Ecotoxicological assessments of atmospheric biomonitors exposed to urban pollution in a Brazilian metropolis.

Subcellular metal distribution assessments are the most adequate biomonitoring approach to evaluate metal toxicity, instead of total metal assessments This study aimed to assess subcellular metal distributions and associations to the main metal exposure biomarker, metallothionein (MT), in two bromeliad species (Tillandsia usneoides and Tillandsia stricta) exposed established in industrial, urban, and port areas in the metropolitan region of Rio de Janeiro, southeastern Brazil, through an active biomonitoring approach conducted one year. Metals and metalloids in three subcellular fractions (insoluble, thermolabile and thermostable) obtained from the MT purification process were determined by inductively coupled plasma mass spectrometry (ICP-MS). Lower MT concentrations were observed both during the dry sampling periods, associated to the crassulacean acid metabolism (CAM) and during the COVID-19 pandemic, due to reduced urban mobility, decreasing pollutant emissions. The percentage of non-bioavailable metals detected in the insoluble fraction increased throughout the sampling period for both species. Several metals (Cr, Co, Cu, Cd, Mn, Ni, Se, and Zn), most associated with vehicle emissions, the main pollutant source in urban centers, were detected in the thermostable fraction and are, thus, associated with MT through the MT-metal detoxification route. Insoluble metal concentrations were higher in T. stricta, indicating that this species seems less susceptible to cellular metal exposure damage. A potential protective effect of Se and Fe was detected against Pb, suggested by a strong negative correlation, which may be attributed to antioxidant roles and similar uptake routes, respectively.

Disruption of a three-component solution as a novel strategy for Cu and Ni extraction from vegetable oils for their determination by GF AAS.

In this work, we propose a novel approach for extracting Cu and Ni from vegetable oils (which can be expanded to other metals). The method is based on the transference of the analytes to an aqueous acid phase due to the disruption of a three-component solution. The extraction was carried out in two steps. In the first step, a three-component solution was prepared comprising the sample, 1-octanol, and HNO3 solution. Next, the homogeneous system was disrupted by adding 1.0 mL of deionized water, and two phases were formed. The aqueous extract deposited in the bottom of the flask was collected with a micropipette, and Cu and Ni were determined by graphite furnace atomic absorption spectrometry (GF AAS). The developed method presented limits of quantification (LOQ) of 0.25 and 0.17 ng g-1 for Cu and Ni, respectively, and was successfully applied in the analysis of eleven oil samples from different origins.

Coastal upwelling influences population structure of dusky grouper Epinephelus marginatus: An integrative approach based on otolith chemistry and muscle stable isotopes.

The dusky grouper (Epinephelus marginatus) is an overfished and threatened fish species with coastal distribution. In the Southwestern Atlantic, it occurs across a broad region influenced by two major oceanographic features: the Cabo Frio (23°S) and the Cabo Santa Marta (28°S) upwelling systems. Along the Brazilian coast, the species may present continuous or discrete populations, depending on the methodological approach used. In this study we combined otolith chemistry and muscle stable isotope analyses to examine the population structure of dusky groupers and its association with the two upwelling systems. Fish were collected in shallow coastal waters of the Southwest Atlantic Ocean, covering the southeastern and southern Brazilian coasts, among Macaé (22°S), Santos (24°S), Florianópolis (27°S), and in Rio Grande (32°S). The results show three statistically well-separated population groups along the region. We named these population groups as North (north of Cabo Frio); Center (between upwelling regions); and South (south of the Cabo Santa Marta system). Our findings allow to suggest that the upwelling systems may influence the distribution of E. marginatus stocks along the Brazilian south-western coast, even though a causal effect may not be attributed at this point. Overall, this combined approach, leveraging information from distinct natural tags, and reflecting variability of water chemistry and food webs with latitude, allowed us to enhance our understanding on how major upwelling systems influence the structuring of fish populations along the southwestern Atlantic Ocean.

