Determination of Cd(II) and Cd-metallothioneins in biological extracts using baker's yeast and inductively coupled plasma optical emission spectrometry

The use of Saccharomyces cerevisiae as a sorbent material to separate Cd(II) and Cd-metallothionein complex (Cd-MT) has been explored. Solid-liquid phase extractions were carried out in batch mode and the main parameters of the process (pH, temperature, time of incubation, amount of biomass and analyte) were evaluated. Under optimized conditions, the yeast quantitatively retain (94 +/- 5%) the Cd(II) while 97 +/- 2% of the Cd-MT remain in the supernatant. on base of the findings of this study, a simple method is proposed to determine Cd(II) and Cd-MT in cytosols extracted from mouse kidney and crab hepatopancreas. Inductively coupled plasma optical emission spectrometry was used to quantify the analytes in solid and liquid phase. Determination of Cd in the solid phase was carried out by introducing a slurry of the yeast (0.0625 g/10 mL) directly to the inductively coupled plasma optical emission spectrometer. Mixed standards solutions, which also have been submitted to the extraction procedure, were used to quantify the analytes in the samples. Thus, matrix effects due to nebulization of the slurry were overcame. Limits of detection (3 sigma) for Cd(II) and Cd-MT were 1.5 and 1.2 mu g L-1, respectively. Relative standard deviations of signals were 4.2% for measurements in the slurry of solid phase and 2.1% for measurements in the liquid phase. Recoveries of the analytes in cytosol samples were between 76 and 114%. The concentrations of Cd(II) (2.4 +/- 0.5 mu g L-1) and Cd-MT (3.0 +/- 0.5 mu g L-1) found by using the proposed approach were close to those found by tangential-flow ultrafiltration technique (2.6 +/- 0.7 mu g L-1 for Cd(II) and 3.7 +/- 1.7 mu g L-1 for Cd-MT).

Consolidation and break-up of the South American platform in southeastern Brazil: Tectonothermal and denudation histories

The different tectonic stages that occurred at the end of the Proterozoic and during the Phanerozoic have an important bearing on the tectonothermal history of the South American Platform and its consolidation. Geochronological data (U/Pb monazite, Ar-40/Ar-39 whole rock) and apatite fission-track analysis, from Precambrian rocks of the southeastern Brazilian coastline, permit the modeling of a long-term thermal history of the crust and constrain variable denudation rates.Using these data, a temperature-time diagram reflects a period of accelerated exhumation during the end of the Brasiliano Orogeny, followed by long stability and reactivation of the platform during the Rifting Phase of the South Atlantic Ocean.U/Pb zircon and monazite (blocking temperature of ca. 650degreesC) data from a series of igneous bodies suggest that a tangential and transpressional tectonic regime occurred between 625 and 610 Ma. During the following escape tectonics, between 610 and 590 Ma the exhumation process indicates cooling rates of ca. 12degreesC/Ma. Ar-40/Ar-39 biotite ages between 540 and 510 Ma (ca. 300degreesC) and a corrected fission-track age on apatites (100degreesC) of 480 Ma indicate an exhumation event related to block tectonics with huge vertical displacement along shear zones.A long stabilization phase, with low exhumation, and cooling rate around 0.25degreesC/Ma was recorded from the Cambro/Ordovician to the Mesozoic. At 65 Ma an acceleration of the exhumation through denudation and reworking of the South American surface with cooling rate of 1.5degreesC/Ma is observed.The uplift of the Mantiqueira and Serra do Mar mountain ranges along the southeast Brazilian coastline works as a climatic barrier provoking lateral erosional processes causing long-term scarp retreat, combined with intense, but progressive denudation towards the continent. A denudation of 2.5 to 4 km was calculated for such processes. This lateral retreat of escarpments and flexural response can provide important insights regarding marginal isostatic uplift and the evolution of offshore sedimentary basins of southeast Brazil.

