Use of Fourier transform infrared spectrometry as a continuous emission monitor

This paper describes the use of a Fourier transfer infrared (FTIR) spectrometer, integrated with a sampling system and a control software, as a continuous emission monitor (CEM) for on-line measurement of most volatile organic and some inorganic compounds from various gas emissions. The time response of the system was tested experimentally, and can be approximated by a complete mixing model. In order to validate the measurement accuracy of the system, spiking tests are suggested. This paper discusses considerations in designing the spiking test and analyzing the spiking results. Field test results show that the FTIR-CEM has a stable performance and can be applied to stack emission monitoring, process monitoring, and unknown HAPs identification in many thermal treatment processes.     

Headspace-SPME-GC-MS Identification of Volatile Organic Compounds Released from Expanded Polystyrene

A method for the identification of volatile organic compounds (VOCs) released from packaging expanded polystyrene (EPS) is presented. Headspace solid-phase microextraction (HS-SPME) with a 75-m carboxen-polydimethylsiloxan fiber was used as sample preparation technique before the determination of the volatile organic compounds by gas chromatography–mass spectrometry (GC-MS). For separation of compounds, two fused silica capillary columns of different polarity (DB-5ms and BPX-50) were used. Styrene monomer with his impurities and oxidation products, as well as residual pentane, were identified in the headspace of EPS.     

超滤膜系统污染物的形貌及组成分析

通过SEM、能谱、FTIR以及电感耦合等离子体质谱的分析方法对被污染超滤膜面的无机污染物、有机污染物和微生物进行了识别和分析。研究结果表明:超滤膜面无机污染物主要为Fe(OH)3、Cu(OH)2、Al(OH)3和Si等胶体物和少量CaSO4;有机污染物主要为多菌霉素类化合物;微生物可能富含铁类化合物。同时污染膜的清洗液分析结果说明该超滤膜污染物主要为无机胶体和有机物。     

Emissions from baled municipal solid waste: II. Effects of different treatments and baling techniques on the emission of volatile organic compounds.

This paper focuses on the volatile organic compound emissions from baled municipal solid waste (MSW). The analytical methodology was based on sampling with adsorbent tubes once a month during seven occasions within a time period of 1 year. Automated analyses were carried out on-line work-up with thermal desorption directly connected to a gas chromatograph-mass spectrometer. The effect of different baling techniques, cylindrical and rectangular baling was compared. It was found that cylindrically baled MSW emitted larger concentration of esters than their rectangular counter parts. Conversely, aromatic compounds emissions dominated in rectangularly baled MSW. This indicates that different degradation mechanisms operate in the waste bales. Cylindrical and rectangular bales are generally wrapped with six layers of 250 microm thick low density polyethylene (LDPE). It was observed that by wrapping an extra six layers of LDPE film onto the bales, the emissions from cylindrical bales increased while emissions from the rectangular counterpart decreased. Over time, the volatile organic compound emissions from cylindrical bales decreased two orders of magnitudes from 96.2 +/- 20.8 microg m(-3) in September 2003 to 0.80 +/- 0.07 microg m(-3) in July 2004. The rectangular bales exhibited an almost identical relative emission reduction from 54.4 +/- 4.3 microg m(-3) in September 2003 to 0.46 +/- 0.02 microg m(-3) in July 2004. Future work will concentrate on full-scale storages, taking into account waste type, storage size, temperature development and the different baling techniques among other variables.     

Comparison of different procedures to stabilize biogas formation after process failure in a thermophilic waste digestion system: influence of aggregate formation on process stability

