Enhanced removal of rare earth elements from aqueous media: exploring the potential of AM-3 and AM-4 titanosilicates.

This study investigates the impact of three key variables on the performance of nanoporous AM-3 and layered AM-4 titanosilicates in removing nine REEs (Y, La, Ce, Pr, Nd, Eu, Gd, Tb, and Dy) from natural mineral water and identifies optimal operational conditions using Response Surface Methodology (RSM). The experimental conditions were determined by a Box-Behnken Design of 3 factors-3 levels (pH 4, 6, and 8; sorbent dose 20, 100, and 180 mg/L; and element concentration 1, 3, and 5 µmol/L). Three-dimensional response surfaces were used to assess the linear, quadratic, and interaction influences of each factor on the REEs' removal percentage. The pH was the most significant factor in the removal process using AM-3, while the sorbent dose was more important for AM-4. The results highlighted the sorbents' strong capacity for REE removal. The optimal operating conditions obtained by RSM were applied to aqueous solutions with salinity 10 (common in coastal and transitional systems) and 30 (average seawater salinity). The results showed that AM-3 has a strong potential for removing REEs in solutions with salinity 10 and 30, while AM-4 was less efficient due to competition between REEs and other ions present in the solution.

Removal of chromium(III) from contaminated waters using cobalt ferrite: how safe is remediated water to aquatic wildlife?

The release of hazardous elements by industrial effluents to aquatic ecosystems is a potential threat to the environment. Chromium (Cr) is one of the elements whose levels in several freshwater ecosystems should be reduced to promote water reuse. In recent years, magnetic materials have gained increasing interest as sorbents because of their easy removal from treated water through magnetic separation. In this study, colloidal cobalt ferrite (CoFe2O4) particles were investigated as magnetic sorbents for chromium-aqueous chemical species. The oxidative stress responses of Mytilus galloprovincialis mussels exposed to 200 µg/L of Cr, resembling remediated water, were evaluated. More than 95% of Cr was removed from contaminated solutions by CoFe2O4 aqueous suspensions at pH 6 and pH 10. The kinetics of sorption experiments were examined using pseudo-1st order, pseudo-2nd order and Elovich models to evaluate which mathematical model has a better adjustment to the experimental data. The present study revealed that the levels of Cr that remained in remediated water induced limited biochemical changes in mussels, being considered safe for aquatic systems. Overall, the use of cobalt ferrite-based sorbents may constitute a promising approach to remediate contaminated water.

Eco-friendly methodology for removing and recovering rare earth elements from saline industrial wastewater.

In this study, response surface methodology (RSM) was applied with a Box-Behnken design to optimize the biosorption (removal and bioconcentration) of rare earth elements (REEs) (Y, La, Ce Eu, Gd, Tb) by living Ulva sp. from diluted industrial wastewaters (also containing Pt and the classic contaminants Hg, Pb, Zn, Cu, Co, and Cd). Element concentration (A: 10-190 µg/L), wastewater salinity (B: 15-35), and Ulva sp. dosage (C: 1.0-5.0 g/L) were the operating parameters chosen for optimization. Analysis of the Box-Behnken central point confirmed the reproducibility of the methodology and p-values below 0.0001 validated the developed mathematical models. The largest inter-element differences were observed at 24 h, with most REEs, Cu, Pb and Hg showing removals ≥ 50 %. The factor with the greatest impact (positive) on element removal was the initial seaweed dosage (ANOVA, p < 0.05). The optimal conditions for REEs removal were an initial REEs concentration of 10 µg/L, at a wastewater salinity of 15, and an Ulva sp. dosage of 5.0 g/L, attaining removals up to 88 % in 24 h. Extending the time to 96 h allowed seaweed dosage to be reduced to 4.2 g/L while achieving removals ≥ 90 %. The high concentrations in REE-enriched biomass (∑REEs of 3222 µg/g), which are up to 3000 times higher than those originally found in water and exceed those in common ores, support their use as an alternative source of these critical raw materials.

Application of response surface methodology and box-behnken design for the optimization of mercury removal by Ulva sp.

Mercury (Hg) is a global and top priority contaminant, toxic at low concentrations. Although it has been progressively eliminated from processes, this metal continues to circulate in the atmosphere, soil, and water. In this work, the Response Surface Methodology (RSM) combined with a Box-Behnken Design (3 factors - 3 levels) was used to optimize key operational conditions that influence the removal and uptake of Hg by living macroalga Ulva sp. in a complex mixture containing several elements used in industry (potentially toxic elements, rare earth elements, and platinum-group elements) (initial concentration 10, 100 and 190 µg/L, salinity 15, 25 and 35, seaweed stock density 1.0, 3.0 and 5.0 g/L). Results evidenced the great capability of Ulva sp. to remove Hg, with removal efficiencies between 69 % and 97 %. 3-D surfaces showed that the most impactful variable was seaweed stock density, with higher densities leading to higher removal. Regarding the uptake, a positive correlation between initial concentration and qt values was observed. The appliance of RSM made possible to obtain optimal operating conditions for removing virtually 100 % of Hg from waters with high ionic strength, which is a pivotal step in the direction of the application of this remediation biotechnology at large scale.

