UV-visible spectroscopy of organic carbon particulate sampled from ethylene/air flames

A systematic comparison of spectra obtained with extra and in situ diagnostics in the soot preinception region of rich, premixed ethylene air flames suggests that combustion generated organic carbon (OC) particulate can be extracted from flames and isolated from other flame material for further chemical analysis. Both the trend with height above the burner and the form of UV fluorescence and absorption spectra from extra situ sampled material captured in water agree with those measured in situ. These results show that the OC particulate formed in flames is partially water soluble. However, the collection efficiency can be increased using less polar solvents, like acetonitrile and dichloromethane. The fluorescence spectra from the water samples are comprised both a naphthalene-like component and a broad band UV fluorescence component similar to that observed in situ which is attributed to flame generated OC particulate. The broad band UV fluorescence centered around 320 nm is also observed very early in flames and does not change considerably with increasing flame residence time. These results support previous hypotheses that the UV broad band fluorescence is from carbonaceous material comprised two-ring aromatics, formed earlier than soot in the flame, and is still present along with soot at higher heights or flame residence times.     

Combustion of gasolines in premixed laminar flames European certified and California phase 2 reformulated gasoline

Two gasoline qualities, European unleaded certified gasoline (EUCG) and California phase 2 reformulated gasoline (P2 RFG), were analysed. EUCG contained about twice the amount of alkyl benzenes compared to P2 RFG and a large amount of cyclohexane. As a balance, P2 RFG contained higher amounts of isooctane and MTBE. The gasolines were burned in a premixed laminar flame burner at 1 atm and at about stoichiometric fuel/air ratio. The species profiles were measured using on-line GC/MS. About 40 compounds were be detected in the gasoline flames. The EUCG resulted in formation of more reactive and toxic compounds. The combustion profiles of the fuel components showed a similar slope, which suggests that the fuel components burn quite independently of each other. Ethene and propene were the dominating species produced from the two gasolines. Commonly, substantial amounts of higher alkenes were found. Combustion of P2 RFG produced higher amounts of isobutene, propene, propyne, propadiene and methanol compared to combustion of EUCG. The high amount of isobutene is reasonably a result of high concentration of isooctane and MTBE in the fuel. The high amount of methanol formed is probably due to the MTBE present in the gasoline. EUCG produced significantly higher amounts of 1,3-butadiene, which quite likely is formed from the cyclohexane in the fuel. The benzene profiles from both gasolines shows an almost constant level up to 800 microm from the burner surface; this is probably due to formation of benzene from alkyl benzenes.     

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.     

紫外光(UV)光解油田采出水中多环芳烃

为了探讨紫外光光解人工模拟油田采出水中多环芳烃的降解效率,利用自制反应装置对油田采出水中多环芳烃(PAHs)的紫外光光解做了一个初步研究。研究结果证明,紫外光光解对油田采出水中的多环芳烃萘和芴有显著的降解能力。实验室的测试表明,与紫外UVA(365 nm)、UVB(308 nm)的光照相比,紫外UVC(254 nm)在光照60 min的条件下,2种多环芳烃各自的去除率都近似达到了99%。可见,在光解效力和暴露时间两方面,紫外UVC对采出水中萘和芴的去除具有相对稳定和比较高的效率。     

The oxidative polymerization of aromatic molecules in the interlayer of montmorillonites studied by resonance Raman spectroscopy

The adsorption and reaction of aromatic molecules in the interlayer of transition-metal ion(Cu²⁺, Fe³⁺, Ru³⁺)-exchanged montmorillonites have been investigated by resonance Raman spectroscopy. Some mono-substituted benzenes are found to form cation radicals of 4,4′-substituted biphenyl together with those having the composition of the parent molecules. Benzene, biphenyl and p-terphenyl polymerize to form the poly-p-phenylene cation. Thus, the cation radicals or cations may remain stable when para-positions of the benzene ring are occupied by a stable substituent, or undergo polymerization when the para-position is open. Phenols behave differently in that the polymerization via the ortho-position also occurs and the reaction is faster in aerobic than in anearobic conditions.     

