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Archives of Environmental Contamination and Toxicology (v.50, #2)
Organochlorine Insecticides in Mudflats of Hong Kong, China by H. L. Wong; J. P. Giesy; P. K. S. Lam (pp. 153-165).
Organochlorine (OC) insecticides were measured in different environmental compartments (including seawater, sediment, and biota) at six sites within the Mai Po Marshes Nature Reserve (MPMNR) and at one site in A Chau (AC) in Hong Kong in June 2002 (wet season) and January 2003 (dry season). MPMNR is a Wetland of International Importance (Ramsar site) situated in the western part of Hong Kong, whereas AC is a relatively remote island in Starling Inlet on the eastern side of the New Territories of Hong Kong. Generally, concentrations of OC insecticides in water, sediment, and biota were greater at MPMNR than at AC. Hexachlorobenzene, dichloro-diphenyl-trichloroethane, and hexachlorocyclohexanes were detected in all samples collected from MPMNR. Preliminary risk assessments were performed by comparing the measured concentrations of OCs in different environmental compartments with the corresponding guidelines promulgated by various environmental protection authorities. Concentrations of some OCs in sediments from certain locations in MPMNR were consistently greater than their corresponding sediment guideline values. These results suggest that the sediment OC concentrations in the sediments of MPMNR might pose a risk to aquatic organisms. Despite this, concentrations of OCs in biota samples were much lower than the relevant guideline values promulgated by government agencies to protect the health of human consumers. It is postulated that the management practices adopted at MPMNR have been effective in limiting the bioaccumulation window (duration) for OCs. This situation may have been aided by a frequent exchange of water between the tidal shrimp ponds at MPMNR and the open sea, again attributable to management practices. The low-cost maintenance practices adopted at MPMNR may potentially be applicable to wetlands in other southeastern Asian countries, thus allowing sustainable fishery production and wildlife conservation.
Spatial Distribution of Polychlorinated Biphenyls in Coastal Marine Sediments Receiving Industrial Effluents in Kuwait by Bondi Gevao; Mirza U Beg; Ali Al-Omair; Murad Helaleh; Jamal Zafar (pp. 166-174).
The concentrations of polychlorinated biphenyls (PCBs) were measured in surficial sediments receiving industrial and municipal effluents in Kuwait. The ΣPCB concentrations varied by two orders of magnitude ranging from 0.4 to 84 μg kg−1 dw. The homologue distribution in the study favored the more chlorinated congeners and generally followed the order: penta-PCBs > hexa-PCBs > tetra-PCBs ≈ hepta-PCBs, with the dominant congeners being 138, 101, 110, 180, 153, 132, 149, and 118. The spatial distribution revealed significant intersite difference in concentration, with high levels encountered close to a harbor and several wastewater outlets suggesting that point source input is the primary delivery mechanism of PCBs to the sediment. This study suggests that atmospheric deposition of PCBs may not be a significant delivery mechanism to sediments in Kuwait possibly due to low annual precipitation and high annual temperatures that are experienced in the Arabian Gulf. The implication of this observation is that PCBs in air are likely to remain in the gas phase long enough to be subject to long-range atmospheric transport to other regions.
Effects of the Herbicides Roundup and Avans on Euglena gracilis by Madonna Pettersson; Nils G. A. Ekelund (pp. 175-181).
Glyphosate is the active ingredient in a range of widely used herbicides. The aim of this work is to evaluate the effects of two commercial herbicides, Roundup and Avans, on the motility, velocity, and gravitactic orientation of the aquatic flagellate Euglena gracilis. An early warning system, called ECOTOX, has been used for monitoring the different parameters of movement. The motility was not affected by Roundup and Avans after short period tests (0, 30, and 60 s). However, gravitactic orientation of the cells was affected at concentrations of 1.25 g l−1 and above when treated with Avans, whereas treatments with Roundup showed no specific changes after short period tests. Velocity of the cells was affected by both herbicides, but the effects of Avans were shown to occur at lower concentrations in comparison to Roundup. Avans showed lower no observable effect concentration (NOEC) values in comparison to Roundup for the different parameters after short period tests. After long period (7 days) tests, NOEC values were similar except for the upward swimming, where Avans had a NOEC value of 100 μg l−1 and Roundup 200 μg l−1. The results demonstrate that Avans containing trimethylsulfonium salt of glyphosate is more toxic to E. gracilis than Roundup, which contained isopropylamine salt of glyphosate.
