PCDDs, PCDFs, and PCBs concentrations in breast milk from two areas in Korea: body burden of mothers and implications for feeding infants

We determined breast milk concentration of polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in 24 mothers living in Korea, and assessed the maternal body burden based on PCDDs/PCDFs and PCBs concentrations in breast milk and an infant intake rate through breast-feeding based on their concentration in breast milk. PCDDs/PCDFs and PCBs levels in breast milk from primipara mothers were found to be higher than those from multipara mothers. For total PCDDs/PCDFs TEQ level, 2,3,4,7,8-PeCDD was the predominant congener, and the proportion of 2,3,7,8-TCDD was less than 3% of total PCDDs/PCDFs TEQ level. For PCBs TEQ level, PCB-126 was the predominant congener. Maternal body burden levels of PCDDs/PCDFs and PCBs based on their concentrations in breast milk were 268-622 TEQ ng. The daily dioxin intakes of mothers were predicted to be 0.78-2.18 TEQ pg/kg/day for PCDDs/PCDFs and 0.34-0.66 TEQ pg/kg/ day for PCBs. For the first year, the body burden of an infant was predicted to be 212 TEQ ng and the daily intake of an infant was predicted to be 85 TEQ pg/kg/day, assuming the mean dioxin-related compounds concentration (27.54 TEQ pg/g fat).     

Formation and emission status of PCDDs/PCDFs in municipal solid waste incinerators in Korea

This study was carried out to examine the formation and the emission status of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) in the flue gases of commercial-scale municipal solid waste (MSW) incinerators, and thus to provide the engineering data for the reduction of PCDDs/PCDFs emitted from MSW incinerators. The formation concentrations of the PCDDs/PCDFs generated at the outlet of waste heat boilers (WHB) were in the range of 1.18-29.61 ng-TEQ/N m3 (average 5.75 ng-TEQ/N m3), while the emission concentrations at the stacks were in the range of 0.026-4.548 ng-TEQ/N m3 (average 0.924 ng-TEQ/N m3). Two major 2,3,7,8-substituted congeners were 2,3,4,7,8-PeCDF and 2,3,4,6,7,8-HxCDF, and their concentrations were up to 50% and 64% of total TEQ values at the outlet of WHB and the stack, respectively. From the results of multi-regression analysis, the formation concentration of PCDDs/PCDFs could be predicted as follows with the correlation factor of r2 = 0.962: PCDDs/PCDFs (ng-TEQ/N m3) = 3.036 (Cl) + 0.094 (T1) - 0.472 (Combustibles) + 0.059 (CO) - 0.039 (THC) - 3.366 (H) + 22.157, where T1 (degrees C) is the temperature at the outlet of the WHB. Cl, Combustibles and H are given as percentages and the others are in parts per million.     

Prediction of the retentions of polybrominated dibenzo-p-dioxins (PBDDs) by using the retentions of polychlorinated dibenzo-p-dioxins (PCDDs)

The retention equations In k' = A + B/T of 49 polychlorinated dibenzo-p-dioxins (PCDDs) and 4 polybrominated dibenzo-p-dioxins (PBDDs) in gas chromatography (GC) have been investigated to evaluate the properties of regression coefficients A and B. The quantitative relationships between A and B values of PCDDs and those of PBDDs are found. The regression equations derived have correlation coefficients greater than 0.997. The A, B values of any PBDD can be predicted by using the A, B values of the PCDD according to these relationships. Using these predicted A and B values, the retention times of all PBDDs can be predicted at any temperature program. It is very useful to identify the peak position of any PBDD because at present there are only a few standards of PBDDs available.     

A pilot and field investigation on mobility of PCDDs/PCDFs in landfill site with municipal solid waste incineration residue

A field investigation by boring was carried out in a landfill site primarily with municipal solid waste incineration residue. From the collected core samples, vertical profiles of homologous content of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in the landfill layer were traced and the behavior of PCDDs/PCDFs was examined. In addition, a pilot-scale study was conducted on the PCDDs/PCDFs leached from incineration fly ash and the treated one using large landfill simulation columns (lysimeters) and the leaching behavior of PCDDs/PCDFs was examined. As a result, it was found that the coexistence of dissolved coloring constituents (DCCs), which might be composed of constituents like dissolved humic matters having strong affinity for hydrophobic organic pollutants, could enhance the leachability of PCDDs/PCDFs, thus contributing to the vertical movement and leaching behavior of PCDDs/PCDFs in the landfill layers of the incineration residue. Moreover, it is highly probable that DCCs derive from the unburned carbon in the bottom ash mixed and buried with the fly ash containing a high content of PCDDs/PCDFs.     

