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.

A comprehensive assessment of leachate contamination at a non-operational open dumpsite: mycoflora screening, metal soil pollution indices, and ecotoxicological risks.

The final disposal of municipal solid waste (MSW) in dumpsites is still a reality worldwide, especially in low- and middle-income countries, leading to leachate-contaminated zones. Therefore, the aim of this study was to carry out soil and leachate physicochemical, microbiological, and toxicological characterizations from a non-operational dumpsite. The L-01 pond samples presented the highest physicochemical parameters, especially chloride (Cl; 4101 ± 44.8 mg L-1), electrical conductivity (EC; 10,452 ± 0.1 mS cm-1), and chemical oxygen demand (COD; 760 ± 6.6 mg L-1) indicating the presence of leachate, explained by its close proximity to the landfill cell. Pond L-03 presented higher parameters compared to pond L-02, except for N-ammoniacal and phosphorus levels, explained by the local geological configuration, configured as a slope from the landfill cell towards L-03. Seven filamentous and/or yeast fungi genera were identified, including the opportunistic pathogenic fungi Candida krusei (4 CFU) in an outcrop sample. Regarding soil samples, Br, Se, and I were present at high concentrations leading to high soil contamination (CF ≤ 6). Pond L-02 presented the highest CF for Br (18.14 ± 18.41 mg kg-1) and I (10.63 ± 3.66 mg kg-1), while pond L-03 presented the highest CF for Se (7.60 ± 1.33 mg kg-1). The most severe lethal effect for Artemia salina was observed for L-03 samples (LC50: 79.91%), while only samples from L-01 were toxic to Danio rerio (LC50: 32.99%). The highest lethality for Eisenia andrei was observed for L-02 samples (LC50: 50.30%). The applied risk characterization indicates high risk of all proposed scenarios for both aquatic (RQ 375-909) and terrestrial environments (RQ > 1.4 × 105). These findings indicate that the investigated dumpsite is contaminated by both leachate and metals, high risks to living organisms and adjacent water resources, also potentially affecting human health.

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.

Estimation of total arsenic contamination and exposure in Brazilian rice and infant cereals.

Arsenic (As) causes health effects, especially cancer. Rice (Oryza sativa L.) can contain high As concentrations. Using ICP-MS, we quantified the total As (tAs) levels in the main brands of rice (n = 103) and infant cereals (n = 27) consumed by Brazilians. The levels were compared to the maximum limits prescribed by regulatory agencies. We estimated the daily intake (EDI) of As by Brazilians by combining the mean As concentration determined in the white rice samples with per capita daily consumption divided by the average body weight as reported by the Brazilian Institute of Geography and Statistics in 2010. The possible health risk for consumers was assessed by calculating the margin of exposure (MOE) as prescribed by the Joint FAO/WHO Expert Committee on Food Additives (JECFA). Moreover, tAs was determined in 11 pesticides used by Brazilian farmers. The tAs levels in the rice ranged from 0.003 to 1.3 mg kg-1. Approximately 27% of the white rice contained tAs levels above the limit set by Mercosul (0.3 mg kg-1) and 45% were above the limit set by the European Commission (0.2 mg kg-1). In the infant cereals, tAs levels ranged from 0.003 to 0.243 mg kg-1. In the pesticides, tAs levels ranged from 0.005 to 0.315 mg L-1. The EDI showed that, on average, Brazilians consume 4.13 µg As kg-1 BW weekly. In addition, a low MOE was observed, demonstrating that high use of rice presents a risk of high inorganic (iAs) exposure, which represents a public health concern.

Toxic elements in packed red blood cells from smoker donors: a risk for paediatric transfusion?

