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SSRN Id4786309
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2 in food: selection of the best calibration model
3 José Manuel Veiga-del-Baño a, José Oliva a, Miguel Ángel Cámara a, Pedro Andreo-
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4 Martínez a *, Miguel Motas b
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7 b Department of Toxicology, Faculty of Veterinary, University of Murcia, Campus of Espinardo, 30100
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8 Murcia, Spain.
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*Corresponding author: Pedro Andreo-Martínez. E-mail: pam11@um.es
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22 Abstract
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23 In this study, an automated package was developed to calculate the best calibration
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25 development in the package is based on three requirements for routine food pesticide
26 analysis; good working range fitness for samples with high Maximum Residue Limits
27 (MRLs), detection capability for pesticide analysis with MRLs close to the limit of
28 quantitation and a simple working range problem detection model. The requirements are
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29 combined in a simple scoring system above 100.
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30 The package has been tested in the analysis of pesticides of pepper and wheat flour. The
31 results show that the package can be used for different pesticides in a quick and visual
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32 way, and also allows evaluation of matrix effects between different matrix calibrations.
33 For the pesticide tested with the package, the weighted linear calibration gave the best
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34 score over the simple linear calibration and the second order calibration.
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37 Pesticides;
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45 Introduction
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46 Pesticides are widely used in agriculture to protect livestock and crops, with more than
47 4.0 million tonnes used annually worldwide to control a wide range of pests [1]. In this
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48 sense, around 333,000 tonnes of pesticides were used in 2021, with more than 400 new
50 The widespread use of pesticides on crops requires the monitoring of pesticide residues
51 to ensure food quality and safety. For this reason, Maximum Residue Limits (MRLs)
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52 have been set by various regulations around the world to prevent toxicity problems
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53 associated with excessive use of pesticides [3]. In the European Union (EU), for
56 The development of appropriate methods to assess food safety in accordance with the
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57 requirements of international quality standards is one of the main objectives in pesticide
58 analysis [6]. In order to determine as many pesticides as possible in the most cost-
59 effective way and with the least amount of effort, multi-residue methods (MRMs) are
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60 required. Until now, pesticides have usually been determined by classical analytical
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61 methods such as gas chromatography (GC) and liquid chromatography (LC) coupled
62 with mass spectrometry (MS), and the most widely used pesticide residue extraction
63 method in routine laboratories today is the method with the acronym "Quick, Easy,
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64 Cheap, Effective, Rugged, and Safe" (QuEChERS). The QuEChERS method involves
65 two steps, the first being an initial extraction with different salt formulations to drive the
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66 separation of the organic extraction solvent and water. The second, where an aliquot of
67 the organic phase goes through a clean-up process in dispersive solid phase extraction
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68 (d-SPE) using different sorbents to remove the matrix component prior to injection by
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70 The extraction method in QuEChERS has been subject to certain variations and
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71 modifications to cover a wide range of products, such as the addition of water (for
72 spices, flour and other dehydrated matrices) or the addition of a buffer method when
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74 The clean-up approaches aim to reduce the Matrix Effect (ME) in the variability of
75 foods that can be analysed, such as foods with chlorophyll or carotenoids and other
76 natural colours (e.g. spices), fat or lipid content (e.g. nuts), essential oils and flavonoids
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77 (e.g. herbs), etc [9]. These ME lead to analytical problems that affect in the accuracy of
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78 the results and can be seen in the recovery of pesticides by reducing or increasing the
79 acceptable value for the purpose of validation from 70% to 120% [6, 10].
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One of the most common approaches to reducing ME methods is the matrix-matched
81 calibration (MMC) [11]. Some of its advantages include the wide range of matrices that
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82 can be used [9, 10, 12, 13], its use in GC and LC, and its use in conjunction with other
84 The use of MMC is widely described for calibration purposes [15, 16], and used in
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85 different fields of instrumental analysis [17-19], but especially in MS for the effects on
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88 enhancement of the analyte signal, affecting the reproducibility and trueness of the
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89 result [20].
