Thermal and thermo-chemical pre-treatment of four waste residues and the effect on acetic acid production and methane synthesis

In this study four diverse solid waste substrates (coal, Kraft pulp solids, chicken feathers and chicken processing waste) were thermally pre-treated (70, 140 and 200 °C), under an inert (nitrogen) or oxidative (oxygen) atmosphere, and then anaerobically digested. Membrane inlet mass spectrometry during the thermal and thermo-chemical reactions was successfully used to establish oxygen and carbon dioxide gas fluxes and product formation (acetic acid). There was significant solids hydrolysis pre-treatment at 200 °C under an oxidative atmosphere, as indicated by a decrease in the volatile suspended solids and an increase in dissolved organic carbon. Greater concentrations of volatile fatty acids were produced under oxidative conditions at higher temperatures. The methane yield more than tripled for feathers after pre-treatment at 140 °C (under both atmospheres), but decreased after oxidative pre-treatment at 200 °C, due to the destruction of available carbon by the thermo-chemical reaction. Methane yield more than doubled for the Kraft pulp solids with the 200 °C pre-treatment under oxidative conditions. This study illustrated the power of wet oxidation for solids destruction and its potential to improve methane yields generated during anaerobic digestion.     

Effects of flue gas composition on the catalytic destruction of chlorinated aromatic compounds with a V-oxide catalyst

When using catalytic flue gas cleaning, several flue gas compounds may influence oxidation reactions of hazardous volatile organic compounds, possibly leading to lower reaction rates and, thus, to an incomplete destruction. Experimental investigations were performed with regard to the influence of selected flue gas compounds, like hydrogen chloride, sulfur dioxide, oxygen, and water vapour, on the catalytic destruction behavior of chlorobenzenes under flue gas cleaning conditions of an incineration plant. For this purpose, a metal oxide catalyst was operated at different temperatures at a space velocity of 3600 h-1 in a laboratory-scale fixed bed reactor with model flue gases, and with real flue gases generated from the TAMARA waste incineration plant. The results obtained from the studies with model flue gas were analyzed with respect to reaction kinetics. These kinetics were applied for comparison with the experimental data gained in the real flue gas.     

CHANGES IN MAJOR AND TRACE COMPONENTS OF LANDFILL GAS DURING SUBSURFACE MIGRATION

A gas plume emanating from the Foxhall Landfill in Suffolk (U.K.) has been defined within unsaturated ferruginous sands on the basis of elevated concentrations of methane, carbon dioxide and volatile organic compounds (VOCs). The plume is relatively narrow, extends more than 100 m from the landfill boundary, and lies mainly between 2 m bgl (below ground level) and the water table at 9.5 m bgl. With increasing distance along the axis of the plume, the ratio of methane to carbon dioxide gradually decreases, while nitrogen increases. Oxygen appears beyond 80 m from the landfill boundary. Stable carbon and hydrogen isotope ratios in methane become heavier with distance, while carbon dioxide becomes isotopically lighter with respect to stable carbon. This provides strong evidence for microbially mediated methane oxidation. Zones of black reduced sediment near the landfill suggest that ferric iron [Fe(III)] may be acting as an electron acceptor for oxidation. No thermal anomaly was observed, thus suggesting that the rate of oxidation/flux of methane is low. Volatile organic compounds in the plume were trapped using a combination of sorbants (Tenax GR, Haysep Q and Carbosieve S-III), and desorbed thermally into a GC/MS for semi-quantitative analysis. The 79 VOCs identified were similar to those found in other landfills, and their concentrations, both in the landfill and in the soil gas, were broadly related to their volatility. Only two compounds (vinyl chloride and dichlorofluoromethane) approached or exceeded the long-term exposure limit (LTEL, as defined by the U.K. Health and Safety Executive, 1992) outside the landfill. Halogenated compounds (dichlorodifluoromethane, dichlorofluoromethane and trichlorofluoromethane) were found to be most mobile but their concentration profiles suggest that they may have been flushed out of the landfill during its early stages. It is suggested that the association of volatile halogenated compounds with methane is good evidence that they are derived from a landfill.     

