Direct and Simultaneous Determination of Several Impurity Elements in Manganese Tetroxide using ICP-AES

A rapid method for the determination of impurity elements, such as Zn, Ni, Co, Cr, Cu, Cd and Pb in manganese tetroxide was developed, using inductively coupled plasma atomic emission spectrometry （ICP-AES）. The critical instrumental parameters such as sample flow rate and radio frequency incident were thoroughly optimized. The effect of matrix was also examined. The sensitivity was investigated using calibration curves obtained in presence of the matrix. The obtained recoveries for Ni, Co, Cr, Cu, and Cd at the μg· g^ -1 level were satisfactory and practically independent of the matrix used for the calibration standards. The recoveries of Pb and Zn were less suffwient. The method can be applied for routine analysis and quality control purposes at μg· g^-1 level of concentration.

Determination of trace impurity elements in MnZn ferrite powder by direct current glow discharge mass spectrometry

An analytical method for the determination of 26 impurity elements （such as Li, Be, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V, Cr, Co, Ni, Ga, Ge, Y, Nb, Mo, Ag, Cd, Sb, W and Pb） in MnZn ferrite powder by direct current glow discharge mass spectrometry （GD-MS） was established. MnZn ferrite powder was mixed with copper powder, used as a conductor, and pressed. The effects of MnZn ferrite powder preparation conditions and glow discharge parameters for the sensitivity and stability of signal analysis were investigated. By determining the choice of isotope and the application of the mass resolutions of 4000 （MR, medium resolution） and 10000 （HR, high resolution）, mass spectral interference was eliminated. The contents of impurity elements in MnZn ferrite powder was calculated by subtraction after normalizing the total signal of Mn, Zn, Fe, O and Cu. The results showed that the detection limit of 26 kinds of impurity elements was between 0.002 and 0.57 μg/g, and the relative standard deviation （RSD） was between 3.33% and 32.35%. The accuracy of this method was verified by the ICP-MS. The method was simple and practical, which is applied to the determination of impurity elements in MnZn ferrite powder.

Determination of impurity elements in MnZn ferrites by inductively coupled plasma mass spectrometry

An inductively coupled plasma mass spectrometry(ICP-MS) method was developed for the determination of Na, Mg, Al,K, Ca, Ti, Cr, Co, Ni, Cu, Ga, As, Mo, Ag, Cd and Pb in MnZn ferrites. The sample was digested by HNO3+HCl with microwave digestion followed by dilution with ultrapure water, then the above 16 impurity elements in the solution were analyzed directly by ICP-MS. The impurity elements were introduced by the helium gas or hydrogen gas into the octopole reaction system(ORS) to eliminate the polyatomic interferences caused by the high salty matrixes. The matrix effect was minimized through matrix matching,and Be, Y and Rh were used as internal standard elements. The working parameters of the instrument were optimized. The results show that the method has good precision and high accuracy. The detection limits for the investigated elements are in the range of0.9-37.5 ng/L, the relative standard deviation of each element is within 1.1%-4.8%, and the recovery of each element is 90%-108%.

Features of rare earth elements geochemistry in coals of Central Kazakhstan

This research presents the results of a comprehensive study of mineralogical and geochemical features of REE distribution in coals of Central Kazakhstan deposits—Karaganda coal basin and Shubarkol deposit,which have large hard coal reserves and are industrially important for the coal industry of Kazakhstan;the research is based on 205 samples of clayey interlayers and coal seams.It shows basic patterns of distribution and features of concentration for impurity elements,gives an estimate of the impurity elements concentration,including REE,defines conditions and factors of their accumulation,and studies features of their forms in coal and coal-bearing rocks,which allows estimating the mechanisms of their migration and conditions of accumulation.According to the results of geochemical indicators,the article establishes the factors of REE dislocation,reveals the composition of margin rocks that have influenced REE concentration in coal seams,and the presented latest data on mineralogy allowed to establish the ways of their transportation to the paleobasin during the synand epigenetic periods of formation of the coal deposits of Central Kazakhstan being researched.It was found that the coals are insignificantly enriched with heavy lanthanides from Ho to Lu.The distribution curves of UCC normalized REE values in the coals are similar and coincide,but they are less than the average value for world coal,and amount to only one-third of the UCC.It was found that the highest concentrations of all REE are characteristic of clayey interlayers and oxidized coals.The La/Yb ratio in this case increases upwards along the section,indicating mainly clastogenic mechanism of REE delivery to the coals.In coal and clay samples,the predominant mineral form of REE is light lanthanide phosphates.Identified particles of REE from minerals and their composition peculiarities suppose autigene nature of their formation.The formation of the bulk of autigene minerals occurred during the maturation of brown coals and their transformation into hard ones.

