Classical analysis including trace-matrix separation versus solid state mass spectrometry: A comparative study for the analysis of high purity Mo,W and Cr

The applicability of GDMS, SIMS, SSMS, NAA and TMS with AAS, ICP-OES and ICP-MS end determination for routine bulk ultratrace analysis of high purity refractory metals was investigated. Due to the heterogeneous distribution of trace elements in the sub-ppm range, sample consumption and analysis time have a tremendous influence on quantification with procedures of low sample consumption. As an example, GDMS, which is commonly used for ultrapure material certification by most of the manufacturers in Europe and the USA, exhibits discrepancies by more than one order of magnitude for repetitive analyses of a series of trace components in the same sample. Furthermore, results of different laboratories using the same instrument are frequently not comparable. Due to easy standardization and large sample consumption TMS procedures combined with FAAS, GFAAS, ICP-AES and ICP-MS as methods of end determination exhibit better precision and accuracy than GDMS and SIMS. Detection limits are comparably low or even better in case of ICP-MS end determination. TMS procedures are less expensive and less time consuming than highly sophisticated analytical techniques like GDMS, SIMS or NAA. Additionally, they can be easily applied by experienced personnel in a well equipped industrial analytical laboratory.List of Acronyms Used AAS Atomic Absorption Spectrometry - FAAS Flame Atomic Absorption Spectrometry - GDMB Gesellschaft Deutscher Metallhütten- und Bergleute - GDMS Glow Discharge Mass Spectrometry - GFAAS Graphite Furnace Atomic Absorption Spectrometry - ICP-AES Inductively Coupled Plasma Atomic Emission Spectrometry - ICP-MS Inductively Coupled Plasma Mass Spectrometry - IDMS Isotope Dilution Mass Spectrometry - NAA Neutron Activation Analysis - SIMS Secondary Ion Mass Spectrometry - SSMS Spark Source Mass Spectrometry - TMS Trace-Matrix Separation - VLSI Very Large Scale Integration - XRFS X-Ray fluorescence Spectroscopy Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

Determination of trace level of selenium and mercury in photographic emulsions by atomic spectroscopy techniques

Trace level of selenium and mercury in photographic emulsion are used to improve photographic properties. The presence of silver halide in photographic emulsion does not allow the application of the most common analytical methods such as Hydride Generation Atomic Absorption Spectrometry (HG-AAS) and cold vapour Atomic Absorption Spectrometry (CV-AAS). Besides, silver removal was not quantitative, leading to a significant loss of the analytes and low reproducibility. The present work suggest the use of inductively coupled plasma Atomic Emission Spectrometry (ICP-AES) equipped with Ultrasonic Nebulizer (USN) for direct aqueous samples analysis at microgram l-1 level (d.l. 5.1 ppb for Hg and 6.1 ppb for Se).     

Simultaneous determination of elemental content in water samples by total reflection X-ray fluorescence and atomic absorption spectrometry

An analytical exercise between two laboratories was performed in order to compare the elemental composition of a water sample. The metal concentration of Cr, Cu, Fe, Mn, Ni, Pb, and Zn in the water sample was analyzed by Total Reflection X-Ray Fluorescence and Atomic Absorption Spectrometry. The analysis by Total Reflection X-Ray Spectrometry was realized by an Ital Structures TX-2000 and the analysis by Atomic Absorption Spectrometry was made by a Perkin Elmer Spectrophotometer Model 3110. Results show a good agreement in the metal concentrations obtained by both techniques. The variation coefficient between the results with both techniques was less than 14%. Therefore, it is possible to conclude that both techniques are reliable and adequate for the determination of these elements in environmental water samples.     

