Epäpuhtauksien poistaminen sinkkisulfaattiliuoksista käyttäen selektiivisiä ioninvaihtimia

Diplomityössä on tutkittu kuparin, koboltin, nikkelin ja kadmiumin poistamista sinkkisulfaattiliuoksista käyttäen uusia silikarunkoisia kelatoivia erotusmateriaaleja. Vertailukohteena on käytetty perinteisiä kaupallisia polymeerirunkoisia kelatoivia ioninvaihtohartseja. Laboratoriokokeissa selvitettiin erotusmateriaalien adsorptio- ja ioninvaihto-ominaisuuksia tasapaino- ja kolonnikokeilla. Silikarunkoisten erotusmateriaalien kemiallista kestävyyttä tutkittiin olosuhteissa, jotka vastaavat prosessisyklin eri vaiheita. Metallien adsorptiomekanismien selvittämiseksi erotusmateriaaleille tehtiin happo-emäs ja sulfaattititraukset. Tasapainokokeet osoittivat, että silikarunkoisilla erotusmateriaaleilla saatiin kupari erotettua väkevistä sinkkisulfaattiliuoksista polymeerirunkoisia kelatoivia ioninvaihtohartseja paremmin. Tutkituilla erotusmateriaaleilla ja ioninvaihtohartseilla ei havaittu merkittävää selektiivisyyttä koboltille, nikkelille tai kadmiumille sinkin ja kuparin läsnä ollessa. Kolonnikokeilla yritettiin löytää paras esikäsittely-lataus-eluointisykli kuparin talteenottoon väkevistä sinkkisulfaattiliuoksista silikarunkoisilla erotusmateriaaleilla. Kolonnikokeissa esikäsittely tehtiin laimealla NaOH:lla, jonka jälkeen petiin syötettiin hapanta sinkkisulfaattiliuosta. Eluointi onnistui hyvin laimealla rikkihapolla. Kolonnikokeiden tulokset osoittivat, että kupari on mahdollista erottaa väkevistä sinkkisulfaattiliuoksista. Silikarunkoisten erotusmateriaalien kemiallista kestävyyttä tutkittaessa havaittiin materiaalien kestävän hyvin happoja ja 60 oC:en lämpötilaa. Sitä vastoin alkaalisissa olosuhteissa tapahtui silikan liukenemista. Tutkituilla erotusmateriaaleilla havaittiin kuparin sitoutumista sekä ioninvaihtomekanismin avulla että sitoutuneena neutraalina suolana.

Metal dealing at the origin of the Chordata phylum: The metallothionein system and metal overload response in Amphioxus.

Non-vertebrate chordates, specifically amphioxus, are considered of the utmost interest for gaining insight into the evolutionary trends, i.e. differentiation and specialization, of gene/protein systems. In this work, MTs (metallothioneins), the most important metal binding proteins, are characterized for the first time in the cephalochordate subphylum at both gene and protein level, together with the main features defining the amphioxus response to cadmium and copper overload. Two MT genes (BfMT1 and BfMT2) have been identified in a contiguous region of the genome, as well as several ARE (antioxidant response element) and MRE (metal response element) located upstream the transcribed region. Their corresponding cDNAs exhibit identical sequence in the two lancelet species (B. floridae and B. lanceolatum), BfMT2 cDNA resulting from an alternative splicing event. BfMT1 is a polyvalent metal binding peptide that coordinates any of the studied metal ions (Zn, Cd or Cu) rendering complexes stable enough to last in physiological environments, which is fully concordant with the constitutive expression of its gene, and therefore, with a metal homeostasis housekeeping role. On the contrary, BfMT2 exhibits a clear ability to coordinate Cd(II) ions, while it is absolutely unable to fold into stable Cu (I) complexes, even as mixed species. This identifies it as an essential detoxification agent, which is consequently only induced in emergency situations. The cephalochordate MTs are not directly related to vertebrate MTs, neither by gene structure, protein similarity nor metal-binding behavior of the encoded peptides. The closest relative is the echinoderm MT, which confirm proposed phylogenetic relationships between these two groups. The current findings support the existence in most organisms of two types of MTs as for their metal binding preferences, devoted to different biological functions: multivalent MTs for housekeeping roles, and specialized MTs that evolve either as Cd-thioneins or Cu-thioneins, according to the ecophysiological needs of each kind of organisms.

Electrochemical synthesis of mesoporous CoPt nanowires for methanol oxidation

A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W) microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane"s channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter) dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.

Análise potenciométrica de redissolução com ultramicroeletrodos: fundamentos e aplicações na determinação de metais traços

The Potentiometric Stripping Analysis (PSA) is described with emphasis on ultramicroelectrode applications with a laboratory developed computer based instrumentation. The technique potentialities as compared with the voltammetric approach are pointed out based on the current literature. Some results of trace metals analysis including zinc, cadmium, lead and copper in vinegar and canned food samples are presented. The mainly advantage found in our laboratory was the technique capability to analyse natural samples with minimum matrix interference and the low level of noise found in our determinations.

