X-ray fluorescence spectrometry applied to digital mapping of soil fertility attributes in tropical region with elevated spatial variability.

Portable X-ray fluorescence (pXRF) spectrometry offers valuable information for prediction models of soil fertility attributes spatial variation, although this approach is yet scarce in tropical regions. This study aims to predict and build spatial variability maps of soil pH, remaining phosphorus (P-Rem), soil organic matter (SOM) and sum of bases (SB) using pXRF results through stepwise multiple linear regression (SMLR) and Random Forest (RF) in a highly variable tropical area. Composite samples from soil A horizon were collected at 90 points throughout the campus of the Federal University of Lavras, Minas Gerais, Brazil, for pH, P-Rem, SOM, SB and pXRF analyses. RF predictions showed the highest accuracies, especially for P-Rem and SB (R² values of 0.66 and 0.55, respectively). Attributes that showed higher R² in punctual predictions also exhibited higher R² in spatial predictions. Data obtained from pXRF in tandem with RF can be used to assist prediction models for soil fertility attributes, consequently enabling the digital mapping of such attributes and helping to improve the knowledge about the spatial variability of such attributes in soils of tropical climate. This technique can therefore assist in the identification and orientation of adequate management practices in tropical agricultural practices.

Assessment of iron-rich tailings via portable X-ray fluorescence spectrometry: the Mariana dam disaster, southeast Brazil.

On November 5, 2015, the Fundão dam collapsed and released > 60 million m3 of iron-rich mining sediments into the Doce river basin, covering >1000 ha of floodplain soils across ~80 km from the rupture. The characterization of alluvial mud covering and/or mixed with native soil is a priority for successful environmental rehabilitation. Portable X-ray fluorescence (pXRF) spectrometry was used to (1) assess the elemental composition of native soils and alluvial mud across impacted riparian areas; and 2) predict fertility properties of the mud and soils that are crucial for environmental rehabilitation and vegetation establishment (e.g., pH, available macro and micronutrients, cation exchange capacity, organic matter). Native soils and alluvial mud were sampled across impacted areas and analyzed via pXRF and conventional laboratory methods. Random forest (RF) regression was used to predict fertility properties using pXRF data for pooled soil and alluvial mud samples. Mud and native surrounding soils were clearly differentiated based on chemical properties determined via pXRF (mainly SiO2, Al2O3, Fe2O3, TiO2, and MnO). The pXRF data and RF models successfully predicted pH for pooled samples (R2 = 0.80). Moderate predictions were obtained for soil organic matter (R2 = 0.53) and cation exchange capacity (R2 = 0.54). Considering the extent of impacted area and efforts required for successful environmental rehabilitation, the pXRF spectrometer showed great potential for screening impacted areas. It can assess total elemental composition, differentiate alluvial mud from native soils, and reasonably predict related fertility properties in pooled heterogeneous substrates (native soil + mud + river sediments).

Comparison of bioaccessibility methods in spiked and field Hg-contaminated soils.

Estimating bioaccessible content of mercury in soils is essential in evaluating risks that contaminated soils pose. In this study, soil samples spiked with HgCl2 through adsorption were used to test the effects of liming, soil organic matter, soil depth, and Hg concentration on the following bioaccessibility tests: dilute nitric acid at room temperature, dilute nitric acid at body temperature, Simplified Bioaccessibility Extraction Test (SBET) method, and gastric phase of the In vitro Gastrointestinal (IVG) protocol. Soil and sediment samples from Descoberto, Minas Gerais (Brazil), a city with a well-known record of Hg contamination from artisanal mining, were subjected to these bioaccessibility tests for the first time, and the different methods of estimating bioaccessible content were compared. Bioaccessible fractions in spiked samples ranged from 10% to 60%, and this high bioaccessibility was due to the highly soluble species of Hg and the short time under adsorption. In general, clay and organic matter decreased bioaccessible content. Although the soil in Descoberto is undoubtedly polluted, mercury bioaccessibility in that area is low. In general, dilute nitric acid estimated higher bioaccessible content in soil samples, whereas the SBET method estimated higher bioaccessible content in sediment samples. In multivariate analysis, two groups of bioaccessibility tests arise: one with the two nitric acid tests, and the other with SBET and the gastric phase of the IVG protocol. The addition of pepsin and glycine in the last two tests suggests a more reliable test for assessing mercury bioaccessibility.

