Enhancing iron biogeochemical cycling for canga ecosystem restoration: insights from microbial stimuli.

Introduction: The microbial-induced restoration of ferruginous crusts (canga), which partially cover iron deposits and host unique ecosystems, is a promising alternative for reducing the environmental impacts of the iron mining industry. Methods: To investigate the potential of microbial action to accelerate the reduction and oxidation of iron in substrates rich in hematite and goethite, four different microbial treatments (water only as a control - W; culture medium only - MO; medium + microbial consortium - MI; medium + microbial consortium + soluble iron - MIC) were periodically applied to induce iron dissolution and subsequent precipitation. Except for W, all the treatments resulted in the formation of biocemented blocks. Results: MO and MI treatments resulted in significant goethite dissolution, followed by precipitation of iron oxyhydroxides and an iron sulfate phase, due to iron oxidation, in addition to the preservation of microfossils. In the MIC treatment, biofilms were identified, but with few mineralogical changes in the iron-rich particles, indicating less iron cycling compared to the MO or MI treatment. Regarding microbial diversity, iron-reducing families, such as Enterobacteriaceae, were found in all microbially treated substrates. Discussion: However, the presence of Bacillaceae indicates the importance of fermentative bacteria in accelerating the dissolution of iron minerals. The acceleration of iron cycling was also promoted by microorganisms that couple nitrate reduction with Fe(II) oxidation. These findings demonstrate a sustainable and streamlined opportunity for restoration in mining areas.

Maternal methylmercury exposure during early-life periods adversely affects mature enamel structure of offspring rats at human exposure levels: a concern for oral health.

Although there are many studies on the health effects of methylmercury (MeHg) toxicity during in utero and early development, little is known about its effects on mineralized tissues present in the oral cavity, such as enamel structure. Therefore, this study evaluated the effects of MeHg exposure on the physico-chemical, ultrastructural and functional properties of mature tooth enamel. Specifically, we studied offspring of mothers exposed to MeHg during the prenatal and postnatal periods which are the developmental stages associated with tooth enamel formation. Female rats were exposed to MeHg at a dose of 40 µg/kg/day for 42 days of pregnancy and lactation. The enamel of offspring was analyzed by (1) Fourier Transform Infrared Spectroscopy and Raman to assess physicochemical composition, (2) Scanning Electron Microscopy for ultrastructural evaluation, (3) Transmitted Polarizing Light Microscopy for analysis of the enamel extracellular matrix, and (4) resistance and hardness were evaluated by microhardness. The results showed that MeHg exposure during this sensitive enamel formation period induced changes in inorganic and organic content and enamel prisms ultrastructure alterations and disturbed the organic extracellular matrix due to a decreased enamel strength. These novel findings establish for the first time that maternal exposure to MeHg pre and postnatal promoted relevant changes in mature enamel of their offspring rats.

Changes in the surface water quality of a tropical watershed in the southeastern amazon due to the environmental impacts of artisanal mining.

The expansion of areas of human occupation and the increase in economic activity and deforestation are negatively impacting the Amazon ecosystem. Situated in the Carajás Mineral Province in the southeastern Amazon, the Itacaiúnas River Watershed (IRW) encompasses several active mines and has a historical record of intense deforestation primarily linked with the expansion of pasturelands, but also of urban areas, and mining activities. Industrial mining projects are subjected to strict environmental control, but artisanal mining (ASM; 'garimpos') sites have not been controlled, despite their known environmental impacts. In recent years, the opening and expansion of ASM in the IRW for the exploitation of mineral resources (Au, Mn, and Cu) have been remarkable. This study presents evidence of anthropogenic impacts, mainly caused by ASM, on the quality and hydrogeochemical characteristics of the IRW surface water. The hydrogeochemical data sets of two projects carried out in the IRW, during 2017 and from 2020 until present, were used to evaluate these impacts within the region. Water quality indices were calculated for the surface water samples. For the whole IRW, water collected during the dry season tended to yield better quality indicators in comparison to those collected during the rainy season. Two sampling sites at Sereno Creek showed very poor water quality and extremely high concentrations of Fe, Al, and potentially toxic elements over time. From 2016 to 2022, ASM sites increased markedly. Moreover, there are indications that Mn exploitation via ASM in Sereno hill is the main source of contamination in the area. New trends of ASM expansion were observed along the main watercourses, related to the exploitation of Au from alluvial deposits. Similar anthropogenic impacts are registered in other regions of the Amazon and environmental monitoring should be encouraged to assess the chemical safety of strategic areas.

