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Salinity modulation of neodymium and dysprosium toxicity in mussels: A comprehensive analysis of adult and sperm responses
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Electrical and electronic equipment reaching the end of its useful life is currently being disposed of at such an alarmingly high pace that raises environmental concerns. Together with other potentially dangerous compounds, electronic waste contains the rare-earth element gadolinium (Gd), which has already been reported in aquatic systems. Additionally, the vulnerability of aquatic species to this element may also be modified when climate change related factors, like increase in temperature, are taken into consideration. Thus, the present study aimed to evaluate the toxicity of Gd under a scenario of increased temperature in Mytilus galloprovincialis mussels. A multi-biomarker approach and Gd bioaccumulation were assessed in mussels exposed for 28 days to 0 and 10 μg/L of Gd at two temperatures (control – 17 °C; increased – 22 °C). Results confirmed that temperature had a strong influence on the bioaccumulation of Gd. Moreover, mussels exposed to Gd alone reduced their metabolism, possibly to prevent further accumulation, and despite catalase and glutathione S-transferases were activated, cellular damage seen as increased lipid peroxidation was not avoided. Under enhanced temperature, cellular damage in Gd-exposed mussels was even greater, as defense mechanisms were not activated, possibly due to heat stress. In fact, with increased temperature alone, organisms experienced a general metabolic depression, particularly evidenced in defense enzymes, similar to the results obtained under Gd-exposure. Overall, this study underlines the importance of conducting environmental risk assessment taking into consideration anticipated climate change scenarios and exposures to emerging contaminants at relevant environmental concentrations.
Growing extraction and usage of rare earth elements and yttrium (REY) for medical and industrial applications has resulted in increased discharges into the marine environment. Using Mytilus spp. Mussels and Tapes spp. clams as bioindicator organisms, we analyzed 15 REY in soft tissues of specimens collected at two potentially polluted sites in Southern Norway: in the vicinity of an industry producing gadolinium-based MRI contrast agents (GBCAs) (Lindesnes) and in an industrially-affected fjord (Porsgrunn). The spatial distribution of REY and shale-normalized fractionation patterns were determined to assess the potential anthropogenic contribution of REY at the sites. At both sites, the REY fractionation pattern in soft tissue was characterized by enrichment of light rare earth elements (LREE) over heavy rare earth elements (HREE), while also displaying negative cerium and small positive gadolinium (Gd) anomalies. LREEs contributed to over 80% of the total REY concentrations, with increasing relative enrichment following higher total REY. Gd anomalies remained conserved in most sites despite significant differences in total REY; however, a high Gd anomaly (Gd/Gd* = 4.4) was found downstream of the GBCA industry spillwater outlet, indicating biotic uptake of excess anthropogenic Gd at this site. Total REY concentrations in clams in Porsgrunn were one order of magnitude higher than in mussels in Lindesnes. This may be attributable to freshwater influences in Porsgrunn, where clams collected closer to the river mouth had significantly higher total REY concentrations. This study constitutes the first assessment of REY concentrations in marine bivalves in Norway and can provide useful information for future biomonitoring studies on REY contamination.
Mercury (Hg) is one of the most hazardous pollutants, due to its toxicity, biological magnification and worldwide persistence in aquatic systems. Thus, new efficient nanotechnologies (e.g. graphene oxide functionalized with polyethyleneimine (GO-PEI)) have been developed to remove this metal from the water. Aquatic environments, in particular transitional systems, are also subjected to disturbances resulting from climate change, such as salinity shifts. Salinity is one of the most relevant factors that influences the distribution and survival of aquatic species such as mussels. To our knowledge, no studies assessed the ecotoxicological impairments induced in marine organisms exposed to remediate seawater (RSW) under different salinity levels. For this, the focus of the present study was to evaluate the effects of seawater previously contaminated with Hg and remediated with GO-PEI, using the species Mytilus galloprovincialis, maintained at three different salinities (30, 20 and 40). The results obtained demonstrated similar histopathological and metabolic alterations, oxidative stress and neurotoxicity in mussels under RSW treatment at stressful salinity conditions (20 and 40) in comparison to control salinity (30). On the other hand, the present findings revealed toxicological effects including cellular damage and histopathological impairments in mussels exposed to Hg contaminated seawater in comparison to non-contaminated ones, at each salinity level. Overall, these results confirm the high efficiency of GO-PEI to sorb Hg from water with no noticeable toxic effects even under different salinities, leading to consider it a promising eco-friendly approach to remediate contaminated water.
Simple Summary
The burbot (Lota lota) is the only endangered or threatened freshwater gadoid that usually spawns in icy waters (<6 °C), and whereas the sperm bioenergetics of many fish species have been studied in the context of adaptation to warmer environments, the sperm of cold-water fish are the least explored. Therefore, this study was undertaken to determine both the roles of the most important energy-supplying pathway(s) in the burbot before and after sperm become motile at the spawning temperature, and the mitochondrial adaptation at the maximum temperature that is tolerable. The results reveal that burbot sperm have a naturally low oxygen consumption rate (respiration) and a limited capacity for enhancement under exposure to an uncoupler. Oxidative phosphorylation is more realized near the critical thermal tolerance limit. However, similar to the sperm of most other freshwater species, this pathway, which occurs during motility, is insufficient to fulfill the large energy demands of the motile sperm. Therefore, be it at the spawning temperature or at a higher temperature, the majority of the energy required for motility is derived from pre-stored ATP reserves produced during a quiescent state.
