Congener Patterns Research Articles

Brominated flame retardants and perfluorinated compounds in indoor dust from homes and offices in Flanders, Belgium

The increasing time spent indoors combined with the abundant usage of diverse indoor chemicals led to concerns involving the impact of these compounds on human health. The current study focused on two groups of important indoor contaminants i.e. Brominated flame retardants (BFRs) and Perfluorinated compounds (PFCs). Concentrations of both compound classes have been measured in Flemish indoor dust samples from homes and offices. ΣPolybrominated diphenyl ethers (PBDEs) (BDE 47, 99, 100, 154, 153, 197, 196 and 203) and BDE 209 in homes ranged between 4–1214 ng g −1 dw (median 35) and <5–5295 ng g −1 dw (median 313), respectively. Hexabromocyclododecane (ΣHBCD) levels ranged from 5 to 42 692 ng g −1 dw (median 130), with α-HBCD being the major isomer (mean 59%). In addition, tetrabromobisphenol A (TBBPA) ranged between <3 and 419 ng g −1 dw (median 12). For all BFRs, median levels in office dust were up to an order of magnitude higher than in home dust. ΣPFCs (sum of perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonic acid (PFOS), perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA)) concentrations in homes ranged from 0.2 to 336 ng g −1 (median 3.0 ng g −1). Levels in office dust were higher ( p < 0.01) than in house dust with ΣPFCs ranging between 2.2 and 647 ng g −1 (median 10 ng g −1) and median (PFOA) and perfluorooctane sulfonate values of 2.9 and 2.2 ng g −1, respectively. The congener pattern was dominated by PFOA, followed by PFOS. Calculated human exposure was below the reference dose values set by the US-EPA for BDE 209, HBCD and below the provisional tolerable daily intakes proposed by European Food Safety Authority for PFOS and PFOA.

Occurrence of PCBs in raw and finished drinking water at seven public water systems along the Hudson River

Polychlorinated biphenyls (PCBs) were measured in raw and finished drinking water at seven Public Water Systems (PWSs) along the Hudson River as part of a baseline monitoring program prior to the extensive sediment dredging of the Upper Hudson River. Water samples were either analyzed using an Aroclor method (based on USEPA Method 508) or a congener method (Modified Green Bay Mass Balance Method). Using the congener-based method, raw water concentrations ranged from <9.3 to 164.3 ng/L and finished water concentrations ranged from <9.3 to 186.6 ng/L. Using the Aroclor method, finished water concentrations ranged from <5.0 to 200.9 ng/L. Most finished water samples above 73.0 ng/L were from a PWS with wells drilled near the river. Excluding the well data, total PCB concentrations in raw water at systems in the Upper River were similar to concentrations at systems in the Lower River, though the congener patterns differed. Paired comparison of total PCB concentrations using the two analytical methods showed good agreement, although raw water showed a different relationship than finished water.

Elevated PCDD/F Levels and Distinctive PCDD/F Congener Profiles in Free Range Eggs

Chicken eggs are one of the most important foods in the human diet all over the world, and the demand for eggs from free range hens has steadily increased. Congener-specific analyses of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were performed on 6 free range and 12 caged chicken egg samples collected in Taiwan. The mean level of PCDD/Fs in the free range egg samples was 5.7 (1.79/0.314) times higher than those in the caged egg samples. Principle component analysis revealed that at least three characteristic patterns of PCDD/F congener were observed among the 18 egg samples. The different PCDD/F congener patterns between free range and caged egg samples may reflect distinctive exposure scenarios among the free range and caged hens. We suggest that the differences of PCDD/F levels and congener patterns between free range and caged egg samples give rise to the issues related to the safety of eating free range chicken eggs. The present data may provide useful information for further investigation of the possible PCDD/F sources in the contaminated free range eggs.

