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.     

PCDD/F and "Dioxin-like" PCB emissions from iron ore sintering plants in the UK

Investigations have been carried out at the three Corus UK sinter plants over the period 2002-2004 to characterise the emissions of both 2,3,7,8-PCDD/Fs and WHO-12 PCBs, to estimate annual mass releases of these organic micro-pollutants using the I-TEF and WHO-TEF schemes, and to investigate the formation of PCBs in the iron ore sintering process. Results showed that the sintering of iron ore produces a characteristic WHO-12 PCB and PCDD/F congener pattern that is substantially the same for all UK sinter plants. With regard to WHO-12 PCBs, the most abundant congeners were typically PCBs 118 (6-9 ngNm(-3)), 105 (2-4 ngNm(-3)) and 77 (2-3 ngNm(-3)). All other WHO-12 PCBs were also detected at concentrations around 1 ngNm(-3). All sinter plants investigated exhibited very similar TEQ concentrations. WHO-12 PCB emissions were in the range 0.042-0.111 ngWHO-TEQNm(-3), whereas PCDD/F emissions ranged from 0.39 to 1.62 ngWHO-TEQNm(-3). PCDF congeners were the main contributors to the overall TEQ in sintering emissions (ca. 85%). Amongst WHO-12 PCBs, PCB 126 was the only noteworthy contributor to total TEQ (ca. 5-7%), a similar contribution to that from PCDDs. Based on the measurements that Corus UK has undertaken at these three sinter plants, annual mass releases of WHO-12 PCBs and PCDD/Fs have been calculated. For UK sinter plants, a total mass release of 29.5 g WHO-TEQ per annum [WHO-12 PCBs+PCDD/Fs] has been estimated, representing 9% of the total PCDD/F emissions to the UK atmosphere. Measurements were also carried out at a UK sinter plant to determine the windleg emission profile of WHO-12 PCBs. Results showed that WHO-12 PCBs were formed in the same regions of the sinter strand as 2,3,7,8-PCDD/Fs, indicating that there was a strong correlation between the formation of WHO-12 PCBs and PCDD/Fs in the iron ore sintering process.     

Formation and mitigation of PCDD/Fs in iron ore sintering

The sintering of iron ore is presently a significant industrial source of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) worldwide owing to the fundamental requirement of the operation of a high temperature process to pre-treat fines and to recycle plant by-products arising from the integrated iron and steelworks. The process is a noteworthy contributor of PCDD/F indirectly due to decreasing PCDD/F releases from municipal solid waste incineration. Commonly PCDD/F formation from the process is associated with the addition of oily mill scales although raw material containing a combination of C, Cl and specific metal catalyst has been shown to drastically increase PCDD/F formation in the process. The degenerate graphitic structure of carbon present in coke fuel and soot formed and the chemistry of catalytic metals and Cl are important factors. A review on PCDD/F emission in this process has been carried out, including examination of its formation mechanism, congener distribution, contributing factors and mitigation strategies, with emphasis on the use of inhibiting compound to achieve suppression. A detailed analysis of the de novo and precursor theories of formation and the contributing factor is given since the subject of PCDD/F formation is still controversial. The de novo formation pathway identified in sinter plants and controlled studies performed in the laboratory as well as at pilot-scale are discussed; where appropriate, a comparison is drawn between sintering and other thermal processes emitting PCDD/Fs. Summary of the latest developments in PCDD/F downstream abatement strategies presently employed in full scale industrial plants is provided. Potential inhibiting compounds are discussed in terms of their mode of action and merits under sintering conditions.     

Atmospheric particle size distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) and their implications for wet and dry deposition

Concurrent measurements of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) in different size fractions of atmospheric particulate matter are presented for a winter and a summer sampling period. The PCDD/Fs and PAHs were primarily associated with particles of <1.35 μm aerodynamic diameter. The particle size distributions were similar for the compounds within each substance group and, surprisingly, also between the PCDD/Fs and PAHs. Changes in the particle size distribution of particle mass were reflected in the particle size distributions of the PCDD/Fs and PAHs.The data were employed to identify those particle size fractions dominating the wet and dry particle bound deposition of PCDD/Fs and PAHs and, furthermore, to assess the relative contributions of wet and dry deposition to the total particle bound deposition fluxes. The calculations indicate that coarse particles contribute most to the dry deposition while, in contrast, the wet deposition of the PCDD/Fs and PAHs is dominated by fine particles. Furthermore, it is estimated that in Bayreuth wet deposition dominates the total particle bound deposition of PCDD/Fs and PAHs.     

