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—visDRS）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25～30nm,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％。     

Photoinduced degradation of sulfonamides,kinetic, and structural characterization of transformation products and assessment of environmental toxicity

This study focuses on the degradation of the sulfonamide antibiotics, sulfadiazine, sulfamethazine, sulfamethoxazole, and sulfathiazole, using ultraviolet irradiation in various conditions. Different pHs were investigated in combination with the addition of hydrogen peroxide and further oxygen removal. High-performance liquid chromatography electrospray ionization ion-trap mass spectrometry was used to identify and elucidate degradation products and to establish concentration–time curves. Previously unknown degradation products could be characterized. Reaction rate constants of all compounds and transformation products were determined. The parent sulfonamides decayed according to first-order kinetics, while the concentrations of the transformation products varied with time according to a subsequent reaction of an intermediate product. Quantum efficiencies were analyzed for mechanistic purposes. As example, sulfamethoxazole was added to effluents from a wastewater treatment plant and irradiated. Phototoxicity and environmental hazard were assessed through quantitative structure-activity relationship computations. In addition, the minimal inhibition concentrations were determined for Pseudomonas fluorescens and Bacillus subtilis. Conclusions for UV-C irradiation as a fourth purification wastewater treatment stage were derived.     

Thermal degradation kinetics and mechanisms of Posidonia Oceanica under inert and oxidative atmospheres

The thermal degradation characteristics of Posidonia Oceanica (PO), a marine biomass abundantly available on the coastal zone of the Mediterranean Basin, were investigated using thermogravimetric analysis under inert and oxidative atmospheres. The kinetic parameters of the both thermal degradations conditions were determined using n-reaction order model. Coats–Redfern and Phadnis–Deshpande methods were used to discuss the probable degradation mechanisms. Results showed that PO is an attractive alternative for energy production owing to its elevated heating value. Moreover, PO thermal degradation follows the usual shape of biomass decomposition. Hence, under inert atmosphere, its thermal degradation had two different stages after moisture release. The first stage corresponded to the volatiles release while the second stage corresponded to the char formation. The solid-state decomposition mechanisms followed by the devolatilization step of PO were two or three dimensional diffusion controlled reaction. However, the decomposition mechanism during PO char formation corresponded to a nucleation and growth mechanism. Under oxidative atmosphere, two stages were also observed corresponding to volatiles release and char combustion, respectively. The solid-state mechanism of volatiles release followed three dimensional diffusion controlled reaction while the char combustion mechanism corresponded to a contracting area phase boundary controlled reaction.     

神农架大九湖泥炭藓沼泽湿地对镉(Ⅱ)、铜(Ⅱ)、铅(Ⅱ)、锌(Ⅱ)的净化模拟

在2007年8月研究的基础上,于2008年7月在神农架大九湖泥炭藓沼泽湿地采用自制简易模拟装置进行现场模拟实验,深入研究了泥炭藓沼泽湿地对不同浓度的金属污染物镉（Ⅱ）、铜（Ⅱ）、铅（Ⅱ）、锌（Ⅱ）的净化作用。研究表明：泥炭藓沼泽湿地对各种金属污染物都有很强的去除能力,2小时后的去除效果强弱顺序为Pb>Cu>Cd>Zn;4种金属任一时刻的去除速率都随初始浓度的增加而增大,低初始浓度先于高初始浓度达到平衡;泥炭藓沼泽湿地的稀释功能在污染物去除中起着重要作用。通过双常数速率模型得到了去除速率与实验时间的关系;拟二级动力学模型和修改后的拟一级动力学模型能够很好地描述泥炭藓沼泽湿地去除金属污染物的动态过程,拟二级动力学模型的拟合效果更佳,通过修改后的拟一级动力学模型可以计算出稀释作用对湿地净化的贡献率。为评估泥炭藓沼泽湿地净水价值、保护和合理利用泥炭藓沼泽湿地提供科学依据。     

