冷焰ICP—MS法测定高纯稀土氧化物中铁和钙的研究

用冷焰技术对高纯稀土氧化物中Ｆｅ和Ｃａ的分析方法进行了研究。估算了测定范围和检出限，探讨了内标元素对基体影响的校正作用，测定了加标回波度，对半定量法和定量法的结果作了比较。表明次序焰条件下，痕量Ｆｅ的测定是可行的，但Ｃａ的测定结果仍不理想；ＱＡ法明显优于ＴＱ法。     

单柱离子色谱法测定过热器管垢和锅炉垢中铁、镁和钙的含量

首先用碱熔融法分解试样,然后加抗坏血酸将试液中的Ｆｅ３＋还原为Ｆｅ２＋,再用离子色谱法测定试液中的Ｆｅ２＋,Ｍｇ２＋和Ｃａ２＋。采用Ｓｈｉｍ－ｐａｃｋＩＣ－Ｃｌ阳离子交换柱分离样品离子,以０．２５ｍｍｏｌ／Ｌ乙二胺－０．５０ｍｍｏｌ／Ｌ柠檬酸（ｐＨ４．５０）为流动相,以ＣＤＤ－６Ａ电导检测器检测,使被测组分得到满意的分离和检测。Ｆｅ,Ｍｇ和Ｃａ的加标回收率均在９０％以上。测定结果与原子吸收光谱法测定结果相近。     

活动性肺结核患者头发微量元素分析

通过ＥＰＭ－８１０Ｑ电子探针扫描分析电镜，对在治疗中５３例结核患者头发Ｍｇ、Ａｌ、Ｃｄ、Ｃａ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ、Ｐｂ、Ｓｅ１１种元素含量进行分析，并与健康人头发比较。结果表明：结核组中Ｃａ、Ｚｎ元素含量低于健康组，Ｃｕ、Ｆｅ元素含量高于健康组（Ｐ〈０．０１）。     

乙肝患者头发微量元素分析

应用装有ＥＰＭ－８１０Ｑ电子探针扫描分析电镜，对５０例乙肝患者头发中Ｍｇ、Ａｌ、Ｃｄ、Ｃａ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ、Ｐｂ、Ｓｅ１１种元素含量进行分析，并与健康人头发进行比较。结果表明：乙肝组中Ｚｎ含量低于健康组，Ｃｕ、Ｃｄ、Ｆｅ含量高于健康组（Ｐ〈０．０１）。     

Ce~（3＋）在钙钛矿型KMF_3（M＝Mg、Ca、Sr、Ba）基质中的发光特性

采用高温固相反应法，在Ａｒ气氛中合成了ＫＭＦ３（Ｍ＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ）基质化合物和掺杂Ｃｅ３＋的磷光体。经Ｘ射线衍射分析确定，ＫＭｇＦ３和ＫＣａＦ３属于立方晶系、钙钛矿型结构，ＫＳｒＦ３和ＫＢａＦ３具有类似的结构。测定了ＫＭＦ３∶Ｃｅ３＋的发光光谱，观察到与其结构对应的分为二种不同的光谱结构，讨论了Ｃｅ３＋的取代格位     

Ce^3＋在钼钛矿型KMF3（M=Mg,Ca,Sr,Ba）基质中的发光特性

采用高温固相反应法，在Ａｒ气氛中合成了ＫＭＦ３（Ｍ＝Ｍｇ，Ｃａ，Ｓｒ，Ｂａ）基质化合物和掺杂Ｃｅ＾３＋的磷光体。经Ｘ射线衍射分析确定，ＫＭｇＦ３和ＫＣａＦ３属于立方晶系、钙钛矿型结构，ＫＳｒＦ３和ＫＢａＦ３具有类似的结构。测定了ＫＭＦ３：Ｃｅ＾３＋的发光光谱，观察到与其结构对应的分为二种不同的光谱结构，讨论了Ｃｅ＾３＋的取代格信。     

