Assessment of metal and trace element concentrations in the Cananeia estuary, Brazil, by neutron activation and atomic absorption techniques

Twenty six bottom sediment samples were collected from the Cananeia estuary in summer and winter of 2005. Multielemental analysis was carried out by instrumental neutron activation analysis. Total mercury was determined by cold vapor atomic absorption. As, Cr, Hg and Zn concentrations were compared to the Canadian oriented values (TEL and PEL). Sample points 4 and 9 presented higher concentration for most elements and As and Cr exceeded the TEL values. Organic matter (>10%) associated with siltic and clay sediments was observed. Climatic conditions, hydrodynamic and biogeochemical processes promote differences in seasonal concentrations of elements at some points, which contribute to special distributions.

Preliminary Findings on the Effects of Occupational Exposure to Mercury Vapor Below Safety Levels on Visual and Neuropsychological Functions

Objective: To evaluate whether there are visual and neurophysical decrements in workers with low exposure to Hg vapor. Methods: Visual fields, contrast sensitivity, color vision, and neuropsychological functions were measured in 10 workers (32.5 +/- 8.5 years) chronically exposed to Hg vapor (4.3 +/- 2.8 years; urinary Hg concentration 22.3 +/- 9.3 mu g/g creatinine). Results: For the worst eyes, we found altered visual field thresholds, lower contrast sensitivity, and color discrimination compared with controls (P < 0.05). There were no significant differences between Hg-exposed subjects and controls on. neuropsychological tests. Nevertheless, duration of exposure was statistically correlated to verbal memory and depression scores. Conclusions: Chronic exposure to Hg vapor at currently accepted safety levels was found to be associated with visual losses but not with neuropsychological dysfunctions in the sample of workers studied. (J Occup Environ Med. 2009,51:1403-1412)

Visual field losses in workers exposed to mercury vapor

Visual field losses associated with mercury (Hg) exposure have only been assessed in patients exposed to methylmercury. Here we evaluate the automated visual field in 35 ex-workers (30 males; 44.20+/-5.92 years) occupationaly exposed to mercury vapor and 34 controls (21 males; 43.29+/-8.33 years). Visual fields were analyzed with the Humphrey Field Analyzer II (model 750i) using two tests: the standard automated perimetry (SAP, white-on-white) and the short wavelength automated perimetry (SWAP, blue-on-yellow) at 76 locations within a 27 degrees central visual field. Results were analyzed as the mean of the sensitivities measured at the fovea, and at five successive concentric rings, of increasing eccentricity, within the central field. Compared to controls, visual field sensitivities of the experimental group measured using SAP were lower for the fovea as well as for all five eccentricity rings (p<0.05). Sensitivities were significantly lower in the SWAP test (p<0.05) for four of the five extra-foveal eccentricity rings; they were not significant for the fovea (p = 0.584) or for the 15 degrees eccentricity ring (p = 0.965). These results suggest a widespread reduction of sensitivity in both visual field tests. Previous reports in the literature describe moderate to severe concentric constriction of the visual field in subjects with methylmercury intoxication measured manually with the Goldman perimeter. The present results amplify concerns regarding potential medical risks of exposure to environmental mercury sources by demonstrating significant and widespread reductions of visual sensitivity using the more reliable automated perimetry. (C) 2007 Elsevier Inc. All rights reserved.

Effect of Brazil Nut Supplementation on Plasma Levels of Selenium in Hemodialysis Patients: 12 Months of Follow-up

