Sources and relative importance of PCDD and PCDF emissions

Polychlorinated dioxins (PCDD) and dibenzofurans (PCDF) have been identified in technical products and pesticides, most of which are not very widely used today. Other sources are incinerators of various types like MSW incinerators, hazardous waste incinerators and industrial incinerators. PCDDs and PCDFs have also been identified in exhausts from cars running on leaded gasoline with halogenated additives. Background levels of PCDDs and PCDFs have been identified in fish and other aquatic organisms from the Great Lakes and the Baltic Sea, and also in human adipose tissue samples from U.S.A., Canada, Sweden, Japan and Vietnam as well as in samples of breast milk from Sweden, Denmark, West Germany, the Netherlands, Yugoslavia and Vietnam. The isomeric pattern in all these biological samples is very similar. The relative importance of different sources to the general background is difficult to estimate although the contribution of direct inhalation from point sources like MSW incinerators is small.     

Problems associated with the measurement of PCDD and PCDF emissions from waste incineration plants

Fly ash and stack gases from municipal waste and industrial incinerators in the F.R.G. have been analyzed for dioxins (PCDD and PCDF). Most of the currently used procedures of stack gas sampling for PCDD/PCDF have been compared and were found to be equally effective. Differences are found, however, in the recovery of surrogates added to the sampling train before sampling, which makes it difficult to validate the sampling procedure. The analysis for PCDD%PCDF in stack gas or fly ash samples from municipal waste incinerators can no longer be considered an analytical problem. Thirty samples of stack gas from a single (old) municipal waste incinerator showed wide variation in PCDD/PCDF emission, indicating that single measurements are not useful in characterizing a plant for average PCDD/PCDF emission. It will be extremely difficult to correlate plant operating conditions to PCDD/PCDF stack gas emissions or PCDD/PCDF fly ash concentrations, because the effects produced by changing conditions are obscured by the variations which occur in PCDD/PCDF concentrations during steady conditions. The variations found under steady conditions can be explained by the proposed mechanisms of PCDD/PCDF formation and decomposition at low temperatures catalyzed by fly ash. Incineration of hospital waste and pyrolytic reclamation of copper in cables and aluminium produced significant emission of PCDD/PCDF. A major noncombustion source of higher chlorinated PCDD/PCDF (tetra- to octa-isomers) is pentachlorophenol, a widespread preservative which contributes to the PCDD/PCDF concentrations found, for example, in sewage sludge, river sediments and house dust.     

Repartition of PCDD and PCDF in the emissions of municipal solid waste incinerators between the particulate and volatile phases

The present paper refers to the results of a research project on the polychlorinated dibenzyil-p-dioxin (PCDD) and polychlorinated dibenzofurans repartition in particulate and volatile phase in emissions from municipal solid waste incinerators. The distribution of such micropollutants between the different phases is analyzed in terms of absolute weights and in terms of 2, 3, 7, 8 TCDD Equivalents. This paper shows that more than half of the total content of PCDD/Fs emitted are adsorbed in the fly ash, with the remaining part in the volatile phase. Such repartition is inverted if the PCDD/Fs are expressed in terms of 2, 3, 7, 8 TCDD Equivalent.     

Recent findings on the formation and decomposition of PCDD/PCDF in municipal solid waste incineration

The thermal formation of PCDD/PCDF in fly ashes of refuse incineration plants preferably in the low-temperature region of the boiler at 3002C is fully confirmed. Important parameters for the reaction of formation are the oxygen content and the water vapor in the offgas. Elemental carbon in the fly ash acts as an adsorbent to the precursor compounds. The oxidation of carbon may serve as a basis for the mechanism of PCDD/PCDF formation. Both reactions proceed by the Deacon process scheme. The catalytic action of CuCl₂ can be counteracted by the addition of NH₃.     

The influence of fly ash load and particle size on the formation of PCDD,PCDF, PCBz and PCB in a pilot incinerator

A laboratory-scale, fluidized bed reactor fuelled by a synthetic fuel was used to study the influence of fly ash load, particle size, temperature and residence time on the low-temperature formation of chlorinated aromatic compounds. Large fly ash particles were removed from the flue gases by means of a cyclone at the entrance to the cooling section of the reactor. The experimental variables were varied according to an experimental plan of full factorial design. Polychlorinated dibenzo-p-dioxins, dibenzo-furans, polychlorinated benzenes and biphenyls were analysed in the collected flue gas samples. Despite the fact that most of the fly ash load was removed by the cyclone, formation of chlorinated aromatics occurred to the same extent as in earlier experiments, without the cyclone. These results demonstrate the importance of small fly ash particles in the post-combustion formation of chlorinated aromatics.     

