熔片X射线荧光光谱法测定锡矿石中八种重金属元素

建立了X射线荧光光谱法测定锡矿石中8种重金属元素Fe,Cu,Zn,As,Sn,Sb,Pb,Bi的分析方法。通过固体纯物质机械混合研磨配制了校准曲线所用的标准样品。采用混合熔剂(Li2B4O7:Li BO2:Li F=10:2.5:1,质量比)加氧化剂Li NO3熔融制备了X射线荧光法所用玻璃片样品(混合熔剂:Li NO3:试样=20:3:1质量比)。在高温熔融过程中,易挥发元素As,Pb一直存在于熔体中,未随熔融时间的增加而出现挥发损失。使用外加内标元素法(In和Co)对元素Sn,Sb,Fe的吸收增强效应进行校正,其它元素使用Compton散射线内标法进行校正。采用干扰曲线法校正Pb Lα对As Kα以及Sn Lβ1背景峰对Sb Lα的谱线重叠干扰。各元素检出限分别为Fe 0.0074%,Cu 0.0043%,Zn 0.0025%,As 0.0036%,Sn 0.019%,Sb 0.010%,Pb 0.0039%,Bi 0.0026%。对国家一级标准物质锡精矿GBW07232和锡矿石GBW07281分别进行10次制样测量,各元素精密度(RSD)在0.11%~18%之间。     

微波消解-电感耦合等离子体质谱(ICP-MS)法同时测定畜禽粪便中7种重金属元素

粪便样品干燥、研磨后,称取0.25 g样品,加入8 mL硝酸,采用微波消解方法进行前处理.采用KED模式消除质谱干扰,采用内标校正消除非质谱干扰(Ge作为Cu、Zn、Cr的内标,Bi作为Hg和Pb的内标,Rh作为As和Cd的内标),建立了可同时测定畜禽粪便中Cu、Zn、Cr、As、Cd、Pb、Hg 7种重金属元素的微波...     

激光剥蚀-电感耦合等离子体质谱对高温合金中17种痕量元素的测定

建立了镍基高温合金中Sc、Cu、Zn、Ga、Ge、As、Ag、Cd、In、Sn、Sb、Te、Ce、Hf、Tl、Pb、Bi17种痕量元素的激光剥蚀-电感耦合等离子体质谱测定方法。对激光剥蚀进样及质谱分析条件进行了优化,通过激光对样品表面的层层剥蚀顺利完成了对低沸点杂质元素的测定。采用格栅扫描采样,严格控制样品的聚焦位置和散焦距离以保证采样的准确性,由高温合金系列标准物质建立了18种痕量元素的校正曲线,其中14种痕量元素的线性相关性较好(r2≥0.99),In、Sn、Sb、Ce、Tl、Pb、Bi等超痕量元素的检出限和气体空白分别低于或接近0.000 005%和0.000 001%。方法对镍基高温合金样品中Cu、Ga、Ag、Cd、In、Sn、Sb、Te、Hf、Tl、Pb和Bi等痕量元素的测定结果与参考值吻合较好,且大部分元素的RSD(n=4)小于或接近30%。     

高纯钛的辉光放电质谱法多元素分析

采用辉光放电质谱法(GD-MS)测定高纯钛中Mg、Al、Cr、Fe、V、Mn、Co、Ni、Cu、Zn、As、Sn、Sb、Ta、W、Pb、Bi等痕量杂质元素,并对GD-MS工作参数及条件进行了优化。主要元素与内标校正ICP-MS法定量分析的结果一致,对结果差异的原因进行分析,论述了Element GD辉光放电质谱仪在痕量杂质元素分析方面的优势。     

LA-ICP-MS法测定纯铜及铜丝中的各元素

采用冷等离子体模式,以63Cu为内标,研究了单点激光剥蚀电感耦合等离子体质谱法(LA-ICP-MS)测定纯铜及铜丝中各元素的方法。优化了仪器参数;给出了样品直径对结果的影响,锌的信号随着直径的减小而减弱,硒的信号随着直径的减小而增强;研究了分馏效应,Cd,Sb,Pb,Bi分馏因子(FI)在0.80左右有分馏效应;采用不同系列铜标准物质制作了校准曲线以考察基体效应,Mn,Ni,Zn,Pb,Bi的线性相关系数大于0.99,基体效应不明显,其它元素有基体效应。建立了测定纯铜及铜丝中P,Mn,Fe,Ni,Zn,As,Se,Ag,Cd,Sn,Sb,Pb,Bi等元素的直接测定方法,但硫不能测定,也不能用56Fe作为铁的检测同位素,标准物质的测定值与认定值基本吻合,除Mn含量低外,其它元素的RSD(n=5)在2.1%~16%之间。     