91 guides and standards for pesticides [14] and has been widely studied in different and
92 complex samples analysed by GC or LC [21-24] as a suitable option for the use in the
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94 uncertainty in the SANTE 11312/2021 [6] guideline for pesticide analysis. However,
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95 although there are many studies on the influence of the matrix on pesticide analysis and
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96 quantification errors [25], there is no information on the selection of appropriate
98 significant for the overall uncertainty of pesticide analysis, as the most important
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99 contributing factors are precision and recovery [26], it is necessary to choose a
100 calibration model that minimises this contribution, or to quickly visualise which factors
101 influence the use of one model or another in routine analysis. In addition, for pesticide
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102 analysis, it is necessary that the calibration model allows the most accurate
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103 quantification of concentrations close to the first calibration point for those pesticides
104 with very low MRLs such as carbofuran [sum of carbofuran (including any carbofuran
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formed from carbosulfan, benfuracarb or furathiocarb) and 3-OH-carbofuran expressed
106 as carbofuran] with an MRL of 0.002 mg/kg in tomatoes, while at the same time
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107 quantifying other pesticides with much higher MRLs at the upper end of the calibration
108 range (e.g. famoxadone with an MRL of 2 mg/kg in tomatoes). In this case, the
110 Although the software of commercial chromatographs has many numerical and
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111 graphical tools, there is no way to simultaneously compare the calibration models of
112 different pesticides, nor the influence of their use on the parameters that can influence
113 the quantification of results, such as detection capability or goodness of fit, in routine
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117 better calibration model using different tools and a scoring system based on the SANTE
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118 and ISO requirements for these pesticides analysed for use in validation, and to reduce
119 the quantification error in routine analysis used in different MME calibrations through
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120 numerical and graphical analysis. To evaluate the package, 23 pesticides were analysed
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121 by LC and GC using pepper as a matrix line. This package was also used to detect
122 MME between pepper and wheat flour in the pesticides analysed by GC.
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123
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126 The R package was developed using the RStudio IDE Desktop 2023.09.0 tool, and R
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127 4.2.2 was used to analyse the data and generate the graphs [27]. This software is free
128 and can be used in both desktop and cloud versions. RStudio allows to create scripts and
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129 use loops with code written in R. The R package ChemACal (chemical analytical
130 calibration) can be used to automate by loop all pesticides analysed by GC-MS/MS and
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131 LC-MS/MS simultaneously. An example of the loop can be provided on request to the
132 authors.
134 The proposed workflow for the analysis of the calibration data is a sequential process
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135 consisting of three steps (Figure 1). In step 1, data are exported from the commercial
136 software coupled to the chromatography system. In step 2, the R package needs two
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137 different data sets with the information to evaluate the calibration. The data must be
138 imported in csv, xlsx or other type of format. In the first dataset it is necessary to
139 include different columns with the names of all the pesticides and in the second dataset
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140 all the calibration data with two columns for each pesticide named in the first dataset.
141 The first column of the second data set contains the concentration information and the
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142 second column the instrumental response (area) for each concentration. As a safety
143 measure, for each pair of values of concentration and instrumental response, it is
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144 assessed whether the number of concentration data is the same as the response and if
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145 not, it is moved to the next pesticide.
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146
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147 Figure 1. ChemACal sequential process.
148 Step 3, described in sections 2.2.1 and 2.2.2, is the evaluation and scoring algorithm
151 There are several alternatives to evaluate linearity based on graphical (residual plot,
152 linearity plot), statistical test (ANOVA, ANOVA-LOF, Mandel, significance of the
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154 instrumental analysis [15, 28-32], since their use is appropriate for the evaluation of the
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155 calibration model, taking into account their advantages and disadvantages.
156 The algorithm used focused on evaluating, on the one hand, the God of Fitness (GOF)
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157 in all the range of calibration and, on the other hand, the Capability of Detection (COD)
158 of each calibration model. According to section 6.2.1 in the UNE-CEN/TS 17061 [14]
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159 of use of the simplest acceptable calibration, the linear, the weighted linear and the
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160 second order models were calculated.
