Identification and Prioritization of Environmental Organic Pollutants: From an Analytical and Toxicological Perspective.

Exposure to environmental organic pollutants has triggered significant ecological impacts and adverse health outcomes, which have been received substantial and increasing attention. The contribution of unidentified chemical components is considered as the most significant knowledge gap in understanding the combined effects of pollutant mixtures. To address this issue, remarkable analytical breakthroughs have recently been made. In this review, the basic principles on recognition of environmental organic pollutants are overviewed. Complementary analytical methodologies (i.e., quantitative structure-activity relationship prediction, mass spectrometric nontarget screening, and effect-directed analysis) and experimental platforms are briefly described. The stages of technique development and/or essential parts of the analytical workflow for each of the methodologies are then reviewed. Finally, plausible technique paths and applications of the future nontarget screening methods, interdisciplinary techniques for achieving toxicant identification, and burgeoning strategies on risk assessment of chemical cocktails are discussed.

Occurrence and Ecological Risk of Alkylamine Triazines in Chinese Estuarine Sediments: An Emerging Class of Persistent, Mobile, and Toxic Substances.

Identifying persistent, mobile, and toxic (PMT) substances from synthetic chemicals is critical for chemical management and ecological risk assessment. Inspired by the triazine analogues (e.g., atrazine and melamine) in the original European Union's list of PMT substances, the occurrence and compositions of alkylamine triazines (AATs) in the estuarine sediments of main rivers along the eastern coast of China were comprehensively explored by an integrated strategy of target, suspect, and nontarget screening analysis. A total of 44 AATs were identified, of which 23 were confirmed by comparison with authentic standards. Among the remaining tentatively identified analogues, 18 were emerging pollutants not previously reported in the environment. Tri- and di-AATs were the dominant analogues, and varied geographic distributions of AATs were apparent in the investigated regions. Toxic unit calculations indicated that there were acute and chronic risks to algae from AATs on a large geographical scale, with the antifouling biocide cybutryne as a key driver. The assessment of physicochemical properties further revealed that more than half of the AATs could be categorized as potential PMT and very persistent and very mobile substances at the screening level. These results highlight that AATs are a class of PMT substances posing high ecological impacts on the aquatic environment and therefore require more attention.

Occurrence and Distribution of Antibacterial Quaternary Ammonium Compounds in Chinese Estuaries Revealed by Machine Learning-Assisted Mass Spectrometric Analysis.

Antimicrobial resistance (AMR) undermines the United Nations Sustainable Development Goals of good health and well-being. Antibiotics are known to exacerbate AMR, but nonantibiotic antimicrobials, such as quaternary ammonium compounds (QACs), are now emerging as another significant driver of AMR. However, assessing the AMR risks of QACs in complex environmental matrices remains challenging due to the ambiguity in their chemical structures and antibacterial activity. By machine learning prediction and high-resolution mass spectrometric analysis, a list of antibacterial QACs (n = 856) from industrial chemical inventories is compiled, and it leads to the identification of 50 structurally diverse antibacterial QACs in sediments, including traditional hydrocarbon-based compounds and new subclasses that bear additional functional groups, such as choline, ester, betaine, aryl ether, and pyridine. Urban wastewater, aquaculture, and hospital discharges are the main factors influencing QAC distribution patterns in estuarine sediments. Toxic unit calculations and metagenomic analysis revealed that these QACs can influence antibiotic resistance genes (particularly sulfonamide resistance genes) through cross- and coresistances. The potential to influence the AMR is related to their environmental persistence. These results suggest that controlling the source, preventing the co-use of QACs and sulfonamides, and prioritizing control of highly persistent molecules will lead to global stewardship and sustainable use of QACs.

Unique Double and Triple Decker Arrangements of Rare-Earth 9,10-Diborataanthracene Complexes Featuring Single-Molecule Magnet Characteristics.

