The use of trichloroacetic acid imprinted polymer coated quartz crystal microbalance as a screening method for determination of haloacetic acids in drinking water

An alternative screening method for haloacetic acids (HAAs) disinfection by-products in drinking water is described. The method is based on the use of piezoelectric quartz crystal microbalance (QCM) transducing system, where the electrode is coated with a trichloacetic acid-molecularly imprinted polymer (TCAA-MIP). This MIP comprises a crosslinked poly(ethyleneglycoldimethacrylate-co-4-vinylpyridine). The coated QCM is able to specifically detect the analytes in water samples in terms of the mass change in relation to acid-base interactions of the analytes with the MIP. The TCAA-MIP coated QCM showed high specificity for the determination of TCAA in aqueous solutions containing inorganic anions, but its sensitivity reduced in water samples containing hydrochloric acid due to a mass loss at the sensor surface. Cross-reactivity studies with HAA analogs (dichloro-, monochloro-, tribromo-, dibromo-, and monobromo-acetic acids) and non-structurally related TCAA molecules (acetic acid and malonic acid) indicated that recognition of the structurally related TCAA compounds by the TCAA-MIP-based QCM is due to a carboxylic acid functional group, and probably involves a combination of both size and shape selectivity. The total response time of sensor is in the order of 10 min. The achieved limits of detection for HAAs (20-50 μg l⁻¹) are at present higher than the actual concentrations found in real-life samples, but below the guidelines for the maximum permissible levels (60 μg l⁻¹ for mixed HAAs). Recovery studies with drinking water samples spiked with TCAA or spiked with mixtures of HAAs revealed the reproducibility and precision of the method. The present work has demonstrated that the proposed assay can be a fast, reliable and inexpensive screening method for HAA contaminants in water samples, but further refinement is required to improve the limits of detection.     

Temperature and pressure effects on zeta potential values of reservoir minerals

An experimental study of the effect of temperature and pressure on zeta potential of typical reservoir minerals, including quartz, kaolinite, and calcite, is presented. Experiments included the design and construction of an electrophoretic cell for zeta potential measurements at variable pressure and temperature. Electrolyte concentration was varied in the range from 0.0001 to 0.1 M in the pH range from 2 to 9. For all the minerals it is found that the zeta potential decreases with temperature at a rate characteristic of each mineral; values are around -2.3 mV/degrees C for quartz, -0.96 mV/degrees C for kaolinite, and -2.1 mV/degrees C for calcite for pressure values less than 45 psi. The effect of pressure is found to depend on the mineral nature and pH of the electrolytic solution. In the case of quartz, a systematic increase in the value of the zeta potential with pressure is observed, whereas a decreasing trend is measured for the kaolinite. In the case of calcite, a decreasing trend is observed for pressures up to 45 psi, whereas the experimental data suggest an increasing trend for higher pressure values.     

石英晶体微天平用于微囊藻毒素在聚合物涂覆的金片表面吸附

合成了具有不同功能化的聚苯乙烯树脂,利用石英晶体微天平对树脂和微囊藻毒素相互吸附作用进行实时监测和研究．研究发现,吸附的pH和表面性质对于吸附量有重要的影响,而温度影响不大,中性pH氨基树脂对微囊藻毒素的吸附效果最好.     

石英粉/磷酸盐缓冲溶液体系中羟自由基荧光分光光度法定量检测研究

为了定量检测石英粉/磷酸盐缓冲溶液体系中极低浓度的羟自由基(·OH),依据对苯二甲酸(TA)在pH中性的缓冲溶液中与羟自由基反应生成唯一稳定且具有很强荧光特性的产物即2-羟基对苯二甲酸(HOTP),本文建立了滤液最大激发/发射波长EX_max/EM_max=316 nm/422 nm处的荧光强度与HOTP浓度关系的标准曲线,通过检测石英粉与缓冲溶液作用之后滤液的荧光强度,从而间接测定了体系产生的·OH累积浓度。通过重复试验并分析五个不同实验条件下体系产生的·OH累积浓度,最小检出限达到1.59×10-10 mol·L-1,相对偏差为1.20%~7.89%,标准偏差为1.09×10-9~2.17×10-9 mol·L-1,相对标准偏差为3.5%~5.8%,说明该方法具有较高的精确度和较好的重复性。该方法可用于定量检测pH中性溶液中极低浓度的·OH,与其他方法相比,具有明显的检测限低、成本低、灵敏度高、稳定性和重现性好等优势。     

