Mechanisms of molecular product and persistent radical formation from the pyrolysis of hydroquinone

Hydroquinone is considered to be one of the major, potential molecular precursors for semiquinone-type radicals in the combustion of complex polymeric and oligomeric structures contained in biomass materials. Comprehensive product yield determinations from the high-temperature, gas-phase pyrolysis of hydroquinone in two operational modes (rich and lean hydrogen conditions) are reported at a reaction time of 2.0s over a temperature range of 250-1000 degrees C. Below 500 degrees C, p-benzoquinone is the dominant product, while at temperatures above 650 degrees C other products including phenol, benzene, styrene, indene, naphthalene, biphenylene, phenylethyne, dibenzofuran and dibenzo-p-dioxin are formed. Hydrogen-rich conditions initially inhibit hydroquinone decomposition (below 500 degrees C) but promote product formation at higher temperatures. The decomposition process apparently proceeds via formation of a resonance stabilized p-semiquinone radical. Detailed mechanisms of formation of stable molecular species as well as stable radicals are proposed.     

Characterization and source presumption of wintertime submicron organic aerosols at Saitama,Japan, using the Aerodyne aerosol mass spectrometer

The chemical composition and size distribution of submicron aerosols were analyzed at a suburban site at Saitama, Japan, in the winter of 2004/2005, using an Aerodyne aerosol mass spectrometer. Although organics and nitrate were the dominant species during the sampling period, a large fraction of sulfate was observed at the accumulation mode when mass loading was low and wind speed was high. The size distributions of m/z 44 (mostly CO₂⁺) and sulfate aerosols during periods of high wind speed showed remarkable similarities in the accumulation mode, indicating that oxygenated organics were aged aerosols and internally mixed with sulfate. Ozone concentrations were also increased during these high wind speed periods although nighttime (e.g., 12/17 2004), indicating that the oxygenated compounds were strongly influenced by transported and aged air masses. The diurnal profiles of ultrafine-mode organics and hydrocarbon-like organic aerosols (HOA) were similar to NO_X derived from traffic and other combustion sources. The temporal variation of oxygenated organic aerosols (OOA) agreed well with that of nitrate as a secondary aerosol tracer, and the diurnal profile of the OOA fraction of organics increased during the day associated with higher UV light intensity. The result of time and size-resolved chemical composition of submicron particles indicated that the OOA is associated with both photochemical activity and transboundary pollution, and ultrafine-mode organic and HOA aerosols are mainly associated with combustion sources.     

A review of biomarker compounds as source indicators and tracers for air pollution

An overview of the application of organic geochemistry to the analysis of organic matter on aerosol particles is presented here. This organic matter is analyzed as solvent extractable bitumen/ lipids by gas chromatography-mass spectrometry. The organic geochemical approach assesses the origin, the environmental history and the nature of secondary products of organic matter by using the data derived from specific molecular analyses. Evaluations of production and fluxes, with cross-correlations can thus be made by the application of the same separation and analytical procedures to samples from point source emissions and the ambient atmosphere. This will be illustrated here with typical examples from the ambient atmosphere (aerosol particles) and from emissions of biomass burning (smoke). Organic matter in aerosols is derived from two major sources and is admixed depending on the geographic relief of the air shed. These sources are biogenic detritus (e.g., plant wax, microbes, etc.) and anthropogenic particle emissions (e.g., oils, soot, synthetics, etc.). Both biogenic detritus and some of the anthropogenic particle emissions contain organic materials which have unique and distinguishable compound distribution patterns (C₁₄-C₄₀). Microbial and vascular plant lipids are the dominant biogenic residues and petroleum hydrocarbons, with lesser amounts of the pyrogenic polynuclear aromatic hydrocarbons (PAH) and synthetics (e.g., chlorinated compounds), are the major anthropogenic residues. Biomass combustion is another important primary source of particles injected into the global atmosphere. It contributes many trace substances which are reactants in atmospheric chemistry and soot paniculate matter with adsorbed biomarker compounds, most of which are unknown chemical structures. The injection of natural product organic compounds into smoke occurs primarily by direct volatilization/steam stripping and by thermal alteration based on combustion temperature. Although the molecular composition of organic matter in smoke particles is highly variable, the molecular tracers are generally still source specific. Retene has been utilized as a tracer for conifer smoke in urban aerosols, but is not always detectable. Dehydroabietic acid is generally more concentrated in the atmosphere from the same emission sources. Degradation products from biopolymers (e.g., levoglucosan from cellulose) are also excellent tracers. An overview of the biomarker compositions of biomass smoke types is presented here. Defining additional tracers of thermally-altered and directly-emitted natural products in smoke aids the assessment of the organic matter type and input from biomass combustion to aerosols. The precursor to product approach of compound characterization by organic geochemistry can be applied successfully to provide tracers for studying the chemistry and dispersion of ambient aerosols and smoke plumes. Presented at the 6th FECS Conference on Chemistry and the Environment, Atmospheric Chemistry and Air Pollution, August 26–28, 1998, Copenhagen.     

