Tracing isotopically labeled selenium nanoparticles in plants via single-particle ICP-mass spectrometry.

Agronomic biofortification using selenium nanoparticles (SeNPs) shows potential for addressing selenium deficiency but further research on SeNPs-plants interaction is required before it can be effectively used to improve nutritional quality. In this work, single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) was used for tracing isotopically labeled SeNPs (82SeNPs) in Oryza sativa L. tissues. For this purpose, SeNPs with natural isotopic abundance and 82SeNPs were synthesized by a chemical method. The NPs characterization by transmission electron microscopy (TEM) confirmed that enriched NPs maintained the basic properties of unlabeled NPs, showing spherical shape, monodispersity, and sizes in the nano-range (82.8 ± 6.6 nm and 73.2 ± 4.4 nm for SeNPs and 82SeNPs, respectively). The use of 82SeNPs resulted in an 11-fold enhancement in the detection power for ICP-MS analysis, accompanied by an improvement in the signal-to-background ratio and a reduction of the size limits of detection from 89.9 to 39.9 nm in SP-ICP-MS analysis. This enabled 82SeNPs to be tracked in O. sativa L. plants cultivated under foliar application of 82SeNPs. Tracing studies combining SP-ICP-MS and TEM-energy-dispersive X-ray spectroscopy data confirmed the uptake of intact 82SeNPs by rice leaves, with most NPs remaining in the leaves and very few particles translocated to shoots and roots. Translocation of Se from leaves to roots and shoots was found to be lower when applied as NPs compared to selenite application. From the size distributions, as obtained by SP-ICP-MS, it can be concluded that a fraction of the 82SeNPs remained within the same size range as that of the applied NP suspension, while other fraction underwent an agglomeration process in the leaves, as confirmed by TEM images. This illustrates the potential of SP-ICP-MS analysis of isotopically enriched 82SeNPs for tracing NPs in the presence of background elements within complex plant matrices, providing important information about the uptake, accumulation, and biotransformation of SeNPs in rice plants.

A Simple, Ecofriendly, and Fast Method for Nitrate Quantification in Bottled Water Using Visible Spectrophotometry.

There are many works associating the presence of nitrate in water and the occurrence of cancer in humans. The most common method for quantifying nitrate in water is based on the use of toxic cadmium as a reductant. In this work, a new approach was developed for the quantification of nitrate in bottled water with indirect spectrophotometry using Zn0 as a reductant. Nitrate is reduced to nitrite using Zn0 in a buffered medium (acetate/acetic acid) and quantified with visible spectrophotometry using the Griess reaction between sulfanilamide and N-(1-naphthyl)-ethylenediamine. The influence of pH, buffer solution (constitution and concentration), Zn0 (mass and granulometry), and agitation time on the efficiency of nitrite generation was evaluated. The optimal conditions were an acetate-acetic acid buffer solution with a concentration and pH of 0.75 mol L-1 and 6.00, respectively, and a Zn0 particle size of 20 MESH and Zn0 mass of 300 mg. The limits of detection and quantification (LoD and LoQ) were 0.024 and 0.08 mg L-1, respectively. The method's accuracy and precision were evaluated using the analysis of commercial bottled water. In conclusion, the use of Zn0 instead of cadmium provided a green method with excellent LoD/LoQ. Further, the method proved to be simple and easy to apply during outdoor analysis.

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.

Essential and Toxic Elements in Infant Cereal in Brazil: Exposure Risk Assessment.

Infant cereals, one of the first solid foods introduced to infants, have been reported to pose risks to human health because they contain toxic elements and an excess of essential elements. The objective of this study was to assess the cancer and non-cancer risk of exposure to essential and toxic elements in infant cereal in Brazil. In our analyses, we included data from 18 samples of infant cereals made from different raw materials and estimated the incremental lifetime cancer risks and non-cancer hazard quotients (HQs) for their consumption. Rice cereal is particularly concerning because it is immensely popular and usually contains high levels of inorganic arsenic. In addition to arsenic, we assessed aluminum, boron, barium, cadmium, chromium, copper, lead, manganese, nickel, selenium, silver, strontium, and zinc. The cancer risk was highest for rice cereal, which was also found to have an HQ > 1 for most of the tested elements. Inorganic As was the element associated with the highest cancer risk in infant cereal. All of the infant cereals included in this research contained at least one element with an HQ > 1. The essential and non-essential elements that presented HQ > 1 more frequently were zinc and cadmium, respectively. The cancer and non-cancer risks could potentially be decreased by reducing the amount of toxic and essential elements (when in excess), and public policies could have a positive influence on risk management in this complex scenario.

