International Journal of Advanced Research and Development

www.multidisciplinaryjournal.net
ISSN: 2455-4030
Received: 26-06-2023, Accepted: 11-07-2023, Published: 27-07-2023
Volume 8, Issue 4, 2023, Page No. 17-20

Detection of pesticide residues from the local grapes variety madrasa and tabrizi

Yolchuyeva E A, Nasibova G R, Gurbanova N T, Valiyeva L T, Rustamova A A

Department of Chemistry, Azerbaijan State Agricultural University, Ganja, Azerbaijan

Abstract
This study was conducted to investigate the pesticide residue concentrations from grape consumption in Arebaijan. A total of
samples of grapes variety Madrasa and Tabriziwere collected from the Shamkir area in 2020. The pesticide residues were
analyzed by gas-liquid chromatography. A total of 3 different pesticide residues were found and 2 residues exceeded MRLs.
The most frequently detected pesticide residues were metalaxyl, acetamiprid and dimetomorph.

Keywords: Pesticide, grape, detection, analysis, pesticide, residue

Introduction pests, but also for domestic use to control fleas on cats and
Pesticides are essential tools to increase agricultural dogs. Acetamiprid is an α-chloro -N-heteroaromatic
productivity and cultivation convenience. However, compound [5]. It is a neonicotinoid with a chloropyridinyl
pesticides inevitably remain in agricultural products and soil group and it is comparable to other neonicotinoids such
[1]
. Excessive use of pesticides causes these chemicals and as imidacloprid, nitenpyram and thiacloprid. These
metabolites to remain in the environment and food, causing substances all have a 6-chloro-3-pyridine methyl group but
serious problems in the ecosystem and public health [2]. differ in the nitroguanidine, nitromethylene, or
Chronic human exposure to unsafe levels of pesticides can cyanoamidine substituent on an acyclic or cyclic moiety [6].
cause a wide range of diseases affecting human health. Chemical structure of acetamiprid:
Pesticides have potential adverse effects on human health
such as carcinogenesis, immunotoxicity, birth defects,
genetic changes, neurological toxicity and endocrine
disruption. Fruits and vegetables are usually consumed
directly without processing after washing, so they are the
main cause of pesticide residue ingestion in humans [3].
Samples for analyse are grapes variety Madrasa and Tabrizi
were collected from the Shamkir area. Grapes may contain
toxic residual pesticides due to the use of pesticides during
the production process of agricultural products.
Pesticide residues in agricultural products are usually
Dimethomorph -local systemic fungicide with good
monitored with reference to maximum residue limits
protective and antisporulation activity. Inhibits the
(MRLs), which represent the highest concentration of
formation of the oomycete cell wall.- 3-(4-chlorophenyl)-3-
pesticide residues that is legally permitted or accepted in
(3,4-dimethoxyphenyl)-1-morpholin-4-ylprop-2-en-1-one.
food commodities after the use of pesticides [4].
Chemical structure of dimetomorph:
Data analysis and processing:
The objects of research are two grape varieties madrasa and
tabrizi. Instrumental work to determine the residual amounts
of pesticides in the specified material were performed in the
People's Reference Laboratory of the Azerbaijan Institute of
Food Safety. In the objects under study, the content of
nitrogen-containing fungicide preparations containing a
phenyl residue using the example of acrobat and ridomil
gold was determined by gas chromatography (GC)
according to approved methods as well as the mospilan
insecticide. The active ingredients of these pesticides in the
composition of acrobat-dimetamorph in tthe composition of
ridomil gold -mancozeb and metalaxil in the composition of
mospilan - asetamiprid. Metalaxyl -systemic, phenylamide fungicide with protective
Acetamiprid is an organic compound with the chemical and curative mode of action, acts by suppressing sporangial
formula C10H11ClN4. Acetamiprid is an insecticide formation, mycelial growth and the establishment of new
belonging to the chloropyridiny lneonicotinoids, this family infections. Disrupts fungal nucleic acid synthesis - RNA
of insecticides was introduced in the early 1990s.This ploymerase 1.
compound is an insecticide that is introduced for controlling Chemical structure of metalaxyl:

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residues were purchased by Accustandard (New Haven, CT,

