Measurements of labile Cd, Cu, Ni, Pb, and Zn levels at a northeastern Brazilian coastal area under the influence of oil production with diffusive gradients in thin films technique (DGT)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Engineered nanoparticles and organic matter: a review of the state-of-the-art

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

A critical comparison of different approaches to sediment-quality assessments in the Santos estuarine system in Brazil

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Corrosion resistance of Ni-Cr alloys in different mouthwashes

Several alloys have been used for prosthodontics restorations in the last years. These alloys have a number of metals that include gold, palladium, silver, nickel, cobalt, chromium and titanium and they are used in oral cavity undergo several corrosion. Corrosion can lead to poor esthetics, compromise of physical properties, or increased biological irritation. The objective of this study was evaluated corrosion resistance of two alloys Ni-Cr and Ni-Cr-Ti in three types of mouthwashes with different active ingredients: 0.5g/l cetylpyridinium chloride + 0.05% sodium fluoride, 0.05% sodium fluoride + 0.03% triclosan (with fluor) and 0.12% chlorohexidine digluconate. The potentiodynamic curves were performed by means of an EG&G PAR 283 potentiostat/galvanostat. The counter electrode was a platinum wire and reference electrode was an Ag/AgCl, KCl saturated. Before each experiment, working electrodes were mechanically polished with 600 and 1200 grade papers, rinsed with distilled water and dried in air. All experiments were carried out at 37.0oC in conventional three-compartment double wall glass cell containing mouthwashes. The microstructures of two alloys were observed in optical microscopy. Analysis of curves showed that Ni-Cr alloy was less reactive in the presence of 0.12% chlorohexidine digluconate while Ni-Cr-Ti alloy was more sensitive for others two types of mouthwashes (0.5g/l cetylpyridinium chloride + 0.05% sodium fluoride  and 0.05% sodium fluoride + 0.03% triclosan). This occurred probably due presence of titanium in this alloy. Microstructural analysis reveals the presence of dendritic and eutectic microstructures for NiCr and Ni-Cr-Ti, respectively.

Nutrients and Nonessential Elements in Soil after 11 Years of Wastewater Irrigation

Irrigation of citrus (Citrus aurantium L. x Citrus paradise Macf.) with urban reclaimed wastewater (RWW) can be economical and conserve fresh water. However, concerns remain regarding its deleterious effects on soil quality. We investigated the ionic speciation (ISP) of RWW and potential impacts of 11 yr of irrigation with RWW on soil quality, compared with well-water (WW) irrigation. Most of nutrients (similar to 53-99%) in RWW are free ionic species and readily available for plant uptake, such as: NH4+, NO3-, K+, Ca2+, Mg2+, SO42-, H3BO3, Cl-, Fe2+, Mn2+, Zn2+, Co2+, and Ni2+, whereas more than about 80% of Cu, Cr, Pb, and Al are complexed with CO3-, OH-, and/or organic matter. The RWW irrigation increased the availability and total concentrations of nutrients and nonessential elements, and soil salinity and sodicity by two to three times compared with WW-irrigated soils. Although RWW irrigation changed many soil parameters, no difference in citrus yield was observed. The risk of negative impacts from RWW irrigation on soil quality appears to be minimal because of: (i) adequate quality of RWW, according to USEPA limits; (ii) low concentrations of metals in soil after 11 yr of irrigation with RWW; and (iii) rapid leaching of salts in RWW-irrigated soil during the rainy season.

