Investigation of artifacts caused by deuterium background correction in the determination of phosphorus by electrothermal atomization using high-resolution continuum source atomic absorption spectrometry

The artifacts created in the measurement of phosphorus at the 213.6-nm non-resonance line by electrothermal atomic absorption spectrometry using line source atomic absorption spectrometry (LS AAS) and deuterium lamp background correction (D₂ BC) have been investigated using high-resolution continuum source atomic absorption spectrometry (HR-CS AAS). The absorbance signals and the analytical curves obtained by LS AAS without and with D₂ BC, and with HR-CS AAS without and with automatic correction for continuous background absorption, and also with least-squares background correction for molecular absorption with rotational fine structure were compared. The molecular absorption due to the suboxide PO that exhibits pronounced fine structure could not be corrected by the D₂ BC system, causing significant overcorrection. Among the investigated chemical modifiers, NaF, La, Pd and Pd + Ca, the Pd modifier resulted in the best agreement of the results obtained with LS AAS and HR-CS AAS. However, a 15% to 100% higher sensitivity, expressed as slope of the analytical curve, was obtained for LS AAS compared to HR-CS AAS, depending on the modifier. Although no final proof could be found, the most likely explanation is that this artifact is caused by a yet unidentified phosphorus species that causes a spectrally continuous absorption, which is corrected without problems by HR-CS AAS, but which is not recognized and corrected by the D₂ BC system of LS AAS.     

Investigation of phosphorus atomization using high-resolution continuum source electrothermal atomic absorption spectrometry

The atomization of phosphorus in electrothermal atomic absorption spectrometry has been investigated using a high-resolution continuum source atomic absorption spectrometer and atomization from a graphite platform as well as from a tantalum boat inserted in a graphite tube. A two-step atomization mechanism is proposed for phosphorus, where the first step is a thermal dissociation, resulting in a fast atomization signal early in the atomization stage, and the second step is a slow release of phosphorus atoms from the graphite tube surface following the adsorption of molecular phosphorus at active sites of the graphite surface. Depending on experimental conditions only one of the mechanisms or both might be active. In the absence of a modifier and with atomization from a graphite or tantalum platform the second mechanism appears to be dominant, whereas in the presence of sodium fluoride as a modifier both mechanisms are observed. Intercalation of phosphorus into the graphite platform in the condensed phase has also been observed; this phosphorus, however, appears to be permanently trapped in the structure of the graphite and does not contribute to the absorption signal.     

Determination of cadmium in coal using solid sampling graphite furnace high-resolution continuum source atomic absorption spectrometry

This work describes the development of a method to determine cadmium in coal, in which iridium is used as a permanent chemical modifier and calibration is performed against aqueous standards by high-resolution continuum source atomic absorption spectrometry (HR-CS AAS). This new instrumental concept makes the whole spectral environment in the vicinity of the analytical line accessible, providing a lot more data than just the change in absorbance over time available from conventional instruments. The application of Ir (400 g) as a permanent chemical modifier, thermally deposited on the pyrolytic graphite platform surface, allowed pyrolysis temperatures of 700 °C to be used, which was sufficiently high to significantly reduce the continuous background that occurred before the analyte signal at pyrolysis temperatures <700 °C. Structured background absorption also occurred after the analyte signal when atomization temperatures of >1600 °C were used, which arose from the electron-excitation spectrum (with rotational fine structure) of a diatomic molecule. Under optimized conditions (pyrolysis at 700 °C and atomization at 1500 °C), interference-free determination of cadmium in seven certified coal reference materials and two real samples was achieved by direct solid sampling and calibrating against aqueous standards, resulting in good agreement with the certified values (where available) at the 95% confidence level. A characteristic mass of 0.4 pg and a detection limit of 2 ng g^–1, calculated for a sample mass of 1.0 mg coal, was obtained. A precision (expressed as the relative standard deviation, RSD) of <10% was typically obtained when coal samples in the mass range 0.6–1.2 mg were analyzed.Dedicated to the memory of Wilhelm Fresenius     

Method development for the determination of cadmium in fertilizer samples using high-resolution continuum source graphite furnace atomic absorption spectrometry and slurry sampling

