Arrested municipal solid waste incinerator fly ash as a source of polynuclear aromatic hydrocarbons (PAHs) to the environment

Arrested fly ash samples from most currently operating municipal solid waste (MSW) incinerators on the U.K. mainland have been analysed for polynuclear aromatic hydrocarbons (PAHs). The ashes have a mean ΣPAH content of about 227 μg kg⁻. This is generally lower than concentrations observed in U.K. surface soils. Benzo[ghi] perylene was the most abundant individual compound, and the most frequently detected. The ΣPAH content of ashes does not appear to be related to incinerator type, but rather it is likely that poor gas phase combustion favours higher PAH levels. The significance of PAHs in ash residues and their possible fate following disposal to landfill are discussed.     

Sedimentary Record of Polycyclic Aromatic Hydrocarbons in the Gulf of Trieste (Northern Adriatic Sea)

To reconstruct a history of polycyclic aromatic hydrocarbon (PAH) pollution in the Gulf of Trieste, one of the largest urbanized areas in the Adriatic Sea, we analyzed three long sediment cores collected between 1996 and 1997. Concentrations of total PAHs, the sum of 16 PAH compounds and six of their methylated analogues, in all three cores show a decrease from 600–800 ng g⁻¹, at the surface, to levels below 250 ng g⁻¹ in deepest layers (down to 3 m). The same trend was shown with separate representative pyrogenic PAHs (pyrene, benzofluoranthene and phenanthrene). Using Hg as a recent geochronological tracer, we observe an increasing input of PAHs since the beginning of the 20th Century and, especially, after the Second World War coinciding with increasing industrialization and urbanization of the region. This correlation is supported by PAH ratios that are indication of combustion processes and represent a marker for anthropogenic inputs. No correlation exists between PAHs and black carbon within the core profiles, indicating two different fractions of the ‘black carbon continuum’.     

Behavior of PAHs from sewage sludge incinerators in Korea

Although production of sewage sludge increases every year, its proper treatment has only been recently raised as a new issue, as current landfill and ocean dumping arrangements are expected to become increasingly difficult to manage in the future. The Korean Ministry of Environment plans to diversify its processing facilities and expand its processing systems by 2011, with the purpose of processing all sludge produced in Korea. According to this plan, incineration (including incineration of municipal wastes) will process 30% of the entire sewage sludge throughout the country in 2011. This study reviews the characteristics of PAH, which is one of the organic substances found in sewage sludge during the incinerating process. The total amount of PAH produced from sewage sludge incineration was found to be 6.103 mg/kg on average, and investigation performed on 16 PAHs of inlets and outlets of the air control devices at five full-scale incineration facilities showed that concentrations of the PAHs on the inlet and on the outlet ranged from 3.926 to 925.748 microg/m(3) and from 1.153 to 189.449 microg/m(3), respectively. In the case of the incineration facility fed with municipal waste (95%) and sewage sludge (5%), the total of the PAH emissions concentration was higher than that found at the incineration facilities used exclusively to treat sewage. The combustion of waste vinyl and plastics contained in municipal waste fed into the facility might contribute to the high levels of PAHs in the stack gas. However more investigation is needed on the production mechanism of PAHs at different operating conditions of the incineration facilities, such as the types of waste, and other relevant factors.     

