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.     

Disposition of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in two Norwegian epibenthic marine food webs

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are a group of halogenated hydrocarbons, comprising 210 different, theoretically possible congeners. They are relatively hydrophobic and persistent to biodegradation, thereby rendering them subject to bioaccumulation. This study was conducted in Frierfjord and Eidangerfjord in the Grenland fjord system, Norway, heavily polluted by PCDD/PCDF discharges from the magnesium production at Herøya from 1951 to 2001. Pooled samples of surface-sediments and the following organisms were collected for the Frierfjord and Eidangerfjord study areas: common shrimp (Crangon crangon), polychaetes (mainly Nereis diversicolor), shore crab (Carcinus maenas), cod (Gadus morhua), flounder (Platichthys flesus), trout (Salmo trutta), herring (Clupea harengus), benthic amphipods and zooplankton. Concentrations of 2,3,7,8-PCDD/Fs were quantified in pooled samples for all species. The relative abundances of stable isotopes of nitrogen (δ¹⁵N) were evaluated in the organisms as a measure of chemically-derived trophic level. Contrary to earlier studies on other persistent organochlorines, it was found that the concentrations of PCDD/Fs declined with increasing trophic level. Principal Component Analysis (PCA) also showed differences between species in the pattern of PCDD/Fs. Higher chlorinated congeners constituted lower percentages of the PCDD/F-concentrations higher in the food chain as compared to lower trophic levels. In general, congener patterns did not differ between fjords. Infauna (polychaetes) and zooplankton had congener patterns most similar to the pollution source. The results indicate lower accumulation of higher chlorinated congeners in species at higher trophic levels (fish), presumably due to low membrane permeability (high molecular size) and possibly slow transport through intestinal aqueous phases because of low aqueous solubility.     

Vehicle dependent bioavailability of polychlorinated dibenzo-p-dioxins (PCDDs) and -dibenzofurans (PCDFs) in the rat

PCDDs and PCDFs were administered as fly ash (500 mg) or fly ash extract to male Wistar rats. The extract was administered orally and intravenously by using arachidis oil and miglyol 812 as oily vehicles. Liver retentions were determined after 48 hours as a degree of bioavailability. In all experiments only the 2,3,7,8-substituted congeners, with the exception of 2,3,4,6,7-PnCDF, were detected in the liver. The dose was 10 to 40 ng for each congener. The lowest bioavailability was found in the experiments with crude or hydrochloric acid pretreated fly ash. Liver retentions were comparable for both experiments with fly ash (0.4 – 3.8%) and were approximately 10 times higher in the oral experiments with oily vehicles. Miglyol 812 produced slightly lower liver retentions compared with arachidis oil. Intravenous dosage with miglyol 812 resulted in liver retentions twice as high as oral administration with this vehicle.     

A congener-specific survey for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) contamination in Masan Bay, Korea

A congener-specific determination of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in 21 surface sediments from Masan Bay, Korea revealed that the most toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was detected in 76% of the samples and 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF) in 100% of the samples analyzed. The concentration range of SigmaPCDDs and SigmaPCDFs are: 230-6900; 120-16700pgg(-1) dry mass respectively. WHO Toxic Equivalents (WHO-TEQ) in Masan Bay sediment ranged from 0.53 to 99ng TEQkg(-1)d.m. for PCDDs; 4 to 1300ngTEQkg(-1)d.m. for PCDFs. In comparison with an earlier survey, the concentrations of dioxins and furans have more than doubled and the SigmaWHO-TEQ values have increased 15 times within a decade. Both point and non-point sources of pollution are suspected, especially, local sewage treatment plants are found to contribute.     

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.     

Global pollution monitoring of polychlorinated dibenzo-p-dioxins (PCDDs), furans (PCDFs) and coplanar polychlorinated biphenyls (coplanar PCBs) using skipjack tuna as bioindicator

In order to elucidate the global distribution of dioxins and related compounds, such as PCDDs, PCDFs and coplanar PCBs, levels of these compounds were determined in the muscle of skipjack tuna (Katsuwonus pelamis) collected from the offshore waters and open seas near Japan, Taiwan, Philippines, Indonesia, Seychelles and Brazil, and the Japan Sea, the East China Sea, the South China Sea, the Indian Ocean and the North Pacific Ocean. PCDDs, PCDFs and coplanar PCBs were detected in almost all the specimens collected from all the locations surveyed, indicating widespread contamination by these compounds in the marine environment. Higher concentrations of dioxins and coplanar PCBs were detected in the samples from temperate Asian regions, plausibly due to larger usage and anthropogenic generation in highly industrialized countries around the East China Sea and the South China Sea, such as Japan, Korea, Taiwan, Hong Kong and coastal China.     