Background: Large amounts of reactive oxygen species are produced in hemodialysis (HD) patients, and, at higher concentrations, reactive oxygen species are thought to be involved in the pathogenesis of cardiovascular disease. It has been proposed that selenium (Se) may exert an antiatherogenic influence by reducing oxidative stress. The richest known food source of Se is the Brazil nut (Bertholletia excelsa, family Lecythidaceae), found in the Amazon region. Objective: The objective of this work was to determine if Se plasma levels in HD patients submitted to a program of supplementation during 3 months with 1 Brazil nut by day could be sustained after 12 months. Methods: A total of 21 HD patients (54.2 +/- 15.2 years old; average time on dialysis, 82.3 +/- 51.6 months; body mass index, 24.4 +/- 3.8 kg/m(2)) from the RenalCor Clinic in Rio de Janeiro, Brazil, were followed up 12 months after the supplementation study ended. The Se plasma levels were determined by atomic absorption spectrophotometry with hydride generation. Results: The Se Plasma levels (17.3 +/- 19.9 mg/L) were below the normal range (60 to 120 mu g/L) before nut supplementation, and after 3 months of supplementation, the levels increased to 106.8 +/- 50.3 mu g/L (P < .0001). Twelve months after supplementation, the plasma Se levels decreased to 31.9 +/- 14.8 mu g/L (P < .0001). Conclusions: The data showed that these patients were Se deficient and that the consumption of Brazil nut was effective to increase the Se parameters of nutritional status. Se levels 12 months after the supplementation period were not as low as presupplementation levels but yet significantly lower, and we needed to motivate patients to adopt different dietary intake patterns. (C) 2012 by the National Kidney Foundation, Inc. All rights reserved.

Heavy metals in vegetables and potential risk for human health

Ingestion of vegetables containing heavy metals is one of the main ways in which these elements enter the human body. Once entered, heavy metals are deposited in bone and fat tissues, overlapping noble minerals. Slowly released into the body, heavy metals can cause an array of diseases. This study aimed to investigate the concentrations of cadmium, nickel, lead, cobalt and chromium in the most frequently consumed foodstuff in the Sao Paulo State, Brazil and to compare the heavy metal contents with the permissible limits established by the Brazilian legislation. A value of intake of heavy metals in human diets was also calculated to estimate the risk to human health. Vegetable samples were collected at the Sao Paulo General Warehousing and Centers Company, and the heavy metal content was determined by atomic absorption spectrophotometry. All sampled vegetables presented average concentrations of Cd and Ni lower than the permissible limits established by the Brazilian legislation. Pb and Cr exceeded the limits in 44 % of the analyzed samples. The Brazilian legislation does not establish a permissible limit for Co contents. Regarding the consumption habit of the population in the Sao Paulo State, the daily ingestion of heavy metals was below the oral dose of reference, therefore, consumption of these vegetables can be considered safe and without risk to human health.

Effect of Different Radiopacifying Agents on the Physicochemical Properties of White Portland Cement and White Mineral Trioxide Aggregate

Introduction: The aim of this study was to evaluate the pH, calcium ion release, setting time, and solubility of white mineral trioxide aggregate (WMTA) and white Portland cement (WPC) combined with the following radiopacifying agents: bismuth oxide (BO), calcium tungstate (CT), and zirconium oxide (ZO). Methods: Fifty acrylic teeth with root-end filling material were immersed in ultrapure water for measurement of pH and calcium release (atomic absorption spectrophotometry) at 3, 24, 72, and 168 hours. For evaluation of setting time, each material was analyzed according to the American Society for Testing and Materials guidelines 266/08. The solubility test was performed according to American National Standards Institute/American Dental Association specification no. 57/2000. Solubility, setting time, and pH values were compared by using analysis of variance and Tukey test, and the values of calcium release were compared by the Kruskal-Wallis and Miller tests. The significance level was set at 5%. Results: The pH and calcium release were higher at 3 and 24 hours. WPC was the material with the higher values for both properties. WMTA had the greatest solubility among all materials (P < .05). All radiopacifiers increased the setting time of WPC, and WMTA had the shortest setting time among all materials (P < .05). Conclusions: All materials released calcium ions. Except for WPC/CT at 168 hours, all materials promoted an alkaline pH. On the basis of the obtained results, ZO and CT can be considered as potential radiopacifying agents to be used in combination with Portland cement. (J Endod 2012;38:394-397)

Changes in the surface of four calcium silicate-containing endodontic materials and an epoxy resin-based sealer after a solubility test

