Photocatalytic degradation of dyes on a magnetically separated photocatalyst under visible and UV irradiation

A novel kind of magnetically separable photocatalyst of TiO2/SiO2/gamma-Fe2O3 (TSF) is prepared. Scanning tunnel microscope (STM) and X-ray diffractometer (XRD) were used to characterize the structure of the photocatalyst. In the TSF photocatalyst, a TiO2 shell is for photocatalysis, a gamma-Fe2O3 core as a carrier is for separation by the magnetic field and a SiO2 membrane between the TiO2 shell and the gamma-Fe2O3 core is used to weaken the adverse influence of gamma-Fe2O3 on the photocatalysis of TiO2. Three kinds of dyes, Fluoresein, Orange II and Red acid G, were used to examine the photocatalytic activity of TSF. Due to strong UV adsorption of the gamma-Fe2O3, the photocatalytic activity of TSF was lower than that of the pure TiO2. Deducting the light absorption of the gamma-Fe2O3 particles, the photocatalytic activity of TSF was found to be higher than that of the P25 under UV irradiation. On the other hand, the photocatalytic activity of TSF under visible irradiation was much lower than that of the P25 TiO2 even deducting the visible light absorption of the gamma-Fe2O3 particles. Differences in the photocatalytic mechanisms under UV and visible irradiation lead to the differences in the photodegradation characteristics of dyes on TSF. The recycled TSF exhibited a good repeatability of photocatalytic activity.     

Influence of photolysis on multispectral photoacoustic measurement of nitrogen dioxide concentration

Multispectral photoacoustic instruments are commonly used to measure aerosol and nitrogen dioxide (NO₂) light absorption coefficients to determine the radiation budget of the atmosphere. Here a new photoacoustic system is developed to explore the effect of photolysis on the measured signal in a multispectral photoacoustic spectrometer. In this system, a 405-nm laser is used primarily as light source for photolysis. Additionally, a well-overlapped 532-nm laser, modulated at the resonant frequency of the photoacoustic instrument, is used to probe the NO₂ concentration. As a result, the photolysis effect at 405 nm can be observed by the photoacoustic instrument through the 532-nm laser. This work determines an 11% reduction of the photoacoustic signal caused by the photolysis effect for typical conditions, which needs to be taken into account when calibrating multispectral photoacoustic spectrometers with NO₂.

Implications: Multispectral photoacoustic instruments are commonly used to measure aerosol and nitrogen dioxide (NO₂) light absorption coefficients to determine the radiation budget of the atmosphere. A 405-nm laser is often used in these multispectral photoacoustic instruments. Although NO₂ absorbs strongly at 405 nm, it also has a strong photolysis pathway that is accessible by light of the same wavelength. Photolysis reduces the photoacoustic signal, necessitating special care when interpreting photoacoustic measurements. This paper offers a method for the multispectral photoacoustic instrument user to quantify the influence of the 405-nm NO₂ photolysis effect on the photoacoustic signal.     

Treatment of oily port wastewater effluents using the ultraviolet/hydrogen peroxide photodecomposition system.

This paper presents the nonselective degradation of mechanically pretreated oily wastewater by hydrogen peroxide (H2O2) in the presence and absence of UV irradiation. The effect of chemical oxidation on wastewater biodegradability was also examined. The exclusive use of H2O2 photolyzed by daylight results in quite efficient degradation rates for the low peroxide concentrations used. Higher hydrogen peroxide concentrations inhibit degradation of organic contaminants in the wastewater. The degradation rates of all contaminants are relatively high with an advanced oxidation system (UV/H2O2), but degradation efficiencies are not distinguishably different when 20 or 45 minutes of UV irradiation is used. The excess of H2O2 used in the process can inhibit phenolic degradation and may lead to the formation of a new phenolic fraction. The biodegradability of port wastewater did not increase significantly following the application of the advanced oxidation process.     

