Coal combustion byproducts-fly ash (FA), bottom ash (BA), and ash and slag waste (ASW)-are of considerable interest for the development of their application as soil ameliorants since these harmful wastes are produced in large quantities and need to be utilized or processed. Moreover, if FA is studied quite well in this respect, much less data exists on the BA and ASW, with fewer opportunities for their other economically justified use. Thus, this research focused on the possibility of FA and BA (ASW) application as soil ameliorants. Ash samples from power plants in European Russia were selected since they are not studied in detail before. To estimate the impact of ash application, changes in key indicators reflecting the soil quality, its suitability for growing safe products were assessed: particle size distribution, acidity, nutrient, and potentially toxic elements (PTEs; heavy metals and metalloids) concentration, and their potential availability for plants. The application of ash samples to soddypodzolic soil contributed to pH normalization, confirming the possibility of using these wastes as a stabilizer of soil acidity at the optimum ratio of ash to the soil of 1:2 or 1:5. ASW samples can aggregate with soil particles, contributing to agrophysically valuable aggregates 250-2000 mu m. Despite the contents of PTEs, ASW can be considered a safe material as the legislatively established standards are not exceeded.

A critical review of the methods for producing pyrolysis waste oils was carried out, the possibilities and limitations of each approach were discussed. Liquid pyrolysis products (pyrolysis oils) are promising source of valuable chemical compounds, and can be also used as a fuel. A reliable analysis of pyrolysis oils is necessary to study their component composition, basic characteristics and to select the most suitable methods for the extraction of the necessary compounds. It is known that the results of GC-MS analysis of liquid pyrolysis products are usually ambiguous: there are problems of peaks overlapping and incorrect interpretation of the data, due to the complexity of the matrix and the multicomponent composition of the object. The paper presents data on the chemical composition of pyrolysis oils obtained by elemental analysis, IR spectroscopy, NMR spectrometry, GC-MS, GC-GC/MS. Based on the presented results, pyrolysis oil usually contains aromatic compounds, water-soluble substances and hydrocarbons. It was found out that there are conflicting data on the chemical composition of the pyrolysis oils of waste tires in the scientific literature. It is proposed to carry out sequential extraction sample preparation of pyrolysis mixtures to increase the reliability and accuracy of the componential and quantitative composition of the GC-MS method. Obviously, a reliable analysis of complex pyrolysis mixtures without preliminary targeted sample preparation seems unlikely.

A critical review of the methods for producing pyrolysis waste oils was carried out, the possibilities and limitations of each approach were discussed. Liquid pyrolysis products (pyrolysis oils) are promising source of valuable chemical compounds, and can be also used as a fuel. A reliable analysis of pyrolysis oils is necessary to study their component composition, basic characteristics and to select the most suitable methods for the extraction of the necessary compounds. It is known that the results of GC-MS analysis of liquid pyrolysis products are usually ambiguous: there are problems of peaks overlapping and incorrect interpretation of the data, due to the complexity of the matrix and the multicomponent composition of the object. The paper presents data on the chemical composition of pyrolysis oils obtained by elemental analysis, IR spectroscopy, NMR spectrometry, GC-MS, GC-GC/MS. Based on the presented results, pyrolysis oil usually contains aromatic compounds, water-soluble substances and hydrocarbons. It was found out that there are conflicting data on the chemical composition of the pyrolysis oils of waste tires in the scientific literature. It is proposed to carry out sequential extraction sample preparation of pyrolysis mixtures to increase the reliability and accuracy of the componential and quantitative composition of the GC-MS method. Obviously, a reliable analysis of complex pyrolysis mixtures without preliminary targeted sample preparation seems unlikely.

A method for the extraction sample preparation of pyrolysis oil obtained from the waste automobile tires with the subsequent GC-MS component and quantitative analysis has been proposed and tested. The method is based on the sequential extraction of pyrolysis oil components from its hexane solution by several selective solvents and reagents, followed by the separation of the components from the extracts and their GC-MS analysis. Pyrolysis oil can be separated into water-soluble polar substances of relatively low molecular weight, including organic acids and bases; water-insoluble substances with polar functional groups in the molecule; multi-core condensed structure arenas; aliphatic and naphthenic hydrocarbons that do not contain other classes of organic compounds. A hexane solution of pyrolysis oil was subsequently extracted with water (with additions of mineral acid and alkali), ethylene glycol (with additions of mineral acid and alkali), dimethyl sulfoxide, and then treated with oleum. As a result, it was found by using the chromato-distributive method that the pyrolysis oil contains saturated and unsaturated hydrocarbons, derivatives of benzenes, naphthalenes, polycyclic aromatic hydrocarbons, sulfur- and nitrogen-containing organic compounds, phenols, etc. It was shown that the preliminary extraction separation of the components of pyrolysis oil can increase the number of identified oil components and increase the reliability of GC-MS analysis. Keywords: pyrolysis of automobile tyres, extraction, chromato-distributive method DOI: http://dx.doi.org/10.15826/analitika.2019.23.3.004 (Russian) 1 S. M. Leschev, 1,2 T. M. Henarava, 2 V. V. Sauchyn, 3 V. V. Levkina 1 Belarusian State University, Republic of Belarus, 22006 Minsk, Leningradskaia st., 4 2 A.V. Luikov Heat and Mass Transfer Institute of the National Academy of Sciences of Belarus, Brovki st., 15, Minsk, 220072, Republic of Belarus 3 Moscow State University of M.V. Lomonosov, Leninskie Gory, 1, Moscow, 119991,Russian Federation

The work presents the comparison results of the quantitative and qualitative composition of hydrocarbon compounds that can be obtained as a result of secondary and tertiary methods of influence on organic-rich rocks (on the example of the Bazhenov Formation rocks) with a high oil-generating potential. It is shown that as a result of extraction of bitumoids presented in open pores, realisation the generation potential and the production of synthetic oil, it is possible to produce hydrocarbon compounds, the amount of which reaches 35 kg and 20 kg per 1 m3 of rock, respectively. Products possess high maturity and are identical in composition to the oil extracted from these rocks by standard technology of development. It was found that with the development of appropriate technologies of subsequent influence on the formation by secondary and tertiary methods, oil production can be significantly increased in the future.

