Risk Analysis of Volatile Organic Compounds Through Daily Life Cycle in the Industrial City in Korea

This study analyzed the risk of exposure to volatile organic compounds (VOCs) through a study of activity patterns in the Korean industrial city, Ulsan. The daily life cycle patterns(LCPs) of 331 people in Ulsan were surveyed and the average LCPs in Ulsan were obtained by statistical analysis. Nine to twelve personal air samples of VOC exposure at the breathing zones were collected at each LCP. This included hours for sleeping,cooking and eating, going to and from work, working, participating in field or outdoor activities, reading, watchingTV, and shopping. The components and concentrations of the collected VOCs were identified by a Gas Chromatography-MassDetector (GC-MS). The overall reproducibility of all GC analytical procedures of the simultaneously collected duplicatesample pairs represented a mean of percent differences rangingfrom about 9 to 13%. For the general population of Ulsan, thecarcinogenic and non-carcinogenic risk of exposure to theVOCs during the LCPs was evaluated. The carcinogenic riskwas analyzed using both the chronic daily exposure orlifetime average daily exposure (CDI) and the cancerpotency factor. The non-carcinogenic risk was analyzedusing both the CDI and the chronic reference dose.The major chemical forms of the identified VOCs were oxidized forms (43%), aliphatic alkanes (29%) and aromatics (15%). Even though the highest total exposure strength per unit time of each activity was observed during shopping, the highest totalamount of exposure to VOCs was identified as the exposure duringwork. The total carcinogenic risk of exposure to the carcinogenicVOCs through daily life cycle in Ulsan was 2.0 × 10^-4which is substantially exceeding the permissible carcinogenicrisk level, 10^-5 10^-6. The carcinogenic riskduring most of the life cycle activities, except forreading, mainly performed indoors, was higher than that ofthe activities performed outdoors. The carcinogenic risk bybenzene exposure was about 56% (time weighted average) ofthe total carcinogenic risk by the exposure to thecarcinogenic VOCs. During cooking and eating, shopping andout door activities, however, the carcinogenic risk by theexposure to chlorinated compounds like chloroform exceededthe exposure to benzene. The overall hazard index (non-carcinogenic risk) by a chronic exposure to carcinogenicand non-carcinogenic VOCs through daily life cycle in Ulsanwas evaluated as 3.91 × 10^-1, which is much less than1.0 considered as a hazard level to human health, and thusit seems likely not to produce a severe health hazard.     

Inventory and treatment of compost maturation emissions in a municipal solid waste treatment facility

Emissions of volatile organic compounds (VOCs) from the compost maturation building in a municipal solid waste treatment facility were inventoried by solid phase microextraction and gas chromatography–mass spectrometry. A large diversity of chemical classes and compounds were found. The highest concentrations were found for n-butanol, methyl ethyl ketone and limonene (ppm_v level). Also, a range of compounds exceeded their odor threshold evidencing that treatment was needed. Performance of a chemical scrubber followed by two parallel biofilters packed with an advanced packing material and treating an average airflow of 99,300 m³ h^?1 was assessed in the treatment of the VOCs inventoried. Performance of the odor abatement system was evaluated in terms of removal efficiency by comparing inlet and outlet abundances. Outlet concentrations of selected VOCs permitted to identify critical odorants emitted to the atmosphere. In particular, limonene was found as the most critical VOC in the present study. Only six compounds from the odorant group were removed with efficiencies higher than 90%. Low removal efficiencies were found for most of the compounds present in the emission showing a significant relation with their chemical properties (functionality and solubility) and operational parameters (temperature, pH and inlet concentration). Interestingly, benzaldehyde and benzyl alcohol were found to be produced in the treatment system.     

