Congener-specific Concentrations Research Articles

Global squid contamination by halogenated polycyclic aromatic hydrocarbons and its trade induced risk transfer

Squid is traded globally as an important food resource. However, the occurrence of carcinogenic halogenated polycyclic aromatic hydrocarbons (HPAHs) in squid and the risk of their transfer through trade is little understood or recognized. Here, we comprehensively evaluated the occurrence and risk transfer by quantifying the congener-specific concentrations of HPAHs in 121 squid samples collected from the Pacific, Atlantic and Indian oceans. This was the first time that nine of the 36 target chlorinated and brominated PAH congeners had been detected in squid. The HPAHs exhibited growth-dilution effects in the squid. The lipid content of squid was the most significant factor influencing HPAH bioaccumulation, while differences in squid growth and local ocean contamination influenced by geographical distribution also affected HPAH bioaccumulation. The redistribution and risk transfers of HPAHs in squid as a food could be affected by international trading. The cancer risks from squid consumption in China and Mexico were increased by 50 % and 30 %, respectively, because of international squid trading.

Polychlorinated Naphthalene Congener Profiles in Common Vegetation on the Tibetan Plateau as Biomonitors of Their Sources and Transportation.

Polychlorinated naphthalenes (PCNs) are globally transported, carcinogenic, persistent organic pollutants (POPs) that were recently added to the Stockholm Convention with 184 parties. The Tibetan Plateau plays an important role in the global transportation and distribution of POPs. Knowledge of PCN sources and transportation on the Tibetan Plateau is important for their control globally. In this study, we quantified the congener-specific concentrations of PCNs in lichen, moss, soil, and air samples collected on the Tibetan plateau and found that common lichens were effective biomonitors for predicting atmospheric PCNs in this area. The physiochemical properties of the PCNs, the temperatures, and the lichen lipid contents were identified as important factors influencing PCN partitioning between lichens and air. Lichen-air partitioning equations were established and used to predict PCN concentrations in air in Southeast Tibet. The lichens could be used as PCN biomonitors to clarify their spatial variations, sources, and transportation in the southeast of the plateau. PCN concentrations in lichens increased with altitude, suggesting that high-mountain cold-trapping influenced the PCN transportation behavior. Principal component analysis and linear discriminant analysis showed that the major source of PCNs in this region was long-range atmospheric transportation via the Indian monsoon in summer and wind from Southwest Asia in winter. This study provides a novel method using PCN congener profiles as fingerprints and statistical models for studying the geochemical effects of conditions in high-mountain regions on the contamination behaviors of 75 congeners of the notorious PCNs.

Levels of PCDD/Fs, PBDEs, and PBDD/Fs in Breast Milk from Southern Taiwan.

This study investigates the congener-specific concentrations of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs), and polybrominated diphenyl ethers (PBDEs) in 25 breast milk samples from southern Taiwan. Most investigated congeners in Taiwanese breast milk are detectable except for PBDD/Fs. The geometric means of PCDD/Fs and PBDEs in the breast milk are 2.44pg WHO2005-TEQ/g lipid and 2810pg/g lipid. Several PCDD/F and PBDE congeners were highly correlated to each other like 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF (r = 0.919, p < 0.001). The longest duration of menstruation could be predicted by BDE-153 (β = 0.252) and 1,2,3,4,6,7,8-HpCDF (β = 0.345) with adjustment of confounders using a multiple stepwise linear regression model (r = 0.963, p < 0.001).

