Detection of distribution of copper inside and outside of lysosomes in cultured hepatolenticular degeneration fibroblasts by electron probe X-ray microanalysis

OBJECTIVE: To observe the distribution of copper in the subcellular structure for the understanding of primary pathogenesis of hepatolenticular degeneration (HLD). METHODS: Skin fibroblasts taken from HLD patients were cultured as an in vitro model of HLD, and the control cells taken from healthy volunteers were clutured in the same way. The distribution of copper inside and outside of lysosomes in fibroblasts was detected by quantitative electron probe X-ray microanalysis. The relationship between the subcellular location of copper and the genotype of the patients, and relationship between the distribution of copper and the course of the disease were analyzed. RESULTS: The content of Cu^(2+) inside lysosomes of HLD cells (14.6±2.1 mmol/kg) and of heterozygote cells (11.6±0.6 mmol/kg) was higher than that of normal cells (4.5±1.2 mmol/kg) (P<0.01). The content of Cu^(2+) outside lysosomes of HLD cells (17.5±4.2 mmol/kg) and of heterozygote cells (12.0±0.9 mmol/kg) was higher than that of normal cells (4.7±1.2 mmol/kg) (P<0.01). The distribution of copper in the subcellular structure was correlated with disease courses of HLD patients. With the progression of the disease, more copper was deposited in lysosomes (r=0.85, P<0.01). The content of copper in the diffused cytoplasmic compartment in HLD cells was correlated with that of sulfur (r=0.86, P<0.05), but not in heterozygote and normal cells. CONCLUSIONS: In the early stage of HLD, copper is accumulated outside lysosome, which is paralleled with increase of metallothionein-like proteins (copper and sulfur-binding proteins). With the development of the disease, more copper is deposited inside lysosome than outside lysosome. We conclude that the up-regulation expression of copper and sulfur-binding proteins and copper accumulation in lysosomes may play an important role in lowering the ATP7B gene mutation-induced toxic effects of free copper on the cell.

Electron probe microanalysis оf experimentally stimulated osteoarthrosis in dogs

AIM To develop methods of articular cartilage preparation for X-ray-electron probe microanalysis and to study its elements content in experimental osteoarthrosis.METHODS Twenty dogs aged 2-8 years were divided in research(aged 2 years, induction of osteoarthrosis-IOA) and intact group. Intact group included three subgroups(aged 2, 5 and 8 years). Samples of cartilage after araldite saturation and pouring were partially cut into semithin sections stained with methylene blue and with methylene blue-basic fuchsin. Their smooth surfaces were investigated by X-ray-electron probe microanalysis. Spatial distribution of sulfur, calcium and phosphorus and their concentrations(weight %) were investigated.RESULTS X-ray electron probe microanalysis revealed non-uniformsulfur distribution in cartilage of intact animals: Its content increases from superficial zone to deep one, this regularity was preserved in animals with IOA. Differences of IOA with spontaneous chondropathy were revealed. Spontaneous aging was characterized by calcium and phosphorus storage in deep and calcified zones and compensatory increase of sulfated glycosaminoglycans in intermediate and deep cartilage zones as evidenced by the metachromatic reaction and microanalysis data. Unlike spontaneous chondropathy connected with aging in experimentally stimulated osteoarthrosis more intensive storage of calcium but minor phosphorus in intermediate zone were marked. In IOA the calcified cartilage thinning and osteoclastic resorption are apparent with few changes of elements composition; the only difference from control is minority phosphorus content.CONCLUSION The obtained results demonstrate specific tricks of X-ray electron probe microanalysis and its possibility in the research of mechanisms of articular cartilage alterations in osteoarthrosis.

