Catalytic oxidation of gaseous PCDD/Fs with ozone over iron oxide catalysts

Catalytic oxidation of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) with ozone (catalytic ozonation) over nano-sized iron oxides (denoted as FexOy) was carried out at temperature of 120-180 degrees C. The effects of operating temperature, ozone concentration, space velocity (SV) and water vapor contents on PCDD/F removal and destruction efficiencies via catalytic ozonation were investigated. High activity of the iron oxide catalyst towards PCDD/F decomposition was observed even at low temperatures with the aid of ozone. The PCDD/F removal and destruction efficiencies achieved with FexOy/O3 at 180 degrees C reach 94% and 91%, respectively. In the absence of ozone, the destruction efficiencies of all PCDD/F congeners are below 20% and decrease with increasing chlorination level of PCDD/F congener at lower temperature (120 degrees C). However, in the presence of ozone, the destruction efficiencies of all PCDD/F congeners are over 80% on FexOy/O3 at 180 degrees C. Higher temperature and ozone addition increase the activity of iron oxide for the decomposition of PCDD/Fs. Additionally, in the presence of 5% water vapor, the destruction efficiency of the PCDD/Fs is above 90% even at lower operating temperature (150 degrees C). It indicates that the presence of appropriate amount of water vapor enhances the catalytic activity for the decomposition of gas-phase PCDD/Fs.     

The dioxin/POPs legacy of pesticide production in Hamburg: Part 2—waste deposits and remediation of Georgswerder landfill

α-HCH, β-HCH, and γ-HCH (lindane) were listed as persistent organic pollutants in the Stockholm Convention. Therefore, they need to be globally addressed including the wastes remaining from historic use and production. While at most lindane production sites the unintentionally produced 85 % HCH waste isomers have been deposited, at a former pesticide factory in Hamburg-Moorfleet HCH waste isomers have been recycled from 1953 to 1984 by thermal decomposition to chlorobenzenes and resulted in high polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran (PCDD/PCDF)-contaminated residues. The management of the PCDD/PCDF-contaminated waste from the former pesticide factory in Hamburg has been assessed and quantified. Based on past accredited PCDD/PCDF measurements, the registered 3,700 tonnes of disposed thermal HCH decomposition residue contained 333 to 854 kg of PCDD/PCDF toxicity equivalent (I-TEQ) in 53–102 tonnes total sum of PCDD/PCDF. The wastes have been deposited together with other wastes in landfills in Hamburg and other parts of Germany. For the Georgswerder landfill (Hamburg), where approximately 50 % of the PCDD/PCDF is disposed, current and previous situation and remediation activities are described. While PCDD/PCDF leaching from the landfill is controlled and incinerated, more water soluble organochlorines (vinyl chloride, cis-1,2-dichlorethene, chlorobenzenes) and benzene remain as a challenge for groundwater management. A comprehensive aftercare program has been established and will need to be operated by future generations including renewal of containment systems. Former lindane/HCH productions need—in addition to HCH deposits—to be assessed for possible recycling practice of HCH and related PCDD/PCDF-containing deposits. This could systematically be addressed within the Stockholm Convention implementation.     

Relevance of PCDD/PCDF formation for the evaluation of POPs destruction technologies--review on current status and assessment gaps

One important criterion for assessment of a POPs destruction technology is the potential formation of new POPs and other toxic by-products, in particular whether the highly toxic PCDDs/PCDFs are formed and under which operation conditions their formation is relevant. For incineration processes the formation mechanisms of PCDDs/PCDFs have been investigated thoroughly and strategies and technologies were developed to minimize their formation and emission. A detailed assessment of non-combustion technologies with respect to PCDD/PCDF formation is, however, lacking to date. A comparison of reaction conditions for PCDD/PCDF formation from precursor formation studies and actual applied conditions of a broad range of POPs destruction technologies in the present paper indicates that the operation conditions for a number of destruction technologies have the potential to generate high concentrations of PCDDs/PCDFs if dioxin precursors are present and that also PCDD/PCDF de novo formation can take place. Therefore a strategy and regulations for a more profound assessment and monitoring of the fate of PCDD/PCDF formation and emission is essential for the evaluation of POP destruction technologies and for a sound risk management of POPs. The present paper aims to provide a critical impulse in this respect, discusses the relevant formation pathways with respect to POPs destruction technologies and proposes a basic framework on how evaluations may be performed.     

