Characterization of nutrient deficiency in Hancornia speciosa Gomes seedlings by omitting micronutrients from the nutrient solution

Hancornia speciosa Gomes (Mangaba tree) is a fruit tree belonging to the Apocynaceae family and is native to Brazil. The production of seedlings of this species is limited by a lack of technical and nutritional expertise. To address this deficiency, this study aimed to characterize the visual symptoms of micronutrient deficiency and to assess growth and leaf nutrient accumulation in H. speciosa seedlings supplied with nutrient solutions that lack individual micronutrients. H. speciosa plants were grown in nutrient solution in a greenhouse according to a randomized block design, with four replicates. The treatments consisted of a group receiving complete nutrient solution and groups treated with a nutrient solution lacking one of the following micronutrients: boron (B), copper (Cu), iron (Fe), manganese (Mn), zinc (Zn), and molybdenum (Mo). The visual symptoms of nutrient deficiency were generally easy to characterize. Dry matter production was affected by the omission of micronutrients, and the treatment lacking Fe most limited the stem length, stem diameter, root length, and number of leaves in H. speciosa seedlings as well as the dry weight of leaves, the total dry weight, and the relative growth in H. speciosa plants. The micronutrient contents of H. speciosa leaves from plants receiving the complete nutrient solution treatment were, in decreasing order, Fe>Mn>Cu>Zn>B.

Production and quality of Anacardium othonianum Rizz. seedlings grown in different substrates

This study aimed to evaluate the effect of substrate on growth, emergence, nutrition, and quality of Anacardium othonianum Rizz. (cerrado cashew tree) seedlings. The experiment was conducted in a greenhouse at the Plant Tissue Culture Laboratory on the Rio Verde campus. The following substrates were used: 1) Bioplant®, 2) Mecplant® (MP) + carbonized rice husk (CRH) (7:3), 3) fine-grained vermiculite (FGV), 4) FGV+CRH (3:1), 5) FGV+CRH (1:1), 6) FGV+CRH (1:3), and 7) sugarcane bagasse (SB) + sugarcane mill filter cake (FC) (3:2). Emerged seedlings were counted at 2-day intervals for 38 days following emergence of the first seedling. At 39, 64, and 89 days after seeding (DAS), the following variables were measured: stem length (SL), stem diameter (SD), and number of leaves (NL). Accumulated dry weight, quality indices, and leaf macro- and micronutrient levels were determined at 89 DAS. Plants grown in the FGV and FGV+CFH (1:3) substrates had shorter stem lengths than the plants grown in other substrates. Increases in seedling growth were smaller between 64 and 89 DAS compared to the initial period of the experiment. The highest leaf N concentrations were found in the SB+FC substrate treatment group; P and K concentrations were higher for the MP+CRH (7:3), SB+FC, and Bioplant® treatments; and Ca levels were higher for the SB+FC and MP+CRH (7:3) substrate treatments. The MP+CRH (7:3) substrate treatment group had the highest leaf B and Mn micronutrient concentrations, and plants from the Bioplant® substrate group had the highest leaf B micronutrient content. Mg, S, Cu, Zn, and Fe concentrations did not differ among the different substrates. The plant traits that differed most among the treatments included stem length for the FGV and FGV+CRH (1:3) substrate groups and leaf nutrient concentrations, which were higher for the SB+FC group followed by the MP+CRH and Bioplant® treatments.

Quantitative elemental analysis of dry-ashed bark and wood samples of birch, spruce and pine from south-western Finland using PIXE

A total of over 200 different samples of bark and wood of Silver birch, Norway spruce and Scots pine were analysed. Samples were taken from several areas in western Finland, some with known sources of atmospheric heavy metal emission (Harjavalta, Ykspihlaja). Also analytical data for pine needles from some sites are reported. The chemical analyses were performed by thick-target particle-induced X-ray emission (PIXE) spectrometry after preconcentration by dry ashing of samples at 550oC. The following elements were quantified in most of the samples: P, S, K, Ca, Mn, Fe, Ni, Cu, Zn, Rb, Sr, Cd, Ba and Pb. The ash percentage and the chemical composition of ashes of different wood materials were also obtained, as dry ashing was used in the analytical procedure. The variations in elemental concentrations in wood and bark of an individual tree, expressed as RSDs, were mostly in the range 10 – 20 %. For several trees of the same species sampled from small areas (< 1 ha), the variations in elemental concentrations were surprisingly high (RSDs 20 – 50 %). In the vicinity of metal plants, effects of strong atmospheric heavy metal pollution (pollution factor above 100) were observed in pine bark. The increase of heavy metal content in wood samples from the same sites was quite small. Elemental concentrations in ashes of bark and wood, from areas with no local source of atmospheric pollution, were relatively uniform. Based on this observation an alternative way of demonstrating atmospheric pollution of tree bark is discussed.

