Major aromatic VOC in the ambient air in the proximity of an urban landfill facility

In this study, the environmental behavior of major aromatic VOC (including benzene, toluene, ethylbenzene and xylene, commonly called BTEX) in the ambient air was investigated from a mid-size municipal landfill site located in Dae Gu city, Korea in the winter of 2004. A series of field campaigns were conducted in the course of the study to cover eight different locations within and near this landfill site along with a number of VOC vent systems. The mean concentrations of different VOC species in ambient air fell in a comparable range of at or above a few ppb (e.g., the most abundant toluene 10 ppb). An inspection of the VOC data sets at the studied LF sites also indicated that they are quite analogous to those typically found in other urban areas in terms of their absolute magnitude and relative pattern (e.g., the general dominance of toluene over the other species). In light of the fact that there is active ventilation of landfill gas (LFG: e.g., with their LFG concentrations above a few to a few tens of ppm) in the study area with no other distinct source processes, it can be concluded that the effects of the landfill processes may be as important as other point sources in maintaining VOC concentration levels in certain urban areas.     

Performance of BTX degraders under substrate versatility conditions

A microbial consortium acclimatized with benzene, toluene or xylene (BTX) was employed to study the degradation pattern of these compounds individually under aerobic conditions. Batch and continuous experiments were conducted to evaluate the adaptability of the enriched cultures under substrate versatility conditions. The bio-kinetic parameters obtained under substrate versatility conditions were compared with those of a single substrate condition. Similar degradation patterns were observed for all the substrates with inhibition occurring at higher concentration (approximately 150 mg/L for benzene and xylene, and approximately 200 mg/L for toluene). Toluene degradation was highest, followed by benzene and xylene in the aqueous phase. Adaptation to a more toxic compound like benzene and xylene improved the utilization of toluene. On the other hand, microbes grown on a less toxic compound (toluene) grew at a lower rate in the presence of more toxic compounds. Suitable kinetic parameters such as micro(max) (maximum specific growth rate per hour), Ks (half saturation constant, mg/L), and KI (threshold substrate inhibition constant, mg/L) were determined using Haldane and Levenspiel substrate inhibition models. The Haldane equation seems to be an adequate expression for the system. The degradation behavior of pollutants in the gas phase was also evaluated using a toluene acclimatized biotrickling filter operated in continuous mode. The biotrickling filter acclimatized with toluene could degrade benzene and xylene with a lower elimination capacity. But, the system could recover its original efficiency quite fast even after a prolonged shock loading. The degradation was better for toluene, followed by benzene and xylene.     

Influence of ethanol-gasoline blended fuel on emission characteristics from a four-stroke motorcycle engine

Emission characteristics from a four-stroke motorcycle engine using 10% (v/v) ethanol-gasoline blended fuel (E10) were investigated at different driving modes on the chassis dynamometers. The results indicate that CO and HC emissions in the engine exhaust are lower with the operation of E10 as compared to the use of unleaded gasoline, whereas the effect of ethanol on NO(X) emission is not significant. Furthermore, species of both unburned hydrocarbons and their ramifications were analyzed by the combination of gas chromatography/mass spectrometry (GC/MS) and gas chromatography/flame ionization detection (GC/FID). This analysis shows that aromatic compounds (benzene, toluene, xylene isomers (o-xylene, m-xylene and p-xylene), ethyltoluene isomers (o-ethyltoluene, m-ethyltoluene and p-ethyltoluene) and trimethylbenzene isomers (1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene)) and fatty group ones (ethylene, methane, acetaldehyde, ethanol, butene, pentane and hexane) are major compounds in motorcycle engine exhaust. It is found that the E10-fueled motorcycle engine produces more ethylene, acetaldehyde and ethanol emissions than unleaded gasoline engine does. The no significant reduction of aromatics is observed in the case of ethanol-gasoline blended fuel. The ethanol-gasoline blended fuel can somewhat improve emissions of the rest species.     

