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42ОБЗОРНАЯ СТАТЬЯ
IRSTI 31.19.29
M.R.Mamedova1 , A.B.Ibraimov2, A.N.Kunanov2, M.BAlimzhanova1' 2, Z.A.Tukenova3
GREEN METHODS OF ANALYSIS OF PESTICIDES IN CEREALS: OVERVIEW
1al-Farabi Kazakh National University, Faculty of Physics and Technology, 050070, 71 al-Farabi Ave, Almaty, Kazakhstan 2al-Farabi Kazakh National University, Faculty of Chemistry and Chemical Technology, 050070, 71 al-Farabi Ave, Almaty, Kazakhstan 3LLP Kazakh U.U. Uspanov Research Institute of Soil Science and Agricultural Chemistry, 050060, 75 В al-Farabi Ave, Almaty, Kazakhstan, e-mail: mamedova.madina@kaznu.kz
Abstract. Pesticides have been used all over the world since the mid-twentieth century to protect cereals and their derivatives in agriculture from pests, insects and fungi. The release of pesticides into the environment makes up a fraction of one percent of the total amount of chemical pollutants, but given that these compounds are aimed at suppressing certain groups of organisms, pesticides and their transformation products have a toxic effect on various forms of biota and on human health when ingested with vegetables and fruits, including from their surface, if they are poorly washed. And also, from cereals, as they can be absorbed into them from the soil. There are no safe pesticides, even when used in small quantities, they can cause various allergic reactions and poisoning. In the production of agricultural products, approved pesticides are used, but this does not negate the fact that long-term use of the drug can have negative consequences. Therefore, constant monitoring of the residual amount of pesticides in these products reduces the risk to human health and the environment. Hence, there is a need for efficient, rapid and cost-effective methods for the determination of pesticide residues. The article reflects the methods of sample preparation in the analysis of pesticides in grain crops, as well as features of the method of solid-phase micro extraction of one of the methods of environmental, green chemistry in the preparation of samples.
Key words: cereals, pesticides, methods of sample preparation, solid-phase micro extraction method, chromatography.
Balanced nutrition plays an im- their toxicity. Moreover, the entry of pesti-portant role in one's health and life. Fresh cides into the soil, in addition to their di-fruits and vegetables and cereals are an rect application is associated with water-important part of a balanced diet because ing plants and the runoff of sediments they contain a significant amount of nutri- from the surface of plants, the drift of ents and minerals [1]. The growing popula- drugs during the processing of fields, fortions around the world have led to the in- est lands, etc. The possibility of accumula-creased demand for food, hence using pes- tion of pesticides in the soil is determined ticides have become important to protect by the conditions of their use the plants before and after harvest [2]. Alt- (consumption rates, frequency of treat-hough the use of pesticides has played a ment), stability and solubility of drugs, soil key role in providing large quantities of type, its pH, temperature and humidity, inexpensive fruits and vegetables [3], they leaching conditions, inactivating effect of have side effects. Insecticides, herbicides, plants, penetration depth, etc. As a result and fungicides have been used effectively of chemical and biological processes in the to combat pests, fungi, and weeds. Howev- soil, the content of pesticides in it usually er, they enter fruit and vegetable cells and decreases, nevertheless, their residual remain in waste. This process may possibly amounts range from hundredths to tens of result in contamination of the products micrograms per 1 kg. The least stable pes-and poses a threat to human health due to ticides are in sandy soils, the most stable in
soils with a high content of clay, organic matter, iron, aluminum and manganese ions. Being in the soil, pesticides are exposed to the action of abiotic factors, and microorganisms play a significant role in their decomposition [4].
Grain is one of the products that is produced and consumed worldwide. This is because they supply essential minerals, vitamins and other microelements as a source of energy due to their high content of essential fatty acids, nutrients and dietary fibers. They are the basis for making a large variety of products. Various types of agrochemicals are used in agriculture to increase productivity. Insecticides, fungicides, herbicides and plant growth regulators are administrated to cereal production throughout the growing season, insecticides being the most frequently used Chlorpyrifos-methyl, pirimifos-methyl, chlorpyrifos, malathion, dichlorodiphe-nylethane are illustrative examples. Chlorpyrifos and its derivatives, malathion, chlorpyrifos, dichlorodiphenylethane (DDD) was banned in several states of US and in EU due to the health complications in young children (especially in fetuses) and adults [5-6]. Unfortunately, some of these pesticides were accumulated during Soviet Union and are still finding application in most Central Asian countries. Grain crops are often sprayed with insecticides even though some of them are banned in certain countries (for example, malathion, pirimi-phos-methyl, chlorpyriphos-methyl, del-tamethrin, d-phenothrin, tetramethrin, pirimicarb, or dichlorvos) [7-10]. To reduce the effect of the fungus, strobilurin, azoxystrobin, trifloxistrobin, kresoxim-methyl, as well as nitrogen fungicides chlo-rothalonil, propiconazole, epoxiconazole, tebuconazole, and boskalid are usually used. In cereal production, chlormecate, mepiquat, imazaquin, trinexapac-ethyl and 2-chlorethylphosphonic acid are used to reduce plant stems and thus reduce their ability to move [11, 12].
