Evaluation of a quantitative method for trace impurities in arsenous acids by synchrotron radiation X-ray fluorescence spectrometry and inductively coupled plasma-atomic emission spectrometry.

Thirteen arsenous acid samples of known origins and refining methods were collected. Each sample was subjected to quantitative analysis of any impurity elements present using synchrotron radiation X-ray fluorescence spectrometry (SR-XRF) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). The trace elements selected were Sn, Sb and Bi for the reasons that they were considered not to be changed by their circumstances and that they showed high sensitivity to SR-XRF. These results obtained by both methods were compared and the correlation between these two methods was determined. The quantification of trace impurities obtained by SR-XRF using As as an internal standard showed good agreement with the results obtained by ICP-AES. The discrimination of refining method became possible by the comparison of these impurities' contents measured with non-destructive SR-XRF using several arsenous acid particles.     

Determination of additives in PVC material by UV laser ablation inductively coupled plasma atomic emission spectrometry

UV laser ablation inductively coupled plasma atomic emission spectrometry (LA-ICP-AES) has been applied to the direct determination of additives in solid poly(vinyl chloride) materials. A Nd:YAG laser, operating at its fourth harmonic (266 nm), was used with a beam masking device, in the most reproducible conditions, to introduce solid particles into the plasma torch of a simultaneous ICP-AES system. Emphasis was placed on both precision and accuracy in the analysis of PVC materials by LA-ICP-AES. A series of six in-house PVC reference materials was prepared by incorporating several additives in increasing concentrations. Three alternative methods were evaluated to certify the amount of incorporated elements: ICP-AES with sample dissolution, NAA and XRF. Satisfactory results and good agreement were obtained for seven elements (Al, Ca, Cd, Mg, Sb, Sn and Ti) among the ten incorporated. Sample homogeneity appeared to be satisfactory, and calibration graphs obtained by LA-ICP-AES for several elements are presented. Finally, the performance of the technique in terms of repeatability (1.6-5%), reproducibility (2–5%), and limits of detection was investigated.     

Laser defocusing effects on laser ablation inductively coupled plasma-atomic emission spectrometry: different ablation interactions between the laser and low-alloy steel, Fe pellets, and a pond sediment pellet.

The ablation interaction between a laser and solid samples, which affects the analytical performance for laser ablation inductively coupled plasma atomic emission spectrometry (LA-ICP-AES), was studied. The emission intensities of elements observed by LA-ICP-AES (LA-ICP-AES element signal intensities) for different solid samples were measured under different laser defocusing conditions with a fixed laser output energy. It was found that the optimum laser defocusing conditions were dependent on the different solid samples with different sample characteristics, and also on the different elements with different elemental characteristics in each solid sample. A low-alloy steel, pellets containing different Fe concentrations (0 - 100% Fe pellet), and a pond sediment pellet were used as different solid samples. The variations of the LA-ICP-AES Fe signal intensities observed under different laser defocus conditions were completely different between the low-alloy steel and the pond sediment pellet. The changes in the LA-ICP-AES Fe signal intensities for 90 and 100% Fe pellets were similar to that of the low-alloy steel. However, pellets with lower Fe concentrations (less than 70%) showed different trends and the defocusing behavior became closer to that of the pond sediment pellet. The LA-ICP-AES signal intensities of other elements were also evaluated, and were compared for different solid samples and different defocusing behavior. It was observed that the changes in the LA-ICP-AES signal intensities of almost all elements in the pond sediment pellet showed a similar trend to those of Fe for different laser defocus positions; that is, the elemental fractionation for these elements in the pond sediment pellet seemed to be relatively small. On the contrary, it was found that the LA-ICP-AES Si, Ti, and Zr signal intensities for low-alloy steel showed different trends compared to those of other elements, including Fe, under different defocusing conditions; that is, the elemental fractionation observed for the low-alloy steel was larger than that of the pond sediment pellet. From these results, different ablation interactions between the laser and the different solid samples were considered, and attributed to the sample characteristics, such as the matrix, hardness, and conductivity. Elemental fractionation was attempted to be explained by using elemental characteristics, such as the melting point and ionization energy of the elements.     

