Distribution of 25 semi-volatile organic compounds of two urban lakes in Wuhan, China

In this study, the levels of 25 semi-volatile organic compounds (SVOCs) were measured in samples of water, suspended particulate matter (SPM) and sediment from two urban lakes in Wuhan, China. The total concentrations of 25 SVOCs varied from 529.4 to 2168.9 ng/L, 120.7 to 22543.7 ng/g dry weight and 1577.3 to 61579.6 ng/g dry wt. in water, SPM and sediment, respectively. The concentration of SVOCs in SPM was 9-10 times higher than that in water, and the concentration of SVOCs in sediment 1.5-2 times higher than that in SPM. The level of total SVOC25 in the samples from Moshuihu Lake was higher than that in Yuehu Lake. Among the 25 SVOCs, phthalate compounds were on the highest level in all observed samples ranging between 441.9-1831.2 ng/L, 116.3-17566.8 ng/g, dry wt. and 6432.8-48177.6 ng/g dry wt. in water, SPM and sediment, respectively. Bis(2-ethylhexyl)phthalate, the predominant component of the analyzed pollutants, was in the range from 246.7 to 537.5 ng/l, 51.2 to 15540.0 ng/g dry wt. and 468.2 to 45010.3 ng/g dry wt. in water, SPM and sediment, respectively. The content of PAHs, dinitrotoluene and isophoton in sediment was higher than that in water and SPM at most of the locations. The possible sources of the pollutants and their inter-relation with human activities were discussed.

Seasonal variations of estrogenic compounds and their estrogenicities in influent and effluent from a municipal sewage treatment plant in China

The seasonal variations of estrogenic compounds and the estrogenicities of influent and effluent were investigated by OF chemical analysis and in vitro assay in a municipal sewage treatment plant in Wuhan (China). The levels of eight estrogenic compounds, including 17 beta-estradiol (E-2) estrone (E-1), estriol (E-3) diethylstilbestrol (DES), 17 alpha-ethinylestradiol, nonylphenol (NP), 4-tert-octylphenol (OP), and bisphenol A (BPA), were measured by gas chromatography-mass spectrometry. Total estrogenic activity of sewage was quantitatively assessed using primary cultured hepatocytes of male Megalobrama amblycephala Yih using vitellogenin as a biomarker. The E-2 equivalents (EEQs) obtained from the chemical analysis were consistent with those measured by bioassay. The natural (E-1, E-2, and E-3) and synthetic (DES) estrogens, as well as NP, were the main contributors of the total EEQs of influent and effluent in the present study. The levels of natural estrogens E-1 and E-3 in the influent and effluent were higher in winter than in summer, whereas the situation for NP and OP was the reverse. The levels of E-2, DES, and BPA varied little among different seasons. 17 alpha-Ethinylestradiol was not detected in the influent and effluent. The estrogenicities of the influent and of the primary and secondary effluents were all higher in summer than in winter. Estrogenic activities in winter mainly originated from natural (E-1, E-2, and E-3) and synthetic (DES) estrogens, whereas the increase of EEQs in summer was contributed by NP The results from chemical analysis and bioassay demonstrate that estrogenic compounds cannot be entirely removed by the existing sewage treatment process, which should be further improved to protect aquatic ecosystems and human health.

Perfluorinated compounds in the Pearl River and Yangtze River of China

A total of 14 perfluorinated compounds (PFCs) were quantified in river water samples collected from tributaries of the Pearl River (Guangzhou Province, south China) and the Yangtze River (central China). Among the PFCs analyzed, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the two compounds with the highest concentrations. PFOS concentrations ranged from 0.90 to 99 ng/1 and < 0.01-14 ng/1 in samples from the Pearl River and Yangtze River, respectively; whereas those for PFOA ranged from 0.85 to 13 ng/l and 2.0-260 ng/l. Lower concentrations were measured for perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctanesulfoamide (PFOSA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorononaoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA). Concentrations of several perfluorocarboxylic acids, including perfluorododecanoic acid (PFDoDA), perfluorotetradecanoic acid (PFTeDA), perfluorohexadecanoic acid (PFHxDA) and perfluorooctadecanoic acid (PFOcDA) were lower than the limits of quantification in all the samples analyzed. The highest concentrations of most PFCs were observed in water samples from the Yangtze River near Shanghai, the major industrial and financial centre in China. In addition, sampling locations in the lower reaches of the Yangtze River with a reduced flow rate might serve as a final sink for contaminants from the upstream river runoffs. Generally, PFOS was the dominant PFC found in samples from the Pearl River, while PFOA was the predominant PFC in water from the Yangtze River. Specifically, a considerable amount of PFBS (22.9-26.1% of total PFC analyzed) was measured in water collected near Nanjing, which indicates the presence of potential sources of PFBS in this part of China. Completely different PFC composition profiles were observed for samples from the Pearl River and the Yangtze River. This indicates the presence of dissimilar sources in these two regions. (c) 2007 Elsevier Ltd. All rights reserved.

