Determination of the Localized Surface Plasmon Resonance Alteration of AgNPs via Multiwavelength Evanescent Scattering Microscopy for Pb(II) Detection.

We developed multiwavelength evanescent scattering microscopy (MWESM), which can acquire plasmonic nanoparticle images at the particle level using the evanescent field as the incident source and distinguish different LSPR (localized surface plasmon resonance) spectral peaks among four wavelengths. Our microscope could be easily and simply built by modifying a commercial total internal reflection fluorescence microscope (TIRFM) with the substitution of a beamsplitter and the addition of a semicircular stop. The ultrathin depth of illumination and rejection of the reflected incident source together contribute to the high sensitivity and contrast of single nanoparticle imaging. We first validated the capability of our imaging system in distinguishing plasmonic nanoparticles bearing different LSPR spectral peaks, and the results were consistent with the scattering spectra results of hyperspectral imaging. Moreover, we demonstrated high imaging quality from the aspects of the signal/noise ratio and point spread function of the single-particle images. Meaningfully, the system can be utilized in rapidly determining the concentration of toxic lead ions in environmental and biological samples with good linearity and sensitivity, based on single-particle evanescent scattering imaging through the detection of the alteration of the LSPR of silver nanoparticles. This system holds the potential to advance the field of nanoparticle imaging and foster the application of nanomaterials as sensors.

Unique dissolved organic matter molecules and microbial communities in rhizosphere of three typical crop soils and their significant associations based on FT-ICR-MS and high-throughput sequencing analysis.

Using cucumber, maize, and ryegrass as model plants, the diversity and uniqueness of the molecular compositions of dissolved organic matter (DOM) and the structures of microbial communities in typical crop rhizosphere soils, as well as their associations, were investigated based on high-resolution mass spectrometry combined with high-throughput sequencing. The results showed that the rhizosphere contained 2200 organic molecules that were not identified in the non-rhizosphere soils, as characterized by FT-ICR-MS. The rhizosphere DOM molecules generally contained more N, S, and P heteroatoms, stronger hydrophilicity, and more refractory organic matter, representing high and complex chemical diversity characteristics. 16SrRNA sequencing results demonstrated that Proteobacteria, Actinomycetes and Firmicutes were the dominant flora in the soils. Plant species could significantly change the composition and relative abundance of rhizosphere microbial populations. The microbial community structures of rhizosphere and non-rhizosphere soils showed significant differences at both the phylum and class levels. Multiple interactions between the microorganisms and DOM compositions formed a complex network of relationships. There were strong and remarkable positive or negative couplings between different sizes and categories of DOM molecules and the specific microbial groups (P < 0.05, |R| ≥ 0.9) in the rhizosphere soils as shown by network profiles. The correlations between DOM molecules and microbial groups in rhizosphere soils had plant species specificity. The results above emphasized the relationship between the heterogeneity of DOM and the diversity of microbial communities, and explored the molecular mechanisms of the biochemical associations in typical plant rhizosphere soils, providing a foundation for in-depth understanding of plant-soil-microbe interactions.

Characterization of non-volatile organic contaminants in coking wastewater using non-target screening: Dominance of nitrogen, sulfur, and oxygen-containing compounds in biological effluents.

While abundant volatile compounds (VOCs) have been identified in coking wastewater, the structures and occurrence of non-volatile organic compounds (non-VOCs) have remained unknown. In this study, 3966 non-VOCs belonging to 24 groups were tentatively identified for the first time in wastewater from four biological coking wastewater treatment systems in northern China using a non-target screening technique. A total of 227 compounds with CHNO, CHO, CHOS, and CHNOS elemental compositions were assigned with level 2 identification confidence, and 19 of them were confirmed with authentic standards, with 9-methyl-9H-carbazole-3-carbaldehyde (1706.3-2032.7 µg/L) and 3-Indolyl acetic acid monomethyl terephthalate (773.7-1449.9 µg/L) as the top two compounds in the influents, and 9-methyl-9H-carbazole-3-carbaldehyde (31.8-130.1 µg/L) and monomethyl terephthalate (13.9-196.6 µg/L) as the top two in the effluents. The four groups of substances accounted for 93.4% and 71.5% of the total responses of tentatively identified compounds in the influents and biological effluents, respectively, and were estimated to contribute 32.3-48.9% of the chemical oxygen demand in the biological effluents. In comparison with those in the influent, abundant S-containing compounds (CHOS and CHNOS, 35.2% of the total responses) were observed in the biological effluents, suggesting their highly bio-refractory characteristics. The advanced treatment process using synchronized oxidation-adsorption could almost completely remove the CHOS and CHNOS compounds from the biological effluents.

