Identification and occurrence of analogues of dechlorane 604 in Lake Ontario sediment and their accumulation in fish.

The dechlorane family of flame retardants, which includes Mirex (also known as Dechlorane), Dechlorane Plus (DP), and Dechloranes (Dec) 602, 603, and 604, were manufactured at a facility along the Niagara River, upstream of Lake Ontario. Some of these compounds remain in use. In a previous study, we found Mirex and Dec602 to have greater bioaccumulation potentials than Dec604 and DP based on calculated biota-sediment accumulation factors (BSAFs). In this study, analogues of Dec604, containing fewer bromines and mixed substitutions of bromine and chlorine, were identified in Lake Ontario sediment and fish using high and ultrahigh resolution mass spectrometric techniques. The tribromo-Dec604 (Br3Dec604) analogue, known as Dechlorane 604 Component B (Dec604 CB), was present in lake trout and whitefish at concentrations of 10-60 ng/g lipid weight, approximately 50-200 times greater than concentrations measured for Dec604. In addition, BrDec604 and Br2Dec604 analogues, and mixed Br2Cl2Dec604, Br3ClDec604, Br2ClDec604, and BrCl2Dec604 analogues were also present. We have shown that solutions of Dec604 and Dec604 CB exposed to UV-light undergo photodebromination and give rise to the analogues found in sediment and fish. Dec604 CB and other lesser halogenated analogues of Dec604 show greater bioaccumulation potentials than Dec604, Dec602 and DP, based on BSAFs, which highlight the need to consider likely impurities and degradation products in the assessment of persistent, bioaccumulative, and toxic compounds.

A pilot study for foetal exposure to multiple persistent organic pollutants and the development of infant atopic dermatitis in modern Japanese society.

Increasing evidence supports that harmful chemicals accumulating in the human body may pose a significant threat to infant health through foetal exposure. Persistent organic pollutants (POPs) are thought to enhance the risk for later development of allergic disease like atopic dermatitis (AD). However, few studies have evaluated the effect of foetal exposure to various POPs on the development of AD in early infancy. Here, we describe the impact of foetal exposure to a number of POPs on the occurrence of AD in 7-month-old infants. The participants were 81 infants with or without AD who participated in a birth cohort study, where the concentrations of 15 polychlorinated biphenyl (PCBs) congeners, dichlorodiphenyltrichloroethane (p,p'-DDT), dichlorodiphenyldichloroethylene (p,p'-DDE), ß-hexachlorocyclohexane (ß-HCH), hexachlorobenzene (HCB), cis-nonachlor, trans-nonachlor, mirex, oxychlordane, and 27 polybrominated diphenyl ether (PBDEs) congeners were measured in the umbilical cord tissues collected immediately after birth. At 7 months, 27 of the 81 infants (33.8%) were diagnosed with AD. Of all POPs examined, total concentrations of 27 PBDE congeners were associated with a significantly decreased incidence of AD. Notably, the concentration of 27 PBDEs was significantly lower in AD infants than in non-AD infants (P<0.01), and the risk of AD development decreased with increasing PBDE levels. These results suggest that foetal exposure to PBDEs is a possible contributing factor to reducing AD in early infancy.

Organochlorine concentrations (PCBs, DDTs, HCHs, HCB and MIREX) in delphinids stranded at the northeastern Brazil.

Organochlorine compounds are highly persistent in the environment, causing bioaccumulation and biomagnification through the marine food chain. To verify the bioaccumulation pattern of DDT and its metabolites, as well as PCBs, Mirex, HCHs and HCB, samples of subcutaneous adipose tissue from 25 Guiana dolphins (Sotalia guianensis), two Fraser's dolphins (Lagenodelphis hosei), two spinner dolphins (Stenella longirostris), one spotted dolphin (Stenella frontalis), and one striped dolphin (Stenella coeruleoalba) were analyzed. The collected specimens were found stranded in northeastern Brazil between 2005 and 2011. The concentrations were reported in µg·g(-1) lip, varying from 0.02 to 17.3 for ΣPCB, from 0.003 to 5.19 for ΣDDT, from 0.005 to 0.16 for ΣHCH, from 0.002 to 0.16 for HCB, and from 0.02 to 2.38 for Mirex. The PCBs dominated the bioaccumulation pattern for both the Guiana and spinner dolphins; for the other species, DDT was the major compound. A discriminant function analysis revealed the differences in the organochlorine accumulation patterns between the Guiana dolphin (S. guianensis) and the continental shelf/oceanic dolphins (S. frontalis and S. longirostris). The results also show that the concentrations of organochlorine compounds found in the delphinids in northeastern Brazil were lower than the delphinids found in other regions of Brazil, as well as other locations worldwide with intense agroindustrial development and/or a larger population.

