黄土剖面中赤铁矿和针铁矿的定量分析与气候干湿变化研究

为了了解黄土剖面中赤铁矿和针铁矿的分布特征,文章采用对铁氧化物矿物灵敏的漫反射光谱法(DRS),开展了赤铁矿和针铁矿的鉴定和测定研究,提出了定量分析赤铁矿和针铁矿含量的DRS新方法.选择天然典型黄土和古土壤样品,首先采用柠檬酸盐-重碳酸盐-连二亚硫酸盐(CBD)方法去除其中成壤成因的铁氧化物矿物,以其为基体配制含不同赤铁矿和针铁矿的系列标样,然后进行DRS测试和多元逐步回归分析,分别建立测定赤铁矿和针铁矿含量的校准方程并加以检验.利用DRS方法,分析了多个黄土剖面的赤铁矿和针铁矿含量,发现黄土-古土壤剖面的赤铁矿/针铁矿比值可作为东亚季风干/湿变化的敏感指标.该比值较高时反映了干燥土壤环境,而较低时指示了潮湿土壤环境.对灵台和洛川剖面中赤铁矿/针铁矿比值的分析,初步揭示了2.6Ma年以来黄土高原东亚季风阶段性变强的特征.     

长江三角洲东部岛屿风尘堆积赤铁矿和针铁矿含量及古气候意义

长江三角洲东延海域嵊山岛屿风尘堆积地层是记录晚更新世晚期东亚季风演变的重要载体。采用漫反射光谱（DRS）法、柠檬酸钠-重碳酸钠-连二亚硫酸钠（CBD）浸提法结合标准赤铁矿、针铁矿建立标准铁氧化物含量与反射率之间的校准方程,定量重建了东部岛屿风尘堆积的赤铁矿、针铁矿含量的变化特征。结果显示,东海嵊山岛风尘堆积中赤铁矿的含量为0.18%~0.40%,平均值为0.31%,针铁矿的含量为0.7%~1.19%,平均值为1.11%。根据赤铁矿、针铁矿含量特征结合地球化学和环境磁学参数,分析其记录的古环境信息:54~46 ka B.P.时期内气候相对干燥,季风降水减弱,46~39 ka B.P.时期内气候相对潮湿,季风降水增强;46±4 ka B.P.时期的高值可能指示了一个冷事件。     

基于漫反射光谱的铁氧化物定量分析在南方黄土中的适用性研究

基于漫反射光谱(DRS)的铁氧化物定量分析已用于北方黄土的研究,而在南方黄土中的适用性尚不清楚。本文选取江西九江黄土为研究对象,采用柠檬酸钠-重碳酸钠-连二亚硫酸钠(CBD)方法去除其中的游离铁,以此为基体分别加入不同比例的赤铁矿和针铁矿,通过多元线性回归方法建立了标样的铁氧化物含量与光谱反射率之间的校准方程。经检验,校准方程应用于未经CBD处理的剖面天然样品时,获得的赤铁矿含量较准,而针铁矿含量不准。原因可能在于:(1)混合体系中,赤铁矿与针铁矿互为基体,赤铁矿对针铁矿的干扰远大于针铁矿对赤铁矿的影响,这种差异在南方地区尤为明显;(2)CBD处理不能完全清除南方黄土中的针铁矿,可能与样品中含有部分结晶较好、粒度较粗的针铁矿有关,这也增加了针铁矿定量分析的不准确性;(3)铝的同晶替代现象对南方黄土影响更为显著,其中受晶格结构等影响,针铁矿的铝替代量比赤铁矿更大,可能对定量分析结果的准确性影响也更大。因而在南方黄土中,基于DRS的铁氧化物定量分析方法对于赤铁矿是适用和有效的,对于针铁矿的应用则需要慎重。     

