The analysis of conductive solid samples by r.f. capacitively coupled plasma at atmospheric pressure

A radiofrequency capacitively coupled plasma (rf CCP) with tip-ring electrode geometry has been used for the analysis of Al, Co, Cr, Cu, Mn, Mo, Ni, and V in low and medium alloyed steel. The sample is used as one of the electrodes of the plasma torch. The influence of plasma power, argon flow rate and distance between the electrodes on the analytical signals has been studied. The limits of detection are in the range of 0.001 to 0.048%. The dynamic range is three orders of magnitude.     

Analytical performance of an r.f. capacitively coupled plasma for atomic emission with tip-ring electrode geometry

A low to medium power radiofrequency capacitively coupled plasma is characterized as spectral source for atomic emission. The signal to background ratio and the limits of detection were determined for 19 elements as a function of the plasma torch geometry and the observation point.     

Analytical performance of an r.f. capacitively coupled plasma for atomic emission with tip-ring electrode geometry

A low to medium power radiofrequency capacitively coupled plasma is characterized as spectral source for atomic emission. The signal to background ratio and the limits of detection were determined for 19 elements as a function of the plasma torch geometry and the observation point.     

A new microwave plasma at atmospheric pressure

Plasma at atmospheric pressure can be obtained by surface wave propagation with a surfatron. If the plasma is produced within a quartz tube, it is constricted to a diameter of approx. 1 or 2 mm but its length can attain some tens of centimeters with microwave power as low as 100 W. This plasma is quite uniform along the axis, with a typical electron density of 3 × 10¹⁴ electrons/cm³. Since the excitation and gas temperatures are lower than 4000 K, the plasma is far from local thermodynamic equilibrium. High stability and repeatability is achieved with an argon flow of 0.2–17 l/min. Applications are foreseen in the field of optical spectroscopy and plasma chemistry.     

Laser vaporization of solid metal samples into an inductively coupled plasma

A laser vaporization-inductively coupled plasma system has been developed and tested for the direct analysis of solid metal samples. In this system the sample (normal emission spectroscopy metal disc standards) is vaporized utilizing a pulsed ruby laser and the vaporized material is swept into the ICP. Multichannel spectral data are simultaneously acquired using a photodiode array spectrometer. System parameters that have been investigated include ICP emission signal duration, number of laser shots to be used for a determination, the time between laser shots, free running or Q-switched laser operation, and the effect of laser focus. Analytical curves are presented for aluminum and brass samples.     

Heating of powders in an r.f. inductively coupled plasma under dense loading conditions

A study was carried out of the heating of powders in an r.f. inductively coupled plasma under dense loading conditions. The results obtained using a mathematical model taking into account plasma-particle interaction effects reveal an important cooling of the plasma caused by the presence of the particles. This, in turn, gave rise to a corresponding drop of the efficiency of the melting of the particles in the plasma. The effect is shown to depend strongly on the thermodynamic properties of the material of the powder.     

Laser Doppler anemometry under plasma conditions. Part II. Measurements in an inductively coupled r.f. plasma

Laser Doppler anemometry is used for the measurements of the plasma and particle velocity profiles in the coil region of an inductively coupled r.f. plasma. Results are reported for a 50 mm i.d. induction plasma torch operated at atmospheric pressure with argon as the plasma gas. The oscillator frequency is 3 MHz and the plate power is varied between 4.6 and 10.5 kW. Plasma velocity measurements are obtained using a fine carbon powder as a tracer. Measurements are also given for larger silicon particles ( ) centrally injected into the discharge under different operating conditions.Nomenclature d _p particle diameter - P ₀ plasma power - Q ₁ powder carrier gas flow rate - Q ₂ plasma gas flow rate - Q ₃ sheath gas flow rate - r distance in the radial direction - V axial plasma velocity - V _p axial particle velocity - Z distance in the axial direction - standard deviation     

Direct solid atomic emission spectrometric analysis of metal samples by an argon microwave plasma torch coupled to spark ablation