Combustion kinetics of sewage sludge and combustible wastes

This study estimated the kinetics of the mono- and co-combustion of sewage sludge pellets and combustible wastes such as municipal solid waste (MSW) and refuse-derived fuel (RDF). Sewage sludge was manufactured into pellets with a diameter of 8, 12, or 16 mm and a length of 30 mm. The RDF was composed of paper and plastics and was formed into pellets with a diameter of 8 mm and a length of 30 mm. MSW samples were synthesized using combustible wastes such as garbage, paper, plastics, and wood. The MSW was adjusted to have a moisture content of around 40% after shredding to under 10 mm. A laboratory-scale batch type stoker incinerator was used for the combustion and the gas composition of the flue gas was measured. The activation energy was calculated using the experimental results, and then the relation of the decomposition rate and reaction time was evaluated using the shrinking core model. The decomposition rate of the sludge pellets decreased as their diameter and moisture content increased, and the co-combustion of sludge pellets and combustible waste was affected by the amount of combustible waste. The individual combustion rates of the cylindrical sludge pellets or RDF were mainly controlled by the chemical reaction, but in the case of shredded MSW it was mostly influenced by gas diffusion. The rate for the co-combustion of sludge pellets and combustible wastes was mainly determined by the combustion rate of the combustible waste. The activation energy of the 8-mm-diameter sludge pellets was between 6.70 and 10.0 kcal/mol, according to the moisture content, but it was lower for MSW and RDF. In the case of MSW co-combustion, the reaction rate accelerated as the moisture content of the sludge pellets decreased, but it was markedly increased by the addition of RDF, regardless of the sludge moisture content.     

End-of-life vehicle recycling and automobile shredder residue management in Japan

The Japanese Government introduced the Law on Recycling of End-of-Life Vehicles (ELV Recycling Law) in 2002. This law requires manufacturers to retrieve chlorofluorocarbons (CFCs), airbags, and automobile shredder residue (ASR) from ELVs and to properly recycle the remaining materials. This framework is compared with European ELV directives. Pilot-scale incineration plant testing has revealed a greater formation of by-product persistent organic pollutants (POPs) during the primary combustion of ASR compared to normal municipal solid waste. This may be attributed to the abundance of chlorine, Cu, and Fe in ASR, as Cu and Fe have been found to catalyze the formation of POPs under certain conditions. However, most by-product POPs were destroyed by the secondary combustion, and almost all were removed after flue gas treatment. The direct melting system is a shaft-type gasification and melting technology that has proved effective in many municipal solid waste applications. This system can be applied to ASR recycling for effective decomposition of brominated flame retardants and polybrominated dioxins.     

Characterization of municipal solid waste combustion in a grate furnace

The objective of this paper is to evaluate the combustion process of municipal solid waste combustion in a grate furnace both experimentally and numerically by using data of a reference experiment with over-stoichiometric primary air supply. Measurements were carried out inside the combustion chamber of a pilot plant by monitoring temperatures and sampling gaseous combustion products along the bed surface. The data were assessed using elemental and energy balances. Experimental data of the axial temperature profiles of the flue gas, the fuel bed and the grate bars, as well as local gas flows and the flue gas composition measured above the fuel bed along the grate were used to describe the conversion process, including drying and carbon burnout. These data served as input to model the thermo- and fluid dynamic processes of the gas phase above the bed inside the combustion chamber. For this purpose the commercial code FLUENT was employed to carry out the simulations. Thus, the turbulent temperature, flow and species distributions in the combustion chamber of the pilot waste incinerator TAMARA were predicted. The results of the FLUENT modeling showed that under the prevailing conditions the flue gas burnout is almost completed before entering the first flue due to high temperatures, effective mixing and sufficient residence times of the flue gas inside the combustion chamber. This agrees well with the experimental results inside the first flue. On the basis of the above mentioned results, design and parametric studies can be carried out in a more efficient way by saving cost and time.     

An investigation on pollutant emissions from co-firing of RDF and coal

Pollutant emissions from co-firing of refuse derived fuel (RDF) and coal were investigated in a vortexing fluidized bed combustor (VFBC). RDF-5 was made of common municipal solid waste (MSW). CaCO₃ was injected in the combustor to absorb HCl at 850 °C. The results show that NO_x and HCl emissions increase with RDF-5 co-firing ratio. The NO_x concentration in flue gas at the bottom of the combustor is higher than that at the top. However, the trend of HCl released is reverse compared with NO_x emissions. It was found that the HCl concentration decreases with increasing the molar ratio of Ca/Cl. However, the effect of CaCO₃ addition on HCl retention is not significant when the molar ratio of Ca/Cl is higher than 5. The chlorine content in fly ash increases obviously with the molar ratio of Ca/Cl. PCDD/Fs emissions decrease slightly with an addition of CaCO₃. In this study incomplete combustion is regarded as the main cause for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) formation.     