Mercury in multimedia system of Itacaiúnas Basin, Brazilian Amazon: An integrated approach to understand its distribution, origin, and ecological risk.

This study presents the first integrated study on total Hg (THg) level in surface soil (SS), bottom soil (BS), stream sediments (SD), lake sediments (LS), stream water (SW), and lake water (LW) of Itacaiúnas River Watershed (IRW), Brazil to investigate the source and distribution of Hg in different environmental media considering contrasts of geological domains and sub-basins and its potential ecological and human risk. Hg content in most of the soils and sediments were above the upper crustal average values (56 µg/kg), however, when compared to the legal limits set by the Resolution CONAMA (Conselho Nacional de Meio Ambiente: soil 500 µg/kg; sediment 486 µg/kg), only 1 soil sample from Parauapebas sub-basin and 4 sediment samples from Violão Lake exceeded the limit. None of the SW and LW samples (<0.2 µg/L; CONAMA limit for Class II freshwater) are markedly contaminated by Hg. The SS and BS show similar contents and spatial distribution of Hg with higher contents being registered mostly in the Itacaiúnas and Parauapebas sub-basins, which are closely correlated with SD. This suggests that Hg levels are largely of geogenic origin and anthropogenic effect is highly limited. Principal Component Analysis (PCA) results show that Hg is strongly associated with total organic carbon (TOC), loss on ignition (LOI), and SO3, indicating organic matter as the main factor controlling the distribution of Hg and this is the major cause of accentuated Hg enrichment in lake sediments. The ecological risk index revealed a low pollution risk for most of the solid samples, except 11% LS and <1.5% SS and SD samples, which registered moderate risk. Health risk assessment indicated no adverse non-carcinogenic health effect on either adults and children in terms of Hg contamination. This information will be useful for Hg risk assessment in the Carajás region and future environmental research in this direction in the Amazonia.

In utero and lactational exposure to methylmercury elicits physical-chemical and morphological damages in the alveolar bone of offspring rats: The first toxicological findings.

Methylmercury (MeHg) is the most common organic form of mercury (Hg) that humans are exposed and is considered an environmental pollutant. Several populations that live in endemic regions of MeHg exposure are subject to the toxicant for long periods, including pregnant women and children, causing damage to several organs during early periods of development. Alveolar bone is an essential structure for the oral cavity, responsible for supporting teeth and masticatory forces. However, evidence on the effects of MeHg on alveolar bone and the intrauterine and lactation period is lacking. Thus, this study aimed to investigate the effects of MeHg exposure during gestation and lactation on the developing alveolar bone of offspring rats after maternal exposure. Dams were exposed during 41 days of pregnancy and lactation, and the mandibles of the offspring were collected. The alveolar bone was analyzed by Fourier Transform Infrared Spectroscopy to evaluate the physicochemical composition; by Scanning Electron Microscopy for ultrastructural evaluation; by histopathological, histochemical, and morphometric for tissue analyses. In addition, bone quality was assessed by X-ray microtomography. MeHg exposure altered the mineral composition and caused histological damage associated with a lower quantity and thickness of bone trabeculae, as well as reduced osteocyte density and collagen fiber content. A reduction in trabecular thickness and bone volume and an increase in trabecular spaces were observed and were associated with anatomical compromise of the vertical bone dimensions. Thus, the results suggest that the developing alveolar bone is susceptible to the toxic effects of MeHg when organisms are exposed during intrauterine and lactation periods. From a translational perspective, these changes in the alveolar bone can help us understand possible abnormalities induced by toxic metals and highlight the need for care for structures other than those already seen as targets for damage triggered by environmental MeHg exposure.

Effects of inorganic mercury exposure in the alveolar bone of rats: an approach of qualitative and morphological aspects.

BACKGROUND: In comparison to organic mercury (MeHg), the environmental inorganic mercury (IHg) can be found in some skin-lightening cosmestics were considered "harmless" for a long time. However, recent studies have shown that long-term exposure to low doses of IHg may affect biological systems. Therefore, this study investigated the effects of IHg long-term exposure to the alveolar bone of adult rats. METHODS: Adult Wistar rats were distributed in control and HgCl2 exposed (0.375 mg/kg/day). After 45 days, the rats were euthanized and both blood and hemimandibles were collected. Total blood Hg levels were measured and both inorganic and organic components of the alveolar bone were determined through XRD and ATR-FTIR. The microstructure of the alveolar bone was assessed by using micro-CT and the morphometric analysis was performed by using stereomicroscopy. RESULTS: Alterations in the physicochemical components of the alveolar bone of exposed animals were observed. The bone changes represented a tissue reaction at the microstructural level, such as bone volume increase. However, no significant dimensional changes (bone height) were observed. CONCLUSION: Exposure to IHg at this dose can promote microstructural changes and alteration in the organic and inorganic components in the alveolar bone.