BACKGROUND AND OBJECTIVES: Smokers currently have no defined restrictions for blood donation. However, cigarette smoke contains toxic substances such as carbon monoxide (CO) and trace elements that can affect the packed red blood cells (PRBCs) quality and safety of transfusion. This study evaluated the effects of smoking on the concentration of essential and trace elements and on carboxyhemoglobin (COHb) levels in PRBCs from smoker donors. MATERIALS AND METHODS: A matched case-control study was conducted to compare COHb levels, determined by the CO-oximetry method, and levels of trace (Cd, Pb, Cr, Ni, As and Hg) and essential (Ca, Mg, Cu, Fe, Mn, Mo, Se and Zn) elements evaluated by inductively coupled plasma mass spectrometry, in PRBCs from smoker (n = 36) and non-smoker (n = 36) donors at Hospital de Clínicas de Porto Alegre, Brazil. RESULTS: Mean COHb level was 14 times higher in the PRBCs obtained from smoker donors (5·9 [4·0-9·1] vs. 0·4 [0·2-0·8]%). Cadmium (1·0 [1·0-1·8] µg/l vs. undetectable) and lead (27 [21-36] vs. 19 [14-26] µg/l) levels were significantly higher in the PRBCs from smokers. Moreover, except for molybdenum, levels of all essential elements were lower in smoker PRBCs. CONCLUSION: The PRBCs donated by smokers contain toxic elements that are probably not safe for transfusion in children. Our results might support changes in the current guidelines of blood banks to improve the transfusion safety through inclusion of inquiry about smoking in the clinical screening, labelling and reserve PRBCs from smoker donors for adults or less critical recipients.

Sublethal psychotropic pharmaceutical effects on the model organism Danio rerio: Oxidative stress and metal dishomeostasis.

Contaminants of emerging concern have become an important environmental problem, especially pharmaceutically active compounds (PhACs), since, after use, these drugs return to the environment, contaminating aquatic ecosystems. Some may display the ability to bioaccumulate and biomagnify throughout the food chain, leading to potential environmental and human deleterious effects which are, however, still largely unknown. In this context, the aim of the present study was to evaluate the effect of two psychotropic drugs commonly found in the environment, carbamazepine (CBZ) and clonazepam (CZP), both isolated and co-administrated, on oxidative stress biomarkers and essential metal homeostasis in Danio rerio fish specimens. No studies are available to data in this regard concerning CZP effects on fish. Reduced Glutathione (GSH), Metallothionein (MT), Catalase (CAT) and Glutathione S-Transferase (GST) were determined, as well as essential metals in fish liver, kidney and brains. Significant oxidative stress effects were observed for several biomarkers, where brain GST activity was the most affected, mainly with regard to CBZ exposure, while GST and CAT activity in the liver were downregulated in the co-administration mixture. In addition, dishomeostasis of several essential elements was detected in all analyzed organs, with a synergistic action of CBZ and CZP in brain, decreasing basal Mg, Al, K, Fe, Co, Ni and Cu levels in this organ, the target site for these drugs in humans. The brain organ was the most affected as observed by altered GST activity and metal dyshomeostasis concerning exposure to both compounds. These compounds, thus, present health risks to the aquatic biota, due to the evidenced deleterious effects and their constant release into the environment due to widespread use. Steps are needed to implement adequate legislation for risk analysis and decision-making in order to mitigate the effects of these emerging contaminants on aquatic ecosystem health.

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).

Exposure to environment chemicals and its possible role in endocrine disruption of children from a rural area.

Endocrine disrupting chemicals (EDCs), including pesticides and metals, are present in rural areas, endangering the health of exposed populations. This work aimed to investigate the possible association between the exposure to these xenobiotics and thyroid dysfunction in children living in a rural community of Southern Brazil. Fifty-four children aged 5-16 years participated in this study. Peripheral biomarker evaluations were performed in periods of low and high exposure to pesticides. Thyroid ultrasonography was evaluated in the high exposure period. Blood levels of chromium (Cr), manganese (Mn), mercury (Hg), and lead (Pb), as well as hair Pb levels were positively correlated with thyroid stimulating hormone (TSH) concentrations and negatively associated with free thyroxine (fT4) levels in the low exposure period. Prolactin was positively associated with hair Mn in both periods. In the ultrasound tests, the majority of children presented a normal echogenicity of thyroid. Glucose was inversely associated with the biomarker of exposure to cholinesterase inhibitor insecticides, butyrylcholinesterase (BuChE). Lipid profile was above the recommended levels in both periods. In summary, our results show that children environmentally exposed to a mixture of xenobiotics in an agricultural community may have health impairments, especially on thyroid function, dyslipidemia, and glucose homeostasis disruption.

