Determination And Photodegradation Drugs And Personal Care Products In Drinking Water And Beverage

The presence of pharmaceuticals in the environment is a very important problem that requires analytical solutions. The low pharmaceuticals levels in the environmental samples require high sensitive and selective analytical procedures, and effective methods to degrade them into non-toxic small molecule compounds. In this paper, the hollow fiber membrane liquid phase microextraction (HF-LPME) technology followed by liquid chromatography-mass spectrometry (LC MS) technology is established, and through the visible light degradation technique, we study drugs and personal care products in drinking water as follows:1. A two-phase HF-LPME coupling with UPLC-MS/MS method was developed for determination of four non-steroidal anti-inflammatory drugs (NSAIDs)-salicylic acid, ibuprofen, naproxen and diclofenac in real water samples. The influencing parameters of HF-LPME sample preparation method, such as organic solvents (acceptor phase), pH of sample solution (donor phase), extraction time, stirring speed, extraction temperature and ionic strength were systematically optimized. Through the developed determination method, high enrichment factors (195to346) were achieved for the four drugs. The instrumental calibration curves of salicylic acid, naproxen, diclofenac, ibuprofen show good linear relations (R>0.998) in the concentration range of1-500,5-2500,10-5000and5-2500μg·L-1, respectively. Limits of detection (LOD) of salicylic acid, naproxen, diclofenac, ibuprofen in water were0.5,0.5,1.0,1.25μg·L-1, respectively. The determination method has been applied for the real samples (purified water, tap water, juice, soda and energy drinks).2. Photocatalytic degradation of four non-steroidal anti-inflammatory drugs (NSAIDs)-salicylic acid, ibuprofen, naproxen and diclofenac in water has been investigated using a novel P25-TiO2/tetraethyl orthosilicate (TEOS) film on glazed ceramic surface under a visible light incubator. Influences of main parameters, such as adsorption, stir, initial pH, amount of P25-TiO2/TEOS and irradiation time has been studied. Results show that the degradations of four NSAIDs obtained maximum and equilibrium effect within10h of irradiation at pH6.0condition. The maximum degradation effects of salicylic acid, ibuprofen, naproxen and diclofenac under optimum conditions are76%,85%,94%and65%, respectively. The photocatalytic degradation reactions follow first order kinetics.Naproxen is selected as the representative to analyze the photocatalytic products, and a probable photocatalytic degradation pathway of naproxen is put forward. To support the degradation kinetics study a rapid, sensitive and accurate UPLC-MS/MS method has been developed.3. Establish a two-phase CNTs-HF-LPME and UPLC-MS/MS technology combined detection of water indomethacin, naphthalene nabumetone, sulindac and etodolac analytical methods. Optimize the hollow fiber liquid phase microextraction conditions:extraction reagents, given phase pH, extraction temperature, extraction time, speed, etc., to obtain the optimum extraction conditions. Indomethacin, nabumetone, sulindac, and etodolac have good linear relationship (R>0.997) at5-2500,1-500,5-2500and5-2500μg·L-1, respectively. The recoveries of four drugs at three levels are between59%-116%. Detection limits of indomethacin, nabumetone, sulindac and etodolac are1.00,0.50,2.50and5.00μg·L"’, respectively. The real samples (tap water, yuandadu park water, forest park water) were tested.4. A ultra-high performance liquid chromatography system coupled with triple quadruple tandem mass spectrometry (UPLC-MS/MS) procedure for the qualitative and quantitative detection of y-hydroxybutyrate (GHB), y-butyrolactone (GBL), and1,4-butanediol (1,4-BD) in beverage was established. After filtered with0.22μm PES filters, compounds were separated in3minutes by Waters Atlantis T3 column (2.1x150mm,3.0μm; Waters, Milford, MA, USA) with gradient elution using water (A) and methanol (B) at the flow rate of0.25mL·min-1. Samples were monitored via the ES1+ionization method and quantified by multiple reaction monitoring (MRM). The calibrations were performed and good linear relationship (R>0.99) was observed within the concentration range of0.1-5.0mg·mL-1in GHB and0.5-10.0mg·mL-1in GBL and1,4-BD. The limits of detection were20-50μg·L-1and limits of quantity were50-200μg·L-1. The relative standard deviations (RSD) of between-day and within-day were less than9.51%in UPLC/MS/MS. This method is simple, rapid and has high sensitivity which can be applied to qualitative and quantitative detection of illegally added GHB and related substances in beverages.