Congener Groups Research Articles

Deconvolution of Soft Ionization Mass Spectra of Chlorinated Paraffins To Resolve Congener Groups.

We describe and illustrate a three-step data-processing approach that enables individual congener groups of chlorinated paraffins (CPs) to be resolved in mass spectra obtained from either of two soft ionization methods: electron capture negative ionization mass spectrometry (ECNI-MS) or atmospheric pressure chemical ionization mass spectrometry (APCI-MS). In the first step, general fragmentation pathways of CPs are deduced from analysis of mass spectra of individual CP congeners. In the second step, all possible fragment ions in the general fragmentation pathways of CPs with 10 to 20 carbon atoms are enumerated and compared to mass spectra of CP mixture standards, and a deconvolution algorithm is applied to identify fragment ions that are actually observed. In the third step, isotope permutations of the observed fragment ions are calculated and used to identify isobaric overlaps, so that mass intensities of individual CP congener groups can be deconvolved from the unresolved isobaric ion signal intensities in mass spectra. For a specific instrument, the three steps only need to be done once to enable deconvolution of CPs in unknown samples. This approach enables congener group-level resolution of CP mixtures in environmental samples, and it opens up the possibility for quantification of congener groups.

Endocrine disrupting chemicals and ovulation: Is there a relationship?

Although the potential for endocrine disrupting chemicals (EDCs) to disrupt female fecundity is great, few studies have assessed the threat to human reproduction. This study investigates levels of organochlorines in relation to their impact on women’s menstrual cycles and ovulatory status.To address concerns of the Akwesasne Mohawk community in upstate New York regarding well-established exposure to EDCs, women’s fertility and reproductive health endpoints, we recruited 215 women between the ages of 21 and 38 years to measure menstrual cycle characteristics and levels of local pollutants. Of these, 155 women collected saliva over the course of their menstrual cycle allowing for analysis of estradiol and progesterone levels and the determination of ovulatory status in relationship to their serum pollutant levels. A subset of participants (15) who did not commence cycling within a month of their enrollment were not included in the analysis, hence reducing the sample size to 140 participants. Additionally, a lipid panel, estradiol and progesterone were assessed in serum on Day 3 of the menstrual cycle.Median cycle length for women in the sample was 29 days. After aligning the cycles, 110 women were considered ovulatory and 45 (29%) anovulatory. Concentrations of groups of more persistent PCBs congeners, HCB, and p,p’-DDE did not differ significantly with ovulatory status. However, a sub-group of low-chlorinated PCB congeners, considered to be estrogenic were significantly higher among anovulatory women. These findings suggest that certain EDC’s, ubiquitous in our environment, may adversely affect menstrual cycles and thus have the capacity to impair reproductive function, including likelihood of conception.

Temporal trends of polychlorinated biphenyls serum levels in subjects living in a highly polluted area in Italy from 2003 to 2015: a population-based cohort study.

Introduction A chemical factory located in Brescia, an industrialized town in North Italy, produced polychlorinated biphenyls since the 1930s to the 1980s, determining a relevant pollution of soil, food and people. Since 2001, after a survey carried out in the general population living in the town, the individuals with serum levels of polychlorinated biphenyls higher than the reference entered a follow-up study for evaluating the temporal trend of their polychlorinated biphenyls serum levels. Methods We performed a prospective cohort study including subjects with at least three polychlorinated biphenyls measures during the period 2003-2015. We evaluated the temporal trends of total polychlorinated biphenyls serum levels using mixed models with a cubic-spline for time. We also stratified the analysis for the most commonly found congeners (IUPAC codes 138,153, 170, 180, 194 and 209) and subjects’ age. Results A total of 128 subjects were enrolled (mean age 57.7 years). The mean of polychlorinated biphenyls decreased from 58.35 ng/ml at the beginning (0-3 years) to 40.62 ng/ml at the end (9-12 years) of the follow-up. Polychlorinated biphenyls reduction over time was confirmed when using multivariate mixed models adjusted for age, and when analysing the major congeners separately. Finally, we evaluated the temporal trend according to age tertiles using mixed models with cubic splines terms for polychlorinated biphenyls. From baseline to twelve years, mean values of polychlorinated biphenyls levels increased with age and decreased over time, for each age category: from 43.05 ng/ml to 26.57 ng/ml, from 54.95 ng/ml to 31.30 ng/ml and from 75.36 ng/ml to 49.42 ng/ml for ages ≤55 years, 56-65 and ≥66 years, respectively. Conclusions A significant decrease of the serum concentrations of polychlorinated biphenyls was observed in subjects with high values of these chemicals at enrolment, over a 12 year period. The decrease was evident for each congener and age group.