超临界二氧化碳在环境保护中的应用

超临界CO2具有气体的低粘度、高扩散系数和液体的高密度特性，且具有化学惰性，无毒、无腐蚀性，临界状态容易实现，是一种性能优良的环境友好溶剂。文章概述了超临界CO2在去除环境污染物、取代传统工艺助剂或溶剂以减少有机物和废水排放以及分析测试等方面的应用。     

Pilot Scale Demonstration of the Electrochemical Peroxidation Process at a Petroleum Spill Site

In a pilot test experiment involving approximately 200,000 gallons of groundwater, Electrochemical Peroxidation (ECP) was used to degrade aqueous phase volatile organic compounds (VOCs) including benzene, toluene, ethylbenzene, and xylene (BTEX) compounds and methyl tertbutyl ether (MTBE) from a petroleum spill. ECP involves a form of the Fenton's Reagent reaction, which uses electrochemically generated iron and dilute hydrogen peroxide (<30 mg/L) to break down organic molecules through oxidation to carbon dioxide and water. This article discusses a pilot scale demonstration of the ECP technology and its application to aqueous phase organic contaminants. The remedial approach used at the pilot test site involves three phases: (1) ex‐situ chemical oxidation, (2) in‐situ oxidation by reinjection of treated effluent near the plume origin, and (3) reestablishment of aerobic biodegradation as the residual hydrogen peroxide discharged to a series of upgradient wells degrades to oxygen. Analytical results of the pilot demonstration indicate that the ex‐situ chemical oxidation reduced total BTEX concentrations in groundwater from over 1,000 ppb to undetectable concentrations (<1 ppb). © 2000 John Wiley & Sons, Inc.     

USING ISOTOPIC AND MOLECULAR DATA TO MODEL LANDFILL GAS PROCESSES

Using a large data set, a preliminary investigation has been made to evaluate the usefulness of stable isotope ratios for improving our understanding of methane and carbon dioxide generation in landfills. Included are approximately 130 landfill gas samples from across the U.S.A., and 18 recent samples from: (1) an Argonne Laboratory study area in the Brea-Olinda Landfill, Orange County, California (U.S.A); and (2) several Los Angeles County landfills, California (U.S.A). The following isotope ratios were examined: δ¹³C for methane, δ¹³C for carbon dioxide and δD for methane. Using simple ratio plots supplemented by mass-balance calculations, these data show promise for indicating the relative contributions of the four major carbon cycle processes in landfills, namely: (1) direct oxidation of organic material to carbon dioxide; (2) methane generation from fermentation (acetate cleavage); (3) methane generation from carbon dioxide reduction; and (4) methane oxidation to carbon dioxide by methanotrophic bacteria. Both the methane generation and oxidation reactions are central to an explanation of the trends discussed herein. The data also suggest that direct oxidation of organic matter in the refuse may be contributing to the observed isotopic ratios in some cases. The trends observed at the Brea-Olinda site were similar to trends using the large U.S. database, suggesting that isotopic techniques may be useful to better constrain carbon cycle processes common to all landfill settings.     

Kinetic study of permanganate oxidation of tetrachloroethylene at a high pH under acidic conditions

Since carbon compounds are the main component of dense nonaqueous phase liquids (DNAPLs), the end products of all in situ chemical oxidation (ISCO) will include carbon dioxide. If the production rate of carbon dioxide exceeds the capacity of water to remove the carbon dioxide, degassing will occur. The uncontrolled carbon dioxide gas may change the flow patterns, remobilize the pooled DNAPL, transport DNAPL vapor, and reduce the relative permeability to the aqueous phase. Under high pH buffered conditions, most of the carbon dioxide will be dissolved in water. In this study, potassium permanganate oxidation of tetrachloroethylene (PCE) was conducted using a sodium carbonate buffered solution (1 g/L, pH = 10.6 ± 0.1) at three different temperatures (5, 10, and 20°C) and three potassium permanganate concentrations (0.2, 1, and 5 g/L). Extensive kinetic studies suggest that the overall oxidation is a second‐order reaction and pseudo‐first‐order with respect to PCE and potassium permanganate, respectively. The second‐order rate constant and the activation energy were 0.028 ± 0.001 M^?1s^?1 at 20°C and 43.9 ± 2.85 kJ/M, respectively. This study provides a base for further experimental and field studies on potassium permanganate oxidation of PCE under natural or artificial high pH buffered conditions. © 2004 Wiley Periodicals, Inc.     

