Human and environmental exposure to rare earth elements in gold mining areas in the northeastern Amazon.

Rudimentary methods are used to exploit gold (Au) in several artisanal mines in the Amazon, producing hazardous wastes that may pose risks of contamination by rare earth elements (REEs). The objectives of this study were to quantify the concentrations of REEs and assess their environmental and human health risks in artisanal Au mining areas in the northeastern Amazon. Thus, 25 samples of soils and mining wastes were collected in underground, colluvial, and cyanidation exploration sites, as well as in a natural forest that was considered as a reference area. The concentrations of REEs were quantified using alkaline fusion and inductively coupled plasma mass spectrometry, and the results were used to estimate pollution indices and risks associated with the contaminants. All REEs showed higher concentrations in waste deposition areas than in the reference area, especially Ce, Sc, Nd, La, Pr, Sm, and Eu. Pollution and enrichment levels were higher in the underground and cyanidation mining areas, with very high contamination factors (6.2-27) for Ce, Eu, La, Nd, Pr, Sm, and Sc, and significant to very high enrichment factors (5.5-20) for Ce, La, Nd, Pr, and Sc. The ecological risk indices varied from moderate (167.3) to high (365.7) in the most polluted sites, but risks to human health were low in all areas studied. The results of this study indicate that artisanal Au mining has the potential to cause contamination, enrichment, and ecological risks by REEs in the northeastern Amazon. Mitigation measures should be implemented to protect the environment from the negative impacts of these contaminants.

Magnesium-enriched poultry manure enhances phosphorus bioavailability in biochars.

Pyrolysis of calcium-rich feedstock (e.g., poultry manure) generates semi-crystalline and crystalline phosphorus (P) species, compromising its short-term availability to plants. However, enriching poultry manure with magnesium (Mg) before pyrolysis may improve the ability of biochar to supply P. This study investigated how increasing the Mg/Ca ratio and pyrolysis temperature of poultry manure affected its P availability and speciation. Mg enrichment by ∼2.1% increased P availability (extracted using 2% citric and formic acid) by 20% in Mg-biochar at pyrolysis temperatures up to 600 °C. Linear combination fitting of P K-edge XANES of biochar, and Mg/Ca stoichiometry, indicate that P species, mainly Ca-P and Mg-P, are altered after pyrolysis. At 300 °C, adding Mg as magnesium hydroxide [Mg(OH)2] created MgNH4PO4 (18%) and Mg3(PO4)2.8H2O (23%) in the biochar, while without addition of Mg Ca3(PO4)2 (11%) predominated, both differing only for pyrophosphate, 33 and 16%, respectively. Similarly, the P L2,3 edge XANES data of biochar made with Mg were indicative of either MgHPO4.3H2O or Mg3(PO4)2.8H2O, in comparison to CaHPO4.2H2O or Ca3(PO4)2 without Mg. More importantly, hydroxyapatite [Ca5(PO4)3(OH)] was not identified with Mg additions, while it was abundant in biochars produced without Mg both at 600 (12%) and 700 °C (32%). The presence of Mg formed Mg-P minerals that could enhance P mobility in soil more than Ca-P, and may have resulted in greater P availability in Mg-enriched biochars. Thus, a relatively low Mg enrichment can be an approach for designing and optimize biochar as a P fertilizer from P-rich excreta, with the potential to improve P availability and contribute to the sustainable use of organic residues.

Levels and environmental risks of rare earth elements in a gold mining area in the Amazon.

Artisanal gold (Au) mining may have increased the concentrations of rare earth elements (REEs) in the Serra Pelada mine (southeastern Amazon, Brazil), which has not been evaluated so far. The objectives of this study were to determine the concentrations of cerium (Ce), lanthanum (La), scandium (Sc), and yttrium (Y) in the surroundings of the Serra Pelada mine, as well as the environmental risks associated with these elements. Therefore, 27 samples were collected in agricultural, forest, mining, and urban areas, and submitted to chemical and particle size characterization. The concentrations of REEs were quantified by inductively coupled plasma mass spectrometry (ICP-MS) and used to estimate pollution indices and environmental risks of the studied elements. All REEs had higher levels in the anthropized areas when compared to the forest area, except Sc in the mining and urban areas. Pollution load indices revealed that all areas are contaminated (>1) by the combined effect of REEs, especially the agricultural areas (index of 2.3). The element of greatest enrichment in the studied areas was Y, with enrichment factors of 18.2, 39.0, and 44.4 in the urban, agriculture, and mining areas, respectively. However, the potential ecological risk indices were low (<150) in all areas, indicating that there are no current environmental risks by the studied REEs.

