Simultaneous sampling of PCDD/PCDF inside the combustion chamber and on four boiler levels of a waste incineration plant

At a MSWI (municipal solid waste incinerator) plant PCDD/PCDF samples (gasphase and particulates) were taken simultaneously be a shock-freezing method in the incinerator combustion chamber at approx. 800°C and in four sampling sections in the boiler at about 490°C, 370°C, 330°C and 270°C. In this way PCDD/PCDF-formation in the flow through the boiler was determined. Two data sets were evaluated. A considerable PCDD/PCDF-formation had occurred already at boiler temperatures of about 490°C; the highest concentration, however, was found at the end of the boiler at about 300°C. The accompanying measuring program of plant parameters made the calculation of the PCDD/PCDF mass flows possible, which allowed the inclusion of the PCDD/PCDF-content in the ESP dust in the mass flow calculations.     

Comparison of PCDD/PCDF levels in soil, grass, cow''s milk, human blood and spruce needles in an area of PCDD/PCDF contamination through emissions from a metal reclamation plant

When in the vicinity of a metal reclamation plant in Tyrol, Austria, increased PCDD/PCDF levels were found in soil and spruce needles, the extent of grass contamination as well as the PCDD/PCDF content in milk of cows fed with hay from this area was determined. The milk samples showed a significant increase in PCDD/PCDF levels compared to control samples. In a blood sample of a farmer a significant increase in PCDD/PCDF levels was found. Correlations in PCDD/PCDF levels between soil, spruce needles, grass, cow's milk and human blood will be presented.     

Quality control for sampling of PCDD/PCDF emissions from open combustion sources

Both long duration (>6 h) and high temperature (up to 139 °C) sampling efforts were conducted using ambient air sampling methods to determine if either high volume throughput or higher than ambient air sampling temperatures resulted in loss of target polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) from a polyurethane foam (PUF) sorbent. Emissions from open burning of simulated military forward operating base waste were sampled using EPA Method TO-9A for 185 min duration using a filter/PUF/PUF in series combination. After a 54 m³ sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6 h of ambient air sampling (171 m³) was conducted and the second PUF was analyzed to determine if the PCDD/PCDF transferred from the filter and the first PUF. Less than 4.4% of the initial PCDD/PCDF was lost to the second PUF. To assess the potential for blow off of PCDD/PCDF analytes during open air sampling, the mobility of spiked mono- to hepta-PCDD/PCDF standards across a PUF sorbent was evaluated from ambient air temperatures to 145 °C with total volumes between 600 L and 2400 L. Lower molecular weight compounds and higher flow amounts increased release of the spiked standards consistent with vapor pressure values. At 600 L total sampled volume, the release temperature for 1% of the tetra-CDD (the lowest chlorinated homologue with a toxic compound) was 87 °C; increasing the volume fourfold reduced this temperature to 73 °C.     

Formation and destruction of PCDD/F inside a grate furnace

Formation and destruction of polychlorinated dibenzo-p-dioxins and dibenzofurans PCDD/F during the combustion process was investigated experimentally in a pilot plant. All important process steps like the burnout of the fuel bed on the grate, the burnout of the flue gas inside the combustion chamber, the heat recovery in a boiler as well as influences of the fuel composition are described in detail.

High concentrations especially of PCDF are formed during the burnout of the fuel bed. The formation reaction is mainly influenced by the fuel composition and the burnout characteristic of the fuel bed. Fuels with low chlorine and low metal content (Cu) result only in negligible concentrations of PCDD/F.

Under stable combustion conditions characterized by an excellent flue gas burnout PCDD/F will almost be completely destroyed already inside the combustion chamber. “Cold strands” of unburned flue gas (high CO concentrations) caused by disturbed combustion conditions will result in high concentrations of PCDD and especially of PCDF in the raw gas.

A second place of PCDD/F formation is the well-known boiler section. Here fly ash deposits containing residual carbon (mainly soot particles) are the source for the formation reaction. Under stationary effective combustion conditions, they are dominant for PCDD/F concentrations in the raw gas over a very long period of time.

Stationary efficient flue gas burnout (especially soot) together with effective boiler cleaning will guaranty low concentrations of PCDD/F in the flue gas in front of the flue gas cleaning system.     

