酸碱滴定法测定天然石膏中碳酸盐的不确定度评定

对酸碱滴定法测定天然石膏中碳酸盐的结果进行不确定度评定。测量过程中的不确定度主要来源于样品制备过程引入的不确定度、滴定导致的不确定度、标定NaOH标准滴定溶液和HCl标准溶液引起的不确定度及重复性实验引起的不确定度等。合成各不确定度分量,并乘以扩展因子2得到扩展不确定度。对于CO₂平均含量为8.66%（质量分数）的天然石膏样品,其扩展不确定度为0.17%。     

P256强碱性阴离子树脂分离富集-5-Br-PADAP分光光度法测定铀矿石中微量铀结果不确定度评定

对以P₂₅₆强碱性阴离子树脂分离富集,5-Br-PADAP分光光度法测定铀矿石中微量铀含量的测定结果进行了不确定度评定。分析了不确定度的主要来源,提供了引入不确定度的各参数和计算方法,对各不确定度分量进行分析计算,最终合成标准不确定度和扩展不确定度。     

岩溶碳汇效应研究中“碳”测定的不确定度分析——以溶解性无机碳为例

为建立非分散红外吸收法测定岩溶区流域水体中溶解性无机碳(DIC)分析结果不确定度的评定方法,采用不确定度连续传递模式,对两个岩溶地下水样的DIC测定结果的不确定度进行了评定。其主要做法是:先采用双误差回归方式对校准曲线进行拟合,对评定过程中各个不确定度分量进行量化,然后合成得到DIC测定结果的不确定度评定模型。通过实验结果计算表明:(1)测定结果的不确定度主要来源于标准溶液引入的不确定度、曲线拟合产生的不确定度和测定过程产生的不确定度。(2)样品的DIC含量越低,其相对不确定度越大,且校准曲线在拟合过程中所引入的不确定度对其测定结果的总不确定度具有较大的贡献率。      

海南岛北部中三叠世A型花岗岩的成因及其地质意义

海南岛北部儋州地区大面积出露三叠纪花岗岩体,其岩石成因与构造背景对揭示华南中生代构造演化具有重要意义。LA-ICP-MS锆石U-Pb定年结果显示儋州大王岭花岗岩体的侵位时间为243±1.8 Ma,表明该岩体形成于中三叠世早期。儋州大王岭花岗岩相对富铝(Al₂O₃=15.08%～15.49%)、钾(K₂O=4.90%～5.63%)和稀土元素(∑REE=331～369μg/g),属钾玄质钙碱性系列;A/CNK值为0.93～0.95,属于准铝质。岩体相对富集轻稀土元素,轻重稀土元素分异明显(La_N/Yb_N=29.2～43.1),显示明显的Eu负异常(δEu=0.18～0.21)。样品具有相对高的Ga/Al值,结合(Nb+Zr+Ce+Y)含量指示其属于A型花岗岩。较低的锆石Hf同位素(ε_Hf(t)=-13.9～-10.0)及较老的Hf同位素二阶段模式年龄(t_DM2=1.54～1.73 Ga),反映其可能源自海南岛早–中元古代变质基底(如抱板群...     

西藏念青唐古拉山帕戈勒中新世二云母花岗岩成因机制及对稀有金属铍成矿能力的指示

淡色花岗岩是研究浅部地壳物质成分和碰撞造山带地球动力学过程的理想对象,也是稀有金属成矿的重要载体。本文研究的帕戈勒二云母花岗岩发育在西藏冈底斯念青唐古拉复式花岗岩岩基的西南侧,以岩株和岩枝形式产出,局部偶见绿柱石。精细的锆石U-Pb定年显示,岩体结晶成岩年龄为18.4 Ma和17.6 Ma,形成于中新世。岩体具有高的SiO₂(72.78%～75.53%)和K₂O(4.83%～5.52%)含量,低的Al₂O₃(13.42%～14.60%)、MgO(0.10%～0.24%)、TFe₂O₃(0.86%～1.65%)含量,A/CNK为1.04～1.12,属于过铝质高钾钙碱性-钾玄质花岗岩。(⁸⁷Sr/⁸⁶Sr)_i=0.712139～0.713545,ε_Nd(t)=-9.0～-8.3,Nd二阶段模式年龄t_DM2=1211～1468 Ma,²⁰⁶     

