State Key Laboratory of Organic Geochemistry

The efficiency of photocatalytic inactivation towards <italic>Escherichia coli</italic> K-12 is highly dependent on the dominantly exposed facets of BiOBr.

A novel passive water sampler (diffusive gradients in thin-films for organics, o-DGT) was previously developed and successfully tested in the laboratory, but has not yet been validated in the field. Here, o-DGT samplers were deployed in the influent and effluent of a typical UK wastewater treatment plant (WWTP); the influent was also sampled with a conventional automatic sampler (Auto) and by grab (Grab) sampling. All the samples were analyzed by LC-MS/MS for 40 target antibiotics (including 16 sulfonamides (SAs), 12 fluoroquinolones, 6 macrolides, 2 ionophores, 2 diaminopyimidines, 1 aminocoumarin, and 1 lincosamide). The diffusion coefficients (D) of these antibiotics in o-DGT, measured in the laboratory, ranged from 0.58 × 10(-06) to 6.24 × 10(-06) cm(2) s(-1). The derived surface area normalized sampling rates (RS/A, 0.54-5.74 mL d(-1) cm(-2)) were comparable with those for another passive sampler called POCIS. Fourteen antibiotics were detected in the actively sampled water samples, with 10 of the 14 detected in o-DGT devices deployed for more than 7 days. Most of the antibiotics detected in o-DGT, except sulfapyridine, were continually accumulated by o-DGT for ~10 days. Deployment for 7 days is recommended to integrate ambient concentrations over time, without risks of reaching capacity and significant biofouling. Diffusive boundary layer (DBL) thickness had less effect on the o-DGT measurement than reported for other passive samplers. The comparison between o-DGT and Auto and Grab samplings showed that o-DGT was more efficient in terms of cost, time, and labor. This study demonstrates for the first time in a real environment that o-DGT is an effective tool for the routine monitoring of antibiotics in wastewaters and provides a powerful approach to studying their occurrence, fate, and behavior in the environment.

Abstract Photooxidation of 4‐nitrophenol (4‐NP) in water by the UV/H 2 O 2 advanced oxidation process was carried out in order to investigate the kinetics and pathway of 4‐NP degradation. The experimental results showed that the photodegradation of 4‐NP accorded well with pseudo‐first order kinetics. The effects of different parameters, such as H 2 O 2 dosage, pH value and various anion scavengers on the degradation of 4‐NP have been investigated in detail. It was found that acidic conditions are more favorable to the degradation of 4‐NP but many anions, such as HCO 3 − , NO 3 − and Cl − , slow down the photooxidation rate of 4‐NP. Hydroquinone, 1,2,4‐trihdroxybenzene, 4‐nitropyrogallol, and 4‐nitrocatechol were tentatively identified as the intermediates of 4‐NP degradation by GC/MS after samples were derivatized by N , O ‐bis(trimethylsilyl)‐trifluoroacetamide (BSTFA). A degradation pathway was proposed to account for the observed intermediates produced during 4‐NP degradation by the UV/H 2 O 2 process. Copyright © 2003 Society of Chemical Industry

Polybrominated diphenyl ethers (PBDEs) were determined in 60 surface soils from two e-waste recycling sites (Qingyuan and Guiyu, China) and their surrounding areas to assess the extent and influence of PBDEs from e-waste recycling sites on the surrounding areas. A total of 32 surface soils from industrial areas in South China were also investigated for comparison. The mean concentrations of total PBDEs in the e-waste recycling sites of Guiyu and Qingyuan were 2,909 and 3,230 ng/g dry weight, respectively, whereas the PBDE concentrations decreased dramatically (1-2 orders of magnitude) with increasing distance from the recycling site, suggesting that the e-waste recycling activities were the major source of PBDEs in the surrounding areas. Decabromodiphenyl ethers accounted for 77.0 to 85.8% of total PBDEs in e-waste recycling areas, whereas it accounted for 90.2% in industrial areas. Principal component analysis showed that the major source of PBDEs in e-waste recycling areas were a combination of penta-, octa-, and deca-BDE commercial formulations, whereas deca-BDE commercial formulations were the major source of PBDE congeners in industrial areas. The inventories of PBDEs gave preliminary estimates of 6.22 tons and 13.4 tons for the e-waste recycling areas and industrial areas. The results suggested that significantly higher PBDEs in the e-waste recycling sites have already affected surrounding areas negatively within a relatively large distance. Because of the environmental persistence, bioaccumulation, and toxicity of PBDEs, improving the recycling techniques employed at such facilities and developing e-waste management policies are necessary.

