Adsorption characteristics of copper ion on nanoporous silica

Adsorption by nanoporous media is critically involved in many fundamental geological and geochemical processes including chemical weathering,element migration and enrichment,environmental pollution,etc.Yet,the adsorption behavior of metal ions on nanoporous materials has not been systematically investigated.In this study,MCM-41 material with a monodisperse pore size(4.4 nm)and a large BET specific surface area(839 m^2/g)was hydrothermally prepared and used as a model silica adsorbent to study the adsorption characteristics of Cu^2+as a representative metal ion.The Cu^2+adsorption capacity was found to increase with increasing suspension pH in the range from 3 to 5 and to decrease in the presence of NaNO3.At 25℃,pH=5,and a solid-to-liquid ratio of 5 g/L,the adsorption capacity was determined to be 0.29 mg/g,which can be converted to a dimensionless partition coefficient of 45,indicating a strong enriching effect of nanoporous silica.The adsorption isotherm and kinetic data were fitted to several commonly used thermodynamic,kinetic,and diffusion models.The adsorption mechanism was also studied by Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy and synchrotron-based X-ray absorption spectroscopy.The results suggest that Cu2+ion adsorption is an entropy-driven endothermal process,possibly involving both outer-sphere and inner-sphere complexes.     

南大洋普里兹湾沉积物中生物硅的溶解度研究

本文利用中国南极科学考察航次获得的沉积物样品,采用分批（batch）实验方法,获取实验室生物硅溶解度,并结合间隙水中可溶性硅剖面,对普里兹湾沉积物中生物硅的溶出过程进行了初步研究。研究结果如下：在25℃,pH 8条件下,普里兹湾IV-10、 IS-4站表层沉积物中生物硅的实验室溶解度分别为1936、1539μmol/dm3,不同层次沉积物溶出结果显示随深度增加溶解度值降低。根据实验室溶解度数据与间隙水硅酸盐Cd的分析比较,表明研究站位沉积物生物硅的早期成岩过程中生物硅的溶出还伴随有其他化学过程。     

The silica supersaturated waters of northern Evia and eastern central Greece

The area of north Evia and eastern central Greece is characterized by strong geomorphological contrast and is built up mainly of consolidated rocks. Unconsolidated young sediments of Pleistocene to Holocene age cover the valley and basin flats, forming the most productive aquifers in this area. However, two more types of aquifers can be distinguished within the consolidated rock area. The first one is associated with karstified limestones and the second with strongly tectonized ultramafic rocks. The schist–chert formation, with intercalations of shales and cherts, seals the ultramafic masses underneath. Surface and spring waters associated with ultramafic rocks in north Evia and eastern central Greece were studied. Two types of water can be distinguished: (1) high Mg²⁺ and SiO₂ , bicarbonate as the dominant anion, pH 7·4–9·2, temperature 9·5–16·3 °C, low TDS (total dissolved solutes) (459–1037 mg/l), found both in peridotite and serpentinite areas, classified as Mg–HCO₃ type; (2) high Ca²⁺, low Mg²⁺ and SiO₂ , hydroxyl ion as the major anion, pH 11·2, temperature 28 °C, very low TDS (122 mg/l), found in peridotite areas, classified as Ca–OH type. The studied waters are highly supersaturated with respect to quartz, amorphous silica, brucite and most low temperature magnesium silicates (antigorite, sepiolite, talc, etc.). These waters show relatively narrow SiO₂ concentration ranges and a trend parallel to the amorphous silica saturation surface. The silica supersaturated waters have the potential to precipitate silica and consequently could affect the people of the local communities that use it as drinking water, causing health problems (kidney stones). Copyright © 1999 John Wiley & Sons, Ltd.     

长江口邻近海域沉积物和间隙水中硅的研究

以2011年6月和8月在长江口邻近海域采集的沉积物和间隙水样品为研究对象,讨论了沉积物中生物硅（BSi）和间隙水中溶解硅（DSi）的分布情况和影响因素,并初步探讨了生物硅的循环和保存。结果表明,表层沉积物中BSi的含量较低,且均小于1%。柱状沉积物中BSi的含量范围为0.34%~0.52%。C3、D1站位柱状沉积物中BSi的记录主要是由早期成岩过程控制,33#站位的分布特征主要是由水动力等变化控制。沉积物间隙水中DSi的浓度范围为101.6~263.9 μmol/L,低于纯BSi的溶解度;间隙水的pH值越大,沉积物的含水率越低,还原性越强,间隙水中DSi的含量越高。3站位生物硅的埋藏效率均较高,表明长江口邻近海域是潜在的硅的汇。沉积通量的分布与沉积速率和埋藏效率的分布一致,均有近岸高于远海的趋势。     

渤海表层沉积物中的生物硅

采用0.1 mol/L HCl和1%Na2CO3两步连续提取法,对103个渤海表层沉积物样品的生物硅含量进行了分析,结果表明,渤海表层沉积物中生物硅含量范围为7.3~54.7 g/kg,均值31.5 g/kg,高于其他相关调查,原因可能是由于采用0.1 mol/L HCl提取过程中,破坏了生物硅表面的金属氧化膜。对沉积物生物硅含量的空间分布表征显示,莱州湾是沉积物生物硅的低值区、而渤海湾与辽东湾之间的河北沿岸海域是相对高值区,初步认为是陆源营养物质的输入与黄河泥沙长期不断输入干扰沉积环境的稳定性,造成了该海域表层沉积物生物硅分布差异。主成分分析显示,生物硅含量与沉积物黏粒含量、细粉砂、有机氮、有机碳的含量均呈极显著正相关(P0.01),进一步证实沉积物粒度特征和营养环境对生物硅积累的影响。     

