Consultant Guide/1989

The European Economic Community (EEC) has proposed strict limits on emissions of dioxins and furans from hazardous waste incinerators. The proposed limit is 0.1 ng/Nm³, expressed as the 2,3,7,8 TCDD toxic equivalent of 17 specific dioxin and furan congeners. These limits will potentially redefine technology selection and design for combustion, energy recovery, and air pollution control. The EPA has a different approach for controlling emissions of products of incomplete combustion (PICs) and reformation products such as dioxins and furans. Rather than limiting these contaminants individually and quantitatively, EPA proposes controlling them by assuring good combustion as measured by stack emissions of carbon monoxide (CO) and total hydrocarbons (THC).

Dioxins and furans are combustion by-products and emission control relies mainly on control of the combustion process. These compounds can also be reformed from certain precursor compounds and elements in lower temperature regions of the system downstream of the combustion process. Air pollution control technologies have demonstrated the ability to remove dioxins and furans as contaminants on fine particulate.

This paper will discuss the two regulatory approaches, the mechanisms for the formation and reformation of dioxins and furans, and the technologies available to control emissions.     

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.     

Concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in soil in the vicinity of a landfill

Estonia still has no waste incineration facilities, which would act as substantial sources of dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) pollution. As landfill fires may serve as sources of dioxins, we focused on the concentrations of PCDD and PCDF in soil samples taken in the vicinity of the landfill located at south-east Estonia in the course of our inventory. Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in five soil samples taken in the vicinity of the Laguja landfill in south-east Estonia. The four soil samples were taken in southern, eastern, western and northern parts not further than 300 m from the landfill, and one sample was taken at the distance of 3 km from the landfill. The PCDD/F concentrations in all soil samples were at background level (0.64-2.33 pg I-TEQ WHO/g dry weight). To maintain this situation, the administrator of the landfill must avoid landfill fires, which are one of the reasons for the generation of dioxins and furans.     

Behavior of PCNs, PCDDs, PCDFs, and dioxin-like PCBs in the thermal destruction of wastes containing PCNs

In the first known study to characterize the emissions of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) from the thermal treatment of wastes containing PCNs, the formation and decomposition behavior of these pollutants was investigated both at laboratory scale and at plant scale. Exhaust gas measurements from laboratory-scale combustion of rubber belts containing PCNs (FB belts) were used as the basis for calculations predicting that the incremental dioxin toxic equivalency (TEQ) emissions from municipal solid waste (MSW) incinerators would be less than 0.1 ng/m3 N. In order to directly examine co-incineration of FB belts with MSW and to address potential differences between the laboratory experiment and full-scale MSW incinerators, experiments were conducted using a larger scale thermal treatment test facility with sampling and analysis at several points in the thermal treatment process. Congener specific analysis of PCNs clearly showed that both destruction and synthesis simultaneously occurred during combustion in the kiln. Most of the PCNs were destroyed by secondary combustion, and almost all PCNs were removed after flue gas treatment. Almost all PCDDs/DFs were synthesized as by-products of kiln combustion, most of them were destroyed by the secondary combustion, and almost all dioxins (PCDDs/DFs and dl-PCBs) were removed after flue gas treatment. The TEQ emission levels were less than 0.1 ng/m3 N for all plant-scale tests, and differences in TEQ emission levels were very small. Adding wastes containing PCNs to MSW will not influence thermal treatment emissions to the environment from modern solid waste incinerators.     

Release of polychlorinated dibenzo-p-dioxins and dibenzofurans by setting off fireworks.