The determination of cadmium (Cd) in fertilizers is of major interest, as this element can cause growth problems in plants, and also affect animals and humans. High-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) with charge-coupled device (CCD) array detection overcomes several of the limitations encountered with conventional line source AAS, especially the problem of accurate background measurement and correction. In this work an analytical method has been developed to determine Cd in fertilizer samples by HR-CS GF AAS using slurry sampling. Both a mixture of 10 μg Pd + 6 μg Mg in solution and 400 μg of iridium as permanent modifier have been investigated and aqueous standards were used for calibration. Pyrolysis and atomization temperatures were 600 °C and 1600 °C for the Pd-Mg modifier, and 500 °C and 1600 °C for Ir, respectively. The results obtained for Cd in the certified reference material NIST SRM 695 (Trace Elements in Multi-Nutrient Fertilizer) of 16.7 ± 1.3 μg g⁻¹ and 16.4 ± 0.75 μg g⁻¹ for the Pd-Mg and Ir modifier, respectively, were statistically not different from the certified value of 16.9 ± 0.2 μg g⁻¹ on a 95% confidence level; however, the results obtained with the Ir modifier were significantly lower than those for the Pd-Mg modifier for most of the samples. The characteristic mass was 1.0 pg for the Pd-Mg modifier and 1.1 pg Cd for the Ir modifier, and the correlation coefficients (R²) of the calibration were > 0.99. The instrumental limits of detection were 7.5 and 7.9 ng g⁻¹, and the limits of quantification were 25 and 27 ng g⁻¹ for Pd-Mg and Ir, respectively, based on a sample mass of 5 mg. The cadmium concentration in the investigated samples was between 0.07 and 5.5 μg g⁻¹ Cd, and hence below the maximum value of 20 μg g⁻¹ Cd permitted by Brazilian legislation.     

Internal standardization and least-squares background correction in high-resolution continuum source flame atomic absorption spectrometry to eliminate interferences on determination of Pb in phosphoric acid

In this work the least-squares background correction (LSBC) and internal standardization (IS) techniques were combined to eliminate spectral and transport interferences in the determination of Pb in phosphoric acid by high-resolution continuum source atomic absorption spectrometry (HR-CS AAS). Blanks, samples and reference solutions [0.10–1.00 mg L^− 1 Pb in 1% (v/v) HNO₃] were spiked with 4.00 mg L^− 1 Co used as internal standard. For absorbance measurements at the wavelength integrated absorbance equivalent to 9 pixels, correlations between the ratio of absorbance of Pb to absorbance of Co and the analyte concentration were close to 0.9992. Relative standard deviations of measurements varied from 0.6 to 4% and 1 to 7% (n = 12) without and with IS/LSBC techniques, respectively. Recoveries for Pb spikes were in the 96–104% and 76–180% range with and without IS/LSBC, respectively. The limit of detection improved with IS/LSBC techniques. Accuracy of the proposed method was checked for the determinations of Pb in commercial phosphoric acid samples and results obtained with IS were better than those without IS.     

Determination of iodine via the spectrum of barium mono-iodide using high-resolution continuum source molecular absorption spectrometry in a graphite furnace

Molecular absorption spectra of the diatomic molecules AlI, GaI, InI, TlI, MgI, CaI, SrI and BaI, generated in a graphite furnace, were studied using a high-resolution echelle spectrometer with the aim of finding a simple, reliable and sensitive analytical method for the determination of iodine. Among them, the barium mono-iodide (BaI) was found to have the strongest absorption bands around 538 nm and 560 nm, each of them consisting of a series of well-resolved rotational lines with half-widths of about 40–50 pm. The strongest BaI line, the band head at 538.308 nm has been evaluated systematically for its analytical use for the determination of iodine. High concentrations of hydrochloric acid (or chloride), hydrofluoric acid (or fluoride), iron, potassium and sodium resulted in significant reduction of the BaI molecular absorption. Apart from this, no other serious spectral or non-spectral interference has been observed. Different chemical forms of iodine, such as iodide, iodate and organically bound iodine produced identical BaI absorption sensitivity. The detection limit for iodine was 600 pg, and the calibration curve was linear up to 250 ng iodine. Two real samples with different chemical forms of iodine were analyzed using the proposed method. One sample was an iodide pill with a specified iodide content of 200 mg, the other one was a thyroid hormone pill with a specified content of 63.5 mg. The results were in good or satisfactory agreement with those of independent methods, the potentiometric titration and the inductively coupled plasma time-of-flight mass spectrometry (ICP-ToF-MS); the deviations were 2% and 8% for the iodide and the thyroid hormone sample, respectively. The relative standard deviation of the analytical results (n = 3) was below 2%.     

