Thyroid Hormone Receptor Agonistic and Antagonistic Activity of Newly Synthesized Dihydroxylated Polybrominated Diphenyl Ethers: An In Vitro and In Silico Coactivator Recruitment Study.

Dihydroxylated polybrominated diphenyl ethers (DiOH-PBDEs) could be the metabolites of PBDEs of some organisms or the natural products of certain marine bacteria and algae. OH-PBDEs may demonstrate binding affinity to thyroid hormone receptors (TRs) and can disrupt the functioning of the systems modulated by TRs. However, the thyroid hormone disruption mechanism of diOH-PBDEs remains elusive due to the absence of diOH-PBDEs standards. This investigation explores the potential disruptive effects of OH/diOH-PBDEs on thyroid hormones via competitive binding and coactivator recruitment with TRα and TRß. At levels of 5000 nM and 25,000 nM, 6-OH-BDE-47 demonstrated significant recruitment of steroid receptor coactivator (SRC), whereas none of the diOH-PBDEs exhibited SRC recruitment within the range of 0.32-25,000 nM. AutoDock CrankPep (ADCP) simulations suggest that the conformation of SRC and TR-ligand complexes, particularly their interaction with Helix 12, rather than binding affinity, plays a pivotal role in ligand agonistic activity. 6,6'-diOH-BDE-47 displayed antagonistic activity towards both TRα and TRß, while the antagonism of 3,5-diOH-BDE-100 for TRα and TRß was concentration-dependent. 3,5-diOH-BDE-17 and 3,5-diOH-BDE-51 exhibited no discernible agonistic or antagonistic activities. Molecular docking analysis revealed that the binding energy of 3,3',5-triiodo-L-thyronine (T3) surpassed that of OH/diOH-PBDEs. 3,5-diOH-BDE-100 exhibited the highest binding energy, whereas 6,6'-diOH-BDE-47 displayed the lowest. These findings suggest that the structural determinants influencing the agonistic and antagonistic activities of halogen phenols may be more intricate than previously proposed, involving factors beyond high-brominated PBDEs or hydroxyl group and bromine substitutions. It is likely that the agonistic or antagonistic propensities of OH/diOH-PBDEs are instigated by protein conformational changes rather than considerations of binding energy.

Deriving aquatic PNECs of endocrine disruption effects for PFOS and PFOA by combining species sensitivity weighted distributions and adverse outcome pathway networks.

Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), as emerging endocrine-disrupting chemicals (EDCs), pose adverse effects on aquatic organisms. Conventional ecological risk assessment (ERA) not fully considering the mode of toxicity action of PFOS and PFOA, may result in an underestimation of risks and confuse decision-makers. In the study, we developed species sensitivity weighted distribution (SSWD) models based on adverse outcome pathway (AOP) networks for deriving predicted no-effect concentrations (PNECs). Three kinds of weighting criteria (intraspecies variation, trophic level abundance, and data quality) and weighted log-normal distribution methods were adopted. The developed models considered the inter/intraspecies variation and integrated nontraditional endpoints of endocrine-disrupting effects. The PNECs of endocrine disruption effects were derived as 2.52 µg/L (95% confidence intervals 0.667-9.85 µg/L) for PFOS and 18.7 µg/L (5.40-71.0 µg/L) for PFOA, which were more conservative than those derived from the SSD method and were comparable with the values in the literature based on the chronic toxicity data. For PFOS, the effect of growth and development was the most sensitive; however, for PFOA, the effect of reproduction was the most sensitive in the effects of growth and development, reproduction, biochemistry and genetics, and survival. The endocrine-disrupting effects of PFOS and PFOA are significant and need to be fully recognized in the ERA. This study provided an ERA framework that can improve the ecological relevance and reduce the uncertainty of PNECs of EDCs.

Fluorescent/Colorimetric Dual-Mode Discriminating Gln and Val Enantiomers Based on Carbon Dots.

