Development of a simple and sensitive method for the characterization of odorous waste gas emissions by means of solid-phase microextraction (SPME) and GC-MS/olfactometry

A solid-phase microextraction (SPME) method has been developed for the extraction of odorous compounds from waste gas. The enriched compounds were characterized by gas chromatography-mass spectrometry (GC-MS) and gas chromatography followed by simultaneous flame ionization detection and olfactometry (GC-FID/O). Five different SPME fiber coatings were tested, and the carboxen/polydimethylsiloxane (CAR/PDMS) fiber showed the highest ability to extract odorous compounds from the waste gas. Furthermore, parameters such as exposure time, desorption temperature, and desorption time have been optimized. The SPME method was successfully used to characterize an odorous waste gas from a fat refinery prior to and after waste gas treatment in order to describe the treatment efficiency of the used laboratory scale plant which consisted of a bioscrubber/biofilter combination and an activated carbon adsorber. The developed method is a valuable approach to provide detailed information of waste gas composition and complements existing methods for the determination of odors. However, caution should be exercised if CAR/PDMS fibers are used for the quantification of odorous compounds in multi-component matrices like waste gas emissions since the relative affinity of each analyte was shown to differ according to the total amount of analytes present in the sample.     

The potential to reduce emissions of airborne microorganisms by means of biological waste gas treatment systems

Investigations regarding the reduction of airborne germs in the waste gas of biowaste composting processes have been carried out at the Hamburg University of Science and Technology and the University of Leipzig. Numerous waste gas treatment plants, ranging from laboratory-scale to technical-scale, have been available at the institutes of these two project partners. All plants consisted of bioscrubber/biofilter combinations. The results showed that these biological systems designed for odour control are able to successfully reduce bioaerosol emissions, even though a reduction to background levels could not be achieved. The bioscrubber, if equipped with a droplet separator, proved to be mainly responsible for the reduction, whereas the biofilter acted as a source for microbial emissions originating from the filter material. It could be observed that the microbial population changed while passing the treatment system, indicating the ability of biological waste gas treatment systems to retain potentially pathogenic microorganisms from waste gases.     

恶臭气体生物处理技术研究进展

介绍了恶臭气体的种类、危害、特征、处理方法及原理；概述了恶臭气体的3种主要生物处理方法：生物滤池、生物滴滤池和生物洗涤器，介绍3种方法的工艺流程、技术特点及最新研究进展；提出了生物法处理恶臭气体亟需解决的问题及研究方向。     

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.     

Odour control at biowaste composting facilities

There are several options to effectively reduce odorous emissions at composting facilities depending on the type of composting system used. Some of the more relevant measures for open and enclosed composting facilities are presented in this article. Results from different investigations on odour reduction efficiencies of biological waste gas treatment systems at various scales are presented. Biofilter/bioscrubber combinations were used and different biofilter materials were tested. The more relevant odorous substances in the waste gas were identified, and their reduction in the different systems was measured. The biofilter proved to be mainly responsible for efficient odour degradation. The investigations presented in this article revealed that screened compost was very effective, and proved to be a low cost biofilter material for odour degradation purposes. Screened compost showed higher degradation rates than a coke-compost mixture newly developed by the University of Leipzig. Furthermore, it seems that enclosed systems have advantages when compared to conventional open single bed biofilters.     

Characterization and determination of the odorous charge in the indoor air of a waste treatment facility through the evaluation of volatile organic compounds (VOCs) using TD–GC/MS