Persistent organic pollutants in ringed seals from the Russian Arctic.

Organochlorine compounds total DDT (ΣDDT), total HCH isomers (ΣHCH), toxaphenes (sum of Parlar 26, 50, 62), mirex, endrin, methoxychlor, total chlorinated benzenes (ΣCBz), total chlordane compounds (ΣCHL), polychlorinated biphenyls (total of 56 congeners; ΣPCBs), polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and polybrominated diphenyl ethers (sum of 7 tri- to hepta congeners; ΣPBDEs) were analysed in the blubber of adult ringed seals from the four areas of the Russian Arctic (White Sea, Barents Sea, Kara Sea and Chukchi Sea) collected in 2001-2005. Ringed seals from the south-western part of the Kara Sea (Dikson Island - Yenisei estuary) were the most contaminated with ΣDDTs, ΣPCBs, ΣCHL, and mirex as compared with those found in the other three areas of Russian Arctic, while the highest mean concentrations of ΣHCHs and PCDD/Fs were found in the blubber of ringed seals from the Chukchi Sea and the White Sea, respectively. Among all organochlorine compounds measured in ringed seals from the European part of the Russian Arctic, concentrations of ΣDDT and ΣPCBs only were higher as compared with the other Arctic regions. Levels of all other organochlorine compounds were similar or lower than in seals from Svalbard, Alaska, the Canadian Arctic and Greenland. ΣPBDEs were found in all ringed seal samples analysed. There were no significant differences between ΣPBDE concentrations found in the blubber of ringed seals from the three studied areas of the European part of the Russian Arctic, while PBDE contamination level in ringed seals from the Chukchi Sea was 30-50 times lower. ΣPBDE levels in the blubber of seals from the European part of the Russian Arctic are slightly higher than in ringed seals from the Canadian Arctic, Alaska, and western Greenland but lower compared to ringed seals from Svalbard and eastern Greenland.

Differences between Arctic and Atlantic fjord systems on bioaccumulation of persistent organic pollutants in zooplankton from Svalbard.

Differences in bioaccumulation of persistent organic pollutants (POPs) between fjords characterized by different water masses were investigated by comparing POP concentrations, patterns and bioaccumulation factors (BAFs) in seven species of zooplankton from Liefdefjorden (Arctic water mass) and Kongsfjorden (Atlantic water mass), Svalbard, Norway. No difference in concentrations and patterns of POPs was observed in seawater and POM; however higher concentrations and BAFs for certain POPs were found in species of zooplankton from Kongsfjorden. The same species were sampled in both fjords and the differences in concentrations of POPs and BAFs were most likely due to fjord specific characteristics, such as ice cover and timing of snow/glacier melt. These confounding factors make it difficult to conclude on water mass (Arctic vs. Atlantic) specific differences and further to extrapolate these results to possible climate change effects on accumulation of POPs in zooplankton. The present study suggests that zooplankton do biomagnify POPs, which is important for understanding contaminant uptake and flux in zooplankton, though consciousness regarding the method of evaluation is important.

Bottlenose dolphins as indicators of persistent organic pollutants in the western North Atlantic Ocean and northern Gulf of Mexico.