钙长石质玉中钙铬榴石的谱学研究

所研究钙长石质玉中的绿色矿物是以钙铬榴石为主的石榴石,钙铬榴石在天然条件下非常稀有,颜色为翠绿色,品质高的钙铬榴石可与翡翠、祖母绿相媲美。前人对石榴石系列的其他端元矿物具有较为充分的研究,但对钙铬榴石的研究较少,且未见对钙长石质玉中钙铬榴石光谱特征的相关报道。使用JXA-8230电子探针确定样品石榴石平均组分为Uvt_49.66Grs_36.04Adr_13.58Pr_p0.67Sps_0.06,为以钙铬榴石为主的钙系石榴石。经Bruker Senterra R200L拉曼光谱仪测定样品拉曼位移为1 000,890,879,830,618,589,530,508,399,370,270,240和176 cm-1,受不同三价阳离子Cr3+,Al3+和Fe3+替代的相互影响而发生相应的偏移;用Bruker Vertex80红外光谱仪测定样品红外振动频率为1 019,951,908,844,826,721,669,608,538,496,462,430和413 cm-1,受不同组分晶胞体积及三价阳离子的质量分数影响,发生规律性振动偏移;通过Jasco MSV-5200显微紫外-可见光谱仪及近红外分光光度计测定样品,可见区Cr3+宽吸收带为439和613nm,存在453和685 nm吸收肩峰,同时可见Fe3+ 371 nm吸收肩峰,钙铬榴石主要致色离子为Cr3+。钙长石质玉中钙铬榴石的详细谱学研究为稀有钙铬榴石矿物的鉴定提供了丰富的谱学数据,为相似品独山玉进行区分奠定基础。     

浙江三个新石器时代遗址出土玉玦科技分析

玉玦是我国新石器时代广泛出现的一类重要玉器。环太湖流域新石器时代遗址中出土的大量玉玦,具有鲜明时代和地域特征,为探索中国玉文化起源和传播提供了重要实物。为获取环太湖流域新石器时代玉玦的基础材料学信息(如主要矿物组成、硬度等),以及探索玉料随时间演变规律和可能的原料来源,本文以浙江省境内3个代表性新石器时代遗址--田螺山、仙坛庙和江家山遗址出土的玉玦为研究对象,采用X射线衍射(XRD)和质子激发X射线荧光(PIXE)分析技术对其进行了无损分析检测。研究结果表明： 从河姆渡文化至崧泽文化晚期,所分析玉玦的主要组成矿物为萤石、迪开石、石英、白云母、透闪石和蛇纹石等,以萤石、玉髓和迪开石为主,且时代早于透闪石和蛇纹石。结合已有的研究成果,探讨了相关遗址出土玉玦的原料随时间变化特征、原料来源,以及玉玦的材料学特征与加工工艺之间的内在联系。     

The dependence of quartz OSL on stimulation energy

Quartz is the mineral most commonly used for sediment dating. In dating practice, the optically stimulated luminescence (OSL) of quartz is measured mainly using the stimulation light whose wavelength is 470 ± 30 nm. The parameters of traps active in the OSL process are also determined for this stimulation band. The zeroing of the OSL is the fundamental condition of applicability of the luminescence dating for specific sediment and takes place in sunlight whose spectrum differs significantly from the band 470 ± 30 nm. In order to be able to know the course of OSL process in nature, a wider knowledge of the dependency of the trap parameters on the stimulation band is needed. Here the results are presented for the OSL measurements carried out with different wavelengths of stimulation light. For each stimulation band the components of the OSL signal are determined by the fitting procedure, and in this way the wavelength dependence of an individual component is found. The experiment has been repeated for two temperatures of OSL detection – the room temperature, which corresponds to natural conditions, and for 125 °C, which is the temperature usually applied for OSL measurement in dating. Four OSL components are presented in both experimental series. The values of their optical cross-section changes along with stimulation energy and temperature, as it is predicted by the model of OSL process including crystal lattice vibrations.     