Investigations of ash topography/morphology and their relationship with heavy metals leachability

The leachability of heavy metals such as chromium (Cr), lead (Pb) and cadmium (Cd) from the ash material obtained from waste combustion was studied. The effects of ash surface topography and morphology on the leachability of these elements were examined using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The AFM (scan size 10 x 10 microns) and SEM images of the simulated ash pellet obtained at various operating temperatures (1000, 1400 and 1500 degrees C) showed significant microstructural and topographical changes. Ash pellets treated at 1000 degrees C contain porous and non-continuous surface. On the other hand, the ash pellet obtained at higher temperature (1500 degrees C) was found to contain a smooth, continuous and non-porous surface. The AFM height profile studies indicated that the top surface variation of the ash pellet at 1000, 1400 and 1500 degrees C were found to be -40.0 to 25.5, -3.7 to 4.7 and -0.10 to 0.66 nm respectively. The SEM analyses also confirmed the presence of smooth, non-porous outer surface of ash formed at 1500 degrees C. In addition, it also showed the presence of compact and rigid interior for the same ash pellet. The leachability of the heavy metals was determined using standard toxicity characteristic leaching procedure (TCLP) test and the samples were analysed using atomic absorption spectroscopy. The results showed that the TCLP leaching ratios of the heavy metals were Cr = 0.30, Pb = 0.05 and Cd = 0.09 at 1000 degrees C. However, the ash obtained at 1400 degrees C showed negligible heavy metals leaching ratio while at 1500 degrees C no leachability was detected (TCLP concentration dropped to nondetectable levels). The use of high temperature treatment enabled the immobilization of heavy metals in the ash preventing their leaching. Such ash can be considered as a non-hazardous material for reuse or safe disposal.     

Evaluation of the thermal/optical reflectance method for quantification of elemental carbon in sediments

The IMPROVE thermal/optical reflectance (TOR) method, commonly used for EC quantification in atmospheric aerosols, is applied to soils and sediments and compared with a thermochemical method commonly applied to these non-atmospheric samples. TOR determines elemental carbon (EC) by an optical method, but it also yields thermally defined EC fractions in a 2% O2/98% He oxidizing atmosphere at 550 degrees C (EC1), 700 degrees C (EC2), and 800 degrees C (EC3). Replicate TOR TC, OC, and EC values exhibited precisions of approximately +/-10% as determined from multiple analyses of the same samples. EC abundances relative to total mass concentrations were within the ranges reported by other methods for diesel exhaust soot, n-hexane soot, wood and rice chars, and coals, as well as for environmental matrices. A direct comparison with the chemothermal (CTO) method of Gustafson et al. for ten soil and sediment samples demonstrated that almost all of the OC and EC1 are eliminated, as is part of the EC2. The CTO soot carbon is bounded by the EC3 and EC2+EC3 fractions of the IMPROVE TOR analysis. It might be possible to adjust these fractions to obtain better agreement between atmospheric aerosol and soil/sediment analysis methods. Given its linking the EC measurement in the atmosphere to sediments, the TOR method will not only provide useful information on the explanation and comparison between different environmental matrices, but also can be used to derive information on global cycling of EC.     