Determination of trace elements in olive oil by ICP-AES and ETA-AAS: A pilot study on the geographical characterization

The determination of trace elements in edible oils is important because of both the metabolic role of metals and possibilities for adulteration detection and oil characterization.The most commonly used techniques for the determination of metals in oil samples are inductively coupled plasma atomic emission spectrometry (ICP-AES) and atomic absorption spectrometry (AAS). For this study, a microwave assisted decomposition of the olive oil in closed vessels using a mixture of nitric acid and hydrogen peroxide was applied as sample preparation.The low achievable LODs enable the determination by ICP-AES of even very low concentrations of most elements of interest. The proposed ICP-AES method permits the determination of Ca, Fe, Mg, Na, and Zn in olive oils. Elements present in small amounts (Al, Co, Cu, K, Mn, Ni) were measured by ETA-AAS in the same sample digest. The concentrations of Al, Co, Cu, K, Mn, and Ni were in the range from 0.15 to 1.5 μg/g and differ according to the geographical origin of the oils. For the amounts of Fe, Mg, Na, and Zn in the samples, no significant differences according to the geographical origin of the oils could be observed, the mean concentrations being 15.31, 3.26, 33.10, and 3.39 μg/g, respectively. The Ca content varies in the range of 1.3 to 9.0 μg/g.The dependency of the trace elemental content of olive oils on their geographical origin can be used for their local characterization.     

Detection of heavy metals in Arabian crude oil residue using laser induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) was applied for the elemental analysis of Arabian crude oil residue samples. The spectra due to trace elements such as Ca, Fe, Mg, Cu, Zn, Na, Ni, K and Mo were recorded using this technique. The dependence of time delay and laser beam energy on the elemental spectra was also investigated. Prior to quantitative analysis, the LIBS system was calibrated using standard samples containing these trace elements. The results achieved through this method were compared with conventional technique like inductively coupled plasma.     

Speciation of Se,Fe and Zn in Human Milk Whey: The use of Instrumental Neutron Activation Analysis (INAA) to corroborate element profiles measured with Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES)

In human milk trace elements normally exist in a form which can easily be absorbed by the newborn infant. For investigations of the bioavailability of trace elements it is necessary to carry out a speciation analysis of the elements of interest. An independent analytical method has been used for the quality control of the shape of the element profiles obtained from the speciation analysis of Se, Fe and Zn in individual samples of human milk whey after chromatographic separation. For the element detection in the untreated milk fractions Instrumental Neutron Activation Analysis (INAA) was chosen as the reference method. Element distribution patterns have been obtained with Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) using on-line digestion of the fraction, reduction and hydride formation of Se ("T"-mode). Prior results are compared with those obtained by means of element detection in the untreated fractions ("U"-mode) with ICP-AES. The elution profiles of Se, Fe and Zn in human milk whey obtained by means of ICP-AES detection using the "T"-mode show good agreement with the distribution patterns obtained with INAA. Recoveries of 103% for Fe, 86% for Zn and 87% for Se were obtained. The element distribution patterns of Fe and Zn obtained with ICP-AES speciation using the "T"-mode also show good agreement with those obtained by means of ICP-AES using the "U"-mode.     

Enhancements in laser ablation inductively coupled plasma-atomic emission spectrometry based on laser properties and ambient environment

Analytical performance of laser ablation inductively coupled plasma-atomic emission spectrometry (ICP-AES) depends critically on the interaction between the laser light and the sample. The analyte emission line intensity in ICP-AES depends on the quantity of mass ablated. The effect of laser parameters (wavelength, pulse duration, and power density) was investigated for increasing the quantity of ablated mass. For fixed laser beam energy, the ablated mass can change 2 to 3 orders of magnitude by changing the laser beam spot size on the sample. The ablated mass quantity also depends on laser pulse duration and wavelength; and on ambient gas in the sample chamber. The shorter the pulse duration and wavelength, the higher the quantity of ablated mass. By using He in the chamber, the amount of mass increases by a factor of 2 for 30 ns excimer laser ablation and by an order of magnitude for ps-laser ablation.     

