以PMBP为化学改进剂的电热蒸发/ICP-AES测定痕量钪的研究

报道了以１－苯基－３－甲基－４－苯甲酰基－吡唑酮［５］（ＰＭＢＰ）为化学改进剂的ＥＴＶ－ＩＣＰ－ＡＥＳ测定痕量钪的新方法．详细研究了金属螯合物在石墨炉内的形成、挥发及其影响因素；发现过量ＰＭＢＰ的存在有利于该螯合物的形成，并定量蒸发／传输至等离子体中．在优化的实验条件下，钪的检出限为０．３ｎｇ／ｍＬ，相对标准偏差为２．４％（ｃ＝０．１μｇ／ｍＬ，ｎ＝７）．本法已用于标准参考物机动车尾气尘粒中钪的测定，获得了满意的结果．     

电热蒸发进样/电感耦合等离子体原子发射光谱的蒸发过程研究

本文考察了电热蒸发进样 ETV/ICP-AES 技术中蒸发电流对不同挥发性元素的信号强度及峰形的影响;探索了蒸发器体积及其结构对分析物蒸发行为和信号的影响;本文还探索了平台技术在 ETV-ICP-AES 中的应用。并相应得出了一些有益的结论。     

聚三氟氯乙烯化学改进剂在电热蒸发(ETV)-ICP-AES直接测定生物试样中微量钛的应用

本文首次提出以聚三氟氯乙烯（ＰＴＦＣＥ）为化学改进剂，应用于悬浮体制样ＥＴＶ－ＩＣＰ－ＡＥＳ直接测定固体生物试样中微量钛。实验采用５％ＰＴＦＣＥ，促进Ｔｉ的蒸发。方法的绝对检出限为２ｐｇ（按５σ计），ＲＳＤ为２．６％（ｎ＝５）。该法用于直接测定ＧＢＷ０８５０５茶叶粉末样品中的Ｔｉ，结果与参考值吻合，回收率为９７．３～１０５．４％。     

以PMBP为萃取剂和化学改进剂/电热蒸发电感耦合等离子体原子发射光谱测定二氧化锆中痕量铕

提出了用β－二酮类试剂１－苯基－３－甲基－４苯甲酰基－吡唑酮［５］（ＰＭＢＰ）为萃取剂和 化学改进剂的电热蒸发电感耦合等离子体原子发射光谱（ＥＴＶ—ＩＣＰ—ＡＥＳ）测定高纯ＺｒＯ２ 中痕量Ｅｕ的新方法。讨论了影响Ｅｕ－ＰＭＢＰ 螯合物蒸发的主要因素。在优化实验条件下，Ｅｕ 的检出限为０．９μｇ／Ｌ，相对标准偏差为３．４％，试样分析的回收率为９４．５％～１０５．２％．     

一种用于电热蒸发-原子光谱的微型化固相萃取技术

与传统的液 液萃取相比 ,固 液萃取技术具有省时、溶剂用量少、不易乳化和高富集因子等优点[1],它可与各种检测方法联用[2 ],已在痕量无机物或有机物的分离富集与测定中广泛应用 .但是常规的固相萃取中的洗脱过程存在洗脱体积大 ,时间长及要求二次处理等缺点 ,这与电热蒸发 (ＥＴＶ)进样 /电感耦合等离子体原子发射光谱 /质谱 (ＩＣＰ ＡＥＳ/ＭＳ)和电热原子吸收光谱 (ＥＴＡＡＳ)很不匹配 .基于此 ,本文设计了一种填充有Ｐ5 0 7萃淋树脂 ( 1 40目 )的超微柱 ( 0 6μｍ(ｉ.ｄ .)× 1 0ｍｍ) .它既可用作分离富集柱 ,又可作为ＥＴＶ ＩＣＰ…     

电感耦合等离子体发射光谱法(ICP-OES)测定钴白合金中的锗

建立了一种电感耦合等离子体原子发射光谱法(ICP-OES)测定钴白合金中锗含量的分析方法,确定了溶样方法和分析谱线,进行了基体元素的干扰等实验,对方法精密度和准确度进行了考察,结果表明,方法的检出限为0.043 μg/mL,对钴白合金中锗的测定结果与其它标准分析方法分析结果基本一致,方法的相对标准偏差RSD在1.1%~1.9%(n=7),样品的加标回收率在98.5 %~102.1 %。所建立的方法准确、快速,适用于钴白合金中锗的测定。     