Trends in Preconcentration Procedures for Metal Determination Using Atomic Spectrometry Techniques

 Methods for metal preconcentration are often described in the literature. However, purposes are often different, depending on whether the methods are applied in environmental, clinical or technological fields. The respective method needs to be efficient, give high sensitivity, and ideally also is selective which is useful when used in combination with atomic spectroscopy. This review presents the actual tendencies in metal preconcentration using techniques such as Flame Atomic Absorption Spectrometry (FAAS), Electrothermal Atomic Absorption Spectrometry (ETAAS), Hydride Generation Atomic Absorption Spectrometry (HGAAS), Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Procedures based on related to electrochemical, coprecipitation/precipitation, liquid–liquid and solid–liquid extraction and atom trapping mechanisms are presented. Correspondence: Department of Analytical Chemistry, Universidade Estadual de Campinas – UNICAMP, P.O. Box 6154, 13083-970 Campinas, Brazil. e-mail: zezzi@iqm.unicamp.br Received December 20, 2001; accepted October 11, 2002     

Ultratrace and microdistribution analysis in material sciences

Summary All-rounders and experts are two basic types of scientists. A harmonic cooperation between these two groups is essential for today's large study groups engaged in materials development. Materials development programmes in many high-tech countries are major fields of research supported by special financial arrangements (e.g. COST, EURAM or BRITE-programmes in Europe). Modern materials development is not possible without analytical guidance. This is not always realized by all engaged partners and it is a main obligation of analytical chemists to make aware of the role of a potent materials characterization in relevant development programmes. This should be demonstrated in two essential relevant areas: a) Bulk trace and ultra trace analysis of metals. Many important metal properties are directly or indirectly influenced by trace elements. In complex systems like fusion reactors or microelectronic components, trace contents of even minor metal parts might decisively influence system properties. As refractory metals and their silicides gain rising importance in VLSI microelectronic applications, their ultratrace characterization becomes a major challenge. Essential progress was possible by the complementary application of mass-spectrometric methods. Latest results and a critical survey will be given, including GDMS, SIMS, SSMS, IDMS and ICP-MS.Surprisingly, however, highest sensitivities and best detection limits were recently achieved by a combination of trace-matrix separation procedures and final end determination with ICP-MS. This combination also proved to be the most economic and safest approach from the view point of accuracy and precision. b) The analytical characterization of discontinuities and heterogeneities in solid matter. Practical examples are again taken from the study of refractory and hard metals and ceramics. A survey is given as to the manifold effects, heterogeneities and discontinuities exert on modern high-tech materials: as a function of their average diameter, they can either strengthen the material (dispersion strengthening), or they can cause deterioration of material properties e.g. as points of crack initiation, by grain boundary embrittlement etc. Together with most important methods for detection and characterization of heterogeneities and discontinuities, their evaluation and possible prevention during materials fabrication are discussed and pertinent examples are given. The phenomena of heterogeneous particles and pores are elucidated in more detail.

Acronyms used

1 Abbreviations for European research programmes AGATA Advanced Gas Turbines for Automobiles - BRITE Basic Research for Industrial Technologies for Europe - COST Cooperation in Science and Technology - EURAM European Research Activities Programme on Materials 2 Abbreviations in the field of refractory metals technology ADM Ammonium-Di-Molybdate - APT Ammonium-Para-Tungstate - HP High Purity - MHC Molybdenum-based alloy containing 1.2% Hf and 0.1% C - NS Non-sag (tungsten, used for lamp filaments and evaporative metallization techniques) - ODS Oxide Dispersion Strengthened - RM Refractory Metal - TZM Molybdenum-base alloy containing 0.5% Ti, 0.08% Zr and 0.025% C - UHP Ultra High Purity - VLSI Very large scale integration - ZHM Molybdenum-base alloy containing 0.40% Zr, 1.2% Hf and 0.15% C 3 Analytical technique names AA Activation Analysis - AAS Atomic Absorption Spectrophotometry - AES Auger Electron Spectrometry or Atomic Emission Spectrometry (only used in this work where it is clear that Auger Electron Spectrometry is not meant) - EDX(RS) Energy Dispersive X-Ray Spectrometry - EELS Electron Energy Loss Spectrometry - EP(X)MA Electron Probe X-Ray Microanalysis - GDMS Glow Discharge Mass Spectrometry - GFAAS Graphite Furnace Atomic Absorption Spectrometry - ICP-OES, MS Inductively Coupled Plasma — Optical Emission Spectrometry, Mass Spectrometry - ID-MS Isotope Dilution — Mass Spectrometry - LAS Classical photometry (Liquid Absorption — Spectrophotometry) - LEED Low Energy Electron Diffraction - MS Mass Spectrometry - NAA Neutron Activation Analysis - OES Optical Emission Spectrometry - SEM Scanning Electron Microscopy - SIMS Secondary Ion Mass Spectrometry - SSMS Spark Source Mass Spectrometry - TEM Transmission Electron Microscopy - TMS Trace-Matrix Separation (procedure) - WLD(-XRS) Wave Length Dispersive — XRS - XR(F)S X-Ray (Fluorescence) Spectrometry     