Open burning of household waste: Effect of experimental condition on combustion quality and emission of PCDD, PCDF and PCB

Open burning for waste disposal is, in many countries, the dominant source of polychlorinated dibenzodioxins, dibenzofurans and biphenyls (PCDD/PCDF/PCB) release to the environment. To generate emission factors for open burning, experimental pile burns of about 100 kg of household waste were conducted with emissions sampling. From these experiments and others conducted by the same authors it is found that less compaction of waste or active mixing during the fire - “stirring” - promotes better combustion (as evidenced by lower CO/CO₂ ratio) and reduces emissions of PCDD/PCDF/PCB; an intuitive but previously undemonstrated result. These experiments also support previous results suggesting PCDD/PCDF/PCB generation in open burning - while still highly variable - tends to be greater in the later (smoldering) phases of burning when the CO/CO₂ ratio increases.     

Formation characteristics of PCDD and PCDF during pyrolysis processes

In recent years, pyrolysis processes have become technologies developed to industrial scale and discussed as alternatives to the existing waste combustion technology. However, little information is published regarding PCDD/F formation characteristics during pyrolysis processes. Two common shredder fractions – industrial light shredder (ILS) and refrigerators (REF) – both with high chlorine and copper content were pyrolysed for this pyrolysis study using a pilot plant with a capacity of 100 kg/h. At oxygen concentrations below 2% and temperatures between 430°C and 470°C, considerable amounts of PCDD/F were formed during the pyrolysis. More than 90% of total TEQ was found in the oil fraction (gas phase). The PCDD/PCDF ratio and the homologue pattern differed significantly from those formed during waste incineration. Considering mono- to octachlorinated congeners, up to 400 times more PCDF were formed compared to PCDD. For the investigated pyrolysis conditions, the formation of low chlorinated congeners was highly favoured. The distribution of TEQ within the individual congeners were very similar in all investigated runs. More than 80% of total TEQ stem from 2,3,7,8-substituted T₄CDF and P₅CDF. The isomer pattern, however, did not show significant differences compared to the common waste incineration pattern suggesting that the basic formation routes are similar.     

Intra- and inter- laboratory variability in paper industry PCDD/PCDF analysis

Studies were conducted to quantify variability for pulp industry wastewater effluent, pulp and sludge analyses. Intralaboratory variability studies indicated that there is a potential for greater between batch variability in results than for within a batch. Intralaboratory relative standard deviations for replicate analyses ranged from 6% to 60%. Interlaboratory studies, using standard reference materials showed relative standard deviations from 4% to 135%. There appeared to be little dependance of variability on concentration, suggesting matrix effects were very important. In general, effluent variability was greater than observed for pulps or sludges. Analysis of reference standards indicated that 13% to 17% variability can be attributed to differences in calibration standards. A limited study of full congener PCDD/PCDF analysis variability showed it to be greater than observed for TCDD/TCDF.     

Influence of pesticides contamination on the emission of PCDD/PCDF to the land from open burning of corn straws

Open burning of crop residues has been identified as an important emission source of PCDD/PCDF to the environment. This paper presents the first known data on the emission of PCDD/PCDF to the land considering the influence of pesticides applied in crops planting. Emission factor for PCDD/PCDF to the land from open burning of corn straw with pesticides contamination ranged from 0.07 to 0.57 ng WHO₂₀₀₅-TEQ/kg straw burned with a mean value of 0.24 ng WHO₂₀₀₅-TEQ/kg straw burned and median value of 0.20 ng WHO₂₀₀₅-TEQ/kg straw burned, respectively. The concentration was 35 to 270 times higher than that without additional pesticide contaminated. Initial observation was that emission factor for PCDD/PCDF from open burning of crop residues was overestimated in the former UNEP Dioxin Toolkit. Pesticides contamination should be considered in some hotpots where special and over dosed pesticides has been sprayed especially in developing countries.     