In conclusion, pesticide residue monitoring is important not only to ensure food security but also for the good industry practice, so it is important to develop highly sensitive, selective analytical methodologies that can now identify them by the required MPL (maximum permissible levels). Analysis of pesticide residues in various food and grain samples is currently a top priority in laboratories for controlling human health and quality.
Methods of sample preparation in the analysis of pesticides in cereals
Monitoring the residual quantities of pesticides in cereals and their derivatives contributes to the development of analytical methods aimed at detecting large numbers of pesticides through a single analysis. In addition, although research methods have been developed for the residual amount of one type pesticide, their cost and volume of work performed are generally a problem for laboratories. Due to the variety of pesticides and the intrinsic complexity of the matrices, different methods of sample pretreatment have been proposed. In some samples, high lipid content prevented the analysis. Most of the work on solvent extraction of pesticides from grain samples used gas chromatography with selective detection systems. Other methods have also been proposed (i.e., spectrofluorometry, resonance scattering, voltamperometry, enzyme-linked immunoenzyme analysis), but these methods can only identify one pesticide [13-15].
The determination of residual amounts of pesticides in food requires a long and labor-consuming sample preparation using highly toxic organic solvents (acetonitrile, chloroform, methylene chloride, acetone, methanol, toluene, etc.). Classical sample preparation involves extraction with an organic solvent, purification by passing through an adsorbent and concentrating by evaporation of the solvent. On average, 100-150 mL of solvent is required to prepare 1 sample, most of
which is released into the atmosphere during the analysis or is sent to waste [16].
In recent years, the QUEChERS method (fast, simple, inexpensive, efficient, durable and safe) has been proposed as an effective means of detecting pesticides in matrices. However, other methods, such as ultrasonic extraction, pressurized liquid extraction, sorbent-based processes, such as solid phase extraction, matrix solid phase extraction, sorption extraction, solid phase microextraction, have their own advantages and disadvantages.
1.1 Solvent extraction method
Simple solvent-based extraction methods are used to detect pesticides in wheat, rice, corn, soybeans and some derivatives [17-19]. Solid samples (e. g. millet) are often finely stirred before extraction and then sonicated by mixing with solvents to facilitate extraction. Solvents such as acetonitrile, ethyl acetate, methanol and ethanol are often used for the extraction of polar pesticides. For example, even if ethyl acetate is not mixed with water [20], it is equivalent to solvents in detecting polar and non-polar pesticides and has shown good results in detecting pesticides in high fat foods. However, most polar pesticides are easily extracted from ethyl acetate and their degree of extraction is relatively small, so in their work Na2SO4 is added to enhance extraction process. Acetone, n-hexane and dichloro-methane are used to extract low-polar pesticides, for the better extraction additional stages of cleaning can be used to eliminate compounds that may interfere with chromatographic analysis [21,22].
A liquid separation process after solvent extraction has been used [23-24]. However, as a result, the volume of organic solvents used and the sample pre-treatment time for analysis increased. In some cases, gel-conducting chromatog-raphy was used for additional cleaning instead of separating the fluid. Uygun et al.
Identified phosphor organic pesticides (malaoxon, isomalathion, and fenitroox-one) in barley and malt, and Zhang et al. in multicellular pesticides [25]. Chen et al. Identified carbofuran in rice extracting pesticide samples using Triton X-100 as extractant, which is a non-ionic surfactant containing a hydrophilic polyethylene oxide group and a hydrophilic lipophilic or hydrophobic group [26]. As a result, the average value of the high-performance liquid chromatography after extraction was in the range of 88-92 % [27]
Soler C. Proposed the use of di-chloromethane to detect carbosulfan in rice. The detection threshold was in the range of 58-93 % of 3-15 mcg / kg [28].
1.2 Pressurized liquid extraction method
When extracting compounds under pressure, solvents are used at high or low temperatures and pressures (vaporized) to extract solid or semi-solid matrices, which has been developed as an alternative to current extraction methods [2933]. During liquid extraction under pressure, the solubility of the target analytes increases at high temperatures due to a decrease in the viscosity of the solvents, which also reduces the interaction of ana-lytes and increases the diffusion of ana-lytes through the matrix. Compared to other methods, liquid extraction under pressure consumes a small amount of solvent, works quickly and has high efficiency, high degree of automation, good sample ability and safe operation.
1.3 Solid phase extraction method
Solid-phase extraction is one of the
most used methods for sorbent extraction [34-38], sometimes being coupled with pressurized liquid extraction [39] or microwave extraction [40]. Solid-phase extraction allows e.g. the detection of pesticides in rice, wheat, as well as corn, oats, barley. The method also shows good results in the detection of pesticides in wheat flour and in bread made from that flour [41].
