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® 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 SnCl2, 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 SnCl2 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. (C) 2000 Elsevier Science B.V.

Preconcentration and determination of mercury(II) at a chemically modified electrode containing 3-(2-thioimidazolyl)propyl silica gel

A mercury-sensitive chemically modified graphite paste electrode was constructed by incorporating modified silica gel into a conventional graphite paste electrode. The functional group attached to the (3-chloropropyl) silica gel surface was 2-mercaptoimidazole, giving a new product denoted by 3-(2-thioimidazolyl)propyl silica gel, which is able to complex mercury ions. Mercury was chemically adsorbed on the modified graphite paste electrode containing 3-(2-thioimidazolyl)propyl silica (TIPSG GPE) by immersion in a Hg(II) solution, and the resultant surface was characterized by cyclic and differential pulse anodic stripping voltammetry. One cathodic peak at 0.1 V and other anodic peak at 0.34 V were observed on scanning the potential from -0.1 to 0.8 V (0.01 M KNO3; ν = 2.0 mV s-1 νs. Ag/AgCl). The anodic peak at 0.34 V show an excellent sensitivity for Hg(II) ions in the presence of several foreign ions. A calibration graph covering the concentration range from 0.02 to 2 mg L-1 was obtained. The detection limit was estimated to be 5 μg L-1. The precision for six determinations of 0.05 and 0.26 mg L-1 Hg(II) was 3.0 and 2.5% (relative standard deviation), respectively. The method can be used to determine the concentration of mercury(II) in natural waters contaminated by this metal. 2005 © The Japan Society for Analytical Chemistry.

Evaluating quality of life in mercury intoxicated people in urban-industrial environments through short-form 36 application

Context and objective: Records of contact with mercury (Hg) exist for more than 3500 years and several problems related to the use of this element can be noticed. Considering inexistence of current reports about it, quality of life perception evaluation was studied in people chronically intoxicated by mercury in an industrial environment. Design and setting: This is a cross-sectional descriptive observational study. Information from 47 urban-industrial workers from lamps manufacturing in São Paulo, clinically diagnosed as intoxicated by mercury and currently followed by the Occupational Health Service of Faculdade de Medicine da Universidade de São Paulo, with average age of 41.7 years old, was considered. Methods: SF36 questionnaire application was performed, with inferences tested by χ-square proof, by Spearman linear correlation and Mann-Whitney non-parametric test, adopting p < 0.05 as significant level. Results: In the eight domains, observed medians are 40% for physical functioning; 0 for physical function; 30% for body pain; 30% for general health; 22.2% for vitality; 50% for social functioning; 0 for emotional role and 36% for mental health. Correlation between age and SF36 domains does not reveal statistical significance, except for physical functioning, indicating that lower scores presented by older people in this domain are not followed by changes on other ones. Conclusions: Values obtained in people chronically intoxicated by mercury are actually lower, in the motor and mental scope components. Some instruments domains are higher for men than for women. Older ages are inversely associated to good performance in physical function domain. © Copyright Moreira Jr. Editora. Todos os direitos reservados.

Seasonal behavior of mercury species in waters and sediments from the Negro River Basin, Amazon, Brazil

Total (HgT), reactive (HgR) and organic (Hg ORG) mercury species have been quantified in non-filtered waters collected from the Negro River Basin, Amazon (from January/2002 through January/2004), in both black and white water bodies. Black waters presented the highest HgT, HgORG and HgR concentration (29.1 ng L-1, 1.63 ng L-1 and 3.9 ng L-1, respectively), while, white waters presented the lowest HgT, Hg ORG and HgR concentration (8.8 ng L-1, 0.49 ng L-1 and 1.2 ng L-1, respectively). An inverse correlation between HgT and the water level over the basin was obtained, although the HgORG concentration has increased in the first rainy months and then decreased as the water level rose. Total mercury in surface sediments (0-10 cm) ranged from 70 to 271 mg kg-1 being the methylmercury 0.47-1.79 % of this stock. The results indicate that HgR and the labile dissolved organic matter were introduced into the aquatic environment during the flooding season, especially in the earlier stages, thus contributing to mercury methylation. ©2007 Sociedade Brasileira de Química.

Voltammetry of mercury (II) based on an organo-clay modified graphite electrode

Organo-clay complex of ligand-hexadecyltrimethylammonium with montmorillonite was made for the purpose of application as a preconcentration agent in a chemically modified carbon paste electrode for determination of mercury (II) in aqueous solution. It was found out that the adsorption of Hg(II) by organo-clay complex is independent of the pH of the solution. It was also found out that the adsorption of the remaining metals Cd(II), Ps(II), Cu(II), Zn(II), and Ni(II) was dependent on the changes in pH solutions and increased when it varies from 1 to 8. The resultant material was characterized by cyclic and differential pulse anodic voltammetry using a modified graphite paste electrode in different supporting electrolytes. The mercury response was evaluated with respect to pH, electrode composition, preconcentration time, mercury concentration, possible interferences and other variables.

