Modeling aerosol formation in opposed-flow diffusion flames

The microstructures of atmospheric pressure, counter-flow, sooting, flat, laminar ethylene diffusion flames have been studied numerically by using a new kinetic model developed for hydrocarbon oxidation and pyrolysis. Modeling results are in reasonable agreement with experimental data in terms of concentration profiles of stable species and gas-phase aromatic compounds. Modeling results are used to analyze the controlling steps of aromatic formation and soot growth in counter-flow configurations. The formation of high molecular mass aromatics in diffusion controlled conditions is restricted to a narrow area close to the flame front where these species reach a molecular weight of about 1000 u. Depending on the flame configuration, soot formation is controlled by the coagulation of nanoparticles or by the addition of PAH to soot nuclei.     

Formation of PCDF, PCDD, PCB, and PCN in de novo synthesis from PAH: mechanistic aspects and correlation to fluidized bed incinerators

The difference of polychlorinated dibenzofurans (PCDF) isomer patterns between stoker type incinerators and some fluidized bed incinerators (FBI) is a key to understand the formation mechanisms in both types of incinerators. The total yield and the isomer patterns of PCDF, polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN), and polychlorinated benzenes (PCBz) formed via de novo synthesis from polycyclic aromatic hydrocarbons (PAH) indicate that chlorinated aromatics in the FBI are formed as a result of PAH breakdown. The detailed analysis of the isomer patterns of PCDF, PCB and PCN gives a first insight into the transformation mechanism of the PAHs and the sequence of degradation, chlorination and oxygen insertion. The major chlorination takes part at the position of the C-C cleavage during degradation of the PAHs. Further chlorination of the hydrogen position of the former PAH takes part preferably in ortho-position to this chlorination or is directed by incorporated oxygen. A perylene structure in soot is proposed as basis for the observed PCDF pattern in the FBI. Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated phenols (PxCP) were formed in lower concentrations from the de novo experiments indicating an additional formation pathway for these compounds in the FBI.     

On the possibility for separate determination of pyrolyzed products (soot and polycyclic aromatic hydrocarbons) in aerosols by EPR spectrometry

The present paper demonstrates the applicability of EPR spectrometry for separate estimation of soot (EC) and polycyclic aromatic hydrocarbons (PAH) in aerosols. The content of EC is obtained directly because of their paramagnetic properties whereas diamagnetic PAH, adsorbed on the soot, are converted to paramagnetic forms by oxidation over silica/alumina catalyst. In order to fulfill the goal of our study at this stage only few samples of aerosols are investigated after being collected at four different locations: near and distant to motorway, office and cafeteria. The obtained results show that the quantities of soot and PAH in all cases are μg m⁻³. However, their content varies depending on the place of sample collection. The following order of decreasing soot quantity is found: motorway>urban air>cafeteria>office whereas for PAH the order is cafeteria≅motorway>urban air>office. The obtained results are discussed in the light of the pollution sources at the sampling places.     

Characterization of carbonaceous combustion residues: II. Nonpolar organic compounds

Aromatic and aliphatic fractions of black carbon (BC) solvent extracts were examined by gas chromatography/mass spectrometry to determine how differences in broad chemical and physical features are correlated with the load, composition, "extractability" and bioavailability of organic compounds. Diesel soot, urban dust and chimney soot had concentrations of n-alkanes >20 microg/g and of carcinogenic polycyclic aromatic hydrocarbons (PAHs)>8 microg/g. These high levels of solvent-extractable compounds were interpreted as resulting from combustion at temperatures below optimum values for BC formation. PAH concentrations normalized to the amount of soot carbon in chimney soot were close to values for diesel soot. However, the high proportion of polar amorphous organic matter in chimney soot suggests a higher bioavailability for associated PAHs. Carbon black, vegetation fire residues, and straw and wood charcoals had only residual concentrations of n-alkanes (<9 microg/g) and PAHs (<0.2 microg/g). PAH distributions were mostly unspecific, while the overall signature of the aliphatic fraction varied with BC origin. Molecular markers among plant-derived BC included steroid and sesquiterpenoid hydrocarbons. Molecular fingerprints suggest that compounds associated with fossil BC might be more refractory than those associated with plant-derived BC.     

