Fe(III) and Fe(II) induced photodegradation of nonylphenol polyethoxylate (NPEO) oligomer in aqueous solution and toxicity evaluation of the irradiated solution.

Photodegradation of nonylphenol tri-ethoxylate (NPEO3) in aqueous solution, and the effects of Fe(III) or Fe(II) were studied. The increasing degradation kinetics of NPEO3 were observed when 500µM Fe(III) or Fe(II) was present in the solutions. Altered formation of NPEO oligomers with shorter EO chains, including nonyphenol (NP), NPEO1 and NPEO2, was observed in water and in solutions containing Fe(III) or Fe(II). The molar percentage yields of NP and NPEO1,2 production from NPEO3 photodegradation were approximately 20% in NPEO3 solution, while NPEO3 solution with Fe(III), this percentage increased to approximately 50%. In solution with Fe(II), the molar balance between the photodegradation of NPEO3 and the production of NP and NPEO1,2 was observed. A luminescent bacterium, Vibrio fischeri, was used to identify changes in the toxicity of NPEO3 solutions during the photodegradation process under different conditions, while dose addition (DA) model was used to estimate the toxicity of products. Toxicity of NPEO3/water solution increased significantly following the irradiation of UVA/UVB mixture. In contrast, obviously decreasing toxicity was observed when NPEO3 underwent photodegradation in the presence of Fe(III).

Gamma radiation/H2O2 treatment of a nonylphenol ethoxylates: Degradation, cytotoxicity, and mutagenicity evaluation.

Gamma radiation/H2O2 treatment of nonylphenol polyethoxylates (NPEO) was performed and treatment effect was evaluated on the basis of degradation, chemical oxygen demand (COD) and total organic carbon (TOC), and toxicity reduction efficiencies. The radiolytic by-products were determined by Fourier Transform Infrared Spectroscopy (FTIR), High-Performance Liquid Chromatography (HPLC), and Gas Chromatography-Mass Spectrometry (GC-MS) techniques. Low mass carboxylic acids, aldehyde, ketone, and acetic acid were identified as the by-products of the NPEO degradation. NPEO sample irradiated to the absorbed dose of 15 kGy/4.58% H2O2 showed more than 90% degradation. Allium cepa (A. cepa), brine shrimp, heamolytic tests were used for cytotoxicity study, while mutagenicity was evaluated through Ames test (TA98 and TA100 strains) of treated and un-treated NPEO. The reductions in COD and TOC were greater than 70% and 50%, respectively. Gamma radiation/H2O2 treatment revealed a considerable reduction in cytotoxicity and mutagenicity. A. cepa, heamolytic and shrimp assays showed cytotoxicity reduction up to 68.65%, 77%, and 94%, respectively. The mutagenicity reduced up to 62%, 74%, and 79% (TA98) and 68%, 78%, and 82% (TA100), respectively of NPEO-6, NPEO-9, and NPEO-30 irradiated to the absorbed dose of 15 kGy/4.58% H2O2. NPEO-6 detoxified more efficiently versus NPEO-9 and NPEO-30 and results showed that Gamma radiation/H2O2 treatment has the potential to mineralize and detoxify NPEO.

Degradation of the commercial surfactant nonylphenol ethoxylate by advanced oxidation processes.

Four different oxidation process, namely direct photolysis (DP) and three advanced oxidation processes (heterogeneous photocatalysis - HP, eletrochemical oxidation - EO and photo-assisted electrochemical oxidation - PEO) were applied in the treatment of wastewater containing nonylphenol ethoxylate (NPnEO). The objective of this work was to determine which treatment would be the best option in terms of degradation of NPnEO without the subsequent generation of toxic compounds. In order to investigate the degradation of the surfactant, the processes were compared in terms of UV/Vis spectrum, mineralization (total organic carbon), reaction kinetics, energy efficiency and phytotoxicity. A solution containing NPnEO was prepared as a surrogate of the degreasing wastewater, was used in the processes. The results showed that the photo-assisted processes degrade the surfactant, producing biodegradable intermediates in the reaction. On the other hand, the electrochemical process influences the mineralization of the surfactant. The process of PEO carried out with a 250W lamp and a current density of 10mA/cm(2) showed the best results in terms of degradation, mineralization, reaction kinetics and energy consumption, in addition to not presenting phytotoxicity. Based on this information, this process can be a viable alternative for treating wastewater containing NPnEO, avoiding the contamination of water resources.