Decomposition of paper wastes in presence of ceramics and cement raw material

Paper recycling is an environmental important activity that is carried out in all the countries, but during the recycling process a paper waste is produced. Generally these wastes are placed in landfill sites but it is possible to profit it as secondary fuel and raw material in manufacture furnaces.

In this work the combustion of the waste papers with cement and ceramic raw material has been studied with the objective to analyse the interaction of these substances with the emitted pollutants like PAHs and PCDD/Fs.

The results of the study show that the presence of inorganic material produces an increment in the lighter PAH emission but chlorinated compounds are not affected. The PCDD/F emission level found in the combustion of this waste is quite low compared with other wastes subjected to similar conditions.     

Characteristics of dioxins and metals emission from radwaste plasma arc melter system

This study investigated the emission characteristics of PCDD/Fs and the partitioning of three heavy metals (Cd, Hg and Pb) and two radioactive metal surrogates (Co and Cs) in a radwaste plasma arc melter system. Typical mixtures of low-level radioactive wastes were simulated as the trial burn surrogate wastes. The emission of PCDD/Fs and the partitioning of the metals were strongly influenced by the feed waste stream and melter operating temperature, respectively. The emissions of PCDD/Fs, cadmium and lead were greatly enhanced when the polyvinyl chloride was included in the feed waste stream. Most of the nonvolatile cobalt partitioned into the glass. A significant quantity of cesium, cadmium and lead was vaporized during the highest melter temperature test. A lower melter temperature resulted in more cesium, cadmium and lead species remaining in the glass. The results of this study suggest that wet scrubbing as well as a low-temperature two-step fine filtration, or both of them together could not effectively capture the gas-phase or fine particle phase PCDD/Fs and mercury species. In order to effectively treat low-level radioactive waste streams, the tested high-temperature melter should include an adsorption system, which could collect the gas-phase PCDD/Fs and mercury species.     

National PCDD/PCDF release inventories under the Stockholm Convention on Persistent Organic Pollutants

National inventories to estimate releases of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans have been undertaken since the mid 1980s. These inventories were scattered and hard to compare since there was no harmonized method available. With the conclusion of the Stockholm Convention on Persistent Organic Pollutants and its entry into force, Parties to the Convention at the global level, have to establish PCDD/PCDF release inventories and report these results. UNEP Chemicals has developed a methodology that allows developing and developed countries to make estimates of PCDD/PCDF releases into the environment along all vectors. Presently, there are 23 national release inventories available that have been made with this methodology, the Toolkit. Among the most important sources, open fires in agriculture/forests as well as open burning of wastes have been identified as the major sources of PCDD/PCDF. The results from these inventories may serve as the starting point for interventions to reduce or eliminate sources of PCDD/PCDF by application of best available techniques and best environmental practices. The Toolkit will be updated as needs arise.     

Innovative PCDD/F-containing gas stream generating system applied in catalytic decomposition of gaseous dioxins over V2O5-WO3/TiO2-based catalysts