An analysis of synergistic and antagonistic behavior during BTEX removal in batch system using response surface methodology

The removal of benzene, toluene, ethylbenzene and xylene (BTEX) as quaternary mixtures were studied in batch systems using a well-defined mixed microbial culture. The synergistic and antagonistic effects of total BTEX removal (BTEXT-RE) due to the presence of mixed substrate was evaluated through experiments designed by response surface methodology (RSM). The low and high concentrations of individual BTEX were 15 and 75 mg l(-1), respectively. The results showed that, increasing the concentration of xylene increased the cumulative BTEX removal (BTEXT-RE), however the reverse occurred when benzene concentrations were increased from low to high levels. A mixed response of increasing and decreasing trend in the BTEXT-RE value was observed when either of toluene or ethylbenzene concentration was increased. When the concentrations of individual BTEX compounds were 30 mg l(-1), the BTEXT-RE was about 58%. Complete BTEXT-RE was achieved at optimal BTEX concentrations of 48.1, 45.6, 49.3 and 56.6 mg l(-1). The RSM approach was found efficient in explaining the main, squared and interaction effects among individual BTEX concentrations on the BTEXT-RE in a more statistically meaningful way.     

Substrate interactions during anaerobic biodegradation of BTEX by the mixed cultures under nitrate reducing conditions

The enriched BTEX-degrading bacteria were used to investigate the substrate interactions during anaerobic biodegradation of all the possible BTEX binary combinations. Beneficial and detrimental substrate interactions were observed in comprehensive mixtures of benzene, toluene, ethylbenzene, o-xylene, m-xylene and p-xylene. The amendment of toluene or ethylbenzene could stimulate benzene degradation. Lower concentrations of m-xylene would enhance the degradation of benzene, whereas degradation of benzene was inhibited with higher concentrations of m-xylene. The simultaneous presence of toluene and ethylbenzene could stimulate the degradation of each other. The addition of toluene stimulated o-xylene degradation, whereas the amendment of ethylbenzene inhibited the degradation of o-xylene. Lower concentrations of toluene or ethylbenzene would enhance the degradation of m-xylene and p-xylene, whereas higher concentrations of toluene or ethylbenzene had a slight inhibitory effect on m-xylene and p-xylene degradation. The amendment of benzene, m-xylene or p-xylene would inhibit the degradation of other BTEX compounds. When the concentration of BTEX mixtures was over 150mg/l, the degradation of benzene, o-xylene, m-xylene and p-xylene was severely inhibited.     

Adsorption behaviors of volatile organic compounds (VOCs) on porous clay heterostructures (PCH)

Porous clay heterostructures (PCHs) are capable of adsorbing volatile organic compounds (VOCs). In this study, PCH was synthesized by modifying bentonite (Bent) with cetyltrimethylammonium bromide (CTMAB) and dodecylamine (DDA). Adsorption of six volatile organic compounds (VOCs) including acetone, toluene, ethylbenzene, o-xylene, m-xylene and p-xylene by PCH was investigated. It was observed that adsorption capacities of VOCs were strongly dependent on their properties including cross-sectional area, polarizability, enthalpy of vaporization and critical volume by the multiple linear regression (MLR) approach. Furthermore, PCH had higher adsorption affinity for the aliphatic hydrocarbon compound (acetone) than that for aromatic compounds, which could be attributed to the HOMO energy effects of VOCs. Therefore, PCH could be attractive candidate adsorbents for VOC removal.     

Emission characteristics of VOCs from athletic tracks

Dynamic and flow-through flux chambers are convenient tools for field measurements of gas or VOC emission flux from solid surfaces in the field. This study was undertaken to collect on site and quantify the emissions of volatile organic compounds (VOCs) released from athletic running tracks. Three typical types of tracks, one synthetic rubber and two tracks (types I and II) consisting mainly of polyurethane, were studied. They were all installed with adhesives and backings, both of which contributed significant amount of VOCs. VOCs released from the track surface were collected with a flux chamber and subsequently analyzed by a gas chromatograph/mass spectrometer (GC/MS). Also, for each track and at each selected time the emission flux and mass emission were measured on site under outdoor conditions over a period of 40 min. GC/MS analyses show that the VOCs emitted include 2-methyl furan, butanal, methyl ethyl ketone, benzene, heptane, methyl isobutyl ketone, toluene+octane, hexanal, nonane+ethylbenzene, xylenes+styrene, propyl benzene, decane, 1,3,5-trimethyl benzene, 1,2,4-trimethyl benzene, 1,2, 3-trimethyl benzene and undecane. Of these, hexanal was the common and principal compound for all three types of tracks. 2-Methyl furan and methyl isobutyl ketone were the characteristic compounds for the synthetic rubber and the type II of polyurethane tracks, respectively. In the field studies, no unique compounds were found in the type I of polyurethane tracks. For each of these three types of tracks the total-VOCs emission flux was correlated to the track age and track surface temperature. The results of multiple regression analysis showed good correlation. The type II polyurethane track had the highest decay rate, while the synthetic rubber track had the lowest decay rate. Two years after the track installation, the VOC concentrations measured at 1.5 m above the track, the breathing height of school children, were not significantly higher than the background levels.     

