Atomic Spectrometry Method Research Articles

Yesterday's problems are here to stay: Invisible exposure to geogenic metal (loid)s of arsenic, boron, and lithium in the Atacama Desert

AbstractIn this paper, we review the three natural contaminants (arsenic, boron, and lithium) that affected the ancient Andean populations of northern Chile. We debate the natural setting and the toxicity of these elements upon ancient populations exposed and their biocultural significance. This review demonstrates that recent advances in sensitive analytical atomic and mass spectrometry methods have immensely contributed to understanding the extent of exposure to geogenic metal (loid)s by ancient Andeans using well preserved tissues such as hair, bones, and teeth. In addition, the synthesized evidence shows that ancient Atacama Desert populations were significantly affected simultaneously by multiple potentially toxic chronic endemic regional hydro contaminants. Last, we suggest that future archaeometric and archaeological analysis need to consider ancient multicontaminants as an important factor when analyzing diet and health conditions.

Using the sorption properties of diatomite from the Aktobe deposit in improving the quality of drinking water in Western Kazakhstan

The paper describes the results of monitoring studies of the quality of tap water in the city of Uralsk. A solution was found to use natural reserves of the mineral diatomite in the purification of drinking water. The natural sorbent diatomite was modified with hydrochloric acid before testing. Natural and modified diatomite samples were studied using X-ray fluorescence analysis and electron microscopy. In acid-activated diatomite, the specific surface area and porosity increase by 2.5 times. Xray fluorescence analysis of the elemental composition showed an increase in the silicon content in the sorbent. Organoleptic and physicochemical properties were studied in the original and diatomite-treated water: turbidity, taste, smell, color, hardness, permanganate oxidation, pH, iron and copper ions. The efficiency of sorption with respect to heavy metals was tested using the model toxicant copper sulfate. Determinations of copper and iron ions were carried out using the atomic spectrometry method. Hardness, permanganate oxidation, pH and organoleptic parameters were determined by standard methods. Treatment of water with natural and modified diatomite made it possible to significantly reduce water pollution according to the studied parameters. Filtering water with a modified diatomite sorbent allows you not only to purify water from unwanted impurities, but also to adjust its salt composition due to the intake of silicon. Based on the results of the work, we can conclude that, compared to natural, modified diatomite has higher adsorption properties in relation to copper and iron cations, increases pH, and also contributes to more effective water purification from unwanted impurities.

Analysis of accumulation and acute phytotoxic reactions of Ocimum basilicum to lead contamination in the initial phases of plant development

It was noted that contamination of agricultural water and substrates with heavy metals is a serious environmental problem that can reduce both plant productivity and the safety of plant production used for food purposes or as forage. Lead, being one of the most common ecotoxicants among heavy metals, often ends up in water used for irrigating open and closed ground crop systems. The experimental model was based on the method for determining acute phytotoxicity according to GOST 33777-2016, with the introduction of the necessary corrective changes that do not conflict with GOST. Analytical work was based on the methods of atomic emission spectrometry and optical microscopy. Based on the data obtained, it is necessary to note the barrier function of basil seed exudate, which is expressed in the fact that the exudate absorbs most of the ecotoxicant compound from the solution, as well as deprivation of root hair growth and low variability of Pb(CH3COO)2 phytotoxicity for different varieties. The phytotoxicity of lead is expressed in this study along a gradient in which at the maximum concentration of Pb(CH3COO)2 we obtain an acute, but non-lethal toxic reaction. Exudate plays a protective role in the first days of seed germination, but does not exclude necrosis of root hairs and, subsequently, of the root not protected by exudate.

Validation of the Randox colorimetric assays for serum copper and zinc.

