Levels and possible sources of PCDD/PCDF in sediment and pike samples from Swedish lakes and rivers. (Part one)

One goal of the Swedish survey project is to discover possible sources of PCDD/F. Bottom sediment and pike were sampled at various sites near different types of industries along the coast line of two lakes and one river. The results show background levels of PCDD/F in some lakes which can only be explained by atmospheric input. In some lakes paper mill emissions of chlorinated PCDD/F give high levels of local contamination (≈1 ng/g IG) within short distances (<1 km) from the source. PCDD/F from paper mill effluents are transported long distances and traces can be detected over the entire lake area. The PCDD/F levels in pike are correlated with levels in the underlying sediment.     

Concentrations of polychlorinated dibenzo-p-dioxins and furans in fish downstream from a Ky-5 manufacturing

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in seven fish species, burbot (Lota lota), pike (Esox lucius), perch (Perca fluviatilis), pikeperch (Stizopedion lucioperca), bream (Abramis brama), salmon (Salmo salar) and Baltic herring (Clupea harengus membras) in River Kymijoki and its estuary polluted by Ky-5 manufacturing. The fish were caught at 14 localities along the river and its estuary. The selected species represent different trophic levels and/or inhabit different environments. The concentrations of PCDD/Fs were low, in most samples below 1 pg g(-1) ITEQ (NATO/CCMS 1988) fresh weight (fw) in muscle, except salmon and Baltic herring. These two species graze at the open sea and consequently accumulate contaminants at a large area in the Baltic Sea. The lipid content in salmon and Baltic herring was an order of magnitude higher than in other species. PCDD/Fs in fish muscle showed only slightly elevated levels in the Kymijoki area and its estuary as compared to the levels in the same species in Finnish freshwaters and sea areas. The concentration of the main impurities of the fungicide Ky-5 was higher in the Kymijoki River downstream the Ky-5 manufacturing place compared to the up-stream locations. The PCDD/F concentrations in fish liver and spawn were 10-100 times higher than the concentration in muscle, because of the much higher lipid concentrations of these organes. Consequently, the tolerable daily intake values could be as much as 100 times smaller (M. Korhonen, M. Verta, T. Vartiainen, Organohalog. Comp. 32 (1997) 305-310; P. Mikkelson, J. Paasivirta, H. Kiviranta, Organohalog. Comp. 39 (1998) 59-62).     

PCDD/F and PCB history in dated sediments of a rural lake

Concentrations of polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and biphenyls (PCB) were analysed from a sediment core, which had been sampled from a remote lake in Finland. The deepest subsamples were analysed from a depth of 4.0 m, and were more than 8000 years old. At the surface of the sediment core, low levels of industrial background contamination were detected. The sum of 2,3,7,8-substituted PCDD/Fs was 35 ng/kg d.w. (dry weight), or 1.2 ng/kg d.w. in WHO's toxicity equivalent, WHO-TEQ. The annual accumulation rate of 2,3,7,8-substituted PCDD/Fs was 1.26 ng m(-2) a(-1). Deeper in the core, PCDD/F concentrations ranged between 2.11 and 11.1 ng/kg d.w. (0.24 and 1.70 ng/kg d.w. WHO-TEQ) and the accumulation rate was 0.11 ng m(-2) a(-1). A characteristic PCDD/F congener profile was found in all pre-industrial sediment layers. The order of concentrations was OCDD > 1,2,3,4,6,7,8-HpCDD > 1,2,3,7,8,9-HxCDD > 1,2,3,4,7,8-HxCDD > 2,3,7,8-TCDD, and concentrations of 2,3,7,8-chlorinated dibenzofurans were below the detection limit. Similar congener profiles have previously been described in samples for which natural PCDD/F formation has been proposed. PCBs were present at low levels in all of the sediment samples. The sum of the PCB concentrations of the sediment subsamples ranged between 50 and 2540 ng/kg d.w., and the three predominant congeners in the core were PCBs 18, 52, and 110.     