铁（氢）氧化物悬液中磷酸盐的吸附-解吸特性研究

铁（氢）氧化物对P的吸持和释放在一定程度上决定着P的生物有效性和水体富营养化。以两种环境中常见晶质铁氧化物（针铁矿和赤铁矿）为对照,采用X射线衍射（XRD）、透射电镜（TEM）、热重分析（TGA）和孔径分析以及动力学和吸附-解吸热力学平衡等技术方法,研究了弱晶质水铁矿对P吸附-解吸特性,并探讨了相关机制。实验表明,三种矿物对P的吸附分为起始的快速反应和随后的慢速反应,它们均符合准一级动力学过程,反应中OH释放明显滞后于P吸附,P吸附经历了从外围到内囤配位、单齿到多齿配位过渡的过程,与晶质氧化铁比,水铁矿吸附容量和OH释放量更大、慢速吸附反应更快、存在缓慢扩散反应阶段,吸附容量依次是：水铁矿（436μmol／m^2）〉针铁矿（262μmol／m^2）〉赤铁矿（228μmol／m^2）,针铁矿和赤铁矿吸附P符合L（Langmuir）模型,而水铁矿更符合F（Fremldlictl）模型。中性盐介质（KCl）中在最大吸附量时P的解吸率依次为：水铁矿（85％）〈针铁矿（10％）〈赤铁矿（125％）,柠檬酸通过配体解吸和诱导溶解两种机制促进P的解吸,最大吸附量时解吸率依次是：针铁矿（25％）〈水铁矿（32％）〈赤铁矿（50％）。     

广西贵港岩溶地质高背景区富含铁锰结核土壤的矿物学与重金属地球化学特征

岩溶地质高背景区土壤中普遍存在的铁锰结核对重金属的赋存状态和有效性有重要影响。选择广西贵港覃塘岩溶地质高背景区富含铁锰结核的表层土壤(0~20 cm)为研究对象,筛分出不同粒径的铁锰结核(10~120目)和细粒径土壤(<120目)样品进行化学分析,针对以下三个方面开展研究:(1)重金属(As、Cd、Cr、Cu、Hg、Ni、Pb和Zn)在铁锰结核和细粒径土壤中的分布分配规律和铁氧化物矿物的组成;(2)铁氧化物矿物对富含铁锰结核的土壤中Cd等重金属富集的影响;(3)重金属在富含铁锰结核的土壤中的赋存机制。研究发现,铁锰结核中的Fe和Mn以及Cd等重金属含量随着粒径的增大而不断增加,说明Cd等重金属元素更倾向于在大粒径铁锰结核中富集;土壤中Cd等重金属总量的约90%赋存在结核中,表明研究区土壤中重金属主要以结核形式赋存;富含铁锰结核的土壤中赤铁矿和针铁矿的平均含量分别为0.61%和4.94%,且结核粒径越大,针铁矿和赤铁矿含量越高;除Hg外,Cd等重金属含量与针铁矿和赤铁矿的含量均呈现极显著正相关,与赤铁矿的相关性稍优于针铁矿,表明铁氧化物矿物与富含铁锰结核土壤中的Cd等重金属元素富集密切相关。铁锰结核的存在既能促进Cd等重金属在土壤中的富集,又能降低土壤中重金属的生物有效性,研究结果为解释岩溶地质高背景区土壤Cd等重金属元素高含量、低生物有效性提供了理论依据。     

漫反射光谱赤铁矿和针铁矿定量研究进展

沉积物-古土壤是记录古环境演化及古气候变迁的有效载体,利用沉积物-古土壤对气候环境信息的记录来研究全球变化问题,已成为当前地球科学研究的热点课题。赤铁矿和针铁矿是沉积物-古土壤中常见的次生矿物,二者含量的变化能有效反映成土过程中冷、暖、干、湿的变化。然而,赤铁矿和针铁矿在沉积物-古土壤中结晶度差且含量低,因此,对二者进行有效定量一直是研究的难题。近年来,漫反射光谱(DRS)分析在沉积物-古土壤中赤铁矿和针铁矿的定量研究中取得了一系列显著的成果。本文系统总结了漫反射光谱在赤铁矿和针铁矿定量中的原理,并对3种常见定量方法及其应用进行归纳,同时对定量过程中存在的问题和发展趋势进行深入讨论。     

