The anisotropic etching behavior of single-crystal silicon and the behavior of SiO2 and Si3N4 in an ethylenediaminebased solution as well as in aqueous KOH, NaOH, and LiOH were studied. The crystal planes bounding the etch front and their etch rates were determined as a function of temperature, crystal orientation, and etchant composition. A correlation was found between the etch rates and their activation energies, with slowly etching crystal surfaces exhibiting higher activation energies and vice versa. For highly concentrated KOH solutions, a decrease of the etch rate with the fourth power of the water concentration was observed. Based on these results, an electrochemical model is proposed, describing the anisotropic etching behavior of silicon in all alkaline solutions. In an oxidation step, four hydroxide ions react with one surface silicon atom, leading to the injection of four electrons into the conduction band. These electrons stay localized near the crystal surface due to the presence of a space charge layer. The reaction is accompanied by the breaking of the backbonds, which requires the thermal excitation of the respective surface state electrons into the conduction band. This step is considered to be rate limiting. In a reduction step, the injected electrons react with water molecules to form new hydroxide ions and hydrogen. It is assumed that these hydroxide ions generated at the silicon surface are consumed in the oxidation reaction rather than those from the bulk electrolyte, since the latter are kept away from the crystal by the repellent force of the negative surface charge. According to this model, monosilicic acid Si(OH)4 is formed as the primary dissolution product in all anisotropic silicon etchants. The anisotropic behavior is due to small differences of the energy levels of the backbond surface states as a function of the crystal orientation.
The etching behavior of highly boron doped silicon in aqueous solutions based of ethylenediamine, KOH, NaOH, and LiOH was studied. For all etchants, a strong reduction of the etch rate for boron concentrations exceeding approximately 2 9 10 ~9 cm -3 was observed. This value is in good agreement with published data for the onset of degeneracy of p-type silicon. The reduction of the etch rate was found to be inversely proportional to the fourth power of the boron concentration.
The microbial degradation of hydrocarbons was studied in an artificially contaminated sandy soil, using a pilot-scale percolator system. After a short lag period, an intensive degradation occurred, which diminished in time and completely stopped in the end, despite large residual contaminations (residues of 56% diesel fuel, 20% n-hexadecane and 3.5% phenanthrene at the initial loadings of each 3000 mg/kg). The remaining pollutant content was influenced by the kind of hydrocarbon but was nearly independent of its initial loading. According to a model-aided analysis of the carbon dioxide production during remediation, the observed stagnation of degradation was caused by a limited bioavailability of the pollutants. The degradation in the soil-free aqueous phase was more extensive than in the soil, which suggests that the limited bioavailability in the soil can be attributed mainly to matrix-dependent rather than substrate-dependent influences. Generally, fine particles and organic matter are mainly responsible for the adsorption of pollutants to the soil matrix. Our sandy soil also bound hydrocarbons adsorptively although it contained neither silty material nor significant amounts of organic matter. As shown by Brunauer Emmett Teller (BET) analysis, the soil particles were covered by micropores, which enlarged the soil surface by a factor of 120 in comparison with the macroscopic surface area. The microporosity is the reason for the hydrocarbons being more strongly adsorbed to the sandy soil than expected.
The core stages of a sediment remediation process--the conditioning of dredged sludge by plants and the solid-bed leaching of heavy metals using microbially produced sulfuric acid--were tested on a pilot scale using a highly polluted river sediment. Conditioning was performed in 50 m3 basins at sludge depths of 1.8 m. During one vegetation period the anoxic sludge turned into a soil-like oxic material and became very permeable to water. Reed canary grass (Phalaris arundinacea) was found to be best suited for conditioning. Bioleaching was carried out in an aerated solid-bed reactor of 2000 L working volume using oxic soil-like sediment supplemented with 2% sulfur. When applying conditioned sediment, the oxidation of easily degradable organic matter by heterotrophic microbes increased the temperature up to 50 degrees C in the early leaching phase, which in turn temporarily inhibited the sulfur-oxidizing bacteria. Nevertheless, most of the metal contaminants were leached within 21 days. Zn, Cd, Mn, Co, and Ni were removed by 61-81%, Cu was reduced by 21%, while Cr and Pb were nearly immobile. A cost-effectiveness assessment of the remediation process indicates it to be a suitable treatment for restoring polluted sediments for beneficial use.
The objective of the present study was to compare the concentrations of acute phase proteins and selected variables of protein metabolism in dairy cows of the Slovak Spotted breed from 4 weeks before parturition to 10 weeks after parturition. Acute phase proteins -haptoglobin (Hp) and serum amyloid A (SAA) -and variables of protein metabolism -total proteins, albumin, urea, creatinine, total immunoglobulins -were evaluated in blood serum. Significant differences were found in average values of the Hp and SAA concentrations in several groups during the monitored period (P < 0.05 and P < 0.001, respectively). The Hp and SAA concentrations in cows during the early postparturient period were significantly higher compared with the later postparturient period. Throughout the monitored time we found differences in mean values of total proteins (P < 0.001), urea (P < 0.001), and total immunoglobulins (P < 0.05). The concentrations of albumin decreased progressively in the postparturient period until 4 weeks after parturition. In the assessment of correlations between the monitored variables in the mentioned period we found significant correlations between Hp and SAA (r = 0.916; P < 0.001), total proteins and urea (r = 0.668; P < 0.05), total proteins and total immunoglobulins (r = 0.827; P < 0.01), and between total immunoglobulins and urea (r = 0.899; P < 0.001). The above mentioned results indicate that in the time around parturition there are significant changes in concentrations of acute phase proteins, as well as in the whole protein metabolism of dairy cows. These facts suggest that the postparturient period is a critical biological phase, throughout which there is the highest incidence of metabolic disorders.Haptoglobin, serum amyloid A, periparturient period, protein profile
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