Correlation relationships between physico-chemical properties and gas chromatographic retention index of polychlorinated-dibenzofurans

Correlation relationships between physico-chemical properties including vapor pressures (P), water solubilities (S), Henry's law constants (H(c)), n-octanol-water partition coefficients (K(ow)), sediment-water partition coefficient (K(pw)) and biotic lipid-water partition coefficient (K(bw), bioconcentration factor) of polychlorinated-dibenzofurans (PCDFs) and their gas chromatographic retention indices (GC-RIs) were established. A model equation between GC-RIs (= RI) and these physico-chemical properties (K) of PCDFs was in a form of log K = aRI2 + bRI + c with correlation coefficients (R2) greater than 0.94, except H(c). These equations were derived from six experimental data (five experimental data for log K(bw)) in each physico-chemical properties of PCDFs reported previously. The values of log P, log S, log H(c), log K(ow), log K(pw) and log K(bw) of PCDFs predicted by these equations based on their GC-RIs in the present study derviated from those calculated by the solubility parameters for fate analysis method in a previous study by 0.49, 0.32, 0.11, 0.34, 0.14 and 0.22 log units, respectively.     

Peak identification for PCDD/Fs in environmental samples at different temperature programs

A method has been developed for peak recognition of 136 polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at different temperature programs. Their retention behaviours are predicted on the basis of an identification database of retention values (A, B) of gas chromatography. By the retention times of 13C labelled 2,3,7,8-substituted PCDD/F internal standards, the retentions of all PCDDs and PCDFs can be calculated. After comparison with the retentions of practical environmental samples, the predicted values have been proved to be very accurate.     

Bioavailability of PCDDs and PCDFs on fly ash after semi-chronic oral ingestion by guinea pig and syrian golden hamster

Groups of guinea pigs and syrian golden hamster (n = 5) were fed 2.5% HCL pre-treated fly ash from the electrostatic precipitator of a municipal incinerator during one, two and three months, respectively, in the diet. The livers were analyzed for tetra-, penta- and hexa-chlorinated dibenzo(p)dioxins (PCDDs) and dibenzofurans (PCDFs).In the livers of the hamsters 2,3,7,8-substituted PCDDs and PCDFs were the major isomers retained. In the livers of the guinea pigs 2,3,7,8 substituted PCDDs and PCDF congeners were retained, but also a number of otherwise substituted PCDFs. These other PCDF congeners included some having a 2,3,6,7 or alternate chlorine substitution pattern. Those congeners retained in the livers were generally below 5% of the group dose. The PCDF congener which had the highest retention in the livers of guinea pig was 1,2,3,7,8-PnCDF, 11.3% after 95 days. In the livers of the hamsters highest retention was found for 2,3,4,7,8-PnCDF, 8.4% after 95 days. For most 2,3,7,8-substituted PCDDs and PCDFs the retention in the livers of the guinea pigs and hamsters was not significantly different during the whole period, which could indicate a bioconcentration approaching a linear relationship to the administered dose. Constant relative concentrations in the livers were found for the 2,3,7,8- substituted penta- and hexa-chlorinated PCDDs and PCDFs in both species during the three time periods.     

Isomer dependent bioavailability of polychlorinated dibenzo-p-dioxins and dibenzofurans from municipal incinerator fly ash to carp

The isomer dependent bioavailability of PCDDs and PCDFs from municipal incinerator fly ash to freshwater fish was determined. It was observed that carp exposed to fly ash in a continuous flow exposure readily accumulated select isomers of PCDDs and PCDFs. A preference for greater retention of isomers substituted in the 2, 3, 7 and 8 positions was observed. The Bioavailability Index (ratio of contaminant level in fish to level in fly ash) decreased with increasing degree of chlorination.     

