Prediction of dioxin/furan incinerator emissions using low-molecular-weight volatile products of incomplete combustion

Emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from incinerators and other stationary combustion sources are of environmental concern because of the toxicity of certain PCDD/F congeners. Measurement of trace levels of PCDDs/Fs in combustor emissions is not a trivial matter. Development of one or more simple, easy-to-measure, reliable indicators of stack PCDD/F concentrations not only would enable incinerator operators to economically optimize system performance with respect to PCDD/F emissions, but could also provide a potential technique for demonstrating compliance status on a more frequent basis. This paper focuses on one approach to empirically estimate PCDD/F emissions using easy-to-measure volatile organic C2 chlorinated alkene precursors coupled with flue gas cleaning parameters. Three data sets from pilot-scale incineration experiments were examined for correlations between C2 chlorinated alkenes and PCDDs/Fs. Each data set contained one or more C2 chloroalkenes that were able to account for a statistically significant fraction of the variance in PCDD/F emissions. Variations in the vinyl chloride concentrations were able to account for the variations in the PCDD/F concentrations strongly in two of the three data sets and weakly in one of the data sets.     

Modeling the atmospheric transport and deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in North America

The atmospheric fate of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was simulated for the year 2000 in North America using a SMOKE/CMAQ-based chemical transport model that was modified for this purpose. The 1999 USEPA emission inventories of PCDD/Fs and criteria pollutants were used. The 1995 Canadian emission inventory of criteria pollutants and the 1995 Canadian area source emissions for PCDD/Fs were used with the 2000 Canadian point source emissions. Modifications to CMAQ involved coupling it with dual organic matter (OM) absorption and black carbon (BC) adsorption models to calculate PCDD/F gas–particle partitioning. The model satisfactorily reproduced the particle bound fractions at all rural sites for which there were measured data and across the whole domain, the modeled vs. measured differences in particle bound fractions were less than 20% for nearly all congeners. The model predicted ambient air PCDD/F concentrations were also consistent with measurements. Simulated deposition fluxes were within 58% of direct measurements. PCDD/F atmospheric depositions to each of the Great Lakes were estimated for the year 2000. The results indicate that approximately 76% of the total deposition of PCDD/Fs to the Great Lakes (in W-TEQ, or toxic equivalent units as defined by the World Health Organization) is attributed to PCDD/Fs absorbed into OM in aerosol. For all of the lakes, more than 92% of all deposition is particle phase wet deposition and only 5–8% is particle phase dry deposition. Wet deposition from the gas phase is negligible. Of the 17 toxic PCDD/F congeners, the Cl_4–5DD/F compounds contribute approximately 70% to the total atmospheric deposition to the Great Lakes. The seasonal changes in the PCDD/F deposition flux track variations in ambient temperature.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

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.     

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans in atmosphere; evaluation of predicting models

The gas/particle partitioning of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) was measured at three sites for a year in order to monitor the variation of PCDD/Fs levels and describe their partitioning. The air concentrations of PCDD/Fs ranged from 71 to 1161 fg I-TEQ/m³ and large changes in these levels did not correlate with seasonal changes during this study. Different homolog patterns were observed in the gas/particle phase. High chlorinated dioxin/furans dominated the particle phase while low chlorinated dioxin/furans dominated the gas phase. The high correlation coefficient between log [(PCDD/Fs_vap)(TSP)/(PCDD/Fs_pat)] and 1/T was observed in lower chlorinated dioxin/furans unlike in OCDD/F. The slope of homolog ranged from −0.410 to −1.025 and that of 2,3,7,8-substituted isomers ranged from −0.379 to −0.772 in plots of the log partition coefficient (K_p) versus the log subcooled vapor pressure (P_L°).The octanol/air partition coefficient (K_oa)-based model of PCDD/Fs is more compatible with experimental data than those of the Junge–Pankow model that tends to overestimate results, even though both models include some level of uncertainty. However, both models can underestimate the particle phase of PCDD/Fs, especially when the ambient air temperature is extremely low in winter.     