161 Several assumptions used in routine pesticide analysis have been made, such as that the
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162 calibration standard is injected only once, and for this the simplest weight (w) used was
164 Equation 1 shows the algorithm used to evaluate the GOF based in the residual standard
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165 deviation (Sy) according to Mandel GOF indicated in the ISO 8466-1 [33] and the ISO
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166 8466-2 [34], but expressed as relative residuals (Syrel) [30]. On the other hand, Equation
167 2 to 5 show the algorithm for evaluating the detection capability based on ISO 11843-2
170 Where N is the number of calibration points, p is the point for calculating the degree of
171 freedom; 2 for linear cases and 3 for second-order calibration. The yi represents the
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172 experimental response and yi the response applied the model of calibration and 𝑦 is the
𝑆𝑦 1 2
𝑥
175 COD = δ × 𝑏
× 1+𝑁+𝑆 Equation 2 (linear case)
𝑥𝑥
176 Where δ is the value of the non-centrality parameter with N-2 degrees of freedom and a
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177 relative error of 5%, b is the slope for the calibration model, 𝑥 is the mean concentration
178 for the calibration points expressed by Equation 3, and Sxx is the sum of the squared
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180 Equation 3 shows the mean concentration for the calibration points
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181 Sxx = ∑N
i=1 𝑤𝑖(𝑥𝑖 ― 𝑥) Equation 3
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182 Equation 4 shows the sum of the squared deviations of the calibration points.
∑N
i=1 𝑤𝑖 × 𝑥𝑖
183 𝑥= Equation 4
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𝐹
184 In the case of linear calibration without weight the value of wi is 1, and F is the number
185 of calibration points. If the weight 1/x is used, wi is 1/xi and the value of F is ∑N
i=1 𝑤𝑖.
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186 Equation 5 shows the COD of each calibration model in the second order case.
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𝑆𝑦
187 COD = δ × 𝑏𝑠 ×
∑N 2 2 ∑N 2
2 i=1 𝑥𝑖 i=1 𝑥𝑖
(𝑥 ― 𝑥2) × 𝑄𝑥4 + (𝑥2 ― ) × 𝑄𝑥𝑥 ― 2 × (𝑥 ― 𝑥) × (𝑥2 ― ) × 𝑄𝑥3
188 1+
1
+ 𝑁er 𝑁 Equation 5
𝑁 2
𝑄𝑥4 × 𝑄𝑥𝑥 ―(𝑄𝑥3)
193 The algorithm used to score the best calibration model is based on a simple scoring
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194 system where 30 points are given for the minimum COD calculated and the other 30
195 points for the minimum Syrel or GOF obtained. The other 40 points are allocated to the
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196 model based on the Mandel test as defined in ISO 8466-1 [33], giving priority to linear
197 calibrations over second order calibrations [as defined by UNE-CEN/TS-17061 [14]]. A
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199
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201 To assist in the selection of the best calibration model, a difference DS2 of the sums of
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202 squared deviations is calculated from the residual standard deviation according to
203 Equation 6. er
204 𝐷𝑆2 = (N ― 2) × 𝑆2𝑦𝑙 ― (N ― 3) × 𝑆2𝑦𝑠 Equation 6
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205 Where Syl is the residual standard deviation in the linear case (linear and linear
206 weighted) and Sys is the residual standard deviation in the second order calibration.
207 By applying an F-test [33] to the value of DS2 and Sys, the calibration function can be
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208 estimated: it is linear in the working range examined. If it is concluded that it is not
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209 linear, a check shall be made whether there is a maximum or minimum within the
𝑏
211 𝑥∗ = ― 2𝑐 Equation 7
212 Where x* must be between the first and last calibration point. The terms b and c refer to
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216 2.2.3. Algorithm for matrix effect
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217 Equation 8 shows the matrix effect between the MMC used. The ME was calculated
218 from slopes of calibration curves of the different matrices used [36] and evaluated
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219 according to the established range of low (<20%), moderate (20-50%) and high (>50%)
220 [21].
