Clean and accurate soil quality monitoring in mining areas under environmental rehabilitation in the Eastern Brazilian Amazon.

Soil quality monitoring in mining rehabilitation areas is a crucial step to validate the effectiveness of the adopted recovery strategy, especially in critical areas for environmental conservation, such as the Brazilian Amazon. The use of portable X-ray fluorescence (pXRF) spectrometry allows a rapid quantification of several soil chemical elements, with low cost and without residue generation, being an alternative for clean and accurate environmental monitoring. Thus, this work aimed to assess soil quality in mining areas with different stages of environmental rehabilitation based on predictions of soil fertility properties through pXRF along with four machine learning algorithms (projection pursuit regression, PPR; support vector machine, SVM; cubist regression, CR; and random forest, RF) in the Eastern Brazilian Amazon. Sandstone and iron mines in different chronological stages of rehabilitation (initial, intermediate, and advanced) were evaluated, in addition to non-rehabilitated and native forest areas. A total of 81 soil samples (26 from sandstone mine and 55 from iron mine) were analyzed by both traditional wet-chemistry methods and pXRF. The available/exchangeable contents of K, Ca, B, Fe, and Al, in addition to H+Al, cation exchange capacity at pH = 7, Al saturation, soil organic matter, pH, sum of bases, base saturation, clay, and sand were accurately predicted (R2 > 0.70) using pXRF data, with emphasis on the prediction of Fe (R2 = 0.93), clay content (R2 = 0.81), H+Al (R2 = 0.81), and K+ (R2 = 0.85). The best predictive models were developed by RF and CR (86%) and when considering pXRF data + mining area + stage of rehabilitation (73%). The results highlight the potential of pXRF to accurately assess soil properties in environmental rehabilitation areas in the Amazon region (yet scarcely evaluated under this approach), promoting a more agile and cheaper preliminary diagnosis compared to traditional methods.

Combined effects of hydrothermally-altered feldspar and water regime on cadmium minimization in rice.

The accumulation of cadmium (Cd) in grains and edible parts of crops poses a risk to human health. Because rice is the staple food of more than half of the world population, reducing Cd uptake by rice is critical for food safety. HydroPotash (HYP), an innovative potassium fertilizer produced with a hydrothermal process, has the characteristics of immobilizing heavy metals and potential use for remediating Cd-contaminated soils. The objective of this study was to evaluate the HYP as a soil amendment to immobilize Cd in acidic soils and to reduce the accumulation of Cd in rice tissues. The experiment was performed in a greenhouse with a Cecil sandy loam soil (pH 5.3 and spiked with 3 mg Cd kg-1) under either flooding conditions (water level at 4 cm above the soil surface) or at field capacity. Two hydrothermal materials (HYP-1 and HYP-2) were compared with K-feldspar + Ca(OH)2 (the raw material used for producing HYP), Ca(OH)2, zeolite, and a control (without amendment). After 30 days of soil incubation, HydroPotashs, the raw material, and Ca(OH)2 increased both soil solution pH and electrical conductivity. These materials also decreased soluble Cd concentration (up to 99.7%) compared with the control (p < 0.05). After 145 days, regardless of the materials applied, plant growth was favored (up to 35.8%) under the flooded regime. HydroPotash-1 was more effective for increasing dry biomass compared with other amendments under both water regimes. HydroPotashs reduced extractable Cd in soil, Cd content in plant biomass at tillering and maturing stage, and were efficient in minimizing Cd accumulation in rice grains.

Hydrothermally-altered feldspar reduces metal toxicity and promotes plant growth in highly metal-contaminated soils.

Novel green technologies for soil remediation have been focusing on altering soil properties and improving soil health. Hydrothermally-altered feldspar (HYP, HydroPotash), recently developed, is being related as both an efficient amendment to immobilize heavy metals in soils and a plant nutrients source, consisting in a promising technology for revegetation of contaminated sites. In order to evaluate the effectiveness of using HYP for phytostabilization programs, two different soils (Technosol and Oxisol) collected from a smelting site were amended with increasing doses of HYPs (HYP-1 and HYP-2): 15, 30, 60, and 120 Mg ha-1. For comparison, a control (soil without amendment) and a soil amended with zeolite (clinoptilolite) were also included as treatments. After 90 days of incubation, HYPs decreased up to 83.8 % of Cd availability and reduced exchangeable Al up to 100 %. HydroPotash increased pH, cation exchange capacity, and contents of potassium, calcium, and phosphorus, as well as microbial biomass carbon, and fluorescein diacetate hydrolysis of soils. Andropogon gayanus, Eucalyptus grandis, and Heterocondylus vitalbae started growing from the dose of 15 Mg ha-1 HYPs in the Oxisol and 60 Mg ha-1 HYPs in the Technosol. Principal component analysis indicates that plant shoot dry weight was negatively correlated with extractable Cd and Zn and positively with pH, CEC, and Ca content. Besides promoting plant growth, HYPs reduced heavy metals (Cd and Zn) absorption by plants, indicating that HYP has potential use as an amendment in phytostabilization programs.