Serum copper and zinc are measured to assess deficiency and toxicity. Atomic absorption spectrophotometry and mass spectrometry methods are expensive and require highly trained staff. Colorimetric assays are available from Randox which are inexpensive and can be automated. We validated serum copper and zinc colorimetric assays on the Binding Site Optilite analyser including comparison with flame atomic absorption spectrophotometry (FAAS) and inductively coupled plasma-mass spectrometry (ICP-MS). Accuracy, imprecision, lower limit of quantitation, and linearity were ascertained. The impact of triglycerides, bilirubin, nickel, and iron on assay performance was also investigated. Comparison of results from colorimetric analysis of patient and external quality assurance samples with those obtained by FAAS and ICP-MS was undertaken. Intra-, and inter-assay imprecision was <9%. Serum copper and zinc assays were linear between 1.8-35.6 and 2.3-45.7 µmol/L, respectively. Agreement was good between colorimetry and FAAS (intercept = -0.7, slope = 1.04) and ICP-MS (intercept = 0.6, slope = 0.99) for serum copper in patients' samples. For serum zinc, agreement was poor between colorimetry and FAAS (intercept = 2.2, slope = 0.87) and ICP-MS (intercept = 1.9, slope = 0.98) in patients' samples. There was a poor concordance in assessment of hypozincaemia between colorimetry and FAAS/ICP-MS. The Randox colorimetric assay for serum copper on the Optilite is simple to perform, has a short analysis time, and measured concentrations compare well with FAAS and ICP-MS. Due to poor agreement with FAAS and ICP-MS, colorimetry is not suitable for the measurement of serum zinc.

Methods of Atomic Spectroscopy in Studying Properties and the Behavior of Nanoscale Magnetic Materials in Biological Systems

Methods of Atomic Spectroscopy in Studying Properties and the Behavior of Nanoscale Magnetic Materials in Biological Systems

Methods of Atomic Spectroscopy in Studying Properties and the Behavior of Nanoscale Magnetic Materials in Biological Systems

In this review, we provide an overview of methods for synthesizing magnetic nanoparticles (MNPs) with potential applications to biomedical research. We explore how the structure and properties of these particles are related to their diverse uses in medical diagnostics and bioanalysis. Special emphasis is placed on MNPs containing noble metals, which serve as biomarkers or active agents. Specifically, we focus on the application of direct and combined methods of atomic spectroscopy (ETAAS, AES/ICP–MS) to biomedical research. Experimental approaches to studying the behavior and transformations of MNPs in vitro and in vivo are considered. The importance of proper sample preparation in simulating the behavior of nanoparticles in biological media is highlighted. We also examine the significance of preparation techniques for the accurate determination of dissolved and nanosized forms in biological samples. Lastly, we assess the potential for the comprehensive studies of MNP behavior within complex biological systems, pointing toward future directions in this dynamic and promising field of research.

DETERMINATION OF THE TRACE ELEMENT COMPOSITION OF BLACK SHALE ROCKS AND ORES. CERTIFIED REFERENCE MATERIALS OF SLg-1 AND SChS-1

A set of methods for studying the trace element composition of black shales has been developed, including various options for preparing samples for analysis to determine individual groups of elements, including PGE and gold, by atomic spectroscopy methods (ICP-AES, ICP-MS, ETAAS). Data on the content of 54 elements in certified reference materials (CRMs) of black shale rocks SLg-1 and SChS-1 were obtained. The metrologically characterized data will make it possible to use these CRMs for a detailed study of the composition of rocks and ores containing carbonaceous matter. The relevance of the problem is due to the absence of natural multi-element CRMs, in which elevated and clarke contents of gold, silver, as well as all PGEs, are simultaneously certified.

The content of chemical elements-antioxidants in the tissues of benign and malignant tumors

Background. Copper, zinc, manganese, and selenium play the role of cofactors in the enzymatic link of the antioxidant system and can be singled out as a special group of antioxidant elements. Reorganizations of the antioxidant system during carcinogenesis are reflected in the levels of these bioelements.&#x0D; Aim. Analysis of the antioxidant element concentrations in benign and malignant tumor tissues and assessment of the possibility of their use as markers of neoplasms.&#x0D; Material and methods. Using the methods of atomic emission and mass spectrometry with inductively coupled argon plasma, the concentrations of Cu, Zn, Mn and Se were measured in the tissues of benign and malignant neoplasms (surgical material) of 131 residents of Magadan. The objects of the study were benign neoplasia of the intestine, breast and ovary, as well as malignant neoplasia of the intestine, breast, uterus and lung. The ShapiroWilk test, the MannWhitney U test, and correlation analysis were used. Changes were considered significant at p 0.05.&#x0D; Results. In a benign process, all antioxidant elements, in a malignant process, Cu and Zn turned out to be differentiating. The maximum levels of Cu, Zn, Mn and Se were recorded in benign and malignant tumors of the intestine (2.09 and 2.57; 62.99 and 22.22; 0.35 and 0.29; 0.33 and 0.30 g/g, respectively), minimal in benign and malignant breast tumors (0.58 and 0.88; 8.74 and 10.41; 0.08 and 0.19; 0.11 and 0.21 g/g). The value of the Cu/Zn ratio corresponded to the range of 0.0740.111 and significantly prevailed in cancer (p 0.05). Significant correlations (p 0.037) were recorded only in tumors of the intestine and breast and differed in multidirectional dynamics. Their number decreased in bowel cancer and increased in breast cancer.&#x0D; Conclusion. Malignant neoplasms are distinguished by a higher level of antioxidant elements and atypism of the microelement profile.