Aim To compare the changes in the surface structure and elemental distribution, as well as the percentage of ion release, of four calcium silicate-containing endodontic materials with a well-established epoxy resin-based sealer, submitted to a solubility test. Methodology Solubility of AH Plus, iRoot SP, MTA Fillapex, Sealapex and MTA-Angelus (MTA-A) was tested according to ANSI/ADA Specification 57. The deionized water used in the solubility test was submitted to atomic absorption spectrophotometry to determine and quantify Ca2+, Na+, K+, Zn2+, Ni2+ and Pb2+ ions release. In addition, the outer and inner surfaces of nonsubmitted and submitted samples of each material to the solubility test were analysed by means of scanning electron microscopy and energy-dispersive spectroscopy (SEM/EDX). Statistical analysis was performed by using one-way anova and Tukeys post hoc tests (a = 0.05). Results Solubility results, in percentage, sorted in an increasing order were -1.24 +/- 0.19 (MTA-A), 0.28 +/- 0.08 (AH Plus), 5.65 +/- 0.80 (Sealapex), 14.89 +/- 0.73 (MTA Fillapex) and 20.64 +/- 1.42 (iRoot SP). AH Plus and MTA-A were statistically similar (P > 0.05), but different from the other materials (P < 0.05). High levels of Ca2+ ion release were observed in all groups except AH Plus sealer. MTA-A also had the highest release of Na2+ and K+ ions. Zn+2 ion release was observed only with AH Plus and Sealapex sealers. After the solubility test, all surfaces had morphological changes. The loss of matrix was evident and the filler particles were more distinguishable. EDX analysis displayed high levels of calcium and carbon at the surface of Sealapex, MTA Fillapex and iRoot SP. Conclusions AH Plus and MTA-A were in accordance with ANSI/ADAs requirements regarding solubility whilst iRoot SP, MTA Fillapex and Sealapex did not fulfil ANSI/ADAs protocols. High levels of Ca2+ ion release were observed in all materials except AH Plus. SEM/EDX analysis revealed that all samples had morphological changes in both outer and inner surfaces after the solubility test. High levels of calcium and carbon were also observed at the surface of all materials except AH Plus and MTA-A.

A forensic study: Lead determination in gunshot residues

Electrochemical lead analyses of gunshot residues (GSRs) were performed using an acidic solution with a bare gold microelectrode in the presence of chloride ions. GSRs from four different guns (0.38 in. revolver, 12 caliber pump-action shotgun, 0.38 repeating rifle, and a 0.22 caliber semi-automatic rifle) and six different types of ammunition (CleanRange (R), normal, semi-jacketed, especial 24g (R), 3T (R), CBC (R), and Eley (R)) were analyzed. Results obtained with the proposed methodology were compared with those from an atomic absorption spectrometry analysis, and a paired Student's t-test indicated that there was no significant difference between them at the 95% confidence level. With this methodology, a detection limit of 1.7 nmol L-1 (3 sigma/slope), a linear range between 10 and 100 nmol L-1, and a relative standard deviation of 2.5% from 10 measurements were obtained. (C) 2011 Elsevier B.V. All rights reserved.

Evidence of zinc deficiency in competitive swimmers

Objective: The aim of this study was to assess the nutritional zinc (Zn) status of elite swimmers during different training periods. Methods: A longitudinal paired study was performed at the University of Sao Paulo in eight male swimmers 18 to 25 y old who had been swimming competitively at the state and national levels for at least 5 y. The swimmers were evaluated over a total period of 14 wk: before the basic and specific preparatory period (BSPP-baseline), at the end of the basic and specific preparatory period (post-BSPP), and at the end of the polishing period (PP). Levels of Zn were determined in the plasma, erythrocyte, urine, and saliva by atomic absorption spectrophotometry. Anthropometric measurements and a 3-d food record were also evaluated. Results: The median plasma Zn concentration was below the reference value in all training periods (BSPP-baseline 59 mu g/dL, post-BSPP 55.9 mu g/dL, after PP 58.8 mu g/dL, P > 0.05), as were threshold values for erythrocytes (BSPP-baseline 36.5 mu g of Zn/g of hemoglobin, post-BSPP 42 mu g of Zn/g of hemoglobin, after PP 40.7 mu g of Zn/g of hemoglobin, P > 0.05), urinary Zn (BSPP-baseline 280 mu g/24 h, post-BSPP 337 mu g/24 h, after PP 284 mu g/24 h, P > 0.05), and salivary Zn (BSPP-baseline 66.1 mu g/L, post-BSPP 54.1 mu g/L, after PP 79.7 mu g/L, > 0.05). Salivary Zn did not correlate with plasma and erythrocyte Zn levels. Conclusion: The results suggest that the elite swimmers studied presented a possible Zn deficiency and that salivary Zn was not adequate to evaluate the Zn nutritional status. (C) 2012 Elsevier Inc. All rights reserved.

