Chromium uptake and adsorption in marine phytoplankton - Implications for the marine chromium cycle

Using the radioisotope 51Cr, we investigated the controls of cellular Cr accumulation in an array of marine phytoplankton grown in environmentally relevant Cr concentrations (1–10 nM). Given the affinity of Cr(III) for amorphous Fe-hydroxide mineral surfaces, and the formation of these mineral phases on the outside of phytoplankton cells, extracellular Cr was monitored in a model diatom species (Thalassiosira weissflogii) as extracellular Fe concentrations varied. Extracellular Cr in T. weissflogii increased with increasing extracellular Fe, demonstrating that Cr may be removed from seawater via extracellular adsorption to phytoplankton. Short-term Cr(VI) and Cr(III) uptake experiments performed with T. weissflogii demonstrated that Cr(III) was the primary oxidation state adsorbing to cells and being internalized by them. Cellular Cr:C ratios (<0.5 μmol Cr mol C−1) of the eight phytoplankton species surveyed were significantly lower than previously reported Cr:C ratios in marine particles with a high biogenic component (10–300 μmol Cr mol C−1). This indicates that Cr(III) likely accumulates in marine particles due to uptake and/or adsorption. Mass balance calculations demonstrate that surface water Cr deficits can be explained via loss of Cr(III) to exported particles, thereby providing a mechanism to account for the nutrient depth profile for Cr in modern seawater. Given the large fractionation of stable Cr isotopes during Cr(VI) reduction, Cr(III) associated with exported organic carbon is likely enriched in lighter isotopes. Most sedimentary Cr isotope studies have thus far neglected internal fractionating processes in the marine Cr cycle, but our data indicate that loss of Cr to exported particles may be traced in the sedimentary d53Cr record.

Construcció d'un elèctrode d'ió selectiu amb membrana de PVC i marro de cafè com a ionòfor

Els elèctrodes són instruments d’anàlisi molt emprats per la seva gran eficiència, fàcil utilització, de resposta “in situ” i que ocupen poc espai. Tot i això, existeix una problemàtica actual dels elèctrodes, que és la no comercialització d’elèctrodes per tots els metalls que trobem dissolts en solucions d’interès analític. Per aquest motiu s’estudien possibles substàncies dins la formació de la membrana dels elèctrodes, ionòfors, que reaccionin amb espècies iòniques amb inexistència d’elèctrodes comercials. S’han dut a terme estudis amb residus vegetals com a ionòfors. Algunes dels biomaterials estudiats són la rapa i la iohimbe per a la detecció del Cr(VI) i l’Hg(II). Aquestes han sigut les motivacions que han dut a construir un elèctrode de ió selectiu amb membrana de PVC i marro de cafè com a ionòfor, i seguidament avaluar-ne la seva resposta

Adsorció de crom (VI) i crom (III) en solució amb closca de cranc

En l’eliminació del crom en suspensió de les aigües residuals de les indústries es realitzen dos processos: una precipitació en medi àcid on es redueix el crom (VI) a crom (III) en què s’elimina la major part del crom, i el següent tractament es fa per bescanvi iònic o per adsorció. Els adsorbents emprats actualment tenen un elevat cost i s’està estudiant nous adsorbents, com a substituts dels tradicionals, de baix cost. Dins d’aquest adsorbents de baix cost es troben els bioadsorbents, biomaterials amb gran capacitat d’adsorció. L’objectiu del projecte es va centrar en l’estudi de l’adsorció de crom trivalent i hexavalent en solucions aquoses utilitzant com a adsorbent el residu industrial de closca de cranc, provinent d’una indústria alimentària de barretes de cranc

Simultaneous determination of chromium(VI) and chromium(III) of bioavailable fraction in bottom mud by flow injection-atomic absorption spectroscopy

A rapid and sensitive method for separation and determination of Cr(VI) and Cr(III) in bottom mud of lake by flow injection on-line preconcentrtion system and GFAAS was developed. The available Cr(VI) and Cr(III) were extracted by HOAc or EDTA + NH4 NO3 and adsorbed simultaneously by an anion and a cation resin microclummn and then eluted simultaneously by 2 mol/L NH4 NO3 + 0.05 mol/L ascorbate and 2 mol/L H2SO4, respectively. The elution was performed for 50 s after adsorption for 2 min, and the efficiencies of elution were 85.4% - 94.8% and 96.7% - 106% for Cr(VI) and Cr(M) respectively. The detection limits of the method were 0.9 mu g/L and 2.7 mu g/L with relative standard deviations of 3.5% and 6.4% for the determination of Cr(VI) and Cr(III) in sample, respectively.

