具磷灰石假象绿松石的岩石矿物学及谱学特征

采用x射线粉晶衍射（XRD）、博里叶变换红外光谱（FTI码以及拉曼光谱等方法对安徽马鞍山具磷灰石假象的绿松石进行了研究。结果表明：其主要矿物组成为绿松石,保留了磷灰石六边形的形态特征。XRD~U试的特征谱线d值为36745～36748（111）、29008～29025（123）、34247～34293（2101、32709～32781（113）、61626～61781（011）3020130～20162（301）,与绿松石的标准衍射谱线基本致。红外光谱测试分析表明：3510～3465cm。间的谱带归属绿松石0（OH）的伸缩振动,3300～3070cm’间的谱带归属为绿松Nu（M-H。O）伸缩振动,1210-1012cm’间的谱带归属为绿松石U3口O。）ira缩振动,在838cm。附近的吸收谱带归属为绿松石6（OH）弯曲振动,655-480cm。间的谱带归属为绿松石u4（P04）弯曲振动。拉曼光谱测试分析表明：3466cm’附近的尖锐拉曼谱峰归属于绿松石（OH）基团的伸缩振动所致,宽缓的拉曼谱峰3281cm’~03078cm’归属于绿松石中水合络离子的伸缩振动,798cm’谱峰则是由于OH的弯曲振动所致。     

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.     

Sorption Characteristics of Rare Earth Element Eu^3＋ onto Silica-Water Interfaces Studied by Fluorescence Spectroscopy

The sorption of Eu species onto nano-size silica-water interfaces was investigated using fluorescence spectroscopy for Ph ranges of 1-8.5 and an initial Eu concentration (Ceu) of 2×10-4 M. The sorption rate of Eu was initially low, but significantly increased at Ph>4. The sorption density of Eu species on a silica surface was ～1.58×10-7 mol/m2 when the dissolved Eu species were completely sorbed onto silica-water interfaces at Ph=～5.8. The sorbed Eu species at Ph<6 is aquo Eu3 , which is sorbed onto silica-water interfaces as an outer-sphere complex at Ph<5, but may be sorbed as an inner-sphere bidentate complex at 5相似文献   

腐殖酸三维荧光光谱特性研究

腐殖质的荧光特性被广泛用来解析其在各种天然环境中的来源及分布.由于荧光光谱分析具有灵敏度高,选择性好,且不破坏样品结构的优点,非常适合用来研究腐殖质的结构和官能团等特征.利用三维荧光激发-发射光谱研究了 Fluka腐殖酸的荧光光谱特性,结果显示,离子强度(0～0.05 mol/L KClO4)对 Fluka腐殖酸的三维荧光光谱特性影响非常小,而腐殖酸的浓度(5～100 mg/L)和溶液 pH(2～12)对其三维荧光光谱特性影响显著.当腐殖酸浓度增大时,荧光峰出现明显红移现象.荧光强度一般随着 pH的升高而增大,当 pH大于 10后呈下降趋势,我们从垃圾渗滤液溶解有机质的实验结果中也得到相同结论;在浓度为 50 mg/L和 100 mg/L的 Fluka腐殖酸中,荧光峰 B(fulvic-like)的荧光强度却在 pH=5.0左右时达到最大值,与前人报道的土壤富里酸的行为一致,质子化常数 lgK′ HL分别为 3.57和 3.13,与二羧基化合物接近,说明荧光峰 B可能与 Fluka腐殖酸结构中的羧基有关;荧光峰 A与荧光峰 B的荧光强度比值 r(A/B)在 0.61～2.59之间,并且在 pH=2～11范围内, r(A/B)与 pH具有较好的线性相关关系,表明荧光峰 A和荧光峰 B随着 pH值的改变有着相同的变化趋势.     

Ab-initio calculations of the proton location in topaz-OH,Al<Subscript>2</Subscript>SiO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>

