Inner-Helmholtz potential development at the hematite (α-Fe2O3) (0 0 1) surface

Electric potentials of the (0 0 1) surface of hematite were measured as a function of pH and ionic strength in solutions of sodium nitrate and oxalic acid using the single-crystal electrode approach. The surface is predominantly charge-neutral in the pH 4-14 range, and develops a positive surface potential below pH 4 due to protonation of μ-OH⁰ sites (pK_1,1,0,int = −1.32). This site is resilient to deprotonation up to at least pH 14 (−pK_−1,1,0,int ? 19). The associated Stern layer capacitance of 0.31-0.73 F/m² is smaller than typical values of powders, and possibly arises from a lower degree of surface solvation. Acid-promoted dissolution under elevated concentrations of HNO₃ etches the (0 0 1) surface, yielding a convoluted surface populated by sites. The resulting surface potential was therefore larger under these conditions than in the absence of dissolution. Oxalate ions also promoted (0 0 1) dissolution. Associated electric potentials were strongly negative, with values as large as −0.5 V, possibly from metal-bonded interactions with oxalate. The hematite surface can also acquire negative potentials in the pH 7-11 range due to surface complexation and/or precipitation of iron species (0.0038 Fe/nm²) produced from acidic conditions. Oxalate-bearing systems also result in negative potentials in the same pH range, and may include ferric-oxalate surface complexes and/or surface precipitates. All measurements can be modeled by a thermodynamic model that can be used to predict inner-Helmholtz potentials of hematite surfaces.     

218P0 测量法寻找基岩裂隙水研究

论述了利用218P₀测量法寻找基岩裂隙水的基本原理;阐明了水、氡在断裂等构造条件下,运移、汇集、赋存的特征及富氡富水、氡少水贫和同步对应,及部位一致的基本规律。介绍了高值异常峰顶型、低值异常凹斗型、无异常平缓型三种曲线类型及其分析方法。试验实践证明,此法具有轻便快速、高效准确、省时省力等优点,辅以其它方法找水定井,成井率达到98.2%.实践意义大,推广价值高。     

ET0计算公式的最新进展与普适性评估

通过对ET₀计算公式研究进展的总结,分析了在世界上三个时期比较有代表性的计算蒸发腾发量(ET₀)的主要公式:修正Penman(MP)公式、Penman-Monteith(PM)公式及标准ASCE-PM公式;以20世纪90年代末期和21世纪初期世界上最新的19个用Lysimeter实验值率定ET₀计算值的实验成果为基础,对于不同气候条件下ET₀计算方法的普适性分析评估认为:虽PM公式应用效果较好的地区较多,但也有不少地区效果欠佳,MP等公式在一部分地区较好,PM与MP公式并非普适性的,要特别关注标准ASCE-PM公式,总之,这类半理论(半经验)公式均有一定的地区性。仅通过MP、PM公式的计算比较,不能简单地评定哪种公式最优或哪种公式计算ET₀值大(或值小),应针对不同地理及气候条件,要经Lysimeter的实验结果才能进行率定比较。文中也对今后研究提出相应建议,有助于ET₀计算公式学科的深入研究。     

海河流域ET0演变规律及灵敏度分析

根据国家气象站1956-2000年逐日气象资料,采用Penman-Monteith公式和灵敏指数法,分析了海河流域潜在蒸发蒸腾(ET₀)的演变规律及与气象要素的灵敏关系。结果表明:全流域45年ET₀呈下降趋势,但年际间呈现4个阶段;逐旬呈倒"V"字型,61.6%集中于4月中旬到8月上旬。在空间上,年和旬值呈现上游小下游大。通过ET₀与气象要素演变的比较及灵敏性分析发现,全流域年ET₀演变与年均风速、日照时数以及短波辐射相似,与温度相反。旬ET₀演变与旬平均温度、实际水汽压、日照时数以及短波辐射相似,但对各要素的灵敏系数以短波辐射最大,其它要素则随时空变化,且彼此的灵敏系数相差较大。分析表明在气象要素的综合作用下,造成全流域ET₀降低的主要原因可能在于短波辐射、日照时数的变化。     

