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Full Research Article

Comparative Evaluation of EN 15662 and QuEChERS Methods for the Determination of Fenoxaprop-p-ethyl and Propargite-NH4 Pesticide Residues by LC-MS/MS in Cucumber

P
Priyanka Gour1,*
http://orchid.org/0009-0004-1611-9222
P
Purnima Dashora1
http://orchid.org/0009-0004-2777-2841
R
Ravi Sethi2
http://orchid.org/0009-0002-3306-1136
1Department of Chemistry, Pacific Academy of Higher Education and Research University, Pacific Hills, Pratapnagar Extn, Airport Road, Debari, Udaipur-313 024, Rajasthan, India.
2Food Analyst, Public Health Laboratory, Govt. Maharana Bhupal Hospital Campus, Udaipur-313 024, Rajasthan, India.

ABSTRACT

Background: The application of two widely used sample preparation methods (EN 15662 and QuEChERS) in determination of pesticide residues in food matrices was compared and evaluated. The aim was to evaluate the efficiency, accuracy, practicality of methods regarding extraction recovery and analytical performance, particularly for Fenoxaprop-p-ethyl and Propargite-NH4.

Methods: The results show that both the QuEChERS and EN 15662 methods can effectively use liquid chromatography-mass spectrometry (LC-MS/MS) for detecting target analytes. Slightly higher recovery rate of the EN 15662 method indicates that this method has higher accuracy and precision for these compounds. 

Result: In contrast, the QuEChERS method offers a faster sample preparation process and exhibits acceptable performance, making it a suitable choice when time efficiency is the primary consideration. The results suggest that the choice of method can be based on the characteristics of a specific pesticide and laboratory priorities, such as speed or sensitivity. The assessment results can provide informed decision support for pesticide residue testing for research and regulatory quality purposes.

INTRODUCTION

The QuEChERS (Rapid, simple, inexpensive, efficient, durable and safe) process is a simplifying and efficient technique designed specifically for routine pesticide residue analysis. This procedure includes extraction with acetonitrile, following salt partitioning and finally purification steps utilizing “dispersive solid-phase extraction (D-SPE)”. Owing to its high speed and low solvent consumption, it is ideal for high-throughput testing of various pesticides in range of food matrices, including crops with high water content like cucumbers (Plonka et al., 2025; Musarurwa et al., 2019). The EN method specifically refers to European standard EN 15662, which is the standard and validated version of QuECheRS technique for pesticide residue analysis in European Union. The main differences are in standardization and buffer composition; EN 15662 uses a citrate-buffered extraction system to improve stability and reproducibility across different laboratories and matrices. While both methods are efficient and effective, the EN method is suitable for regulatory compliance, while the general QuEChERS protocol is suitable for routine analysis (Mao et al., 2020). This study established method for evaluating dissipation of proporgite in pigeon pea using LC-ESI-MS/MS which has higher sensitivity, selectivity and specificity compared to other analytical techniques. Analogous effectiveness of LC-MS/MS for determination of indoxacarb residues in Pigeon pea green pods and dry grains (Naik et al., 2022). Pesticides divided into various groups based on the type of pest they target: Insecticides- used to kill insects, Fungicides-used to control fungal infections, Rodenticides-effective against rodents like rats and mice, Herbicides-used to eliminate unwanted weeds, often replacing manual weeding, Plant Growth Regulators-substances that influence plant development and growth (Lee et al., 2018). LC-MS is powerful analytical process which integrates sensitive and selective detection of mass spectrometry (MS) with separation capabilities of “high performance liquid chromatography (HPLC)” (Govind et al., 2023). HPLC remains crucial for minimizing matrix interferences that may affect ionization efficiency. When atmospheric pressure ionization (API) is used, both solvent removal and ionization occur at atmospheric pressure within the source, enhancing the method’s ability to detect trace-level analytes having high sensitivity and selectivity (Hamdy et al., 2019; Fernandez et al., 2008). HPLC has previously been employed for pesticide residue analysis in crops like chilli (Reddy et al., 2007) and tomato (Romeh et al., 2009) Pesticides currently used by farmers and to assess the presence of various pesticide residues in different vegetable crops (Nishant et al., 2016). However, during past years, combination of chromatography and MS has become selected method for detecting trace pesticide residues as result of higher sensitivity and accuracy (Lacina et al., 2010). Convert liquid analytes into gaseous ions suitable for detection. The most challenging part of the process is effectively removing the solvent while maintaining the vacuum environment required for the mass spectrometer. With the advent of thermal spraying and particle beam interfaces, popularity of LC-MS has increased significantly. Developing “Electrospray Ionization (ESI)” and “Atmospheric Pressure Chemical Ionization (APCI)”, both ESI and APCI fall under category of API techniques, operating at ambient pressure and offering gentle ionization conditions that help preserve molecular integrity in which analyte ions initially present in liquid phase transferred into gas phase for mass spectrometric analysis (Masia et al., 2014; Ecobichon, 2001). Electrostatic repulsion in the droplets causes them to undergo Columbic fission, resulting in the formation of even smaller droplets. APCI refers to vaporizing a sample before ionization. Under the action of a corona discharge needle, producing reagent ions, which transfer charge to analyte (Mezcua et al., 2008; Soler  et al., 2007).                                 

