CO adsorption over Pd nanoparticles:a general framework for IR simulations on nanoparticles

CO vibrational spectra over catalytic nanoparticles under high coverages/pressures are discussed from a DFT perspective. Hybrid B3LYP and PBE DFT calculations of CO chemisorbed over Pd4 and Pd13 nanoclusters, and a 1.1 nm Pd38 nanoparticle, have been performed in order to simulate the corresponding coverage dependent infrared (IR) absorption spectra, and hence provide a quantitative foundation for the interpretation of experimental IR spectra of CO over Pd nanocatalysts. B3LYP simulated IR intensities are used to quantify site occupation numbers through comparison with experimental DRIFTS spectra, allowing an atomistic model of CO surface coverage to be created. DFT adsorption energetics for low CO coverage (θ → 0) suggest the CO binding strength follows the order hollow > bridge > linear, even for dispersion-corrected functionals for sub-nanometre Pd nanoclusters. For a Pd38 nanoparticle, hollow and bridge-bound are energetically similar (hollow ≈ bridge > atop). It is well known that this ordering has not been found at the high coverages used experimentally, wherein atop CO has a much higher population than observed over Pd(111), confirmed by our DRIFTS spectra for Pd nanoparticles supported on a KIT-6 silica, and hence site populations were calculated through a comparison of DFT and spectroscopic data. At high CO coverage (θ = 1), all three adsorbed CO species co-exist on Pd38, and their interdiffusion is thermally feasible at STP. Under such high surface coverages, DFT predicts that bridge-bound CO chains are thermodynamically stable and isoenergetic to an entirely hollow bound Pd/CO system. The Pd38 nanoparticle undergoes a linear (3.5%), isotropic expansion with increasing CO coverage, accompanied by 63 and 30 cm− 1 blue-shifts of hollow and linear bound CO respectively.

