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.     

Mechanical–Thermal Properties and VOC Emissions of Natural-Flour-Filled Biodegradable Polymer Hybrid Bio-Composites

The mechanical–thermal properties and volatile organic compound (VOC) emissions of natural-flour-filled, biodegradable polymer bio-composites were investigated according to variation in porous inorganic filler types. At a porous inorganic filler content of 3%, the tensile and flexural strengths of the hybrid bio-composites were not significant changed. However, the coefficient of thermal expansion and thermal expansion of the bio-composites were slightly decreased. Furthermore, the incorporation of the porous inorganic materials into bio-composites slightly increased the E’ values of the hybrid bio-composites over the entire temperature range, although the tan δ_max temperature (T _g) of the hybrid bio-composites was not significantly changed. At a porous inorganic filler content of 3%, the various odor and VOC emissions of the hybrid bio-composites were significantly decreased because the various oxidation and thermal degradation gases of the natural flour and matrix were absorbed in the pore structures of the porous inorganic fillers and thereby prevented the migration into the final products.     

Swine manure composting by means of experimental turning equipment

The purpose of research was to test the effectiveness of a prototype of a turning machine and to evaluate the feasability of a farm-scale composting process of the solid fraction of swine manure. A qualitative evaluation of the process and final product was made by monitoring the following parameters: process temperature, oxygen concentration inside the biomass, gaseous emissions (CH4, CO2, NH3, N2O), respiration index, humification index, total and volatile solids, carbon and nitrogen, pH and microbial load. The prototype proved to be very effective from a technical-operational point of view. The composting process exhibited a typical time-history, characterised by a thermophilic phase followed by a curing phase [Chiumenti, A., Chiumenti, R., Diaz, L.F., Savage, G.M., Eggerth, L.L., Goldstein, N., 2005. Modern Composting Technologies. BioCycle-JG Press, Emmaus, PA, USA]. Gas emissions from compost the windrow were more intense during the active phase of the process and showed a decreasing trend from the thermophilic to the curing phase. The final compost was characterized by good qualitative characteristics, a significant level of humification [Rossi, L., Piccinini, S., 1999. La qualità agronomica dei compost derivanti da liquami suinicoli. (Agronomic quality of swine manure compost). L'informatore Agrario 38, 29-31] and no odor emissions. This method of managing manure represents an effective, low cost approach that could be an interesting opportunity for swine farms.     

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.     

Effect of Orientation on the Morphology and Mechanical Properties of PLA/Starch Composite Filaments

Polylactic acid (PLA)/starch fibers were produced by twin screw extrusion of PLA with granular or gelatinized starch/glycerol followed by drawing through a set of winders with an intermediate oven. At 30% starch, fibers drawn 2–5x were highly flexible (elongation 20–100%) while undrawn filaments were brittle (elongation 2–9%). Tensile strength and moduli increased with increasing draw ratio but decreased with increasing starch content. Mechanical properties were better for composites made with gelatinized starch/glycerol than granular starch. In conclusion, orientation greatly increases the flexibility of PLA/starch composites and this may be useful not only in fibers but also possibly in molded articles. Other advantages of starch addition could include fiber softness without added plasticizer, moisture/odor absorbency and as a carrier for active compounds.     

HZ-16型大孔树脂吸附处理含RDT-8废水

采用HZ-16型大孔树脂对含三（三溴苯氧基）三嗪（RDT-8）废水进行吸附及脱附处理。实验结果表明：在废水流量为4.0 BV/h的条件下,树脂最佳吸附工艺条件为出水体积88.0 BV,此条件下出水COD小于291 mg/L,挥发酚质量浓度小于0.08 mg/L;在脱附液流量为0.5 BV/h的条件下,树脂最佳脱附工艺条件为脱附液体积3.0 BV,此条件下脱附液中挥发酚质量浓度为30.6 mg/L,挥发酚脱附率高达76.4%。在最佳吸附-脱附工艺条件下,连续进行10次动态吸附-脱附实验,吸附出水中COD为137~294 mg/L,COD去除率为72.5%~89.1%,挥发酚质量浓度稳定在0.05 mg/L以下,挥发酚去除率为99.8%~100%,说明HZ-16型大孔树脂的吸附-脱附性能稳定。     

Determination of nitrous oxide, methane, and ammonia emissions from a swine waste composting process

