Source identification of PCDD/Fs in agricultural soils near to a Chinese MSWI plant through isomer-specific data analysis

Isomer-specific data were investigated in order to identify the sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in agricultural soils, including Fluvo-aquic and paddy soils, in the vicinity of a Chinese municipal solid waste incineration (MSWI) plant. Homologue and isomer profiles of PCDD/Fs in soils were compared with those of potential sources, including combustion sources, i.e., MSWI flue gas and fly ash; and the impurities in agrochemicals, such as the pentachlorophenol (PCP), sodium pentachlorophenate (PCP-Na) and 1,3,5-trichloro-2-(4-nitrophenoxy) benzene (CNP). The results showed that the PCDD/F isomer profiles of combustion sources and agricultural soils were very similar, especially for PCDFs, although their homologue profiles varied, indicating that all the isomers within each homologue behave identically in the air and soil. Moreover, factor analysis of the isomer compositions among 33 soil samples revealed that the contamination of PCDD/Fs in agricultural soils near the MSWI plant were primarily influenced by the combustion sources, followed by the PCP/PCP-Na and CNP sources. This implication is consistent with our previous findings based on chemometric analysis of homologue profiles of soil and flue gas samples, and identifies PCP/PCP-Na as an additional important source of PCDD/Fs in the local area. This makes the similarities and differences of isomer profiles between Fluvo-aquic and paddy soils more explainable. It is, therefore, advisable to use isomer-specific data for PCDD/F source identifications where possible.     

Investigation on organic pollutants from a domestic heating system using various solid biofuels

Various herbaceous biofuels (straw, whole plant cereals and set aside hay) and spruce wood were tested for their potential to form PCDD/F, PCPh, PCBz and PAH during combustion. The trials were conducted in an automatically charged multi-fuel furnace for domestic applications (50 kWth). Both, flue gas and the different ash fractions were analysed. CO-emission results show, that combustion conditions were relatively uniform (mean CO-level: 200 mg/m3 at 13% O2 in flue gas). Likewise, the TOC- and PAH-emissions in the fuel gas remained constantly on a relatively low level. However, for the PCDD/F, PCPh and PCBz increased emissions were detected when herbacious fuels were applied. This may be attributed to their higher chlorine concentration and the high ash content, which is responsible for increased dust emissions during combustion. Similar observations were also found for the PCDD/F-concentrations in the ashes. Combustion chamber ashes usually showed a drastically reduced contamination with highly toxical compounds, compared to the ash fraction from the heat exchanger ash or to chimney soot.     

Experimental and statistical determination of indicator parameters for the evaluation of fly ash and boiler ash PCDD/PCDF concentration from municipal solid waste incinerators

On-line detectable indicator parameters in the flue gas of municipal solid waste incinerators (MSWI) such as chlorinated benzenes (PCBz) are well known surrogate compounds for gas-phase PCDD/PCDF concentration. In the here presented work derivation of indicators is broadened to the detection of fly and boiler ash fractions with increased PCDD/PCDF content. Subsequently these fractions could be subject to further treatment such as recirculation in the combustion chamber to destroy their PCDD/PCDF and other organic pollutants' content. Aim of this work was to detect suitable on-line detectable indicator parameters in the gas phase, which are well correlated to PCDD/PCDF concentration in the solid residues. For this, solid residues and gas-phase samples were taken at three MSWI plants in Bavaria. Analysis of the ash content from different plants yielded a broad variation range of PCDD/PCDF concentrations especially after disturbed combustion conditions. Even during normal operation conditions significantly increased PCDD/PCDF concentrations may occur after unanticipated disturbances. Statistical evaluation of gas phase and ash measurements was carried out by means of principal component analysis, uni- and multivariate correlation analysis. Surprisingly, well known indicators for gas-phase PCDD/PCDF concentration such as polychlorinated benzenes and phenols proved to be insufficiently correlated to PCDD/PCDF content of the solid residues. Moreover, no single parameter alone was found appropriate to describe the PCDD/PCDF content of fly and boiler ashes. On the other hand, multivariate fitting of three or four parameters yielded convenient correlation coefficients of at least r=0.8 for every investigated case. Thereby, comprehension of plant operation parameters such as temperatures and air flow alongside concentrations of inorganic compounds in the gas phase (HCl, CO, SO2, NOx) gave the best results. However, the suitable set of parameters suited best for estimation of PCDD/PCDF concentration in solid residues has to be derived anew for each individual plant and type of ash.     