Methyl chloride purification for the silicone industry

This study experimentally investigated methyl chloride (MeCl) purification method using an inhouse designed and built volumetric adsorption/desorption rig. MeCl is an essential raw material in the manufacture of silicone however all technical grades of MeCl contain concentrations (0.2 - 1.0 % wt) of dimethyl ether (DME) which poison the process. The project industrial partner had previously exhausted numerous separation methods, which all have been deemed not suitable for various reasons. Therefore, adsorption/desorption separation was proposed in this study as a potential solution with less economic and environmental impact. Pure component adsorption/desorption was carried out for DME and MeCl on six different adsorbents namely: zeolite molecular sieves (types 4 Å and 5 Å); silica gels (35-70 mesh, amorphous precipitated, and 35-60 mesh) and granular activated carbon (type 8-12 mesh). Subsequent binary gas mixture adsorption in batch and continuous mode was carried out on both zeolites and all three silica gels following thermal pre-treatment in vacuum. The adsorbents were tested as received and after being subjected to different thermal and vacuum pre-treatment conditions. The various adsorption studies were carried out at low pressure and temperature ranges of 0.5 - 3.5 atm and 20 - 100 °C. All adsorbents were characterised using Brunauer Emmett Teller (BET), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDXA) to investigate their physical and chemical properties. The well-known helium (He) expansion method was used to determine the empty manifold and adsorption cell (AC) regions and respective void volumes for the different adsorbents. The amounts adsorbed were determined using Ideal gas laws via the differential pressure method. The heat of adsorption for the various adsorbate-adsorbent (A-S) interactions was calculated using a new calorimetric method based on direct temperature measurements inside the AC. Further adsorption analysis included use of various empirical and kinetic models to determine and understand the behaviour of the respective interactions. The gas purification behaviour was investigated using gas chromatography and mass spectroscopy (GC-MC) analysis. Binary gas mixture samples were syringed from the manifold iii and AC outlet before and after adsorption/desorption analysis through manual sample injections into the GC-MS to detect and quantify the presence of DME and ultimately observe for methyl chloride purification. Convincing gas purification behaviour was confirmed using two different GC columns, thus giving more confidence on the measurement reliability. From the single pure component adsorption of DME and MeCl on the as received zeolite 4A subjected to 1 h vacuum pre-treatment, both gases exhibited pseudo second order adsorption kinetics with DME exhibiting a rate constant nearly double that of MeCl thus suggesting a faster rate of adsorption. From the adsorption isotherm classification both DME and MeCl exhibited Type II and I adsorption isotherm classifications, respectively. The strength of bonding was confirmed by the differential heat of adsorption measurement, which was found to be 23.30 and 10.21 kJ mol-1 for DME and MeCl, respectively. The former is believed to adsorb heterogeneously through hydrogen bonding whilst MeCl adsorbs homogenously via van der Waal’s (VDW) forces. Single pure component adsorption on as received zeolite 5A, silica gels (35-70, amorphous precipitated and 35-60) resulted in similar adsorption/desorption behaviour in similar quantities (mol kg-1). The adsorption isotherms for DME and MeCl on zeolite 5A, silica gels (35-70, amorphous precipitated and 35-60) and activated carbon 8-12 exhibited Type I classifications, respectively. Experiments on zeolite 5A indicated that DME adsorbed stronger, faster and with a slightly stronger strength of interaction than MeCl but in lesser quantities. On the silica gels adsorbents, DME exhibited a slightly greater adsorption capacity whilst adsorbing at a similar rate and strength of interaction compared to MeCl. On the activated carbon adsorbent, MeCl exhibited the greater adsorption capacity at a faster rate but with similar heats of adsorption. The effect of prolonged vacuum (15 h), thermal pre-treatment (150 °C) and extended equilibrium time (15 min) were investigated for the adsorption behaviour of DME and MeCl on both zeolites 4A and 5A, respectively. Compared to adsorption on as received adsorbents subjected to 1 h vacuum the adsorption capacities for DME and MeCl were found to increase by 1.95 % and 20.37 % on zeolite 4A and by 4.52 % and 6.69 % on zeolite 5A, respectively. In addition the empirical and kinetic models and differential heats of adsorption resulted in more definitive fitting curves and trends due to the true equilibrium position of the adsorbate with the adsorbent. Batch binary mixture adsorption on thermally and vacuum pre-treated zeolite 4A demonstrated purification behaviour of all adsorbents used for MeCl streams containing DME impurities, with a concentration as low as 0.66 vol. %. The GC-MS analysis showed no DME detection for the tested concentration mixtures at the AC outlet after 15 or 30 min, whereas MeCl was detectable in measurable amounts. Similar behaviour was also observed when carrying out adsorption in continuous mode. On the other hand, similar studies on the other adsorbents did not show such favourable MeCl purification behaviour. Overall this study investigated a wide range of adsorbents (zeolites, silica gels and activated carbon) and demonstrated for the first time potential to purify MeCl streams containing DME impurities using adsorption/desorption separation under different adsorbent pre-treatment and adsorption operating conditions. The study also revealed for the first time the adsorption isotherms, empirical and kinetic models and heats of adsorption for the respective adsorbentsurface (A-S) interactions. In conclusion, this study has shown strong evidence to propose zeolite 4A for adsorptive purification of MeCl. It is believed that with a technical grade MeCl stream competitive yet simultaneous co-adsorption of DME and MeCl occurs with evidence of molecular sieiving effects whereby the larger DME molecules are unable to penetrate through the adsorbent bed whereas the smaller MeCl molecules diffuse through resulting in a purified MeCl stream at the AC outlet. Ultimately, further studies are recommended for increased adsorption capacities by considering wider operating conditions, e.g. different adsorbent thermal and vacuum pre-treatment and adsorbing at temperatures closer to the boiling point of the gases and different conditions of pressure and temperature.