Progress in direct solid sampling analysis using line source and high-resolution continuum source electrothermal atomic absorption spectrometry

The literature about direct solid sample analysis of the past 10–15 years using electrothermal atomic absorption spectrometry has been reviewed. It was found that in the vast majority of publications aqueous standards were reported as having been used for calibration after careful program optimization. This means the frequently expressed claim that certified reference materials with a matrix composition and analyte content close to that of the sample have to be used for calibration in solid sample analysis is not confirmed in the more recent literature. There are obviously limitations, and there are examples in the literature where even calibration with certified reference materials did not lead to accurate results. In these cases the problem is typically associated with spectral interferences that cannot be corrected properly by the systems available for conventional line source atomic absorption spectrometry, including Zeeman-effect background correction. Using high-resolution continuum source atomic absorption spectrometry, spectral interferences become visible owing to the display of the spectral environment at both sides of the analytical line at high resolution, which makes program optimization straightforward. Any spectrally continuous background absorption is eliminated automatically, and even rapidly changing background absorption does not cause any artifacts, as measurement and correction of background absorption are truly simultaneous. Any kind of fine-structured background can be eliminated by “subtracting” reference spectra using a least-squares algorithm. Aqueous standards are used for calibration in all published applications of high-resolution continuum source atomic absorption spectrometry to direct solid sample analysis. This contribution is based on a presentation given at the Colloquium for Analytical Atomic Spectroscopy (CANAS ‘07) held March 18–21, 2007 in Constance, Germany.     

Unusual calibration curves observed for iron using high-resolution continuum source graphite furnace atomic absorption spectrometry

The simultaneous determination of cadmium and iron in plant and soil samples has been investigated using high-resolution continuum source graphite furnace atomic absorption spectrometry. The primary cadmium resonance line at 228.802 nm and an adjacent secondary iron line at 228.726 nm, which is within the spectral interval covered by the charge-coupled device (CCD) array detector, have been used for the investigations. Due to the very high iron content in most of the soil samples the possibility has been investigated to reduce the sensitivity and extend the working range by using side pixels for measurement at the line wings instead of the line core. It has been found that the calibration curves measured at all the analytically useful pixels of this line consisted of two linear parts with distinctly different slopes. This effect has been independent of the positioning of the wavelength, i.e., if the Cd line or the Fe line was in the center of the CCD array. The most likely explanation for this unusual behavior is a significant difference between the instrument width Δλ_Instr and the absorption line width Δλ_Abs, which is quite pronounced in the case of Fe. Using both parts of the calibration curves and simultaneous measurement at the line center and at the wings made it possible to extend the working range for the iron determination to more than three orders of magnitude.     

High-resolution continuum source electrothermal atomic absorption spectrometry — An analytical and diagnostic tool for trace analysis

The literature about applications of high-resolution continuum source atomic absorption spectrometry (HR-CS AAS) with electrothermal atomization is reviewed. The historic development of HR-CS AAS is briefly summarized and the main advantages of this technique, mainly the ‘visibility’ of the spectral environment around the analytical line at high resolution and the unequaled simultaneous background correction are discussed. Simultaneous multielement CS AAS has been realized only in a very limited number of cases. The direct analysis of solid samples appears to have gained a lot from the special features of HR-CS AAS, and the examples from the literature suggest that calibration can be carried out against aqueous standards. Low-temperature losses of nickel and vanadyl porphyrins could be detected and avoided in the analysis of crude oil due to the superior background correction system. The visibility of the spectral environment around the analytical line revealed that the absorbance signal measured for phosphorus at the 213.6 nm non-resonance line without a modifier is mostly due to the PO molecule, and not to atomic phosphorus. The future possibility to apply high-resolution continuum source molecular absorption for the determination of non-metals is discussed.     