Herein, we present the first report on the synthesis of rare-earth complexes featuring a 9,10-diborataanthracene ligand. This 14-π-electron ligand is highly reductive and was previously used in small-molecule activation. Salt elimination reactions between dipotassium 9,10-diethyl-9,10-diborataanthracene [K2(DEDBA)] and [LnIII(η8-CotTIPS)(BH4)(thf)x] (CotTIPS=1,4-(iPr3Si)2C8H6) in a 1 : 1 ratio yielded heteroleptic sandwich complexes [K(η8-CotTIPS)LnIII(η6-DEDBA)] (Ln=Y, Dy, Er). These compounds form Lewis-base-free one-dimensional coordination polymers when crystallised from toluene. In contrast, reaction of [K2(DEDBA)] and [LnIII(η8-CotTIPS)(BH4)(thf)x] in a 1 : 2 ratio led to the formation of heteroleptic triple-decker complexes [(η8-CotTIPS)LnIII(µ-η6:η6-DEDBA)LnIII(η8-CotTIPS)] (Ln=Y, Dy, Er). Notably, these are not only the first lanthanide triple-decker compounds featuring a six-membered ring as a deck but also the first trivalent lanthanide triple-decker featuring a heterocycle in the coordination sphere. Magnetic investigations reveal that [K(η8-CotTIPS)LnIII(η6-DEDBA)] (Ln=Dy, Er) and [(η8-CotTIPS)ErIII(µ-η6:η6-DEDBA)ErIII(η8-CotTIPS)] exhibit Single-Molecule Magnet (SMM) behaviour. In the case of [(η8-CotTIPS)LnIII(µ-η6:η6-DEDBA)LnIII(η8-CotTIPS)] (Ln=Dy, Er), the introduction of a second near lanthanide ion results in strong antiferromagnetic interactions, allowing the enhancement of the magnetic characteristic of the system, compared to the quasi isolated counterpart. This research renews the overlooked coordination chemistry of the DBA ligand and expands it to encompass rare-earth elements.

Hilbert Space in Isotopologue Dy(III) SMM Dimers: Dipole Interaction Limit in [163/164Dy2(tmhd)6(tape)]0 Complexes.

Single-molecule magnets are molecular complexes proposed to be useful for information storage and quantum information processing applications. In the quest for multilevel systems that can act as Qudits, two dysprosium-based isotopologues were synthesized and characterized. The isotopologues are [164Dy2(tmhd)6(tape)] (1(I=0)) and [163Dy2(tmhd)6(tape)] (2(I=5/2)), where tmhd = 2,2,6,6-tetramethylheptandionate and tape = 1,6,7,12-tetraazaperylene. Both complexes showed slow relaxation at a zero applied magnetic field with dominant Orbach and Raman relaxation mechanisms. µSQUID studies at milli-Kelvin temperatures reveal quasi-single ion loops, in contrast with the expected S-shape (near zero field) butterfly loops, characteristic of antiferromagnetically coupled dimeric complexes. Through analysis of the low-temperature data, we find that the interaction operating between Dy(III) is small, leading to a small exchange biasing from the zero-field transition. The resulting indirectly coupled nuclear states are degenerate or possess a small energy difference between them. We, therefore, conclude that for the creation of Qudits with enlarged Hilbert spaces, shorter Dy(III)···Dy(III) distances are deemed essential.

An Integrated Workflow Assisted by In Silico Predictions To Expand the List of Priority Polycyclic Aromatic Compounds.

The limited information in existing mass spectral libraries hinders an accurate understanding of the composition, behavior, and toxicity of organic pollutants. In this study, a total of 350 polycyclic aromatic compounds (PACs) in 9 categories were successfully identified in fine particulate matter by gas chromatography high resolution mass spectrometry. Using mass spectra and retention indexes predicted by in silico tools as complementary information, the scope of chemical identification was efficiently expanded by 27%. In addition, quantitative structure-activity relationship models provided toxicity data for over 70% of PACs, facilitating a comprehensive health risk assessment. On the basis of extensive identification, the cumulative noncarcinogenic risk of PACs warranted attention. Meanwhile, the carcinogenic risk of 53 individual analogues was noteworthy. These findings suggest that there is a pressing need for an updated list of priority PACs for routine monitoring and toxicological research since legacy polycyclic aromatic hydrocarbons (PAHs) contributed modestly to the overall abundance (18%) and carcinogenic risk (8%). A toxicological priority index approach was applied for relative chemical ranking considering the environmental occurrence, fate, toxicity, and analytical availability. A list of 39 priority analogues was compiled, which predominantly consisted of high-molecular-weight PAHs and alkyl derivatives. These priority PACs further enhanced source interpretation, and the highest carcinogenic risk was attributed to coal combustion.

