同步辐射软X射线吸收谱与发射谱测定天然针铁矿能带结构

天然半导体矿物由于成分、缺陷复杂,传统测试方法如紫外可见漫反射等难以准确测定其禁带宽度.本文以针铁矿为例,通过第一性原理计算得到纯针铁矿及掺Al针铁矿的电子结构.计算结果显示,纯针铁矿导带底与价带顶均由Fe3d与O2p轨道组成,而当含杂质Al时,Al2p与O2p发生杂化参与了价带组成.在此基础上,利用同步辐射X射线氧的K边吸收谱与发射谱对纯针铁矿及天然针铁矿的能带结构进行了测定.结果表明,天然含Al的针铁矿禁带宽度为2.30eV,小于纯针铁矿(2.57eV).本研究提供了一种测定天然氧化物矿物禁带宽度的新方法,为深入研究天然半导体可见光催化活性产生机制提供了理论依据.     

涉及埃达克岩实验的若干基本概念与问题辨析

根据热力学原理,部分熔融是相变的一种表现形式。当岩石沿p-T轨迹穿过固相线时即可发生熔融。自然界岩石常见的不一致熔融行为可以导致残留相具有不同于源岩的整体成分与矿物组合。残留相与源岩可以属于不同的变质相,岩性也可以不同。"C型埃达克岩"含有含水矿物,它们不是干体系熔融的产物。实验岩石学研究表明,基性成分(SiO_250%)体系较中性、酸性体系在1.0~2.0 GPa压力条件下失水熔融时更易于形成"榴辉岩质"的残留相。源岩除SiO_2以外的其它主要氧化物会影响残留相中各矿物的比例,进而影响熔体的Sr、Y及HREE含量。因此,"C型埃达克岩"高Sr低HREE特征的形成取决于熔融温压条件以及源岩的主量元素、微量元素组成等多重因素。高钾含量(K_2O≈1.0%)的基性、中基性源岩形成的熔体成分与"C型埃达克岩"相比过于富Al或富Na。中等富钾的基性源岩的低程度熔融可以形成高硅的"C型埃达克岩",但无法形成中性的"C型埃达克岩"。     

固相吸附毒素跟踪技术(SPATT)在浙江南麂海域的应用

浙江南麂岛海域是我国近岸贝类的重点养殖区,近年来一直遭受脂溶性贝类毒素(lipophilic shellfish toxins,LSTs)的污染,威胁着人类健康。为了建立有效的食品安全预警方法,本研究利用固相吸附毒素跟踪技术(solid phase adsorption toxin tracking,SPATT)在该海域进行了为期一年的野外监测和LSTs毒素分析。结果表明:7种LSTs毒素在SPATT(DIAION?HP20)中被检出,分别是大田软海绵酸(okadaic acid,OA)、鳍藻毒素-1(dinophysistoxin-1,DTX-1)、虾夷扇贝毒素(yessotoxin,YTX)及其衍生物homo YTX、扇贝毒素-2(pectenotoxin-2,PTX-2)及其衍生物7-epi-PTX2sa和环亚胺毒素(gymnodimine,GYM);有8种毒素在厚壳贻贝(Mytilus galloprovincialis)中被检出,分别是OA、DTX1、homo YTX、PTX2、7-epi-PTX2sa、GYM、原多甲藻酸贝类毒素-3(azaspiracid-3,AZA-3)和虾夷扇贝毒素衍生物45-OH-homo YTX。整体而言,SPATT(HP20)中吸附的毒素种类与贝肉中监测出的毒素种类大体上一致,且两者间OA、DTX1和PTX2的浓度在时间上具有较好的相关性,可见SPATT(HP20)对这些LSTs毒素具有较高的灵敏度,有望作为水体中LSTs毒素的预警监测材料。南麂岛海域LSTs分布特征明显,夏季最高,其次是春秋季,冬季最低,其中2014年夏季贝肉中OA毒素含量高达77.19ng/g贝肉,超出国家限量标准(45ng/g贝肉)比例达11.76%,为浙江南麂海域贻贝的食用安全带来隐患。     

Stability and capsizing analysis of nonlinear ship rolling in wind and stochastic beam seas

