Production of Laccase from Coriolus versicolor and Its Application in Dye Decolorization in Combination with UV/H2O2 Technique

The relative ability of Coriolus versicolor to grow on coir fiber as a ligninocellulosic material was examined. Addition of yeast extract to the culture increased laccase activity, which was further enhanced to the level of 1976 U/L by addition of 1 mM copper sulfate. Laccase thus produced was used without further purification for the decolorization of various dye solutions. Decolorization efficiency was compared with the conventional environment friendly oxidation technique using hydrogen peroxide in the presence of UV radiations. Laccase showed good decolorization in most of the cases. Excellent results were achieved when the dye solution was treated successively with laccase and UV/H₂O₂ wherein more than 80% decolorization was achieved. This value is remarkably higher than that attained either by the enzyme or UV/H₂O₂ photolysis alone.     

Influence of Oxidative Treatment on the AOX‐formation Potential of Aromatic Sulfonates

Aromatic sulfonates can be found in drinking water. Thus, they must have passed water treatment and survived ozonation. Degradation of aromatic sulfonates can be achieved by the UV/H2O2‐process. Since drinking water is often treated with chlorine as a disinfectant, the formation of disinfection by‐products has to be considered. Therefore, the production of AOX (on activated carbon adsorbable organic halogens) after chlorination of the sulfonates with and without preoxidation was investigated. Instead of the analysis of the individual degradation products, the determination of the sum parameter AOX was used as a fast screening method. The investigated sulfonates were: anthraquinone‐2‐sulfonate, naphthalene‐2‐sulfonate, 2‐aminonaphthalene‐1‐sulfonate, and 4,4′‐diaminostilbene‐2,2′‐disulfonate. All sulfonates containing amino groups showed high potentials of AOX formation. The preoxidation with ozone increased the potentials of AOX formation in general. Treating the sulfonates by using the UV/H2O2‐process, the formation potentials run to zero after going through a maximum value.     

Solar UV variability: Effects on stratospheric ozone,trace constituents and thermal structure

The effect of long-term (11-year solar cycle) solar UV variability on stratospheric chemical and thermal structure has been studied using a time-dependent one-dimensional model. Previous studies have suggested substantial variations in local and total ozone, and in stratospheric thermal structure from solar minimum to solar maximum. It is shown here that significant variations also occur in some of the trace constituents. Members of the HO _x family and N₂O exhibit the largest variations, and these changes, if detected, may provide additional means of verifying the presence of solar UV variability and its effects. Some of the species show large phase differences with the assumed solar flux variation. The role of chemical and transport time constants on the time variations of the trace species is examined. Comparisons with reported ozone and temperature data show reasonable agreement for the period 1960 to 1972.     

Association of Humic Substances: Verification of Lambert‐Beer Law

The precision UV/Vis‐absorption spectra of a naturally occurring aquatic humic substance were measured in the range of concentration 0.003 to 1.4 g/L DOC (dissolved organic carbon). Lambert‐Beer law is well obeyed at low concentrations whereas deviations have been observed for DOC concentrations above 0.1 g/L: they are interpreted in terms of self‐solvation and formation of micelles.     

Degradation of Aqueous Atrazine and Metazachlor Solutions by UV and UV/H2O2 — Influence of pH and Herbicide Concentration Abbau von Atrazin und Metazachlor in wäßriger Lösung durch UV und UV/H2O2 — Einfluß von pH und Herbizid-Konzentration

The degradation of two pesticides: atrazine and metazachlor was investigated in aqueous solution under UV-irradiation with and without H₂O₂. Rate constants of the photochemical degradation were determined applying a first order kinetics and quantum yields of the processes were calculated. This approach leads to an apparent decrease of the quantum yield with increasing initial pesticide concentration. At low H₂O₂ initial concentrations, the pesticide degradation was shown to be much more efficient than the degradation under UV-irradiation only. However, at high H₂O₂ concentrations (>2 mmol L^?1), the efficiency of the UV/H₂O₂ system dropped down and the quantum yields of degradation were lower than for the direct photolysis. In the absence of H₂O₂, no influence of the pH value on the photodegradation of the pesticides could be noticed in a range between pH 3 and pH 11. At low H₂O₂ initial concentrations, the photochemical degradation of the pesticides was much faster at pH 3 and pH 7 compared with the degradation at pH 11. The results emphasize the potential of optimized reaction conditions in advanced oxidation.     

