Typescript. / Thesis (Ph. D.)--University of Hawaii, 1964. / Bibliography: leaves [83]-86. / viii, 86 l tables, 12 mounted graphs

Typescript. / Thesis (Ph. D.)--University of Hawaii at Manoa, 1974. / Bibliography: leaves 160-167. / xiv, 167 leaves ill

A desorption technique was employed to evaluate chemisorption of ammonia by clays under moist conditions. In equilibria involving ammonia, all factors favoring volatilization losses of gaseous ammonia would undoubtedly exert an influence on the ultimate equilibria which are reached. Investigation of the relationship between pH and ammonia equilibria in soils revealed that an increase in the concentration of ammonium ions, applied as ammonium sulfate, stimulated ammonia losses from fine-textured soils at pH's ranging from 4.5 to 7.1. Ammonia volatilization was directly related to the initial pH of the soil and increased with an increase in pH. It was postulated that ammonia may be volatilized, even from acid soils, due to the equilibrium NH₄⁺ + OH⁻ ⇌ NH₃ + H₂O. By using initial concentrations of ammonium ions from ammonium sulfate applied, initial pH of an aqueous suspension of the soil and a value K_b = 1.80 x 10⁻⁵, values of ammonia losses were predicted. The linear relationship found between predicted and measured amounts of ammonia losses from acid as well as neutral soils, was interpreted as evidence of the existence of the proposed volatilization mechanism in soils. In attempting to evaluate the characteristics of ammonia retention by homo-ionic bentonites and kaolinites under moist conditions, it was found that base-saturated clays did not chemisorb ammonia in a fashion which could be described by Langmuir's adsorption isotherms. The S-shaped curves did not necessarily reflect polymolecular sorption. In strong contrast, chemisorption of ammonia by Al-saturated clays, followed Langmuir's equation almost perfectly. Evaluation of the inverse values of the differential slopes of two straight line segments obtained in the desorption isotherms corresponded closely to values obtained for the permanent charge (CEC) and the total charge (total CEC) developed at a specific pH higher than 6 respectively. It was shown that if sufficient ammonia is applied, exchangeable Al⁺⁺⁺ of Al-compounds may be precipitated as Al(OH)₃. An attempt to evaluate pseudo-equilibrium constants for aluminum-clay ammonia equilibria by using Langmuir's adsorption equation, was unsatisfactory. Chemical kinetic studies indicated that ammonia volatilization reactions could be described by a fast reaction and a slow reaction. The slow reaction represented chemisorption of ammonia on the permanent charge exchange sites. Extrapolation of the slow reaction to zero time yielded values corresponding closely to the CEC permanent charge. Investigation of the effects of CO₂, the NH₄⁺ concentration is increased, resulting in more effective replacement of basic cations for "permanent charge" exchange spots. The lower pH and higher effective NH₄⁺ concentration resulted in higher retention of NH₄⁺ in Na⁺- and K⁺-clays. The most striking retention of NH₄⁺ was obtained in Mg- and particularly in Ca-bentonites. It is believed that the Ca and Mg ions, exchanged by NH₄⁺ ions, are effectively removed from the soil solution as a result of the precipitation of these compounds which are sufficiently insoluble to ensure conservation of ammonia as chemisorbed ammonium ions. / Ph. D.

Call number: LD2668 .T4 1984 M93 / Master of Science

Indiana University-Purdue University Indianapolis (IUPUI) / The characterization of the nutrients nitrogen, phosphorus and carbon (NPC) export to streams during storms is an integral part of understanding processes affecting water quality. Despite the fact that excessive levels of these nutrients in the Mississippi River basin adversely affects water quality in the Gulf of Mexico, little research has been conducted on NPC dynamics during storms on larger (>20 km2) agriculturally dominated Midwestern watersheds. This project examined the storm export of nitrate, ammonium, total phosphorus, and dissolved organic carbon (DOC) in the upper Eagle Creek Watershed (UECW) (274 km2) in Central Indiana, USA. Water samples were collected during five winter and spring storms in 2007 and 2008 on the rising and falling limb of the hydrograph, in order to characterize NPC dynamics during storm events. Stream discharge and precipitation was monitored continuously, and major cations were used to examine changes in source water over the duration of the storm and assist in the determination of potential flowpaths. DOC, total P, and TKN (Total Kjeldahl Nitrogen) tended to peak with discharge, while nitrate usually exhibited a slight lag and peaked on the receding limb. Total phosphorus, NH3-, TKN, and DOC appear to be delivered to the stream primarily by overland flow. NO3--N appear to be delivered by a combination of tile drain and macropore flow. Overall UECW displayed smoother nutrient export patterns than smaller previously studied watersheds in the area suggesting that scale may influence nutrient export dynamics. Further research is underway on a 3000 km2 watershed in the area to further examine the role scale may play in nutrient export patterns.