间接原子吸收法测定苯并三氮唑

乙酸钠介质中 ,加入过量的铜 (Ⅱ )与苯并三氮唑生成沉淀 ,用火焰原子吸收法测定上清液中剩余的铜(Ⅱ ) ,工作曲线法测定了工业合成样品及内燃机冷却水中的苯并三氮唑。该方法测定苯并三氮唑线性范围为1 2mg/L～ 30mg/L ,回收率 (n =5)为 98.9～ 1 0 1 .0 %。文中还测定了难溶化合物的溶解度、溶度积和化合物的组成比。     

Differentiation of two main ammunition brands in Chile by Regularized Discriminant Analysis (RDA) of metals in gunshot residues

Conventionally, chemical patterns of gunshot residues (GSR) can be used for identification of a suspect involved in criminal fire arm incidents. Furthermore, metals composition in GSR is well related with the ammunition brand. In Chile the two main ammunition brands used are FAMAE and CBC. Metals, such as Pb, Ba, Sb, Cu, Zn and Ca are common elements detected in both brands. This work describes the application of both conventional and chemometric analysis of data (Regularized Discriminant Analysis, RDA) for differentiation of ammunition brands according to the metal patterns of GSR collected from shooter individuals. Real samples of GSR were collected from hands (dorsal region) of both shooters and non-shooters. Metals were analyzed using the techniques Atomic Absorption Spectrometry (AAS) and Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-OES). By means of conventional plotting techniques for differentiation, such as binary and ternary plots, differences between the two brands are observed although without quantitative certainty. For the first time, applying chemometric analysis, such as regularized discriminant analysis (RDA), the investigated ammunition brands can be classified and differentiated correctly with 100% certainty.     

Flow injection determination of Pb and Cd traces with graphite furnace atomic absorption spectrometry

The preconcentration and recovery of lead and cadmium traces at ng l(-1) level were evaluated in standard solutions and natural aqueous samples using a FIAS (Flow Injection Atomic Spectrometry) apparatus. The method is based on retention of the complex formed between Pb or Cd and 1,2-dihydroxy-3,5-benzendisulphonic acid (Tiron) on a macroporous anion-exchange resin. The recovery of the analytes was obtained by elution with 0.1 M HCl and their determination was performed by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). The detection limits were 9 and 7 ng l(-1) for Pb and Cd respectively. The effects of sample solution pH and composition and of interfering agents as well as reagent purity are discussed. The technique was applied to the analysis of natural waters.     

Determination of trace alkaline metals in quartz by flame atomic emission and atomic absorption spectrometry

Flame Atomic Emission Spectrometry (FAES) and Electrothermal Atomizer Atomic Absorption Spectrometry (ETA-AAS) were assessed for the determination of K and Na in quantities of less than 10 μg g⁻¹ in quartz. The advantages of the direct AAS technique (samples were atomized directly in solid form) are described as less time-consuming and do not require extensive sample preparation. The FAES technique was applied as the control method using water standard solutions for calibration. The results obtained by the two methods agree well in the concentration ranges from 0.5 to 20 μg ml⁻¹.     

