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The separation of chiral compounds is an interesting and challenging topic in analytical chemistry, especially in environmental fields. Enantioselective degradation or bioaccumulation has been observed for several chiral pollutants. Polycyclic musks are chiral and are widely used as fragrances in a variety of personal care products such as soaps, shampoos, cosmetics and perfumes. In this study, the gas chromatographic separation of chiral polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclo-penta-γ-2-benzopyrane (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetra-hydronaphthalene (AHTN), 6-acetyl-1,1,2,3,3,5-hexamethylindane (AHDI), 5-acetyl-1,1,2,6-tetramethyl-3-iso-propylindane (ATII), and 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone (DPMI) was achieved on modified cyclodextrin stationary phase (heptakis (2,3-di-O-methyl-6-O-tert-butyl-dimethylsilyl-β-CD in DV-1701)). Separation techniques are coupled to tandem mass spectrometry (MS-MS), as it provides the sensitivity and selectivity needed. River and wastewaters (influents and effluents of wastewater treatment plants (WWTPs)) in the Nakdong River were investigated with regard to the concentrations and the enantiomeric ratios of polycyclic musks. HHCB was most frequently detected in river and wastewaters, and an enantiomeric enrichment was observed in the effluents of one of the investigated wastewater treatment plants (WWTPs). We reported the contamination of river and wastewaters in Korea by chiral polycyclic musks. The results of this investigation suggest that enantioselective transformation may occur during wastewater treatment.

Although Dechlorane Plus (DP) has been used as a polychlorinated flame retardant for almost half a century, its detection in the environment was not reported until 2006. The subsequent intensive research has confirmed its global ubiquity. A few reviews have presented the properties, analytical methods and environmental occurrence of DP and related compounds in the past several years. The present review emphasizes on the environmental behavior of DP isomers which is assessed by the variation of the isomer ratio of DP in various matrices. Other aspects including the analytical methods, emission sources, general environmental occurrence and bioaccumulation of DP are also summarized. In this review, three typical emission sources in the environment are categorized after introducing the measurement method of DP. The temporal-spatial distribution is then evaluated at the global scale, which provides an integrated representation of the environmental occurrence of DP and potential impact on the human health and ecosystems. The variations of DP isomer ratio in various matrices reinforce its source related distribution and their stereoselective bioaccumulation. Thereafter, DP related compounds and dechlorinated analogs are briefly summarized in regards to their occurrence in various matrices, suggesting their ubiquity in the environment and bioavailability. Further studies are required to better assess the exposures and toxicological effects of DP and its analogs. A special concern is the serious contamination in e-waste recycling areas in developing countries, where long-term monitoring data on the association of DP exposure and adverse effects to human health and ecosystems is urgently needed., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Dechlorane Plus (DP) is a flame retardant used as a substitute of Mirex since 1970s, but it was not detected in the environment until 2006. Since then, this compound and its main relatives, Dechlorane 602, 603 and 604, have been mainly studied in environmental matrices for monitoring purposes, but the dietary exposure to them has been hardly investigated so far. In the present study, we determined this family of compounds in fish and vegetable oil samples from Catalonia (Spain), most of them used as health supplements. Determination was carried out by gas chromatography-high resolution mass spectrometry (GC-HRMS), after a clean up in a multilayer silica column and preparative high performance liquid chromatography (HPLC) equipped with a pyrenyl(ethyl) column. Concentrations of Dechlorane compounds were between below the limit of detection and 384.2 pg g(-1). Although there are only few studies about the presence of these pollutants in food or feed, concentrations obtained indicated that these compounds are in the same order in fish and vegetable oil health supplements as the few other food and feed studies., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Dechloranes (Decs) have been recently found to occur widely in the environment even in the remote polar regions. However, the understanding of their environmental fate is rather limited. The Tibetan Plateau (TP) may be an important indicator region to study the long-range atmospheric transport and their fates of these emerging contaminants since it has very limited local sources. In the present study, Dechlorane plus (DP), Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603) and Dechlorane 604 (Dec 604) were analyzed in lichen samples from the southeast TP. The results showed that only DP and Dec 602 were detected, with a detection frequency of 89% and 100%, respectively. The average concentrations (dry weight) of ΣDP and Dec 602 were 318 pg g(-1) (20-1132 pg g(-1)) and 167 pg g(-1) (27-843 pg g(-1)), respectively. The DP concentration in this study was much higher than those in moss from the remote Ny-Ålesund, Arctic. The concentrations of Dec 602 were found to generally increase with increasing altitude, while DP concentrations seemingly showed an opposite altitudinal trend along the mountain slopes. No stereoselective accumulation or transformation of anti-DP and syn-DP was observed in lichens and the altitudinal behavior of the two isomers was similar. This research documented that Decs are prone to undergo LRAT and cold-trapping by the mountains in the southeast TP., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The environmental occurrence of dechlorination moieties from the high production volume flame retardant, Dechlorane Plus (DP), has largely been documented; however, the sources have yet to be well understood. In addition, few laboratory-based studies exist which identify the cause for the occurrence of these chemicals in the environment or humans. Anaerobic dechlorination of the two DP isomers was investigated using a laboratory-simulated wastewater treatment plant (WWTP) environment where anaerobic digestion is used as part of the treatment regime. Known amounts of each isomer were added separately to sewage sludge which provided the electron-donating substrate and at prescribed time points in the incubation, a portion of the media was removed and analyzed for DP and any dechlorination metabolites. After 7 days, monohydrodechlorinated products were observed for both the syn- and anti-DP which were continued throughout the duration of our study (49 days) in an increasing manner giving a calculated formation rate of 0.48 ± 0.09 and 0.79 ± 0.12 pmols/day for syn- and anti-DP, respectively. Furthermore, we observed a second monohydrodechlorinated product only in the anti-DP isomer incubation medium. This strongly suggests that anti-DP is more susceptible to anaerobic degradation than the syn isomer. We also provide compelling evidence to the location of chlorine loss in the dechlorination DP analogues. Finally, the dechlorination DP moieties formed in our study matched the retention times and identification of those observed in surficial sediment located downstream of the WWTP.

Locating sources of persistent organic pollutants (POPs) to the atmosphere can sometimes be difficult. We suggest that tree bark makes an excellent passive atmospheric sampler and that spatial analysis of tree bark POPs concentrations can often pinpoint their sources. This is an effective strategy because tree bark is lipophilic and readily adsorbs and collects POPs from the atmosphere. As such, tree bark is an ideal sampler to find POPs sources globally, regionally, or locally. This article summarizes some work on this subject with an emphasis on kriged maps and a simple power-law model, both of which have been used to locate sources. Three of the four examples led directly to the pollutant's manufacturing plant.

Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), Dechlorane 604 (Dec 604), Dechlorane 604 component B (Dec 604 CB) and Dechlorane Plus (DP) were analyzed in soil and fish collected across e-waste recycling sites in Guiyu. The results indicate that soil and fish are contaminated with dechlorane compounds especially Dec 602 and DP which show high concentrations in the samples near recycling sites. Dec 604 and Dec 604 CB are not detected. The photo-degradation experiment indicates that Dec 604 and Dec 604 CB have much faster degradation rates compared to other dechloranes, suggesting they might be more vulnerable to degradation during recycling processes and further studies are needed for assessing the environmental fate and persistence of their degradation products. Dec 602 has not been manufactured in China, the detection of Dec 602 in soil and fish implies that it might be from imports of recyclable materials from developed countries., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Dechloranes, including Dechlorane Plus (syn- and anti-isomers), Dechlorane 602, Dechlorane 603, Dechlorane 604, Chlordene Plus, and Mirex are used as flame-retardants and were recently found in human serum of the European population. In order to investigate if food consumption would possibly be a significant route of exposure, we developed a method for the measurement of Dechloranes in food and feed. We showed that it was possible to extend the scope of the regular polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin like (DL-), and non-dioxin like (NDL-) regulated PCBs clean-up and fractionation procedure to Dechloranes and that no compound degradation occurred during the strong acidic treatments used for lipid digestion. Dechloranes were measured by gas chromatography coupled to triple quadrupole mass spectrometry (GC-QQQMS/MS). We optimized injection parameters by face centered experimental design (FCD). The electron ionization fragmentation was investigated to set appropriate multiple reaction monitoring (MRM) transitions. Instrumental and method limits of quantitation (iLOQs and mLOQs) were determined following EU guidelines for dioxin analyses in food. A total of 88 samples were analyzed to assess the prevalence of this route of exposure to humans. Average levels of the sum of Dechloranes ranged from 10 to 31pg/g fat, with the exception of fish, feed additives, and corn that were reported in pg/g wet weight at average levels of 9, 12, and 2pg/g ww. Based on Belgian food habits, a dietary intake was estimated to be 136pg/day. The relatively low reported levels indicate that other routes of human exposure should be considered., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Atmospheric particles were collected in several cities in Japan (Sapporo, Sagamihara, Kanazawa, and Kitakyushu), Korea (Busan), and China (Beijing) using a high-volume air sampler equipped with a quartz fiber filter. The summer and winter samples were analyzed using gas chromatography-high-resolution mass spectrometry for Dechlorane Plus (DP). Decabromodiphenyl ether (BDE-209) was also analyzed for the samples from Kanazawa and Beijing. DP was detected in all samples. The mean total DP (ΣDP) concentration was highest (6.7 pg/m(3)) and lowest (0.87 pg/m(3)) in the winter samples from Sagamihara and Busan, respectively. The seasonal variation of DP concentrations varied by sampling site in this study. BDE-209 was detected in all the analyzed samples except for one of the Kanazawa winter samples. BDE-209 concentration was considerably higher in Beijing than in Kanazawa. Significant correlations were found between the concentrations of ΣDP and BDE-209 in the winter samples from Kanazawa and in both summer and winter samples from Beijing. This similarity in the atmospheric behavior of DP and BDE-209, especially in winter, is assumed to reflect a common end usage and release mechanism.

Levels of dechlorane plus (DP) and "DP-like" compounds were measured in indoor dust samples collected across China. The concentrations of ΣDP and "DP-like" compounds ranged from 0.35 to 1,000 ng g(-1) and<0.21 to 2.4 ng g(-1), respectively. The total DP concentration in urban sites were significantly higher than those of rural sites, while no significant difference was found for "DP-like" compounds, suggesting different sources of these compounds. Significant positive correlations were found between fsyn and latitude, and between fsyn and longitude. The deleterious risk associated with DP exposure via indoor dust for the general population in China was low and safer than expectation. For estimating human exposure via indoor dust, sensitivity analysis showed that more attention should be given to the influential variables such as the level of pollutants, body weight, and the amount of ingestion and adsorption., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Fourteen polybrominated diphenyl ethers (PBDEs), 14 non-BDE flame retardants (FRs), and 25 organochlorine pesticides (OCPs) were analyzed in air samples collected at Little Fox Lake (LFL) in Canada's Yukon Territory from August 2011 to December 2014. LFL is a long-term monitoring station operated under the Northern Contaminants Program (NCP) and one of only a few stations that contribute to the assessment of air pollution levels and pathways to the sub-Arctic region. BDE-47 was the most abundant congener among the 14 PBDEs, followed by BDE-99. Non-BDE FRs pentabromotoluene (PBT) and dechlorane plus (DP) were detected in all the samples. Dechlorane 602, 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), hexabromobenzene (HBB), and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) were also detected in >75% of all samples. PBDEs have shown a decreasing tendency as of 2013, which may reflect the phase-out of penta- and octa-BDE mixtures has led to significant decline in the atmosphere. The highest concentrations of OCPs were observed for hexachlorobenzene (HCB), with a median concentration of 61 pg/m(3), followed by α-hexachlorocyclohexane (α-HCH) and α-endosulfan. Potential source contribution function (PSCF) highlights Northern Canada, Pacific, and East Asia as potential sources in warm seasons; whereas in cold seasons, the chemicals mainly came from the Pacific Rim.

The combination of hyperpolarized Xe with chemical exchange saturation transfer (Hyper-CEST) is a powerful NMR technique to detect highly dilute concentrations of Xe binding sites using RF saturation pulses. Crucially, that combination of saturation pulse strength and duration that generates the maximal Hyper-CEST effect is a priori unknown. In contrast to CEST in proton MRI, where the system reaches a steady-state for long saturation times, Hyper-CEST has an optimal saturation time, i.e. saturating for shorter or longer reduces the Hyper-CEST effect. Here, we derive expressions for this optimal saturation pulse length. We also found that a pulse strength, B1, corresponding to five times the Xe exchange rate, k(BA) (i.e. B1 = 5 k(BA)/γ with the gyromagnetic ratio of (129)Xe, γ), generates directly and without further optimization 96% of the maximal Hyper-CEST contrast while preserving spectral selectivity. As a measure that optimizes the amplitude and the width of the Hyper-CEST response simultaneously, we found an optimal saturation pulse strength corresponding to √2 times the Xe exchange rate, i.e. B1=√2k(BA)/γ. When extremely low host concentration is detected, then the expression for the optimum saturation time simplifies as it approaches the longitudinal relaxation time of free Xe., (Copyright © 2015 John Wiley & Sons, Ltd.)

For the first time, a sensitive and specific method was developed and fully validated for the quantification of the EU marker residue of tiamulin, 8-α-hydroxy-mutilin, in rabbit muscle and liver tissues using liquid chromatography combined with positive heated electrospray ionization triple quadrupole mass spectrometry. The mass spectrometer was operated in the selected reaction monitoring (SRM) mode with selection of the [M + H](+) ion in both quadrupoles 1 and 3, resulting in the SRM transition m/z 337.25 > 337.25 for quantification. Chromatography was performed using a Hypersil Gold C18 column using a gradient elution program with water and methanol as mobile phases. The sample preparation procedure for the analysis of 8-α-hydroxy-mutilin in liver and muscle samples consisted of three main steps: (1) extraction of the tissue matrix using 0.1 N hydrochloric acid/acetone (50/50, v/v), (2) hydrolysis of tiamulin and metabolites to 8-α-hydroxy-mutilin in alkaline medium at 45 °C, and (3) liquid-liquid extraction in acidic medium using ethyl acetate. This is the first method presenting fully validated results, encompassing a linearity of 50 to 2,000 μg/kg, within-run and between-run accuracy and precision, limit of quantification (50 μg/kg for both muscle and liver tissues), limit of detection (muscle, 11.9 μg/kg; liver, 20.6 μg/kg), extraction recovery (muscle, 66.2%; liver, 75.5%), signal suppression and enhancement (muscle, 51.7%; liver, 43.3%), carryover, applicability and practicability, and stability during storage and analysis. This novel method is therefore sensitive enough to be used for residue depletion studies of tiamulin in rabbits and for food safety monitoring with respect to MRL compliance of residues.

