On-line monitoring of a frontal chromatographic separation using inductively coupled plasma atomic emission spectroscopy

A test array is described employing a destructive analytical technique for the long-term monitoring of an industrial-scale separation process. As an example, we chose frontal chromatography as the separation and ICP/AES as the analytical method. The feed solution of the process was conveyed by a process pump via the separation unit to a sample station, where a small portion was diverted and transported by a roller pump into the spectrometer. We equipped our array with different loops for operating the process, calibrating the instrument and verifying the calibration. We obtained identical results for the different loops by absorbing the pulsation of the process pump and arranging for identical suction lines of the spectrometer pump. Based on the results, we redesigned the sample station for a technical application using only commercially available parts.     

A magnetically excited microwave plasma source for atomic emission spectroscopy with performance approaching that of the inductively coupled plasma

A novel magnetically excited microwave plasma emission source was developed and tested. Unlike previous microwave plasma sources which couple energy from the microwave electric field, this source couples energy from the magnetic field. The resultant plasma shape allows easy entrainment of wet sample aerosol, such as is produced by a conventional inductively coupled plasma (ICP) nebulizer and spray chamber, into the core of the plasma. Plasma support gas can be either nitrogen or air although better sensitivity is achieved using nitrogen. Good stability of operation was observed for both aqueous and organic solvents over a wide range of sample flows. The measured performance when used as a spectroscopic source in conjunction with an echelle polychromator showed detection limits approaching those of commercial ICP sources.     

Ultrasensitive determination of mercury by solution anode glow discharge atomic emission spectrometry coupled with hydride generation

An innovative method for the ultrasensitive detection of mercury by solution anode glow discharge atomic emission spectroscopy (SAGD-AES) coupled with hydride generation (HG) was first investigated. In this method, the mercury vapor generated by the HG was transmitted to the SAGD through the miniature hollow tungsten tube for excitation and detected by a miniaturized spectrograph. A thorough parametric evaluation of the HG and SAGD system was performed, including the type and concentration of carrier acid, He flow rate, concentrations of NaBH₄, discharge current and discharge gap. Under optimal operating conditions, the detection limit for Hg²⁺ achieved 0.03 μg/L, with a relative standard deviation of 1.1% at the Hg²⁺ concentration of 5 μg/L. Moreover, the correlation coefficient of the calibration curve was 0.9996 in the range between 0.1 and 10 μg/L. The accuracy and practicability of HG-SAGD-AES were verified by measuring GBW09101b (human hair), GBW10029 (fish), soil and rice samples. The results showed good agreement with the certified values and values from direct mercury analyzer (DMA).     

Carbon-related matrix effects in inductively coupled plasma atomic emission spectrometry

In Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES), it has been observed that the emission intensity of some atomic lines is enhanced or depressed by the presence of carbon in the matrix. The goal of this work was to investigate the origin and magnitude of the carbon-related matrix effects in ICP-AES. To this end, the influence of the carbon concentration and source (i.e. glycerol, citric acid and potassium hydrogen phthalate), the experimental conditions and sample introduction system on the aerosol characteristics and transport, plasma excitation conditions and the emission intensity of several atomic and ionic lines of a total of 15 elements has been studied. Results indicate that carbon related matrix effects do not depend on the carbon source and they become more severe when the amount of carbon loaded into the plasma increases, i.e., when using: (i) carbon concentrations higher than 5 g L^− 1; (ii) high sample uptake rates; and (iii) efficient sample introduction systems. Thus, when introducing carbon into the plasma, the emission intensity of atomic lines with excitation energies below 6 eV is depressed (up to 15%) whereas the emission intensity of atomic lines of higher excitation energies (i.e. As and Se) are enhanced (up to 30%). The emission intensity of the ionic lines is not affected by the presence of carbon. The origin of the carbon-related interferences on the emission intensity of atomic lines is related to changes in the line excitation mechanism since the carbon containing solutions show the same aerosol characteristics and transport efficiencies as the corresponding aqueous solutions. Based on the previous findings, a calibration approach for the accurate determination of Se in a Se-enriched yeast certified material (SELM-1) has been proposed.     