Air-cooled cold trap channel integrated in a microfluidic device for monitoring airborne BTEX with an improved detection limit

We integrated an air-cooled cold trap (CT) channel in a microfluidic device for monitoring airborne benzene, toluene, ethylbenzene, and xylene (BTEX) gases and demonstrated its effect on improving the detection limit of the microfluidic device. The device consists of concentration and detection cells formed of 3 x 1 cm Pyrex plates. We first introduced a sample gas into the concentration cell, and the gas was adsorbed onto an adsorbent in the channel. We then raised the temperature using a thin-film heater and introduced the desorbed gas into the detection cell. To prevent dilution of the gas before detection, we propose an improvement to the concentration cell structure that involves the integration of the CT channel. We examined the CT effect by comparing three types of concentration cell with different channel structures. We found that we could detect a gas concentration about 2 orders of magnitude lower than in our previous work by optimizing the channel structure and integrating a CT channel. As an example of BTEX detection,we obtained a 0.05 ppm detection limit for toluene gas with a sampling time of 30 min.     

Adsorption of BTEX from aqueous solution by macroreticular resins

Theoretical and experimental investigations were conducted on the adsorption of benzene, toluene, ethylbenzene and xylene (BTEX) by macroreticular resins. A mass transfer model based on the squared-driving force principle is presented for describing the BTEX transfer between the aqueous and solid phases. Also proposed is a theoretical model for describing the BTEX breakthrough curves of the adsorption column. While the mass transfer model involves only an overall mass transfer coefficient, the column adsorption model has two model parameters. Those parameters are conveniently estimated using the observed mass transfer and breakthrough data. The predictions using the proposed models were found to compare well with the experimental data of batch and column BTEX adsorption tests.     

水中甲苯的不确定度分析与评定

介绍了澳大利亚检测机构NARL对水中苯、甲苯、乙苯、二甲苯进行气相色谱-质谱联用分析,通过建立数学模型,识别不确定度的来源主要有浓缩时的气体流速、温度、玻璃量器的使用情况及气质联用仪的操作情况,评定不确定度的每一分量主要有方法回收率、样品回收率、均匀性、精密度、变异系数,据此方法可得到其他的苯系物成分的不确定度.所得结果符合ISO/IEC17025的要求.该方法具有快速、准确的特点.     

Fiber-optic laser-induced fluorescence probe for the detection of environmental pollutants

Laser-induced fluorescence (LIF) spectroscopy in combination with fiber optics is shown to be a powerful tool for qualitative and quantitative diagnostics of environmental pollutants in water and soil. Timeintegrated data accumulation of the LIF signals in early and late time windows with respect to the excitation pulse simplifies the method so that it becomes attractive for practical applications. Results from field measurements are reported, as oil contaminations under a gas station and in an industrial sewer system are investigated. A KrF-excimer laser and a hydrogen Raman shifter can be applied for multiwavelength excitation. This allows a discrimination between benzene, toluene, xylene, and ethylbenzene aromatics and polycyclic aromatic hydrocarbon molecules in the samples under investigation. For a rough theoretical approach, a computer simulation is developed to describe the experimental results.     

Highly selective GaN-nanowire/TiO2-nanocluster hybrid sensors for detection of benzene and related environment pollutants

Nanowire-nanocluster hybrid chemical sensors were realized by functionalizing gallium nitride (GaN) nanowires (NWs) with titanium dioxide (TiO(2)) nanoclusters for selectively sensing benzene and other related aromatic compounds. Hybrid sensor devices were developed by fabricating two-terminal devices using individual GaN NWs followed by the deposition of TiO(2) nanoclusters using RF magnetron sputtering. The sensor fabrication process employed standard microfabrication techniques. X-ray diffraction and high-resolution analytical transmission electron microscopy using energy-dispersive x-ray and electron energy-loss spectroscopies confirmed the presence of the anatase phase in TiO(2) clusters after post-deposition anneal at 700?°C. A change of current was observed for these hybrid sensors when exposed to the vapors of aromatic compounds (benzene, toluene, ethylbenzene, xylene and chlorobenzene mixed with air) under UV excitation, while they had no response to non-aromatic organic compounds such as methanol, ethanol, isopropanol, chloroform, acetone and 1,3-hexadiene. The sensitivity range for the noted aromatic compounds except chlorobenzene were from 1% down to 50 parts per billion (ppb) at room temperature. By combining the enhanced catalytic properties of the TiO(2) nanoclusters with the sensitive transduction capability of the nanowires, an ultra-sensitive and selective chemical sensing architecture is demonstrated. We have proposed a mechanism that could qualitatively explain the observed sensing behavior.     

