•Metagenomic method was introduced into in situ PAHDGs investigation.•Genes involved in three processes for PAH degrading were identified simultaneously.•Plasmid-carrying-PAHDGs were used to evaluate horizontal gene transfer probability.Bacterial degradation is an important clearance pathway for organic contaminants from highly human-impacted environments. However, it is not fully understood how organic contaminants are selected for degradation by bacteria and genes in aquatic environments. In this study, PAH degrading bacterial genera and PAH-degradation-related genes (PAHDGs) in sediments collected from the Pearl River (PR), the Pearl River Estuary (PRE) and the South China Sea (SCS), among which there were distinct differences in anthropogenic impact, were analyzed using metagenomic approaches. The diversity and abundance of PAH degrading genera and PAHDGs in the PR were substantially higher than those in the PRE and the SCS and were significantly correlated with the total PAH concentration. PAHDGs involved with the three key processes of PAH degradation (ring cleavage, side chain and central aromatic processes) were significantly correlated with each other in the sediments. In particular, plasmid-related PAHDGs were abundant in the PR sediments, indicating plasmid-mediated horizontal transfer of these genes between bacteria or the overgrowth of the bacteria containing these plasmids under the stresses of PAHs. Our results suggest that PAH degrading bacteria and genes were rich in PAH-polluted aquatic environments, which could facilitate the removal of PAHs by bacteria.Download high-res image (180KB)Download full-size image

•PAHs enriched antibiotic resistance genes (ARGs) in the soils.•ARGs associated with aromatic antibiotics were dominant in the PAHs-polluted soils.•Most of ARGs could encode efflux transporters.•ARGs were sparsely carried by plasmids.•ARGs were significantly correlated with Proteobacteria in the soils.The prevalence of antibiotic resistance genes (ARGs) in modern environment raises an emerging global health concern. In this study, soil samples were collected from three sites in petrochemical plant that represented different pollution levels of polycyclic aromatic hydrocarbons (PAHs). Metagenomic profiling of these soils demonstrated that ARGs in the PAHs-contaminated soils were approximately 15 times more abundant than those in the less-contaminated ones, with Proteobacterial being the preponderant phylum. Resistance profile of ARGs in the PAHs-polluted soils was characterized by the dominance of efflux pump-encoding ARGs associated with aromatic antibiotics (e.g., fluoroquinolones and acriflavine) that accounted for more than 70% of the total ARGs, which was significantly different from representative sources of ARG pollution due to wide use of antibiotics. Most of ARGs enriched in the PAHs-contaminated soils were not carried by plasmids, indicating the low possibilities of them being transferred between bacteria. Significant correlation was observed between the total abundance of ARGs and that of Proteobacteria in the soils. Proteobacteria selected by PAHs led to simultaneously enriching of ARGs carried by them in the soils. Our results suggested that PAHs could serve as one of selective stresses for greatly enriching of ARGs in the human-impacted environment.Download high-res image (187KB)Download full-size image

•Environmental applications of AIMS to date have been summarized in detail.•Features and adaptions of AIMS for different environmental samples have been discussed.•AIMS methods allow for analyzing trace pollutants in complex environmental samples.•The rapid-developing AIMS will apply increasingly in environmental analysis.Continuous pollution issues with increasing types of contaminants have emerged in recent years and attracted global attention. Fast, precise, and reliable analytical methods for screening and determination of targeted and unknown pollutants are desired to evaluate the changing pollution situations and potential environmental effects. The rapid development of ambient ionization mass spectrometry (AIMS) renders good opportunities to in-situ, real-time, and rapid analysis for trace emerging environmental pollutants with minimal or no sample pretreatment. In this review article, the ionization mechanisms, configurations of the instruments, hyphenations with various compatible pretreatment means and analytical devices, and operation parameters are discussed. In particular, the typical applications of AIMS for detecting multitude of pollutants present in various environmental samples are summarized.