Treatment of solutions containing nonylphenol ethoxylate by photoelectrooxidation.

In this work the photoelectrooxidation (PEO) was applied in the treatment of a solution containing nonylphenol ethoxylate surfactant (NP4EO). The use of different lamps (125 and 250 W), current density (5 and 10 mA cm(-2)) and treatment time (0, 60, 120, 180 and 240 min) were investigated. The samples were characterized by UV/Vis, total organic carbon (TOC), gas chromatography associated to mass spectroscopy (GC/MS) and ecotoxicity. The reaction kinetics were calculated and the light flux and pH were measured. The results of analysis by UV/Vis show that there is degradation of nonylphenol ethoxylated in the treatment time of 240 min for all configurations, and the configurations that used a 250 W lamp and a current density of 10 mA cm(-2) obtained better results, with a reduction of 83% in TOC, indicating a high mineralization of the surfactant. It was further found in the GC/MS that the configurations that used the 125 W lamp promoted a smaller incident light flux on the solution, and, regardless of the applied current density, it was generated the reaction intermediate nonylphenol, more toxic than the parent compound. The opposite can be observed when a 250 W lamp was used, which produced a higher incident light flux. Based on the degradation products detected, a simplified mechanism for degradation of nonylphenol ethoxylate was proposed. Although a treatment time of 240 min with photoelectrooxidation with different configurations was not effective in the complete mineralization of the compound, a promising process was developed with the treatment using a lamp of 250 W and a current density of 10 mA cm(-2), which generated a solution with less toxicity than the original one.

The hydroxyl radical scavenging effect of textile preparation auxiliaries on the photochemical treatment of nonylphenol ethoxylate.

The present paper deals with the effects of frequently used textile preparation chemicals and common ions on the H2O2/UV-C treatment of a commercially important and slowly biodegradable nonionic surfactant, namely a nonylphenol bearing 10 ethoxylated chains. For this purpose, the effect of soda ash carbonate (0-5.0 g L(-1)), two phosphonic acid-based organic sequestering agents (0-2.5 g L(-1)) and chloride (0-3.0 g L(-1)) at two different pH values (3.5 and 10.5) as hydroxyl radical scavengers was experimentally investigated. Among the studied textile preparation chemicals and hydroxyl radical scavengers, the decreasing order of hydroxyl radical scavenging capacity was established as diethylene triamine pentamethylene phosphonic acid > 1-hydroxy ethylidene-1,1-diphosphonic acid > soda ash carbonate at pH 10.5 > chloride at pH 3.5 > chloride at pH 10.5.

Fabrication of submicrometer biomolecular patterns by near-field exposure of plasma-polymerized tetraglyme films.

Plasma-polymerized tetraglyme films (PP4G) have been modified by exposure to ultraviolet (UV) light from a frequency-doubled argon ion laser (244 nm) and characterized using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). XPS data indicated that the ether component of the C 1s spectrum declined after UV exposure, while components due to carbonyl and carboxylate groups increased. The film was physically eroded by UV exposure: after 100 s the rate of erosion reached a steady state of 0.05 nm s(-1). The coefficient of friction, measured by friction force microscopy (FFM), increased substantially following exposure to UV light, reaching a limiting value after 10 min exposure, in agreement with the time taken for the ether and carboxylate components in the C 1s spectrum to reach a limiting value. Samples exposed to UV light through a mask yielded excellent frictional contrast. When immersed in solutions of proteins and protein-functionalized nanoparticles labeled with fluorescent markers, selective adsorption occurred onto the exposed regions of these samples. Excellent fluorescence contrast was obtained when samples were characterized by confocal microscopy, indicating that the exposed areas become adhesive toward proteins, while the masked areas remain resistant to adsorption. Submicrometer structures have been formed by exposing PP4G films to UV light using a scanning near-field optical microscope coupled to a UV laser. Structures as small as 338 nm have been formed and used to immobilize proteins. Again, excellent contrast difference was observed when labeled proteins were adsorbed and characterized by confocal microscopy, suggesting a simple and effective route to the formation of submicrometer scale protein patterns.