Fundamental study of the behavior of chlorine during the combustion of single RDF

A fundamental study of the combustion characteristics and the de-HCl behavior of a single refuse-derived fuel (RDF) pellet was carried out to explain the de-HCl phenomena of RDF during fluidized bed combustion and to provide data for the development of high efficiency power generation technology using RDF. In this research, combustion and pyrolysis experiments were carried out in an electrical furnace using a series of model and actual RDF samples. The de-HCl capability of Ca(OH)2 in RDF was evaluated by measuring the emission fraction of HCl in the flue gas and the capture fraction of Cl in the residue. It was found that the capture fraction of Cl components in the residue increased from 0 to nearly 70% when the molar ratio of Ca/Cl was changed from 0 to around 13. Apparently, the capture fraction also decreased with increasing oxygen concentration in the feed gas. The devolatilization process of RDF was confirmed to be a very important part of de-HCl process. The effect of temperature profile of the RDF pellet on the de-HCl process, as it varies with the heating rate of RDF and the oxygen concentration in the vicinity of the sample, is discussed.     

The significance of polynuclear aromatic hydrocarbons applied to agricultural soils in sewage sludges in the U.K.

The ubiquity of polynuclear aromatic hydrocarbons (PAHs) in sewage sludges is now well documented. Since PAHs exhibit carcinogenic/mutagenic behaviour concern has been expressed over their fate following sludge application to agricultural soils. This paper presents a resume of the behaviour of sludge applied PAHs in soils and their propensity to transfer from the soil into plant tissues. This information is used to assess the environmental significance of PAHs in sludge amended soils. Sludge PAH inputs to the U.K. environment are compared with other known sources, such as waste disposal and atmospheric deposition and the possible impact of sludge application on human exposure is considered. It is concluded that at present there is no necessity to specifically regulate PAH inputs to agricultural soils in sewage sludge.     

Simulation of the flue gas cleaning system of an RDF incineration power plant

Because of the stringent pollutant emission standards introduced with the European Union guidelines for waste incineration, it is very important to optimize the flue gas cleaning systems which are able to result in a low environmental impact according to the emission limits. In this paper a thermochemical model has been proposed for the simulation of the flue gas cleaning system of an RDF incineration plant. The model simulates the operation of the flue-gas treatment section and the combustion section by using a simplified approach. The combustion includes the grate incinerator and the post-combustion chamber, while the cleaning section includes the NO(x) reduction process (urea injection) and the scrubbing of SO(2) and HCl (Ca(OH)(2) as sorbent). The modelling has been conducted by means of ASPEN PLUS code. The simulation results have been validated with the operating data. The model proposed by the authors can be a useful tool in both evaluating the efficiency of the gas cleaning system by verifying the environmental pollution of an incinerator power plant in nominal operating conditions and in forecasting the efficiency of the cleaning system in off-design operating conditions.     

Combustion and inorganic bromine emission of waste printed circuit boards in a high temperature furnace

High temperature combustion experiments of waste printed circuit boards (PCBs) were conducted using a lab-scale system featuring a continuously-fed drop tube furnace. Combustion efficiency and the occurrence of inorganic bromine (HBr and Br₂) were systematically studied by monitoring the main combustion products continuously. The influence of furnace temperature (T) was studied from 800 to 1400 °C, the excess air factor (EAF) was varied from 1.2 to 1.9 and the residence time in the high temperature zone (RT_HT) was set at 0.25, 0.5, or 0.75 s.Combustion efficiency depends on temperature, EAF and RT_HT; temperature has the most significant effect. Conversion of organic bromine from flame retardants into HBr and Br₂ depends on temperature and EAF. Temperature has crucial influence over the ratio of HBr to Br₂, whereas oxygen partial pressure plays a minor role. The two forms of inorganic bromine seem substantially to reach thermodynamic equilibrium within 0.25 s. High temperature is required to improve the combustion performance: at 1200 °C or higher, an EAF of 1.3 or more, and a RT_HT exceeding 0.75 s, combustion is quite complete, the CO concentration in flue gas and remained carbon in ash are sufficiently low, and organobrominated compounds are successfully decomposed (more than 99.9%).According to these results, incineration of waste PCBs without preliminary separation and without additives would perform very well under certain conditions; the potential precursors for brominated dioxins formation could be destroyed efficiently. Increasing temperature could decrease the volume percentage ratio of Br₂/HBr in flue gas greatly.     

