Removal of lead(II) and cadmium(II) from aqueous solutions using grape stalk waste

The sorption of lead and cadmium from aqueous solutions by grape stalk waste (a by-product of wine production) was investigated. The effects of the contact time, pH of the solution, ionic medium, initial metal concentration, other metal ions present and ligands were studied in batch experiments at 20 degrees C. Maximum sorption for both metals was found to occur at an initial pH of around 5.5. The equilibrium process was described well by the Langmuir isotherm model, with maximum grape stalk sorption capacities of 0.241 and 0.248 mmol g(-1) for Pb(II) and Cd(II), respectively, at pH around 5.5. Kinetic studies showed good correlation coefficients for a pseudo-second-order kinetic model. The presence of NaCl and NaClO(4) in the solution caused a reduction in Pb and Cd sorption, the latter being more strongly suppressed. The presence of other metals in the uptake process did not affect the removal of Pb, while the Cd uptake was much reduced. HCl or EDTA solutions were able to desorb lead from the grape stalks completely, while an approximately 65% desorption yield was obtained for cadmium. From the results obtained it seems that other mechanisms, such as surface complexation and electrostatic interactions, must be involved in the metal sorption in addition to ion exchange.     

Characterisation of products of tricalcium silicate hydration in the presence of heavy metals

The hydration of tricalcium silicate (C(3)S) in the presence of heavy metal is very important to cement-based solidification/stabilisation (s/s) of waste. In this work, tricalcium silicate pastes and aqueous suspensions doped with nitrate salts of Zn(2+), Pb(2+), Cu(2+) and Cr(3+) were examined at different ages by X-ray powder diffraction (XRD), thermal analysis (DTA/TG) and (29)Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). It was found that heavy metal doping accelerated C(3)S hydration, even though Zn(2+) doping exhibited a severe retardation effect at an early period of time of C(3)S hydration. Heavy metals retarded the precipitation of portlandite due to the reduction of pH resulted from the hydrolysis of heavy metal ions during C(3)S hydration. The contents of portlandite in the control, Cr(3+)-doped, Cu(2+)-doped, Pb(2+)-doped and Zn(2+)-doped C(3)S pastes aged 28 days were 16.7, 5.5, 5.5, 5.5, and <0.7%, respectively. Heavy metals co-precipitated with calcium as double hydroxides such as (Ca(2)Cr(OH)(7).3H(2)O, Ca(2)(OH)(4)4Cu(OH)(2).2H(2)O and CaZn(2)(OH)(6).2H(2)O). These compounds were identified as crystalline phases in heavy metal doping C(3)S suspensions and amorphous phases in heavy metal doping C(3)S pastes. (29)Si NMR data confirmed that heavy metals promoted the polymerisation of C-S-H gel in 1-year-old of C(3)S pastes. The average numbers of Si in C-S-H gel for the Zn(2+)-doped, Cu(2+)-doped, Cr(3+)-doped, control, and Pb(2+)-doped C(3)S pastes were 5.86, 5.11, 3.66, 3.62, and 3.52. And the corresponding Ca/Si ratios were 1.36, 1.41, 1.56, 1.57 and 1.56, respectively. This study also revealed that the presence of heavy metal facilitated the formation of calcium carbonate during C(3)S hydration process in the presence of carbon dioxide.     

Highly acidic phosphorus-containing porous carbons: synthesis and physicochemical properties

Phosphorus-containing carbon porous materials were obtained by pyrolysis of sucrose in the presence of phosphoric acid at a temperature 400 and 800 °C. Synthesized samples were characterized by elemental analysis, infrared spectroscopy, nitrogen adsorption–desorption, the measurement of cation-exchange capacity (CEC) and sorption capacity for lead ions, potentiometric titration. It was shown that phosphorus-containing carbon sorbents have acidic properties and they are characterized by high cation-exchange capacity (up to 5.9 mmol/g). The samples which were synthesized at 800 °C have the highest content of acid groups, as well as phosphorus and oxygen. Detected surface acidic groups are phosphorus-containing (pК ~1.7–1.9) and represent residua of acid phosphates and polyphosphates, connected with carbon framework. High CEC of synthesized materials can be attributed to a significant degree of phosphorylation of sucrose through the large number of hydroxyl groups. P-containing acid groups on the surface of carbon framework provide high adsorption of heavy metals ions (in particular lead). Thus, the obtained P-containing carbon sorbents can be used as effective cation-exchangers for the removal of cations of heavy metals from aqueous solutions.     