Antimicrobial and optical properties of a new biogenic silica-coated silver nanoparticles incorporated into experimental resin.

Background: Evaluate the effects of incorporating silica-coated silver nanoparticles (Ag@SiO2 NPs) into odontological clinic resin materials. Material and Methods: Silver nanoparticles coated with silicon dioxide were added to the experimental resin matrix at 1, 3, and 5wt%. Degree of conversion (DC), optical properties (total transmittance and color change), and microstructural analysis were evaluated. Materials were tested for silver ion release, cytotoxicity in dental pulp fibroblasts, Streptococcus mutans biofilm growth by Colony-Forming Unit (CFU) and confocal laser scanning microscopy (CLSM). Results: Groups had a similar DC, despite significant differences observed in transmittance and color change analysis for all groups with NPs. Silver ion release values were below the detection limit after 72h for all groups, and NPs incorporation did not show a statistical difference from the control on pulp fibroblasts assay. After 72h, the CFU count was significantly reduced by 74% from 3wt% of Ag@SiO2NPs. CLSM evaluation on S. mutans colonies showed a dose-dependent decrease in the emitted fluorescence. Conclusions: The application of Ag@SiO2 NPs in a resinous matrix, demonstrates a significant reduction of S. mutans CFU in oral biofilm, at concentrations from 3wt%, without an increase in cytotoxicity. The reduced transmittance values did not affect the DC, although a significant color change was perceived in all concentrations. Key words:Nanoparticles, Silver Compounds, Composite Dental Resin, Anti-Bacterial Agent, Optical Imaging.

Multiple potentially toxic elements in urban gardens from a Brazilian industrialized city.

Urban agriculture should be promoted as long as the food produced is safe for consumption. Located in the metropolitan region of São Paulo-Brazil, Santo André has intense industrial activities and more recently an increasing stimulus to urban gardening. One of the potential risks associated to this activity is the presence of potentially toxic elements (PTEs). In this study, the concentration of PTEs (As, Ba, Cd, Co, Cu, Cr, Ni, Mo, Pb, Sb, Se, V and Zn) was evaluated by soil (n = 85) and soil amendments (n = 19) in urban gardens from this municipality. Only barium was above regulatory limits in agricultural soil ranging from 20 to 112 mg kg-1. Geochemical indexes (Igeo, Cf and Er) revealed moderate to severe pollution for As, Ba, Cr, Cu, Pb Se and Zn, especialy in Capuava petrochemical complex gardens. A multivariate statistical approach discriminated Capuava gardens from the others and correlated As, Cr and V as main factors of pollution. However, carcinogenic and non-carcinogenic risks were below the acceptable range for regulatory purposes of 10-6-10-4 for adults. Soil amendments were identified as a possible source of contamination for Ba, Zn and Pb which ranged from 37 to 4137 mg kg-1, 20 to 701 mg kg-1 and 0.7 to 73 mg kg-1, respectively. The results also indicated the presence of six pathogenic bacteria in these amendments. Besides that, the occurrence of antimicrobial resistance for Shigella, Enterobacter and Citrobacter isolates suggests that soil management practices improvement is necessary.

Implications of ZnO Nanoparticles and S-Nitrosoglutathione on Nitric Oxide, Reactive Oxidative Species, Photosynthetic Pigments, and Ionomic Profile in Rice.

Zinc is an important nutrient for several plants and humans. Nitric oxide (NO) is a free radical that is important to biological processes that mediate the growth and mitigation of biotic and abiotic stresses in plants. The present study investigated the enzymatic and photosynthetic profile and the accumulation of macro- and microelements in rice plants (Oryza sativa L.) that received foliar treatments of zinc oxide nanoparticles (ZnO NPs), nitric oxide donor (GSNO), and the association of both (GSNO-ZnO NPs). Zinc concentration in rice husks increased by 66% and 68% in plants treated with ZnO NPs and GSNO-ZnO NPs, respectively. The GSNO treatment caused an increase of 25% in the Fe concentration in the rice grains. Only a small disturbance of the antioxidant system was observed, with increases in H2O2, S-NO, and NO2-, mainly in the group treated with GSNO-ZnO NPs; however, the disturbance did not affect the yield, the growth, or vital processes, such as as photosynthetic pigments production. There was an increase in chlorophyll B of 290% and an increase in chlorophyll A of 187% when ZnO NPs was applied. GSNO-ZnO NPs increased chlorophyll B by 345% and chlorophyll A by 345%, indicating that the treatments GSNO, ZnO NPs, and GSNO-ZnO NPs reduced possible oxidative stress and helped as protective treatments.