Numerical studies of the heterogeneous combustion of char using detailed chemistry

The oxidation of graphite is used as a model system for the combustion of char. In order to understand this oxidation process a stagnation-point flow of an oxygen stream on a graphite surface is investigated numerically. The chemical reactions in the gas phase as well as on the surface are modelled by a series of elementary steps. The surface reactions take into consideration the different surface complexes formed, the influence of the geometry of the graphite surface and the interaction of gas-phase molecules with surface complexes. The rate coefficients used are estimated by applying methods of the microkinetic analysis of heterogeneous catalytic reactions. The mechanism is used to simulate the combustion rate of a graphite surface and the ratio of CO to CO2 formed on the surface. The simulation results are compared with experimental data and a good agreement is achieved. Furthermore, the fraction of char-bound nitrogen converted to N2 and N2O is calculated.     

Further Effects of Temperature and Pressure on Photochemical Oxidant Production

A procedure is described for producing a sulfur dioxide (SO₂) contaminated atmosphere within a body plethysmograph, exposing man to this atmosphere while maintaining the SO₂ concentration at a given level, and measuring the concentration with less than a oneminute lag time. A syringe is used to introduce incremental volumes of SO₂ limiting the maximum SO₂ concentration in the chamber and assuring safety of the subject. A Titrilog SO₂ analyzer with its rapid response characteristics provides quick measurement of the SO₂ concentration. The body plethysmograph used in this manner serves simultaneously as a pulmonary function measuring device and as an exposure chamber.     

An evaluation of the green chelant EDDS to enhance the stability of hydrogen peroxide in the presence of aquifer solids

Hydrogen peroxide is a widely used in situ chemical oxidation reagent which relies on catalysts to generate the suite of reactive species that are required to aggressively remediate contaminated soils and groundwater. In the subsurface environment these catalysts are usually transition metals that are added to the injected solution, or are naturally occurring. Chelating agents are widely used to maintain an adequate dissolved transition metal concentration in near-neutral pH conditions; however, they can also be used to improve the persistence of H(2)O(2) in situations when the aquifer solids have sufficient transition metal content. Ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) have been considered to be the most effective chelants and therefore are the most widely used. While previous research efforts have focused on the chelating agent efficiency, the long-term fate of these chelants in the natural subsurface environment is a concern since both EDTA and NTA are non-readily biodegradable. The focus of this investigation was to evaluate the potential of using the environmentally friendly or green chelating agent ethylenediaminedisuccinate (EDDS) as an alternative to EDTA or NTA to suppress the catalytic activity of naturally-occurring transition metals. A series of batch reactor and column experiments were performed using five different aquifer materials and the results demonstrate that EDDS has a comparative chelating efficiency to that of EDTA. The addition of EDDS was able to reduce the H(2)O(2) decomposition rates in the presence of the aquifer materials used in this investigation by 24-97% in well-mixed batch systems, and by 20% and 38% in the column trials where H(2)O(2) was detected in the effluent.     

Battelle Forecasts U.S. To Reach $61.8 Billion R&D Funding in 1980

A technique for locating a source of odor which is considered to be a community air pollution nuisance, PONG2, was described in Paper I. Selected members of the public are asked to record the times at which they notice an unpleasant odor. A local meteorological station supplies the Pasquill stability and the wind-speed and direction for the locality at the time of complaint. This data is used to determine a region upwind of the location of the complaint in which the source of odor may lie. By overlaying the different regions generated by different complaints, PONG2 identifies the most probable location of the odor source. In this paper an enhanced form of PONG2 is used to identify odor sources when several may be involved. Simulations suggest a rule of thumb for deciding when a location identified by PONG2 should be considered to be a likely source of odor. The technique is applied to data from a survey conducted near Melbourne, Australia.     

