Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

复杂区域四边形网格生成的一种改进方法

提出了一种改进的四边形网格生成算法。该法在行波法生成平面三角形网格的基础上，将一个三角形单元分解为三个四边形单元。经过优化处理，获得优良的计算域四边形网格。针对岩土工程结构问题，还提出了网格剖分中尖灭不连续面和锚杆及锚索的处理方案。地下洞室和边坡算例表明了这种方法的可行性和可靠性。     

Rietveld定量方法在蒸发岩矿物组分分析中的精确度评价和误差来源

Rietveld物相定量分析(RQPA)方法在地质学中已有大量应用,在蒸发岩定量分析中,对精确度的评价和误差控制是提高分析质量的重要因素。本文对人工配制和野外采集的样品(石膏和钾盐)进行RQPA分析,并与化学分析结果对比,评价其精确度并分析其主要的误差来源。结果表明:人工配制的氯化钠-氯化钾二元物相的绝对误差为0.4%~0.9%;氯化钠-氯化钾-碳酸钙三元物相的绝对误差为0.1%~1.2%;二元物相样品10次分析的标准偏差为0.702%,相对标准偏差为1.74%(氯化钾)和1.17%(氯化钠);野外采集的石膏和钾盐样品的RQPA分析结果与化学分析结果具有很好的一致性。表明RQPA方法在蒸发岩矿物组分定量分析中具有较高的精确度,其误差主要来源于样品性质、样品制备、测试条件和精修过程等。RQPA方法具有减弱择优取向效应、无需纯样以及提高数据利用率等优点,与化学分析技术联用在蒸发岩矿产勘探、储量评价以及工业应用中具有广泛的前景。     

State of seawater intrusion and its adaptive management countermeasures in Longkou City of China

Longkou City is a coastal area,and lacks water resources.The overexploitation of groundwater causes seawater intrusion.At present,seawater intrudes an area of 68 km2.With the decrease of groundwater extraction,the seawater intrusion area has generally declined.The paper expounds the development process of seawater intrusion as well as the corresponding prevention and control measures of using groundwater replenishment and groundwater throttling in Longkou City.In view of the seawater intrusion problem in Longkou City,some adaptive management countermeasures are put forward,which include:Adjusting industrial and agricultural structure,promoting economic and social development to match water resources;improving water usage structure,optimizing the utilization of water resources;advancing the construction of a water-saving society,using water resources efficiently;implementing inter-basin water transfer,using water resources rationally;developing and utilizing unconventional water sources,making full use of water resources;strengthening water infrastructure construction,increasing the development and utilization potential of water resources;carrying out ecological restoration,protecting water resources and ecological environment;improving the management informationalization level,strengthening the capabilities of groundwater monitoring and management;increasing publicity,improving public awareness of participation.     

自适应海洋观测

“自适应海洋观测”指固定或移动的海洋观测平台能够根据海洋环境和信号的变化,自主调节测量和运行参数,获取最关键的海洋信息.自主水下航行器运用自适应检测和采样技术,在研究上升流锋面等实验中显示出前所未有的观测准确度和效率.一个海洋观测系统的综合效能,取决于固定平台和移动平台的功能互补以及自适应观测能力的增强.     

Landslide susceptibility modeling based on ANFIS with teaching-learning-based optimization and Satin bowerbird optimizer

As threats of landslide hazards have become gradually more severe in recent decades,studies on landslide prevention and mitigation have attracted widespread attention in relevant domains.A hot research topic has been the ability to predict landslide susceptibility,which can be used to design schemes of land exploitation and urban development in mountainous areas.In this study,the teaching-learning-based optimization(TLBO)and satin bowerbird optimizer(SBO)algorithms were applied to optimize the adaptive neuro-fuzzy inference system(ANFIS)model for landslide susceptibility mapping.In the study area,152 landslides were identified and randomly divided into two groups as training(70%)and validation(30%)dataset.Additionally,a total of fifteen landslide influencing factors were selected.The relative importance and weights of various influencing factors were determined using the step-wise weight assessment ratio analysis(SWARA)method.Finally,the comprehensive performance of the two models was validated and compared using various indexes,such as the root mean square error(RMSE),processing time,convergence,and area under receiver operating characteristic curves(AUROC).The results demonstrated that the AUROC values of the ANFIS,ANFIS-TLBO and ANFIS-SBO models with the training data were 0.808,0.785 and 0.755,respectively.In terms of the validation dataset,the ANFISSBO model exhibited a higher AUROC value of 0.781,while the AUROC value of the ANFIS-TLBO and ANFIS models were 0.749 and 0.681,respectively.Moreover,the ANFIS-SBO model showed lower RMSE values for the validation dataset,indicating that the SBO algorithm had a better optimization capability.Meanwhile,the processing time and convergence of the ANFIS-SBO model were far superior to those of the ANFIS-TLBO model.Therefore,both the ensemble models proposed in this paper can generate adequate results,and the ANFIS-SBO model is recommended as the more suitable model for landslide susceptibility assessment in the study area considered due to its excellent accuracy and efficiency.     

