Sample preparation followed by high performance liquid chromatographic (HPLC) analysis for monitoring muconic acid as a biomarker of occupational exposure to benzene.

Factors affecting solid phase extraction (SPE) of trans,trans-muconic acid (ttMA), as a benzene biomarker, including sample pH, sample concentration, sample volume, sample flow rate, washing solvent, elution solvent, and type of sorbent were evaluated. Extracted samples were determined by HPLC-UV (high performance liquid chromatography-ultraviolet). The analytical column was C18, UV wave length was 259 nm, and the mobile phase was H(2)O/methanol/acetic acid run at flow rate of 1 ml/min. A strong anion exchange silica cartridge was found successful in simplifying SPE. There was a significant difference between recoveries of ttMA when different factors were used (p < .001). An optimum recovery was obtained when sample pH was adjusted at 7. There was no significant difference when different sample concentrations were used (p > .05). The optimized method was then validated with 3 different pools of samples showing good reproducibility over 6 consecutive days and 6 within-day experiments.     

Sample Preparation Followed by High Performance Liquid Chromatographic (HPLC) Analysis for Monitoring Muconic Acid as a Biomarker of Occupational Exposure to Benzene

Factors affecting solid phase extraction (SPE) of trans,trans-muconic acid (ttMA), as a benzene biomarker, including sample pH, sample concentration, sample volume, sample flow rate, washing solvent, elution solvent, and type of sorbent were evaluated. Extracted samples were determined by HPLC-UV(highperformance liquid chromatography-ultraviolet). The analytical column was C18, UV wave length was 259 nm, and the mobile phase was H2O/methanol/acetic acid run at flow rate of 1 ml/min. A strong anion exchange silica cartridge was found successful in simplifying SPE. There was a significant difference between recoveries of ttMA when different factors were used (p < .001). An optimum recovery was obtained when sample pH was adjusted at 7. There was no significant difference when different sample concentrations were used (p > .05). The optimized method was then validated with 3 different pools of samples showing good reproducibility over 6 consecutive days and 6 within-day experiments.     

Optimization of Headspace Solid Phase Microextraction Procedure for Trace Analysis of Toluene

This study describes optimization of headspace solid phase microextraction followed by gas chromatography equipped with a flame ionization detector for toluene at trace level in spiked urine. The parameters affecting the extraction and gas chromatographic determination of analytes were studied: extraction time and temperature; desorption time and temperature; addition of NaCl; and pH, volume and agitation of the sample. Optimized headspace extraction was carried out at 30 °C for 6 min in the presence of 0.2 g-m^-1of NaCl in the sample solution. Also, sample volume and sample pH were optimized at 5 ml and 7 (neutral pH), respectively. Desorption of the analytes was carried out at 250 °C for 60 s. The optimized procedure was validated with 3 different pools of spiked urine; it showed good reproducibility over 6 consecutive days and 6 within-day experiments. The study also determined the accuracy, linearity and detection limits of this method.     

畜牧业污水中大环内酯和拟除虫菊酯类驱虫剂物质的LCMSMS检测

采用无需衍生化的同相萃取为前处理手段,高效液相色谱-串联四极杆质谱联用技术(LCMSMS)为检测手段,在电喷雾电离正离子模式下,对澳大利亚畜牧业污水中常见的大环内酯和拟除虫菊酯两类共7种驱虫剂物质的残留,建立了一次进样下的有效快速分析方法.经一系列优化试验,确定了以50%丙酮+50%乙腈为洗提剂、每次4 mL共8 mL的洗提方法.结果表明,该固相萃取技术(SPE)的加标回收试验结果较好,各化合物的平均回收率为95.50%～108.00%,相对标准差范围为0.73%-8.82%.以含10mmoL/L醋酸铵、0.1%甲酸的超纯水和甲醇混合溶液为流动相,以准分子离子峰[M+NH_4]~+、[M+H]~+作为母离子的定量离子对,所建立的1～500 ng/mL范围内的8点校正曲线中.各物质的相关系数均高于0.998 0,定量限范围为0.03-2.47 ng/mL.实际样品测定时.不同处理流程中各化合物的残留浓度有较好地体现.     