Selected pyrotechnic articles were set off under laboratory conditions. Residues and vapors of smoke as well as unburnt charges were analyzed for polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/F) and their precursors chlorinated benzenes and phenols. The contamination of the selected products with these organic xenobiotics proved to be very variable. Remains of fireworks contained octachlorinated dioxins and furans up to 142 ng I-TEQ/kg as well as hexachlorobenzene in the range of 0.05 to 1,400 mg/kg. The deflagration of detonating compositions usually resulted in a dispersion of contaminants, whereas continuously burning flare compositions partially led to a thermal decomposition of organic pollutants. A significant rate of formation of polychlorinated dioxins and furans was observed when setting off blue-lightning rockets and fountains. Further investigations revealed that even high temperatures during the deflagration of black powder charges could not suppress the formation of PCDD/F from appropriate precursors.     

Formation of chlorinated and brominated dioxins and other organohalogen compounds at the pilot incineration plant VERONA

Experiments were conducted at the VERONA pilot plant, an incineration plant with stationary grate and separate post-combustion chamber, using wood and propane as basic combustible materials and with controlled dosage of various bromine-, chlorine- and copper-containing compounds. The behaviour of the following compounds was studied in the combustion chamber, after the post-combustion chamber and after the heat exchanger: polychlorinated phenols (PCPh), polybrominated phenols (PBrPh), polychlorinated benzenes (PCBz), polybrominated benzenes (PBrBz), polychlorinated dioxins and furans (PCDD/F) and polybrominated dioxins and furans (PBDD/F). The bromine co-incineration leaded to very high bromophenol concentrations after the post-combustion chamber. The formation of brominated and mixed-halogenated phenols and the further reaction to halogenated dioxins is apparently a relevant reaction mechanism for dioxin formation in processes involving bromine. This assumption is supported by the high formation rates of PBDD/F found in the heat exchanger, which were 4-20 times higher than those of PCDD/F. Moreover, the strong correlations found between the formation rates of PCPh, PCBz and PCDD/F in the heat exchanger indicate that in addition considerable new formation of dioxins takes place through de novo synthesis. Experiments involving the variation of primary operational parameters and fuel properties have shown that the quality of post-combustion plays a much greater role than the other parameters. Furthermore, it became apparent that the congeners of the chlorophenols and of the chlorobenzenes, measured in various incineration stages, do not correlate closely with the dioxin concentrations after the heat exchanger.     

Statistical investigation of polychlorinated dibenzo-p-dioxins and dibenzofurans in the ambient air of Houston, Texas

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (dioxins and furans) are persistent, bioaccumulative and highly toxic chemical constituents that appear in the environment at very low and difficult to measure levels. Although dioxins and furans are widely recognized as toxic contaminants needing regulation, their temporal and spatial concentration profiles and the factors impacting their partitioning and congener distribution are only moderately understood. This paper presents the results from one of the most extensive ambient air dioxin and furan sampling efforts conducted in a geographic area to date. The data consist of monthly ambient concentrations of 17 of the most toxic congeners of dioxins and furans collected at five locations in Houston, Texas over a calendar year. The results showed a total annual mean dioxin and furan congener concentration of 1047 fg/m3 and an annual mean summation operatorI-TEQ concentration of 15 fg I-TEQ/m3 (16 fg WHO-TEQ/m3). These results, when compared with proximate data from the USEPA National Dioxin Ambient Monitoring Network (NDAMN), revealed significant (at the P0.05 level) differences between Houston and the NDAMN sites, suggesting the existence of local dioxin sources. A temporal analysis of the data showed that the congener concentration distribution varies over time, depending on the level of chlorination, type of congener, and temperature. The results also suggested that the fluctuations of congener concentrations and I-TEQ concentrations are closely correlated with minimum relative humidity, mean temperature, and mean NOx concentration.     