PCDD/F concentrations in soil and vegetation in the vicinity of a municipal waste incinerator after a pronounced decrease in the emissions of PCDD/Fs from the facility

Emission of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) by municipal solid waste incinerators (MSWI) is an issue of great concern. In 1997, an adaptation to the EU legislation on pollutant emissions from the stack was carried out in an MSWI from Tarragona (Catalonia, Spain). As a result, PCDD/F emissions were significantly reduced. The aim of this study was to determine the current levels of PCDD/Fs in soil and vegetation samples collected near the facility and to compare these levels with those obtained in previous surveys (1996 and 1997). In the period 1997-1999, PCDD/F concentrations in vegetation samples were significantly decreased (60%). By contrast, the levels of PCDD/Fs in soil samples increased slightly (14%, P > 0.05) during the same period. An exhaustive analysis of the present data indicates that other emission sources of PCDD/Fs have also a notable environmental impact on the area under direct influence of the MSWI.     

Concentrations of PCDD/PCDF in soil close to a secondary aluminum smelter

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) were analyzed in samples of the emissions from a secondary aluminum smelter (ALS) and soil samples around the plant. The purpose was to estimate the impact of the emissions on the surrounding environment.PCDD/F soil concentrations were higher in the proximity of the plant, exceeding the limit adopted in Italy in soils for green areas and residential uses and the upper limit of several reference concentrations. The most contaminated sites were less than 500 m from the plant and the dioxin concentration with the distance from the ALS.Principal component analysis (PCA) showed that emissions from the ALS were the source of PCDD/F contamination in the soils closest to the plant. Multivariate data analyses such as PCA are therefore useful to identify sources of emission causing contamination.     

Congener profiles of PCDD/Fs in soil and vegetation samples collected near to a municipal waste incinerator

Recently, we measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in soil and herbage samples collected in the vicinity of a municipal solid waste incinerator (MSWI) from Tarragona (Catalonia, Spain). Since these concentrations could be increased by the presence of other emission sources of PCDD/Fs in the same area in which the MSWI is placed, the main goal of the present study was to determine the PCDD/F congener profiles in the soil and vegetation samples collected in 1996 and again in 1997 near to the facility and to compare with those from samples collected in a close area outside of direct emissions of the plant. From an accurate inspection of the PCDD/F congener profiles, it was concluded that PCDD/F emissions from the MSWI here examined are neither the only nor the main responsible for the presence of PCDD/Fs in the samples of environmental matrices collected in the area under direct influence of the plant.     

Concentrations of PCDD/PCDF in soil close to a secondary aluminum smelter

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) were analyzed in samples of the emissions from a secondary aluminum smelter (ALS) and soil samples around the plant. The purpose was to estimate the impact of the emissions on the surrounding environment.PCDD/F soil concentrations were higher in the proximity of the plant, exceeding the limit adopted in Italy in soils for green areas and residential uses and the upper limit of several reference concentrations. The most contaminated sites were less than 500 m from the plant and the dioxin concentration with the distance from the ALS.Principal component analysis (PCA) showed that emissions from the ALS were the source of PCDD/F contamination in the soils closest to the plant. Multivariate data analyses such as PCA are therefore useful to identify sources of emission causing contamination.     

Atmospheric bulk deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the vicinity of an iron and steel making plant

An IRA-743 resin bulk sampler was validated to monitor long-term bulk deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Six consecutive sampling campaigns (2008-2009) were conducted at four sites around steel complexes in Pohang, South Korea to investigate spatial and seasonal variations of PCDD/F bulk deposition. The bulk deposition within the steel complex showed the highest ∑_4-8PCDD/F (Tetra-Octa) fluxes, ranging from 204 to 608 (mean: 352) pg m⁻² d⁻¹, indicating steel complexes were major sources of PCDD/Fs. The homologue profiles were dominated with lower chlorinated PCDFs. Furthermore, the prevailing winds were confirmed to influence the spatial distribution of PCDD/F deposition. There were apparent seasonal variations of the bulk deposition at each site, and seasonal homologue patterns of PCDD/Fs were clearly observed. According to the passive air sampling, however, no significant seasonal change of ambient air concentrations of PCDD/Fs was observed. Therefore, it was concluded that the seasonal variations of deposition fluxes of PCDD/Fs probably resulted from temperature-dependent gas/particle partitioning.     