Characteristics of products and PCDD/DF emissions from a pyrolysis process of urethane/styrofoam waste from electrical home appliances

A plastic fraction consisting mainly of polyurethane/styrofoam waste is generated after separating valuable spare parts and metals from used electrical home appliances. In Korea, such waste is currently incinerated in cement kilns or is landfilled. However, owing to its high volatile matter content, conversion into gaseous or liquid pyrolysis products is a preferable alternative. A pyrolysis process of polyurethane and styrofoam waste from electrical home appliances was evaluated by characterizing the products generated at 500°–800°C. The para meters determined were the yields of gas, oil, and char; the characteristics of the remaining char; and the con centration of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzo-furans in the product gas. As expected, the char yield decreased at higher temperatures, whereas gas and oil yields showed increasing tendency. The oil products could be used as storable fuels with a calorific value of 6000–8000 kcal/kg. Fine pores were observed in the char. The adsorption and decolorizing ability of the char were almost the same as those of activated carbon, so that pyrolysis char has potential for use as a sorbent. Further feasibility studies will be needed before utilizing pyrolysis technology to recover either fuels or usable products from polyurethane/styrofoam waste.     

Impact on health of chlorinated dioxins and other trace organic emissions

The potential health effects of incineration of municipal solid waste (MSW) have been studied by the Swedish National Institute of Environmental Medicine.The greatest concern for health effects relates to the emission of PCDDs and PCDFs (“dioxins”). MSW incineration is presently estimated to be a large source for the emission of these compounds into ambient air. Based upon animal experiments, and by applying safety factors in the range 200–1000, a highest tolerable daily intake (TDI) has been estimated to be 1–5 pg kg⁻¹ of TCDD for humans. This TDI-value has been extended to cover all the congeners of PCDDs and PCDFs by the application of the concept of “TCDD-equivalents” (Eadon et al., 1983). The high concentrations found in human breast milk and fish indicate that the TDI value may be exceeded, especially among breast-milk fed babies. If the emission can be reduced to the proposed Swedish limit value of 0.1 ng m⁻³ n TCDD-equivalents, or less, the contribution from this source will be lowered. MSW incineration can be considered acceptable when the following aspects are taken into account: the risk estimation for TDI is conservative; there is no indication that man belongs to the most sensitive species although infants may be particularly sensitive; available studies indicate that the concept of TCDD-equivalents used overestimates the effect of mixtures of PCDDs and PCDFs; present levels in fish and human milk reflect the cumulative effect of many years of emission. Besides PCDDs and PCDFs, MSW incineration also gives rise to relatively high emissions of PAH, chlorinated PAH, phenols, benzenes and mutagenic substances under less well controlled combustion conditions. The emission of organic compounds is generally dependent on the combustion efficiency. If the combustion process is optimized and advanced flue-gas cleaning is applied so that the emission of TCDD-equivalents does not exceed 0.1 ng m⁻³, emission of other organics probably will not cause significant health hazards.     

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.     

Contribution of waste segregation to GHG emissions,land usage,and health risk of NMVOC exposure: a study in Malaysia

Journal of Material Cycles and Waste Management - The present study examined greenhouse gas (GHG) emissions, land usage, cost of land use, and health risk exposure to non-methane volatile organic...     

Spatial variability of nitrous oxide and methane emissions from an MBT landfill in operation: Strong N2O hotspots at the working face

Mechanical biological treatment (MBT) is an effective technique, which removes organic carbon from municipal solid waste (MSW) prior to deposition. Thereby, methane (CH₄) production in the landfill is strongly mitigated. However, direct measurements of greenhouse gas emissions from full-scale MBT landfills have not been conducted so far. Thus, CH₄ and nitrous oxide (N₂O) emissions from a German MBT landfill in operation as well as their concentrations in the landfill gas (LFG) were measured. High N₂O emissions of 20–200 g CO₂ eq. m^?2 h^?1 magnitude (up to 428 mg N m^?2 h^?1) were observed within 20 m of the working face. CH₄ emissions were highest at the landfill zone located at a distance of 30–40 m from the working face, where they reached about 10 g CO₂ eq. m^?2 h^?1. The MBT material in this area has been deposited several weeks earlier. Maximum LFG concentration for N₂O was 24.000 ppmv in material below the emission hotspot. At a depth of 50 cm from the landfill surface a strong negative correlation between N₂O and CH₄ concentrations was observed. From this and from the distribution pattern of extractable ammonium, nitrite, and nitrate it has been concluded that strong N₂O production is associated with nitrification activity and the occurrence of nitrite and nitrate, which is initiated by oxygen input during waste deposition. Therefore, CH₄ mitigation measures, which often employ aeration, could result in a net increase of GHG emissions due to increased N₂O emissions, especially at MBT landfills.     