Levels, fluxes and time trends of persistent organic pollutants in Lake Thun, Switzerland: Combining trace analysis and multimedia modeling

Levels, mass fluxes, and time trends of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in Lake Thun, a peri-Alpine lake, are investigated. We present measurements of PBDEs and PCBs in air, lake water, lake sediment, and tributary water. These measurements are combined with a multimedia fate model, based on site-specific environmental parameters from the lake catchment. Measured loadings of PBDEs and PCBs in air and tributaries were used to drive the model. The model satisfactorily reproduces PBDE and PCB congener patterns in water and sediment, but it tends to yield concentrations in water below the measurements and concentrations in sediment exceeding the measurements. A sensitivity analysis reveals that partitioning of PBDEs and PCBs between the aqueous dissolved phase and suspended particulate matter in the water column strongly affects the model results, in particular the concentrations in water and sediment. For lower-brominated PBDEs, approximately 70% and 30% of input into the lake stems from atmospheric deposition and from tributaries, respectively. For heavier PBDEs and all PCBs, rivers appear to deliver the major load (64–92%). Waste water effluents are of minor importance. 50–90% of the total input is buried in the permanent sediment. Sediment burial makes PBDEs and PCBs less available for recycling in the environment, and reduces concentrations in the outflowing river. If use of deca-BDE increases in the future, levels in Lake Thun will follow the same trend. If the use and resulting environmental emissions decrease, concentrations in water will rapidly decline, according to our calculations, while sediment levels will decrease at a considerably slower rate.

Comparison of PCB congener profiles in the embryos and principal prey of a breeding colony of black-crowned night-herons

We compared polychlorinated biphenyl (PCB) congener profiles of embryos of black-crowned night-herons ( Nycticorax nycticorax) nesting in an urban-industrialized area of Chicago, Illinois, USA, with those of regurgitated food boluses from nestlings and their primary prey. Consistent with previous studies of piscivorous birds, the PCB burden of embryos was shifted towards more heavily chlorinated congeners (those with 6, 7, and 8 chlorines), when compared to prey. The PCB congener profiles for measured and homolog concentrations in alewife ( Alosa pseudoharengus) collected from Lake Michigan at the Chicago, Illinois, waterfront, closely resembled that of regurgitated food boluses collected from nestlings at the Lake Calumet colony. Also, alewife from Illinois and regurgitates were not clearly differentiated by the discriminant analyses for measured, proportional, and homolog concentrations. Congener profiles in alewife from the highly contaminated Indiana Ship Canal, which had a much higher PCB burden (geometric average = 1061.7 ng/g ww [95% CI = 648.6−1061.7 ng/g ww]) than did alewife from Illinois (158.1 [135.8−184.5] ng/g ww) and regurgitates (212.3 [177.0−254.7] ng/g ww), reflected a less-chlorinated mixture (i.e., Aroclor 1242). These results are consistent with our observations, which indicated that many of the adults of this colony were foraging along the Chicago waterfront, where alewife had lower PCB burdens. Because the congener patterns of the prey differ, the PCB congener profiles can be used to elucidate foraging patterns of colonial piscivorous birds and determine relative risks to exposed populations.

Indoor and outdoor air PBDE levels in a Southwestern US city

Levels of polybrominated diphenyl ether (PBDE) flame retardants have been increasing in humans and the environment for the past few decades. Human levels are markedly higher in the US than Europe. Although food appears to be a significant route of intake, food PBDE levels are not substantially higher in the US than Europe. House and office dust appear to be major routes of exposure with air believed to usually provide a lesser route of intake. Because there are very few measurements of airborne PBDE that have been performed in relevant microenvironments in the US, increased efforts to assess airborne PBDE in the US as sources of exposure are needed. This study reports, for the first time from a Southwestern US city in Texas, the results of measurements of airborne PBDE in multiple locations, two outdoor and six indoor (residential and office) from active air sampling with collection of a combination of both vapor- and particulate-phase PBDE. Higher PBDE levels were measured in indoor than outdoor air, which confirms previous findings. Of 11 measured congeners including BDE 209, total PBDE levels in two outdoor air samples were 112 and 125 pg m−3 and the indoor air levels ranged from 175 to 1232 pg m−3 with a median of 572 pg m−3. These findings suggest that sources of air contamination with PBDE may be similar in Texas as elsewhere in North America. However, more sampling is required to (1) better determine if this is the case and (2) attempt to characterize potential sources of PBDE contamination in both indoor and outdoor air by analysis of congener patterns.