Levels of polybrominated diphenyl ethers (PBDEs) and dechlorane plus (DPs) were investigated in the Indus River Basin from Pakistan. Concentrations of ∑PBDEs and ∑DPs were ranged between 0.05 and 2.38 and 0.002-0.53 ng g(-1) in the surface soils while 1.43-22.1 and 0.19-7.59 pg m(-3) in the passive air samples, respectively. Black carbon (fBC) and total organic carbon (fTOC) fractions were also measured and ranged between 0.73 and 1.75 and 0.04-0.2%, respectively. The statistical analysis revealed strong influence of fBC than fTOC on the distribution of PBDEs and DPs in the Indus River Basin soils. BDE's congener profile suggested the input of penta-bromodiphenylether (DE-71) commercial formulation in the study area. Soil-air partitioning of PBDEs were investigated by employing octanol-air partition coefficients (KOA) and black carbon-air partition coefficients (KBC-A). The results of both models suggested the combined influence of total organic carbon (absorption) and black carbon (adsorption) in the studied area., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Three dibenzocyclooctadiene lignans: deoxyschizandrin (1), gomisin A (2) and schizandrin (3) were isolated from biomass extracts of Schisandra chinensis (Turcz.) Baill. shoot-differentiating callus cultures. The mentioned lignans were not isolated earlier from in vitro cultures of this plant species. This is the first report concerning on isolation of dibenzocyclooctadiene lignans from in vitro cultures of Schisandra chinensis.

The occurrence and spatial distribution of dechloranes including mirex, dechlorane plus (DP), dechlorane (Dec) 602, Dec 603, and Dec 604 in surficial sediments of Lake Taihu were investigated in this study. The concentrations of mirex and DP ranged from below detection limit (BDL) to 1.29 ng g(-1) dw and 0.051 to 2.10 ng g(-1) dw, respectively. Dec 602, Dec 603, and Dec 604 on the other hand, were BDL in any of the samples. The contamination levels of DP were higher than that of Mirex at 21 of all 22 sampling sites. Levels of mirex and DP in the lake sediments were correlated when an extremely high mirex value was removed. Both mirex and DP levels were correlated with the amount of organic matters in the sediment samples. Spatial distribution of mirex and DP suggested that these two chemicals in the lake had similar input sources except for one site. Comparison to previously reported flame retardants' levels in the sediments shows that DP levels were similar with the levels of tetrabromobisphenol A, hexabromocyclododecane but lower than PBDEs and organophosphates levels in Lake Taihu. The higher levels in the north-east part of Lake Taihu adjacent to two major cities: Wuxi and Suzhou, indicated that city effluent might be a major source for DP contamination in the lake.

Dechlorane Plus (DP) and a dechlorinated product of DP were measured in 34 matched human hair and serum samples (19 males and 15 females) collected from e-waste recycling workers in South China. The DP (sum of syn- and anti-DP) concentrations in hair and serum samples ranged from 6.3 to 1100 ng g(-1) dry weight and from 22 to 1400 ng g(-1) lipid weight (lw). The levels of anti-Cl11-DP ranged from 0.02 to 1.8 ng g(-1) in hair and from not detected to 7.9 ng g(-1) lw in serum. Significant positive correlations for both DP and anti-Cl11-DP concentrations between hair and serum samples were found (p<0.05), indicating hair to be a suitable matrix for human DP exposure. However, a significant difference was found in the DP isomer composition between hair and serum, suggesting stereoselective bioaccumulation during the absorption of DP into hair. A sharp gender difference was found in the levels of DP in hair. Moreover, syn-DP, anti-DP and anti-Cl11-DP in hair significantly correlated with those in serum for male samples, but not for female samples. The observed gender differences in the present study may be, in part, ascribed to the much longer hair exposure time for females than males due to the difference in sampling distance from the scalp., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

This study investigates associations between serum concentrations of emerging and legacy halogenated flame retardants (HFRs) in 46 Norwegian women and measured indoor air and dust concentrations of the HFRs as well as detailed information on diet and household factors. Hexabromobenzene (median 0.03ng/g lipid) and Dechlorane 602 (median 0.18ng/g lipid) were detected in about 50% of the samples and Dechlorane Plus syn (median 0.45ng/g lipid) and anti (median 0.85ng/g lipid) in more than 78%. The most abundant polybrominated diphenyl ethers were 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153; median 0.82ng/g lipid) and 2,2',4,4'-tetrabromodiphenyl ether (BDE-47; median 0.49ng/g lipid) detected in more than 70% of the samples. In the bivariate analysis, no consistent associations were observed between the biomonitoring data and measured concentrations in indoor air and dust. On the other hand, consumption of specific food items (mainly lamb/mutton and margarine) correlated significantly with more than two HFR serum concentrations, while this was not the case for household factors (electronic appliances). Only the significant bivariate associations with diet were confirmed by multivariate linear regression analyses, which might indicate a higher contribution from food compared to the indoor environment to the variation of the body burden of these HFRs., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Chlorinated flame retardants, particularly dechlorane plus (DP), were widely used in commercial applications and are ubiquitous in the environment. A total of seven species of aquatic organisms were collected concurrently from the region of a chemical production facility in Huai’an, China. DP and structurally related compounds including mirex, dechloranes 602, 603, 604, chlordene plus (CP), DP monoadduct (DPMA), and two dechlorinated breakdown products of DP, decachloropentacyclooctadecadiene (anti-Cl(10)-DP) and undecachloropentacyclooctadecadiene (anti-Cl(11)-DP), were detected in these aquatic organisms. Nitrogen stable isotope ratios were also measured to determine the trophic levels of the organisms. Trophic magnification factors (TMFs) for these chemicals were calculated with values ranging from 1.0 to 3.1. TMFs for CP, mirex, anti-DP, and ∑DP were statistically greater than 1, showing evidence of biomagnification in the food web. Concentration ratios of anti-Cl(11)-DP to anti-DP showed a significant relationship with trophic level, implying that anti-Cl(11)-DP had a higher food-web magnification potential than its precursor. The biota-sediment accumulation factors and TMFs for DP demonstrated stereoselectivity, with syn-DP having a greater bioaccumulation potential than anti-DP in the aquatic environment.

Following the ban of polybrominated diphenyl ethers, other halogenated flame retardants (FRs) might be used increasingly. This study has analyzed hexabromocyclododecane (HBCD), 1,2-bis(2,4,6-tribromophenoxy)-ethane (BTBPE), 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and dechloraneplus (DP) in Greenland air over the course of a year. Moreover, BTBPE, DPTE, DP, 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), bis(2-ethylhexyl) tetrabromophthalate (TBPH) and decabromodiphenylethane (DBDPE) were analyzed in samples of polar bear, ringed seal, black guillemot and glaucous gull from Greenland. HBCD in air appeared low, while mean concentrations of syn- and anti-DP were 2.3 and 5.2 pg/m(3), respectively. BTBPE and DPTE were undetectable in air. Detection frequencies in biota were <50% for BTBPE, TBPH and DBDPE, but near 100% for the remaining compounds. Ringed seals from East Greenland had highest mean concentrations of TBB, DPTE, syn- and anti-DP (1.02, 0.078, 0.096 and 0.42 ng/g wet weight, respectively). Our study documents the long-range transport and, to some extent, bioaccumulation of these novel FRs.