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.

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.

Determination and Evaluation of Metallothionein and Metals in Mugil cephalus (Mullet) from Pontal Bay, Brazil.

To assess environmental contamination, studies have been increasingly carried out using biomarkers to diagnose the effects of toxic metal exposure, such as metallothionein (MT). In this context, the aims of the present study were to determine Cd, Cu, Ni and Pb concentrations, by ICP-MS, in liver samples from Mugil cephalus from the municipality of Ilhéus, located in North-Southeastern Brazil, in the state of Bahia, which has been increasingly suffering from anthropogenic pressure, and to quantify total MT in liver and gills. Among essential metals, copper (199.2 µg g-1) presented concentrations approximately 7 times higher than allowed by the World Health Organization (30 µg g-1). Liver samples showed higher concentrations than gills. Metallothionein concentrations indicate differential contamination along the study area. The first sampling showed higher induction of MT synthesis overall. Differences between liver and gill MT concentration trends were relatively minor, which may indicate the adequacy of analyzing gills in an environmental monitoring context.

Associations among environmental exposure to manganese, neuropsychological performance, oxidative damage and kidney biomarkers in children.

Environmental exposure to manganese (Mn) results in several toxic effects, mainly neurotoxicity. This study investigated associations among Mn exposure, neuropsychological performance, biomarkers of oxidative damage and early kidney dysfunction in children aged 6-12 years old. Sixty-three children were enrolled in this study, being 43 from a rural area and 20 from an urban area. Manganese was quantified in blood (B-Mn), hair (H-Mn) and drinking water using inductively coupled plasma mass spectrometry (ICP-MS). The neuropsychological functions assessed were attention, perception, working memory, phonological awareness and executive functions - inhibition. The Intelligence quotient (IQ) was also evaluated. The biomarkers malondialdehyde (MDA), protein carbonyls (PCO), δ-aminolevulinate dehydratase (ALA-D), reactivation indexes with dithiothreitol (ALA-RE/DTT) and ZnCl2 (ALA-RE/ZnCl2), non-protein thiol groups, as well as microalbuminuria (mALB) level and N-acetyl-ß-D-glucosaminidase (NAG) activity were assessed. The results demonstrated that Mn levels in blood, hair and drinking water were higher in rural children than in urban children (p<0.01). Adjusted for potential confounding factors, IQ, age, gender and parents' education, significant associations were observed mainly between B-Mn and visual attention (ß=0.649; p<0.001). Moreover, B-Mn was negatively associated with visual perception and phonological awareness. H-Mn was inversely associated with working memory, and Mn levels from drinking water with written language and executive functions - inhibition. Rural children showed a significant increase in oxidative damage to proteins and lipids, as well as alteration in kidney function biomarkers (p<0.05). Moreover, significant associations were found between B-Mn, H-Mn and Mn levels in drinking water and biomarkers of oxidative damage and kidney function, besides between some oxidative stress biomarkers and neuropsychological tasks (p<0.05). The findings of this study suggest an important association between environmental exposure to Mn and toxic effects on neuropsychological function, oxidative damage and kidney function in children.

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.

An environmental forensic approach for tropical estuaries based on metal bioaccumulation in tissues of Callinectes danae.

The blue crab Callinectes danae is distributed throughout the Atlantic coast and this study aimed to evaluate a environmental forensics approach that could be applied at tropical estuarine systems where this species is distributed, based on the metal concentrations in its tissues. For this purpose, blue crab samples were collected in 9 sites (distributed in 3 areas) along the Santos Estuarine System, state of São Paulo, Brazil. The concentrations of Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn were determined in gills, hepatopancreas and muscle tissues. Sediment samples were collected and analyzed in these same sites. A data distribution pattern was identified during both sampling periods (August and December 2011). In order to validate this model, a new sampling campaign was performed in March 2013 at the Santos Estuarine System and also at Ilha Grande (state of Rio de Janeiro). These data were added to the previous database (composed of the August and December 2011 samples) and a discriminant analysis was applied. The results confirmed an environmental fingerprint for the Santos Estuarine System.