•Analysis of single cells by ambient MS has been reviewed.•Strategies to achieve single-cell ambient MS analysis were categorized.•Different ambient ionization techniques for single-cell analysis were discussed.•Cellular and subcellular ingredients analyzed by ambient MS were summarized.Analysis of chemicals at single-cell level plays an important role in the investigation of cell genomics, transcriptomics, proteomics, and metabolomics, and it also provides significant insight in life science, biological, medicinal, pharmacological, pathological, and toxicological studies. As a newly developed technique, ambient mass spectrometry has been proven to be a powerful tool for rapid, direct, and straightforward analysis of cellular and subcellular ingredients and metabolites under ambient and open-air conditions. In this review article, we discuss the fields of ambient mass spectrometry for analysis of single cells that have been published to date. Different strategies for application of various ambient ionization techniques to achieve single-cell mass spectrometric analysis are categorized and commented, and the typical analyses and applications are summarized and discussed.

A dichloro-substituted triphenylethylene derivative (TrPECl2) with aggregation-induced emission (AIE), photochromism and photoresponsive wettability has been synthesized. The new compound shows fast-response photochromic behaviour with good ON/OFF repeatability by utilizing a proposed stilbene-type intramolecular photocyclization in the solid state. Compared with the more usual diphenylethylene derivatives, the photochromic properties of the triphenylethylene derivative are much more striking and easier to achieve. The triphenylethylene derivative also displays AIE properties leading to strong fluorescence in the solid state. Therefore, both the ultraviolet-visible absorption and fluorescence emission are drastically changed during the photochromic processes. Furthermore, the morphology of the TrPECl2 microcrystalline surface could be controlled by irradiation. The wettability of the surface could be drastically decreased with contact angles of a water droplet changing from 73° to 118°. The triphenylethylene derivative with a simple molecular structure is, therefore, attractive for multifunctional materials.

The contributions of abiotic and biotic processes in an estuarine aquatic environment to the removal of four phenolic endocrine-disrupting chemicals (EDCs) were evaluated through simulated batch reactors containing water-only or water-sediment collected from an estuary in South China. More than 90% of the free forms of all four spiked EDCs were removed from these reactors at the end of 28 days under aerobic conditions, with the half-life of 17α-ethynylestradiol (EE2) longer than those of propylparaben (PP), nonylphenol (NP) and 17β-estradiol (E2). The interaction with dissolved oxygen contributed to NP removal and was enhanced by aeration. The PP and E2 removal was positively influenced by adsorption on suspended particles initially, whereas abiotic transformation by estuarine-dissolved matter contributed to their complete removal. Biotic processes, including degradation by active aquatic microorganisms, had significant effects on the removal of EE2. Sedimentary inorganic and organic matter posed a positive effect only when EE2 biodegradation was inhibited. Estrone (E1), the oxidizing product of E2, was detected, proving that E2 was removed by the naturally occurring oxidizers in the estuarine water matrixes. These results revealed that the estuarine aquatic environment was effective in removing free EDCs, and the contributions of abiotic and biotic processes to their removal were compound specific.

•Strategies for coupling SPME to AMS were summarized and discussed.•Advances and applications of SPME-AMS to date have been reviewed in details.•SPME coupled with AMS enhances significant advantages of both techniques.•SPME-AMS has great potential in analysis of trace compounds.The rapid development of solid-phase microextraction (SPME) coupled with ambient mass spectrometry (AMS) in recent years gives us the opportunities for direct and straightforward analysis of trace analytes in complex biological, environmental, forensic, food, individual small organism, and even single cell samples under ambient and open-air condition. This review article summarized the field of SPME coupled with AMS that has been published to date. The strategies for coupling SPME to AMS were summarized and discussed, and the typical applications of SPME coupled with AMS were commented.