DETERMINATION OF IMPURITY ELEMENTS IN ALUMINIUM

Twenty five impurity elements in aluminium applied as reactor material are determined. Titanium and nickel are determined with epithermal neutron activation analysis (NAA), magnesium and silicon by inductance coupling plasma emission spectra (ICP), other elements by thermal NAA. The fission coefficient of uraniumis given by an experiment, the interferences of uranium to Ce, Nd, Mo, Zr, La, Sin are subtracted. The detection limits of these methods to all of impurity elements in aluminium are calculated.

First-principles Investigation on Solution Hardening of Interstitial Impurity Elements (O,N) inγ-TiAl

We have calculated the electronic Structures of O-doped and N-doped r-TiAl using the firstprinciples discrete variational method (DVM) with the aim to understand the solution hardening effects of oxygen and nitrogen in r-TiAl. Our combination analysis on the electronic density, density of states (DOS) and the local environment total bond orders (LTBO) will show that, X atom (X is O or N) can strongly bind with its six surrounding atoms via electronic hybridizations of Ti-3d/X-2p and Al-3p/X-2p. As a sequence, there forms a 'hard' cohesive region around the impurity atom. A pinning model based on the calculations is proposed to explain the hardening effects. The consistent results are obtained between the present calculation and formal test experiments.

Electronic Theoretical Study of the Interaction between Rare Earth Elements and Impurities at Grain Boundaries in Steel

The model of dislocations was used to construct the model of grain boundary (GB) with pure rare earths, and rare earth elements and impurities. The influence of the interaction between rare earth elements and impurities on the cohesive properties of 5.3° low angle GB of Fe was investigated by the recursion method. The calculated results of environment sensitive embeding energy( E ESE ) show that the preferential segregation of rare earth elements towards GBs exists. Calculations of bond order integrals (BOI) show that rare earth elements increase the cohesive strength of low angle GB, and impurities such as S, P weaken the intergranular cohesion of the GB. So rare earth element of proper quantity added in steel not only cleanses other harmful impurities off the GBs, but also enhances the intergranular cohesion. This elucidates the action mechanism of rare earth elements in steel from electronic level and offers theoretical evidence for applications of rare earth elements in steels.

Impurity Profiling of Solid Oral Drug Products to Sail through GDUFA-II Requirements

Defining impurity profile is key element to ensure safe, efficacious and quality human drugs. Impurity profiling changed/transformed drastically over the years. Guidelines, specifications and requirements are evolving. Initially impurity profiling was based on simple methods later by degradation studies, then to understand drug strength and efficacy chiral impurities and stereo isomers were included followed by residual solvents, polymorphic forms, genotoxic impurity studies. Currently, elemental impurities are the latest addition. As per the GDUFA II guidelines to improve review efficiency and reduce review cycles, data requirements have changed. Based on recent guidance and review points, Impurity profiling has significant importance in ANDA filing and to ensure approval within 10 months (first cycle approval) which is an exiling aspect for industries to enter into the generic market quickly. Hence, Impurity profile is a key aspect scientifically, regulatory wise and commercially also. This is a review article on impurity profiling of Solid oral drug substances and products as per GDUFA II requirements the reference documents for the review are ICH guidance, relevant FDA GDUFA guidance and common industry practices.

电感耦合等离子体-质谱法测定枸橼酸三乙酯中7种元素杂质

目的建立测定枸橼酸三乙酯中镉(Cd)、铅(Pb)、砷(As)、汞(Hg)、钴(Co)、钒(V)、镍(Ni)7种元素杂质残留量的电感耦合等离子体-质谱法。方法采用在线内标法,载气为氦气,等离子体模式为HMI-8,载气、雾化气、辅助气流量均为0.8 L/min,等离子气流量为15.0 L/min,蠕动泵转速为0.10 r/min,雾化室温度为2℃。结果V,Co,Ni,As,Cd,Pb元素的质量浓度在0~20.0 ng/mL范围内,Hg元素的质量浓度在0~5.0 ng/mL范围内,与仪器响应值线性关系良好(r≥0.9995,n=7);精密度试验结果的RSD均小于3%(n=6);加样回收率分别为97.58%,96.12%,96.56%,100.25%,96.63%,99.80%,106.73%,RSD分别为1.11%,1.29%,2.43%,1.09%,0.89%,1.26%,4.48%(n=9)。23批样品中7种元素杂质含量均低于控制阈值。结论该方法操作简便、精密度好、结果准确,可用于枸橼酸三乙酯中痕量元素杂质的含量测定。