Effluents from MBT plants: Plasma techniques for the treatment of VOCs

Mechanical–biological treatments (MBTs) of urban waste are growing in popularity in many European countries. Recent studies pointed out that their contribution in terms of volatile organic compounds (VOCs) and other air pollutants is not negligible. Compared to classical removal technologies, non-thermal plasmas (NTP) showed better performances and low energy consumption when applied to treat lowly concentrated streams. Therefore, to study the feasibility of the application of NTP to MBTs, a Dielectric Barrier Discharge reactor was applied to treat a mixture of air and methyl ethyl ketone (MEK), to simulate emissions from MBTs. The removal efficiency of MEK was linearly dependent upon time, power and specific input energy. Only 2–4% of MEK was converted to carbon dioxide (CO₂), the remaining carbon being involved in the formation of byproducts (methyl nitrate and 2,3-butanedione, especially). For future development of pilot-scale reactors, acting on residence time, power, convective flow and catalysts will help finding a compromise between energy consumption, desired abatement and selectivity to CO₂.     

Treatment of tar pond sludge in a circulating fluidized bed combustor

A series of tests to burn mixtures of tar pond sludge and coal was carried out using a mini‐circulating fluidized bed combustor (mini‐CFBC). During the tests, carbon dioxide, oxygen, carbon monoxide, sulfur dioxide, and nitrogen oxides in the flue gas were monitored continuously. Stack gas sampling was carried out for hydrochloric acid, metals, particulate matter, volatile organic compounds (VOCs), total hydrocarbons, semivolatile organic compounds (SVOCs), dioxins and furans (PCDD/Fs), and polychlorinated biphenyls (PCBs). Results showed that hydrochloric acid, mercury, particulate matter, PCDD/F, and metal concentrations were all below both the current limits and the gas‐release limits to be implemented in 2008 in Canada. The new 2008 emissions limits will reduce the maximum allowable concentrations of most pollutants by half. Thus, the maximum concentration for particulate matter will be 5 mg/m³ (from the current maximum concentration of 10 mg/m³);the maximum concentration for hydrochloric acid will be 5 mg/m³ (from 10 mg/m³); and the‐maximum concentration for dioxins and furans will be 0.032 ng/m toxic equivalent (from 0.08 ng/mcurrently). Sulfur capture efficiency was 89–91 percent. The percentage of fuel nitrogen converted to nitrogen oxides was of the order of 4.7 to 6.1, which is significantly lower than that of conventional pulverized coal‐fired boilers and well within the normal range for fluidized bed combustors (FBCs). PCB and polycyclic aromatic hydrocarbon (PAH) emissions levels were comparable or lower than levels reported in the literature for industrial‐scale FBCs. VOC concentrations were low except for benzene, for which the concentration was higher than that reported for pulverized coal‐fired utility boilers. In addition, carbon monoxide concentration was high at 1,200 to 2,200 parts per million. However, these carbon monoxide concentrations are typical of the mini‐CFBC firing coal. The trials showed that for 10 percent by weight tar pond sludge mixed with 90 percent by weight coal, the combustion was both stable and efficient. The tests demonstrated that CFBC technology is an environmentally sound option for eliminating tar pond waste sludge. © 2005 Wiley Periodicals, Inc.     

State-of-the-art VOC abatement from soil-venting operations

The development of treatment technologies to limit the discharge of volatile organic compounds (VOCs) into the atmosphere has proceeded apace with the increasing use of soil venting for the remediation of contaminated soil. This article surveys the commonly-used emission control systems that have developed under air pollution control regulations in California. Emphasis is on equipment operating characteristics, typical performance results (destruction efficiencies of VOCs), and operating costs. A recently commercialized process for treating halogen-containing VOCs is described, and some operating and cost data are included.     

Impact of different plants on the gas profile of a landfill cover

Methane is an important greenhouse gas emitted from landfill sites and old waste dumps. Biological methane oxidation in landfill covers can help to reduce methane emissions. To determine the influence of different plant covers on this oxidation in a compost layer, we conducted a lysimeter study. We compared the effect of four different plant covers (grass, alfalfa + grass, miscanthus and black poplar) and of bare soil on the concentration of methane, carbon dioxide and oxygen in lysimeters filled with compost. Plants were essential for a sustainable reduction in methane concentrations, whereas in bare soil, methane oxidation declined already after 6 weeks. Enhanced microbial activity - expected in lysimeters with plants that were exposed to landfill gas - was supported by the increased temperature of the gas in the substrate and the higher methane oxidation potential. At the end of the first experimental year and from mid-April of the second experimental year, the methane concentration was most strongly reduced in the lysimeters containing alfalfa + grass, followed by poplar, miscanthus and grass. The observed differences probably reflect the different root morphology of the investigated plants, which influences oxygen transport to deeper compost layers and regulates the water content.     