Advanced oxidation of arsenic species in aqueous solutions

Ingestion of arsenic from contaminated water is a serious problem and affects the health of more than 100 million people worldwide. Traditional water purification technologies are generally not effective or cost prohibitive for the removal of arsenic to acceptable levels (≤10 ppb). Current multi-step arsenic removal processes involve oxidation, precipitation and/or adsorption. Advanced Oxidation Technologies (AOTs) may be attractive alternatives to existing treatments. The reactions of inorganic and organic arsenic species with reactive oxygen species were studied to develop a fundamental mechanistic understanding of these reactions, which is critical in identifying an effective and economical technology for treatment of arsenic contaminated water. ^ Detailed studies on the conversion of arsenite in aqueous media by ultrasonic irradiation and TiO2 photocatalytic oxidation (PCO) were conducted, focusing on the roles of hydroxyl radical and superoxide anion radical formed during the irradiation. ·OH plays the key role, while O2 -· has little or no role in the conversion of arsenite during ultrasonic irradiation. The reaction of O2-· does not contribute in the rapid conversion of As(III) when compared to the reaction of As(III) with ·OH radical during TiO2 PCO. Monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) are readily degraded upon TiO2 PCO. DMA is oxidized to MMA as the intermediate and arsenate as the final product. For dilute solutions, TiO2 also may be applicable as an adsorbent for direct removal of arsenic species, namely As(III), As(V), MMA and DMA, all of which are strongly adsorbed, thus eliminating the need for a multi-step treatment process. ^ Phenylarsonic acid (PA) was subjected to gamma radiolysis under hydroxyl radical generating conditions, which showed rapid degradation of PA. Product analysis and computational calculation both indicate the arsenate group is an ortho, para director. Our results indicate · OH radical mediated processes should be effective for the remediation of phenyl substituted arsonic acids. ^ While hydroxyl radical generating methods, specifically AOTs, appear to be promising methods for the treatment of a variety of arsenic compounds in aqueous media, pilot studies and careful economic analyses will be required to establish the feasibility of AOTs applications in the removal of arsenic. ^

Adsorption and desorption of phosphate on limestone in experiments simulating seawater intrusion

This study investigates the potential release of from carbonate aquifers exposed to seawater intrusion. Adsorption and desorption of in the presence of deionized water (DIW) and seawater were conducted on a large block of Pleistocene age limestone to simulate the effects of seawater intrusion into a coastal carbonate aquifer at the laboratory scale. The limestone showed strong adsorption of in DIW, while adsorption was significantly less in the presence of seawater. Dissolution of CaCO3 was found to prevent adsorption at salinities less than 30 psu. Adsorption of was limited at higher salinities (30–33 psu), due to competition with ions for adsorption sites. At a salinity3 precipitated. Concentrations of between 2 and 5 μmol/L were released by desorption when the limestone was exposed to seawater. The results of this study suggest that as seawater intrudes into an originally freshwater coastal aquifer, adsorbed may be released into the groundwater. Consequently, adsorbed is expected to be released from coastal carbonate aquifers world-wide as sea level continues to rise exposing more of the freshwater aquifer to seawater.

The effect of iron oxide nanoparticles on the fate and transformation of arsenic in aquatic environments

Iron oxides and arsenic are prevalent in the environment. With the increase interest in the use of iron oxide nanoparticles (IONPs) for contaminant remediation and the high toxicity of arsenic, it is crucial that we evaluate the interactions between IONPs and arsenic. The goal was to understand the environmental behavior of IONPs in regards to their particle size, aggregation and stability, and to determine how this behavior influences IONPs-arsenic interactions. ^ A variety of dispersion techniques were investigated to disperse bare commercial IONPs. Vortex was able to disperse commercial hematite nanoparticles into unstable dispersions with particles in the micrometer size range while probe ultrasonication dispersed the particles into stable dispersions of nanometer size ranges for a prolonged period of time. Using probe ultrasonication and vortex to prepare IONPs suspensions of different particle sizes, the adsorption of arsenite and arsenate to bare hematite nanoparticles and hematite aggregates were investigated. To understand the difference in the adsorptive behavior, adsorption kinetics and isotherm parameters were determined. Both arsenite and arsenate were capable of adsorbing to hematite nanoparticles and hematite aggregates but the rate and capacity of adsorption is dependent upon the hematite particle size, the stability of the dispersion and the type of sorbed arsenic species. Once arsenic was adsorbed onto the hematite surface, both iron and arsenic can undergo redox transformation both microbially and photochemically and these processes can be intertwined. Arsenic speciation studies in the presence of hematite particles were performed and the effect of light on the redox process was preliminary quantified. The redox behavior of arsenite and arsenate were different depending on the hematite particle size, the stability of the suspension and the presence of environmental factors such as microbes and light. The results from this study are important and have significant environmental implications as arsenic mobility and bioavailability can be affected by its adsorption to hematite particles and by its surface mediated redox transformation. Moreover, this study furthers our understanding on how the particle size influences the interactions between IONPs and arsenic thereby clarifying the role of IONPs in the biogeochemical cycling of arsenic.^