Following a process failure in a full-scale biogas reactor, different counter measures were undertaken to stabilize the process of biogas formation, including the reduction of the organic loading rate, the addition of sodium hydroxide (NaOH), and the introduction of calcium oxide (CaO). Corresponding to the results of the process recovery in the full-scale digester, laboratory experiments showed that CaO was more capable of stabilizing the process than NaOH. While both additives were able to raise the pH to a neutral milieu (pH>7.0), the formation of aggregates was observed particularly when CaO was used as the additive. Scanning electron microscopy investigations revealed calcium phosphate compounds in the core of the aggregates. Phosphate seemed to be released by phosphorus-accumulating organisms, when volatile fatty acids accumulated. The calcium, which was charged by the CaO addition, formed insoluble salts with long chain fatty acids, and caused the precipitation of calcium phosphate compounds. These aggregates were surrounded by a white layer of carbon rich organic matter, probably consisting of volatile fatty acids. Thus, during the process recovery with CaO, the decrease in the amount of accumulated acids in the liquid phase was likely enabled by (1) the formation of insoluble calcium salts with long chain fatty acids, (2) the adsorption of volatile fatty acids by the precipitates, (3) the acid uptake by phosphorus-accumulating organisms and (4) the degradation of volatile fatty acids in the aggregates. Furthermore, this mechanism enabled a stable process performance after re-activation of biogas production. In contrast, during the counter measure with NaOH aggregate formation was only minor resulting in a rapid process failure subsequent the increase of the organic loading rate.     

石化企业固定顶储罐挥发性有机物排放量影响因素的分析

采用美国国家环保局推荐的储罐挥发性有机物(VOCs)排放量定量计算方法,以北京某石化企业轻柴油固定顶储罐为案例对象,计算了固定顶储罐的总损失。通过对不同参数进行调节,比较分析了各变量对损失量的影响程度,得出了影响固定顶储罐静置储藏损失和工作损失的关键参数和次要参数。并在此基础上,提出了降低固定顶储罐VOCs排放量的对应措施。实验结果表明:影响固定顶储罐静置储藏损失的关键参数为油品蒸气相对分子质量、日平均液体表面温度和液体存储高度,次要参数为日环境温差和罐漆太阳能吸收率;影响工作损失的关键参数为油品蒸气相对分子质量、日平均液体表面温度和年净周转量。     

A review of aqueous-phase VOC transport in modern landfill liners

Leachates from municipal solid waste (MSW) and hazardous waste landfills contain a wide range of volatile organic compounds (VOCs) in addition to inorganic compounds. VOCs have been shown to migrate and contaminate the surrounding environment and impair the use of groundwater. Therefore, the effectiveness of modern landfill liner systems to minimize migration of VOCs is of concern. Most modern landfills employ a composite liner consisting of a geomembrane overlying a compacted clay liner or a geosynthetic clay liner. The geomembrane is often believed to be the primary barrier to contaminant transport. However, for VOCs, the clay component usually controls the rate of transport since VOCs are shown to diffuse through geomembrane at appreciable rates. Additionally, analyses have shown that transport of volatile organic compounds (VOCs) generally is more critical than transport of inorganic compounds (e.g., toxic heavy metals), even though VOCs are often found at lower concentrations in leachates. Therefore, the effectiveness of modern landfill liner systems to minimize migration of VOCs and transport of VOCs through clay liners and modeling of transport through composite liners merit scrutiny. This paper presents a review of recent research by the author and others on these topics. A systematic and comprehensive approach to determine mass transport parameters for transport of VOCs in liquid phase through compacted clay liners, geosynthetic clay liners (GCLs), and geomembranes has enabled to develop realistic models to predict mass flux of VOCs through modern composite liners and provide a quantitative basis to evaluate potential for transport of dissolved VOCs and the equivalency of different composite liners.     

A practical approach to steam‐enhanced dual‐phase extraction: A case study

This article presents the results of a pilot test that was conducted to determine the effectiveness of using steam‐enhanced dual‐phase extraction (DPE) at a former industrial site in New York. The pilot test proved that steam‐enhanced DPE was very effective at removing significant contaminant mass from the subsurface in a relatively short time period. Concentrations of volatile organic compounds and semivolatile organic compounds in the vapor stream and groundwater were successfully reduced, in some cases by orders of magnitude. Based on the results of the steam‐enhanced DPE pilot test, the final remedy for the site includes implementing this technology at selected areas as an alternative to DPE alone or other remedial alternatives, such as excavation or groundwater pump and treat. © 2003 Wiley Periodicals, Inc.     