Analysis of target compounds in individual small organisms is of significant importance for biological, environmental, medicinal, and toxicological investigation. In this study, we reported the development of a novel solid-phase microextraction (SPME) based ambient mass spectrometry (MS) method named surface-coated probe nanoelectrospray ionization (SCP-nanoESI)-MS for analysis of target compounds in individual small organisms with sizes at micrometer-to-millimeter level. SCP-nanoESI-MS analysis involves three procedures: (1) modification of adsorbent at the surface of a fine metal probe to form a specially designed surface-coated SPME probe with probe-end diameter at several-micrometer level, (2) application of the surface-coated SPME probe for enrichment of target analytes from individual small organisms, and (3) employment of a nanospray tip and some solvent to desorb the analytes and induce nanoESI for mass spectrometric analysis under ambient condition. A SCP-nanoESI-MS method for determination of the perfluorinated compounds (PFCs) in individual Daphnia magna was developed. The method showed satisfactory linearities for analysis of real Daphnia magna samples, with correlation coefficient values (R2) of 0.9984 and 0.9956 for perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), respectively. The limits of detection were 0.02 and 0.03 ng/mL for PFOS and PFOA, respectively. By using the proposed method, the amount, bioaccumulation kinetics, and distribution of PFOS and PFOA in individual Daphnia magna were successfully investigated.

•The sample preparation time was greatly shorten (∼15 min) by SLE compared with present methods in literature.•The sensitivity and selectivity were improved and analytical time was shortened by employing gas chromatography–tandem mass spectrometry (GC–MS/MS).•The developed method was proved to be rapid, precise and accurate.•The developed method has potential for high-throughput analysis of PCMs in biological fluids for health impact assessment.A rapid, precise and accurate method for the simultaneous determination of 5 polycyclic musks (PCMs) in biological fluids was developed by solid supported liquid–liquid extraction (SLE) coupled with gas chromatography–tandem mass spectrometry (GC–MS/MS). All parameters influencing SLE-GC–MS performance, including electron energy of electron-impact ionization source, collision energy for tandem mass spectrometer when operated in selected-reaction monitoring (SRM) mode, type and volume of elution reagent, nitrogen evaporation time, pH and salinity of sample have been carefully optimized. Eight milliliter of n-hexane was finally chosen as elution reagent. Blood and urine sample could be loaded into SLE cartridge without adjusting pH and salinity. Deuterated tonalide (AHTN-d3) was chosen as internal standard. The correlation coefficient (r2) of the calibration curves of target compounds ranged from 0.9996 to 0.9998. The dynamic range spanned over two orders of magnitude. The limit of detection (LOD) of target compounds in blood and urine ranged from 0.008 to 0.105 μg L−1 and 0.005 to 0.075 μg L−1, respectively. The developed procedure was successfully applied to the analysis of PCMs in human blood and urine obtaining satisfying recoveries on low, medium and high levels. The method was compared with SLE-GC–MS and shown one to two orders of magnitude improvement in sensitivity.

Coupling solid-phase microextraction (SPME) with ambient mass spectrometry using surface coated wooden-tip probe was achieved for the first time and applied in the analysis of ultra trace perfluorinated compounds (PFCs) in complex environmental and biological samples. We modified n-octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride on the surface of sharp wooden tip via silanization to form a novel SPME probe, which was then used for highly selective enrichment of PFCs from complex matrices and applied as a solid substrate to induce electrospray ionization for mass spectrometric analysis. The porous structural surface together with the dual extraction mechanisms (reversed phase adsorption and ion exchange adsorption) demonstrated that the SPME probe has an outstanding enrichment capacity, enhancing sensitivity by approximately 4000–8000 folds for the detection in aqueous samples, and 100–500-fold in whole blood and milk samples. The method showed good linearity, with correlation coefficient values (r2) of no less than 0.9931 for eight target PFCs. The limits of detection and qualification of the eight PFCs were 0.06–0.59 and 0.21–1.98 ng/L, respectively. Quantification of real samples was achieved by isotope internal standard calibration curve method or isotope dilution method, and ultratrace levels of PFCs present in lake water, river water, whole blood, and milk samples had been successfully detected and qualified.

