988 resultados para oxalic acid


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This investigation used a combination of techniques, such as X-ray diffraction, inductively coupled plasma optical emission spectroscopy and infrared spectroscopy, to determine the dissolution mechanisms of the Bayer precipitate and the associated rate of dissolution in acetic, citric and oxalic acid environments. The Bayer precipitate is a mixture of hydrotalcite, calcium carbonate and sodium chloride that forms during the seawater neutralisation of Bayer liquors (waste residue of the alumina industry). The dissolution rate of a Bayer precipitate is found to be dependent on (1) the strength of the organic acid and (2) the number of donating H+ ions. The dissolution mechanism for a Bayer precipitate consists of several steps involving: (1) the dissolution of CaCO3, (2) formation of whewellite (calcium oxalate) when oxalic acid is used and (3) multiple dissolution steps for hydrotalcite that are highly dependent on the pH of solution. The decomposition of the Al–OH hydrotalcite layers resulted in the immediate formation of Al(OH)3, which is stable until the pH decreases below 5.5. This investigation has found that the Bayer precipitate is stable across a wide pH range in the presence of common organic acids found in the rhizosphere, and that initial decomposition steps are likely to be beneficial in supporting plant growth through the release of nutrients such as Ca2þ and Mg2þ.

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Basidiomycetous white-rot fungi are the only organisms that can efficiently decompose all the components of wood. Moreover, white-rot fungi possess the ability to mineralize recalcitrant lignin polymer with their extracellular, oxidative lignin-modifying enzymes (LMEs), i.e. laccase, lignin peroxidase (LiP), manganese peroxidase (MnP), and versatile peroxidase (VP). Within one white-rot fungal species LMEs are typically present as several isozymes encoded by multiple genes. This study focused on two effi cient lignin-degrading white-rot fungal species, Phlebia radiata and Dichomitus squalens. Molecular level knowledge of the LMEs of the Finnish isolate P. radiata FBCC43 (79, ATCC 64658) was complemented with cloning and characterization of a new laccase (Pr-lac2), two new LiP-encoding genes (Pr-lip1, Pr-lip4), and Pr-lip3 gene that has been previously described only at cDNAlevel. Also, two laccase-encoding genes (Ds-lac3, Ds-lac4) of D. squalens were cloned and characterized for the first time. Phylogenetic analysis revealed close evolutionary relationships between the P. radiata LiP isozymes. Distinct protein phylogeny for both P. radiata and D. squalens laccases suggested different physiological functions for the corresponding enzymes. Supplementation of P. radiata liquid culture medium with excess Cu2+ notably increased laccase activity and good fungal growth was achieved in complex medium rich with organic nitrogen. Wood is the natural substrate of lignin-degrading white-rot fungi, supporting production of enzymes and metabolites needed for fungal growth and the breakdown of lignocellulose. In this work, emphasis was on solid-state wood or wood-containing cultures that mimic the natural growth conditions of white-rot fungi. Transcript analyses showed that wood promoted expression of all the presently known LME-encoding genes of P. radiata and laccase-encoding genes of D. squalens. Expression of the studied individual LME-encoding genes of P. radiata and D. squalens was unequal in transcript quantities and apparently time-dependent, thus suggesting the importance of several distinct LMEs within one fungal species. In addition to LMEs, white-rot fungi secrete other compounds that are important in decomposition of wood and lignin. One of these compounds is oxalic acid, which is a common metabolite of wood-rotting fungi. Fungi produce also oxalic-acid degrading enzymes of which the most widespread is oxalate decarboxylase (ODC). However, the role of ODC in fungi is still ambiguous with propositions from regulation of intra and extracellular oxalic acid levels to a function in primary growth and concomitant production of ATP. In this study, intracellular ODC activity was detected in four white-rot fungal species, and D. squalens showed the highest ODC activity upon exposure to oxalic acid. Oxalic acid was the most common organic acid secreted by the ODC-positive white-rot fungi and the only organic acid detected in wood cultures. The ODC-encoding gene Ds-odc was cloned from two strains of D. squalens showing the first characterization of an odc-gene from a white-rot polypore species. Biochemical properties of the D. squalens ODC resembled those described for other basidiomycete ODCs. However, the translated amino acid sequence of Ds-odc has a novel N-terminal primary structure with a repetitive Ala-Ser-rich region of ca 60 amino acid residues in length. Expression of the Ds-odc transcripts suggested a constitutive metabolic role for the corresponding ODC enzyme. According to the results, it is proposed that ODC may have an essential implication for the growth and basic metabolism of wood-decaying fungi.