Discrimination and quantification of amino acid (AA) enantiomers are particularly important for diagnosing and treating diseases. Recently, dual-mode probes have gained a lot of research interest because they can catch more detecting information compared with the single-mode probes. Thus, it is of great significance to develop a dual-mode sensor realizing AA enantiomer discrimination conveniently and efficiently. In this work, carbon dot L-TCDs were prepared by N-methyl-1,2-benzenediamine dihydrochloride (OTD) and l-tryptophan. With the assistance of H2O2, L-TCDs show an excellent discrimination performance for enantiomers of glutamine (Gln) and valine (Val) in both fluorescent and colorimetric modes. The fluorescence enantioselectivity of Gln (FD/FL) and Val (FL/FD) is 5.29 and 4.13, respectively, and the colorimetric enantioselectivity of Gln (ID/IL) and Val (IL/ID) is 13.26 and 3.42, individually. The chiral recognition mechanism of L-TCDs was systematically studied. L-TCDs can be etched by H2O2, and the participation of AA enantiomers results in different amounts of the released OTD, which provides fluorescent and colorimetric signals for identifying and quantifying the enantiomers of Gln and Val. This work provides a more convenient and flexible dual-mode sensing strategy for discriminating AA enantiomers, which is expected to be of great value in facile and high-throughput chiral recognition.

Assessment of heavy metal contamination of an electrolytic manganese metal industrial estate in northern China from an integrated chemical and magnetic investigation.

Heavy metal concentrations (Al, V, Mn, Fe, Co, Ni, Cu, Zn, and Pb) and the magnetic properties of soil and sediment samples in/around an electrolytic manganese metal (EMM) industrial estate in northern China were investigated. Potential enrichment of Mn, Zn, and Pb was found in/around the core area of the EMM industrial estate; however, the pollution load index (PLI) values did not indicate severely polluted levels. For adults, all hazard index (HI) values of noncarcinogenic risks in the soil samples were below the safe level of 1.00. For children, none of the HI values exceeded the safe level, except Mn (HI = 1.23) in one industrial estate sample. The particle size of magnetic materials was mostly in the range of stable single-domain, and coarser ferrimagnetic phases enhanced the magnetic parameters in the industrial estate soils. Highly positive correlations were found between magnetic parameters, heavy metal concentrations, and PLI values, demonstrating that the magnetic parameters are an efficient proxy for assessing heavy metal contamination. Enrichment of Mn, Zn, and Pb was mainly derived from the EMM industry. The data showed that the EMM industrial estate under cleaner production had limited adverse impacts on the adjacent environment from the perspective of heavy metal contamination.

Occurrence and ecological risk assessment of 2,2',4,4'-tetrabromodiphenyl ether and decabromodiphenyl ether in surface waters across China.

Polybrominated diphenyl ethers (PBDEs) are efficient brominated flame retardants and are released into various environmental media via usage, recycling and disposal. This study investigated the concentrations and ecological risks of two typical PBDEs, 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) and decabromodiphenyl ether (BDE-209), in surface waters across China from 2011 to 2018. The results showed that the concentration of BDE-209 (8.25 ng L-1) was higher than that of BDE-47 (1.02 ng L-1), and the concentrations of BDE-47 and BDE-209 in the lakes (2.56 ng L-1 and 22.19 ng L-1, respectively) were higher than those in the rivers (0.58 ng L-1 and 7.05 ng L-1, respectively). In addition, the concentration of BDE-209 in the wet season (2.61 ng L-1) was lower than that in the dry season (10.83 ng L-1), whereas the concentration of BDE-47 in the wet season (0.24 ng L-1) was a little lower than that in the dry season (0.99 ng L-1). BDE-47 and BDE-209 concentrations showed a gradual decrease in surface waters across China during the eight-year period. Based on the species sensitivity distribution (SSD) models, the 5% hazardous concentration (HC5) and predicted no-effect concentration (PNEC) values were derived using the acute and chronic toxicity data of BDE-47 and BDE-209. Results showed that the PNEC values based on the acute and chronic toxicity data were 2.08 µg L-1 and 0.52 µg L-1 for BDE-47, respectively and 370 µg L-1 and 0.34 µg L-1 for BDE-209, respectively. The risk quotient (RQ) values of BDE-47 in surface waters across China were far smaller than 0.1 (low ecological risk). Similarly, the RQ values of BDE-209 were also smaller than 0.1, except for those at Baiyangdian Lake and Chaohu Lake, where the probability of 0.1 ≤ RQ < 1.0 (medium ecological risk) was approximately 10% based on 10,000 Monte Carlo simulations.