The amounts of harmful gas emissions from the process of composting swine waste were determined using an experimental composting apparatus. Forced aeration (19.2–96.1 l/m³/min) was carried out continuously, and exhaust gases were collected and analyzed periodically. With weekly turning and the addition of a bulking agent in order to decrease the moisture content and increase air permeability, the temperature of most of the contents rose to 70°C and composting was complete within 3–5 weeks. NH₃, CH₄, and N₂O emissions were high in the early stage of composting. About 10%–25% of the nitrogen in the raw material was lost as NH₃ gas during composting. The emission rate of NH₃ mainly depended on the aeration rate, so that as the aeration rate rose, the level of NH₃ emissions increased. The CH₄ and N₂O emissions could be kept lower with adequate treatment at more than 40 l/m³/min aeration. N₂O may be mainly the result of the denitrification of NO _x -N in the additional matured compost used as a composting accelerator. Received: September 11, 1998 / Accepted: November 8, 1999     

Sulfide emissions from different areas of a municipal solid waste landfill in China

Degradation of municipal solid waste in landfills generates sulfide compounds, which are considered one of the main sources of odor emissions. Field sampling was conducted at surfaces of operating, inoperative, and soil-covered areas of a landfill site in northern China to characterize the sulfide compounds. The results showed that dimethyl disulfide dominated the sulfide compounds, accounting for up to 73.6% of the total detected sulfide. With the biggest odor concentration of 365, diethyl sulfide was the most significant sulfide compound. The estimated sulfide emission rates at surfaces of operating and soil-covered areas were similar, and the emission rate of dimethyl disulfide at Surface of Operating Area was up to 345.9 μg/m³ h. Dimethyl disulfide could be released from the fresh waste, and its normalized concentration at 0.2 m beneath operating surface was 10.4 times that at 0.4 m.     

Treatment of Sydney N.S. tar pond sludge in a pilot‐scale rotary kiln

Tar pond wastes from Sydney, Nova Scotia, containing 50 ppm or more of polychlorinated biphenyls (PCBs) were treated in a pilot‐scale rotary kiln. In order to use the existing feed system attached to the rotary kiln, the wastes were first oven‐dried. Stack gas sampling was conducted during the test, which included measurement of volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), semi‐volatile organic compounds (SVOCs), HCl, and metals. The purpose of this study was to determine emissions from treatment of the tar pond waste using rotary kiln technology. It was found that the dried sludge could sustain combustion in the kiln without any supporting fuel. The emissions of polychlorinated dibenzodioxins/furans (PCDD/Fs) were higher than the Canadian Council of Ministers of the Environment (CCME) air emissions guidelines, and the reasons for this are discussed. © 2008 Wiley Periodicals, Inc.     

Odor compounds from different sources of landfill: characterization and source identification

This study investigated the odor compounds from different areas in a landfill site, which included the municipal solid waste (MSW)-related area, the leachate-related area and the sludge-related area. Nine sampling points were placed and 35 types of odorous substances were measured and quantified from these grabbed samples. The results showed that the main odorous substances emitted from landfill site were styrene, toluene, xylene, acetone, methanol, n-butanone, n-butylaldehyde, acetic acid, dimethyl sulfide, dimethyl disulfide and ammonia. In the MSW-related area, the highest concentrations of oxygenated compounds were observed at the gas extraction wells (GW), while sulfur compounds were rare. Ammonia in the sludge-related area was very abundant. Sludge discharge area (SD1) and sludge disposal work place (SD2) were representative points of pre- and post-drying, in which the characterizations of the emitted odorous gas were different. After chemical drying, the concentration of ammonia increased, whereas those of volatile fatty acids and sulfur compounds decreased. In the leachate-related area, relatively low concentrations of all those odorants were detected in leachate storage pool (LS), which may be due to the enclosure operation of the leachate storage pool. Using principal components analysis and cluster analysis, GW, SD1 and SD2 were distinguished from the other sampling points. The typical odorants in GW were acetaldehyde, ethyl benzene, xylene, methylamine and dimethyl formamide. The typical odorants in SD1 were methyl mercaptan, valeric acid and isovaleric acid, while those in SD2 were carbon disulfide, acetone, 3-pentanone, methanol and trimethylamine. The typical odorants in other sampling points were hydrogen sulfide, n-butylaldehyde and acetic acid.     