Development of effective PCDD/F (polychlorinated dibenzo-p-dioxin and dibenzofuran) control technologies is essential for environmental engineers and researchers. In this study, a PCDD/F-containing gas stream generating system was developed to investigate the efficiency and effectiveness of innovative PCDD/F control technologies. The system designed and constructed can stably generate the gas stream with the PCDD/F concentration ranging from 1.0 to 100ng TEQ Nm(-3) while reproducibility test indicates that the PCDD/F recovery efficiencies are between 93% and 112%. This new PCDD/F-containing gas stream generating device is first applied in the investigation of the catalytic PCDD/F control technology. The catalytic decomposition of PCDD/Fs was evaluated with two types of commercial V(2)O(5)-WO(3)/TiO(2)-based catalysts (catalyst A and catalyst B) at controlled temperature, water vapor content, and space velocity. 84% and 91% PCDD/F destruction efficiencies are achieved with catalysts A and B, respectively, at 280 degrees C with the space velocity of 5000h(-1). The results also indicate that the presence of water vapor inhibits PCDD/F decomposition due to its competition with PCDD/F molecules for adsorption on the active vanadia sites for both catalysts. In addition, this study combined integral reaction and Mars-Van Krevelen model to calculate the activation energies of OCDD and OCDF decomposition. The activation energies of OCDD and OCDF decomposition via catalysis are calculated as 24.8kJmol(-1) and 25.2kJmol(-1), respectively.     

Cleaner co-combustion of lignite-biomass-waste blends by utilising inhibiting compounds of toxic emissions

In this paper, the co-combustion behaviour of coal with wastes and biomass and the related toxic gaseous emissions were investigated. The objective of this work is to add on towards a cleaner co-combustion of lignite-waste-biomass blends by utilizing compounds that could inhibit the formation of toxic pollutants. A series of co-combustion tests was performed in a pilot scale incinerator, and the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were measured. The co-combustion behaviour of lignite with olive kernels, MDF and sawdust was studied and the ability of additives such as urea, almond shells and municipal sewage sludge to reduce the PCDD/F emissions was examined. All blends were proven good fuels and reproducible combustion conditions were achieved. The addition of inhibitors prior to combustion showed in some cases, relatively high PCDD/F emissions reduction. Among the inhibitors tested, urea seems to achieve a reduction of PCDD/F emissions for all fuel blends, while an unstable behaviour was observed for the others.     

Results from the first year of the Swedish dioxin survey

PCDD/F levels are presented for food baskets, raw and fried herring, wolf muscle and moose tallow collected from the same area, three burbot liver samples, a sediment core from the Baltic Sea and leach water from three garbage dumps. Levels in food baskets were at or below detection limits making the estimation of intake via the diet difficult. Frying herring produces no net change in PCDD/F levels. Moose have lower PCDD/F levels than wolf from the same area. Levels in burbot liver samples are much higher near industrial discharges than in a more undisturbed area. The top 4 cm of the sediment core contain the highest levels of PCDD/F. Thereafter the levels drop and reach a low level. This low level is probably caused by contamination during sampling and is not evidence of PCDD/F presence far back in time. Leach water from city dumps contains low levels of PCDD/F but that from a dump that takes industrial wastes had higher levels and a different congener pattern.     

PCDD/DF in leachates from Korean MSW landfills

We analyzed levels of PCDD/DF in leachate liquid and solid from five Korean municipal solid waste landfills to investigate the relationship between PCDD/DF and dissolved organic carbon and suspended solids in raw leachate. The concentrations of PCDD/DF ranged from 173.2 to 1329.4 pg/l and 4.1 to 46.22 pg-TEQ/l. The range of PCDD/DF was 123.2-1161.3 pg/l in leachate solid and 50.0-383.3 pg/l in leachate liquid. Our results indicated that PCDD/DF in solid play a major role in determining their concentration levels, and the distribution of isomers in solid was almost the same as in liquid leachate. In addition, highly chlorinated PCDD/DF, such as HpCDD/DF and OCDD/DF, accounted for more than 70% of all isomers. Levels of PCDD/DF in liquid were strongly correlated with dissolved organic carbon concentrations, which increase the leachability (R2 = 0.92 in Korean leachate) of PCDD/DF from contaminant sources. Despite this high linearity between dissolved organic carbon and dissolved PCDD/DF, we observed no strong relationship between dissolved organic carbon and solid phase PCDD/DF (R2 = 0.001). Dissolved organic carbon scarcely affects dissolved PCDD/DF to be combined with solids. As a result, it is not appropriate for incinerated ash to be dumped with municipal solid wastes, as they have a large potential to result in high levels of organic matter, and therefore PCDD/DF, in leachate.     