MATERIALS AND METHODS

Chemicals and reagents
 
This practical work was completed in 2025 at the Udaipur Public Health Laboratory in Rajasthan. Acetonitrile (LC/MS grade), water (LC/MS grade), methanol (LC/MS grade), ammonium format (LC/MS Grade), acetic Acid (LC/MS Grade), formic acid (LC/MS Grade), anhydrous magnesium sulfate, sodium acetate, primary and secondary amines, C18, pesticides, certified reference material/ standards.
 
List of instruments
 
UHPLC Ultimate 3000, TSQ Quantis triple quadrupole tandem mass spectrometer, ultrasonic water bath: PCi Analytics, Centrifuge: REMI, Vortex Mixer: Abdos, Micropipette: ThermoScientific; Stirring and grinding machine: Philips.
 
Pesticide’s calibration standard solution
 
Standards procured from Dr Ehrenstorfer Ltd. from Germany, where all the standards were individually wrapped in vials. Standard Concentration = Weight of Std. X Purity, X 1000/final Volume X100 Preparation of 10 mg/L standard solution Mixute: Transferred 0.1 ml of stock standard (Standard 1000 mg/L) to 10 mL volumetric flask, made up with a diluent acetonitrile. All Standards were prepared individually at ground level of 1000 mg/L. For concentration of 1000 mg/L, 10 g of powdered form of the standard was taken in 15 mL centrifuge tube, to which 10 mL of methanol was later added. i.e., 10 mg standard/10 mL = 1 mg/ml = 1000 mg/L of which further 10mg/L and 0.01mg/L working stock standard prepared and used for analysis. “Maximum Residual Limit (MRL)” as per Food Safety and Standards (Contaminants, Toxins, Residues) Regulation, 2011. Target compounds: Fenoxaprop-p-ethyl and Propargite-NH4. Their MRL value for Cucumber in mg/kg is 0.01.
 
Matrix match linearity preparation
 
To prepare a 1mg/L standard solution: Take 0.1 ml of mixed stock standard (10 mg/L standard solution) into 2 ml vial and dilute with 0.9ml of acetonitrile. To prepare a 0.1 mg/L standard solution, transfer 0.1 ml of mixed stock standard solution (1 mg/liter standard solution) into a 2 ml vial and dilute with 0.9 ml of acetonitrile. To prepare 0.01 mg/L standard solution: To Prepare 0.01 mg/L standard solution: Take 0.1 ml of mixed stock standard solution (0.1 mg/liter standard solution) to a 2 ml vial and dilute with 0.9 ml of acetonitrile. Preparation matrix, blank- Add equal amounts of water and matrix extract as shown in Table 1.

Table 1: List of solvent and matrix concentration levels.


 
The European norm standard EN method
 
Cucumber (500 g) sample obtained from an organic farm in Udaipur, Rajasthan, India. After cleaning, the sample is placed in a mixing grinder for grinding. The European Norm Standard EN 15662:2018 using for the extraction as well as cleanup is described below: 15 gram of homogenized sample taking into 50 ml centrifuge tubes (spiking done at three level 0.01 µg/kg, 0.025 µg/kg, 0.050 µg/kg for recovery). 15 ml of acidified LC-grade water (1% acetic acid) and acetonitrile adding into the centrifuge tube and it leaving for soaking for 15 minutes.4gram MgSO4 + 1 gram, NaCl + 1 gram, Na3 Citrate. 2H2O + 0.5 g, sodium citrate. 15 ml H2O was added to each tube and shaken vigorously for 5 mins. Then, sample was centrifuged at 4500 rpm for 10 mins. Transfer 2 ml aliquot of supernatant to 15 ml tubes (Tolgyesi  et al., 2022).
 