The characterisation of polycyclic aromatic hydrocarbons emissions from burning of different firewood species in Australia

Four kinds of woods used for residential heating in Australia were selected and burned under two burning conditions in a domestic wood heater installed in a laboratory. The selected wood species included pine (Pinus radiata), red gum (Eucalvptus camaldulensis), sugar gum (Eucalyptus cladocalyx) and yellow box (Eucalyptus melliodora). The two different burning conditions represented fast burning and slow burning, with the air inlet of the combustion chamber respectively 'full open' and 'half open'. By sampling and analysing particulate and gaseous emissions from the burning of each load of wood under defined experimental conditions, PAHs emissions and their profiles in the particulate and gaseous phases were obtained. 16 species out of the 18 selected PAHs were detected. Of these, seven species were detected in the gaseous phase and most were lower molecular weight compounds.Similarly, more than 10 species of PAHs were detected in the particulate phase and these were mostly heavier molecular weight compounds. Under both burning conditions, emission levels for total PAHs and total genotoxic PAHs were the highest for pine and lowest for sugar gum, with red gum being the second highest, followed by yellow box. Using the specific sampling method, gaseous PAHs accounted for above 90% mass fraction of total PAHs in comparison to particulate PAHs (10%). The majority of the genotoxic PAHs were present in the particulate phase. PAHs emission levels in slow burning conditions were generally higher than those in fast burning conditions.     

Monitoring of polycyclic aromatic hydrocarbons in a produced water disposal area in the Potiguar Basin,Brazilian equatorial margin

Environmental Science and Pollution Research - The Potiguar Basin has oil and gas production fields offshore and onshore. All treated produced water (PW) from these fields is discharged through...     

Polycyclic aromatic hydrocarbons in leaf cuticles and inner tissues of six species of trees in urban Beijing

Leaf samples of six tree species were collected along urban roadsides and a campus site in Beijing for measurement of polycyclic aromatic hydrocarbons (PAHs). PAHs in leaves were attributed to two fractions, leaf cuticles and inner leaf tissues, using sequential extraction. Total concentrations of 16 PAHs in the cuticles and the inner tissues were 69.3+/-64.6 microg g(-1) (d.w.) and 1.07+/-0.2 microg g(-1) (d.w.) at roadside and 57.5+/-52.6 microg g(-1) and 0.716+/-0.2 microg g(-1) on campus, respectively. The lipid-normalized inner tissue PAHs varied from 5.8 microg g(-1) to 15.0 microg g(-1). Similarities in PAH spectra between leaf cuticles and airborne particles and between the inner tissues and gaseous phase imply that airborne particulates and gaseous PAHs are likely the sources of PAHs for cuticles and the inner tissues, respectively. Difficulty in migration of heavier PAHs into inner tissues could be another reason.     

Chemometric tools applied to optimize a fast solid-phase microextraction method for analysis of polycyclic aromatic hydrocarbons in produced water

Environmental Science and Pollution Research - Chemometric tools are powerful strategies to efficiently optimize many processes. These tools were employed to optimize a fast-solid phase...     

Accumulation of weathered polycyclic aromatic hydrocarbons (PAHs) by plant and earthworm species

Experiments were conducted to assess the bioavailability of polyclycic aromatic hydrocarbons (PAHs) in soil from a Manufactured Gas Plant site. Three plant species were cultivated for four consecutive growing cycles (28 days each) in soil contaminated with 36.3 microg/g total PAH. During the first growth period, Cucurbita pepo ssp. pepo (zucchini) tissues contained significantly greater quantities of PAHs than did Cucumis sativus (cucumber) and Cucurbita pepo ssp. ovifera (squash). During the first growth cycle, zucchini plants accumulated up to 5.47 times more total PAH than did the other plants, including up to three orders of magnitude greater levels of the six ring PAHs. Over growth cycles 2-4, PAH accumulation by zucchini decreased by 85%, whereas the uptake of the contaminants by cucumber and squash remained relatively constant. Over all four growth cycles, the removal of PAHs by zucchini was still twice that of the other species. Two earthworm species accumulated significantly different amounts of PAH from the soil; Eisenia foetida and Lumbricus terrestris contained 0.204 and 0.084 microg/g total PAH, respectively, but neither species accumulated measurable quantities 5 or 6 ring PAHs. Lastly, in abiotic desorption experiments with an aqueous phase of synthetically prepared organic acid solutions, the release of 3 and 4 ring PAHs from soil was unaffected by the treatments but the desorption of 5-6 ring constituents was increased by up to two orders of magnitude. The data show that not only is the accumulation of weathered PAHs species-specific but also that the bioavailability of individual PAH constituents is highly variable.     

