Concentrations Of Polychlorinated Dibenzofurans Research Articles

Gaseous emissions from co‐combustion of biosolids from the meat processing industry with wood

AbstractFlotation sludge from the meat processing industry can be applied as biofuel in already existing plant‐scale boilers. This biosolid is rich in oil and grease and has higher energetic content on a dry ash‐free basis (22.74 and 27.71 MJ kg−1) than the wood‐based fuel (16.62 and 16.16 MJ kg−1). Co‐combustion trials were performed at a pilot‐scale cyclonic combustor (100 kg h−1) and at an industrial flamotubular rotatory grate‐fired system (6000 kg h−1), co‐firing pre‐dried and centrifuged flotation sludges (respectively) and wood at a mass ratio of 1:3. At a moisture content of 60.13 wt%, the lower heating value of the centrifuged sludge was 10.24% lower compared to wood, thus reducing it to at least 40 wt% would be advisable to obtain energy gains in the industrial plant when operating the co‐combustion. The emissions were evaluated and compared to emission standards, including the characterization of polycyclic aromatic hydrocarbons and polychlorinated dibenzo‐p‐dioxins and polychlorinated dibenzofurans (given as Toxicity Equivalent Factors at O2ref = 7%), which have not yet been reported. The 16 target polycyclic aromatic hydrocarbons were identified at pilot and plant scales (0.582 ± 0.143 μg Nm−3 and 0.602 ± 0.506 μg Nm−3, respectively) being lower than the Danish reference standard (5.0 μg Nm−3). The polychlorinated dibenzo‐p‐dioxins and polychlorinated dibenzofurans concentrations were 0.0004 ± 0.0001 ng Nm−3 at pilot scale and 0.3617 ± 0.1310 ng Nm−3 at plant scale, both below the Brazilian and American standards but differed greatly between the scales, requiring further investigation since their formation can occur due to combustion and postcombustion conditions.

Exploring the associations of serum concentrations of PCBs, PCDDs, and PCDFs with walking speed in the U.S. general population: Beyond standard linear models

Studies have shown that persistent organic pollutants (POPs) can have various health effects. However, little is known about the effects of multiple chemicals with possible common sources of exposure on walking speed, a proxy index reflecting lower limb neuromuscular function and physical function. We simultaneously applied multiple linear and nonlinear statistical models to explore the complex exposure-response relationship between a mixture of 22 selected POPs and walking speed. A total of 14 polychlorinated biphenyls (PCBs), 3 polychlorinated dibenzo-p-dioxins (PCDDs), and 5 polychlorinated dibenzofurans (PCDFs) were measured in the serum of participants in the National Health and Nutrition Examination Survey (NHANES) from 1999 to 2002. Walking speed was measured during a physical examination. Linear regression (LR), least absolute shrinkage and selection operator (LASSO), and group LASSO were used to evaluate the linearity of mixtures, while restricted cubic spline (RCS) regression, random forest (RF), and Bayesian kernel machine regression (BKMR) models were used to evaluate the nonlinearity of mixtures. Potential confounders were adjusted in the above models. A total of 436 subjects were included in our final analysis. The results of the LR model did not identify any POP exposure that was significantly associated with walking speed. The LASSO results revealed an inverse association of one PCDD congener and two PCDF congeners with walking speed, while the group LASSO analysis identified PCDFs at the exposure level and at the group level. In the RCS analysis, two PCB congeners presented significant overall associations with walking speed. The PCB congener PCB194 showed statistically significant effects on the outcome (P = 0.01) when a permutation-based RF was used. The BKMR analysis suggested that PCBs and PCDFs (probabilities = 0.887 and 0.909, respectively) are potentially associated with walking speed. Complex statistical models, such as RCS regression, RF and BKMR models, can detect the nonlinear and nonadditive relationships between PCBs and walking speed, while LASSO and group LASSO can identify only the linear relationships between PCDFs and walking speed. Fully considering the influence of collinearity in each method during modelling can increase the comprehensiveness and reliability of conclusions in studies of multiple chemicals.