Abundant microbes including bacteria, fungi, or algae are capable of biodegrading polycyclic hydrocarbons (PAHs). However, pure cultures never occur in the contaminated environments. This study aimed to understand the general potential mechanisms of interactions between microbes under pollution stress by constructing a consortium of PAH-degrading microalga (Selenastrum capricornutum) and bacterium (Mycobacterium sp. strain A1-PYR). Bacteria alone could grow on the pyrene, whereas the growth of algae alone was substantially inhibited by the pyrene of 10 mg L–1. In the mixing culture of algae and bacteria, the growth rate of algae was significantly increased from day 4 onward. Rapid bacterial degradation of pyrene might mitigate the toxicity of pyrene to algae. Phenolic acids, the bacterial degradation products of pyrene, could serve as the phytohormone for promoting algal growth in the coculture of algae and bacteria. In turn, bacterial growth was also enhanced by the algae presented in the mixing culture. Consequently, the fastest degradation of pyrene among all biodegradation systems was achieved by the consortium of algae and bacteria probably due to such interactions between the two species by virtue of degradation products. This study reveals that the consortium containing multiple microbial species is high potential for microbial remediation of pyrene-contaminated environments, and provides a new strategy to degrade the recalcitrant PAHs.

•We review coupling solid-phase microextraction (SPME) with mass spectrometry (MS).•Principles, developments and applications for techniques coupling SPME with MS.•SPME coupled with MS integrates significant advantages of both techniques.•We particularly emphasize SPME coupled with ambient MS (AMS).Solid-phase microextraction (SPME) has experienced significant development since its introduction as a sample-pretreatment technique in the early 1990s. SPME is suitable for interfacing with chromatography and mass spectrometry (MS), but progress in coupling with chromatography has exceeded that with MS. In the past two decades, efforts have been made to couple SPME and MS with different applications in various research fields. Based on these previous studies, this review article summarizes historical developments, principles and operation, practical applications, and recent trends in SPME coupled with five types of MS: (1) electron-impact MS, (2) inductively-coupled plasma MS, (3) laser-desorption/ionization MS, (4) atmospheric-pressure ionization MS and (5) ambient MS (AMS). We particularly emphasize efforts on SPME coupled with AMS.

A sample preparation method for the determination of hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) in sediment samples was developed using gas chromatography–mass spectrometry (GC–MS). Dispersive liquid–liquid microextraction (DLLME) with derivatization was performed following the subcritical water extraction (SWE) that provided which was provided by accelerated solvent extraction (ASE). Several important parameters that affected both SWE extraction and DLLME, such as the selection of organic modifier, its volume, extraction temperature, extraction pressure and extraction time were also investigated. High sensitivity of the hydroxylated PAHs derivatives by N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBSTFA) could be achieved with the limits of detection (LODs) ranging from 0.0139 (2-OH-nap) to 0.2334 μg kg−1 (3-OH-fluo) and the relative standard deviations (RSDs) between 2.81% (2-OH-phe) and 11.07% (1-OH-pyr). Moreover, the proposed method was compared with SWE coupled with solid phase extraction (SPE), and the results showed that ASE–DLLME was more promising with recoveries ranging from 57.63% to 91.07%. The proposed method was then applied to determine the hydroxylated metabolites of phenanthrene in contaminated sediments produced during the degradation by two PAH-degraders isolated from mangrove sediments.Graphical abstractHighlights► We combine subcritical water extraction (SWE) with dispersive liquid–liquid microextraction (DLLME). ► Subcritical water is used as the extraction solvent for SWE and the sample solution for the following DLLME. ► Acetonitrile is used as the organic modifier for SWE and disperser solvent for DLLME in succession. ► We examine changes of OH-PAHs during the degradation by microorganism.

