NH4Cl水溶液的微观结构和宏观物性研究

通过拉曼光谱、同步辐射X射线散射和密度泛函理论(DFT)模拟,研究了质量分数为1.0 %-28.0 %的NH₄Cl水溶液的微观结构变化。同时在室温下测量了粘度、接触角和电导率。由拉曼光谱和密度泛函理论模拟结果可知,当溶质浓度升高至10.0 %时,在2900 cm_-1^和3100 cm_-1^{附近出现了明显的}N-H作用峰,且随着质量分数的升高,NH₄Cl水溶液中的氢键类型发生了转变。X射线散射结果表明,当NH₄Cl水溶液质量分数升高至10.0 %时,差值对分布函数G(r)在2.98 ?附近出现明显双峰,表明在该浓度下溶液中NH₄₊^-Cl_-^{接触离子对开始成为主要微观作用形式。对}NH₄Cl水溶液的宏观物性研究表明,粘度、接触角和电导率均随着NH₄Cl水溶液质量分数的增加而增大。作者推断,NH₄Cl水溶液中氢键类型的转变、O-H...N键占比增多以及逐渐增加的NH₄₊^-Cl_-^{接触离子对},是粘度和接触角随溶质浓度增加而增加的微观本质因素;电导率的增加与溶液中有效导电离子数量增加有关。     

Three steps of serpentinization in an eclogitized oceanic serpentinization front (Lanzo Massif – Western Alps)

The Lanzo peridotite massif is a fragment of oceanic lithosphere generated in an ocean–continent transition context and eclogitized during alpine collision. Despite the subduction history, the massif has preserved its sedimentary oceanic cover, suggesting that it may have preserved its oceanic structure. It is an exceptional case for studying the evolution of a fragment of the lithosphere from its oceanization to its subduction and then exhumation. We present a field and petrological study retracing the different serpentinization episodes and their impact on the massif structure. The Lanzo massif is composed of slightly serpentinized peridotites (<20% serpentinization) surrounded by an envelope of foliated serpentinites (100% serpentinization) bordered by oceanic metabasalts and metasedimentary rocks. The limit between peridotites and serpentinites defines the front of serpentinization. This limit is sharp: it is marked by the presence of massive serpentinites (80% serpentinization) and, locally, by dykes of metagabbros and mylonitic gabbros. The deformation of these gabbros is contemporaneous with the emplacement of the magma. The presence of early lizardite in the peridotites testifies that serpentinization began during the oceanization, which is confirmed by the presence of meta‐ophicarbonates bordering the foliated serpentinite envelope. Two additional generations of serpentine occur in the ultramafic rocks. The first is a prograde antigorite that partially replaced the lizardite and the relict primary minerals of the peridotite during subduction, indicating that serpentinization is an active process at the ridge and in the subduction zone. Locally, this episode is followed by the deserpentinization of antigorite at peak P–T (estimated in eclogitized metagabbros at 2–2.5 GPa and 550–620 °C): it is marked by the crystallization of secondary olivine associated with chlorite and/or antigorite and of clinopyroxene, amphibole and chlorite assemblages. A second antigorite formed during exhumation partially to completely obliterating previous textures in the massive and foliated serpentinites. Serpentinites are an important component of the oceanic lithosphere generated in slow to ultraslow spreading settings, and in these settings, there is a serpentinization gradient with depth in the upper mantle. The seismic Moho limit could correspond to a serpentinization front affecting the mantle. This partially serpentinized zone constitutes a less competent level where, during subduction and exhumation, deformation and fluid circulation are localized. In this zone, the reaction kinetics are increased and the later steps of serpentinization obliterate the evidence of this progressive zone of serpentinization. In the Lanzo massif, this zone fully recrystallized into serpentinite during alpine subduction and collision. Thus, the serpentinite envelope represents the oceanic crust as defined by geophysicists, and the sharp front of serpentinization corresponds to an eclogitized seismic palaeo‐Moho.     

Raman spectroscopic analysis of cyanobacterial colonization of hydromagnesite, a putative martian extremophile

Raman spectra of an extremophile cyanobacterial colony in hydromagnesite from Lake Salda in Turkey have revealed a biogeological modification which is manifest as aragonite in the stratum associated with the colony. The presence of key spectral biomarkers of organic protectant molecules such as β-carotene and scytonemin indicate that the survival strategy of the cyanobacteria is significantly one of UV-radiation protection. The terrestrial location of this extremophile is worthy of consideration further because of its possible putative link with the “White Rock” formations in Sabaea Terra and Juventae Chasma on Mars.     

