The Physiological, Enzymatic, and Genetic Characterization of Staphylococcus sp. Chromium (VI) Reductase Function

A strain of Staphylococcus isolated by Dr. Fekete at the Sandia National Laboratory toxic metal dumping site in Sandia, New Mexico. has been found to reduce toxic Cr(VI) to the less toxic Cr(IlI) state. We have ascertained the environmental parameters for optimal bacterial growth and Cr(VI) reduction. This knowledge may be employed in a comprehensive bioremediation scheme designed to accelerate natural reparation of that Sandia ecosystem. In addition we have investigated the genetic and enzymatic basis for this Cr(VI) reducing ability. This information may allow us to create more effective bioremediation schemes based on the comprehensive knowledge of enzyme and gene function. Preliminary investigations have been carried out toward this end which may serve as the basis for a more thorough investigation.

Application of mesoporous SBA-15 silica functionalized with 4-amino-2-mercaptopyrimidine for the adsorption of Cu(II), Zn(II), Cd(II), Ni(II), and Pb(II) from water

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

Synthesis of high-surface-area gamma-Al2O3 from aluminum scrap and its use for the adsorption of metals: Pb(II), Cd(II) and Zn(II)

Several types of alumina were synthesized from sodium aluminate (NaAlO2) by precipitation with sulfuric acid (H2SO4) and subsequently calcination at 500 degrees C to obtain gamma-Al2O3. The precursor aluminate was derived from aluminum scrap. The various gamma-Al2O3 synthesized were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), adsorption-desorption of N-2 (S-BET) and scanning electron microscopy (SEM). XRD revealed that distinct phases of Al2O3 were formed during thermal treatment. Moreover, it was observed that conditions of synthesis (pH, aging time and temperature) strongly affect the physicochemical properties of the alumina. A high-surface-area alumina (371 m(2) g(-1)) was synthesized under mild conditions, from inexpensive raw materials. These aluminas were tested for the adsorption of Cd(II), Zn(II) and Pb(II) from aqueous solution at toxic metal concentrations, and isotherms were determined. (C) 2012 Elsevier B.V. All rights reserved.

Molecular and functional characterization of the chemotactic genes in the PCBs-degrader Pseudomonas pseudoalcaligenes KF707

Although bacteria represent the simplest form of life on Earth, they have a great impact on all living beings. For example the degrader bacterium Pseudomonas pseudoalcaligenes KF707 is used in bioremediation procedures for the recovery of polluted sites. Indeed, KF707 strain is know for its ability to degrade biphenyl and polychlorinated biphenyls - to which is chemotactically attracted - and to tolerate the oxydative stress due to toxic metal oxyanions such as tellurite and selenite. Moreover, in bioremediation processes, target compounds can be easily accessible to KF707 through biofilm formation. All these considerations suggest that KF707 is such a unique microorganism and this Thesis work has been focused on determining the molecular nature of some of the peculiar physiological traits of this strain. The genome project provided a large set of informations: putative genes involved in the degradation of aromatic and toxic compounds and associated to stress response were identified. Notably, multiple chemotactic operons and cheA genes were also found. Deleted mutants in the cheA genes were constructed and their role in motility, chemotaxis and biofilm formation were assessed and compared to those previously attributed to a cheA1 gene in a KF707 mutant constructed by a mini-Tn5 transposon insertion and which was impaired in motility and biofilm development. The results of this present Thesis work, taken together, were interpreted to suggest that in Pseudomonas pseudoalcaligenes KF707 strain, multiple factors are involved in these networks and they might play different roles depending on the environmental conditions. The ability of KF707 strain to produce signal molecules possibly involved in cell-to-cell communication, was also investigated: lack of a lux-like QS system - which is conversely widely present in Gram negative bacteria – keeps open the question about the actual molecular nature of KF707 quorum sensing mechanism.