Abstract
Regarding the sperm of cold-water fish, the contributions of different bioenergetic pathways, including mitochondrial respiration, to energy production at the spawning temperature and its adaptation at the maximum critical temperature (CTmax) are unclear. The roles of glycolysis, fatty acid oxidation, oxidative phosphorylation (OXPHOS) at 4 °C, and OXPHOS at 15 °C for energy production in burbot (Lota lota) spermatozoa were studied by motility and the oxygen consumption rate (OCR) (with and without pathway inhibitors and the OXPHOS uncoupler). At both temperatures, the effects of the inhibitors and the uncoupler on the motility duration, curvilinear velocity, and track linearity were insignificant; in addition, the OCRs in activation and non-activation media differed insignificantly and were not enhanced after uncoupler treatment. After inhibitor treatment in both media, OXPHOS was insignificantly different at the 2, 30, and 60 s time points at 4 °C but was reduced significantly at the 30 and 60 s time points after treatment with sodium azide at 15 °C. In conclusion, for burbot sperm at both the spawning temperature and the CTmax, the energy synthesized via OXPHOS during motility was insufficient. Therefore, the majority of the energy required to sustain motility was derived from pre-accumulated energy produced and stored during the quiescent state of the spermatozoa.
Exposure to a variety of environmental factors such as temperature, pH, oxygen and salinity may influence the oxidative status in aquatic organisms. The present review article focuses on the modulation of oxidative stress with reference to the generation of reactive oxygen species (ROS) in aquatic animals from different phyla. The focus of the review article is to explore the plausible mechanisms of physiological changes occurring in aquatic animals due to altered salinity in terms of oxidative stress. Apart from the seasonal variations in salinity, global warming and anthropogenic activities have also been found to influence oxidative health status of aquatic organisms. These effects are discussed with an objective to develop precautionary measures to protect the diversity of aquatic species with sustainable conservation. Comparative analyses among different aquatic species suggest that salinity alone or in combination with other abiotic factors are intricately associated with modulation in oxidative stress in a species-specific manner in aquatic animals. Osmoregulation under salinity stress in relation to energy demand and supply are also discussed. The literature survey of >50 years (1960–2020) indicates that oxidative stress status and comparative analysis of redox modulation have evolved from the analysis of various biotic and/or abiotic factors to the study of cellular signalling pathways in these aquatic organisms.
Rare earth elements (REEs) have been recently identified as emergent contaminants because of their numerous and increasing applications in technology. The impact of REEs on downstream ecosystems, notably aquatic organisms , is of particular concern, but has to date been largely overlooked. The purpose of this study was thus to evaluate the toxicity of lanthanide metals, lutetium (Lu) and dysprosium (Dy) in rainbow trout after 96 h of exposure. The lethal concentration (LC50) was determined and the expression of 14 genes involved in different pathways such as oxidative stress, xenobiotic detoxification, mitochondrial respiration, DNA repair, protein folding and turnover, inflammation, calcium binding and ammonia metabolism were quantified in surviving fish. In parallel, lipid peroxidation (LPO), DNA damage (DSB), metallothionein level (MT) and cyclooxygenase activity (COX) were examined. The acute 96 h-LC 50 data revealed that Lu was more toxic than Dy (1.9 and 11.0 mg/L, respectively) and was able to affect all investigated pathways by changing the expression of the studied genes, to the exception of superoxide dismutase (SOD), catalase (CAT) and glutathione-S-transferase (GST). It also induced a decrease in DNA repair at concentrations 29 times below the LC 50. This suggests that Lu could trigger a general stress to disrupt the cell homeostasis leading to genotoxicity without promoting oxidative stress. However, Dy induced modulation in the expression of genes involved in the protection against oxidative stress, detoxification, mitochondrial respiration, immunomodulation, protein turnover and an increase in the DNA strand breaks at concentrations 170 times lower than LC 50. Changes in mRNA level transcripts could represent an early signal to prevent against toxicity of Dy, which exhibited inflammatory and genotoxic effects. This study thus provides useful knowledge enhancing our understanding of survival strategies developed by rainbow trout to cope with the presence of lanthanides in the environment.
Nanoparticles are considered potential candidates for a new class of magnetic resonance imaging (MRI) contrast agents. Negative MRI contrast agents require high magnetic moments. However, if nanoparticles can exclusively induce transverse water proton spin relaxation with negligible induction of longitudinal water proton spin relaxation, they may provide negative contrast MR images despite having low magnetic moments, thus acting as an efficient T2 MRI contrast agent. In this study, carbon-coated paramagnetic dysprosium oxide (DYO@C) nanoparticles (core = DYO = DyxOy; shell = carbon) were synthesized to explore their potential as an efficient T2 MRI contrast agent at 3.0 T MR field. Since the core DYO nanoparticles have an appreciable (but not high) magnetic moment that arises from fast 4f-electrons of Dy(III) (⁶H15/2), the DYO@C nanoparticles exhibited an appreciable transverse water proton spin relaxivity (r2) with a negligible longitudinal water proton spin relaxivity (r1). Consequently, they acted as a very efficient T2 MRI contrast agent, as proven from negative contrast enhancements seen in the in vivo T2 MR images.