Thermal remediation of PCDD/Fs contaminated soil by zone combustion process

A new thermal process has been proposed for remediating soils contaminated by chlorinated organic compounds, e.g., PCDD/Fs and PCBs. This is to apply the "zone combustion process" which utilizes stable combustion of coke particles in the packed bed to soils with air flow across the bed. The usefulness and validity were obtained the results showing that more than 98.9% of PCDD/Fs in the soil was successfully removed in a laboratory-scale experiment. Some pretreatment of the soil sample, such as drying, pre-granulation and addition of limestone was found to make the removal efficiency better. Although, some fundamentals on the behavior of PCDD/Fs, e.g., decomposition/vaporization ratios and formation of other compounds cannot be certainly identified yet, the present results clearly show a way to remediate the contaminated soils and solid wastes.     

Destruction of PCDD/Fs by SCR from flue gases of municipal waste incinerator and metal smelting plant

Partitioning of PCDD/F congeners between vapor/solid phases and removal and destruction efficiencies achieved with selective catalytic reduction (SCR) system for PCDD/Fs at an existing municipal waste incinerator (MWI) and metal smelting plant (MSP) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP, operating temperature: 230 degrees C), wet scrubbers (WS, operating temperature: 70 degrees C) and SCR (operating temperature: 220 degrees C) as major air pollution control devices (APCDs). PCDD/F concentration measured at stack gas of the MWI investigated is 0.728 ng-TEQ/Nm(3). The removal efficiency of WS+SCR system for PCDD/Fs reaches 93% in the MWI investigated. The MSP investigated is equipped with EP (operating temperature: 240 degrees C) and SCR (operating temperature: 290 degrees C) as APCDs. The flue gas sampling results also indicate that PCDD/F concentration treated with SCR is 1.35 ng-TEQ/Nm(3). The SCR system adopted in MSP can remove 52.3% PCDD/Fs from flue gases (SCR operating temperature: 290 degrees C, Gas flow rate: 660 kN m(3)/h). In addition, the distributions of PCDD/F congeners observed in the flue gases of the MWI and MSP investigated are significantly different. This study also indicates that the PCDD/F congeners measured in the flue gases of those two facilities are mostly distributed in vapor phase prior to the SCR system and shift to solid phase (vapor-phase PCDD/Fs are effectively decomposed) after being treated with catalyst. Besides, the results also indicate that with SCR highly chlorinated PCDD/F congeners can be transformed to lowly chlorinated PCDD/F congeners probably by dechlorination, while the removal efficiencies of vapor-phase PCDD/Fs increase with increasing chlorination.     

The Spanish dioxin inventory part I: Incineration as municipal waste management system

The main objectives of the Spanish dioxin inventory and the incidence of municipal waste incinerators in the PCDD/Fs releases in the period from January 1997-November 1999 are presented. Preliminary data about the stack emission levels, fly ashes and slags as solid residues and the PCDD/Fs input in the USW are also presented to elaborate an initial balance for the incineration sector. A great decrease, from 20 to 1.2 g I-TEQ/y, from incineration gas emissions has been observed since 1996. The preliminary balance in the MWI sector suggests an overall PCDD/Fs destruction. The calculated emission factor, 1.06 microg I-TEQ/Mg, indicates a high quality of the air pollution control systems. The assumption of PCDD/Fs in the USW permits an initial evaluation of other waste management systems.     