Toxicity Assessment of Two Soils from Jales Mine (Portugal) Using Plants: Growth and Biochemical Parameters by Susana Loureiro; Conceição Santos; Glória Pinto; Armando Costa; Marta Monteiro; António J. A. Nogueira; Amadeu M. V. M. Soares (pp. 182-190).
Contaminants in soils can enter food chains through primary producers. Bioavailable contaminants can induce growth, and reproductive or biochemical changes in plants. To evaluate the bioavailability of heavy metals in two soils from Jales mine surroundings, bioassays with the plants Brassica rapa (RCBr) and Avena sativa were performed. Biochemical parameters (protein and malondialdehyde [MDA] content, and catalase and peroxidase activities) were also measured. The soils had different heavy metal contents: JNC soil contained low heavy metal concentrations, whereas JC soil had high heavy metal contents. Results stressed the difference between species sensitivity, with A. sativa showing no toxicity effects when exposed to both soils. On the other hand, B. rapa presented a decrease in growth parameters when exposed to JNC soil and no changes when exposed to JC soil. A Life Cycle Bioassay confirmed this trend for B. rapa exposed to JNC soil, but also evidenced that JC soil was affecting B. rapa in terms of flower and seed pod production. Biochemical assays showed that plants affected by heavy metals also displayed oxidative stress, with an increase in MDA production, reduction of protein content, and reduction of catalase and peroxidase activities. All bioassays revealed that JNC soil, although with a lower heavy metal content, had a higher bioavailable fraction when compared to JC soil, which consequently increased its toxicity to plants.
Remediation of Soil Contaminated with 2,4-Dichlorophenol by Treatment of Minced Shepherd’s Purse Roots by Jong-Woo Park; Bo-Kyung Park; Jang-Eok Kim (pp. 191-195).
This study investigated the applicability of minced shepherd’s purse root containing high peroxidase activity as a catalytic agent instead of purified and immobilized peroxidase for the remediation of soil contaminated with phenolic pollutants, using 2,4-dichlorophenol (2,4-DCP) as a model pollutant. The removal of 2,4-DCP in the soil was extremely fast when treated with peroxide and minced shepherd’s purse root, and maximal removal was achieved within 10 min. Increasing the reaction temperature did not significantly influence removal of 2,4-DCP incubated with shepherd’s purse. The removal of 2,4-DCP was dependent on the amount of shepherd’s purse and the soil moisture content. Increasing the amount of shepherd’s purse and moisture mixed with soil caused an increased removal of 2,4-DCP. Calcium peroxide was more effective than hydrogen peroxide, and maximal removal was achieved in 20 mM of both peroxides. The efficiency of 2,4-DCP removal decreased with increasing 2,4-DCP concentration but was greater than 60% at 500 to 1000 mg kg-1. Our results provide strong evidence that shepherd’s purse can be used to remediate soil contaminated with phenolic pollutants.
Toxicity Identification Evaluation of Five Metals Performed with Two Organisms (Daphnia magna and Lactuca sativa) by B. Fjällborg; B. Li; E. Nilsson; G. Dave (pp. 196-204).
When trying to identify the main toxicants in effluents, natural waters, sediments, soil leachates, and leachates from products, the Toxicity Identification Evaluation (TIE) procedure has proven useful. To enhance the use of this procedure for soil, sewage, and sediment samples, we wanted to evaluate this TIE procedure, regarding metal toxicity, for the 96-h root elongation test performed with Lactuca sativa (lettuce) seeds. We also wanted to evaluate the effect of TIE treatment on the toxicity of Mn and Fe to Daphnia magna. Bioassays were performed with Daphnia magna (48-h immobility) and lettuce seeds (96-h root elongation) to determine the effect concentrations for both organisms of Ag, Cu, Fe, Mn, and Zn. The TIE was then performed at the determined Daphnia 48-h EC84 and Lactuca 96-h EC50 for each metal. Our results showed that the order of the metal toxicity was Ag>Cu>Zn>Fe>Mn, for Daphnia and Ag = Zn = Fe = Cu > Mn for lettuce seeds. We also found that toxicity of the metals for Daphnia magna was reduced according to the prevailing knowledge regarding Cu, Zn, and Ag. However, the toxicity of Ag and Cu for Daphnia was also reduced by filtration through a C18 resin. Toxicity of Mn and Fe was reduced by filtration through a CM resin and increase of pH. For lettuce seeds, toxicity of the metals was reduced by the same treatments as for Daphnia magna with the exception of EDTA addition, which did not affect Cu toxicity to lettuce seeds. No effects were found for filtration through a C18 resin. We suggest that the TIE procedure using lettuce seeds can be used in toxicity identification of metals. However, the effects of pH manipulations were often stronger with lettuce and should be interpreted with care.
