Persistent and toxic chemical pollutants in fish consumed by Asians in Chicago, United States.

Consumption of seafood brings health benefits but may increase the ingestion of contaminants. Compared with other ethnic groups in the U.S., Asians consume seafood more frequently. However, there is little information about how culturally specific fish consumption contributes to exposure to toxicants. In this work, we surveyed fish consumption among Chinese, Korean and Vietnamese communities and purchased 103 seafood samples from local markets in Chicago. Each sample was analyzed for mercury (Hg) and 92 organic chemicals including polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), and Dechlorane Plus and related compounds (DPs). The rank order of pollutant concentration in all samples was Hg â‰« Σ66PCBs > Σ17OCPs > Σ8PBDEs > Σ8DPs. Positive correlations were noted among most contaminant groups. Bluefish, pike and tuna steak had the highest mean Hg (>1 mg/kg). The mean Σ66PCBs was highest in pike and bluefish (>100 ng/g) followed by pollock and mackerel (>40 ng/g). Overall, octopus, shrimp and tilapia were the least contaminated; while pike, bluefish, and pollock were the most contaminated. Omega-3 fatty acids were more strongly affiliated with the organic contaminants than mercury. A risk assessment identified seven types of fish that should have consumption limitations and six that should not be consumed. For these seafoods, consumption advice based on Hg levels would adequately protect health. In the survey participants, 17% of seafood mass consumed is from types of fish that should be limited to 1 or 2 meals/week, while 7% of the seafood mass consumed comes from types that should not be consumed at all. This work adds additional contaminants to the profile of health risks resulting from fish consumption among Asian Americans, which can be used in interventions aimed at conserving consumption of healthy fish while avoiding contaminants.

Deviations from Beer's law in electronic absorption and circular dichroism: Detection for enantiomeric excess analysis.

The electronic absorption (UV) to circular dichroism (CD) signal ratio can be used for enantiomeric excess (ee) analysis within linear range. However, CD detection often requires a high sample concentration where deviations from Beer's law may occur. Individual enantiomers of four chiral compounds were separated from commercial racemates by semipreparative high-performance liquid chromatography (HPLC) with chiral columns. They were used to trace possible deviations in both UV and CD detection on achiral HPLC with a photodiode array detector and a CD detector. The CD/UV ratios for samples with the same ee value decreased by up to 7.8 to 52% when the injection volume increased, indicating that the linear standard curve of ee versus CD/UV is only valid within a narrow range. To extend the sample amount to a wider range, a data-processing method was developed based on two second-order polynomial functions, which were constructed to fit the relationship between the intensities of the UV and CD signals for two enantiomers. Moreover, a more simplified method based on a third-order polynomial function was established to calculate the ee values. The variations between the predicted and experimental ee values were within ±0.08 for both methods. To our knowledge, this is the first study that the deviations from Beer's law are considered in both UV and CD detection for ee analysis.

Photochemical degradation of polyhalogenated carbazoles in hexane by sunlight.

Polyhalogenated carbazoles (PHCZs) are a class of halogenated dibenzopyrrole, which have been increasingly detected in the environment and found to be bioaccumulative and potentially toxic. However, their environmental transformation potential is largely unknown. In this study, UV absorption spectra of carbazole (CZ) and 10 PHCZs were obtained with wavelength range 290-400 nm, and three peaks were identified in most cases with the highest occurring around 300 nm. Hexane solutions of CZ, 10 individual PHCZs, and a sediment extract containing nine other PHCZs were separately irradiated under natural sunlight in order to investigate their photodegradation kinetics and pathways. The pseudo-first-order reaction rate constants (k) of these PHCZs varied from 0.183 h-1 to 2.394 h-1, and increased exponentially with increasing numbers of chlorines and bromines in PHCZ molecules. Contribution to ln k from each bromine atom is more than doubling of that from each chlorine atom. Stepwise reduction debromination was confirmed to be one of the photodegradation mechanisms for both brominated and mixed halogenated (containing both bromine and chlorine) carbazoles. Only sporadic dechlorinated products were found during the photolysis of chlorinated carbazoles. By adopting a simplified kinetic approach, we estimated that dehalogenation contributed approximately 20% to 51% of the total loss of the parent PHCZs.

Enantioseparation and identification for the rationalization of the environmental impact of 4 polychlorinated biphenyls.

Polychlorinated biphenyls (PCBs) are harmful and persistent organic pollutants that have long been used in industrial manufacturing. Their persistence leads to accumulation in the food chain causing potential toxic effects. As 19 out of 78 of the chiral congeners have stable atropisomers at ambient temperature, we studied some typical enantiomers: PCB45, PCB95, PCB136, and PCB149. The chiral stationary phases OD-H and OJ-H were used for separation in analytic high-performance liquid chromatography (HPLC), as well as for collection in semi-preparative HPLC. The resolution was optimized with respect to n-hexane-based mobile phases, temperature, and flow rate. All pure enantiomers were recovered from semi-preparative HPLC within 15 minutes for practical purpose. Characterization of the absolute configurations were conducted with a combination of theoretical and experimental electronic circular dichroism measurements. The enantiomers of PCB45, PCB95, PCB136, and PCB149 proved to be eluted as R > S, S > R, R > S, and S > R, respectively. Molecular structures (eg, substituent groups) and properties (eg, bond lengths, bond angles, and dipole moments) were quantitatively analyzed to understand the toxicity effect of PCBs. In summary, we have developed a well-established methodology of collection and configuration identification for analogous PCB derivatives.

