Reduction of mercury(II) by tropical river humic substances (Rio Negro) - A possible process of the mercury cycle in Brazil

The evolution of elemental Hg from its environmental compounds has already been supposed to be an important process within the global mercury cycle. The present study characterizes the abiotic reduction of Hg(II) ions by typical river humic substances (HS) conventionally pre-isolated by the adsorbent XAD 8 from the Rio Negro near Manaus, Brazil. For the investigation of this reduction process a special reaction and Hg(0) trapping unit combined with cold-vapor atomic absorption spectrometry (CVAAS) was developed. Preconcentration of traces of mercury(II), if required, was obtained by a home-made FIA system using microcolumns filled with the Hg(II)-selective collector CheliteS(R) (Serva Company). The effect of environmentally relevant parameters such as the pH value, the Hg(II)/HS ratio and the HS concentration on the I-IE;(II) reduction process was studied as a function of the time. The Hg(0) production was highest at pH 8.0 and in the case of decreasing HS amounts (0.5 mg) when about 65% of initially 1.0 mug Hg(H) was reduced within 50 h. Moreover, the reduction efficiency of HS towards HE;(II) strongly depended on the HS concentration but hardly on the Hg(II)/HS ratio. The reduction kinetics followed a relatively slow two-step first-order mechanism with formal rate constants of about 0.1 and 0.02 h(-1), respectively. Based on these findings the possible relevance of the abiotic evolution of mercury in humic-rich aquatic environments is considered. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Molecular characterization of Acidithiobacillus ferrooxidans and A-thiooxidans strains isolated from mine wastes in Brazil

Nineteen strains of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans, including 12 strains isolated from coal, copper, gold and uranium mines in Brazil, strains isolated from similar sources in other countries and the type strains of the two species were characterized together with the type strain of A. caldus by using a combination of molecular systematic methods, namely ribotyping, BOX- and ERIC-PCR and DNA-DNA hybridization assays. Data derived from the molecular fingerprinting analyses showed that the tested strains encompassed a high degree of genetic variability. Two of the Brazilian A. ferrooxidans organisms (strains SSP and PCE) isolated from acid coal mine waste and uranium mine effluent, respectively, and A. thiooxidans strain DAMS, isolated from uranium mine effluent, were the most genetically divergent organisms. The DNA-DNA hybridization data did not support the allocation of Acidithiobacillus strain SSP to the A. ferrooxidans genomic species, as it shared only just over 40% DNA relatedness with the type strain of the species. Acidithiobacillus strain SSP was not clearly related to A. ferrooxidans in the 16S rDNA tree.

Solid-state reactions of mercury with pure noble metals - Part 2. Mercury-iridium system

Thermogravimetry, cyclic voltammetry and other analytical techniques were used to study the reactions of mercury with pure iridium. The results allowed to suggest when subjected to heat or anodic stripping voltammetry an electrodeposited mercury film reacts with Ir substrate and at least three mass loss steps and three peaks appear in the mercury desorption process. The first two were attributed to Hg(0) species removal like a mercury bulk and a mercury monolayer. The last can be ascribed to the mercury removal from a solid solution with iridium.

A Preliminary and Qualitative Metallomics Study of Mercury in the Muscle of Fish from Amazonas, Brazil

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

Simultaneous solidification of two catalyst wastes and their effect on the early stages of cement hydration

Two catalyst wastes (RNi and RAI) from polyol production were considered as hazardous, due to their respective high concentration of nickel and aluminum contents. This article presents the study, done to avoid environmental impacts, of the simultaneous solidification/stabilization of both catalyst wastes with type II Portland cement (CP) by non-conventional differential thermal analysis (NCDTA). This technique allows one to monitor the initial stages of cement hydration to evaluate the accelerating and/or retarding effects on the process due to the presence of the wastes and to identify the steps where the changes occur. Pastes with water/cement ratio equal to 0.5 were prepared, into which different amounts of each waste were added. NCDTA has the same basic principle of Differential Thermal Analysis (DTA), but differs in the fact that there is no external heating or cooling system as in the case of DTA. The thermal effects of the cement paste hydration with and without waste presence were evaluated from the energy released during the process in real time by acquiring the temperature data of the sample and reference using thermistors with 0.03 A degrees C resolution, coupled to an analog-digital interface. In the early stages of cement hydration retarding and accelerating effects occur, respectively due to RNi and RAl presence, with significant thermal effects. During the simultaneous use of the two waste catalysts for their stabilization process by solidification in cement, there is a synergic resulting effect, which allows better hydration operating conditions than when each waste is solidified separately. Thermogravimetric (TG) and derivative thermogravimetric analysis (DTG) of 4 and 24 h pastes allow a quantitative information about the main cement hydrated phases and confirm the same accelerating or retarding effects due to the presence of wastes indicated from respective NCDTA curves.

Methyl(2-mercapto-4-methylpyrimidinato)mercury(II): A methylmercury(II) derivative with an unusual metal-metal interaction

4-Methylpyrimidine-2-thione reacts with methylmercury hydroxide to give the thiolate derivative HgMe(SC4H2N2Me-2), the X-ray structure of which reveals pairs of molecules with a mercury-mercury distance of 3.10 Å.