Study of air pollution in the area of compact accommodation of students (campuses) of three universities in Vladivostok city

The article presents the results of the study of airborne particulate matter in Vladivostok city in three areas of compact residence of students (university campuses) using the methods of laser particle size analysis and atomic emission spectrometry. It is shown that the atmospheric air in these areas of the city is polluted with airborne particulate matter with diameter less than 10 μm (PM10). In 5 out of 13 points, we found PM10 microparticles hazardous to health in significant proportions – from 39.9% to 99.5%. The maximum content of particles of the smallest fraction was detected in the Maritime State University campus (railway dead end near the Vladivostok commercial port). The content of particles of heavy metals (I and II hazard class) in the air was identified as well.

New Chelate Resins Prepared with Direct Red 23 for Cd2+, Ni2+, Cu2+ and Pb2+ Removal.

In this paper, two chelate resins prepared by a simple procedure were used for the removal of Cd2+, Ni2+, Cu2+, and Pb2+ (M2+) from aqueous solutions. Amberlite IRA 402 strongly basic anion exchange resin in Cl- form (IRA 402 (Cl-) together with Amberlite XAD7HP acrylic ester co-polymer (XAD7HP) were functionalized with chelating agent Direct red 23 (DR 23). The chelate resins (IRA 402-DR 23 and XAD7HP-DR 23) were obtained in batch mode. The influence of interaction time, pH and the initial concentration of DR 23 solution was investigated using UV-Vis spectrometry. The time necessary to reach equilibrium was 90 min for both resins. A negligible effect of adsorption capacity (Qe) was obtained when the DR 23 solution was adjusted at a pH of 2 and 7.9. The Qe of the XAD7HP resin (27 mg DR 23/g) is greater than for IRA 402 (Cl-) (21 mg DR 23/g). The efficiency of chelating resins was checked via M2+ removal determined by the atomic adsorption spectrometry method (AAS). The M2+ removal by the IRA 402-DR 23 and XAD7HP-DR 23 showed that the latter is more efficient for this propose. As a consequence, for divalent ions, the chelated resins followed the selectivity sequence: Cd2+ &gt; Cu2+ &gt; Ni2+ &gt; Pb2+. Additionally, Cd2+, Cu2+ and Ni2+ removal was fitted very well with the Freundlich model in terms of height correlation coefficient (R2), while Pb2+ was best fitted with Langmuir model for IRA 402-DR 23, the Cu2+ removal is described by the Langmuir model, and Cd2+, Ni2+ and Pb2+ removal was found to be in concordance with the Freundlich model for XAD7HP-DR 23. The M2+ elution from the chelate resins was carried out using 2 M HCl. The greater M2+ recovery from chelating resins mass confirmed their sustainability. The chelate resins used before and after M2+ removal by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) analysis were evaluated.