高效液相色谱法测定地下水中苯并(a)芘的不确定度评定

通过对高效液相色谱法测定地下水中苯并(a)芘含量的全过程分析,确定了测定结果不确定度的来源。采用不确定度连续传递模型,对引入的不确定度分量进行评定,并采用最小二乘法对标准曲线进行拟合,确定了地下水中苯并(a)芘含量标准不确定度由样品取样量、样品定容体积及测定体积、样品重复性测定、标准溶液浓度和标准曲线拟合误差6部分不确定度合成。通过对2个不同含量样品测定结果不确定度评定,证明苯并(a)芘含量越低,测定结果的相对标准不确定度越大;且样品重复性测定和标准曲线拟合误差是测定结果不确定度的重要来源。     

川西李家沟锂多金属矿区晚三叠世花岗细晶岩脉的成因：地球化学、锆石U-Pb年龄和Hf同位素的证据

李家沟锂多金属矿床位于松潘-甘孜褶皱造山带东南缘,是近年来在区内发现的超大型锂多金属矿床,矿区内广泛发育花岗细晶岩脉。本文对花岗细晶岩脉进行了全岩地球化学测试、锆石U-Pb定年和Hf同位素分析,探讨其岩石成因及地质意义。花岗细晶岩锆石U-Pb加权平均年龄为200±2 Ma,属晚三叠世—早侏罗世。岩石具高硅(w(SiO₂)=73.27%～75.14%)、富铝(w(Al₂O₃)=14.8%～15.25%)、富碱(w(Na₂O+K₂O)=4.86%～8.08%)、贫钙(w(CaO)=0.45%～1.45%)的特征,A/CNK值均大于1.1,属中钾-高钾钙碱性强过铝质S型花岗岩。微量元素表现出Rb、Th、U、K的正异常和Ba、Sr、P、Ti相对负异常。稀土元素显示轻稀土富集、重稀土亏损及弱的负Eu异常(δEu=0.68～0.81)。岩石中锆石ε_Hf(t)值和对应的二阶模式年龄(t_DM2)较为均一,分别为-6.36～-3.39和1 424～1 ...     

与遂安石共生的电气石矿物学特征及其地质意义

在对宽甸砖庙硼矿床的研究中发现了电气石与遂安石共生的现象,电气石为钙镁电气石,由电子探针分析结果计算的晶体化学式为:(Ca_0.59Na_0.355K_0.06)(Mg_2.557Fe_0.1512+Ti_0.013Cr_0.002Ni_0.006)(Al_5.416Fe_0.5642-（BO₃）₃Si _6.16 O₁₆（OH）₄,同围岩中的电气石相比:（1）淡绿色,多色性弱;（2）折射率为Ne=1.646,Ns=1.624;（3）成分上富Mg（MgO 11.47％）和Ca（CaO3.14％）;相对贫Na（Na₂O 1.09％）,Fe（FeO4.63％）和Al（Al₂O₃26.69％）（4）结构上d₁₀₁=3.393A,a₀=15.957±0.002,c₀=7.227±0.001;（5）红外光谱晶格Si-O₄四面体振动I₁₀₀₁>I₁₀₃₆。这些标型特征具有硼矿床的找矿指示意义。     

微波消解-荧光法检测土壤中微量铀的不确定度评定

文章介绍了微波消解-荧光法检测土壤中铀的含量的不确定度评定。采用微波消解作为样品前处理方法,配制了专属的抗干扰试剂,消除了测量时候由于pH值带来的干扰,建立了不确定度的测量模型,并明确了各不确定度分量的来源,分别是样品电子天平的称量、测量重复性和工作曲线系列溶液配制等。经过评定,测量重复性对不确定度产生显著影响,其次是仪器在测量过程中引入的不确定度,微波消解-荧光法测定土壤中铀含量的结果为（7.45±0.32） mg/kg （包含因子k=2）,这表明该方法具有较高的可靠性和准确性。     

