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.

Microplastics in marine mussels, biological effects and human risk of intake: A case study in a multi-stressor environment.

This study documented seasonal levels of microplastics (MPs) and biomarkers (condition index, neurotoxicity, energy, oxidative stress) in mussels (Mytilus galloprovincialis), and water physico-chemical parameters in the Douro estuary (NE Atlantic coast), and estimated the human risk of MP intake (HRI) through mussels. Mussel stress was determined through the Integrated Biomarker Response (IBR). HRI was estimated from mussel MP concentrations and consumer habits. MPs were mainly micro-fibres (72 %) with varied chemical composition. Seasonal MP means (±SEM) in mussels ranged from 0.111 ± 0.044 (spring) to 0.312 ± 0.092 MPs/g (summer). Seasonal variations of mussel stress (IBR: 1.4 spring to 9.7 summer) and MP concentrations were not related. MeO-BDEs, PBDEs, temperature, salinity and other factors likely contributed to mussel stress variation. HRI ranged from 2438 to 2650 MPs/year. Compared to the literature, MP contamination in mussels is low, as well as the human risk of MP intake through their consumption.

Algal sorbents and prospects for their application in the sustainable recovery of rare earth elements from E-waste.

Efficient and sustainable secondary sourcing of Rare-Earth Elements (REE) is essential to counter supply bottlenecks and the impacts associated with primary mining. Recycled electronic waste (E-waste) is considered a promising REE source and hydrometallurgical methods followed by chemical separation techniques (usually solvent extraction) have been successfully applied to these wastes with high REE yields. However, the generation of acidic and organic waste streams is considered unsustainable and has led to the search for "greener" approaches. Sorption-based technologies using biomass such as bacteria, fungi and algae have been developed to sustainably recover REE from e-waste. Algae sorbents in particular have experienced growing research interest in recent years. Despite its high potential, sorption efficiency is strongly influenced by sorbent-specific parameters such as biomass type and state (fresh/dried, pre-treatment, functionalization) as well as solution parameters such as pH, REE concentration, and matrix complexity (ionic strength and competing ions). This review highlights differences in experimental conditions among published algal-based REE sorption studies and their impact on sorption efficiency. Since research into algal sorbents for REE recovery from real wastes is still in its infancy, aspects such as the economic viability of a realistic application are still unexplored. However, it has been proposed to integrate REE recovery into an algal biorefinery concept to increase the economics of the process (by providing a range of additional products), but also in the prospect of achieving carbon neutrality (as large-scale algae cultivation can act as a CO2 sink).

Trace elements in relation to trophic ecology of long-distance migratory shorebirds and seabirds in West Africa.

Shorebirds and seabirds are abundant predators in coastal habitats worldwide, relying upon a high diversity of benthic invertebrates and fish, respectively. While occupying different trophic guilds, they are differently exposed to element contamination entering the coastal food web. Therefore, these birds have been used as bioindicators of environmental contamination in marine ecosystems. We analysed the concentration of trace elements in blood samples of 16 shorebird and seabird migratory species in a major non-breeding site, the Bijagós Archipelago, in regard to their trophic ecology. Overall, our study shows low exposure of this bird community to toxic elements, except for Hg. Most species presented Hg burdens within the moderate toxicity threshold, but one species (Dunlin) presented values at a potential high Hg toxicity risk. We found a positive relationship between Se and Ni concentrations and δ15N values (a proxy for trophic level). In addition, a positive relationship was found between δ13C (a proxy for habitat characteristics) and Hg, Fe, Cu and Mn, while the opposite pattern was recorded for As. Differences were also shown for several trace elements between the two studied trophic guilds: concentrations of As, Pb and Se were higher in pelagic fish consumers (seabirds), whereas Cr, Fe and Sr burdens were higher in benthic invertebrate consumers (shorebirds). Although previous studies in the same site revealed very high concentrations of Cd and Pb in some of the prey species of shorebirds and seabirds (bivalves and fishes), values found in birds for these two elements suggest no toxicological risk. Thus, exposure to toxic elements is not currently a threat to coastal bird populations, namely those facing apparent local declines in Guinea-Bissau, one of the most important non-breeding quarters for of West Africa. Still, Hg burdens were high in some species, deserving further monitoring.