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White-rot fungi are wood degrading organisms that are able to decompose all wood polymers; lignin, cellulose and hemicellulose. Especially the selective white-rot fungi that decompose preferentially wood lignin are promising for biopulping applications. In biopulping the pretreatment of wood chips with white-rot fungi enhances the subsequent pulping step and substantially reduces the refining energy consumption in mechanical pulping. Because it is not possible to carry out biopulping in industrial scale as a closed process it has been necessary to search for new selective strains of white-rot fungi which naturally occur in Finland and cause selective white-rot of Finnish wood raw-material. In a screening of 300 fungal strains a rare polypore, Physisporinus rivulosus strain T241i isolated from a forest burn research site, was found to be a selective lignin degrader and promising for the use in biopulping. Since selective lignin degradation is apparently essential for biopulping, knowledge on lignin-modifying enzymes and the regulation of their production by a biopulping fungus is needed. White-rot fungal enzymes that participate in lignin degradation are laccase, lignin peroxidase (LiP), manganese peroxidase (MnP), versatile peroxidase (VP) and hydrogen peroxide forming enzymes. In this study, P. rivulosus was observed to produce MnP, laccase and oxalic acid during growth on wood chips. In liquid cultures manganese and veratryl alcohol increased the production of acidic MnP isoforms detected also in wood chip cultures. Laccase production by P. rivulosus was low unless the cultures were supplemented with sawdust and charred wood, the components of natural growth environment of the fungus. In white-rot fungi the lignin-modifying enzymes are typically present as multiple isoforms. In this study, two MnP encoding genes, mnpA and mnpB, were cloned and characterized from P. rivulosus T241i. Analysis of the N-terminal amino acid sequences of two purified MnPs and putative amino acid sequence of the two cloned mnp genes suggested that P. rivulosus possesses at least four mnp genes. The genes mnpA and mnpB markedly differ from each other by the gene length, sequence and intron-exon structure. In addition, their expression is differentially affected by the addition of manganese and veratryl alcohol. P. rivulosus produced laccase as at least two isoforms. The results of this study revealed that the production of MnP and laccase was differentially regulated in P. rivulosus, which ensures the efficient lignin degradation under a variety of environmental conditions.

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There has been increasing interest on various properties and applications of electronically conducting polymers. Polyethylenedioxythiophene (PEDOT) is an interesting polymer of this type as it exhibits very high ionic conductivity. In the present study, PEDOT has been electrochemically deposited on stainless steel (SS) substrate for supercapacitor studies. PEDOT/SS electrodes prepared in 0.1M H2SO4 in presence of a surfactant, sodium dodecylsulphate (SDS), have been found to yield higher specific capacitance (SC) than the electrodes prepared from neutral aqueous electrolyte. The effects of concentration of H(2)SO4(,) concentration of SDS, potential of deposition, and nature of supporting electrolytes used for capacitor studies on SC of the PEDOT/SS electrodes have been studied. SC values as high as 250 F/g in 1M oxalic acid have been obtained during the initial stages of cycling. However, there is a rapid decrease in SC on repeated charge-discharge cycling. Spectroscopic data reflect structural changes in PEDOT on extended cycling. (C) 2007 Wiley Periodicals, Inc.

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The crystal structure of copper ammonium oxalate dihydrate (space group P1̃) has been derived from a refinement of the two-dimensional (hk0) and (0kl) x-ray data using the atomic coordinateis of the isomorphous salt CuK 2(C2O4)2.2H2O as the starting point of the analysis. In contrast to the chromium complexes of oxalic acid the C-C bonds in both the two nonequivalent oxalate ions in the unit cell are single bonds (1.58 and 1.61 Å) consistent with the conclusion of Jeffrey and Parry that the carboxyl groups of the oxalate ion are separated by a pure a bond with little or no π conjugation across the molecule. Both the oxalate ions are slightly nonplanar. The copper ions occupy the special positions (0, 0, 0) and 0, 1/2, 0) and their coordination is of the distorted octahedral type with four nearest oxygen neighbors ( ≃ 2 Å) at the corners of a square and two more distant atoms along the octahedral bond direction. The environment of the NH4+ ions consists of eight nearest oxygen atoms at a mean distance of 3 Å.