A Novel Method for Profiling and Quantifying Short- and Medium-Chain Chlorinated Paraffins in Environmental Samples Using Comprehensive Two-Dimensional Gas Chromatography-Electron Capture Negative Ionization High-Resolution Time-of-Flight Mass Spectrometry.

Chlorinated paraffins (CPs) are complex technical mixtures containing thousands of isomers. Analyzing CPs in environmental matrices is extremely challenging. CPs have broad, unresolved profiles when analyzed by one-dimensional gas chromatography (GC). Comprehensive two-dimensional GC (GC×GC) can separate CPs with a high degree of orthogonality. A novel method for simultaneously profiling and quantifying short- and medium-chain CPs, using GC×GC coupled with electron capture negative ionization high-resolution time-of-flight mass spectrometry, was developed. The method allowed 48 CP formula congener groups to be analyzed highly selectively in one injection through accurate mass measurements of the [M - Cl](-) ions in full scan mode. The correlation coefficients (R(2)) for the linear calibration curves for different chlorine contents were 0.982 for short-chain CPs and 0.945 for medium-chain CPs. The method was successfully used to determine CPs in sediment and fish samples. By using this method, with enhanced chromatographic separation and high mass resolution, interferences between CP congeners and other organohalogen compounds, such as toxaphene, are minimized. New compounds, with the formulas C9H14Cl6 and C9H13Cl7, were found in sediment and biological samples for the first time. The method was shown to be a powerful tool for the analysis of CPs in environmental samples.

Occurrences, sources and risk assessment of short- and medium-chain chlorinated paraffins in sediments from the middle reaches of the Yellow River, China

Chlorinated paraffins (CPs), one class of hydrophobic and toxic compounds, are easily adsorbed into sediments and then pose potential risks to the ecosystem and human health. However, few researches on short- and medium-chain CPs (SCCPs and MCCPs) in sediments have been performed. In order to comprehensively investigate the spatial distributions, sources, and ecological risks of CPs, sediments collected from the middle reaches of the Yellow River were analyzed by two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC × GC–TOFMS). The concentrations of SCCPs and MCCPs ranged from 11.6 to 9.76 × 103 ng/g dry weight (dw) and from 8.33 to 168 ng/g dw, respectively. No significant correlation was found between total organic carbon (TOC) and CP concentrations (P > 0.05). The spatial distributions showed that contamination levels of CPs were relevant to human activities. In addition, two types of sediment samples were classified by hierarchical cluster analysis (HCA) and results indicated the predominant congener groups were C10Cl6–7 for SCCPs and C14Cl7–8 for MCCPs. Principal component analysis (PCA) revealed that SCCPs and MCCPs in the sediments may have different sources, and SCCPs are likely to come from the production and use of CP-42 and CP-52. Moreover, complex environmental processes, including long-range transportation via the atmosphere and/or river, deposition and degradation of CPs, resulted in increased abundances of short chain and low chlorinated congeners in sediment samples compared with commercial mixtures, and different homolog patterns among samples. The significant negative correlation between SCCP concentrations and MCCP/SCCP ratios could be related to long-range transport of CPs. A preliminary risk assessment indicated that CPs at current levels posed no significant ecological risk.