Geochemistry study of soil affected catastrophically by tsunami disaster triggered by 2004 Indian Ocean earthquake using a fourth harmonics (λ = 266 nm) Nd:YAG laser induced breakdown spectroscopy

In this work, laser induced breakdown spectroscopy (LIBS) analysis of the soil samples collected from Aceh, a place in Indonesia worst affected by 2004 Indian Ocean tsunami, was conducted. In the LIBS experimental system, a high energy pulsed laser beam was focused on the tsunami affected soil samples and the atomic emission lines, originating from the laser induced plasma were recorded using locally developed laser induced breakdown spectrometer. Our results show that the concentrations of many elements especially terrestrial markers, namely titanium, iron, and carbonate marker such as magnesium, are higher in the tsunami-affected samples than that in the unaffected samples collected from the same neighborhood. The quantification of Ti, Fe and Mg were carried out using Ti II 334.94, Fe I 438.35, and Mg I 277.98 nm atomic transition lines respectively by drawing the calibration curve by preparing the samples of known concentrations in unaffected soil matrix. In order to ensure accurate quantification, the local thermal equilibrium of the laser-induced plasma was verified using Mc Writher criterion, for which the plasma temperature was estimated using linearized Boltzmann plot for six iron atomic transition lines and the electron number density in the plasma was estimated using Stark broadened Fe I 540.4 nm atomic lines. The estimated temperature and electron number density of the laser induced plasma are 9642 K and 3.5 × 10¹⁶ cm^?3 respectively. The concentrations of Ti, Fe and Mg in tsunami unaffected soil are 0.09, 3.2 and 0.02 w/w% and in tsunami affected soil are 0.14, 7.9 and 0.048 w/w% respectively. These values are in good agreement with XRF data. The elemental ratios extracted from LIBS signal intensity revealed that LIBS emission intensity ratios of several elements, such as Si/Ti, Al/Ti and Sr/Ba are potential candidates as the distinctive geochemical signature for identification the soil impacted and unimpacted by the 2004 Indian Ocean giant tsunami. The advantage of using LIBS for the elemental analysis is that the sample can be analyzed in its pristine form without any need cumbersome sample preparation method, which has the risk of bringing in external additives through chemicals used for the sample preparation. Other advantages of LIBS technique are that the analysis can be in situ and can be carried out remotely.     

Analysis of glass by UV laser ablation inductively coupled plasma atomic emission spectrometry. Part 2. Analytical figures of merit

Two lasers working in the UV part of the spectrum have been used for the direct analysis of glass samples by laser ablation ICP-AES. An XeCl excimer laser (308 nm) and a Nd:YAG laser operating at the third harmonic (355 nm) and the fourth harmonic (266 nm) have been selected. The energy was 70 mJ and 5 mJ for the excimer laser and the Nd:YAG laser, respectively, with a 10 Hz repetition rate. Figures of merit such as repeatability, reproducibility, accuracy and limits of detection have been studied. Si was used as an internal standard to improve the repeatability, the reproducibility and the accuracy. Use of internal standardardization led to an RSD of less than 1% for most elements and to a linear calibration graph irrespective of the colour of the glass samples. Limits of detection in the solid were of the same magnitude as those obtained using sample dissolution and pneumatic nebulization. Results confirmed that the XeCl laser provided the best results of detection whereas the Nd:YAG laser, particularly at 266 nm, was less sensitive to glass colour.     

Characterizing ablation and aerosol generation during elemental fractionation on absorption modified lithium tetraborate glasses using LA-ICP-MS