Alzheimer's Disease and Toxins Produced by Marine Dinoflagellates: An Issue to Explore.

This paper examined the toxins naturally produced by marine dinoflagellates and their effects on increases in ß-amyloid plaques along with tau protein hyperphosphorylation, both major drivers of Alzheimer's disease (AD). This approach is in line with the demand for certain natural compounds, namely those produced by marine invertebrates that have the potential to be used in the treatment of AD. Current advances in AD treatment are discussed as well as the main factors that potentially affect the puzzling global AD pattern. This study focused on yessotoxins (YTXs), gymnodimine (GYM), spirolides (SPXs), and gambierol, all toxins that have been shown to reduce ß-amyloid plaques and tau hyperphosphorylation, thus preventing the neuronal or synaptic dysfunction that ultimately causes the cell death associated with AD (or other neurodegenerative diseases). Another group of toxins described, okadaic acid (OA) and its derivatives, inhibit protein phosphatase activity, which facilitates the presence of phosphorylated tau proteins. A few studies have used OA to trigger AD in zebrafish, providing an opportunity to test in vivo the effectiveness of new drugs in treating or attenuating AD. Constraints on the production of marine toxins for use in these tests have been considered. Different lines of research are anticipated regarding the action of the two groups of toxins.

Linking trophic ecology with element concentrations in a coastal fish community of the Bijagós Archipelago, West Africa.

We report the concentration of 13 elements in the muscle and liver of 17 coastal fish species of the Bijagós Archipelago, Guinea-Bissau, and link element concentrations to trophic ecology as assessed by carbon (δ13C) and nitrogen (δ15N) stable isotopes. We found higher concentrations of Hg, Fe, Mn, Cu, Zn, Se and As in liver as compared to muscle tissue, and the opposite pattern for Sr and Ca in all fish species. The concentration of Hg and Se in muscle samples increased significantly with δ15N, suggesting a biomagnification of these elements in this food chain. The concentrations of Ca and Sr, Fe and Cr, Ca and Mn, and Fe and Mn were positively correlated to each other in more than 50% of the studied species. Fish constitute the most important animal protein source for people in Guinea-Bissau, and thus assessing the concentrations of potentially toxic elements is relevant for human health.

Factors influencing sorption of trace elements in contaminated waters onto ground nut shells.

Biosorbent materials such as nut shells has been considered a promising alternative to the classic methods to remove potentially toxic elements from contaminated waters, improving water quality for other uses. The present study evaluated the sorption capacity of almond, hazelnut, pistachio and walnut shells for the single and simultaneous removal of As, Cd, Co, Hg, Ni, Pb and Zn from contaminated waters. The influence of key parameters such as sorbent dose, ionic strength (ultrapure water vs. mineral water), element competition (mono-vs. multi-element spiked solution) and initial element concentration (maximum allowed value in wastewater discharges and ten times lower) was assessed. Hazelnut shells stood out as the material with higher potential to remove Cd, Co, Hg, Ni, Pb and Zn in the tested conditions, achieving up to 99% of removal (Cd and Pb). Arsenic was not removed by none of the studied materials and the removal of Cr was only obtained in a simple matrix and in mono-element solution (41% of removal). An increase of matrix complexity negatively affected the sorption capacity of all the biosorbents in the removal of all the elements tested. The same behavior was obtained when the elements were simultaneously present in solution, with Pb, Cd and Hg being highly influenced by the presence of other elements. The increase in sorbent dose from 1 to 5 g/L allowed to at least duplicate the removal of Cd, Co, Ni and Zn by all the biosorbents. When decreasing the initial element concentration ten times the maximum allowed value in wastewater discharges, a significant increase of elements removal was attained, more pronounced for Hg and Pb. The possibility to change initial conditions towards high efficiencies validate the high potential of those biosorbents to be used in water remediation, with special focus on hazelnut shells, although other sorbents such as walnut or almond shells can be considered efficient with appropriate initial conditions and depending on the target elements to be removed.