The design and characteristics of direct current glow discharge atomic emission source operated with plain and hollow cathodes

A compact direct current glow discharge atomic emission source has been designed and constructed for analytical applications. This atomic emission source works very efficiently at a low-input electrical power. The design has some features that make it distinct from that of the conventional Grimm glow discharge source. The peculiar cathode design offered greater flexibility on size and shape of the sample. As a result the source can be easily adopted to operate in Plain or Hollow Cathode configuration. I-V and spectroscopic characteristics of the source were compared while operating it with plain and hollow copper cathodes. It was observed that with hollow cathode, the source can be operated at a less input power and generates greater Cu I and Cu II line intensities. Also, the intensity of Cu II line rise faster than Cu I line with argon pressure for both cathodes. But the influence of pressure on Cu II lines was more significant when the source is operated with hollow cathode.     

Total protein determinations by particle beam/hollow cathode optical emission spectroscopy (PB/HC-OES) system III: Investigation of carrier salts for enhanced particle transport

Particle beam hollow cathode optical emission spectroscopy (PB/HC-OES) is evaluated as a generic tool for total protein determinations by monitoring the carbon atomic emission (C (I) 193.0 nm) resultant from dissociated analyte species. Previous studies demonstrated the capability of the PB/HC-OES system for total protein determinations with limits of detection for bovine serum albumin (BSA) samples being at the single-nanogram level for 200 l injections. Non-linear behavior across the concentration range in the calibration curve was observed due to the poor transport of small particles (owing to low analyte concentrations) through the PB interface. The potential use of non-volatile salts as carrier agents is investigated in the determination of protein samples by PB/HC-OES. A range of chloride salts (different cations), potassium salts (different anions), and an organic modifier (ammonium acetate) is investigated here for possible use as carriers upon addition as sample injection matrices for protein samples. The analyte response curves of BSA samples with KCl added as the sample injection matrix show higher sensitivity, better linearity (R²) and subsequently lower detection limits in comparison to those obtained with water, HCl, KNO₃ or ammonium acetate as carrier matrices.     

Microwaves spark emission spectroscopy for the analysis of cations:A simple form of atomic emission spectroscopy

A novel method for the cation analysis was investigated.The analysis is based on the sparking of the salts of metals in a microwave oven after placing in a graphite cell.The graphite cell absorbs microwaves and produces high temperature which converts the salt into light emitting species.The colour of light was found to dependent on the nature of cation,however,the intensity of the emitted light was found to be depending upon the form and shape of the graphite assembly in addition to the concentration of the salt.This communication presents explanation for all these observations and for the systematic and quantitative analysis using microwave spark emission technique.     

Evaluation of a hollow cathode atomic emission source designed for continuous solution sample introduction

A hollow cathode discharge capable of continuous operation with solution sample introduction is described. Discharge current densities up to 0.64 are maintained in a helium plasma. Analyte emission intensities are optimized in terms of anode placement in relation to the hollow cathode, carrier gas flow rate, discharge current and sample solution flow rate. Detection limits for selected elements are reported and range from 0.03 for Li to 200 for Zn. Temporal stability of the discharge is examined and a calibration curve for Li is presented.     

光谱分析新光源的完善及发射光谱仪的改造

设计了一种高能火花光源,并用该光源在具有较低电离电位基体中分析有较高激发线的杂质,如ZrO2中Hf;Nb2O5中Ta和MoO3中W,分析灵敏度提高了约10倍。用在较长波段分析气体杂质（如O和C）也是可能的。     

Optical emission spectroscopy as a real time diagnostic tool for plasma-assisted deposition of TiN

Real-time optical emission spectroscopy (OES) was used to monitor the deposition of TiN both from mixtures of tetrakis(dimethylamino)titanium (TDMATi)-N₂ and TiCl₄-H₂-N₂ in an electron cyclotron resonance chemical vapor deposition system. The accurate control of the ratio of the emission intensities of ionized nitrogen at 391.4 nm and molecular nitrogen at 357.7 nm (N ₂ ⁺ /N₂) led to low temperature deposition of stoichiometric TiN (Ti/N ≈ 1) and very low resistivity in both cases. It was found that high ion density plasmas are crucial for a considerable reduction of the deposition temperature while maintaining good film quality. OES shows that the abundance of certain excited plasma species is not only dependent on the gas mixture and the deposition parameters, such as total pressure and microwave power, but also is strongly affected by the magnetic field configuration. The deposition rate and the film resistivity can be related to the emission intensity ratio, I(N ₂ ⁺ )/I(N₂). Finally, the two processes are compared in terms of the quality of as-deposited and heat-treated films. The comparison shows that the films obtained with TDMATi exhibit lower resistivity and are thermally more stable than with TiCl₄.     