基于氢火焰离子化检测仪响应因子的设备泄漏排放核算

氢火焰离子化检测仪(FID)是检测设备泄漏挥发性有机物(VOCs)的主要仪器。通过变异系数分析了FID响应因子与FID型号、被测气体种类和被测气体浓度的关系,并进行了实例验证。分析结果表明,FID响应因子与各因素关联强度的排序为:被测气体种类FID型号被测气体浓度。响应因子应用实例的验证结果表明:对于芳烃重整装置145个接触甲苯、二甲苯两组分物料的泄漏设备,响应因子修正后的排放量计算值仅为修正前的18.68%;MTBE装置涉甲醇设备的甲醇排放量计算值修正后为修正前的3倍左右。在此基础上,就设备泄漏VOCs污染源,提出通过响应因子实现排放量精细化核算的建议。     

Atmospheric emissions and attenuation of non-methane organic compounds in cover soils at a French landfill

In addition to methane (CH(4)) and carbon dioxide (CO(2)), landfill gas may contain more than 200 non-methane organic compounds (NMOCs) including C(2+)-alkanes, aromatics, and halogenated hydrocarbons. Although the trace components make up less than 1% v/v of typical landfill gas, they may exert a disproportionate environmental burden. The objective of this work was to study the dynamics of CH(4) and NMOCs in the landfill cover soils overlying two types of gas collection systems: a conventional gas collection system with vertical wells and an innovative horizontal gas collection layer consisting of permeable gravel with a geomembrane above it. The 47 NMOCs quantified in the landfill gas samples included primarily alkanes (C(2)-C(10)), alkenes (C(2)-C(4)), halogenated hydrocarbons (including (hydro)chlorofluorocarbons ((H)CFCs)), and aromatic hydrocarbons (BTEXs). In general, both CH(4) and NMOC fluxes were all very small with positive and negative fluxes. The highest percentages of positive fluxes in this study (considering all quantified species) were observed at the hotspots, located mainly along cell perimeters of the conventional cell. The capacity of the cover soil for NMOC oxidation was investigated in microcosms incubated with CH(4) and oxygen (O(2)). The cover soil showed a relatively high capacity for CH(4) oxidation and simultaneous co-oxidation of the halogenated aliphatic compounds, especially at the conventional cell. Fully substituted carbons (TeCM, PCE, CFC-11, CFC-12, CFC-113, HFC-134a, and HCFC-141b) were not degraded in the presence of CH(4) and O(2). Benzene and toluene were also degraded with relative high rates. This study demonstrates that landfill soil covers show a significant potential for CH(4) oxidation and co-oxidation of NMOCs.     

Study of the VOC emissions from a municipal solid waste storage pilot-scale cell: comparison with biogases from municipal waste landfill site

The emission of volatile organic compounds (VOCs) from municipal solid waste stored in a pilot-scale cell containing 6.4 tonnes of waste (storage facility which is left open during the first period (40 days) and then closed with recirculation of leachates during a second period (100 days)) was followed by dynamic sampling on activated carbon and analysed by GC–MS after solvent extraction. This was done in order to know the VOC emissions before the installation of a methanogenesis process for the entire waste mass. The results, expressed in reference to toluene, were exploited during the whole study on all the analyzable VOCs: alcohols, ketones and esters, alkanes, benzenic and cyclic compounds, chlorinated compounds, terpene, and organic sulphides.The results of this study on the pilot-scale cell are then compared with those concerning three biogases from a municipal waste landfill: biogas (1) coming from waste cells being filled or recently closed, biogas (2) from all the waste storage cells on site, and biogas (3) which is a residual gas from old storage cells without aspiration of the gas. The analysis of the results obtained revealed: (i) a high emission of VOCs, principally alcohols, ketones and esters during the acidogenesis; (ii) a decrease in the alkane content and an increase in the terpene content were observed in the VOCs emitted during the production of methane; (iii) the production of heavier alkanes and an increase in the average number of carbon atoms per molecule of alkane with the progression of the stabilisation/maturation process were also observed.Previous studies have concentrated almost on the analysis of biogases from landfills. Our research aimed at gaining a more complete understanding of the decomposition/degradation of municipal solid waste by measuring the VOCs emitted from the very start of the landfill process i.e. during the acidogenesis and acetogenesis phases.     