Optimization of process parameters for transalkylation of toluene to xylene using response surface methodology

ABSTRACT

H-beta zeolite was modified by the ion exchange method to replace its H⁺ ions with Ce⁴⁺ ions. The catalytic performance of this cerium exchanged beta zeolite was evaluated for vapor phase transalkylation of 1,2,4 TMB (1,2,4 trimethylbenzene) with toluene for the production of xylene in a fixed bed, down-flow reactor. The modified zeolite was found to be highly active for this transalkylation reaction. The response surface methodology (RSM) is used for designing the experiments. The effect of three important reaction parameters viz. temperature, reactant ratio, and space time on response variables (toluene conversion and xylene selectivity) is studied and discussed. All the three selected reaction parameters were found to be significant for the toluene conversion; whereas, xylene selectivity was not much influenced by the temperature. The optimum values of the reaction parameters predicted by the model (temperature: 409.7°C, reactant ratio: 2.024, and space time: 4.451) were validated by an experimental run. The results of the experimental run were in close agreement with the model predicted results.     

Evaluation of natural attenuation rate at a gasoline spill site

Contamination of groundwater by gasoline and other petroleum-derived hydrocarbons released from underground storage tanks (USTs) is a serious and widespread environmental problem. Natural attenuation is a passive remedial approach that depends upon natural processes to degrade and dissipate contaminants in soil and groundwater. Currently, in situ column technique, microcosm, and computer modeling have been applied for the natural attenuation rate calculation. However, the subsurface heterogeneity reduces the applicability of these techniques. In this study, a mass flux approach was used to calculate the contaminant mass reduction and field-scale decay rate at a gasoline spill site. The mass flux technique is a simplified mass balance procedure, which is accomplished using the differences in total contaminant mass flux across two cross-sections of the contaminant plume. The mass flux calculation shows that up to 87% of the dissolved total benzene, toluene, ethylbenzene, and xylene (BTEX) isomers removal was observed via natural attenuation at this site. The efficiency of natural biodegradation was evaluated by the in situ tracer method, and the first-order decay model was applied for the natural attenuation/biodegradation rate calculation. Results reveal that natural biodegradation was the major cause of the BTEX mass reduction among the natural attenuation processes, and approximately 88% of the BTEX removal was due to the natural biodegradation process. The calculated total BTEX first-order attenuation and biodegradation rates were 0.036 and 0.025% per day, respectively. Results suggest that the natural attenuation mechanisms can effectively contain the plume, and the mass flux method is useful in assessing the occurrence and efficiency of the natural attenuation process.     

Absorption of a volatile organic compound by a jet loop reactor with circulation of a surfactant solution: performance evaluation

Biofiltration shows high efficiency for the removal of industrial waste gases and reliable operational stability at low investment and operating cost, especially when the VOC concentration is low, such as 100 ppmv (micro LL(-1)) or less. However, it has been reported that the abrupt change in VOC concentrations leads to the failure of the biofilter. Hence, the pretreatment of waste gases is necessary to ensure the stable operation of the biofilter. The objective of this study is to develop a jet loop reactor (JLR) with circulation of a surfactant solution to lower the concentration of VOCs, especially hydrophobic VOCs. Toluene and Tween 81 were used as a model industrial waste gas and a surfactant, respectively. Among several non-ionic surfactants tested, Tween 81 showed the most rapid dissolution of toluene. When a JLR is replaced with fresh Tween 81 solution (0.3% w/v) every hour, it successfully absorbed for 48 h over 90% of the toluene in an inlet gas containing toluene at 1000 ppmv (microL L(-1)) or less. Therefore, JLR with circulation of a surfactant solution is believed to ensure the stable operation of the biofilter even with the unexpected increase in the VOC concentrations.     