The investigation of photocatalysts and iron based materials in the oxidation and adsorption of toxic organic and chromium materials

The presences of heavy metals, organic contaminants and natural toxins in natural water bodies pose a serious threat to the environment and the health of living organisms. Therefore, there is a critical need to identify sustainable and environmentally friendly water treatment processes. In this dissertation, I focus on the fundamental studies of advanced oxidation processes and magnetic nano-materials as promising new technologies for water treatments. Advanced oxidation processes employ reactive oxygen species (ROS) which can lead to the mineralization of a number of pollutants and toxins. The rates of formation, steady-state concentrations, and kinetic parameters of hydroxyl radical and singlet oxygen produced by various TiO2 photocatalysts under UV or visible irradiations were measured using selective chemical probes. Hydroxyl radical is the dominant ROS, and its generation is dependent on experimental conditions. The optimal condition for generation of hydroxyl radical by of TiO2 coated glass microspheres is studied by response surface methodology, and the optimal conditions are applied for the degradation of dimethyl phthalate. Singlet oxygen (1O2) also plays an important role for advanced processes, so the degradation of microcystin-LR by rose bengal, an 1O2 sensitizer was studied. The measured bimolecular reaction rate constant between MC-LR and 1O2 is ∼ 106 M-1 s-1 based on competition kinetics with furfuryl alcohol. The typical adsorbent needs separation after the treatment, while magnetic iron oxides can be easily removed by a magnetic field. Maghemite and humic acid coated magnetite (HA-Fe3O4) were synthesized, characterized and applied for chromium(VI) removal. The adsorption of chromium(VI) by maghemite and HA-Fe3O4 follow a pseudo-second-order kinetic process. The adsorption of chromium(VI) by maghemite is accurately modeled using adsorption isotherms, and solution pH and presence of humic acid influence adsorption. Humic acid coated magnetite can adsorb and reduce chromium(VI) to non-toxic chromium (III), and the reaction is not highly dependent on solution pH. The functional groups associated with humic acid act as ligands lead to the Cr(III) complex via a coupled reduction-complexation mechanism. Extended X-ray absorption fine structure spectroscopy demonstrates the Cr(III) in the Cr-loaded HA-Fe 3O4 materials has six neighboring oxygen atoms in an octahedral geometry with average bond lengths of 1.98 Å.

Evaluation and measurement of chromium in sea water in order to remove it with mineral absorbent kaolin for desalination

Today, the use of heavy metals and chemical products industry expanded. The presence of significant amounts of, pollutants in industrial waste water can lead to serious risks to the environment and human health have heavy metals like chromium is one example of the future of salmon knock pond environment. Chromium is an essential element in the diet, but high doses of this element is very dangerous. Hence the use of chemical methods as a tool for the removal of metals from waste water pond be used. The aim of this study was to investigate the mineral kaolin adsorbents for the removal of chromium is water. Thus, the effect of different concentrations of absorbent micro amounts of chromium absorption and variable temperature, pH and electrolytes were studied. During the investigation of spectroscopic instrument (Varian) UV-VIS are used. Comparison of the absorption mechanism of chromium adsorption by the adsorbent with nano-absorbent kaolin kaolin was investigated. According to the studies done in the same conditions of temperature, pH and shaking rate of chromium absorption by nano kaolin kaolin is much more attractive. Therefore, its use as an adsorbent abundant, cheap, accessible, efficient and effective is proposed.

Low temperature solar cooling system with absorption chiller and desiccant wheel

Nowadays Solar Cooling systems are becoming popular to reduce the carbon footprint of air conditioning. The use of an absorption chiller connected to solar thermal panels is increasing, but little study has been carried out to assess the advantage of join together an absorption chiller and a desiccant wheel to remove the sensible heat and the latent heat in different ways than the current design adopted in the industry. In this work I assess the possibility of implement a desiccant wheel in a conventional solar cooling system and the possibility of recovering the heat rejected by the absorption chiller which is then used for the regeneration of the desiccant wheel. The implementation of a desiccant wheel and the recovery of the heat rejected could provide a significant energy saving when compared to traditional solar cooling system. The results assist in the practical development of a solar cooling system which simultaneously uses absorption and adsorption technology.

X-ray spectroscopic study of chromium, nickel, and molybdenum compounds

Chemical shifts in the K-absorption edges, AE, of a series of chromium, nickel, and molybdenum compounds have been investigated. The AE values in a given series vary in the same direction as the metal-core-level binding energies obtained from X-ray photoelectron spectroscopy. The AI3 values are related to the effective atomic charge of the metal by a parabolic relation. In the case of molybdenum compounds, the chemical shifts of the K, emission lines vary in the same manner as M.

