Comparative analysis of X-ray fluorescence methods for elemental composition determination of the archaeological ceramics from low sample quantity

Wavelength-dispersive X-ray fluorescence analysis (WDXRF) and total-reflection X-ray fluorescence (TXRF) analysis were applied to study the elemental composition of the Late Neolithic ancient ceramics collected at the Popovsky Lug burial site (Kachug, Upper Lena river, Russia). Semi-quantitative non-destructive analysis of ceramic pieces showed that measurements of the upper and lower sides of the ceramic are less informative than the measurement of its cut. Various sample preparation techniques for the low quantity of crushed ceramics such as fusion, pressing and preparation of suspensions were compared to preserve the material. Samples were prepared as 150 mg fused beads and 250 mg pressed pellets for WDXRF, and as suspensions of 20 mg sample based on the aqueous solution of the Triton X-100 surfactant for TXRF. Certified methods were used to validate the obtained contents of rock-forming oxides and inductively coupled plasma mass spectrometry was used to confirm the results of trace elements determination. Based on the carried-out studies, a combination of the wavelength-dispersive X-ray fluorescence analysis (glass) and total-reflection X-ray fluorescence analysis (suspension) methods was chosen to obtain the data on the elemental bulk composition of archaeological ceramics. The proposed combination allowed the quantitative determination of Na, Mg, Al, Si, P, K, Ca, Ti, Mn, Fe, V, Cr, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Pb, and Ba from the sample of crushed ceramics weighing only about 170 mg.

Stages of arc atomic emission spectrometry development as applied to the solid geological samples’ analysis

The atomic emission spectrometry (AES) with arc discharge method evolution is inextricably linked with the fundamental scientific discoveries made in the 19th and 20th centuries, and it also reflects the change of scientific paradigms in a specific field of natural science – analytical chemistry. Theoretical comprehension and generalization of experimental data, along with the improving spectral equipment and methodological techniques for determining the elemental and material composition of solid geological samples, increased the accuracy of the analysis results i.e. the results were translated from qualitative to semi-quantitative and quantitative. Modern computerized equipment for direct AES with arc discharge provides minimal errors in measuring the spectral intensity due to the high stability of the excitation source of the spectra of atoms and molecules, the use of high-power polychromators and express digital recording of spectra by multi-channel detectors. However, in the commercial software of spectrometers, only the methods of manual spectra processing proposed in the 30s of the last century are programmed. That limits the possibilities of improving the analysis quality. The time has come to use the developed concept of computer processing of big spectral data, which is based on the information models of chemical analysis and the back propagation of error, in order to select the best models. Current article shows that the information models of computer spectra interpretation obtained from direct arc AES multi-element techniques of geological samples’ analysis using the injection-spillage method provide better quantitative results (category III of accuracy) due to a more complete account of spectral and matrix influences compared to the routine processing techniques.

Capabilities and limitations of tin direct determination using the spectrometry methods with inductively coupled plasma in Azov and Black sea waters

The current study discussed the capabilities and limitations of tin direct determination in the waters of the Black and Azov Seas using the ICP-MS and ICP-AES methods without the separation and concentration of the analyte. The conditions for the analysis of waters, the influence of dilution and matrix components on the results of the analysis were established. As the salinity of the seawater increased, the slope of the calibration curve decreased, regardless of the detection method used. The leveling of the matrix effect of seawater on the analytical signal of tin was achieved by diluting the sample up to 100 times. A significant decrease in the analytical signal of tin was observed on the samples of seawater characterized by the high salinity. These methods allowed determining tin at the concentrations ranging from 0.33 μg/dm3 (ICP-MS), 0.37 μg/dm3 (ICP-AES) to 5 μg/dm3 in natural (fresh) water or seawater with low salinity level according to the calibration curve of the deionized water. For ICP-MS and ICP-AES determination of tin in seawater with the salinity level above 6‰ and tin concentration of more than 5 μg/dm3, it was required to use the calibration dependence constructed on the model seawater considering the salinity of the object. The studies have shown that the content of tin in the Kuban River is 0.13 μg/dm3. In the Sea of Azov, the concentration of tin in the water, depending on the sampling site, was less than 0.33 μg/dm3 (Taman) and 1.8 μg/dm3 (Temryuk, commercial port). In the Black Sea, the concentration of tin in the seawater samples from Novorossiysk city was higher and ranged from 0.55 μg/dm3 (embankment) to 1.5 μg/dm3 (seaport) and 2.1 μg/dm3 (grain terminal).

