Does reactive surface area depend on grain size? Results from pH 3, 25 circle C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 mu m were dissolved in pH 3, HCl at 25 degrees C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 X 10(-10) mol(feldspar) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 X 10(-10) mol(feldspar) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol(feldspar) g(-1) s(-1). For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 x 10(-12) mol(biotite) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 X 10(-12) mol(biotite) g(-1) s(-1). For all normalising terms rates varied significantly (p <= 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over wich they would change significantly. (c) 2006 Elsevier Inc. All rights reserved.

Thermopile radiometer signal conditioning for surface atmospheric radiation measurements

A highly stable microvolt amplifier for use with atmospheric broadband thermopile radiometers is described. The amplifier has a nominal gain of 500, for bipolar input signals in the range +/- 10 mV from a floating source. The noise level at the input is less than 5 mu V (at 100 k Omega input impedance), permitting instantaneous diffuse solar radiation measurements to 0.5 W m(-2) resolution with 12 bit analog to digital conversion. The temperature stability of gain is better than 5 ppm/degrees C (-4 to 20 degrees C). Averaged over a decade of use, the long term drift of the amplifier gain is less than similar to 0.02%/yr. As well as radiometers measuring solar and terrestrial radiations, the amplifier has also been successfully used with low level signals from thermocouples and ground heat flux plates.

Effect of pH, temperature and surface contact on the elaboration of fimbriae and flagella by Salmonella serotype Enteritidis

Survival of enteric pathogens exposed to various environmental stresses depends upon a number of protective responses, some of which are associated with induction of virulence determinants. Flagella and fimbriae are putative virulence determinants of Salmonella spp, and ELISAs specific for the detection of flagella and SEF21, SEF14 and SEF17 fimbriae were used to assess the effect of temperature and pH upon their elaboration by isolates of Salmonella serotype Enteritidis in planktonic growth and on the surface of two-dimensional gradient agar plates, For three phage type 4 isolates of Enteritidis of comparative clinical provenance, similar phenotypes for the elaboration of these surface antigens were observed. SEF14 fimbriae were elaborated in planktonic growth at 37 degrees C, but not 20 degrees C, at pH 4.77 and above but not at pH 4.04; whereas on agar gradient plates SEF14 fimbriae were elaborated poorly but with best yields at pH 4.04, SEF17 fimbriae were elaborated in planktonic growth at 20 degrees C, but not at 37 degrees C, at pH 6.18 and above but not at pH 5.09 or below; whereas on agar gradient plates SEF17 fimbriae were elaborated well even at pH 4.65, SEF21 fimbriae were expressed very poorly under all conditions tested, Planktonic growth at 37 degrees C induced least flagella whereas growth at 20 degrees C, and particularly surface growth at lower pH values, induced a 'hyper-flagellate' phenotype, Single colonies allowed to form on gradient agar plates were shown to generate different colonial morphologies which were dependent on initial pH. These results demonstrate that the physicochemical environment is an important determinant of bacterial response, especially the induction of putative virulence factors.

The influence of Fe-rich coatings on the dissolution of anorthite at pH 2.6

Surface coatings are very common on mineral grains in soils but most laboratory dissolution experiments are carried out on pristine, uncoated mineral grains. An experiment designed to unambiguously isolate the effect of surface coatings on mineral dissolution from any influence of solution saturation state is reported. Two aliquots of 53 to 63 mum anorthite feldspar powder were used. One was dissolved in pH 2.6 HCl, the other in pH 2.6 FeCl3 solution, both for similar to6000 h in flow-through reactors. An amorphous Fe-rich, Al-, Ca- and Si-free orange precipitate coated the anorthite dissolved in the FeCl3 solution. BET surface area of the anorthite increased from 0.16 to 1.65 m(2) g(-1) in the HCl experiment and to 3.89 m(2) g(-1) in the FeCl3 experiment. The increase in surface area in the HCl experiment was due to the formation of etch pits on the anorthite grain surface whilst the additional increase in the FeCl3 experiment was due to the micro- and meso-porous nature of the orange precipitate. This precipitate did not inhibit or slow the dissolution of the anorthite. Steady state dissolution rates for the anorthite dissolved in the HCl and FeCl3 were similar to2.5 and 3.2 X 10(-10) mol(feldspar) m(-2) s(-1) respectively. These rates are not significantly different after the cumulative uncertainty of 17% in their value due to uncertainty in the inputs parameters used in their calculation is taken into account. Results from this experiment support previous theoretical and inference-based conclusions that porous coatings should not inhibit mineral dissolution. Copyright (C) 2003 Elsevier Ltd.

