Long-term automated sampling of PCDD/PCDF flue gas: current status and critical issues

After entry into force of the Stockholm Convention and Aarhus Protocol and in order to implement the upcoming European legal background, the European countries are asked to apply control measures to reduce the release of persistent organic pollutants (POPs) such as dioxins and furans (PCDD/PCDF) and polychlorinated biphenyls as well as to establish POPs release inventories. In this perspective, development of measuring techniques of emissions is a focal issue in acquiring useful information. In this paper, results of various measurement campaigns at different municipal waste incineration (MWI) plants using long-term automated sampling of PCDD/PCDF are presented. The samples collected from both manual and automated campaigns were analyzed following the European Standard EN-1948:2006 by high-resolution gas chromatograph/high-resolution mass spectrometer. Performances of two different commercial systems have been investigated. Anomalous values occurred during one long-term campaign (22.16 pg I-toxic equivalent (TEQ)/Nm(3)), compared to average values (4-5 pg I-TEQ/Nm(3)) of the MWI. At this maximum value, a main occurrence of abnormal and instable operating conditions has been found. Sampling based on long-term basis was found to be more reliable to monitor PCDD/PCDF emissions than occasional short-term sampling. Nevertheless, the results of long-term campaigns demonstrate that emission levels detected in 15-30 days campaigns, when unsteady operating conditions can occur, as start-up and shut down, are not immediately comparable to the typical levels in a 6-8 h, when operating conditions are generally stable. Moreover, there are often differences observed in the congener profiles between short- and long-term campaigns.     

Search for industrial sources of PCDD/PCDFs: II. Metal chlorides

FeCl₃, AlCl₃, CuCl₂, CuCl, SiCl₄ and TiCl₄ were analysed for their content of PCDD/PCDFs and other chloroaromatic compounds. FeCl₃ and AlCl₃ contain OCDF and H₇CDF in ppb- and hexachlorobenzene in ppm-range; CuCl₂ and CuCl contain lower concentrations of OCDF, H₇CDF and additionally OCDD, H₇CDD and hexachlorobenzene in ppb/ppt-range. SiCl₄ and TiCl₄ contain no measurable quantities of PCDD/PCDFs and hexachlorobenzene. A correlation between the PCDD/PCDF - and hexachlorobenzene-content is postulated for products of industrial sytheses involving high temperatures. The origin of the organic substances in a process of inorganic chemistry could be oils on the waste metals which are used in the manufacture of metal chlorides.     

Certification of a long-term sampling system for PCDFs and PCDDs in the flue gas from industrial facilities

AMESA (adsorption method for sampling of dioxins) is a fully automatic system for long term monitoring of dioxin emissions from industrial processes based on the adsorption method. The system has been tested and undergoing a certification procedure according to the German guidelines for certification of systems for continuous monitoring of special substances. The certification covered parameters such as disposability of the system, reproducibility of the results and comparability of the sampling method with German and European standard methods. Furthermore break through, blanks and sample storability were investigated. The results prove that AMESA is a state of the art sampling system for continuous monitoring of dioxin/furan emissions.     

Accurate sampling of PCDD/F in high temperature flue-gas using cooled sampling probes

In a laboratory-scale combustion reactor, flue-gas samples were collected at two temperatures in the post-combustion zone, 700 °C and 400 °C, using two different water-cooled sampling probes. The probes were the cooled probe described in the European Standard method EN-1948:1, referred to as the original probe, and a modified probe that contained a salt/ice mixture to assist the cooling, referred to as the sub-zero probe. To determine the efficiency of the cooling probes, internal temperature measurements were recorded at 5 cm intervals inside the probes. Flue-gas samples were analyzed for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs). Samples collected at 700 °C using the original cooling probe showed higher concentrations of PCDD/Fs compared to samples collected using the sub-zero probe. No significant differences were observed between samples collected at 400 °C. The results indicated that artifact formation of PCDD/Fs readily occurs during flue-gas sampling at high temperatures if the cooling within the probe is insufficient, as found for the original probe at 700 °C. It was also shown that this problem could be alleviated by using probes with an enhanced cooling capacity, such as the sub-zero probe.Although this may not affect samples collected for regulatory purposes in exit gases, it is of great importance for research conducted in the high-temperature region of the post-combustion zone.     