Formation, release and control of dioxins in cement kilns

Co-processing of hazardous wastes in cement kilns have for decades been thought to cause increased emissions of PCDD/PCDFs--a perception that has been evaluated in this study. Hundreds of PCDD/PCDF measurements conducted by the cement industry and others in the last few years, on emissions and solid materials, as well as recent test burns with hazardous wastes in developing countries do not support this perception. Newer data has been compared with older literature data and shows in particular that many emission factors have to be reconsidered. Early emission factors for cement kilns co-processing hazardous waste, which are still used in inventories, are shown to be too high compared with actual measurements. Less than 10 years ago it was believed that the cement industry was the main contributor of PCDD/PCDFs to air; data collected in this study indicates however that the industry contributes with less than 1% of total emissions to air. The Stockholm Convention on POPs presently ratified by 144 parties, classifies cement kilns co-processing hazardous waste as a source category having the potential for comparatively high formation and release of PCDD/PCDFs. This classification is based on early investigations from the 1980s and 1990s where kilns co-processing hazardous waste had higher emissions compared to those that did not burn hazardous waste. However, the testing of these kilns was often done under worst case scenario conditions known to favour PCDD/PCDF formation. More than 2000 PCDD/PCDF cement kiln measurements have been evaluated in this study, representing most production technologies and waste feeding scenarios. They generally indicate that most modern cement kilns co-processing waste today can meet an emission level of 0.1ngI-TEQ/m(3), when well managed and operated. In these cases, proper and responsible use of waste including organic hazardous waste to replace parts of the fossil fuel does not seem to increase formation of PCDD/PCDFs. Modern preheater/precalciner kilns generally seems to have lower emissions than older wet-process cement kilns. It seems that the main factors stimulating formation of PCDD/PCDFs is the availability of organics in the raw material and the temperature of the air pollution control device. Feeding of materials containing elevated concentrations of organics as part of raw-material-mix should therefore be avoided and the exhaust gases should be cooled down quickly in long wet and long dry cement kilns without preheating. PCDD/PCDFs could be detected in all types of solid samples analysed: raw meal, pellets and slurry; alternative raw materials as sand, chalk and different ashes; cement kiln dust, clinker and cement. The concentrations are however generally low, similar to soil and sediment.     

The formation of polychlorinated dibenzo-p-dioxins/dibenzofurans from carbon model mixtures containing ferrous chloride

The potential to form polychlorinated dibenzo-p-dioxins/furans (PCDD/F) was investigated in carbon model systems containing ferrous chloride tetrahydrate and a matrix representative of that found in particle emission from the catalytic extraction process (CEP) for wastes. Various types of carbons were used resulting in different PCDD/F yields but, with one exception, similar homologue distributions. Due to the similarity between the turbostratic structure of the carbon in the representative CEP dusts and the carbon blacks used in the model system, experiments were performed using two carbon blacks (termed CBA and CBB). On a mass basis, CBB was more reactive over the temperature range of 275-325 degrees C and reaction times of 20-60 min in the formation of PCDD/F; as well as more adsorptive in terms of the desorption of PCDD/F. On a volume basis, the reactivities and adsorptivities were similar. A maximum in PCDD/F formation occurred at an oxygen concentration of 2% in nitrogen.     

Suppressing effect of goethite on PCDD/F and HCB emissions from plastic materials incineration

Polyethylene (PE) and polyvinyl chloride (PVC) are the leading plastics in total production in the world. The incineration of plastic-based materials forms many chlorinated compounds, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). In this study the addition of goethite (alpha-FeOOH) was investigated to determine its suppressing effect on the emission of PCDD/Fs and hexachlorobenzene (HCB) during the combustion of wastes containing PE and PVC. Goethite was being considered since it acts as a dioxin-suppressing catalyst during incineration. Results showed that incorporation of goethite greatly reduced the generation of PCDD/Fs and HCB in the exhaust gas and fly ash. The concentration of PCDD/Fs in flue gas decreased by 45% for lab-scale and 52% for small incinerator combustion experiments, where the goethite ratios in feed samples were 0.54% and 0.34%, respectively. Under the same conditions, the concentration of HCB in flue gas decreased by 88% and 62%, respectively. The present study showed a possible mechanism of the suppressing effect of the goethite for PCDD/F formation. It is likely that iron chlorides react with particulate carbon to form organo-chlorine compounds and promote PCDD/F formation in the gas phase. XRD analysis of combustion ash revealed that the goethite was partially dehydrated and converted to alpha-Fe(2)O(3) and Fe(3)O(4) but no iron chlorides formation. Therefore the goethite impregnated plastics can contribute the reduction of PCDD/Fs and HCB in the exhaust gas during incineration of MSW.     

