Characterisation of polycyclic aromatic hydrocarbons in flue gas and residues of a full scale fluidized bed combustor combusting non-hazardous industrial waste.

This paper studies the fate of PAHs in full scale incinerators by analysing the concentration of the 16 EPA-PAHs in both the input waste and all the outputs of a full scale Fluidized Bed Combustor (FBC). Of the analysed waste inputs i.e. Waste Water Treatment (WWT) sludge, Refuse Derived Fuel (RDF) and Automotive Shredder Residue (ASR), RDF and ASR were the main PAH sources, with phenanthrene, fluoranthene and pyrene being the most important PAHs. In the flue gas sampled at the stack, naphthalene was the only predominant PAH, indicating that the PAHs in FBC's combustion gas were newly formed and did not remain from the input waste. Of the other outputs, the boiler and fly ash contained no detectable levels of PAHs, whereas the flue gas cleaning residue contained only low concentrations of naphthalene, probably adsorbed from the flue gas. The PAH fingerprint of the bottom ash corresponded rather well to the PAH fingerprint of the RDF and ASR, indicating that the PAHs in this output, in contrast to the other outputs, were mainly remainders from the PAHs in the waste inputs. A PAH mass balance showed that the total PAH input/output ratio of the FBC ranged from about 100 to about 2600 depending on the waste input composition and the obtained combustion conditions. In all cases, the FBC was clearly a net PAH sink.

Optimising energy recovery and use of chemicals, resources and materials in modern waste-to-energy plants.

Due to ongoing developments in the EU waste policy, Waste-to-Energy (WtE) plants are to be optimized beyond current acceptance levels. In this paper, a non-exhaustive overview of advanced technical improvements is presented and illustrated with facts and figures from state-of-the-art combustion plants for municipal solid waste (MSW). Some of the data included originate from regular WtE plant operation - before and after optimisation - as well as from defined plant-scale research. Aspects of energy efficiency and (re-)use of chemicals, resources and materials are discussed and support, in light of best available techniques (BAT), the idea that WtE plant performance still can be improved significantly, without direct need for expensive techniques, tools or re-design. In first instance, diagnostic skills and a thorough understanding of processes and operations allow for reclaiming the silent optimisation potential.

Destruction and formation of PCDD/Fs in a fluidised bed combustor co-incinerating automotive shredder residue with refuse derived fuel and wastewater treatment sludge.

During an eight day trial automotive shredder residue (ASR) was added to the usual waste feed of a Fluidized Bed Combustor (FBC) for waste-to-energy conversion; the input waste mix consisted of 25% ASR, 25% refuse-derived fuel (RDF) and 50% wastewater treatment (WWT) sludge. All inputs and outputs were sampled and the concentration of the 17 PCDD/Fs with TEF-values was determined in order to obtain "PCDD/F fingerprints". The ASR contained approximately 9000 ng PCDD/Fs/kg(DW), six times more than the RDF and 10 times more than the WWT sludge. The fingerprint of ASR and RDF was dominated by HpCDD and OCDD, which accounted for 90% of the total PDDD/F content, whereas the WWT sludge contained relatively more HpCDFs and OCDF (together 70%). The flue gas cleaning residue (FGCR) and fly and boiler ash contained approximately 30,000 and 2500 ng PCDD/Fs/kg(DW), respectively. The fingerprints of these outputs were also dominated by HpCDFs and OCDF. The bottom ash contained only OCDD and OCDF, in total 8 ng PCDD/Fs/kg (DW). From the comparison of the bottom ash fingerprints with the fingerprints of the other output fractions and of the inputs, it could be concluded that the PCDD/Fs in the waste were destroyed and new PCDD/Fs were formed in the post combustion process by de novo synthesis. During the ASR-co-incineration, the PCDD/F congener concentrations in the fly and boiler ash, FGCR and flue gas were 1.25-10 times higher compared to the same output fractions generated during incineration of the usual waste mix (70% RDF and 30% WWT sludge). The concentration of the higher chlorinated PCDD/Fs increased most. As these congeners have the lowest TEF-factors, the total PCDD/F output, expressed in kg TEQ/year, of the FBC did not increase significantly when ASR was co-incinerated. Due to the relatively high copper levels in the ASR, the copper concentrations in the FBCs outputs increased. As copper catalysis the de novo syntheses, this could explain the increase in PCDD/F concentrations in these outputs.

