The Development of a Rapid, Cost-Effective, and Green Analytical Method for Mercury Speciation.

Mercury is a naturally occurring metal found in various inorganic and organic forms within the environment. Due to its high toxicity, there is global concern regarding human exposure to this element. The combination of high-performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICP-MS) is commonly used to analyze the different forms of mercury in a sample due to its high sensitivity and ability to selectively detect mercury. However, the traditional HPLC-ICP-MS methods are often criticized for their lengthy analysis times. In this study, we have refined the conventional approach by transitioning to ultra-high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (UHPLC-ICP-MS). This modification has resulted in significant reductions in runtime as well as reagent and argon usage, thereby offering a more rapid, environmentally friendly, and cost-effective method. We successfully adapted an HPLC-ICP-MS method to UHPLC-ICP-MS, achieving the analysis of Hg2+ and MeHg+ within 1 min with a mobile phase consumption of only 0.5 mL and a sample volume of 5.0 µL; this is a major advance compared to HPLC analysis with run times generally between 5 and 10 min. The method's performance was assessed by analyzing muscle and liver tissue samples (serving as reference material) from fish, demonstrating the versatility of the method in relation to different complex matrices.

Levels and health risk assessment of twenty-one current-use pesticides in urban and riverside waters of the Brazilian Amazon Basin.

In Brazil, the favorable weather conditions and abundant land contribute to the thriving agricultural production. Brazilian crops extensively employ pesticides due to their high efficacy, cost-effectiveness, and permissive regulatory framework. However, pesticide use also endangers water resources, animal organisms, and human health. Due to the lack of data on pesticide use in the Amazonas forest-based Brazil, the present study aimed to assess the levels of twenty-one current-use pesticides (CUPs) from five different classes in river waters collected from urban and riverside areas in this region. Moreover, the non-carcinogenic risks associated with water consumption were also characterized. Thirteen CUPs were detected in concentrations above the limit of detection (LOD) in at least one of the water samples, and most pesticides were detected in riverside areas. In contrast, only 18% of the analyzed samples were considered "clean," with only one compound detected. Fenitrothion showed the highest concentration, with a mean value of 4.86 ng/mL (0.30-14.3 ng/mL). Up to 33% of the samples showed levels of fipronil above the LOD, an issue of environmental and human health concern, mainly because of the adverse effects observed in honeybees. Despite this, the human health risk assessment showed a target hazard quotient below one (HQ < 1) in adults for all substances, suggesting that pesticide exposure through water consumption should not mean risk for the riverside populations. Taking into account the large extension of Brazil, as well as its different agricultural practices throughout the country, it would be of great importance to conduct extensive research in other areas. It would help to gain knowledge in this field and to promote eco-friendly alternatives to mitigate pesticide use and, consequently, to reduce their potential adverse effects on human health and the ecosystems.

Hydroxymethylnitrofurazone lymphatic uptake with nanostructured lipid carrier after oral administration in rats.

Background: Leishmaniasis, caused by the protozoan Leishmania sp., infects phagocyte cells present in lymphatic organs. This study demonstrates the influence of nanostructured lipid carrier-loaded hydroxymethylnitrofurazone (NLC-NFOH) on lymphatic uptake using a chylomicron-blocking flow model in rats. Method: Lymphatic uptake of NFOH was assessed 1 h after oral administration of dimethyl sulfoxide with NFOH or NLC-NFOH with and without cycloheximide pretreatment. Result: Dimethyl sulfoxide with NFOH and NLC-NFOH showed NFOH serum concentrations of 0.0316 and 0.0291 µg/ml, respectively. After chylomicron blocking, NFOH was not detected. Conclusion: Despite log P below 5, NFOH was successfully taken up by the lymphatic system. Long-chain fatty acids and particle size might be main factors in these findings. NLC-NFOH is a promising and convenient platform for treating leishmaniasis via oral administration.

Levels of organic pollutants and metals/metalloids in infant formula marketed in Brazil: Risks to early-life health.