纳米计量学的基础技术组件

为了满足ASTROD激光宇航动力学任务慨念计划的高精度要求 ,以及实现新质量标准 ,我们开始进行次纳米激光测长与纳米定位控制的研究。本文将回顾我们在清华大学与工研院测量中心的研究成果 ,介绍如何利用外差式激光干涉仪、挠性微动台与压电陶瓷 ,进行次纳米激光测长与纳米定位控制。此研究成果将做为ASTROD计划中 ,无拖曳航天技术的研发基础。之后讨论如何将纳米定位控制系统与扫描穿隧显微镜进行整合 ,完成计量型扫描穿隧显微镜 ,进一步将微结构的测量尺寸直接追溯至长度标准。     

High-precision analysis of carbon isotopic composition for individual CO2 inclusions via Raman spectroscopy to reveal the multiple-stages evolution of CO2- bearing fluids and melts

The carbon isotopic composition of CO₂ inclusions trapped in minerals reflects the origin and evolution of CO₂-bearing fluids and melts, and records the multiple-stages carbon geodynamic cycle, as CO₂ took part in various geological processes widely. However, the practical method for determination isotope composition of individual CO₂ inclusion is still lacking. Developing a microanalytical technique with spatial resolution in micrometers to precisely determinate the δ¹³C value of individual CO₂ inclusion, will make it possible to analyze a tiny portion of a zoning mineral crystal, distinguish the differences in micro-scale, and possible to find many useful information that could not be obtained with the bulk extraction and analysis techniques. In this study, we systematically collected Raman spectra of CO₂ standards with different δ¹³C values (?34.9 ‰ to 3.58 ‰) at 32.0 °C and from ～7.0 MPa to 120.0 MPa, and developed a new procedure to precisely determinate the δ¹³C value of individual CO₂ inclusion. We investigated the relationship among the Raman peak intensity ratio, δ¹³C value, and CO₂ density, and established a calibration model with high accuracy (0.5 ‰?1.5 ‰), sufficient for geological application to distinguish different source of CO₂ with varying δ¹³CO₂. As a demonstration, we measured the δ¹³C values and the density of CO₂ inclusions in the growth zones of alkali basalt-hosted corundum megacrysts from Changle, Shandong Province. We found the significant differences of density and δ¹³C between the CO₂ inclusions in the core of corundum and those inclusions in the outer growth zones, the δ¹³C value decreases from core to rim with decreasing density: δ¹³C values are from ?7.5 ‰ to ?9.2 ‰ for the inclusions in the core, indicating the corundum core was crystallized from mantle-derived magmas; from ?13.5 ‰ to ?18.5 ‰ for CO₂ inclusions in zone 1 and from ?16.5 ‰ to –22.0 ‰ for inclusions in zone 2, indicating the outer zones of corundum grew in a low δ¹³C value environment, resulted from an infilling of low δ¹³C value fluid and/or degassing of the ascending basaltic magma.     

Crucial control on magmatic-hydrothermal Sn deposit in the Tengchong block,SW China: Evidence from magma differentiation and zircon geochemistry

Magmatic-hydrothermal Sn deposits are commonly associated with high silica magmas, but why most global high silica granites do not bear economic Sn ore grades remains unclear. Two crucial factors controlling magmatic-hydrothermal Sn mineralization, including advanced fractionation and depressurization-induced rapid cooling, were revealed in the case study of the Guyong granitic pluton linked with the Xiaolonghe Sn deposit, in the Tengchong block, SW China. The Guyong granitic pluton comprises three petrological facies: less evolved biotite syenogranite, evolved alkali granite and leucogranite, and highly evolved facies (the protolith of greisenized granite). Similar crystallization ages (～77 Ma) and gradual contact between different petrological facies indicate the Guyong granitic pluton records a continuous fractionation process. Monte Carlo-revised Rayleigh fractionation model suggests the fractionation degree of the Guyong pluton is markedly high (>87 wt.%) that can only be achieved by a high initial water (≥4 wt.%) content in the parent granitic magma revealed by rhyolite-MELTS calculation. Advanced degree fractionation causes the first Sn enrichment but it also significantly increases the viscosity of evolved magmas, suppressing the exsolution and transport of hydrothermal fluids. Hence, it must be compensated by the second critical factor: depressurization-induced rapid cooling, reflected by the occurrence of highly metamict zircons in the greisenized granite. The highly metamict feature, indicated by the large full width at half maximum (FWHM) values of zircon ν₃(SiO₄) peak (>19.5 cm^?1), suggests these zircons do not experience thermal annealing but rapidly ascend into a shallow cooling environment. Depressurization-induced rapid cooling facilitates exsolution and transport of hydrothermal fluids, interacting with wall rocks and resulting in Sn mineralization.     