Occurrence and Temporal Trends of Benzotriazole UV Stabilizers in Mollusks (2010-2018) from the Chinese Bohai Sea Revealed by Target, Suspect, and Nontarget Screening Analysis.

Benzotriazole UV stabilizers (BZT-UVs), including 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole (UV-328) that is currently under consideration for listing under the Stockholm Convention, are applied in many commodities and industrial products. However, limited information is available on the interannual variation of their environmental occurrence. In this study, an all-in-one strategy combining target, suspect, and nontarget screening analysis was established to comprehensively explore the temporal trends of BZT-UVs in mollusks collected from the Chinese Bohai Sea between 2010 and 2018. Significant residue levels of the target analytes were determined with a maximum total concentration of 6.4 × 103 ng/g dry weight. 2-(2-Hydroxy-3-tert-butyl-5-methyl-phenyl)-5-chloro-benzotriazole (UV-326), 5-chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole (UV-327), and 2-(2-hydroxy-5-methylphenyl) benzotriazole (UV-P) were the predominant analogues, and UV-328 was the most frequently detected BZT-UV with a detection frequency (DF) of 87%. Whereas five biotransformation products and six impurity-like BZT-UVs were tentatively identified, their low DFs and semi-quantified concentrations suggest that the targeted analytes were the predominant BZT-UVs in the investigated area. A gradual decrease in the total concentrations of BZT-UVs was observed, accompanied by downward trends of the abundant compounds (e.g., UV-326 and UV-P). Consequently, the relative abundance of UV-327 increased because of its consistent environmental presence. These results suggest that continuous monitoring and risk assessment of BZT-UVs other than UV-328 are of importance in China.

A Critical Review on Transplacental Transfer of Per- and Polyfluoroalkyl Substances: Prenatal Exposure Levels, Characteristics, and Mechanisms.

Prenatal exposure to perfluoroalkyl and polyfluoroalkyl substances (PFASs) has aroused public concerns as it can pose multiple health threats to pregnant women and cause adverse birth outcomes for fetuses. In previous studies, the prenatal exposure levels and transplacental transfer efficiencies (TTE) of PFASs have been reported and discussed. Specifically, the binding affinities between PFASs and some transporters were determined, demonstrating that the TTE values of PFASs are highly dependent on their binding behaviors. To summarize primary findings of previous studies and propose potential guidance for future research, this article provides a systematic overview on levels and characteristics of prenatal exposure to PFASs worldwide, summarizes relationships between TTE values and structures of PFASs, and discusses possible transplacental transfer mechanisms, especially for the combination between PFASs and transporters. Given the critical roles of transporters in the transplacental transfer of PFASs, we conducted molecular docking to further clarify the binding behaviors between PFASs and the selected transporters. We proposed that the machine learning can be a superior method to predict and reveal behaviors and mechanisms of the transplacental transfer of PFASs. In total, this is the first review providing a comprehensive overview on the prenatal exposure levels and transplacental transfer mechanisms of PFASs.

Occurrence and Ecological Impact of Chemical Mixtures in a Semiclosed Sea by Suspect Screening Analysis.

Stress from mixtures of synthetic chemicals is among the key issues that have significant adverse impacts on the marine ecosystems. A robust screening workflow integrating toxicological-based ranking schemes is still deficient for comprehensive investigation on the main constituents in chemical mixtures that contribute to the ecological risks. In this study, the presence and compositions of a collection of priority pollutants were monitored by suspect screening analysis of seawater and estuarine water samples from the semiclosed Bohai Sea. In total, 108 organic pollutants in nine use categories were identified. Pesticides, intermediates, plastic additives, and per- and polyfluoroalkyl substances were the extensively detected chemical groups. Varied distribution patterns of the pollutants were illustrated intuitively in distinctive sampling areas by hierarchical cluster analysis, which were mainly influenced by run-off inputs, ocean currents, and chemical use history. Ecological risks of chemicals with quantified residue levels were first assessed by the toxicity-weighted concentration ranking scheme, and pentachlorophenol was found as the main contributor in the investigating areas. By optimization of multiple alternative variables (e.g., instrumental response and detection frequency), extended ranking of all the identified pollutants was plausible under the toxicological priority index framework. Similarity in toxicological endpoints of the prioritized pollutants could further been screened by ToxAlerts. Aromatic amine was highlighted as the most frequently detected structural alert (SA) for genotoxic carcinogenicity and mutagenicity. These findings fully demonstrate rationality of the ranking schemes integrated into the suspect screening analysis for profiling contamination characteristics, assessing ecological risk potentials, and prioritizing SAs.