Evaluation of relative effect potencies (REPs) for dioxin-like compounds to derive systemic or human-specific TEFs to improve human risk assessment.

Toxic equivalency factors (TEFs) are generally applied for estimating human risk of dioxins and dioxin-like compounds using systemic (e.g., blood) levels, even though these TEFs are established based on intake doses in rodent studies. This review shows that systemic relative effect potencies (REPs) can deviate substantially from intake REPs, but are similar to in vitro-derived REPs. Interestingly, the in vitro REPs for 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) and 2,3,4,7,8-pentachlorodibenzofuran (4-PeCDF) are up to one order of magnitude higher than their in vivo REPs and WHO-TEFs, based on oral intake. In addition, clear species-differences in in vitro REPs were apparent for some congeners. Especially the human-derived REP for polychlorinated biphenyl 126 is one to two orders of magnitude lower than rodent REPs and its current WHO-TEF. Next, suggested adapted systemic or human-specific TEFs for these congeners were applied to calculate changes in systemic TEQ concentrations in studies from the USA, Germany and Japan and compared with either the JECFA TDI or USEPA RfD of TCDD. Overall, the effect of such TEF changes for these three congeners on total TEQ roughly balances each other out in the general population. However, results may be different for situations in which a specific group of congeners dominates. For those congeners that show a distinct deviation between either intake and systemic REPs or between rodent- and human-based in vitro REPs, we propose that especially REPs derived from human-based in vitro models are weighted more heavily in establishing systemic or human-specific TEF values to improve human health risk assessment.

Quantification of short- and medium-chain chlorinated paraffins in environmental samples by gas chromatography quadrupole time-of-flight mass spectrometry

Chlorinated paraffins (CPs) are technical products produced and used in bulk for a number of purposes. However, the analysis of CPs is challenging, as they are complex mixtures of compounds and isomers. We herein report the development of an analytical method for the analysis of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) using quadrupole time-of-flight high-resolution mass spectrometry (GC-NCI-qTOF-HRMS). This method employs gas chromatography with a chemical ionization source working in negative mode. The linear relationship between chlorination and the CP total response factors was applied to quantify the CP content and the congener group distribution patterns. In a single injection, 24 SCCP formula groups and 24 MCCP formula groups were quantified. Extraction of accurate masses using qTOF-HRMS allowed the SCCPs and MCCPs to be distinguished, with interference from other chemicals (e.g., PCBs) being largely avoided. The SCCP and MCCP detection limits were 24–81ng/mL and 27–170ng/mL, respectively. Comparison of the obtained results with analytical results from gas chromatography coupled with electron capture negative ionization low-resolution mass spectrometry (GC-ECNI-LRMS) indicate that the developed technique is a more accurate and convenient method for the analysis of CPs in samples from a range of matrices.

Diabetes Prevalence in Relation to Serum Concentrations of Polychlorinated Biphenyl (PCB) Congener Groups and Three Chlorinated Pesticides in a Native American Population.