Searching for the perfect surface area normalizing term - a comparison of BET surface area-, geometric surface area- and mass-normalized dissolution rates of anorthite and biotite

Dissolution rates were calculated for a range of grain sizes of anorthite and biotite dissolved under far from equilibrium conditions at pH 3, T = 20 degrees C. Dissolution rates were normalized to initial and final BET surface area, geometric surface area, mass and (for biotite only) geometric edge surface area. Constant (within error) dissolution rates were only obtained by normalizing to initial BET surface area for biotite. The normalizing term that gave the smallest variation about the mean for anorthite was initial BET surface area. In field studies, only current (final) surface area is measurable. In this study, final geometric surface area gave the smallest variation for anorthite dissolution rates and final geometric edge surface area for biotite dissolution rates. (c) 2005 Published by Elsevier B.V.

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH I experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost similar to 9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >similar to 2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction. (C) 2008 Elsevier Ltd. All rights reserved.

The development and contribution of surface charge by crop residues in two Malawian acid soils

The effects of maize and soya bean residues on the pH and charge of a loamy sand (Kawalazi) and a sandy clay loam (Naming'omba) from Malawi were measured to determine both the indirect effect of the residues on soil charge through the changes in pH, and the direct contribution of charge carried on the residue surfaces. The soils had pH values (10 mM CaCl2) of 4.3 and 5.0 and organic matter contents were 1.4% and 2.7%, respectively. The clay fractions were dominated by kaolinite and goethite, and mica was present in both samples. The soils were incubated for 28 days with maize (Zea mays) and soya bean (Glycine max) residues. The maximum addition of residue (12.0%) in the Kawalazi and Naming'omba soils increased the pH from 4.3 and 5.0 to 4.8 and 5.3 (maize) and to 9.0 and 8.8 (soya bean), respectively. Negative charge increased from 2.1 and 4.7 cmol(c) kg(-1) to 3.8 and 7.5 (maize) and to 5.3 and 9.3 cmol(c) kg(-1) (soya bean). Positive charge increased from 0.72 and 0.62 to 0.87 and 0.85 cmol(c) kg(-1) (maize) and to 0.75 and 0.68 (soya bean). The charge contribution by the residues was calculated by difference between the charge on a sample incubated with residue and the charge on a soil without residue limed to the same pH value. Up to 100 cmolc negative charge and 10 cmol(c) of positive charge per kg of residue were directly contributed to the soil-residue mixture, the amounts depending on the type of residue, the extent to which the residue was decomposed in the soil and the pH of the mixture. The Anderson and Sposito method [Soil Sci. Soc. Am. J. 55 (1991) 1569] was used to partition the permanent negative charge (holding Cs+) from variable negative charge (holding Li+). In the pH range 3.7-6.5 the maize residue contributed between 3 and 26 cmol(c) of variable charge per kg of residue in the Kawalazi soil and between 6 and 25 cmol(c) per kg of residue in the Naming'omba soil. For soya bean the values were between I and 28 and between 4 and 68 cmolc per kg of residue, respectively. At a given pH value, the charge tended to increase with time of incubation and for a given addition of residue, pH decreased during incubation. Addition of residues contributed no permanent negative charge and the charge on the soil measured by Cs adsorption was independent of pH change caused by the residue showing that the method is valid for soil-residue mixtures. With time there was a decrease in the amount of permanent charge probably due to masking as humic material become adsorbed on mineral surfaces. (C) 2003 Elsevier Science B.V. All rights reserved.