Design, synthesis and structure-activity relationship optimization of phenanthridine derivatives as new anti-vitiligo compounds.

Humans have been suffering from vitiligo for a long time. Target vitiligo drugs have yet been approved. Activation of Wnt/ß-catenin signalling has potential in the therapeutic use of vitiligo, so exploring new drugs that specifically directly activate Wnt is worthwhile to obtain new anti-vitiligo agents. In this work, two portions design and synthesis were put into effect. firstly, 17 phenanthridine derivatives with C-4 substitutes were designed and synthesized, which compounds 4, 6, 12, 13 served as H-acceptor with protein showed enhance melanogenesis activity; Secondly, 7 hybrid new scaffolds of compounds were designed and synthesized, scaffold hopping compound 36 that aromatic benzene was replaced pyrazole on ring C showed enhance melanogenesis and tyrosinase activity; The last and most important, a comprehensive optimization and SARs of compound 36 were carried out, compounds 41 and 43 shared phenolic hydroxyl or 3-methyl-pyridine substitutes at C-7 position remarkably improved the capacity of melanogenesis and tyrosinase activity. Compound 43 were identified as new anti-vitiligo agents that specifically activate the Wnt/ß-catenin signalling pathway by targeting Axin. Structure-activity relationship analysis implied that H-acceptor substitutions at the C-4 position and phenolic hydroxyl or pyridine substitutions at the C-7 position would improve the activities of the compounds. These findings reveal a new therapeutic strategy for vitiligo, and compounds 41 and 43 may represent potential compounds for vitiligo treatment.

Recognition and Prioritization of Chemical Mixtures and Transformation Products in Chinese Estuarine Waters by Suspect Screening Analysis.

Chemical mixtures in surface waters could have significant impacts on exposure risks to human beings and pollution stress to aquatic system. By suspect screening analysis of high-resolution mass spectrometry data, occurrence, and compositions of ToxCast chemicals were investigated in grab estuarine water samples from a combination of 20 rivers that represents approximately 70% of the total river flow discharge along the east coast of China. In total, 59 ToxCast chemicals in seven use categories were identified, in which pesticides, intermediates, and pharmaceuticals were the abundant analogues. Significant differences in pollutant composition profiles were noticed, which possibly reflected singular release pattern and geographical-relevant usage preference (especially for herbicides and fungicides in the pesticide category). With the aid of tentative quantitative/semiquantitative measurement, essential contributors to the cumulative pollutant mass discharges and aquatic acute toxicity potentials were focused onto few particular chemicals. Existence of transformation products was further explored, which indicated that the fates of the selected parent ToxCast chemicals could be influenced by dominating transformation reactions (e.g., N-dealkylation and hydroxylation) and possible environmental factors (i.e., microbial activity). The results emphasize the necessity of suspect screening analysis for assessing the influence of terrestrial emissions of pollutants to the surrounding environment.

Identification of N-Nitrosamines and Nitrogenous Heterocyclic Byproducts during Chloramination of Aromatic Secondary Amine Precursors.

With diminishing pristine water, wastewater-affected waters that contain complex anthropogenic compounds are becoming important sources of drinking water and the compounds will inevitably react with disinfectants to form disinfection byproducts (DBPs). Secondary amines such as diphenylamine (DPA) analogues are considered as potential precursors of N-nitrosamines. In this study, an in situ 14N/15N-labeling and screening workflow was used to systematically investigate the formation of nitrogenous DBPs (N-DBPs) and putative reaction pathways. Twenty-four pairs of N-DBPs were generated and identified from chloramination of DPA through two main pathways, in which chloramines reacted with the amino and phenyl functional groups to form N-nitrosodiphenylamine and monochlorinated 5,10-dihydro-phenazine (Cl-DiH-Phe), respectively. Cl-DiH-Phe could further produce phenazine and the coupling products with another DPA molecule. Selective N-DBP formation was pH and dose-dependent, and the same reactions were observed for additional two aromatic DPA analogues. Effects of alkyl substituents on the formation pathways were investigated using a series of dialkyl and N-alkyl aromatic analogues. Only the amino pathway to form nitrosamines was noticed for dialkyl amines, nevertheless, both the main reactions occurred for N-alkyl aromatic amines. These findings suggested that the reaction with chloramines through a phenyl pathway was likely to be crucial for novel nitrogenous heterocyclic byproducts.