Lutetium oxide analysis by direct arc atomic emission spectrometry

The requirements for the composition of initial oxides for the lutetium orthosilicate crystals are quite stringent: the content of the basic substance Lu2O3 is 99.999 wt%. Critical are coloring impurities: Fe, Ni, Cr, Co, Cu, V, Mn, the content of each should be no more than 0.0005 - 0.0010 wt%, Pr, Nd, Sm, Er, Tb, Yb no more than 0.0005 wt% for each one. It is also necessary to control the content of Al, As, Bi, Cd, Mg, Mo, Pb, Sb, Si, Sn, Ti, Zn, Y, La, Ce, Sc, Eu, Gd, Dy, Ho, Tm. To determine the impurity composition of lutetium oxide, one of the promising methods of analysis is direct arc atomic emission spectroscopy (DC Arc). The advantages of this method are the determination of the chemical composition without sample dissolution, a wide range of concentrations (10-6 - 10-1% wt%), a large number of determined elements. To realize the potential analytical capabilities of the method, the experimental conditions were studied: the interelectrode distance, the shape and size of graphite electrodes, the ratio of Lu2O3 to the spectral buffer, the type of carriers and operating modes of the generator. For most elements, the limits of determination are n ∙ 10-6 - n ∙ 10-4 wt%, that is significantly lower than in the current methods of DC Arc. The trueness of results is controlled by ICP-MS. The complex application of new approaches and modern capabilities of spectral equipment made it possible to develop a method with improved metrological characteristics.

Isotope analysis of highly enriched “silicon-28” by high-resolution inductively coupled plasma mass spectrometry using an internal standard

In order to study the isotopic effects in semiconductor materials, single crystals of high chemical and isotopic purity are required. The reliability of the obtained data on the magnitude and the direction of isotopic shifts depends on the accuracy of determining the concentration of all stable isotopes. In the isotopic analysis of enriched “silicon-28” with a high degree of enrichment (> 99.99%), it is necessary to determine the impurities of 29Si and 30Si isotopes at the level of 10-3 ¸ 10-5 at. %. At this concentration level, these isotopes can be considered as impurities. It is difficult to achieve high measurement accuracy with simultaneous registration of the main and “impurity” isotopes in such a wide range of concentrations. The registration of analytical signals of silicon isotopes must be carried out in the solutions with different matrix concentrations. The use of the solutions with the high concentration of the matrix element requires the introduction of corrections for matrix noise and the drift of the instrument sensitivity during the measurement. It is possible to reduce the influence of the irreversible non-spectral interference and sensitivity drift by using the method of internal standardization. The inconsistency of the literature data on the selection criteria for the internal standard required studying the behavior of the signals of the “candidates for the internal standard” for the ELEMENT 2 single-collector high-resolution inductively coupled plasma mass spectrometer on the matrix element concentration and the nature of the solvent, as well as on the solution nebulizing time. Accounting for the irreversible non-spectral matrix noise and instrumental drift in isotopic analysis of enriched “silicon-28” and initial 28SiF4 by inductively coupled plasma mass spectrometry had allowed us to reduce by 3-5 times the random component and by more than an order of magnitude the systematic component of the measurement error in comparison with the external standard method. This made it possible to carry out, with sufficient accuracy, the operational control of the isotopic composition of enriched “silicon-28”, both in the form of silicon tetrafluoride and polycrystalline silicon obtained from it, using a single serial device in the range of isotopic concentrations 0.0001–99.999%.