Automotive shredder residue (ASR): reviewing its production from end-of-life vehicles (ELVs) and its recycling, energy or chemicals' valorisation.

ASR is in Europe classified as hazardous waste. Both the stringent landfill legislation and the objectives/legislation related to ELV treatment of various countries, will limit current landfilling practice and impose an increased efficiency of the recovery and recycling of ELVs. The present paper situates ASR within the ELV context. Primary recovery techniques recycle up to 75% of the ELV components; the remaining 25% is called ASR. Characteristics of ASR and possible upgrading by secondary recovery techniques are reviewed. The latter techniques can produce a fuel- or fillergrade ASR, however with limitations as discussed. A further reduction of ASR to be disposed of calls upon (co-)incineration or the use of thermo-chemical processes, such as pyrolysis or gasification. The application in waste-to-energy plants, in cement kilns or in metallurgical processes is possible, with attention to the possible environmental impact: research into these impacts is discussed in detail. Pyrolysis and gasification are emerging technologies: although the sole use of ASR is debatable, its mixing with other waste streams is gradually being applied in commercial processes. The environmental impacts of the processes are acceptable, but more supporting data are needed and the advantage over (co-)incineration remains to be proven.

Study of composition change and agglomeration of flue gas cleaning residue from a fluidized bed waste incinerator.

Blocking of the collection hoppers of the baghouse filters in a fluidized bed incinerator for co-incineration of high calorific industrial solid waste and sludge was observed. The composition of the flue gas cleaning residue (FGCR), both from a blocked hopper and from a normal hopper, was investigated by (differential) thermogravimetric analysis, quantitative X-ray powder diffraction and wet chemical analysis. The lower elemental carbon concentration and the higher calcium carbonate concentration of the agglomerated sample was the result of oxidation of carbon and subsequent reaction of CO2 with CaO. The evolved heat causes a temperature increase, with the decomposition of CaOHCl as a consequence. The formation of calcite and calcium chloride and the evolution of heat caused agglomeration of the FGCR. Activated lignite coke was replaced by another adsorption agent with less carbon, so the auto-ignition temperature increased; since then no further block formation has occurred.

Assessment of the impact on human health of industrial emissions to air: does the result depend on the applied method?

The impact on human health of substances emitted to air by the Flemish industry was calculated with characterization factors (CFs) provided by the CML, Eco-indicator 99, EPS, EDIP and USEtox impact assessment methods. A comparison of the results pointed out that the choice of the CFs can greatly influence conclusions on the trend of the impact over time and on the relative contribution of the individual substances. If the impact on human health of organic substances and heavy metals was assessed separately, the differences between methods were less pronounced. In this case, the impacts on human health obtained by simply dividing the emitted masses of substances by the respective minimal risk concentrations or minimal risk doses, were comparable to those calculated with the CFs of the model-based methods.

Mass balance for POPs in a real scale fluidized bed combustor co-incinerating automotive shredder residue.

The European directive 2000/53/EC implies a "reuse and recovery" rate for end-of-life vehicles (ELVs) of 95% to be reached by the year 2015. One of the options to increase the actual average European "reuse and recovery" rate of approximately 78% (EU 15, 2008) is incineration of automotive shredder residue (ASR) with energy-recovery. The mass balance and the congener fingerprints for PCDD/Fs, dioxin-like PCBs, PCBs and PAHs in a real scale fluidized bed combustor (FBC) incinerating 25% ASR with 25% refuse derived fuel (RDF) and 50% waste water treatment sludge (WWT sludge) were investigated. The PCDD/F, dioxin-like PCB, PCB and PAH concentrations in this input waste mix were more than hundred times higher than in the usual waste feed of the incinerator (30% RFD and 70% WWT sludge). In the outputs of the FBC, however, the concentrations of these POP groups were comparable or only slightly higher than in the outputs generated during the incineration of the usual waste feed. The considered POPs in the waste were destroyed efficiently and the formation of new POPs during cooling of the flue gas appeared to a large extent independent of the POP concentrations in the incinerated waste.

