Health risk assessment and quality reference values of potentially toxic elements in soils of the Southwestern Amazonas State - Brazil.

The geochemical processes involved in the Amazon soils formation are not totally understood because its geological and pedological features were formed during different geological events and different times. The Southwestern region of Amazonas State is an example of a region where the soils were developed from rocks formed by sedimentary processes and, nowadays, the soils continue receiving seasonal inputs from the Andes sediments. Data on geochemical patterns of this region are scarce, and there is no information about the possible effects of the natural or unnatural enrichment of potentially toxic elements (PTEs). Thus, this study represents the first research into the geochemical patterns of PTEs in soils of Southwestern Amazonas State. Further, we carried out a human health risk assessment and a proposal for Quality Reference Values (QRV) for thirteen PTEs (As, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Ti, V, Zn and Zr). Our findings showed that the PTEs contents in soil samples collected in the lowland areas are strongly influenced by sediments inputs, while samples localized in the highland areas are weakly influenced by sediments inputs and present depletion of PTEs. Barium, Cr, Cu, Ni and Pb were the PTEs most influenced by sediment's deposition. The soil contamination assessment showed the existence of enrichment of the potentially toxic elements in soil samples, which may be a consequence of the natural inputs of the Andean sediments. Furthermore, Co and Cr exceed the safety zone for carcinogenic risk assessment, which indicates the need to monitor these elements and their possible effects on the health of the population in this region.

Potential of plant species adapted to semi-arid conditions for phytoremediation of contaminated soils.

Physical and chemical remediation techniques used in contaminated areas are expensive and damaging to the soil structure. Biological alternatives, such as phytoremediation, are economical and applicable to large areas. The main limitation of phytoremediation is identifying plants that are both capable of stabilizing and/or absorbing metals from soil and adapted to edaphoclimatic conditions of the contaminated areas. The objective of this study is to evaluate the ability of plant species adapted to Brazilian semi-arid conditions to grow in soils contaminated with Pb. A greenhouse experiment was carried out in a 4 × 5 factorial: four plant species (M. oleifera, P. juliflora, A. peregrina, and U. ruziziensis) and five Pb concentrations in soil (0.0; 0.52; 1.05; 2.10, and 4.20 g kg-1). All species grew at all Pb levels, but only P. juliflora and A. peregrina did not exhibit significant reductions in most growth variables. U. ruziziensis, despite showing reductions in growth variables, was the species with the highest dry matter accumulation in both shoots and roots, in addition to accumulating higher amounts of Pb. We conclude that the species P. juliflora, A. peregrina and U. ruziziensis are more suitable for cultivation in soils containing high levels of Pb.

Predictive modeling of contents of potentially toxic elements using morphometric data, proximal sensing, and chemical and physical properties of soils under mining influence.

Several anthropic activities, especially mining, have contributed to the exacerbation of contents of potentially toxic elements in soils around the world. Mines can release a large amount of direct sources of contaminants into the environment, and even after the mines are no longer being exploited, the environmental liabilities generated may continue to provide contamination risks. Potentially toxic elements (PTEs), when present in the environment, can enter the food chain, promoting serious risks to human health and the ecosystem. Several methods have been used to determine the contents of PTEs in soils, but most are laborious, costly and generate waste. In this study, we use a methodological framework to optimize the prediction of levels of PTEs in soils. We used a total set of 120 soil samples, collected at a depth of 0-10 cm. The covariate database is composed of variables measured by proximal sensors, physical and chemical soil characteristics, and morphometric data derived from a DEM with a spatial resolution of 30 m. Five machine learning algorithms were tested: Random Forests, Cubist, Linear Model, Support Vector Machine and K Nearest Neighbor. In general, the Cubist algorithm produced better results in predicting the contents of Pb, Zn, Ba and Fe compared to the other tested models. For the Al contents, the Support Vector Machine produced the best prediction. For the Cr contents, all models showed low predictive power. The most important covariates in predicting the contents of PTEs varied according to the studied element. However, x-ray fluorescence measurements, textural and morphometric variables stood out for all elements. The methodology structure reported in this study represents an alternative for fast, low-cost prediction of PTEs in soils, in addition to being efficient and economical for monitoring potentially contaminated areas and obtaining quality reference values for soils.

Human health risk assessment and geochemical mobility of rare earth elements in Amazon soils.

