Analysis of atmospheric behavior of PCDDs/PCDFs by a one-compartment box model

The overall atmospheric behavior of PCDDs/PCDFs in the Kanto region, Japan, was simulated by a one-compartment box model. For each homologue the relative significance and temperature dependences of dry deposition, wet deposition, degradation, and advection in both gas and particulate phases were examined and compared. The results of the model calculation suggested that the rates for dry deposition are comparable to those for wet deposition, and the rates for advection are comparable to those for bulk (dry+wet) depositions in the Kanto region. On the other hand, the rates of degradation for PCDDs/PCDFs in the atmosphere in the Kanto region would be negligible. The emission rates and the bulk deposition fluxes in the entire Kanto region estimated by the model calculation based on observed air concentrations were 0.084-0.90 kg-TEQ/month and 0.045-0.43 kg-TEQ/month, respectively. These estimated emission rates and bulk deposition fluxes were slightly higher than the estimated emission rate based on observed emission concentrations and the estimated bulk deposition fluxes based on observed deposition fluxes collected on water deposition surface, respectively. This study showed the model calculation can be available for understanding of the overall atmospheric behavior, verification of the source inventory, and estimation of deposition flux on the actual environment including various deposition surfaces.     

Degradation half-life times of PCDDs, PCDFs and PCBs for environmental fate modeling

Literature search of the knowledge on the degradation of persistent organic pollutants (POPs) in environmental compartments air, water, soil and sediment was done in purpose to find properties of POPs of interest for modeling. One degradation process, hydrolysis (chemical degradation), was omitted as negligibly slow for POPs studied. The other two, photolysis and biodegradation processes, were considered separately in purpose to develop estimation procedures. The estimates can be given as pseudo first-order rate constants kP for photolysis and kB for biodegradation. For each compartment, an overall degradation rate is k(tot) = kP + kB and lifetime t(1/2) = ln 2/k(tot). The latter values, lifetimes in each compartment, will be used as input parameters to the Baltic Sea model.     

Congener-specific intake fractions for PCDDs/DFs and Co-PCBs: modeling and validation

Intake fractions (iFs) for emissions to air, water, and soil for 17 PCDDs/DFs and 12 Co-PCBs were calculated with a level III multimedia model and a food-chain exposure model in succession. The two integrated models were tested by comparing the predicted and measured concentrations in the environment and by comparing intakes through food. Measurement-based iFs were also calculated and compared with the model-based iFs. The air concentrations predicted by the fate model were close to the median of the observed concentrations, whereas the predicted soil and water concentrations were one-third to one-tenth the observed concentrations. This difference was large in case of PCDDs and Co-PCBs, which was explained by the past pollution such as commercial PCB products and PCDD impurities in chloronitrofen (CNP) and pentachlorophenol (PCP). For fish, the predicted and observed exposures agreed well each other. For meat and milk, the predicted exposures were about 10 times the observed exposures for PCDDs/DFs, whereas the predicted and observed values agreed well for Co-PCBs. When the model was modified to consider feeding of fish meal to livestock and geographic bias in feed-grass production, the predicted congener profile was comparable to the measured profile. The comparison also suggested that chickens should be modeled separately from other terrestrial livestock. The model-based iFs for air emission of OCDD and 2378-TCDD were 0.001% and 0.1%, respectively. The iFs of most Co-PCBs were higher than those of PCDDs/DFs. These iF differences suggest the importance of the fate factor in assessing emissions of the 29 congeners.     

Congener profiles of PCDDs, PCDFs, and dioxin-like PCBs in the breast milk samples in Tokyo, Japan

Exposure to dioxins has raised much public concern recently. We determined the congeners' distribution of polychlorinated-dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in the breast milk samples collected in Tokyo, Japan. Breast milk was taken from 240 mothers, 30 days after delivery in 1999 and 2000 in Tokyo, Japan. The actual concentration and TEQ concentration of PCDDs (14 congeners), PCDFs (15 congeners), and dl-PCBs (12 congeners), and each congener's contribution to the total TEQ level were calculated. Among all the samples, PCDDs accounted for 34.8%, PCDFs accounted for 23.5%, dl-PCBs accounted for 41.7%, which was also similar in the breast milk from the primiparae and secundiparae. The main contributors to the total TEQ with increasing percentages were 2,3,4,7,8-PeCDF, 1,2,3,7,8-PeCDD and 3,3',4,4',5-PCB (#126), and they accounted for more than 65% of the total TEQ. Detailed congener analysis in breast milk samples is effective to understand dioxin sources.     