Design considerations regarding an atomizer for multi-element electrothermal atomic absorption spectrometry

The methodology of simultaneous multi-element electrothermal atomic absorption spectrometry (ETAAS-Electrothermal Atomic Absorption Spectrometry) stipulates rigid requirements to the design and operation of the atomizer. It must provide high degree of atomization for the group of analytes, invariant respective to the vaporization kinetics and heating ramp residence time of atoms in the absorption volume and absence of memory effects from major sample components. For the low resolution spectrometer with a continuum radiation source the reduced compared to traditional ETAAS (Electrothermal Atomic Absorption Spectrometry) sensitivity should be, at least partially, compensated by creating high density of atomic vapor in the absorption pulse. The sought-for characteristics were obtained for the 18 mm in length and 2.5 mm in internal diameter longitudinally heated graphite tube atomizer furnished with 2-4.5 mg of ring shaped carbon fiber yarn collector. The collector located next to the sampling port provides large substrate area that helps to keep the sample and its residue in the central part of the tube after drying. The collector also provides a “platform” effect that delays the vaporization and stipulates vapor release into absorption volume having already stabilized gas temperature. Due to the shape of external surface of the tube, presence of collector and rapid (about 10 °C/ms) heating, an inverse temperature distribution along the tube is attained at the beginnings of the atomization and cleaning steps. The effect is employed for cleaning of the atomizer using the set of short maximum power heating pulses. Preparation, optimal maintenance of the atomizer and its compliance to the multi-element determination requirements are evaluated and discussed. The experimental setup provides direct simultaneous determination of large group of element within 3-4 order concentration range. Limits of detection are close to those for sequential single element determination in Flame AAS with primary line source that is 50-1000 times higher than the limits obtainable with common ETAAS (Electrothermal Atomic Absorption Spectrometry) instrumentation.     

Determination of trace and toxic elements in Korean rice CRM by INAA, ICP and AAS

Trace and toxic elements in Certified Reference Material (CRM) made of Korean rice at the Korea Research Institute of Standards and Science have been analyzed by Instrumental Neutron Activation Analysis (INAA). Data intercomparison from the measurement with those of Atomic Absorption Spectrometry (AAS) and Induced Coupled Plasma Spectrometry (ICPS) has been studied. The powdered samples were sterilized at 1.5·10⁶ rad in the bottles using a⁶⁰Co source after sieving and spiking to specific elements such as As, Cd, Cr, Cu and Hg and then the homogeneity of samples was assessed. Rice flour (SRM 1568a) and standard solutions made by the National Institute of Standards Technology (NIST) were used to construct the calibration curves for the INAA and the chemical methods, respectively. The uncertainties and concentration of constituent elements were determined and the possibility of their use for analytical quality control was considered.     

Different Lubricating Oil Treatments for the Determination of Cu,Cr, Fe,Ni, Sb,Pb, and Zn by HR-CS FAAS

Abstract

Microwave-assisted acid decomposition, direct dilution in kerosene, and oil-in-water emulsion were evaluated as lubricating oil pretreatment procedures for Cu, Cr, Fe, Ni, Pb, Sb, and Zn determination by High-Resolution Continuum Source Flame Atomic Absorption Spectrometry (HR-CS FAAS). For wet digestion, results were compared with those obtained by Flame Atomic Absorption Spectrometry (FAAS). The ultrasound probe used in emulsions sonication contaminated samples with Cr, although better results have been observed for the other six elements in this condition. In general, recovery percentages ranging from 81–106% (Cu), 80–107% (Cr), 85–114% (Fe), 82–116% (Ni), 86–117% (Pb), 85–115% (Sb), and 81–114% (Zn) were obtained. The HR-CS FAAS showed to be faster and more sensitive than FAAS.     

