Contribution to the study of the solid-state reaction of mercury with pure rhodium

Thermogravimetry (TG) and other analysis techniques (EDX, SEM, Mapping surface, X-ray diffraction, inductively coupled argon plasma emission spectroscopy and atomic spectrometry with cold vapor generation) were used to study the reaction of Hg with Rh. The results permitted the suggestion that, when subjected to heat, an electrodeposited Hg film reacts with Rh to form intermetallic products with different stabilities, as indicated by at least three mass loss steps. In the first step, between room temperature and 160°C, only the bulk Hg is removed. From this temperature up to about 175°C, the mass loss can be attributed to the desorption of a film of metallic Hg. The last step, from 175 to 240°C, can be ascribed to the removal of Hg from a thin dark film of RhHg2.

Water sorption thermodynamic properties applied to persimmon skin and pulp

Moisture equilibrium data of persimmon skin and pulp were determined using the static gravimetric method. Adsorption and desorption isotherms were obtained in the range of 20-70°C, to water activities (a w) from 0.02 to 0.85. The application of the GAB model to the experimental results, using direct nonlinear regression analysis, provided a good agreement between experimental and calculated values. The net isosteric heat of sorption was estimated from equilibrium sorption data, using the Clausius-Clapeyron equation. Isosteric heats of sorption were found to increase with increasing temperature and could be well adjusted by an exponential relationship. The enthalpy-entropy compensation theory was applied to sorption isotherms and plots of ΔH versus ΔS for skin and pulp provided the isokinetic temperatures, indicating an enthalpy controlled sorption process. © 2000 Elsevier Science B.V.

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.

Sorption isotherm, glass transitions and state diagram for freeze-dried plum skin and pulp

Differential scanning calorimetry (DSC) was used to determine phase transitions of freeze-dried plums. Samples at low and intermediate moisture contents, were conditioned by adsorption at various water activities (0.11≤a w≤0.90) at 25°C, whereas in the high moisture content region (a w>0.90) samples were obtained by direct water addition, with the resulting sorption isotherm being well described by the Guggenheim-Anderson-deBoer (GAB) model. Freeze-dried samples of separated plum skin and pulp were also analysed. At a w≤0.75, two glass transitions were visible, with the glass transition temperature (T g) decreasing with increasing a w due to the water plasticising effect. The first T g was attributed to the matrix formed by sugars and water. The second one, less visible and less plasticised by water, was probably due to macromolecules of the fruit pulp. The Gordon-Taylor model represented satisfactorily the matrix glass transition curve for a w≤0.90. In the higher moisture content range T g remained practically constant around T g′ (-57.5°C). Analysis of the glass transition curve and the sorption isotherm indicated that stability at a temperature of 25°C, would be attained by freeze dried plum at a water activity of 0.04, corresponding to a moisture content of 12.9% (dry basis). © 2006 SAGE Publications.

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.

Response surface methodology applied to the evaluation of the SO 2 sorption process in two Brazilian limestones

This paper proposes a response surface methodology to evaluate the influence of the particle size and temperature as variables and their interaction on the sulfation process using two Brazilian limestones, a calcite (ICB) and a dolomite (DP). Experiments were performed according to an experimental design [central composite rotatable design (CCRD)] carried out on a thermogravimetric balance and a nitrogen adsorption porosimeter. In the SO 2 sorption process, DP was shown to be more efficient than ICB. The best results for both limestones in relation to conversion and Brunauer-Emmett-Teller (BET) surface area were obtained under central point conditions (545 μm and 850 C for DP and 274 μm and 815 C for ICB). The optimal values for conversion were 52% for DP and 37% for ICB. For BET surface area, the optimal values were 35 m2 g-1 for DP and 45 m2 g-1 for ICB. A relationship between conversion and pore size distribution has been established. The experiments that showed higher conversions also exhibited more pores in the region between 20 and 150 Å and larger BET surface area, indicating that the amount of smaller pores may be an important factor in the reactivity of limestones. © 2013 American Chemical Society.

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.

Sorption and desorption of phosphate on biochar and biochar-soil mixtures

The term biochar refers to materials with diverse chemical, physical and physicochemical characteristics that have potential as a soil amendment. The purpose of this study was to investigate the P sorption/desorption properties of various slow biochars and one fast pyrolysis biochar and to determine how a fast pyrolysis biochar influences these properties in a degraded tropical soil. The fast pyrolysis biochar was a mixture of three separate biochars: sawdust, elephant grass and sugar cane leaves. Three other biochars were made by slow pyrolysis from three Amazonian tree species (Lacre, Ingá and Embaúba) at three temperatures of formation (400 °C, 500 °C, 600 °C). Inorganic P was added to develop sorption curves and then desorbed to develop desorption curves for all biochar situations. For the slow pyrolysis, the 600 oC biochar had a reduced capacity to sorb P (4-10 times less) relative to those biochars formed at 400 °C and 500 °C. Conversely, biochar from Ingá desorbed the most P. The fast pyrolysis biochar, when mixed with degraded tropical mineral soil, decreased the soil's P sorption capacity by 55% presumably because of the high soluble, inorganic P prevalent in this biochar (909 mg P/kg of biochar). Phosphorus desorption from the fast pyrolysis biochar/soil mixture not only exhibited a common desorption curve but also buffered the soil solution at a value of ca. 0.2 mg/L. This study shows the diversity in P chemistry that can be expected when biochar is a soil amendment and suggests the potential to develop biochars with properties to meet specific objectives. © 2013 British Society of Soil Science.