An experimental and numerical study of the effects of dimethyl ether addition to fuel on polycyclic aromatic hydrocarbon and soot formation in laminar coflow ethylene/air diffusion flames

The effects of dimethyl ether addition to fuel on the formation of polycyclic aromatic hydrocarbons and soot were investigated experimentally and numerically in a laminar coflow ethylene diffusion flame at atmospheric pressure. The relative concentrations of polycyclic aromatic hydrocarbon species and the relative soot volume fractions were measured using planar laser-induced fluorescence and two-dimensional laser-induced incandescence techniques, respectively. Experiments were conducted over the entire range of dimethyl ether addition from pure ethylene to pure dimethyl ether in the fuel stream. The total carbon mass flow rate was maintained constant when the fraction of DME in the fuel stream was varied. Numerical calculations of nine diffusion flames of different dimethyl ether fractions in the fuel stream were performed using a detailed reaction mechanism consisting of 151 species and 785 reactions and a sectional soot model including soot radiation, inception of nascent soot particle due to collision of two pyrene molecules, heterogeneous surface growth and oxidation following the hydrogen abstraction acetylene addition mechanism, soot particle coagulation, and PAH surface condensation. The addition of a relatively small amount of dimethyl ether to ethylene was found experimentally to increase the concentrations of both polycyclic aromatic hydrocarbons and soot. The synergistic effect on polycyclic aromatic hydrocarbons persists over a wider range of dimethyl ether addition. The numerical results reproduce the synergistic effects of dimethyl ether addition to ethylene on both polycyclic aromatic hydrocarbons and soot, though the magnitude of soot volume fraction overshoot and the range of dimethyl ether addition associated with the synergistic effect of soot are less than those observed in the experiment. The synergistic effects of dimethyl ether addition to ethylene on many hydrocarbon species, including polycyclic aromatic ones, and soot can be fundamentally traced to the enhanced methyl concentration with the addition of dimethyl ether to ethylene. Contrary to previous findings, the pathways responsible for the synergistic effects of benzene, polycyclic aromatic hydrocarbons, and soot in the ethylene/dimethyl ether system are found to be primarily due to the cyclization of l-C₆H₆ and n-C₆H₇ and to a much lesser degree due to the interaction between C2 and C4 species for benzene formation, rather than the propargyl self-combination reaction route, though it is indeed the most important reaction for the formation of benzene.     

高效液相色谱(HPLC)在火灾原因鉴定中的应用

介绍了利用高效液相色谱鉴定汽油、煤油、柴油等石油系列为基质的常见助燃剂的分析方法。模拟火灾现场制备上述助燃剂的新鲜、挥发、过火、燃烧烟尘以及常见干扰物燃烧样品 ,并对其进行了分析研究     

Electrokinetic remediation of metals and organics from historically contaminated soil

The electrokinetic remediation of an historically contaminated soil is described. The soil was contaminated with a range of metals including lead, zinc, manganese, copper and arsenic, polycyclic aromatic hydrocarbons (PAHs) and benzene, toluene, ethylbenzene and xylene (BTEX). A small‐scale experiment (973.2 g dry weight soil), utilising a planar electrode configuration, investigated the potential for moving metals and organics. After 23 days treatment at a current density of 3.72 A /m⁻², 44% of calcium and 29% of manganese were removed from the soil at the cathode. Of the other contaminating metals, zinc and lead moved towards the cathode, but with no significant removal from the soil. Movement of PAHs was also observed, with a 94% reduction in concentration in the third of the soil closest to the anode after 23 days. A larger scale experiment (46.7 kg dry weight soil) utilised a hexagonal array of tubular anodes surrounding a central tubular cathode. Treatment for 112 days led to acidification of the soil to pH 2.59 closest to the anode in a direct line between the anode and cathode. Soil not directly in line between the electrodes was not acidified significantly. Movement of metal ions was observed, in line with the electrodes, with concentrations of lead and arsenic increasing to 162% and 171% of starting concentrations closest to the anode, respectively, and those of zinc, copper and manganese decreasing to 42%, 68% and 57%, respectively. At positions not directly in line with the electrodes, no significant metal movements were observed. Overall, there was no significant removal of contaminating metals from the soil. PAHs and BTEX compounds were moved by electroosmosis towards the cathode, with soil concentrations of PAHs reduced from 720 mgkg⁻¹ to 4.7 mgkg⁻¹ after 22 days. PAHS (28 mg) and benzene (9660 mg) were recovered in granular activated carbon (GAC) columns. © 2000 Society of Chemical Industry     

Monitoring of pollution in Egyptian Red Sea

The level of the Egyptian Red Sea water pollution by oil was studied to assess the general pattern of oil pollutants and to evaluate the hydrocarbon origin (anthropogenic, petrogenic or biogenic) with emphasis on the poly aromatic hydrocarbons in surface water. The oil extracted from the samples was analyzed by gas chromatography to determine the concentrations and distribution of aliphatic and alicyclic n-alkanes. Results obtained indicate that most of the organic species present in water samples consist of petrogenic hydrocarbons with additional biogenic types. High performance liquid chromatography (HPLC) technique was used to study the poly aromatic hydrocarbons (PAHs) fingerprints of the studied water samples. The results obtained indicate the presence of PAHs of both pyrogenic and petrogenic origins.     

