Aquatic humus from an unpolluted Brazilian dark-brown stream: general characterization and size fractionation of bound heavy metals

The main pool of dissolved organic carbon in tropical aquatic environments, notably in dark-coloured streams, is concentrated in humic substances (HS). Aquatic HS are large organic molecules formed by micro-biotic degradation of biopolymers and polymerization of smaller organic molecules. From an environmental point of view, the study of metal-humic interactions is often aimed at predicting the effect of aquatic HS on the bioavailability of heavy metal ions in the environment. In the present work the aquatic humic substances (HS) isolated from a dark-brown stream (located in an environmental protection area near Cubatao city in São Paulo-State, Brazil) by means of the collector XAD-8 were investigated. FTIR studies showed that the carboxylic carbons are probably the most important binding sites for Hg(II) ions within humic molecules. C-13-NMR and H-1-NMR studies of aquatic HS showed the presence of constituents with a high degree of aromaticity (40% of carbons) and small substitution. A special five-stage tangential-flow ultrafiltration device (UF) was used for size fractionation of the aquatic HS under study and for their metal species in the molecular size range 1-100 kDa (six fractions). The fractionation patterns showed that metal traces remaining in aquatic HS after their XAD-8 isolation have different distributions. Generally, the major percentage of traces of Mn, Cd and Ni (determined by ICP-AES) was preferably complexed by molecules with relatively high molecular size. Cu was bound by fractions with low molecular size and Co showed no preferential binding site in the various humic fractions. Moreover, the species formed between aquatic HS and Hg(II), prepared by spiking (determined by CVAAS), appeared to be concentrated in the relatively high molecular size fraction F-1 (> 100 kDa).

An evaluation into the potential of biological processing for the removal of metals from sewage sludges

The use of sewage sludge in agricultural land as a means of sludge disposal and recycling has been shown to be economical and suitable because of the presence of nutrients such as nitrogen and phosphorus. However, municipal sludges often contain high quantities of toxic metals and other compounds that must be removed for its safe use in agricultural soils. The biological leaching of metals from sewage sludges has been shown to be a promising technique for metal detoxifying in such complex matrix. The process efficiency is dependent on several physico-chemical parameters, such as total solids concentration, metal forms, pH-ORP, and temperature. Scale-up of the process has not yet been defined and is still pursuing the correct operational design. Current research involving the bioleaching of metals from sewage sludge and its application to land, which affects soil physical properties, are presented and discussed.

Study of the alkaline earth metals with 8-hydroxyquinolinate derivatives - Calcium complexes

Metal complexes of calcium with 5,7-dibromo, 7-iodo and 5-chloro-7-iodo-8-hydroxyquinolate were precipitated in aqueous ammonia and acetone medium, except for the solid state compound with 5,7-dichloro-8-hydroxyquinoline which hasn't been obtained under these conditions. The complexes obtained through the mentioned precipitation are Ca[(C9H4ONBr2)(2)](3).H2O, Ca[(C9H5ONI)(2)].2H(2)O and Ca[(C9H4ONICl)(2)].2.5H(2)O. Their intermediate from the thermal decomposition found through TG/DTA curves in air indicated the presence of different kinds of calcium carbonates related to the reversibility and crystalline structure, depending on the original compounds. The initial compounds and the intermediate from the thermal decomposition were also characterized through IR spectra and X-ray diffraction.

Solid-state reactions of mercury with pure noble metals - Part 2. Mercury-iridium system

Thermogravimetry, cyclic voltammetry and other analytical techniques were used to study the reactions of mercury with pure iridium. The results allowed to suggest when subjected to heat or anodic stripping voltammetry an electrodeposited mercury film reacts with Ir substrate and at least three mass loss steps and three peaks appear in the mercury desorption process. The first two were attributed to Hg(0) species removal like a mercury bulk and a mercury monolayer. The last can be ascribed to the mercury removal from a solid solution with iridium.