Rare earth elements (REEs) are a grouping of elements that encompasses lanthanides, yttrium and scandium due to their similar chemical properties and occurrence in ore deposits. Over the past few decades, economic interest in REEs has increased due to their use in several types of industries such as high-tech, medicine and agriculture. Extraction of REEs has been followed, in general, by incorrect disposal of tailing and waste, creating hazardous conditions in several countries. However, the magnitude of the possible impacts on ecosystem and human health are relatively unknown, especially in tropical systems. Thus, the objectives of this study were to assess the geochemical mobility and the bioaccessibility of REEs based on a series of chemical extractions and in vitro essay. We also tested two promising simple protocols (0.01 mol L-1 CaCl2 and 0.43 mol L-1 HNO3) for measuring REE bioaccessible fractions through a single extraction. Our findings show that the bioavailable fractions represent less than 20% of the ΣREEs fraction in all soil samples examine. Similarly, the oral bioaccessibility obtained by two in vitro methods (Gastric protocol and Gastric-Intestinal protocol) and by the single extraction tests represented less than 20% of the ΣREE contents. The non-carcinogenic risks and the carcinogenic risks associated to REEs oral exposure were low for children and adults. The extractions with 0.01 mol L-1 CaCl2 showed great potential as a method for measuring the REEs bioaccessible fraction.

Geochemical signatures and natural background values of rare earth elements in soils of Brazilian Amazon.

Rare earth elements (REEs) are generally defined as a homogenous group of elements with similar physical-chemical properties, encompassing Y and Sc and the lanthanides elements series. Natural REEs contents in soils depend on the parent material, the soil genesis processes and can be gradually added to the soil by anthropogenic activities. The REEs have been considered emerging pollutants in several countries, so the establishment of regulatory guidelines is necessary to avoid environmental contamination. In Brazil, REE soils data are restricted to some regions, and knowledge about them in the Amazon soils is scarce, although this biome covers more than 40% of the Brazilian territory. Thus, the objectives of this study were to determine the REE content in soils of two hydrographic basins (Solimões and Rio Negro) of the Amazon biome, establish their Quality Reference Values (QRV) and to investigate the existence of enrichment of REEs in urban soils. The ΣREE(Y + Sc) content of Solimões surface samples was 109.28 mg kg-1 and the ΣREE(Y + Sc) content in the subsurface samples was 94.11 mg kg-1. In soils of Rio Negro basin, the ΣREE(Y + Sc) was 43.95 15 mg kg-1 surface samples and 38.40 mg kg-1 in subsurface samples. The ΣREE(Y + Sc) in urban topsoils samples was 38.62 mg kg-1. The REEs contents pattern in three studied areas are influenced in different amplitude by natural soil properties. The REEs content in urban topsoils were slightly higher than the Rio Negro pristine soils, but the ecological risk was low. QRVs recommend for Solimões soils ranged from 0.01 (Lu) to 145.6 mg kg-1 (Ce) and for Rio Negro soils ranged from 0.05 (Lu) to 15.8 mg kg-1 (Ce).

Health risks of potentially toxic trace elements in urban soils of Manaus city, Amazon, Brazil.

The city of Manaus is the biggest industrial city of the north Brazilian region, and a haphazard urbanization process characterizes it. The continuous urbanization and industrialization processes have increased the levels of trace elements in the urban environment and have posed great threat on human health. It is, then, essential to assess the pollution levels and the potential risks of the trace elements presence in urban soils. Therefore, the purpose of this study was to investigate the status of trace elements soils pollution and their human health risks to the population of Manaus City. Twenty-two soil samples were collected from the surface layer (0-20 cm), and the contents of Ba, Cr, Mn, Zn, Co, Ni, Cu, Cd and Pb were analyzed. Results showed the predominance of kaolinite, gibbsite and goethite as the main minerals of the clay fraction. The trace elements contents were affected by both natural sources and anthropic activities such as industrial operations and vehicular emissions. The soil contamination assessment by Enrichment Factor showed the existence of eight samples classified as considerably contaminated and two samples classified as highly contaminated. Geoaccumulation index also showed the existence of eight samples exhibiting considerable contamination and one sample showing high contamination. The non-carcinogenic health risk was considered low (HI < 1) to both children and adults. However, the carcinogenic risk of Cd and Pb was higher than the safety limits (CRtotal > 1 × 10-6), indicating that the long exposure to contaminated soils increases the probability of children's cancer occurrence.

Risk assessment of trace elements pollution of Manaus urban rivers.

