Advanced oxidation and a metrological strategy based on CLC-MS for the removal of pharmaceuticals from pore & surface water.

In this work, it is studied the photolysis, electrolysis, and photo-electrolysis of a mixture of pharmaceutics (sulfadiazine, naproxen, diclofenac, ketoprofen and ibuprofen) contained in two very different types of real water matrices (obtained from surface and porewater reservoirs), trying to clarify the role of the matrix on the degradation of the pollutants. To do this, a new metrological approach was also developed for screening of pharmaceuticals in waters by capillary liquid chromatography mass spectrometry (CLC-MS). This allows the detection at concentrations lower than 10 ng mL-1. Results obtained in the degradation tests demonstrate that inorganic composition of the water matrix directly influences on the efficiency of the drugs removal by the different EAOPs and better degradation results were obtained for experiments carried out with surface water. The most recalcitrant drug studied was ibuprofen for all processes evaluated, while diclofenac and ketoprofen were found to be the easiest drugs for being degraded. Photo-electrolysis was found to be more efficient than photolysis and electrolysis, and the increase in the current density was found to attain a slight improvement in the removal although with an associated huge increase in the energy consumption. The main reaction pathways for each drug and technology were also proposed.

Rapid determination of malondialdehyde in serum samples using a porphyrin-functionalized magnetic graphene oxide electrochemical sensor.

An electrochemical sensor based on a screen-printed carbon electrode (SPCE) modified with porphyrin-functionalized magnetic graphene oxide (TCPP-MGO) was developed for the sensitive and selective determination of malondialdehyde (MDA), an important biomarker of oxidative damage, in serum samples. The coupling of TCPP with MGO allows the exploitation of the magnetic properties of the material for separation, preconcentration, and manipulation of analyte, which is selectively captured onto the TCPP-MGO surface. The electron-transfer capability in the SPCE was improved through derivatization of MDA with diaminonaphthalene (DAN) (MDA-DAN). TCPP-MGO-SPCEs have been employed to monitor the differential pulse voltammetry (DVP) levels of the whole material, which is related to the amount of the captured analyte. Under optimum conditions, the nanocomposite-based sensing system has proved to be suitable for the monitoring of MDA, presenting a wide linear range (0.01-100 µM) with a correlation coefficient of 0.9996. The practical limit of quantification (P-LOQ) of the analyte was 0.010 µM, and the relative standard deviation (RSD) was 6.87% for 30 µM MDA concentration. Finally, the developed electrochemical sensor has demonstrated to be adequate for bioanalytical applications, presenting an excellent analytical performance for the routine monitoring of MDA in serum samples.

Ionic liquid and magnetic multiwalled carbon nanotubes for extraction of N-methylcarbamate pesticides from water samples prior their determination by capillary electrophoresis.

A simple and rapid microextraction procedure is reported on the use of ionic liquid (IL) in combination with magnetic multiwalled carbon nanotubes (MMWCNTs). The procedure is based on temperature-controlled IL dispersive liquid phase microextraction (DLPME) and MMWCNTs, for selective preconcentration of N-methylcarbamate pesticides in water samples, followed by their hydrolysis in alkaline buffer, prior to being analyzed by capillary electrophoresis. The extraction procedure uses small volume of organic solvents, and there is no need for centrifugation. In the experimental approach the IL was quickly disrupted by an ultrasonic probe, heated with the temperature controlled at 90 °C and dispersed in water samples in a homogenous form. At this stage, N-methylcarbamate pesticides migrate into the IL. Then the solution was cooled and small amounts of MMWCNTs were dispersed into the sample solutions to adsorb the ionic liquid containing the analytes and phase separation was completed. The ionic liquid allowed the microextraction of the analytes and a small volume of dichloromethane (DCM) was used for elution. MMWCNTs favored the adsorption of the ionic liquid with the analytes and improved the final recovery with respect to the use of simple magnetic nanoparticles as a sorbent material. Under the optimum conditions, limit of quantifications (LOQ) were achieved in the 5.6-9.3 ng mL-1 range, with recoveries between 85.0% and 102.4%.