Chronic exposure to nitric oxide sensitizes prostate cancer cells and improved ZnO/CisPt NPs cytotoxicity and selectivity.

The co-therapy of common chemotherapeutics with nitric oxide (NO), an endogenous signaling molecule, is proposed as an alternative to sensitize cancer cells and enhance treatments' efficacy. Herein, we have synthesized cisplatin-releasing zinc oxide nanoparticles (ZnO/CisPt NPs), which promoted a sustained and pH targeted release, able to release a higher amount of CisPt at tumor microenvironment conditions. This material was combined with a chronic NO treatment, at low concentration, in prostate cancer cells (PC3). NO treatment enhanced the S-NO concentration in PC3 cells, suggesting the nitrosylation or transnitrosylation processes enhancement, which are directly related to S-NO binding to proteins, function alterations and cancer cells death. Indeed, these mechanisms directly impacted the cytotoxic effect of ZnO/CisPt NPs, inducing a 30 % higher viability reduction of PC3 cells after NO treatment, along with a higher selectivity index when compared to normal human fibroblasts (FN1).

Impact of DNA repair polymorphisms on DNA instability biomarkers induced by lead (Pb) in workers exposed to the metal.

Although the mechanisms of Pb-induced genotoxicity are well established, a wide individual's variation response is seen in biomarkers related to Pb toxicity, despite similar levels of metal exposure. This may be related to intrinsic variations, such as genetic polymorphisms; moreover, very little is known about the impact of genetic variations related to DNA repair system on DNA instability induced by Pb. In this context, the present study aimed to assess the impact of SNPs in enzymes related to DNA repair system on biomarkers related to acute toxicity and DNA damage induced by Pb exposure, in individuals occupationally exposed to the metal. A cross-sectional study was run with 154 adults (males, >18 years) from an automotive batteries' factory, in Brazil. Blood lead levels (BLL) were determined by ICP-MS; biomarkers related to acute toxicity and DNA instability were monitored by the buccal micronucleus cytome (BMNCyt) assay and genotyping of polymorphisms of MLH1 (rs1799977), OGG1 (rs1052133), PARP1 (rs1136410), XPA (rs1800975), XPC (rs2228000) and XRCC1 (rs25487) were performed by TaqMan assays. BLL ranged from 2.0 to 51 µg dL-1 (mean 20 ± 12 µg dL-1) and significant associations between BLL and BMNCyt biomarkers related to cellular proliferation and cytokinetic, cell death and DNA damage were observed. Furthermore, SNPs from the OGG1,XPA and XPC genes were able to modulate interactions in nuclear bud formation (NBUDs) and micronucleus (MNi) events. Taken together, our data provide further evidence that polymorphisms related to DNA repair pathways may modulate Pb-induced DNA damage; studies that investigate the association between injuries to genetic material and susceptibilities in the workplace can provide additional information on the etiology of diseases and the determination of environmentally responsive genes.

Selenium Biofortification Enhanced Grain Yield and Alleviated the Risk of Arsenic and Cadmium Toxicity in Rice for Human Consumption.

Arsenic (As) and Cadmium (Cd) are toxic to rice plants. However, selenium (Se) has the potential to regulate As and Cd toxicity. The present study aimed to evaluate the co-exposure to As5+ and Se6+ species in two rice cultivars, BRS Pampa and EPAGRI 108. The plants were divided into six groups and cultivated until complete maturation of the grains, under greenhouse conditions. Regarding total As and inorganic As (i-As) accumulation in grains, the highest concentrations were found for BRS Pampa. For Se, EPAGRI 108 presented the highest concentration of inorganic and organic Se (i-Se and o-Se). The exposure assessments showed that Se biofortification can mitigate the As accumulation in rice and, consequently, the risk of As and Cd toxicity in grains for human consumption. The combined effect of As and Se in rice plants could represent an alternative to biofortify this food in a safe way and with a higher percentage of bioavailable Se. Although Se is able to mitigate As toxicity in rice plants, in the present study we showed that co-exposure in different cultivars under the same growing conditions may present different responses to As and Se exposure.