Occurrence of legacy and emerging organic pollutants in whitemouth croakers from Southeastern Brazil

The whitemouth croaker (Micropogonias furnieri) is one of the most commercially important species along the Atlantic coast of South America. Moreover, some of its biological traits (long life span, inshore feeding, high trophic position) make this species a suitable sentinel of coastal pollution. Here, we investigated contamination by multiple legacy and emerging organic pollutants, such as brominated and chlorinated flame retardants, polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), in whitemouth croakers from two estuaries (Guanabara and Sepetiba Bays) located in industrialized and urbanized areas in Rio de Janeiro State, Southeastern Brazil. Furthermore, we assessed how biological and ecological features could explain the observed contamination patterns. Regarding brominated flame retardants, concentrations of polybrominated diphenyl ethers (PBDEs) varied from 7.6 to 879.7 pg g−1 wet weight (w.w.), with high contribution of tetra-, penta-, hexa- and deca-BDEs. The sum of chlorinated flame retardants (dechlorane-related compounds, ΣDRC) ranged from <LOD to 41.1 pg g−1 w.w., mostly represented by Dechlorane 603 and Dechlorane Plus (DP). Concentrations of PCDDs and PCDFs varied from <LOD to 1.7 pg g−1 w.w., while the Toxic Equivalent (TEQ-PCDD/Fs) levels ranged from 0.1 to 0.2 pg g−1 w.w. Positive correlations between δ15N and concentrations of tri-, tetra- and penta-BDEs, as well as ΣDRC, DP and anti-DP isomers suggested that ecological factors (namely biomagnification along the food web) influence contamination of whitemouth croakers in the estuaries studied. Moreover, the sum of PBDEs (ΣPBDE), tri- and tetra-BDEs concentrations were negatively correlated with fish size, suggesting that depuration by fishes and/or habitat shift throughout the whitemouth croaker's life cycle might also influence concentrations. Overall, our study emphasized the need for further investigations to help understand the complex patterns of bioaccumulation and biomagnification that seem to exist in Southeastern Brazil.

Perinatal polychlorinated biphenyls and polychlorinated dibenzofurans exposure are associated with DNA methylation changes lasting to early adulthood: Findings from Yucheng second generation

Epigenome-wide DNA methylation has not been studied in men perinatally exposed to PCBs and dioxins. Therefore, we examined whether perinatal exposure to polychlorinated biphenyls (PCBs) and polychlorinated dibenzofurans (PCDFs) induces sustained methylation changes lasting to early adulthood. We used the Illumina HumanMethylation450 BeadChip to assess DNA methylation in whole blood among Yucheng second generation (people perinatal exposed to high PCBs and PCDFs) compared with referents. Thirty male offspring from the Yucheng cohort were randomly selected and matched with 30 male offspring from the Yucheng’ neighborhood referents with similar backgrounds. Methylation differences between the Yucheng second generation and non-exposed referents were identified using a P value < 1.06 × 10−7. Differential DNA methylation with epigenome-wide statistical significance was observed for 20 CpGs mapped to 11 genes, and 19 CpGs were correlated with gestational levels of PCBs or PCDF toxic equivalency (PCDF-TEQ) with the same direction of effect. Among the 11 genes, AHRR and CYP1A1 are involved in the aryl hydrocarbon receptor signaling pathway known to mediate dioxin toxicity. MYO1G, FRMD4A, ARL4C, OLFM1, and WWC3 were previously reported to be related to carcinogenesis. This is the first study examining genome-wide DNA methylation among people perinatally exposed to high concentrations of PCBs and PCDFs. We observed novel differential methylation of several genes, indicating that modifications of DNA methylation associated with perinatal PCB and PCDF exposure may persist in exposed offspring for more than 20 years. Furthermore, involvement of several carcinogesis-related genes suggested a potential in utero epigenetic mechanisms.