改性半焦脱除烟气中SO2的研究

对内蒙工业副产褐煤半焦（比表面积49.187m^2／g,孔容0.0351cm^2／g）,采用加压水热化学活化法,HNO3活化法和高温煅烧相结合的方法制备出半焦烟气脱硫剂,并对脱硫剂的脱硫性能进行固定床活性评价。分析表明,其脱硫效果比较好,转化率维持在50％以上的累计硫容可达24．30％,脱硫时间长达35h,远远高于原料半焦的脱硫效果（硫容为0．68％,时间为1．5h）;同时采用水洗法对脱硫剂进行再生,其再生液可用来制备浓度为9.01％的稀硫酸。     

The kinetics of catalytic incineration of dimethyl sulfide and dimethyl disulfide over an MnO/Fe2O3 catalyst

The catalytic incineration of dimethyl sulfide and dimethyl disulfide [(CH3)2S and (CH3)2S2] over an MnO/Fe2O3 catalyst was carried out in a bench-scale catalytic incinerator. Three kinetic models (i.e., the power-rate law, the Mars and Van Krevelen model, and the Langmuir-Hinshelwood model) were used to analyze the results. A differential reactor design was used for best fit of kinetic models in this study. The results show that the Langmuir-Hinshelwood model may be feasible to describe the catalytic incineration of (CH3)2S and (CH3)2S2. This suggests that the chemical adsorption of O2 molecules is important in this incineration.     

机械絮凝池内部流场数值模拟和絮凝效果分析

通过对机械絮凝池内不同进水流量和不同桨板转速的流场分别进行数值模拟,计算得到湍动能k和湍动耗散率ε等水力参数,并结合混凝实验分析水流对絮凝效果的影响。结果表明:湍动能k和湍动耗散率ε可以作为评价絮凝是否充分的标准;机械絮凝池最佳水力停留时间为18 min;平均k值为0.00613～0.00212 m2/s2,平均ε值为0.00869～0.00199 m2/s3时,机械絮凝池装置的絮凝效果比较理想。     

Defining the photochemical contribution to particulate matter in urban areas using time-series analysis

The objective of this project is to demonstrate how the ambient air measurement record can be used to define the relationship between O3 (as a surrogate for photochemistry) and secondary particulate matter (PM) in urban air. The approach used is to develop a time-series transfer-function model describing the daily PM10 (PM with less than 10 microm aerodynamic diameter) concentration as a function of lagged PM and current and lagged O3, NO or NO2, CO, and SO2. Approximately 3 years of daily average PM10, daily maximum 8-hr average O3 and CO, daily 24-hr average SO2 and NO2, and daily 6:00 a.m.-9:00 a.m. average NO from the Aerometric Information Retrieval System (AIRS) air quality subsystem are used for this analysis. Urban areas modeled are Chicago, IL; Los Angeles, CA; Phoenix, AZ; Philadelphia, PA; Sacramento, CA; and Detroit, MI. Time-series analysis identified significant autocorrelation in the O3, PM10, NO, NO2, CO, and SO2 series. Cross correlations between PM10 (dependent variable) and gaseous pollutants (independent variables) show that all of the gases are significantly correlated with PM10 and that O3 is also significantly correlated lagged up to two previous days. Once a transfer-function model of current PM10 is defined for an urban location, the effect of an O3-control strategy on PM concentrations is estimated by calculating daily PM10 concentrations with reduced O3 concentrations. Forecasted summertime PM10 reductions resulting from a 5 percent decrease in ambient O3 range from 1.2 microg/m3 (3.03%) in Chicago to 3.9 microg/m3 (7.65%) in Phoenix.     

