Ozone Degradation by Fluoride onto Plasma-Treated Activated Carbon in CF4

The ozone degradation of fluorine was investigated using the tetrafluoromethane plasma-treated activated carbon (PT-AC). The ozone in the stratosphere has been degraded by the chloride and bromide radicals which are produced from chlorofluorocarbons and bromofluorocarbons, respectively. However, we believe that fluorine also was related to the ozone degradation. The fluoride was introduced onto the activated carbon surface by tetrafluoromethane plasma treatment. The breakthrough curve of ozone onto PT-AC was measured to elucidate the relationship between the ozone and the fluoride. The amount of ozone adsorbed/degraded onto the PT-AC was larger than the amount that was adsorbed/degraded onto the untreated activated carbon. The amount of fluoride ion eluted from the PT-AC before the adsorption/degradation of ozone was larger than that which eluted after the adsorption/degradation of ozone. These results indicated that the ozone was degraded by the fluoride on the PT-AC surface.     

Inactivation of Photosensitizing Merocyanine Dyes by Plasma, Serum and Serum Components

Abstract— Merocyanine dyes with an oxygen in the electron donor heterocycle were rapidly degraded by plasma, serum and serum components. Replacement of the oxygen by a sulfur or selenium atom rendered the dyes refractory to degradation. The degradation of labile merocyanine dyes was temperature dependent and oxygen independent. The plasma component that was responsible for the degradation of merocyanine dyes was sensitive to heat and detergent, suggesting an enzymatic process. The identification of the structural requirements for sensitivity/resistance to degradation provides the experimenter with a simple means to manipulate the stability of mer-ocyanines in high serum or plasma environments and may expand the clinical utility of merocyanine photosen-sitizers beyond their traditional role in the extracorporeal purging of bone marrow grafts.     

Photofading of ballpoint dyes studied on paper by LDI and MALDI MS

The determination of the age of an ink entry from a questioned document is often a major problem and a controversial issue in forensic sciences. Therefore, it is important to understand the aging process of the different components found in ink. The aim of this work is to characterize the degradation processes of methyl violet and ethyl violet, two typical ballpoint dyes by using laser desorption/ionization (LDI) and matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS), and to evaluate the possible application of the method to forensic examination of documents. The mass spectrometric methods were first tested and were found to be adequate for the purpose of this work. Moreover, it is possible to analyze the dye from a stroke directly from the paper (LDI-MS), so the sample preparation is minimized. The degradation of the dyes methyl violet and ethyl violet in strokes from a ballpoint pen was studied under laboratory conditions influenced by different factors such as light, wavelength of light, heat, and humidity. Then, strokes from the same ballpoint were aged naturally in the dark or under the influence of light over one year and then analyzed. The results show that the degradation of these dyes strongly depends on light fluence. Humidity also increases degradation, which can be explained by the basicity of the paper. The influence of heat on the degradation process was found to be rather weak. It was also observed that the dyes from the ink strokes did not show significant degradation after one year of storage in the dark. In conclusion, the storage conditions of a questioned document and the initial composition of the dyes in the ink have to be known for correct interpretation of the age of an ink entry. Measurements over longer periods of time are necessary to follow the degradation of dyes exempt from light exposure. LDI was found adequate and very useful for the analysis of ballpoint dyes directly from paper without further pretreatment.     

Surface Modification of (001) Facets Dominated TiO2 with Ozone for Adsorption and Photocatalytic Degradation of Gaseous Toluene

This study investigated the positive effect of surface modification with ozone on the photocatalytic performance of anatase TiO₂ with dominated (001) facets for toluene degradation. The performance of photocatalyst was tested on a home-made volatile organic compounds degradation system. The ozone modi cation, toluene adsorption and degradation mechanism were established by a combination of various characterization methods, in situ diffuse reflectance infrared fourier transform spectroscopy, and density functional theory calculation. The surface modi cation with ozone can significantly enhance the photocatalytic degradation performance for toluene. The abundant unsaturated coordinated 5c-Ti sites on (001) facets act as the adsorption sites for ozone. The formed Ti-O bonds reacted with H₂O to generate a large amount of isolated Ti_5c-OH which act as the adsorption sites for toluene, and thus significantly increase the adsorption capacity for toluene. The outstanding photocatalytic performance of ozone-modified TiO₂ is due to its high adsorption ability for toluene and the abundant surface hydroxyl groups, which produce very reactive OH radicals under irradiation. Furthermore, the O₂ generated via ozone dissociation could combine with the photogenerated electrons to form superoxide radicals which are also conductive to the toluene degradation.     