Electron probe microanalysis for revealing occurrence mode of scandium in Bayer red mud

Red mud is a bauxite residue generated during the process of alumina production. In this research, the occur- rence mode of scandium in the Bayer red mud was investi- gated mainly by electron probe microanalysis （EPMA）. The Bayer red mud used in this work is composed of 21.47 wt% hematite, 12.13 wt% goethite, 8.86 wt% gibbsite, 5.02 wt% perovskite, 9.70 wt% quartz, 3.23 wt% anhydrite, 29.92 wt% Na_2Al_2Si_5O_14 and 9.67 wt% Al_3Fe_5O_12. Besides, the scandium content in the Bayer red mud is 84.32 × 10-6, indicating that this Bayer red mud is an important scandium resource deserving exploitation. The EPMA results show that the scandium within the Bayer red mud is mainly occurring in the iron minerals of hematite and goethite with the isomorphism form, but its distribution is not homogeneous in these iron minerals with the Sc_2O_3 content between 330 × 10-6 and 2040 × 10-6. This study provides a theoretical base for the further experimental work on the scandium extraction from this Bayer red mud.

Effect of Beam Current and Diameter on Electron Probe Microanalysis of Carbonate Minerals

The effect of operating conditions on the time-dependent X-ray intensity variation is of great importance for the optimal EPMA conditions for accurate determinations of various elements in carbonate minerals. Beam diameters of 0, 1, 2, 5, 10, 15, and 20 μm, and beam currents of 3, 5, 10, 20,and 50 nA were tested. Ca, Mg, Zn, and Sr were found to be more sensitive to electron beam irradiation as compared to other elements, and small currents and large beam diameters minimized the timedependent X-ray intensity variations. We determined the optimal EPMA operating conditions for elements in carbonate: 10 μm and 5 nA for calcite;10 μm and 10 nA for dolomite;5 μm and 10 nA or 10 μm and 20 nA for strontianite;and 20 nA and 5 μm for other carbonate. Elements sensitive to electron beam irradiation should be determined first. In addition, silicate minerals are preferred as standards rather than carbonate minerals.

A double toroidal analyzer for scanning probe electron energy spectrometer

An ultra-high vacuum （UHV） compatible electron spectrometer employing a double toroidal analyzer has been de- veloped. It is designed to be combined with a custom-made scanning tunneling microscope （STM） to study the spatially localized electron energy spectrum on a surface. A tip-sample system composed of a piezo-driven field-emission tungsten tip and a sample of highly ordered pyrolytic graphite （HOPG） is employed to test the performance of the spectrometer. Two-dimensional images of the energy-resolved and angle-dispersed electrons backscattered from the surface of HOPG are obtained, the performance is optimized and the spectrometer is calibrated. A complete electron energy loss spectrum covering the elastic peak to the secondary electron peaks for the HOPG surface, acquired at a tip voltage of -140 V and a sample current of 0.5 pA, is presented, demonstrating the viability of the spectrometer.

东昆仑大格勒富铌碳酸岩矿物学特征

东昆仑大格勒地区新发现一套碱性岩-碳酸岩杂岩体,具有很好的铌等稀有金属成矿潜力。本文在岩相学研究基础上,结合背散射电子图像,应用电子探针能谱半定量分析和波谱定量分析技术,对东昆仑大格勒富铌碳酸岩中的铌矿物进行了原位微区成分分析。岩相学观察表明,铌矿物主要为铌铁矿族、铌钙矿、烧绿石、褐铈铌矿、铌易解石,含铌矿物为含铌钛铁矿、斜锆石。铌矿物嵌布粒度较细,嵌布关系紧密而复杂。其中,铌铁矿族常与磁铁矿、铌钙矿、褐铈铌矿和磷灰石紧密共生,多以细粒状集合体呈浸染状、星散型沿磁铁矿裂纹与边部进行交代。铌钙矿、烧绿石和褐铈铌矿常与铌铁矿、磁铁矿和磷灰石紧密共生,铌钙矿局部与铌铁矿呈不规则状接触分布,烧绿石呈不规则状沿铌铁矿边部分布,褐铈铌矿多以团块状沿铌铁矿边部分布。铌易解石与磁铁矿紧密共生,呈不规则状接触。初步推断铌矿物包括岩浆期形成的烧绿石和铌易解石,热液期形成的铌铁矿、铌钙矿、烧绿石和褐铈铌矿。矿物组合初步显示,大格勒富铌碳酸岩中的铌至少经过了岩浆和热液两个时期的富集。电子探针分析结果表明,主要铌矿物的Nb_(2)O_(5)平均含量分别为:铌铁矿族69.92%,铌钙矿59.55%,烧绿石59.14%,褐铈铌矿43.12%,铌易解石41.55%;含铌矿物的Nb_(2)O_(5)平均含量分别为:含铌钛铁矿1.33%,斜锆石1.22%。其中,铌铁矿族和铌钙矿、烧绿石为可选且具有工业价值的铌矿物。