Spark ablation has been combined to microwave plasma torch atomic emission spectrometry for the direct analysis of compact metallic samples. The material is ablated by a medium voltage spark (450 V, 370 Hz) in a point-to-plane configuration and swept into a 100-W, 2.45-GHz argon microwave discharge. The microwave plasma is observed end-on and the radiation analysed with a polychromator. The detection limits for Fe, Ni, Pb and Sn in brass, Cr, Cu, Ni, Mn, Mo, Si and V in steel and Cu, Fe, Mg, Mn, Si and Zn in aluminium with the microwave plasma torch in the case of measurements with a polychromator are in the μg/g range and by a factor of up to 20 higher than those obtained with spark ablation coupled to inductively coupled plasma atomic emission spectrometry using a high resolution sequential spectrometer. The stability of the emission signal depends on the element studied and relative standard deviations usually are between 0.5 and 3.5%. In the case of low-alloy steels, the linearity and the precision of the calibration could be improved by internal standardisation. Several elements (Cr, Cu, Ni, Si and V) could be determined in a steel sample (BAS SS 410/1) with high accuracy and precision.     

Elemental analysis of bead samples using a laser-induced plasma at low pressure

An Nd:YAG laser (1064 nm, 8 ns, 30 mJ) was focused on various types of fresh, fossilized white coral and giant shell samples, including samples of imitation shell and marble. Such samples are extremely important as material for preparing prayer beads that are extensively used in the Buddhist faith. The aim of this research was to develop a non-destructive method to distinguish original beads from their imitations by means of spectral measurements of the carbon, hydrogen, sodium and magnesium emission intensities and by measuring the hardness of the sample using the ratio between Ca (II) 396.8 nm and Ca (I) 422.6 nm. Based on these measurements, original fresh coral beads can be distinguished from any imitation made from hard wood. The same technique was also effective in distinguishing beads made of shell from its imitation. A spectral analysis of bead was also performed on a fossilized white coral sample and the result can be used to distinguish to some extent the fossilized white coral beads from any imitation made from marble. It was also found that the plasma plume should be generated at low ambient pressure to significantly improve the hydrogen and carbon emission intensity and also to avoid energy loss inside the crater during laser irradiation at atmospheric pressure. The results of this study confirm that operating the laser-induced plasma spectroscopy at reduced ambient pressure offers distinct advantage for bead analysis over the conventional laser-induced breakdown spectroscopy (LIBS) technique operated at atmospheric pressure.     

Quantitative analysis of trace lead in tin-base lead-free solder by laser-induced plasma spectroscopy in air at atmospheric pressure.

A quantitative analysis of trace lead in tin-base lead-free solder was carried out with laser-induced plasma spectroscopy (LIPS). In order to evaluate the applicability of the technique for rapid in situ analytical purposes, measurements were performed in air at atmospheric pressure, and the emission characteristics of the plasma produced by a Q-switched Nd:YAG laser over a laser energy range of 10 - 90 mJ were investigated using time-resolved spectroscopy. The experimental results showed that the emission intensity of the analysis line (Pb I 405.78 nm) was maximized at a laser energy of around 30 mJ, and a time-resolved measurement of a spectrum with a delay time of 0.4 micros after the laser pulse was effective for reducing the background continuum. Based on the results, lead-free solder certified reference materials were analyzed for trace lead (concentration 174 - 1940 ppm), and a linear calibration curve was obtained with a detection limit of several tens ppm.     

Graphite furnace for alternative combination with d.c. arc or inductively coupled plasma. Introduction and analysis of solid samples

Summary A graphite furnace and d.c. arc combined source with the use of halogenating atmosphere in the furnace is described. The construction makes possible the introduction and analysis of both liquid and solid samples at minimum risk of contamination. Spectrographic detection resulted in background equivalent mass values below 10 ng for 22 from 36 elements applied in solution (Ar + CCl₄ atmosphere and NaCl matrix). The intensity-time profiles indicated high rates of distillation of the impurities (including B, Cr, Hf, Mo, Ti, V, W and Zr) from silicon carbide and silicon nitride samples in the first 40 s of heating under chlorination (CCl₄ vapour). Two versions of the exit part of the furnace are described for coupling to an ICP source; one of them has been used for the determination of titanium in alumina (spectrometric detection). Standardization with solution standards for solid sample analysis was unsuccessful. Based on the analytical curve obtained with variable amounts of solid standards (5–20 mg), a detection limit of 0.32 g/g Ti was found for 20 mg alumina.     

