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.     

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.     

Assessment of current serum levels of PCDD/Fs, dl-PCBs and PBDEs in a Dutch cohort with known perinatal PCDD/F exposure

As part of a longitudinal cohort study, now in its second decade, we determined PCDDs/Fs dl-PCBs and PBDEs in serum of adolescents with known perinatal PCDD/F exposure. Of the original cohort, 33 adolescents aged 14-19 years, who had been studied previously during their neonatal (n=60), toddler and pre-pubertal period (n=41) agreed to participate in the current follow-up. PCDD/F-, dl-PCB- and PBDE congeners were measured using GC/MS. Current serum levels of PCDD/Fs determined in our cohort were relatively low (mean of 2.2pg/g) compared to the perinatal exposure. No correlation between perinatal exposure and current serum PCDD/F was found. Planar PCB TEQ levels were 2.2pg/g. Current summation operatorPBDE levels were 8.7ng/g lipid. There was one outlier with a summation operatorPBDE of 74ng/g lipid. The presence of this high value indicates that the exposure pathway is different from PCDD/F and PCB, most likely by dust and food contaminated with dust. Concluding we can say that current PCDD/F levels are quite low compared to the perinatal PCDD/F exposure of the cohort. PBDE levels however are relatively high compared to other European countries, more research on possible health effects of these levels, especially for subjects with outlier concentrations, should be performed.     

Estimation and characterization of PCDD/Fs, dl-PCBs, PCNs, HxCBz and PeCBz emissions from magnesium metallurgy facilities in China

Magnesium production is considered to be one potential source of unintentional persistent organic pollutants (unintentional POPs). However, studies on the emissions of unintentional POPs from magnesium metallurgy are still lacking. Emissions of unintentional POPs, such as polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), polychlorinated naphthalenes (PCNs), hexachlorobenzene (HxCBz) and pentachlorobenzene (PeCBz) are covered under the Stockholm Convention. In this study, these emissions were investigated through a magnesium smelting process. Stack gas and fly ash samples from a typical magnesium plant in China were collected and analyzed to estimate the emissions of unintentional POPs from magnesium metallurgy. Emissions factors of 412 ng TEQ t⁻¹ for PCDD/Fs, 18.6 ng TEQ t⁻¹ for dl-PCBs, 3329 μg t⁻¹ for PCNs, 820 μg t⁻¹ for HxCBz, and 1326 μg t⁻¹ for PeCBz were obtained in 2009. Annual emissions from magnesium metallurgy in China were estimated to be 0.46 g WHO-TEQ for PCDD/Fs and dl-PCBs, 1651 g for PCNs, 403 g for HxCBz and 653 g for PeCBz, respectively.     

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

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

Ambient air monitoring of PCDD/Fs and co-PCBs in Gyeonggi-do, Korea

We started the monitoring for PCDD/Fs in ambient air and soil in August 2001, and co-PCBs in January 2002. Decreasing of PCDD/Fs and co-PCBs levels in ambient air were observed. The higher PCDD/Fs levels were found in winter and lower in autumn. We found that the industrial incinerators influenced the PCDD/Fs levels in ambient air. In the 2,3,7,8-substituted PCDD/Fs concentration profiles, the three major congeners occupied 67% of the total mass. In case of co-PCBs, PCB#118, #105 and #77 were observed as the main congeners. Five cluster groups discriminated by ratio of four components, O(8)CDD, 1,2,3,4,6,7,8-H(7)CDD, 1,2,3,4,6,7,8-H(7)CDF and O(8)CDF, were obtained from HCA (hierarchical cluster analysis).     