Frequency dependence of electron temperature in hollow cathode-type discharge as measured by several different floating probe methods

We measured electron temperatures through a hollow cathode-type discharge tube using several different floating probe methods. This method detected a shift in the floating potential when an AC voltage was applied to a probe through an intermediary blocking capacitor. The shift in the floating potential is described as a function of the electron temperature and the applied AC voltage. In this study, the effects of the frequency and waveform on the electron temperatures were systematically investigated. The electron temperature measured when using the floating probe method with applied sinusoidal and triangular voltages was lower than that measured with an applied rectangular voltage.The value in the high frequency range was close to that of the tail electron temperature.

Electron Temperature Measurement by Floating Probe Method Using AC Voltage

This study presents a novel floating probe method to measure electron temperatures using a hollow cathode-type discharge tube. The proposed method detects a shift in the floating potential when an AC voltage is applied to a probe through an intermediary blocking capacitor. The shift in the floating potential is described as a function of the electron temperature and the applied AC voltage. The floating probe method is simpler than the Langmuir probe method because it does not require the measurement of volt-ampere characteristics. As the input AC voltage increases, the electron temperature converges. The electron temperature measured using the floating probe method with an applied sinusoidal voltage shows a value close to the first （tail） electron temperature in the range of the floating potential.

STEM朗奇图和电子束斑模拟插件

在扫描透射电子显微镜(STEM)中,实现原子级分辨率的关键在于精确的像差校正,这通常依赖于朗奇图的测量和优化。对于STEM的新手而言,理解和优化朗奇图是一项极具挑战性的任务,往往需要长时间的实践积累才能掌握。本研究介绍了一种朗奇图及电子束斑模拟分析插件,用户可直接调整各种像差参数(包括像散、球差、慧差等),实时观察这些参数变化如何影响朗奇图,从而更直观地理解各种像差对朗奇图和电子束斑的影响。此外,插件还提供focus wobble功能,动态显示不同焦距下的朗奇图和电子束斑,模拟实际实验过程中在正焦附近循环调焦时的朗奇图和电子束斑。该插件不仅为初学者理解像差方程提供了直观图像演示,进而更加便捷和迅速地掌握球差校正电镜的调节和使用,也为研究人员提供了一种展示像差方程、朗奇图和电子束斑的图形化工具。

基于耳石微化学的大洋河刀鲚生境履历研究

为探明大洋河刀鲚(Coilia nasus)的“生境履历”,利用电子探针微区分析技术(EPMA)对2020年7月和9月采自大洋河下游水域20尾刀鲚的矢耳石进行了锶(Sr)和钙(Ca)的微化学分析研究。定量线分析结果显示,刀鲚样本均为淡水起源,淡水生境Sr/Ca比值在(1.49±0.61—2.75±0.53),淡水系数(Fc)在(0.08—0.52),淡水区域径长在(150—900μm)。进入第二变化阶段后“生境履历”波动显著,Sr/Ca比值变化可将大洋河刀鲚分为3种模式,第一种是中高值区(半咸水或海水)越冬,繁殖季溯河洄游至低值区(淡水);第二种是长期栖息于中高值区,无溯河洄游现象;第三种是在中高值区和低值区多次转换,DYH 05、19个体最高完成9次转换。Sr面分析结果也与上述Sr/Ca比值结果相同。这三种模式直观地反映出大洋河刀鲚群体“生境履历”的多样性特点。