The nonlinearity and related band strength of carbon monoxide when applied in ambient air measurement using open long-path Fourier transform infrared spectrometry

The accuracy of CO concentration determination by open-path Fourier transform infrared (FTIR) spectrometry has been re-evaluated in detail. The evaluation focuses on the correction of the calibration curve--the integrated intensity of a standard spectrum--that is used as a comparison spectrum when doing quantitative analysis of CO. Results show that the calibration curve (with 0.5 cm(-1) or 1 cm(-1) resolution) is apparently inclined to be nonlinear under standard conditions, and that the threshold point of nonlinearity is approximately 0.1 atm-cm. Two commercial FTIR field monitoring systems have been used to investigate the nonlinearity trend. The experimental method consists of using open-path FTIR systems in combination with nondispersive infrared (NDIR) monitors to establish the calibration curve in a semi-closed corridor The results have been double-checked using closed-cell dynamic equilibrium systems. When the optical density is larger than a certain value, the curves begin to bend, and when the optical density approaches zero, the band strength is around 178 +/- 3 atm(-1) cm(-2) and 173 +/- 2 atm(-1) cm(-2), respectively, for 0.5 and 1 cm(-1) resolution at standard temperature and pressure (STP). These values are quite different from other published data that have been acquired by the pressurized method or by high-resolution (<0.006 cm(-1)) spectrometers. It is thought that a higher accuracy is achieved when these new calibration results are used to quantify the CO concentration. The error in concentration determination within 0.1 optical density is less than 2%, and that in the higher optical density region is less than 5%.     

Cationic surfactant as a sensitizer for the spectrophotometric determination of hydrogen sulphide in air and evaluation of a new absorbing medium containing triethanolamine-zinc acetate-sodium hydroxide

An extractive spectrophotometric method for the determination of trace amounts of hydrogen sulphide after fixing the gas in triethanolamine (TEA)-zinc acetate-sodium hydroxide solution is described. The method is based on the reaction of iodate with hydrogen sulphide in the presence of acid and excess chloride ion leading to the formation of ICl2- species which is used to iodinate 2',7'-dichlorofluorescein to form 2',7'-dichloro-4',5'-diiodofluorescein. The iodinated product formed is extracted into an organic solvent and sensitized by equilibrating with a cationic surfactant, cetrimide, in the presence of acetate buffer (pH 5.9 +/- 0.1). The colour system obeys Beer's law over the range 0-1 microg of hydrogen sulphide and the relative standard deviation is 2.4% for 10 determinations at 0.75 microg of hydrogen sulphide. The effect of interfering gases on the determination is discussed. The proposed absorbing solution has been evaluated using a hydrogen sulphide permeation device. This absorbing solution has an absorption efficiency of > 93% at a flow rate of 1.5 litre min(-1) for a sampling period of 2 h. The fixed H2S is stable for 40 days. The method has been applied to determine residual H2S levels in a laboratory fume hood and in the vicinity of sewage pumping station. The method can be used to determine as little as 0.05 microg of hydrogen sulphide.     

Degradation of bisphenol A using UV and UV/H2O2 processes

Bisphenol A (BPA; 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol) is a substance typically used in the plastic industry. It is used in the production of epoxy resins, polycarbonate, or fire retardants or as a stabilizer and an antioxidant in numerous types of plastics. Bisphenol A is introduced into the environment via municipal and industrial wastewater. Because of its hydrophobic properties, BPA has the potential for sorption on activated sludge during the biological wastewater treatment processes. This study investigated the degradation of BPA by means of UV-radiation and in the UV/H2O2 process with the presence and absence of hydrocarbonate ions (HCO3(-)) as hydroxyl radicals (OH*) scavengers. The calculated value of quantum yield was equal to 0.18, and the value of BPA rate constant with hydroxyl radicals was equal to 3.3 x 10(9) M(-1) s(-1).     

Oxidative co-treatment using hydrogen peroxide with anaerobic digestion of excess municipal sludge.

The effect of an oxidative co-treatment on anaerobic digestion of a mixture of primary and waste activated sludge was investigated. The oxidant used in this study was hydrogen peroxide (H2O2). A maximum improvement in solid destruction of 15.2% was achieved in the overall process, with a dosage of 2.0 g H2O2/g influent volatile suspended solids (VSS(influent)). All configurations operated at this dosage also showed statistically significant increases in solids removal. A statistically significant enhancement in overall solids destruction was observed for the lower oxidant dosage (0.5 H2O2/g VSS(influent)). Surprisingly, for 1.0 g H2O2/g VSS(influent), only one of the three configurations involving oxidative co-treatment showed significant increases in solids destruction. Special attention was paid to the performance of this process relative to fecal coliforms destruction. Class A biosolids were obtained for all the different hydrogen peroxide dosages used when oxidative co-treatment is combined with a two-stage anaerobic digestion process.     