Current evidence links oxidative stress (OS) to male infertility, reduced sperm motility, sperm DNA damage and increased risk of recurrent abortions and genetic diseases. A review of PubMed, Medline, Google Scholar, and Cochrane review databases of published articles from years 2000–2018 was performed focusing on physiological and pathological consequences of reactive oxygen species (ROS), sperm DNA damage, OS tests, and the association between OS and male infertility, pregnancy and assisted reproductive techniques outcomes. Generation of ROS is essential for reproductive function, but OS is detrimental to fertility, pregnancy, and genetic status of the newborns. Further, there is a lack of consensus on selecting OS test, type, and duration of antioxidants treatment as well as on the target patients group. Developing advanced diagnostic and therapeutic options for OS is essential to improve fertility potential and limit genetic diseases transmitted to offspring.
In the present work, the effects of Dy (dysprosium) additions (0, 0.05, 0.1, 0.15, 0.2, and 0.3wt%) on the microstructure and mechanical properties of hypereutectic Al–Si alloy have been studied. An inductively coupled plasma optical emission spectrometry (ICP-OES) apparatus was employed to measure the alloy composition. The specimens were examined using optical microscopy (OM) and scanning electron microscopy (SEM) equipped with an energy dispersive spectrometer (EDS). In the as-cast state, increasing the Dy content to 0.15% resulted in the refinement of the primary Si morphology from irregular polyhedral and branched shapes to fine polyhedral shapes, with the average size decreasing by 21% from 48 to 38 μm. Additionally, the eutectic Si transformed from coarse, uneven short rod-like structures to fibrous ones. Moreover, the tensile strength increased to 233 MPa, marking an 18.8% improvement, while the elongation reached 1.1%, indicating a significant increase of 267%. After T6 heat treatment, with a Dy content of 0.2%, the size of primary Si and eutectic Si did not change significantly compared with the 0.15% Dy addition. However, the mechanical properties of the alloy were optimized at this Dy content due to the fragmentation of the Al–Si-Fe-Mn phase and Al2Cu phase. The tensile strength increased to 242 MPa, reflecting a 14.7% improvement, and the elongation improved to 1.28%, representing a 60% enhancement compared with the alloy without Dy addition.
Nowadays, it is of utmost importance to consider climate change factors, such as ocean warming, since the risk of negative impacts derived from increased surface water temperature is predicted to be high to the biodiversity. The need for renewable energy technologies, to reduce greenhouse gas emissions, has led to the increasing use of rare earth elements (REE). Dysprosium (Dy) is widely used in magnets, motors, electrical vehicles, and nuclear reactors, being considered a critical element to technology due to its economic importance and high supply risk. However, the increasing use of this element contributes to the enrichment of anthropogenic REE in aquatic systems. Nevertheless, the information on the potential toxicity of Dy is limited. Moreover, the effects of pollutants can be amplified when combined with climate change factors. Thus, this study aimed to assess the effects of Dy (10 μg/L) in the species Mytilus galloprovincialis under actual (17 °C) and predicted warming conditions (21 °C). The Dy concentration in contaminated mussels was similar between temperatures, probably due to the detoxification capacity in individuals under these treatments. The combined stressors affected the redox balance, but higher impacts were caused by Dy and warming acting alone. In terms of cellular damage, although Dy acting alone was prejudicial to mussels, warming and both stressors acting together induced higher levels of LPO and PC. The histopathological effects in the digestive tubules of Dy were independent of the temperature tested. Regarding the sperm, only warming induced cellular damage however both stressors acting alone and together impaired the movement of the sperm. Overall, this study highlights that warming might influence the effects induced by Dy, but greater impacts were caused by the metal. Eventually, the tested stressors may have consequences on mussels' reproduction capacity as well as their growth, abundance, and survival.
The Integrated Biomarker Response (IBR) is one of the most used index in biomonitoring, especially the IBRv2 integrating a reference condition. However, some limitations remain for its routine and large-scale use. The IBRv2 is proportional to the total number of biomarkers, is dependent on the nature of biomarkers and considers all biomarkers modulations, even small and biologically non-significant. In addition, IBRv2 relies on reference values but the references are often different between each study, making it difficult to compare results between studies and/or campaigns. To overcome these limitations, the present work proposed a new index called IBR-T ("Integrated Biomarker Response - Threshold") which considers the threshold values of biomarkers by limiting the calculation of the IBR value to biomarkers with significant modulations. The IBRv2 and the IBR-T were calculated and compared on four datasets from active biomonitoring campaigns using Dreissena polymorpha, a bivalve widely used in freshwater biomonitoring studies. The comparison between indices has demonstrated that the IBR-T presents a better correlation (0.907 < r2 < 0.998) with the percentage of biomarkers significantly modulated than the IBRv2 (0.002 < r2 < 0.759). The IBRv2 could not be equal to 0 (0.915 < intercept <1.694) because the value was dependent on the total number of biomarkers, whereas the IBR-T reached 0 when no biomarker was significantly modulated, which appears more biologically relevant. The final ranking of sites was different between the two index and the IBR-T ranking tends to be more ecologically relevant that the IBRv2 ranking. This IBR-T have shown an undeniable interest for biomonitoring and could be used by environmental managers to simplify the interpretation of large datasets, directly interpret the contamination status of the site, use it to decision-making, and finally to easily communicate the results of biomonitoring studies to the general public.