Bioaccumulation and biotransformation of tetrabromoethylcyclohexane (TBECH) in maize (Zea mays L.): Stereoselective driving roles of plant biomacromolecules.

The bioaccumulation and biotransformation of tetrabromoethylcyclohexane (TBECH) in maize were investigated. Furthermore, the roles of plant biomacromolecules such as lipid transfer proteins (LTPs), CYP and GST enzymes in driving the biological processes of TBECH stereoisomers were explored. The uptake and translocation of TBECH in maize were diastereo- and enantio-selective. Isomerization from α- to δ-TBECH and ß- to γ-TBECH, and metabolites of debromination, hydroxylation and TBECH-GSH adducts were identified in maize roots. The gene expressions of LTPs, CYPs and GSTs were extensively changed in maize after exposure to technical TBECH. CYP and GST enzyme activities as well as GST31 and CYP71C3v2 gene expressions were selectively induced or inhibited by TBECH diastereomers over time. TBECH was able to dock into the active sites and bind with specific residues of the typical biomacromolecules ZmLTP1.6, GST31 and CYP71C3v2, indicating their roles in the bioaccumulation and metabolization of TBECH. Binding modes and affinities to biomacromolecules were significantly different between α- and ß-TBECH, which contributed to their stereo-selectivity. This study provided a deep understanding of the biological fate of TBECH, and revealed the driving molecular mechanisms of the selectivity of TBECH stereoisomers in plants.

Biochemical and molecular responses of maize (Zea mays L.) to 1,2-dibromo-4-(1,2 dibromoethyl) cyclohexane (TBECH) diastereomers: Oxidative stress, DNA damage, antioxidant enzyme gene expression and diversity of root exudates.

The phytotoxicities of TBECH diastereomers to plants at the biochemical and molecular levels were investigated in a hydroponic study by using maize as a model plant. The results showed that TBECH could induce the production of two species of reactive oxygen species (ROS), O2•- and H2O2, in maize tissues. The accumulation of ROS was the highest when maize was exposed to ß-TBECH. TBECH enhanced the phosphorylation of plant histone, and the contents of γ-H2AX in maize followed the order ß-TBECH > αß-TBECH > γδ-TBECH > γ-TBECH. Transcriptome profiling revealed that antioxidant enzyme genes (AEGs) were over-expressed in maize when stressed by technical grade TBECH. The RT-PCR detection further validated that three typical AEGs, including CAT, SOD, and POD genes, were time-dependent and selectively expressed under the influence of TBECH diastereomers. Molecular compositions of maize root exudates characterized by FT-ICR-MS were significantly different among the four groups of TBECH diastereomer treatments. TBECH diastereomers specifically affected the chemical diversity and abundance of root exudates. New insights into the biochemical effects of TBECH on plants are provided in this work, which is helpful to deepening the understanding of their stereo-selectivity.

A feasible strategy to improve confident elemental composition determination of compounds in complex organic mixture such as natural organic matter by FTICR-MS without internal calibration.

Confident elemental composition determination of compounds in complex samples such as natural organic matter (NOM) by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is challenging due to the interference between multiple components in these samples during detection. Here the performance of Solarix 15T-FTICR-MS in terms of accurate relative natural isotope abundance (RIA) and mass measurements for elemental composition determination of compounds in complex samples such as NOM was systematically evaluated. The optimal sweep excitation power values ranging from 20% to 22% was found to significantly diminish the underestimation of RIA measurement for 13C1 peaks of NOM components by FTICR-MS. Random error was found to be one of the main sources for the RIA errors of 13C1 peaks with S/N ratios <25. The mean averaged RIA errors of less than 10% could be obtained by averaging the measured RIAs of each 13C1 peaks in five replicated runs. By adjusting the total ion abundance of NOM complex sample between 3.8-E7 and 1.4-E8 which was simultaneously similar to that of external calibrant during detection, mass errors of lower than 1 ppm for NOM components with m/z lower than 700 Da could be obtained without internal calibration. Meanwhile, a linear correlation between mass errors of ions in NOM complex sample and their m/z values could be obtained. The mass error deviation derived from the linearity was firstly used as new criterion to reduce the number of false formula candidates. A novel strategy of combination of high mass accuracy, high spectral accuracy, and mass error deviation for elemental composition determination of unknown compounds in complex sample such as NOM by FTICR-MS was proposed and applied for different complex samples. Compared to the traditional method, about one fold increasement in the number of the unique formula assignments for measured ions was obtained by using our strategy.

Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent.

Molecular level characterization of dissolved organic sulfur (DOS) by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR MS) is necessary for further understanding of the role of DOS in the environment. Here, ESI spray solvent, a key parameter for ion production during ESI process, was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS. 100% MeOH as spray solvent was found for the first time to remarkably enhance the ionization efficiency of the majority of CHOS-molecules in NOM, which facilitated a total of 1473 CHOS-molecular formulas with one sulfur atom to be detected. The number of CHOS-molecular formulas obtained using 100%MeOH as spray solvent increased notably over 740 in comparison with those using 50% MeOH aqueous solution (731) or 50% ACN aqueous solution (653). Moreover, due to the enhancement of ionization efficiency of DOS during ESI processes, the tandem mass spectra of the NOM CHOS-molecules could be easily obtained using 100% MeOH as spray solvent, which were hardly obtained using 50% MeOH aqueous solution as spray solvent. The results of the tandem mass spectra suggested the first discovery of organosulfates or sulfonic acids in Suwannee River NOM sample. A simple method based on 100% MeOH as ESI spray solvent for advanced molecular characterization of DOS by ESI-FTICR MS was proposed and applied, and the results revealed more molecular information of DOS in sea DOM samples.

Ion Accumulation Time Dependent Molecular Characterization of Natural Organic Matter Using Electrospray Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

Natural organic matter (NOM) is a complex organic mixture and plays a crucial role in environmental processes. By using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), detailed molecular information on NOM could be achieved. In this paper, ion accumulation time (IAT), a key parameter of FTICR-MS for complex mixture detection, was the focus, and its effect on the molecular characterization of NOM by FTICR-MS was systematically investigated. A notable feature of selective detection of NOM molecules by FTICR-MS with different IAT was observed. Most of the polar molecules with high O/C ratio (O/C ratio >0.5) could be easily detected by FTICR-MS with a short IAT, but extending IAT led to the ion intensities of these molecules decreasing or even disappearing. Meanwhile, a large number of unsaturated and aromatic molecules with low O/C ratio (O/C ratio <0.6) and low polarity, all of which could not be observed with a short IAT, were remarkably detected by extending IAT. Results also revealed that the unsaturated and aromatic molecules, which could only be observed by extending the IAT, were not generated by the fragmentation of molecules in NOM or from the dissociation of NOM aggregations but originally existed in NOM samples. The selective detection of NOM molecules caused by IAT extension was possibly attributed to their different polarity and different stability in the collision cell. On the basis of these results, a novel strategy of combining mass spectrometric data of NOM obtained with different IAT by FTICR-MS was proposed. With this strategy, more than 4715 CHO-molecular formulas were assigned, where about 2000 more formulas were obtained in comparison with using a short IAT (2733 CHO-molecular formulas identified) solely. The strategy is simple and robust and can be used as an alternative method to obtain more molecular information on NOM in the environment.

Comprehensive characterization of natural organic matter by MALDI- and ESI-Fourier transform ion cyclotron resonance mass spectrometry.

Natural organic matter (NOM) is a complex and non-uniform mixture of organic compounds which plays an important role in environmental processes. Due to the complexity, it is challenging to obtain fully detailed structural information about NOM. Although Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) has been demonstrated to be a powerful tool for providing molecular information about NOM, multiple ionization methods are needed for comprehensive characterization of NOM at the molecular level considering the ionizing selectivity of different ionization methods. This paper reports the first use of matrix assisted laser desorption/ionization (MALDI) method coupled with FT-ICR-MS for molecular characterization of NOM within a mass range of 200-800 Da. The mass spectral data obtained by MALDI were systematically compared with data generated by electrospray ionization (ESI). It showed that complementary molecular information about NOM which could not be detected by ESI, were provided by MALDI. More unsaturated and aromatic constituents of NOM with lower O/C ratio (O/C ratio<0.5) were preferentially ionized in MALDI negative mode, whereas more polar constituents of NOM with higher O/C ratio were preferentially ionized in ESI negative mode. Molecular anions of NOM appearing at even m/z in MALDI negative ion mode were detected. The results show that NOM molecules with aromatic structures, moderate O/C ratio (0.7>O/C ratio>0.25) and lower H/C ratio were liable to form molecular anions at even m/z, whereas those with higher H/C ratio are more likely to form deprotonated ions at odd m/z. It is speculated that almost half of the NOM molecules identified by MALDI may be aromatic or condensed aromatic compounds with special groups which are liable to absorb electron from other molecules to generate free radical anions during MALDI ionization.