A simplified clean-up procedure for the rapid determination of PCDDs and PCDFs based on retention on activated carbon AX-21

Different 2,3,7,8-substituted polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs) were investigated for their retention behaviour on a disposable minicolumn containing activated carbon AX-21. Elution behaviour and recovery were examined, using native and radiolabelled PCDD and PCDF isomers.

A comparison of the total mass chromatograms of PCDDs and PCDFs in an extract from animal adipose tissue, before and after activated carbon treatment, demonstrates the efficiency of this cleanup step with respect to the elimination of interfering compounds.     

Levels of PCDDs and PCDFs in two kinds of fast foods in Korea

We initiated an attempt to gather preliminary Korean fast food data on the concentrations, whole weight and international toxic equivalent (TEQ), in two kinds of fast foods, hamburger and fried chicken. The levels of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) in hamburgers are detected to be lower than in fried chickens. Total TEQ level of PCDDs in fried chicken is 47.45 times higher than in hamburger. In case of PCDFs, it is 48.61 times. Even though these are compared to the only one brand and three samples each, we think that these high levels of PCDDs/PCDFs in fried chicken are very important data because of the potentially increasing daily intake. If we continue to survey for PCDDs/PCDFs in fast foods more even, especially fried chicken, these data will be useful to calculate the estimated daily intake of TEQ levels of PCDDs/PCDFs in Korea.     

Emissions of Chlorinated Organics from Two Municipal Incinerators in Ontario

In this paper the results of sampling for trace chlorinated organics at two municipal refuse incinerators in Ontario are presented. The information may be of Interest to individuals concerned with the assessment of PCDD/PCDF (polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran) emissions from incineration of refuse and their impact on the energyfrom- waste program. PCDDs, PCDFs, PCBs (polychlorinated biphenyls), CBs (chlorobenzenes) and CPs (chlorophenols) were quantified in all process streams including refuse, ash and stack emissions. Manual sorting of refuse and collection of ash samples were carried out simultaneously with three 24-hour continuous stack sampling tests at each plant. The results suggested that the total output of PCDDs and PCDFs varied proportionately with their input at both incinerators. However, the input of PCDDs/PCDFs could not account for their total output. The chemistry of PCDDs/PCDFs in the input and output streams were different in that only heptachlorinated and octachlorinated species were present in significant quantities in the refuse while lower chlorinated species were predominant in stack emissions and ash streams. There was no correspondence between the Input of PCBs/CBs/CPs and the output of PCDDs/PCDFs. The output of PCDDs/PCDFs, however, varied Inversely with the total output of PCBs/CBs/CPs, suggesting that the latter compounds could have been partially responsible for the formation of PCDDs and PCDFs. The PCDF emissions were also affected by combustion conditions; they were higher in magnitude and consisted of predominantly tetrachlorinated and pentachlorinated species at the plant where the combustion temperatures were lower.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in rice straw smoke and their origins in Japan