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.     

Emission characteristics of PCDD/Fs, PCBs, chlorobenzenes, chlorophenols, and PAHs from polyvinylchloride combustion at various temperatures

The effect of temperature on polyvinylchloride (PVC) combustion using a downstream tubular furnace was investigated for the formation of polycylcic aromatic hydrocarbons (PAHs) and chlorinated compounds. As the temperature increased, higher levels of PAHs were generated. Chlorinated compounds reached a peak at 600 degrees C, with low emissions recorded at 300 and 900 degrees C. There was a close correlation (R2 = 0.97) among polychlorinated biphenyls (PCBs), hexachlorobenzene, pentachlorobenzene, and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). PAHs at all temperatures were analyzed in the gas phase. PCDD/Fs and PCBs were emitted as a solid phase at 300 and 600 degrees C and as a gas phase at 900 degrees C. For some PAHs, chlorobenzenes, and PCDD/Fs, a mathematical equation between the gas and solid phase and the reciprocal temperature in semilog proportion was derived. The proposed equation, which is log (amount in gas phase/amount in solid phase) = -A/T + B, where T is the temperature of the furnace and A and B are constants, for these species relating their gas/solid distributions showed a good relationship.     

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.     

Concentration of organic micropollutants in the atmosphere of Trieste, Italy

Purpose

PCDD/Fs, PCBs, and PAHs, ubiquitous environmental pollutants which are part of the POPs, are mainly produced by anthropogenic activities as well as by natural processes. Occurrences of these pollutants in different sites in Trieste are presented. PCDD/Fs distribution and their possible emission sources are discussed.

Methods

Air samples were collected in different sites near the industrial area, in the city center, and in a background area, using a high-volume sampler equipped with a quartz fiber filter and a PUF. Each sampling lasted a week.

Results

The concentrations of the organochlorinated pollutants are consistent with literature data (??PCDD/Fs and ??dl-PCBs were 5?C38?fg TEQ/Nm³ and 4?C31?fg TEQ/Nm³, respectively), and an apparent seasonal trend was found with slightly higher concentrations in the winter and lower levels in both summer campaigns. Moreover, the isomer profile of each sampling campaign was compared to the fingerprint of a sintering plant, a cement plant, and an incinerator, the main industrial activities in Trieste.

Conclusions

The organic micropollutants were detected in levels consistent with literature data. The results show that the pollutants are uniformally distributed in the atmosphere of Trieste. PCDD/F fingerprints in each site remained almost identical during summer and winter, confirming the yearly prevalence of the emissions from the nearby sintering plant.     

Sources of dioxins in the United Kingdom: the steel industry and other sources

Several countries have compiled national inventories of dioxin (polychlorinated dibenzo-p-dioxin [PCDD] and polychlorinated dibenzofuran [PCDF]) releases that detail annual mass emission estimates for regulated sources. High temperature processes, such as commercial waste incineration and iron ore sintering used in the production of iron and steel, have been identified as point sources of dioxins. Other important releases of dioxins are from various diffuse sources such as bonfire burning and domestic heating. The PCDD/F inventory for emissions to air in the UK has decreased significantly from 1995 to 1998 because of reduced emissions from waste incinerators which now generally operate at waste gas stack emissions of 1 ng I-TEQ/Nm3 or below. The iron ore sintering process is the only noteworthy source of PCDD/Fs at integrated iron and steelworks operated by Corus (formerly British Steel plc) in the UK. The mean waste gas stack PCDD/F concentration for this process is 1,2 ng I-TEQ/Nm3 based on 94 measurements and it has been estimated that this results in an annual mass release of approximately 38 g I-TEQ per annum. Diffuse sources now form a major contribution to the UK inventory as PCDD/Fs from regulated sources have decreased, for example, the annual celebration of Bonfire Night on 5th November in the UK causes an estimated release of 30 g I-TEQ, similar to that emitted by five sinter plants in the UK.     