Biogeochemical Controls on PCB Deposition in Hudson Bay

PCB concentrations, congener patterns, and fluxes were examined in 13 dated and organically characterized (C, N, delta(13)C, delta(15)N) marine sediment cores from Hudson Bay, Canada, to investigate the importance of organic matter (OM) supply and transport to PCB sequestration. Drawdown of PCBs, supported by marine primary production, is reflected in elevated summation operatorPCB concentrations and more highly chlorinated PCB signatures in surface sediments underlying eutrophic regions. Sediments in oligotrophic regions, which are dominated by "old" marine OM, have lower PCB concentrations and weathered signatures. For the surface of Hudson Bay, average atmospheric deposition appears to be very low (ca. 1.4 pg summation operatorPCBs cm(-2) a(-1)) compared to fluxes reported for nearby lakes (ca. 44 pg summation operatorPCBs cm(-2) a(-1)). (210)Pb fails to provide a means to normalize the fluxes, highlighting important differences in the biocycling of (210)Pb and PCBs. Unlike (210)Pb, atmospheric PCB exchange with the water's surface is partially forced by the aquatic organic carbon cycle. The extremely low atmospheric deposition of PCBs to the surface of Hudson Bay is likely a reflection of the Bay's exceptionally low productivity and vertical carbon fluxes. If future marine production and vertical flux of carbon increase due to loss of ice cover or change in river input as consequences of global warming, PCB deposition would also increase.

Dioxin, Dioxin–Like PCBs and Indicator PCBs in Some Medicinal Plants Irrigated with Wastewater in Ismailia, Egypt

Wastewater is often leaden with various contaminants that may accumulate in soils and can under some conditions enter the agricultural food chain. Concentrations of PCDD/Fs, DL-PCBs and NDL-PCBs have been determined using GC/HRMS in three of the commonly used medicinal plant (henna, rosemary, and moghat) grown on raw wastewater. In the case of henna and rosemary plants, all wastewater irrigated samples showed higher content of the studied contaminants than freshwater irrigated samples, while moghat samples, whether irrigated with freshwater or wastewater, had more or less the same content of the studied contaminants. Concentrations in plant samples ranged between 0.00004 and 0.865 pg WHO TEQ/g wet w for PCDDs, and between 0.03 and 1.86 pg WHO TEQ/g wet w for the PCDFs. Levels of PCB TEQ ranged from 0.005 to 0.76 pg/g wet w. In descending order, rosemary, henna, and moghat had the highest concentrations of total TEQ (PCDD/Fs + DL-PCBs). The congeners pattern in henna and rosemary samples was generally characterized by the dominance of PCDFs with a significant contribution from the lower (mono- to tri-) PCDFs. In moghat samples the profile was dominated by PCDDs, with OCDD contributing 100% to PCDDs. PCBs contribution to the total TEQ was on average 25%, 7% and 2% in rosemary, moghat and henna respectively. For NDL-PCBs, the sum concentration of 17 PCBs congeners increased from 2.65 to 4.13 ng/kg wet w in henna, and from 4.64 to 7.16 ng/ kg wet w in rosemary due to the irrigation with wastewater. Congener PCB 28 was the main contributor (60%) to sum 6 indicators in all samples, followed by PCB 52 (18%) and PCB 101 (6%).