The influence of sample matrix composition, absorption behavior and laser aerosol particle size distribution on elemental fractionation in laser ablation inductively coupled plasma mass spectrometry was studied for nanosecond laser ablation at a wavelength of 266 nm. To this end, lithium tetraborate glass samples with different iron oxide contents and trace amounts of a group of 11 elements were prepared synthetically. The samples were characterized in terms of optical absorbance, melting points, trace element concentrations and homogeneity. UV/VIS spectra showed that sample absorption rises with increasing Fe₂O₃ content. Crater depths and time-dependent particle size distributions were measured, and ablated and transported sample volumes were estimated. Furthermore, the laser aerosol was filtered using a particle separation device and transient ICP-MS signals were acquired with and without filtering the aerosol. The results demonstrate that the amount of ablated sample is related to the absorption coefficient of the sample and therefore to the optical penetration depth of the laser beam into the sample. The higher energy densities resulting from the shorter penetration depths result in smaller average particle sizes for highly absorbing samples, which allows more efficient transport to and atomization and excitation of the ablated material within the ICP. The particle size distribution changes continuously with ablation time, and larger particle fractions occur mainly at the beginning of the ablation, which leads to particle-related fractionation processes at the beginning of the transient signal. Exceeding a critical depth to diameter ratio, laser-related elemental fractionation processes occur. Changes in the volatile to non-volatile element intensity ratio after the aerosol is filtered indicate that particle size-related enrichment processes contribute to elemental fractionation.     

Application of a microwave-based desolvation system for multi-elemental analysis of wine by inductively coupled plasma based techniques

Elemental wine analysis is often required from a nutritional, toxicological, origin and authenticity point of view. Inductively coupled plasma based techniques are usually employed for this analysis because of their multi-elemental capabilities and good limits of detection. However, the accurate analysis of wine samples strongly depends on their matrix composition (i.e. salts, ethanol, organic acids) since they lead to both spectral and non-spectral interferences. To mitigate ethanol (up to 10% w/w) related matrix effects in inductively coupled plasma atomic emission spectrometry (ICP-AES), a microwave-based desolvation system (MWDS) can be successfully employed. This finding suggests that the MWDS could be employed for elemental wine analysis. The goal of this work is to evaluate the applicability of the MWDS for elemental wine analysis in ICP-AES and inductively coupled plasma mass spectrometry (ICP-MS). For the sake of comparison a conventional sample introduction system (i.e. pneumatic nebulizer attached to a spray chamber) was employed. Matrix effects, precision, accuracy and analysis throughput have been selected as comparison criteria. For ICP-AES measurements, wine samples can be directly analyzed without any sample treatment (i.e. sample dilution or digestion) using pure aqueous standards although internal standardization (IS) (i.e. Sc) is required. The behaviour of the MWDS operating with organic solutions in ICP-MS has been characterized for the first time. In this technique the MWDS has shown its efficiency to mitigate ethanol related matrix effects up to concentrations of 1% (w/w). Therefore, wine samples must be diluted to reduce the ethanol concentration up to this value. The results obtained have shown that the MWDS is a powerful device for the elemental analysis of wine samples in both ICP-AES and ICP-MS. In general, the MWDS has some attractive advantages for elemental wine analysis when compared to a conventional sample introduction system such as: (i) higher detection capabilities; (ii) lower ethanol matrix effects; and (iii) lower spectral interferences (i.e. ArC(+)) in ICP-MS.     

Metal imaging on surface of micro- and nanoelectronic devices by laser ablation inductively coupled plasma mass spectrometry and possibility to measure at nanometer range

An analytical mass spectrometric method for the elemental analysis of nano-bioelectronic devices involved in bioengineering research was developed and applied for measurements of selected metals (Au, Ti, Pt, Cr, etc. ) on interdigitated electrode array chips (IDA-chip). An imaging laser ablation inductively coupled plasma mass spectrometric (LA-ICP-MS) procedure was used to map the elements of interest on the surface of the analyzed sample. The obtained images of metals were in a good agreement and corresponded to the micro- and nanofabricated metal electrode pattern. For the analysis at nanometer resolution scale a NF-LA-ICP-MS (NF-near-field) procedure was applied, which utilize thin Ag needle to enhance laser beam energy and improve spatial resolution of the method. The results show a ∼100× enhancement of analyte signal, when the needle was positioned in the “near-field region” to the sample surface and the laser shot was performed. In addition, mass spectrometric studies of reproducibly for five separated NF-LA shots in different places of analyzed sample yielded an RSD of the measurement of 16%.     