Degradation Pathway of the Photochemical Oxidation of Ethylenediaminetetraacetate (EDTA) in the UV/H2O2-process

The degradation pathway for the oxidation of EDTA in the UV/H₂O₂-process was investigated. In absence of iron ions, the mineralization of EDTA is dominated by the reaction of the HO-radicals generated by the photolysis of H₂O₂. The organic degradation products iminodiacetate (IMDA), glycinate, oxamate, glyoxylate, oxalate and formate, and the inorganic degradation products carbon dioxide, ammonia, nitrate, nitrite, and cyanate were found. In the presence of iron ions, photolytic decarboxylation processes inside the complex get an important role during degradation, and the organic degradation products ethylenediaminetriacetate (ED3A), ethylenediaminediacetate (EDDA), ethylenediaminemonoacetate (EDMA) were also found. By combining product studies with balances of carbon and nitrogen, the degradation pathway in the UV/H₂O₂-process could be elucidated. The degradation of EDTA was fast (k_deg = 0.012 s^–1), and no toxic degradation products were identified. Therefore, the process is well suited for the elimination of EDTA in water treatment.     

On the use of UV spectrophotometry to assess dissolved organic carbon origin variations in the Upper Rhône River

To detect temporal changes and the origin of the refractory dissolved organic matter in the Upper Rhône River, UV light absorbance (A) at 285 nm and quantitative dissolved organic carbon (DOC) measurements were carried out. Data from 63 visits to the main channel over a period of two years and from visits to different waterbodies in the alluvial plain before and after a flood are presented. There was a good correlation between A (0.019–0.160) and the DOC content (1.40–9.81 mg/L) for the waterbodies, but not for the river axis with lower A (0.013–0.044) and DOC content (1.13–2.20 mg/L). Due to this good correlation, the DOC content could be quantified for the waterbodies by absorbance measurements only. For the river water this indirect determination of the DOC content was not possible. However, the A/DOC ratio showed changes in the composition of DOC of river water and provided indications about the origin of the dissolved organic matter in the Upper Rhône River.     

Performance of A Combination Process of UV/H2O2/Micro‐Aeration for Oxidation of Dichloroacetic Acid in Drinking Water

The decomposition of dichloroacetic acid (DCAA) in water using a UV/H₂O₂/micro‐aeration process was investigated in this paper. DCAA cannot be removed by UV radiation, H₂O₂ oxidation or micro‐aeration alone, while UV/H₂O₂/micro‐aeration combination processes have proved effective and can degrade this compound completely. With initial concentrations of about 110 μg/L, more than 95.1% of DCAA can be removed in 180 min under UV intensity of 1048.7 μW/cm², H₂O₂ dosage of 30 mg/L and micro‐aeration flow rate of 2 L/min. However, more than 30 μg/L of DCAA was left after 180 min by UV/H₂O₂ combination process without micro‐aeration with the same UV intensity and H₂O₂ dosage. The effects of applied UV radiation intensity, H₂O₂ dose, initial DCAA concentration and pH on the degradation of DCAA have been examined in this study. Degradation mechanisms of DCAA with hydroxyl radical oxidation have been discussed. The removal rate of DCAA was sensitive to operational parameters. There was a linear relationship between rate constant k and UV intensity and initial H₂O₂ concentration, which indicated that a higher removal capacity can be achieved by improvement of both factors. A newly found nitrogenous disinfection by‐product (N‐DBP)‐DCAcAm, which has the potential to form DCAA, was easier to remove than DCAA by UV/H₂O₂ and UV/H₂O₂/micro‐aeration processes. Finally, a preliminary cost comparison revealed that the UV/H₂O₂/micro‐aeration process was more cost‐effective than the UV/H₂O₂ process in the removal of DCAA from drinking water.     