Molecular detection using metallic nanowires with quantized conductance

This thesis studies the adsorption of molecules with different binding strengths onto copper nanowires with prestabilized conductance values fabricated by an electrochemical method. Since the diameters of these wires are comparable to the wavelength of conduction electrons the conductance of the nanowires is quantized, and the adsorption of even a few molecules onto atomically thin wires changes the conductance from integer values to fractional ones. These changes are proportional to the binding strength of the adsorbed molecules. The decrease in conductance is hypothesized to be caused by the scattering of the conduction electrons by the adsorbed molecules. The sensitivity of molecular adsorption-induced conductance change can be used for the development of a chemical sensor. The stabilized copper nanowires obtained in this thesis may also be used for other purposes, such as interconnecting conductors between nanodevices and digital switches in functional nanoelectronic circuitry.

AFM and SPR studies of protein adsorption at solid/liquid interface

Membrane-like structure formed by surfactant molecules of didodecyldimethylammonium bromide (DDAB) on both HOPG and gold electrodes were studied with AFM and SPR techniques. The study shows that the thickness of the adsorbed layer of DDAB is strongly dependent on the concentration of the vesicle solution. We have also investigated the adsorption of redox protein, Cytochrome c, on graphite electrode with in situ tapping mode AFM. The protein adsorbs spontaneously onto the electrode covered with an adsorbed phosphate layer and forms a uniform monolayer. The adsorbed protein exhibits a reversible electron transfer at 0.17 V (Ag/AgCI) once the electrode potential has been increased to 0.75V. Using surface plasmon resonance spectroscopy we have measured subtle conformational change in protein, Cyt c, due to electron transfer of a single electron on MPA-coated gold electrode. The electron transfer induced change in the resonant angle is about 0.006 deg., which corresponds to ~ 0.2 A decreases in the thickness. This is consistent with that reduced state is more compact than the oxidized state.

Desenvolvimento de bionanocompósitos: nano e microcristais de celulose com poli (álcool vinílico) e poli (ácido lático)

This work has the main objective to obtain nano and microcrystals of cellulose, extracted from the pineapple leaf fibres (PALF), as reinforcement for the manufacture of biocomposite films with polymeric matrices of Poly(vinyl alcohol) (PVA) and Poly(lactic acid) (PLA). The polymer matrices and the nano and microcrystals of cellulose were characterised by means of TGA, FTIR and DSC. The analysis was performed on the pineapple leaves to identify the macro and micronutrients. The fibers of the leaves of the pineapple were extracted in a desfibradeira mechanical. The PALF extracted were washed to remove washable impurities and subsequently treated with sodium hydroxide (NaOH) and sodium hypochlorite (NaClO) in the removal of impurities, such as fat, grease, pectates, pectin and lignin. The processed PALF fibers were hydrolysed in sulfuric acid (H2SO4) at a concentration of 13.5 %, to obtain nano and microcrystals of cellulose. In the manufacture of biocomposite films, concentrations of cellulose, 0 %, 1 %, 3 %, 6 %, 9% and 12% were used as reinforcement to the matrices of PVA and PLA. The PVA was dissolved in distilled water at 80 ± 5 oC and the PLA was dissolved in dichloromethane at room temperature. The manufacture of biocompósitos in the form of films was carried out by "casting". Tests were carried out to study the water absorption by the films and mechanical test of resistance to traction according to ASTM D638-10 with a velocity of 50 mm/min.. Chi-square statistical test was used to check for the existence of significant differences in the level of 0.05: the lengths of the PALF, lengths of the nano and microcrystals of cellulose and the procedures used for the filtration using filter syringe of 0.2 μm or filtration and centrifugation. The hydrophilicity of biocompósitos was analysed by measuring the contact angle and the thickness of biocompósitos were compared as well as the results of tests of traction. Statistical T test - Student was also applied with the significance level (0.05). In biodegradation, Sturm test of standard D5209 was used. Nano and microcrystals of cellulose with lengths ranging from 7.33 nm to 186.17 nm were found. The PVA films showed average thicknesses of 0.153 μm and PLA 0.210 μm. There is a strong linear correlation directly proportional between the traction of the films of PVA and the concentration of cellulose in the films (composite) (0,7336), while the thickness of the film was correlated in 0.1404. Nano and microcrystals of cellulose and thickness together, correlated to 0.8740. While the correlation between the cellulose content and tensile strength was weak and inversely proportional (- 0,0057) and thickness in -0.2602, totaling -0,2659 in PLA films. This can be attributed to the nano and microcrystals of cellulose not fully adsorbed to the PLA matrix. In the comparison of the results of the traction of the two polymer matrices, the nano and microcrystals have helped in reducing the traction of the films (composite) of PLA. There was still the degradation of the film of PVA, within a period of 20 days, which was not seen in the PLA film, on the other hand, the observations made in the literature, the average time to start the degradation is above 60 days. What can be said that the films are biodegradable composites, with hydrophilicity and the nano and microcrystals of cellulose, contribute positively in the improvement of the results of polymer matrices used.