Effect of Silica Fume on Compressive Strength of Oil-Polluted Concrete in Different Marine Environments

In the present research, effect of silica fume as an additive and oil polluted sands as aggregates on compressive strength of concrete were investigated experimentally. The amount of oil in the designed mixtures was assumed to be constant and equal to 2% of the sand weight. Silica fume accounting for 10%, 15% and 20% of the weight is added to the designed mixture. After preparation and curing, concrete specimens were placed into the three different conditions: fresh, brackish and saltwater environments (submerged in fresh water, alternation of exposed in air & submerged in sea water and submerged in sea water). The result of compressive strength tests shows that the compressive strength of the specimens consisting of silica fume increases significantly in comparison with the control specimens in all three environments. The compressive strength of the concrete with 15% silica fume content was about 30% to 50% higher than that of control specimens in all tested environments under the condition of using polluted aggregates in the designed mixture.     

安徽巢湖地区中二叠统栖霞组灰岩中燧石成因

安徽省巢湖地区中二叠统栖霞组以发育一套滨海沼泽－浅海碳酸盐台地环境为主的细碎屑岩至碳酸盐岩沉积建造为特征,灰岩中常见结核状及条带状燧石。燧石多为椭球状和串珠状,部分燧石与灰岩间发育宽约0.5 cm的过渡带。镜下观察灰岩为微晶生物碎屑灰岩;过渡带也多由微晶方解石组成,多数钙质生物壳体被石英充填或半充填,扫描电镜下可见方解石微溶、石英充填溶孔的现象;燧石主要为隐晶及微晶石英,生物碎屑类型与灰岩中基本一致,且多被石英交代。岩石学特征表明死亡的生物在腐烂降解过程中形成的有机酸抑制了碳酸钙的沉淀,并使部分生物碎屑及灰泥发生溶蚀,胶质二氧化硅沉淀,形成燧石结核。燧石中w(Al)/w(Al+Fe+Mn)平均值为0.63,远大于热水沉积硅质岩的最大值0.35;Fe/Ti平均值为9.5,小于热水成因的最小值20;Al-Fe-Mn三角图投点位于非热液成因区域;燧石中Al₂O₃含量平均值为0.20%,远高于MgO、Na₂O、K₂O的含量。分析认为,该区燧石结核的二氧化硅可能来源于陆源物质。     

赤道太平洋上层水体颗粒态生物硅分布及与营养盐的关系

依托中国“大洋一号”第20和第21调查航次,分析测定了东、西赤道太平洋4个站位的颗粒态生物硅浓度及其粒级结构。结果显示赤道太平洋采样站各层位颗粒态生物硅(PBSi)总浓度分布范围为5~65 nmol/dm³,东赤道太平洋的调查站位颗粒态生物硅的总浓度平均值达46 nmol/dm³,是西赤道太平洋的近3倍。PBSi的粒径结果显示在东赤道太平洋调查站位0.8~20 μm粒径颗粒是PBSi的主要来源,其平均贡献率高达64%;而在西赤道太平洋2种粒径的生物硅贡献率相当。营养盐分布对PBSi的浓度及粒径分布有显著的影响,并在一定程度上控制了“硅质泵”的组成结构,是控制大洋生物泵运转的重要因素。     

烟台四十里湾表层沉积物中生物硅的研究

以烟台四十里湾作为研究区域,分析了16个站位表层沉积物中生物硅的含量,探讨沉积物中生物硅对内湾环境的指示作用.结果表明,污水排放区、垃圾倾倒区沉积物中生物硅含量较高(平均值分别为0.71％和0.78％),对应上层水体的富营养化;航道区生物硅含量很低(平均值0.37％),与航船扰动造成的低生产力状况符合.沉积物中生物硅含量较好地反映了上层水体的浮游植物状况,并与上层营养盐浓度具有很好的对应关系.研究表明,沉积环境能够明显影响沉积物中生物硅的沉积和保存.     

A modified method for biogenic silica determination

We describe a modified method for the determination of biogenic silica (BSi) in lacustrine sediment samples with BSi concentrations >0.5% SiO₂ (detection limit). To speed up the leaching procedure (48 samples per day), we suggest the use of Teflon autoclaves that can be left unattended (no stirring of the solution) for 3 h at 100°C in an oven. We suggest a volume correction by Na measurement to account for volume errors during pipetting off a hot solution. We also propose to carry out a correction for minerogenic silica by the simultaneous determination of Al in the leachate. Analytical precision and accuracy of the proposed method are 2.4% (relative standard deviation) and 70–110% recovery (relative to the mean of four international reference sediment samples), respectively. Additionally, we demonstrate that pre-treatment of the samples with H₂O₂ and/or HCl prior to alkaline leaching is not necessary for all samples. Due to the great diversity of lacustrine and marine sediments, however, the pre-treatment procedure should be tailored for samples from different sites.