Chronic exposure to lead acetate promotes changes in the alveolar bone of rats: microstructural and physical-chemical characterization.

There are a few data relating to the effects of lead (Pb) exposure on the alveolar bone, which has very distinct morphophysiological characteristics and is of great importance in the oral cavity. In this context, the aim of this study was to investigate the changes promoted after long-term exposure to Pb in the microstructure of the alveolar bone of rats. Twenty adult Wistar rats were exposed to 50 mg/kg/day of lead acetate for 55 days. These animals were euthanized and had their mandible removed. Each mandible was divided into hemimandibles, and the alveolar bone was used for bone lead quantification, crystallinity analysis, microstructure evaluation by the percentage of bone volume (BV/TV), number of trabeculae (Tb.N), thickness of the trabecular (Tb.Th), and trabecular space (Tb.Sp). Morphometric analysis of the exposed root area was also performed. Long-term exposure to Pb resulted in high levels of Pb in the alveolar bone but showed no changes in the organization of crystallinity. The microstructural analyses showed a reduction of BV/TV, Tb.Th, and Tb.N and increase of Tb.Sp parameters, resulting in an increase in the exposed root area and an alveolar bone loss in height. The findings of this study reveal the ability of Pb to alter the alveolar bone microstructure after long-term exposure to the metal, possibly due to changes in tissue homeostasis, contributing to the reduction of bone quality.

New Clayey Deposit and Their Potential as Raw Material for Red or Structured Ceramics: Technological Characterization.

Mineralogical and technological characterization of ceramic raw materials from a new deposit located at Caxias city, Maranhão State-Brazil, was accomplished to determine their potential as raw materials for the ceramics industry in northeastern Brazil. The ceramic raw materials were collected from three different locations on the site and characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), differential thermal analysis (DTA), and thermogravimetry (TG). The XRF analysis of the fraction < 2 µm revealed that most samples had SiO2 (35-51 wt%), Al2O3 (19-29 wt%), Fe2O3 (2-21 wt%), MgO (0.7 to 4.5 wt%) and K2O (0.9 to 5 wt%) as components. Quartz, kaolinite, illite, hematite and montmorillonite were the main mineral phases identified. DTA and TG analysis confirmed the mineral identification. The technological potential of the ceramic raw materials was investigated by: cation exchange capacity (CEC), plastic behavior (Atterberg Limits), linear shrinkage at 950 °C (LSF), flexural strength (FS), apparent porosity (AP), water absorption (WA) and bulk density (BD). The main experimental results-WA (9-17%), AP (19-31%), FS (2.0-23 MPa), and the Atterberg limits-indicated that the ceramic raw materials investigated have high potential to be used to develop mass for red or structured ceramics, such as bricks and roof tiles.

Long-term exposure to low doses of aluminum affects mineral content and microarchitecture of rats alveolar bone.

Aluminum (Al) is one of the most found elements in nature in many forms, and human exposure can be quite common. Therefore, it is important to investigate the effects of exposure to Al mainly at low doses and for a prolonged period, in order to simulate human exposure in the periodontium, an important structure for support and protection of the teeth. This investigation aimed to study the aluminum chloride (AlCl3) toxicological effects in the mineral composition and micromorphology of the alveolar bone of rats. Two groups of eight male Wistar rats were used for the experiment. AlCl3 group was exposed to AlCl3 orally at a dose of 8.3 mg/kg/day for 60 days, while the control group received only distilled water. After that, the mandibles were collected and submitted to the following analyses: Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray microtomography analysis; blood was also collected for determination of Al circulating levels. Our data showed that AlCl3 was capable of increasing Al circulating levels in blood. It was able to promote changes in the mineral content and triggers significant changes in the mineralized bone microstructure, such as number and thickness of trabeculae, being associated with alveolar bone-loss.

Source and background threshold values of potentially toxic elements in soils by multivariate statistics and GIS-based mapping: a high density sampling survey in the Parauapebas basin, Brazilian Amazon.