微波消解-电感耦合等离子体质谱(ICP-MS)法同时测定土壤中11种金属元素

称取0.25g样品加入5mL硝酸和2mL氢氟酸,用微波消解技术对样品进行前处理。以Re作为As、Pb、Tl的内标,Rh作为Cd、Co、Cr、Ni的内标,Bi作为Be、Cu、Zn的内标,Tb作为V的内标,建立了KED模式下微波消解电感耦合等离子体质谱(ICP-MS)法同时测定土壤中Be、As、Cd、Co、Cr、Cu、Ni、Pb、Tl、V、Zn等11种金属元素的方法。方法线性关系良好,线性相关系数均在0.999以上,检出限为0.002～0.054mg/kg。检测土壤标准物质GSS-17、GSS-18验证方法准确性,结果显示测定值均在标准差允许范围内,相对标准偏差在0.29%～5.3%,是一种快速、可靠的土壤中多种金属元素同时检测方法。     

微波消解-电感耦合等离子体质谱法(ICP-MS)同时测定土壤中11种金属元素

称取0.25 g样品加入5ml硝酸和2ml氢氟酸,用微波消解技术对样品进行前处理。以Re作为As、Pb、Tl的内标,Rh作为Cd、Co、Cr、Ni的内标,Bi作为Be、Cu、Zn的内标,Tb作为V的内标,建立了KED模式下可同时测定土壤中Be、As、Cd、Co、Cr、Cu、Ni、Pb、Tl、V、Zn 11种金属元素的微波消解ICP-MS方法。该方法线性关系良好,线性相关系数均在0.9990以上,检出限为0.002mg/kg-0.054 mg/kg。检测土壤标准物质GSS-17、GSS-18验证方法准确性,结果显示测定值均在标准差允许范围内,相对标准偏差在0.29%-5.33%,是一种快速、可靠的土壤多种金属元素检测方法。     

微波消解-电感耦合等离子体质谱(ICP-MS)法同时测定土壤中11种金属元素

称取0.25 g样品加入5 mL硝酸和2 mL氢氟酸,用微波消解技术对样品进行前处理。以Re作为As、Pb、Tl的内标,Rh作为Cd、Co、Cr、Ni的内标,Bi作为Be、Cu、Zn的内标,Tb作为V的内标,建立了KED模式下微波消解电感耦合等离子体质谱(ICP-MS)法同时测定土壤中Be、As、Cd、Co、Cr、Cu、Ni、Pb、Tl、V、Zn等11种金属元素的方法。方法线性关系良好,线性相关系数均在0.999以上,检出限为0.002~0.054 mg/kg。检测土壤标准物质GSS-17、GSS-18验证方法准确性,结果显示测定值均在标准差允许范围内,相对标准偏差在0.29%~5.3%,是一种快速、可靠的土壤中多种金属元素同时检测方法。     

大洋多金属结核中27个元素的快速分析

利用飞利浦PW2400X射线荧光光谱仪测定了多金属结核中的Na2O、MgO、Al2O3、SiO2、P2O5、SO3、Cl、K2O、CaO、TiO2、V、Mn、Fe、Co、Ni、Cu、Zn、As、Rb、Sb、Y、Zr、Mo、Ba、La、Ce和Pb27种组分。采用粉末直接压片法制样,理论α系数（对分析线波长大于铁吸收限的元素）和以RhKβ１康普顿峰为背景的峰／背比法９对于其分析线波长小于铁吸收限的元素）校正元素间的吸收－增强效应,用国际锰结核标准样品建立校准方程（同时包括谱线重叠校正项）,方法经标准物质检验,具有较好准确度,能满足大洋多金属结构资源调查、评价要求。对主、次和绝大多数痕量组分,方法的相对标准偏差（ＲＳＤ,n=10）小于５％。与其他多元素分析方法相比,制样简单快速,而且是一种“环境友好”的“绿色”分析方法。     