Mechanism of TiO2-assisted photocatalytic degradation of dyes under visible irradiation: photoelectrocatalytic study by TiO2-film electrodes

Photoelectrocatalytic degradation of various dyes under visible light irradiation with a TiO(2) nanoparticles electrode has been investigated to reveal the mechanism for TiO(2)-assisted photocatalytic degradation of dyes. The degradation of both cationic and anionic dyes at different biases, including the change in the degradation rate of the dyes and the photocurrent change with the bias potential, the degraded intermediates, the voltage-induced adsorption of dyes, the accumulation of electrons in the TiO(2) electrode, the effect of various additives such as benzoquinone (BQ) and N,N-dimethyl aniline (DMA), and the formation of active oxygen species such as O(2)(*-) and H(2)O(2) were examined by UV-visible spectroscopy, HPLC, TOC, and spin-trap ESR spectrometry. It was found that the dyes could controllably interact with the TiO(2) surface by external bias changes and charging of dyes. The cationic dyes such as RhB and MG underwent efficient mineralization at negative bias, but the N-dealkylation process predominated at positive bias under visible light irradiation. The discolorations of the anionic dyes SRB and AR could not be accelerated significantly at either negative or positive bias. At a negative bias of -0.6 V vs SCE, O(2)(*-) and dye(*+) were formed simultaneously at the electrode/electrolyte interface during degradation of cationic RhB. In the case of anionic dyes, however, it is impossible for the O(2)(*-) and dye cationic radical to coexist at the electrode/electrolyte surface. Experimental results imply both the superoxide anionic radical and the dye cationic radical are essential to the mineralization of the dyes under visible light-induced photocatalytic conditions.     

Vibrational spectroscopy to study degradation of natural dyes. Assessment of oxygen-free cassette for safe exposition of artefacts

An important issue connected with conservation chemistry is how to improve the storage and exposure conditions in order to suppress the fading and degradation of dyes and other components of paintings. Although the oxygen-free exposure cassettes are commonly known in museums, there is still lack of information in the literature about the effect of anoxic conditions on the degradation of dyes. This study is an attempt to start a database formation on the dyes degradation. Five commercial dyes (indigo, dragon’s blood, curcumin, madder, carminic acid) were submitted to accelerated ageing by exposure to intensive light in the visible range in both oxygen-free (anoxia) and -rich conditions. Degradation of the samples was investigated by several analytical techniques (attenuated total reflectance infrared spectroscopy, Raman spectroscopy, reflectance UV–Vis spectroscopy, X-ray fluorescence spectroscopy and optical microscopy). The conclusions are based on the estimators (derived from the determination of colour differences from Vis spectra and from the changes in FTIR and Raman vibrational bands intensity). According to them, only indigo, dragon’s blood and curcumin show greater stability in anoxic conditions in comparison with oxygen-rich ones while madder, carminic acid undergo greater degradation.     

Kinetic relationships and mechanism of ozone reaction with polystyrene in CCl4 solution

In this work a study is made of the degradation on ozonation of unfractionated polystyrene (PS) in CCl₄ solution. It was found that the ozone attack of PS molecules is accompanied by hydrogen abstraction from tertiary CH bonds and by the formation of ozonides due to the reaction of ozone with the aromatic rings. A scheme of PS degradation in solution is suggested; several kinetic parameters are evaluated.     