Coordination Properties of Ionic Liquid-Mediated Chromium(II) and Copper(II) Chlorides and Their Complexes with Glucose

The structural and coordination properties of complexes formed upon the interaction of copper(II) and chromium(II) chlorides with diallrylimidazolium chloride (RMlm(+)Cl(-)) ionic liquids and glucose are studied by a combination of density functional theory (DFT) calculations and X-ray absorption spectroscopy (XAS). In the absence of the carbohydrate substrate, isolated mononuclear four-coordinated MeCl42- species (Me = Cu, Cr) dominate in the ionic liquid solution. The organic part of the ionic liquid does not directly interact with the metal centers. The interactions between the RMlm(+) cations and the anionic metal chloride complexes are limited to hydrogen bonding with the basic Cl- ligands and the overall electrostatic stabilization of the anionic metal complexes. Exchange of Cl ligands by a hydroxyl group of glucose is only favorable for CrCl42-. For Cu2+ complexes, the formation of hydrogen bonded complexes between CuCl42- and glucose is preferred. No preference for the coordination of metal chloride species to specific hydroxyl group of the carbohydrate is found. The formation of binuclear metal chloride complexes is also considered. The reactivity and selectivity patterns of the Lewis acid catalyzed reactions of glucose are discussed in the framework of the obtained results.

EPR, optical absorption and luminescence studies of Cr3+-doped antimony phosphate glasses

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Thermal Treatments of Fe—Mn Alkoxide of Glycerol: Infrared absorption and emission

Synthetic Fe—Mn alkoxide of glycerol samples are submitted to controlled heating conditions and examined by IR absorption spectroscopy. On the other hand, the same sample is studied by infrared emission spectroscopy (IRES), upon heating in situ from 100 to 600°C. The spectral techniques employed in this contribution, especially IRES, show that as a result of the thermal treatments ferromagnetic oxides (manganese ferrite) are formed between 350 and 400°C. Some further spectral changes are seen at higher temperatures.

Optical absorption and EPR studies on tenorite mineral

Optical absorption and EPR studies of the mineral tenorite, a cupric oxide, which originated from Mexico and contains 54.40 wt% of CuO. EPR spectral results indicate two Cu(II) closely interacting ions to give a d2 type structure. The calculated spin Hamiltonian at Rt and LNT are g = 2.160 and D = 125 G . The intensity of resonance line is not the same in low and high field regions. The optical absorption spectrum is due to Cu(II) which three sets of energies indicating Cu(II) in two independent tetragonal C4v symmetry, in addition to d2 structure of octahedral coordination. The octahedral and tetragonal field parameters are compared with those reported for several other copper containing minerals.

Characterisation of organoclays and adsorption of p-nitrophenol : environmental application

Organoclays were synthesised through ion exchange of a single surfactant for sodium ions, and characterised by a range of method including X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and transmission electron microscopy (TEM). The change in surface properties of montmorillonite and organoclays intercalated with the surfactant, tetradecyltrimethylammonium bromide (TDTMA) were determined using XRD through the change in basal spacing and the expansion occurred by the adsorbed p-nitrophenol. The changes of interlayer spacing were observed in TEM. In addition, the surface measurement such as specific surface area and pore volume was measured and calculated using BET method, this suggested the loaded surfactant is highly important to determine the sorption mechanism onto organoclays. The collected results of XPS provided the chemical composition of montmorillonite and organoclays, and the high-resolution XPS spectra offered the chemical states of prepared organoclays with binding energy. Using TGA and FT-IR, the confirmation of intercalated surfactant was investigated. The collected data from various techniques enable an understanding of the changes in structure and surface properties. This study is of importance to provide mechanisms for the adsorption of organic molecules, especially in contaminated environmental sites and polluted waters.

Homo- and heteronuclear meso,meso-(E)-Ethene-1,2-diyl-Linked Diporphyrins : preparation, X-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations

Homo-and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M 210 (M 2=H 2/Ni, Ni 2, Ni/Zn, H 4, H 2Zn, Zn 2) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H 2, Ni, and ZnTriPP on the other (M 211), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni 2 bis(TriPP) complex Ni 210, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni II porphyrins, and the (E)-C 2H 2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H 410 and H 2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni 210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron paramagnetic resonance, optical absorption and Raman spectral studies on a pyrite/chalcopyrite mineral

Pyrite and chalcopyrite mineral samples from Mangampet barite mine, Kadapa, Andhra Pradesh, India are used in the present study. XRD data indicate that the pyrite mineral has a face centered cubic lattice structure with lattice constant 5.4179 Å. Also it possesses an average particle size of 91.9 nm. An EPR study on the powdered samples confirms the presence of iron in pyrite and iron and Mn(II) in chalcopyrite. The optical absorption spectrum of chalcopyrite indicates presence of copper which is in a distorted octahedral environment. NIR results confirm the presence of water fundamentals and Raman spectrum reveals the presence of water and sulfate ions.