Characterization of legacy organic carbon in a culturally eutrophic lake : the role of the historic carbon deposition in the time course and extent of lake recovery

The time course of lake recovery after a reduction in external loading of nutrients is often controlled by conditions in the sediment. Remediation of eutrophication is hindered by the presence of legacy organic carbon deposits, that exert a demand on the terminal electron acceptors of the lake and contribute to problems such as internal nutrient recycling, absence of sediment macrofauna, and flux of toxic metal species into the water column. Being able to quantify the timing of a lake’s response requires determination of the magnitude and lability, i.e., the susceptibility to biodegradation, of the organic carbon within the legacy deposit. This characterization is problematic for organic carbon in sediments because of the presence of different fractions of carbon, which vary from highly labile to refractory. The lability of carbon under varied conditions was tested with a bioassay approach. It was found that the majority of the organic material found in the sediments is conditionally-labile, where mineralization potential is dependent on prevailing conditions. High labilities were noted under oxygenated conditions and a favorable temperature of 30 °C. Lability decreased when oxygen was removed, and was further reduced when the temperature was dropped to the hypolimnetic average of 8° C . These results indicate that reversible preservation mechanisms exist in the sediment, and are able to protect otherwise labile material from being mineralized under in situ conditions. The concept of an active sediment layer, a region in the sediments in which diagenetic reactions occur (with nothing occurring below it), was examined through three lines of evidence. Initially, porewater profiles of oxygen, nitrate, sulfate/total sulfide, ETSA (Electron Transport System Activity- the activity of oxygen, nitrate, iron/manganese, and sulfate), and methane were considered. It was found through examination of the porewater profiles that the edge of diagenesis occurred around 15-20 cm. Secondly, historical and contemporary TOC profiles were compared to find the point at which the profiles were coincident, indicating the depth at which no change has occurred over the (13 year) interval between core collections. This analysis suggested that no diagenesis has occurred in Onondaga Lake sediment below a depth of 15 cm. Finally, the time to 99% mineralization, the t99, was viewed by using a literature estimate of the kinetic rate constant for diagenesis. A t99 of 34 years, or approximately 30 cm of sediment depth, resulted for the slowly decaying carbon fraction. Based on these three lines of evidence , an active sediment layer of 15-20 cm is proposed for Onondaga Lake, corresponding to a time since deposition of 15-20 years. While a large legacy deposit of conditionally-labile organic material remains in the sediments of Onondaga Lake, it becomes clear that preservation, mechanisms that act to shield labile organic carbon from being degraded, protects this material from being mineralized and exerting a demand on the terminal electron acceptors of the lake. This has major implications for management of the lake, as it defines the time course of lake recovery following a reduction in nutrient loading.

Occupational beryllium exposure: Reconciling federal policies, regulations and contractor implementation guides to protect worker health

Beryllium is a widely distributed, highly toxic metal. When beryllium particulates enter the body, the body's defense mechanisms are engaged. When the body's defenses cannot easily remove the particulates, then a damage and repair cycle is initiated. This cycle produces chronic beryllium disease (CBD), a progressive, fibrotic respiratory involvement which eventually suffocates exposed individuals. ^ Beryllium disease is an occupational disease, and as such it can be prevented by limiting exposures. In the 1940s journalists reported beryllium deaths at Atomic Energy Commission (AEC) facilities, the Department of Energy's (DOE) predecessor organization. These reports energized public pressure for exposure limits, and in 1949 AEC implemented a 2 μg/m3 permissible exposure limit (PEL). ^ The limits appeared to stop acute disease. In contrast, CBD has a long latency period between exposure and diagnosable disease, between one and thirty years. The lack of immediate adverse health consequences masked the seriousness of chronic disease and pragmatically removed CBD from AEC/DOE's political concern. ^ Presently the PEL for beryllium at DOE sites remains at 2 μg/m 3. This limit does not prevent CBD. This conclusion has long been known, although denied until recently. In 1999 DOE acknowledged the limit's ineffectiveness in its federal regulation governing beryllium exposure, 10 CFR 850. ^ Despite this admission, the PEL has not been reduced. The beryllium manufacturer and AEC/DOE have a history of exerting efforts to maintain and protect the status quo. Primary amongst these efforts has been creation and promotion of disinformation within peer reviewed health literature which discusses beryllium, exposures, health effects and treatment, and targeting graduate school students so that their perspective is shaped early. ^ Once indoctrinated with incorrect information, professionals tend to overlook aerosol and respiratory mechanics, immunologic and carcinogenic factors. They then apply tools and perspectives derived from the beryllium manufacturer and DOE's propaganda. Conclusions drawn are incorrect. The result is: health research and associated policy is conducted with incorrect premises. Effective disease management practices are not implemented. ^ Public health protection requires recognition of the disinformation and its implications. When disinformation is identified, then effective health policies and practices can be developed and implemented. ^