Application of Dielectric Barrier Discharge Reactor Immersed in Wastewater to the Oxidative Degradation of Organic Contaminant

Dielectric barrier discharge (DBD) is an effective method available for the production of ozone and ultraviolet light. The wastewater treatment system of this study was designed to utilize both ozone and ultraviolet light produced in the DBD reactor for the degradation of organic contaminant. The DBD reactor consisted of a quartz cylinder and a coaxial ceramic tube inside of which a steel rod was placed. The DBD reactor was immersed in the wastewater that was grounded. In this case, the wastewater acted not only as an electrode but also as the cooling medium for the DBD reactor. An azo dye, Acid Red 27, was used as the organic contaminant. In this system, the organic contaminant was degraded by two oxidation pathways induced by ozone and ultraviolet light. The concentration of ozone, the ultraviolet radiation intensity and the degradation efficiency of the organic contaminant were measured by varying the discharge. The results showed that the present system was very effective for the degradation of the organic contaminant. The energy requirement for the degradation was found to be 0.654 kJ/mg, which is much smaller value than those obtained with an ultraviolet/photocatalytic process.     

铜和铝离子/UV催化臭氧降解偶氮二异丁腈废水研究

利用多相催化臭氧(O3)工艺处理偶氮二异丁腈(AIBN)废水,探讨不同催化O3体系(Cu2+、Al3+、Cu2++Al3+/UV催化O3)对AIBN废水中氰类污染物的降解特性,并对不同催化O3体系的动力学特性进行研究。结果表明,金属离子对催化O3工艺的处理效率具有明显影响,不同催化O3工艺对CN-去除作用都呈现起始去除速率较高而后减弱的特点,其中Cu2+和Al3+共同催化O3工艺的整体去除率较高,优于单独Cu2+和Al3+的催化性能。这可能是由于p H变化、金属离子与CN-配合作用、金属离子和O3作用的综合影响结果。动力学研究结果表明,不同催化O3体系降解AIBN废水中的CN-污染物的氧化反应符合准一级动力学反应,表观反应速率常数k在0.0245~0.00301 min-1之间。     

Effect of ozone on poly(vinyl chloride) degradation

The influence of ozone on the kinetics and mechanisms of poly(vinyl chloride) degradation has been studied. The rate constants for reaction of ozone with saturated and unsaturated units of macromolecules have been measured. The products of the reaction of ozone with double bonds are inactive and do not influence the subsequent thermal dehydrochlorination of the polymer. The products of reaction of ozone with saturated units greatly increase dehydrochlorination.     

Influence of ozone treatment on structure and thermal properties of bis-2-hydroxyethyl terephthalate-based copolymers

Polyesters are a particularly interesting group of polymers because of their ester bonds in the main chain, which are sensitive to degradation. It has been shown that aromatic polyesters [eg. poly(ethylene terephthalate) (PET)] can be degraded when they are copolymerized with aliphatic polyesters. In this regard, the objective of our previous study was to obtain and investigate new copolymers with some fragments of PET and its hydrolytic degradation. In this work, the impact of ozone degradation on properties of bis-2-hydroxyethyl terephthalate-based copolymers was researched. Apart from the bis-2-hydroxyethyl terephthalate, the copolymers comprised oligomers of lactic acid and glycolic acid in different combination. During ozone degradation, samples were kept for 24 h in atmosphere containing 0.51 vol.% of ozone. Structure changes were determined by means of FTIR spectroscopy. In the IR spectra of ozonised samples, new bonds characteristic for ozonised polymers were observed. Thermal properties of copolymers before and after degradation process were reviewed based on differential scanning calorimetry (DSC) and thermogravimetry. DSC results revealed that melting point increased, especially for copolymers displaying higher quantity of PET units.     