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Sparingly soluble neodymium copper oxalate (NCO) single crystals were grown by gel method, by the diffusion of a mixture of neodymium nitrate and cupric nitrate into the set gel containing oxalic acid. Tabular crystal, revealing well-defined dissolution figures has been recorded. X-ray diffraction studies of the powdered sample reveal that NCO is crystalline. Infrared absorption spectrum confirmed the formation of oxalato complex with water of crystallization, while energy dispersive X-ray analysis established the presence of neodymium dominant over copper in the sample. X-ray photoelectron spectroscopic studies established the presence of Nd and Cu in oxide states besides (C2O4)(2-) oxalate group. The intensities of Nd (3d(5/2)) and Cu (2p(3/2)) peaks measured in terms of maximum photoelectron count rates also revealed the presence of Nd in predominance. The inductively coupled plasma analysis supports the EDAX and XPS data by the estimation of neodymium percentage by weight to that of copper present in the NCO sample. On the basis of these findings, an empirical structure for NCO has been proposed. The implications are discussed.

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We report the synthesis of various morphological micro to nano structured zinc oxide crystals via simple precipitation technique. The growth mechanisms of the zinc oxide nanostructures such as snowflake, rose, platelets, porous pyramid and rectangular shapes were studied in detail under various growth conditions. The precursor powders were prepared using several zinc counter ions such as chloride, nitrate and sulphate along with oxalic acid as a precipitating agent. The precursors were decomposed by heating in air resulting in the formation of different shapes of zinc oxide crystals. Variations in ZnO nanostructural shapes were possibly due to the counter ion effect. Sulphate counter ion led to unusual rose-shape morphology. Strong ultrasonic treatment on ZnO rose shows that it was formed by irregular arrangement of micro to nano size hexagonal zinc oxide platelets. The X-ray diffraction studies confirmed the wurzite structure of all zinc oxide samples synthesized using different zinc counter ions. Functional groups of the zinc oxalate precursor and zinc oxide were identified using micro Raman studies. The blue light emission spectra of the various morphologies were recorded using luminescence spectrometer. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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We demonstrate an electrochemical technique for the large scale synthesis of high quality few layer graphene sheets (FLGS) directly from graphite using oxalic acid (a weak acid) as the electrolyte. One of the interesting observations is that the FLGS are stable at least up to 800 degrees C and hence have potential application in solid oxide fuel cells as a gas diffusion layer.

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The combustion of oxidizer zinc nitrate and fuel oxalic acid results in quasi-fibrous zinc oxide. The processing parameters including oxidizer to fuel ratio, time and temperature were optimized for the resultant crystal structure and morphology. Pure hexagonal phase formation does not depend on the fuel ratio, but a stoichiometric ratio of oxidizer to fuel at 450 degrees C and 30 min results in highly crystalline ZnO with 3 mu m length and 0.5 mu m width. This quasi-fiber originates from partial fusion of near spherical, similar to 60 nm particles during the rapid rate of reaction in the combustion process. Transmission electron microscopic analysis confirms the anisotropic primary particle orientation and pore distribution within the developed quasi-fibrous particles. The degradation of methyl orange was assessed by degrading the dye in the presence of the synthesized ZnO (2.95 eV) under both UV and visible light. Quasi-fibrous zinc oxide exhibits effective photocatalytic efficiency under visible light irradiation.

