# Current Trends in Fully Automated On-Line Analytical Techniques for Beverage Analysis
## 6 On-Line Fully Automated Extraction-Chromatography-Mass Spectrometry
This methodology demonstrated to be easily operated without solvent use, reliable and efficient in the multi-residue analysis of pesticides. \begin{table}
\begin{tabular}{c c c c c c} \hline \hline
**Matrix** & **Analyte** & **Extraction Method/Device** & **Separation/Detection** & **LOD 1 (\(\upmu\)g/L)** & **Ref.** \\ \hline \multirow{2}{*}{Bottled Water} & \multirow{2}{*}{Tiazzes} & In-tube SPME, packed GO-amino silica particles & UHPLC-ESI-MS/MS & 0.0011–0.0029 & [89] \\ \hline \multirow{2}{*}{Breast milk} & UV-Filters residues & TFC, TransendT\({}^{\upmu}\) TL-X-1, Cyclone & TFC-HPLC-ESI-MS/MS & 0.1–1.5 (\(\upmu\)g/kg) & [86] \\ \hline \multirow{2}{*}{Infant formula} & \multirow{2}{*}{Melamine} & TFC, TransendTLX-2, Cyclone & \multirow{2}{*}{TFC-APCI-LC-MS/MS} & \multirow{2}{*}{27 (\(\upmu\)g/kg)} & \multirow{2}{*}{[90]} \\  & & MCX-2 cation exchanger turboflow\({}^{\upmu}\) column & & & \\ \hline \multirow{2}{*}{Milk} & Sulfonamide antibiotics & SPE, silica-based ionic liquid (IL) & SPE-LC-ESI-TOF-MS & 1.5–2.25 & [91] \\ \hline \multirow{3}{*}{Milk} & Veterinary drugs & TFC, TransendT\({}^{\upmu}\) TLX-1, Turboflow\({}^{\upmu}\) cyclone column (50 \(\times\) 1.0 mm, 60 \(\upmu\)m particle size, 60 Å pore size) & TFC-ESI-LC-MS/MS & 0.2–2.0 (\(\upmu\)g/kg) & [83] \\ \hline \multirow{2}{*}{Milk and dairy products} & \multirow{2}{*}{Affatoxin M1} & SPE, C18 cartridge & UHPLC-ESI-MS/MS & \
\begin{tabular}{} \end{tabular} &
\begin{tabular}{} \end{tabular} \\ \hline \multirow{2}{*}{Skimmed Milk} & \multirow{2}{*}{Antibiotics} & TFC, TransendT\({}^{\upmu}\) TLX-1, Cyclone & UHPLC-ESI-MS/MS & 0.0005–0.0007 & [92] \\ \cline{2-2} \cline{4-4}  & & Pcolumn (50 \(\times\) 0.5 mm, 60 \(\upmu\)m particle size, 60 Å pore size) & & & \\ \hline \multirow{2}{*}{Tea} & Pesticides & HS-SPME, PDMS/DVB fiber & GC-MS/MS & 1–5 (\(\upmu\)g/kg) 2 & [93] \\ \hline \multirow{2}{*}{Whole milk} & Quinolone antibacterial & In-tube SPME, monolithic microcolumn Poly(MAA-co-EGDMA) & LC-ESI-QTOF-MS & 0.2–3.0 & [94] \\ \hline \multirow{2}{*}{Wine} & Ochratoxin A & In-tube SPME, packed C18 particles in a peek tube & UHPLC-ESI-MS/MS & 0.02 & [73] \\ \hline \multirow{2}{*}{Wine, sprits, vinegars} & Ochratoxin A & SPE, Oasis MAX cartridge Phenols & HPLC-ESI-MS/MS & 0.012 & [95] \\ \cline{2-2} \cline{4-4}  & \multirow{2}{*}{Phenols} & SPE, HyperSep\({}^{\upmu}\) Retain PEP cartridge & UHPLC-ESI-Q-Orbitrap & 0.1-5\({}^{2}\) & [96] \\ \hline \end{tabular}  
\({}^{1}\) LOD: Limit of Detection; 2 LOQ: Limit of Quantification.  
\end{table} 
Table 4: Representative applications of on-line extraction—chromatography—tandem mass spectrometry to the analysis of beverages. [PERSON] et al. [96] analyzed 56 phenolic natural compounds presented in wine, spirits and vinegar samples using an on-line SPE-HPLC-Q-Orbitrap system. The coupling of SPE as sample preparation step and the high resolution of Orbitrap-MS analyzer allowed the detection and quantification of phenolic compounds in all matrices with a good LOQs, accuracy and precision. Two approaches were compared to evaluate the matrix effect; with SPE clean-up and direct injection, almost all compounds showed an improved response when the SPE cartridge were used because it reduces the interferents that reach the detector. In a truboflowTM-ESI-LC-MS/MS system, [PERSON] et al. [83] determined 88 veterinary drug residues in milk samples. This methodology demonstrated to be fast (39 min in total) and required a prior sample preparation step to precipitate the proteins by addition of a solvent followed by centrifugation. Then the supernatant was directly injected in the analytical equipment. In comparison to traditional procedures, it was demonstrated to be simple, quick and very sensitive for the analysis VDs, allowing the analysis of routine of milk samples. Another interesting approach is the use of emerged materials in the extraction devices, showing some superior characteristics when compared to conventional materials. [PERSON] et al.