Rapid soil analyses of overburden material from historic mines with SNMS

Plasma-based Secondary Neutral Mass Spectrometry (SNMS) is designed and usually used for depth-resolved determination of the elements in inhomogeneous samples. This report shows that it is also advantageous for the quantification of the total elemental inventory of granular material. As an example of such an application, the quantitative elemental analysis of soil samples from residues of three historic mines in Baden-Württemberg is presented. The results obtained with SNMS, using a high primary energy of E_p = 1340 eV, were compared to the concentrations measured by Atomic Absorption Spectroscopy (AAS) and X-Ray Fluorescence (XRF). A reasonable correspondence was found with a mean deviation between all three methods of about 50%. However, SNMS measurements of standard soils, without any matrix adaptation of the elemental sensitivities, exhibited mean deviations from the certified concentrations of only 20–30 wt% down to concentrations below 10^–2 wt%. The advantages of SNMS against AAS and XRF are its simple sample preparation and the rapid detection of all elements in the analyzed material within some 10 min. In each of the three samples chromium, nickel, copper, zink and lead (only sample HS 64) were found in concentrations exceeding the limiting values of the German Sewage Sludge Ordinance (SSO).     

Elemental content of Vietnamese rice. Part 2. Multivariate data analysis

Rice samples were obtained from the Red River region and some other parts of Vietnam as well as from Yanco, Australia. These samples were analysed for 14 elements (P, K, Mg, Ca, Mn, Zn, Fe, Cu, Al, Na, Ni, As, Mo and Cd) by ICP-AES, ICP-MS and FAAS as described in Part 1. This data matrix was then submitted to multivariate data analysis by principal component analysis to investigate the influences of environmental and crop cultivation variables on the elemental content of rice. Results revealed that geographical location, grain variety, seasons and soil conditions are the most likely significant factors causing changes in the elemental content between the rice samples. To assess rice quality according to its elemental content and physio-biological properties, a multicriteria decision making method (PROMETHEE) was applied. With the Vietnamese rice, the sticky rice appeared to contain somewhat higher levels of nutritionally significant elements such as P, K and Mg than the non-sticky rice. Also, rice samples grown during the wet season have better levels of nutritionally significant mineral elements than those of the dry season, but in general, the wet season seemed to provide better overall elemental and physio-biological rice quality.     

New methods for the direct determination of dissolved inorganic, organic and total carbon in natural waters by Reagent-Free Ion Chromatography and inductively coupled plasma atomic emission spectrometry

New methods have been developed and applied successfully for the determination of dissolved inorganic, organic and total carbon in water samples. The new methods utilize two instrumental setups, Reagent-Free™ Ion Chromatography (RF™-IC) and inductively coupled plasma atomic emission spectrometry (ICP-AES). Dissolved inorganic carbon (DIC) was measured in untreated samples along with Cl⁻, F⁻ and SO₄²⁻ using RF™-IC and by in-line mixing with 0.1 M HNO₃ to enhance CO₂ removal in the nebulizer, followed by ICP-AES analysis. Total dissolved carbon (TDC) was measured by in-line mixing with 0.1 M NaOH following ICP-AES analysis. Dissolved organic carbon (DOC) was obtained as the difference between DIC and TDC. Only non-volatile organic carbon could be detected by the present method. The workable limits of detection obtained in the present study were 0.5 mM (RF™-IC) and 0.1 mM (ICP-AES) for dissolved inorganic and organic carbon, respectively. The power of the new methods lies in routine analysis of DIC and DOC in samples of natural waters of variable composition and salinity using analytical techniques and facilities available in most laboratories doing water sample analysis. The techniques are sensitive and precise, can be automated using gas-tight sample vials and auto-samplers, and are independent of most elemental interferences with the exception of chloride overload by saline samples when using RF™-IC. The new methods were successfully applied for analysis of DIC and DOC in selected samples of natural and synthetic waters.     