Synthesis, characterization and thermal behaviour of solid 2-methoxybenzoates of trivalent metals

Solid-state Ln(L)(3) compounds, where Ln stands for trivalent Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y and L is 2-methoxybenzoate have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results provided information on the composition, dehydration, coordination mode, structure, thermal behaviour and thermal decomposition.

2-Mercaptobenzothiazole clay as matrix for sorption and preconcentration of some heavy metals from aqueous solution

2-Mercaptobenzothiazole loaded on previously polystyrene treated clay was prepared, characterized and used for sorption and preconcentration of Hg(II) Pb(II), Zn(II) and Cd(II) from an aqueous solution. The support used was a natural clay previously treated with sulphuric acid solution. Adsorptiou isotherms of metal ions from aqueous solutions as function of pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The chemically treated clay was very selective to Hg(II) in solution in which Zn(II), Cd(II), Pb(II) and some transition metal ions were also present.

Sorption and preconcentration of some heavy metals by 2-mercaptobenzothiazole-clay

2-Mercaptobenzothiazole loaded on previously treated clay was prepared, characterized and used for sorption and preconcentration of Hg(II), Pb(II), Zn(II), Cd(II), Cu(II) and Mn(II) from an aqueous solution. The support used was a natural clay previously treated with sulphuric acid solution. Adsorption isotherms of metal ions from aqueous solutions as function of pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The chemically treated clay was very selective to Hg(II) in solution in which Zn(II), Cd(II), Pb(II), Cu(II) and Mn(II) were also present. © 1995.

Lattice dynamics of noble metals on effective three-body interaction

Quite recently we modified the original model of Sarkar et al. for cubic metals in extending the ion-ion interaction, ion-electron interaction and the introduction of crystal equilibrium condition. We applied our scheme to alkali metals. We studied here the lattice dynamics of noble metals on our approach by calculating phonon dispersion relations along the three principal symmetry directions, [ξ00], [ξξ00] and [ξξξ] and the (θ-T) curves of three noble metals: copper, silver and gold. We obtained reasonable agreement with the experimental findings.

Relative lability of trace metals complexed in aquatic humic substances using ion-exchanger cellulose-hyphan

The purpose of this paper is to characterize the lability/inertness metal fractions complexed by aquatic humic substances (HS) in relation to pH, complexation time, and HS concentration. HS were preconcentrated by ultrafiltration and complexed with bivalent metal ions. These fractions were characterized by ion exchange with the chelating collector cellulose Hyphan by applying batch procedure. The metals were determined by atomic absorption spectrometry. The results show that the distribution coefficients, Kd, decreased with HS presence, and that the relative lability of metal fractions complexed by HS is dependent on variables such as pH, complexation time, and HS concentration. Until c.a. 15 min, the metal change between aquatic HS and ion exchanger occurs following a 2 order reaction. Afterwards, the remaining metal fraction in the HS reacts following a 1st order reaction. For traces of metal ions bound to dissolved HS, the lability orderPb > Mn > Cd, Ni > Cu is revealed. ©1997 Soc. Bras. Química.

Preconcentration of heavy metals ions from aqueous solutions by means of cellulose phosphate: An application in water analysis

Cellulose phosphate (CELLPHOS) was studied as a collector for analytical preconcentration of traces of Cd(II), Cr(III), Cu(II) and Ni(II) from aqueous sample solution. It has been proved that using chromatographic columns packed with CELLPHOS for preconcentration and 1.0 mol 1 -1 HCl for elution the adsorbed analytes are quantitatively enriched. An enrichment factor of 20 (100 ml sample, 5 ml concentrate) was achieved by this separation procedure, which was applied to a series of water analyses (river, sea, bog water).