Variation in, and Causes of, Toxicity of Cigarette Butts to a Cladoceran and Microtox by T. Micevska; M. St. J. Warne; F. Pablo; R. Patra (pp. 205-212).
Cigarette butts are the most numerically frequent form of litter in the world. In Australia alone, 24–32 billion cigarette butts are littered annually. Despite this littering, few studies have been undertaken to explore the toxicity of cigarette butts in aquatic ecosystems. The acute toxicity of 19 filtered cigarette types to Ceriodaphnia cf. dubia (48-hr EC50 (immobilization)) and Vibrio fischeri (30-min EC50 (bioluminescence)) was determined using leachates from artificially smoked cigarette butts. There was a 2.9- and 8-fold difference in toxicity between the least and most toxic cigarette butts to C. cf. dubia and V. fischeri, respectively. Overall, C. cf. dubia was more inherently sensitive than V. fischeri by a factor of approximately 15.4, and the interspecies relationship between C. cf. dubia and V. fischeri was poor (R2 = 0.07). This poor relationship indicates that toxicity data for cigarette butts for one species could not predict or model the toxicity of cigarette butts to the other species. However, the order of the toxicity of leachates can be predicted. It was determined that organic compounds caused the majority of toxicity in the cigarette butt leachates. Of the 14 organic compounds identified, nicotine and ethylphenol were suspected to be the main causative toxicants. There was a strong relationship between toxicity and tar content and between toxicity and nicotine content for two of the three brands of cigarettes (R2 > 0.70) for C. cf. dubia and one brand for V. fischeri. However, when the cigarettes were pooled, the relationship was weak (R2 < 0.40) for both test species. Brand affected the toxicity to both species but more so for V. fischeri.
Predicting the Toxicity of Substituted Phenols to Aquatic Species and Its Changes in the Stream and Effluent Waters by Yong G. Lee; Seok H. Hwang; Sang D. Kim (pp. 213-219).
The changes in the acute toxicity of 16 phenols toward Selenastrum capricornutum and Daphnia magna were examined as a function of their physical/chemical properties. The results demonstrated that phenols with a higher octanol-water partition coefficient (Kow) had a higher toxicity toward aquatic organisms. The toxicity of phenols was closely related to the log Kow values, with correlation coefficients of 0.93 (except for the nitrophenols) and 0.89 for S. capricornutum and D. magna, respectively. The changes in the phenols toxicities in the site waters (i.e., stream and effluent waters) were investigated by calculating the water effect ratios (WER) from the results of the toxicity tests in the site waters using D. magna. The results showed that the degree of ionization for each phenolic compound was altered by the differences in the dissociation constant (pKa), and the change in the toxicity could be predicted. Therefore, the WER should be considered when the toxicity of phenolic compounds is estimated in site waters. The quantitative structure-activity relationships (QSAR) study showed that the toxicity of the phenols to D. magna could be predicted by the hydrophobicity (log Kow) alone and by combining the log Kow with pKa, while the toxicity to S. capricornutum was predicted by a combination of hydrophobicity (log Kow) and ELUMO (or pKa).
Ecological Effects of Spring and Late Summer Applications of Lambda-Cyhalothrin on Freshwater Microcosms by R. P. A. Van Wijngaarden; T. C. M. Brock; P. J. van den Brink; R. Gylstra; S. J. Maund (pp. 220-239).