The position of hydrogen in the structure of topaz-OH was determined by means of ab-initio quantum-mechanic calculations. Static lattice energy calculations predict the existence of four non-equivalent positions of protons, which are characterized by O4–H1... O1, O4–H2... O2, O4–H3... O3 and O4–H4... O4 hydrogen bonds. The distribution of the protons between positions of local equilibrium is controlled by the proton–proton avoidance rule and the strength of the hydrogen bonds. The most favourable configuration of hydrogen atoms is achieved for adjacent protons, which form O4–H3... O3 and O4–H4... O4 hydrogen bonds, respectively. The thermal excitation of atoms at a temperature of 55 K is large enough for the hydrogen atoms occasionally to change their positions to form O4–H1... O1 and O4–H2... O2 bonds. At ambient pressures and higher temperatures the protons are in a dynamic exchange between the allowed positions of local minima. As a consequence, for nearly room-temperature conditions, the dynamic change between different structural configurations leads to the violation of all possible symmetry elements and with that to space group #E5/E5#1. The flipping of the protons between different sites is achieved by simple rotation of the OH-dipole and does not produce any significant distortion of the framework of topaz, whose symmetry remains that of the space group Pbnm. Therefore, no reduction of symmetry has been observed in former X-ray studies on topaz-OH. Calculated IR absorption spectra of topaz-OH were found to be in good agreement with measured spectra. According to the calculations, the two favourable configurations of protons might correspond to the measured peak splitting within the OH-stretching range. An experimentally observed low-frequency band at 3520 cm^–1 was assigned to the OH-stretching of the O4–H3... O3 bond, while the band at 3600 cm^–1 was attributed to OH-stretching of the O4–H4... O4 hydrogen bond. The broad peak in FAR-IR frequency range at 100–150 cm^–1 is attributed to the stretching of H3... O3 and H4... O4 contacts. The rate of proton exchange at 670 K among different sites was estimated by ab-inito molecular dynamic simulations. The calculations predict that flipping of adjacent protons between O4–H3... O3 and O4–H4... O4 bonds at 670 K occur at a rate of about 1.96 THz.     

Thermal decomposition of NH4-analcime

The thermal decomposition of ammonium-exchanged natural analcime is characterized by gas chromatography, IR spectroscopy and X-ray diffraction. The de-ammoniation and dehydroxylation proceed in parallel throughout the decomposition, which evidences the instability of the protonated analcime framework. The mechanism of degassing of NH₄-analcime changes throughout its decomposition. At the initial step, the mechanism of de-ammoniation consists in thermal dissociation of NH₄⁺ molecule onto NH₃ and proton (framework OH group) and diffusion of NH₃ out of the structure. Subsequent decomposition and removal of the OH groups lead to a progressive loss of crystallinity. At this step, an apparent activation energy for NH₃ desorption is estimated to be 145(±13) kJ mol^–1. This value is within the upper limit of the activation energy characteristic for the NH₃ desorption from proton centres in large-pore zeolites. At the final step, the adsorption of NH₃ and protons onto the defect centres in the amorphosed aluminosilicate framework results in a significant increase of an apparent activation energy for the de-ammoniation and dehydroxylation up to 270(±20) kJ mol^–1.     

基于可见—近红外反射光谱的典型农田重金属污染风险分类研究

对于人为因素或自然因素造成的农田土壤重金属元素污染,需要进行大面积的土壤环境质量调查和分类管控,然而传统的采样测试方法存在工作量大、代价高等问题。可见—近红外（Vis-NIR）反射光谱是一种快速低成本获取土壤理化信息的手段。为研究Vis-NIR反射光谱预测模型划分土壤重金属污染风险类别的能力,文章以典型人为污染地区（浙江温岭）和典型地质高背景地区（广西横县）的390份农田土壤为样本,测定8种重金属元素（As、Cd、Cr、Cu、Hg、Ni、Pb和Zn）的含量和pH值,并测定土壤Vis-NIR光谱。使用偏最小二乘（PLS）和支持向量机（SVM）算法建立回归模型,对土壤重金属含量和pH值进行预测,并基于预测值进行土壤重金属污染风险分类。结果显示,温岭土壤主要污染元素Cd和Cu的光谱模型回归预测偏差（RPD）分别为1.23和1.19,预测机制与有机质有关。横县土壤主要污染元素As和Cd的RPD分别为1.98和1.93,预测机制与铁氧化物和粘土矿物有关。地质高背景土壤重金属与铁氧化物的正相关性普遍较强,使得光谱模型对重金属含量预测准确度较高。温岭和横县土壤pH值的光谱模型RPD分别为1.76和1.68。土壤重金属污染风险光谱分类的总体 准确度分别为75.0%~100%（温岭）和80.0%~100％（横县）。将Vis-NIR光谱与遥感技术相结合,对农田土壤重金属污染风险进行快速分类总体是可行的。     

Transformation of ammonium nitrogen and response characteristics of nitrifying functional genes in tannery sludge contaminated soil