Chemical characterization of emissions from a municipal solid waste treatment plant

Gaseous emissions are an important problem in municipal solid waste (MSW) treatment plants. The sources points of emissions considered in the present work are: fresh compost, mature compost, landfill leaks and leachate ponds. Hydrogen sulphide, ammonia and volatile organic compounds (VOCs) were analysed in the emissions from these sources. Hydrogen sulphide and ammonia were important contributors to the total emission volume. Landfill leaks are significant source points of emissions of H₂S; the average concentration of H₂S in biogas from the landfill leaks is around 1700 ppmv. The fresh composting site was also an important contributor of H₂S to the total emission volume; its concentration varied between 3.2 and 1.7 ppmv and a decrease with time was observed. The mature composting site showed a reduction of H₂S concentration (<0.1 ppmv). Leachate pond showed a low concentration of H₂S (in order of ppbv). Regarding NH₃, composting sites and landfill leaks are notable source points of emissions (composting sites varied around 30–600 ppmv; biogas from landfill leaks varied from 160 to 640 ppmv).Regarding VOCs, the main compounds were: limonene, p-cymene, pinene, cyclohexane, reaching concentrations around 0.2–4.3 ppmv.H₂S/NH₃, limonene/p-cymene, limonene/cyclohexane ratios can be useful for analysing and identifying the emission sources.     

The use of life cycle assessment for the comparison of biowaste composting at home and full scale

Environmental impacts and gaseous emissions associated to home and industrial composting of the source-separated organic fraction of municipal solid waste have been evaluated using the environmental tool of life cycle assessment (LCA). Experimental data of both scenarios were experimentally collected. The functional unit used was one ton of organic waste. Ammonia, methane and nitrous oxide released from home composting (HC) were more than five times higher than those of industrial composting (IC) but the latter involved within 2 and 53 times more consumption or generation of transport, energy, water, infrastructures, waste and Volatile Organic Compounds (VOCs) emissions than HC. Therefore, results indicated that IC was more impacting than HC for four of the impact categories considered (abiotic depletion, ozone layer depletion, photochemical oxidation and cumulative energy demand) and less impacting for the other three (acidification, eutrophication and global warming). Production of composting bin and gaseous emissions are the main responsible for the HC impacts, whereas for IC the main contributions come from collection and transportation of organic waste, electricity consumption, dumped waste and VOCs emission. These results suggest that HC may be an interesting alternative or complement to IC in low density areas of population.     

Volatilization and Biodegradation of VOCs in Membrane Bioreactors (MBR)

Volatilization and biodegradation are major competitive volatile organic compound (VOC) removal mechanisms in biological wastewater treatment process, which depend on compound specific properties and system design/operational parameters. In this study, a mathematical model was used to determine major removal pathways at various organic loading rates (OLR), solids residence time (SRT) and dissolved oxygen (DO) concentrations in a biological process for vinyl acetate. Model results showed that biological treatment process should be designed with long SRT, high OLR and low DO concentrations to maximize biodegradation and minimize volatilization of VOCs. Unless a VOC is toxic to microorganisms under the given conditions, low VOC emission rates are an inherent advantage of MBRs, which operate at higher OLR and longer SRT compared to conventional activated sludge process. A lab scale membrane bioreactor (MBR) was operated at varying OLR to investigate the relative volatilization and biodegradation rates for acetaldehyde, butyraldehyde and vinyl acetate. Synthetic wastewater containing three VOCs was introduced to the MBR. The DO concentration and SRT was maintained at 2.0 mg L^{− 1} and 100 days, respectively. The overall VOC removal rate was more than 99.7% for three VOCs at all the OLR. For vinyl acetate, the biodegradation rate increased from 93.87 to 99.40% and the volatilization removal rate decreased from 6.09 to 0.59% as OLR was increased from 1.1 to 2.0 kg COD m^{− 3} d^{− 1}. It was confirmed that a MBR can be a promising solution to reduce VOC emissions from wastewater.     

Occupational hygiene in terms of volatile organic compounds (VOCs) and bioaerosols at two solid waste management plants in Finland