Infant formula intake is recommended to ensure comprehensive nutritional and caloric fulfillment when exclusive breastfeeding is not possible. However, similarly to breast milk, infant formulas may also contain pollutants capable of inducing endocrine-disrupting and neurotoxic effects. Thus, considering the sensitivity of their developing physiological systems and that infants have heightened susceptibility to environmental influences, this study was aimed at assessing the contents of essential elements, and inorganic and organic pollutants in infant formulas marketed in Brazil. Additionally, health risk assessments for selected contaminants were also performed. Measured contents of essential elements (Ca, Fe, Mg, Mn, Cu, Se, and Zn) were congruent with label information. Nevertheless, some toxic elements (Pb, Cd, As, Ni, and Al) were also detected. Notably, in the upper-bound scenario, Pb and Cd surpassed established threshold values when comparing the estimated daily intake (EDI) and tolerable daily intake (TDI - 3.57 and 0.36 µg/kg bw, respectively). Bisphenol P (BPP) and benzyl butyl phthalate (BBP) were frequently detected (84 % detection rate both) with elevated contents (BPP median = 4.28 ng/g and BBP median = 0.24 ng/g). Furthermore, a positive correlation (0.41) was observed between BPP and BBP, implying a potential co-occurrence within packaging materials. Methyl-paraben also correlated positively with BBP (0.57), showing a detection rate of 53 %. The cumulative PBDE contents ranged from 0.33 to 1.62 ng/g, with BDE-154 and BDE-47 the dominant congeners. When comparing EDI values with TDIs, all organic pollutants remained below the thresholds across all exposure scenarios. Moreover, non-carcinogenic risks were below the threshold (HQ > 1) when dividing the EDIs by the respective reference doses for chronic exposure. While the current findings may suggest that infant formula intake poses no immediate risk in terms of the evaluated chemicals, it remains imperative to conduct further research to safeguard the health of infants considering other chemicals, as well as their potential cumulative effects.

Association between urinary concentrations of toxic metals/metalloids and oxidative stress in Brazilians living in areas affected by the Fundão dam failure.

The Fundão Dam failure has been the most significant environmental disaster in Brazil. The catastrophe released large amounts of mining waste into the environment, including toxic metals/metalloids, which are recognized to induce carcinogenic effects. The urinary levels of 8-hydroxy-2'-deoxyguanosine (8OHdG), a widely accepted oxidative stress and carcinogenesis biomarker, provide a potential tool for assessing the disaster's health implications. This study investigated the association between urinary levels of some toxic metals/metalloids and 8OHdG in Brazilian individuals living in areas affected by the Fundão dam failure. Urinary concentrations of arsenic (As), cadmium (Cd), mercury (Hg), nickel (Ni), and lead (Pb) were determined using inductively coupled plasma mass spectrometry, while 8OHdG was analyzed by liquid chromatography-tandem mass spectrometry. Non-parametric bootstrap regression was used to estimate the associations between the urinary levels of toxic elements and 8OHdG. The results showed that except for Hg, urinary concentrations of all metals/metalloids analyzed here exceeded the reference ranges for the Brazilian population. The regression analysis revealed that As (0.337; CI 95%: 0.203; 0.474), Cd (0.268; CI 95%: 0.036; 0.520), and Ni (0.296; CI 950.108; 0.469) were positively associated with creatinine-adjusted urinary 8OHdG levels. Associations were not found for Hg (0.0122; CI 95%: -0.155; 0.183) and Pb (0.201; CI 95%: -0.040; 0.498). The current findings suggest that high exposure to toxic metals/metalloids might increase 8OHdG levels with potential adverse health effects. This study is the first one in which the relationship between toxic metals/metalloids and oxidative stress biomarkers is investigated in populations affected by environmental disasters. Further prospective studies are necessary to monitor exposure levels and explore additional health impacts.

Risk characterization of human exposure to polycyclic aromatic hydrocarbons in vulnerable groups.

Nowadays, anthropogenic activities are a significant source of environmental pollutants at an alarming rate. Polycyclic aromatic hydrocarbons (PAHs) are widely spread and well-known mutagenic and carcinogenic legacy pollutants of public health concern. In underdeveloped countries like Brazil, limited data are available in the scientific literature on the risk assessment of exposure to PAHs, leading to a risk underestimation, especially in the vulnerable groups of the population. In the current investigation, we have measured seven PAH metabolites in healthy vulnerable groups (n = 400), including pregnant and lactating women, newborns, and children. Besides, according to the United States Environmental Protection Agency (US.EPA) guidelines, the risk characterization of this exposure was performed by calculating estimated daily intake, hazard quotient, hazard index, and cancer risk. The highest levels and detection rates for all metabolites were found in pregnant women, with 15.71 ng/mL for the ∑OH-PAHs, presumably due to the increased metabolic rate related to pregnancy. The lowest ∑OH-PAHs were detected in infants, with 2.33 ng/mL due to unmatured metabolism. When analyzing the health hazards, the non-carcinogenic risk - as a sum of all PAH metabolites, we observed a health risk (in all groups) above the limit that the US.EPA considers without significant potential health risk. Regarding cancer risks, benzo[a]pyrene levels in all the groups indicated a potential risk. In general, higher levels of potential cancer risk were observed for lactating women, which implies risks to them and their infants. Low molecular weight PAHs (naphthalene, fluorene, and phenanthrene) are associated with acute toxic effects. Their high detection rate (i.e., naphthalene: 100 %) demonstrates their extensive exposure, making these PAHs a priority for human biomonitoring. Besides, benzo[a]pyrene is carcinogenic to humans, being also important to monitor its levels since our risk assessment showed a high cancer risk to this PAH.