Natural, anthropogenic and fossil organic matter in river sediments and suspended particulate matter: a multi-molecular marker approach

Different classes of organic matter (OM) have been systematically investigated in sediments and suspended particulate matter (SPM) along the Danube River in order to understand causes of compositional changes. Analytical pyrolysis revealed the dominance of natural organic matter (NOM) in most of the samples. The predominance of aquatic biomass is evident mainly from the abundance of organonitrogen compounds and phenol distributions. As the river enters a forested gorge, the terrestrial component of the NOM in sediments is more significant. This is reflected in abundant methoxyphenols and a very high carbon preference index. SPM sample from a tributary shows a unique geochemical signature. It contains abundant carboxylic acids, amines, isoprenoids in the pyrolyzate, and is dominated by phytol and 24-methyl-cholesta-5,24(28)-dien-3β-ol in the extract, produced by a diatom bloom. Wax esters with a relatively high proportion of short, methyl-branched alkyl-chains appear together with abundant phytadienes and n-C₁₇ alkane in some samples, suggesting a microbial origin. Anthropogenic OM from runoff and atmospheric deposition was evident from a minor input of polycyclic aromatic hydrocarbons (PAHs) originating from mixed combustion sources. Multivariate analysis using PAH data led us to define simple molecular ratios to distinguish the PAH composition in sand and silty sediments. The newly defined ratios are the alkylated phenanthrenes and anthracenes ratio (APA; C₁-C₃/C₀-C₃ phenanthrenes and anthracenes) and the PAH ring number ratio (RN; 5-6 ring parent PAHs/all parent PAHs). This demonstrates that alkylated, as well as 5-6 ring PAHs are better preserved in the finer than in coarser grained sediments. A ubiquitous, but minor input of petroleum-related contamination with a uniform composition was evident in all samples as revealed by the analysis of petroleum biomarkers. This study demonstrates that the investigation of different classes of riverine OM requires a detailed molecular analysis, applying a series of analytical techniques and adequate statistical data treatment.     

Polycyclic aromatic hydrocarbons (PAHs) in urban surface dust of Guangzhou, China: Status, sources and human health risk assessment

Ninety-six urban surface dust samples collected from Guangzhou, a typical urban center in South China, were analyzed for 16 PAHs (2-6 rings). ∑ PAHs concentrations in the urban surface dust ranged from 0.84 to 12.3 μg/g with a mean of 4.80 μg/g. High molecular weight compounds (4-6 rings) contributed to 62 to 94% of ∑ PAHs mass in the surface dust samples. Four hotspots with highest ∑ PAHs were identified via kriging prediction mapping, representing the highly-urbanized regions: central downtown, highway and industrial area. Two major origins of PAHs inputs to urban surface dust were identified as vehicle emissions (51.9%) and coal combustion (26.8%). The 95% UCL of Incremental Lifetime Cancer Risk (ILCR) due to human exposure to urban surface dust PAHs in central South China was 3.03 × 10⁻⁶ for children and 2.92 × 10⁻⁶ for adults.     

ALTERED MOBILITY OF BENZ[a]ANTHRACENE IN THE PRESENCE OF p-XYLENE AND ITS IMPACT ON RISK IN THE SUBSURFACE

Concerns over soil and groundwater contamination by PAHs have been raised as they are often introduced into the subsurface as nonaqueous-phase liquid (NAPL) mixtures. However, characterizing the risk posed by a mixture of chemicals is a challenging task due to its uncertainty in quantifying the effects of the interaction between substances. This study focuses on the effects of phase-transforming interaction on the fate, transport, and risk assessment of a PAH in a PAH - NAPL mixture. The cell test was carried out using benz[a]anthracene (BaA) and p-xylene to verify the increased mobility of highly sorbed pollutants in the presence of less sorbed, mobile liquid pollutants. The experimental results showed that BaA had greater mobility in the presence of p-xylene than in its absence. The main transport mechanisms in the vadose zone were by dissolution into p-xylene or water. The developed model showed that transport of BaA was significantly faster in the presence of NAPL, but needs improvement. As well, risk assessment indicated that the oral carcinogenic risk of BaA calculated with the concentration in groundwater was 15～ 87 times larger when mixed with NAPL than when present as a single contaminant. This study demonstrated that consideration of phase-transforming interaction is necessary to analyze the risk of a PAH - NAPL mixture. The improvement of the transport model will be the topic of our continuing research.     

CHARACTERIZATION OF SELECTED SPECIATED ORGANIC COMPOUNDS ASSOCIATED WITH PARTICULATE MATTER IN AMBIENT AIR OF THE OUTSKIRTS OF ROME

The organic fraction of airborne particulate matter includes a wide variety of organic compounds, but the present research focus is on Polycyclic Aromatic Hydrocarbons (PAHs) and their nitrated derivatives (nitro-PAHs) because of the well-known health risk associated with these organics. In order to identify and assess the sources of hydrocarbon inputs into the environment n-alkanes content and the relative carbon preference index were utilized.

Special consideration was given to nitro-PAHs. The aim of this work was to demonstrate the presence in atmosphere of nitro-PAHs not usually studied, which may be responsible for part of the high direct-acting mutagenic activity of unknown origin observed for the airborne particulate material.

Of the 38 particulate-associated nitro-PAH compounds measured, 21 were described for the first time and 17 were detected in real samples, although those 21 nitro-PAHs were reported as positional isomers of corresponding PAHs, with the position of the NO₂ group not determined.