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VOLUME 11 NUMBER 1 2018 ISSN 2218-7979 International Journal of Biology and Chemistry Al-Farabi Kazakh National University International Journal of Biology and Chemistry is published twice a year by al-Farabi Kazakh National University, al-Farabi ave., 71, 050040, Almaty, the Republic of Kazakhstan website: http://ijbch.kaznu.kz/ Any inquiry for subscriptions should be sent to: Prof. Mukhambetkali Burkitbayev, al-Farabi Kazakh National University al-Farabi ave., 71, 050040, Almaty, Republic of Kazakhstan e-mail: Mukhambetkali [email protected] © 2018 al-Farabi Kazakh National University Printed in Kazakhstan EDITORIAL The most significant achievements in the field of natural sciences are reached in joint col- laboration, where important roles are taken by biology and chemistry. Therefore publication of a Journal, displaying results of current studies in the field of biology and chemistry, facilitates highlighting of theoretical and practical issues and distribution of scientific discoveries. One of the basic goals of the Journal is to promote the extensive exchange of information between the scientists from all over the world. We welcome publishing original papers and mate- rials of biological and chemical conferences, held in different countries (after the process of their subsequent selection). Creation of special International Journal of Biology and Chemistry is of great importance, because a great amount of scientists might publish their articles and it will help to widen the ge- ography of future collaboration. We will be glad to publish also the papers of the scientists from the other continents. The Journal aims to publish the results of the experimental and theoretical studies in the field of biology, biotechnology, chemistry and chemical technology. Among the emphasized subjects are: modern issues of technologies for organic synthesis; scientific basis of the production of physiologically active preparations; modern issues of technologies for processing of raw materi- als, production of new materials and technologies; study on chemical and physical properties and structure of oil and coal; theoretical and practical issues in processing of hydrocarbons; modern achievements in the field of nanotechnology; results of studies in the fields of biology, biotechnol- ogy, genetics, nanotechnology, etc. We hope to receive papers from a number of scientific centers, which are involved in the ap- plication of the scientific principles of biology, biotechnology, chemistry and chemical technol- ogy on practice and carrying out research on the subject, whether it relates to the production of new materials, technology and ecological issues. International Journal of Biology and Chemistry 11, № 1, 4 (2018) IRSTI 31.19.29 1*D. Orazbayeva, 1B. Kenessov, 2J.A. Koziel 1Al-Farabi Kazakh National University, Faculty of Chemistry and Chemical Technology, Center of Physicochemical Methods of Research and Analysis, Almaty, Kazakhstan 2Iowa State University, Department of Agricultural and Biosystems Engineering, Ames, IA 50011, USA *e-mail: [email protected] Quantification of naphthalene in soil using solid-phase microextraction, gas-chromatography with mass-spectrometric detection and standard addition method Abstract: Development of simple, fast and accurate methods for quantification of volatile organic compounds (VOCs) in soil samples is important for providing greater efficiency of analytical laboratories in Kazakhstan and other developing countries. Naphthalene is a model polycyclic aromatic hydrocarbon (PAH), belonging to a group of compounds of significant concern due to environmental impact. Solid- phase microextraction (SPME) is an optimal method for solvent-free automated sample preparation for determination of VOCs in environmental samples. In this work, the method for quantification of naphthalene in soil based on headspace SPME, gas chromatography with mass spectrometric detection, and standard addition calibration was developed. The parameters of SPME and sample equilibration after spiking with standards were optimized for better control of the soil matrix effect. The SPME temperature 80 °C provided the greatest accuracy of naphthalene responses for soils with different matrix and humidity. Equilibration of soil samples after spiking with standards for 6 h at 80 °C provided stabilization of responses in soils with different matrix and water content. The greatest accuracy and precision were achieved after equilibration of the samples for 8 h. The method provides recoveries of 105-119% in the concentration range 0.01-0.1 ng g-1 with detection limit 0.001 ng g-1. The developed method was applied for quantification of naphthalene in real soil samples collected in Almaty, Kazakhstan. The measured