PCDDs/PCDFs and dioxin-like PCBs: recent body burden levels and their determinants among general inhabitants in Japan

OBJECTIVE: The objective was to grasp the recent body burden levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DL-PCBs) and to investigate their determinants among general inhabitants in Japan. METHODS: This study was performed on 1374 participants aged 15-73 years, who were not occupational exposure to PCDDs/PCDFs and DL-PCBs, living widely in 75 different residential areas of 25 prefectures in Japan. Seven PCDDs, ten PCDFs, twelve DL-PCBs, which are assigned a toxicity equivalent factor, and biochemical factors were determined in fasting blood. A questionnaire survey on life-style was also performed. RESULTS: The median of total toxicity equivalent (TEQ) was 20pgTEQ/g lipid. The TEQs of PCDDs/PCDFs, DL-PCBs and total TEQ increased with age. The intake frequency of fish-and-shellfish was positively associated with the TEQ of DL-PCBs in both sexes. Current smoking was negatively related to the TEQ of DL-PCBs in male subjects but not in female subjects. Feeding status was significantly related to the TEQs of PCDDs/PCDFs, DL-PCBs and total TEQ, being lowest in breast feeding and highest in never and bottle feeding. According to the results of subgroup analysis, parity was not associated with the TEQs. CONCLUSIONS: The fish-and-shellfish consumption may contribute to the accumulation of DL-PCBs, and smoking may induce some biological action for the elimination of DL-PCBs from the human body. Breast feeding is considered to be one of the major excretory pathways of PCDDs/PCDFs and DL-PCBs in women, while parity may not largely contribute to the elimination of these pollutants.     

Levels and profiles of PCDDs,PCDFs and cPCBs in Belgian breast milk. Estimation of infant intake

Congener-specific analyses of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 20 non-pooled breast milk samples collected in or close to an industrial area of Wallonia (Belgium). PCDD/F concentrations ranged between 16.0 and 52.1 pg TEQ/g fat, with a mean value of 29.4 pg TEQ/g fat. If coplanar PCBs (77, 126, 169) are included in TEQ calculations, levels ranged between 22.2 and 100.2 pg TEQ/g fat, with a mean value of 40.8 pg TEQ/g fat. It appears that 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and PCB-126 account for more than 90% of the TEQ. Estimated PCDD/F dietary intake is 76 pg TEQ/kg body weight (bw)/day. This value is almost 20 times higher than the World Health Organization tolerable daily intake. A value of 103 pg TEQ/kg bw/day represents the intake of PCDDs, PCDFs and cPCBs (no mono-ortho PCBs included).     

Atmospheric concentrations of PCDDs/PCDFs in southern California.

A comprehensive air toxics measurements program designed to establish baseline concentrations of atmospheric polychlorinated dioxins and dibenzofurans (PCDDs/PCDFs) in the South Coast Air Basin has been completed. The program utilized state-of-the-art air sampling and laboratory analysis techniques (HRGC/HRMS) to quantify the fifteen 2,3,7,8-substituted PCDDs/PCDFs congeners of primary toxicological significance. This study, which included nine discrete sampling sessions between December 1987 and March 1989, provides the first systematic assessment of ambient PCDDs/PCDFs concentrations in the state of California. The highest PCDDs/PCDFs concentrations noted during this study occurred in December 1987. This period was dominated by off-shore air flows, suggesting a regional air mass and transport phenomena. Concentrations of the PCDDs/PCDFs were diminished markedly in subsequent sampling sessions where air flow patterns were primarily of on-shore or of coastal origin. Ambient PCDDs/PCDFs concentrations, expressed as toxic equivalents, were highest during the December 1987 sampling period. The El Toro monitoring site, located approximately 40 miles southeast of Los Angeles, consistently showed the lowest measured ambient PCDDs/PCDFs concentrations and toxic equivalents values. In the majority of the sessions and samples examined the PCDDs/PCDFs congener profiles strongly suggest combustion source influences. Typical of combustion source profiles, 1,2,3,4,6,7,8-HpCDD was the predominant 2,3,7,8-substituted species and most prevalent PCDD after OCDD. The congener of highest toxicological significance, 2,3,7,8-TCDD, was reported below the 10-20 fg/m3 detection limit for most of the ambient air samples selected for analysis.     