On the possibilities of high-resolution continuum source graphite furnace atomic absorption spectrometry for the simultaneous or sequential monitoring of multiple atomic lines

This paper explores the potential of commercially available high-resolution continuum source graphite furnace atomic absorption spectrometry instrumentation for the simultaneous or sequential monitoring of various atomic lines, in an attempt to highlight the analytical advantages that can be derived from this strategy. In particular, it is demonstrated how i) the monitoring of multiplets may allow for the simple expansion of the linear range, as shown for the measurement of Ni using the triplet located in the vicinity of 234.6 nm; ii) the use of a suitable internal standard may permit improving the precision and help in correcting for matrix-effects, as proved for the monitoring of Ni in different biological samples; iii) direct and multi-element analysis of solid samples may be feasible on some occasions, either by monitoring various atomic lines that are sufficiently close (truly simultaneous monitoring, as demonstrated in the determination of Co, Fe and Ni in NIST 1566a Oyster tissue) or, alternatively, by opting for a selective and sequential atomization of the elements of interest during every single replicate. Determination of Cd and Ni in BCR 679 White cabbage is attempted using both approaches, which permits confirming that both methods can offer very similar and satisfactory results. However, it is important to stress that the second approach provides more flexibility, since analysis is no longer limited to those elements that show very close atomic lines (closer than 0.3 nm in the ultraviolet region) with a sensitivity ratio similar to the concentration ratio of the analytes in the samples investigated.     

Direct and simultaneous determination of Cr and Fe in crude oil using high-resolution continuum source graphite furnace atomic absorption spectrometry

A simple, fast and sensitive direct method for the simultaneous determination of Cr and Fe in crude oil samples is proposed using high-resolution continuum source graphite furnace atomic absorption spectrometry. No sample preparation is used except for a 10-minute homogenization in an ultrasonic bath. Aliquots of 0.1–4 mg of the samples are weighed onto solid sampling platforms and analyzed directly using aqueous standards for calibration. The simultaneous determination was possible because there is a secondary Fe line at 358.120 nm in the vicinity of the most sensitive Cr line at 357.868 nm, and both absorption lines were within the wavelength interval covered by the linear charge-coupled device array detector. It has also been of advantage that the sensitivity ratio between the two analytical lines corresponded roughly to the concentration ratio of the two elements found in crude oil, and that both analytes have very similar volatility, so that no compromises had to be made regarding pyrolysis and atomization temperatures. Two oil reference materials have been analyzed and the results were in agreement with the certified or reported values. Characteristic masses of 3.6 pg and 0.5 ng were obtained for Cr and Fe, respectively. The limits of detection (3σ, n = 10) were 1 µg kg^− 1 for Cr and 0.6 mg kg^− 1 for Fe, and the precision, expressed as the relative standard deviation, ranged from 4 to 20%, which is often acceptable for a rapid direct analytical procedure. Five crude oils samples were analyzed.     

Determination of aluminum in highly concentrated iron samples: Study of interferences using high-resolution continuum source atomic absorption spectrometry

High-resolution continuum source atomic absorption spectrometry (HR-CS AAS) has been used to investigate spectral and non-spectral interferences found with a conventional line source atomic absorption spectrometer in the determination of aluminum in pharmaceutical products containing elevated iron and sugar concentrations. A transversely heated graphite furnace was used as the atomizer in both spectrometers. The two most sensitive aluminum lines at 309.3 nm and 396.2 nm were investigated and it was found that an iron absorption line at 309.278 nm, in the vicinity of the aluminum line at 309.271 nm, could be responsible for some spectral interference. The simultaneous presence of iron and the organic components of the matrix were responsible for radiation scattering, causing high continuous and also structured background absorption at both wavelengths. The aluminum and iron absorption could not be separated in time, i.e., the iron interference could not be eliminated by optimizing the graphite furnace temperature program. However, an interference-free determination of aluminum was possible carrying out the measurements with HR-CS AAS at 396.152 nm after applying least squares background correction for the elimination of the structured background. Analytical working range and other figures of merit were determined and are presented for both wavelengths using peak volume registration (center pixel ± 1) and the center pixel only. Limits of detection and characteristic masses ranged from 1.1 to 2.5 pg and 13 to 43 pg, respectively. The method was used for the determination of the aluminum contamination in pharmaceutical formulations for iron deficiency treatment, which present iron concentrations from 10 to 50 g l^− 1. Spike recoveries from 89% to 105% show that the proposed method can be satisfactorily used for the quality control of these formulations.     