Silicone sensing phase for detection of aromatic hydrocarbons in water employing near-infrared spectroscopy

The use of silicone for detection of aromatic hydrocarbons in water using near-infrared spectroscopy is proposed. A sensing phase of poly(dimethylsiloxane) (PDMS) was prepared, and a rod of this material was adapted to a transflectance probe for measurements from 850 to 1800 nm. Deionized water samples contaminated separately with known amounts of benzene, toluene, ethylbenzene, and m-xylene were used for evaluation of the PDMS sensing phase, and measurements were made in a closed reactor with constant stirring. Equilibrium states were obtained after 90, 180, 360, and 405 min for benzene, toluene, ethylbenzene, and m-xylene, respectively. The PDMS sensing phase showed a reversible response, presenting linear response ranges up to 360, 290, 100, and 80 mg L(-1), with detection limits of 8.0, 7.0, 2.6, and 3.0 mg L(-1) for benzene, toluene, ethylbenzene, and m-xylene, respectively. Reference spectra obtained with different rods showed a relative standard deviation of 0.5%, indicating repeatability in the sensing phase preparation. A relative standard deviation of 6.7% was obtained for measurements performed with six different rods, using a 52 mg L(-1) toluene aqueous solution. The sensing phase was evaluated for identification of sources of contamination of water in simulated studies, employing Brazilian gasoline type A (without ethanol), gasoline type C (with 25% of anhydrous ethanol), and diesel fuel. Principal component analysis was able to classify the water in distinct groups, contaminated by gasoline A, gasoline C, or diesel fuel.     

Volatile organic compounds at an urban monitoring station in Korea

Measurements of 56 volatile organic compounds (VOC) were undertaken at a monitoring site in Seoul, Korea in 2004. The VOC pollution at the site was evaluated for both functional groups and individual compounds. The highest concentrations for the functional groups were recorded by aromatic (AR: 430ppbC) followed by paraffin (PR), olefin (OF), and alkyne (AK). The mean concentrations of individual VOCs ranged from 0.05ppb (1-hexene) to 39.8ppb (toluene). For the VOC groups, there were peak concentrations during winter (AK and OF) and summer (AR). Although most aromatic VOCs generally peaked during summer, this was not true for benzene (e.g., winter peak). The distribution of VOCs at the study site was characterized by significantly enhanced concentrations of toluene and aromatic VOCs from local industrial and mobile sources. Despite excursions that were occasionally observed from aromatic groups or benzene, strong correlations occurred frequently between different groups and between individual components. The overall results of this study suggest that anthropogenic emissions have contributed greatly to increases in VOC pollution at the study site.     

Toluene pyrolysis in an electric ARC: Products analysis

Toluene pyrolysis in a submerged carbon arc produced at least 72 different molecular species as detected by gas-chromatography coupled with mass spectrometry (GC-MS). The most abundant products found were bibenzyl (1,2-diphenylethane), naphthalene and biphenylene. Furthermore, also diethynylbenzene isomers, fluorene, diphenymethane, indene and biphenyl were produced in appreciable amounts. The formation mechanisms of these and other minor products are discussed mainly in the light of the benzyl radical and its decay into other products. Among polyynes, only 1,3,5,7-octatetrayne was produced above 1% relative yield. The results are discussed in comparison to the products detected in toluene pyrolysis under other experimental conditions, such as shock tube pyrolysis and toluene flames. Furthermore, a comparison with the products obtained from the benzene pyrolysis is reported.     

缓冲器缸筒成形工艺

针对缓冲器缸筒产品结构特点及性能要求,结合热冲压(挤盂+热变薄拉深)及冷变薄拉深成形工艺的特点,对缓冲器缸筒成形工艺方案,热冲压(挤盂+热变薄拉深)毛坯的形状和尺寸,热冲压(挤盂+热变薄拉深)及冷变薄拉深成形工艺等关键技术问题进行了研究。试验结果表明采用热冲压(挤盂+热变薄拉深)和冷变薄拉深相结合的工艺方法对缓冲器缸筒进行成形加工高效而经济,比传统热冲压后机械加工的成形工艺原材料利用率提高25%左右,同时所生产的产品尺寸稳定,力学性能一致性好。     

铁屑材料压制工艺及性能研究

为研究铁屑热压成型工艺,将表面处理后的Q195切屑经压实、加热、热复压工序,得到具有一定强,度和塑性的金属材料.通过压缩试验和金相观察,考察工艺参数对材料组织及性能的影响.研究表明:冷压烧结不能使金属切屑之间实现冶金结合,必需进行热复压;随着压制力及压制温度的提高,材料的密度和变形抗力增大;在小变形情况下,试件的变形抗...