电感耦合等离子体原子发射光谱法测定钨合金中镍、铁、钴和锰

采用电感耦合等离子体原子发射光谱法测定钨合金中镍、铁、钴和锰的含量。优化的试验条件如下:1柠檬酸溶液用量为2mL;2过氧化氢溶液用量为12mL;3称样量为0.100 0g;4氨水溶液用量为2mL。选择镍、铁、钴、锰的分析谱线分别为221.647,233.280,228.616,259.373nm。4种元素在一定的质量浓度范围内与其发射强度呈线性关系,方法的检出限(3s/k)在0.018~0.083mg·L-1之间。方法应用于标准物质(JBWY05901)的分析,测定值与认定值相符。方法用于生产样品和合成样品的分析,测定值的相对标准偏差(n=6)在0.72%~3.9%之间。     

小体积外循环进样ICP-AES直接测定薄膜样品成份

本文试用小体积外循环进样系统,不称样重、不计试液体积,用归一计算法(或摩尔比法)ICP-AES直接进行小试样样品的成份测定,方法简便、快速,分析结果满意。     

碱熔-ICP-AES测定电镀废弃物中的镍

采用过氧化钠分解试样,盐酸浸取,通过仪器参数的优化、共存元素干扰等实验,建立了电感耦合等离子体原子发射光谱法测定电镀废弃物中镍含量的方法。方法的测定范围ω(Ni)1.00%~10.00%。经加标回收实验,镍元素的加标回收率为99.0%~107%(n=3),方法准确可靠,完全能够满足此类物料中镍含量的检验工作。     

电感耦合等离子体原子发射光谱法(ICP-AES)测定铁镍软磁合金中的镍

研究了电感耦合等离子体原子发射光谱法(ICP-AES)快速测定铁镍软磁合金中的镍含量,确定了最佳测定条件,以波长221.647nm作为镍的分析线,对溶解酸和酸浓度的影响进行探讨,选择钇作为内标元素。分析试样得到结果的相对标准偏差RSD小于0.91%(n=6),方法回收率为99.8%~100.1%(n=6),分析结果与丁二酮肟分光光度法相一致。电感耦合等离子体原子发射光谱法比传统的化学法准确、快速,已成功用于生产中。     

Determination of platinum, palladium and rhodium in biological and environmental samples by low temperature electrothermal vaporization inductively coupled plasma atomic emission spectrometry with diethyldithiocarbamate as chemical modifier

A novel method for inductively coupled plasma atomic emission spectrometry (ICP-AES) determination of trace amounts of Pt(II), Pd(II) and Rh(III), based on gaseous compounds introduction into the plasma as their diethyldithiocarbamate complexes by electrothermal vaporization (ETV), was developed. At the temperature of 1100 °C, the trace amounts of Pt, Pd and Rh were vaporized into plasma. The factors affecting the formation of the chelates and their vaporization behaviors, such as ashing temperature and time, vaporization temperature and time, pH and the concentration of chelating reagents were studied in detail. Under the optimized conditions, the limits of detection (LODs) (3σ) of Pt, Pd and Rh for tested solutions were 5.4, 1.4 and 0.8 ng ml⁻¹, and for actual sample (auto-catalyst NIST SRM 2557) were 0.27, 0.07 and 0.04 μg g⁻¹, respectively. The relative standard deviations (RSDs) for Pt, Pd and Rh were 1.4, 2.6 and 2.4% (C_Pt=0.5 μg ml⁻¹, C_Pd,Rh=0.25 μg ml⁻¹, n=7), respectively. The linear ranges of calibration graphs for Pt, Pd and Rh cover three orders of magnitude. Compared with conventional electrothermal vaporization technique, using the reagent of diethyldithiocarbamate as chemical modifier could not only enhance the analytical sensitivities, but also reduce the vaporization temperature. By combination with a separation/preconcentration step, the proposed method had been successfully applied to the analysis of the artificial seawater, tap water and urine with recoveries ranging from 91 to 106%. The two certified reference material meager platinpalladium ore GBW 07293 and auto-catalyst NIST SRM 2557 was also analyzed for validation, and the determined values obtained were in good agreement with the certified values.     

Low-temperature electrothermal vaporization of thenoyltrifluoroacetone complex of Sc(III) and Y(III) for sample introduction in an inductively coupled plasma atomic emission spectrometry,and their determination in biological samples

A new method for inductively coupled plasma atomic emission spectrometry (ICP-AES) determination of trace Sc and Y, based on gaseous compound introduction into the plasma as their thenoyltrifluoroacetone (TTA) complexes by electrothermal vaporization was developed. Using the reagent TTA as chemical modifier can not only enhance the analytical signals, but also reduce the vaporization temperature. At a temperature of 1,000 °C the trace Sc and Y can be vaporized completely into ICP. The factors affecting the formation of the chelate and its vaporization behavior, such as drying time, vaporization temperature/time, reaction medium and the amount of TTA, were investigated in detail. Under the optimized conditions (drying temperature/time 100 °C/10 s, vaporization temperature/time 1,000 °C/4 s), the limits of detection for Sc and Y were 19 pg and 34 pg (3), respectively, and the relative standard deviations for Sc and Y were 4.2% (c _Sc=0.2 g mL^–1; n=7) and 2.6% (c _Y=0.5 g mL^–1; n=7). The linear ranges of the calibration graphs cover three orders of magnitude. The method was applied to the analysis of the biological reference materials (GBW 07602, bush branches and leaves; GBW 07604, poplar leaves), and the results obtained were in good agreement with the certified values.     