Clean up
 
Add 150 mg MgSO4, 50 mg “primary and secondary amine (PSA)” +5 mg “graphite carbon black (GCB)”, adding into each tube and shaking vigorously for 5 minutes. Vortex for 1min and centrifuge 4500rpm for 10mins. Transfer extract into a 2 ml Ria cap vial. Add 1 ml of supernatant to the Ria vial + Add 50 µl 10% diethyl glycol (DEG) in methanol. Evaporate under Nitrogen at 40°C 10-15 min, (N2 Pressure 10-20 Psi). Add 1 ml of 1:1 mobile phase during reconstitution. A: B +25 µl of Thiomethoxam- D3 (1 ppm) + Vortex + Sonicate. The filtrate has been filtered using 0.2 micrometre nylon filter membrane into RIA vial. Transfer 1 ml solution into Ria vial, mix 50 µl of internal standard mixture, then inject into LC-MS/MS instrument for analysis (Toth  et al., 2022; Lobbert et al., 2021).
 
The QuEChERS method
 
AOAC 2007.01 version was used for the extraction and cleanup, as described below: Cucumber (500 g) of sample procured from the market.15 grams of homogenized sample is taken into 50 ml centrifuge tubes (spiking done at three levels: 0.01 µg/kg, 0.025 µg/kg, 0.050 µg/kg for recovery).15 ml of acidified LC-grade water (1% Acetic acid) is added to the centrifuge tube. Then, acetonitrile is added to the centrifuge tube. Soak for 15 minutes. 6 grams of magnesium sulfate, C18+GCB+Shake well. 1.5 g sodium acetate is added to each tube and shaken vigorously for 1 minute. Vortex sample in the Centrifuge Tube. Then, the sample has been centrifuged at 4500 rpm for 10 mins. Transfer 2 ml aliquot of supernatant to 15 ml tubes (Wilkkowska et al., 2011).
 
Clean up
 
Add 150 mg MgSO4, 50 mg PSA + C18 + GCB has been added into each tube and shaken vigorously for 5 minutes. Vortex for 1min and centrifuge it at 4500 rpm for 10 min. Transfer extract to 2 ml vial. Put 1ml of supernatant into Ria vial + 50 µl 10% DEG in methanol. Evaporate under Nitrogen at 40ºC 10-15min, (N2 Pressure 10-20 Psi). Add 1 ml of 1:1 mobile phase during reconstitution. A: B +25 µl of Thiomethoxam- D3 (1ppm) + Vortex + Sonicate. The filtrate has been filtered using 0.2 µm nylon membrane into Ria vial. Transfer 1 ml of the solution to autosampler vial, add 50 µl of internal standard mixture and then inject it into LC-MS/MS for analysis (Santana-Mayor  et al., 2019).

RESULTS AND DISCUSSION

Linearity curve/calibration curve
 
Linearity denotes ability of analytical technique for producing test outcomes which are proportional to concentration of the analyte in the sample within specific range. Evaluation is typically carried out through analyzing series of standard solutions at various concentrations (such as 10, 25, 50 µg/kg). This relationship was assessed by constructing calibration curve and calculating the coefficient of determination (R2 = 0.999-1.000) using linear regression summarized in Table 2 and a linearity graph was provided in Fig 1, Fig 2, Fig 3 and Fig 4 (Moosavi et al., 2009; Tan et al., 2012).

Table 2: According with EN/QuEChERS linearity.



Fig 1: Calibration curve fenoxaprop-ethyl-a.



Fig 2: Calibration curve propargite-NH4.



Fig 3: Calibration curve fenoxaprop-ethyl-a.



Fig 4: Calibration curve propargite-NH4.


 
Accuracy
 
The extent to which measured value corresponds to the actual (true) value is referred to as accuracy. This is expressed as recovery rate (spiking recovery rate) when known quantity of analyte is integrated into a sample. Three spiking levels: 10 µg/kg: Recovery rate = 97.5%; 25 µg/kg: Recovery rate = 97.2%; 50 µg/kg: Recovery rate = 99.3% (Van Eckhart  et al., 2009; Zhou  et al., 2005).
 
Recovery (%)
 
Recovery refers to the percentage of an analyte that is extracted and detected from a matrix (e.g., cucumber) compared to the theoretical amount spiked. It shows the accuracy of the method (Benedetti et al., 2020). Relative Standard Deviation (RSD) Percentage: %RSD is measure of accuracy-how closely the findings of repeated measurements are close to each other. This is calculated as standard deviation divided by mean, multiplied by 100. Limit of Quantification (LOQ): LOQ is lowest concentration of analyte which could be detected with acceptable precision and accuracy. In this sample, limits of quantitation were 10, 25, 50 µg/kg, correspondingly summarized in Table 3 and Table 4 (Jan et al., 2025).