环氧丙烷在不同条件下的反应稳定性研究

环氧丙烷具有较强化学活性,分析了环氧丙烷生产过程中可能出现的安全问题;测试了不同温度、pH值和铁离子存在条件下环氧丙烷的反应稳定性。结果表明,环氧丙烷在低pH值和铁离子存在的环境中容易发生强烈放热反应。根据环氧丙烷工业化生产的特点,提出了相应的控制条件。     

用盐桥支撑双分子层脂膜模拟研究锌离子跨细胞膜输运

采用盐桥支撑技术制备镶嵌胆固醇的双分子层卵磷脂(脑磷脂)膜,用以模拟细胞膜.用正辛烷做溶剂,对不同卵磷脂(脑磷脂)与胆固醇配比进行制膜,膜的稳定性均超过100h.实验发现,纯脂质体不能输运重金属离子,胆固醇能输运重金属离子.胆固醇与重金属离子之间存在吸附作用,无化学反应.采用电化学工作站对双分子层脂膜的稳定性、离子通透性、双层膜中胆固醇对离子通透性的影响等进行了研究,并利用实验制备的双分子层脂膜模拟研究锌离子跨细胞膜的输运过程,建立了锌离子跨细胞膜的吸附-扩散模型,该模型计算值与实验值基本吻合.     

磷矿浆催化氧化湿法脱硝研究

采用液相催化氧化NO_x的方法,通过磷矿浆中过渡金属离子的催化作用,达到净化电厂烟气中NO的目的。考察了烟气含氧量、吸收温度、磷矿浆固液比及气体流量对磷矿浆湿法脱硝的影响。结果表明,试验最佳条件为NO进口质量浓度670 mg/m~3、磷矿浆吸收温度25℃、固液比500 g/L、流量0.3 L/min、含氧量20%;优化条件下的磷矿浆脱除效率最高可达88.9%。随着磷矿浆湿法催化氧化脱硝反应的进行,p H值不断下降,导致磷矿浆逐渐失效,需补入新鲜矿浆,维持吸收液的p H值以保证良好脱硝率。     

固体高分子膜电解法(SPE)处理苯并红紫4B废水的研究

采用固体高分子膜作隔膜,以Pt网上附着的β-PbO2作催化剂,建立了一个高效的催化电解装置(SPE).用此装置处理难降解的苯并红紫4B模拟染料废水,苯并红紫4B的质量浓度为0.1 g/L.结果表明,此法对苯并红紫4B废水的色度和TOC具有良好的去除效果,催化电解过程中产生的原子氢对染料分子中发色键的破坏起决定性作用,当电流密度为0.24 A/era2、电压为3.9 V时,对染料苯并红紫废水,处理120min后,废水的色度明显下降,由处理前的红色变为几乎无色,TOC的去除率为42%,SO42-的生成率为78%.催化电解是染料废水绿色降解的重要途径之一.     

金属网篮交叉点法预测烟草的临界自燃条件

使用金属网篮模拟了小尺寸的烟草热自燃实验,利用交叉点法测量自热过程烟草内部温度数据并求解反应动力学参数,根据求解所得动力学参数成功预测了大尺寸情况下堆积烟草的热自燃临界条件,得到烟草贮存的临界堆积厚度与临界环境温度之间的函数关系,为烟草的安全存贮提供方法指导。     

Preparation of Co–MgO mixed oxide nanocatalysts for low temperature CO oxidation: Optimization of preparation conditions

In this study, a series of Co–MgO mixed oxides (30 wt.% Co) were prepared by co-precipitation method and employed as catalyst in low temperature CO oxidation reaction. The preparation conditions were optimized by the Taguchi method of experimental design to synthesize a sample with high catalytic performance toward CO oxidation reaction. The effects of four variables, pH of solution, aging temperature, aging time and molarity of precursor solution at three levels were investigated. The optimized sample was characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of oxygen (O₂-TPD), N₂ adsorption/desorption, thermal gravimetric and differential thermal analysis (TGA/DTA), and transmission electron microscopy (TEM) techniques. The results revealed that the optimized sample showed a mesoporous structure with a narrow pore size distribution centered in the range of 7–17 nm and particle size about 5.5 nm. It was found that the molarity of solution and aging time had the most influence on the CO conversion, respectively. The catalytic results showed that the highest CO conversion obtained from samples synthesized by Taguchi orthogonal array was about 90% at 200 °C, while the CO conversion for optimized sample was 95%. In addition, the effect of operational conditions was studied over optimized sample.     