Seasonal variations of polybrominated flame retardants bound to car dust under Mediterranean climate

Polybrominated diphenyl ethers (PBDEs) are commercial flame retardants that have been commonly used in vehicle interior to reduce fire-related hazards. Due to high temperatures and intense insolation that can be attained inside cars parked in the sun, additive PBDEs are prone to leach out and attach to in-vehicle dust, as well as to photo-debrominate. This study examines seasonal variations of concentrations of three common PBDE congeners (BDE-47, BDE-99 and BDE-209) in car dust in Israel. The overall concentrations of these BDEs ranged from 1 to 29μg/g, and were higher in the summer than in the winter (average of 10.2 and 5.3μg/g, respectively). Congener-specific concentrations showed distinct seasonal pattern, representing the interplay between leaching, evaporation and photodebromination. Photolysis of the three congeners, while adsorbed on glass filters and exposed to solar radiation, revealed first order kinetics with debromination rates on the order of 10−2/min. Hence, seasonal variations of the meteorological conditions were found to affect the in-vehicle PBDE concentrations, and are therefore expected also to affect the exposure of passengers to PBDEs.

Feasibility Study of Feces for Noninvasive Biomonitoring of Brominated Flame Retardants in Toddlers

This study investigated the feasibility of using feces as a noninvasive matrix to estimate serum concentrations of brominated flame retardants (BFRs) in toddlers for biomonitoring purposes. Tri- to decabrominated diphenyl ethers (tri-decaBDEs), isomer-specific hexabromocyclododecanes, and 16 emerging BFRs were determined in feces from 22 toddlers (11-15 months of age), and results were compared to previously analyzed matched serum samples. BDE-47, -153, -196, -197, -203, -206, -207, -208, and -209 were detected in the feces creating a matched data set (feces-serum, n = 21). Tetra-octaBDE concentrations were significantly higher (Student's paired comparisons t test, α = 0.05) in serum versus feces with BDE-153 having the highest mean difference between the sample matrices. BDE-209 was found in significantly higher concentrations in feces compared to serum. Significant correlations (Pearson's, α = 0.05) between congener-specific concentrations in feces and serum were found for all BDEs except BDE-197 and -203. The feces-serum associations found can be used to estimate serum concentrations of tetra-decaBDEs from feces concentrations and enable a noninvasive sampling method for biomonitoring BDEs in toddlers.

PCDD/Fs, PCBs and PBDEs in zooplankton in the Baltic Sea – Spatial and temporal shifts in the congener-specific concentrations

In the marine food-webs, zooplankton is a key element in the transfer of persistent organic pollutants to higher trophic levels. We determined the congener-specific concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in offshore zooplankton (size from 0.2 to 20mm) collected in 2001, 2002 and 2010 in the northern and central Baltic Sea. Of the PCDD/Fs, the concentrations of 2378-TCDF were from 18 to 47 and of 23478-PeCDF from 7.9 to 29pgg−1fat and showed little temporal differences. However, 1234678-HpCDF and OCDF were abundant in 2001–2002 especially in the eastern Gulf of Finland (average concentrations 50 and 89pgg−1fat, respectively). In 2010 the concentrations of these two congeners were lower, 29 and 30pgg−1fat, respectively, but still substantially higher than in the other surveyed areas. The principal components analysis (PCA) supported that area-specific patterns in pollution strongly contributed to the congener profiles particularly in surface sediment and in sediment trap material, but even in zooplankton. The concentrations of the PCBs were highest in the Gulf of Finland and in the Bothnian Bay. The concentrations of most PCBs were somewhat lower in 2010 than in 2001–2002. Of the dioxin-like PCBs, the concentrations of PCB-77 were highest (271–572pgg−1fat) but PCB-126 (32–113pgg−1fat) contributed from 85% to 91% of the total toxicity of PCBs due to its higher toxic potency. Of the PBDEs, the BDE47 and BDE99 were the most abundant (concentrations from 1.2 to 4.6 and from 0.4 to 3.3ngg−1 fat, respectively). The concentrations of most PBDEs were lower in 2010 than in 2001/2002 except in the eastern Gulf of Finland.

