•Environmental behaviour of SCCPs was investigated in both aquatic and terrestrial ecosystems in the Arctic.•No biomagnification of SCCPs was found between cod and gammarid species.•SCCPs were bio-accumulated in vegetation samples in the terrestrial ecosystems.•The number of carbon atoms had a greater influence on the BAFs of SCCPs in terrestrial species than that of the number of chlorine atoms.The environmental behaviour of short-chain chlorinated paraffins (SCCPs) was investigated in both aquatic and terrestrial ecosystems in the Arctic. The mean concentrations of SCCPs in the aquatic and terrestrial samples were 178.9 ng/g dry weight (dw) and 157.2 ng/g dw, respectively. Short carbon chain (C10) and less-chlorinated (Cl6) congener groups were predominant in the Arctic samples, accounting for 48.6% and 34.8% of the total SCCPs, respectively. The enrichment of lighter SCCP congener groups (i.e., fewer chlorine atoms with shorter carbon chain lengths) indicated that the fractionation process occurred during long-range transport. The biomagnification factor (BMF) was 0.46 from gammarid to cod, which indicated that the SCCPs did not biomagnify between these two species. The soil–vegetation bioaccumulation factor (BAF) of SCCPs was 29.9, and C13 and Cl7, 8 congener groups tended to accumulate in the terrestrial vegetation. Regression analysis (BAFs = 10.9 × #C + 5.6 × #Cl − 125.2, R = 0.53, P < 0.01) showed that the number of carbon and chlorine atoms influenced the bioaccumulative behaviour of SCCPs and suggested that the number of carbon atoms had a greater influence on the BAFs of SCCPs in the terrestrial ecosystem than did the number of chlorine atoms.Download high-res image (205KB)Download full-size image

Polybrominated diphenyl ethers (PBDEs), one typical type of persistent environmental contaminant, have toxicological effects such as disrupting thyroid homeostasis in the human body. The high binding affinities of hydroxylated metabolites of PBDEs (OH-PBDEs) with transthyretin (TTR) were considered to be one major reason for their extraordinary capacity of passing through the blood–brain barrier via competitive thyroid hormone (T4) transport protein binding. Recent findings showed that sulfated PBDEs can be formed in human liver cytosol as phase-II metabolites. However, experimentally determined data for the TTR binding potential of the sulfated PBDEs are still not available. Therefore, molecular docking and molecular dynamics (MD) simulations were employed in the present study to probe the molecular basis of TTR interacting with hydroxylated and sulfated PBDEs at the atomic level. The docking scores of LeDock were used to construct the structure-based predictive model. The calculated results showed that the sulfated PBDEs have stronger affinity for TTR than the corresponding OH-PBDEs. Further analysis of structural characteristics based on MD simulations indicated that upon the binding of PBDE metabolites, the stability of TTR was enhanced and the dissociation rate of the tetrameric protein structure was potentially decreased. Subsequent binding free energy calculations implied that van der Waals interactions are the dominant forces for the binding of these metabolites of PBDEs at the T4 site of TTR. The residues Ser117/Ser117′ and Lys15/Lys15′ were identified, by both residue energy decomposition and computational alanine-scanning mutagenesis methods, as key residues which play an important role in determining the binding orientations of the –OSO3− group of sulfated PBDEs by formation of either hydrogen bonds or electrostatic interactions, respectively. In general, the combination of docking calculations with MD simulations provided a theoretically toxicological assessment for the metabolites of PBDEs, deep insight into the recognition mechanism of TTR for these compounds, and thus more comprehensive understanding of the thyroid-related toxic effects of PBDEs as well.

