铁同位素的MC-ICP-MS测定方法与地质标准物质的铁同位素组成

详细报道了在低分辨和高分辨模式下运用MC-ICP-MS进行Fe同位素比值高精度测试的方法,对Fe同位素测定过程中谱峰干扰、基质效应、浓度效应、仪器测试的长期重现性等问题进行了评估,并对两种运行模式的测试结果进行了对比.在95%的可信度范围内,所建方法的外部精度优于0.5ε/ainu,达到国际同类实验室的先进水平,并且低分辨和高分辨两种模式下获得的Fe同位素测试结果是一致的.在此基础上对国家地质标准物质GBW07105(玄武岩)和GBW 07111(花岗闪长岩)进行了Fe同位素测定.相对于Fe同位素国际标样IRMM-014,GBW07105的Fe同位素成分为:ε57Fe=1.9±0.3(20),ε56Fe=1.3±0.2(2σ),ε57/56Fe=0.6±0.1(2σ);GBW 07111的Fe同位素成分为:ε57Fe=1.8±0.4(2σ),ε56Fe=1.2±0.2(2σ),ε57/56Fe=0.6±0.1(2σ).     

绿片岩-低角闪岩相变质条件下磁铁铁矿与黄铁矿间的Fe同位素分馏

对辽宁省鞍山一本溪地区经历了绿片岩一低角闪岩相变质的新太古代条带状铁建造中磁铁矿和黄铁矿矿物对的Fe同位素分析结果显示:相对于标准IRMM-014,所有样品的磁铁矿和黄铁矿均显示Fe的重同位素富集;且黄铁矿的Fe同位素比值均大于磁铁矿的Fe同位素比值(ε57Fe黄铁矿ε57Fe磁铁矿),两种矿物的Fe同位素比值之差为△57Fe黄铁矿-磁铁矿=2.23～5.13.黄铁矿富集铁的重同位素表明矿物的Fe同位素组成并不代表其原始沉积的特征,而是在区域变质作用过程中Fe同位素发生了交换的结果.由同位素平衡判别图解可知,在绿片岩一低角闪岩相变质作用中,磁铁矿-黄铁矿间的Fe同位素基本达到了平衡,且在平衡条件下黄铁矿比磁铁矿更富集Fe的重同位素,二者之间的Fe同位素平衡分馏系数α黄铁矿-磁铁矿≈1.000 4‰±0.06‰(2σ).这一研究成果是对变质作用过程中Fe同位素的地球化学行为认识的重要进展.     

SO4^2-改性铁铝复合层柱粘土的制备及其催化性能研究

由共聚法制得的铁铝复合交联剂交换钠基蒙脱石层间的水合钠离子,再经SO42-改性处理制备了铁铝复合层柱粘土固体超强酸催化剂.利用xRD、FT-IR和BET法对催化剂的结构进行了表征.以乙酸正丁酯的合成反应为探针反应对催化剂的活性进行了测试.通过正交实验确定了铁铝复合交联粘土SO42-改性最佳工艺条件.研究了催化剂对探针反应的选择性及重复使用情况.结果表明:在由实验确定的最佳改性工艺条件下,乙酸的转化率达92.2%,反应中无副产物产生,催化剂具有较好的重复使用性能.     

On the relevance of iron adsorption to container materials in small-volume experiments on iron marine chemistry: Fe-aided assessment of capacity, affinity and kinetics

Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron ⁵⁵Fe was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25–70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments.The present data indicate that for PMMA with specific surface (S)-to-volume (V) ratio S/V, both iron capacity (42 ± 16 × 10^− 9 mol/m² or 1.7 × 10^− 9 mol/L recalculated for the S/V-specific PMMA bottles used) and affinity (log K_Fe'W = 11.0 ± 0.3 m²/mol or 12.4 ± 0.3 L/mol, recalculated for the S/V-specific PMMA bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored.Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10 ⁻⁴–10^− 5 L/s and rate constants for association in the order of 10⁸ L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-term dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry.     

Fe(OH)_3胶体与铜离子作用的研究

使用切向流超滤系统得到粒度较均匀的Fe(OH)3胶体,进而对Fe(OH)3胶体粒子与Cu2 的作用进行了研究,并将实验结果与南沙群岛海区表层水中铜与胶体物质结合状况的调查数据进行了比较分析,得到如下结果:(1)在海水介质中,铜在Fe(OH)3胶体上结合的百分率(pH>5)随pH的升高而下降,随着Fe(OH)3胶体浓度的减小而下降?(2)在天然海水介质中,使铜在Fe(OH)3胶体上结合的百分率在50%-70%的有机物浓度为1.0mg·L-1,有机物浓度的增大使铜与无机胶体结合的百分率有下降的趋势?     

塔里木克拉通东北缘二叠纪镁铁质岩浆氧化物与硫化物成矿条件对比

塔里木克拉通东北缘坡北、磁海等地二叠纪幔源岩浆活动形成了镍钴硫化物矿床和铁钴氧化物矿床，两者赋矿镁铁 超镁铁岩体的年龄相近(290~260 Ma)，主、微量元素和Sr Nd Hf同位素组成相似，分配系数接近的微量元素比值分布于相同趋势线，揭示两者岩浆源区相同，可能为俯冲板片流体交代的亏损地幔或软流圈地幔。两类矿床镁铁 超镁铁质岩中Co与Ni含量正相关，Co主要富集在基性程度高的岩石中；块状硫化物与磁铁矿矿石中Co与Ni相关性差，Co和Ni具有不同的富集机制，Co热液富集作用明显。北山镁铁 超镁铁杂岩体是地幔柱相关软流圈上涌，诱发俯冲板片交代的亏损岩石圈地幔发生部分熔融，形成的高镁母岩浆演化过程中经历壳源混染、硫化物饱和富集镍钴形成铜镍钴硫化物矿床，富铁母岩浆氧逸度高、富水，岩浆分离结晶磁铁矿、叠加热液作用富集钴，形成铁钴氧化物矿床。     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

低聚合羟基铁离子-蒙脱石复合体吸附砷的实验研究

将提纯的钙蒙脱石与羟基铁离子溶液作用，制备了低聚合羟基铁－蒙脱石复合体，用化学分析，电子探针分析，粉晶X射线衍射分析，差热分析和穆斯堡尔谱分析等手段。对蒙脱石原样，低聚合羟基铁－蒙脱石复合体和相同条件下制备的铁的含水氧化物进行了表征。在实际土壤的酸度（pH=4-7)和温度（18－40℃）条件下，进行了低聚合羟基铁－蒙脱石复合体吸附有害元素砷的实验，探讨了复合体的砷吸附能力与pH值，温度，吸附时间，砷初始浓度，离子强度间的关系，并与蒙脱石和铁的含水氧化物的砷吸附行为进行了对比，研究表明，在实验条件下，低聚合羟基铁－蒙脱石复合体对砷具有明显的亲合力，低聚合羟基铁－蒙脱石复合体吸附砷的过程有可能是地表岩石和土壤中重要的地球化学过程，是影响砷地地表，特别是土壤中迁移，富集的重要因素。     

Cathodoluminescence of authigenic albite

Authigenic albites in carbonate rocks typically grow in a high-grade diagenetic to low-grade metamorphic environment and often show Roc-Tourné-twinning sensu Füchtbauer. Based on an investigation of four Middle to South European occurrences, they show Mn²⁺- and Fe³⁺-activated cathodoluminescence (CL), as revealed by combined high resolution spectroscopy of cathodoluminescence emission (HRS-CL), electron paramagnetic resonance (EPR), and proton-induced X-ray emission (μPIXE).