Hydrothermally-altered feldspar as an environmentally-friendly technology to promote heavy metals immobilization: Batch studies and application in smelting-affected soils.

Hydrothermally-altered feldspar (HydroPotash, HYP) possesses, among other physicochemical properties, high pH buffering and cation exchange capacity. Therefore, it may potentially remove heavy metals from aqueous solutions and immobilize these metals in contaminated soil. This study aimed to evaluate the capabilities of two types of HydroPotash (HYP-1 and HYP-2) and a zeolite sample (a commercial adsorbent) for immobilizing cadmium (Cd), zinc (Zn), and lead (Pb) from both aqueous solution and contaminated soils from a Zn-smelting area (classified as soilhigh, soilintermediate, and soillow based on their level of soluble metal concentration). Sorption studies in natural suspension pH showed that HYPs removed 63.8-99.9% Zn, 20.6-40.7% Cd, and 68.4-99.7% Pb from aqueous solution. In the batch test with controlled pH (at pH 5.5), HYPs sorbed more Cd than zeolite. Analyses of scanning electron microscopy-energy dispersive X-ray spectroscopy after desorption showed the presence of Pb at HYP-2, indicating that this metal was effectively adsorbed. In soilhigh HYPs immobilized 99.9% of Zn, Cd, and Pb after one week of soil incubation with these products. The HYPs immobilization effect persisted up to 84 days of soil incubation with these products. The increased soil pH promoted by HYPs appears to be the main factor controlling metal sorption. In conclusion, HydroPotash can be used as an adsorbent/amendment to effectively immobilize heavy metals in both water and contaminated soils by precipitation and adsorption. Our findings indicate the high potential of this material for Cd, Zn, and Pb stabilization, which is of great relevance when recovering areas affected by mining/smelting activities with multi-element contamination.

Interactions of cadmium and zinc in high zinc tolerant native species Andropogon gayanus cultivated in hydroponics: growth endpoints, metal bioaccumulation, and ultrastructural analysis.

Cadmium (Cd) and zinc (Zn) toxicity causes physiological disorders and harms plants, interfering with the rehabilitation of areas affected by mining activities. This study evaluated how the exposure to Zn and/or Cd affects the growth of native andropogon grass (Andropogon gayanus Kunth) plants originally found in areas contaminated with Cd and/or Zn due to zinc mining activities. Plants were cultivated for 7 weeks in a nutrient solution treated with Zn (142.3-854.0 µM) or Cd (0.9-13.3 µM) separately or combined with a molar ratio of 64:1 (Zn:Cd). A control treatment was grown in a complete Hoagland and Arnon solution (without Cd). Plant height, stem diameter, internode length, dry weight, Cd and Zn concentration, and accumulation in shoots/roots, as well as ultrastructure of roots and leaves were analyzed at the end of the experiment. The root dry weight was not significantly affected by the addition of the metals. Moreover, Zn provided higher shoot dry weight (up to 160%) relative to control. Andropogon grass tolerated both metals better separately than when applied together. Transmission electron microscopy analyses showed modifications such as vesiculation and vacuolation in the ultrastructure of andropogon tissues by Cd and/or Zn. The andropogon grass was tolerant to the doses tested, evidencing that it has potential for recovering areas contaminated with Zn and/or Cd.

Assessing the most sensitive and reliable endpoints in plant growth tests to improve arsenic risk assessment.