Historical trends of PCDD/Fs and dioxin-like PCBs in sediments buried in a reservoir in Northern Taiwan

Polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF) and polychlorinated biphenyl (PCB) concentrations were analyzed at 1-2cm intervals in a sediment core collected from a reservoir in Northern Taiwan to evaluate the organic pollution history. The highest PCDD/F (14.4ng TEQ/kg d.w.) and PCB (0.261ng TEQ(WHO)/kg d.w.) concentrations were determined at 13-15cm (estimated year: 1992). The ages of the levels of sediment core were estimated from the sedimentation rate. Analysis results demonstrate that the PCDD/F concentration of the sediment core measured in the reservoir reached their peak when the municipal waste incinerators (MWIs) in the area started to operate. Furthermore, the decrease in sediment core PCDD/F concentration is related to the time of enforcement of the PCDD/F emission limit set by the Environmental Protection Administration (EPA) in Taiwan. Significant distribution of OCDD in homologue profiles was noted in archived soil samples in Taiwan in which the major input of PCDD/Fs was thought to be atmospheric. Major PCB congeners found in the sediment core were the major components of the commercial PCB products. Input fluxes of PCDD/Fs (5.75-158ng-I-TEQ/m(2)-yr) and PCBs (0.248-3.71ng TEQ(WHO)/m(2)yr) into the reservoir of interest are also calculated from the concentration and sedimentation rate of the sediment. The results reveal that considerable amounts of PCDD/Fs and PCBs were carried into the reservoir of interest in the flood stage but not during normal stage.     

Distribution of PCDDs and PCDFs in Soils Collected from the Denver Front Range - Principal Components Analysis of Diffuse Dioxin Sources (10 pp)

Background, Aims and Scope The Rocky Mountain Arsenal (RMA) is a US Army facility located northeast of Denver, Colorado that has been listed on the National Priorities List (NPL). It is currently being re-mediated under the authority of the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) and the Superfund Amendments and Reauthorization Act of 1986 (SARA). As part of the remediation activities at RMA, indications were found that a source of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) had existed on the RMA. As a result, investigations were undertaken to assess the possible nature and extent of any potential sources of PCDDs and PCDFs on the RMA site. In addition, other studies were conducted that examined PCDD/PCDF contamination in the Denver area. The goal of these studies was to examine nature and extent of PCDD/PCDF contamination both on the RMA as well as in the surrounding Denver area. The intent of this study was to characterize sources of dioxins (PCDDs) and dibenzofurans (PCDFs) at low environmental concentrations which might have originated from diffuse sources in the Denver Colorado area and in particular, the Rocky Mountain Arsenal (RMA) using Principal Component Analysis (PCA). Methods Over 200 soil samples were collected from the RMA and the Denver area. From the RMA, soil was collected as part of three studies that included a (1) random site-wide sampling of the RMA, (2) soils from the Western Tier Parcel (WTP), and (3) soils from Historic Use areas. Denver area soil samples were collected from five different land use categories: Residential, Agricultural, Open Space, Commercial, and Industrial. PCA was conducted on concentrations of 17 2,3,7,8-substuituted PCDD and PCDF congeners in 220 soil samples collected from the RMA and the Denver Front Range region. Results and Discussion PCA demonstrated the presence of possible minor sources of dioxins on the RMA. Current remediation efforts on RMA will result in the removal of these sources. Samples from the RMA were identified by the presence of a congener profile containing higher chlorinated PCDFs while the Denver Front Range areas were characterized by the presence of higher chlorinated PCDD congeners. The presence of a PCDF signature for the RMA samples does not necessarily indicate a major source of these contaminants on-site. Indeed, the relatively diffuse nature of the sample clusters would argue strongly against the presence of a single large source. Instead, the predominance of the PCDF congeners probably indicates the mixed industrial activities that took place on and near the site. Conclusion PCA results indicate that PCDD/PCDF profiles in soils collected from the RMA differed from those collected from the outlying Denver areas but that a major source of these contaminants was not present. Rather, the diffuse nature of sample clusters from the PCA indicated that the congener profile of RMA samples was most likely a result of the mixed industrial activities that historically have taken place on and near the site. PCA also indicated that many of the 'open area' (peripheral site-wide) RMA soils samples did not differ from Denver are reference congener profiles. This finding was also true for samples collected from the WTP that were essentially indistinguishable from Off-RMA reference samples. In addition, total TEQ concentrations in soils collected from WTP were similar to those measured in soils collected from the Denver Front Range areas indicating that lack of a major source of PCDD/PCDF within the WTP zones of the RMA. Recommendation and Outlook Analytical as well as statistical results of the soil congener data indicate that the WTP soils are indistinguishable from soils collected from non-industrial areas in the Denver area. This finding would support the recent 'de-listing' of the WTP from the other RMA areas and its' transfer to other authorities in the Denver area.     