Monitoring the effects of atmospheric ethylene near polyethylene manufacturing plants with two sensitive plant species

Data of a multi-year (1977-1983) biomonitoring programme with marigold and petunia around polyethylene manufacturing plants was analysed to assess plant responses to atmospheric ethylene and to determine the area at risk for the phytotoxic effects of this pollutant. In both species, flower formation and growth were severely reduced close to the emission sources and plant performance improved with increasing distance. Plants exposed near the border of the research area had more flowers than the unexposed control while their growth was normal. Measurements of ethylene concentrations at a border site revealed that the growing season mean was 61.5 g m(-3) in 1982 and 15.6 g m(-3) in 1983. In terms of number of flowers, petunia was more sensitive than marigold and adverse effects were observed within ca. 400 m distance from the sources for marigold and within ca. 460 m for petunia. The area at risk (ca. 870 m) for ethylene-induced growth reduction was also limited to the industrial zone. Plants were more sensitive to ethylene in terms of growth reduction than in terms of inhibition of flowering. In the Netherlands, maximum permissible levels of ethylene are currently based on information from laboratory and greenhouse studies. Our results indicate that these levels are rather conservative in protecting field-grown plants against ethylene-induced injury near polyethylene manufacturing plants.     

Rapid quantification of polycyclic aromatic hydrocarbons in hydroxypropyl-beta-cyclodextrin (HPCD) soil extracts by synchronous fluorescence spectroscopy (SFS)

Synchronous fluorescence spectroscopy (SFS) was directly applied to rapidly quantify selected polycyclic aromatic hydrocarbons (PAHs: benzo[a]pyrene and pyrene) in aqueous hydroxypropyl-beta-cyclodextrin (HPCD) soil extract solutions from a variety of aged contaminated soils containing four different PAHs. The method was optimized and validated. The results show that SFS can be used to analyse benzo[a]pyrene and pyrene in HPCD based soil extracts with high sensitivity and selectivity. The linear calibration ranges were 4.0x10(-6)-1.0x10(-3)mM for benzo[a]pyrene and 6.0x10(-6)-1.2x10(-3)mM for pyrene in 10mM HPCD aqueous solution alone. The detection limits according to the error propagation theory for benzo[a]pyrene and pyrene were 3.9x10(-6) and 5.4x10(-6)mM, respectively. A good agreement between SFS and HPLC was reached for both determinations of PAHs in HPCD alone and in soil HPCD extracts. Hence, SFS is a potential means to simplify the present non-exhaustive hydroxypropyl-beta-cyclodextrin (HPCD)-based extraction technique for the evaluation of PAH bioavailability in soil.     

Comparisons of three plant species in accumulating polycyclic aromatic hydrocarbons (PAHs) from the atmosphere: a review

Environmental Science and Pollution Research - Plant leaves play a key role in the accumulation of PAHs, as they are able to capture PAHs from the air. In this paper, the mechanism, including...     

A field comparison of ethylene vinyl acetate and low-density polyethylene thin films for equilibrium phase passive air sampling of polycyclic aromatic hydrocarbons

Ethylene vinyl acetate (EVA) and low-density polyethylene (LDPE) were compared as thin film polymer passive air samplers for polycyclic aromatic hydrocarbons (PAHs). These samplers were co-deployed for periods of up to 27 days at an urban field site in Brisbane. Despite demonstrated air side resistance to mass transfer, sampling rate ratios indicate rapid accumulation kinetics for EVA compared with LDPE. Confirming theoretically predicted values, sampler-air partition coefficients were greater for EVA as compared with LDPE. The relatively high capacity of EVA films may be an advantage in terms of sensitivity, when film thickness and hence amounts accumulated at equilibrium, are low.Predictions of times to effective equilibrium $(t_{\mathrm{eq}(95\%)})$ were made for a nominal film thickness of 1 μm. These predictions indicate that both types of films would be effective equilibrium phase samplers for predominantly vapour phase PAHs with log octanol-air partition coefficients $(\log K_{\mathrm{OA}})$ values of ⩽8.7 (pyrene). Despite comparatively rapid linear stage kinetics for EVA, the predicted times to effective equilibrium for PAHs are less for LDPE. This arises due to the relative magnitude of their respective K_SA values. The predicted times to equilibrium (25 °C) for pyrene for example are approximately 94 and 34 days for EVA and LDPE, respectively.     

Simultaneous absolute measurements of gaseous nitrogen species in urban ambient air by long pathlength infrared and ultraviolet-visible spectroscopy

Two new long pathlength spectrometers, utilizing 25-m basepath multiple reflection optical systems, were employed for the first time during an intercomparison of measurement methods for atmospheric nitrogenous species held at Claremont, CA, 11–19 September 1985. Measurement of nitrogenous species using these closed optical path systems, as opposed to single pass systems extending several kilometers, permit the resulting in situ absolute spectroscopic data to serve as benchmark values for point monitors employing denuders or filter packs. The FT-IR spectrometer was operated at a total pathlength of 1150 m and spectral resolution of 0.125 cm⁻¹, with corresponding detection sensitivities of 160 nmolem⁻³ for HNO₃ and 60 nmole m⁻³ for NH₃ (4 and 1.5 ppb, respectively). Concurrent measurements of HONO, NO₂ and NO₃ radicals were conducted with the differential optical absorption spectrometer operated at 800 m total pathlength with detection limits of 24, 160 and 0.8 nmole m⁻³ (0.6, 4 and 0.02 ppb) for HONO, NO₂, and NO₃ radicals, respectively.     

