Trace cisplatin adsorption by thiol-functionalized sponge (TFS) and Sn/SnO2-coated TFS: Adsorption study and mechanism investigation.

To remove trace cisplatin from aqueous solution, commercial sponges were functionalized by esterification with 3-mercaptopropionic acid, followed by reduction with Na2S·9H2O or SnCl2·2H2O. The resulting thiol-functionalized sponges (TFSs), TFS_1 and TFS_2, were tested for the removal of cisplatin (235 µg L-1) achieving maximum removal of 95.5 ± 0.8% and 99.5 ± 0.1% respectively, which were significantly higher than the non-functionalized counterpart. The successful grafting of thiol groups, verified through FTIR, elemental analysis, SEM-EDS, and XPS characterization, facilitated Pt-S complexation during adsorption. The aqua-derivatives of cisplatin, formed through hydration, complexed with thiol sites through ligand displacement. Additionally, the presence of Sn/SnO2 coating on TFS_2 further enhanced the adsorption process. The rapid adsorption process conformed to pseudo-second-order kinetic model, involving both diffusion and chemisorption. While the Langmuir isotherm model generally described the monolayer adsorption behavior of cisplatin, the aggregation of Sn/SnO2 onto TFS_2 at 343 K introduced surface heterogeneity, rendering the Freundlich model a better fit for the adsorption isotherm. Differential pH dependence and the evaluation of mean free energy, derived from the Dubinin-Radushkevich isotherm model, indicated that cisplatin adsorption onto TFS_1 involved physisorption, including electrostatic attraction, while chemisorption predominated for TFS_2. Increasing the temperature notably promoted adsorption by facilitating the thermal-favored formation of Pt-S bonds.

Assessment of sediment pollution by metals. A case study from Cienfuegos Bay, Cuba.

Sediments were grouped in three zones of the bay: two in the northern basin with higher metal contamination; and another in the southern basin, where lithogenic metals were predominant. Sediment pollution classification made using Index of geoaccumulation and Enrichment factor was consistent, indicating higher accumulation of Cd and Pb in the northern basin. The negative influence of activities linked to petrol was predicted by V/Ni and V/(Ni+V) ratios. Cd and Pb did not represent a potential risk; while Cu and Ni could be risky for biota in most sediment, according to Screening Quick Reference Tables (SQuiRTs). Comparison of bioavailable fraction of metals with references in SQuiRTs corroborated the low potential damage on the biota due to As, Cd, Pb, Cr, Zn; and a higher potential damage due to Cu; while an attenuation of the risk due to Ni predicted by SQuiRTs could be expected.

Combining contamination indexes, sediment quality guidelines and multivariate data analysis for metal pollution assessment in marine sediments of Cienfuegos Bay, Cuba.

The purpose of the present work was to combine several tools for assessing metal pollution in marine sediments from Cienfuegos Bay. Fourteen surface sediments collected in 2013 were evaluated. Concentrations of As, Cu, Ni, Zn and V decreased respect to those previous reported. The metal contamination was spatially distributed in the north and south parts of the bay. According to the contamination factor (CF) enrichment factor (EF) and index of geoaccumulation (Igeo), Cd and Cu were classified in that order as the most contaminated elements in most sediment. Comparison of the total metal concentrations with the threshold (TELs) and probable (PELs) effect levels in sediment quality guidelines suggested a more worrisome situation for Cu, of which concentrations were occasional associated with adverse biological effects in thirteen sediments, followed by Ni in nine sediments; while adverse effects were rarely associated with Cd. Probably, Cu could be considered as the most dangerous in the whole bay because it was classified in the high contamination levels by all indexes and, simultaneously, associated to occasional adverse effects in most samples. Despite the bioavailability was partially evaluated with the HCl method, the low extraction of Ni (<3% in all samples) and Cu (<55%, except sample 3) and the relative high extraction of Cd (50% or more, except sample 14) could be considered as an attenuating (Ni and Cu) or increasing (Cd) factor in the risk assessment of those element.

Revisiting methods for the determination of bioavailable metals in coastal sediments.

A simple methodology for the determination of bioavailability of fourteen metals in coastal sediments has been developed by simulating the conditions of digestive process of marine fishes. With this aim, a representative sediment composite sample was treated with hydrochloric acid solutions at different pH values, temperatures and contact times, in the presence and absence of Pepsin and Trypsin. The addition of Pepsin and Trypsin did not affect the extraction of most elements. As a result of the present study, the digestion with a hydrochloric acid solution at pH 1, 40°C and 12h is proposed. Adjustments of the temperature and time reaction could be made according to the specific ecosystem under study. The amount of metal extracted by other methods based on acetic acid was lower than that extracted by HCl treatment proposed.

Comparative study of digestion methods EPA 3050B (HNO3--H2O2--HCl) and ISO 11466.3 (aqua regia) for Cu, Ni and Pb contamination assessment in marine sediments.

Knowing the metal extraction capacity of a digestion method is crucial for a better environmental interpretation of metal concentrations determined in sediments. One of the main problems at the present is the lack of harmonization of information obtained by two of the most popular sediment partial digestion methods: ISO 11466.3 (aqua regia) and EPA 3050B (HNO3--H2O2--HCl). In the present work, the amount of Cu, Ni and Pb leached by using both methods was compared with the total content of those elements in marine sediments collected, as an example, from the Cienfuegos Bay, Cuba. Similar amounts of Cu were extracted by both methods; while leaching of Ni and Pb were different. Generally, the EPA method extracted more Ni than the ISO method. In contrast, Pb was extracted in a larger amount by the ISO method. Some explanations are given for the observed results. X-ray Diffraction, X-ray Fluorescence, Particle Induced X-ray Emission Spectrometry and Energy Dispersive X-ray coupled to Scanning Electron Microscopy were employed for this purpose. On the other hand, none of the methods studied extracted simultaneously the fraction of all the metals, probably provided by human activity (Theoretical Anthropogenic Fraction) in both sediments studied. The use of ISO 11466.3 or EPA 3050B is recommended since the analytical performance parameters of both, in combination with Flame Atomic Absorption Spectrometry, are adequate. For a better environmental interpretation of the analytical results, information on the extraction efficiency of the selected method for specific elements and sediments under study should also be provided, together with the determined concentrations.