微波消解-电感耦合等离体子质谱法(ICP-MS)同时测定畜禽粪便中7种重金属元素

粪便样品干燥、研磨后,称取0.25 g样品,加入8 mL硝酸,采用微波消解方法进行前处理。采用KED模式消除质谱干扰,采用内标校正消除非质谱干扰(Ge作为Cu、Zn、Cr的内标,Bi作为Hg和Pb的内标,Rh作为As和Cd的内标),建立了可同时测定畜禽粪便中Cu、Zn、Cr、As、Cd、Pb、Hg 7种重金属元素的微波消解-电感耦合等离子体质谱法。方法线性相关系数均在0.9995以上,检出限为0.005~0.305μg/L,加标回收率为83.6%~112%,相对标准偏差为0.70%~5.6%。方法灵敏度、准确度和精密度高,实用性强,适用于同时检测畜禽粪便中多种重金属元素,对畜禽粪便的科学还田具有指导意义。     

高能偏振能量色散X射线荧光光谱法分析古陶瓷

以国家地质标准样品制作工作曲线,用粉末压片法制样,高能偏振能量色散X射线荧光光谱法测定古陶瓷中包括15种稀土元素在内的56种元素,通过对6个陶瓷胎标准样品分析,结果表明:钪、钒、锰、铬、锌、镓、锗、铷、锶、钇、锆、铌、镉、锡、铯、钡、镧、铈、镨、钕、钆、钬、铒、铥、镱、镥、钍、铀等28种痕量元素测定值均在参考值的不确定度3～4倍范围,其他痕量元素如镍、铜、钼、锑、钐、铕、铽、铪、铅、铋等10种元素合格率为50%～83%。钠、镁、钾、钙、铁的氧化物和钛等6个项目均在允许误差范围内。氯、硫、磷的合格率均为66.6%。二氧化硅和三氧化二铝测定值和波长色散X射线荧光光谱熔融法测定结果相比,绝对误差分别在0.95%～4.46%和0.60%～1.66%之间。     

X射线荧光光谱法测定黏土中的主次组分

采用熔融玻璃片制样,选用标准样品,以经验α系数和散射线内标法校正元素谱线重叠干扰和基体效应,使用ZSX Primus Ⅱ X射线荧光光谱仪对黏土样品中的Al₂O₃、SiO₂、Fe₂O₃、CaO、MgO、K₂O、Na₂O、MnO、P₂O₅、TiO₂、Cu、Cr等组分进行测定,分析结果与标准值和化学值相吻合,12次测定的相对标准偏差小于10%.     

The application of discontinuous,countercurrent, liquid-liquid extraction to the study of the distribution of metal ions between hydrochloric acid and methyl isobutyl ketone

Summary The extraction of the elements Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb and Bi from hydrochloric acid into methyl isobutyl ketone has been studied as a function of hydrochloric acid concentration. The results are presented in graphical form. The data were obtained by studying the distribution patterns of the elements after equilibration on a Craig countercurrent liquid-liquid extraction apparatus.

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Zusammenfassung Die Extraktion der Elemente Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb und Bi mit Methylisobutylketon aus salzsaurer Lösung als Funktion der Säurekonzentration wurde studiert. Die Ergebnisse wurden aus den Spitzen der Verteilungskurven nach Einstellung des Gleichgewichts in einem diskontinuierlichen Gegenstrom-flüssig-flüssig-Extraktionsapparat berechnet.

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Résumé On a étudié l'extraction des éléments Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb et Bi en solution chlorhydrique par la méthylisobutylcétone. On présente les résultats sous forme graphique. Les données ont été obtenues en étudiant les diagrammes de distribution des éléments après équilibrage sur un appareil Craig à extraction à contre-courant liquide-liquide.

     

X射线荧光光谱法测定红土镍矿中多种元素

分别研究了采用压片、熔片两种制样方法,用X射线荧光光谱法(XRF)测定了红土镍矿中的9种元素。压片法重点研究了基体效应校正,经散射线作内标和经验系数法校正后,可准确测定除二氧化硅、氧化镁外的7种元素,方法简便、快速;而熔片法着重研究了熔剂和熔样温度的选择,经基体效应校正,各分析元素的结果准确度完全可与化学法相媲美,其相对标准偏差(RSD)在0.50%～3.00%间。     

Rapid qualitative determination of main components in archeological samples by radioisotope-excited X-ray fluorescence analysis

Archeological specimen were examined by the radioisotope-excited X-ray method to determine their chemical composition. Individual K and L X-rays of Fe, Ni, Cu, Zn, Pb, Mo, Ag, In, Sn, Sb, and Ba were induced by using²⁴¹Am−I and²⁴¹Am−Tm source—target assemblies. A lithium drifted silicone diode coupled to a 400-channel analyzer was used for detection. No sample preparation was required and all the elements were measured simultaneously in 40 min counting time.     