Estudo cinético por TG e DSC da decomposição térmica de alguns adutos de haletos de cádmio

By DSC data, the kinetical parameters Ea , n and A were calculated for the thermal decomposition of the adducts CdCl2.2dmf, CdCl2.dmf and CdBr2.dmf (dmf= dimethylformamide) by using Rogers and Smith method. The found values were : Ea = 85, 176 and 101 kJ mol-1 , n= 0.23, 0.25, and 0.17, A= 2.40x10(9), 1.89x10(19) and 1.07x10(9) respectively. By TGA data, the kinetical patameters for the thermal decomposition of the adduct CdCl2.1,5 dmeu (dmeu=dimethylethyleneurea) were calculated by using five different methods.

Metals and Selenium as bioindicators of geographic and trophic segregation in Giant Petrels Macronectes spp.

We analysed concentrations of cadmium, lead, mercury and selenium in blood from males and females of the 2 sibling species of giant petrels, the northern Macronectes halli and the southern M. giganteus, breeding sympatrically at Bird Island (South Georgia, Antarctica). Blood samples were collected in 1998 during the incubation period, from 5 November to 10 December. Between species, cadmium and lead concentrations were significantly higher for northern than for southern giant petrels, which probably resulted from northern giant petrels wintering in more polluted areas (mainly on the Patagonian Shelf and Falkland Islands) compared to southern giant petrels (wintering mainly around South Georgia and the South Sandwich Islands). Between sexes, cadmium concentrations were significantly higher for females than for males in both species, corresponding to the more pelagic habits of females compared to the more scavenging habits of males. Lead and cadmium concentrations in circulating blood decreased significantly over the incubation period, suggesting that when breeding at Bird Island, exposure to the source of pollution had ended, and these metals had been cleared from the blood and excreted, or rapidly transferred to other tissues. Association of lead and cadmium with a common source of pollution was further corroborated by a significant positive correlation between the levels of the 2 elements found. Mercury levels were similar between the species, but showed an opposite trend between sexes, with males showing higher levels than females in northern giant petrels, and the opposite was true in southern giant petrels, with no changes throughout incubation. Selenium levels were similar between sexes, but significantly greater for northern than for southern giant petrels. Moreover, there was a significant increase in the selenium levels over the incubation period in northern giant petrels. Age of adult birds did not affect metal concentrations. Coefficients of variation of metal levels were consistently lower for northern than for southern giant petrels, particularly for mercury, suggesting that the former species is more dietary specialised than the latter. Contaminant analyses, when combined with accurate information on seabird movements, obtained through geolocation or satellite tracking, help us to understand geographic variation of pollution in the marine environment.

Utilização de eletrodos potenciométricos de amálgama em estudos de complexação de substâncias húmicas

Potentiometric amalgam electrodes of lead, cadmium, and zinc are proposed to study the complexation properties of commercial and river sediment humic acids. The copper complexation properties of both humic acids were studied in parallel using the solid membrane copper ion-selective electrode (Cu-ISE). The complexing capacity and the averaged conditional stability constants were determined at pH 6.00 ± 0.05 in medium of 2x10-2 mol L-1 sodium nitrate, using the Scatchard method. The lead and cadmium amalgam electrodes presented a Nernstian behavior from 1x10-5 to 1x10-3 moles L-1 of total metal concentration, permitting to perform the complexation studies using humic acid concentrations around of 20 to 30 mg L-1, that avoids colloidal aggregation. The zinc amalgam electrode showed a subnernstian linear response in the same range of metal concentrations. The Scatchard graphs for both humic acids suggested two classes of binding sites for lead and copper and one class of binding site for zinc and cadmium.

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.

Adsorção de zinco e cádmio em colunas de turfa

The aim of this work was to evaluate the adsorption conditions of zinc and cadmium ions from aqueous solutions using a comercially available peat from Balneário Arroio do Silva, Santa Catarina State, Brazil. Adsorption studies were carried out in column experiments using radiotracers of the studied metals (65Zn and 115Cd). The pH influence and the interference of other ions, such as Na+, Ca2+, Fe3+ and Al3+on the adsorption process were investigated. The results showed that peat columns are able to retain more than 99% of metal ions in solution in a range of pH from 3,7 to 6,5. Ca2+ and Al3+ ions were the main interferent on adsorption of Zn and Cd ions in solution.

Baterias de níquel-hidreto metálico, uma alternativa para as baterias de níquel-cádmio

Nickel metal hydride (Ni-MH) batteries have emerged as an alternative for replacement of nickel-cadmium batteries, because of their more environmental compatibility and high energy capacity. In this article, we described the properties and applications for Ni-MH batteries, giving some emphasis on the metal-hydride electrode, including the description of composition, the charge storage capacity and the discharge profile. The key component of the nickel-metal hydride electrode is a hydrogen storage alloy whose composition is formulated to obtain a high stable material over a large number of charge-discharge cycles.

