Chiral Signatures Research Articles

Effects of thiol antioxidants on the atropselective oxidation of 2,2',3,3',6,6'-hexachlorobiphenyl (PCB 136) by rat liver microsomes.

Chiral polychlorinated biphenyl (PCB) congeners, such as PCB 136, are atropselectively metabolized to various hydroxylated PCB metabolites (HO-PCBs). The present study investigates the effect of two thiol antioxidants, glutathione and N-acetyl-cysteine (NAC), on profiles and chiral signatures of PCB 136 and its HO-PCB metabolites in rat liver microsomal incubations. Liver microsomes prepared from rats pretreated with phenobarbital were incubated with PCB 136 (5 μM) in the presence of the respective antioxidant (0-10 mM), and levels and chiral signatures of PCB 136 and its HO-PCB metabolites were determined. Three metabolites, 5-136 (2,2',3,3',6,6'-hexachlorobiphenyl-5-ol), 4-136 (2,2',3,3',6,6'-hexachlorobiphenyl-4-ol), and 4,5-136 (2,2',3,3',6,6'-hexachlorobiphenyl-4,5-diol), were detected in all incubations, with 5-136 being the major metabolite. Compared to microsomal incubations without antioxidant, levels of 4,5-136 increased with increasing antioxidant concentration, whereas levels of PCB 136 and both mono-HO-PCBs were not affected by the presence of either antioxidant. PCB 136, 4-136, and 5-136 displayed significant atropisomeric enrichment; however, the direction and extent of the atropisomeric enrichment was not altered in the presence of an antioxidant. Because 4,5-136 can either be conjugated to a sulfate or glucuronide metabolite that is readily excreted or further oxidized a potentially toxic PCB 136 quinone, the effect of both thiol antioxidants on 4,5-136 formation suggests that disruptions of glutathione homeostasis may alter the balance between both metabolic pathways and, thus, PCB 136 toxicity in vivo.

Signatures of material and optical chirality: Origins and measures

Chirality in materials and light is of abiding interest across a broad range of scientific disciplines. This article discusses present and emerging issues in relation to molecular and optical chirality, also including some important developments in chiral metamaterials. Quantifying the chirality of matter or light leads to issues concerning the most appropriate measures, such as a helicity parameter for specific chiral chromophores and technical measures of light chirality. An optical helicity and chirality density depend on a difference between the numbers of left- and right-handed photons in a beam. In connection with circularly polarised luminescence, adoption of the Stokes parameter to spontaneous emission from chiral molecules invites critical attention. Modern spectroscopic techniques are often based on the different response arising from left-handed circularly polarised light compared to right-handed light. This dissimilarity can be exploited as a foundation for the separation of chiral molecules, promising new avenues of application.

Enantiomeric distribution of selected terpenes for authenticity assessment of Australian Melaleucaalternifolia oil

The growing awareness of a mounting trend toward adulteration of essential oil products has resulted in considerable interest among producer and consumer industries to develop suitable and cost-effective methods for authenticity control. In response to this trend, this study reports authenticity assessment of Australian tea tree oil (TTO) by means of stereospecific analysis of designated chiral monoterpenes present within the oil. Enantioselective gas chromatography (eGC) coupled with either flame ionization detection or mass spectrometry was used to determine the enantiomeric distribution of terpinen-4-ol and α-terpineol, both key chemical markers in TTO. Consistent enantiomeric ratios of 68.5±0.2% (+): 31.5±0.2% (–) for terpinen-4-ol and 74.2±1.4% (+): 25.8±1.4% (–) for α-terpineol were observed for the 57 authentic 100% pure Australian TTOs analyzed, which were sourced directly from different plantation sites throughout Australia. On the other hand, considerable variations from these ratios were observed for a number of commercial TTOs sampled from different continents, with 50% of the samples varying markedly from the ∼68.5% value found for (+) terpinen-4-ol. Robustness of the method and reliability of the attained results were evaluated by cross-checking data derived from the two independent analyses performed in this study. To the best of our knowledge, this work encapsulates the most comprehensive dataset currently available for the enantiomeric distribution of terpinen-4-ol and α-terpineol in pure Australian TTO, and which can serve as an important reference for detection of variation in commercially-sourced samples, and be a potential indicator of adulteration. Additionally, results of this study proved the considerable potential of using chiral compositions of terpinen-4-ol and α-terpineol as chiral signatures for authenticity assessment of TTO.