晋中马兰黄土的K0固结特性

静止土压力系数K₀描述土体的原位应力状态,是许多工程计算的重要参数。本文通过等应变速率K₀固结试验,研究原状和重塑马兰黄土的K₀变化规律,并探讨这种变化与内部结构的关系。结果表明：(1)原状和重塑马兰黄土的K₀均不是恒定值,根据土体结构的变化,其固结过程可分为初始阶段和稳定阶段。初始阶段K₀(以K_0i表示)随含水率的增加呈线性增长,稳定阶段K₀(以K_0s表示)随含水率的增加呈双曲线增长,且K_0s始终大于K_0i。(2)原状马兰黄土的K_0i小于重塑马兰黄土,原因在于原状马兰黄土具有很强的簇聚结构,这种竖向结构弱化了水平应力的增长;而重塑马兰黄土趋于均质,呈各向同性,进而导致较高的K_0i。(3)稳定阶段,原状马兰黄土的初始结构被破坏,与重塑马兰黄土近似,使得两者的K_0s相近。(4)相较于其他类土,原状马兰黄土的...     

218P0测深法寻找基岩地下水实用研究

阐明了一种新的找水方法——218P₀测深法。对其操作过程和根据实测曲线识别含水层、确定含水层数、分析富水性,以及计算含水层底板埋深的方法作了分析,并对有关机理作了初步探讨。     

基于三轴试验的黄土K0固结特性研究

静止土压力系数(K₀)是岩土工程中计算侧向土压力的关键参数,原状和重塑黄土的K₀系数在固结过程中的发展规律明显区别于黏土或砂土。为研究围压和初始孔隙比对原状和重塑黄土的K₀系数的影响,采用加装高精度局部径向位移计(LVDT)的应力路径三轴仪开展了K₀固结试验研究,结果表明:(1)重塑黄土的K₀系数受初始孔隙比(e₀)的影响较为明显,当试样的初始孔隙比减小(从0.775变为0.503),其K₀系数的最大降幅为55%;然而原状黄土的K₀系数受有效围压(σ₃′)的影响较为明显,比如在σ₃′ < 350kPa时,K₀系数为0.77~0.85,在σ₃′>350kPa时,K₀系数为0.46~0.51;(2)在固结过程中,原状黄土试样和重塑黄土试样的K₀系数均发生陡降,具体表现为重塑黄土密样(e₀<0.6)的陡降发生在固结的起始阶段,重塑黄土松样(e₀ ≈ 0.77)的陡降发生在有效围压接近100kPa,而原状黄土试样的陡降发生在有效围压为350kPa附近;(3)在相同的有效围压和密度条件下,原状黄土的K₀系数大于重塑黄土。采用核磁共振技术(NMR)获取了重塑和原状黄土的孔隙分布,并辅以试样的超孔隙水压力、排水体积等数据进行了讨论,发现结构性是造成黄土K₀系数差异的主要原因。     

两种不同假设下的Af-K0关系和不排水强度

根据一个新的孔隙水压力方程和两种不同的假设, 建立了两个不同的A_f-K₀关系式并进行了比较; 分析了相应假设下不排水强度的特点.      

Thermal expansion along the NaAlSi2O6–NaFe3+Si2O6 and NaAlSi2O6–CaFe2+Si2O6 solid solutions