Pang et al. Identified 362 of 405 multicellular pesticides in corn, wheat, oats, rice and barley with GC-MS but the 43 pesticides that were not detectable by GC-MS were analyzed immediately after extraction with LC-MS/MS acetonitrile solvent. The extracted solutions are subjected to two different solid-phase extraction methods based on the properties of the pesticides being analyzed. The analysis was tested on NH2 and acetonitrile cartridges. Preliminary tests have shown that the cartridge has less adsorption on pesticides detected with the GC-MS than on the Alumina N cartridge, which was more effective on LC-MS/MS carbonate-based pesticides [42].
In conclusion, these parameters are crucial for obtaining relevant information in the target analyzes. Solid phase extraction reduces the amount of extractable compounds but increases the extraction time. And this is a disadvantage of the solid-phase extraction method.
1.4 Matrix solid-phase dispersion method
In addition to solid-phase extraction, matrix solid-phase dispersion (MSPD) has been used in several cases to detect pesticides from cereals [43, 44]. Moreover, MSPD and MSPD followed by gas chroma-tography coupled with electron capture detection GC-ECD methods, used to detect
Table 1 - Gas chromatographic methods fo cides in cereals.
pesticide residues in wheat or rice, are mixed in appropriate solid sorbents such as acetonitrile n-hexane, ethylacetate (1040 ml range), which are used to achieve complete sample disintegration and dispersing [45].
As with any other method, pesticide detection is influenced by several experimental parameters (e.g. sample size, solid sorbent, type and amount of eluting solvent) for solid phase dispersion. In previous studies, these parameters have been studied and optimized using a step-by-step approach that varies by one factor, despite the emergence of chemometric methods [46].
Matrix solid-phase dispersion is a good alternative to classical extraction methods. Since the cereals are solid specimens, the use of a solid-phase matrix dispersion method will allow no prior solvent extraction. The complete destruction of the specimen and the dispersion of its particles into very small dimensions provide an enlarged surface area for subsequent specimen removal. Sample preparation and cleaning are performed simultaneously using a small amount of adsorbent and solvent. In table 1 gas chromatographic methods for determining the residual amount of pesticides in cereals for the last ten years are summarized.
determining the residual amount of pesti-
Identifiable Sam- Methods and conditions of Results of pre-sample prep- Refer-
substance ple analysis aration and specification ence
1 2 3 4 5
Ametryn, rice Method: SPME-GC-MS 10 g of rice is replaced with [42]
prometryn, terbutryn, atrazine, Equipment: Shimadzu GC-2014 gas chromatograph. Mass spectrometer in electronic shock a 25 ml vial. 12.5 ml of methanol and very pure water (pH = 7) are poured
simazine, ionization mode (70 eV). over.
propazine, Column: SPB-50 Detection limit: 9 - 85 ng/ml
cyanazine (50 mx0.25 mmx0.12^m) Fiber: 20 mm polymer coated aluminum wire Tex = 12 min; tex = 25°C; Tdesorb = 1 min; tdesorb = 250°C; Recovery Rate:> 85 %
Continuation of the table 1
1 2 3 4 5
24 pesticide wheat Method: QuEChERS GC-MS Equipment: CP-8400 gas Chromatograph Varian CP-3800 equipped with autosamplers. Mass spectrometer in electronic shock ionization mode (70 eV). Column: VF-5 MS (30 mxO.25 mmx0.25 ^m) In 10 g of wheat sample, mix for 10 minutes with 10 ml of acetonitrile and 1 % acetic acid. Then, 3 g of anhydrous MgSO4, 1.7 g of CH3COONa, 1.0 g of Na3C6H5O7, and cen- trifuged for 8 min (4500 rpm). The supernatant was then centrifuged again with 600 mg MgSO4 and 600 mg C18. Detection Range: 2.5-5 mcg/kg Recovery Rate: 70-120 % [43]
simeconazole wheat, rice Method: QuEChERS GC-MS Equipment: Trace GC Ultra Gas Chromatograph Mass spectrometer in ionization mode with positive charge (70 eV). Column: BGB-172 (30 mxO.25 mmx0.25 ^m) 20 g of wheat, 20 ml of ace-tonitrile were added to the rice sample and incubated for 60 minutes at room temperature. Then 4 g of anhydrous MgSO4 and 1 g of NaCl are added and the mixture is dehydrated. Detection range: 0.4 -0.9 mcg/kg [44]
Fluroxypyr-meptyl wheat Method: SPE GC-ECD Equipment: Shimadzu 2014 Gas Chromatograph Mass spectrometer in electronic shock ionization mode (70 eV). Column: HP-5 (30 mxO.25 mmx0.25 ^m) 10 g of wheat sample is ground and 30 ml of methanol: water (5:1 ratio) are extracted. It is then filtered and extracted 3 times with 20 ml of dichloromethane. Then they are eluted on Flo-risil cartridge. Detection limit: 0.0005 ng/ml Recovery Rate: 84.45 -108.2 % [45]
