Review of analytical methods available for measuring PPCPs in water Praveen Kumar Reddy Y *, Amlan Rath, Balakrishna K, Sruthi Balakrishnan, Udayashankar.

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Review of analytical methods available for measuring PPCPs in water Praveen Kumar Reddy Y *, Amlan Rath, Balakrishna K, Sruthi Balakrishnan, Udayashankar HN Department of Civil Engineering, Manipal Institute of Technology, Manipal University, Manipal – * Presence of pharmaceuticals and personal care products (PPCPs) in water and wastewater can pose unknown amount of risk to the health of humans and the aquatic environment. Their detection in the natural environment is made possible by development of chromatography and mass spectrometric techniques like GC-MS, GC-MS/MS, LC-MS, HPLC-MS and LC-MS/MS. The widely adopted procedure is to extract PPCPs by solid phase extraction (SPE) through Oasis® HLB cartridge coupled with LC-MS. SPME (Solid phase micro extraction) and LPME(Liquid phase micro extraction) are used for the smaller volumes of samples. It is evident that there is no single method for the detection and extraction of all category of pharmaceuticals and personal care products. Discussion Conclusion References Andreozzi, R., Raffaele, M., Nicklas, P., Pharmaceuticals in STP effluents and their solar photo degradation in aquatic environment. Chemosphere 50, Fatta, D., Achilleos, A., Nikolaou, A., Meric, S., Analytical methods for tracing pharmaceutical residues in water and wastewater. TrAC Trends in Analytical Chemistry 26, Hao, C., Zhao, X., Yang, P., GC-MS and HPLC-MS analysis of bioactive pharmaceuticals and personal-care products in environmental matrices. TrAC Trends in Analytical Chemistry 26, Hirsch, R., Ternes, T., Haberer, K., Mehlich, A., Ballwanz, F., Kratz, K., Determination of antibiotics in different water compartments via liquid chromatography“ electrospray tandem mass spectrometry. Journal of Chromatography A 815, Huggett, D., Khan, I., Foran, C., Schlenk, D., Determination of beta-adrenergic receptor blocking pharmaceuticals in united states wastewater effluent. Environmental Pollution 121, Trace amounts of PPCPs can pose a serious threat to the human life. There are many advanced analytical methods optimized to quantify pharmaceuticals in water. SPE method with specific sorbents is extensively used technique in terms of speed and in minimizing solvent. There is a need to develop new techniques for the complex environmental matrices and to analyze the metabolites of pharmaceutical compounds. GC-MS and GC MS/MS, LC-MS and LC MS/MS are the standard analytical methods to detect the lower concentrations of PPCPs from μg/l to ng/l. It is concluded from this review that there is no single method available for the detection and extraction of all category of pharmaceuticals and personal care products CTAC Andreozzi et al., 2003 reported the extraction and analysis of acidic and neutral pharmaceuticals by SPE-GC-MS and LC- MS (recoveries>60%) with the exceptions of gemfibrozil (46%), clofibrate (33%) sulfamethoxazole (40%) and ciprofloxacin (34–35%). Huggett et al., 2003 used a method combining SPE (derivatization with MSTFA, N-Methyl-N-(trimethylsilyl)– trifluoro-acetamide) with GC-MS to determine β-blockers in pharmaceutical wastewaters with a successful recovery of > 90%. Investigations by Hirsch et al., 1998 determined various antibiotics in STP effluents and river-water samples using HPLC-MS analysis. Sulfadiazine Sulfadimidine Metronidazole Tylosin Erythromycin Norfloxacin Ofloxacin Trimethoprim HPLC-MS(SPE) Acetylsalicylic acid Gemfibrozil Naproxen Ketoprfen Diclofenac Triclosan Tonalide Cholorobenzene GC-MS²(SPE)LC-MS²(SPE) Clobfibric acid Caffiene Ciproflaxin Trimethroprim Sulfadiazine Procaine Enrofoxacin Diazepam Ibuprofen Caffeine Sulfamethoxazole Paracetmol Fig. 3 Detection methods applied for common pharmaceuticals in water Abstract  Presence of pharmaceuticals in trace levels in different water bodies is a major concern around the world.  The major sources of pharmaceutical pollutants in water are from hospitals, drug industries and household waste.  To find out the transport of PPCPs in the environment, a sensitive and effective analysis is needed. Source: Shore et al. Phil. Trans. R. Soc. B 2014;369:  Sample extraction is an important step in pharmaceutical analysis. SPE (solid phase extraction) is frequently used technique for the extraction process. The sorbents like ENV+, Oasis HLB, Strata-X, Lichrolut C18 and Lichorlut EN has been used for cleanup and preconcentration of pharmaceuticals in waters. (Fatta et al., 2007)  LC-MS/MS technique is being used for the determination of PPCPs especially for the degradable polar molecules. LC-MS system is relies on API and APCI and ESI for different kinds of samples, whereas GC- MS with tandem MS/MRM provides additional selectivity and sensitivity. (Hao et al., 2007) Fig.1 Pathways of pharmaceutical releases to freshwaters. Fig. 2 Schematic view of sample preparation and analysis Introduction Review of experimental methods