Effect of carbonation on the leaching of organic carbon and of copper from MSWI bottom ash.

In Flanders, the northern part of Belgium, about 31% of the produced amount of MSWI bottom ash is recycled as secondary raw material. In view of recycling a higher percentage of bottom ash, a particular bottom ash fraction (Ø 0.1-2mm) was studied. As the leaching of this bottom ash fraction exceeds some of the Flemish limit values for heavy metals (with Cu being the most critical), treatment is required. Natural weathering and accelerated carbonation resulted in a significant decrease of the Cu leaching. Natural weathering during 3 months caused a decrease of Cu leaching to <50% of its original value, whereas accelerated carbonation resulted in an even larger decrease (to ca. 13% of its initial value) after 2 weeks, with the main decrease taking place within the first 48 h. Total organic carbon decreased to ca. 70% and 55% of the initial concentration in the solid phase, and to 40% and 25% in the leachate after natural weathering and after accelerated carbonation, respectively. In the solid material the decrease of the Hy fraction was the largest, the FA concentration remained essentially constant. The decrease of FA in the leachate can be attributed partly to an enhanced adsorption of FA to Fe/Al (hydr)oxides, due to the combined effect of a pH decrease and the neoformation of Al (hydr)oxides (both due to carbonation). A detailed study of adsorption of FA to Fe/Al (hydr)oxides showed that significant adsorption of FA occurs, that it increases with decreasing pH and started above pH 12 for Fe (hydr)oxides and around 10 for Al (hydr)oxides. Depending whether FA or Hy are considered the controlling factor in enhanced Cu leaching, the decreasing FA or Hy in the leachate explains the decrease in the Cu leaching during carbonation.

Mass balance for POPs in hazardous and municipal solid waste incinerators.

The amount of different persistent organic pollutants (POPs) in the input of waste incinerators was compared to that in the output. Three cases were considered: a rotary kiln incinerating hazardous waste, a grate furnace incinerating municipal solid waste (MSW) and the same grate furnace co-incinerating plastics of waste of electrical and electronic equipment (WEEE) and automotive shredder residue (ASR) with MSW. The mass balance for PCBs in the rotary kiln indicates that these POPs are destroyed effectively during incineration. The grate furnace can be a sink or source of PCDD/Fs and PCBs depending on the concentrations in the incinerated waste. In order to compare the total amount of POPs in input and output, a methodology was developed whereby the amount of POPs was weighed according to minimal risk doses (MRDs) or cancer potency factors. For both incinerators the PCDD/Fs, PCBs and polyaromatic hydrocarbons (PAHs) are the main contributors to total weighed POP output. In MSW, the PCDD/Fs, PBDD/Fs and polybrominated diphenylethers (PBDEs) are the main contributors to the weighed POP input. The ratios of the weighed POP-input over -output clearly indicate that the rotary kiln incinerating hazardous waste is a weighed POP sink. The grate furnace incinerating MSW is a weighed POP sink or source depending on the POP-concentrations in the waste, but the difference between output and input is rather limited. When e.g. ASR and plastics of WEEE, containing high concentrations of PBDEs and PCBs, are co-incinerated in the grate furnace, it is clearly a weighed POP sink.

Technical and economical evaluation of water recycling in the carwash industry with membrane processes.