First metal and metalloid study assessment for the Black Triggerfish Melichthys niger (Bloch, 1786): Baseline data from a pristine South Atlantic oceanic island.

Metal and metalloid concentrations in Black Triggerfish, Melichthys niger (Tetraodontiformes, Balistidae), and sediments from Trindade Island, an isolated, pristine, and understudied environment in the Southwestern Atlantic Ocean were determined. Several elements were detected in sediment, including Rare Earth Elements (REE). Hg and the REE Nd were, however, not detected. Elements determined in triggerfish are indicative of systemic circulation and the presence of toxic elements indicates an exposure source. No significant associations were detected between elements in fish organs and total length, suggesting no bioaccumulation with age, nor between organs and sediment, indicating probable dietary origin. Biliary excretion indicated a local chronic source of As and Cd and non-quantifiable REE elimination. Hg concentrations were over thresholds that affect fish biochemistry processes. These baseline data are valuable concerning elemental contamination in remote oceanic islands, with the potential to be applied to future biomonitoring efforts and conservation measures for reef ecosystems worldwide.

Metal exposure and oxidative stress biomarkers in a Brazilian agricultural community.

We examined the association between exposure to metals, metalloids, and oxidative stress biomarkers among rural community residents in Brazil. Multiple linear regression was used to evaluate associations between serum metal and metalloid concentrations and blood oxidative stress biomarkers, adjusting for sex, age, education, smoking, and alcohol use. After adjustment for covariates, glutathione peroxidase activity (GPx) was inversely and significantly associated with an increase in serum arsenic (As) levels. Positive and significant associations were seen between elevated glutathione reductase (GR) activity and serum cadmium (Cd), barium (Ba), and lead (Pb) concentrations. In addition, we observed a significant increase in malondialdehyde (MDA) levels in association with an increase in Ba levels. These findings suggest that toxic metals and metalloids such as As, Ba, Cd, and Pb alter antioxidant enzyme activities. In addition, Ba seems to promote lipid peroxidation.

A Review on Atmospheric Analysis Focusing on Public Health, Environmental Legislation and Chemical Characterization.

Atmospheric pollution has been considered one of the most important topics in environmental science once it can be related to the incidence of respiratory diseases, climate change, and others. Knowing the composition of this complex and variable mixture of gases and particulate matter is crucial to understand the damages it causes, help establish limit levels, reduce emissions, and mitigate risks. In this work, the current scenario of the legislation and guideline values for indoor and outdoor atmospheric parameters will be reviewed, focusing on the inorganic and organic compositions of particulate matter and on biomonitoring. Considering the concentration level of the contaminants in air and the physical aspects (meteorological conditions) involved in the dispersion of these contaminants, different approaches for air sampling and analysis have been developed in recent years. Finally, this review presents the importance of data analysis, whose main objective is to transform analytical results into reliable information about the significance of anthropic activities in air pollution and its possible sources. This information is a useful tool to help the government implement actions against atmospheric air pollution.

Arsenic contamination in widely consumed Caribbean sharpnose sharks in southeastern Brazil: Baseline data and concerns regarding fisheries resources.

Although shark meat is consumed worldwide, elevated arsenic (As) concentrations have been increasingly reported. The Caribbean sharpnose shark (Rhizoprionodon porosus) is a widely consumed fishing resource in Brazil, with scarce information on As burdens to date. Herein, commercial-sized juvenile Caribbean sharpnose sharks from Rio de Janeiro (Brazil) were assessed in this regard, presenting significantly higher hepatic As concentrations in males (8.24 ± 1.20 mg kg-1 wet weight; n = 12) compared to females (6.59 ± 1.87 mg kg-1 w.w.; n = 8), and a positive correlation (r = 0.74) was noted between female muscle and liver As concentrations, indicating systemic inter-tissue transport not evidenced in males. Arsenic concentrations were over the maximum permissible As limit established in Brazilian legislation for seafood and calculated Target Hazard Quotients suggest consumption risks, although cancer risks were not evidenced. Therefore, Public Health concerns with regard to Caribbean sharpnose shark As burdens deserve careful attention.