An in situ study of the role of surface films on granular iron in the permeable iron wall technology

Permeable walls of granular iron are a new technology developed for the treatment of groundwater contaminated with dissolved chlorinated solvents. Degradation ofthe chlorinated solvents involves a charge transfer process in which they are reductively dechlorinated, and the iron is oxidized. The iron used in the walls is an impure commercial material that is covered with a passive layer of Fe2O3, formed as a result of a high-temperature oxidation process used in the production of iron. Understanding the behaviour of this layer upon contact with solution is important, because Fe2O3 inhibits mechanisms involved in contaminant reduction, including electron transfer and catalytic hydrogenation. Using a glass column specially designed to allow for in situ Raman spectroscopic and open circuit potential measurements, the passive layer of Fe2O3 was observed to be largely removed from the commercial product, Connelly iron, upon contact with Millipore water and with a solution of Millipore water containing 1.5 mg/l trichloroethylene (TCE). It has been previously shown that Fe2O3 is removed from iron surfaces upon contact with solution by an autoreduction reaction; however, prior to this work, the reaction has not been shown to occur on the impure commercial iron products used in permeable granular iron walls. The rate of removal was sufficiently rapid such that the initial presence of Fe2O3 at the iron surface would have no consequence with respect to the performance of an in situ wall. Subsequent to the removal of Fe2O3 layer, magnetite and green rust formed at the iron surface as a result of corrosion in both the Millipore water and the solution containing TCE. The formation of these two species, rather than higher valency iron oxides and oxyhydroxides, is significant for the technology. The former can interfere with contaminant degradation because they inhibit electron transfer and catalytic hydrogenation. Magnetite and green rust, in contrast, will not inhibit the mechanisms involved in contaminant reduction, and hence their formation is beneficial to the long-term performance of the iron material.     

State of energy consumption and CO2 emission in Bangladesh

Carbon dioxide (CO2) is one of the most important gases in the atmosphere, and is necessary for sustaining life on Earth. It is also considered to be a major greenhouse gas contributing to global warming and climate change. In this article, energy consumption in Bangladesh is analyzed and estimates are made of CO2 emission from combustion of fossil fuel (coal, gas, petroleum products) for the period 1977 to 1995. International Panel for Climate Change guidelines for national greenhouse gas inventories were used in estimating CO2 emission. An analysis of energy data shows that the consumption of fossil fuels in Bangladesh is growing by more than 5% per year. The proportion of natural gas in total energy consumption is increasing, while that of petroleum products and coal is decreasing. The estimated total CO2 release from all primary fossil fuels used in Bangladesh amounted to 5072 Gigagram (Gg) in 1977, and 14 423 Gg in 1995. The total amounts of CO2 released from petroleum products, natural gas, and coal in the period 1977-1995 were 83 026 Gg (50% of CO2 emission), 72 541 Gg (44% of CO2 emission), and 9545 Gg (6% CO2 emission), respectively. A trend in CO2 emission with projections to 2070 is generated. In 2070, total estimated CO2 emission will be 293 260 Gg with a current growth rate of 6.34% y . CO2 emission from fossil fuels is increasing. Petroleum products contribute the majority of CO2 emission load, and although the use of natural gas is increasing rapidly, its contribution to CO2 emission is less than that of petroleum products. The use of coal as well as CO2 emission from coal is expected to gradually decrease.     