The high temperature volume and axial parameters for six C2/c clinopyroxenes along the NaAlSi₂O₆–NaFe³⁺Si₂O₆ and NaAlSi₂O₆–CaFe²⁺Si₂O₆ joins were determined from room T up to 800°C, using integrated diffraction profiles from in situ high temperature single crystal data collections. The thermal expansion coefficient was determined by fitting the experimental data according to the relation: ln(V/V ₀) = α(T − T ₀). The thermal expansion coefficient increases by about 15% along the jadeite–hedenbergite join, whereas it is almost constant between jadeite and aegirine. The increase is related to the Ca for Na substitution into the M2 site; the same behaviour was observed along the jadeite–diopside solid solution, which presents the same substitution at the M2 site. Strain tensor analysis shows that the major deformation with temperature occurs in all samples along the b axis; on the (010) plane the higher deformation occurs in jadeite and aegirine at a direction almost normal to the tetrahedral–octahedral planes, and in hedenbergite along the projection of the longer M2–O bonds. The orientation of the strain ellipsoid with temperature in hedenbergite is close to that observed with pressure in pyroxenes. Along the jadeite–aegirine join instead the high-temperature and high-pressure strain are differently oriented.     

六氟化硫法测量33S/32S、34S/32S和36S/32S的方法研究

六氟化硫法是测量硫同位素组成的新方法。与传统的二氧化硫法相比，六氯化硫法有灵敏度高，准确度高，能同时测定扩δ³³S、δ³⁴S和δ³⁶S的优越性。本文介绍了国内第一台同位素分析用的六氟化硫制样装置，并报导了对硫化银、黄铁矿、黄铜矿、陨硫铁、方铅矿和闪锌矿等天然硫化物用六氟化硫法进行硫同位素测定的结果。结果表明，我们的装置和方法达到了国际上现有的水平，并在操作的方便性、可靠性及样品适用范围方面有所改进。     

考虑K0固结的软土基坑工程三维非线性有限元分析

为考虑基坑工程的空间效应,土体分别采用K0固结和正常固结试样固结不排水(CU)试验得到的Duncan-Chang非线性弹性模型和Mohr-Coulomb理想弹塑性模型,运用ABAQUS软件按照三维实体单元、壳单元、梁单元考虑接触相互作用的耦合有限元法,建立了福州市一典型软土基坑工程整体三维有限元分析模型,对基坑施工的各工况下整个体系的响应进行了数值模拟"目标试验",并与实测结果和二维数值模拟结果进行了比较,结果表明,采用K0固结试样CU试验参数的Duncan-Chang模型对该基坑进行的三维非线性数值模拟分析方法是较为可靠的,较之Mohr-Coulomb理想弹塑性模型和二维有限元分析,其结果的优势是明显的,是值得推崇和具有较好应用价值的方法。     

Thermodynamic analysis of the system Na2O-K2O-CaO-Al2O3-SiO2-H2O-F2O?1: Stability of fluorine-bearing minerals in felsic igneous suites