​

Table 3: Recovery and precision data according with EN.



​

Table 4: Recovery and precision data according with QuEChERS.



Chromatogram peaks
 
Chromatographic peaks of propyneNH„  represent the retention behavior and detector response of the compound when analyzed under the given chromatographic conditions. The sharp and symmetrical peaks indicate high separation efficiency and stable instrument performance, suggesting that propargyl ammonium is well separated from other matrix components. Retention time of peak corresponds to specific interaction between alkyne -NH4 and the stationary and mobile phases, reflecting its polarity and affinity in the chromatographic system provided in Fig 5. Similarly, Fig 6 shows the chromatographic peaks of Fenoxaprop-p-ethyl, indicating that the compound has been successfully detected and has a clear and distinct peak at its characteristic retention time. The absence of overlapping or tailed peaks indicates that this method has high selectivity and accuracy for the quantification of ethyl phenoxypropionate. The intensity (height or area) of peak is directly proportional to concentration of analyte, confirming sensitivity of the method for pesticide residue analysis. These chromatograms collectively validate that the analytical method can effectively separate and quantify propyne ammonium salt and acetonitrile fluoxazolyl propyl ester, ensuring its reliability in routine monitoring or residue determination (Raina, 2011).

Fig 5: Chromatogram peak of propargite-NH4.



Fig 6: Chromatogram peak of fenoxaprop-p-ethyl.


 
Data interpretation
 
Fenoxaprop-p-ethyl under the EN method, recovery observed at 10 µg/kg (97.59), 25 µg/kg (97.28%) and the highest at 50 µg/kg (99.39%). The %RSD values across all levels are below 5%, specifically 4.82% (10 µg/kg), 2.13% (25 µg/kg) and 1.08% (50 µg/kg), which indicates excellent precision and reproducibility. These values   fall within the generally accepted threshold range of d”20% for residue analysis as specified in the SANTE/12682/2019 guideline. With the QuEChERS method, recoveries are slightly lower at the 10 µg/kg level (90.45%) but improved significantly at 25 and 50 µg/kg, reaching 97.98% and 98.68%, respectively. The %RSD values are again within acceptable limits: 4.46% (10 µg/kg), 3.94% (25 µg/kg), 1.14% (50 µg/kg). Such outcomes demonstrate that QuEChERS technique provides both reliable accuracy and reproducibility, particularly at higher concentrations summarized in Table 3 and Table 4 (Wille et al., 2007).

CONCLUSION

Comparative evaluation of EN 15662 and QuEChERS methods showed that integration of the two extraction techniques with LC-MS/MS analysis can effectively determine the residues of Fenoxaprop-p-ethyl and Propargite-NH4 in cucumber food matrices. However, there are significant differences in recycling rates and operational efficiency. The EN 15662 method includes a buffer extraction step, which slightly improves the recovery of ethyl phenoxypropionate and exhibits lower matrix interference, making it more suitable for samples with complex matrices. On the other hand, the QuEChERS method provided faster sample preparation with comparable sensitivity for Propargite-NH4, while both methods meet the validation criteria outlined by international guidelines. The EN 15662 method is preferred in regulatory settings where precision and accuracy are critical, whereas QuEChERS offers advantages for high-throughput routine analysis. Although EN performs slightly better in terms of accuracy at lower concentrations, QuEChERS performs as well as or even better in terms of recovery performance at higher concentrations.

ACKNOWLEDGEMENT

This study was supported by the Udaipur Public Health Laboratory in Rajasthan, which provided the necessary facilities, resources and technical assistance to enable the research to be successfully completed.
 
Disclaimers
 
The views and findings presented in this article are entirely of author and may not be representative of their institution. Despite their best efforts to ensure information is accurate and complete, the authors assume all responsibility for any direct or indirect damage resulting from utilization of this content. 
 
Informed consent
 
All experimental procedures including animals have been reviewed and approved by institution’s Laboratory Animal Care Committee and all operations and care procedures were performed as per guidelines developed by university’s Laboratory Animal Care Committee.

CONFLICT OF INTEREST

There are no conflicts of interest in publishing this article, according to author. Additionally, external funding or sponsorship impacted study’s design, data collection, analysis, manuscript preparation, or decision to publish.

