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Sonochemical preparation of composite nanoparticles of Au/gamma-Fe2O3 and magnetic separation of glutathione.

We prepared Au/gamma-Fe2O3 composite nanoparticles by sonochemically reducing Au(III) ions employing no stabilizer in the aqueous solution to form stable Au nanoparticles and allowing them to attach onto the surface of gamma-Fe2O3 particles with an average size of 21 nm. Size of the formed Au nanoparticle depended on the initial concentration of Au(III) ions. The number of the Au nanoparticles, supported on each gamma-Fe2O3 particle was controlled by changing the relative amounts of Au(III) ions and gamma-Fe2O3 particles. The composite nanoparticles exhibited a high affinity with glutathione, a tripeptide with mercapto group so that separation and manipulation of glutathione in aqueous solutions could be performed by application of external magnetic field. Because the surfaces of the Au nanoparticles were not shielded by any stabilizers, or naked, sonochemically prepared Au/gamma-Fe2O3 composite nanoparticles seemed to show stronger affinity to the glutathione than those by the radiochemical method.

Benzamides↗

Light-absorption ratio variation approach to determination of nickel (II) in ng/ml level with 1, 5-di(2-hydroxy-5-sulfophenyl)-3-cyanoformazan.

The light-absorption ratio variation approach (LARVA) has been described and applied to the quantitative detection of ultramicro amounts of Ni by spectrophotometry, which raises notably the detection sensitivity. The complexation between 1, 5-di(2-hydroxy-5-sulfophenyl)-3-cyanoformazan (DSPCF) and Ni(II) at pH 9.11 was investigated and the binary complex was characterized by the spectral correction technique. Results have shown that deltaAr-1 (deltaAr--light-absorption ratio variation) is linear in the range of Ni(II) between 5 and 200 ng/ml. The limit of detection (3sigma) of Ni(II) is only 1.3 ng/ml. The complexation is selective in the presence of fluoride, hexametaphosphate, ethylene diamine tetraacetate and thioglycollic acid. It has been applied to analysis of water quality with satisfactory results.

Environmental Monitoring↗

Accelerated mineralization of the drug Diclofenac via Fenton reactions in a concentric photo-reactor.

The complete mineralization of concentrated solutions of Diclofenac (2-[(2,6-dichlorophenyl) amino] benzene-acetic acid) sodium salt C14H10C12NO2Na was carried out in a concentric cylindrical immersion photoreactor in batch mode operation. Irradiation with a lamp emitting light at 254 nm (400 W) achieved total mineralization of Diclofenac solutions (0.062 mM or TOC 20 mg C l(-1)) in times under an hour. The mineralization was carried out via Fenton photo-assisted treatment. A determination of the solution parameters was carried out to optimize the time of the Diclofenac pretreatment, the type and intensity of the light source, the effect of the concentrations of Fe-ions and the oxidant added in solution and the reactor recirculation rate. Diclofenac disappearance was monitored by high liquid pressure chromatography (HPLC). Concomitantly, the aromatic and aliphatic intermediates were also monitored under low-energy (36 W) light irradiation at 366 nm in order to be able to detect the intermediates by HPLC in the minute time scale. The decrease of the chemical oxygen demand was followed during Diclofenac degradation. The activation energy for the mineralization of Diclofenac was determined to be 4.02 Kcal mol(-1).

Anti-Inflammatory Agents, Non-Steroidal↗

Occurrence and source of brominated organic compounds in surface waters.

Monitoring of organic halogen compounds, measured as adsorbable organically bound bromine (AOBr), in an eutrophic lake, which is influenced by treated waste water, revealed repeatedly high concentrations of organobromine compounds in late summer, whereas five times lower values were measured during the rest of the year. It was possible to reproduce the in situ observed AOBr increase in the laboratory. Batch experiments were performed with lake water from two different lakes and an algae culture. It could be shown that the AOBr production is not limited to strong waste water influenced lakes. Furthermore, the AOBr formation requires light and the presence of algae, and thus is most probably biotic in nature. A low content of nutrients favours the formation of organic bromine compounds. To our knowledge this is the first report about the seasonally occurrence of naturally produced organic bromine compounds in lakes/surface waters.