Factors affecting occupational hygiene were measured at the solid waste transferring plant at Hyvinkää and at the optic separation plant in Hämeenlinna. Measurements consisted of volatile organic compounds (VOCs) and bioaerosols including microbes, dust and endotoxins.The most abundant compounds in both of the plants were aliphatic and aromatic hydrocarbons, esters of carboxylic acids, ketones and terpenes. In terms of odour generation, the most important emissions were acetic acid, 2,3-butanedione, ethyl acetate, alpha-pinene and limonene due to their low threshold odour concentrations. At the optic waste separation plant, limonene occurred at the highest concentration of all single compounds of identified VOCs. The concentration of any single volatile organic compound did not exceed the occupational exposure limit (OEL) concentration. However, 2,3-butanedione as a health risk compound is discussed based on recent scientific findings linking it to lung disease.Microbe and dust concentrations were low at the waste transferring plant. Only endotoxin concentrations may cause health problems; the average concentration inside the plant was 425 EU/m³ which clearly exceeded the threshold value of 90 EU/m³. In the wheel loader cabin the endotoxin concentrations were below 1 EU/m³. High microbial and endotoxin concentrations were measured in the processing hall at the optic waste separation plant. The average concentration of endotoxins was found to be 10,980 EU/m³, a concentration which may cause health risks. Concentrations of viable fungi were quite high in few measurements in the control room. The most problematic factor was endotoxins whose average measured concentrations was 4853 EU/m³.     

Biofiltration treatment of odors from municipal solid waste treatment plants

An in situ compost biofilter was established for the treatment of odors from biostabilization processing of municipal solid waste. The concentrations of total volatile organic compounds (VOCs) in odors and their components were measured. Biofilter media was characterized in terms of total carbon (TC), total nitrogen (TN), total phosphorus (TP), organic matter (OM), pH value and determination of bacterial colony structure. Gas chromatography–mass spectrometry (GC–MS) analysis showed that the main components of the produced gas were benzene, toluene, ethylbenzene and xylene (BTEX) along with other alkanes, alkenes, terpenes, and sulphur compounds. The compost biofilter had remarkable removal ability for alkylated benzenes (>80%), but poor removal for terpenes (～30%). Total VOC concentrations in odors during the biostabilization process period ranged from 0.7 to 87 ppmv, and the VOC removal efficiency of the biofilter varied from 20% to 95%. After about 140 days operation, TN, TC, TP and OM in compost were kept almost stable, but the dissolved N, NH₄–N and NO₃–N experienced an increase of 44.5%, 56.2% and 76.3%, respectively. Dissolved P decreased by 27.3%. The pH value experienced an increase in the early period and finally varied from 7.38 to 8.08. Results of bacterial colony in packing material indicated that bacteria and mold colony counts increased, but yeasts and actinomyces decreased along with biofilter operation, which were respectively, 3.7, 3.4, 0.04 and 0.07 times of their initial values.     

Emissions from baled municipal solid waste: I. Methodological approach for investigation of gaseous emissions.

This paper presents a methodological approach for the study of volatile organic compounds (VOCs) in air, emitted during storage of municipal solid waste in bales. Determination of VOCs was based on sampling with adsorbent tubes followed by automated analysis using on-line work-up with a thermal desorption unit directly connected to a gas chromatograph-mass spectrometer. Using calculation algorithms and multidimensional statistical analysis of large amounts of data collected, the information was compressed and visualized. The approach was applied to initial measurements of emissions of VOCs from 24 bales composed of municipal solid waste, each bale stored in a wooden box. These bales were produced using the two types of baling equipment available, resulting in cylindrical or rectangular bales, with different densities. Hundreds of different VOCs emitted from these bales sorted out into groups with different chemical structure. Differences in VOC concentrations in air were found between wastes stored in cylindrical or rectangular bales. For instance, it was found that the concentration of VOCs (relative to the concentration of toluene), in the first experiment after storing, for cylindrical bales with six layers of LDPE was 115 +/- 10 microg m(-3), while for rectangular bales it was only 64 +/- 8 microg m(-3). The procedure used for data interpretation suggested different degradation mechanisms in different types of bales. The use of multiple data interfaces, multidimensional statistics and automated chemical analysis methods are likely to be more and more common for waste companies and waste research in the near future. This is due to the interdisciplinary nature of the subject that relies heavily on various areas of science and information technology.     