Fate of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans in a Fly Ash Treatment Plant

Abstract

To understand the fate of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in a fly ash treatment plant that used the Waelz rotary kiln process (hereafter the Waelz process), the samples of input and output media were collected and analyzed. The most important PCDD/F source in input mass was electric arc furnace (EAF) fly ash, which had a mean PCDD/F content of 18.51 ng/g and contributed more than 99% of PCDD/F input mass, whereas the PCDD/F input mass fractions contributed by the coke, sand, and ambient air were only 0.04%, 0.02%, and 0.000002%, respectively. For the PCDD/F output mass in the Waelz process, the major total PCDD/F contents of 43.73 and 10.78 ng/g were in bag-filter and cyclone ashes, which accounted for approximately 69% and 17%, respectively, whereas those of stack flue gas and slag were 14% and 0.423%, respectively. The Waelz process has a dechlorination mechanism for higher chlorinated congeners, but it is difficult to decompose the aromatic rings of PCDD/Fs. Therefore, this resulted in the accumulation of lower chlorinated congeners. The output/input ratio of total PCDD/F mass and total PCDD/F international toxicity equivalence (I-TEQ) was 0.62 and 1.19, respectively. Thus, the Waelz process for the depletion effect of total PCDD/F mass was positive but minor, whereas the effect for total PCDD/F I-TEQ was adverse overall.     

PCDD/Fs and PCBs in airborne particulate matter of the greater Thessaloniki area, N. Greece

Particle-bound polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were monitored at two sites in northern Greece for an eight-month period in 1999. PCDD/F concentrations were close to the lower end of reported values worldwide. Excepting a few cases, the PCDD/Fs homologue profile was stable. The gaseous PCDD/F fractions calculated were found to account for a small percentage of the total concentrations (<2% for OCDD/Fs and HpCDD/Fs, while 30-35% for TCDFs). Particle-bound PCBs were also found at low concentrations which, however, were higher at the urban site. Calculations of the dry deposition of particulate PCDD/ Fs and PCBs gave mean values of 0.52 and 0.59 pg I-TEQ/m2/day of PCDD/Fs, while 242 and 74 pg/m2/day of sigmaPCBs for the urban and the semirural areas respectively. An anticorrelation of PCDD/F concentrations with ambient temperature was derived particularly for the lower chlorinated congeners. A weak association with winds of western and southern origin was also observed. Factor analysis and literature source profiles were employed to identify possible emission sources. It was appeared that the PCDD/F compositional pattern of TSP is influenced by mixed sources the most prominent being uncontrolled fires and car exhausts.     

Assessment of emissions and removal of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) at start-up periods in a hazardous waste incinerator

A study was conducted to observe the changes in polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) levels and congener profiles in the flue gas of a hazardous waste incinerator during two start-up periods. Flue gas samplings were performed simultaneously through Air Pollution Control Devices (APCDs) (including boiler outlet, electrostatic precipitator (ESP) outlet, wet scrubbers (WS) outlet, and activated carbon (AC) filter outlet) in different combustion temperatures during a planned cold (long) start-up and an unplanned warm (short) start-up. The results showed that PCDD/F concentrations could be elevated during the start-up periods up to levels 3–4 times higher than those observed in the normal operation. Especially lower combustion temperatures in the short start-ups may cause high PCDD/F concentrations in the raw flue gas. Assessment of combustion temperatures and Furans/Dioxins values indicated that surface-catalyzed de novo synthesis was the dominant pathway in the formation of PCDD/Fs in the combustion units. PCDD/F removal efficiencies of Air Pollution Control Devices suggested that formation by de novo synthesis existed in ESP also when in operation, leading to increase of gaseous phase PCDD/Fs in ESP. Particle-bound PCDD/Fs were removed mainly by ESP and WS, while gaseous phase PCDD/Fs were removed by WS, and more efficiently by AC filter.

Implications: This paper evaluates PCDD/F emissions and removal performances of APCDs (ESP, wet scrubbers, and activated carbon) during two start-up periods in an incinerator. The main implications are the following: (1) start-up periods increase PCDD/F emissions up to 2–3 times in the incinerator; (2) low combustion temperatures in start-ups cause high PCDD/F emissions in raw gas; (3) formation of PCDD/Fs by de novo synthesis occurs in ESP; (4) AC is efficient in removing gaseous PCDD/Fs, but may increase particle-bound ones; and (5) scrubbers remove both gaseous and particle-bound PCDD/Fs efficiently.     