Chromium Speciation by HPLC-DAD/ICP-MS: Simultaneous Hyphenation of Analytical Techniques for Studies of Biomolecules.

The first element legislated adopting chemical speciation was chromium (Cr) for differentiation between the highly toxic Cr(VI) from the micronutrient Cr(III). Therefore, this work aimed to develop a new analytical method through the coupling of High-Performance Liquid Chromatography with Diode-Array Detection (HPLC-DAD) with inductively coupled plasma mass spectrometry (ICP-MS) to obtain molecular and elemental information simultaneously from a single sample injection. In the first step, a low-cost flow split made of acrylic was developed aiming at optimally directing the sample to the detectors, enabling the HPLC-DAD/ICP-MS coupling. After the extraction of Certified Reference Materials (CRM of natural water NIST1640a and sugar cane leaf agro FC_012017), the recoveries determined by ICP-MS were 99.7% and 85.4%, respectively. Then, the method of HPLC-DAD/ICP-MS was applied for real samples of the CRMs. The presence of possible biomolecules associated with Cr(III) and Cr(VI) species was evaluated, with the simultaneous response detection of molecular (DAD) and elementary (ICP-MS) detectors. Potential biomolecules were observed during the monitoring of Cr(VI) and Cr(III) in sugar cane leaves, water samples and a supplement of Cr picolinate. Finally, the article also discusses the potential of the technique applied to biomolecules containing other associated elements and the need of more bioanalytical methods to understand the presence of trace elements in biomolecules.

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.

Influence of Agaricus bisporus Mushroom on Pb Toxicokinetic in Pregnant Rats.

(Pb) is a toxic metal, responsible for several damages to human health. Agaricus bisporus (Ab) is a mushroom with promising antioxidant properties to be used as an alternative chelator in Pb intoxication. The aim was to understand the Pb toxicokinetic and the potential of Ab as a protective agent. A total of 20 female Wistar rats were distributed into 4 groups (n = 5/group): Control (receiving water); Group Ab 100 mg/kg (gavage); Group Pb 100 mg/L in water; and Group Ab + Pb-100 mg/kg + 100 mg/L (gavage and water). Pb administration occurred daily until the 19th day of pregnancy. On day 19 of gestation, the rats were euthanized, and the blood and tissues were collected for Pb measurement, using an inductively coupled plasma mass spectrometer. The results showed that the levels of Pb in the blood, placenta, and liver of the mothers, and in the brain of the fetuses increased significantly in the Pb group. On the other hand, the combined exposure to Pb + Ab showed a significant decrease in the metal concentration in relation to the Pb group, returning to normal levels. Kidney and bone lead levels also increased significantly in the Pb group. However, in the combined exposure group, levels did not return to the control amounts; there was protection, but the Pb concentration was still significantly higher than in the control. In the brain, no significant differences were observed. In conclusion, we suggest A. bisporus is a natural chelator, because the co-administration of the mushroom was able to interact with Pb ions, minimizing the Pb absorption and distribution. These effects are suggested since A. bisporus have antioxidants and beta glucan that interact with Pb, chelating it and, thus, reducing its toxic effects.

Risk evaluation of occupational exposure of southern Brazilian flower farmers to pesticides potentially leading to cholinesterase inhibition and metals exposure.

This work presents a frequency matched observational study comparing flower farmers exposed to pesticides and unexposed individuals as controls. All subjects were interviewed before plasma and urine collection. Manganese and Zinc were measured in theses samples by using dynamic reaction cell inductively coupled mass spectrometry. Cholinesterase activity was analyzed through spectrophotometry by using a modified version of the Ellman method. Seventy-eight percent of subjects reported occupational contact with pesticides, from which 37% reported exposure for over 9 years. Flower farms farmers had increased odds of having headache and irritability, respectively, by factors of 6.2 and 2.4 than the control subjects. While the odds of exposed subjects to have insomnia was smaller than control subjects by a factor of 0.34. Exposure to pesticides had a significant effect regarding the plasmatic plasma and urinary manganese levels and whole blood cholinesterase activity (p < 0.05). High levels of plasma and urinary manganese, as well as cholinesterase inhibition in whole blood, were evident in the flower farmers who participated in the study.

Evaluation of collision/reaction gases in single-particle ICP-MS for sizing selenium nanoparticles and assessment of their antibacterial activity.