Alkaline Degradation of Dissolved Organic Matter

The degradation of dissolved organic matter (DOM) was studied in alkaline solution. The products were characterised using UV/vis spectroscopy, size‐exclusion chromatography (SEC), and by the analysis of low‐molecular‐weight organic acids (LMWOA). The degradation experiments were performed with water from a brown water lake or its isolated fulvic acid fraction and sodium hydroxide at different reaction times and temperatures. Depending on the wavelength and the reaction time, the UV/vis absorbance between 230 nm and 600 nm increased or decreased. The behaviour of model compounds during reactions in alkaline media was compared to the UV/vis spectroscopic behaviour of DOM. The release of LMWOA was described by kinetic data and compared to the data of model reactions. Evidence was given for the carboxylic esters playing a significant role in the release of LMWOA only during the beginning of the alkaline degradation. The results gained by SEC with on‐line UV and DOC detection showed that the average size of DOM was decreasing, and that a major part of the degradation products consisted of low‐molecular‐weight mono‐ and dicarboxylic acids.     

Treatment of Refractory Organics Contained in Actual Agro‐Industrial Wastewaters by UV/H2O2

In this work, the treatment of actual agro‐industrial wastewaters (IWW) by a UV/H₂O₂ process has been investigated. The aqueous wastes were received from industrial olive oil mills and then treated by laboratory scale physicochemical methods, i. e., coagulation using ferrous and aluminum sulfate, decantation, filtration and adsorption on activated carbon. These wastes are brown colored effluents and have a residual chemical oxygen demand (COD) in the range of 1800 to 3500 mgO₂ L^–1, which cannot be further eliminated with physicochemical processes. The UV/H₂O₂ treatments were carried out under monochromatic irradiation at 254 nm using a thermostated reactor equipped with a mercury vapor lamp located in an axial position. The effects of initial H₂O₂ concentration, initial COD, pH and temperature have been studied in order to determine the optimum conditions for maximum color and COD removals. The experimental results reveal the suitability of the UV/H₂O₂ process for both removal of high levels of COD and effectively decolorizing the solution. In particular, 95% of color removal and 90% of COD removal were obtained under conditions of pH = 5 and 32°C using 2.75 g H₂O₂ g^–1 COD L^–1 during 6 h of UV‐irradiation. The treatment is unaffected by pH over the range 2 to 9. In addition, the COD removal is improved by increasing the temperature, whereas the color removal has not been affected by this parameter. The results show that the hydroxyl radicals generated from the catalytic decomposition of H₂O₂ by UV‐irradiation of the solution could be successfully used to mineralize the organics contained in IWW. The mineralization of the organics seems to occur in three main sequential steps: the first is the rapid decomposition of tannins leading to aromatic compounds, which are confirmed by the decolorization of the IWW; the second step corresponds to the oxidation of aromatics leading to aliphatic intermediates, which occurs by the cleavage of an aromatic ring, and is established by the removal of aromatics, and the final step is the slow oxidation of the aliphatic intermediates, which is measured by the COD removal.     

Degradation of Monoazo Pigments Red 53:1 and Red 48:2 by Fenton,Photo‐Fenton and UV/Peroxide Reactions

The degradation reactions of two monoazo pigments, namely, Red 53:1 and Red 48:2, by Fenton, photo‐Fenton and UV/H₂O₂ systems have been studied. The efficiencies of the Fenton reactions increased with temperature, but the formation of solid agglomerates was observed when the reactions were carried out above 50°C indicating a coagulant action of Fe⁺² or Fe⁺³. Photo‐Fenton reactions irradiated by sunlight presented the best rate constants for cleavage of the azo bond and the naphthalene rings. The UV/H₂O₂ system exhibited the highest efficiency with respect to the consumption of H₂O₂. The presence of a carbonyl group in the ortho position of the naphthol ring hampered the oxidation of pigment Red 48:2 by hydroxyl radicals. This finding may be explained in terms of the acceptor character of the COOH group, and suggests the formation of a complex containing two six‐membered rings between Fe⁺³ and the pigment molecule.     