Mercury fractionation in tropical soils: A critical point of view.

Problems related to specificity and re-precipitation of metals in sequential chemical extractions can impair their routine use. In order to test the efficiency of a sequential chemical procedure, model compounds composed by soil components commonly found in tropical soils such as goethite, Al-goethite, ferrihydrite, hematite, bauxite, and humic acid were incubated with either Hg(NO3)2 or HgSO4 and submitted to chemical extraction. The procedure aims to assess: (i) water soluble Hg; (ii) bioaccessible Hg at pH near human stomach; (iii) Hg associated with organic matter; (iv) reduced Hg; (v) Hg associated with Fe, Al, and Mn oxides; and, (vi) residual Hg. This procedure was also tested via single and sequential extractions using the surface and subsurface samples of two tropical soils, i.e., a Rhodic Acrudox and a Typic Hapludox, with and without lime application. Soil samples were submitted to an adsorption experiment with HgCl2 and a high adsorption percentage was observed. The majority of Hg at both single and sequential procedure was extracted by an acetic acid solution (pH = 2). Liming, soil depth, and soil type were not determinative on Hg extractability. The sequential extraction applied showed a lack specificity of Hg fractions, confirmed by the model components.

Potential of cassava clones enriched with ß-carotene and lycopene for zinc biofortification under different soil Zn conditions.

BACKGROUND: Zinc (Zn) deficiency is a major human health concern worldwide, and biofortification (genetic and agronomic) is a complementary solution for increasing micronutrient contents, including Zn. Cassava (Manihot esculenta Crantz) has been used for Zn biofortification because it is an important staple crop in most countries affected by malnutrition and Zn deficiency. Thus studies on biofortification of this crop can improve its nutritional quality. Zn content in cassava clones enriched with ß-carotene or lycopene and cultivated under different areas and soil managements was investigated to evaluate the influence of genotypic variation and agronomic management on Zn status in the plant. RESULTS: A clone-specific response to total Zn content in the soil was found, with clones 26, 215, and 240 (ß-carotene enriched) and clones 341 and 395 (lycopene enriched) being the most responsive. For both experiments, there was a positive interaction between total soil Zn and Zn content in the roots. CONCLUSIONS: Our results suggest that, by combining plant breeding and agronomic strategies, it is possible to enrich cassava roots with both zinc and ß-carotene or lycopene. © 2018 Society of Chemical Industry.

Evaluation of mercury phytoavailability in Oxisols.

Mercury is a metal which is potentially toxic for the environment. Many factors control its retention in the soil, such as cation exchange capacity, pH, clay content, organic matter, and redox potential. It is important to know the phytotoxic effects of soil Hg to prevent environmental contamination and its entry into the food chain. Several analytical methods are used to measure metal phytoavailability in soils, but none has been reported for Hg in Oxisols, the most common soil class in Brazil and a very important soil class throughout the tropics. The aim of this study was to select the chemical extractor that best correlated the Hg levels in plants and the Oxisols. The soils used were classified as Dystrophic Red-Yellow Oxisol (LVAd) and Dystroferric Red Oxisol (LVdf), which were collected in the 0-0.2-m soil layer. The species selected for cultivation were a monocotyledon, oat (Avena sativa L. cv. São Carlos) and a eudicotyledon, common bean (Phaseolus vulgaris L. cv. Madrepérola). Each test plot was composed of a 500 cm3 pot filled with soil samples contaminated with HgCl2. Treatments were arranged in a completely randomized design, with four replications. The experiment was conducted for 30 days. Mercury contents were separately extracted with the following extractors: USEPA 3051A, Mehlich-1, Mehlich-3, DTPA, and water. Mercury was determined by hydride generation atomic absorption spectroscopy. The extracted contents were correlated with the contents in the tissues of the plants' aerial part by the Pearson correlation. Although it is not considered a standard procedure to evaluate metal phytoavailable contents, the method that presented the best correlations between soil Hg and plant Hg was USEPA 3051A (r = 0.75*). As expected, the worst correlation was with water (r = 0.57* for common bean and r = 0,05ns for oat).

