Measurement of the pesticide methomyl by modified quartz crystal nanobalance with molecularly imprinted polymer

A simple and cost-effective analysis method based on quartz crystal nanobalance (QCN) coated with a molecularly imprinted polymer (MIP) for measurement of methomyl was investigated. In the first part of this study, a sensitive, selective and reliable quartz crystal nanobalance (QCN) sensor was designed for the selective determination of methomyl in aqueous solutions. In the second part, in order to demonstrate the applicability and performance of the fabricated sensor in the real world situation, it was successfully applied for the determination of methomyl residual in photo catalytic degradation by ZnO powders in aqueous solutions. The fabricated sensor presents a high selectivity and sensitivity (4.56 Hz per mg L^?1) for methomyl and it can be used for determination of methomyl concentration ranged between 1 to 45 mg L^?1. Furthermore, good reproducibility, R.S.D. = 2.14% (n = 5) was observed. To investigate the performance of the sensor, the change in the insecticide concentration during the photocatalytic degradation of methomyl by ZnO was investigated by QCN and UV/Vis spectroscopy. Results obtained from QCN sensor and UV/Vis spectroscopy measurement are in good mutual agreement. So the fabricated sensor may provide an efficient, low cost, easy-to-use method for the in-field evaluation of specific targeted analytes in aqueous solutions which in turn may lead to improved food and water safety.     

Control of aliphatic halogenated DBP precursors with multiple drinking water treatment processes: Formation potential and integrated toxicity

The comprehensive control efficiency for the formation potentials(FPs) of a range of regulated and unregulated halogenated disinfection by-products(DBPs)(including carbonaceous DBPs(C-DBPs), nitrogenous DBPs(N-DBPs), and iodinated DBPs(I-DBPs)) with the multiple drinking water treatment processes, including pre-ozonation, conventional treatment(coagulation–sedimentation, pre-sand filtration), ozone-biological activated carbon(O_3-BAC) advanced treatment, and post-sand filtration, was investigated. The potential toxic risks of DBPs by combing their FPs and toxicity values were also evaluated.The results showed that the multiple drinking water treatment processes had superior performance in removing organic/inorganic precursors and reducing the formation of a range of halogenated DBPs. Therein, ozonation significantly removed bromide and iodide,and thus reduced the formation of brominated and iodinated DBPs. The removal of organic carbon and nitrogen precursors by the conventional treatment processes was substantially improved by O_3-BAC advanced treatment, and thus prevented the formation of chlorinated C-DBPs and N-DBPs. However, BAC filtration leads to the increased formation of brominated C-DBPs and N-DBPs due to the increase of bromide/DOC and bromide/DON.After the whole multiple treatment processes, the rank order for integrated toxic risk values caused by these halogenated DBPs was haloacetonitriles(HANs)》haloacetamides(HAMs) haloacetic acids(HAAs) trihalomethanes(THMs) halonitromethanes(HNMs) 》I-DBPs(I-HAMs and I-THMs). I-DBPs failed to cause high integrated toxic risk because of their very low FPs. The significant higher integrated toxic risk value caused by HANs than other halogenated DBPs cannot be ignored.     

焙烧温度对CeO_2(ZrO_2)/TiO_2选择性催化脱硝性能的影响

采用溶胶-凝胶法并以不同温度焙烧制备一系列CeO_2(ZrO_2)/TiO_2(CZT)催化剂,考察了CZT催化剂固相结构、酸量、比表面积等性能与催化活性的关系。采用XRD、BET、NH3-TPD、H2-TPR以及XPS等表征技术对催化剂进行表征。结果表明:焙烧温度为450℃时CZT催化剂具有最高的催化活性,其在240~400℃的温度窗口内活性均高于90%,且具有较好的抗水和抗硫中毒能力。随着焙烧温度的提高,催化剂表面的Ce和Zr原子进入体相晶格且Ce0.5Zr0.5O2向Ce0.75Zr0.25O2转变,导致催化剂的储释氧能力和氧化还原性能降低。另外,锐钛矿和金红石型TiO_2晶粒尺寸的增加,催化剂的有效比表面积和总酸量降低,因此CZT催化活性随着焙烧温度的提高而有所降低。换言之,大的比表面积、良好的氧化还原性能、表面Ce4+的富集以及酸性位的增多均有利于NH3-SCR活性的提高。     

Effects of sludge retention time, carbon and initial biomass concentrations on selection process: From activated sludge to polyhydroxyalkanoate accumulating cultures

Four sequence batch reactors (SBRs) fed by fermented sugar cane wastewater were continuously operated under the aerobic dynamic feeding (ADF) mode with different configurations of sludge retention time (SRT), carbon and initial biomass concentrations to enrich polyhydroxyalkanoate (PHA) accumulating mixed microbial cultures (MMCs) from municipal activated sludge. The stability of SBRs was investigated besides the enrichment performance. The microbial community structures of the enriched MMCs were analyzed using terminal restriction fragment length polymorphism (T-RFLP). The optimum operating conditions for the enrichment process were: SRT of 5 days, carbon concentration of 2.52 g COD/L and initial biomass concentration of 3.65 g/L. The best enrichment performance in terms of both operating stability and PHA storage ability of enriched cultures (with the maximum PHA content and PHA storage yield (Y_PHA/S) of 61.26% and 0.68 mg COD/mg COD, respectively) was achieved under this condition. Effects of the SRT, carbon concentration and initial biomass concentration on the PHA accumulating MMCs selection process were discussed respectively. A new model including the segmentation of the enrichment process and the effects of SRT on each phase was proposed.     