赣南斑岩锡矿田云英岩型锂矿中锂的赋存状态研究

云英岩型锂矿作为近年来新的锂矿类型,具有重要的理论研究和经济价值。然而,在中国南岭及其周缘世界级的钨锡成矿省中,伴生云英岩型锂矿化的综合评价却稍显不足。本课题组在赣南岩背斑岩锡矿田新发现了云英岩型的锂矿,矿体产于密坑山岩体与上覆鸡笼嶂组火山岩的接触带附近的云英岩带内,发育三种矿化类型:云英岩带型和花岗岩、火山岩内的含锂云母-石英脉型。矿体中Li_(2)O的含量最高可达1.04%,主要集中于0.2%~0.3%,具有显著的综合利用价值。为了确定云英岩型锂矿中Li的赋存状态及Li、Sn之间的关系等特征,本文开展了详细的镜下观察,扫描电镜、电子探针和LA-ICP-MS分析,确定了岩背矿田不同于国内外其他典型云英岩型锂矿床大量发育锂云母-铁锂云母系列,其Li载体矿物主要为黑鳞云母,具有高Si、Al、K、Fe、Li的特征,且未经历极端的流体分异演化过程。Li的成矿主要与矿区含斑细粒花岗岩有关,在岩浆晚期高温热液阶段与Sn共同富集,并以Si^(4+)+Li^(+)←→Al^(Ⅳ)+Fe^(T)耦合类质同象形式进入云母。

东昆仑大格勒地区富铌橄榄岩中的含铌矿物组成

铌(Nb)是我国极度紧缺的战略性矿产资源,对外依存度非常高。近期本研究团队在东昆仑大格勒地区发现了志留纪–泥盆纪碱性岩–碳酸岩型铌、磷矿化杂岩体,岩石类型主要为橄榄岩、单斜辉石岩、橄榄辉长岩、角闪石岩和碳酸岩等。橄榄岩中Nb_(2)O_(5)品位为0.5%~0.8%,平均为0.6%,是原始地幔Nb丰度(0.713×10^(-6))的数千倍,显示了Nb元素的超常富集。本文在光学显微镜岩相学研究的基础上,应用电子探针背散射图像、能谱分析及电子探针定量分析技术,对橄榄岩中含铌矿物类型、共生关系及其化学组成进行研究。结果表明,橄榄岩中含铌矿物主要为烧绿石、(铈)铌钙矿、(铈)钙钛铌矿、褐铈铌矿和含铌钛铁矿,其中烧绿石含量最高(约1%)。5种矿物中Nb_(2)O_(5)含量依次为:烧绿石(71.45%~74.50%)、(铈)铌钙矿(50.96%~55.26%)、(铈)钙钛铌矿(43.27%~47.73%)、褐铈铌矿(41.63%~44.26%)以及含铌钛铁矿(4.63%~4.99%)。烧绿石呈半自形粒状晶,充填于磁铁矿等矿物粒间。本研究为东昆仑造山带碱性–碳酸岩型铌矿成矿潜力分析、成矿规律总结以及下一步矿产勘查部署提供了依据。

长江安庆江段存在溯河洄游型和淡水定居型刀鲚实证研究

为了探究长江十年禁渔后安庆江段刀鲚的生境履历,利用X射线电子探针微区分析技术研究安庆江段不同类型长颌刀鲚(Coilia nasus)和短颌刀鲚的耳石Sr和Ca微化学特征。结果显示,根据耳石Sr/Ca值的变化值将安庆江段的短颌刀鲚分为2类,一类是其比值为一直小于3.0的低值,表明其纯淡水的生境履历;另一类是其比值不仅有小于3.0的低值区,还有大于3.0的高值区(小于7.0),表明其不仅有淡水的生境履历,还有高盐度的河口半咸水生境履历。长颌刀鲚的耳石Sr/Ca值均具有小于3.0的低值区和大于3.0(甚至大于7.0)高值区的显著波动,表现为典型的淡水、河口半咸水及海水的溯河洄游型生境履历,Sr含量面分析图谱也可印证上述结果。本研究表明,长江安庆江段刀鲚群体组成较为复杂,同时存在溯河洄游型、淡水定居型短颌刀鲚和溯河洄游型长颌刀鲚3种生态表型个体。