Formation of aromatic chlorinated compounds catalyzed by copper and iron

This study shows the catalyzing effects of iron and copper on the formation of chlorinated compounds such as chlorobenzenes (ClBzs), chlorophenols (CIPhs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Both total concentrations and congener distributions have been studied. The parameters and conditions varied during the combustion tests were the complete and incomplete combustion and the metal and chlorine addition. The incomplete combustion promoted the formation of organic chlorinated compounds in flue gas particles. Highly chlorinated congeners of PCDD/F were dominant in the flue gas particles, whereas the importance of lower chlorinated congener were increased in the gas phase. In the complete combustion conditions the concentrations of PCDD/Fs increased when the degree of chlorination were high, nevertheless the concentrations of tetra and penta PCDD/Fs were higher in the gas phase than the concentrations in the fly ash particles. Organic chlorine promoted the formation of chlorinated compounds more effectively than inorganic chlorine, which instead promoted the formation of PCDD/Fs in the gas phase, especially with copper catalyst. Different concentration levels of chlorinated compounds were observed in the gas phase and in particles when the chlorine source and combustion conditions were varied from incomplete to optimum conditions. Both copper and iron seem to have a catalytic effect on PCDD/F formation.     

NOx Reduction in a Gas Fired Utility Boiler by Combustion Modifications

Data on the effect of several combustion modifications on the formation of nitrogen oxides and on boiler efficiency were acquired and analyzed for a 110 MW gas fired utility boiler. The results from the study showed that decreasing the oxygen in the flue gas from 2.2% to 0.6% reduced the NO_x formation by 33% and also gave better boiler efficiencies. Flue gas recirculation through the bottom of the firebox was found to be ineffective. Staged combustion was found to reduce the NO_x emissions by as much as 55 % while decreasing the efficiency by about 5%. Adjustment of the burner air registers reduced the NO_x formation by about 20 ppm. The lowest NO_x emissions of 42 ppm (at about 3% O₂) in the stack was obtained for air only to one top burner and 0.5% oxygen in the flue gas.     

Determination of polychlorinated dibenzo-p-dioxins and dibenzo-furans in solid residues from wood combustion by HRGC/HRMS

PCDD/PCDF were determined in solid samples from wood combustion. The samples included grate ashes, bottom ashes, furnace ashes as well as fly and cyclone ashes. The solid waste samples were classified into bottom and fly ash from native wood and bottom and fly ash from waste wood. For each of the four classes concentration distribution patterns from individual congeners, the sums of PCDD/PCDF and the international toxicity equivalents (I-TEQ) values are given. The I-TEQ levels of fly ash from waste wood burning can be approximately up to two thousand times higher than the values from fly ashes of natural wood. The I-TEQ levels in bottom ashes from waste wood combustion systems are as low as the corresponding ashes from the combustion of native wood. Grate ash samples from waste wood combustion systems with low carbon burnout show high levels of PCDD/PCDF.     

Dioxins/furans emissions from fluidized bed combustion of salt-laden hog fuel

Polychlorinated dibenzodioxins/furans (PCDD/F) were formed in substantial quantities in a pilot-scale fluidized bed combustor burning salt-laden waste wood, a common fuel for Canadian coastal pulp and paper mills. Formation of PCDD/F increased with increasing chloride content in the feed, and appeared to correlate with the chlorine content in the fly ash. It took a very long time for the ash chlorine content to stabilize, suggesting that chlorine transferred slowly from the flue gas to the ash. The baghouse may contribute largely to formation of the PCDD/F, owing to its temperature range and the potentially long residence time for ash particles. Controlling the baghouse temperature to reduce the PCDD/F formation in the baghouse should be effective in reducing the total emission level. While sulphur addition was found to reduce the emission level by as much as 90%, the emission level was still above the regulated level for the mills burning salt-laden wood under the conditions of the present study. No relation between the emission level and CO concentration in the flue gas was observed.     

