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.

Removal of mercury by silica-supported ionic liquids: Efficiency and ecotoxicological assessment.

Anthropogenic impacts have affected the coastal environment and contributed to its contamination. Mercury (Hg) is widespread in nature and has been shown to be toxic in even the smallest amounts, negatively affecting not only the marine ecosystem but also the entire trophic chain due to its biomagnification. Mercury ranks third on the Agency for Toxic Substances and Diseases Registry (ATSDR) priority list and it is therefore imperative to develop more effective methods than those currently available to avoid the persistence of this contaminant in aquatic ecosystems. The present study aimed to evaluate the effectiveness of six different silica-supported ionic liquids (SIL) in removing Hg from contaminated saline water, under realistic conditions ([Hg] = 50 µg/L), and to ecotoxicologically evaluate the safety of the SIL-remedied water, using as test model the marine macroalga Ulva lactuca. The results revealed that SIL [Si][C3C1im][SCN] (250 mg/L) was the most effective in removing Hg from solution, with a efficiency up to 99 % in just 6 h, that enable to obtain < 1 µg/L Hg (European guideline in drinking water). U. lactuca exposed to either the SIL and/or the remedied water showed no significant changes in relative growth rate and chlorophyll a and b levels, compared to the control condition. Biomarker analysis (LPO, GSH, GSSG, SOD, GPx, CAT and GRed) also showed no significant changes in the biochemical performance of U. lactuca. Therefore, it could be assumed that water treatment with SIL or its presence in an aqueous environment does not pose toxicity levels that could inhibit the metabolism or cause cell damage to U. lactuca.

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.

Validation of a methodology to quantify macro, micro, and potentially toxic elements in food matrices.

To routinely assess whether consumed food meets international guidelines, a single analytical method able to quantify minerals and potentially toxic elements (PTEs) in real food matrices is required. This work validated a simple and efficient method to quantify nine elements in different food matrices by ICP-MS. Samples from local markets (chicken, mussels, fish, rice, and seaweed) and certified reference materials were digested with HNO3 68 % and H2O2 30 %. All performance criteria (working range, linearity, LOD, LOQ, selectivity, repeatability, and trueness) met the requirements of the Portuguese Association of Accredited Laboratories. Comparison between raw and cooked food showed significant changes in most element levels, and PTEs contents complied with the maximum permissible values (EC N° 1881/2006). The minimum and maximum amounts of the foods studied, alone or in combination, raw or cooked, that can be daily consumed to meet EFSA and WHO nutritional and safety requirements were analysed.

Response surface approach to optimize the removal of the critical raw material dysprosium from water through living seaweeds.

Dysprosium (Dy) is a rare earth element with a high economic and strategic value, and simultaneously an emerging contaminant, whose removal from wastewaters is gaining increasing attention. In this work, the Response Surface Methodology (RSM) combined with a Box-Behnken Design (3 factors-3 levels) was used to optimize the key operational conditions that influence the uptake of Dy by two living seaweed, Ulva sp. and Gracilaria sp.. The initial concentration of Dy (10-500 µg/L), water salinity (10-30), and seaweed dosage (0.5-5.5 g/L) were the independent variables, while the removal efficiency (%) and bioaccumulation (q, µg/g) were the response variables. Results highlighted the high capacity of both species to capture Dy. After 168 h, the optimal conditions that led to a maximum of 91 % of Dy removed by Gracilaria sp. were: 500 µg of Dy per L of water, salinity 10, and 5.5 g of seaweed per L. For Ulva sp., a maximum removal percentage of 79 % was achieved in the conditions: any initial concentration of Dy, salinity 20, and seaweed dosage of 3.7 g/L. Independently of the species, the response surfaces showed that the most important variable for the removal is the seaweed dosage, while for bioaccumulation is the initial concentration of Dy. Using RSM, it was possible to obtain the optimal operating conditions for Dy removal from waters, which is a fundamental step toward the application of the proposed technology at large scale.