The aim of the study was to compare the effects of the pyrethroid insecticide lambda-cyhalothrin (treated at 10, 25, 50, 100, 250 ng active ingredient a.i./L) on a drainage ditch ecosystem in spring and late summer. Microcosms (water volume approximately 430 L) were established using enclosures in a 50-cm–deep experimental ditch system containing communities typical of macrophyte-dominated freshwater ecosystems. Effects on macroinvertebrates, zooplankton, phytoplankton, macrophytes, and community metabolism were assessed and evaluated using univariate and multivariate statistical techniques. The macroinvertebrate community responded most clearly to treatment and, as anticipated, insects and crustaceans were among the most sensitive organisms. Statistical analysis showed that the underlying community structure was significantly different between the spring and summer experiments. However, the most sensitive species (Chaoborus obscuripes and Gammarus pulex) were abundant in spring as well as in late summer. In spring and late summer, only slight and transient effects were observed at the community level in the 10-ng/L treatment. Overall, the study did not show substantial differences in the responses of sensitive taxa between spring and late summer treatments, and effects thresholds were similar irrespective of season of treatment.
Alkaline Digestion and Solid Phase Extraction Method for Perfluorinated Compounds in Mussels and Oysters from South China and Japan by M. K. So; S. Taniyasu; P. K. S. Lam; G. J. Zheng; J. P. Giesy; N. Yamashita (pp. 240-248).
Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS), have been identified in the coastal waters of China and Japan. An alkaline digestion method, coupled with solid-phase extraction (SPE), and high-performance liquid chromatography interfaced with high-resolution electrospray tandem mass spectrometry was developed to determine PFCs in mussel and oyster samples from coastal waters of south China and Japan. These techniques produced adequate recoveries and reporting limits with small quantities of PFCs. Concentrations of individual PFCs in mussels and oysters from south China and Japan ranged from 113.6 to 586.0 pg/g, wet weight (ww) for PFOS, 63.1 to 511.6 pg/g, ww for perfluorohexane sulfonate, 9.3 to 30.1 pg/g, ww for perfluorobutane sulfonate and 37.8 to 2957.0 pg/g, ww for perfluorooctane sulfonamide. The quantification of perfluorinated carboxylates was compromised by interferences from carboxylates in the procedural blanks. Perfluoroundecanoate and perfluorononanoate had relatively great blank interferences, which resulted in relatively poor limits of quantification for these compounds. Some PFCs were only identified in a limited number of samples: perfluorododecanoate in samples from Tokyo Bay, Japan (195.9 pg/g, ww); and perfluorodecanoate in Fuzhou, China (131.7 pg/g, ww) and Tokyo Bay (118.6 pg/g, ww). The greatest concentrations of perfluorooctanoate, perfluoroheptanoate, and perfluorohexanoate were observed in samples from Tokyo Bay and Bei Hai, south China.
Seasonal Variations of Selected Biomarkers in Sand Gobies Pomatoschistus minutus from the Guadalquivir Estuary, Southwest Spain by M. Solé; J. Kopecka; L. M. García de la Parra (pp. 249-255).
Sand gobies, Pomatoschistus minutus, were collected monthly from September 2002 to August 2003 at a station situated 8 km upstream from the mouth of the Guadalquivir estuary (southwest Spain). Physical parameters of the water and selected biomarkers of organic pollution were recorded in the fish to discuss its potential as a sentinel species in estuaries. The biomarkers selected were the activities of catalase (CAT), 7-ethoxyresorufin-O-deethylase (EROD), and glutathione S-transferase (GST) in the liver and acethylcholinesterase (AChE) and lipid peroxidation (LP) in the head. The results showed an increase in total protein synthesis in late spring and early summer coinciding with the reproductive period as well as the release of fresh water from a dam situated 110 km upstream. During the same period, a significant depletion of hepatic GST and head AChE but higher LP levels in this tissue suggest exposure to pesticides such as those applied to crops established along the course of the river and reaching the estuary mostly when the freshwater discharges occur. Changes in CAT and EROD activities fluctuated randomly and were not noted as seasonally dependent. Biomarker fluctuations in sand goby are discussed as normal seasonal variations, but other variables—such as potential local pollution inputs—cannot be disregarded.
Survival of Lost River Suckers (Deltistes luxatus) Challenged with Flavobacterium columnare During Exposure to Sublethal Ammonia Concentrations at pH 9.5 by Jeffrey M. Morris; Elaine Snyder-Conn; J. Scott Foott; Richard A. Holt; Michael J. Suedkamp; Hilary M. Lease; Susan J. Clearwater; Joseph S. Meyer (pp. 256-263).