Using an example of tetraphenyltin (TePT), a new method is developed and tested for the isolation and preconcentration of toxic organometallic compounds from soils. It consists in the preconcentration of the target component in an organic layer formed after the splitting of a microemulsion (ME), followed by the determination of TePT by reversed-phase HPLC with spectrophotometric detection. The dependence of the TePT concentration factor in the organic layer formed after the splitting of the ME on the composition of the ME is studied. It is found that, in using a ME of the composition sodium dodecyl sulfate–n-hexane–n-butanol–water (3 : 1.5 : 6 : 89.5, by volume), the concentration factor is maximal and equal to 10. The limit of detection for TePT is 0.1 ng/mL.

A method for identifying straits of rocket kerosene (RG-1 and T-1 brands) and various types of hydrocarbon fuels (aviation fuel TC-1 and diesel fuel) in soil has been developed. The proposed version of identification is based on the preliminary separation of the main components by gas chromatography and their mass spectrometric detection followed by the processing of the data obtained by chemometric methods of analysis (principal component analysis and projection on latent structures with discriminant analysis) using the “MZmineZ,” “iMet-Q,” and “MetaboAnalyst” software. A possibility of the application of the developed approach to the typification of saturated oil fractions of different origin is illustrated.

A method for the extraction sample preparation of pyrolysis oil obtained from the waste automobile tires with the subsequent GC-MS component and quantitative analysis has been proposed and tested. The method is based on the sequential extraction of pyrolysis oil components from its hexane solution by several selective solvents and reagents, followed by the separation of the components from the extracts and their GC-MS analysis. Pyrolysis oil can be separated into water-soluble polar substances of relatively low molecular weight, including organic acids and bases; water-insoluble substances with polar functional groups in the molecule; multi-core condensed structure arenas; aliphatic and naphthenic hydrocarbons that do not contain other classes of organic compounds. A hexane solution of pyrolysis oil was subsequently extracted with water (with additions of mineral acid and alkali), ethylene glycol (with additions of mineral acid and alkali), dimethyl sulfoxide, and then treated with oleum. As a result, it was found by using the chromato-distributive method that the pyrolysis oil contains saturated and unsaturated hydrocarbons, derivatives of benzenes, naphthalenes, polycyclic aromatic hydrocarbons, sulfur- and nitrogen-containing organic compounds, phenols, etc. It was shown that the preliminary extraction separation of the components of pyrolysis oil can increase the number of identified oil components and increase the reliability of GC-MS analysis. Keywords: pyrolysis of automobile tyres, extraction, chromato-distributive method DOI: http://dx.doi.org/10.15826/analitika.2019.23.3.004 (Russian) 1 S. M. Leschev, 1,2 T. M. Henarava, 2 V. V. Sauchyn, 3 V. V. Levkina 1 Belarusian State University, Republic of Belarus, 22006 Minsk, Leningradskaia st., 4 2 A.V. Luikov Heat and Mass Transfer Institute of the National Academy of Sciences of Belarus, Brovki st., 15, Minsk, 220072, Republic of Belarus 3 Moscow State University of M.V. Lomonosov, Leninskie Gory, 1, Moscow, 119991,Russian Federation

Разработан способ идентификации проливов в почве ракетных керосинов (марок РГ-1 и Т-1) и близких к ним по физико-химическим свойствам углеводородных топлив (авиационного керосина марки ТС-1 и дизельного топлива). В основу предложенного варианта идентификации входит предварительное разделение основных компонентов методом газовой хроматографии и их масс-спектрометрическое детектирование, а также обработка полученных данных с помощью хемометрических методов анализа (метода главных компонент и дискриминационного анализа с помощью регрессии на латентные структуры) с помощью программ «MZmine2», «iMet-Q» и «MetaboAnalyst». Проиллюстрирована возможность применения разработанного подхода для типизации насыщенных фракций нефтей, имеющих различное происхождение. A method for identifying straits of rocket kerosene (RG-1 and T-1 brands) and various types of hydrocarbon fuels in the soil (aviation fuel ТС-1 and diesel fuel) has been developed. The proposed variant of identification is based on the preliminary separation of the main components by gas chromatography and their mass spectrometric detection, and processing of the obtained data with chemometric methods of analysis (principal component analysis and projection on latent structures with discriminant analysis) using the programs "MZmine2", "iMet-Q" and "MetaboAnalyst". The opportunity of application of the developed approach for the typification of saturated fractions of oils from different origins is illustrated.

The possibility of using microemulsions as extractants during the extraction of chemical markers from oil samples and their subsequent preconcentration by the decomposition of microemulsions and determination of oil components by the gas chromatography-mass-spectrometry method is shown. Due to hydrophobicity, oil components pass into the organic phase after the decomposition of microemulsions and become concentrated due to the reduction of the volume of one of the phases. It is shown that as the preconcentration of the precipitant increases, the preconcentration coefficient of the chemical markers grows to 8–10. The method itself is characterized by low detection limits, good selectivity, and reproducibility.