Estimating PAH sources in harbor sediments using diagnostic ratios

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the global environment and are subsequently transported into aquatic sediments. As PAHs are formed by various processes, source identification using diagnostic ratios can provide insight to PAH emission sources to distinguish between pyrogenic and petrogenic PAH sources. PAH diagnostic ratios were applied as a forensic source apportionment technique to assess aggregate historical sediment data from 31 small craft harbors (SCHs) across Nova Scotia, Canada. Multiple diagnostic ratios suggest that PAHs present in Nova Scotia SCH sediments are pyrogenic (combustion) in origin, while consistently suggesting that coal‐related PAH sources are potential dominant specific sources. National Institute of Standards and Technology Standard Reference Materials (SRMs) were used as reference for coal tar, urban dust, and diesel exhaust particulates in ratio applications. The SRM for coal tar was most similar to Nova Scotia SCH sediments in multiple ratio applications. Diagnostic ratio results were corroborated by comparing the PAH profile of sediments to source profiles from the literature. Results indicate that Nova Scotia SCH sediments follow global trends by exhibiting a dominant pyrogenic PAH signature, and the specific coal‐related PAH signature of Nova Scotia SCH sediments may be influenced by contamination inputs related to historical industrial coal mining and combustion activities in the province.     

Emission of dioxins/furans and other U-POPs from test burns of non-POP pesticides in a hazardous waste incinerator

This paper presents the results of test burns for obsolete pesticides (OPs) of the permethrin group in a high temperature incinerator (HTI) in Southeast Asia. Three test burn runs were conducted, a baseline run when no OP was fed to the incinerator, and two test runs with different mixtures of OP compounds (formula 1 and 2, refer to Table 1 for detail) containing chlorine in the feeding wastes. The unintentional formed persistent organic pollutants (U-POPs) including 17 dioxins/furans, 12 dioxin-like PCBs and 12 chlorobenzenes (CBs) were monitored in all input materials and all discharges (flue gas, scrubbing liquid and solid residues). The results show relatively high levels of the U-POPs in the flue gas emission with total dioxins/furans of 4.4, 3.4, and 8.4 ng I-TEQ/m³ in the baseline, test run 1 and test run 2, respectively, which are above international acceptable emission levels. The PCB levels in flue gas were, respectively, 0.01, 0.3 and 0.4 ng I-TEQ/m³. The baseline thus had similar U-POPs levels with the OP test runs.In stack emission, approximately 90% of the U-POPs and 100% of CBs were present in gas phase. The emission factors, mass of pollutants per metric ton (tonne) of input waste, of U-POPs associated with fly ash (from bag house) were the highest, followed by flue gas and bottom ash while those associated with scrubbing liquid were relatively low. Among the waste input material only the black toner power contained U-POPs, but at low levels. The profiles of the dioxins/furans and PCBs in the toner waste were significantly different from that in the discharges. Despite the overall good destruction and removal efficiency of permethrin (better than 90%) the high emission of U-POPs and CBs from the test burn is of another more serious concern. To our best knowledge the findings of this study are the first of this kind for the Southeast Asia. The findings emphasize that if not properly conducted a standard destruction technology of a non-POP chemical can lead to a release of a range of more dangerous U-POPs into the environment.     