Production of engineered-biochar under different pyrolysis conditions for phosphorus removal from aqueous solution.

Phosphorus (P) recovery from wastewater through biochar is an alternative to build a sustainable circular economy and save non-renewable P reservoirs. The efficiency of cations in removing P from wastewater under different pyrolysis conditions is still lacking. We aimed at studying P adsorption and release from biochar enriched with Al3+ and Mg2+, prepared under air-limited and N2-flow pyrolysis conditions. Biochar samples were produced from pig manure (PMB) and impregnated, separately, with 20% of AlCl3 and MgCl2 solutions on both pyrolysis conditions. The materials were characterized for pH, electrical conductivity (EC), total nutrient content, ash, specific surface area (SSA), pore-volume, FTIR, XRD, and SEM-EDX. Phosphorus adsorption was studied by kinetics and adsorption isotherms, as well as desorption. The biochar impregnated with Mg2+ and produced in the muffle furnace achieved the maximum P adsorption (231 mg g-1), and 100% of the adsorbed P was released in solutions of Mehlich-1 and citric acid 2%. The pyrolysis conditions had a small or no influence on the biochar properties governing P adsorption, such as chemical functional groups, surface area, quantity and size of pores, and formation of synthetic minerals. Therefore, it is possible to produce biochar without using N2 as a carrier gas when it comes to P adsorption studies. Mechanisms of P removal comprise precipitation with cations, surface complexation, ligand exchange reactions, and electrostatic attraction on the biochar surface. Overall, Mg-impregnated biochar is a suitable matrix to remove P from aqueous media and to add value to organic residues while producing an environmentally friendly material for reuse in soils.

Biochars produced from various agro-industrial by-products applied in Cr(VI) adsorption-reduction processes.

This study aimed to reuse different agro-industrial by-products (poultry litter, pig manure, sewage sludge and coffee husk) for biochar production and to evaluate their Cr(VI) removal capacities in aqueous medium. The biochars showed different morphologies with porous structures. The percentages of Cr(VI) removal from solution were higher in acid medium (pH = 2), reaching values up to 87%. For all biochars, Cr(VI) removal occurs via both adsorption and reduction, being a rapid (30 min) process, which fits best to the pseudo-second order kinetic model. The biochars, especially from coffee husk, were able to reduce up to 20% of Cr(VI) to Cr(III). The maximum Cr(VI) removal capacities ranged from 10.86 mg g-1 (sewage sludge biochar) to 18.52 mg g-1 (coffee husk biochar). Therefore, the production of biochars from the agro-industrial by-products using the same experimental conditions in one single study is important to compare the Cr(VI) removal capacities from different biomasses. Thus, this study explored the corresponding raw material without the need of further treatment. Biochars showed potential for environmental applications considering Cr(VI)-polluted environments. It is hoped to provide basis to future studies using real wastewater samples.

Predicting biochar cation exchange capacity using Fourier transform infrared spectroscopy combined with partial least square regression.

Determination of cation exchange capacity (CEC) in biochar by applying traditional wet methods is laborious, time-consuming, and generates chemical wastes. In this study, models were developed based on partial least square regression (PLSR) to predict CECs of biochars produced from a wide variety of feedstocks using Fourier transform infrared spectroscopy (FTIR). PLSR models used to predict CEC of biochars on weight (CEC-W) and carbon (CEC-C) basis were obtained from twenty-four biochars derived from several origins of feedstock, as well as compositions and mixtures, including four reference biochar samples. Biochars were grouped according to their CEC-W values (range of 4.0 to 150 cmolc kg-1) or CEC-C values (range of 6.0 to 312 cmolc kg-1). FTIR spectra highlighted features of the main functional groups responsible for biochar's CEC, which allowed a high prediction capacity for the PLSR models (R2pred ~ 0.9). Regression coefficients were associated to spectral variables of the organic matrix polar functional groups that contributed positively and negatively for biochar CEC. Phenolic and carboxylic were the main functional groups contributing to a higher biochar CEC, while CH and CC groups decreased the density of negative charges on the charred matrices. Chemometric models were highly robust to estimate biochar CEC, mainly on a weight basis, in a fast, reliable and economic way, compared to CEC conventional laboratory methods.