PCDD/PCDF formation in the chlor-alkali process—laboratory study and comparison with patterns from contaminated sites

Studies on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) during the electrolysis of sodium chloride solution (brine) using graphite or titanium electrodes were carried out at a laboratory scale. High concentrations of PCDFs but no PCDDs were formed in tests using graphite electrodes. With titanium electrodes, PCDFs were only formed when tar pitch was added and mainly originated from the dibenzofuran present in the tar. For the first time, a detailed assessment of the formation of mono- to octachlorinated PCDD/PCDF from tar pitch was investigated. The assessment included of the chlorination steps proved that PCDFs were formed by successive lateral chlorinated from dibenzofuran to MonoCDFs, DiCDFs, and TriCDFs to form the typical known "chlorine pattern" of TetraCDF to OctaCDF with a dominance of 1,2,7,8- and 2,3,7,8-TetraCDFs, 1,2,3,7,8-PentaCDF, and 1,2,3,4,7,8-HexaCDF as marker congeners. The final homologue distributions depended on reaction time and reaction temperature. In addition, electrolysis with non-chlorinated dibenzo-p-dioxins, dibenzofuran, and biphenyl was carried out. As a result, PCDDs, PCDFs, and PCB were formed at comparable yields. Congener patterns in soil samples from a PCDD/F-contaminated site where chlor-alkali electrolysis had been operated for decades in Japan had identical isomer distribution demonstrating the source and contamination potential and risk of these processes. Therefore, sites where in the past 120 years chlor-alkali electrolysis has been operated or where residues from chlor-alkali production or other chlorine using industries have been disposed should be assessed for their pollution level and exposure relevance. The assessment of total organohalogen content revealed that PCDF is only a small fraction of organohalogens in the contaminated soils. For an appropriate risk assessment, also other chlorinated aromatic compounds such as PCBs or PCNs need to be considered.

Identification, Quantification, and Toxicity of PCDDs and PCDFs in Soils from Industrial Areas in the Central and Eastern Regions of Saudi Arabia

This study was conducted to identify and quantify polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in soil samples collected from selected industrial areas in the central and eastern regions of Saudi Arabia. All the investigated compounds of PCDDs/PCDFs were identified in the studied locations. The average concentrations of PCDDs (sum of seven congeners measured) ranged from 11.5 to 59.6 pg g(-1), with a maximum concentration of 125.7 pg g(-1) at an oil refinery station followed by 100.9 pg g(-1) at a cement factory. The average concentrations of PCDFs (sum of 10 congeners measured) accounted for 11.68-19.35 pg g(-1), with a maximum concentration of 38.67 pg g(-1) at the cement factory. It was generally observed that the soil samples collected from industrial areas have substantially high toxicity equivalence (TEQ) values of PCDDs/PCDFs compared to soils of remote areas. Principal component analysis revealed that the cement factories and oil refineries were the primary sources of PCDDs and PCDFs.

PCDDs, PCDFs, and PCBs co-occurrence in TiO2 nanoparticles.

In the present study, we report on the co-occurrence of persistent organic pollutants (POPs) adsorbed on nanoparticular titanium dioxide (TiO2). We report on the finding of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) on the surface of commercially available TiO2 nanoparticles, being formed during the fabrication process of the TiO2. Thereby, the samples comprise PCBs with higher congener numbers or, in the absence of PCBs, a high concentration of PCDDs and PCDFs. This new class of POPs on an active catalytic surface and the great range of applications of nanoparticular TiO2, such as in color pigments, cosmetics, and inks, give rise to great concern due to their potential toxicity.

The exposure of the Croatian population to toxic environmental contaminants – “Dioxin-like” PCBs

