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.     

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.     

Monitoring PCDD/Fs, PCBs and metals in the ambient air of an industrial area of Catalonia, Spain

In 2005 and 2006, the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and metals (As, Be, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sn, Tl and V) were measured in air samples collected in an industrial area of Sant Adrià del Besòs (Barcelona, Catalonia, Spain) where a municipal solid waste incinerator (MSWI) is placed, and in a background/control area. In general terms, concentrations of all environmental pollutants were higher at the industrial site. No significant seasonal/temporal variations were observed in any of the areas. No Pearson correlation was found between the PCDD/F concentrations and the environmental conditions of the two sampling periods considered. Principal component analyses (PCA) were performed to get information on the relationship among samples, pollutants, and emission sources. The results indicate that the MSWI of S. Adrià de Besòs is not a significant emission source of the above compounds for the area under its direct influence. Moreover, a notable difference in the PCDD/F congener profiles was found between ambient air and stack gas emissions, indicating that the current levels of PCDD/Fs are more related to other potential emissions sources rather than to those from the MSWI.     

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.     

Dry deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ambient air

The PCDD/Fs in the ambient air associated with concentration and dry deposition flux of four seasons were characterized in rural area. The mean PCDD/F concentrations were 0.342, 0.221, 0.675, 0.741 pg m(-3) and the mean I-TEQ values were 0.027, 0.016, 0.024, 0.063 pg m(-3) in spring, summer, fall and winter, respectively. Ambient air in winter was higher by a factor of 3.4 and 3.9 for PCDD/F concentration and I-TEQ, respectively, than in summer. The study area is located in a Tropical region. Hence, domestic heating is not found in this area and is not responsible for the elevated winter concentration in comparison to other studies. A smooth plate with a sharp leading edge that is pointed into the wind by a wind vane was used for measuring dry deposition flux of PCDD/Fs. Atmospheric dry deposition fluxes of total PCDD/Fs were 140, 116, 137, and 207 pg m(-2)day(-1) in spring, summer, fall, and winter, respectively, and averaged approximately 150 pg m(-2)day(-1). The total dry deposition flux was found to decrease as the temperature increased. Calculated dry deposition velocities of total PCDD/Fs were 0.45, 0.52, 0.32 and 0.39 cm s(-1) in spring, summer, fall, and winter, respectively, and averaged 0.42 cm s(-1).     

Influence of a municipal solid waste incinerator on ambient air and soil PCDD/Fs levels

To examine the influence of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) emissions from a municipal solid waste incinerator (MSWI) on the environment, we measured the levels of PCDD/Fs in ambient air and soil samples collected near a MSWI in Bucheon, Korea. The PCDD/Fs concentrations in the ambient air samples ranged from 0.22 to 1.16 pg I-TEQm(-3) (13.39-75.16 pg m(-3)), with an average of 0.66 pg I-TEQ m(-3) (35.62 pg m(-3)). The soil samples contained between 1.25 and 74.98 pg I-TEQ g(-1) (38.15-3,303.33 pg g(-1)), with an average of 19.06 pg I-TEQ g(-1) (1,077.11 pg g(-1)). These levels were higher than those previously reported by other investigators in a number of surveys. The furan homologues predominated in the air samples and some soil samples, and the soil PCDD/Fs levels decreased with increasing distance from the MSWI. Comparison of the homologue patterns and a multivariate statistical analysis showed that PCDD/Fs emission from the MSWI directly affected the pattern of PCDD/Fs in air, while the PCDD/Fs patterns in soil differed according to the location relative to the MSWI, roads, and construction sites. These results collectively indicate that the MSWI was the major PCDD/Fs emission source in this area, but that unidentified combustion sources and vehicles might influence the environment to some extent.     

Air concentrations of PCDD/Fs, PCBs and PCNs using active and passive air samplers

The concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) were determined in air samples collected at four sampling sites located in two zones of Barcelona (Spain): near a municipal solid waste incinerator (MSWI) and a combined cycle power plant (3 sites), and at a background/control site. Samples were collected using high-volume active samplers. Moreover, 4 PUF passive samplers were deployed at the same sampling points during three months. For PCDD/Fs, total WHO-TEQ values were 27.3 and 10.9 fg WHO-TEQm(-3) at the urban/industrial and the background sites, respectively. The sum of 7 PCB congeners and the Sigma PCN levels were also higher at the industrial site than at the background site. In order to compare active and passive sampling, the accumulated amounts of PCDD/Fs, PCBs and PCNs in the four passive air samplers, as well as the total toxic equivalents in each sampling site were also determined. To assess the use of PUF passive samplers as a complementary tool for PCDD/F, PCB and PCN monitoring, sampling rates were calculated in accordance with the theory of passive air samplers. PUF disks allowed establishing differences among zones for the POP levels, showing that they can be a suitable method to determine POP concentrations in air in areas with various potential emission sources. Although both particle and gas phase were sorbed by the PUFs, data of gas phase congeners are more reproducible.     

