Many studies have been undertaken to determine the effects of soil and soil properties on migrating metal pollutants. Organic pollutants, however, in addition to their interactions with soil components , are also susceptible to degradation (catabolism) by microorganisms. Soil-microorganism-pollutant interactions have, traditionally, been studied in soil columns (microcosms). One of the shortcomings of column and in situ studies is that the identity and specific effect(s) of the soil component(s) affecting or influencing attenuation are not known and cannot readily be determined. Attenuation effects of the soil components are, therefore, difficult to interpret. ("Attenuation" in this context is the combined effects of both soil adsorption and microbial catabolism). Attenuation studies often only consider the physical conditions such as aeration, permeability, flow rate, temperature, etc. This approach assumes the soil to be a homogeneous matrix with no specific physico-chemical properties attributable to different components within the matrix. Soil physical factors suspected of influencing pollutant attenuation could be misleading without consideration of the physico-chemical interactions between soil components, microorganisms and pollutants. Adhesion of pollutants and microorganisms seems to be most important in this regard. The initial phase of this study was undertaken to examine the effects of three different soil materials on attenuation of key landfill leachate molecules. Examination of the effects of soil surface type on attenuation focused on adsorption / desorption of the pollutant molecules and microorganisms. These experiments sought to investigate the physico-chemical effects of soil, microorganism, pollutant interactions and were done as batch slurry experiments as well as in soil columns. Two soil horizons from the Inanda soil form (humic A and red apedal B) and the topsoil (vertic A) from a Rensburg soil form were used. The Inanda topsoil had a high organic matter content and both the topsoil and subsoil had a kaolinitic clay mineralogy; the Rensburg topsoil clay mineralogy was predominantly smectitic with a relatively low organic matter content. From the batch experiments, the adsorption of a hydrophobic molecule (naphthalene) and a heavy metal (cadmium) were found to be influenced to a significant extent by soil characteristics. Adsorption of naphthalene was due to the soil organic matter (SOM) content whereas cadmium adsorption was due to the cation exchange capacity (CEC) of the soil. Soil characteristics did not seem to have a significant influence on the adsorption of a water soluble compound such as phenol at the concentrations used. Attenuation of naphthalene was found to be affected by adsorption of the pollutant molecule (related to SOM) as well as the CEC of the soil. The attenuation of hydrophobic molecules can possibly be ascribed to the influence of CEC on the microbial population responsible for attenuation. This would seem to indicate interaction between the soil surfaces and the catabolizing microbial population. Desorption of the pollutant (and possibly also of the microbial population) was achieved by the addition of acetonitrile and methanol both of which reduced the polarity of the water. These solvents were also found to be toxic to the catabolizing microbial population at high concentrations. The toxicity thresholds of both solvents for catabolizing microorganisms differed significantly between soil- (> 15 %, v/v) and soil free (< 5 %, v/v) treatments. This discrepancy cannot be accounted for by adsorption and is ascribed to physico-chemical interaction between microorganisms and the soil surfaces. This interaction probably affords protection from, otherwise, toxic concentrations of solvents or metals. The important effects of soil surfaces on attenuation processes were thought to be due to the strong adsorption of naphthalene. Surface attachment of microorganisms was, however, also inferred from results obtained with phenol. This seemed to indicate that microbial attachment to soil surfaces was an important aspect in attenuation and did not occur only because of pollutant adsorption. Soil column experiments were made with both naphthalene and phenol. The naphthalene, which was adsorbed to the soil, did not leach from the columns to any appreciable extent. This was despite the addition of acetonitrile to some columns. This was probably due to greater microbial catabolism caused by desorption and, subsequent, increased soluble concentrations of the molecule. After extraction from the soil at the end of the experiment it was clear that the sterile controls held much higher concentrations of naphthalene than the experimental columns. The soil type and treatments showed little difference in the naphthalen concentration extracted from the soil columns. This did not reflect the differences found between soil materials in the batch experiments and was probably due to the masking effect of the soil physical factors on attenuation processes. Unlike naphthalene, phenol, because of its high solubility, was detected in the column leachates at relatively high concentrations. The phenol concentrations were much higher for the Inanda subsoil (approximately 4 mM) than the Inanda topsoil (approximately 2 mM) and Rensburg topsoil (< 1 mM). The Rensburg topsoil produced the lowest phenol concentrations in the leachate and this can probably be ascribed to the larger quantity of micropores in this soil. Thus, it seems that the soil physical features had a pronounced influence on attenuation. Whether this effect was directly on the studied molecule or indirectly, because of the effects on the microbial population, is not known. Inoculation of the columns with a phenol catabolizing population had only a slight increased effect on leachate phenol concentrations from all columns. This increased effect was, however, only prolonged in the case of the Inanda subsoil. The flow rate through the columns affected leachate phenol concentration which was lower with a slower flow rate and, thus, longer retention time. From the column experiments soil physical parameters were suspected of influencing, and possibly overriding, the soil surface effects on microbial activity (capacity to catabolize a organic molecule of interest). Soil porosity, as caused by different soil materials, was suspected of being the most important soil physical parameter influencing microbial activity. To investigate the potential effect of soil porosity, relatively homogeneous porous media i.e. chromatography packing material and acid washed sand were used. These materials had more defined and distinct porosities and were considered to be suitable for investigating the fundamental influence of porosity on microbial activity. Saturated continuous flow columns were used and three types of packing configurations were tested: chromatography packing (CHROM) material (porous particles); acid washed sand (non-porous) (AWS); and a 1: 1 (w/w) mixture of chromatography packing and acid washed sand (MIX). Only a single water soluble molecule, phenol, was used in this phase of the investigation. Bacterial filtration ("filtration" as a component of "attenuation'') was found to be highest for the CHROM and lowest for the AWS materials. This difference in microbial retention affected the phenol catabolism in response to increased column dilution rates. The CHROM and MIX materials had distinctly different porosities than that of the AWS, due to the internal porosity of the chromatography packing. This greater pore size distribution in the MIX and CHROM packing materials created pores with different effective pore dilution rates within the microcosms at similar overall flow rates. The greater pore size distribution in the MIX and CHROM packing materials facilitated pore colonization since some pores did not participate, or conduct, mass flow as occurred in macropores. This led to different microcolonization effects in the macro- vs micropores. Since the MIX and CHROM packing materials had more micropore colonization sites these packing materials showed a greater range of substrate affinities (i.e. Ks values) for the phenol substrate. The extent to which micropore colonization occurred could be detected by the effect it had on phenol breakthrough curves. In the MIX and CHROM materials, microbial colonization caused blocking of micropores with a subsequent effect on the phenol breakthrough curves. The AWS material, however, which had a low inherent microporosity, showed microbially induced microporosity probably due to biofilm development. The fact that the MIX and CHROM packing materials facilitated micropore colonization was also responsible for the greater resistance to, and the recovery from , potentially inhibitory cadmium concentrations. This effect was also apparent in the presence of acetonitrile, although this effect was not identical to that observed with cadmium. Finally, column pressure build up as a function of pore clogging was determined and was found to occur in the order AWS > MIX > CHROM. This was most likely due to fewer potential liquid flow paths with a higher blocking potential in the AWS. Extrapolation of the fundamentals of the above findings led to the conclusion that soil surface- and soil porosity effects are extremely important factors in determining the behavior of soils as bioreactors. / Thesis (Ph.D.)-University of Natal, Pietermaritzburg, 1995.