In the carwash industry, water recycling is necessary to be in accordance with present and upcoming environmental laws. As this is not possible with traditional techniques, membrane processes (like ultrafiltration (UF) and nanofiltration (NF)) are technically and economically evaluated in this study. Concerning the technical part, there needs to be a compromise between a high permeate permeability on the one hand and a high permeate purity on the other hand. Depending on the use of the purified wastewater, ultrafiltration (to recycle wastewater in the main wash cycle) or nanofiltration (to recycle wastewater in the rinsing step) would be the optimal choice. Concerning the financial part, the implementation of membrane processes in the wastewater purification installation is economically feasible, especially when expensive tap water is used as pure water. These positive evaluations imply that membrane processes can be useful to recycle wastewater in the carwash industry, on condition that the right membrane type (with the least membrane fouling) and the right process format (e.g., hybrid process of UF and/or NF with a biological treatment) is selected.

Influence of treatment techniques on Cu leaching and different organic fractions in MSWI bottom ash leachate.

The leaching of heavy metals, such as copper, from municipal solid waste incinerator (MSWI) bottom ash is of concern in many countries and may inhibit the beneficial reuse of this secondary material. Previous studies have focused on the role of dissolved organic carbon (DOC) on the leaching of copper. Recently, a study of the Energy Research Centre of The Netherlands (ECN) showed fulvic acid-type components to exist in the MSWI bottom ash leachates and to be likely responsible for the generally observed enhanced copper leaching. These findings were verified for a MSWI bottom ash (slashed circle 0.1-2 mm) fraction from an incinerator in Flanders. The filtered leachates were subjected to the IHSS fractionation procedure to identify and quantify the fractions of humic acid (HA), fulvic acid (FA) and hydrophilic organic carbon (Hi). The possible complexation of fulvic acid with other heavy metals (e.g., lead) was also investigated. The identified role of fulvic acids in the leaching of copper and other heavy metals can be used in the development of techniques to improve the environmental quality of MSWI bottom ash. Thermal treatment and extraction with a 0.2 M ammonium-citrate solution were optimized to reduce the leaching of copper and other heavy metals. The effect of these techniques on the different fractions of organic matter (HA, FA, Hi) was studied. However, due to the obvious drawbacks of the two techniques, research is focused on finding other (new) techniques to treat MSWI bottom ash. In view of this, particle size-based separation was performed to evaluate its effect on heavy metal leaching and on HA, FA and Hi in MSWI bottom ash leachates.

Effects of carbonation and leaching on porosity in cement-bound waste.

Porosity is possibly an important parameter with respect to leaching of constituents from cement monoliths. During its lifetime, the pore structure of cementitious matrices changes due to carbonation and leaching. This paper discusses the effects of both accelerated carbonation and continuous leaching on the porosity, and, conversely, how porosity affects leaching properties. Two sample types are investigated: a mortar with MSWI-bottom ash substituting the sand fraction and a cement paste with 30 wt% of the cement substituted by a flue gas cleaning residue. The samples have been intensively carbonated in a 20% CO(2) atmosphere for up to 60 days and were subsequently leached. The porosity was investigated by mercury intrusion porosimetry. Accelerated carbonation decreases total porosity by 12% in the case of 60 days of treatment of bottom ash mortars, whereas continuous leaching during 225 days increases it by 16%. Both carbonation and leaching decrease the amount of smaller capillary pores. Carbonation decreases both porosity and pH. Decreasing porosity diminishes leaching of sodium and potassium, while the decrease in pH increases leaching. However, the former process dominates the latter, resulting in a net decreasing effect of carbonation on the release of sodium and potassium from these cement matrices.

Integrated municipal solid waste treatment using a grate furnace incinerator: the Indaver case.

An integrated installation for treatment of municipal solid waste and comparable waste from industrial origin is described. It consists of three grate furnace lines with flue gas treatment by half-wet scrubbing followed by wet scrubbing, and an installation for wet treatment of bottom ash. It is demonstrated that this integrated installation combines high recovery of energy (40.8% net) with high materials recovery. The following fractions were obtained after wet treatment of the bottom ash: ferrous metals, non-ferrous metals, three granulate fractions with different particle sizes, and sludge. The ferrous and non-ferrous metal fractions can both be recycled as high quality raw materials; the two larger particle size particle fractions can be applied as secondary raw materials in building applications; the sand fraction can be used for applications on a landfill; and the sludge is landfilled. For all components of interest, emissions to air are below the limit values. The integrated grate furnace installation is characterised by zero wastewater discharge and high occupational safety. Moreover, with the considered installation, major pollutants, such as PCDD/PCDF, Hg and iodine-136 are to a large extent removed from the environment and concentrated in a small residual waste stream (flue gas cleaning residue), which can be landfilled after stabilisation.