A comprehensive pollution survey of polychlorinated dibenzo-p-dioxins and dibenzofurans by means of principal component analysis and partial least squares regression

The combined use of principal component analysis and partial least squares regression to the interpretation of polychlorinated dibenzofuran (PCDF) and dibenzo-p-dioxin (PCDD) patterns in crabs are investigated. By exploratory principal component analysis, the PCDFs and the PCDDs are ranked according to their specificity to the emission source. Among the most specific PCDFs to the emission are the 12368/13479-PeCDF and 12478-PeCDF. The 123789-HxCDD isomer is the only specific PCDD to the emission source. Partial least squares regression is used both to explore the determination of sex specific isomers, and in confirmatory analysis by quantitatively relating the pollution waste to the distance from the emission source. 123678-HxCDF is statistically significant for the separation between male and female crabs collected at the same distance from the emission source, while no separation between male and female crabs is evident from 1234789-HpCDF, Octa-CDF, 2,3,7,8-TCDD and Octa-CDD. This observation is somewhat more shaded than what has previously been reported in the literature on differences in male and female crabs. A linear relationship exists between the logtransformed distance and the concentration of PCDFs and PCDDs in male crabs collected between 18 and 33 km from the source. This model underestimates the predicted distance of crabs collected between 33 and 56 km, possible due to a higher sedimentation rate at distances closer to the fjord and the factory.

Although applied to PCDF/PCDD data in this case, the outlined multivariate methods should be applicable to all kind of similar environmental surveys.     

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.     

Use of the metastable atom bombardment (MAB) ion source for the elimination of PCDE interference in PCDD/PCDF analysis

The analysis of polychlorinated dioxins and furans (PCDDs/PCDFs) can produce erroneous results when polychloro diphenyl ethers (PCDEs) are present because they fragment and rearrange under electron ionization to give isobaric ions with PCDFs. Mass information must be generated to indicate the occurrence of possible PCDEs but uncertainty still exists if a PCDE congener has the same retention time as a PCDF congener. The metastable atom bombardment (MAB) ion source does not transfer enough energy to PCDE upon ionization to fragment the molecular ion, thus eliminating the need for PCDE tracking in PCDF analysis. Experiments were conducted with different gases, representing different ionization energies, to demonstrate that PCDE interference can be eliminated from PCDF analysis.     

Electrophilic bromination of dibenzofuran

Dibenzofuran has been brominated under standard electrophilic conditions to yield mono- through octabromodibenzofuran. The GC retention indices for ten products have been measured and correlated with the retention indices for the corresponding chloro dibenzofurans. Mass spectra for the eight major products are reported.     

Formation behavior of PCDD/Fs in PVC pyrolysis with copper oxide

Formation and decomposition behaviors of PCDD/Fs during pyrolysis of polyvinyl chloride (PVC) with CuO have been investigated. These reactions proceed simultaneously, and the rate of decomposition exceeds that of formation with further retention. More 2,3,7,8-TCDD is formed when the dechlorination of PCDD/Fs proceeds significantly. Homologue profile patterns of PCDD/Fs show that the fractions of O8CDD and H6CDFs are relatively larger within PCDDs and PCDFs, respectively. Extremely large amounts of PCDD/Fs are obtained with the long retention time at 200 degrees C. The formation of PCDD/Fs decreases drastically with increase in the molar ratio of CuO/PVC. The acceptability of thermodynamic calculations on the formation of PCDD/Fs is also investigated. The thermodynamic calculated tendency of the effect of oxygen on the formation of PCDD/Fs agrees well with the experimental results, although absolute values of the amount of PCDD/Fs are much different.     

Trend studies of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans in human milk

Human milk has been used in studies of long-term changes in the concentrations of organochlorine contaminants in mothers from the Stockholm region. The previously observed decline (1972 to 1985) in the levels of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) seems to have ceased for certain compounds since the levels were about the same in samples collected in 1985 and 1989. Calculating with the proposed toxicity equivalency factors for the different congeners of PCDDs, PCDFs and PCBs it is seen that the congeners of PCBs contribute more to the possible toxicity than those of PCDDs and PCDFs. The mono-ortho substituted congener 2,3′,4,4′,5-pentachlorobiphenyl (IUPAC No. 118) contributes with the largest part.     

Comparative toxicities of the polychlorinated dibenzofuran (PCDF) and biphenyl (PCB) mixtures which persist in Yusho victims