几种铁（氢）氧化物对溶液中磷的吸附作用对比研究

铁(氢)氧化物不仅是土壤中广泛存在的矿物,也是重要的矿物资源。表生地质作用形成的针铁矿、赤铁矿和无定形氢氧化铁都具有纳米尺度,具有很高的表面积,表现出对磷的专性吸附,是低浓度磷的潜在吸附材料。本文通过铁(氢)氧化物对水溶液中磷酸根的等温吸附实验,初步对比研究了针铁矿、合成氧化铁黄、赤铁矿和无定形氢氧化铁对水中低浓度磷的吸附作用。结果表明,无定形氢氧化铁对水溶液中磷酸根的吸附能力最强(对低浓度磷的吸附达到5.5mg/g),其次是氧化铁黄和针铁矿,赤铁矿的吸附能力最差。几种铁(氢)氧化物对磷吸附容量的差别主要受比表面积控制。无定形氢氧化铁、合成氧化铁黄、针铁矿、赤铁矿对磷的吸附符合Freundlich等温方程。针铁矿和赤铁矿对磷的吸附动力学符合双常数速率方程。     

长江三角洲全新世地层中潮滩沉积磁性特征及其古环境意义

对长江三角洲北翼江苏南通地区NT钻孔（长60.9 m）进行了系统的环境磁学分析,并结合岩性特征、粒度、漫反射光谱（DRS）等手段,探讨了全新世早、晚期潮滩沉积的磁性特征及其古环境意义。NT孔自下而上可分为6层（U1~U6层）,其中U2层下部（49.9~44.8 m）和U6层（7.5~0.3 m）为潮滩沉积,具有较低的退磁参数S比值及较高的硬剩磁（HIRM）和SIRM/χ,表明反铁磁性矿物如赤铁矿、针铁矿等含量和比例较高。结合漫反射光谱（DRS）分析,发现U6层上部盐沼（1.5~0.3 m）赤铁矿和针铁矿富集,U2层下部的盐沼仅富集赤铁矿。这一差异与U2层和U6层形成的时期和沉积环境有关。U2层形成于晚更新世晚期至早全新世,且曾长期暴露地表,有利于赤铁矿的形成,其后随着海平面的持续上升,盐沼不断垂向加积,始终处于水下环境,不利于针铁矿的形成;U6层形成于晚全新世三角洲海岸的进积过程中,氧化还原相互交替的环境有利于针铁矿的形成,后期成陆后的成土作用生成了较多的磁赤铁矿和赤铁矿。研究表明,全新世三角洲发育过程中,不同时期形成的盐沼具有不同的磁性特征,磁性特征的研究可以提供潮滩沉积环境演变的信息,对三角洲古环境重建研究具有重要意义。     

离子吸附型稀土矿床中稀土的富集—分异特征:铁氧化物—黏土矿物复合体的约束

在离子吸附型稀土矿床中,黏土矿物被认为是离子吸附态稀土的主要吸附载体。风化壳中黏土矿物的透射电镜分析发现,黏土矿物普遍与铁氧化物形成复合体,很可能对稀土元素的富集–分异产生重要影响。本研究以广东省梅州市平远县仁居矿区的典型离子吸附型稀土矿床剖面为对象,通过提取富矿层中的细颗粒组分,采用X射线衍射、穆斯堡尔谱和透射电镜,对黏土矿物–铁氧化物复合体进行物相和形貌分析;在此基础上,采用顺序提取法测定不同化学形态的稀土总量,探究黏土矿物和铁氧化物对稀土元素富集–分异的贡献。结果表明,从全风化层到表土层,复合物从长石/伊利石–水铁矿/针铁矿复合体到高岭石/埃洛石–针铁矿/赤铁矿复合体,最终向高岭石–赤铁矿复合体转变。在表土层和全风化层的细颗粒组分中,离子交换态稀土约占25%和80%,而铁氧化物结合态稀土约占75%和20%。在表土层中, Ce的富集导致离子交换态和铁氧化物结合态稀土均富轻稀土。在全风化层中,随着深度的增加,离子交换态稀土由富轻稀土转变为富重稀土,铁氧化物结合态稀土均表现富重稀土的分异特征。离子交换态稀土总量和分异特征主要受黏土矿物–稀土界面作用和淋滤作用控制;而铁氧化物结合态稀土总...     