alachlor, aceto-chlor, preti-lachlor, bu- tachlor, metolachlor, propanil wheat, rice Method: SPE GC-ECD Equipment: Trace GC Ultra Gas Chromatograph Mass spectrometer in electronic shock ionization mode (70 eV). Column: DB-5 (30 mx0.25 mmx0.25 ^m) 2 g of wheat and rice were ground and extracted with 50 ml of acetone. The extract is then evaporated and extracted again with 1 ml of hexane. The graphite is then eluted on the secondary amino matrix. Detection range: 0.8-1.7 ^g/kg Recovery Rate: 82.3-115.8 % [46]
Continuation of the table 1
1 2 3 4 5
a, ß, y,S-HCH p, p'-DDD, p, p'-DDE, o, p'-DDT, p, p'-DDT, a-endosulfan ß-endosulfan heptachlor, heptachlor epoxide, diel-drin, aldrin wheat, rice Method: SPE GC-ECD Equipment Trace GC Ultra Gas Chromatograph Mass spectrometer in electronic shock ionization mode (70 eV). Column: DB-5 (30 m x 0.25 mm x 0.25 ^m) 1 g of wheat and rice sample was homogenized with 2 ml of water and 8 acetonitrile. Then added 2 g of NaCl and shake for 2 minutes. The extract is then evaporated and extracted again with 1 ml of hexane. The graphite is then eluted on the secondary amino matrix. Detection Range: 1.5-4.2 ^g/kg Recovery Rate: 78 -116 % [47]
120 pesticides wheat Method: QuEChERS GC-MS/MS Equipment: Agilent 7890A gas chromatograph Column: HP-5ms Ultra Inert (30 mx0.25 mmx0.5 |im) In 5 g of ground wheat sample, add 10 ml of water and 10 acetonitrile, and shake for 5 minutes. Then, 4 g MgSO4, 1 g CH3COONa, and 1.5 g Na3C6H5O7 were added and centrifuged for 10 min. Then, PSA was added and centrifuged. Recovery Rate: 70-120 % [48]
219 pesticides wheat, rice Method: QuEChERS GC-MS/MS Equipment Agilent 7890A gas chromatograph Column: VF-1701 ms (30 mx0.25 mmx0.5 |im) 5 g of wheat and rice are moisturized by adding 10 ml of water. Then centri-fuged for 5 minutes at 15 ml of acetonitrile, 6 g MgSO4, and 1.5 g CH3COONa. Then 400 ml of PSA, 400 mg of C18 and 1200 mg of MgSO4 were added to 8 ml of supernatant and centrifuged for 5 minutes. Then 3 ml of supernatant is sent for analysis. Detection Range: 5-50 mcg / kg [49]
124 pesticide rice Method: QuEChERS GC-MS/MS Equipment: Gas chromatograph Varian 450 equipped with CP 8400 autosamplers Mass spectrometer in electronic shock ionization mode (70 eV). Column: VF-5 MS (60 mx0.25 mmx0.25 5 grams of rice is replaced with 50 ml of Teflon tube and 10 ml of water and 10 ml of acetonitrile are added. The mixture was kept in the fridge for 30 minutes. Detection range: 0.1-24.4 ^g / kg Recovery Rate: 70-22.7 % [S0]
Continuation of the table 1
1 2 3 4 5
dimetoat, forat, diazinone, methyl parathi-on, forat sulfonate, forat sulfoxide, chlorpyrifos, chlorofenvino-phos, fosalon wheat, rice Method: QuEChERS GC- NPD/MS Equipment: Shimadzu GC - 2010 Gas Chromatograph. Column: DB-1 (30 mx0.25 mmx0.5 ^m) In 10 g of sample, water is added and shaken. Then, 10 ml of ethyl acetate, 4 g of anhydrous MgSO4, and 1.0 g of NaCl were added and centrifuged for 10 minutes (8000 rpm). Aliquot volume 1 ml. Detection Range: 0.001-0.010 ng/kg Recovery Rate: 70.2-95.25 % [51]
demethon-s-methyl, phor-ate, diazinone, chlorpyrifos methyl, tolclo-phos-methyl, pirimifosmetil, malathion rice Method: MA-NPS-DME GC- MS Equipment: Gas chromatograph Shimadzu QP 2010 plus Mass spectrometer in electronic shock ionization mode (70 eV). Column: DB-5 MS (30 mx0.25 mmx0.5 Mm) 1 g of rice was placed on the extractor-will be created. The 2.0 ml hexane was then infused for 200 seconds through the extractor and irradiated with a 150 W microwave. Detection Range: 0.45-1.06 ng/kg [52]
chlorpyrifos, fenitrotion, malathion, met- acriphos, phosphamidone wheat Method: HS-SPME-GC- FPD/MSD Equipment: HP 5890 II gas chromatographs. Column: DB-35 Ultra (50 mx0.25 mmx0.12 ^m) Fiber: DVB/CAR/PDMS 50/30 |im Tex = 45 min tex = 60°C Tdesorb = 3 min tdesorb = 250°C The 1.7 g wheat sample is replaced with a 4 ml vial. Detection limit: 0.05-100 ng/g [53]
Tebuconazole, Carbofuran, Atrazine, sima-zine, Molinate rice Method: SPME-GC-MC Equipment: Shimadzu QP-Plus 2010 gas chromatograph. Column: Rtx-5MS (30 mx0.25 mmx0.5 ^m) Fiber: DVB/CAR/PDMS 50/30^m Tex = 40 min tex = 80°C Tdesorb = 10 min tdesorb = 250°C The 125 mg rice sample is replaced with a 40 ml vial. 25 ml of very clean water is poured into it, according to pH = 2.2. Detection range: 0.46 - 5.9 ng / g Recovery Rate: 76 -109 % [54]
Continuation of the table 1
1 2 3 4 5
23 pesticides wheat, rice Method: QuEChERS GC-MS/MS Equipment: Agilent GC 6890N gas chromatograph Column: Rxi-5 ms (30 mx0.25 mmx0.5 ^m) In 5 g of ground wheat and rice samples was added 10 ml of water and 15 ml acetonitrile was shaken for 1 minute. Then added 6 g MgSO4, 1.7 g CH3COONa, 1.5 g Na3C6H5Oy and cen-trifuged for 10 min. Then 8 ml of supernatant was transferred to a 15 ml vial, 25 mg of PSA and 150 mg of MgSO4 were added and centrifuged for 5 minutes [55]