The influence of the co-exposure to polycyclic aromatic hydrocarbons and toxic metals on DNA damage in brazilian lactating women and their infants: A cross-sectional study using machine learning approaches.

Polycyclic aromatic hydrocarbons (PAHs) and toxic metals are widely spread pollutants of public health concern. The co-contamination of these chemicals in the environment is frequent, but relatively little is known about their combined toxicities. In this context, this study aimed to evaluate the influence of the co-exposure to PAHs and toxic metals on DNA damage in Brazilian lactating women and their infants using machine learning approaches. Data were collected from an observational, cross-sectional study with 96 lactating women and 96 infants living in two cities. The exposure to these pollutants was estimated by determining urinary levels of seven mono-hydroxylated PAH metabolites and the free form of three toxic metals. 8-Hydroxydeoxyguanosine (8-OHdG) levels in the urine were used as the oxidative stress biomarker and set as the outcome. Individual sociodemographic factors were also collected using questionnaires. Sixteen machine learning algorithms were trained using 10-fold cross-validation to investigate the associations of urinary OH-PAHs and metals with 8-OHdG levels. This approach was also compared with models attained by multiple linear regression. The results showed that the urinary concentration of OH-PAHs was highly correlated between the mothers and their infants. Multiple linear regression did not show a statistically significant association between the contaminants and urinary 8OHdG levels. Machine learning models indicated that all investigated variables did not present predictive performance on 8-OHdG concentrations. In conclusion, PAHs and toxic metals were not associated with 8-OHdG levels in Brazilian lactating women and their infants. These novelty and originality results were achieved even after applying sophisticated statistical models to capture non-linear relationships. However, these findings should be interpreted cautiously because the exposure to the studied contaminants was considerably low, which may not reflect other populations at risk.

Recent trends in pesticides in crops: A critical review of the duality of risks-benefits and the Brazilian legislation issue.

Due to the increasing population worldwide, in recent years, an exponential increase in agricultural practices has occurred in order to attend to the growing demand for food. Unfortunately, this increase is not associated with the supply of foodstuffs free of environmental pollutants. In Brazil, agriculture is one of the most important economic pillars, making the country one of the largest consumers of pesticides around the world. The intense use of pesticides, mainly glyphosate, 2,4-D, and atrazine, constitutes an essential factor in the viability of this great agricultural productivity. Sugarcane, corn, soybean, and citrus crops consume around 66% of the total pesticides worldwide, representing 76% of the planted area. Pesticide residues have been frequently detected in food and the environment, becoming a significant concern for human health. Monitoring programs for pesticide use are essential to reduce the potential negative impacts on the environment and improve the overall efficiency and sustainability of their use. However, in Brazil, the approval status of pesticide-active ingredients is very discrepant compared to other agricultural countries. Moreover, the duality of benefits and risks of pesticide application creates an economic and toxicological conflict. In this paper, we have critically reviewed the duality of risks-benefits of the use of pesticides in agriculture and the current Brazilian legislation issues. We have also compared this flawed legislation with other countries with high economic potential. Due to the negative environmental impacts on soil and water by the high levels of pesticides, remediation techniques, sustainable agriculture, and the development of new technologies can be considered some viable alternatives to reduce the levels in these compartments. Besides, this paper includes some recommendations that can be included in the coming years.

Lipidomic profiling of the Brazilian yellow scorpion venom: new insights into inflammatory responses following Tityus serrulatus envenomation.