Improvements to the UK PCDD/F and PCB atmospheric emission inventory following an emissions measurement programme

PCDD/F data are presented from 75 samples of primary emissions sampled between 1995-97 as part of the compliance monitoring survey undertaken by the UK Environment Agency. Municipal solid waste (MSW), chemical waste and clinical waste incinerators, cement kilns, sinter plants and sewage sludge incinerators were the source categories monitored and reported here. Based on this monitoring programme, the previous national UK emission estimates by Eduljee and Dyke (1) of 560-1100 g I-TEQ a(-1) for 1993 have been revised downwards to 220-660 g I-TEQ a(-1). Despite source reduction measures, MSW incinerators remain a significant source of PCDD/Fs to the atmosphere, contributing between 30-50% of the EPCDD/F I-TEQ emission, rather than the approximately 80% they were estimated to contribute in 1993. 2,3,7,8-substituted PCDD/F congener profile data are presented for some of the source categories and generally support the view that differences in the mixtures ('fingerprints') of PCDD/Fs emitted from different sources are observed. New data on the dioxin-like PCB emissions are presented for cement kilns and sinter plants. These show that TEQ-rated PCBs can make an important contribution to the I-TEQ emitted from certain combustion sources. High concentrations of a full range of PCB congeners/homologues have been measured in the atmosphere close to sintering strands, although the precise source of PCBs from this process remains unclear.     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from stack flue gases of sinter plants

This study investigated four sinter plants, classified into two categories--with selective catalytic reduction (SCR) (S1, S2 and S3) and without SCR (S4) as its air pollution control device. Polychlorinated dibenzofurans (PCDFs) are dominant in the stack flue gases of sinter plants with and without SCR. The polychlorinated dibenzofurans/polychlorinated dibenzo-p-dioxins (PCDFs/PCDDs) ratio exceeds 1 extremely. The degree of chlorination of the sinter plant without SCR is towards hepta and hexa congeners while that of the sinter plant with SCR is towards penta and hexa congeners. PCDD/Fs are indeed decomposed (75.5% and 69% on ng and ng TEQ bases, respectively) and not only reduced in degree of chlorination. The overall concentration in the stack flue gas of sinter plants with SCR (7.97-14.1 ng/Nm(3); 0.995-2.06 ng TEQ/Nm(3)) is lower than that of the sinter plant without SCR (28.9 ng/Nm(3); 3.10 ng TEQ/Nm(3)). In Taiwan, based on the emission factors of 0.970 microg TEQ/ton-feedstock (sinter plants with SCR) and 3.13 microg TEQ/ton-feedstock (sinter plant without SCR), the annual PCDD/F emission of 44.7 g TEQ/year from sinter plants is 60 and 121 times higher than those from municipal solid waste incinerators (0.750 g TEQ/year) and MWIs (0.369 g TEQ/year). These results show that sinter plants have become the dominating PCDD/F emission source since tighter emission limits have been applied to incinerators.     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from stack gases of electric arc furnaces and secondary aluminum smelters

This study investigates the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from four electric arc furnaces (EAFs) and eight secondary aluminum smelters (secondary ALSs) in Taiwan. The mean PCDD/F International-Toxicity Equivalents (I-TEQ) concentrations in the stack gases of these EAFs and secondary ALSs are 0.28 ng I-TEQ/Nm3 (relative standard deviation [RSD]= 100%) and 3.3 ng I-TEQ/Nm3 (RSD = 260%), respectively. The high RSDs, especially for those obtained from secondary ALSs, could be caused by the intrinsic differences in their involved feeding materials, furnace operating conditions, and air pollution control devices. The mean I-TEQ emission factor of PCDD/Fs for EAFs (1.8 microg I-TEQ/tonne-feedstock) is lower than that for secondary ALSs (37 microg I-TEQ/tonne-feedstock). This result might be because the involved furnace temperatures for secondary ALSs (650-750 degrees C) are lower than those for EAFs (1600-1700 degrees C), resulting in the deterioration of the combustion condition, leading to the formation of PCDD/Fs during the industrial process. This study found that the total PCDD/F emissions from EAFs (20 g I-TEQ/yr) and secondary ALSs (18 g I-TEQ/yr) are approximately 27, 53, and approximately 24, 49 times higher than those from municipal solid waste incinerators (MSWIs; 0.74 g I-TEQ/yr) and medical waste incinerators (MWIs; 0.37 g I-TEQ/yr), respectively; while those are 44 and 40% of total PCDD/F emission from sinter plants (45 g I-TEQ/ yr), respectively. Considering a more stringent emission limit has been applied to waste incinerators (0.1 ng I-TEQ/Nm3) in Taiwan lately, the results suggest that the control of the emissions from metallurgical processes has become the most important issue for reducing the total PCDD/F emission from industrial sectors to the ambient environment.     