Dioxin analysis in stack emissions, slags and the wash water circuit during high-temperature incineration of chlorine-containing industrial wastes; Part 2

PCB's and polychlorobenzene sumps have been incinerated in a high-temperature installation. The working conditions, wastes, sampling methods and analysis of the stack emissions, slag and wash water are described. No 2,3,7,8-TCDD and only ppt-traces of some PCDD congeners were detected in the stack emission. The performance criteria of the incinerator and the more important sampling procedures are discussed.     

Development of expanded and core kinetic models for the gas phase formation of dioxins from chlorinated phenols

Expanded, 45 reaction, and core, 12 reaction, kinetic models have been developed that account for the major features in the homogeneous formation of polychlorinated dibenzo-p-dioxins (PCDD) from the oxidation of 2,4,6-trichlorophenol (P). The expanded and core schemes provide good agreement between experimental and calculated yields of PCDDs using the CHEMKIN combustion package or the React kinetic program, respectively. Steady-state approximations of the reaction kinetic models including radical-molecule and radical-radical formation pathways of PCDD, as well as oxidative destruction pathways of chlorinated phenoxyl radicals, reveal a competition between reactions of chlorinated phenoxyl radicals with chlorinated phenols, recombination reactions of chlorinated phenoxyl mesomers, and destruction/decomposition of phenoxyl radicals.     

Modeling the formation of PCDD/F in solid waste incinerators

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) appear in unacceptable amounts in the gaseous emissions during the incineration of wastes containing significant quantities of chlorine and metals, such as MSW and medical waste. They are formed both in the gas phase at temperatures above 600 degrees C and on the surface of the solid phase (flyash) in the temperature range 400-225 degrees C. Both the precursor (from existing smaller chlorinated molecules) and de novo (from elemental carbon) routes are involved. An empirically derived global model for their de novo formation on flyash in MSW and medical waste incinerators has now been extended to include the precursor mechanism, and a gas phase formation component, with separate rate expressions for PCDD and PCDF. Homogeneous PCDD formation is governed by the concentration of chlorophenols and PCDF by that of chlorophenols and chlorobenzenes. The result is more complete system which distinguishes between the gas and solid phase contributions to the I-TEQ. An additional step for the adsorption of gaseous PCDD/F back onto the solid phase during cooling suggests this should be minimal in the gas ducts of an incinerator. The extended model has been tested against experimental data collected from a well-controlled pilot incinerator and commercial incinerators, and found to adequately describe the measured outputs. With the model it should be possible to predict the PCDD/F emissions from commercial incinerators, provided that the ash properties and the overall temperature-time profiles are known.     

Infant exposure to polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls (PCDD/Fs, PCBs)--correlation between prenatal and postnatal exposure

Polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) are recognized environmental endocrine disruptors, which are environmentally persistent and may bio-accumulate in human bodies. Pregnant and nursing women may pass these pollutants to their babies both trans-placentally and lactationally. We measured and examined correlations of the levels of PCDD/Fs and PCBs in perinatal venous serum, placenta, umbilical-cord serum (representing prenatal exposure), and breast milk (postnatal exposure). Subjects included pregnant women without clinical complication between the ages of 25 and 35, who delivered their babies during 2000.12.01 and 2001.11.30 in central Taiwan. A total of 20 participants were randomly selected from those provided the four biological specimens for analysis of 17 PCDD/Fs, and 12 dioxin-like PCBs and six indicator PCBs using high-resolution gas chromatography/high-resolution mass spectrometry. Higher PCDD/F levels were found in placenta (10.3 TEq-pg/g lipid) and venous serum (9.1 TEq-pg/g lipid) compared to those in breast milk (7.6 TEq-pg/g lipid). Pearson and Spearman correlation analyses showed well association of PCDD/F and PCB levels between different specimens. The total dioxin/PCB level in milk, venous and cord serum can be well predicted by that in placenta through regression functions. This first study of multi-specimen correlation further established rather consistent ratios of these chemical concentrations in various specimens relative to those in venous serum.