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs), and non-dioxin-like PCBs in paired samples of blood and breast milk collected from 67 secundiparas in Sapporo City, Japan, and combined this data with those of the 30 secundiparas previously measured. The arithmetic mean total toxic equivalents (TEQ-WHO) concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of the 97 secundiparous subjects were 3.0–23 (mean: 13, median: 14) and 2.7–20 (mean: 8.6, median: 8.5) pg TEQ g−1 lipid, respectively. The sums of the concentrations of 56 non-dioxin-like PCB congeners that were measured in the subjects’ blood and breast milk were 16–326 (mean: 107, median: 100) and 12–252 (mean: 73, median: 67) ng g−1 lipid, respectively. The partitioning ratios of individual congeners of PCDDs, PCDFs, dioxin-like PCBs, and non-dioxin-like PCBs from blood to breast milk in secundiparas were almost the same as those of primiparas that have been recently reported, suggesting that the partitioning ratios of these compounds from maternal blood to breast milk in women is little affected by delivery. Furthermore, the partition of PCB congeners with chlorine at the 2-, 3-, 4′-, and 5-positions or the 2-, 4-, 4′-, and 5-positions of the biphenyl ring from the blood to the breast milk tended to occur at a higher level than that of other congeners. In particular, the levels of tetraCB-74 and hexaCB-146 in the breast milk for both primiparous and secundiparous mothers were slightly higher than those in the blood.

The Role of Hydrology in the Polychlorinated Dibenzo--dioxin and Dibenzofuran Distributions in a Lowland River.

Persistent organic pollutants such as polychlorinated dibenzo--dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are environmental contaminants that have widespread distribution and pose a serious threat to aquatic ecosystems. We conducted a study to quantify the distribution, patterns, and transport of PCDDs and PCDFs along the Pilica River in central Poland under different hydrological conditions to estimate the loads of these compounds and understand their fate in aquatic systems. Water samples were collected at five sampling points along the river that represent a range of hydrological conditions including flooding and stable and low water flows. Reduced river water flow was associated with lower average total and toxic equivalent (TEQ) concentrations of PCDDs plus PCDFs: 33.6 pg L and 4.21 pg TEQ L for flooding; 28.3 pg L and 3.6 pg TEQ L for stable flow; 18.4 pg L and 1.0 pg TEQ L for low-water flow. Similar results were observed for daily loadings of total and TEQ concentrations: the highest values were observed during flooding (331.1-839.4 mg d and 27.8-110.7 mg TEQ d), medium under stable hydrological conditions (55.8-121.0 mg d and 7.7-15.3 mg TEQ d), and the lowest values during low water flow (30.9 and 40.3 mg d and 1.4-2.4 mg TEQ d). The results demonstrate that diffuse sources of pollution play a key role during periods of high water flow (i.e., flooding season), whereas point sources of pollution, including municipal and industrial wastewater treatment plant discharges, mainly determine the PCDD and PCDF concentrations seen during low water periods.

Effect of oxygen content on the thermal desorption of polychlorinated biphenyl-contaminated soil.

Oxygen plays an important role during the thermal treatment of soil, contaminated with polychlorinated biphenyls (PCBs), due to the potential oxidation of PCBs to form polychlorinated dibenzofurans (PCDFs). The effect of oxygen content (0, 5, 21 and 100%) in carrier gases on PCBs and PCDD/Fs was studied both in soil and gas after thermal desorption of PCBs contaminated soil at 500 °C. All 209 congeners of PCBs and 136 congeners of PCDD/Fs (P = 4 to 8) were analysed. Oxygen content showed little effect on PCB removal and destruction. Under different carrier gases, the removal efficiency and the destruction efficiency for PCBs attained 93.8-95.5 and 83.0-85.0 %, respectively. The levels of PCDD/Fs in soil and gas were correlated positively with oxygen content. Compared with PCDDs, PCDFs in soil were not effectively removed under oxidative conditions because there was chemistry going on and PCBs were being converted to PCDFs. The total concentration of PCDFs in soil and gas was 2.6, 11.3, 15.6 and 17.5 times of the initial PCDFs concentration (21.9 ng/g) in raw soil with increasing oxygen content. Thus, substantial amounts of PCDFs were generated in the presence of oxygen during the treatment of contaminated soil.

