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.

Interface as the origin of ferromagnetism in cobalt doped ZnO film grown on silicon substrate

We have investigated the magnetic properties of Co-doped zinc oxide (ZnO) film deposited on silicon substrate by magnetron sputtering. Co ions have a valence of 2+ and substitute for Zn sites in the lattice. By using a chemical etching method, an extrinsic ferromagnetism was demonstrated. The observed ferromagnetism is neither associated with magnetic precipitates nor with contamination, but originates from the silicon/silicon oxide interface. This interface ferromagnetism is characterized by being temperature independent and by having a parallel magnetic anisotropy. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.2989128]

Magnetic properties of ZnO-doped cobalt ferrite

The cobalt ferrites with chemical composition Co1+xZnxFe2-2xO4 (r=0.0, 0.1, 0.2, 0.4) were obtained with conventional solid reaction. The ZnO-doped samples have lower lattice constant than CoFe2O4 by adjusting Co ions to the octahedral sites. The results show that doping ZnO could extremely improve the magnetic properties. In comparison with pure CoFe2O4, the little ZnO-doped sample has higher permeability and much lower coercivity at the condition of a little decrease of magnetization saturation. Sample with x=0.1 shows evident magnetostrictive effect at the magnetic field of 30-60 mT while pure cobalt ferrite sample does not, though the saturation magnetostriction decreases. These indicate that ZnO-doping improves the magnetostrictive sensitivity of the cobalt ferrites and have potential applications in magnetoelectric devices and magnetic detector.

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.

(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.

Syntheses, crystallographic and magnetic properties of Nd3Fe29-xCrx and other associated compounds

A systematic study of syntheses and magnetic properties of the Nd-3 Fe29-xCrx (x=4.5, 4.7, 5.0, and 5.5) compounds has been performed. The single-phase compounds of Nd3Fe29-xCrx can be formed in the range 4.5 less than or equal to x less than or equal to 5.5. The Curie temperature Tc, the saturation magnetization M-S at 4.2 K, the anisotropy field H-A at 4.2 K and room temperature, and the intra-sublattice exchange coupling parameter j(FeFe) at 4.2 K for the Nd3Fe29-xCrx compounds decrease with increasing Cr composition from x=4.5 to 5.5, respectively. Nitrogenation and carbonation, unlike hydrogenation, result mainly in improvements of the Curie temperature, the saturation magnetization and the anisotropy field at 4.2 K and room temperature for the Nd3Fe29-xCrx compounds compared with their parent compounds.

High-frequency ferromagnetic resonance on ultrafine cobalt particles

We report on high-frequency (300-700 GHz) ferromagnetic resonance (HF-FMR) measurements on cobalt superparamagnetic particles with strong uniaxial effective anisotropy. We derive the dynamical susceptibility of the system on the basis of an independent-grain model by using a rectangular approach. Numerical simulations give typical line shapes depending on the anisotropy, the gyromagnetic ratio, and the damping constant. HF-FMR experiments have been performed on two systems of ultrafine cobalt particles of different sizes with a mean number of atoms per particles of 150 +/- 20 and 310 +/- 20. In both systems, the magnetic anisotropy is found to be enhanced compared to the bulk value, and increases as the particle size decreases, in accordance with previous determinations from magnetization measurements. Although no size effect has been observed on the gyromagnetic ratio, the transverse relaxation time is two orders of magnitude smaller than the bulk value indicating strong damping effects, possibly originating from surface spin disorders.

Photoluminescence enhancement of porous silicon by organic cyano compounds

A pronounced photoluminescence enhancement on chemically oxidized porous silicon was induced by a series of organic cyano compounds including 1,2-dicyanoethylene (CE), 1,3-dicyanobenzene (1,3-CB), 1,4-dicyanobenzene (1,4-CB), 1-cyanonaphthalene (1-CN), and 9-cyanoanthracene (9-CA). Photoluminescence enhancement effects were reversible for all compounds studies in this work. A dependence of photoluminescence enhancement on the steric effect and the electronic characteristics of these compounds and the structure of the porous silicon substrates were analyzed in terms of the photoluminescence enhancing factors. Surface chemical composition examined by Fourier transform infrared (FTIR) spectra demonstrated that the surface Si-H bonds were not changed and no new luminescent compounds were formed on porous silicon surface during adsorption of cyano compounds. A mechanism based on induced surface states acting as radiative recombination centers by cyano compounds adsorption was suggested.