Chemical transport models

Background, aim, and scope  Improving the parameterization of processes in the atmospheric boundary layer (ABL) and surface layer, in air quality and chemical transport models. To do so, an asymmetrical, convective, non-local scheme, with varying upward mixing rates is combined with the non-local, turbulent, kinetic energy scheme for vertical diffusion (COM). For designing it, a function depending on the dimensionless height to the power four in the ABL is suggested, which is empirically derived. Also, we suggested a new method for calculating the in-canopy resistance for dry deposition over a vegetated surface. Materials and methods  The upward mixing rate forming the surface layer is parameterized using the sensible heat flux and the friction and convective velocities. Upward mixing rates varying with height are scaled with an amount of turbulent kinetic energy in layer, while the downward mixing rates are derived from mass conservation. The vertical eddy diffusivity is parameterized using the mean turbulent velocity scale that is obtained by the vertical integration within the ABL. In-canopy resistance is calculated by integration of inverse turbulent transfer coefficient inside the canopy from the effective ground roughness length to the canopy source height and, further, from its the canopy height. Results  This combination of schemes provides a less rapid mass transport out of surface layer into other layers, during convective and non-convective periods, than other local and non-local schemes parameterizing mixing processes in the ABL. The suggested method for calculating the in-canopy resistance for calculating the dry deposition over a vegetated surface differs remarkably from the commonly used one, particularly over forest vegetation. Discussion  In this paper, we studied the performance of a non-local, turbulent, kinetic energy scheme for vertical diffusion combined with a non-local, convective mixing scheme with varying upward mixing in the atmospheric boundary layer (COM) and its impact on the concentration of pollutants calculated with chemical and air-quality models. In addition, this scheme was also compared with a commonly used, local, eddy-diffusivity scheme. Simulated concentrations of NO₂ by the COM scheme and new parameterization of the in-canopy resistance are closer to the observations when compared to those obtained from using the local eddy-diffusivity scheme. Conclusions  Concentrations calculated with the COM scheme and new parameterization of in-canopy resistance, are in general higher and closer to the observations than those obtained by the local, eddy-diffusivity scheme (on the order of 15–22%). Recommendations and perspectives  To examine the performance of the scheme, simulated and measured concentrations of a pollutant (NO₂) were compared for the years 1999 and 2002. The comparison was made for the entire domain used in simulations performed by the chemical European Monitoring and Evaluation Program Unified model (version UNI-ACID, rv2.0) where schemes were incorporated.     

UV-TiO_2光催化氧化降解双酚A的动力学研究

采用自制光催化氧化反应器,研究了双酚A(BPA)在纳米TiO_2悬浆体系中的光催化氧化特性.结果表明:(1)UV-TiO_2对水中BPA有较强光催化氧化降解作用.在10 W低压汞灯照射下,当纳米TiO_2用量为1.0 g/L、pH为5.5、BPA初始质量浓度为10 mg/L、曝气量为4.0 mL/min、温度为室温、反应时间为120 min时,BPA去除率可达97.1%.当pH≥9.5时,120 min后BPA已经基本光催化氧化降解完全.(2)BPA的光催化氧化降解曲线均很好地符合一级反应动力学方程.其速率常数与纳米TiO_2用量、pH、BPA初始浓度、曝气量有关;促进·OH和电子-空穴对的生成是提高光催化氧化反应速率的重要途径.     

城市生活垃圾典型组分的热解动力学分析

利用热分析仪对城市生活垃圾中典型组分的热解过程进行了热重分析实验,采用不同形式的反应机理函数对实验结果进行了线性拟合计算,得到了针对不同组分的最合理的反应机理函数形式,并求出了相应的反应活化能E及频率因子A,由此构建了能更准确地反映垃圾各组分的热解反应过程的动力学模型。计算结果表明,垃圾中多数组分的热解过程用扩散模型来表示最为合理。     

传感器布设中有效独立法的简捷快速算法

本文提出一个通过正交三角分解快速计算有效独立法系数的方法。有效独立法是传感器布设中影响最广泛的一种方法,它使目标模态尽可能线性独立。传统的有效独立法计算需要对信息阵进行特征值分解或者计算矩阵逆,计算量较大。本文在笔者以前得出的有效独立法与模态动能法关系的基础上,提出先通过对模态矩阵进行正交三角分解(QR),然后比较其行范数即可得到有效独立法的系数,进而对各待选传感器位置进行排序并迭代依次删除。在待选传感器位置比感兴趣的模态数较多时,该法的计算效率明显提高。同时,采用正交三角分解删除一行后的更新算法,进一步提高了迭代计算的效率。最后通过I-40桥的算例表明该法的有效性。     