Evaluation of atmospheric sources of PCDD/Fs, PCBs and PBDEs around a steel industrial complex in northeast China using passive air samplers

The concern about emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) from steel industrial parks has increased in the past decades. In this study, polyurethane foam (PUF)-disk based passive air samples were collected in and around a big steel industrial park of Anshan, Northeast China from June 2008 to March 2009. The levels, seasonal variations and potential sources of PCDD/Fs, PCBs and PBDEs in the atmosphere around the steel industrial complex were investigated, and potential contribution of these three groups of persistent organic pollutants (POPs) from iron and steel production was also assessed. The air concentrations of ∑₁₇PCDD/Fs (summer: 0.02-2.77 pg m⁻³; winter: 0.20-9.79 pg m⁻³), ∑₁₉PCBs (summer: 23.5-155.8 pg m⁻³; winter: 14.6-81.3 pg m⁻³) and ∑₁₃PBDEs (summer: 2.91-10.7 pg m⁻³; winter: 1.10-3.89 pg m⁻³) in this targeted industrial park were relatively low in comparison to other studies, which implied that the industrial activities of iron and steel had not resulted in serious contamination to the ambient air in this area. On the whole, the air concentrations of PCDD/Fs in winter were higher than those of summer, whereas the concentrations of PCBs and PBDEs showed opposite trends. The result from principal component analysis indicated that coal combustion might be the main contributor of PCDD/F sources in this area.     

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.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in Guangzhou,China

Atmospheric deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) was investigated at four locations, namely at Yuancun, Wushan, Haizhu and Changban in Guangzhou City, Guangdong Province. The annual deposition fluxes of tetra- to octa-CDD/Fs (total PCDD/Fs) were found to range from 170 to 3000 (mean 1500) pg m⁻² day⁻¹, and the fluxes of total 2, 3, 7, 8-substituted PCDD/F congeners ranged from 2.1 to 41 (mean 20) pg WHO-TEQ m⁻² day⁻¹ at Wushan. The average deposition fluxes of total 2, 3, 7, 8-substituted PCDD/F congeners in rainy season were found to be 37, 27 and 28 pg WHO-TEQ m⁻² day⁻¹ at Yuancun, Haizhu and Changban, respectively, and the PCDD/F deposition fluxes behaved obviously higher in rainy season than in dry season. Results from regression analysis showed that number of rainy days, the amount of wet precipitation, PCDD/F concentrations in particles and organic carbon content played important roles in the variation of PCDD/F deposition fluxes. Monthly average temperatures change little over the year. Therefore, it only played a minor role in monthly variation of PCDD/F deposition fluxes. Particle deposition fluxes were generally not considered as the factor that could cause the differences in PCDD/F deposition fluxes between rainy and dry season, but were found to be related with PCDD/F deposition fluxes in rainy season or dry season. It was found that the profiles of PCDD/F homologs or congeners in the samples were the same either spatially or temporally, indicating that the PCDD/F emission sources were similar to one another. The similarities in PCDD/F homolog patterns and the differences in deposition fluxes between samples collected from heavy-traffic roadside and nearby residence house roof indicated that vehicle exhaust might be an important source for PCDD/F in Guangzhou. PCDD/F concentrations and profiles of PCDD/F homologs in atmospheric deposition were compared with those in both total suspended particles in air and soils, and conclusions indicated that atmospheric deposition possibly tended to remove lower-chlorinated DD/Fs from air and was one of sources for PCDD/Fs in soils.     

