Two ex situ fungal technologies to treat contaminated soil

Wood-degrading fungi are able to degrade a large range of recalcitrant pollutants which resemble the lignin biopolymer. This ability is attributed to the production of lignin-modifying enzymes, which are extracellular and non-specific. Despite the potential of fungi in bioremediation, there is still an understanding gap in terms of the technology. In this thesis, the feasibility of two ex situ fungal bioremediation methods to treat contaminated soil was evaluated. Treatment of polycyclic aromatic hydrocarbons (PAHs)-contaminated marsh soil was studied in a stirred slurry-phase reactor. Due to the salt content in marsh soil, fungi were screened for their halotolerance, and the white-rot fungi Lentinus tigrinus, Irpex lacteus and Bjerkandera adusta were selected for further studies. These fungi degraded 40 - 60% of a PAH mixture (phenanthrene, fluoranthene, pyrene and chrysene) in a slurry-phase reactor (100 ml) during 30 days of incubation. Thereafter, B. adusta was selected to scale-up and optimize the process in a 5 L reactor. Maximum degradation of dibenzothiophene (93%), fluoranthene (82%), pyrene (81%) and chrysene (83%) was achieved with the free mycelium inoculum of the highest initial biomass (2.2 g/l). In autoclaved soil, MnP was the most important enzyme involved in PAH degradation. In non-sterile soil, endogenous soil microbes together with B. adusta also degraded the PAHs extensively, suggesting a synergic action between soil microbes and the fungus. A fungal solid-phase cultivation method to pretreat contaminated sawmill soil with high organic matter content was developed to enhance the effectiveness of the subsequent soil combustion. In a preliminary screening of 146 fungal strains, 28 out of 52 fungi, which extensively colonized non-sterile contaminated soil, were litter-decomposing fungi. The 18 strains further selected were characterized by their production of lignin-modifying and hydrolytic enzymes, of which MnP and endo-1,4-β-glucanase were the main enzymes during cultivation on Scots pine (Pinus sylvestris) bark. Of the six fungi selected for further tests, Gymnopilus luteofolius, Phanerochaete velutina, and Stropharia rugosoannulata were the most active soil organic matter degraders. The results showed that a six-month pretreatment of sawmill soil would result in a 3.5 - 9.5% loss of organic matter, depending on the fungus applied. The pretreatment process was scaled-up for a 0.56 m3 reactor, in which perforated plastic tubes filled with S. rugosoannulata growing on pine bark were introduced into the soil. The fungal pretreatment resulted in a soil mass loss of 30.5 kg, which represents 10% of the original soil mass (308 kg). Despite the fact that Scots pine bark contains several antimicrobial compounds, it was a suitable substrate for fungal growth and promoter of the production of oxidative enzymes, as well as an excellent and cheap natural carrier of fungal mycelium. This thesis successfully developed two novel fungal ex situ bioremediation technologies and introduce new insights for their further full-scale application. Ex situ slurry-phase fungal reactors might be applied in cases when the soil has a high water content or when the contaminant bioavailability is low; for example, in wastewater treatment plants to remove pharmaceutical residues. Fungal solid-phase bioremediation is a promising remediation technology to ex situ or in situ treat contaminated soil.

Ethylation of benzene: A statistical study

A central composite rotatable experimental design was constructed for a statistical study of the ethylation of benzene in the liquid phase, with aluminum chloride catalyst, in an agitated tank system. The conversion of benzene and ethylene and the yield of monoethyl- and diethylbenzene are characterized by the response surface technique. In the experimental range studied, agitation rate has no significant effect. Catalyst concentration, rate of ethylene Flow, and temperature are the influential factors. The response surfaces may be adequately approximated by planes.

Catalytic cracking of acetic acid to acetic anhydride

Catalytic cracking of acetic acid using triethyl phosphate and silica gel catalysts was investigated. The desired reaction leading to ketene is accompanied by side reactions: two parallel with respect to acetic acid decomposition and the consecutive ketene decomposition reactions. Effect of temperature, catalyst concentration, space velocity, and pressure was studied in detail. Triethyl phosphate was found to be a much better catalyst than silica gel. The optimum yield of ketene was obtained at 750° C, 100 mm. of Hg pressure, and apparent contact time of 5.687 × 10-4 hour.

