Decolorization and toxicity of municipal waste by horseradish (Cochlearia armoracia)

The Municipal Station of Americana, SP, Brazil, treats a volume of 400 l s-1 of effluent, of domestic and textile origin, and produces about 20 t of sludge per day. The plant horseradish, which contains high amount of peroxidases, was able to decolorize this effluent in 2 h and the solid waste in 2 days, at concentrations of 10 and 50%, respectively. However, there was an increase in the toxicity for the bioassays with Hydra attenuatta, Selenastrum capricornutum and lettuce seeds, indicating formation of more toxic substances. Since horseradish showed the ability to decolorize these residues, it can be used as pre-treatment resulting in a sludge of less complex composition.

Cloud point extraction for the determination of copper in environmental samples by flame atomic absorption spectrometry

A simple cloud point extraction procedure is presented for the preconcentration of copper in various samples. After complexation by 4-hydroxy-2-mercapto-6-propylpyrimidine (PTU), copper ions are quantitatively extracted into the phase rich in Triton X-114 after centrifugation. Methanol acidified with 0.5 mol L-1 HNO3 was added to the surfactant-rich phase prior to its analysis by flame atomic absorption spectrometry (FAAS). Analytical parameters including concentrations for PTU, Triton X-114 and HNO3, bath temperature, centrifugation rate and time were optimized. The influences of the matrix ions on the recoveries of copper ions were investigated. The detection limits (3SDb/m, n=4) of 1.6 ng mL-1 along with enrichment factors of 30 for Cu were achieved. The proposed procedure was applied to the analysis of environmental samples.

Removal of copper(II) from sugar-cane spirits employing chitosan

A method employing chitosan as complexant agent in the removal of copper(II) ions generally present in the Brazilian cachaça samples is herein proposed. The efficiency of this method is attributed to its high capacity of metal cations adsorption, mainly due to presence of hydroxyl and amine groups that can serve as chelating sites. The removal of copper(II) ions from this alcoholic beverage was efficient employing either in column and batch system. The analysis were carried out employing the flame atomic absorption spectrometry and the remaining copper(II) concentrations in the treated cachaça were lower than LOD of FAAS technique.

Separation and preconcentration of copper in environmental samples on Amberlite XAD-8 resin after complexation with a carbothioamide derivative

A new solid phase extraction (SPE) method has been developed for the selective separation and preconcentration of Cu (II) ions in food and water samples prior to its flame atomic absorption spectrometry determination. The method is based on the adsorption of the Cu(II) - 2-{[4-Amino-3-(4-methylphenyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]acetyl}-N-phenyl hydrazinecarbothioamide complex on Amberlite XAD-8 resin. The metal complex retained on the resin was eluted with 7.5 mL of 2.0 mol L-1 HCl in acetone. The optimum conditions for the SPE of Cu(II) ions were investigated, and the method was subsequently applied to sea water, stream water, rice, tea, and tobacco samples for the determination of Cu(II) levels.

Preconcentration of copper from natural water samples using ligand-less in situ surfactant-based solid phase extraction prior to FAAS determination

In the present work, a simple and rapid ligand-less, in situ, surfactant-based solid phase extraction for the preconcentration of copper in water samples was developed. In this method, a cationic surfactant (n-dodecyltrimethylammonium bromide) was dissolved in an aqueous sample followed by the addition of an appropriate ion-pairing agent (ClO4-). Due to the interaction between the surfactant and ion-pairing agent, solid particles were formed and subsequently used for the adsorption of Cu(OH)2 and CuI. After centrifugation, the sediment was dissolved in 1.0 mL of 1 mol L-1 HNO3 in ethanol and aspirated directly into the flame atomic absorption spectrometer. In order to obtain the optimum conditions, several parameters affecting the performance of the LL-ISS-SPE, including the volumes of DTAB, KClO4, and KI, pH, and potentially interfering ions, were optimized. It was found that KI and phosphate buffer solution (pH = 9) could extract more than 95% of copper ions. The amount of copper ions in the water samples varied from 3.2 to 4.8 ng mL-1, with relative standard deviations of 98.5%-103%. The determination of copper in water samples was linear over a concentration range of 0.5-200.0 ng mL-1. The limit of detection (3Sb/m) was 0.1 ng mL-1 with an enrichment factor of 38.7. The accuracy of the developed method was verified by the determination of copper in two certified reference materials, producing satisfactory results.

