On-line preconcentration with activated carbon for microwave plasma torch atomic emission spectrometry

This paper presents a method whereby trace elements are adsorbed in NH(4)ClNH(3) medium on activated carbon and then determined by microwave plasma torch atomic emission spectrometry (MPT-AES). The working conditions (including microwave forward power, gas flow rate, NH(3)NH(4)Cl concentration in the sample solution, HCl concentration in the eluant, sample introduction rate and preconcentration time) were investigated in detail. The effects of concomitant ions were studied. The experimental results for such analytes as Pb, Mn, Cd, Cu and Fe indicate that the procedure can eliminate fundamentally the interferences caused by alkali and alkaline earth metal elements and the application of it to the determination of iron in industrial silicon and tap water samples is successful.     

An improved microwave plasma torch for atomic spectrometry

The analytical performance of a microwave plasma torch was improved through mechanical alterations. Several problems reported in earlier designs were addressed: the ignition and stabilization of a helium plasma in the MPT was difficult; high powers were required to both ignite and operate the plasma; otherwise, the plasma would erratically change from an annular to a filament type discharge. In the new torch, the helium discharge was stabilized by replacing the copper central tube with one made of quartz. In addition, air entrainment was alleviated through use of a sheathing gas. This modification simplified the background mass spectrum and raised the effective ionization temperature of the discharge. A detailed schematic diagram of the new microwave plasma torch is presented.     

Flow-injection on-line column preconcentration for low powered microwave plasma torch atomic emission spectrometry

This paper describes an improvement in detection capability of microwave plasma torch atomic emission spectrometry by using a flow-injection on-line column preconcentration system. The analytical performances of Cd, Cu, Mn and Zn were studied. The analytes were preconcentrated with a thiol resin. The preconcentration period, the pH of the sample solution and the HCl concentration in the eluant were examined in detail. Operating conditions were optimized as follows: sample uptake, 1.2 ml min(-1); preconcentration period, l min; pH of sample solution, 9; HCl concentration in the eluant, 1 mol 1(-1). The experimental results show that flow-injection on-line column preconcentration can not only eliminate the effect of some concomitant elements, such as Li, Na and K, on the determination of analyte, but also enhance the sensitivity.     

Use of microwave plasma torch atomic emission spectrometry for the determination of silicon

 A method for the elimination of matrix effects was developed for the determination of trace amounts of silicon by microwave plasma torch atomic emission spectrometry (MPT-AES). The sample solution was introduced into the MPT with a pneumatic nebulizer (PN). When Ar was used as both carrier and support gas, a detection limit of 10.8 ng/ml was obtained. The precision was 4.2% (RSD). The characteristics of the emission spectrum of silicon in MPT was studied in detail. The interference of some concomitant cations with the silicon emission was eliminated by incorporation of a cation-exchange column into the flow injection system. The method has been applied to analyze some practical samples and the results obtained are satisfactory. Received: 23 October 1995/Revised: 16 April 1996/Accepted: 20 April 1996     

Particle sample introduction system for inductively coupled plasma–atomic emission spectrometry

