直接粉末制样-小型偏振激发能量色散X射线荧光光谱法分析地质样品中多元素

采用小型偏振激发能量色散X射线荧光光谱仪,直接粉末制样法,分析了硅酸盐类岩石、土壤、沉积物样品.实验结果表明,主量元素的总分析精度优于2%RSD,主要受制样精度控制.不同含量的痕量元素的总分析精度一般优于5%RSD,含量低时可达约20%RSD.制样精度(方差)在分析总精度(方差)中所占的比例一般大于50%,且元素原子序数越小、含量越高(计数统计涨落小),所占的比例越大.实验还表明,对于大多数元素,在样品量大于1 g后,分析结果变化不显著;但Ba等重元素在样品量小于5 g时结果受样品量影响显著;实际分析中可以不必称量样品,但应保证所使用的样品量大于5 g.通过作为未知样品分析的标准参考物的分析结果和参校标准物质的回算结果的综合考察,并参照中国地质调查局多目标地球化学调查规范(1:25万),该方法在常规情况下可定量分析K、Ca、Ti、V、Cr、Mn、Fe、Ni、Cu、Zn、Ga、As、Rb、Sr、Y、Zr、Nb、Ba、Pb、Th等20个元素,过渡金属元素的测定限在10 mg/kg左右.由于制样方法简单,无需制样设备,该方法适合于车载野外现场快速分析.     

闽西北地区萤石矿成矿地质规律及找矿方向

闽西北地区萤石矿几乎均分布在闽西北隆起带的次一级浦城-洋源隆起和邵武-建宁拗陷带上,带内发育的北东—北北东向压扭性断裂通过燕山早期花岗岩的部位,是矿床的集中分布区域,控矿断裂中破碎带发育且蚀变(硅化)强烈地段是最有利的成矿地段,该地段应成为今后找矿重点。     

碱性溶液中坡缕石水解作用动力学实验研究

对安徽官山地区沉积型、热液型坡缕石进行碱性溶液中水解作用的动力学实验研究.结果表明:沉积型坡缕石较热液型更耐碱,且两种坡缕石均存在明显的差异溶解现象,即四面体硅的溶解速率要略大于八面体铝阳离子的溶解速率.碱溶液中沉积型、热液型坡缕石水解动力学均适宜采用圆柱体扩散控制模型模拟,其浸出率x对反应时间t的关系可表示为(1-x)+xlnx=kt.在实验条件下沉积型坡缕石水解过程中,Al3+和Si4+反应表观活化能分别为18.16 kJ/mol和18.53 kJ/mol.热液型坡缕石水解过程中,Al3+和Si4+反应表观活化能分别为31.2 kJ/mol和32.95 kJ/mol.     

长江口外赤潮多发区近几十年来的古生产力记录及环境意义

选取长江口外赤潮多发区沉积物柱状样,在高分辨率测年基础上,通过有机碳、有机碳同位素(δ13C)、生物硅、绿素等多项指标的分析获得了调查海区古生产力的变化信息。并结合近几十年来营养盐浓度及组成结构的变化探讨了海洋浮游藻类组成结构的变化在海洋古环境中的记录。柱状样年代可追溯到20世纪40年代初。δ13C值在柱中的分布为-26.15×10-3~-19.5×10-3,表明有机碳为陆源与海生的混合。生物标志物在柱状样中的分布可大致分为三个阶段,50年代以前含量均较低;50年代至80年代含量均增加,表明海洋浮游藻类活动强烈且以硅藻为主,与此阶段长江口营养盐浓度迅速增加相对应;80年代以后,生物硅的含量下降至整个柱中最低水平,绿素有所降低,但高于50年代前的水平,而有机碳含量增加,表明在该时段硅藻生物量降低,其他藻类生物量有所增加,这与长江口营养盐氮盐持续增加而硅酸盐逐年降低、氮与磷的含量比值、磷与硅的含量比值迅速增大有关。沉积记录还表明此阶段陆源有机碳的贡献增强。     