Synthesis and thermal study of 8-hydroxy-quinoline derivatives of the alkaline Earth metals: I. Strontium complexes

Strontium complexes of 5,7-dibromo-, 5,7-dichloro-, 7-iodo- and 5-chloro-7-iodo-8-hydroxyquinoline were precipitated from an aqueous ammonia and acetone medium. The complexes obtained were Sr[(C9H4ONBr2)2]·2.5H 2O; Sr[(C9H4ONCl2)(OH)]·1.5H2O; Sr[(C9H5ONI)2]·5H2O and Sr[(C9H4ONICl)(OH)]·1.25H2O. The residues of their thermal decomposition were SrBr2; a mixture of SrCl2, SrCO3 and SrO3 SrCO3, and SrCO3, respectively. All were characterized by means of thermogravimetry, differential thermal analysis, complexometry with EDTA, atomic absorption spectroscopy, IR spectroscopy and X-ray diffraction. © 1999 Akadémiai Kiadó.

Non-nutrient heavy metals in tomato plants cultivated in soil amended with biosolid and sugar-cane bagasse compost

In this study, non-nutrient heavy metal concentrations (Cd, Cr, Ni and Pb) were measured in composts during the composting process, in compost/Red-yellow Latosol mixtures, and in tomato plants. Composts were produced using sugar-cane bagasse, biosolids and cattle manure in the proportions 75-0-25, 75-12.5-12.5, 75-25-0, 50-50-0 or 0-100-0 (composts with 0, 12.5, 25, 50 and 100% biosolids). The composts were applied to the soil, in 6 treatments and a control (mineral fertilization). Control and the 0% biosolids treatments received inorganic nitrogen and all the treatments received the same amount of N, P and K. Tomato plants were cultivated in 24-L pots, in a green house in Jaboticabal, SP, Brazil. The experiment had a split plot design, in randomized blocks. Cadmium, Cr, Ni and Pb concentrations were determined during the composting process (7, 27, 57, 97 and 127 days after compost mounting), in soil (0 and 164 days after mixing) and plants. The samples were subjected to digestion with HNO 3, H2O2 and HCl and the metals were determined by AAS. Negative correlations were observed between Cd, Cr and Pb in the compost and Cd, Cr and Pb plant uptake, as well as Ni in the compost and Ni concentration in the plants. The concentrations of Cd, Cr, Ni and Pb increased during composting. Only Cd levels increased when compost was applied to the soil. The roots accumulated Cr, Ni and Pb, the stems and leaves, Cd and Ni and the fruits did not accumulate any of the metals studied. The composts with biosolids did not increase Cd, Cr, Ni and Pb uptake by plants.

Quantitative analysis of potentially toxic metals in alginates for dental use

Alginate is one the materials most employed in practice to make dental impressions. Substances like zinc, cadmium and lead silicate, which are included in several alginate brands with the aim of improving their physical, chemical and mechanical properties, are a source of serious concern as regards their toxicity. The most serious chronic effect of oral exposure to cadmium is renal toxicity. Assimilation of lead has deleterious effects on the gastrointestinal tract, hematopoietic system, cardiovascular system, central and peripheral nervous systems, kidneys, immune system, and reproductive system. Chronic oral exposures to zinc have resulted in hypochromic and microcyte anemia in some individuals. The aim of the present study was to measure the cadmium, lead and zinc contents of seven brands of alginate for dental use on sale in Brazil. The samples were weighed and placed in the Teflon cups of a closed-system microwave oven. Aqua regia (4mL concentrated HCI:HNO3, 3:1 v/v) and hydrofluoric acid (2mL concentrated HF) were added to the samples, which were then subjected to heating. The samples were then cooled to room temperature and diluted to 25 mL in deionized water in a volumetric glass flask. The samples were diluted in duplicate and analyzed against a reagent blank. The analyses were performed in an atomic absorption flame spectrophotometer. Neither lead nor cadmium was detected. Zinc contents ranged from 0.001% to 1.36% by weight. The alginates exhibited low contents of the metals under study and gave no cause for concern regarding toxicity; even so, it is advisable to monitor potentially toxic materials continually and to analyze their plasmatic levels in the professionals working with them.