Carbon-based nanoparticles (CNPs) have emerged as novel man-made materials with diverse applications, which may present significant risks to organisms. To bridge the gap in our knowledge of nanotoxicology, a number of in vitro or in vivo studies have been carried out. However, toxicity data remains limited. Herein, we employed a biospectroscopy approach to assess CNP-induced effects in zebrafish (Danio rerio). Zebrafish were exposed to Fullerene (C60), long or short multi-walled carbon nanotubes (MWCNTs), or single-walled carbon nanotubes (SWCNTs) for 21 days at two concentrations: 0.1 mg L(-1) or 0.001 mg L(-1). Following exposure, the brain, gills, gonads and liver from zebrafish were interrogated by attenuated total reflection Fourier-transform infrared (ATR-FTIR) or Raman spectroscopy. Computational analysis was then applied to the acquired infrared (IR) spectra, and distinct biochemical segregations between the exposed tissues vs. control were observed with spectral biomarkers of alterations identified. In addition, lipid-to-protein ratios in all four tissues were calculated by the IR spectra; unsaturated lipid levels in brain and gonad were assessed by Raman spectroscopy. Marked lipid alterations were observed. These findings show that biospectroscopy approaches have the potential to detect CNP-induced biochemical alterations in zebrafish.

Temperature measurement using magnetic resonance imaging (MRI) of water self-diffusion is investigated. Diffusion images and derived temperatures are obtained in polyacrylamide gel phantom. The temperatures measured from MRI are compared with those from temperature probes to verify their accuracy. In general, the difference between temperatures determined from MRI diffusion images over 0.3 cm3 regions of interest and from temperature probes were 0.2 degrees C. It is concluded that current MRI technology allows noninvasive temperature tomography that is comparable with invasive thermometry with respect to temperature accuracy, has spatial and time resolutions that would be useful in hyperthermic oncology.

The hydroxyl radical (OH) is one of the most important oxidants controlling the oxidation capacity of the indoor atmosphere. One of the main OH sources indoors is the photolysis of nitrous acid (HONO). In this study, real-time measurements of HONO, nitrogen oxides (NOx) and ozone (O3) in an indoor environment in Guangzhou, China, were performed under two different conditions: (1) in the absence of any human activity and (2) in the presence of cooking. The maximum NOx and HONO levels drastically increased from 15 and 4 ppb in the absence of human activity to 135 and 40 ppb during the cooking event, respectively. The photon flux was determined for the sunlit room, which has a closed south-east oriented window. The photon flux was used to estimate the photolysis rate constants of NO2, J(NO2), and HONO, J(HONO), which span the range between 8 × 10-5 and 1.5 × 10-5 s-1 in the morning from 9:30 to 11:45, and 8.5 × 10-4 and 1.5 × 10-4 s-1 at noon, respectively. The OH concentrations calculated by photostationary state (PSS) approach, observed around noon, are very similar, i.e., 2.4 × 106 and 3.1 × 106 cm-3 in the absence of human activity and during cooking, respectively. These results suggest that under "high NOx" conditions (NOx higher than a few ppb) and with direct sunlight in the room, the NOx and HONO chemistry would be similar, independent of the geographic location of the indoor environment, which facilitates future modeling studies focused on indoor gas phase oxidation capacity.

At present, a technique potentially capable of measuring values of Young's modulus at the nanoscale is atomic force microscopy (AFM) working in the indentation mode. However, the question if AFM indentation data can be translated into absolute values of the modulus is not well-studied as yet, in particular, for the most interesting case of stiff nanocomposite materials. Here we investigate this question. A special sample of nanocomposite material, shale rock, was used, which is relatively homogeneous at the multi-micron scale. Two AFM modes, force-volume and PeakForce QNM were used in this study. The nanoindentation technique was used as a control benchmark for the measurement of effective Young's modulus of the shale sample. The indentation rate was carefully controlled. To ensure the self-consistency of the mechanical model used to analyze AFM data, the model was modified to take into account the presence of the surface roughness. We found excellent agreement between the average values of effective Young's modulus calculated within AFM and the nanoindenter benchmark method. At the same time, the softest and hardest areas of the sample were seen only with AFM.

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was consistent between cell death and cellular ROS for GSOA but not for PSOA, indicating that cellular ROS production does not necessarily represent all processes contributing to cell death caused by PSOA. Combining different acellular and cellular assays can provide a comprehensive understanding of aerosol toxicological properties.