Aluminum slurry coatings to replace cadmium for aeronautic applications

Cadmium has been widely used as a coating to provide protection against galvanic corrosion for steels and for its natural lubricity on threaded applications. However, it is a toxic metal and a known carcinogenic agent, which is plated from an aqueous bath containing cyanide salts. For these reasons, the use of cadmium has been banned in Europe for most industrial applications. However, the aerospace industry is still exempt due to the stringent technical and safety requirements associated with aeronautical applications, as an acceptable replacement is yet to be found. Al slurry coatings have been developed as an alternative to replace cadmium coatings. The coatings were deposited on AISI 4340 steel and have been characterized by optical and electron microscopy. Testing included salt fog corrosion exposure, fluid corrosion exposure (immersion), humidity resistance, coating-substrate and paint-coating adhesion, electric conductivity, galvanic corrosion, embrittlement and fatigue. The results indicated that Al slurry coatings are an excellent alternative for Cd replacement.

Intra-ring variability of Cr, As, Cd, and Pb in red oak revealed by secondary ion mass spectrometry: Implications for environmental biomonitoring

Reconstructing the history of ambient levels of metals by using tree-ring chemistry is controversial. This controversy can be resolved in part through the use of selective microanalysis of individual wood cells. Using a combination of instrumental neutron activation analysis and secondary ion mass spectrometry, we have observed systematic inhomogeneity in the abundance of toxic metals (Cr, As, Cd, and Pb) within annual growth rings of Quercus rubra (red oak) and have characterized individual xylem members responsible for introducing micrometer-scale gradients in toxic metal abundances. These gradients are useful for placing constraints on both the magnitude and the mechanism of heavy metal translocation within growing wood. It should now be possible to test, on a metal-by-metal basis, the suitability of using tree-ring chemistries for deciphering long-term records of many environmental metals.

Remoção de carbonatos para otimizar a biolixiviação de rejeito calcopirítico empregando consórcio de microrganismos

The bioleaching of chalcopyrite has not been applied on a commercial scale due to the low process efficiency, so this process has been extensively studied in recent years. The bioleaching of chalcopyrite tailings becomes even more difficult by the presence of higher amounts of impurities, among them are the carbonates. The presence of carbonates in the ore promotes the increase in pH of the solution and may inhibit the development of bioleaching. Therefore, this research aims to apply the acid treatment for optimization of bioleaching process, in order to recover the lost copper throughout the process besides reducing the content of this toxic metal in the tailings pond. The removal and recovery of toxic metals is very important in protecting the environment and human health. The bioleaching experiments were performed in two stages, the first made up using the pre-treated tailing with sulfuric acid in bioleaching, and the second was made using the tailing without treatment with sulfuric acid addition at the beginning of bioleaching. The acid treatment was carried out in bioreactors with three different volumes of H2SO4 96% and a control experiment. All bioleaching experiments were performed in triplicate over a control, without addition of inoculum. The results showed that acid treatment was effective in removal of carbonates and managed to promote a good performance in the bioleaching of chalcopyrite in both steps studied, it is demonstrated that circa 47% copper recovery can be achieved.

Remoção de carbonatos para otimizar a biolixiviação de rejeito calcopirítico empregando consórcio de microrganismos

The bioleaching of chalcopyrite has not been applied on a commercial scale due to the low process efficiency, so this process has been extensively studied in recent years. The bioleaching of chalcopyrite tailings becomes even more difficult by the presence of higher amounts of impurities, among them are the carbonates. The presence of carbonates in the ore promotes the increase in pH of the solution and may inhibit the development of bioleaching. Therefore, this research aims to apply the acid treatment for optimization of bioleaching process, in order to recover the lost copper throughout the process besides reducing the content of this toxic metal in the tailings pond. The removal and recovery of toxic metals is very important in protecting the environment and human health. The bioleaching experiments were performed in two stages, the first made up using the pre-treated tailing with sulfuric acid in bioleaching, and the second was made using the tailing without treatment with sulfuric acid addition at the beginning of bioleaching. The acid treatment was carried out in bioreactors with three different volumes of H2SO4 96% and a control experiment. All bioleaching experiments were performed in triplicate over a control, without addition of inoculum. The results showed that acid treatment was effective in removal of carbonates and managed to promote a good performance in the bioleaching of chalcopyrite in both steps studied, it is demonstrated that circa 47% copper recovery can be achieved.