Distribution and fate of polybrominated diphenyl ethers in indoor environments of elementary schools

Polybrominated diphenyl ethers (PBDEs) are considered harmful to human health because of their toxicities and persistence in environments. In the current study, the distribution and fate of PBDEs in classrooms and computer rooms in 17 elementary schools in South Korea have been described. Eight congeners (brominated diphenyl ether-28, -47, -99, -100, -153, -154, -183, and -209) in air, floor dust, and product surface dust were measured. While Sigma(8)PBDEs in the air in classrooms showed considerable variations (0.659-1600 pg/m(3), arithmetic mean +/- s.d.: 377 +/- 441 pg/m(3)), those in computer rooms were somewhat similar (134-220 pg/m(3), arithmetic mean +/- s.d.: 169 +/- 40 pg/m(3)). Sigma(8)PBDEs in floor dust varied over a wide range, from 453 to 45,700 ng/g, for all rooms. Based on congener patterns, two groups were created--CL-1 that is dominated by high-brominated congeners and CL-2 primarily comprising low-brominated congeners--for both air and floor dust of classrooms. Surface dust had low concentrations, ranged from ND to 181, from ND to 128, and from ND to 256 pg/cm(2) for desk/chair sets, lockers, and playing tools, respectively. Pearson correlation coefficients were calculated individually for air, floor dust, and surface dust. The results indicate that both surface dust and floor dust may act as a secondary source of PBDEs in indoor environments after emission from facilities. Children have been estimated to have a higher potential exposure to PBDEs than adults. Since children spend most of their day time at school, PBDE distributions in school environments should be a matter of great concern.

Occurrence and levels of polybrominated diphenyl ethers (PBDEs) in recent sediments and marine organisms from Xiamen offshore areas, China

Surface sediments and porewater from 12 sites within Xiamen offshore areas and organisms from a heavily contaminated site Yuandang Lagoon were sampled and analyzed for eight polybrominated diphenyl ethers (PBDEs) congeners (-28, -47, -99, -100, -153, -154, -183 and -209). The total concentrations of eight PBDEs (∑8PBDEs) and BDE-209 in sediments ranged from 0.27 to 76.54ng/g with an average of 16.31ng/g and from 0.10 to 70.11ng/g with an average of 14.94ng/g, respectively. Concentrations of ∑8PBDEs in porewater ranged from 2.5 to 34.1ng/L, with a mean value of 15.3ng/L. In this study, the partition coefficients (log Koc′) of PBDE congeners (without -209) were significantly correlated with their octanol–water partition coefficients (log KOW) (r2=0.74, P<0.01). ∑8PBDE concentrations ranged from 0.33 to 1.26ng/g (lipid weight) in marine organisms, and PBDE congener patterns were significantly different between fish and clam, crab.

Atmospheric PCB congeners across Chicago

We have measured PCBs in 184 air samples collected at 37 sites in the city of Chicago using an innovative system of high-volume air samplers mounted on two health clinic vans. Here we describe results of sampling conducted from November 2006 to November 2007. The samples were analyzed for all 209 PCB congeners using a gas chromatograph with tandem mass spectrometry (GC–MS/MS). The ΣPCBs (sum of 169 peaks) in Chicago ranged from 75 pg m −3 to 5500 pg m −3 and primarily varied as a function of temperature. The congener patterns are surprisingly similar throughout the city even though the temperature-corrected concentrations vary by more than an order of magnitude. The average profile resembles a mixture of Aroclor 1242 and Aroclor 1254, and includes many congeners that have been identified as being aryl hydrocarbon receptor (AhR) agonists (dioxin-like) and/or neurotoxins. The toxic equivalence (TEQ) and neurotoxic equivalence (NEQ) in air were calculated and investigated for their spatial distribution throughout the urban-industrial complex of Chicago. The NEQ concentrations are linearly correlated with ΣPCBs while the TEQ concentrations are not predictable. The findings of this study suggest that airborne PCBs in Chicago are widely present and elevated in residential communities; there are multiple sources rather than one or a few locations of very high emissions; the emission includes congeners associated with dioxin-like or neurotoxic effects and congeners associated with unidentified sources.