Effect of mycorrhizae and pH change at the root-soil interface on phosphorus uptake by Sorghum using a rhizocylinder technique

Sorghum (Sorghum bicolor) was grown for 40 days in. rhizocylinder (a growth container which permitted access to rh zosphere and nonrhizosphere soil), in two soils of low P status. Soils were fertilized with different rates of ammonium and nitrate and supplemented with 40 mg phosphorus (P) kg(-1) and inoculated with either Glomus mosseae (Nicol. and Gerd.) or nonmycorrhizal root inoculum.. N-serve (2 mg kg(-1)) was added to prevent nitrification. At harvest, soil from around the roots was collected at distances of 0-5, 5-10, and 10-20 mm from the root core which was 35 mm diameter. Sorghum plants, with and without mycorrhiza, grew larger with NH4+ than with NO3- application. After measuring soil pH, 4 3 suspensions of the same sample were titrated against 0.01 M HCl or 0.01 M NaOH until soil pH reached the nonplanted pH level. The acid or base requirement for each sample was calculated as mmol H+ or OFF kg(-1) soil. The magnitude of liberated acid or base depended on the form and rate of nitrogen and soil type. When the plant root was either uninfected or infected with mycorrhiza., soil pH changes extended up to 5 mm from the root core surface. In both soils, ammonium as an N source resulted in lower soil pH than nitrate. Mycorrhizal (VAM) inoculation did not enhance this difference. In mycorrhizal inoculated soil, P depletion extended tip to 20 mm from the root surface. In non-VAM inoculated soil P depletion extended up to 10 mm from the root surface and remained unchanged at greater distances. In the mycorrhizal inoculated soils, the contribution of the 0-5 mm soil zone to P uptake was greater than the core soil, which reflects the hyphal contribution to P supply. Nitrogen (N) applications that caused acidification increased P uptake because of increased demand; there is no direct evidence that the increased uptake was due to acidity increasing the solubility of P although this may have been a minor effect.

Fragrance release from the surface of branched poly(amide)s

Enzymes are powerful tools in organic synthesis that are able to catalyse a wide variety of selective chemical transformations under mild and environmentally friendly conditions. Enzymes such as the lipases have also found applications in the synthesis and degradation of polymeric materials. However, the use of these natural catalysts in the synthesis and the post-synthetic modification of dendrimers and hyperbranched molecules is an application of chemistry yet to be explored extensively. In this study the use of two hydrolytic enzymes, a lipase from Candida cylindracea and a cutinase from Fusarium solani pisii, were investigated in the selective cleavage of ester groups situated on the peripheral layer of two families of branched polyamides. These branched polyamides were conjugated to simple fragrances citronellol and L-menthol via ester linkages. Hydrolysis of the ester linkage between the fragrances and the branched polyamide support was carried out in aqueous buffered systems at slightly basic pH values under the optimum operative conditions for the enzymes used. These preliminary qualitative investigations revealed that partial cleavage of the ester functionalities from the branched polyamide support had occurred. However, the ability of the enzymes to interact with the substrates decreased considerably as the branching density, the rigidity of the structure and the bulkiness of the polyamide-fragrance conjugates increased.

pH-mediated interactions between poly(acrylic acid) and methylcellulose in the formation of ultrathin multilayered hydrogels and spherical nanoparticles