氢化物发生-原子荧光光谱法测定地球化学样品中铋结果不确定度评定

按照测量不确定度评定方法,对氢化物发生-原子荧光光谱法测定地球化学样品中铋结果进行不确定度评定。研究发现原子荧光光谱法测定地球化学样品中铋含量的不确定度主要来源于样品制备过程、标准溶液配制过程、校准曲线拟合过程、重复性测量以及分析仪器的不确定度等。通过对各分量的不确定度进行量化,得出合成标准不确定度和扩展不确定度。结果表明最大的不确定度来源于样品制备过程。当样品中铋含量为24.76μg/g时,其扩展不确定度(k=2)为1.40μg/g。     

Critical point properties of electron density distributions for oxide molecules containing first and second row cations

 Minimum energy geometries and electron density distributions, ϱ(r), for ∼40 polyatomic oxide molecules containing first and second row M-cations have been calculated at the Hartree-Fock level with a 6-311++G** basis set. The nature of the bonded interactions in these molecules is examined in terms of the relative electronegativities, χ _M , of the M-cations and the properties of the electron density distribution, ϱ(r _c ), evaluated at the bond critical points, r _c , along each MO bond. As ϱ(r _c ) and the Laplacian of ϱ(r _c ) increase, χ _M increases indicating an increase in the covalent character of the bonded interactions between M and O. The ratios of the curvatures of ϱ(r _c ) indicate that the NO bond is predominantly covalent, that the CO and SO bonds are of intermediate type and that the remaining MO bonds are indicated to be predominantly ionic in character. A comparison of the critical point properties of ϱ(r _c ) and χ _M indicates that the minimum energy MO bond length is an important determinate of the properties of ϱ(r _c ) and the character of the MO bonds. On the other hand, values of the local energy density, H(r _c ), indicate that the LiO, BeO, NaO, MgO and AlO bonds are predominantly ionic and that the BO, CO, NO, SiO, PO and SO bonds are predominantly covalent in character. The χ _M -values provided by the properties of ϱ(r _c ) indicate that the covalent component of a bond increases with decreasing bond length, coordination number and increasing bond strength. Each MO bond seems to represent a unique entity and to possess a distinct set of ϱ(r _c ) properties, the distinction being greater for the more electronegative cations. The bonded radius of the oxide ion, r _b (O), and the χ _M -values determined from ϱ(r _c ) correlate with values determined from promolecule electron density distributions. In addition, r _b (O) and χ _M -values determined from experimental electron density distributions for crystals correlate with values determined from procrystal electron density distributions. The number of critical points and bond paths are modeled rather faithfully by procrystal and promolecule electron density distributions, despite the neglect of the binding forces in their constructions. Received: October 15, 1996/Revised, accepted: February 10, 1997     

Physical properties of the variations of the electric field of the earth preceding earthquakes. II. determination of epicenter and magnitude

As reported in the preceding paper, a transient change of the electric field of the earth (seismic electric signal), hereafter called SES, appears many hours before an earthquake (EQ). By measuring this change in a given direction and dividing it with a suitable relative effective resistivity one obtains a quantity that reflects the current density in this direction. Measurements in two directions (E-W and N-S) give the relative signal intensity J_rel at the station under consideration. By measuring J_rel at a number of stations and considering that it attenuates according to a 1/r-law, the epicenter can be determined with an accuracy usually around 100 km. Once the epicenter has been determined, the product J_rel · r can be evaluated so that the magnitude M can be estimated by resorting to an empirical log(J_rel · r) versus M plot. The uncertainty of M is around 0.5 units. Following Sobolev (1975) and for the statistics to be beyond any doubt, predictions were officially documented before the EQ-occurrence. For 23 earthquakes with a magnitude equal or greater than M_s = 5.0 two events were missed.The present method is compared to other electrical methods used in China, Japan and Soviet Union. A number of problems concerning the origin of the effect, its directivity and the attenuation with distance remain open for further studies.     

Observed and predicted test pile behaviour

The results obtained from a loading test on a bored, cast-in-place pile instrumented with six pairs of load cells at different levels are compared with the results obtained from a non-linear finite element analysis based on the geotechnical parameters of the cohesive soils in which the pile was bored. Settlements computed using deformability parameters obtained by a standard laboratory test were much larger than the measured settlements. Satisfactory results are instead obtained assuming E_i=1000c_u and c_α=c_u. The distribution of the vertical stresses within the pile and of the shear stresses in the soil adjacent to the pile obtained by the numerical analysis are compared with the measured values. A fair agreement is found at loads below failure but differences between experimental and computed values are found at loads close to failure.     