Spatial distribution pattern of dominant tree species in different disturbance plots in the Changbai Mountain.

The effects of disturbance on spatial patterns and species interactions provide critical information on community structure and species coexistence. Two standard plots of 1-ha were set, one of them was a sample plot with retrograde succession after disturbance, and the other one was undisturbed. Spatial indices and Spatial patterns statistics were used to analyze the spatial pattern and inter-specific correlation of main tree species in two plots. Our results showed that the diameter distributions of different species have reverse J-shape, unimodal and bimodal distribution in the disturbed plot, while bell-shaped curves were observed in the undisturbed plot. The distributions of tree species were mainly showed clustered patterns in almost all scales through univariate pair correlation function. Some similar results of the classification of Wiegand scheme of species association consistent with the consequences of the bivariate pair correlation. The mark variograms showed positive autocorrelation at a coarse scale. The current study may aid in efforts of forest management planning and ecosystem services. Meanwhile, different research methods of spatial distribution also help to improve the accuracy of spatial distribution and the interspecific association of tree species.

A tiered probabilistic approach to assess antibiotic ecological and resistance development risks in the fresh surface waters of China.

Exposure to antibiotics can result in not only ecotoxicity on aquatic organisms but also the development of antibiotic resistance. In the study, the ecotoxicity data and minimum inhibitory concentrations of the antibiotics were screened to derive predicted no-effect concentrations of ecological (PNECeco) and resistance development risks (PNECres) for 36 antibiotics in fresh surface waters of China. The derived PNECeco and PNECres values were ranged from 0.00175 to 2351 µg/L and 0.037-50 µg/L, respectively. Antibiotic ecological and resistance development risks were geographically widespread, especially in the Yongding River, Daqing River, and Ziya River basins of China. Based on the risk quotients, 11 and 14 of 36 target antibiotics were at high ecological risks and high resistance development risks in at least one basin, respectively. The higher tiered assessments provided more detailed risk descriptions by probability values and ß-lactams (penicillin and amoxicillin) were present at the highest levels for ecological and resistance development risks. Although there was uncertainty based on the limited data and existing methods, this study can indicate the overall situation of the existing risk levels and provide essential insights and data supporting antibiotic management.

[Role and mechanism of Cortex Moutan components in inhibiting production of toxic advanced glycation end products (AGEs)].

Advanced glycation end products(AGEs) can lead to many diseases such as diabetes and its complications. In this study, an in vitro non-enzymatic glycosylation reaction model-bovine serum albumin/methylglyoxal(BSA/MGO) reaction system was constructed and incubated with Cortex Moutan extract. High performance liquid chromatography(HPLC) and ultra-high performance liquid chromatography with quadrupole time-of-flight mass spectrometry(UPLC-Q-TOF-MS/MS) were used to detect and identify the active components that inhibited the formation of AGEs in the co-incubation solution of Cortex Moutan extract and MGO, and differential components such as salvianan, paeoniside, benzoylpaeoniflorin, mudanpioside J, galloyloxypaeoniflorin, benzoyloxy-paeoniflorin, 5-hydroxy-3 s-hydroxymethyl-6-methyl-2,3-dihydro benzofuran, and galloylpaeoniflorin were screened out, which were inferred to be the potential active components of Cortex Moutan extract to capture MGO. In addition, BSA-glucose reaction system was performed to investigate the influence of different concentrations of Cortex Moutan extract(decoction concentrations: 40, 80, 120, 160, and 200 mg·mL~(-1)) on inhibiting the production of AGEs in vitro. The inhibitory effects of Cortex Moutan extract and the differential components galloylpaeoniflorin and benzoyl paeoniflorin on the production of AGEs in human umbilical vein endothelial cells(HUVECs) induced by high glucose was further evaluated. Cell apoptosis was observed by acridine orange and ethidium bromide(AO/EB) double fluorescence staining. The results showed that Cortex Moutan Cortex extract and its differential components had certain inhibitory effects on the formation of AGEs, and could reduce cell apoptosis. This study provided reference for the treatment of diabetic vascular complications by Cortex Moutan inhibiting the toxic AGEs.