Serum profiles of PCDDs and PCDFs, in individuals near the Escambia Wood Treating Company Superfund site in Pensacola, FL

The Escambia Wood Treating Company (ETC) Superfund site, Pensacola, FL, is contaminated with polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F), benzo(a)pyrene, lead and arsenic from pentachlorophenol (PCP), creosote, and other compounds used to treat utility poles and foundation pilings. Although ETC's operations ceased in 1982, soils in the areas surrounding the facility continue to exhibit elevated levels of contaminants attributable to ETC operations. In July 2000, individuals who may have been affected by contamination from the ETC site, including current and former residents and former workers and their household members were invited to participate in a study, which included a health and exposure history and routine blood analysis. We also conducted a toxicological health evaluation of a subset of these eligible workers/residents by analyzing serum levels of 17 PCDD/F congeners. Members of the ETC cohort exhibited elevated serum PCDD/F relative to the general population, and congener profiles in members of the cohort reflected patterns commonly observed in persons exposed to PCP. Hypertension prevalence in the cohort was found to correlate with PCDD/F levels, although no other significant relationships were identified with monitored health indices.     

A comparison of TEQ contributions from PCDDs,PCDFs and dioxin-like PCBs in sewage sludges from Catalonia,Spain

Eight sewage sludges from rural, urban and industrial wastewater treatment plants (WWTPs) in Catalonia (Spain) were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) to determine the present levels of contamination. A method based on an automated cleanup system followed by an isotope-dilution high-resolution mass spectrometric analysis was employed. Total toxicity equivalent (WHO-TEQ) values were calculated using the toxicity equivalent factors (WHO-TEFs) proposed by WHO for dioxin-like PCBs, PCDDs and PCDFs. The WHO-TEQ(PCDD/F) values for these samples ranged from 4.9 to 20.8 pg/g dry weight (d.w.), with a mean value of 9.3 pg/g d.w., whereas WHO-TEQ(PCB) levels ranged between 1.9 and 6.6 pg/g d.w., with a mean value of 4.2 pg/g d.w. The WHO-TEQ(PCB) contribution varied from 13% to 50%, suggesting that PCB contribution on the toxicity of the samples must be taken into account. Moreover, these contemporary PCDD, PCDF and PCB concentrations were compared with previous data obtained from sewage sludge samples collected during the 80s. Our findings show that contemporary PCDD, PCDF and PCB levels have declined since the 80s.     

Levels of PCBs, PCDDs and PCDFs in commercial butter samples in Spain

Feasibility of three different extraction methods for the simultaneous determination of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in butter is discussed. The method based on liquid-liquid extraction with water of the non fatty solids from butter dissolved in hexane was found to be the most efficient for the determination of the lipid content and the levels of the investigated pollutants. This method was used to evaluate the background levels of PCBs, PCDDs and PCDFs in butters commercially available in Spain. Broad ranges of PCB, specifically, PCDD and PCDF concentrations were found in the different brands analysed. Levels, profiles and patterns of these pollutants in butter were compared with those previously reported for different Spanish dairy products. The toxic tetra-equivalents of 2,3,7,8-TCDD (1-TEQ) averages for PCDDs and PCDFs in the 21 butter samples analysed were 0.41 and 0.70 pg/g fat basis, respectively. These values were similar or lower than those cited in the literature for other countries.     

Occurrence,profile and possible sources of PCNs in Hong Kong soils,and a comparison with PCBs,PCDDs and PCDFs

Polychlorinated naphthalenes (PCNs) have been proposed for inclusion in the annexes of the Stockholm Convention by the European Union, signifying a probable increase in monitoring PCN levels at a global level. Investigations on PCN levels in the environment of Hong Kong have not been reported. In this preliminary investigation, PCN levels in surface soils samples were determined by isotope dilution HRGC/HRMS techniques, and compared with those of polychlorinated biphenyl (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The concentrations of PCNs in the soil samples were 35–883 pg g^?1 (average, 201; and median, 94 pg g^?1), which were lower than those of PCBs PCDDs and PCDFs. This comparison suggested that PCNs are currently not priority POPs compared with dioxins and PCBs in Hong Kong soils. PCDDs were the most important contributor to the sum of toxic equivalents of PCNs, PCBs, PCDDs and PCDFs. OCDD was the most dominant dioxin congener in Hong Kong surface soils. PCB-118 was the most abundant in 12 dl-PCB congeners. PCN congeners indicating thermal related sources (CN52/60, CN66/67 and CN73) were relatively abundant in their respective homologs, which suggested PCN contamination from thermal sources. The ratio of CN73 to CN74 in soil samples suggested the contribution of PCN contaminations in soils from both thermal-related sources and evaporative emissions of technical PCN mixtures.     

