Sorption and desorption of arsenic to ferrihydrite in a sand filter

Elevated arsenic concentrations in drinking water occur in many places around the world. Arsenic is deleterious to humans, and consequently, As water treatment techniques are sought. To optimize arsenic removal, sorption and desorption processes were studied at a drinking water treatment plant with aeration and sand filtration of ferrous iron rich groundwater at Elmevej Water Works, Fensmark, Denmark. Filter sand and pore water were sampled along depth profiles in the filters. The sand was coated with a 100-300 microm thick layer of porous Si-Ca-As-contaning iron oxide (As/Fe = 0.17) with locally some manganese oxide. The iron oxide was identified as a Si-stabilized abiotically formed two-line ferrihydrite with a magnetic hyperfine field of 45.8 T at 5 K. The raw water has an As concentration of 25 microg/L, predominantly as As(II). As the water passes through the filters, As(III) is oxidized to As(V) and the total concentrations drop asymptotically to a approximately 15 microg/L equilibrium concentration. Mn is released to the pore water, indicating the existence of reactive manganese oxides within the oxide coating, which probably play a role for the rapid As(III) oxidation. The As removal in the sand filters appears controlled by sorption equilibrium onto the ferrihydrite. By addition of ferrous chloride (3.65 mg of Fe(II)/L) to the water stream between two serially connected filters, a 3 microg/L As concentration is created in the water that infiltrates into the second sand filter. However, as water flow is reestablished through the second filter, As desorbs from the ferrihydrite and increases until the 15 microg/L equilibrium concentration. Sequential chemical extractions and geometrical estimates of the fraction of surface-associated As suggest that up to 40% of the total As can be remobilized in response to changes in the water chemistry in the sand filter.     

Soft interactions at nanoparticles alter protein function and conformation in a size dependent manner

Weak protein-nanoparticle (NP) interactions are studied in a low binding regime as a model for the soft protein corona around nanoparticles in complex biological fluids. Noncovalent, reversible interactions between Subtilisin Carlsberg (SC) and silica NPs shows significant alteration in conformation and enzymatic activity in a NP-size dependent manner. Very weak interactions between SC and silica NPs were revealed by centrifugation-based separations and further supported by small-angle X-ray scattering, while bovine serum albumin was used as a strongly interacting reference. Secondary and tertiary structure changes of SC were studied via circular dichroism and correlated to enzymatic activity where the enzyme kinetics showed a critical role for nanoparticle size.     

Electrospun polyethylene oxide (PEO) nanofibers containing cyclodextrin inclusion complex

In this study, we obtained functional electrospun nanofibers containing stable fragrance/flavor molecule facilitated by cyclodextrin inclusion complexation. Menthol was used as a model fragrance/flavor molecule and we have electrospun poly(ethylene oxide) (PEO) nanofibers containing cyclodextrin-menthol inclusion complexes (CD-menthol-IC). We used two different solvent systems; water and water:ethanol and three types of CDs; alpha-CD, beta-CD and gamma-CD in order to find the optimal performance for the stabilization of menthol at high temperatures. We observed that the solvent system used for electrospinning process and the types of CDs (alpha-CD, beta-CD and gamma-CD) are very important to obtain CD-menthol-IC which ultimately determines the durability and temperature stability of menthol in the PEO nanofibrous web. We found out that it is better to use water rather than the water:ethanol solvent system for the inclusion complexation and additionally beta-CD and gamma-CD are most favorable choices since they are able to form complexation with menthol in the water solvent system. Despite the high volatility nature of menthol, our results demonstrated that the stability and temperature release of menthol was sustained to a very high and a broad temperature range (100 degrees C-250 degrees C) for PEO nanowebs containing CD-menthol-IC whereas the PEO nanofibers without CD and without CD-menthol complex could not preserve menthol even during storage. In brief, the results are very encouraging and open up for a variety of new exciting possibilities for the development of multi-functional electrospun nanofibers containing cyclodextrin inclusion complexes.     

Mode of action and inhibition of polygalacturonase covalently bound to polysaccharide and glass carriers

Endo-polygalacturonase (EC 3.2.1.15.) from Aspergillus spec. is much changed as far as its mode of action and the interaction with vegetable inhibitors of pectinase (from green beans and cucumbers) are concerned when it is covalently bound to insoluble carriers (Sepharose, cellulose powder, macroporous glass and nonporous ballotinis). Whereas a 2% degradation of substrate by the soluble enzyme caused a 50% decrease of viscosity of citrus pectic acid, the comparable degradation of substrate was increased to a level of about 10% with the investigated polygalacturonase carrier complexes apparently independent of the properties of the carriers and the kind of binding of the enzyme. In contrast to this the higher degradation of substrate of 15 and 20% respectively which was further stated at a 50% decrease of viscosity is unambiguously connected with the carriers and is in direct correlation with the specific activity of the polygalacturonase carrier complexes. Contrary to the soluble enzyme the covalently bound enzyme produces more lower oligomerous galacturonic acids by an exo-mechanism or by multiple attack already at the beginning of the hydrolysis of pectic acid. During the final stage there is an enrichment of trigalacturonic acid besides mono- and digalacturonic acids independent of the state of solution of the enzyme. It could further be stated that the strong inhibition of the soluble endo-polygalacturonase by selected pectinase inhibitors which was described earlier is reduced by degrees with the enzyme covalently bound to the insoluble carriers.     