Background:Exposure to persistent organic pollutants (POPs) is known to increase risk of diabetes.Objective:To determine which POPs are most associated with prevalence of diabetes in 601 Akwesasne Native Americans.Methods:Multiple logistic regression analysis was used to assess associations between quartiles of concentrations of 101 polychlorinated biphenyl (PCBs) congeners, congener groups and three chlorinated pesticides [dichlorodiphenyldichloroethylene (DDE), hexachlorobenzene (HCB) and mirex] with diabetes. In Model 1, the relationship between quartiles of exposure and diabetes were adjusted only for sex, age, body mass index (BMI), and total serum lipids. Model 2 included additional adjustment for either total PCBs or total pesticides.Results:Total serum PCB and pesticide concentrations were each significantly associated with prevalence of diabetes when adjusted only for covariates (Model 1), but neither showed a significant OR for highest to lowest quartiles after additional adjustment for the other (Model 2). When applying Model 2 to PCB congener groups and individual pesticides, there were significant omnibus differences between the four quartiles (all ps < 0.042) for most groups, with the exception of penta- and hexachlorobiphenyls, DDE and mirex. However, when comparing highest to lowest quartiles only non- and mono-ortho PCBs [OR = 4.55 (95% CI: 1.48, 13.95)], tri- and tetrachloro PCBs [OR = 3.66 (95% CI: 1.37, –9.78)] and HCB [OR = 2.64 (95% CI: 1.05, 6.61)] showed significant associations with diabetes. Among the non- and mono-ortho congeners, highest to lowest quartile of dioxin TEQs was not significant [OR = 1.82 (95% CI: 0.61, 5.40)] but the OR for the non-dioxin-like congeners was [OR = 5.01 (95% CI: 1.76, 14.24)].Conclusion:The associations with diabetes after adjustment for other POPs were strongest with the more volatile, non-dioxin-like, low-chlorinated PCB congeners and HCB. Because low-chlorinated congeners are more volatile, these observations suggest that inhalation of vapor-phase PCBs is an important route of exposure.Citation:Aminov Z, Haase R, Rej R, Schymura MJ, Santiago-Rivera A, Morse G, DeCaprio A, Carpenter DO, and the Akwesasne Task Force on the Environment. 2016. Diabetes prevalence in relation to serum concentrations of polychlorinated biphenyl (PCB) congener groups and three chlorinated pesticides in a Native American population. Environ Health Perspect 124:1376–1383; http://dx.doi.org/10.1289/ehp.1509902

Postmating barriers to hybridization between an island’s native eucalypts and an introduced congener

We evaluate postmating barriers to hybridization between an exotic eucalypt and a group of native congeners on the island of Tasmania. We aimed to better understand the basis of reproductive isolation between the species, glean insights into the evolution of isolating mechanisms, and inform genetic risk management. Compatibility between the exotic plantation species Eucalyptus nitens (pollen parent) and 18 native Tasmanian taxa was assayed using experimental crossing for 17 taxa (13,458 flowers pollinated to produce 1058 female × male cross combinations), and previous data for one species. Compatibility was assessed in terms of F1 hybrid production, as well as F1 hybrid survival and growth after 5 years. This data was combined with measurements of style length, and genetic distance from E. nitens to each maternal species, in order to determine the importance of a sequence of prezygotic and postzygotic barriers. We found that the early-acting barrier of style length (prezygotic) had the strongest isolating effect, while later-acting (postzygotic) barriers, affecting early-age growth and survival, contributed little to reproductive isolation. Style length alone explained 46 % of the variation in hybridization rate. Conversely, there was no significant relationship between genetic distance and prezygotic or postzygotic compatibility in these closely related species. This pattern is consistent with selection driving the rapid evolution of prezygotic barriers, while drift-like-processes lead to the more gradual evolution of intrinsic barriers. Although other premating and postmating barriers clearly contribute, our results highlight the important role of early-acting postmating barriers in preventing gene flow from exotic E. nitens plantations.

Toxicokinetics of short-chain chlorinated paraffins in Sprague-Dawley rats following single oral administration.

Short-chain chlorinated paraffins (SCCPs) have attracted considerable attention for their characteristic of persistent organic pollutants. However, very limited information is available for their toxicokinetic characteristics, limiting the evaluation of their health risks. In this study, we performed a toxicokinetics study to explore the absorption and excretion processes of SCCPs (a mixture of C10-, C11-, C12- and C13-CPs) after a single oral administration to the Sprague-Dawley rats. The toxicokinetic results showed that peak blood concentration of total SCCPs was attained at 2.8 day with Cmax value of 2.3 mg L(-1). The half-lives of total SCCPs in blood for the absorption t1/2 (ka), distribution t1/2 (α) and elimination phases t1/2 (β) were calculated to be 1.0, 1.7 and 6.6 days, respectively. During the 28 days post-dosing, about 27.9% and 3.5% of orally administrated SCCPs were excreted through feces and urine without metabolism, respectively. Congener group abundance profiles indicate a relative increase of Cl5-SCCPs in blood and urine in the elimination stage, and a higher accumulation of Cl8-10-SCCPs in feces. The distribution discrepancies of SCCPs congener groups in blood and excreta were more dependent on chlorine contents than on carbon chain lengths.

