## 4 Glyphosate and AMPA in Foods
### Detection and Quantification
Electrospray ionization (ESI) can be applied in both positive and negative ion modes. A method for quantifying glyphosate and AMPA in agricultural samples using the positive ESI mode has been reported. In multiple reaction monitoring mode (MRM), for glyphosate, a precursor ion of 392 \(m/z\) was reported, with product ions at 179, 88, and 214 \(m/z\), and 392\(\rightarrow\)179 as the quantifier transition. For AMPA, the quantifier transition was 334\(\rightarrow\)179, with 156 and 112 as the qualifier's ions [24]. When using negative ESI mode, the quantifier transition for glyphosate was reported as 390\(\rightarrow\)168, with 150 \(m/z\) as the qualifier [50]. The derivatization approach has been used to analyze glyphosate in food matrices (Table 6). [PERSON] et al. [112] developed a derivatized method using FMOC for detecting GLYP and AMPA from soy-based products by LC-MS/MS by multiple transition monitoring (fluorescence detector) and reported accuracy and intermediate precision (91-106%, RSD <10%) in soy protein isolate, where LOQs were 50 \(\upmu\)g/kg for powders and 5 \(\upmu\)g/kg for liquids. They used fragment ions of 170 and 214 \(m/z\) for GLYP and 112 and 156 \(m/z\) \begin{table}
\begin{tabular}{c c c c c c} \hline \hline
**Food Sample** & **GLYP/AMPA** &
\begin{tabular}{c} **Analytical** \\ **Methodology** \\ \end{tabular} & **Column** & **Derivatization** & **Results** & **Ref.** \\ \hline \multirow{2}{*}{Soy-based products} & \multirow{2}{*}{GLYP/AMPA} & \multirow{2}{*}{LC-MS} & ACQUITY UPLC BEH & \multirow{2}{*}{FMOC} & LOQ was 50 and \\  & & & C18 18 \(\upmu\)m, & & 5 \(\upmu\)g/kg \\  & & & 2.1 \(\times\) 100 mm, column & & \\ \hline \multirow{2}{*}{Com} & \multirow{2}{*}{GLYP} & \multirow{2}{*}{UHPLC-MS/MS} & HSST3 (1.8 \(\upmu\)m, & \multirow{2}{*}{FMOC-CI} & LOQ was \\  & & & 2.1 mm \(\times\) 100 mm) & & 0.005 mg/kg \\  & & & from Waters & & \\ \hline \multirow{2}{*}{Baby formula, bovine liver and kidney} & \multirow{2}{*}{GLYP/AMPA} & \multirow{2}{*}{LC-ESI-MS/MS} & Luna column & \multirow{2}{*}{FMOC-CI} & LOQ: 10-25 \(\upmu\)g/kg \\  & & & (150 \(\times\) 2 mm) with & & \\  & & & bonded 3 \(\upmu\)m C18 & & \\ \hline \multirow{2}{*}{Liver of animal origin} & \multirow{2}{*}{GLYP} & \multirow{2}{*}{UPLC-MS/MS} & ACQUITY UTPLC & \multirow{2}{*}{FMOC-CI} & LOQ and LOQ: \\  & & & BEH C18 (1.7 \(\upmu\)m, & 2.1 \(\times\) 100 mm) & & 0.025 mg/kg \\ \hline \multirow{2}{*}{Oat and rye wheat} & \multirow{2}{*}{GLYP/AMPA} & \multirow{2}{*}{LC-MS/MS} & ACQUITY® BRC1 C18 & \multirow{2}{*}{FMOC-CI} & LOQ and LOQ: \\  & & & column (1.7 \(\upmu\)m & & \\  & & & 2.1 \(\times\) 100 mm) & & \\ \hline \multirow{2}{*}{Honey} & \multirow{2}{*}{GLYP/AMPA} & \multirow{2}{*}{HPLC-FLD} & Amime-Ay potassium & \multirow{2}{*}{OPA-MERC} & LOQ: 10-25 \(\upmu\)g/kg \\  & & & (100 mm \(\times\) 4.6 mm, 5 \(\upmu\)m) & & for both \\ \hline \multirow{2}{*}{Soybean} & \multirow{2}{*}{GLYP/AMPA} & \multirow{2}{*}{HPLC} & ODS column (150, & \multirow{2}{*}{DPCS-CI} & LOQ: 0.002 mg/kg \\  & & & 4.6 mm LD, 5 mm) & & for GLYP and \\ \hline \multirow{2}{*}{DPCS-CI: Fluorescent labeling reagent 3,6-dimethoxy-9-phenyl-9H-carbazole1-sulfonyl chloride.} & \multirow{2}{*}{DPCS-CI} & \multirow{2}{*}{DPCS-CI} & LOQ: 0.002 mg/kg \\  & & & 4.6 mm LD, 5 mm) & & 0.001 mg/kg \\ \hline \hline \end{tabular}
\end{table} 
Table 6: Detection of glyphosate in food using derivatization approach. Figure 3: Reaction mechanism of glyphosate derivatization with FMOC-CI (figure made in Chemdraw software V.2.3.1). for AMPA. [PERSON] et al. [119] established a sensitive method for determining GLYP from corn by UHPLC-MS/MS, using FMOC-Cl as the derivatizing agent, and reported LOQ of 5 \(\upmu\)g/kg with good recovery (90-95%) and RSD of 1.24 to 3.35%. They used product ions of 167.8 and 150.0 \(m/z\). Nonetheless, after purification and derivatization, samples were diluted to reduce matrix effects. On the other hand, it has been reported that excess FMOC reagent may affect the reaction mixture [119].