Fate of nickel ion in (II-III) hydroxysulphate green rust synthesized by precipitation and coprecipitation

In order to investigate the efficiency of sulfate green rust (GR2) to remove Ni from solution, GR2 samples were synthesized under controlled laboratory conditions. Some GR2 samples were synthesized from Fe(II) and Fe(III) sulfate salts by precipitation. Other samples were prepared by coprecipitation, of Ni(II), Fe(II) and Fe(III) sulfate salts, i.e., in the presence of Ni. In another sample, Ni(II) sulfate salt was added to pre-formed GR2. After an initial X-ray diffraction (XRD) characterization all samples were exposed to ambient air in order to understand the role of Ni in the transformation of the GR2 samples. XRD was repeated after 45 days. The results showed that Nious GR2 prepared by coprecipitation is isomorphous to Ni-free GR2, i.e. Ni is incorporated into the crystalline structure. Fe(II) was not replaced by Ni(II) in the crystalline structure of GR2 formed prior to exposure to solution-phase Ni. This suggests Ni was adsorbed to the GR2 surface. Sulfate green rust is more efficient in removing Ni from the environment by coprecipitation.

Nickel incorporation in Fe(II, III) hydroxysulfate Green Rust: effect on crystal lattice spacing and oxidation products

Ni(II)-Fe(II)-Fe(III) layered double hydroxides (LDH) or Ni-containing sulfate green rust (GR2) samples were prepared from Ni(II), Fe(II) and Fe(III) sulfate salts and analyzed with X ray diffraction. Nickel is readily incorporated in the GR2 structure and forms a solid solution between GR2 and a Ni(II)-Fe(III) LDH. There is a correlation between the unit cell a-value and the fraction of Ni(II) incorporated into the Ni(II)-GR2 structure. Since there is strong evidence that the divalent/trivalent cation ratio in GR2 is fixed at 2, it is possible in principle to determine the extent of divalent cation substitution for Fe(II) in GR2 from the unit cell a-value. Oxidation forms a mixture of minerals but the LDH structure is retained if at least 20 % of the divalent cations in the initial solution are Ni(II). It appears that Ni(II) is incorporated in a stable LDH structure. This may be important for two reasons, first for understanding the formation of LDHs, which are anion exchangers, in the natural environment. Secondly, this is important for understanding the fate of transition metals in the environment, particularly in the presence of reduced Fe compounds.

Irrigation with domestic wastewater: a multivariate analysis of main soil changes

Irrigation with treated domestic sewage wastewater (TSE) is an agricultural practice to reduce water requirements of agroecossystems and the nutrient load impact on freshwaters, but adverse effects on soil chemical (salinization, sodification, etc.) and soil physical properties (alteration in soil porosity and hydraulic conductivity, etc.) have been reported. This study aimed to define some relationships among these changes in an Oxisol using multivariate analysis. Corn (Zea mays L.) and sunflower (Helianthus annuus L.) were grown for two years, irrigated with TSE. The following soil properties were determined: Ca2+; Mg2+; Na+; K+ and H + Al contents, cationic exchangeable capacity (CEC), sum of bases (SB), base saturation (V), texture (sand, silt and clay), macro-, micro-, and cryptoporosity (V MA, V MI and V CRI), water content at soil saturation (θS) and at field capacity (θFC), residual water content (θR), soil bulk density (d s), water dispersed clay (WDC) and saturated hydraulic conductivity (K SAT). Factor analysis revealed the following six principal factors: Fine Porosity (composed of Na+; K+; WDC, θR, θRFC, and V CRI); Large Porosity (θS, d s, V MA, Vs); Soil CEC (Ca2+; Mg2+; CEC, SB, V); Soil Acidity (H + Al); and Soil Texture (factors 5 and 6). A dual pore structure appears clearly to the factors 1 and 2, with an apparent relationship between fine porosity and the monovalent cations Na+ and K+. The irrigation (with potable sodic tap water or sewage wastewater) only had a significant effect on Fine Porosity and Large Porosity factors, while factors 3 and 4 (Soil CEC and Soil Acidity) were correlated with soil depth. The main conclusion was a shift in pore distribution (large to fine pores) during irrigation with TSE, which induces an increase of water storage and reduces the capacity of drainage of salts.

