The Kinetics of Catalytic Incineration of Dimethyl Sulfide and Dimethyl Disulfide over an MnO/Fe2O3 Catalyst

ABSTRACT

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.     

Preliminary study on removing Cs+/Sr2+ by activated porous calcium silicate—A by-product from high-alumina fly ash recycling industry

¹³⁷Cs⁺/⁹⁰Sr²⁺-containing radioactive wastewater is one of the most important problems that the world has been facing with. A by-product, activated porous calcium silicate, is generated at high levels by the pre-desiliconizing and soda-lime-sintering processes for producing Al₂O₃ from high-alumina fly ash. In order to examine if this by-product could be used as an absorbent for removal of ¹³⁷Cs⁺/⁹⁰Sr²⁺ from radioactive wastewater, various parameters, such as pH, adsorbent dose, contact time, and initial concentration, were discussed. Results indicated that the equilibrium reached in about 2 hr. Activated porous calcium silicate was highly pH sensitive and able to remove Cs⁺/Sr²⁺ in a near-neutral environment. The adsorption equilibrium was best described by Freundlich isotherm equations, and the adsorption of Cs⁺/Sr²⁺ was a physical process. The adsorption kinetic data could be better fitted by the pseudo-second-order model, and the adsorption was controlled by multidiffusion. Current study showed that activated porous calcium silicate has a good adsorption of Cs⁺/Sr²⁺ for their removal. However, other characteristics, such as selectivity because of coexisting cations, elution and regeneration, thermal stability, and acid resistance, should be discussed carefully before using it in an actual field.

Implications:Removing ¹³⁷Cs⁺/⁹⁰Sr²⁺ from radioactive wastewater is one of the tough issues that has been attracting more and more attention world widely, which is the same as fly ash. For recycling high-alumina fly ash, in which Al is extracted to produce Al₂O₃, a huge amount of activated porous calcium silicate is generated year by year. In this paper, this by-product was successfully used as an absorbent to remove ¹³⁷Cs⁺/⁹⁰Sr²⁺ from radioactive wastewater for the first time. Factors that affect the absorbability and the mechanisms were discussed in details, providing a possible choice for disposal of ¹³⁷Cs⁺/⁹⁰Sr²⁺-containing radioactive wastewater.     

Treatment of coking wastewater by an advanced Fenton oxidation process using iron powder and hydrogen peroxide

In this study the treatment of coking wastewater was investigated by an advanced Fenton oxidation process using iron powder and hydrogen peroxide. Particular attention was paid to the effect of initial pH, dosage of H₂O₂ and to improvement in biodegradation. The results showed that higher COD and total phenol removal rates were achieved with a decrease in initial pH and an increase in H₂O₂ dosage. At an initial pH of less than 6.5 and H₂O₂ concentration of 0.3 M, COD removal reached 44-50% and approximately 95% of total phenol removal was achieved at a reaction time of 1 h. The oxygen uptake rate of the effluent measured at a reaction time of 1 h increased by approximately 65% compared to that of the raw coking wastewater. This indicated that biodegradation of the coking wastewater was significantly improved. Several organic compounds, including bifuran, quinoline, resorcinol and benzofuranol were removed completely as determined by GC-MS analysis. The advanced Fenton oxidation process is an effective pretreatment method for the removal of organic pollutants from coking wastewater. This process increases biodegradation, and may be combined with a classical biological process to achieve effluent of high quality.     

Photocatalytic oxidation of monuron in the suspension of WO3 under the irradiation of UV-visible light

A comprehensive study of the degradation of monuron, one of the phenylurea herbicides, was conducted by UV-Vis/WO₃ process. It was found that hydroxyl radicals played a major role in the decay of monuron while other radicals (e.g. superoxide) and hole might also contribute to the decomposition of monuron. The oxidation path likely plays a major role in the generation of hydroxyl radicals. The effects of initial pH level, initial concentration of monuron, and inorganic oxidants on the performance of UV-Vis/WO₃ process were also investigated and optimized. Comparison between monuron decay pathways by UV-Vis/WO₃ and UV/TiO₂ was conducted. The decay mechanisms, including N-terminus demethylation, dechlorination and direct hydroxylation on benzene ring, were observed to be involved in the oxidation of monuron in these two processes. Sixteen intermediates were identified during the photodegradation of monuron and degradation pathways were proposed accordingly.     

组合阳极联合气体扩散阴极电催化降解苯胺

采用气体扩散电极为阴极,钛基氧化物（Ti／SnO2-Sb2O5-IrO2）和金属铁构成组合阳极,构建了新型电化学氧化体系用于降解有机污染物。利用该氧化体系,在不同实验条件下考察了苯胺降解的效果与降解过程的相关规律。结果表明,阴极电位、铁阳极通电时间以及苯胺初始浓度均显著影响苯胺的降解效果。当阴极电位为-0．7V,pH3．0,铁阳极通电时间20min时,电化学处理200mg／L苯胺480min,TOC的去除效率达到80．4％,矿化电流效率（MCE）为8．6％,显示了该氧化体系具有良好的有机物降解能力。此外,苯胺降解过程中氨氮和硝态氮浓度的变化表明,苯胺分子中的氮主要转化为NH4和NO3^-。     

Characteristics of springtime profiles and sources of ozone in the low troposphere over northern Taiwan