An environmentally friendly analytical procedure for nickel determination by atomic and molecular spectrometry after cloud point extraction in different samples

Cloud point extraction (CPE) was employed for separation and preconcentration prior to the determination of nickel by graphite furnace atomic absorption spectrometry (GFAAS), flame atomic absorption spectrometry (FAAS) or UV-Vis spectrophotometry. Di-2-pyridyl ketone salicyloylhydrazone (DPKSH) was used for the first time as a complexing agent in CPE. The nickel complex was extracted from the aqueous phase using the Triton X-114 surfactant. Under optimized conditions, limits of detection obtained with GFAAS, FAAS and UV-Vis spectrophotometry were 0.14, 0.76 and 1.5 mu g L-1, respectively. The extraction was quantitative and the enrichment factor was estimated to be 27. The method was applied to natural waters, hemodialysis concentrates, urine and honey samples. Accuracy was evaluated by analysis of the NIST 1643e Water standard reference material.

Use of Cathorops spixii as bioindicator of pollution of trace metals in the Santos Bay, Brazil

In the present study Cathorops spixii, was evaluated as a bioindicator fish for trace metal pollution. Concentrations of cobalt (Co), iron (Fe), selenium (Se) and zinc (Zn) were determined by Instrumental Neutron Activation Analysis in liver. Mercury (Hg) and methyl-mercury (MeHg) were analyzed by Cold Vapor Atomic Absorption Spectrometry in muscles and livers. High concentrations of Co, Fe, Se and Zn were observed in C. spixii from Santos Bay in comparison to fish collected in a non-polluted site in the same Brazilian coast. These trace metal concentrations were out of the permissible levels for human consumption. Although, Hg and MeHg levels were low, the C. spixii could still be used as an effective bioindicator to observe trace metal behaviors in the environment in function of the bioaccumulation process observed mainly by other analyzed trace metals. Thus, the use of this species is strongly recommended to monitor the effects and behavior of trace metal pollution in aquatic ecosystems in Brazil due to its bioaccumulation function.

An Alternative Method for the Simultaneous Determination of Copper and Lead for Quality Control of Sugar Cane Spirit using a Nanotube-Based Sensor

The development of an electroanalytical method for simultaneous determination of copper and lead ions in sugar cane spirit (cachaca) using carbon paste electrode modified with ascorbic acid and carbon nanotubes (CPE-AaCNT) is described. Squarewave voltammetry (SWV) with anodic stripping was employed, and this technique was optimized with respect to the following parameters: frequency (50 Hz), amplitude (100 mV) and scan increment (9 mV). The analytical curves were linear in the range from 0.0900 to 7.00 mg L-1 for lead and copper. The limits of detection were 48.5 and 23.9 mu g L-1 for lead and copper, respectively. The developed method was applied to the simultaneous determination of copper and lead in five commercial samples of sugar cane spirit. The results were in good agreement with those obtained by F AAS/GF AAS (flame atomic absorption spectrometry/graphite furnace atomic absorption spectrometry) and showed that CPE-AaCNT can be successfully employed in the simultaneous determination of these metals in real sugar cane spirit samples.