内蒙古达里诺尔含金云母辉石岩的发现及其地质意义

对华北克拉通北缘达里诺尔地区鸽子山附近玄武岩中的含金云母辉石岩捕虏体进行了岩石学、矿物学的研究,并对其中的单斜辉石、斜方辉石、金云母和粒间熔体进行了原位微区主、微量元素分析。结果显示,单斜辉石和斜方辉石具有低的Mg^#、Cr 2O 3和高的Al2O3含量,斜方辉石还具有高的MnO含量,这些特征表明辉石岩代表了交代熔体在地幔中冷却固结堆晶形成的岩脉。辉石岩中金云母、粒间熔体的出现及其不平衡的地球化学特征说明辉石岩形成以后又遭受到了多期次的硅酸盐熔体地幔交代作用。结晶出单斜辉石的母岩浆在蛛网图上具有K、Pb元素的弱负异常但不具有Nb、Ta、Ti元素的负异常,推测形成辉石岩的熔体可能来自软流圈地幔。粒间熔体的低SiO2,高MgO和FeO的特征指示其形成于地幔超基性岩的部分熔融,蛛网图上明显的K、Pb正异常以及Nb、Ta负异常说明其源区也存在俯冲沉积物的贡献。基于此,认为中国东部新生代岩石圈地幔经历了多期次地幔交代作用。     

胶州湾沉积物-海水界面硅的交换速率及其影响因素探讨

采用实验室培养法在原位温度和溶氧条件下测定了胶州湾沉积物-海水界面硅的交换速率,并探讨了相关环境因子对界面交换速率的影响机制。结果表明,胶州湾沉积物-海水界面硅的交换表现为从沉积物向水体释放,其交换速率在947~4 889 μmol/（m2·d）范围内,平均速率为1 819 μmol/（m2·d）。表层沉积物中叶绿素a（Chl a）和总有机碳（TOC）是影响胶州湾沉积物-海水界面硅交换速率的主要环境因子,同时表层沉积物的含水率（φ）、生源硅（BSi）和粘土含量以及间隙水中溶解硅酸盐（DSi）对沉积物-海水界面硅的交换也有重要影响。由此可推知,胶州湾沉积物-海水界面硅的交换速率主要受生物活动和溶解-扩散双重过程调控,而表层沉积物粒度与底层水体中DSi对胶州湾硅的释放影响较小。     

Examination of Silicate Limitation of Primary Production in Jiaozhou Bay, North ChinaⅢ.Judgment Method, Rules and Uniqueness of Nutrient Limitation Among N, P, and Si

ＩＮＴＲＯＤＵＣＴＩＯＮＮａｎｄＰｉｎｐｕｔｔｅｄｉｎｔｏＪｉａｏｚｈｏｕＢａｙｂｙｒｉｖｅｒｓａｎｄｂｙｓｅｗａｇｅｅｆｆｌｕｅｎｔｓｏｆｃｉｔｉｅｓ ,ｈａｖｅｍａｄｅｔｈｅＢａｙｂｅｃｏｍｅｍｏｒｅａｎｄｍｏｒｅｅｕｔｒｏｐｈｉｃｄａｙｂｙｄａｙ .Ｓｈｅｎ ( 1994)ｔｈｏｕｇｈｔｔｈａｔｐｈｙｔｏｐｌａｎｋｔｏｎｇｒｏｗｔｈｗａｓｌｉｍｉｔｅｄｂｙｔｈｅｃｈａｎｇｅｆｒｏｍｎｉｔｒｏｇｅｎｔｏｐｈｏｓｐｈｏｒｏｕｓ ;ａｎｄｔｈａｔｔｈｅｓｉｌｉｃａｔｅｃｏｎｃｅｎｔｒａｔｉｏｎｉｎＪｉａｏｚｈ…     

Usable Values of Nickel Ore and Nickel Concentrate Certified Reference Materials

The preparation and characterisation of three nickel ores and two nickel concentrate certified reference materials are described in this paper. The samples of nickel ore and nickel concentrate were collected from the Hongqiling nickel deposit in Jilin province. The raw materials were crushed and passed through a 2.0‐mm sieve. The rough samples were then ground for 48 hr in a high‐alumina ball mill to a final size of < 0.074 mm. Homogeneity of the samples was tested by X‐ray fluorescence spectrometry (WD‐XRF) and inductively coupled plasma‐atomic emission spectrometry (ICP‐AES). The relative standard deviations (RSD) of results on mass fraction measurements by WD‐XRF were < 1.0% m/m for eighteen components. F‐tests showed that all five samples were homogeneous. Nineteen laboratories contributed with measurement results (2127 in total) for the certification of mass fractions for twenty‐three elements and compounds. Twenty‐three components in the nickel ores and twenty components in the nickel concentrates were characterised as certified values, while the Ni mass fractions ranges from 0.1 to 9.02% m/m in these certified reference materials. These five samples were approved as national certified reference materials by the National Organisation of Reference Materials of China in 2012.     