The effects of temperature and oxygen content on the PCDD/PCDFs formation in MSW fly ash

In this study, the effects of the temperature, oxygen content in the gas stream and carbon content in ash particles on PCDD/Fs formation on the fly ash surface were investigated. The optimum temperatures for dioxin formation were found at 350 degrees C for boiler ash, 300 degrees C for cyclone ash and 250 degrees C for ESP ash, respectively. Preliminary results indicate that the optimum temperature will decrease as the particle size decreases. When the O2 concentration is varied between 0% and 100%, the optimum oxygen content for PCDD/Fs formation is found to be at 7.5% for cyclone ash, and the PCDD/PCDF ratio increases with the increase of oxygen content. Dioxin formation is observed even for the gas containing no oxygen passed through the fly ash. Hence, other reacted routes that do not need O2 for dioxin formation take place on fly ash. The carbon content in fly ash is varied between 0% and 20% in this study, and the results have indicated that the maximum dioxin formation is to be found at 5%. The precursors are not injected into the fly ash or gas stream in all formation experiments, however, dioxin is still formed in fly ash. Consequently, other chlorinated routes besides Deacon reactions may take place on the fly ash surface.     

A comparison of PCDD/PCDFs exposure in infants via formula milk or breast milk feeding

Food is the major source for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) accumulation in human body. In infant period, breast milk and formula milk are the major food sources. Congener-specific analyses of 17 PCDD/PCDFs were performed on 10 brands of formula milk samples which were milk-based and 37 breast milk samples collected from women living in southern Taiwan. The levels of 17 PCDD/PCDFs in 10 formula milk samples ranged from 0.468 to 0.962 pg WHO-TEQ/g lipid, with a mean value of 0.713+/-0.163 pg WHO-TEQ/g lipid. For the 37 breast milk samples, their PCDD/PCDF levels were 14.7+/-9.36 pg WHO-TEQ/g lipid, with a range between 4.21 and 52.8 pg WHO-TEQ/g lipid. At 12th month of age for infants, average daily intakes (ADI) of PCDD/PCDFs were 2.1 pg WHO-TEQ/kg/day for the formula-feeding infants, and 13 pg WHO-TEQ/kg/day for the breast-feeding infants. The present data may provide useful information for risk-benefit evaluation of formula- and breast-feeding.     

Air-vegetation transfer of PCDD/PCDFs: an assessment of field data and implications for modeling

This study was designed to evaluate soil and air (gas and particle) transfer of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to vegetation in residential and industrial areas. In a first part, soil-vegetation transfer was assessed. The levels of PCDD/Fs in 120 soil and 120 herbage samples collected from 1996 to 2002 in an industrial area of Montcada (Barcelona, Spain), near a municipal solid waste incinerator (MSWI), were determined. Some additional individual samples were also evaluated. It was concluded that high soil concentrations, which are not at steady state with the air layer above it, show a tendency for PCDD/Fs to escape via volatilization. In a second part of the study, air-vegetation transfer was examined. PCDD/F concentrations from 24 herbage samples were used, while PCDD/F concentrations were also measured in seven high-volume air samples and seven passive air-vapor samples. Scavenging coefficients (m3 air "sampled"/g grass d.m.) ranged from 1.9 to 11.3 m3/g. A good trend with K(OA) was observed for PCDDs (R=0.82), while it was lower for PCDFs (R=0.55). The current results corroborate that PCDD/F concentrations in vegetation are associated with atmospheric deposition. For the highest substituted PCDD/F congeners, the air-particle uptake from plants is the principal pathway. In regions impacted by combustion emission sources, PCDD/F gas-particle partitioning is influenced by a higher concentration of particles in the air. Particles and associated particle-bound PCDD/Fs would sorb to leaf surfaces, and are subject to removal via wash off. However, in areas where emissions to air are not very notable, vapor absorption would be the principal source of vegetation pollution. The results of this investigation can have a potential interest in risk assessment studies and environmental fate models.     

Patterns of PCBs and PCDD/PCDFs in chicken and pork fat following a Belgian food contamination incident

A food contamination incident involving polychlorobiphenyls (PCBs) and PCDD/Fs occurred in 1999 in Belgium. On heavily affected farms, concentrations of PCBs in chicken or pork fat exceeded the Belgium tolerance limit of 200 ng/g lipid weight for the sum of seven marker PCBs. Analysis of contaminated samples showed that the patterns for PCB and PCDD/F congeners differed among feed, chicken fat and pork fat. Lower chlorinated PCBs and polychlorodibenzofurans (PCDFs) including those with high TEFs (PCBs 105, 118, 126 and 2,3,4,7,8-PeCDF) were shown to either bioaccumulate more in chicken fat or to be eliminated more readily in pork. This leads to the possibility that consumption of chicken would result in a higher TEQ human body burden than that from the same consumption of pork. In addition, PCDF congeners with non-2,3,7,8-substitution (e.g., 1,2,4,7,8-PeCDF) were present in chicken fat but absent in pork fat. Since the residue pattern in this commercial episode changes less in the avian species, these results reinforce the value of birds rather than mammals as markers of the source of contamination with persistent organochlorine pollutants.     