基于GIS和RS的市域尺度下的植被NPP研究

在GIS和RS支持下,利用土地利用类型数据、地面气象数据和遥感影像数据,以青岛市为例,研究了市域尺度下的植被NPP空间分布特征.结果表明:青岛市NPP值为0~288 g·m-2·a-2,林地NPP值较高,耕地次之,建成区等区域最小.在小尺度区域内,NPP分布受土地利用类型影响较大,受气象因素影响较小.NPP模块在数据获取上比较容易,仅利用土地利用类型数据、地面气象数据和遥感数据就可以对陆地植被NPP进行计算,实际应用可操作性强.30 m分辨率植被NPP计算值更适宜于在市级小尺度区域内应用.     

厌氧-准好氧联合型生物反应器填埋场产气规律的研究

通过将厌氧型生物反应器填埋场（ANBL）和准好氧矿化垃圾生物反应床（SAARB）串联,组成新型的厌氧-准好氧联合型生物反应器填埋场（AN-SABL）,研究其产气速率、产气量以及产气组分的变化规律,以期为填埋气体的收集、利用和处理提供理论依据.实验表明,AN-SABL中的厌氧填埋单元的产气受到了抑制,其中ANBL2号单元和ANBL3号单元的产气率分别为49 L.kg-1和39 L.kg-1,仅占ANBL1号的94.2%和75.0%,但提高回灌频率,能促进厌氧填埋单元的产气,其甲烷含量最大值可达到62.67%;ANBL夏季产气速率和产气量明显高于冬季,并以12 h为周期交替出现产气高峰;此外,AN-SABL能够促进其厌氧单元的硝化和反硝化作用,N2O的含量受季节和填埋场类型影响显著,其变化范围在0.001 7%～4.017 9%之间.ANBL的累积产气量在初始调整阶段呈对数增长,过渡酸化阶段呈线性增长,酸化产甲烷阶段呈指数增长.     

氨对垃圾焚烧飞灰浸出特性的影响及地球化学模拟

垃圾焚烧飞灰可能因为选择性非催化还原法(SNCR)脱硝过程中氨泄漏、垃圾携带的渗滤液受热挥发等原因而吸附氨.本研究中采用人为添加氨水,在pH为3.66～12.44范围内,研究氨对飞灰中溶解性有机碳(DOC)和重金属浸出的影响,并利用地球化学模拟软件Visual MINTEQ从金属化学形态分布上分析氨对飞灰浸出的影响机制.结果表明,DOC在pH>9和有高浓度氨(≥1 357 mg·L-1)存在时,其浸出量大幅增加,而在浸出液中氨的水平不高于537 mg·L-1时则受氨的影响很小;在pH<6时,飞灰中各金属主要以自由态的金属离子和金属-氯络离子形态大量溶出,且受氨的影响较小;而在pH为8～12的碱性环境中和氨浓度较高时(≥3 253 mg·L-1),氨与金属生成了可溶性的金属-氨配合物,能显著增加Cd、Cu、Ni、Zn的浸出,且在pH=9附近时浸出量达到最大值,但氨对Al和Pb的浸出影响甚微;在pH>12时,Cd、Cu、Ni、Zn主要以羟基金属离子形式存在.在氨浓度为3 253 mg·L-1时,通过利用Visual MINTEQ模拟浸出值与试验数据的对比,发现Al、Pb、Zn的浸出主要由溶解/沉淀模型控制,而Cd、Cu、Ni由溶解/沉淀模型和表面吸附反应模型同时控制,且Visual MINTEQ模型能较好地预测飞灰中Al、Cu、Pb、Zn的浸出特性.     

Simultaneous preconcentration of cadmium and lead in water samples with silica gel and determination by flame atomic absorption spectrometry

A new method that utilizes pretreated silica gel as an adsorbent has been developed for simultaneous preconcentration of trace Cd(II) and Pb(II) prior to the measurement by flame atomic absorption spectrometry. The effects of pH, the shaking time, the elution condition and the coexisting ions on the separation/preconcentration conditions of analytes were investigated. Under optimized conditions, the static adsorption capacity of Cd(II) and Pb(II) were 45.5 and 27.1mg/g, the relative standard deviations were 3.2% and 1.7% (for n = 11), and the limits of detection obtained were 4.25 and 0.60 ng/mL, respectively. The method was validated by analyzing the certified reference materials GBW 07304a (stream sediment) and successfully applied to the analysis of various treated wastewater samples with satisfactory results.     

Application of CGP-cross route process for microstructure refinement and mechanical properties improvement in steel sheets

A modified method of severe plastic deformation (SPD) entitled constrained groove pressing-cross route (CGP-CR) was introduced for imposing a high magnitude of equivalent strain of about 2.32 per pass on the sheet form samples. The major benefit of this improved route compared to previous common route was the more homogeneity of strain in the rolling (RD) and transverse (TD) directions of sheets. In this study, low carbon steel samples were used for examination of evolutions in microstructure and mechanical properties during SPD via CGP-CR process. Mechanical properties improvement were measured by tensile and macro hardness tests. The results indicate that CGP-CR process can effectively improve tensile strength; and also, yield stress and hardness of as-received low carbon steel samples were improved up to about 100% after two deformation passes. Also, high magnitude of inhomogeneity can be observed in hardness distribution through first pass of the process which diminishes in the subsequent passes. Microstructural evolutions during process were monitored by optical microscopy observations and X-ray diffraction analysis. The results demonstrate that initial ferritic microstructure with grain size of about 30 μm was refined to a 225 nm cell structure after two passes of CGP-CR process.