Deposition fluxes of PCDD/Fs in a reservoir system in northern Taiwan

In this study, polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations and depositions in ambient air, water column and sediment were measured at a coupled reservoir-watershed system in northern Taiwan. The atmospheric PCDD/F concentration measured in the vicinity of the reservoir ranged from 4.9 to 39 fg I-TEQ m⁻³ and the Asian dust storm in February accounted for the peak value, which corresponded to a total suspended particle concentration of 128 μg m⁻³. The atmospheric PCDD/F deposition ranged from 1.4 to 19 pg I-TEQ m⁻² d⁻¹, with higher deposition occurring during winter and spring (long-range transport events). During summer, when atmospheric deposition is lower, consecutive tropical cyclones (typhoons) bring heavy rainfall that enhances soil erosion and creates turbidity-driven intermediate flow. This results in significantly higher PCDD/F deposition in water column of the reservoir at 70 m water depth (179 pg I-TEQ m⁻² d⁻¹) than at 20 m (21 pg I-TEQ m⁻² d⁻¹) during typhoon event. The accumulation rate of PCDD/Fs (9.1 ng I-TEQ m⁻² y⁻¹) in the reservoir sediments (depth: 0-2 cm) was consistent with PCDD/F deposition obtained from water column (6.1 and 8.3 ng I-TEQ m⁻² y⁻¹); however, it is significantly higher when compared to the atmospheric deposition (2.0 ng I-TEQ m⁻² y⁻¹). Based on the mass balance between the measurements of atmospheric deposition and sinking particles in water column, around 54-74% of PCDD/F inputs into the reservoir were contributed by the catchment erosion during normal period. However, the PCDD/F input contributed by the enhanced catchment erosion significantly increased to 90% during intensive typhoon events.     

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.     

Characteristics of PAHs, PCDD/Fs and PCBs in sediment following forest fires in northern Alberta

Extensive forest fires occurred in northern Alberta, Canada, in 1998. Polynuclear aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were studied following these forest fires in order to explore natural and anthropogenic influences on the affected forest fire area. Specifically, concentrations and profiles of these compounds were determined in sediment samples. A predominance of alkylated PAH derivatives over parent PAHs were observed at the burned and reference sites. Naturally dervied PAHs were abundant at all sites. A high proportion and concentration of retene was observed at the totally burned site and indicates some inputs from forest fires. Very low concentrations of PCDD/Fs and PCBs were observed at all sites, and the profiles were very similar. This likely reflects common atmospheric contributing sources to the study area.     

Atmospheric deposition of PCDD/Fs measured via automated and traditional samplers in Northern Taiwan

Most polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the atmosphere are bound to particles which are suspended in the atmosphere, and eventually settle on soil, vegetation, water bodies or other receptors in the environment. Monitoring atmospheric deposition fluxes (dry/wet) is important in tracing the environmental fate and behavior of PCDD/Fs. PCDD/F depositions were collected via an automated PCDD/F ambient sampler and traditional cylindrical vessels, respectively, from April 2007 to February 2008. The automated PCDD/F ambient sampler used in this study can prevent both re-suspension and photo degradation of the PCDD/Fs collected and effectively separates the PCDD/F samples into dry and wet contributions. The results indicated that the ambient PCDD/F concentrations collected using the PS-1 sampler ranged from 0.02 pg I-TEQ/m³ to 0.16 pg I-TEQ/m³ in Northern Taiwan. The results also indicated that the PCDD/F deposition flux collected using the automated PCDD/F sampler (17.5 pg I-TEQ/m² d to 25.8 pg I-TEQ/m² d) was significantly higher than that sampled with the cylindrical vessels (2.0 pg I-TEQ/m² d to 9.9 pg I-TEQ/m² d). The difference was attributed to the fact that part of the PCDD/F depositions collected using the traditional cylindrical vessels had undergone photo degradation and evaporation. In addition, the wet deposition flux of PCDD/Fs (39.4 pg I-TEQ/m² rainy day to 228 pg I-TEQ/m² rainy day) observed in this study was significantly higher than the dry deposition flux (12.3 pg I-TEQ/m² sunny day to 16.7 pg I-TEQ/m² sunny day). These results demonstrated that wet deposition is the major PCDD/F removal mechanism in the atmosphere.     

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.     