Avaliação do desempenho da paligorsquita modificada e do carvão da pirólise do lodo de esgoto no processo de degradação fotocatalítica do fenol

The uncontrolled disposal of wastewaters containing phenolic compounds by the industry has caused irreversible damage to the environment. Because of this, it is now mandatory to develop new methods to treat these effluents before they are disposed of. One of the most promising and low cost approaches is the degradation of phenolic compounds via photocatalysis. This work, in particular, has as the main goal, the customization of a bench scale photoreactor and the preparation of catalysts via utilization of char originated from the fast pyrolysis of sewage sludge. The experiments were carried out at constant temperature (50°C) under oxygen (410, 515, 650 and 750 ml min-1). The reaction took place in the liquid phase (3.4 liters), where the catalyst concentration was 1g L-1 and the initial concentration of phenol was 500 mg L-1 and the reaction time was set to 3 hours. A 400 W lamp was adapted to the reactor. The flow of oxygen was optimized to 650 ml min-1. The pH of the liquid and the nature of the catalyst (acidified and calcined palygorskite, palygorskite impregnated with 3.8% Fe and the pyrolysis char) were investigated. The catalytic materials were characterized by XRD, XRF, and BET. In the process of photocatalytic degradation of phenol, the results showed that the pH has a significant influence on the phenol conversion, with best results for pH equal to 5.5. The phenol conversion ranged from 51.78% for the char sewage sludge to 58.02% (for palygorskite acidified calcined). Liquid samples analyzed by liquid chromatography and the following compounds were identified: hydroquinone, catechol and maleic acid. A mechanism of the reaction was proposed, whereas the phenol is transformed into the homogeneous phase and the others react on the catalyst surface. For the latter, the Langmuir-Hinshelwood model was applied, whose mass balances led to a system of differential equations and these were solved using numerical methods in order to get estimates for the kinetic and adsorption parameters. The model was adjusted satisfactorily to the experimental results. From the proposed mechanism and the operating conditions used in this study, the most favored step, regardless of the catalyst, was the acid group (originated from quinone compounds), being transformed into CO2 and water, whose rate constant k4 presented value of 0.578 mol L-1 min-1 for acidified calcined palygorskite, 0.472 mol L-1 min-1 for Fe2O3/palygorskite and 1.276 mol L-1 min-1 for the sludge to char, the latter being the best catalyst for mineralization of acid to CO2 and water. The quinones were adsorbed to the acidic sites of the calcined palygorskite and Fe2O3/palygorskite whose adsorption constants were similar (~ 4.45 L mol-1) and higher than that of the sewage sludge char (3.77 L mol-1).