Pyrolysis of humic acids from digested and composted sewage sludge

Humic acids (HAs) were extracted from four digested sewage sludge samples composted for four months, one, two and four years. HAs were pyrolyzed at three different temperatures applying both conventional and in situ methylation (ISM) pyrolysis. The pyrolysates were analyzed using gas chromatography-mass spectrometry (GC/MS). Derivatization (ISM) and pyrolysis temperature had dramatic effects on the composition and relative amounts of the pyrolysates. Among the derivatized HA fragments aliphatic compounds prevailed under all the pyrolysis conditions tested. Aromatic substances consisting mainly of guaiacyl-type compounds were detected in higher abundances only at elevated temperatures. Without ISM the contribution of aromatic structures to the total pyrogram was considerably greater than that of the aliphatics. Increase of the pyrolysis temperature from 450 degrees C to 600 degrees C had smaller effect on the proportions and composition of the compounds studied than increase from 350 degrees C to 450 degrees C.     

Pyrolytic characteristics of sewage sludge

In this study, a number of different sewage sludge including sludge samples from industrial and hospital wastewater treatment plants were characterized for pyrolysis behavior by means of thermogravimetric analysis up to 800 degrees C. According to the thermogravimetric results, five different types of mass loss behaviors were observed depending on the nature of the sludge used. Typical main decomposition steps occurred between 250 and 550 degrees C although some still decomposed at higher temperatures. The first group (Types I, II and III) was identified by main decomposition at approximately 300 degrees C and possible second reaction at higher temperature. Differences in the behavior may be due to different components in the sludge both quantitatively and qualitatively. The second group (Types IV and V), which rarely found, has unusual properties. DTG peaks were found at 293, 388 and 481 degrees C for Type IV and 255 and 397 degrees C for Type V. Kinetics of sludge decomposition can be described by either pseudo single or multicomponent overall models (PSOM or PMOM). The activation energy of the first reaction, corresponding to the main pyrolysis typically at 300 degrees C, was rather constant (between 68 and 77 kJ mol(-1)) while those of second and third reactions were varied in the range of 85-185 kJ mol(-1). The typical order of pyrolysis reaction was in the range of 1.1-2.1. The pyrolysis gases were composed of both saturated and unsaturated light hydrocarbons, carbon dioxide, ethanol and chloromethane. Most products, however, evolve at a quite similar temperature regardless of the sludge type.     

Filtration of fly ash using a fluidized-bed filter

This study focuses on the control of particulates with a fluidized-bed filter in exhaust gas stream. The fluidized-bed filter classified in the granular bed filtration technology was employed to demonstrate the performance for removal of fly ash at indicated operating velocities, fixed bed heights, and bed temperatures; then the collecting mechanisms of particulates by fluidized-bed filter were studied. The size distribution of fly ash passing through the fluidized-bed filter was also analyzed. The results indicate that at higher operating velocities and fixed bed heights, the removal of fly ash is more efficient and inertial impaction is the main mechanism when the fluidized-bed is operated at room temperature (25 degrees C). While operating at higher temperatures (200 degrees C), efficiency of 93.2% to 99.4% can be achieved for submicron particles. It is supposed to be the diffusion mechanism that is responsible for collecting such small particles, and high temperature is a favorable condition because of diffusion.     

Effects of temperature on wood soot pah decay in atmospheres with sunlight and low NOx

Wood smoke particles were exposed to midday sunlight in outdoor Teflon film chambers. Chamber NO₂ concentrations were limited to 0.03 ppm, and less than 0.01 ppm of photochemically generated ozone was produced. The overall initial rate of PAH decay on soot particles could be approximated by a first order rate expression. At moderate temperatures (~ 20°C) the rate of PAH decay on soot particles was appreciable with atmospheric half-lives of individual PAH in the range of 30–60 min. At temperatures of −7°C the rates of decay were substantially slower with half-lives that extended to many hours if not days. When outdoor temperatures changed from 20°C to −7°C the rate of decay of six different PAH decreased by a factor of four to ten. These experiments strongly suggest that the magnitude of PAH decay on soot particles due to photo-induced processes can be strongly influenced by temperature.     