磷铍钙石中铍元素的电子探针定量分析

前人使用配有LDEB或LDE3H的电子探针,建立了针对铍硅酸盐、铍氧化物以及铍硼酸盐中Be含量的定量分析方法。然而,缺乏对铍磷酸盐矿物中Be含量的定量分析方法。目前,使用配备LSA300分光晶体的电子探针对铍磷酸盐矿物进行分析时,P元素的高级次阶峰会抬高Be Kα峰的上背景值,从而导致Be含量的测量结果不准确。本文使用配备LDE3H分光晶体的电子探针,对江西狮子岭花岗岩中的磷铍钙石,采用不同的加速电压和分析束流,进行最佳定量分析条件的探索。实验结果表明:磷铍钙石的最佳电子探针定量分析条件为:加速电压10kV,分析束流20nA。在此条件下,获得的磷铍钙石P_(2)O_(5)平均含量为43.23%,BeO平均含量为15.39%,CaO平均含量为33.89%,F平均含量为7.94%,BeO标准误差为0.3%。本研究发现配有LDE3H分光晶体的电子探针,可以设置合适的Be背景来消除P的高级次阶峰的干扰。此外,含Be矿物的测量难点与Be特征X射线本身的特征、含Be矿物的晶体结构、化学成分均有关。磷铍钙石定量分析方法的探索,解决了电子探针对铍磷酸盐矿物Be元素进行准确定量时,P元素产生的干扰难题,进一步提升电子探针对铍含量测量的准确度。

川西南峨眉山玄武岩中蚀变绿泥石的成分特征及其地质意义

在火山岩和碎屑岩储层中普遍发育大量绿泥石,影响着物性。为查明火山岩中蚀变绿泥石的成因及其对储层物性的影响,本次工作选取川西南峨眉山典型剖面、ZG1井、ZG2井以及YT1井等系列玄武岩样品进行岩相学研究和电子探针微区成分分析。结果显示:玄武岩中绿泥石大致可分为显晶质、隐晶质和微晶3种结晶类型,总体上属于富铁种属的铁斜绿泥石(辉绿泥石)和铁镁绿泥石,形成于富铁的还原环境;隐晶质与微晶和显晶质绿泥石分别受到岩浆期后热液和来自深部的多期次构造热液叠加蚀变的控制,形成主要表现为Fe^(2+)对Mg^(2+)的成分置换,反映流体具有从碱性向弱酸性-中酸性过渡的变化规律。绿泥石的形成过程对火山岩储集空间的影响具有双重作用:岩浆期后热液的充填结晶充填减少了火山岩原生孔隙并降低储层物性,对火山岩储层起到破坏性作用;多期次构造热液的溶蚀迁移沉淀则产生了新的微孔,对火山岩储层起到建设性作用。

松辽盆地砂岩型铀矿铀含量配分比例的半定量分析

钱家店铀矿是位于松辽盆地南部的复成因砂岩型铀矿,受表生淋滤、辉绿岩中低温热液和深部油气等多流体影响,目前铀矿物赋存状态尚有一定争议,铀在矿石内不同矿物中的配分尚不明确。为了进一步明确铀赋存状态和在不同矿物中的配分,计算钱家店矿石中不同矿物中铀的配分比例,本文运用岩矿鉴定、铀化学逐级提取、电子探针和激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)微区原位分析技术开展综合测试分析。明确了钱家店铀矿物的赋存状态,认为钱家店铀矿物以吸附态为主,约占总铀含量的80%,结合态铀矿物或含铀矿物约占比20%。其中吸附态铀矿物主要富集在方解石等碳酸盐矿物中,占总铀含量的47.86%,其次是在黏土矿物中占17.94%,在铁锰氧化物矿物中占12.21%。独立铀矿物是与黄铁矿密切共生的沥青铀矿为主,约占铀总含量的9.07%,另有少量含钛铀矿物和铀石约占5.08%。这种矿石中各碎屑组分中铀的占比量化研究,为矿床地浸开采及资源量计算提供依据。