Induction of a geochemical barrier for As, Fe and S immobilization in a sulfide substrate

Acid mine drainage (AMD) is an environmental concern due to the risk of element mobilization, including toxic elements, and inclusion in the food chain. In this study, three cover layers were tested to minimize As, Fe and S mobilization from a substrate from former gold mining, containing pyrite and arsenopyrite. For this purpose, different layers (capillary break, sealant and cover layer) above the substrate and the induction of a geochemical barrier (GB) were used to provide suitable conditions for adsorption and co-precipitation of the mobilized As. Thirteen treatments were established to evaluate the leaching of As, Fe and S from a substrate in lysimeters. The pH, As, Fe, S, Na, and K concentrations and total volume of the leachates were determined. Mineralogical analyses were realized in the substrate at the end of the experimental period. Lowest amounts of As, Fe and S (average values of 5.47, 48.59 and 132.89 g/lysimeter) were leached in the treatments that received Na and K to induce GB formation. Mineralogical analyses indicated jarosite formation in the control treatment and in treatments that received Na and K salts. However, the jarosite amounts in these treatments were higher than in the control, suggesting that these salts accelerated the GB formation. High amounts of As, Fe and S (average values of 11.7, 103.94 and 201.13 g/lysimeter) were observed in the leachate from treatments without capillary break layer. The formation of geochemical barrier and the use of different layers over the sulfide substrate proved to be efficient techniques to decrease As, Fe and S mobilization and mitigate the impact of acid mine drainage.

Soil Water Potentials and Capsicum annuum L. under Salinity

ABSTRACT Investigations into water potentials in the soil-plant system are of great relevance in environments with abiotic stresses, such as salinity and drought. An experiment was developed using bell pepper in a Neossolo Flúvico (Fluvent) irrigated with water of six levels of electrical conductivity (0, 1, 3, 5, 7 and 9 dS m-1) by using exclusively NaCl and by simulating the actual condition (using a mixture of salts). The treatments were arranged in a randomized block design, in a 6 × 2 factorial arrangement, with four replicates. Soil matric (Ψm) and osmotic (Ψo) potentials were determined 70 days after transplanting (DAT). Soil total potential was considered as the sum of Ψm and Ψo. Leaf water (obtained with the Scholander Chamber) and osmotic potentials were determined before sunrise (predawn) and at noon at 42 and 70 DAT. There were no significant differences between the salt sources used in the irrigation water for soil and plant water potentials. The supply of salts to the soil through irrigation water was the main factor responsible for the decrease in Ψo in the soil and in bell pepper leaves. The total potential of bell pepper at predawn reached values of -1.30 and -1.33 MPa at 42 and 70 DAT, respectively, when water of 9 dS m-1 was used in the irrigation. The total potential at noon reached -2.19 MPa. The soil subjected to the most saline treatment reached a water potential of -1.20 MPa at 70 DAT. There was no predawn equilibrium between the total water potentials of the soil and the plant, indicating that soil potential cannot be considered similar to that of the plant. The determination of the osmotic potential in the soil solution should not be neglected in saline soils, since it has strong influence on the calculation of the total potential.

Application of 1-methylcyclopropene, calcium chloride and calcium amino acid chelate on fresh-cut cantaloupe muskmelon

The objective of this work was to determine the effects of postharvest application of 1-methylcyclopropene (1-MCP) and two calcium salts, applied individually or combined, on firmness and visual quality of fresh-cut muskmelon stored in air, for 18 days. Two sets of fruits, one of them exposed to 1-MCP at 300 nL L-1, were cut into cubes, dipped in deionized water, or in 1% Ca solutions as CaCl2, or in calcium amino acid chelate (Ca-chelate), placed in clamshell containers, and stored in air at 5±1ºC and 90±5% RH, for 18 days. The assay was conducted using an entirely randomized design, with three replications, in a split plot array. Evaluation of visual appearance, color, flesh firmness, total soluble solids, titratable acidity, and pH was performed right after treatments, and every period of three days, up to eighteen days. Application of 1-MCP at 300 nL L-1, calcium chloride or Ca-chelate, or the combination 1-MCP and calcium, preserved initial freshness and reduced softening of the samples. Ca-chelate synergistically enhanced the effect of 1-MCP on firmness after nine days of storage, while calcium chloride improved firmness of the samples throughout storage. Ca-chelate may serve as an alternative for shelf life extension of cantaloupe fresh-cut muskmelon.