Experimental Verification of Diffusion Battery Theory

The diffusion battery, an assembly of circular tubes or rectangular channels, is one of the best devices available for measuring the size and size distribution of submicron aerosols in the diameter range 0.002 to 0.2 µ m. The performance of these batteries is known from molecular diffusion theory, but until now has not been checked experimentally in this size range because of the lack of the necessary monodisperse aerosols. Experimental measurements on singly charged monodisperse aerosols from 0.01 µm to 0.1 µ m are described using a General Electric and a Pollak condensation nucleus counter to measure the aerosol penetration through the stages of a set of portable diffusion batteries in series. Particle sizes in the range tested could be selected at will by adjusting the voltage of an electric mobility classifier. The fraction of aerosol of a given size passing through each battery stage was found to agree closely with the penetration calculated from molecular diffusion theory for that size. This shows that the theory is correct and confirms that the aerosol produced by the electric mobility classifier was monodisperse. In addition, it was found that the difference in penetration between a charged versus a neutralized aerosol was insignificant except for the smallest aerosols used.     

Dust characteristics over the North Pacific observed through shipboard measurements during the ACE-Asia experiment

To examine the diversity of chemical and physical properties of aerosol particles, in particular dust, over the North Pacific, aerosols were collected along ∼32°N latitude between 140°E and 170°W longitude aboard the NOAA R/V Ronald H. Brown during the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) in the spring 2001. A total of 11,482 aerosol particles were examined through individual-particle analysis. Results indicate that dust particles over this region were dominated primarily by Si-rich particles, including aluminosilicates that contain Fe. Fe is also present as separate Fe-rich particles. Additional common particle types include Ca- and S-rich particles; many of the later appear to represent soil-derived calcium carbonate and its reaction products whereas the former are predominantly reaction products of sea salt and sulfate. Particles are often aggregates of different types including pollution-derived substances and highly heterogeneous, both internally and externally. Dust particles are non-spherical, having circularities from 1.0 up to 4.5, suggesting the high degree of complexity of particle shape. The majority of dust particles were dominated by particles with median diameters from 0.67 to 1.26 μm. However, dust particles with diameters of 5 μm or even larger do exist associated with those events of dust originated from Asian desert areas. The existence of soot and Fe-rich particles over this region indicates the influence of fossil fuel sources in Asia. Aerosol Fe from both Asian desert and fossil fuel combustion may contribute to the nutrient Fe in the surface waters of the North Pacific basin. Therefore, the transport of Asian dust associated with species of fossil fuel burning in the spring may play an important role in altering the natural composition of aerosols over the North Pacific.     

Mass-size distributions of particulate sulfate, nitrate, and ammonium in a particulate matter nonattainment region in southern Taiwan

Concentrations and distributions of three major water-soluble ion species (sulfate, nitrate, and ammonium) contained in ambient particles were measured at three sampling sites in the Kao-ping ambient air quality basin, Taiwan. Ambient particulate matter (PM) samples were collected in a Micro-orifice Uniform Deposit Impactor from February to July 2003 and were analyzed for water-soluble ion species with an ion chromatograph. The PM1/ PM2.5 and PM1/PM10 concentration ratios at the emission source site were 0.73 and 0.53 and were higher than those (0.68 and 0.48) at the background site because there are more combustion sources (i.e., industrial boilers and traffic) around the emission source site. Mass-size distributions of PM NO3- were found in both the fine and coarse modes. SO4(2-)and NH4+ were found in the fine particle mode (PM2.5), with significant fractions of submicron particles (PM1). The source site had higher PM1/PM10(79, 42, and 90%) and PM1/PM2.5 concentration ratios (90, 58, and 93%) for the three major inorganic secondary aerosol components (SO4(2-), NO3-, and NH4+) than the receptor site (65, 27, and 65% for PM1/PM10, 69, 51, and 70% for PM1/PM2.5. Results obtained in this study indicate that the PM1 (submicron aerosol particles) fraction plays an important role in the ambient atmosphere at both emission source and receptor sites. Further studies regarding the origin and formation of ambient secondary aerosols are planned.     