1.5 The method of solid phase microextraction during the pre-sample preparation
A sample preparation process is an important step in analysis, mainly used to enrich the matrix with analytes and to remove interfering components. However, the pre- sample preparation process usually takes a long time and a large amount of organic solvent. Therefore, the development of green technology for pre-sample specimens with high efficiency and simplicity of performed operations is one of the important areas of modern science.
One of the most important advances in sample preparation was the solid phase microextraction method originally described in 1990 by Arthur and Pawliszyn [47]. SPME is a simple and efficient sorption method eliminates the need for solvents and combines sample selection, extraction, and concentration at one stage. It is designed to solve long-lasting solvent-based problems using multi-stage methods that require the use of large quantities of solvent-bearing samples. In some literature, the SPME method is referred to as "green method" because of the non-use of environmentally hazardous solvents. Achieving a balance between the analytes as well as the phase of organic polymer deposited on the fused silica fiber and the matrix of the samples is the principle of SPME.
The solid phase microextraction method saves pre-sample treatment time
and reduces the overall cost of the assay. The purpose of the method is to quickly prepare samples. It offers sample preparation, solvent-free extraction, solid, liquid or gaseous specimens, and low analyte concentrations.
SPME has helped eliminate some of the disadvantages of classical sample preparation methods. The easy automatization of the method has resulted in higher analytical performance [48-50]. Due to its excellent analytical characteristics, including linearity, repeatability, repeatability and low detection range, SPME is an effective and efficient method of extracting pesticide residues in fruits, vegetables and grains. The SPME tool is a quartz-roded syringe, coated with a thin polymer film connected to the plunger. For the extraction of components using SPME, the vial membrane is pierced, the component is extracted onto the film, and the syringe is removed for further desorption in the chromatograph. SPME is a very attractive alternative when preparing specimens that provide high selectivity, sensitivity and versatility at minimum matrix impedances [51, 52].
In conclusion, the need for frequent monitoring of residues of pesticides and other pollutants in food has led to the development of different methods of sample preparation. The SPME method was able to demonstrate good results in a quantitative analysis of pesticide residues in food and agricultural products.
Application of solid phase microextraction in pesticide analysis
Currently monitoring of pesticide residues in food products is the task of ag-rochemical research to conduct a comprehensive assessment of food quality and pollution. Therefore, the analysis of pesticides and agrochemical wastes (fertilizers, pesticides, soil conditioners, antibiotics etc.) in food is of paramount importance for monitoring and security purposes. Sample preparation is the most important step in achieving good quantitative results when determining the residual amount of pesticides from food matrices. The SPME technique has several advantages. Among them are the shortness of sample preparation time, separation and detection compatibility with chromatographic instruments and feed automation [53].
Cortes et.al [54] developed an analytical method in combination with the GC-MS and GC-MS/MS methods to determine the residual amount of 54 pesticides in orange, peach, pineapple juice. The rapid screening method was first performed to detect pesticide-containing juice specimens at concentrations above the predetermined threshold values. Samples were reanalyzed using simple, standard methods to confirm the predefined pesticides. This method reduced the total time of traditional analytical methods by 50 % [55].
SPME has been widely used recently to monitor the residual content of pesticides in water and soil and in edible plant samples. Chai et al. [56] presented the HS-SPME-GC-ECD method using 100 ^m PDMS fiber to determine the residual pesticide content in fruits (strawberries, caramel and guava) and vegetables (cucumbers, tomatoes, and peas). The developed HS-SPME procedure provided a good linear range, accuracy, quantitative detection range and was adequate to analyze pesticide residues in fruits and vegetables. LOD (0.01-1 Mg/l) and the quantitative detection limits of these pesticides were shown in LOQ (0.05-5 Mg/l). The amount of pesti-
cides detected was significantly lower than the permissible levels.