•The effect of concentration on OTC photolysis was pH dependent.•PH was the key factor controlling the direct photolysis rate of OTC.•The photolysis rate increased as temperature increased at neutral pH.•The photolysis quantum yields were derived with the order L2－ > H2L± > HL－ > H3L＋.•A mathematical approach was proposed for calculating the photolysis quantum yield.Oxytetracycline (OTC) commonly undergoes direct photolysis as the main elimination pathway in surface waters. The photolysis of OTC was studied as a function of initial concentration, pH and temperature. The experiments were performed in the absence of oxygen to avoid oxygen induced indirect photolysis. The photolysis rate decreased when increasing the initial OTC concentration, and was accelerated as raising the temperature. pH was the key factor controlling the photolysis rate. By measuring the UV–vis absorption spectra of OTC under various pH conditions and fitting them with global analysis, four OTC species H3L＋, H2L±, HL−, and L2− (L represents OTC) were decomposed, meanwhile, the acid dissociation constant of OTC and the molar absorption coefficient of each species were resolved. Because apparent photolysis rate constants under varied light source conditions are often incomparable, therefore the direct photolysis quantum yield of OTC species were calculated by a mathematical approach which based on the molar absorption coefficients, the species composition and apparent kinetic rates of OTC under experimental pH conditions. The result shows the photolysis quantum yield of OTC followed the order L2－ > H2L± > HL－ > H3L＋. The direct photolysis rates of OTC were tightly correlated to the energy dissipation processes at the excited states, e.g., the excited states inter-/intramolecular proton transfer (ESIPT), and the molecular conformation transfer induced internal energy transmission between ground state and excited state. Fluorescence emission was not an important energy dissipation process. The results of this study provide the useful parameters for predicting the environmental fate of OTC in surface waters. And the approach for calculating the photolysis quantum yield is also available for other antibiotics with multiple pKa values.

Short chain chlorinated paraffins (SCCPs) are not only research focus of environmental issues but also interesting model molecules for organic chemistry which exhibit diverse conformation preference and intramolecular noncovalent interactions (NCIs). A systematic study was conducted to reveal the conformation preference and the related intramolecular NCIs in two C10-isomers of SCCPs, 5,5,6,6-tetrachlorodecane and 4,4,6,6-tetrachlorodecane. The overall conformation profile was determined on the basis of relative energies calculated at the MP2/6-311++G(d,p) level with the geometries optimized by B3LYP/6-311++G(d,p) method. Then, quantum theory of atoms in molecules (QTAIM) has been adopted to identify the NCIs in the selected conformers of the model molecules at both B3LYP/6-311++G(d,p) and M06-2X/aug-cc-pvdz level. Different chlorine substitution modes result in varied conformation preference. No obvious gauche effect can be observed for the SCCPs with chlorination on adjacent carbon atoms. The most stable conformer of 5,5,6,6-tetrachlorodecane (tTt) has its three dihedral angles in the T configuration, and there is no intramolecular NCIs found in this molecule. On the contrary, the chlorination on interval carbon atoms favors the adoption of gauche configuration for the H–C–C–Cl axis. Not only intramolecular H···Cl contacts but also H···H interactions have been identified as driving forces to compensate the instability from steric crowding of the gauche configuration. The gggg and g′g′g′g′ conformers are the most popular ones, while the populations of tggg and tg′g′g′ conformer are second to those of the gggg and g′g′g′g′ conformers. Meanwhile, the M06-2X method with large basis sets is preferred for identification of subtle intramolecular NCIs in large molecules like SCCPs.

In this study, serum and urine samples were collected from 36 occupational workers in a fluorochemical manufacturing plant in China from 2008 to 2012 to evaluate the body burden and possible elimination of linear and branched perfluoroalkyl acids (PFAAs). Indoor dust, total suspended particles (TSP), diet, and drinking water samples were also collected to trace the occupational exposure pathway to PFAA isomers. The geometric mean concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorohexanesulfonate (PFHxS) isomers in the serum were 1386, 371, and 863 ng mL–1, respectively. The linear isomer of PFOS, PFOA, and PFHxS was the most predominant PFAA in the serum, with mean proportions of 63.3, 91.1, and 92.7% respectively, which were higher than the proportions in urine. The most important exposure routes to PFAA isomers in the occupational workers were considered to be the intake of indoor dust and TSP. A renal clearance estimation indicated that branched PFAA isomers had a higher renal clearance rate than did the corresponding linear isomers. Molecular docking modeling implied that linear PFOS (n-PFOS) had a stronger interaction with human serum albumin (HSA) than branched isomers did, which could decrease the proportion of n-PFOS in the blood of humans via the transport of HSA.