Poly(acrylic acid) forms insoluble hydrogen-bonded interpolymer complexes with methylcellulose in aqueous solutions under acidic conditions. In this work the reaction heats and binding constants were determined for the complexation between poly(acrylic acid) and methylcellulose by isothermal titration calorimetry at different pH and findings are correlated with the aggregation processes occurring in this system. The principal contribution to the complexation heat results from primary polycomplex particle aggregation. Transmission electron microscopy of nanoparticles produced at pH 1.4 and 2.4 demonstrated that they are spherical and dense structures. The nanoparticles ranged from 80 to 200 nm, whereas particles formed at pH 3.2 were 20-30 nm and were stabilized against aggregation by a network of uncomplexed macromolecules. For the first time, multilayered materials were developed on the basis of hydrogen-bonded complexes of poly(acrylic acid) and methylcellulose using layer-by-layer deposition on a glass surface. The thickness of these films was a linear function of the number of deposition cycles. The materials were subsequently cross-linked by thermal treatment, resulting in ultrathin hydrogels which detached from the glass substrate upon swelling. The swelling capacity of ultrathin hydrogels differed from the swelling of the thicker films of a similar chemical composition.

Optimization of electroless copper plating on polyethylene films modified by surface grafting of vinyl ether of monoethanolamine

Metallized plastics have recently received significant interest for their useful applications in electronic devices such as for integrated circuits, packaging, printed circuits and sensor applications. In this work the metallized films were developed by electroless copper plating of polyethylene films grafted with vinyl ether of monoethanoleamine. There are several techniques for metal deposition on surface of polymers such as evaporation, sputtering, electroless plating and electrolysis. In this work the metallized films were developed by electroless copper plating of polyethylene films grafted with vinyl ether of monoethanoleamine. Polyethylene films were subjected to gamma-radiation induced surface graft copolymerization with vinyl ether of monoethanolamine. Electroless copper plating was carried out effectively on the modified films. The catalytic processes for the electroless copper plating in the presence and the absence of SnCl2 sensitization were studied and the optimum activation conditions that give the highest plating rate were determined. The effect of grafting degree on the plating rate is studied. Electroless plating conditions (bath additives, pH and temperature) were optimized. Plating rate was determined gravimetrically and spectrophotometrically at different grafting degrees. The results reveal that plating rate is a function of degree of grafting and increases with increasing grafted vinyl ether of monoethanolamine onto polyethylene. It was found that pH 13 of electroless bath and plating temperature 40°C are the optimal conditions for the plating process. The increasing of grafting degree results in faster plating rate at the same pH and temperature. The surface morphology of the metallized films was investigated using scanning electron microscopy (SEM). The adhesion strength between the metallized layer and grafted polymer was studied using tensile machine. SEM photos and adhesion measurements clarified that uniform and adhered deposits were obtained under optimum conditions.

Mechanisms of burst release from pH-responsive polymeric microparticles.

Microencapsulation of drugs into preformed polymers is commonly achieved through solvent evaporation techniques or spray drying. We compared these encapsulation methods in terms of controlled drug release properties of the prepared microparticles and investigated the underlying mechanisms responsible for the “burst release” effect. Using two different pH-responsive polymers with a dissolution threshold of pH 6 (Eudragit L100 and AQOAT AS-MG), hydrocortisone, a model hydrophobic drug, was incorporated into microparticles below and above its solubility within the polymer matrix. Although, spray drying is an attractive approach due to rapid particle production and relatively low solvent waste, the oil-in-oil microencapsulation method is superior in terms of controlled drug release properties from the microparticles. Slow solvent evaporation during the oil-in-oil emulsification process allows adequate time for drug and polymer redistribution in the microparticles and reduces uncontrolled drug burst release. Electron microscopy showed that this slower manufacturing procedure generated non-porous particles whereas thermal analysis and X-ray diffractometry showed that drug loading above the solubility limit of the drug in the polymer generated excess crystalline drug on the surface of the particles. Raman spectral mapping illustrated that drug was homogeneously distributed as a solid solution in the particles when loaded below saturation in the polymer with consequently minimal burst release.