Alkenone sea surface temperatures (SSTs) in the northern South China Sea (SCS) were reconstructed for the last ∼3.8 Ma. The SST difference between the western equatorial Pacific and northern SCS was then estimated, showing a general increase since ∼2.8 Ma. Three features of the SST‐gradient evolution were prominent: 1) low values (&lt;2°C) in the late Pliocene; 2) increased values during the late Pliocene/early Pleistocene (from 1 to 4°C); and 3) high values (∼4°C) by the end of the early Pleistocene. These features were also shown in zonal SST gradient across equatorial Pacific, implying an intimate relationship of the meridional Hadley and East Asian monsoon circulations with the zonal Walker circulation. Moreover, the SST gradient records displayed some characters unique to the equatorial Pacific and not found in benthic δ 18 O record, suggesting that zonal tropical climate change could spread into higher latitude by interactions with meridional circulations.

up-regulation of DNA-PKcs. In addition, TCS blocked the HepG2 cells in S and G2/M phases of cell cycle through down-regulation of cyclin A2 and CDK; while MTCS induced cell cycle arrest at the S phase through up-regulation of cyclin A2 and CDK. Furthermore, TCS activated p53 mediated apoptosis in HepG2 cells in a caspase-independent manner, while MTCS induced apoptosis was dependent on caspase. Moreover, TCS exposure exhibited more severe toxicity in HepG2 cells as compared with MTCS exposure, indicating that the replacement of the ionizable proton in TCS by the methyl group in MTCS is correlated with the cellular toxicity and the molecular mechanism.

A new method for the simultaneous detection of 20 polybrominated diphenyl ethers (PBDEs), 16 polycyclic aromatic hydrocarbons (PAHs), 4 hydroxyl PBDEs (OH-PBDEs) and 10 hydroxyl PAHs (OH-PAHs) in human hair has been developed for the first time. External target analytes from hair (hair-Ex) were ultrasonically extracted with acetone, while the internal target analytes (hair-In) were obtained with further digestion and liquid-liquid extraction of washed hair. Alkaline digestion with liquid-liquid extraction under alkaline and re-acidification combination conditions was the key procedure to successfully extract both parent and metabolic compounds from hair. Both external and internal extracts were purified with gel permeation chromatography, and the parent compounds were subsequently separated from their hydroxylated metabolites with a silica solid phase extraction column prior to instrumental analysis. GC-MS-MS, GC-MS and HPLC-MS-MS were used to analyze PAHs, PBDEs and their hydroxylated metabolites, respectively. The method showed satisfactory accuracy as well as precision, and the recoveries of PBDEs, PAHs, OH-PBDEs and OH-PAHs ranged from 62%-145%, 48%-135%, 60%-146% and 60%-88%, respectively. The developed method was validated in a pilot biomonitoring campaign. All parent analytes were approximately 100% detected in both hair-In and hair-Ex, while no OH-PBDEs were detected in hair-In and hair-Ex. All OH-PAHs were approximately 100% detected in hair-In with a mean Σ10OH-PAHs concentration of 174.7 ng per g dry weight (dw), and the concentration in hair-Ex was 18 times lower than that in hair-In with a relatively lower detection frequency. Both partial least squares discriminant analysis (PLS-DA) and Spearman correlation analysis with the concentration of analytes confirmed that the developed method performed well to distinguish the internal from external exposure to target analytes in hair.

Photocatalytic materials are a potentially effective remediation technology for indoor air purification. In this paper, we assess the impact of photocatalytic paint porosity on the indoor levels of nitrogen oxides (NOx) and nitrous acid (HONO). We observed that the porosity of photocatalytic paints plays a paramount role in the NO2 removal. The increase of pigment volume concentration (PVC), i.e. porosity, from PVC 53% to PVC 80% leads to an increase of the geometric NO2 uptake coefficient from (3.3 ± 0.5) × 10-6 to (3.2 ± 0.1) × 10-4. At the same time, a high quantity of HONO formed by NO2 conversion on the photocatalytic paint is emitted into the air. The formation of HONO, which is considered as a harmful compound and a major player in the oxidative capacity of indoor air, is reduced as the paint porosity increases. Based on these results, further optimization should be considered for future commercialization of photocatalytic paints aimed for indoor applications.

The purpose of this study was to investigate the cytotoxic effects of tributylphosphate (TBP) and tris (2-butoxyethyl) phosphate (TBEP) and to explore the underlying molecular mechanism focusing on oxidative stress, apoptosis, and cell cycle arrest.