等离子体联合技术处理挥发性有机化合物废气的研究进展

挥发性有机化合物（VOCs）废气污染面广、气量大、浓度低,含VOCs废气的排放将会受到越来越严格的控制,需要不断研究开发新的VOCs废气处理技术。等离子体联合技术具有多功能作用的效果,对污染物的降解率、能量利用率及对污染物的选择性均高于单一的等离子体技术。综述了等离子体与吸附剂、催化剂、铁电性物质联合处理VOCs废气技术的研究进展,展望了该技术的发展方向。     

Efforts to develop regulations in Korea similar to the US maximum achievable control technology (MACT) regulations for hazardous waste incinerators

The development of regulations patterned after the United States’ requirement for maximum achievable control technology (MACT) to control hazardous air pollutants from major industrial sources in Korea is in progress. Current management practices and installed air pollution control devices were surveyed; emission tests and continuous emission data collected from facilities under operation were assessed considering other MACT requirements such as reporting, report keeping requirements. Emission sampling and air pollutant analysis were carried out at representative hazardous waste incinerators installed with wet-type and dry-type air pollution control devices. Korean and United States Environmental Protection Agency methods were used for sampling and analysis. The major heavy metals emitted were Zn, Ni, Pb, and Cr. The heavy metal removal efficiency of existing air pollution control devices was greater than 99%. The average mercury removal efficiency was more than 30%. Toluene; m,p-xylene; o-xylene; benzene; dichloromethane; styrene; ethylbenzene; 1,3-dichlorobenzene; and 1,2,4-trimethylbenzene were the major volatile organic compounds emitted. The emissions from field tests were compared, reviewed, and analyzed with respect to MACT regulations to check applicability. Finally, draft guidelines were suggested for effective hazardous air pollutant management in Korea.     

The important role of microwave receptors in bio-fuel production by microwave-induced pyrolysis of sewage sludge

Microwave receptor plays an important role in the microwave pyrolysis of sewage sludge in view of its significant influence on the yield and property of bio-fuel products. The yield and the chemical compositions of bio-fuels (gases and oils) obtained from sewage sludge mixed with different receptors (graphite, residue char, active carbon or silicon carbide) were investigated in this study by Gas Chromatography (GC), Gas Chromatography-Mass Spectrometry (GC-MS), and Fourier Transform Infrared Spectroscopy (FTIR). The results showed that the use of silicon carbide gave rise to the highest final temperature of 1130 °C, resulting in the highest yield of gas fraction (up to 63.2 wt.%). The low heating rate (200 °C/min) which was attributed to the addition of residue char promoted condensation reactions and resulted in an increase in solid yield. The existence of active carbon could prolong the resistance time of volatiles in the hot zone owing to its porous structure, generating the maximum concentration of H₂ + CO (60%) in the pyrolysis gas. When graphite was used, the final low temperature favoured the cyclization of the alkenes, giving rise to a higher concentration of mononuclear aromatics in the pyrolysis oils. The model established in this study revealed that the quantity and quality of the products obtained from the microwave pyrolysis highly depended on the process conditions, which were influenced by the receptor significantly.     

Flame Propagation Across Gelled Alkane-In-Water Emulsions

Flame propagation rates were measured for flames spreading across surfaces of gel-like alkane-in-water emulsions. A long, slender, water-cooled trough was used to contain the mixtures. Abrupt changes in the flame propagation velocities - of nearly two orders of magnitude - were observed to occur near ‘critical’ concentrations of certain alkane/water mixtures. Four alkanes were used - pentane, hexane, heptane, and octane - and fuel rich emulsions (in which water was the continuous phase) were employed. The ability of the aqueous phase of the emulsion to inhibit the release of fuel into the vapor phase plays an important role in the observed behavior. That is, the rate at which fuel can diffuse through both the emulsion and the thin liquid layers that reside on it, is an essential kinetic aspect of the phenomena which determine the flame propagation rate across gelled alkane-in-water emulsions.     

二级膜分离—冷凝—吸附工艺处理石化罐区废气

采用二级膜分离—冷凝—变压吸附工艺回收处理含有高浓度挥发性有机物和苯系物的炼厂罐区外排“呼吸气”。结果表明,进气的非甲烷总烃质量浓度范围41 000~182 000 mg/m³,进气中苯、甲苯和二甲苯的质量浓度分别为400~1 400 mg/m³,150~1 600 mg/m³,300~2 100 mg/m³时,尾气中非甲烷总烃质量浓度始终低于80 mg/m³,去除率均高于99.9%,苯、甲苯和二甲苯的去除率分别为99.6%、99.6%和99.8%。抗冲击负荷实验将进气量提高50%,尾气中非甲烷总烃质量浓度仍低于80 mg/m³。二级膜单元可以高效浓缩轻烃,既回收获得可燃气,又解决了轻烃积累所造成的尾气超标难题。     