Successful UV/oxidation of VOC-contaminated groundwater

Ultraviolet light/oxidation has proven its effectiveness in destroying volatile organic chemicals (VOCs) found in groundwater during a U.S. Environmental Protection Agency (EPA) field study. Under the Superfund Innovative Technology Evaluation (SITE) program, PRC Environmental Management, Inc., and EPA monitored the performance of a system employing advanced oxidation techniques at the Lorentz Barrel & Drum (LB&D) Superfund site in San Jose, California. The firm of Ultrox International (Santa Ana, CA) demonstrated its technology for combining ultraviolet light, hydrogen peroxide and ozone to oxidize toxic organic chemicals found in water. All evaluation criteria were successfully met in the study's results. Greater than 90% of the VOCs were removed. The applicable discharge standards (National Pollution Discharge Elimination System) were attained, and there were no emissions.     

A kinetic analysis of solid waste composting at optimal conditions

This discussion explores the possibility of having a measure of the biodegradable organic carbon content in solid wastes. Currently, indirect measures for determining the concentration of biodegradable organic matter are being used and most of them are based on respiration indices (oxygen consumption or carbon dioxide production) or chemical parameters (volatile solids or total organic carbon). The results obtained for the cumulative carbon dioxide production in composting experiments can be expressed as "aerobic biodegradable carbon" for the wastes that were studied. The calculation of a useful biodegradable C/N can also be obtained from the aerobic biodegradable carbon content. A comparison with some results obtained in measuring the concentration of "anaerobic biodegradable carbon" also is presented.     

双介质阻挡放电法再生吸附五氯酚的活性炭

采用双介质阻挡放电等离子体反应器对吸附了五氯酚的活性炭进行放电再生处理,考察了放电电压、放电时间、氧气流量和活性炭再生次数对再生活性炭的五氯酚去除率的影响.实验结果表明,活性炭再生的最佳条件为:放电电压23 kV,放电时间1.5h,氧气流量2.0 L/min.随活性炭再生次数增加,再生活性炭的五氯酚去除率和活性炭再生率...     

Characterizing emissions from open burning of military food waste and ration packaging compositions

Emissions from open burning of military food waste and ration packaging compositions were characterized in response to health concerns from open burning disposal of waste, such as at military forward operating bases. Emissions from current and prototype Meals, Ready-to-Eat (MREs), and material options for their associated fiberboard packaging were quantified to assess contributions of the individual components. MREs account for 67–100% of the particulate matter (PM), volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated dibenzo-p-dioxins and -furans (PCDDs/PCDFs) emissions when burned in unison with the current fiberboard container and liner. The majority of the particles emitted from these burns are of median diameter 2.5 µm (PM_2.5). Metal emission factors were similar regardless of waste composition. Measurements of VOCs and PAHs indicate that targeted replacement of MRE components may be more effective in reducing emissions than variation of fiberboard-packaging types. Despite MRE composition variation, equivalent emission factors for PM, PAH, VOC, and PCDD/PCDF were seen. Similarly, for fiberboard packaging, composition variations exhibited essentially equivalent PM, PAH, VOC, and PCDD/PCDF emission factors amongst themselves. This study demonstrated a composition-specific analysis of waste burn emissions, assessing the impact of waste component substitution using military rations.     

Methane–benzene binary mixture destruction in a reverse flow catalytic reactor

An experimental study of methane–benzene binary mixture purification in a bench-scale reverse flow reactor is carried out. Results for catalytic oxidation of the two hydrocarbons with remarkably discrepant chemical properties show that autothermal catalytic combustion of very lean combustible concentration can be achieved with periodic feed reversal. Benzene is well removed, but methane conversion is relatively low and mainly determined by the thermal level of the reactor. If methane is added as auxiliary fuel to maintain autothermal operation when the volatile organic compound (VOC) concentration in the contaminated air is too low, an excess amount is needed. The influences of gas superficial velocity, cycle period, and methane-to-benzene ratio are discussed. A mathematical model is developed and solved using a FORTRAN code, with good correspondence being observed between the two approaches. Results of experimental and numerical study indicate that, during catalytic oxidation of lean VOCs in reverse flow reactor, the mutual inhibition effect between different kinds of hydrocarbon can be neglected.     