Sorption of the herbicide dichlobenil and the metabolite 2,6-dichlorobenzamide on soils and aquifer sediments

The worldwide used herbicide dichlobenil (2,6-dichlorobenzonitrile) has resulted in widespread presence of its metabolite 2,6-dichlorobenzamide (BAM) in pore- and groundwater. To evaluate the transport of these compounds we studied the sorption of dichlobenil and BAM in 22 sediment samples of clayey till, sand, and limestone including sediments exhibiting varying oxidation states. Dichlobenil sorbed to all investigated sediments, with a high sorption in topsoils (Kd = 7.4-17.4 L kg(-1)) and clayey till sediments (Kd = 2.7-126 L kg(-1)). The sorption of the polar metabolite BAM was much lower than the sorption of dichlobenil but followed the same tendency with the highest sorption in the topsoils (Kd = 0.24-0.66 L kg(-1)) and in the clayey till sediments (Kd = 0.10-0.93 L kg(-1)). The sorption of both compounds was significantly higher (2-47 times) in the unoxidized (reduced) clayey till than in the weathered (oxidized) clayey till. Such a difference in sorption capacity could neither be explained by a higher organic carbon content, sorption to clay minerals, differences in clay mineralogy, nor by blocking of reactive surface sites on clay minerals by iron oxides. However, by removing an average of 81% of the organic carbon from the reduced clayey till with H2O2, the sorption decreased on average 50%. Therefore, most of the sorption capacity in the reduced clayey till was related to organic carbon, which indicates that sorption processes are affected by changes in organic compound composition due to weathering.     

CO Desorption Rate Dependence on CO Partial Pressure over Platinum Fuel Cell Catalysts

Carbon monoxide adsorption on high area platinum fuel cell catalysts was investigated. Isotopic exchange experiments were performed to determine the exchange rate (k) of CO under different partial pressures of CO (p_CO) in argon. A linear dependence of ln(k) with ln(p_CO) was observed. This pressure dependence of the rate of exchange is explained by considering a change in surface coverage of CO with different CO pressures and a subsequent reduction in the CO binding energy as demonstrated by Density Functional Theory (DFT) calculations. High Pressure Scanning Tunneling Microscopy (HP STM) studies on the Pt(111) surface have also displayed a pressure dependency of the coverage consistent with this data. The relevance of these observations to the Polymer Electrolyte Membrane Fuel Cell (PEMFC) anode reaction is discussed.     

Synthesis and degradation of adenosine triphosphate in cod (Gadus morhua) at subzero temperatures

This study has demonstrated that the extraction step is very important when analysing ATP and its degradation products. An important factor is whether the sample is fresh, frozen or thawed when homogenised since thawing of the sample will lead to rapid loss of ATP. During frozen storage it was found that ATP in cod (Gadus morhua) was stable at −40 °C in small samples for at least 12 weeks. At −20 °C it was found that ATP content increases initially and thereafter falls. It was demonstrated that degradation of ATP in small samples occurs faster at 0 °C than at −2 and −5 °C. Furthermore, it was found that in whole cod ATP could be synthesised at a significant rate at −7 °C. © 1999 Society of Chemical Industry     

Interference of Cyclodextrins with Amylolytic Activity Assays of Cyclodextrin Glycosyltransferases

Cyclodextrin glycosyltransferases (CGTases) catalyse the cyclisation of starch dextrins to cyclodextrins and concomitantly show amylolytic activity which is commonly determined by the starch-iodine assay. In the present study it was found that cyclodextrins interfere with this assay. Adding cyclodextrins in concentrations ranging from 0.01mM to 0.6mM to starch-iodine complex solution resulted in a significant decrease in absorbance at 600nm due to α- and β-cyclodextrin competing with starch in the iodine complex formation. The largest reduction was caused by α-cyclodextrin. Therefore, the use of the starch-iodine assay will result in an overestimation of the amylolytic activity of CGTases – particularly when the enzyme has a high α-cyclodextrin production activity. In contrast, determination of the amylolytic activity by measurement of released reducing sugars with CuSO₄/bicinchonate was not disturbed by cyclodextrins.