Considering the actual seaway condition, stability and capsizing of nonlinear ship rolling system in stochastic beam seas is of significant importance for voyage safety. Safe zone are defined in the phase space plan of the unperturbed Hamilton system to qualitatively distinguish ship motions as capsize and noncapsize. Capsize events are defined by solutions passing out of the safe zone. The probability of such an occurrence is studied by virtue of the random Melnikov function and the concept of phase space flux. In this paper, besides conventional wave excitation, the effect of wind load is also taken into account. The introduction of wind load will lead to asymmetry, in other words, it transforms the symmetric heteroclinic orbits into asymmetric homoclinic orbits. For asymmetric dynamical system, the orbital analytic solutions and its power spectrum are not readily available, and the technique of discrete time Fourier transformation (DTFT) is used. In the end, as verification of theoretical critical significant wave height, capsizing probability contour diagram is generated by means of numerical simulation. The contour diagram shows that these analytical methods provide reliable and predictive results about the likelihood of a vessel capsizing in a given seaway condition.     

A novel method to estimate mineral compositions of mudrocks: A case study for the Canadian unconventional petroleum systems

The mineral composition of mudrocks is an essential attribute in controlling the reservoir quality of unconventional petroleum systems. The present study introduces a semi-quantitative method to estimate mineral phases of mudrocks in various Canadian unconventional hydrocarbon systems using total elemental analysis (inductively coupled plasma-mass spectrometry (ICP-MS)) and Rock-Eval data (total organic carbon (TOC) and mineral carbon (MinC)).This method involves statistical analysis based on a sound knowledge of hydrocarbon source rock inorganic geochemistry. The workflow can be divided into four steps: (i) converting major elements (Si, Al, Fe, K, Na, Ca, Mg, Ti, and P) to their oxides, (ii) inferring modes of occurrence of elements using statistical analysis of geochemical data (major elements, TOC, and MinC), (iii) identifying the mineral types (oxide, aluminosilicates, carbonates, sulfide, and phosphate) according to elemental occurrences and calculating mineral phase concentrations, and (iv) verifying the results by comparing to XRD data on selected samples. The results, especially for brittle minerals such as quartz, carbonates (e.g. calcite, dolomite, and ankerite), and pyrite, show that the estimated mineral compositions correspond closely and consistently with measured mineralogy obtained from XRD. This method takes advantage of bulk geochemical data already available for hydrocarbon potential and chemostratigraphic studies, without devoting additional samples and cost for XRD analysis.     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

Tectono–Thermal Evolution, Hydrocarbon Filling and Accumulation Phases of the Hari Sag, in the Yingen–Ejinaqi Basin, Inner Mongolia, Northern China

This work restored the erosion thickness of the top surface of each Cretaceous formations penetrated by the typical well in the Hari sag, and simulated the subsidence burial history of this well with software BasinMod. It is firstly pointed out that the tectonic subsidence evolution of the Hari sag since the Cretaceous can be divided into four phases: initial subsidence phase, rapid subsidence phase,uplift and erosion phase, and stable slow subsidence phase. A detailed reconstruction of the tectonothermal evolution and hydrocarbon generation histories of typical well was undertaken using the EASY R_0% model, which is constrained by vitrinite reflectance(R_0) and homogenization temperatures of fluid inclusions. In the rapid subsidence phase, the peak period of hydrocarbon generation was reached at c.a.105.59 Ma with the increasing thermal evolution degree. A concomitant rapid increase in paleotemperatures occurred and reached a maximum geothermal gradient of about 43-45℃/km. The main hydrocarbon generation period ensued around 105.59-80.00 Ma and the greatest buried depth of the Hari sag was reached at c.a. 80.00 Ma, when the maximum paleo-temperature was over 180℃.Subsequently, the sag entered an uplift and erosion phase followed by a stable slow subsidence phase during which the temperature gradient, thermal evolution, and hydrocarbon generation decreased gradually. The hydrocarbon accumulation period was discussed based on homogenization temperatures of inclusions and it is believed that two periods of rapid hydrocarbon accumulation events occurred during the Cretaceous rapid subsidence phase. The first accumulation period observed in the Bayingebi Formation(K_1 b) occurred primarily around 105.59-103.50 Ma with temperatures of 125-150℃. The second accumulation period observed in the Suhongtu Formation(K_1 s) occurred primarily around84.00-80.00 Ma with temperatures of 120-130℃. The second is the major accumulation period, and the accumulation mainly occurred in the Late Cretaceous. The hydrocarbon accumulation process was comprehensively controlled by tectono-thermal evolution and hydrocarbon generation history. During the rapid subsidence phase, the paleo temperature and geothermal gradient increased rapidly and resulted in increasing thermal evolution extending into the peak period of hydrocarbon generation,which is the key reason for hydrocarbon filling and accumulation.     