Municipal solid waste treatment facilities are generally faced with odorous nuisance problems. Characterizing and determining the odorous charge of indoor air through odour units (OU) is an advantageous approach to evaluate indoor air quality and discomfort. The assessment of the OU can be done through the determination of volatile organic compounds (VOCs) concentrations and the knowledge of their odour thresholds. The evaluation of the presented methodology was done in a mechanical–biological waste treatment plant with a processing capacity of 245.000 tons year^?1 of municipal residues. The sampling was carried out in five indoor selected locations of the plant (Platform of Rotating Biostabilizers, Shipping warehouse, Composting tunnels, Digest centrifugals, and Humid pre-treatment) during the month of July 2011. VOC and volatile sulphur compounds (VSCs) were sampled using multi-sorbent bed (Carbotrap, Carbopack X, Carboxen 569) and Tenax TA tubes, respectively, with SKC AirCheck 2000 pumps. The analysis was performed by automatic thermal desorption (ATD) coupled with a capillary gas chromatography (GC)/mass spectrometry detector (MSD). One hundred and thirty chemical compounds were determined qualitatively in all the studied points (mainly alkanes, aromatic hydrocarbons, alcohols, aldehydes, esters, and terpenes), from which 86 were quantified due to their odorous characteristics as well as their potentiality of having negative health effects. The application of the present methodology in a municipal solid waste treatment facility has proven to be useful in order to determine which type of VOC contribute substantially to the indoor air odorous charge, and thus it can be a helpful method to prevent the generation of these compounds during the treatment process, as well as to find a solution in order to suppress them.     

Pyrolysis of waste animal fats in a fixed-bed reactor: Production and characterization of bio-oil and bio-char

Several animal (lamb, poultry and swine) fatty wastes were pyrolyzed under nitrogen, in a laboratory scale fixed-bed reactor and the main products (liquid bio-oil, solid bio-char and syngas) were obtained. The purpose of this study is to produce and characterize bio-oil and bio-char obtained from pyrolysis of animal fatty wastes. The maximum production of bio-oil was achieved at a pyrolysis temperature of 500 °C and a heating rate of 5 °C/min. The chemical (GC–MS analyses) and spectroscopic analyses (FTIR analyses) of bio-oil showed that it is a complex mixture consisting of different classes of organic compounds, i.e., hydrocarbons (alkanes, alkenes, cyclic compounds…etc.), carboxylic acids, aldehydes, ketones, esters,…etc. According to fuel properties, produced bio-oils showed good properties, suitable for its use as an engine fuel or as a potential source for synthetic fuels and chemical feedstock. Obtained bio-chars had low carbon content and high ash content which make them unattractive for as renewable source energy.     

Photo-oxidation and Photo-toxicity of Crude and Refined Oils

The fate and effects of an oil spill are effected by solar radiation through the action of photo-oxidation and photo-toxicity. Photo-oxidation, an important process in the weathering of oil, produces a variety of oxidized compounds, including aliphatic and aromatic ketones, aldehydes, carboxylic acids, fatty acids, esters, epoxides, sulfoxides, sulfones, phenols, anhydrides, quinones and aliphatic and aromatic alcohols. Some of these compounds contribute to the marine biota toxicity observed after an oil spill. Photo-toxicity occurs when uptake of certain petroleum compounds, e.g. certain polycyclic aromatic hydrocarbons and benzothiophenes, is followed by solar exposure which results in much greater toxicity than after dark uptake. The mechanism of PAH photo-toxicity includes absorbance of solar radiation by the PAH which produces a free radical and this free radical in turn reacts with oxygen to produce reactive oxygen species that can damage DNA and other cellular macromolecules. While most studies on photo-toxicity have been carried out in the laboratory, there are studies showing that water from an oil spill is photo-toxic to bivalve embryos for at least a few days after the spill. Other studies have found that oil contaminated sediments are photo-toxic to several marine invertebrates. More studies are required to determine if marine fauna at an oil spill site are effected by the action of photo-toxicity and photo-oxidation.     

生物滴滤塔处理模拟印刷有机废气

选取甲苯、乙酸乙酯为目标污染物模拟印刷有机废气,采用生物滴滤塔对其进行处理。从某污水处理厂曝气池活性污泥中筛选出3株能够高效降解甲苯、乙酸乙酯的优势菌种,经鉴定分别为枯草芽孢杆菌（Bacillus subtilis）、蜡状芽胞杆菌（Bacillus cereus）和嗜麦芽寡养单胞菌（Stenotrophomonas maltophilia）。实验结果表明：增大乙酸乙酯配比对VOCs去除率影响不大,而增大甲苯配比导致VOCs去除率下降明显;在进气VOCs质量浓度为约800 mg/m³（甲苯与乙酸乙酯的体积比1∶1）、气体空床接触时间为300 s、菌液喷淋量为800 L/h、菌液温度为25 ℃的条件下,VOCs去除率可达约99%。生物滴滤塔运行一段时间后,对菌种进行再鉴定,结果与处理前一致。     