Emprego de nebulizador pneumático de ICP-MS como câmara de diluição em sistemas de injeção em fluxo para determinações multielementares

An automatic dispenser based on a flow-injection system used to introduce sample and analytical solution into an inductively coupled plasma mass spectrometer through a spray chamber is proposed. Analytical curves were constructed after the injection of 20 to 750 µL aliquots of a multielement standard solution (20.0 µg L-1 in Li, Be, Al, V, Cr, Mn, Ni, Co, Cu, Zn, As, Se, Sr, Ag, Cd, Ba, Tl, Pb) and the acquisition of the integrated transient signals. The linear concentration range could be extended to ca. five decades. The performance of the system was checked by analyzing a NIST 1643d reference material. Accuracy could be improved by the proper selection of the injected volume. Besides good precision (r.s.d. < 2%), the results obtained with the proposed procedure were closer to the certified values of the reference material than those obtained by direct aspiration or by injecting 125 µL of several analytical solutions and samples.

Determinações multi-elementares de metais, Sulfato e Cloreto em amostras de águas por espectrometria de massas com fonte de plasma (ICP-MS)

The multi-element determination of Al, Cr, Mn, Ni, Cu, Zn, Cd, Ba, Pb, SO4= and Cl- in riverine water samples was accomplished by inductively coupled plasma mass spectrometry (ICP-MS). The sample passed through a column containing the anionic resin AG1-X8 and the metals were determined directly. The retained anionic species were eluted and SO4= and Cl- were determined at m/z 48 and 35 correspondent to the ions SO+ and Cl+ formed at the plasma. Accuracy for metals was assessed by analysing the certified reference TM-26 (National Water Research Institute of Canada). Results for SO4= and Cl- were in agreement with those obtained by turbidimetry and spectrophotometry. LOD's of 0.1 µg l-1 for Cd, Ba and Pb; 0.2 µg l-1 for Al, Mn and Cu; 0.5 µg l-1 for Cr; 0.9 for Zn; 2.0 µg l-1for Ni , 60 µg l-1 for S and 200 µg l-1 Cl were attained.

Eletrodissolução de ligas de latão empregando sistemas de análise em fluxo para a determinação de cobre, zinco e chumbo por ICP-AES

An on-line electrodissolution procedure implemented in a flow injection system for determination of copper, zinc and lead in brasses alloys by ICP-AES is described. Sample dissolution procedure was carried out by using a PTFE chamber and a DC power supply with constant current. Solid sample was attached to chamber as anode and a gold tubing coupled in the chamber was used as cathode. An electrolytic solution flowing through the gold tubing closed the electric circuit with sample, in order to provide condition for electric dissolution when the DC power supply was switched on. The best results were achieved by using a 1.5 mol l-1 nitric acid solution as electrolyte and a 2.5 A current intensity. The procedure presented a good performance characterized by a relative standard deviation better than < 5% (n=5) and a sample throughput of 180 determinations per hour for Cu, Zn and Pb. Results were in agreement with those obtained by conventional acid dissolution (99% confidence level).

Substâncias húmicas aquáticas: fracionamento molecular e caracterização de rearranjos internos após complexação com íons metálicos

The aquatic humic substances (AHS) investigated in this study were conventionally isolated from Rio Negro waters - Amazonas State/Brazil by means of the collector XAD 8. A special five-stage tangential-flow ultrafiltration device was used for analytical fractionation of AHS. The fractionation patterns (6 fractions each) showed that metal traces remaining in AHS after their XAD 8 isolation have different size distributions. For instance, the major percentage of traces of Ni, Cu, Zn, Cd and Pb (determined using ICP-AES) was preferably complexed by molecules with relatively high molecular size (30-100 kDa) and the following complexation order was characterized: F2 >> F1 = F4 = F5 > F3 > F6. Moreover, the species formed between AHS and metals prepared by spiking, showed distribution patterns changing as a function of the complexation time (ageing process), indicating a slow transformation process and an inner rearrangements in the binding sites within the AHS molecules.

