PCDD/PCDF Isomer patterns in waste incinerator flyash and desorbed into the gas phase in relation to temperature

The influence of temperature on the PCDD and PCDF isomer profiles of a municipal waste incinerator flyash and the PCDD/PCDF desorbed from the ash under an inert atmosphere was investigated using a bench-scale reactor. Exposure to temperatures of 250 degrees C and above resulted in significant changes in the distribution of isomers within most dioxin and furan congener groups. The PCDD content tended to become more evenly distributed across the range of isomers than was the case for the raw flyash, while the PCDF content became concentrated across a relatively lower number of isomers. In most cases the desorbed PCDD/PCDF were mainly mono- to tri-chlorinated, and hence had a relatively low I-TEQ value. The isomer profiles of the desorbed species were also influenced by temperature. There were some significant differences between the PCDF isomer profiles of the desorbed species and those of the treated flyashes under the same conditions, but no clear differences between the PCDD isomer profiles.     

CuCl2-catalyzed PCDD/F formation and congener patterns from phenols

Homologue and isomer patterns of polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) in CuCl2-catalyzed formation were studied in an isothermal flow reactor using a distribution of 20 phenols as measured in municipal waste incinerator (MWI) exhaust gases. A mixture of 20 phenols was synthesized and used as reactants for this study because phenols are known to be key precursors in the formation of PCDD/F. Experiments were conducted at 400 degrees C. The 92% of nitrogen (N2) and 8% of oxygen (O2) were used as a carrier gas. PCDD/F homologue and isomer patterns with dibenzo-p-dioxin (DD) and dibenzofuran (DF) were obtained from a mixture of 20 phenols. DF+PCDF formation was favored over DD+PCDD formation. The major homologue groups formed were non-chlorinated DD and DF, and PCDD/F homologue fraction decreased with the degree of chlorination. PCDD/F homologue and isomer distributions were almost constant. Phenol and lower chlorinated phenols present in high amount played an important role in PCDD/F congener distributions. The results presented here can be used as characteristics or fingerprints for homologue and isomer patterns of PCDD/F formation attribution in CuCl2-catalyzed reaction from phenols.     

Changes in PCDD/PCDF formation processes during instationary phases of combustor operation--exemplified by the use of Cl4DD isomer patterns

In this paper results of various measurement campaigns at different municipal waste incineration (MWI) plants concerning the change of the PCDD/PCDF isomer distribution in the crude gas during transiently impaired combustion conditions are presented. The focus is on the Cl4DD isomer distributions exemplarily for all other homologue groups to demonstrate the change in PCDD/PCDF formation mechanism at transient combustion conditions. Additionally to crude gas samples, at one plant filter and boiler ash were investigated simultaneously to determine if there is any difference in the isomer distribution between the matrices. For the ash from an electrostatic precipitator (ESP ash), the boiler ash and the corresponding crude gas sample, nearly identical changes in the Cl4DD isomer distribution under transient combustion conditions in relation to the normal operation process could be detected. By comparing the Cl4DD isomer distributions from different incineration plants (two municipal waste incinerators and one little incinerator burning wood chips for heating domestic household) under transient combustion conditions, in all cases the 1,3,6,8- and 1,3,7,9-Cl4DD were dominating the isomer distribution, whereas under normal operation other isomers were predominant. Obviously PCDD/PCDF formation mechanisms under transient combustion conditions are independent from the type of incinerator and of the burned fuel, respectively. Data sets were analyzed with respect to the possible reaction mechanism via chlorophenols and a good correlation of 2,4,6-trichlorophenol during the second phase of a start-up process and during a CO experiment was found. To get more detailed information about possible formation mechanisms, at one plant the dependence of the PCDD/PCDF isomer distribution on the different matrices was studied. Separate analysis of fly ash collected at the boiler exit, subsequent gas phase, ESP ash and boiler ash under normal operation conditions showed that, apart from the fly ash, the Cl4DD isomer distributions are nearly the same in the different matrices. Surprisingly, the Cl4DD isomer distribution of the fly ash was more similar to the distributions found under transient combustion conditions.     

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.     