Tiered ecological risk assessment of nonylphenol and tetrabromobisphenol A in the surface waters of China based on the augmented species sensitivity distribution models.

The ecological risks of nonylphenol (NP) and tetrabromobisphenol A (TBBPA) have received continued attention owing to their large consumption, frequently detection, adverse effects on the reproductive fitness, and lack of risk assessment technical systems. The geometric mean of the median concentrations of NP in the 22 surface waters was 0.278 µg/L, and TBBPA in the seven surface waters was 0.014 µg/L in China. The species sensitivity distribution (SSD) models were augmented by extrapolated reproductive toxicity data of native species to reduce uncertainty. The SSD models and the hazardous concentrations for 5% of species exhibited good robustness and reliability using the bootstrap method and minimum sample size determination. The acute and reproductive predicted no-effect concentrations (PNECs) were derived as 9.88 and 0.187 µg/L for NP, and 56.6 and 0.0878 µg/L for TBBPA, respectively. The risk quotients indicated that 11 of 22 locations for NP, and 3 of 7 locations for TBBPA were at high ecological risk levels based on the reproductive PNECs. Furthermore, the higher tier ecological risk assessment (ERA) based on potential affected fraction and joint probability curves indicated that the ecological risks in the four of above locations needed further concern. The ERA based on both the acute and reproductive toxicity is essential for assessing the ecological risks of NP and TBBPA, otherwise using acute PNECs only may result in an underestimation of ecological risk. The developed tiered ERA method and its framework can provide accurate, detailed, quantitative, locally applicable, and economically technical support for ERA of typical endocrine-disrupting chemicals in China.

A QSAR-ICE-SSD Model Prediction of the PNECs for Per- and Polyfluoroalkyl Substances and Their Ecological Risks in an Area of Electroplating Factories.

Per- and polyfluoroalkyl substances (PFASs) are a class of highly fluorinated aliphatic compounds that are persistent and bioaccumulate, posing a potential threat to the aquatic environment. The electroplating industry is considered to be an important source of PFASs. Due to emerging PFASs and many alternatives, the acute toxicity data for PFASs and their alternatives are relatively limited. In this study, a QSAR-ICE-SSD composite model was constructed by combining quantitative structure-activity relationship (QSAR), interspecies correlation estimation (ICE), and species sensitivity distribution (SSD) models in order to obtain the predicted no-effect concentrations (PNECs) of selected PFASs. The PNECs for the selected PFASs ranged from 0.254 to 6.27 mg/L. The ΣPFAS concentrations ranged from 177 to 983 ng/L in a river close to an electroplating industry in Shenzhen. The ecological risks associated with PFASs in the river were below 2.97 × 10-4.

[Spatial pattern and interspecific association of tree species in coniferous and deciduous broad-leaved mixed forest under different disturbance intensities]. / ä¸åŒå¹²æ‰°å¼ºåº¦ä¸‹é’ˆé˜”æ··äº¤æž—æ ‘ç§ç©ºé—´æ ¼å±€åŠç§é—´å ³è”æ€§.