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    Full Research Article

    Comparative Evaluation of EN 15662 and QuEChERS Methods for the Determination of Fenoxaprop-p-ethyl and Propargite-NH4 Pesticide Residues by LC-MS/MS in Cucumber

    P
    Priyanka Gour1,*
    http://orchid.org/0009-0004-1611-9222
    P
    Purnima Dashora1
    http://orchid.org/0009-0004-2777-2841
    R
    Ravi Sethi2
    http://orchid.org/0009-0002-3306-1136
    1Department of Chemistry, Pacific Academy of Higher Education and Research University, Pacific Hills, Pratapnagar Extn, Airport Road, Debari, Udaipur-313 024, Rajasthan, India.
    2Food Analyst, Public Health Laboratory, Govt. Maharana Bhupal Hospital Campus, Udaipur-313 024, Rajasthan, India.

    ABSTRACT

    Background: The application of two widely used sample preparation methods (EN 15662 and QuEChERS) in determination of pesticide residues in food matrices was compared and evaluated. The aim was to evaluate the efficiency, accuracy, practicality of methods regarding extraction recovery and analytical performance, particularly for Fenoxaprop-p-ethyl and Propargite-NH4.

    Methods: The results show that both the QuEChERS and EN 15662 methods can effectively use liquid chromatography-mass spectrometry (LC-MS/MS) for detecting target analytes. Slightly higher recovery rate of the EN 15662 method indicates that this method has higher accuracy and precision for these compounds. 

    Result: In contrast, the QuEChERS method offers a faster sample preparation process and exhibits acceptable performance, making it a suitable choice when time efficiency is the primary consideration. The results suggest that the choice of method can be based on the characteristics of a specific pesticide and laboratory priorities, such as speed or sensitivity. The assessment results can provide informed decision support for pesticide residue testing for research and regulatory quality purposes.

    INTRODUCTION

    The QuEChERS (Rapid, simple, inexpensive, efficient, durable and safe) process is a simplifying and efficient technique designed specifically for routine pesticide residue analysis. This procedure includes extraction with acetonitrile, following salt partitioning and finally purification steps utilizing “dispersive solid-phase extraction (D-SPE)”. Owing to its high speed and low solvent consumption, it is ideal for high-throughput testing of various pesticides in range of food matrices, including crops with high water content like cucumbers (Plonka et al., 2025; Musarurwa et al., 2019). The EN method specifically refers to European standard EN 15662, which is the standard and validated version of QuECheRS technique for pesticide residue analysis in European Union. The main differences are in standardization and buffer composition; EN 15662 uses a citrate-buffered extraction system to improve stability and reproducibility across different laboratories and matrices. While both methods are efficient and effective, the EN method is suitable for regulatory compliance, while the general QuEChERS protocol is suitable for routine analysis (Mao et al., 2020). This study established method for evaluating dissipation of proporgite in pigeon pea using LC-ESI-MS/MS which has higher sensitivity, selectivity and specificity compared to other analytical techniques. Analogous effectiveness of LC-MS/MS for determination of indoxacarb residues in Pigeon pea green pods and dry grains (Naik et al., 2022). Pesticides divided into various groups based on the type of pest they target: Insecticides- used to kill insects, Fungicides-used to control fungal infections, Rodenticides-effective against rodents like rats and mice, Herbicides-used to eliminate unwanted weeds, often replacing manual weeding, Plant Growth Regulators-substances that influence plant development and growth (Lee et al., 2018). LC-MS is powerful analytical process which integrates sensitive and selective detection of mass spectrometry (MS) with separation capabilities of “high performance liquid chromatography (HPLC)” (Govind et al., 2023). HPLC remains crucial for minimizing matrix interferences that may affect ionization efficiency. When atmospheric pressure ionization (API) is used, both solvent removal and ionization occur at atmospheric pressure within the source, enhancing the method’s ability to detect trace-level analytes having high sensitivity and selectivity (Hamdy et al., 2019; Fernandez et al., 2008). HPLC has previously been employed for pesticide residue analysis in crops like chilli (Reddy et al., 2007) and tomato (Romeh et al., 2009) Pesticides currently used by farmers and to assess the presence of various pesticide residues in different vegetable crops (Nishant et al., 2016). However, during past years, combination of chromatography and MS has become selected method for detecting trace pesticide residues as result of higher sensitivity and accuracy (Lacina et al., 2010). Convert liquid analytes into gaseous ions suitable for detection. The most challenging part of the process is effectively removing the solvent while maintaining the vacuum environment required for the mass spectrometer. With the advent of thermal spraying and particle beam interfaces, popularity of LC-MS has increased significantly. Developing “Electrospray Ionization (ESI)” and “Atmospheric Pressure Chemical Ionization (APCI)”, both ESI and APCI fall under category of API techniques, operating at ambient pressure and offering gentle ionization conditions that help preserve molecular integrity in which analyte ions initially present in liquid phase transferred into gas phase for mass spectrometric analysis (Masia et al., 2014; Ecobichon, 2001). Electrostatic repulsion in the droplets causes them to undergo Columbic fission, resulting in the formation of even smaller droplets. APCI refers to vaporizing a sample before ionization. Under the action of a corona discharge needle, producing reagent ions, which transfer charge to analyte (Mezcua et al., 2008; Soler  et al., 2007).                                 