Manaus is the Capital City of Amazonas State, Brazil, in the heart of the Amazon rainforest. Its metropolitan area has a huge hydrographic basin where the disorganized urbanization has caused adverse effects in the urban rivers and creeks water quality. Thus, this study was conducted to evaluate the contents of Ba, Cr, Mn, Zn, Ni, Cu, the physicochemical parameters and their respective health risks in water samples from rivers and creeks located in urban areas with different degrees of urbanization in two different seasons. The determination of the physicochemical parameters showed the samples collected in areas with riparian vegetation presented mean values of temperature, pH, total dissolved solids and electrical conductivity lower than samples collected in urban environment. The hotspots of trace elements content were associated to the presence of industrial and domestic effluents as the main pollution source. The Water Quality Index results denoted a low water quality in four sampling sites, one during the rainy season and three others during the dry season. The overall non-carcinogenic health in the urban rivers was considered high in regions with huge population and intense anthropogenic activity. The results showed the potential risk of some of the trace elements on human beings, especially on children. The main element contributor to non-carcinogenic risk was Cr, although Mn and Ni also contributed to non-carcinogenic risk in a few areas, mainly for children during the dry season.

Heavy metals in iron ore tailings and floodplain soils affected by the Samarco dam collapse in Brazil.

In November 2015, the Fundão Dam collapsed releasing about 35 million m-3 of iron ore tailings into the environment, which covered approximately 15 km2 of floodplain soils. Four years later, there is still great concern and controversy regarding contamination by heavy metals in the affected areas. Thus, the present study sought to evaluate the heavy metal contents and its distribution in tailings and non-affected soils. Tailings samples were collected in the stretch between Bento Rodrigues and the Candonga hydroelectric plant, in addition to a sample inside the Fundão Dam. Non-affected soils and river sediments from the same region were also collected as a control group. The heavy metal contents in the tailings were lower than in non-affected samples from the same area, discarding the hypothesis of contamination by the tailings mud. The non-affected samples presented high levels of As, Ba, Co, Cr, Cu, Ni and Zn, with at least one sample exceeding the quality reference values (QRV's) established for Minas Gerais state, which indicated a scenario of pre-disaster contamination for the Doce River watershed. Most of the elements (As, Cr, Cu, Ni, V and Zn) were extracted in the residual fraction of the BCR sequential extraction, presenting low risk of release in nature. The health risk assessment for As estimated that all the non-affected soils and sediments from Gualaxo do Norte, Carmo and Doce rivers have carcinogenic risk higher than the acceptable value for children. From our results, it is more likely to conclude that the deposited tailings are not a time-bomb for heavy metals contamination in the region.

Simplex-Centroid mixture design applied to arsenic (V) removal from waters using synthetic minerals.

Arsenic (As) is a toxic and carcinogenic element. Therefore, it is necessary to carry out research on As-contaminated water management in order to achieve the World Health Organization (WHO) standard for drinking water (0.010 mg L-1). A Simplex-Centroid mixture design (SCMD) was used to determine the best mineral composition for both maximum adsorption capacity of As(V) (MAC-As) and residual concentration of As(V) (RC-As), using synthetic poorly crystallized aluminum hydroxide (pAlHyd), calcined layered double hydroxide (cLDH), and two-line ferrihydrite (2ℓFh). The analysis of variance results and the predicted values of models showed a good agreement with the experimental data, indicating that SCMD is a reliable method to optimize As removal through determination of the best mineral composition. The ability of pure synthetic minerals to remove As from water was different among those mixtures thereof, which indicate that the mineral components interacted with each other. Results showed that cLDH was the best As adsorbent. However, it showed a RC-As higher than the WHO standard. The pAlHyd and 2ℓFh exhibited smaller MAC-As, but they lowered RC-As to below 0.010 mg L-1, showing no direct relationship between high MAC-As and low RC-As. Therefore, mineral compositions which combine high adsorption capacity with low residual concentration should work better for removing As from drinking water, ensuring it meets the WHO potability standard. Ternary diagrams for MAC-As and RC-As showed that the best combination for maximizing MAC-As and reducing RC-As should be a mixture of 75-90% of cLDH, 10-20% of pAlHyd, and 0-5% of 2ℓFh.

An overview of the environmental applicability of vermicompost: from wastewater treatment to the development of sensitive analytical methods.