Polychlorinated naphthalene concentrations and profiles in cheese and butter, and comparisons with polychlorinated dibenzo-p-dioxin, polychlorinated dibenzofuran and polychlorinated biphenyl concentrations

Polychlorinated naphthalenes (PCNs) are candidates for inclusion in the Stockholm Convention on persistent organic pollutants. PCNs are structurally and toxicologically similar to 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) and its analogues. Intake in food is considered to be an important human exposure pathway for PCNs. In this preliminary study, cheese and butter samples were analysed for PCNs, polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) using an isotope dilution gas chromatography high-resolution mass spectrometry method. The aim of this study was to evaluate the PCN concentrations in the cheese and butter samples and to compare them with the PCDD, PCDF and PCB concentrations. The PCN concentrations were 5.6–103 pg g−1 of wet weight in the seven cheese samples tested and 5.0–199 pg g−1 of wet weight in the seven butter samples tested. The mass concentrations of lower chlorinated congeners were greater than those of the higher chlorinated congeners. Congeners of CN45/36, CN27/30 and CN33/34/37 were much more abundant than other congeners found in tetrachlorinated PCNs. Congeners of CN51, CN66/67 and CN73 were determined to be the predominant congeners in penta-, hexa- and heptachlorinated homologs, respectively. The PCNs contributed around 5% of the total PCN, PCDD, PCDF and PCB toxic equivalence (TEQ) values. CN73 was found to be the dominant PCN congener and contributed more than 40% to the PCN TEQ value. Congeners CN66/67, CN69 and CN63 were also found at relatively high levels. The PCB congener CB118 was the predominant congener (by mass-based concentration) of the 12 dioxin-like PCBs (dl-PCBs). The PCBs contributed 53.8% of the total TEQ, and congener CB126 contributed more than any other compound that was analysed to the total TEQ. The PCDDs and PCDFs contributed 11.6% and 29.7% of the total TEQ values, respectively.

Isomer pattern and elimination of dioxins in workers exposed at a municipal waste incineration plant.

The aim of this study was to clarify patterns of serum concentrations of dioxins in the employees of a waste incineration plant and to estimate elimination rates and half-lives of serum dioxin isomers, and the maximum serum concentrations of dioxin isomers at the time of plant shutdown. Sixteen subjects participating 3 times or more in annual health examinations during an 8-yr period from 2000 to 2007 were recruited for this study. Serum concentrations of dioxins expressed as TEQ/g lipid decreased gradually after plant shutdown with the highest decrease observed in polychlorinated dibenzofurans (PCDFs) followed by polychlorinated deibenzo-p-dioxins (PCDDs) and then coplanar PCBs. The serum toxic equivalency (TEQ) concentrations of PCDF and PCDD congeners in the employees were higher than those in the general population survey by the Ministry of the Environment, Japan, whereas the serum concentrations of coplanar PCBs were similar to those in the general population. The estimated half-lives and elimination rates of PCDDs and PCDFs in the highly exposed workers increased compared with the moderately exposed workers. The estimated geometric mean serum concentrations of PCDDs, PCDFs and total dioxins at the time of plant shutdown were 35, 53 and 107 pg TEQ/g lipid, respectively.

Unintentional formed PCDDs, PCDFs, and DL-PCBs as impurities in Chinese pentachloronitrobenzene products.

Pentachloronitrobenzene (PCNB) products have been reported to contain relatively high levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) as impurities. No data was available for Chinese PCNB products which are still produced and used in China. Therefore, we analysed Chinese PCNB products, including two raw pesticides and three formulations available on the market. In all samples, PCDDs, PCDFs, and dioxin-like polychlorinated biphenyls (DL-PCBs) were detected at levels exceeding Japanese regulation limits. The concentrations of PCDDs and PCDFs (0.16 to 0.93 ng TEQ g(-1)) were lower than the PCNB formulations measured from the Australian market (3.9 ng TEQ g(-1)). However, the Toxic Equivalent (TEQ) contribution from DL-PCBs (0.7 to 2.5 ng TEQ g(-1)) to total TEQ was higher compared to PCDDs and PCDFs. This discovery demonstrated that it is necessary to consider the DL-PCBs impurity in organochlorine pesticides and other organochlorine chemicals in particular chlorinated aromatic compounds for adequate risk assessment. In addition to DL-PCBs, other unintentionally POPs-hexachlorobenzene (HCB) (3.7 to 52 ng g(-1)) and pentachlorobenzene (PeCBz) (0.04 to 0.3 ng g(-1)) which are listed in the Stockholm Convention-were detected in the PCNB samples. The PCNB production steps were assessed for their unintentional POPs formation potential. Thermolysis of the aromatic compounds using iron chloride (FeCl3) as catalyst is suggested as relevant production step for (DL-)PCBs formation. Since the levels in the formulated PCNB recalculated to active ingredient were higher compared to the raw pesticide, the formulation process (e.g., milling) may also have had an influence on additional PCDD/Fs and PCBs formation.