Root-knot nematode (Meloidogyne spp.) Me resistance genes in pepper (Capsicum annuum L.) are clustered on the P9 chromosome.

The root-knot nematode (Meloidogyne spp.) is a major plant pathogen, affecting several solanaceous crops worldwide. In Capsicum annuum, resistance to this pathogen is controlled by several independent dominant genes--the Me genes. Six Me genes have previously been shown to be stable at high temperature in three highly resistant and genetically distant accessions: PI 322719, PI 201234, and CM334 (Criollo de Morelos 334). Some genes (Me4, Mech1, and Mech2) are specific to certain Meloidogyne species or populations, whereas others (Me1, Me3, and Me7) are effective against a wide range of Meloidogyne species, including M. arenaria, M. javanica, and M. incognita, the most common species in Mediterranean and tropical areas. These genes direct different response patterns in root cells depending on the pepper line and nematode species. Allelism tests and fine mapping using the BSA-AFLP approach showed these genes to be different but linked, with a recombination frequency of 0.02-0.18. Three of the PCR-based markers identified in several genetic backgrounds were common to the six Me genes. Comparative mapping with CarthaGene software indicated that these six genes clustered in a single genomic region within a 28 cM interval. Four markers were used to anchor this cluster on the P9 chromosome on an intraspecific reference map for peppers. Other disease resistance factors have earlier been mapped in the vicinity of this cluster. This genomic area is colinear to chromosome T12 of tomato and chromosome XII of potato. Four other nematode resistance genes have earlier been identified in this area, suggesting that these nematode resistance genes are located in orthologous genomic regions in Solanaceae.

Extraction of heavy metals from municipal solid waste incinerator (MSWI) bottom ash with organic solutions.

Municipal solid waste incinerator (MSWI) bottom ash often cannot be recycled as construction material in Flanders, because leaching of Cu exceeds the limit value of 0.5mg/kg. Leaching of other components such as Mo and Sb is critical as well, but limit values for these elements are to date only informal. A treatment technique was investigated to lower pollutant leaching: extraction with solutions of organic complexants to remove Cu. Six different solutions were used, of which washing with citric acid and ammonium citrate decreases Cu leaching to below the limit value. Extraction was then performed with different concentrations of ammonium citrate. Subsequent washing of the extracted material with distilled water appears to be vital to remove all residual ammonium citrate. Extraction with a 0.2M solution of ammonium citrate followed by three washing steps decreases metal leaching to below the limit values.

Accelerated carbonation for treatment of MSWI bottom ash.

Leaching of heavy metals from MSWI bottom ash exceeds some of the Flemish limit values for recycling the material as granular construction application. In particular, leaching of Cu, Zn and Pb often exceeds the limit value, with Cu being the most critical. In order to recycle bottom ash, treatment is therefore required. The bottom ash studied was divided on-site into four fractions using a large-scale wet sieving installation: a sludge fraction (Ø 0-0.1mm), a sand fraction (Ø 0.1-2mm) and two gravel fractions (Ø 2-6 and 6-50mm). The two gravel fractions complied with the limit values after 3 months of natural ageing. The sand and sludge fraction did not reach the limit value for Cu. Four weeks of accelerated carbonation resulted in an important decrease of Cu leaching from these two fractions, although the limit value is still exceeded. In view of applying carbonation as one of the treatment methods in an integrated industrial application, two tests were additionally performed. The use of stack gas as carbonating medium was verified by setting up an accelerated carbonation experiment at the incineration plant. Also, the depth of carbonation was measured in a 10 cm thick sample of the sand fraction after different periods of treatment. After 3 months of natural ageing only the upper 4 cm underwent a significant carbonation, while after one week of accelerated carbonation the total sample was carbonated. A model was developed to predict these experimental results.