Biochemical metal accumulation effects and metalloprotein metal detoxification in environmentally exposed tropical Perna perna mussels.

Marine bivalves have been widely applied as environmental contamination bioindicators, although studies concerning tropical species are less available compared to temperate climate species. Assessments regarding Perna perna mytilid mussels, in particular, are scarce, even though this is an extremely important species in economic terms in tropical countries, such as Brazil. To this end, Perna perna mytilids were sampled from two tropical bays in Southeastern Brazil, one anthropogenically impacted and one previously considered a reference site for metal contamination. Gill metallothionein (MT), reduced glutathione (GSH), carboxylesterase (CarbE) and lipid peroxidation (LPO) were determined by UV-vis spectrophotometry, and metal and metalloid contents were determined by inductively coupled plasma mass spectrometry (ICP-MS). Metalloprotein metal detoxification routes in heat-stable cellular gill fractions were assessed by size exclusion high performance chromatography (SEC-HPLC) coupled to an ICP-MS. Several associations between metals and oxidative stress endpoints were observed at all four sampling sites through a Principal Component Analysis. As, Cd, Ni and Se contents, in particular, seem to directly affect CarbE activity. MT is implicated in playing a dual role in both metal detoxification and radical oxygen species scavenging. Differential SEC-HPLC-ICP-MS metal-binding profiles, and, thus, detoxification mechanisms, were observed, with probable As-, Cu- and Ni-GSH complexation and binding to low molecular weight proteins. Perna perna mussels were proven adequate tropical bioindicators, and further monitoring efforts are recommended, due to lack of data regarding biochemical metal effects in tropical species. Integrated assessments, as performed herein demonstrate, are invaluable in evaluating contaminated aquatic environments, resulting in more accurate ecological risk assessments.

Rationally designed dipicolinate-functionalized silica for highly efficient recovery of rare-earth elements from e-waste.

Composition of the immobilized layer plays a crucial role in metal adsorption properties of complexing organo-mineral materials. Ignoring the specific features of chemical reactions on solid surface can lead to a significant deterioration in the target properties of the resulted materials. In this research we demonstrated that rationally designed surface-assembling synthesis of organo-silica with covalently immobilized fragments of dipicolinic acid (DPA) resulted in the adsorbent that is capable quantitively recover almost all Rare Earth elements (REEs) from multielement solution with pH > 1.7. In ten consecutive adsorption/desorption cycles no noticeable loss of its efficiency was found, with a mean value of REEs recovery larger than 97%. The adsorbent has been used to recover REEs from model solutions (22 metal ions in 0.5 mol L-1 NaCl) and real leaching solution of waste of fluorescent lamps. It was demonstrated that even 3200-fold excess of Fe and Cu ions only slightly reduces REEs recovery. The adsorbent is capable to recover above 80% of all (except La) REEs from acidic leaching solution from fluorescent lamps with enrichment factors above 600. After adsorption of Eu3+ and Tb3+, the resulting materials exhibited strong red and green luminescence, respectively, indicating chelating mechanism of REEs adsorption on SiO2-DPA.

Contamination and oxidative stress biomarkers in estuarine fish following a mine tailing disaster.