The seasonal effects of manure management and feeding strategies on hydrogen sulphide emissions from stored dairy manure

Journal of Material Cycles and Waste Management - The influence of temperature and storage time on hydrogen sulphide (H2S) emissions from two different dairy manures was investigated over four...     

Estimating the human health risks from polychlorinated dioxins and furans in stack gas emissions from combustion units: implications of USEPA's dioxin reassessment

Shortly after promulgation of the Hazardous Waste Combustor MACT rule established regulatory limits for polychlorinated dioxins and furans (dioxins/furans) in incinerator stack gas, the US Environmental Protection Agency (USEPA) announced that facilities could still be required to demonstrate that stack emissions do not present an unacceptable risk to human health and the environment. Guidance for conducting this risk assessment activity, which was to be required under RCRA omnibus authority, was developed by the agency and released in 1998. The guidance represented an increase in complexity over previous documents developed by the agency and contains multiple chemical, fate and transport, and toxicological parameters which are to be used as default deterministic parameters in a complex series of algorithms which ultimately lead to numerical estimates of risk. As these changes were occurring, USEPA was also moving towards completion of its reassessment of dioxin. That series of documents has been the subject of considerable controversy and has, in several of its various drafts, proposed a number of changes, including modification of the existing toxic equivalency factor (TEF) approach and of the cancer potency factor of 2,3,7,8-tetachlorodibenzo-p-dioxin. At this time it is unclear what the impact of these changes will be on facilities progressing through the permitting process, because it is not intuitively obvious how changes in the risk assessment input parameters will impact the magnitude of the dioxinlfuran risk. In this paper, the receptor usually associated with the highest potential risk from dioxins/furans in a combustion risk assessment, the Subsistence Farmer, will be subjected to a sensitivity analysis to determine which of the multiple default input parameters will have the greatest influence on the potential cancer risk.     

Uncontrolled methane emissions from a MSW landfill surface: Influence of landfill features and side slopes

Sanitary landfills for Municipal Solid Waste (MSW) disposal have been identified as one of the most important anthropogenic sources of methane (CH₄) emissions; in order to minimize its negative effects on the environment, landfill gas (LFG) recovery is a suitable tool to control CH₄ emissions from a landfill site; further, the measurement of CH₄ emissions can represent a good way to evaluate the effectiveness of LFG recovering systems. In general, LFG will escape through any faults in the landfill capping or in the LFG collection system. Indeed, some areas of the capping can be more permeable than others (e.g. portions of a side slope), especially when considering a temporarily capped zone (covered area that is not expected to receive any further waste for a period of at least 3 months, but for engineering reasons does not have a permanent cap yet). These areas, which are characterized by abnormal emissions, are usually defined as “features”: in particular, a feature is a small, discrete area or an installation where CH₄ emissions significantly differ from the surrounding zones. In the present study, the influence that specific features have on CH₄ emissions has been investigated, based on direct measurements carried out in different seasons by means of a flux chamber to the case study of Palermo (IT) landfill (Bellolampo). The results showed that the flux chamber method is reliable and easy to perform, and the contoured flux maps, obtained by processing the measured data were found to be a suitable tool for identifying areas with abnormal (high) emissions. Further, it was found that a relationship between methane emission rates and landfill side slope can be established. Concerning the influence of the temporary HDPE cover system on CH₄ recovery efficiency, it contributed to a significant decrease of the free surface area available for uncontrolled emissions; this aspect, coupled to the increase of the CH₄ volumes collected by the LFG recovery system, led to a significant increase of the recovery efficiency.     

Environmental policy and legal framework for controlling mercury emissions from stationary sources: a case study in Taiwan

Journal of Material Cycles and Waste Management - In recent years, the Taiwan government partnered with the U.S. Environmental Protection Agency (USEPA) Global Mercury Partnership program to follow...     

Effects of a composition change of ordinary Portland cement on waste utilization and CO2 emissions in Japan

Journal of Material Cycles and Waste Management - This paper estimates the effects of a composition change of ordinary Portland cement on waste utilization and CO2 emissions in the Japanese cement...     