Can the recycling of europium from contaminated waters be achieved through living macroalgae? Study on accumulation and toxicological impacts under realistic concentrations.

Europium (Eu) strategic importance for the manufacturing industry, high economic value and high supply risk, categorizes it as critical raw material. Due to anthropogenic contamination, Eu levels in ecosystems have been growing, which opens opportunities for innovation: its recovery and recycling from contaminated water as element source - circular economy. In this pioneering study, six widely available living marine macroalgae (Ulva intestinalis, Ulva lactuca, Gracilaria sp., Osmundea pinnatifida, Fucus vesiculosus and Fucus spiralis) were characterized (water content and specific surface area) and evaluated in the pre-concentration and recovery of Eu from contaminated seawater, under different relevant contamination scenarios (10, 152 and 500 µg L-1). U. lactuca and Gracilaria sp. (3 g L-1, fresh weight) proved to be the most effective in removing Eu, reaching up to 85% in 72 h, while the highest Eu enrichment was observed in U. intestinalis biomass, up to 827 µg g-1 (bioconcentration factor of 1800), which is higher than Eu levels in common apatite ores. The effect of Eu exposure on macroalgae growth rate and organism biochemical performance (LPO, SOD, GPx and GSTs) was also evaluated for the first time, to the best of our knowledge. Although no cellular damage was recorded, findings revealed toxicity and defence mechanisms activation, emphasizing the need of further studies on the potential risks associated with the presence of this emerging contaminant in aquatic ecosystems.

Sustainable recovery of neodymium and dysprosium from waters through seaweeds: Influence of operational parameters.

The high demand for greener energy and technological innovation require some crucial elements, such as the rare earths Nd and Dy. Being considered two of the most critical elements (high supply risk), it is vital to recover them from wastes/wastewaters, for later reuse. Here, the influence of operational parameters, such as biosorbent stock density (0.5, 3.0, and 5.5 g L-1), ionic strength (salinity 10 and 30) and contact time (24, 72 and 168 h), in the biosorption/bioaccumulation of Nd and Dy by two living marine macroalgae was evaluated in artificial seawater, seeking the improvement of the process. Results demonstrated that stock density is the most influential parameter, while the ionic strength showed to be a selective parameter, with a major influence only for Dy removal, which can be attributed to the different chemical characteristics observed between light rare earth elements (LREE) and heavy rare earth elements (HREE). For the ranges studied, the greatest removal/recovery for Gracilaria sp. was achieved with a stock density of 3.0 g L-1 at salinity 10, after 72 h for both REEs. For Ulva lactuca optimal conditions were: stock density of 5.5 g L-1 at salinity 10 with a contact time of 72 h for both REEs. Between species, U. lactuca showed to be the most promising, with removal efficiencies up to 98% for Nd and 89% for Dy. Findings substantiate the potential of the proposed process for obtaining Nd and Dy from secondary sources, particularly from low-level contaminated waters.

Bioaccumulation processes for mercury removal from saline waters by green, brown and red living marine macroalgae.

Mercury is a very toxic metal that persists and accumulates in the living organisms present in the aquatic systems and its elimination is an urgent need. Two green (Ulva intestinalis and Ulva lactuca), brown (Fucus spiralis and Fucus vesiculosus), and red (Gracilaria sp. and Osmundea pinnatifida) marine macroalgae were tested for mercury removal from saline waters. The ability of each species was evaluated to the initial mercury concentrations of 50, 200, and 500 µg dm-3 along 72 h. In general, all species exhibited good performances, removing 80.9-99.9% from solutions with 50 µg dm-3, 79.3-98.6% from solutions with 200 µg dm-3, and 69.8-97.7% from solutions containing 500 µg dm-3 of mercury. Among the macroalgae, Ulva intestinalis showed the highest affinity to mercury and it presented an uptake ability up to 1888 µg g-1 of Hg(II) and bioconcentration factors up to 3823, which proved its promising potential on Hg removal.