含钾岩石微生物转化的分子机制及其碳汇效应

岩石矿物的微生物风化是地球表层系统最为活跃和普遍发生的地质营力之一。微生物对含钾岩石(以硅酸盐矿物为主)的风化能够释放其中的钾、硅和钙等元素,并在合适的环境条件下促进矿物元素的碳酸化沉淀,这是地表元素地球化学循环的重要环节之一。微生物对岩石的生物转化作用既涉及微生物的生长繁殖和代谢调控,也与元素的迁移转化和次生矿物的演化序列有关,具有重要研究价值。采用矿物学、微生物学和分子生物学等相结合的研究方法,有助于系统地研究微生物促进含钾硅酸盐矿物的风化并耦联碳酸化过程及其分子调控机制。研究证实,在纯培养条件下,微生物风化含钾矿物主要采用酸解、螯合、氧化还原等多种方式的协同作用,并可通过调控相关功能基因的表达来响应缺钾的环境以实现其对含钾矿物的有效风化,显然这有赖于微生物通过长期进化而形成的精细的分子调控机制。在土壤生态环境中,微生物对矿物风化的显著特征是该生态环境中微生物群落协同互作的群体作用效应。微生物碳酸酐酶参与的硅酸盐矿物风化伴随碳酸盐矿物的形成过程可能是个长期被忽视的地表碳增汇过程,对该问题的深入探索有助于进一步理解地质演化历史中微生物对碳素迁移转化的驱动机制。加入含钾硅酸盐矿粉的有机肥已经显示出其在土壤改良、作物生长和增加土壤碳汇等方面的正面应用效果,这为利用硅酸盐矿物的生物风化作用来延缓大气CO₂浓度的持续升高提供了新的思路。介绍了有关微生物对含钾岩石生物转化释放钾素的分子机理及其碳汇效应方面的研究进展,以期抛砖引玉,推动该领域研究的快速发展。     

Sodic Pyroxene and Sodic Amphibole as Potential Reference Materials for In Situ Lithium Isotope Determinations by SIMS

Two large pegmatitic crystals of sodic pyroxene (aegirine) and sodic amphibole (arfvedsonite) from the agpaitic igneous Ilímaussaq Complex, south Greenland were found to be suitable as reference materials for in situ Li isotope determinations. Lithium concentrations determined by SIMS and micro‐drilled material analysed by MC‐ICP‐MS generally agreed within analytical uncertainty. The arfvedsonite crystal was homogeneous with [Li] = 639 ± 51 μg g^?1 (2s, n = 69, MC‐ICP‐MS and SIMS results). The aegirine crystal shows strongly developed sector zoning, which is a common feature of aegirines. Using qualitative element mapping techniques (EPMA), the homogeneous core of the crystal was easily distinguished from the outermost sectors of the crystals. The core had a mean [Li] of 47.6 ± 3.6 μg g^?1 (2s, n = 33) as determined by SIMS. The seven micro‐drilled regions measured by solution MC‐ICP‐MS returned slightly lower concentrations (41–46 μg g^?1), but still overlap with the SIMS data within uncertainty. Based on MC‐ICP‐MS and SIMS analyses, the variation in δ⁷Li was about 1‰ in each of the two crystals, which is smaller than that in widely used glass reference materials, making these two samples suitable to serve as reference materials. There was, however, a significant offset between the results of MC‐ICP‐MS and SIMS. The latter deviated from the MC‐ICP‐MS results by ?6.0 ± 1.9‰ (2s) for the amphibole and by ?3.9 ± 1.9‰ (2s) for the aegirine. This indicates the presence of a significant matrix effect in SIMS determinations of Li isotopes for amphibole and pyroxene relative to the basalt glasses used for calibration. Based on the MC‐ICP‐MS results, mean δ⁷Li values of +0.7 ± 1.2‰ (2s, n = 10) for the arfvedsonite crystal and of ?3.7 ± 1.2‰ (2s, n = 7) for the core of the aegirine crystal were calculated. Adopting these values, SIMS users can correct for the specific IMF (instrumental mass fractionation) of the ion probe used. We propose that these two crystals serve as reference materials for in situ Li isotope determinations by SIMS and pieces of these two crystals are available from the first author upon request.