Effects of selected metal oxides on the dechlorination and destruction of PCDD and PCDF

OCDD and OCDF spiked silica/graphite based model fly ash containing various copper compounds and metal oxides were thermally treated under oxygen deficient conditions. All copper compounds tested showed a considerable dechlorination/hydrogenation reaction at 260 °C. After 30 min at 340 °C, less than 1% of the spiked OCDD and OCDF was recovered as T₄CDD/F to OCDD/F. Other compounds tested demonstrated a lower rate of dechlorination compared to the copper compounds. However, all other metal oxides showed a small dechlorination effect at 260 °C, which was considerably increased at 340 °C.

The model fly ash containing the different copper compounds or metal oxides showed comparable PCDD and PCDF isomer patterns after thermal treatment. However, small differences were observed among the different tested compounds. The PCDD and PCDF isomer patterns on the model fly ashes were similar to patterns found during dechlorination experiments on fly ashes from waste incineration processes.

Model fly ash containing Ca(OH)₂ exhibited the highest destruction potential, but a low dechlorination potential. In contrast, model fly ash containing any of the remaining compounds tested, was found to predominantly dechlorinate the spiked OCDD and OCDF.     

Dechlorination and destruction of PCDD,PCDF and PCB on selected fly ash from municipal waste incineration

The potential of fly ash to dechlorinate and destroy PCDD, PCDF and PCB was tested under oxygen deficient conditions in the laboratory. Specifically, two types of fly ash were compared, originating either from a fluidized bed incinerator using Ca(OH)₂ spray (FA1), or a stoker incinerator without Ca(OH)₂ impact (FA2).

Results from the present study indicate that on FA2 type fly ash, the degradation processes of OCDD, OCDF and D₁₀CB occurred primarily via dechlorination/hydrogenation up to temperature settings of 340 °C. In contrast, FA1 type fly ash was found to effect both dechlorination and destruction of these compounds already at temperature settings of 260 °C.

The dechlorination velocity of PCDD and PCDF did not differ significantly. However, the first dechlorination step of OCDF in the 1,9-position occurred faster compared to the first dechlorination step of OCDD.

The isomer pattern resulting from the dechlorination processes was quite similar on both FA1 and FA2, indicating that differences in alkalinity or elemental composition of the two types of fly ashes do not have a significant influence on the position of dechlorination. PCDD and PCDF dechlorination of the 2,3,7,8-positions was not favoured over dechlorination of the 1,4,6,9-positions on either type of fly ash. In contrast, dechlorination of PCB occurred predominantly on the toxicological relevant 3- and 4-positions.

The dechlorination/destruction processes were completed on both types of fly ash at 380 °C within one hour, which correlates well with results obtained from actual plant operation practices.     

Levels and possible sources of PCDD/PCDF in sediment and pike samples from Swedish lakes and rivers. (Part one)

One goal of the Swedish survey project is to discover possible sources of PCDD/F. Bottom sediment and pike were sampled at various sites near different types of industries along the coast line of two lakes and one river. The results show background levels of PCDD/F in some lakes which can only be explained by atmospheric input. In some lakes paper mill emissions of chlorinated PCDD/F give high levels of local contamination (≈1 ng/g IG) within short distances (<1 km) from the source. PCDD/F from paper mill effluents are transported long distances and traces can be detected over the entire lake area. The PCDD/F levels in pike are correlated with levels in the underlying sediment.     

Long-term sampling method for polychlorinated dibenzofurans (PCDFs) and dibenzo(p)dioxins (PCDDs) in flue gas of combustion facilities

A long-term sampling method for PCDF/D in emissions from combustion facilities is presented. The sampling of PCDF/D was performed over a four week period. The results are compared to results of four one-week measurements.     

The role of a steel plant in north-west Italy to the local air concentrations of PCDD/Fs

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are ubiquitous contaminants, mainly released into the environment during combustion processes (point sources), but also from other sources (traffic, uncontrolled combustion).This study aims at investigating the contribution of a steel plant in NW Italy (700 000 tons of steel year⁻¹) to the air concentrations of PCDDs/PCDFs at local level, through the analysis of measured, modelled and literature data. The study was carried out in an area of 600 km², using air quality data measured by the institutional monitoring network, data obtained from AERMOD simulations and literature data.The measured air concentrations were consistent with literature values for similar areas, and both the homologue profiles and PCA analyses showed a clear distinction between the monitoring stations and the source profiles.All the previous results were confirmed by the air dispersion model (AERMOD), that predicted PCDD/F air concentrations due to the steel plant from four to two orders of magnitude lower than those measured in the monitoring stations, highlighting the presence of other sources.This study outlines the limited influence of the source in the local PCDD/F air concentrations and at the same time the usefulness of a joint analysis of measured, literature and calculated data to correctly evaluate the role of a source to the local pollution. The study also highlights the usefulness of AERMOD as a complementary tool to define the correct placement of monitoring stations and to locate those areas expected to have the highest air concentrations deriving from a source.     