Identification of Odor Causing Compounds in a Commercial Dairy Farm

The odorous air emissions from confined animal feeding operations (CAFOs), such as swine, poultry and dairy farms, are increasingly raising community complaints. Odorous emissions can result in health damages, psychological discomforts and adverse aesthetic effects in the community. However, these emissions are not well characterized up to now due to the lack of legislation, the limitations in sampling and instrumentation techniques, and the complexity of the emissions themselves. This study is aimed at the development of a high volume sampler and sorbent assembly to identify the odor causing compounds from a diary CAFO. The sorbent was custom designed to target the potential compounds that may exist in a dairy farm and was validated in laboratory with a synthetic odor from the swine manure. The actual samples at the diary farm were collected in spring and summer of 2005. The sorbents were solvent extracted and individual odor compounds were identified using GC–MS (gas chromatography–mass spectroscopy). The data obtained indicated that high volume sampling can shorten the sampling time from days to within 4 h. Both volatile organic compounds (VOCs) and volatile fatty acids (VFAs) have been identified from the dairy farm, such as phenol, methylphenol, 4-ethyl phenol, indole, methyl indole, benzyl alcohol, hexanoic acid, valeric acid and iso-valeric acid, together with some nitrogen containing compounds that have not been reported before.     

Fiberboard plant emissions control using a silent discharge plasma

A silent discharge plasma reactor was constructed to test a potential industrial application for controlling volatile organic carbon emission from fiberboard manufacturing plants. The reactor consisted of a cylindrical single barrier dielectric barrier discharge cell connected to a high‐voltage ac power supply. Various concentrations of turpene in air were introduced into the reactor under dry and wet conditions. The destruction removal efficiencies (DRE) were monitored using a gas chromatograph mass spectrometer (GCMS) and the concentrations of carbon dioxide generated from the oxidation ofturpene were monitored using a Fourier Transform Infrared Spectrometer (FTIR). It was found that 90 percent of the turpenes could be removed at modest energy densities and that adding water to the gas mix greatly enhanced the destruction of the turpenes. However, even at high energy densities, the oxidation of turpenes did not completely form carbon dioxide. The results suggest that the Silent Discharge Plasma (SDP) system can be used to control the emission of volatile organic compounds (VOCs) from fiberboard plants, but that further testing is needed to limit the emission of carbon monoxide.     

The evaluation of an analytical protocol for the determination of substances in waste for hazard classification

The classification of waste as hazardous could soon be assessed in Europe using largely the hazard properties of its constituents, according to the the Classification, Labelling and Packaging (CLP) regulation. Comprehensive knowledge of the component constituents of a given waste will therefore be necessary. An analytical protocol for determining waste composition is proposed, which includes using inductively coupled plasma (ICP) screening methods to identify major elements and gas chromatography/mass spectrometry (GC–MS) screening techniques to measure organic compounds. The method includes a gross or indicator measure of ‘pools’ of higher molecular weight organic substances that are taken to be less bioactive and less hazardous, and of unresolved ‘mass’ during the chromatography of volatile and semi-volatile compounds. The concentration of some elements and specific compounds that are linked to specific hazard properties and are subject to specific regulation (examples include: heavy metals, chromium(VI), cyanides, organo-halogens, and PCBs) are determined by classical quantitative analysis. To check the consistency of the analysis, the sum of the concentrations (including unresolved ‘pools’) should give a mass balance between 90% and 110%. Thirty-two laboratory samples comprising different industrial wastes (liquids and solids) were tested by two routine service laboratories, to give circa 7000 parameter results. Despite discrepancies in some parameters, a satisfactory sum of estimated or measured concentrations (analytical balance) of 90% was reached for 20 samples (63% of the overall total) during this first test exercise, with identified reasons for most of the unsatisfactory results. Regular use of this protocol (which is now included in the French legislation) has enabled service laboratories to reach a 90% mass balance for nearly all the solid samples tested, and most of liquid samples (difficulties were caused in some samples from polymers in solution and vegetable oil). The protocol is submitted to French and European normalization bodies (AFNOR and CEN) and further improvements are awaited.     