Adsorption↗

Quantitative structure-property relationships on photodegradation of PCDD/Fs in cuticular waxes of laurel cherry (Prunus laurocerasus).

By the use of the partial least squares (PLS) method and 13 fundamental quantum chemical descriptors computed by PM3 Hamiltonian, a OSPR model was developed for first order rate constants of photodegradation of 10 PCDD/Fs dissolved in cuticular wax from laurel cherry (Prunus laurocerasus) leaves and exposed to sunlight. The QSPR showed that photodegradation rates increase with the degree of chlorination of the homologues. PCDD/Fs with large values of Q(Cl) (the largest positive atomic charge on a chlorine atom in a molecule), Q(O)- (the most negative atomic charge on the oxygen atoms in a molecule), and mu (dipole moment) tend to photodegrade fastest. PCDD/Fs with large values of E(lumo) (the energy of the lowest unoccupied molecular orbital), E(homo) (the energy of the highest occupied molecular orbital), and E(lumo) - E(homo) tend to have the lowest photodegradation rates.

Benzofurans↗

Deposition of motor vehicle emissions and winter maintenance along roadside assessed by snow analyses.

A vertical snow-sampling method, where a sample was taken throughout the snowpack, was used to estimate the pollutant load on a roadside where average daily traffic density was about 9100 motor vehicles. The snow samples were collected at two sites, forest and open field, at two distances of 10 and 30 m from the road. The concentrations of inorganic anions (Cl(-), NO(-)(3), SO(2-)(4)), total N, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated phenols (PCPhs) were analysed. The results suggest that on roadsides there is a deposition caused by road traffic emissions and winter maintenance which exceeds normal background deposition. Inorganic anions mainly in particle form, originating from winter maintenance, are deposited near the road. PAHs with low molecular weight (</=252) are mainly in gaseous form and are deposited further away from the road. Also, some PCPhs show similar behaviour. The dispersion is different at the forest site than at the open-field site. Our results also indicate that the vertical snow-sampling method can be used in studying pollutant load from traffic near the roads. However, studies should focus on individual PAH or PCPh compounds as markers of highway pollution. The deposition of mixtures of compounds does not bring sufficient information in the light of present knowledge.

Journal Article↗

Avoiding pitfalls in the determination of halocarboxylic acids: the photochemistry of methylation.

Haloethanoic (haloacetic) acids are formed during chlorination of drinking water and are regulated by the Environmental Protection Agency (EPA). These compounds are normally quantified by gas chromatography with electron capture detection (GC-ECD) as the methyl esters. EPA Method 552 uses diazomethane (CH2N2) for this purpose, but has only been validated by EPA for HAA6: chloro-, dichloro-, bromo-, dibromo-, bromochloro- and trichloroacetic acids. EPA Method 552.2 was developed and validated for all nine analytes (HAA9 = HAA6 + dibromochloro-, bromodichloro- and tribromoethanoic acids). Since the promulgation of Method 552.2, which uses acidic methanol, a debate has ensued over discrepancies observed by various laboratories when using diazomethane instead. In an effort to identify and eliminate potential sources for these discrepancies, a comparative study was undertaken for HAA9. Better accuracy and precision were observed for all HAA9 species by Method 552.2; recoveries were satisfactory in de-ionized and tap water. Method 552 remains satisfactory for HAA6. Systematic differences in instrumental response are observed for the two methods, but these are precise and may be accounted for using similarly treated standards and analyte-fortified (spiked) samples. That notwithstanding, Method 552 (CH2N2) was shown to be unsuitable for dibromochloro-, bromodichloro- and tribromoethanoic acids (HAA9-6). The primary problem appears to be a photoactivated reaction between diazomethane and the HAA9-6 analytes; however, side reactions were found to occur even in the dark. Analyte loss is most pronounced under typical laboratory lighting (white F40 fluorescent lamps + sunlight), but it is also observed under Philips gold F40 lamps (lambda > or = 520 nm), and in the dark.

Carboxylic Acids↗

Treatment of microbiologically polluted aquaculture waters by a novel photochemical technique of potentially low environmental impact.