Qualidade de medições em química analítica. Estudo de caso: determinação de cádmio por espectrofotometria de absorção atômica com chama

Calculation of uncertainty of results represents the new paradigm in the area of the quality of measurements in laboratories. The guidance on the Expression of Uncertainty in Measurement of the ISO / International Organization for Standardization assumes that the analyst is being asked to give a parameter that characterizes the range of the values that could reasonably be associated with the result of the measurement. In practice, the uncertainty of the analytical result may arise from many possible sources: sampling, sample preparation, matrix effects, equipments, standards and reference materials, among others. This paper suggests a procedure for calculation of uncertainties components of an analytical result due to sample preparation (uncertainty of weights and volumetric equipment) and instrument analytical signal (calibration uncertainty). A numerical example is carefully explained based on measurements obtained for cadmium determination by flame atomic absorption spectrophotometry. Results obtained for components of total uncertainty showed that the main contribution to the analytical result was the calibration procedure.

Estudos da deposição em subtensão de cádmio sobre ouro policristalino na presença de diferentes ânions co-adsorvidos

Cadmium UPD on Au was studied by voltammetric and microgravimetric measurements. In the oxide formation/reduction potential region, a mass increasing/decreasing of 32 ng cm-2 was associated to incorporation/elimination of one oxygen per active site. The modifications promoted in the voltammetric and mass profiles by 10-5 M Cd(ClO4)2 are restricted to potentials more negative than 0.4 V. After a 120 s potential delay at 0.05 V, the positive sweep reveals an anodic peak with charge of 40 muC cm-2 and mass decrease of 22 ng cm-2, associated to Cd ads dissolution. Sulphate or chloride was added to the solution without significant influence, due to the low coverage with Cd or anions.

Deposição eletrolítica catódica e anódica simultâneas para minimizar interferências de cobre e chumbo na determinação espectrofotométrica de cádmio em água e alimentos via reação com Verde de Malaquita e iodeto

Simultaneous electrolytic deposition is proposed for minimization of Cu2+ and Pb2+ interferences on automated determination of Cd2+ by the Malachite Green-iodide reaction. During electrolysis of sample in a cell with two Pt electrodes and a medium adjusted to 5% (v/v) HNO3 + 0.1% (v/v) H2SO4 + 0.5 mol L-1 NaCl, Cu2+ is deposited as Cu on the cathode, Pb2+ is deposited as PbO2 on the anode while Cd2+ is kept in solution. With 60 s electrolysis time and 0.25 A current, Pb2+ and Cu2+ levels up to 50 and 250 mg L-1 respectively, can be tolerated without interference. With on-line extraction of Cd2+ in anionic resin minicolumn, calibration graph in the 5.00 - 50.0 µg Cd L-1 range is obtained, corresponding to twenty measurements per hour, 0.7 mg Malachite Green and 500 mg KI and 5 mL sample consumed per determination. Results of the determination of Cd in certified reference materials, vegetables and tap water were in agreement with certified values and with those obtained by GFAAS at 95% confidence level. The detection limit is 0.23 µg Cd L-1 and the RSD for typical samples containing 13.0 µg Cd L-1 was 3.85 % (n= 12).

Pré-concentração de chumbo e cádmio em um sistema de micro extração líquido-líquido e determinação por espectrometria de absorção atômica com chama

A method for determination of lead and cadmium in aqueous samples using solvent microextraction and dithizone as complexing agent with FAAS was developed. Solvent microextraction parameters were optimized. The effect of foreign ions on the extraction yields was studied. The extraction was carried out until the aqueous to organic phase ratio achieved a 250 fold preconcentration of metals. For preconcentration times of 4 min the 3sigma detection limits, relative standard deviations (n=7) and linear calibration ranges were 1.6 mug L-1, 5.8% and 10.0 -- 80.0 mug L-1 for lead and 11.1 ng L-1, 5.9% and 0.3 -- 3.0 mug L-1 for cadmium, respectively. The solvent microextraction procedure presented here was applied to the determination of lead and cadmium in natural waters.

Utilização de zeólita preparada a partir de cinza residuária de carvão como adsorvedor de metais em água

Coal ashes produced in coal-fired power plant could be converted into zeolites and can be used as low-cost adsorbents for the treatment of effluents contaminated with high levels of toxic metals. The capacity of synthetic zeolites for the removal of cadmium, zinc and copper ions from aqueous solutions has been investigated under different operating conditions. Zeolite from bottom chimney showed higher removal efficiency for metals ions than zeolite from feed hopper and mixing mill. The results indicated that the treated bottom ash could be applied in environmental technology as an immobilizer of pollutants.