柴达木盆地东部上石炭统克鲁克组碎屑岩储层特征及控制因素

柴达木盆地上石炭统克鲁克组是该区重要的古生界勘探层位,组内发育多套良好的碎屑岩层。为探究其岩石物性特征及控制因素,本次以野外露头调查为基础,利用普通薄片、铸体薄片鉴定及扫描电镜等手段,结合物性测试和压汞资料,对克鲁克组碎屑岩纵向分布规律,储层岩性、物性、孔喉特征及孔隙类型进行分析。认为克鲁克地层中克2段发育的三角洲前缘亚相和克3段的具障壁海岸潮坪相的大套含砾粗砂岩、粗砂岩砂体原生、次生孔洞发育,孔喉大、分布集中、分选好,为有利的碎屑岩储层。早成岩期压实作用、重结晶及胶结作用对克鲁克组砂岩的原生孔隙破坏严重,晚成岩期储层改造形成的溶孔、裂缝—溶孔是油气成藏的主要储存空间。该研究为预测柴东石炭系克鲁克组油气有利区域提供依据,为今后该地区的油气勘探提供理论支撑。     

Application of Geochemistry and VNIR Spectroscopy in Mapping Heavy Metal Pollution of Stream Sediments in the Takab Mining Area, NW of Iran

This study considered the possibility of using visible and near infrared (VNIR) spectral absorption feature parameters (SAFPs) in predicting the concentration and mapping the distribution of heavy metals in sediments of the Takab area. In total, 60 sediment samples were collected along main streams draining from the mining districts and tailing sites, in order to measure the concentration of As, Co, V, Cu, Cr, Ni, Hg, Ti, Pb and Zn and the reflectance spectra (350–2500 nm). The quantitative relationship between SAFPs (Depth500nm, R610/500nm, R1344/778nm, Area500nm, Depth2200nm, Area2200nm, Asym2200nm) and geochemical data were assessed using stepwise multiple linear regression (SMLR) and enter multiple linear regression (EMLR) methods. The results showed a strong negative correlation between Ni and Cr with Area2200nm, a significant positive correlation between As and Asym2200nm, Ni and Co with Depth2200nm, as well as Co, V and total values with Depth500nm. The EMLR method eventuated in a significant prediction result for Ni, Cr, Co and As concentrations based on spectral parameters, whereas the prediction for Zn, V and total value was relatively weak. The spatial distribution pattern of geochemical data showed that mining activities, along with the natural weathering of base metal occurrences and rock units, has caused high concentrations of heavy metals in sediments of the Sarough River tributaries.     

Composition and origin of the volatile components released from the Pesyanoe aubrite by stepwise crushing and heating

Aubrites are achondritic meteorites (enstatite pyroxenites) that were formed in highly reduced magmatic environments on a differentiated parent body sharing a common oxygen isotope reservoir with enstatite chondrites (EC), Earth and Moon, and could be considered as a geochemical model of the early proto-Earth. Some pyroxenes of the Pesyanoe aubrite have high abundance of gaseous inclusions, captured during the crystallization of the rocks. Investigation of the inclusions by IR spectroscopy reveals presence of OH⁻ groups and C–H bonds. The former are assigned to protonated point defects in enstatite lattice and the latter to compounds occupying void walls. Molecular water and CO₂ were not observed. Volatile components released from the samples of the Pesyanoe enstatite by stepwise crushing and heating are composed of CO₂, H₂O and a non-condensable phase. Hydrogen isotopic composition of volatiles extracted in form of molecular water in Px-separates varies in the range δD = −61 – −84‰ with mean value of δD = −73 ± 16‰ VSMOW and is within the ranges of ECs and Earth’s mantle. The total abundance of H₂ in the pyroxene of Pesyanoe were estimated as at least 0.047 ppm that is too low in comparison with that of enstatite chondrites (≥30 ppm H₂) and could indicate nearly complete degassing of the Pesyanoe primitive precursor material during the Pesyanoe parent body accretion or a mantle degassing in igneous differentiation process. In a last case a primitive precursor could have D/H ratio different from that of enstatite chondrites.