Polychlorinated dibenzo-p-dioxins (PCDDs) and furans (PCDFs) in urban air and deposition in the United Kingdom

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) have been monitored in air and deposition at four UK urban sites (London, Cardiff, Manchester and Stevenage) since the beginning of 1991; data from the first 2 years are presented here. Median Σ2,3,7,8-substituted PCDD/F concentrations in air were 3.2, 4.0, 3.5 and 2.6 pg/m³ respectively for London, Cardiff, Manchester and Stevenage. Median Σ2,3,7,8-substituted PCDD/F deposition fluxes were 1.5 ng/m²/day in London, 1.4 ng/m²/day in Cardiff and Manchester and 0.79 ng/m²/day in Stevenage. Seasonal variations in the PCDD/F concentrations were observed at all sites for both air and deposition, with concentrations/fluxes generally elevated during the winter.     

Patterns of PCDDs and PCDFs in human milk and food and their characterization by artificial neural networks

Artificial neural network (ANN) has been recently introduced as a tool for data analysis. In this study, Kohonen's self-organizing maps (SOMs), a special type of neural network, were applied to a set of PCDD/PCDF concentrations found in 54 human milk and 83 food samples, which were collected in a number of countries all over the world. Data were obtained from the scientific literature. The purpose of the study was to find a potential relationship between PCDD/PCDF congener profiles in human milk and the dietary habits of the different countries in which samples were collected. The comparison of the SOM component planes for human milk and foodstuffs indicates that those countries with a greater fish consumption show also higher PCDD/PCDF concentrations in human milk. SOMs enable both the visualization of sample units and the visualization of congener distribution.     

Determination of PCDDs and PCDFs in different animal feed ingredients

As result of a study to control feedstuff, analyses were carried out to evaluate the contamination caused by PCDDs and PCDFs in different animal feed ingredients. Thirty two samples were selected, including ingredients of animal and mineral origin. For samples of mineral origin, some additives widely employed as binder and anticaking agents, such as bentonite, damoline, kaolin, magnesite, sepiolite and zeolite were selected. And, for ingredients of animal origin, samples of hemoglobin, animal fat, fish oil, fish meal and meat and bone meal were analyzed. The levels ranged from 0.52 to 9.08 pg WHO-TEQ/g fat for samples of animal origin, and from 0.05 to 460.59 pg WHO-TEQ/g for samples of mineral origin. The higher concentrations were observed for the kaolin samples that presented high levels of dioxin contamination.     

PCDDs/PCDFs and PCBs in water samples from the Three Gorge Reservoir

The Three Gorge Reservoir (TGR) is the largest reservoir in China and its water quality is an important health concern, we have determined the concentrations of PCDDs/PCDFs and PCBs in the water samples collected at three seasons: August 2004, January 2005 and August 2005. The results showed that the average WHO-TEQ of total dioxins-like compounds (PCDDs/PCDFs+PCBs) was 0.06558 pg l(-1), ranged from 0.0008 to 0.32439 pg l(-1), which are much lower than other reported water sources. The main dioxins (PCDDs/PCDFs) are hepta- and octa-chlorinated dibenzo-p-dioxins (CDDs) and chlorinated dibenzofurans (CDFs). Since the levels of dioxins may change after the last water-store stage, the present study provides important data to compare the water quality in the TGR in the future.     