Formation of PCDD/PCDF

One option of recycling used contaminated packaging is to recover its high energy content. This can be performed in a normal multi-fuel power plant by co-combustion of packaging-derived fuel (PDF) or refuse-derived fuel (RDF) with fossil fuels, such as coal or peat. This work includes the results of 17 co-combustion tests and an evaluation of the results by the Principal Component Analysis (PCA) and the Partial Least Squares Projections to Latent Structures (PLS). PCA and PLS calculations showed that especially Pb, but also Cr, and Cu correlated with lower chlorinated furans (PCDFs) in the fly ash. Correlation between Sn and lower chlorinated dioxins (PCDDs) in the fly ash was also noticed. CO and PAH emission in the flue gas correlated with total PCDD/Fs in the flue gas. In a real full-scale combustion process, a single parameter in fuel, flue gas or a combustion parameter did not provide a guide to PCDD/F formation or to a level of the total PCDD/F emission, but correlations between different parameters and PCDD/Fs could be found. Although PDFs and RDF had catalytic heavy metals and chlorine, the co-combustion results showed that they can be co-combusted with peat and coal in a fluidized-bed boiler at least up to 26 % with very low total PCDD and PCDF emissions.     

A case study of dioxin monitoring in and around an industrial waste incinerator in Korea

Many studies have been conducted that monitor and trace the sources of polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) by comparing congener patterns of environmental samples with those of possible sources. In this study, we measured PCDD/F concentrations and compared congener patterns of samples of various media found in and around an industrial waste incinerator in Korea, including stack gas, fly ash, bottom ash, ambient air, soil, pine needle, and human blood. We obtained reliable data on the relationship between the PCDD/F distributions in these sources and the environment, and thus found indicators with which to assess the impact of such sources on the surrounding environment. In addition, the difference between the levels of PCDD/Fs in the blood of short-term workers and long-term workers demonstrates that these workers are exposed to the compounds produced by the indicator.     

Levels and characteristic homologue patterns of polychlorinated dibenzo-p-dioxins and dibenzofurans in various incinerator emissions and in air collected near an incinerator

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were monitored in stack gas and fly ash of various Korean incinerators and in air samples collected near the facilities. Concentrations of PCDD/Fs in emissions were investigated, and characteristic PCDD/F homologue patterns were classified using statistical analyses. The PCDD/F emission levels in stack gas and fly ash samples from small incinerators (SIs) were higher than those from municipal solid waste incinerators (MSWIs). The PCDD/F concentrations ranged between 0.38 and 1.16 pg I-TEQ/m3 (21.2-75.2 pg/m3) in ambient air samples. The lower-chlorinated furans were the dominant components in most of the stack gas and fly ash samples from SIs, although this was not the case for fly ash from MSWIs. This homologue pattern is consistent with other studies reporting a high fraction of lower-chlorinated furans in most environmental samples affected by incinerator emissions, and it can be used as an indicator to assess the impact of such facilities on the surrounding environment.     

Environmental release and mass flux partitioning of PCDD/Fs during normal and transient operation of full scale waste to energy plants

The paper reports on global release and mass partitioning in the flux of residues of PCDD/Fs, evaluated with dedicated field campaigns at a municipal solid waste incineration plant during normal and transient operation. Results are compared with those obtained in other installations equipped with furnaces, energy recovery options and flue gas treatment technologies representative of most of the European incineration plants currently in operation. Levels of the pollutants of interest were determined in all the solid, liquid and gaseous residues produced by every single facility, and the results analysed in terms of the effects arising from the fed waste and the configuration of the plant. PCDD/Fs total release between 1.5 and 45 microg I-TEQ per ton of burned waste was evaluated, with lower values resulting from the adoption of catalytic conversion process for flue gas treatment. Most of the mass flux emitted is associated with solid residues deriving from activated carbon PCCD/F dry removal options, with significant contributions also from fly ash produced by particulate removal devices located immediately downstream the boiler and from scrubber blowdowns treatment sludge. During transient operating conditions the dioxin total release may increase by 50% with comparison to steady-state functioning.     