Microplastics in fishes from an estuary (Minho River) ending into the NE Atlantic Ocean.

Wild fish (Cyprinus carpio, Mugil cephalus, Platichthys flesus) from an estuary of the NE Atlantic coast were investigated for plastic contamination (N = 128). From the 1289 particles recovered from fish samples, 883 were plastics. Among these, 84% were fibres and 97% were microplastics. Thirty-six polymers were identified. The number of microplastics (mean ± SD) per individual fish (MP/fish) was 8 ± 6 in C. carpio, 10 ± 9 in M. cephalus and 2 ± 2 in P. flesus. The means of MP/fish per body site were 6 ± 7 in gastrointestinal tract, 0.5 ± 1.1 in gills, 0.3 ± 0.7 in liver and 0.6 ± 1.2 in muscle samples. A few large fibres in liver (≤ 4841 µm) and muscle (≤ 5810 µm) samples were found. The results evidence the existence of high fish contamination by microplastics and reinforce the need of further research on plastic pollution in estuaries.

Selective incorporation of rare earth elements by seaweeds from Cape Mondego, western Portuguese coast.

This study examined the mechanism of incorporation of the rare earth elements (REEs), La, Ce, Nd, Eu, Gd, Tb, Yb, into green (Codium tomentosum, Ulva rigida), red (Gracilaria gracilis, Osmundea pinnatifida, Porphyra sp), and brown seaweeds (Saccorhiza polyschides, Undaria pinnatifida) collected from a single site near the coastline of the Cape Mondego, western Portugal. The concentrations of REEs, Mg, Ca, Al, Fe, Zn, and Cu in the biomasses were determined by inductively-coupled plasma mass spectrometry (ICP-MS). The species showed differences in their incorporation and fractionation of REEs from the same environment: the sum of REEs was higher in U. rigida, C. tomentosum, G. gracilis, and O. pinnatifida (0.7-1.7 µg g-1) than in Porphyra sp., S. polyschides, and U. pinnatifida (0.1-0.2 µg g-1). Ratios of Ce/Yb ranged from 13 (in S. polyschides) to 103 (in U. rigida), indicating different proportions of light and heavy REEs among species. Good correlations were found between Al and Fe (R2 = 0.98), and between these elements and La, Ce, Nd, Gd (R2 = 0.88-0.97) and Yb (R2 = 0.66-0.71) for all species except C. tomentosum and G. gracilis. Profiles of REE values normalised to average upper-continental crust composition indicated positive anomalies of Eu and Tb that reinforced the singularity of these elements in the REE group. Correlations between the REEs and Al or Fe suggest that detrital terrigenous particles, adhered to seaweed walls, may be an important mechanism for the incorporation of REEs by seaweeds. Different patterns for C. tomentosum and G. gracilis may also be indicative of the higher influence of cell wall composition on REE incorporation.

Elemental composition of whole body soft tissues in bivalves from the Bijagós Archipelago, Guinea-Bissau.

Marine bivalves are bioindicators of coastal environmental pollution, integrating monitoring programs worldwide. Nonetheless, the choice of particular species as an indicator requires validation, achieved by understanding the differences in element concentrations among and within species. The present study compares the chemical composition of whole body soft tissues of four common bivalve species from the Bijagós Archipelago, a pristine region of West Africa. Significant differences were recorded in the concentrations of various elements among studied species, which likely arise from species-specific uptake and bioaccumulation processes. Overall, there was a segregation between a group including the bloody cockle Senilia senilis and oyster Crassostrea tulipa (with high Cd and Zn concentrations) versus the two other species, Austromacoma nymphalis (with low Cu and high Mn, Se, Hg, Pb concentrations) and Diplodonta spp. (with high values of Cu, Al, Fe, V, Cr, Hg, Pb). C. tulipa was sampled in two different substrates (rock beds and mangrove roots), and the two groups revealed different chemical profiles, with significantly higher concentrations of P, Si, Zn and Cr and lower Cu in specimens fixed in mangrove roots. These results strongly suggest the influence of small-scale environmental variability on the accumulation of particular elements. We found extremely high Cd concentrations in S. senilis (27.1 ± 7.53 µg g-1 DW) and identified C. tulipa as another high Cd-accumulating species (ca. 10 µg g-1 DW). Our results suggest a detoxifying mechanism linked with the presence of Se to reduce the potential toxic effects of Cd in these two species. Cadmium concentrations reported for some bivalve species in this area largely exceed the maximum values proposed by the European Union, emphasizing the need for a regular contamination assessment.