Determination of trace impurities in boron nitride by graphite furnace atomic absorption spectrometry and electrothermal vaporization inductively coupled plasma optical emission spectrometry using solid sampling

Two digestion-free methods for trace analysis of boron nitride based on graphite furnace atomic absorption spectrometry (GFAAS) and electrothermal vaporization inductively coupled plasma spectrometry optical emission (ETV-ICP-OES) using direct solid sampling have been developed and applied to the determination of Al, Ca, Cr, Cu, Fe, Mg, Mn, Si, Ti and Zr in four boron nitride materials in concentration intervals of 1–23, 54–735, 0.05–21, 0.005–1.3, 1.6–112, 4.5–20, 0.03–1.8, 6–46, 38–170 and 0.4–2.3 μg g^− 1, respectively. At optimized experimental conditions, with both methods, effective in-situ analyte/matrix separation was achieved and calibration could be performed using calibration curves measured with aqueous standard solutions. In solid sampling GFAAS, before sampling, the platform was covered with graphite powder and, for determination of Si, also the Pd/Mg(NO₃)₂ modifier was used. In the determination of all analyte elements by solid sampling ETV-ICP-OES, Freon R12 was added to argon carrier gas. For solid sampling GFAAS and ETV-ICP-OES, the achievable limits of detection were within 5 (Cu)–130 (Si) ng g^− 1 and 8 (Cu)–200 (Si) ng g^− 1, respectively. The results obtained by these two methods for four boron nitride materials of different purity grades are compared each with the other and with those obtained in analysis of digests by ICP-OES. The performance of the two solid sampling methods is compared and discussed.     

Direct solid sampling electrothermal vaporization of alumina for analysis by inductively coupled plasma optical emission spectrometry

A procedure based on electrothermal evaporation (ETV) and inductively coupled plasma atomic emission spectrometry (ICP-OES) for the determination of trace impurities in Al₂O₃ powders without any sample pretreatment is presented. With the aid of matrix modifier the transport and the evaporation efficiency for refractory compounds could be increased by forming halides with a lower boiling point. As calibration is still a problem in direct solid sample analysis, different calibration approaches including the use of certified reference materials from NIST and standard addition of aqueous solutions of analytes were discussed. The accuracy obtained with calibration and with the standard addition method was shown up for the elements Ca, Fe, Ga, Mg, Mn, Na, Ni and V for the case of Al₂O₃ NIST standard reference material (SRM 699). The ETV–ICP-OES method was used for the analysis of Al₂O₃ powders with impurities in the low μg/g range and the results for the elements Ca, Fe, Ga, Mg, Mn, Na, Ni and V obtained with evaporation of discrete powder amounts with ETV–ICP-OES and slurry evaporation under the use of ultrasonic homogenization during the sampling and ETV–ICP-MS were shown to be in a good agreement.     

电感耦合等离子体原子发射光谱法测定高温合金中低含量钇

建立电感耦合等离子体原子发射光谱法测定高温合金中低含量钇的方法。采用盐酸、硝酸、氢氟酸溶解样品,在优化的仪器条件下,采用基体匹配法配制系列标准工作溶液,选择分析线为360.073 nm。钇的含量在0.0005%~0.050%范围内与光谱强度具有良好的线性关系,相关系数为0.99999,检出限为0.000003%。该方法测定结果的相对标准偏差不大于6.0%(n=8),加标回收率为90.0%~104.0%。该方法简便、快速、准确,可用于高温合金中低含量钇的测定。     

Determination of arsenic, lead, selenium and tin in sediments by slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry using Ru as permanent modifier and NaCl as a carrier