Distribuição de metais e caracterização das constantes de troca entre espécies metálicas e frações húmicas aquáticas de diferentes tamanhos moleculares

In this work the metal distribution and exchange constants between metal species and aquatic humic fractions with different molecular sizes were studied. The aquatic humic substances (AHS) were extracted by XAD-8 resin from water sample collected from Itapitanguí river, São Paulo State, Brazil. The AHS were fractionated in six fractions with different molecular sizes (>100 - <5 kDa) and characterized by several techniques. Molar ratios H/C suggested higher aromaticity for fractions F1 and F6 whereas molar ratios C/N didn´t show any differences regarding the humification degree between the fractions. The UV-Vis absorbance a254/a436 ratio showed higher results for F4 and F5, probably by less condensed features. FTIR studies showed high similarity in the functional groups in the fractions. The highest percentage of traces of Co, Al, Fe, Mn, Cu, Zn and Ni (determined by ICP-AES) was preferably complexed by fractions F3 and F4 with a greater amount of dissolved organic carbon (DOC). In addition, the exchange constants, determined by ultrafiltration method, showed complexes AHS-Fe and AHS-Al with higher stability than complexes AHS-Co in all fractions.

Active sulphide mine tailings impoundments as sources of contaminated drainage: controlling factors, methods of characterisation and geochemical constraints for mitigation

Low quality mine drainage from tailings facilities persists as one of the most significant global environmental concerns related to sulphide mining. Due to the large variation in geological and environmental conditions at mine sites, universal approaches to the management of mine drainage are not always applicable. Instead, site-specific knowledge of the geochemical behaviour of waste materials is required for the design and closure of the facilities. In this thesis, tailings-derived water contamination and factors causing the pollution were investigated in two coeval active sulphide mine sites in Finland: the Hitura Ni mine and the Luikonlahti Cu-Zn-Co-Ni mine and talc processing plant. A hydrogeochemical study was performed to characterise the tailingsderived water pollution at Hitura. Geochemical changes in the Hitura tailings were evaluated with a detailed mineralogical and geochemical investigation (solid-phase speciation, acid mine drainage potential, pore water chemistry) and using a spatial assessment to identify the mechanisms of water contamination. A similar spatial investigation, applying selective extractions, was carried out in the Luikonlahti tailings area for comparative purposes (Hitura low-sulphide tailings vs. Luikonlahti sulphide-rich tailings). At both sites, hydrogeochemistry of tailings seepage waters was further characterised to examine the net results of the processes observed within the impoundments and to identify constraints for water treatment. At Luikonlahti, annual and seasonal variation in effluent quality was evaluated based on a four-year monitoring period. Observations pertinent to future assessment and mine drainage prevention from existing and future tailings facilities were presented based on the results. A combination of hydrogeochemical approaches provided a means to delineate the tailings-derived neutral mine drainage at Hitura. Tailings effluents with elevated Ni, SO₄ ^2- and Fe content had dispersed to the surrounding aquifer through a levelled-out esker and underneath the seepage collection ditches. In future mines, this could be avoided with additional basal liners in tailings impoundments where the permeability of the underlying Quaternary deposits is inadequate, and with sufficiently deep ditches. Based on the studies, extensive sulphide oxidation with subsequent metal release may already initiate during active tailings disposal. The intensity and onset of oxidation depended on e.g. the Fe sulphide content of the tailings, water saturation level, and time of exposure of fresh sulphide grains. Continuous disposal decreased sulphide weathering in the surface of low-sulphide tailings, but oxidation initiated if they were left uncovered after disposal ceased. In the sulphide-rich tailings, delayed burial of the unsaturated tailings had resulted in thick oxidized layers, despite the continuous operation. Sulphide weathering and contaminant release occurred also in the border zones. Based on the results, the prevention of sulphide oxidation should already be considered in the planning of tailings disposal, taking into account the border zones. Moreover, even lowsulphide tailings should be covered without delay after active disposal ceases. The quality of tailings effluents showed wide variation within a single impoundment and between the two different types of tailings facilities assessed. The affecting factors included source materials, the intensity of weathering of tailings and embankment materials along the seepage flow path, inputs from the process waters, the water retention time in tailings, and climatic seasonality. In addition, modifications to the tailings impoundment may markedly change the effluent quality. The wide variation in the tailings effluent quality poses challenges for treatment design. The final decision on water management requires quantification of the spatial and seasonal fluctuation at the site, taking into account changes resulting from the eventual closure of the impoundment. Overall, comprehensive hydrogeochemical mapping was deemed essential in the identification of critical contaminants and their sources at mine sites. Mineralogical analysis, selective extractions, and pore water analysis were a good combination of methods for studying the weathering of tailings and in evaluating metal mobility from the facilities. Selective extractions with visual observations and pH measurements of tailings solids were, nevertheless, adequate in describing the spatial distribution of sulphide oxidation in tailings impoundments. Seepage water chemistry provided additional data on geochemical processes in tailings and was necessary for defining constraints for water treatment.