Levels and congener patterns of polychlorinated biphenyls (PCBs) in rural soils of Beijing, China

This study aimed to investigate the levels and congener distribution of PCBs in rural soils of Beijing. The results indicated that the levels of PCBs in Beijing rural soils were relatively high in comparison with their concentrations in other rural areas, but lower than those in many urban areas. The congener profiles were predominated by lowly chlorinated congeners such as Di-CBs, Tri-CBs and Tetra-CBs, which was similar to those in other areas such as Dalian and Hong Kong. The concentrations of PCB congeners weakly correlated with the physicochemical properties of the rural soils, suggesting the little effect of soil properties on concentrations of PCBs.

Survey of Polychlorinated Dibenzo-p-dioxins, Polychlorinated Dibenzofurans, and Non-ortho-polychlorinated Biphenyls in U.S. Meat and Poultry, 2007−2008: Effect of New Toxic Equivalency Factors on Toxic Equivalency Levels, Patterns, and Temporal Trends

A statistically based survey of dioxins and dioxin-like compounds in domestic meat and poultry was conducted by the U.S. Department of Agriculture (USDA) from September 2007 to September 2008. Seventeen toxic polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and four non-ortho-polychlorinated biphenyls (no-PCBs) were measured in 510 beef (steer/heifer), market hog, young turkey, and young chicken samples. The results of the survey showed the sum of PCDD/F and no-PCB toxic equivalencies (sum-TEQs) ranging from not detected to 4.5 pg/g of lipid. Mean sum-TEQ levels for beef, turkey, chicken, and pork were 0.66, 0.61, 0.17, and 0.16 pg/g of lipid, respectively. To compare the new survey data with data from previous USDA surveys in the mid-1990s and 2002-2003, TEQs from all data sets were calculated using the most recent 2005 toxic equivalency factors (TEFs). The results of the recalculation on the older survey data was a small increase (4-13%) in mean TEQs for the mid-1990s data, which initially used pre-1994 TEFs, and a small decrease (2-4%) for the 2002-2003 data, which initially used 1998 TEFs. A comparison of the three surveys indicates declining TEQ trends in all slaughter classes over the 10 year period; however, the congener patterns remain relatively constant between 2002 and 2008, indicating similar animal exposures to dioxins and dioxin-like compounds during these time periods. Several samples from the 2008 survey with the highest TEQ values are undergoing follow-up investigations to determine possible sources that may be contributing to these levels.

PCDD/F, PBDD/F, and PBDE Emissions from Open Burning of a Residential Waste Dump

This work reports on the first known field study determining emission factors for polychlorinated and polybrominated dibenzodioxins/dibenzofurans (P[C/B]DDs/Fs) and polybrominated diphenyl ethers (PBDEs) from open burning of domestic waste. Two burning waste dump sites in Mexico were sampled using high-volume samplers mounted to a mobile sampling boom. Concurrent measurements of CO and CO(2) allowed determination of emission factors via the carbon balance method. PCDD/F emission factors averaged 823 ng toxic equivalency (TEQ)/kg C(burned) (N = 8, 68% relative standard deviation, RSD), a value at least five times higher than those from previous tests with domestic waste burned in barrels and approximately 2000 times higher than those from stacks of modern municipal waste combustors. These emission factors appear to be related to combustion quality, as conditions conducive to smoldering combustion, rather than flaming combustion, resulted in higher emission factors. Emissions of 40 PBDE congeners, likely originating from brominated flame retardants, averaged 724 mug/kg C(burned) (RSD = 96%) and had congener patterns similar to those of reported atmospheric sampling. Emissions of PBDDs/Fs were similar in magnitude to their chlorinated counterparts, averaging 470 ng TEQ/kg C(burned) (RSD = 105%), and may originate as reaction products of PBDE combustion or as thermally desorbed impurities from the PBDE flame retardant.