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A modified solution combustion approach was applied in the synthesis of nanosize SrFeO3-delta (SFO) using single as well as mixture of citric acid, oxalic acid, and glycine as fuels with corresponding metal nitrates as precursors. The synthesized and calcined powders were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis and derivative thermogravimetric analysis (TG-DTG), scanning electron microscopy, transmission electron microscopy, N-2 physisorption methods, and acidic strength by n-butyl amine titration methods. The FT-IR spectra show the lower-frequency band at 599 cm(-1) corresponds to metal-oxygen bond (possible Fe-O stretching frequencies) vibrations for the perovskite-structure compound. TG-DTG confirms the formation temperature of SFO ranging between 850-900 degrees C. XRD results reveal that the use of mixture of fuels in the preparation has effect on the crystallite size of the resultant compound. The average particle size of the samples prepared from single fuels as determined from XRD was similar to 50-35 nm, whereas for samples obtained from mixture of fuels, particles with a size of 30-25 nm were obtained. Specifically, the combination of mixture of fuels for the synthesis of SFO catalysts prevents agglomeration of the particles, which in turn leads to decrease in crystallite size and increase in the surface area of the catalysts. It was also observed that the present approach also impacted the catalytic activity of the SFO in the catalytic reduction of nitrobenzene to azoxybenzene.

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Crystals of voriconazole, an antifungal drug, are soft in nature, and this is disadvantageous during compaction studies where pressure is applied on the solid. Crystal engineering is used to make cocrystals and salts with modified mechanical properties (e.g., hardness). Cocrystals with biologically safe coformers such as fumaric acid, 4-hydroxybenzoic acid, and 4-aminobenzoic acid and salts with hydrochloric acid and oxalic acid are prepared through solvent assisted grinding. The presence (salt) or absence (cocrystal) of proton transfer in these multicomponent crystals is unambiguously confirmed with single crystal X-ray diffraction. All the cocrystals have 1:1 stoichiometry, whereas salts exhibit variable stoichiometries such as HCl salt (1:2) and oxalate salts (1:1.5 and 1:1). The nanoindentation technique was applied on single crystals of the salts and cocrystals. The salts exhibit better hardness than the drug and cocrystals in the order salts drug cocrystals. The molecular origin of this mechanical modulation is explained on the basis of slip planes in the crystal structure and relative orientations of the molecules with respect to the nanoindentation direction. The hydrochloride salt is the hardest solid in this family. This may be useful for tableting of the drug during formulation and in drug development.

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In the present study, we have synthesized Fe, Co and Ni doped BaTiO3 catalyst by a wet chemical synthesis method using oxalic acid as a chelating agent. The concentration of the metal dopant varies from 0 to 5 mol% in the catalysts. The physical and chemical properties of doped BaTiO3 catalysts were studied using various analytical methods such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), BET surface area and Transmission electron microscopy (TEM). The acidic strength of the catalysts was measured using a n-butylamine potentiometric titration method. The bulk BaTiO3 catalyst exhibits a tetragonal phase with the P4mm space group. A structural transition from tetrahedral to cubic phase was observed for Fe, Co and Ni doped BaTiO3 catalysts with an increase in doped metal concentration from 1 to 5 mol%. The particle sizes of the catalysts were calculated from TEM images and are in the range of 30-80 nm. All the catalysts were tested for the catalytic reduction of nitrobenzene to azoxybenzene. The BaTiO3 catalyst was found to be highly active and less selective compared to the doped catalysts which are active and highly selective towards azoxybenzene. The increase in selectivity towards azoxybenzene is due to an increase in acidic strength and reduction ability of the doped metal. It was also observed that the nature of the metal dopant and their content at the B-site has an impact on the catalytic reduction of nitrobenzene. The Co doped BaTiO3 catalyst showed better activity with only 0.5 mol% doping than Fe and Ni doped BaTiO3 catalysts with maximum nitrobenzene conversion of 91% with 78% selectivity to azoxybenzene. An optimum Fe loading of 2.5 mol% in BaTiO3 is required to achieve 100% conversion with 93% selectivity whereas Ni with 5 mol% showed a conversion of 93% and a azoxybenzene selectivity of 84%.