Seasonality of PCDD/Fs in the ambient air of Malopolska Region,southern Poland

Background, aim, and scope  

The aim of the study was to identify the impact of polychlorinated dibenzo-p-dioxin and furan (PCDD/F) emission sources on ambient air concentrations in the Malopolska Region, southern Poland. Three sites were selected: the city center of Krakow (Aleje), an industrial area (Nova Huta), and a rural site (Zakopane). In order to investigate the annual variations of PCDD/F sources, summer and winter time samples were taken.     

Survey of PCDD/Fs and non-ortho PCBs in UK sewage sludges

A survey of PCDD/F and non-ortho PCB concentrations in the mesophilic, anaerobically digested sludge of 14 UK wastewater treatment works was carried out. The range of total Cl1-Cl8DD/F concentrations in the sludges was 8880-428000 pg/g dw with a median of 23300 pg/g dw. The concentrations of the three non-ortho PCBs were in the range 272-63000 pg/g dw with a median of 695 pg/g dw. The PCDD/F I-TEQs of the sludges studied were comparable to those published in the literature with a range of 20-225 pg I-TEQ/g dw and a median of 40.4 pg/g dw. The non-ortho PCBs usually added 2-7 pg/g to the total TEQ with one notable exception which increased the TEQ value 20-fold. With three exceptions, the PCDD/F content of the sludges fell well below the draft EU limit values proposed on 27 April 2000. The homologue group pattern of the PCDD/Fs is dominated by the HpCDDs and OCDD and is consistent with that found in most sewage sludges. There appears to be no correlation between the degree of industrial input and the PCDD/F concentration. This suggests that trade effluent is not always the most significant source of PCDD/Fs to wastewater in the UK.     

Phytoremediation to increase the degradation of PCBs and PCDD/Fs

Phytoremediation is already regarded as an efficient technique to remove or degrade various pollutants in soils, water and sediments. However, hydrophobic organic molecules such as PAHs, PCBs and PCDD/Fs are much less responsive to bioremediation strategies than, for example, BTEX or LAS. PCDD/Fs and PCBs represent 3 prominent groups of persistent organic pollutants that share common chemical, toxicological and environmental properties. Their widespread presence in the environment may be explained by their chemical and biological stability. This review considers their fate and dissipation mechanisms. It is then possible to identify major sinks and to understand biological activities useful for remediation. Public health and economic priorities lead to the conclusion that alternative techniques to physical treatments are required. This review focuses on particular problems encountered in biodegradation and bioavailability of PCDD/Fs and PCBs. It highlights the potential and limitations of plants and micro-organisms as bioremediation agents and summarises how plants can be used to augment bacterial activity. Phytoremediation is shown to provide some new possibilities in reducing risks associated with dioxins and PCBs.     

Structure-related distribution of PCDD/Fs, PCBs and HCB in a river-sea system

Water concentrations of PCDD/Fs, HCB, and non-ortho, mono-ortho, and non-dioxin-like PCBs were measured four times during 1 year in a coastal area of the Baltic Sea, to investigate background levels and distribution behaviour. Sampling sites included two rivers, an estuary, and the sea. Particulate and apparently dissolved concentrations were determined using active sampling (filters + PUFs), while freely dissolved concentrations were determined using passive sampling (POM-samplers). The distribution between particulate + colloidal and freely dissolved phases, in the form of TOC-normalized distribution ratios (K_TOC), was found to be near or at equilibrium. The observed K_TOC were not significantly different between sampling sites or seasons. For PCDD/Fs, the concentrations were significantly correlated to suspended particulate matter (SPM), while no correlation to organic carbon (TOC) was observed. In the estuary and the sea, PCB concentrations were correlated to TOC. The sorption of various congeners to SPM and TOC appeared to be related to both hydrophobicity and 3D-structure. The PCDD/F concentration in the sea decreased to one third in May, likely connected to the increased vertical flux of particles during the spring bloom.     

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/Fs, dioxin-like PCBs and marker PCBs in eggs of peregrine falcons from Germany

Thirty one egg samples of peregrine falcons were collected in different regions of Germany (South-West, North and East) and analysed for PCDD/Fs, PCBs and marker PCBs. Altogether, 37 PCB congeners were determined, allowing a more detailed discussion of different aspects of the relative importance of these individual congeners. For comparison with dioxin data from other studies, differences between toxic equivalency factors (TEF) have to be taken into consideration. The results of this study are discussed on the basis of WHO-TEFs for birds published in 1998. All samples showed high levels of PCDD/Fs (median of all samples: 368 pg WHO-PCDD/F-TEQ/g fat; range 137-1453) and even higher levels of PCBs (median 967 pg WHO-PCB-TEQ/g fat; range 243-7482). The upper range of these levels reach concentrations found at the beginning of the Belgian dioxin crisis when a significant reduction in hens' egg hatchability was observed. The relative contribution of PCBs to the total TEQ is on average 71% (range 55-92%) with a tendency to higher values in South-West Germany compared to different sites in East Germany or one site in northern Germany. Within a region, a wide range of contamination can be found. Even in the same cities (Stuttgart and Ludwigshafen), results derived from eggs collected in the same year (2003) varied by factors 5-10. These findings show the high degree of variation occurring even within the same kind of biological matrix. Therefore, to allow for comparison of regions or time trends, a considerable number of samples has to be analysed.     