A procedure for the determination of As, Pb, Se and Sn in sediment slurries by electrothermal vaporization inductively coupled plasma mass spectrometry is proposed. The slurry, 1 mg ml⁻¹, is prepared by mixing the sample ground to a particle size 50 μm with 5% v/v nitric and 1% v/v hydrofluoric acids in an ultrasonic bath. The slurry was homogenized with a constant flow of argon in the autosampler cup, just before transferring an aliquot to the graphite furnace. The tube was treated with Ru as a permanent modifier, and an optimized mass of 1 μg of NaCl was added as a physical carrier. The pyrolysis temperature was optimized through pyrolysis curves, and a compromised temperature of 800 °C was used; the vaporization temperature was 2300 °C. The effect of different acid concentrations in the slurry on the analyte signal intensities was also evaluated. The accuracy of the method was assured by the analysis of certified reference sediments MESS-2, PACS-2 and HISS-1 from the National Research Council Canada, SRM 2704 and SRM 1646a from the National Institute of Standards and Technology and RS-4 from a round robin test, using external calibration with aqueous standards prepared in the same medium as the slurries. The obtained concentrations were in agreement with the certified values according to the Student's t-test for a confidence level of 95%. The detection limits in the samples were: 0.17 μg g⁻¹ for As; 0.3 μg g⁻¹ for Pb; 0.05 μg g⁻¹ for Se and 0.28 μg g⁻¹ for Sn. The precision found for the different sediment samples, expressed as R.S.D. was 1–8% for As, 2–9% for Pb, 6–12% for Se and 3–8% for Sn (n=5).     

Electrothermal vaporization dynamic reaction cell inductively coupled plasma mass spectrometry for the determination of Fe,Co, Ni,Cu, and Zn in biological samples

Slurry sampling electrothermal vaporization dynamic reaction cell inductively coupled plasma mass spectrometry (ETV-DRC-ICP-MS) has been applied to determine Fe, Co, Ni, Cu, and Zn in biological samples. The influences of instrument operating conditions and slurry preparation on the ion signals were reported. Pd was used as the modifier. The effectiveness of the ETV sample introduction technique and dynamic reaction cell in alleviating various spectral interferences in ICP-MS analysis has been demonstrated. This method has been applied to determine Fe, Co, Ni, Cu, and Zn in NIST SRM 1573a tomato leaves reference material and NRCC DORM-2 dogfish muscle reference material and also real samples such as a tea and a swordfish sample purchased locally. Since the sensitivities of the elements studied in slurry and aqueous solution were different, an analyte addition technique was used for the determinations. The analytical results of the reference materials agreed with the certified values. The precision between sample replicates was better than 6% for all determinations. The method detection limit estimated from analyte addition curves was 0.01, 0.006, 0.007, 0.004, and 0.006 μg g⁻¹ for Fe, Co, Ni, Cu, and Zn, respectively, in the original biological samples.     

Application of low temperature electrothermal vaporization ICP-AES for determination of refractory yttrium with 1-(2-pyridylazo)-2-naphthol as chemical modifier

A low temperature electrothermal vaporization inductively coupled plasma atomic emission spectrometry (ETV-ICP-AES) method was developed for the determination of the refractory yttrium, using 1-(2-pyridylazo)-2-naphthol (PAN) as chemical modifier. The trace yttrium was vaporized as PAN complex into plasma from a graphite furnace at a comparatively low temperature of 1200 °C. The operation conditions were optimized, and the vaporization behavior of Y-PAN chelate and the main factors affecting the determination were investigated in detail. Under the optimized conditions, the detection limit of Y was 0.7 ng ml⁻¹, and the relative standard deviation (R.S.D.) for 0.1 μg ml⁻¹ Y was 4.5% (n=9, v=10 μl). The linear range of calibration curve covered three orders of magnitude. The recommended approach has been applied for analysis of three biological samples with satisfactory results. The accuracy of the method was demonstrated by analyzing two standard reference materials.     

微波消解-电感耦合等离子体发射光谱法测定植物样品中的磷、硫

本方法采用微波消解处理样品,电感耦合等离子体发射光谱法测定植物样品中的磷、硫的含量,选用优化微波消解条件进行消解,磷和硫方法最低检出限分别为0.925mg/kg、1.82 mg/kg。精密度RSD和相对误差RE均小于3%,对新鲜植物样品进行加标回收试验,加标回收率为90.5%~107%,证明本方法既可用于检测干植物样品,又可检测新鲜植物样品。     

电感耦合等离子体原子发射光谱法测定稀土钢中微量镧、铈

采用稀王水溶解样品,选择La408.672 nm、Ce456.236nm为分析线,建立了电感耦合等离子体原子发射光谱法(ICP-OES)测定稀土钢中微量镧、铈的方法。结果表明,各元素校准曲线线性良好,相关系数可达0.99999;方法测定范围为：0.0001%～0.10%。检出限为：镧0.00002%,铈0.00006%。按照实验方法测定标样中镧、铈,结果的相对标准偏差RSD(n=8)为2.18%、1.68%。