Determination of odorous compounds in water by headspace solid-phase microextraction-gas chromatography-mass spectrometry

Three major odorous compounds are 2-methylisoborneol ( 2-MIB), geosmin and beta-cyclocitral, which in water were determined by coupling headspace solid-phase microextraction ( HS-SPME) with gas chromatography-mass spectrometry (GC-MS). The operating conditions of HS-SPME, such as fibre type, salt concentration, water temperature, stirring, absorption time and desorption time were studied and discussed.The highest absorption of the odorous compounds were obtained under the following operating conditions as the addition of 30% ( m/V) NaCl, stirring at 60 degrees C for 40 min, using 65 mu m polydimethyl siloxane/divinylbenzene coated fibre. After the odorous compounds had been absorbed in the fibre under the optimal conditions of HSSPME, they were desorbed at 250 degrees C and determined by GC-MS. The limits of detection for geosmin, beta-cyclocitral and 2-MIB in water were 1. 0, 1. 3, 1. 7 ng/L, and the relative standard deviations for them were 4. 9%, 8. 4%, 6. 2%,respectively. There were good linear correlation (the calibration coefficients were all above 0. 997) for the three odorous compounds in the range of 5 similar to 1000 ng/ L. Therefore, trace levels of the odorous compounds at ng/L in water could be quantified by the simple method with satisfactory result.

Cytological and biochemical alterations in Carassius auratus hepatocytes from exposure to sediment containing dioxins and related compounds

Cytological and biochemical alterations of crucial carp (Carassius auratus) hepatocytes were characterized after exposure to sediments from a lake contaminated with dioxins and other industrial chemicals. Carp were exposed in 20 L water containing 25, 50, or 100 g of contaminated sediment for 2 and 4 weeks. Ultrastructural changes in the liver were characterized by severe enlargement of hepatocytes. Alterations in the cell. included formation of condensed and irregular cell nucleus, polynuclei, dispersed heterochromatin, enlargement of the nucleolus, and degeneration of the nucleus. Mitochondrial numbers were reduced and cristae were deformed. Myelin figures and lysosomes were increased, and sometimes cell organelles and cell matrix were totally lost after 4 weeks of exposure. The ultrastructural alterations were correlated with exposure time and sediment concentrations. Hepatosometic index was significantly increased in experimental groups at 2 and 4 weeks as compared with the control group. EROD enzyme activities were strongly induced in liver. A trend from rough endoplasmic reticulum (RER) to SER was observed. Our results suggest that the dioxin-like compounds bound by sediment were bioavailable to C. auratus and cause sublethal effects.

Analysis of organchlorine compounds in water by solid phase microextraction and gas chromatography

In this work, both,solid phase microextraction (SPME) and solid phase extraction(SPE) were used to enrich organochlorine compounds in water samples and analyzed by gas chromatography with electron capture detector. The operating conditions of SPME have been studied and different kinds of solid phase were compared. Linear alkybenzene sulfonate(LAS) was added to the samples to investigate its effect on the analysis. The results indicated that polyacrylate was better than other commercial solid phases in extraction of moderated polar organic compounds and the sensitivity of SPME was higher than SPE. LAS affect much in liquid-liquid extraction and headspace SPME; but it has little effect on SPE and direct-SPME method. The applications showed that SPME was a fast and effective method in sample preparation.