Characteristic temperatures and electron number densities in an R.F. capacitively coupled plasma

The excitation temperatures of Ar and Fe, the ionization temperatures of Ar and Ca and the electron number densities have been determined for a radiofrequency capacitively coupled plasma in the tip-ring electrode geometry. The temperatures and the electron number densities possess their maximum value close to the electrodes.     

Parametric study of the flow and temperature fields in an inductively coupled r.f. plasma torch

A theoretical investigation of the effect of different parameters on the flow and the temperature fields in a radiofrequency inductively coupled plasma is carried out. The parameters studied are: central injection gas flow rate, total gas flow rate, input power, and the type of plasma gas. The results obtained for argon and nitrogen plasmas at atmospheric pressure indicate that the flow and the temperature fields in the coil region, as well as the heat flux to the wall of the plasma confinement tube, are considerably altered by the changes in the torch operating conditions.     

Characteristic temperatures and electron number densities in an R.F. capacitively coupled plasma

The excitation temperatures of Ar and Fe, the ionization temperatures of Ar and Ca and the electron number densities have been determined for a radiofrequency capacitively coupled plasma in the tip-ring electrode geometry. The temperatures and the electron number densities possess their maximum value close to the electrodes.     

Microwave assisted digestion of atmospheric aerosol samples followed by inductively coupled plasma mass spectrometry determination of trace elements

A microwave digestion method in a closed vessel was developed for the determination of trace metals in atmospheric aerosols using inductively coupled plasma mass spectrometry (ICP-MS). A recovery study for the elements V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Cd, Sb, and Pb was conducted using multi-elemental standard solutions, NIST 1633b Trace Elements in Coal Fly Ash, and NIST 1648 Urban Particulate Matter. A simple digestion method using only HNO₃/H₂O₂ gave good recoveries (90%–108%) for all elements except Cr in SRM 1648, but yielded low recoveries for SRM 1633b. A more robust method using HNO₃/H₂O₂/HF/H₃BO₃ yielded higher recoveries (82%–¶103%) for the lighter elements (V – Zn) in SRM 1633b, and improved the Cr recovery in SRM 1648, but decreased the Se recovery in both SRMs. A comparative analysis of aerosol samples obtained at a remote mountain location Nathiagali, Pakistan (2.5 km above mean sea level), and Mayville, New York, downwind from the highly industrialized Midwestern United States, was carried out using Instrumental Neutron Activation Analysis (INAA) for the elements Cr, Mn, Fe, Co, Zn, As, Se, and Sb. The simple digestion method yielded excellent agreement for Cr, Fe, Zn, As, Se, and Sb, with slopes of the ICP-MS vs. INAA regressions of 0.90–1.00 and R² values of 0.96–1.00. The regressions for Mn and Co had slopes of 0.82 and 0.84 with R² values of 0.83 and 0.82, respectively. Addition of HF/H₃BO₃ did not improve the correlation for any of the elements and degraded the precision somewhat. The technique provides sensitivity and accuracy for trace elements in relatively small aerosol samples used in atmospheric chemistry studies related to SO₂ oxidation in cloud droplets. The ability to determine concentrations of a very large number of elements from a single analysis will permit source apportionment of various trace pollutants and hence strategies to control the sources of air pollution. This is particularly important as the health effects of particulate matter are increasingly recognized.     

Microwave assisted digestion of atmospheric aerosol samples followed by inductively coupled plasma mass spectrometry determination of trace elements