PCBs,PCNs, PCDD/Fs,PAHs and Cl-PAHs in air and water particulate samples--patterns and variations

Methodology for the determination of biologically active polychlorinated biphenyls (PCBs), non-ortho PCBs, polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polycyclic aromatic hydrocarbons (PAHs) was used to investigate concentrations and patterns of certain chlorinated PAH (Cl-PAH) in source related samples using synthetic reference mixtures. Thus, in addition to the above mentioned compounds, mono-heptachlorosubstituted fluorenes, phenanthrenes/anthracenes and pyrenes/fluoranthenes (Cl-PAHs) were measured in vapour and particulate air samples from urban road tunnels, samples of settling particulate matter (SPM), and in bottom sediment samples from two point source locations (pulp and paper, and Mg-plant/Fe-Mn-smelter/chlor-alkali) and in the Baltic Sea. Concentrations in air samples followed: PAHs>PCBs>PCNs>non-ortho PCBs or Cl-PAHs>PCDD/Fs. SPM samples collected at increasing distance to the urban area of Stockholm showed: PAHs>PCBs>PCNs>PCDD/Fs>non-ortho PCBs or Cl-PAHs. For all compound groups there was a tenfold (Cl-PAHs fivefold) concentration decrease in SPM samples from highest levels in the urban water area to lowest levels at a distance of 26 km from city centre. PCB profiles of SPM showed similarities with combined profiles of Aroclor 1242 and 1254. PCN profiles of SPM showed similarities with combined profiles of Halowax 1099 and 1014. A correlation with concentration of all tested Cl-PAH and their corresponding parent PAH was found only for Cl-fluorene.     

The role of a steel plant in north-west Italy to the local air concentrations of PCDD/Fs

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are ubiquitous contaminants, mainly released into the environment during combustion processes (point sources), but also from other sources (traffic, uncontrolled combustion).This study aims at investigating the contribution of a steel plant in NW Italy (700 000 tons of steel year⁻¹) to the air concentrations of PCDDs/PCDFs at local level, through the analysis of measured, modelled and literature data. The study was carried out in an area of 600 km², using air quality data measured by the institutional monitoring network, data obtained from AERMOD simulations and literature data.The measured air concentrations were consistent with literature values for similar areas, and both the homologue profiles and PCA analyses showed a clear distinction between the monitoring stations and the source profiles.All the previous results were confirmed by the air dispersion model (AERMOD), that predicted PCDD/F air concentrations due to the steel plant from four to two orders of magnitude lower than those measured in the monitoring stations, highlighting the presence of other sources.This study outlines the limited influence of the source in the local PCDD/F air concentrations and at the same time the usefulness of a joint analysis of measured, literature and calculated data to correctly evaluate the role of a source to the local pollution. The study also highlights the usefulness of AERMOD as a complementary tool to define the correct placement of monitoring stations and to locate those areas expected to have the highest air concentrations deriving from a source.     

Simultaneous monitoring of PCDD/Fs and PCBs in contaminated air with semipermeable membrane devices and fresh spruce needles

The contaminated air with burning plastic floor and electronic scrap was monitored with semipermeable membrane devices (SPMDs) and fresh unpolluted spruce needles at the same time for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It was found that there were more polychlorinated dibenzofurans (PCDFs) than polychlorinated dibenzo-p-dioxins (PCDDs) collected from contaminated air. The total amounts of PCBs were much higher than that of PCDD/Fs, but the contribution of them to the WHO-TEQ was less than that of PCDD/Fs. Triolein-containing SPMDs can absorb much more PCDD/Fs and PCBs than spruce needles when they were exposed in contaminated air simultaneously. The logarithm of the concentrations of PCDD/Fs and PCBs in SPMDs and in spruce needles at the same sampling time exhibited a significant linear correlation, the correlation coefficients were larger than 0.86 for PCDD/Fs and 0.92 for PCBs. SPMDs and spruce needles are effective passive air sampler for PCDD/Fs and PCBs. SPMDs and spruce needles can complement each other in passive air sampling.     