Treatment of hydrocarbon contamination under flow through conditions by using magnetite catalyzed chemical oxidation

Soil pollution by hydrocarbons (aromatic and aliphatic hydrocarbons) is a major environmental issue. Various treatments have been used to remove them from contaminated soils. In our previous studies, the ability of magnetite has been successfully explored to catalyze chemical oxidation for hydrocarbon remediation in batch slurry system. In the present laboratory study, column experiments were performed to evaluate the efficiency of magnetite catalyzed Fenton-like (FL) and activated persulfate (AP) oxidation for hydrocarbon degradation. Flow-through column experiments are intended to provide a better representation of field conditions. Organic extracts isolated from three different soils (an oil-contaminated soil from petrochemical industrial site and two soils polluted by polycyclic aromatic hydrocarbon (PAH) originating from coking plant sites) were spiked on sand. After solvent evaporation, spiked sand was packed in column and was subjected to oxidation using magnetite as catalyst. Oxidant solution was injected at a flow rate of 0.1 mL min^?1 under water-saturated conditions. Organic analyses were performed by GC–mass spectrometry, GC–flame ionization detector, and micro-Fourier transform infrared spectroscopy. Significant abatement of both types of hydrocarbons (60–70 %) was achieved after chemical oxidation (FL and AP) of organic extracts. No significant by-products were formed during oxidation experiment, underscoring the complete degradation of hydrocarbons. No selective degradation was observed for FL with almost similar efficiency towards all hydrocarbons. However, AP showed less reactivity towards higher molecular weight PAHs and aromatic oxygenated compounds. Results of this study demonstrated that magnetite-catalyzed chemical oxidation can effectively degrade both aromatic and aliphatic hydrocarbons (enhanced available contaminants) under flow-through conditions.     

Oxidation of polycyclic aromatic hydrocarbons by fungal isolates from an oil contaminated refinery soil

BACKGROUND AND OBJECTIVE: Indigenous soil microorganisms are used for the biodegradation of petroleum hydrocarbons in oily waste residues from the petroleum refining industry. The objective of this investigation was to determine the potential of indigenous strains of fungi in soil contaminated with petroleum hydrocarbons to biodegrade polycyclic aromatic hydrocarbons (PAH). MATERIALS AND METHODS: Twenty one fungal strains were isolated from a soil used for land-farming of oily waste residues from the petrochemical refining industry in Singapore and identified to genus level using laboratory culture and morphological techniques. Isolates were incubated in the presence of 30 mg/L of phenanthrene over a period of 28 days at 30 degrees C. The most effective strain was further evaluated to determine its ability to oxidise a wider range of PAH compounds of various molecular weight i.e acenaphthene, fluorene, fluoranthene, chrysene, benzo(a)pyrene and dibenz(ah)anthracene RESULTS AND DISCUSSION: After 28 days of incubation, 18 of the 21 fungal cultures were capable of oxidising over 50% of the phenanthrene present in culture medium, relative to abiotic controls. Fungal isolate, Penicillium sp. 06, was able to oxidise 89% of the phenanthrene present. This isolate could also oxidise more than 75% of the acenaphthene, fluorene and fluoranthene after 30 days of incubation. However, the oxidation of high molecular weight PAH i.e. chrysene, benzo(a)pyrene and dibenz(ah)anthracene by the Penicillium sp. 06 isolate was limited, where the extent of oxidation was inversely proportional to PAH molecular weight. CONCLUSIONS: Fungal isolate, Penicillium sp. 06, was effective at oxidising a range of PAH in petroleum contaminated soils, but higher molecular weight PAH were more recalcitrant. RECOMMENDATIONS AND OUTLOOK: There is potential for the re-application of this fungal strain to soil for bioremediation purposes.     

