Levels of 2,3,7,8-Tetrachlorodibenzo- -dioxin (2,3,7,8-TCDD) in adipose tissue of U.S. Vietnam veterans seeking medical assistance

2,3,7,8-Tetrachlorodibenzo- -dioxin (2,3,7,8-TCDD) was detected in an earlier study in adipose tissue of U.S. veterans who were exposed to Agent Orange in Vietnam. The levels appear to be directly related to the intensity of exposure¹. We now report on a group of thirteen Vietnam veterans who were screened for 2,3,7,8-TCDD in adipose tissue. All the veterans had sought medical assistance and some had health effects that may be ascribed to exposure to 2,3,7,8-TCDD. Also included are control patients who were taken from the population of the U.S. 2,3,7,8-TCDD was detected in most of the adipose tissue samples at levels ranging from 2 to 14 ppt. No significant differences in the tissue levels of Vietnam veterans and the other persons were found in this preliminary study.     

Variation of dioxins and furans in human tissues

A number of chlorinated dibenzo-p-dioxins (PCDDs) and chlorinated dibenzofurans (PCDFs) occur in human adipose tissue at levels from 5 pg/g for 2, 3, 7, 8-TCDD to approximately 1000 pg/g for octachlorodibenzo-p-dioxin (OCDD). The variation of these compounds in tissues has been studied with respect to age, sex, tissue type, and country. A sampling of 46 adipose tissues from Canada in 1976 has shown a positive correlation of 2,3,7,8-TCDD level of detectable samples with age but not sex. This relationship is supported by the analysis for the first time of tissue from a 6 month old infant and the demonstration of little or no measurable levels of PCDDs/PCDFs. Three additional tissue types, pancreas, brain, and testis, from two autopsies were assayed for PCDDs/PCDFs for the first time but little or none were found even though the first two tissues had up to 10% lipid. A small sampling of adipose tissue from the general population in Japan in 1984 contained generally the same types and concentrations of PCDDs/PCDFs as are found in tissues from other industrialized countries.     

Colloid facilitated transport of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to the groundwater at Ma Da Area, Vietnam

PCDD/Fs are hydrophobic organic substances and strongly sorbing to soil particles. Once adsorbed to soil particles they are believed to be virtually immobile. However, research in the last decades confirmed that strong sorbing contaminants may reach the groundwater via colloid-facilitated transport. This pathway has not been investigated before in Vietnam. Ma Da area, 100 km north of Ho Chi Minh City, was repeatedly sprayed during the Vietnam War (1962–1971) with herbicides like Agent Orange containing, beside others, the teratogenic contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). 11 surface soil samples and 12 water samples were collected in Ma Da area for analysis of PCDD/Fs in solids. Soil TCDD concentrations ranged from 1–41 ppt with a mean of 8.8 ppt and a mean I-TEQ of 9.7 ppt. Two surface water samples showed colloid bound TCDD (7 and 19 ppt). Groundwater samples showed elevated colloid bound PCDD concentrations (mean 770 ng/kg), mainly octachlorodibenzo-p-dioxin. Groundwater colloids separated by filtration did not show any TCDD. The results support that TCDD/Fs can be relocated from the top soil to the groundwater by colloidal pathway. They did not provide evidence that the dioxins bound to groundwater colloids are leftovers from the Second Indochinese War. However, this study reinforces that the colloidal transport pathway has to be included investigating the relocation of strong sorbing organic contaminants.     

Levels and congener profiles of PCBs and PCDD/Fs in blue shark (Prionace glauca) liver from the South-Eastern Mediterranean Sea (Italy)

Liver of blue shark (Prionace glauca) specimens from the South-Eastern Mediterranean Sea were analyzed for the presence of polychlorinated biphenyls (PCBs), including coplanar congeners, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). PCBs were the dominant chemicals, followed by PCDFs and PCDDs. The pattern of PCB congener concentrations in the hepatic tissue was dominated by higher chlorinated compounds. The specific profile of toxic PCDD/F congeners was characterized mainly by 2,3,7,8-TCDF and 2,3,7,8-TCDD, followed by 1,2,3,6,7,8-HxCDD and 2,3,4,6,7,8-HxCDF. The total 2,3,7,8-TCDD toxic equivalent (TEQs) was 149 pg g⁻¹ lipid wt. The profile of TEQ shows that PCDDs present the greatest risk to this species contributing to total toxicity with a percentage approximately of 60%, while the contribution of PCDFs and DL-PCBs is almost the same being 22.4% and 21.6%, respectively. Further investigations are urgently needed to characterize the PCDD/Fs contamination levels not only in elasmobranch fish but in all Mediterranean marine biota.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in marine mammals in the Canadian North

