Graphite Furnace Molecular Absorption Spectrometry Research Articles

Determination of Fluorine by Ion-Selective Electrode and High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry with Respect to Animal Feed Safety.

Fluorine, depending on its concentration and chemical form, is essential or toxic to humans and animals. Therefore, it is crucial to be able to determine it reliably. In this study, fluorine was determined in animal feed after extraction with HCl (gastric juice simulation). The standard potentiometric method with a fluoride-selective electrode (ISE) and newly developed high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS GFMAS) method was applied. Feed samples turned out to be a challenge for HR-CS GFMAS. Chemical interferences (formation of competing molecules, CaF, GaCl, and GaP, instead of the target GaF molecule) and spectral effects (including a phosphorous molecule spectrum and atomic lines) were identified. An additional difficulty was caused by reagent contamination with F and memory effects. Difficulties were eliminated/reduced. The quality of ISE analysis was multi-directionally verified (including comprehensive proficiency testing). A risk of inaccuracy at low F concentration, where the calibration relationship is nonlinear, was investigated. The results of both methods were consistent, which confirms the accuracy of the methods and informs that the extracted fluorine is in fluoride form. The results of extensive ISE tests conducted in Poland in 2021-2023 have shown that, in most cases, the fluoride content is significantly lower than the threshold values.

Second-order calibration high-resolution continuum source graphite furnace molecular absorption spectrometry-based determination of bromine and fluorine

In this study, we report the simultaneous determination of bromine and fluorine using Second-Order Calibration High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry (HR CS MAS). The instrumental data acquired correspond to the time versus wavelength matrix per sample that were analyzed using Parallel Factor Analysis (PARAFAC), along with Unfold and N-way Partial Least Squares combined with a post-calibration step known as Residual Bilinearization (U and N PLS/RBL). Despite the significant difference in sensitivity between bromine and fluorine, all approaches provided reasonably accurate results when predicting both analytes in synthetic mixtures within a controlled environment. The relative prediction error (REP) values for bromine were 29.8 % (PARAFAC), 23.6 % (N-PLS/RBL), and 13.1 % (U-PLS/RBL), while for fluorine, the REP values were 3.4 % (PARAFAC), 3.5 % (N-PLS/RBL), and 3.2 % (U-PLS/RBL). When applying this approach to predict unknown samples, a comparison was made between the estimated nominal concentrations of fluorine and bromine obtained using either a reference method or based on labeled values or spiked mass, and those obtained using the proposed method. It was observed that PARAFAC was unable to predict the samples accurately, whereas the REP values for the prediction of bromine and fluorine using N-PLS/RBL and U-PLS/RBL methods were 19.3 %/19.2 % and 13.6 %/13.1 %, respectively.

General Applicability of High-Resolution Continuum-Source Graphite Furnace Molecular Absorption Spectrometry to the Quantification of Oligopeptides Using the Example of Glutathione

This communication introduces the first-time application of high-resolution continuum-source molecular absorption spectrometry (HR CS MAS) for the quantification of a peptide. The graphite furnace technique was employed and the tripeptide glutathione (GSH) served as a model compound. Based on measuring sulfur in terms of carbon monosulfide (CS), a method was elaborated to analyze aqueous solutions of GSH. The most prominent wavelength of the CS molecule occurred at 258.0560 nm and was adduced for monitoring. The methodological development covered the optimization of the pyrolysis and vaporization temperatures. These were found optimally to be 250 °C and 2250 °C, respectively. Moreover, the effect of modifiers (zirconium, calcium, magnesium, palladium) on the absorption signals was investigated. The best results were obtained after permanent coating of the graphite tube with zirconium (total amount of 400 μg) and adding a combination of palladium (10 µL, 10 g L−1) and calcium (2 µL, 1 g L−1) as a chemical modifier to the probes (10 µL). Aqueous standard samples of GSH were used for the calibration. It showed a linear range of 2.5–100 µg mL−1 sulfur contained in GSH with a correlation coefficient R2 > 0.997. The developed method exhibited a limit of detection (LOD) and quantification (LOQ) of 2.1 µg mL−1 and 4.3 µg mL−1 sulfur, respectively. The characteristic mass accounted for 5.9 ng sulfur. The method confirmed the general suitability of MAS for the analysis of an oligopeptide. Thus, this study serves as groundwork for further development in order to extend the application of classical atomic absorption spectrometry (AAS).