汶川地震断裂带岩脉矿物拉曼谱峰特征

对汶川地震断裂带深溪沟出露的基岩错动面两侧岩脉中的石英矿物进行了拉曼谱峰测定, 并根据所测石英的464 cm-1拉曼谱峰向高波数的偏移量估算了断裂带中的压应力分布。测试结果表明, 错动面附近岩脉中石英的464 cm-1拉曼谱峰向高波数偏移量为3.29 cm-1, 相应的压应力值为368.63 MPa, 明显低于错动面两侧应力积累, 这可能是由于错动面的多次活动导致了应力不断得到释放。断裂南东盘(下盘)远离错动面, 岩脉中石英的464 cm-1拉曼谱峰向高波数偏移量具有增加的趋势, 相应的应力积累也逐渐增强, 距错动面21 m处的石英样品的464 cm-1拉曼谱峰向高波数偏移4.40 cm-1, 相应压应力可达到494.77 MPa。剖面北西盘(上盘)在距错动面10 m处, 样品464 cm-1拉曼谱峰的偏移量达到最大值, 相应的应力积累为519.87 MPa, 其后远离错动面应力积累开始减弱, 在北西盘17 m处, 应力积累骤然下降至400.37 MPa。在西北盘距错动面27 m处, 岩脉石英的464 cm-1拉曼谱峰向高波数偏移量下降至3.21 cm-1, 应力已经减弱到359.59 MPa, 这可能是由于该处位于断裂带的边缘, 远离错动面, 受到了较小的断层活动的影响。因此, 汶川地震断裂带内的应力虽然得到部分释放, 但剩余的应力分布并不均匀, 而且在局部还存在较高的应力积累, 这反应了断裂带中岩石的力学性质在空间上具有不均匀性。     

基于纳米β分子筛的石英晶体微天平沙林传感器研究

以纳米β(Cuβ)分子筛为敏感膜,结合石英晶体微天平(QCM)制备了对神经毒剂沙林(GB)敏感的传感器。结果表明,纳米β(Cuβ)分子筛对GB响应较纳米ZSM-5更灵敏,在热空气吹扫下可连续多次检测,其灵敏度为23.6Hz/(mg.m-3)(26.8Hz/(mg.m-3)),检出限(S/N=3)为0.96mg.m-3(0.90mg.m-3);线性范围1.50～18.24mg.m-3,线性相关系数为0.9910(0.9888)。该法在毒剂检测中具有一定的应用前景。     

聚甲基丙烯酸甲酯-牛血清白蛋白核壳纳米粒子在金表面的吸附过程及在传感器中的应用

利用铜离子引发体系, 制备出核层为聚甲基丙烯酸甲酯(PMMA)壳层为牛血清白蛋白(BSA)的PMMA-BSA核壳纳米粒子. 通过透射电子显微镜(TEM)表征, 直接观察到PMMA-BSA纳米粒子的核壳结构.结合X射线光电子能谱(XPS)测试, 分析PMMA-BSA纳米粒子的表面成分, 证明PMMA-BSA纳米粒子的壳层是BSA. 利用带耗散的石英晶体微天平(QCM-D)研究了PMMA-BSA纳米粒子在金片表面的吸附行为. 频率的迅速下降, 耗散因子的快速上升, 说明PMMA-BSA粒子快速地吸附到金片表面. 利用磷酸盐缓冲液反复冲洗时, 频率和耗散没有变化, 表明PMMA-BSA 纳米粒子在金片上吸附较牢固. 以金电极为基底电极, 吸附PMMA-BSA纳米粒子后, 利用戊二醛修饰粒子壳层, 再通过氨基与醛基的反应来固定葡萄糖氧化酶, 制备出电流型葡萄糖传感器. 电化学测试表明该传感器对葡萄糖具有良好的电流响应, 在0.3 V的工作电位下, 响应电流与葡萄糖浓度在0.20-5.85 mmol·L^-1范围内呈现出较好的线性关系, 相关系数为0.989. 传感器的灵敏度高达28.6 μA·L·mmol^-1·cm^-2, 响应时间仅为11 s. 传感器还具有良好的稳定性, 在25℃下储存30 d, 响应电流仅下降了16%.