Aircraft Release of Sulfur Hexafluoride as an Atmospheric Tracer

Abstract

The effect of temperature on polyvinylchloride (PVC) combustion using a downstream tubular furnace was investigated for the formation of polycylcic aromatic hydrocarbons (PAHs) and chlorinated compounds. As the temperature increased, higher levels of PAHs were generated. Chlorinated compounds reached a peak at 600°C, with low emissions recorded at 300 and 900°C. There was a close correlation (R² = 0.97) among polychlorinated bi-phenyls (PCBs), hexachlorobenzene, pentachloroben-zene, and polychlorinated dibenzo-p-dioxins and poly-chlorinated dibenzofurans (PCDD/Fs). PAHs at all temperatures were analyzed in the gas phase. PCDD/Fs and PCBs were emitted as a solid phase at 300 and 600°C and as a gas phase at 900°C. For some PAHs, chloroben-zenes, and PCDD/Fs, a mathematical equation between the gas and solid phase and the reciprocal temperature in semilog proportion was derived. The proposed equation, which is log (amount in gas phase/amount in solid phase) = ?A/T + B, where T is the temperature of the furnace and A and B are constants, for these species relating their gas/solid distributions showed a good relationship.     

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.     

Levels of PCDD/FS in ambient air and soil in the vicinity of a municipal solid waste incinerator in Hsinchu

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined in twenty-one ambient air samples, eight soil samples and two stack gas samples, collected near or in a municipal solid waste incinerator (MSWI) in Hsinchu, Taiwan. A systematic decrease of PCDD/Fs in the ambient air from the northeastern area was observed. PCDD/Fs levels measured in the ambient air range from 0.058 to 0.127 pg-TEQ/m3. Higher PCDD/Fs levels in the ambient air were found during winter. In addition, PCDD/Fs levels measured in the soil range from 0.524 to 5.02 pg-TEQ/g d.m. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) did not provide sufficient evidence that the environmental PCDD/Fs contamination was caused by emissions from the Hsinchu MSWI. An unknown PCDD/Fs source was proposed using congener profile analysis and supported by both PCA and HCA.     

Characteristics of dioxins and metals emission from radwaste plasma arc melter system

This study investigated the emission characteristics of PCDD/Fs and the partitioning of three heavy metals (Cd, Hg and Pb) and two radioactive metal surrogates (Co and Cs) in a radwaste plasma arc melter system. Typical mixtures of low-level radioactive wastes were simulated as the trial burn surrogate wastes. The emission of PCDD/Fs and the partitioning of the metals were strongly influenced by the feed waste stream and melter operating temperature, respectively. The emissions of PCDD/Fs, cadmium and lead were greatly enhanced when the polyvinyl chloride was included in the feed waste stream. Most of the nonvolatile cobalt partitioned into the glass. A significant quantity of cesium, cadmium and lead was vaporized during the highest melter temperature test. A lower melter temperature resulted in more cesium, cadmium and lead species remaining in the glass. The results of this study suggest that wet scrubbing as well as a low-temperature two-step fine filtration, or both of them together could not effectively capture the gas-phase or fine particle phase PCDD/Fs and mercury species. In order to effectively treat low-level radioactive waste streams, the tested high-temperature melter should include an adsorption system, which could collect the gas-phase PCDD/Fs and mercury species.     

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.     

Atmospheric pollution by PAHs, PCDD/Fs and PCBs simultaneously collected at a regional background site in central Italy and at an urban site in Rome

Concentrations of PAHs and PCDD/Fs were measured throughout one year, and PCBs during the second semester, at a rural site in a natural park representative of background pollution in central Italy; results were compared with simultaneous measurements performed at an urban site in Rome 60km away. Twenty-four daily samples were collected at each site by a high-volume PM(10) sampler from February 2000 to January 2001. After ultrasonic extraction and clean-up by TLC, samples were analysed by GC-MS. Mean concentrations of benzo[a]pyrene (BaP, as a marker of carcinogenic PAHs), summation operatorPCDD/Fs and summation operator64 PCBs in Rome were, respectively: 1.1ngm(-3), 65fgWHO-TEQm(-3), 553pgm(-3). The background concentrations were, respectively: 0.016ngm(-3), 3fgWHO-TEQm(-3), and 94pgm(-3). Hence, BaP, and the other PAHs, showed the highest urban-background gradient (two orders of magnitude) and PCBs the lowest. The background pollution levels of BaP and PCDD/Fs were in agreement with the few available background/remote measurements in Europe. In Rome PAHs and PCBs, but not PCDD/Fs, were clearly seasonal; the PCDD/F TEQ was moderately correlated with BaP (P<0.001). At the background site, the seasonality of PAHs was less marked, while it could not be assessed for PCDD/Fs and PCBs. The PCB TEQ accounted for 4% and 15% of total (PCDD/Fs+PCBs) TEQ at the urban and background site, respectively. Mean PM(10) concentration was 54microgm(-3) in Rome and 15microgm(-3) at the background site.     