A Mechanistic Model for the Water-Gas Shift Reaction over Noble Metal Substituted Ceria

The water-gas shift (WGS) reaction was carried out in the presence of Pd and Pt substituted nanocrystalline ceria catalysts synthesized by solution combustion technique. The catalysts were characterized by powder XRD and XPS. The noble metals were found to be present in ionic form substituted for the cerium atoms. The catalysts showed highactivity for the WGS reaction with high conversions below 250 degrees C. The products of reaction were only carbon dioxide and hydrogen, and no hydrocarbons were observed even in trace quantities. The reactions were carried out with different amounts of noble metal ion substitution and 2% Pt substituted ceria was found to be the best catalyst. The various possible mechanisms for the reaction were proposed and tested for their consistency with experimental data. The dual site mechanism best described the kinetics of the reaction and the corresponding rate parameters were obtained.

Benedict-Webb-Rubin equation of state constants for N2O4 ⇄ 2NO2,NO,and O2

Benedict-Webb-Rubin equation of state constants for NO, O2, and the equilibrium mixture N2O4 ⇄ 2NO2 are reported.

Vapor-liquid equilibrium data for the system n-heptane-n-butyl alcohol at medium pressures

Vapor-liquid equilibrium data for the system n-heptane-n-butyl alcohol at pressures of 1445, 2205, 2965, and 3725 mm. of Hg have been reported. The data are correlated with Chao's modified Redlich-Kister equation.

Oxidation of acetaldehyde to acetic acid in a sparger reactor

The kinetics of oxidation of acetaldehyde to acetic acid was studied in a sparger reactor using manganese acetate as the catalyst. Data obtained in a stirred tank reactor are used for analyzing the sparger reactor data. The rate of chemical reaction is extremely fast and can be neglected for the rate equation of the sparger reactor. A kinetic model applicable at any temperature and concentration within the range of the variables studied is developed which predicts the performance of the sparger reactor satisfactorily.

Vapor-liquid equilibrium data for the systems diisopropyl ether-n-heptane and diisopropyl ether-carbon tetrachloride at medium pressures

Vapor-liquid equilibrium data for the systems diisopropyl ether-n-heptane and diisopropyl ether-carbon tetrachloride have been reported at pressures of 760, 1520, and 2280 mm. of Hg. The systems form ideal mixtures under the pressure range studied.

A novel fibre-coated sorbent for rapid removal of heavy metals from wastewater. Sorption of Zinc(II) from dilute aqueous solutions in the presence of high concentrations of common salts

The commercial acrylic fibre "Cashmilon" was partially hydrolyzed to convert a fraction of its nitrile (-CN) groups to carboxylic acid (-COOH) groups and then coated with polyethylenimine (PEI) resin and cross-linked with glutaraldehyde to produce a novel gel-coated fibrous sorbent with multiple functionalities of cationic, anionic and chelating types, and significantly faster sorption kinetics than bead-form sorbents. The sorption properties of the fibrous sorbent were measured using Zn(II) in aqueous solution as the sorbate to determine the effects of pH and the presence of common ions in the solution on the sorption capacity. The rate of sorption on the gel-coated fibre was measured in comparison with that on Amberlite IRA-68 weak-base resin beads, to demonstrate the marked difference between fibre and bead-form sorbents in their kinetic behaviour.

A novel sheet 4f-3d mixed-metal pyridine dicarboxylate: synthesis, structure, photophysical properties and its transformation to a perovskite oxide

The synthesis, characterization and photophysical properties of a 4f-3d mixed metal compound, Gd(H2O)(3)Co[C5N1H3-(COO)(2)](3), are described; the structure is unique, consisting of sheets with large pores ( ca. 7 angstrom diameter) in the sheets and transforms to a perovskite oxide at moderate temperatures.

Thermal Conductivities of Organic Liquids-A New Correlation.

A new equation for predicting the thermal conductivities of organic liquids using dimension-less analysis is given. The equation (Equation Presented) correlates 51 different liquids tested within 11% average error and 17% standard deviation. A comparison of the proposed equation with the available correlations and its application to some industrially important liquids show that this equation can be safely used to calculate the thermal conductivities at 20°C. and 1 atm. pressure for organic liquids of known molecular weight. Cp and ΔHv - the only two parameters for which experimental values must be known for making use of this equation - can be calculated using other well known correlations. The proposed equation is not applicable to inorganic liquids.

On latent heat of vaporization, surface tension, and temperature

A semitheoretical equation for latent heat of vaporization has been derived and tested. The average error in predicting the value at the normal boiling point in the case of about 90 compounds, which includes polar and nonpolar liquids, is about 1.8%. A relation between latent heat of vaporization and surface tension is also derived and is shown to lead to Watson's empirical relation which gives the change of latent heat of vaporization with temperature. This gives a physico-chemical justification for Watson's empirical relation and provides a rapid method of determining latent heats by measuring surface tension.