Phytostabilisation : use of wetland plants to treat mine tailings

Mine tailings can be rich in sulphide minerals and may form acid mine drainage (AMD) through reaction with atmospheric oxygen and water. AMD contains elevated levels of metals and arsenic (As) that could be harmful to animals and plants. An oxygen-consuming layer of organic material and plants on top of water-covered tailings would probably reduce oxygen penetration into the tailings and thus reduce the formation of AMD. However, wetland plants have the ability to release oxygen through the roots and could thereby increase the solubility of metals and As. These elements are released into the drainage water, taken up and accumulated in the plant roots, or translocated to the shoots. The aim was to examine the effects of plant establishment on water-covered mine tailings by answering following questions: A) Is plant establishment on water-covered mine tailings possible? B) What are the metal and As uptake and translocation properties of these plants? C) How do plants affect metal and As release from mine tailings, and which are the mechanisms involved? Carex rostrata Stokes, Eriophorum angustifolium Honck., E. scheuchzeri Hoppe, Phragmites australis (Cav.) Steud., Salix phylicifolia L. and S. borealis Fr. were used as test plants. Influences of plants on the release of As, Cd, Cu, Pb, Zn and in some cases Fe in the drainage water, and plant element uptake were studied in greenhouse experiments and in the field. The results obtained demonstrate that plant establishment are possible on water-covered unweathered mine tailings, and a suitable amendment was found to be sewage sludge. On acidic, weathered tailings, a pH increasing substance such as ashes should be added to improve plant establishment. The metal and As concentrations of the plant tissue were found to be generally higher in roots than in shoots. The uptake was dependent on the metal and As concentrations of the tailings and the release of organic acids from plant roots may have influenced the uptake. The metal release from tailings into the drainage water caused by E. angustifolium was found to depend greatly on the age and chemical properties of the tailings. However, no effects of E. angustifolium on As release was found. Water from old sulphide-, metal- and As-rich tailings with low buffering capacity were positively affected by E. angustifolium by causing higher pH and lower metal concentrations. In tailings with relatively low sulphide, metal and As contents combined with a low buffering capacity, plants had the opposite impact, i.e. a reduction in pH and elevated metal levels of the drainage water. The total release of metal and As from the tailings, i.e. drainage water together with the contents in shoots and roots, was found to be similar for C. rostrata, E. angustifolium and P. australis, except for Fe and As, where the release was highest for P. australis. The differences in metal and As release from mine tailings were mainly found to be due to the release of O2 from the roots, which changes the redox potential. Release of organic acids from the roots slightly decreased the pH, although did not have any particular influence on the release of metal and As. In conclusion, as shown here, phytostabilisation may be a successful technique for remediation of mine tailings with high element and sulphide levels, and low buffering capacity.