Effect of formulation and repeated applications on the enantioselectivity of metalaxyl dissipation and leaching in soil.

Soil incubation and column leaching experiments were conducted to address the question of whether the type of formulation (unsupported versus clay supported) and repeated applications of the chiral fungicide (RS)-metalaxyl affected the enantioselectivity of its dissipation and leaching in a slightly alkaline, loamy sand agricultural soil. Regardless of the type of formulation and the number of fungicide applications, the R-enantiomer of metalaxyl was degraded faster than the S-enantiomer, but the individual degradation rates of R- and S-metalaxyl were highly affected by the different application regimes assayed (t1/2 = 2-104 days). Repeated applications accelerated the degradation of the biologically active R-metalaxyl enantiomer, whereas they led to slower degradation of the non-active S-metalaxyl enantiomer. The type of formulation had less influence on the dissipation rates of the enantiomers. For all formulations tested, soil column leachates became increasingly enriched in S-enantiomer as the number of fungicide applications was increased, and application of metalaxyl to soil columns as clay-based formulations reduced the leaching of both enantiomers. Pesticide application conditions can greatly influence the enantioselective dissipation of chiral pesticides in soil, and hence are expected to exert a great impact on both the biological efficacy and the environmental chiral signatures of pesticides applied as mixtures of enantiomers or racemates to agricultural soils.

Hepatic metabolism affects the atropselective disposition of 2,2',3,3',6,6'-hexachlorobiphenyl (PCB 136) in mice.

To understand the role of hepatic vs extrahepatic metabolism in the disposition of chiral PCBs, we studied the disposition of 2,2′,3,3′,6,6′-hexachlorobiphenyl (PCB 136) and its hydroxylated metabolites (HO-PCBs) in mice with defective hepatic metabolism due to the liver-specific deletion of cytochrome P450 oxidoreductase (KO mice). Female KO and congenic wild type (WT) mice were treated with racemic PCB 136, and levels and chiral signatures of PCB 136 and HO-PCBs were determined in tissues and excreta 3 days after PCB administration. PCB 136 tissue levels were higher in KO compared to WT mice. Feces was a major route of PCB metabolite excretion, with 2,2′,3,3′,6,6′-hexachlorobiphenyl-5-ol being the major metabolite recovered from feces. (+)-PCB 136, the second eluting PCB 136 atropisomers, was enriched in all tissues and excreta. The second eluting atropisomers of the HO-PCBs metabolites were enriched in blood and liver; 2,2′,3,3′,6,6′-hexachlorobiphenyl-5-ol in blood was an exception and displayed an enrichment of the first eluting atropisomers. Fecal HO-PCB levels and chiral signatures changed with time and differed between KO and WT mice, with larger HO-PCB enantiomeric fractions in WT compared to KO mice. Our results demonstrate that hepatic and, possibly, extrahepatic cytochrome P450 (P450) enzymes play a role in the disposition of PCBs.

Polychlorinated biphenyls in surface soils of the Central Tibetan Plateau: Altitudinal and chiral signatures

The soils in the Central Tibetan Plateau (CTP), which is a unique background region, play an important role in the fate of the global cycling of polychlorinated biphenyls (PCBs). Forty-four soil samples from across the CTP were collected at altitudes between 3711 m and 5352 m, and the concentrations of 122 PCB congeners were measured from 66.98 to 150.81 ng/kg. The concentration of PCBs was positively correlated with the sampling altitude and clay content. Furthermore, enantiomeric fractions (EFs) of CB-95, CB-136 and CB-149 in soils of CTP were first determined. A (+)-enantiomer excess was identified for CB-136 and CB-149 in all of the samples investigated. Additionally, enantiomer-specific excess was found for CB-95. The dominance of enantiomer-specific excess decreased with increased the sampling altitude and congener concentration. It is likely that the addition of enantiomeric mixtures of PCBs from the atmosphere changed the EFs in the soils according to the altitude.

Chiral signature of α-HCH and o,p′-DDT in the soil and grass of the Central Tibetan Plateau, China

Enantiomeric fraction (EF) of organochlorine pesticides (OCPs) has been used as a signature for tracing the source and following pathways. The chiral analysis was performed for α-HCH and o,p′-DDT in paired soil and grass samples from the Central Tibetan Plateau (CTP), a unique background region. In the case of α-HCH, excess of (−) α-HCH was predominant in 83.3% of soil samples, and 80% of grass samples showed excess of (+) enantiomer. For o,p′-DDT, 90.9% of grass samples showed excess of (−) o,p′-DDT while 50% of soil samples showed excess of the (−) enantiomer. A correlation between EFs of soil and grass was not observed for either compound. The EFs of both compounds were correlated with soil concentration and with change of sampling altitude, within EFs being lower than racemic. However, these trends were not found in grass. Our study provides a database of EFs and signatures for OCPs in the CTP, one background region of the world.