POPs in the Lagoon of Venice: budgets and pathways

Dioxins and furans (PCDD/Fs), polychlorobiphenyls (PCBs) and hexachlorobenzene (HCB) in the ecosystem of the Lagoon of Venice were studied, in order to provide a general picture of conditions in the lagoon in terms of contamination by persistent organic pollutants (POPs). We present here novel data on atmospheric deposition, water, sediment and clam samples collected in the lagoon during the period January 2001-December 2004. Atmospheric deposition was sampled monthly at six sites located both close and far from large industrial and urban sources. Water samples were collected monthly from fifteen stations, and twenty-five samples of sediments and clams (Tapes philippinarum) were collected in four areas where clams are farmed and harvested inside the lagoon. All samples were analysed for PCDD/Fs, PCBs and HCB by HRGC/HRMS in the same laboratory. All samples examined (atmospheric deposition and water) substantially confirmed the spatial pattern reported in previously published data on sediments and atmospheric deposition: the zone surrounding the Porto Marghera petrochemical plant always had the highest levels of POPs (i.e., PCDD/Fs: atmosphere approximately 6 pg of 2,3,7,8-TCDD equivalents (I-TE) m(-2)d(-1); water 0.37 pg I-TEl(-1); sediment: 300 ng kg(-1); clam 2.8 pg I-TE g(-1)), and the minima were found at points on the margins of the lagoon (PCDD/Fs: atmosphere approximately 1 pg I-TEm(-2)d(-1); water 0.05 pg I-TEl(-1); sediment: approximately 5 ng kg(-1); clam approximately 0.2 pg I-TE g(-1)). Intermediate values were often encountered in the historical city centre of Venice and in the central part of the lagoon. To confirm this, new data on correlation between levels of PCDD/F in sediments and clams are reported, both for absolute values and for the PCDD/F "fingerprint". There is always a clear fingerprinting signature (PCDF/PCDD>1) for samples collected near Porto Marghera, and the opposite (PCDF/PCDD<1) in the rest of the lagoon.     

PCDD/F levels in food and canteen meals from southern Germany

Analysis of food samples collected in 1997 and 1998 in Bavaria, Germany showed that PCDD/F levels in food of animal origin, with the exception of fish, have decreased to low levels way below 1 pg I-TEQ/g fat. Lowest PCDD/F contents were found in pork (mean: 0.27 pg I-TEQ/g fat) followed by poultry and cow's milk (mean: approx. 0.5 pg I-TEQ/g fat). Average contamination levels determined in beef and eggs lay in the range from 0.7 to 0.8 pg I-TEQ/g fat. PCDD/F levels in fish were clearly higher than levels in meat, milk and egg samples (mean: 5.6 pg I-TEQ/g fat). Comparison of topical levels with former results from Bavaria show that the recently detected decline of contamination of food has continued during the past few years. In addition to investigations of unprepared food, we analysed prepared canteen meals over a period of 1 year. The average PCDD/F level found in canteen food (0.37 pg I-TEQ/g fat) was in good conformity with determined PCDD/F levels in unprepared food regarding the estimated fat composition of prepared meals. The average consumption of fat per meal via canteen food was 21.1 g and the average PCDD/F intake per meal was 7.6 pg I-TEQ. On the supposition that determined PCDD/F levels in canteen food on fat basis are representative of total fat consumed by humans (102 g fat/day), the daily PCDD/F intake would amount to a mean value of 36.7 pg I-TEQ corresponding to 0.52 pg I-TEQ/kg body weight.     

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

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

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.     

PCDD/Fs in ambient air collected in Zagreb, Croatia

Levels of PCDD/Fs were measured at four different sites in Zagreb, capital of Croatia. Also one sample was taken during spontaneously initiated open fire on a landfill and one sample where garden waste of unknown content was burnt. Over period 1997–2000, 28 samples were collected and levels ranged between 9 and 306 fg I-TEQ m⁻³, except in the sample collected during landfill fire. Air PCDD/F levels in Zagreb at four sites were different and the highest levels were observed in industrial area. Seasonal variation of levels is also evident with higher levels in winter than in summer. Our results show that PCDD/F levels in ambient air collected in Zagreb are at lower end of the published data range. In general, homologue profiles were quite similar for all locations, the concentration of PCDD homologues increased while the concentration of PCDF homologues decreased with increasing degree of chlorination. PCDD/F levels in the landfill fire sample was 13 200 fg I-TEQ m⁻³ which are much higher than levels in garden waste burning sample or in sample collected at industrial site. During landfill fire, the concentration of 2,3,7,8-TCDF becomes even higher than the concentration of OCDF and is equal to the concentration of 1,2,3,4,6,7,8-HpCDF.     