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.     

Generation of PCDD/F in Fly Ash from Municipal Solid Waste Incinerators

Abstract

Fly ash from municipal solid waste incinerators (MSWIs) has been characterized in terms of polychlorinated dibenzyl-p-dioxin and polychlorinated dibenzofuran (PCDD/F) content. Increasing values of PCDD/Fs have been found to correlate with decreasing temperatures of sampling points in flue gas treatment lines of the plants, confirming other researchers’ findings about temperature as the major controlling parameter for the PCDD/F formation. Measured PCDD/F ratios show that de novo synthesis is the dominant formation mechanism. The increasing trends of particulate-bound PCDD/Fs can be explained not only through the dominant de novo synthesis process but also considering the adsorption of gaseous PCDD/Fs on fly ash deposits, even outside the typical de novo synthesis temperature ranges. The effective role of a post-combustor unit, imposed by Italian law to destroy PCDD/Fs, also needs to be carefully reconsidered.     

Effect of liquid inhibitors on PCDD/F formation. Prediction of particle-phase PCDD/F concentrations using PLS modelling with gas-phase chlorophenol concentrations as independent variables

Emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from municipal waste incineration are currently a subject of considerable public concern because of their extreme toxicity. PCDD/F formation in incineration processes is being studied widely, but little work has been done on their inhibition. We studied the effect of two liquid inhibitors, sodium ammonium hydrogen phosphate (NAHF) and urea (H2NCONH2), on PCDD/F formation in the combustion of liquid fuel doped with copper and chlorine using a pilot-scale plant. The inhibitors were injected into the flue gas stream at a temperature of 725 degrees C, whereupon both the chlorophenol and PCDD/F concentrations decreased. Particle-phase PCDD/F concentrations in particular decreased by up to 90% with NAHF and 70% with urea, but gas phase reduction took place only with urea. The results suggest that the formation of PCDD/Fs is hindered in the particle phase at the early stages of the PCDD/F formation chain, probably even before precursors such as chlorophenols have been formed. As a consequence, particle-phase PCDD/F concentrations can be predicted by a PLS (partial least-squares) approach with the gas-phase chlorophenol concentrations as independent variables. The structure and partial charges of Cu(+)-urea complex were calculated by the HF/3-21G basis set.     

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.     

Melting and incineration plants of municipal waste. Chemical and biochemical diagnosis of thermal processing samples (emission,residues)

Control of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in emissions and thermal residues from incinerators has been a cause of public concern for more than one decade. Recently, several studies showed that other persistent organic pollutants (POPs) such as coplanar polychlorinated biphenyls (co-PCBs) also have dioxin-like activity and are released from incinerators. Therefore, the present study was aimed at making a risk assessment about dioxin-like activity in extracts of thermal waste residues (e.g. combustion gas; fly ash, slag) from incineration and melting processes in Germany and Japan. For this purpose, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (co-PCBs), polychlorinated naphthalenes (PCNs) and polyaromatic hydrocarbons (PAHs) were analyzed by chemical analysis. Additionally, 2, 3, 7, 8-TCDD equivalents (EROD-TEQs) were determined by in vitro Micro-EROD bioassay using rat H4IIE hepatoma cells. EROD-TEQs could be correlated to I-TEQ values (from PCDD/Fs/co-PCBs) analyzed by chemical analysis resulting in a maximal sixfold higher estimate. Our study indicates minor influences of co-PCBs, PAHs and PCNs to the sum of dioxin-like toxicity in the extracts of thermal waste residues as determined here. Furthermore, we showed that the levels of dioxins and co-PCBs contained in slag from melting processes and bottom ashes from incineration processes were lower by 1-2 orders of magnitude than that in fly ash.     