Photochemical properties of selected flavonol dyes: Effects on their separation using capillary electrophoresis

Flavonols are naturally occurring dyes that can be extracted from plants. Because of their antioxidant properties, they are thought to have health benefits. In this study, the photochemical degradation properties of selected flavonols were investigated. Dilute solutions of dyes were exposed to light from a broadband visible light source, and the rate of photodegradation was determined by measuring the decrease in fluorescence of the dyes with respect to time. At pH 9.24, the first-order rate constants for 10?µg?mL^?1 solutions of myricetin, quercetin, kaempferol, and morin were 0.468, 0.162, 0.108, and 0.126?s^?1, respectively. Interestingly, the stability of these historical dyes was also found to be greatly affected by pH. Awareness of the photochemical properties and stability of flavonol dyes is very important for capillary electrophoresis (CE) separations. Photodegradation of the flavonol dyes under the alkaline conditions (pH 9.2) used in CE can have a profound effect on the reproducibility of repeated separations. Even a modest decrease in pH (pH 8.5) greatly improved the stability of these dyes and enabled the successful separation of these flavonol dyes with minimal degradation over time.     

Degradation of 4-Chlorophenol by High-Voltage Pulse Corona Discharges Combined with Ozone

Degradation of aqueous 250 mg/L 4-chlorophenol (4-CP) by high-voltage pulse corona discharges combined with ozone was investigated to gain insight into factors affecting enhancement of the combined system. High-voltage pulse corona discharges, ozonation, and a combination of the two were used to facilitate the degradation of aqueous 4-CP. Experimental results indicate that the treatment of 4-CP using a combination of high-voltage pulse corona discharges and ozonation within 30 min resulted in the almost degradation (96%) and a 51% reduction of the chemical oxygen demand (COD). This apparent synergistic effect may be attributed to the enhancement of ozone decomposition. The degradation of aqueous 4-CP by high-voltage pulse corona discharges combined with ozone was found to be affected by ozone concentration, substrate concentration, and interelectrode separations. The increase of ozone concentration leads to an increase of 4-CP conversion and COD removal. The conversion of 4-CP decreased with increase in 4-CP concentration and interelectrode separations.     

Highly Efficient Photodegradation of Organic Pollutants Assisted by Sonoluminescence

The mechanism of the photodegradation of azo dyes via ultrasonication is studied using a combination of the high‐performance liquid chromatography and UV–vis spectroscopy with detailed analysis of the kinetics. Based on the kinetics studies of the sonodegradation, it was proposed that the degradation of azo dyes was a multistage process that involved: (1) the direct attack of azo bonds and phenyl rings of dyes by the sonochemically formed reactive oxygen species; (2) the activation of semiconductor particles by the light emitted during cavitation and the triggering of the photocatalytic pathways of dye degradation and (3) increase of the adsorption capacity of the semiconductor particles due to the sonomechanically induced interparticle collisions. The detailed kinetics study can help in following an effective process up‐scaling. It was demonstrated that extremely short pulses of light flashes in a cavitated mixture activated the surface of photocatalysts and significantly enhanced dye degradation processes.     

空心球状碘氧化铋的制备及其对染料的吸附降解性能

通过溶剂热法制备出空心球状的碘氧化铋,采用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)和物理吸附仪等技术手段对样品的结构和性能进行了表征。选用阳离子型染料罗丹明B和阴离子型染料活性蓝KN-R来研究BiOI的吸附性能和光催化活性。结果表明,在不同的溶液初始pH值下BiOI对不同结构和类型的染料表现出不同的吸附性和光催化降解性。BiOI对罗丹明B和活性蓝KN-R均有较高的吸附性和降解率,且光催化降解效率可以达到96.2%和92.5%。捕捉实验表明,h+在光催化降解中起主要作用。     

超声波辐照和臭氧氧化协同降解废水中的结晶紫

采用超声波辐照、臭氧氧化以及超声波辐照-臭氧氧化降解废水中的结晶紫;考察了废水初始pH、超声波功率和频率、氧气流量、反应温度等因素对降解效率的影响.结果表明:超声波和臭氧对结晶紫的降解具有协同作用;当废水溶液初始质量浓度为200mg.L-1、pH为10.0时,控制超声波功率和频率分别为100 W和30kHz,氧气流量为0.4L.min-1,反应温度为25℃,反应时间为90 min,则总有机碳(TOC)的去除率可达89.2%,相应的一级反应速率常数为2.38×10-2min-1.     