Effect of improving flue gas cleaning on characteristics and immobilisation of APC residues from MSW incineration.

The flue gas cleaning system of a MSW incinerator with a capacity of 350 kt/year was changed to improve the HCl elimination efficiency. Instead of the semi-wet operating spray reactor and subsequent baghouse, a two-step wet flue gas cleaning was added behind the baghouse. Elemental composition, X-ray powder diffraction patterns and TGA measurements showed that the resulting APC residue was totally different from the former residue. As a consequence, leaching characteristics of both residues also differed and another treatment was required prior to disposal. For the former residue, mainly leaching of Pb (>100 mg/l), necessitated treatment prior to landfilling. The lower alkalinity of the new residue resulted in a leachate pH of 9.7 and a Pb concentration of 0.8 mg/l. The leachate pH of the former residue was 12.4. The leaching of Pb and Zn increased above 100 mg/l when immobilising the new residue with cement. Better results were obtained when immobilising with micro silica. The high CaCl2 x 2H2O content of the new residue brought along clogging of the bag filter system. Adding 1.4% of CaO (or 1.9% of Ca(OH)2) to the residue already improved these inconveniences but again significantly changed the leaching behaviour of the residue.

Variation in stakeholder opinion on countermeasures across Europe.

A compendium of agricultural countermeasures and rural waste disposal options has been compiled as part of the EC STRATEGY (Sustainable Restoration and Long-Term Management of Contaminated Rural, Urban and Industrial Ecosystems) project. The compendium was discussed by the FARMING (Food and Agriculture Restoration Management Involving Networked Groups) network of stakeholders during meetings of national panels in the UK, Finland, Belgium, Greece and France in 2002. Their preliminary feedback has been summarised in terms of whether an option is generally acceptable, unacceptable or only acceptable under specific circumstances. A considerable divergence of opinion between national panels was apparent for many of the options considered. This could be attributed to differences in geomorphology, climate, land management, infrastructure, consumer confidence, sociopolitical context and culture. Where consensus was reached between stakeholders it was generally for those countermeasures that provide public reassurance, sustain farming practices and minimise environmental impact. Furthermore, whilst there was general agreement that contaminated food should not enter the food chain, many of the options proposed for its subsequent management were not generally acceptable to stakeholders.

Achievements, difficulties and future challenges for the FARMING network.

The EC FARMING network (Food and Agriculture Restoration Management Involving Networked Groups) was set up to bring together the many and diverse stakeholders who would be involved in intervention following wide scale radioactive contamination of the food chain, so that acceptable strategies can be developed for maintaining agricultural production and safe food supply. The network comprises stakeholder panels in the UK, Finland, Belgium, France and Greece that have met regularly since 2001 to debate, discuss and exchange opinion on the acceptability, constraints and impact of various countermeasure options and strategies. The objectives of this paper are to consolidate the main achievements of the FARMING project over the period 2000-2004, to highlight the various difficulties that were encountered and to discuss the challenges for engaging stakeholders in off-site emergency management and long-term rehabilitation in the future.

Attitude of a group of Belgian stakeholders towards proposed agricultural countermeasures after a radioactive contamination: synthesis of the discussions within the Belgian EC-FARMING group.

In the case of radioactive contamination of the environment with an impact on the food chain, the remediation strategy will not only be based on scientific knowledge and technical experience, but will also be dictated by peculiarities of the country. These characteristics include the agro-industrial structure, the local and international economical contexts and the political configuration including the distribution of responsibilities and competencies. This paper identifies and illustrates the most relevant characteristics of the Belgian agricultural system and political environment; it also describes the past experience with food chain contamination, which is expected to influence the attitude of Belgian stakeholders, who would be involved in the setting up of countermeasure strategies for maintaining agricultural production and food safety. The picture drawn explains why several countermeasures aiming to reduce the contamination in food products, although scientifically sound and technically feasible, are hardly acceptable or even not acceptable at all, to the stakeholders.