Concentrations,atmospheric partitioning,and air–water/soil surface exchange of polychlorinated dibenzo-p-dioxin and dibenzofuran along the upper reaches of the Haihe River basin,North China

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) were overall measured and compared in ambient air, water, soils, and sediments along the upper reaches of the Haihe River of North China, so as to evaluate their concentrations, profiles, and to understand the processes of gas–particle partitioning and air–water/soil exchange. The following results were obtained: (1) The average concentrations (toxic equivalents, TEQs) of 2,3,7,8-PCDD/PCDF in air, water, sediment, and soil samples were 4,855 fg/m³, 9.5 pg/L, 99.2 pg/g dry weight (dw), and 56.4 pg/g (203 fg TEQ/m³, 0.46 pg TEQ/L, 2.2 pg TEQ/g dw, and 1.3 pg TEQ/g, respectively), respectively. (2) Although OCDF, 1,2,3,4,6,7,8-HpCDF, OCDD, and 1,2,3,4,6,7,8-HpCDD were the dominant congeners among four environmental sinks, obvious discrepancies of these congener and homologue patterns of PCDD/PCDF were observed still. (3) Significant linear correlations for PCDD/PCDF were observed between the gas–particle partition coefficient (K _p) and the subcooled liquid vapor pressure (P _L ⁰) and octanol–air partition coefficient (K _oa). (4) Fugacity fraction values of air–water exchange indicated that most of PCDD/PCDF homologues were dominated by net volatilization from water into air. The low-chlorinated PCDD/PCDF (tetra- to hexa-) presented a strong net volatilization from the soil into air, while high-chlorinated PCDD/PCDF (hepta- to octa-) were mainly close to equilibrium for air–soil exchange.     

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.     

Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) isomer patterns from municipal waste combustion: formation mechanism fingerprints

Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) byproducts can be formed in combustion systems by a variety of mechanisms. While total PCDD/F emissions and, to a lesser extent, homologue distributions from incinerators have been found to vary widely depending on combustion conditions, PCDD/F isomer distributions do not. Formation mechanisms can be grouped into two general categories: condensation of precursors, such as chlorinated phenols, and formation from particulate carbon, termed de novo synthesis. In addition to these mechanisms, chlorination and dechlorination reactions may affect isomer patterns. In this work, isomer patterns from field and laboratory municipal waste combustion samples are compared with computed thermodynamic distributions and those from the following experimental investigations: both gas-phase and metal-catalyzed condensation of chlorinated phenols, chlorination of dibenzo-p-dioxin and dibenzofuran, and dechlorination of octachlorodibenzo-p-dioxin and octachlorodibenzofuran. PCDD/F isomer patterns produced by different formation mechanisms in controlled experiments are distinct and robust, largely unaffected by combustion conditions. PCDD isomer patterns from municipal waste combustion are most similar to those produced by CuCl(2)-catalyzed phenol condensation from 10 chlorinated phenols. PCDF isomer patterns are most similar to those produced by chlorination and dechlorination.     

Occurrence, possible sources, and temporal trends of polychlorinated dibenzo-p-dioxins and dibenzofurans in water and sediment from the lower Yangtze River basin, Jiangsu and Shanghai areas of Eastern China

The concentrations, compositional profiles, and possible sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) in water column and surface sediment samples from the lower reaches of the Yangtze River were investigated, and the potential risks posed by these chemicals were evaluated. Concentrations of the 17 2,3,7,8-substituted PCDD/PCDF in the water and sediment samples ranged from 0.45 to 10.0 pg TEQ/L (mean 2.34 pg TEQ/L) and from 0.31 to 51 pg TEQ/g dw (mean 5.25 pg TEQ/g dw), respectively. Water and sediments from the Nanjing–Nantong sections of the Yangtze River were found to have elevated PCDD/PCDF levels, and the PCDD/PCDF TEQ concentrations in 13 sediment samples exceeded the probable effect levels (PEL), above which adverse biological effects are likely. Multivariate statistical analysis indicated that the principal PCDD/PCDF contamination source for the water and sediment was the production and use of pentachlorophenol (PCP) or sodium pentachlorophenate (PCP-Na). PCDD/PCDF concentrations were stable over time near the Yangtze River Estuary but had increased sharply in recent decades in the Nanjing–Nantong section, which will have been related to the growth in industrial activities and other anthropogenic PCDD/PCDF sources. Total organic carbon (TOC) and PCDD/PCDF concentrations correlated significantly (R?=?0.474, P?<?0.01), suggesting that TOC plays an important role in the transport and re-distribution of PCDD/PCDF in the Yangtze River basin.     

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.     

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.     