Arsenic (As) is toxic to humans and the environment. Its toxicity has been assessed in many ways, including plant growth tests integrated in As risk assessments (RA). The tiered approach used in RA schemes assumes that lower tiers are more conservative than higher tiers. Plant growth tests may comprise lower tier of a RA and include the measurement of several endpoints. However, only few of these endpoints are highly sensitive and reliable, which makes them more appropriate to comprise lower tiers. Therefore, the selection of those endpoints is needed. The present study aimed to evaluate the most appropriate endpoints of plant growth tests to use in lower tier As RA schemes. This selection of endpoints was based on their sensitivity and reliability, using different tropical soils and plant species. In order to achieve this objective, six plant species were exposed to eight levels of As contamination (0; 8; 14.5; 26; 46.5; 84; 150; 270 mg kg-1), in three different tropical soils (Oxisol, Inceptisol, and tropical artificial soil). The endpoints measured were: first germination count (FrC), plant height (PH), relative leaf area (RLA), stem diameter (SD), total germination (TG), germination speed index (GSI), dry mass (DM), number of completely expanded leaves (CEL), plant survival (PS), soil plant analysis development chlorophyll level (SPAD), and the final germination count (FnC). Toxic values for 50% of effect were estimated for each endpoint within each species and test soil, to rank them according to their sensitivity and reliability. The most sensitive endpoints were: FrC, RLA, DM, GSI, PH, and FnC, while the most reliable endpoints were: FrC, DM, GSI, DM, PH, FnC, and TG. Our findings suggest that FrC, DM, GSI, PH, and FnC are the most adequate endpoints to be used in plant growth tests as lower tiers of As RA in tropical regions.

Assessing the Brazilian prevention value for soil arsenic: Effects on emergence and growth of plant species relevant to tropical agroecosystems.

One of the entry routes of arsenic (As) into the food chain is through the consumption of edible parts of crops contaminated by this element. Different plant species present distinctive As accumulation and tolerance capacities. These differences are also influenced by As availability and speciation in soils. This study assessed the effect of As contamination on plant emergence and initial growth, as well as on accumulated As contents in different crops grown in tropical soils. In addition, it was intended to verify the protection level of the current soil As prevention value adopted in Brazil, which should be applicable for conceivably other tropical soils in Latin America. Plants of maize, rice, sorghum, common bean, sunflower, and radish were cultivated in two different tropical soils (Oxisol and Inceptisol) and in a standard substrate (tropical artificial soil - TAS) dosed with As (0; 8; 14.5; 26; 46.5; 84; 150; 270 mg kg-1). Early germination, total dry mass, As content, and bioconcentration factor were evaluated. The EC20 and EC50 values (the As concentration for 20% or 50% of effect relative to control treatment) based on total As concentration were more variable among different soils than the corresponding EC20 and EC50 values based on extractable (phytoavailable) As concentration. From the studied species, common bean was the most sensitive and maize was the least sensitive to As. Those species were the ones that accumulated the lowest As levels in shoot tissues. Arsenic concentrations measured in plant tissues and estimated bioaccumulation factors were not related to relative As toxicity among species. Data obtained suggest that the current Brazilian prevention value for arsenic is adequate for soils with high arsenic adsorption capacity.

Ecological risk assessment of cerium for tropical agroecosystems.

Cerium (Ce) is present in high technology materials and in mineral P fertilizers and the use and discharge of such resources may change the natural status of Ce in the soil environment. Brazilian soils in farming areas are significantly exposed to increased levels of unintentionally-added Ce through intensive input of phosphate fertilizers. The aims of this study were to evaluate the ecotoxicological risk to plants growing in tropical soils contaminated with Ce, as well as to create a database to support future legislation regulating the limits of this element in Brazilian and conceivably other tropical soils. Eight crop species (corn, sorghum, rice, wheat, soybeans, sunflower, radish, and beans) were exposed to a Ce concentration gradient in two typical tropical soils (Oxisol and Inceptsol), and an artificial soil. Our findings showed that among the endpoints measured, Ce phytotoxicity was more pronounced on shoot dry matter than on percent germination and germination speed index. Sensitivity of plants is species specific and our data showed that sunflower and radish exposed to Ce were the most sensitive crop species. Soil properties such as pH, cation exchange capacity, and organic carbon may have influenced the severity of Ce phytotoxicity. Because of that, the Oxisol contaminated with this element caused higher phytotoxicity than the other soils tested. Our risk assessment results (hazardous concentration, HC5 = 281.6 mg Ce kg-1) support the idea that unintentional Ce input through P fertilizers does not pose a risk to soils of Brazilian agroecosystems.