Soil Fulvic Acid Degradation By Ozone In Aqueous Medium

Armadale Armadale soil fulvic acid (SFA) was found to contain several loosely bound organic impurities which could be removed by ethyl acetate extraction. The ozonation of purified Armadale SFA at a variety of dosages was characterized by monitoring the UV absorbance, weight loss, pH changes, total acidity, molecular weight and elemental composition. SFA could only be partially degraded even under ozone dosages as high as SFA/O₃ (w/w) of 1:6. At high ozone dosages (SFA/O3 1:6) mostly aliphatic compounds rich in oxygen were produced, whereas at low ozone dosages (SFA/O₃ < 1:0.5) mainly benzene polycarboxylic acids and polyhydroxy benzene polycarboxylic acids were found. The solid material bisolated from the chlorination (0.5 mg/L residual level) of residues from the ozonation (SFA/O₃ 1:0.2 to 1:0.5) of Contech SFA did not contain any chlorinated products.     

Empirically and Theoretically–Based Models for Predicting Brominated Ozonated By–Products

During water treatment, ozonation of waters containing bromide ion producesboth organic and inorganic disinfection byproducts. Bromide ion concentrations in U.S. waters range from 0.01 to 2 mg/L (Krasner, 1989). Bromoformand dibromoacetic acid (DBAA) are the major organic byproducts and bromateion is the major inorganic byproduct derived from ozonation. Bromoform is a known carcinogen and the existence of bromate ion in water supplies also is of public health concern (Lykins, 1986). Bromate ion causes renal failure and hearing loss in laboratory animals and in human beings (Kruithof, 1992). The provisional guideline for bromate ion as proposed by the World Health Organization is 25 pg/L and may be exceeded in water treatment processesusing ozone. Also draft drinking water regulations in the U.S. will specify a maximum contaminant level (MCL) of 10 µg/L for bromate ion and a bestavailable treatment (BAT) of pH adjustment.     

Effect of Micro-Mixing Conditions on Predictions of Cryptosporidium Inactivation in an Ozone Contactor

The U.S. EPA is considering segregated flow analysis as an alternative calculation method to determine Cryptosporidium parvum inactivation credit in continuous-flow ozone contactors in drinking water treatment facilities. A computer method is presented in which C. parvum inactivation in the reactive flow segment of a hypothetical ozone contactor with a pre-determined residence time distribution is calculated based on the assumption of either completely segregated or completely micro-mixed flow. In a series of computer simulations using typical ozonation conditions in a water treatment facility, inactivation predicted assuming complete segregation was 0.3 to more than 2.0 log greater than that predicted assuming complete micro-mixing, depending on the level of back-mixing, ozone decomposition rate and inactivation level. CFSTR-in-series model predictions of inactivation were between those of segregated flow analysis and micro-mixed analysis. It was concluded that segregated flow analysis calculations may result in significant over-prediction of C. parvum inactivation credit in ozone contactors and should be used with caution.     

By-products Formation during the Ozonation of the Reactive Dye Uniblu-A

The degradation by ozone of the hydrolyzed Uniblu-A (Uniblu-OH), i.e. the compound found in the spent bath resulting from dyeing process with the reactive dye Uniblu-A, has been studied with the aim of identifying intermediate as well as end by-products formed. The experimental results, obtained by ozonating (16 mg O₃/L in the feed gas at 100 mL/min) aqueous solutions (500 ml) of Uniblu-OH (40 mg/L), in the presence or not of t-butanol, show that the oxy-dye is completely removed within 30 minutes and that its decay results only slightly affected by the presence of t-butanol. Several organic by-products have been identified by liquid chromatography-mass spectrometry (turboionspray interface) as a result of the oxy-dye degradation. Such by-products result from oxidation of the amino group, hydroxylation of the aromatic rings, cleavage of the alkyl chain, cleavage of the sulfoalkylbenzene group leaving substituted anthraquinone structures and cleavage of the latter structures leading to phthalic acid. Such by-products are further degraded leading to the formation of low molecular weight aldehydes and acids, nitrate and sulphate. As for the formation of inorganic end by-products, after 120 minutes of ozonation, the percentages of nitrate and sulphate conversion resulted 6 and 7 %, 53 and 89% in the absence and in the presence of t-butanol respectively.     