Measuring chirality in NMR in the presence of a time-dependent electric field

Traditional nuclear magnetic resonance (NMR) experiments are "blind" to chirality since the spectra for left and right handed enantiomers are identical in an achiral medium. However, theoretical arguments have suggested that the effective Hamiltonian for spin-1/2 nuclei in the presence of electric and magnetic fields can be different for left and right handed enantiomers, thereby enabling NMR to be used to spectroscopically detect chirality even in an achiral medium. However, most proposals to detect the chiral NMR signature require measuring signals that are equivalent to picomolar concentrations for (1)H nuclei, which are outside current NMR detection limits. In this work, we propose to use an AC electric field that is resonantly modulated at the Larmor frequency, thereby enhancing the effect of the chiral term by four to six orders of magnitude. We predict that a steady-state transverse magnetization, whose direction will be opposite for different enantiomers, will build up during application of an AC electric field. We also propose an experimental setup that uses a solenoid coil with an AC current to generate the necessary periodic electric fields that can be used to generate chiral signals which are equivalent to the signal from a (1)H submicromolar concentration.

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 0.14–4.08ngg−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.

Elevated Levels of Polychlorinated Biphenyls in Plants, Air, and Soils at an E-Waste Site in Southern China and Enantioselective Biotransformation of Chiral PCBs in Plants

E-waste that contains polychlorinated biphenyls (PCBs) is moved across national boundaries, often from industrialized countries in the northern hemisphere, where the items were formerly used, to subtropical and tropical regions in southeastern Asia and Africa. As a result, there is a high likelihood that PCBs will be released into the environment from a primary source due to the elevated temperatures encountered in these low-latitude regions. In the present study, PCBs and enantiomer fractions (EFs) of chiral PCBs (PCB 84, 95, 132, 136, 149, and 183) were analyzed in air, eucalyptus leaves, pine needles, and soil at an e-waste site and a rural site in southern China. The concentrations of PCBs at the e-waste site ranged from 7825 to 76330 pg/m(3), 27.5 to 1993 ng/g, and 24.2 to 12045 ng/g in the air (gas plus particle), plant leaves, and soils, respectively. The atmospheric PCB composition profiles in the present study indicated relatively high abundances of penta- and hexa-PCBs, which were different from those previously observed in the air across China. The Clausius-Clapeyron regression analysis indicated that evaporation from local contaminated surfaces constitutes a primary emission source of PCBs in the air at the e-waste site. The chiral signatures of PCBs in the air at the e-waste site were essentially racemic (mean EFs = (0.484 ± 0.022)-(0.499 ± 0.004) in the gaseous phase) except for PCB 84 (0.420 ± 0.050), indicating that racemic sources dominate the PCB emission in the air. PCB chiral signatures in the soils ((0.422 ± 0.038)-(0.515 ± 0.016)) were similar to those in the air except for PCB 95. However, the chiral PCBs in the plants (especially the eucalyptus leaves) had significantly nonracemic residues ((0.368 ± 0.075)-(0.561 ± 0.045)) compared to those in the air and soil. This finding suggests that enantioselective biotransformation of these atropisomeric PCBs was very likely to occur in the plant leaves, possibly due to metabolism by cytochrome P-450 enzymes in leaves. To our knowledge, this is the first report on the enantioselective metabolism of chiral PCBs in plants under field conditions.

Microsomal Oxidation of 2,2′,3,3′,6,6′-Hexachlorobiphenyl (PCB 136) Results in Species-Dependent Chiral Signatures of the Hydroxylated Metabolites