Persistent organic pollutants (POPs) including legacy POPs (PCBs, chlordanes, mirex, DDTs, HCB, and dieldrin) and polybrominated diphenyl ether (PBDE) flame retardants were determined in 300 blubber biopsy samples from coastal and near shore/estuarine male bottlenose dolphins (Tursiops truncatus) sampled along the U.S. East and Gulf of Mexico coasts and Bermuda. Samples were from 14 locations including urban and rural estuaries and near a Superfund site (Brunswick, Georgia) contaminated with the PCB formulation Aroclor 1268. All classes of legacy POPs in estuarine stocks varied significantly (p < 0.05) among sampling locations. POP profiles in blubber varied by location with the most characteristic profile observed in bottlenose dolphins sampled near the Brunswick and Sapelo estuaries along the Georgia coast which differed significantly (p < 0.001) from other sites. Here and in Sapelo, PCB congeners from Aroclor 1268 dominated indicating widespread food web contamination by this PCB mixture. PCB 153, which is associated with non-Aroclor 1268 PCB formulations, correlated significantly to human population indicating contamination from a general urban PCB source. Factors influencing regional differences of other POPs were less clear and warrant further study. This work puts into geographical context POP contamination in dolphins to help prioritize efforts examining health effects from POP exposure in bottlenose dolphins.

Concentration and bioaccumulation of dechlorane compounds in coastal environment of northern China.

Dechloranes, including Dechlorane Plus (DP), Mirex (Dechlorane), Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), and Dechlorane 604 (Dec 604), were determined using GC-MSD for water, sediment and oyster samples collected at 15 sampling sites near the Bohai and Huanghai Sea shore area of northern China in 2008. DP and Mirex were detected in most water, sediment, and oyster samples, which indicated widespread distribution of these two compounds. The mean concentrations in water, sediment and oyster samples, respectively, were 1.8 ng/L, 2.9 ng/g dry weight (dw) and 4.1 ng/g wet weight (ww) for total DP, and 0.29 ng/L, 0.90 ng/g dw, and 2.0 ng/g ww for Mirex. Dec 602 and Dec 603 were not detected in water but in small portions of the sediment and oyster samples, showing a low level of contamination by these two chemicals in the region. Strong and significant correlations were found between total DP and Mirex concentrations in water, sediment and oyster samples, probably suggesting similar local sources of these two chemicals. Dec 604 was not found in any samples. The biota-sediment accumulation factor (BSAF) of DP, Mirex, and Dec 602 declined along with the increase of their logarithm of octanol-water partition coefficients (log Kow), possibly indicating that compounds with lower log Kow (like Mirex and Dec 602) accumulated more readily in biota. The mean fractional abundance of syn-DP (fsyn) was 0.34 in water samples, a value lower than that in Chinese commercial mixture (0.41), while the mean fsyn for surface sediment (0.44) and oyster (0.45) samples were higher than technical values. Enrichment of syn-DP in oyster was in agreement with previously reported findings in Great Lakes fish. Enrichment of syn-DP in marine surface sediments, however, is contrary to data reported for fresh water sediments. To our knowledge this is the first report of Dec 602, Dec 603, and Dec 604 in a marine environment and also the first report of Dechloranes in marine biota.

Polychlorinated biphenyls and organochlorine pesticides in local waterbird eggs from Hong Kong: risk assessment to local waterbirds.

The contamination status of the marine environment in Hong Kong was studied by measuring concentrations of organochlorine (OC) pollutants (i.e., hexachlorobenzene, aldrin, dieldrin, endrin, mirex, total heptachlor, total chlordane, total DDTs, total PCBs, and total toxaphenes) in the eggs of selected waterbird species from different locations around the city: Little Egret (Egretta garzetta) and Chinese Pond Heron (Ardeola bacchus) from Mai Po Village, Great Egret (Ardea alba) and Black-crowned Night Heron (Nycticorax nycticorax) from A Chau, and Chinese Pond Heron (A. bacchus) from Ho Sheung Heung. The mean concentrations of total PCBs and total DDTs ranged from 191-11,100 ng g(-1) lipid and 453-49,000 ng g(-1) lipid, respectively. Recent exposure of waterbirds to technical chlordane was found in Hong Kong. The risk characterization demonstrated potential risks to birds associated with exposure to DDE, which was found to cause a reduction in survival of young in Hong Kong Ardeids based on the endpoint in the risk assessment.

Dechlorane plus and related compounds in peregrine falcon (Falco peregrinus) eggs from Canada and Spain.