Due to the high prevalence and clinical relevance, scorpionism is a critical public health issue in several Brazilian regions. Tityus serrulatus, commonly known as the Brazilian yellow scorpion, is the most venomous genus found in Brazilian fauna and associated with severe clinical manifestations such as localized pain, hypertension, sweating, tachycardia and complex hyperinflammatory responses. In general, T. serrulatus venom contains a complex mixture of active compounds, including proteins, peptides, and amino acids. Although knowledge of the protein fractions of scorpion venom is available, venom lipid components are not yet comprehensively known. The aim of the present study was to determine and characterize the lipid constituents/profile of the T. serratus venom utilizing liquid chromatography coupled with high-resolution mass spectrometry. Lipid species (164 in total) belonging to 3 different lipid categories, glycerophospholipids, sphingolipids, and glycerolipids, were identified. A further search on MetaCore/MetaDrug platform, which is based upon a manually curated database of molecular interactions, molecular pathways, gene-disease associations, chemical metabolism, and toxicity information, exhibited several metabolic pathways for 24 of previously identified lipid species, including activation of nuclear factor kappa B and oxidative stress pathways. Further several bioactive compounds, such as plasmalogens, lyso-platelet-activating factors, and sphingomyelins, associated with systemic responses triggered by T. serrulatus envenomation were detected. Finally, lipidomic data presented provide advanced and valuable information to better comprehend the mechanisms underlying the complex pathophysiology induced by T. serrulatus envenomation.

Arsenic in Mining Areas: Environmental Contamination Routes.

The emission and accumulation of toxic elements such as arsenic in various environmental compartments have become increasingly frequent primarily due to anthropogenic actions such as those observed in agricultural, industrial, and mining activities. An example of environmental arsenic contamination in Brazil exists in the city of Paracatu, MG, due to the operation of a gold mine. The aim of this work is to evaluate the routes and effects of arsenic contamination in environmental compartments (air, water, and soil) and environmental organisms (fish and vegetables) from mining regions as well as the trophic transfer of the element for a risk assessment of the population. In this study, high levels of arsenic were found in the waters of the Rico stream ranging from 4.05 µg/L during the summer season to 72.4 µg/L during the winter season. Moreover, the highest As concentration was 1.668 mg kg-1 in soil samples, which are influenced by seasonal variation and by proximity to the gold mine. Inorganic and organic arsenic species were found above the allowed limit in biological samples, indicating the transfer of arsenic found in the environment and demonstrating a great risk to the population exposed to this area. This study demonstrates the importance of environmental monitoring to diagnose contamination and encourage the search for new interventions and risk assessments for the population.

Association between Polymorphisms of Hemochromatosis (HFE), Blood Lead (Pb) Levels, and DNA Oxidative Damage in Battery Workers.

Occupational exposure to lead (Pb) continues to be a serious public health concern and may pose an elevated risk of genetic oxidative damage. In Brazil, car battery manufacturing and recycling factories represent a great source of Pb contamination, and there are no guidelines on how to properly protect workers from exposure or to dispose the process wastes. Previous studies have shown that Pb body burden is associated with genetic polymorphisms, which consequently may influence the toxicity of the metal. The aim of this study was to assess the impact of Pb exposure on DNA oxidative damage, as well as the modulation of hemochromatosis (HFE) polymorphisms on Pb body burden, and the toxicity of Pb, through the analysis of 8-hydroxy-2'-deoxyguanosine (8-OHdG), in subjects occupationally exposed to the metal. Male Pb-exposed workers (n = 236) from car battery manufacturing and recycling factories in Brazil participated in the study. Blood and plasma lead levels (BLL and PLL, respectively) were determined by ICP-MS and urinary 8-OHdG levels were measured by LC-MS/MS, and genotyping of HFE SNPs (rs1799945, C → G; and 1800562, G → A) was performed by TaqMan assays. Our data showed that carriers of at least one variant allele for HFE rs1799945 (CG + GG) tended to have higher PLL than those with the non-variant genotype (ß = 0.34; p = 0.043); further, PLL was significantly correlated with the levels of urinary 8-OHdG (ß = 0.19; p = 0.0060), while workers that carry the variant genotype for HFE rs1800562 (A-allele) showed a prominent increase in 8-OHdG, as a function of PLL (ß = 0.78; p = 0.046). Taken together, our data suggest that HFE polymorphisms may modulate the Pb body burden and, consequently, the oxidative DNA damage induced by the metal.

Artisanal Gem Mining in Brazil: A Source of Genotoxicity and Exposure to Toxic Elements.