Herein we report the electrochemical synthesis of porous Pr(OH)3 nanobelt arrays (NBAs), nanowire arrays (NWAs), nanowire bundles (NWBs), and nanowires (NWs) and their applications as dye absorbents in water treatment. These Pr(OH)3 nanostructures exhibit high efficient and selective adsorption of the dyes with amine (−NH2) functional groups such as Congo red, reactive yellow, and reactive blue. The high efficiency and selectivity is attributed to the large effective surface area of the porous structure, plentiful hydroxyl groups, and basic sites on the Pr(OH)3 surface. Furthermore, the toxicity studies of these porous Pr(OH)3 nanostructure show a negligible effect on seed germination, indicating that they hold great potential as environmentally friendly absorbents in water treatment.

A simple, precise and accurate method for the simultaneous determination of four UV filters and five polycyclic musks (PCMs) in aqueous samples was developed by solid-phase microextraction coupled with gas chromatography–mass spectrometry (SPME-GC–MS). The operating conditions affecting the performance of SPME-GC–MS, including fiber thickness, desorption time, pH, salinity, extraction time and temperature have been carefully studied. Under optimum conditions (30 μm PDMS fiber, 7 min desorption time, pH 7, 10% NaCl, 90 min extraction time at 24 °C), the correlation coefficients (r2) of the calibration curves of target compounds ranged from 0.9993 to 0.9999. The limit of detection (LOD) and limit of quantification (LOQ) ranged from 0.2 to 9.6 ng L−1 and 0.7 to 32.0 ng L−1, respectively. The developed procedure was applied to the determinations of four UV filters and five PCMs in river water samples and internal standard was used for calibration to compensate the matrix effect. Good relative recoveries were obtained for spiked river water at low, medium and high levels. The proposed SPME method was compared with traditional SPE procedure and the results found in river water using both methods were in the same order of magnitude and both are quite agreeable.

A simple and fast sample preparation method for the determination of nonylphenol (NP) and octylphenol (OP) in aqueous samples by simultaneous derivatization and dispersive liquid–liquid microextraction (DLLME) was investigated using gas chromatography–mass spectrometry (GC/MS). In this method, a combined dispersant/derivatization catalyst (methanol/pyridine mixture) was firstly added to an aqueous sample, following which a derivatization reagent/extraction solvent (methyl chloroformate/chloroform) was rapidly injected to combine in situ derivatization and extraction in a single step. After centrifuging, the sedimented phase containing the analytes was injected into the GC port by autosampler for analysis. Several parameters, such as extraction solvent, dispersant solvent, amount of derivatization reagent, derivatization and extraction time, pH, and ionic strength were optimized to obtain higher sensitivity for the detection of NP and OP. Under the optimized conditions, good linearity was observed in the range of 0.1–1000 μg L−1 and 0.01–100 μg L−1 with the limits of detection (LOD) of 0.03 μg L−1 and 0.002 μg L−1 for NP and OP, respectively. Water samples collected from the Pearl River were analyzed with the proposed method, the concentrations of NP and OP were found to be 2.40 ± 0.16 μg L−1 and 0.037 ± 0.001 μg L−1, respectively. The relative recoveries of the water samples spiked with different concentrations of NP and OP were in the range of 88.3–106.7%. Compared with SPME and SPE, the proposed method can be successfully applied to the rapid and convenient determination of NP and OP in aqueous samples.

