficients that are in agreement with accepted literature values. New data is presented concerning four light oxygenated hydrocarbons. RECOMMENDATIONS AND OUTLOOK: A large amount of detailed information concerning individual heterogeneous reactions is necessary in order to model the composition of motor vehicle emissions. We look forward to increasing the size of this database. Results for a series of alcohols and alkanes will be presented in a forthcoming publication.

Carbon↗

A comparison of carbon black with soot.

Carbon black is frequently confused with soot. In order to clarify the distinction between these materials, we have examined 6 carbon blacks and 18 samples of soot. Carbon black is composed of turbostratic colloidal aggregates which we call aciniform carbon (AC). Chimney soots from domestic wood or coal fires contain very little AC, while in diesel soots the solid particulates are essentially all AC. All soots examined contain much more extractable organic material and/or ash than does carbon black. Ames Salmonella assays were carried out on solvent extracts. The results were calculated as net revertants per mg of the original soot or carbon black. On this basis, the majority of the soot extracts assayed were at a much higher level of mutagenicity than any of the carbon black extracts. For several reasons, even greater differences in mutagen availability would be expected if the unextracted materials were compared in vivo.

Air Pollutants↗

Oxidative stress and NFkappaB activation in the lungs of rats: a synergistic interaction between soot and iron particles.

Particulate matter (PM) has been associated with a variety of adverse health effects primarily involving the cardiopulmonary system. However, the precise biological mechanisms to explain how exposure to PM exacerbates or directly causes adverse effects are unknown. Particles of varying composition may play a critical role in these effects. To study such a phenomenon, a simple, laminar diffusion flame was used to generate aerosols of soot and iron particles in the ultrafine size range. Exposures of healthy adult rats were for 6 h/day for 3 days. Conditions used included exposure to soot only, iron only, or a combination of soot and iron. We found animals exposed to soot particles at 250 microg/m3 had no adverse respiratory effects. Exposure to iron alone at a concentration of 57 microg/m3 also had no respiratory effects. However, the addition of 45 microg/m3 of iron to soot with a combined total mass concentration of 250 microg/m3 demonstrated significant pulmonary ferritin induction, oxidative stress, elevation of IL-1beta, and cytochrome P450s, as well as activation of NFkappaB. These findings suggest that a synergistic interaction between soot and iron particles account for biological responses not found with exposure to iron alone or to soot alone.

Administration, Inhalation↗

Origin of carbon in polychlorinated dioxins and furans formed during sooting combustion.

The importance of solid- and gas-phase carbon precursors for the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs) during sooting combustion was investigated in an entrained flow reactor (EFR). Experiments were performed at various methane (CH4) flame equivalence ratios with or without gas-phase chlorine (Cl2) and fly ash, to provide a realistic environment for carbon reactions and PCDD/DF formation. Selected experiments were conducted with labeled 13CH4 and 37Cl2 to investigate the relative roles of different carbon and chlorine species for the formation of PCDD/DF. The presence of soot and ash were the two major factors controlling the PCDD/DF yields. The 16 PCDD/DF homologues as well as other analyzed chlorinated aromatics were formed by reaction pathways that varied with degree of chlorination. The mono- and dichlorinated homologues were formed by gas-phase, catalytic, or noncatalytic flame product reactions, occurring during soot formation in the near flame zone and/or at lower reaction temperatures (<650 degrees C) in the postcombustion zone. Meanwhile, the higher (tri- to octa-) chlorinated homologues were mainly formed in the postcombustion zone (<650 degrees C) by fly ash-catalyzed de novo synthesis of the soot. Of these, the PCDD/DFs were formed from high carbon number (>C12) fragments in the solid soot structure, while the PCDDs, at least in part, were also formed by reaction of two C6 fragments. The tri- to hexachlorinated DD/DF homologues were formed via a relatively fast de novo synthesis occurring during the first minutes of reactions on the continuously formed soot particles, whereas de novo synthesis on an aged soot matrix was the major pathway for the hepta- and octachlorinated congeners.

Benzofurans↗