Sonochemical synthesis of Au-TiO2 nanoparticles for the sonophotocatalytic degradation of organic pollutants in aqueous environment.

Au-TiO2 photocatalysts were sonochemically prepared by three different procedures and their photocatalytic and sonophotocatalytic efficiencies were evaluated by studying the degradation of a representative organic pollutant, nonylphenol ethoxylate (NPE) surfactant in aqueous solutions. In the first procedure, Au-TiO2 nanoparticles were prepared by depositing sonochemically synthesized gold nanoparticles on Degussa P25 TiO2 by stirring in the absence of an ultrasonic field. In the second procedure, Au nanoparticles were sonochemically synthesized and simultaneously deposited on Degussa P25 TiO2 particles. In the third procedure, Au-TiO2 nanoparticles were sonochemically synthesized by the simultaneous irradiation of an aqueous solution containing AuCl4- and titanium tetraisopropoxide. The prepared nanoparticles were characterized by UV-vis spectroscopy and transmission electron microscopy (TEM). The catalytic activities of these nanomaterials were compared for the degradation of a polydisperse nonylphenol ethoxylate, Teric GN9 by photocatalysis and sonophotocatalysis under visible light/high frequency ultrasound irradiation. The catalysts did not show a synergetic effect towards the sonophotocatalytic degradation of Teric GN9. This might be due to the interference of the degradation products generated during the simultaneous irradiation by light and ultrasound.

Photolysis of nonylphenol ethoxylates: the determination of the degradation kinetics and the intermediate products.

The photolysis of nonylphenol ethoxylates with an average oligomers length of ten ethoxylate units (NPEO(10)) in aqueous solution under UV, as well as the influence of humic acid (HA) on the photolysis was studied. A 125W high-pressure mercury lamp was employed as the light source. The intermediate products from the photolysis were determined by LC-MS. The results indicated that NPEO(10) underwent direct photolysis upon exposed to UV. The degradation pathway was complex. Besides the generally proposed degradation pathway of ethylene oxide (EO) side chains shortening, the oxidation of alkyl chain and EO chain led to intermediates having both a carboxylated (as well as carbonylated) ethoxylate and alkyl chain of varying lengths. The hydrogenation of benzene ring was also detected. The kinetics data showed that the first order reaction kinetics could be well used to describe the kinetics of NPEO(10) degradation. In the presence of dissolved organic matter by HA addition, the performance of NPEO(10) photodegradation was reduced. The photolysis rate decreased with increased HA concentration.

Degradation of nonylphenol polyethoxylates by ultraviolet B irradiation and effects of their products on mammalian cultured cells.

Nonylphenol polyethoxylates (NPEOs) are widely used as non-ionic surfactants and their biodegradation products such as 4-n-nonylphenol are stable and have been demonstrated to be cytotoxic. In the aquatic environment, these compounds are usually exposed to sunlight, and while the correlation between the biodegradation of NPEOs and changes in cytotoxicity has been reported, the relationship between the photodegradation of NPEOs and cytotoxicity has not. In this study, we investigated the degradation of NPEO by ultraviolet (UV) irradiation, especially UVB irradiation, and the effects on mammalian cell lines. NPEO with a smaller number of ethylene oxide (EO) units showed greater cytotoxicity. Although NPEO (10) completely inhibited the proliferation of the cells, NPEO (70) showed no toxicity. UVB irradiation significantly induced a shortening of the side chain, which was due to the production of ROS. The EO side chain of NPEO (10), was gradually degradated, but that of NPEO (70) was degradated near the benzene ring. Furthermore, the degradation of the benzene ring was more effective in NPEO (70) than NPEO (10). The toxicity of NPEO (10) in cultured cells decreased following UVB irradiation, whereas that of NPEO (70) was induced after UVB irradiation at 500 J/cm2 and disappeared at 1000 J/cm2. This might be due to the production of NPEO with a short side chain and 4-n-nonylphenol by the degradation of EO and due to the degradation of the benzene ring at higher doses of UVB irradiation. This study shows the significance of UV exposure to the degradation of alkylphenol polyethoxylates in the environment.