化学原料药元素杂质控制策略探索与思考

元素杂质影响药品安全性和有效性,国际人用药品注册技术协调会(ICH)在2022年4月发布了《Q3D(R2):元素杂质指导原则》最终版。本文参考Q3D(R2)分析了化学原料药中元素杂质,识别出各种潜在来源的可能元素杂质,对生产角度各环节元素杂质的控制策略进行讨论,为后续药品研发、生产、质量控制和上市变更研究,提供了新的研究思路。

天然石英矿物微量元素赋存特征研究进展及对高纯石英找矿的指示

目前,中国4N8以上高纯石英高度依赖进口,高纯石英是保障中国芯片安全、光纤安全、光伏安全、高端器件安全的战略矿产。笔者通过国内外对石英的微量(杂质)元素分布特征研究相关的文献进行了梳理和总结,并结合近年来找矿勘查实践认识。研究发现,控制4N以上中高端高纯石英杂质元素的种类主要是类质同象,包括有B、Li、Al、Ge、Ti、Fe、Mn、K和P等元素。中国高纯石英找矿方向包括变质重结晶石英、钨锡矿床云英岩和石英脉、花岗伟晶岩石英、高分异演化花岗岩石英等,其中4N以上中高端高纯石英可能为非成矿花岗伟晶岩。高纯石英矿床形成的地质背景、物质组成、物质来源、控制因素等与成矿有关的理论,即建立高纯石英成矿模型,可能是中国高纯石英矿床的找矿勘查突破的基础。这些研究除了能够很好地指导高纯石英找矿,同时也是示踪钨、锡、铌、钽和锂等金属矿床岩浆-热液演化过程的关键。中国高纯石英地质勘查处于起步阶段,笔者总结近年攻关中国高纯石英找矿勘查理论和技术研究,以供同行参考。

联用扫描电子显微镜-能谱法和电感耦合等离子体质谱法核取证表征铀矿石浓缩物

该研究建立了联合扫描电子显微镜-能谱法(SEM-EDS)、全溶/电感耦合等离子体质谱法(ICP-MS)和萃淋去铀电感耦合等离子体质谱法(CL-TBP/ICP-MS)鉴别铀矿石浓缩物(UOC)中60余种杂质元素种类和含量的方法。通过SEM-EDS得到5种UOC的表面微观形貌,并结合ICP-MS得到的N、O、S、K和Cl等基体元素的含量信息,可初步判断不同UOC的生产方式及其化学组成。全溶/ICP-MS方法可快速测定Na、Ca、Fe等含量较高的基体元素,特别在测量W、Sn等易吸附或水解元素含量方面具有优势。CL-TBP/ICP-MS方法的优势在于可获得包含极低含量目标元素在内的60种元素的种类和浓度,对重点关注的稀土元素的检出限可达10-9 g/g量级。根据稀土元素含量及其分布模式信息,可有效鉴别不同来源的UOC,并初步推测其成矿类型。该方法操作简便、结果准确、重现性好,可为铀矿石浓缩物和其他铀基体材料的核取证表征、解析溯源、数据库建设等提供参考和技术支持。

ICP-MS法测定明胶元素杂质与风险评估

目的建立ICP-MS法测定明胶中Cd、Pb、As、Hg、Co、V、Ni、Li、Sb、Ba、Mo、Cu、Sn和Cr等14种元素杂质的残留量,并对其元素杂质进行风险评估。方法样品经微波消解后采用在线内标ICP-MS法,以Sc、In、Ge和Bi为内标,Li采用非碰撞模式测定,其余元素采用He碰撞模式,等离子体模式为HMI-8,雾化室温度2.0℃。结果14种元素杂质在线性范围内相关系数r均大于0.9932;加样回收率在77.1%~105.8%范围内,RSD(n=6)在0.7%~4.4%范围;精密度RSD在0.6%~7.5%范围;18批样品中,3批样品Pb元素超过ICHQ3D口服和注射浓度控制阈值,1批次样品Ni元素超过注射浓度控制阈值。结论建立的方法灵敏度高、精密度、准确度良好,能够很好地控制明胶中的痕量元素杂质;根据ICHQ3D指导原则进行风险评估,明胶12种元素杂质存在风险系数较低,Pb和Ni 2种元素杂质存在风险系数较高,为明胶的风险评估提供了参考。