Matrix effect in high-performance liquid chromatography-tandem mass spectrometry analysis of antibiotics in environmental water samples.

This paper describes the matrix effect during the analysis of ten antibiotic compounds in water by SPE followed by HPLC-ESI-MS/MS. The target analytes were tetracycline, oxytetracycline (tetracyclines), sulfathiazole, sulfamethazine, sulfadiazine (sulfonamides), erythromycin-H(2)O, roxithromycine, spiramycin (macrolides), ofloxacin, and norfloxacin (quinolones). The matrix effect was examined for internal standards and the target analytes in five different water matrixes, with signal suppression being increased in the order: ultrapure water, tap water, river water, sewage effluent, and sewage influent. A combined application of the internal standards and matrix-matched extract calibration was shown to be successful in compensating the matrix effect for the analytes. The procedural recovery of the target compounds in sewage effluents and influents was higher than in river water samples, which was further enhanced by sample acidification to pH 2. The validity of the internal standard based matrix-matched calibration approach was verified by the standard addition method.

Proton sponge-functionalized silica as high performance adsorbents for solid-phase extraction of trace perfluoroalkyl sulfonates in the environmental water samples and their direct analysis by MALDI-TOF-MS.

1,8-Bis(dimethylamino)naphthalene (DMAN), a classical 'proton sponge', was functionalized on silica particles as a novel solid-phase extraction (SPE) adsorbent (DMAN@silica) for extracting perfluoroalkyl sulfonates (PFSs). High reproducibility and excellent extraction capability for PFSs were obtained in a wide pH range (3.0~8.5). The adsorbed PFSs on DMAN@silica sorbents could be efficiently eluted by 1,8-bis(tetramethylguanidino)naphthalene (TMGN) solution which is a proton sponge with higher proton affinity than DMAN. The elution could be directly analyzed by MALDI-TOF-MS using TMGN as matrix. Clear mass spectra for the PFSs were obtained due to no matrix ions interference observed. Furthermore, a novel strategy based on the DMAN@silica-SPE enrichment, followed by MALDI-TOF-MS analysis, was proposed and applied for PFSs quantification in environmental water samples. The calibration curves of each of the target analytes showed a wide linear dynamic range of response (0.1-10 ng L(-1) for perfluorooctane sulfonate (PFOS), perfluorohexyl sulfonate (PFHxS) and perfluorobutylsulfonate (PFBS)), which were over 2 orders of magnitude. The detection limits for PFOS, PFHxS, and PFBS were 0.021, 0.016, and 0.013 ng L(-1), respectively (S/N = 3). Recoveries of PFOS, PFHxS, and PFBS are in the ranges of 92-104%, 95-102%, and 98-109% for spiked river water samples. These results indicated that the prepared DMAN@silica adsorbents could efficiently enrich PFSs and that the proposed method is reliable.

Quantitative detection of trace perfluorinated compounds in environmental water samples by Matrix-assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry with 1,8-bis(tetramethylguanidino)-naphthalene as matrix.

Determination of perfluorinated compounds (PFCs) is very important because of their potential hazards to the environment and human health. In present work, 1,8-bis (tetramethylguanidino)-naphthalene (TMGN), a superbasic proton sponge, was firstly employed as the matrix for quantitative detection of acidic PFCs in environmental water samples by Matrix-assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry (MALDI-TOF-MS). Several acidic PFCs, such as perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), were selected as model analytes for demonstrating the feasibility of the detection method. The results showed that deprotonated ions of these PFCs were detected without any other matrix ions interference. The achieved sensitivity with TMGN for PFOS detection was ten-fold higher than that with 1,8-bis (dimethyl-amino)-naphthalene (DMAN) which was used for the detection of fatty acid by MALDI-TOF-MS. The high sensitivity of this method made it feasible to monitor and quantify acidic PFCs in complicated environmental water samples. Furthermore, a novel combined strategy of solid phase extraction (SPE) followed by MALDI-TOF-MS detection was developed for quantifying PFCs in environmental water samples. The calibration curves with a wide linear dynamic range (0.1-10 ng L(-1) for PFOS, PFHxS, and PFBS, and 0.5-50 ng L(-1) for PFOA, PFNA, and PFDA.) were obtained. The limit of detection (LOD) for PFOS of this method was 0.015 ng L(-1) (a signal-to-noise ratio of 3), which was lower than the LOD (0.036 ng L(-1)) obtained by high-pressure liquid chromatography/tandem mass spectrometry (LC-MS/MS) method. Moreover, the strategy was used to detect the selected PFCs in water samples collected from Xiaoqinghe river and Gaobeidian wastewater. The achieved concentrations of PFCs were closed to those obtained by LC-MS/MS method. It is indicated that the proposed MALDI-TOF-MS method with TMGN as the matrix is much reliable and can be used as an alternative method to detect trace PFCs in environmental water samples.