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) contained in the smoke generated from rice straw burning in post-harvest paddy fields in Japan were analyzed to determine their congener profiles. Both the apportionment of toxic equivalent (TEQ) by using indicative congeners and the comparison of the homolog profiles showed that the PCDDs/PCDFs/DL-PCBs present in the rice-straw smoke were greatly influenced by those present as impurities in pentachlorophenol (PCP) and chlornitrofen (CNP, 4-nitrophenyl-2,4,6-trichlorophenyl ether) formulations that had been widely used as herbicides in paddy fields in Japan. Further, in order to investigate the effects of paddy-field soil on the PCDDs/PCDFs/DL-PCBs present in rice-straw smoke, PCDD/PCDF/DL-PCB homolog profiles of rice straw, rice-straw smoke and paddy-field soil were compared. Rice-straw smoke was generated by burning rice straw on a stainless-steel tray in a laboratory. The results suggested that the herbicides-originated PCDDs/PCDFs/DL-PCBs and the atmospheric PCDDs/PCDFs/DL-PCBs contributed predominantly to the presence of PCDDs/PCDFs/DL-PCBs in the rice-straw smoke while the contribution of PCDDs/PCDFs/DL-PCBs formed during rice straw burning was relatively minimal. The major sources of the PCDDs/PCDFs/DL-PCBs found in the rice-straw smoke were attributed primarily to the paddy-field soil adhered to the rice straw surface and secondarily to the air taken by the rice straw. The principal component analysis supported these conclusions. It is concluded that rice straw burning at paddy fields acts as a driving force in the transfer of PCDDs/PCDFs/DL-PCBs from paddy-field soil to the atmosphere.     

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.     

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.     

Development and applications of a mass spectrometry/mass spectrometry method for the quantification of polychlorinated dibenzo-p-dioxins and dibenzofurans

Mass spectrometry/mass spectrometry (MS/MS) has been demonstrated to be a valuable technique in the analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs, PCDFs). In this study, we demonstrate both the value and limitations of high-resolution mass spectrometry (HRMS) and MS/MS in the analysis of PCDDs and PCDFs. We have found that in certain cases, MS/MS can solve analytical problems that cannot be solved by high-resolution mass spectrometry and we demonstrate the reliability and reproducibility of MS/MS in the analysis of PCDDs and PCDFs in environmental matrices.     

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.     

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.     

Use of a column leaching test to study the mobility of chlorinated HOCs from a contaminated soil and the distribution of compounds between soluble and colloid phases

An equilibrium and recirculation column test for hydrophobic organic chemicals (ER-H test) was used to study the leaching behaviour of chlorophenols (CPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) from contaminated soil. A 50% increase in the pore water velocity was shown to have little or no effect on the mobility of CPs, PCDEs, PCDFs and PCDDs. The standard deviations of truly dissolved compounds, CPs, were between 19% and 65% between the tests. However, the repeatability of the ER-H test decreased with increases in the hydrophobicity of the studied compounds; the standard deviations for PCDEs, PCDFs and PCDDs ranged from 53% to 110%, 57% to 77% and 110% to 130%, respectively. The influence of colloids on the release of these compounds was also examined. Up to 30% of the CPs in the soil were leached, of which 1-3% were associated with colloids. The PCDEs, PCDFs and PCDDs were found to be preferably associated with the particulate fraction of the leachate, and less than 0.2% of these compounds were mobilised.     

A survey of drinking water supplies in the Province of Ontario for dioxins and furans

A survey of drinking water supplies in the Province of Ontario was initiated in 1983 to determine the extent of their contamination by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). This drinking water survey arose from concerns regarding the discovery of PCDDs and PCDFs in sport fish from western Lake Ontario in the early 1980's.A total of 49 water supplies throughout all Regions of Ontario have been examined to date. Water supplies in the vicinity of chemical industries and pulp and paper mills were sampled more frequently; as many as 20 times. Detection limits were in the low parts per quadrillion (ppq) range for all tetra- to octachlorinated PCDDs and PCDFs.As of February 1989, 4, 347 results were received for 399 raw and treated water samples. Only 37 positive results were reported, constituting less than 1 percent of the total number of results. The O₈CDD congener accounted for 36 of the 37 positive results. The 2,3,7,8- TCDD isomer was not detected in any sample.     

Removal efficiencies of PCDDs/PCDFs by air pollution control devices in municipal solid waste incinerators

Removal efficiencies of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) by air pollution control devices (APCDs) in the commercial-scale municipal solid waste (MSW) incinerators with a capacity of above 200 ton/day were evaluated. The removal efficiencies of PCDDs/PCDFs were up to 95% when the activated carbon (AC) was injected in front of electrostatic precipitator (EP). Spray dryer absorber/bag filter (SDA/BF) had high removal efficiency (99%)) of PCDDs/PCDFs when a mixture of lime and AC was sprayed into the SDA. When the AC was not added in scrubbing solution, the whole congeners of PCDDs/PCDFs were enriched in the wet scrubber (WS) with negative removal efficiencies of -25% to -5731%. Discharge of PCDDs/PCDFs was decreased with increasing the proportions of AC added in scrubbing solution. Selective catalytic reduction (SCR) system had the removal efficiencies of up to 93% during the test operation.     

Photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in aqueous solutions and in organic solvents

Aqueous solutions of selected polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were prepared using a generator column and exposed to UV (300 nm) light in the laboratory and to sunlight in an outdoor environment. In the laboratory, additional exposures were also carried out using 60% acetonitrile/water solutions. At 300 nm di- and tetra PCDDs had higher first-order photodegradation rate constants in 60% acetonitrile/water than in pure water. The solvent effect was reversed for PCDFs. These results may be a reflection of the higher polarity of PCDFs compared to PCDDs. In both the indoor and outdoor exposures photodegradation rates decreased with increasing concentrations of chlorination. However, OCDF exposed to 300 nm light in 60% acetonitrile/water and to sunlight in pure water photodegraded more rapidly than tetra CDF. Photolysis rates in sunlight were considerably slower (t(1/2) of 6.4-23 h) than photolysis rates at 300 nm in the laboratory (t(1/2) of 4.3-680 min), reflecting the lower intensity of sunlight in the 300 nm region of the UV/Vis spectrum. The extent of dechlorination of the PCDDs/PCDFs was less than 20% and reductive dechlorination does not appear to be a major process in the photodegradation of PCDDs/PCDFs in aqueous solutions.     

Apportionment of TEQs from four major dioxin sources in Japan on the basis of five indicative congeners

The major sources of dioxins (polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs)) in the environment in Japan have been considered to be combustion by-products, pentachlorophenol (PCP) formulations, chlornitrofen (CNP, 4-nitrophenyl-2,4,6-trichlorophenyl ether) formulations, and PCB products. Data on PCDDs, PCDFs and DL-PCBs from the four sources were analyzed, and indicative congeners whose concentrations were highly correlated with WHO-2006 toxic equivalencies (TEQs) were identified for each source sample. The indicative congeners for combustion by-products, PCP formulations, and CNP formulations were 2,3,4,7,8-pentachlorodibenzofuran, 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin, and 1,2,3,7,8-pentachlorodibenzo-p-dioxin, respectively; for PCB products, the indicative congeners were IUPAC Nos. #126- and #105-pentachlorobiphenyls. Moreover, using the data on PCDDs, PCDFs and DL-PCBs, we developed a set of equations for estimating the apportionment of TEQs from the four sources by using only the concentrations of the above-mentioned five indicative congeners. The equations were used along with the analysis results of different types of environmental samples collected from Japan, to determine the TEQ contributions of the four sources. The obtained values of TEQ contributions seemed to be reasonable. The estimation method was developed by using the data on major dioxin sources in Japan, and therefore, it is generally adaptable to environmental samples from any part of Japan. The method may be usable for regions outside Japan if source identification is carried out and the estimation equations are modified appropriately.     

Assessment of human exposure to PCDDs,PCDFs and Co-PCBs using hair as a human pollution indicator sample I: Development of analytical method for human hair and evaluation for exposure assessment

Dioxins including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (Co-PCBs) are highly toxic. Even at environmental pollution levels, they cause hormonal damage in women, and they have been shown to induce immunosuppression and genital function damage in humans. In this study, a new method using isotope dilution was established to detect PCDDs, PCDFs and Co-PCBs in human hair. This method, comprised of washing and cutting of hair, alkaline decomposition, hexane extraction, multilayer silica gel column chromatography, high performance liquid chromatography with a porous graphite carbon column and analysis by high resolution gas chromatography/high resolution mass spectrometry, enabled us to analyze PCDDs, PCDFs and Co-PCBs at trace levels of less than pg/g with good reproducibility. In addition, there was a correlation between some isomers in human hair and blood collected from identical donors. Human hair analysis is useful to evaluate human risk assessment including that due to environmental pollution.