In vitro selection of bacteria with potential for use as probiotics in marine shrimp culture

The objective of this work was to isolate strains of lactic acid bacteria with probiotic potential from the digestive tract of marine shrimp (Litopenaeus vannamei), and to carry out in vitro selection based on multiple characters. The ideotype (ideal proposed strain) was defined by the highest averages for the traits maximum growth velocity, final count of viable cells, and inhibition halo against nine freshwater and marine pathogens, and by the lowest averages for the traits duplication time and resistance of strains to NaCl (1.5 and 3%), pH (6, 8, and 9), and biliary salts (5%). Mahalanobis distance (D²) was estimated among the evaluated strains, and the best ones were those with the shortest distances to the ideotype. Ten bacterial strains were isolated and biochemically identified as Lactobacillus plantarum (3), L. brevis (3), Weissella confusa (2), Lactococcus lactis (1), and L. delbrueckii (1). Lactobacillus plantarum strains showed a wide spectrum of action and the largest inhibition halos against pathogens, both Gram-positive and negative, high growth rate, and tolerance to all evaluated parameters. In relation to ideotype, L. plantarum showed the lowest Mahalanobis (D²) distance, followed by the strains of W. confusa, L. brevis, L. lactis, and L. delbrueckii. Among the analyzed bacterial strains, those of Lactobacillus plantarum have the greatest potential for use as a probiotic for marine shrimp.

Somatic embryogenesis from zygotic embryos of Euterpe oleracea Mart.

The aim of this work was to study the morphogenetic responses of zygotic embryos of açai palm (Euterpe oleracea Mart.) submitted to several conditions of in vitro culture. Several research experiments were conducted, in laboratory, using vegetable material collected from açai palm plants at Embrapa Amazon Oriental, Belém-PA, Brazil. It was possible to verify the expression of a direct, repetitive and no-synchronized model of somatic embryogenesis in mature zygotic embryos cultivated in primary MS medium supplemented with 2,4-D (339.36 muM) and transferred to a secondary MS medium in the presence of NAA (0.537 muM) and 2iP (12.30 muM). The conversion of somatic embryos into seedlings was reached after 210 days with the transfer of the cultures to a third medium with sucrose and mineral salts concentrations reduced to a half, without growth regulators.

In vitro organogenesis in some citrus species

In vitro organogenesis of Citrus was studied for the genotypes Citrus sinensis cv. 'Natal', C. limonia, C. volkameriana, and C. aurantium, with the use of epicotyl segments-derived explants, cultured in MT salts and vitamins medium supplemented with different concentrations of 6-benzylaminopurine (BAP - 0.0; 0.5; 1.0; 1.5 or 2.0 mg L-1). For the recalcitrant genotypes C. limonia and C. aurantium the in vitro organogenesis was also studied with internodal segments-derived explants, cultured in MT salts and vitamins medium supplemented with 0; 0.5; 1.0; 2.0, or 4.0 mg L-1 of BAP. The efficiency of culture medium supplementation with the combination of BAP (0.0; 1.0, or 2.0 mg L-1) and NAA (1-naphthaleneacetic acid - 0.0; 0.3, or 0.5 mg L-1) in the development of adventitious shoots was evaluated for C. aurantium. Culture medium supplementation with BAP is not essential for the adventitious shoots development in the four genotypes studied when epicotyl segments-derived explants are used. In general, culture media supplementation with BAP decreased the percentage of responsive explants excepted for C. sinensis cv. 'Natal' and C. limonia when the concentrations of 1.5 and 2.0 mg/L were used. The presence of cytokinin, in concentrations up to 2 mg/L, stimulated the in vitro organogenesis when internodal segments-derived explants were used for C. limonia and C. aurantium. For C. aurantium no adventitious shoots developed in explants (internodal segments) cultured in basal culture medium, without BAP supplementation. Although no statistic differences could be detected, culture media supplementation with the combination of BAP and NAA favored the development of adventitious shoots in C. aurantium. The best concentration of NAA varied according to BAP concentration. The results presented herein, show that Citrus in vitro organogenesis depends on the interaction of culture medium composition, explant differentiation level, and genotype.