Impact of selenium supply on Se-methylselenocysteine and glucosinolate accumulation in selenium-biofortified Brassica sprouts.

Brassica sprouts are widely marketed as functional foods. Here we examined the effects of Se treatment on the accumulation of anticancer compound Se-methylselenocysteine (SeMSCys) and glucosinolates in Brassica sprouts. Cultivars from the six most extensively consumed Brassica vegetables (broccoli, cauliflower, green cabbage, Chinese cabbage, kale, and Brussels sprouts) were used. We found that Se-biofortified Brassica sprouts all were able to synthesize significant amounts of SeMSCys. Analysis of glucosinolate profiles revealed that each Brassica crop accumulated different types and amounts of glucosinolates. Cauliflower sprouts had high total glucosinolate content. Broccoli sprouts contained high levels of glucoraphanin, a precursor for potent anticancer compound. Although studies have reported an inverse relationship between accumulation of Se and glucosinolates in mature Brassica plants, Se supply generally did not affect glucosinolate accumulation in Brassica sprouts. Thus, Brassica vegetable sprouts can be biofortified with Se for the accumulation of SeMSCys without negative effects on chemopreventive glucosinolate contents.

Genotypic variation of zinc and selenium concentration in grains of Brazilian wheat lines.

Exploration of genetic resources for micronutrient concentrations facilitates the breeding of nutrient-dense crops, which is increasingly seen as an additional, sustainable strategy to combat global micronutrient deficiency. In this work, we evaluated genotypic variation in grain nutrient concentrations of 20 Brazil wheat (Triticum aestivum L.) accessions in response to zinc (Zn) and Zn plus selenium (Se) treatment. Zn and Se concentrations in grains exhibited 2- and 1.5-fold difference, respectively, between these wheat accessions. A variation of up to 3-fold enhancement of grain Zn concentration was observed when additionally Zn was supplied, indicating a wide range capacity of the wheat lines in accumulating Zn in grains. Moreover, grain Zn concentration was further enhanced in some lines following supply of Zn plus Se, showing stimulative effect by Se and the feasibility of simultaneous biofortification of Zn and Se in grains of some wheat lines. In addition, Se supply with Zn improved the accumulation of another important micronutrient, iron (Fe), in grains of half of these wheat lines, suggesting a beneficial role of simultaneous biofortification of Zn with Se. The significant diversity in these wheat accessions offers genetic potential for developing cultivars with better ability to accumulate important micronutrients in grains.

Assessment of the anticancer compounds Se-methylselenocysteine and glucosinolates in Se-biofortified broccoli (Brassica oleracea L. var. italica) sprouts and florets.

Broccoli (Brassica oleracea L. var. italica) is a rich source of chemopreventive compounds. Here, we evaluated and compared the effect of selenium (Se) treatment on the accumulation of anticancer compounds Se-methylselenocysteine (SeMSCys) and glucosinolates in broccoli sprouts and florets. Total Se and SeMSCys content in sprouts increased concomitantly with increasing Se doses. Selenate was superior to selenite in inducing total Se accumulation, but selenite is equally effective as selenate in promoting SeMSCys synthesis in sprouts. Increasing sulfur doses reduced total Se and SeMSCys content in sprouts treated with selenate, but not in those with selenite. Examination of five broccoli cultivars reveals that sprouts generally have better fractional ability than florets to convert inorganic Se into SeMSCys. Distinctive glucosinolate profiles between sprouts and florets were observed, and sprouts contained approximately 6-fold more glucoraphanin than florets. In contrast to florets, glucosinolate content was not affected by Se treatment in sprouts. Thus, Se-enriched broccoli sprouts are excellent for simultaneous accumulation of chemopreventive compounds SeMSCys and glucoraphanin.