ICP-AES法测定废电解铝阳极碳块中铁、锂、钾、钙、镁含量

废电解铝阳极碳块经过高温碳化,通过盐酸-硝酸-高氯酸三酸溶解完全后,冷却,完全溶解盐类加入10 mL 1.19 g/mL的盐酸,在优选出最优的仪器工作状态下,创建了ICP-AES法测定废电解铝阳极碳块样品中Fe、Li、K、Ca、Mg的化学分析方法。每个元素的校准曲线相关系数均大于0.999,同时对以上多种元素进行检出限、加标回收试验研究,结果表明其相对标准偏差(n=8)为0.60%~2.24%,加标回收率在97.1%~104%。

GH4742合金真空自耗铸锭中夹杂物分布特征

以ϕ570 mm的合金锭作为自耗重熔的电极,通过起弧、稳定熔炼和热封顶三个阶段,制备ϕ660 mm的真空自耗铸锭,熔炼过程共历时860 min。采用场发射电子扫描显微镜和夹杂物自动扫描系统,分析了真空自耗重熔GH4742合金工业铸锭内部及其特征位置(锭冠、搁架、橘皮)处夹杂物的分布规律。结果表明,GH4742合金真空自耗铸锭中夹杂物的类型主要有Ti(C,N)、LaAlO_(3)-Ti(C,N)、Ti(C,N)-(Ti,Nb,Mo)C及LaAlO_(3)-Ti(C,N)-(Ti,Nb,Mo)C四种。夹杂物的尺寸主要以<3μm的小尺寸夹杂物为主,从中心到边缘夹杂物的尺寸逐渐降低,夹杂物的数量密度逐渐增多。铸锭中部中心处夹杂物的尺寸最大,最大平均尺寸为4.14μm。铸锭底部中心处的夹杂物数量最少,数量密度为13.23个/mm^(2)。铸锭锭冠、橘皮及搁架处分布着聚集的氧化物夹杂,这是电极上脱落的氧化物在熔池流动作用下运动到铸锭边缘,被边缘凝固区域捕捉形成的。

ICP-MS法测定葡甲胺中10种元素杂质的残留量

目的:建立ICP-MS法检测葡甲胺原料中10种元素杂质的方法。方法:以密闭高压微波消解法处理样品,采用ICP-MS法测定1类元素杂质砷(As)、镉(Cd)、汞(Hg)、铅(Pb)、2A类元素杂质钴(Co)、镍(Ni)、钒(V)、3类元素杂质锂(Li)、锑(Sb)、铜(Cu)的含量,并以全定量方式定量。结果:各元素杂质线性相关系数r均大于0.997;加样回收率在93.6%~116.8%,回收率RSD均低于7.4%;精密度RSD均低于5.4%;11批样品中镍元素含量低于ICH Q3D(R2)元素指导原则中2A类元素杂质的口服用每日允许暴露量(PDE),但高于注射用PDE;其余9种元素杂质含量均低于该指导原则中1类、2A、3类元素杂质的口服及注射用PDE。结论:该方法灵敏度高,精密度良好,能够准确地测定葡甲胺中1类、2A、3类元素杂质的含量;9批葡甲胺存在镍元素残留较高的风险。

高纯金中金含量的测定—差减法

高纯金饰品当前是珠宝市场的消费热点之一。为了准确测定高纯金中的金含量,本文应用电感耦合等离子体质谱仪(ICP-MS)测定高纯金中银(Ag)、镉(Cd)、硒(Se)、砷(As)、锑(Sb)、碲(Te)、铋(Bi)、铜(Cu)、铱(Ir)、锰(Mn)、镍(Ni)、铅(Pb)、钯(Pd)、铂(Pt)、锡(Sn)、钛(Ti)、锌(Zn)、铬(Cr)、铑(Rh)19种杂质元素的含量,联合电感耦合等离子发射光谱仪(ICP-AES)测定高纯金中铁(Fe)、铝(Al)、钠(Na)、镁(Mg)4种杂质元素的含量,最后用差减法得到其中金含量。结果表明,实验精密度(RSD,n=11)为1.05%~3.78%,加标回收率为93.0%~109.0%。本方法能够满足高纯金中杂质元素的测试要求,为其中金含量的测定提供了更精准、更环保的检测方法。