Levels and homologue profiles of PCDD/Fs in sediments along the Swedish coast of the Baltic Sea

Background, aim, and scope  The primary aim of this study was to explore the variations in PCDD/F levels and homologue profiles of Baltic surface sediments by comprehensively analyzing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in samples from a large number of sites, encompassing not only previously known hotspot areas, but also sites near other potential PCDD/F sources, in pristine reference areas (in which there was no industrial activity) and offshore sites. Materials and methods  Surface sediment samples (146 in total) were collected at various points along the Swedish coast and offshore areas. In addition, bulk deposition was sampled, monthly, at a single site in northern Sweden during 1 year. The concentrations of tetra- through octa-substituted CDD/Fs were determined in both matrices. Results  Highly elevated concentrations of PCDD/Fs were found at many sites in coastal areas and concentrations were also slightly elevated in some offshore areas. Homologue profiles varied substantially amongst samples from coastal sites, while those from offshore and other pristine sediments were relatively similar. The offshore sediments showed different profiles from those observed in the deposition samples. Sediment levels of PCDD/Fs were not generally significantly correlated to organic carbon levels, except in some pristine areas. Comparison of data obtained in this and previous studies suggest that both their levels and profiles are similar today to those observed 20 years ago in coastal and offshore areas. The only detected trend is that their levels appear to have decreased slightly in the offshore area of the Bothnian Sea. Discussion  The localization of hotspot areas along the coast, the lack of consensus between PCDD/F profiles of sediments and general background, and their weak correlations with organic carbon suggest that PCDD/Fs in the study area largely originate from local/regional emissions. However, due to complicating factors such as sediment dynamics and land upheaval, it is not possible to conclude whether these pollutants derive from recent emissions or from a combination of recent emissions and re-distribution of previous inputs. Conclusions  The results show that: elevated levels of PCDD/Fs are present in both coastal and offshore areas of the Baltic Sea, the major hotspots are close to the shore, and there are large variations in profiles, indicating that local emissions are (or have been) the major causes of pollution. Recommendations and perspectives  In order to identify other hotspot areas and trace sources, comprehensive analysis of PCDD/Fs in surface sediments is needed in all areas of the Baltic Sea that have not been previously investigated. The high levels of PCDD/Fs observed in surface sediments also indicate a need to elucidate whether they are due mainly to current emissions or a combination of recent pollution and re-distribution of historically deposited pollutants. To do so, better understanding of sediment dynamics and present-day inputs, such as riverine inputs, industrial effluents, and leakage from contaminated soil is required. There are indications that contaminated sediments have a regional impact on fish contamination levels. However, as yet there is no statistically robust evidence linking contaminated sediments with elevated levels in Baltic biota. It should also be noted that the Baltic Sea is being massively invaded by the deep-burrowing polychaete Marenzielleria ssp., whose presence in sediments has been shown to increase water concentrations of hydrophobic pollutants. In awareness of this, it is clear that high levels in sediments cannot be ignored in risk assessments. In order to investigate the emission trends more thoroughly, analysis of PCDD/Fs in offshore sediment cores throughout the Baltic Sea is also recommended. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Formation of PCDD/Fs in the sintering process: role of the grid-Cr2O3 catalyst in the de novo synthesis

The sintering process is among the major sources of the very toxic polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in the environment. At the industrial scale, it has been shown that dust collected on the grid, which supports the feed, contains PCDD/Fs amounts between the values found in the bottom of the cake and the values found on dust collected during gas sampling in the wind boxes. This fact suggests that the grid, containing 25wt.% of chromium, could have a catalytic activity in PCDD/Fs formation during the sintering process. This research tries to study this potential role. The de novo synthesis of PCDD/Fs is simulated at laboratory scale by thermal treatments of samples mixed with grid filings or Cr2O3. The thermal experiments performed with E.S.P. dust (dust collected in the electrostatic precipitator of a sintering plant) or graphite mixed with grid filings do not allow to confirm a role of the grid in PCDD/Fs formation during the industrial process. On the other hand, it has been shown that Cr2O3 can be considered as a catalyst in the de novo synthesis of PCDD/Fs. This compound takes place in the two steps of the de novo synthesis: the degradation of the carbon matrix as well as the chlorination reactions.