Nationwide monitoring of atmospheric PCDD/Fs and dioxin-like PCBs in South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were measured in ambient air samples collected from different parts of South Korea in 2008, and the measured levels were used for assessing the spatial and temporal distribution of atmospheric PCDDFs and DL-PCBs in South Korea. The average concentrations of atmospheric PCDD/Fs and DL-PCBs among the 37 sites were 28 fg I-TEQ m⁻³ (ND ∼ 617) and 1 fg WHO-TEQ m⁻³ (ND ∼ 0.016). Elevated atmospheric levels of PCDD/Fs and DL-PCBs observed at residential/industrial sites and in the north-west of Korea, indicated a potential contribution and impacts of anthropogenic sources of PCDD/Fs and DL-PCBs. These levels were similar or lower than those previously reported in other ambient air surveys. Average concentrations of PCDD/Fs showed small seasonal variations (ANOVA analysis, p = 0.144). The highest concentrations of PCDD/Fs were observed during winter, followed by spring, autumn and summer. Atmospheric PCDD/Fs and DL-PCBs in South Korea rapidly decreased during the last 10 years (1998-2008), demonstrating the efficiency of stricter regulations and the application of best available technologies/best environmental practices at emission sources. Comparison of the congener profiles and principal component analysis showed that current atmospheric PCDD/Fs are mostly influenced by industrial sources and PCBs from old commercial PCB uses. Nationwide POPs monitoring will continue and allows an effective evaluation of the implementation of the Stockholm Convention on POPs.     

Levels and trends of PCDD/Fs and PCBs in human milk in Finland

Word Health Organization, WHO/EURO, has coordinated two rounds of follow-up studies on levels of PCDDs, PCDFs, and PCBs in human milk which were analyzed as two pooled samples from each participating country, one from urban and the other one from rural area. Finland has taken part to both of those studies and we are now reporting results of all the second round randomly sampled human milk samples (84 samples) from Southern (20) and Eastern (64) Finland. The levels of PCDD/Fs and PCBs in human milk in Southern Finland were considerably higher than in Eastern Finland. The level of PCDD/Fs in human milk in Southern Finland was the same as in the Central Europe but the level in Eastern Finland was similar to levels in Norway and eastern parts of Europe. The concentrations of PCDD/Fs and PCBs showed a significant decrease from 1987 to 1994. Declining of PCDD/Fs and PCBs was 36 and 49% in primiparae mothers' milk, respectively. This decrease in concentrations of PCDD/F and PCB was slightly greater in Eastern than in Southern Finland.     

Models for gas/particle partitioning,transformation and air/water surface exchange of PCBs and PCDD/Fs in CMAQ

We have added the capability to simulate polychlorinated biphenyls (PCBs) and polychlorinated dibenzo [p] dioxins and polychlorinated dibenzo-furans (PCDD/Fs) to the Community Multiscale Air Quality (CMAQ) modeling system, thus taking advantage of the latter's capability to simulate atmospheric advection, diffusion, gas-phase chemistry, cloud/precipitation, and aerosol processes. The modifications reported here include the addition to the CMAQ system of two gas/particle partitioning models options: the Junge–Pankow adsorption model and the K_OA absorption model, as well as chemical transformations and atmosphere/water surface exchange processes for these semi-volatile organics. Simulations for the purpose of model testing and validation were conducted for the years 2000 and 2002 on a domain covering most of North America. Both partitioning models give reasonable results when compared with available measurements. The model predictions of deposition and air concentrations also agree well with measurements. The modeling results also indicate that the long-range transport is important and anthropogenic emissions of PCBs and PCDD/Fs are dominant although surface exchange of PCBs may be important for some clean locations.     

Occurrence of PCDD/Fs and dioxin-like PCBs in superficial sediment of Portuguese estuaries

Superficial sediments collected from seven estuarine systems located along the Portuguese coast were analyzed for 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), and 12 dioxin-like polychlorinated biphenyls (dl-PCBs). Total PCDD/F concentration ranged from 4.6 to 464 pg g^?1 dry weight (dw), while that of dl-PCBs varied from 26.6 to 8,693 pg g^?1 dw. In general, the highest PCDD/F and dl-PCB concentrations were associated with densely populated and industrially impacted areas. Additionally, PCDD/F revealed a predominance of octachlorodibenzodioxin (OCDD) to total PCDD/Fs, while PCB 118 was the major contributor to total dl-PCBs. This study provided a global perspective of the contamination status of Portuguese estuaries by dioxin-like compounds and allowed a comparison between the investigated systems and other systems worldwide. PCDD/F and dl-PCB levels found in the collected sediments were lower than those of highly impacted areas from different parts of the globe. Nevertheless, comparison with guidelines and quality standards from other countries indicated that some Portuguese estuarine areas with a high industrialization level present PCDD/F and dl-PCB concentrations in superficial sediment that may constitute a risk to aquatic organisms.