Evaluation of genotypic variation of broccoli (Brassica oleracea var. italic) in response to selenium treatment.

Broccoli (Brassica oleracea var. italic) fortified with selenium (Se) has been promoted as a functional food. Here, we evaluated 38 broccoli accessions for their capacity to accumulate Se and for their responses to selenate treatment in terms of nutritional qualities and sulfur gene expresion. We found that the total Se content varied with over 2-fold difference among the leaf tissues of broccoli accessions when the plants were treated with 20 µM Na(2)SeO(4). Approximately half of total Se accumulated in leaves was Se-methylselenocysteine and selenomethionine. Transcriptional regulation of adenosine 5'-phosphosulfate sulfurylase and selenocysteine Se-methyltransferase gene expression might contribute to the different levels of Se accumulation in broccoli. Total glucosinolate contents were not affected by the concentration of selenate application for the majority of broccoli accessions. Essential micronutrients (i.e., Fe, Zn, Cu, and Mn) remained unchanged among half of the germplasm. Moreover, the total antioxidant capacity was greatly stimulated by selenate in over half of the accessions. The diverse genotypic variation in Se, glucosinolate, and antioxidant contents among accessions provides the opportunity to breed broccoli cultivars that simultaneously accumulate Se and other health benefit compounds.

Selenium accumulation in lettuce germplasm.

Selenium (Se) is an essential micronutrient for animals and humans. Increasing Se content in food crops offers an effective approach to reduce the widespread selenium deficiency problem in many parts of the world. In this study, we evaluated 30 diverse accessions of lettuce (Lactuca sativa L.) for their capacity to accumulate Se and their responses to different forms of Se in terms of plant growth, nutritional characteristics, and gene expression. Lettuce accessions responded differently to selenate and selenite treatment, and selenate is superior to selenite in inducing total Se accumulation. At least over twofold change in total Se levels between cultivars with high and low Se content was found. Synergistic relationship between Se and sulfur accumulation was observed in nearly all accessions at the selenate dosage applied. The change in shoot biomass varied between lettuce accessions and the forms of Se used. The growth-stimulated effect by selenate and the growth-inhibited effect by selenite were found to be correlated with the alteration of antioxidant enzyme activities. The different ability of lettuce accessions to accumulate Se following selenate treatment appeared to be associated with an altered expression of genes involved in Se/S uptake and assimilation. Our results provide important information for the effects of different forms of Se on plant growth and metabolism. They will also be of help in selecting and developing better cultivars for Se biofortification in lettuce.

Environmental behavior of arsenic(III) and (V) in soils.

This paper presents an evaluation of the environmental behavior of arsenic species in soils (F. F. Dias, Master Thesis, University of Delaware, 1997). The results obtained were used to determine adsorption constants that were incorporated in mathematical models using forward and backward stepwise linear regression to correlate data. The amount of adsorption was significantly different depending on soil properties, such as organic matter, iron oxide content, and surface area. Arsenic speciation on the soil surface was deduced from desorption data, with As(V) being more strongly retained in the soil. As(III) was oxidized on the soil surface and desorbed as As(V); an important factor since As(V) is less toxic. In order to develop an adequate adsorption model, Langmuir and Freundlich isotherms were obtained for each soil without pH alteration. Results indicated that the maximum amount of As(V) adsorbed was greater than the amount of As(III) adsorbed. Adsorption edges for As(III) and As(V), with pH varying from 3 to 10, were obtained at concentrations that ranged from 0.1 to 200 mg L(-1). The soils studied exhibited an L-type Langmuir isotherm. Maximum As(III) adsorption occurred around pH 6 to 9, while maximum As(V) adsorption occurred in the 4 to 5 pH range. Experiments to determine arsenic kinetics were carried out and showed that adsorption and desorption equilibrium was reached within 48 hours for both species.