Aquatic humus from an unpolluted Brazilian dark-brown stream: general characterization and size fractionation of bound heavy metals

The main pool of dissolved organic carbon in tropical aquatic environments, notably in dark-coloured streams, is concentrated in humic substances (HS). Aquatic HS are large organic molecules formed by micro-biotic degradation of biopolymers and polymerization of smaller organic molecules. From an environmental point of view, the study of metal-humic interactions is often aimed at predicting the effect of aquatic HS on the bioavailability of heavy metal ions in the environment. In the present work the aquatic humic substances (HS) isolated from a dark-brown stream (located in an environmental protection area near Cubatao city in São Paulo-State, Brazil) by means of the collector XAD-8 were investigated. FTIR studies showed that the carboxylic carbons are probably the most important binding sites for Hg(II) ions within humic molecules. C-13-NMR and H-1-NMR studies of aquatic HS showed the presence of constituents with a high degree of aromaticity (40% of carbons) and small substitution. A special five-stage tangential-flow ultrafiltration device (UF) was used for size fractionation of the aquatic HS under study and for their metal species in the molecular size range 1-100 kDa (six fractions). The fractionation patterns showed that metal traces remaining in aquatic HS after their XAD-8 isolation have different distributions. Generally, the major percentage of traces of Mn, Cd and Ni (determined by ICP-AES) was preferably complexed by molecules with relatively high molecular size. Cu was bound by fractions with low molecular size and Co showed no preferential binding site in the various humic fractions. Moreover, the species formed between aquatic HS and Hg(II), prepared by spiking (determined by CVAAS), appeared to be concentrated in the relatively high molecular size fraction F-1 (> 100 kDa).

Reduction of mercury(II) by tropical river humic substances (Rio Negro) - Part II. Influence of structural features (molecular size, aromaticity, phenolic groups, organically bound sulfur)

The influence of structural features of tropical river humic substances (HS) on their capability to reduce mercury(II) in aqueous solutions was studied. The HS investigated were conventionally isolated from Rio Negro water-Amazonas State/Brazil by means of the collector XAD 8. In addition, the isolated HS were on-line fractionated by tangential-flow multistage ultrafiltration (nominal molecular-weight cut-offs: 100, 50, 30, 10, 5 kDa) and characterized by potentiometry and UV/VIS spectroscopy. The reduction of Hg(II) ions to elemental Hg by size-fractions of Rio Negro HS was assessed by cold-vapor AAS (CVAAS). UV/VIS spectrometry revealed that the fractions of high molecular-size (F-1 > 100 kDa and F-2: 50-100 kDa) have a higher aromaticity compared to the fractions of small molecular-size (F-5: 5-10 kDa, F-6: < 5 kDa). In contrast, the potentiometric study showed different concentration of functional groups in the studied HS fractions. The reduction of Hg(II) by aquatic HS fractions at pH 5 proceeded in two steps (I, II) of slow first order kinetics (t(1/2) of I: 160 min, t(1/2) of II: 300 min) weakly influenced by the molecular-size, in contrast to the differing degree of Hg(II) reduction (F-5 > F-2 > > F-1 > F-3 > F-4 > > F-6). Accordingly, Hg(II) ions were preferably reduced by HS molecules having a relatively high ratio of phenolic/carboxylic groups and a small concentration of sulfur. From these results a complex 'competition' between reduction and complexation of mercury(II) by aquatic HS occurring in tropical rivers such as the Rio Negro can be suggested. (C) 2003 Elsevier B.V. All rights reserved.

Influence of membrane-solution interface on the selectivity of SnO2 ultrafiltration membranes

SnO2 supported membranes, presenting 3.0 nm average pore size, have been produced by sol casting on alumina tubular substrate using aqueous colloidal suspensions prepared by sol-gel route. The selectivity and flux throughout SnO2 membrane were analyzed by permeation experiments, using a laboratory tangential filtration pilot equipped with a monotubular membrane. To evaluate the effect of the surface charge at the membrane-solution interface, aqueous salt solutions (NaCl, Na2SO4, CaCl, and CaSO4) of different ionic strength have been filtered and the results correlated with the values of zeta potential measured at several pH. The results show that the retention coefficient is dependent on the electrolyte present in aqueous solution decreasing as: (dication, monoanion) > (monocation, monoanion) approximate to (monocation, dianion) > (dication, dianion). The surface charge and the cation adsorption capacity play a determinant role in these selectivity sequences. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Determination of labile inorganic and organic species of Al and Cu in river waters using the diffusive gradients in thin films technique