Enhanced regulations, centralized dismantling processes, and sophisticated recycling technologies have been implemented in some e-waste dismantling areas in China with regard to environmental and economic aspects since 2005. In this study, rice grain samples were collected from 2006 to 2010 in an e-waste dismantling area to investigate the temporal trends and spatial distribution of As, Cd, Cu, and Pb. Geometric means of As, Cd, Cu, and Pb in rice samples from the e-waste dismantling area were 111, 217, 4676, and 237 ng g–1, respectively. Levels of Pb showed a significant decreasing trend during the sampling period, whereas the other three elements remained relatively constant or even increased. Concentrations of Cd, Cu, and Pb in the e-waste dismantling area were significantly higher than those in the non-e-waste dismantling area (p < 0.05), which showed a close connection between e-waste dismantling activities and elevated Pb, Cu, and Cd contents. Risk assessment for human via rice consumption indicated that over 60% of the hazard quotient of Cd exceeded 1 in the e-waste dismantling area. Our study implied that stricter implementation of regulatory measures might lead to positive effects in controlling the release of some heavy metals to the environment. However, environmental behaviors differed with geochemical characteristics of individual elements. Further remediation actions to reduce heavy metal pollution to the surrounding environment might still be needed.

In the present work, the infrared (IR) and Raman spectra of 2,2′,4,4′-tetrabromodiphenyl ether have been measured in the ranges of 400–4000 cm−1 and 100–4000 cm−1. The geometry optimized by the density functional theory Becke-3-Lee-Yang-Parr (B3LYP) method with the 6-31G(d) basis set was in good agreement with the experimental data of analogues. The results have shown that the dihedral angle of biphenyl ether significantly increases with the addition of bromine substitution. The vibrational frequencies were evaluated by the B3LYP method in conjunction with basis sets of 6-31G(d), 6-31G(2df,p), 6-311+G(d,p), 6-311G+(2df,p), and 6-311++G(d,p), separately. The scaled frequencies resulted in excellent agreement with the observed spectral patterns. The correlation analysis and statistical comparisons indicated that the basis sets larger than 6-31G(d) resulted in no significant improvement in the accuracy of the vibration frequencies. The detailed assignments were performed according to the calculated results for B3LYP/6-31G(d) and then compared with those from a previous study on 4,4′-dibromodiphenyl ether. The absence of coupling of C–O stretching and adjacent C–H in-plane deformation indicated a strong steric effect owing to the ortho bromine atoms in the title compound. Moreover, the quantum theory of atoms in molecules (QTAIM) and the Moller–Plesset second-order perturbation (MP2) method are applied to exclude the possible formation of intramolecular non-covalent interactions such as Br⋯Br and C–H⋯Br.

•Occurrence of SCCPs in Antarctic biota samples were investigated for the first time.•Shorter chain congeners have higher potential for long-range transport.•C10 congeners and Cl6–7 congeners predominated in Antarctic samples.•Anthropogenic discharge introduced contemporary SCCPs to the local environment.•SCCPs showed biomagnification potential between Ngas and Agas samples.As a candidate persistent organic pollutant of the Stockholm Convention, short-chain chlorinated paraffins (SCCPs) have recently received particular attention. In this study, we investigated, for the first time, the concentrations of SCCPs in biota samples collected from the Fildes Peninsula at King George Island and Ardley Island, Antarctica. The concentrations of SCCPs ranged from 3.5 to 256.6 ng/g (dry weight, dw), with a mean of 76.6 ± 61.8 ng/g dw, which was lower than those detected in mid- and low-latitude regions. The long-range transport behaviour of SCCPs was confirmed by both the detection of SCCPs in Antarctic remote areas and their special congener profiles. Short carbon chain (C10) congeners predominated in the Antarctic samples, which accounted for 56.1% of the total SCCP contamination. Such enrichment of C10 congeners indicated the high potential for the long-range transport of shorter chain congeners. In addition, SCCPs tended to be enriched in the species with high lipid contents. The biomagnification potential of SCCPs was found between Archeogastropoda (Agas) and Neogastropoda (Ngas), and the biomagnification factors of shorter chain congeners of SCCPs were higher than that of the longer chain ones. Considering that the endemic species in polar regions may be sensitive and vulnerable to the adverse effects of environmental contaminants, more attention should be paid on the bioaccumulation and toxicological risks of SCCPs in polar environments.Download high-res image (232KB)Download full-size image