Development and characterization of a new, relatively inexpensive, computer-controlled, particle sample introduction (PSI) system for programmable delivery of small amounts of diluted powdered samples into an inductively coupled plasma (ICP) and measurement by atomic emission spectrometry (AES) is described. The PSI was developed for use with non-hygroscopic particles, in particular those with a particle weight in the ng range (i.e., with a diameter in low μm-range) and for solids that can be converted to a powder (i.e., a collection of particles). In this first report on PSI–ICP–AES, linearity of calibration curves and plasma loading concerns were addressed using three modes of operation. In the first mode, the PSI operated similar to a nebulizer and it delivered to the plasma for a period of 5–10 s a relatively constant amount of particles diluted with graphite. In the second mode, the PSI delivered to the plasma a small “puff” of a diluted sample, thus generating a transient, time-domain signal with duration of about a second. In the third mode, an even smaller “puff” was delivered to the plasma and, using high-speed data acquisition (in the kHz range), time-resolved emission signals from individual, μm-diameter and ng-weight particles were observed. Thus, the PSI can also be thought of as a nano-particle (i.e., ng rather than nm) sample introduction system. Similarly, the high-speed, wide-bandwidth single-channel time-resolved data acquisition mode enabled the determination of particle-size distribution. In addition, a dual-channel (or dual-element) mode enabled homogeneity studies on a per-individual-particle basis. In all modes, linear calibration curves were obtained (provided that plasma loading was avoided). Per-cent relative standard deviation ranged between 3.1% and 4.2% for Ni in certified reference materials but was as high as 50% for heterogeneous soil samples. Tungsten emission signals from refractory tungsten carbide powders were enhanced using mixed gases and by modifying the chemical environment of the ICP using SF₆. Furthermore, when coupled with high-speed data acquisition, PSI brought unique capabilities to ICP–AES for homogeneity studies from individual ng-weight particles and for the determination of particle size distributions. Overall, it was concluded that PSI is an attractive alternative to powder sample introduction systems described in the literature.     

Determination of carbon in aqueous solutions by atmospheric-pressure helium microwave induced plasma atomic emission spectrometry with gas-phase sample introduction technique.

A trace amount of carbon was determined by atmospheric-pressure helium microwave induced plasma atomic emission spectrometry (He-MIP-AES) with gas-phase sample introduction technique. This method was applied for the generation of a continuous flow of carbon dioxide by the acidification of carbonate ion and hydrogen carbonate ion for the determination of carbon. The generated carbon dioxide was separated from the solution by a simple gas-liquid separator, dried with a desiccant and swept into the MIP with helium carrier gas for analysis. Of the acids and drying agents investigated, hydrochloric acid for acidification and anhydrous calcium chloride as a desiccant were found to be the most appropriate for the generation of carbon dioxide. Under the optimized experimental conditions, the best attainable detection limits at C (I) 193.09 and C (I) 247.86 nm lines were 7.89 and 8.10 microg/l with linear dynamic ranges of 100 to 10,000 and 100 to 20,000 microg/l for carbon, respectively. The presence of many diverse elements and ions was found to cause a more or less depressing interference by the proposed technique. However, no interference was observed from the following elements and ions: Ca, K, Rb, Br-, Cl-, F- and I-. Finally, the present method has been applied to the determination of carbon in several water samples.     

Microwave desolvation for acid sample introduction in inductively coupled plasma atomic emission spectrometry

This study deals with the behaviour of a microwave desolvation system (MWDS) with acid solutions in inductively coupled plasma atomic emission spectrometry. Hydrochloric, nitric, sulphuric and perchloric acids at different concentrations (up to 0.6 mol l⁻¹) have been tested. Sample uptake rate (Q_l) was also varied. The parameters evaluated for each variable were analyte and solvent transport rates and emission intensity. The combination of low acid concentrations (0.05–0.1 mol l⁻¹) and low liquid flows (0.4 ml min⁻¹) leads to the highest analyte transport rate and emission signal and to the lowest solvent transport rate. For Q_l higher than 1.9 ml min⁻¹, the use of an impact bead is advisable. Among the acids tested, sulphuric and perchloric acids give rise to higher emission intensities than hydrochloric acid and nitric acid. Nonetheless, the limits of detection (LODs) obtained with the MWDS are about the same magnitude irrespective of the solution employed. The LODs reached when using the MWDS are similar to those obtained with a desolvation system based on infrared heating of the aerosol.     