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

Dobras em bainha macroscopicas relacionadas ao cisalhamento ductil de baixo angulo da nappe Araxa-Canastra no sudoeste de Minas Gerais

In the Proterozoic fold-thrust belt of Southwestern Minas Gerais, sheath folds belonging to Araxa-Canastra Group were mapped. These structures are explained by a tangential shear related to nappe transport, which acted together with an additional transcurrent shear, driven by a lateral ramp. An interesting feature recognized in these sheath folds is the striking obliquity between the hinge line of the macro structure and the hinge lines of the parasitic folds in the sheath fold closure. -English summary

Tectonic setting and U/Pb zircon dating of the plutonic Socorro Complex in the Transpressive Rio Paraíba do Sul Shear Belt, SE Brazil

The Precambrian Rio Paraíba do Sul Shear Belt comprises a 200-km-wide anastomosing network of NE-SW trending ductile shear zones extending over 1000 km of the southeastern coast of Brazil. Granulitic, gneissic-migmatitic, and granitoid terrains as well as low- to medium-grade metavolcanosedimentary sequences are included within it. These rocks were affected by strong contractional, tangential tectonics, due to west-northwestward oblique convergence of continental blocks. Subsequent transpressional tectonics accomodated large dextral, orogen-parallel movements and shortening. The plutonic Socorro Complex is one of many deformed granites with a foliation subparallel to that of the shear belt and exposes crosscutting relationships between its tectonic, magmatic, and metamorphic structures. These relationships point to a continuous magmatic evolution related to regional thrusts and strike slip, ductile shear zones. The tectonic and magmatic structural features of the Serra do Lopo Granite provide a model of emplacement by sheeting along shear zones during coeval strike-slip and cross shortening of country rocks. Geochronological data indicate that the main igneous activity of Socorro Complex spanned at least 55 million years, from the late stage of the northwestward ductile thrusting (650 Ma), through right-lateral strike slip (595 Ma) deformation. The country rocks yield discordant age data, which reflect a strong imprint of the Transamazonian tectono-metamorphic event (1.9 to 2.0 Ma). We propose a model for the origin of calcalkaline granites of the Ribeira Belt by partial melting of the lower crust with small contributions of the lithospheric mantle during transpressional thickening of plate margins, which were bounded by deep shear zones. The transpressional regime also seems to have focused granite migration from deeper into higher crustal levels along these shear zones.

Análise do comportamento de rebolos convencionais na retificação de aços frágeis e dúcteis

The aim of this work war to study the behavior of the plan tangential grinding process with conventional grinding wheels, under several machining conditions and a selected dressing condition. The analysis of the grinding performance was done regarding the cutting surface wear behavior of the grinding wheel for brittle and ductile steels workpieces. The grinding input parameters, which were, cutting speed, workpiece speed and cutting feed, were chosen based on the grinding machine characteristics. The results discussion emphasized the wear mechanism of the grinding wheel cutting surface and the cutting phenomenology of the grinding process.

Transpressional tectonics and strain partitioning during oblique collision between three plates in the Precambrian of southeast Brazil

This paper is part of the special publication Continental transpressional and transtensional tectonics (eds R.E. Holdsworth, R.A. Strachan and J.F. Dewey). Two orogenic belts have been recognized in south- east Brazil, which are interpreted to have been formed as a product of diachronous collisions between three continental plates. Wide crustal-scale shear belts have developed both between and inboard of the collided and amalgamated plate borders. These shear belts record frontal, oblique or lateral displacements during oblique plate convergence and A-type subduction. The overall structural style of each belt depends on the angle subtended between the plate boundary and the convergence vector. The E-W branch between the Sao Paulo and Brasilia plates the Campo do Meio strike-slip shear belt, has undergone dominantly sinistral wrench dominated transpression along a set of folds and shear zones dipping southwards. The NE-SW branch between the Sao Paulo and Vitoria plates, the Paraiba do Sul strike-slip shear belt, has undergone a partitioned dextral transpression, whereas the north-south branch between the Brasilia and Vitoria plates is essentially a frontal thrust system with only a weak component of dextral strike-slip. These complex structural patterns, formed at deep to mid-crustal levels, reflect temporal and spatial partitioning at all scales between flattening and non- coaxial deformation, and down-dip and strike-slip shearing, in tangential as well as in transcurrent structural domains. Additionally, this area demonstrates that regional flower structures, lateral extrusion and other secondary deformations across the yz sections of transpressional belts are important in accommodating shortening in obliquely convergent orogens.