Investigations of ground-based clouds at the Mt. Brocken

Results of the 1996 field season (April-November) of the cloud chemistry program starting in 1992 at the Mt. Brocken are presented. The mountain site (1142 m a.s.l.) is located in the Harz Mountains/Germany. For a large part of the database (about 40%), both cloud water and drizzle and/or precipitation were present at the same time. A separation into two groups was done: non-precipitating clouds and mixed category of events. More than 2000 one hour samples were collected and analysed for major ions. The mean cloud water pH for the frostfree period in 1996 was 3.9. Histograms giving the distribution of pH values show that the pH values of samples from non-precipitating clouds ranges from 2.5 up to values > 8 and that the distribution is bimodale. For the 1996 field season period as a whole, pH values of cloud water were lower than those of mixed samples (cloud water, drizzle, precipitation) at the Brocken site. This was related to higher concentrations of all ions in cloud water. Cloud base measurements using a ceilometer confirmed the correlation between liquid water content and height above cloud base and consequently the influence of sampling height relative to the cloud base on the total ionic content of cloud water. Received: 17 November 1997 / Revised: 4 February 1998 / Accepted: 9 February 1998     

Investigations of ground-based clouds at the Mt. Brocken

Results of the 1996 field season (April-November) of the cloud chemistry program starting in 1992 at the Mt. Brocken are presented. The mountain site (1142 m a.s.l.) is located in the Harz Mountains/Germany. For a large part of the database (about 40%), both cloud water and drizzle and/or precipitation were present at the same time. A separation into two groups was done: non-precipitating clouds and mixed category of events. More than 2000 one hour samples were collected and analysed for major ions. The mean cloud water pH for the frostfree period in 1996 was 3.9. Histograms giving the distribution of pH values show that the pH values of samples from non-precipitating clouds ranges from 2.5 up to values > 8 and that the distribution is bimodale. For the 1996 field season period as a whole, pH values of cloud water were lower than those of mixed samples (cloud water, drizzle, precipitation) at the Brocken site. This was related to higher concentrations of all ions in cloud water. Cloud base measurements using a ceilometer confirmed the correlation between liquid water content and height above cloud base and consequently the influence of sampling height relative to the cloud base on the total ionic content of cloud water. Received: 17 November 1997 / Revised: 4 February 1998 / Accepted: 9 February 1998     

The Analysis of Cobalt in High Purity Nickel for Reactor Neutron Dosimetry by Means of Ion Exchange Combined with ICP-AES and Ion Exchange Combined with GF-AAS

Abstract

This paper describes the determination of Co in two samples of high purity Ni by means of ion-exchange in combination with Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) and by means of Graphite Furnace - Atomic Absorption Spectrometry (GF-AAS). These samples were both Nickel metal of 99.75%. nominal purity of which one was in the form of a 0.1 mm thick foil and the other a 0.5 mm diameter wire. The Co content in these; samples was determined in the process of a certification campaign and these samples are intended to serve as reference material for Reactor Neutron Dosimetry. The sample treatment and the detection of Co both via ICP-AES and GF-AAS are discussed. The values obtained for both Nickel samples are in accordance with the later certified value.     

Determination of Cd levels in smoke condensate of Brazilian and Paraguayan cigarettes by Thermospray Flame Furnace Atomic Absorption Spectrometry (TS-FF-AAS)