Selenium nanoparticles (SeNPs) have recently attracted attention because they combine the benefits of Se and lower toxicity compared to other chemical forms of this element. In this study, SeNPs were synthesized by a green method using ascorbic acid as the reducing agent and polyvinyl alcohol as stabilizer. The nanoparticles were widely characterized. To determine the total concentration of Se by ICP-MS, several isotopes and the use of He as collision gas were evaluated, which was effective in minimizing interferences. A method for sizing SeNPs by single particle ICP-MS (SP-ICP-MS) was developed. For this purpose, He and H2were evaluated as collision/reaction gases, and the second one showed promising results, providing an average diameter of 48 nm for the SeNPs. These results agree with those obtained by TEM (50.1 nm). Therefore, the SP-ICP-MS can be implemented for characterizing SeNPs in terms of size and size distribution, being an important analytical tool for Se and other widely studied nanoparticles (e.g. Ag, Au, Ce, Cu, Fe, Zn). Finally, the antibacterial activity of SeNPs was assessed. The SeNPs showed bacteriostatic activity against three strains of Gram-positive bacteria and were particularly efficient in inhibiting the growthE. faecaliseven at very low concentrations (MIC < 1.4 mg l-1). In addition, a bactericidal activity of SeNPs againstS. aureuswas observed. These nanoparticles may have potential application in pharmaceutical industry, biomedicine and agriculture.

Study of controlled migration of cadmium and lead into foods from plastic utensils for children.

Lead (Pb) is a highly neurotoxic chemical element known for reducing intelligence quotient (IQ) and promoting antisocial behavior in children and adolescents, while cadmium (Cd) is a carcinogenic bioaccumulative element. Both these metals are included in the priority pollutant list of the United States Environmental Protection Agency and in the WHO List of Chemicals of Major Public Health Concern, where contaminated foods and beverages are the most common pathways of exposure. The objective of this study was to determine total Cd and Pb levels in colored plastic utensils (cups, mugs, bowls, feeding bottles, and plates) for use by children and to measure the specific migration of these elements into beverages and foods. Total contaminant levels were determined using a handheld X-ray fluorescence analyzer. Specific migration tests were conducted using the simulant solutions acetic acid 3% (m/v) and water. Migration levels were determined by ICP-MS. Specific migration tests for Pb were also performed on commercially available samples (cola soft drink, orange juice, vinegar, and milk), with levels determined by graphite-furnace atomic absorption spectrometry (GF-AAS). A total of 674 utensils were analyzed in loco at major commercial centers in Greater São Paulo, of which 87 were purchased for containing Cd and Pb concentrations above permitted limits. Mean concentrations of the metals detected in the purchased utensils were 1110 ppm for Pb and 338 ppm for Cd. For specific migration assays, Pb levels were 187, 13, and 380 times above the permitted limit (0.01 mg.kg -1) for acetic acid, water, and orange juice, respectively. Cd levels were 50 and 2.4 times above the maximum permitted limit (0.005 mg.kg -1) for acetic acid and water, respectively. The districts where the utensils were purchased were grouped according to their social vulnerability index and compared using ANOVA. Pb levels were different between low and medium/high social vulnerability groups (p = 0.006). The findings corroborate the initial hypothesis that these utensils constitute a major source of exposure to PTEs such as Cd and Pb, pointing to the need for stricter regulation and inspection by the Brazilian regulatory agencies.

Determination of 14 trace elements in blood, serum and urine after environmental disaster in the Doce River basin: Relationship between mining waste and metal concentration in the population.

BACKGROUND: Exposure to chemical substances after an environmental disaster can cause both toxic effects and changes in the health status of people who live in or have proximity to environments of this nature, so that the concern with populations is growing. METHODS: In this cross-sectional study, blood, serum and urine samples were collected from 100 volunteers from Santo Antônio do Rio Doce, eight from Ilha das Pimentas and 50 from the control group; and analyzed by inductively coupled plasma mass spectrometry for biomonitoring of Al, As, Ba, Cd, Co, Cu, Cr, Fe, Hg, Mn, Ni, Se, Pb, Zn. In addition, a comprehensive questionnaire was applied to collect demographic and socioeconomic information, as well as lifestyle. RESULTS: The concentrations of As, Al, Cd, Ni and Mn were above the reference value in some biological matrices, with more pronounced exposure in Ilha das Pimentas. The concentrations of As, Cd, Cu, Co, Pb and Zn showed statistical differences regarding gender in the different biological matrices. The trace elements in the blood, serum and urine showed significant correlations when considering age and habits such as the consumption of cigarettes, alcoholic beverages and fish. The main correlations were observed between Co, Cr, Mn, Ni and Pb in the blood and cigarette consumption. CONCLUSION: This is the first study in these regions after the environmental disaster and confirmation of the diagnosis and health care of the participants should be promoted for clinical investigation and the eventual need for treatment. Human biomonitoring demonstrated high concentrations of some toxic elements, with more accentuated exposure in Ilha das Pimentas.