Estudo multivariado de solos urbanos da cidade de Teresina

The concentrations of Cu, Pb, Zn, Cr, Ni, Al, Mn and Fe were measured by atomic absorption spectrometry, of 19 topsoil samples collected in the Teresina city urban area to discriminate natural and anthropic contributions and identify possible sources of pollution. The average concentrations of Cu, Zn, Pb and Cr of the urban soils were 6.11, 8.56, 32.12 and 7,17 mg/kg-1, respectively. Statistical analysis techniques, such as principal component analysis (PCA) and hierarchical cluster analysis (HCA), were used to analyze the data. Mn, Ni and Cr levels were interpreted as natural contributions, whereas Pb, Zn and, in part, Cu were accounted for mainly by anthropic activities. High Pb levels were observed in the ancient avenues.

Análise estatística e optimização de perfis de redução termoprogramada (TPR)

The effect of operational variables and their interaction in TPR profiles was studied using a fractional factorial experimental design. The heating rate and the reducing agent concentration were found to be the most important variables determining the resolution and sensitivity of the technique. They showed opposite effects. Therefore, they should be manipulated preferentially in order to obtain optimized TPR profiles. The effect of sample particle size was also investigated. The tests were carried out within a Cu/Zn/Al2O3 catalyst used for the water-gas shift reaction that presented two distinct species of Cu2+ in TPR profiles.

Retenção de metais pesados em micélio de fungos micorrízicos arbusculares

This work evaluated the kinetics as well as the retention capacity of Cu, Zn, Cd, and Pb by arbuscular mycorrhizal fungi (AMF) mycelium. The metal retention is a fast process with Cu being retained 3, 30, and 60 times faster than Zn, Cd, and Pb, respectively. Metal retention capacity varied amongst the different tested AMF species and decreased in the following order: Cu>Zn>>Cd>Pb. The Glomus clarum mycelium showed the highest retention capacity for Cu, Cd and Pb, whereas Zn was mostly retained by Gigaspora gigantea mycelium. The simultaneous application of all tested metals in solution decreased Cu and Zn retention by AMF mycelium. The high retention capacity of Cu and Zn by mycelium of G. clarum and G. gigantea suggests a promising use of these isolates in phytoremediation.

Caracterização dos níveis de elementos químicos em solo, submetido a diferentes sistemas de uso e manejo, utilizando espectrometria de fluorescência de raios-x por energia dispersiva (EDXRF)

This study aimed to evaluate the chemical elements levels in soil, submitted to different management systems and use by the Energy Dispersive X-Ray Fluorescence Spectrometry - EDXRF. The systems were T1 - agro forestry (SAF), T2 - Native Field (CN), T3 - Native Forest (NM), T4 - Tillage Forest (PF); T5 - conventional tillage system (SPC) and T6 - System tillage (NT). Samples were collected at 0-10 and 10-20 cm, dried and ground for analysis in EDX-720. The soil showed no difference in the average concentrations of chemical elements analyzed in the profiles, but the systems presented different concentrations of metal elements, and T3 had the highest K, Ca and Zn at 0-10 cm and higher contents of K, Ca, Cu, Zn and Mn in the layer of 10-20 cm.

Desenvolvimento de microcélula eletroquímica para estudos de microrregiões

The construction and optimization of a device that can be applied to electrochemical studies in flat micro regions are described. This was developed as an attempt to study small regions of metallic samples, whose properties may differ completely from its macroscopic behavior and for studies in highly resistive medium. Some results were obtained for individual grains of polycrystalline samples, welded regions, pure copper, platinum, glassy carbon, single crystals of Cu-Zn-Al alloy, and steel in biodiesel without electrolyte intentionally added. The device showed to be useful for the proposed purpose, allowing to be automated and has potential possibilities of other applications.

Synthesis, characterization and thermal behaviour on solid pyruvates of some bivalent metal ions

Solid state M-L compounds, were M stands for bivalent Mn, Fe, Co, Ni, Cu, Zn and L is pyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), X-Ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, ligand denticity, and thermal decomposition of the isolated compounds.