Photochemical Degradation of Hydrophilic Xenobiotics in the UV/H2O2-process. Influence of Bicarbonate on the Degradation Rate of EDTA, 2-Amino-1-naphthalenesulfonate,Diphenyl-4-sulfonate,and 4,4′-Diaminostilbene-2,2′-disulfonate

Hydrophilic xenobiotics can be eliminated in the UV/H₂O₂-process. The oxidation in this process is enhanced by the photolytically generated HO radicals. Bicarbonate is able to scavenge HO radicals. So it was expected that the degradation rates of the investigated xenobiotics were affected by the influence of bicarbonate. In contrast to the widely described decrease of the degradation rate, a much more complex situation was found in this investigation. The degradation rates of 2-amino-1-naphthalenesulfonate and diphenyl-4-sulfonate were decreased and reached for high concentrations of bicarbonate the values of the photolytical degradation rate. The degradation of 4,4′-diaminostilbene-2,2′-disulfonate was accelerated significantly in the presence of bicarbonate. The degradation rate of EDTA was increased at small concentrations of bicarbonate and decreased at higher concentrations.     

Degradation of organic matter from wastewater using advanced primary treatment by O3 and O3/UV in a pilot plant

The oxidation of organic matter from wastewater using ozone, ultraviolet radiation and ozone/UV oxidation was evaluated in a pilot plant, applying a continuous effluent arising from the Autonomous Metropolitan University wastewater treatment plant. The oxidation was measured as the efficiency to remove organic load, measured as chemical oxygen demand. The use of ozone and UV was evaluated separately and in combination through a continuous process. Three different ozone doses (0.6–1.2 mg O₃/L) and three different UV radiation fluencies (6.7–20.12 mJ/cm²) were assessed. A synergistic effect of the combined process ozone/UV was demonstrated, and a maximal chemical oxygen demand reduction was achieved both processes. Due to residence times used (less than 1 min), 36% of chemical oxygen demand reduction was obtained when ozone treatment was evaluate separately and only 9% using ultraviolet radiation.     

SSBUV and NOAA-11 SBUV/2 Solar Variability Measurements

The Shuttle SBUV (SSBUV) and NOAA-11 SBUV/2 instruments measured solar spectral UV irradiance during the maximum and declining phase of solar cycle 22. The SSBUV data accurately represent the absolute solar UV irradiance between 200–405 nm, and also show the long-term variations during eight flights between October 1989 and January 1996. These data have been used to correct long-term sensitivity changes in the NOAA-11 SBUV/2 data, which provide a near-daily record of solar UV variations over the 170–400 nm region between December 1988 and October 1994. The NOAA-11 data demonstrate the evolution of short-term solar UV activity during solar cycle 22.     

淡水中对紫外光敏感的磷化合物研究简述

湖泊、沼泽与河流等淡水生态系统中在的一些对紫外光敏感的磷化合物,它们在紫外光（或太阳光）的作用下释放正磷酸根。本文对其形成释放机制、生态学意义以及铁和腐殖质的调节作用等作了扼要的综述。     

Photochemical Degradation of Hydrophilic Xenobiotics in the UV/H2O2-process. Influence of Humic Matter on the Degradation Rate of 2-Amino-1-naphthalenesulfonate and Ethylenediaminetetraacetate

Photochemical oxidation methods are able to eliminate hydrophilic xenobiotics with a high efficiency. In waters with high DOC values caused by humic substances (HS) which are able to absorb UV light, problems can result. The degradation rates of the micropollutants using irradiation wavelengths in the range between λ = 200 nm to λ = 260 nm are significantly influenced by HS. This is mainly caused by the high absorption of the HS at shorter wavelength. In the presence of HS, the photolytic degradation of EDTA and FeEDTA was slowed down by an inner filter effect. A similar tendency could be seen for the photolytic degradation of 2-amino-1-naphthalenesulfonate where additional effects to the inner filter effect were also operating. In the UV/H₂O₂-process, the decrease of the degradation rate could be assigned to the ability of the HS to scavenge HO radicals.