We explored the effects of disturbance densities on the spatial pattern and the association of tree species in the coniferous broadleaved mixed forest in Pangquangou Nature Reserve of Guandi Mountain. Using three factors including canopy density, stand density and number of stumps, we classified the disturbance intensities of different forest stands into three levels, non-disturbance, moderate disturbance, and severe disturbance. The spatial distribution pattern and the association of different tree species were analyzed by spatial point pattern K2 function. The results showed that the diameter distribution of trees in undisturbed plots was inverted 'J' type, while that of moderate disturbance and serious disturbance plots was under bimodal curve distribution. The stand distribution pattern showed a small-scale aggregated distribution under undisturbed and moderately distur-bance, and a random distribution under heavy disturbance. At the small scale, the coniferous and broadleaved species showed no correlation in undisturbed stands, were positively correlated in moderately disturbed stands, and negatively correlated in seriously disturbed stands. At large scale, they were no correlated in both moderately and seriously disturbed stands. The results suggested that abundance of trees with small diameter in the forests was negatively with disturbance intensity, which led to the lower degree of intraspecific aggregation at small scale. Meanwhile, appropriate levels of disturbance would benefit the collaborative use of environmental resources for trees. Our results revealed the impacts of disturbance density on forest community structure and could provide theoretical basis for forest management.

A stable low-temperature H2-production catalyst by crowding Pt on α-MoC.

The water-gas shift (WGS) reaction is an industrially important source of pure hydrogen (H2) at the expense of carbon monoxide and water1,2. This reaction is of interest for fuel-cell applications, but requires WGS catalysts that are durable and highly active at low temperatures3. Here we demonstrate that the structure (Pt1-Ptn)/α-MoC, where isolated platinum atoms (Pt1) and subnanometre platinum clusters (Ptn) are stabilized on α-molybdenum carbide (α-MoC), catalyses the WGS reaction even at 313 kelvin, with a hydrogen-production pathway involving direct carbon monoxide dissociation identified. We find that it is critical to crowd the α-MoC surface with Pt1 and Ptn species, which prevents oxidation of the support that would cause catalyst deactivation, as seen with gold/α-MoC (ref. 4), and gives our system high stability and a high metal-normalized turnover number of 4,300,000 moles of hydrogen per mole of platinum. We anticipate that the strategy demonstrated here will be pivotal for the design of highly active and stable catalysts for effective activation of important molecules such as water and carbon monoxide for energy production.

Maximizing the Synergistic Effect of CoNi Catalyst on α-MoC for Robust Hydrogen Production.

We report the syntheses of highly dispersed CoNi bimetallic catalysts on the surface of α-MoC based on the strong metal support interaction (SMSI) effect. The interaction between the nearly atomically dispersed Co and Ni atoms was observed for the first time by the real-space chemical mapping at the atomic level. Combined with the ability of α-MoC to split water at low temperatures, the as-synthesized CoNi/α-MoC catalysts exhibited robust and synergistic performance for the hydrogen production from hydrolysis of ammonia borane. The metal-normalized activity of the bimetallic 1.5Co1.5Ni/α-MoC catalyst reached 321.1 molH2·mol-1CoNi·min-1 at 298 K, which surpasses all the noble metal-free catalysts ever reported and is four times higher than that of the commercial Pt/C catalyst.

Occurrence and emission of phthalates, bisphenol A, and oestrogenic compounds in concentrated animal feeding operations in Southern China.

Phthalates (PAEs), bisphenol A (BPA), and oestrogenic compounds have become major concerns due to their endocrine-disrupting effect. However, few studies related to the occurrence of PAEs, BPA, and oestrogen in food and compost from different growth age livestock have been conducted. In this study, faeces, urine and food samples were collected from a typical livestock (cow) and a special livestock (pigeon) from concentrated animal feeding operations (CAFOs). The daily total oestrogen excretion of a single cow ranged from 192 µg/day to 671 µg/day, which was significantly higher than that of a single pigeon (0-0.01 µg/day). Conjugated oestrogens represented 22.0-46.0% of the total oestrogens excreted from cow faeces and 80.7-91.8% of those from cow urine, indicating that the form of the excreted oestrogens depends on the livestock species and type of excrement. BPA was all detected in all livestock manure and food, and the concentration in pigeon was 9.2-40.2 ng/g and 23.1 ng/g respectively, while that in cattle was 50.5-72.0 ng/g and 41.1 ng/g respectively. The results indicated that the food is significant sources of BPA entering the process of cow and pigeon breeding. Diethyl phthalate (DEP) was detected at high frequency in pigeon faeces samples, suggesting that pigeons were highly exposed to these plasticisers. The total oestradiol equivalent quantity (EEQt) of livestock origin in aquatic environments was estimated to be 2.99 ng/L, which was higher than the baseline hazard value (1 ng/L) (Xu et al., 2018). The study provides data on the emissions and sources of PAEs, BPA, and oestrogenic compounds from different livestock in CAFOs and demonstrates that food is a significant source of BPA entering livestock.