Evaluation of PCDD/Fs patterns emitted from incinerator via direct ambient sampling and indirect serum levels assessment of Taiwanese

The aim of this study was to evaluate the PCDD/Fs patterns in ambient air based on data information emitted from incinerator generated from ambient air measurements and those in serum. Four circular zones, namely A, B, C, and D, were identified based on simulated ambient annual average PCDD/Fs concentrations, from a selected municipal waste incinerator. Sixteen ambient samples were taken from the 4 circular zones across 4-seasons. Eighty-nine volunteers were recruited according to the demographic distribution within each zone. PCDD/Fs profiles were documented both for air and serum samples collected. Comparing to the congener patterns from ambient air and serum samples, we found that OCDD, OCDF, 1,2,3,4,6,7,8-HpCDD, and 1,2,3,4,6,7,8-HpCDF were the predominant groups among 17 congeners from both the ambient air and serum sample. And, factor analysis showed the distribution patterns of PCDD/Fs from ambient air and serum samples are almost identical across different zones, except for congener patterns of serum samples from residents in zone C. In addition, the average PCDD/Fs level significantly reduced for about 10 folds than those of the other three seasons when the incinerator was shut down in one of sampling periods. We might conclude that ambient air exposure was the most important contributor to PCDD/Fs levels in ambient air but not the single in serum. Therefore, another or more powerful source, such as occupational exposure, dietary intake or the consumption of local food, should be further investigated at the same time.     

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.     

Concentrations of PCDD/PCDFs in plasma of subjects living in the vicinity of a hazardous waste incinerator: follow-up and modeling validation

In 2007, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs) were determined in plasma of non-occupationally exposed subjects living near the only hazardous waste incinerator (HWI) in Spain (Constantí, Tarragona County, Catalonia). These data were compared with the levels found in two previous surveys performed in 1998 (baseline) and 2002. The current mean PCDD/PCDF concentration in plasma was 9.36pg I-TEQg(-1) of lipid (range: 1.76-23.44pg I-TEQg(-1) of lipid). It means a significant reduction of the mean PCDD/PCDFs levels in plasma in comparison to the concentrations found in 1998 and 2002 (27.01 and 15.70pg I-TEQg(-1) of lipid, respectively). This important decrease agrees well with the notable reduction in the dietary intake of PCDD/PCDFs recently noted for the population of the same area (210.1pg I-TEQd(-1), 63.8pgWHO-TEQd(-1), and 27.8pgWHO-TEQd(-1), in 1998, 2002 and 2007, respectively). The current data were also used to predict theoretical PCDD/PCDF concentrations in plasma by executing a single-compartment empirically-based pharmacokinetic model on the basis of the daily intake of these pollutants by the local population.     

Atmospheric deposition of PCDD/Fs measured via automated and traditional samplers in Northern Taiwan

Most polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the atmosphere are bound to particles which are suspended in the atmosphere, and eventually settle on soil, vegetation, water bodies or other receptors in the environment. Monitoring atmospheric deposition fluxes (dry/wet) is important in tracing the environmental fate and behavior of PCDD/Fs. PCDD/F depositions were collected via an automated PCDD/F ambient sampler and traditional cylindrical vessels, respectively, from April 2007 to February 2008. The automated PCDD/F ambient sampler used in this study can prevent both re-suspension and photo degradation of the PCDD/Fs collected and effectively separates the PCDD/F samples into dry and wet contributions. The results indicated that the ambient PCDD/F concentrations collected using the PS-1 sampler ranged from 0.02 pg I-TEQ/m³ to 0.16 pg I-TEQ/m³ in Northern Taiwan. The results also indicated that the PCDD/F deposition flux collected using the automated PCDD/F sampler (17.5 pg I-TEQ/m² d to 25.8 pg I-TEQ/m² d) was significantly higher than that sampled with the cylindrical vessels (2.0 pg I-TEQ/m² d to 9.9 pg I-TEQ/m² d). The difference was attributed to the fact that part of the PCDD/F depositions collected using the traditional cylindrical vessels had undergone photo degradation and evaporation. In addition, the wet deposition flux of PCDD/Fs (39.4 pg I-TEQ/m² rainy day to 228 pg I-TEQ/m² rainy day) observed in this study was significantly higher than the dry deposition flux (12.3 pg I-TEQ/m² sunny day to 16.7 pg I-TEQ/m² sunny day). These results demonstrated that wet deposition is the major PCDD/F removal mechanism in the atmosphere.     

