## 2 Basis of the QuEChERS Method
As it can be observed, this strategy has been mainly applied to the determination of PAs in honey samples, followed by the analysis of herb samples (highlighting oregano) and (herbal) teas (including both the dry product and the beverage) (Figure 4 and Table 1), likewise, its application to cereal samples, such as wheat, sorghum and quinoa. In contrast, to a lesser extent, it has been applied to the analysis of legumes (pea and soy) and vegetables (leek) (Table 1 and Figure 4). It has also been used in products employed as food supplements, such as pollen, and in feed and forage samples (Table 1 and Figure 4). Figure 2: Schematic layout of the original QuEChERS procedure with its two differentiated steps. Figure 4: Overview of the different food and feed matrices used as samples for the determination of pyrrolidine alkaloids by modified QuEChERS method over the last 11 years (2011–2022). Data obtained from Scopus, Web of Science and Google search engines up to March 2022. Figure 3: Most notable modifications of the original QuEChERS procedure. PSA: primary secondary amine; TSCDH: trisodium citrate dihydrate; DSHCSH: disodium hydrogen citrate sesquihydrate; C18: octadecylsilane, GCB: graphitized carbon black; MWCNTs: multiwalled carbon nanotubes. \begin{table}
\begin{tabular}{c c c c c c c c c} \hline \hline
**Sample (Amount)** & **Analytes** & \multicolumn{4}{c}{**QuaCELERs**} & \multicolumn{1}{c}{**Analysis**} & \multicolumn{1}{c}{**Recovery (\%)**} & \multicolumn{1}{c}{**LOQ**} & \multicolumn{1}{c}{**Ref.**} \\ \cline{2-9}  & **Extraction Solvent** & **Partition Salts** & **Clean-Up** & & & & & \\ \hline Honey (1.5 g) & 9 PAs & LLE with 10 mL. & 4 g MgCo\({}_{4}\) & 150 mg PSA & HPLC-Q-Orbitrap- & 92-115 & 0.1–0.7 ug/Kg & [19] \\  & & H\({}_{\rm{3}}\)CO\({}_{3}\) (0.1 M). & 1 g TSDCH & 900 mg MgCo\({}_{3}\) & MS/MS & & \\  & & addition of zinc dust. & 0.5 g S/BCHSH & & ESI positive in mode & & \\  & & Supernatnat with 10 & 1 g NaCl & & HRSM mode & & \\  & & mL. ACM & 1 g NaCl & & Column: CS at 35 °C & & \\ \hline Honey (2.5 g) & 9 PAs & LLE with 10 mL, & 4 g MgCo\({}_{4}\) & 150 mg PSA & UHPLC-Q-MS & 67–122 & 0.081-4.35 & [20] \\  & & H\({}_{\rm{3}}\)CO\({}_{3}\) (0.05 M). & 1 g TSDCH & 45 mg Co\({}_{3}\) (5.5 M) & ESI positive in mode & & \\  & & addition of zinc dust. & 0.5 g S/BCHSH & 900 mg MgCo\({}_{3}\) & Solid mode & & \\  & & mg. ACM & & Column: CS at 34 °C & & & \\ \hline Honey (1 g) & 16 & Dilution with 4 mL & 0.8 g MgCo\({}_{4}\) & dSFE (500 mg MgCo\({}_{4}\)) & HPLC-TQ-MS & 97–105 & 1–50 mg/Kg & [21] \\  & & water, followed by 4 & 0.2 g TSDCH & ESI positive in mode & & \\  & & mL. ACM & 0.1 g S/BCHSH & & Column: CS & & \\ \hline Honey (5 g) & 7 & 10 mL water followed & 4 g MgCo\({}_{4}\) & - & HPLC-QTRAP-MS/MS & 50–100 & - & [22] \\  & & by 10 mL. ACM & 1 g NaCl & ESI Positive in mode & & \\  & & & and Mylar mode & & & & \\ \hline Honey and & 7 PAs & 1 mL water followed & 1 g NaCl & 50 mg PSA & UHPLC-QTRAP-MS/MS & 61–120 & 1–20 pg/Kg & [23] \\ herbal beverage & & by 5 mL. ACM & & ESI Positive in mode & & \\ (1 g) & & & & & & & \\ \hline Bottled tea (4 mL) and & 27 & _BettiL_ rate 4 mL of & _BettiL_ rate & _BettiL_ rate - & UHPLC-TQ-MS/MS & 88–107 & 2,88 mg/L & [24] \\ and ten leaves (2) & 7/PAs/PAs & 15/PAs/PAs & & MPP & 22.2 g & _Tale_ length 500 mg PSA, & ESI Patterson mode & 0.19-16/L & \\ \(\delta\) & & 7/PAs/PAs & 25 mL & 0.6 g TSDCH & 0.2 g & MgCM mode & & \\  & & water followed by 10 & DSHCHI, 0.6 g NaCl & & & & \\  & & mL. ACM with 176 & _Tale_ rate 84 MgCo\({}_{4}\) & & & & \\  & & formic acid & 1 g TSDCH, 0.5 g & & & & \\  & & & DSHSHC, 1.6 g NaCl & 400 mg & & & \\ \hline Teas and herbs (1 & 28 & 30 mL AN-water & 6 g MgCo\({}_{4}\) & 400 mg PSA & HPLC-Q-Orbitrap- & 87–111 & 5 mg/Kg & [25] \\ \(\delta\)) & PAs/PANOs & (?525, \(\eta\)/3) with 0.5\% & 1.5 g CH\({}_{3}\)CONA & 400 mg CCS & MS/MS & & \\  & & formic acid & & 400 mg GCR & ESI positive in mode & & \\  & & formic acid & & 1200 mg MgCo\({}_{4}\) & HRMS mode & & \\  & & & Column: CS at 40 °C & & & \\ \hline \hline \end{tabular}
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