Environmental and occupational exposure to toxic metals has led many people around the world to have serious health problems. Mining activities contribute to an increased risk of exposure to these elements. In this work, a study of environmental biomonitoring and routes of exposure to toxic metals in a region of artisanal mining was performed. This study was carried out in the district of Taquaral de Minas, located in the Jequitinhonha Valley in the state of Minas Gerais. The valley is one of the wealthiest and highest gem-producing areas in Brazil. Five artisanal mines were sampled (Bode, Pirineu, Pinheira, Lajedo, and Marmita). Several potentially toxic metals (Be, Zn, Mn, Ba Cd, Hg, and U) were investigated in the soils and dust over the rocks and the soils. Samples from 22 individuals occupationally exposed and 17 unexposed persons, who formed the reference group, were analyzed for trace elements by an inductively coupled plasma mass spectrometer. The genotoxicity was evaluated by the micronucleus test in buccal mucosa epithelial cells, where the following changes were scored: micronuclei (MN) binucleate (BN) cells and kariolytic (KL) cells. The MN test showed significantly increased frequencies in all alterations of exposed individuals compared to the controls (p < 0.05, Student's t-test). The urine analysis showed levels of Cr, Ni Ba, Pb, and As in the blood, which were higher than the ATSDR recommended levels. The association between the MN test and the trace element concentrations found in the blood and urine was significant (p < 0.05). The higher the number of years of working, the higher the concentrations in the blood were, due to chronic exposure. The results of the present study indicate environmental contamination and a potential risk to the health of miners, suggesting an intervention.

Evidence on Neurotoxicity after Intrauterine and Childhood Exposure to Organomercurials.

Although the molecular mechanisms underlying methylmercury toxicity are not entirely understood, the observed neurotoxicity in early-life is attributed to the covalent binding of methylmercury to sulfhydryl (thiol) groups of proteins and other molecules being able to affect protein post-translational modifications from numerous molecular pathways, such as glutamate signaling, heat-shock chaperones and the antioxidant glutaredoxin/glutathione system. However, for other organomercurials such as ethylmercury or thimerosal, there is not much information available. Therefore, this review critically discusses current knowledge about organomercurials neurotoxicity-both methylmercury and ethylmercury-following intrauterine and childhood exposure, as well as the prospects and future needs for research in this area. Contrasting with the amount of epidemiological evidence available for methylmercury, there are only a few in vivo studies reporting neurotoxic outcomes and mechanisms of toxicity for ethylmercury or thimerosal. There is also a lack of studies on mechanistic approaches to better investigate the pathways involved in the potential neurotoxicity caused by both organomercurials. More impactful follow-up studies, especially following intrauterine and childhood exposure to ethylmercury, are necessary. Childhood vaccination is critically important for controlling infectious diseases; however, the safety of mercury-containing thimerosal and, notably, its effectiveness as preservative in vaccines are still under debate regarding its potential dose-response effects to the central nervous system.

Potential Health Risk to Brazilian Infants by Polybrominated Diphenyl Ethers Exposure via Breast Milk Intake.

Polybrominated diphenyl ethers (PBDEs) are ubiquitous flame retardants and are environmentally persistent. PBDEs show endocrine disruption, neurotoxicity, and lower birth weight in infants, and their human body burden has become a public health concern. The infants' exposure begins in the prenatal period and continues via breast milk ingestion, although, little is known about the factors that may influence this exposure. In this study, PBDE levels in Brazilian breast milk were assessed in 200 lactating women. The risk assessment of infants' exposure to PBDE was performed through the estimated daily intake (EDI) calculation. The geometric mean (GM) of ∑PBDEs levels was 2.33 (0.14-6.05) ng/g wet weight. At least one PBDE congener was detected in the samples, and the 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) showed a 100% of detection rate (GM of 1.05 ng/g). Location of residence, maternal level education, monthly salary, and race were positively associated with PBDE levels (p < 0.05). The EDI of BDE-47 was higher in Belo Horizonte (8.29 ng/kg/day) than in Viçosa (6.36 ng/kg/day), as well as for the ∑PBDEs (19.77 versus 12.78 ng/kg/day) (p < 0.05). Taking the high detection rate of PBDEs in breast milk and their toxicity, continuous studies on infant exposure, fetal growth, and child neurodevelopment are requested.

Legacy and emerging pollutants in Latin America: A critical review of occurrence and levels in environmental and food samples.