磁相变材料热膨胀与磁致伸缩效应测试

基于综合物理性能测试系统的低温与磁场环境,采用应变片测试方法开发了磁相变材料热膨胀系数的表征方法,验证了测试结果的可靠性,并开展了磁相变材料LaFe11Co0.8Si1.2负膨胀性能的研究。结果表明:在居里温度处,LaFe11Co0.8Si1.2材料的热膨胀量随温度的升高而减小,这是因为材料发生了铁磁性向顺磁性的磁相变,导致其产生磁致伸缩效应,抵消了原子非简谐振动引起的热胀冷缩,最终导致材料发生负热膨胀现象。

碳酸盐岩微观测试技术对比与应用——以济阳坳陷乐安油田潜山为例

微观测试结果能反映很多油藏信息。目前关于微孔缝的镜下测试技术不断丰富,但仍缺少对微孔缝最全面的微观分析。为了便于对比各类测试技术,以济阳坳陷乐安油田草桥潜山区域为典型代表实例,先采用不同的精细微观专项测试技术对孔缝储集空间特征进行分析,具体包括微溶孔电子探针成分分析、扫描电镜、薄片和阴极发光测试等技术,然后总结了通过各种不同的微观测试技术观察到的现象及规律。具体结果和得出认识如下:通过电子探针成分分析技术,能够分辨出灰岩微溶孔内诸如有机质、方解石、黄铁矿、白云石、石膏等成分;薄片内可见灰岩含油段砾间砾内孔洞发育,溶蚀孔洞边部有轻微方解石化;通过扫描电镜分析,能够分辨出代表区块的白云岩结晶孔比灰岩溶蚀孔大两个以上数量级,能通过晶间孔或溶蚀孔推断岩石的脆性以及是否易于压裂;通过岩样阴极发光测试,能够区分出共有几期成分不同的孔洞充填物;通过扫描电镜和压汞都可以得到孔喉大小,比较两项技术,扫描电镜得到的是局部纳米级的孔喉直径,而压汞测试得到的是单块样品微米级孔喉半径。从应用对象来看,前者适合对应到矿物的孔喉,后者更适合开发区块的孔喉对比研究。

高碳中锰耐磨钢凝固过程溶质微观偏析模型

通过定向凝固、电子探针(EPMA)、Factsage等多种实验与理论计算相结合的手段对中锰耐磨钢凝固过程溶质元素微观偏析行为进行了系统研究.研究表明在定向凝固试验中当拉速为50μm·s-1时,中锰钢的二次枝晶间距平均值为59.77μm;中锰钢凝固过程组织转变为L→L+γ→γ属于奥氏体凝固模式,无包晶反应的发生,也无铁素体相及其他相的出现;中锰钢定向凝固过程中Mn、Cr在枝晶间的含量明显高于枝晶内,表明Mn、Cr元素发生了明显的正偏析行为;通过对各特征参数求解,构建了中锰钢溶质元素微观偏析模型,发现中锰钢定向凝固过程中Mn元素偏析指数与Brody–Flemings模型符合较好,而Cr元素偏析指数与Clyne–Kurz模型分布较为一致.

“雅安绿”图章石的宝石矿物学特征研究

图章石普遍“缺蓝少绿”,“雅安绿”以其明艳的绿色成为近年图章石的重要品种,而迄今为止,关于“雅安绿”图章石相关报道较少,且易与其它绿色图章石相混淆,故本文对“雅安绿”图章石这一品种进行深入研究,为其鉴别提供一定的依据。主要采用X射线粉末衍射、拉曼光谱、扫描电子显微镜、电子探针及紫外-可见光谱对“雅安绿”图章石样品的矿物组成、微形貌特征、化学成分、颜色成因进行测试分析。结果表明,“雅安绿”图章石样品中的绿色基质的矿物组成为白云母,黄色杂质矿物组成主要为白云石和黄铁矿,并含少量的石英、磷灰石和金红石。扫描电子显微镜观察发现,“雅安绿”图章石样品中的白云母呈假六方片状,呈三维空间无序排列;可见自形黄铁矿及完全解理块状的白云石。紫外-可见光光谱分析认为,“雅安绿”图章石样品的翠绿色主要由白云母中微量元素Cr引起。