Chiral polychlorinated biphenyls (PCBs) display variable atropisomeric enrichment in wildlife and animal models, especially at higher trophic levels. These differences in PCBs’ chiral signatures are, at least in part, due to species-dependent oxidation of PCBs to hydroxylated PCB metabolites (OH-PCBs). Here, we investigate the hypothesis that the cytochrome P450 (P450) enzyme-mediated oxidation of chiral PCBs results in species-dependent differences in the chiral signatures of OH-PCBs (i.e., the direction and extent of OH-PCBs’ atropisomeric enrichment). To investigate this hypothesis, we incubated PCB 136, a representative chiral PCB, with pooled human liver microsomes (HLMs) or liver microsomes from male guinea pig, hamster, monkey, mouse, and rabbit or female dog and determined average profiles and chiral signatures of the OH-PCBs. 2,2′,3,3′,6,6′-Hexachlorobiphenyl-4-ol (4–136) was the major metabolite in incubations with HLMs and monkey and rabbit microsomes. 2,2′,3,3′,6,6′-Hexachlorobiphenyl-5-ol (5–136) was the major metabolite formed by microsomes from all other species. Both 4–136 and 5–136 were formed atropselectively in all microsomal incubations; however, the direction and extent of the atropisomeric enrichment of both OH-PCB metabolites showed considerable differences across microsomal preparations obtained from different species. These differences in OH-PCBs’ atropisomeric enrichment may not only be toxicologically relevant but may also be useful to study sources and transport of OH-PCBs in the environment.

Temporal and spatial variation in polychlorinated biphenyl chiral signatures of the Greenland shark (Somniosus microcephalus) and its arctic marine food web

Polychlorinated biphenyls (PCBs) chiral signatures were measured in Greenland sharks (Somniosus microcephalus) and their potential prey in arctic marine food webs from Canada (Cumberland Sound) and Europe (Svalbard) to assess temporal and spatial variation in PCB contamination at the stereoisomer level. Marine mammals had species-specific enantiomer fractions (EFs), likely due to a combination of in vivo biotransformation and direct trophic transfer. Greenland sharks from Cumberland Sound in 2007–2008 had similar EFs to those sharks collected a decade ago in the same location (PCBs 91, 136 and 149) and also similar to their conspecifics from Svalbard for some PCB congeners (PCBs 95, 136 and 149). However, other PCB EFs in the sharks varied temporally (PCB 91) or spatially (PCB 95), suggesting a possible spatiotemporal variation in their diets, since biotransformation capacity was unlikely to have varied within this species from region to region or over the time frame studied.

Residues and enantiomeric profiling of organochlorine pesticides in sediments from Xinghua Bay, southern East China Sea

The spatial distribution and chiral signatures of organochlorine pesticides (OCPs) in the surface sediments of Xinghua Bay, southern East China Sea, were investigated. The total OCP concentrations ranged from 9.15 to 40.5 ng/g dry weight, with a predominance of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs). The isomer ratios of α-HCH/γ-HCH (less than 1.0) and the predominant β-HCH implied that HCH residues were derived not only from historical technical HCH use but also from the additional use of lindane in this area. The isomer ratios of p,p′-DDT/(p,p′-DDD + p,p′-DDE) and o,p′-DDT/p,p′′-DDT, and a strong correlation (R = 0.83, P < 0.001) between p,p′-DDE and o,p′-DDT depicted a cocktail input pattern of dicofol-type DDT and technical DDT. Moreover, the fact that only cis-chlordane was detectable for all sampling stations suggested the past application of technical chlordane. Based on the sediment quality guidelines (SQG), γ-HCH is the main OCP species of ecotoxicological concern in Xinghua Bay. Enantiomeric analysis showed that the (+)-enantiomers of α-HCH and o,p′-DDT were more prevalent than the (−)-enantiomers in most samples, whereas both racemic and nonracemic residues existed for o,p′-DDD. These results implied that the SQG of chiral OCPs should be reassessed using concentrations of their individual enantiomers.

Oxidation of Polychlorinated Biphenyls by Liver Tissue Slices from Phenobarbital-Pretreated Mice Is Congener-Specific and Atropselective