A study of the bonded interactions in nitride molecules in terms of bond critical point properties and relative electronegativities

Bond critical point properties calculated for the MN bonds in a number of geometry optimized nitride molecules containing first- and second-row M cations are compared with those calculated for a number of oxide molecules. As reported for the oxides, the value of the electron density, ρ(r _c ), at the bond critical points, r _c , increases with decreasing bond length while for the more electronegative cations, the local energy density, H(r _c ) decreases nonlinearly in value as the relative electronegativities of the M-cations, χ _M , tend to increase. In the majority of cases, χ_M, |λ₁|/λ₃ and ∇²ρ(r _c ) increase with decreasing minimum energy bond lengths. The bond lengths adopted by the molecules are indicated to be an important determinant of the critical point properties of the electron density distributions. The relative electronegativities derived from the electron density distributions of the nitrides agree with those derived for the oxides and Pauling’s electronegativities to within ∼5%, on average. Received: 3 February 1997 / Revised, accepted: 11 July 1997     

Dielectric constants of tephroite,fayalite and olivine and the oxide additivity rule

The dielectric constants and dissipation factors of synthetic tephroite (Mn₂SiO₄), fayalite (Fe₃SiO₄) and a forsteritic olivine (Mg_1.80Fe_0.22SiO₄) were measured at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: tephroite, κ′_a= 8.79 tan δ_a = 0.0006 κ′_b = 10.20 tan δ_b = 0.0006 κ′_c= 8.94 tan δ_c= 0.0008 fayalite, gk′_a = 8.80 tan δ_a = 0.0004 gk′_b= 8.92 tan δ_b = 0.0018 gk′_c = 8.58 tan δ_c = 0.0010 olivine, gk′_a = 7.16 tan δ_a = 0.0006 gk′_b = 7.61 tan δ_b = 0.0008 gk′_c = 7.03 tan δ_c = 0.0006 The low dielectric constant and loss of the fayalite indicate an exceptionally low Fe³⁺ content. An FeO polarizability of 4.18 ų, determined from α_D(FeO) = [α_D (Fe₂SiO₄)-α_D(SiO₂)]/2, is probably a more reliable value for stoichiometric FeO than could be obtained from Fe_xO where x = 0.90–0.95. The agreement between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to α_D(M₂M′X₂) = 2α_D(MX) + α_D(M′X₂) is ～+2.8% for tephroite and +0.2% for olivine. The deviation from additivity in tephroite is discussed.     

A comparison between Shields' threshold criterion and the movement of loosely packed gravel in a tidal channel

Observations of the threshold of movement of loosely packed gravel in a tidal current are described. For gravel with equivalent ‘spherical’ diameters D in the range 0.2 ?D? 5.0cm the critical friction velocity u*_c, corresponding to the initiation of sediment transport, is given by u*_c=7.0 D^0.2. At large values of D within the quoted range, the value u*_c is significantly lower than would be obtained by a Shields experiment (u*_c∞D^0.5). By comparing our values of u*_c with those obtained under well-controlled laboratory conditions, the discrepancy with Shields is shown to be due to the open spacing between, and exposure of, individual pebbles on the seabed. By comparing our results with those from upland gravel streams and flume experiments, it is suggested that Shields assumed an excessively large water depth to particle size ratio as a constraint within which the critical sediment entrainment number 0_c is valid.     

土壤中总有机碳环境标准样品研制

土壤环境标准样品是土壤生态环境监测质量控制的重要技术工具.目前,土壤中总有机碳环境标准样品仍为中国环境标准样品体系的空缺,特别是配套燃烧氧化-非分散红外法的土壤标准样品一直未曾问世.本文以有机碳含量较高的农用地土壤为原材料,经干燥、研磨、混匀、装瓶、灭菌等加工步骤,制备获得土壤中总有机碳环境标准样品.分层随机抽取10瓶...     