Environmental Polychlorinated Biphenyl Exposure and Breast Cancer Risk: A Meta-Analysis of Observational Studies.

BackgroundAssociation between polychlorinated biphenyl (PCB) exposure and breast cancer risk has been widely studied, but the results remain controversial. We performed a meta-analysis to evaluate the evidences from observational studies on PCB exposure and breast cancer risk.MethodsRelevant studies with data on internal PCB dose were identified from PubMed, EMBASE, CBM and CNKI databases through November 2014. Multivariable-adjusted odds ratio (OR) with 95% confidence intervals (CIs) were applied to assess the association between PCB exposure and breast cancer risk. Heterogeneity test, sensitivity analysis, subgroup analysis and publication bias test were also performed. To further explore the association between specific groups of PCB congeners and breast cancer, we examined the PCB congeners classified, according to their structural, biological and pharmacokinetics properties, as group I (potentially estrogenic), group II (potentially anti-estrogenic and immunotoxic, dioxin-like), and group III (phenobarbital, CYP1A and CYP2B inducers, biologically persistent).ResultsOf 660 studies screened, 25 studies which met criteria were selected, involving a total of 12866 participants (6088 cases and 6778 controls) from eight countries. The results showed that the risk of breast cancer was associated with group II (OR = 1.23, 95% CI: 1.08–1.40) and group III (OR = 1.25, 95% CI: 1.09–1.43) PCBs, but not with group I (OR = 1.10, 95%CI: 0.97–1.24) PCBs or total PCB exposure (OR = 1.09, 95%CI: 0.97–1.22).ConclusionsOur meta-analysis based on the selected studies found group II and group III PCB exposure might contribute to the risk of breast cancer. More studies in developing countries with higher PCB levels are needed, as well as studies to explore the relationships between mixtures of organochlorine compounds and breast cancer risk.

A new species of Schizopera (Copepoda: Harpacticoida) from Japan, its phylogeny based on the mtCOI gene and comments on the genus Schizoperopsis

The predominantly marine genus Schizopera Sars, 1905 has only two significant inland water species-flocks, one in the ancient African Lake Tanganyika and the other in subterranean waters of Western Australia. Discovery of Schizopera abei sp. nov. from several interstitial locations in the vicinity of the ancient Lake Biwa has wider implications for the study of morphological homoplasies in the genus, as well as for the study of freshwater invasions in harpacticoid copepods. The new Schizopera species belongs to a small group of congeners with a two-segmented endopod of the fourth leg, which used to be recognised as a separate genus, Schizoperopsis Apostolov, 1982. Our reconstructed phylogenies based on the mtCOI partial sequences suggest that this character probably evolved convergently in at least some Schizopera, thus rendering the genus Schizoperopsis polyphyletic. However, almost all basal nodes in our cladograms are weakly supported, which shows limitations of a single-gene approach for reconstructing phylogenetic relationships. The new species is the first member of its genus from Japanese inland waters, and it has no close relatives among extent congeners anywhere in the world. We speculate that its ancestor may have invaded Lake Biwa, and subsequently its surrounding subterranean waters, from brackish areas around central Japan, presumably during a period of high sea water level through its major outflow river. This discovery may provide further support for the hypothesis about the role of ancient lakes as biodiversity pumps for subterranean habitats.http://zoobank.org/urn:lsid:zoobank.org:pub:1F71F7AD-B7C8-4AD3-BE44-5E1BEE4E2AA8

Fast quantification of chlorinated paraffins in environmental samples by direct injection high-resolution mass spectrometry with pattern deconvolution.