A microwave digestion method in a closed vessel was developed for the determination of trace metals in atmospheric aerosols using inductively coupled plasma mass spectrometry (ICP-MS). A recovery study for the elements V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Cd, Sb, and Pb was conducted using multi-elemental standard solutions, NIST 1633b Trace Elements in Coal Fly Ash, and NIST 1648 Urban Particulate Matter. A simple digestion method using only HNO3/H2O2 gave good recoveries (90%-108%) for all elements except Cr in SRM 1648, but yielded low recoveries for SRM 1633b. A more robust method using HNO3/H2O2/HF/H3BO3 yielded higher recoveries (82%-103%) for the lighter elements (V-Zn) in SRM 1633b, and improved the Cr recovery in SRM 1648, but decreased the Se recovery in both SRMs. A comparative analysis of aerosol samples obtained at a remote mountain location Nathiagali, Pakistan (2.5 km above mean sea level), and Mayville, New York, downwind from the highly industrialized Midwestern United States, was carried out using Instrumental Neutron Activation Analysis (INAA) for the elements Cr, Mn, Fe, Co, Zn, As, Se, and Sb. The simple digestion method yielded excellent agreement for Cr, Fe, Zn, As, Se, and Sb, with slopes of the ICP-MS vs. INAA regressions of 0.90-1.00 and R2 values of 0.96-1.00. The regressions for Mn and Co had slopes of 0.82 and 0.84 with R2 values of 0.83 and 0.82, respectively. Addition of HF/H3BO3 did not improve the correlation for any of the elements and degraded the precision somewhat. The technique provides sensitivity and accuracy for trace elements in relatively small aerosol samples used in atmospheric chemistry studies related to SO2 oxidation in cloud droplets. The ability to determine concentrations of a very large number of elements from a single analysis will permit source apportionment of various trace pollutants and hence strategies to control the sources of air pollution. This is particularly important as the health effects of particulate matter are increasingly recognized.     

Detection of ions by replacement-ion chromatography coupled to a microwave-induced nitrogen discharge at atmospheric pressure

The capabilities and limitations of replacement-ion chromatography (RIC) using a lithium-based replacement method and a microwave-induced nitrogen discharge at atmospheric pressure as the detector are critically evaluated for the determination of anions and cations. The system, including chromatographic columns, interface, and plasma-emission source, provides detection limits of 30–300 ng for anions and 100–500 ng for cations. Detectability and precision of the instrument are ultimately limited by multiplicative noise sources. The limitations imposed by multiplicative noise on RIC detection are assessed, and guidelines are presented that will allow judicious choice of alternative RIC detectors in the future.     

Use of a novel array detector for the direct analysis of solid samples by laser ablation inductively coupled plasma sector-field mass spectrometry

The use of laser ablation (LA) as a sample-introduction method for inductively coupled plasma mass spectrometry (ICP-MS) creates a powerful tool for trace elemental analysis. With this type of instrument, high analyte spatial resolution is possible in three dimensions with ng/g limits of detection and minimal sample consumption. Here, simultaneous detection is used to eliminate the correlated noise that plagues the ablation process. This benefit allows analyses to be performed with single laser pulses, resulting in improved depth resolution, even less sample consumption, and improved measurement precision. The new instrument includes an LA sample-introduction system coupled to an ICP ionization source and a Mattauch-Herzog mass spectrograph (MHMS) fitted with a novel array detector. With this instrument, absolute limits of detection are in the tens to hundreds of fg regime and isotope-ratio precision is better than 0.02% RSD with a one-hour integration period. Finally, depth-profile analysis has been performed with a depth resolution of 5 nm per ablation event.     

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.     

Matrix effects during analysis of plasma samples by electrospray and atmospheric pressure chemical ionization mass spectrometry: practical approaches to their elimination

Some cases of occurrence of matrix effects (mostly ion suppression) in protein-precipitated plasma samples, and their influence on the validity of plasma concentrations and pharmacokinetic parameters, are discussed. The comparison of matrix effects using either electrospray (TurboIonspray, TISP) or atmospheric pressure chemical ionization (APCI) indicated that APCI is less prone to matrix effects. Nevertheless, TISP is usually the first choice of ionization technique since unknown thermally labile metabolites might be present in the plasma samples causing erroneous results. A high impact of ion suppression on the plasma concentrations after intravenous (i.v.) administration was found, depending on the drug formulation (vehicle). Since ion suppression caused significantly lower plasma concentrations (by a factor of up to 5.5) after i.v. dosing, the area under the curve (AUC) was underestimated and the plasma clearance was consequently erroneously high, with an impact on drug candidate selection. By simple stepwise dilution (e.g. 10-fold and 50-fold) of the supernatant of protein-precipitated plasma samples, including all calibration and quality control samples, the matrix effects were recognized and eliminated.