Characterization of Carbonyl Disinfection By-Products During Ozonation, Chlorination, and Chloramination of Dissolved Organic Matters.

Carbonyl compounds are an important class of by-products that are generated in disinfection reactions. These chemicals are ingredients contributing to toxicology in the drinking water system, the compositions and structures of which are worthy of attention. In this study, a chemical derivatization method based on simultaneous light/heavy isotope labeling was established for general recognition of carbonyl compounds and carbonyl disinfection by-products (DBPs) as per the humic substance reference standard (Suwannee river fulvic acid II, SRFA) before and after ozonation, chlorination, and chloramination. Decomposition of macromolecular components into polar carbonyl species was observed to be the most prominent pathway in ozone treatment due to the efficient reactivity of ozone with phenols and alkoxy aromatic rings. As a result, alteration of molecular characteristics was noticed. For instance, ozone-induced carbonyl DBPs in the highly oxygenated compound classes (0.67 ≤ O/C ≤ 1.2, 0.6 < H/C ≤ 1.5) possessed higher O/C but contained less oxygen numbers and carbon numbers. Cl/Br-carbonyl-DBPs were identified after chlorination and chloramination, and I-carbonyl-DBPs were found in ozone and chloramine treatments. Several major halogenated carbonyl homologues were further recognized, including halogenated 4-oxobutenoic acid analogues, halogenated 2,5-dioxohex-3-enoic acid analogues, and halogenated 4-cyclopentene-1,3-diones analogues. These findings illustrate the presence of abundant carbonyl DBPs in water disinfection, and hence their impacts on human health deserve further investigation.

No intrauterine vertical transmission in pregnancy with COVID-19: A case report.

The coronavirus disease 2019 (COVID-19) has been a worldwide pandemic diseases, nearly 400,000 people died at now. The data of status of pregnant women and neonates after infection of severe acute respiratory syndrome coronavirus 2 (SARS-COV-2) is limited. We report a case of pregnant woman in her third trimester with critical COVID-19, and amniotic fluid, umbilical cord blood, placenta, and neonatal gastric fluid were retained during cesarean section. The SARS-COV-2 nucleic acid test results of these specimens were negative. There is no evidence of intrauterine vertical transmission during delivery in the third trimester, but the data are limited and need to be further explored.

Three Cadmium Tartratoborates with Good Second Harmonic Generation (SHG) or Luminescence Performances.

Three new cadmium(II) tartratoborates, namely, Cd5[(C4H2O6)2B]2(H2O)8·3H2O (1), K2Cd4[(C4H2O6)2B]2(H2O)2 (2), and Li0.92K1.08Cd1.5[(C4H2O6)2B](H2O)2 (3), have been successfully synthesized by the hydrothermal method. Compounds 1-3 belong to centric C2/ c, acentric Pc, and the polar C2, respectively. Through based on the same hybrid borate-tartrate [(C4H2O6)2B]5- anions, they exhibit different structures. The [(C4H2O6)2B]5- anion is composed of two tartrate anions and a B(OH)4- unit. Compound 1 features a novel 3D network formed by 2D {Cd3[(C4H2O6)2B]2(H2O)2}4- anionic layers and [Cd2O10] dimers, forming tunnels of large 14-MRs which are filled by the non-coordination water molecules. Compound 2 has a characteristic 3D network based on {Cd2[(C4H2O6)2B]}- units interlinked via carboxylate groups, forming tunnels of 11-MRs, half of which stuffed with the K+ ions. Compound 3 features 2D {Cd4[(C4H2O6)4B]}3+ layers which are separated by K/Li ions. Luminescent studies suggest that they emit blue light. Compounds 2 and 3 display phase-matchable second harmonic generation signs of about 3.2× and 1.5× KH2PO4, respectively.