流动注射光度法测定铁的研究Ⅱ．Fe（Ⅲ）－CAS－SAS胶束体系

用自行组装的ＦＩＡ装置，对Ｆｅ（Ⅲ）－ＣＡＳ－表面活性剂体系进行了系统研究。着重考察了表面活性剂的影响。选择了Ｆｅ（Ⅲ）－ＣＡＳ－ＴｒｉｔｏｎＸ－１００－ＨＤＭＡＡ混合胶束体系，拟定了Ｆｅ（Ⅲ）的ＦＩＡ光度法，用于总铁量的测定。方法的线性范围、检测限及采样速度分别为０～０．６ｍｇ·Ｌ￣（－１）、０．００２ｍｇ·Ｌ￣（－１）和９０样次ｈ￣（－１）。该法用于天然水或某些工业用水中总铁量的测定，结果满意。     

几个分子和负离子的QCI势能曲线

用ＱＣＩＳＤ（Ｔ）／６３１１＋Ｇ（３ｄｆ，２ｐ）（简称ＱＣＩ）计算了ＢＨ－（２Π），ＢＦ－（２Π），ＢＨ（１∑），ＢｅＨ－（１∑），ＢｅＦ－（１∑）和ＢＦ（１∑）的较完整的势能曲线，探讨了这些体系的稳定性和解离过程．同时用Ｍｏｒｓｅ函数和ＥＲ函数拟合得到势能曲线，用拟合结果计算谐性频率和非谐性频率，并与已有的实验数据（ＢＨ和ＢＦ分子）进行比较，由此考察了ＱＣＩ理论方法在远离平衡构型时的可靠性．对于因单参考态近似导致的反常势能曲线进行了ＣＡＳＳＣＦ计算．还比较了ＱＣＩ和Ｇ２理论中标准的ＭＰ２（ｆｕｌ）／６３１平衡几何构型及其对ＱＣＩ总能量的影响．     

THE EXCITED STATES AND VIBRATIONAL FREQUENCIES OF Bli_2~e（e＝0，＋1，－1）CLUSTERS

ＴＨＥＥＸＣＩＴＥＤＳＴＡＴＥＳＡＮＤＶＩＢＲＡＴＩＯＮＡＬＦＲＥＱＵＥＮＣＩＥＳＯＦＢｌｉ：（ｅ＝０，＋１，－１）ＣＬＵＳＴＥＲＳＴＨＥＥＸＣＩＴＥＤＳＴＡＴＥＳＡＮＤＶＩＢＲＡＴＩＯＮＡＬＦＲＥＱＵＥＮＣＩＥＳＯＦＢｌｉ：（ｅ＝０，＋１，－１）Ｃ...     

流动注射光度法测定铁的研究：Ⅱ.Fe（Ⅲ）—CAS—SAS胶束体系

用自行组装的ＦＩＡ装置，对Ｆｅ（Ⅲ）－ＣＡＳ－表面活性剂体系进行了系统研究。着重考察了表面活性剂的影响，选择了Ｆｅ（Ⅲ）－ＣＡＳ－ＴｒｉｔｏｎＸ－１００－ＨＤＭＡＡ混合胶束体系，拟定了Ｆｅ（Ⅲ）的ＦＩＡ光度法，用于总铁量的测定，方法的线性范围，检测限及采样速度分别为０～０．６ｍｇ．Ｌ＾－１，０．００２ｍｇ．Ｌ＾－１和９０样次ｈ＾－１，该法用于天然水或某些工业用水总铁量的测定，结果满意。     