Chlorinated paraffins (CPs) are high production volume chemicals, but data about their environmental fate are scarce. CP mixtures composed of thousands of isomers represent a major challenge for quantification at low levels in environmental samples. Here, we present a novel analytical method for analysis of short-chain, medium-chain, and long-chain CPs in a single injection, that also yields information about congener group pattern. Our detection method is based on direct injection into an atmospheric pressure chemical ionization source operated in negative ion mode under chlorine-enhanced conditions, followed by quadrupole time-of-flight high-resolution mass spectrometry (APCI-qTOF-HRMS) operated in full-scan mode. A mathematical algorithm is applied to deconvolute the CP patterns in the analyzed samples into a linear combination of patterns of technical CP mixtures and to quantify CPs using technical mixtures as external calibration standards. For CP mixtures with known composition, the new method provided concentrations that were within a factor of 1.2 of the target value. Accuracies for CPs spiked to sediment and fish extracts were between 91% and 123%. Concentrations determined in unspiked field samples were within a factor of 5 for short-chain CPs and a factor of 16 for medium-chain CPs of results obtained with an independent method based on gas chromatography/electron capture negative ionization high-resolution mass spectrometry (GC/ECNI-HRMS). The presented APCI-qTOF-HRMS pattern deconvolution method is an interesting alternative for CP analysis in environmental samples. It is particularly sensitive for medium- and long-chain CPs and has the advantage of being extremely fast (instrumental analysis time, less than 1 min).

Levels of short chain chlorinated paraffins in pine needles and bark and their vegetation-air partitioning in urban areas

Short chain chlorinated paraffins (SCCPs) have been of considerable concern in recent years due to their high production volumes, environmental persistency and potential for long range atmospheric transport. Vegetation can take up considerable amounts of semivolatile organic compounds from the atmosphere and can act as indicators of local contamination. Paired pine needles and bark were sampled around Beijing during winter and summertime to investigate the distribution of SCCPs in urban areas. Levels in bark samples ranged 5.79–37.5 μg/g on a lipid normalized basis (lw) with a geometric mean (GM) of 16.9 μg/g lw whereas levels were 3.03–40.8 (GM 11.8) μg/g lw for needles. Average congener group abundance profiles showed equal contribution of all four carbon groups (C10–13) in wintertime whereas higher abundances of C10 and C11 groups were found during summer. Uptake of SCCPs occurred mainly via kinetically limited gaseous deposition and particle bound deposition in the investigated area.

An integrative risk assessment approach for persistent chemicals: A case study on dioxins, furans and dioxin-like PCBs in France

For persistent chemicals slowly eliminated from the body, the accumulated concentration (body burden), rather than the daily exposure, is considered the proper starting point for the risk assessment. This work introduces an integrative approach for persistent chemical risk assessment by means of a dynamic body burden approach. To reach this goal a Kinetic Dietary Exposure Model (KDEM) was extended with the long term time trend in the exposure (historic exposure) and the comparison of bioaccumulation with body burden references for toxicity. The usefulness of the model was illustrated on the dietary exposure to PolyChlorinatedDibenzo-p-Dioxins (PCDDs), PolyChlorinatedDibenzoFurans (PCDFs) and PolyChlorinated Biphenyls (PCBs) in France. Firstly the dietary exposure to these compounds was determined in 2009 and combined with its long term time trend. In order to take differences between the kinetics of PCDD/F and dl-PCBs into account, three groups of congeners were considered i.e. PCDD/Fs, PCB 126 and remaining dl-PCBs. The body burden was compared with reference body burdens corresponding to reproductive, hepatic and thyroid toxicity. In the case of thyroid toxicity this comparison indicated that in 2009 the probability of the body burden to exceed its reference ranged from 2.8% (95% CI: 1.5–4.9%) up to 3.9% (95% CI: 2.7–7.1%) (18–29 vs. 60–79year olds). Notwithstanding the decreasing long-term time trend of the dietary dioxin exposure in France, this probability still is expected to be 1.5% (95% CI: 0.3–2.5%) in 2030 in 60–79 olds. In the case of reproductive toxicity the probability of the 2009 body burden to exceed its reference ranged from 3.1% (95% CI: 1.4–5.0%) (18–29year olds) to 3.5% (95% CI: 2.2–5.2%) (30–44year olds). In 2030 this probability is negligible in 18–29year olds, however small though significant in 30–44year olds (0.7%, 95% CI: 0–1.6%). In the case of hepatic toxicity the probability in 2009 even in 60–79year olds already was negligible. In conclusion this approach indicates that in France dioxin levels in food form a declining, though still present, future health risk with respect to thyroid and reproductive toxicity.