•Formation of several radical species from BP and CP molecules are easily to occur.•The combination of phenoxy radicals with BP/CP tends to produce PXDDs.•The reactions of phenyl and phenoxyl diradicals with BP/CP exclusively produce PXDFs.•A new radical/molecule mechanism for the formation of PXDFs was proposed.This study investigates reaction pathways for the formation of pre-PXDD/F intermediates via a radical/molecule mechanism. Thermodynamic and kinetic parameters for the combination reactions of 2-bromophenol (2-BP) and 2-chlorophenol (2-CP) precursors with key radical species including the phenoxy radicals, the phenyl radicals and the phenoxyl diradicals were calculated in detail. The couplings of phenoxy radicals with 2-B(C)P tend to produce pre-PXDD intermediates of halogenated o-phenoxyphenol. The combinations of phenyl and phenoxyl diradicals with 2-B(C)P produce two types of structures, i.e., dihydroxybiphenyl and o-phenoxyphenyl, which exclusively act as prestructures of PXDFs. These condensation reactions, especially those involving the phenyl C atom sites in phenyl and phenoxyl diradicals, are proven to be both thermodynamically and kinetically favorable and are nearly comparable with the corresponding steps involved in the radical/radical reactions. Most importantly, reactions of phenyl and phenoxyl diradicals with halogenated phenols solely lead to the formation of PXDFs, which to some extent provides a plausible explanation for the high PXDF-to-PXDD ratios in the real environment. Therefore, our study reveals the pivotal role of the radical/molecule mechanism in homogeneous gas-phase PXDD/F formation, especially in PXDF formation. The present results fill in a knowledge gap that has hitherto existed regarding dioxin formation and improve our understanding of PXDD/F formation characteristics in the environment.Download high-res image (210KB)Download full-size image

Short-chain chlorinated paraffins (SCCPs) are still controversial candidates for inclusion in the Stockholm Convention. The inherent mixture nature of SCCPs makes it rather difficult to explore their environmental behaviors. A virtual molecule library of 42,720 C10-SCCP congeners covering the full structure spectrum was constructed. We explored the structural effects on the thermodynamic parameters and environmental degradability of C10-SCCPs through semi-empirical quantum chemical calculations. The thermodynamic properties were acquired using the AM1 method, and frontier molecular orbital analysis was carried out to obtain the EHOMO, ELUMO and ELUMO–EHOMO for degradability exploration at the same level. The influence of the chlorination degree (NCl) on the relative stability and environmental degradation was elucidated. A novel structural descriptor, μ, was proposed to measure the dispersion of the chlorine atoms within a molecule. There were significant correlations between thermodynamic values and NCl, while the reported NCl-dependent pollution profile of C10-SCCPs in environmental samples was basically consistent with the predicted order of formation stability of C10-SCCP congeners. In addition, isomers with large μ showed higher relative stability than those with small μ. This could be further verified by the relationship between μ and the reactivity of nucleophilic substitution and OH attack respectively. The C10-SCCP congeners with less Cl substitution and lower dispersion degree are susceptible to environmental degradation via nucleophilic substitution and hydroxyl radical attack, while direct photolysis of C10-SCCP congeners cannot readily occur due to the large ELUMO–EHOMO values. The chlorination effect and the conclusions were further checked with appropriate density functional theory (DFT) calculations.Download high-res image (85KB)Download full-size image

Polybrominated diphenyl ethers (PBDEs) have been shown to alter thyroid hormone level in experimental animals. One of the possible mechanisms for hormone disruption is the competitive binding of hydroxylated PBDEs (OH-PBDEs) with hormone transport proteins. In this study, binding interaction of 14 diversely structured OH-PBDEs with two thyroxine transport proteins was investigated by fluorescence displacement assay, circular dichroism, and molecular docking. Binding affinity of the 14 OH-PBDEs with transthyretin (TTR) and thyroxine-binding globulin (TBG) was measured by competitive fluorescence displacement assay. The binding constant was found to fall in the range of 1.4 × 107 M−1 and 6.9 × 108 M−1 for TTR, and between 6.5 × 106 M−1 and 2.2 × 108 M−1 for TBG. Binding affinity increased significantly with bromination number from 1 to 4, whereas 5- and 6-brominated diphenyl ethers did not show any further increase. Protein secondary structural change of TTR and TBG upon binding with 5-OH-BDE-047 was investigated by circular dichroism. The spectral change displayed a pattern similar to the one with thyroxine, suggesting that the environmental chemical binds to the two proteins at the same sites as the hormone. In molecular docking analysis, a ligand-binding channel in TTR was revealed for OH-PBDEs binding, which appeared to be mostly hydrophobic inside but guarded by positively charged residue Lys15 at the entrance. Binding affinity of the 14 OH-PBDEs with TTR could be rationalized reasonably well by their pocket binding mode and hydrophobic characteristics. Based on the binding constant obtained in this work, possibility of in vitro competitive displacement of thyroid hormones from the transport proteins by OH-PBDEs was evaluated.

