Ademir dos Santos

Preconcentration and determination of Cu(II) in a fresh water sample using modified silica gel as a solid-phase extraction adsorbent

A method was developed to attach 4-amino-2-mercaptopyrimidine (AMP) onto silica gel surface and to determine trace metals. The surface functionalization reaction was performed with a silylant agent, chloropropyltrimethoxysilane (Si-CPTS), and the product, Si-AMP, was characterized by FT-IR and elemental analysis to evaluate the surface modification. The functionalized silica was applied in the sorption of Cu(II) ions from an aqueous medium. The series of adsorption isotherms were adjusted to a modified Langmuir equation and the maximum number of moles of adsorbed copper was 0.447 mmol g(-1). The modified material was placed in a preconcentration system, where it reached an approximately 20-fold enrichment factor using 5mg of Si-AMP. The proposed method was applied in the preconcentration and determination of Cu(II) in a fresh water sample from the Paraná river and was validated through a comparative analysis of a standard reference material (1643e).

Determination of mercury in agroindustrial samples by flow-injection cold vapor atomic absorption spectrometry using ion exchange and reductive elution

A flow-injection system with a Chelite-S(R) cationic resin packed minicolumn is proposed for the determination of trace levels of mercury in agroindustrial samples by cold vapor atomic absorption spectrometry. Improved sensitivity and selectivity are attained since mercuric ions are on-line concentrated whereas other potential interferents are discarded. With on-line reductive elution procedure, concentrated hydrochloric acid could be replaced by 10% w/v SnCl(2), in 6 M HCl as eluent. The reversed-intermittent stream either carries the atomic mercury to the flow cell in the forward direction or removes the residue from reactor/gas-liquid separator to a discarding flask in the opposite direction. Concentration and volume of reagent, acidity, flow rates, commutation times and potential interfering species were investigated. For 120 s preconcentration time, the proposed system handles about 25 samples h(-1) (50.0-500 ng l(-1)), consuming about 10 ml sample and 5 mg SnCl(2) per determination. The detection limit is 0.8 ng l(-1) and the relative standard deviation (RSD) (n=12) of a 76.7 ng l(-1) sample is about 5%. Results are in agreement with certified value of standard materials at 95% confidence level and good recoveries (97-128%) of spiked samples were found.

Bioaccumulation of metals in aquatic insects of streams located in areas with sugar cane cultivation

Streams located in areas of sugar cane cultivation receive elevated concentrations of metal ions from soils of adjacent areas. The accumulation of metals in the sediments results in environmental problems and leads to bioaccumulation of metal ions by the aquatic organisms. In the present study, bioaccumulation of the metals ions Al, Cd, Cr, Cu, Fe, Mg, Mn and Zn in aquatic insects in streams impacted by the sugar cane was evaluated. The results pointed out that the insects were contaminated by the sediment and that the collector organisms as Chironomus species accumulated higher concentration of metals than the predator organisms.

4-amine-2-mercaptopyrimidine modified silica gel applied in Cd(II) and Pb(II) extraction from an aqueous medium

4-amine-2-mercaptopyrimidine modified silica gel applied in Cd(II) and Pb(II) extraction from an aqueous medium This paper discusses silica surface modification by a process involving a two-step reaction: anchoring of a silylating agent, followed by an attachment of a 4-amino-2-mercaptopyrimidine molecule. The modified material (Si-BP) was successfully characterized by the FTIR spectra, which revealed amine absorption bands, and through 13C and 29Si NMR spectra, which confirm the proposed structure of the modified silica (Si-BP). Si-BP was used to extract cadmium and lead from an aqueous medium at 298 K. The Si-BP kinetics towards metal ions was very fast, i.e., about 10 minutes, although extraction was significantly impaired at pH 3. The series of adsorption isotherms were adjusted to a modified Langmuir equation and the maximum extraction capacity was 0.193 and 0.387 mmol g-1 for Cd(II) and Pb(II), respectively. An analysis of the Ø values lead to the inference that the resulting metal ligand complex was type 1:1.