基于移动式监测的道路PM2.5浓度精细化时空模拟

作为主要的大气污染指标,PM_2.5浓度常来源于固定环境监测站点的监测与遥感影像数据,但时空精度普遍不足,难以揭示微尺度下城市内部PM_2.5时空分布情况。本文利用移动式监测方法,选择典型工作日(2017年11月27日),对广州市主城区道路以1 s和1 m为时空粒度进行PM_2.5浓度数据采集,并以早、晚出行高峰时段为对象,通过机器学习方法模拟道路PM_2.5精细化时空分布格局。结果表明,主城区早高峰道路PM_2.5浓度值相近的平均范围为24 m,晚高峰为15 m,PM_2.5浓度存在微尺度的时空异质性。利用多层感知器(MLP)构建的早、晚高峰PM_2.5浓度模型,拟合度分别达到0.70和0.68,明显优于传统的普通最小二乘法(OLS)线性回归模型。模型揭示出早高峰主城区全路网PM_2.5平均浓度为30.19μg/m3,晚高峰达到44.55μg/m3,部分高达94.82μg/m3,且“西高东低”的分布特征显著。本文提出的PM     

Characterisation of tobelite (NH4)Al2[AlSi3O10](OH)2 and ND4-tobelite (ND4)Al2[AlSi3O10](OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

Tobelite (NH₄) Al₂ [AlSi₃O₁₀] (OH)₂, the ammonium analogue of muscovite, and its deuterated form ND₄-tobelite (ND₄) Al₂ [AlSi₃O₁₀] (OD)₂ have been synthesised at 600?°C and 200 and 500 Mpa using a well homogenised, stoichiometric SiO₂-Al₂O₃ oxide mix with Al₂O₃ in excess of 5 mol% and a 25% NH₃ solution whose relative abundance was such that the amount of NH₄ ⁺ stoichiometrically available was in excess of 50%. Characterisation of both tobelite and ND₄-tobelite using IR-spectroscopy, Rietveld refinement of X-ray powder diffraction data, and electron microprobe analysis indicate that, similar to K⁺ in muscovite, the NH₄ ⁺ or ND₄ ⁺ molecule occupies the interlayer site. IR absorption bands caused by NH₄ ⁺ and ND₄ ⁺ can be explained, to a very good approximation, on the basis of T_d symmetry. Nevertheless, substantial line broadening and the occurrence of shoulders indicate a deviation from ideal T_d symmetry. However, even at 77?K, no discrete splitting of the degenerate states could be confirmed. The OH stretching frequencies observed for synthetic tobelite are quite similar to those for muscovite, indicating that the replacement of K⁺ by NH₄ ⁺ has no effect. The low FWHH of the OH bands indicate that the hydroxyl groups are well ordered within the structure. Rietveld refinement of tobelite and ND₄-tobelite indicates that all samples synthesised consist of the 3 different mica polytypes which are typical of muscovite – namely 1M (C2/m), 2M ₁ (C2/c) and 2M ₂ (C2/c). Tobelite and ND₄-tobelite synthesised at 500 Mpa principally contain the 1M polytype, whereas the principle polytype for ND₄-tobelite synthesised at 200 Mpa, is 2M ₂. Rietveld refinement of X-ray diffraction spectra for tobelite synthesised at 200 Mpa was problematic due to the very broad FWHH of the X-ray peaks indicating poor crystallinity. In comparision to synthetic muscovite, the cell dimensions observed for tobelite and its deuterated analogue are quite similar except for the lattice constant c. Due to the larger radius of NH₄ ⁺ or ND₄ ⁺ compared to K⁺ cation, the c-direction is expanded form 10.275 Å in muscovite to approximately 10.540 Å in tobelite and ND₄-tobelite.     

Synthesis, crystal structure and crystal chemistry of ferri-clinoholmquistite, ?Li 2Mg 3Fe 3+ 2Si 8O 22(OH) 2

This work reports the synthesis of ferri-clinoholmquistite, nominally _Li2(Mg₃Fe³⁺₂)Si₈O₂₂(OH)₂, at varying f_O2 conditions. Amphibole compositions were characterized by X-ray (powder and single-crystal) diffraction, microchemical (EMPA) and spectroscopic (FTIR, Mössbauer and Raman) techniques. Under reducing conditions ( NNO+1, where NNO = Nickel–Nickel oxide buffer), the amphibole yield is very high (>90%), but its composition, and in particular the FeO/Fe₂O₃ ratio, departs significantly from the nominal one. Under oxidizing conditions ( NNO+1.5), the amphibole yield is much lower (<60%, with Li-pyroxene abundant), but its composition is close to the ideal stoichiometry. The exchange vector of relevance for the studied system is ^M2(Mg,Fe²⁺) ^M4(Mg,Fe²⁺) ^M2Fe³⁺_–1 ^M4Li_–1, which is still rather unexplored in natural systems. Amphibole crystals of suitable size for structure refinement were obtained only at 800 °C, 0.4 GPa and NNO conditions (sample 152), and have C2/m symmetry. The X-ray powder patterns for all other samples were indexed in the same symmetry; the amphibole closest to ideal composition has a = 9.428(1) Å, b = 17.878(3) Å, c = 5.282(1) Å, = 102.06(2)°, V = 870.8(3) ų. Mössbauer spectra show that Fe³⁺ is strongly ordered at M2 in all samples, whereas Fe²⁺ is disordered over the B and C sites. FTIR analysis shows that the amount of ^CFe²⁺ increases for increasingly reducing conditions. FTIR data also provide strong evidence for slight but significant amounts of Li at the A sites.     

自适应卡尔曼滤波在航空重力异常解算的应用研究

依据航空重力测量基本原理,构建了航空重力异常解算的卡尔曼滤波模型,将新息自适应卡尔曼滤波器(IAE,Innovation based Adaptive Estimation)应用于量测噪声未知的航空重力异常解算.针对IAE滤波器滑动窗口宽度难以准确确定的问题,通过对多个不同滑动窗口新息协方差估计的加权平均,获得改进的IAE滤波器,该IAE滤波器不仅具有量测噪声自适应估计能力,还能实现滑动采样窗口的优化选取.试验结果表明,IAE滤波器可以降低因量测噪声统计信息不明引起的解算误差,改进IAE解算的重力异常误差约为1 mGal.