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in pooled samples of ringed seal (Phoca hispida) blubber, beluga (Delphinapterus leucas) blubber and polar bear (Ursus maritimus) liver and fat from several areas throughout the Canadian north and compared to mean PCB and HCB levels in the same samples. All seal samples, and all but one polar bear sample, had detectable 2,3,7,8-TCDD at concentrations ranging from 2 to 37 ng/kg, but TCDD was not found in beluga blubber (< 2 ng/kg). All seal samples and one of three beluga samples contained 2,3,7,8-TCDF at levels of 2 to 7 ng/kg, but TCDF was not found in any bear sample. TCDF must therefore be cleared rapidly by polar bears. No other PCDF congeners were found at detection limits of 4 to 8 ng/kg. OCDD concentrations in seal blubber and polar bear samples ranged from not detected (< 8 ng/kg) to 43 ng/kg. No apparent biomagnification of TCDD, OCDD or TCDF occurred from seal to bear fat, similar to previous findings for DDT, and unlike SigmaPCBs and HCB which biomagnified 6- to 17-fold. Highest concentrations of 2,3,7,8-TCDD and OCDD in seals and bears were found in the central Canadian Arctic Archipelago, and lowest were found in Hudson Bay, the reverse of PCB concentration distribution. The reason for higher levels of TCDD and OCDD in the Arctic than in the sub-Arctic is suggested to be trans-polar movement of aerosols with combustion-related origins in Eurasia. Levels of 2,3,7,8-TCDF were more evenly distributed throughout the North, and were positively correlated with PCB, but not with HCB or 2,3,7,8-TCDD levels in seals.     

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.     

Polychlorinated dibenzodioxins and polychlorinated dibenzofurans in sewage sludges

A municipal sewage sludge from Syracuse, New York and a largely domestic sludge from Sodus, New York were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) using combined gas chromatography and high resolution mass spectrometry (GC/HRMS). Concentrations in ppt of the following PCDDs were found in the syracuse sludge: tetrachlorodibenzo-p-dioxins (TCDDs), 150, hexachlorodibenzo-p-dioxins (HxCDDs), 2100, heptachlorodibenzo-p-dioxins (HCDDs), 6300, octachlorodibenzo-p-dioxins (OCDDs), greater than 60,000. The following ppt concentrations were found in the Sodus sludge: TCDDs, 7200, HxCDDs, 300, HCDDs, 900, OCDDs 7500. The TCDD was a single but not the highly toxic 2,3,7,8-isomer. PCDFs were mostly nondetectable in the sludges. The toxicology and potential for environmental contamination by these compounds are discussed.     

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.     

Bald eagle mortality and chlorinated hydrocarbon contaminants in livers from British Columbia, Canada, 1989-1994

Between 1989 and 1994, we obtained 278 carcasses of bald eagles (Haliaeetus leucocephalus) found dead or dying in British Columbia, Canada. All specimens were necropsied and the cause of death determined wherever possible. Livers from a subset of 75 birds were analyzed for polychlorinated biphenyl (PCB) and organochlorine (OC) pesticide residues. A further subset of 19 eagles found dead around the Strait of Georgia, an area of known pulp mill pollution, in summer, and therefore presumably resident birds, were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) and non-ortho PCBs. Liver concentrations ranged from less than 1 to 190 mg/kg for DDE, and up to 72 mg/kg for total PCBs. Concentrations of other OCs were generally less than 1 mg/kg, with the exception of chlordane-related compounds which were occasionally over 2 mg/kg. All birds analyzed for PCDDs and PCDFs contained detectable concentrations of the major 2,3,7,8-substituted isomers. Some birds were very contaminated; one eagle found near a kraft pulp mill site in 1990 contained: 400 ng/kg 2,3,7,8-TCDD, 1400 ng/kg 1,2,3,7,8-PnCDD and 4400 ng/kg 1,2,3,6,7,8-HxCDD. Birds with higher PCB and dichlorodiphenyldichloroethane (DDE) concentrations appeared to weigh less, and there was a significant negative relationship between both PCBs and DDE and numeric scoring of body condition, reflecting the well known process of starvation-induced mobilization of body lipids and contaminants. Birds with higher 2,3,7,8-TCDD concentrations tended to have unusually low concentrations of 2,3,7,8-TCDF, interpreted to indicate hepatic cytochrome P4501A-type induction by TCDD and subsequent metabolism of TCDF.     

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).     