Major characteristics of microplastics in mussels from the Portuguese coast.

The present study reports the quantity, shape, colour and chemical properties of microplastics (MP) and MP-like in whole soft tissues of the mussel Mytilus spp. collected in January and February 2019 from four natural banks in the Portuguese coast. Three sites are located in estuarine areas influenced by anthropogenic pressures and freshwater discharges, and one in the coast far from urbanised areas. An alkaline digestion (KOH) of biological tissues was used and a polymeric identification of 20% of the visually sorted particles was achieved using the Fourier-transform mid-infrared spectroscopy (FT-MIR). MP and MP-like concentrations ranged from 0.54 to 3.0 items g-1 without significant differences among the sites. Particle size varied from 36 to 4439 µm, being fibers the most abundant shape (50%) followed by films (22%) and spherules (18%). FT-MIR revealed that 69% of the analysed particles were plastic, being identified six polymers and two polymeric blends, and 32% were cellulose-based materials. Fibers identified in mussel tissues were mainly composed of cotton and viscose (77%). This study emphasizes the importance of the polymer's spectroscopic identification after microscopic observation to recognise MP.

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.

Nutshells as Efficient Biosorbents to Remove Cadmium, Lead, and Mercury from Contaminated Solutions.

The release of potentially toxic elements into the environment, and their effects on aquatic ecosystems still present a real threat. To avoid such contamination, the use of biological sorbents as an alternative to conventional and expensive water remediation techniques has been proposed. The present study evaluated the potential of 0.5 g L-1 of peanut, hazelnut, pistachio, walnut, and almond shells to remove the requisite concentrations of cadmium (Cd), lead (Pb), and mercury (Hg) from contaminated water. Hazelnut shells were identified as the sorbent with the highest potential and were evaluated in mono- and multi-contaminated mineral water. The influence of sorbent-intrinsic and solution-intrinsic characteristics were assessed. Differences among sorbents were attributed to varying percentages of their main components: cellulose, hemicellulose, and lignin. Matrix complexity increase caused a decrease in Cd removal, presumably due to the diminution in electrostatic interaction, and complexation with anions such as Cl-. When simultaneously present in the solution, contaminants competed, with Pb showing higher affinity to the sorbent than Hg. High efficiencies (>90%) obtained for hazelnut shells for all elements in ultrapure water and for Pb and Hg in mineral water) reveals the high potential of this low-cost and abundant waste for use in the remediation of contaminated waters (circular economy).

Multi-elemental composition of white and dark muscles in swordfish.

Concentrations of 16 elements (K, Na, Mg, Ca, Fe, Zn, Hg, Se, As, Cu, Cd, Mn, Ni, Cr, Pb and Co) were determined in dorsal white and dark muscle of Xiphias gladius, sampled at various positions of a single swordfish and at the same position of eight specimens. Hg was quantified by thermal decomposition atomic absorption spectrometry (LECO AMA-254) and the rest of the elements by inductively coupled plasma optical emission spectrometry (ICP OES) or mass spectrometry (ICP MS). Element partitioning differed in dark and white muscle. Dark muscle was particularly enriched in Fe (median 13 times) and Cu (9) and moderately enhanced in Se, Mn, Zn and Cd (2.8-4.0). Dark:white ratios of the potentially toxic elements (As, Cr, Hg, Ni and Pb) varied from 0.9 to 1.4, pointing to a similar distribution between the two muscles types and indicating no additional risk in the consumption of dark muscle.