Microbial oxidation of methane from old landfills in biofilters

Landfill gas emissions are among the largest sources of the greenhouse gas methane. For this reason, the possibilities of microbial methane degradation in biofilters were investigated. Different filter materials were tested in two experimental plants, a bench-scale plant (total filter volume 51 l) and a pilot plant (total filter volume 4 m3). Three months after the beginning of the experiment, very high degradation rates of up to 63 g CH4/(m3h) were observed in the bench-scale plant at mean methane concentrations of 2.5% v/v and with fine-grained compost as biofilter material. However, the degradation rates of the compost biofilter decreased in the fifth month of the experiment, probably due to the accumulation of exopolymeric substances formed by the microorganisms. A mixture of compost, peat, and wood fibers showed stable and satisfactory degradation rates around 20 g/(m3h) at mean concentrations of 3% v/v over a period of one year. In this material, the wood fibers served as a structural material and prevented clogging of the biofilter. Extrapolation of the experimental data indicates that biofilters for methane oxidation have to be at least 100 times the volume of biofilters for odor control to obtain the same cleaning efficiency per unit volume flow of feed gas.     

Biodiesel production from vegetable oil and waste animal fats in a pilot plant

In this study, corn oil as vegetable oil, chicken fat and fleshing oil as animal fats were used to produce methyl ester in a biodiesel pilot plant. The FFA level of the corn oil was below 1% while those of animal fats were too high to produce biodiesel via base catalyst. Therefore, it was needed to perform pretreatment reaction for the animal fats. For this aim, sulfuric acid was used as catalyst and methanol was used as alcohol in the pretreatment reactions. After reducing the FFA level of the animal fats to less than 1%, the transesterification reaction was completed with alkaline catalyst. Due to low FFA content of corn oil, it was directly subjected to transesterification. Potassium hydroxide was used as catalyst and methanol was used as alcohol for transesterification reactions. The fuel properties of methyl esters produced in the biodiesel pilot plant were characterized and compared to EN 14214 and ASTM D6751 biodiesel standards. According to the results, ester yield values of animal fat methyl esters were slightly lower than that of the corn oil methyl ester (COME). The production cost of COME was higher than those of animal fat methyl esters due to being high cost biodiesel feedstock. The fuel properties of produced methyl esters were close to each other. Especially, the sulfur content and cold flow properties of the COME were lower than those of animal fat methyl esters. The measured fuel properties of all produced methyl esters met ASTM D6751 (S500) biodiesel fuel standards.     

Performance of a passively vented field-scale biofilter for the microbial oxidation of landfill methane

An upflow biofilter system was operated on a passively vented landfill for the treatment of residual landfill methane. Biofilter methane emissions as a basis for determining methane removal rates were assessed by manual and automated chamber measurements, by measuring methane concentrations in the top layer gaseous phase in combination with gas flow rates, and by evaluating the methane load in the reverse gas flow following the change of landfill gas flux direction as governed by the course of barometric pressure. Methane removal rates were very high with maximum values of 80 g h(-1) m(-3). For the observed cases, the limit of biofilter methane oxidation capacity was not reached and absolute removal rates were thus linearly correlated to the amount of methane entering the filter. The analysis of methane loads flowing back from the biofilter following phases of longer, continuous and non-oscillating landfill gas emission, however, revealed that in these situations biofilter performance is restricted by deficient oxygen supply. At the oxygen-restricted capacity limit, removal rates are influenced by temperature (positively), methane influx (negatively) and flow rate (negatively) as a measure for the displacement of oxygen. These situations, however, account for only 12% of all emission phases. The investigated biofilter capacity, as derived from laboratory analyses of methanotrophic activities, is sufficient to oxidise 62% of the methane load emitted annually. Field and laboratory data provide a stable basis for the dimensioning of filters in future applications.     