Formation of toxic chemicals including dioxin-related compounds by combustion from a small home waste incinerator

We investigated combustion in a small home waste incinerator and analyzed both flue gas and residual ash for formation of the dioxin-related compounds polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and coplanar polychlorinated biphenyls and their precursors polychlorinated benzenes, polychlorinated phenols, polychlorinated diphenyl ethers, and polychlorinated biphenyls. Particularly, we investigated the effect of the incinerated material's composition on both the congener ratios of released compounds and the total concentration of all congeners of each compound. Eight different samples were prepared for incineration with four samples consist entirely paper, dead leaves, natural wood, or building materials. The remaining four samples contained mostly paper, but also other components such as fiber, non-chlorine-containing plastics, chlorine-containing plastics, and copper electric wire. The presence of non-chlorine-containing plastic in combustion samples did not increase overall dioxin or dioxin-precursor emissions. In contrast, chlorine-containing plastic resulted in a several-fold increase in total polychlorinated dioxins released, in both flue gas and residual ash. Copper wire resulted in a further several-fold increase in total polychlorinated dioxins and dioxin precursors released, with one exception: the addition of chlorine-containing plastic resulted in a many-fold increase in polychlorinated biphenyls, but only a modest further increase ( approximately 52%) with the further addition of copper. Homologue ratios tended toward higher-chlorine compounds as chlorine-containing plastic and Cu were added, but the results were far from uniform. Our results show that toxic dioxin release from small home waste incinerators must be considered significant, especially if even small amounts of chlorine-containing plastics or copper are burned.     

Levels, persistence and bioavailability of organic contaminants present in marine harbor sediments impacted by raw sewage

As part of a program to investigate the levels, fate and bioaccumulation of organic contaminants in a polluted marine harbor, organochlorine compounds including the polychlorinated biphenyls (PCBs), dichloro diphenyltrichloroethane and metabolites (DDTs), chlordanes, dibenzo-p-dioxins (Ds) and dibenzofurans (Fs), polycyclic aromatic hydrocarbons (PAHs) and sulphur hetero cycles were analysed in sediments spiked with St. John's Harbor sludge. Winter flounder (Pseudopleuronectes americanus) were exposed to these sediments containing six levels of harbor sludge during four winter months. Following exposure, sediments were reanalysed to investigate the persistence of the contaminants. The primary contaminants detected were PAHs (approximately 5000 ng/g), predominantly alkylated phenanthrenes, fluoranthene and pyrene; PCBs with a predominance of Aroclor 1260 signature (approximately 64 ng/g), DDTs (approximately 5 ng/g), hepta and octachloro dioxins and furans (approximately 0.5 ng/g) with very low levels of less chlorinated congeners. The PAHs degraded with an estimated half life of 2 to 3 months, while no significant degradation could be attributed to the other compounds. Bioaccumulation to muscle showed the potential uptake of contaminants in biota inhabiting the harbor. A dose-response relationship was observed between spiked sediments and the concentrations of PCB congener 153 and unresolved congeners 138/163/164 in muscle. Of the dioxins and furans, only 2, 3, 7, 8-tetrachlorofuran was detectable in muscle and at a similar concentration in all exposures indicating a similar bioavailability independent of the fraction of sludge in sediments. Of the PAHs, only naphthalene and methyl naphthalenes were detected in muscle, but did not display a dose-response. One bile metabolite of pyrene was quantified and demonstrates metabolism. Biota-sediment accumulation factors were of 0.2 to 7 indicating that equilibrium was approached, with the exception of the hepta and octachloro dioxins and furans which were not significantly bioaccumulated.     

Export of toxic chemicals - a review of the case of uncontrolled electronic-waste recycling

This paper reviews the concentrations of persistent organic pollutants such as flame retardants (PBDEs), dioxins/furans (PCDD/Fs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and heavy metals/metalloid concentrations of different environmental media at Guiyu, a traditional rice-growing village located in southeastern Guangdong Province (PR China), which has turned into an intensive electronic-waste (e-waste) recycling site. Incomplete combustion of e-waste in open air and dumping of processed materials are the major sources of various toxic chemicals. By comparing with existing data available in other areas and also guidelines adopted in different countries, it is obvious that the environment is highly contaminated by these toxic chemicals derived from the recycling processes. For example, the monthly concentration of the sum of 22 PBDE congeners contained in PM(2.5) (16.8ngm(-3)) of air samples at Guiyu was 100 times higher than published data. In order to safeguard the environment and human health, detailed investigations are urgently needed, especially on tracking the exposure pathways of different toxic chemicals which may affect the workers and local residents especially mothers, infants and children.     