Improvement of antioxidant status after Brazil nut intake in hypertensive and dyslipidemic subjects.

OBJECTIVES: To investigate the effect of partially defatted Granulated Brazil nut (GBN) on biomarkers of oxidative stress and antioxidant status of hypertensive and dyslipidemic patients on nutrition and drug approaches. METHODS: Ninety one hypertensive and dyslipidemic subjects of both genders (51.6 % men), mean age 62.1 ± 9.3 years, performed a randomized crossover trial, double-blind, placebo controlled. Subjects received a diet and partially defatted GBN 13 g per day (≈227.5 µg/day of selenium) or placebo for twelve weeks with four-week washout interval. Anthropometric, laboratory and clinic characteristics were investigated at baseline. Plasma selenium (Se), plasma glutathione peroxidase (GPx3) activity, total antioxidant capacity (TAC), 8-epi PGF2α and oxidized LDL were evaluated at the beginning and in the end of each intervention. RESULTS: GBN intake significantly increased plasma Se from 87.0 ± 16.8 to 180.6 ± 67.1 µg/L, increased GPx3 activity in 24,8% (from 112.66 ± 40.09 to 128.32 ± 38.31 nmol/min/mL, p < 0,05), and reduced 3.25% of oxidized-LDL levels (from 66.31 ± 23.59 to 60.68 ± 20.88 U/L, p < 0.05). An inverse association between GPx3 and oxidized LDL levels was observed after supplementation with GBN by simple model (ß -0.232, p = 0.032) and after adjustment for gender, age, diabetes and BMI (ß -0.298, p = 0.008). There wasn't association between GPx3 and 8-epi PGF2α (ß -0.209, p = 0.052) by simple model. CONCLUSION: The partially defatted GBN intake has a potential benefit to increase plasma selenium, increase enzymatic antioxidant activity of GPx3 and to reduction oxidation in LDL in hypertensive and dyslipidemic patients. TRIAL REGISTRATION: ClinicalTrials.gov Identifier NCT01990391; November 20, 2013.

Tissue distribution of residual antimony in rats treated with multiple doses of meglumine antimoniate.

Meglumine antimoniate (MA) and sodium stibogluconate are pentavalent antimony (SbV) drugs used since the mid-1940s. Notwithstanding the fact that they are first-choice drugs for the treatment of leishmaniases, there are gaps in our knowledge of their toxicological profile, mode of action and kinetics. Little is known about the distribution of antimony in tissues after SbV administration. In this study, we evaluated the Sb content of tissues from male rats 24 h and three weeks after a 21-day course of treatment with MA (300 mg SbV/kg body wt/d, subcutaneous). Sb concentrations in the blood and organs were determined by inductively coupled plasma-mass spectrometry. In rats, as with in humans, the Sb blood levels after MA dosing can be described by a two-compartment model with a fast (t1/2 = 0.6 h) and a slow (t1/2 >> 24 h) elimination phase. The spleen was the organ that accumulated the highest amount of Sb, while bone and thyroid ranked second in descending order of tissues according to Sb levels (spleen >> bone, thyroid, kidneys > liver, epididymis, lungs, adrenals > prostate > thymus, pancreas, heart, small intestines > skeletal muscle, testes, stomach > brain). The pathophysiological consequences of Sb accumulation in the thyroid and Sb speciation in the liver, thyroid, spleen and bone warrant further studies.

Metal, metallothionein and glutathione levels in blue crab (Callinectes sp.) specimens from southeastern Brazil.