The Lost River sucker (Deltistes luxatus) is a federally listed, endangered species inhabiting the hypereutrophic waters of Upper Klamath Lake in southern Oregon, USA. High pH (≥10) and elevated ammonia concentrations (≥1 mg NH3-N/L) often occur during blooms of cyanobacteria (Aphanizomenon flos-aquae) in the lake, with major fish kills sometimes following a mid- or late-summer “crash” of the cyanobacterial population. Previous histopathology analyses and bacterial sampling indicated that infections of the pathogenic bacterium Flavobacterium columnare might contribute to the fish kills. We hypothesized that prior exposure to adverse water quality conditions increases the susceptibility of Lost River suckers to F. columnare infections. To test this, we exposed juvenile Lost River suckers to four sublethal ammonia concentrations at pH 9.4 for 62 d. On day 31, fish in half of the aquaria were exposed to F. columnare. As expected, survival of the Lost River suckers decreased in aquaria inoculated with F. columnare. Ninety-four percent of the fish that died were infected by F. columnare in the gills, kidney, or skin, whereas none of the survivors or unexposed control fish was infected. However, contrary to our hypothesis, survival of the fish exposed to F. columnare increased significantly (p < 0.05) as unionized ammonia concentrations increased. Our results suggest that complex interactions can complicate prediction of the responses of fish to concurrent chemical stressors and bacterial pathogens.
Factors Affecting the Toxicity of Methylmercury Injected into Eggs by G. H. Heinz; D. J. Hoffman; S. L. Kondrad; C. A. Erwin (pp. 264-279).
We developed a standardized protocol for comparing the sensitivities of the embryos of different bird species to methylmercury when methylmercury was injected into their eggs. During the course of developing this protocol, we investigated the effects of various factors on the toxicity of the injected methylmercury. Most of our experiments were done with chicken (Gallus domesticus), mallard (Anas platyrhynchos), and ring-necked pheasant (Phasianus colchicus) eggs, all of which were purchased in large numbers from game farms. A smaller amount of work was done with double-crested cormorant (Phalacrocorax auritus) eggs collected from the wild. Several solvents were tested, and corn oil at a rate of 1 μl/g egg contents was selected for the final standardized protocol because it had minimal toxicity to embryos and because methylmercury dissolved in corn oil yielded a dose–response curve in a range of egg concentrations that was similar to the range that causes reproductive impairment when the mother deposits methylmercury into her own eggs. The embryonic stage at which eggs were injected with corn oil altered mercury toxicity; at early stages, the corn oil itself was toxic. Therefore, in the final protocol we standardized the time of injection to occur when each species reached the morphologic equivalent of a 3-day-old chicken embryo. Although solvents can be injected directly into the albumen of an egg, high embryo mortality can occur in the solvent controls because of the formation of air bubbles in the albumen. Our final protocol used corn oil injections into the air cell, which are easier and safer than albumen injections. Most of the methylmercury, when dissolved in corn oil, injected into the air cell passes through the inner shell membrane and into the egg albumen. Most commercial incubators incubate eggs in trays with the air cell end of the egg pointing upward, but we discovered that mercury-induced mortality was too great when eggs were held in this orientation. In addition, some species of bird eggs require incubation on their sides with the eggs being rolled 180° for them to develop normally. Therefore, we adopted a procedure of incubating the eggs of all species on their sides and rolling them 180° every hour. Little has been published about the conditions of temperature, humidity, and the movements to which eggs of wild birds need to be subjected for them to hatch optimally under artificial incubation. Not unexpectedly, hatching success in an artificial incubator is generally less than what natural incubation by the parents can achieve. However, the survival of control embryos of most wild bird species was good (generally ≥ 80%) up to within 1 or 2 days of hatching when we incubated the eggs at 37.5°C (or 37.6°C for gallinaceous species) at a relative humidity that resulted in an approximate 15% to 16% loss in egg weight by the end of incubation and by incubating the eggs on their sides and rolling them 180°/h. To improve statistical comparisons, we used survival through 90% of incubation as our measurement to compare survival of controls with survival of eggs injected with graded concentrations of mercury.