Feng et al. [63] proposed the HS-SPME/GC-MS method for identifying 8 pesticides in tea samples. Compared to simple sample preparation methods, the recommended method is quick, simple, highly sensitive, and saves extraction solvents. This optimized method allowed to improve good separation rate (86.7-112.8 %) and LOD (1.2-22.1 ng/g) using 100 ^m PDMS fiber.
Saraji et al. prepared a polypyrrole/ sol-gel composite coated SPME fiber by electrochemical deposition. The authors analyzed the phosphor-organic pesticides in cucumber and lettuce leaves using the GC-NPD method. Fiberglass-coated SPME has shown better extraction efficiency than commercial fiber. LOD levels and separation rates (80-109 %) were excellent [57]. Wang et al. Used the technique for preparing a water-compatible molecular imprinted polymer for SPME using a diazinon matrix as a sol-gel functional monomer and polyethylene glycol. MIP-coated fiber showed significantly higher extraction ability than unimpressed polymer and commercial fiber. Due to its unique adsorption, it showed excellent thermal and chemical stability. MIP-SPME-GC-NPD was developed and displayed on LOD (0.017-0.77 mg/kg) for OPP evaluation in agriculture samples [58].
Melo at al. [59-65] have developed a method to identify the 10 most frequently used pesticides in the production of lettuce (acetamiprid, azoxystrobin, cyprodinil, fenhexamid, fludioxonil, folpet, iprodione, metalaxil, pirimicarb, and tolyfluanid). This method has been efficient for quantitative determination of fludioxonil, folate, iprodi-one, azoxystrobin, cyprodinil, fenhexamid, and tolyfluanid in salad leaves at concentrations from 0.8 to 25.6 mg/kg. However, this SPME fiber does not extract acetam-iprid, metalaxyl and pirimicarb were extracted only at concentrations greater than 20 mg/kg.
Detection of pesticides in food using SPME
Chromatographic analysis of pesticide residues in food, fruit and vegetable samples has been extensively studied since the introduction of SPME. Currently, SPME has been successfully used for analytical purposes in the identification of many pesticides in various foods [66, 67].
Chlororganic semi-and pyrethroid pesticides, bifenthrin residues in celery, garlic, and cabbage were identified by Zeng et al. [68] Good results were obtained by using 70 |j.m polymethylphenylsiloxane-coated fibers obtained by Sol-gel technology. The above-mentioned fiber demonstrated the best efficiency of pesticide extraction compared to commercially available fibers. The extraction efficiency is explained by the long fiber cover, the porous nature and the presence of a phenyl group. Vegetable samples are mixed with a solution, then acetone is added, dried, and treated with ultrasound. Then, it was extracted in DI-SPME mode at room temperature. The obtained data showed good results compared to the analyses performed in the HS-SPME mode. The acquired specimens are desorbed using the GC-ECD method. Quantitative evaluation was analyzed in three copies by addition of fresh vegetables. The degree of recovery pesticides ranged from 42.9 to 105.3 %, the RSD has shown 2.6 to 16.2 %, and the LOD 0.13 - 1.45 ng/g [69].
Chai et al. [70] have developed the HS-SPME-GC-ECD method for the analysis of phosphororganic (diazinon, profeno-phos and quinalphos) and a- and p>-endosulfan and chlorothalonil in tomatoes and guava. In the developed method, 100 Hl of 20 % methanol-acetone (1+1 vol/vol.), 10 % NaCl in purified water were used to obtain a total mass of 5 g. The resulting mixture was extracted with 100 |j.m PDMS fiber which was selected due to its low LOD and high sensitivity to all the studied pesticides. The extraction was performed in HS mode (800 rpm) by constant stirring at 60 °C for 30 minutes. Desorbed at 240 °
C for 6 minutes after optimizing the required parameters. Addition of water provides recovery from 82 to 97 %, and LOD ranges from 0.1 to 1 ng/l.
Chai et al. Evaluated the use of GC-NPD in combination with SPME to identify five OPPs from tomatoes. This method involves simultaneous cooling of the fiber used in the HS mode and heating of the sample matrix. The developed method demonstrated better extraction efficiency in terms of sensitivity, linearity and recovery than traditional HS-SPME. The homogenized sample of 5 g of tomatoes was extracted at 80 °C for 30 min and desorbed at 270°C for 2 min. The method showed acceptable linearity recovery and LOD [71].
Chai and Tan validated HS-SPME optimized parameters for detection of profenophos, quinalphos, a- and p>-endosulfan in strawberries, guava, cucumber, tomato, bag, using a previously developed method [72]. Thermal desorption was performed at 240 °C for 10 minutes instead of 6 minutes, which helped to overcome the problem of reducing the temperature of the gas chromatography injector port and transporting. As a result, 10 minutes of desorption compared to 4 minutes of desorption yielded the best extraction efficiency. The median recovery rates for each pesticide were 71 to 98 % when enriched at three levels and RSD less than 5 % (n=3). Relapse (0.3-3.7 %) and intermediate accuracy (0.8-2.5 %) were satisfactory for all the studied samples. LOD showed quantitative determination using 0.01-1 ^g/l and LOQ 0.05-5 ^g/l.