There are a limited number of scientific reports available regarding polybrominated diphenyl ethers (PBDEs) and dechlorane plus (DP) screening levels and ecological risk assessment in environmental compartments. The present study was aimed to assess the screening-level risk assessment, congener-specific analysis, and spatial distribution pattern of PBDEs and DP in water and sediment. Samples were collected from upstream feeding tributaries (Nullah Aik and Nullah Palkhu) of the River Chenab, Pakistan. ∑PBDE concentrations in water and sediment ranged from 0.48 to 73.4 ng L(-1) and 0.35 to 88.1 ng g(-1) (dw), respectively, whereas levels of ∑DP in water and sediment were 0.01-4.58 and 0.10-12.5 ng g(-1) dw, respectively. Ratio for fsyn in sediment (ng g(-1)) and water (ng L(-1)) ranged between 0.59-0.64 and 0.60-0.68, respectively, which reflected no use of industrial mixture of DP isomers in the study area. Potential risks to ecological integrities through contaminated water and sediments in the study area were deemed marginal at the present time as assessed on the basis of the available and current toxicological data. The scarcity of data on levels, source apportionment, and detected permissible limits of PBDEs and DP warrant future auxiliary study of this group of contaminants.

This paper reported the occurrence and concentrations of macrocyclic-, polycyclic- and nitro musks in cosmetics and household commodities collected from Japan. The high concentrations and detection frequencies of Musk T, habanolide, and exaltolides were found in commercial products, suggesting their large amounts of production and usage in Japan. Polycyclic musks, HHCB and OTNE, also showed high concentrations in cosmetics and products. The estimated dairy intakes of Musk T and HHCB by the dermal exposure to commercial products were 7.8 and 7.9 μg/kg/day in human, respectively, and perfume and body lotion are dominant exposure sources. We also analyzed synthetic musks in house dusts. Polycyclic musks, HHCB and OTNE, showed high concentrations in samples, but macrocyclic musks were detected only in a few samples, although these types of musks were highly detected in commercial products. This is probably due to easy-degradation of macrocyclic musks in indoor environment. The dairy intakes of HHCB by dust ingestions were 0.22 ng/kg/day in human, which were approximately five orders of magnitudes lower than those of dermal absorption from commercial household commodities., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Models that predict the fate of petroleum fuels in the environment are often required for effective remediation of fuel-contaminated sites. In this research, an environmental fuel spill was simulated by means of a diesel/water microcosm, in which the temporal changes in composition were assessed during evaporation by gas chromatography-mass spectrometry (GC-MS). First-order kinetic rate constants were calculated for 51 selected compounds and utilized to develop predictive models for evaporation rate constants, using GC retention indices on a nonpolar stationary phase. Models were initially developed to predict rates of evaporation of compounds from individual classes (normal alkane, branched alkane, alkyl benzene, and polycyclic hydrocarbon) and then expanded to include all compounds (comprehensive model). Using the comprehensive model, the rate constants were predicted with a mean absolute percent error (MAPE) of 10%, whereas the class-specific models resulted in less error (4-8%). These models were employed to predict the fraction remaining of the total fuel (6% error) as well as the fraction remaining of individual compounds (13% MAPE). Accurate models such as these will facilitate remediation of environmental releases of petroleum products., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The populations of American (Anguilla rostrata) and European eels (Anguilla anguilla) have been declining rapidly in the last decades. Organic contaminants are suspected to be one of the possible causes for the decline; however, so far there have been few investigations of the uptake of specific compounds by different life cycle stages (e.g. freshwater or marine stage) and how the contamination patterns develop throughout the eel's life cycle. In the present study we measured concentrations of polybrominated diphenylethers (PBDEs), alternate brominated flame retardants (alternate BFRs) and Dechloranes (Decs) in different life stages of European and American eels to compare the contamination patterns and their development throughout the eel's life cycle. In general, concentrations of flame retardants (FRs) were similar to or higher in American than in European eels, and a greater number of FRs were detected. PBDE congeners that are characteristic of the Penta-PBDE formulation were the most abundant FRs in all adult eels as well as American glass eels. In European glass eels the alternate BFR 2,3-dibromopropyl-2,4,6-tribromophenylether (DPTE) and Dechlorane Plus were the dominating FRs, with average concentrations of 1.1±0.31 ng g(-1) ww and up to 0.32 ng g(-1) ww respectively. Of the PBDEs BDE-183 was the most abundant congener in European glass eels. Low concentrations (less than 10% of the total contamination) of Tetra and Penta-PBDEs in juvenile European eels indicated that bans of technical Penta-PBDE in the European Union are effective. Enrichment of PBDEs was observed over the life stages of both European and American eels. However, a greater relative contribution of PBDEs to the sum FR contamination in American eels indicated an on-going exposure to these substances. High contributions of alternate BFRs in juvenile eels indicated an increased use of these substances in recent years. Concentrations seemed to be driven primarily by location, rather than life stage or age., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

A method for the determination of chlorinated flame retardants: Dechlorane Plus, Dechlorane (Dec) 602, Dec 603 and Dec 604, in marketed fish is described. The method involves the use of matrix solid-phase dispersion (MSPD) prior to their determination by gas chromatography-electron-capture negative-ion chemical-ionisation mass spectrometry (GC-ECNICI-MS). Parameters that affect the extraction efficiency of the target analytes from fish samples were optimised using a Box-Behnken design method. MSPD integrated the extraction and clean-up procedures into a single step, which provides the benefits of being simple and convenient. The optimal extraction conditions involved dispersing a freeze-dried fish (1-g) in 2-g of silica gel, and packed with 1-g of Florisil, and then the target analytes were eluted with 20 mL of n-hexane. The limits of quantification were 9-15 pg/g-lipid weight. Preliminary results showed that the total concentrations of the target analytes ranged from 0.15 to 1.3 ng/g-lipid weight., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Occurrence of new toxic chemicals in sludge from wastewater treatment plants (WWTPs) is of concern for the environment and human health. Alternative halogenated flame retardants (HFRs) are a group of potentially harmful organic contaminants in the environment. In this study, a nationwide survey was carried out to identify the occurrence of HFRs and their potential dehalogenated products in sewage sludge from 62 WWTPs in China. Of all 20 target chemicals analyzed, decabromodiphenyl ethane (DBDPE), hexabromocyclododecane (HBCD) and 1, 2-bis (2,4,6-tribromophenoxy)-ethane (BTBPE) were detected in all sludge samples, and the concentrations were in the range of 0.82-215, 0.09-65.8, and 0.10-2.26 ng g(-1) d.w., respectively. Dechlorane Plus (DP) was found in 60 of 62 samples, and the concentration ranged from nd-298 ng g(-1) with a mean of 18.9 ng g(-1) d.w. The anti-DP fractional abundance fanti (0.79) in the samples was much higher than the commercial DP composition (fanti=0.59), indicating a stereoselective degradation. Comparison with global sludge concentrations of HFRs indicate that China is at the medium pollution level in the world. Principal components analysis revealed that strong correlations existed between ln-transformed concentrations (natural logarithm) of the dominant BFRs and total organic carbon (TOC) as well as industrial wastewater proportion, influent volume and serving population. Significant linear relationships (R=0.360-0.893, p<0.01) were found among emerging brominated flame retardants (BFRs), suggesting their common commercial applications and release sources to the environment. Two kinds of dehalogenated products, pentabromocyclododecane (PBCD) and undecachloropentacyclooctadecadiene (Cl11-DP), derived from HBCD and DP, were also identified in sewage sludge for the first time.