Exploring the Occurrence and Temporal Variation of ToxCast Chemicals in Fine Particulate Matter Using Suspect Screening Strategy.

Existence of emerging contaminants in the environment is of great importance for health risk assessment. The consensus on categories and numbers of the emerging contaminants in airborne fine particulate matter (PM2.5) is still extremely deficient. In this study, an in-house data set was constructed containing 890 unique ToxCast (Phase I and Phase II) chemicals. Occurrence and temporal variation of the chemicals was investigated by a suspect screening workflow in 60 PM2.5 samples from January to December of 2016 in Beijing. Eighty-nine compounds were identified in 12 substance categories, which covered a broad range of physicochemical properties. Quantification/semiquantification results showed that phthalates, phenols, and carboxylic esters were the three most predominant categories, with mean concentrations of 7.82, 4.42, and 4.11 ng/m3, respectively. Four diverse temporal variation patterns were discerned, which could be explained by correlations of chemical concentrations (or instrumental responses) with meteorological parameters. An extended retrospective suspect screening was also performed to reveal the presence of several analogues of the identified chemicals that were not included in the data set. Another 75 pollutants were tentatively recognized, and comparison of estimated composition profiles based on instrumental responses suggested the identified ToxCast chemicals are a notable subset of typical emerging contaminants. The results might facilitate ranking of organic pollutants with active biological effects in PM2.5 samples.

Occurrence and Degradation Potential of Fluoroalkylsilane Substances as Precursors of Perfluoroalkyl Carboxylic Acids.

Polyfluoroalkylsilanes (PFASis) are a class of artificial chemicals with wide applications in surface coating, which arouse attention due to their hydrophobic/oleophobic properties and potential biological effects. In this study, a robust high-resolution mass spectrometry method through direct injection into a Fourier transform ion cyclotron resonance instrument was established, with the aid of CF2-scaled Kendrick mass defect analysis and isotope fine structure elucidation. The occurrence of 8:2 polyfluoroalkyl trimethoxysilane (8:2 PTrMeOSi) and 8:2 polyfluoroalkyl triethoxysilane (8:2 PTrEtOSi), as well as their cationic adducts, solvent substitutions, and other compound analogues, were identified in commercial antifingerprint liquid products. In the hydroxyl radical-based total oxidizable precursor assay, differential molar yields of products were observed with regard to varied PFASi carbon-chain lengths and terminal groups. The yields of perfluoroalkyl carboxylic acids (PFCAs) from 8:2 PTrMeOSi conversion were the highest (92 ± 9%, n = 3), with the C ( n - 1) perfluoroheptanoic acid (PFHpA, 49 ± 11%, n = 3) as the dominating product. Distinct conversion of 8:2 PTrMeOSi in the simulated solar exposure experiments found that C ( n) perfluorooctanoic acid (PFOA, 0.6 ± 0.04 ‰, n = 3) was predominant, and 8:2 fluorotelomer carboxylic acid (8:2 FTCA, 0.59 ± 0.08‰, n = 3), 8:2 fluorotelomer unsaturated carboxylic acid (8:2 FTUCA, 0.09 ± 0.00‰, n = 3) intermediates were also observed. To our knowledge, this is the first report regarding the occurrence and degradation potential of several fluoroalkylsilane substances as PFCA precursors.

Multiple Metabolic Pathways of 2,4,6-Tribromophenol in Rice Plants.