13C CPMAS NMR spectroscopy as a versatile and quantitative tool for determination of mercury adsorption capacity in thiol-functionalized mesoporous silica SBA-1

13C cross-polarization magic angle spinning (CPMAS) NMR spectroscopy is demonstrated to be a valuable characterization tool for quantitative measurements of Hg2+ adsorption capacity in thiol-functionalized mesoporous silica SBA-1 (Santa Barbara Amorphous-1). This is the first report on the investigation of the spectral change in the 13C CP signals for mercaptopropyl-functionalized mesoporous materials doped with different Hg2+ concentrations. The chemical shift of the carbon atom adjacent to the thiol group is sensitive to the binding of the mercury ion, and its peak intensity can be used as a quantitative sensor for the amount of the mercury ion adsorbed. The 13C CPMAS NMR results are in good agreement with inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis.     

Characterization of chemically modified corncobs and its application in the removal of metal ions from aqueous solution

The objective of this work was to convert corncobs to activated carbon by low temperature chemical treatment for removing copper from wastewater. The parameters for developing a new adsorbent i.e. sorption capacity, selectivity, regenerability, suspension test, and kinetics were investigated. All studies were performed in batch experiments. Removal of copper from aqueous solutions varied with the amount of adsorbent, metal ion concentration, agitation time, solution pH and the species of copper present. It was found that the effect of temperature was very small. The Langmuir model was found to best fit the equilibrium isotherm data. Kinetics of copper removal at two different temperatures obeyed Lagergren pseudo-first-order equation. Effect of water hardness, other cations (Pb(2+) and Zn(2+)) on copper removal was also studied. Experiments with anionic and cationic complexes of copper showed that anionic copper species are not removed at all by the prepared material. To observe the nature of surface and pore structure scanning electron microscope (SEM) images of modified corncobs were used. To study the interaction forces between the adsorbent and the metal ion functional group analysis with infrared spectroscopy and proximate analysis were carried out. In addition, recovery of the metals ion and regeneration of spent adsorbent was possible by acidified hydrogen peroxide. Since the uptake capacity of the prepared adsorbent is 26mg Cu/g for copper, it can be a potential adsorbent for removing and recovering other heavy metal ions from contaminated wastewaters. The sorption capacity of the treated corncobs for copper was better than the reported capacity of other activated carbons prepared from agricultural sources.     

Photolytic breakdown of fullerene C60 cages in an aqueous suspension

Fullerene C60, a class of carbon nanomaterials, is widely used and is likely to reach the environment. The degradation and transformation of C60 aqueous suspensions exposed to simulated sunlight were studied. C60 aqueous suspensions prepared by stirring pristine C60 in water under sunlight exposure undergo breakdown with formation of a mixture of compounds with unknown chemical structure. The mass and infrared spectrometric analysis of the breakdown products shows the presence of broken C60 cages, as well as of oxygen and hydrogen atoms in their structure. The presence of oxygen in the breakdown products indicates a possible interaction of C60 molecule with oxygen from the air as well as with water. Interaction with water could also explain the presence of H atoms in the breakdown products. This demonstrates that fullerenes C60 are not stable in the environment and that the breakdown products should be considered when evaluating the environmental impact of fullerenes C60.     

Towards full-structure determination of bimetallic nanoparticles with an aberration-corrected electron microscope

To fully understand the properties of functional nanostructures such as catalytic nanoclusters, it is necessary to know the positions of all the atoms in the nanostructure. The catalytic properties of metal nanoclusters can often be improved by the addition of a second metal, but little is known about the role of the different metals in these bimetallic catalysts, or about their interactions with each other and the support material. Here we show that aberration-corrected scanning transmission electron microscopy of supported rhodium-iridium clusters, combined with dynamic multislice image simulations, can identify individual atoms, map the full structure, and determine changes in the positions of metal atoms in sequential images. This approach could help in the development of new and improved catalysts and other functional nanostructures.     

