钠基蒙脱土水合演化机制

为了查明钠基蒙脱土的水合演化过程,以天然钠基蒙脱土为研究对象,开展在相对湿度（ ）为0～0.98区间的水汽等温吸-脱附试验,通过吸附速率曲线、BET曲线界定钠基蒙脱土各水合阶段及相应的水合主控因素;通过测定晶层 值变化规律,从吸附水影响黏土矿物晶层厚度的角度探讨钠基蒙脱土的水合演化特征;基于傅里叶红外光谱,从水分子结构伸缩振动信息角度对钠基蒙脱土水合演化过程进行定性定量验证;通过热重/差热分析,以吸附水相变所需能量与吸附水重量变化的角度解释钠基蒙脱土的吸附水特征与其水合机制的关系。试验结果表明：在较低相对湿度下（0 0.15）,以钠基蒙脱土矿物外表面吸附为主,形成表面吸附水;0.15 0.40为钠基蒙脱土层间阳离子水合阶段;0.40 0.98,为晶层内外表面水合阶段,水分子逐步完整的包裹蒙脱土,形成多层吸附层。钠基蒙脱土的水合演化过程受控于层间钠离子与晶层基面,层间钠离子的水合能影响了钠基蒙脱土水合演化的起始顺序。     

碳酸氢钠冷却结晶动力学

碳酸氢钠(NaHCO_3)俗称小苏打,其产品质量取决于颗粒的大小,晶体的形貌和样品的纯度等诸多因素。本论文基于连续稳态MSMPR结晶器原理,研究了不同停留时间下,碳酸氢钠从碳酸钠溶液中冷却结晶过程动力学。利用实验数据建立了NaHCO_3的结晶动力学操作模型。实验和计算结果表明,随停留时间的增加,NaHCO_3过饱和度降低,晶体生长速率和成核速率均减小,相应的平均粒径增加,细颗粒含量减小;适当延长停留时间是制取高品质小苏打产品的有效途径。冷却结晶过程可有效增加小苏打产量,小苏打收率维持在55%左右。此外,一定Na_2CO_3存在下冷却结晶碳酸氢钠晶体形态由细长的针状变为规整的片状。     

银量法测定化学试剂氯化钠中氯化钠纯度的不确定度评定

针对银量法测定化学试剂氯化钠中氯化钠纯度,讨论了氯化钠纯度测定结果的测量不确定度的来源及评定方法,当K=2,氯化钠纯度测定结果的扩展不确定度为(99.70±0.64)%。     

敞开酸溶和偏硼酸锂碱熔ICP-MS法测定多金属矿中的稀土元素及铌钽锆铪

用电感耦合等离子体质谱法(ICP-MS)测定地质样品中的稀土及难熔元素,混合酸敞开酸溶法和碱熔融法是两种主要的溶样方法。但地质样品组分复杂,元素之间存在相互共生的现象,对于特殊元素、特殊样品用传统酸溶法会造成部分元素消解不完全,使测定结果不准确;而碱熔法的操作过程繁琐,且溶液盐度高,易产生基体干扰和堵塞仪器进样系统。本文改进了传统四酸和五酸体系,采用氢氟酸-硝酸-硫酸敞开酸溶体系,用国家一级标准物质制作标准曲线测定15种稀土元素,方法准确度(ΔlgC)为0.001～0.027。同时改进了偏硼酸锂碱熔法,样品用偏硼酸锂碱熔提取,加入氢氧化钠调节溶液至碱性条件,所测元素与偏硼酸锂共沉淀后过滤分离熔剂,再用硝酸复溶测定15种稀土元素及铌钽锆铪。两种溶样方法的测定值与认定值的相对误差为1.09%～9.30%。将混合酸敞开酸溶法测定稀土元素、偏硼酸锂碱熔法测定铌钽锆铪的结果与其他实验室密闭酸溶法相比,两组数据的相对偏差为0.13%～15.32%。本实验表明,混合酸敞开酸溶法适用于测定地质样品中的稀土元素,偏硼酸锂碱熔法不仅适用于测定地质样品中的稀土元素及铌钽锆铪,也适用于测定如古老高压变质岩石及铝含量高的样品中的铌钽锆铪。     

采用SDS研究泥蚶血红蛋白(Tg-HbⅡ)具有过氧化物酶及抗菌活性的结构基础

泥蚶血红蛋白(Tg-HbⅡ)除了具有携氧功能外,还具有过氧化物酶活性和抗菌活性。本文采用分光光度法、光谱法和分子对接等技术研究了十二烷基硫酸钠(SDS)对Tg-HbⅡ的结构、过氧化物酶活性及抗菌活性的影响,以探讨Tg-HbⅡ具有过氧化物酶活性及抗菌活性的结构基础。研究结果显示,SDS的疏水烷基长链可嵌入到Tg-HbⅡ血红素口袋内部,与近端His104形成氢键,断裂血红素铁与His104的配位键,使Tg-HbⅡ的Soret带吸收峰降低并发生位移;此外,SDS还可与血红素口袋中的氨基酸形成疏水相互作用,改变血红素口袋原有结构,使得部分疏水氨基酸暴露,导致外源荧光强度增强,最大发射波长红移。SDS可以抑制Tg-HbⅡ的过氧化物酶活性,当SDS浓度为2 mmol•L^–1时,Tg-HbⅡ的酶活性仅为原来的20%,在琼脂扩散实验中失去对枯草芽孢杆菌的抗菌活性。以上结果表明,SDS通过破坏血红素口袋的内部结构抑制Tg-HbⅡ的过氧化物酶活性,使其失去抗菌活性,血红素疏水口袋是Tg-HbⅡ具有过氧化物酶活性和抗菌活性的关键结构。本研究为进一步研究Tg-HbⅡ的抗菌机理奠定基础。     

Pseudocycnus appendiculatus Heller, 1868 (copepoda,dichelesthiidae) in New Zealand waters

Pseudocycnus appendiculatus Heller is described and recorded, for the first time from New Zealand, on Thunnus alalunga (Bonnaterre, 1788). Pseudocycnus spinosus Pearse, 1951 and P. thynnus Brandes, 1955 are thought to be synonyms of P. appendiculatus. Other species previously placed in the genus are discussed and the action of Yamaguti (1963) in removing them to other genera supported. It is suggested that the family Pseudocycnidae Yamaguti, 1963 cannot be differentiated from the family Dichelesthiidae Bassett‐Smith, 1898.     