Polycyclic aromatic hydrocarbons (PAH) in top soil, leachate and groundwater from Ruseifa solid waste landfill, Jordan

The distribution profiles and pathways of polynuclear aromatic hydrocarbons in the surroundings of Ruseifa landfill area in Jordan were investigated for surface sediments, leachate, and groundwater. The total concentration of 16 polycyclic aromatic hydrocarbons (PAHs) in sediments ranged from 286 to 1704 ppm with an average value of 751 ppm. Meanwhile, concentrations of PAH in groundwater ranged between 7.1 and 12.6 ppm with an average value of 9.1 ppm. The PAH in leachate varied between 0.10 and 0.40 with an average value of 0.29 ppm. The overall PAH distribution profiles appeared to be similar for leachate and groundwater dominated by 2–3 rings system molecules. While, the sediments profile was dominated by 4–6 rings system molecules which indicated the loss of low molecular weight compounds of PAH and accumulation of higher molecular weight of PAH under prevailing semiarid and hot climatic conditions.     

PAH Growth from the pyrolysis of CPD, indene and naphthalene mixture

In this study, the addition of cyclopentadienyl (CPDyl) moieties to aromatic rings has been investigated experimenNaphthalene was selected as the representative aromatic compound and its pyrolytic reactivity was studied first to obtain background information for the pyrolysis of cyclopentadiene-indene-naphthalene mixture. The experiments were conducted in a 5 s laminar flow reactor over the temperature range of 700-850 degrees C with 50 degrees C increments. PAH growth from naphthalene pyrolysis is mainly attributed to aryl-aryl addition of naphthyl radicals and naphthalene fragmentation, with lower product formation rates comparing with hydrocarbons with CPDyl moieties. The results indicate that naphthalene is less reactive than the CPDyl containing hydrocarbon radical-molecule addition of CPDyl radicals to naphthalene results in phenanthrene, which can also be formed substantially from other growth pathways. This addition occurs mainly at low temperatures and is less favored due to the competition from more reactive indenyl and CPDyl radicals. CPDyl radical addition to naphthalene exhibits limited aromatic growth due to the aromaticity restrictions of naphthalene. The studies of hydrocarbons with and without CPDyl moieties suggest that the reaction pathways of CPDyl bearing hydrocarbons are different from those without these moieties and cannot be adequately accounted for by the existing acetylene addition and aryl-aryl addition mechanisms.     

Removal of aqueous-phase polynuclear aromatic hydrocarbons using aspen wood fibers

Roadway runoff derived polynuclear aromatic hydrocarbons (PAHs) impact the quality of surface and ground water. Inexpensive aspen wood fibers have been investigated as a means to remove dissolved PAH under laboratory conditions. Our isotherm experiments demonstrated that the uptake of naphthalene, fluorene, anthracene, and pyrene required up to 12.5 days to reach equilibrium. Aspen wood-water sorption coefficients, Kww, were linearly correlated to octanol-water partition coefficients and the molecular weight of the studied PAH compounds. The correlation between Kww and molecular weight was the most significant. Column experiments were carried out to study the sorption and desorption of fluorene, anthracene, and pyrene under dynamic conditions. The results indicate linear sorption, but non-linear desorption behavior. The degree of desorption was inversely correlated to a compound's hydrophobicity. Flow interruption experiments showed that sorption and desorption was rate limited. A mass balance of the sorption and desorption tests indicated that sorptive uptake exceeded desorptive release over a given number of pore volumes. Further, absolute mass-removal efficiency increased with the molecular weight and hydrophobicity of the PAH compound. Batch and column studies demonstrated that aspen wood has the potential to become an effective remedial agent for PAH in stormwater runoff or other PAH contaminated waters.     