Equilibrium studies for the sorption of zinc and copper from aqueous solutions using sugar beet pulp and fly ash

In the present work, the abilities of native sugar beet pulp (SBP) and fly ash (FA) to remove copper (Cu(2+)) and zinc (Zn(2+)) ions from aqueous solutions were compared. The SBP and FA, an industrial by-product and solid waste of sugar industry, were used for the removal of copper and zinc from aqueous water. Batch adsorption experiments were performed in order to evaluate the removal efficiency of SBP and lignite-based FA. The effect of various operating variables, i.e. initial pH, adsorbent dose, initial metal ion concentration, and time on adsorption of copper and zinc onto the SBP and FA, has been studied. The sorption process was relatively fast and equilibrium was reached after about 60 min of contact. As much as 60-97% removal of copper and zinc for SBP and FA are possible in about 60 min, respectively, under the batch test conditions. Uptake showed a pH-dependent profile. The overall uptake for the SBP is at a maximum at pH 5.5 and gives up to 30.9 mg g(-1) for copper and at pH 6.0 and gives 35.6 mg g(-1) for zinc for SBP, which seems to be removed exclusively by ion exchange and physical sorption. Maximum adsorption of copper and zinc occurred 7.0 and 7.84 mg g(-1) at a pH value of 5.0 and 4.0 for FA, respectively. A dose of 8 g l(-1) of SBP and 8 g l(-1) FA were sufficient for the optimum removal of both the metal ions. The sorption data were represented by the Freundlich for SBP and the Langmuir and Freundlich for FA. The sorption data were better represented by the Langmuir isotherm than by the Freundlich one for FA in the adsorption of zinc ion, suggesting that the monolayer sorption, mainly due to ion exchange. The presence of low ionic strength or low concentration of Na and Cl ions does not have a significant effect on the adsorption of these metals by SBP and FA. The SBP and FA are shown to be effective metal adsorbents for these two metals.     

Investigation of the Interactions and Bonding between Carbon and Group VIII Metals at the Atomic Scale

The nature and dynamics of bonding between Fe, Ru, Os, and single‐walled carbon nanotubes (SWNTs) is studied by aberration‐corrected high‐resolution transmission electron microscopy (AC‐HRTEM). The metals catalyze a wide variety of different transformations ranging from ejection of carbon atoms from the nanotube sidewall to the formation of hollow carbon shells or metal carbide within the SWNT, depending on the nature of the metal. The electron beam of AC‐HRTEM serves the dual purpose of providing energy to the specimen and simultaneously enabling imaging of chemical transformations. Careful control of the electron beam parameters, energy, flux, and dose allowed direct comparison between the metals, demonstrating that their chemical reactions with SWNTs are determined by a balance between the cohesive energy of the metal particles and the strength of the metal–carbon σ‐ or π‐bonds. The pathways of transformations of a given metal can be drastically changed by applying different electron energies (80, 40, or 20 keV), thus demonstrating AC‐HRTEM as a new tool to direct and study chemical reactions. The understanding of interactions and bonding between SWNT and metals revealed by AC‐HRTEM at the atomic level has important implications for nanotube‐based electronic devices and catalysis.     

X-ray-diffraction characterization of Pt(111) surface nanopatterning induced by C60 adsorption

Understanding the adsorption mechanisms of large molecules on metal surfaces is a demanding task. Theoretical predictions are difficult because of the large number of atoms that have to be considered in the calculations, and experiments aiming to solve the molecule-substrate interaction geometry are almost impossible with standard laboratory techniques. Here, we show that the adsorption of complex organic molecules can induce perfectly ordered nanostructuring of metal surfaces. We use surface X-ray diffraction to investigate in detail the bonding geometry of C(60) with the Pt(111) surface, and to elucidate the interaction mechanism leading to the restructuring of the Pt(111) surface. The chemical interaction between one monolayer of C(60) molecules and the clean Pt(111) surface results in the formation of an ordered sqrt[13] x sqrt[13]R13.9 degrees reconstruction based on the creation of a surface vacancy lattice. The C(60) molecules are located on top of the vacancies, and 12 covalent bonds are formed between the carbon atoms and the 6 platinum surface atoms around the vacancies. In-plane displacements induced on the platinum substrate are of the order of a few picometres in the top layer, and are undetectable in the deeper layers.     

Morphological instability leading to formation of porous anodic oxide films

Electrochemical oxidation of metals, in solutions where the oxide is somewhat soluble, produces anodic oxides with highly regular arrangements of pores. Although porous aluminium and titanium oxides have found extensive use in functional nanostructures, pore initiation and self-ordering are not yet understood. Here we present an analysis that examines the roles of oxide dissolution and ionic conduction in the morphological stability of anodic films. We show that patterns of pores with a minimum spacing are possible only within a narrow range of the oxide formation efficiency (the fraction of oxidized metal atoms retained in the film), which should exist when the metal ion charge exceeds two. Experimentally measured efficiencies, over diverse anodizing conditions on both aluminium and titanium, lie within the different ranges predicted for each metal. On the basis of these results, the relationship between dissolution chemistry and the conditions for pore initiation can now be understood in quantitative terms.     

