利用漫反射光谱鉴定红粘土中针铁矿和赤铁矿

针铁矿(Gt)和赤铁矿(Hm)是广泛存在于土壤和沉积物中的重要铁矿物。这两种矿物在土壤和沉积物中含量很低,常规的测试手段很难有效地测定其含量。利用反射光谱联合加热处理的方法,可对土壤及沉积物样品中针铁矿和赤铁矿进行定性或半定量测定。实验结果显示,样品加热到300℃后,针铁矿的反射光谱的一阶导数特征峰发生了变化,赤铁矿的一阶导数特征峰却没有明显的变化。因此加热前后样品反射光谱一阶导数的变化取决于针铁矿和赤铁矿的含量。利用这种方法估计黄土高原第三纪红粘土样品中的赤铁矿含量约为0.3%～0.4%,针铁矿含量约为0.5%～1%。     

柴达木盆地早始新世大暖期古土壤中赤铁矿和针铁矿的定量分析及其气候意义

赤铁矿和针铁矿是古土壤中常见的两种风化产物,定量研究赤铁矿和针铁矿有利于了解成壤时期古气候特征。文章利用可见光波段的漫反射光谱法对早始新世大暖期期间柴达木盆地大红沟剖面路乐河组古土壤中的铁氧化物矿物进行了定量分析。测试结果清晰显示了赤铁矿和针铁矿的存在,其中赤铁矿含量约在0.09~17.16 g/kg之间,针铁矿的含量大致为0.13~24.6 g/kg;针铁矿（Gt）相对赤铁矿（Hm）平均含量较高（Gt/Hm变化范围0.04~34.34,平均值约为2.18）,且数据存在较大波动。古土壤在早始新世大暖期时经历了3个阶段的古气候变化,早期古降雨量偏高,针铁矿/赤铁矿平均值为3.06,数据波动明显,指示相对温暖湿润且干湿波动大的气候条件;中期时古降雨量稍低,针铁矿/赤铁矿平均值降低至1.75,指示相对干旱的气候条件;晚期时古降雨量增加,针铁矿/赤铁矿平均值升高至1.80,指示相对温暖湿润的气候条件。其中早期的路乐河组古土壤对应了全球早始新世气候大暖期的峰值,路乐河组古土壤整体的古气候特征是对全球早始新世气候大暖期的区域响应。

     

近红外漫反射光谱在沉积物化学成分分析中的研究进展

沉积物中有机质及相关元素含量、重金属含量等是研究环境污染和古环境的依据。利用近红外漫反射光谱测定沉积物中的化学成分,方法简便、快捷、价廉。本文概述了近红外漫反射光谱测定沉积物中化学成分的基本流程、样品制备及建模方法,介绍了如何通过选择建模样品、利用光谱预处理及回归分析等方法提高近红外光谱模型的定量能力,综述了近红外漫反射光谱分析沉积物中的有机碳、总氮、总磷、生物硅、重金属含量等方法。但是利用近红外光谱分析沉积物中的化学成分研究起步较晚,仍存在很多问题,有必要深入探讨近红外光谱分析沉积物的化学成分时产生误差的机理,进一步开展建模样品的计算机选择方法、光谱预处理方法和数学模型优化等方面的研究,提高近红外漫反射光谱分析沉积物中化学成分的精密度和准确度。     

南海沉积物漫反射光谱反映的220ka以来东亚夏季风变迁

对南海越南岸外“太阳号”95航次17954孔220ka以来的沉积样品进行了漫反射光谱分析, 并从中提取F1和F2两个主因子及亮度和红度等漫反射光谱特征值, 发现漫反射光谱F1值和亮度反映了沉积物中的碳酸盐含量, 而漫反射光谱F2值和红度反映了沉积物中的铁氧化物含量, 后者可用作东亚夏季风的替代性指标.17954孔沉积物的漫反射光谱F2值显示, 倒数第二次冰消期东亚夏季风快速增长时间约在129ka; 本次工作还发现东亚夏季风在两次冰消期前的氧同位素2阶段和6阶段晚期各有一个异常强盛的时期.漫反射分析结果显示东亚夏季风主要受控于太阳辐射强度变化, 并明显地受低纬地区气候的影响.      