BACKGROUND: The Rio Doce estuary, in Brazil, was impacted by the deposition of iron mine tailings, caused by the collapse of a dam in 2015. Based on published baseline datasets, the estuary has been experiencing chronic trace metal contamination effects since 2017, with potential bioaccumulation in fishes and human health risks. As metal and metalloid concentrations in aquatic ecosystems pose severe threats to the aquatic biota, we hypothesized that the trace metals in estuarine sediments nearly two years after the disaster would lead to bioaccumulation in demersal fishes and result in the biosynthesis of metal-responsive proteins. METHODS: We measured As, Cd, Cr, Cu, Fe, Mn, Pb, Se and Zn concentrations in sediment samples in August 2017 and compared to published baseline levels. Also, trace metals (As, Cd, Cr, Cu, Fe, Hg, Mn, Pb, Se and Zn) and protein (metallothionein and reduced glutathione) concentrations were quantified in the liver and muscle tissues of five fish species (Cathorops spixii, Genidens genidens, Eugerres brasilianus, Diapterus rhombeus and Mugil sp.) from the estuary, commonly used as food sources by local populations. RESULTS: Our results revealed high trace metal concentrations in estuarine sediments, when compared to published baseline values for the same estuary. The demersal fish species C. spixii and G. genidens had the highest concentrations of As, Cr, Mn, Hg, and Se in both, hepatic and muscle, tissues. Trace metal bioaccumulation in fish was correlated with the biosynthesis of metallothionein and reduced glutathione in both, liver and muscle, tissues, suggesting active physiological responses to contamination sources. The trace metal concentrations determined in fish tissues were also present in the estuarine sediments at the time of this study. Some elements had concentrations above the maximum permissible limits for human consumption in fish muscles (e.g., As, Cr, Mn, Se and Zn), suggesting potential human health risks that require further studies. Our study supports the high biogeochemical mobility of toxic elements between sediments and the bottom-dwelling biota in estuarine ecosystems.

Total and subcellular Ti distribution and detoxification processes in Pontoporia blainvillei and Steno bredanensis dolphins from Southeastern Brazil.

Titanium (Ti), used in many dailyuse products, such as shampoos and sunscreen filters, in the form of TiO2 nanoparticles (NPs), may elicit adverse marine biota effects. Marine mammal Ti data is scarce, and subcellular distribution and detoxification information is non-existent. Ti concentrations and metalloprotein detoxification in Pontoporia blainvillei and Steno bredanensis dolphins from Southeastern Brazil were assessed. Metallothionein (MT) concentrations were determined spectrophotometrically, total and subcellular Ti, by ICP-MS and detoxification, by HPLC-ICP-MS. Ti detoxification occurred through MT complexation. Statistical Ti-MT associations were observed in S. bredanensis liver, indicating TiO2 NPs contamination, as Ti binds to MT only as NPs. MT-Ti correlations were observed for both the coastal (P. blainvillei) and offshore (S. bredanensis) dolphins, evidencing oceanic TiO2 diffusion. Ti detoxification through binding to reduced glutathione occurred in both species. Thermostable subcellular fractions are a valuable tool for cetacean Ti detoxification assessments and should be applied to conservation efforts.

Coastal zone use and migratory behaviour of the southern population of Mugil liza in Brazil.

We analysed the ratios Sr:Ca and Ba:Ca in the otoliths of 55 adults of the southern population of Mugil liza in Brazil (Paraná to Rio Grande do Sul) to investigate its coastal zone use and migratory behaviour. All individual M. liza analysed had Sr:Ca and Ba:Ca values indicating that their birth was in the marine environment, which is consistent with the southern population migration to spawn in the ocean,. Juveniles exhibited at least three coastal use and recruitment strategies (contingents): the majority (89%) of M. liza juveniles migrated toward brackish water. They entered the estuary before completing the first year of life (64%) or after (25%) their first year of life. The remaining 11% did not appear to enter brackish or freshwater water as a nursery or at any point in their life cycle. Some adults returned to the estuary after spawning in the ocean but others (of both sexes) never returned to the estuary after spawning, remaining in the marine environment. The pattern of juvenile habitat use in the Brazilian southern population of M. liza seems to be recurrent throughout the extent of its distribution as a consequence of the reproductive spawning aggregation behaviour, which mixes all contingents (with marine or estuarine preferences).

Subcellular metal distributions and metallothionein associations in rough-toothed dolphins (Steno bredanensis) from Southeastern Brazil.