The behaviour of resin-bond diamond wheels in the grinding of advanced ceramics

Results are reported of the behaviour of the plane tangential grinding process using diamond grinding wheels. Grinding performance is analysed in terms of the wear behaviour of the wheel in the grinding of ceramic. Discussion of the results concentrates on the wear mechanism of the diamond wheel and the process of material removal.

Advanced ceramics: Evaluation of the mechanism of stock removal and ground surface quality

The aim of this work is to evaluate the mechanism of stock removal and the ground surface quality of advanced ceramics grounded by a plane tangential grinding process with diamond grinding wheels. The analysis of the grinding performance was done regarding the cutting surface wear behavior of the grinding wheel for ceramic workpieces. The discussion about the results emphasized the wear mechanism of the grinding wheel cutting surface and the cutting phenomenology of the grinding process. The grounded surface was evaluated using Scanning Electron Microscopy (SEM). © 1999 Society of Automotive Engineers, Inc.

Transient flow of the oil-refrigerant mixture through the radial clearance in rolling piston compressors

Unsteady flow of oil and refrigerant gas through radial clearance in rolling piston compressors has been modeled as a heterogeneous mixture, where the properties are determined from the species conservation transport equation coupled with momentum and energy equations. Time variations of pressure, tangential velocity of the rolling piston and radial clearance due to pump setting have been included in the mixture flow model. Those variables have been obtained by modeling the compression process, rolling piston dynamics and by using geometric characteristics of the pump, respectively. An important conclusion concerning this work is the large variation of refrigerant concentration in the oil-filled radial clearance during the compression cycle. That is particularly true for large values of mass flow rates, and for those cases the flow mixture cannot be considered as having uniform concentration. In presence of low mass flow rates homogeneous flow prevail and the mixture tend to have a uniform concentration. In general, it was observed that for calculating the refrigerant mass flow rate using the difference in refrigerant concentration between compression and suction chambers, a time average value for the gas concentration should be used at the clearance inlet.

Advanced ceramics: Evaluation of the mechanism of stock removal and ground surface quality

The aim of this work is to evaluate the mechanism of stock removal and the ground surface quality of advanced ceramics machined by a surface grinding process using diamond grinding wheels. The analysis of the grinding performance was done regarding the cutting surface wear behavior of the grinding wheel for ceramic workpieces. The ground surface was evaluated using Scanning Electron Microscopy (SEM). As a result it can be said that the mechanism of material removal in the grinding of ceramic is largely one of brittle fracture. The increase of the hmax can reduce the tangential force required by the process. Although, it results in an increase in the surface damage, reducing the mechanical properties of the ground component.

Estudo comparativo do desempenho de rebolos com grãos superabrasivos e convencionais

Grinding is a precision machining process which is widely used in the manufacture of components requiring fine tolerances and smooth surfaces. There are several imput parameters (cutting conditions, cutting fluid and grinding wheel type used, dressing conditions etc.) which can affect the process variables (tangential and normal cutting forces, roughness, grinding temperatures, G ratio, etc.) leading to differences in the roughness, in the surface integrity and in the mechanical strength of the ground component. Consequently, the imput parameters must be controlled in order to insure the workpiece final quality. This paper presents a comparative evaluation of the performance of two types of grinding wheels [a conventional (Al2O3) and a superabrasive (CBN)] when grinding a VC131 steel, by the analysis of specific process variables when varying the cutting conditions. Highest values of G ratio and lowest workpiece roughness was observed when using CBN grinding wheels. This confirms the global trend of replacement of alumina grinding wheels by CBN, when grinding DTG (difficult to grind) materials.