Biodegradation of aromatic hydrocarbons by Haloarchaea and their use for the reduction of the chemical oxygen demand of hypersaline petroleum produced water

Ten halophilic Archaea (Haloarchaea) strains able to degrade aromatic compounds were isolated from five hypersaline locations; salt marshes in the Uyuni salt flats in Bolivia, crystallizer ponds in Chile and Cabo Rojo (Puerto Rico), and sabkhas (salt flats) in the Persian Gulf (Saudi Arabia) and the Dead Sea (Israel and Jordan). Phylogenetic identification of the isolates was determined by 16S rRNA gene sequence analysis. The isolated Haloarchaea strains were able to grow on a mixture of benzoic acid, p-hydroxybenzoic acid, and salicylic acid (1.5 mM each) and a mixture of the polycyclic aromatic hydrocarbons, naphthalene, anthracene, phenanthrene, pyrene and benzo[a]anthracene (0.3 mM each). Evaluation of the extent of degradation of the mixed aromatic hydrocarbons demonstrated that the isolates could degrade these compounds in hypersaline media containing 20% NaCl. The strains were shown to reduce the COD of hypersaline crude oil reservoir produced waters significantly beyond that achieved using standard hydrogen peroxide treatment alone.     

Flamelet modeling of NO formation in laminar and turbulent diffusion flames

The applicability of the laminar flamelet concept for the formation and destruction of nitric oxides in laminar and turbulent diffusion flames has been studied. In a first step, temperatures and species concentrations in an axisymmetric laminar diffusion flame have been calculated (i) by solving the detailed conservation equations and (ii) by applying the laminar flamelet concept. The main purpose of this step was the identification of differences between results from both approaches. It turned out that for highly temperature sensitive or relatively slow chemical processes, the inclusion of the full range of the prevailing scalar dissipation rates plays a major role for the calculated species concentrations. This behavior is obvious from the concept of the laminar flamelet model, where the scalar dissipation rate can be discussed in terms of the reciprocal of a residence time for attaining chemical equilibrium. In a second step, flamelet modeling of NOx formation was extended to a turbulent hydrogen diffusion flame. In both the steps, the flow fields of the flames were calculated by solving the Navier-Stokes equations in axisymmetric formulation using the SIMPLER algorithm. For the turbulent flow, Favre-averaged equations have been used and turbulence was modeled with the standard k-epsilon model including a correction term for axisymmetric systems. The averaging of the species concentrations was accomplished with presumed shape probability density functions (pdfs). The pdf of the mixture fraction was described with a beta-function whereas that of the scalar dissipation rate was assumed to be log-normal. Buoyancy effects have been taken into account. The calculated temperatures and concentrations were compared with data from different experiments.     

Biodegradation of aromatic compounds by white rot and ectomycorrhizal fungal species and the accumulation of chlorinated benzoic acid in ectomycorrhizal pine seedlings

The capability of different white rot (WR, Heterobasidion annosum, Phanerochaete chrysosporium, Trametes versicolor) and ectomycorrhizal (ECM, Paxillus involutus, Suillus bovinus) fungal species to degrade different aromatic compounds and the absorption of 3-chlorobenzoic acid (3-CBA) by ECM pine seedlings was examined. The effect of aromatic compounds on the fungal biomass development varied considerably and depended on (a) the compound, (b) the external concentration, and (c) the fungal species. The highest effect on the fungal biomass development was observed for 3-CBA. Generally the tolerance of WR fungi against aromatic compounds was higher than that of the biotrophic fungal species. The capability of different fungi to degrade aromatic substances varied between the species but not generally between biotrophic and saprotrophic fungi. The highest degradation capability for aromatic compounds was detected for T. versicolor and H. annosum, whereas for Phanerochaete chrysosporium and the ECM fungi lower degradation rates were found. However, Paxillus involutus and S. bovinus showed comparable degradation rates at low concentrations of benzoic acid and 4-hydroxybenzoic acid. In contrast to liquid cultures, where no biodegradation of 3-CBA by S. bovinus was observed, mycorrhizal pines inoculated with S. bovinus showed a low capability to remove 3-CBA from soil substrates. Additional X-ray microanalytical investigations showed, that 3-CBA supplied to mycorrhizal plants was accumulated in the root cell cytoplasm and is translocated across the endodermis to the shoot of mycorrhizal pine seedlings.