Identification of unknown compound extracted from the hair of exhumed human remains using mass spectrometric and gas chromatographic data

The real example of GC-MS identification of unknown constituent of human hair extract belonging to the exhumed remains is considered. The identification of this constituent (molecular weight 238 Da) was unsuccessful using both its standard mass spectrum (electron ionization) in combination with lib­ra­ry search, and its GC retention index value (~1540 on semi-standard non-polar polydimethyl siloxane stationary phases with 5% phenyl groups). However, its identification appea­red to be possible using the original algorithm of data processing. This approach implies revealing the structural analogues of unknown analytes, primarily their homologues which differ by molecular masses on ± 14 Da and by composition on CH2 homolo­go­us difference. This approach allowed revealing such analogues of unknown analyte as Flavesone (2,2,4,4-tetramethyl-2-isobutyrylcyclohexa-1,3,5-trione), Leptospermone (2,2,4,4-tetramethyl-2-isopentanoylcyclohexa-1,3,5-trione), and some others. All these compounds belong to a rather “exotic” class of natural compounds knows as cyclic b-triketones. Based on the obtained data, the possible structure of the constitu­ent under the consideration was proposed as 2,2,4,4-tetramethyl-2-propionylcyclohexa-1,3,5-trione. The principal fea­ture of cyclic b-triketones is their existence in a few tautomeric forms. Another tautomer of triketone under discussion is 5-hydroxy-2,2,6,6-tetramethyl-4-propionyl-4-en-1,3-dio­ne (CAS № 87552-01-0). This compound is found to be the constituent of Leptosper­mum scoparium essential oil and some other plants, and it belongs to the group of structural analogues of Flave­sone. The most known pharmaceutical application of essential oils containing these compounds are the components of conditioners for hair and skin. The results confirm this formerly un­known component does not belong to the group of toxic substances. This excludes the criminal origin of the remains.

Microextraction flotamicroextraction flotation concentration and determination of chloroacetic acids in watertion concentration and determination of chloroacetic acids in water

The flotation-assisted liquid-liquid microextraction method of mono-, di -, and trichloroacetic acids (CAAs) has been developed. Methyl tert-butyl ether (MTBE) was used as an extractant. The emulsification was performed by the ultrasonic irradiation. The microextraction procedure was carried out in a 27 ml special tube. It was equipped with the capillaries for sampling the extract and an air outlet. A salting-out additive (Na2SO4) was used to reduce the solubility of MTBE in water and to increase the extraction efficiency of CAAs. The air passage through the emulsion of the extractant was carried out using the eight-channel capillary bubbler. The organic matrix replacement was applied for ion chromatographic determination of CAAs with the conductivity detection. Current study showed the advantages of the flotation-assisted demulsification over the centrifugal one. The concentration factors of chlorinated acetic acids were 2-3 times higher. The detection limits of CAAs in water were reduced to (5·10-4 - 4·10-3 mg/l). The extraction time was reduced by more than three times. The trueness of the determination of HUC impurities was confirmed by the addition method. The statistical insignificance of the systematic error in comparison with the random error was shown. The developed method of preconcentration in combination with ion chromatography made it possible to determine the concentrations of CAAs 40-1250 times lower than the normalized SanPiN and WHO. This allowed conducting a highly sensitive determination of CAAs in water long before the onset of the critical ecological state.

Voltammetric sensor based on the copper (II) amino acid complex for the determination of tryptophan enantiomers