Concentrations of Mirex, Dechlorane (Dec) Plus (DP), Dec 602, Dec 603, and Dec 604 were significantly higher in peregrine falcon (Falco peregrinus) eggs from Canada than Spain, with the former having the only measurable concentrations of the dechlorinated DP products, decachloropentacyclooctadecadiene (aCl10DP) and undecachloropentacyclooctadecadiene (aCl11DP). Large variations also occurred in the in ovo concentrations of the DP monoadduct, DPMA. This is the first study to report the accumulation and metabolism of DP by peregrines, both DP and dechloranes in European biota, as well as dechloranes in a terrestrial organism and one at the top of the food web. The geographical differences in the measured in ovo concentrations reflect local exposure of the adult peregrines on their breeding grounds, likely differences in diet of the adults, the production of DP on the Niagara River, and the greater use of Mirex and dechloranes as flame retardants in North America than Europe.

Long-term trends of polychlorinated biphenyls and chlorinated pesticides in franciscana dolphin (Pontoporia blainvillei) from Southern Brazil.

Selected POPs were analyzed in blubber samples of Pontoporia blainvillei from Southern Brazil to appraise temporal trend over a 10 year period (1994-2004). Overall, levels of POPs were relatively low, especially when compared to Northern Hemisphere concentrations. Apart from Mirex and PCBs, which showed stable concentrations, DDTs, HCB, CHLs, Dieldrin levels presented a slight decrease over the studied period. In addition, the increase in the PCBs/DDTs ratio supports the idea that inputs of DDTs are decaying faster than PCBs.

Prenatal exposure to mirex impairs neurodevelopment at age of 4 years.

BACKGROUND: Some studies have suggested that certain organochlorine (OC) compounds may impair neurodevelopment in animals and humans. The objective of this study was to investigate the association between prenatal exposure to an OC pesticide, mirex, and cognitive development in children at age of 4 years. METHODS: A population-based birth cohort in Granada (Spain) recruited between 2000 and 2002 was studied between 2005 and 2006, when the children were 4 years old. Complete data for analyses, including mirex determination in placentas, were gathered on a random sample of 104 children. A standardized version of the McCarthy Scales of Children's Abilities (MSCA) was used to assess children's motor and cognitive abilities. Multivariate analyses were performed to evaluate the relation between MSCA scores and prenatal exposure to mirex, adjusting for potential confounders. RESULTS: The presence of mirex in placenta was inversely associated with cognitive development at 4 years of age: children with prenatal exposure to mirex (>or=limit of quantification: 26%; median: 1.4 ng/g placenta) showed a decrease of 5.15 points in working memory and of 7.33 points in the quantitative area with respect to children of the same age not prenatally exposed to mirex. CONCLUSION: The deficit found in intellectual function during early childhood suggests that prenatal exposure to mirex may have a significant impact on school performance.

ABAM, a model for bioaccumulation of POPs in birds: validation for adult herring gulls and their eggs in Lake Ontario.

An Avian BioAccumulation Model (ABAM) of persistent organic pollutant (POP) uptake and elimination in adult life-stage of birds was validated by simulation of concentrations of DDE, dieldrin, mirex, and HCB in herring gull eggs in Lake Ontario for the years 1985, 1990, and 1992. These chemicals represented a range of whole-body half-lives of 82-265 days in the gull. Dietary intake of POPs by a female gull was simulated by a dynamic bioenergetics model which included dependence on temperature, photoperiod, egg production, and feeding chicks. Concentrations in the two main prey fish of the gull in Lake Ontario were used for POP exposure. Clearance from the female was based on a two compartment toxicokinetic model. Egg concentrations were estimated from egg/whole body female concentration ratios. Simulated concentrations were compared to measured concentrations in gull eggs from 4 different colonies in the northern part of Lake Ontario. Simulations using a diet of 81% fish and 19% uncontaminated food resulted in the best fit with least variance among predicted and measured data. The mean ratio of predicted to measured concentrations in eggs was 1.0 +/- 0.27 among chemicals, years, and colonies for this exposure scenario. This result was in excellent agreement with field assessments of herring gull diet composition in Lake Ontario of 80-82% fish. The ability to perform accurate a priorisimulations for the range of test conditions employed in the validation constituted a rigorous test of the soundness of the model's structure and parameterization. With species-specific adjustments, ABAM can be regarded as a general model for lipophilic POPs bioaccumulation in birds.