𝑆𝑙𝑜𝑝𝑒 𝑚𝑎𝑡𝑟𝑖𝑥 2
221 𝑀𝐸(%) = 100 × (𝑆𝑙𝑜𝑝𝑒 𝑚𝑎𝑡𝑟𝑖𝑥 1 ―1) Equation 8
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222 Where slope matrix 1 is the slope in the calibration model selected for the MMC used as
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223 reference (in this case of pepper) and slope matrix 2 is the slope in the same calibration
224 model used to evaluate the ME (in this case of wheat flour).
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225 2.3. Pesticide analysis
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226 The QuEChERS extraction, based on the E1 extraction of UNE [37], used 10 grams for
227 pepper and 5 grams for wheat flour in a 50 ml polypropylene tube without addition of
228 water. Then 10 ml of acetonitrile was added and the mixture was shaken for 1 minute.
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229 After shaking, the salt extraction kit was added and the mixture was centrifuged at 3000
230 rpm for 5 minutes. A clean-up based on C2 EN 15662 of UNE [37] clean-up using PSA
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231 was performed on the organic aliquot obtained and finally it was centrifuged again at
232 3000 rpm for 5 minutes to obtain the final aliquot for GC-MS/MS and LC-MS/MS
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233 analysis.
234 A total of 10 pesticides were analysed by GC-MS/MS in pepper and wheat flour
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235 matrices using an Agilent 7890 (Santa Clara, USA) GC system coupled to a 7000A
236 quadrupole tandem mass spectrometer. The chromatographic separation was performed
237 on a RESTEK RTx-5MS column (30 m, 0.25 mm, i.d., 0.5 µm). Helium was used as the
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238 carrier gas at a constant flow rate of 1.2 mL/min, while argon was used as the collision
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239 gas. The oven temperature was adjusted as follows: the initial temperature was set at 70
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240 °C for 2 min, then increased to 150 °C at a rate of 25 °C min-1, to 200 °C at 3 °C min-1
241 with a hold time of 1 min, and finally to 280 °C at 10 °C min-1 with a hold time of 10
242 min. The total run time was 45 min. The temperatures of the transfer line and ion source
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243 were set at 280 °C and 250 °C respectively. The mass spectrometer was operated in
244 multiple reaction monitoring (MRM) mode with three mass transitions. The calibration
245 range used for pepper and wheat flour was between 3 and 100 ng/ml.
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246 A total of 13 pesticides were analysed by LC-MS/MS in pepper matrix using an Agilent
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247 liquid chromatography system (Santa Clara, USA) coupled to a 6470 triple quadrupole
250 of 0.1 ml at 40 ºC. The elution solvents used were water 5 mM ammonium formate with
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251 0.01% formic acid (A) and methanol 5 mM ammonium formate with 0.01% formic acid
252 (B). The gradient elution was performed as follows: 40% solvent B for 0-5 min,
253 changing to 60% solvent B for 6-12 min and finishing with 100% solvent B for 17-20
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254 min. Pesticides were analysed using programmed MRM in positive and negative modes
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255 simultaneously. Ion source parameters included optimised drying gas temperature,
256 drying gas flow rate, nebuliser pressure, sheath gas temperature and flow rate, capillary
257 voltage, nozzle voltage and high and low radiofrequency voltage. The calibration range
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259 MRM transitions and retention times for the pesticides tested are given in
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261
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263 3.1. Evaluation of the calibration data
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264 GC-MS/MS and LC-MS/MS data calibration exported and processed by the doEvalCal
265 function are shown in Table 1 and 2. Table 2 shows only the information calculated by
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266 Equations 1 to 6 and the score obtained, but other information such as the regression
267 equation, the coefficient of determination and the minimum response for the first
268 calibration point are shown for comparison with the commercial software used by the
269 chromatograph.