UV-sensitive P compounds: Release mechanism, seasonal fluctuation and inhibitory effects on alkaline phosphatase activity in a shallow Chinese freshwater lake (Donghu Lake)

Filtrable phosphorus compounds in a shallow Chinese freshwater lake (Donghu Lake) were fractionated by Sephadex G-25 gel-filtration chromatography. Some portions of those compounds released soluble reactive phosphorus upon irradiation with low dose ultraviolet light. Catalase and a hydroxyl radical scavenger (mannitol) markedly prevented photosensitive phosphorus release. The observed effects may be explained by the action of oxidizing reagents such as hydroxyl radicals, produced in photochemical reactions between UV irradiation and humic substances in the water. There was a strong seasonality in UV-sensitive P (UVSP) release. Michaels constants (K-m) of total alkaline phosphatase in the lake water showed a direct positive relation to UVSP. Plot of K-m against the UVSP/phosphomonoester ratio reveals a strong relationship between the two variables. These results suggest that in some situations UVSP may be a competitive inhibitor of alkaline phosphatase activity in the lake. The competitive inhibition of fractionated UVSP on alkaline phosphatase reagent (Sigma) apparently supports this hypothesis.

Rapid bioassay as indicator of potentially harmful effects for dioxin-like compounds in sample of Ya-Er Lake, China: Requirements for clean-up and comparison to chemical analysis

A rapid bioassay was established measuring the extracts of wildlife samples which were taken from Ya-Er Lake area, China. In extracts of these samples containing PCDD/Fs and PCBs, bioassay and chemically derived TCDD-equivalents (TEQs) were nearly identical. Our results indicate this bioassay is an excellent complement to chemical residue analysis and a useful tool in understanding the complex interactions of halogenated hydrocarbons. However, it must be mentioned that the proper prior clean-up method is very important for using the bioassay.

Role of interface dipole in metal gate/high-k effective work function modulation by aluminum incorporation

The interface dipole and its role in the effective work function (EWF) modulation by Al incorporation are investigated. Our study shows that the interface dipole located at the high-k/SiO2 interface causes an electrostatic potential difference across the metal/high-k interface, which significantly shifts the band alignment between the metal and high-k, consequently modulating the EWF. The electrochemical potential equalization and electrostatic potential methods are used to evaluate the interface dipole and its contribution. The calculated EWF modulation agrees with experimental data and can provide insight to the control of EWF in future pMOS technology.

Optical properties of aluminum-, gallium-, and indium-doped Bi4Ti3O12 thin films

Undoped and Al-, Ga-, and In-doped Bi4Ti3O12 thin films were prepared on fused quartz substrates by chemical solution deposition. Their microstructures and optical properties were investigated by x-ray diffraction and UV-visible-NIR spectrophotometer, respectively. The optical band-gap energies, Urbach energies, and linear refractive indices of all the films are derived from the transmittance spectrum. Following the single oscillator model, the dispersion parameters such as the average oscillator energy (E-0) and dispersion energy (E-d) are achieved. The energy band gap and refractive indices are found to decrease with introducing the dopants of Al, Ga, and In, which is useful for the band-gap engineering and optical waveguide devices. The refractive index dispersion parameter (E-0/S-0) increases and the chemical bonding quantity (beta) decreases in all the films compared with those of bulk. It is supposed to be caused by the nanosize grains in films. (c) 2009 American Institute of Physics. [DOI 10.1063/1.3138813]

Chemical liquid phase deposition of thin aluminum oxide films

Thin aluminum oxide films were deposited by a new and simple physicochemical method called chemical liquid phase deposition (CLD) on semiconductor materials. Aluminum sulfate with crystallized water and sodium bicarbonate were used as precursors for film growth, and the control of the system's pH value played an important role in this experiment. The growth rate is 12 nm/h with the deposition at [Al-2(SO4)(3)]=0.0837 mol.L-1, [NaHCO3]=0.214 mol.L-1, 15 degreesC. Post-growth annealing not only densifies and purifies the films, but results in film crystallization as well. Excellent quality of Al2O3 films in this work is supported by electron dispersion spectroscopy, Fourier transform infrared spectrum, X-ray diffraction spectrum and scanning electron microscopy photograph.