Phase transition behaviour of sodium oleate aerosol particles

Field measurements have shown that organic surfactants are significant components of atmospheric aerosols. While fatty acids, among other surfactants, are prevalent in the atmosphere, the influence of these species on the chemical and physical properties of atmospheric aerosols remains not fully characterized. In order to assess the phase in which particles may exist, a detailed study of the deliquescence of a model surfactant aerosol has been carried out. Sodium oleate was chosen as a surfactant proxy relevant in atmospheric aerosol. Sodium oleate micelle aerosol particles were generated nebulizing a sodium oleate aqueous solution. In this study, the water uptake and phase transition of sodium oleate aerosol particles have been studied in a room temperature aerosol flow tube system (AFT) using Fourier transform infrared (FTIR) spectroscopy. Aerosol morphology and elemental composition were also analysed using scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDX) techniques. The particles are homogeneously distributed as ellipsoidal-shape aggregates of micelles particles with an average size of ∼1.1 μm. The deliquescence by the sodium oleate aerosol particles was monitored by infrared extinction spectroscopy, where the dried aerosol particles were exposed to increasing relative humidity as they passed through the AFT. Observations of the infrared absorption features of condensed phase liquid water enable to determine the sodium oleate deliquescence phase transition at 88±2%.     

Experimental and modeling study of the effect of CH(4) and pulverized coal on selective non-catalytic reduction process

The reduction of nitric oxide using ammonia combined with methane and pulverized coal additives has been studied in a drop tube furnace reactor. Simulated flue gas with 1000ppm NO(x) and 3.4% excess oxygen was generated by cylinder gas. Experiments were performed in the temperature range of 700-1200 degrees C to investigate the effects of additives on the DeNO(x) performance. Subsequently, a kinetic mechanism was modified and validated based on experimental results, and a computational kinetic modeling with CHEMKIN was conducted to analyze the secondary pollutants. For both methane and pulverized coal additives, the temperature window is shifted towards lower temperatures. The appropriate reaction temperature is shifted to about 900 and 800 degrees C, respectively with 1000ppm methane and 0.051gmin(-1) pulverized lignite coal. The addition of methane and pulverized coal widens the temperature window towards lower temperature suggesting a low temperature application of the process. Furthermore, selective non-catalytic reduction (SNCR) reaction rate is accelerated evidently with additives and the residence time to complete the reaction is shortened distinctly. NO(x) reduction efficiency with 80% is achieved in about 0.3s without additive at 1000 degrees C. However, it is achieved in only about 0.2s with 100ppm methane as additive, and only 0.07 and 0.05s are needed respectively for the cases of 500 and 1000ppm methane. The modified kinetic modeling agrees well with the experimental results and reveals additional information about the process. Investigation on the byproducts where NO(2) and N(2)O were analyzed by modeling and the others were investigated by experimental means indicates that emissions would not increase with methane and pulverized coal additions in SNCR process and the efficacious temperature range of SNCR reaction is widened approximately with 100 degrees C.     

Internally mixed sea salt, soot, and sulfates at Macao, a coastal city in South China