Effect of copper chloride on the emissions of PCDD/Fs and PAHs from PVC combustion

The influences of temperature, air flow and the amount of copper chloride upon the types and amount of the toxic emissions such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) during combustion of polyvinyl chloride (PVC) were investigated. The mechanism concerning the effect of temperature and copper chloride on the PCDD/Fs and PAHs formation was discussed. The results shown that without copper chloride, trace amounts of PCDD/Fs and large amounts of PAHs were found in the emissions from the pure PVC combustion under various combustion conditions. The addition of copper chloride enhanced PCDD/Fs formation, but it seems that the formation of PAHs decreased with increasing amount of copper chloride, and greater total amount of PAHs were produced at the higher temperature under our experimental conditions.     

The relative contribution of wood and poly(vinyl chloride) to emissions of PCDD and PCDF from house fires

Emissions of PCDD/F from poly(vinyl chloride) (PVC) burned in house fires has been estimated at <1 g I-TEQ/yr in the US. In the current literature-based study, amounts of wood (21,000 kg) and PVC (180 kg) in a new house of standard construction are calculated and previously published emission factors for wood (0.01–173 μg/t) and PVC (3–6554 μg/t) are reported. Test conditions under which emission factors are generated differ and may not be directly comparable. Typically, PVC is tested at small-scale under relatively poor combustion conditions and wood is tested at large-scale under good combustion conditions. Thus, overall emission from combustion of these two materials of construction in house fires on an as-used basis is estimated to be similar (on the order of 1 g/yr) and a small contributor to the PCDD/F sources inventory. No speculation is made with respect to contents, roofing or other materials of construction.     

Contaminant risks from biosolids land application: contemporary organic contaminant levels in digested sewage sludge from five treatment plants in Greater Vancouver,British Columbia

This study examines the potential for environmental risks due to organic contaminants at sewage sludge application sites, and documents metals and various potential organic contaminants (volatile organics, chlorinated pesticides, PCBs, dioxins/furans, extractable petroleum hydrocarbons, PAHs, phenols, and others) in current production biosolids from five wastewater treatment plants (WWTPs) within the Greater Vancouver Regional District (GVRD). There has been greater focus in Europe, North America and elsewhere on metals accumulation in biosolids-amended soil than on organic substances, with the exception of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans. Another objective, therefore, was to evaluate the extent to which management of biosolids re-use based on metal/metalloid levels coincidentally minimizes environmental risks from organic contaminants. Historical-use contaminants such as chlorophenols, PCBs, and chlorinated pesticides were not detected at environmentally relevant concentrations in any of the 36 fresh biosolids samples, and appear to have virtually eliminated from sanitary collection system inputs. The few organic contaminants found in freshly produced biosolids samples that exhibited high concentrations relative to British Columbia and Canadian soil quality benchmarks included p-cresol, phenol, phenanthrene, pyrene, naphthalene, and heavy extractable petroleum hydrocarbons (HEPHs--nCl9-C34 effective carbon chain length). It was concluded that, with the exception of these petroleum hydrocarbon constituents or their microbial metabolites, the mixing of biosolids with uncontaminated soils during land application and based on the known metal concentrations in biosolids from the Greater Vancouver WWTPs investigated provides adequate protection against the environmental risks associated with organic substances such as dioxins and furans, phthalate esters, or volatile organics. Unlike many other organic contaminants, the concentrations of petroleum hydrocarbon derived substances in biosolids has not decreased within the last decade or more in the WWTPs studied, and--unlike persistent chlorinated compounds--the associated PAHs and other hydrocarbon constituents merit careful consideration, especially in the context of repeated land-application of biosolid.     