Fast and effective arsenic removal from aqueous solutions by a novel low-cost eggshell byproduct.

Developing alternative green solutions for local and correct recycling of eggshells waste (ES) are needed by the egg-processing industries. In this study, we proposed transforming ES into a novel low-cost chemical compound named hydroxyl-eggshell (ES-OH) and investigated its capacity for arsenic (As) removal from aqueous solutions. Laboratory experiments were conducted to investigate the effects of ES-OH doses, pH, kinetics, and isotherms on As removal efficiency. The kinetics study showed that ES-OH removed nearly all As from solution in less than 15 min. The pseudo-second-order model described the process, and the maximum As removal capacity predicted by the Langmuir isotherm model was 529 mg g-1. Using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy with energy dispersive X-ray detector (SEM-EDS), and X-ray diffraction (XRD), we found that the As removal mechanism by ES-OH was due to vladimirite precipitation, followed by weak electrostatic interactions between the precipitate and arsenate ions. Finally, after an economic analysis, we conclude that besides being a novel and economical income source, egg-producing companies might implement the ES-OH production process as a local environmentally-friendly way of recycling eggshells and reducing water As contamination.

Long-term effect of biochar-based fertilizers application in tropical soil: Agronomic efficiency and phosphorus availability.

Incorporation of phosphorus (P) into an organic matrix may be an effective strategy to increase plant P use efficiency in high P-fixing soils. The objective of this work was to evaluate the effect of biochar-based fertilizers (BBFs), produced from poultry litter (PLB) and coffee husk (CHB) enriched with phosphoric acid and magnesium oxide, in combination with triple superphosphate (TSP) on plant growth and soil P transformations. Treatments were prepared as: TSP, CHB, PLB, CHB + TSP [1:1], CHB + TSP [3:1], PLB + TSP [1:1] and PLB + TSP [3:1]; with numbers in brackets representing the proportion of BBF and TSP on a weight basis. Cultivations were: Mombasa grass, maize, and common bean interspersed with fallow periods. After cultivations, a sequential extraction procedure was employed to determine P distribution among different P pools. A kinetic study was performed and revealed that TSP released approximately 90% of total P, and BBFs less than 10% in the first hour. BBF alone or in combination with TSP presented higher or similar biomass yields, relative agronomic effectiveness, and P uptake when compared with TSP. As for the soil, BBFs increased non-labile P fractions, which can be due to pyrophosphate formed during pyrolysis. According to these results, BBFs could totally or partially replace conventional soluble P fertilizers without compromising crop yield either in the short and long-term.

Biochar as composite of phosphate fertilizer: Characterization and agronomic effectiveness.

Organomineral phosphate fertilizers (OMP) may reduce phosphate release rate and its direct contact to the soil solid phase, increasing the effectiveness of phosphorus (P) fertilization. This study aimed to evaluate the effect of granulating biochar (BC) with triple superphosphate (TSP) in two forms (blend or coated) and three proportions (5, 15 and 25%, w/w) on the P release kinetics and plant growth. A successive plant trial using two soils of contrasting P buffering capacities and five P doses (0, 20, 40, 80 and 120 mg kg-1) was set to investigate the agronomic effectiveness of OMP that presented the slowest P release kinetic. The kinetic test showed that within the first 1.5 h, TSP, OMP blend and OMP coated fertilizers released 92, 82 and 36% of total P, respectively. Thereby, BC addition to TSP reduced the P release rate, mainly due to coating. The fertilizers coated with 15% and 25% BC (C15 and C25, respectively) presented the slowest P release rate. For the plant trial, C15 was chosen because it requires less BC when compared with C25 fertilizer. In the first crop, C15 provided more P to plants, especially in the soil with high P buffering capacity, which increased by 10% and 20% the P uptake and the P recovered by the plant when compared with TSP, respectively. In the sandy soil, fertilizers C15 and TSP showed the same performances regarding yield, P uptake and P recovery rate. At consecutive cultivation, regardless of the soil type, P sources (C15 and TSP) did not differ in yield, P uptake and P recovery. Therefore, biochar-based organomineral phosphate fertilizer can enhance P use efficiency in high P-fixing tropical soils, increasing P recovery and uptake when compared with TSP.