Avaliação do desempenho da paligorsquita modificada e do carvão da pirólise do lodo de esgoto no processo de degradação fotocatalítica do fenol

The uncontrolled disposal of wastewaters containing phenolic compounds by the industry has caused irreversible damage to the environment. Because of this, it is now mandatory to develop new methods to treat these effluents before they are disposed of. One of the most promising and low cost approaches is the degradation of phenolic compounds via photocatalysis. This work, in particular, has as the main goal, the customization of a bench scale photoreactor and the preparation of catalysts via utilization of char originated from the fast pyrolysis of sewage sludge. The experiments were carried out at constant temperature (50°C) under oxygen (410, 515, 650 and 750 ml min-1). The reaction took place in the liquid phase (3.4 liters), where the catalyst concentration was 1g L-1 and the initial concentration of phenol was 500 mg L-1 and the reaction time was set to 3 hours. A 400 W lamp was adapted to the reactor. The flow of oxygen was optimized to 650 ml min-1. The pH of the liquid and the nature of the catalyst (acidified and calcined palygorskite, palygorskite impregnated with 3.8% Fe and the pyrolysis char) were investigated. The catalytic materials were characterized by XRD, XRF, and BET. In the process of photocatalytic degradation of phenol, the results showed that the pH has a significant influence on the phenol conversion, with best results for pH equal to 5.5. The phenol conversion ranged from 51.78% for the char sewage sludge to 58.02% (for palygorskite acidified calcined). Liquid samples analyzed by liquid chromatography and the following compounds were identified: hydroquinone, catechol and maleic acid. A mechanism of the reaction was proposed, whereas the phenol is transformed into the homogeneous phase and the others react on the catalyst surface. For the latter, the Langmuir-Hinshelwood model was applied, whose mass balances led to a system of differential equations and these were solved using numerical methods in order to get estimates for the kinetic and adsorption parameters. The model was adjusted satisfactorily to the experimental results. From the proposed mechanism and the operating conditions used in this study, the most favored step, regardless of the catalyst, was the acid group (originated from quinone compounds), being transformed into CO2 and water, whose rate constant k4 presented value of 0.578 mol L-1 min-1 for acidified calcined palygorskite, 0.472 mol L-1 min-1 for Fe2O3/palygorskite and 1.276 mol L-1 min-1 for the sludge to char, the latter being the best catalyst for mineralization of acid to CO2 and water. The quinones were adsorbed to the acidic sites of the calcined palygorskite and Fe2O3/palygorskite whose adsorption constants were similar (~ 4.45 L mol-1) and higher than that of the sewage sludge char (3.77 L mol-1).

Catalisadores bifuncionais à base de silicoaluminofosfato e fosfatos de nióbio para emprego em reações de hidroisomerização e hidrocraqueamento do n-hexadecano

Lubricants and cutting middle distillates typically have large amounts of n-paraffins to increase its freezing point and fluidity. Accordingly, the removal of n-paraffins of long chain lubricants oils and diesel is essential to get a product with good cold flow properties. The development of new catalysts, which exhibit thermal stability and catalytic activity for the hydroisomerization reaction is still a challenge. Thus, silicoaluminophosphates (SAPO) were synthesized by different routes. Have been used also post-synthesis treatment for obtaining hybrid structures and others synthesis have been carried out with mesoporous template (soft and hard-template). Therefore, SAPO have been impregnated with H2PtCl6 solution by the incipient wetness method. Then assessments of catalytic activities in hydroisomerization and hydrocracking reactions of hexadecane have been held. Besides SAPO, niobium phosphate - NbP - were also impregnated with platinum and evaluated in the same reaction. After impregnation, these catalysts have been characterized by X-ray diffraction (XRD), nitrogen adsorption, infrared spectroscopy with adsorbed pyridine (IV-PY), scanning electron microscopy (SEM) and resonance nuclear magnetic 29Si (29Si-NMR). The characterization results by XRD have shown that it has been possible to obtain mesoporous SAPOs. However, for the syntheses with soft template there was collapse of the structure after removal of the organic template. Even so, these catalysts have been actives. It was possible to obtain hybrid materials through the synthesis of SAPO-11 made with hard templates and by means of post-synthesis treatments samples of SAPO-11. Moreover, NbP has shown characteristic XRD of amorphous materials, with high acidity and were active in the conversion of hexadecane.