臭氧氧化—生物活性炭滤池深度处理制革废水二级出水

采用臭氧氧化—生物活性炭滤池组合工艺深度处理制革厂的生化出水.在臭氧加入量为25 mg/L,氧化时间为25min、生物活性炭滤池HRT为lh的条件下,处理后废水平均COD为51mg/L,平均TOC为15.1mg/L,平均UV254(波长254 nm处单位比色皿光程下的吸光度)为0.12,平均氨氮质量浓度为0.51 mg/L,出水水质达到GB18918-2002《城镇污水处理厂污染物排放标准》中的一级B排放标准.     

Occupational hygiene in a Finnish drum composting plant

Bioaerosols (microbes, dust and endotoxins) and volatile organic compounds (VOCs) were determined in the working air of a drum composting plant treating source-separated catering waste. Different composting activities at the Oulu drum composting plant take place in their own units separated by modular design and constructions. Important implication of this is that the control room is a relatively clean working environment and the risk of exposure to harmful factors is low. However, the number of viable airborne microbes was high both in the biowaste receiving hall and in the drum composting hall. The concentration (geometric average) of total microbes was 21.8 million pcs/m3 in the biowaste receiving hall, 13.9 million pcs/m3 in the drum composting hall, and just 1.4 million pcs/m3 in the control room. Endotoxin concentrations were high in the biowaste receiving hall and in the drum composting hall. The average (arithmetic) endotoxin concentration was over the threshold value of 200 EU/m3 in both measurement locations. In all working areas, the average (arithmetic) dust concentrations were in a low range of 0.6-0.7 mg/m3, being below the Finnish threshold value of 5 mg/m3. In the receiving hall and drum composting hall, the concentrations of airborne microbes and endotoxins may rise to levels hazardous to health during prolonged exposure. It is advisable to use a respirator mask (class P3) in these areas. Detected volatile organic compounds were typical compounds of composting plants: carboxylic acids and their esters, alcohols, ketones, aldehydes, and terpenes. Concentrations of VOCs were much lower than the Finnish threshold limit values (Finnish TLVs), many of the quantified compounds exceeded their threshold odour concentrations (TOCs). Primary health effects due VOCs were not presumable at these concentrations but unpleasant odours may cause secondary symptoms such as nausea and hypersensitivity reactions. This situation is typical of composting plants where the workers are exposed to dozens of VOCs simultaneously. The odour units (OU/m3) were measured using olfactometer. The numbers were 23,000 OU/m3 at the output end of the composting drum and 6300 OU/m3 in the exhaust pipe. Inside the composting hall, the number of odour units was 500 and 560 OU/m3.     

微生物菌剂强化处理油砂

研究了微生物菌剂对油砂的处理效果，并通过第15天和第30天两次追加微生物菌剂和营养物质来加速分解石油类污染物。试验结果表明，经过56d的处理，菌剂强化处理单元最终油去除率达到47．4％；添加营养物质和农家肥的对照单元油去除率为23．6％，证明土著菌种在得到适宜的营养和共代谢基质后降解了部分石油；未做任何处理的原始油砂单元含油量基本没有变化。通过气相色谱一质谱联用分析表明，微生物菌剂对于较少碳原子数的有机物质有较好的降解效果。处理单元中随着石油分解过程的进行，系统pH会有一个明显的下降过程。通过对照单元细菌数的检测发现，改善营养物质和氧含量，可以提高土著菌种的石油降解件能。     

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.     

