As olive leaves constitute the main by-product of the olive oil industry with important environmental and economic impact, there is an increasing demand for its valorization. In the present work, we report the development and application of immobilized enzyme batch bioreactors for the chemo-enzymatic treatment of an aqueous Olea europaea leaf extract rich in oleuropein to produce an extract enriched in hydroxytyrosol and other oleuropein hydrolysis products. To this end, a robust biocatalyst was developed through the immobilization of β-glucosidase on chitosan-coated magnetic beads which exhibited high hydrolytic stability after 240 h of incubation at 37 °C. The biocatalyst was successfully used in both a rotating bed-reactor and a stir-tank reactor for the modification of the olive leaf extract leading to high conversion yields of oleuropein (exceeding 90%), while an up to 2.5 times enrichment in hydroxytyrosol was achieved. Over 20 phenolic compounds (from different classes of phytochemicals such as flavonoids, secoiridoids, and their derivatives) were identified, in the extract before and after its modification through various chromatographic and spectroscopic techniques. Finally, the biological activity of both extracts was evaluated. Compared to the non-modified extract, the modified one demonstrated 20% higher antioxidant activity, seven-fold higher antibacterial activity, and enhanced cytotoxicity against leiomyosarcoma cells.

Atmospheric pollution is one of the main concerns in modern society and it poses a direct impact on the environment and public health. Therefore, an enormous number of environmental samples are collected and analyzed around the world on a daily basis. In order to obtain reliable and comparable results, it is paramount to establish a well-defined protocol for environmental sampling and analysis considering the more relevant variations associated with these activities and the processes that affect the distribution of the analytes in the environment. The present case study proposes a protocol to determine the amounts of the platinum group elements (PGEs: palladium, platinum, rhodium) due to atmospheric deposition in Tibouchina granulosa leaves that takes into account the estimation of measurement uncertainties including the sampling component. The samples were collected at a standardized height, in the second node of the branches, with approximately 2 months of environmental exposure. The particulate matter was extracted from the leaf surface by acid leaching using an ultrasonic bath followed by aqua regia digestion. Platinum (Pt), palladium (Pd), and rhodium (Rh) were separated from impurities by cation chromatography and analyzed by ICP-MS. The measurement uncertainties found were in the range of 24 to 33% while the analytical uncertainty lied between 4.5 and 7.3%. The results were expressed regarding metrological aspects, with the expanded uncertainty, within a 95% confidence level, to allow for a more robust interpretation of their relevance in the environmental and regulatory context.

This work shows that ZrO₂, used as a modifier of TiO₂, can be highly effective as a co-catalyst in the photoelectrocatalytic degradation of dibutyl phthalate (DBP). The monoclinic phase of ZrO₂ was easily obtained by chemical deposition on TiO₂ nanotubes (Ebg ~3.06 eV), increasing the occurrence of hydroxyl groups and acidity on the surface of the material, as observed by electrophoretic mobility measurements. The optimized photoelectrocatalysis conditions were bias potential of 1.5 V, 0.1 M Na₂SO₄ (initial pH 6) supporting electrolyte, 6 ppm of DBP, and UV/Vis irradiation. These conditions resulted in complete removal of DBP, down to the limit of detection of the chromatographic method used, with up to complete TOC removal after 60 min of treatment. The effects of pH, bias potential, DBP concentration, and applied potential were investigated. The method was compared with photocatalysis and photolysis. An oxidation mechanism is proposed, based on intermediates detected by LC-MS/MS during 10 min of photoelectrocatalysis.

Carbamazepine (CBZ) is one of the most widely used antiepileptic drugs in Malaysia. It was detected frequently in wastewater. The electrochemical treatment process has been applied for the degradation of CBZ using graphite–PVC as an anode under these conditions: 0.5 g sodium chloride (NaCl)) as supporting electrolyte, 5 V and 0–60 min electrolysis time in 100 mL of solution. However, 10,11-dihydro10-hydroxy carbamazepine (HDX-CBZ) and 10,11-epoxycarbamazepine (EPX-CBZ) as the main by-product have been analysed and quantified using liquid chromatography–time of flight/mass spectrometry (LC-TOF/MS). Both by-products were analysed in positive ionization mode, and they were separated on a chromatographic C18 column (5 μm, 2 mm × 150 mm) at a flow rate of 0.3 mL/min. Solid-phase extraction (SPE) was applied as a pre-concentration step for the enhancement of the sensitivity and detectability for both HDX-CBZ and EPX-CBZ by-products. Methanol (MeOH) has been selected as the best elution solvent for both by-products compared to methyl tertiary butyl ether (MTBE) and acetone (AC). However, the recovery was 85% and 92% for HDX-CBZ and EPX-CBZ by-products, respectively. The limit of quantification (LOQ) was 0.588 and 0.109 µg/L for HDX-CBZ and EPX-CBZ by-products, respectively. After 20 min of electrolysis time, both by-products HDX-CBZ and EPX-CBZ appeared at maximum concentrations of 343 and 144 μg/L then they were decreased to 17.2 and 9.8 μg/L, respectively, after 40 min. At the end of electrochemical treatment, both by-products were completely eliminated after 60 min.

The expansion of agricultural activities causes habitat loss and fragmentation and the pollution of natural ecosystems through the intense use of pesticides, which may affect the populations of amphibian anurans that inhabit agricultural areas. The present study evaluated the in situ bioaccumulation of pesticides in a population of Leptodactylus luctator that occupies farmland in southern Brazil. We also compared the genotoxicity of L. luctator populations from farmland and forested areas in the same region. We analyzed the micronuclei and nuclear abnormalities of 34 adult anurans, 19 from farmland, and 15 from the forested area. We also assessed the presence of 32 pesticides in liver samples obtained from 18 farmland-dwelling anurans, using chromatographic analysis. We recorded significantly higher rates of nuclear abnormalities in the individuals from the farmland, in comparison with the forest. We detected nine pesticides in the liver samples, of which, deltamethrin was the most common and carbosulfan was recorded at the highest concentrations. The bioaccumulation of pesticides and the higher levels of genotoxic damage found in the anurans from agricultural areas, as observed in the present study, represent a major potential problem for the conservation of these vertebrates, including the decline of their populations and the extinction of species.