The effects of substrate pre-treatment on anaerobic digestion systems: a review

Focus is placed on substrate pre-treatment in anaerobic digestion (AD) as a means of increasing biogas yields using today's diversified substrate sources. Current pre-treatment methods to improve AD are being examined with regard to their effects on different substrate types, highlighting approaches and associated challenges in evaluating substrate pre-treatment in AD systems and its influence on the overall system of evaluation. WWTP residues represent the substrate type that is most frequently assessed in pre-treatment studies, followed by energy crops/harvesting residues, organic fraction of municipal solid waste, organic waste from food industry and manure. The pre-treatment effects are complex and generally linked to substrate characteristics and pre-treatment mechanisms. Overall, substrates containing lignin or bacterial cells appear to be the most amendable to pre-treatment for enhancing AD. Approaches used to evaluate AD enhancement in different systems is further reviewed and challenges and opportunities for improved evaluations are identified.     

Effects of a temporary HDPE cover on landfill gas emissions: multiyear evaluation with the static chamber approach at an Italian landfill

According to the European Landfill Directive 1999/31/EC and the related Italian Legislation (“D. Lgs. No. 36/2003”), monitoring and control procedures of landfill gas emissions, migration and external dispersions are clearly requested. These procedures could be particularly interesting in the operational circumstance of implementing a temporary cover, as for instance permitted by the Italian legislation over worked-out landfill sections, awaiting the evaluation of expected waste settlements.A possible quantitative approach for field measurement and consequential evaluation of landfill CO₂, CH₄ emission rates in pairs consists of the static, non-stationary accumulation chamber technique. At the Italian level, a significant and recent situation of periodical landfill gas emission monitoring is represented by the sanitary landfill for non-hazardous waste of the “Fano” town district, where monitoring campaigns with the static chamber have been annually conducted during the last 5 years (2005-2009). For the entire multiyear monitoring period, the resulting CO₂, CH₄ emission rates varied on the whole up to about 13,100 g CO₂ m⁻² d⁻¹ and 3800 g CH₄ m⁻² d⁻¹, respectively.The elaboration of these landfill gas emission data collected at the “Fano” case-study site during the monitoring campaigns, presented and discussed in the paper, gives rise to a certain scientific evidence of the possible negative effects derivable from the implementation of a temporary HDPE cover over a worked-out landfill section, notably: the lateral migration and concentration of landfill gas emissions through adjacent, active landfill sections when hydraulically connected; and consequently, the increase of landfill gas flux velocities throughout the reduced overall soil cover surface, giving rise to a flowing through of CH₄ emissions without a significant oxidation. Thus, these circumstances are expected to cause a certain increase of the overall GHG emissions from the given landfill site.     

Particulate and gaseous emissions during fluidized bed combustion of semi-dried sewage sludge: Effect of bed ash accumulation on NOx formation

Combustion of two semi-dried sewage sludges in a 110 mm has been characterized in terms of particulate and gaseous emissions. Sludges differed in that they had been conditioned – at the flocculation stage of wastewater treatment – either with Ca-based inorganics or with polyelectrolytes. Combustion was efficient for both sewage sludges under all the operating conditions tested. Significant differences have instead been observed between the two types of sewage sludges as regards particulate and macro-pollutant gaseous emissions (SO₂, NO_x). NO_x formation is significantly influenced by ash accumulation inside the bed only when sewage sludge conditioned with Ca-based inorganics is fired. The time-resolved profiles of NO_x concentration and the mass flow rate of the elutriated fines have been worked out to evaluate the fuel nitrogen yield to NO_x as a function of ash accumulated inside the bed divided by the air mass feed rate. Experimental results have been compared with data present in literature.     

Composition of a Spanish sewage sludge and effects on treated soil and olive trees

The effects of sewage sludge (SL) application on the soil and olive trees (Olea europaea L., cultivar: cornicabra) were studied. The plants were grown in 8.5L pots and subjected to the following treatments: 0, 3.66, 7.32, 14.65, 29.3, 58.6, and 117.2 g SL kg(-1) soil that corresponded, respectively, to 0, 4, 8, 16, 32, 64 and 128 M g ha(-1) dry weight of sewage sludge. The application of SL at the rates 64 and 128 M g ha(-1) produced leaf tip burning and leaf drop after 120 days, although cumulative metal pollutant loading rates was below USEPA and European regulations. This toxicity symptom could be caused by the high sodium levels in the leaves (over 0.19%), which can damage olive tree development. The Na contents of leaves were well correlated with soil Na content (r2: 0.91). In general, SL rates significantly increased the level of Cr, Ni, Cu, Zn, Cd and Pb in soil and plants, but these concentrations were in the normal ranges, except for the Zn concentration, which was over the critical soil content for the rates of 32, 64, 128 Mg ha(-1) but not in the leaves. Results suggested that regulations about the utilization of sewage sludge on agricultural land should consider the limit values for salt, and not only metals, that may be added to soil, in order to minimize the risk of negative effects to plant health.