Human exposure to dioxins and furans: application of the substance flow analysis to health risk assessment

Substance Flow Analysis (SFA) is an important instrument that allows for the undertaking of environmental management for a specific contaminant. 'Control Analysis' is a tool that assesses the effect on a target flow of changes in flows forming part of a control basis set. The purpose of the present study was to perform a modeling of the annual PCDD/F flows in Tarragona Province and to apply the model for human health risk assessment. The validation of the model has been evaluated by comparing estimated fluxes with experimental values. Eleven subsystems, as well as a set of 88 flows of the system in Tarragona Province were considered. The total PCDD/F accumulation in Tarragona Province was between 62.6 and 159.5 g I-TEQ/y. Accumulation in sediments (27.9-74.6 g I-TEQ/y) and soils (35.0-80.8 g I-TEQ/y) are the two principal modes of deposition. Estimated flow in human adipose tissue means a mean intake of PCDD/F (via ingestion and inhalation) of 243 pg I-TEQ/person/day. The food chain pathway accounts for 99% of the total daily intake. As a result of the simulation, a 100% decrease in industrial emissions would cause a 1.7% reduction in the PCDD/F accumulation in humans. In turn, a 100% reduction of PCDD/Fs in the industrial waste waters would cause only an insignificant 0.1% decrease in the accumulation of PCDD/Fs in humans.     

Temporal and local trends of PCDD/F levels in cow's milk in Switzerland

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) were determined in 30 Swiss cow's milk samples collected at dairy farms in the vicinity to point sources, in rural/alpine areas distant to known sources, and from tanks in large industrial milk processing plants. The contaminant concentrations in samples collected in 2001 were compared to data from analyses conducted in 1984 and 1990/1991 at the same sites. In 2001, the PCDD/F levels in milk from farms near point sources (0.63+/-0.26 ng I-TEQ/kg milk fat) are slightly but significantly higher in than milk from remote areas (0.36+/-0.09 ng I-TEQ/kg milk fat). Consumer milk collected at the processing plants had intermediary levels (0.51+/-0.19 ng I-TEQ/kg milk fat). However, milk in 2001 was significantly less contaminated than the samples collected in 1990/1991 and 1984. This trend is particularly pronounced near point sources but is also apparent in consumer milk and milk from remote areas. No geographical gradient in the atmospheric input of PCDD/F in Switzerland was found. The reduction in PCDD/F levels in dairy milk is paralleled by and correlated to the remediation of known PCDD/F emitting industries, as enforced by federal authorities.     

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.     

PCDD/Fs and PCBs in Baltic herring during the 1990s

Baltic herring samples caught from the Baltic Sea during the spring periods of 1993-1994 and 1999 were analysed for polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and polychlorinated biphenyls (PCB). For analyses, 1570 individual herring were combined to 120 pools. Correlations between concentrations of congeners 1,2,3,7,8-PeCDD, 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF, and 2,3,4,6,7,8-HxCDF, and age of herring were the strongest (r>0.8) followed by correlations between PCB congeners PCB 105, 118, 126, 156, 169 and 180 (r>0.7), and age of herring. Due to higher fat percentage in herring in the Gulf of Bothnia the concentrations of PCDD/Fs and PCBs on fresh weight (fw) basis were higher than in herring in the Gulf of Finland. The concentrations of WHO(PCDD/F)-TEQs ranged from 1 to 27 pg/g fw, depending on the age and catchment area of herring, and concentrations of WHO(PCB)-TEQs reached 32 pg/g fw. Between the two studied time points no clear downward trend in concentrations was observed.     

PCDD/F in waste water discharges from flue gas scrubbers of waste incinerators and coal operated power plants

Scrubber water samples from different combustion plants and gypsum samples as obtained in the flue gas washing with lime water were analyzed for PCDD/F. Three of the investigated nine scrubber water samples showed PCDD/F contents between 0,4 and 11,5 ng I-TEq/1 where as in the 17 gypsum samples examined only in a few cases very low levels of HpCDD and OCDD could be detected.     

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.     