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.

Biochemical performance of mussels, cockles and razor shells contaminated by paralytic shellfish toxins.

Marine toxins in bivalves pose an important risk to human health, and regulatory authorities throughout the world impose maximum toxicity values. In general, bivalve toxicities due to paralytic shellfish toxins (PSTs) above the regulatory limit occur during short periods, but in some cases, it may be extended from weeks to months. The present study examines whether cockles (Cerastoderme edule), mussels (Mytilus galloprovincialis) and razor shells (Solen marginatus) naturally exposed to a bloom of Gymnodinium catenatum activated or suppressed biochemical responses as result of the presence of PSTs in their soft tissues. Toxins (C1+2, C3+4, GTX5, GTX6, dcSTX, dcGTX2+3 and dcNEO) and a set of biomarkers (ETS, electron transport system activity; GLY, glycogen; PROT, protein; SOD, superoxide dismutase; CAT, catalase; GPx, glutathione peroxidase; GST, glutathione S-transferases; LPO, lipid peroxidation; reduced (GSH) and oxidized (GSSG) glutathione contents and AChE, acetylcholinesterase activity) were determined in the three bivalve species. Specimens were harvested weekly in Aveiro lagoon, Portugal, along thirteen weeks. This period included three weeks in which bivalve toxicity exceeded largely the regulatory limit and the subsequence recovery period of ten weeks. Biochemical performance of the surveyed species clearly indicated that PSTs induce oxidative stress and neurotoxicity, with higher impact on mussels and razor shells than in cockles. The antioxidant enzymes CAT and GPx seemed to be the biomarkers better associated with toxin effects.

Sorption of okadaic acid lipophilic toxin onto plastics in seawater.

The present study tested under laboratorial conditions the sorption of okadaic acid (OA), a lipophilic toxin produced by marine phytoplankton, onto 6-mm plastic circular fragments. Fragments (4 g L-1) of polyethylene terephthalate (PET), polypropylene (PP), expanded polystyrene (EPS) and non-expanded polystyrene (PS) were exposed for 96 h to seawater spiked with 10 ng mL-1 of OA. Results of the experiments showed a broad percentage of OA removed from the water by plastics after 48 h of exposure: 30 ± 5.1% (PET), 37 ± 9.5% (PP), 62 ± 7.1% (EPS) and 83 ± 1.9% (PS). Sorption appears to be highly influenced by polymer's characteristics, such as polarity and degree of crystallinity. Further studies are needed to clarify the effect of the contact area on sorption by expanded plastics. These results point to the plausible interaction of OA and plastics in coastal waters.

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.

Influence of toxic elements on the simultaneous uptake of rare earth elements from contaminated waters by estuarine macroalgae.

The present study tested whether the presence of potentially toxic elements (PTEs) (Cd, Cr, Cu, Pb, Hg and Ni), commonly found in wastewaters, interferes with the ability of macroalgae (Ulva intestinalis, Ulva lactuca, Fucus spiralis, Fucus vesiculosus, Gracilaria sp. and Osmundea pinnatifida) to remove rare earth elements (REEs) (La, Ce, Pr, Nd, Eu, Gd, Tb, Dy and Y), which are key elements for most high technologies (e.g. electronics, aerospace, renewable energy). Results proved the high capacity of living macroalgae to remove REEs from multielement solutions, with the following sequence of bioconcentration factors being observed: U. intestinalis (2790) > Gracilaria sp. (2119) > O. pinnatifida (1742) > U. lactuca (1548) > F. vesiculosus (944) > F. spiralis (841). Competition among REEs to sorption sites on the six macroalgae was minor due to the chemical similarities between the elements. However, Ce and Y were the less removed while Gd, La and Eu the most removed among REEs. Ionic strength was an important factor in the sorption process, with salinity affecting differently the six macroalgae. Surprisingly, the presence of potential toxic elements in solution enhanced the removal of REEs. The most plausible explanation is the preferentially complexation of those elements by carbonates over REEs, which facilitates the binding of REEs cations onto the surface of macroalgae.