Ação promotora do berílio em catalisadores da síntese do estireno

The catalytic dehydrogenation of ethylbenzene in presence of steam is the main commercial route to produce styrene. The industrial catalysts are potassium- and chromia-doped hematite which show low surface areas leading to bad performance and short life. In order to develop catalysts with high areas, the effect of beryllium on the textural properties and on the catalytic performance of this iron oxide was studied. The influence of the amount of the dopant, the starting material and the calcination temperature were also studied. In sample preparations, iron and beryllium salts (nitrate or sulfate) were hydrolyzed with ammonia and then calcinated. The experiments followed a factorial design with two variables in two levels (Fe/Be= 3 and 7; calcination temperature= 500 and 700ºC). Solids without any dopant were also prepared. Samples were characterized by elemental analysis, infrared spectroscopy, surface area and porosity measurements, X-ray diffraction, DSC and TG. The catalysts were tested in a microreactor at 524ºC and 1 atm, by using a mole ratio of steam/ ethylbenzene=10. The selectivity was measured by monitoring styrene, benzene and toluene formation. It was found that the effect of beryllium on the characteristics of hematite and on its catalytic performance depends on the starting material and on the amount of dopant. Surface areas increased due to the dopant as well as the nature of the precursor; samples produced by beryllium sulfate showed higher areas. Beryllium-doped solids showed a higher catalytic activity when compared to pure hematite, but no significant influence of the anion of starting material was noted. It can be concluded that beryllium acts as both textural and structural promoter. Samples with Fe/Be= 3, heated at 500ºC, lead to the highest conversion and were the most selective. However, catalysts prepared from beryllium sulfate are the most promising to ethylbenzene dehydrogenation due to their high surface area which could lead to a longer life.

Desenvolvimento de um processo de lixiviação dos concentrados de manganês em sais fundidos

The NaCl- KCl system as fused-salt solvent for leaching has shown to have some advantages over traditional solvents. In this work the solubility of copper, nickel and cobalt oxide in this system, as impurities in manganese concentrate, was studied. The euthetic mixture of NaCl - KCl at 700ºC was used at several fusion times and the dissolved metals were determined by Atomic Absorption Spectrometry. The results have shown that in these conditions only copper was solubilized.

Hidrólise seletiva de carboxiamidas de resíduos de asparagina e glutamina em colágeno: preparação e caracterização de matrizes aniônicas para uso como biomateriais

This work describes the selective hydrolysis of carboxyamide groups of asparagine and glutamine of collagen matrices for the preparation of negatively charged collagen biomaterials. The reaction was performed in the presence of chloride and sulfate salts of alkaline and alkaline earth metals in aqueous dimethylsulfoxide solution and, selectively hydrolysis of carboxyamide groups of collagen matrices was promoted without cleavage of the peptide bond. The result is a new collagen material with controlled increase in negative charge content. Although triple helix secondary structure of tropocollagen was preserved, significative changes in thermal stabilities were observed in association with a new pattern of tropocollagen macromolecular association, particularly in respect microfibril assembly, thus providing at physiological pH a new type of collagen structure for biomaterial preparation, characterized by different charge and structural contents .

Solubilidade do SrO em NaCl-Kcl fundido a 727ºC

The solubility product value of SrO has been found to be equal to 10-4,2 (molality scale) in molten equimolar mixture of NaCl and KCl at 727ºC, using a potentiometric method involving a calcia stabilized zirconia membrane electrode. This value, which is in a logical agreement with other alkaline-earth oxide determined solubilities, is compared to those of 10-5,8, 10-3,0 and 10-3,08 (molality scale) found in the litterature 33, 22 and 5 years ago, respectively. Such discrepencies have called the attention of the authors, their possible reasons (methodology, titrating agent) are analyzed and a theoretical discussion, for considering the authors' value as more reliable, is given in this paper.

Avaliação da fitodisponibilidade de cádmio, chumbo e crômio, em soja cultivada em latossolo vermelho escuro tratado com fertilizantes comerciais

The aim of this work was to evaluate the availability of the toxic heavy metals: cadmium, lead and chromium, in soybean, from some fertilizers. Five fertilizers and soluble salts contend Cd, Pb and Cr were used. All the treatments were accomplished in vases of 2,5 L with application of two doses, 50 and 100 kg.ha-1 for the fertilizers and 25 and 50 kg.ha-1 for the salts.

Reações de contração de anel promovidas por sais de tálio(III)

Thallium(III) salts promote a number of different reactions useful in organic synthesis. In this paper, the ring contraction of ketones and olefins, mediated by thallium(III) salts, is exhaustively reviewed.