Multi-step approach for comparing the local air pollution contributions of conventional and innovative MSW thermo-chemical treatments

In the sector of municipal solid waste management the debate on the performances of conventional and novel thermo-chemical technologies is still relevant. When a plant must be constructed, decision makers often select a technology prior to analyzing the local environmental impact of the available options, as this type of study is generally developed when the design of the plant has been carried out. Additionally, in the literature there is a lack of comparative analyses of the contributions to local air pollution from different technologies. The present study offers a multi-step approach, based on pollutant emission factors and atmospheric dilution coefficients, for a local comparative analysis. With this approach it is possible to check if some assumptions related to the advantages of the novel thermochemical technologies, in terms of local direct impact on air quality, can be applied to municipal solid waste treatment. The selected processes concern combustion, gasification and pyrolysis, alone or in combination. The pollutants considered are both carcinogenic and non-carcinogenic. A case study is presented concerning the location of a plant in an alpine region and its contribution to the local air pollution. Results show that differences among technologies are less than expected. Performances of each technology are discussed in details.     

Environmental monitoring of PCDD/Fs and metals in the vicinity of a cement plant after using sewage sludge as a secondary fuel

In 2005, the partial substitution (20%) of fossil fuel by sewage sludge was tested in a Spanish cement plant. In order to establish the environmental impact for the surroundings, in 2006, the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and heavy metals (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sn, Tl, V, and Zn) were monitored in soil and vegetation samples collected near the cement plant. The temporal trends in the pollutant levels were studied by comparing the concentrations with those obtained in a previous survey (2003) in the same sampling sites. Very slight changes of the PCDD/F concentrations in both monitors were registered in the period 2003–2006 (0.17–0.15 and 0.94–1.10 ng I-TEQ kg⁻¹ dw in herbage and soil, respectively). In turn, there was a notable heterogeneity in the evolution of metal levels, which varied according to each particular element. Anyhow, the current levels of organic and inorganic pollutants are in the low part of the range in comparison with other zones impacted by cement plants, as well as industrial and urban areas worldwide. The human health risks derived from the exposure to PCDD/Fs and metals were also assessed. Although the cancer risks due to PCDD/Fs slightly increased, a reduction of the total carcinogenic risks, including metals, was noted. In conclusion, there were not observed impact changes for the environmental and the local population as a consequence of using sewage sludge as secondary fuel.     

Formation of dioxins from combustion of polyvinylidene chloride in a well-controlled incinerator

Polyvinylidene chloride (PVDC; polymer of 1,1-dichloroethylene) was combusted with paper in a well-controlled, small-scale incinerator at an average grate temperature of 700 °C, and then dioxins (PCDDs, PCDFs, and coplanar-PCBs) formed in the exhaust gases were analyzed by gas chromatography/mass spectrometry. PVDC lowered the combustion temperature due to its less flammable character. The amount of total dioxins (PCDDs + PCDFs + coplanar-PCBs) formed in the exhaust gas was 58.0 ng/g of a combustion sample and its toxicity equivalency quantity (TEQ) value was 0.64 ng-TEQ/g. The amount of PCDDs formed in the sample ranged from 2.33 ng/g (Cl₈-isomer) to 0.048 ng/g (Cl₁-isomer). The lower the number of chloride, the less production of PCDDs. On the other hand, there was no relation between the number of chloride and PCDF formation. The amount of PCDFs formed in the sample ranged from 8.02 ng/g (Cl₂-isomer) to 4.46 ng/g (Cl₈-isomer). A polyvinylchloride (PVC) sample produced 207 ng/g of total dioxins and a PVDC sample produced 57.4 ng/g of total dioxins when they were combusted under the same conditions. An approximately equal composition of dioxin isomers was formed from PVDC and PVC samples. Paper was found to contribute to PCDF formation when it was combusted with plastics.     