Kinetics and mechanism of color removal of methylene blue with hydrogen peroxide catalyzed by some supported alumina surfaces

The catalyzed kinetics of the oxidative mineralization of the cationic dye methylene blue, phenothiazonium, 3,7-bis(dimethylamino)-chloride, with hydrogen peroxide were studied both in buffered and unbuffered solutions. The supported alumina catalysts used were in the form of copper(II), cobalt(II), manganese(II), and nickel(II)-ions. Also, some copper(II)-complexes were used, e.g. copper(II)-ammine ([Cu(amm)4]2+), copper(II)-ethylenediamine ([Cu(en)2]2+) and copper(II)-monoethanolamine ([Cu(mea)2]2+). The reaction is first order with respect to methylene blue. On the other hand, the order with respect to hydrogen peroxide is concentration range dependent. This range depends strongly on the catalyst used. At lower [H2O2], the order was 1 which then decreases with increasing [H2O2] passing through 0 at the maximum rate and finally becomes negative. This phenomenon is parallel to the formation of a colored intermediate on the surface of the catalyst. This suggests that the intermediate has an inhibiting effect on the rate of color removal. Moreover, the rate of the reaction was found to be strongly dependent on the pH of the solution and its ionic strength. It increases with increasing both pH and the concentration of added potassium chloride. Also, the rate of reaction is inhibited in presence of sodium dodecylsulfate anionic surfactant. The repeated use of the different catalysts showed that their catalytic activities are almost unaffected. A reaction mechanism was proposed with the formation of free radicals as reactive intermediates.     

Methods to determine response factors for infrared gas imagers used as quantitative measurement devices

Response factors (RF) can be used to characterize relative sensitivity of one compound vs. another compound for the same measurement instrument. Use of RF allows the analysts/operators to calibrate the instrument with one compound and make measurement for a large number of compounds. This method is adopted for Flame Ionization Detector (FID) based survey instruments used in the Leak Detection and Repair (LDAR) practice for control of fugitive emissions of volatile organic compounds. Gas detecting Infrared (IR) cameras have been used for leak detection. However, the RF for IR cameras has not been well established despite some attempt to develop a method for IR camera RF. In addition to a method proposed earlier (Method 1), two new methods for IR camera RF are proposed in this paper: Method 2 based on theoretical approach and Method 3 based on experimental approach. All three methods are examined and compared. Both Methods 2 and 3 have shown the ability to characterize the behavior of RF for various compounds and substantially higher accuracy than Method 1. Method 2 provides a mechanism to generate RF for a large number of compounds without conducting experiments, and is recommended for implementation. The RF derived from this method can be used both in the emerging field of Quantitative Optical Gas Imaging (QOGI) and to answer the most common question that IR camera users ask—whether a particular compound can be imaged by a particular IR camera.Implications: Infrared imager is an efficient tool for detecting gas leaks from process equipment and has been used in leak detection and repair (LDAR) programs for control of fugitive emissions. However, the information regarding which chemical compounds can be imaged and how sensitive a given infrared imager is for various compounds is limited. A theoretical method is presented in this paper that can answer these questions without conducting resource-intensive experiment. The results of this theoretical method has good agreement with experimental data. The method has been used to predict relative sensitivity for 398 compounds.     

Degradation of the antifouling compound Irgarol 1051 by manganese peroxidase from the white rot fungus Phanerochaete chrysosporium

Irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine), a derivative of s-triazine herbicide, is an antifouling compound used as an alternative to organotins. The compound is highly persistent and is known to be biodegraded only by the white rot fungus, Phanerochaete chrysosporium. We used partially purified manganese peroxidase (MnP) prepared from P. chrysosporium to evaluate its capacity to degrade Irgarol 1051. MnP degraded Irgarol 1051 to two major products, one identified as M1 (identical to GS26575, 2-methylthio-4-tert-butylamino-6-amino-s-triazine) and the other not identified but with same mass spectrum as M1 and a different ultraviolet spectrum. This report clearly demonstrates that this ligninolytic enzyme is involved in the degradation of Irgarol 1051.