A high-density regional-scale soil geochemical survey comprising 727 samples (one sample per each 5 × 5 km grid) was carried out in the Parauapebas sub-basin of the Brazilian Amazonia, under the Itacaiúnas Basin Geochemical Mapping and Background Project. Samples were taken from two depths at each site: surface soil, 0-20 cm and deep soil, 30-50 cm. The ground and sieved (< 75 µm) fraction was digested using aqua regia and analyzed for 51 elements by inductively coupled plasma mass spectrometry (ICPMS). All data were used here, but the principal focus was on the potential toxic elements (PTEs) and Fe and Mn to evaluate the spatial distribution patterns and to establish their geochemical background concentrations in soils. Geochemical maps as well as principal component analysis (PCA) show that the distribution patterns of the elements are very similar between surface and deep soils. The PCA, applied on clr-transformed data, identified four major associations: Fe-Ti-V-Sc-Cu-Cr-Ni (Gp-1); Zr-Hf-U-Nb-Th-Al-P-Mo-Ga (Gp-2); K-Na-Ca-Mg-Ba-Rb-Sr (Gp-3); and La-Ce-Co-Mn-Y-Zn-Cd (Gp-4). Moreover, the distribution patterns of elements varied significantly among the three major geological domains. The whole data indicate a strong imprint of local geological setting in the geochemical associations and point to a dominant geogenic origin for the analyzed elements. Copper and Fe in Gp-1 were enriched in the Carajás basin and are associated with metavolcanic rocks and banded-iron formations, respectively. However, the spatial distribution of Cu is also highly influenced by two hydrothermal mineralized copper belts. Ni-Cr in Gp-1 are highly correlated and spatially associated with mafic and ultramafic units. The Gp-2 is partially composed of high field strength elements (Zr, Hf, Nb, U, Th) that could be linked to occurrences of A-type Neoarchean granites. The Gp-3 elements are mobile elements which are commonly found in feldspars and other rock-forming minerals being liberated by chemical weathering. The background threshold values (BTV) were estimated separately for surface and deep soils using different methods. The '75th percentile', which commonly used for the estimation of the quality reference values (QRVs) following the Brazilian regulation, gave more restrictive or conservative (low) BTVs, while the 'MMAD' was more realistic to define high BTVs that can better represent the so-called mineralized/normal background. Compared with CONAMA Resolution (No. 420/2009), the conservative BTVs of most of the toxic elements were below the prevention limits (PV), except Cu, but when the high BTVs are considered, Cu, Co, Cr and Ni exceeded the PV limits. The degree of contamination (Cdeg), based on the conservative BTVs, indicates low contamination, except in the Carajás basin, which shows many anomalies and had high contamination mainly from Cu, Cr and Ni, but this is similar between surface and deep soils indicating that the observed high anomalies are strictly related to geogenic control. This is supported when the Cdeg is calculated using the high BTVs, which indicates low contamination. This suggests that the use of only conservative BTVs for the entire region might overestimate the significance of anthropogenic contamination; thus, we suggest the use of high BTVs for effective assessment of soil contamination in this region. The methodology and results of this study may help developing strategies for geochemical mapping in other Carajás soils or in other Amazonian soils with similar characteristics.

Acetylation of Eugenol over 12-Molybdophosphoric Acid Anchored in Mesoporous Silicate Support Synthesized from Flint Kaolin.

A new prepared catalyst, 12-molybdophosphoric acid (HPMo) anchored to the mesoporous aluminosilicate AlSiM, synthesized from Amazon kaolin, was characterized and used as a heterogeneous acid catalyst for the production of eugenyl acetate by acetylation of eugenol with acetic anhydride. The effect of various reaction parameters, such as catalyst concentration, eugenol/acetic anhydride molar ratio, temperature and reaction time, was studied to optimize the conditions of maximum conversion of eugenol. The kinetics studies showed that in eugenol acetylation, the substrate concentration follows a first order kinetics. The results of activation energy was 19.96 kJ mol-1 for HPMo anchored to AlSiM. The reuse of the catalyst was also studied and there was no loss of catalytic activity after four cycles of use (from 99.9% in the first cycle to 90% in the fifth cycle was confirmed), and an excellent stability of the material was observed. Based on catalytic and kinetic studies, HPMo anchored to AlSiM is considered an excellent catalyst.

Dental enamel bleached for a prolonged and excessive time: Morphological changes.