Particle transport in a He-microchip plasma atomic emission system with an ultrasonic nebulizer for aqueous sample introduction

The transport efficiency of dried particles generated from an ultrasonic nebulizer (USN) was studied to improve the analytical performance of a lab-made, He-microchip plasma system, in which a quartz tube (~ 1 mm i.d.) was positioned inside the central channel of a poly(dimethylsiloxane) (PDMS) polymer chip. The polymer microchip plasma has the advantages of low cost, small size, easy handling and design, and self-ignition with long stabilization (> 24 h). However, direct introduction of aqueous solution into the microplasma for the detection of metals remains problematic due to plasma instability. In addition, the much smaller size of the system can cause signal suppression due to low transport efficiency. Therefore, knowledge of particle transport efficiency in this microplasma system is required to enhance the sensitivity and stability. The weight of transported particles in the range of 0.02 to 10 mg m^− 3 was measured using a piezobalance with a precision of 0.4–17.8%, depending on the operating conditions. The significant effects of the USN operating conditions and the physical properties of the tubing, namely, length, inner diameter and surface characteristics, on the number of particles transported from the nebulizer to the microplasma were studied. When selected metals, such as Na, Mg and Pb, at a concentration of 5 mg L^− 1 were nebulized, transported particles were obtained with a mass range of 0.5–5 mg m^− 3, depending on atomic weights. For application of the He-rf-microplasma, the atomic emission system was optimized by changing both the radio frequency (rf) power (60–200 W) and cooling temperature of the USN (− 12–9 °C). The limits of detection obtained for K, Na and Cu were 0.26, 0.22, and 0.28 mg L^− 1, respectively. These results confirmed the suitable stability and sensitivity of the He-rf-PDMS microchip plasma for application as an atomization source.     

Modified Babington nebulizer for inductively coupled plasma atomic emission spectrometry.

A PTFE Babingtonnebulizer equipped with a hood was investigated for inductively coupled plasma atomicemission spectrometry in conjunction with a PTFE cyclone chamber, in order to nebulize various sample solutions containing high salts, hydrofluoric acid and/or suspended solid. A hood of 3 mmphi (nozzle side) - 5 mmphi (outlet side) and 6 mm in length gave a comparable or higher sensitivity compared to a system with a commercially available concentric nebulizer and a glass cyclone chamber. Moreover, the present nebulizer was fully interchangeable with a concentric one at normal argon pressure, attaining sufficient stability, a short wash-out time and good nebulizing of high matrices solutions. The present system was successfully applied to the determination of trace impurities in highly pure silica powders.     

A microwave plasma cavity assembly for atomic emission spectrometry

Although inductively coupled plasmas (ICPs) are widely used for multielement analysis microwave induced plasma (MIP) offers a great potential for a variety of applications. Modifications to incorporate MIP into commercial ICP direct reading spectrometer systems have been developed. A direct reading échelle spectrometer is described which opens new possibilities for the successful construction of commercial MIP-AES systems with the potential to run all of the typical methods worked out for earlier ICP-AES applications. Use of flow injection techniques and automation to couple with in situ concentration will likely offer a further improvement in the analytical performance of this system. Due to the capabilities demonstrated by this spectrometer it appears that hybrid instruments will be increasingly important for future developments in optical spectrometry. This is particularly true for very demanding areas such as atomic emission spectrometry. The system could be readily commercialized.     

A microwave plasma cavity assembly for atomic emission spectrometry

Although inductively coupled plasmas (ICPs) are widely used for multielement analysis microwave induced plasma (MIP) offers a great potential for a variety of applications. Modifications to incorporate MIP into commercial ICP direct reading spectrometer systems have been developed. A direct reading échelle spectrometer is described which opens new possibilities for the successful construction of commercial MIP-AES systems with the potential to run all of the typical methods worked out for earlier ICP-AES applications. Use of flow injection techniques and automation to couple with in situ concentration will likely offer a further improvement in the analytical performance of this system. Due to the capabilities demonstrated by this spectrometer it appears that hybrid instruments will be increasingly important for future developments in optical spectrometry. This is particularly true for very demanding areas such as atomic emission spectrometry. The system could be readily commercialized.     

