Current environmental policies aim to reduce the levels of toxic substances in aquatic ecosystems and to promote the water reuse after appropriate treatment of wastewater.Chromium is a hazard element present in effluents of various industries that should be reduced to achieve the objectives of those policies. Most of the results reported in the literature concern the use of nanomaterials for chromium sorption dissolved either in synthetic or mono-elemental spiked solutions. The present work reviews the results of research undertaken in the last decade on the application of various nanomaterials to decrease chromium concentrations in contaminated waters. Major factors influencing the removal efficiency were examined. Because most of the published studies are based on simple experiments with deionised water and mono contamination further studies are suggested focused on effects of natural and artificial chelators, interferences of other trace elements competing with chromium sorption, reduction the sorbent mass per water volume.
In the last decade different approaches have been applied for water remediation purposes, including the use of nanoparticles(NPs) to remove metals and metalloids from water. Although studies have been done on the toxic impacts of such NPs, very scarce information is available on the impacts of water after decontamination when discharged into aquatic environments. In this way, the present study we aimed to evaluate the ecotoxicological safety of seawater previously contaminated with arsenic (As) and remediated by using manganese-ferrite (MnFe2O4) nanoparticles (NPs). For this, mussels Mytilus galloprovincialis were exposed for 28 days to different conditions, including clean seawater (control), As (1000 µg L-1) contaminated and remediated (As 70 µg L-1) seawater, water containing manganese-ferrite (MnFe2O4) nanoparticles (NPs) (50 mg L-1) with and with the presence of As. At the end of exposure, concentrations of As in mussels tissues were quantified and biomarkers related to mussels' metabolism and oxidative stress status were evaluated. Results revealed that mussels exposed to water contaminated with As and to As+NPs accumulated significantly more As (between 62% to 76% more) than those exposed to remediated seawater. Regarding biomarkers, our findings demonstrated that in comparison to remediated seawater (conditions a, b, c) mussels exposed to contaminated seawater (conditions A, B, C) presented significantly lower metabolic activity, lower expenditure of energy reserves, activation of antioxidant and biotransformation defences, higher lipids and protein damages and greater AChE inhibition. Furthermore, organisms exposed to As, NPs or As+NPs revealed similar biochemical effects, both before and after water decontamination. In conclusion, the present study suggests that seawater previously contaminated with As and remediated by manganese-ferrite (MnFe2O4) NPs presented significantly lower toxicity than As contaminated water, evidencing the potential use of these NPs to remediate seawater contaminated with As and its safety towards marine systems after discharges to these environments.
Humans are typically exposed to environmental contaminants’ mixtures that result in different toxicity than exposure to the individual counterparts. Yet, the toxicology of chemical mixtures has been overlooked. This work aims at assessing and comparing viability and cell cycle of A549 cells after exposure to single and binary mixtures of: titanium dioxide nanoparticles (TiO2NP) 0.75–75 mg/L; cerium oxide nanoparticles (CeO2NP) 0.75–10 μg/L; arsenic (As) 0.75–2.5 mg/L; and mercury (Hg) 5–100 mg/L. Viability was assessed through water-soluble tetrazolium (WST-1) and thiazolyl blue tetrazolium bromide (MTT) (24 h exposure) and clonogenic (seven-day exposure) assays. Cell cycle alterations were explored by flow cytometry. Viability was affected in a dose- and time-dependent manner. Prolonged exposure caused inhibition of cell proliferation even at low concentrations. Cell-cycle progression was affected by TiO2NP 75 mg/L, and As 0.75 and 2.5 μg/L, increasing the cell proportion at G0/G1 phase. Combined exposure of TiO2NP or CeO2NP mitigated As adverse effects, increasing the cell surviving factor, but cell cycle alterations were still observed. Only CeO2NP co-exposure reduced Hg toxicity, translated in a decrease of cells in Sub-G1. Toxicity was diminished for both NPs co-exposure compared to its toxicity alone, but a marked toxicity for the highest concentrations was observed for longer exposures. These findings prove that joint toxicity of contaminants must not be disregarded.
Bimodal nanoprobes comprising both magnetic and optical functionalities have been prepared via a sequential two-step process. Firstly, magnetite nanoparticles (MNPs) with well-defined cubic shape and an average dimension of 80 nm were produced by hydrolysis of iron sulfate and were then surface modified with silica shells by using the sol-gel method. The Fe3O4@SiO2 particles were then functionalized with the fluorophore, fluorescein isothiocyanate (FITC), mediated by assembled shells of the cationic polyelectrolyte, polyethyleneimine (PEI). The Fe3O4 functionalized particles were then preliminary evaluated as fluorescent and magnetic probes by performing studies in which neuroblast cells have been contacted with these nanomaterials.
The technical feasibility of using stopper-derived cork as an effective biosorbent towards bivalent mercury at environmentally relevant concentrations and conditions was evaluated in this study. Only 25 mg/L of cork powder was able to achieve 94 % of mercury removal for an initial mercury concentration of 500 μg/L. It was found that under the conditions tested, the efficiency of mercury removal expressed as equilibrium removal percentage does not depend on the amount of cork or its particle size, but is very sensitive to initial metal concentration, with higher removal efficiencies at higher initial concentrations. Ion exchange was identified as one of the mechanisms involved in the sorption of Hg onto cork in the absence of ionic competition. Under ionic competition, stopper-derived cork showed to be extremely effective and selective for mercury in binary mixtures, while in complex matrices like seawater, moderate inhibition of the sorption process was observed, attributed to a change in mercury speciation. The loadings achieved are similar to the majority of literature values found for other biosorbents and for other metals, suggesting that cork stoppers can be recycled as an effective biosorbent for water treatment. However, the most interesting result is that equilibrium data show a very rare behaviour, with the isotherm presenting an almost square convex shape to the concentration axis, with an infinite slope for an Hg concentration in solution around 25 μg/L.
This work reports the preparation of ferro-magnetic nickel nanowires (NiNW) coated with dithiocarbamate-functionalized siliceous shells and its application for the uptake of aqueous Hg(II) ions by magnetic separation. NiNW with an average diameter and length of 35 nm and 5 μm, respectively, were firstly prepared by Ni electrodeposition in an anodic aluminum oxide template. The NiNW surfaces were then coated with siliceous shells containing dithiocarbamate groups via a one-step procedure consisting in the alkaline hydrolytic co-condensation of tetraethoxysilane (TEOS) and a siloxydithiocarbamate precursor (SiDTC). A small amount of these new nanoadsorbents (2.5 mg·L(-1)) removed 99.8% of mercury ions from aqueous solutions with concentration 50 μg·L(-1) and in less than 24 h of contact time. This outstanding removal ability is attributed to the high affinity of the sulfur donor ligands to Hg(II) species combined with the high surface area-to-volume ratio of the NiNW.
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