Solid phase microextraction (SPME) as an effective means to isolate degradation products in polymers

A new sample preparation technique, solid phase microextraction (SPME), was compared with direct headspace-GC-MS with respect to the type and amount of identified compounds. Three types of LDPE films containing photosensitising additives according to the Scott-Gilead patents and pure LDPE were used as model substances. The polyethylene films were thermally aged at 80‡C after the induction period was surpassed by subjecting the materials to 100 h of UV radiation. The new SPME method was developed using nonpolar poly(dimethylsiloxane) and polar carbowax fibers to extract the low molecular weight products formed in the polyethylene films during aging. Many more products were identified after SPME followed by GC-MS than after direct headspace-GC-MS of the samples. The SPME method allowed the identification of homologous series of carboxylic acids, ketones, and furanones, while direct headspace-GC-MS identified only a few carboxylic acids (C1-C6) and small amounts of some ketones and furanones. In general, SPME was more effective in extracting less volatile products, and in particular, the polar carbowax fiber identified also C7-C12 carboxylic acids and 4-oxopentanoic acid. By SEC and FTIR we confirmed that the number and amount of former degradation products correlated well with the decrease in molecular weights and the amount of formed carbonyl compounds.     

Performance of Trickle-Bed Air Biofilter: A Comparative Study of a Hydrophilic and a Hydrophobic Voc

Two lab-scale trickle-bed air biofilters were operated for investigating the difference in performance between a hydrophilic and a hydrophobic volatile organic compound (VOC). Methyl isobutyl ketone (MIBK) and styrene were selected as a model hydrophilic and hydrophobic VOCs, respectively. Effects of loading rates, biofilter re-acclimation, removal profile along biofilter depth, nitrogen consumption, and CO₂ production were compared under three operating conditions, namely, backwashing and two non-use periods (starvation and stagnant). Consistent over 99% removal efficiency up to loading rates of 3.26 kg COD/m³-day was obtained for the MIBK biofilter at 0.76 min empty bed retention time (EBRT) and 1.5 L/d nutrient flow. A similar performance for the styrene biofilter was obtained for loading rates up to 1.9kg COD/m³-day at 2.02 min EBRT and 2.4 L/d nutrient flow. The MIBK biofilter required only an initial acclimation period of 16 days while styrene biofilter required 46 days. Non-use periods can be used as another means of biomass control for both biofilters when the employed loading rate did not exceed 1.27 and 2.17 kg COD/m³-day for styrene and MIBK biofilters, respectively. The re-acclimation of both biofilter was delayed with increase of loading rate. MIBK biofilter re-acclimated in 90 min, while styrene biofilter re-acclimated in more than 600 min. Under similar loading rates, MIBK biofilter utilized less biofilter depth than styrene biofilter. Nitrogen consumption behaviors were apparently different between the two biofilters. Styrene biofilter had higher CO₂ production than MIBK biofilter and its CO₂ production was closely related to the theoretical complete chemical oxidation.     

聚乙烯副产物聚乙烯蜡的热解及轻质馏分的GC-MS分析

采用高温模拟蒸馏、红外光谱和热重分析等方法对聚乙烯副产物聚乙烯蜡进行了表征。在间歇高压反应釜中对聚乙烯副产物聚乙烯蜡进行了热解,并通过正交实验考察了热解温度、停留时间和初始压力对液相产物收率的影响。利用GC-MS技术对液相产物轻质馏分(低于200℃)进行了分析。结果表明:聚乙烯副产物聚乙烯蜡主要由长链脂肪烃(C_(14)~C_(70))组成;热解发生的温度范围为175~490℃;热解温度和停留时间是影响液相产物收率的主要因素;液相产物轻质馏分的碳数分布在C_9~C_(20),主要为α-烯烃(占比32.79%)和正构烷烃,其中单体烃含量最高的是1-癸烯(占比8.46%),它是制备高级合成润滑油聚α-烯烃的优质原料。     

生物滴滤塔处理含H_2S和NH_3气体的中试研究

利用生物滴滤塔对含H_2S和NH_3气体的处理进行了中试研究.经培养驯化的活性污泥在生物滴滤塔上挂膜后,对H_2S和NH_3的去除率分别达85%和90%以上,处理后NH_3出口质量浓度小于0.2 mg/m~3、H_2S出口质量浓度小于0.001 mg/m~3,均达到GB14554-93<恶臭污染物排放标准>和TJ36-79<工业企业设计卫生标准>.对装置连续运行的稳定性研究表明,NH_3和H_2S的去除率均能保持稳定.