Occurrence of organic pollutants in recovered soil fines from construction and demolition waste

The objective of this study was to characterize recovered soil fines from construction and demolition (C&D) waste recycling facilities for trace organic pollutants. Over a period of 18 months, five sampling trips were made to 14 C&D waste recycling facilities in Florida. Screened soil fines were collected from older stockpiles and newly generated piles at the sites. The samples were analyzed for the total concentration (mg/kg) of a series of volatile organic compound (VOCs) and semi-volatile organic compounds (semi-VOCs). The synthetic precipitation leaching procedure (SPLP) test was also performed to evaluate the leachability of the trace organic chemicals. During the total analysis only a few volatile organic compounds were commonly found in the samples (trichlorofluoromethane, toluene, 4-isopropyltoluene, trimethylbenzene, xylenes, and methylene chloride). A total of nine VOCs were detected in the leaching test. Toluene showed the highest leachability among the compounds (61.3-92.0%), while trichlorofluoromethane, the most commonly detected compound from both the total and leaching tests, resulted in the lowest leachability (1.4-39.9%). For the semi-VOC analysis, three base-neutral semi-VOC compounds (bis(2-ethylhexyl)phthalate, butyl benzyl phthalate, and di-n-butyl phthalate) and several PAHs (acenaphthene, pyrene, fluoranthene, and phenanthrene) were commonly detected in C&D fines samples. These compounds also leached during the SPLP leaching test (0.1-25%). No acid extractable compounds, pesticides, or PCBs were detected. The results of this study were further investigated to assess risk from land applied recovered soil fines by comparing total and leaching concentrations of recovered soil fines samples to risk-based standards. The results of this indicate that the organic chemicals in recovered soil fines from C&D debris recycling facilities were not of a major concern in terms of human risk and leaching risk to groundwater under reuse and contact scenarios.     

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.     

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.     

催化氧化技术治理苯化工装置和罐区含氮挥发性有机物废气

采用催化氧化技术对某石化企业苯胺、硝基苯等生产装置和罐区的含氮挥发性有机物(NVOCs)废气进行集中处理,建成了一套20 000 Nm~3/h规模的安全高效处理装置。采用自主研发的WSH-2N型蜂窝状Pt-Pd-Ce催化剂,在高效氧化有机物的同时,高选择性地将有机氮转化为N_2。运行结果表明,净化气非甲烷总烃质量浓度低于15 mg/m~3,非甲烷总烃去除率大于99%,NO_x质量浓度低于10 mg/m~3,苯、苯胺、硝基苯、环己烷等特征有机污染物浓度均低于检出限,各项指标优于国内外现有技术。     

Characterization of wood plastic composites made from landfill-derived plastic and sawdust: Volatile compounds and olfactometric analysis

Application of wood plastic composites (WPCs) obtained from recycled materials initially intended for landfill is usually limited by their composition, mainly focused on release of volatile organic compounds (VOCs) which could affect quality or human safety. The study of the VOCs released by a material is a requirement for new composite materials. Characterization and quantification of VOCs of several WPC produced with low density polyethylene (LDPE) and polyethylene/ethylene vinyl acetate (PE/EVA) films and sawdust were carried out, in each stage of production, by solid phase microextraction in headspace mode (HS-SPME) and gas chromatography–mass spectrometry (GC–MS). An odor profile was also obtained by HS-SPME and GC–MS coupled with olfactometry analysis. More than 140 compounds were observed in the raw materials and WPC samples. Some quantified compounds were considered WPC markers such as furfural, 2-methoxyphenol, N-methylphthalimide and 2,4-di-tert-butylphenol. Hexanoic acid, acetic acid, 2-methoxyphenol, acetylfuran, diacetyl, and aldehydes were the most important odorants. None of the VOCs were found to affect human safety for use of the WPC.     

Effect of Changing VOC Influent Composition on the Microbial Community Structure of TBABs

Microbial communities in trickle bed air biofilters (TBABs) were evaluated under conditions of interchanging the feed volatile organic compounds (VOCs) and VOC mixtures. Three independent TBABs (Biofilter “A,” “B,” and “C”) were run under interchanging VOCs conditions with different initial VOCs. Two aromatic compounds (toluene and styrene) and two oxygenated compounds (methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK)) were interchanged as single solutes. Two other TBABs “D” and “E” were run for two VOC mixtures. Biofilter “D” had a VOC mixture with equal molar ratio of the four components and Biofilter “E” received a VOC mixture with its composition based on EPA 2003 emission report. Denaturing gradient gel electrophoresis (DGGE) analysis of 16S rRNA genes was used to assess the microbial richness in TBABs for treating the VOC mixtures and the impact of interchanging VOCs on the bacterial community structure in the biofilters. The results from DGGE indicated that the microbial community structure in the biofilter was different after each interchange of VOCs. Some bands of microbial species faded and some bands were strengthened. For the two TBABs treating VOC mixtures, the microbial species did not show significant difference, but the richness among these species was different from each other.     