PCDD/Fs in ambient air in north-east Italy: The role of a MSWI inside an industrial area

The stack gases of a municipal solid waste incinerator (MSWI), and ambient air were sampled in four locations around the plant for the analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs). The sampling area was close to an industrial area near Trieste, in north-east Italy. The purpose of the study was to estimate the impact of the MSWI emissions and to distinguish the contribution of these emissions from other potential emission sources in the industrial area.PCDD/F atmospheric concentrations were similar to those generally detected in urban–rural areas with one location about 2–3 times more contaminated than the others. Since the most contaminated location was inside the industrial area but upwind of the MSWI, principal component analysis (PCA) was used to establish whether other sources were the cause. This analysis clearly showed that a local steel plant’s emission was the main source of PCDDs/Fs in ambient air. This study highlights the usefulness of multivariate data analysis such as PCA to identify, among different potential emission sources, the one really responsible for the contamination.     

Gas-particle partitioning of PCDD/Fs in Nagoya urban air, Japan

Polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) in the atmosphere were sampled by a high-volume filter/sorbent air sampler at an urban (Nagoya, Japan) site from May 2000 to January 2001 under the average ambient temperatures ranging from 1 degrees C to 33 degrees C. The gas and particle phase concentrations of PCDD/Fs were measured and then the field gas-particle partitioning data were used to assess the Junge-Pankow adsorption model and the K(OA) absorption model. For both PCDDs and PCDFs, passable agreement was obtained between the measured and predicted particulate-band fraction (phi) values by the Junge-Pankow model, but the model tends to overpredict phi for all individual Cl4-8DD/F congeners, especially for the lower chlorinated congeners. On the other hand, good agreement was obtained between the measured and predicted log K(p) values by the K(OA) model for both PCDDs and PCDFs. However, the K(OA) absorption model did not fit the field data at low ambient temperature below 5 degrees C. The disagreement at low ambient temperatures was estimated to arise from the gas adsorption artifacts during the sampling. From the validation by the field measurement data in Nagoya urban air, it is found that the K(OA) absorption model is capable of predicting more accurately gas-particle partitioning of PCDD/Fs than the Junge-Pankow adsorption model.     

Study of PCDD/Fs distribution in fly ash,ash deposits,and bottom ash from a medical waste incinerator in China

Over the past decades in China, the number of medical waste incinerators (MWIs) has been rising rapidly, causing emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). In this study, samples of fly ash, ash deposits, and bottom ash from typical MWIs were analyzed for PCDD/Fs and their distribution characteristics. Results showed international toxic equivalent (I-TEQ) values in the range of 6.9–67 ng I-TEQ/g in fly ash and ash deposits, whereas the concentration in bottom ash was extremely low (only 1.33 pg I-TEQ/g), yet the generation of PCDD/Fs was mostly de novo synthesis in fly ash and ash deposits according to the ratio of PCDFs to PCDDs; the major distribution differences of PCDD/Fs in fly ash was manifested by the content of toxic furan 2,3,7,8-TCDF, but other toxic PCDD/Fs showed similar distribution. Other findings are that 2,3,4,7,8-PeCDF had the most contribution to TEQ concentration, and that the most abundant toxic furan congener is 1,2,3,4,6,7,8-HpCDF. Correlation analysis showed that there was no significant correlation between PCDD/Fs concentration and several other physical and chemical parameters.