In this study, the concentrations of Cd in smoke condensate of Paraguayan and Brazilian full flavor normal size cigarettes were determined. A “fishtail” chimney was used to confine and direct cigarette smoke to an impaction trap followed by 3 MCE (mixed cellulose ester) filters for smoke collection. The smoke condensate collected at the first two collection stages (chimney and impactor) was prepared as Triton X-100 slurry samples and the 3 MCE filters (third collection stage) used to collect smoke were microwave digested. Samples were analyzed by Thermospray Flame Furnace Atomic Absorption Spectrometry (TS-FF-AAS) for Cd and the results obtained were compared with Graphite Furnace Atomic Absorption Spectrometry (GFAAS). No significant differences were found between the values obtained with TS-FF-AAS and GFAAS at a 95% confidence level. The total concentration of Cd in the smoke of Brazilian and Paraguayan cigarettes tested ranged from 187 to 281 ng/cigarette and from 176 to 271 ng/cigarette, respectively. The LODs for Cd using TS-FF-AAS and GFAAS, were 5.8 and 1.5 ng/cigarette, respectively, for the analysis of smoke condensate from 1 cigarette. The main advantages of using the simple TS-FF-AAS system are its low running costs and the analysis time when compared to GFAAS.     

金测定的方法验证及质量控制图的建立

对DZ/T 0279.19–2016 《区域地球化学样品分析方法第19部分:金量测定泡沫塑料富集–石墨炉原子吸收光谱法》进行了实验室方法验证,并建立了相应的质量控制图。结果表明,实验室具备采用泡沫塑料富集–石墨炉原子吸收光谱法测定金的资源和技术能力,建立的质量控制图能够对分析系统进行有效核查。     

Ultrasound-assisted emulsification of cosmetic samples prior to elemental analysis by different atomic spectrometric techniques

In this work, ultrasound-assisted emulsification with a probe system is proposed as a rapid and simple sample treatment for atomic spectrometric determinations (Electrothermal Atomic Absorption Spectrometry, Inductively Coupled Plasma Optical Emission Spectrometry, Flame Atomic Absorption Spectrometry and Cold Vapour Atomic Absorption Spectrometry) of trace elements (As, Cd, Cr, Cu, Hg, Mg, Mn, Ni, Sr and Zn) in cosmetic samples such as shampoos, gel (hair gel), crèmes (body milk, hair conditioner) and oil (body oil). The type of dispersion medium, the sample mass-to-dispersion medium volume ratio, as well as the parameters related to the ultrasound-assisted emulsification (sonication amplitude and treatment time) were exhaustively studied. Only 1 min of ultrasonic shaking and a dispersion medium containing 0.5% (w/v) of SDS + 3% (v/v) of HNO₃ or HCl allows obtaining a stable emulsion at least for 3 months. Thermal programs, nebulization of emulsions, speed of pumps and concentration of reagents used in cold vapour generation were optimized. Calibration using aqueous standards was feasible in all cases. Calibration by the standard addition method and recovery studies was also applied for validation. Microwave-assisted digestion and Inductively Coupled Plasma Mass Spectrometry were used for comparison purposes. Relative standard deviations from analysis of five independent emulsions were less than 9% in all cases.     

Silicon determination in milk by electrothermal atomic absorption spectrometry using palladium as chemical modifier

A direct method for silicon determination in milk samples by Electrothermal Atomic Absorption Spectrometry was developed. Palladium was used as chemical modifier at a concentration of 610 mg L(-1); with this modifier, silicon was stable up to 1800 degrees C. The precision and accuracy of the method were investigated. The detection limit was 16.2, 2.7 and 7.2 micro g L(-1) for cows' milk, human milk and infant formula, respectively. The method was applied to silicon determination in 17 infant formula samples, 13 human milk samples and 12 cows' milk samples.     

Determination of trace elements in cloud water and aerosols using instrumental neutron activation analysis and hydride generation with atomic absorption spectrometry

Cloud water and aerosol samples were collected at Whiteface Mountain, NY using the ASRC omnidirectional cloud water collector and high volume samples respectively. Trace element concentrations in cloud water samples were determined by neutron activation analysis and hydride generation with atomic absorption spectrometry. Agreement between the two methods for Se concentration was excellent (0.98±0.05). Aerosol samples were also analyzed for trace elements by neutron activation. Elemental analysis of cloud water and aerosols provide information useful to the study of microphysical and chemical interactions in cloud systems.