石英砂表面铁胶膜的合成——pH和铁摩尔比[Fe(Ⅱ)]/[Fe(Ⅲ)]的影响

本研究以石英砂为载体,在其颗粒表面合成铁胶膜,并探讨合成体系不同初始pH(5,6,7)及铁摩尔比(R=[Fe(Ⅱ)]/[Fe(Ⅲ)])等条件对铁胶膜形成的影响。研究表明,在初始pH相同的情况下,当R为0时,铁胶膜的矿物成分为弱晶质的水铁矿;R为0.01时的矿物成分为赤铁矿;R分别为0.02、0.04、0.06和0.10时为针铁矿,且随着R增加,X射线衍射(XRD)图谱中针铁矿的峰强度逐渐增加,扫描电镜(SEM)可观察到针铁矿晶形逐渐变大,且在R为0.10时晶体形貌最大;当R为0.50和体系只加入Fe(Ⅱ)时合成的铁矿物主要为针铁矿与磁铁矿的混合物。当R一定时,随着合成体系初始pH的增加,胶膜中针铁矿的XRD峰强度逐渐增强,在初始pH为7时其峰最强,且晶形逐渐变大。     

北大西洋ODP1049C孔Aptian-Albian期高频旋回大洋红层的成因:矿物学证据

北大西洋ODP171B航次1049C孔Aptian-Albian期沉积以出现大洋红层与灰色、白色沉积物高频旋回为特征。为了探讨大洋红层的成因,本文进行了矿物学、地球化学、沉积学等方面的研究。漫反射光谱、磁化率和活性铁数据表明,赤铁矿、针铁矿的出现是导致样品由白色向红色转变的矿物学原因。棕色和橙色样品中出现赤铁矿和针铁矿的特征峰,FeR/FeT平均值分别为0.23和0.24,明显区别于其他颜色的样品。磁化率与红层成良好的正相关关系,说明铁氧化物矿物含量的变化是导致磁化率变化的原因。X射线衍射结果表明,不论颜色如何,样品中均含伊利石、高岭石、蒙脱石、绿泥石等粘土矿物,其分布与样品颜色没有直接关系,很可能反映当时物源区气候稳定。ODP1049C孔岩芯沉积物出现橙色、棕色、白色、灰色等颜色的高频变化,颜色过渡接触界线清晰,说明导致红色变化的赤铁矿和针铁矿是沉积期低温氧化的产物。棕色样品中CaCO3含量最低,推测红层所对应的氧化条件是由于较低的有机质堆积速率造成的。     

Constraining the colouration mechanisms of Cretaceous Oceanic Red Beds using diffuse reflectance spectroscopy

We have used diffuse reflectance spectroscopy to investigate the colouration mechanisms of hematite in Cretaceous Oceanic Red Beds (CORBs). Data for samples of CORBs from the Chuangde section in Tibet, Vispi Quarry section in Italy, and Core 12X of Ocean Drilling Program Hole 1049C in the North Atlantic were compared with calibration datasets obtained for hematite in different crystalline forms (kidney and specular hematite) and calcite matrix. Spectra for hematite in either pure form or in calibration datasets show that the centre of the reflection peak shifts to a longer wavelength and depth (D) decreases as the crystallinity of the hematite increases. Compared with specular hematite, the presence of just 0.5% of kidney hematite can cause a much deeper absorption peak and greater redness value, which indicates that kidney hematite has a higher colouration capacity than specular hematite. However, both kidney and specular hematite exhibit a good correlation between the redness value for each calibration dataset and the absorption peak depth. In all three studied sections, hematite is the main iron oxide mineral responsible for colouration. Spectral features such as absorption peak depth and peak centre reveal that hematite crystallinity gradually decreases from red shale to limestone to marl. Based on a spectral comparison of red shale in the Chuangde section before and after citrate–bicarbonate–dithionite (CBD) treatment, we found that two forms of hematite are present: a fine-grained and dispersed form, and a detrital form. The former is relatively poorly crystalline hematite, which has a much stronger colouration capacity than the detrital form. In the Vispi Quarry section and Core 12X of ODP Hole 1049C, a good correlation between the absorption peak depth of hematite and redness value indicates that the red colouration is caused by hematite of similar crystallinity in each section.     