Plasma behavior during electrothermal vaporization sample introduction in inductively coupled plasma atomic emission spectrometry

Electrothermal vaporization (ETV) sample introduction in inductively coupled plasma atomic emission spectrometry suffers from severe matrix effects. In the present study, the differences between wet and dry plasma conditions are studied. In addition, the influence of the sample composition was investigated. An inductively coupled plasma optical emission spectrometer, with detection based on charge transfer, allowed the simultaneous measurement of ionic and atomic emission line intensities during the transient signal. Mg and Cr were the test elements. The ion-to-atom line ratio increases at higher power settings, but the changes were larger when a nebulizer was used for sample introduction than with ETV sample introduction. The decrease of ion-to-atom line ratios at increasing observation height was more pronounced when ETV was used, due to the absence of water vapor. The gas flow rate showed a stronger influence for nebulization than for ETV. In the presence of a calcium matrix, lower ion-to-atom line ratios were observed, but the ratio did not change significantly within the transient emission signal. Similar line ratios were observed for different amounts of calcium matrix. The values of ion-to-atom line ratios for Mg and Cr indicate that the plasma ionization and thermal characteristics are not modified due to the presence of the calcium matrix.     

电热蒸发进样电感耦合等离子体原子发射光谱（ETV－ICP－AES）联用技术研究

本文采用国产部件组装了一套ＥＴＶ－ＩＣＰ－ＡＥＳ仪器体系，对装置的连接及操作参数进行优化。深入系统地考察了分析物的蒸发过程和传输过程，提出了难熔元素的蒸发和传输机理。研究了ＥＴＶ－ＩＣＰ－ＡＥＳ中基体效应，提出了以聚四氟乙烯为氟化剂，氟化辅助ＥＴＶ－ＩＣＰ－ＡＥＳ测定难熔元素的新方法，应用于环境和生物标样中痕量元素分析，获得满意结果。     

Microwave plasma torch analytical atomic spectrometry

The microwave plasma torch (MPT), as a relative new source, has found extensive use in atomic spectrometry. In this review, the fundamental features and characteristics of the MPT are summarized and compared with other kinds of analytical atomic sources, such as the more popularly used inductively coupled plasma (ICP), the direct current plasma (DCP), as well as other kinds of microwave plasmas (MWPs). Since the MPT offers some attractive features, it has been used as an excitation source for atomic emission spectrometry (MPT-AES), including the atomic emission detection (AED) for gas chromatography (GC), liquid chromatography (LC) and supercritical fluid chromatography (SFC). Also, it has been used either as an ionization source for atomic mass spectrometry (MPT-AMS) or an atomization source for atomic fluorescence spectrometry (MPT-AFS). The historical development and recent improvements in these MPT atomic spectrometric techniques are evaluated with emphasis on the analytical advantages and limitations. In addition, the future research directions and the application prospects of MPT atomic spectrometry (MPT-AS) are discussed.     

Determination of trace Ag, Au, Ge, Pb, Sn and Te by microwave plasma torch atomic emission spectrometry coupled with an electrothermal vaporization sample introduction system

An electrothermal vaporization (ETV) sample introduction device tantalum filament was combined with microwave plasma torch atomic emission spectrometry (MPT-AES) for determination of several trace elements. Some operating parameters of the system were optimized. The effects of easily ionized elements (EIEs) on the emission intensities of the tested elements were studied in detail. It was revealed that there was no interference resulting from small amount of sample matrix; while with the existence of large amount of sample matrix, the method of standard addition could be used to determine trace elements in samples. So, no modifier was required in this method. The results indicated that ETV-MPT-AES not only has the advantage of micro sample consumption (a volume of 3 mul for each injection), but also offers high sensitivities for the determination of Ag, Au, Ge, Pb, Sn and Te as compared with those obtained with pneumatic nebulization (PN) MPT-AES.     

Simultaneous electrothermal vaporization and nebulizer sample introduction system for inductively coupled plasma mass spectrometry