Ecotoxicological research and related legislation in Serbia

Introduction  

Several hot spots of severe freshwater pollution and sediment contamination (mostly heavy metals, polyaromatic hydrocarbons and polychlorinated biphenyls) have been identified in Serbia as the consequence of outdated environmental legislation, negligible amounts of properly treated waste waters and accidental spills.     

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.     

Effect of solid waste landfill organic pollutants on groundwater in three areas of Sicily (Italy) characterized by different vulnerability

The aim of this study was to obtain information on the presence and levels of hazardous organic pollutants in groundwater located close to solid waste landfills. Eighty-two environmental contaminants, including 16 polycyclic aromatic hydrocarbons (PAHs), 20 volatile organic compounds (VOCs), 29 polychlorinated biphenyls (PCBs), 7 dioxins (polychlorinated dibenzo-p-dioxins, PCDDs) and 10 furans (polychlorinated dibenzofurans, PCDFs) were monitored in areas characterised by different geological environments surrounding three municipal solid waste landfills (Palermo, Siculiana and Ragusa) in Sicily (Italy) in three sampling campaigns. The total concentrations of the 16 PAHs were always below the legal threshold. Overall, the Fl/Fl + Py diagnostic ratio revealed that PAHs had a petrogenic origin. VOC levels, except for two notable exceptions near Palermo landfill, were always below the legal limit. As concerns PCB levels, several samples were found positive with levels exceeding the legal limits. It is worth noting that the % PCB distribution differs from that of commercial compositions. In parallel, some samples of groundwater containing PCDDs and PCDFs exceeding the legal threshold were also found. Among the 17 congeners monitored, the most abundant were the highest molecular weight ones.

     

Post-combustion syntheses of PCDD/F and PBDD/F from halogen-rich fuel is suppressed by a pebble heater technology

GOAL, SCOPE AND BACKGROUND: Changes in German and European legislation shifted processing of polymer-rich shredding residues (SR) from landfill to thermal treatment. However, when waste of electric and electronic equipment (WEEE) is the source of SR, thermal treatment is complicated by halogens as well as the presence of polybrominated dioxins and furans (PBDD/F) and brominated flame retardants (BFR). Hence, WEEE requires high temperature incineration with sufficient residence times. Post-combustion synthesis of polyhalogenated dioxins and furans (PXDD/F) is dominant in the temperature range between 250-450 degrees C. Thus, a very rapid gas cooling from 450 degrees to 250 degrees C is important for proper raw gas treatment. The pebble heater technology developed by ATZ Entwicklungszentrum (Sulzbach-Rosenberg, Germany) might serve as an alternative to the state-of-the-art quench cooling. It is based on the application of a pebble bed of natural bulk material, which the exhaust gases flows through radially. It provides an excellent heat transfer and a temperature gradient in the range of 1,500-2,000 K/m. The paper presents data of a pilot application of the pebble heater technology for the treatment of raw gas derived from the incineration of polymeric materials from WEEE. METHODS: A liquid fuel was chosen in order to minimise technical modifications of the plant. It was analysed for halogens by x-ray fluorescence, for brominated flame retardants by HPLC-UV/MS and for PXDD/F by GC-HRMS. Combustion gases were rapidly cooled down to temperatures below 200 degrees C and emissions of PBDD/F and PCDD/ F were estimated without further off-gas treatment. PBDD/F emissions were computed as PCDD/F toxicity equivalents applying two different calculation approaches. RESULTS AND DISCUSSION: PCDD/F emissions accounted for 0.04 ng I-TEQ/Nm3 and are in compliance with European emission limits. Calculated PBDD/F toxicity equivalents exceeded the emission limit of 0.1 ng I-TEQ/Nm3 by factors of 75 and 208 depending on the calculation approach. A mass balance of PBDD/F and PCDD/F congeners revealed an efficient elimination of more than 95% in most cases. Lower reduction rates (76% for 2,3,7,8-TeBDF and 82% for 1,2,3,7,8-PeBDF) were attributed to incomplete combustion. An intended recovery of halogens by one-stage scrubbing downstream of the pebble heater was ineffective, recovering 28% of the applied chlorine and 9% of the bromine, only. CONCLUSIONS: Our pilot incineration test indicates that the pebble heater technology can effectively suppress a post-combustion synthesis of PCDD/F and PBDD/F, resulting in low PCDD/F emission levels without further off-gas treatment. The presented data state that WEEE is sensible to incomplete combustion, which will lead to increased PBDD/F emissions without increasing PCDD/F emission limits. This finding is especially relevant for small and low-technical incineration appliances, which have been reported to treat WEEE in developing countries and are considered to serve as a significant source of PXDD/F these days. RECOMMENDATIONS AND PERSPECTIVES: Monitoring of PCDD/F emissions only might considerably underestimate the total emission of dioxins and dioxin-like compounds. It is therefore an ineffective means for assessing resulting health risks, at least for those waste treatment plants which are considered to handle the increasing amounts of PBDD/ F-containing polymers from WEEE in future. Consequently, it is recommended to initiate a screening programme for PXDD/F emissions in large scale incineration facilities which are capable of treating WEEE shredder residues.     

