Transformation of Fe （Ⅱ） and Fe （Ⅲ） in Enclosures of Dongshan Bay

根据2008年8月与11月在东山湾海域获得的调查资料对表层水中溶解态Fe（II）和Fe（III）含量、浮游植物叶绿素a、营养元素及其浓度等环境参数进行分析。结果表明,夏、秋季海水中Fe（II）浓度及其在总溶解铁中所占比例均与浮游植物叶绿素a呈正相关,其相关系数分别为0.7959、0.9219。现场围隔实验表明,海水中总溶解态Fe含量在24 h内有较大的变化,最大减少量达到17.4%。DS2站点海水中Fe（II）浓度及其在总溶解铁中所占比例随光照强度增加而增加。最高值与初始值相比较,叶绿素a较高的DS2站点海水中Fe（II）浓度增加较叶绿素a较低的DS5号站点高0.053μg/L。Fe（II）和Fe（III）加富实验研究了溶解态的Fe（II）和Fe（III）在海水中相互转化。高浓度的Fe（II）在海水中被氧化成Fe（III）,海水中浮游植物也会引发光还原作用使Fe（III）还原成Fe（II）。     

小体积萃取-石墨炉原子吸收法测定高纯硝酸钡中纳克级重金属元素

本文研究了石墨炉原子吸收光谱法测定高纯硝酸钡中超痕量重金属元素的分析技术。提出在大量钡基体存在时,采用小体积萃取体系APDC-MIBK同时萃取纳克级的Fe、Cu、Co和Ni。该法具有灵敏度高、无干扰、操作方便和减少沾污等特点。方法检出限为:Fe 7.2ng/g、Cu 12.8ng/g、Co 4.4ng/g和Ni 6.7ng/g。应用于红外光纤原料硝酸钡、硝酸铝中痕量重金属的测定,效果良好。     

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?     

南沙群岛南科1井白云岩发育特征及铁白云石成因机制的初步研究

南海自新生代以来发育了大量的碳酸盐岩台地和生物礁,并普遍发生白云岩化作用,具有广阔的油气勘探前景。文章通过开展岩相学观察、矿物学分析、常微量元素和碳氧同位素分析,同时结合Fe组分及Fe同位素地球化学分析,对南沙群岛南科1井白云岩的发育特征和成岩环境进行了系统研究。结果表明:南科1井上中新统—下更新统白云岩主要形成于近地表环境中,溶蚀孔隙发育,残余结构明显。白云岩层中发育有多个与暴露成因有关的界面,未发现石膏层的存在。同时,白云岩普遍具有低Fe、Mn和Sr的特征以及与现代海水相似的REE分布模式, δ¹³C和δ¹⁸O多为正值,但不存在相关性。整体来看,白云岩可能形成于轻微蒸发海水的渗透回流作用,还受到了与古气候变冷有关的海平面下降的控制。此外,南科1井岩芯中多个层位发育铁白云石,并且集中分布在暴露面附近。Fe组分和Fe同位素组成结果显示,白云岩中Fe主要来源于海水中碳酸盐的沉淀,成岩过程中基本不存在额外的陆源或热液来源的Fe混入。铁白云石主要形成于低温和浅埋藏环境中,大气淡水对生物骨架、生物碎屑以及自生碳酸盐矿物的淋滤-溶解作用为其提供了重要的...     

西藏谢通门县德新铅锌矿地质特征及找矿标志

德新铅锌矿位于西藏自治区谢通门县,地处西藏冈底斯Cu、Mo、Pb、Zn、Au、Fe成矿带中段。矿体主要赋存于岩浆岩与第三系火山岩的接触带,地层、岩浆岩控制了矿体的总体展布方向和空间位置。早期东西向构造对成矿起了导矿作用,晚期近南北向、北西、北东向构造是主要的容矿、储矿构造。属标准的地层、构造、岩浆岩＂三位一体＂的成矿模式。矿床成因可能属火山隐爆角砾岩型。本文提出了区内8条找矿标志。     