Evaluation of Variations in Ground-Level Ozone (O3) Concentrations

This article presents the results of measuring the concentrations of ground-level ozone (O₃) in ambient air and meteorological parameters (atmospheric pressure, temperature, wind speed, and relative humidity during the year 2008. The measurements were performed at measuring station located near Campo Grande, away from local sources of O₃. Fourier analysis, Principal Component Analysis (PCA) and Multiple Linear Regression (MLR) were used as tools for mathematical analysis of the indicated occurrence. The results of Fourier analysis indicate that not only the daily cycles but also the weekly and monthly cycles are visible in all periods as well as the 12-h cycles. The statistical analysis of the obtained data, based on PCA have shown that approximately 60% of the variance in the measured values can be described with two factors. The attempt of O₃ distribution modeling, using MLRA, resulted in a linear model whose coefficient of determination was equal to R² = 0.98. The results of the study indicate that all these methods are useful for understanding the impact of meteorological parameters on variations of ozone concentration over time.     

Vinyl monomers bearing chromophore moieties and their polymers. VII. Synthesis,photochemical, and initiation behavior of acrylic monomers bearing phenothiazine oxide moieties and their polymers

Four acrylic monomers bearing phenothiazine oxide moieties, that is, N-acryloyl-phenothiazine-5-oxide (APTO), N-acryloyl-2-chlorophenothiazine-5-oxide (ACPTO), N-acryloyl-phenothiazine-5,5-dioxide (APTDO), and N-acryloyl-2-chlorophenothiazine-5,5-dioxide (ACPTDO) were synthesized by oxidation of corresponding N-acryloyl-phenothiazine (APT) and N-acryloyl-2-chlorophenothiazine (ACPT) using sodium perborate as an oxidant. These monomers could easily be polymerized by initiation of AIBN. The emission fluorescence spectra of the monomers and their polymers were recorded, and the results indicated that these 4 new monomers possess a fluorescence structural self-quenching effect (SSQE), as we have reported previously. Moreover, with the change of the electronic structure of sulfur atom in the phenothiazine chromophore, that is, from sulfide to sulfoxide and sulfone groups, the tendency of SSQE of these monomers is in the order of APT > APTO > APTDO. This would be ascribed mainly to the decrease of electron-donating abilities of monomers in a sequence of sulfide, sulfoxide, and sulfone groups; that is, at the sulfur atom of these monomers, APT has 2 lone-pair electrons, APTO has 1 lone-pair electrons, and APTDO completely loses its lone-pair electrons. Based on the exciplex formation, the monomers APTO, APTDO, ACPO, and ACPTDO could act as sensitizers for the photopolymerization of acrylonitrile (AN). The combination of APTO or ACPTO with organic peroxides such as BPO could also initiate the polymerization of vinyl monomers, such as AN, by redox nature. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1191–1199, 1998     

Evaluation Of Genotoxicity Of Bromate Ion Produced During Ozonation

Bromate ion formation during ozonation processes in water works is regarded as an issue of great interest because of its potential for carcinogenicity. In this research, genotoxicity of bromate ion was investigated by the umu-test using Salmonella typhimurium TA 1535/pSK1002. The time-course study showed that the umuC gene related to error-prone repair of damaged DNA was induced by bromate ion after 12 hours exposure of the test strain. However, a further study revealed that this induction was inactivated by metabolism with rat liver microsome when bromate ion concentration was less than 0.88 mg BrO₃ ^?/mg as protein of the S9 fraction. This inactivation was assumed to depend on -SH compounds in liver microsome.     

Electrocatalytic tandem Knoevenagel–Michael addition of barbituric acids to isatins: Facile and efficient way to substituted 5,5′-(2-oxo-2,3-dihydro-1H-indole-3,3-diyl)bis(pyrimidine-2,4,6-(1H,3H,5H)-trione) scaffold

Electrocatalytic transformation of isatins and barbituric acids in ethanol in an undivided cell in the presence of sodium bromide as an electrolyte results in the formation of substituted 5,5′-(2-oxo-2,3-dihydro-1H-indole-3,3-diyl)bis(pyrimidine-2,4,6(1H,3H,5H)-triones) in 89–95% substance yields and 890–950% current yields. The developed efficient electrocatalytic approach to medicinally relevant 5,5′-(2-oxo-2,3-dihydro-1H-indole-3,3-diyl)bis(pyrimidine-2,4,6(1H,3H,5H)-trione) scaffold is 10 times faster than general chemical method, is beneficial from the viewpoint of diversity-oriented large-scale processes and represents novel example of facile environmentally benign synthetic concept for electrocatalytic tandem reaction strategy.     