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.     

Surface contamination with PASH, PAH and PCDD/F after fire accidents in private residences

Surface samples were taken from two private residences after real fire accidents. The goal was, to determine the surface contaminations with polycyclic aromatic sulfur heterocycles (PASH), as representatives of a substance class, not investigated in this context, by now, polycyclic aromatic hydrocarbons (PAH) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F). Analytical method for the determination of PASH was developed for the respective matrix. Concentrations measured ranged between 1.70 and 465 micrograms/m2 for PASH, 34.3 and 58,800 micrograms/m2 for PAH (EPA), and 4.15 and 1,300 ng/m2 for PCDD/F, as well. Obviously, PASH were formed during the fire accidents. Nevertheless, PAH were the most relevant pollutants after these small fires.     

Levels of dioxin-like compounds in sewage sludge determined with a bioassay based on EROD induction in chicken embryo liver cultures

A bioassay for the detection of dioxin-like compounds was used to estimate levels in sewage sludge from Swedish sewage treatment plants (STPs). The sludge extracts were HPLC-separated into three fractions containing a) monoaromatic/aliphatic, b) diaromatic (e.g. polychlorinated biphenyls [PCBs], polychlorinated dibenzodioxins and polychlorinated dibenzofurans [PCDDs/Fs]), and c) polyaromatic compounds (e.g. polycyclic aromatic hydrocarbons [PAHs]). The bioassay, which is based on EROD (7-ethoxyresorufin O-deethylase) induction in cultured chicken embryo livers detected dioxin-like activity in all unfractionated extracts and in the di- and polyaromatic fractions of all sludge extracts, but not in the monoaromatic/aliphatic fractions. The levels ranged between 6 and 109 pg bio-TEQ/g sludge (d.w.). In sediment samples from rural lakes in Sweden, levels of about 5 pg bio-TEQ/g (d.w.) have been found. The polyaromatic fractions of the sludge samples were potent in the bioassay, probably due to various PAHs and other polyaromatics in the sludge. The levels of six PAHs that are screened for in the sludge at Swedish STPs accounted for only 3-10% of the observed EROD-induction by the polyaromatic fractions. Consequently, many other polyaromatic EROD-inducing compounds were present in the sludge. Inclusion of a biological test like the chicken embryo liver bioassay in the screening of sludge would improve the ability to detect the presence of bioactive dioxin-like compounds. A theoretical estimation of bio-TEQ concentrations in farm-soil following long-term application of sludge with bio-TEQ concentrations similar to those observed in this investigation indicated that the bio-TEQ levels in soil would increase very slowly over time. The chicken embryo liver bioassay proved useful in assessing levels of dioxin-like compounds in sewage sludge and it gives valuable complementary information to chemical analysis data.