•A rapid and fully automatic on-line Turboflow SPE HPLC-MS/MS method was developed.•This method has been applied to the analysis of trace PFASs in human serum successfully.•The method presented its advantages in detecting short- (C < 6) and long-chain PFASs (C > 12).•Matrix effects were well corrected by internal isotope standards and the optimized on-line SPE parameters.A rapid and fully automatic method for determining 21 per- and polyfluoroalkyl substances (with carbon chains ranging from C4 to C18, including 13 PFCAs, 5 PFSAs, 2 Cl-PFESAs, and PFOSA) in human serum samples was developed. The HPLC parameters, Turboflow column, mobile phase, sample injection volume, loading flow rate, and sample cleanup and elution time were optimized. 25 μL serum sample was directly injected into the developed on-line Turboflow SPE HPLC–MS/MS system for analysis after dilution. Matrix effects were corrected due to the matrix removal efficiency of the Turboflow column and sufficient types of internal isotope standards that were used. The established method showed a good linearity (r2 > 0.99), rapid processing time (20 min per sample), satisfactory recoveries (matrix spiked recoveries range from 84.6% to 114%) and precision (intra-day and inter-day RSDs ranged from 1.5% to 9.2% and from 1.1% to 7.0%, respectively). The limits of detection (LODs) of the 21 analyzed PFASs were between 0.008 and 0.19 ng mL−1. The LODs of short- and long-chain PFASs, such as PFBA, PFPeA, PFHxDA, and PFODA, were 0.008, 0.022, 0.15 and 0.19 ng mL−1, respectively; the spiked recoveries of these PFASs were 101, 105, 87.1, and 85.8%, respectively. Both the LODs and recoveries were better than previous studies. Further, serum PFASs concentrations detected by the presented on-line SPE method were consistent with the traditional off-line SPE method (r: 0.98–0.99), which verified the accuracy and applicability of the present method. The method shows good practical prospects in the analysis of trace per- and polyfluoroalkyl substances in human serum.

•Models of PFSAs adsorption on hydrated hematite (0 0 0 1) surface are presented.•PFOS have higher adsorption intensity than other short chain PFSAs on hematite/water interface.•The mechanism relies on the fluorine-hydrogen interaction is presented.•An appeal to the public to be vigilant of the potential problems may be caused by the short chain PFSAs in environment.Short chain perfluorinated sulfonic acids (PFSAs) that were introduced as alternatives for perfluorooctane sulfonic acid (PFOS) have been widely produced and used. However, few studies have investigated the environmental process of short chain PFSAs, and the related adsorption mechanisms still need to be uncovered. The water-oxide interface is one of the major environmental interfaces that plays an important role in affecting the adsorption behaviour and transport potential of the environmental pollutant. In this study, we performed molecular dynamics simulations and quantum chemistry calculations to investigate the adsorption mechanisms of five PFSAs and their adsorption on hydrated hematite surface as well. Different to the vertical configuration reported for PFOS on titanium oxide, all PFSAs share the same adsorption configuration as the long carbon chains parallel to the surface. The formation of hydrogen bonds between F and inter-surface H helps to stabilize the unique configuration. As a result, the sorption capacity increases with increasing C-F chain length. Moreover, both calculated adsorption energy and partial density of states (PDOS) analysis demonstrate a PFSAs adsorption mechanism in between physical and chemical adsorption because the hydrogen bonds formed by the overlap of F (p) orbital and H (s) orbital are weak intermolecular interactions while the physical adsorption are mainly ascribed to the electrostatic interactions. This massive calculation provides a new insight into the pollutant adsorption behaviour, and in particular, may help to evaluate the environmental influence of pollutants.Download high-res image (828KB)Download full-size image