Mouse models are powerful tools to study the developmental neurotoxicity of polychlorinated biphenyls (PCBs); however, studies of the oxidation of chiral PCB congeners to potentially neurotoxic hydroxylated metabolites (OH-PCBs) in mice have not been reported. Here, we investigate the atropselective oxidation of chiral PCB 91 (2,2',3,4',6-pentachlorobiphenyl), PCB 95 (2,2',3,5',6-pentachlorobiphenyl), PCB 132 (2,2',3,3',4,6'-hexachlorobiphenyl), PCB 136 (2,2',3,3',6,6'-hexachlorobiphenyl), and PCB 149 (2,2',3,4',5',6-hexachlorobiphenyl) to OH-PCBs in liver tissue slices prepared from female mice. The metabolite profile of PCB 136 typically followed the rank order 5-OH-PCB > 4-OH-PCB > 4,5-OH-PCB, and metabolite levels increased with PCB concentration and incubation time. A similar OH-PCB profile was observed with the other PCB congeners, with 5-OH-PCB/4-OH-PCB ratios ranging from 2 to 12. More 5-OH-PCB 136 was formed in liver tissue slices obtained from animals pretreated with phenobarbital (P450 2B inducer) or, to a lesser extent, dexamethasone (P450 2B and 3A enzyme inducer) compared to tissue slices prepared from vehicle-pretreated animals. The apparent rate of 5-OH-PCBs formation followed the approximate rank order PCB 149 > PCB 91 > PCB 132 ∼ PCB 136 > PCB 95. Atropselective gas chromatography revealed a congener-specific atropisomeric enrichment of major OH-PCB metabolites. Comparison of our results with published OH-PCB patterns and chiral signatures (i.e., the direction and extent of the atropisomeric enrichment) from rat liver microsomal revealed drastic differences between both species, especially following the induction of P450 2B enzymes. These species differences in the metabolism of chiral PCBs should be considered in developmental neurotoxicity studies of PCBs.

Discrete Nanocubes as Plasmonic Reporters of Molecular Chirality

One of the most intriguing structural properties, chirality, is often exhibited by organic and bio-organic molecular constructs. Chiral spectral signatures, typically appearing in the UV range for organic materials and known as circular dichroism (CD), are widely used to probe a molecular stereometry. Such probing has an increasingly broad importance for biomedical and pharmacological fields due to synthesis/separation/detection of homochiral species, biological role of chiral organization, and structural response to environmental conditions and enantiomeric drugs. Recent theoretical and experimental works demonstrated that the CD signal from chiral organic molecules could appear in the plasmonic (typically, visible) band when they coupled with plasmonic particles. However, the magnitude of this CD signal, induced by discrete nonchiral plasmonic particles, and its native molecular analog were found to be comparable. Here we show that shaped nonchiral nanoparticles, namely, gold/silver core/shell nanocubes, can act as plasmonic reporters of chirality for attached molecules by providing a giant, 2 orders of magnitude CD enhancement in a near-visible region. Through the experimental and theoretical comparison with nanoparticles of other shapes and materials, we demonstrate a uniqueness of silver nanocube geometry for the CD enhancement. The discovered phenomenon opens novel opportunities in ultrasensitive probing of chiral molecules and for novel optical nanomaterials based on the chiral elements.

Handedness detected by microwaves

Traditional methods for detecting and identifying the handedness of molecules — their chirality — have been based on the same theoretical concept. A technique has been reported that departs from this paradigm. See Letter p.475 Chiral molecules exist as enantiomers that form non-superimposable mirror images, and chirality has a fundamental role in many aspects of chemistry and biology. It is notoriously difficult to detect and quantify chirality because conventional spectroscopic methods exploit weak effects that produce weak signals. Patterson et al. now show that microwave spectroscopy combined with a switched electric field can map the sign of an electric dipole Rabi frequency — a variable that depends directly on the chirality of the molecule — onto the phase of emitted microwave radiation. The effect is then used to determine the chirality of cold gas-phase molecules, illustrated with S and R enantiomers of 1,2-propanediol and their racemic mixture. The method produces large and definitive signatures of chirality, and is both sensitive and species-selective — making it a potentially ideal and unique tool for determining the chirality of multiple species in a mixture.

Enantiomer-specific detection of chiral molecules via microwave spectroscopy

Chirality plays a fundamental part in the activity of biological molecules and broad classes of chemical reactions, but detecting and quantifying it remains challenging. The spectroscopic methods of choice are usually circular dichroism and vibrational circular dichroism, methods that are forbidden in the electric dipole approximation. The resultant weak effects produce weak signals, and thus require high sample densities. In contrast, nonlinear techniques probing electric-dipole-allowed effects have been used for sensitive chiral analyses of liquid samples. Here we extend this class of approaches by carrying out nonlinear resonant phase-sensitive microwave spectroscopy of gas phase samples in the presence of an adiabatically switched non-resonant orthogonal electric field; we use this technique to map the enantiomer-dependent sign of an electric dipole Rabi frequency onto the phase of emitted microwave radiation. We outline theoretically how this results in a sensitive and species-selective method for determining the chirality of cold gas-phase molecules, and implement it experimentally to distinguish between the S and R enantiomers of 1,2-propanediol and their racemic mixture. This technique produces a large and definitive signature of chirality, and has the potential to determine the chirality of multiple species in a mixture.