Catalisadores bifuncionais à base de silicoaluminofosfato e fosfatos de nióbio para emprego em reações de hidroisomerização e hidrocraqueamento do n-hexadecano

Lubricants and cutting middle distillates typically have large amounts of n-paraffins to increase its freezing point and fluidity. Accordingly, the removal of n-paraffins of long chain lubricants oils and diesel is essential to get a product with good cold flow properties. The development of new catalysts, which exhibit thermal stability and catalytic activity for the hydroisomerization reaction is still a challenge. Thus, silicoaluminophosphates (SAPO) were synthesized by different routes. Have been used also post-synthesis treatment for obtaining hybrid structures and others synthesis have been carried out with mesoporous template (soft and hard-template). Therefore, SAPO have been impregnated with H2PtCl6 solution by the incipient wetness method. Then assessments of catalytic activities in hydroisomerization and hydrocracking reactions of hexadecane have been held. Besides SAPO, niobium phosphate - NbP - were also impregnated with platinum and evaluated in the same reaction. After impregnation, these catalysts have been characterized by X-ray diffraction (XRD), nitrogen adsorption, infrared spectroscopy with adsorbed pyridine (IV-PY), scanning electron microscopy (SEM) and resonance nuclear magnetic 29Si (29Si-NMR). The characterization results by XRD have shown that it has been possible to obtain mesoporous SAPOs. However, for the syntheses with soft template there was collapse of the structure after removal of the organic template. Even so, these catalysts have been actives. It was possible to obtain hybrid materials through the synthesis of SAPO-11 made with hard templates and by means of post-synthesis treatments samples of SAPO-11. Moreover, NbP has shown characteristic XRD of amorphous materials, with high acidity and were active in the conversion of hexadecane.

Polonium-210 and Lead-210 activities measured on 17 water bottle profiles and 50 surface water samples during POLARSTERN cruise ARK-XXII/2

Polonium-210 and Lead-210 have been measured in the water column and on suspended particulate matter during the POLARSTERN cruise ARK-XXII/2. The data have been submitted to Pangaea following a Polonium-Lead intercalibration exercise organized by GEOTRACES, where the AWI lab results range within the data standard deviation from 10 participating labs. Polonium-210 and Lead-210 in the ocean can be used to identify the sources and sinks of suspended matter. In seawater, Polonium-210 (210Po) and Lead-210 (210Pb) are produced by stepwise radioactive decay of Uranium-238. 210Po (138 days half life) and 210Pb (22.3 years half life) have high affinities for suspended particles. Those radionuclides are present in dissolved form and adsorbed onto particles. Following adsorption onto particle surfaces, 210Po especially is transported into the interior of cells where it bonds to proteins. In this way, 210Po also accumulates in the food chain. 210Po is therefore considered to be a good tracer for POC, and traces particle export over a timescale of month. 210Pb (22.3 years half life) adsorbs preferably onto structural components of cells, biogenic silica and lithogenic particles, and is therefore a better tracer more rapidly sinking matter. Our goal during ARK XXII/2 was to trace pathways of particulate and dissolved matter leaving the Siberian Shelf. The pathways of particulate and dissolved matter will be followed by the combined use of 210Po and 234Th as a tracer pair (and perhaps 210Pb) for particle flux (Cai, P.; Rutgers van der Loeff, MM (2008) doi:10.1594/PANGAEA.708354). This information gathered from the water column will be complemented with the results of the 210Po-210Pb study in sea ice (Camara-Mor, P, Instituto de Ciencias del Mar-SCIC, Barcelona, Spain) to provide a more thorough picture of particle transport from the shelf to the open sea and from surface to depth.