Studies on sampling methods for PCDDs and PCDFs in stack emission

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in stack emission exist both as vapor and sorbed onto the surface of particles. The partition between the two phases is of a dynamic nature and changes rapidly with temperature. When monitoring stack emissions, a sampling method must be used that efficiently collects both phases as well as any condensation aerosol formed in the sampling train. In this study, the two sampling methods used in Sweden, the cooled probe polyurethane foam plug (PUFP) sampling train and the sampling train recommended by the Swedish Environmental Protection Board has been tested for particle collection ability. The results show that an aerosol filter has to be introduced after the condensor in order to collect particle bound PCDDs and PCDFs efficiently.     

Comparison of various sampling methods for PCDDs and PCDFs in stack gas

There have been discussions about how complete PCDDs and PCDFs are sampled from stack gas of waste combustion plants by various sampling methods. In Germany, at present, a sampling method is used, which was first proposed by Nottrodt et al.¹, consisting of a filter device, condenser, and an absorption train. Since this sampling procedure complicates sampling and analysis, we compared this “standard procedure” with a “dilution method”, where only a filter, impregnated with paraffin, is used as trapping device, and also tested the effectiveness of XAD-2 as an adsorption trap.

As standard procedure the standard train was always used in parallel to other sampling methods. The results of four parallel sampling periods confirmed, that comparable results are obtained, when parallel sampling is carried out with the standard train.

The result of our investigation can be summarized as follows: The total emission of PCDDs and PCDFs determined by different sampling procedures varies only insignificantly. This means that sampling and analysis for PCDDs and PCDFs in stack gas could be simplified considerably.     

Evaluation of PCDD/F pollution in surface sediments of Izmit Bay

This study evaluates PCDD/F pollution in the surface sediments of Izmit Bay (Turkey) and assesses the possible sources of PCDD/F inputs to the bay. The results showed that concentrations of toxic PCDD/F congeners in the sediments varied between 0.45 and 255 ng WHO₂₀₀₅-TEQ/kg dry weight. Pollution mapping shows that PCDD/F levels in the central section of Izmit Bay are much higher than those in the eastern and the western sections. Sediments collected from the northern part of the central section showed very high PCDD/F concentrations. The samples reveal three different congener profiles dominated by OCDF, 1,2,3,4,6,7,8-HpCDF, and OCDD respectively. The dominance of OCDF in the sediment samples taken from the central section was attributed to the former production of vinyl chloride monomer in the area, while that of 1,2,3,4,6,7,8-HpCDF was attributed to the (previously unknown) use of a chlorophenol-based fungicide in the region. The OCDD dominated group was explained by the use of pentachlorophenol. The results indicate that historic industrial discharges are the main contributor to the PCDD/F pollution in the sediments.     

Formation of artefacts while sampling emissions of PCDD/PCDF from open burning of biomass

Emission factors for PCDD/PCDF determined from open combustion are used to estimate national emission budgets; therefore, it is important to have confidence in their accuracy. It has been suspected that artefacts may form due to the presence of hot metal surfaces of sampling equipment, thus skewing emission factors. In this study, emissions of PCDD/PCDF from open burning of forest biomass over a brick hearth were sampled. Five experiments were carried out using a portable sampler. Experiments were designed where the key variable, sample hood and inlet temperatures were manipulated. Other variables such as fuel origin, type and density were consistent. The measured concentration of PCDD/PCDF in the smoke samples ranged from 0.01 μg TEQ (t fuel)⁻¹ at the lowest maximum hood temperature (185 °C) to 15 μg TEQ (t fuel)⁻¹ at the highest maximum hood temperature (598 °C). when hood inlet temperatures exceeded 400 °C emission factors were significantly elevated and this is attributed to the formation of artefacts that can cause the over estimation of emission factors. The increase in hood temperature also resulted in a change in the PCDD/PCDF congener and homologue profile of the emissions. For example at the lowest temperature (Fire 1) the PCDD/PCDF ratio measured was 50:1, whereas at the highest temperature (Fire 5) this ratio was about 0.53:1. When the sampler hood and inlet temperatures were kept in the normal operating range of <200 °C, emission factors were comparable to those observed in many previous studies in Australia with emissions dominated by PCDD.     