To quantify the possible sources of the high ambient ozone concentration in the low troposphere over Taiwan, ozone sounding data from a two-year intensive field measurement program conducted in April and early May of 2004 and 2005 in northern Taiwan has been examined. We found that the vertical ozone distributions and occurrence of enhanced ozone in the lower troposphere (below 6 km) mainly resulted from (1)Type NE: the long-range transport of ozone controlled by the prevailing northeasterly winds below 2 km, (2)Type LO: the local photochemical ozone production process, and (3)Type SW: the strong southwest/westerly winds aloft (2–6 km). In the boundary layer (BL), where Asian continental outflow prevails, the average profile for type NE is characterized by a peak ozone concentration of nearly 65 ppb at about 1500 m altitude. For type LO, high ozone concentration with an average ozone concentration greater than 80 ppb was also found in the BL in the case of stagnant atmospheric and sunny weather conditions dominated. For type SW, significant ozone enhancement with average ozone concentration of 70–85 ppb was found at around 4 km altitude. It is about 10 ppb greater than that of the types NE and LO at the same troposphere layer owing to the contribution of the biomass burning over Indochina. Due to Taiwan's unique geographic location, the complex interaction of these ozone features in the BL and aloft, especially features associated with northeasterly and south/southwesterly winds, have resulted in complex characteristics of ozone distributions in the lower troposphere over northern Taiwan.     

Comparison of summer and winter California central valley aerosol distributions from lidar and MODIS measurements

Aerosol distributions from two aircraft lidar campaigns conducted in the California Central Valley are compared in order to identify seasonal variations. Aircraft lidar flights were conducted in June 2003 and February 2007. While the ground PM_2.5 (particulate matter with diameter ≤ 2.5 μm) concentration was highest in the winter, the aerosol optical depth (AOD) measured from the MODIS and lidar instruments was highest in the summer. A multiyear seasonal comparison shows that PM_2.5 in the winter can exceed summer PM_2.5 by 68%, while summer AOD from MODIS exceeds winter AOD by 29%. Warmer temperatures and wildfires in the summer produce elevated aerosol layers that are detected by satellite measurements, but not necessarily by surface particulate matter monitors. Temperature inversions, especially during the winter, contribute to higher PM_2.5 measurements at the surface. Measurements of the mixing layer height from lidar instruments provide valuable information needed to understand the correlation between satellite measurements of AOD and in situ measurements of PM_2.5. Lidar measurements also reflect the ammonium nitrate chemistry observed in the San Joaquin Valley, which may explain the discrepancy between the MODIS AOD and PM_2.5 measurements.     

Photochemical degradation of ciprofloxacin in UV and UV/H2O2 process: kinetics, parameters, and products

Photochemical degradation of fluoroquinolone ciprofloxacin (CIP) in water by UV and UV/H₂O₂ were investigated. The degradation rate of CIP was affected by pH, H₂O₂ dosage, as well as the presence of other inorganic components. The optimized pH value and H₂O₂ concentration were 7.0 and 5 mM. Carbonate and nitrate both impeded CIP degradation. According to liquid chromatography–tandem mass spectrometry analysis, four and 16 products were identified in UV and UV/H₂O₂ system, respectively. Proposed degradation pathways suggest that reactions including the piperazinyl substituent, quinolone moiety, and cyclopropyl group lead to the photochemical degradation of CIP. Toxicity of products assessed by Vibrio qinghaiensis demonstrated that UV/H₂O₂ process was more capable on controlling the toxicity of intermediates in CIP degradation than UV process.     

Copper ultrastructural localization, subcellular distribution, and phytotoxicity in Hydrilla verticillata (L.f.) Royle

Laboratory experiments were conducted to investigate copper (Cu) subcellular distribution and toxicity in Hydrilla verticillata. Fronds were subjected to different concentrations (15, 75, and 150 μM) of Cu for 7 days. Cu grains were found in cell walls, plasmodesmata, and within the nuclei and chloroplasts using the autometallographic technique. Subcellular fractionation of Cu-containing tissues indicated that in leaves subjected to high Cu concentrations, 59–65 % of the element was located in the cell wall fraction, followed by cell organelles (21–30 %) and the soluble fraction (10–14 %). The levels of K, P, Zn, and Mg declined under all Cu concentrations, but Ca, Mn, and Fe contents reached their peak at 15 μM Cu and decreased thereafter. F _v/F _m, F ₀, and F _m fell significantly in line with the decrease in pigment content. Cu exposure also caused significant damage to the chloroplasts, mitochondria, and nuclei, including disintegration of the chloroplasts and vacuolization of the mitochondria and nuclei, all of which suggested that Cu hastened plant senescence. The Cu maximum permissible concentration for H. verticillata was 10 μM, which was less than the existing general water quality standard. This suggested that H. verticillata could be used to assess Cu phytotoxicity.     

低剂量臭氧的直接通加对活性污泥的活性、微生物种群及污泥减量化的影响

研究构建了2个容积为1.1 L的好氧活性污泥反应器（即1号和2号反应器）1,号反应器每天直接通加低剂量臭氧（投加量为0.01 g O3/g TSS）,不加臭氧的2号反应器作为对照平行运行,均采用每天换一次人工污水的充/排式操作。运行71 d的结果表明2,个反应器对人工污水COD的处理效果基本相同。反应器运行40 d后1,号反应器的污泥浓度比2号反应器的污泥浓度低1 400～1 700 mg/L并可稳定在8 200 mg/L,污泥减量化效果明显。低剂量臭氧的直接通加明显降低了胞内ATP浓度,并影响了微生物的抗氧化活性,2号反应器的平均超氧化物歧化酶和过氧化氢酶酶活比1号反应器分别高了24.3%和9.5%。PCR-DGGE对两反应器微生物种群的分析结果表明：Uncultured gammaproteobacteria bacteri-um、Nannocystis exedens和Uncultured actinobacterium为1号反应器的主要种群;而2号反应器的主要种群为Uncultured bacte-rium和Uncultured gammaproteobacteria bacterium。