Mercury, copper, and zinc concentrations in extracted human teeth

Amalgam has been used as a filling material for over 150 years. Mercury, copper, and zinc are present in restoration. The aim of this study was to compare mercury, copper, and zinc concentrations in extracted human teeth with amalgam restorations and teeth without restorations. Thirty-two teeth, 15 restored with dental amalgam and 17 without restorations, were chemically analyzed in an Optima 3300 DV (Perkin Elmer) plasma emission spectrometer. Mercury, copper, and zinc were found in human teeth regardless of the presence of amalgam restorations. The highest mercury concentrations were found in the coronary portions of the teeth with amalgam restorations. Copper concentrations were very high. Zinc concentrations in the teeth without restoration were lower than those seen in the coronary portion of the teeth with restorations. © 2009 Heldref Publications.

Determination of Mg (II) in biodiesel by adsorptive stripping voltammetry at a mercury film electrode in the presence of sodium thiopentone

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Direct simultaneous determination of Pb(II) and Cu(II) in biodiesel by anodic stripping voltammetry at a mercury-film electrode using microemulsions

A mercury film electrode was used to determine direct and simultaneously Pb(II) (at -410 mV) and Cu(II) (at -100 mV) in biodiesel by anodic stripping voltammetry. A linear response was obtained for Pb(II) and Cu(II) in the 2.00 × 10-8-1.00 × 10-7 mol L-1 concentration range and detection limits were 2.91 × 10-9 mol L-1 and 4.69 × 10-9 mol L-1 for Pb(II) and Cu(II), respectively, with recovery around of 100.0%. © 2012 Elsevier Ltd. All rights reserved.

Mercury concentrations in south atlantic swordfish, Xiphias gladius, Caught off the Coast of Brazil

This study evaluated the concentrations of mercury in fillets (anterior, middle, and end regions) from the swordfish, Xiphias gladius, and the relationships between mercury concentration and fish weight, as well as the region of collection. Of a total of 697 swordfish analyzed, 11 had mercury concentrations above 1 mg/kg, 421 were between 0.5 and 1.0 mg/kg, and 265 were below 0.5 mg/kg. The anterior and posterior regions had greater concentrations of mercury than the middle region, and fish caught off the northern coast of Brazil had a higher concentration than those caught off the southern coast. © 2013 Springer Science+Business Media New York.

GFAAS determination of mercury in muscle samples of fish from Amazon, Brazil

In the present study, a simple, rapid and sensitive method was developed for the determination of mercury concentrations in the muscle tissue of fish from the Brazilian Amazon using graphite furnace atomic absorption spectrometry (GFAAS) following acid mineralization of the samples in an ultrasonic cold water bath. Using copper nitrate as a chemical modifier in solution and sodium tungstate as permanent modifier, we were able to attain thermal stabilization of the mercury up to the atomisation temperature of 1600 °C in the GFAAS assay. The calculated limits of detection (LOD) and quantification (LOQ) were 0.014 and 0.047 mg kg-1, respectively. © 2013 Elsevier Ltd. All rights reserved.

Comparative study of human exposure to mercury in riverside communities in the Amazon region

Four populations in the Amazon area were selected for a comparative study of mercury-exposed and non-exposed populations: São Luiz do Tapajós, Barreiras, Panacauera, and Pindobal Grande. The highest mercury levels in human hair samples were found in São Luiz do Tapajós and Barreiras, greatly exceeding the limits established by the World Health Organization. Panacauera showed an intermediate level below 9 µg/g. This was the first comparative and simultaneous evaluation of mercury exposure in the Amazon area. Also, thanks to this type of monitoring, we were able to eliminate the uncertainties about the reference dose. On the basis of these data, we can conclude that the mercury levels detected in exposed populations of the Tapajós River basin may be dangerous not only because they are above the World Health Organization limits, but also because the simultaneous mercury detection in non-exposed populations with similar characteristics provided a valid control and revealed lower mercury levels. Our results support the importance of continuous monitoring in both exposed and non-exposed populations.

A first evaluation on the use of Ardea albus feathers as bioindicators of mercury burden in Amazonian ecosystems

O objetivo deste estudo foi avaliar as concentrações de mercúrio total em penas de Ardea albus coletadas em uma assembléia de aves localizada nas imediações da cidade de Belém, Pará, com vistas a investigar a possibilidade do uso desta espécie nos estudos de biomonitoramento deste metal. Para determinação de mercúrio total foi utilizada a espectrofotometria de absorção atômica com amalgamação. A concentração média de mercúrio total nas penas do corpo foi 2,2 ± 1,5 µg.g-1 e nas penas das asas foi 1.3 ± 0.9 µg/g-1. Não foi observada correlação entre a concentração de mercúrio total e o comprimento das penas do corpo e da asa. Foi observado teor de mercúrio total superior a 5 µg.g-1 em apenas uma amostra de pena do corpo.