Paleoclimatic approach to the origin of the coloring of Turonian pelagic limestones from the Vispi Quarry section (Cretaceous,central Italy)

Samples of Turonian white to light gray and red limestones from the Vispi Quarry section in central Italy have been examined by X-ray Diffractometry (XRD), Electron Probe Micro-analysis (EPMA), Electron Spin Resonance (ESR), and Ultra violet-visible-near infrared (UV-VIS-NIR) Diffuse Reflectance Spectroscopy (DRS). The ESR, EPMA and XRD results suggest that Mn²⁺ was well-incorporated into the structure of calcite during the precipitation of the limestones. Amorphous ferric oxide (most probably hematite) and the Mn²⁺-bearing calcite endowed the limestone with a red color as the major pigmentation, and the Mn²⁺-bearing calcite gave it a pink tinge. The mineral assemblage is composed mainly of detrital boehmite and quartz, which are interpreted as having been imported from the Eurasian paleo-continent into the ocean by seasonal northeasterly winds. The boehmite formed by dehydration of gibbsite as an end-product of intensive chemical weathering of Fe, Mg, and Al-bearing aluminosilicates exposed in a subtropical environment. XRD results for the residues of Cretaceous Oceanic Red Beds (CORBs) dissolved in dilute acetum differed from those from Cretaceous Oceanic White Beds (COWBs) in that they contain hematite. This suggests that no hematite was imported into the ocean during the precipitation of the white limestone, and may explain why the same detrital origin for red and white limestones resulted in different colors by suggesting that climatic variations occurred on the paleo-continent during the precipitation of these two types of limestone. The presence of boehmite and hematite suggests that, during the Late Cretaceous, central Italy lay within a subtropical climatic zone with a seasonal alternation of warm rainy winters and hot, dry summers during the formation of the CORBs, and a continuously warm climate during the formation of the COWBs. The Mn/Fe(mol) ratios in the shells of spherical carbonate assemblages (probable microfossils) suggested that the ocean was much richer in iron during the precipitation of COWBs.     

Origin of red beds in the Ringerike Group (Silurian) of Norway

The Ringerike Group is a meandering fluviatile succession which is about 60% red. Most of the red zones are formed of mudrocks and siltstones and correspond to the fine members of fining-upwards cyclothems. The majority of coarse members are drab coloured.Textural studies of thin and polished sections show that the red colour is caused by finely crystalline hematite as matrix and grain-coatings. This hematite apparently crystallized post-depositionally. Hematite also occurs in other textural sites: within altered phyllosilicates, as detrital grains and as totally pseudomorphed phyllosilicates. This, and the lack of consistency between colour and clay mineralogy, suggests that the red beds have had a long and complex diagenetic history.Iron analyses indicate that the red beds are enriched in Fe³⁺ and total iron (FeO) by about 1%. This is thought to have been derived from the pre-depositional weathering of iron minerals and introduced into the sediments as amorphous iron hydroxide or iron-bearing clays. Crystallization of iron hydroxide under oxidizing conditions and the post-depositional alteration of iron-silicates and oxides is thought to be responsible for the formation of the red beds.     

Quantitative mineralogical and chemical assessment of the Nkout iron ore deposit,Southern Cameroon

The Nkout deposit is part of an emerging iron ore province in West and Central Africa. The deposit is an oxide facies iron formation comprising fresh magnetite banded iron formation (BIF) at depth, which weathers and oxidises towards the surface forming caps of high grade hematite/martite–goethite ores. The mineral species, compositions, mineral associations, and liberation have been studied using automated mineralogy (QEMSCAN^®) combined with whole rock geochemistry, mineral chemistry and mineralogical techniques. Drill cores (saprolitic, lateritic, BIF), grab and outcrop samples were studied and divided into 4 main groups based on whole rock Fe content and a weathering index. The groups are; enriched material (EM), weathered magnetite itabirite (WMI), transitional magnetite itabirite (TMI) and magnetite itabirite (MI). The main iron minerals are the iron oxides (magnetite, hematite, and goethite) and chamosite. The iron oxides are closely associated in the high grade cap and liberation of them individually is poor. Liberation increases when they are grouped together as iron oxides. Chamosite significantly lowers the liberation of the iron oxides. Automated mineralogy by QEMSCAN^® (or other similar techniques) can distinguish between Fe oxides if set up and calibrated carefully using the backscattered electron signal. Electron beam techniques have the advantage over other quantitative mineralogy techniques of being able to determine mineral chemical variants of ore and gangue minerals, although reflected light optical microscopy remains the most sensitive method of distinguishing closely related iron oxide minerals. Both optical and electron beam automated mineralogical methods have distinct advantages over quantitative XRD in that they can determine mineral associations, liberation, amorphous phases and trace phases.     