Properties and Analysis of Liquid Alternative Fuels I: Fatty Acid Esters

The importance of alternative fuels is constantly growing due to environmental reasons, saving fossil fuels and reducing the dependence of the world countries on the supply of fossil raw materials from politically unstable regions. This article is further in a series of review articles focused on an overview of technical requirements and testing methods for selected alternative fuels. It is also the first in a series of papers focused on liquid alternative fuels. The aim of this series of articles is to provide an overview of the required properties of individual alternative fuels, the possibilities of their analysis and the importance of the individual analyzes. This article focuses on fuels containing fatty acid esters.Biodiesel can be burned in diesel engines either in a mixture with conventional diesel or as an individual fuel. Unlike conventional diesel, which is composed of hydrocarbons of petroleum origin, biodiesel contains fatty acid methyl esters. In addition to this main component, glycerol (by-product of transesterification), methanol, free fatty acids, glycerides (mono-, di- and tri-), catalyst residues, water, and possibly other components can be present also. These contaminants can, in certain concentrations, cause some undesirable properties both in pure biodiesel and in biodiesel/diesel blends. Compared to conventional diesel, biodiesel has a higher density and viscosity, but a slightly lower higher heating value, and considerably worse oxidation stability. In terms of pollutant emissions, the combustion of biodiesel produces less hydrocarbons, carbon monoxide and solid particles, but slightly more nitrogen oxides than the combustion of mineral diesel. Gas chromatography, infrared spectroscopy, titration methods, and atomic spectroscopy methods have typically been used for the evaluation of these fuels. In addition to the properties monitored by these methods, conventional fuel parameters such as density, viscosity, low-temperature properties, oxidation stability, corrosion properties, flash point, cetane number, and others are monitored for biodiesel and biodiesel/diesel blends. In general, it can be stated that the analysis of fuels containing biodiesel is well managed. Instrumental equipment and (modified) analytical methods used for the analysis of conventional liquid fuels can be used to analyze these fuels.

Utilization of overburden in formulations of environmentally friendly compositional materials for road construction

The possibility of utilization of overburden rocks of the Chernovsky brown coal and Baleysko-Taseevsky gold occurrences (Trans-Baikal Region) in the road construction industry is studied. Polymeric additives Cryogelite and StabOL were chosen as stabilizing additives in the compositions of road-building composites. The initial mineral samples were examined by methods of atomic emission spectrometry with inductively coupled plasma, powder diffraction, and infrared spectroscopy. It was found that the introduction to formulation of composites with use of overburden rocks of 8 wt. % Portland cement and 10 wt. % fly ash, as well as stabilizing additives Cryogelit (Chernovskoe occurrence) and StabOL (Baleysko-Taseevskoe occurrence), allows to obtain samples with strength grade M40 and frost resistance grade F15. The biotesting method proved that the obtained composites do not have an acute toxic effect on test objects and are safe for the environment and human health.

Evaluation of Arsenic Concentration in Poultry and Calf Meat Samples by Hydride Generation Atomic Fluorescence Spectrometry

A simple, cost effective hydride generation atomic florescence spectrometry (HG-AFS) method was used for determination of total arsenic (As) in poultry and calf meat samples. The samples were digested in long necked glass digestion tubes using concentrated HNO3, HClO4 and H2SO4 as a mixture. The volume of acids (HNO3, HClO4) and the amount of sample to be used for digestion were optimized to achieve appropriate digestion. The accuracy of the proposed HG-AFS method was tested with certified reference material (DOLT 3 Dogfish Liver, NRC, Canada) and obtained results were in good agreement with certified value. The method limit of detection (LOD) value was calculated as 0.3 ng/g and dynamic range was 25 – 5000 pg/ml. Arsenic concentrations of poultry and calf meat samples were determined accurately by using aqueous calibration standards. Totally 31 samples (calf, chicken and turkey) obtained from local markets were analyzed. It was found that the average As concentration in calf meat (12.1 ± 3.9 ng/g) was significantly higher than the poultry samples whereas the arsenic concentrations were similar in turkey (3.1 ± 1.2 ng/g) and chicken (2.8 ± 1.1 ng/g) samples. In addition, dietary intake estimation of arsenic through consumption of calf and poultry meat was calculated and according to the gathered results daily intake of arsenic via calf meat was almost two times higher than poultry meat.

Can the Application of Municipal Sewage Sludge Compost in the Aided Phytostabilization Technique Provide an Effective Waste Management Method?