Toxicity and accumulation of 6-OH-BDE-47 and newly synthesized 6,6'-diOH-BDE-47 in early life-stages of Zebrafish (Danio rerio).

Dihydroxylated polybrominated diphenyl ethers (diOH-PBDEs) appear to be natural products or metabolites of PBDEs in some marine organisms, yet its toxicity is still largely unknown. With a newly lab-synthesized diOH-PBDE, 6,6'-dihydroxy-2,2',4'4'-tetrabromodiphenyl ether (6,6'-diOH-BDE-47) in hand, the present study has provided the first data set to compare 6-hydroxy-2,2',4'4'- tetrabromodiphenyl ether (6-OH-BDE-47) and 6,6'-diOH-BDE-47 for their acute toxicity and accumulation, and thyroid hormone levels in treated zebrafish larvae. By real time-PCR technique, transcripts of hypothalamic-pituitary-thyroid axis associated genes were also investigated in developing larvae at 96 h post fertilization (96 hpf). Apparently, 6,6'-diOH-BDE-47 was less toxic than that of 6-OH-BDE-47: 1) the 96-h LC50 (96-h median lethal concentration) of 6-OH-BDE-47 and 6,6'-diOH-BDE-47 were 235 nM and 516 nM, respectively; 2) although severe developmental delays and morphological deformities were observed in zebrafish larvae in high exposure doses, at the exposure concentration of 1-50 nM, the accumulated 6-OH-BDE-47 and 6,6'-diOH-BDE-47 is ranged between 226-2279 nmol/g and 123-539 nmol/g in treated larvae; and 3) for 6-OH-BDE-47, its bioconcentration factor (BCF) were 1.83- to 4.30-fold more than that of 6,6'-diOH-BDE-47, suggesting that the lower internal exposure concentration of 6,6'-diOH-BDE-47 may lead to lower toxicity. The increased thyroid hormone levels were recorded for 1 nM of 6-OH-BDE-47 and 20 nM of 6,6'-diOH-BDE-47, and the exposures both significantly increased thyroid gland-specific transcription of thyroglobulin gene, indicating an adverse effect associated with the HPT axis. Therefore, 6,6'-diOH-BDE-47, with lower toxicity compared to that of 6-OH-BDE-47, still possesses hazards and environmental risk.

6-OH-BDE-47 exposure-induced Parkinson's disease pathology in Sprague Dawley rat.

6-Hydroxy-BDE-47 (6-OH-BDE-47) is an important in vivo metabolite derived from 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), a ubiquitous environmental pollutant. The chemical has been widely detected in environmental and biological samples. However, as a potential neurotoxin, whether 6-OH-BDE-47 could promote the development of typical neurodegenerative diseases such as Parkinson's disease (PD) is still unknown. Here, we tested the potential PD-related neurotoxic effect of 6-OH-BDE-47 in rat. The chemical with levels of 0.1, 1 and 10 µg was stereotaxically injected into the right midbrain regions of rat where contain abundant dopaminergic neurons. The resulting deteriorated motor function and decreased levels of striatal dopamine and nigrostriatal tyrosine hydroxylase indicate the dopaminergic neuron loss after the injection. Proteomics study revealed that protein degradation pathways were affected. Western blot analysis confirmed that 6-OH-BDE-47 could inhibit ubiquitination and autophagy, resulting in the increased formation of α-synuclein (α-syn) aggregate, an important pathological hallmark of PD. Overall, our study demonstrated that the 6-OH-BDE-47 administration could induce motor defect by impairing dopaminergic system and promote α-syn aggregation by inhibiting ubiquitination and autophagy, suggesting that the occurrence of 6-OH-BDE-47 in brain could be a risk for developing PD.