The applicability of a novel procedure for the disinfection of microbiologically polluted waters from fish-farming ponds, based on the combined action of visible light (including sunlight) and porphyrin-type photosensitising agents, has been investigated using (a) cell cultures of a Gram-positive bacterium (meticillin-resistant Staphylococcus aureus), a Gram-negative bacterium (Escherichia coli) and a fungal pathogen (Saprolegnia spp.); (b) pilot aquaculture plants involving either spontaneously or artificially Saprolegnia-infected rainbow trout (Oncorhynchus mykiss). The results obtained by using two cationic porphyrins, namely a tetra-substituted N-methyl-pyridyl-porphine (C1) and its analogue where one N-methyl group had been replaced by a N-tetradecyl chain (C14), and low intensity visible light irradiation showed an extensive (up to 6-7 log) decrease in the bacterial/fungal population after short incubation and irradiation times in the presence of micromolar photosensitiser concentrations. Moreover, C14 showed some toxic effect also in the absence of light. Extension of these studies to the pilot plants indicated that both C1 + light and C14 can prevent Saprolegnia infections or promote the cure of saprolegniasis in infected trout by treatments with submicromolar porphyrin doses. The procedure appears to be of low cost and to have a low environmental impact.

Animals↗

Comparison of two direct-reading instruments (FM-7400 and Fibrecheck FC-2) with phase contrast optical microscopy to measure the airborne fibre number concentration.

The use of direct-reading instruments to measure the airborne fibre number concentration is on the increase. The response of two of these instruments (FM-7400 and Fibrecheck FC-2) was compared with the conventional method of sampling on filters and counting by phase contrast microscopy. Four types of fibres were studied at different concentrations and relative humidity levels. The FM-7400 can be calibrated by the manufacturer for two different levels of sensitivity (standard and high). For the tests where it was set to the sensitivity level with which it had been calibrated, the ratio of the concentration measured by the instrument to the concentration obtained by the conventional method varied in the range 0.5-1 for the different types of fibres studied (chrysotile, glass wool and ceramic fibres). The Fibrecheck FC-2 is a much less versatile instrument. On the basis of a calibration allowing correct detection of asbestos fibres, it greatly overestimated the concentration of man-made mineral fibres. In its normal calibration state a fine chrysotile aerosol was poorly detected. For man-made mineral fibres, the response was highly dependent on the nature of the fibres. These instruments require calibration with the type of fibres to be studied. Unfortunately, this operation is not always accessible to the user and may require the services of a specialized laboratory, as the manufacturer is not always in a position to carry this out.

Aerosols↗

Formation and fate of gaseous and particulate mutagens and carcinogens in real and simulated atmospheres.

The growing use of coal for heating and electric power generation and diesel engines in light duty motor vehicles will increase not only the existing atmospheric concentrations of criteria pollutants such as NO2, SO2, O3 and fine particulates, but also the concentrations of a number of highly reactive gaseous copollutants such as HONO, HONO2, PAN and the nitrate radical, NO3. These gaseous noncriteria pollutants are of interest not only because of their roles in the chemistry of the "clean" and polluted troposphere, including "acid rain," but also because they may pose health risks disproportionate to their relatively low ambient concentrations, and through complex heterogeneous reactions, they may serve as precursors or catalysts in the formation of "nonclassical" particulate mutagens and carcinogens such as certain nitroarenes associated with combustion generated particulate polycyclic organic matter (POM). Results of research efforts to establish current ambient levels of these noncriteria pollutants and to develop an understanding of their sources, formation and sinks are reported here. First, long pathlength (greater than or equal to 1 km) infrared and UV-visible spectroscopic studies of ambient levels of gaseous HONO, NO3, HONO2, PAN, HCHO and HCOOH in southern California atmospheres are described, and data given on their ambient concentrations. Second, an integrated chemical/microbiological investigation is described. It is directed toward identifying the nature of direct-acting mutagens found in extracts of diesel and ambient POM, as well as those formed upon exposure of environmentally relevant PAH to simulated natural and polluted atmospheres. The identification of certain of these mutagens, including a newly identified class of mutagenic PAH-lactones is discussed, along with the mechanisms of their formation and fate in the natural and polluted troposphere.

Air Pollutants↗

Sensitivity metric approach for retrieval of aerosol properties from multiangular and multispectral polarized radiances.

