Multiclass Analysis for the Determination of Pharmaceuticals and Their Main Metabolites in Leafy and Root Vegetables.

The irrigation of soils with reclaimed contaminated wastewater or its amendment with sewage sludge contributes to the uptake of pharmaceuticals by vegetables growing in the soil. A multiresidue method has been devised to determine five pharmaceuticals and nine of their main metabolites in leafy and root vegetables. The method employs ultrasound-assisted extraction, clean-up via dispersive solid-phase extraction, and analysis through liquid chromatography-tandem mass spectrometry. Box-Behnken design was used to refine variables such as extraction solvent volume, time of extraction, number of extraction cycles, and the type and amount of d-SPE sorbent. The method achieved linearity (R2) greater than 0.994, precision (relative standard deviation) under 16% for most compounds, and detection limits ranging from 0.007 to 2.25 ng g-1 dry weight. This method was applied to a leafy vegetable (lettuce) and to a root vegetable (carrot) sourced from a local market. Parent compounds were detected at higher concentrations than their metabolites, with the exception of carbamazepine-10,11-epoxide.

Comparison of Different Techniques for the Determination of Platinized Cytostatic Drugs in Urine Samples.

Platinum-based cytostatic drugs are one of the most widely used cancer treatments. They are excreted via the urinary tract and can reach the environment through wastewater, posing a risk to human health due to their side effects. Four identification and quantification techniques, including liquid chromatography (LC) separation coupled to (i) a diode array ultraviolet (UV(DAD)) (ii), mass spectrometer in single ion monitoring mode (LC-MS) and (iii) multiple reaction monitoring mode (LC-MS/MS) and (iv) derivatization with diethyldithiocarbamate prior to LC-MS/MS analysis, have been optimized and compared for the multiresidue determination of main platinized cytostatic drugs (cisplatin, carboplatin, and oxaliplatin) in urine samples. Parameters that affect the efficiency of the chromatographic separation and analytical determination of different methods (column, mobile phase, wavelength, precursor ions, fragmentor, and product ions) were optimized. Analytical features, such as matrix effect, sensitivity, precision, selectivity, and linearity, were calculated. In terms of selectivity, the derivatization technique was discarded since it was only applicable to the platinated sum. A high dilution of the sample with LC-UV(DAD) was needed to reduce the matrix effect. Overall, the LC-MS/MS method presented the best analytical features (% RSD ≤ 12.8%, R2 ≥ 0.991, or method-detection limits between 0.01-1 µg mL-1). The selected method was applied to the quantification of platinized cytostatic drugs in hospital urine samples from oncologic patients.

Enantioselective LC-MS/MS determination of antidepressants, ß-blockers and metabolites in agricultural soil, compost and digested sewage sludge.

In this work, an analytical method was optimised and validated for the simultaneous extraction and enantioselective determination of chiral ß-blockers, antidepressants and two of their metabolites in agricultural soils, compost and digested sludge. Sample treatment was based on ultrasound-assisted extraction and extract clean-up by dispersive solid-phase extraction. Analytical determination was carried out by liquid chromatography-tandem mass spectrometry using a chiral column. Enantiomeric resolutions were in the range from 0.71 to 1.36. Accuracy was in the range from 85 to 127% and precision, expressed as relative standard deviation, was lower than 17% for all the compounds. Method quantification limits were below 1.21-52.9 ng g-1 dry weight (dw) in soil, 0.76-35.8 ng g-1 dw in compost and 13.6-90.3 ng g-1 dw in digested sludge. Application to real samples revealed enantiomeric enrichment in the range especially in compost and digested sludge (enantiomeric fractions up to 1).

Adsorption of Fluoroquinolone Antibiotics from Water and Wastewater by Colemanite.

Pharmaceutical residues in water and wastewater have become a worldwide problem with environmental and public health consequences. Antibiotics are of special importance because of the emergence of antibiotic-resistant genes. This study evaluates the adsorptive removal of four common fluoroquinolone antibiotics by using natural colemanite as an alternative adsorbent for the first time. Batch adsorption experiments were conducted for the mixture of fluoroquinolones as well as for individual compounds during the isotherm studies. Adsorption kinetic results indicated that the process followed the pseudo-second-order (PSO) model, while the Langmuir model described the sorption isotherms. The effects of pH and temperature on adsorption performance were determined, and the results indicated that the adsorption was endothermic and spontaneous, with increasing randomness at the solid-liquid interface. The effects of real water and wastewater matrices were tested by using tap water, surface water, and wastewater samples. Reusability experiments based on five adsorption-desorption cycles indicated that the adsorption performance was mostly retained after five cycles. The adsorption mechanism was elucidated based the material characterization before and after adsorption. The results indicate that colemanite can be used as an effective and reusable adsorbent for fluoroquinolone antibiotics as well as for other pollutants with similar physicochemical properties.

Green Assessment of Analytical Procedures for the Determination of Pharmaceuticals in Sewage Sludge and Soil.

The main difficulties when analyzing pharmaceutically active compounds (PhACs) in solid environmental samples is the complexity of the samples and the low concentration levels of such pollutants. Most efforts are focused in achieving good analytical performance parameters such as high recoveries or low detection limits without considering if the methods are environmentally friendly. In this work, the main tools proposed for assessing the greenness of analytical methodologies (Analytical Eco-scale, Green Analytical Procedure Index (GAPI), and Analytical GREEnness metric (AGREE)) have been applied to nine analytical procedures that include recent important analytical tendencies. The three metrics identified the paper spray ionization method as the greenest procedure since it used untreated samples for direct mass spectrometry analysis. Using Analytical Eco-scale, most of the evaluated procedures were rated as "acceptable green". However, the use of internal standards resulted key in the environmental impact of the method which provided contradictory results versus other metrics. GAPI found greenness similarities between most of selected methods, hindering a greenness classification. AGREE allowed the weighting of each evaluation criterion providing a greenness ranking. The application of each metric detecting their weaknesses and strengths was discussed. The incorporation of validation analytical features in greenness metrics was a gap revealed.

Alginate/geopolymer hybrid beads as an innovative adsorbent applied to the removal of 5-fluorouracil from contaminated environmental water.

Water contaminated by cytostatic drugs has many negative impacts on the ecosystems. In this work, cross-linked adsorbent beads based on alginate and a geopolymer (prepared from an illito-kaolinitic clay) were developed for a promising decontamination of the 5-fluorouracil (5-FU) cytostatic drug from water samples. The characterization of the prepared geopolymer and its hybrid derivative was performed by scanning electron microscopy, X-ray diffraction, Fourier transform infrared and termogravimetric analysis. Batch adsorption experiments indicated that alginate/geopolymer hybrid beads (AGHB) allow an excellent 5-FU removal efficiency of up to 80% for a dosage adsorbent/water of 0.002 g/mL and a concentration of 5-FU of 2.5 mg/L. The adsorption isotherms data follow well the Langmuir model. The kinetics data favor the pseudo-second-order model. The maximum adsorption capacity (qmax) was 6.2 mg/g. The optimal adsorption pH was 4. Besides pore filling sorption process, the carboxyl and hydroxyl groups from alginate immobilized onto the geopolymer matrix favored the retention of 5-FU ions by hydrogen bonds. Common competitors, such as dissolved organic matter, do not significantly affected the adsorption. In addition, this material has not only eco-friendly and cost-effective advantages but also excellent efficiency when applied to real environmental samples such as wastewater and surface water. This fact suggests that it could have a great application in the purification of contaminated water.