The impact of pharmaceuticals on marine invertebrates has been a topic of rising concern, with an increasing number of studies regarding the impacts on bivalves. However, very few investigated the toxicity of mixtures of pharmaceuticals. This knowledge gap was investigated in the present study, where the toxicity of 17α-ethinyl estradiol (EE2) and Salicylic acid (SA) mixture was evaluated. To this end, Mytilus galloprovincialis mussels were chronically subjected to both pharmaceuticals, acting alone and in combination, and the effects at the cellular level were measured. The Independent Action (IA) model was performed aiming to compare obtained with predicted responses. The integrated biomarker response (IBR) index was used to assess the overall biochemical response given by mussels. The results obtained revealed that the most stressful condition was caused by the combined effect of EE2 and SA, with the highest metabolic capacity, antioxidant (catalase activity) and biotransformation (carboxylesterases activity) activation and cellular damage in organisms exposed to the mixture of both drugs in comparison to responses observed when each drug was acting alone. Predicted responses obtained from the IA model indicate that caution should be paid as frequent deviations to observed responses were found. This study highlights the need for future studies considering the mixture of pollutants, mimicking the actual environmental conditions.
Climate-associated factors and pollutants, such as rare earth elements (REEs), have been identified as contributors to environmental change. However, the toxicity resulting from the combination of these stressors has received little attention. Neodymium (Nd) is a REE that has been widely used, and this study aimed to evaluate the responses of Mytilus galloprovincialis to Nd exposure (10 µg/L) under actual (17 ºC) and warming conditions (21 ºC) after fourteen days of exposure followed by fourteen days of recovery (without Nd), analyzing Nd accumulation, histopathological and biochemical alterations. The results showed that increased temperature and Nd exposure caused histopathological injuries in the gills. Contaminated mussels at 17 ºC suffer cellular damage, while at 21 ºC, mussels were able to avoid cellular damage. After the recovery period, no improvements in gill’s status were found and cellular damage was still present, highlighting the impacts caused by previous exposure to Nd.
One of the most discussed aspects of the cost-effectiveness sampling of benthic macrofauna is the choice of the sieve mesh size. Although other studies have tested the cost-effectiveness of mesh-size choice, especially in estimating biodiversity, they largely overlook the effect on the perceived species-environment relationship. In this sense, this study aimed to understand the effects of mesh-size choice on the relationship between macrobenthic communities with benthic habitats and environmental gradients. Samples were grouped in biological groups, based on species composition similarity, and in sedimentary habitats, according to environmental variables. Using a 0.5 mm mesh size sieve significantly enhanced the abundance and biodiversity, even at the high taxonomic level of class/order. However, its use did not introduce changes in the identified biological clusters. Distinct biological groups matching distinct sedimentary conditions could only be identified for habitats characterized by predominance of medium silt and coarse sand. Specific biological groups were not found for very fine sand and coarse silt habitats, which can be attributed to transitional fauna or unmeasured variables. This result indicates the need for caution in using benthic habitat mapping as a direct surrogate of species assemblages. Although species composition varied in all biological groups with sieve mesh-size choice, no changes were found in the multivariate relationship between macrobenthic assemblages and environmental variables. In conclusion, sieving through 0.5 mm mesh size should be considered in studies aiming at biodiversity assessments, as the number of species and overall abundance more than doubled in comparison to the 1.0 mm mesh size. However, to study the relationship between biological assemblages and the benthic environment and habitats, we recommend the more cost-effective sieving through a 1.0 mm mesh size.
The geochemistry of rare earth elements (REEs) has been studied for a long time and has allowed us to highlight enrichments or depletions of REEs in aquatic ecosystems and to estimate anthropogenic inputs through normalization of data to different reference materials. This review of current literature on REE normalization highlighted the large number of different reference materials (a total of 12), as well as different anomaly calculation methods. This statement showed a real need for method harmonization to simplify the comparison between studies, which is currently very difficult. Normalization to Post-Archean Australian Shale (PAAS) emerged as being the most used (33 % of reported studies) regardless of the location and the nature of the studied samples and seem to of higher quality. The interest of other reference materials was nevertheless underlined, as they could better represent the geographical situation or the nature of samples. Two main anomaly calculation methods have been highlighted: the linear interpolation/extrapolation and the geometric extrapolation using logarithmic modeling. However, due to variations in the estimation of neighbors' values, these two methods produce many different equations for anomaly calculation of a single element. Current normalization practices based on shales and chondrites are suitable for abiotic samples but are questionable for biota. Indeed, normalization is increasingly used in studies addressing ecotoxicological issues which focus on biota and often aim to estimate the anthropogenic origin of bioaccumulated REEs. Due the interspecific variability, as well as the complexity of mechanisms occurring in organisms when exposed to contaminants, new reference materials need to be established to consider the bioaccumulation/metabolization processes and the anthropogenic inputs of REEs based on the results of biotic samples.
Marine ecosystems are suffering from the gradual rise in temperature due to climate change. Warming scenarios and the intensification of extreme climate events, such as marine heatwaves (MHWs), have been affecting marine organisms. In addition, they are also threatened by anthropogenic pollution. Lithium (Li) is an emerging pollutant that has become a major concern due to its increasing use in a variety of applications. Understanding its influence on marine environments in combination with warming scenarios is crucial, as very little is known about its impact on marine organisms, especially when also considering the increasingly concerning impacts of climate change. With this in mind, this research aims to assess how different scenarios of increasing temperature may affect the response of Mytilus galloprovincialis to Li. Mussels bioaccumulation levels, as well as physiological and biochemical biomarkers were analyzed after 28 days of exposure to Li under different temperature scenarios (control - 17 °C; warming - 21 °C and marine heatwave - MHW). The results indicate that mussels accumulated Li, independently of the temperature scenario. The respiration rate was higher in contaminated mussels than in the non-contaminated ones, with no differences among temperature scenarios. Furthermore, the metabolic rate decreased in non-contaminated mussels exposed to 21 °C and MHW, while mussels exposed to the combination of (Li and MHW) presented the highest metabolic rate. The mussels exposed to MHW and Li evidenced the highest cellular damage but Li was not neurotoxic in M. galloprovincialis. This study highlighted that MHW + Li was the most stressful condition, inducing clear negative effects in this species that can impair the growth and reproduction of an entire population. In general, the present results highlight the importance of future studies in which it is necessary to combine the effects of pollutants and climate change scenarios, namely extreme weather events such as marine heatwaves.
