Exposed weathering profiles of a series of Pololu lava flows in Kohala, Hawaii are ideal for investigating the sequence of reactions/reaction pathways of weathered basalt. Weathering reactions for saprolites show mineral sequences that include feldspar → halloysite ± gibbsite + solutes; clinopyroxene → hematite + minor halloysite + solutes; olivine → hematite + solutes; magnetite → hematite or other Fe-oxides/hydroxides. However, the presence of smectite in four samples suggests that smectite-group clays may form as short lived intermediates at the base of the weathering profile. Regionally, on Kohala, soils and saprolites are dominated by halloysite with small quantities of other clays such as kaolinite, gibbsite, and smectite. However, one horizon in the weathering profile at the study site in Kohala is dominated by gibbsite. Smectite is found at the base of the profile above impermeable areas where mass leaching has left increased alkaline and alkaline earth elemental (Mg, Ca, Na, and K) abundances relative to the parent rock. The amount of elemental gain varies from -5% to +75% for samples with smectite. Different climates generate different weathering profile depths. MASW (multi-channel analysis of surface waves) shows that the depth of the weathering profile is 15 meters. Seismic profiles correlate the depth of the weathering profile inland (~15 meters), with cliff face (~13 meters). Other than the gibbsite horizon, most mineral zones are too thin to be resolved through second-order velocity variations. P-wave reflection surveys are unsuitable for imaging the base of the weathering front because the transition to fresh rock may be gradational. However, within the saprolite section, boundaries between relict lava flow textures produce reflections that mimic expected stratigraphic patterns. Perpendicular to the shoreline, reflectors dip gently seaward, whereas parallel to the shoreline, lenticular packages of relict lava flows are observed.

Aflatoxin is a potent biological toxin produced by fungi Aspergillus flavus and A. parasiticus. Current quantification methods for aflatoxins are mostly established on immunoaffinity columns which are both costly and labor intensive. Inspired by smectites’ high aflatoxin adsorption capacity and affinity, a novel aflatoxin quantification sensor based on smectite-polyacrylamide (PAM) nanocomposite was fabricated. First, a smectite-PAM nanocomposite film was synthesized on flat silicon substrates which assembled smectite particles from the clay suspension. A layer-by-layer assembly process was developed to achieve uniform morphology and thickness of the nanocomposite films. During the aflatoxin quantification process, positive correlations between the fluorescence intensity from the aflatoxin B1 (AFB1) adsorbed smectite-PAM nanocomposite films and the AFB1 concentration in the test solutions were obtained. The smectite-PAM nanocomposite film has shown similar AFB1 adsorption capabilities as the smectite. Second, the smectite-PAM nanocomposite film was optimized in order to achieve the aflatoxin quantification at ppb level (below 20ppb) in corn extraction solutions. The smectite was modified by Ba2+, which had demonstrated to be able to improve its aflatoxin adsorption capacity. PAM aqueous solutions with the mass concentration ranging from 0.8% to 0.001% were tested. The results showed that the nanocomposite synthesized from 0.005% concentration of PAM solution generated the best properties. After the optimization, the smectite-PAM nanocomposite films achieved the detection of aflatoxin B1, B2, G1 and G2 (AFB2, AFG1 and AFG2) in 10 ppb corn extraction solution. Aflatoxin quantifications in AFB1 and AFB2 mixture solution, AFB1 and AFB2 mixture solution and AFB1 and AFG1 mixture solution were conducted, and the recoveries of last test ranged from 90.52% to 110.11% at low aflatoxin concentration (below 20 ppb). Third, in order to shorten the quantification duration and simplify the detection process, a novel aflatoxin detection array based on smectite-PAM nanocomposite and an improved fluorometric quantification method were developed. Through a microfluidic chip, the reaction time was reduced to 10~20min. Two concentration levels (20~80ppb/5~15ppb) of aflatoxin B1 spiked corn extraction solutions were tested. In the fluorometric quantification step, a common lab-use 365 nm ultraviolet lamp replaced the spectrofluorometer which simplified and accelerated the process.