PCDD and PCDF concentrations in a traffic tunnel environment

In an effort to understand the fundamental aspects of air quality in traffic tunnel environments, field campaigns were conducted to measure polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and other important pollutants within two traffic tunnels in Nam San (NS) and Hong Ji (HJ) in Korea in 2009 and 2010. The mean concentrations of ∑PCDD/Fs (in fg/m3) at the two tunnel sites were 1270 (±880) and 1200 (±810), respectively. These values were moderately lower than those measured at a non-tunnel urban background site (1350 (±780) fg/m3) — selected as a reference in this study. In addition, seasonal patterns of dioxin concentrations were clearly evident at the traffic tunnels like the urban reference site, showing higher levels during the winter (and spring) than the summer (and fall). The observed seasonal variations were driven by changes in the concentrations of ∑PCDF congeners, while ∑PCDD concentrations showed little seasonality. The results of our study suggest that there is no significant difference in source characteristics between the two investigated tunnel sites and urban location, although the role of gasoline and diesel fueled vehicles are considered as the major source in determining the PCDDs and PCDF levels in a tunnel environment. However, given the relative increase in other important ambient pollutant (e.g. PM10) concentrations over ∑PCDD/Fs in tunnel air (compared to urban background air), the balance of sources in tunnels is clearly different from those in urban air overall.

Detailed analysis of PCBs and PCDD/Fs impurities in a dielectric oil sample (ASKAREL Nr 1740) from an imported transformer in China

Homolog and congener profiles of polychlori- nated biphenyls (PCBs), polychlorinated dibenzo-p- dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in commercial PCBs formulations are useful information for the source appointment of PCBs contam- ination as well as the risk assessment caused by potential exposure. Dielectric oil (ASKAREL Nr 1740) in an imported transformer found in China was sampled and analyzed by isotope dilution technology using high resolution gas chromatography-high resolution mass spectrometry (HRGC/HRMS). The detailed homolog and congener profiles of PCBs obtained were compared with those of known Aroclor formulations. High similarity in the homolog profile between the oil sample and Aroclor 1260 was found, with the hexachlorinated and hepta- chlorinated biphenyls accounting for more than 80.2% of the total PCBs concentration. Severn indicator PCBs contribute about 30%, while 12 PCB congeners (i.e., #153, #143, #168, #180, #149, #165, #138, #170, #190, #187, #174, #181) account for more than 50% of the total PCB concentrations. Total concentration of PCDDs, PCDFs and dioxin-like PCBs (DL-PCBs) was found to be 740 ng TEQ/g, of which 620 ng TEQ/g came from DL-PCBs. The contribution of PCDDs to the total TEQ was neglectable. The concentration of PCDFs homologs follows the order of OCDF>HxCDFs>HpCDFs>PeCDFs>TeCDFs, which is in consistence with the previous study on Aroclor 1260. Three DL-PCBs congeners (i.e., #118, #156, #157) accounted for 77% of the total concentration of DL-PCBs, also they contribute 72% in the TEQ caused by DL-PCBs.