Multivariate relationships between molecular descriptors and isomer distribution patterns of PCBs formed during household waste incineration

The congener-specific concentrations of mono- to deca-chlorinated biphenyls (PC1-10B) in post-combustion zone flue gases from a laboratory-scale fluidized bed reactor were evaluated and correlated with a set of physicochemical properties and chlorine substitution descriptors. The objective was to identify parameters that affect post-combustion zone polychlorinated biphenyl (PCB) formation and interpreting observed correlations by using principal component analysis (PCA), and bidirectional orthogonal projections to latent structures (O2PLS). Both physicochemical variables and chlorine substitution descriptors were shown to have significant effects on the PCB congener distribution; however, the physicochemical descriptors were more influential in all-homologue models, whereas the chlorine substitution descriptors had a greater impact in single-homologue models, which suggests that PCB formation in general may be under thermodynamic control, whereas the distribution of isomers within homologues is more sensitive to chlorine substitution parameters. The EHOMO and ELUMO variables notably influenced both the PCA and the O2PLS models, which indicate that reactivity and polarization in the molecular structures of the PCBs is of importance.

Environmental fractionation of PCBs and PBDEs during particle transport as recorded by sediments in coastal waters

The Strait of Georgia (British Columbia, Canada) is a hydrologically complex inland sea with a rich abundance and diversity of species of aquatic life. Marine sediments, as both a sink for hydrophobic contaminants and a potential source for aquatic food webs, were collected from 41 sites throughout the 6,900-km(2) Strait of Georgia. The congener-specific concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), including BDE-209, were measured. Urban harbors represented hotspots for both PCBs and PBDEs, whereas PBDEs were also found at high concentrations near municipal outfalls. Patterns of PCB distribution were consistent with historical point source emissions in urban areas and environmental distillation toward lighter profiles in remote sites over time. The single congener BDE-209 dominated the PBDEs, accounting for 52% of the average total concentration. However, nonurban deep-water sediment PBDE profiles were both heavier and had higher concentration-weighted average log K(OW) (octanol-water partition coefficient) values compared to shallow samples (percent BDE-209 of total PBDE, 66 versus 32%; log K(OW) , 9.5 versus 8.2, respectively). Collectively, our results suggest that although source signals largely explain PCB and PBDE hotspots in the Strait of Georgia, the combination of physicochemical properties and environmental processes drive divergent compositional fates for the PCBs and the heavier PBDEs in the sediments of the Strait of Georgia.

CONGENER PATTERN AND TOXICITY OF POLYCHLORINATED BIPHENYLS IN AQUATIC ORGANISMS FROM AN ELECTRONIC AND ELECTRICAL WASTE AREA

Electronic and electrical waste (E-waste) is a waste type consisting of any broken or unwanted electrical or electronic appliance. Obsolete E-waste has become a serious problem. Many previous studies showed that persistent organic pollutants (POPs) and heavy metals caused serious contamination in air, soil, sediment and freshwater. It is drawing more and more attentions because of its adverse impacts on environment and human health. According to the State Environmental Protection Administration of China, 70% of worldwide e-waste has been sent to China. Taizhou region in Zhejiang Province is one of the most intensive E-waste processing sites in China. Polychlorinated biphenyls (PCBs) were widely used worldwide as coolants and insulators in electrical capacitors and transformers, and as plasticizers in paint and rubber sealant. Large quantities of PCBs have since entered the environment through leakage, disposal, and evaporation. PCBs stability is also responsible for their continued presence in the environment even decades. Environmental levels of PCBs are traditionally measured as total PCB based on Aroclor equivalent analysis, as opposed to congener-specific concentrations, due to analytical limitations and/or cost differentials. To evaluate the true risk of PCBs to human and ecosystem health, more complex and, in turn, costly Dioxin-Like PCB-specific analytical methods (e. g., U. S. EPA method 1668a) are available. Dioxin-like PCBs (dl-PCBs) are a group of 12 PCBs that share a common toxic mechanism with the most toxic dioxin compound (i.e., 2 3, 7, 8-tetrachlorodibenzop-dioxin or 2, 3, 7, 8-TCDD) and generally are among the most toxic PCB congeners as they incur toxic effects at relatively lower concentrations than those of non-dl-PCBs. In the present study, samples of winkle, loach and crucian carp were collected from the e-waste area (Taizhou, Zhejing) in 2006. DI-PCBs were determined in the samples using isotope dilution Gas Chromatography/Mass Spectrometry (CC/MS) method. Our results showed that the average concentrations of PCBs were 1303. 53, 3845. 00 and 5645. 34 ng/g lipid weight in winkle, loach and crucian carp, respectively. Toxic equivalencies (TEQs) were determined to be 1.35, 8.44 and 29.18 pg WHO-TEQ/g wet weight in winkle, leach and crucian carp, respectively. TEQs in winkle and crucian carp exceed the European maximum permissible level (2006) of TEQs in fish for human food. In addition, PCB 118 was major congener and constituted 57.73%-61.22% and 44.27%-50.61% of total PCBs and TEQs, respectively. Furthermore, PCB 118 was found to have linear correlations to the total PCBs and TEQs. The correlative coefficients (R-2) were 0.9988 (P < 0.0001) and 0.9873 (P < 0.0001). These results indicated that aquatic organisms from the e-waste area have been seriously contaminated by PCBs which might come from Aroclor 1254 released from E-waste dismantling.