Simultaneous determination of Cd and Fe in sewage sludge by high-resolution continuum source electrothermal atomic absorption spectrometry with slurry sampling

This work describes the method development for the simultaneous determination of Cd and Fe using the main resonance line of Cd at 228.802 nm and a secondary Fe line at 228.725 nm, and high-resolution continuum source electrothermal atomic absorption spectrometry (HR-CS ET AAS). Two certified reference materials and two ‘real’ samples of industrial and domestic sewage sludge have been analyzed as slurries prepared in a mixture of HF and HNO₃. The simultaneous determination has been performed using a short temperature program of only 30 s, without a pyrolysis stage and with two atomization stages, at 1300 °C and 2300 °C, taking into consideration the significantly different thermal characteristics of Cd and Fe. Structured background, which is likely due to the presence of one or more diatomic molecules, including SiO, has been detected. However, there has been no spectral overlap between molecular bands and the atomic lines of Cd and Fe, making possible the determination to be carried out using only automatic correction for continuous background. Calibration against aqueous standards lead to good agreement between certified or informed values and the determined values, at a statistical confidence level of 95%; recovery tests were performed for real samples, resulting in recoveries ranging from 90 to 105%. Detection limits of 0.03 and 90 µg g^{− 1} for Cd and Fe, respectively, have been obtained, which are adequate for the purpose.     

Development of a simple method for the determination of nitrite and nitrate in groundwater by high-resolution continuum source electrothermal molecular absorption spectrometry

In this work, it was developed a method for the determination of nitrite and nitrate in groundwater by high-resolution continuum source electrothermal molecular absorption spectrometry of NO produced by thermal decomposition of nitrate in a graphite furnace. The NO line at 215.360 nm was used for all analytical measurements and the signal obtained by integrated absorbance of three pixels. A volume of 20 μL of standard solution or groundwater sample was injected into graphite furnace and 5 μL of a 1% (m/v) Ca solution was co-injected as chemical modifier. The pyrolisis and vaporization temperatures established were of 150 and 1300 °C, respectively. Under these conditions, it was observed a difference of thermal stability among the two nitrogen species in the presence of hydrochloric acid co-injected. While that the nitrite signal was totally suppressed, nitrate signal remained nearly stable. This way, nitrogen can be quantified only as nitrate. The addition of hydrogen peroxide provided the oxidation of nitrite to nitrate, which allowed the total quantification of the species and nitrite obtained by difference. A volume of 5 μL of 0.3% (v/v) hydrochloric acid was co-injected for the elimination of nitrite, whereas that hydrogen peroxide in the concentration of 0.75% (v/v) was added to samples or standards for the oxidation of nitrite to nitrate. Analytical curve was established using standard solution of nitrate. The method described has limits of detection and quantification of 0.10 and 0.33 μg mL⁻¹ of nitrogen, respectively. The precision, estimated as relative standard deviation (RSD), was of 7.5 and 3.8% (n = 10) for groundwater samples containing nitrate–N concentrations of 1.9 and 15.2 μg mL⁻¹, respectively. The proposed method was applied to the analysis of 10 groundwater samples and the results were compared with those obtained by ion chromatography method. In all samples analyzed, the concentration of nitrite–N was always below of the limit of quantification of both the methods. The concentrations of nitrate–N varied from 0.58 to 15.5 μg mL⁻¹. No significant difference it was observed between the results obtained by both methods for nitrate–N, at the 95% confidence level.     

Solid sampling-graphite furnace atomic absorption spectrometry for the direct determination of silver at trace and ultratrace levels

In this work, the possibilities of solid sampling-graphite furnace atomic absorption spectrometry for the direct determination of silver in solid samples of very different nature (a biological sample, a soil, an ore concentrate and a polymer) and showing substantial differences in their analyte content (from approximately, 40 ng g⁻¹ up to 350 μg g⁻¹) have been evaluated, the goal always being to develop fast methods, only relying on the use of aqueous standards for calibration.Different factors had to be taken into account in order to develop suitable procedures for all the samples under investigation. Among the most important ones, the following can be mentioned: (i) optimization of the temperature program in order to selectively atomize the analyte; (ii) the use of chemical modifiers (such as Pd or HNO₃), depending on the sample characteristics; (iii) appropriate wavelength, argon flow and sample mass selection (depending on the analyte content); (iv) the use of 3-field mode Zeeman-effect background correction in order to further expand the linear range up to 1000 ng of Ag, which was needed for analysis of the sample showing the highest Ag content (polypropylene).The procedures finally proposed show interesting features for the determination of silver in solid samples: the advantage of using aqueous standard solutions for calibration, a high sample throughput (approximately, 15 min per sample), a low detection limit (2 ng g⁻¹), sufficient precision (R.S.D. values in the vicinity of 10%) and a reduced risk of analyte losses and contamination.     