EPA's National Dioxin Air Monitoring Network (NDAMN): Design, implementation, and final results

The U.S. Environmental Protection Agency (U.S. EPA) established the National Dioxin Air Monitoring Network (NDAMN) in June of 1998, and operated it until November of 2004. The objective of NDAMN was to determine background air concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs). NDAMN started with 10 sampling sites, adding more over time until the final count of 34 sites was reached by the beginning of 2003. Samples were taken quarterly, and the final sample count was 685. All samples were measured for 17 PCDD/PCDF congeners, 8 PCDD/PCDF homologue groups, and 7 dl-PCBs (note: 5 additional dl-PCBs were added for samples starting in the summer of 2002; 317 samples had measurements of 12 dl-PCBs). The overall average total toxic equivalent (TEQ) concentration in the United States was 11.2 fg TEQ m−3 with dl-PCBs contributing 0.8 fg TEQ m−3 (7%) to this total. The archetype dioxin and furan background air congener profile was seen in the survey averages and in most individual samples. This archetype profile is characterized by low and similar concentrations for tetra – through hexa PCDD/PCDF congeners, with elevations in four congeners – a hepta dioxin and furan congener, and both octa congeners. Sites were generally categorized as urban (4 sites), rural (23 sites), or remote (7 sites). The average TEQ concentrations over all sites and samples within these categories were: urban = 15.9 fg TEQ m−3, rural = 13.9 fg TEQ m−3, and remote = 1.2 fg TEQ m−3. Rural sites showed elevations during the fall or winter months when compared to the spring or summer months, and the same might be said for urban sites, but the remote sites appear to show little variation over time. The four highest individual moment measurements were 847, 292, 241, and 132 fg TEQ m−3. For the 847 and 292 fg TEQ m−3 samples, the concentrations of all congeners were elevated over their site averages, but for the 241 and 132 fg TEQ m−3 measurements, only the PCDD congeners were elevated while PCDF and dl-PCB concentrations were similar to the site averages.

Annual and seasonal variations in atmospheric PCDDs/PCDFs and dioxin-like PCBs levels in satellite cities of Seoul, Korea during 2003–2009

Long-term measurements of atmospheric polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) were conducted in six satellite cities of Seoul, the capital of South Korea, from January 2003 to December 2009. Of the six sites, three were located in residential areas (Suwon, Anyang, and Seongnam) and the other three were in industrial areas (Ansan, Bucheon, and Siheung). For the 7 years, the average concentrations of PCDDs/PCDFs and dl-PCBs were higher at industrial sites than those at residential sites, and their lowest and highest concentrations were 0.113 ± 0.073 pg international toxicity equivalency quantity (I-TEQ) m−3 and 0.0071 ± 0.0040 pg World Health Organization (WHO)-TEQ m−3 at Seongnam and 0.625 ± 0.597 pg I-TEQ m−3 and 0.0376 ± 0.0285 pg WHO-TEQ m−3 at Ansan, respectively. The annual averages of these compounds tended to decrease from 2003 to 2009, with the most apparent change in 2006 when the regulation of dioxin emission standard was reinforced for flue gas from incineration facilities. Complying with the reinforced standard, the concentrations of PCDFs were reduced more effectively than those of PCDDs, leading to increase in ratios of PCDDs to PCDFs since 2006. Additionally, a seasonal tendency was observed for PCDDs/PCDFs with higher concentrations in winter than summer, which was opposite for dl-PCBs. This seasonal difference suggests their sources such as combustion processes and volatilization and the influence of synoptic-scale circulation. The congener profiles indicated that 1,2,3,4,6,7,8-HpCDF, OCDF, OCDD, and 1,2,3,4,6,7,8-HpCDD were the most abundant, comprising 65.0% of the 17 toxic 2,3,7,8-substituted PCDDs/PCDFs mass. The three congeners of 2,3′,4,4′,5-PeCB, 2,3,3′,4,4′-PeCB, and 3,3′,4,4′-TeCB comprised 75.9% of the 12 dl-PCBs.

Dioxin congener patterns in commercial catfish from the United States and the indication of mineral clays as the potential source