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 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.     

Partitioning of dioxin and dibenzofuran congeners between plasma and cell fractions of blood from 10 adult male patients

We previously characterized levels of dioxin and dibenzofuran congeners in adipose tissue and plasma fraction of blood collected from 20 adult males, using paired speciments. It has been found that the 2,3,7,8-TCDD level reported on a lipid basis was similar, although not identical, in plasma lipid and in adipose tissue lipid from the same patients, however, higher levels of the more chlorinated dioxins and dibenzofurans existed in plasma lipid as compared to adipose tissue lipid. This study reports measurements from ten individuals' blood cell fraction and compares this to the plasms fraction and to adipose tissue lipid. In all cases where readily detectable amounts of PCDD/Fs were found, a minimum of 85% was in the plasma fraction and less than 15% in the cellular component. Congeners varied in percentage for each component.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in eggs of eight avian species from Dongting Lake, China

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in eggs of eight avian species collected from Dongting Lake of China to assess residue levels, accumulation patterns, and toxic potential in different avian species. Concentrations of total 2,3,7,8-substituted PCDD/Fs were in the range of 10.8-182pgg(-1) lipid weight. Eggs of great egret and lesser pied kingfisher contained higher levels of PCDD/Fs than eggs of other species, indicating the specific exposure and accumulation of PCDD/Fs relating to feeding habits and the life span. PCDD/Fs congener patterns varied among species. The patterns of PCDD/Fs in the eggs may be influenced by feeding habits, specific elimination, and metabolism. In general, concentrations of PCDDs were higher than those of PCDFs in avian eggs. On basis of lipid weight, total 2,3,7,8-TCDD toxic equivalents (TEQs) calculated based on the WHO TEFs for birds ranged from 2.04 to 42.0pgg(-1); and on basis of wet weight, total WHO-TEQs ranged from 0.19 to 1.59pgg(-1). 2,3,7,8-TCDF, 2,3,4,7,8-PeCDF, 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD were the major contributors to TEQ concentration in most avian eggs, whereas 1,2,3,4,7,8-HxCDD also accounted for a major portion of TEQs in eggs of azure-winged magpie. Values of TEQs in avian eggs were lower than toxic threshold values, implying risk reduction and natural restoration of PCDD/Fs contamination in Dongting Lake region.     

Embryonic abnormalities and organochlorine contamination in double-crested cormorants (Phalacrocorax auritus) and Caspian terns (Hydroprogne caspia) from the upper Great Lakes in 1988

Persistent organochlorine contaminants including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were determined in eggs with normal and deformed embryos collected in 1988 from different colonies during an epizootiological survey of double-crested cormorants (Phalacrocorax auritus) and Caspian terns (Hydroprogne caspia) from the upper Great Lakes. PCBs and p,p'-DDE were found in the highest concentrations in eggs of both species. The residue pattern of PCB isomers and chlordane compounds suggested that double-crested cormorants have greater metabolic capacity to degrade contaminants than Caspian terns. According to the toxicity evaluation using the 2,3,7,8-TCDD equivalents (TEQs) approach, non-ortho coplanar PCBs contributed much more toxicity than PCDDs and PCDFs. Total TEQ of dioxin-like compounds was likely associated with occurrence of live-deformed embryos in double-crested cormorants eggs. The toxic effects of these contaminants were also estimated in Caspian tern eggs, where elevated levels of coplanar PCBs, PCDDs and PCDFs were observed in concordance with increased rate of anomalies in eggs during a breeding season in the Great Lakes.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in Great Barrier Reef (Australia) dugongs (Dugong dugon)

Fat tissue samples from dugong (Dugong dugon) carcasses stranded at three sites along the Great Barrier Reef were analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Relatively high levels of PCDDs were determined in all three dugongs. In particular OCDD, the PCDD/F congener that is usually considered the least bioavailable of all 2,3,7,8 substituted congeners, was found at levels higher than reported for other marine mammals. Tissue accumulation of PCDDs by dugongs may be a consequence of sediment and/or seagrass ingestion during feeding, microbial biotransformation of PCDD precursors in the animal's hindgut or, alternatively, the possession of a selective degradation capability for PCDFs.     