Biogenic components, major, trace and rare earth elements of equatorial Pacific Ocean surface sediments (Table 1)

We have analyzed the major, trace, and rare earth element composition of surface sediments collected from a transect across the Equator at 135°W longitude in the Pacific Ocean. Comparing the behavior of this suite of elements to the CaCO3, opal, and Corg fluxes (which record sharp maxima at the Equator, previously documented at the same sampling stations) enables us to assess the relative significance of the various pathways by which trace elements are transported to the equatorial Pacific seafloor. The 1. (1) high biogenic source at the Equator, associated with equatorial divergence of surface water and upwelling of nutrient-rich water, and 2. (2) high aluminosilicate flux at 4°N, associated with increased terrigenous input from elevated rainfall at the Intertropical Convergence Zone (ITCZ) of the tradewinds, are the two most important fluxes with which elemental transport is affiliated. The biogenic flux at the Equator transports Ca and Sr structurally bound to carbonate tests and Mn primarily as an adsorbed component. Trace elements such as Cr, As, Pb, and the REEs are also influenced by the biogenic flux at the Equator, although this affiliation is not regionally dominant. Normative calculations suggest that extremely large fluxes of Ba and P at the Equator are carried by only small proportions of barite and apatite phases. The high terrigenous flux at the ITCZ has a profound effect on chemical transport to the seafloor, with elemental fluxes increasing tremendously and in parallel with Ti. Normative calculations, however, indicate that these fluxes are far in excess of what can be supplied by lattice-bound terrigenous phases. The accumulation of Ba is greater than is affiliated with biogenic transport at the Equator, while the P flux at the ITCZ is only 10% less than at the Equator. This challenges the common view that Ba and P are essentially exclusively associated with biogenic fluxes. Many other elements (including Mn, Pb, As, and REEs) also record greater accumulation beneath the ITCZ than at the Equator. Thus, adsorptive scavenging by terrigenous paniculate matter, or phases intimately associated with them, appears to be an extremely important process regulating elemental transport to the equatorial Pacific seafloor. These findings emphasize the role of vertical transport to the sediment, and provide additional constraints on the paleochemical use of trace elements to track biogenic and terrigenous fluxes.

(Table 1) Sr, Nd and Os isotopic composition from marine sediments of the Bengal Fan

Sr, Nd, and Os isotopic data are presented for sediments from diverse locations in the Bay of Bengal. These data allow the samples to be divided into three groups, related to their sedimentary contexts. The first group, mainly composed of sediments from the shelf off Bangladesh and the currently active fan, has Sr and Nd characteristics consistent with a dominantly Himalayan source. Their 187Os/188Os ratios (~1.2-1.5) show that the average detrital material delivered by the Ganga-Brahmaputra (G-B) river system is not unusually radiogenic. A large difference in 187Os/188Os ratio exists between these Bengal Fan sediments and Ganga bedloads (187Os/188Os ~2.5, Pierson-Wickmann et al. (2000, doi:10.1016/S0012-821X(00)00003-0)). This difference mainly reflects addition of a less radiogenic Brahmaputra component, though mineralogical sorting and loss of radiogenic Os during transport may also play some role. The second sample group contains sediments from elsewhere in the Bay, particularly those located on the continental slope. They display Os isotopic compositions (0.99-1.11) similar to that of present seawater and higher Os and Re concentrations. These characteristics suggest the presence of a large hydrogenous contribution, consistent with the lower sedimentation rate of these samples. Sr and Nd ratios indicate that a significant fraction of these sediments is derived from erosion of non-Himalayan sources, such as the Indo-Burman range. These observations could be explained by the deflection of sediments from the G-B river system by westward currents in the head of the Bay. The third group contains only one sample, but shows that in addition to a Himalayan source, sediment discharge from Sri Lanka may influence the detrital component in the distal part of the fan. The similarity between the isotopic compositions of the group I R/V Sonne samples and those of Ocean Drilling Program Leg 116 (France-Lanord et al., 1993; Reisberg et al., 1997, doi:10.1016/S0012-821X(00)00003-0) suggests that the material eroding in the Himalayas has been roughly constant since the Miocene. The high Os isotopic ratios of leachates of both Sonne group I and Miocene Leg 116 sediments imply that much of the leachable highly radiogenic Os component was conserved during transport through the estuary or interaction with seawater. In constrast, samples with lower, but still relatively high, sedimentation rates (Sonne groups II and III and Pliocene Leg 116) seem to have significantly adsorbed or exchanged Os and Re with seawater. This suggests that in some cases the Os isotopic ratios of leachates of detrital sediments can be used to constrain the ancient marine Os record, or conversely, to date unfossiliferous sediments.