一体化碰撞反应 (iCRC)-电感耦合等离子体质谱法测定地质样品中痕量稀土元素

钡以及轻稀土元素氧化物对中、重稀土元素的干扰一直是质谱测试中存在的问题。建立了石墨粉垫底碳酸钠-硼酸混合熔剂熔融前处理样品,以_¹⁰³Rh为内标校正,一体化碰撞反应-电感耦合等离子体质谱仪法测定地质样品中稀土元素含量的方法。探讨了碳酸钠-硼酸混合熔剂熔融前处理样品注意事项、碰撞模式下碰撞气流量和离子透镜的参数的优化、干扰校正试验等问题,采用国家标准物质GBW07403、GBW07405、GBW07427、GBW07429验证,实验结果表明,各元素线性关系良好,相关系数均大于0.999,方法检出限在0.01～0.03mg/kg之间,相对误差为0.13%～7.1%,相对标准偏差为0.79%～6.59%,测试结果与标准值相吻合。对实际样品分析,得到平滑的球粒陨石归一化的稀土元素配分曲线,证明测定结果是合理可信的。该方法熔剂用量少,过程空白低,对器皿的侵蚀小,直接加热浸取,简化了操作过程,适用于大批量地质样品中稀土元素的测定。     

电感耦合等离子体质谱法(ICP-MS)测定高纯氧化铒中稀土杂质

从同位素的选择、基体效应,内标元素的选择及仪器工作条件等方面对实验参数进行了优化,重点研究了等离子体功率及仪器分辨率的改变对铒基体所形成的氢化物多原子离子干扰的影响。通过提高等离子体功率、改变仪器分辨率及数学方程校正等方法,减少和剔除了ErH对Ho和Tm测定的干扰。实验中选取Cs为内标元素,测定了不同含量的高纯氧化铒样品。分析结果与标准加入法结果进行了比较,之间无显著性差异。     

Direct determination of trace rare earth elements in high purity Y2O3 using fluorination assisted electrothermal vaporization inductively coupled plasma atomic emission spectrometry with slurry sampling

A new method for the determination of trace amounts of 14 rare earth elements in high purity Y₂O₃ using fluorination assisted electrothermal vaporization inductively coupled plasma atomic emission spectrometry with slurry sampling was developed. A polytetrafluoroethylene (PTFE) emulsion was used as a fluorinating reagent to promote the vaporization of the analytes from graphite furnace. The main factors affecting analytical signals were investigated systematically. The interference of matrix could be minimized in the presence of PTFE. Under optimum conditions, the detection limits for rare earth elements were 0.032 ng～2.52 ng and the relative standard deviations were in the range of 1.4% to 4.3%. The proposed method was applied to the direct analysis of high purity Y₂O₃ powder with satisfactory results.     

Direct determination of rare earth impurities in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry

A novel method was developed for the direct determination of trace quantities of rare earth elements (REEs) in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry (ICP-MS) in this work. The mass spectra overlap interferences arose from Er matrix on the neighbouring and monoisotopic analytes of ¹⁶⁵Ho(100) and ¹⁶⁹Tm(100) were eliminated by adjusting instrumental peak resolution value from 0.7 to 0.3 amu. The matrix suppression effect of Er on the ion peak signals of REEs impurities was effectively compensated with spiking In as internal standard element. The limit of quantitation (LOQ) of REEs impurities was from 0.0090 to 0.025 μg g⁻¹, the recoveries of spiked sample for REEs were found to be in the range of 90.3-107% through using the proposed method and relative standard deviation (R.S.D.) varied between 2.5% and 6.7%. The novel methodology had been found to be suitable for the direct determination of trace REEs impurities in 99.999-99.9999% high purity Er₂O₃ and the results obtained from this method keep in good agreement with that acquired from high resolution ICP-MS.     