Physico-chemical properties of sol-gel synthesized titanosilicates for the uptake of radionuclides from aqueous solutions

Harnessing the power of nuclear reactions has brought huge benefits in terms of nuclear energy, medicine and defence as well as risks including the management of nuclear wastes. One of the main issues for radioactive waste management is liquid radioactive waste (LRW). Different methods have been applied to remediate LRW, thereunder ion exchange and adsorption. Comparative studies have demonstrated that Na2Ti2O3SiO4·2H2O titanosilicate sorption materials are the most promising in terms of Cs+ and Sr2+ retention from LRW. Therefore these TiSi materials became the object of this study. The recently developed in Ukraine sol-gel method of synthesizing these materials was chosen among the other reported approaches since it allows obtaining the TiSi materials in the form of particles with size ≥ 4mm. utilizing inexpensive and bulk stable inorganic precursors and yielded the materials with desirable properties by alteration of the comparatively mild synthesis conditions. The main aim of this study was to investigate the physico-chemical properties of sol-gel synthesized titanosilicates for radionuclide uptake from aqueous solutions. The effect of synthesis conditions on the structural and sorption parameters of TiSi xerogels was planned to determine in order to obtain a highly efficient sorption material. The ability of the obtained TiSis to retain Cs+, Sr2+ and other potentially toxic metal cations from the synthetic and real aqueous solutions was intended to assess. To our expectations, abovementioned studies will illustrate the efficiency and profitability of the chosen synthesis approach, synthesis conditions and the obtained materials. X-ray diffraction, low temperature adsorption/desorption surface area analysis, X-ray photoelectron spectroscopy, infrared spectroscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy was used for xerogels characterization. The sorption capability of the synthesized TiSi gels was studied as a function of pH, adsorbent mass, initial concentration of target ion, contact time, temperature, composition and concentration of the background solution. It was found that the applied sol-gel approach yielded materials with a poorly crystalline sodium titanosilicate structure under relatively mild synthesis conditions. The temperature of HTT has the strongest influence on the structure of the materials and consequently was concluded to be the control factor for the preparation of gels with the desired properties. The obtained materials proved to be effective and selective for both Sr2+ and Cs+ decontamination from synthetic and real aqueous solutions like drinking, ground, sea and mine waters, blood plasma and liquid radioactive wastes.

Studies on the effect of toxic heavy metal mercury on the physiology and biochemistry of an estuarine crab Scylla serrata (Forskal)

This thesis Entitled studies on the effect of toxic heavy metal mercury on the physiology and biochemistry of an estuarine crab scylla serrata (Forskal). Evaluate the toxicity of three sub lethal concentrations of mercury, viz., 0.009 mg/l, 0.02 mg/1, and 0.04 mg/l on the mud crab, Scylla serrata through bioaccumulation, and depuration studies. To characterize the biochemical responses to the sub-lethal stress of mercury in chelate muscles, abdominal muscles, hepatopancreas and gills. To study the activity pattern of acid and alkaline phosphatases in mercury-exposed crabs. To evaluate the induced changes in these tissues through histopathological studies,The Cochin backwaters is one of the most productive and biologically active backwater systems, and is the habitat of varieties of fishes, mollusks, and crustaceans, though this water body also receives tons of effluents from factories located on the banks of the river, Periyar.To study the activity levels of acid and alkaline phosphatases in crabs, at three time periods, exposed to three sub lethal concentration of mercury,

Peroxides in ordered nanoporous silicas: clean alternatives to transition metal oxidants for the removal of toxic gases

Ordered nano-structured MCM-48 silica containing sodium peroxydisulfate is a novel, highly effective material for the decomposition of HCN under ambient conditions.