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Crop-available zinc is affected by P-Zn interactions in soils. Orthophosphate (OP) additions may decrease or have no effect, while pyrophosphate (PP) may increase or have no effect on Zn solubility. Mechanisms involved in the interactions are not well understood and need to be quantified on agricultural soils subjected to P fertilization. / Top and sub-samples from three Quebec agricultural soils were equilibrated with OP or PP solutions, then with Zn solutions, and finally with solutions containing neither P nor Zn. The first equilibration evaluated P sorption effects on soil cation exchange capacity (CEC), the second equilibration evaluated Zn sorption (Zn$ sb{ rm s}$) after P sorption, and the third Zn desorption (Zn$ sb{ rm D}$) as related to added P. Subsequently, Zn fractions were extracted sequentially with KNO$ sb3$ (Zn$ sb{ rm KNO3}$), NaOH (Zn$ sb{ rm NaOH}$) solutions and concentrated HNO$ sb3$ + H$ sb2$O$ sb2$ (Zn$ sb{ rm HNO3}$). Autoclaved soils were used for OP and PP comparisons, and non-autoclaved soils were used for OP determinations. / Autoclaving reduced dithionite-citrate extractable Fe and Al materials. In both autoclaved and non-autoclaved soils, one mmole sorbed P as PP or OP resulted in increases in CEC from 0.52-1.24 mmole (+). Comparison between OP and PP in the autoclaved soils indicated that the increased CEC per mmole sorbed was greater with sorbed OP than with PP, while at the same rate of P addition, the absolute increased CEC was more with sorbed PP than with OP due to greater P sorption as PP compared to OP. Both sorbed OP or PP in autoclaved soils and sorbed OP in non-autoclaved soils increased specific Zn sorption in association with oxide materials. The effect was more significant with PP than with OP, as indicated by the observations: (1) P sorption increased Zn sorption but reduced Zn desorption, (2) P sorption reduced KNO$ sb3$- but increased NaOH- and HNO$ sb3$-extractable Zn, and (3) P sorption increased the difference between Zn sorbed and Zn extracted with KNO$ sb3$. These effects were more significant in coarser than finer textured soils. Results suggested that Zn fertilizers should be separated from P fertilizers to avoid enhanced Zn sorption and reduced Zn desorption.