纳米氧化锌光催化降解有机染料性能的研究

用自制的纳米ZnO在室外阴天、太阳光照射、室内紫外灯照射等条件下对不同有机染料的降解性能作了系统的研究。结果表明纳米ZnO在太阳光照射条件下对弱碱性有机染料溶液的降解效果较好。本文还比较了自制纳米ZnO与纳米TiO2对有机染料的降解性能，结果表明ZnO的降解效果优于TiO2。     

Determination of particle-associated hydroxynitropyrenes with correction for chemical degradation on a quartz fibre filter during high volume air sampling

A correction method for the determination of atmospheric monohydroxylated derivatives of 1-nitropyrene (hydroxy-1-nitropyrenes, OHNPs) based on their degradation rates during high volume air sampling was established. OHNPs adsorbed directly on a quartz fibre filter (QFF) or on airborne particles collected on a QFF were exposed to ambient air passively or actively in a high volume air sampling system. The influence of ozone flux and exposure time on the degree of degradation of OHNPs was investigated. Up to 50% of OHNPs degraded over 1 h of exposure to ambient air containing ～60 ppbv of ozone in the active system. The degradation rate constants of OHNPs were found to correlate with the number of ozone molecules passing through the QFF in a unit time (N_O3) during high volume air sampling. The chemical loss of OHNPs under high volume air sampling conditions was successfully evaluated by the exposure time and the pseudo-first-order rate constant for OHNP degradation estimated from the correlation with N_O3. Concentrations of 3-, 6-, and 8-hydroxy-1-nitropyrenes in airborne particles collected in Osaka, Japan were determined using the established correction method.     

Reaction of a phospholipid monolayer with gas-phase ozone at the air-water interface: measurement of surface excess and surface pressure in real time

The reaction between gas-phase ozone and monolayers of the unsaturated lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, POPC, on aqueous solutions has been studied in real time using neutron reflection and surface pressure measurements. The reaction between ozone and lung surfactant, which contains POPC, leads to decreased pulmonary function, but little is known about the changes that occur to the interfacial material as a result of oxidation. The results reveal that the initial reaction of ozone with POPC leads to a rapid increase in surface pressure followed by a slow decrease to very low values. The neutron reflection measurements, performed on an isotopologue of POPC with a selectively deuterated palmitoyl strand, reveal that the reaction leads to loss of this strand from the air-water interface, suggesting either solubilization of the product lipid or degradation of the palmitoyl strand by a reactive species. Reactions of (1)H-POPC on D(2)O reveal that the headgroup region of the lipids in aqueous solution is not dramatically perturbed by the reaction of POPC monolayers with ozone supporting degradation of the palmitoyl strand rather than solubilization. The results are consistent with the reaction of ozone with the oleoyl strand of POPC at the air-water interface leading to the formation of OH radicals. The highly reactive OH radicals produced can then go on to react with the saturated palmitoyl strands leading to the formation of oxidized lipids with shorter alkyl tails.     

Synergetic effect of ozone and ultrasonic radiation on degradation of chitosan

Under conditions of continuous ozone gas application and constant ultrasonic radiation (UR), chitosan was effectively degraded. The existence of a synergetic effect of ozone and ultrasonic radiation on the degradation of chitosan was demonstrated by means of determination of viscosity-average molecular weight. The efficiency of the ozone and ultrasonic radiation treatment compared with acid hydrolysis on degradation of chitosan was investigated. In addition, the structure of the degraded chitosan was characterized by FT-IR and ¹³C NMR spectral analyses. The whole initial chitosan's monomer structure still existed in the resulting degraded chitosan with different low molecular weight. The pilot study of the chemical stability of the degraded chitosan was carried out. There was no significant change of the total degree of deacetylation (DD) of degraded chitosan compared with the initial chitosan. The combined O₃/UR technique is promisingly suitable for scale-up manufacture of low-molecular-weight chitosan.