How safe are the new green energy resources for marine wildlife? The case of lithium.

Considering the increasing use of Lithium (Li) and the necessity to fulfil this demand, labile Li occurrence in the environment will be enhanced. Thus, additional research is needed regarding the presence of this element in marine environment and its potential toxic impacts towards inhabiting wildlife. The aim of the present study was to evaluate Li toxicity based on the exposure of Mytilus galloprovincialis to this metal, assessing the biochemical changes related with mussels' metabolism, oxidative stress and neurotoxicity. For this, organisms were exposed to different Li concentrations (100, 250, 750 µg/L) for 28 days. The results obtained clearly demonstrated that Li lead to mussels' metabolism depression. The present study also revealed that, especially at the highest concentrations, antioxidant and biotransformation enzymes were not activated, leading to the occurrence of lipid peroxidation and loss of redox homeostasis, with increased content in oxidized glutathione in comparison to the reduced form. Furthermore, after 28 days, higher Li exposure concentrations induced neurotoxic effects in mussels, with a decrease in acetylcholinesterase enzyme activity. The responses observed were closely related with Li concentrations in mussels' tissues, which were more pronounced at higher exposure concentrations. Such results highlight the potential toxic effects of Li to marine species, which may even be higher under predicted climate changes and/or in the presence of other pollutants.

Influence of salinity and rare earth elements on simultaneous removal of Cd, Cr, Cu, Hg, Ni and Pb from contaminated waters by living macroalgae.

Potentially toxic elements (PTEs) are of major concern due to their high persistence and toxicity. Recently, rare earth elements (REEs) concentration in aquatic ecosystems has been increasing due to their application in modern technologies. Thus, this work aimed to study, for the first time, the influence of REEs (lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium and yttrium) and of salinity (10 and 30) on the removal of PTEs (Cd, Cr, Cu, Hg, Ni and Pb) from contaminated waters by living macroalgae (Fucus spiralis, Fucus vesiculosus, Gracilaria sp., Osmundea pinnatifida, Ulva intestinalis and Ulva lactuca). Experiments ran for 168 h, with each macroalga exposed to saline water spiked with the six PTEs and with the six PTEs plus nine REEs (all at 1 µmol L-1) at both salinities. Results showed that all species have high affinity with Hg (90-99% of removal), not being affected neither by salinity changes nor by the presence of other PTEs or REEs. Cd showed the lowest affinity to most macroalgae, with residual concentrations in water varying between 50 and 108 µg L-1, while Pb removal always increased with salinity decline (up to 80% at salinity 10). REEs influence was clearer at salinity 30, and mainly for Pb. No substantial changes were observed in Ni and Hg sorption. For the remaining elements, the effect of REEs varied among algae species. Overall, the results highlight the role of marine macroalgae as living biofilters (particularly U. lactuca), capable of lowering the levels of top priority hazardous substances (particularly Hg) and other PTEs in water, even in the presence of the new emerging contaminants - REEs. Differences in removal efficiency between elements and macroalgae are explained by the contaminant chemistry in water and by macroalgae characteristics.

Assessment of marine macroalgae potential for gadolinium removal from contaminated aquatic systems.

Gadolinium (Gd) is a rare earth associated with hospital and urban wastewaters due to its application as a contrast agent for magnetic resonance imaging. In this work, the uptake of Gd from contaminated seawater by three living marine macroalgae, Ulva lactuca (Chlorophyta), Fucus spiralis (Phaeophyta) and Gracilaria sp. (Rhodophyta) was studied along 72 h. Surface analysis (FTIR), water content, kinetic modelling, and Gd quantification in seawater and biomass were performed. All species were able to accumulate Gd from seawater with 10, 157, and 500 µg Gd L-1, although green and red macroalgae performed better, following the order: green > red > brown. Removal efficiencies reached 85%, corresponding to a bioconcentration factor of 1700. In more complex solutions that intended to mimic real contaminated environments, namely mixtures with other rare earth elements (Y, La, Ce, Pr, Nd, Eu, Tb, Dy), and with potentially toxic elements commonly found in wastewaters (Cr, Ni, Cu, Cd, Hg, Pb), at two salinities (10 and 30), the macroalgae kept its efficiency: 84% and 88% of removal by green and red macroalgae, respectively. Overall, findings evidence that living macroalgae could be a countermeasure to the increasing anthropogenic enrichment of Gd observed in the aquatic environment.

