利用钾长石粉水热合成13X沸石分子筛的实验研究

对综合利用钾长石提钾工艺中的重要高附加值副产品13X沸石分子筛的合成进行了实验研究。对福建沙县的钾长石粉加入配料NaCO3进行焙烧实验，确定培烧的最佳工艺参数为：钾长石粉：NaCO3=1：1．30(摩尔比)，焙烧温度为845℃，焙烧时间为150min；优化的水热合成条件为M2O／SiO2(mo1)=1．50，H2O／M2O(mo1)=40．0，合成时间为8h，晶种加入量为9．0％。对合成样品化学成分分析、X射线物相分析、红外光谱分析、扫描电镜分析表明，合成13X沸石分子筛结晶完好，性能优良．水热反应经由溶解水合反应和聚合浓缩反应两大阶段。     

Aragonite and calcite preservation in sediments from Lake Iznik related to bottom lake oxygenation and water column depth

This study examines the forcing mechanisms driving long‐term carbonate accumulation and preservation in lacustrine sediments in Lake Iznik (north‐western Turkey) since the last glacial. Currently, carbonates precipitate during summer from the alkaline water column, and the sediments preserve aragonite and calcite. Based on X‐ray diffraction data, carbonate accumulation has changed significantly and striking reversals in the abundance of the two carbonate polymorphs have occurred on a decadal time scale, during the last 31 ka cal bp . Different lines of evidence, such as grain size, organic matter and redox sensitive elements, indicate that reversals in carbonate polymorph abundance arise due to physical changes in the lacustrine setting, for example, water column depth and lake mixing. The aragonite concentrations are remarkably sensitive to climate, and exhibit millennial‐scale oscillations. Extending observations from modern lakes, the Iznik record shows that the aerobic decomposition of organic matter and sulphate reduction are also substantial factors in carbonate preservation over long time periods. Lower lake levels favour aragonite precipitation from supersaturated waters. Prolonged periods of stratification and, consequently, enhanced sulphate reduction favour aragonite preservation. In contrast, prolonged or repeated exposure of the sediment–water interface to oxygen results in in situ aerobic organic matter decomposition, eventually leading to carbonate dissolution. Notably, the Iznik sediment profile raises the hypothesis that different states of lacustrine mixing lead to selective preservation of different carbonate polymorphs. Thus, a change in the entire lake water chemistry is not strictly necessary to favour the preservation of one polymorph over another. Therefore, this investigation is a novel contribution to the carbon cycle in lacustrine systems.     

X射线衍射技术应用于宝石鉴定-合成及晶体结构研究进展

因宝石检测常附带无损要求、宝石评价具科学性和不确定性等特点,X射线衍射(XRD)在宝石学这门矿物学的分支学科中的应用具有特殊性,其应用领域主要集中在三个方面。①宝石鉴定领域:对单晶宝石和多晶宝石进行物相鉴定、宝石产地特征研究以及宝石矿物多型的种类划分等。例如根据XRD图谱,可将品种繁多的微晶石英隐晶质变种玉髓中不同的SiO₂质矿物相精确区分;通过黏土矿物成分及其含量可将鸡血石中"地"的种类进行划分。②宝石矿物的晶体结构研究:对成分复杂的单晶宝石进行晶体化学分析、获取矿物类质同象替代情况、利用结晶度划分宝石品质。例如晶格参数中的c/a比值可将绿柱石的Al八面体类质同象替代和Be四面体类质同象替代进行区分;软玉中通过XRD数据计算出的结晶度与软玉的品质关系密切。③宝石学研究技术的开发:对宝石的优化处理过程进行监测,在宝石合成过程中检验矿物晶形大小、结晶质量及内应力等,以有机宝石的晶体结构为基础的人工养殖技术研究。例如尖晶石在热处理过程中,Mg离子由四面体中的T位迁移至八面体中的M位,导致M-O和T-O键长随温度变化,并反映在尖晶石的色调中;在托帕石合成过程中,XRD数据显示770~800℃时形成含氟托帕石(与天然托帕石结构相同),而在950℃和1000℃出现含氟托帕石离解成刚玉和莫来石。目前,我国在宝石学的XRD应用方面起步较晚,国外在宝石鉴定、优化与合成方面的应用相对成熟。本文认为,该技术与扫描电镜、质子探针等分析技术的联用仍有很大发展空间。     

TRMM卫星降水数据在小尺度流域的评估与应用

选取史灌河流域上游黄泥庄站以上集水区域为研究流域,以地面站点观测为基准数据,评估TRMM 3B42V7版本卫星降水数据的精度,并采用上述两种降水数据驱动栅格型新安江模型,模拟黄泥庄站日径流和月径流过程。结果表明:2001~2010年TRMM 3B42V7降水数据与雨量站数据累积量的偏差不大,仅为1.71%,但相关系数较低,采用TRMM降水数据模拟的日径流能基本再现黄泥庄站的日径流过程,但对洪峰的模拟精度较低;TRMM月降水数据精度较高,相关系数为0.96,能够较为精确地模拟黄泥庄站的月径流过程。     

脊尾白虾(Exopalaemon carinicauda)维甲酸X受体基因克隆及其在温盐胁迫和蜕皮周期中的表达分析

为了明确脊尾白虾维甲酸X受体基因在环境胁迫和蜕皮周期中的作用,本研究通过RACE技术克隆了脊尾白虾(Exopalaemon carinicauda)维甲酸X受体c DNA全长,命名为Ec RXR基因,该c DNA序列全长为1323 bp,开放阅读框(ORF)为855 bp,编码一个284个氨基酸组成的蛋白质,分子量为30.918 k Da,理论等电点为PI为6.788;Ec RXR基因推导氨基酸序列经Blastp在线比对分析显示,Ec RXR与已知甲壳动物RXR的同源性为71%—90%;系统进化树分析结果显示,脊尾白虾Ec RXR的氨基酸序列与日本沼虾RXR的氨基酸序列聚为一支。荧光定量RT-PCR分析表明,Ec RXR基因在各组织中均有表达,而在眼柄相对表达量较高,血淋巴中最低。Ec RXR基因在蜕皮周期中的表达规律表明,Ec RXR基因表达在不同蜕皮时期存在明显变化,在眼柄、肝胰腺、胃和肠中整体呈现上升趋势,在鳃中呈现先下降后上升的趋势,在表皮中呈现逐渐降低的趋势。Ec RXR基因在温度、盐度胁迫过程中的表达规律分析结果发现,温度、盐度胁迫均可显著改变Ec RXR基因在鳃和肝胰腺中的表达模式,温度胁迫下Ec RXR基因在鳃中呈先上升后下降的表达趋势,肝胰腺中整体呈先上升后下降再上升再下降的表达趋势;盐度对鳃和肝胰腺的调控模式相同,均呈先升高后下降的变化趋势。本研究结果表明Ec RXR基因在脊尾白虾蜕皮发育、酶活性调控及渗透压调节中发挥重要作用,为深入研究甲壳动物维甲酸X受体基因的功能提供了重要的基础信息。     

Copper Speciation in a Collection of Geochemical Reference Materials Using Sequential Extraction and Evaluation of the Validity Using XANES Spectroscopy

Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.