Thermodynamic analysis of the system Na₂O-K₂O-CaO-Al₂O₃-SiO₂-H₂O-F₂O_–1 provides phase equilibria and solidus compatibilities of rock-forming silicates and fluorides in evolved granitic systems and associated hydrothermal processes. The interaction of fluorine with aluminosilicate melts and solids corresponds to progressive fluorination of their constituent oxides by the thermodynamic component F₂O_–1. The chemical potential (F₂O_–1) buffered by reaction of the type: MO_n/2 (s)+n/2 [F₂O_–1]=MF_n (s, g) where M=K, Na, Ca, Al, Si, explains the sequential formation of fluorides: carobbiite, villiaumite, fluorite, AlF₃, SiF₄ as well as the common coexistence of alkali- and alkali-earth fluorides with rock-forming aluminosilicates. Formation of fluorine-bearing minerals first starts in peralkaline silica-undersaturated, proceeds in peraluminous silica-oversaturated compositions and causes progressive destabilization of nepheline, albite and quartz, in favour of villiaumite, cryolite, topaz, chiolite. Additionally, it implies the increase of buffered fluorine solubilities in silicate melts or aqueous fluids from peralkaline silica-undersaturated to peraluminous silica-oversaturated environments. Subsolidus equilibria reveal several incompatibilities: (i) topaz is unstable with nepheline or villiaumite; (ii) chiolite is not compatible with albite because it only occurs only at very high F₂O_–1 levels. The stability of topaz, fluorite, cryolite and villiaumite in natural felsic systems is related to their peralkalinity (peraluminosity), calcia and silica activity, and linked by corresponding chemical potentials to rock-forming mineral buffers. Villiaumite is stable in strongly peralkaline and Ca-poor compositions (An_<0.001). Similarly, cryolite stability requires coexistence with nearly-pure albite (An_<2). Granitic rocks with Ca-bearing plagioclase (An_>5) saturate with topaz or fluorite. Crystallization of topaz is restricted to peraluminous conditions, consistent with the presence of Li-micas or anhydrous aluminosilicates (cordierite, garnet, andalusite). Fluorite is predicted to be stable in peraluminous biotite granites, amphibole-, clinopyroxene- or titanite-bearing calc-alkaline suites as well as in peralkaline granitic and syenitic rocks. Fluorine concentrations in felsic melts buffered by the coexistence of F-bearing minerals and feldspars increase from peralkaline through metaluminous to mildly peraluminous compositions. At low-temperature conditions, the hydrothermal evolution of peraluminous granitic and greisen systems is controlled by white mica-feldspar-fluoride equilibria. With decreasing temperature, topaz gradually breaks down via: (i) (OH)F_–1 substitution and fluorine transfer to fluorite by decalcification of plagioclase below 600 °C, (ii) formation of muscovite and additional fluorite at 475–315 °C, and (iii) formation of paragonite and cryolite, consuming F-rich topaz and albite below 315 °C. These equilibria explain the absence of magmatic fluorite in Ca-bearing topaz granitic rocks; its abundance in hydrothermal rocks is due to: (i) closed-system defluorination of topaz, (ii) open-system decalcification of plagioclase or (iii) hydrolytic alteration. These results provide a complete framework for the investigation of fluorine-bearing mineral stabilities in felsic igneous suites.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.Editorial responsibility: T.L. Grove     

Early diagenetic vivianite [Fe3(PO4)2 · 8H2O] in a contaminated freshwater sediment and insights into zinc uptake: A μ-EXAFS, μ-XANES and Raman study

The sediments in the Salford Quays, a heavily-modified urban water body, contain high levels of organic matter, Fe, Zn and nutrients as a result of past contaminant inputs. Vivianite [Fe₃(PO₄)₂ · 8H₂O] has been observed to have precipitated within these sediments during early diagenesis as a result of the release of Fe and P to porewaters. These mineral grains are small (<100 μm) and micron-scale analysis techniques (SEM, electron microprobe, μ-EXAFS, μ-XANES and Raman) have been applied in this study to obtain information upon the structure of this vivianite and the nature of Zn uptake in the mineral. Petrographic observations, and elemental, X-ray diffraction and Raman spectroscopic analysis confirms the presence of vivianite. EXAFS model fitting of the FeK-edge spectra for individual vivianite grains produces Fe–O and Fe–P co-ordination numbers and bond lengths consistent with previous structural studies of vivianite (4O atoms at 1.99–2.05 Å; 2P atoms at 3.17–3.25 Å). One analysed grain displays evidence of a significant Fe³⁺ component, which is interpreted to have resulted from oxidation during sample handling and/or analysis. EXAFS modelling of the Zn K-edge data, together with linear combination XANES fitting of model compounds, indicates that Zn may be incorporated into the crystal structure of vivianite (4O atoms at 1.97 Å; 2P atoms at 3.17 Å). Low levels of Zn sulphate or Zn-sorbed goethite are also indicated from linear combination XANES fitting and to a limited extent, the EXAFS fitting, the origin of which may either be an oxidation artifact or the inclusion of Zn sulphate into the vivianite grains during precipitation. This study confirms that early diagenetic vivianite may act as a sink for Zn, and potentially other contaminants (e.g. As) during its formation and, therefore, forms an important component of metal cycling in contaminated sediments and waters. Furthermore, for the case of Zn, the EXAFS fits for Zn phosphate suggest this uptake is structural and not via surface adsorption.     