Determination of Copper, Iron, Nickel and Zinc in fuel kerosene by FAAS after adsorption and pre-concentration on 2-aminothiazole-modified silica gel

Silica gel chemically modified with 2-Aminotiazole groups, abbreviated as SiAT, was used for preconcentration of copper, zinc, nickel and iron from kerosene, normally used as a engine fuel for airplanes. Surface characteristics and surface area of the silica gel were obtained before and after chemical modification using FT-IR, Kjeldhal and surface area analysis (B.E.T.). The retention and recovery of the analyte elements were studied by applying batch and column techniques. The experimental parameters, such as shaking time in batch technique, flow rate and concentration of the eluent (HCl- 0.25-2.00 mol L-1) and the amount of silica, on retention and elution, have been investigated. Detection limits of the method for copper, iron, nickel and zinc are 0.77, 2.92, 1.73 and 0.097 mg L-1, respectively. The sorption-desorption of the studied metal ions made possible the development of a preconcentration method for metal ions at trace level in kerosene using flame AAS for their quantification.

Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 silica in the determination of copper

The performance of a carbon paste electrode (CPE) modified with SBA-15 nanostructured silica organofunctionalised with 2-benzothiazolethiol for determination of Cu(II) ions in sugar cane spirit (cachaça) is described, based on differential pulse anodic stripping voltammetry (DPASV) procedure. The Cu(II) oxidation peak was observed at 0.03 V (vs. SCE) in phosphate solution (pH 3.0). The results were obtained using optimised conditions such as 100 mV pulse amplitude, 3 min accumulation time, 25 mV s-1 scan rate in phosphate solution pH 3.0, resulting in a linear dynamic range from 8.0 x 10-7 to 1.0 x 10-5 mol L-1 Cu(II) and a limit of detection 2.0 x10-7 mol L-1. Cu(II) spiked in a cachaça sample was determined with 102.5 % mean recovery at mmol L-1 level. Interference from other metallic cations present in the sample was avoided by the standard addition procedure.

Synthesis and magnetic studies of copper(II)-lanthanide(III) 5-bromosalicylideneglycylglycine

The physico-chemical properties of the new 3d-4f heteronuclear complexes with general formula LnCu3(C11H8N2 O4Br)3·13H2O (where Ln = Pr, Eu, Gd, Tb, Er, Yb and H3(C11H8N2 O4Br) - 5-bromosalicylideneglycylglycine) were studied. The compounds were characterized by elemental, spectral and thermal analyses and magnetic measurements. The formation of Schiff base is evidenced by a strong band at ca. 1646-1650 cm-1 attributable to C=N stretching mode. The presence of water molecules is confirmed by broad absorptions with maximum at 3360 - 3368 cm-1. The Cu(II)-Ln(III) complexes are stable up to ca. 318 K. During dehydration process the water molecules are lost probably in two stages. The magnetic susceptibility data for these complexes change with temperature according to the Curie-Weiss law.

Determination of copper at wide range concentrations using instrumental features of high-resolution continuum source flame atomic absorption spectrometry

This work describes a method to determine Cu at wide range concentrations in a single run without need of further dilutions employing high-resolution continuum source flame atomic absorption spectrometry. Different atomic lines for Cu at 324.754 nm, 327.396 nm, 222.570 nm, 249.215 nm and 224.426 nm were evaluated and main figures of merit established. Absorbance measurements at 324.754 nm, 249.215 nm and 224.426 nm allows the determination of Cu in the 0.07 - 5.0 mg L-1, 5.0 - 100 mg L-1 and 100 - 800 mg L-1 concentration intervals respectively with linear correlation coefficients better than 0.998. Limits of detection were 21 µg L-1, 310 µg L-1 and 1400 µg L-1 for 324.754 nm, 249.215 nm and 224.426 nm, respectively and relative standard deviations (n = 12) were £ 2.7%. The proposed method was applied to water samples spiked with Cu and the results were in agreement at a 95% of confidence level (paired t-test) with those obtained by line-source flame atomic absorption spectrometry.