Effect of aeration rate and moisture content on the emissions of selected VOCs during municipal solid waste composting

The influence of the industrial control composting conditions (aeration 0.005–0.300?L_air?kg^?1 and moisture 40–70?%) of municipal solid waste on the composition of the selected compound emitted (limonene, β-pinene, 2-butanone, undecane, phenol, toluene, dimethyl sulfide, dimethyl disulfide) was studied. The highest emissions of volatile organic compounds (VOCs) were observed in the early stages of the processes. At the end of the process, low concentrations of the emitted compounds were found. Aeration rate had a strong effect on emissions. High aeration rate (0.300?L_air?kg^?1?min^?1) caused normally high emissions of all selected compounds whereas low aeration rates (0.05?L_air?kg^?1?min^?1) could cause anaerobiosis problems and generation of organic sulphur compounds. We observed that the effect of the moisture upon the emitted concentrations varied depending on the studied compound.     

Adsorbable organic halides (AOX), AOX formation potential, and PCDDs/DFs in landfill leachate and their removal in water treatment processes

Adsorbable organic halides (AOX) and AOX formation potential (AOXFP) were investigated in 46 landfill lea-chates as potentially toxic parameters. AOX in landfill leachate was within the range <10–2200 μg Cl/l, and AOXFP was within 51–15 000 μg Cl/l. AOX and AOXFP correlated with chemical oxygen demand (COD). AOX discharge from closed landfills was generally lower than that from operating landfills. The molar ratio of AOXFP/total organic carbon (TOC) suggested that organic compounds in a leachate have a double bond every 15–190 carbons under the supposition that one chlorine would add to one double bond. The five landfills discharging high-level AOXFP (>4000 μg Cl/l) were all landfills where sludge had been dumped. The removal efficiencies of three parameters through leachate treatment processes were as follows: polychlorinated dibenzo-dioxins/dibenzo-furans (PCDDs/DFs) > TOC > AOX. PCDDs/DFs were substantially removed at p.p.t. levels, while AOX was hardly removed at relatively low levels. Received: February 14, 2000 / Accepted: January 9, 2001     

New methods for fast on-site measurement of odorous compounds

New methods for measurement of odorous gases, especially for aerosol-bound chemical compounds, have been developed in the Department of Measurement Technology (Technical University of Hamburg Harburg--MT-TUHH). Odorous compounds in the waste gases produced by the food industry were analysed based on high-volume aerosol sampling techniques, enrichment on solid phase micro extraction (SPE) cartridges and analytical measurement techniques using thermal desorption gas chromatography-mass spectrometry. The analysis results were compared to classic analytical procedures using adsorbence materials (Tenax) for enrichment. In comparison to aerosol sampling, analysis of Tenax samples was found to be ineffective, especially for analyzing polar semi volatile compounds. In addition, sensor arrays were also used in the study to characterize odors of different waste gases emitted by food production facilities. Measuring the odor units of the waste gas of a fat producing factory, the results of sensor-array-measurements show good correlation with results obtained with olfactometric measurements.     

Development and evaluation of a mass spectrometer-based continuous emission monitor for volatile organic compound emissions from combustion devices

A mass spectrometer-based continuous emission monitor (MS-CEM) for organic compound emissions from combustion devices was developed and evaluated at the Louisiana State University (LSU) pilot-scale rotary kiln incinerator (RKI). The MS-CEM consists of a stack probe, heat-traced sampling line, vacuum pump, particulate filter, Nafion@ dryer and mass spectrometer. The mass spectrometer includes a computer that controls and optimizes the operation of the unit. The MS-CEM is capable of continuously analyzing up to 40 different volatile organic compounds on a real-time basis. The MS-CEM is capable of analyzing, computing and recording the analytical results for each and up to 40 different organic compounds in less than 0.3 s. Four different volatile organic compounds were mixed together and injected into the baghouse inlet while simultaneously analyzing each organic component exiting the RKI stack gas. The results obtained from MS-CEM were compared with the material balance values. The system response time (including the MS-CEM) varies from 1.1 to 1.5 min.     

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.     

Extension of EU Emissions Trading Scheme to Other Sectors and Gases: Consequences for Uncertainty of Total Tradable Amount

Emissions trading in the European Union (EU), covering the least uncertain emission sources of greenhouse gas emission inventories (CO₂ from combustion and selected industrial processes in large installations), began in 2005. During the first commitment period of the Kyoto Protocol (2008–2012), the emissions trading between Parties to the Protocol will cover all greenhouse gases (CO₂, CH₄, N₂O, HFCs, PFCs, and SF₆) and sectors (energy, industry, agriculture, waste, and selected land-use activities) included in the Protocol. In this paper, we estimate the uncertainties in different emissions trading schemes based on uncertainties in corresponding inventories. According to the results, uncertainty in emissions from the EU15 and the EU25 included in the first phase of the EU emissions trading scheme (2005–2007) is ±3% (at 95% confidence interval relative to the mean value). If the trading were extended to CH₄ and N₂O, in addition to CO₂, but no new emissions sectors were included, the tradable amount of emissions would increase by only 2% and the uncertainty in the emissions would range from −4 to +8%. Finally, uncertainty in emissions included in emissions trading under the Kyoto Protocol was estimated to vary from −6 to +21%. Inclusion of removals from forest-related activities under the Kyoto Protocol did not notably affect uncertainty, as the volume of these removals is estimated to be small.     