Direct observation of the mixing state of aerosol particles in a coastal urban city is critical to understand atmospheric processing and hygroscopic growth in humid air. Morphology, composition, and mixing state of individual aerosol particles from Macao, located south of the Pearl River Delta (PRD) and 100 km west of Hong Kong, were investigated using scanning electron microscopy (SEM) and transmission electron microscopy coupled with energy-dispersive X-ray spectrometry (TEM/EDX). SEM images show that soot and roughly spherical particles are prevalent in the samples. Based on the compositions of individual aerosol particles, aerosol particles with roughly spherical shape are classified into coarse Na-rich and fine S-rich particles. TEM/EDX indicates that each Na-rich particle consists of a Na-S core and NaNO3 shell. Even in the absence of heavy pollution, the marine sea salt particles were completely depleted in chloride, and Na-related sulfates and nitrates were enriched in Macao air. The reason could be that SO2 from the polluted PRD and ships in the South China Sea and NO2 from vehicles in the city sped up the chlorine depletion in sea salt through heterogeneous reactions. Fresh soot particles from vehicular emissions mainly occur near curbside. However, there are many aged soot particles in the sampling site surrounded by main roads 200 to 400 m away, suggesting that the fresh soot likely underwent a quick aging. Overall, secondary nitrates and sulfates internally mixed with soot and sea salt particles can totally change their surface hygroscopicity in coastal cities.     

Use of rare earth tracers for the study of diesel emissions in the atmosphere

The emissions of diesel vehicles mainly contain soot, which is difficult to distinguish from soot originating from other sources. The use of a tracer which can be detected in extremely low mass concentrations and does not occur normally in the atmospheric aerosol can help to differentiate between aerosols from different sources. The rare earth element Dysprosium has proven useful for this purpose. It can be detected by neutron activation analysis in quantities of nanograms and does not occur naturally.An organic, diesel soluble Dysprosium compound was added to the fuel. During the combustion process the Dysprosium is oxidized and attaches to the formed soot particles. For the atmospheric filter samples an extraction technique was used.This marking method has been successfully applied for an extended field experiment.     

新型多级冲击采样器切割粒径的标准粒子实验分析

大气溶胶对环境污染、气候变化以及人体健康有着重要的影响,大气溶胶的采集和分析已成为当前大气环境研究领域中的一个重要课题.论述的新型多级冲击采样器能够实现大气溶胶颗粒物按空气动力学粒径的大小7级分离采集,提供大致均匀的平面样品以进行后续的物理、化学分析,同时保证各分级切割粒径的稳定性.利用振动孔溶胶发生器产生均匀、粒径大致相同、单分散相的1.5～17μm空气动力学粒径标准粒子,对新型多级冲击采样器前三级的切割粒径和收集效率进行鉴定性分析实验,结果表明,能够满足对大气溶胶颗粒物分级采集的要求.     

A case study of optical and chemical ground apportionment for urban aerosols in Thessaloniki

Urban aerosol characterization gathering ground-based in situ and sunphotometer measurements have been performed for the city of Thessaloniki for two specific days: the 12th and 13th of June 1997. A representative aerosol model for Thessaloniki aerosols was tentatively constructed for each day. Four components have been selected from our chemical measurements: black carbon (BC), particulate organic matter (POM), inorganic fine water soluble particles (WS) and a residue coarse component which mainly contains coarse dust and sea-salt particles (CC). Size distribution and complex refractive index for (WS) and (CC) components were determined from published data. (CC) has been shown to have a small optical effect compared to the submicron components. Size distribution for carbonaceous particles was obtained from sensitivity tests on particulate number and visible Angström exponent. The impact of relative humidity on extinction and scattering coefficients has been calculated on 13 June with Mie theory and Hänel relationships. Parameters needed for this calculation were well known for WS particles only. For POM particles we have used the experimental curve of hygroscopic factors obtained by Hobbs et al. (1997) for urban aerosols sampled on the East coast of United States to determine the hydrophilic dependency of POM particles. Relative humidity has been shown to be an important parameter even for values lower than 50%. Optical apportionment calculation has been realized pointing out that more than 45% of the total extinction coefficient is due to (POM) particles and about 20 and 30% to (WS) and (BC), respectively.     

Equilibrium temperatures of aerosol particles in outdoor exposure chambers

It has been suggested that radiational heating of atmospheric soot particles could affect the stability of organic compounds on the aerosols as these systems age in the atmosphere. To investigate this possibility, we introduce a simple equation for calculating the equilibrium temperature of atmospheric particles. The results show that under typical conditions, the temperature difference between the particles and the surrounding air is less than 0.01 K.