Exploring associations between serum levels of select organochlorines and thyroxine in a sample of New York state sportsmen: the New York State Angler Cohort Study.

This preliminary study investigated associations between environmental organochlorine compounds and thyroid function in a sample of 66 sportsmen selected from among participants in the New York State Angler Cohort Study. A cross-sectional design was employed with the primary goal of the analysis being the generation of specific testable hypotheses. Blood samples were analyzed for compounds based on a priori identified literature-cited evidence of thyroid disruption. These included hexachlorobenzene and polychlorinated biphenyl congeners 19, 28, 47, 118, 153, 169, 180, 183, and 187. Time of sample collection, serum triglycerides, cholesterol, high- and low-density lipoproteins, age, body mass index, and cigarette smoking were considered for each participant. Potential associations between organochlorine compounds and serum total thyroxine, controlling for potential confounders, were examined using multivariable linear regression models. The models reported consisted of all variates being entered ("full" model, R2=0.380, P=0.136) and stepwise selection of variates ("reduced" models, alpha=0.15) using the criterion of maximum partial correlation at each step. Several procedures were considered to address contaminant data below the limit of detection in the reduced models with no change in selected predictors. Hexachlorobenzene (beta=-0.113) and age (beta=0.007) were selected as predictors of serum T4 in the reduced models (R2=0.083, P=0.065). Power analysis suggested that by doubling the sample size the existing results would be statistically significant with a type I error of 0.05 and a power of 0.80. These findings are important in the design of a new specific study of thyroid function and environmental contaminants.

Comparative biodegradation of alkyl halide insecticides by the white rot fungus, Phanerochaete chrysosporium (BKM-F-1767).

The ability of Phanerochaete chrysosporium to degrade six alkyl halide insecticides (aldrin, dieldrin, heptachlor, chlordane, lindane, and mirex) in liquid and soil-corncob matrices was compared by using 14C-labeled compounds. Of these, only [14C]lindane and [14C]chlordane underwent extensive biodegradation, as evidenced by the fact that 9.4 to 23.4% of these compounds were degraded to 14CO2 in 30 days in liquid cultures and 60 days in soil-corncob cultures inoculated with P. chrysosporium. Although [14C]aldrin, [14C]dieldrin, [14C]heptachlor, and [14D]mirex were poorly mineralized, substantial bioconversion occurred, as determined by substrate disappearance and metabolite formation. Nonbiological disappearance was observed only with chlordane and heptachlor.

Regional mirex distribution and its effects on gamma-aminobutyric acid and flunitrazepam binding in mouse brains.

Following ip injection of [14C]mirex, its regional distribution was studied parallel to its in vitro effects on [3H]-gamma-aminobutyric acid (GABA) and [3H]flunitrazepam (FNZ) binding to, and [3H]GABA release from, synaptosomes of various mouse brain regions, in order to determine the relationship between relative mirex distribution and its neurotoxic effects mediated through the GABA receptor-ionophore complex. The pattern of mirex uptake into cerebral cortex (CC), brainstem (BS), and cerebellum (CB) showed an initial linear dose-dependent uptake, followed by a decline at higher concentration. The Vmax and Km values determined for the linear mirex uptake phase indicated varied affinities by brain regions, CB and BS being more susceptible to mirex uptake than CC. Both synaptosomal GABA binding and FNZ binding were significantly reduced by mirex in the order of BS approximately equal to CB greater than CC for GABA, and BS approximately equal to CC greater than CB for FNZ. However, mirex lacked any significant effect on the Ca2+-dependent, K+-stimulated release of GABA from radio-prelabeled synaptosomes. While the data indicate no significant differences between brain regions in mirex uptake, they suggest that regional specificities do exist with respect to the inhibition caused by mirex on GABA and FNZ binding to synaptosomes. Unlike the major effects of chlordecone (an analog of mirex) on the dopaminergic system, mirex seems to be primarily neurotoxic through its more specific interaction with the GABA and FNZ binding sites.