Acid mine drainage (AMD), formed by the instability of sulfides, typically generates acidity and releases potentially toxic elements and sulfate to the environment, among other pollutants. An example is the group of rare earth elements (REE) that may have high toxic behavior. This toxicity leads to degradation of soils, water reservoirs and rivers, promoting serious risks for the ecosystems. So, the main goal of the present work is to study the hydrochemical properties of a system with mine-influenced waters during the rainy season, focusing on the origin, evolution/behavior, and concentration of REE. The study area is the São Domingos mining complex, located in one of the largest metallogenetic provinces in the world (Iberian Pyrite Belt), known by the evidences of AMD contamination. The obtained results reveal extraordinarily low pH (0.4), high electrical conductivity, reaching 26,200 μS/cm, and high values of sulfate and acidity. Regarding the REE, the determined concentration exceeded that observed in normal pH of neutral freshwaters by 2–3 times the order of magnitude. The results revealed that Y and Ce are distinguished in practically all sampled sites, due to its higher concentrations, with maximum values of 221.8 and 166.9 μg/L. In general, the concentrations increase as the water pH decreases. The statistical analysis indicates that REE elements may have a common origin, mutual dependence, and similar behavior during transport with typical AMD elements and composition of host rocks. Most samples show enrichment in middle REE (MREE) (Gdn/Lun), like the classic signature of AMD. In turn, colloids and AMD-precipitates may be participating in the incorporation of these elements. Therefore, due to potential risk of impacts on ecosystems, REE are a topic of relevant interest for future studies in order to assist monitoring processes and help government decisions related to water quality management.
Neodymium-based metal-organic framework (Nd-MOF) has been prepared as an efficient heterogeneous catalyst in the click synthesis of benzylidine-2-phenylhydrazine analogs for the first time. In the presence of Nd-MOF, the reaction proceeds with mild conditions and a comparable yield has been achieved with less reaction time. In order to synthesize the [Nd(NDC)1.5(DMF)(H2O)0.5.0.5DMF]n, neodymium is used as a metal node to act as a cation and naphthalene-2,6-dicarboxylic acid as a well-extended organic linker as a dicarboxylate anion for building good coordinated 3D polymer. The synthesized Nd-MOF nanocatalyst was characterized by Powder XRD, BET, TGA, FT-IR, SEM-EDX, and TEM. Finally, the obtained products were examined through ¹H NMR, ¹³C NMR, ¹⁵N NMR and FT-IR. The nanocatalyst was completely recyclable and reusable for ten cycles without any loss of catalytic efficiency. Further, the nanocatalyst shows a crucial role in reducing the reaction time under mild experimental conditions. Additionally, the target molecules were afforded simple handling, eco-friendly and excellent yields with maximum efficiency.
Dysprosium (Dy) promoted Co/Al2O3 catalysts with different Dy loadings (0-3 wt%) were synthesized via an impregnation approach for methane dry reforming. Promoter addition enhanced the basicity of catalysts owing to the basic attribute of Dy2O3. Co3O4 crystallite sizes were reduced from 8.15 to 6.68 nm with 0.1–0.3 wt%Dy promotion due to the diluting effect, resulting in higher metal dispersion. Particularly, at 973 K, 0.3 wt%Dy appeared as the best promoter loading and achieved the highest CH4 conversion, as well as H2 and CO yields of the corresponding 79.4%, 65.8% and 89.2% because of growing basic site density and the enhancing number of Co active sites. The temperature-programmed oxidation analyses also revealed that 0.3%Dy-10%Co/Al2O3 suppressed carbonaceous deposition from 12.84% to 7.76% since the extra oxygen mobility and redox cycling of Dy2O3 could effectively oxidize surface carbonaceous species to CO and H2.
The level of pollution becomes more and more of a pressuring matter for humankind at a worldwide level. Often the focus is on the effects that we can directly and see such as decreased air quality and higher than normal temperatures and weather, but the effects we cannot see are frequently overlooked. For at least the past decade increasing importance has been given towards the effects of pollution of living animals or non-target organisms and plants. For this purpose, one model animal that surfaced is the purpose, one model animal surfaced is Mytilus galloprovincialis. As all mussels, this species is capable of bio-accumulating important quantities of different xenobiotics such as pesticides, paints, medicines, heavy metals, industrial compounds, and even compounds marketed as antioxidants and antivirals. Their toxic effects can be assessed through their impact on oxidative stress, lysosomal membrane stability, and cell viability through trypan blue exclusion test and neutral red retention assay techniques. The purpose of this paper is to highlight the benefits of using M. galloprovincialis as an animal model for toxicological assays of various classes of xenobiotics by bringing to light the studies that have approached the matter.