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) in the serum of US Air Force veterans in 2002

We measured levels of PCDDs, PCDFs, non-ortho, and mono-ortho substituted PCBs in 106 US Air Force Vietnam veterans, participants of the Air Force Health Study (AFHS) who attended the final medical examination in 2002. Twelve veterans were Ranch Hands involved in aerial spraying of herbicides in Vietnam (1962-1971), and 94 were Comparisons who flew transport missions in Southeast Asia (SEA) during the same time period. These veterans had no previous 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) measurement because they had not attended any of the previous AFHS examinations, or their previous measurements were missing or not valid. The mean TCDD levels in 2002 were 1.7 pg/g lipid in Comparisons and 5.5 pg/g lipid in Ranch Hands. The mean PCDD toxic equivalent - TEQ (1997) in Comparisons was 12.6 pg/g lipid, 5.4 pg/g lipid for PCDFs, 5.2 pg/g lipid for non-ortho PCBs, and 9.4 pg/g lipid for mono-ortho PCBs, with a total mean TEQ (1997) of 32.6 pg/g lipid. Corresponding mean TEQs in Ranch Hands were 15.5 pg/g lipid for PCDDs, 4.6 pg/g lipid for PCDFs, 2.2 pg/g lipid for non-ortho PCBs, and 9.3 pg/g lipid for mono-ortho PCBs, yielding the total mean TEQ (1997) of 31.6pg/g lipid. Using the re-evaluated 2005 WHO TEFs, the total mean TEQs (2005) decreased by about 28% in both Comparisons and Ranch Hands, to 23.6 pg/g lipid and 22.8 pg/g lipid, respectively. This was mainly due to changes of TEFs for the group of mono-ortho PCBs, which decreased the mono-ortho PCBs TEQs by almost 90% in both Ranch Hands and Comparisons.     

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in waterbird eggs of Hong Kong, China

Concentrations of PCDD/Fs, PCBs and PBDEs were measured in 56 egg samples collected from waterbirds of different species (Great Egret, Little Egret, Night Heron and Chinese Pond Heron) from different regions of Hong Kong (Ho Sheung Heung, Mai Po Village and Mai Po Lung Village) during 2000 and 2006. Dominance of 2,3,4,7,8-PeCDF indicates a signature associated with commercial usage of PCBs. Although no significant variations were observed within- and between-site in the levels of PCDD/Fs, coplanar PCBs and PBDEs, the concentrations of coplanar PCBs were much higher than PCDD/Fs. Similarity in composition profiles of PCDD/F and coplanar PCBs from different egretries is possibly associated with non-point sources of these contaminants to Hong Kong. Predominant accumulation of BDE-47, BDE-99 and BDE-100 suggested the penta-BDE technical mixtures usage in Hong Kong and its vicinity. Toxic equivalency and Monte Carlo simulation technique showed potential risks on waterbirds due to their exposure to PCDD/Fs.     

The influence of sewage sludge applications to agricultural land on human exposure to polychlorinated dibenzo-p-dioxins (PCDDs) and -furans (PCDFs)

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) are organic chemicals of suspected extreme toxicity. PCDD/Fs are ubiquitous in the environment and relatively enriched in sewage sludges. The deliberate application of sewage sludge to agricultural land can therefore potentially increase exposure of the human population to these compounds via transfers through the foodchain. This paper presents a protocol for assessing the background human exposure to all seventeen 2,3,7,8-substituted PCDD/Fs for which toxic equivalent factors (TEFs) are available. Background daily human exposure in the UK to 2,3,7,8-T(4)CDD and I-TEQ are calculated to be 0.0239 ng and 0.203 ng, respectively. The potential increases in crop plant and livestock tissue PCDD/F concentrations, and hence in human exposure, following applications of sewage sludge to agricultural land are quantified for different sludge application scenarios. The key role of PCDD/F transfer into livestock via ingestion of sludge adhered to vegetation in determining increases in human exposure is demonstrated.     

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in breast milk of first-time Irish mothers: impact of the 2008 dioxin incident in Ireland

The 2008 dioxin incident in Ireland resulted in elevated concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in Irish pork and pork products, due to the consumption of contaminated animal feed by pigs. In order to investigate any resulting impact on the Irish population, these contaminants were measured in pooled breast milk samples from 109 first-time mothers, collected in 2010. A comparison of the results with similar data from 2002 revealed generally lower concentrations of PCDD/Fs and dioxin-like PCBs in the 2010 samples, confirming the declining trend reported by many authors. Contaminant concentration levels for both 2002 and 2010 were generally slightly lower than those reported internationally, with a mean combined PCDD/F and PCB WHO-TEQ of 9.66 pg g⁻¹ fat, for an overall pooled sample of milk from 2010. An apparent slight increase in PCDFs was observed between 2002 and 2010 (from 2.73 pg WHO-TEQ g⁻¹ fat to 3.21 pg WHO-TEQ g⁻¹ fat), with the main contributory congener being 2,3,4,7,8-PentaCDF. While it cannot be totally discounted that the slight increase in 2,3,4,7,8-PentaCDF and in the overall PCDF WHO-TEQ in breast milk could be attributable to consumption of Irish pork during the 2008 incident, we consider that it is more likely that this was due to other factors, including the predominantly urban/industrial sampling locations for the 2010 samples, compared to 2002.     