H2O2在α-Fe2O3表面非均相氧化SO2机理的模拟研究

通过密度泛函理论模拟了H_2O_2和SO_2气体在矿物氧化物(α-Fe_2O_3)表面上的非均相反应,研究了H_2O_2和SO_2在α-Fe_2O_3(001)表面的吸附机制和氧化机制。研究结果表明,SO_2、H_2O_2均在α-Fe_2O_3(001)表面通过Fe原子进行吸附,H_2O_2相比于SO_2优先吸附在α-Fe_2O_3(001)表面,且H_2O_2在表面的赋存形式趋向于两个·OH形式吸附。通过二者共吸附的局域态密度、差分电荷密度、Mulliken电荷布局分析结果发现,SO_2和H_2O_2的共吸附形式是通过H_2O_2产生的·OH吸附在α-Fe_2O_3(001)表面,同时SO_2被H_2O_2产生的·OH氧化[S(SO_2)-电荷布局:0. 79 e→1. 32 e; O(H_2O_2)-电荷布局:-0. 77 e→-1. 11 e]形成·OH+SO_2团簇。模拟结果表明大气微量气体H_2O_2能够在矿物氧化物表面介导SO_2吸附并促进SO_2的转化,为理解H_2O_2在大气中非均相氧化SO_2的反应过程提供了理论依据。     

Hydrous olivine (Mg1? y? Fe2+y)2? x ?v x ? SiO4H2 x – a new DHMS phase of variable composition observed as nanometer-sized precipitations in mantle olivine

 An olivine grain from a peridotite nodule 9206 (Udachnaya kimberlite, Siberia) was investigated by TEM methods including AEM, HRTEM, SAED and EELS techniques. A previous study of the 9206 olivine sample revealed OH absorption bands in the IR spectrum and abundant nanometer-sized OH-bearing inclusions, of hexagonal-like or lamellar shape. Inclusions, which are several hundred nm in size, consist of 10 ? phase, talc and serpentine (chrysotile and lizardite). The lamellar (LI) and hexagon-like small inclusions of several ten nm in size (SI) are the topic of the present paper. AEM investigations of the inclusions reveal Mg, Fe and Si as cations only. The Mg/Si and Fe/Si atomic ratios are lower in the inclusions than in the host olivine. The Si concentration in the olivine host and both lamellar inclusions and small inclusions is the same. A pre-peak at 528eV was observed in EEL spectra of LI and SI, which is attributed to OH⁻ or Fe³⁺. From these data it is concluded that there is a OH⁻- or Fe³⁺-bearing cation-deficient olivine-like phase present. HRTEM lattice fringe images of LI and SI exhibit modulated band-like contrasts, which are superimposed onto the olivine lattice. Diffraction patterns (Fourier-transforms) of the HREM images as well as SAED patterns show that the band-like contrasts in HRTEM images of the inclusions are caused by periodic modulations of the olivine lattice. Three kinds of superperiodicity in the olivine structure such as 2a, 3a and 3c, were observed in SAED patterns. The corresponding olivine supercells labelled here as Hy-2a, Hy-3a and Hy-3c were derived. The M1-vacancies located in the (100) and (001) octahedral layers of the olivine lattice are suggested to form ordered arrays of planar defects (PD), which cause the band-like contrasts in HRTEM patterns as well as the superperiodicity in the SAED patterns. The vacancy concentrations as well as the chemical composition of Hy-2a, Hy-3a and Hy-3c olivine supercells were calculated using crystal chemical approaches, assuming either {(OH)^< _O−V^" _Me−(OH)^< _O}^↔, or {F e ^< _Fe −H _Me ^′}^↔ or {2F e ^< _Fe −V _Me ^"}^↔ point defect associates. The calculated theoretical compositions Mg_1.615Fe⁺² _0.135v_0.25SiO₄H_0.5 (Hy-2a) and Mg_1.54Fe²⁺ _0.12v_0.33SiO₄H_0.66 (Hy-3a and Hy-3c) are in a good agreement with the AEM data on inclusions. Hy-2a, Hy-3a and Hy-3c are considered to be a hydrous olivine with the extended chemical formula (Mg_1-yFe²⁺ _y)_2−xv_xSiO₄H_2x. The crystal structure of hydrous olivine is proposed to be a modular olivine structure with Mg-vacant modules. The crystal chemical formula of hydrous olivines in terms of a modular structure can be written as [MgSiO₄H₂] · 3[Mg_1.82Fe_0.18SiO₄] for Hy-2a, [MgSiO₄H₂] · 2[Mg_1.82Fe_0.18SiO₄] for Hy-3a and Hy-3c. Hydrous olivine is suggested to be exsolved from the olivine 9206, which has been initially saturated by OH-bearing point defects. The olivine 9206 hydration as well as the following exsolution of hydrous olivine inclusions is suggested to occur at high pressure-high temperature conditions of the upper mantle. Received: 15 January 2001 / Accepted: 2 July 2001     