Dietary exposure to PCDD/PCDFs by individuals living near a hazardous waste incinerator in Catalonia, Spain: temporal trend

The levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were measured in foodstuffs randomly acquired in July 2006 in various locations of Tarragona County (Catalonia, Spain), which are near a hazardous waste incinerator (HWI). A total of 35 composite samples, belonging to various food groups (vegetables, pulses, cereals, fruits, fish and seafood, meat and meat products, eggs, milk, dairy products, and oils and fats) were analyzed by HRGC/HRMS. The dietary intake of PCDD/PCDFs was subsequently determined and compared with a previous survey performed in 2002. For calculations, recent data on consumption of the selected food items were used. Total dietary intake of PCDD/PCDFs for the general population of Tarragona County was estimated to be 27.81 pg WHO-TEQ/day, value notably lower than that found in the 2002 study, 63.80 pg WHO-TEQ/day. Fish and seafood (28%), oils and fats (22%), eggs (17%), and dairy products (11%) were the most important contributors to this intake, while pulses (1%), milk (2%), vegetables (3%) and fruits (3%) showed the lowest contribution to total WHO-TEQ. The current PCDD/PCDF intake is also considerably lower than the intake estimated in 1998 for the population of the same geographical area, 210.1 pg I-TEQ/day, when a baseline study was carried out during the construction of the HWI. The present intake is also compared with the dietary intakes of PCDD/PCDFs recently (2006-2007) reported for a number of regions and countries.     

Evaluation of PCDD/Fs characterization in animal feed and feed additives

Safety control of feed and feed additives is necessary to have safe food of animal origin. Based on media reports, nine incidents regarding dioxins and/or PCBs contaminations occurred worldwide during the last decade. Korea is a country which imports feed and feed additives. In this study, various kinds of feed and feed additives were analyzed to monitor the contamination level of dioxins. The level of PCDD/Fs in fish oil was the highest with a concentration of 23.33ngkg(-1), which is equivalent to a toxicological concentration of 4.68ngWHO-TEQ/kg. Feed from animals origin such as chicken meal, animal fat, fish meal, fish oil, and shell powder showed relatively higher concentrations of PCDD/Fs. Feed from plants origin, minerals, and additives ranged from non-detects for bit pulp and ethoxyquin to 8.28ngkg(-1) for dl-methionine. From a toxicological point of view, the highest concentration in vitamins was 0.08ngWHO-TEQ/kg among the feed additives. 2,3,4,7,8-PeCDF was the dominant congener in samples of fish oil, fish meal, and shell powder. Animal fat showed that the pattern of PCDD/Fs depends on the sources of contamination. A sample of animal fat showed 1,2,3,4,7,8-HxCDF and the other sample showed 1,2,3,4,7,8-HxCDD as a primary congener. Generally, low levels of PCDDs were detected in feed additives. Patterns of PCDD/Fs in choline chloride were different with that in choline chloride from an incident in Europe in 2000.     

Evaluation of the emission characteristics of PCDD/Fs from electric arc furnaces

Distribution of PCDD/F (polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran) congeners at two electric arc furnaces (EAFs) in Taiwan is evaluated via intensive stack sampling and analysis. Two kinds of exhaust system in EAFs including stack system and shutter system are selected for measuring dioxin emissions. In addition, dioxin emissions during oxidation and reduction stages at EAF-A were characterized. Results indicate that the PCDD/F concentration of stack gas in EAF-A was 4.39 ng/N m³ while total Toxic Equivalent Quantity (TEQ) concentration was 0.35 ng I-TEQ/N m³. The PCDD/F concentration of stack gas in EAF-B was 2.20 ng/N m³ and the TEQ concentration was 0.14 ng I-TEQ/N m³. 1,2,3,4,6,7,8-H_pCDF, OCDD and OCDF are the major contributors of the dioxin concentrations for two EAFs investigated and the percentage of PCDD/F in particulate phase increases as the chlorination level of the PCDD/F congener increases. The results obtained on gas/particulate partitioning of PCDD/Fs in flue gases prior to the APCD in EAFs indicate that more than 90% exists in particulate phase. In EAF-A, the PCDD/F concentration during oxidation stage is slightly higher than that measured during reduction stage, including the sampling points of CO converter outlet, prior to bag filter and stack. Majority of PCDD/Fs emitted from steel-making processes exists in particulate-phase (about 60–70%) at both EAFs investigated.