In this paper, a Dy³⁺:Ca2Al2SiO7 single crystal was grown successfully by the Czochralski technique. The effective segregation coefficient of Dy³⁺ ions in Dy³⁺:Ca2Al2SiO7 crystal was measured to be 1.12. The crystal's spectroscopic properties were investigated in detail. The absorption cross sections at 452 nm are 1.03 × 10⁻²¹ cm², and 0.98 × 10⁻²¹ cm² with the full width at half maximum 10.79 and 4.89 nm for π- and σ-polarizations, respectively. Based on the Judd-Ofelt theory, the radiative transition probabilities, fluorescence branching ratios, and radiative lifetime of Dy³⁺:Ca2Al2SiO7 crystal were obtained. The emission cross sections at 574 nm are 13.82 × 10⁻²¹ cm², and 8.33 × 10⁻²¹ cm² for π- and σ-polarizations, respectively. The fluorescence decay time of ⁴F9/2 multiplet is 334.9 μs, and the fluorescence quantum efficiency is 58.6%. These results show that Dy³⁺:Ca2Al2SiO7 crystal is a promising yellow laser material suitable for commercial 450 nm blue laser diode pumping.
Increased Rare earth elements (REE) usage culminates in discharges into the environment. Mussels have been chosen as models in biomonitoring, hence, REE concentrations in Mytilus galloprovincialis from six locations on the Portuguese coast were accessed to determine natural concentrations and possible linkage to local ecosystem characteristics and temporal variations, by determining them in distinct seasons (autumn and spring). Samples from Porto Brandão (located on the south bank of the Tagus estuary) exhibited the highest REE concentrations, while mussels from Aljezur (the southernmost point on the Portuguese coast) exhibited the lowest, in both seasons. Overall, ∑REE concentration was greater in the spring. LREE enrichment relative to HREE occurs and a negative Ce and Eu anomaly was observed. This study constitutes the first assessment of REE composition on this model species in the Portuguese coast, in two distinct seasons and contributes to a better understanding of REE uptake for future biomonitoring studies.
The increase of the worlds' population is being accompanied by the exponential growth in waste of electrical and electronic equipment (e-waste) generation as a result of the rapid technological implementations. The inappropriate processing and disposal of this e-waste, containing rare-earth elements (REEs) such as gadolinium (Gd), may enhance its occurrence in the environment. In particular, the presence of Gd in marine systems may lead to environmental risks which are still unknown, especially considering foreseen climate modifications such as water salinity shifts due to extreme weather events. Within this context, the present study intended to assess the combined effects of Gd at variable salinities. For that, biochemical modifications were assessed in mussels, Mytilus galloprovincialis, exposed to Gd (0 and 10 μg/L) and different salinity levels (20, 30 and 40), acting individually and in combination. A decrease in salinity, induced an array of biochemical effects associated to hypotonic stress in non-contaminated and contaminated mussels, including metabolism, antioxidant and biotransformation defenses activation. Moreover, in Gd-contaminated organisms, the increase in salinity was responsible for a significant reduction of metabolic and defense mechanisms, possibly associated with a mussels’ physiological response to the stress caused by the combination of both factors. In particular, Gd caused cellular damage at all salinities, but mussels adopted different strategies under each salinity to limit the extent of oxidative stress. That is, an increase in metabolism was associated to hypotonic stress and Gd exposure, an activation of defense enzymes was revealed at the control salinity (30) and a decrease in metabolism and non-activation of defenses, associated with a possible physiological defense trait, was evidenced at the highest salinity. The different strategies adopted highlight the need to investigate the risk of emerging contaminants such as REEs at present and forecasted climate change scenarios, thus providing a more realistic environmental risk assessment.
The multiplicity and wide variety of applications of electrical and electronic equipment has largely increased with the technological and economic progress and, in consequence, the amount of generated waste of electrical and electronic equipment (WEEE). Due to inappropriate processing and disposal of WEEE, different chemical elements and compounds, including rare-earth elements such as Lanthanum (La) have been released in the environment. Nevertheless, the environmental risks resulting from La presence are almost unknown, especially in marine systems, which may be challenged by foreseen climate changes such as water salinity shifts. Within this context, the present study aimed to understand the combined effects of salinity and La by assessing biochemical alterations in mussels Mytilus galloprovincialis exposed to La (0 and 10 μg/L) at different salinity levels (20, 30 and 40). A decrease in salinity caused a wide range of biochemical changes to both non-contaminated and contaminated organisms, such as metabolism, antioxidant and biotransformation defenses activation, associated to hypotonic stress. Furthermore, the decrease in salinity enhanced the effects of La exposure seen as an increase on lipid and protein cellular damage in those exposed, probably due to free metal ions increase at lower salinities, resulting in a higher bioaccumulation and toxicity. In general, La exposure caused cellular damage and inhibition of antioxidant defenses in contaminated mussels when compared to non-contaminated ones, with cellular damages being higher at the lowest salinity. Overall, the present study highlights the need to investigate the presence and impacts of emerging contaminants of WEEE source at environmental relevant concentrations, not just at present but also under forecasted climate change scenarios, thus providing a more realistic environmental risk assessment.
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 U. 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, Ulva 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.
In the present study, the combined effects of pH, dissolved oxygen (DO) and temperature levels on the antiox-idant responses of the mussel Mytilus coruscus were evaluated. Mussels were exposed to two pH (8.1, 7.7-acidi-fication), two DO (6 mg L − 1 , 2 mg L − 1-hypoxia) and two temperature levels (20 • C, 30 • C-warming) for 30 days. SOD, CAT, MDA, GPx, GSH, GST, TAOC, AKP, ACP, GPT, AST levels were measured in the gills of mussels. All tested biochemical parameters were altered by these three environmental stressors. Values for all the test parameters except GSH first increased and then decreased at various experimental treatments during days 15 and 30 as a result of acidification, hypoxia and warming. GSH content always increased with decreased pH, decreased DO and increased temperature. PCA showed a positive correlation among all the measured biochemical indexes. IBR results showed that M. coruscus were adversely affected by reduced pH, low DO and elevated temperature.