Bromophenols occur naturally and are used globally as man-made additives in various industrial products. They are decomposition products of many emerging organic pollutants, such as tetrabromobisphenol A, polybrominated dibenzo- p-dioxin (PBDD), polybrominated diphenyl ethers (PBDE), and others. To characterize their biotransformation pathways, bromophenol congener 2,4,6-tribromophenol, being used most frequently in the synthesis of brominated flame retardants and having the greatest environmental abundance, was selected to hydroponically expose rice plants. After exposure for 5 days, 99.2% of 2,4,6-tribromophenol was metabolized by rice. Because of the lack of relative reference standards, an effective screening strategy was used to screen for potential metabolites that were further qualitatively identified by gas and liquid chromatography combined with high-resolution mass spectrometry. Forty transformation products were confirmed or tentatively identified at different confidence levels, including 9 phase I and 31 phase II metabolites. A large number of metabolites (39) were found in rice root, and 10 of them could be translocated and detected in rice stems or leaves. Many transformation pathways were proposed, including debromination, hydroxylation, methylation, coupling reactions, sulfation, and glycosylation. It was remarkable that a total of seven hydrophobic, persistent, and toxic OH-PBDEs and PBDD/Fs were found, indicating the biotic dimeric reactions of 2,4,6-tribromophenol that occurred in the rice plants. These results improve our understanding of the transformation and environmental fates of bromophenols, and they indicate new potential sources for OH-PBDEs and PBDD/Fs in the environment, especially in food chains.

Diagnostic Value of Non-Real-Time Radial Probe Endobronchial Ultrasound (RP-EBUS) Guided Positioning Method for Peripheral Pulmonary Lesions.

BACKGROUND The aim of this study was to analyze the diagnostic value of thin bronchoscopy lung biopsy for peripheral pulmonary lesions under non-real-time guidance of radial ultrasound (RP-EBUS). MATERIAL AND METHODS We used a retrospective analysis of ultrasound images of 165 patients with peripheral pulmonary disease admitted to Suzhou Municipal Hospital Affiliated to Nanjing Medical University from February 2016 to December 2018 who were given RP-EBUS examination. Ultrasound images were obtained for all patients. There were 76 patients treated using traditional positioning method as the control group; 89 patients were treated by probe combined with bronchoscopy positioning method as the research group where the biopsy of the lesion along the path of the ultrasound probe was taken. The positive rate of the 2 methods was observed, and the factors affecting the quality of ultra-thin bronchoscopy under RP-EBUS non-real-time guidance were analyzed. RESULTS The detection rate of the study group was 77.64%, which was significantly higher than that in control group, which was 63.16% (χ²=5.238, P<0.05). The number of biopsies in the study group was 6±1.25, which was significantly lower than that of the control group which was 9±1.87 (t=4.116, P<0.05). The diagnostic positive rate of the RP-EBUS probe was significantly higher than that of the RP-EBUS probe (χ²=5.081, P<0.05). CONCLUSIONS The diagnostic positive rate of RP-EBUS non-real-time guided subtotal bronchoscopy lung biopsy for peripheral lung disease using probe combined with bronchoscopy positioning method was higher than the traditional positioning method, and the number of biopsies in the study group was significantly lower than that in the control group, which was related to the size, location, whether the probe was wrapped, or the characteristics of the ultrasound image.

Emerging aromatic secondary amine contaminants and related derivatives in various dust matrices in China.

Aromatic secondary amines (Ar-SAs), constituted of several analogues with varied substitutions in molecular structure, are among the most frequently used anthropogenic antioxidants. Despite the reported toxicity effects, little information is available on their environmental contamination, except for few particular congeners such as diphenylamine. In this study, the occurrence of two kinds of Ar-SAs, substituted diphenylamines (S-DPAs) and novel substituted p-phenylenediamines (S-PPDs), was investigated in dust samples collected from outdoor rubber playgrounds and residential houses. Seven S-DPAs (GM: 102 ng/g) and two S-PPDs (GM: 20.9 ng/g) were detected in indoor dust. Significantly higher concentrations of S-DPAs (GM: 422 ng/g) and S-PPDs (GM: 31.6 ng/g) were observed in playground dust (p < 0.05). Different dominant Ar-SA congeners were found for indoor dust (low molecular weight Ar-SAs) and playground dust (high molecular weight Ar-SAs), indicating varied sources of Ar-SAs for different dust matrices. Apart from these parent chemicals, three diphenylamine derivatives, including N-nitrosodiphenylamine, 2-nitrodiphenylamine, and 4-nitrodiphenylamine, were also confirmed in indoor dust (GM: 35.7 ng/g) and playground dust (GM: 7.88 ng/g). A preliminary estimated daily intake calculation via dust ingestion indicated no immediate health risk to Chinese population. To our knowledge, this is the first report on the occurrence of a wide range of Ar-SAs and related derivates in dust matrices.