Smectite clay has been shown in studies over the past 20 years to sorb aflatoxin B1 (AfB1) in animal feed and thereby reduce its toxic influence on animals. In this study, 20 smectite samples were selected from industrial products or reference minerals. In the initial steps, it was shown that AfB1 entered the interlayer galleries of smectites and a 10-fold range in sorption ability was observed in a set of 20 smectite samples. Yet, it was not clear which clay properties (CEC, pH, base saturation) influenced this variation. In an effort to further explore properties that might influence the sorption of AfB1, three good sorbent samples were chosen from our set of 20 samples along with one sample of low sorption capacity. Those samples were fractionated into sand, silt, coarse clay (CC), and fine clay (FC) fractions. From all sample fractions, sorption isotherms and X-ray diffraction patterns were obtained. Additionally, a vermiculite and a palygorskite were examined with regard to sorption capacity. Concentration of smectite and their adsorption test suggest that differences in smectite composition are responsible for difference in sorption, not so much their relative abundance or other mineral phases. Initial infrared analysis indicates that weathered aluminous smectites, which have no octahedral iron or magnesium, belong to the poor AfB1 sorbents. Palygorskite and vermiculite are not effective sorbents. Based on the findings in this study, tentative quality criteria of sorbent selection for their use in animal feed were established. These criteria are: pH between 6.5 and 8.5, CEC > 75cmolc/kg, organic carbon < 2.5 g/kg, expression of XRD smectite peak and AlFeOHbending in FTIR and Langmuir adsorption capacity for AfB1 > 0.40 mol/kg.

The proportion of authigenic to detrital clay minerals in terrestrial sediments is variable. It has previously been hypothesized that pure Mg-silicates in regions such as Amboseli Basin in Kenya occur due to the absence of Al-rich detritus. We tested this by replicating two Mg-silicate synthesis experiments while adding Al-rich smectite. The first study produced an X-ray amorphous Mg-silicate gel, with little response to addition of Al-rich smectite. The second experiment shifted the 060 peak associated with clay octahedral sheets, suggesting we synthesized trioctahedral domains in a smectite structure. Peak height increased linearly with more heating, indicating crystallinity changes. These results confirm that Al-rich detritus can influence the mineralogy of authigenic clays in saline, alkaline settings. By examining how clay neoformation is affected by silica saturation, we can better understand how the clays found in Neogene lacustrine environments are formed and the climate and of that time.

A Portuguese clay (BRN) from the North East city of Bragança was collected and characterized in terms of health treatment and applied towards the preparation of nanocomposites with Polylactide (PLA). The silt-clay fraction of BRN is mainly composed of smectite with less illite, kaolinite and other minerals. The physicochemical properties are applicable for the topical applications and are mainly influenced by smectite. With the hazardous elements present, further bioavailability tests should be conducted. PLA nanocomposites with BRN and Wyoming montmorillonite SWy-2 (MMT) were respectively prepared through the solution casting method with ultrasonic stirring and using cetyltrimethylammonium bromide (CTAB) as the surfactant. The X-ray diffraction patterns show the exfoliated structures in most samples. Thermal gravimetric analysis reveals the increased thermal stability of the nanocomposites. The complexes were also characterized by nitrogen adsorption, infrared analysis and nuclear magnetic resonance for comparing the differences between BRN and MMT.

Title from PDF of title page (University of Missouri--Columbia, viewed on March 2, 2010). The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file. Dr. William Likos, Thesis Supervisor. Vita. Includes bibliographical references.