Bioaccumulation and trophic transfer of short chain chlorinated paraffins in a marine food web from Liaodong Bay, North China.

Short chain chlorinated paraffins (SCCPs) are under the evaluation for inclusion into the Stockholm Convention on persistent organic pollutants. However, information on their bioconcentration and biomagnification in marine ecosystems is unavailable, limiting the evaluation of their ecological risks. In this study, seawater, sediment, zooplankton, invertebrates, and fishes collected from Liaodong Bay, Bohai Sea, North China were analyzed to investigate the residual level, congener group profile, bioaccumulation, and trophic transfer of SCCPs in a marine food web. The total concentrations of SCCPs ranged from 4.1 to 13.1 ng L(-1) in seawater, 65 to 541 ng g(-1) (dw) in sediment, and 86 to 4400 ng g(-1) (ww) in organisms. Correspondence analysis indicated the relative enrichment of C10Cl5 and C11Cl5 formula groups in most aquatic organisms. Both the logarithm bioaccumulation factors (log BAFs: 4.1-6.7) and biota-sediment accumulation factors (BSAFs: 0.1-7.3) of individual congeners implied the bioaccumulation of SCCPs. The trophic magnification factor (TMF) of ∑SCCPs was determined to be 2.38 in the zooplankton-shrimp-fish food web, indicating biomagnification potential of SCCPs in the marine ecosystem. The TMF values of individual congener groups significantly correlated with their log KOW values.

The stability of iso-α-acids and reduced iso-α-acids in stored blood specimens

The long-term stability of the iso-α-acids, and three structurally similar but chemically altered iso-α-acids (known as ‘reduced iso-α-acids’ and consisting of the rho-, tetrahydro- and hexahydro-iso-α-acid groups) were investigated in whole blood. Pools of blank blood spiked with the four beer-specific ingredient congener groups at two different concentration levels were stored at 20°C, 4°C and −20°C; and extracted in duplicate in weeks 1, 3, 5 and 8, using a previously published method. A loss of 15% of the initial concentration was considered to indicate possible instability and losses greater than 30% demonstrated significant losses. The individual analytes within the four iso-α-acid groups were also measured to determine which iso-α-acids were subject to greater degradation and were responsible for the overall group instability. All four iso-α-acid groups showed significant losses after 8 weeks of storage under room temperature conditions in particularly the natural iso-α-acid group where major losses were observed (96% and 85% losses for low and high concentrations, respectively). Some degradation in all iso-α-acid groups were seen at 4°C samples predominantly due to the ‘n’ analogs of the groups showing an increased instability in blood. The −20°C storage conditions resulted in minimal changes in concentrations of all analytes. Higher than frozen storage temperatures can result in substantial changes on the stability of the iso-α-acid type groups in blood. The aim of this study was to highlight the stabilities of the IAA analytes in order to assist in the interpretation of IAA in stored blood specimens.