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本文以桃(Prunus persica L. cv. Bayuecui.)栽培种‘八月脆’和芒果(Mangifera indica L.)栽培种‘圣心’为材料,研究外源草酸对采后果实的生理生化效应及其作用机理,为果实贮藏保鲜提供新方法。采后桃果实用1、5 mM的草酸溶液浸果10 min,以浸水10 min为对照,然后在常温下贮藏,测定果实在贮藏期间对草酸处理的一些生理生化反应。芒果经采后杀菌剂(post- P)、采后草酸(post-OA)、采前+采后草酸(pre-OA + post-OA)、采前Ca + 采后草酸处理(pre-Ca + post-OA)处理,以采后浸水为对照,然后分别将果实在常温(25 C)、低温(14 C)和控制性气调(3% CO2 + 2% O2 ,14 ± 1 C)下贮藏,测定草酸处理对芒果的成熟进程、病情发展及其相关生理指标的影响。研究结果表明如下: 1.与对照相比,草酸处理的桃果实在贮藏期间果实的电解质渗漏量和呼吸速率降低、果实硬度高、果实的抗氧化酶(超氧化物岐化酶、SOD;过氧化物酶,POD;过氧化氢酶、CAT;抗坏血酸过氧化物酶、APX)和多酚氧化酶(PPO)活性提高、脂氧合酶(LOX)活性降低。同时,在贮藏后期,果实的活性氧自由基(ROS)产量(超氧阴离子、O2.;过氧化氢、H2O2)和丙二醛(MDA)含量降低。草酸的这些生理效应有利于保持膜的完整性和延缓桃果实的成熟;草酸诱导POD、SOD、PPO活性可能有助于提高采后果实的抗病性。 2.外源5、10 mM浓度的草酸(pH值中和或不中和)对芒果炭疽病原菌(Colletotrichum gloeosporioides)孢子萌发和菌丝生长均表现出显著的抑制作用。这种作用不仅与草酸降低培养基(PDA)的pH值相关,而且与草酸独特的化学特性相关。 3.在常温、低温和控制性气调贮藏下,采后草酸、采前 + 采后草酸、采前Ca + 采后草酸处理均能有效减缓芒果果实的软化速率,延缓芒果的成熟进程,降低芒果的病情指数,同时改善芒果成熟时的表皮着色,对果实完全后熟时的可溶性固形物(SSC)、可滴定酸(TA)含量、果肉口感均没有产生负面的影响。 4.草酸处理增强芒果细胞膜的稳定性,诱导提高芒果抗氧化酶活性,特别是提高果皮SOD、APX活性,降低LOX活性,以及降低果皮O2.、H2O2 和果肉H2O2含量,抑制采后果实的乙烯生物合成。这些生理生化效应与延缓芒果的成熟衰老和提高果实的抗病性相关。 5. 采后草酸、采前 + 采后草酸和采前Ca + 采后草酸处理表现出高效低廉、无毒无副作用、易操作等优点,是芒果采后贮藏保鲜的可供选、具有实际应用前景的新方法。