A voltammetric sensor based on a composite of polyarylene phthalide and graphitized carbon black Carboblack C modified with chelate complexes of L-argenato-L-alaninate of copper (II) has been developed for the recognition and selective determination of tryptophan enantiomers. The conditions for modifying the sensor are optimized, the effective surface area (A = 4.38 ± 0.06 mm2) and the effective resistance (Ret = 1.29 ± 0.08 kΩ) are calculated. The optimal conditions for recording voltammograms of tryptophan enantiomers are selected: the range of operating potentials is 0.5-1.2 V, the potential sweep rate is 20 mV/s, the holding time of the electrode in the test solution is 5 s. The electrochemical and analytical characteristics of the sensor were studied when registering differential pulse voltammograms of tryptophan enantiomers. It is shown that the dependence of the analytical signal on the concentration is linear in the range from 1.25·10-6 to 1·10-3 M with detection limits of 0.90·10-6 M for L-Trp and 0.66·10-6 M for D-Trp. The developed sensor shows the greatest sensitivity to D-Trp. The sensor has been successfully tested to determine the content of L- and D-Trp in enantiomer solutions in the presence of excipients that are part of medicines and biologically active additives. The proposed sensor allows the determination of tryptophan enantiomers in human urine and blood plasma. To evaluate the analytical capabilities of the sensor, the "entered-found" method was used. When determining tryptophan enantiomers in model solutions, the relative standard deviation does not exceed 2.3 %, and the relative error is 1.7 %. When determining D- and L-Trp in biological fluids, the relative standard deviation ranges from 0.3-1.7 %, and the relative error ranges from 0.3-5.6 %. The research results show that there is no significant systematic error.

Bilayer capillary coatings based on nanosized ion-exchangers for the capillary electrochromatography analyses of biogenic amines and amino acids

Nanoparticles are widely used in capillary electrophoresis as stationary phases adsorbed on the internal capillary walls for the separation and concentration of analytes in capillary electrochromatography. The fastest and simplest approach for the formation of coatings is a physical adsorption of nanoparticles. Nevertheless, the formed coatings frequently possess low stability. The layer-by-layer approach for the formation of stabile and dense coating of internal capillary walls based on negatively charged nanosized cation-exchanger was proposed. The method included the sequential alteration of appositively charged layers of nanosized ion-exchangers. The proposed “anion-exchanger – cation-exchanger” bilayer coating possesses high stability in wide pH range (2-10) and provides up to 120 analyses without the need of re-coating. The coating was applied for the separation and on-line concentration of catecholamines and amino acids in capillary electrochromatography mode. High efficiencies were achieved (N = 450-720 th. t.p./m and N = 400-520 th. t.p./m for cathecholamies and amino acids, respectively), while the analysis time was significantly decreased. It was established, that high concentration of negatively charged functional groups on the capillary surface led to the increase of stacking efficiency factors due to the interactions between analytes and functional groups of the modifier on the capillary walls. It contributed to the 2-4 times reduced detection limits (LODs) of analytes compared to the mono-layer coatings (LODs of catecholamines = 3-4 ng/mL, LODs of amino acids = 40-100 ng/mL).

Results accuracy of the simultaneous Na, K, Li, Rb and Cs determination in geochemical objects using the flame atomic emission spectrometry

One of the most important challenges in the simultaneous determination of the five alkaline elements is that their abundance differs thousands of times in natural samples. Therefore, usually the analysis of the same samples is performed using several analytical methods or techniques. An atomic emission spectrometry is the most selective method for the determination of alkaline elements in wide ranges of their contents. The reliable and correct simultaneous determination of major and trace elements contents by one method is economically attractive for classifying rocks, reconstructing the conditions of their formation, etc. The atomic emission spectrometry technique of the simultaneous determination of the five alkaline elements was developed with the use of the modern equipment. The accuracy and trueness of the developed technique results were evaluated in the current study. The technique features were the preparation and the analysis of the high-salt solutions of the geochemical samples, and the use of a low-temperature propane-butane flame and multichannel photoelectric recording of the spectra for the simultaneous determination of alkali metals contents. A specific data processing ensured accounting for the spectral background and minimizing the interferences when calibrating by CRMs with various compositions and genesis. The determined concentrations ranges of alkaline elements in natural and man-made environments had been expanded by improving the detection limits and using several analytical lines of Na, K and Rb with different spectral features. FAES results were compared with the results of XRF, ICP-MS, the standard addition and dilution methods, and its accuracy and trueness were found to be satisfactory for the requirements of geological and geochemical studies.