Main drivers of mercury levels in Southern Ocean lantern fish Myctophidae.

Myctophids are the most abundant fish group in the Southern Ocean pelagic ecosystem and are an important link in the Antarctic marine food web. Due to their major ecological role, evaluating the level of mercury (Hg) contamination in myctophids is important as a step towards understanding the trophic pathway of this contaminant. The concentrations of total Hg were determined in muscle, gill, heart and liver tissue of 9 myctophid species to quantify tissue partitioning variability between species. Organic Hg concentration and proportion in muscle was also determined. Hg concentrations were higher in the liver and heart than in muscle and gills, but the proportion of organic Hg was almost 100% in muscle, indicating that the main uptake route for Hg is through the diet. Most of the species analysed have similar vertical and horizontal distributions, and similar feeding modes and prey. Geographical and temporal variability of Hg concentrations was examined using samples from 3 different sampling cruise (2007/08, 2015/16 and 2016/17) and 2 locations (South Georgia and South Orkneys Islands). Our results appear to indicate a decreasing trend in Hg contamination over the last decade, particularly gill tissue, which is in agreement with a previous study on squid from the same region. There was no significant variability in Hg concentration between the different sampling locations. Hg levels were consistent with values reported previously for myctophids around the world, indicating low global-scale geographic variability. A positive relationship between fish size and Hg concentration was found for most species, with the exception of Electrona antarctica females, which may be explained through Hg elimination by egg laying. We estimate that myctophids collectively comprise a Southern Ocean mercury 'reserve' of ≈1.82 metric tonnes.

Toxicological assessment of anthropogenic Gadolinium in seawater: Biochemical effects in mussels Mytilus galloprovincialis.

Recently, anthropogenic enrichment of rare earth elements (REEs) have been reported in natural environments, due to increasing use and discharges of hospital/industrial wastewaters. Gadolinium (Gd), which is mainly used as contrast agent for magnetic resonance imaging in medical exams, may reach concentrations in water up to two orders of magnitude larger than baseline levels. Nevertheless, in marine systems scarce information is available concerning the toxicity of REE towards inhabiting organisms. This study aimed to evaluate the biochemical impact of anthropogenic Gd in the Mediterranean mussel Mytilus galloprovincialis, which is a species of commercial interest and one of the most accepted pollution bioindicator. Organisms were exposed to different concentrations of Gd (0, 15, 30, 60, 120 µg/L) for 28 days. At the end of the experiments, biomarkers related to mussels' metabolic (electron transport system activity and energy reserves content), oxidative stress status (cellular damage and the activity of antioxidant and biotransformation enzymes) and neurotoxic effects (activity of the enzyme Acetylcholinesterase) were measured, as well as Gd bioconcentration in organisms. Results showed a high content of Gd (2.5 ±â€¯0.50 µg/g) in mussels exposed to the highest concentration, contrary to those at control condition and at 15 and 30 µg/L of Gd (levels below 0.38 µg/g). Although no mortality was observed during the experimental period, exposure to Gd strongly affected the biochemical performance of M. galloprovincialis, including the decrease on mussels' metabolism, induction of oxidative stress and neurotoxicity, particularly evidenced at intermediate concentrations. These results may indicate that up to certain stressful levels, although lowering their metabolism, organisms may be able to activate defence strategies to avoid cellular injuries which, on the other hand, may compromise mussels physiological performance such as growth and reproduction success. Nevertheless, our findings support that the widespread utilization of Gd may represent an environmental risk in the future.