The presence of pharmaceuticals in the marine environment is a growing problem of global importance. Although awareness of the significance of this issue is increasing, many questions related to the ecotoxicology of pharmaceuticals remain unclear. Diclofenac is one of the drugs most commonly detected in the marine environment and its potential toxicity has been previously highlighted, thus its impact on organisms deserves a special attention. Therefore, in this study, a thorough analysis of the effects of diclofenac on a condition and tissue level of a model representative of marine invertebrates - Mytilus trossulus - was performed. During the 25-day experiment, divided into exposure and depuration phases, bivalves were exposed to two environmentally relevant drug concentrations of 4 and 40 μg/L. The study showed that mussels absorb diclofenac in their tissues and the highest recorded concentration was 1.692 μg/g dw on day 8. Moreover, the content of diclofenac metabolites (4-OH and 5-OH diclofenac) was also examined, but they were not detected either in water or in tissues. Although exposure to low diclofenac concentrations did not significantly affect the condition index of organisms, changes in numerous histopathological parameters were noted. Performed histological examination provided additional valuable information on the influence of drugs on the functioning of invertebrates. Nevertheless, applicability of histopathological techniques in ecotoxicology of drugs requires additional evaluation in future studies.
The use of carbon nanotubes (CNTs) is rapidly increasing and several scientific studies have addressed their toxicological properties. However, only a very small number of publications have deal with the interaction between CNTs and other molecules. Triclosan (TCS) is an antibacterial agent used in personal care and household products. Commonly detected in aquatic ecosystems, there is a strong evidence that aquatic biota is sensitive to this compound. Aside from emergent pollutants, aquatic organisms are continuously subjected to abiotic variations including salinities. Therefore, the main goal of the present study was to better understand how physio-chemical interactions of CNTs with TCS under different salinity levels (37, 28 and 19) affect the mussel species Mytilus galloprovincialis through the evaluation of biochemical alterations on gametes (sperms) and adult tissues, providing more ecologically relevant information on organisms' responses. The results showed toxicological effects in terms of sperm metabolic activity and intracellular reactive oxygen species production as well as cellular damage and alteration of metabolic capacity at the adult's stage when exposed to both contaminants acting alone and in combination, under tested salinities. Moreover, when the mussels were exposed to the combination of both contaminants, they showed major toxic impacts on both assessed biological levels (adult tissues and sperms) especially under control salinity. This suggests that toxicity upon mixture exposure compared to single-substance exposure may impair mussels' populations, affecting reproduction success and growth.
The rare earth element (REE) contamination of urban wastewater, which was collected from open sewers and the inlet of a wastewater treatment plant in Cotonou (Benin), was assessed. The drinking water distributed to the inhabitants of Cotonou and water samples from private wells were also analyzed. The sampling occurred between October and December 2016 and the samples were analyzed by ICP-MS. Although the only magnetic resonance imaging facility in Cotonou opened in November 2016, pollution by anthropogenic gadolinium (Gd), which is included in phase contrast agents, was observed: there was 30–620 times more Gd in wastewater samples than in drinking and well water samples. Europium was another REE presenting positive anomalies. It is hypothetized than the europium came from the leachates of solid waste piles in the street. In the absence of any wastewater treatment, the REEs found in the wastewater are spread to the aquatic environment. It would be interesting to monitor the wastewater REEs over the long term. So far, the aquifers used for water provision have not been polluted by the anthropogenic REEs.
With the technological advances and economic development, the multiplicity and wide variety of applications of electrical and electronic equipment have increased, as well as the amount of end-of-life products (waste of electrical and electronic equipment, WEEE). Accompanying their increasing application, there is an increasing risk to aquatic ecosystems and inhabiting organisms. Among the most common elements present in WEEE are rare earth elements (REE) such as Dysprosium (Dy). The present study evaluated the metabolic and oxidative stress responses of mussels Mytilus galloprovincialis exposed to an increasing range of Dy concentrations, after a 28 days experimental period. The results obtained highlighted that Dy was responsible for mussel's metabolic increase associated with glycogen expenditure, activation of antioxidant and biotransformation defences and cellular damage, with a clear loss of redox balance. Such effects may greatly impact mussel's physiological functions, including reproduction capacity and growth, with implications for population conservation. Overall the present study pointed out the need for more research on the toxic impacts resulting from these emerging pollutants, especially towards marine and estuarine invertebrate species.
The wide range of applications of rare earth elements (REE) is leading to their occurrence in worldwide aquatic environments. Among the most popular REE is Neodymium (Nd), being widely used in permanent magnets, lasers, and glass additives. Neodymium-iron-boron (NdFeB) magnets is the main application of Nd since they are used in electric motors, hard disk drives, speakers and generators for wind turbines. Recent studies have already evaluated the toxic potential of different REE, but no information is available on the effects of Nd towards marine bivalves. Thus, the present study evaluated the biochemical alterations caused by Nd in the mussel Mytilus galloprovincialis exposed to this element for 28 days. The results obtained clearly demonstrated that Nd was accumulated by mussels, leading to mussel's metabolic capacity increase and GLY expenditure, in an attempt to fuel up defense mechanisms. Antioxidant and biotransformation defenses were insufficient in the elimination of ROS excess, resulting from the presence of Nd and increased electron transport system activity, which caused cellular damages (measured by lipid peroxidation) and loss of redox balance (assessed by the ratio between reduced and oxidized glutathione). The results obtained clearly highlight the potential toxicity of REEs and, in particular of Nd, with impacts at cellular level, which may have consequences in mussel's survival, growth and reproduction, affecting mussel's population.