Polycyclic aromatic hydrocarbon (PAH) emission from co-firing municipal solid waste (MSW) and coal in a fluidized bed incinerator

Polycyclic aromatic hydrocarbons (PAH) emissions from a commercial municipal solid waste incinerator (MSWI) were studied. A MSW–coal mixture and coal only were used as fuel for the fluidized bed incinerator. Seven sampling points were chosen according to the classified four PAH emission pathways: flue gas, residue, ash and water. The mixture of MSW and coal resulted in PAH emission more than that of coal only, and PAH emission increased with increasing MSW mass percentage. Calcium oxide (CaO) or calcium carbonate (CaCO₃) was added as a desulfurizer. PAH emission also changed with different desulfurizers because of their different influences on heat balance. The PAH toxic equivalent (TEQ) of all operating conditions was also examined, showing that total daily PAH emission from MSWI can be determined.     

Energy implications of mechanical and mechanical–biological treatment compared to direct waste-to-energy

Primary energy savings potential is used to compare five residual municipal solid waste treatment systems, including configurations with mechanical (MT) and mechanical–biological (MBT) pre-treatment, which produce waste-derived fuels (RDF and SRF), biogas and/or recover additional materials for recycling, alongside a system based on conventional mass burn waste-to-energy and ash treatment. To examine the magnitude of potential savings we consider two energy efficiency levels (state-of-the-art and best available technology), the inclusion/exclusion of heat recovery (CHP vs. PP) and three different background end-use energy production systems (coal condensing electricity and natural gas heat, Nordic electricity mix and natural gas heat, and coal CHP energy quality allocation).The systems achieved net primary energy savings in a range between 34 and 140 MJ_primary/100 MJ_{input waste}, in the different scenario settings. The energy footprint of transportation needs, pre-treatment and reprocessing of recyclable materials was 3–9.5%, 1–18% and 1–8% respectively, relative to total energy savings. Mass combustion WtE achieved the highest savings in scenarios with CHP production, nonetheless, MBT-based systems had similarly high performance if SRF streams were co-combusted with coal. When RDF and SRF was only used in dedicated WtE plants, MBT-based systems totalled lower savings due to inherent system losses and additional energy costs. In scenarios without heat recovery, the biodrying MBS-based system achieved the highest savings, on the condition of SRF co-combustion. As a sensitivity scenario, alternative utilisation of SRF in cement kilns was modelled. It supported similar or higher net savings for all pre-treatment systems compared to mass combustion WtE, except when WtE CHP was possible in the first two background energy scenarios. Recovery of plastics for recycling before energy recovery increased net energy savings in most scenario variations, over those of full stream combustion. Sensitivity to assumptions regarding virgin plastic substitution was tested and was found to mostly favour plastic recovery.     

Characteristics of azaarenes and dioxins in gases emitted from waste incinerators

In this study, we propose an analytical method to determine the fourteen of azaarenes present in flue gas samples collected according to Japanese Industrial Standard K 0311, which designates the method for the determination of dioxins in flue gas. Azaarenes can be analyzed using the acidic water phase after shaking extraction with dichloromethane, which is unnecessary for dioxin analysis. Flue gas samples were obtained from 24 waste incinerators in Japan, and azaarenes were detected in all the flue gas samples (0.21–3800 μg/m³ _N). The most abundant of the detected compounds were quinoline and isoquinoline. The concentration of azaarenes had a tendency to increase with that of polychlorinated dibenzo-p-dioxins and dibenzofurans. The isomer distribution of heptachloro-dibenzofurans (HpCDFs) was calculated using the computed Gibbs energy of formation (ΔG _f ) obtained by the semiempirical molecular orbital method at various temperatures. The calculated isomer distribution was fitted to the measured value of HpCDFs. It seems that the temperature obtained from the fitting calculations is an indicator of the cooling capacity of the combustion gas in an incinerator. The computed ΔG _f also explained the measured isomer distributions of azaarenes. It is suggested that the isomer distribution of azaarenes in the combustion process is thermodynamically controlled. This work was presented in part at the International Conference on Combustion, Incineration/Pyrolysis, and Emission Control, 2006, Kyoto     

Comparison of coal/solid recovered fuel (SRF) with coal/refuse derived fuel (RDF) in a fluidized bed reactor