Application of magnetite-activated persulfate oxidation for the degradation of PAHs in contaminated soils

In this study, feasibility of magnetite-activated persulfate oxidation (AP) was evaluated for the degradation of polycyclic aromatic hydrocarbons (PAHs) in batch slurry system. Persulfate oxidation activated with soluble Fe(II) (FP) or without activation (SP) was also tested. Kinetic oxidation of PAHs was tracked in spiked sand and in aged PAH contaminated soils at circumneutral pH. Quartz sand was spiked with: (i) single model pollutant (fluorenone) and (ii) organic extract isolated from two PAH contaminated soils (H and NM sampled from ancient coking plants) and was subjected to oxidation. Oxidation was also performed on real H and NM soils with and without an extraction pretreatment. Results indicate that oxidation of fluorenone resulted in its complete degradation by AP while abatement was very low (<20%) by SP or FP. In soil extracts spiked on sand, significant degradation of 16 PAHs was observed by AP (70-80%) in 1 week as compared to only 15% by SP or FP systems. But no PAH abatement was observed in real soils whatever the treatment used (AP, FP or SP). Then soils were subjected to an extraction pretreatment but without isolation of organic extract from soil. Oxidation of this pretreated soil showed significant abatement of PAHs by AP. On the other hand, very low degradation was achieved by FP or SP. Selective degradation of PAHs was observed by AP with lower degradation efficiency towards high molecular weight PAHs. Analyses revealed that no by-products were formed during oxidation. The results of this study demonstrate that magnetite can activate persulfate at circumneutral pH for an effective degradation of PAHs in soils. However, availability of PAHs and soil matrix were found to be the most critical factors for degradation efficiency.     

The persistence of polynuclear aromatic hydrocarbons (PAHs) in sewage sludge amended agricultural soils

In 1968, five metal enriched sewage sludges containing different concentrations of polynuclear aromatic hydrocarbons (PAHs) were applied to different plots on field soils at two experimental sites, Luddington and Lee Valley, in the UK. This resulted in substantial increases in the total PAH soil concentrations in all plots. Since application, losses have occurred, with the high molecular weight PAHs being more persistent. Calculated half-lives range from under 2 years for naphthalene to over 9 years for benzo[ghi]perylene and coronene. The losses of PAH compounds in these field experiments can be related, in part, to their physico-chemical properties, notably the octanol: water partition coefficient.     

Particle-bound PAH content in ambient air

Ambient air samples from a traffic intersection, an urban site and a petrochemical-industrial site (PCI) were collected by using several dry deposition plates, two Microorifice uniform deposited impactors (MOUDIs), one Noll Rotary Impactor (NRI) and several PS-1 (General Metal Work) samplers from March 1994 to June 1995 in southern Taiwan, to characterize the atmospheric particle-bound PAH content of these three areas. Twenty-one individual polycyclic aromatic hydrocarbons (PAHs) were analyzed primarily by using a gas chromatograph/mass spectrometer (GC/MS). In general, the sub-micron particles have a higher PAH content. This is due to the fact that soot from combustion sources consists primarily of fine particles and has a high PAH content. In addition, a smaller particle has a higher specific surface area and therefore may contain more organic carbon, which allows for more PAH adsorption. For a particle size range between 0.31 and 3.2 microm, both Urban/Traffic and PCI/Traffic ratios of particle-bound total-PAH content have the lowest values, ranging from 0.25 to 0.28 (mean = 0.26) and from 0.07 to 0.13 (mean = 0.10), respectively. This indicates that, during the accumulation process, the PAH mass shifted from a particle phase to a gas phase, or the particles aggregated with lower PAH-content particles, resulting in a reduction in particle-bound PAH content. By using the particle size distribution data, the dry deposition model in this study can provide a good prediction for the PAH content of dry deposition materials. In general, lower molecular weight PAHs had a larger fraction of dry deposition flux contributed by the gas phase; for 2-ring PAH (50.4, 46.3 and 28.4%), 3-ring PAHs (15.2, 15.4 and 11.7%) and 4-ring PAHs (13.0, 3.60 and 5.01%) for the traffic intersection, urban and PCI sites, respectively. For higher molecular weight PAHs-5-ring, 6-ring and 7-ring PAHs-their cumulation fraction (F%) of dry deposition flux contributed by the gas phase was lower than 3.26%. At the traffic intersection, urban and PCI sites, the mass median diameter of dry deposition materials (MMD(F)) of individual PAHs was between 25.3 and 49.6 microm, between 27.6 and 43.9 microm, and between 19.1 and 41.9 microm, respectively. This is due to the fact that PAH dry-deposition primarily resulted from gravitational settling of the coarse particulates (> 10 microm).     