This work aimed to evaluate the roughness, microhardness, ultrastructure, chemical composition and crystalline structure in submitted teeth to a prolonged home bleaching regimen with 10% carbamide peroxide (10% PC) for different periods. The specimens were divided into the following groups: G1: negative control (application of water-soluble gel); G2: tooth whitening group (positive control), under application time recommended by the manufacturer (4h/14 days); G3: prolonged whitening 50%, under prolonged time recommended by the manufacturer in 50% (4h/21 days); G4: excessive whitening 100%, under exceeded manufacturer recommended time by 100% (4h/ 28 days). The results were evaluated descriptively and analytically. There were no changes in the roughness in any of the evaluated groups. However, the microhardness decreased in the G4 group. Scanning electron microscopy showed changes in the enamel surface of groups G2, G3 and G4. Dispersive X-ray spectroscopy identified changes in the concentration of chemical elements O, Mg, P, K in all groups. Thus, this study showed that prolonged home bleaching could cause changes in the ultrastructure, chemical composition and microhardness of the enamel.

Avaliação de arsênio total, de elementos traços e bacteriológica em águas de consumo na comunidade do Elesbão, Município de Santana, estado do Amapá, Brasil / Total arsenic, trace elements and bacteriologycal evaluation in drinking water at Elesbão district, Santana city, Amapa state, Brazil

A mineração de manganês na Serra do Navio - AP foi desenvolvida pela empresa ICOMI Indústria e Comércio de Minérios S.A no período de 1957 a 1997 e o minério transportado até o Porto de Santana, às margens do rio Amazonas, a 30 Km de Macapá, capital do Estado do Amapá. Entre 1973 e 1983, a empresa manteve em funcionamento uma Usina de Pelotização nesta área, e os rejeitos gerados, contendo arsênio (As), depositados numa lagoa artificial, atingiram as águas superficiais de drenagens próximas. A possibilidade de exposição das populações levou a determinação de arsênio total nas águas de consumo humano coletadas a partir de 52 residências localizadas no entorno da área industrial nos meses de maio e novembro de 2003 e março de 2004. O trabalho se desenvolveu a partir de cinco grupos organizados geograficamente pela proximidade da área industrial: Comunidade do Elesbão (ELB), Rua Delta (DEL), Comunidade do Matapi (MAT), Rua da Olaria (OLA) e Bairro da Hospitalidade (HSP). As residências foram investigadas a partir do tipo de tratamento, residencial (RES) ou público (PUB), e captação, rio Amazonas (AMA) ou poços artesianos e ou amazonas (PCO). Os teores de As foram quantificados por Espectrometria de Absorção Atômica com Sistema de Geração de Hidretos (HG-AAS), apresentando ótima recuperação analítica e reprodutibilidade. Para complementação das análises, foram avaliados os teores de elementos traços (Ba, Cd, Cr, Cu, Fe, Mn, Na, Pb e Zn) e padrões bacteriológicos. Os resultados demonstraram que as águas de consumo das comunidades investigadas não apresentaram níveis anômalos de As e outros elementos traços, diferente dos padrões bacteriológicos, que estavam inadequados em cerca de 60 por cento das amostras, segundo Portaria 518 de 2004 do Ministério da Saúde.

Arsenic occurrence in Brazil and human exposure.

Environmental exposure to arsenic (As) in terms of public health is receiving increasing attention worldwide following cases of mass contamination in different parts of the world. However, there is a scarcity of data available on As geochemistry in Brazilian territory, despite the known occurrence of As in some of the more severely polluted areas of Brazil. The purpose of this paper is to discuss existing data on As distribution in Brazil based on recent investigations in three contaminated areas as well as results from the literature. To date, integrated studies on environmental and anthropogenic sources of As contamination have been carried out only in three areas in Brazil: (1) the Southeastern region, known as the Iron Quadrangle, where As was released into the drainage systems, soils and atmosphere as a result of gold mining; (2) the Ribeira Valley, where As occurs in Pb-Zn mine wastes and naturally in As-rich rocks and soils; (3) the Amazon region, including the Santana area, where As is associated with manganese ores mined over the last 50 years. Toxicological studies revealed that the populations were not exposed to elevated levels of As, with the As concentrations in surface water in these areas rarely exceeding 10 microg/L. Deep weathering of bedrocks along with formation of Fe/Al-enriched soils and sediments function as a chemical barrier that prevents the release of As into the water. In addition, the tropical climate results in high rates of precipitation in the northern and southeastern regions and, hence, the As contents of drinking water is diluted. Severe cases of human As exposure related to non-point pollution sources have not been reported in Brazil. However, increasing awareness of the adverse health effects of As will eventually lead to a more complete picture of the distribution of As in Brazil.