Elemental distribution in breast tissue samples using X-ray fluorescence microtomography

Summary The X-ray fluorescence microtomography (XRFMT) is a non-destructive technique, based on the detection of X-ray fluorescence emitted by the elements in the sample, and it is used to complement other techniques for sample characterization. In this work some tissues of human breast (healthy tissue, benign tumor and malignant tumor) have been analyzed in order to verify the efficiency of the system in the determination of the elemental distribution in these types of samples. The experiments were performed at the X-ray fluorescence beam line (D09B-XRF) of the Brazilian Synchrotron Light Source (LNLS), Campinas, Brazil. A white beam was used for the excitation of the elements and an HPGe detector detected the fluorescence photons. The incident beam was monitored by an ionization chamber and a fast scintillator detector was used to detect the transmitted radiation. All the tomographies have been reconstructed using a filtered-back projection algorithm. In the tissues samples, the elements of higher concentration were Zn, Cu and Fe.     

Analysis of liquid samples using dried-droplet laser ablation inductively coupled plasma mass spectrometry

In this study we developed a dried-droplet method for laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method provides accurate and precise results when building calibration curves and determining elements of interest in real liquid samples. After placing just 1 μL of a liquid standard solution or a real sample onto the filter surface and then converting the solution into a very small, thin dry spot, the sample could be applied as an analytical subject for LA. To demonstrate the feasibility of this proposed method, we used LA-ICP-MS and conventional ICP-MS to determine the levels of 13 elements (Li, V, Mn, Co, Ni, Cu, Zn, As, Mo, Cd, Sb, Tl, and Pb) in five water samples. The correlation coefficients obtained from the various calibration curves ranged from 0.9920 (²⁰⁵Tl) to 0.9998 (⁵¹V), sufficient to allow the determination of a wide range of elements in the samples. We also investigated the effects of Methylene Blue (MB) and the NaCl concentration on the elemental analyses. MB could be used as an indicator during the ablation process; its presence in the samples only negligibly influenced the intensities of the signals of most of the tested elements. Notably, high NaCl contents led to signal suppression for some of the elements. In comparison with the established sample introduction by nebulization, our developed technique abrogates the need for time-consuming sample preparation and reduces the possibility of sample contamination.     

Use of monte carlo modeling to aid interpretation and quantification of the low energy-loss electron yield at low primary energies

Experimental low-loss electron (LLE) yields were measured as a function of loss energy for a range of elemental standards using a high-vacuum scanning electron microscope operating at 5 keV primary beam energy with losses from 0 to 1 keV. The resulting LLE yield curves were compared with Monte Carlo simulations of the LLE yield in the particular beam/sample/detector geometry employed in the experiment to investigate the possibility of modeling the LLE yield for a series of elements. Monte Carlo simulations were performed using both the Joy and Luo [Joy, D.C. & Luo, S., Scanning 11(4), 176988 (2005)] to assess the influence of the more recent stopping power data on the simulation results. Further simulations have been conducted to explore the influence of sample/detector geometry on the LLE signal in the case of layered samples consisting of a thin C overlayer on an elemental substrate. Experimental LLE data were collected from a range of elemental samples coated with a thin C overlayer, and comparisons with Monte Carlo simulations were used to establish the overlayer thickness.     

Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry

Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n = 3, 1σ). A good agreement between experimental results and the certified values was also observed.     

Application of energy dispersive X-ray fluorescence spectrometry as multielemental analysis to determine the elemental composition of crumb rubber samples

The elemental content of different rubber samples was analyzed using different analytical methods (inductively coupled atomic emission spectroscopy and non-polarized energy dispersive X-ray fluorescent spectroscopy). A new application of energy dispersive X-ray spectrometry as an analytical method for the determination of elemental content of rubber samples was investigated. Control analyses were also carried out to compare the results by ICP-AES. In one hand four samples contained same quality of elements (Mg, Si, P, S, Ca, Fe, Zn), while another four samples were without phosphorous. On the other hand there were significant differences in the ratio of C/H in the case of each sample. Based on the results, it was concluded that the X-ray spectrometry as an analytical method is well-applicable to determine the elemental composition of rubber samples, but the calibration is a key part of the analysis. A good correlation was observed between the different methods, but the correlation was the function of characteristic of matrices. Significant matrix effect from the presence of phosphor was observed in the case of some samples, while the change of C/H ratio could not result notable matrix effect.