Effect of leachate irrigation on methane oxidation in tropical landfill cover soil

The effect of leachate irrigation on methanotrophic activity in sandy loam-based landfill cover soil with vegetation was investigated. Laboratory-scale experiments were conducted to investigate the methane oxidation reaction in cover soil with and without plants (tropical grass). The methane oxidation rate in soil columns was monitored during leachate application at different organic concentrations and using different irrigation patterns. The results showed that the growth of plants on the final cover layer of landfill was promoted when optimal supplement nutrients were provided through leachate irrigation. The vegetation also helped to promote methane oxidation in soil, whereas leachate application helped increase the methane oxidation rate in nonvegetated cover soil. Intermittent application of leachate (once every 4 days) improved the methane oxidation activity as compared to daily application. Nevertheless, the adverse effects of organic overloading on methane oxidation rate and plant growth were also observed.     

Fundamental processes and implications during in situ aeration of old landfills

Results of investigations from many old landfills in Germany and Europe indicate that significant emissions occur under conventional landfill operating conditions (i.e., anaerobic conditions). Significant emissions via the gas phase are predicted to last at least three decades after landfill closure, while leachate emissions are predicted to continue for many decades, potentially even lasting for centuries. When considering the specific type and quality, and quite often lack of, protection barriers associated with old landfills, these leachate and gas emissions may result in a significant negative impact on the environment. However, complete sealing of the landfill only temporarily reduces emissions because dry-conservation of the biodegradable waste fraction results, thus not allowing any severe reduction in the emission and hazardous potential of the landfill to occur. If noticeable damage of the surface capping system occurred in these landfills, infiltrating water would restart the interrupted emission formation. In contrast, aerobic in situ stabilization by means of low pressure aeration attempts to stabilize and modify the inventory of organic matter inside the landfill, acting to reduce the emission potential in a more sustainable manner. By enabling faster and more extensive aerobic degradation processes in the landfill (compared with anaerobic processes), the organics (e.g., hydrocarbons) are degraded significantly faster, resulting in an increased carbon discharge via the gas phase, as well as reduced leachate concentrations. Because carbon dioxide (CO(2)) is the main compound in the extracted off-gas (instead of methane (CH(4)), which dominated under anaerobic landfill conditions), the negative impact of diffuse LFG emissions towards an increased global warming effect may be significantly lowered. With respect to leachate quality, a reduction of organic compounds as well as ammonia-nitrogen can be expected. In addition to these positive ecological effects, aerobic in situ stabilization is associated with significant cost savings potential due to both quantitative and qualitative reductions in the aftercare period. This paper describes the fundamental processes and implications of in situ landfill aeration. Additionally, possible criteria for defining an endpoint of the active aeration process are presented and discussed.     

Characteristics of environmental factors and their effects on CH4 and CO2 emissions from a closed landfill: An ecological case study of Shanghai

To elucidate the influence of landfill gas (LFG) emission on environmental factors, an ecological investigation that was primarily concerned with the characteristics of vegetation, cover soil, and solid waste in the landfill was carried out. Temporal and spatial variations in vegetation diversity and coverage and their effects on reducing the emission of methane in the landfill were investigated. The results showed that both vegetation coverage and diversity increased with elapsed landfill closure time. The transition trend of the vegetation species was from perennial plant (Phragmites australis) to annual plants. Perennial vegetation was the dominant type of vegetation during the early closure period, and annual vegetation coverage increased with closure time. Vegetation preferentially appeared in areas of comparatively high depth of cover soil, which was characterized by high moisture retentiveness that enabled vegetation growth. The concentrations of methane and carbon dioxide in the cover soil significantly decreased with increasing closure time. The concentrations of methane and carbon dioxide from bare cover soil were higher than those from vegetated cover soil whereas the CO₂ flux of bare cover soil was less than that of vegetated cover soil.     

Control of GHG emission at the microbial community level

All organic material eventually is decomposed by microorganisms, and considerable amounts of C and N end up as gaseous metabolites. The emissions of greenhouse relevant gases like carbon dioxide, methane and nitrous oxides largely depend on physico-chemical conditions like substrate quality or the redox potential of the habitat. Manipulating these conditions has a great potential for reducing greenhouse gas emissions. Such options are known from farm and waste management, as well as from wastewater treatment. In this paper examples are given how greenhouse gas production might be reduced by regulating microbial processes. Biogas production from manure, organic wastes, and landfills are given as examples how methanisation may be used to save fossil fuel. Methane oxidation, on the other hand, might alleviate the problem of methane already produced, or the conversion of aerobic wastewater treatment to anaerobic nitrogen elimination through the anaerobic ammonium oxidation process might reduce N2O release to the atmosphere. Changing the diet of ruminants, altering soil water potentials or a change of waste collection systems are other measures that affect microbial activities and that might contribute to a reduction of carbon dioxide equivalents being emitted to the atmosphere.