Carbohydrate radicals: from ethylene glycol to DNA strand breakage.

Radiation-induced DNA strand breakage results from the reactions of radicals formed at the sugar moiety of DNA. In order to elucidate the mechanism of this reaction investigations were first performed on low molecular weight model systems. Results from studies on deoxygenated aqueous solutions of ethylene glycol, 2-deoxy-D-ribose and other carbohydrates and, more relevantly, of D-ribose-5-phosphate have shown that substituents can be eliminated from the beta-position of the radical site either proton and base-assisted (as in the case of the OH substituent), or spontaneously (as in the case of the phosphate substituent). In DNA the C(4') radical undergoes strand breakage via this type of reaction. In the presence of oxygen the carbon-centred radicals are rapidly converted into the corresponding peroxyl radicals. Again, low molecular weights models have been investigated to elucidate the key reactions. A typical reaction of DNA peroxyl radicals is the fragmentation of the C(4')-C(5') bond, a reaction not observed in the absence of oxygen. Although OH radicals may be the important direct precursors of the sugar radicals of DNA, results obtained with poly(U) indicate that base radicals may well be of even greater importance. The base radicals, formed by addition of the water radicals (H and OH) to the bases would in their turn attack the sugar moiety to produce sugar radicals which then give rise to strand breakage and base release. For a better understanding of strand break formation it is therefore necessary to investigate in more detail the reactions of the base radicals. For a start, the radiolysis of uracil in oxygenated solutions has been reinvestigated, and it has been shown that the major peroxyl radical in this system undergoes base-catalysed elimination of O2-., a reaction that involves the proton at N(1). In the nucleic acids the pyrimidines are bound at N(1) to the sugar moiety and this type of reaction can no longer occur. Therefore, with respect to the nucleic acids, pyrimidines are good models only in acid solutions where the O2-. elimination reaction is too slow to compete with the bimolecular reactions of the peroxyl radicals. Moreover, the long lifetime of the radical sites on the nucleic acid strand may allow reactions to occur which are kinetically of first order, and which cannot be studied in model systems at ordinary dose rates. It is therefore suggested to extend model system studies to low dose rates and to oligonucleotides. Such studies might eventually reveal the key reactions in radical-induced DNA degradation.

Controlled slow release of chemotherapeutic drugs for cancer from matrices prepared by radiation polymerization at low temperatures.

The vinyl polymer-chemotherapeutic agent composites of various shapes (rod, tablet, membrane, microsphere, and powder) were prepared by radiation polymerization at low temperatures for the purpose of durable controlled slow release of drugs from implanted matrices. Bleomycin hydrochloric acid, mitomycin C, and 5-fluorouracil were tested as chemotherapeutic drugs entrapped in poly(diethylene glycol dimethacrylate) including a small quantity of a polymer such as poly(styrene), poly(vinyl formal), poly(vinyl acetate), poly(methyl methacrylate) on polyethylene glycol No. 600. The release rates from the matrices depended much on the kind of polymer, drug, and monomer concentration in polymerization and also on the shape of the composite. The release of these drugs from polymer matrices obeyed the diffusion-controlled release mechanism based on Higuchi's equation and was durable for more than thirty days. It was found that the release rate can be controlled easily by design of the shapes and structures of the polymer matrices.