Hydrolysis and adsorption-desorption reaction of pyrophosphate (PP) and orthophosphate (OP) were studied in two Quebec soils (St. Bernard and Dalhousie) and three minerals (goethite, kaolinite, and montmorillonite). Soil and soil mineral samples were fractionated by size into two separates. / Soil and goethite samples adsorbed more OP than PP whereas kaolinite and montmorillonite adsorbed similar amounts of OP and PP. Pyrophosphate and orthophosphate adsorption was found to be related significantly to extractable Fe. Furthermore, kaolinite and montmorillonite desorbed similar amounts of OP and PP whereas more OP than PP was desorbed from soil and goethite samples. Moreover, adsorption of OP and PP was found to be mainly chemical adsorption. Smaller particle size induced higher P adsorption and desorption from both P sources compared with the coarse particle size. / Goethite samples had slower rates of hydrolysis compared to soil and clay mineral samples. Furthermore, kalolinite and montmorillonite did not increase the rate of PP hydrolysis even with reduced adsorption of PP compared to soil and goethite samples. Chemical hydrolysis was found to be a significant portion of the total hydrolysis. Smaller particle size and high PP adsorption induced smaller PP hydrolysis than with coarse particles. Moreover, added OP reduced the amount of PP remaining nonhydrolyzed. First-order rates of PP hydrolysis were faster in nonautoclaved than autoclaved samples. Rate of PP hydrolysis increased with increased temperature and the effect of temperature was more obvious in the autoclaved than nonautoclaved samples.

Typescript. / Thesis (Ph. D.)--University of Hawaii at Manoa, 1974. / Bibliography: leaves 191-204. / xvii, 204 leaves ill

Thesis (M.S. - Watershed Management)--University of Arizona. / Includes bibliographical references.

Thesis(M.S.)--Auburn University, 2006. / Abstract. Includes bibliographic references.

Thesis (Ph. D.)--University of Adelaide, Dept. of Soil Science, 1995. / Includes bibliographical references.