Metals are subject to internal subcellular compartmentalization, altering their bioavailability. Thus, subcellular metal assessments are crucial in biomonitoring efforts. Metal distribution in three subcellular fractions (insoluble - ISF, thermolabile - TLF and thermostable - TSF) were determined by ICP-MS in Steno bredanensis specimens from Southeastern Brazil. Associations between metals, metallothionein (MT) and reduced glutathione (GSH) were also investigated. Differential metal-detoxification mechanisms were observed. MT detoxification was mostly noted for As, Cd, and Pb, while Cu, Cr, Hg, Ni, Se and Ti displayed lower MT-associations. Fe, Zn and Se, on the other hand, were poorly associated to MT, and mostly present in the ISF, indicating low bioavailability. This is the first report on subcellular Sn and Ti distribution in cetaceans and the first in this species in Brazil. Potential protective roles of essential metals against toxic elements are postulated. This study indicates that important biochemical detoxification information is obtained through subcellular fraction analyses in marine mammals.

Leave forever or return home? The case of the whitemouth croaker Micropogonias furnieri in coastal systems of southeastern Brazil indicated by otolith microchemistry.

Movements of coastal fish species between estuarine systems (rearing grounds) and adjacent platforms (spawning grounds) are complex and can be influenced by multiple biotic and abiotic factors associated with the life cycle of each species. Understanding fish movement patterns between these habitats is crucial for sustainable management of these resources. We aimed to identify movement patterns of the whitemouth croaker Micropogonias furnieri, an important fishery resource along the southeastern Brazilian coast, through characterization of elemental concentration profiles in otoliths. Signal intensity ratios of Sr86:Ca43 and Ba138:Ca43, measured by a Laser ablation inductively coupled to a plasma mass spectrometry (LA-ICPMS), were analysed. Juveniles and adults fish from three semi-enclosed systems (two bays and one coastal lagoon) and adults from nine adjacent coastal areas were examined. Three main behavioural patterns were identified: 1) Marine Migrant, with a unique and definitive movement from the estuarine area towards the adjacent platform when adult; 2) Estuarine Visitor, with movements from the estuarine area towards the adjacent platform when adult but also performing excursions back to the estuarine areas and back again to the adjacent platform; and 3) Nearshore Resident, with occurrence in the adjacent coastal areas that are influenced by estuarine systems. Estuarine areas with large sea connections (e.g., bays) favour more frequent fish entrances and exits compared with coastal lagoons that have a narrow sea connection. The high eurioic condition and capacity related to adapting to different environmental conditions were detected in this study for M. furnieri, a likely strategy to maintain variation in life histories and successfully adapt to coastal marine systems.

Biliary and hepatic metallothionein, metals and trace elements in environmentally exposed neotropical cichlids Geophagus brasiliensis.

One of the metal detoxifying mechanisms that occurs in fish is metallothionein (MT) induction and metal binding. Hepatic MT induction has been well described, but biliary MT metal detoxification has only recently been described in fish. In this scenario, metal-metal interactions have been increasingly evaluated to further understand the behavior of these contaminants regarding homeostasis and biological functions, as well as their toxic effects. Studies, however, have been mainly conducted concerning the elemental pair Se-Hg, and scarce reports are available concerning other metal pairs. Therefore, this study aimed to evaluate biliary and hepatic MT metal detoxification mechanisms in a territorial neotropical cichlid, Geophagus brasiliensis. Fish were sampled from the anthropogenically impacted estuarine Rodrigo de Freitas Lagoon, located in Southern Rio de Janeiro, and trace elements and MT were determined by inductively coupled plasma mass spectrometry (ICP-MS) and UV-Vis spectrophotometry, respectively, in fish liver and bile. MT in bile were significantly lower than in liver. Significant differences between bile and liver were observed for many trace elements, and, although most were higher in liver, Cd and Ni were significantly higher in bile, indicating efficient excretion from the body via the biliary route. A significant correlation was observed between MT and Fe in bile, and between MT in liver and Cu and Zn in bile. Molar ratio calculations demonstrated protective elements effects against Al, As, Cd, Hg, Pb and V in both bile and liver, as well as some novel interrelationships, indicating the importance of these investigations regarding the elucidation of element detoxifying mechanisms. Furthermore, investigation of other elemental associations may aid in decision-making processes regarding environmental contamination scenarios linked to public health.