An investigation of the waters around Macau collected 43 phytoplankton species belonging to 29 genera and 5 phyla, including 32 species from 22 genera of Bacillariophyta, 7 species from 3 genera of Pyrrophyta, 2 species from 2 genera of Cyanophyta, and 1 genus and 1 species from both Euglenophyta and Chromophyta. The dominant phytoplankton species in the study areas were Skeletonema costatum (Greville) Cleve, Aulacoseira granulata (Ehrenberg) Simonsen, Thalassiothrix frauenfeidii Grunow, and Thalassionema nitzschioides Grunow. The phytoplankton abundance in the waters around Macau was between 46,607.14 and 1,355,000 cells/m3, with the highest abundance noted in station S8. Diatoms were the main contributor to phytoplankton abundance in station S8, accounting for 96.2% of the total abundance. Station S4 exhibited the lowest phytoplankton abundance of 46,607.1 cells/m3, with diatoms and Chromophytaaccounting for 58.6% and 29.9% of the total phytoplankton abundance, respectively. Biodiversity analysis results showed that the phytoplankton richness index was 1.18−3.61, the uniformity index was 0.24−0.78, and the Shannon−Wiener index was 0.94−3.41. Correlation analysis revealed that ammonia nitrogen was significantly negatively correlated with the phytoplankton richness, uniformity, and Shannon−Wiener indices. Nitrite nitrogen, nitrate nitrogen, inorganic nitrogen, salinity, turbidity, and pH were positively correlated with the phytoplankton evenness index and Shannon−Wiener index. Cluster and non-metric multidimensional scaling analyses demonstrated that the phytoplankton community structure in the waters around Macau could be divided into three groups, with A. granulata, S. costatum, T. frauenfeidii, T. nitzschioides, Chaetoceros curvisetus Cleve, and Chaetoceros diadema (Ehrenberg) Gran being predominant in different grouping communities (contribution% > 10%). Biota-Environment Stepwise Analysis (BIOENV) showed a significant correlation between the phytoplankton community and nitrite nitrogen content in the waters around Macau (correlation: 0.5544, Mantel test: statistic 0.4196, p = 0.009), which was consistent with the results of the canonical correspondence analysis.

Dependence of deliquescence relative humidity of perchlorates on temperature.

Modification of nanoscale zero-valent iron (nZVI) with reducing sulfur compounds has proven to improve the reactivity of nZVI towards recalcitrant halogenated organic contaminants. In this study, we develop a novel method for the preparation of sulfidated nZVI (S-nZVI) with S0 (a low cost and available reducing sulfur agent) dissolved in ethanol under mild conditions and apply it for the transformation of tetrabromobisphenol A (TBBPA), a potential persistent organic pollutant. Surface analysis shows that S0 dissolved in ethanol has been successfully doped into nZVI via a reaction with Fe0 to form a relatively homogeneous layer of FeS/FeS2 on the nZVI surface. The H2 production test and the electrochemical analysis show that the FeS/FeS2 layer not only slows the H2 evolution reaction but also enhances the electron transfer. Debromination kinetics indicate that the resulting S-nZVI with a S/Fe ratio of 0.015-0.05 possesses higher debromination activity for TBBPA and its debromination products (i.e., tri-BBPA, di-BBPA, mono-BBPA and BPA) in comparison with nZVI. Among them, S-nZVI at a S/Fe of 0.025 (S-nZVIS-0.025) has the greatest debromination rate constant (kobs) of 1.19 ± 0.071 h-1 for TBBPA. It debrominates TBBPA at a faster rate than other conventional S-nZVI made from Na2S and Na2S2O4 and has been successfully applied in the treatment of TBBPA-spiked environmental water samples (including river water, groundwater, and tap water). The results suggest that the modification of nZVI with S0 dissolved in ethanol is a simple, safe, inexpensive, and effective sulfidation technique, which can be applied for the large-scale production of S-nZVI for treating contaminated water.

We describe a homemade high-resolution orthogonal-injection time-of-flight (O-TOF) mass spectrometer combing a heated capillary inlet. The O-TOF uses a heated capillary tube combined with a radio-frequency only quadrupole (rf-only quadrupole) as an interface to help the ion transmission from the atmospheric pressure to the low-pressure regions. The principle, configuration of the O-TOF, and the performance of the instrument are introduced in this paper. With electrospray ion source, the performances of the mass resolution, the sensitivity, the mass range, and the mass accuracy are described. We also include our results obtained by coupling atmospheric pressure matrix-assisted laser deporption ionization with this instrument.

In this work, a CoCu alloy magnetic unit was implanted in a photocatalytic system to improve photoinduced charge separation efficiency by regulating the electron transfer pathway via a giant magnetoresistance (GMR) effect, which achieved significantly enhanced hydrogen production activity driven by visible light. The amount of H2 produced in 3 h over the Pt@CoCu alloy decorated graphene (G) photocatalyst was about 12.2 times higher than that of Pt/G, and the highest apparent quantum efficiency (AQE) reached 34.4% at 520 nm.