异养硝化细菌Acinetobacter junii NP1的同步脱氮除磷特性及动力学分析

针对传统生物脱氮除磷过程存在工艺流程复杂、抗冲击负荷能力差、基建与运行费用高等问题,以具有高效脱氮除磷功能的异养硝化细菌Acinetobacter junii NP1为研究对象,开展其同步脱氮除磷性能、影响因子及动力学分析.结果表明,菌株NP1具有高效的异养硝化能力,氨氮最大去除率达99. 12%,反应过程只有少量的硝化中间产物积累,并且能够耐受较高的氨氮负荷.菌株NP1同时具有良好的好氧反硝化特性,能够利用亚硝酸盐和硝酸盐进行生长代谢,最大去除率分别为91. 40%和95. 10%.此外,菌株NP1异养硝化过程还伴随着同步的聚磷作用,适当的氮磷比有利于氮磷的同步去除,当氮磷比为5∶1时,最大氨氮和磷酸盐去除率分别为99. 21%和88. 35%.菌株NP1生长特性符合Logistic模型(R~2 0. 99),氮素和磷酸盐降解过程则与修饰的Compertz模型相匹配(R~2 0. 99),拟合所得氮和磷酸盐最大转化速率R_m为:氨氮硝氮亚硝氮,迟滞时间t_0为:硝氮亚硝氮氨氮.通过基质降解动力学以及氮磷去除率分析,最佳条件是碳源为琥珀酸钠、C/N=10、T=30℃以及r=160 r·min~(-1).     

不同施氮水平对再生水灌溉土壤释氮节律的影响

土壤供氮能力是影响土壤氮素利用效率的一个重要指标,再生水灌溉和施氮水平均影响着土壤供氮能力,研究不同施氮水平对长期再生水灌溉土壤氮素的转化特征可为合理施肥及农产品增产增效提供理论依据.本研究选择河南新乡洪门试验站温室大棚内长期再生水灌溉和清水灌溉土壤,试验共设8个处理:A(N200)(施氮量200 mg·kg-1)、A(N160)(施氮量160 mg·kg-1)、A(N140)(施氮量140 mg·kg-1)、A(N100)(施氮量100 mg·kg-1)、A(N0)(施氮量0 mg·kg-1)、E(清水灌溉常规施氮)、CK(清水灌溉不施氮)、Re CK(再生水灌溉不施氮),采用实验室内常温培养法,分别在培养的7、14、21、28、35、42 d测定土壤铵态氮、硝态氮及全氮含量,并分析了土壤氮素矿化量和氮素矿化速率的变化,通过Freundlich线性等温吸附模型及一级动力学方程拟合了土壤吸附参数Kd和氮素矿化势N0.结果发现,培养前期土壤氮素矿化较快,释放的氮量较高,中后期变化较慢,土壤供氮平稳,同一时段不同处理间土壤累积矿化氮量存在显著差异(p0.05),表明不同外源氮肥输入对土壤氮素的矿化能力影响显著,A(N160)处理的供氮能力最强;同时,在培养前期Re CK处理的土壤氮素矿化累积量显著高于CK处理,表明再生水灌溉较清水灌溉促进了土壤氮素的矿化,显著提高了土壤氮素活性;土壤氮素的矿化速率随着培养时间的增加而逐渐降低,但降幅依次减小并趋于平稳,且不同施氮处理再生水灌溉土壤氮素矿化速率显著高于清水灌溉;不同土壤肥力水平(B0)、外源施氮A(N160)调控,土壤氮素矿化潜势可表达为N0=B0+117.5072t-0.1062.因此,外源氮肥输入显著影响了土壤氮素释放节律,再生水灌溉辅以适宜的施氮量可促进土壤氮素矿化,提高土壤氮素活性.