A Polydimethylsiloxane Rod Extraction-Based Method for the Determination of Pharmaceuticals and Triclosan by Liquid Chromatography in Water Samples.

A new analytical method for the determination of naproxen, ketoprofen, diclofenac, carbamazepine, and triclosan (TCS) in water samples by liquid chromatography is developed and validated. The method is based on the extraction of the analytes by a polydimethylsiloxane (PDMS) rod. The different parameters affecting extraction, such as the addition of salt, pH, initial volume, extraction and elution times and elution solvent, as well as the application of sonication, are studied. The results showed that the detection limits are all in the 0.1-0.3 µg L-1 range except for carbamazepine (6 µg L-1) with relative standard deviations in the range of 0.4%-9.7%. The method developed, which was validated by analysing spiked surface water samples at 10, 25 and 75 µg L-1 gave recoveries of between 84.8% and 111.2%. In the case of carbamazepine, a recovery of 99.1% was obtained at 75 µg L-1. The main advantage of the developed method is that allows high performance liquid chromatography-diode array detection, which is widely available in non-specialised laboratories, to be applied for pharmaceuticals and TCS determination in surface waters after performing a preconcentration/clean-up step with PDMS rods as it has been shown by analysing real water samples.

Granulated cork as biosorbent for the removal of phenol derivatives and emerging contaminants.

This study evaluated the ability of cork to adsorb a broad range of phenolic, pharmaceutical and cosmetic compounds: phenol, 2-chlorophenol, 2-nitrophenol, 2,4-dichlorophenol, pentachlorophenol carbamazepine, naproxen, ketoprofen, diclofenac, triclosan, and methyl paraben. The effect of variables such as the compound concentrations and the amount of cork were studied resulting in a highly pH dependence in the case of phenolic compounds. Maximum removal percentages and uptake values of 75% (1.61 mg/g) for 2,4-dichlorophenol, 55% (1.25 mg/g) for 2-nitrophenol, 45% (1.47 mg/g) for 2-chlorophenol, 20% (0.63 mg/g) for phenol, and 100% for pentachlorophenol, were obtained for a 30 mg L-1 solution at pH 6, showing that the adsorption process increased with greater electronegativity of the phenolic substituting group. Removal percentages and uptakes of 82% (3.56 mg/g) for naproxen, 57% (2.31 mg/g) for ketoprofen, 50% (1.84 mg/g) for carbamazepine, 50% (1.78 mg/g) for methyl paraben, 100% for sodium diclofenac, and 100% for triclosan, were obtained using 5 mg of cork and a 1 mg L-1 solution of each compound. The adsorption process was almost complete after 30 min for all the micropollutants. Experimental equilibrium data were analysed by Freundlich and Langmuir adsorption models. Cork has proved to be an effective sorbent for the removal of phenols and emerging contaminants from contaminated waters and is a readily available material that can be acquired at minimal or no cost in cork-producing areas.