A sample pretreatment method for the determination of 18 chlorophenols (CPs) in aqueous samples by derivatization liquid-phase microextraction (LPME) was investigated using gas chromatography–mass spectrometry. Derivatization reagent was spiked into the extraction solvent to combine derivatization and extraction into one step. High sensitivity of 18 CPs derivatives could be achieved after optimization of several parameters such as extraction solvent, percentage of derivatization reagent, extraction time, pH, and ionic strength. The results from the optimal method showed that calibration ranging from 0.5 to 500 μg L−1 could be achieved with the RSDs between 1.75% and 9.39%, and the limits of detection (LOD) are ranging from 0.01 to 0.12 μg L−1 for the CPs. Moreover, the proposed LPME method was compared with solid-phase microextraction (SPME) coupled with on-fiber derivatization technique. The results suggested that using both methods are quite agreeable. Furthermore, the recoveries of LPME evaluated by spiked environmental samples ranged from 87.9% (3,5-DCP) to 114.7% (2,3,5,6-TeCP), and environmental water samples collected from the Pearl River were analyzed with the optimized LPME method, the concentrations of 18 CPs ranged from 0.0237 μg L−1 (3,5-DCP) to 0.3623 μg L−1 (2,3,6-TCP).

A fully automated sample pretreatment method was developed for the detection of mono and dihydroxy metabolites of polycyclic aromatic hydrocarbons (PAHs) by gas chromatography–mass spectrometry in the selected ion monitoring mode. Direct immersion solid-phase microextraction for the extraction of target compounds and the headspace on-fiber silylation with N,O-bis(trimethylsilyl)trifluoroacetamide were performed automatically by a multipurpose autosampler (MPS2). The operating conditions including extraction time, derivatization time, ionic strength, pH, and incubation temperature were optimized. Calibration responses of nine metabolites of PAHs over a concentration range of 0.1–100 μg L−1 with a correlation coefficient of 0.999 were obtained. The detection limits of the nine metabolites in mini pore water, minimal salts medium and soil extract culture medium were in the range of 0.001–0.013, 0.002–0.024 and 0.002–0.134 μg L−1, respectively, while the respective quantification limits were 0.003–0.044, 0.005–0.081 and 0.008–0.447 μg L−1. The reliability was confirmed by the traditional solid-phase extraction method. The proposed method could be used to analyze the metabolites of PAHs degraded by microorganisms such as algae and to determine the biodegradation pathways of PAHs.

The influence of growth medium on cometabolic degradation of polycyclic aromatic hydrocarbons (PAHs) was investigated when Sphingomonas sp. strain PheB4 isolated from surface mangrove sediments was grown in either phenanthrene-containing mineral salts medium (PMSM) or nutrient broth (NB). The NB-grown culture exhibited a more rapid cometabolic degradation of single and mixed non-growth substrate PAHs compared to the PMSM-grown culture. The concentrations of PAH metabolites were also lower in NB-grown culture than in PMSM-grown culture, suggesting that NB-grown culture removed metabolites at a faster rate, particularly, for metabolites produced from cometabolic degradation of a binary mixture of PAHs. Cometabolic pathways of single PAH (anthracene, fluorene, or fluoranthene) in NB-grown culture showed similarity to that in PMSM-grown culture. However, cometabolic pathways of mixed PAHs were more diverse in NB-grown culture than that in PMSM-grown culture. These results indicated that nutrient rich medium was effective in enhancing cometabolic degradation of mixed PAHs concomitant with a rapid removal of metabolites, which could be useful for the bioremediation of mixed PAHs contaminated sites using Sphingomonas sp. strain PheB4.

•Bacterial strain of Sphingobium sp. MP9-4 was isolated to degrade alkylated PAHs.•Detailed metabolism map of 1-methylphenanthrene (1-MP) was delineated.•1-MP was initially oxidized via benzene ring and methyl-group attacks.•Monooxygenase and dioxygenase systems were involved in 1-MP degradation.Alkylated polycyclic aromatic hydrocarbons (PAHs) are abundant in petroleum, and alkylated phenanthrenes are considered as the primary PAHs during some oil spill events. Bacterial strain of Sphingobium sp. MP9-4, isolated from petroleum-contaminated soil, was efficient to degrade 1-methylphenanthrene (1-MP). A detailed metabolism map of 1-MP in this strain was delineated based on analysis of metabolites with gas chromatograph–mass spectrometer (GC–MS). 1-MP was initially oxidized via two different biochemical strategies, including benzene ring and methyl-group attacks. Benzene ring attack was initiated with dioxygenation of the non-methylated aromatic ring via similar degradation pathways of phenanthrene (PHE) by bacteria. For methyl-group attack, mono oxygenase system was involved and more diverse enzymes were needed than that of PHE degradation. This study enhances the understanding of the metabolic pathways of alkylated PAHs and shows the significant potential of Sphingobium sp. MP9-4 for the bioremediation of alkylated PAHs contaminated environments.