Dechlorane Plus (DP) isomers, along with two dechlorinated metabolites were measured in environmental matrices, chyme and digestive tract contents and tissues of chicken from an e-waste recycling site located in South China. Soil is proved to be the main source of DP in chicken rather than food because soil contributes more than 94% of total DP in chyme. In the gastrointestinal tract absorption processes, no selective absorption was observed for DP isomers during the ingestion processes. The tissue distribution of DP isomers in chicken exhibits complicated characteristics. The lipid contents in tissues are the main factors in the tissue distribution of DP, while the different blood perfusion state and the different tissue functions also seem to influence the tissue distribution of DP. The fat, brain, and liver exhibit higher fanti values (0.65, 0.64, and 0.64) than the other tissues (0.54-0.59). The elevated fanti values of DP from the contamination source (0.52 in soil) to chicken suggest stereoselective bioaccumulation of anti-DP in chicken. The similar ratios of anti-Cl11-DP to anti-DP between soil and chicken imply that anti-Cl11-DP mainly derives from the uptake from environment rather than in vivo dechlorination., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

This study aimed to investigate the liver protection effect of Schisandra chinensis (Turcz.) Baill. (SC) lignans and its combination with Rubus idaeus (RI) on chronic alcohol-induced mice. A low level of SC lignans (SL) was prepared from the clear juice of sarcocarp. Lignans were further extracted from the SC seeds and added to the SL to form high-level SC lignans (SH). Moreover, RI clear juice lyophilized powder was mixed with SL (SR), and the liver protection effects of SL, SH and SR were investigated. Male ICR mice were administered with the corresponding samples and gastrically infused with 50% alcohol (1 h later) once per day for 60 d. In the in vitro study, the characteristic lignans in the SC clear juice and the seed extract were analyzed by high performance liquid chromatography (HPLC). The total phenolic content (TPC) and antioxidant capability of SL, SH, and SR were determined. The results of the in vivo study showed that SC lignans exhibited a dose-dependent effect on the regulation of hepatic antioxidant status, serum transaminases levels, hyperlipidemia and hepatic fat deposition in mice. However, hepatic lesions were observed in the SH mice, which indicated a potential side effect caused by long-term consumption of SH under chronic alcohol administration. By contrast, SR exhibited a similar hepatoprotective effect as SH without any abnormality found in the histological analysis. After analysis with HPLC, Schizandrol A and Schizandrol B were identified in the SC clear juice, and two more kinds of lignans, Schisandrin A and Schisandrin B, were identified in the seed extracts. The SR sample had the highest TPC and exhibited the best antioxidant capability. In conclusion, RI strengthened the liver protection effect of SC lignans effectively and safely, which was probably achieved by enhancing the antioxidant status and the positive effect of their combination was possibly attributed to both lignans and polyphenols. This study demonstrated that the combination of low-level SC lignans and RI might be used as a potential safe formula for beverage development to alleviate the adverse effects of long-term alcohol consumption.

An on-line coupling solid-phase extraction (SPE) has been developed for the first time to preconcentrate trace amounts of 17 musk fragrances extensively used in personal care products (6 polycyclic musks, 3 nitro musks, 7 macrocyclic musks and 1 polycyclic musk degradation product) from wastewater samples, prior to analysis by gas chromatography and mass spectrometry through an on-column interface. A 10 mm × 2 mm I.D. precolumn packed with Oasis HLB (60 μm) or C18 (60 μm) was compared for the optimization of the solid-phase extraction process. The parameters affecting the transfer of the analytes from the precolumn to the GC system (e.g. flow-rate, temperature and solvent vapor exit time) as well as SPE parameters (e.g. sample flow, sample volume, elution solvent, etc.) were optimized. An organic modifier such as methanol was added to the sample before the extraction process to avoid adsorption problems. The use of the MS detector under selected ion monitoring acquisition enabled the analytes to be quantified at low ng L(-1) levels, preconcentrating only 10 mL of sample, and the limits of detection were between 1 and 30 ng L(-1). The method was applied for the determination of musk fragrances in wastewater samples from three urban wastewater treatment plants (WWTPs). The analysis of influent urban wastewater revealed that galaxolide, tonalide and ambrettolide were the most abundant musk compounds with concentrations ranging between 18 ng L(-1) and 45,091 ng L(-1), 852 ng L(-1) and 49,904 ng L(-1) and 507 ng L(-1) and 21,528 ng L(-1) respectively. The remaining musks were present at lower concentrations and two of the macrocyclic musk studied (musk MC4 and civetone) were not detected. The analysis of effluent wastewater showed a decrease in the concentrations of all of the compounds present in influent samples, with the decrease being more significantly in the case of polycyclic and nitro musks than for macrocyclic musks. Only HHCB-lactone remained constant or increased its concentration., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The dechlorane family of flame retardants, which includes Mirex (also known as Dechlorane), Dechlorane Plus (DP), and Dechloranes (Dec) 602, 603, and 604, were manufactured at a facility along the Niagara River, upstream of Lake Ontario. Some of these compounds remain in use. In a previous study, we found Mirex and Dec602 to have greater bioaccumulation potentials than Dec604 and DP based on calculated biota-sediment accumulation factors (BSAFs). In this study, analogues of Dec604, containing fewer bromines and mixed substitutions of bromine and chlorine, were identified in Lake Ontario sediment and fish using high and ultrahigh resolution mass spectrometric techniques. The tribromo-Dec604 (Br3Dec604) analogue, known as Dechlorane 604 Component B (Dec604 CB), was present in lake trout and whitefish at concentrations of 10-60 ng/g lipid weight, approximately 50-200 times greater than concentrations measured for Dec604. In addition, BrDec604 and Br2Dec604 analogues, and mixed Br2Cl2Dec604, Br3ClDec604, Br2ClDec604, and BrCl2Dec604 analogues were also present. We have shown that solutions of Dec604 and Dec604 CB exposed to UV-light undergo photodebromination and give rise to the analogues found in sediment and fish. Dec604 CB and other lesser halogenated analogues of Dec604 show greater bioaccumulation potentials than Dec604, Dec602 and DP, based on BSAFs, which highlight the need to consider likely impurities and degradation products in the assessment of persistent, bioaccumulative, and toxic compounds.

Dechlorane Plus (DP) has been detected extensively in both biotic and abiotic matrices, and stereoselective enrichment of Dechlorane Plus isomers has also been observed in organisms. In this laboratory study, Ulva pertusa were firstly exposed to known Dechlorane Plus concentrations for 21d (uptake period), and then transferred to clean seawater for 14d (depuration period) to investigate the kinetics of Dechlorane Plus isomers in U. pertusa. Dechlorane Plus isomers reached steady-state after 21d of exposure. The mean fractional abundance of syn-DP (fsyn) exceeded than that of 0d (0.23±0.02) during uptake, but decreased during depuration. This study is the first to define the kinetics of stereoselective enrichment of Dechlorane Plus isomers in U. pertusa using two-box kinetic model. The uptake rate constants of the syn- and anti-DP were 0.164±0.056d(-1) and 0.083±0.071d(-1), respectively. The depuration rate constants were 0.337±0.057d(-1) (syn-DP) and 0.236±0.095d(-1) (anti-DP), suggesting that syn-DP is eliminated quicker than anti-DP by U. pertusa. These results are consistent with observation of fsyn and stereoselective enrichment of Dechlorane Plus isomers in U. pertusa., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Willow tree bark samples from urban and rural sites in Inner Mongolia, Ningxia Province, and Gansu Province, in the Yellow River basin, were analyzed for polybrominated diphenyl ethers (PBDEs), dechlorane plus (DP), and dioxin-like polychlorinated biphenyls (DL-PCBs) to compare their relative levels in air in these areas (i.e., treating bark as a passive air sampler). No difference was found between the pollutant concentrations in Salix matsudana and Salix babylonica bark samples. The mean concentrations of the total PBDEs, DP, and total DL-PCBs were 13000 ± 6400, 46 ± 44, and 26 ± 17 pg/g dry weight, respectively, with urban samples containing much higher concentrations (19000 ± 5700 pg/g, 51 ± 27 pg/g, and 37 ± 29 pg/g dry wt in PBDEs, DP, and DL-PCBs, respectively) than rural samples (10000 ± 5200 pg/g, 45 ± 53 pg/g, 22 ± 9 pg/g dry wt). A strong positive correlation between PBDEs and DP was found in all of the samples (r=0.712, p=0.006), but correlations between PCBs and the other pollutants were only found in the rural samples. The total DL-PCB concentration in the tree bark correlated with population density., (© 2014 SETAC.)