Congener specific distribution and bioaccumulation of short-chain chlorinated paraffins in Liao estuary

Short-chain chlorinated paraffins(SCCPs) is a new candidate of persistent organic pollutants by the "Stockholm Convention". In this study, the occurrence, congener specific profiles, source and biota-sediment accumulation factor(BSAF) of SCCPs in sediments and biota samples collected from the Liao river estuary were investigated. The concentrations of SCCPs range from 64.9 to 1683.4 ng/g dw(mean 419.7) in the sediments and 1.55 to 11.9 μg/g dw(mean 6.14). C10 and C11 homologue groups of SCCPs are predominant in the sediments and organism with the summed relative contribution of 69.5% and 84.0%, respectively. Cl5, Cl6 and Cl7 congeners are the main congener groups in the sediments and organisms with the total relative contribution of 84.5% and 90.8%, respectively. The results also imply that the major pollution sources of SCCPs in this area are the productive activities and usage of CP-42 and CP-52, and one major source route is the riverine input. The average BSAF of ∑SCCPs(2.34) is higher than 1 shows an obvious bioaccumulation in mollusks. Significant negative correlation between BSAF and chlorine atoms(P0.05) is observed, indicating that the behavioral enrichment of zoobenthos and fish are quite different due to the influence of physicochemical properties and feeding way.

Serum concentrations of polychlorinated biphenyls (PCBs) in participants of the Anniston Community Health Survey

Serum concentrations of 35 ortho-substituted polychlorinated biphenyl congeners (PCBs) were measured in 765 adults from Anniston, Alabama, where PCBs were manufactured between 1929 and 1971. As part of the Anniston Community Health Survey (ACHS), demographic data, questionnaire information, and blood samples were collected from participants in 2005–2007. Forty-six percent of study participants were African-American, 70% were female, and the median age was 56years. The median concentration of the sum of 35 PCB congeners (ΣPCBs) was 528ng/g lipid, with a 90th percentile of 2600ng/g lipid, minimum of 17.0ng/g lipid, and maximum of 27,337ng/g lipid. The least square geometric mean ΣPCBs was more than 2.5 times higher for African-American participants than for White participants (866ng/g lipid vs. 331ng/g lipid); this difference did not change materially after adjustment for age, sex, body mass index (BMI) and current smoking. In spite of large differences in absolute PCB levels, relative contributions of individual congeners to ΣPCBs were quite similar between race groups. Nevertheless, while percent contributions to ΣPCBs for most of the most abundant penta- to heptachlorobiphenyls were higher among African-Americans, the percentages were higher in Whites for the lower-chlorinated PCBs 28 and 74 and for octa- to decachlorinated PCBs. No major differences were observed in geometric mean ΣPCBs between women and men when adjusted for age, race, BMI and current smoking (516ng/g lipid vs. 526ng/g lipid). Principal component analysis revealed groups of co-varying congeners that appear to be determined by chlorine substitution patterns. These congener groupings were similar between ACHS participants and the National Health and Nutrition Examination Survey (NHANES) 2003–04 sample of the general United States population, despite ACHS participants having serum concentrations of ΣPCBs two to three times higher than those in comparable age and race groups from NHANES.

A nanocomposite disk prepared from reduced graphene oxide and gold nanoparticles for the preconcentration of heterocyclic aromatic amines prior to their determination by HPLC

We report on a preconcentration disk for the determination of trace amounts of heterocyclic aromatic amines (HAAs) in the groups of quinoline and quinoxaline congeners as possible human carcinogens. The disk is based on nanocomposite (NC) prepared from graphene oxide as the precursor and from gold nanoparticles that act as building blocks to form a three-dimensional NC. If deposited in the sampling valve of a HPLC system, the material displays excellent extraction capability for HAAs owing to its large surface and π-π stacking interaction. Following an optimization of the extraction parameters, the method was successfully applied to the simultaneous determination of polar HAAs in meat samples with detection limit of 0.09 to 0.16 ng g−1 and recoveries of 69.5 to 122.7 %. The disk was used in more than 150 subsequent preconcentration cycles without obvious loss of the absorption capability. The results reveal that this new NC represents an excellent sorbent for purposes of preconcentration.