    MATERIALS AND METHODS

    Chemicals and reagents
     
    This practical work was completed in 2025 at the Udaipur Public Health Laboratory in Rajasthan. Acetonitrile (LC/MS grade), water (LC/MS grade), methanol (LC/MS grade), ammonium format (LC/MS Grade), acetic Acid (LC/MS Grade), formic acid (LC/MS Grade), anhydrous magnesium sulfate, sodium acetate, primary and secondary amines, C18, pesticides, certified reference material/ standards.
     
    List of instruments
     
    UHPLC Ultimate 3000, TSQ Quantis triple quadrupole tandem mass spectrometer, ultrasonic water bath: PCi Analytics, Centrifuge: REMI, Vortex Mixer: Abdos, Micropipette: ThermoScientific; Stirring and grinding machine: Philips.
     
    Pesticide’s calibration standard solution
     
    Standards procured from Dr Ehrenstorfer Ltd. from Germany, where all the standards were individually wrapped in vials. Standard Concentration = Weight of Std. X Purity, X 1000/final Volume X100 Preparation of 10 mg/L standard solution Mixute: Transferred 0.1 ml of stock standard (Standard 1000 mg/L) to 10 mL volumetric flask, made up with a diluent acetonitrile. All Standards were prepared individually at ground level of 1000 mg/L. For concentration of 1000 mg/L, 10 g of powdered form of the standard was taken in 15 mL centrifuge tube, to which 10 mL of methanol was later added. i.e., 10 mg standard/10 mL = 1 mg/ml = 1000 mg/L of which further 10mg/L and 0.01mg/L working stock standard prepared and used for analysis. “Maximum Residual Limit (MRL)” as per Food Safety and Standards (Contaminants, Toxins, Residues) Regulation, 2011. Target compounds: Fenoxaprop-p-ethyl and Propargite-NH4. Their MRL value for Cucumber in mg/kg is 0.01.
     
    Matrix match linearity preparation
     
    To prepare a 1mg/L standard solution: Take 0.1 ml of mixed stock standard (10 mg/L standard solution) into 2 ml vial and dilute with 0.9ml of acetonitrile. To prepare a 0.1 mg/L standard solution, transfer 0.1 ml of mixed stock standard solution (1 mg/liter standard solution) into a 2 ml vial and dilute with 0.9 ml of acetonitrile. To prepare 0.01 mg/L standard solution: To Prepare 0.01 mg/L standard solution: Take 0.1 ml of mixed stock standard solution (0.1 mg/liter standard solution) to a 2 ml vial and dilute with 0.9 ml of acetonitrile. Preparation matrix, blank- Add equal amounts of water and matrix extract as shown in Table 1.

    Table 1: List of solvent and matrix concentration levels.


     
    The European norm standard EN method
     
    Cucumber (500 g) sample obtained from an organic farm in Udaipur, Rajasthan, India. After cleaning, the sample is placed in a mixing grinder for grinding. The European Norm Standard EN 15662:2018 using for the extraction as well as cleanup is described below: 15 gram of homogenized sample taking into 50 ml centrifuge tubes (spiking done at three level 0.01 µg/kg, 0.025 µg/kg, 0.050 µg/kg for recovery). 15 ml of acidified LC-grade water (1% acetic acid) and acetonitrile adding into the centrifuge tube and it leaving for soaking for 15 minutes.4gram MgSO4 + 1 gram, NaCl + 1 gram, Na3 Citrate. 2H2O + 0.5 g, sodium citrate. 15 ml H2O was added to each tube and shaken vigorously for 5 mins. Then, sample was centrifuged at 4500 rpm for 10 mins. Transfer 2 ml aliquot of supernatant to 15 ml tubes (Tolgyesi  et al., 2022).
     