Mercury(II) and thallium(III) organometallic derivatives of 2-Mercaptobenzoxazole

Some derivatives of 2-mercaptobenzoxazole (HL) of the type MRnL [M = Hg or Tl, R = Me or Ph and n = 1 (Hg) or 2 (Tl)] have been prepared. The structure of HgMeL has been determined by an X-ray diffraction study; in the crystal there are two independent planar molecules in each asymmetric unit, with the ligand in its thiolic form and an almost linear CHgS linkage. Weak intramolecular and intermolecular secondary interactions complement the mercurysulphur bond. The spectroscopic (IR, Raman, mass, 13C-NMR), conductimetric, and dipolar properties of this and the other compounds are discussed. © 1991.

Contribution to the study of the reaction of mercury with platinum and a platinum-iridium alloy

Thermogravimetry (TG) and other analysis techniques have been used to study the reaction of mercury with Pt and a PtIr alloy. The results suggested that, when heated, the electrodeposited Hg film reacts with Pt or with PtIr to form products of different stabilities, indicated by at least three weight loss steps. In the first step, between room temperature and 170°C, only the bulk Hg is removed. From this temperature to about 280°C the mass loss can be attributed to the desorption of a monolayer of mecury. The last step, from 280 to ≈600°C, can be ascribed to the removal of Hg from a solid solution with Pt and PtIr alloy. © 1995.

Interaction of mercury(II) with humic substances from the Rio Negro (Amazonas State, Brazil) by means of an ion exchange procedure

The aquatic humic substances (HS) investigated in this study with respect to their binding capability towards mercury(II) were isolated from the river Rio Negro, Amazonas State - Brazil, by means of the adsorbent XAD 8. Labile/inert fractions of inorganic Hg(II) complexes formed with these HS were characterized using an ion-exchange batch and column technique, respectively, based on Chelite S. This collector exhibits high Hg(II) distribution coefficients, Kd, up to the order of 104 decreasing, however, in the case of small Hg(II)/HS ratios (< 0.1 μg Hg(II) / mg HS). The influence of different complexation parameters (ratio of Hg(II)/HS, pH, contact time, complexing time) relevant for Hg(II) binding in aquatic environments was assessed. The Hg(II) lability in dissolved HS is mainly influenced by the mass ratio of Hg(II)/HS and the ageing of Hg(II)-HS species formed. This is particularly obvious in the case of low Hg(II) loading of HS where slow transformation processes of freshly formed Hg(II)-HS species significantly decrease their lability, leading to incomplete recoveries (< 20%) of the total Hg(II) bound to HS.

Re-evaluation of antibiotic and mercury resistance in Escherichia coli populations isolated in 1978 from Amazonian rubber tree tappers and Indians

A study was carried out to assess the stability of antimicrobial susceptibility of wild isolates upon long-term storage using fifty-three Escherichia coli strains isolated in 1978 from feces of healthy children from the Amazon region in Brazil, exposed to low levels of antimicrobial agents, and examined for resistance to mercury and four antibiotics. All of the strains were kept in Lignieres medium at room temperature and were transferred to fresh media four times during this period. Thirty-five out of the 53 strains analyzed in 1978 were viable. Upon recovery, antibiotic and mercury resistance was estimated. All of the 35 strains maintained their original phenotype in a stable fashion, except for one multiresistant strain which became susceptible to kanamycin. Fifty-four percent of the strains exhibited a resistance phenotype, among which 47% had conjugative plasmids.

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.

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.

Maturity degree of composts from municipal solid wastes evaluated by differential scanning calorimetry

Differential scanning calorimetry (DSC) in association with chemical analysis was applied to assess the maturity reached by the organic fraction of Municipal Solid Wastes (MSW) subjected to composting processes with manual and fixed aeration and sampled at different composting times. Thermograms showed that the difference in the treatments, i.e., the manual aeration and the fixed aeration, had no relevant effect on the stabilization and maturation of OM in the substrates. Common thermal effects observed were: a low temperature endotherm assigned to dehydration and/or loss of peripheral polysaccharides chains; a medium temperature exotherm assigned to loss of peptidic structures, and a high temperature exotherm assigned to oxydation and polycondensation of aromatic nuclei of the molecule. Results obtained suggest that in the experimental conditions used, a shorter time of composting (about 30 d) appears adequate, in order to limit the extended mineralization of OM, whereas a prolonged composting time (up to 132 d) would produce a compost of poor quality with high ash content and low OM content.

Oil wastes as unconventional substrates for rhamnolipid biosurfactant production by Pseudomonas aeruginosa LBI

Oil wastes were evaluated as alternative low-cost substrates for the production of rhamnolipids by Pseudomonas aeruginosa LBI strain. Wastes obtained from soybean, cottonseed, babassu, palm, and corn oil refinery were tested. The soybean soapstock waste was the best substrate, generating 11.7 g/L of rhamnolipids with a surface tension of 26.9 mN/m, a critical micelle concentration of 51.5 mg/L, and a production yield of 75%. The monorhamnolipid RhaC10C10 predominates when P. aeruginosa LBI was cultivated on hydrophobic substrates, whereas hydrophilic carbon sources form the dirhamnolipid Rha2C10C10 predominantly. © 2005 American Chemical Society and American Institute of Chemical Engineers.

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.