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  果实为开花植物所特有的发育器官,在种子的成熟和传播过程中发挥着重要作用。同时,肉质果实中含有丰富的营养物质,包括纤维素、维生素、抗氧化剂等,成为人们饮食的重要组成部分。由于果实的成熟衰老和抗病性直接影响果品的质量和市场价值,因此,研究果实成熟衰老和抗病性的调控机制具有重要的理论意义和应用前景。本文主要利用蛋白质组学的方法,探讨外源化学物质抑制果实成熟衰老和诱导抗病性的调控机制。 1. 硅对果实的抗病性诱导:用硅酸钠(1%)处理采后的甜樱桃果实,再接种褐腐病原菌(Molinilia fracticola),置于20C下,观测贮藏期间果实的发病率,并分析硅处理后诱导的主要蛋白质及调控机制。研究结果表明:硅酸钠处理可显著抑制贮藏期间褐腐病的发生,其抑病机理与硅诱导PR-蛋白的表达,提高果实的抗氧化水平,减轻由病原菌侵染造成的氧化胁迫相关。同时,硅处理还能保护细胞骨架结构,有利于增强果实对病原菌入侵的抵抗力。 2. 水杨酸对果实的抗病性诱导:用水杨酸(SA,2mM)在果园处理三种成熟度的甜樱桃果实,然后接种青霉病原菌(Penicillium expansum)观察其发病情况,并取样分析参与抗病性应答的主要蛋白质及调控机制。试验结果表明:SA处理能显著降低青霉病的发病率和抑制病斑扩展,而且SA对低成熟度甜樱桃果实的抗性诱导效果更好。在八成熟的果实中,有5个热激蛋白和4个脱氢酶蛋白被SA诱导,这些蛋白参与了糖酵解和三羧酸循环。抗氧化蛋白和PR蛋白主要参与较低成熟度果实的抗性应答,而热激蛋白和脱氢酶在较高成熟度果实的抗性应答中更明显,SA诱导的抗性与代谢途径相关。   3. 草酸对果实的抗性诱导:用5mM的草酸处理冬枣果实后,接种青霉菌(P. expansum),观察果实发病情况,测定果实相关的生理指标,分析参与果实抗性应答的主要蛋白质及调控机制。结果表明:草酸能明显延缓冬枣果实的衰老,提高果实对青霉菌的抗性。草酸处理能抑制果实乙烯的释放量和呼吸强度,延缓叶绿素的降解,减少乙醇积累。利用蛋白质组学的研究方法证实了在25个参与了草酸处理应答的蛋白中,胱硫醚-β-合酶结构域包含蛋白(CBB domain-containing protein)和3个与光合作用相关蛋白[二磷酸核酮糖羧化酶/加氧酶(Ribulose bisphosphate carboxylase/oxygenase activase, chloroplast precursor),二磷酸核酮糖羧化酶/加氧酶大亚基结合蛋白(RuBisCO large subunit-binding protein subunit beta, chloroplast precursor),植物光系统Ⅱ放氧复合蛋白2(PSII oxygen-evolving complex protein 2)]的表达量上调,乙醇脱氢酶的表达量出现下调。草酸处理还提高了与乙烯合成前体相关蛋白的表达,抑制了ACC合成酶的活性。草酸提高果实抗病的机制与延缓果实成熟衰老和保持果实抗性有关。 4. 果实衰老的调控机制:采用高氧(100%)和低氧(2-3%)处理苹果果实,观察果实衰老的进程,并基于蛋白质组学的研究方法,探讨苹果果实衰老与线粒体蛋白质组的关系。结果表明,在苹果衰老过程中有22个蛋白的表达量发生变化,这些蛋白主要参与了三羧酸循环,电子传递,碳代谢和胁迫应答。高氧处理能诱导氧化胁迫,加速了果实的衰老。质谱鉴定结果证明:在高氧胁迫下,超氧化物歧化酶(manganese superoxide dismutase,MnSOD)和线粒体外膜通道蛋白(porin) 的表达量降低,MnSOD的活性受到抑制,由此提高了线粒体中超氧阴离子的含量,增加了蛋白质的氧化损伤。 此外,高氧处理改变了porin的功能,导致了线粒体膜的透势发生变化,从而引起外膜损伤。由此阐明了活性氧在果实的成熟衰老调控中的重要作用。

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This study investigates the ozonation of 17 alpha-ethinylestradiol (EE2) in aqueous solution. The affecting factors on the degradation of EE2 were studied and described in details, such as initial EE2 concentration, initial pH value and ozone concentration. In addition, some parameters such as pH. electrical conductivity, mineralization efficiency and degradation products were monitored during the process. The mineralization efficiency of EE2 could reach 53.9%. During the ozonation process the rapid decrease of pH and the sharp increase of electrical conductivity indicated the fort-nation of acidic by-products, small fragments and ions which were confirmed by high performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GUMS) analysis. Results showed that there were intermediate products of smaller molecule with higher polarity produced during the course of EE2 degradation. Then a possible reaction pathway for EE2 degradation involving all intermediates detected is proposed. During the ozonation process EE2 was first oxidized into hydroxyl-semiquinone isomers which were subsequently degraded into low molecular weight compounds such as oxalic acid, malonate, glutarate, and so on. Furthermore. these organic acids are easily oxidized by ozone into carbon dioxide (CO2). This work shows that ozonation process is promising for the removal of EE2. The results can provide some useful information for the potential treatment of EE2 by ozonation in aqueous solution. (c) 2005 Elsevier B.V. All rights reserved.