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。     

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.     

江苏南通黄泥山黄土漫反射光谱特征及古环境意义

选取长江下游江苏南通黄泥山黄土堆积为研究对象,运用磁滞回线、热磁曲线与漫反射光谱特征分析其磁性矿物组成,结合色度参数、地球化学特征,探讨黄泥山黄土记录的古环境信息。研究发现,黄泥山黄土中亚铁磁性矿物主要为磁铁矿、磁赤铁矿,不完整反铁磁性矿物主要为赤铁矿（Hm）、针铁矿（Gt）。剖面中Hm/Gt值在U1（147~124 cm）和U3（39~0 cm）层中小于1,在U2（123~40 cm）层中大于1,这指示U1、U3层形成于相对干燥的气候环境,U2层形成于相对湿润的气候环境。色度参数亮度（L^*）、红度（a^*）值与磁化率（χ）及总铁的百分含量（TFeOx%）、化学风化指数（CIA）随深度变化趋势相关性明显,且指示U1和U3层经历了相对U2层较弱的成壤作用。因此,黄泥山黄土漫反射光谱特征及色度参数L^*和a^*值可作为黄土风化与夏季风强度的替代性指标。与其他典型黄土剖面特征对比,黄泥山黄土总体上经历了相对干冷的气候环境,其中U2阶段的沉积环境相对暖湿,U1和U3较为干冷。该研究对长江下游地区古气候干湿变化及古环境重建具有一定的参考价值。

     

沉积物中铁氧化物的定量方法及其 在白垩纪大洋红层中的应用

赤铁矿和针铁矿是自然界中最稳定的两种铁氧化物,广泛存在于地球的各个圈层。很多沉积物的颜色都是由它们引 起的,它们的形成和保存具有重要的环境指示意义。实验室中赤铁矿和针铁矿的表征和鉴定手段很多,但受其含量低、结 晶差、颗粒细小难分离等因素的困扰以及某些测试方法自身的限制,能用于铁氧化物定量分析的方法很少。文中就常用的 基于X射线衍射（XRD） 和漫反射光谱（DRS） 的铁氧化物定量方法进行了系统评价。在定性分析的基础上,采用基于 XRD的K值法获得西藏床得剖面红色页岩中赤铁矿的含量为3.81％~8.11％,采用DRS与多元线性回归相结合的方法获得北 大西洋ODP1049C孔12X岩芯段棕色层中赤铁矿和针铁矿的含量分别为0.13％~0.82％和0.22%~0.81％,橙色层中赤铁矿和 针铁矿的含量分别为0.19%~0.46％和0.29%~0.67％。与其它分析结果的比较表明,这两种定量方法在白垩纪大洋红层中的 应用是可行的。但在实际应用时,首先要通过XRD和DRS相结合来提高定性分析的准确性,然后通过综合分析铁氧化物的 预判含量范围和结晶程度来选择合适的定量方法。     

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。     

3Ma以来黄土高原朝那黄土-红粘土序列赤铁矿记录及其古气候意义

土壤和前期研究表明黄土-红粘土序列的赤铁矿含量与环境密切相关,对气候的干湿变化非常敏感,气候越湿热,赤铁矿含量越高。本文研究表明黄土-红粘土样品漫反射光谱一阶导数曲线在555~575nm间的峰面积作为赤铁矿指数可以客观有效地指示赤铁矿含量的高低。通过黄土高原朝那剖面红粘土-黄土序列的系统漫反射光谱分析,建立了3Ma以来黄土高原赤铁矿含量变化记录,揭示赤铁矿含量在约2.5Ma,1.5Ma,0.6Ma和0.15Ma显著阶段性减小,指示了黄土高原阶段性变冷干的演化历史。     

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.     