Dual-opposite end multiple injection method applied to sequential determination of Na+, K+, Ca+2, Mg+2 ions and free and total glycerol in biodiesel by capillary zone electrophoresis.

A novel method for the sequential determination of sodium, potassium, calcium, and magnesium and free and total glycerol in biodiesel by capillary zone electrophoresis is proposed herein. The inorganic cations were separated along an effective length of 43.5 cm. The samples to quantify the free and total glycerol were injected into the opposite capillary end, close to the detection window, with an effective length of 8.5 cm. It was possible to achieve the separation of six analytes within 3 min. The quantification limits for the cations and glycerol ranged from 0.071 to 0.5 mg kg-1 to and 0.0017% to 0.017% w/w, respectively. Despite the complexity of the injection steps, the values for the instrumental, intraday and interday precision were better than 2.13, 4.49 and 5.68% (RSD), respectively, for the cations and the free and total glycerol. The method has good accuracy and specificity, which was statistically confirmed through an interlaboratory assay, where the method was compared with official methods.

Investigating heavy metal bioaccumulation by macrofauna species from different feeding guilds from sandy beaches in Rio de Janeiro, Brazil.

The relationship between metal accumulation and feeding behavior of macrofauna species is a key concept to understand the bioavailability of different metals in the marine environment. We examined and compared the concentrations of eight heavy metals (Cr, Zn, Pb, Ni, Cu, Cd, Co and V) in different feeding guilds of macrofauna species, from a data set including 68 sandy beaches along the Rio de Janeiro coast. For this purpose, macrofauna species were classified in five feeding guild categories: carnivorous, herbivorous, detritivorous, suspensivorous and filter feeders. The coast of Rio de Janeiro was divided into seven regions according to environmental characteristics and historical human activities. For each region, generalized linear models were adjusted to test for differences between feeding guild abundances. Redundancy Analysis was performed to explore the relationship among the feeding guilds composition and the environmental variables. We found high variability in abundance and composition among feeding guilds, linked with environmental heterogeneity. In general, carnivorous species showed a higher heavy metal concentrations compared to other trophic guilds evaluated. However, bioaccumulation across the feeding guild was not the rule and patterns varied across regions. Our hypothesis is that variations are probably related to the different magnitudes of metal contamination along the coast as also in to the trophic structure found in each beach. This data highlighted the crucial role of the relationship between variability of environmental drivers and bioaccumulation in macrofauna species in sandy beaches ecosystem.

Metal-based superoxide dismutase and catalase mimics reduce oxidative stress biomarkers and extend life span of Saccharomyces cerevisiae.

Aging is a natural process characterized by several biological changes. In this context, oxidative stress appears as a key factor that leads cells and organisms to severe dysfunctions and diseases. To cope with reactive oxygen species and oxidative-related damage, there has been increased use of superoxide dismutase (SOD)/catalase (CAT) biomimetic compounds. Recently, we have shown that three metal-based compounds {[Fe(HPClNOL)Cl2]NO3, [Cu(HPClNOL)(CH3CN)](ClO4)2 and Mn(HPClNOL)(Cl)2}, harboring in vitro SOD and/or CAT activities, were critical for protection of yeast cells against oxidative stress. In this work, treating Saccharomyces cerevisiae with these SOD/CAT mimics (25.0 µM/1 h), we highlight the pivotal role of these compounds to extend the life span of yeast during chronological aging. Evaluating lipid and protein oxidation of aged cells, it becomes evident that these mimics extend the life expectancy of yeast mainly due to the reduction in oxidative stress biomarkers. In addition, the treatment of yeast cells with these mimics regulated the amounts of lipid droplet occurrence, consistent with the requirement and protection of lipids for cell integrity during aging. Concerning SOD/CAT mimics uptake, using inductively coupled plasma mass spectrometry, we add new evidence that these complexes, besides being bioabsorbed by S. cerevisiae cells, can also affect metal homeostasis. Finally, our work presents a new application for these SOD/CAT mimics, which demonstrate a great potential to be employed as antiaging agents. Taken together, these promising results prompt future studies concerning the relevance of administration of these molecules against the emerging aging-related diseases such as Parkinson's, Alzheimer's and Huntington's.