Fisher法在土壤污染综合评价优化布点中的应用

根据Fisher最优分割的理论,研究其应用于土壤环境监测优化布点的可行性。以福建省闽江河口湿地土壤重金属污染综合评价为实例,用Fisher法计算不同分类方式下的最小误差函数,确定最优的分割方法,确定优化布点方案。结果表明,原布设的8个监测点用Fisher法优化为3个典型点位,可客观反映闽江河口湿地土壤重金属污染的综合评价结果。     

Simultaneous photocatalytic treatment of Cr(VI), Ni(II) and SDBS in aqueous solutions: Evaluation of removal efficiency and energy consumption

Simultaneous photocatalytic reduction of poisonous Cr(VI) and Ni(II) ions, coupled with photocatalytic oxidation of sodium dodecyl benzene sulfonate (SDBS) were studied with a trace amount of commercial titania nanoparticles and by means of a direct-photo-irradiation reactor. The co-presence of metal ions and SDBS causes metal ions reduction as well as SDBS oxidation to enhance and energy efficiency to improve. XRD, XPS and FTIR analysis were used to characterize TiO₂ particles before and after usage with the aim of evaluating the mechanism of reactions. The effect of major operating parameters, pH and temperature, was investigated. Under conditions of [Cr(VI)]₀ = [Ni(II)]₀ = 5 mg/L, [SDBS]₀ = 10 mg/L, [TiO₂] = 40 mg/L, pH 6 and T = 35 °C; the removal efficiencies of 55.4%, 71.2% and 57.2% were obtained, respectively, for Cr(VI) and Ni(II) reduction, as well as for SDBS oxidation, after 110 min operation. The relevant kinetic model jointed with the Arrhenius equation was introduced. Pseudo-first-order reactions are relevant. Energy consumption (electrical and thermal) evaluations revealed that operations at higher temperatures provide significant cost reduction. Meantime, a criterion was proposed for a consistent assessment of this kind of processes.     

Self-ignition of dust at reduced volume fractions of ambient oxygen

Experiments were performed to investigate the self-ignition behaviour of accumulations of four different technical dusts at oxygen volume fractions ranging from 1.3 to 21%. For this purpose a laboratory oven used for hot storage testing was modified to allow flushing with the pre-mixed oxygen/nitrogen mixture of the desired composition. It was found that for all sample volumes investigated the self-ignition temperatures were higher the lower was the oxygen volume fraction. In addition, the type of reaction changed obviously, since the apparent activation energy significantly decreased at oxygen volume fractions below 6%. However, it was still possible to observe exothermic effects at oxygen volume fractions as low as 1.3%. A numerical model was established to simulate the process of self-ignition including the coupled heat and mass transfer within the dust accumulation using a finite element solver. The model consists of six balance equations for the heat transfer and the transport of five chemical species. It shows that the model reflects self-ignition in dust accumulations with satisfying accuracy, as long as the input data generated by preceding experiments are reliable.     

不同类型活性炭处理废水中重金属离子的研究进展

重金属对人体的显著毒性和难降解的特性,使重金属水体污染成为全球性关注的环境问题。本文综述了重金属废水的危害、来源及常用处理方法,比较了不同类型活性炭处理废水中重金属离子的差异,阐述了不同类型活性炭处理技术的优势和特点,并对今后的重金属废水处理技术研究方向进行了展望。     

Effects of metal ions on thermal hazard of tert-butyl peroxy-3,5,5-trimethylhexanoate

As a commonly used initiator for polyethylene, tert-butyl peroxide 3,5,5-trimethylhexanoate (TBPTMH), with the molecular formula of C₁₃H₂₆O₃, is more likely to decompose and cause fires and explosions. Understanding the thermal risks of TBPTMH mixed with common metal ions, potentially in containers and pipes, is important. In this work, by using differential scanning calorimetry (DSC) and Phi-Tec adiabatic calorimetry, the effects of CuCl₂, FeCl₃, CuBr_2, and FeBr₃ on the thermal decomposition of TBPTMH were investigated. Adiabatic kinetic analysis was performed and the apparent activation energy (E_a) was calculated by thermodynamic analysis. Time to maximum rise under adiabatic conditions (TMR_ad) and the self-accelerating decomposition temperature (SADT) under different packing qualities were reckoned. It was found that the thermal risk of TBPTMH was increased while mixing these metal ions, especially CuBr₂. To ensure the safety of the substance in process industry, the temperature of TBPTMH in the presence of metal should be governed below 39.48 °C. This work was expected to provide some guidance for improving the process safety of TBPTMH.     

铂载钴钼二元硫化物对H_2S电催化活性研究

为考察溶胶凝胶法制备的Co-Mo二元硫化物对H_2S气体的电催化活性,通过循环伏安法和Tafel曲线分析对铂载不同Co、Mo掺杂比的电催化剂进行表征.结果表明,不同阳极电催化剂交换电流密度J_0由大到小依次为,铂载n(Co):n(Mo)=2:3、铂载n(Co):n(Mo)=2:1、铂载n(Co):n(Mo)=1:1和铂,即铂载n(Co):n(Mo)=2:3阳极电催化剂具有较好的活性,这与循环伏安曲线测试结果一致.电解质溶液pH值为6～7时,随着温度的升高铂载n(co):n(Mo)=2:3阳极电催化剂活性呈现上升的趋势.优化后的Co、Mo掺杂原子比约为0.66,此类电催化剂在操作温度80℃下,交换电流密度为1.318mA/cm~2,表观活化焙值为616.6 kJ/mol .研究表明,铂载钴钼二元硫化物适合作为低温H_2S燃料电池阳极电催化剂,其中Co、Mo掺杂比对电催化活性影响较大.     