Plasma cleaning and the removal of carbon from metal surfaces

In an investigation of the plasma cleaning of metals and the plasma etching of carbon, a mass spectrometer was used as a sensitive process monitor. CO₂ produced by the plasma oxidation of carbon films or of organic contamination and occluded carbon at the surfaces of metals proved to be the most suitable gas to monitor. A good correlation was obtained between the measured etch rate of carbon and the resulting CO₂ partial pressure monitored continuously with the mass spectrometer.The rate of etching of carbon in an oxygen-argon plasma at 0.1 Torr was high when the carbon was at cathode potential and low when it was electrically isolated in the plasma, thus confirming the findings of previous workers and indicating the importance of ion bombardment in the etching process. Superficial organic contamination on the surfaces of the metals aluminium and copper and of the alloy Inconel 625 was quickly removed by the oxygen-argon plasma when the metal was electrically isolated and also when it was at cathode potential. Occluded carbon (or carbides) at or near the surfaces of the metals was removed slowly and only when the metal was at cathode potential, thus illustrating again the importance of ion bombardment.     

Effect of the charge state (z = -1, 0, +1) on the nuclear magnetic resonance of monodisperse Au25[S(CH2)2Ph]18(z) clusters

Monodisperse Au(25)L(18)(0) (L = S(CH(2))(2)Ph) and [n-Oct(4)N(+)][Au(25)L(18)(-)] clusters were synthesized in tetrahydrofuran. An original strategy was then devised to oxidize them: in the presence of bis(pentafluorobenzoyl) peroxide, the neutral or the negatively charged clusters react as efficient electron donors in a dissociative electron-transfer (ET) process, in the former case yielding [Au(25)L(18)(+)][C(6)F(5)CO(2)(-)]. As opposed to other reported redox methods, this dissociative ET approach is irreversible, easily controllable, and clean, particularly for NMR purposes, as no hydrogen atoms are introduced. By using this approach, the -1, 0, and +1 charge states of Au(25)L(18) could be fully characterized by (1)H and (13)C NMR spectroscopy, using one- and two-dimensional techniques, in various solvents, and as a function of temperature. For all charge states, the NMR results and analysis nicely match recent structural findings about the presence of two different ligand populations in the capping monolayer, each resonance of the two ligand families displaying distinct NMR patterns. The radical nature of Au(25)L(18)(0) is particularly evident in the (1)H and (13)C NMR patterns of the inner ligands. The NMR behavior of radical Au(25)L(18)(0) was also simulated by DFT calculations, and the interplay between theory and experiments revealed a fundamental paramagnetic contribution coming from Fermi contact shifts. Interestingly, the NMR patterns of Au(25)L(18)(-) and Au(25)L(18)(+) were found to be quite similar, pointing to the latter cluster form as a diamagnetic species.     

Gate effect of vacancy-type defect of fullerene cages on metal-atom migrations in metallofullerenes

Metal-atom migration outside from a defective fullerene cage of a metallofullerene Gd@C(82) (Ca@C(82)), where the Gd(3+) (Ca(2+)) ion is incorporated inside the C(2)(v)()-C(82) cage, is discussed in detail at the B3LYP DFT level of theory. The metal-atom migrations are initiated by the formation of vacancy-type defects involving two coordinatively unsaturated C atoms. This step, which is assumed to proceed due to energy-particle irradiation, leads to the formation of antibonding orbitals between the two C atoms. Since the antibonding orbitals can interact with vacant d-orbitals of the Gd(3)(+)() ion in an in-phase fashion, the attractive interactions allow the Gd ion to insert into the two C atoms in the defect. As a result, the metal ion passes through the defect under energy-particle irradiation. In contrast, the Ca(2+) ion with the vacant s-orbitals does not have such orbital interactions, and thus, a C-C bond is reformed between the two C atoms, which prohibits the Ca ion from penetrating the defected C(82) cage. DFT calculations nicely demonstrate that the orbital interactions control metal-atom migration around the defect site using their orbital symmetries, and therefore, the vacancy-type defect acts as a "gate" that permits a specific atom to go out from a defected fullerene cage.     