Study of the Catalytic Ozonation of Humic Substances in Water and Their Ozonation Byproducts

It is shown that using transition metals, especially Mn(II) and Ag(I), during ozonation of humic substances in water allows important reductions in the content of organic matter. Characterization of the organic compounds resulting from ozonation was made by concentrating the sample through liquid-liquid extraction or derivation with PFBOA.HCl, along with the GC/MS and GC/ECD techniques. In total, 110 different organic compounds were identified using GC/MS; mainly carboxylic acids, aromatics, hydrocarbons, aldehydes, ketones, and furan-carboxylic acids. The percentages of elimination or formation levels reached during ozonation are discussed.     

A study on the prediction of ozone formation in air pollution

Two prediction schemes-time series analysis and parameter estimation method-were investigated to predict the formation of ozone in Seoul, Korea. Moving average method and double exponential smoothing method are applied to the time-series analysis. Three typical methods, such as extended least squares (ELS), recursive maximum likelihood (RML) and generalized least squares (GLS), were used to predict ozone formation in a real time parameter estimation. Autoregressive moving average model with external input (ARMAX) is used as the model of the parameter estimation. To test the performance of the ozone formation prediction schemes proposed in the present work, the prediction results of ozone formation were compared to the real data. From the comparison it can be seen that the prediction scheme based on the parameter estimation method gives a reasonable accuracy with limited prediction horizon.     

Incorporation of manganese complexes into xylanase: new artificial metalloenzymes for enantioselective epoxidation

Here we report the best artificial metalloenzyme to date for the selective oxidation of aromatic alkenes; it was obtained by noncovalent insertion of Mn^III‐meso‐tetrakis(p‐carboxyphenyl)porphyrin [Mn(TpCPP), 1 ‐Mn] into a host protein, xylanase 10A from Streptomyces lividans (Xln10A). Two metallic complexes—N,N′‐ethylene bis(2‐hydroxybenzylimine)‐5,5′‐dicarboxylic acid Mn^III [(Mn‐salen), 2 ‐Mn] and 1 ‐Mn—were associated with Xln10A, and the two hybrid biocatalysts were characterised by UV–visible spectroscopy, circular dichroism and molecular modelling. Only the artificial metalloenzyme based on 1 ‐Mn and Xln10A was studied for its catalytic properties in the oxidation of various substituted styrene derivatives by KHSO₅: after optimisation, the 1 ‐Mn ‐ Xln10A artificial metalloenzyme was able to catalyse the oxidation of para‐methoxystyrene by KHSO₅ with a 16 % yield and the best enantioselectivity (80 % in favour of the R isomer) ever reported for an artificial metalloenzyme.     

Guideline for Measurement of Ozone Concentration in the Process Gas From an Ozone Generator

A joint meeting of members of the Quality Assurance Committees of the International Ozone Association Pan American Group (PAG), European-African Group (EAG), and Nippon Islands Group (NIG) was held in Oxford, Ohio on November 8 and 9, 1995. The purpose of the meeting was to establish a single, shared guideline for ozone concentration measurement in the gas phase and, in particular, from commercial ozone generators.     

Practical suggestions for meeting USEPA compliance monitoring requirements and in‐plant operational control of chlorine dioxide in drinking water.

An overview of current US Environmental Protection Agency (EPA) compliance objectives in the use and control of chlorine dioxide (ClO₂) in public drinking water treatment will be presented. Although these objectives were proposed in the 1994 Disinfectants/Disinfection Byproducts Rule (D/DBP), simple modifications to the frequency and approved list of analytical methods in the final Rule will greatly enhance public health protection afforded by operators at water treatment plants.

Ongoing concerns of acute health risks are associated with overexposure to ClO₂ or its principal DBP, the chlorite ion. Water leaving the plant needs to be monitored for both compounds on a daily basis using either approved or newly‐devised, more accurate methods such as Lissamine Green B. Monthly determinations for chlorite and chlorate ion species, using approved ion chromatography (EPA method 300.0 or 300.1), must also be carried out on samples from 3 locations in the distribution system. Lack of control of the generation process can influence purity of the ClO₂, possibly leading to elevated levels of undesirable byproducts associated with its use. Notable organoleptic episodes of peculiar and unusually obnoxious character may result from such high levels in finished waters. Specific examples of simplified testing methods and suggestions for operator and process control are outlined. Operational steps may be taken that ensure accurate ClO₂ feed control, equipment reliability and simple assessment of finished water for residual oxidants. Such operator‐based practices can be easily established on a day‐to‐day basis. These practices compliment the recent USEPA D/DBP Stage 1 final compliance monitoring schedules, provide adequate in‐plant operator control of chemical feed, and can lead to avoidance of severe public notification required by USEPA in the event of non‐compliance.     