Heavy metal contamination in sandy beach macrofauna communities from the Rio de Janeiro coast, Southeastern Brazil.

We evaluated concentrations of eight heavy metals Cr, Zn, Pb, Ni, Cu, Cd, Co and V, in tissues of representative macrofauna species from 68 sandy beaches from the coast of Rio de Janeiro state. The links between contamination levels and community descriptors such as diversity, evenness, density and biomass, were also investigated. Metal concentrations from macrofaunal tissues were compared to maximum permissible limits for human ingestion stipulated by the Brazilian regulatory agency (ANVISA). Generalized linear models (GLM's) were used to investigate the variability in macrofauna density, richness, eveness and biomass in the seven different regions. A non-metric multidimensional scaling analysis (n-MDS) was used to investigate the spatial pattern of heavy metal concentrations along the seven regions of Rio de Janeiro coast. Variation partitioning was applied to evaluate the variance in the community assemblage explained by the environmental variables and the heavy metal concentrations. Our data suggested high spatial variation in the concentration of heavy metals in macrofauna species from the beaches of Rio de Janeiro. This result highlighted a diffuse source of contamination along the coast. Most of the metals concentrations were under the limits established by ANVISA. The variability in community descriptors was related to morphodynamic variables, but not with metal contamination values, indicating the lack of direct relationships at the community level. Concentration levels of eight heavy metals in macrofauna species from 68 sandy beaches on Rio de Janeiro coast (Brazil) were spatially correlated with anthropogenic activities such as industrialization and urbanization.

Differential metallothionein, reduced glutathione and metal levels in Perna perna mussels in two environmentally impacted tropical bays in southeastern Brazil.

Mussel farming is an important economic activity in Brazil, and these organisms are consumed by the majority of the population in most coastal zones in the country. However, despite the increasing pollution of aquatic ecosystems in Brazil, little is known about the biochemical activity in mussels in response to metal exposure. In this context, the aim of the present study was to investigate metal and metalloid exposure effects in Perna perna mussels, by determining metal levels, the induction of metallothionein (MT) synthesis, and oxidative stress, in the form of reduced glutathione (GSH) in 3 contaminated areas from the Guanabara Bay in comparison to a reference site, Ilha Grande Bay, both in summer and winter. Metal and metalloid concentrations were also compared to Brazilian and international guidelines, to verify potential health risks to human consumers. Mussels from all sampling sites were shown to be improper for human consumption due to metal contamination, including Ilha Grande Bay, which has previously been considered a reference site. Several statistically significant correlations and seasonal differences were observed between MT, GSH and metals and metalloids in both analyzed tissues. A Discriminant Canonical Analysis indicated that the digestive gland is a better bioindicator for environmental contamination by metals and metalloids in this species and offers further proof that MT variations observed are due to metal exposure and not oxidative stress, since GSH influence for both muscle tissue and the digestive glands was non-significant in this analysis. These results show that P. perna mussels are an adequate sentinel species for metal contamination with significant effects on oxidative stress and metal exposure biomarkers. To the best of our knowledge, this is the first study to report metals, metalloids, MT and GSH levels in the muscle tissue of this species.