Burial Records of Reactive Iron in Cretaceous Black Shales and Oceanic Red Beds from Southern Tibet

One of the new directions in the field of Cretaceous research is to elucidate the mechanism of the sedimentary transition from the Cretaceous black shales to oceanic red beds. A chemical sequential extraction method was applied to these two types of rocks from southern Tibet to investigate the burial records of reactive iron. Results indicate that carbonate-associated iron and pyrite are relatively enriched in the black shales, but depleted or absent in red beds. The main feature of the reactive iron in the red beds is relative enrichment of iron oxides （largely hematite）, which occurred during syn-depostion or early diagenesis. The ratio between iron oxides and the total iron indicates an oxygen-enriched environment for red bed deposition. A comparison between the reactive iron burial records and proxies of paleo-productivity suggests that paleo-productivity decreases when the ratio between iron oxides and the total iron increases in the red beds. This phenomenon could imply that the relationship between marine redox and productivity might be one of the reasons for the sedimentary transition from Cretaceous black shale to oceanic red bed deposition.     

Iron mineralization in the Garagu Formation of Gara Mountain,Duhok Governorate,Kurdistan, NE Iraq: geochemistry,mineralogy and origin

The iron mineralization is hosted in carbonate beds of the Garagu Formation (Early Cretaceous) at Gara Mountain, Duhok Governorate, Kurdistan Region, NE Iraq. The Garagu Formation is composed of a series of limestone and siltstone beds with iron-rich beds in the middle part. The iron-rich limestones are iron-rich oolitic grainstone and bioclastic wackestone with hematite and goethite minerals. Geochemical results drawn from this study indicate that the percentage of iron in these beds reaches 19.73 %. Moreover, petrographical investigation of thin and polished sections reveals the presence of different types of fossils, indicating an open marine interior platform depositional environment. Different iron minerals, including hematite, goethite, siderite, pyrite and magnetite, were identified in the sections, and their geneses were related to syngenetic and diagenetic processes. The geochemical distribution of major and trace elements, as well as the V/Ni, V/(V+Ni), V/Cr and Sr/Ba ratios, indicates a reducing environment during the precipitation of carbonate sediments and a subsequent oxidizing condition during the concentration of iron minerals via diagenesis.     

福建白垩系沙县组地层磁学特征及其环境意义

广泛分布于中国南方的白垩系巨厚地层被认为是河湖相沉积,蕴含着丰富的古气候古环境变化的信息。白垩纪是典型的温室时期,其气候特征可以为当代和未来温室气候研究提供重要借鉴。对位于中国东南的福建省三明市沙县和永安地区的白垩系沙县组典型地层进行了系统的环境磁学参数测量,结合漫反射光谱(DRS)和色度指标,探讨了该地层磁学特征及其环境指示意义和红色的成因。结果表明:1)红色调和黄色调地层的主要磁性矿物分别为赤铁矿和针铁矿,均含有顺磁性矿物和极少量的亚铁磁性矿物;2)相对于粗粒的砂岩,细粒的粉砂岩赤铁矿含量较高;3)红色赤铁矿与黄色针铁矿均形成于成岩阶段之前,具体形成阶段与形成原因需要具体分析;4)红色调地层的赤铁矿指示高温的气候环境;黄色调地层的针铁矿指示局部的湿润环境。磁学参数变化的具体环境指示意义需要进一步研究。