Application of the ISCST3 model for predicting PCDD/F concentrations in agricultural soil in the vicinity of a MSWI plant in China

Based on the Industrial Source Complex Short-Term Version 3 (ISCST3) model, a simplified modeling approach was developed to predict concentrations of congeners of polychlorinated-p-dioxins and dibenzofurans (PCDD/Fs) of agricultural soil, within a radius of 3 km from a municipal solid waste incinerator (MSWI) plant after its 4-year operation in Hangzhou, China. Comparisons were made between the measured and estimated congener-specific concentrations and the international-toxic equivalent (I-TEQ) values of soil samples with respect to distance from the stack. The results indicate that the predictions of soil PCDD/F concentrations and I-TEQ values were generally lower than their observations, and that the higher the degree of under-estimation seems, the greater the further downwind one gets. Nevertheless, most of the predictions were in good agreement with the trend of measured ones and were within a factor of ten for samples located within 1 km of the plant. Besides, analysis of contributions of various deposition pathways confirms that in addition to wet particle deposition, the dry gaseous deposition is essential for realistic prediction of PCDD/F depositions to soil, especially for tetra- and penta-chlorinated dioxins.

Estrogenic Activity of Polychlorinated Biphenyls Present in Human Tissue and the Environment

This study evaluated the estrogenicity of polychlorinated biphenyls (PCBs) present in environmental media and human tissue and assessed exposure pathways for PCB-derived estrogenic potency in air, soil, and dust from New Bedford, MA, an area with a PCB-contaminated Superfund site. Thirty-four PCB congeners were assayed for estrogenic potency using E-SCREEN, an assay based on the estrogen-dependent proliferation of MCF-7 cells in vitro. Childhood exposure to estradiol-equivalents via PCBs in environmental media was estimated byweighting previously reported New Bedford congener-specific concentrations by their relative estrogenic potency and published inhalation and soil ingestion rates. Thirteen congeners were weakly estrogenic in E-SCREEN: PCBs 17, 18, 30, 44, 49, 66, 74, 82, 99, 103, 110, 128, and 179. These PCBs were typically 6 orders of magnitude less potent than 17beta-estradiol, with proliferative potencies ranging from 0.0007% to 0.0040%. Of the environmental media assessed, air (inhalation) had the highest PCB-derived estradiol-equivalent exposure. PCB estrogenic potency information from this study provides an important resource both for preliminary estimation of routes of human exposure to xenoestrogens and for application to human health studies focused on estrogen-responsive health outcomes, such as reproductive development and related malignancies.

