## 4 Applications of Microextraction Techniques to the Determination of Organic Micropolultants
### Pharmaceuticals
\begin{table}
\begin{tabular}{p{142.3 pt} p{142.3 pt} p{142.3 pt} p{142.3 pt} p{142.3 pt} p{142.3 pt} p{142.3 pt} p{142.3 pt}} \hline \hline
**Compounds** & **Matrix** & \begin{tabular}{c} **Extraction** \\ **Technique** \\ \end{tabular} & **Optimal Times** & **Handing** & \begin{tabular}{c} **Recovery** \\ **Accuracy (\%)** \\ \end{tabular} & **LOD** & **Ref.** \\ \hline Pharmaceuticals (paracetamol, caffeine, antityping, propranolol hydrochloride, pridion methanesulfonate, carbamazepine, diclofenac) & Wastewater & SBSE & \begin{tabular}{c} Extraction: 60 min \\ Desorption 10 min \\ \end{tabular} & \
\begin{tabular}{c} Better than \\ commercial coatings \\ \end{tabular} & 1-50 & 15-50 & [96] \\ \hline Sutin drugs (atorvastatinatin, finvastatin, lavasatin, pavasatinatin, finvastatin, invastatin, invvastatin) & Pure water, wastewater and river water & DLLME &
\begin{tabular}{c} Centrifugation: \\ 10 min (two times) \\ \end{tabular} & Faster & 13–92 & 0.09–17.0 & [97] \\ \hline Arrihisto residue (erythromycin, spizamycin, ilmicos, sulfthiazol, sulfamethazine, sulfamethazine, coysterracycline, citepfloxacin) & & & & 0-38 & 0.08 & [97] \\ \hline \hline \end{tabular}
\end{table} 
Table 3: _Cont._[PERSON] [99] used DLLME with LC-MS detection to extract anti-inflammatory pharmaceuticals from environmental samples. Chloroform was the extractant, and acetone was the dispersant. Under the optimised conditions, a two-step extraction with sonication was used; the LOQs ranged from 0.5 to 10 \(\mathrm{ng\cdot L}^{-1}\). [PERSON] and [PERSON] [100] developed a similar microextraction technique using ethanol as the dispersant and trichloroethylene as the extractant for the determination of clotrimazole in river water and wastewater effluent samples from wastewater treatment plants. The LOQ was approximately 0.7 \(\mathrm{ng\cdot L}^{-1}\). Hollow fibre-protected liquid-phase microextraction (HF-LPME) was used by different researchers. [PERSON] _et al._[101] used a hollow fibre liquid-phase microextraction (Accurel Q3/2 polypropylene tubular membranes) to extract/enrich acidic drugs from wastewater samples. After optimising the LPME method, very clean extracts could be obtained, avoiding signal suppression during the LC-MS/MS analysis of the analytes; the limits of quantification ranged from 0.5 to 42 \(\mathrm{ng\cdot L}^{-1}\). Additionally, [PERSON] _et al._[102] developed a similar technique able to accommodate large-sample-volume extractions in a single step for extracting antidepressant drugs from environmental waters. Compared to studies with small sample volumes, the closure of the hollow fibre and the type of liquid membrane were critical for large-volume extractions. Finally, [PERSON] _et al._[103] used HF-LPME with UHPLC-MS/MS to determine 11 antibiotics in river water samples. The parameters were optimised to provide LODs from 10 to 250 \(\mathrm{ng\cdot L}^{-1}\). Good recoveries (79.2%-118%) were obtained using this technique, except in the study conducted by [PERSON] _et al._[102]. However, the authors obtained better enrichment factors by using large sample volumes, obtaining LODs in the range of \(\mathrm{pg\cdot L}^{-1}\).