Diagnostic value of copper parameters to predict growth of suckling calves grazing native range in Argentina

A study was conducted to evaluate the predictive diagnostic value of different copper (Cu) parameters as indicators of average daily gain (ADG) in growing calves. The effects in calves of cow Cu supplementation in the last one-third gestation period were also evaluated. Five supplementation trials, with a total of 300 calves, were carried out. Two groups of 30 calves were randomly assigned to each trial, one group was parenterally supplemented (SG) and the other was not supplemented (NSG). Trials began when calves were three-month-old and ended at weaning time. At each sampling calves were weighed and blood was taken to determine Cu concentrations in plasma, Whole Blood (WB), Red Cells (RC) and Packed Cell Volume (PCV). Liver samples from six animals of each group were taken both at the beginning and at the end of the trial. In two trials the mothers of the SG received Cu supplementation at the last one- third gestation period. Four of the five trials exhibited low ADG in the NSGs. In these groups, plasma Cu concentration decreased rapidly before low ADG was detected, which occurred with values remaining below 25µg/dl. The decrease of RC Cu concentration was considerably slow. WB showed an intermediate position. PCV in the SGs was higher than in the NSGs in all trials. Cow supplementation was insufficient to generate a liver storage able to last after calves reached the 3 months of age. These data could be useful to predict the risk of low ADG in grazing calves.

Antimicrobial activity and acute and chronic toxicity of the essential oil of Lippia origanoides

Currently, there is a growing interest in medicinal plants, because of an increased demand for alternate therapies. In this study, the antimicrobial activity and toxicity of the essential oil of Lippia origanoides (L. origanoides) were investigated. The essential oil of L. origanoides was extracted by steam-dragging distillation and its constituents were identified by chromatography coupled with mass spectrometry. Among the 15 compounds identified, the most abundant were carvacrol (29.00%), o-cymene (25.57%), and thymol methyl ether (11.50%). The essential oil was studied in antimicrobial assays to determine the MIC and MBC. The results indicated that a concentration of 120μL/mL of oil was sufficient to inhibit the growth of the following microorganisms: Escherichia coli (ATCC 25922), Staphylococcus aureus (ATCC 25923) and Salmonella cholerasuis (ATCC 10708). Acute and chronic toxic effects of orally administered oil were investigated in Wistar rats by using standard methods. Doses of 30, 60 and 120mg/kg of the essential oil did not induce significant changes in weight, behavior or hematological and biochemical parameters in the animals. There were no signs of any histopathological changes to the liver, kidneys or heart of the treated rats, suggesting that Lippia origanoides oil is non-toxic after oral administration in acute or chronic toxicity studies. The results obtained in this study show that the essential oil of L. origanoides has a high safety margin, with no detectable toxic effects in rats treated with doses to 120mg/kg. In addition, L. origanoides oil demonstrated potent antimicrobial activity against S. aureus, E. coli and S. cholerasuis. Based on these findings, this essential oil may have practical application as a veterinary antimicrobial.

Study of the embryofeto-toxicity of Crown-of-Thorns (Euphorbia milii) latex, a natural molluscicide

The crude latex of Crown-of-Thorns (Euphorbia milii var. hislopii) is a potent plant molluscicide and a promising alternative to the synthetic molluscicides used in schistosomiasis control. The present study was undertaken to investigate the embryofeto-toxic potential of E. milii latex. The study is part of a comprehensive safety evaluation of this plant molluscicide. Lyophilized latex (0, 125, 250 and 500 mg/kg body weight) in corn oil was given by gavage to Wistar rats (N = 100) from days 6 to 15 of pregnancy and cesarean sections were performed on day 21 of pregnancy. The numbers of implantation sites, living and dead fetuses, resorptions and corpora lutea were recorded. Fetuses were weighed, examined for external malformations, and fixed for visceral examination, or cleared and stained with Alizarin red S for skeleton evaluation. A reduction of body weight minus uterine weight at term indicated that E. milii latex was maternally toxic over the dose range tested. No latex-induced embryolethality was noted at the lowest dose (125 mg/kg) but the resorption rate was markedly increased at 250 mg/kg (62.5%) and 500 mg/kg (93.4%). A higher frequency of fetuses showing signs of delayed ossification (control: 17.4%; 125 mg/kg: 27.4% and 250 mg/kg: 62.8%; P<0.05 vs control) indicated that fetal growth was retarded at doses ³ 125 mg latex/kg body weight. No increase in the proportion of fetuses with skeletal anomalies was observed at the lowest dose but the incidence of minor skeletal malformations was higher at 250 mg/kg body weight (control: 13.7%; 125 mg/kg: 14.8%; 250 mg/kg: 45.7%; P<0.05 vs control). Since a higher frequency of minor malformations was noted only at very high doses of latex which are embryolethal and maternally toxic, it is reasonable to conclude that this plant molluscicide poses no teratogenic hazard or, at least, that this possibility is of a considerably low order of magnitude