Since 1991 the US Department of Agriculture (USDA) has conducted annual surveys of pesticide residues in foods under the Agricultural Marketing Service's Pesticide Data Program (PDP). To assess chemical residues in domestically marketed catfish products, 1479 catfish samples were collected during the 2008–2010 PDPs. A subset of 202 samples was analysed for 17 toxic polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). The average pattern of the individual PCDD/F congener concentrations in the catfish was rather unique in that it had almost no measurable amounts of polychlorinated dibenzofurans (PCDFs), but all PCDDs were present. This pattern was more dominant in the domestically produced catfish products than in the imported products (China/Taiwan). Comparison of the pattern to known sources of PCDD/Fs showed strong similarities to the pattern of PCDD/Fs found in kaolin clays which have often been used as anti-caking agents in animal feeds. To investigate whether catfish feeds may be the source of the PCDD/Fs found in the catfish, archived catfish feed data from a US Food and Drug Administration (USFDA) database were examined. In 61 out of 112 feed samples, the PCDD concentrations were 50 times higher than the PCDF concentrations and resembled the pattern found in the catfish products and in clays mined in the south-eastern United States. Although the source of PCDD/Fs in domestically marketed catfish products cannot be definitively established, mined clay products used in feeds should be considered a likely source and, given the wide concentration range of PCDD/Fs that has been found in clays, a critical control point for PCDD/Fs entrance to the food supply.

Characterization of placental transfer of polychlorinated dibenzo‐p‐dioxins, dibenzofurans and polychlorinated biphenyls in normal pregnancy

Prenatal exposure to dioxins may result in many adverse health effects. However, the mechanisms by which dioxins are transferred from mother to fetus through the placenta are not well understood. The aim of this study was to investigate the differences in dioxin concentrations between maternal blood, the placenta, and cord blood in normal pregnant women, and to identify which individual congeners of these compounds are transferred from mother to fetus through the placenta. Samples were collected from 19 pregnant Japanese women. Specific congeners of seven polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), and four non-ortho polychlorinated biphenyls (PCBs) were analyzed. The TEQ concentrations of PCDDs, PCDFs, and non-ortho PCBs were 8.03, 3.39, and 3.95 pg TEQ/g lipid, respectively, in the maternal blood; 8.78, 3.61, and 0.87 pg TEQ/g lipid in the placenta; and 4.33, 1.25, 1.08 pg TEQ/g lipid in the cord blood. Among specific congeners, 1,2,3,7,8-PentaCDD and 2,3,4,7,8-PentaCDF exhibited a placenta to maternal blood ratio greater than 1.0, while OctaCDD exhibited the greatest cord blood to placenta ratio. The cord blood to maternal blood ratio of total PCDDs was significantly higher than that of total PCDFs and total non-ortho PCBs. The dioxin concentration in cord blood was approximately half of the amount in maternal blood, despite congeners showing a high toxic equivalency factor accumulating in the placenta. PCDDs were transferred more readily than PCDFs and non-ortho PCBs from maternal blood to the fetus through the placenta.

Dietary‐ and tissue‐based exposure of belted kingfisher to PCDFs and PCDDs in the Tittabawassee River floodplain, Midland, MI, USA

Concentrations of polychlorinated dibenzofurans (PCDFs) and other dioxin-like compounds in soils and sediments of the Tittabawassee River and associated floodplains downstream of Midland, Michigan, USA, are greater than upstream sites. As a result of these concentrations, which are some of the greatest ever reported, a site-specific exposure assessment of belted kingfisher breeding in the assessment area was conducted. To reduce the uncertainty associated with predicting exposure from abiotic matrices, concentrations of residues were quantified in site-specific prey items and in eggs and nestlings of belted kingfisher. Dietary exposure, expressed as the potential average daily dose, based on site-specific concentrations of PCDFs, polychlorinated dibenzo-p-dioxins (PCDDs), and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ(WHO-Avian)) in prey items was consistently greater along the Tittabawassee River than in associated reference areas and further downstream sites in the Saginaw River. Concentrations of PCDD/DFs in eggs and nestlings of belted kingfisher varied among sampling areas, being greater in both eggs and nestlings nesting along the Tittabawassee River compared to those of belted kingfisher from upstream reference areas. Geometric mean concentrations of PCDD/DFs were 130 and 200 ng/kg wet weight in eggs and nestlings of belted kingfisher, respectively. These concentrations are the equivalent of 84 and 95 ng TEQ(WHO-Avian)/kg. Site-specific biomagnification factors for select PCDD/DF congeners ranged from <1.0 to 1.8 in belted kingfisher.