(1) Background: sewage sludge is a by-product of wastewater treatment, which needs to be managed appropriately, e.g., in composting processes. The application of municipal sewage sludge composts (MSSCs) as a soil amendment is a potential way to effectively manage sewage sludge. (2) Methods: this paper presents the results of a vegetation pot experiment undertaken to assess the suitability of Dactylis glomerata L. and MSSC in the aided phytostabilization technique when applied on soils from an area effected by industrial pressure; this is characterized by high levels of heavy metal (HM). The contents of HMs in the test plant (the roots and above-ground parts), as well as in the soil and MSSC, were determined via an atomic spectrometry method. (3) Results: the application of MSSC positively contributed to an increased production of plant biomass and an increase in the pH in the soil. Concentrations of Cu, Cd, Pb, Zn, and Cr were higher in the roots than in the above-ground parts of Dactylis glomerata L. The addition of MSSC contributed most significantly to the considerable reduction in Ni, Pb, and Zn contents in the soil after the experiment. (4) Conclusions: MSSC can support the phytostabilization of soils contaminated with high levels of HMs.

Determination of alkali metal interference factors in reforming catalyst by atomic absorption spectrometry and elimination method

Determination of alkali metal interference factors in reforming catalyst by atomic absorption spectrometry and elimination method

Determination of heavy metals concentration in waste water of Warri Refining and Petrochemicals Company (WRPC)

Waste water from some industries contain high levels of contaminant such as colloid, suspended and dissolved minerals. Heavy metals have negative impact on all forms of life in the environment. Crude oil refining makes use of large volume of water, whence generate large quantities of waste water which must comply with stringent environmental guidelines. To this end, several treatment methods have been explored in order to keep contaminants levels within limits. This study investigated the presence of heavy metals in discharged waste water effluents from the premises of Warri Refining and Petrochemical Company LTD into the Ubeji creek. The analysis was carried out using the Flame Atomic Adsorption Spectrometry method. Standard solution used for calibration were prepared for the five heavy metals analysed. Results showed average concentrations of chromium was within the acceptable limit. The overall results show that effluent water from WRPC has concentrations of heavy metals that is within the prescribed acceptable limits for discharge into the environment.

Developing the atomic spectrometry techniques for cobalt and nickel analysis

The existing methods standardized for to cobalt and nickel analysis, i.e. GOST 13047–2014, GOST 6012–2011 and GOST 8776–2010, don’t correspond to the current and future requirements to these metals in terms of impurities concentration. GOST 13047–2014 provides single-element analysis applications that establish a sample preparation for single element only, takes a lot of efforts and an extremely long time, consume a lot of chemical reagents and are associated with a significant harmful impact on the environment. Being a multielement technique, atomic emission spectrometry with DC-arc spectrum excitation is associated with a high consumption of chemical reagents and a significant environmental impact. It doesn’t allow determining the sulfur and other important impurities. All standard techniques are based on the obsolete principle to dissolve the samples in glass beakers on hot plates. The authors of this paper propose to standardize the methods of atomic emission spectrometry and mass spectrometry (MS) with inductively coupled plasma (ICP) to run cobalt and nickel analysis. 2.5 g samples of cobalt and nickel were proposed to decompose in a mixture of acids in closed polypropylene vessels heated in HotBlock systems at the temperature of 110 оC. This saved up to 5 cm3 of nitric acid and up to 5 cm3 of hydrochloric acid. The solutions of nickel and cobalt were analyzed for impurities on an iCAP 6500 Duo spectrometer at low plasma discharge power and using the base lines as an internal standard. This helped to improve the detection limits of impurities. To select optimal wavelengthes, full spectra of analyzed solutions were captured. Isotope 185Re was chose as internal standard and a collision and reaction cell was used to remove interfering polyatomic ions on an ICP-MS spectrometer iCAP Qc. Nickel and cobalt samples as well as CRMs were analyzed. The impurities detection limits with the current and future cobalt and nickel grades. The methods developed may create the basis for a new GOST standard applicable to cobalt and nickel analysis.