Modeling of Combined Aerosol and Photooxidant Processes in the Mediterranean Area

The combined UAM-AERO/RAMS modeling system has been applied to study the dynamics of photochemical gaseous species and particulate matter processes in the eastern Mediterranean area between the Greek mainland and the island of Crete. In particular, the modeling system is applied to simulate atmospheric conditions for two periods, i.e., 13-16 July 2000 and 26-30 July 2000. The spatial and temporal distributions of both gaseous and particulate matter pollutants have been extensively studied together with the identification of major emission sources in the area. New pre-processors were developed for the UAM-AERO model for evaluating detailed emission inventories for biogenic compounds, resuspended dust and sea salt. Comparison of the modeling results with measured data was performed and satisfactory agreement was found for a number of gaseous species. However, the model underestimates the PM₁₀ measured concentrations during summer. This is mainly due to the considerable underestimation of particulate matter emissions and in particular dust resuspension, the effect of forest fire emissions and the contribution of Saharan dust episodes.     

Formation of persistent chlorinated aromatic compounds in simulated and real fly ash from iron ore sintering

Effects of carbon concentration and Cu additive in simulated fly ash (SFA) and real fly ash (RFA) on the formation of polychlorinated dibenzofurans (PCDFs), polychlorinated dibenzo-p-dioxins (PCDDs), chlorobenzenes, and polychlorinated biphenyls which were all regarded as persistent chlorinated aromatics in iron ore sintering were investigated. In the annealing process of SFA with various carbon contents, the yield of chlorinated aromatics and the I-TEQ obtained their maximum at 10 wt% carbon content. Active carbon in SFA acted as the carbon source as well as an adsorbent which led to higher production of PCDD/F in solid phase at 10 wt% carbon content. The increase of carbon content will be beneficial on the formation of 2,3,7,8-Chloro-substituted PCDF compared with 2,3,7,8-Chloro-substituted PCDD. In addition, the CuCl₂·2H₂O was a much more powerful catalyst in the formation of chlorinated aromatic compounds compared with elementary Cu, since it served as both a catalyst and a chlorine donor. However, the RFA behaved similarly with SFA with elementary Cu in the formation of chlorinated aromatic compounds. The effect of carbon content and copper additives on formation of 2,3,7,8-chloro-substituted congeners displayed similar characteristics with the tetra- to octa-PCDD/F isomers and even the total PCDD/Fs.     

Monitoring of odor compounds produced by solid waste treatment plants with diffusive samplers

Nuisance caused by odors is one of the most important problems for waste management plants. To control an odor nuisance, it must first be quantified. The analytical difficulties in odor measurements are related to the high number of volatile components (belonging to several chemical classes), above all when the concentration is lower than the detection limit of the technique used for the measurement. In this work, 2-butanone, alpha-pinene, tetrachloroethylene, dimethyldisulfide, beta-pinene, limonene, phenol and benzoic acid are determined, because they are representative of some important classes of compounds with higher odor impact. The compounds are sampled with thermal desorbable radial diffusive samplers Radiello containing Tenax cartridges. The analytical repeatability and the complete thermal desorption of the cartridges were verified for each odor compound; the relative standard deviations for repeated samples and the recovery percentage were, respectively, less than 7% and about 97% for all compounds. The measurements of the linearity of sampling showed no systematic difference according to the collection period. The comparison between the odor threshold and the limit of detection demonstrated that this method is reliable for the recognition and quantification of odor compounds, allowing Public Administration to impose legal limits and the control agencies to verify them.     

石化企业VOCs无组织排放源强的反演模拟

针对石化行业面源无组织排放VOCs难以准确定量的问题,建立了基于开路式傅里叶变换红外光谱技术(OP-FTIR)的面源污染源源强反演模型,并进行了现场模拟试验。试验结果表明,风向、风速、大气稳定度、监测距离、数据处理周期等都是影响反演模型准确性的重要灵敏度参数。以反演源强Q_P与实际排放量Q的比值(Q_P/Q)为量化指标,对各影响因素进行优化处理,确定了构建反演模型适用的边界条件。当各灵敏度参数稳定于适用边界条件之内时,Q_P/Q为0.85~0.90。