多硅白云母b0值对澜沧群中压和高压变质的反映

多硅白云母b₀值作为相对地质压力计的理论和方法,已受到各国地质学家的普遍重视。本文以澜沧群多硅白云母作为研究对象,提出运用多硅白云母b₀值区分不同压力变质的方法。研究结果表明澜沧群经历了中压和高压变质作用,两期变质的多硅白云母b₀值分别为9.027Å和9.047Å。     

折射波法反演t0差数时距曲线法的自动化解释

本文介绍利用微型计算机对浅层初至折射波法野外采集的资料用t₀ 差数时距曲线法进行自动化解释的原理、程序框图和应用实例.在程序设计中为简化震源深度校正的步骤,采用了“震源深度简易校正”的方法^[1].利用微型计算机进行自动化解释,不仅可以提高工效几百倍,而且可以消除人工解释过程中的展点、绘图、画辅助线以及读数等方面引起的误差.     

CaMnSi2O6-CaAlSiAlO6系统的实验研究

冶金炉渣是在迅速冷却的条件下结晶的,铸石是在熔体的固相线以下恒温结晶的,这两种情况皆属不平衡状态。过去的硅酸盐体系的实验研究几乎仅局限于平衡状态,对非平衡状态研究甚少,只是近来才开始这方面的研究。在硅锰渣铸石和硅锰渣微晶铸石中,主要矿物为锰铸普通辉石--钙锰辉石与钙契尔马克分子（CaAlSiAlO₆）以及少量的Mg₂Si₂O₆的固溶体,其次是钙蔷薇辉石和钙长石,另外还有极少量的方锰石、硫化锰等。     

泥炭质土K0固结不同开挖路径应力-应变关系研究

基坑开挖过程中不同部位的土体会因不同的卸荷力学行为而表现出动态的破坏特性。为研究基坑土体开挖过程中复杂的卸荷应力路径,利用TSZ-1S应力控制式三轴仪分别对湖相沉积的泥炭质土进行固结不排水及K₀固结下的加、卸荷试验,并按侧向、轴向、轴侧向同时卸荷等不同卸荷条件制定试验方案,模拟基坑开挖过程中不同部位土体卸荷路径下的应力-应变曲线、卸荷剪切破坏时的强度及初始切线模量等的变化规律。试验结果表明：土体的应力-应变特性与应力路径密切相关,各路径下应力-应变曲线都近似呈双曲线型;卸荷剪切破坏时强度明显低于加荷破坏。对不同卸荷路径下初始切线模量(E_i)的研究发现,E_i受侧向卸荷影响较大,卸荷后E_i有所提高,轴向卸荷对其影响较小。对各应力-应变曲线进行归一化处理,构建了考虑不同归一化因子的归一化方程,以该方程为基础对不同应力路径下的泥炭质土进行归一化处理,并对结果进行了验证,效果良好。本研究可为泥炭质土场地上基坑在不同卸荷路径下的变形参数和本构关系的研究提供参考。