PCDDs/PCDFs, dl-PCBs and HCB in the flue gas from coal fired CFB boilers

The aim of the project was to measure the actual emissions of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and hexachlorobenzene (HCB) from four selected power plants in Poland in order to update the national inventory of PCDDs/PCDFs emission. Relatively low PCDDs/PCDFs as well as dl-PCBs concentrations in flue gas obtained in measurements in this study for four different circulated fluidized bed (CFB) boilers indicate practical absence of any hazards caused by PCDDs/PCDFs emission from these units. The results of PCDDs/PCDFs determination obtained in this study indicate that hard coal combustion in large CFB in the four central heating plants (CHP) is not a significant source of PCDDs/PCDFs emission to the environment even if operated by co-firing of waste coal. PCDDs/PCDFs concentration in flue gases as well as emission factors were recorded in the range of 0.012-0.060ngI-TEQ/m(n)(3) and 7.51-46.4mugI-TEQ/TJ, respectively. Dl-PCBs concentration was practically below the LOQ=0.006ng WHO-PCB TEQ/m(n)(3) in all experiments. HCB concentration as well as emission factors were recorded in the range of 11.5-42.0ng/m(n)(3) and 6.19-26.7mg/TJ, respectively, where the highest value was obtained for co-firing of waste coal, however. Obtained in this work emission factors will be used for national emission inventory purposes instead of the factors proposed by Toolkit or taken from previous measurements. However, consideration should be given to the fact that the measurements in most cases are related to single installations. Therefore, the need for further development of national factors for the power generation industry in Poland is desired.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in urban and suburban areas of Korea

Bulk atmospheric samples (wet and dry) were collected monthly throughout a year at urban and suburban areas of Korea to assess the deposition flux and seasonal variations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The PCDDs/DFs deposition fluxes ranged from 1.0 to 3.7 ng TEQ/m²/year in the urban area and from 0.5 to 4.6 ng TEQ/m²/year in the suburban area. The deposition fluxes of PCDDs/DFs in this study were comparable to or lower than those previously reported at different locations. The atmospheric deposition fluxes of particles and PCDDs/DFs in winter tended to be higher than those in summer. However, monthly variations between particle and PCDDs/DFs deposition fluxes were small, and the correlation coefficients between the deposition fluxes of air particles and each homologue group of PCDDs/DFs varied according to the degree of chlorination of the homologue group. The deposition velocity of PCDDs/DFs in the urban area was estimated at 0.04 cm/s, which is a lower value than those found in other studies. The two most likely factors affecting the monthly variation of deposition fluxes are the ambient temperature and the amount of precipitation. In particular, the ambient temperature had an influence on the lower chlorinated homologues of PCDDs/DFs while precipitation had an influence on the higher chlorinated PCDDs/DFs. The PCDDs/DFs profiles in atmospheric deposition bulk samples showed a similar pattern at the urban and suburban sites. The possibility of the loading of PCDDs/DFs by Asian dust events could be partly confirmed by investigation of homologue profiles.     

Levels of PCDDs, PCDFs and PCBs in Belgian and international fast food samples

Congener-specific analyses of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were performed on twenty-eight non-pooled fast food samples collected in Belgium, Switzerland, Czech Republic, United States of America and Australia. PCDD/F and PCB concentrations for the four investigated types of meals were very low. PCDD/F values ranged from non-detected to 1.40 pg WHO-TEQ/g fat and from 0.79 to 2.08 pg WHO-TEQ/g fat for lower and upper bound, respectively. Major contributors to the PCDD/F TEQ were 1,2,3,4,7,8-HxCDD, 1,2,3,6,7,8-HxCDD, 2,3,7,8-TCDF and 2,3,4,7,8-PeCDF. The relative contribution of PCBs to the total TEQ was 68%. For adults, an average estimated intake was 6.7 pg WHO-TEQ/kg bw/month, including consumption of all types of analyzed meals, representing 9.5% of the PTMI. For child, a value of 14.5 pg WHO-TEQ/kg bw/month was obtained, representing 20.6% of the PTMI.     

Development of GC capillary column for isomer-specific separation of toxic isomer of PCDDs and PCDFs in environmental samples

Analysis of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) has been performed using gas chromatography mass spectrometry (GC-MS). Analysis of the most toxic isomers, in particular, 2,3,7,8-substituted PCDD/PCDF in the presence of other isomers requires a special isomer specific capillary column or high performance liquid chromatography (HPLC) fractionation prior to GC-MS analysis. Commercially available long (>50 m) polar columns can separate 2,3,7,8-TCDD from other tetra isomers. However, those columns are not satisfactory for the analyses of total PCDD/PCDF in the environmental samples. Gas chromatography -high resolution mass spectrometry (GC-HRMS) and GC-MS/MS techniques are not helpful in the analysis of 2,3,7,8-TCDD unless it is separated from the other tetra isomers. The analysis of 2,3,7,8-TCDD and total PCDD and PCDF in a single GC-MS run can ease the laborious techniques presently used. In this study we have developed a new stationary phase for the GC capillary column. The capillary column developed using this new stationary phase showed unsurpassed selectivity for the separation of 2,3,7,8-TCDD from other tetra isomers. There are several advantages of the newly developed GC capillary column.