A practical method for the determination of sulphur in coal samples by high-resolution continuum source flame atomic absorption spectrometry

Sulphur in coal was determined using a high-resolution continuum source flame atomic absorption spectrophotometer (HR-CS-FAAS) with actylene/air flame. The C-S absorption band at 258.056 nm was found the most suitable analytical line with respect to sensitivity and spectral interferences. The instrumental parameters were optimized. The coal samples were dried and dissolved using microwave-assisted digestion technique. The validity of the method was tested using standard reference material and certified values were found in the limits of 95% confidence level. Since the concentrations of matrix elements of coal other than carbon are low enough not to cause any spectral interferences, the linear calibration method was applied in all quantifications without any problem. The calibration standards were prepared in sulphuric acid. The method was accurate, fast, simple and sensitive. The limit of detection (LOD, 3δ, N = 10) and the limit of quantification (LOQ, 10δ, N = 10) were found to be 0.01 and 0.03% (w/w), respectively. The sulphur concentrations of various kinds of the coal samples received around Turkey were determined. The sulphur contents of the coal samples were ranged from ≤LOQ to 1.2%.     

Slurry sampling and high-resolution continuum source flame atomic absorption spectrometry using secondary lines for the determination of Ca and Mg in dairy products

The present paper proposes a simple and fast analytical procedure for the sequential multi-element determination of Ca and Mg in dairy products employing sampling slurry and high resolution-continuum source flame atomic absorption spectrometry (HR-CS FAAS). Considering the high concentration of these species in these matrices, the analytical measurements were carried out at the secondary lines of 239.856 and 202.852 for Ca and Mg, respectively. The experimental conditions established for the preparation of the slurries during the optimization step were: 2.0 mol L^{− 1} hydrochloric acid, sonication time of 20 min and sample mass of 1.0 g for a slurry volume of 25 mL. Experiments demonstrated that the analytical curves can be established using the external calibration technique employing aqueous standards. The method allows the determination of Ca and Mg with limits of quantification of 0.038 and 0.016 mg g^{− 1}, respectively. The precision was evaluated under reproducibility and repeatability conditions and expressed as relative standard deviation. The results varied from 2.7 to 2.9% (all tests with n = 10) and using a yogurt sample containing Ca and Mg concentrations of 1.40 and 0.13 mg g^{− 1}, respectively.The accuracy was confirmed by the analysis of a certified reference material of non-fat milk powder furnished by the National Institute of Standard and Technology. The proposed method was applied for the determination of Ca and Mg in yogurt, cow milk and milk powder samples. The samples were also analyzed after complete acid digestion and Ca and Mg determination by HR-CS FAAS. No statistical difference was observed between the results obtained by both of the procedures performed.     

Determination of heavy metals in activated charcoals and carbon black for Lyocell fiber production using direct solid sampling high-resolution continuum source graphite furnace atomic absorption and inductively coupled plasma optical emission spectrometry

Reactivity and concentration of additives, especially activated charcoal, employed for the Lyocell process, enhance the complexity of reactions in cellulose/N-methylmorpholine-N-oxide monohydrate solutions. Analytical control of the starting materials is a basic requirement to know the concentration of heavy metals, which are potential initiators of autocatalytic reactions. Seven activated charcoal and two carbon black samples have been analyzed regarding their content of seven elements, Cr, Cu, Fe, Mn, Mo, Ni and V using direct solid sampling high-resolution continuum source graphite furnace AAS (SS-HR-CS GF AAS) and inductively coupled plasma optical emission spectrometry (ICP OES) after microwave-assisted acidic digestion as a reference method. The limits of detection of the former technique are 1-2 orders of magnitude lower than those of ICP OES and comparable to those of more sophisticated techniques. For iron the working range of HR-CS GF AAS has been expanded by simultaneous measurement at two secondary absorption lines (344,099 nm and 344,399 nm). Partial least-squares regression between measured and calculated temperatures for beginning exothermicity (T_on) has been used to investigate the prediction capability of the investigated techniques. Whereas the ICP OES measurements for seven elements resulted in an error of prediction of 3.67%, the results obtained by SS-HR-CS GF AAS exhibited a correlation coefficient of 0.99 and an error of prediction of only 0.68%. Acceptable correlation has been obtained with the latter technique measuring only three to four elements.     