Research of composition and properties of ash and slag waste from the Thermal Power Plant of Trans-Baikal region for decrease of anthropogenic impact on environment

The anthropogenic impact on environment of ash and slag waste of CHP 1 and CHP 2 (Chita) and CHP Priargunsky Industrial Mining and Chemical Union (Krasnokamensk) is considered. These wastes cause irreparable damage to the environment, occupy a significant area, lead to a deterioration of the environmental situation in the surrounding areas. Liquidation of such objects of accumulated harm to the environment is the most important state task in the areas of national economy and environmental protection. Rapid recycling of ash and slag waste is possible in road construction (the main material-intensive sector of the national economy) due to large-capacity direct use. This will effectively reduce the anthropogenic impact on the environment and significantly reduce the use of mineral raw. The principal possibility of using of fly ash as a secondary mineral raw material in compositions of road soil concrete is substantiated. The methods of atomic emission spectrometry with inductively coupled plasma, differential scanning calorimetry and thermogravimetry were used to study the composition and properties of fly ash of CHP, which is a first-class mineral raw based on the specific effective activity of natural radionuclides (226Ra, 232Th, 40K), which allows their use in the construction industry without restrictions. It has been established that fly ash is non-porous, its hydraulic properties are classified as latent-active and can be added to road cement soils modified with additives of different nature.

Matrix-matched two-point calibration based on the standard dilution analysis method

A two-point calibration, based on the standard dilution analysis (SDA) method, is used to achieve accurate results while analyzing complex-matrix samples by different atomic spectrometry methods. Only two calibration solutions are required per sample. Solution 1 (S1) is 50% sample and 50% of a standard containing the analytes and an internal standard (IS), and Solution 2 (S2) is 50% sample and 50% blank. The concentration of analyte in the sample is calculated from (i) the slope and intercept of an analyte vs. IS plot, (ii) the concentration of analyte in the standard added to S1, and (iii) the signal intensity of the IS present in S1. Unlike recently published work on SDA, the method presented here requires no mixing of S1 and S2, no second IS species, and no instrumental modifications or extra equipment. In this proof-of-concept study, the new approach has been used to determine Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn in different matrices: 1% v/v HNO3, 20% v/v HNO3, 0.1% m/v Na, and 0.1% m/v Ca. The analytes were accurately determined by microwave-induced plasma optical emission spectrometry (MIP OES), inductively coupled plasma OES (ICP OES), and ICP mass spectrometry (ICP-MS) using the new method. The results were compared to those from external standard calibration (EC), internal standardization (IS), and standard additions (SA). Similar and often superior recoveries compared with EC, IS and SA were achieved with the matrix-matched two-point calibration method.

Mercury in samples of gas mixtures – a review of mercury sampling and determination methods

The determination of the composition of gas mixtures, especially those analytes which exist, for example, as contaminants for the main components of the gas mixture, very often requires the concentration of the analyte so that it can be quantified. The analysis of gaseous environmental samples, including air and air samples at workplaces, is difficult, which results from: the need to work with samples with an extensive matrix and heterogeneous distribution of pollutants, the stability of the analyte and the presence of interfering substances (interferents) in the sample. On the other hand, the analysis of trace components of gaseous fuels is difficult due to the need to collect a suitably concentrated sample so that these components can be quantified. This article provides an overview and analysis of the methods used for the collection and determination of mercury in gas mixtures. Currently, there are standardized mercury collection and determination methodologies dedicated to matrices such as air, workplace air, waste gases or natural gas. These are both manual and fully automated methods. Most of the methods described in the literature on the subject consist of two stages, i.e. the stage of collecting a sample for a solid or liquid sorbent and the stage of desorption and determination of the mercury content in the collected sample using methods dedicated to the analysis of this element. The most frequently used methods for collecting mercury samples in gas mixtures are: the gold amalgamation method and the sorption methods on powder sorbents (such as activated carbon, hopcalite, impregnated silica gel), glass fibers, impregnated cellulose filters and liquid sorbents (such as e.g. acids). The methods of sample desorption are varied and depend on the material on which the analyte has been absorbed and the selected mercury determination method. Three methods are mainly used to analyze samples for mercury content, i.e. the cold vapor atomic absorption spectrometry method (CV-AAS), the cold vapor fluorescence atomic spectrometry method (CV-AFS) and the inductively coupled plasma mass spectrometry method (ICP-MS). However, it should be kept in mind that although the methods available and used for the analysis of mercury content in gas are standardized, they are not resistant to the presence of hydrocarbons and hydrogen sulphide in the tested samples. These are the compounds that are most often mentioned as substances interfering in the determination of mercury in gases using the above-mentioned methods.