Aging of biochar-based fertilizers in soil: Effects on phosphorus pools and availability to Urochloa brizantha grass.

Water-soluble phosphate fertilizers release phosphorus (P) to soils promptly, causing P fixation and low plant availability in highly weathered tropical soils. Therefore, the development of strategies to improve P use efficiency is needed. We hypothesized that biochar-based fertilizers (BBFs) can provide available P to plants and improve P use efficiency when compared with soluble fertilizers. Thus, triple superphosphate (TSP) and phosphoric acid (H3PO4) were pyrolyzed with and without magnesium oxide (MgO) and poultry litter to produce slow-release P BBFs. A pot experiment under greenhouse conditions was performed to evaluate agronomic efficiency of BBFs compared with TSP in an Oxisol. The treatments were incubated over 100 days after the application of 25, 50, 100, and 200 mg kg-1 of P. Three controls were used, including 200 mg kg-1 of P as TSP incubated for 100 days (named TSPincubation) and applied immediately before sowing (named TSPplanting) and a negative control (without P). Marandu grass (Urochloa brizantha cv. Marandu) was cultivated in pots for three cycles of 40 days each. After cultivation, a sequential extraction procedure was used to determine the P distribution among different P pools. The shoot dry matter yield in the first cropping cycle was higher at the highest P rate for TSPplanting. PLB-H3PO4-MgO showed 9% increase in the shoot dry matter when compared with TSPincubation in the first cropping cycle. In subsequent cropping cycles, all BBFs promoted higher biomass yield when compared with TSPplanting. There was an increase in the labile and moderately labile P fractions in soil after cultivation with PLB-TSP. The results suggest that BBFs can enhance P use efficiency in tropical soils in the middle- to long-term run due to slow-release profile that prevent P fixation and promote higher residual effect of fertilization.

Combining biochar and sewage sludge for immobilization of heavy metals in mining soils.

Excess heavy metal concentrations in mining areas is a worldwide problem due to their toxicity and persistence. Applying amendments to those areas is a cost-effective remediation technique that would aid revegetation efforts. The aim of this work was to study the ability of sewage sludge-derived biochar (SSB), wood charcoal powder (hereafter named wood biochar - WB), raw sewage sludge (SS), and their blending (WB/SS) to improve soil properties and to immobilize Cd, Pb, and Zn after their addition to heavy-metal contaminated soils from a Zn-mining area. Biochar was prepared from dried sewage sludge and a greenhouse experiment was set using different amendment doses (WB = 30 and 60 g kg-1, SS = 10 and 20 g kg-1). Addition of wood biochar and sewage sludge-derived biochar to soils led to increased leachate and soil pH. Biochar materials were responsible for the greatest reduction of Cd, Pb, and Zn bioavailability. The use of sewage sludge-derived biochar or the combination of sewage sludge with wood biochar in mining areas are potential alternatives for reusing and aggregating value to these locally available wastes, offering an opportunity to solve both soil remediation and waste disposal problems at once.

Agronomic efficiency of phosphate fertilizers produced by the re-use of a metallurgical acid residue.

The production of fertilizers with industrial wastes reduces the environmental impacts of waste disposal and improves environmental sustainability by generating added-value products. Our objective with this study was to evaluate the agronomic performance and potential soil/plant contamination with heavy metals of alternative phosphate (P) fertilizers, obtained from the acidulation of phosphate rocks (PR) by a metallurgical acidic waste. Seven P fertilizers were evaluated: three PR (Araxá, Patos, and Bayóvar), their respective acidulated products (PAPR), and triple superphosphate fertilizer (TSP). A greenhouse trial was carried out to test the agronomic performances of fertilizers in a sequentially cultivated maize-soybean-white oat. The reaction of PR with acid waste was effective to increase their solubility and improve plant yield and P uptake compared to their natural PR. There was a cumulative recovery by plants of 1.4 and 8.1% of added P via PR and PAPR, respectively. No increase in heavy metal (Cd, Pb, Cr, and Ni) availability in soil or accumulation in shoots was observed, indicating that the PAPR were environmentally safe. The usage of acid waste to produce P fertilizers therefore represents a strategic way to employ marginal products for the production of fertilizers.