Importance of Arctic Zooplankton Seasonal Migrations for α-Hexachlorocyclohexane Bioaccumulation Dynamics

Like most zooplankton, Calanus hyperboreus undergoes seasonal migration spending late spring and summer grazing at the surface and the rest of the year in diapause at depth. As a result, in the Arctic Ocean this copepod resides for part of the year in the hexachlorocyclohexane (HCH) enriched surface water and for part of the year at depth where HCH undergoes significant microbial degradation resulting in far lower concentrations (~3 times for α-HCH). We collected C. hyperboreus from summer and winter from the Amundsen Gulf and measured their α-HCH concentrations, enantiomeric compositions, and bioaccumulation factors (BAFs) to investigate how this copepod responds to the change in exposure to α-HCH. C. hyperboreus collected in winter were also cultured for 5 weeks under surface water conditions without feeding to investigate bioconcentration dynamics following spring ascent. Concentration of α-HCH was 2-3 times higher in individuals from the summer than those from the winter. Log BAF from the summer (feeding period) does not exceed log BCF (bioconcentration factor) from the culturing experiment (no feeding) suggesting that α-HCH concentration in C. hyperboreus is maintained through equilibration rather than feeding. After the spring ascent from deep waters, C. hyperboreus approach equilibrium partitioning with the higher surface water concentrations of α-HCH within 3-4 weeks with about 60% of bioconcentration taking place in the first week. The C. hyperboreus α-HCH chiral signature also reflects ambient seawater and can therefore be used as a determinant of residence depth. Even though a single cycle of seasonal migration does not result in a significant redistribution of α-HCH in the water column, this process could have a significant cumulative effect over longer time scales with particular local importance where the zooplankton biomass is high and the ocean depth is great enough to provide substantial vertical concentration gradients.

Polychlorinated biphenyls in human hair at an e-waste site in China: Composition profiles and chiral signatures in comparison to dust

We analyzed the polychlorinated biphenyls (PCBs) in human hair collected from an electronic waste (e-waste) recycling area in southern China and compared their composition profiles and chiral signatures to those of workplace and domestic dust. The PCB concentrations showed significant age dependence in dismantling workers' hair but not in residents' hair. Among residents, PCB concentrations decreased in the following order: elderly people>students>pre-school children>adults. The PCB homologue and congener profiles of the workers' hair were similar to those of the workplace dust. However, the PCB homologue profile of the residents' hair was clearly different from that of the domestic dust. The chiral congener CB95 generally exhibited a racemic or near-racemic composition in both hair and dust, with enantiomer fractions (EFs) ranging from 0.485 to 0.525 in hair and from 0.479 to 0.504 in dust. The EFs of CB132 in dust (0.477–0.513) were closer to a racemic chiral signature than those in hair (0.378–0.521), but this difference was not significant. Our results suggest that the chiral signature of PCBs may be a better tool than the PCB composition profile for identifying the external and internal sources of organic contaminants in human hair. Further measurements of chiral PCB signatures in hair and blood from the same individuals are needed to identify the external and internal sources of PCBs in human hair.

Assessing ongoing sources of dissolved-phase polychlorinated biphenyls in a contaminated stream

Few studies assess the potential of ongoing sources of "fresh" polychlorinated biphenyls (PCBs) to aquatic systems when direct discharge to the environment has been eliminated. In the present study, the authors used single-layered, low-density polyethylene samplers (PEs) to measure total PCB concentrations, congener profiles, and enantiomeric fractions (EFs) in a contaminated stream and to provide multiple lines of evidence for assessing ongoing inputs of PCB. Concentrations were well above background levels that have been monitored for years. Concentrations significantly increased with distance, the farthest downstream PE concentrations being almost five times greater than those at 79 m downstream of a historical point source. The PCBs in the PEs at 79 m downstream of the contamination source were dominated by low K(OW) congeners, similar to those in the mixture of Aroclors 1016 and 1254 (4:1 v/v) historically released from the former capacitor manufacturer. The only two chiral congeners detected in the PEs downstream were PCBs 91 and 95. The EF values were nonracemic for PCB 91, while the values were either racemic or near racemic for PCB 95. Increased PCB concentrations with distance and a congener composition of predominantly low-weight congeners in the PEs at 79 m downstream of the plant site suggested an ongoing PCB source from the plant site. Chiral signatures suggested aerobic biotransformation of dissolved PCBs but did not shed any light on possible ongoing PCB inputs.