Substance-specific detection and pursuit of non-eliminable compounds during biological treatment of waste water from the pharmaceutical industry

Up to now comprehensive examination and assessment of the elimination behaviour of many different pollutants in biological waste water treatment failed above all because of limited possibilities to pursue polar organic compounds of anthropogenic and biogenic origin. In this case the behaviour of waste water constituents during the treatment of waste water from the pharmaceutical industry was studied with the help of mass-spectrometric detection (MS). After completest possible extraction and concentration by liquid/liquid and solid phase extraction (SPE) from samples of influent and effluent of a pilot plant, substance-specific determination and identification was done after chromatographic separation and with the help of mixture analysis, respectively. Separation by gas chromatography coupled with MS was applied to pursue the organic compounds, which are volatile without decomposition, during the waste water treatment process. Flow injection analysis (FIA) bypassing the analytical column combined with soft-ionizing interfaces served for screening of the polar compounds. Then they were separated by liquid chromatographic methods to recognize changes in the qualitative and quantitative compound spectrum. Mixture analysis by FIA combined with tandem mass spectrometry (FIA/MS/MS) was used for identification of the pollutants without previous chromatographic separation. A laboratory-made daughter ion library helped to identify some of the poorly eliminable pollutants detected. The presentation of the monitoring procedures applied was made in such a way that the treatment results were visually recognizable. Due to the use of time-saving FIA/MS, this method may serve for substance-specific monitoring of the treatment of possibly problematic waste waters. ©     

Influence of Traffic Emissions Estimation Variability on Urban Air Quality Modelling

The main objective of this work is to analyse how uncertainties in emission data of nitrogen oxides (NO_x) and volatile organic compounds (VOC), originated from road traffic, influence the model prediction of ozone (O₃) concentration fields. Different methods to estimate emissions were applied and results were compared in order to obtain their variability. Based on these data, different emission scenarios were compiled for each pollutant considering the minimum and the maximum values of the estimated emission range. These scenarios were used as input to the MAR-IV mesoscale modelling system. Simulations have been performed for a summer day in the Northern Region of Portugal. The different approaches to estimate NO_x and VOC traffic emissions show a significant variability of absolute values and of their spatial distribution. Comparison of modelling results obtained from the two scenarios presents a dissimilarity of 37% for ozone concentration fields as a response of the system to a variation in the input emission data of 63% for NO_x and 59% for VOC. Far beyond all difficulties and approximations, the developed methodology to build up an emission data base shows to be consistent and an useful tool in order to turn applicable an air quality model. Nevertheless, the sensitivity of the model to input data should be considered when it is used as a decision support tool.     

The performance of a natural treatment system for landfill leachate with special emphasis on the fate of organic pollutants.

A natural treatment system for the treatment of leachate was studied at Moskogen landfill in southern Sweden. This facility consists of three consecutive ponds and a soil-plant (SP)-system. A test area, receiving water from the third pond with the same hydraulic load as the SP-system, was used for estimation of the latter system. Quality parameters including biochemical oxygen demand, total organic carbon, ammonium, nitrate, orthophosphate, and total suspended solids along the treatment line were determined as well as soluble metals (Cu, Cd, Zn, Cr, Ni, and Pb). In addition a thorough investigation along the treatment line has also been performed concerning volatile organic compounds and semi-volatile organic compounds. Non-polar organic compounds were investigated using gas chromatography-mass spectrometry. Quantification was based on the assumption of equal response for the compounds found in comparison with the chosen marker substances. For polar, water-soluble compounds the measurements were restricted to phenolic compounds using high-performance liquid chromatography. Several different types of organic compounds were found in the raw leachate including aromatics, benzene-sulfonamides, biphenyls, naphthalene, organic phosphates, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, phenols and phthalates. The treatment system efficiently reduced organic pollutants, heavy metals, and nitrogen/phosphorous compounds. Most metals and organic compounds in the leachate were already significantly reduced to a low level in the treatment ponds and ammonium-N was efficiently transformed to nitrate-N in the SP-system.