Twin formation in hematite during dehydration of goethite

Twin formation in hematite during dehydration was investigated using X-ray diffraction, electron diffraction, and high-resolution transmission electron microscopy (TEM). When synthetic goethite was heated at different temperatures between 100 and 800 °C, a phase transformation occurred at temperatures above 250 °C. The electron diffraction patterns showed that the single-crystalline goethite with a growth direction of [001]_G was transformed into hematite with a growth direction of [100]_H. Two non-equivalent structures emerged in hematite after dehydration, with twin boundaries at the interface between the two variants. As the temperature was increased, crystal growth occurred. At 800 °C, the majority of the twin boundaries disappeared; however, some hematite particles remained in the twinned variant. The electron diffraction patterns and high-resolution TEM observations indicated that the twin boundaries consisted of crystallographically equivalent prismatic (100) (010), and (1\(\bar{1}\)0) planes. According to the total energy calculations based on spin-polarized density functional theory, the twin boundary of prismatic (100) screw had small interfacial energy (0.24 J/m²). Owing to this low interfacial energy, the prismatic (100) screw interface remained after higher-temperature treatment at 800 °C.     

Studies on the solid acidity of heated and cation-exchanged montmorillonite using n-butylamine titration in non-aqueous system and diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy

The effects of heating and cation exchange on the solid acidity of montmorillonite were investigated using n-butylamine titration in non-aqueous system and diffuse reflectance Fourier transform infrared spectroscopy. The number of total, Brønsted, and Lewis acid sites showed the same modulation tendency with increasing heating temperature, reaching a maximum at 120 °C and subsequently decreasing until it reaches a minimum at 600 °C. The Lewis acid sites result from unsaturated Al³⁺ cations, and their number increased with the heating temperature due to the dehydration and dehydroxylation of montmorillonite. The generation and evolution of Brønsted acidity were mainly related to interlayer-polarized water molecules. Water adsorbed on the unsaturated Al³⁺ ions also acted as a Brønsted acid. The acid strength of the Brønsted acid sites was dependent on the polarization ability of the exchangeable cation, the amount of interlayer water, and the degree of dissociation of the interlayer water coordinated to exchangeable cations. All cation-exchanged montmorillonites exhibited different numbers of acid sites and various distributions of acid strength. Brønsted acidity was predominant in Al³⁺-exchanged montmorillonite, whereas the Na⁺- and K⁺-exchanged montmorillonites showed predominantly Lewis acidity. Moreover, Mg²⁺- and Li⁺-exchanged montmorillonites exhibited approximately equal numbers of Brønsted and Lewis acid sites. The Brønsted acidity of cation-exchanged montmorillonite was positively correlated with the charge-to-radius ratios of the cations, whereas the Lewis acidity was highly dependent on the electronegativity of the cations. The acid strengths of Al³⁺- and Mg²⁺-exchanged montmorillonites were remarkably higher than those of monovalent cation-exchanged montmorillonites, showing the highest acid strength (H ₀ ≤ ?3.0). Li⁺- and Na⁺-exchanged montmorillonites exhibited an acid strength distribution of ?3.0 < H ₀ ≤ 4.8, with the acid strength ranging primarily from 1.5 to 3.3 in Li⁺-exchanged montmorillonite, whereas only weaker-strength acid sites (1.5 < H ₀ ≤ 4.8) were present in K⁺-exchanged montmorillonite. The results of the catalysis experiments indicated that montmorillonite promoted the thermal decomposition of the model organic. The catalytic activity showed a positive correlation with the solid acidity of montmorillonite and was affected by cation exchange, which occurs naturally in geological processes.     

SO2、NO2与针铁矿、赤铁矿、磁铁矿的非均相反应

硫酸盐是大气颗粒物的重要组分,SO2与矿质颗粒物的非均相反应可能是硫酸盐和水溶性铁形成的重要途径之一,但目前对该反应途径的研究比较有限.本研究开展了不同相对湿度条件下SO2((7.14±0.29)μg/L)、NO2((5.13±0.21)μg/L)与针铁矿、磁铁矿、赤铁矿的非均相反应,定量分析了产物硫酸盐、硝酸盐以及水...     