Comparison of PCDD and PCDF in flyash collected from muncipal incinerators of different countries

Flyash samples were collected from the electrostatic precipitators of seven municipal refuse incinerators of four different countries. Analytical results of PCDD and PCDF in these samples shows a very similar iosmer distribution pattern for all PCDD/PCDF although concentrations of PCDD and PCDF vary. These results imply that PCDD/PCDF were formed through the same mechanism in those incinerators regardless of garbage composition or incinerator design.     

Development of GC capillary column for isomer-specific separation of toxic isomer of PCDDs and PCDFs in environmental samples

Analysis of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) has been performed using gas chromatography mass spectrometry (GC-MS). Analysis of the most toxic isomers, in particular, 2,3,7,8-substituted PCDD/PCDF in the presence of other isomers requires a special isomer specific capillary column or high performance liquid chromatography (HPLC) fractionation prior to GC-MS analysis. Commercially available long (>50 m) polar columns can separate 2,3,7,8-TCDD from other tetra isomers. However, those columns are not satisfactory for the analyses of total PCDD/PCDF in the environmental samples. Gas chromatography -high resolution mass spectrometry (GC-HRMS) and GC-MS/MS techniques are not helpful in the analysis of 2,3,7,8-TCDD unless it is separated from the other tetra isomers. The analysis of 2,3,7,8-TCDD and total PCDD and PCDF in a single GC-MS run can ease the laborious techniques presently used. In this study we have developed a new stationary phase for the GC capillary column. The capillary column developed using this new stationary phase showed unsurpassed selectivity for the separation of 2,3,7,8-TCDD from other tetra isomers. There are several advantages of the newly developed GC capillary column.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in paddy soils and river sediments in Akita, Japan

Paddy soils and sediments from the Yoneshirogawa, Omonogawa, and Koyoshigawa River Basins in Akita were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The levels and compositions in those samples including soils from non-agricultural areas (non-agricultural soils) were investigated using isomer-specific analysis to determine characteristic sources. The PCDD/PCDF compositions in the samples were compared with respect to possible sources. The PCDD/PCDF concentrations in paddy soils were much higher than those in the non-agricultural soils and much higher than those found in other parts of Japan. Although PCDD/PCDFs were ubiquitous in sediments from river sources to mouths of the respective river basins, those concentrations were much lower than those from paddy soils and non-agricultural soils, and from other parts of Japan. Comparison of PCDD/PCDF homologues and isomer compositions for samples indicated that compositions of paddy soils and sediments, except for those from river sources, had similar characteristics to PCDD/PCDFs originating from impurities in herbicides, 2,4,6-trichlorophenyl 4-nitrophenyl ether (CNP) and pentachlorophenol (PCP), and that compositions of river-source sediments and non-agricultural soils resembled those of atmospheric depositions. Results of statistical analyses suggest that PCDD/PCDF contamination of paddy soils and sediments is attributable mainly to three sources: CNP, PCP, and atmospheric deposition. Results of this study also demonstrate that CNP and PCP are not only important contaminants of local areas of Japan, but that they exist throughout Akita, in northern Japan. We therefore conclude that PCDD/PCDF pollution caused by those compounds has a widespread influence on paddy soils and river sediments in Japan.     

Concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans and non-ortho substituted biphenyls in polar bear milk from Svalbard (Norway)

Polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and non-ortho substituted biphenyls (PCB, CB) were determined in 6 polar bear milk samples from Svalbard (Norway). For these compounds, no data for polar bears have been reported before from this region. Most of the PCDD/PCDF congeners were found at detectable levels. Concentrations expressed as 2,3,7,8-TCDD equivalents (Nordic model) were in the order of 1–3 pg/g⁻¹ fat (0.2–1.6 pg ml⁻¹ milk) which is comparable with ringed and harp seal blubber from the same region. On whole milk basis, concentrations were similar to those found in human milk. An estimation of the daily uptake via milk showed that the intake is lower for polar bears compared to humans. As in human milk, relatively high levels of OCDD were found in some polar bear milk samples. The PCDD/PCDF congener pattern in the milk was different to that found in polar bear fat from the Canadian Arctic. Non-ortho substituted PCB levels in polar bear milk were similar to those found in polar bear fat from the Canadian North. However, CB 77 or 169 dominated in the milk while CB 126 was the most abundant congener in fat. PCDD/PCDF levels expressed as 2,3,7,8-TE were highly correlated with the fat content of the milk. No correlation between CB and PCDD/PCDF concentrations was found. Some data indicate that PCDD/PCDF concentrations in polar bear milk decrease with increasing time after delivery.     

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.     