Spatial distribution and implications to sources of halogenated flame retardants in riverine sediments of Taizhou, an intense e-waste recycling area in eastern China.

Concentrations and spatial distribution pattern of organohalogen flame retardants were investigated in the riverine surface sediments from Taizhou, an intensive e-waste recycling region in China. The analytes were syn- and anti- Dechlorane Plus (DP), Dechloranes 602, 603, and 604, a DP monoadduct, two dechlorinated DPs and 8 congeners of polybrominated diphenyl ethers (PBDEs). The concentrations of Σ8PBDEs, ΣDP, ΣDec600s, and ΣDP-degradates ranged from <100 to 172,000, 100 to 55,000, not detectable (nd) to 1600, and nd to 2800 pg/g dry weight, respectively. BDE-209 and DP, both have been manufactured in China, had similar spatial distribution patterns in the study area, featured by distinctly recognizable hotspots some of which are in proximity to known e-waste dumping or metal recycling facilities. Such patterns were largely shared by Dec602 and dechlorinated DP, although their concentration levels were much lower. These major flame retardants significantly correlate with each other, and cluster together in the loading plot of principle component analysis. In contrast, most non-deca PBDE congeners do not correlate with DPs. Dec604 stood out having distinctly different spatial distribution pattern, which could be linked to historical use of mirex. Organic matter content of the sediment was not the dominant factor in determining the spatial pattern of pollution by halogenated flame retardants in the rivers of this study.

Metolachlor stereoisomers: Enantioseparation, identification and chiral stability.

Metolachlor is a chiral herbicide consisting of four stereoisomers, which is typically used as a racemic mixture or is enriched with the herbicidally active 1'S-isomers. Because studies on the enantioselective behavior of phyto-biochemical processes and the environmental fate of metolachlor have become significant, a practical method for analyzing and separating metolachlor stereoisomers must be developed. In the present study, the enantiomeric separation of metolachlor was achieved using OD-H, AS-H, OJ-H and AY-H chiral columns. The effects of different organic modifiers in an n-hexane-based mobile phase were investigated, and various temperatures and flow rates, which may influence metolachlor separation, were also explored. The optimal resolution was obtained using an AY-H column with n-hexane/EtOH (96/4) as the mobile phase at a rate and temperature of 0.6mLmin(-1) and 25°C, respectively. The absolute configuration of the four stereoisomers was identified as αSS, αRS, αSR, αRR using computed and experimentally measured ECD and VCD spectra. Thermal interconversion and solvent stability experiments were also performed. Pure metolachlor stereoisomers in different organic solvents and water at 4°C or 30°C were stable. These results were used to establish a sound method for analyzing, preparing, characterizing, and preserving individual metolachlor stereoisomers in most natural environments.

Residues and chiral signatures of organochlorine pesticides in mollusks from the coastal regions of the Yangtze River Delta: source and health risk implication.

The residues and enantiomeric fractions of organochlorine pesticides (OCPs) were measured in 11 mollusk species collected from the coastal areas along the Yangtze River Delta to evaluate the status, potential sources, and health risks of pollution in these areas. The concentrations of DDTs, HCHs, and chlordanes ranged from 6.22 to 398.19, 0.66-7.11, and 0.14-4.08 ng g(-1) based on wet weight, respectively; DDTs and HCHs have the highest values, globally. The DDTs increased and the HCHs decreased compared to historical data. Both the box-and-whisker plots and the one-way ANOVA tests indicated that the OCP levels varied little between sampling locations and organism species. The compositions of the DDTs and HCHs suggested a cocktail input pattern of fresh and weathered technical products. The comparative EF values for the α-HCH between the sediments and mollusks, as well as the lack of any discernible difference in the relative proportions of HCH isomers among different species from the same sampling site implied that the HCH residues in the mollusks came directly from the surrounding environment. However, the biotransformation of DDTs in mollusks cannot be precluded. The assessments performed based on several available guidelines suggested that although no significant human health risks were associated with the dietary intake of OCPs, the concentrations of DDTs exceeded the maximum residual limits of China and many developed nations. Moreover, an increased lifetime cancer risk from dietary exposure to either DDTs or HCHs remains a possibility. Because non-racemic OCP residues are common in the mollusk samples, our results suggest a need to further explore the levels and toxicity of the chiral contaminants in mollusks and other foodstuff to develop the human risk assessment framework based on chiral signatures.

Residues, sources and tissue distributions of organochlorine pesticides in dog sharks (Mustelus griseus) from Zhoushan Fishing Ground, China.

Ten dog sharks (Mustelus griseus) collected from Zhoushan Fishing Ground, China, were analysed for organochlorine pesticides in various tissues, including muscle, liver, skin, gill and fin, with the aim to study the residues, sources and tissue distributions of these chemicals in high trophic level marine fishes. The concentrations of DDTs, HCHs, and chlordanes varied from 7.27-26.62, 2.67-3.35, and 0.54-0.61 ng/g wet weight, respectively, with the estimated daily intake far below the acceptable daily intake and Chinese edible hygienic criteria. Data from the tissue distribution suggested a tendency of DDTs and chlordanes to accumulate in the liver, but for HCHs, direct gill penetration may be an important means of entrance. In addition, the compositional profiles indicated that the residues of HCHs and chlordanes mainly originated from the historical usage of these chemicals. However, the predominant maternal compounds and the o,p'-DDT/p,p'-DDT ratios reflected a recent use of dicofol.