A cold plasma dielectric barrier discharge atomic emission detector for atmospheric mercury

An automated atmospheric elemental mercury analyzer based on the dielectric barrier discharge (DBD) atomic emission technique was developed. The instrument is based on a gold-on tungsten coiled filament preconcentrator fashioned from commercial quartz-halogen lamps, a DBD excitation source and a radiation detector. An in-house program provided system control and data collection. Several types of radiation detectors, e.g., charge coupled device (CCD) array spectrometers, photomultiplier tubes (PMTs) and phototube (PT) are investigated. An argon plasma provided better performance than a nitrogen plasma. With ∼0.88 standard liters per min sampling rate and preconcentration for 2 min, the estimated (S/N = 3) detection limit was 0.12 ng/L (Hg⁰), the linear range extended at least to 6.6 ng Hg/L. Typical RSD values for determination at the single digit ng/L level ranged from 2.8 to 4.9%. In 19 separate calibrations conducted over 7 days, the calibration slope had a standard error of 1%. The system was applied to the determination of atmospheric mercury in two different locations.     

Environmental applications of capillary gas chromatography coupled with atomic emission detection — a review

Environmental applications of capillary gas chromatography coupled with atomic emission derection (GC-AED) have been reviewed with emphasis on both the commercial and laboratory-built systems. Attention was focused on (1) element-selective detection of non-metallic as well as metallic pollutants, (2) identification of contaminants, and (3) sample preparation considerations.     

Determination of butyltin species by GC/atomic emission spectroscopy

A commercially available atomic emission detector coupled to a capillary column-containing gas chromatograph (;GC/AE) was utilized to detect organotin compounds. The response for tin was found to be dependent on the flow rate of the make-up gas. At flow rates of 174 cm³ min^?1, 6 × 10^?12 g of tin could be detected. Lower flow rates decreased the sensitivity. Response curves for two different pressures were established and both plots exhibited curvature at low concentrations. Extracted fish and sediment samples were analysed on the GC/AE system. The technique is element-specific. The presence of tin compounds could be confirmed by examining the emission spectra taken at the retention time of the peak.     

Investigation of a novel hollow cathode configuration for Grimm-type glow discharge emission

A hollow cathode configuration was designed for a Grimm-type glow discharge atomic emission spectrometer (GD-AES). The operating conditions including the hollow cathode dimension, applied pulsed voltage and argon pressure, were optimized. The 10-μs pulses at 1.8 kV in a 3-torr discharge worked best. A pulsed hollow cathode Grimm discharge (HCG) offers several advantages: efficient excitation and ionization; high sensitivity; temporal spectral resolution; and rapid sample interchange. The capability of this source for the determination of elemental composition in metals, alloys and in solution residues is investigated. Samples used in this study included copper and steel standards.     

Evaluation of a low-resolution near-IR monochromator for atomic emission detection in capillary gas chromatography

A single 0.2 m focal length near-IR monochromator providing a 0.8–3.2 nm effective bandpass was evaluated as spectrometer for F-, Cl-, Br-, I-, S-, and P-selective atomic emission detection in capillary gas chromatography. With optimized plasma conditions and careful wavelength selection, interferences from eluting hydrocarbons were almost eliminated for all the elements studied (element-to-carbon selectivities between 1000:1 and 10000:1). For Cl and S, other heteroatoms were found not to cause cross-interferences. F-, Br-, I-, and P-selective detection, however, was complicated by this second type of non-specificity. For these atoms, elemental confirmation was carried out by analyzing the samples also for heteroatoms potentially causing interferences.     