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270 Table 1. Results applying doEvalCal function to matrix-matched calibration by GC-
271 MS/MS.
Compound
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Model
Linear
COD
2.27
GOF
1.5
SCORE
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Chlorpropham
Linear-Weighted 0.53 1.5 86
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Second-order 1.43 0.8 41
Linear 3.13 2.1 33
Fenpropathrin Linear-Weighted 0.645 2.3 77
Second-order 0.805 0.5 54
Linear 4.6 3.1 9
endimethalin Linear-Weighted 0.964 3.5 65
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Second-order 1.97 1 56
Linear 2.98 2 64
Cyproconazole Linear-Weighted 0.766 2 66
Second-order 1.87 1.1 42
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Linear 5.22 3.3 41
Pyriproxyfen Linear-Weighted 1.25 3.6 82
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Second-order 2.81 1.5 43
272 COD: Capability of detection in ng/ml; GOF: Good of Fitness in percentage; Score: Scoring after
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274
276 MS/MS.
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Compound Model COD GOF SCORE
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Linear 2.31 4.2 61
Mandipropamid
Linear-Weighted 0.835 4.2 100
Second-order 2.78 4.3 38
er Linear 1.35 2.5 82
Spirotetramat (sum) Linear-Weighted 0.563 2.8 77
Second-order 1.56 2.5 41
Linear 2.94 5.1 82
Spirotetramat enol Linear-Weighted 1.2 5.4 78
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Second-order 3.59 5.8 36
Linear 2.79 5 53
Acetamiprid Linear-Weighted 0.753 5.3 93
Second-order 2.8 4.1 38
Linear 1.08 2 82
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0.653 1.2 88
Pyraclostrobin Linear-Weighted 0.382 1.5 74
Second-order 0.836 1.4 40
Linear 2.55 4.4 43
Spinosad Linear-Weighted 0.732 5 83
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Second-order 4.81 7.2 35
Linear 3.16 5.9 62
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Spiromesifen Linear-Weighted 1.22 6.8 96
Second-order 3.79 5.9 40
Linear 5.77 10.3 50
Thiacloprid Linear-Weighted 1.46 10.9 91
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Second-order 3.91 7.7 41
277 COD: Capability of detection in ng/ml; GOF: Good of Fitness in percentage; Score: Scoring after
279 Tables 1 and 2 show that the model with the best score in most of the pesticide is in the
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280 linear weighted calibration mainly due to a minimum COD and a good GOF, which
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281 ensures that values can be quantified close to the limit of quantification and that the
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On the other hand, the GOF results do not show that the use of a second-order
284 calibration is always an improvement over a linear calibration. Clear examples of such
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285 cases are cyprodinil, dimetomorph in GC-MS/MS or mandipropamid and spirotetramat
286 in LC-MS/MS, where there are cases where the second-order values are higher than the
287 linear case. For example, spriodiclofen has a second-order GOF value of 7.2 versus 6.6
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288 in the linear weighted case. The same situation is repeated for the calculation of COD,
289 where the linear-weighted calibration generally gives a better COD than the linear or
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291 of the two factors, GOF and COD, together with minimal model error, gives the best
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292 results in the linear-weighted calibration compared to the second-order calibration. This
293 confirms the statement in the UNE-CEN/TS-17061 [14] standard that the use of linear
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294 calibration models is preferable to more complex models such as second order models.
295 The linear calibration versus the linear-weighted calibration, although the GOF is
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296 similar, e.g. spiromesifen has a GOF value of 5.9 in the linear case versus 6.8 in the
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297 linear-weighted case, always gives better results in COD with the linear-weighted
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298 calibration (1.22 versus 3.66 ng/ml).
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300 The package has two graphical tools. The first allows filtering by type of calibration and
301 by COD limit, i.e. if the pesticide analysed must have at least a limit of quantification of
302 0.005 mg/kg, it is necessary to have a COD limit of 0.003 mg/L in the calibration data.
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303 The doGrafXcrit function allows a quick visualisation of the number of compounds that
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304 satisfy this condition, as shown in Figure 3.
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306 Figure 3. Visualization of compounds for a type of calibration and COD limit.
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307 Figure 3 also shows that the linear calibration does not meet the COD limit of 0.003
308 µg/ml for 57% of the compounds. So, a priori, it would not be the best calibration to use
309 for the pesticides analysed. To be able to visualise which is the best calibration by
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310 comparing the different calibrations, a new graphical tool is needed. The visualisation of
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311 all the information obtained by the doEvalCal function is realised by the doGrafBcal
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312 function. This function is used to obtain data from GOF (Equations 1 to 3), COD
313 (Equations 4 to 6), the calculated score and the instrumental response of the first point
314 of calibration. The graphical results are grouped by type of calibration and with a radius
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315 in the bubble chart depending on the value of COD.