Using pH abnormalities in diseased skin to trigger and target topical therapy

Abstract Purpose: The pH discrepancy between healthy and atopic dermatitis skin was identified as a site specific trigger for delivering hydrocortisone from microcapsules. Methods: Using Eudragit L100, a pH-responsive polymer which dissolves at pH 6, hydrocortisone-loaded microparticles were produced by oil-in-oil microencapsulation or spray drying. Release and permeation of hydrocortisone from microparticles alone or in gels was assessed and preliminary stability data was determined. Results: Drug release from microparticles was pH-dependent though the particles produced by spray drying also gave significant non-pH dependent burst release, resulting from their porous nature or from drug enrichment on the surface of these particles. This pH-responsive release was maintained upon incorporation of the oil-in-oil microparticles into Carbopol- and HPMC-based gel formulations. In-vitro studies showed 4 to 5-fold higher drug permeation through porcine skin from the gels at pH 7 compared to pH 5. Conclusions: Permeation studies showed that the oil-in-oil generated particles deliver essentially no drug at normal (intact) skin pH (5.0 – 5.5) but that delivery can be triggered and targeted to atopic dermatitis skin where the pH is elevated. The incorporation of these microparticles into Carbopol- and HPMC-based aqueous gel formulations demonstrated good stability and pH-responsive permeation into porcine skin.

Influence of fermentation conditions on the surface properties and adhesion of Lactobacillus rhamnosus GG

Background: The surface properties of probiotic bacteria influence to a large extent their interactions within the gut ecosystem. There is limited amount of information on the effect of the production process on the surface properties of probiotic lactobacilli in relation to the mechanisms of their adhesion to the gastrointestinal mucosa. The aim of this work was to investigate the effect of the fermentation pH and temperature on the surface properties and adhesion ability to Caco-2 cells of the probiotic strain Lactobacillus rhamnosus GG. Results: The cells were grown at pH 5, 5.5, 6 (temperature 37 °C) and at pH 6.5 (temperature 25 °C, 30 °C and 37 °C), and their surfaces analysed by X-ray photoelectron spectrometry (XPS), Fourier transform infrared spectroscopy (FT-IR) and gel-based proteomics. The results indicated that for all the fermentation conditions, with the exception of pH 5, a higher nitrogen to carbon ratio and a lower phosphate content was observed at the surface of the bacteria, which resulted in a lower surface hydrophobicity and reduced adhesion levels to Caco-2 cells as compared to the control fermentation (pH 6.5, 37 oC). A number of adhesive proteins, which have been suggested in previous published works to take part in the adhesion of bacteria to the human gastrointestinal tract, were identified by proteomic analysis, with no significant differences between samples however. Conclusions: The temperature and the pH of the fermentation influenced the surface composition, hydrophobicity and the levels of adhesion of L. rhamnosus GG to Caco-2 cells. It was deduced from the data that a protein rich surface reduced the adhesion ability of the cells.

Long-term conditioning of soil by plantation eucalypts and pines does not affect growth of the native jarrah tree

Plant species can condition the physico-chemical and biological properties of soil in ways that modify plant growth via plant–soil feedback (PSF). Plant growth can be positively affected, negatively affected or neutrally affected by soil conditioning by the same or other plant species. Soil conditioning by other plant species has particular relevance to ecological restoration of historic ecosystems because sites set aside for restoration are often conditioned by other, potentially non-native, plant species. We investigated changes in properties of jarrah forest soils after long-term (35 years) conditioning by pines (Pinus radiata), Sydney blue gums (Eucalyptus saligna), both non-native, plantation trees, and jarrah (Eucalyptus marginata; dominant native tree). Then, we tested the influence of the conditioned soils on the growth of jarrah seedlings. Blue gums and pines similarly conditioned the physico-chemical properties of soils, which differed from soil conditioning caused by jarrah. Especially important were the differences in conditioning of the properties C:N ratio, pH, and available K. The two eucalypt species similarly conditioned the biological properties of soil (i.e. community level physiological profile, numbers of fungal-feeding nematodes, omnivorous nematodes, and nematode channel ratio), and these differed from conditioning caused by pines. Species-specific conditioning of soil did not translate into differences in the amounts of biomass produced by jarrah seedlings and a neutral PSF was observed. In summary, we found that decades of soil conditioning by non-native plantation trees did not influence the growth of jarrah seedlings and will therefore not limit restoration of jarrah following the removal of the plantation trees.