电感耦合等离子体发射光谱法测定铅锌矿中15个主次量元素

铅锌矿多元素同时测定中,样品预处理过程受多种不同因素的影响,单因素试验往往无法同时为多因素实验提供合理的优化方案。本文采用盐酸-硝酸溶矿,考察了样品预处理过程中混合酸配比、混合酸体积、消解时间及消解温度对消解效果的影响,利用正交试验设计及极差分析确定了最优消解条件:盐酸-硝酸混合酸配比3∶1,混合酸体积10 m L,消解时间120 min,消解温度90℃,用电感耦合等离子体发射光谱法同时测定铅锌矿中15个主次量元素(铅锌铜锰砷银铋镉钴镍镓铟钼锗锑)的含量。在最优条件下,用富铅锌矿石国家标准物质(GBW 07165)进行试验,大多数元素的精密度(RSD,n=12)和准确度小于5%,方法检出限为0.0019~0.048μg/g。基于铅锌矿主要是以硫化物形式存在,采用一系列硫化物国家标准物质验证方法的准确度及可行性,检测结果基本都在标准值的误差范围内。应用该方法分析湖南某矿区中大批量铅锌矿样品,标样质量统计合格率为100%,密码质量统计合格率大于97%。     

电感耦合等离子体发射光谱法测定硼硅酸盐玻璃中的硼等常见元素

硼硅酸盐玻璃中的硼、钙、镁、铝、铁、钛、硅等常见元素普遍采用各元素分别测定的方式进行分析,分析效率很低;而且硼的测定普遍采用容量法,当B2O3含量低于1%时,容量法测定误差较大。本文以KOH熔融的方式消解样品,采用电感耦合等离子体发射光谱法(ICP-AES)进行分析。通过实验研究了KOH用量和不同称样量对B2O3测定结果的影响。结果表明,KOH用量在3 g以上时有较好的熔样效率和熔样效果,称样量低于0.4 g对B2O3测定结果无明显影响,考虑到其他元素的测定,确定了KOH用量优选3 g,称样量优选0.1 g。在此条件下,测定B2O3等常见元素的精密度(RSD,n=6)≤2%,加标回收率在96.0%~105.6%之间,除Si O2测定误差较大外,其他元素的测定结果均令人满意。本方法确定的B2O3的定量限为0.067%,且对于B2O3最高含量达到16%的测定结果也令人满意,因此可测定B2O3含量的范围至少为0.067%~16%。当样品中的B2O3含量高于4%时,方法准确度和精密度与国家标准分析方法(容量法)相当;当B2O3含量低于1%时,方法准确度和精密度都优于容量法。与现有报道相比,本方法显著拓宽了B2O3的测定范围,并具有良好的准确度,而且在B2O3准确测定的同时,也实现了Ca、Mg、Al、Fe、Ti的定量分析和Si的半定量分析,大大提高了分析效率,可以实现硼硅酸盐玻璃中B2O3等常见元素的准确快速分析。     

载炭泡塑吸附-电感耦合等离子体发射光谱法测定金矿石的金量

载炭泡塑吸附法对金有良好的吸附性能,但只能用于抽滤吸附不能振荡吸附,分析手续繁杂。本文以载炭泡塑振荡吸附-电感耦合等离子体发射光谱法测定金矿石的金量。样品在650℃高温灼烧2 h,用50%王水和10%氯化铁加热溶解,溶液冷却后加入5%高锰酸钾氧化,用中密度规格的载炭泡塑两次振荡吸附溶液中的金,然后于580℃高温灼烧后以50%王水溶解灰分,直接用ICP-OES测定金量。方法检出限(3σ)为0.002μg/g,精密度(RSD,n=11)小于3.7%。本方法对金的吸附率大于99.9%,测定范围为0.01~90μg/g,对不同类型金矿石的适应性强,解决了以往泡塑吸附法吸附率较低、标准系列与样品需同时预处理的问题,对低含量和高含量样品均有较高的准确度。     

电感耦合等离子体质谱法测定灌木枝叶中微量元素的样品预处理方法研究

利用电感耦合等离子体质谱法(ICP-MS)测定植物样品中微量元素的关键技术是消除植物样品的有机基体效应,本文通过预处理方法中的酸消解体系、称样量和消解方式消除其影响。以国家标准物质灌木枝叶组合样(GBW07603)为材料进行研究,对比分析了硝酸-过氧化氢、硝酸-氢氟酸、硝酸-氢氟酸-过氧化氢3种酸溶体系的消解效果,以确定最佳酸溶体系,进而定量研究2种称样量(50 mg和100 mg)和3种消解方式(密封高压二次消解、密封高压一次消解、微波消解)的消解效果,并以In作为内标采用ICP-MS测定微量元素含量。结果表明:硝酸-氢氟酸-过氧化氢酸溶体系的消解效果最好;50 mg的测定值更接近于参考值;微波消解法的测定值明显偏低,而密封高压二次消解法是灌木枝叶样品预处理的有效方法。