Kaolinic clay derived PCDD/Fs in the feed chain from a sorting process for potatoes

At the end of 2004, during a routine monitoring project, high levels of PCDDs in milk from two farms were found. Using a bioassay and the congener patterns obtained by HRGC/HRMS, the source was traced back to the use of kaolinic clay for sorting potatoes in a production process of French fries. Rest products, especially peelings after scrubbing, were used as feed for dairy cows. Levels of PCCD/Fs in this product amounted to 44 ng WHO 1998-TEQ kg −1 (88% dw). The maximum level observed in milk was 20 pg WHO 1998-TEQ g −1 fat. A Physiologically Based PharmacoKinetic (PB-PK) model was used to model three data obtained before eliminating the source in order to estimate the starting time of the contamination of the cows, the steady-state level after prolonged contamination and the kinetics of the decrease in the levels after removal of the source. Samples of milk were continuously collected for several months showing a decrease to levels below the product limit of 3 pg WHO 1998-TEQ g −1 fat within 2 months, in excellent agreement with the decrease predicted by the PB-PK model. Different batches of clay were sampled and analysed, showing varying levels of especially PCDDs. All clays were confirmed to be kaolinic clay using X-ray analysis. Other by-products used for animal feed were also contaminated and led to precautionary measures at a few hundred farms, especially pig farms. However, levels in other animal derived products like pig meat did not exceed the product limits.

Polychlorinated biphenyls, dioxins, furans, and organochlorine pesticides in spotted sandpiper eggs from the upper Hudson River basin, New York

In 2004, spotted sandpipers (Actitis macularia) were studied on the Hudson River near Fort Edward south to New Baltimore, NY and on two river drainages that flow into the Hudson River. Concentrations of 28 organochlorine pesticides, 160 polychlorinated biphenyl (PCB) congeners, and 17 dioxin and furan (PCDD-F) congeners were quantified in eggs collected on and off the Hudson River. The pattern of organochlorine pesticides and PCDD-F congeners did not differ significantly between eggs collected on and off the Hudson River. In contrast, the pattern of PCB congeners differed significantly between the Hudson River and other rivers. Total PCBs were significantly greater in eggs from the Hudson River (geometric mean = 9.1 microg PCBs/g wet weight) than from the other two rivers (0.6 and 0.6 microg PCBs/g wet weight). Seven of 35 (20%) eggs exceeded 20 microg PCBs/g wet weight, the estimated threshold for reduced hatching in tree swallows (Tachycineta bicolor) and some raptor species; the maximum concentration was 72.3 microg PCBs/g wet weight. Models that predicted nest survival and egg success (the proportion of eggs hatching in a clutch if at least one egg hatched) as functions of contaminant levels were poorly distinguished from models that presumed no such associations. While small sample size could have contributed to the inability to distinguish among contaminant and no toxicant models, we cannot rule out the possibility that contaminant concentrations on the Hudson River were not sufficiently high to demonstrate a relationship between contaminant concentrations and reproductive success.

Polychlorinated biphenyls, dioxins, furans, and organochlorine pesticides in belted kingfisher eggs from the upper Hudson River basin, New York, USA

Nesting belted kingfishers (hereafter kingfishers, Ceryle alcyon) were studied on the Hudson River near Fort Edward south to New Baltimore (NY, USA) and three nearby river drainages in 2004. Concentrations of 28 organochlorine pesticides, 160 polychlorinated biphenyl (PCB) congeners, and 17 dioxin and furan (PCDD-F) congeners were quantified in kingfisher eggs. The pattern of organochlorine pesticides and PCDD-F congeners did not differ significantly between 14 eggs collected from individual nests on the Hudson River and five eggs similarly collected on three other nearby rivers. In contrast, the pattern of PCB congeners in eggs collected on the Hudson River differed significantly from the other rivers. The differences in patterns of PCB congeners were associated with a higher representation of lower-numbered congeners on the Hudson River than the other rivers. The higher prevalence of the lower-numbered congeners and lower prevalence of the higher-numbered congeners is consistent with Aroclor 1016 and 1242 being the source of the PCBs on the Hudson River. Concentrations in a sample egg collected at each nest were compared to nest survival and egg success (the proportion of eggs hatching in a clutch if at least one egg hatched) of the remaining eggs in the clutch. Models that predicted nest survival and egg success as functions of contaminant levels were poorly distinguished from models that presumed no such associations. Small sample sizes could have contributed to the inability to distinguish among contaminant and no toxicant models. However, we cannot rule out the possibility that contaminant concentrations on the Hudson River were not sufficiently high to demonstrate a relationship between contaminant concentrations and reproductive success in kingfishers.