Magnetic ordering and irreversible magnetization between ZFC and FC states in RCo5Ga7 compounds

The magnetic properties of RCo5Ga7 (R = Y, Tb, Dy, Ho and Er) compounds which crystallize in the ScFe6Ga6-type structure have been studied. The compounds with R, Y, Tb, Dy, Ho and Er display behaviour similar to semiconductors. The Co transition metal sublattice is ferrimagnetic with a very low spontaneous magnetization. The ferrimagnetic ordering observed for R = Y, Tb, Dy, Ho and Er is due to the transition metal sublattice with transition temperatures at about 295 K. At low temperatures, the magnetic ordering for R Tb, Dy, Ho and Er is due to the rare-earth sublattice, which is ferromagnetic with a Curie temperature below 5 K. By fitting the linear part of the inverse magnetization, the effective magnetic moment of the R ion is found to be close to its expected theoretical value, with paramagnetic Curie temperatures below 5 K. Due to the paramagnetic nature of the R sublattice above 60 K, the ferrimagnetic ordering temperature of the Co sublattice does not vary with the type of rare-earth ion. The irreversibility of the magnetization of YCo5Ga7, as measured in zero-field cooled (ZFC) and field cooled (FC) states, is attributed to movement of domain walls. Application of a large enough applied field completes the movement of the domain wall from the low-temperature to the high-temperature one at 5 K. With a very low magnetic field 100 Oe, the difference between the ZFC and the FC shrinks. (C) 2004 Elsevier B.V. All rights reserved.

Surface-enhanced resonant Raman spectroscopy (SERRS) of single-walled carbon nanotubes absorbed on the Ag-coated anodic aluminum oxide (AAO) surface

In this paper, we developed a new kind of substrate, the silver-coated anodic aluminum oxide (AAO), to investigate the characters of surface-enhanced resonant Raman scattering (SERRS) of the dilute single-walled carbon nanotubes. Homogeneous Ag-coated AAO substrate was obtained by decomposing the AgNO3 on the surface of AAO. single-walled carbon nanotubes (SWNTs) were directly grown onto this substrate through floating catalyst chemical vapor deposition method (CVD). SERRS of SWNTs was carried out using several different wavelength lasers. The bands coming from metallic SWNTs were significantly enhanced. The two SERRS mechanisms, the "electromagnetic" and "chemical" mechanism, were mainly responsible for the experiment results. (c) 2005 Elsevier B.V. All rights reserved.

(Ga,Mn,N) compounds growth with mass-analyzed low energy dual ion beam deposition

The (Ga,Mn,N) samples were grown by the implantation of low-energy Mn ions into GaN/Al2O3 substrate at different elevated substrate temperatures with mass-analyzed low-energy dual ion beam deposition system. Auger electron spectroscopy depth profile of samples grown at different substrate temperatures indicates that the Mn ions reach deeper in samples with higher substrate temperatures. Clear X-ray diffraction peak from (Ga,Mn)N is observed in samples grown at the higher substrate temperature. It indicates that under optimized substrate temperature and annealing conditions the solid solution (Ga,Mn)N phase in samples was formed with the same lattice structure as GaN and different lattice constant. (C) 2003 Elsevier Science B.V. All rights reserved.

(Ga,Mn,As) compounds grown on semi-insulating GaAs with mass-analyzed low energy dual ion beam depositionw

The (Ga,Mn,As) compounds were obtained by the implantation of Mn ions into semi-insulating GaAs substrate with mass-analyzed low energy dual ion beam deposition technique. Auger electron spectroscopy depth profile of a typical sample grown at the substrate temperature of 250degreesC showed that the Mn ions were successfully implanted into GaAs substrate with the implantation depth of 160 nm. X-ray diffraction was employed for the structural analyses of all samples. The experimental results were greatly affected by the substrate temperature. Ga5.2Mn was obtained in the sample grown at the substrate temperature of 250degreesC. Ga5.2Mn, Ga5Mn8 and Mn3Ga were obtained in the sample grown at the substrate temperature of 400degreesC. However, there is no new phase in the sample grown at the substrate temperature of 200degreesC. The sample grown at 400degreesC was annealed at 840degreesC. In this annealed sample Mn3Ga disappeared, Ga5Mn8 tended to disappear,Ga5.2Mn crystallized better and a new phase of Mn2As was generated. (C) 2002 Elsevier Science B,V. All rights reserved.