The use of vermicompost (humified material) for treating wastewaters, remediating polluted soils, improving agricultural productivity, protecting crop production, and developing sensitive analytical methods is reviewed here, covering the past 17 years. The main advantages of vermicompost, considering all applications covered in this paper, comprise (i) easy acquisition, (ii) low costs, (iii) structural, chemical, and biological characteristics responsible for exceptional adsorptive capacities as well as pollutant degradation, and (iv) the promotion of biocontrol. Specifically, for wastewater decontamination, a considerable number of works have verified the adsorption of toxic metals, but the application of vermicompost is still scarce for the retention of organic compounds. Problems related to the final disposal of enriched vermicompost (after treatment steps) are often found, in spite of some successful destinations such as organic fertilizer. For decontaminating soils, the use of vermicompost is quite scarce, mainly for inorganic pollutants. In agricultural productivity and biocontrol, vermicompost imparts remarkable benefits regarding soil aggregation, plant nutrition, and the development of beneficial microorganisms against phytopathogens. Finally, the use of vermicompost in sensitive analytical methods for quantifying toxic metals is the newest application of this adsorbent.

Metais pesados em amostras biológicas de bovinos / Heavy metals in cattle biological samples

O objetivo deste trabalho foi determinar a concentração de metais pesados no sangue (Pb, Ni e Cd), soro (Cu e Zn), pelo e leite (Pb, Ni, Cd, Cu e Zn) de bovinos criados em área industrializada (com siderúrgicas) e não-industrial do Estado de Minas Gerais, em amostras coletadas em duas épocas (inverno e verão), buscando avaliar a contaminação em animais em função do ambiente de exposição e da estação do ano. O local de criação dos animais afetou significativamente somente a concentração de Cu obtida nas amostras de soro, com maiores valores determinados no grupo de bovinos da região industrializada. A época de amostragem afetou a concentração dos metais Cu (soro), Zn (soro e leite), Pb (sangue) e Cd (sangue e pelo), com as determinações efetuadas no verão proporcionando maiores teores do que as executadas no inverno, à exceção do Cd avaliado no pelo. Interações significativas (P<0,05) entre área de criação e época do ano foram verificadas para Cu (pelo e leite), Zn (pelo) e Ni (soro, pelo e leite). Os resultados obtidos indicam que a presença de siderúrgicas em determinada região não implica, necessariamente, incrementos nas concentrações de metais pesados em matrizes biológicas de bovinos. Pode haver influência da sazonalidade nas concentrações de metais pesados obtidas nessas matrizes, fato que deve ser considerado em programas de monitoramento ambiental.

The aim of this research was to determine the heavy metals concentration in blood (Pb, Ni and Cd), serum (Cu and Zn), hair and milk (Pb, Ni, Cd, Cu and Zn) of cattle raised in industrial (with steel mill) and non-industrial areas in Minas Gerais, Brazil. The samples were collected during summer and winter, aiming to verify animals contamination related to environment and year season. The environment significantly influenced the concentration of Cu obtained on serum samples, with higher values for cattle from the industrialized area. The sampling time affected the concentration of Cu (serum), Zn (serum and milk), Pb (blood) and Cd (blood and hair), with higher values for summer, except for Cd measured on hair. Meaningful interactions (P<0.05) between environment and year season were identified for Cu (hair and milk), Zn (hair) and Ni (serum, hair and milk). The results obtained show that the presence of steel mills in a determined area does not mean, necessarily that higher concentration of heavy metals will be found in cattle biological matrices. The seasonality can influence the heavy metal concentration obtained from these matrices, fact that should be considered in environment monitoring programs.

Caracterização do amido de grão-de-bico (Cicer arietinum L) / Chickpea (Cicer arietinum L) starch characterization

O objetivo deste trabalho foi extrair e caracterizar o amido de grão-de-bico quanto a sua composição química, estrutural e morfológica, propriedades térmicas e tecnológicas. O rendimento apresentado no processo de extração foi de 28 por cento, com alta pureza. A observação em microscopia eletrônica de varredura mostrou grânulos de amido com formato cilíndrico e oval, com dimensões de 20 um de comprimento e 10 um de largura. O padrão de cristalinidade mostrado por difratometria de raios X foi do tipo C, típico de leguminosas. A análise das propriedades de pasta foi efetuada por calorimetria diferencial de varredura (DSC) e analisador rápido de viscosidade (RVA). Em DSC, foi encontrada a temperatura inicial de gelatinização de 65,51 graus C, a final de 86,90 graus C e a entalpia de gelatinização de 12,12 J/g. O RVA mostrou temperatura inicial de gelatinização de 73,1 graus C, valores elevados de viscosidade, baixa quebra e alta tendência à retrogradação. O amido apresentou pouco inchamento e solubilidade, mesmo na temperatura de 90 graus C. O gel de amido de grão-de-bico mostrou-se turvo e com alta sinérese e apresentou elevada dureza e elasticidade em análise de perfil de textura.