Using Radiocarbon to Apportion Sources of Polycyclic Aromatic Hydrocarbons in Household Soot

To determine whether polycyclic aromatic hydrocarbons (PAHs) in household soot were derived from the combustion of scrap wood or creosote that was impregnated in the wood (or some combination of both), the molecular composition and radiocarbon ( 14 C) content of the total carbon and several PAHs in the soot was investigated. The 5730-year half-life of 14 C makes it an ideal marker for identifying creosote-derived PAHs ( 14 C-free) versus those derived from the combustion of wood (contemporary 14 C). The 14 C abundance of phenanthrene, fluoranthene, pyrene, and retene was determined by accelerator mass spectrometry after solvent extraction and purification by preparative capillary gas chromatography. The molecular analysis (presence of retene and 1,7-dimethylphenanthrene) and bulk 14 C content (contemporary) of the soot indicated that wood combustion was a strong source of carbon to the soot. The 14 C of retene in two soot samples was also contemporary, indicating that it was derived from the combustion of the scrap wood. These results are consistent with previous work that has suggested that retene is an excellent marker of wood combustion. However, the 14 C content of phenanthrene, fluoranthene, and pyrene in one soot sample was much lower and revealed that these compounds had a mixed creosote and wood source. Using an isotopic mass balance approach, we estimate that 40 to 70% of phenanthrene, fluoranthene, and pyrene were derived from the combustion of the scrap wood. The results of this study show that molecular marker and bulk 14 C analysis can be potentially misleading in apportioning sources of every PAH, and that molecular-level 14 C analysis of PAHs can be a powerful tool for environmental forensics.     

A detailed numerical study of the evolution of soot particle size distributions in laminar premixed flames

In this work, two numerical techniques, viz. the method of moments and a discrete h-p-Galerkin method, have been applied for numerical simulation of soot formation in a laminar premixed acetylene/oxygen/argon flame. From the evolution of the PAH and the soot particle size distributions, new insight into the different processes of soot formation is provided. For this, the single submodels have been examined with respect to their influence on the PAH and the soot particle size distributions. The particle inception step was studied in detail by comparing the simulated PAH size distributions with experimental results. Additionally, an estimation of the interaction energy of layered PAH dimers was performed by quantum chemical calculations. From these results, some evidence for the particle inception model employing coalescence of PAH molecules has been found. The numerical results for the gas phase chemical species, the particle number densities and volume fractions of soot as well as for the soot particle size distributions are compared with experimental data. Thereby, the consistency of the entire model is demonstrated.     

Polycyclic aromatic hydrocarbon composition in soils and sediments of high altitude lakes

Polycyclic aromatic hydrocarbons (PAH) in lake sediments and nearby soils of two European high mountain regions, Pyrenees and Tatra, have been studied. Similar mixtures of parent PAH were observed in all cases, indicating predominance of airborne transported combustion products. Nevertheless, the composition of these atmospherically long-range transported PAH was better preserved in the superficial layers of soils than sediments. This difference points to significant PAH degradation process, e.g. during lake water column transport, before accumulation in the latter. Post-depositional transformation was also different in both types of environmental compartments. Thus, lake sediments exhibit higher preservation of the more labile PAH involving lower degree of post-depositional oxidation. However, they also show the formation of major amounts of perylene by diagenetic transformation in the deep sections. This compound is not formed in soils where downcore enrichments of phenanthrene are observed, probably as a consequence of diagenetic aromatization of diterpenoids.     

Polycyclic aromatic hydrocarbon transport processes on the scale of a flood event in the rural watershed of Le Bebec, France

Transport processes of polycyclic aromatic hydrocarbons (PAHs) were investigated in a rural watershed in France, which led to new quantitative results on the scale of a flood event. For that purpose, principal components analysis (PCA) combined with signal decomposition of PAH Breakthrough curves were used. The results obtained by PCA enabled us to distinguish (i) the transport of low molecular weight PAHs in dissolved form and (ii) the transport of high molecular weight PAHs in particulate form. The intermediate molecular weight PAHs are distributed in these two clusters. The application of a signal decomposition method confirms the results of PCA and makes it possible to quantify the mass PAH resulting, respectively, from resuspension (13.3mg, i.e. 77% of the total mass) and from direct transfer (2.8mg=16% of the total mass). For the resuspension phase, desorption of PAH (38% of the total exported mass) could be also distinguished from sediment resuspension (39%).     