The release of zinc and lead from mine tailings

Mining and processing of metal ores are important causes of soil and groundwater contamination in many regions worldwide. Metal contaminations are a serious risk for the environment and human health. The assessment of metal contaminations in the soil is therefore an important task. A common approach to assess the environmental risk emanating from inorganic contaminations to soil and groundwater is the use of batch or column leaching tests. In this regard, the suitability of leaching tests is a controversial issue. In the first part of this work the applicability and comparability of common leaching tests in the scope of groundwater risk assessment of inorganic contamination is reviewed and critically discussed. Soil water sampling methods (the suction cup method and centrifugation) are addressed as an alternative to leaching tests. Reasons for limitations of the comparability of leaching test results are exposed and recommendations are given for the expedient application of leaching tests for groundwater risk assessment. Leaching tests are usually carried out in open contact with the atmosphere disregarding possible changes of redox conditions. This can affect the original metal speciation and distribution, particularly when anoxic samples are investigated. The influence of sample storage on leaching test results of sulfide bearing anoxic material from a former flotation dump is investigated in a long-term study. Since the oxidation of the sulfide-bearing samples leads to a significant overestimation of metal release, a feasible modification for the conduction of common leaching tests for anoxic material is proposed, where oxidation is prevented efficiently. A comparison of leaching test results to soil water analyzes have shown that the modified saturation soil extraction (SSE) is found to be the only of the tested leaching procedures, which can be recommended for the assessment of current soil water concentrations at anoxic sites if direct investigation of the soil water is impossible due to technical reasons. The vertical distribution and speciation of Zn and Pb in the flotation residues as well as metal concentrations in soil water and plants were investigated to evaluate the environmental risk arising from this site due to the release of metals. The variations in pH and inorganic C content show an acidification of the topsoil with pH values down to 5.5 in the soil and a soil water pH of 6 in 1 m depth. This is due to the oxidation of sulfides and depletion in carbonates. In the anoxic subsoil pH conditions are still neutral and soil water collected with suction cups is in equilibrium with carbonate minerals. Results from extended x-ray absorption fine-structure (EXAFS) spectroscopy confirm that Zn is mainly bound in sphalerite in the subsoil and weathering reactions lead to a redistribution of Zn in the topsoil. A loss of 35% Zn and S from the topsoil compared to the parent material with 10 g/kg Zn has been observed. 13% of total Zn in the topsoil can be regarded as mobile or easily mobilizable according to sequential chemical extractions (SCE). Zn concentrations of 10 mg/L were found in the soil water, where pH is acidic. Electron supply and the buffer capacity of the soil were identified as main factors controlling Zn mobility and release to the groundwater. Variable Pb concentrations up to 30 µg/L were observed in the soil water. In contrast to Zn, Pb is enriched in the mobile fraction of the oxidized topsoil by a factor of 2 compared to the subsoil with 2 g/kg Pb. 80% of the cation exchange capacity in the topsoil is occupied by Pb. Therefore, plant uptake and bioavailability are of major concern. If the site is not prevented from proceeding acidification in the future, a significant release of Zn, S, and Pb to the groundwater has to be expected. Results from this study show that the assessment of metal release especially from sulfide bearing anoxic material requires an extensive comprehension of leaching mechanisms on the one hand and on weathering processes, which influence the speciation and the mobility of metals, on the other hand. Processes, which may change redox and pH conditions in the future, have to be addressed to enable sound decisions for soil and groundwater protection and remediation.

High-Speed Laser Processing of Thin Single and Multi-Layer Films

Theoretical models are developed for the continuous-wave and pulsed laser incision and cut of thin single and multi-layer films. A one-dimensional steady-state model establishes the theoretical foundations of the problem by combining a power-balance integral with heat flow in the direction of laser motion. In this approach, classical modelling methods for laser processing are extended by introducing multi-layer optical absorption and thermal properties. The calculation domain is consequently divided in correspondence with the progressive removal of individual layers. A second, time-domain numerical model for the short-pulse laser ablation of metals accounts for changes in optical and thermal properties during a single laser pulse. With sufficient fluence, the target surface is heated towards its critical temperature and homogeneous boiling or "phase explosion" takes place. Improvements are seen over previous works with the more accurate calculation of optical absorption and shielding of the incident beam by the ablation products. A third, general time-domain numerical laser processing model combines ablation depth and energy absorption data from the short-pulse model with two-dimensional heat flow in an arbitrary multi-layer structure. Layer removal is the result of both progressive short-pulse ablation and classical vaporisation due to long-term heating of the sample. At low velocity, pulsed laser exposure of multi-layer films comprising aluminium-plastic and aluminium-paper are found to be characterised by short-pulse ablation of the metallic layer and vaporisation or degradation of the others due to thermal conduction from the former. At high velocity, all layers of the two films are ultimately removed by vaporisation or degradation as the average beam power is increased to achieve a complete cut. The transition velocity between the two characteristic removal types is shown to be a function of the pulse repetition rate. An experimental investigation validates the simulation results and provides new laser processing data for some typical packaging materials.