Dioxins in adipose tissue of women in Southern Spain

Seventeen polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were quantified in adipose tissue samples of non-occupationally exposed women living in Southern Spain. Geometric mean levels of sum of congeners and WHO(PCDD/F)-TEQ(2005) were 410 and 17.9pgg(-1) fat, respectively. Among PCDDs, octachlorodibenzo-p-dioxin (OCDD) showed the highest concentration with a mean value of 265pgg(-1) fat, followed by 1,2,3,6,7,8-HxCDD (49.3pgg(-1) fat) and 1,2,3,4,6,7,8-HpCDD (45.2pgg(-1) fat). These three congeners were responsible for around 90% of the sum of all PCDD/F congeners in adipose tissue. The geometric mean 2,3,7,8-TCDD value was 1.87pgg(-1) fat. 2,3,4,7,8-PeCDF (8.43pgg(-1) fat) showed the highest concentration among the PCDFs, followed by 1,2,3,4,7,8-HxCDF (4.17pgg(-1) fat) and 1,2,3,6,7,8-HxCDF (3.28pgg(-1) fat), and these three congeners were responsible for 4% of the sum of all studied PCDD/F congeners in adipose tissue and 76% of the sum of ten PCDFs. 1,2,3,7,8,9-HxCDF was the only congener not quantified in any sample, while 1,2,3,4,7,8,9-HpCDF, 1,2,3,7,8-PeCDF, OCDF and 2,3,7,8-TCDF were found in 5, 16, 16 and 19 samples, respectively. All other congeners were quantifiable in all 20 samples. Congeners contributing most to the WHO(PCDD/F)-TEQ(2005) were 1,2,3,7,8-PeCDD (31.6%), 1,2,3,6,7,8-HxCDD (28.3%) and 2,3,4,7,8-PeCDF (14.6%). The body burden of log-transformed WHO(PCDD/F)-TEQ(2005) levels increased with age (B=0.02; 95% CI=0.01, 0.03; p=0.02). Although these adipose tissue PCDD/F levels are similar to previously published findings in Spain and other European countries, further research is needed to determine trends in the exposure of women to these chemical residues.     

Polychlorinated dibenzodioxins and dibenzofurans in butter from different states in Australia

Nine samples of butter from producers in various states of Australia were analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Detectable concentrations of 2,3,7,8-chlorine substituted PCDD/Fs were found in all samples. The mean PCDD/F concentration expressed as 2,3,7,8-TCDD equivalents (TEQs) was 0.19 pg TEQ g-1 fat. The highest concentration (0.46 pg TEQ g-1 fat) was observable in a sample from Victoria which is the most densely populated state. Overall the results indicate that PCDD/F concentrations in dairy products from Australia are low in comparison to the levels in dairy products of industrialized countries on the Northern Hemisphere. As expected, this study provides evidence that the environmental and consequently the human body burden of PCDD/Fs to be relatively low in Australia.     

A survey of PCDD and PCDF in French long-life half-skimmed drinking milk

A national survey was carried out in order to assess the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in long-life half-skimmed drinking milk produced and consumed in France. 151 Samples were collected from 33 dairy establishments selected for their production amounts following a random sampling scheme. 148 of the 151 results were finally used for statistical assessment. The mean concentration of 2,3,7,8-TCDD toxicity equivalent found is 0.65 pg/g of milk fat. This result is far below the threshold recommended by the European Union.     

Assigning concentration values for dioxin and furan congeners in human serum when measurements are below limits of detection: an observational approach

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in dietary sources for humans have been declining over the previous two decades. These declines have been accompanied by decreases in concentrations of these compounds in humans, as evidenced by measurements in blood and milk. Because of the decreasing concentrations of PCDD/PCDFs in the environment and in humans, measuring PCDD/PCDF congeners in humans has become increasingly difficult, despite advances in analytic methods. An observational approach was recently described to address the quandary of non-detectable results in determining toxic equivalents. This approach, called the congener ratio approach, is specifically for cases where concentrations of 2,3,7,8-TCDD (TCDD) are below the limit of detection (LOD), and where concentrations of 1,2,3,7,8-pentachlorodibenzo-p-dioxin (PeCDD) are equal to or above the LOD. Development of this approach relied on evaluating data on measured concentrations of TCDD and PeCDD in human serum from the general population. The congener ratio approach for TCDD and PeCDD was based on the concentration of TCDD being approximately 40% that of PeCDD in serum from the general population. Additional analyses presented here reveal that when concentrations of both congeners are above the LOD, the data appear to generally support the congener ratio approach for TCDD and PeCDD, with the caveat that gender may affect the ratio. However, the TCDD/PeCDD relation is less clear when TCDD is less than the LOD; in this situation, the relation overpredicts levels of TCDD approximately 80% of the time for the 2001-2002 NHANES database. Using the congener ratio approach for other PCDD/PCDF congeners requires assessing the correlation and the frequency of detection for both TCDD and PeCDD.