In Vitro Hepatotoxic and Neurotoxic Effects of Titanium and Cerium Dioxide Nanoparticles, Arsenic and Mercury Co-Exposure.

Considering the increasing emergence of new contaminants, such as nanomaterials, mixing with legacy contaminants, including metal(loid)s, it becomes imperative to understand the toxic profile resulting from these interactions. This work aimed at assessing and comparing the individual and combined hepatotoxic and neurotoxic potential of titanium dioxide nanoparticles (TiO2NPs 0.75-75 mg/L), cerium oxide nanoparticles (CeO2NPs 0.075-10 µg/L), arsenic (As 0.01-2.5 mg/L), and mercury (Hg 0.5-100 mg/L) on human hepatoma (HepG2) and neuroblastoma (SH-SY5Y) cells. Viability was assessed through WST-1 (24 h) and clonogenic (7 days) assays and it was affected in a dose-, time- and cell-dependent manner. Higher concentrations caused greater toxicity, while prolonged exposure caused inhibition of cell proliferation, even at low concentrations, for both cell lines. Cell cycle progression, explored by flow cytometry 24 h post-exposure, revealed that TiO2NPs, As and Hg but not CeO2NPs, changed the profiles of SH-SY5Y and HepG2 cells in a dose-dependent manner, and that the cell cycle was, overall, more affected by exposure to mixtures. Exposure to binary mixtures revealed either potentiation or antagonistic effects depending on the composition, cell type and time of exposure. These findings prove that joint toxicity of contaminants cannot be disregarded and must be further explored.

Can water remediated by manganese spinel ferrite nanoparticles be safe for marine bivalves?

In the last few years the use of nanoparticles (NPs) such as the manganese spinel ferrite (MnFe2O4) has been increasing, with a vast variety of applications including water remediation from pollutants as metal(oid)s. Although an increasing number of studies already demonstrated the potential toxicity of NPs towards aquatic systems and inhabiting organisms, there is still scarce information on the potential hazard of the remediated water using NPs. The present study aimed to evaluate the ecotoxicological safety of Pb contaminated seawater remediated with MnFe2O4, NPs, assessing the toxicity induced in mussels Mytilus galloprovincialis exposed to contaminated seawater and to water that was remediated using MnFe2O4, NPs. The results obtained demonstrated that seawater contaminated with Pb, NPs or the mixture of both (Pb + NPs) induced higher toxicity in mussels compared to organisms exposed to Pb, NPs and Pb + NPs after the remediation process. In particular, higher metabolic depression, oxidative stress and neurotoxicity were observed in mussels exposed to contaminated seawater in comparison to mussels exposed to remediated seawater.

Spinel-type ferrite nanoparticles for removal of arsenic(V) from water.

Spinel ferrite particles (Fe3O4, MnFe2O4, and CoFe2O4) were investigated as magnetic nanosorbents for removing arsenic from spiked water samples. The nanosorbents were collected via magnetic separation from aqueous solutions spiked with an arsenic concentration that mimics the amount of this contaminant in real water samples. This research shows that using amounts of CoFe2O4 or MnFe2O4 as low as 40 mg/L, the arsenic content in the contaminated water decreased for levels below the maximum admitted value by the World Health Organization for drinking waters (10 µg/L). Moreover, these magnetic nanosorbents also showed good performance for As(V) sorption, when applied to aqueous matrices with variable ionic strength and in the mixtures of other several hazardous contaminants. The good performance observed for the MnFe2O4 and CoFe2O4 ferrites contrasts with the one observed for Fe3O4 nanosorbent, whose efficiency is lower in the removal of As(V) from water, nevertheless increased with the presence of other elements in solution.

Unravelling the Potential Cytotoxic Effects of Metal Oxide Nanoparticles and Metal(Loid) Mixtures on A549 Human Cell Line.

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) 0.0.75-10 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.

Remediation of arsenic from contaminated seawater using manganese spinel ferrite nanoparticles: Ecotoxicological evaluation in Mytilus galloprovincialis.

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. As such, in the present study we aimed to evaluate the ecotoxicological safety of seawater previously contaminated with arsenic (As) and remediated by using manganese-ferrite (MnFe2O4-NPs) 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 MnFe2O4- NPs (50 mg L-1) with and without 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% and 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 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.

Reliable quantification of mercury in natural waters using surface modified magnetite nanoparticles.