Linearly polarized radiation is sensitive to the microphysical properties of aerosols, namely, to the particle-size distribution and refractive index. The discriminating power of polarized radiation increases strongly with the increasing range of scattering angles and the addition of multiple wavelengths. The polarization and directionality of the Earth's reflectances (POLDER) missions demonstrate that some aerosol properties can be successfully derived from spaceborne polarimetric, multiangular measurements at two visible wavelengths. We extend the concept to analyze the retrieval capabilities of a spaceborne instrument with six polarimetric channels at 412, 445, 555, 865, 1250, and 2250 nm, measuring approximately 100 scattering angles covering a range between 50 and 150 deg. Our focus is development of an analysis methodology that can help quantify the benefits of such multiangular and multispectral polarimetric measurements. To that goal we employ a sensitivity metric approach in a framework of the principal-component analysis. The radiances and noise used to construct the sensitivity metric are calculated with the realistic solar flux for representative orbital viewing geometries, accounting for surface reflection from the ground, and statistical and calibration errors of a notional instrument. Spherical aerosol particles covering a range of representative microphysical properties (effective radius, effective variance, real and imaginary parts of the refractive index, single-scattering albedo) are considered in the calculations. We find that there is a limiting threshold for the effective size (approximately 0.7 microm), below which the weak scattering intensity results in a decreased signal-to-noise ratio and minimal polarization sensitivity, precluding reliable aerosol retrievals. For such small particles, close to the Rayleigh scattering limit, the total intensity provides a much stronger aerosol signature than the linear polarization, inspiring retrieval when the combined signals of intensities and the polarization fraction are used. We also find a strong correlation between aerosol parameters, in particular between the effective size and the variance, which forces one to simultaneously retrieve at least these two parameters.

Aerosols↗

Use of artificial streams for toxicological research.

A review of the literature pertaining to the use of artificial streams as research tools in both toxicant and nontoxicant studies was conducted. This document summarizes that review and provides an assessment of the value of artificial streams in toxicological research. Descriptions are presented of the major types of artificial streams including considerations for the physical design of those streams based on their intended use. Research representative of nontoxicant behavioral, productivity, and trophic relationship studies is summarized to provide a background for the more in-depth discourse on toxicant research. Toxicant research is reviewed in relation to environmental factors such as physical type of artificial stream, light, water, and substrate and experimental conditions including biota tested, method of biota introduction, measured parameters, and toxicant. Comparisons and assessment are presented concerning the use of the appropriate artificial system for addressing various types of toxicant research emphasizing simple vs. complex systems.

Animals↗

Combination effect of light and toxicity in algal tests.

The sensitivity of Scenedesmus subspicatus against potassium dichromate is positively correlated to the photon flux density during the algal growth inhibition test. Low photon flux densities led to significantly reduced maximum effects and higher EC50 levels. To improve the testing of colored substances, we distinguished between the toxic effect (chemical part, represented by potassium dichromate) and the shading effect (physical part, simulated by reduced light intensities during the test) of a hypothetical light absorbing substance. The contribution of these single effects to the total inhibition varied greatly. At high concentrations of potassium dichromate (1.6 and 3.2 mg L(-1)) the physical part never exceeded 25% of the total inhibition, not even at strongest light reduction, while at low concentrations (0.2 and 0.4 mg L(-1)) the physical effect became more prominent when halving the amount of available light. Further, the combination effect of the chemical and the physical effect could be calculated well only by using the concept of independent action. Thus, if chemical and physical effects are measured in combination, as is the case in tests with dye-stuffs, the current test protocol for the algal growth inhibition test may lead to incorrect estimations of the toxic potential.

Chlorophyta↗

[Photoelectrocatalytic degradation of Rhodamine B using mesh Ti/TiO2 electrode].

An innovative mesh titanium dioxide (TiO2) electrode was prepared by anodisation. The morphology and the crystalline texture of the TiO2 film on electrode were examined by SEM and Raman spectroscopy respectively. The results indicated that the structure and properties of the film depended on anodisation rate, and the anatase was the dominant component under the controlled experimental conditions. Biasing could increase the efficiency of photocatalytic degradation of organic matters. Mineralization Rhodamine B (Rh B) was complete relatively in photoelectro-catalytic (PEC) oxidation. Both chromogen destruction of Rh B and de-ehtylation in PEC degradation took place simultaneously.

Catalysis↗