Orientador: Meuris Gurgel Carlos da Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-15T16:01:50Z (GMT). No. of bitstreams: 1 Bertagnolli_Caroline_M.pdf: 6983617 bytes, checksum: 383caf10321743b4b7b79a1b893b1b0d (MD5) Previous issue date: 2010 / Resumo: Argilas bentonitas depois de submetidas a tratamentos químicos aumentam suas potencialidades para maior variedade de uso na remediação ambiental. As argilas organofílicas preparadas a partir de sais quaternários de amônio, que possuam pelo menos uma cadeia com 12 ou mais carbonos, destacam-se como adsorvente para separação de compostos orgânicos da água. Neste trabalho, foram obtidas argilas organofílicas a partir das argilas esmectitas do tipo Verde-Lodo e Bofe provenientes do município de Boa Vista - PB, utilizando os sais quaternários cloreto de cetil piridínio e cloreto de benzalcônio. A argila comercial Spectrogel, fornecida pela empresa Spectrochem também foi estudada para fins de comparação com as amostras produzidas em laboratório. O material obtido foi caracterizado por difração de raios-X, microscopia eletrônica de varredura, espectroscopia de raios-X por energia dispersiva, termogravimetria, calorimetria diferencial de varredura, espectroscopia na região do infravermelho e fisissorção de N2. As argilas modificadas tiveram sua afinidade avaliada em ensaios de capacidade de hidratação em água, sorção e expansão em derivados do petróleo, no caso, gasolina, óleo diesel, óleo lubrificante e querosene. Para o conjunto argila/derivado do petróleo que apresentou melhor comportamento e para amostra comercial, foram realizadas cinéticas de remoção e ensaios em banho finito a temperatura ambiente, para avaliar a separação deste poluente presente em meio aquoso. Os resultados da caracterização indicam a efetivação do processo de organofilização e as mudanças ocorridas na estrutura física e química das argilas. Os ensaios de capacidade de hidratação mostraram a falta de afinidade da argila modificada pela água, enquanto os ensaios de sorção e expansão confirmam o caráter organofílico, evidenciando o potencial de uso das argilas modificadas como alternativa aos tratamentos existentes para remoção de compostos orgânicos de água / Abstract: Bentonite clays organically modified with quaternary ammonium salt, whose features enable the interaction with organic compounds, have great potential use for environmental remediation such as adsorption of organic compounds from wastewater. In this work, organophilic clays 'Verde-Lodo' and 'Bofe' bentonite from the State of Paraíba (Brazil) were organofilizated by intercalation of two different quaternary salts. The surfactants used were cetyl-pyridinium chloride and benzalkonium chloride. The commercial clay Spectrogel, provided by Spectrochem, was also studied for comparison with samples produced in laboratory. The obtained material had been characterized by use of X-ray diffraction, scanning electron microscopy, energy dispersive X-ray techniques, termogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy and N2 adsorption-desorption. The organophilic character was evaluated by swelling capacity test in water. The clay likeness for petroleum derived: gasoline, diesel oil, lubricant oil and kerosene oil were defined by sorption and swelling tests. The clay/petroleum derived that showed the best performance and commercial clay were performed kinetic removal and bath sorption, to evaluate the separation of this pollutant in water. The hydrophobic and organophilic character were observed by swelling capacity test in water, sorption and swelling tests. The potential for removal of petroleum derived from wastewaters was verified, it was showing potential use for environmental remediation / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

A Portuguese clay (BRN) from the North East city of Bragança was collected and characterized in terms of health treatment and applied towards the preparation of nanocomposites with Polylactide (PLA). The silt-clay fraction of BRN is mainly composed of smectite with less illite, kaolinite and other minerals. The physicochemical properties are applicable for the topical applications and are mainly influenced by smectite. With the hazardous elements present, further bioavailability tests should be conducted. PLA nanocomposites with BRN and Wyoming montmorillonite SWy-2 (MMT) were respectively prepared through the solution casting method with ultrasonic stirring and using cetyltrimethylammonium bromide (CTAB) as the surfactant. The X-ray diffraction patterns show the exfoliated structures in most samples. Thermal gravimetric analysis reveals the increased thermal stability of the nanocomposites. The complexes were also characterized by nitrogen adsorption, infrared analysis and nuclear magnetic resonance for comparing the differences between BRN and MMT.

Shrinking and swelling in Yazoo Clay is a cause of concern for construction projects in Mississippi. This thesis investigated the effects of adding lime and Douglas Fir biochar on the shrinking and swelling capabilities of Yazoo Clay. Samples of Yazoo Clay were mixed with the additives in defined ratios and subjected to the free swell test and the COLE(rod) test. Biochar addition reduced the COLE(rod) of the samples a large amount, while increasing the swelling potential of the clay samples. The addition of lime slightly reduced both the shrinking and swelling potentials of the samples. The mineralogical variability of Yazoo Clay vertically and horizontally could limit the applicability of these results across the formation and is important to be considered before further application. While constrained to one location, this study showed the influence of biochar and lime on the shrinking and swelling capabilities of Yazoo Clay.

No description available.