Bioactivity of extracts from extremophile microalgae Coccomyxa sp. on chloride cells in operculum tissue of Fundulus heteroclitus

Microalgae have been studied because of their great potential as a source of new compounds with important value for biotechnology and to understand their strategies of survival in extreme environments. The microalgae Coccomyxa sp., studied in this thesis, is a poly-extremophile witch was isolated from the acid mine drainage of S. Domingos mine. This environment is characterized by low pH (<3) and high concentration of metals, such as copper and iron. The main purpose of the present work was to evaluate the potential bioactivity in an ex-vivo animal model (Fundulus heteroclitus), and expression on selected genes, of cellular extracts obtained from cultures of Coccomyxa sp. at pH 7 without or with exposure to copper (0.6mM Cu²+). The extracts of Coccomyxa sp. cultured at pH 7 exposed to copper show a great potential to be used as epithelial NKCC inhibitors, revealing their potential use as diuretics, but did not show significant effects on gene expression. Coccomyxa sp. could be a good source of cellular extracts with a great potential to be used in pharmaceutical and biotechnology industries.

Dynamic properties of wood using the Split-Hopkinson Pressure Bar

Strain rate significantly affects the strength of a material. The Split-Hopkinson Pressure Bar (SHPB) was initially used to study the effects of high strain rate (~103 1/s) testing of metals. Later modifications to the original technique allowed for the study of brittle materials such as ceramics, concrete, and rock. While material properties of wood for static and creep strain rates are readily available, data on the dynamic properties of wood are sparse. Previous work using the SHPB technique with wood has been limited in scope to variability of only a few conditions and tests of the applicability of the SHPB theory on wood have not been performed. Tests were conducted using a large diameter (3.0 inch (75 mm)) SHPB. The strain rate and total strain applied to a specimen are dependent on the striker bar length and velocity at impact. Pulse shapers are used to further modify the strain rate and change the shape of the strain pulse. A series of tests were used to determine test conditions necessary to produce a strain rate, total strain, and pulse shape appropriate for testing wood specimens. Hard maple, consisting of sugar maple (Acer saccharum) and black maple (Acer nigrum), and eastern white pine (Pinus strobus) specimens were used to represent a dense hardwood and a low-density soft wood. Specimens were machined to diameters of 2.5 and 3.0 inches and an assortment of lengths were tested to determine the appropriate specimen dimensions. Longitudinal specimens of 1.5 inch length and radial and tangential specimens of 0.5 inch length were found to be most applicable to SHPB testing. Stress/strain curves were generated from the SHPB data and validated with 6061-T6 aluminum and wood specimens. Stress was indirectly corroborated with gaged aluminum specimens. Specimen strain was assessed with strain gages, digital image analysis, and measurement of residual strain to confirm the strain calculated from SHPB data. The SHPB was found to be a useful tool in accurately assessing the material properties of wood under high strain rates (70 to 340 1/s) and short load durations (70 to 150 μs to compressive failure).

AN ASSESSMENT OF BALLAST SOURCE'S QUALITY AND LOCATIONS WITH RESPECT TO MDOT'S UPGRADE OF THE WOLVERINE RAILROAD LINE FOR HIGH SPEED RAIL USEAGE