Cortes-Aguado et al. Provided an analytical method for detecting 54 pesticide residues in orange, peach and pineapple juice samples. A fast screening is an analytical method that is quite new. In this method, the sample process is semiautomatic, which significantly reduces human error. Preprocessing of the specimen includes pretreatment of 1 ml of ethylacetate with 1ml of homogenized samples and centrifugation within 2 minutes. The re-
sulting mixture was extruded at 250 °C for 9 minutes at room temperature in DI-SPME mode using 65 ^m PDMS/DVB fiber. The RSD showed good recovery rates between 2-17 %. The LOD and LOQ were between 0.01 and 16.7 and 0.1 and 50 ng/l, respectively, and the linear range was from 0.01 to 1 ^g/l, above 0.99 for all r2 specimens [73].
Menezes et al. Developed an analytical method for the simultaneous detection of 14 pesticide residues in mango using the SPME-GC/MS method. The 3g sample was transferred to a 10 ml measuring flask and filled with an alcohol-water mixture of 50 |il of the concentrated pesticide solution. The resulting mixture was extracted for 30 min in a 10-ml hermetically sealed in the DI-SPME mode at 50°C for 50 minutes and stirring at 250 rpm. The mean relative recovery rate (n = 3) ranged from 71.6 to 117.5 %. The method was of good accuracy, selective and sensitive. The residual pesticide levels were below the maximum permissible values [74].
Guillet et al. Developed a method that involves the use of microwave energy for rapid and controlled pre-extraction of the residual amount of pesticides from 25 tomatoes. Extraction was performed using 100 |j.m PDMS fiber (for water-insoluble pesticides) and 60 ^m PDMS/DVB fiber (for water-soluble pesticides) and a room temperature of 45 rpm for 500 min. LOD (0.01-7.62 |J.g/kg) and LOQ (0.20-25.4 ^g/ kg) were significantly lower than the permissible threshold values for all pesticides studied [75].
CONCLUSION
QuEChERS has been found to be a fast and effective method that allows you to extract residual amounts of target compounds while removing unwanted interferences such as organic acids, lipids, pigments, sugars, and others. It was revealed that the QuEChERS method is free of the drawbacks of traditional methods of sample preparation, such as the duration of the extraction procedure, the use of haz-
ardous solvents, and radically simplifies the analysis of pesticide residues in food.
It has been established that to achieve accurate and complete determination of pesticides, new modern analysis systems are used. Chromato-mass spectrometry in combination with QuEChERS technology opens new opportunities in the analysis of residual amounts of pesticides in agricultural products. Tandem mass spectrometry detectors with HPLC or GLC allow for a group analysis of many compounds with exceptionally high selectivity and sensitivity and extrude methods such as gas and high-performance liquid chromatography with various detectors.
However, because of the high cost of chromatographs with tandem mass spec-trometric detectors, the institutions and laboratories of developing countries cannot afford to purchase these devices.
The method of solid phase microextraction (SPME) is the most promising and most widespread of alternative "green" methods of sample preparation in the analysis of volatile pesticides. Solid phase microextraction, which combines sample selection, extraction, concentration and simultaneous enrichment, is a simple and efficient method of sample preparation. This method has gained advantages over traditional methods such as ease of use, low cost, low solvent consumption, speed, high enrichment and ease of automation. Due to its high elasticity, SPME is widely used for the analysis of volatile and nonvolatile compounds in complex matrices, especially in food samples. Given that microextraction is one of the important fields in pre-modern sample processing, it is expected that the use of the SPME method for food analysis will increase in the future. The need to regularly monitor pesticide residues and identify other contaminants in food has led to the development of various sampling methods. Currently, the SPME method involves world scientific laboratories to determine the residual amount of pesticides
ACKNOWLEDGMENT This work was conducted under the project AP08857501 «Improvement and development of highly sensitive methods for ensuring food safety in Kazakhstan» funded by the Ministry of Education and Science of Kazakhstan from 2020 to 2022.