熔融制样–X射线荧光光谱法同时测定铀钼矿中主次成分

采用混合熔剂熔融制样,建立了同时测定铀钼矿中U,Mo,SiO_2,Fe_2O_3,Al_2O_3等的X射线荧光光谱法。以Li_2B_4O_7–LiBO_2作为熔融试剂,NH_4NO_3作为样品的氧化剂,样品与熔剂的质量比为1∶10。除使用铀矿石国家标准物质外,主要选取人工混合校准样品及历年实验室比对的铀钼矿校准样品绘制成工作曲线。采用理论系数法校正样品的基体效应,用Br Kα,Zr Kα,U Lα,Ba Lα,Zn Kα谱线扣除相应元素的谱线重叠干扰。该方法各组分测定结果的相对标准偏差均小于2.0%(n=10);用标准物质验证方法的准确度,测定值相对误差在0.00~8.00%之间,与标准值基本吻合。该法应用于生产实验中,可以满足对铀钼矿准确、快速的测量要求。     

Direct determination of trace elements in tungsten products using an inductively coupled plasma optical emission charge coupled device detector spectrometer

An echelle inductively coupled plasma optical emission spectrometer equipped with a segmented array of charge coupled device detectors was used for the direct determination of trace impurities in tungsten products. No sample preparation was necessary. The multicomponent spectral fitting software provided by the instrument was used for the correction of spectral interference and background. The detection limits of the trace elements Al, As, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Ni, P, Pb, Sb, Sn, Ti and V in tungsten matrix were obtained under optimized operating conditions. The accuracy of the proposed method was assessed using three National Reference Materials. As a result of their ultra-trace concentrations in the reference materials, As, Pb and Sn could not be determined satisfactorily. The concentrations found for the other elements agreed quite well with those of the certified values of the reference materials.     

Application of the mnf controlled dc generator to the spectral analysis of impurities in lead

A method for the determination of impurities in lead is described. The sample is excited by the new MNF controlled arc generator. The method is suitable for determination of the following seven impurities into the ranges of concentration shown: Sb (50–5400 p.p.m.),As (20–1000 p.p.m.), Bi (10–940p.p.m.),Cu (1–760 p.p.m.), Zn (8–280p.p.m.), Ag (5–160p.p.m.) and Sn (5–1800 p.p.m.). The average square error is 3.0%.     

Determination of Te,Bi, Ni,Sb and Au by X-ray fluorescence spectrometry following electroenrichment on a copper cathode

The electrodepositons of Te, Bi, Ni, Sb and Au from aqueous solution of pH = 1 on the cathode surface have been studied for X-ray fluorescence analysis (XRF). A special holder for a copper electrode has been constructed to perform the electrodeposition process on only one side of the electrode. After electrolysis, the copper electrode can be easily removed from the holder; after rinsing it with water and drying it can be analyzed by XRF. The proposed method of sample preparation and preconcentration of Te, Bi, Ni, Sb, Au provides suitable samples which are devoid of the negative and undesirable effects of XRF analysis, such as particle size and matrix effects. The influence of time on the deposition yield has been examined. The method of preconcentration is efficient. The inhomogeneity of the prepared specimens has been studied using internal standard method. The calibration is based on using synthetic standards, certified reference materials and standard addition method. The best results are achieved by the standard addition method. The agreement between results obtained with XRF analysis and certified values is satisfactory and indicates the usefulness of the proposed method for determination of Te, Bi, Ni, Sb and Au in anode slime.     

Chloroform extraction of ethyl xanthate complexes from sulphuric acid media

The chloroform extraction of 30 elements (Fe, Co, Ni, Zn, Cd, Ge, Sn, V, As, Sb, Bi, Cu, Ag, Au, Mn, Re, Ga, In, Tl, Se, Te, Cr, Mo, U, Pt, Pd, Rh, Ir, Ru and Ce) from 0.1-8M sulphuric acid in the presence of potassium ethyl xanthate has been studied. Pd(II), Bi, As(III), Sb(III), Se(IV) and Te(IV) are completely extracted and Au(III) is largely extracted over the range of acid concentration investigated. Fe(II), Tl(I), Rh(III) and Cr(VI) are only slightly extracted and Se(VI), Te(VI), Ru(III), Cr(III), Mn(II), Zn, Ce(IV), Ir(IV) and Ge(IV) are not extracted at all. Depending on the acid concentration, the remaining elements are all partly extracted. Results are compared with those obtained in an earlier study of the extraction of xanthate complexes from hydrochloric acid media. The processes involved in the formation of some xanthate complexes and potential analytical separations are discussed.