Wastewater treatment plants (WWTPs) are considered an important medium for the transport and transformation of organic pollutants, such as polybrominated diphenyl ethers (PBDEs) and dechlorane plus (DP). However, limited data on PBDEs and no data on DP were available regarding wastewater and sludge from China, especially in Shanghai, one of the most developed cities in China. This study examined the occurrence of PBDEs and DP in a conventional WWTP in Shanghai for one year. The levels of the total PBDEs in the influent and dewatered sludge ranged from 5.31 to 27.9 ng/L and 31.0 to 99.5 ng/g, respectively, which were at the low end of the global range. DP was reported in wastewater with a mean concentration of 0.46 ng/L (range: 0.05 to 1.40 ng/L) and sludge contained DP in the range of 1.1 to 2.0 ng/g. For both PBDEs and DP, there were no significant seasonal variations observed in the four seasons. Indoor dust and outdoor air could be two main sources of PBDEs and DP in the WWTP. In both the influent and sewage sludge, BDE-209 was the most abundant congener, with contributions to the total PBDE levels ranging from 52.9 to 82.6% and 82.7 to 84.0%, respectively. The fraction of anti-DP was consistently higher than that of syn-DP, and the average of fsyn ranged from 0.16 to 0.33, which fell in the range of two commercial DP mixtures. The annual releases of PBDEs and DP via sewage sludge from WWTPs in Shanghai were estimated to be 6,370 g and 164.8 g, respectively. The fate and risk of these compounds after being released into the environment require further research. To the best of our knowledge, this study is the first to report on the occurrence of DP in wastewater., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The occurrence of classical (polybrominated diphenyl ethers, PBDEs) and emerging FRs (dechloranes, hexabromobenzene (HBB), pentabromoethyl benzene (PBEB) and decabromodiphenyl ethane (DBDPE)) in unborn eggs of 14 different species from Doñana Natural Space and surrounding areas was studied. PBDEs, Dec-602, Dec-603 and DP were detected in all the species, whereas HBB, PBEB, DBDPE and Dec-604 were not detected in any sample. ΣPBDE and ΣDechlorane levels ranged from 1.40 to 90.7, and from 0.77 to 260 ng/g lw, respectively. BDE-209 was the most abundant BDE congener in almost all the species, whereas Dec-602 was the predominant among dechloranes. In general, levels of PBDEs and dechloranes were similar and even higher for dechloranes, probably indicating the increasing use of dechloranes as a result of legal restrictions on PBDEs. In both cases, the most contaminated specie was the white stork. Using stable isotope characterization, differences among species and possible biomagnification processes were also evaluated. PBDE levels increased as the trophic position increased, showing biomagnification capacity. The same behavior was observed for Dec-602 and Dec-603; however, DP levels were not linearly correlated with trophic level. These results show that more attention should be given to emerging FRs such as dechloranes since they show similar environmental behavior as PBDEs., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

A total of 175 samples, composed of 35 different foodstuffs, were obtained from retail markets in Korea and analyzed to investigate the contamination status and dietary intake of Dechlorane compounds. The concentrations of Dechlorane Plus (DP), mirex, Dechlorane (Dec) 602 and 603 ranged from ND to 169.85 pg/g wet weight (ww), 107.30 pg/g ww, 20.81 pg/g ww, 0.41 pg/g ww, respectively, while Dechlorane (Dec) 604 was not detected in any samples. Strong correlations between anti- and syn-DP and between mirex and Dec 602 were observed. The average anti-isomer fractional abundance (fanti) was 0.78±0.11 which was larger than the technical DP value (fanti=0.75). The estimated dietary daily intake of DP, 11.2×10(3) pg/day, was one to three orders of magnitude higher than other Dechloranes. Grain was the most contributed food group to dietary daily intake of DP for Korean population., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In this study, Dechlorane Plus (DP) concentrations were analyzed in marine sediments (depth: ~10 cm) from two Korean industrial bays. Two sediments were fractionated into 5 sizes by using gravitational split-flow thin fractionation technique and DP distribution was investigated in different particle size fractions. Elevated DP levels in surface sediments were observed at the site closest to land and industrial area. The highest concentrations of DP were detected in the finest grain-size (<10 μm, 451.2 and 149.9 pg/g dry weight for the two bays). The fraction of anti-DP to the total DP (fanti) in the two fractionated samples increased with reduced grain-size and significantly correlated with organic carbon content (OC), which can be caused by preferential adsorption of anti-DP or higher biodegradation rates of syn-DP in the fine particles. To provide insight into such mechanism, simulated experiments were conducted using activated charcarbon (ACC) to adsorb DP dissolved in methanol and molecular descriptors of both isomers were estimated using Gaussian 03. The adsorption results revealed that syn-DP was preferentially adsorbed by ACC, suggesting syn-DP is more hydrophobic than anti-DP. The preferential adsorption of syn-DP by ACC also supported the hypothesis that the enrichment of anti-DP was more likely due to preferential biodegradation of syn-DP in the sediment. Molecular characterization of anti-DP and syn-DP showed that syn-DP had a higher dipole moment, slightly larger Van der Waals volume, but smaller maximal diameter, which might explain its higher uptake rate in biota., (Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.)

Dechlorane Plus (DP) was determined in aquatic environment including sediment, sediment core, water, and fish species in a highly industrialized area in Pearl River Delta, South China. DP was analyzed in sediments and water at concentration ranging from 0.08 to 19.4 ng/g dry weight and from 0.24 to 0.78 ng/L, respectively. DP was detected in 80% of fish samples with concentration between undetectable level to 189 ng/g lipid weight. DP levels were significantly higher in the top layer (depth less than 36 cm with concentration ranging from 0.35 to 57.6 ng/g) than in the lower section (concentration ranging from 0.02 to 0.72 ng/g), indicating an increase in DP contamination in recent years. The fraction of anti-DP in the sediment and water are close to that in the technical mixtures implying no stereospecific degradation occurring. An enrichment of syn-DP was observed in three fish species suggesting that a stereospecific metabolism of anti-DP and/or stereoselective uptake of syn-DP occurring in fish species. The calculated BSAFs are 0.024, 0.037, and 0.10 for DP, in mud carp, nile tilapia, and plecostomus, respectively, suggesting relatively low bioavailability of DP isomers in the sediments., (Copyright © 2014 Elsevier B.V. All rights reserved.)