Dielectric constants of chrysoberyl,spinel, phenacite,and forsterite and the oxide additivity rule

The dielectric constants and dielectric loss values of BeAl₂O₄ (chrysoberyl), MgAl₂O₄ (spinel), Be₂SiO₄ (phenacite), and Mg₂SiO₄ (forsterite) were measured at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: chrysoberyl, κ′ _a =9.436, κ′ _b =9.071, κ′ _c =8.269; spinel, κ′ _a =8.18; phenacite, κ′ _a =6.28, κ′ _c =6.06; and forsterite, κ′ _a =6.867, κ′ _b =7.392, κ′ _c =6.739. The agreement between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to α_D(M₂M′X₄) = 2α_D(MX)+α_D(M′X₂) is ~ 1.0%.     

The Variance-Based Cross-Variogram: You Can Add Apples and Oranges

The variance-based cross-variogram between two spatial processes, Z₁ (·) and Z₂ (·), is var (Z₁ ( u ) – Z₂ ( v )), expressed generally as a bivariate function of spatial locations uandv. It characterizes the cross-spatial dependence between Z₁ (·) and Z₂ (·) and can be used to obtain optimal multivariable predictors (cokriging). It has also been called the pseudo cross-variogram; here we compare its properties to that of the traditional (covariance-based) cross-variogram, cov (Z₁ ( u ) – Z₁ ( v ), Z₂ ( u ) – Z₂ ( v )). One concern with the variance-based cross-variogram has been that Z₁ (·) and Z₂ (·) might be measured in different units (apples and oranges). In this note, we show that the cokriging predictor based on variance-based cross-variograms can handle any units used for Z₁ (·) and Z₂ (·); recommendations are given for an appropriate choice of units. We review the differences between the variance-based cross-variogram and the covariance-based cross-variogram and conclude that the former is more appropriate for cokriging. In practice, one often assumes that variograms and cross-variograms are functions of uandv only through the difference u – v. This restricts the types of models that might be fitted to measures of cross-spatial dependence.     

The production of iron oxide during peridotite serpentinization: Influence of pyroxene

Serpentinization produces molecular hydrogen(H2)that can support communities of microorganisms in hydrothermal fields;H2 results from the oxidation of ferrous iron in olivine and pyroxene into ferric iron,and consequently iron oxide(magnetite or hematite)forms.However,the mechanisms that control H2 and iron oxide formation are poorly constrained.In this study,we performed serpentinization experiments at 311℃ and 3.0 kbar on olivine(with 5% pyroxene),orthopyroxene,and peridotite.The results show that serpentine and iron oxide formed when olivine and orthopyroxene individually reacted with a saline starting solution.Olivine-derived serpentine had a significantly lower FeO content(6.57±1.30 wt.%)than primary olivine(9.86 wt.%),whereas orthopyroxene-derived serpentine had a comparable FeO content(6.26±0.58 wt.%)to that of primary orthopyroxene(6.24 wt.%).In experiments on peridotite,olivine was replaced by serpentine and iron oxide.However,pyroxene transformed solely to serpentine.After 20 days,olivine-derived serpentine had a FeO content of 8.18±1.56 wt.%,which was significantly higher than that of serpentine produced in olivine-only experiments.By contrast,serpentine after orthopyroxene had a slightly higher FeO content(6.53±1.01 wt.%)than primary orthopyroxene.Clinopyroxene-derived serpentine contained a significantly higher FeO content than its parent mineral.After 120 days,the FeO content of olivine-derived serpentine decreased significantly(5.71±0.35 wt.%),whereas the FeO content of orthopyroxene-derived serpentine increased(6.85±0.63 wt.%)over the same period.This suggests that iron oxide preferentially formed after olivine serpentinization.Pyroxene in peridotite gained some Fe from olivine during the serpentinization process,which may have led to a decrease in iron oxide production.The correlation between FeO content and SiO_2 or AI_2 O_3 content in olivine-and orthopyroxene-derived serpentine indicates that aluminum and silica greatly control the production of iron oxide.Based on our results and data from natural serpentinites reported by other workers,we propose that aluminum may be more influential at the early stages of peridotite serpentinization when the production of iron oxide is very low,whereas silica may have a greater control on iron oxide production during the late stages instead.