The effect of oils on PAH, PCDD, PCDF, and PCB emissions from a spark engine fueled with leaded gasoline

The effect of synthetic and mineral oils on the formation of polyaromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) in emissions from a spark ignition engine was studied on a Skoda Favorit engine fueled with leaded gasoline. The test cycle simulated urban traffic conditions on a chassis dynamometer, in accordance with the ECC 83.00 test. The data for selected PAHs as well as PCDDs, PCDFs, and PCBs congener profiles are presented. PCDD/Fs emissions for an unused oil and the oil after 10000-km operation varied from 300 to 2000 fmol/m3, PCBs emissions from 75 to 178 pmol/m3, and PAHs emissions from 150 to 420 microg/m3. The content of PCBs in oils varied from 2 to 920 mg/kg.     

Correlation of PCDD/PCDF and CO values in a MSW incinerator--indication of memory effects in the high temperature/cooling section

The correlation of PCDD/PCDF levels with the CO emissions in a full-scale municipal waste incinerator was assessed during a four-week measurement effort. PCDD/PCDF concentrations in fly ashes-containing more than 99% of the total PCDD/PCDF burden of the fluidized bed incinerator (FBI)-were measured and compared with the emitted CO concentrations. The CO concentration during the sampling time showed no significant correlation to the PCDD/ PCDF amount in fly ash (R2 = 0.078). However, a comparison of the time integrated CO concentration several hours before sampling lead to a correlation with the PCDD/PCDF burden. Maximum correlation was found for the time integrated CO values of 3 and 4 h before sampling (R2 = 0.467 and R2 = 0.457 respectively). This indicates a memory effect in the high temperature cooling section of several hours. Possible mechanisms leading to the memory effect are discussed. The correlation of PCDD/PCDF with CO concentration demonstrate that the combustion conditions play an important role for PCDD/PCDF formation in FBIs. However the variability in the correlation of CO to PCDD/PCDF levels show that other factors have a significant influence on PCDD/PCDF formation.     

Experimental evaluation of PCDD/Fs and PCBs release and mass balance of a WTE plant

The behaviour of waste incineration plants with respect to organic toxic trace contaminants such as PCDDs, PCDFs and, to a minor extent, PCBs, is still a matter of concern for the public opinion and the decision makers. It is therefore very important, first, to evaluate the release of these organic toxic trace contaminants in the environment during waste incineration, not only through the stack gas emission but also with the solid and liquid residues, and then to compare the total release with the input through the treated waste in order to assess the plant behaviour as a “sink” rather than a “source” of organic toxic trace contaminants. The experimental investigation carried out on an Italian full scale incineration plant has shown a total 17 PCDD/Fs and 12 dioxin-like PCBs release of 5.5-27 μg WHO-TEQ per tonne of treated waste and an input flux of 1.6-44 μg WHO-TEQ per tonne of waste, with the difference between the input and the output fluxes rather small and the plant behaviour toward organic trace toxic contaminants in average neutral. Results are compared with similar evaluations conducted in the last decade on a number of waste-to-energy (WTE) plants operating in Italy.     

二次风喷嘴角度对炉排式垃圾焚烧炉内燃烧及选择性非催化还原脱硝的影响

利用CFD技术,对某城市处理量为750 t·d-1的垃圾焚烧炉内燃烧与选择性非催化还原脱硝（SNCR）过程进行建模分析,重点研究了二次风喷嘴角度的改变对焚烧炉内燃烧温度场的影响及其对提高SNCR脱硝效率的作用。模拟结果表明,焚烧炉二次风喷嘴角度调整为相互交叉45°,可以改善炉内燃烧状况,促进炉膛内烟气与空气的混合,使炉膛内温度场分布均匀,有利于SNCR还原反应;二次风喷嘴角度改变后,在一定程度上保证了SNCR系统喷入的尿素液滴在炉膛内的停留时间。与平行二次风相比,使用交叉二次风送风方案,前墙喷嘴脱硝效率提高4.8%,后墙喷嘴脱硝效率提高了19.7%。