Investigation of PCDD/Fs and dl-PCBs in fish from the southern Baltic Sea during the 2002–2006 period

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) in the southern Baltic herring (Clupea harengus), sprat (Sprattus sprattus), and salmon (Salmo salar) are reported.The significant interspecies and season-specific differences in PCDD/Fs and dl-PCBs concentrations were observed. The contribution of dl-PCBs to the total toxicity equivalents (TEQs) ranged between 50% and 70%, dependently on fish species. In all samples, concentrations of PCDF were higher in comparison with that of PCDD.The permissible limits of the content of PCDD/Fs and dl-PCBs (8 pg g⁻¹ fresh weight for the sum of PCDD/Fs and dl-PCBs, and 4 pg g⁻¹ fresh weight for the PCDD/Fs) were exceeded mainly in salmon samples (in 80% of salmon samples studied). The elevated levels of PCDD/F and dl-PCB were observed only in two of seventy two herring samples, and in ten of 62 sprat samples.The multiple regression analysis revealed that fish lipid content, and concentration of PCB 153, used simultaneously, might be useful in the prediction of TEQ values of fish samples. These two variables explained more than 80% of total variance. For all fish species studied, the correlation coefficients obtained with the multiple regression analysis were higher than that obtained with the regression analysis involving total TEQ values, and only one independent variable: fish lipid content.     

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).     

Occurrence of PCDD/Fs in urban air before and after the ban of leaded gasoline

The source of PCDDs and PCDFs in automotive exhaust is not yet fully explained. The chlorinated hydrocarbons used in the formulation of lead-alkyl additives were suspected as a possible major source. Based on this, the decreasing use of leaded gasoline followed by its final ban (occurred on 1/1/2002, in Italy) should have resulted in a decreasing presence of PCDD/Fs in urban air and possibly some differences in their profile. To investigate these aspects, we monitored PCDD/Fs for one year starting in September 2001, at a medium-traffic road site in Rome, with weekly frequency. Results were then compared with those obtained in a previous study performed before the ban (from February 2000 to January 2001) at the same site. As compared with the previous study, the yearly-averaged overall PCDD/F concentration, as toxic equivalent of 2,3,7,8-TCDD, decreased from 60 to 50 fg m(-3) I-TEQ; it remained unchanged, however, if one sample with a particularly high PCDD/F content was excluded from each data set. The monthly trend confirmed the one found in the former study. On an annual basis, the two mean congener profiles were almost identical. The concentration levels and the constancy of profiles, as calculated for the two periods, do not support the hypothesis of a major role of leaded gasoline, substantially different from unleaded one, in contributing to PCDD/F air pollution.     

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.     

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.     

Empirical relationship between precision and ultra-trace concentrations of PCDD/Fs and dioxin-like PCBs in biological matrices

Dioxin analysis in food and feed can be characterized as an analytical application where very high accuracy is required at very low levels of contamination. Gas chromatography (GC) in combination with 13C-label isotope dilution (ID) high resolution mass spectrometry (HRMS) is the reference congener-specific technique characterized by pronounced selectivity, precision and trueness at parts-per-trillion (ppt) and sub-parts-per-trillion (sub-ppt) levels. The quality of the analytical data produced routinely by a laboratory should be adequate for its intended purpose, i.e., one will seek a compromise between the cost and time needed and the consequences of incorrect decisions due to erroneous results. The requirements for reproducibility are usually dependent on the analyte concentrations and have been expressed in various empirical functions. While Horwitz or modified functions are widely useful for many purposes, it would be difficult to expect these functions to cover every analytical problem. This study reports on precision characteristics achieved by the GC-ID-HRMS reference method for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in food and feed in two interlaboratory method-performance studies among expert laboratories with long-standing experience in this field. Striking linear functions in log scale between reproducibility standard deviation and congener's level over a concentration range of 10(-8)-10(-14)g per g fresh weight are observed. The data fit very well to a Horwitz-type function of the form sR=0.153c0.904, where sR and c are dimensionless mass ratios expressed in pg g(-1) on fresh weight, regardless of the nature of the toxic congeners, food and feed matrices, or sample preparation methods. We demonstrate that the proposed function is suitable for use as a fitness-for-purpose criterion for proficiency assessment in interlaboratory comparisons on dioxins and related compounds in food.