316 Figure 4 shows three colours for the type of calibration: purple for linear calibration,
317 green for weighted calibration and yellow for second order calibration. This graph
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318 allows all the information and compound names to be displayed interactively, e.g.
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319 thiacloprid appears with all this information but for all the circles can be conveniently
320 displayed. er
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321
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323 Figure 4 also quickly shows that the linear weighted calibration (green bubbles) has the
324 best results (x-axis) and the bubbles with less radius (better COD). The worst
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325 calibration is the linear calibration for a worst COD and therefore a low value in the
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326 score. The two bubbles with the two worst GOF values (values above 9 on the y-axis)
328 calibration has a higher GOF value (10.9), but with a COD of 0.0015 µg/ml it is
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329 sufficient to meet the limit of 0.003 µg/ml, which would not be met in the linear
331 Figure 5 shows the graphical option doGraphME. This option allows the visualisation of
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332 the pesticides classified according to their matrix effect (low, medium and high). For the
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333 pesticides analysed with different MME calibrations (pepper and wheat flour), the
334 results of Figure 5 show that only cyprodinil has a high matrix effect (>100) and the rest
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335 of the pesticides have a low matrix effect.
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336
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337 Figure 5. Matrix effect in pesticides analyzed with two different MME calibration.
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340 4. Conclusions
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341 The results of this study showed that the new R package could be used to select the best
342 calibration in pesticide analysis where many pesticides could be analysed. Using the
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343 package, the best model calibration obtained was the linear-weighted calibration, where
344 the better evaluation was based on good GOF and COD values compared to other
345 models evaluated as the classical linear calibration and the second-order calibration.
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346 This package was also found to be suitable for testing matrix effects against different
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347 types of matrix calibration.
348 All information can be quickly visualised through data sets or various graphical tools
352 The authors declare that this research did not receive any specific grant from funding
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354
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355 6. Funding
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356 This research did not receive any specific grant from funding agencies in the public,
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359
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362 7. References
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363 [1] B. Liu, Y. Fan, H. Li, W. Zhao, S. Luo, H. Wang, B. Guan, Q. Li, J. Yue, Z. Dong, Y. Wang, L.
364 Jiang, Control the Entire Journey of Pesticide Application on Superhydrophobic Plant
365 Surface by Dynamic Covalent Trimeric Surfactant Coacervation, 31 (2021) 2006606.
366 https://doi.org/10.1002/adfm.202006606
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367 [2] Eurostat, Pesticide sales. Available on:
368 https://ec.europa.eu/eurostat/databrowser/view/aei_fm_salpest09/default/table?lan
369 g=en, 2023.
370 [3] J.M. Veiga-del-Baño, J.J. Cuenca-Martínez, P. Andreo-Martínez, M.Á. Cámara, J. Oliva, M.
371 Motas, Uncertainty and associated risks in the analysis of pesticides in homogeneous
372 paprika samples, Food Chem., 429 (2023) 136963.
373 https://doi.org/10.1016/j.foodchem.2023.136963
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374 [4] EC, Regulation (EC) No 396/2005 of the European Parliament and of the Council of 23
375 February 2005 on maximum residue levels of pesticides in or on food and feed of plant
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376 and animal origin and amending Council Directive 91/414/EEC Text with EEA relevance.
377 Available online: https://eur-lex.europa.eu/legal-
378 content/EN/ALL/?uri=celex%3A32005R0396, (2005).
379 [5] P. Kuchheuser, M. Birringer, Pesticide residues in food in the European Union: Analysis of
380 notifications in the European Rapid Alert System for Food and Feed from 2002 to 2020,
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381 Food Control, 133 (2022) 108575. https://doi.org/10.1016/j.foodcont.2021.108575
382 [6] SANTE, Guidance SANTE 11312/2021 – Analytical quality control and method validation
383 procedures for pesticide residues analysis in food and feed. Available on:
384 https://www.accredia.it/en/documento/guidance-sante-11312-2021-analytical-
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