Determination of Chlorine in Plastics via SrCl by Solid-Sampling High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry

Solid sampling high resolution continuum source molecule absorption spectrometry (SS-HR-CS MAS) was applied for the determination of chlorine in plastic using the strontium monochloride (SrCl) molecule. For this purpose, 10 µL of 20 g L−1 strontium (prepared from Sr(NO3)2) solution were pipetted with aqueous Cl standards or 0.05 to 4 mg of slivered plastic samples on a platform and introduced into the furnace. Chlorine was determined with the molecular absorption of SrCl at 635.862 nm using 1100 °C and 2200 °C for the pyrolysis and vaporization temperatures, respectively. Aqueous standards were used for calibration. The accuracy of the method was evaluated using a certified polyethylene reference material. The limit of detection and characteristic mass values of the method were 2.5 ng and 0.4 ng, respectively. The chlorine concentrations in various polyethylene beverage containers were determined.

Formation of calcium monofluoride in graphite furnace molecular absorption spectrometry, part 2: interference mechanisms of chloride, bromide and sulfate salts

In this study, the interference mechanisms of chloride, bromide and sulfate together with sodium in the determination of CaF by high resolution continuum source molecular absorption spectrometry were investigated.

Application of Solid Sampling for the Determination of Total Fluorine in Fish and Seafood by High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry

ABSTRACTTotal fluorine concentrations in some fish species and seafood such as mussels, squid (calamary), and shrimp were determined using the molecular absorption of calcium monofluoride (CaF) generated in a graphite furnace using a high-resolution continuum source atomic absorption spectrometer and direct solid sampling. The fish fillets and seafood were dried at 110°C, minced finely, put on the platform using masses less than 1.2 mg, and introduced to the graphite furnace with 20 µg of calcium by a solid sampling accessory. The effects of CaF wavelength, graphite furnace program, amount of sample introduced to the furnace, the use of modifier on the determination of fluorine were investigated and optimized. The absolute limit of detection and characteristic mass of the method were 0.28 and 0.14 ng of fluorine, respectively. By applying the optimized parameters, the concentrations of fluorine in various fish species and seafood were determined.

Formation of calcium monofluoride in graphite furnace molecular absorption spectrometry, part I: interference mechanisms of competitive metals Ga, Al, Ba, and Sr

In this study, the formation mechanisms of CaF and the interference mechanisms of Al, Ba, Ga and Sr on the determination of F via CaF were studied.

Determination of Chlorine in Crude Oil by High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry Using AlCl, InCl, and SrCl Molecules

In this work, high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS) using AlCl, InCl, and SrCl molecules was proposed for direct Cl determination in crude oil. Crude oil analysis was performed by pipetting masses of crude oil directly on the graphite platform. Calibration was performed using aqueous standard solutions containing chlorine. A solution containing Sr2+ ions should be used to increase the sensitivity for AlCl and InCl molecules. For SrCl, only Sr2+ solution was used and the graphite platform should be covered with a Zr permanent modifier. Accuracy was evaluated using certified reference material (NIST 1634c, fuel oil) and also by comparison of results obtained with HR-CS GF MAS to those obtained by microwave-induced combustion (MIC), microwave-assisted extraction (MAE), ASTM D6470-99, and neutron activation analysis (NAA). Significant differences were not observed by comparison of results obtained by HR-CS GF MAS to the certified reference value and...

Determination of Total Sulfur in Food Samples by Solid Sampling High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry

The determination of sulfur in food samples via the rotational molecular absorption of carbon monosulfide (CS) was performed using a solid sampling high-resolution continuum source electrothermal atomic absorption spectrophotometer (SS-HR-CS-ETAAS). In the presence of plenty of carbon in the graphite furnace as well as in food samples, CS was formed in the gas phase without the addition of any molecule forming element externally. The effects of the wavelength selected to detect CS, graphite furnace program, amount of sample, coating of the graphite tube and platform with Ir, and the use of a Pd modifier on the accuracy, precision, and sensitivity were investigated and optimized. Sulfur was determined in an iridium-coated graphite tube/platform at 258.056 nm by applying a pyrolysis temperature of 1000 °C and a molecule forming temperature of 2400 °C. The calibration curve prepared from Na2S was linear between 0.01 μg (LOQ) and 10 μg of S. The accuracy of the method was tested by analyzing certified reference spinach and milk powder samples by applying a linear calibration technique prepared from aqueous standard. The results were in good agreement with certified values. The limit of detection and characteristic mass of the method were 3.5 and 8.1 ng of S, respectively. By applying the optimized parameters, the concentrations of S in onion and garlic samples were determined.