Feasibility of employing permanent chemical modifiers for the determination of cadmium in coal using slurry sampling electrothermal atomic absorption spectrometry

Iridium and ruthenium, alone and in combination with tungsten, thermally deposited on the platform of a transversely heated graphite tube, were investigated for their suitability as permanent chemical modifiers for the determination of cadmium in coal slurries by electrothermal atomic absorption spectrometry (ET AAS). The conventional mixed palladium and magnesium nitrates (Pd–Mg) modifiers, added in solution, were also investigated for comparison. The latter one showed the best performance for aqueous solutions, and the mixed W–Ir and W–Ru permanent modifiers had the lowest stabilizing power. All of the investigated modifiers lost some of their stabilizing power when coal slurries were investigated. The Pd–Mg modifier, pure Ir and Ru, and a mixture of 300 μg W + 200 μg Ir could stabilize Cd at least to a pyrolysis temperature of 600 °C, whereas all the other combinations already failed at temperatures above 500–550 °C. Additional investigations of the supernatant liquid of the slurries supported the assumption that the high acid concentration of the slurries and/or a concomitant leaching out of the coal might be responsible for the reduced stabilizing power of the modifiers. The maximum applicable pyrolysis temperature of 600 °C was not sufficient to reduce the background absorption to a manageable level in the majority of the coal samples. High-resolution continuum source ET AAS revealed that the continuous background absorption was exceeding values of A = 2, and was overlapping with the analyte signal. Although the latter technique could correct for this background absorption, some analyte was apparently lost with the rapidly vaporizing matrix so that the method could not be considered to be rugged. A characteristic mass of 1.0 pg and a detection limit of 0.6 ng g^− 1 could be obtained under these conditions.     

Fast sequential multi-element determination of Ca,Mg, K,Cu, Fe,Mn and Zn for foliar diagnosis using high-resolution continuum source flame atomic absorption spectrometry: Feasibility of secondary lines,side pixel registration and least-squares background correction

The fast sequential multi-element determination of Ca, Mg, K, Cu, Fe, Mn and Zn in plant tissues by high-resolution continuum source flame atomic absorption spectrometry is proposed. For this, the main lines for Cu (324.754 nm), Fe (248.327 nm), Mn (279.482 nm) and Zn (213.857 nm) were selected, and the secondary lines for Ca (239.856 nm), Mg (202.582 nm) and K (404.414 nm) were evaluated. The side pixel registration approach was studied to reduce sensitivity and extend the linear working range for Mg by measuring at wings (202.576 nm; 202.577 nm; 202.578 nm; 202.580 nm; 202.585 nm; 202.586 nm; 202.587 nm; 202.588 nm) of the secondary line. The interference caused by NO bands on Zn at 213.857 nm was removed using the least-squares background correction. Using the main lines for Cu, Fe, Mn and Zn, secondary lines for Ca and K, and line wing at 202.588 nm for Mg, and 5 mL min^− 1 sample flow-rate, calibration curves in the 0.1–0.5 mg L^− 1 Cu, 0.5–4.0 mg L^− 1 Fe, 0.5–4.0 mg L^− 1 Mn, 0.2–1.0 mg L^− 1 Zn, 10.0–100.0 mg L^− 1 Ca, 5.0–40.0 mg L^− 1 Mg and 50.0–250.0 mg L^− 1 K ranges were consistently obtained. Accuracy and precision were evaluated after analysis of five plant standard reference materials. Results were in agreement at a 95% confidence level (paired t-test) with certified values. The proposed method was applied to digests of sugar-cane leaves and results were close to those obtained by line-source flame atomic absorption spectrometry. Recoveries of Ca, Mg, K, Cu, Fe, Mn and Zn in the 89–103%, 84–107%, 87–103%, 85–105%, 92–106%, 91–114%, 96–114% intervals, respectively, were obtained. The limits of detection were 0.6 mg L^− 1 Ca, 0.4 mg L^− 1 Mg, 0.4 mg L^− 1 K, 7.7 µg L^− 1 Cu, 7.7 µg L^− 1 Fe, 1.5 µg L^− 1 Mn and 5.9 µg L^− 1 Zn.