Fate of polycyclic aromatic hydrocarbons during composting of lagooning sewage sludge

The fate of 16 polycyclic aromatic hydrocarbons (PAHs), targeted by the USEPA agency, has been investigated during composting of lagooning sludge. Composting shows efficient decrease of the content and the bioavailability of each PAH. Biodegradation and sorption are suggested as the main mechanisms contributing to this decrease. During the stabilization phase of composting, extensive microbial degradation of PAHs, mainly those with a low number of aromatic rings, was achieved following development of intense thermophilic communities. However, partial sorption of PAH to non-accessible sites temporarily limits the mobility mainly of PAHs with a high number of aromatic rings plus acenaphthene and acenaphthylene, and allows them to escape microbial attack. During the maturation phase, the development of a mesophilic population could play an important role in the degradation of the remaining PAH. During this phase of composting, PAH sequestration and binding of their oxidative metabolites within new-formed humic substances might also explain PAH decrease at the end of composting. The tendency of change of content or bioavailability of various PAH compounds during composting is found to be strongly related to the number of their aromatic rings, their molecular weight and structure.     

The effect of temperature on the rate of disappearance of polycyclic aromatic hydrocarbons from soils

The effect of temperature on the range and rate of disappearance of four polycyclic aromatic hydrocarbons (PAHs; fluorene, anthracene, pyrene and chrysene) added as a mixture of pure compounds to two different soils (light loam and loamy sand) was investigated over 180 days in a laboratory experiment. An increase in temperature from 10 to 25 degrees C enhanced the losses of all four PAHs from both soils. The effect of temperature on the rate of PAH disappearance depended on the physico-chemical properties of the compound and of the soil. The long half-lives at lower temperatures as obtained in the laboratory tests may suggest high persistence of higher molecular weight PAHs under some field conditions.     

Distribution of PCNs, PCBs, and other POPs together with soot and other organic matter in the marine environment of the Grenlandsfjords, Norway

The apparently dissolved concentration of polychlorinated naphthalenes (PCNs) and three planar polychlorinated biphenyls (pPCBs) were sampled and analysed in the water column of a marine fjord system. We also measured how much of these persistent organic pollutants (POPs) were associated with suspended particles. The field observations showed that an unexpectedly high portion of the pollutants were particle-associated. The factor of deviation from model predictions had positive linear regression on the soot carbon:particulate organic carbon ratio of the particles, and on estimates of the soot-water distribution coefficient for the PCNs. The spatial distribution of surface sediment concentrations of PCNs and polycyclic aromatic hydrocarbons (PAH) were found to consistently follow the sediment content of soot (f(SC)) to a larger extent than the bulk organic matter (f(OC)). There were no systematic differences in the strength of correlation of sediments concentrations of other POPs, i.e. octachlorostyrene and organochlorine pesticides with sediment concentration to f(SC) and f(OC). Mechanisms possible of generating these types of observations, e.g. adsorption to soot carbon in the marine particle, are discussed.     

Increased retention of polycyclic aromatic hydrocarbons in soils induced by soil treatment with humic substances

The analytical recovery of a mixture of polycyclic aromatic hydrocarbons (PAHs) was determined from a soil before and after oxidation with hydrogen peroxide, and subsequently treated with increasing amounts of an exogenous humic acid and subjected to different incubation periods. The release of PAHs from soil depended on the specific structure and physico-chemical properties of each PAH, and increased with additions of exogenous humic materials for both the oxidized and non-oxidized soil as well as with time of PAH permanence in soil. PAH recoveries were lower in the non-oxidized soil, thereby revealing the importance of native organic matter in increasing PAH retention in soils. This study shows that mobility of PAHs in soils can be controlled by soil conditioning with humic substances.