Application of an active attachment model as a high-throughput demineralization biofilm model

Objectives: To investigate the potential of an active attachment biofilm model as a highthroughput demineralization biofilm model for the evaluation of caries-preventive agents. Methods: Streptococcus mutans UA159 biofilms were grown on bovine dentine discs in a highthroughput active attachment model. Biofilms were first formed in a medium with high buffer capacity for 24 h and then subjected to various photodynamic therapies (PACT) using the combination of Light Emitting Diodes (LEDs, Biotable (R)) and Photogem (R). Viability of the biofilms was evaluated by plate counts. To investigate treatment effects on dentine lesion formation, the treated biofilms were grown in a medium with low buffer capacity for an additional 24 h. Integrated mineral loss (IML) and lesion depth (LD) were assessed by transversal microradiography. Calcium release in the biofilm medium was measured by atomic absorption spectroscopy. Results: Compared to the water treated control group, significant reduction in viability of S. mutans biofilms was observed when the combination of LEDs and Photogem (R) was applied. LEDs or Photogem (R) only did not result in biofilm viability changes. Similar outcomes were also found for dentine lesion formation. Significant lower IML and LD values were only found in the group subjected to the combined treatment of LEDs and Photogem (R). There was a good correlation between the calcium release data and the IML or LD values. Conclusions: The high-throughput active attachment biofilm model is applicable for evaluating novel caries-preventive agents on both biofilm and demineralization inhibition. PACT had a killing effect on 24 h S. mutans biofilms and could inhibit the demineralization process. (C) 2011 Elsevier Ltd. All rights reserved.

Physicochemical properties of endodontic sealers of different bases

Objective: To assess the setting time (ST), flow (FL), radiopacity (RD), solubility (SB) and dimensional change following setting (DC) of different sealers (AH Plus (R), Polifil, Apexit Plus (R), Sealapex (R), Endomethasone (R) and Endofill (R)) according to American National Standards Institute/American Dental Association (ANSI/ADA) Specification 57. Material and methods: Five samples of each material were used for each test. For ST, cast rings were filled with sealers and tested with a Gillmore needle. For FL, the sealer was placed on a glass plate. After 180 s, another plate with 20 g and a load of 100 g were applied on the material, and the diameters of the discs formed were measured. In RD, circular molds were filled with the sealers, radiographed and analyzed using Digora software. For SB, circular molds were filled with the sealers, a nylon thread was placed inside the material and another glass plate was positioned on the set, pressed and stored at 37 degrees C. Samples were weighed, placed in water, dried and reweighed. The water used for SB was analyzed by atomic absorption spectrometry. For DC, circular molds were filled with the sealers, covered by glass plates and stored at 37 degrees C. Samples were measured and stored in water for 30 days. After this period, they were dryed and measured again. Results: Regarding ST, AH Plus (R), Apexit (R) and Endofil (R) sealers are in accordance with ANSI/ADA standards. Endomethasone's manufacturer did not mention the ST; Polifil is an experimental sealer and Sealapex (R) did not set. Considering RD, SB and DC, all sealers were in accordance with ANSI/ADA. The spectrometric analysis showed that a significant amount of K+ and Zn2(+) ions was released from Apexit Plus (R) and Endofill (R), respectively. Conclusion: Except for DC, all other physicochemical properties of the tested sealers conformed to ANSI/ADA requirements.

Biomonitoring of coastal regions of So Paulo State, Brazil, using mussels Perna perna

The marine environment is constantly affected by anthropic actions, with causes consequent degradation of the waters and marine biota by various discharges of xenobiotics. In the present study, the focus was the study of a region of the marine coast of the State of So Paulo (city of Santos), which is one of the most industrialized parts of Brazil and suffers also from a strong impact of domestic effluents. The mussel Perna perna, very abundant in the coast of the State of So Paulo, Brazil, was selected as the biomonitoring organism for the determination of inorganic elements and a passive biomonitoring was performed. The organisms were collected at two sites in So Paulo State coast: Cocanha beach in Caraguatatuba (mussel farm) and Santos Bay (Itaipu and Palmas). Seasonally, the Perna perna were collected between September/08 and July/09 in each study sites. After removal and sample preparation, the elements As, Co, Cr, Fe, Se and Zn were determined by instrumental neutron activation analysis (INAA) and Cd, Pb and Hg were determined by atomic absorption spectroscopy (AAS) in this organism.