Implications: This paper is of interest because it presents the emission performances of PCDD/Fs in ash from medical waste incineration in China. PCDD/F contents in fly ash and ash deposits vary between 6.9 and 67.3 ng I-TEQ/g. However, the concentration in bottom ash was extremely low (only 1.33?×?10^?3 ng I-TEQ/g). The fingerprints of PCDD/Fs in fly ash are almost similar, except for 2,3,7,8-TCDF. There is no marked correlation between PCDD/Fs and other physicochemical properties.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

Estimation and characterization of unintentionally produced persistent organic pollutant emission from converter steelmaking processes

Unintentionally produced persistent organic pollutants (UP-POPs) including polychlorinated dibenzo-p-dioxins, and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) were characterized and quantified in stack gas and fly ash from the second ventilation systems in five typical converters in five different steelmaking plants. The 2378-substituted PCDD/Fs (2378-PCDD/Fs) and dioxin-like PCB (dl-PCBs) toxic equivalents (TEQs) were 1.84–10.3 pg WHO-TEQ Nm^?3 in the stack gas and 5.59–87.6 pg WHO-TEQ g^?1 in the fly ash, and the PCN TEQs were 0.06–0.56 pg TEQ Nm^?3 in the stack gas and 0.03–0.08 pg TEQ g^?1 in the fly ash. The concentrations of UP-POPs in the present study were generally lower than those in other metallurgical processes, such as electric arc furnaces, iron ore sintering, and secondary metallurgical processes. Adding scrap metal might increase UP-POP emissions, indicating that raw material composition was a key influence on emissions. HxCDF, HpCDF, OCDF, HpCDD, and OCDD were the dominant PCDD/Fs in the stack gas and fly ash. TeCB and PeCB were dominant in the stack gas, but HxCB provided more to the total PCB concentrations in the fly ash. The lower chlorinated PCNs were dominant in all of the samples. The 2378-PCDD/F, dl-PCB, and PCN emission factors in stack gases from the steelmaking converter processes (per ton of steel produced) were 1.88–2.89, 0.14–0.76_, and 229–759 μg t^?1, respectively.     

Simultaneous removal of PCDD/Fs and mercury by activated carbon from a full-scale MSW incinerator in southeast China

This study emphasized on the removal performance of polychlorinated-ρ-dibenzodioxins and dibenzofurans (PCDD/Fs) and mercury by different activated carbon injection (ACI) rates from a full-scale (700 t/d) MSW incinerator. The result exhibited that the emission standard of PCDD/Fs and mercury could be met when the ACI rate reached 50 mg/Nm³ and 30 mg/Nm³, respectively. Lower chlorinated PCDD/Fs and PCDFs showed higher removal efficiencies compared with highly chlorinated PCDD/Fs and PCDDs, which could be attributed to the larger competitiveness of highly volatile congeners in AC adsorption than the lower volatile ones. AC turned out to have different adsorption selectivity for CP-routes PCDD/Fs congeners, among which 1379-TCDD was preferred to be absorbed while others exhibited little or poor selectivity for AC adsorption. The removal efficiency of PCDD/Fs was positively correlated with ACI rate at 99% confidence interval with a linear relationship (R²?=?0.98). Also, the outlet concentration of mercury decreased with the increase of ACI rate in a nearly linear function (R²?=?0.96). These results will be meaningful for the rational use of AC for pollutants control.

     

PCBs and PCDD/Fs in lake sediments of Grosser Arbersee, Bavarian Forest, South Germany

Despite their environmental importance, there are still relatively few historical studies of the environmental occurrence of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), especially in middle Europe. Trends in PCBs and PCDD/Fs were, therefore, assessed in lake sediments of the Grosser Arbersee over the past 130 years (1860-1990). Ballschmiter-PCB concentrations (congeners # 28, 52, 101, 138, 153, 180) increased between 1946 and 1972 from 4.2 to 32.0 microg kg(-1) dry wt, but have since decreased to 25.6 microg kg(-1) dry wt. High chlorinated PCB congeners reached their maxima earlier (1968-1972) than low chlorinated congeners (1985-1991). These trends were consistent with patterns expected from the production and use of PCBs and their precursors. PCDD/F concentrations increased between 1950 from 0.6 microg kg(-1) dry wt to 2.3 microg kg(-1) dry wt in 1977, falling to 1.7 microg kg(-1) dry wt by 1993. PCDF concentrations exceeded those of PCDD until 1968, but afterwards PCDDs (especially OCDD) were predominant. These patterns suggest that domestic heating and waste combustion were the most likely sources, but pollution from local industries, such as metal smelting and glass production, might also have been involved. The data provide a valuable case study from central Europe which confirms the overall declining trends of PCB and PCDD/F contamination shown elsewhere.