Induction of the hepatic cytochrome P-450 dependent monooxygenase system by cis- and trans-5,10-dihydrogen mirex.

The hepatic induction of cytochrome P-450-dependent monooxygenase components by cis- and trans-5,10-dihydrogen mirex was studied in male and female laboratory rats. There were sex-dependent differences between the two isomeric derivatives of mirex. The cis-isomer significantly increased aniline hydroxylase activity in the female, but not in the male. In contrast, aminopyrine N-demethylase was significantly increased by the cis-isomer in both sexes. The trans-isomer increased the hydroxylase and N-demethylase activities in both sexes. The cis-isomer induced NADPH-cytochrome c reductase in the female, and the trans-isomer did not. Both isomers induced hepatic reductase activity in the male rat. No sex-dependent differences in the hepatic induction of cytochrome P-450 were observed for either isomer.

In vitro binding of mirex by mouse hepatocytes.

Mirex (dodecachlorooctahydro-1,3,4-metheno-2H-cyclobuta[cd]+ ++pentalene) is a hepatic tumorigen that is shown to cause marked disturbances in hepatic cell ploidy in rodents. Kinetic measurements of [14C]mirex binding were performed in freshly prepared diploid (DP) and polyploid (PP) hepatocytes, as well as in erythrocytes, under controlled conditions. The binding of mirex to hepatocytes, irrespective of their ploidy, was partially Na+-dependent and totally Ca2+-independent. Variations in temperature and pH appeared to significantly inhibit mirex binding; the optimum binding was seen at 37 degrees C under physiological pH. The saturation kinetic data revealed that PP cells were saturated at a very low concentration of mirex (two- to threefold) compared to DP, exhibiting a high-affinity binding of mirex to PP with a low Km (347 nM) and Vmax (102 nmol/mg X min). The Km (550 nM) and Vmax (340 nmol/mg X min) values determined for DP cells were of higher magnitude, like those of erythrocytes (Km, 819 nM; Vmax, 330 nmol/mg X min), indicating that distinct differences exist in the binding affinities of three cell types. However, erythrocytes and DP cells showed close similarity in their Vmax values. Interestingly, mirex levels in the lipid compartments of DP and PP cells revealed no apparent differences. The results are discussed in terms of the possible susceptibility of PP cells and their role in the initiation of toxic response leading to hepatotumorigenesis in rodents.

Uptake and disposition of mirex in hepatocytes and subcellular fractions in CD1 mouse liver.

In vivo uptake and disposition of [14C]mirex by CD1 mouse liver subcellular fractions and cells of different nuclear ploidy were examined following single or multiple doses of mirex injected intraperitoneally. Significant amounts of mirex were rapidly taken up by liver (21-29%), suggesting that liver is one of the primary sites of accumulation of the chemical. Among subcellular fractions, mirex was predominantly distributed in mitochondria and microsomes in the irreversibly bound form (about 20%), although its levels fluctuated considerably with time. Mirex was completely dissociated with trichloroacetic acid treatment from both nuclear and plasma membrane fractions, although the total uptake by these fractions was markedly high. The time course of uptake and concentration-dependent disposition of mirex revealed that polyploid hepatocytes selectively accumulated higher amounts of the chemical (two to three times) compared to diploid hepatocytes. The increased affinity of polyploid cells to mirex may indicate a greater susceptibility of this cell type to the chemical insult and also may suggest a possible early involvement of polyploids in the tumorigenic process in rodent livers.

Evaluation of mirex, photomirex and chlordecone in the terrestrial aquatic laboratory model ecosystem.

The insecticides mirex and chlordecone and the mirex photodegradation product, photomirex, were evaluated in a terrestrial aquatic laboratory model ecosystem. Although chlordecone was to some extent degraded during the 33 days, neither mirex nor photomirex produced identifiable levels of decomposition products in the water or in any of the organisms of the model ecosystem. All three compounds accumulated significantly in the organisms of the model ecosystem, with chlordecone the least bioaccumulative and photomirex the most bioaccumulative.