Sodium fluoroacetate (1080) residues in longfin eels,Anguilla dieffenbachii,following exposure to contaminated water and food

Captive longfin eels (Anguilla dieffenbachii) were exposed to the vertebrate pesticide sodium fluoroacetate (1080) in the water column and through the ingestion of cereal pellet baits or possum muscle and gut tissue that contained 1080 residue. No mortality or unusual behaviour (in comparison with the controls) occurred in eels that were exposed to 1080. However, significantly greater weight loss occurred in eels exposed to 1080 compared with those eels that were not. No residue was detected in tissues of eels exposed to 1080 cereal baits through ingestion and direct (dermal and respiratory) absorption, or through direct absorption only. Low concentrations of 1080 were detected in muscle tissue of eels that consumed contaminated possum muscle (x = 0.0174 μg/g) or gut (x = 0.0306 μg/g) tissue. The primary factors affecting the concentration of 1080 detected in eel tissue included the dose of 1080 (mg/kg) that each eel" receiveddate="and number of days since the eel last fed on contaminated tissue. Based on the 1080 concentrations measured in eels in this study, the risk of acute poisoning to humans from eating contaminated eel flesh is considered extremely low. Even so, national and international perceptions and food safety standards have the potential to limit eel exports and/or close an eel fishery if 1080 residue was discovered in tissue.     

温度改性水玻璃固化黄土机制研究

硅化法是湿陷性黄土地基处理的主要化学方法之一,为了提高固化效果需要对水玻璃溶液进行改性。对温度改性水玻璃溶液固化黄土进行了试验研究,并通过化学组成和矿物成分分析、微观结构分析探讨了温度改性水玻璃固化黄土的机制。试验结果表明：在20～80 ℃范围内,随着温度的升高,水玻璃固化黄土的强度有明显提高;X射线衍射图谱中部分矿物衍射强度降低并出现密集低矮的非晶质物相峰群;SEM图像显示随着温度的升高凝胶薄膜增多;MIP（压汞试验）数据显示,随着温度的升高,孔隙表面积增大。水玻璃溶液固化黄土的强度随温度增加的机制在于：生成的非晶质物相和凝胶薄膜随着温度的升高而增加,促使最可几孔径的减小和小孔隙的增多,强化了骨架颗粒的连接强度,并将骨架颗粒黏结成为一个空间网状整体,从而改善了土体的强度。     

Mechanisms and factors affecting the adsorption of sodium alginate onto modified clays

Algal organic materials (AOMs) are one critical factor affecting the efficiency of modified clays used for the mitigation of harmful algal blooms (HABs). This study was conducted to develop a deeper understanding of the mechanisms and factors affecting the adsorption of AOMs onto modified clays. Sodium alginate (polysaccharide) and kaolinite modified with polyaluminium chloride (PACl) were used as AOMs and modified clay model substances, respectively, and the effects of modifier dosage, contact time, solution pH and ionic strength were investigated through batch adsorption experiments. Kinetics revealed that the alginate adsorption rate was described well by a pseudo-second order model. PACl effectively enhanced the adsorption capacity of kaolinite and increased the adsorption rate, and the optimum additive amount of PACl was 5%. The experimental data fitted both the Freundlich and Langmuir adsorption equations well. The adsorption thermodynamics for alginate onto modified clays suggests that alginate adsorption is a spontaneous process. The adsorption of alginate onto modified clays was highly dependent on pH, with a decrease in adsorption observed with increased pH to 9.48, but the opposite was true above pH 9.48. Finally, adsorption increased with increasing ionic strength.     

不同钠吸附比含水介质中胶体迁移-沉积动力学

以滨海含水介质中天然胶体为研究对象,采用自行设计的室内土柱装置,研究不同钠吸附比胶体在滨海含水介质中迁移动态特征,测定了胶体沉积动力学曲线,计算了胶体总沉积率和沉积速率常数,最后对胶体迁移沉积机理进行了探讨。研究结果表明,胶体的穿透曲线与示踪离子相比,存在一个临界孔隙体积数(临界点),在临界点之前胶体的迁移速度大于示踪离子,之后则相反;胶体未发生完全穿透,钠吸附比SAR为0,2.85和∞;出水胶体最大相对浓度为0.65,0.16和0.70;胶体在含水介质迁移过程中发生了沉积,沉积量随孔隙体积数的增加而增加。胶体在含水介质中迁移的总沉积率分别为50.96%、87.95%和54.24%。钠吸附比SAR=2.85时沉积动态曲线为直线,沉积速率常数为0.151h-1,而钠吸附比SAR为0和∞时胶体沉积动态曲线为分段直线,拐点前后胶体沉积速率常数分别为0.072 h-1、0.048h-1和0.211 h-1、0.194 h-1。研究结果用双电子层理论可以很好地解释。