Assessment of risk to human health from simultaneous exposure to multiple contaminants in an artisanal gold mine in Serra Pelada, Pará, Brazil.

Contamination of soil, water and plants caused by gold mining is of great societal concern because of the risk of environmental pollution and risk to human health. The aim of the present study was to evaluate the risk to human health from ingestion of As, Ba, Co, Cu, Cd, Cr, Ni, Pb, Se and Ni present in soil, sterile and mineralized waste, and water and plants at a gold mine in Serra Pelada, Pará, Brazil. Samples of soil, sterile and mineralized waste, water and plants were collected around an artisanal gold mine located in Serra Pelada. The mean concentrations of potentially toxic elements in the soil were higher than the soil quality reference values as defined in the legislation, which may be attributeable to past mining activities. Water from the area close to the mine exhibited As, Ba and Pb concentrations exceeding the reference values established by the World Health Organization, deemed unfit for human consumption. Plants exhibited high Pb concentrations, representing a food safety risk to the population. The mean hazard index (HI) values were below the acceptable limit (1.0) established by the United States Environmental Protection Agency, although the highest HI values observed for adults and children were higher than the respective acceptable limits. Environmental contamination and risk to human health were heterogeneous in the surroundings of the mine. Mitigation strategies need to be adopted to decrease the risks of contamination to the environment and to the local population.

Bioconcentration factors and the risk concentrations of potentially toxic elements in garden soils.

Empirical models describe soil-plant transfers to explain the variations in the occurrence of potentially toxic elements (PTE) in soils and to estimate the Bioconcentration Factor (BCF). In this study, results were selected based on data in the literature on soils of humid tropical and temperate regions to evaluate soil-plant transfer models, to calculate the BCF and to derive risk concentrations of Cu, Cr, Pb, Ni and Zn present in the exposure pathway leading to the consumption of contaminated vegetables. The Cetesb (Environmental Agency of the State of Sao Paulo, Brazil) mathematical model was used to derive the risk posed by soil concentrations in urban and rural exposure scenarios. The results of the pseudo total contents of PTE in the soil and the contents absorbed by plants were compared and the BCFs were calculated by the use of geometric means, including a correction factor appropriate to each particular type of soil. Differences were observed between BCFs calculated for each climate region: humid tropical (HTR) and temperate (TE), which the first one presented the highest values to BCF in leaves and the lowest BCF values for root, except Ni, compared to second one. The soil concentrations with the highest risk were found in humid tropical regions as compared with those found in temperate regions, except for Ni. The obtained BCFs may contribute to any future revisions of guideline values as well as help other state environmental agencies to establish their own guideline values.

Cadmium background concentrations to establish reference quality values for soils of São Paulo State, Brazil.

Proper assessment of soil cadmium (Cd) concentrations is essential to establish legislative limits. The present study aimed to assess background Cd concentrations in soils from the state of São Paulo, Brazil, and to correlate such concentrations with several soil attributes. The topsoil samples (n = 191) were assessed for total Cd contents and for other metals using the USEPA 3051A method. The background concentration was determined according to the third quartile (75th). Principal component analysis, Spearman correlation, and multiple regressions between Cd contents and other soil attributes (pH, cation exchange capacity (CEC), clay content, sum of bases, organic matter, and total Fe, Al, Zn, and Pb levels) were performed. The mean Cd concentration of all 191 samples was 0.4 mg kg(-1), and the background concentration was 0.5 mg kg(-1). After the samples were grouped by parent material (rock origin) and soil type, the background Cd content varied, i.e., soils from igneous, metamorphic, and sedimentary rocks harbored 1.5, 0.4, and 0.2 mg kg(-1) of Cd, respectively. The background Cd content in Oxisols (0.8 mg kg(-1)) was higher than in Ultisols (0.3 mg kg(-1)). Multiple regression demonstrated that Fe was primarily attributed to the natural Cd contents in the soils (R (2) = 0.79). Instead of a single Cd background concentration value representing all São Paulo soils, we propose that the concentrations should be specific for at least Oxisols and Ultisols, which are the primary soil types.