Photoacid generator formation for the selective enrichment of perfluoroalkyl sulfonates and their direct analysis by MALDI-TOF-MS.

Triphenylsulfonium chloride (TPSC) was employed as a bifunctional agent for the selective enrichment of perfluoroalkyl sulfonates by triphenylsulfonium perfluorosulfonic acid (TPA, a photoacid generator) precipitation, and for the direct detection of perfluorosulfonic acid by MALDI-TOF-MS, using the triphensylsulfonium group of TPA as a matrix.

Sedimentary records of DDT and HCH in the Pearl River Delta, South China.

Tropical regions in developing countries are thought to be significant sources of organochlorine pesticides in the global context, owing to high rate of use and only a recent production ban or restriction on application of these pesticides. In the present paper, DDT and HCH in eight 210Pb-dated sedimentary cores from the Pearl River Delta, South China, were analyzed in order to reconstruct the time trends of these persistent organic pollutants in this tropical region. The sedimentary inventories of sigmaDDT and sigmaHCH through the cores ranged from 36.6 to 1109.5 ng/cm2 and from 11.2 to 226.3 ng/cm2, respectively, and their spatial distribution implies that the water flows from the Humen, Jiaomen, Hongqili, and Hengmen outlets rather than the Xijiang flow from Modaomen outlet, supplied the major historical input of DDT to the estuary. Although a production ban of technical HCH and DDT was imposed in China in 1983, their sedimentary fluxes display increasing trends or strong rebounds in the 1990s as recorded in the core profiles, characteristic of the increasing ratios of (DDE + DDD)/DDT and DDE/DDT. It is suggested that an enhanced land soil runoff in the process of large-scale land transform, as well as a higher river water flow in early 1990s, had mobilized these pesticides from soil to the sedimentary system in the region.

An innovative Ti/Tio2 mesh photoelectrode for methyl orange photoelectrocatalytic degradation.

A new type of photoelectrode was innovated by anodising titanium mesh in H2SO4 solution and named Ti/TiO2 mesh electrode. The structural and surface morphology of the Ti/TiO2 mesh was examined by X-ray diffraction, Laser Raman spectra and scanning electronic microscopy (SEM). The results indicated that its crystal structure, morphology and the size of pore were affected greatly by the anodisation voltage, current density. The photoelectrocatalytic (PEC) oxidation of methyl orange (MO) solution using the Ti/TiO2 mesh was investigated. The results demonstrated that Ti/TiO2 mesh prepared at 160 V and 110 mA cm(-2) had the best PEC activity. The PEC oxidation efficiency could be significantly enhanced by applying an optimal electrical bias voltage between the working electrode and counter electrode. It was found that the best performance of PEC oxidation was achieved by applying an electrical bias of 0.6 V. It is suggested that the recombination of electrons and holes was hindered owing to applying electrical bias voltage.

Chlorinated and polycyclic aromatic hydrocarbons in riverine and estuarine sediments from Pearl River Delta, China.

Spatial distribution of chlorinated hydrocarbons [chlorinated pesticides (CPs) and polychlorinated biphenyls (PCBs)] and polycyclic aromatic hydrocarbons (PAHs) was measured in riverine and estuarine sediment samples from Pearl River Delta, China, collected in 1997. Concentrations of CPs of the riverine sediment samples range from 12 to 158 ng/g, dry weight, while those of PCBs range from 11 to 486 ng/g. The CPs concentrations of the estuarine sediment samples are in the range 6-1658 ng/g, while concentrations of PCBs are in the range 10-339 ng/g. Total PAH concentration ranges from 1168 to 21,329 ng/g in the riverine sediment samples, whereas the PAH concentration ranges from 323 to 14,812 ng/g in the sediment samples of the Estuary. Sediment samples of the Zhujiang River and Macao harbor around the Estuary show the highest concentrations of CPs, PCBs, and PAHs. Possible factors affecting the distribution patterns are also discussed based on the usage history of the chemicals, hydrologic condition, and land erosion due to urbanization processes. The composition of PAHs is investigated and used to assess petrogenic, combustion and naturally derived PAHs of the sediment samples of the Pearl River Delta. In addition, the concentrations of a number of organic compounds of the Pearl River Delta samples indicate that sediments of the Zhujiang river and Macao harbor are most likely to pose biological impairment.