Assessment of PCDD/F risk after implementation of emission reduction at a MSWI

Municipal solid waste incinerators (MSWIs) have been shown to be important sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The emission of PCDD/Fs by MSWIs is a controversial subject in human health risk assessment. In this study the effect of a MSWI on a residential area was assessed before and after the installation of an additional treatment system for flue gas. This additional treatment system resulted in a dramatic decrease in PCDD/F concentrations in stack flue gas samples by 99.98%, while the concentrations in air decreased by approximately 50% (36,500 and 0.75 pg I-TEQ m(-3) for air in 1999; 3.5 and 0.38 pg I-TEQ m(-3) in 2002; 1.6 and 0.076 pg I-TEQ m(-3) in 2005 for stack gas and air, respectively). Considering the congener distributions of PCDD/Fs between stack flue gas and air samples, the study area seemed to have been contaminated by other urban sources as well as the MSWI. ISC3 model results support the conclusion that this incinerator became only a minor contributor to the study area after installation of the supplementary systems. This resulted from both proper MSWI operation using modern technology and additional sources of contaminants in this region. Finally, PCDD/F uptake by humans through inhalation of contaminated air was estimated. Assuming that inhalation exposure contributes 10% of total exposure, total exposure was lower than WHO guidelines. These results confirm that proper operation and maintenance of the incinerator led to a reduction in emissions and potential health impacts of PCDD/Fs.     

PCDD/F mass balance in the flue gas cleaning units of a MSW incineration plant

With the main purpose of evaluating PCDD/F presence and the corresponding mass balance over the emissions control system, an extensive study was performed on a municipal solid waste full scale incinerator equipped with a best available technology flue gas treatment line. Present paper reports the main results obtained, with particular reference to the PCDD/F concentration profiles and mass balances derived for every process unit of the flue gas control system. Total release evaluated for the plant is also outlined compared with data on PCDD/F content of raw waste and with reference values included in most recent guidelines.     

PCDD/PCDF emissions from small firing systems in households

This report presents results of emission measurements of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in the flue gas of seven oil, nine gas, and two wood firing systems under laboratory conditions. The burn rate of the combustion was in the range of the rated useful heat output. Two additional test series varied the amount of combustion air and thus the heat output. The PCDD/PCDF emissions for oil- and gas-fired boilers are in the range of 0.0020-0.0142 ng I-TEQ/m3 (referring to 3% O2 in the dry flue gas). No correlation between the combustion technique and the PCDD/PCDF emissions could be established. In the tests with the wood-fired furnaces PCDD/PCDF concentrations in the flue gas ranging from 0.014 to 0.076 ng I-TEQ/m3 (referring to 13% O2 in the dry flue gas) were found. A significant correlation between the firing rate of the heating insert and the measured PCDD/PCDF concentrations was found. On examination of three typical 2,3,7,8-CDD/CDF congener profiles, a comparable pattern could be observed with natural gas and light fuel oil. The congener distribution for wood combustion is considerably different.     

Nitrogen oxides emissions from the MILD combustion with the conditions of recirculation gas

The nitrogen oxides (NO_x) reduction technology by combustion modification which has economic benefits as a method of controlling NO_x emitted in the combustion process, has recently been receiving a lot of attention. Especially, the moderate or intense low oxygen dilution (MILD) combustion which applied high temperature flue gas recirculation has been confirmed for its effectiveness with regard to solid fuel as well. MILD combustion is affected by the flue gas recirculation ratio and the composition of recirculation gas, so its NO_x reduction efficiency is determined by them. In order to investigate the influence of factors which determine the reduction efficiency of NO_x in MILD coal combustion, this study changed the flow rate and concentration of nitrogen (N₂), carbon dioxide (CO₂) and steam (H₂O) which simulate the recirculation gas during the MILD coal combustion using our lab-scale drop tube furnace and performed the combustion experiment. As a result, its influence by the composition of recirculation gas was insignificant and it was shown that flue gas recirculation ratio influences the change of NO_x concentration greatly. Implications: We investigated the influence of factors determining the nitrogen oxides (NO_x) reduction efficiency in MILD coal combustion, which applied high-temperature flue gas recirculation. Using a lab-scale drop tube furnace and simulated recirculation gas, we conducted combustion testing changing the recirculation gas conditions. We found that the flue gas recirculation ratio influences the reduction of NO_x emissions the most.