Metal concentrations (Cu, Pb, Zn and Cd) were determined in muscle, gills, soft tissues and eggs in male, non-ovigerous and ovigerous female Callinectes sp. specimens from a reference site in Southeastern Brazil. Metallothionein (MT) and reduced glutathione (GSH) levels were also determined. Results demonstrate that sex has a significant influence on metal, MT and GSH concentrations. Significant maternal transfer of Pb and Zn from ovigerous females to eggs was verified, while female crabs, both ovigerous and non-ovigerous, showed elevated GSH and MT in viscera when compared to males, indicating possible MT role in excreting metals to eggs in ovigerous females of this species. Several strong statistical correlations between metals and MT indicate MTs role in detoxification of both toxic and essential elements in different organs. Pb and Zn were significantly correlated to GSH, indicating oxidative stress caused by the former and a direct link between Zn and GSH in maintaining homeostasis. Regarding human consumption, metal concentrations were lower than the maximum permissible levels established by international and Brazilian regulatory agencies, indicating that this species is safe for human consumption concerning this parameter. The presence of metals in Callinectes sp., however, is still of importance considering that this is a key species within the studied ecosystem and, therefore, plays a major role in the transference of pollutants to higher trophic levels. In addition, the presence of significant metal concentrations found in eggs must be considered in this context, since crab eggs are eaten by several other species, such as shorebirds, seabirds, and fish. Also, to the best of our knowledge, this is the first study regarding both MT and GSH levels in Callinectes sp. eggs and is of interest in the investigation of molecular mechanisms regarding metal exposure in these crustaceans. Data reported in this study support the conclusions from previous reports, provide mechanistic insights regarding metal exposure, metallothionein and oxidative stress induction in this species and also present novel data regarding eggs.

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.

Rare Earth Element Accumulation in Fiddler Crabs (Minuca rapax) from the Rio Doce Tropical Estuary Strongly Affected by Mine Tailings Following the Fundão Disaster.

A mining tailing dam rupture in Brazil in November 2015 released millions of tons of mining waste into the Rio Doce ecosystem, leading to long-term aquatic ecosystem impacts. Although multiple lines of evidence indicate tailings associations with potentially toxic elements in estuarine sediments and biological impact and bioaccumulation pathways in fishes, the extent of contamination in base benthic species is still largely unknown. Moreover, Rare Earth Elements (REE) have not received any attention in this regard. This study assessed REE in fiddler crabs (Minuca rapax) sampled from the Rio Doce estuary in 2017, nearly 2 years after the disaster. The ΣREE in crab hepatopancreas and muscle were high (327.83 mg kg-1 w.w. and 33.84 mg kg-1 w.w., respectively, compared to other assessments in crabs, indicating a preference for REE bioaccumulation in the hepatopancreas compared to muscle. Neodimium, La, and Ce were detected at the highest concentrations. The REE from the Rio Doce Basin were, thus, transported and deposited in the estuary with the mine tailings slurry, leading to bioaccumulation in crabs. This may lead to trophic effects and other ecological impacts not readily measured by typical impact assessment studies, revealing an invisible and not typically acknowledged damage to the Rio Doce estuary.

Environmental impact assessment of end-of-life fluorescent lamps in Rio de Janeiro, Brazil, under different recycling rate scenarios.

Fluorescent lamps are hazardous materials, as they contain toxic elements, which may lead to environmental contamination. Therefore, assessing potential environmental impacts arising from inadequate lamp disposal is paramount. Studies addressing the Life Cycle Analysis (LCA) of end-of-life fluorescent lamps are, however, still scarce, and inappropriate lamp disposal remains a matter of concern, especially in developing and underdeveloped countries. In Brazil, fluorescent lamps are still used countrywide and are often inadequately discarded. However, studies assessing fluorescent lamp impacts and potential impact reduction through enhanced recycling are still scarce in the country, despite Brazil's size and high waste generation rates. Furthermore, Brazil's lamp recycling program is a recent measure and still falls short of the country's needs. Thus, this study aimed to assess potential environmental impacts of end-of-life fluorescent lamps in Rio de Janeiro, the second largest capital in Brazil, to the best of our knowledge, for the first time. Potential impact reductions due to higher recycling program adherence considering 5, 20, 80 and 100 % recycling rates were also assessed. The findings indicate that the impact categories most influenced by end-of-life lamps were terrestrial ecotoxicity, human non-carcinogenic toxicity, global warming potential, and fossil resource scarcity. Increased recycling rates, in turn, reduced the environmental impact potential for all evaluated categories, reaching an almost 90 % reduction in most categories when applying a 100 % recycling rate. The current national program target recycling rate of 20 %, however, already contributes to an average impact reduction of over 70 %, comprising a more viable national application rate and already significantly contributing to reduced impacts.