High concentrations of ammonium nitrogen released from tannery sludge during storage in open air may cause nitrogen pollution to soil and groundwater. To study the transformation mechanism of NH₄⁺-N by nitrifying functional bacteria in tannery sludge contaminated soils, a series of contaminated soil culture experiments were conducted in this study. The contents of ammonium nitrogen (as NH₄⁺-N), nitrite nitrogen (as NO₂^?-N) and nitrate nitrogen (as NO₃^?-N) were analyzed during the culture period under different conditions of pollution load, soil particle and redox environment. Sigmodial equation was used to interpret the change of NO₃^?-N with time in contaminated soils. The abundance variations of nitrifying functional genes (amoA and nxrA) were also detected using the real-time quantitative fluorescence PCR method. The results show that the nitrification of NH₄⁺-N was aggravated in the contaminated silt soil and fine sand under the condition of lower pollution load, finer particle size and more oxidizing environment. The sigmodial equation well fitted the dynamic accumulation curve of the NO₃^?-N content in the tannery sludge contaminated soils. The Cr(III) content increased with increasing pollution load, which inhibited the reproduction and activity of nitrifying bacteria in the soils, especially in coarse-grained soil. The accumulation of NO₂^?-N contents became more obvious with the increase of pollution load in the fine sand, and only 41.5% of the NH₄⁺-N was transformed to NO₃^?-N. The redox environment was the main factor affecting nitrification process in the soil. Compared to the aerobic soil environment, the transformation of NH₄⁺-N was significantly inhibited under anaerobic incubation condition, and the NO₃^?-N contents decreased by 37.2%, 61.9% and 91.9% under low, medium and high pollution loads, respectively. Nitrification was stronger in the silt soil since its copy number of amoA and nxrA genes was two times larger than that of fine sand. Moreover, the copy numbers of amoA and nxrA genes in the silt soil under the aerobic environment were 2.7 times and 2.2 times larger than those in the anaerobic environment. The abundance changes of the amoA and nxrA functional genes have a positive correlation with the nitrification intensity in the tannery sludge-contaminated soil.     

微波等离子体原子发射光谱法测定偏远矿区海泡石中的主微量元素

海泡石是具有层状结构的含水富镁硅酸盐黏土矿物,其中无机元素含量是揭示其成矿物质来源、成矿流体性质和矿床成因的重要依据,通常采用电感耦合等离子体发射光谱/质谱法（ICP-OES/MS）进行测定,等离子体（ICP）的高温激发会产生成大量谱线干扰,维持ICP稳定工作需使用高纯氩气,持续供气对于偏远矿区海泡石的检测还将面对气体采购和运输不便的问题。本文基于微波等离子体原子发射光谱（MP-AES）的低温激发技术减少光谱干扰,建立了准确测定偏远矿区海泡石中主量元素Mg、Al、Ca、Fe、K、Na和微量元素Cu、Zn、Mn、Pb含量的分析方法。利用硝酸-盐酸-氢氟酸混合酸对海泡石进行微波消解,避免了样品处理过程中分析元素的损失,加快了样品处理速度,同时提高了样品溶液的稳定性。通过选择各元素光谱线的分析波长,并利用快速线性干扰校正（FLIC）技术校正光谱干扰,以Lu为内标元素校正基体效应,提高了灵敏度和准确度。各元素的检出限为0.19~14.6μg/L。海泡石国家标准物质（GBW07138）各元素测定值与认定值的相对误差在-5.0%~6.7%之间。本方法具有检出限低、线性范围宽、结果准确等优点;MP-AES采用自带的氮气发生器为等离子体提供氮气作为工作气,无需引入复杂气体,提高了分析效率,尤其适用于气体采购和运输不便的偏远矿区。     

CVD合成钻石的层状生长结构和紫外荧光特征

最近NGTC实验室检测出多批次CVD合成钻石,这些CVD合成钻石均具有明显的鉴定特征,使用钻石观测仪（DiamondViewTM）观察可见蓝色、橙红色荧光和蓝色磷光以及细密层状生长纹理,光致发光光谱中可见737 nm处的特征发光线.这些特征均与其生长结构及生长过程中进入钻石晶体中的杂质有关.笔者以最近检测过程中发现的一颗CVD合成钻石为例,使用高倍率显微技术对其层状结构的微细特征及其在钻石观测仪下的荧光特征的关系进行了详细观察和对比.结果显示,此样品与之前检测到的CVD合成钻石略有差异.此次检测到的样品在钻石观测仪（DiamondViewTM）下观察具有较宽的层状生长分区,层与层之间的分界线十分明显且在高倍显微镜下也可见到细微的生长特征.通过对样品特征的分析,了解了晶体生长过程中多阶段生长条件的变化,更直观的展现了CVD合成钻石的生长过程.