直流电压下油纸绝缘纤维杂质迁移运动特性及动力分析模型

换流变压器阀侧绕组运行过程中长期承受直流电场分量,其内部纤维杂质易积聚成桥,严重影响复合绝缘性能。为此,探究了直流电压下油纸绝缘纤维杂质迁移运动特性,对其轨迹、速度、偏移距离等特征参数进行了定量分析。在此基础上,建立了直流电压下纤维杂质动力分析模型,还原了纤维杂质的整个运动轨迹,并定量解释了其运动过程中速度及偏移距离变化的动力学机制。结果表明:球板电极下,单个纤维杂质在电极间往复运动,同时向强场区域水平迁移。其单次运动周期分为“抬升”、“上升”、“下降”3个阶段,最大运动速度可达10^(2)mm/s量级。随加压时间增加,油中纤维杂质在强场区域积聚为杂质小桥,小桥间因同号电荷相斥最终呈现中间密集而边缘稀疏的形态特征。仿真研究纤维杂质迁移运动特性,发现其“上升”阶段运动速度先急速增大再缓慢增加,“下降”阶段速度则先急剧增大至极大值而后逐渐减小,最大加速度可达10^(2)m/s^(2)量级。进一步地,纤维杂质运动过程中水平方向偏移距离随碰撞次数增加逐渐减小,其关系服从指数函数。以上研究可明确直流电压下纤维杂质全运动过程,实现杂质动力学特征定量计算,为后续纤维杂质绝缘危害性评估工作提供理论依据。

ICP-MS 法测定药用辅料蔗糖中元素杂质的含量

目的:建立ICP-MS法测定药用辅料蔗糖中砷(As)、镉(Cd)、汞(Hg)、铅(Pb)、钴(Co)、镍(Ni)、钒(V)、锂(Li)、锑(Sb)、铜(Cu)等10种元素的含量,评估其风险。方法:将药用辅料蔗糖溶解在0.1%HNO_(3)溶液中,采用ICP-MS法,设定测定模式为STD模式,通过优化仪器参数,测定蔗糖中^(75)As、^(111)Cd、^(202)Hg、^(208)Pb、^(59)Co、^(60)Ni、^(51)V、~7Li、^(121)Sb、^(63)Cu等10种元素的含量。结果:As、Cd、Pd、Co、Ni、V、Li、Sb、Cu等10种元素在0~100 ng·mL^(-1)范围内线性良好(r不低于0.99);Hg在0~2 ng·mL^(-1)范围内线性良好(r=0.999 1)。10种元素的平均回收率在99.8%~100.0%,RSD小于5%(n=6)。结论:方法易操作、准确度高,可用于药用辅料蔗糖中10种元素杂质的含量测定。通过结果可见,药用辅料蔗糖中含上述十种元素量远低于ICH Q3D中规定值,风险较小,修订标准时可不再单独考虑重金属项。

电感耦合等离子体质谱法测定明胶空心胶囊中元素杂质残留量

目的建立测定明胶空心胶囊中镉、铅、砷、汞、钴、钒、镍、铬、铁、锌10种元素杂质残留量的电感耦合等离子体质谱(ICP-MS)法。方法以钪、铟、锗、铋元素为内标,载气为氦气,等离子体模式为HMI-8,载气流量为0.8 L/min,雾化气流量为0.8 L/min,辅助气流量为0.8 L/min,等离子气流量为15.0 L/min,蠕动泵转速为0.10 r/min,雾化室温度为2.0℃。结果10种元素杂质在各自质量浓度范围内与其响应值线性关系良好(r≥0.9986,n=7);加样回收率为93.26%~104.84%,RSD为0.62%~3.66%(n=6);精密度试验结果的RSD为1.23%~3.20%(n=6)。测定的36批样品中,4批样品中铅元素含量超过ICH Q3D口服限度,4批样品中铬元素含量超过控制阈值,3批样品中铁元素含量超过30μg/g。结论该方法灵敏度高,精密度和准确度均良好,能很好地控制明胶空心胶囊中的痕量元素杂质。所测36批样品有7种元素杂质的风险系数较低,铅、铬、铁3种元素杂质的风险系数较高。