Spatial and temporal distribution of octylphenol (OP) and nonylphenol (NP) in Mai Po Marshes, a subtropical estuarine wetland in Hong Kong, were investigated. Surface water samples were collected every month from 11 sites during the period of September-December 2004. Concentrations of OP and NP ranged from 11.3 to 348 ng/L and from 29 to 2591 ng/L, respectively. The high levels of NP and OP were found in November and December than in September and October. The levels of OP and NP have no significant spatial differences except September. Total organic matter in the sediments appeared to be an important factor in controlling the fate of these compounds in the aquatic environment.

•Parent and oxygenated PAHs were ubiquitous in mangrove sediments of Hong Kong.•The contamination of parent and oxygenated PAHs were at the middle-to-high level.•Parent and carbonylic PAHs were originated from petroleum combustion in sediments.•The source of hydroxylated PAHs was more complicated.•TOM was an important factor for regulating the spatial distribution of oxygenated PAHs.Parent and oxygenated polycyclic aromatic hydrocarbons (PAHs) were investigated in mangrove sediments of Hong Kong. Most of the analytes were detected, and the dominant carbonylic and hydroxylated PAHs in mangrove sediments were 9-fluorenone and 2-hydroxy fluorene, respectively. The concentration of 9-fluorenone and 9,10-anthraquinone was higher than their parent PAHs. Moreover, the concentration of total organic matter (TOM) related with those of the parent PAHs and carbonylic PAHs, except for hydroxylated PAHs, which indicated that TOM was not the only factor regulating the distribution of oxygenated PAHs. Nevertheless, the parent PAHs in mangrove sediments was correlated positively with carbonylic PAHs which demostrated not only the similar source but also the fate of these two compound class. However, hydroxylated PAHs had different source by comparing with parent PAHs and carbonylic PAHs, they were probably originated from biodegradation and accumulated in mangrove sediments.

•A surface-coated wooden-tip ESI-MS method was developed.•A specially design surface-coated wooden-tip SPME probe was prepared.•The probe showed high enrichment capacity toward fluoroquinolones and macrolides.•Trace fluoroquinolones and macrolides in real water were detected and quantified.In this study, a surface-coated wooden-tip electrospray ionization mass spectrometry (SCWT-ESI-MS) method was developed for rapid and sensitive analysis of trace fluoroquinolone and macrolide antibiotics in water. First, a SCWT solid-phase microextration (SPME) probe was prepared, via silanization and sulfonation for modification of a layer of adsorbent containing both C8-chain and sulfo group on the surface of wooden tips. Then, the SCWT-SPME probe was applied for extraction of trace fluoroquinolone and macrolide antibiotics in water. The specially designed adsorbent gave the probe desirable enrichment capacity towards fluoroquinolone and macrolide antibiotics, with enrichment factors of approximately 100–500 folds for six target analytes. After extraction, the loaded SCWT-SPME probe was directly applied for ambient MS analysis. With the application of a high voltage and some spray solvent on the SCWT-SPME probe, analytes enriched on the probe was desorbed and ionized for mass spectrometric analysis under ambient and open-air conditions. The method was sensitive, with limits of detection and quantification of 1.8–4.5 ng/L and 5.9–15.1 ng/L, respectively. The method also showed good linearity, with correlation coefficient values (r2) of no less than 0.9940 for six target analytes. The developed method was successfully applied for the analysis of six fluoroquinolone and macrolide antibiotics in tap and river water samples, and no antibiotic was found in tap water but some antibiotics were detected in river water with concentrations at dozens to hundreds nanogram-per-liter level. Standard addition experiments were also performed, and the obtained recoveries were 89–102% for tap waters and 82–92% for river waters, respectively. All the experimental results demonstrated that our proposed SCWT-ESI-MS method was rapid, sensitive, and reliable for analyzing trace antibiotics in water.