Titanium dioxide (TiO2) particles have been widely used in various industrial applications and consumer products. Due to their large production and use, they will eventually enter into aquatic environments. Once in the aquatic environment TiO2 particles may interact with the organisms and induce toxic effects. Since the most common crystallographic forms of TiO2 are rutile and anatase, the present study evaluated the effect of these two forms of TiO2 particles in Mytilus galloprovincialis. For this, mussels were exposed to different concentrations of rutile and anatase particles (0, 5, 50, 100 µg/L) for twenty-eight days. Ti concentrations, histopathological alterations and biochemical effects were evaluated. Similar Ti concentrations were found in mussels exposed to rutile and anatase, with the highest values in mussels exposed to the highest exposure concentration. Histopathological results demonstrated that both forms of TiO2 induced alterations on gills and digestive glands along the increasing exposure gradient. Biochemical markers showed that mussels exposed to rutile maintained their metabolic capacity (assessed by the activity of the Electron Transport System, ETS), while anatase increased the metabolism of mussels. Mussels exposed to rutile increased their detoxifying defences which, due to the low tested concentrations, were sufficient to avoid cellular damage. On the other hand, mussels exposed to anatase suffered cellular damages despite the increase of the antioxidant defences which may be related to the high ETS activity. Both rutile and anatase particles were toxic to M. galloprovincialis, being the highest oxidative stress exerted by the crystalline form anatase.
Mussels, such as the marine bivalve Mytilus galloprovincialis are sentinels for marine pollution but they are also excellent bioindicators under laboratory conditions. For that, in this study we tested the modulation of biochemical responses under realistic concentrations of the toxic metal Lead (Pb) in water for 28 days under different conditions of salinity and temperature, including control condition (temperature 17 ± 1.0 °C and salinity 30 ± 1.0) as well as those within the range expected to occur due to climate change predictions (± 5 in salinity and + 4 °C in temperature). A comprehensive set of biomarkers was applied to search on modulation of biochemical responses in terms of energy metabolism, energy reserves, oxidative stress and damage occurrence in lipids, proteins as well as neurotoxicity signs. The application of an integrative Principal Coordinates Ordination (PCO) tool was successful and demonstrated that Pb caused an increase in the detoxification activity mainly evidenced by glutathione S-transferases and that the salinities 25 and 35 were, even in un-exposed mussels, responsible for cell damage seen as increased levels of lipid peroxidation (at salinity 25) and oxidised proteins (at salinity 35).
Samarium (Sm) and yttrium (Y) are commonly used rare earth elements (REEs) but there is a scarcity of information concerning their biological effects in non-target aquatic organisms. The purpose of this study was to determine the bioavailability of those REEs and their toxicity on Dreissena polymorpha after exposure to increasing concentration of Sm and Y for 28 days at 15 °C. At the end of the exposure period, the gene expression of
superoxide dismutase (SOD), catalase (CAT), metallothionein (MT), glutathione S-transferase (GST), cytochrome c oxidase 1 (CO1) and cyclin D (Cyc D) were analysed. In addition, we examined lipid peroxidation (LPO), DNA strand breaks (DSB), GST and prostaglandin cyclooxygenase (COX) activities. Results showed a concentration dependent increase in the level of the REEs accumulated in the soft tissue of mussels. Both REEs decreased CAT but did not significantly modulated SOD and MT expressions. Furthermore, Sm3+ up-regulated GST, CO1 and Cyc D, while Y3+ increased and decreased GST and CO1 transcripts levels, respectively. Biomarker activities showed no oxidative damage as evidenced by LPO, while COX activity was decreased and DNA strand breaks
levels were changed suggesting that Sm and Y exhibit anti-inflammatory and genotoxic effects. Factorial analysis revealed that the major impacted biomarkers by Sm were LPO, CAT, CO1 and COX, while GST gene expression, COX, Cyc D and CAT as the major biomarkers affected by Y. We conclude that these REEs display different mode
of action but further investigations are required in order to define the exact mechanism involved in their toxicity.
Control strategies and routine biomonitoring programs are commonly performed worldwide using sentinel marine invertebrates, such as mussels of the genus Mytilus, for assessing the "health status" of the aquatic environment. Those species can accumulate and tolerate xenobiotics at levels higher than those being present into the aquatic environment, thus providing accurate and reliable biological endpoints (e.g. physiological, behavioral, cellular, biochemical and molecular indices) that can be measured in their tissues. Taking under consideration the significance of bivalves for assessing the environmental hazard of xenobiotics being present into the water medium, as well as the key role of digestive gland as a target-tissue for the compounds ingested in the organism, the present study aimed to summarize available data on the effects of different categories of xenobiotic compounds, previously characterized as a potential threat for the marine ecosystems. In this context, different types of pharmaceuticals and personal care products (PPCPs), biocides, microplastics (MPs) and nanoparticles (NPs), currently investigated in mussels' digestive gland, using a battery of experimental approaches and analytical methods, as well as stress indices evaluation, are briefly described and further discussed in order to elucidate not only the presence and the toxic mode of action of xenobiotics, but also the important role of the digestive gland as a reliable target-tissue for investigating the effects of xenobiotics at cellular, biochemical, and molecular levels.