The toxic Yusho oil contained a mixture of polychlorinated biphenyls (PCBs) which were contaminated by other halogenated aromatics including the highly toxic polychlorinated dibenzofurans (PCDFs). It has been reported that the PCBs and PCDFs which persist in the liver of victims still suffering from Yusho poisoning include the following compounds; 2,3′,4,4′,5-penta-,2,2′,4,4′,5,5′-,2,2′,3′,4,4′,5- and 2,3,3′,4,4′,5-hexa, 2,2′,3,4,4′,5,5′- and 2,2′,3,3′,4,4′,5-heptachlorobiphenyls and the 2,3,7,8-tetra-, 1,2,4,7,8-, 1,2,3,7,8- and 2,3,4,7,8-penta- and 1,2,3,4,7,8-hexachlorodibenzofurans. All of these PCBs and PCDFs have been synthesized and reconstituted to approximate their composition in human liver. A comparison of the dose-response effects of the reconstituted PCB and PCDF mixtures in causing weight loss, thymic atrophy and the induction of cytochrome P-448-dependent monooxygenases indicated that the PCDF mixture was at least 700 times more active than the PCBs. Since the ratio of PCBs/PCDFs persisting in Yusho patients' blood and liver was less than 600:1 and 5:1 respectively, the results suggest that the PCDFs are the major etiologic agent in Yusho poisoning.     

PCDDs, PCDFs emission control by dry scrubbing system

Presently, in Japan there are no limitations on the emission of PCDDs or PCDFs, but in order to study the feasibility of dry type air pollution control, a pilot plant was constructed in 1988 and the removal efficiencies for PCDDs, acid gas and heavy metals were measured.At the same time PCDDs concentration was compared with that of a previously installed electrostatic precipitator (ESP) plus wet scrubber line.In this paper, the following two items are reported.

1. (1) The difference in the amounts of PCDDs and PCDFs produced due to differences in gas temperature and retention time in ESP and fabric filter (FF).

2. (2) Removal efficiencies of PCDDs and PCDFs of fabric filter.

PCDDs concentration, generally 100–200 ng/Nm³ at the boiler outlet (ESP inlet and/or Quench Reactor (QR) inlet), increased several times at the ESP outlet, but it showed almost no increase at the QR outlet due to a sudden temperature drop. The temperature was 280–310°C, and the gas retention time was 12 sec. during passage through ESP so that it is thought that PCDD was formed under these conditions.On the other hand, a removal efficiency of approx. 90% was obtained with the fabric filter, and the PCDD at the bag outlet was at a sufficiently low level.     

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.     

Bio-availability of PCDDs and PCDFs on fly ash after semi-chronic oral ingestion by the rat

Groups of rats (n = 5) were fed a diet containing 2.5% RCl pre-treated fly ash from the electrostatic precipator of a municipal incinerator during 34, 59 and 99 days. Livers were analysed for 2,3,4,7,8-pentachlorodibensofuran and higher chlorinated dibenso(p)dioxins (PCDDs) and dibensofurans (PCDFs). All isomers retained in the liver had a 2,3,7,8-chlorine substitution pattern. Total group dose varied between 0.2 and is μg for each individual retained compound. Retention in the liver was highest for 2,3,4,7,8-PnCDF, being 14% of the dose for the group killod on day 99. The other isomers detected in the livers had a retention generally below 10%. The 2,3,7,8-substituted hexa- and hepta- chlorinated PCDDs and PCDFs were retained in the liver in constant relative concentrations throughout the experiment, which closely approached a linear relationship to the administered dose.     

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.     

Concentration changes of PCDDs, PCDFs, and dioxin-like PCBs in human breast milk samples as shown by a follow-up survey

Breast milk is known to discharge dioxins from the human body. However, to date, no direct comparison has been made of the concentrations of dioxin analogues in breast milk obtained from identical population after successive deliveries. We present here follow-up survey results of PCDDs, PCDFs, and dioxin-like PCBs concentrations in human breast milk samples from 35 women living in Tokyo from whom samples had been obtained and analyzed to determine the corresponding concentrations in the past. The average concentrations of total PCDDs, PCDFs, dioxin-like PCBs were 8.5, 5.5, 11 TEQ pg/g fat for the first samples and 5.4, 4.0, 6.6 TEQ pg/g fat for the second samples, respectively. The degrees of reduction of total PCDDs and total dioxin-like PCBs were higher than that of total PCDFs because 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3',4,4',5-PeCB (#126), which were the predominant congeners among PCDDs, PCDFs, and dioxin-like PCBs, respectively, had different degrees of reduction. Moreover we observed a significant increase of the concentrations of PCDDs, PCDFs, and dioxin-like PCBs in samples from three women in this follow-up survey, and the patterns of increased isomers differed among the three samples. It was conjectured that the increase of the concentrations was due mainly to dietary intake between deliveries. It is important for pregnant women to have a balanced diet to mitigate the exposure of infants to these chemicals.     

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.     

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.     

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.