NMR Studies of the Dynamic Motion of Encapsulated Ions and Clusters in Fullerene Cages: A Wheel Within a Wheel

Nuclear magnetic resonance (NMR) has provided an important approach to investigate the structure and dynamics of encapsulated metal ions and clusters in endohedral metallofullerenes (EMFs). In this paper, we review NMR studies of the environment and dynamics of dimetallic, trimetallic nitride, metal carbide and metal cyanide clusters encapsulated in EMFs. The NMR chemical shielding parameter is a sensitive probe for monitoring the carbon cage (¹³C) and encapsulated clusters (¹³C, ¹⁴N, ¹³⁹La, ⁴⁵Sc, and ⁸⁹Y). Future NMR EMF studies could be very fruitful and help elucidate coupled motion between the carbon cage and encapsulated cluster or other “wheel within a wheel” motional processes.     

Comparison of adsorption capacity of young brown coals and humic acids prepared from different coal mines in Anatolia

Binding of Zn2+ and Cd2+ cations to relatively young brown coals YBC (lignite), humic acids (HAs) and commercial humic acid (CHA) were studied in aqueous media at pH 2.7-6 by polarographic method. This study was conducted to evaluate the removal of heavy metals in an aquatic system without prior treatment. The general principles of cation binding to YBC and humic materials are discussed. Sorption of heavy metal ions (Zn2+ and Cd2+) on samples of YBCs from three areas (Ilgin, Beysehir, and Ermenek) in the vicinity of the city of Konya in Anatolia (Turkey) were compared with sorption of these metal ions on HAs, prepared from these YBCs. The ability of both types of sorbent to remove metals from aqueous solutions was studied as a function of pH and concentration of initial metal solutions. Sorption depends strongly on pH, the origin of the YBC and on the nature of the metal ion. Whereas, for YBCs the main ligand groups seem to be carboxylate ions, this is not the case for the HA polymers, prepared from three YBCs, which differ substantially from properties of commercial samples of "HA". The process is very efficient especially in the case of low concentrations of pollutants in water, where common methods are either economically unfavorable or technically complicated. Of the two metal ions examined, Cd2+ was found to form the most stable HA complexes, followed by Zn. Effective removal of metals was demonstrated at pH-values of 5-5.7. The adsorption isotherm was measured at 25 degrees C, using adsorptive solutions at the optimum pH-value to determine the adsorption capacity. An important aspect of the proposed method was that the removal was performed on several metals at a pH-range in which a given metal undergoes an adsorption process making the method useful for wastewater treatment.     

Analysis of amino acid isotopomers using FT-ICR MS

Fluxes through known metabolic pathways and the presence of novel metabolic reactions are often determined by feeding isotopically labeled substrate to an organism and then determining the isotopomer distribution in amino acids in proteins. However, commonly used techniques to measure the isotopomer distributions require derivatization prior to analysis (gas chromatography/mass spectrometry (GC/MS)) or large sample sizes (nuclear magnetic resonance (NMR) spectroscopy). Here, we demonstrate the use of Fourier transform-ion cyclotron resonance mass spectrometry with direct infusion via electrospray ionization to rapidly measure the amino acid isotopomer distribution in a biomass hydrolysate of the soil bacterium Desulfovibrio vulgaris Hildenborough. By applying high front-end resolution for the precursor ion selection followed by sustained off-resonance irradiation collision-induced dissociation, it was possible to determine exactly and unambiguously the specific locations of the labeled atoms in the amino acids, which usually requires a combination of 2-D 13C NMR spectroscopy and GC/MS. This method should be generally applicable to all biomass samples and will allow more accurate determination of metabolic fluxes with less work and less sample.     

Effective removal of zinc ions from aqueous solutions using crab carapace biosorbent

The carapace of the crab (Cancer pagurus), a waste material disposed of by the seafood industry, has recently been shown to have potential as a biosorbent for the removal of metals from aqueous media. Crab carapace in the particle size ranges 0.25-0.8mm and 0.8-1.5mm were used to investigate the effects of agitation speed, contact time, metal concentration and initial pH on the removal of Zn(2+). In sequential-batch process Zn(2+) uptakes of 105.6 and 67.6 mg/g were recorded for 0.25-0.8 mm and 0.8-1.5 mm particles, respectively, while values of 141.3 and 76.9 mg/g were recorded in fixed-bed column studies. Binary-metal studies showed that the presence of Cu(2+) or Pb(2+) significantly suppressed Zn(2+) uptake. This study confirms that crab carapace may be considered a viable and cost-effective alternative to commercial activated carbon or ion-exchange resins for the removal of metals from aqueous media.