The Michigan Department of Transportation is evaluating upgrading their portion of the Wolverine Line between Chicago and Detroit to accommodate high speed rail. This will entail upgrading the track to allow trains to run at speeds in excess of 110 miles per hour (mph). An important component of this upgrade will be to assess the requirement for ballast material for high speed rail. In the event that the existing ballast materials do not meet specifications for higher speed train, additional ballast will be required. The purpose of this study, therefore, is to investigate the current MDOT railroad ballast quality specifications and compare them to both the national and international specifications for use on high speed rail lines. The study found that while MDOT has quality specifications for railroad ballast it does not have any for high speed rail. In addition, the American Railway Engineering and Maintenance-of-Way Association (AREMA), while also having specifications for railroad ballast, does not have specific specifications for high speed rail lines. The AREMA aggregate specifications for ballast include the following tests: (1) LA Abrasion, (2) Percent Moisture Absorption, (3) Flat and Elongated Particles, (4) Sulfate Soundness test. Internationally, some countries do require a highly standard for high speed rail such as the Los Angeles (LA) Abrasion test, which is uses a higher standard performance and the Micro Duval test, which is used to determine the maximum speed that a high speed can operate at. Since there are no existing MDOT ballast specification for high speed rail, it is assumed that aggregate ballast specifications for the Wolverine Line will use the higher international specifications. The Wolverine line, however, is located in southern Michigan is a region of sedimentary rocks which generally do not meet the existing MDOT ballast specifications. The investigation found that there were only 12 quarries in the Michigan that meet the MDOT specification. Of these 12 quarries, six were igneous or metamorphic rock quarries, while six were carbonate quarries. Of the six carbonate quarries four were locate in the Lower Peninsula and two in the Upper Peninsula. Two of the carbonate quarries were located in near proximity to the Wolverine Line, while the remaining quarries were at a significant haulage distance. In either case, the cost of haulage becomes an important consideration. In this regard, four of the quarries were located with lake terminals allowing water transportation to down state ports. The Upper Peninsula also has a significant amount of metal based mining in both igneous and metamorphic rock that generate significant amount of waste rock that could be used as a ballast material. The main drawback, however, is the distance to the Wolverine rail line. One potential source is the Cliffs Natural Resources that operates two large surface mines in the Marquette area with rail and water transportation to both Lake Superior and Lake Michigan. Both mines mine rock with a very high compressive strength far in excess of most ballast materials used in the United States and would make an excellent ballast materials. Discussions with Cliffs, however, indicated that due to environmental concerns that they would most likely not be interested in producing a ballast material. In the United States carbonate aggregates, while used for ballast, many times don't meet the ballast specifications in addition to the problem of particle degradation that can lead to fouling and cementation issues. Thus, many carbonate aggregate quarries in close proximity to railroads are not used. Since Michigan has a significant amount of carbonate quarries, the research also investigated using the dynamic properties of aggregate as a possible additional test for aggregate ballast quality. The dynamic strength of a material can be assessed using a split Hopkinson Pressure Bar (SHPB). The SHPB has been traditionally used to assess the dynamic properties of metal but over the past 20 years it is now being used to assess the dynamic properties of brittle materials such as ceramics and rock. In addition, the wear properties of metals have been related to their dynamic properties. Wear or breakdown of railroad ballast materials is one of the main problems with ballast material due to the dynamic loading generated by trains and which will be significantly higher for high speed rails. Previous research has indicated that the Port Inland quarry along Lake Michigan in the Southern Upper Peninsula has significant dynamic properties that might make it potentially useable as an aggregate for high speed rail. The dynamic strength testing conducted in this research indicate that the Port Inland limestone in fact has a dynamic strength close to igneous rocks and much higher than other carbonate rocks in the Great Lakes region. It is recommended that further research be conducted to investigate the Port Inland limestone as a high speed ballast material.

Comparison of Moe's Scale of Hardness with the Rockwell, Brinell, and Scaleroscope Scales.

Moe's scale of hardness as used in mineralogy is admittedly rather indefinite, and no exact hardnesses are measured. The Rockwell, Brinell, and Scaleroscope machines give quite definite results which may be easily reproduced at any time. The purpose of this investigation is to determine whether any definite relation exists between Moe's hardness and the hardness as measured by those machines commonly used for the determination of hardness of metals. If such a relation were found it would provide a more definite and accurate measure of the hardness of minerals.

Electrolytic Recovery of Copper and Zinc from Brass.

The reclamation of metals from scrap is becoming increasingly important in the metallurgical industry. Copper, because it does not corrode readily and is electronegative to most common metals, is peculiarly adapted to reclamation.

The Anodic Polishing of Copper in Solutions of Orthophosphoric Acid

The electrolytic cleaning of metals by anodic methods has been known for many years. It was recognized long ago that when the temperature and concentration of the electro­lyte were properly regulated, bright clean surfaces were obtained.

The Electrodeposition of Iron-Manganese Alloys

Although the alteration of properties resulting from the alloying of metals in their usual commercial forms has been extensively investigated, the field of electrodeposition of alloys is believed generally not to have received the atten­tion that it merits.