An experimental study was undertaken to compare the differences between municipal solid waste (MSW) derived solid recovered fuel (SRF) (complying with CEN standards) and refuse derived fuel (RDF). Both fuels were co-combusted with coal in a 50 kW fluidised bed combustor and the metal emissions were compared. Synthetic SRF was prepared in the laboratory by grinding major constituents of MSW such as paper, plastic, textile and wood. RDF was obtained from a local mechanical treatment plant. Heavy metal emissions in flue gas and ash samples from the (coal + 10% SRF) fuel mixture were found to be within the acceptable range and were generally lower than that obtained for coal + 10% RDF fuel mixture. The relative distribution of heavy metals in ash components and the flue gas stream shows the presence of a large fraction (up to 98%) of most of the metals in the ash (except Hg and As). Thermo-gravimetric (TG) analysis of SRF constituents was performed to understand the behaviour of fuel mixtures in the absence and presence of air. The results obtained from the experimental study will enhance the confidence of fuel users towards using MSW-derived SRF as an alternative fuel.     

Energy from Waste – Clean,efficient, renewable: Transitions in combustion efficiency and NOx control

Traditionally EfW (Energy from Waste) plants apply a reciprocating grate to combust waste fuel. An integrated steam generator recovers the heat of combustion and converts it to steam for use in a steam turbine/generator set. This is followed by an array of flue gas cleaning technologies to meet regulatory limitations.Modern combustion applies a two-step method using primary air to fuel the combustion process on the grate. This generates a complex mixture of pyrolysis gases, combustion gases and unused combustion air. The post-combustion step in the first pass of the boiler above the grate is intended to “clean up” this mixture by oxidizing unburned gases with secondary air.This paper describes modifications to the combustion process to minimize exhaust gas volumes and the generation of noxious gases and thus improving the overall thermal efficiency of the EfW plant. The resulting process can be coupled with an innovative SNCR (Selective Non-Catalytic Reduction) technology to form a clean and efficient solid waste combustion system.Measurements immediately above the grate show that gas compositions along the grate vary from 10% CO, 5% H₂ and 0% O₂ to essentially unused “pure” air, in good agreement with results from a mathematical model. Introducing these diverse gas compositions to the post combustion process will overwhelm its ability to process all these gas fractions in an optimal manner. Inserting an intermediate step aimed at homogenizing the mixture above the grate has shown to significantly improve the quality of combustion, allowing for optimized process parameters. These measures also resulted in reduced formation of NO_x (nitrogenous oxides) due to a lower oxygen level at which the combustion process was run (2.6 vol% O_2, wet instead of 6.0 vol% O_2, wet).This reduction establishes optimal conditions for the DyNOR? (Dynamic NO_x Reduction) NO_x reduction process. This innovative SNCR technology is adapted to situations typically encountered in solid fuel combustion. DyNOR? measures temperature in small furnace segments and delivers the reducing reagent to the exact location where it is most effective. The DyNOR? distributor reacts precisely and dynamically to rapid changes in combustion conditions, resulting in very low NO_x emissions from the stack.     

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.     

Changes in microbial properties and nutrient dynamics in bagasse and coir during vermicomposting: Quantification of fungal biomass through ergosterol estimation in vermicompost

In this experiment, different microorganisms viz., Trichoderma viridae, Aspergillus niger and Bacillus megaterium were inoculated in bagasse and coir with the objective to study their effect on nutrient dynamics and microbial properties, specially effect on fungal status in these waste materials. Fungal biomass (FBC) was calculated from the ergosterol content in the vermicompost samples. Inoculation of B. megaterium registered comparatively higher TP content in the final stabilized product. Vermicomposting increased microbial biomass carbon (MBC) and nitrogen (MBN) content in bagasse and coir. Microbial biomass carbon to nitrogen ratio (MBC/ MBN) was comparatively narrower in fungi inoculated vermicomposts and FBC/MBC ratio was increased up to 11.69 from 9.51 of control during vermicomposting.