The increase and indiscriminate use of personal care products, food products, fertilizers, pesticides, and health products, among others, have resulted/are resulting in extensive environmental contamination. Most of these products contain traces of widespread chemicals, usually known as emerging pollutants (EPs) or pollutants of emerging concern (PEC). The Latin American (LA) region comprises 20 countries with different social and cultural aspects, with 81 % of the population living in urban areas. The LA region has some countries on the top list of users/consumers of EPs, from pesticides and fertilizers to personal care products. However, there is a gap in information related to the distribution of EPs in the environment of this region, with very few existing review texts exploring this issue. Therefore, this present paper advances this approach. An exhaustive literature review, with the selection of 176 documents, provided unique up-to-date information on the presence/distribution of 17 classes of legacy or emerging pollutants in different food and environmental matrices (soil, sediment, water, and air). The study shows that the wide distribution and recorded levels of these pollutants in the continental environment are potential risks to human health, mainly through food and drinking water ingestion. Polycyclic aromatic hydrocarbons are pollutants of deep public concern since they show carcinogenic properties. Several classes of pollutants, like endocrine disruptors, have caused harmful effects on humans and the environment. Besides that, pharmaceutical products and pesticides are compounds of high consumption worldwide, being environmental contamination a real and ongoing possibility. Finally, gaps and future research needs are deeply pointed out.

Levels of phthalates and bisphenol in toys from Brazilian markets: Migration rate into children's saliva and daily exposure.

Bisphenols (BPs) and phthalate esters (PAEs) are extensively used in toys and childcare products. Therefore, children may be exposed to these compounds, causing potential adverse effects. Despite the strict control of the levels of these contaminants in toys by some nations, routine testing in Brazil is very scarce. The present study was aimed at determining the concentrations of PAEs and BPs in toys commercialized in Brazil, employing GC-MS and LC-MS/MS, respectively. Furthermore, the migration capacity of PAEs into saliva and the daily intake (EDI) were also estimated. Di-2-ethylhexyl phthalate (DEHP) was the PAE with the highest detection rate (93%) and migration rate (0.26 µg/min). Moreover, the levels of DEHP in some samples were above the threshold values set by the European Commission and the Brazilian Institute of Metrology, Standardization, and Industrial Quality. Among the BPs analogs, BPA and BPS presented the highest positive detection rates (72% and 30%, respectively). However, their levels were below the permitted values in all analyzed samples. A daily intake of DEHP was estimated at 29.8 µg/kg bw/day, being this exposure similar to those found in other countries and below the EFSA acceptable intake limit (50 µg/kg bw/day). However, our data are referred to exposure through oral contact with the analyzed toys, while the contribution of other potential sources, such as food consumption, were not here considered. To the best of our knowledge, this is the first study estimating the exposure of Brazilian children to PAEs and BPs, considering toys as the exposure source. These preliminary data may become a valuable guide for the control of EDC levels in toys commercialized in Brazil, as well as for future studies regarding estimation of exposure to EDCs by children taking into account multiple potential sources.

Urinary levels of monohydroxylated polycyclic aromatic hydrocarbons in Brazilian children and health risk assessment: a human biomonitoring-based study.

Monitoring human exposure to polycyclic aromatic hydrocarbons (PAHs) is a public health concern. Children are a vulnerable subgroup of the population with limited human biomonitoring data worldwide. Thus, this study aimed to measure the levels of seven PAH metabolites in urine from Brazilian children and provide risk assessment values for this exposure. Our data show naphthalene was the major contributor to children's exposure to PAHs, with a 100% detection rate. Children in urban regions presented higher exposure to PAHs, with higher concentrations of 2-naphthol in the southeast (1.09 ng/mL, p < 0.05). Furthermore, the highest concentration of 2-naphthol was found in older children (p = 0.02), suggesting a possible difference in dietary habits. Exposure to the carbaryl insecticide is suggested based on the high concentrations of 1-naphthol (1.29 ng/mL) and considering the ratio 1-naphthol/2-naphthol (1.78). Moreover, the positive correlation between the metabolites of fluorine and pyrene also suggests exposure to PAHs by petrol combustion. The risk assessment of the PAH exposure was evaluated using the estimated daily intake (EDI) for two naphthalene metabolites in the study with a 100% detection rate. The EDI was 14.47 ng/kg BW/day. The risk assessment to the PAH exposure revealed a non-carcinogenic risk profile, with a hazard quotient of 0.71. To the best of our knowledge, this study is the first to provide levels of PAHs in Brazilian children.