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TYËIH
М. Р. Мамедова1, А.Б.Ибраимов2, А.Н. Кунанов2, М.Б. Алимжанова1,2, З.А.Тукенова3 ДЭНД1 ДАKЫЛДАРДАFЫ ПЕСТИЦИДТЕРД1 ТАЛДАУДЫН, ЖАСЫЛ ЭД1СТЕР1: ШОЛУ 1эл-Фараби атындагы Казак улттыцуниверситету Физика-техникалык факультету 050060, Алматы к., эл-Фараби дацгылы, 71, Казакстан 2 эл-Фараби атындагы Казак улттыцуниверситету Химия жэне химиялык технология факультету 050060, Алматы к., эл-Фараби дацгылы, 71, Казакстан 3 в. О. Оспанов атындагы Казак топырактану жэне агрохимия гылыми-зерттеу институт, 050070, Алматы к., эл-Фараби дацгылы, 75 В, Казакстан
e-mail: mamedova.madina@kaznu.kz Пестицидтер XX гасырдыц ортасынан бастап 6yk^ элемде, ауыл шаруашылыгында дэндьда;ылдарды жэне олардыц туындыларын eндiру Yшiн паидаланылуда. Кептеген пестицидтер, эйресе фунгицидтер мен инсектицидтер эр тYрлi аурулардыц алдын алу жэне тсу кезшде ешмдткп арттыру Yшiн ;олданылады. Пестицидтердщ ;оршаган ортага шыгарылуы химиялы; ластаушы заттардыц жалпы саныныц бiр паиызын ;ураиды, б1ра; бул ;осылыстар организмдердщ белгт бiр топтарын, пестицидтер мен олардыц трансформация ешмдерш басуга багытталганын ескере отырып, олар биотаныц эр тYрлi тYрлерiне жэне агзага кекешстер мен жемiстер ар;ылы енiп, оныц iшiнде олар нашар жуылган болса адам денсаулыгына улы эсер етедь Сонымен ;атар, олар дэндi да;ылдардан топыра;тан йцш кету ар;ылы енедь Kазiргi тацда, ;аушйз пестицидтер жо;, тiптi аз мелшерде ;олданган кезде де олар эртYрлi аллергиялы; реакциялар мен улануды тудыруы мYмкiн. Ауылшаруашылы; eнiмдерiн eндiруде макулданган
пестицидтер ;олданылады, 6ipan; бул препаратты уза; уа;ыт ;олданудьщ жагымсыз салдары болуы MYMKiH екендiгiн жо;;а шыгармайды. Демек, осы eнiмдердегi пестицидтердщ ;алдык;тарын Yнемi ба;ылау адам денсаулыгы мен ;оршаган ортага ;аушт азаитады. Сондьщтан пестицидтердщ ;алдык;тарын аньщтаудьщ тшмдь жылдам жэне Yнемдi эдiстерi ;ажет. Ма;алада дэндi да;ылдардагы пестицидтердi талдауга сынама даиындау эдiстерi, сондаи-а; сынамаларды даиындауда экологиялы; жасыл химия эдктершщ бiрi болып табылатын ;атты фазалы микроэкстракция эдганщ ерекшелiктерi кeрсетiлген.
TyuiHdi свздер: дэндьда;ылдар, пестицидтер, сынаманы даиындау эдктеръ ;атты фазалы микроэкстракция эдга, хроматография
РЕЗЮМЕ
М.Р.Мамедова1, А.Б.Ибраимов2, А.Н.Кунанов2, М. Б. Алимжанова1'2, З.А.Тукенова3 ЗЕЛЕНЫЕ МЕТОДИКИ АНАЛИЗА ПЕСТИЦИДОВ В ЗЕРНОВЫХ КУЛЬТУРАХ: ОБЗОР 1Казахский национальный университет им. аль-Фараби, физико-технический факультет, 050060, г. Алматы, пр-т аль-Фараби, 71, Казахстан 2Казахский национальный университет им. аль-Фараби, химико-технологический факультет, 050060, г. Алматы, пр-т аль-Фараби, 71, Казахстан
3ТОО Казахский научно-исследовательский институт почвоведения и агрохимии им. У.У. Успанова, 050070, г. Алматы, пр-т аль-Фараби, 75 В, Казахстан
e-mail: mamedova.madina@kaznu.kz Пестициды используются во всем мире, начиная с середины XX века, для производства зерновых культур и их производных в сельском хозяистве. Многие пестициды, особенно фунгициды и инсектициды, используются для предотвращения различных заболевании и повышения урожаиности во время созревания. Поступление пестицидов в окружающую среду составляет долю одного процента от общего количества химических загрязнителеи, но, учитывая, что эти соединения нацелены на подавление определенных групп организмов, пестициды и продукты их трансформации оказывают токсическое воздеиствие на здоровье человека, попадая в организм с овощами и фруктами, в том числе с их поверхности, если плоды плохо вымыты и на различные формы биоты. А также, из злаков, так как они могут всасываться в них из почвы. Безопасных пестицидов не существует, даже при использовании в малых количествах они могут вызывать различные аллергические реакции и отравления. При производстве сельскохозяиственнои продукции используются одобренные пестициды, но это не отменяет того факта, что у длительного использования препарата могут быть негативные последствия. Следовательно, постоянныи мониторинг остаточного количества пестицидов в этих продуктах снижает риск для здоровья человека и окружающеи среды. Поэтому необходимы эффективные, экспрессные и экономически выгодные методики определения остаточных количеств пестицидов. В статье отражены методы подготовки проб при анализе пестицидов в зерновых культурах, а также особенности метода твердофазнои микроэкстракции однои из методов экологическои, зеленои химии при подготовке проб.
Ключевые слова: злаки, пестициды, методы пробоподготовки, метод твердофазнои микроэкстракции, хроматография.