Toxicity of a cyanobacterial extract containing microcystins to mouse lungs

Toxic cyanobacteria in drinking water supplies can cause serious public health problems. In the present study we analyzed the time course of changes in lung histology in young and adult male Swiss mice injected intraperitoneally (ip) with a cyanobacterial extract containing the hepatotoxic microcystins. Microcystins are cyclical heptapeptides quantified by ELISA method. Ninety mice were divided into two groups. Group C received an injection of saline (300 µl, ip) and group Ci received a sublethal dose of microcystins (48.2 µg/kg, ip). Mice of the Ci group were further divided into young (4 weeks old) and adult (12 weeks old) animals. At 2 and 8 h and at 1, 2, 3, and 4 days after the injection of the toxic cyanobacterial extract, the mice were anesthetized and the trachea was occluded at end-expiration. The lungs were removed en bloc, fixed, sectioned, and stained with hematoxylin-eosin. The percentage of the area of alveolar collapse and the number of polymorphonuclear (PMN) and mononuclear cell infiltrations were determined by point counting. Alveolar collapse increased from C to all Ci groups (123 to 262%) independently of time, reaching a maximum value earlier in young than in adult animals. The amount of PMN cells increased with time of the lesion (52 to 161%). The inflammatory response also reached the highest level earlier in young than in adult mice. After 2 days, PMN levels remained unchanged in adult mice, while in young mice the maximum number was observed at day 1 and was similar at days 2, 3, and 4. We conclude that the toxins and/or other cyanobacterial compounds probably exert these effects by reaching the lung through the blood stream after ip injection.

Evaluation of cardiovascular toxicity of carbon nanotubes functionalized with sodium hyaluronate in oral regenerative medicine

It has been demonstrated that carbon nanotubes (CNTs) associated with sodium hyaluronate (HY-CNTs) accelerate bone repair in the tooth sockets of rats. Before clinical application of HY-CNTs, it is important to assess their biocompatibility. Moreover, cardiac toxicity may be caused by the translocation of these particles to the blood stream. The aim of this study was to evaluate possible changes in cardiovascular function in male Wistar rats whose tooth sockets were treated with either CNTs or HY-CNTs (100 μg/mL, 0.1 mL). Blood pressure and heart rate were monitored in conscious rats 7 days after treatment. Cardiac function was evaluated using the Langendorff perfusion technique. The data showed no changes in blood pressure or heart rate in rats treated with either CNTs or HY-CNTs, and no significant changes in cardiac function were found in any of the groups. To confirm these findings, experiments were conducted in rats injected intraperitoneally with a high concentration of either CNTs or HY-CNTs (0.75 mg/kg). The same parameters were analyzed and similar results were observed. The results obtained 7 days following injection indicate that the administration of low concentrations of CNTs or HY-CNTs directly into tooth sockets did not cause any significant change in cardiovascular function in the rats. The present findings support the possibility of using these biocomposites in humans.

THE COPPER INTERFERENCE WITH THE MELANOGENESIS OF Cryptococcus neoformans

Melanin is a pigment produced by laccase, a phenoloxydase enzyme, and is related to the virulence of Cryptococcus neoformans as it is also considered an adaption mechanism to environmental conditions and protection against UV radiation, phagocytic system attack and antifungal drugs. Laccase synthesis is stimulated by several factors, including copper metabolism. The current study shows C. neoformans strains with higher melanization intensity when grown in L-dopa medium supplemented with different concentrations of copper sulfate. This increase shows that melanization rates may be enhanced in the presence of copper ions and may also enhance the virulence of C. neoformans in infected patients that present increasing copper concentrations in serum, such as those with HIV. The virulence of these strains may also be increased in the environment, where this metal is available as CuSO4 in algicidal and fungicidal compounds.