Emissions of PCDD and PCDF from combustion of forest fuels and sugarcane: a comparison between field measurements and simulations in a laboratory burn facility

Release of PCDD and PCDF from biomass combustion such as forest and agricultural crop fires has been nominated as an important source for these chemicals despite minimal characterisation. Available emission factors that have been experimentally determined in laboratory and field experiments vary by several orders of magnitude from <0.5 μg TEQ (t fuel consumed)⁻¹ to >100 μg TEQ (t fuel consumed)⁻¹. The aim of this study was to evaluate the effect of experimental methods on the emission factor.A portable field sampler was used to measure PCDD/PCDF emissions from forest fires and the same fuel when burnt over a brick hearth to eliminate potential soil effects. A laboratory burn facility was used to sample emissions from the same fuels. There was very good agreement in emission factors to air (EF_Air) for forest fuel (Duke Forest, NC) of 0.52 (range: 0.40-0.79), 0.59 (range: 0.18-1.2) and 0.75 (range: 0.27-1.2) μg TEQ_WHO2005 (t fuel consumed)⁻¹ for the in-field, over a brick hearth, and burn facility experiments, respectively. Similarly, experiments with sugarcane showed very good agreement with EF_Air of 1.1 (range: 0.40-2.2), 1.5 (range: 0.84-2.2) and 1.7 (range: 0.34-4.4) μg TEQ (t fuel consumed)⁻¹ for in-field, over a brick hearth, open field and burn facility experiments respectively. Field sampling and laboratory simulations were in good agreement, and no significant changes in emissions of PCDD/PCDF could be attributed to fuel storage and transport to laboratory test facilities.     

A national inventory to estimate release of polychlorinated dibenzo-p-dioxins and dibenzofurans in Portugal

Taking into account current environmental concerns, the main objective of this work focused a national inventory aiming to estimate the amount of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) released in Portugal in 2006. The methodology used was based on the Standardized Toolkit for Identification and Quantification of Dioxins and Furan Releases, developed by UNEP Chemicals, in 2005. The method allows the assessment of the amount of PCDD/PCDF released into the environment along five vectors involving air, water, land, products and residues. Facing some difficulties mainly regarding to the availability of data for some activities known to produce PCDD/PCDF, three scenarios (Sc1 to Sc3) corresponding to lower, central and upper estimates were established. The Sc1 scenario (lower estimate) includes the situations where in case of doubt or scarce information, reduced or none emission values were assumed, Sc2 refers to a central estimate, which is believed to be the most realistic for the Portuguese situation, while Sc3 corresponds to the worst case (upper estimate). The results obtained pointed out that the total amount of PCDD/PCDF emitted in Portugal during the period under analysis was in the range of 51.2-217.9 g TEQ year⁻¹, with the most likely value of 95.2 g TEQ year⁻¹ achieved under the Sc2 scenario. This study also showed that the methodology developed by UNEP Chemicals is a very simple one, and the main difficulty is the availability of data. The main indicators calculated in this study were 8.98 μg TEQ/(year person) by taking into account the total amount of PCDD/PCDF released, and 3.63 μg TEQ/(year person) when only air emissions were considered.     

Emissions of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans from Various Industrial Sources

Abstract

This study characterized the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from the stack flue gases of 17 industrial sources, which were classified into 10 categories. The results show that the mean PCDD/PCDF concentration of secondary zinc smelter (Zn-S) and secondary copper smelter (Cu-S) is 2.44 ng international toxic equivalent (I-TEQ)/Nm³ (N represents normal conditions at 0 °C, 760 mmHg), which was found to be significantly greater than that of industrial waste incinerators (mean concentration = 0.15 ng I-TEQ/Nm³). These results imply that the controlling of secondary metallurgical melting processes is more important than industrial waste incineration for the reduction of PCDD/PCDF emissions. The mean emission factors of cement production, Zn-S and Cu-S, are 0.052, 1.99, and 1.73 μg I-TEQ/t product, respectively. For industrial waste incineration, the mean emission factors of waste rubber, waste liquor, waste sludge, industrial waste solid (IWI)-1, IWI-2, IWI-3, and IWI-4 are 0.752, 0.435, 0.760, 6.64, 1.67, 2.38, and 0.094 μg I-TEQ/t feed, respectively. Most of the PCDD/PCDF emission factors established in this study are less than those reported in previous studies, which could be because of the more stringent regulations for PCDD/PCDF emissions in recent years.     

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

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

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.