Determination of newly synthesized dihydroxylated polybrominated diphenyl ethers in sea fish by gas chromatography-tandem mass spectrometry.

Dihydroxylated polybrominated diphenyl ethers (diOH-PBDEs) can be natural products of marine organisms or the metabolites of PBDEs. The optimal determination method and concentration of diOH-PBDEs in seafood are unknown due to a lack of commercially available standards. In the present study, diOH-PBDEs were synthesized, and an efficient measurement method for OH-PBDEs and diOH-PBDEs in sea fish muscle samples, including extraction, clean-up and gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis, was established. Pressurized liquid extraction (PLE) followed by partitioning with a KOH solution and florisil cartridge clean-up proved to be a reliable and robust method for detecting all OH-PBDEs/diOH-PBDEs. GC-MS/MS with an electron ionization (EI) source analysis was a sensitive analytical instrument for OH-PBDEs/diOH-PBDEs. The recovery using this method ranged from 19% to 101%, 28%-88% and 42%-90% for 10 ng, 20 ng and 40 ng spiking levels, respectively. The equipment detection limits (EDLs) were in the range of 0.31-2.78 pg/µL, and the limits of detection (LOD) for the method were in the range of 5.07-38.74 pg/g wet weight. Concentrations of diOH-PBDEs in the marine fish muscle samples were in the range of 32.43-1528.63 pg/g wet weight. Similar compositions of OH-PBDEs/diOH-PBDEs were found within the same family of marine fish.

The characteristics of oestrone mobility in water and soil by the addition of Ca-biochar and Fe-Mn-biochar derived from Litchi chinensis Sonn.

In this study, the effect of biochar (BC) derived from Litchi chinensis Sonn. and its modification, including Ca-biochar (Ca-BC) and Fe-Mn-biochar (Fe-Mn-BC), on the transportation of oestrone (E1) in water and soil was investigated. Fe-Mn-BC showed better adsorption ability than other types of biochar (BC, Ca-BC) under different conditions (humic acid, pH, ionic strength) in an aqueous environment. The maximum mass of sorbent at 298 K increased from 1.12 mg g-1 (BC) to 4.18 mg g-1 (Fe-Mn-BC). Humic acid had a greater impact on aqueous E1 adsorption on these biochars than did the pH and ionic strength. Fe-Mn-BC as a soil amendment had a great control of E1 transport in soil, and no leachate of E1 was observed in the column experiment. E1 mobility showed strong retardation in amended soil with Ca-BC (Rf = 11.2) compared with raw soil (Rf = 7.1). These results suggested that Fe-Mn-BC was more effective in controlling E1 transportation, and Fe-Mn-BC could be used as an alternative and inexpensive adsorbent to reduce E1 contaminants from water and soil.

Construction of a sp3 /sp2 Carbon Interface in 3D N-Doped Nanocarbons for the Oxygen Reduction Reaction.

The development of highly efficient metal-free carbon electrocatalysts for the oxygen reduction reaction (ORR) is one very promising strategy for the exploitation and commercialization of renewable and clean energy, but this still remains a significant challenge. Herein, we demonstrate a facile approach to prepare three-dimensional (3D) N-doped carbon with a sp3 /sp2 carbon interface derived from ionic liquids via a simple pyrolysis process. The tunable hybrid sp3 and sp2 carbon composition and pore structures stem from the transformation of ionic liquids to polymerized organics and introduction of a Co metal salt. Through tuning both composition and pores, the 3D N-doped nanocarbon with a high sp3 /sp2 carbon ratio on the surface exhibits a superior electrocatalytic performance for the ORR compared to that of the commercial Pt/C in Zn-air batteries. Density functional theory calculations suggest that the improved ORR performance can be ascribed to the existence of N dopants at the sp3 /sp2 carbon interface, which can lower the theoretical overpotential of the ORR.