—Review Paper—Application Of Ozone for Treatment of Swimming Pool Water in the Federal Republic of Germany

In the fields of application of ozone plants produced by the German ozone industry, the treatment of pool water is foremost. Especially the precursors of the chlorine-nitrogen compounds (combined chlorine) and the chlorine-carbon compounds (haloforms) which, for reasons of health, are reckoned among the undesirable substances in pool water, can be considerably reduced through the use of ozone during pool water treatment. The efficiency of the treatment processes depends substantially on the reaction period of the ozone with the pool water contaminants, as is shown by tests with new processes having long ozone contact periods.     

Synthesis,properties and pyrolysis of siloxane‐ and imide‐modified epoxy resin cured with siloxane‐containing dianhydride

Hydrosilylation of nadic anhydride with tetramethyl disiloxane yielded 5,5′‐(1,1,3,3‐tetramethyl disiloxane‐1,3‐diyl)‐bis‐norborane‐2,3‐dicarboxylic anhydride (I), which further reacted with 4‐aminophenol to give N,N′‐bis(4‐hydroxyphenyl)‐5,5′‐bis‐(1,1,3,3‐tetramethyl disiloxane‐1,3‐diyl)‐bis‐norborane‐2,3‐dicarboximide (II). Epoxidation of II with excess epichlorohydrin formed a siloxane‐ and imide‐modified epoxy oligomer (ie diglycidyl ether of N,N′‐bis(4‐hydroxyphenyl)‐5,5′‐bis(1,1,3,3‐tetramethyl disiloxane‐1,3‐diyl)‐bis‐norborane‐2,3‐dicarboximide) (III). Equivalent ratios of III/I of 1/1 and 1/0.8 were prepared and cured to produce crosslinked materials. Thermal mechanical and dynamic mechanical properties were investigated by TMA and DMA, respectively. It was noted that each of these two materials showed a glass transition temperature (T_g) higher than 160 °C with moderate moduli. The thermal degradation kinetics was studied with dynamic thermogravimetric analysis (TGA) and the estimated apparent activation energies were 111.4 kJ mol^?1 (in N₂), 117.1 kJ mol^?1 (in air) for III/I = 1/0.8, and 149.2 kJ mol^?1 (in N₂), 147.6 kJ mol^?1 (in air) for III/I = 1/1. The white flaky residue of the TGA char was confirmed to be silicon dioxide, which formed a barrier at the surface of the polymer matrix and, in part, accounted for the unique heat resistance of this material. Copyright © 2005 Society of Chemical Industry     

Synthesis of novel phosphorous‐containing biphenol, 2‐(5, 5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorin‐6‐yl)‐1,4‐benzenediol and its application as flame‐retardant in epoxy resin

A novel phosphorous‐containing biphenol, 2‐(5,5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorin‐6‐yl)‐ 1,4‐benzenediol (DPODB), was prepared by the addition reaction between 5,5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorinane phosphonate (DPODP) and p‐benzoquinone (BQ). The compound (DPODB) was used as a reactive flame retardant in o‐cresol formaldehyde novolac epoxy resin (CNE) for electronic application. The structure of DPODB was confirmed by FTIR and NMR spectra. Thermal properties of cured epoxy resin were studied using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The flame retardancy of cured epoxy resins was tested by UL‐94 vertical test and achieved UL‐94 vertical tests of V‐0 grade (nonflammable). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3842–3847, 2006     

Energy conversion and temperature dependence in ozone generator fed by synthetic air