•Nutrient broth could enhance the whole degradation rate of pyrene.•Bacteria could achieve a higher degradation efficiency per cell in the PAH substrates.•Good correlations between bacterial degradation rate and 4,5-pyrenediol or nidA gene•Growth patterns regulated degradation pathway and dioxygenase expression.Pyrene degradation by Mycobacterium sp. strain A1-PYR was investigated in the presence of nutrient broth, phenanthrene and fluoranthene, respectively. Fast bacterial growth in the nutrient broth considerably enhanced pyrene degradation rate, whereas degradation efficiency per cell was substantially decreased. The addition of nutrient broth could not alter the transcription levels of all dioxygenase genotypes. In the PAH-only substrates, bacterial growth completely relied on biological conversion of PAHs into the effective carbon sources, which led to a higher degradation efficiency of pyrene per cell than the case of nutrient broth. Significant correlations were only observed between nidA-related dioxygenase expression and pyrene degradation or bacterial growth. The highest pyrene degradation rate in the presence of phenanthrene was consistent with the highest transcription level of nidA and 4,5-pyrenediol as the sole initial metabolite. This study reveals that bacterial growth requirement can invigorate degradation of PAHs by regulating metabolic pathway and genotypic enzyme expression.Download high-res image (118KB)Download full-size image

•Coupling slug-flow microextraction with paper spray mass spectrometry was developed.•Quantitative analysis of macrolide antibiotics in whole blood and milk was achieved.•Analysis of perfluorinated compounds in individual Daphnia magna was reached.Analysis of trace compounds in small-volume complex samples is of importance for forensic, clinical, pharmaceutical, environmental, and life science investigation. In this study, we reported the coupling of slug-flow microextraction with paper spray mass spectrometry for rapid analysis of trace analytes in small volume of complicated biological samples such as whole blood, milk, and body fluid, etc. The method is performed by applying a disposable glass capillary for rapid extraction of a small amount of complex samples using a small amount of organic solvent; the loaded organic solvent was then spotted onto a paper triangle and dried out; subsequently, a high voltage and some spray solvent were applied onto the paper triangle for mass spectrometric analysis. By using the proposed method, high sensitivity and satisfactory precision for quantitative analysis of trace macrolide antibiotics in whole bloods and milks as well as perfluorinated compounds in individual small organisms have been successfully achieved. In addition, investigation of bioaccumulation of perfluorinated compounds in individual small organisms has been reached.

A dichloro-substituted triphenylethylene derivative (TrPECl2) with aggregation-induced emission (AIE), photochromism and photoresponsive wettability has been synthesized. The new compound shows fast-response photochromic behaviour with good ON/OFF repeatability by utilizing a proposed stilbene-type intramolecular photocyclization in the solid state. Compared with the more usual diphenylethylene derivatives, the photochromic properties of the triphenylethylene derivative are much more striking and easier to achieve. The triphenylethylene derivative also displays AIE properties leading to strong fluorescence in the solid state. Therefore, both the ultraviolet-visible absorption and fluorescence emission are drastically changed during the photochromic processes. Furthermore, the morphology of the TrPECl2 microcrystalline surface could be controlled by irradiation. The wettability of the surface could be drastically decreased with contact angles of a water droplet changing from 73° to 118°. The triphenylethylene derivative with a simple molecular structure is, therefore, attractive for multifunctional materials.