A mixture of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and non-ortho polychlorinated biphenyls (PCBs) changed the lipid content of pregnant Long Evans rats

Pregnant Long Evans rats received 1.0 μg/kg of dioxin toxic equivalents (TEQ) by oral gavage on the 15th gestational day (GD 15), using a dosing mixture that contained two polychlorinated dioxins, four polychlorinated furans and three non-ortho polychlorinated biphenyls (PCBs). Rats were sacrificed on GD 16, GD 21 and postnatal day 4 (PND 4). The lipid content of fetus, pup, placenta and maternal liver, serum and adipose tissue were determined. Treated GD 16 and GD 21 fetuses had identical lipid content to the control group, yet the lipid content of treated pups on PND 4 was 32% higher than that of the control group. On the other hand, the lipid content of placenta, liver, and serum from the treated dams was 44–50%, 24%, and 38% lower than that of the control group, respectively. Thus, a low-dose mixture of dioxin-like compounds can cause changes in lipid content. The lipid content of offspring was not affected until they were exposed via lactation.     

Dioxins (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo-furans) in traditional clay products used during pregnancy

Geophagy, the practice of consuming clay or soil, is encountered among pregnant women in Africa, Eastern Asia and Latin America, but also in Western societies. However, certain types of clay are known to contain high concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The aim of this study was to determine the PCDD/F contents of orally consumed clays purchased from Dutch and African markets. Congener patterns were compared with those of pooled human milk samples collected in eight African countries, to investigate a possible relationship with clay consumption. From the Dutch market thirteen clay products were examined, seven of African and six of Suriname origin. From seven African countries, twenty clay products were collected. All 33 clay products were screened with a cell-based bioassay and those showing a high response were analyzed by GC/HRMS. High PCDD/F concentrations were measured in three clay products from the Dutch market, ranging from 66 to 103 pg TEQ g^-1, whereas clay products from African countries were from 24 to 75 pg TEQ g^-1. Patterns and relatively high concentrations of PCDD/Fs in human milk samples from the Democratic Republic of the Congo and Côte d’Ivoire suggest a relationship with the consumption of contaminated clay. Frequent use of PCDD/F contaminated clay products during pregnancy may result in increased exposure of the mother and subsequently the developing fetus and new-born child. The use of these contaminated clays during pregnancy should be carefully considered or even discouraged.     

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.     

Rat metabolism of polychlorinated dibenzo-p-dioxins

In rats, dibenzo-p-dioxin, 1-chlorodibenzo-p-dioxin, 2-chlorodibenzo-p-dioxin, 2,3-dichlorodibenzo-p-dioxin, 2,7-dichlorodibenzo-p-dioxin, 1,2,4-trichlorodibenzo-p-dioxin and 1,2,3,4-tetrachlorodibenzo-p-dioxin are metabolized to mono- and dihydroxy derivatives, whilst in case of dibenzo-p-dioxin and both the two monochloro isomers, also sulphur containing metabolites are excreted. Primary hydroxylation exclusively takes place at the 2-, 3-, 7- or 8-position in the molecule. In none of the experiments metabolites resulting from fission of the C-O bonds (ortho, ortho'-dihydroxychlorodiphenyl ethers, chlorocatechols) or hydroxylated derivatives thereof, were detected. No metabolites were found from octachlorodibenzo-p-dioxin.     

Analysis of mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDD/PXDFs) in soil by gas chromatography tandem mass spectrometry (GC-MS/MS)

Mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDD/PXDFs, X = Br, Cl) are formed through combustion processes, and may be more toxic than their corresponding chlorinated and brominated analogues. With 4600 potential congeners, limited analytical standards, and complex environmental matrices, PXDD/PXDFs present a significant analytical challenge. Gas chromatography tandem mass spectrometry (GC-MS/MS) offers both selectivity and sensitivity through multiple reaction monitoring of unique transitions in a novel approach to PXDD/PXDF congener identification. Method validation was performed through analysis of soil samples obtained from a recycling plant fire. Of the PXDD/PXDFs examined, monobromo-dichlorodibenzofuran was the most prevalent, ranging in concentration from 8.6 ng g⁻¹ to 180 ng g⁻¹. Dibromo-dichlorodibenzo-p-dioxin, a compound of toxicological concern, ranged from 0.41 ng g⁻¹ to 10 ng g⁻¹. Concentrations of PXDD/PXDFs were between 6% and 10% that of the corresponding polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs), with the exception of dibromo-dichlorodibenzo-p-dioxin concentrations, which were 36% that of tetrachlorodibenzo-p-dioxins. Higher levels of polybrominated PXDD/PXDFs may indicate a significant bromine source was present during combustion.     

Monitoring of air pollution by polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans of pine needles in Korea

The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.