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.     

Characterization and control of odorous gases at a landfill site: a case study in Hangzhou, China

Municipal solid waste (MSW) landfills are one of the major sources of offensive odors potentially creating annoyance in adjacent communities. At the end of May 2007, an odor pollution incident occurred at the Tianziling landfill site, Hangzhou, China, where the residents lodged complaints about the intense odor from the landfill, which drew a significant attention from the government. In this study, ambient air monitoring was conducted at the Tianziling landfill site. The main odor composition of the gas samples collected on June 1st 2007 and the reduction of various odorous gases from the samples collected on June 1st 2009 due to the applied odor control techniques were determined using gas chromatography-mass spectrometry (GC-MS). In addition, variations of primary odorous gaseous (NH₃ and H₂S) concentrations at different locations in the landfill site from July 2007 to June 2009 were also investigated by using classical spectrophotometric methods. Results showed that a total of 68 volatile compounds were identified among which H₂S (56.58-579.84 μg/m³) and NH₃ (520-4460 μg/m³) were the notable odor components contributing to 4.47-10.92% and 83.91-93.94% of total concentrations, respectively. Similar spatial and temporal shifts of H₂S and NH₃ concentrations were observed and were significantly affected by environmental factors including temperature, air pressure and wind direction. Odor pollution was worse when high temperature, high humidity, low air pressure, and southeast, northeast or east wind appeared. Moreover, the environmental sampling points of the dumping area and the leachate treatment plant were found to be the main odor sources at the Tianziling landfill site. The odor control technologies used in this project had a good mitigating effect on the primary odorous compounds. This study provides long-term valuable information concerning the characteristics and control of odors at landfill sites in a long run.     

精对苯二甲酸生产企业挥发性有机物泄漏检测与排放估算

采用泄漏检测与修复(LDAR)技术分析了某精对苯二甲酸生产装置动静密封点的泄漏情况,共完成1 367个密封点的现场LDAR检测,测出28个泄漏点,总泄漏检出率为2.05%。其中储存单元的泄漏点数量较氧化单元和精制单元高,泄漏程度也较严重。泄漏点主要集中在法兰、开口管线和泵三类密封点;涉及轻液的泄漏密封点数量较多。依据LDAR检测结果,采用相关方程法估算设备动静密封点泄漏产生的挥发性有机物(VOCs)排放量约为4.999 t/a。法兰的VOCs泄漏排放量最大,约占63.89%,其次是泵和采样连接系统,占泄漏排放量的20.78%和7.89%。     

Desulfurization of coke oven gas from the coking of coking coal blended with a sorbent and waste plastic

A new way to implement the simultaneous reutilization of solid waste, the desulfurization of coke oven gas (COG), and even the desulfurization of coke by the co-coking of coking coal (CC) and waste plastic (WP) blended with a sorbent is proposed; the evolution of H₂S and the removal efficiency of H₂S from COG during the co-coking process were investigated in a lab-scale cylindrical reactor. The experimental results indicated that for the coking of CC blended with ZnO, Fe₂O₃, or blast furnace dust (BFD) as a sorbent, the instantaneous concentration of H₂S in COG was lower than 500 mg/m³ (which meets the technical specification requirement of the Chinese Cleaner Production Standard–Coking Industry, HJ/T 126-2003) when the molar ratio between the key component of the sorbent and the volatile S in CC or the CC/WP blend, n _Zn+Fe/n _S, was about 1.2 for ZnO and Fe₂O₃, but not for BFD under the same conditions, suggesting that ZnO and Fe₂O₃ are promising sorbents, but that BFD must be treated chemical or thermally before being used as a sorbent because of the size and complicated nature of the influence of its phase/chemical composition on its desulfurization ability. However, for the co-coking of CC and WP blended with ZnO as a sorbent, n _Zn+Fe/n _S must increase to 1.4 and 1.7 for 100/2 and 100/5 blends of CC/WP, respectively, to ensure a satisfactory efficiency for H₂S removal from COG. Part of this paper was presented at the International Symposium on EcoTopia Science 2005 (ISET05), Aug 8–9, 2005, Chikusa-ku, Nagoya, Japan