    Clean up
     
    Add 150 mg MgSO4, 50 mg “primary and secondary amine (PSA)” +5 mg “graphite carbon black (GCB)”, adding into each tube and shaking vigorously for 5 minutes. Vortex for 1min and centrifuge 4500rpm for 10mins. Transfer extract into a 2 ml Ria cap vial. Add 1 ml of supernatant to the Ria vial + Add 50 µl 10% diethyl glycol (DEG) in methanol. Evaporate under Nitrogen at 40°C 10-15 min, (N2 Pressure 10-20 Psi). Add 1 ml of 1:1 mobile phase during reconstitution. A: B +25 µl of Thiomethoxam- D3 (1 ppm) + Vortex + Sonicate. The filtrate has been filtered using 0.2 micrometre nylon filter membrane into RIA vial. Transfer 1 ml solution into Ria vial, mix 50 µl of internal standard mixture, then inject into LC-MS/MS instrument for analysis (Toth  et al., 2022; Lobbert et al., 2021).
     
    The QuEChERS method
     
    AOAC 2007.01 version was used for the extraction and cleanup, as described below: Cucumber (500 g) of sample procured from the market.15 grams of homogenized sample is taken into 50 ml centrifuge tubes (spiking done at three levels: 0.01 µg/kg, 0.025 µg/kg, 0.050 µg/kg for recovery).15 ml of acidified LC-grade water (1% Acetic acid) is added to the centrifuge tube. Then, acetonitrile is added to the centrifuge tube. Soak for 15 minutes. 6 grams of magnesium sulfate, C18+GCB+Shake well. 1.5 g sodium acetate is added to each tube and shaken vigorously for 1 minute. Vortex sample in the Centrifuge Tube. Then, the sample has been centrifuged at 4500 rpm for 10 mins. Transfer 2 ml aliquot of supernatant to 15 ml tubes (Wilkkowska et al., 2011).
     
    Clean up
     
    Add 150 mg MgSO4, 50 mg PSA + C18 + GCB has been added into each tube and shaken vigorously for 5 minutes. Vortex for 1min and centrifuge it at 4500 rpm for 10 min. Transfer extract to 2 ml vial. Put 1ml of supernatant into Ria vial + 50 µl 10% DEG in methanol. Evaporate under Nitrogen at 40ºC 10-15min, (N2 Pressure 10-20 Psi). Add 1 ml of 1:1 mobile phase during reconstitution. A: B +25 µl of Thiomethoxam- D3 (1ppm) + Vortex + Sonicate. The filtrate has been filtered using 0.2 µm nylon membrane into Ria vial. Transfer 1 ml of the solution to autosampler vial, add 50 µl of internal standard mixture and then inject it into LC-MS/MS for analysis (Santana-Mayor  et al., 2019).

    RESULTS AND DISCUSSION

    Linearity curve/calibration curve
     
    Linearity denotes ability of analytical technique for producing test outcomes which are proportional to concentration of the analyte in the sample within specific range. Evaluation is typically carried out through analyzing series of standard solutions at various concentrations (such as 10, 25, 50 µg/kg). This relationship was assessed by constructing calibration curve and calculating the coefficient of determination (R2 = 0.999-1.000) using linear regression summarized in Table 2 and a linearity graph was provided in Fig 1, Fig 2, Fig 3 and Fig 4 (Moosavi et al., 2009; Tan et al., 2012).

    Table 2: According with EN/QuEChERS linearity.



    Fig 1: Calibration curve fenoxaprop-ethyl-a.



    Fig 2: Calibration curve propargite-NH4.



    Fig 3: Calibration curve fenoxaprop-ethyl-a.



    Fig 4: Calibration curve propargite-NH4.


     
    Accuracy
     
    The extent to which measured value corresponds to the actual (true) value is referred to as accuracy. This is expressed as recovery rate (spiking recovery rate) when known quantity of analyte is integrated into a sample. Three spiking levels: 10 µg/kg: Recovery rate = 97.5%; 25 µg/kg: Recovery rate = 97.2%; 50 µg/kg: Recovery rate = 99.3% (Van Eckhart  et al., 2009; Zhou  et al., 2005).
     
    Recovery (%)
     
    Recovery refers to the percentage of an analyte that is extracted and detected from a matrix (e.g., cucumber) compared to the theoretical amount spiked. It shows the accuracy of the method (Benedetti et al., 2020). Relative Standard Deviation (RSD) Percentage: %RSD is measure of accuracy-how closely the findings of repeated measurements are close to each other. This is calculated as standard deviation divided by mean, multiplied by 100. Limit of Quantification (LOQ): LOQ is lowest concentration of analyte which could be detected with acceptable precision and accuracy. In this sample, limits of quantitation were 10, 25, 50 µg/kg, correspondingly summarized in Table 3 and Table 4 (Jan et al., 2025).