This study investigates some aspects of the environmental fate of galaxolide (HHCB) and tonalide (AHTN) musk fragrances, paying particular attention to the phenomenon of atmospheric transport of these substances. The problem was addressed theoretically and experimentally. Firstly, the application of a multimedia model allowed the analysis of their potential atmospheric transport. The obtained results argued in favor of a possible phenomenon of medium range atmospheric transport for both substances. These theoretical findings were supported by the experimental results, which showed their presence both in the fresh fallen snow and in water samples taken from the Frodolfo, a glacial stream that originates from the Forni Glacier (Alps, Northern Italy). Furthermore, the analysis of the air back-trajectories highlighted the prevalence of air masses of local origins that reached the sampling area passing through a densely anthropized area of Northern Italy. Finally, the experimental results discussed here gave evidences of accumulation of these two compounds in the glacier., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The effect of plant growth regulator forchlorfenuron (CPPU) 1 x 10(-6), 0.67 x 10(-6), 0.5 x 10(-6) on fruit morphology and effective components lignans was studied. Those morphologies were the combination of four basic morphological changes. The result showed, diametre were increased and longitudinal diametre of fruits were inhibited by foliage fertilizers including CPPU. At the same time, 1 000-grain weight and yield showed the varying degrees increase under CPPU. The order of the degree was 0.5 x 10(-6) > 1 x 10(-6) > 0.67 x 10(-6). Six lignans content of Schisandra chinensis of different harvest time and different CPPU processing groups were determined, the results showed that lignans accumulation occurred mainly in periods of premature the half mature fruiting stages. Under the 0.67 x 10(-6) CPPU treatment, schisandrol B, schisandrin B, schisandrin C content of S. chinensis showed different increase.

To establish a method for determination contents of schizandrin, tanshinone I, cryptotanshinone, tanshinone II (A) and schizandrin B in rongxin pills. The HPLC method was performed on an Agilent C18. The mobile phase was composed of methnol and water wish gradient elution. The flow rate was 1.0 mL x min(-1). The column temperature was 30 degrees C and the detection wavelength wash 240 nm. The linear of schizandrin, tanshinone I, cryptotanshinone, Tanshinone II (A) and schizandrin B were 3.000-48.00 (r = 1.000), 3.985-63.76 (r = 0.999 9), 6.370-101.9 (r = 1.000), 8.690-139.0 (r = 0.999 9), 1.700-27.20 mg x L(-1) (r = 0.999 9), respectively. The average recoveries were 98.44%, 100.3%, 99.29%, 99.07%, 98.42%, and RSDs were 0.61%, 1.1%, 0.52%, 0.72%, 0.97%. The method is convenient, accurate and has good precision. It can be used for determination of the preparation.

Hydrophobic organic contaminants in soils may pose toxicity or transfer to food chains after their uptake to soil biota. However, uptake data for earthworms are usually limited, as: (a) only fixed exposure times are studied instead of whole uptake kinetics and (b) studies including compounds with different environmental properties and more than two soils of different properties are quite rare. In our study, five persistent organic pollutants (phenanthrene, pyrene, lindane, p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT), and polychlorinated biphenyl congener No. 153 (PCB 153)) were added to six soils of a wide range of soil properties. Detailed kinetics of uptake to earthworms Eisenia fetida were measured. Results indicated that an equilibrium of concentrations for p,p'-DDT and PCB 153 was reached after 11 days of exposure in all soils. Uptake of phenanthrene, pyrene, and lindane was strongly influenced by the decrease in concentrations in the soils, resulting in peak-shaped accumulation curves. Only in soils with the highest total organic carbon content (7.9 and 20.2%), the equilibrium of lindane concentrations was achieved (after 17 and 5 days of exposure, respectively). We recommend calculating bioaccumulation factors as a ratio of the uptake and elimination rate constants to precise the risk assessment., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Deoxyschizandrin is an active lignin ingredient originating from Schisandra chinensis (Turcz.) Baill or Schisandrae Sphenantherae Fructus. In the present study, a novel and efficient strategy was developed for the in vivo screening and identification of deoxyschizandrin metabolites using ultra high performance liquid chromatography combined with triple TOF mass spectrometry (UPLC-TOF/MS/MS). This strategy was characterized by the following: a novel and unique multiple mass defect filter (MMDF) combined with an on-line data acquisition method that is dependent on dynamic background subtraction (DBS) was developed to trace all of the probable metabolites of deoxyschizandrin. The MMDF and DBS methods could trigger an IDA scan for the low-level metabolites that are masked by background noise and endogenous components. A combination of data processing methods including extracted ion chromatography (XIC), mass defect filtering (MDF), product ion filtering (PIF) and neutral loss filtering (NLF) were employed to identify the metabolites of deoxyschizandrin. Next, the structures of the metabolites were elucidated based on an accurate mass measurement, the fragmentation patterns of the parent drug and relevant drug bio-transformation knowledge. Finally, an important parameter ClogP was used to estimate the retention time of isomers. Based on the proposed strategy, 51 metabolites (including 49 phase I and 2 phase II metabolites) were identified in rats after the oral administration of deoxyschizandrin. Among these metabolites, 41 metabolites were characterized in the rat urine, and 28 metabolites were identified in the rat bile. The results indicated that oxidization was the main metabolic pathway and that the methoxy group and the biphenyl cyclooctene were the metabolic sites. Conjugation with sulfate and cysteine groups produced two phase-II metabolites. This study firstly reported the description of deoxyschizandrin metabolism in vivo. This study provided a practical strategy for rapidly screening and identifying metabolites, and this methodology can be widely applied for the structural characterization of the metabolites of other compounds., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Dechlorane plus (DP) is a high-productive volume substance which had been identified as ubiquitous pollutant and has been widely detected in biota. In the present study, common carp (Cyprinus carpio) was exposed to known amounts of commercial DP-25 under laboratory conditions. The gastrointestinal absorption and tissue-specific bioaccumulation of DP and its dechlorinated analogs in common carp were investigated. The higher absorption efficiencies but lower assimilation efficiencies of anti-isomers indicated stereoselective metabolism of anti-isomers in fish. Linear uptake curves were seen in serum and muscle, but the depuration curves for all the four tissues (muscle, serum, liver and gonad) did not follow the first-order kinetics. The liver exhibited a high affinity for anti-isomers during the experiment. Other tissues, such as serum, muscle, and gonad, showed a selective accumulation of syn-DP in the early stages of the experiment, particularly the serum. However, the deviation of fanti between different tissues disappeared at late stages of the experiment, and the fanti values in all tissues were close to that in commercial mixtures. Our results suggest that the bioaccumulation of DP is a complex and multi-factorial process., (© 2013 Published by Elsevier Inc.)

Eighty-seven soil samples collected from North China were analyzed for Dechlorane Plus (DP). The concentrations of DP ranged from not detectable (ND) to 12.21 ng/g with a mean of 0.55 ng/g. The mean concentrations of total DP and syn-DP in four regions of North China were in the following order: Jingjin (Beijing and Tianjin) > Shandong > Shanxi > Hebei, while the mean concentrations of anti-DP in the four regions were in a different order: Shandong > Jingjin > Shanxi > Hebei. The mean f syn values for Jingjin (0.27), Hebei (0.24), and Shanxi (0.24) were close to 0.25, while the mean f syn value for Shandong (0.31) was closer to 0.35. In addition, the f syn value for Shandong was significantly higher (P < 0.01) than those of the other regions (Jingjin, Heibei, and Shanxi), indicating specific sources of DP. Syn-DP displayed a strong linear relationship with anti-DP (R(2) = 0.74), indicating that no obvious stereoselective process occurred in the soil of North China. Ordinary kriging was undertaken to map the spatial patterns of DP. High concentrations of DP in soils were present in south of Shanxi, central Hebei, south of Tianjin, and the south and northeast of Shandong, which were suggested to be connected with human activities such as e-waste dismantling.