Monitoring of polychlorinated dibenzo-p-dioxins and dibenzofurans, dioxin-like PCBs and polycyclic aromatic hydrocarbons in food and feed samples from Ismailia city, Egypt

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyl (PCBs) and polycyclic aromatic hydrocarbons (PAHs) have been determined using GC/HRMS in food (butter, seafood and meat) and feed samples (chicken, cattle and fish) purchased from Ismailia city, Egypt. PCDD/F concentrations in food samples ranged between 0.12 and 3.35 pg WHO TEQ/g wet w, while those in feed samples were between 0.08 and 0.2 pg WHO TEQ/g dry w. Levels of PCB TEQ ranged from 0.14 to 3.2 pg/g wet w in the food samples. The feed samples have an average of 0.35 pg PCB TEQ /g dry w. In this study, butter samples showed the highest contamination levels of PCDD/Fs and PCBs. The PCBs contribution to the total TEQ was on average 63% in seafood and on average 49% for meat and butter. The highest contamination levels of PCDD/Fs and PCBs were found in butter samples. The butter TEQ content is several times higher than that reported in all EU countries and exceeded the EU limits, while the PCDD/F levels in seafood and the feed samples is far below the current EU limit. Generally, congener profiles in the food samples reflect the non-industrialized nature of the city and suggest solid waste burning as a significant source of emission. Nevertheless, the profiles for butter suggest an impact from various sources. In the case of the sum of 16 PAH contamination levels in food samples were in the range of 11.7-154.3 ng/g wet w and feed samples had a range of 116-393 ng/g dry w. Benzo(a)pyrene (BaP) has been detected in the range of 0.05-3.29 ng/g wet w in the food samples; butter showed the highest contamination which exceeded the EU standard set for fats and oil. Fingerprints of PAHs suggested both petrogenic and pyrolytic sources of contamination.     

Estimation of PCDD/F distribution and fluxes in the Venice Lagoon,Italy: combining measurement and modelling approaches

The available experimental information on the occurrence of PCDD/Fs in the Venice Lagoon, Italy, was compiled and used to calculate fugacities for the environmental compartments of sediment, suspended particulate matter (SPM), water and air and then used to estimate fugacity ratios and assess the likely net direction of flux between media. The bottom sediment: SPM fugacity ratios for different PCDD/Fs indicate conditions close to equilibrium, suggestive of the close coupling of SPM with re-suspended sediment. Sediment/water and the sediment/air fugacity ratios suggest that net flux directions vary depending on the congener and the location within the lagoon. Net sediment-water-air movement (i.e. re-mobilisation/volatilisation) is suggested for the lighter congeners from the industrial canals, where the highest PCDD/F concentrations in the lagoon occur. The tendency to volatilise increases with decreasing congener molecular weight. In contrast, net deposition (air-water-sediment) appears to be occurring for the heaviest (hepta- and octa-) substituted PCDD/Fs. OCDF represents a marker of the industrial district of the lagoon, decreasing in concentration and as a fraction of total PCDD/Fs with increasing distance. The fugacity-based quantitative water air sediment interaction (QWASI) mass-balance model was applied to the central part of the lagoon. The key parameters for the determination of the model output, identified by a sensitivity analysis, were: the sediment active depth, the sediment re-suspension and deposition rates, and the total input of PCDD/Fs to the system. The QWASI model also indicates the tendency for the lighter PCDD/Fs to be released from surface sediment to the water column.     

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.     

Analysis of dioxin-like compounds in vegetation and soil samples burned in Catalan forest fires. Comparison with the corresponding unburned material

Only a few data are reported about the formation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in forest fires. However, the inventories of sources undertaken by several European and American countries consider natural fires as a possible source of PCDD/F and, in some cases, as one of the most important. In our work we have analysed vegetation and soil samples burned in four forest fires which happened in Catalonia in the summer of 1998. The concentration of dioxin-like compounds (PCDD/F, non-ortho polychlorinated bi-phenyls (PCB) and mono-ortho PCB) has been compared to the concentration present in the corresponding unburned material collected in places near the fires but not affected. The results of this preliminary study show very low concentrations in all the samples, both burned and unburned. Although a change in the profile (proportional increase of tetrachlorinated congeners in PCDD/F) is observed in burned samples compared to unburned ones, the absolute values of concentration decrease in most samples. Therefore, natural fires seem not to be an important source of dioxin-like compounds. These results will be confirmed with air emissions measurements in future studies.