Degradation of Praguicide Disulfoton Using Nanocompost and Evaluation of Toxicological Effects.

Organophosphates (OPPs) are an important element of modern agriculture; however, because they are being used excessively, their residues are leaching and accumulating in the soil and groundwater, contaminating aquatic and terrestrial food chains. An important OPP called disulfoton is frequently used to eradicate pests from a wide range of crops, including Brazil's coffee crops. Additionally, it does not easily degrade in the environment, and as such, this compound can slowly build up in living organisms such as humans. Moreover, this compound has been classified as "extremely hazardous" by the World Health Organization. This study evaluated the degradation efficiency of disulfoton using a Fenton-like reaction catalyzed by magnetite nanoparticles and determined the toxicity of the by-products of the degradation process using the bioindicator Allium cepa. Further, the removal efficiency of disulfoton was determined to be 94% under optimal conditions. On the other hand, the Allium cepa bioassay showed different toxic, cytotoxic, genotoxic, and mutagenic outcomes even after the remediation process. In conclusion, the Fenton process catalyzed by magnetite nanoparticles presents great efficiency for the oxidation of disulfoton. However, it is important to highlight that the high degradation efficiency of the Fenton-based process was not sufficient to achieve detoxification of the samples.

Levels of polybrominated diphenyl ethers in Brazilian food of animal origin and estimation of human dietary exposure.

Polybrominated diphenyl ethers (PBDEs) are persistent organic pollutants, commonly used as flame retardants in a wide variety of products. In the last years, the concentration of PBDEs is increasing in the environment, turning human exposure more common. Since the diet is the primary source of human exposure, several surveys evaluate the levels of PBDEs in foods to estimate the dietary intake and the hazard index (HI). However, this data is limited in Brazil. Thus, this study aims to determine the level of seven PBDE congeners (BDE-28, 47, 99, 100, 153, 154, 183) in Brazilian food of animal origin. The total concentration of PBDE (∑PBDE) determined in the food samples were 2.29 (0.92-4.85) ng/g wet weight (ww), 1.98 (1.23-3.12) ng/g ww, 1.91 (1.23-3.12) ng/g ww, and 4.42 (1.26-8.42) ng/g ww in eggs, fish, seafood, and milk, respectively. BDE-47 was the most abundant compound. Based on consumer habits and the found levels of PBDEs in Brazilian food, we estimated the daily intake of ∑PBDEs as 3.25 (0.02-2.19) ng/kg bw per day. Surprisingly, the PBDE levels in milk samples were higher than those found in reported studies in other countries, and the consumption of milk products give a higher relative contribution to PBDEs exposure. The HI was <1. A complete risk assessment of the human exposure to PBDEs most likely could be evaluated considering all commercial PBDEs congeners and other exposure sources of these contaminants.

Risk assessment of the chiral pesticide fenamiphos in a human model: Cytochrome P450 phenotyping and inhibition studies.

Fenamiphos (FS) is a chiral organophosphate pesticide that is used to control nematodes in several crops. Enantioselective differences may be observed in FS activity, bioaccumulation, metabolism, and toxicity. Humans may be exposed to FS through occupational and chronic (food, water, and environmental) exposure. FS may cause undesirable CYP450 pesticide-drug interactions, which may impact human health. Here, the CYP450 isoforms involved in enantioselective FS metabolism were identified, and CYP450 inhibition by rac-FS, (+)-FS, and (-)-FS was evaluated to obtain reliable information on enantioselective FS risk assessment in humans. CYP3A4 and CYP2E1 metabolized FS enantiomers, and CYP2B6 may participate in rac-FS metabolism. In addition, rac-FS, (+)-FS, and (-)-FS were reversible competitive CYP1A2, CYP2C19, and CYP3A4/5 inhibitors. High stereoselective inhibition potential was verified; rac-FS and (-)-FS strongly inhibited and (+)-FS moderately inhibited CYP1A2. Stereoselective differences were also detected for CYP2C19 and CYP3A4/5, which were strongly inhibited by rac-FS, (+)-FS, and (-)-FS. Our results indicated a high potential for CYP450 drug-pesticide interactions, which may affect human health. The lack of stereoselective research on the effect of chiral pesticides on the activity of CYP450 isoforms highlights the importance of assessing the risks of such pesticides in humans.