Probing the local environment of substitutional Al$$^{}$$ in goethite using X-ray absorption spectroscopy and first-principles calculations

We present experimental and calculated Al K-edge X-ray absorption near-edge structure (XANES) spectra of aluminous goethite with 10–33 mol% of AlOOH and diaspore. Significant changes are observed experimentally in the near- and pre-edge regions with increasing Al concentration in goethite. First-principles calculations based on density functional theory (DFT) reproduce successfully the experimental trends. This permits to identify the electronic and structural parameters controlling the spectral features and to improve our knowledge of the local environment of \(\hbox {Al}^{3+}\) in the goethite–diaspore partial solid solution. In the near-edge region, the larger peak spacing in diaspore compared to Al-bearing goethite is related to the nature (Fe or Al) of the first cation neighbours around the absorbing Al atom (Al*). The intensity ratio of the two near-edge peaks, which decreases with Al concentration, is correlated with the average distance of the first cations around Al* and the distortion of the \(\hbox {AlO}_6\) octahedron. Finally, the decrease in intensity of the pre-edge features with increasing Al concentration is due to the smaller number of Fe atoms in the local environment of Al since Al atoms tend to cluster. In addition, it is found that the pre-edge features of the Al K-edge XANES spectra enable to probe indirectly empty 3d states of Fe. Energetic, structural and spectroscopic results suggest that for Al concentrations around 10 mol%, Al atoms can be considered as isolated, whereas above 25 mol%, Al clusters are more likely to occur.     

Determination of metamorphic grade in siliceous muscovite-bearing rocks in Madagascar using reflectance spectroscopy

Visible short-wave infrared laboratory reflectance spectra of quartzites and micaschists from the Precambrian basement of central-western Madagascar are dominated by the muscovite spectrum. The spectra were measured from rock samples collected along an E–W traverse across a metamorphic sequence recording progressively higher metamorphic grades. The wavelength of the Al–OH band around 2200 nm decreased westward and was inversely correlated with Al^VI content of muscovite in rocks showing the same nonlimiting assemblage. This shift is correlated also with an increase of band intensity, which is attributed to the progressive increase of metamorphic grade. All of these variations in rock spectral properties can be detected by the high spectral resolution MIVIS and AVIRIS sensors, as well as by the lower resolution TM sensor.     

基于反射光谱的珠江口咸潮遥感方法

为监测珠江口河网区水体的盐度变化,基于同步测量的水体黄色物质、盐度和水体表面光谱数据,利用MATLAB分析了水体光谱反射率和黄色物质浓度之间的关系。结果表明:在磨刀门水道,反射率与黄色物质在400nm处的吸收系数g₄₀₀有较好关系,在R₇₀₄/R₅₁₃处,R²=0.70;在虎门水道,g₄₀₀与反射率比值R₇₀₃/R₄₈₈之间也有较强的负相关,R²=0.58。同样,又分析了磨刀门和虎门水道黄色物质吸收系数与表面盐度的关系,都发现了较好的相关性,R²>0.67。根据以上分析,得到了一种珠江口河网区水体表面盐度监测的新方法,并采用中等分辨率成像光谱仪(MERIS)的模拟数据来进行模型验证,结果表明利用MERIS数据对珠江口河网区咸潮进行监测是可行的(均方根误差小于0.308%)。     

同步辐射软X射线吸收谱与发射谱测定天然针铁矿能带结构

天然半导体矿物由于成分、缺陷复杂,传统测试方法如紫外可见漫反射等难以准确测定其禁带宽度.本文以针铁矿为例,通过第一性原理计算得到纯针铁矿及掺Al针铁矿的电子结构.计算结果显示,纯针铁矿导带底与价带顶均由Fe3d与O2p轨道组成,而当含杂质Al时,Al2p与O2p发生杂化参与了价带组成.在此基础上,利用同步辐射X射线氧的K边吸收谱与发射谱对纯针铁矿及天然针铁矿的能带结构进行了测定.结果表明,天然含Al的针铁矿禁带宽度为2.30eV,小于纯针铁矿(2.57eV).本研究提供了一种测定天然氧化物矿物禁带宽度的新方法,为深入研究天然半导体可见光催化活性产生机制提供了理论依据.