The novel analytical application of the combination of an inline electrothermal vaporization (ETV) and nebulization source for inductively coupled plasma mass spectrometry (ICP-MS) has been studied. Wet plasma conditions are sustained during ETV introduction by 200 mL/min gas flow through the nebulizer, which is merged with the ETV transport line at the torch. The use of a wet plasma with ETV introduction avoided the need to change power settings and torch positions that normally accompany a change from wet to dry plasma operating conditions. This inline-ETV source is shown to have good detection limits for a variety of elements in both HNO₃ and HCl matrices. Using the inline-ETV source, improved limits of detection (LOD) were obtained for elements typically suppressed by polyatomic interferences using a nebulizer. Specifically, improved LODs for ⁵¹V and ⁵³Cr suffering from Cl interferences (⁵¹ClO⁺ and ⁵³ClO⁺ respectively) in a 1% HCl matrix were obtained using the inline-ETV source. LODs were improved by factors of 65 and 22 for ⁵¹V and ⁵³Cr, respectively, using the inline-ETV source compared to a conventional concentric glass nebulizer. For elements without polyatomic interferences, LODs from the inline-ETV were comparable to conventional dry plasma ETV-ICP time-of-flight mass spectrometry results. Lastly, the inline-ETV source offers a simple means of changing from nebulizer introduction to inline-ETV introduction without extinguishing the plasma. This permits, for example, the use of the time-resolved ETV-ICP-MS signals to distinguish between an analyte ion and polyatomic isobar.     

A novel sample introduction system for microwave-induced plasma optical emission spectrometry

A newly developed micro-sampling technique using a discrete sample introduction system (DSIS) has been demonstrated for simultaneous multi-element analysis by microwave-induced plasma optical emission spectrometry (MIP-OES). A microliter volume of sample solution (20 μl) is manually inserted into a Teflon microsampling device and subsequently pumped at low solution uptake rates of <100 μl min⁻¹ to a Meinhard-type concentric nebulizer and then into a 250-W helium plasma. The performance of DSIS-MIP-OES was demonstrated by the determination of major (Na, K, Ca, Mg), minor (Cu, Fe, Zn) and trace (Sr) elements in two clinical standard certified reference materials (serum, hair). Standard microaddition procedures were used to minimize possible matrix interference. The detection limit (3σ) obtained was 10, 30, 50, 100, 10, 5, 20 and 40 ng ml⁻¹ for Ca, Cu, Fe, K, Mg, Na, Sr and Zn, respectively. The method offers relatively good precision (RSD ranged from 5 to 14%) and microsampling capability. Agreement between analytical results and certified values for the test elements was good. The method could be useful as a routine clinical laboratory procedure.     

微波等离子体炬原子发射光谱法测定原油中的钒

采用微波等离子体炬原子发射光谱法(MPT-AES)测定原油中的钒。详细考察了分析谱线、载气流量、工作气流量、氧屏蔽气流量和微波功率对钒发射强度的影响。实验结果表明:在分析谱线289.332nm,微波功率90W,载气流量1350m L·min-1,工作气流量650m L·min-1条件下,测得钒的检出限为56.2ng·m L-1,钒含量在0~100μg·m L-1范围符合线性关系。对原油中常见的共存元素影响进行考察,3倍的铜,10倍的镁、铁对钒的测定无影响;1倍的钙、镍、钠、锌、锰干扰钒的测定。测试体系对乙二胺四乙酸二钠有一定的允许量,适量的乙二胺四乙酸二钠溶液可大幅度提高共存元素的允许量。原油中钒测定结果的相对标准偏差不大于4.1%,加标回收实验的回收率为95.6%~104.3%。     

微波消解-微波等离子体炬原子发射光谱法测定合金钢中的铜、锰、钼

用微波等离子体炬 (MPT)为激发光源 ,氩气为等离子体工作气体 ,用气动雾化进样 ,研究了微波消解 微波等离子体炬原子发射光谱法 (MPT AES)测定合金钢中铜、锰、钼的方法。考察了微波功率、载气流量、工作气流量、氧屏蔽气流量等实验参数对测定铜、锰、钼的影响。对微波消解合金钢样品的消解条件进行了考察 ,建立了最佳消解程序。测定铜、锰、钼的检出限分别为 3.3、3.7和 42ng mL ,RSD(n =6)分别为 1 7%、2 .4%、3.8% ,并且测得它们的线性范围分别为0 .0 2～ 5 0 μg mL、0 .0 4～ 5 0 μg mL和 0 .2 0～ 5 0 μg mL。