Effect of Various Copper Supplements to Feed of Laying Hens on Cu Content in Eggs, Liver, Excreta, Soil, and Herbage by M Skřivan; V Skřivanová; M Marounek (pp. 280-283).
Copper is often added to poultry diets as an antimicrobial agent at doses greatly exceeding the nutritional requirement. In this study, the basal diet of laying hens containing 9.2 mg Cu/kg was supplemented with CuSO4ċ5H2O at 0, 25, 65, 115, and 240 mg Cu/kg dry matter (DM). At Cu dietary concentration just below the level permitted by the European Union (35 mg/kg), the Cu content in the egg yolk was significantly (p < 0.05) increased by 26%, and nonsignificantly by 4.1, 9.1, and 7.9% in the egg white, eggshell, and liver, respectively. When Cu concentration in the diet was doubled, the effect of Cu on Cu content in eggshell and liver was statistically significant as well. In no liver sample was the hygienic limit of Cu content (80 mg/kg) exceeded. Supplementation of diets with Cu increased Cu concentration in excreta linearly from 25.3 to 396.8 mg/kg DM. Dried excreta were used for fertilization of grassland at 21 g N/m2. Three months later, soil and herbage were sampled and analyzed. The Cu concentration in soil increased from 25.3 to only 46.4 mg/kg DM when dietary Cu concentration rose from 9.2 to 243.7 mg Cu/kg DM. Corresponding Cu concentrations in herbage were 6.8 and 19.2 mg/kg DM. It can be concluded that the deposition of Cu in eggs and liver of hens fed Cu-supplemented diets does not represent a hygienic risk. The accumulation of Cu in soil fertilized with excreta of Cu-fed hens and in herbage was limited.
Mercury and Selenium in Livers of Waterfowl Harvested in Northern Canada by Birgit M. Braune; Brian J. Malone (pp. 284-289).
Total mercury and selenium were measured in livers of green-winged teal, northern pintails, buffleheads, king eiders, Barrow’s and common goldeneyes, surf and white-winged scoters collected from 12 sites across northern Canada between 1988 and 1994. Hepatic mercury concentrations were <1.0 mgċkg−1 ww in 80% of the birds analyzed. Mercury levels did not vary much among species, with green-winged teal, northern pintails, and white-winged scoters, in particular, generally having quite low levels (<0.5 mgċkg−1 ww). Northern pintails had the lowest Se concentrations (<2.5 mgċkg−1 ww) overall whereas the higher Se concentrations (10–20 mgċkg−1 ww) were found in the king eiders and scoters. Selenium showed a much greater variation in concentrations, particularly in the king eiders and scoters. Hepatic mercury concentrations found in the waterfowl analyzed in this study were an order of magnitude lower than toxicological threshold levels found in the literature. However, hepatic selenium concentrations in 33% of the females exceeded 3.0 mgċkg−1 ww and some king eiders as well as some surf and white-winged scoters contained hepatic selenium concentrations >10 mgċkg−1 ww suggesting levels of potential concern.
Occurrence of Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers in Belgian Human Adipose Tissue Samples by C. Naert; M. Piette; N. Bruneel; C. Van Peteghem (pp. 290-296).
Levels of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were measured in 53 human adipose tissue samples. The samples consisted of adipose tissue from 31 men and 22 women having a mean age of 53 years. No information about diet or occupational exposure was collected. Cleanup was performed using a glass column containing acidified silica, deactivated alumina, and anhydrous sodium sulphate. Subsequently, samples were analyzed by high-resolution gas chromatography/tandem mass spectrometry. PBDE concentrations (sum of BDEs 28, 47, 99, 100, 154, 153, and 183) ranged between 1.23 and 57.2 ng g−1 lipid weight and were comparable with levels in samples from other European countries. The sum of seven International Council for the Exploration of the Sea (ICES) indicator PCB congeners (PCBs 28, 52, 101, 118, 138, 153, and 180) ranged from 126 to 2090 ng g−1 lipid weight. No age dependency was found for PBDEs (Pearson correlation −0.023, p = 0.873), whereas PCBs showed higher correlation coefficients with age (Pearson correlation 0.613, p < 0.0005). There was no relationship between PBDE and PCB levels (Pearson correlation −0.010, p = 0.943).