Distribuição de mercúrio em diferentes solos da Bacia do médio Rio Negro-AM: influência da matéria orgânica no ciclo biogeoquímico do mercúrio

Soils play an important role in the biogeochemical cycle of mercury as a sink for and source of this metallic species to atmospheric and hydrological compartments. In the study reported here, various types of soil were evaluated to ascertain the influence of parameters such as pH, organic matter content, Fe, Al, sand, silt, clay, C/H, C/N, C/O atomic ratios, and cation exchange capacity on the distribution of Hg in Amazonias mid-Negro River basin. The data obtained were interpreted by multivariate exploratory analyses (hierarchical cluster analysis and principal component analysis), which indicated that organic matter plays an important role in mercury uptake in the various soils studied. The soils in floodable areas were found to contain 1.5 to 2.8-fold higher Hg concentrations than those in non-floodable areas. Since these soils are flooded almost year-round, they are less available to participate in redox processes at the soil/atmosphere interface. Hence, floodable areas, which comprise humic-rich soils, accumulate more mercury than non-floodable soils, thus playing an important role in the biogeochemical cycle of Hg in Amazonias mid-Negro River basin.

Interaction between humic substances and metallic ions: a selectivity study of humic substances and their possible therapeutic application

The complexation capacity of humic substances extracted from peat samples taken from the Mogi River in Ribeirao Preto, SP, Brazil, was determined using metal ions (Al(III), Pb(II), Cr(VI) and Cd(II)), yielding the following order of affinity: Cr(VI)< Cd(II)<Pb(II)<Al(III). An oral LD50 test showed that these humic substances are nontoxic up to a maximum concentration of 512 mg kg-1. These findings reinforce the possibility of using humic substances as a metal detoxicant.

Sediment grain size distribution and heavy metals determination in a dam on the Paraná River at Ilha Solteira, Brazil

This paper reports on a preliminary evaluation of the grain size distribution of cadmium, lead and copper in sediment from Catarina Beach, Ilha Solteira, in the state of São Paulo, Brazil. Surface sediments were fractionated with < 63 μ m nylon sieves and subjected to three digestion procedures: the proposed open digestion, the standard USEPA-3050B and closed digestion in a Teflon tube. The metals were determined by atomic absorption spectrometry. The results of the three procedures showed no significant differences. The 309 mg Kg1 concentration of copper found at the P3 sampling point exceeded the PEL (probable effect level) value of 197 mg Kg1, which represents an environmental hazard to aquatic organisms. The sediments organic matter content determined by the loss on ignition was 6.8, 1.7 and 0.6% in the P3, P1 and P2 samples, respectively. The distribution of metal concentrations in sieved sediment followed the order P3 < P2 < P1 thereby suggesting an interaction with organic matter.

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 Cubatão 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. 13C-NMR and 1H-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 F1 (> 100 kDa).

Evaluating the use of predatory insects as bioindicators of metals contamination due to sugarcane cultivation in neotropical streams

Streams located in areas of sugarcane cultivation receive high concentrations of metal ions from soils of the adjacent areas causing accumulation of metals in the aquatic sediment. This impact results in environmental problems and leads to bioaccumulation of metal ions in aquatic organisms. In the present study, metal concentrations in different predatory insects were studied in streams near sugarcane cultivation and compared to reference sites. Possible utilisation of predatory insects as bioindicators of metal contamination due to sugarcane cultivation from 13 neotropical streams was evaluated. Ion concentrations of Al, Cd, Cr, Cu, Zn, Fe, and Mn in adult Belostomatidae (Hemiptera) and in larvae of Libellulidae (Odonata) were analysed. Nine streams are located in areas with sugarcane cultivation, without riparian vegetation (classified as impacted area) and four streams were located in forested areas (reference sites). Metal concentrations in insects were higher near sugarcane cultivations than in control sites. Cluster analysis, complemented by an ANOSIM test, clearly showed that these insect groups are good potential bioindicators of metal contamination in streams located in areas with sugarcane cultivation and can be used in monitoring programmes. We also conclude that Libellulidae appeared to accumulate higher concentrations of metals than Belostomatidae.

CARACTERIZAÇÃO DE LODO GERADO EM ESTAÇÕES DE TRATAMENTO DE ÁGUA: PERSPECTIVAS DE APLICAÇÃO AGRÍCOLA

The work reported here involved the characterization of sludges produced at water treatment plants in Jaboticabal-SP using FeCl3 as flocculant, and in Taquaritinga-SP and Manaus-AM using Al2(SO4)3 as flocculant. An evaluation was also made of the interaction of organic matter extracted from the sludges with different metal species. The results indicated that all the sludges produced at water treatment plants have an important agricultural potential and that their use depends on the characteristics of the raw water and the type of flocculant employed in conventional treatment. The humic substances extracted from the sludges showed different affinities for metal species, favoring eventual exchanges between potentially toxic metals and macro- and micronutrients. An alternative for the use of sludge in agriculture is to pretreat it to remove potentially toxic metals and enrich it with micro- and macronutrients that can be released to the plant.