Mercury toxicity in the Amazon: contrast sensitivity and color discrimination of subjects exposed to mercury

We measured visual performance in achromatic and chromatic spatial tasks of mercury-exposed subjects and compared the results with norms obtained from healthy individuals of similar age. Data were obtained for a group of 28 mercury-exposed subjects, comprising 20 Amazonian gold miners, 2 inhabitants of Amazonian riverside communities, and 6 laboratory technicians, who asked for medical care. Statistical norms were generated by testing healthy control subjects divided into three age groups. The performance of a substantial proportion of the mercury-exposed subjects was below the norms in all of these tasks. Eleven of 20 subjects (55%) performed below the norms in the achromatic contrast sensitivity task. The mercury-exposed subjects also had lower red-green contrast sensitivity deficits at all tested spatial frequencies (9/11 subjects; 81%). Three gold miners and 1 riverine (4/19 subjects, 21%) performed worse than normal subjects making more mistakes in the color arrangement test. Five of 10 subjects tested (50%), comprising 2 gold miners, 2 technicians, and 1 riverine, performed worse than normal in the color discrimination test, having areas of one or more MacAdam ellipse larger than normal subjects and high color discrimination thresholds at least in one color locus. These data indicate that psychophysical assessment can be used to quantify the degree of visual impairment of mercury-exposed subjects. They also suggest that some spatial tests such as the measurement of red-green chromatic contrast are sufficiently sensitive to detect visual dysfunction caused by mercury toxicity.

Cytotoxicity and genotoxicity of low doses of mercury chloride and methylmercury chloride on human lymphocytes in vitro

Mercury is a xenobiotic metal that is a highly deleterious environmental pollutant. The biotransformation of mercury chloride (HgCl2) into methylmercury chloride (CH3HgCl) in aquatic environments is well-known and humans are exposed by consumption of contaminated fish, shellfish and algae. The objective of the present study was to determine the changes induced in vitro by two mercury compounds (HgCl2 and CH3HgCl) in cultured human lymphocytes. Short-term human leukocyte cultures from 10 healthy donors (5 females and 5 males) were set-up by adding drops of whole blood in complete medium. Cultures were separately and simultaneously treated with low doses (0.1 to 1000 µg/l) of HgCl2 and CH3HgCl and incubated at 37ºC for 48 h. Genotoxicity was assessed by chromosome aberrations and polyploid cells. Mitotic index was used as a measure of cytotoxicity. A significant increase (P < 0.05) in the relative frequency of chromosome aberrations was observed for all concentrations of CH3HgCl when compared to control, whether alone or in an evident sinergistic combination with HgCl2. The frequency of polyploid cells was also significantly increased (P < 0.05) when compared to control after exposure to all concentrations of CH3HgCl alone or in combination with HgCl2. CH3HgCl significantly decreased (P < 0.05) the mitotic index at 100 and 1000 µg/l alone, and at 1, 10, 100, and 1000 µg/l when combined with HgCl2, showing a synergistic cytotoxic effect. Our data showed that low concentrations of CH3HgCl might be cytotoxic/genotoxic. Such effects may indicate early cellular changes with possible biological consequences and should be considered in the preliminary evaluation of the risks of populations exposed in vivo to low doses of mercury.

Cytogenetic damage related to low levels of methyl mercury contamination in the Brazilian Amazon

The mercury rejected in the water system, from mining operations and lixiviation of soils after deforestation, is considered to be the main contributors to the contamination of the ecosystem in the Amazon Basin. The objectives of the present study were to examine cytogenetic functions in peripheral lymphocytes within a population living on the banks of the Tapajós River with respect to methylmercury (MeHg) contamination, using hair mercury as a biological indicator of exposure. Our investigation shows a clear relation between methylmercury contamination and cytogenetic damage in lymphocytes at levels well below 50 micrograms/gram, the level at which initial clinical signs and symptoms of mercury poisoning occur. The first apparent biological effect with increasing MeHg hair level was the impairment of lymphocyte proliferation measured as mitotic index (MI). The relation between mercury concentration in hair and MI suggests that this parameter, an indicator of changes in lymphocytes and their ability to respond to culture conditions, may be an early marker of cytotoxicity and genotoxicity in humans and should be taken into account in the preliminary evaluation of the risks to populations exposed in vivo. This is the first report showing clear cytotoxic effects of long-term exposure to MeHg. Although the results strongly suggest that, under the conditions examined here, MeHg is both a spindle poison and a clastogen, the biological significance of these observations are as yet unknown. A long-term follow-up of these subjects should be undertaken.