concentration of naphthalene in real soil samples varied in the range of 1.4 to 47 ng g-1. In five out of ten collected soil samples concentration exceeded a maximum permissible concentration of 15 ng g-1. Key words: naphthalene, soil analysis, solid-phase microextraction, standard addition, gas chromatography. Introduction silica gel) and an evaporative concentration [3–5], which can result in the emission of toxic compounds Naphthalene is a ubiquitous pollutant found in to an environment. many environmental samples of air, water, soil. It The most promising “green” method of sample is a confirmed carcinogen and mutagen linked to preparation for the determination of volatile and semi- hemolytic anemia and cataracts in humans [1,2]. volatile organic compounds (VOCs and SVOCs) Along with other polycyclic aromatic hydrocarbons in soils is solid-phase microextraction (SPME) [6]. (PAHs), naphthalene can be released into the envi- SPME combines sampling, extraction, concentration, ronment during transportation, storage, and use of and purification steps into one easily automated op- crude oil and oil products [2]. The soil is often the eration. During SPME, VOCs are transferred onto the main sink of PAHs spills. polymer coating from a headspace (HS) above a soil Standard methods for quantification of naphtha- sample. Extracted analytes are then desorbed in an in- lene in soil require waste-generating, costly and time- let of a gas chromatograph for analysis (Figure 1). This consuming sample preparation using toxic organic method does not require organic solvents and provides solvents (e.g., acetonitrile, acetone, chloroform, di- an ideal combination of simplicity and sensitivity. ethyl ether, methanol). The extraction of an analyte Available SPME-based methods for quantifica- from soil is followed by purification of the extracts tion of naphthalene and other PAHs in soil include by passing through adsorbent (e.g., aluminum oxide, preliminary extraction with a surfactant solution [7] © 2018 al-Farabi Kazakh National University Printed in Kazakhstan D. Orazbayeva et al. 5 or an organic solvent [8], while SPME is conducted in the best accuracy of naphthalene responses for soils direct-immersion (DI) mode. For headspace SPME, with different matrix and humidity. Soil equilibration extraction is conducted with simultaneous heating of temperature and time after spiking with naphthalene the sample and cooling of a fiber coating (cold-fiber standard were optimized. The developed method SPME) [9–11], or at low-pressure conditions (vac- was successfully applied for the analysis of real soil uum-assisted HS-SPME) [12]. The main limitations samples. of CF-SPME and vacuum-assisted HS-SPME are the complexity of method instrumentation and its auto- Materials and methods mation, along with no commercial availability. The accuracy of SPME-based quantification of Reagents, materials, and samples VOCs and SVOCs in soil is affected by a matrix ef- Naphthalene (99%) was purchased from Meryer fect, which results in variable extraction efficiencies (China). Methanol (HPLC grade) purchased from of analytes from samples having different physico- AppliChem (Germany) was used for the prepara- chemical properties. To overcome the matrix effect, tion of standard solutions. SPME fiber – 100 µm two main approaches are used: control of the matrix polydimethylsiloxane (PDMS) was purchased from effect by obtaining a calibration plot for each type of Supelco (USA). Soil sampling and calibration were soil; and a decrease of the matrix effect by increas- performed in 20-mL crimp-top headspace vials ing the extraction temperature, addition of water, or (HTA, Italy) with PTFE/silicone septa (Zhejiang using cold-fiber SPME [13]. The main difficulty in Aijiren Technology Co., China). All vials and septa using the first approach is a long and often inefficient were washed with distilled water and pre-conditioned equilibration of samples after their spiking with stan- at 140 °C for 2 h before analysis. dards [14; 15]. Two different soil types were used: clay and chernozem having humus content 0.90 and 45%, re- spectively. These soils will be referred hereinafter as Fiber Extraction Desorption soils with ‘low’ and ‘high’ humus content (LHC and 12assembly over soil 3in GC inlet HHC), respectively. Both soils were collected near Almaty, Kazakhstan. Soils were cleaned from pos- sible naphthalene residues and water by heating in a drying furnace at 150 °C for 6 h. Parameters of gas chromatography-mass spec- trometry (GC-MS) analysis Protecting He Inlet liner GC-MS analyses were performed on the needle 6890N/5973N system (Agilent, USA) equipped with CF a Combi-PAL autosampler (CTC Analytics, Swit- Fiber zerland). Separation was conducted using a polar 60 C coating HS m x 0.25 mm DB-WAXetr