Dust samples were collected in Beijing, China, from four different indoor microenvironments (office, hotel, kindergarten, and student dormitory) and one outdoor (road dust) microenvironment. These five composite samples were fractionated into 13 sequential size fractions and an individual fraction of <50 μm for further analysis. In the fractions of <50 μm, nine phosphorus flame retardants (∑PFRs), four novel brominated flame retardants (∑NBFRs), and two Dechlorane Plus isomers (DPs) showed the highest concentrations in hotel dust (124,000 ng g(-1)), dormitory dust (14,200 ng g(-1)), and kindergarten dust (231 ng g(-1)), respectively. Nevertheless, nine polybrominated diphenyl ethers (∑PBDEs) were the dominant flame retardants (FRs) (96% of total FRs) in road dust, with the maximum concentration of 23,700 ng g(-1), higher than in any indoor dust. The FR contamination varied strongly among different types of microenvironments, leading to high human exposure to various FRs. Concentrations of FRs did not increase constantly with a particle size decrease. Fractions with a particle size around 900, 100, and 10 μm could represent peak values, while valley values were commonly detected around fractions with a particle size around 40 μm. Large differences were found between indoor dust and road dust. In road dust, FRs were mainly enriched in fractions of <50 μm. The organic content of dust, FR application, and consequent abrasion processes of FR-containing materials might be the determinants of the FR concentrations. Volatilization and abrasion were considered to be important migration pathways for FRs. DPs and BDE-209 were sought to be mainly applied in abrasion-proof materials, while most phosphorus flame retardants (PFRs) were probably added in a large proportion in materials easy to wear.

Coronene is a high molecular weight polycyclic aromatic hydrocarbon with seven aromatic rings. It, more specifically a lower ratio of Benzo[a]pyrene to Coronone (BaP/COR), is suggested as a marker for vehicle emission. In the present study, emissions of Coronene were measured from residential combustions of wood, crop straw, and pellets. The detection of COR in non-vehicle emission sources, and comparable BaP/COR ratios between the solid fuel combustion and vehicle emissions indicated that the generality of COR or the BaP/COR ratio as markers for the vehicle emission would be questionable, especially for the area where solid fuel combustion dominated the PAHs emission., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

This study estimated daily exposure to Dechlorane Plus (DP) and polybrominated diphenyl ethers (PBDE) via inhalation and diet. Samples of atmospheric particles and food (obtained by market basket method) from Osaka, Japan were analyzed for DP (syn-, anti-) and PBDE using gas chromatography-mass spectrometry. DP was detected in both atmospheric particles and food samples. Among the atmospheric particles, DP was detected in all samples. ΣDP concentration was 7.1-15.4 pg m(-3) and anti-DP was the dominant residue among DP isomers. PBDE was also detected in all the atmospheric particles. ΣPBDE concentration was 9.9-23.3 pg m(-3). In the market basket study, DP was detected in Groups Ш (sugar and confectionary), V (legumes and their products), X (fish, shellfish, and their products), and XI (meat and eggs) at concentrations of 3.3, 2.8, 1.9, and 1.5 pg g(-1) wet wt, respectively. PBDE was detected in Groups Ш, IV (oils and fats), V, X, XI, and XШ (seasonings and other processed foods) at concentrations of 153, 79.1, 74.6, 308, 94.8, and 186 pg g(-1) wet wt, respectively. The daily intake of ΣDP (750 pg day(-1)) via inhalation and diet was approximately one percent of that for ΣPBDE (62 ng day(-1))., (© 2013 Published by Elsevier Inc.)

This study aimed to investigate the in vivo behaviors of the main components in traditional Chinese medicine (TCM) fomulae. The plasma pharmacokinetics, tissue distribution and excretion of the main component-schisandrin in rats after oral administration of a classical TCM prescription, shengmaisan (SMS), were studied by a developed and validated UPLC-MS/MS method. The separation of schisandrin was achieved on a UPLC HSS T3 column with a mobile phase consisting of acetonitrile and water at a flow rate of 0.5 mL/min by linear gradient elution. The MS/MS detection was carried out by monitoring the fragmentation of m/z 415.22 → 384.26 for schisandrin on a triple quadrupole mass spectrometer. The result showed that the method was suitable for the quantification of schisandrin in plasma, tissue and excreta samples with satisfactory selectivity, precision, accuracy, sensitivity, linearity and recovery. Pharmacokinetic results showed a rapid absorption phase with the mean Tmax of 0.17 h and a relatively slow elimination proceeding with a half-life (T1/2 ) of 5.24 ± 1.28 h. The tissue distribution showed the maximum concentration distributions of schisandrin after oral administration of SMS were in the order of small intestine > large intestine > lung > liver > kidney > spleen > heart > brain. Only 0.005-0.006% of schisandrin was recovered in feces and was not detected in urine., (Copyright © 2013 John Wiley & Sons, Ltd.)

No scientific data is available on emerging contaminants including Polybrominated Diphenyl Ethers (PBDEs) and Dechloran Plus (DP) levels in the environment in Pakistan. Levels of PBDEs and DP were determined in the soil, sediment and atmospheric samples along the stretch of River Ravi in Punjab Province. Average concentrations of ΣPBDEs in atmosphere, soils and sediments were 36 pg m(-3), 40 ng g(-1) and 640 ng g(-1). BDE-209 was the most abundant PBDE congener, showing that deca-BDE accounts for most of the total PBDE emitted in the environment of Pakistan. Total DP levels were calculated as 88 pg m(-3), 0.8 ng g(-1) and 1.9 ng g(-1) in air, soil and sediment samples, respectively. The lower average fractions of anti-DP showed significant differences to those of the technical mixtures, indicating the lack of DP production source in Pakistan., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The impact of eight household micropollutants (erythromycin, ofloxacin, ibuprofen, 4-nonylphenol, triclosan, sucralose, PFOA and PFOS (PFAAs)) on the laboratory bacterial strain Escherichia coli MG1655 and on activated sludge from an urban wastewater treatment plant was studied. Growth-based toxicity tests on E. coli were performed for each micropollutants. The effect of micropollutants on activated sludge (at concentrations usually measured in wastewater up to concentrations disturbing the bacterial growth of E. coli) was examined in batch reactors and by comparison to a control reactor (without micropollutants). The bound extracellular polymeric substances (EPS) secreted by the sludge were measured by size exclusion chromatography and their overexpression was considered as an indicator of bacteria sensitivity to environmental changes. The chemical oxygen demand (COD) and the ammonium concentration were monitored to evaluate the biomass ability to remove the macropollution. Some micropollutants induced an increase of bound EPS in activated sludge flocs at concentrations depending on the micropollutant: erythromycin from 100 μg/L, ofloxacin from 10 μg/L, triclosan from 0.5 μg/L, 4-nonylphenol from 5000 μg/L and PFAAs from 0.1 μg/L. This suggests that the biomass had to cope with new conditions. Moreover, at high concentrations of erythromycin (10 mg/L) and ibuprofen (5 mg/L) bacterial populations were no longer able to carry out the removal of macropollution. Ibuprofen induced a decrease of bound EPS at all the studied concentrations, probably reflecting a decrease of general bacterial activity. The biomass was not sensitive to sucralose in terms of EPS production, however at very high concentration (1 g/L) it inhibited the COD decrease. Micropollution removal was also assessed. Ibuprofen, erythromycin, ofloxacin, 4-nonylphenol and triclosan were removed from wastewater, mainly by biodegradation. Sucralose and PFOA were not removed from wastewater at all, and PFOS was slightly eliminated by adsorption on sludge., (Copyright © 2013 Elsevier B.V. All rights reserved.)