Integration of proteomic and metabolomic analyses: New insights for mapping informal workers exposed to potentially toxic elements.

Occupational exposure to potentially toxic elements (PTEs) is a concerning reality of informal workers engaged in the jewelry production chain that can lead to adverse health effects. In this study, untargeted proteomic and metabolomic analyses were employed to assess the impact of these exposures on informal workers' exposome in Limeira city, São Paulo state, Brazil. PTE levels (Cr, Mn, Ni, Cu, Zn, As, Cd, Sn, Sb, Hg, and Pb) were determined in blood, proteomic analyses were performed for saliva samples (n = 26), and metabolomic analyses in plasma (n = 145) using ultra-high performance liquid chromatography (UHPLC) coupled with quadrupole-time-of-flight (Q-TOF) mass spectrometry. Blood PTE levels of workers, controls, and their family members were determined by inductively coupled plasma-mass spectrometry (ICP-MS). High concentration levels of Sn and Cu were detected in welders' blood (p < 0.001). Statistical analyses were performed using MetaboAnalyst 4.0. The results showed that 26 proteins were upregulated, and 14 proteins downregulated on the welder group, and thirty of these proteins were also correlated with blood Pb, Cu, Sb, and Sn blood levels in the welder group (p < 0.05). Using gene ontology analysis of these 40 proteins revealed the biological processes related to the upregulated proteins were translational initiation, SRP-dependent co-translational protein targeting to membrane, and viral transcription. A Metabolome-Wide Association Study (MWAS) was performed to search for associations between blood metabolites and exposure groups. A pathway enrichment analysis of significant features from the MWAS was then conducted with Mummichog. A total of 73 metabolomic compounds and 40 proteins up or down-regulated in welders were used to perform a multi-omics analysis, disclosing seven metabolic pathways potentially disturbed by the informal work: valine leucine and isoleucine biosynthesis, valine leucine and isoleucine degradation, arginine and proline metabolism, ABC transporters, central carbon metabolism in cancer, arachidonic acid metabolism and cysteine and methionine metabolism. The majority of the proteins found to be statistically up or downregulated in welders also correlated with at least one blood PTE level, providing insights into the biological responses to PTE exposures in the informal work exposure scenario. These findings shed new light on the effects of occupational activity on workers' exposome, underscoring the harmful effects of PTE.

Potentially Toxic Elements in Costume Cosmetics Used by Children and Adults Are Associated with Cancer Risk.

(1) Background: Costume cosmetics, such as face paints and pancakes, are used by adults and children during Halloween, Carnival, or children's parties. However, the metallic-based pigments used as dyes in these products may contain toxic elements associated with different levels of exposure. Objectives: (a) to determine the Al, As, Ba, Cd, Co, Cr, Cu, Ni, Pb, Sb, Sn, and Sr concentrations in face paints and pancakes; and (b) to estimate cancer and non-cancer risks posed by the concentrations of each element in these products for dermal and ingestion exposure scenarios during children and adult use. (2) Methods: A total of 95 samples of face paints and pancakes (four brands in different textures and colors) were purchased at the largest high-street commercial center in São Paulo city, Brazil. An extraction procedure with nitric acid was carried out using a graphite-covered digester block. Toxic element determinations were performed using an ICP-MS. (3) Results: The non-cancer risks estimated were lower than 1, except for dermal exposure in adults for some target systems. High cancer risk values raise concerns in both groups. The risk for children ranged from 10-8 to 10-5 and proved higher in cases of accidental exposure by ingestion. For occupational exposure in adults, cancer risks were even higher, ranging from 10-3 to 10-5, with the highest values associated with dermal exposure. (4) Conclusions: The study results suggest the presence of potentially toxic elements (PTEs) in cosmetics should be regulated/monitored to protect human health, especially for occupational exposure and use by children.