Comparison of Risk Assessment Methodologies for Exposure of Mink to PCBs on the Kalamazoo River, Michigan

Risk assessments are generally based on exposures predicted by use of simple models of accumulation from abiotic compartments or the diet. The use of tissue-specific measurements of residue concentrations in wildlife tissues is more accurate and subject to less uncertainty, but these data are often not available. This report compares the results of two different site-specific approaches for assessing the risk of PCBs to mink residing along the Kalamazoo River, MI. The first approach was based on hepatic concentrations of PCBs and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) of mink. The second approach was based on measured concentrations of both PCBs and TEQs in the diets of mink. For each of these methodologies, assessments were based on no observed adverse effect levels (NOAELs) or concentrations (NOAECs) and lowest observed adverse effect levels (LOAELs) or concentrations (LOAECs). Samples of mink (Mustela vison) and its diet were collected from within the Kalamazoo River Area of Concern (KRAOC) and an upstream reference area in the Fort Custer Recreation Area (FC). Hazard quotient (HQ) values were calculated based on congener-specific concentrations of PCBs or TEQs, several toxicity reference values (TRVs), and several assumed dietary compositions. Mean total hepatic concentrations of PCBs were 2.7 and 2.3 mg PCBs/kg, ww, in mink from the KRAOC and FC, respectively. HQs based on the LOAEC and mean hepatic PCB concentrations ranged from 0.37 to 0.87 at KRAOC and 0.31-0.73 at FC. HQs based on PCBs in the diet ranged from 0.20 to 1.8 at KRAOC and from 0.04 to 0.35 at FC. Dietary HQs were less than 10-fold different than tissue-based HQs.

Congener-specific concentrations and carbon stable isotope ratios (δ 13C) of two technical toxaphene products (Toxaphene® and Melipax®)

In this study we compared the contribution of individual congeners and the ratios of stable carbon isotopes of two technical toxaphene products. The former US-American product Toxaphene® was from 1978 and the East-German product Melipax® from 1979. Both technical products showed the known complexity in GC/ECD measurements. Contributions of 24 peaks to each of the technical products were determined by gas chromatography in combination high resolution electron capture negative ion mass spectrometry (GC/ECNI-HRMS). The percentages of the compounds studied in the technical mixtures ranged from ∼0.05% to ∼2.5% but showed some individual differences. 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025 or P-62) was identified as a major congener in both mixtures. 2-Endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679 or P-50) were found at similar concentration in both technical products. Identical amounts of Melipax or Toxaphene were combusted to CO 2 in an element analyzer and their δ 13C values were determined relative to the international standard Vienna PeeDee belemnite (VPDB). The mean δ 13C values of both products varied by 2.8% (determined at two different locations) which is roughly one order of magnitude more than the precision obtained in repetitive analyses of the individual products. Thus, both investigated products could be unequivocally distinguished by stable isotope ratio mass spectrometry (IRMS). IRMS analyses may thus be a suitable tool for tracing back toxaphene residues in environmental and food samples to the one or both of the products.

Determination of tissue–blood partition coefficients for a physiological model for humans, and estimation of dioxin concentration in tissues

The tissue–blood partition coefficients for a physiologically based pharmacokinetic (PBPK) model were determined, and the concentrations of 17 congeners of polychlorinated dibenzo- p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in tissues in Japanese people were estimated using the model. According to the PBPK model established by Lawrence and Gobas [Chemosphere 35 (1997) 427–452], we assumed a steady-state fugacity model for Japanese people in general, and set the route of PCDD/Fs exposure only from food intake. The required partition coefficients for liver, kidney, adipose, muscle, skin, bile, gut and viscera (richly perfused tissue) were calculated using available autopsy data from eight Japanese men and women who were not accidentally exposed to PCDD/Fs. For validation of the partition coefficients, estimated PCDD/F concentrations in liver, kidney, fat, blood and muscle using the model were compared to other two sets of measured concentration data in Japanese tissues. Good agreement was obtained between estimated data and measured data, and most of the measured data were within the simulated concentration range in liver, kidney, blood and muscle. From these results, our model and calculated partition coefficients seem applicable for the estimation of congener-specific concentrations in human tissues.