鄂东鸡冠嘴矿区成矿岩体锆石SHRIMP U-Pb定年及其意义

鄂东鸡冠嘴铜金(铁)矿床位于阳新岩体西北端,与铜绿山铜金矿床毗邻。矿区成矿岩体主要岩性为石英正长闪长玢岩、石英闪长岩、闪长岩和安山玢岩。其中石英正长闪长玢岩与成矿关系密切。在前人矿床地质特征研究基础上,笔者对成矿岩体进行了锆石SHRIMP U-Pb定年,获得石英正长闪长玢岩和闪长岩的年龄为146±2Ma(95%可信度,MSWD=1.3)和132±4Ma(95%可信度,MSWD=3)。测定结果表明,区内石英正长闪长玢岩和闪长岩分属燕山早期和燕山晚期岩浆活动的产物。鉴于矿体在空间上主要赋存于岩体内外接触带及层间破碎带中,推测成矿作用应略晚于石英正长闪长玢岩(146±2Ma)而早于闪长岩侵位的时间(132±4Ma),这与前人获得长江中下游铜铁金成矿带代表性矿床的辉钼矿Re-Os模式年龄分布在134.7～143Ma的研究结果一致。     

Electronic absorption spectra of Fe2+ ions in oxygen-based rock-forming minerals at temperatures between 297 and 600 K

 Polarized electronic single crystal spectra of natural Fe²⁺ ion-bearing oxygen-based minerals, in which ferrous ions enter octahedral sites of different symmetry and distortion (olivine, cordierite, ortho- and clinopyroxene, amphibole), eightfold sites in garnet (almandine) and clinopyroxene (M2), and tetrahedral sites in spinel, were studied at temperatures from 300 to ca. 600 K. In the minerals studied, the spin-allowed bands of Fe²⁺ display rather variable temperature behaviour. In most cases, due to the thermal expansion of the Fe²⁺-bearing polyhedra, bands shift to lower energies upon increasing temperature, though there are some exceptions to this rule: in cases of other than sixfold octahedral or close to octahedral coordination, in almandine and spinel the bands shift to higher energies, which can be explained by an increase in distortions of the Fe²⁺-bearing polyhedra. Splitting of the excited ⁵ E _g-level of Fe²⁺ ions usually, but not always, increases with temperature, reflecting thermally induced increase in distortion of the Fe²⁺-bearing sites in the minerals studied. Integral intensities of the bands in question do not always obey the general rule, according to which intensity should increase with temperature, when the 3d ^N-centred site is centrosymmetric, or should remain unchanged when the 3d ^N site lacks an inversion centre. The experimental results show that the response of the characteristics of absorption bands such as width, intensity and energy caused by dd transitions of Fe²⁺ in oxygen-based minerals to increasing temperature is not always uniform and is at variance with expectation. This temperature dependence cannot be used directly to solve band assignment problems, as earlier proposed in the literature. Received: 22 December 1999 / Accepted: 30 October 2000     

Magnetic phase diagrams of Mg-, Fe-, (Cu + Ti)- and Cu-substituted braunite Mn<Superscript>2+</Superscript>Mn<Subscript>6</Subscript><Superscript>3+</Superscript>SiO<Subscript>12</Subscript>

 The magnetic behavior of the Jahn-Teller structure braunite, (Mn²⁺ _1−yM _y )(Mn³⁺ _{6− x} M_x)SiO₁₂, is strongly influenced by the incorporation of elements substituting manganese. Magnetic properties of well-defined synthetic samples were investigated in dependence on the composition. The final results are presented in magnetic phase diagrams. To derive the necessary data, ac susceptibility and magnetization of braunites with the substitutional elements M = Mg, Fe, (Cu+Ti) and Cu were measured. Whereas the antiferromagnetic ordering temperature, T _N , of pure braunite is hardly affected by the substitution of nonmagnetic Mg, it is rapidly suppressed by the substitution of magnetic atoms at the Mn positions. Typically for a concentration (x, y) ≥ 0.7 of the substituted elements, a spin glass phase occurs in the magnetic phase diagrams. Additionally, for the braunite system with Fe³⁺ substitutions, we observe in the concentration range 0.2 < x< 0.7 a double transition from the paramagnetic state, first to the antiferromagnetic state, followed by a transition to a spin glass state at lower temperatures. The unusual change of the magnetic properties with magnetic substitution at the Mn positions is attributed to the peculiar antiferromagnetic structure of braunite, which has been resolved recently. Received: 19 April 2001 / Accepted: 6 September 2001