磷灰石在废水治理中的应用

由于具有特殊的晶体化学特点，天然磷灰石可以作为一种新型环境功能矿物材料用于对含重金属废水的处理。对Cd^2 ,Pb^2 ,Fe^2 ,[UO2]^2 ,Cu^2 ,Zn^2 ,Cr^6 ,和Hg^2 等离子的吸附实验结果表明，磷灰石对绝大多数重金属离子去除效果很好。在室温和pH为3、作用时间为60min的实验条件下，Pb^2 去除率可达99．4％，饱和吸附容量超过1100mg/g。主要的去除机理包括吸附、表面络合、溶解－沉淀以及重金属离子与晶格中之间的离子交换作用。一般而言，被吸附的重金属离子可固化在晶格中而不出现解吸，因此不会产生二次污染。影响去除效果的因素包括磷矿石的类型、磷灰石的矿物成分、介质pH值、温度、吸附时间、离子的初始浓度、样品的粒度和用量等。通常，羟基磷灰石的效果优于氟磷灰石的，硅质磷块岩的效果优于钙质磷块岩的，结构碳酸根的存在能量增加比表面积从而增加反应活性。对于不同离子，最佳pH值条件不同。温度的升高有利于反应的快速进行，但一般地说60－180min即可达到平衡。     

尼龙6纳米纤维膜富集/固相表面荧光法快速检测水体痕量多环芳烃研究

以静电纺丝法自制的尼龙6纳米纤维膜为吸附材料,建立了快速测定水体痕量多环芳烃(PAHs)的固相表面荧光光谱法(SSF)。将直径为5 cm的尼龙6纳米纤维膜作为滤膜用于抽滤菲、芘、荧蒽的水溶液,将膜自然晾干后置于可变角粉末样品池上,利用荧光分光光度计测量膜表面PAHs的三维固相表面荧光光谱特征,确定最佳激发发射波长,考察荧光强度随溶液初始质量浓度的线性变化关系。结果表明,菲、芘、荧蒽的最大激发发射荧光中心分别位于Ex/Em=255nm/368 nm、Ex/Em=340 nm/376 nm和Ex/Em=290 nm/437 nm处。当抽滤水样体积为500 m L时,菲、芘、荧蒽荧光强度与初始质量浓度之间的标准曲线分别为y=9432.4x+261.1,线性范围为5~500ng/m L;y=753480x+805.51,线性范围为0.2~10 ng/m L;y=9946.06x+603.48,线性范围为10~400 ng/m L,检出限分别为0.973 ng/m L、0.016 2 ng/m L和0.089 6 ng/m L。当质量浓度分别为100 ng/m L、10ng/m L和50 ng/m L时,7次测量的相对标准偏差(RSD)分别为7.1%、2.6%和5.1%,平均值相对误差分别为1%、2%和-0.2%。自来水低中高3个质量浓度的平均加标回收率分别为87.2%~98.2%、101%~120%、85.8%~92.3%。本方法具有简便、经济、灵敏度高等优点,适合于水体痕量PAHs的快速测定。     

数值模拟方法在壁面烧损痕迹的应用

本文作者对FDS源程序进行了改进，并利用改进后程序计算火灾过程中壁面热解形成图痕，作为火灾调查的方法之一，初步分析壁面烧损痕迹发展特征。该方法可以根据火灾场景、壁面材料、起火点功率的不同计算研究壁面燃烧痕迹形成规律，并提出使用该方法对火灾调查提供理论依据的可行性和重大意义。     

基于灰色神经网络优化组合模型的火灾预测研究

为了提高火灾事故预测的精度,根据我国火灾事故数据样本较小,波动性较大的特点,将遗传算法优化的灰色无偏预测模型与遗传算法优化的BP神经网络模型结合起来,建立灰色神经网络优化组合模型,充分发挥无偏灰色预测模型适用于小样本的数据预测的优势与BP神经网络处理非线性问题的优点。分别采用遗传算法优化后的无偏灰色GM（1,1）模型、遗传算法优化的BP神经网络预测模型与灰色神经网络优化组合模型对我国1998-2008年的火灾事故进行拟合,并对2009-2011年的火灾事故发生数进行预测。结果表明:灰色神经网络优化组合模型的预测误差最小,精度最高,适用于火灾事故的预测。