复合型CoO/TiO2光催化剂降解亚甲基蓝动力学研究

以钛酸四丁酯为前驱体,采用溶胶凝胶法,制备了CoO掺杂的TiO2光催化剂。利用X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）、紫外可见漫反射（UV-vis DRS）对催化剂进行了分析、表征。以中压汞灯为光源,研究了亚甲基蓝（MB）在CoO/TiO₂微粒水悬浮液中的降解动力学。结果表明：所制备的催化剂活性组分主要是锐钛矿型的二氧化钛和CoO固溶体,粒径为25～30 nm,分布均匀。亚甲基蓝的光催化降解动力学满足一级动力学,在一定的浓度范围内,反应速率常数随初始浓度增大而减少,适当的掺钴量可以有效地提高TiO₂光催化活性,其最佳掺杂量重量百分比为0.25%。     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

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^-。     

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.     

Fenton试剂氧化苯酚过程中Fe（Ⅱ）浓度的变化

考察了Fenton试剂氧化降解苯酚过程中Fe(Ⅱ)浓度的变化,并通过实验探讨了其变化的原因.实验结果表明,在Fenton反应发生的第1 rain内,Fe(Ⅱ)浓度可降低到初始浓度的60%左右,随着反应的继续Fe(Ⅱ)浓度在大约20min降低到最小值,然后开始增大,说明了Fe(Ⅲ)还原作用的存在;Fenton试剂氧化降解苯酚的中间产物包括对苯二酚、邻苯二酚、间苯二酚和苯醌等,其中前三者能对Fe(Ⅲ)有效还原,是Fenton试剂氧化降解苯酚过程中Fe(Ⅲ)还原的主要途径之一.     

A batch study on the bio-fixation of carbon dioxide in the absorbed solution from a chemical wet scrubber by hot spring and marine algae

Carbon dioxide mass transfer is a key factor in cultivating micro-algae except for the light limitation of photosynthesis. It is a novel idea to enhance mass transfer with the cyclic procedure of absorbing CO(2) with a high performance alkaline abosorber such as a packed tower and regenerating the alkaline solution with algal photosynthesis. Hence, the algae with high affinity for alkaline condition must be purified. In this study, a hot spring alga (HSA) was purified from an alkaline hot spring (pH 9.3, 62 degrees C) in Taiwan and grows well over pH 11.5 and 50 degrees C. For performance of HSA, CO(2) removal efficiencies in the packed tower increase about 5-fold in a suitable growth condition compared to that without adding any potassium hydroxide. But ammonia solution was not a good choice for this system with regard to carbon dioxide removal efficiency because of its toxicity on HSA. In addition, HSA also exhibits a high growth rate under the controlled pHs from 7 to 11. Besides, a well mass balance of carbon and nitrogen made sure that less other byproducts formed in the procedure of carboxylation. For analysis of some metals in HSA, such as Mg, Mn, Fe, Zn, related to the photosynthesis increased by a rising cultivated pH and revealed that those metals might be accumulated under alkaline conditions but the growth rate was still limited by the ratio of bicarbonate (useful carbon source) and carbonate. Meanwhile, Nannochlopsis oculta (NAO) was also tested under different additional carbon sources. The results revealed that solutions of sodium/potassium carbonate are better carbon sources than ammonia carbonate/bicarbonate for the growth of NAO. However, pH 9.6 of growth limitation based on sodium was lower than one of HSA. The integrated system is, therefore, more feasible to treat CO(2) in the flue gases using the algae with higher alkaline affinity such as HSA in small volume bioreactors.