Low power capacitively coupled plasma microtorch for simultaneous multielemental determination by atomic emission using microspectrometers

A new, low power capacitively coupled plasma microtorch (30 W, 13.56 MHz, 0.5 L min^?1 Ar) was investigated in conjunction with commercially available microspectrometers for the simultaneous multielemental analysis by atomic emission spectrometry of liquid samples without desolvation. Emission spectrum is simpler than in ICP-AES, the resonance lines are the most intense, so that a microspectrometer with FWHM of at least 1.5 nm is satisfactory for the record. The deviation from the Boltzmann distribution for Fe I has demonstrated the departure from the LTE in plasma. The non-spectral matrix effects of Li, Na, K, Ca and Mg on analytes emission are depressive and depend on matrix volatility, ionization potential of the interferent and analyte excitation energy. The detection limits (μg mL^?1) are in the range 0.003 (Li) and 1.5 (Mn). The use of the standard additions method allowed the simultaneous determination of elements in environmental certified reference materials with overall recovery of 95 ± 10% and relative standard deviation of 1.7–8.2%. Compared to the traditional ICP, the microtorch has a simple construction, runs at low argon flow and can be integrated in a portable system suitable for in-situ simultaneous determination of elements.     

Model of microsecond pulsed glow discharge in hollow cathode for mass spectrometry

A new model for microsecond pulsed glow discharge in a hollow cathode and its afterglow is described. The model is based on the Monte-Carlo method together with a new method for electrical field calculation, which is based on some phenomenological laws of plasma behavior. The afterglow model uses continuity and Poisson equations. A qualitative agreement between the model results and results published in experimental and theoretical works is demonstrated. Some processes in the microsecond pulsed discharge in the hollow cathode, such as sputtering, ionization and transfer of sample, are investigated. The model is successfully used for the optimization of the operational parameters of the time-of-flight mass spectrometer with ionization by microsecond pulsed glow discharge in a hollow cathode.     

Detection of metal ions by atomic emission spectroscopy from liquid-electrode discharge plasma

In this paper, the discharge ignited in a capillary connecting two beakers filled with electrolyte solution is investigated. During the experiment, an external electrical voltage is applied through two platinum electrodes dipped in the beakers. A gas bubble forms inside the capillary when the applied voltage is higher than 1000 V. Since the beakers are tilted slightly, after generation, the bubble moves slowly to the uphill outlet of the capillary due to buoyancy. When the bubble reaches the end of the capillary, it cracks and a bright discharge is ignited. The emission spectra of the discharge plasma are related to the metal ions dissolved in the solution and thus can be used for metal ion detection. An application of the system to measurement of water hardness is shown.     

Determination of metal concentrations in lichen samples by inductively coupled plasma atomic emission spectroscopy technique after applying different digestion procedures

Three digestion procedures have been tested on lichen samples for application in the determination of major, minor and trace elements (Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, V and Zn) in lichen samples collected in Aegean Region of Turkey by inductively coupled plasma atomic emission spectrometer (ICP-AES). The acid mixture of concentrated HNO₃, H₂O₂ and HF were used. The instrument was optimized using lichen matrix considering RF power, nebulizer pressure, auxiliary flow rate and pump rate. The accuracy of the overall analyses was first estimated by analysis of two certified reference materials. Good agreement between measured and reference values were found for almost all elements. As the second way of determining the accuracy, results obtained from independent analytical techniques (ICP-AES and instrumental neutron activation analysis (INAA)) were compared for all elements by analyzing real samples. Correlation coefficients of two techniques for the elements ranged between 0.70 (Mg) and 0.96 (Fe). Among the three digestion systems, namely microwave, open vessel and acid bomb, microwave digestion system gave the best recovery results. The method detection limit (MDL) was computed using reagent blanks of microwave digestion system since it provides cleaner sample preparation. Detection limit is adequate for all elements to determine the elements in lichen samples. The precision was assessed from the replicate analyses of reagent blanks of microwave digestion system and was found to be less than 1.5% relative standard deviation (R.S.D.).     

Pulsed discharge emission detector — Application to analytical spectroscopy of permanent gases

Summary This publication contains our initial development of a pulsed discharge emission detector (PDED) (patent pending). It uses a pulsed high voltage discharge in helium, which provides a stable source for atomic and polyatomic emission spectroscopy. We have evaluated this detector for both quantitative and qualitative analysis of a range of chemical compounds. Emission spectra observed from the pulsed high voltage discharge are valuable for spectral analysis. The results obtained for selected permanent gases in the ultraviolet, visible and infrared regions of the optical spectrum indicate that these spectra can be used for compound identification after a chromatographic separation. The data are unique in our opinion and serve as a basis for the future development and investigation of the analytical significance of this detection method.Dedicated to Professor Leslie S. Ettre on the occasion of his 70th birthday.