A homogenous chemical kinetic model consisting of 21 species and 118 reactions is applied to investigate energy conversion and its temperature dependence in ozone generator fed by synthetic air. The portion of electric energy converted into reaction heat, gas heating and heat loss to surroundings (by convection) in terms of the total electric energy input, the conversion ratios η_reaction, η_gas, and η_loss, are obtained. The detailed reaction pathway including the degree of transformation among species for ozone production is also obtained via simulation of the reaction kinetics. In addition, sensitivity analysis and rate-of-production analysis for the three foremost species O₃, O, and N₂(A) are performed to understand quantitatively the temperature dependence of sensitivity coefficient and production rate for each individual reaction. η_reaction shows a steep rise at low specific energy, but then suffers a gradual decrease at high specific energy. η_loss has a contrary behavior. And η_gas increases steadily with the increase of specific energy. The η_reaction peak of 35.1% is achieved at specific energy of 0.17 J/cm³ at the conditions under investigation. Additionally, inlet gas temperature only has a small effect on energy conversion. Moreover, high gas temperature in discharge gap is confirmed to be not favorable for ozone formation from the view of reaction heat. The sensitivity coefficients of reactions with electron participation are sensitive to gas temperature. O+O₂+O₂→O₂+O₃ and O+O₂+N₂→N₂+O₃ account for about 70% and 30% of generated ozone respectively at the given conditions. And e+O₂→e+O+O, N₂(A)+O₂→N₂O+O, and N₂(A)+O₂→O+O+N₂ are responsible for about 51.3%, 14.7%, and 32.0% of oxygen atom, respectively.     

The Use of an Unusual Rearrangement Sequence for the Syntheses of 3‐(1‐Aminoalkylidene)‐3H‐thiophen‐2‐ones and two Examples of their Surprising Electrophilic‐Induced Dimerization Reactions

The reaction of 2‐amino‐3‐carbomethoxythiophene ( 1a ) and 2‐amino‐3‐carboethoxy‐4,5‐dimethylthiophene ( 1b ) with methyl‐ or ethylmagnesium chloride leads to new 3‐(1‐aminoalkylidene)‐3H‐thiophen‐2‐ones 4a—d in good yields (60—87%). Treatment of the compounds 4a and 4c with catalytic amounts of p‐TsOH in boiling CHCl₃ afforded the (±)‐4,4′‐bis‐(1‐aminoalkylidene)‐3′,4′‐4H,2′H‐[2,3′]bithiophenyl‐5,5′‐diones 9a and 9b as new interesting heterocycles in preparatively useful yields (60/mdash;65%).     

Quantification of the Bactericidal,Fungicidal, and Sporicidal Efficacy of the JLA Ltd. Ozone Laundering System

The objective of this study was to demonstrate the bactericidal, fungicidal, and sporicidal efficacy of the in-use concentration of ozone in solution generated continuously by the JLA Limited OTEX validated ozone laundering system against a range of typical microorganisms associated with laundering applications. The study used the JLA HC 100 laundering machine as the containment vessel. Test microbial suspensions were introduced directly into the drum of the laundering machine containing a known level of water in the presence of soluble ozone. Using standard microbiological techniques, the numbers of surviving bacteria, mold spores or bacterial spores were determined, and reductions in viable counts were calculated. The following test organisms were employed: Pseudomonas aeruginosa, Methicillin-Resistant Staphylococcus aureus (MRSA), Enterococcus faecalis, E. coli, Acinetobacter baumannii, Aspergillus niger (spores), and Clostridium difficile (spores). All tests used multiple contact times of 0, 1, 3, 5, 7, 11 and 15 minutes at 20 °C±2 °C. Levels of ≤0.25 mg/L of dissolved ozone had minimal effect on the bacteria. Levels of >0.45 mg/L ozone showed good biocidal activity, except against Acinetobacter baumannii, which showed strong resistance to ozone. Against fungal spores, dissolved ozone levels of >1.2 mg/L were required to obtain a 2.8 log reduction. For Clostridium difficile spores, a dissolved ozone level between 0.90 and 1.20 mg/L gave >1.6 log reduction with no discernable spore recovery. In every instance, the control tests (no ozone) recovered levels of microorganisms that proved that the action of the laundering machine has no antimicrobial activity, and that the log reductions obtained are solely due to the effects of dissolved ozone.     

The “Big Switch”: Los Angeles Aqueduct Filtration Plant Treatment Of California State Project Water

Plant-scale tests were run in October 1987 and October 1988 to evaluate the ability of the 26.3-m³/s (600-mgd) Los Angeles Aqueduct Filtration Plant (LAAFP) to treat one of the source waters -- California State project water (SPW) -- used by the Metropolitan Water District of Southern California and to determine CT^a values for its ozone contact basins. During the test period, a large amount of water quality and operating data was collected, providing insight into the effectiveness of the preozonation/direct filtration process (followed by chlorination or chloramination) on SPW. This paper describes the results of the full-scale testing.