USA). For the extraction of pesticide residues, acetonitrile,
acetone, dichloromethane and n-hexane used in this
experiment were purchase with HPLC grade reagents
(Muskegon, MI, USA). These analyzes were performed on
an Agilent 7820 A gas liquid chromatography instrument
(USA). The sample is homogenized. After homogenization
we add a part to the centrifuge tube. Due to the presence of
80% water in the composition, we do not add water. Add 10
ml of acetonitrile to the sample. Close the centrifuge and
turn it on for one minute. 4g of MgSO4, 1g of NaCl, 1 g of
trinitrate citrate dihydrate, 0.5 g of disodium
hydrocitratesesguigitrate buffer-salt mixture were added to
The analysis of samples according to the presented methods the resulting suspension. Vortex vigorously for one minute.
allows for a qualitative analysis of these fungicides and a After that stir in a centrifuge for five minutes. Add 6 ml of
quantitative determination of the insecticide residue in the an aliquot of acetonitruleic phase to the resulting solution.
grapes [6]. A modified, efficient, and sensitive acetate- We move it in the centrifuge. The solution is isolated and
buffered QuEChERS extraction method was developed for from the pure extract we take 1 ml. To increase the acidity
the quantitative study of 3 commonly applied multiclass add 10 μl of formic acid solution [8]. Switch to avto sample
pesticides on grapes. Samples were extracted with acidified mode and start chromatographic analysis. The high
acetonitrile, buffered with acetate salt. To minimize the performance liquid chromatography (HPLC) was carried out
matrix interferences, clean-up of the rehydrated samples on Ultimate 3000 (Dionex, Sunnyvale, California, USA)
was optimized by comparison with different sorbents with UV-VWD detector. Chromatographic separation was
(alumina, silica gel, florisil, primary secondary amine performed on a Capcell Core C18 column
(PSA), and chitosan). The method validation parameters (4.6 mm × 100 mm, 2.7 µm particle size, Osaka Soda,
were evaluated as per European Union (EU) guidelines Osaka, Japan). HPLC conditions consisted of mobile phase
(SANTE/12682/2019). For 3 pesticides, % recovery of 69 to A (5% acetonitrile in water), mobile phase B (20%
121.8% with an associated precision (RSD ≤ 20%) was methanol/80% acetonitrile, v/v), 10 µL injection volume,
achieved at the fortification levels that were 0.5 to 2 times 1.0 mL/min flow rate and 40 °C oven temperature [9]. UV
of European Union maximum residue limits (EU-MRLs) [6]. absorbance was monitored at 220 nm and 250 nm. The
The validated method was successfully employed for the gradient program was as follows: initial (90% A/10% B), 0–
analysis of grapes variety Madrasa and Tabrizi isamples 13 min (10–80% B), 13–16 min (20% A), 16–16.1 min (20–
(n = 20) collected from Shamkir region of Azerbaijan. The 90% A) and 16.1–20 min (90% A/10% B) [10].
most frequently detected residues weredimetomorph, As a result dimetamorph and metalaxyl were found in the
metalaxyl and acetamiprid. The concentration of all the madrasa grape variety, acetamiprid and metalaxyl were
detected pesticides in real samples was below the EU-MRLs found in the tabrizi grape variety from the vineyard in the
[7]
. Shamkir region. Below are the chromatograms for the
The 400 pesticide standards used to analyze pesticide detection of the listed compounds.

Fig 1: Chromatogram graph for the determination of metalaxyl in a sample of variety tabrizi from a vineyard on the territory of Shamkir by
gas-liquid chromatography

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Fig 2: Chromatogram graph for the determination of dimetomorph in a sample of variety madrasa from a vineyard on the territory of
Shamkir by gas-liquid chromatography

Fig 3: Chromatogram graph for the determination of metalaxyl in a sample of variety madrasa from a vineyard on the territory of Shamkir
by gas-liquid chromatography

The amount of acetamiprid was 8.55 ppb, the amount madrasa variety by quantitative analysis is 14.05 ppb, the
ofmetalaxyl was 92.528 ppb in tabrizi variety using amount of metalaxyl was 92.628 ppb.
quantitative analysis. The amount of dimetomorph in the Below is a list of grape samples that should be used to
determine pesticides:

Pesticides Variety Amount Of Pesticides

Metalaxyl Tabrizi 92.528 ppb
Dimetamorph Madrasa 14.05 ppb
Acetamiprid Tabrizi 8.55 ppb
Metalaxyl Madrasa 92.628 ppb

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Conclusion
In the paper two grape varieties - madrasa, and tabrizi from
the grape sites of the Ganja-Gazakh zone of Azerbaijan are
studied, some pesticides: acetamiprid, metalaxyl and
dimetomorph are determined in the considered samples.
Analysis of the quantitative determination of pesticides are
carried out in the considered samples.

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