    ​

    Table 3: Recovery and precision data according with EN.



    ​

    Table 4: Recovery and precision data according with QuEChERS.



    Chromatogram peaks
     
    Chromatographic peaks of propyneNH„  represent the retention behavior and detector response of the compound when analyzed under the given chromatographic conditions. The sharp and symmetrical peaks indicate high separation efficiency and stable instrument performance, suggesting that propargyl ammonium is well separated from other matrix components. Retention time of peak corresponds to specific interaction between alkyne -NH4 and the stationary and mobile phases, reflecting its polarity and affinity in the chromatographic system provided in Fig 5. Similarly, Fig 6 shows the chromatographic peaks of Fenoxaprop-p-ethyl, indicating that the compound has been successfully detected and has a clear and distinct peak at its characteristic retention time. The absence of overlapping or tailed peaks indicates that this method has high selectivity and accuracy for the quantification of ethyl phenoxypropionate. The intensity (height or area) of peak is directly proportional to concentration of analyte, confirming sensitivity of the method for pesticide residue analysis. These chromatograms collectively validate that the analytical method can effectively separate and quantify propyne ammonium salt and acetonitrile fluoxazolyl propyl ester, ensuring its reliability in routine monitoring or residue determination (Raina, 2011).

    Fig 5: Chromatogram peak of propargite-NH4.



    Fig 6: Chromatogram peak of fenoxaprop-p-ethyl.


     
    Data interpretation
     
    Fenoxaprop-p-ethyl under the EN method, recovery observed at 10 µg/kg (97.59), 25 µg/kg (97.28%) and the highest at 50 µg/kg (99.39%). The %RSD values across all levels are below 5%, specifically 4.82% (10 µg/kg), 2.13% (25 µg/kg) and 1.08% (50 µg/kg), which indicates excellent precision and reproducibility. These values   fall within the generally accepted threshold range of d”20% for residue analysis as specified in the SANTE/12682/2019 guideline. With the QuEChERS method, recoveries are slightly lower at the 10 µg/kg level (90.45%) but improved significantly at 25 and 50 µg/kg, reaching 97.98% and 98.68%, respectively. The %RSD values are again within acceptable limits: 4.46% (10 µg/kg), 3.94% (25 µg/kg), 1.14% (50 µg/kg). Such outcomes demonstrate that QuEChERS technique provides both reliable accuracy and reproducibility, particularly at higher concentrations summarized in Table 3 and Table 4 (Wille et al., 2007).

    CONCLUSION

    Comparative evaluation of EN 15662 and QuEChERS methods showed that integration of the two extraction techniques with LC-MS/MS analysis can effectively determine the residues of Fenoxaprop-p-ethyl and Propargite-NH4 in cucumber food matrices. However, there are significant differences in recycling rates and operational efficiency. The EN 15662 method includes a buffer extraction step, which slightly improves the recovery of ethyl phenoxypropionate and exhibits lower matrix interference, making it more suitable for samples with complex matrices. On the other hand, the QuEChERS method provided faster sample preparation with comparable sensitivity for Propargite-NH4, while both methods meet the validation criteria outlined by international guidelines. The EN 15662 method is preferred in regulatory settings where precision and accuracy are critical, whereas QuEChERS offers advantages for high-throughput routine analysis. Although EN performs slightly better in terms of accuracy at lower concentrations, QuEChERS performs as well as or even better in terms of recovery performance at higher concentrations.

    ACKNOWLEDGEMENT

    This study was supported by the Udaipur Public Health Laboratory in Rajasthan, which provided the necessary facilities, resources and technical assistance to enable the research to be successfully completed.
     
    Disclaimers
     
    The views and findings presented in this article are entirely of author and may not be representative of their institution. Despite their best efforts to ensure information is accurate and complete, the authors assume all responsibility for any direct or indirect damage resulting from utilization of this content. 
     
    Informed consent
     
    All experimental procedures including animals have been reviewed and approved by institution’s Laboratory Animal Care Committee and all operations and care procedures were performed as per guidelines developed by university’s Laboratory Animal Care Committee.

    CONFLICT OF INTEREST

    There are no conflicts of interest in publishing this article, according to author. Additionally, external funding or sponsorship impacted study’s design, data collection, analysis, manuscript preparation, or decision to publish.

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