电感耦合等离子体质谱法(ICP-MS)测定稀土矿中钇、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥和钪量

通过用四酸与微波消解法溶解样品对比,建立了用硝酸、盐酸、氢氟酸、高氯酸分解样品,采用电感耦合等离子体质谱法(ICP-MS)测定稀土矿中16种元素含量。方法采用_¹⁰³Rh作为内标消除干扰,确定了最优测定条件,16种稀土元素检出限为0.0029-0.0099ng/mL,测定范围为0.0005-0.020%。精密度试验、加标回收试验及标准物质检测,结果验证了方法的可行性及准确性。该方法简单易操作,结果可靠,能满足实验分析要求。     

用电感耦合等离子体质谱法测定高纯稀土中稀土杂质时的基体影响

考察了基体对待测稀土杂质元素信号的影响，研究了内标对基体效应的补偿作用。对于不同的基体元素最佳的内标元素是不一致的，Ｇａ、Ｉｎ、Ｉ、Ｃｓ和Ｔｌ是稀土纯度分析中合适的内标元素。内标法简便易行，效果好，其测定方法的精度和回收率令人满意。     

ICP-MS测定高纯氧化铒中稀土杂质的研究

从同位素的选择、基体效应,内标元素的选择及仪器工作等方面对实验参数进行了优化,重点研究了等离子体功率及仪器分辩率的改变对铒基体所形成的氢化物多原子离子干扰的影响。通过提高等离子体功率、改变仪器分辨率及数学方程校正等方法,减小和剔除了ErH对Ho和Tm测定的干扰。实验中选取Cs为内标元素,测定了不同含量的高纯氧化铒样品。分析结果与标准加入法结果进行了比较,之间无显著性差异。     

感耦等离子体发射光谱法测定高纯氧化钇中的痕量稀土元素

本文采用国产WPG-100型一米光栅摄谱仪、GP3.5-D1型高频等离子体发生器、气动雾化器,以不去溶方式进样直接测定纯度为99.995%的氧化钇中十四个稀土杂质元素。其中除镨(17μg/g)和钸(7μg/g)外,测定下限均为0.3-3μg/g(以氧化物计)。当被测元素的含量为3-17μg/g时,相对标准偏差为2.3-7.3%(钸和镨除外)。样品用盐酸溶解,酸度和共存元素的影响很小,方法简便、快速。     

Determination of rare earth impurities in high purity europium oxide by inductively coupled plasma-mass spectrometry and evaluation of concentration values for europium oxide standard material

Direct determinations of 13 rare earth elements (La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Yb, Lu and Y) in high purity europium oxide by inductively coupled plasma mass spectrometry (ICP-MS) have been reported. The operating parameters of the instrument were optimized and the spectral interferences and the matrix effects were investigated. Using Ga or Rh as the internal standard can eliminate most of the matrix effects. The detection limits (3 sigma, n=10, integral time=1s) are 0.013-0.085 ng mL(-1) and the reproducibility (n=11) is 0.9-3%. The recoveries of spiking samples are 80-108%. Europium oxide standard material was made and its concentration values were evaluated by various techniques from 10 collaborating laboratories. By comparison of the results of ICP-MS with the results of other techniques, we have validated that ICP-MS is an accurate and reliable technique for analysis of ultratrace impurities in high purity rare earth matrix.     

Direct determination of trace rare earth elements in high purity Y2O3 using fluorination assisted electrothermal vaporization inductively coupled plasma atomic emission spectrometry with slurry sampling

A new method for the determination of trace amounts of 14 rare earth elements in high purity Y₂O₃ using fluorination assisted electrothermal vaporization inductively coupled plasma atomic emission spectrometry with slurry sampling was developed. A polytetrafluoroethylene (PTFE) emulsion was used as a fluorinating reagent to promote the vaporization of the analytes from graphite furnace. The main factors affecting analytical signals were investigated systematically. The interference of matrix could be minimized in the presence of PTFE. Under optimum conditions, the detection limits for rare earth elements were 0.032 ng∼2.52 ng and the relative standard deviations were in the range of 1.4% to 4.3%. The proposed method was applied to the direct analysis of high purity Y₂O₃ powder with satisfactory results. Received: 19 June 1999 / Revised: 10 December 1999 / Accepted: 16 December 1999