Reliable determination of mercury (Hg) in natural waters is a major analytical challenge due to its low concentration and to the risk of Hg losses or contamination during sampling, storage and pre-treatment of samples. The present work proposes a simple, efficient, sensitive and easy-handling methodology for extraction, pre-concentration and quantification of total dissolved mercury in natural waters, using iron oxide nanoparticles (NPs) coated with silica shells functionalized with dithiocarbamate groups (Fe3O4@SiO2SiDTC). Ten mg L-1 of these NPs were sufficient to remove 83-97% of 500 to 10 ng L-1 of Hg in ultra-pure water and artificial seawater, used as model Hg solutions, within 24 h. Mercury sorbed to the NPs was then measured directly by thermal decomposition atomic absorption spectrometry with gold amalgamation. The detection limit of approximately 1.8 ng L-1 is lower than the values reported in dispersive solid phase extraction for other magnetic sorbents. As a proof-of-concept, the proposed methodology was successfully tested in real samples of fresh and saline waters and more than 91% of Hg was recovered. With this methodology the extraction and pre-concentration steps may be carried out in situ decreasing the risk of Hg losses or contamination during sampling, storage and pre-treatment of water samples.

Mercury in river, estuarine and seawaters - Is it possible to decrease realist environmental concentrations in order to achieve environmental quality standards?

Dithiocarbamate-functionalized magnetite nanoparticles (Fe3O4@SiO2/SiDTC) have been investigated as a convenient and effective sorbent for mercury removal from river, estuarine and sea waters, and their capability to decrease realistic environmental concentrations to the new environmental quality standards was evaluated. The sorption kinetics was well described by the Elovich model and the initial sorption rate was dependent of the sorbent dose. Except for river water sample, the Fe3O4@SiO2/SiDTC particles uptake 99.9% or more of the Hg(II) in the waters (initially at the concentration of 50 µg/L), allowing to reach residual concentrations lower than the new environmental quality standards (70 ng/L) with only 10 mg/L of sorbent material. The distribution coefficients of mercuric ions between the magnetic particles and the different natural water types were above 103 mL/g for the river water and above 105 mL/g for the estuarine and sea waters. The differences observed between the water types can be attributed to different water composition (effect of the matrix), which plays an important role in the efficiency of the water treatment.

Remediation of mercury contaminated saltwater with functionalized silica coated magnetite nanoparticles.

The study aimed to evaluate the efficiency of dithiocarbamate functionalized silica coated magnetite nanoparticles (NPs) for Hg decontamination of saltwater either contaminated with Hg alone or with As and Cd. For this, the residual levels of Hg in seawater were assessed and Hg-contaminated or Hg+As+Cd-contaminated seawater toxicity to aquatic biota, before and after the sorption process, was compared. The results showed that under highly competitive conditions (water salts, Cd and As), the removal of Hg from seawater, by using these magnetic NPs, for the lowest concentration (50µg/L) was superior to 98% and for the highest concentration (500µg/L) ranged between 61% to 67%. Despite the great affinity of the magnetic NPs for Hg, they were not effective at removing As and Cd from seawater. In relation to the ecotoxicity endpoints after remediation, the mixture with lower Hg concentration exhibited no toxicity to rotifer Brachionus plicatilis and bacteria Vibrio fischeri ; however, the mixture with higher concentration revealed toxicity. In addition, the toxicity of bacteria V. fischeri, rotifer B. plicatilis and algae Phaeodactylum tricornutum, whose responses where inhibited during its exposure to the non-remediate sample was considerably reduced after treatment with NPs. Furthermore, microalgae P. tricornutum appears to be most sensitive species while Artemia franciscana showed no toxic effects to the tested solutions. Both chemical and ecotoxicological approaches revealed a high efficiency for the remediation of Hg-contaminated saltwater.

Ferromagnetic sorbents based on nickel nanowires for efficient uptake of mercury from water.

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.

Competitive effects on mercury removal by an agricultural waste: application to synthetic and natural spiked waters.

In this work, the efficiency of a local and highly, available agricultural waste, the raw rice husk, was used to remove mercury (Hg) from synthetic and natural waters, spiked with concentrations that reflect the contamination problems found in the environment. Different operating conditions were tested, including initial pH, ionic strength, the presence of co-ions (cadmium) and organic matter. The sorption efficiency of rice husk was slightly affected by the presence H+ ions (pH range between 3 and 9), but in the presence of NaNO3 and NaCl electrolytes and in binary solutions containing Cd2+ and H2+, the sorption efficiency was dependent on the nature and levels of the interfering ion and on the initial concentration of Hg+ used. Nevertheless, in a situation of equilibrium the effect of those ions was negligible and the removal efficiency ranged between 82% and 94% and between 90% and 96% for an initial Hg2+ concentration of 0.05 mg L(-1) and 0.50 mg L(-1), respectively. In more complex matrices, i.e. in the presence ofhumic substances and in natural river waters, the speciation and dynamics of Hg was changed and a fraction of the metal becomes unavailable in solution. Even then, the values obtained for Hg removal were satisfactory, i.e. between 59% and 76% and 81% and 85% for an initial concentration of Hg2+ of 0.05 and 0.50 mg L(-1), respectively.

Cork stoppers as an effective sorbent for water treatment: the removal of mercury at environmentally relevant concentrations and conditions.

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.

Fluorescent Magnetic Bioprobes by Surface Modification of Magnetite Nanoparticles.

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.