Validation of modeling approach to evaluate congener-specific concentrations of polychlorinated dibenzo- p-dioxins and dibenzofurans in air and soil near a solid waste incinerator

A concise modeling approach using long-term averaged meteorological data was developed to estimate site-specific concentrations of congeners of polychlorinated dibenzo- p-dioxins and dibenzofurans (PCDD/Fs) near a solid waste incinerator. This approach consists of calculation of atmospheric dispersion, dry and wet deposition of gaseous and particle-bound congeners, and non-steady-state concentrations in soil. The predictability of this approach was evaluated by comparison of calculated concentrations of congeners in soil with those measured at eight locations near a municipal solid waste incinerator (MSWI). The variation of these concentrations due to variability of meteorological parameters is small. A considerable number of mean values show good agreement with measured concentrations within a factor of three. The reasonable agreement between calculated and measured concentrations indicates that algorithms for the calculation of vapor-phase deposition and non-steady-state concentrations in soil must be included in the modeling approach for an accurate estimation of the concentrations of congeners of PCDD/Fs emitted from MSWIs to the atmosphere. For a detailed estimation of site-specific concentrations, it is important to specify the bulk density of soil in the evaluated area, together with meteorological parameters.

Factors affecting organochlorine contaminant concentrations in milk and blood of northern fur seal ( Callorhinus ursinus) dams and pups from St. George Island, Alaska

Levels of organochlorine contaminants in blood of northern fur seal ( Callorhinus ursinus) pups and the blood and milk of their dams early in the lactation period are reported here. The contaminants included 15 selected individual polychlorinated biphenyl (PCB) congeners and DDT metabolites identified through high-performance liquid chromatography. Congeners CB-77, -81, -126, -169 and -189 were below the limits of detection in milk and blood samples analyzed. Congener-specific concentrations of PCBs in the blood of pups were compared based on the age of their dam (≤5 years or >7 years). Pups of young (presumably primiparous) dams had significantly elevated levels of CBs-101, -118, -128, -138, -153/87, -170/194, and -180 than pups of older (multiparous) dams. Congeners CB-128 and -170/194 were detected in the blood of pups of young dams but not in the blood of pups of older dams nor in any of the dams blood. Additionally, pups had higher blood levels in seven of 10 detected PCB congeners as compared to the levels measured in milk when adjusted for lipid content. Levels of DDT metabolites and toxic equivalency quotients of dioxin-like congeners followed similar trends. Lipid-normalized concentrations of CB-101 and total PCBs were significantly higher in the blood of dams than in their milk. CB-128, -156, -157, -170/194, p,p′-DDT, o,p′-DDT, p,p′-DDD and o,p′-DDD were not detected in dam blood samples, but were detected in milk samples. Calculation of ‘biomagnification factors’ from milk to pup blood indicated a biomagnification of CB-101, -105, -118, -138, -153/87, and -180. Significant mean accumulation factors ranged from 1.5 to 7.5. Inter-annual differences in exposure levels and specific congener concentrations in both milk and blood were apparent. Northern fur seal pups, especially first-born, have a substantial exposure to organochlorine contaminants at a critical developmental stage.

Group separation of ortho -PCBs, coplanar non- ortho -PCBs and PCDDs/PCDFs using an alumina column as an one-step clean-up procedure

A novel, simple inexpensive and rapid clean-up procedure is presented for the separation and quantitative determination of polychlorinated biphenyls (ortho-PCBs), coplanar non-ortho-PCBs (PCB No. 77, 126, 169) and polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in environmental samples. This clean-up procedure is the first method separating ortho-PCBs, non-ortho-PCBs and PCDD/PCDFs in one step with a single activated alumina column. Firstly, the ortho-PCBs are eluted from the activated alumina with a non-polar solvent. The non-ortho-PCBs are isolated in the second fraction with a more polar solvent-mixture, and finally the PCDD/PCDFs are collected in a polar fraction. This clean-up procedure was used to determine the congener-specific concentrations of ortho-PCBs, non-ortho-PCBs 77, 126 and 169 and PCDD/PCDFs in two different seepage waters and in one sewage sludge by HRGC and HRMS. The toxic equivalent quantities (TEQs) of the individual PCDD/PCDF-congeners and some toxic coplanar PCB-congeners were estimated.