Congener fingerprints of tetra- through octa-chlorinated dibenzo- p-dioxins and dibenzofurans in Baltic surface sediments and their relations to potential sources

Comprehensive congener fingerprints of polychlorinated dibenzo- p-dioxins and dibenzofurans (PCDD/Fs), including non-2,3,7,8-substituted congeners, in 142 surface sediment samples from the Baltic Sea were characterized by Principal Component Analysis (PCA). The pattern analysis revealed source specific indicators of chlorophenol use, high temperature processes, chlorine bleach/chloralkali production and a source signature suggested to originate from pulp/paper or related production. Congener patterns in sediments from offshore and pristine coastal areas showed strong resemblance to patterns of atmospheric deposition and flue gases, indicating that these sources have high impact in areas that are not affected by point sources. Prominent contributors to the patterns of hotspot areas along the Swedish coast included chlorophenol indicators and a source characterized by hexa-CDDs while the contribution of the traditional chlorine bleach pattern was weaker. This study demonstrates the importance of comprehensive PCDD/F congener analysis for identifying links to candidate sources.

Hierarchical cluster analysis of polychlorinated dioxins and furans in Michigan, USA, soils: Evaluation of industrial and background congener profiles

As part of the University of Michigan Dioxin Exposure Study, soil samples were collected from 766 residential properties near the Tittabawassee River between Midland and Saginaw; near the Dow Chemical Facility in Midland; and, for comparison, in the other areas of Midland and Saginaw Counties and in Jackson and Calhoun Counties, all located in the state of Michigan, USA. A total of 2,081 soil samples were analyzed for 17 polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). In order to better understand the distribution and sources of the PCDD/F congeners in the study area, hierarchical cluster analysis (HCA) was used to statistically group samples with similar congener patterns. The analysis yielded a total of 13 clusters, including: 3 clusters among the soils impacted by contamination present in the Tittabawassee River sediments, a cluster comprised mainly of samples collected within the depositional area of the Dow incinerator complex, a small cluster of samples with elevated 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TCDD), and several clusters exhibiting background patterns. The clusters related to the Tittabawassee River floodplain contamination all contained elevated PCDF levels and were differentiated from one another primarily by their relative concentrations of higher-chlorinated PCDDs, a difference likely related to both extent and timing of impacts from Tittabawassee sediments. The background clusters appear to be related to combustion processes and are differentiated, in part, by their relative fractions of TCDD. Thus, HCA was useful for identifying congener profile characteristics in both contaminated and background soil samples.

Patterns and concentration levels of polybrominated diphenyl ethers (PBDEs) in placental tissue of women in Denmark

The levels and congener patterns of PBDEs were investigated in human placental samples in Denmark. The median concentrations of ∑PBDE tri-hepta and BDE-209 in the 50 samples were 1.22 and 1.14 ng g −1 lw, respectively, with the total sum ranging from 0.51 to 17.1 ng g −1 lw, which is similar to previous placental studies. The PBDE content in placental tissue was dominated by BDE-209, which accounted for approximately 50% of the total amount of PBDEs. BDE-47, -99, and -153 were detected in all samples. Approximately equal amounts of BDE-47 and BDE-153 were observed in the placental tissue, which is in agreement with previous European studies of human serum. Principal Component Analysis (PCA) was performed to analyze congener patterns within and between mothers. The loading plot showed groupings of the measured PBDE variables in three groups, representative of Penta-, Octa- and Deca-BDE technical mixtures. Congeners representing the individual technical mixtures were close to orthogonal or inversely correlated, indicating variation in the congener patterns of internal exposure corresponding to the patterns of technical mixtures used in products. Visualisation of the participant objects according to body mass index (BMI), revealed inherent congener patterns (19% X-variance) showing increased frequency for participants within the highest BMI group to have elevated concentrations of BDE-209 in the placental tissue.