Feasibility of high-resolution continuum source molecular absorption spectrometry in flame and furnace for sulphur determination in petroleum products

For the first time, high-resolution molecular absorption spectrometry with a high-intensity xenon lamp as radiation source has been applied for the determination of sulphur in crude oil and petroleum products. The samples were analysed as xylene solutions using vaporisation in acetylene-air flame or in an electrothermally heated graphite furnace. The sensitive rotational lines of the CS molecule, belonging to the ∆ν = 0 vibrational sequence within the electronic transition X 1∑ + → A 1П, were applied. For graphite furnace molecular absorption spectrometry, the Pd + Mg organic modifier was selected. Strong interactions with Pd atoms enable easier decomposition of sulphur-containing compounds, likely through the temporal formation of Pd xS y molecules. At the 258.056 nm line, with the wavelength range covering central pixel ± 5 pixels and with application of interactive background correction, the detection limit was 14 ng in graphite furnace molecular absorption spectrometry and 18 mg kg −1 in flame molecular absorption spectrometry. Meanwhile, application of 2-points background correction found a characteristic mass of 12 ng in graphite furnace molecular absorption spectrometry and a characteristic concentration of 104 mg kg −1 in flame molecular absorption spectrometry. The range of application of the proposed methods turned out to be significantly limited by the properties of the sulphur compounds of interest. In the case of volatile sulphur compounds, which can be present in light petroleum products, severe difficulties were encountered. On the contrary, heavy oils and residues from distillation as well as crude oil could be analysed using both flame and graphite furnace vaporisation. The good accuracy of the proposed methods for these samples was confirmed by their mutual consistency and the results from analysis of reference samples (certified reference materials and home reference materials with sulphur content determined by X-ray fluorescence spectrometry).

Electrothermal volatilization flame and graphite furnace atomic absorption spectrometric investigations on the determination of calcium in gallium

Electrothermal volatilization flame atomic absorption spectrometry (ETV-FAAS) was used for element-specific detection in the vapour evolved during heating of a graphite furnace (GF). The studies, combined with graphite furnace atomic absorption spectrometry (GFAAS) and GF molecular absorption spectrometry (GFMAS) were intended to provide a better understanding of the volatilization mechanisms of calcium and gallium. Both elements were applied as minor and major components in nitric acid, hydrochloric acid and ammonium chloride media. Low heating rates (20–50°C/s) were used in the volatilization studies and the figures of merit were compared with those obtained from conventional pyrolysis curves. It was concluded that gallium, when introduced in nitric acid solution and at the 10 ng level, was evaporated between 900 and 1000°C in the form of Ga 2O. When gallium was the matrix element (10 μg range) the major fraction vaporized in the 1120–2300°C range, producing Ga 2O(g) and Ga(g) as major and minor components, respectively. A 1 ng mass of calcium vaporized rapidly above 1520°C with the evolution of atomic vapour, and this process overlapped in part with the vaporization of gallium matrix. Volatilization of gallium in the pyrolysis stage could be performed to a degree sufficient to eliminate the interference of up to 3 g l gallium in nitric acid medium on the determination of calcium using Zeeman-effect background correction. A detection limit of 0.06 μg g Ca in gallium was found if random contamination during dissolution was avoided. Microgram amounts of calcium introduced in HCl solution vaporized as CaCl 2 and CaO, the oxide being formed by a heterogeneous phase hydrolysis. The addition of excess NH 4Cl did not retard the hydrolysis of calcium chloride, while this additive promoted the vaporization of gallium in the form of chloride.

Determination of Fluorine, Chlorine, and Bromine by Molecular Absorption Spectrometry

Fluorine was determined by molecular absorption spectrometry (MAS) in a graphite tube furnace, and fluorine, chlorine, and bromine were determined in a flame. For the fluorine work, aluminum nitrate was added as a reagent to produce aluminum fluoride molecules whose absorbance was monitored with emission from a platinum hollow cathode lamp (HCL) at 227.45 nm. A deuterium arc lamp was employed for background correction. For the furnace work, barium nitrate was used as a chemical modifier to increase the absorption signal. After optimization of the chemical and furnace conditions, a detection limit of 160 pg F was obtained, with a linear dynamic range of two orders of magnitude. Graphite furnace MAS was used to accurately determine fluoride in dental rinse and National Institute of Standards and Technology oyster tissue, but the precision was between 21 and 23%. Low recoveries were obtained for the determination of trifluoroacetic acid and l,2,2,3-tetrafluoropropan-1-ol by graphite furnace MAS. The detection limit for F by flame MAS was 13 mg liter −1 which is a factor of 5 lower than the best reported flame MAS detection limit. Chlorine was determined by flame MAS with the aluminum chloride molecule. Excitation was done at 261.4 nm with a lead HCL. and a detection limit of 180mg liter −1 was obtained. Flame MAS of bromine was done by use of AlBr (excitation at 279.0 nm with an arsenic HCL) and InBr (excitation at 284.3 nm with a chromium HCL), but very poor detection limits were obtained: 24.5 g liter −1 and 500mg liter −1, respectively.